Pi bonding and negative hyperconjugation in mono-, di-, and triaminoborane, -alane, -gallane, and -indane

A systematic quantum chemical investigation of mono-, di-, and triaminoborane, -alane, -gallane, and -indane is carried out to determine quantitatively the effects of pi bonding and negative hyperconjugation on structures, energetics, and rotational barriers in these systems. Pi bonding plays a significant role in the aminoborane compounds, but becomes rapidly less significant in the aminoalanes, -gallanes, and -indanes. For each main-group metal X investigated, X-N rotational barriers are found to be essentially equal depending only on the number of remaining in-plane amino groups. The contribution of negative hyperconjugation to reducing rotational barriers, as assessed from natural bond orbital (NBO) delocalization energies, is independent of the pyramidalization of the out-of-plane amino group, and is also dependent only on the number of rotated groups. Optimized tris[bis(trimethylsilyl)amino]-substituted structures of boron, aluminum, gallium, and indium are found to compare quite well with available experimental structural data, and exhibit X-N torsion angles that are independent of the central metal atom.     

Aromaticity and antiaromaticity in fulvenes, ketocyclopolyenes, fulvenones, and diazocyclopolyenes

The structures, energies, natural charges, and magnetic properties of 3-, 5-, 7-, and 9-membered cyclic polyenes 1-4, respectively, with exocyclic methylene, keto, ketenyl, and diazo substituents (a-d, respectively) were computed at the B3LYP/6-311G+ **//B3LYP/6-311+G** level to elucidate their aromatic and antiaromatic properties. The corresponding conjugated cyclic cations le and 3e were also studied. The criteria used are isomerization energies (ISE), magnetic susceptibility exaltations (lambda), aromatic stabilization energies (ASE), nucleus independent chemical shifts (NICS), and bond length alternation (deltaR). Planar C2v structures were found to be the lowest energy minima with the exceptions of diazocyclopropene (1d), cycloheptafulvenone (3c), diazocycloheptatriene (3d), and all of the cyclononatetraene derivatives (4). The fulvenes (1a-4a) have modest aromatic or antiaromatic character, and are used as standards for comparison. By these criteria the ketenylidene and diazo cyclopropenes and cycloheptatrienes 1,3-c,d and oxo cyclopentadiene and cyclononatetraene 2,4b are antiaromatic, while the 5- and 9-ring ketenyl and diazo compounds and 3- and 7-ring ketones are aromatic. The degree of aromatic/antiaromatic character decreases with ring size. The consistent agreement with Hückel rule predictions for all the criteria shows their utility for the evaluation of the elusive properties of aromaticity and antiaromaticity.     

Phosphorimetric determination of procaine,phenobarbital, cocaine,and chlorpromazine in blood serum,and cocaine and atropine in urine

A new sensitive and rapid method is proposed for the determination of procaine, cocaine, phenobarbital and chlorpromazine in blood serum, and cocaine and atropine in urine. The drug is extracted from the biological fluid using chloroform or ether, the solvent is evaporated and the resulting residue is dissolved in EPA; the EPA solution is measured phosphorimetrically. Recoveries of 100 ± 6% and relative standard deviations of 2–5% are obtained for most drugs.     

Nodal,ionic, and atomic radii,in compounds

The distance in an atom from the nucleus to the final node in the wavefunction of a valence electron has been defined as the nodal radius. This parameter, in conjunction with a Thomas-Fermi pseudo-potential, is used to calculate the nearest-neighbor distance in some octet compounds. Calculated values of the atomic radii are compared with the semi-empirical ionic and tetrahedral radii for atoms in these compounds.     

Determination of Cd, Co, Cr, Cu, Fe, Ni and Pb in Milk, Cheese and Chocolate

 Combined analytical procedures consisting of wet digestion step followed by instrumental determination – differential pulse cathodic stripping voltammetry (DPCSV) or electrothermal atomic absorption spectrometry (ETAAS) – as well as a direct analysis method – slurry sampling ETAAS – for the determination of Cd, Co, Cr, Cu, Fe, Ni and Pb in milk, cheese and chocolate are described and compared. Wet digestion using a mixture of HNO₃-HClO₄-H₂O₂ is proposed for complete matrix decomposition prior to trace analyte determinati on by DPCSV or ETAAS. A mixture of HNO₃-H₂O₂ is used for slurry preparation. Optimal instrumental parameters for trace analyte measurements are presented. The reliability of the procedures has been verified by analyzing standard reference materials. Results obtained are in good agreement with the certified values and the relative standard deviations (for these results) are in the range 5–10% for wet digestion DPCSV or ETAAS and 3–9% for slurry sampling ETAAS in the range of 2 μgċg⁻¹ (Cd) to 12 μgċg⁻¹ (Fe). Received August 24, 1999. Revision January 20, 2000.     

