Theoretical total ionization cross-sections of CH x,CF x,SiH x,SiF x ( ) and CCl 4 targets by electron impact

Total ionization cross-sections of electron impact are calculated for the molecular targets CH_x, CF_x, SiH_x, SiF_x (x = 1-4) and CCl₄ at incident energies 20-3 000 eV. The calculation is based on Complex Scattering Potential approach, as developed by us recently. This leads to total inelastic cross-sections, from which the total ionization cross-sections are extracted by reasonable physical arguments. Extensive comparisons are made here with the previous theoretical and experimental data. The present results are satisfactory except for the CF_x and SiF_x (x = 1-3) radicals, for which the experimental data are lower than most of the theories by more than 50%. Received 23 May 2002 / Received in final form 24 October 2002 Published online 21 January 2003 RID="a" ID="a"e-mail: knjoshipura@yahoo.com     

Enrichment of Zinc and Iron Micronutrients in Lentil (Lens culinaris Medik.) through Biofortification

Biofortification of pulse crops with Zn and Fe is a viable approach to combat their widespread deficiencies in humans. Lentil (Lens culinaris Medik.) is a widely consumed edible crop possessing a high level of Zn and Fe micronutrients. Thus, the present study was conducted to examine the influence of foliar application of Zn and Fe on productivity, concentration, uptake and the economics of lentil cultivation (LL 931). For this, different treatment combinations of ZnSO₄·7H₂O (0.5%) and FeSO₄·7H₂O (0.5%), along with the recommended dose of fertilizer (RDF), were applied to the lentil. The results of study reported that the combined foliar application of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at pre-flowering (S1) and pod formation (S2) stages was most effective in enhancing grain and straw yield, Zn and Fe concentration, and uptake. However, the outcome of this treatment was statistically on par with the results obtained under the treatment ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage. A single spray of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage enhanced the grain and straw yield up to 39.6% and 51.8%, respectively. Similarly, Zn and Fe concentrations showed enhancement in grain (10.9% and 20.4%, respectively) and straw (27.5% and 27.6% respectively) of the lentil. The increase in Zn and Fe uptake by grain was 54.8% and 68.0%, respectively, whereas uptake by straw was 93.6% and 93.7%, respectively. Also the benefit:cost was the highest (1.96) with application of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage. Conclusively, the combined use of ZnSO₄·7H₂O (0.5%) + FeSO₄·7H₂O (0.5%) at S1 stage can contribute significantly towards yield, Zn and Fe concentration, as well as uptake and the economic returns of lentil to remediate the Zn and Fe deficiency.     

Protecting group free glycosylation: one-pot stereocontrolled access to 1,2-trans glycosides and (1→6)-linked disaccharides of 2-acetamido sugars

Unprotected 2-acetamido sugars may be directly converted into their oxazolines using 2-chloro-1,3-dimethylimidazolinium chloride (DMC), and a suitable base, in aqueous solution. Freeze drying and acid catalysed reaction with an alcohol as solvent produces the corresponding 1,2-trans-glycosides in good yield. Alternatively, dissolution in an aprotic solvent system and acidic activation in the presence of an excess of an unprotected glycoside as a glycosyl acceptor, results in the stereoselective formation of the corresponding 1,2-trans linked disaccharides without any protecting group manipulations. Reactions using aryl glycosides as acceptors are completely regioselective, producing only the (1→6)-linked disaccharides.

Un-protected 2-acetamido sugars are stereoselectively converted into 1,2-trans glycosides and (1→6)-linked disaccharides without any protecting groups. Reaction proceeds via intermediate oxazolines which react with acceptors under acid catalysis.     

Dispersion-corrected density functional theory calculations of the molecular binding of n-alkanes on Pd(111) and PdO(101)

We investigated the molecular binding of n-alkanes on Pd(111) and PdO(101) using conventional density functional theory (DFT) and the dispersion-corrected DFT-D3 method. In agreement with experimental findings, DFT-D3 predicts that the n-alkane desorption energies scale linearly with the molecule chain length on both surfaces, and that n-alkanes bind more strongly on PdO(101) than on Pd(111). The desorption energies computed using DFT-D3 are slightly higher than the measured values for n-alkanes on Pd(111), though the agreement between computation and experiment is a significant improvement over conventional DFT. The measured desorption energies of n-alkanes on PdO(101) and the energies computed using DFT-D3 agree to within better than 2.5 kJ/mol (< 5%) for chain lengths up to n-butane. The DFT-D3 calculations predict that the molecule-surface dispersion energy for a given n-alkane is similar in magnitude on Pd(111) and PdO(101), and that dative bonding between the alkanes and coordinatively unsaturated Pd atoms is primarily responsible for the enhanced binding of n-alkanes on PdO(101). From analysis of the DFT-D3 results, we estimate that the strength of an alkane η(2)(H, H) interaction on PdO(101) is ~16 kJ/mol, while a single η(1) H-Pd dative bond is worth about 10 kJ/mol.     

