NMR studies of solid state—solvent and H/D isotope effects on hydrogen bond geometries of 1:1 complexes of collidine with carboxylic acids

¹H and ¹⁵N NMR spectra of 10 complexes exhibiting strong OHN hydrogen bonds formed by ¹⁵N-labeled collidine and different proton donors, partially deuterated in mobile proton sites, have been observed by low-temperature NMR spectroscopy using a low-freezing CDF₃/CDF₂Cl mixture as polar aprotic solvent. The following proton donors have been used: HCl, formic acid, acetic acid, various substituted benzoic acids and HBF₄. The slow hydrogen bond exchange regime could be reached below 140 K, which allowed us to resolve ¹⁵N signal splittings due to H/D isotopic substitution. The valence bond order model is used to link the observed NMR parameters to hydrogen bond geometries. The results are compared to those obtained previously [Magn. Reson. Chem. 39 (2001) S18] for the same complexes in the organic solids. The increase of the dielectric constant from the organic solids to the solution (30 at 130 K) leads to a change of the hydrogen bond geometries along the geometric correlation line towards the zwitterionic structures, where the proton is partially transferred from oxygen to nitrogen. Whereas the changes of spectroscopic and, hence, geometric parameters are small for the systems which are already zwitterionic in the solid state, large changes are observed for molecular complexes which exhibit almost a full proton transfer from oxygen to nitrogen in the polar liquid solvent.     

Simple route to 3-(2-indolyl)-1-propanones via a furan recyclization reaction

A simple route to 1-R-3-(2-indolyl)-1-propanones has been elaborated based on recyclization of 2-(2-aminobenzyl)furan derivatives. Being a modification of the Reissert indole synthesis, our approach employs the furan ring as a source of carbonyl function. This approach is general and allows varying of substituents in aromatic ring as well as in 3-position of indole nucleus.     

Nitro derivatives of 3-hydroxyquinoline

The nitration of 3-hydroxyquinoline with concentrated nitric acid in sulfuric acid at ?30 to +30°C gives 5-nitro-3-hydroxyquinoline (85–92%) and 7-nitro-3-hydroxyquinoline (7–12%). 4-Nitro-3-hydroxyquinoline is formed in 70% yield by nitration in acetic acid. 4,5-Dinitro-3-hydroxyquinoline is formed by further nitration of 4- and 5-nitro-3-hydroxyquinolines.     

Alkylation of salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides with alkyl halides and dimethyl sulfate

Salts ofN-(β-hydroxyalkyl)-N′-hydroxydiazeneN-oxides, RCH(OH)CH₂N(O)=NO⁻ M⁺ (R=Me, Prⁱ, or Bu^t; and M=Li, Na, K, Ag, NH₄, or Me₄N), were prepared. Their alkylation with alkyl halides R′X (X=Cl, Br, or I) and dimethyl sulfate was studied. Generally, alkylation afforded mixtures ofN-(β-hydroxyalkyl)-N′-alkoxydiazeneN-oxides RCH(OH)CH₂N(O)=NOR′ andO-alkyl-N-(β-hydroxyalkyl)-N-nitrosohydroxylamines RCH(OH)CH₂N(NO)OR′. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1996–2001, October, 1998.     

Measurements of the spin rotation parameterR in high energy elastic scattering and helicity amplitudes at Serpukhov energies

The spin rotation parameterR in pp and ⁺ p elastic scattering at 45 GeV/c has been measured at the Serpukhov accelerator, for ¦t¦ ranging from 0·2 to 0·5 (GeV/c)². The results are presented, together with previousR measurements at lower energies, and are compared with the predictions of Regge pole models. The equality of the values forR in proton-proton and pion-proton scattering, within the experimental errors, is a test of factorization of the residues.Ans-channel helicity amplitude analysis for pion-nucleon scattering at 40 GeV/c is made using all available data, Significant results are obtained for the isoscalar exchange amplitudes. The helicity flip in isoscalar exchange is non negligible. The energy dependence of this amplitude, at 6, 16 and 40 GeV/c, is compared with predictions of Reggs pole models.Presented by L.van Rossum at the Symposium on Hadron-Hadron Scattering at High Energies, Liblice, Czechoslovakia, June 16–21, 1975.     

Manifestation of a semimetallic state in cyclotron resonance in low-symmetry HgTe-based quantum wells

Cyclotron-resonance measurements in 21-nm-thick HgTe/CdHgTe quantum wells of different crystallographic orientations have been performed. It has been found that, in contrast to the structures with the (001) orientation of the quantum-well plane, (013)-oriented quantum wells are semimetallic and their absorption spectra exhibit both electron and hole cyclotron-resonance lines. The simultaneous presence of the two types of charge carriers originates from an overlap between the upper heavy-hole quantum-confinement subbands hh1 and hh2. This overlap is caused by the strong interaction of these subbands with the Dyakonov-Khaetskii interface state. Calculations carried out using the eight-band kp-Hamiltonian indicate that, for known values of the band-structure parameters, the overlap between hh2 and hh1 subbands does not occur; this result is in agreement with the cyclotron-resonance data for (001)-oriented structures. The enhanced interaction between heavy-hole and interface states owing to the existence of steps at low-symmetry heterointerfaces may be the mechanism responsible for the appearance of an overlap between subbands in HgTe quantum wells with orientation different from (001).     

Effect of humidity on the conductivity of graphite oxide during its photoreduction

The influence of humidity on the conductivity of graphite oxide (GO) films has been considered. Graphite oxide films of a 200–500 nm thickness become conductors to have a conductivity of 10^?6 to 10^?2 S/cm when humidity increases from 30 to 100%. Film morphology varies during the course of water diffusion. Ultraviolet light-mediated reduction of GO decreases the sensitivity to humidity until its complete disappearance.     

Radiation enhanced P-diffusion in germanium

Abstract

Cascade size may affect phase stability under irradiation because of two distinct contributions: the replacement to displacement cross-section ratio depends on the deposited energy density; ballistic jumps which tend to disorder ordered compounds occur by bursts, while thermal jumps which restore long range order occur one by one.

The latter effect cannot be handled by standard rate theory. A stochastic treatment of the problem, based on a Fokker Planck approximation of the relevant master equation is summarized. It is shown that the possible values of the long range order parameter under irradiation are not affected by the size of the cascade but that the respective stability of the former is cascade size sensitive. As a consequence, the stability diagram of phases under irradiation varies with the size of the cascades. A numerical example of this is given for the B2 structure.