K-H_2 Quasi-molecular absorption detected in the T-dwarf epsilon Indi Ba

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基于双分子识别荧光猝灭法高选择性测定多巴胺

合成的 MBA- DSP- CdT e QDs 探针具有光学性质稳定、发射光谱宽而且连续, 同时还具有很宽的荧光激发波长范围, 其发射峰峰形近似对称, 半峰宽约 60 nm ; 与多巴胺结合后, M BA- DSP- CdT e QDs 探针( 542 nm) 到 M BA- DSP- CdT e QDs 探针的发射波长逐渐红移, 且荧光强度逐渐被猝灭( 图 4) 。 3. 3 pH 值的影响
4 冰箱中存放, 利用该探针分别在 7, 30, 60 和
120 d 进行对多巴胺进行测定, 测定结果的相对偏差分别为 3. 8% , 4. 1% , 3. 5% 和 5. 2% , 结果表明该探针至少
在 120 d 内, 能够使用, 且测定结果良好。为了研究制备
的探针的重现性, 对该探针分别用于 4 种浓度( 0. 5, 1. 0, 5. 0 和 10. 0 mmol/ L) 多巴胺的测定, 每个浓度测定5 次,
在邻苯二甲酸氢钾- 氢氧化钠、醋酸-醋酸钠、磷酸氢二钠- 柠檬酸、PBS 缓冲介质中进行测定。结果表明, PBS 缓冲溶液最适宜。探针荧光强度变化的适宜酸度范围为 pH 5. 5~ 8. 0。pH = 7. 4 时, 荧光强度强且与生物体液中酸度基本一致, 适宜用量为 1. 2~ 1. 8 mL 。因此在后续实验中选择 1. 5 m L pH
2011-04- 09 收稿; 2011-05-12 接受本文系国家自然科学基金 ( N os. 21175058, 51003039 ) , 山东省自然科学基金 ( N o. ZR2011BQ 019 ) , 山东省科技发展计划 ( N os . 2011GG B01153, 2009G G 20003022) 资助

Bethe Ansatz Solutions and Excitation Gap of the Attractive Bose-Hubbard Model

a r X i v :c o n d -m a t /0108314v 1 [c o n d -m a t .s t a t -m e c h ] 20 A u g 2001Bethe Ansatz Solutions and Excitation Gap of the Attractive Bose-Hubbard ModelDeok-Sun Lee and Doochul KimSchool of Physics,Seoul National University,Seoul 151-747,KoreaThe energy gap between the ground state and the ﬁrst excited state of the one-dimensional attractive Bose-Hubbard Hamiltonian is investigated in connection with directed polymers in random media.The excitation gap ∆is obtained by exact diagonalization of the Hamiltonian in the two-and three-particle sectors and also by an exact Bethe Ansatz solution in the two-particle sector.The dynamic exponent z is found to be 2.However,in the intermediate range of the size L where UL ∼O (1),U being the attractive interaction,the eﬀective dynamic exponent shows an anomalous peak reaching high values of 2.4and 2.7for the two-and the three-particle sectors,respectively.The anomalous behavior is related to a change in the sign of the ﬁrst excited-state energy.In the two-particle sector,we use the Bethe Ansatz solution to obtain the eﬀective dynamic exponent as a function of the scaling variable UL/π.The continuum version,the attractive delta-function Bose-gas Hamiltonian,is integrable by the Bethe Ansatz with suitable quantum numbers,the distributions of which are not known in general.Quantum numbers are proposed for the ﬁrst excited state and are conﬁrmed numerically for an arbitrary number of particles.I.INTRODUCTIONThe dynamics of many simple non-equilibrium sys-tems are often studied through corresponding quantum Hamiltonians.Examples are the asymmetric XXZ chain Hamiltonian and the attractive Bose-Hubbard Hamilto-nian for the single-step growth model [1]and the directed polymers in random media (DPRM)[2],respectively.The single-step growth model is a Kardar-Parisi-Zhang (KPZ)universality class growth model where the inter-face height h (x,t )grows in a stochastic manner under the condition that h (x ±1,t )−h (x,t )=±1.The process is also called the asymmetric exclusion process (ASEP)in a diﬀerent context.The evolution of the probability distri-bution for h (x,t )is generated by the asymmetric XXZ chain Hamiltonian [3].The entire information about the dynamics is coded in the generating function e αh (x,t ) .Its time evolution,in turn,is given by the modiﬁed asym-metric XXZ chain Hamiltonian [4–6],H XXZ (α)=−L i =1e 2α/L σ−i σ+i +1+12L i =1(b i b †i +1+b †i b i +1−2)−UL i =1b †ib i (b †ib i −1)4Lρ(1−ρ)and −n√4Lρ(1−ρ)≫1and the density of particles is ﬁ-nite in the limit L →∞,∆(α)behaves as ∆(α)∼L −1.However,when α∆(α)∼L−3/2[3,11].The dynamic exponent z=3/2is a characteristic of the dynamic universality class of the KPZ-type surface growth.When the number of par-ticles isﬁnite and the density of particles is very low, it is known that∆(α)∼L−2[12].However,whenα<0,which corresponds to the ferromagnetic phase, most Bethe Ansatz solutions are not available althoughthe Bethe Ansatz equations continue to hold.Asαbe-comes negative,the quasi-particle momenta appearing inthe Bethe Ansatz equations become complex,so solutions are diﬃcult to obtain analytically.The attractive Bose-Hubbard Hamiltonian is expected to have some resemblance to the ferromagnetic phaseof the asymmetric XXZ chain Hamiltonian consider-ing the equivalence ofαand−n.The equivalence isidentiﬁed indirectly by comparing the two scaling vari-ablesα LU under the relation U= 4ρ(1−ρ)or the two generating functions exp(αh(x,t) and Z(x,t)n under the relation Z(x,t)=e−h(x,t).In contrast to the asymmetric XXZ chain Hamiltonian,theBose-Hubbard Hamiltonian does not satisfy the Bethe Ansatz except in the two-particle sector[13].Instead, the attractive delta-function Bose-gas Hamiltonian,H D(n)=−1∂x2i−Ui<jδ(x i−x j),(4)which is the continuum version of the attractive Bose-Hubbard Hamiltonian,is known to be integrable by the Bethe Ansatz.The attractive delta-function Bose gas has been studied in Refs.[14]and[15].The ground-state energy is obtained from the Bethe Ansatz solution by us-ing the symmetric distribution of the purely imaginary quasi-particle momenta.However,the structure of the energy spectra is not well known for the same reason as in the asymmetric XXZ chain Hamiltonian withα<0. The unknown energy spectra itself prevents one from un-derstanding the dynamics of DPRM near the stationary state.In this paper,we discuss in Section II the distribu-tion of the quantum numbers appearing in the Bethe Ansatz equation for theﬁrst excited state of the attrac-tive delta-function Bose-gas Hamiltonian,the knowledge of which is essential for solving the Bethe Ansatz equa-tion.In Section III,the excitation gap of the attractive Bose-Hubbard Hamiltonian with a small number of par-ticles is investigated through the exact diagonalization method.We show that the gap decays as∆∼L−2,i.e., z=2,but that the exponent becomes anomalous when U∼L−1.The emergence of the anomalous exponent is explained in connection with the transition of theﬁrst excited state from a positive energy state to a negative energy state.The Bethe Ansatz solutions in the two-particle sector show how the behavior of the gap varies with the interaction.We give a summary and discussion in Section IV.II.QUANTUM NUMBER DISTRIBUTION FOR THE FIRST EXCITED STATEIn this section,we study the Bethe Ansatz solutions for the ground state and theﬁrst excited state of the attrac-tive delta-function Bose-gas Hamiltonian.The eigenstate of H D(n),Eq.(4),is of the formφ(x1,x2,...,x n)= P A(P)exp(ik P1x1+ik P2x2+···+ik P n x n),(5)where P is a permutation of1,2,...,n and x1≤x2≤...≤x n with no three x’s being equal.The quasi-particle momenta k j’s are determined by solving the Bethe Ansatz equations,k j L=2πI j+ l=jθ(k j−k l2+j,(j=1,2,...,n),(7)and the quasi-particle momenta are distributed symmet-rically on the imaginary axis in the complex-k plane. Care should be taken when dealing with theﬁrst excited state.For the repulsive delta-function Bose-gas Hamilto-nian,where U is replaced by−U in Eq.(4),the quantum numbers for one of theﬁrst excited states areI j=−n+12.(8)However,for the attractive case,by following the move-ment of the momenta as U changes sign,weﬁnd that the quantum numbers for theﬁrst excited state should be given byI j=−n−12(=I1).(9)That is,the two quantum numbers I1and I n become the same.Such a peculiar distribution of I j’s does not ap-pear in other Bethe Ansatz solutions such as those for the XXZ chain Hamiltonian or the repulsive delta-function Bose-gas Hamiltonian.We remark that even though the two I j’s are the same,all k j’s are distinct;otherwise,the wavefunction vanishes.Such a distribution of quan-tum numbers is conﬁrmed by the consistency between the energies obtained by diagonalizing the Bose-HubbardHamiltonian exactly and those obtained by solving the Bethe Ansatz equations with the above quantum num-bers for very weak interactions,for which the two Hamil-tonians possess almost the same energy spectra.When there is no interaction(U=0),all quasi-particlemomenta,k j’s,are zero for the ground state while for theﬁrst excited state,all the k j’s are zero except thelast one,k n=2π/L.In the complex-k plane,as the very weak repulsive interaction is turned on,the n−1momenta are shifted inﬁnitesimally from k=0withk1<k2<···<k n−1,and the n th momentum is shifted inﬁnitesimally to the left from k=2π/L.All the mo-menta remain on the real axis.When the interaction is weakly attractive,the n−1momenta become complexwith Im k1<Im k2<···<Im k n−1and Re k j≃0for j=1,2,...,n−1,and the n th momentum remains on thereal axis,but is shifted to the left.Figure1shows the dis-tribution of the quantum numbers and the quasi-particlemomenta in the presence of a very weak attractive in-teraction.The quasi-particle momenta are obtained by solving Eq.(6).Knowledge of the distribution of the quantum num-bers is essential for solving the Bethe Ansatz equations of the attractive delta-function Bose-gas Hamiltonian.For the original attractive Bose-Hubbard Hamiltonian,the Bethe Ansatz solutions are the exact solutions for the two-particle sector only,but are good approximate so-lutions in other sectors provided the density is very low and the interaction is very weak.This is because the Bethe Ansatz for the Bose-Hubbard Hamiltonian fails once states with sites occupied by more than three parti-cles are included.Thus,for the sectors with three or more particles,the Bethe Ansatz solutions may be regarded as approximate eigenstates provided states with more than three particles at a site do not play an important role in the eigenfunctions.In Ref.[13],it is shown that the error in the Bethe Ansatz due to multiply-occupied sites (occupied by more than three particles)is proportional to U2,where U(>0)in Ref.[13]corresponds to−U in Eq.(2).This applies to the attractive interaction case also.For the repulsive Bose-Hubbard Hamiltonian,the Bethe Ansatz is a good approximation when the density is low and the interaction is strong because the strong re-pulsion prevents many particles from occupying the same site[16].For the attractive Bose-Hubbard Hamiltonian, the Bethe Ansatz is good when the density is low and the interaction is weak because a weak attraction is better for preventing many particles from occupying the same site and because the error is proportional to U2.III.POWER-LA W DEPENDENCE ANDANOMALOUS EXPONENTWe are interested in the scaling limit L→∞with the scaling variable n√byE 0=−4sinh 2 κ2Lcosh2q 2L sinh2q2sinh κ−U,(12)andqL =logU +2cos(πU −2cos(π2s κ−s U,(14)which gives s κ≃1.151.When the size of the system L is increased by δL with U =U∗,the changes of κand q ,δκand δq ,are,from Eqs.(12)and (13),δκ=−πs κ(4s κ2−s U 2)L 2≡−πΓδL(4/π)s U −s U 2+4δLL 2.(15)The perturbative expansion ∆(L +δL )≃∆(L )(1−z (δL/L )),under the assumption that ∆(L )∼L −z ,gives the value of z eﬀat U ∗:z eﬀ=21+s κΓ+Σlog((L −1)/(L +1))(17)by using the solutions of Eqs.(12)and (13)for suﬃciently large L .As discussed above,the exponent z eﬀshows an anomalous peak near U =U ∗or UL/π=s U and ap-proaches 2.0as UL/π→0or ∞.Figure 6shows a plot of z eﬀversus the scaling variable UL/πat L =10000.IV.SUMMARY AND DISCUSSIONAs the asymmetric XXZ chain generates the dy-namics of the single-step growth model,the attractive Bose-Hubbard Hamiltonian governs the dynamics of the DPRM.We studied the attractive Bose-Hubbard Hamil-tonian and its continuum version,the attractive delta-function Bose-gas Hamiltonian concentrating on the be-havior of the excitation gap,which is related to the char-acteristics of DPRM relaxing into the stationary state.For the attractive delta-function Bose gas Hamiltonian,The quantum numbers for the ﬁrst excited state in the Bethe Ansatz equation are found for the attractive delta-function Bose gas Hamiltonian,and the distribution of the quasi-particle momenta is discussed in the presence of a very weak attractive interaction.Our result is the start-ing point for a further elucidation of the Bethe Ansatz solutions.We show that the excitation gap depends on the size of the system as a power law,∆∼L −z ,and that the exponent z can be calculated by using an exact diag-onalization of the attractive Bose-Hubbard Hamiltonian in the two-and the three-particle sectors and by using the Bethe Ansatz solution in the two-particle sector.The exponent z is 2.0.However,for the intermediate region where UL ∼O (1),the eﬀective exponent z eﬀshows a peak.The equivalence of the diﬀerential equations govern-ing the single-step growth model and DPRM implies some inherent equivalence in the corresponding Hamil-tonians.The power-law behavior of the excitation gap,∆∼L −2,for the attractive Bose-Hubbard Hamiltonian with a very weak interaction is the same as that for the asymmetric XXZ chain Hamiltonian with a small num-ber of particles,which is expected considering the rela-tion U =4ρ(1−ρ).The fact that the excitation gap behaves anomalously for U ∼L −1implies the possibility of an anomalous dynamic exponent z for a ﬁnite scaling variable n√[1]M.Plischke,Z.Racz,and D.Liu,Phys.Rev.B 35,3485(1987).[2]M.Kardar,Nucl.Phys.B 290[FS20],582(1987).[3]L.H.Gwa and H.Spohn,Phys.Rev.A 46,844(1992).[4]B.Derrida and J.L.Lebowitz,Phys.Rev.Lett.80,209(1998).[5]D.-S.Lee and D.Kim,Phys.Rev.E 59,6476(1999).[6]B.Derrida and C.Appert,J.Stat.Phys.94,1(1999).[7]J.Krug and H.Spohn,in Solids Far from Equilibrium ,edited by C.Godr´e che (Cambridge University Press,Cambridge,1991),p.412.[8]B.Derrida and K.Mallick,J.Phys.A 30,1031(1997).[9]S.-C.Park,J.-M.Park,and D.Kim,unpublished.[10]E.Brunet and B.Derrida,Phys.Rev.E 61,6789(2000).[11]D.Kim,Phys.Rev.E 52,3512(1995).[12]M.Henkel and G.Sch¨u tz,Physica A 206,187(1994).[13]T.C.Choy and F.D.M.Haldane,Phys.Lett.90A ,83(1982).[14]E.H.Lieb and W.Liniger,Phys.Rev.130,1605(1963).[15]J.G.Muga and R.F.Snider,Phys.Rev.A 57,3317(1998).[16]W.Krauth,Phys.Rev.B 44,9772(1991).(a)ω-0.10.1-0.50.5(b)Re k Im k 0FIG.1.For the ﬁrst excited state,(a)the quantum num-bers I j ’s are depicted in the complex-ωplane with ω=e 2πiI/L and (b)the quasi-particle momenta k j ’s are shown in the complex-k plane.Here,the size of the system L is 20,the number of particles n is 10,and the attractive interaction U is 0.0025.The ﬁlled circle in (a)is where the two quantum numbers overlap.0.5 1102030EL n =2 U =0.05ground state first excited state0.5 1102030EL n =2 U =0.5ground state first excited state-3.4-3.3-3.2 102030EL n =2 U =5ground state first excited state0.5 11020 30EL n =3 U =0.05ground state first excited state-0.5 0 0.5 1020 30ELn =3 U =0.5ground state first excited state-12.17-12.16-12.15 1020 30ELn =3 U =5ground state first excited stateFIG.2.Ground-state energies and ﬁrst excited-state ener-gies are plotted versus the size of the system L (4≤L ≤30)for U =0.05,0.5,and 5in the two-and the three-particle sectors.The dotted line represents E =0.For all values of U and L ,the ground-state energy is negative.On the other hand,when U =0.5,the excited-state energy becomes nega-tive near L ≃14in the two-particle sector and L ≃6in the three-particle sector.The signs of the excited-state energies for U =0.05and 5do not change in the range of L shown here.0.0010.010.1110102030∆LU=0.05U=0.5U=5FIG.3.Log-log plot of the excitation gaps (∆)versus the size of the system (L )in the two-particle sector.Data for U =0.05and 5approach straight lines with slope z =2.0,but those for U =0.5show a strong crossover before approach-ing the asymptotic behavior.The solid line for U =0.5is that ﬁtted in the range 14≤L ≤18,and shows an eﬀective z ≃2.4.0.00010.001 0.010.1110102030∆LU=0.05U=0.5U=5FIG.4.Same as in Fig.3,but for the three-particle sec-tor.The ﬁtted solid line used the data for 8≤L ≤12,and has a slope of approximately 2.7.(a)k (b)k FIG.5.Distributions of the quasi-particle momenta,k j ’s,for the ground state (ﬁlled circles)and the ﬁrst excited state (open circles)are shown in the complex-k plane for n =2.The size of the system L is 100and the interaction U is (a)0.001and (b)0.1.22.22.4s U510z e f fU L/πFIG.6.Eﬀective exponent z eﬀin the two-particle sector versus the scaling variable UL/πat L =10000.The interac-tion U varies from 0.0001to 0.001.At UL/π=s U ≃2.181,z eﬀ≃2.401.。

