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951.
A facile approach to chiral dihydroquinazolinone derivatives has been described via biomimetic asymmetric reduction of quinazolinones with chiral and regenerable NAD(P)H models. The utility of this method was demonstrated by a concise synthesis of the bromodomain protein divalent inhibitor.  相似文献   
952.
953.
The present study is concerned with the application of nonaqueous capillary electrophoresis (NACE) with electrochemical detection (ED) to the separation and quantitative determination of hydrazine (Hy) and its methyl derivatives. The best performance of NACE-ED was found when using 4 mM sodium acetate/10 mM acetic acid/methanol: acetonitrile = 1:2 as the running buffer, with a bare platinum working electrode set at +1.0 V in an end-column amperometric detection cell. The choice and ratio of suitable solvents for the separation and injection media played an essential role for the performance characteristics of the method. The limits of detection for Hy, methylhydrazine, symmetrical dimethylhydrazine, and unsymmetrical dimethylhydrazine were 5, 2, 12, and 1 ng/mL, respectively. This is between one and two orders of magnitude lower than that achieved by previously reported CE-ED methods in aqueous buffer systems in conjunction with various types of chemically modified electrodes. The practical utility of the new NACE-ED methodology is demonstrated in terms of the determination of traces of Hys in spiked environmental samples containing a wide range of explosives and related compounds.  相似文献   
954.
Photochemical reactions (lambda irr = 254 nm) of substituted benzyldiphenylphosphine oxides 1a-e have been investigated in benzene and acetonitrile. alpha-Cleavage from the singlet excited state is proposed as the primary process, and products formed both before and after escape of the primary intermediates from the solvent cage result. Radicals 2 and 3 are observed by nanosecond flash photolysis following excitation of 1a at 266 nm in acetonitrile. Acetone sensitization of 1a,b fails to improve the efficiency of product formation. The quantum yields of disappearance of 1a,b are unaffected by O2, and mechanisms for product formation from 1a in the presence of oxygen are proposed.  相似文献   
955.
Many studies have focused on effective ways to exploit enzyme immobilization on an electrode surface to help improve the performance of enzymatic electrochemical biosensors. Herein, a novel glucose sensor was fabricated by immobilizing glucose oxidase (GOx) onruthenium-based conjugated polymer (CP) and metal-organic framework (MOF) nanocomposites. This has not only reduced the applied potential to 0.2 V (vs. Ag/AgCl), but also improved the effective surface area for enzyme immobilization.PPG@Ru@UiO-66-NH2 was tailored by controlled chemical synthesis from a pre-synthesized water-soluble conjugated polymer (poly(N-phenylglycine)) and metal-organic framework (UiO-66-NH2). The resulting nanocomposites were characterized using Fourier transform infrared spectroscopy, X-ray fluorescence, scanning electron microscopy, and cyclic voltammetry. The PPG@Ru@UiO-66-NH2/GOx coated electrodedisplayed a linear measurementrange for glucose from 1 mM to 10 mM, with a sensitivity of 45.92 μA ⋅ mM−1cm−1 and limit of detection of5 μM( ). Furthermore, the practical application of the fabricatedglucosesensor was tested in simulative blood samples with satisfactoryaccuracy. This approach alsoopens a new door for applications regarding both enzymatic electrochemical biosensors and enzymatic biofuel cells (EBFCs).  相似文献   
956.
Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for C–C bond formation. A decarboxylative cross-coupling method is described to afford substituted alkynes from various carboxylic acids using copper catalysts CuCl and Cu(acac)2. The photoexcitation of copper acetylides with electron-rich NEt3 as a ligand provides a general strategy to generate a range of alkyl radicals from RAEs of carboxylic acids, which can be readily coupled with a variety of aromatic alkynes. The scope of this cross-coupling reaction can be further expanded to aliphatic alkynes and alkynyl silanes using a catalytic amount of preformed copper-phenylacetylide. In addition, DFT calculations revealed the favorable reaction pathway and that the bidentate acetylacetonate ligand of the copper intermediate plays an important role in inhibiting the homo-coupling of the alkyne.

Redox-active esters (RAEs) as alkyl radical precursors have demonstrated great advantages for Cu-catalysed C–C bond formation.  相似文献   
957.
