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51.
Roman F. Nalewajski Sebastito J. Formosinho Ant
nio J.C. Varandas Janusz Mrozek 《International journal of quantum chemistry》1994,52(5):1153-1176
The recently introduced set of the quadratic, two-electron covalent and ionic valence indices is used to investigate the bond-breaking–bond-forming (BB-BF ) process in an atom exchange reaction between H2 and X (X = H, F—I) as well as in the O2—H system. Valence changes accompanying selected charge reorganizations are examined within the three-orbital model and valence diagrams for symmetric transition states (TS s) are given. The UHF valence data for Li2O and CO2 and the H—H—X, O—O—H, and O—H—O (ABC) TS s (collinear and angular) are reported and compared to valence data in the separated fragments limits (SFL ), AB and BC. The overall valence, ν(ABC), and the total (ionic plus covalent) diatomic valences, νAB and νBC, are used as measures of the overall bond-order in a concerted BB–BF reaction, to test the postulate of the bond-energy–bond-order (BEBO ) model. In collinear TS s of H2X, ν ? ?1, i.e., one bonding electron pari, is found to be roughly preserved, whereas in the angular H2X and in collinear O—H—O TS s, the effect of increased valence at the saddle-point is observed, relative to that of diatomic fragments (reactiants or products). For the angular O—O—H TS , a similar increase in | ν (ABC)| relative to both O2 and OH SFL s is detected; smaller changes relative to the O2 data are found in the collinear TS . This observation is in agreement with earlier predictions from the intersecting-state model. The relative diatomic valences, ν/ν and ν/ν, are shown to conserve the overall relative bond multiplicity around 1 in both collinear and angular TS s of the H2—X systems. © 1994 John Wiley & Sons, Inc. 相似文献
52.
Roman MC 《Journal of AOAC International》2004,87(1):1-14
An international collaborative study was conducted of a high-performance liquid chromatography (HPLC)-UV method for the determination of the major (ephedrine [EP] and pseudoephedrine [PS]) and minor (norephedrine [NE], norpseudoephedrine [NP], methylephedrine [ME], and methylpseudoephedrine [MP]) alkaloids in selected dietary supplements representative of the commercially available products. Ten collaborating laboratories determined the ephedrine-type alkaloid content in 8 blind replicate samples. Five products contained ephedra ground herb or ephedra extract. These 5 products included ground botanical raw material of Ephedra sinica, a common powdered extract of Ephedra sinica, a finished product containing only Ephedra sinica ground botanical raw material, a complex multicomponent dietary supplement containing Ma Huang, and a high-protein chocolate flavored drink mix containing Ma Huang extract. In addition, collaborating laboratories received a negative control and negative control spiked with ephedrine alkaloids at high and low levels for recovery studies. Test extracts were treated to solid-phase extraction using a strong-cation exchange column to help remove interferences. The HPLC analyses were performed on a polar-embedded phenyl column using UV detection at 210 nm. Repeatability relative standard deviations (RSDr) ranged from 0.64-3.0% for EP and 2.0-6.6% for PS, excluding the high protein drink mix. Reproducibility relative standard deviations (RSDR) ranged from 2.1-6.6% for EP and 9.0-11.4% for PS, excluding the high protein drink mix. Recoveries ranged from 84.7-87.2% for EP and 84.6-98.2% for PS. The data developed for the minor alkaloids are more variable with generally unsatisfactory HORRATS (i.e., >2). However, since these alkaloids generally add little to the total alkaloid content of the products, the method gives satisfactory results in measuring total alkaloid content (RSDr 0.85-3.13%; RSDR 2.03-10.97%, HORRAT 0.69-3.23, exclusive of the results from the high protein drink). On the basis of these results, the method is recommended for Official First Action for determination of EP and PS in dietary supplements exclusive of the high protein drinks. 相似文献
53.
The modified ionic and covalent valence indices are introduced, defined in the framework of the two-particle density matrix, with respect to the reference state of separated atoms or ions (SAL ). They include only quadratic contributions in changes of the molecular charge-and-bond order matrix elements, relative to the SAL . General properties of the modified valence indices are examined and illustrative qualitative results for model systems are presented. Numerical UHF SCF MO valence data for selected diatomic and triatomic molecules are reported and interpreted in terms of the valence saturation effect and the ionic vs. covalent valence competition. A three-orbital valence model of a symmetric transition state of the bond-forming–bond-breaking reaction supports the BEBO model postulate of preservation of the total “bond order.” The model predictions are compared with the UHF numerical values. © 1994 John Wiley & Sons, Inc. 相似文献
54.