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J. Photochem. and Photobiol. C; Photochem. Rev. 2004, 5, 169-182

Journal of Photochemistry and Photobiology C:Photochemistry Reviews5(2004)169–182ReviewDiarylethene as a photoswitching unitKenji Matsuda,Masahiro Irie∗Department of Chemistry and Biochemistry,Graduate School of Engineering,Kyushu University,6-10-1Hakozaki,Higashi-ku,Fukuoka812-8581,JapanAccepted9July2004AbstractPhotochromic compounds reversibly change not only the absorption spectra but also their geometrical and electronic structures.The molecular structure changes induce physical property changes of the molecules such asﬂuorescence,refractive index,polarizability,electrical conductivity,and magnetism.In this review,among the physical properties that can be photoswitched by using diarylethenes as a photoswitching unit,ﬂuorescence,electrical conductivity,and magnetism are featured.©2004Japanese Photochemistry Association.Published by Elsevier B.V.All rights reserved.Keywords:Photochromism;Photoswitching;Diarylethene;Metal complex;Fluorescence;Phosphorescence;FRET;Single molecule;Electrical conductivity; Molecular magnetismContents1.Introduction (170)2.Photoswitching ofﬂuorescence (170)2.1.Photoswitching ofﬂuorescence (170)2.2.Emission from metal complexes (172)2.3.Fluorescence resonance energy transfer(FRET) (173)2.4.Photochromism at the single-molecule level (174)3.Photoswitching of electrical conductivity (176)4.Photoswitching of magnetism (177)4.1.Intramolecular magnetic interaction in diarylethenes (177)4.2.Photoswitching of magnetism using a diarylethene (177)4.3.Photoswitching using an array of diarylethenes (180)5.Conclusions (181)Acknowledgements (181)References (181)∗Corresponding author.Fax:+81926423568.E-mail address:irie@cstf.kyushu-u.ac.jp(M.Irie).1389-5567/$20.00©2004Japanese Photochemistry Association.Published by Elsevier B.V.All rights reserved.170K.Matsuda,M.Irie/Journal of Photochemistry and Photobiology C:Photochemistry Reviews5(2004)169–182 1.IntroductionPhotochromism refers to a reversible phototransformationof a chemical species between two forms having different ab-sorption spectra[1–4].Photochromic compounds reversiblychange not only the absorption spectra but also their geo-metrical and electronic structures.The molecular structurechanges induce physical property changes of the molecules,such asﬂuorescence,refractive index,polarizability,elec-trical conductivity,and magnetism.Photoswitching of thesephysical properties can be accomplished by appropriate de-sign of the molecules.By feeding back the evaluation of thephysical properties to the molecular design,more sophisti-cated photoresponsive molecular systems can be constructed.Diarylethenes with heterocyclic aryl groups are wellknown as thermally irreversible,highly sensitive,and fatigue-resistant photochromic compounds[5,6].The photochromicreaction is based on a reversible transformation between theopen-ring isomer,with a hexatriene structure,and the closed-ring isomer,with a cyclohexadiene structure,according to theWoodward–Hoffmann rule(Scheme1).While the open-ringisomer1a is colorless in most cases,the closed-ring isomerhas a color of yellow,red,or blue,depending on the molecularstructure.The difference in color is due to the difference in the ge-ometrical and electronic structures.In the open-ring isomer,free rotation is possible between the ethene moiety and thearyl group.Therefore,the open-ring isomer is non-planar andthe␲-electrons are localized in the two aryl groups.More-over,the open-ring isomer has two conformations,with thetwo rings in mirror symmetry(parallel conformation)andin C2symmetry(antiparallel conformation)[7].The photo-cyclization reaction can proceed only from the antiparallelconformation(Scheme2).On the other hand,the closed-ring isomer has a planar structure and there exist two enan-tiomers(R,R and S,S),originating from two asymmetric car-bon atoms.The closed-ring isomer is regarded as an alternatepolyene and the␲-electrons are delocalized throughout themolecule.These structure differences resulted in the differ-ence in the physical properties.For example,the closed-ringisomer has a higher polarizability,because the closed-ringisomer has more delocalized␲-electrons[8,9].Photochromic materials have the characteristic featurethat the function is based on the structure changes of singlemolecules.Therefore,photochromic reactions can be usednot only to control the bulk physical properties but also toswitch single-molecule devices.As components of molec-ular electronics,it is desirable to develop various typesofScheme2.Conformations of diarylethenes.molecular switching devices[10–12].In this sense,the pho-tochromic diarylethene is one of the most promising candi-dates for applications in molecular electronics.In this review,among the various physical properties which can be photoswitched by using diarylethenes as a pho-toswitching unit,molecules which changeﬂuorescence,elec-trical conductivity,and magnetism upon photoirradiation aredescribed.2.Photoswitching ofﬂuorescence2.1.Photoswitching ofﬂuorescenceFor the application of photochromic compounds in record-ing media,non-destructive readout capability is one of themost important requirements.In a conventional transmit-tance readout method,the readout light always induces a pho-tochromic reaction to some extent.Therefore,the recordedinformation is destroyed after many readout operations.Onthe other hand,aﬂuorescence readout method is more sensi-tive than the transmittance readout method.When veryweakK.Matsuda,M.Irie /Journal of Photochemistry and Photobiology C:Photochemistry Reviews 5(2004)169–182171Scheme 4.readout power is used,the destruction of the recorded infor-mation can be minimized [13,14].Several ﬂuorescent photoswitching molecules have been synthesized.Diarylethene 2is a ﬂuorescent photoswitching molecule synthesized by Tsivgoulis and Lehn (Scheme 3)[15,16].The open-ring isomer 2a is converted to the closed-ring isomer 2b in methanol by irradiation with UV light (λ<400nm)with conversion of 92%,and the closed-ring isomer 2b returns to the open-ring isomer 2a by irradiation with vis-ible light (λ>600nm)quantitatively.The absorption band at 459nm,which appeared in both isomers,is assigned to the absorption of the pyridyl–dithienothiophene–thiophene moiety.When excited in the 400–500nm region,the open-ring isomer 2a showed ﬂuorescence with an emission max-imum at 589nm,but the closed-ring isomer 2b showed al-most no ﬂuorescence (less than 3%of that of the open-ring isomer).The open-ring isomer is in the “ON”state and the closed-ring isomer is in the “OFF”state.When the ﬂuores-cence can be detected without inﬂuencing the ratio of the two isomers,the ﬂuorescence readout method becomes non-destructive.Actually,both cyclization and cycloreversion re-actions hardly took place when the molecule was excited with a narrow range of the excitation wavelength (450–460nm).The molecule has quasi-non-destructive capability.Diarylethene 3,with a 4-formylthiophene group,exhibits a ﬂuorescence-photoswitching property (Scheme 4)[17].By irradiation with 301nm light,the open-ring isomer 3a showed ﬂuorescence,with an emission maximum at 420nm,but the closed-ring isomer 3b did not show any ﬂuorescence.Triphenylimidazole is known as a compound with a high ﬂuorescence quantum yield (48%).Diarylethene 4,with a triphenylimidazole group,was synthesized (Scheme 5)[18].The open-ring isomer 4a showed ﬂuorescence at 390and 410nm,with a ﬂuorescence quantum yield of 7.7%when excited at 313nm,but the closed-ring isomer 4b did not show any ﬂuorescence.In spite of the relatively high ﬂuorescence yield,4a showed a high cyclization quantum yield of 0.49.The cycloreversion quantum yield was 1/10of that of the cyclization reaction.Osuka et al.reported the synthesis and ﬂuorescence be-havior of diarylethene 5,with a tetraphenylporphyrin moiety (Scheme 6)[19].The open-ring isomer 5a showed ﬂuores-cence at 650and 717nm when excited at 420nm,but the closed-ring isomer 5b showed only weak ﬂuorescence.The energy transfer from the excited porphyrin to the closed-ring isomer of the diarylethene prohibits the ﬂuorescence.The conversion from the open-to the closed-ring isomers under irradiation with 330nm light was 75%,and the cyclization and cycloreversion quantum yields were determined to be 4.3×10−2and 1.8×10−3,respectively.Bis(diarylethene)6has two diarylethenes and one ﬂuo-rescent bis(phenylethynyl)anthracene (Scheme 7)[20].The ﬂuorescence quantum yield of bis(phenylethynyl)anthracene was determined to be 0.83for the open-ring isomer 6a and 0.001for the closed-ring isomer 6b .Relatively large ﬂuores-cence switching was observed in this molecule.The open-ring isomer 6a showed laser emission by excitation with 337.1nm laser pulses and the laser emission intensity could be reversibly switched by alternative irradiation with UV and visible light.Tian et al.reported ﬂuorescence-photoswitching systems using tetraazaporphyrin–diarylethene hybrid 7(Scheme 8)[21].This molecule,having four diarylethene units,exhibits a photochromic property by irradiation with UV and visible light.It was suggested that the cyclization reaction occurs at two opposite positions of the tetraazaporphyrin.The open-ring isomer 7a is ﬂuorescent,but the closed-ring isomer 7b is non-ﬂuorescent.The near-IR emission maximum of the172K.Matsuda,M.Irie /Journal of Photochemistry and Photobiology C:Photochemistry Reviews 5(2004)169–182Scheme 6.open-ring isomer was observed at 689nm when excited at 480nm.The detailed mechanism of the ﬂuorescence from 1,2-bis(3-methyl-2-thienyl)ethene 8a was studied in solution as well as in the single-crystalline phase (Scheme 9)[22].The characteristic ﬂuorescence of the crystal at 520nm was attributed to the ﬂuorescence from aggregates of the di-arylethene molecules in the crystal.Similar bathochromic ﬂuorescence was also observed in the concentrated hexane solution of the molecule.The structure of the aggregatewasestimated from the ﬂuorescence anisotropy and X-ray crys-tallographic analysis of the single crystal.The closed-ring isomer did not show any ﬂuorescence.Kryschi and co-workers reported the ﬂuorescence dynam-ics on an anthracene-substituted diarylethene 9a (Scheme 10)[23].The non-reacting parallel conformer is suggested to con-tribute to the ﬂuorescence.2.2.Emission from metal complexesBranda and co-workers reported phosphorescence-switching molecules with transition metals (Scheme 11)[24,25].In molecule 10a ,a diarylethene with two pyridyl groups is axially coordinated to ruthenium porphyrins.The open-ring isomer 10a is converted to the closed-ring isomer 10b with a conversion of 95%by irradiation with 365nm light.The closed-ring isomer 10b is converted back to the open-ring isomer completely by irradiation with visible light (470nm <λ<685nm).The open-ring isomer 10a showed phosphorescence at 730nm when excited with visible light (400nm <λ<480nm).On the other hand,the closed-ring isomer 10b did not show any phosphorescence.Con-veniently,both the open-and closed-ring isomers of the cen-tral bispyridyl diarylethene unit are transparent in this re-gion.Therefore,irradiation with light in the wavelength range (400nm <λ<480nm)scarcely induces photochemical in-terconversion in either direction.Non-destructive readout isK.Matsuda,M.Irie /Journal of Photochemistry and Photobiology C:Photochemistry Reviews 5(2004)169–182173Scheme8.Scheme 9.Fern´a ndez-Acebes and Lehn developed a novel di-arylethene tungsten complex 11,in which the closed-ring isomer shows stronger ﬂuorescence than the open-ring iso-mer (Scheme 12)[26].When excited at 240nm,the ﬂuores-cence quantum yield of the closed-ring isomer 11b was 0.15,while the ﬂuorescence quantum yield of the open-ring iso-mer 11a was only 0.03.Irradiation with 240nm light did not induce any photochromic reaction in either direction,so that non-destructive readout can be achieved in this system.Diarylethene 12is also reported to show emission from the closed-ring isomer (Scheme 13)[27].The open-ring isomer 12a showed ﬂuorescence at 450nm,with ﬂuorescence quan-tum yield of 1.1%,while the ﬂuorescence maximum shifted to 650nm when 12a converted to 12b .The ﬂuorescence at 650nm was ascribed to that from excited 12b .De Cola and co-workers reported the emission behavior of diarylethene Ru and Os complexes 13(Scheme 14)[28].The emission from the triplet metal-to-ligand charge-transfer (3MLCT)state was observed at 630and 759nm for Ru and Os complexes,respectively.Interestingly,in the Ru complex,a photocyclization reaction of the diarylethene unitthrougha 3MLCT state was observed.Neither closed-ring isomer showed any emission.2.3.Fluorescence resonance energy transfer (FRET)FRET is widely used for imaging and analysis of biological reaction processes.Jares-Erijman and co-workers reported photoswitchable FRET systems using diarylethenes (Scheme 15)[29].The FRET systems are useful to analyze the reaction kinetics in detail in biological systems.In these systems,Lucifer Yellow is used as a ﬂuorescence donor moiety and is connected to a diarylethene photochromic pound 14shows a typical example.The closed-ring isomer of the diarylethene unit in 14b has an absorption band overlapping the emission band of the donor.When the diarylethene is in the open-ring form,the donor ﬂuorescence is not perturbed by the diarylethene unit and gives strong acceptor-free ﬂuorescence.On the other hand,when the diarylethene converts to the closed-ring form,energy transfer from the donor to the acceptor diarylethene closed-ring form takes place,and the ﬂuorescence is quenched.The quenching efﬁciency is dependent on the distance (or the intermolecular chain length)between the donor and the acceptor chromophores.The FRET systems can be used as nanoscale rulers.The energy transfer is also used to control the electron transfer between porphyrin and fullerene in diarylethene–porphyrin–fullerene triad 15(Scheme 16)[30].Neither the triad open-ring isomer 15a nor the closed-ring isomer 15b showed ﬂuorescence.The model diarylethene–porphyrin dyad compound showed ﬂuorescence from the porphyrin174K.Matsuda,M.Irie /Journal of Photochemistry and Photobiology C:Photochemistry Reviews 5(2004)169–182Scheme 11.when the diarylethene was in the open-ring form.In the closed-ring form,the ﬂuorescence was quenched by the en-ergy transfer from porphyrin to the closed-ring form.In the triad open-ring form (15a ),the photoinduced electron trans-fer from porphyrin to fullerene took place,but the energy transfer prohibited the electron transfer in the closed-ring form (15b ).An anthracene–diarylethene–pyridinium triad 16a was studied in terms of photoinduced electron transfer by Port and co-workers (Scheme 17)[31].The open-ring isomer showed ﬂuorescence with vibrational structures characteristic of an-thracene.The transient spectral measurement showed the ap-pearance of the absorption of the anthracene radical cation,suggesting a photoinduced electron transfer.On the other hand,the closed-ring isomer showed neither ﬂuorescence nor the anthracene radical cation absorption band.The quenching by the closed-ring isomer is considered to affect the electrontransfer.2.4.Photochromism at the single-molecule levelPhotochromic compounds have the feature that the perfor-mance can be detected at a single-molecule level.If a single molecule works as one bit of memory,the ultimate in high-density optical memory can be realized.As a ﬁrst step to this end,photoswitching of the ﬂuorescence of photochromic molecules was followed at the single-molecule level by ir-radiation with UV and visible light [32].Photoswitching of a single molecule has not yet been observed,since con-ventional photochromic molecules readily decompose under high power laser light.The molecule used in this experi-ment was diarylethene 17,in which a highly fatigue-resistant diarylethene and a ﬂuorescent bis(phenylethynyl)anthracene are connected with an adamantane spacer (Scheme 18).When the diarylethene moiety is in the open-ring isomer state,the bis(phenylethynyl)anthracene moiety emits strong ﬂuores-cence,with a ﬂuorescence quantum yield of 0.73.UponK.Matsuda,M.Irie /Journal of Photochemistry and Photobiology C:Photochemistry Reviews 5(2004)169–182175Scheme 13.irradiation with UV light,the diarylethene moiety under-goes a cyclization reaction to give the closed-ring isomer.In the closed-ring isomer state,the ﬂuorescence is quenched to a ﬂuorescence quantum yield of less than 0.001.In the ensemble toluene solution,the ﬂuorescence intensity grad-ually changed upon irradiation with UV or visible light.The analogue-type photoresponse in the ensemble system changed to the digital one at the single-molecule level.Fig.1shows the ﬂuorescence image and digital switching behavior of single molecules embedded in a polymer ﬁlm revealed by confocal microscopy.Initially,a ﬁlm containingnon-Scheme 15.ﬂuorescent 17b molecules was dark,but when irradiated with visible light for 10s,four molecules switched to the ﬂuo-rescent “ON”state.Upon irradiation with weak ultraviolet light for 3s,the ﬂuorescent molecules switched to the non-ﬂuorescent “OFF”state.This digital reversible switching is due to the photochromic reactions.The time trace of the pho-toresponse of a single molecule is shown in Fig.1(b).Start-ing in the “OFF”state,the non-ﬂuorescent molecule abruptly switched to the ﬂuorescent state due to photochromism from176K.Matsuda,M.Irie /Journal of Photochemistry and Photobiology C:Photochemistry Reviews 5(2004)169–182Scheme16.Scheme 17.17b to 17a .The ﬂuorescent molecule switched to the non-ﬂuorescent state as a result of photochromism from 17a to 17b .The ﬂuorescent diarylethene may ﬁnd application in the design of erasable media for ultrahigh-density optical data storage.3.Photoswitching of electrical conductivityIn conductive molecular wires,electrons are delocalized in the ␲-system.If the ␲-conjugated length or ␲-overlaps between adjacent molecules are controlled,electrical con-duction can be modulated.The idea to control the electri-cal conductivity using photochromic compounds was ﬁrst illustrated by Lehn and co-workers [33,34].They used di-arylethene 18a (Scheme 19).The open-ring isomer 18a is quantitatively converted to the closed-ring isomer 18b by ir-radiation with 365nm light,and the closed-ring isomer 18b with visible light (λ>600nm).The cyclic voltammogram of the open-ring isomer 18a showed a reductive wave at −1.04V (versus SCE),but the closed-ring isomer 18b underwent a re-duction process at −0.23V (versus SCE).The conjugation between the two positively charged moieties in the closed-ring isomer 18b decreased the reduction potential to a much less negative value.Diarylethenes are incorporated in the main chain of the conductive polymer 19(Scheme 20)[35].The colorless open-ring isomer 19a converted to the colored closed-ring isomer 19b ,which has an absorption maximum at 560nm,by irradiation with 313nm light.The conversion ratio from the open-to the closed-ring isomers in THF was 35%.While the electrical conductivity of a ﬁlm of the open-ring isomer 19a was 5.3×10−13S cm −1,in the photostationary state the con-ductivity increased to 1.2×10−12S cm −1.The closed-ring isomer is more conductive.The change in the ␲-conjugationK.Matsuda,M.Irie /Journal of Photochemistry and Photobiology C:Photochemistry Reviews 5(2004)169–182177Scheme 18.4.Photoswitching of magnetism 4.1.Intramolecular magnetic interaction in diarylethenesThere is an important characteristic feature in the elec-tronic structure changes of diarylethenes with regard to mag-netic interactions [36].Fig.2shows the open-ring isomer 20a and the closed-ring isomer 20b of radical-substituted diarylethenes with simpliﬁed structures.While there is no resonant closed-shell structure for 20a ,there exists 20b as a resonant quinoid-type closed-shell structure for 20b .While the open-ring isomer 20a exists as a non-Kekul´e biradical,theclosed-ring isomer 20b exists as a normal Kekul´e molecule.The calculated shapes of the two SOMOs of 20a are separated in the molecule and there is no overlap [37].This conﬁgura-tion is a typical disjoint biradical,in which the intramolecular radical–radical interaction is weak [38,39].In the open-ring isomer,the bond alternation is discontinued at the 3-position of the thiophene rings.This is the origin of the disjoint na-ture of the electronic conﬁguration of 20a .In the case of the closed-ring isomer 20b ,the ground electronic state has no unpaired electrons.In this singlet ground state,the magnetic interaction is strongly antiferromagnetic.The electronic structure change of radical-substituted di-arylethenes accompanying the photochromism is thetrans-Fig.1.(a)Fluorescence images and (b)time traces of single ﬂuorescence-photoswitching molecules.formation of a disjoint non-Kekul´e structure to a closed-shell Kekul´e structure.It is inferred from the above consideration that the interaction between spins in the open-ring isomer of the diarylethene is weak,while signiﬁcant antiferromagnetic interaction takes place in the closed-ring isomer.In other words,the open-ring isomer is in an “OFF”state,and the closed-ring isomer is in an “ON”state.4.2.Photoswitching of magnetism using a diarylethene Two radicals are introduced to a diarylethene,as shown in 21(Scheme 21),in which 1,2-bis(2-methyl-1-benzothiophen-3-yl)perﬂuorocyclopentene is employed as a178K.Matsuda,M.Irie /Journal of Photochemistry and Photobiology C:Photochemistry Reviews 5(2004)169–182Scheme20.Scheme21.Fig.2.The open-ring isomer 20a and the closed-ring isomer 20b of the radical-substituted diarylethene.photochromic spin coupler and nitronyl nitroxides as spin sources [37,40].In solution,21a showed ideal photochromic behavior by irradiation with UV and visible light.Although the radical moiety absorbs in the region from 550to 700nm,it did not prohibit the photochromic reaction.Magnetic susceptibilities of 21a and 21b were mea-sured on a SQUID susceptometer in microcrystalline form.χT –T plots are shown in Fig.3.The data were analyzed in terms of a modiﬁed singlet–triplet two-spin model (the Bleaney–Bowers-type)in which two spins (S =1/2)cou-ple antiferromagnetically within a biradical molecule by ex-change interaction J .The best-ﬁt parameters,obtained by means of a least-squares method,were 2J /k B =−2.2±0.04K for 21a and 2J /k B =−11.6±0.4K for 21b .Although the in-Fig.3.Temperature dependence of the magnetic susceptibility of 21a ( )and 21b ( )(χT –T plot).ring isomer 21a is small,the spins of 21b have a remarkable antiferromagnetic interaction (2J /k B =−11.6K).The open-ring isomer 21a had a twisted molecular struc-ture and a disjoint electronic conﬁguration.On the other hand,the closed-ring isomer 21b had a planar molecular struc-ture and a non-disjoint electronic conﬁguration.The photoin-duced change in magnetism agrees well with the prediction that the open-ring isomer has an “OFF”state and the closed-ring isomer has an “ON”state.Although the switching of the exchange interaction was detected by a susceptibility measurement of biradical 21,both the open-and closed-ring isomers 21a and 21b had nine-line ESR spectra,which means that the exchange interaction be-tween the two radicals was much stronger than the hyperﬁne coupling constant in both isomers.To detect the change of the exchange interaction by ESR spectroscopy,the value of the interaction should be comparable to the hyperﬁne coupling constant.To decrease the exchange interaction biradicals 22(n =1,2),in which p -phenylene spacers were incorporated,Scheme 22.Nitronyl nitroxides themselves have two identical nitro-gen atoms to give ﬁve-line ESR spectra with relative in-tensities 1:2:3:2:1and a 7.5G spacing.When two nitronyl nitroxides are magnetically coupled via an exchange inter-action,the biradical gives a nine-line ESR spectrum with relative intensities 1:4:10:16:19:16:10:4:1and a 3.7G spac-ing.If the exchange interaction is smaller than the hyperﬁne coupling in the biradical,the two nitroxide radicals are mag-netically independent and give the same spectrum as the inde-pendent monoradical.In intermediate situations the spectrum becomes complex.Diarylethenes 22a (n =1,2)underwent reversible pho-tochromic reactions in ethyl acetate solution by alternative ir-radiation with 313nm UV light and 578nm visible light.The changes in the ESR spectra accompanying the photochromic reaction were examined for diarylethenes 22a (n =1,2).Fig.4shows the ESR spectra at different stages of the photochromic reaction of 22a (n =1).The ESR spectrum of 22a (n =1)showed a complex of 15lines.This suggests that the two spins of the nitronyl nitroxide radicals are coupled by an exchange interaction that is comparable to the hyperﬁne coupling con-stant.Upon irradiation with 366nm light,the spectrum con-verted completely to a nine-line spectrum,corresponding to the closed-ring isomer 22b (n =1).The nine-line spectrum indicates that the exchange interaction between the two spins in 22b (n =1)is much larger than the hyperﬁne couplingconstant.Fig.4.ESR spectral changes for 22a (n =1)along with photochromism (benzene solution,1.1×10−4M):(a)initial;(b)irradiation with 366nm light for 1min;(c)4min;(d)irradiation with >520nm light for 20min;(e)50min.Table 1Magnetic interaction between two nitronyl nitroxide connected by di-arylethene photoswitchesOpen-ring form isomer Closed-ring form isomer ESR line shape |2J /k B |(K)ESR line shape |2J /k B |(K)219Lines2.29Lines 11.622(n =1)15Lines1.2×10−3<3×10−49Lines >0.0422(n =2)5Lines <3×10−4Distorted 9lines 0.01023(n =1)13Lines 5.6×10−3<3×10−49Lines >0.0423(n =2)5Lines<3×10−49Lines>0.04An ESR spectral change was also observed for 22a (n =2).The open-ring isomer 22a (n =2)had a ﬁve-line spectrum,while the closed-ring isomer 22b (n =2)had a distorted nine-line spectrum.Based on the simulation of the ESR spectra,the dependence of the exchange interaction on the ␲-conjugated chain length was estimated and is shown in Table 1.The exchange interaction change in 22a (n =1,2)upon photoir-radiation was more than 30-fold.Oligothiophenes are good candidates for conductive molecular wires.The thiophene-2,5-diyl moiety has been used as a molecular wire unit for energy and electron transfer and serves as a stronger magnetic coupler than p -phenylene.Diarylethenes 23a (n =1,2)having two nitronyl nitroxideScheme23.Fig.5.Photochromic reaction and schematic illustration of diarylethene 24.radicals at both ends of a molecule containing oligothiophene spacers were prepared (Scheme 23)[43,44].Photochromic reactions and an ESR spectral change were also observed for 23a (n =1,2).Table 1lists the exchange interaction between the two diarylethene-bridged nitronyl nitroxide radicals.For all ﬁve biradicals,the closed-ring isomers have stronger interactions than the open-ring iso-mers.The exchange interactions through the oligothiophene spacers were larger than the corresponding biradicals with oligophenylene spacers.The efﬁcient ␲-conjugation in thio-phene spacers resulted in large exchange interactions between the two nitronyl nitroxide radicals.In the case of bithiophene spacers,the exchange interaction difference between open-and closed-ring isomers was estimated to be more than 150-fold.4.3.Photoswitching using an array of diarylethenes When a diarylethene dimer is used as a switching unit [45],there are three kinds of photochromic states:open–open (OO),closed–open (CO),and closed–closed (CC).From the analogy of an electric circuit,it is inferred that the dimer has two switching units in series.The dimer 24,which has 28carbon atoms between two nitronyl nitroxide radicals,was prepared (Fig.5).A p -phenylene spacer was introduced so that the cyclization reaction could occur at both diarylethene moieties.Bond alternation is discontinued at the open-ring form moieties of 24(OO)and 24(CO).As a result,the twospins at both ends of 24(OO)and 24(CO)cannot interact with each other.On the other hand,the ␲-system of 24(CC)is delocalized throughout the molecule,and the exchange interaction between the two radicals is expected to occur.24(OO)underwent a photochromic reaction by alternate irradiation with UV and visible light.Upon irradiation of the ethyl acetate solution of 24(OO)with 313nm light,an absorption at 560nm appeared.The color of the solution changed from pale blue to red-purple,and then to blue-purple.The red spectral shift suggests the formation of 24(CC).The isosbestic point was maintained at an initial stage of irradia-tion,but it later deviated.The blue-purple solution was com-pletely bleached by irradiation with 578nm light.24(CO)and 24(CC)were isolated from the blue-purple solution by HPLC.24(CC)has an absorption maximum at 576nm,which is red-shifted as much as 16nm in comparison with 24(CO).ESR spectra of isolated 24(OO),24(CO),and 24(CC)were measured in benzene at room temperature (Fig.6).The spectra of 24(OO)and 24(CO)are of the ﬁve-line type,sug-gesting that the exchange interaction between the two nitronyl nitroxide radicals is much smaller than the hyperﬁne coupling constant (2J /k B <3×10−3K).However,the spectrum of 24(CC)is a clear nine-line type,indicating that the exchange interaction between the two spins is much larger than the hyperﬁne coupling constant (2J /k B >0.04K).The result indicates that each diarylethene chro-mophore serves as a switching unit to control the magnetic in-teraction.The magnetic interaction between terminal nitronyl。

