A configuration interaction study of phosphine using bonded functions

A computational study is made of the effect of basis set upon the energy, properties and inversion barrier of the phosphine molecule. The calculations are performed at both the SCF and CI level. The flexibility of the double zeta basis is discussed in the light of the results.     

Reaction of undecyl radicals with aromatic hydrocarbons

A competition method (R^.+O₂RO ₂ ^. , R^.+XHRH+X^.) is proposed to measure the relative rate constants for the interaction of alkyl radicals with different organic compounds. Partial (per C–H bond) rate constants have been determined for the reaction of undecyl radicals with cumene, ethylbenzene and toluene.

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(R^.+O₂RO ₂ ^. , R^.+XHRH+X^.), . ( C–H ) , .

     

Reaction of di- and trisubstituted ethynylsilanemagnesium halides with dimethylethynylfluorosilane

Conclusions The reaction of magnesium bromide derivatives of di- and triethynylsilanes with dimethylethynylfluorosilane gave 1,2-disubstituted silylacetylenes containing ethynyl and vinyl groups at the silicon atoms.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2614–2616, November, 1984.     

Theoretical approach and the practice to the evaluation of structural parameters characterizing concentration polarization alongside ion-exchange membranes by means of dielectric measurement

As the application of a dielectric theory proposed previously (J Membrane Sci 64:153–161 (1991)), theoretical formulation and the practical procedure of dielectric analysis are developed to calculate the structural parameters such as the conductivity gradient and the thickness of the concentration polarization layer, the capacitances and the conductances of the two adjoining aqueous phases from the observed dielectric parameters. The procedure of calculation consequent upon the theoretical formulation was applied to double relaxation data observed for cation-exchange membrane systems under application of d.c. bias voltage. As a consequence, the structural parameters of concentration polarization were readily obtained with accuracy.     

An efficient synthesis of [1,1]ferrocenophane via 1,1′-bis(6-fulvenyl)ferrocene

[1,1]Ferrocenophane can be prepared by reduction of 1,1′-bis(6-fulvenyl)ferrocene with complex borohydrides to give the dianion of 1,1′-bis(cyclopentadienylmethyl)ferrocene. Reaction of this dianion with ferrous chloride produces the ferrocenophane in good yield.     

The mass spectra of 2-alkyl N-methyl pyrrolidines

The mass spectra of a series of 2-alkyl N-methyl pyrrolidines have been examined and fragments which may be pyrrole type structures are apparent. These ions are most prominent in the spectra of the long chain alkyl derivatives.     

Flow-injection determination of nonylphenol in liquid media using a piezoelectric immunosensor

A piezoelectric flow immunosensor for the rapid determination of nonylphenol in aqueous solutions was developed. An aminophenol-protein conjugate (4-AP-GA-BSA) immobilized on the presilanized surface of a silver electrode was used as a bioreceptor coating of the sensor. The effects of the nature and concentration of monoclonal and polyclonal antibodies on the analytical signal of the sensors were studied; the activity of immunoreagents was evaluated based on the binding constants K _b. The cross reactions of various phenols with antibodies were studied and the cross reaction percentages were found. A procedure for the flow-injection determination of nonylphenol in liquid media was developed using a piezoelectric immunosensor as a detector. The calibration graph was linear over the concentration range 1–20 ng/mL; the detection limit for nonylphenol was 0.8 ng/mL.     

Dynamics of photodissociation of 3,3,3-d(3)-propene at 157 nm: site effect and hydrogen migration

In a preceding paper [Lee et al., J. Chem. Phys. 119, 827 (2003)], we measured the kinetic-energy distributions P(E(t)) and branching ratios of products from photolysis of propene at 157 nm using time-of-flight spectroscopy combined with photoionization. In the present work, hydrogen migration before fragmentation and a site effect on P(E(t)) and branching ratios were revealed from the photodissociation of CD(3)CHCH(2). Labeling of the methyl group with deuterium enabled us to differentiate between elimination of atomic and molecular hydrogen from the vinyl moiety and from the methyl moiety; the P(E(t)) and relative yields for the formation of H, D, H(2), HD, and D(2) were measured. Deuterium labeling allowed us to also differentiate the fragmentation after hydrogen transfer from that before hydrogen migration. The observation of isotopic variants of CD(3) and C(2)H(3) radicals in the C-C bond cleavage provides evidence for hydrogen transfer of propene because of site specificity. The fraction of fragmentation after hydrogen transfer is estimated to be 25%. The isotope-specific branching ratios for five dissociation pathways of CD(3)CHCH(2) were evaluated.     

A chemoenzymatic approach to glycopeptide antibiotics

Many biologically active natural products are constrained by macrocyclization and modified with carbohydrates. These two types of modifications are essential for their biological activities. Here we report a chemoenzymatic approach to make carbohydrate-modified cyclic peptide antibiotics. Using a thioesterase domain from the decapeptide tyrocidine synthetase, 13 head-to-tail cyclized tyrocidine derivatives were obtained with one to three propargylglycines incorporated at positions 3-8. These cyclic peptides were then conjugated to 21 azido sugars via copper(I)-catalyzed cycloaddition. Antibacterial and hemolytic assays showed that the two best glycopeptides, Tyc4PG-14 and Tyc4PG-15, have a 6-fold better therapeutic index than the natural tyrocidine. We believe this method will also be useful for modifying other natural products to search for new therapeutics.     

Direct analysis of selected N-acyl-L-homoserine lactones by gas chromatography/mass spectrometry

A rapid, simple and selective method involving direct separation by gas chromatography (GC) with electron ionization mass spectrometry (EI-MS) was employed to determine some N-acylhomoserine lactones (AHLs). Using GC/EI-MS, simultaneous separation and characterization of AHLs were possible without prior derivatization. Informative fragmentation patterns were obtained to identify the structures of N-acyl chains of AHLs. Electron ionization resulted in a common fragmentation pattern with the most abundant ion at m/z 143 and other minor peaks at m/z 71, 57, and 43. The presence of AHLs in extracts of Burkholderia cepacia strains was achieved in selected ion monitoring mode by using the prominent fragment at m/z 143.