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11.
Thalidomide is a potent anticancer therapeutic drug whose mechanism of action has not yet been elucidated. In this report, experimental Raman spectroscopy is used to determine and characterize the vibrational frequencies of the drug. These normal modes are then compared to their quantum mechanical counterparts, which have been computed using density functional theory. Upon analysis of the spectra, we found that there was a high level of agreement between the wavenumbers. As such, this spectroscopic technique may be a viable tool for examining the way in which this drug interacts with its target molecules.  相似文献   
12.
In recent years an increasing amount of interest has been directed at the study and routine testing of polymorphisms responsible for variations in drug metabolism. Most of the current methods involve either time-consuming electrophoresis steps or specialized and expensive equipment. In this context, we have developed a rapid, simple and robust method for genotyping of CYP2D6*3, CYP2D6*4, CYP2C19*2, CYP2C19*3 and TPMT*2 single nucleotide polymorphisms (SNP). Genomic DNA is isolated from whole blood and the segments that span the SNP of interest are amplified by PCR. The products are subjected directly (without purification) to two primer extension (PEXT) reactions (three cycles each) using normal and mutant primers in the presence of biotin-dUTP. The PEXT primers contain a (dA)30 segment at the 5′ end. The PEXT products are detected visually by a dry-reagent dipstick-type assay in which the biotinylated extension products are captured from immobilized streptavidin on the test zone of the strip and detected by hybridization with oligo(dT)-functionalized gold nanoparticles. Patient samples (76 variants in total) were genotyped and the results were fully concordant with those obtained by direct DNA sequencing.  相似文献   
13.
The Ar(4s,3P2) + H(1S,2S) reaction, which gives excited H(n=2) atoms, has been studied. The room temperature rate constant for Lyman-α (2p-1s) excitation was measured as 2.4 × 10?10 cm3 mol?1 s?1. The method was based upon comparison of the Lyman-α emission intensity with the Kr resonance emission intensity produced from Ar(3P2) + Kr, which has a known rate constant. The H atom excitation, which has a large energy defect of 1.3 eV, is discussed in terms of a curve crossing mechanism.  相似文献   
14.
Plasma produced by a (1064 nm) Nd:YAG laser focused onto a graphite target at different nitrogen pressures in the range of 1–90 mTorr, was studied spectroscopically. In the spectral range of 350–600 nm, emission lines of CI neutral carbon (501.12, and 505.21 nm), NI neutral nitrogen (493.5 nm), CII (426.72, 463.7, 515.11 nm), and CIII ions (465.02 and 569.59 nm), and NII ions (501.06, and 500.73 nm), were dominating. Bands of C2 Swan (d3Πg → a3Πu, Δ ν=2, 1, 0, −1), and CN Violet (B2Σ +→ X2Σ+, Δ ν=1, 0, −1) systems, and ionic emissions from the First Negative system N2+ (band head at 391.44 nm), were faintly observed under our specific experimental conditions. From the band intensities, vibrational temperature for CN and C2 was calculated to be 1.25 and 0.31 eV at 90 mTorr, respectively. The electron density and temperature, measured by Stark broadening, assuming a local thermodynamic equilibrium (LTE), were found to be 2.1× 1017 cm−3 and 0.33 eV at 1mTorr, respectively. The validity of the LTE is discussed according to the results discussed. Pressure dependence shows a decrease in the vibrational temperature when nitrogen pressure increases, while the electron density and temperature increase.  相似文献   
15.
16.
Reversing the polarity of the cycloaddition partners in Dane’s steroid synthesis provides ready access to enantiomerically pure, functionally-rich steroidal structures.  相似文献   
17.