拉曼光谱――羟基鉴定法

拉曼光谱――羟基鉴定法00光照射到物质上发生弹性散射和非弹性散射.弹性散射的散射光是与激发光波长相同的成分.非弹性散射的散射光有比激发光波长长的和短的成分,统称为拉曼效应。

拉曼光谱分析技术是以拉曼效应为基础建立起来的分子结构表征技术,其信号来源与分子的振动和转动。

其谱线数目、位移值和谱带强度等直接反映了分子的构成及构象信息。

拉曼光谱的应用范围遍及化学、物理学、生物学和医学等各个领域，对于纯定性分析、高度定量分析和测定分子结构都有很大价值。

拉曼光谱技术的优越性拉曼光谱技术是一种分析技术,由于它能够获得物质的分子信息而被应用于文物的分析中,特别是拉曼光谱作为无损的分析方法,最适合应用于文物的原位分析。

a.定性分析:不同的物质具有不同的特征光谱，因此可以通过光谱进行定性分析。

b.结构分析:对光谱谱带的分析,又是进行物质结构分析的基础。

c.定量分析:根据物质对光谱的吸光度的特点,可以对物质的量有很好的分析能力。

d.提供快速、简单、可重复、且更重要的是无损伤的分析，它无需样品准备，样品可直接通过光纤探头或者通过玻璃、石英、和光纤测量e.因为激光束的直径在它的聚焦部位通常只有0.2-2毫米，常规拉曼光谱只需要少量的样品就可以得到。

