Effects of mixed H2O‐CH3CN solvents on the rate of hydrazinolysis of N‐phenylphthalimide: Spectral and kinetic evidence for the occurrence of N‐aminophthalimide on the reaction path

Kinetic study on the cleavage of N‐phenylphthalimide (NPhPT) in the presence of 0.05 M NH₂NH₂ and mixed H₂O‐CH₃CN solvents reveals the occurrence of reaction scheme where A, B, C, C₁, An, E, and F represent NPhPT, o‐CO^?₂C₆H₄CONHC₆H₅, o‐CONHNH₂C₆H₄‐ CONHC₆H₅, N‐aminophthalimide, aniline, o‐CO^?₂C₆H₄CONHNH₂, and o‐CONHNH₂C₆H₄‐CONHNH₂, respectively. But, in the presence of either nonbuffered ?0.20 M NH₂NH₂ hydrazine buffer of pH ～7.30–8.26 with total buffer concentration ([Buf]_T) of >0.02 M, further conversion of F to 2,3‐dihydrophthalazine‐1,4‐dione (DHPD) has been detected depending upon the length of the reaction time (t), the values of [Buf]_T, and pH. It has been shown that the rate of conversion of C₁ to F is much faster than that of C to C₁ which is much faster than that of F to DHPD. The reaction step A → C involves general base (GB) catalysis, while step C → C₁ seems to involve specific base–general acid (GA) and GB‐GB catalysis. © 2005 Wiley Periodicals, Inc. Int J Chem Kinet 37: 147–161, 2005     

Sesquiterpenoids—27: X-ray crystallographic analysis of istanbulin-B,A 1-oxo-eremophilenolide

The stereochemistry of istanbulin-B has been defined by X-ray crystal-structure analysis. Rings A and B are transfused, with the Me groups at C(4) and C(5) cis. The α,β-unsaturated,γ -lactone ring is essentially planar. Crystals of istanbulin-B are orthorhombic, space group P2₁2₁,2₁, with a = 6.729(2), b = 13.447(3), c = 14.721(3)Â,and Z = 4. The crystal structure was determined by direct phasing and the atomic parameters were subsequently adjusted by least-squares calculations that converged at R 38% over 1179 diffractometer |F_a| values     

Ruthenium Cluster Chemistry with Ph2PC6H4-4-C≡CH

The new phosphines Ph₂PC₆H₄-4-CCR [R=SiMe₃ (1), H (2)] have been used to prepare Ru₃(CO)₉(Ph₂PC₆H₄-4-CCSiMe₃)₃ (4) and Ru(CCC₆H₄-4-PPh₂)(PPh₃)₂(-C₅H₅) (3), respectively, the latter with a pendent phosphine. Reaction of 4 with carbonate or fluoride affords Ru₃(CO)₉(Ph₂PC₆H₄-4-CCH)₃ (5) with pendent terminal alkynyl groups, the identity of which was confirmed by a structural study. Reaction of 5 with [Ru(NCMe)(PPh₃)₂(-C₅H₅)]PF₆ or reaction of Ru₃(CO)₁₂ with 3 gives Ru₃(CO)₉{(Ph₂PC₆H₄-4-CC)Ru(PPh₃)₂(-C₅H₅)}₃ (6). Complexes 3–6 have been studied by cyclic voltammetry. Proceeding from Ru₃(CO)₁₂ to 4 or 5 shifts the cluster-centred reduction to more negative potential and affords facile cluster-centred oxidation. Proceeding from 4/5 and 3 to 6 results in similarly-located cluster-centred reduction and peripheral ruthenium-centred oxidation, but results in a lack of observable cluster-centred oxidation. Crystal data for 5·C₆H₁₄: space group P¯1, a=12.760(1) Å, b=17.077(1) Å, c=17.924(2) Å, =108.656(5)°, =96.344(5)°, =93.523(5)°, V=3658.4(6) ų, Z=2, R=0.078, R_w=0.105 for 5008 reflections [I>2.00(I)].     

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.     

Deprotonation-electrophile trapping of terminal epoxides

Organolithium-induced deprotonation of terminal epoxides in the presence of appropriate diamine ligands allows trapping with a range of electrophiles, yielding functionalised di- and tri-substituted epoxides in good yields and with control of stereochemistry at the epoxide.     

The Role of Carnitine Acyltransferases in the Maintenance of Cell Function

Summary. Carnitine acyltransferases catalyse equilibria between acyl-CoA esters and the respective acylcarnitines. Therefore, they act not only as pathway enzymes, but also as modulators of acyl-CoA concentrations within individual sub-cellular compartments. Because acyl-CoA esters are potent biologically active metabolites, carnitine acyltransferase activities are potentially able to affect a diverse range of physiological processes, ranging from insulin secretion, to appetite control, and insulin sensitivity of tissues. The distinctive subcellular distributions of the different types of carnitine acyltransferases also enables them to participate in the transfer of acyl moieties across intracellular membranes, and of particular acylcarnitine esters across the plasma membrane and into the plasma. Pharmacological strategies that make use of these properties to improve cell function are discussed.     

