A Green Light-Triggerable RGD Peptide for Photocontrolled Targeted Drug Delivery: Synthesis and Photolysis Studies
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We describe for the first time the synthesis and photochemical properties of a coumarin-caged cyclic RGD peptide and demonstrate that uncaging can be efficiently performed with biologically compatible green light. This was accomplished by using a new dicyanocoumarin derivative (DEAdcCE) for the protection of the carboxyl function at the side chain of the aspartic acid residue, which was selected on the basis of Fmoc-tBu SPPS compatibility and photolysis efficiency. The shielding effect of a methyl group incorporated in the coumarin derivative near the ester bond linking both moieties in combination with the use of acidic additives such as HOBt or Oxyma during the basic Fmoc-removal treatment were found to be very effective for minimizing aspartimide-related side reactions. In addition, a conjugate between the dicyanocoumarin-caged cyclic RGD peptide and ruthenocene, which was selected as a metallodrug model cargo, has been synthesized and characterized. The fact that green-light triggered photoactivation can be efficiently performed both with the caged peptide and with its ruthenocenoyl bioconjugate reveals great potential for DEAdcCE-caged peptide sequences as selective drug carriers in the context of photocontrolled targeted anticancer strategies.Keywords:
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Azobenzene molecules show excellent application potential in many fields due to their photoisomerization properties. Azobenzene molecules will gradually change from trans-structure to cis-structure under the irradiation of UV. In this paper, we have synthesized 4,4'-dibromoazobenzene molecules and characterized their photoisomerization properties. We found that with the extension of UV time, the trans absorption peak at 343 nm decreased significantly, while the cis absorption peak at 435 nm showed an upward trend. Furthermore, photoisomerization of azobenzene is not a first-order reaction.
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Abstract This work is devoted to the study of cis-trans photoisomerization of 1,2-di(1-naphtyl)-ethylene (DNE) in the condensed phase. The reaction of photoisomerization of the diaryl-ethylene is well known,1 the reaction of cis-trans photoisomerization occurring even at 77°K. This reaction is believed to occur with a decrease of the molecular volume.2 Therefore, we supposed that the reaction of cis-trans isomerization would occur in the condensed solid state.
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Bioconjugation is a chemical strategy to form a covalent linkage between two molecules, at least one of which is a biomolecule. Bioconjugation has been a booming research topic along with the development of organic chemistry. The advancement of bioconjugation has greatly promoted many fields like analysis, medicine, and material science. In the past several years, various synthetic methodologies have been employed for bioconjugation chemistry, mainly containing two aspects: one is the conjugation based on the modification of extrinsic functional groups on the biomolecules, followed by covalent linking with expected reporters or targeting units. Another strategy is the direct conjugation of some functional units to the native groups in the biomolecule without any previous modification. Both of them have advantages and insufficiencies in some aspects, which depend on their specific application areas. In the past two decades, alkyne-related polymer chemistry has been a constant research interest for Tang and coworkers, which has also inspired the research progress in bioconjugation. In this chapter, the progress of metal-free bioconjugation based on activated alkynes is summarized and some representative works are displayed for further elaborations. The screening of activated alkynes to improve reactivity and general applicability for bioconjugation is also discussed; we hope the noted activated alkynes will inspire the applications of modern bioconjugation.
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We herein report the synthesis and analysis of a novel aza-BODIPY-antibody conjugate, formed by controlled and regioselective bioconjugation methodology. Employing the clinically relevant antibody, which targets HER2 positive cancers, represents an excellent example of an antibody targeting strategy for this class of near-IR emitting fluorophore. The NIR fluorescence and binding properties were validated through in vitro studies using live cell confocal imaging.
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Phytochromes' ring D orientational changes are tracked during Z-to-E photoisomerization by polarization resolved femtosecond visible pump-infrared probe spectroscopy. Two distinct Pr isoforms Pr-I and Pr-II exhibit photoisomerization yields of 3% and 29%, respectively.
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Cinnamate derivatives show a variety of photo-induced reactions. Among them is trans-cis photoisomerization, which may involve the nonradiative decay (NRD) process. The extended multistate complete active space second-order perturbation (XMS-CASPT2) method was used in this study as a suitable theory for treating multireference electronic nature, which was frequently manifested in the photoisomerization process. The minimum energy paths of the trans-cis photoisomerization process of cinnamate derivatives were determined, and the activation energies were estimated using the resulting intrinsic reaction coordinate (IRC) paths. Natural orbital analysis revealed that the transition state's (TS) electronic structure is zwitterionic-like, elucidating the solvent and substituent effect on the energy barrier of photoisomerization paths. Furthermore, it was found that the charge on the pyramidalized carbon atom at the TS structure was strongly correlated with the activation energy barrier for the cinnamate derivatives. Thus, it seemingly provided a physical picture of the photoisomerization of cinnamates and was a good descriptor potentially applicable to molecular design for controlling the rate constant of the photoisomerization reaction.
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