New ligands H(2)L2-H(2)L6 comprise the cyclen macrocycle which is N,N'-dialkylated at the 1,7-nitrogen atoms by three- and four-carbon alkyl chains bearing terminal sulfonic (C(3) H(2)L2), phosphonic (C(3) H(2)L3, C(4) H(2)L4) or carboxylic acid (C(3) H(2)L5, C(4) H(2)L6) groups, and HL7 is N-monoalkylated by a four-carbon sulfonic acid group. The ligands were prepared by alkylation of a bridged bisaminal intermediate. The syntheses of cobalt(III) complexes containing a tetradentate cyclen, N,N'-1,7-Me(2)cyclen, cyclam or L2-L7 ligand together with the bidentate 8-quinolinato (8QO(-)) ligand, of interest as it is a model for a more potent cytotoxic analogue, were investigated. Coordination of ligands (L) cyclen, N,N'-1,7-Me(2)cyclen or cyclam to cobalt(III) was achieved using Na(3)[Co(NO(6))] to form [Co(L)(NO(2))(2)](+). HOTf (trifluoromethansulfonic acid) was used to prepare the triflato complexes [Co(L)(OTf)(2)](+), followed by substitution of the labile triflato ligands to yield [Co(L)(8QO)](ClO(4))(2) isolated as the perchlorate salts. One further example containing cyclam and the 5-hydroxymethyl-8-quinolinato ligand was also prepared by this method. Complexes containing the pendant arm ligands L2-L6 were prepared from the cobalt precursor trans-[Co(py)(4)Cl(2)](+). Reaction of this complex with H(2)L2·4HCl and 8QOH produced [Co(L2)(8QO)] in one step and contains two deprotonated sulfonato pendant arms. The reaction of H(2)L3·4HBr with [Co(py)(4)Cl(2)](+) gave [Co(L3)]Cl in which L3 acts as a hexadenate ligand with the three-carbon phosphonato side chains coordinated to cobalt. H(2)L5·4HCl bearing three-carbon carboxylic acid pendant arms gave a similar result. The four-carbon ligands were coordinated to cobalt by reaction of [Co(py)(4)Cl(2)](+) with H(2)L4·4HBr or H(2)L6·4HCl to give [Co(HL4)Cl(2)] or [Co(H(2)L6)Cl(2)]Cl, which in turn with 8QOH gave the 8QO(-) complexes [Co(L4)(8QO)] bearing anionic phosphate pendant arms or [Co(H(2)L6)(8QO)]Cl(2) containing neutral carboxylic acid side chains. The reaction of Na(3)[Co(CO(3))(3)] with the mono-N-alkylated ligand HL7·4HCl and then HOTf gave [Co(L7)(CO(3))] and then in turn [Co(L7)(OTf)(2)]. The carbonato complex [Co(L7)(CO(3))] with [8QO](2)[SO(4)] produced [Co(L7)(CO(3))]. All complexes containing L7 bear an anionic sulfonato group on the side chain. The synthesis and characterisation of the six new ligands based on N-alkylated cylen ligand and the cobalt complexes outlined above are described, along with cyclic voltammograms of the 8QO(-) complexes and the molecular structures determined by X-ray crystallography of [Co(cyclen)(H(2)O)(2)](OTf)(3) (formed by aquation of the triflato complex), [Co(cyclen)(8QO)](ClO(4))(2), Co(L2)(8QO)·2H(2)O, Co(L4)(8QO)·6H(2)O and [Co(H(2)L6)Cl(2)]Cl·H(2)O. These demonstrate the coordination of the cyclen ligand in the folded anti-O,syn-N configuration with the N-alkylated nitrogens occupying apical positions.  相似文献   
18.
Zinc metal reduction of the cobalt(III) complex [Co(1,4-bcc)](+) (1,4-bcc = 1,4-bis-carboxymethylcyclam) produces the corresponding cobalt(II) complex which crystallises as the coordination polymer {[Co(1,4-bcc)]ZnCl(2)}(n). A method has been developed for removal of the cobalt(III) ion from [Co(1,4-bcc)](+) and isolation of the free ligand as its hydrochloride salt, H(2)(1,4-bcc).4HCl. This has been used for the preparation of new metal complexes, and the syntheses and characterisation of the copper(ii), nickel(ii), zinc(ii) and chromium(iii) complexes containing the 1,4-bcc ligand are described. X-Ray crystal structures of {[Co(1,4-bcc)]ZnCl(2)}(n).2.5H(2)O, {[Cu(1,4-bcc)]CuCl(2)}(n).0.25MeOH.H(2)O and [Cu(1,4-bcc)H]ClO(4) show the complexes to have the trans(O) geometry of the 1,4-bcc ligand, while the structure of [Cr(1,4-bcc)H(0.5)](ClO(4))(1.5).EtOH exhibits the cis(O) configuration.  相似文献   
19.
Convergence of Rothe's method for the fully nonlinear parabolic equation ut+F(D2u, Du, u, x, t)=0 is considered under some continuity assumptions on F. We show that the Rothe solutions are Lipschitz in time, Hölder in space, and they solve the equation in the viscosity sense. As an immediate corollary we get Lipschitz behavior in time of the viscosity solutions of our equation.  相似文献   
20.
Methylol cellulose solutions in dimethylsulfoxide exhibit a viscosity maximum at 18% w/v followed by a minimum at 20%, as is characteristic of lyotropic liquid crystals. The biphasic solutions exhibit areas of clear and cloudy appearance. The latter are birefringent. The highly anisotropic solutions are uniformly briefringent and in the 25–33% w/v concentration region they are brightly colored. The optical rotations of the mesomorphic phases are high, indicating a cholesteric structure. The sign of the optical rotation depends on the solution concentration and at high concentrations (25+% w/v) varies with the area of the solution viewed.  相似文献   
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