Application of parahydrogen for mechanistic investigations of heterogeneous catalytic processes

Parahydrogen-induced polarization technique (PHIP), based on the pairwise addition of molecular hydrogen to a substrate, was successfully applied to obtain novel information on the mechanisms of heterogeneous catalytic hydrogenation, hydrodesulfurization, and oligomerization processes. In particular, the PHIP effects were observed upon hydrogenation with parahydrogen catalyzed by the immobilized neutral complexes of rhodium and iridium, which confirms the similarity in the mechanisms of homogeneous and heterogeneous hydrogenation for such systems. In the study of acetylene oligomerization, a significant NMR signal enhancement was revealed for a number of C₄ oligomers, with the enhancement levels by far exceeding that observed in hydrogenation of carbon-carbon triple bonds. The mechanistic features of heterogeneous hydrogenation of a number of six-membered cyclic hydrocarbons over supported metal catalysts were investigated, and their hydrogenation scheme based on the pairwise addition of molecular hydrogen was proposed. Furthermore, the PHIP technique revealed that heterogeneous hydrodesulfurization of thiophene mainly proceeds via hydrogenation followed by a C—S bond cleavage. A significant enhancement of sensitivity in combination with characteristic line shapes of NMR signals make the PHIP method a unique and highly informative tool for the investigation of heterogeneous catalytic processes.     

Effect of the nature of sulfur compounds on their reactivity in the oxidative desulfurization of hydrocarbon fuels with oxygen over a modified CuZnAlO catalyst

The reactivity of thiophene, dibenzothiophene (DBT), and 4,6-dimethyldibenzothiophene (4,6-DMDBT), which are the representatives of the main classes of sulfur compounds that are the constituents of diesel fractions, was studied in the course of their oxidative desulfurization with oxygen on a CuO/ZnO/Al₂O₃ catalyst modified with boron and molybdenum additives. At T ≥ 375°C, the reactivity increased in the order thiophene < DBT < 4,6-DMDBT. The degree of sulfur removal in the form of SO₂ from hydrocarbon fuel, which was simulated by a solution of 4,6-DMDBT in toluene, was 80%. Under the assumption of a first order reaction with respect to sulfur compound and oxygen, the apparent activation energies of the test processes were calculated. An attempt was made to reveal the role of the adsorption of sulfur compounds in the overall process of oxidative desulfurization with the use of X-ray diffraction analysis, X-ray photoelectron spectroscopy, and differential thermal and thermogravimetric analysis with the massspectrometric monitoring of gas phase composition.     

Experimental study of the decay φ→ηγ in multiphoton final state

The φ(1020)→ηγ→3π ⁰ γ decay is studied in the SND experiment at the VEPP-2M e ⁺ e ⁻ collider. The measurements give a branching ratio Bφ→ ηγ)=(1.246±0.025±0.057)%. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 7, 549–551 (10 October 1998) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Configurational Stability of 1,1′-Bi-2-naphthol in Superacid System HSO3F–SbF5–SO2ClF

Russian Journal of Organic Chemistry - Although 1,1′-bi-2-naphthol (BINOL) is known to racemize in aqueous mineral acids and much more readily in superacids, it retains its initial...     

Analysis of e + e −→π+π−π+π− and e + e −→π+π−π0π0 processes in the energy range of \sqrt 2 = 0.98 - 1.38 GeV in experiments with a spherical neutral detector

The cross sections of the e ⁺ e ^?→π⁺π^?π ⁺π^?, e ⁺ e ^?→π⁺π^?π⁰π ⁰, and e ⁺ e ^?→ωπ→ π⁺π^?π ⁰π⁰ processes, as well as the e ⁺ e ^?→π⁺π^?π⁰π⁰ process with subtracted contribution of the ωπ intermediate state, are measured in experiments with a spherical neutral detector on the VEPP-2M collider in the energy range 0.98–1.38 GeV. About 41 000 events of the e ⁺ e ^?→π⁺π^?π⁺π ^? process and more than 54 000 events of the e ⁺ e ^?→π⁺π ^?π⁰π⁰ process have been selected in experiment. The statistical error in determining the cross section is 2–20%, while the systematic error is 7 and 8%.     

Synthesis of Derivatives of the Optically Active β‐Amino Acids from (+)‐Car‐2‐ene

The reaction of (+)‐car‐2‐ene ( 4 ) with chlorosulfonyl isocyanate (=sulfuryl chloride isocyanate; ClSO₂NCO) led to the tricyclic lactams 6 and 8 corresponding to the initial formation both of the tertiary carbenium and α‐cyclopropylcarbenium ions (Scheme 2). A number of optically active derivatives of β‐amino acids which are promising compounds for further use in asymmetric synthesis were synthesized from the lactams (see 16, 17 , and 19 – 21 in Scheme 3).     

Structure and properties of aqueous dispersions of sodium dodecyl sulfate with carbon nanotubes

The dispersing action of the surfactant (sodium dodecyl sulfate, SDS) on the carbon nanotubes (CNT) in aqueous medium has been studied. Electron microscopy, molecular docking, NMR and IR spectroscopies were applied to determine the physical-chemical properties of CNT dispersions in SDS—water solutions. It was established that micellar adsorption of the surfactant on the surface of carbon material and solubilization of SDS in aqueous medium contribute to improving CNT dispersing in water solutions. It was shown that the non-polar hydrocarbon radicals of a single surfactant molecule form the highest possible number of contacts with the graphene surface. Upon increase of the SDS in solution these radicals form micelles connected with the surface of the nanotubes. At the sufficiently high SDS concentration the nanotube surface becomes covered with an adsorbed layer of surfactant micelles. Water molecules and sodium cations are concentrated in spaces between micelles. The observed pattern of micellar adsorption is somewhat similar to a loose bilayer of surfactant molecules.     

Localization of Frenkel Excitons at Dislocations

It is shown that if dislocations are present in a crystal, Frenkel excitons are localized at them. The dispersion equation for localized excitons is derived and examined. The localized wave amplitude is determined as a function of the distance from the dislocation. The frequency gap separating localized oscillations from bulk ones is found. __________ Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 23–25, July, 2005.     

Solvation state of iron(III) in aqueous solutions of dimethyl sulfoxide. Complex formation ability of iron(III) with respect to derivatives of <Emphasis Type="Italic">sym</Emphasis>-triazine and bis(hydrazinocarbonylmethyl) sulfoxide

Parameters of the solvation equilibria \({\left[ {Fe{{\left( {{H_2}O} \right)}_6}} \right]^{3 + }} + nDMSO \rightleftarrows {\left[ {Fe{{\left( {{H_2}O} \right)}_{6 - n}}{{\left( {DMSO} \right)}_n}} \right]^{3 + }} + n{H_2}O\) have been determined in aqueous-dimethyl sulfoxide solutions (0–90 vol% DMSO) by means of spectrophotometry and mathematical modeling of equilibria. Iron(III) is not involved in the complex formation with derivatives of sym-triazine: 2,4-diamino-6-(carbamoylmethylsulfinylmethyl)-1,3,5-triazine and 2,4-diamino-6-(acetohydrazidomethylsulfinylmethyl)-1,3,5-triazine in aqueous DMSO medium (40 vol % DMSO). Bis(hydrazinocarbonylmethyl) sulfoxide forms two complexes with iron(III), with 1: 1 and 1: 2 compositions; in contrast to the Cu(II) and Ni(II) complexes, in the iron complexes the ligand exists in the amide form. The most probable structures of the complexes have been revealed by molecular mechanics simulation and (in selected cases) using the DFT/B3LYP/6-31++G(d,p) density functional theory method.