Rate coefficients and products for gas‐phase reactions of chlorine atoms with cyclic unsaturated hydrocarbons at 298 K

Rate coefficients for the reaction of Cl atoms with cycloalkenes have been determined using the relative rate method, at 298 K and atmospheric pressure of N₂. Reference molecule was n‐hexane, and the concentrations of the organics were followed by gas chromatographic analysis. Cl atoms were prepared by photolysis of trichloroacetyl chloride at 254 nm. The relative rates of reactions of Cl atoms with cycloalkenes, with respect to n‐hexane, are measured as 1.12 ± 0.38, 1.31 ± 0.14, and 1.69 ± 0.18 for cyclopentene, cyclohexene, and cycloheptene, respectively. Considering the absolute value of the rate coefficient of the reaction of Cl atom with n‐hexane as 3.03 ± 0.06 × 10^?10 cm³ molecule^?1 s^?1, the rate coefficient values for cyclopentene, cyclohexene, and cycloheptene are calculated to be (3.39 ± 1.08) × 10^?10, (3.97 ± 0.43) × 10^?10, and (5.12 ± 0.55) × 10^?10 cm³ molecule^?1 s^?1, respectively. The experiments for each molecule were repeated six to eight times, and the slopes and the rate coefficients given above are the average values of these measurements, and the quoted error includes 2σ as well as all other uncertainties in the measurement and calculations. The rate coefficient increases linearly with the number of carbon atoms, with an increment per additional CH₂ group being (8.7 ± 1.6) × 10^?12 cm³ molecule^?1 s^?1. Chloroketones and chloroalcohols, along with unsaturated ketones and alcohols, were found to be the major products of Cl‐atom‐initiated oxidation of cycloalkenes in the presence of air. The atmospheric implications of these results are discussed, along with a comparison with the reported structure activity relationships. © 2009 Wiley Periodicals, Inc. Int J Chem Kinet 42: 98–105, 2010     

High‐performance liquid chromatography/mass spectrometric and proton nuclear magnetic resonance spectroscopic studies of the transacylation and hydrolysis of the acyl glucuronides of a series of phenylacetic acids in buffer and human plasma

The use of high‐performance liquid chromatography/mass spectrometry (HPLC/MS) and proton nuclear magnetic resonance (¹H NMR) spectroscopy for the kinetic analysis of acyl glucuronide (AG) isomerisation and hydrolysis of the 1‐β‐O‐acyl glucuronides (1‐β‐O‐AG) of phenylacetic acid, (R)‐ and (S)‐α‐methylphenylacetic acid and α,α‐dimethylphenylacetic acid is described and compared. Each AG was incubated in both aqueous buffer, at pH 7.4, and control human plasma at 37°C. Aliquots of these incubations, taken throughout the reaction time‐course, were analysed by HPLC/MS and ¹H NMR spectroscopy. In buffer, transacylation reactions predominated, with relatively little hydrolysis to the free aglycone observed. In human plasma incubations the calculated rates of reaction were much faster than for buffer and, in contrast to the observations in buffer, hydrolysis to the free aglycone was a significant contributor to the overall reaction. A diagnostic analytical methodology based on differential mass spectrometric fragmentation of 1‐β‐O‐AGs compared to the 2‐, 3‐ and 4‐positional isomers, which enables selective determination of the former, was confirmed and applied. These findings show that HPLC/MS offers a viable alternative to the more commonly used NMR spectroscopic approach for the determination of the transacylation and hydrolysis reactions of these AGs, with the major advantage of having the capability to do so in a complex biological matrix such as plasma. Copyright © 2010 John Wiley & Sons, Ltd.     

Realization of a unique time evolution unitary operator in Klein Gordon theory

The scattering theory for the Klein Gordon equation, with time-dependent potential and in a non-static space-time, is considered. Using the Klein Gordon equation formulated in the Hubert spaceL ²(R ³) and the Einstein’s relativistic equation in the spaceL ²(R ³, dx) and establishing the equivalence of the vacuum states of their linearized forms in the Hubert spaceL ²(R ³) with the help of unique symmetric symplectic operator, the time evolution unitary operatorU(t) has been fixed for the Klein Gordon equation, incorporating either the positive or negative frequencies, in the infinite dimensional Hubert spaceL ²(R ³).     

Optical diffraction in twisted liquid-crystalline media-phase grating mode

We have calculated the diffraction of light perpendicular to the twist axis in a chiral smectic C liquid crystal. In contrast to a cholesteric liquid crystal, in a chiral smectic C liquid crystal we find extra orders which form the odd orders in the diffraction pattern. For an incident linearly polarized light, at a general azimuth, these odd orders are linearly polarized and the even orders are elliptically polarized. The intensities of the odd orders are always independent of the azimuth of the incident light, while this is possible for even orders only at a particular tilt angle of the chiral smectic C liquid crystal. Also, for the incident vibration parallel or perpendicular to the twist axis the odd orders are polarized in the orthogonal linear state with respect to incident vibration, while the even orders are in the same linear state.     

