刺激相应聚合物小结
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Redox-responsive Macromolecules
Fig. 5 Schematic showing structure, redox properties, and proposed selfassembly of MO 65(L0.5/F0.5)20 copolypeptides into vesicles A. R. Rodriguez, J. R. Kramer and T. J. Deming, Biomacromolecules,2013, 14, 3610–3614.
Figure 2. (A) Transmittance vs temperature for 1 wt % P(MEO2MA-co-PEGMA2080) aqueous solution at the wavelength of 500 nm. (B) Optical photographs of 1 wt % P(MEO2MA-co-PEGMA2080) aqueous solution at different temperatures. K. C. Tam, ; et al, ACS Macro Lett. 2012, 1, 632–635.
Stimuli-Responsive Macromolecules
Thermoresponsive
Ionic strength responsive
Biomolecule responsive
Solubility, conformation and hydrophilic/hydrophobic transitions
Glucose-Sensitive Macromolecules
Figure 9. (A) Rh values of P(NIPAM-PBA) microgels (10.0 Scheme 3. Complexation Equilibrium between mol % PBA) as a function of glucose concentration, measured Phenylboronic Acid Derivative and Glucose in 0.005 M phosphate buffers of different pH values at T ) 25 °C. (B) Rh,0.05M/ Rh,0, the ratio of the particle size in the presence of 0.050 M glucose and that in the absence of glucose, as a function of pH value. Scheme 4 . Synthesis of Glucose-Sensitive P(NIPAM-PBA) Microgels with Pendant Phenylboronic Acids Zhang Y, Guan Y, Zhou S, Biomacromolecules 2006, 7, 3196-3201
Figure 1 | ‘Galaxy’ of nanostructured stimuli-responsive polymer materials.
Stimuli-responsive of macromolecules
Photoresponsive Redoxresponsive
pH responsive
Thermo-responsive Macromolecules
Figure 4. (a) Plots of transmittance as a function of temperature for aqueous solutions (2 mg/mL) of poly-L-EG2Glu and poly-L-EG3Glu. Solid line: heating; dashed line: cooling. (b) LCST of poly(EG2Glu- EG3Glu) copolypeptides as a function of sample composition.
Stimuli Responsive Macromolecules and Their Assemblies
Introduction
Stimuli-responsive polymers, also named ‘‘smart’’ polymers, can undergo chemical structure change or physical property variation in response to environmental stimuli, such as temperature, pH, ionic strength, light, biomolecules, etc.
Photo-responsive Macromolecules
Fig. 7 Schematic representation of doubleresponsive micellization of ‘‘schizophrenic’’ PSPMA-b-PDEGMMA in aqueous solution. Depending on temperature and light, the block copolymer formed micellar structures with various segments as core and corona, respectively Fig. 8 Common photo-responsive chemistries Q. Jin, G. Liu and J. Ji, J. Polym. Sci., A: Polym. Chem. 2010, 48, 2855–2861.
From an application perspective, relatively little attention has been paid to translate the fundamental understanding in molecular design criteria to develop polymers that would be biocompatible and biodegradable.
Thermo-responsive Macromolecules
Temperature responsive materials have been among the most studied stimuliresponsive materials for several decades due to their various applications. Also, the use of temperature as a stwk.baidu.commulus is potentially cheap and convenient.
Photo-responsive Polypeptides
Fig. 6 Schematic illustration of photo-responsive micellization/dissolution process for the PLGASP-b-PEO block copolymer. V. K. Kotharangannagari, R. Mezzenga, Macromolecules, 2011, 44, 4569–4573.
pH-responsive Macromolecules
Scheme 2. Formation of PMPC-b-PDPA Block Copolymer Vesicles Figure 6. Variation of hydrodynamic diameter of self-assembled colloidal aggregates formed by a PMPC25-b-PDPA120 copolymer in aqueous solution versus solution pH (the initial copolymer concentration at pH 2 was 1.0 g/L). Armes S P, JACS 2005 127, 17982-17983
Conclusions and Perspectives
The structural responses have often involved phase transformations, assembly formations or disassembly. The functional responses have involved molecular release, solubility variations, or color/fluorescence changes. Guided by these, stimuli responsive polymers have the potential to profoundly influence a broad spectrum of fields including surface science, sensing, tissue engineering, and drug delivery.
Scheme 1 LCST behavior of PNIPAM Thayumanavan S. et al. Chem. Soc. Rev. 2013, 42, 7421--7435
Thermo-responsive Macromolecules
Figure 3. Schematic illustration of twostage thermally induced aggregation process for random copolymer P(MEO2MA-co- PEGMA2080) in water