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51.
Dr. Yu‐Chang Liu Dr. Christian Merten Prof. Dr. Jan Deska 《Angewandte Chemie (International ed. in English)》2018,57(37):12151-12156
Alcohol dehydrogenases can act as powerful catalysts in the preparation of optically pure γ‐hydroxy‐δ‐lactones by means of an enantioconvergent dynamic redox isomerization of readily available Achmatowicz‐type pyranones. Imitating the traditionally metal‐mediated “borrowing hydrogen” approach to shuffle hydrides across molecular architectures and interconvert functional groups, this chemoinspired and purely biocatalytic interpretation effectively expands the enzymatic toolbox and provides new opportunities in the assembly of multienzyme cascades and tailor‐made cellular factories. 相似文献
52.
《Journal of polymer science. Part A, Polymer chemistry》2018,56(2):194-202
This article reports a synthetic methodology for single step preparation of telechelic poly(disulfide)s (PDS) by step‐growth polymerization between a di‐thiol and a commercially available monomer 2,2′‐dithiodipyridine in presence of a functional group appended pyridyl disulfide moiety as the “mono‐functional impurity” (MFI). Redox‐destructible well‐defined segmented PDSs with functional chain terminal, predicted and tunable degree of polymerization and narrow polydispersity index (<2.0) could be synthesized under a mild reaction condition. Using an appropriate MFI, PDS could be synthesized with trithiocarbonate chain terminals in a single step, which could be further used as macro chain‐transfer agent (CTA) for chain growth polymerization under RAFT mechanism producing ABA type tri‐block copolymer wherein the B block consists of the degradable PDS chain. By copolymerization between a hydrophobic di‐thiol monomer and a hydroxyl group appended di‐thiol monomer, PDS could be prepared with pendant hydroxyl functional group which was utilized to initiate ring opening polymerization of cyclic lactide monomers producing well‐defined degradable graft‐copolymer. The pendant hydroxyl groups were further utilized to anchor a polar carboxylic group to the degradable PDS backbone which under basic condition showed aqueous self‐assembly generating micelle‐like structure with hydrophobic guest encapsulation ability and glutathione responsive sustained release. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 194–202 相似文献
53.
Enhancing the Value of Free Metals in the Synthesis of Lanthanoid Formamidinates: Is a Co‐oxidant Needed?
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Prof. Dr. Glen B. Deacon Prof. Dr. Peter C. Junk Dr. Daniel Werner 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(1):160-173
Treatment of N,N′‐bis(aryl)formamidines (ArFormH), N,N′‐bis(2,6‐difluorophenyl)formamidine (DFFormH) or N,N′‐bis(2,6‐diisopropylphenyl)formamidine (DippFormH), with europium metal in CH3CN is an efficient synthesis of the divalent complexes: [{Eu(DFForm)2(CH3CN)2}2] ( Eu1 ) or [Eu(DippForm)2(CH3CN)4] ( Eu2 ). The synthetic method was extended to ytterbium, but the metal required activation by addition of Hg0. With DFFormH in CH3CN, [{Yb(DFForm)2(CH3CN)}2] ( Yb1 ) was obtained in good yield, and [Yb(DFForm)2(thf)3] ( Yb3 ) was obtained from a synthesis in CH3CN/THF. Thus, this synthetic method completely circumvents the use of either salt metathesis, or redox transmetallation/protolysis (RTP) protocols to prepare divalent rare‐earth formamidinates. Heating Yb1 in PhMe/C6D6 resulted in decomposition to trivalent products, including one from a CH3CN activation process. For a synthetic comparison, divalent ytterbium DFForm and DippForm complexes were synthesised by RTP reactions between Yb0, Hg(R)2 (R=Ph, C6F5), and ArFormH in THF, leading to the isolation of either [Yb(DFForm)2(thf)3] ( Yb3 ), or the first five coordinate rare‐earth formamidinate complex [Yb(DippForm)2(thf)] ( Yb4 b ), and, from adjustment of the stoichiometry, trivalent [Yb(DFForm)3(thf)] ( Yb6 ). Oxidation of Yb3 with benzophenone (bp), or halogenating agents (TiCl4(thf)2, Ph3CCl, C2Cl6) gave [Yb(DFForm)3(bp)] or [Yb(DFForm)2Cl(thf)2], respectively. Furthermore, the structural chemistry of divalent ArForm complexes has been substantially broadened. Not only have the highest and lowest coordination numbers for divalent rare‐earth ArForm complexes been achieved in Eu2 and Yb4 b , respectively, but also dimeric Eu1 and Yb1 have highly unusual ArForm bridging coordination modes, either perpendicular μ‐1κ(N:N′):2κ(N:N′) in Eu1 , or the twisted μ‐1κ(N:N′):2κ(N′:F′) DFForm coordination in Yb1 , both unprecedented in divalent rare‐earth ArForm chemistry and in the wider divalent rare‐earth amidinate field. 相似文献
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56.
