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131.
Ali Mohammad Akbar Edwards Alice A. Tuah Jauyah Hossain Mir Ezharul Nazimuddin Mohamed 《Transition Metal Chemistry》1997,23(1):41-44
A new, potentially polydentate sulfur–nitrogen chelating agent, 2,6–bis(N-methyl-S-methyldithiocarbazato)pyridine (L) has
been synthesized and characterized. With nickel(II) salts, the ligand yields complexes of empirical formula NiLX2·nH2O (X=Cl−,
NCS− or NO3−; n=0 or 1) in which it behaves as a quadridentate NSSN chelating agent, coordinating to the nickel(II) ion via
the two amino nitrogen atoms and the two sulfur atoms. Magnetic and spectral evidence support a distorted octahedral structure
for these complexes. The ligand reacts with copper(II), platinum(II) and palladium(II) salts to yield homo-binuclear complexes
of general formula [M2LX4]·nSol (M=CuII, PtII or PdII; X=Cl− or Br−; n=0.5, 1 or 2; Sol=H2O, MeOH or MeCOMe), in which each
of the metal ions is in a square-planar environment. These complexes have been characterized by a variety of physicochemical
techniques.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
132.
Hybrid linear analysis (HLA), as a recent factor-based multivariate calibration technique, was applied for the spectrophotometric determination of ternary mixtures of pseudoephedrine hydrochloride (PSU), dextromethorphan hydrobromide (DXT), and sodium benzoate (BNZ). The utilized HLA was assisted by a wavelength selection procedure which was based on the calculation of the net analyte signal (NAS) regression plot in any considered wavelengths window for each test sample, in addition to a moving window strategy for searching the region with maximum linearity of NAS regression plot (minimum error indicator (EI)). HLA was applied because it was simpler to adapt to the NAS regression plot methodology, and also used less factors than partial least squares (PLS). An orthogonal array design was applied for formation of calibration and prediction sets in the concentration ranges 0-7500 μmol L−1 for PSU, 0-300 μmol L−1 for DXT, and 0-1400 μmol L−1 for BNZ. The method had the ability to select wavelength regions that minimize the effect of non-linearity of the spectral data, in addition to that of non-modeled interferences. The application of the selected wavelength regions improved the obtained relative standard error of predictions for PSU, DXT, and BNZ, respectively, from 5.24, 8.67, and 5.48% to 2.19, 5.21, and 3.62% (using lower number of factors). To check the ability of the proposed method in selection of linear regions of spectra, a test for detecting non-linear regions of spectral data in multivariate spectroscopic assays was also described. Additives in the commercial syrup samples did not interfere with their determinations. The method was successfully applied for the determination of pseudoephedrine HCl, dextromethorphan HBr, and sodium benzoate in cough suppressant syrup samples. 相似文献
133.
Harp GP Rangwalla H Yeganeh MS Dhinojwala A 《Journal of the American Chemical Society》2003,125(37):11283-11290
Surface-sensitive infrared-visible sum frequency generation spectroscopy (SFG) in total internal reflection geometry has been used to study the structure of poly(vinyl n-octadecyl carbamate-co-vinyl acetate) (PVNODC) or poly(octadecyl acrylate) (PA-18) in contact with a deuterated or hydrogenated polystyrene (dPS or hPS) layer. SFG spectra from the PVNODC (or PA-18)/hPS interface show methyl and methylene peaks corresponding to PVNODC (or PA-18) and phenyl peaks corresponding to the PS. Analysis suggests that the methyl groups are tilted at angles less than 30 degrees with respect to the surface normal. The presence of a strong methylene peak suggests the PVNODC alkyl side chains contain more gauche defects at the PS/PVNODC interface in comparison to PVNODC (or PA-18)/air interfaces. On heating, the SFG intensity from the PS/PA-18 interface drops sharply near the bulk melting temperature (T(m)) of PA-18. Interestingly, a similar drop in SFG signal is also observed for the PS phenyl groups. This demonstrates the ability of the phenyl group at the PS/PA-18 interface to rearrange itself upon the solid-to-liquid transition of the PA-18 alkyl side chain, at a temperature well below the bulk PS glass transition temperature. For PS/PVNODC interfaces, the drop in SFG intensity is gradual and in agreement with the three broad transitions of PVNODC observed in the bulk. 相似文献
134.
Mohammad M. Fares Adeeb S. El-Faqeeh 《Journal of Thermal Analysis and Calorimetry》2005,82(1):161-166
Summary Thermal degradation under N2atmosphere and thermoxidative degradation under air atmosphere of increasingly grafting efficiency values (i.e. GE%=0.0 to 35.5) for starch and starch grafted with N-tert-butylacrylamide thermosensitive copolymers (starch-g-BAM) by Ozawa and Kissinger methods using thermogravimetric analysis
(TG) and differential scanning calorimetry techniques (DSC) at 10, 30 and 50% mass losses respectively have been studied.
Influence of physical inter and intra molecular interactions on grafting and consequently on activation energy of degradation
(Ea,d) was investigated using Ozawa's method, whereas linear dependence of Ea,don GE% by scaling relations using Kissinger's method was determined. Furthermore, the thermoxidative degradation induces the possibility
of molecular rearrangement, cyclization and partial crosslinking that is deduced from the activation energy of degradation
(Ea,d) and residual mass of TG profile. Thermal stability of starch does not alter as a result of different grafting efficiency
percentages. 相似文献
135.
