Experimental IR and Raman spectra and quantum chemical studies of molecular structures, conformers and vibrational characteristics of L-ascorbic acid and its anion and cation

IR and spectra of the L-ascorbic acid (L-AA) also known as vitamin C have been recorded in the region 4000-50 cm(-1). In order to make vibrational assignments of the observed IR and Raman bands computations were carried out by employing the RHF and DFT methods to calculate the molecular geometries and harmonic vibrational frequencies along with other related parameters for the neutral L-AA and its singly charged anionic (L-AA(-)) and cationic (L-AA(+)) species. Significant changes have been found for different characteristics of a number of vibrational modes. The four ν(O-H) modes of the L-AA molecule are found in the order ν(O(9)-H(10))>ν(O(19)-H(20))>ν(O(7)-H(8))>ν(O(14)-H(15)) which could be due to complexity of hydrogen bonding in the lactone ring and the side chain. The CO stretching wavenumber (ν(46)) decreases by 151 cm(-1) in going from the neutral to the anionic species whereas it increases by 151 cm(-1) in going from the anionic to the cationic species. The anionic radicals have less kinetic stabilities and high chemical reactivity as compared to the neutral molecule. It is found that the cationic radical of L-AA is kinetically least stable and chemically most reactive as compared to its neutral and anionic species.     

DFT and ab initio quantum chemical studies on p-cyanobenzoic acid

The Fourier transform infrared (FTIR) and FT-Raman spectra of p-cyanobenzoic acid (CBA) have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. The complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the observed FTIR and FT-Raman data. The vibrational frequencies determined experimentally were compared with theoretical wavenumbers obtained from ab initio HF and DFT-B3LYP gradient calculations employing 6-31G**, 6-311++G** and cc-pVTZ basis sets for the optimised geometry of the compound. The geometry and normal modes of vibration obtained from the HF and DFT methods are in good agreement with the experimental data. The normal coordinate analysis was also carried out with ab initio force fields utilising Wilson's FG matrix method. The interactions of cyano and carboxylic acid groups with the skeletal vibrational modes were investigated.     

Use of a crown ether-heteropoly acid precipitate as a potassium ion-selective membrane electrode

Summary A Potassium ion-selective electrode based on dibenzo-18-crown-6-tungstophosphoric acid precipitate membrane is prepared and conditions for the best functioning have been investigated. The working concentration and pH-range of the electrode is 2.0×10^–2 to 1.3×10^–6 mol/l and 2.9–6.5, respectively. The selectivity coefficient values for a large number of cations are quite low except for caesium and ammonium ions. The electrode can tolerate non-aqueous content upto 20%.

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Kaliumion-sensitive Membranelektrode auf Basis von Kronenether-Heteropolysäure

     

Efficient allylation of aldehydes with allyltributylstannane catalyzed by CuI

Cuprous iodide has been found to be a very effective catalyst for allylation of aldehydes with allyltributylstannane. The catalytic system efficiently promotes the allylation reaction in DMF to produce homoallylic alcohols in high yield.     

Positive values of non-homogeneous indefinite quadratic forms of type (1, 4)

Let Г_r,n—r denote the infimum of all number Г > 0 such that for any real indefinite quadratic form inn variables of type (r, n—r), determinantD ≠ 0 and real numbers c₁; c₂,…, c_n, there exist integersx ₁,x₂,…,x_n satisfying 0 < Q(x₁+c₁,x₂ + c₂,…,x_n + c_n) ≤(Г|Z > |)^1/n. All the values of Г_r,n—r are known except for г_1,4. Earlier it was shown that 8 ≤Г_1,4 ≤16. Here we improve the upper bound to get Г_1,4 < 12.     

Equivalence of the angular forces in the lattice dynamics of fcc metals

The expressions for the Clark, Gazis and Wallis type of angular forces are rederived in the caseof fcc metals. These expressions are now foundtobe equivalent to the deLauney type of angular forces.     

Investigation of anomalons in He fragments

We have studied the mean free path of He fragments from projectile beams of Ar, Fe and Kr of energy 1 ? E ?2A GeV at different distances $\text{(L ? 2.5}\text{cm}\text{)}$ from their production point and found that they are the same, independent of their (i) energy, (ii) target size, (iii) target excitation, (iv) He multiplicities and (v) production angles.     

Transfer of charge in liquid alloys

Hard sphere diameters of liquid alkali metal alloys (Na-Cs and K-Rb) are calculated at 373 K ensuring the minimum Helmholtz free energy of the system. These diameters are then used to fix the packing density of the alloy. On alloying, the hard sphere diameters of Na in Na-Cs and K in K-Rb alloys expand whereas those of Cs and Rb contract.     

Angular forces in the lattice dynamics of b.c.c. metals

The lattice dynamics of the b.c.c. lattice has been investigated using the central and the angular forces which are in general rotationally invariant. It has been observed that the four force constants are related to three elastic constants only. Dispersion curves for sodium were calculated and were found to be in excellent agreement with experiment.