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31.
Heinz Günter Viehe Zdenek Janousek 《Angewandte Chemie (International ed. in English)》1973,12(10):806-818
Dichloromethylenammonium salts, particularly dichloromethylenedimethylammonium chloride, occupy a unique place as stable but reactive building blocks for synthesis. They contain three mobile chlorine atoms activated by an amino group on the same carbon atom. These salts can be regarded as chlorinated Vilsmeier or Mannich reagents and are thus at a higher oxidation level. As in the Mannich or Vilsmeier reaction, the carbon condenses here as an electrophile with formation of C? C or C? hetero atom bonds in a variety that is still far from being exhausted. 相似文献
32.
The development of piezoelectric immunosensors for human serum albumin (HSA) is reported. The piezoelectric crystals were modified either with monoclonal antibody AL-01 (direct assay) or with HSA (competitive assay). Measurements were carried out in the flow-through mode. Affinity interaction between albumin and the antibody was characterised. With immobilised antibody and HSA in solution, the kinetic association rate constant k(a) was 18 100 l mol(-1) s(-1) and the dissociation constant k(d) was 0.00369 s(-1). For the opposite arrangement (immobilised HSA), a slower dissociation was observed, k(d) was 0.00085 s(-1). A competitive assay for HSA was developed with working range of 1-5 mug ml(-1) and a total time for one analysis equal to 17 min. Samples of urine were analysed after tenfold dilution. The developed system was successfully evaluated on real samples from diabetic patients and the obtained results correlated well with the standard reflectometric assay of proteins in urine. 相似文献
33.
E. Makrlík P. Vaňura P. Selucký 《Journal of Radioanalytical and Nuclear Chemistry》2006,267(3):533-535
Summary Extraction of microamounts of calcium by a nitrobenzene solution of hydrogen dicarbollylcobaltate (H+B-) in the presence of 18-crown-6 (18C6, L) has been investigated. The equilibrium data have been explained assuming that the
complexes HL+, CaL2+and CaL are extracted into the organic phase. The values of extraction and stability constants of the complex species in nitrobenzene
saturated with water have been determined. 相似文献
34.
In this contribution, the on-line coupling of solid phase extraction (SPE), based on a restricted-access material (RAM), with sequential injection technique (SIA) for the analysis of biological samples, is described. The SIA-RAM system was tested with a new potential antileucotrienic drug (VUFB-19363 (Quinlukast)) for serum analysis. The method is based on SPE with the novel internal-surface reversed-phase column packing material-alkyl-diol silica (ADS). The supports tolerate direct and repetitive injection of proteinaceous fluids (plasma, serum) and allow reversed-phase partitioning at the internal surface. A column packed with a 25 microm C18 alkyl-diol support was used for direct serum injection. Using a 6-port selection valve and the system of three mobile phases, the polar matrix compounds and metabolites are removed by sequentially aspirated mobile phases with lower content of the organic part (methanol-water (2:98) and following acetonitrile-water (20:80)) to the waste, and then, the analyte enriched on the column is eluted by a strong mobile phase (acetonitrile-methanol-water (40:20:40)) to the UV detector without transfer loss. With the fully automated SIA system, a total analysis time of less than 10 min was achieved. The only off-line sample pre-treatment step required to remove particulate matter was centrifugation. The studies showed a range of linearity (2-40 microg ml(-1)) and a high recovery (93.6-96.8%) of drug from the biological matrix with coefficients of variation (RSD) less than 5.0% (n = 6). This paper introduces a new, simple and robust analytical technique suitable for screening determination and direct analysis of drugs in biological materials. 相似文献
35.
Boca R Gembický M Herchel R Haase W Jäger L Wagner C Ehrenberg H Fuess H 《Inorganic chemistry》2003,42(22):6965-6967
Triethylenetetramine (L(4)) was used as a tetradentate blocking ligand that, after complexation with Ni(II), leaves two sites ready for ligation with tricyanomethanide. The formed binuclear complex [L(4)Ni(NCC(CN)CN)(2)NiL(4)](ClO(4))(2) exhibits a ferromagnetic coupling with J/hc = +0.15 cm(-1) and g(Ni) = 2.126; below 16 K, a ferromagnetic ordering is evidenced by ac magnetic susceptibility (both in-phase and out-of-phase), magnetization, field-cooled magnetization, and zero-field-cooled magnetization measurements. 相似文献
36.
Z. Janout S. Pospíšil M. Vobecký 《Journal of Radioanalytical and Nuclear Chemistry》1980,56(1-2):71-81
A Doppler broadening is described of the 4438 keV spectral gamma-line observed by means of a Ge(Li) detector during the deexcitation
of nuclei of12C in an inelastic scattering12C(n, n′γ)12C using an241Am−Be source as well as during the reaction9Be(α, nγ)12C taking place in the Am−Be source. The FWHM of the spectral line is equal to (90±4) keV in the latter reaction and (64±8)
keV in the former process. Experimental values agree well with theoretical ones.
