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991.
A means to induce dehydrodimerization of Seebach's oxazolidinone (5), the stereochemical outcome of which is entirely temperature dependent, is described. The resultant dimers 3 and 4 are precursors to (R,R)-alpha,alpha'-biproline (1) and meso-alpha,alpha'-biproline (2), respectively. An organohypobromite and an iminium halide are proposed to serve as electrophiles in the reaction with the enolate of 5 to give 3 and 4, respectively.  相似文献   
992.
Thermal behaviour of M(OH)2(8-HQ)2 (M=Ni, Cu and Zn; 8-HQ=8-hydroxyquinoline) has been studied by dynamic TG and DTA methods in nitrogen atmosphere. The percent weights lost in different temperature range was calculated from TG curves. The mode of decomposition has been supported by endotherms observed in DTA curves of the respective compounds.  相似文献   
993.
One isomer, LC of the isomeric Me8[14]anes, LA, LB and LC; on reaction with Ni(NCS)2 produces a six coordinate octahedral diisothiocyanato complex, [NiLC(NCS)2]. This complex undergoes axial substitution reactions with the small ligands to yield corresponding monosubstituted derivatives having general formula [NiLC(NCS)X] whereas X = Cl, Br, I, NO2 or NO3. The complexes have been characterized on the basis of analytical, spectroscopic, magnetic and conductance data. The structure of [NiLC(NCS)2] (triclinic, space group P?1, α = 8.0421(17) Å, β = 8.9085(18) Å, χ = 9.687(2) Å, α = 67.561(3) Å, β = 82,896(4) Å, ζ = 598.7(2) Å3, = 2, Dc = 1.352 mg/m3, μ(Mo ) = 1.003 mm?1) was confirmed by X-ray crystallography.  相似文献   
994.
Controlled and efficient activation is the crucial aspect of designing an effective prodrug. Herein we demonstrate a proof of concept for a light activatable prodrug with desired organelle specificity. Mertansine, a benzoansamacrolide, is an efficient microtubule-targeting compound that binds at or near the vinblastine-binding site in the mitochondrial region to induce mitotic arrest and cell death through apoptosis. Despite its efficacy even in the nanomolar level, this has failed in stage 2 of human clinical trials owing to the lack of drug specificity and the deleterious systemic toxicity. To get around this problem, a recent trend is to develop an antibody-conjugatable maytansinoid with improved tumor/organelle-specificity and lesser systematic toxicity. Endogenous CO is recognized as a regulator of cellular function and for its obligatory role in cell apoptosis. CO blocks the proliferation of cancer cells and effector T cells, and the primary target is reported to be the mitochondria. We report herein a new mitochondria-specific prodrug conjugate (Pro-DC) that undergoes a photocleavage reaction on irradiation with a 400 nm source (1.0 mW cm−2) to induce a simultaneous release of the therapeutic components mertansine and CO along with a BODIPY derivative (BODIPY(PPH3)2) as a luminescent marker in the mitochondrial matrix. The efficacy of the process is demonstrated using MCF-7 cells and could effectively be visualized by probing the intracellular luminescence of BODIPY(PPH3)2. This provides a proof-of-concept for designing a prodrug for image-guided combination therapy for mainstream treatment of cancer.

Simultaneous release of two therapeutic reagents, mertansine and CO through photo-induced cleavage of a mitochondria-specific prodrug with improved drug efficacy.  相似文献   
995.
The reaction of ammonium tetrathiometalate (NH4)2[MS4] (M = W or Mo) with the R(+) or S(?) forms of the organic amine α‐methylbenzylamine [PhCH(CH3)NH2] results in the formation of the corresponding non‐centrosymmetric bis(α‐methylbenzylammonium) tetrathiometalate complexes [PhCH(CH3)NH3]2[MS4] (R‐ammonium M = W 1 ; R‐ammonium M = Mo 2 ; S‐ammonium M = W 3 , S‐ammonium M = Mo 4 ) which were characterized by elemental analysis, IR, Raman, UV‐Vis and CD spectra, X‐ray powder diffractometry and single crystal X‐ray crystallography. Compounds 1 ‐ 4 crystallize in the chiral space group P21 and constitute the first examples of structurally characterized chiral organic ammonium group VI tetrathiometalates. The structures of 1 ‐ 4 consist of two crystallographically independent chiral organic ammonium cations and a tetrahedral tetrathiometalate dianion. The N‐H···S and C‐H···S interactions between the anions and cations organise them such that the organic ammonium ions always point towards the S atoms of [MS4]2?.  相似文献   
996.
