A comparative analysis of various gradient methods for geometry optimization at the ab initio SCF-MO level

Various techniques, already suggested for improving the computational efficiency of the force relaxation method, have been applied here in conjunction with the variable metric algorithms suggested by Murtagh and Sargent and by Fletcher. Various tests have been performed to assess the computational efficiency of the resulting minimization procedures. In addition, procedures where the steps are defined in terms of a parabolic fitting of the forces in approximated normal coordinates have been tested. In all cases the forces are computed analytically.     

Matrix-isolation FT-IR spectra and theoretical study of dimethyl sulfate

The preferred conformations of dimethyl sulfate and their vibrational spectra were studied by matrix-isolation FT-IR spectroscopy and theoretical methods (DFT and MP2, with basis sets of different sizes, including the quadruple-zeta, aug-cc-pVQZ basis). Conformer GG (of C2 symmetry and exhibiting OSOC dihedral angles of 74.3 degrees ) was found to be the most stable conformer in both the gaseous phase and isolated in argon. Upon annealing of the matrix, the less stable observed conformer (GT; with C1 symmetry) quickly converts to the GG conformer, with the resulting species being embedded in a matrix-cage which corresponds to the most stable matrix-site for GG form. The highest energy TT conformer, which was assumed to be the most stable conformer in previous studies, is predicted by the calculations to have a relative energy of ca. 10 kJ mol-1 and was not observed in the spectra of the matrix-isolated compound.     

Simplified chemical and radiochemical synthesis of 2-arachidonoyl-glycerol, an endogenous ligand of cannabinoid receptors

Endocannabinoids have emerged as a new class of lipid mediators, with manifold roles in the central nervous system and in the periphery. Several studies have identified 2-arachidonoyl-glycerol (2-AG) as a major endogenous agonist of cannabinoid receptors. Here, the chemical synthesis of 2-AG is reported, along with the synthesis of its tritium-labeled derivative. These unlabeled and radiolabeled compounds are suitable tools for unravelling some metabolic routes and biological activities of 2-AG in various cells and tissues.     

Baeyer-Villiger oxidation with potassium peroxomonosulfate supported on acidic silica gel

[reaction: see text] Potassium peroxomonosulfate deposited onto silica SiO2 x KHSO5 efficiently reacts with ketones in dichloromethane at room temperature to give the corresponding esters or lactones in quantitative yields. This method avoids hydrolysis of the reaction products. The Baeyer-Villiger reaction is catalyzed by potassium hydrogensulfate present in the supported reagent.     

Conformational studies by dynamic NMR. 94.1 cogwheel pathway for the stereomutations of durene derivatives containing the mesityl ring

The low-temperature NMR spectra of 1,4-bis(mesitoyl)durene, 1, and of 1,4-bis(mesitylethenyl)durene, 2, reveal the presence of syn and anti rotamers at the equilibrium, their relative proportions depending on the dielectric constant of the solvent. In solution the more stable rotamer of 1 is the anti whereas, in the case of 2, the more stable is the syn. Depending on the crystallization solvent employed the more (anti) and the less stable (syn) rotamers were both observed (X-ray diffraction) in the solid state of 1. On the other hand, only the less stable rotamer (anti) was found to be present in the solid state of 2. As shown by MM calculations, the syn-to-anti interconversion occurs via a correlated process (cogwheel pathway) involving the mesityl-C and durene-C bond rotations: the dynamic NMR technique yields an experimental barrier of 8.2 kcal mol(-)(1) for 1 and 13.1 kcal mol(-)(1) for 2. In the case of derivative 2 a second barrier, due to a second type of correlated rotation process (torsion), was also determined (8.6 kcal mol(-)(1)). As a consequence of the restriction of this second torsional motion the anti rotamer of 2 displays two distinguishable NMR spectra at -133 degrees C, corresponding to a pair of conformers with different symmetry (anti C(i)() and anti C(2)).     

Multielemental analysis of food and agricultural matrixes by inductively coupled plasma-mass spectrometry

The suitability of quadrupole inductively coupled plasma-mass spectrometry (ICP-MS) for multielemental analysis of food following microwave closed vessel digestion of samples was evaluated in relation to analytical challenges presented by some major food and agricultural matrixes. Fifteen key analytes (Al, As, Cd, Co, Cr, Cu, Fe, Mn, Mo, Ni, Pb, Se, Sn, V, Zn) were determined in 9 reference materials representative of 3 major groups of staple foods (cereals, seafood, and meat). For all measurements, the method of external calibration was used and Rh was selected as internal standard. Matrix-induced interferences were evaluated for each material, and suitable methods to overcome them were applied. Spectral interferences caused by C, Cl, and Ca content of digestates were quantitated and corrected by entering a simple system of mathematical correction equations into the instrument software before each analytical run. Full mastering of interferences together with adoption of a series of measures to control the reliability of analytical measurements produced accurate results for all the analytes. A standard analytical protocol is outlined for the benefit of both research and routine high-throughput laboratories that perform ICP-MS analyses of food.     