[formula: see text] The reaction of secondary and primary alcohols with highly fluorinated 3,4,5-tris(5,5,6,6,7,7,8,8,9,9,10,10,11,11,12,12,12-heptadecafluorododecan- 1-yloxy)benzoic acid in the presence of Ph3P and DIAD in THF at room temperature (fluorous Mitsunobu) resulted in a simple, chromatography-free isolation protocol with excellent yields (83-96%). 相似文献
55.
Piotr Kutrowski Dominika Sukowska Renata Pytlowany Roman Dziembaj 《Reaction Kinetics and Catalysis Letters》2004,81(1):3-11
Catalytic performance of Ba(OH)2 and Sr(OH)2 in self-condensation of acetone was examined in the temperature range from 273 to 303 K. A kinetic model of second order with respect to acetone was used for interpretation of the results obtained for the diacetone alcohol formation.This revised version was published online in December 2005 with corrections to the Cover Date. 相似文献
56.
Marcos J Pascual JA de la Torre X Segura J 《Journal of mass spectrometry : JMS》2002,37(10):1059-1073
A fast and sensitive method for the comprehensive screening of anabolic agents and other banned doping substances using gas chromatography/tandem mass spectrometry (GC/MS/MS) with an external ionization ion trap mass spectrometer is presented. The method takes advantage of the resolving power of MS/MS to eliminate background interferences, thus speeding up the chromatographic analysis. For each compound, different fragmentation reactions were studied and their collision energies optimized to obtain the best sensitivity in terms of their signal-to-noise ratio (S/N). A dramatic reduction in overall analysis time was achieved compared with other common approaches. More than 50 substances could finally be monitored in less than 7.4 min with detection limits (S/N >3) lower than 0.5 ng ml(-1) for most of the compounds with special sensitivity requirements according to the International Olympic Committee (IOC). A validation procedure for qualitative analysis was performed. The selectivity of the method showed that no interfering peaks were observed at the retention time of the analytes. Good intermediate precision, below 25% for most of the compounds, and robustness were observed. The optimized method was successfully applied to analyse more than 100 real human urine samples with optimum sensitivity and specificity rates. 相似文献
57.
58.
Roman Luboradzki Janusz Lipkowski Yurii A. Simonov Marina S. Fonari Edward V. Ganin Arkadii A. Yavolovskii 《Journal of inclusion phenomena and macrocyclic chemistry》1995,23(3):181-193
An X-ray—diffraction study is reported for two molecular complexes containing 3,4-diamino-1,2,5-oxadiazole as guest (G) with 18-crown-6 (18-C-6) andcis-anti-cis-dicyclohexano-18-crown-6 (DCH-6B) as host. Both complexes are of the polymeric-chain structure with the guest molecule bridging two crown neighbours. ComplexI: [18-C-6*G*H2O], 111, monoclinic,P21/n,a=8.171(1),b=15.042(2),c=16.209(6) Å, =101.15(2)°, finalR-factor 0.068. ComplexII: [DCH-6B*G], 11, monoclinicC2/c,a=21.212(4),b=9.380(2),c=13.049(3) Å, =108.61(3)°, finalR 0.047. 相似文献
59.
Roman B?aszczyk 《Tetrahedron letters》2007,48(33):5859-5863
An efficient, diastereoselective synthesis of 5-substituted (2-thioxo-imidazolidin-4-yl)phosphonic acid diethyl esters from metallated diethyl isothiocyanatomethylphosphonate and activated imines has been developed. The three-step transformation of imidazolidine-2-thione derivatives into 1,2-diaminoalkylphosphonic acids is also described. 相似文献
60.
Tomcík P Jencusová P Krajcíková M Bustin D Brescher R 《Analytical and bioanalytical chemistry》2005,383(5):864-868
An interdigitated microelectrode array (IDA) was applied to the determination of formaldehyde released from textiles produced
in industry. The proposed method is based on formaldehyde reaction with hypobromite which is formed in weakly basic media
by control current electrooxidation of bromide on the generator segment of the IDA array. The unreacted hypobromite diffuses
through the gap between individually polarisable IDA segments and it is amperometrically detected on the collector segment
of the IDA. The efficiency of this nonconvective transfer process in the absence of formaldehyde was substantially higher
(78%) in comparison with that when using the rotating ring disc electrode. The influence of the added formaldehyde on the
transfer process can be utilised to develop a simple and sensitive analytical procedure for formaldehyde detection with a
detection limit of 4×10−6 mol dm−3. 相似文献