这是拉曼光谱相对常规红外光谱一个很大的优势。

而且，拉曼显微镜物镜可将激光束进一步聚焦至20微米甚至更小，可分析更小面积的样品。

什么是羟基:羟基是由氢和氧两种原子组成的一价离子团(-OH)，即氢氧根。

中国化学家借用汉字羟表示(-OH)。

"羟"字中左边的羊表示氧，右边的表示氢，读音取氢(qing)之qi，取氧(yang)之韵母ang，合起来念-"抢"。

羟基在高温下不稳定，在常温、常压地表环境下是稳定的，其在陶瓷釉面中的含量与陶瓷烧造出窑时间成正比关系。

羟基是鉴定古陶瓷真伪的定性、定量物质。

羟基鉴定方法原理:(一)陶瓷在烧造过程中会发生一系列的物理和化学变化。

First-principle study of excitonic self-trapping in diamond

a rXiv:mtrl -th/9522v14Fe b1995First-principle study of excitonic self-trapping in diamond Francesco Mauri ∗and Roberto Car Institut Romand de Recherche Num´e rique en Physique des Mat´e riaux (IRRMA)IN-Ecublens 1015Lausanne,Switzerland Abstract We present a ﬁrst-principles study of excitonic self-trapping in diamond.Our calculation provides evidence for self-trapping of the 1s core exciton and gives a coherent interpretation of recent experimental X-ray absorption and emission data.Self-trapping does not occur in the case of a single valence exciton.We predict,however,that self-trapping should occur in the case of a valence biexciton.This process is accompanied by a large local relaxation of the lattice which could be observed experimentally.PACS numbers:61.80.−x,71.38.+i,71.35+z,71.55.−iTypeset using REVT E XDiamond presents an unusually favorable combination of characteristics that,in connection with the recent development of techniques for the deposition of thin diamondﬁlms,make this material a good candidate for many technological applications.Particularly appealing is the use of diamond in electronic or in opto-electronic devices,as e.g.UV-light emitting devices.Moreover,diamond is an ideal material for the construction of windows that operate under high power laser radiation or/and in adverse environments.It is therefore interesting to study radiation induced defects with deep electronic levels in the gap,since these can have important implications in many of these applications.Excitonic self-trapping is a possible mechanism for the formation of deep levels in the gap.The study of such processes in a purely covalent material,like diamond,is interesting also from a fundamental point of view.Indeed,excitonic self-trapping has been studied so far mostly in the context of ionic compounds,where it is always associated with,and often driven by,charge transfer eﬀects.In a covalent material the driving mechanism for self-trapping is instead related to the diﬀerence in the bonding character between the valence and the conduction band states.Both experimental data and theoretical arguments suggest the occurrence of self-trapping processes in diamond.In particular,a nitrogen(N)substitutional impurity induces a strong local deformation of the lattice[1–3]that can be interpreted as a self-trapping of the donor electron.The structure of a1s core exciton is more controversial[4–9].Indeed the similarity between an excited core of carbon and a ground-state core of nitrogen suggests that the core exciton should behave like a N impurity.However,the position of the core exciton peak in the diamond K-edge absorption spectra is only0.2eV lower than the conduction band minimum[4,7,8],while a N impurity originates a deep level1.7eV below the conduction band edge[10].On the other hand,emission spectra[8]suggest that a1s core exciton should self-trap like a N impurity.Finally,we consider valence excitations.In this case experimental evidence indicates that a single valence exciton is of the Wannier type,i.e.there is no self-trapping.To our knowledge,neither experimental nor theoretical investigations on the behavior of a valence biexciton in diamond have been performed,although simple scalingarguments suggest that the tendency to self-trap should be stronger for biexcitons than for single excitons.In this letter,we present a detailed theoretical study of excitonic self-trapping eﬀects in diamond.In particular,we have investigated the Born-Oppenheimer(BO)potential energy surfaces corresponding to a core exciton,a valence exciton and a valence biexciton in the context of density functional theory(DFT),within the local density approximation(LDA) for exchange and correlation.Our calculation indicates that the1s core exciton is on a diﬀerent BO surface in absorption and in emission experiments.Indeed X-ray absorption creates excitons in a p-like state as required by dipole selection rules.Subsequently the system makes a transition to an s-like state associated to a self-trapping distortion of the atomic lattice,similar to that found in the N impurity case.These results provide a coherent interpretation of the experimental data.In addition,our calculation suggests that self-trapping should also occur for a valence biexciton.This is a prediction that could be veriﬁed experimentally.Let us start by discussing a simple model[11,12].In diamond,the occupied valence and the lower conduction band states derive from superpositions of atomic sp3hybrids having bonding and antibonding character,respectively.Thus,when an electron,or a hole,or an electron-hole pair is added to the system,this can gain in deformation energy by relaxing the atomic lattice.Scaling arguments suggest that the deformation energy gain E def∝−1/N b, where N b is the number of bonds over which the perturbation is localized.This localization,due to quantum conﬁnement.The in turn,has a kinetic energy cost E kin∝+1/N2/3bbehavior of the system is then governed by the value of N b that minimizes the total energy E sum=E def+E kin.Since the only stationary point of E sum is a maximum,E sum attains its minimum value at either one of the two extrema N b=1or N b=∞.If the minimum occurs for N b=1,the perturbation is self-trapped on a single bond which is therefore stretched.If the minimum occurs for N b=∞,there is no self-trapping and the perturbation is delocalized.When N p particles(quasi-particles)are added to the system,one can showthat,for a given N b,E def scales as N2p,while E kin scales as N p.As a consequence,the probability of self-trapping is enhanced when N p is larger.This suggests that biexcitons should have a stronger tendency to self-trap than single excitons[12,13].In order to get a more quantitative understanding of self-trapping phenomena in dia-mond,we performed self-consistent electronic structure calculations,using norm-conserving pseudopotentials[14]to describe core-valence interactions.The wave-functions and the electronic density were expanded in plane-waves with a cutoﬀof35and of140Ry,respec-tively.We used a periodically repeated simple cubic supercell containing64atoms at the experimental equilibrium lattice constant.Only the wave-functions at theΓpoint were con-sidered.Since the self-trapped states are almost completely localized on one bond,they are only weakly aﬀected by the boundary conditions in a64atom supercell.The eﬀect of the k-point sampling was analysed in Ref.[3]where similar calculations for a N impurity were performed using the same supercell.It was found that a more accurate k-point sampling does not change the qualitative physics of the distortion but only increases the self-trapping energy by20%compared to calculations based on theΓ-point only[3].In order to describe a core exciton we adopted the method of Ref.[15],i.e.we generated a norm conserving pseudopotential for an excited carbon atom with one electron in the1s core level andﬁve electrons in the valence2s-2p levels.In our calculations for a valence exciton or biexciton we promoted one or two electrons,respectively,from the highest valence band state to the lowest conduction band state.Clearly,our single-particle approach cannot account for the(small)binding energy of delocalized Wannier excitons.However our approach should account for the most important contribution to the binding energy in the case of localized excitations.Structural relaxation studies were based on the Car-Parrinello(CP) approach[16].We used a standard CP scheme for both the core and the valence exciton, while a modiﬁed CP dynamics,in which the electrons are forced to stay in an arbitrary excited eigenstate[12,17],was necessary to study the BO surfaces corresponding to a valence biexciton.All the calculations were made more eﬃcient by the acceleration methods of Ref.[18].Weﬁrst computed the electronic structure of the core exciton with the atoms in the ideal lattice positions.In this case the excited-core atom induces two defect states in the gap:a non-degenerate level belonging to the A1representation of the T d point group,0.4eV below the conduction band edge,and a3-fold degenerate level with T2character,0.2eV below the conduction band edge.By letting the atomic coordinates free to relax,we found that the absolute minimum of the A1potential energy surface correponds to an asymmetric self-trapping distortion of the lattice similar to that found for the N impurity[3].In particular, the excited-core atom and its nearest-neighbor,labeled a and b,respectively,in Fig.1, move away from each other on the(111)direction.The corresponding displacements from the ideal sites are equal to10.4%and to11.5%of the bond length,respectively,so that the (a,b)-bond is stretched by21.9%.The other atoms move very little:for instance the nearest-neighbor atoms labeled c move by2.4%of the bond length only.This strong localization of the distortion is consistent with the simple scaling arguments discussed above.As a consequence of the atomic relaxation,the non-degenerate level ends up in the gap at1.5eV below the conduction band edge,while the corresponding wavefunction localizes on the stretched bond.The3-fold degenerate level remains close to the conduction band edge,but since the distortion lowers the symmetry from T d to C3v,the3-fold degenerate level splits into a2-fold degenerate E level and a non-degenerate A1level.In Fig.2we report the behavior of the potential energy surfaces corresponding to the ground-state,the A1and the T2core exciton states as a function of the self-trapping dis-tortion.Notice that the distortion gives a total energy gain of0.43eV on the A1potential energy surface.The same distortion causes an increase of the ground-state energy of1.29 eV.Our calculation indicates that the core-exciton behaves like the N impurity[3],support-ing,at least qualitatively,the validity of the equivalent core approximation.The similar behavior of the A1level in the core exciton and in the N impurity case was also pointed out recently in the context of semi-empirical CNDO calculations[9].The diﬀerences between the core exciton and the impurity[3]are only quantitative:in particular,the relaxationenergy and especially the distance of the A1level from the conduction band edge are smaller for the core exciton than for the N impurity.Our results suggest the following interpretation of the experimental data of Refs.[4,8]: (i)During X-ray absorption the atoms are in the ideal lattice positions.Dipole transitions from a1s core level to a A1valence level are forbidden,but transitions to the T2level are allowed.In our calculation the T2level is0.2eV lower than the conduction band edge,in good agreement with the core exciton peak observed in X-ray absorption spectra[4,8].(ii) On the T2BO potential energy surface the lattice undergoes a Jahn-Teller distortion which lowers its energy(see Fig.2).(iii)Since the LO phonon energy in diamond(0.16eV)is comparable to the energy spacing between the A1and the T2surfaces,which is less than 0.2eV after the Jahn-Teller distortion,the probability of a non-adiabatic transition from the T2to the A1surface is large.(iv)On the A1level the system undergoes a strong lattice relaxation resulting in a localization of the exciton on a single bond.(v)The self-trapping distortion induces a Stokes shift in the emitted photon energy.If the atomic relaxation were complete the Stokes shift would be equal to1.9eV,which correponds(see Fig.2) to the energy dissipated in the T2-A1transition(0.2eV),plus the energy gained by self trapping on the A1surface(0.43eV),plus the energy cost of the self-trapping distortion on the ground-state energy surface(1.29eV).The data reported in Ref.[8]show a shift of about1eV in the positions of the peaks associated to the1s core exciton in X-ray absorption and emission spectra.The emission peak is very broad,with a large sideband that corresponds to Stokes shifts of up to5eV.As pointed out in Ref.[8],this large sideband is likely to be the eﬀect of incomplete relaxation. This is to be expected since the core exciton lifetime should be comparable to the phonon period[8].As a consequence,the atomic lattice would be able to perform only a few damped oscillations around the distorted minimum structure during the lifetime of the core exciton.We now present our results for the valence excitations.While in the case of a single exciton the energy is minimum for the undistorted crystalline lattice,in the case of a biex-citon weﬁnd that the energy is minimized in correspondence of a localized distortion of theatomic lattice.This is characterized by a large outward symmetric displacement along the (111)direction of the atoms a and b in Fig.1.As a result the(a,b)-bond is broken since the distance between the atoms a and b is increased by51.2%compared to the crystalline bondlength.This distortion can be viewed as a kind of local graphitization in which the atoms a and b change from fourfold to threefold coordination and the corresponding hy-bridized orbitals change from sp3to sp2character.Again,in agreement with the model based on simple scaling arguments,the distortion is strongly localized on a single bond.As a matter of fact and with reference to the Fig.1,the atoms c and d move by1.2%of the bondlength,the atoms e and f move by2.3%,and the atoms not shown in theﬁgure by less than0.9%.The self-trapping distortion of the biexciton gives rise to two deep levels in the gap: a doubly occupied antibonding level,at1.7eV below the conduction band edge,and an empty bonding level,at1.6eV above the valence band edge.Both states are localized on the broken bond.In Fig.3we show how diﬀerent BO potential energy surfaces behave as a function of the self-trapping distortion of the valence biexciton.In particular,from thisﬁgure we see that,while for the biexciton there is an energy gain of1.74eV in correspondence with the self-trapping distortion,the same distortion has an energy cost of1.49eV for the single exciton,and of4.85eV for the unexcited crystal.We notice that,while DFT-LDA predicts self-trapping for the valence biexciton,it does not do so for the single exciton,in agreement with experiment.Similarly to the case of the core exciton the major experimental consequence of the self-trapping of the valence biexciton is a large Stokes shift in the stimulated-absorption spontaneous-emission cycle between the exciton and the biexciton BO surfaces.As it can be seen from Fig.3,this Stokes shift should be equal to3.23eV,i.e.to the sum of the energy gain of the biexciton(1.74eV)and of the energy cost of the exciton(1.49eV) for the self-trapping relaxation.The fundamental gap of diamond is indirect.Thus the spontaneous decay of a Wannier exciton in an ideal diamond crystal is phonon assistedand the radiative lifetime of the exciton is much longer than in direct gap semiconductors. However,after self-trapping of the biexciton,the translational symmetry is broken and direct spontaneous emission becomes allowed.As a consequence the radiative life time of the self-trapped biexciton is much smaller than that of the Wannier ing the DFT-LDA wavefunctions,we obtained a value of∼7ns for the radiative lifetime of the biexciton within the dipole approximation.This is several orders of magnitude larger than the typical phonon period.Therefore the self-trapping relaxation of the valence biexciton should be completed before the radiative decay.A self-trapped biexciton is a bound state of two excitons strongly localized on a single bond.Thus the formation of self-trapped biexcitons requires a high excitonic density.To realize this condition it is possible either to excite directly bound states of Wannier excitons, or to create a high density electron-hole plasma,e.g.by strong laser irradiation.In the second case many self-trapped biexcitons could be produced.This raises some interesting implications.If many self-trapped biexcitons are created,they could cluster producing a macroscopic graphitization.Moreover,since the process of self-trapping is associated with a relevant energy transfer from the electronic to the ionic degrees of freedom,in a high density electron hole plasma biexcitonic self-trapping could heat the crystal up to the melting point in fractions of a ps,i.e in the characteristic time of ionic relaxation.Interestingly,melting ofa GaAs crystal under high laser irradiation has been observed to occur in fractions of a ps[19].In Ref.[19]this phenomenon has been ascribed to the change in the binding properties due to the electronic excitations.Our study on diamond leads one to speculate that in a sub-picosecond melting experiment self-trapping phenomena could play an important role.In conclusion,we have studied excited-state BO potential energy surfaces of crystalline diamond within DFT-LDA.Our calculation predicts self-trapping of the core exciton and provides a coherent description of the X-ray absorption and emission processes,which com-pares well with the experimental data.Moreover,we also predict self-trapping of the valence biexciton,a process characterized by a large local lattice relaxation.This implies a strong Stokes shift in the stimulated absorption-spontaneous emission cycle of about3eV,whichcould be observed experimentally.It is a pleasure to thank F.Tassone for many useful discussions.We acknowledge support from the Swiss National Science Foundation under grant No.20-39528.93REFERENCES∗Present address:Departement of Physics,University of California,Berkeley CA94720, USA.[1]C.A.J.Ammerlaan,Inst.Phys.Conf.Ser.59,81(1981).[2]R.J.Cook and D.H.Whiﬀen,Proc.Roy.Soc.London A295,99(1966).[3]S.A.Kajihara et al,Phys.Rev.Lett.66,2010(1991).[4]J.F.Morar et al,Phys.Rev.Lett.54,1960(1985).[5]K.A.Jackson and M.R.Pederson,Phys.Rev.Lett.67,2521(1991).[6]J.Nithianandam,Phys.Rev.Lett.69,3108(1992).[7]P.E.Batson,Phys.Rev.Lett.70,1822(1993).[8]Y.Ma et al,Phys.Rev.Lett.71,3725(1993).[9]A.Mainwood and A.M.Stoneham,J.Phys.:Condens.Matter6,4917(1994).[10]R.G.Farrer,Solid State Commun.7,685(1969).[11]W.Hayes and A.M.Stoneham,Defects and defect processes in nonmetallic solids,(Wiley&Sons,New York,1985)pags.29-38.[12]F.Mauri,R.Car,(to be published).[13]The number of equal particles that can be accommodated on one bond of the crystal inthe same quantum state is limited by the Pauli principle.Thus no more than two holes or/and two electrons with opposite spins can be localized on one bond of a sp3bonded semiconductor.[14]G.Bachelet,D.Hamann,and M.Schl¨u ter,Phys.Rev.B26,4199(1982).[15]E.Pehlke and M.Scheﬄer,Phys.Rev.B47,3588(1993).[16]R.Car and M.Parrinello,Phys.Rev.Lett.55,2471(1985).[17]F.Mauri,R.Car and E.Tosatti,Europhys.Lett.24,431(1993).[18]F.Tassone,F.Mauri,and R.Car,Phys.Rev.B50,10561(1994).[19]orkov,I.L.Shumay,W.Rudolph,and T.Schroder,Opt.Lett.16,1013(1991);P.Saeta,J.-K.Wang,Y.Siegal,N.Bloembergen,and E.Mazur,Phys.Rev.Lett.67, 1023(1991);K.Sokolowski-Tinten,H.Schulz,J.Bialkowski,and D.von der Linde, Applied Phys.A53,227(1991).FIGURESFIG.1.Atoms and bonds in the ideal diamond crystal(left panel).Atoms and bonds after the self-trapping distortion associated with the valence biexciton(right panel).In this case the distance between the atoms a and b increases by51.2%.A similar but smaller distortion is associated with the core exciton:in this case the(a,b)distance is increased by21.9%.FIG.2.Total energy vs self-trapping distortion of the core-exciton.Theﬁgure displays the BO potential energy surfaces correponding to the ground-state,the A1,and the T2core exciton states.FIG.3.Total energy as a function of the self-trapping distortion of the biexciton.The BO energy surfaces correponding to the ground state,the valence exciton,and the valence biexciton are shown in theﬁgure.a b ce df(111)ground stateA 1−core excitonT 2−core excitonconduction ideal lattice distorted latticeground statebi−excitonexcitondistorted lattice ideal lattice。