Synthesis of 1,2-cis-Configurated Glycosylphosphonates

A synthesis of 1,2-cis-configurated, non-isosteric phosphonate analogues of aldose-1-phosphates is described. Treatment of 1-O-acyl-glycoses 1 , 7 , 13 , and 19 with trialkyl phosphite in the presence of trimethylsilyl trifluoromethanesulfonate gave the 1,2-cis-configurated glycosylphosphonates 2 , 4 , 8 , 10 , 14 , 16 , 20 , and 22 as the major anomers and the 1,2-trans-configurated glycosylphosphonates 3 , 5 , 9 , 11 , 15 , 17 , 21 , and 23 as the minor anomers. The 1,2-cis-configurated phosphonates 4 , 10 , 16 , and 22 were deprotected to give the (β-D -glucopyranosyl)phosphonate 6 , the (β-D -mannopyranosyl)phosphonate 12 , the (β-D -ribofuranosyl)phosphonate 18 , and the (β-D -arabinofuranosyl)phosphonate 24 , respectively, in high yields. The preferred formation of 1,2-cis-configurated phosphonates is explained by postulating an equilibrium between the anomeric phosphonium-salt intermediates (such as 25 and 26 ) and a stabilization of the cis-configurated salts through formation of a pentacoordinated species (such as 28 ).     

A convenient protocol for selective cleavage of 2-hydroxy acid amides. Application to semisynthesis of the cyclic heptapeptide aza HUN-7293

A two-step protocol for the first chemoselective cleavage of 2-hydroxy acid amides has been developed. Mesylation of the model substrate 2-(hydroxypropionylamino)-4-methylpentanoic acid methyl ester (11) followed by treatment with N-ethylthiourea (13) allows cleavage of 2-hydroxy acid amides under smooth conditions. Successful application of this methodology to the open-chain transesterification product 15 (methylester) of the cyclic heptadepsipeptide HUN-7293, a potent inhibitor of inducible cell adhesion molecule expression, delivered the corresponding hexapeptide 18 with unprotected N-terminus in 70-75% yield. This result demonstrates that the protocol developed even works in the presence of an ester and several methylated and unmethylated amide bonds. Finally, a sequence of ligation of methyl D-dehydroglutaminate (20) to the C-terminus of the saponification product 21, followed by the degradation protocol and ring closure, allowed chemical "point mutation" at the DGCN site affording the aza analogue of HUN-7293 (24) in 15% overall yield. To the best of our knowledge this is the first report on chemoselective cleavage of 2-hydroxy acid amides.     

Di- and trinuclear Zn2+ complexes of calix[4]arene based ligands as catalysts of acyl and phosphoryl transfer reactions

The calix[4]arene scaffold, blocked in the cone conformation by proper alkylation of the lower rim hydroxyls, was used as a convenient molecular platform for the design of bi- and trimetallic Zn2+ catalysts. The catalytic activity of the Zn2+ complexes of calix[4]arenes decorated at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with 2,6-bis[(dimethylamino)methyl]pyridine units were investigated in the cleavage of ester 6 and of the RNA model compound HPNP. High rate enhancements, up to 4 orders of magnitude, were observed in a number of catalyst-substrate combinations. Interestingly the order of catalytic efficiency among regioisomeric dinuclear complexes in the cleavage of ester 6 is 1,2-vicinal > 1,3-distal, but it is reversed in the reaction of HPNP. The higher efficiency of trinuclear compared to dinuclear complexes provides an indication of the cooperation of three Zn2+ ions in the catalytic mechanism.     

Nanoscale borromeates

[Structure: See text] In addition to a parent zinc(II) Borromean ring (BR) complex, the preparation and characterization of two hexasubstituted BR complexes with either 4-acetoxymethylphenyl or 4-methylthiophenyl substituents associated in turn with all six pyridyl rings has been achieved convergently in good yields by appealing to the dynamic features of the reactions between primary amino groups in a preformed acyclic ligand and 2,6-diformylpyridine. Two molecules of the acyclic ligands react with two molecules of 2,6-diformylpyridine to form a cyclic [2 + 2] tetraimine in the presence of Zn(II) ions as templates in 2-propanol at 70 degrees C. The successful preparation of the two derivatives by convergent template-directed syntheses opens up opportunities to self-assemble, under equilibrium control, numerous nanoscale metallo-organic particles with potentially useful properties.