We report here porphodilactol derivatives and their corresponding metal complexes. These systems show promise as “all-in-one” phototheranostics and are predicated on a design strategy that involves controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. The requisite balance was achieved by tuning the aromaticity of these porphyrinoid derivatives and forming complexes with one of two lanthanide cations, namely Gd3+ and Lu3+. The net result led to a metalloporphodilactol system, Gd-trans-2, with seemingly optimal ISC efficiency, photothermal conversion efficiency and fluorescence properties, as well as good chemical stability. Encapsulation of Gd-trans-2 within mesoporous silica nanoparticles (MSN) allowed its evaluation for tumour diagnosis and therapy. It was found to be effective as an “all-in-one” phototheranostic that allowed for NIR fluorescence/photoacoustic dual-modal imaging while providing an excellent combined PTT/PDT therapeutic efficacy in vitro and in vivo in 4T1-tumour-bearing mice.

We report here porphodilactol derivatives and their corresponding metal complexes as “all-in-one” phototheranostics by controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation.  相似文献   
958.
末端碳链长度对偶氮苯自组装膜结构的影响   总被引:4,自引:0,他引:4  
The end-group dominated molecular orientation in the azobenzene self-assembled monolayers (SAMs), CnAzoC2SH (n=1-4), on gold was evaluated for the first time by grazing incidence reflection absorption FTIR spectroscopy (RA-FTIR). All these azobenzene SAMs have highly-organized and closely-parked structures, with the molecule tilting away gradually from surface normal direction with the increase of end group alkyl length.  相似文献   
959.
A particular pathology of certain W5Si3-type A5B3 structures (I4/mcm) appears to arise because of unduly close approaches of the A1-type atoms on the cell faces at , 0, () that occur with the larger and more electropositive A and/or in the presence of smaller B atoms. A structure refinement of binary Ba4.81Pb3 indicates such a marginal stability in that the Ba atoms in the facial Ba0.81 chains exhibit an extreme displacement ellipsoid along . Although Ca5Sn3 and La5Ga3 binaries are unknown in this structure type, five stable ternary derivatives of these have been synthesized via substitution reactions and characterized by single crystal X-ray diffraction means: Ca4Sn3.223(4)Mg0.777, Ca4Sn3Cu1.30(4), Ca4.66(6)Sn3Zn0.704(4), La4.81(1)Ga1.38(2)Al1.62, and La4.762(5)Ga1.5(1)Zn1.5. Only the Ca-Sn-Zn phase exhibits lower symmetry, P4/mbm. The problematic A1 sites exhibit diverse changes in these, whereas the surrounding B2 tetrahedra are largely unaltered. The Ca-Sn results are, respectively: direct Mg/Sn substitution at the Ca1 site; mixed fractional distribution of the smaller Cu at two sites around the A1 position with an unresolved disorder; a pair of apparently independent modes, fractional Ca in the normal position and fractional Zn rectangles thereabout. The two La-Sn phases contain normal Ga,Al (Ga,Zn) tetrahedral chains with pairs of fractional disordered La atoms along , 0, z. Each can be rationalized in terms of a reasonable incommensurate structure. Electronic effects may also be operable.  相似文献   
960.
Mechanistic studies of the enolization of 2-methylcyclohexanone mediated by lithium hexamethyldisilazide (LiHMDS; TMS2NLi) in toluene and toluene/amine mixtures are described. NMR spectroscopic studies of LiHMDS/ketone mixtures in toluene reveal the ketone-complexed cyclic dimer (TMS2NLi)2(ketone). Rate studies using in situ IR spectroscopy show the enolization proceeds via a dimer-based transition structure, [(TMS2NLi)2(ketone)]++. NMR spectroscopic studies of LiHMDS/ketone mixtures in the presence of relatively unhindered trialkylamines such as Me2NEt reveal the quantitative formation of cyclic dimers of general structure (TMS2NLi)2(R3N)(ketone). Rate studies trace a >200-fold rate acceleration to a dimer-based transition structure, [(TMS2NLi)2(R3N)(ketone)]++. Amines of intermediate steric demand, such as Et3N, are characterized by recalcitrant solvation, saturation kinetics, and exceptional (>3000-fold) accelerations traced to the aforementioned dimer-based pathway. Amines of high steric demand, such as i-Pr2NEt, do not observably solvate (TMS2NLi)2(ketone) but mediate enolization via [(TMS2NLi)2(R3N)(ketone)]++ with muted accelerations. The most highly hindered amines, such as i-Bu3N, do not influence the LiHMDS structure or the enolization rate. Overall, surprisingly complex dependencies of the enolization rates on the structures and concentrations of the amines derive from unexpectedly simple steric effects. The consequences of aggregation, mixed aggregation, and substrate-base precomplexation are discussed.  相似文献   
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