Automated structure verification based on 1H NMR prediction

A unique opportunity exists when an experimental NMR spectrum is obtained for which a specific chemical structure is anticipated. A process of Verification--the confirmation of a postulated structure--is now possible, as opposed to Elucidation-the de novo determination of a structure. A method for automated structure verification is suggested, which compares the chemical shifts, intensities and multiplicities of signals in an experimental 1H NMR spectrum with those from a predicted spectrum for the proposed structure. A match factor (MF) is produced and used to classify the spectrum-structure match into one of three categories, correct, ambiguous, or incorrect. The verification result is also augmented by the spectrum assignment obtained as part of the verification process. This method was tested on a set of synthetic spectra and several sets of experimental spectra, all of which were automatically prepared from raw data. Taking into account even the most problematic structures, with many labile protons present and poor prediction accuracy, 50% of all spectra can still be automatically verified without any false positives or negatives. In a blind test on a typical set of data, it is shown that fewer than 31% of the structures would need manual evaluation. This means that a system is possible whereby 69% of the spectra are prepared and evaluated automatically, and never need to be seen or evaluated by a human.     

Structure Elucidator: a versatile expert system for molecular structure elucidation from 1D and 2D NMR data and molecular fragments

StrucEluc is an expert system that allows the computer-assisted elucidation of chemical structures based on the inputs of a series of spectral data including 1D and 2D NMR and mass spectra. The system has been enabled to allow a chemist to utilize fragments stored in a fragment database as well as user-defined fragments submitted by the chemist in the structure elucidation process. The association of fragments in this way has been shown to dramatically speed up the process of structure generation from 2D NMR data and has helped to minimize or eliminate the need for user intervention thereby further enabling the vision of automated elucidation. The use of fragments has frequently transformed very difficult 2D NMR elucidation challenges into easily solvable tasks. A strategy to utilize molecular fragments has been developed and optimized based on specific challenging examples. This strategy will be described here using real world examples. Experience gained by solving more than 150 structure elucidation problems from a variety of literature sources is also reviewed in this work.     

Assessment of turbulence modeling for gas flow in two-dimensional convergent–divergent rocket nozzle

In the present study, the turbulent gas flow dynamics in a two-dimensional convergent–divergent rocket nozzle is numerically predicted and the associated physical phenomena are investigated for various operating conditions. The nozzle is assumed to have impermeable and adiabatic walls with a flow straightener in the upstream side and is connected to a plenum surrounding the nozzle geometry and extended in the downstream direction. In this integrated component model, the inlet flow is assumed a two-dimensional, steady, compressible, turbulent and subsonic. The physics based mathematical model of the considered flow consists of conservation of mass, momentum and energy equations subject to appropriate boundary conditions as defined by the physical problem stated above. The system of the governing equations with turbulent effects is solved numerically using different turbulence models to demonstrate their numerical accuracy in predicting the characteristics of turbulent gas flow in such complex geometry. The performance of the different turbulence models adopted has been assessed by comparing the obtained results of the static wall pressure and the shock position with the available experimental and numerical data. The dimensionless shear stress at the nozzle wall and the separation point are also computed and the flow field is illustrated. The various implemented turbulence models have shown different behavior of the turbulent characteristics. However, the shear-stress transport (SST) k–ω model exhibits the best overall agreement with the experimental measurements. In general, the proposed numerical procedure applied in the present paper shows good capability in predicting the physical phenomena and the flow characteristics encountered in such kinds of complex turbulent flow.     

Analysis of nitrated polycyclic aromatic hydrocarbons

Many nitrated polycyclic aromatic hydrocarbons (NPAH) that are present in low concentrations in the environment and in emission sources have been shown to be mutagenic and/or carcinogenic. This paper reviews the current methods of analysis of these compounds with the emphasis on NPAH measurements in ambient particulate matter samples.