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51.
52.
Spatial and temporal electrochemical control of singlet oxygen production and decay in photosensitized experiments 总被引:1,自引:0,他引:1
Ijeri VS Daasbjerg K Ogilby PR Poulsen L 《Langmuir : the ACS journal of surfaces and colloids》2008,24(3):1070-1079
Active spatial and temporal modulation of domains of singlet oxygen activity is demonstrated using electrochemical tools. Using singlet oxygen microscopy in photosensitized experiments, it is shown that singlet oxygen concentrations around an ultramicroelectrode can be controlled by applying a bias voltage to the electrode. Two phenomena that can be exploited separately or collectively are examined: (1) the singlet oxygen concentration can be altered by local oxidation or reduction of the photosensitizer, which is the precursor to singlet oxygen, and (2) the reduction of oxygen to produce the superoxide anion which, among other things, is an effective singlet oxygen quencher, results in a local decrease in the concentration of singlet oxygen around the electrode. Both of these phenomena depend significantly on the diffusion of molecules along concentration gradients established by the biased electrode. The results reported herein demonstrate that one can indeed exert local electrochemical control and readily manipulate the population of singlet oxygen produced in a photosensitized process. 相似文献
53.
Gloriam DE Wellendorph P Johansen LD Thomsen AR Phonekeo K Pedersen DS Bräuner-Osborne H 《Chemistry & biology》2011,18(11):1489-1498
GPRC6A is a Family C G protein-coupled receptor recently discovered and deorphanized by our group. This study integrates chemogenomic ligand inference, homology modeling, compound synthesis, and pharmacological mechanism-of-action studies to disclose two noticeable results of methodological and pharmacological character: (1) chemogenomic lead identification through the first, to our knowledge, ligand inference between two different GPCR families, Families A and C; and (2) the discovery of the most selective GPRC6A allosteric antagonists discovered to date. The unprecedented inference of?pharmacological activity across GPCR families provides proof-of-concept for in?silico approaches against Family C targets based on Family A templates, greatly expanding the prospects of successful drug design and discovery. The antagonists were tested against a panel of seven Family A and C G protein-coupled receptors containing the chemogenomic binding sequence motif where some of the identified GPRC6A antagonists showed some activity. However, three compounds with at least ~3-fold selectivity for GPRC6A were discovered, which present a significant step forward compared with the previously published GPRC6A antagonists, calindol and NPS 2143, which both display ~30-fold selectivity for the calcium-sensing receptor compared to GPRC6A. The antagonists constitute novel research tools toward investigating the signaling mechanism of the GPRC6A receptor at the cellular level and serve as initial ligands for further optimization of potency and selectivity enabling future ex?vivo/in?vivo pharmacological studies. 相似文献
54.
Lars J. Wesenberg Erika Diehl Till J. B. Zähringer Carolin Dörr Dr. Dieter Schollmeyer Dr. Akihiro Shimizu Prof. Dr. Jun-ichi Yoshida Prof. Dr. Ute A. Hellmich Prof. Dr. Siegfried R. Waldvogel 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(72):17574-17580
The efficient production of many medicinally or synthetically important starting materials suffers from wasteful or toxic precursors for the synthesis. In particular, the aromatic non-protected primary amine function represents a versatile synthetic precursor, but its synthesis typically requires toxic oxidizing agents and transition metal catalysts. The twofold electrochemical amination of activated benzene derivatives via Zincke intermediates provides an alternative sustainable strategy for the formation of new C−N bonds of high synthetic value. As a proof of concept, we use our approach to generate a benzoxazinone scaffold that gained attention as a starting structure against castrate-resistant prostate cancer. Further improvement of the structure led to significantly increased cancer cell line toxicity. Thus, exploiting environmentally benign electrooxidation, we present a new versatile and powerful method based on direct C−H activation that is applicable for example the production of medicinally relevant compounds. 相似文献
55.
A Gallium‐Substituted Distibene and an Antimony‐Analogue Bicyclo[1.1.0]butane: Synthesis and Solid‐State Structures 下载免费PDF全文
M. Sc. Lars Tuscher Dr. Chelladurai Ganesamoorthy Dieter Bläser Dr. Christoph Wölper Prof. Dr. Stephan Schulz 《Angewandte Chemie (International ed. in English)》2015,54(36):10657-10661
RGa {R=HC[C(Me)N(2,6‐iPr2C6H3)]2} reacts with Sb(NMe2)3 with insertion into the Sb? N bond and elimination of RGa(NMe2)2 ( 2 ), yielding the Ga‐substituted distibene R(Me2N)GaSb?SbGa(NMe2)R ( 1 ). Thermolysis of 1 proceeded with elimination of RGa and 2 and subsequent formation of the bicyclo[1.1.0]butane analogue [R(Me2N)Ga]2Sb4 ( 3 ). 相似文献
56.