Photophysical investigations of coumarin-7 (C7) dye in different solvents using absorption, steady-state fluorescence and time-resolved fluorescence measurements reveal the behavioral changes of the dye in nonpolar and other solvents. In moderate to higher polarity solvents, the experimental parameters such as fluorescence quantum yield (Phif), fluorescence lifetime (tauf), radiative rate constant (k(f)), nonradiative rate constant (k(nr)) and Stokes' shift (Deltav) follow almost linear correlations with the Lippert-Mataga solvent polarity parameter Deltaf but show unusual deviations in nonpolar solvents. From the observed results, it is inferred that the dye exists in a planar intramolecular charge transfer structure in moderate to higher polarity solvents, but in nonpolar solvents, the dye exists in a nonplanar structure with its 7-NEt2 group adopting a pyramidal type of configuration. Unlike some of the other coumarin dyes, namely coumarin-120 (C120) (4-CH3-7-NH2-1,2-benzopyrone) and coumarin-151 (C151) 4-CF3-7-NH2-1,2-benzopyrone), which also show similar structural changes in nonpolar and other solvents, the C7 dye does not show any activation-controlled deexcitation process in nonpolar solvents. This is attributed to the very slow flip-flop motion of the 7-NEt2 group of the C7 dye in comparison with the very fast flip-flop motion of the 7-NH2 group in the C120 and C151 dyes. Qualitative potential energy diagrams are presented to rationalize the observed results of C7 dye and to compare these with those of the other dyes such as C120 and C151. A support for the observed results and interpretation has also been obtained from quantum chemical calculations on the structures of the C7 dye.  相似文献   
997.
Fibers consisting of a rigid rod polymer and thermoset resin matrices were prepared. Poly(benzo-[1,2-d : 5,4-d′]bisoxazole-2,6-diyl)-1,4-phenylene} (PBO) in polyphosphoric acid (PPA) was blended with isophthaloyl bis-4-benzocyclobutene (1) or 2,6-bis-4-benzocyclobutene benzo[1,2-d: 5,4-d′]bisoxazole (2), and fibers were spun from these dopes. As-spun fibers that did not show phase segregation between the two components as examined with an optical microscope, were soluble in methanesulfonic acid (MSA). After heat treat-ment, the fibers swelled but did not dissolve in MSA. A fiber cross section of heat-treated PBO-1 fiber showed well-dispersed benzocyclobutene polymer domains of 200–500 Å by transmission electron microscopy (TEM). Films cast from MSA solutions of PBO and 2 were homogeneous, and TEM of heat-treated fiber showed only one phase. A molecular composite fiber was made. Some of these fibers showed 20–30% improvement in compressive strength over unmodified PBO fiber. © 1995 John Wiley & Sons, Inc.  相似文献   
998.
Eleven TLC solvent systems were evaluated for the separation of prostaglandins F, E2 and D2, thromboxane B2, 12-OH-5,8,10-heptadecatrienoic acid (HHT), 12-OH-5,8,10,14-eicosatetraenoic acid (HETE), and arachidonic acid (AA) from each other. A three-solvent development TLC procedure, which can conveniently be used for routine resolution of mixtures of these metabolites on a single TLC plate, is reported. The method was used for quantification of the metabolites formed from 14C-labeled AA by washed human platelets.  相似文献   
999.
A practical and general one-pot synthesis of 1-substituted-10-methyl-1,2,3,4-tetrahydropyrazino[1,2-a]indoles is described. The approach uses 2-(3-methyl-1H-indol-1-yl) ethylamine, benzotriazole and aldehydes in the presence of catalytic amount of acid catalysts (AlCl3, ZnCl2, ZnBr2, p-TsOH, CH3SO3H) and proceeds in high yields via iminium cation intramolecular cyclization. The mechanism of the observed intramolecular cyclization reaction has been investigated theoretically by means of PM3 semiempirical method and results were consistent with the experimental results.  相似文献   
1000.
Design and characterization of programmable DNA nanotubes   总被引:4,自引:0,他引:4  
DNA self-assembly provides a programmable bottom-up approach for the synthesis of complex structures from nanoscale components. Although nanotubes are a fundamental form encountered in tile-based DNA self-assembly, the factors governing tube structure remain poorly understood. Here we report and characterize a new type of nanotube made from DNA double-crossover molecules (DAE-E tiles). Unmodified tubes range from 7 to 20 nm in diameter (4 to 10 tiles in circumference), grow as long as 50 microm with a persistence length of approximately 4 microm, and can be programmed to display a variety of patterns. A survey of modifications (1) confirms the importance of sticky-end stacking, (2) confirms the identity of the inside and outside faces of the tubes, and (3) identifies features of the tiles that profoundly affect the size and morphology of the tubes. Supported by these results, nanotube structure is explained by a simple model based on the geometry and energetics of B-form DNA.  相似文献   
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