Presented at the Instrumental Activation Analysis Conference, IAA 79, June 4–8, 1979, Klučenice, Czechoslovakia. 相似文献
37.
Six new dinuclear or trinuclear FeIII complexes involving tetradentate Schiff bases N,N′-bis(salicylidene)ethylenediamine
(salenH2) or bis(salicylidene)-o-phenylenediamine (salophH2) with 2,5-pyridinedicarboxylic acid, acetylenedicarboxylic acid
or 1,3,5-benzenetricarboxylic acid have been synthesized and characterized by means of elemental analysis, i.r. spectroscopy,
thermal analyses, conductivity measurements and variable-temperature magnetochemical measurements to the temperature of liquid
nitrogen. The complexes can be characterized as high-spin distorted octahedral FeIII bridged by carboxylic acids. The dicarboxylic
or tricarboxylic acids play a role as bridges for weak antiferromagnetic intramolecular exchange. The antiferromagnetic coupling
parameters J vary in the -1.99 to -5.47cm-1 range for the dimers, whilst the values are -2.35 and -1.42cm-1 for the salen
and saloph trimers, respectively. One complex, namely [{Fe(saloph)}2(2,5-dicarpy)]middot H2O, obeys the Curie-Weiss law.
This revised version was published online in June 2006 with corrections to the Cover Date. 相似文献
38.
Pokorný J 《Bioelectrochemistry (Amsterdam, Netherlands)》2004,63(1-2):321-326
Microtubules, which are thought to be the primary organizers of the cytoskeleton, are electrical polar structures with extraordinary elastic deformability at low stress and with energy supply from hydrolysis of guanosine triphosphate (GTP) to guanosine diphosphate (GDP). At least a part of the energy supplied from hydrolysis can excite vibrations. Energy is mainly lost by viscous damping of the surrounding cytosol. Viscous damping is diminished by a slip layer which is formed by an attracted ionic charge layer and by a thin surface layer of the microtubule. Relaxation time caused by viscous damping may be several orders of magnitude greater than period of vibrations at 10 MHz. Energy supplied to the microtubule is of the order of magnitude of 10(-14) W cm(-1) (per unit length of the microtubule). 相似文献
39.
Interaction in Crystals: The Keyboard of Na⊕ Coordination Numbers in Its Carbazole Anion Salts Some local minima in the shallow potential of the system carbazole anion, sodium cation, and the ethers tetrahydrofuran, 1,2-dimethoxyethane, diglyme, triglyme, tetraglyme, 15-crown-5 as well as 2.2.1-cryptand are explored experimentally and by quantum-chemical calculations. Three prototype contact-ion multiples of Na⊕-solvated carbazole anion M? salts have been crystallized and structurally characterized: polyether-solvated monomers [M?Na⊕solv]1, solvent-shared dimers [M?Na⊕solv]2, and solvent-separated polyions [(M?)nNa?solv](n?1)? [Na⊕solv](n?1). The Na⊕ coordination numbers stretch from 3 to 7 as illustrated by the compounds [(M?)3Na+]??[Na+(2.2.1-crytand)]2 for 3 and 7, [(M?)2Na+(THF)2]? [Na⊕(2.2.1-cryptand)] for 4 and 7, [M? Na+(diglyme)]2 for 5, or [M? Na+(l 5-crown-5)] for 6. Structural comparison is based on literature analogies as well as on results of MNDO calculations concerning charge distribution and enthalpies of formation. Taken together, the results demonstrate the delicate energy balance, by which cation solvation can influence the formation of organic salts. 相似文献
40.
Detlef Schrder Jessica Loos Helmut Schwarz Roland Thissen Jana Roithova Zdenek Herman 《International journal of mass spectrometry》2003,230(2-3):113
Singly and doubly charged C4H3+/2+ ions generated upon electron ionization (EI) of the neutral precursors 1,3-butadiene, benzene, and exo-methylene cyclopropane, respectively, are examined by sector-field mass-spectrometry. Charge stripping of the mass-selected monocations affords the corresponding dications and charge exchange of the C4H32+ dications allows for the reverse redox process. Refined analysis and additional MS/MS studies suggest that the monocations are mixtures of isomeric ions formed upon ionization, whereas only a single type of dication seems to be formed. As an average of energy-resolved measurements, a vertical ionization energy of IEv(C4H3+)=16.5±0.4 eV is derived. In addition to the experimental work, density functional theory is used for a computational exploration of the mono- and dicationic species. The best theoretical estimates are IEa(C4H3+)=16.33 eV and IEv(C4H3+)=16.49 eV for the most stable isomer H2C=C---CCH+. Combination of the experimental and theoretical findings leads to the conclusion that the diacetylene cation C4H2+ has indeed a positive proton affinity of PA(C4H2+)=1.50±0.42 eV. 相似文献