Protolytic reactions of 3,3'-dimethylnaphthidine and 3,3'-dimethoxybenzidine

The dissociation constants of diprotonated 3,3'-dimethylnaphthidine (DMN) and 3,3'-dimethoxybenzidine (DMB) have been determined spectrophotometrically. They are: pK(a1) = 2.62 +/- 0.03, pK(a2) = 3.33 +/- 0.09 for DMN: pK(a1) = 2.83 +/- 0.07, pK(a2) = 4.05 +/- 0.12 for DMB. The molar absorptivities (l.mole(-1).cm(-1)) of all forms of the indicators have been also determined: epsilon(B) = 1.68 x 10(4), epsilon(BH(+)) = 9.34 x 10(3), epsilon(BH(2+)(2)) = 1.80 x 10(3) at 300 nm for DMB; epsilon(B) = 7.33 x 10(3), epsilon(BH(+)) = 3.73 x 10(3), epsilon(BH(2+)(2)) = 0 at 330 nm for DMN.     

Use of SPE—TLC for Quality Control of Rhodiola rosea Extracts

SPE and TLC have been used for qualitative and quantitative analysis of salidroside, rosavin, rosarin, and rosin in commercially available dry extracts from Rhodiola rosea roots. The best separation of all the compounds was achieved on silica gel TLC plates with ethyl acetate—methanol—water, 77 + 13 + 10 (v/v), as mobile phase. UV detection was performed at λ = 215 nm for salidroside and at λ= 245 nm for the rosavins (rosavin, rosarin, and rosin). Detection limits for salidroside and the rosavins were 90 ng and 60 ng per spot, respectively. Results from quantitative analysis confirmed the manufacturer’s declaration of the amounts of salidroside and the rosavins in the extracts.

     

Retention Behavior of New Oral Antidiabetic Drugs in Reversed-Phase Chromatography

JPC – Journal of Planar Chromatography – Modern TLC - The thin-layer chromatographic behavior of three of the newest oral antidiabetic agents, pioglitazone, rosiglitazone, and...     

Do intramolecular halogen bonds exist? Ab initio calculations and crystal structures’ evidences

Cl···O intramolecular contacts are analysed here. Hence the Cambridge Structural Database (CSD) search was performed to find five-membered Cl–C=C–C=O pseudo-rings closed through Cl···O intramolecular contacts. Such rings were analysed and it was found that some of Cl···O distances are smaller than the corresponding sum of van der Waals radii. Additionally ab initio MP2/6-311++G(d,p) calculations and AIM analyses were carried out here on 3-chloropropenal and its fluoro derivatives to deepen the nature of intramolecular Cl···O interactions, some of findings may indicate that they are attractive and stabilizing ones. This paper is dedicated to Prof. T. M. Krygowski on the occasion of his 70th birthday     

Solvation force for long-ranged wall--fluid potentials

The solvation force of a simple fluid confined between identical planar walls is studied in two model systems with short ranged fluid-fluid interactions and long-ranged wall-fluid potentials decaying as -Az(-p),z--> infinity, for various values of p. Results for the Ising spins system are obtained in two dimensions at vanishing bulk magnetic field h=0 by means of the density-matrix renormalization-group method; results for the truncated Lennard-Jones (LJ) fluid are obtained within the nonlocal density functional theory. At low temperatures the solvation force f(solv) for the Ising film is repulsive and decays for large wall separations L in the same fashion as the boundary field f(solv) approximately L(-p), whereas for temperatures larger than the bulk critical temperature f(solv) is attractive and the asymptotic decay is f(solv) approximately L(-(p+1)). For the LJ fluid system f(solv) is always repulsive away from the critical region and decays for large L with the the same power law as the wall-fluid potential. We discuss the influence of the critical Casimir effect and of capillary condensation on the behavior of the solvation force.     

Proton nuclear magnetic resonance characterisation of glycosaminoglycans using chemometric techniques

Various types of glycosaminoglycans (GAGs) including heparins, chondroitin sulfates, dermatan sulfate and hyaluronic acid were studied from their proton nuclear magnetic resonance (1H NMR) spectra using chemometric techniques. Despite the complexity of the 1H NMR signals, data analysis using principal component analysis enabled the different GAG classes to be distinguished and permitted their classification according to their chemical structure. The analysis of the composition of the major disaccharide unit and other relevant chemical structures in the heparin samples was performed using partial least squares regression.     

Luminescence Properties of Tb-Doped Yttrium Disilicate Prepared by the Sol–Gel Method

A sol–gel method for the synthesis of nanosized powders of yttrium disilicate doped with Tb^{3 +} is presented. The influence of grain size and annealing temperature on the structure and luminescence properties of the materials obtained has been investigated. The preparation of glass-ceramic composite has been also described. The effect of incorporating the nanocrystals into sol–gel silica glasses on their physicochemical properties has been shown and discussed. A lack of influence of the annealing above 1300°C on the lifetimes measured for the nanocrystals embedded in the glass, as compared to the Y₂Si₂O₇:Tb^{3 +} powders, has been observed.     

Molybdenum(VI) and molybdenum(V) mononuclear and dinuclear complexes with 1,3-diphenyl-1,3-propanedione

Summary The synthesis and the dinuclear or mononuclear nature of several molybdenum(VI) and molybdenum(V) oxocomplexes derived from 1,3-diphenyl-1,3-propanedione (HLL) are described. These complexes were identified by i.r. and electronic spectra, magnetic susceptibility and analytical data, and are assigned the following formulae: [MoO₂(LL)₂], [Mo₂O₅(LL)₂], [Mo₂O₄(LL)₂], [MoOCl(LL)₂], [MoCl₂(LL)] and [MoO(OH)(LL)₂)]. The low magnetic moments of the dinuclear complexes are due, in part, to intramolecular interactions. The i.r. data show that the dionate is bound by two oxygen atoms forming a chelate six-membered ring.     

Insights into the structure of cyclohexane from femtosecond degenerate four-wave mixing spectroscopy and ab initio calculations

In this paper, we report the use of femtosecond time-resolved degenerate four-wave mixing rotationally resolved spectroscopy to obtain very accurate structural information on the symmetric top cyclohexane. Apart from highlighting the versatility of this method in determining accurate structures of large and complex molecules without dipole moment, the present study also details the comparison of the experimentally determined rotational constant B(0) with that obtained from high-level ab initio calculations. The theoretical calculations, which were carried out at both the second-order M?ller-Plesset (MP2) and coupled-cluster with single, double, and perturbative triple substitutions [CCSD(T)] levels of theory, also take into account vibrational averaging effects. A detailed investigation of the vibrational averaging effects reveals that the corrections emerge from only the six highly symmetric A(1g) modes, a justification of which is provided by an analysis of these modes.