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Photolytic Labeling and Its Applications in Protein Drug Discovery and Development
摘要: In this mini-review, the major types of photolytic labeling reagents are presented together with their reaction mechanisms. The applications of photolytic labeling in protein drug discovery and development are then discussed; these have expanded from studies of protein-protein interactions in vivo to protein-matrix interactions in lyophilized solids. The mini-review concludes with recommendations for further development of the approach, which include the need for new and more chemically diverse photo-reactive reagents and better understanding of the mechanisms of photolytic labeling reactions in various media.
关键词: protein drug,diazirine,lyophilized solid,photolytic labeling,carbene,protein-protein interaction,benzophenone,phenyl azide
更新于2025-09-09 09:28:46
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Carbohydrate Functionalization of Few-Layer Graphene through Microwave-Assisted Reaction of Perfluorophenyl Azide
摘要: The excellent physical and chemical properties of graphene make it an attractive nanomaterial and a component in high-performance nanocomposite materials. To prepare graphene-based nanocomposite materials, the chemical functionalization is often necessary. Water-soluble ligands such as carbohydrates not only make the functionalized graphene compatible with aqueous media, but also introduce bio-recognition which is important for graphene to be used in biotechnology. In this study, we report the derivatization of few-layer graphene (FLG) with carbohydrates through microwave-assisted reaction of perfluorophenyl azide (PFPA). FLG was first treated with PFPA under microwave radiation. Subsequent conjugation with glycosyl amine gave carbohydrate-presenting FLG. Thermogravimetric analysis showed that microwave radiation gave a higher degree of functionalization compared to conventional heating, with higher weight losses for both PFPA and Man ligands. The carbohydrates (mannose and galactose) retained their bioactivity, as demonstrated by the lectin binding assays. Higher degree of binding towards lectins was obtained for the carbohydrate-functionalized FLG prepared by microwave radiation than the conventional heating.
关键词: microwave radiation,perfluorophenyl azide,graphene,carbohydrate,lectin
更新于2025-09-04 15:30:14
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Azide Passivation of Black Phosphorus Nanosheets: Covalent Functionalization Affords Ambient Stability Enhancement
摘要: Two-dimensional (2D) black phosphorus (BP) has been attracting ever-growing interest due to its unique band structure, but suffers from low ambient stability owing to its high reactivity to oxygen. Covalent functionalization has been demonstrated to passivate the reactive BP effectively, however the reported covalent functionalization methods are quite limited to aryl diazonium and nucleophilic additions affording P-C and P-O-C single bonds, for which the retaining of one unpaired electron in the Group-VA phosphorus atom hampers the passivation effect. Herein, we report for the first time covalent azide functionalization of BP nanosheets (BPNSs), leading to significant enhancement of the ambient stability of BP as confirmed by UV-vis spectroscopic studies. The most stable configuration of the azide functionalized BPNSs is predicted by theoretical calculations, featuring the grafting of benzoic acid moiety onto BPNSs (f-BPNSs) via the unprecedented P=N double bonds formed through in-situ nitrene as a reactive intermediate.
关键词: covalent functionalization,2D nanosheets,nitrene,black phosphorus,azide
更新于2025-09-04 15:30:14
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Phase behavior of main-chain liquid crystalline polymer networks synthesized by alkyne–azide cycloaddition chemistry
摘要: Liquid crystalline polymer networks (LCNs) couple polymer chain organization to molecular ordering, the switching of which has been shown to impart stimuli-responsive properties, including actuation and one-way shape memory, to the networks. While LCNs have long been proposed as artificial muscles, recent reports have also suggested potential as dynamic biomaterial substrates. In contrast to many existing LCNs synthesized using hydrophobic spacers, this work investigates networks synthesized using more hydrophilic spacers to promote interaction with water. A challenge with such materials is liquid crystalline phases could be disrupted in hydrated networks. This work thus investigates the impact of polyether spacers and mesogen composition on the phase behavior of LCNs. Main-chain LCNs were synthesized using alkyne–azide cycloaddition ("click" chemistry), where two different mesogens (5yH and 5yMe) and a non-LC monomer (5yTe) were coupled with one of two different polyether spacers, poly(ethylene glycol) and poly(propylene glycol), and a crosslinker. The chemistry led to high gel fraction materials, the workup of which resulted in networks that displayed no difference in cellular toxicity due to leachable components compared to tissue culture plastic control. Calorimetric analysis, dynamic mechanical analysis, and X-ray scattering revealed the LC microstructure and temperature-responsive properties of the networks. The use of low molecular weight polyether spacers was found to prevent their crystallization within the LC network, and adjusting mesogen composition to enhance its LC phase stability allowed the use of spacers with larger molecular weights and pendant groups. Hydrated networks were found to rearrange their structure compared to dry networks, while maintaining their LC phases. Like other crosslinked LC materials, the networks display shape changes (actuation) that are tied to changes in LC ordering. The result is a new synthetic approach for polydomain networks that form stable LC phases that are tailorable using polyether spacers and may enable future application as hydrated, stimuli-responsive materials.
关键词: Liquid crystalline polymer networks,Phase behavior,Alkyne–azide cycloaddition,Stimuli-responsive materials,Polyether spacers
更新于2025-09-04 15:30:14