Finite Larmor radius effect on thermosolutal instability of a plasma in porous medium

The thermosolutal instability of a plasma in porous medium is considered in the presence of finite Larmor radius effect. The finite Larmor radius, stable solute gradient and magnetic field introduce oscillatory modes in the systems which were nonexistent in their absence. For stationary convection, the finite Larmor radius and stable solute gradient have stabilizing effects on the thermosolutal instability in porous medium. In presence of finite Larmor radius effect, the medium permeability has a destabilizing (or stabilizing) effect and the magnetic field has a stabilizing (or destabilizing) effect under certain condition whereas in the absence of finite Larmor radius effect, the medium permeability and the magnetic field have destabilizing and stabilizing effects, respectively, on thermosolutal instability of a plasma in porous medium. The sufficient conditions for nonexistence of overstability are obtained.The financial assistance to Mr. Sunil in the form of Senior Research Fellowship of the Council of Scientific and Industrial Research (CSIR), New Delhi is gratefully acknowledged.     

Wild African elephants (Loxodonta africana) discriminate between familiar and unfamiliar conspecific seismic alarm calls

The ability to discriminate between call types and callers as well as more subtle information about the importance of a call has been documented in a range of species. This type of discrimination is also important in the vibrotactile environment for species that communicate via vibrations. It has recently been shown that African elephants (Loxodonta africana) can detect seismic cues, but it is not known whether they discriminate seismic information from noise. In a series of experiments, familiar and unfamiliar alarm calls were transmitted seismically to wild African elephant family groups. Elephants respond significantly to the alarm calls of familiar herds (p=0.004) but not to the unfamiliar calls and two different controls, thus demonstrating the ability of elephants to discriminate subtle differences between seismic calls given in the same context. If elephants use the seismic environment to detect and discriminate between conspecific calls, based on the familiarity of the caller or some other physical property, they may be using the ground as a very sophisticated sounding board.     

Quantitative determination of isoquinoline alkaloids and chlorogenic acid in Berberis species using ultra high performance liquid chromatography with hybrid triple quadrupole linear ion trap mass spectrometry

Berberis species are well known and used extensively as medicinal plants in traditional medicine. They have many medicinal values attributable to the presence of alkaloids having different pharmacological activities. In this study, a method was developed and validated as per international conference on harmonization guidelines using ultra high performance liquid chromatography with hybrid triple quadrupole‐linear ion trap mass spectrometry operated in the multiple reaction monitoring mode for nine bioactive compounds, including protoberberine alkaloids, aporphine alkaloids and chlorogenic acid. This method was applied in different plant parts of eight Berberis species to determine variations in content of nine bioactive compounds. The separation was achieved on an ACQUITY UPLC CSH? C₁₈ column using a gradient mobile phase at flow rate 0.3 mL/min. Calibration curves for all the nine analytes provided optimum linear detector response (with R² ≥0.9989) over the concentration range of 0.5–1000 ng/mL. The precision and accuracy were within RSDs ≤2.4 and ≤2.3%, respectively. The results indicated significant variation in the total contents of the nine compounds in Berberis species.     

A Facile Diversity‐Oriented Multicomponent One‐Pot Synthesis of 3‐Amino‐6,7‐dihydrobenzo[c]thiophen‐4(5H)‐one Derivatives from α‐Oxo‐N,S‐ketene Acetal

A convenient one‐pot multicomponent method for the preparation of 3‐amino‐6,7‐dihydrobenzo[c]thiophen‐4(5H)‐one derivative has been developed. Reaction of 1,3‐cyclohexanedione and phenyl isothiocynate gave α‐oxo‐N,S‐ketene acetal that were reacted in situ with 2‐chloromethylquniazoline‐4‐one derivatives, in the presence of sodium hydride to afford the target compound in reasonable overall yields.     

FeCl3 catalysed two consecutive aminomethylation at the α-position of the β-dicarbonyl compounds: an easy access to hexahydropyrimidines and its spiro analogues

Multicomponent synthesis of 1,3-diaryl-hexahydropyrimidines by a one-pot reaction of 1,3-dicarbonyl compounds, amines and formaldehyde catalysed by FeCl₃ in dichloromethane at room temperature (25-30 °C) has been reported. Double amino methylation occurs at the α-position of the 1,3-dicabonyl compounds/β-keto esters. The same methodology leads to spiro compounds with indane-1,3-dione. In this reaction, six molecules condense in one pot to form six new covalent bonds, thus, creating high atom economy. This is the first report of the synthesis of the substituted hexahydropyrimidines involving β-keto esters and its spiro analogues with indane-1,3-dione.     

胶束催化体系中的对映选择性环醚化反应

The enantioselective cycloetherification of substituted keto phenols into their corresponding dihydrobenzofuran derivatives was carried out using hydrogen peroxide and chiral quaternary ammonium iodide in micellar media. This approach increased the conversion rate of cycloetherification and also widened the scope of this particular reaction for various substituted keto phenols with electron withdrawing as well as electron donating functionalities. The use of a surfactant in the cycloetherification reaction ...