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991.
Rodríguez JL Souto RM Fernández-Mérida L Pastor E 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(9):2134-2142
Spectroelectrochemical studies on the reactivity of butanol isomers on Pt electrodes in perchloric acid medium led to the observation of structural effects that result from the different arrangements of atoms in the organic molecules. The use of differential electrochemical mass spectrometry (DEMS) to detect volatile products showed that all four isomers react on the electrode, though different product yields were observed for each compound. In spite of the differences in the electrochemical behaviour of the butanol isomers, a series of general processes accounts for the results obtained. The formation of strongly adsorbed residues by a dehydration process leading to the formation of a C=C bond was proposed for all isomers. Electroreduction of the adsorbates produces C(4) and C(3) alkanes, and the latter reveal the existence of a fragmentation process. The C(4) hydrocarbons can be formed by hydrogenation of these residues and by hydrogenolysis of alcohol molecules in the bulk solution which react at the electrode with adsorbed hydrogen. On the other hand, CO(2) is formed during electrooxidation of the adsorbed species. Partial-oxidation products containing a carbonyl group were detected from 0.2 M solutions of 1-butanol, isobutyl alcohol and sec-butyl alcohol. The tertiary alcohol tert-butyl alcohol only reacts in its adsorbed state. 相似文献
992.
Xu M Brahmachary E Janco M Ling FH Svec F Fréchet JM 《Journal of chromatography. A》2001,928(1):25-40
Uniformly sized macroporous polymer beads, which can be used as chiral stationary phase (CSP), have been prepared by the staged templated suspension polymerization process using chiral monomer as one of the copolymerization components. This approach enables the preparation of CSPs for which properties such as pore size, pore volume, surface area, chemistry, and chiral ligands can be tuned over a broad range. Several types of well-defined chiral monomers were prepared and allowed to assess synergistic effect of multiple selectors attached to a branched linker as well as the effect of the length and chemistry of the linker. Microscale batch screening was used for simple and rapid evaluation of selectivity. The most promising candidate CSPs were prepared on a larger scale and packed into HPLC columns. Their performance was demonstrated on the separation of racemic N-(3,5-dinitrobenzoyl)-alpha-amino acid alkylamides. The highest separation factors alpha of up to 27 were observed for CSPs prepared from monomers containing the branched spacer. These highly selective CSPs also enabled the separation of larger amounts of the target racemates upon column overload conditions. 相似文献
993.
Gutiérrez L Alzuet G Borrás J Castiñeiras A Rodríguez-Fortea A Ruiz E 《Inorganic chemistry》2001,40(13):3089-3096
New Cu(II) complexes of sulfamethazine (4-amino-N-[4,6-dimethyl-2-pyrimidinyl]benzenesulfonamide, HL) [Cu(2)(CH(3)COO)(2)(L)(2)].2dmf (1) and ([Cu(L)(2)].2H(2)O)(infinity) (2) were prepared and structurally characterized. Compound 1 crystallizes in the monoclinic system, space group P2(1)/n, with a = 8.9486(9) A, b = 15.0956(12) A, c = 16.542(3) A, beta = 105.584(15) degrees, and Z = 2. Compound 2 crystallizes in the monoclinic system, space group P2(1)/c, with a = 13.8097(8) A, b = 14.5765(4) A, c = 13.7853(15) A, beta = 96.033(9) degrees, and Z = 1. In compound 1 two copper ions are linked by two syn-syn acetates and two nonlinear NCN bridging groups pertaining to the deprotonated sulfamethazine ligands. Each copper center presents a nearly square planar geometry. Magnetic susceptibility data for 1 show a strong antiferromagnetic coupling with 2J = -216.7 cm(-)(1). The EPR spectra at the X- and Q-band frequencies present the signals corresponding to the dinuclear entity, being the zero-field splitting parameter, D = 0.265 cm(-)(1). The antiferromagnetic exchange coupling is discussed using DFT calculations on some model compounds with NCN bridging ligands and also on model structures with mixed mu-acetato and NCN bridges. The copper in the polymeric compound 2 is five coordinate. The CuN(5) chromophore has a highly distorted square pyramidal geometry with small axial N-Cu-N angles of 65.53(14) and 59.90(13) degrees. In the structure a sulfamethazinate anion binds to one copper through the sulfonamido and pyrimidine N atoms and to an adjacent copper via the amino N atom. 相似文献
994.
E. V. Kalashnikova K. D. Shcherbakova E. Smolková-Keulemansová L. Feltl 《Chromatographia》1992,33(1-2):10-12
Summary A study has been made of the interaction between graphitized thermal carbon-black and cyclodextrins and a series of 28 derivatives of benzene (benzene, alkyl-, isoalkyl-, dialkyl-, trialkylbenzenes, vinyl-, and allyl-benzene). The specificretention volumes form the basis for a discussion of the mechanism of interaction and drawing conclusions for the practical separation of isomeric compounds. 相似文献
995.
