Comprehensive quantum chemical calculations and molecular docking analysis of uracil mustard by first principle

Uracil mustard belongs to the nitrogen mustard family and is primarily used in anticancer drugs. The research that follows, investigates many quantum chemical features such as the computation of global minimum energies with no negative wavenumber values using the Density Functional Theory (DFT) with Becke three functional and 6-311G (d, p)/6–311++G (d, p) basis sets. All the vibrational modes have been calibrated and justified in comparison to their experimental counterparts. Mustard's polarizability and hyperpolarizability components, Natural Bond Analysis (NBO), electronic properties, Fukui function analysis, various global parameters, Quantum Theory of Atoms In Molecule (QTAIM) analysis, ADMET analysis, and docking analysis have all been investigated using the same theory and basis sets, indicating its biochemical significance. The biological activity of the molecule is reported by using PASS software. The Full fitness score and binding affinity parameters are utilized to determine the binding strength with 6cq3 protein. The acidity of the title molecule is calculated in water solvent by polarizable continuum model (PCM) solvent effects (estimated in water). The HOMO, LUMO, and MESP plots are used to explore the nature of binding and surfaces. The Fukui functions are computed using Mulliken atomic charges for neutral atoms, cations, and anions. The Ultraviolet–visible (UV–vis) of the molecule is computed employing the TD-DFT method.     

The use of multivariate modelling of near infra-red spectra to predict the butter fat content of spreads

In order to obtain a rapid method that can detect adulteration of butter fats with cheaper vegetable fats, the use of NIR spectroscopy and multivariate modelling was explored. For model building and validation, an extensive set of samples was collected, consisting of 152 butter samples, 42 oils and 200 blends thereof. Variations in butter fat composition are reflected in distinct NIR spectral regions. Principal components analysis and partial least square discriminant analysis was used to inspect the variation within the sample set. As reference values for training partial least squares models, butter fat levels as declared by suppliers were taken, as well as C4:0 fatty acid levels as measured directly by GC. All samples were used for training, except for 100 blends, which were used later for validation. Different pre-processing and PLS approaches were explored, resulting in models that had a RMSEPs for butter fat and C4:0 fatty acid level in the range of 4.3-8.2 and 0.33-0.38% (w/w), respectively. The performance of NIR in assessment of C4:0 fatty acid levels is lower as for GC, but this disadvantage is outweighed by shorter measurement times and the lower skill levels required. Furthermore NIR is able to assess overall levels of butter fat, in addition to the indirect indicator provided by the C4:0 fatty acid level.     

Synthesis and electrochemical studies of heterobinuclear complexes containing copper and molybdenum nitrosyl groups linked by Schiff base ligands

The reaction of [MoCl(NO)T_p ^* = tris(3,5-dimethylpyrazolylborate] with copper Schiff base complexes derived by condensation of one mole each of 2,5-dihydroxybenzaldehyde and salicylaldehyde with α,ω diamines [NH₂(CH₂) _n NH₂, n = 2–4] yields heterobinuclear complexes with two potential redox centres. I.r., electronic and e.s.r. spectroscopic properties of these complexes are described. Cyclic voltammetric data of the base complexes in DMSO reveal that the copper redox centres undergo irreversible one electron reduction at potentials which vary slightly with the polymethylene carbon chain backbone of the Schiff base ligands. Incorporation of [MoCl(NO)T_p ^*]⁺ groups in the copper Schiff base complexes, results to a slight anodic shift (100 mV) in the reduction potential of the copper centre which remains invariant as the polymethylene carbon chain lengthens. Electrochemical data of the heterobinuclear complexes using CH₂Cl₂ and DMSO as solvents indicate the solvent dependence of the reduction potentials of these complexes. In CH₂Cl₂, the reduction potential of the copper centre shifts cathodically by 100 mV, while that of the molybdenum centre shifts anodically by 200 mV. However, accumulated electrochemical data of the heterobinuclear complexes indicate minimal electronic interactions between the copper and molybdenum redox centres. This revised version was published online in June 2006 with corrections to the Cover Date.     

A MODEL FOR ESTIMATING PREMIUMS TO REDUCE IRRIGATION ON FARMS

Abstract This paper aims to determine the minimum agri‐environmental premium per hectare that farmers should receive to reduce crop irrigation. To this end, the authors develop a mixed‐integer quadratic model using a new methodology based on traditional positive mathematical programming, which allows the inclusion in the model of crop variants that are not present in the baseline situation of the farms. What is shown is that the results obtained with this new methodology, using the cost average approach of calibration, are the same as those obtained with an empirical method, when there is no change of crop distribution after the changeover from irrigated to nonirrigated farms. The theoretical results are compared with those obtained using the calibration with exogenous elasticities and are illustrated numerically for a representative farm of an area around Spain's Tablas de Daimiel in which the use of groundwater for crop irrigation has led to the ongoing deterioration of wetlands that depend on the same source of water, endangering the region's environmental sustainability.     

The 4 A 2→2 E transitions of 2[Cr(en)3Cl3]KCl. 6H2O in strong magnetic fields

The Zeeman effect of the R absorption lines for the pure compound 2[Cr(en)₃Cl₃]KCl.6H₂O has been measured photographically, using a strong pulsed magnet with fields of up to 200 000 gauss at 77 K. The results indicate g _∥ (⁴ A ₂) = 1·82 , g _⊥(⁴ A ₂) = 1·90 with g _∥(ē) = -1·82 and g _∥ (2ā) = 1·82. The uncertainties are of the order of ± 0·05.     

Synthesis and electrochemical studies of heterobinuclear zinc and molybdenum mononitrosyl complexes linked by Schiff base ligands

The reaction of 1 mol equivalent of MoCl₂(NO)T^* _p [T^* _p = tris(3,5 dimethylpyrazolyl)borate] with one mole equivalent of the zinc Schiff base complexes obtained from the condensation of 2,5-dihydroxybenzaldehyde, salicylaldehyde and a series of , diamines [NH₂(CH₂) _n NH₂, n = 2–4] is described, together with the i.r.; u.v.–vis. and ¹H-n.m.r. spectroscopic properties of these products. Cyclic voltammetric data in CH₂Cl₂ reveal that the binuclear complex products undergo reversible one-electron reductions associated with the MoCl(NO)T^* _p centre. No zinc-based redox processes in the new complexes could be detected on the cyclic voltammetry timescale. The behaviour of the MoCl(NO)T^* _p centre in DMSO indicates that the complexes undergo irreversible reductions at anodically shifted potentials (in comparison with the reduction of binuclear complexes in CH₂Cl₂), indicating that reductions of the binuclear complexes are solvent dependent.