利用多氟丙烯酸酯添加剂提升准二维钙钛矿发光二极管性能

物理化学学报Acta Phys. -Chim. Sin. 2023, 39 (12), 2301024 (1 of 8)Received: January 14, 2023; Revised: February 13, 2023; Accepted: February 14, 2023; Published online: February 28, 2023. *Correspondingauthors.Emails:****************.cn(P.C.);*******************.cn(Q.C.);*******************.cn(L.C.).The project was supported by the Ministry of Science and Technology of China (2021YFA1202802), the National Natural Science Foundation of China (21875280, 21991150, 21991153, 22022205), the CAS Project for Young Scientists in Basic Research (YSBR-054), the Special Foundation for Carbon Peak Neutralization Technology Innovation Program of Jiangsu Province (BE2022026) and the Natural Science Foundation Project of Chongqing (CSTB2022NSCQ-MSX0438). 科技部国家重点研发计划(2021YFA1202802), 国家自然科学基金(21875280, 21991150, 21991153, 22022205), 中国科学院稳定支持基础研究领域青年团队计划(YSBR-054), 江苏省碳达峰碳中和科技创新专项资金(BE2022026)和重庆市自然科学基金(CSTB2022NSCQ-MSX0438)资助项目© Editorial office of Acta Physico-Chimica Sinica[Article]doi: 10.3866/PKU.WHXB202301024Incorporation of a Polyfluorinated Acrylate Additive for High-Performance Quasi-2D Perovskite Light-Emitting DiodesTao Zhang 1,2, Simin Gong 3, Ping Chen 3,*, Qi Chen 1,2,*, Liwei Chen 2,4,*1 School of Nano-Tech and Nano-Bionics, University of Science and Technology of China, Hefei 230026, China.2 i -Lab, CAS Key Laboratory of Nanophotonic Materials and Devices, Suzhou Institute of Nano-Tech and Nano-Bionics,Chinese Academy of Sciences, Suzhou 215123, Jiangsu Province, China.3 Chongqing Key Laboratory of Micro&Nano Structure Optoelectronics, School of Physical Science and Technology, Southwest University, Chongqing 400715, China.4 In-situ Center for Physical Sciences, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.Abstract: Quasi-two-dimensional (quasi-2D) perovskites are one of the most promising luminescent layer candidates for light-emitting diodes (LEDs) because of their excellent optoelectronic properties such as large exciton binding energy, efficient energy transfer, high photoluminescence quantum yield, and adjustable band gap. However, the formation of a large number of low-dimensional phases and surface/interface defects during solution processing of quasi-two-dimensionalperovskite films gives rise to an increase in non-radiative recombination, resulting in deteriorated light-emitting diode performance. It is highly desirable to simultaneously realize low-dimensional phase formation inhibition and surface/interface defect passivation during quasi-two-dimensional perovskite film formation. Herein, we report a multifunctional additive, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane (OFHDODA), which has strong physical and chemical interactions with the PEA 2Cs 2Pb 3Br 10 precursor that can effectively suppress non-radiative recombination in the perovskite films. The distinct C ＝C peak in the Fourier transform infrared spectroscopy (FTIR) spectra and the F 1s peak in the X-ray photoelectron spectroscopy (XPS) spectra showed that OFHDODA molecules were successfully incorporated into the perovskite films, and most OFHDODA molecules existed as monomers. With the addition of OFHDODA, the photoluminescence quantum yield (PLQY) of the perovskite film increased from 19.7% to 49.0%, and the PL emission wavelength red-shifted from 508 to 511 nm. It was demonstrated that hydrogen bond interactions between the polyfluorine structure and PEA + can tune perovskite crystallization dynamics, which inhibit the formation of low-dimensional phases, as shown by the reduced peak intensities at 403 nm (n = 1), 434 nm (n = 2), and 465 nm (n = 3) in the absorption spectra. The strong Lewis base moiety of the ester groups passivates the unsaturated Pb 2+ defects at the surface and grain boundaries of the perovskite films, as evidenced by the Pb 4f peak shift in the XPS spectra and the C ＝O shift in the FTIR spectra. The trap-filled limiting voltage (V TFL ) decreased in both hole-only and electron-only devices, which also proves the reduction of Pb 2+ defects. At the optimized OFHDODA concentration, the scanning electron microscopy (SEM) and atomic force microscopy (AFM) results from the perovskite films show lower roughness and smoother surface potential, which promotes superior interfacial contact. As a result, perovskite LEDs with a device structure of indium tin oxide glass/poly (9-vinylcarbazole)/perovskite/1,3,5-tris(1-phenyl-1H -benzimidazol-2-yl)benzene/8-hydroxyquinolinolato-lithium/Al exhibitedanimproved maximum external quantum efficiency (EQE) from 8.55% to 13.76%, improved maximum brightness from 16400 to 17620 cd∙m−2, and increased lifetime from 8 min to 12 min. This process provides an effective way to suppress non-radiative recombination in quasi-2D perovskites via additive molecular structure design, leading to superior electroluminescence performance.Key Words: Quasi-two-dimensional perovskite; Non-radiative recombination; Low-dimensional inhibition;Defect passivation; Polyfluorinated acrylate additive利用多氟丙烯酸酯添加剂提升准二维钙钛矿发光二极管性能张涛1,2，龚思敏3，陈平3*，陈琪1,2,*，陈立桅2,4,*1中国科学技术大学纳米技术与纳米仿生学院，合肥2300262中国科学院苏州纳米技术与纳米仿生研究所创新实验室，中科院纳米光子材料与器件重点实验室，江苏苏州215123 3西南大学物理科学与技术学院，微纳结构光电子学重庆市重点实验室，重庆4007154上海交通大学化学与化工学院物质科学原位中心，上海200240摘要：准二维钙钛矿由于具有较大的激子结合能和高效的能量转移等优势，在发光二极管(light-emitting diodes，LED)中的应用前景被广泛看好。

食品添加剂特丁基对苯二酚的太赫兹光谱及其检测分析

食品添加剂特丁基对苯二酚的太赫兹光谱及其检测分析张曼;蔡禾;沈京玲【摘要】Terahertz time-domain spectroscopy (THz-TDS) technique has a wide range of applications in nondestructive testing.After many years study, people have found that many materials have characteristic absorptions in terahertz range. This letter studies the THz spectra of tert-butylhydroquinone (TBHQ), a food additive that was reported excessively in Mak chicken of McDonald. The authors applied terahertz nondestructive testing technique in identifying this material, testing the absorption and refractive index. The absorption spectra of TBHQ and flour mixture in 0. 2～2. 2 THz were also investigated. The simulation of vibration for single molecular was undertaken. The results represent that this method is possible by comparing the difference in absorption lines and this method paves the way for detecting food additives.%太赫兹时域光谱(THz-TDS)技术对物质进行无损检测是太赫兹应用领域的一个研究热点.针对近日报道检查出部分麦当劳的"麦乐鸡"添加剂中含有的一种化学成分一特丁基对苯二酚(TBHQ)含量超标,应用太赫兹无损检测技术对其作定性识别.测得该种化学成分在0.2～2.2 THz的吸收谱和折射率曲线,并将其以不同比例与面粉均匀混合,测得混和物和面粉在0.2～2.2 THz的吸收谱.同时对TBHQ进行理论模拟作为对比.结果表明,通过太赫兹波段吸收曲线的特征差异检测TBHQ是可行的,为无损食品添加剂的检测提供一种新型的方法.【期刊名称】《光谱学与光谱分析》【年(卷),期】2011(031)007【总页数】5页(P1809-1813)【关键词】太赫兹时域光谱;特丁基对苯二酚(TBHQ);面粉;频谱;吸收谱【作者】张曼;蔡禾;沈京玲【作者单位】首都师范大学物理系,北京市太赫兹波谱与成像重点实验室,太赫兹光电子学教育部重点实验室,北京100048;首都师范大学物理系,北京市太赫兹波谱与成像重点实验室,太赫兹光电子学教育部重点实验室,北京100048;首都师范大学物理系,北京市太赫兹波谱与成像重点实验室,太赫兹光电子学教育部重点实验室,北京100048【正文语种】中文【中图分类】O433.5太赫兹(terahertz,THz)电磁波通常指频率范围在0.1～10太赫兹(波长在30μm～3 mm)范围内的电磁辐射(1 THz=1012 Hz)。

光学名词中英文对照

incoherence addition interference phenomenon of light coherent condition single photon interference relationship between optical path difference and phase difference wavefront-splitted interference Young＇s double-slit interference experiment Thomas Young interference pattern (fringe) order of interference nonlocalized interference nonlocalized fringe Fresnel bimirror Fresnel biprism Lloyd mirror visibility wave train coherence time coherence length temporal coherence spatial coherence critical width of light source interference aperture angle partially coherent light amplitude-splitted interference film interference equal-inclination interference equal-inclination fringes localized interference
泰勒判据象分辨本領物镜的分辨本領相对孔径
Taylor criterion image resolving power resolving power of objective relative aperture

质谱分析法中英文专业词汇

质谱分析法：mass spectrometry质谱：mass spectrum，MS棒图：bar graph选择离子检测：selected ion monitoring ，SIM直接进样：direct probe inlet ，DPI接口：interface气相色谱－质谱联用：gas chromatography-mass spectrometry，GC-MS 高效液相色谱－质谱联用：high performance liquid chromatography-mass spectrometry，HPLC-MS电子轰击离子源：electron impact source，EI离子峰：quasi-molecular ions化学离子源：chemical ionization source，CI场电离：field ionization，FI场解析：field desorptiion，FD快速原子轰击离子源：fast stom bombardment ，FAB质量分析器：mass analyzer磁质谱仪：magnetic-sector mass spectrometer四极杆质谱仪（四极质谱仪）：quadrupole mass spectrometer紫外－可见分光光度法：ultraviolet and visible spectrophotometry;UV-vis 相对丰度（相对强度）：relative avundance原子质量单位:amu离子丰度：ion abundance基峰：base peak质量范围：mass range分辨率：resolution灵敏度：sensitivity信噪比：S/N分子离子：molecular ion碎片离子：fragment ion同位素离子：isotopic ion亚稳离子：metastable ion亚稳峰：metastable peak母离子：paren ion子离子：daughter含奇数个电子的离子：odd electron含偶数个电子的离子：even eletron，EE 均裂：homolytic cleavage异裂（非均裂）：heterolytic cleavage 半均裂：hemi-homolysis cleavage重排：rearragement分子量：MWα－裂解：α-cleavage 电磁波谱：electromagnetic spectrum光谱：spectrum光谱分析法：spectroscopic analysis原子发射光谱法：atomic emission spectroscopy肩峰：shoulder peak末端吸收：end absorbtion生色团：chromophore助色团：auxochrome红移：red shift长移：bathochromic shift短移：hypsochromic shift蓝（紫）移：blue shift增色效应（浓色效应）：hyperchromic effect 减色效应（淡色效应）：hypochromic effect 强带：strong band弱带：weak band吸收带：absorption band透光率：transmitance,T吸光度：absorbance谱带宽度：band width杂散光：stray light噪声：noise暗噪声：dark noise散粒噪声：signal shot noise闪耀光栅：blazed grating全息光栅：holographic graaing光二极管阵列检测器：photodiode array detector偏最小二乘法：partial least squares method ,PLS褶合光谱法：convolution spectrometry 褶合变换：convolution transform,CT离散小波变换：wavelet transform,WT 多尺度细化分析：multiscale analysis供电子取代基：electron donating group 吸电子取代基：electron with-drawing group荧光：fluorescence荧光分析法：fluorometryX-射线荧光分析法：X-ray fulorometry 原子荧光分析法：atomic fluorometry分子荧光分析法：molecular fluorometry 振动弛豫：vibrational relexation内转换：internal conversion外转换：external conversion 体系间跨越：intersystem crossing激发光谱：excitation spectrum荧光光谱：fluorescence spectrum斯托克斯位移：Stokes shift荧光寿命：fluorescence life time荧光效率：fluorescence efficiency荧光量子产率：fluorescence quantum yield荧光熄灭法：fluorescence quemching method散射光：scattering light瑞利光：Reyleith scanttering light拉曼光：Raman scattering light红外线：infrared ray,IR中红外吸收光谱：mid-infrared absorption spectrum,Mid-IR远红外光谱：Far-IR微波谱：microwave spectrum,MV红外吸收光谱法：infrared spectroscopy 红外分光光度法：infrared spectrophotometry振动形式：mode of vibration伸缩振动：stretching vibrationdouble-focusing mass spectrograph 双聚焦质谱仪trochoidal mass spectrometer 余摆线质谱仪ion-resonance mass spectrometer 离子共振质谱仪gas chromatograph-mass spectrometer 气相色谱-质谱仪quadrupole spectrometer 四极（质）谱仪Lunar Mass Spectrometer 月球质谱仪Frequency Mass Spectrometer 频率质谱仪velocitron 电子灯；质谱仪mass-synchrometer 同步质谱仪omegatron 回旋质谱仪。

硫化物标准溶液稳定性与标准曲线范围的探讨

硫化物是重要的水质监测项目，准确测定其含量，对了解水源水污染及污水处理状况有重要的意义。

在《HJ/ T 200-2005 水质硫化物的测定气相分子吸收光谱法》[1]中未给出标准溶液的有效使用时间和标准曲线的斜率（a）、截距（b）的参考范围。

在孙瑞、张丽萍、连正豪[2-4]等人的研究中知道，实际检测中硫化物标准溶液稳定性差，标准曲线斜率、截距波动大，这都将导致硫化物检测结果偏差大。

而目前对这两者的研究文献相对较少，故本文将结合硫化物标准溶液稳定性和标准曲线范围对气相分子吸收光谱法检测水质中硫化物的方法进行探讨。

1　方法原理硫化物在10%磷酸介质中将硫化物瞬间转变成H2S，用空气将该气体载入气相分子吸收光谱仪的吸光管中，在202.6nm波长处测得的吸光度与硫化物浓度遵守比耳定律。

2　实验部分2.1　仪器与试剂气相分子吸收光谱仪（上海北裕公司GMA3386）；实验用水，均为电导率≤1μS/cm的去离子水；10%磷doi：10.3969/j.issn.1004-275X.2018.05.062硫化物标准溶液稳定性与标准曲线范围的探讨陈海莹，欧嘉辉，陈　飒（中山公用水务有限公司水质监测中心，广东　中山　528400）摘　要：用气相分子吸收光谱仪测定水质中硫化物的方法，探讨硫化物标准溶液稳定性与标准曲线范围两者的关系，得出用0.4%氢氧化钠溶液作为介质并保存在棕色瓶中的硫化物标准溶液在试验前2h内有较好的稳定性，标准曲线斜率（a）参考范围0.0667 ± 0.0005，截距参考（b）范围0.0001 ± 0.0005，解决《HJ/T 200-2005 水质硫化物的测定气相分子吸收光谱法》标准方法中未对硫化物标准溶液的酸碱度和使用时间及曲线截距范围的说明，以供检测人员试验参考。

关键词：硫化物；稳定性标；准曲线；气相分子吸收光谱法中图分类号：X830 文献标识码：B 文章编号：1004-275X（2018）05-093-03Discussion on the Stability and Standard Curve Range of Sulfide Standard SolutionChen Haiying，Ou Jiahui，Chen Hao（Water Quality Monitoring Center，Zhongshan Public Water Co.，Ltd.，Zhongshan 528400，China）Abstract：The method of gas sulfide absorption spectrometer for the determination of sulfide in water was studied. The relationship between the stability of sulfide standard solution and the range of standard curve was discussed. The vulcanization of 0.4% sodium hydroxide solution as medium and stored in brown bottle was obtained. The material standard solution has good stability within 2 hours before the test. The slope of the standard curve（a）reference range 0.0667 ± 0.0005，intercept reference（b）range 0.0001 ± 0.0005，to solve the “HJ/T 200-2005 water quality sulfide The determination of the pH，time of use，and curve intercept range of the sulfide standard solution in the standard method for the determination of gas phase molecular absorption spectroscopy is for reference by test personnel.Key words：Sulfide；Stability criterion；Quasi-curve；Gas-phase molecular absorption spectroscopy3　结论1）钙镁结晶采用废液直接浸出，控制温度65~75℃、时间为1h左右、液固比4：1的条件下，锌浸出率大于99%，钙浸出率小于0.1%，浸出液可以直接返回锌湿法系统使用，浸出渣主要成份为二水硫酸钙。