Dr. Nikhil S. Malvankar Dr. Tünde Mester Prof. Mark T. Tuominen Prof. Derek R. Lovley 《Chemphyschem》2012,13(2):463-468
Supercapacitors have attracted interest in energy storage because they have the potential to complement or replace batteries. Here, we report that c‐type cytochromes, naturally immersed in a living, electrically conductive microbial biofilm, greatly enhance the device capacitance by over two orders of magnitude. We employ genetic engineering, protein unfolding and Nernstian modeling for in vivo demonstration of charge storage capacity of c‐type cytochromes and perform electrochemical impedance spectroscopy, cyclic voltammetry and charge–discharge cycling to confirm the pseudocapacitive, redox nature of biofilm capacitance. The biofilms also show low self‐discharge and good charge/discharge reversibility. The superior electrochemical performance of the biofilm is related to its high abundance of cytochromes, providing large electron storage capacity, its nanostructured network with metallic‐like conductivity, and its porous architecture with hydrous nature, offering prospects for future low cost and environmentally sustainable energy storage devices. 相似文献
57.
Jiawei Zhang Yiliu Liu Bin Yuan Prof. Zhiqiang Wang Prof. Monika Schönhoff Prof. Xi Zhang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(47):14968-14973
Stable multilayer films with cucurbit[8]uril have been fabricated on the basis of the alternating layer‐by‐layer assembly of a novel side‐chain pseudopolyrotaxane and a photoreactive polyanion. The as‐prepared multilayer films exhibit good properties as surface‐imprinted multilayers, because cucurbit[8]uril molecules that are locked inside the multilayers can act as nanocontainers with specific binding to certain guest molecules, and the loading and release of the guest is redox‐controllable and reversible. 相似文献
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59.
Li Zhao Qiangjun Ling Xiong Liu Chaodong Hang Qiuxia Zhao Fangfei Liu Haibin Gu 《应用有机金属化学》2018,32(2)
Owing to their unique broken symmetry, amphiphilic Janus dendrimers and dendons provide fascinating properties for material, biological, pharmaceutical and biomedical applications. The integration of various organometallic moieties into these macromolecules will further offer the opportunity to form complex and intelligent architectures and materials. Here, we report a novel, simple and multifunctional Janus dendron containing redox‐reversible hydrophobic ferrocene (Fc) unit, complexing‐effective 1,2,3‐triazole ligand and biocompatible hydrophilic triethylene glycol termini. Silver and gold nanoparticles were firstly successfully prepared by using the Janus dendron as the reducing agent of Au(III) and Ag(I), and the stabilizer of the corresponding nanoparticles. The redox response of the Fc moiety was then employed to trigger the release of model drug, rhodamine B, encapsulated in supramolecular micelles formed by the self‐assembly of the Janus dendron. Finally, the precise and excellent metal‐complexing ability of the triazole group in this dendron was fully utilized to stabilize a water‐soluble Cu(I) catalyst, forming supramolecular nanoreactors for the catalysis of the copper(I)‐catalyzed azide alkyne cycloaddition click reaction in only water. The multifunctional characteristics of this dendron highlight the potential for organometallic Janus dendrimers and dendrons in the fields of functional materials and nanomedicines. 相似文献
60.
Redox‐responsive core cross‐linked micelles of poly(ethylene oxide)‐b‐poly(furfuryl methacrylate) by Diels‐Alder reaction for doxorubicin release
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Cuong M. Q. Le Hai Ha Pham Thi Xuan Thang Cao Gun‐Do Kim Chul‐Woong Oh Kwon Taek Lim 《Journal of polymer science. Part A, Polymer chemistry》2016,54(23):3741-3750
Redox‐responsive core cross‐linked (CCL) micelles of poly(ethylene oxide)‐b‐poly(furfuryl methacrylate) (PEO‐b‐PFMA) block copolymers were prepared by the Diels‐Alder click‐type reaction. First, the PEO‐b‐PFMA amphiphilic block copolymer was synthesized by the reversible addition‐fragmentation chain transfer polymerization. The hydrophobic blocks of PFMA were employed to encapsulate the doxorubicin (DOX) drug, and they were cross‐linked using dithiobismaleimidoethane at 60 °C without any catalyst. Under physiological circumstance, the CCL micelles demonstrated the enhanced structural stability of the micelles, whereas dissociation of the micelles took place rapidly through the breaking of disulfide bonds in the cross‐linking linkages under reduction environment. The core‐cross‐linked micelles showed fine spherical distribution with hydrodynamic diameter of 68 ± 2.9 nm. The in vitro drug release profiles presented a slight release of DOX at pH 7.4, while a significant release of DOX was observed at pH 5.0 in the presence of 1,4‐dithiothreitol. MTT assays demonstrated that the block copolymer did not have any practically cytotoxicity against the normal HEK293 cell line while DOX‐loaded CCL micelles exhibited a high antitumor activity towards HepG2 cells. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3741–3750 相似文献