Determination of disulfiram by micellar liquid chromatography in illicit preparations

Presently, disulfiram is used in aversion therapy for recovering alcoholics. It acts by inhibiting aldehyde dehydrogenase, leading to high blood levels of acetaldehyde. A simple direct injection micellar liquid chromatographic procedure was developed to determine disulfiram in illicit preparations (ayurvedic, herbal, divine ash, and traditional medicine), as well as in pharmaceuticals and biological samples (urine). After application of a predictive optimization strategy, the proposed method was developed using a 0.1 M sodium dodecyl sulfate-butanol 4% (v/v) buffered to pH 7 as the mobile phase at a flow rate of 1 mL/min, an octyl silyl (C8) 150 mm column, and diode array detection at 248 nm. Under the above conditions, the analysis time was below 8 min. Validation studies were based on U.S. Food and Drug Administration guidelines. The LOD (3 x SD criterion) was 15 ng/mL and LOQ (10 x SD criterion) was 70 ng/mL for disulfiram. The intraday and interday precisions were below 3.5%, recoveries were in the range of 97-102%, and robustness was below 3%. The optimized and validated micellar liquid chromatographic method was successfully applied to the determination of disulfiram in ayurvedic, herbal, divine ash, and other samples. The procedure developed could also be used in the fields of QC, routine analysis, and pharmacokinetic studies.     

Novel products from C6H5 + C6H6/C6H5 reactions

To date only one product, biphenyl, has been reported to be produced from C(6)H(5) + C(6)H(6)/C(6)H(5) reactions. In this study, we have investigated some unique products of C(6)H(5) + C(6)H(6)/C(6)H(5) reactions via both experimental observation and theoretical modeling. In the experimental study, gas-phase reaction products produced from the pyrolysis of selected aromatics and aromatic/acetylene mixtures were detected by an in situ technique, vacuum ultraviolet (VUV) single photon ionization (SPI) time-of-flight mass spectrometry (TOFMS). The mass spectra revealed a remarkable correlation in mass peaks at m/z = 154 {C(12)H(10) (biphenyl)} and m/z = 152 {C(12)H(8) (?)}. It also demonstrated an unexpected correlation among the HACA (hydrogen abstraction and acetylene addition) products at m/z = 78, 102, 128, 152, and 176. The analysis of formation routes of products suggested the contribution of some other isomers in addition to a well-known candidate, acenaphthylene, in the mass peak at m/z = 152 (C(12)H(8)). Considering the difficulties of identifying the contributing isomers from an observed mass number peak, quantum chemical calculations for the above-mentioned reactions were performed. As a result, cyclopenta[a]indene, as-indacene, s-indacene, biphenylene, acenaphthylene, and naphthalene appeared as novel products, produced from the possible channels of C(6)H(5) + C(6)H(6)/C(6)H(5) reactions rather than from their previously reported formation pathways. The most notable point is the production of acenaphthylene and naphthalene from C(6)H(5) + C(6)H(6)/C(6)H(5) reactions via the PAC (phenyl addition-cyclization) mechanism because, until now, both of them have been thought to be formed via the HACA routes. In this way, this study has paved the way for exploring alternative paths for other inefficient HACA routes using the PAC mechanism.     

Microwave-assisted regioselective addition of P(O)-H bonds to alkenes without added solvent or catalyst

The addition of P(O)-H bonds to alkenes has been accomplished using microwave irradiation in the absence of added solvent and catalyst. In addition to single addition reactions, tandem hydrophosphinylation reactions with alkynes afforded unsymmetrical species such as phosphine oxide-phosphinates. [reaction: see text]     

Conjugate addition of 2- and 4-pyridylcuprates: an expeditious asymmetric synthesis of natural (-)-evoninic acid

[reaction: see text] The scope and limitations of the conjugate addition of 2- and the first 4-pyridyl Gilman homocuprates to various alpha,beta-unsaturated Michael acceptors are delineated. The conjugate addition of the cuprate of 2-bromo-3-methylpyridine to (E)-methyl crotonate then diastereoselective enolate alkylation and lipase-mediated enantioselective ester hydrolysis have enabled an efficient four-step first asymmetric synthesis of the Celastraceae sesquiterpenoid esterifying ligand (-)-(1'S,2'S)-evoninic acid.     