药物分析常用英语词汇

药物分析专业英语词汇表Aabsorbance吸收度absorbanceratio吸收度比值absorption吸收absorptioncurve吸收曲线absorptioncoefficient吸收系数accuratevalue准确值Acid—dyecolormcty酸性染料比色法acidimcty酸量法acidity酸度activity活度adjustedretentiontime调整保留时间absorbent吸收剂absorption吸附alkalinity碱度alumina氧化铝，矾土ambienttemperature室温ammoniumthiocyanate硫氰酸铵analyticalqualitycontrol分析质量控制anhydroussubstance 干燥品antioxidant抗氧剂applicationofsample点样areanormalizationmethod面积归一法arsenic砷arsenicsport砷斑assay含量测定assaytolerance含量限度attenuation衰减acidburette酸式滴定管alkaliburette碱式滴定管amortar研钵Bbackextraction反萃取bandabsorption谱带吸收batch批batchnumber批号Benttendorlfmethod白田道夫法betweendayprecision日间密度精biotransformation生物转化blanktest空白试验boilingrange沸程BritishPharmacopeia英国药典bromatetitration溴酸盐滴定法brominemethod溴量法bromothymolblue溴麝香酚蓝bulkdrug原料药by—product副产物breaker烧杯buretteglassbeadnozzle滴定管brownacidburette棕色酸式滴定管Ccalibrationcurve校正曲线calomelelectrode甘汞电极calorimetry量热分析capacityfactor容量因子capillarygaschromatography毛细管气相色谱法carriergas载气characteristicsdescription性状chelatecompound螯合物chemicalequivalent化学当量Chinesepharmacopeia中国药典Chinesematerialmedicine中成药Chinesematerialmidicalpreparation中药制剂chiral手性的chiralcarbonatom手性碳原子chromatogram色谱图chromatography色谱法chromatographiccolumn色谱柱chromatographiccondition色谱条件clarity澄清度coefficientofdistribution分配系数coefficientofvariation变异系数colorchangeinterval变色范围colorreaction显色反应colormetry比色法columnefficiency柱效columntemperature柱温comparativetest比较试验completenessofsolution溶液的澄清度conjugate缀合物concentration—timecurve浓度时间曲线confidenceinterval置信区间confidencelevel置信水平controlledtrial对照试验correlationcoefficient相关系数contrasttest对照试验congealingpoint凝点contentunifarmity装量差异controlledtrial对照试验correlationcoefficient相关系数contrasttest对照试验counterion反离子cresalred甲酚红cuvettecell比色池cyanide氰化物casserolesmall勺皿Ddead—stoptitration永定滴定法deadtime死时间deflection偏差deflectionpoint拐点degassing脱气deionizedwater去离子水deliquescence潮解depressorsubstancestest降压物质检查法desiccant干燥剂detection检查developingreagent展开剂developingchamber展开室deviation偏差dextrose右旋糖diastereoisomer非对映异构体diazotization重氮化differentialthermalanalysis差示热分析法differentialscanningcalorimetry差示扫描热法Gutzeit古蔡daytodayprecision日间精密度dissolution溶出度directinjection直接进样2,6-dichlorindophenoltitration2,6-二氯靛酚滴定法digestion消化diphastictitration双向滴定disintegrationtest崩解试验dispersion分散度dissolubility溶解度dissolutiontest溶解度检查distillingrange滴程distributionchromatography分配色谱dose剂量drugqualitycontrol药品质量控制dryingtoconstantweight干燥至恒重duplicatetest重复试验diskmethodwatermethod压片法Eeffectiveconstituent有效成分effectiveplatenumber有效板数effectiveofcolumn柱效electrophoresis电泳elimination消除eluate洗脱液elution洗脱enamtiomer对映体endabsorption末端吸收endogenoussubstances内源性物质enzymedrug酶类药物enzymeinduction酶诱导enzymeinhibition酶抑制epimer差向异构体equilibriumconstant平衡常数errorinvolumetricanalysis容量分析误差exclusionchromatography排阻色谱法expirationdate失效期externalstandardmethod外标法extract提取物extrationgravimetry提取重量法extractiontitration提取容量法extrapolatedmethod外插法Erlenmeyerflask锥形瓶evaporatingdishsmall蒸发皿elongatedbulb胖肚electronicbalanceMettlerAL204MettlerAL204电子天平Ffactor系数fehling’sreaction斐林实验filter过滤finenessoftheparticles颗粒细度flowrate流速fluorescentagent荧光剂fluorescencespectrophotometry荧光分光光度法fluorescencedetection荧光检测器fluorescenceanalysis荧光分析法foreignpigment有色杂质formulary处方集free游离freezingtest冻结试验fusedsilica熔融石英filterpaper滤纸Ggaschromatography气相色谱法gas-liquidchromatography气液色谱法gaspurifier气体净化器Generalidentificationtest一般鉴别试验generalnotices凡例Generalrequirements(药典)通则goodclinicalpractices药品临床管理规范goodlaboratorypractices药品实验室管理规范goodmanufacturingpractices(GMP)药品生产质量管理规范goodsupplypractices(GSP)药品供应管理规范gradientelution梯度洗脱grating光栅gravimetricmethod重量法Gutzeittest古蔡(检砷)法glassfunnellongstem玻璃漏斗gradcylinder量筒glassrod玻棒graduatedpipettes刻度吸管GC气相色谱Hheavymetal重金属halfpeakwidth平峰宽heatconductivity热导率heightequivalenttoatheoreticalplate理论塔板高度heightofaneffectiveplate有效塔板高度high-performanceliquidchromatography(HPLC)高效液相色谱法high-performancethin-layerchromatography(HPTLC)高效薄层色谱法hydrate水合物hydrolysis水解hydrophilicity亲水性hydrophobicity疏水性hydroxylvalue羟值hyperchromiceffect浓色效应hypochromiceffect淡色效应HHS-typeconstanttemperaturewaterbathHHS型恒温水锅HPLC高效液相色谱法Iidentification鉴别ignitiontoconstantweight灼烧至恒重immobilephase固定相immunoassay免疫测定impurity杂质inactivation失活index索引indicatorelectrode指示电极indicator指示剂inhibitor抑制剂injectingseptum进样隔膜胶垫instrumentalanalysis仪器分析injectionvalue进样阀insulinassay胰岛素生物检测法integrator积分仪intercept截距interface接口internalstandardsubstance内标物质Internationalunit国际单位invitro体外invivo体内iodide碘化物iodoformreation碘仿反应iodometry碘量法ionpairchromatography离子对色谱ionsuppression离子抑制ionsuppression离子抑制ionicstrength离子强度ion-pairingagent离子对试剂ionization电离isoabsorptivepoint等吸收点isocraticelution等溶剂组成洗脱isoelectricpoint等电点isoosmoticsolution等渗溶液irreversibleindicator不可逆指示剂irreversiblepotential不可逆电位KKarlFischertitration卡尔-费舍尔滴定Kjeldahlmethodfornitrogen凯氏定氮法Koberreagent 科伯试剂Kovatsretentionindex科瓦茨保留指数Llabelledamount标示量leadingpeak前延峰levelingeffect均化效应licensedpharmacist执业药师limitcontrol限量控制limitofdetection检测限limitofquantitation定量限limittest杂质限度试验lossondrying干燥失重lowpressuregradientpump氧压梯度泵linearityandrange线性及范围linearityscanning线性扫描luminescence发光litmuspaper石蕊试纸lyophilization冷冻干燥Mmainconstituent主成分make-upgas尾吹气maltolreaction麦芽酚试验Marquistest马奎斯试验massanalyzerdetector质量分析检测器massspectrometricanalysis质谱分析massspectrum质谱图meandeviation平均偏差meltingpoint熔点meltingrange熔距metabolite代谢物metastableion亚稳离子micellarchromatography胶束色谱法microanalysis微量分析microcrystal微晶microdialysis微透析migrationtime迁移时间Milliporefiltration微孔过滤mobilephase流动相molecularformula分子式monitor检测monochromator单色器monographs正文Nnaturalproduct天然产物Nessler’sreagent碱性碘化汞试液neutralization中和nitrogencontent总氮量nonaqueousacid-basetitration非水酸碱滴定nonprescriptiondrug,overthecounterdrugs非处方药nonspecificimpurity一般杂质non-volatilematter不挥发物normalphase正相normalization归一化法Nesslercolorcomparisontube纳氏比色管Onotice凡例octadecylsilanebondedsilicagel十八烷基硅烷键合硅胶odorless辛基硅烷odorless无臭officialname法定名officialtest法定试验on-columndetector柱上检测器on-columninjection柱头进样onthedriedbasis按干燥品计opalescence乳浊opticalactivity光学活性opticalisomerism旋光异构opticalpurity光学纯度organicvolatileimpurities有机挥发性杂质orthogonaltest正交试验orthophenanthroline邻二氮菲outlier可疑数据overtones倍频封oxidation-reductiontitration氧化还原滴定oxygenflaskcombustion氧瓶燃烧Ppackedcolumn填充柱packingmaterial色谱柱填料palladiumioncolorimetry钯离子比色法parention母离子particulatematter不溶性微粒partitioncoefficient分配系数patternrecognition(ppm)百万分之几peaksymmetry峰不对称性peakvalley峰谷peakwidthathalfheight半峰宽percenttransmittance透光百分率pHindicatorabsorbanceratiomethodpH指示剂吸光度比值法pharmaceuticalanalysis药物分析pharmacopeia药典pharmacy药学photometer光度计polarimetry旋光测定法polarity极性polydextrangel葡聚糖凝胶potentiometer电位计potentiometrictitration电位滴定法precipitationform沉淀形式precision精密度preparation制剂prescriptiondrug处方药pretreatment预处理primarystandard基准物质principalcomponentanalysis主成分分析prototypedrug原型药物purification纯化purity纯度pyrogen热原pycnometermethod比重瓶法plasticwashbottle洗瓶platformbalance天平pipette移液管pyknowmeterflasks容量瓶Qqualitycontrol质量控制qualityevaluation质量评价qualitystandard质量标准quantitativedetermination定量测定quantitativeanalysis定量分析quasi-molecularion准分子离子Rracemization消旋化randomsampling随机抽样rationaluseofdrug合理用药readilycarbonizablesubstance易炭化物质reagentsprayer试剂喷雾剂recovery回收率referenceelectrode参比电极relatedsubstance相关物质relativedensity相对密度relativeintensity相对强度repeatability重复性replicatedetermination平行测定reproducibility重现性residualbasichydrolysismethod剩余碱水解法residualliquidjunctionpotential残余液接电位residualtitration剩余滴定residuceonignition炽灼残渣resolution分辨率responsetime响应时间retention保留reversedphasechromatography反相色谱法reverseosmosis反渗透rinse淋洗robustness可靠性round修约reagentbottles试剂瓶roundbottomflask圆底烧瓶rubbersuctionbulb洗耳球Ssafety安全性Sakaguchitest坂口试验saltbridge盐桥saltingout盐析sampleapplicator点样器sampleapplication点样sampling取样saponificationvalue皂化值saturatedcalomelelectrode饱和甘汞电极selectivity选择性significantdifference显着性水平significanttesting显着性检验silicaget硅胶silverchlorideelectrode氯化银电极similarity相似性sodiumdodecylsulfate十二基酸钠solid-phaseextraction固相萃取solubility溶解度specificabsorbance吸收系数specification规格specificity专属性specificrotation比旋度specificweight比重spiked加入标准的splitinjection分流进样sprayreagent显色剂stability稳定性standardcolorsolution标准比色液standarddeviation标准差standardization标定standardsubstance标准品statisticalerror统计误差sterilitytest无菌试验stocksolution储备液stoichiometricpoint化学计量点storage贮藏straylight杂散光substrate底物substituent取代基sulfate硫酸盐sulphatedash硫酸盐灰分support载体suspension旋浊度swellingdegree膨胀度symmetryfactor对称因子systematicerror系统误差separatingfunnel分液漏斗stopcock玻璃活塞scissors剪刀spiritlamp酒精灯silicagelGthinlayer硅胶G薄层板Ttable片剂tailingfactor拖尾因子tailingpeak拖尾峰testsolution试液thermalanalysis热分析法thermalconductivitydetector热导检测器thermogravimetricanalysis热重分析法TheUnitedStatesPharmacopoeia美国药典ThePharmacopoeiaofJapan日本药局方thinlayerchromatography薄层色谱thiochromereaction硫色素反应thymol百里酚thymolphthalein百里酚酞titer滴定度three-dimensionalchromatogram三维色谱图titrant滴定剂titrationerror滴定误差titrimetricanalysis滴定分析法tolerance容许限totalash总灰分totalqualitycontrol全面质量控制traditionaldrugs传统药traditionalChinesemedicine中药turbidance浑浊turbidimetricassay浊度测定法turbidimetry比浊度turbidity浊度Uultracentrifugation超速离心ultravioletirradiation紫外线照射unduetoxicity异常毒性uniformdesign均匀设计uniformityofdosageunits含量均匀度uniformityofvolume装量均匀性uniformityofweight重量均匀性Vvalidity可靠性variance方差viscosity粘度volatileoildeterminationapparatus挥发油测定器volatilization挥发性volumetricanalysis容量分析volumetricsolution滴定液volumetricflasks比重瓶Wwavelength波长wavenumber波数weighingbottle称量瓶weighingform称量形式well-closedcontainer密闭容器whiteboard白瓷板XxylenecyanolblueFF二甲苯蓝FFxylenolorange二甲酚橙ZZigzagscanning锯齿扫描zwitterions两性离子Zymolysis酶解作用zoneelectrophoresis区带电泳。

Quasi-static and dynamic fracture behavior of composite sandwich beams

$Quasi-static and dynamic fracture behavior of composite sandwich beams$

Ó 2010 Elsevier Ltd. All rights reserved.
1. Introduction
Nowadays, due to the combining features of high bending stiffness and low weight, composite sandwich materials/structures have been widely used in marine, transportation, civil construction and aerospace applications. The sandwich interface, which transfers stress and other physical responses between the core and the facing sheet, is one kind of adhesive material showing viscoelastic characters. The performance of adhesive layer has signiﬁcant inﬂuence on the physical, chemical, mechanical properties and service life of the composite sandwich structures. However, due to the anisotropy and nonhomogeneity of composite sandwich structures, the interface debonding between the core and the facing is one of the often-encountered failure modes during the processes of manufacturing, testing, transportation or service. Then, crack initiation and instable growth will affect transferring of mechanical responses between the core and the facing sheet and eventually lead to overall failure [1].

