Model-independent constraints on spin observables

We discuss model-independent constraints on spin observables in exclusive and inclusive reactions, with special attention to the case of photoproduction.     

Electrical and chemical characteristics of nano-meter gold encapsulated in mesoporous and microporous channels and cages of FSM-16 and Y zeolites

The dc and ac conductivities as well as the dielectric constant () were measured for different zeolites encapsulated gold (AuCl₃) samples at different temperatures (300-500 K) and various frequencies (5 kHz-1 MHz). The conductivity was found to change in the order Au/FSM-27>Au/NaY>Au/FSM-47. Sorbed water contained inside zeolites assists greatly the proton mobility (zeolite protons) and the ion mobility (Na⁺ and Au⁺) and hence enhance the electric conduction in the temperature range 300-373 K. Raising the temperature over 373 K induces dehydration effect that assists the metallic gold formation and thus a dramatic loss in conductivity was revealed. The conduction mechanism was expected to be partially ionic and partially electronic. The IR study showed that the exposure of Au zeolites to CO gas produced a characteristic band of Au⁺-CO at 2180 cm⁻¹ that tends to decrease with temperatures and even vanishes at 376 K in favor of Au⁰-CO at 2128 cm⁻¹. Similarly, a phase transition at 338 K, that occurs in the range 300-376 K, was confirmed by DTA to further emphasize the temperature regions of either Au⁺ cations (338 K) or Au⁰ (376 K) formation.     

Unexpected acidity enhancement triggered by AlH3 association to phosphines

The complexes formed by the interaction between a series of phosphines R-PH(2) (R = H, CH(3), c-C(3)H(5), C(6)H(5)) and AlH(3) have been investigated through the use of high-level G4 ab initio calculations. These very stable complexes behave as much stronger acids than the isolated phosphines. This dramatic acidity enhancement, which can be as high as 174 kJ mol(-1), results from a much greater stabilization of the anionic deprotonated species with respect to the neutral one, upon AlH(3) association. This effect depends quantitatively on the nature of the substituent R and is smaller for R = C(6)H(5) because of the conjugation of the P lone pair with the aromatic system. More unexpectedly, however, the phosphine-alane complexes, RPH(2):AlH(3), are more acidic than the corresponding phosphine-borane RPH(2):BH(3) analogues. This unexpected result is due to the enhanced stability of the anionic deprotonated species for complexes involving AlH(3), because the delocalization of the newly created P lone pair with the P-Al bonding density is more favorable when the Lewis acid is aluminum trihydride than when it is borane.     

On the convergence of a class of algorithms using linearly independent search directions

Powell has shown that the cyclic coordinate method with exact searches may not converge to a stationary point. In this note we consider a more general class of algorithms for unconstrained minimization, and establish their convergence under the assumption that the objective function has a unique minimum along any line.     

Facile synthesis and antimicrobial evaluations of some novel pyrazolo[3,4-b]selenolo[3,2-e]pyrazines and their related heterocycles

A new series of pyrazolopyrazinoselenolotriazolopyrimidines was synthesized by a facile method based on condensation of 5-amino-3-methyl-1-phenyl-1H-pyrazolo[3,4-b]selenolo[3,2-e]pyrazine-6-carbonitrile ( 3 ) with triethyl orthoformate followed by intramolecular cyclization with hydrazine to afford 7-amino-8-imino-3-methyl-1-phenyl-1,8-dihydro-7H-pyrazolo[3″,4″:5′,6′]pyrazino[2′,3′:4,5] selenolo[3,2-d]pyrimidine ( 5 ). The latter compound was utilized as a multipurpose precursor for the construction of other new triazoles fused to the pyrazolopyrazino- selenolopyrimidine moiety. Alternatively, acetylation and chloro-acetylation of compound 3 using acetic anhydride and chloroacetyl chloride yielded the acetyl amino 11 and chloroacetamido 12 derivatives, respectively. Compound 12 underwent nucleophilic substitution upon reaction with morpholine to provide the morpholinyl acetamide 13 . Furthermore, the pyrazolopyridoselenolopyrazine ring system 14 was synthesized by the reaction of the o-amino-carbonitrile 3 with malononitrile. Assignment of the chemical structures for the new compounds was confirmed depending on elemental and spectral techniques. On the other hand, most of the synthesized compounds revealed promising results against various bacterial and fungal strains.     

Synthesis of novel dispiro-oxindoles via 1,3-dipolar cycloaddition reactions of azomethine ylides

The 1,3-dipolar cycloaddition of 1-allyl-5-haloisatin derivatives as dipolarophiles with the azomethine ylides generated in situ from N-allylisatin and l-proline to furnish novel dispiro-oxindoles has been investigated. The structures and relative stereochemistry of both types of cycloadducts were confirmed by single crystal X-ray diffraction, ¹H and ¹³C NMR spectroscopy and mass spectrometry.     

Clonal structure and variation in virulence of Salmonella enteritidis isolated from mice, chickens, and humans

The clonal analysis of a diverse collection of Salmonella Enteritidis indicates that most strains belong to a single multilocus genotype (i.e., ET-3) regardless of phage type, geographic origin, or time of isolation that spanned over 2 decades (1978 to 2004). Attachment and invasion assays, however, indicate that, among ET-3 isolates, there is a distinct invasive bacterial subpopulation that is more readily recovered from eggs and clinical cases in humans than from chicken cecal samples. These observations support the hypothesis that the specialized ability of S. Enteritidis to infect the avian reproductive tract and contaminate eggs has been critical in its emergence as a frequent cause of human illness.     

Effect of mordenite dealumination on the structure of encapsulated molybdenum catalysts

A series of dealuminated mordenites treated under various conditions of acid leaching was impregnated in an aqueous solution of ammonium heptamolybdate to achieve a loading of 12 wt% Mo. These samples were characterized by XRD, UV-DRS, N(2) adsorption, TGA, and FTIR techniques. Special attention was given to the far-IR measurements and IR study of surface hydroxyl groups before and after dealumination. A polymolybdate species was recognized by the appearance of bands at 344, 319, and 236 (229) cm(-1) due to the vibrational modes of delta(Mo-O) and delta(Mo-O-Mo), respectively. The disappearance of the 236 cm(-1) band as well as that at 344 cm(-1) in favor of the 319 cm(-1) band, with the dealumination, was related to the high dispersion of Mo species in the produced mesopore surface assessed by the N(2) adsorption at 77 K. No bands due to bulk MoO(3) were detected from the IR and XRD results. A strong interaction between Mo species and dealuminated mordenite surfaces (OH groups) was recognized by a decrease in intensity and a marked shift of the band at 3745 to 3727 cm(-1) as well as the appearance of a new band at 3668 cm(-1). The latter band was produced by the interaction of the framework Al-OH with Mo species. The BET surface areas of Mo-dealuminated mordenite samples were higher than the corresponding Mo-free ones. The diffuse reflectance measurements suggested that Mo cations are predominantly present as an octahedrally coordinated Mo(6+), along with some tetrahedral Mo(6+). New spectral features as a consequence of dealumination events in the far-IR range were evaluated and discussed.