Congresses, conferences, symposia, meetings, and seminars held in 1994

Information Congresses, Conferences, Symposia, Meetings, and Seminars in the Field of Chemical Sciences Held with the Participation of the Russian Academy of Sciences

Congresses, conferences, symposia, meetings, and seminars held in 1994     

Congresses,conferences, symposia,meetings, and seminars held in 1994

Information Congresses, Conferences, Symposia, Meetings, and Seminars in the Field of Chemical Sciences Held with the Participation of the Russian Academy of Sciences

International conference on chemical and biological disarmament and conversion (MOSCON-94)     

Congresses,Conferences, Symposia,Meetings, and Seminars held in 1994

Information

Congresses, Conferences, Symposia, Meetings, and Seminars held in 1994     

Congresses, conferences, symposia, meetings, and seminars held in 1994

Information

Congresses, conferences, symposia, meetings, and seminars held in 1994     

Content,design, and representation in chemistry

The aim of this paper is to engage with the interplay between representational content and design in chemistry and to explore some of its epistemological consequences. Constraints on representational content arising from the aspectual structure of representation can be manipulated by design. Designs are epistemologically important because representational content, hence our knowledge of target systems in chemistry, can change with design. The significance of this claim is that while it has been recognised that the way one conveys information makes a difference to the inferences one can draw from representations in spite of the invariance of informational content, the present paper argues that in chemistry and biochemistry it is often the case that designs have cognitive priority relative to informational content.     

Polarization, steric, and focusing micro-thermal field-flow fractionation principles, theory, instrumentation, and applications in polymers and particles analysis

The benefits of the miniaturization of the separation channel for Thermal field-flow fractionation (TFFF) are analyzed theoretically and studied experimentally. It is found that the operational variables influencing the efficiency and resolution of the separation can be optimized and that the concept of a micro-TFFF is meaningful. A miniaturized TFFF channel was proposed and constructed. It has been demonstrated experimentally that micro-TFFF allows one to carry out high-performance separations under carefully chosen experimental conditions. This new technique is highly competitive in comparison with size-exclusion chromatography (SEC) of macromolecules with molar masses up to roughly one million gram per mole. However, the versatility of micro-TFFF is superior to SEC for macromolecules of ultra-high molar masses, as well as colloidal sub-micron, and micron-sized particles of synthetic, natural, or biological origin. The free choice of the carrier liquids without any modification of the separation system affords an advantage to micro-TFFF. The experimental implementation and application to polymer and particle analysis confirmed the potential of micro-TFFF.     

Zigzags, railroads, and knots in fullerenes

Two connections between fullerene structures and alternating knots are established. Knots may appear in two ways: from zigzags, i.e., circuits (possibly self-intersecting) of edges running alternately left and right at successive vertices, and from railroads, i.e., circuits (possibly self-intersecting) of edge-sharing hexagonal faces, such that the shared edges occur in opposite pairs. A z-knot fullerene has only a single zigzag, doubly covering all edges: in the range investigated (n /= 38, all chiral, belonging to groups C(1), C(2), C(3), D(3), or D(5). An r-knot fullerene has a railroad corresponding to the projection of a nontrivial knot: examples are found for C(52) (trefoil), C(54) (figure-of-eight or Flemish knot), and, with isolated pentagons, at C(96), C(104), C(108), C(112), C(114). Statistics on the occurrence of z-knots and of z-vectors of various kinds, z-uniform, z-transitive, and z-balanced, are presented for trivalent polyhedra, general fullerenes, and isolated-pentagon fullerenes, along with examples with self-intersecting railroads and r-knots. In a subset of z-knot fullerenes, so-called minimal knots, the unique zigzag defines a specific Kekulé structure in which double bonds lie on lines of longitude and single bonds on lines of latitude of the approximate sphere defined by the polyhedron vertices.     

Catalysis in the Synthesis of S,N-Heterocycles and O,N-, S,N-, and O,S,N-Macroheterocycles

The review systemizes and generalizes published data on the catalytic syntheses of six-, seven-, and eight-membered S,N-heterocycles and O,N-, S,N-, and O,S,N-macroheterocycles.     

Congresses,Conferences, Symposia,Meetings, and Seminars held in 1994

Information

Congresses, Conferences, Symposia, Meetings, and Seminars held in 1994