Ali Morsali Elaheh K. Goharshadi G. Ali Mansoori Mohsen Abbaspour 《Chemical physics》2005,310(1-3):11-15
A simple and accurate expression for radial distribution function (RDF) of the Lennard-Jones fluid is presented. The expression explicitly states the RDF as a continuous function of reduced interparticle distance, temperature, and density. It satisfies the limiting conditions of zero density and infinite distance imposed by statistical thermodynamics. The distance dependence of this expression is expressed by an equation which contains 11 adjustable parameters. These parameters are fitted to 353 RDF data, obtained by molecular dynamics calculations, and then expressed as functions of reduced distance, temperature and density. This expression, having a total of 65 constants, reproduces the RDF data with an average root-mean-squared deviation of 0.0152 for the range of state variables of 0.5 T* 5.1 and 0.35 ρ* 1.1 (T*=kT/ε and ρ* = ρσ3 are reduced temperature and density, respectively). The expression predicts the pressure and the internal energy of the Lennard-Jones fluid with an uncertainty that is comparable to that obtained directly from the molecular dynamics simulations. 相似文献
136.
Ali Mohammad Akbar Mirza Aminul Huq Keng See Tho Wai Butcher Raymond J. 《Transition Metal Chemistry》2003,28(2):241-245
Condensation of 2,6-diacetylpyridine (dap) with S-methyldithiocarbazate (smdtc) in a 1:2 molar ratio yields a bicondensed pentadentate Schiff base (H2dapsme) which reacts with K2MCl4 (M = PdII, PtII) giving stable complexes of empirical formula, [M(dapsme)] · 0.5Me2CO. These complexes have been characterized by a variety of physico-chemical techniques. Condensation of dap with smdtc in a 1:1 molar ratio also yields the bicondensed Schiff base (H2dapsme) as the major product, but a mono-condensed one-armed Schiff base (Hmdapsme) is also obtained as a minor product. The latter reacts with K2PdCl4 in an EtOH–H2O mixture yielding a crystalline complex of empirical formula, [Pd(mdapsme)Cl], the crystal structure of which has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the ligand is coordinated to the palladium(II) ion as a uninegatively charged tridentate chelating agent via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the oxygen atom of the acetyl group does not participate in coordination. 相似文献
137.
Mohammad Reza Ganjali Morteza HosseiniFatemeh Basiripour Mehran JavanbakhtOmid Reza Hashemi Majid Faal RastegarMojtaba Shamsipur Gerald.W Buchanen 《Analytica chimica acta》2002,464(2):181-186
A novel selective membrane electrode for determination of ultra-trace amount of lead was prepared. The PVC membrane containing N,N′-dimethylcyanodiaza-18-cown-6 (DMCDA18C6) directly coated on a graphite electrode, exhibits a Nernstian response for Pb2+ ions over a very wide concentration range (from 1.0×10−2 to 1.0×10−7 M) with a limit of detection of 7.0×10−8 M (∼14.5 ppb). It has a fast response time of ∼10 s and can be used for at least 2 months without any major deviation in potential. The electrode revealed very good selectivity with respect to all common alkali, alkaline earth, transition and heavy metal ions. The proposed sensor was used as an indicator electrode in potentiometric titration of lead ions and in determination of lead in edible oil, human hair and water samples. The proposed sensor was found to be superior to the best Pb2+-selective electrodes reported in terms of detection limit and selectivity coefficient. 相似文献
138.
DFT method (B3LYP) with 6-31G* basis set was utilized in the computation of a fully optimized structure, net atomic charges and spin densities of the intermediate of cytochrome P-450-oxoiron(IV) porphyrin cation radical, compound I – in the presence of axial ligand such as thiolate (SMe−) imidazole (IM), phenoxide (OPh−), methoxide (OMe−) and chloride (Cl−). The results show doublet states in compound I are about 2–4 kcal/mol more stable than quartet states for all aforementioned ligands, and the doublet state is the ground state in all cases. However, electron donor ability of the ligands are in the order of SMe− > IM > OMe− > OPh− > Cl−. Also the active oxidant intermediate of cytochrome P-450 between different mesomeric structures select sulfur oxygen radical type structure and can be viewed as (RS↓)Fe↑(IV)(O↑)(Por). In horseraddish peroxidase (HRP) and peroxidase with histidine axial ligand π cation radical character of porphyrin ring is preferred (Im)Fe↑(IV)(O↑)(Por↓). For the ligands such as OMe−, OPh− and Cl− oxidation mainly took place on the iron and the active intermediate can be viewed as (L)Fe↑(V)(O)(Por) with one unpaired electron localized on the iron. 相似文献
139.
Reduced viscosity polymer matrices for microchip electrophoresis of double-stranded DNA 总被引:1,自引:0,他引:1
On a polymethylmethacrylate (PMMA) microchip, double-stranded DNA fragments with a wide size range from 50 bp to 20 kbp were separated by two polymer solutions. One was a hydroxypropylmethylcellulose-4000 (HPMC-4000) solution of 1.3% (w/v) to separate fragments below 590 bp, and another was a mixed four molecular weight poly(ethylene oxide) solution at a total concentration of 0.1% to separate fragments above 520 bp. The widths at half height (wh) of the fragments had a good relationship with their migration times (tR) in both polymer solutions. Such a relationship was suitable for obtaining the wh values of unresolved peaks, calculating the resolution of two adjacent fragments, and optimizing microchip separation matrices. Based on the relativity, a low viscosity medium containing 2% HPMC-50 and 8% glucose was optimized for high-performance separation of a phiX174 HaeIII restriction fragment digest. 相似文献
140.
Ethyl oxo-(2-oxo-cycloalkyl)-ethanoates undergo a smooth reaction with triphenylphosphine and dialkyl acetylenedicarboxylates via intramolecular Wittig reaction to produce spiro-cyclobutene derivatives. These spiro systems undergo electrocyclic ring opening reaction to produce electron-deficient 1,3-dienes, which spontaneously cyclize to 2H-pyran derivatives. 相似文献