抗体和寡核苷酸双标记纳米金生物探针的制备及生物学特性

Vo.l30高等学校化学学报No.1 2009年1月CHEM I CAL J OURNAL OF CH I NESE UN I VERSI T I E S60~63抗体和寡核苷酸双标记纳米金生物探针的制备及生物学特性李富荣1,乔飞燕2,孔小丽1,周汉新1,齐晖1,任莉莉1(1.暨南大学第二临床医学院(深圳人民医院)临床医学研究中心,深圳518020;2.兰州大学化学化工学院,兰州730000)摘要纳米金通过静电吸附抗体,与寡核苷酸共价结合制备双标记纳米金生物探针,比较了双标记纳米金生物探针和单标记抗体IgG或ss-DNA的稳定性和反应性.结果表明,在水溶液中纳米金由于ss-DNA的结合使IgG抗体的吸附能力明显改善,IgG的吸附也影响二硫苏糖醇(DDT)对ss-DNA的解离作用.双标记纳米粒上覆盖(50?15)条ss-DNA和(10?2)条IgG,较单标记ss-DNA纳米金上的(70?15)条要少.斑点免疫和杂交实验证明,纳米金表面标记的IgG和ss-DNA具有良好生物学活性.双标记纳米金生物探针在超微量蛋白质的检测中具有应用价值.关键词金纳米粒子;生物探针;寡核苷酸;抗体中图分类号O629.7文献标识码A文章编号0251-0790(2009)01-0060-04目前,在早期癌抗原及某些神经肽等极微量抗原检测上,荧光标记及酶标记技术还缺乏足够的灵敏性,在一些超微量蛋白,如早期肿瘤抗原和神经肽的检测,同位素的检测灵敏性虽然可达到1L g/mL,但需要特殊的设备和安全保护,限制了其使用.由于纳米金具有很强的免疫标记能力,可以和很多基团进行键合,其共轭化合物有很宽的p H稳定性、很高的离子强度以及离子稳定性,为生物学检测提供了一个很好的平台[1,2].纳米金已经被应用到许多超敏感生物传感器上[3~6].M irkin等[7~9]建立了/生物条码核酸芯片检测法0,成功应用于PSA,H CG及AFP等超微量物质的检测,检测下限比传统的ELI SA低6个数量级.目前有关双标记纳米金生物探针制备报道甚少,有关双标记后抗体和DNA 的相互影响及其在应用中活性的保持等尚待研究.本文就双标记纳米金生物探针的制备和生物学特性进行了探索研究,并对纳米金上抗体和ss-DNA吸附的稳定性进行了探讨.1实验部分1.1材料与仪器胶体金粒径为(10?5)nm(上海久山化工有限公司);羊抗兔Ig G(北京鼎国生物技术公司); ss-DNA由上海生工生物工程公司人工合成,硫醇修饰的ss-DNA序列:5c-GCTAGTGAAC AC AGTTGTG-TAAAAAAAAAA(C H2)3-S H-3c,互补序列:5c-ACACAACTGTGTTC ACTAGCTTTTTTTTTTCGATCACT-TGTGTCAACACA-3c.上游引物:5c-GCTAGTGAACACAGT-3c,下游引物:5c-(T)10AC AC-3c,硝酸纤维素膜(碧云天生物技术研究所);其它化学试剂均为分析纯;实验用水为灭菌二次水.DU800紫外分光光度计(美国Beckm an公司);透射电子显微镜(TEC HA I-10,荷兰P H I LI PS);H S-3垂直混合器(宁波新芝生物科技股份有限公司);0122L m微孔滤膜(北京鼎国生物技术公司).1.2金纳米粒子生物探针的制备1.2.1纳米金抗体(I gG-Au)的标记将金纳米粒子用0122L m的微孔滤膜进行过滤.取5mL纳米金粒子溶液,用K2C O3调pH值为9,加入25L g羊抗兔I gG,摇匀5m i n后,迅速加入250L L质量分数收稿日期:2008-04-23.基金项目:国家/八六三0计划项目(批准号:2003BA310A23)和深圳市科技局计划项目(批准号:2004B110)资助.联系人简介:李富荣,男,博士,研究员,博士生导师,主要从事医用纳米技术研究.E-m ai:l frli62@yahoo.co m为1%的聚乙二醇(PEG)溶液,在常温下放置2~3h ,在4e 低温下离心30m i n ,吸去上清液,在沉淀中加入p H =712的磷酸盐缓冲溶液(PBS),除去未结合的抗体和PEG ,重复操作2次后,将样品溶于5mL 0105%的PEG (pH =710的PBS 和0105%的叠氮钠)溶液,于4e 下冷藏保存备用.1.2.2 纳米金单链寡核苷酸(Au -DNA )标记将515m g 硫醇荧光团标记的ss -DNA 与5mL 纳米金混合,振摇3m in 后室温孵育12h ,加入500m L 012m o l/L NaC l 和500mL 10mm o l/L PBS(p H =710)后,于45e 孵育12h ,以14000r/m i n 离心20m i n ,移去上层清液,重复操作2次,除去未反应的DNA,沉淀物溶于相同溶液,于4e 保存备用.1.2.3 抗体和ss -DNA 双标记纳米金(I gG -Au -DNA )生物探针的制备将515m g 硫醇荧光团标记ss -DNA 与5mL I gG-Au 溶液混合,振摇5m in 后于室温孵育12h ,加入500L L 015m ol/L NaC l 和500mL 10mm o l/L PBS(pH =710),室温放置2h ,以14000r /m i n 离心20m i n ,移去上层清液,重复操作2次,除去未反应的DNA,沉淀物溶于相同溶液,于4e 保存备用.1.3 生物学特性检测1.3.1 样品电镜检测用微量取样器分别取一定量液体样品加入铜网中,在白炽灯下烘烤015h ,直到液体蒸干后,放入透射电子显微镜中检测.1.3.2 聚丙烯酰胺凝胶(PAEG )电泳检测采用2mL 制备好的双标记纳米金生物探针,加入二硫苏糖醇(DTT),低温超速离心后取上清液,作为PCR 扩增样品.采用20L L 反应体系进行扩增,预变性94e 5m i n ,94e 30s ,50e /60e 30s ,72e 30s ,循环扩增35次,最后于72e 延伸3m in .将扩增产物用饱和尿素处理,高温55e 水浴10m i n ,速冻,加入7m o l/L 尿素,用体积分数为15%的变性PAGE 分析.每孔点样20L L ,以溴酚蓝为对比示踪剂,以合成的15,30和50bp 寡核苷酸混合物为M ar ker ,电压80V,对1h 后溴化乙锭(EB)染液中凝胶成像系统进行观察拍照.1.3.3 ss -DNA 连接率的检测取2mL 制备好的双标记纳米金生物探针(217nmo l/L),加入011m o l/L DTT 至终浓度为0101mo l/L ,静置30m i n ~1h .每3m i n 紫外扫描1次,观察DTT 取代纳米金探针上硫醇修饰的寡核苷酸的动力学变化,并以纳米金溶胶和普通免疫金探针作对照,通过溶液荧光检测寡核苷酸的数量.1.3.4 抗体活性检测剪取2c m @4c m 的硝酸纤维素膜,在pH =910的碳酸钠溶液中浸泡10m i n .干燥后在其表面涂覆一层环形羊抗兔I gG,湿盒37e 作用20m i n ,洗涤2~3次,滤纸吸干.将10L L 样品(金纳米粒子、抗体修饰的金纳米粒子和ss -DNA 修饰的金纳米粒子)加入到环形圈内,37e 孵育,在有颜色变化前用PBST [PBS(10mm ol/L ,p H =710)和Tw een -20,体积比20B 1]洗涤后读取结果.2 结果和讨论2.1 纳米金生物探针的制备Ig G 或ss -DNA 标记纳米金制备已有相关报道[10~12],关于I gG 和ss -DNA 双标记纳米金则尚未见报道.选择将纳米金与I gG 抗体结合后再与ss -DNA 结合的方法.如果纳米粒先被ss -DNA 修饰,将影响下一步与Ig G 的结合,主要是由硫醇修饰的ss -DNA 吸附到纳米金表面形成一个密封层所致.没有修饰的胶体金在高浓度盐溶液条件下处于不稳定状态,当加入015m o l/L HC l 溶液时,纳米金溶液就会发生聚集,颜色会迅速由红变蓝,这主要是溶液中残留的负离子在纳米金周围形成负电荷层,在纳米颗粒之间形成聚合力的缘故[13].I gG 和Ig G /ss -DNA 可以改变纳米颗粒表面的电荷,使修饰后的纳米金处于稳定状态.没有修饰的纳米金在015m ol/L NaC l 溶液中会发生聚集[图1(A )],在相同条件下,Ig G-A u[图1(B )]和I gG-Au -DNA [图1(C )]仍保持稳定状态,没有发生聚集.而个别纳米金聚集形成二聚体的现象,可能是抗体和寡核苷酸修饰不足,处于不稳定状态所致.ss -DNA 修饰较Ig G 修饰简单,纳米金和寡核苷酸的反应需在高浓度的氯化钠溶液以及pH 为710的磷酸盐缓冲溶液中完成,纳米金表面修饰抗体后,微粒间的稳定性大大提高,又可使ss -DNA 在其表面结合,在高浓度的盐溶液中不会发生聚集,解决了纳米金在免疫试验中假阳性的问题.没有修饰纳米金的紫外-可见光谱最大吸收值在518nm,修饰抗体后的金纳米粒子的吸收峰发生了轻微的移动,61 N o .1 李富荣等:抗体和寡核苷酸双标记纳米金生物探针的制备及生物学特性Fig .1 TEM i m ages of unm od ified gold nanopartic l es(A),Ig G-Au(B )and Ig G-Au -DNA (C )F i g .2 UV -V is spec tra of unm od ified gold nanoparticles(a ),Ig G-Au(b )and IgG -Au -DNA(c )nanoparticles 从518nm 处移向522n m.而抗体和ss -DNA 共同修饰的金纳米粒子的吸收峰在524nm 处(图2),表明纳米金对周围环境非常敏感.由图2可见,吸附了抗体和DNA的纳米金的紫外-可见光谱没有发生明显改变,表明纳米金没有明显变化.2.2 IgG 和ss -DNA 连接数量利用考马斯亮蓝(G -250)检测纳米金上覆盖IgG 的数量.G-250与蛋白质通过范德华力相互作用,形成蛋白质-考马斯亮蓝复合物,使考马斯亮蓝最大吸收峰,从465nm 红移到595nm.由于此结合物的吸光度远高于考马斯亮蓝在465n m 处的吸光度,从而大大提高了蛋白质的测量灵敏度[14].用此法检测Ig G-A u 和I gG -Au -DNA 的离心上清液,结果表明,吸附在纳米金上的I gG 数量为(10?2)个.纳米金的荧光最大吸收峰值位于524nm,表面结合DNA 后,由于荧光共振能量转移(FRET )作用,纳米金粒子表面标记的荧光发生猝灭.由于ss -DNA 可以被更强结合力的分子(如DTT )所取代,使标记的ss -DNA 寡核苷酸被释放出来,通过测定荧光密度计算出ss -DNA 的数量.结果表明,每个I gG -Au 和Ig G-Au-DNA 表面覆盖的寡核苷酸分别为(70?15)条和(50?15)条ss -DNA,标记在纳米金表面的Ig G 和DNA 的比值约为2B 5.由于每个DTT 分子有2个硫醇团,通过共价键可结合2个纳米金.当在DNA 修饰的纳米颗粒中加入DTT,可替代寡核苷酸发生纳颗米粒聚集使颜色由红变蓝,颜色反应可用来检测这种替代的发生[见图3(A )].加入DTT 后,纳米金谱带变宽,并逐步从524nm 转移到650nm,这段时间大约需要2m i n .原来的524n m 谱带完全消失,但移动速度在双标记纳米金上变化较慢,在30m i n 后仍能看到524nm 谱带.这主要是Ig G-Au-DNA 上的Ig G 较大,可能阻碍了DTT 进入纳米金表面所致.F i g .3 T i me evo l u ti on of UV -V is spectra of A u -DNA (A )and Ig G-Au -DNA (B )after adding DTT2.3 纳米金表面的抗体活性利用斑点免疫技术检测纳米金表面Ig G 的含量(见图4).在Ig G-Au 和Ig G-Au-DNA 覆盖区可见颜色沉淀,表明发生抗原抗体反应;而无Ig G 区没有颜色变化.表明Ig G-Au 和I gG-Au -DNA 生物探针上62高等学校化学学报 V o.l 30F ig .4 Dot i mmuno -gold nanop rob e d etec ti on ofIgG -Au (A ),Ig G-Au -DNA (B )and unm od ified gold nanoparticles(C)抗体保留了生物活性.Ig G -Au 和Ig G -Au -D NA 纳米颗粒之间没有明显差异,说明吸附ss -DNA 不影响Ig G 的反应.2.4 纳米金上ss -DNA 的活性为了证明纳米金表面的寡核苷酸是否可与互补序列杂交,设计了一个互补寡核苷酸.这个序列有两个相同部分可与纳米金上寡核苷酸互补并可与2个纳米金发生反应,通过杂交出现纳米金聚集,30m in 后ss -DNA 修饰的纳米颗粒溶液会变蓝,Ig G-Au-DNA 纳米颗粒紫外吸收峰移到580nm 处,表明纳米金上的寡核苷酸与互补寡核苷酸发生杂交,发生凝聚.参考文献[1] Oli ver C..M ethod sM o.l B i o.l [J],1999,115(3):347)54[2] W ill n er I .,Bas n ar B .,W ill ner B..FEBS .J .[J],2007,274(2):302)309[3] Par k S.J .,Taton T .A .,M irk i n C. A..S ci ence[J],2002,295(5559):1503)1506[4] Fan C.,W ang S.,H ong J .W.,et al ..Proc .Nat.l A cad .Sc.i USA[J],2003,100(11):6297)6301[5] Xiao Y.,Patols ky F .,Katz E.,et al ..Science[J],2003,299(5614):1877)1881[6] Dub ertret B .,C al a m e M.,L i b chaber A .J ..Nat .B iotechno.l [J],2001,19(4):365)370[7] N a m J .M.,Thaxton C.S.,M irk i n C. A..Science[J],2003,301(5641):1884)1886[8] S t oeva S .I .,Lee J .S.,Sm ith J . E.,e t al ..J .Am.Che m.Soc .[J],2006,128(26):8378)8379[9] S t oeva S .I .,Lee J .S.,Thax t on C .S .,et al ..Ange w.Che m.In t .E d .Eng.l [J],2006,45(20):3303)3306[10] G eorgan opou l ou D.G.,C hang L .,N a m J .M.,e t al ..Proc .Nat.l A cad .USA[J],2005,102(7):2273)2276[11] K i m E.Y.,S tanton J .,Vega R .A .,e t al ..Nu c.l Aci ds .Res .[J ],2006,34(7):47)54[12] A ckerson C.J .,SykesM.T.,Kornberg R.D ..P roc .Nat.l Acad .S c.i U SA[J],2005,102(38):13383)13385[13] K anaras A .G .,W ang Z .,Bat es A. D.,et a l ..Ange w.Che m.In t .E d .Eng.l [J],2003,42(2):191)194[14] YAN Q i u-Pi ng(颜秋平),LI Fu -Rong(李富荣),TANG Shun -Q ing(汤顺清),e ta l ..Ch i n .J .B i om ed .Eng .(中国生物医学工程报)[J ],2006,25(3):305)309Preparati on and B i ological Characterization of Antibody andDNA Dua-l labeled Gold NanoparticlesL I Fu-Rong 1*,Q I A O Fe-i Yan 2,KONG X iao -L i 1,Z HOU H an-X i n 1,Q IH ui 1,RE N L-i Li1(1.C linicM ed ical Research C enter,T he 2nd ClinicM edical College(Shenzhen P eop le c s H osp ital),J i nan Un i ver sit y,Shenzhen 518020,China ;2.D epart m ent of Che m istry and Che m ical Eng i neering,Lanzhou Universit y,Lanzhou 730000,Chi na)Abst ract Go ld nanoparticles labe l e d by both anti b ody (I gG)and sing le stranded DNA (ss -DNA )w ere syn -thesized and characterized .The stability and reactiv ity of the dua-l labeled nanoparticles w ere co m pared w ith t h e conventi o na l I gG or ss -DNA m odified nanoparticles .It w as found that the Ig G adsor pti o n si g nifican tl y i m -proved t h e stab ility of the nanoparticles in aqueous so l u tion,w hich is bene ficial f o r attach i n g ss -DNA.The presence o f Ig G a lso effective l y pr ohibits the desorption o f ss -DNA against d ith i o thre ito l(DTT)displace m en.t The coverage on dua-l labeled nanoparticles w as found to be (50?15)ss -DNA /nanoparticle and (10?2)I gG /nanoparticle ,respectively ,co m pared to the value o f (70?15)ss -DNA /nanopartic le of on l y ss -DNA-la -beled go l d nanoparticles .Do -t i m m uno and cross -linking experi m ents confir m ed that bo t h the Ig G and ss -DNA retained their bioacti v ity on the nanopartic le surface .The dua-l labe led nanopartic les have potential to be used as novel b i o -probes for ultrasensiti v e detection .K eywords Gold nanopartic le ;B i o -probes ;DNA;Anti b ody (Ed .:H,J ,Z)63 N o .1 李富荣等:抗体和寡核苷酸双标记纳米金生物探针的制备及生物学特性。

聚二甲基硅氧烷芯片自由酶反应器检测葡萄糖

聚二甲基硅氧烷芯片自由酶反应器检测葡萄糖作者：仲海燕周洁余晓冬陈洪渊【摘要】应用电泳中介微分析（EMMA）技术，构建聚二甲基硅氧烷（PDMS）芯片自由酶反应器，在线检测葡萄糖（Glu），在十字形的芯片通道上，采用自制的碳纤维微电极检测葡萄糖氧化酶（GOD）催化氧化Glu生成的H2O2，并对检测电位、GOD浓度、GOD进样时间、分离电压等参数进行了优化，测定了该自由酶反应器的线性范围和检出限，考察了其重现性及稳定性。

结果表明，此自由酶反应器制作方便，操作简单，重现性好，Glu浓度在0.1～20 mmol/L之间有较好的线性关系（r=0.997），检出限为19.8 μmol/L（S/N=3）。

【关键词】自由酶反应器；葡萄糖；电泳中介微分析；聚二甲基硅氧烷芯片The Key Lab of Analytical Chemistry for Life Science, Ministry of Education, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093)Abstract Microfluidic enzyme based reactor could be used to detect the biomolecules with high sensitivity and selectivity. Based on the electrophoretic mediated microanalysis (EMMA) method, a new kind of free enzyme based poly(dimethylsiloxane) (PDMS) microchip was developed to detect glucose (Glu). On line catalysis reaction of Glu by glucose oxidase (GOD) was carriedout on the chip. The product H2O2 was detected using single carbon fibre cylindrical electrode. Factors influencing the separation and detection, such as detection potential, GOD concentration, GOD injection time and separation voltage, were investigated and optimized. Results showed that the peak current had a good linear relationship with Glu concentration in the range of 0.1－20 mmol/L (R=0.997). The detection limit of Glu was 19.8 μmol/L (S/N=3). In addition, the PDMS enzyme based reactor had long term stability and excellent reproducibility (RSD=2.02%, n=10). It was easy to fabricate and operate, which showed great potential application in bioanalysis.Keywords Free enzyme based microchip; Glucose; Electrophoretic mediated microanalysis; Poly(dimethylsiloxane)1 引言近年来，基于酶催化反应的微流控芯片备受关注。