Aminoboranes have been shown to be highly efficient and mild iminium ion generators in the Mannich-type aminative coupling of aldehydes with silyl ketene acetals. By using aminoboranes bearing bulky amino groups, such as a diisopropylamino group, free secondary amines can be successfully used as the amino component in a three-component Mannich reaction with aldehydes and silyl ketene acetals. 相似文献
57.
Kiryutin AS Morozova OB Kuhn LT Yurkovskaya AV Hore PJ 《The journal of physical chemistry. B》2007,111(38):11221-11227
Relative values of the 1H and 13C isotropic hyperfine couplings in the cationic oxidized tryptophan radical TrpH*+ in aqueous solution are determined. The data are obtained from the photo-CIDNP (chemically induced dynamic nuclear polarization) enhancements observed in the microsecond time-resolved NMR spectra of the diamagnetic products of photochemical reactions in which TrpH*+ is a transient intermediate. The method is validated using the tyrosyl neutral radical Tyr*, whose 1H and 13C hyperfine couplings have previously been determined by electron paramagnetic resonance spectroscopy. Good agreement is found with hyperfine coupling constants for TrpH*+ calculated using density functional theory methods but only if water molecules are explicitly included in the calculation. 相似文献
58.
Suci PA Berglund DL Liepold L Brumfield S Pitts B Davison W Oltrogge L Hoyt KO Codd S Stewart PS Young M Douglas T 《Chemistry & biology》2007,14(4):387-398
Nanomedicine directed at diagnosis and treatment of infections can benefit from innovations that have substantially increased the variety of available multifunctional nanoplatforms. Here, we targeted a spherical, icosahedral viral nanoplatform to a pathogenic, biofilm-forming bacterium, Staphylococcus aureus. Density of binding mediated through specific protein-ligand interactions exceeded the density expected for a planar, hexagonally close-packed array. A multifunctionalized viral protein cage was used to load imaging agents (fluorophore and MRI contrast agent) onto cells. The fluorescence-imaging capability allowed for direct observation of penetration of the nanoplatform into an S. aureus biofilm. These results demonstrate that multifunctional nanoplatforms based on protein cage architectures have significant potential as tools for both diagnosis and targeted treatment of recalcitrant bacterial infections. 相似文献
59.
We have synthesized a new class of flexible zwitterions 6a-e, in which a carboxylate is linked via an alkyl chain with variable length (one to five methylene groups) to a guanidiniocarbonylpyrrole cation. The self-association properties of these zwitterions were determined by NMR dilution studies in DMSO and by ESI-MS experiments. The stability and hence also the size of the aggregates formed via self-assembly is critically dependent on the length and therefore flexibility of the spacer. Whereas the smallest zwitterion 6a forms large aggregates already at low concentrations, the more flexible zwitterions only form small oligomers (6b) or dimers (6c-e) at much larger concentrations. The differences between the five zwitterions can be explained based on the different extent of intramolecular ion pairing within the monomers. Any intramolecular ion pairing, which becomes possible with increasing linker length, stabilizes the monomer and therefore destabilizes any oligomer. 相似文献
60.
Kenneth Ekman Lars Ekholm Jan H. Nsman 《Journal of polymer science. Part A, Polymer chemistry》1995,33(16):2699-2703
The radiation induced graft copolymerization of m-isopropenyl-α,α-dimethyl benzyl iso-cyanate (m-TMI) and styrene onto polypropylene was carried out. The extent of grafting increased with increasing amount of styrene and with increased radiation dose. A graft load of 180% was obtained by immersing a 50 kGy pre-irradiated film in a monomer solution containing 25 mol % m-TMI and 75 mol % styrene. The graft copolymer is suitable for covalently binding nonpolymerizable stabilizers with a suitable nucleophilic moiety. In this work the isocyanate moiety of the graft copolymer was allowed to react with 4-amino-2,2,6,6-tetramethyl piperidine, a hindered amine light stabilizer. Fourier trans-formed infrared spectroscopy confirmed the formation of an urea moiety. © 1995 John Wiley & Sons, Inc. 相似文献