SDP diagonalizations and perspective cuts for a class of nonseparable MIQP

We present a new approach, requiring the solution of a SemiDefinite Program, for decomposing the Hessian of a nonseparable mixed-integer quadratic problem to permit using perspective cuts to improve its continuous relaxation bound. The new method favorably compares with a previously proposed one requiring a minimum eigenvalue computation.     

Promotion by phosphorus compounds of ruthenium-catalyzed methyl formate homologation

Trivalent phosphorus compounds are promoters for methyl formate homologation to ethanol and ethyl formate catalyzed by ruthenium compounds in the presence of iodide at 220°C and 27 MPa of synthesis gas. Under these conditions the phosphines are quaternized, but decomposition of phosphonium salts occurs during the reaction. Promotion is also observed for methyltriphenyl-phosphonium bromide and triphenylphosphine sulfide, but benzyltrimethyl-ammonium bromide, triphenylarsine, and triphenylantimony are not effective. The major ruthenium species present is Ru(CO)₃I₃^- but with triphenylantimony a trimethylantimony complex, Ru(CO)₂(Sb(CH₃)₃)₂I₂, can be isolated in high yield.     

Nouveaux exemples d'acétonides d'aldéhydosucres furanniques

Further examples of O-isopropylidenaldehydosugars in the furanose series Formyl-bearing furanose derivatives 1–3 (α-D -xylo or α-D -erythro configurations) and 5–8 (configurations α-D -ribo, α-D -lyxo, β-L -threo and D -arabino) have been prepared by classical synthetic steps and their properties mainly spectroscopic, reported. The coupling constant between the formyl and the vicinal proton is always small. Like other members of the series, these new aldehydosugars constitute very useful and flexible synthetic intermediates.     

The reactivity of the A-CH=N-NR-CX-B system. 1,3,4-Oxadiazoles and 2,3,4,5-tetrahydro-1,2,4-triazin-3-ones through the 1–5 and 1–6 cyclization reactions of α-thienylglyoxal monosemicarbazones

The factors influencing the reactivity of α-thienylglyoxal monosemicarbazones when treated with cyclizing reagents (bromine/sodium acetate and hydrobromic acid in acetic acid) were investigated. Depending on the experimental conditions, on the position of the substituent on the semicarbazide residue, and on the cyclizing agent, the substrates 1a-e give the semicarbazone bromides 2a-b, 5 , the 1,3,4-oxadiazoles 3a-c , the 1,2,4-triazine 11 and the 2,3,4,5-tetrahydro-1,2,4-triazine-3-ones 6, 8 and 9 . Compound 6 by thermolysis undergoes ring contraction in the Δ²-1,3,4-oxadiazoline 12 , while treatment with base involves the conversion of 6 into 1,2,4-triazol-5-one 13 . Ir, nmr and mass spectra support the reported structures.     

Substitutional carbon defects in silicon: A quantum mechanical characterization through the infrared and Raman spectra

The infrared (IR) and Raman spectra of eight substitutional carbon defects in silicon are computed at the quantum mechanical level by using a periodic supercell approach based on hybrid functionals, an all electron Gaussian type basis set and the CRYSTAL code. The single substitutional C _s case and its combination with a vacancy (C _sV and C _sSiV) are considered first. The progressive saturation of the four bonds of a Si atom with C is then examined. The last set of defects consists of a chain of adjacent carbon atoms C, with i = 1–3. The simple substitutional case, C _s, is the common first member of the three sets. All these defects show important, very characteristic features in their IR spectrum. One or two C related peaks dominate the spectra: at 596 cm⁻¹ for C _s (and C _sSiV, the second neighbor vacancy is not shifting the C _s peak), at 705 and 716 cm⁻¹ for C _sV, at 537 cm⁻¹ for C and C (with additional peaks at 522, 655 and 689 for the latter only), at 607 and 624 cm⁻¹, 601 and 643 cm⁻¹, and 629 cm⁻¹ for SiC, SiC, and SiC, respectively. Comparison with experiment allows to attribute many observed peaks to one of the C substitutional defects. Observed peaks above 720 cm⁻¹ must be attributed to interstitial C or more complicated defects.     

Reactivity of 2-amino-1,3,4-thiadiazoles. Nucleophilic behaviour of some 2-amino-1,3,4-thiadiazoles: Model compounds

The ambident nucleophilic behaviour of some 2-amino-5-H-1,3,4-thiadiazoles in alkylation, acylation and nitrosation reaction has been verified. The structures assigned to the 2-amino-1,3,4-thiadiazoles ( 1a-i ) and to the Δ²-1,3,4-thiadiazolines ( 2a-e ) agree with the spectral data.     

α-Hydroxyalkylation of heteroaromatic bases by alcohols and hydroxylamine-O-sulphonic acid

The homolytic decomposition of hydroxylamine-O-sulphonic acid in alcoholic solvents was investigated in the presence or absence of protonated heteroaromatic bases and Fe(II) salt. The addition of the α-hydroxyalkyl radicals to the base and their oxidation by Fe(III) salt to the corresponding alkyl cyanide were competitive processes. A redox chain process involving the amino radical cation, NH₃^t., is suggested and the factors affecting the yields of the homolytic substitution are discussed.     

An Investigation of Complexation of Cadmium(II) with Arginine

Among amino acids, arginine is important in human physiology because it plays an important role in cardiovascular and depression problems. In this paper the behavior of arginine as a ligand toward cadmium(II) [Cd(II)] in two different ionic media: 1.00 mol·dm^?3 NaCl and NaClO₄, is studied. Knowledge of the species formed between Cd(II) and arginine in a wide concentration range is useful also in biology. This system was investigated using two different methods in two ranges of hydrogen ion concentration. In acidic solutions, electromotive force measurements are performed using glass and Cd amalgam electrodes. In basic solutions, polarography was used and the shift of the half wave potential was measured as a function of the ligand concentration. The experimental data obtained in NaCl solutions are explained by assuming the formation of the species [CdL], [CdHL], [CdL₂], [CdHL₂] and [CdH₂L₂]. The data obtained in NaClO₄ solutions are explained by assuming the formation of the species [CdL], [CdHL], and [CdH₂L₂]. In both cases the stability constants are reported.