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• W2003803584 abstract "High molecular weight poly(l-glutamic acid) was chemically modified with a spiropyran reagent to give polypeptides containing 35 and 85 mol % spiropyran units in the side chains. To investigate the photochromic and conformational behavior in acid conditions, the polypeptides were dissolved in hexafluoro-2-propanol (HFP) and a small amount of trifluoroacetic acid was added (TFA, c = 5 × 10-4 g/mL). In the absence of acid, the same polypeptides were found to respond to light, giving reversible coil/α-helix transitions. In the presence of TFA, by contrast, photoisomerization of the chromophores in the side chains did not result in any conformational variation of the macromolecular main chains, and CD spectra showed that the macromolecules adopted a random coil structure, both in the dark and after light exposure. However, when appropriate amounts of cosolvents such as methanol (MeOH) or trifluoroethanol (TFE) were added to the HFP/TFA solutions, the system again responded to light, giving reversible coil/α-helix transitions of the macromolecular structure. The extent of the photoinduced conformational changes depended on solvent composition and the photoresponse could be modulated by the combined action of light and chemical environment. For HFP/MeOH solvent mixture, it is possible to trigger the photostimulated coil/α-helix transition in a narrow window of solvent composition, so that the system is characterized by a gated photoresponse. The molecular processes responsible for the observed photoinduced conformational changes are discussed on the basis of absorption and fluorescence results. These results also allow us to set up a detailed picture of the molecular mechanisms responsible for the described chemo-modulated photosensory system." @default.
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• W2003803584 date "1999-09-30" @default.
• W2003803584 modified "2023-09-24" @default.
• W2003803584 title "Photoresponsive Polypeptides. Photochromic and Conformational Behavior of Spiropyran-Containing Poly(<scp>l</scp>-glutamate)s under Acid Conditions" @default.
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• W2003803584 doi "https://doi.org/10.1021/ma990796q" @default.
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