分析化学中英语简称

第一章绪论分析化学：analytical chemistry定性分析：qualitative analysis定量分析：quantitative analysis物理分析：physical analysis物理化学分析：physico-chemical analysis仪器分析法：instrumental analysis流动注射分析法：flow injection analysis；FIA顺序注射分析法：sequentical injection analysis;SIA化学计量学：chemometrics第二章误差的分析数据处理绝对误差：absolute error相对误差：relative error系统误差：systematic error可定误差：determinate error随机误差：accidental error不可定误差：indeterminate error准确度：accuracy精确度：precision偏差：debiation，d平均偏差：average debiation相对平均偏差：relative average debiation标准偏差（标准差）：standerd deviation;S相对平均偏差：relatibe standard deviation;RSD变异系数：coefficient of variation误差传递：propagation of error有效数字：significant figure置信水平：confidence level显著性水平：level of significance合并标准偏差（组合标准差）：pooled standard debiation 舍弃商：rejection quotient ;Q化学定量分析第三章滴定分析概论滴定分析法：titrametric analysis滴定：titration容量分析法:volumetric analysis化学计量点：stoichiometric point等当点：equivalent point电荷平衡：charge balance电荷平衡式：charge balance equation质量平衡：mass balance物料平衡：material balance质量平衡式：mass balance equation第四章酸碱滴定法酸碱滴定法：acid-base titrations质子自递反应：autoprotolysis reaction质子自递常数：autoprotolysis constant质子条件式:proton balance equation酸碱指示剂：acid-base indicator指示剂常数：indicator constant变色范围：colour change interval混合指示剂：mixed indicator双指示剂滴定法：double indicator titration第五章非水滴定法非水滴定法：nonaqueous titrations质子溶剂：protonic solvent酸性溶剂：acid solvent碱性溶剂：basic solvent两性溶剂:amphototeric solvent无质子溶剂：aprotic solvent均化效应：differentiating effect区分性溶剂：differentiating solvent离子化：ionization离解：dissociation结晶紫：crystal violet萘酚苯甲醇: α-naphthalphenol benzyl alcohol奎哪啶红：quinadinered百里酚蓝：thymol blue偶氮紫：azo violet溴酚蓝：bromophenol blue第六章配位滴定法配位滴定法：compleximetry乙二胺四乙酸：ethylenediamine tetraacetic acid,EDTA 螯合物：chelate compound金属指示剂：metal lochrome indcator第七章氧化还原滴定法氧化还原滴定法：oxidation-reduction titration 碘量法：iodimetry溴量法：bromimetry ]溴量法：bromine method铈量法：cerimetry高锰酸钾法：potassium permanganate method条件电位：conditional potential溴酸钾法：potassium bromate method硫酸铈法：cerium sulphate method偏高碘酸：metaperiodic acid高碘酸盐：periodate亚硝酸钠法：sodium nitrite method重氮化反应：diazotization reaction重氮化滴定法：diazotization titration亚硝基化反应：nitrozation reaction亚硝基化滴定法：nitrozation titration外指示剂：external indicator外指示剂：outside indicator重铬酸钾法：potassium dichromate method第八章沉淀滴定法沉淀滴定法：precipitation titration容量滴定法：volumetric precipitation method 银量法：argentometric method第九章重量分析法重量分析法：gravimetric analysis挥发法：volatilization method引湿水（湿存水）：water of hydroscopicity包埋(藏)水：occluded water吸入水：water of imbibition结晶水：water of crystallization组成水：water of composition液-液萃取法：liquid-liquid extration溶剂萃取法：solvent extration反萃取：counter extraction分配系数：partition coefficient分配比：distribution ratio离子对（离子缔合物）：ion pair沉淀形式：precipitation forms称量形式：weighing forms《分析化学》下册仪器分析概述物理分析：physical analysis物理化学分析：physicochemical analysis仪器分析：instrumental analysis第十章电位法及永停滴定法电化学分析：electrochemical analysis电解法：electrolytic analysis method电重量法：electtogravimetry库仑法：coulometry库仑滴定法：coulometric titration电导法：conductometry电导分析法：conductometric analysis电导滴定法：conductometric titration电位法：potentiometry直接电位法：dirext potentiometry电位滴定法：potentiometric titration伏安法：voltammetry极谱法：polarography溶出法：stripping method电流滴定法：amperometric titration化学双电层：chemical double layer相界电位：phase boundary potential金属电极电位：electrode potential化学电池：chemical cell液接界面：liquid junction boundary原电池：galvanic cell电解池：electrolytic cell负极：cathrode正极：anode电池电动势：eletromotive force指示电极：indicator electrode参比电极：reference electroade标准氢电极：standard hydrogen electrode 一级参比电极：primary reference electrode 饱和甘汞电极：standard calomel electrode银－氯化银电极：silver silver-chloride electrode液接界面：liquid junction boundary不对称电位：asymmetry potential表观PH值：apparent PH复合PH电极：combination PH electrode离子选择电极：ion selective electrode敏感器：sensor晶体电极:crystalline electrodes均相膜电极：homogeneous membrance electrodes非均相膜电极：heterog eneous membrance electrodes非晶体电极：non- crystalline electrodes刚性基质电极：rigid matrix electrode流流体载动电极：electrode with a mobile carrier气敏电极：gas sensing electrodes酶电极：enzyme electrodes金属氧化物半导体场效应晶体管：MOSFET离子选择场效应管：ISFET总离子强度调节缓冲剂：total ion strength adjustment buffer,TISAB永停滴定法：dead-stop titration双电流滴定法（双安培滴定法）：double amperometric titration第十一章光谱分析法概论普朗克常数：Plank constant电磁波谱：electromagnetic spectrum光谱：spectrum光谱分析法：spectroscopic analysis原子发射光谱法：atomic emission spectroscopy质量谱：mass spectrum质谱法：mass spectroscopy,MS第十二章紫外－可见分光光度法紫外－可见分光光度法：ultraviolet and visible spectrophotometry;UV-vis 肩峰：shoulder peak末端吸收：end absorbtion生色团：chromophore助色团：auxochrome红移：red shift长移：bathochromic shift短移：hypsochromic shift蓝（紫）移：blue shift增色效应（浓色效应）：hyperchromic effect减色效应（淡色效应）：hypochromic effect强带：strong band弱带：weak band吸收带：absorption band透光率：transmitance,T吸光度：absorbance谱带宽度：band width杂散光：stray light噪声：noise暗噪声：dark noise散粒噪声：signal shot noise闪耀光栅：blazed grating全息光栅：holographic graaing光二极管阵列检测器：photodiode array detector 偏最小二乘法：partial least squares method ,PLS 褶合光谱法：convolution spectrometry褶合变换：convolution transform,CT离散小波变换：wavelet transform,WT多尺度细化分析：multiscale analysis供电子取代基：electron donating group吸电子取代基：electron with-drawing group第十三章荧光分析法荧光：fluorescence荧光分析法：fluorometryX-射线荧光分析法：X-ray fulorometry原子荧光分析法：atomic fluorometry分子荧光分析法：molecular fluorometry振动弛豫：vibrational relexation内转换：internal conversion外转换：external conversion体系间跨越：intersystem crossing激发光谱：excitation spectrum荧光光谱：fluorescence spectrum斯托克斯位移：Stokes shift荧光寿命：fluorescence life time荧光效率：fluorescence efficiency荧光量子产率：fluorescence quantum yield荧光熄灭法：fluorescence quemching method散射光：scattering light瑞利光：Reyleith scanttering light拉曼光：Raman scattering light第十四章红外分光光度法红外线：infrared ray,IR中红外吸收光谱：mid-infrared absorption spectrum,Mid-IR远红外光谱：Far-IR微波谱：microwave spectrum,MV红外吸收光谱法：infrared spectroscopy红外分光光度法：infrared spectrophotometry振动形式：mode of vibration伸缩振动：stretching vibration对称伸缩振动：symmetrical stretching vibration不对称伸缩振动：asymmetrical stretching vibration弯曲振动：bending vibration变形振动：formation vibration面内弯曲振动:in-plane bending vibration,β剪式振动：scissoring vibration,δ面内摇摆振动：rocking vibration,ρ面外弯曲振动：out-of-plane bending vibration,γ面外摇摆振动：wagging vibration,ω蜷曲振动：twisting vibration ,τ对称变形振动：symmetrical deformation vibration ,δs不对称变形振动：asymmetrical deformation vibration, δas特征吸收峰:charateristic avsorption band特征频率：characteristic frequency相关吸收峰：correlation absorption band杂化影响：hybridization affect环大小效应：ring size effect吸收峰的强度：intensity of absorption band环折叠振动：ring prckering vibration第十五章原子吸收分光光度法原子光谱法：atomic spectroscopy原子吸收分光光度法：atomic absorption spectrophotometry,AAS 原子发射分光光度法：atomic emmsion spectrophotometry,AES原子荧光分光光度法：atomic fluorescence spectrophotometry,AFS第十六章核磁共振波谱法核磁共振：nuclear magnetic resonance,NMR核磁共振波谱：NMR spectrum核磁共振波谱法：NMR spectroscopy扫场：swept field扫频：seept frequency连续波核磁共振：continuous wave NMR,CW NMRFourier变换NMR：PFT-NMR,FT-NMR二维核磁共振谱：2D-NMR质子核磁共振谱：proton magnetic resonance spectrum,PMR 氢谱：1H-NMR碳－13核磁共振谱：13C-NMR spectrum,13CNMR自旋角动量：spin angular momentum磁旋比：magnetogyric ratio磁量子数：magnetic quantum number,m进动：precession弛豫历程：relaxation mechanism局部抗磁屏蔽：local diamagnetic shielding屏蔽常数：shielding constant化学位移：chemical shift国际纯粹与应用化学协会：IUPAC磁各向异性：magnetic anisotropy远程屏蔽效应：long range shielding effect结面：nodal plane自旋－自旋偶合：spin-spin coupling自旋－自旋分裂：spin=spin splitting单峰：singlet,s双峰：doublet,d三重峰：triplet,t四重峰：quartet，q五重峰：quintet六重峰：sextet七重峰：septet/heptet， h八重峰：octet， o多重峰：multipet，m偕偶：geminal coupling邻偶：vicinal coupling远程偶合：long range coupling磁等价：magnetic eqivalence自旋系统：spin system一级光谱：first order spectrum二级光谱（二级图谱）：second order spectrumC-H光谱：C-H correlated spectroscopy,C-H COSY第十七章质谱法质谱分析法：mass spectrometry质谱：mass spectrum,MS棒图：bar graph选择离子检测：selected ion monitoring ,SIM直接进样：direct probe inlet ,DPI接口：interface气相色谱－质谱联用：gas chromatography-mass spectrometry,GC-MS高效液相色谱－质谱联用：high performance liquid chromatography-mass spectrometry,HPLC-MS电子轰击离子源：electron impact source,EI离子峰：quasi-molecular ions化学离子源：chemical ionization source,CI场电离：field ionization,FI场解析：field desorptiion,FD快速原子轰击离子源：fast stom bombardment ,FAB质量分析器：mass analyzer磁质谱仪：magnetic-sector mass spectrometer四极杆质谱仪（四极质谱仪）：quadrupole mass spectrometer原子质量单位:amu离子丰度：ion abundance相对丰度(相对强度)：relative avundance基峰：base peak质量范围：mass range分辨率：resolution灵敏度：sensitivity信噪比：S/N分子离子：molecular ion碎片离子：fragment ion同位素离子：isotopic ion亚稳离子：metastable ion亚稳峰：metastable peak母离子：paren ion子离子：daughter含奇数个电子的离子：odd electron含偶数个电子的离子：even eletron,EE均裂：homolytic cleavage异裂（非均裂）：heterolytic cleavage半均裂：hemi-homolysis cleavage重排：rearragement分子量：MWα－裂解：α-cleavage第十八章色谱分析法概论色谱法（层析法）：chromatography固定相：stationary phase流动相：mobile phase超临界流体色谱法：SFC高效毛细管电泳法：high performance capillary electroporesis,HPEC 气相色谱法：gas chromatography,GC液相色谱法：liquid cromatography,LC超临界流体色谱法：supercritical fluid chromatography,SFC气-固色谱法：GSC气-液色谱法：GLC液-固色谱法：LSC液-液色谱法：LLC柱色谱法：column chromatography填充柱：packed column毛细管柱：capillary column微填充柱：icrobore packed column高效液相色谱法：high performance liquid chromatography,HPLC平板色谱法：planar平板色谱法：plane chromatography纸色谱法：paper chromatography薄层色谱法：thin layer chromatography,TLC薄膜色谱法;thiin film chomatography毛细管电泳法：capillary electrophoresis,CE分配色谱法：partition chromatography吸附色谱法：adsorpion chromaography离子交换色谱法：ion exchange chromatography,IEC空间排阻色谱法：steric exclusion chromatography,SEC亲和色谱法：affinity chromatography分配系数：distribution cofficient狭义分配系数：partition coefficient凝胶色谱法：gel chromatography凝胶渗透色谱法：gel permeation chromatography,GPC凝胶过滤色谱法：gel filtration chromatography,GFC渗透系数：permeation coefficien;Kp化学键合相色谱法：chemically bonded-phase chromatography分配系数：distribution coefficient靛菁绿：indocyanine气相色谱－傅立叶变换红外光谱：GC-FTIR第十九章经典液相色谱法薄层色谱法：TLC吸附：adsorption活化：activation脱活性：deactivation交联度：degree of cross linking交换容量：exchange capacity薄层板：thin layer plate展开剂：developing solvent ,developer临界胶束浓度：criticak micolle concentration ,CMC相对比移值：relative Rf, Rr分离度：resolution ,R分离数：separation number,SN煅石膏：Gypsum羧甲基纤维素钠：CMC-Na吸收光谱联用：TLC-UV薄层色谱－荧光联用：TLC-F薄层色谱－红外吸收光谱联用：TLC-IR薄层色谱法：TLC-MS纸色谱法：paper chromatography上行展开：ascending development下行法展开：descending development双向展开：two dimensional develoooment第二十章气相色谱法气相色谱法：gas chromatography前延峰：leading peak拖尾峰：tailing peak对称因子：symmetry factor,fs保留时间：retention time保留体积：retention volume死时间：dead time调整保留时间：asjusted retention time半峰宽：peak width at half height,W1/2 or Y1/2峰宽：peak width,W等温线：isotherm理论塔板高度：height equivalent to atheoretical plate化学键合相：chemically bonded phase丁二酸二乙二醇聚酯：polydiethylene glycol succinate,PDEGS,DEGS 高分子多孔微球：GDX苯乙烯：STY乙基乙烯苯：EST二乙烯苯：DVB涂壁毛细管柱：wall coated open tubular column,WCOT载体涂层毛细管柱：supprot coated open tubular column,SCOT热导检测器：thermal conductivity detector,TCD氢焰离子化检测器：hydrogen flame ionization detector,FID电子捕获检测器：electron capture detector ,ECD噪声：noise,N漂移:drift,d灵敏度：sensitivity检测限(敏感度)：detectability,D,M分离度：resolution归一化法：normalization method外标法：external standardization第二十一章高效液相色谱法高效液相色谱法：high performance liquid chromatography,HPLC高速液相色谱法：high speed LC,HSLC高压液相色谱法：high pressure LC,HPLC高分辨液相色谱法：high resolution LC,HRLC液固吸附色谱法（液固色谱法）：liquid-solid adsorption chromatography,LSC 液液色谱法：liquid-liquid chromatography,LLC正相：normal phase,NP反相：reversed phase,RP化学键合相色谱法：bonded phase chromatography,BPC十八烷基：octadecylselyl,ODS离子对色谱法：paired ion chromatography,PIC反相离子对色谱法：RPIC离子抑制色谱法：ion suppression chromatography,ISC离子色谱法：ion chromatography,IC手性色谱法：chiral chromatography,CC环糊精色谱法：cyclodextrin chromatography,CDC胶束色谱法：micellar chromatography,MC亲和色谱法：affinity chromatography,AC固定相：stationary phase化学键合相：chemically bonde phase封尾、封顶、遮盖：end capping手性固定相：chiral stationary phase,CSP恒组成溶剂洗脱：isocraic elution梯度洗脱：gradient elution紫外检测器：ultraviolet detector,UVD荧光检测器：fluorophotomeric detector,FD电化学检测器：ECD示差折光检测器：RID光电二极管检测器：photodiode array detector ,DAD三维光谱－波谱图：3D-spectrochromatogram蒸发光散射检测器：evaporative light scattering detector,ELSD安培检测器：ampere detector,AD高效毛细管电泳法：high performance capillary electrophoresis,HPCE 淌度：mobility电泳：electrophoresis电渗：electroosmosis动力进样：hydrodynamic injection电动进样：electrokinetic injection毛细管区带电泳法：capillary zone electrophoresis,CZE胶束电动毛细管色谱：micellar electrokinetic capillary chromatography,MECC毛细管凝胶电泳：capillary gel electrophoresis,CGE筛分：sieving。

Optical Processes in Semiconductors

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(E)
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# of carriers
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Rabsorption v f ( Ev ) c ( Ec )(1 f ( Ec )) Remission v (1 f ( Ev )) c ( Ec ) f ( Ec ) Rnet Remission Rabsorption Rnet ( EFc EFv ) Eg
Gain and loss at T=0 K
at different pumping rates g
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N2 >N1
E EgBiblioteka Gain and loss at T>0 K
g
laser
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E Eg
Gain and loss at T>0 K
ZnSe
InP
Bandgap rules
The bandgap increases with decreasing lattice constant.
The bandgap decreases with increasing temperature.
Interband vs Intraband
•Nonlinear crystals
The energy bands One atom Two interacting atoms N interacting atoms