Spectroelectrochemistry and DFT analysis of a new {RuNO}n redox system with multifrequency EPR suggesting conformational isomerism in the {RuNO}7 state

The compound [Ru(NO)(bpym)(terpy)](PF6)3, bpym = 2,2'-bipyrimidine and terpy = 2,2':6',2"-terpyridine, with a {RuNO}6 configuration (angle Ru-N-O 175.2(4) degrees ) was obtained from the structurally characterized precursor [Ru(NO2)(bpym)(terpy)](PF6), which shows bpym-centered reduction and metal-centered oxidation, as evident from EPR spectroscopy. The relatively labile [Ru(NO)(bpym)(terpy)](3+), which forms a structurally characterized acetonitrile substitution product [Ru(CH3CN)(bpym)(terpy)](PF6)2 upon treatment with CH3OH/CH3CN, is electrochemically reduced in three one-electron steps of which the third, leading to neutral [Ru(NO)(bpym)(terpy)], involves electrode adsorption. The first-two reduction processes cause shifts of nu(NO) from 1957 via 1665 to 1388 cm(-1), implying a predominantly NO-centered electron addition. UV-vis-NIR Spectroscopy shows long-wavelength ligand-to-ligand charge transfer absorptions for [Ru(II)(NO(-I))(bpym)(terpy)]+ in the visible region, whereas the paramagnetic intermediate [Ru(NO)(bpym)(terpy)](2+) exhibits no distinct absorption maximum above 309 nm. EPR spectroscopy of the latter at 9.5, 95, and 190 GHz shows the typical invariant pattern of the {RuNO}7 configuration; however, the high-frequency measurements at 4 and 10 K reveal a splitting of the g1 and g2 components, which is tentatively attributed to conformers resulting from the bending of RuNO. DFT calculations support the assignments of oxidation states and the general interpretation of the electronic structure.     

Vibrational self-alignment of a rigid object exploiting friction

In this paper, one-dimensional self-alignment of a rigid object via stick-slip vibrations is studied. The object is situated on a table, which has a prescribed periodic motion. Friction is exploited as the mechanism to move the object in a desired direction and to stop and self-align the mass at a desired end position with the smallest possible positioning error. In the modeling and analysis of the system, theory of discontinuous dynamical systems is used. Analytic solutions can be derived for a model based on Coulomb friction and an intuitively chosen table acceleration profile, which allows for a classification of different possible types of motion. Local stability and convergence is proven for the solutions of the system, if a constant Coulomb friction coefficient is used. Next, near the desired end position, the Coulomb friction coefficient is increased (e.g. by changing the roughness of the table surface) in order to stop the object. In the transition region from low friction to high friction coefficient, it is shown that, under certain conditions, accumulation of the object to a unique end position occurs. This behavior can be studied analytically and a mapping is given for subsequent stick positions.     

Thermal performance of heat pipe with suspended nano-particles

Nanofluids are employed as the working medium for a conventional cylindrical heat pipe. A cylindrical copper heat pipe of 19.5?mm outer diameter and 400?mm length was fabricated and tested with two different working fluids. The working fluids used in this study are DI-water and Nano-particles suspension (mixture of copper nano particle and DI-water). The overall heat transfer coefficient of the heat pipe was calculated based on the lumped thermal resistance network and compared with the heat transfer coefficient of base fluid filled heat pipe. There is a quantitative improvement in the heat transfer coefficient using nano-particles suspension as the working medium. A heat transfer correlation was also developed based on multiple regression least square method and the results were compared with that obtained by the experiment.     

Dynamic curving cracks in functionally graded materials under thermo-mechanical loading

Mixed-mode dynamic crack growth along an arbitrarily smoothly varying path in functionally graded materials (FGMs) under thermo-mechanical loading is studied. The property gradation in FGMs is considered by varying shear-modulus, mass density, thermal conductivity and coefficient of thermal expansion exponentially along the gradation direction. Asymptotic analysis in conjunction with displacement potentials is used to develop the stress fields around propagating cracks in FGMs. Asymptotic temperature fields are developed first for the exponential variation of thermal conductivity and later these temperature fields are used to derive thermo-mechanical stress fields for a curving crack in FGMs. Using these thermo-mechanical stress fields, various components of the stresses are developed and the effect of curvature parameters, temperature and gradation on these stresses are discussed. Finally, using the minimum strain energy density criterion, the effect of curvature parameters, crack-tip speeds, non-homogeneity values and temperature gradients on crack growth directions are determined and discussed.     

Evidence of Impact at the Permian/Triassic Boundary from Mössbauer Spectroscopy

Sediment samples from Spiti valley, India, deposited about 250 Million years ago during the Permian-Triassic transition, have been analysed. ⁵⁷Fe Mössbauer spectroscopic studies show that iron occurs mainly as nanoparticles of hematite and goethite with a broad size distribution. The results show a high degree of resemblance with the Cretaceous-Tertiary boundary (65 My) samples where an asteroidal impact is believed to have caused mass extinction.