Micellar liquid chromatography: suitable technique for screening analysis

The screening capability of micellar liquid chromatography (MLC) is discussed using the reported chromatographic data of several sets of compounds (amino acids, beta-blockers, diuretics, phenethylamines, phenols, polynuclear aromatic hydrocarbons, steroids and sulfonamides) and new results (sulfonamides and steroids). The chromatographic data are treated with an interpretive optimisation resolution procedure to obtain the best separation conditions. Usually, the pH and the concentration of surfactant (sodium dodecyl sulfate, SDS, or cetyltrimethylammonium bromide) for the optimal mobile phase were 2.5-3 and < 0.12 M, respectively. The nature and concentration of organic solvent depended on the polarity of the eluted compounds: a low volume fraction of propanol (approximately 1%, v/v) was useful to separate the amino acids, with log P(o/w) < -1 (where P(o/w) is the octanol-water partition coefficient). A greater concentration of this solvent (approximately 5-7%) was needed for compounds in the range -1 < log P(o/w) < 2, as with the studied diuretics and sulfonamides, and a high concentration of propanol (approximately 15%) or a low concentration of butanol (< 10%) had to be used for less polar compounds with 1 < log P(o/w) < 3, such as the beta-blockers. Pentanol (< 6%) was more suitable for the even less polar compounds with log P(o/w) > 3, such as the steroids. For basic drugs such as the phenethylamines (0 < log P(o/w) < 1.7), eluted with a micellar eluent of anionic SDS, propanol was too weak. A study is also shown for mixtures of sulfonamides (log P(o/w) = -1.2 to 1.7) and steroids (log P(o/w) = 3.0-8.1) eluted from conventional C18 columns with SDS mobile phases containing acetonitrile and 1-pentanol, respectively, which are compared with classical acetonitrile-water and methanol-water mixtures. The results complement a previous study on beta-blockers (log P(o/w) = -0.03 to 2.8) and reveal that MLC is a very competitive technique for the screening of compounds against conventional RPLC, due to its peculiar behaviour with regard to the selectivity and elution strength. The concentration of organic solvent needed to obtain sufficiently low retention times (even for highly hydrophobic steroids with log P(o/w) = 7-8) is also appreciably smaller for MLC, which reduces the environmental impact of the mobile phases.     

Technological quality determination of pharmaceutical disintegrant by DSC cooling and DSC photovisual

A number of disintegrants are available on the market. They improve tablets’ disintegration. The objective of this work is the comparison of the technological quality parameters of disintegrants using different analytical techniques. Three batches of disintegrants and their binary mixtures (water:disintegrants) were investigated. Cooling experiments were used from –30 up to 200°C. The data obtained showed calorimetric differences between the samples. In the binary mixtures water showed different crystallization behaviour from the one found in the literature. According to the results DSC technique helped the quality control of different disintegrants.     

Characterization and quantitation of mixtures of alkyl ether sulfates and carboxylic acids by capillary electrophoresis with indirect photometric detection

The separation, characterization, and determination of mixtures of alkyl ether sulfates (AES) and fatty acids (C10-C16) in background electrolytes (BGEs) containing acetonitrile (ACN)-water mixtures is addressed. Due to inhibition of the ionization of the carboxylate groups, the migration time and the resolution between the fatty acids decreased when the water content of the BGE was reduced, but efficiency and resolution between the AES oligomers improved. The migration times increased and resolution improved by substituting 5% ACN by an equivalent amount of dioxane. A complete separation of the two surfactant classes, up to the AES oligomers with 8 ethylene oxide units (EOs) with respect to C10, with excellent resolution between the AES oligomers, while preserving a satisfactory resolution between the fatty acids, was achieved with a BGE containing 5 mM trimethoxybenzoic acid, 7 mM dipentylamine, 85% ACN, 5% dioxane, and 10% water. The two surfactant classes were increasingly resolved by further reducing the water content of the BGE. Thus, C2 (acetate) was resolved from the AES oligomers up to 7 EOs using 90% ACN and 5% dioxane, but the resolution between the heavier fatty acids was poor with this BGE. Identification of the AES oligomers was eased by the excellent regularity of the successive migration times; thus, within each AES subclass or series of oligomers with the same number of carbon atoms in the alkyl chain, the migration times decreased following a mild curve as the number of EOs increased. The way how the data obtained by indirect photometry (corrected peak areas that are proportional to the molar concentrations) should be managed to avoid systematic error when the calibration curve is constructed using an AES standard with an oligomer distribution different from that of the samples is discussed and equations are given. Decyl sulfate was successfully used as internal standard. The detection limits (S/N = 3) were of ca. 2 microM for individual AES oligomers.     

Kinetics and Mechanism of Ni(II) Chelation in Model and Real Solutions of Xylem Sap of Quercus ilex

The kinetics of formation and dissociation of Ni(II) complexes with oxalic and citric acids was studied by cyclic voltammetry in model solutions of xylem sap of Q. ilex (the dominant tree growing on serpentine soils of Northeast Portugal) using representative concentrations, pH and ionic strength. The role of magnesium on complex formation was analyzed from solutions where Mg is present at concentration levels found in the xylem sap of Q. ilex growing on both nonserpentine and serpentine soils. Kinetics studies were also done in diluted solutions of real xylem sap samples, spiked with increasing amounts of magnesium. The values obtained for the apparent rate constants were those anticipated by the proposed model. To test the validity of the methodology and mechanisms, formation rate constants, k_f (M^?1 s^?1) of Ni(II) complexes with citrate and oxalate were evaluated that compare with the values from Eigen mechanism.