Preconcentration was effected using a 50 mm × 2 mm i.d. minicolumn packed with a spherical cellulose sorbent with chemically bound quinolin-8-ol function groups (Ostorb Oxin). The column was connected to the nebulizer of the atomic absorption spectrometer and the sample solution and eluent (2 M hydrochloric acid) were sucked through it at a flow-rate of 2–3 ml min?1 by utilizing the negative pressure of the nebulizer. The experimental design was tested with the determination of traces of copper. Peak-area and peak-height measurements were compared. Owing to the simple calibration, the former method was used for quantification. The dynamic range was from 0.3 ng ml?1 (detection limit) to 5 μg ml?1 (breakthrough). The reproducibility in the concentration range 25 ng ml?1-5 μg ml?1 was better than 5%. Water-soluble inorganic salts, ammonia and sodium hydroxide were analysed. The accuracy of the results was checked by anodic-stripping voltammetry and by electrothermal AAS. 相似文献
996.
An automatic flow method for the determination of total aliphatic amines has been developed. Using an integrated micro extraction unit at the detection point that allows continuous on-line monitoring of small organic plug from which amines are extracted. It is based on the formation of ion-pairs between aliphatic amines and sodium 1,2-naphthoquinone-5-sulphonate that are subsequently extracted into chloroform. The gradual enrichment of the organic phase with the ion-pair is continuously monitored at 460 nm. Absorbance readings at a fixed time and the slopes of absorbance-time recordings are the measured parameters used for determination purposes. The proposed method has been applied to the determination of total aliphatic amines in both synthetic and real (food) samples. 相似文献
997.
M. Bokor T. Marek K. Süvegh K. Tompa A. Vértes Zs. Nemes-vetéssy K. Burger 《Journal of Radioanalytical and Nuclear Chemistry》1996,211(1):247-253
The complexes [Zn(1-propyltetraole)6](BF4)2 (Zn-ptz) and [Fe(methyltetrazole)6](BF4)2 (Fe-mtz) were investigated by positron annihilation and solid-state NMR spectroscopy. For Zn-ptz signs of structural rearrangements were found between 70 and 145 K. For the spin-crossover complex Fe-mtz a transition affecting the high-spin stat Fe2+ ions at lattice site B occurs below 15 K. 相似文献
998.
Measurement has been made of the dependence of the molecular weight distribution on the ratio of the catalytic system components and on the polymerization time for polycaprolactam obtained by anionic polymerization. A bimodal character of the curves was observed for products made using molar ratios of activator (N-benzoylcaprolactam) to initiator (sodium dihydro-bis(methoxyethoxy)aluminate) of 1:1 and 1:3, when the polymerization times were less than 1 hr. This course is explained by the influence of fast side-reactions, mainly condensations. For a ratio of 3:1 of the components of the catalytic system, smooth integral distribution curves are obtained, accounting for a very fast decrease in the strong base concentration in the initial stages of the polymerization. 相似文献
999.
In distinction to Extended Hückel Theory which predicts as the most stable conformation of free zwitterionic GABA a totally extended form, PCILO and SCF ab initio studies show that the intrinsically preferred conformation of the isolated molecule is a highly folded one, resulting from strong interactions between the two charged ends. Computations are also carried out for hydrated GABA in the supermolecule approach allowing moreover for the flexibility of binding of some of the water molecules of the first hydration shell. They predict the coexistence in solution of a large number of conformations showing different degrees of folding (or extension), a result confirmed by recent NMR studies. This and a number of similar results show that we have to adapt our thinking on the role of conformations in pharmacological activity to this situation, which was frequently obscured by the more abundant results of X-ray crystallography yielding a single conformation. 相似文献
1000.
Christer Albano William Dunn Ulf Edlund Erik Johansson Bo Nordén Michael Sjöström Svante Wold 《Analytica chimica acta》1978,103(4):429-443
Problems of pattern recognition in chemistry and other subjects can be divided conveniently into four different types depending on the level of scope of the problem.(1) Classification into one of a number of defined classes. As an example blood samples taken from persons known to be either controls or welders are considered. The problem is whether trace element concentrations in these samples contain information on whether or not a person is a welder.(2) Level 1 plus the possibility that an object is an outlier, i.e. does not belong to any of the defined classes. As an example, the üse of 13C-n.m.r. data to decide whether 2-substituted norbornanes have the exo or endo structure is discussed. (2A) Level 2, asymmetric. This situation occurs when one class does not have a systematic structure, but another class is homogeneous and can be described by a level 2 model. This occurs in the classification of materials or compounds as good or bad, active or inactive, and in binary classifications. As an example the use of trace element data to classify steel samples as having good or poor properties of strength is discussed.(3) Level 2 plus the ability to relate the variables measured to external properties of continuous character. As an example, the classification of a series of chemical compounds as β -receptor blockers, β -receptor stimulants, or neither, on the basis of their structural variables is discussed. In addition, relations between these structural variables and the measured biological activity are sought within each of the two classes.(4) Level 3 with the difference that several external property variables in the objects are measured. It may be desirable to use variables of the objects both for classification and for relations to several property variables: such examples are numerous in analytical chemistry. 相似文献