Effect of chromatographic conditions on liquid chromatographic chiral separation of terbutaline and salbutamol on Chirobiotic V column

In this study, a method for enantioseparation of terbutaline and salbutamol was established using Chirobiotic V column as a stationary phase. Polar ionic mode applying mobile phase containing ammonium nitrate in 100% ethanol, pH 5.1 was found to give the best separation. The salt concentration in the mobile phase and pH value were found to be the most important chromatographic factors affecting separation. Separation of enantiomers of these two basic analytes was complete in less than 10 min without applying ammonium trifluoroacetate (ATFA) or triethylamine (TEA) salts.     

Spectroscopic characterization, X-ray structure, antimicrobial activity and DFT calculations of novel dipicolinate copper(II) complex with 2,6-pyridinedimethanol

Novel dipicolinate complex of copper(II) ion, [Cu(dmp)(dpc)]·0.8H(2)O [dmp: 2,6-pyridinedimethanol; dpc: dipicolinate or pyridine-2,6-dicarboxylate], has been prepared and fully characterized by single crystal X-ray structure determination. The central copper(II) ion is bonded to dpc and dmp ligands through pyridine nitrogen atom together with two oxygen atom, forming the distorted octahedral geometry. The complex molecules, connected via O-H···O hydrogen bonds, form a supramolecular structure. H(2)dpc, [Cu(dpc)(H(2)O)(3)] and [Cu(dmp)(dpc)]·0.8H(2)O were screened for antimicrobial activity against Gram-positive, Gram-negative bacteria and yeast. H(2)dpc and [Cu(dpc)(H(2)O)(3)] exhibited antibacterial and antifungal activity, while [Cu(dmp)(dpc)]·0.8H(2)O exhibited activity only for Gram-positive bacteria. The geometry optimization and EPR parameters were carried out using the following unrestricted hybrid density functionals: LSDA, BPV86, B3LYP, B3PW91, MPW1PW91, PBEPBE and HCTH. Although the supramolecular interactions have some influences on the molecular geometry in solid state phase, calculated data show that the predicted geometries can reproduce the structural parameters. The electronic station in the frontier orbitals of the copper complex calculated from the experimental data is compared to the results of time-depended DFT calculations with the polarizable continuum model. Calculated vibrational frequencies are consistent with the experimental IR data.     

Hybrids of organic molecules and flat, oxide-free silicon: high-density monolayers, electronic properties, and functionalization

Since the first report of Si-C bound organic monolayers on oxide-free Si almost two decades ago, a substantial amount of research has focused on studying the fundamental mechanical and electronic properties of these Si/molecule surfaces and interfaces. This feature article covers three closely related topics, including recent advances in achieving high-density organic monolayers (i.e., atomic coverage >55%) on oxide-free Si(111) substrates, an overview of progress in the fundamental understanding of the energetics and electronic properties of hybrid Si/molecule systems, and a brief summary of recent examples of subsequent functionalization on these high-density monolayers, which can significantly expand the range of applicability. Taken together, these topics provide an overview of the present status of this active area of research.     

Rational development of a selection model for solvent gradients in single-step separation of ginsenosides from Panax ginseng using high-speed counter-current chromatography

A new model of solvent gradients selection was rationally developed for the preparative separation of target compounds. The solvent gradients were selected based on a three-stage screening process where stationary phase retention was ensured by introducing a new parameter termed as the phase ratio. The phase ratio was calculated after mixing the upper phase of a solvent system with the lower phase of a different solvent system (1:1, v/v). The developed model was applied to the one-step separation of eight ginsenosides from Panax ginseng. Three gradients were selected on the basis of new model and eight ginsenosides, Rb(1), Rb(2), Rc, Rd, Re, Rg(1), Rf, and Rh(1), were efficiently separated by high-speed counter-current chromatography coupled with evaporative light scattering detector. The structures of all compounds were characterized by electrospray-ionization mass spectrometry and nuclear magnetic resonance spectroscopy.     

Random Čech complexes on Riemannian manifolds

In this paper we study the homology of a random ?ech complex generated by a homogeneous Poisson process in a compact Riemannian manifold M. In particular, we focus on the phase transition for “homological connectivity” where the homology of the complex becomes isomorphic to that of M. The results presented in this paper are an important generalization of 7 , from the flat torus to general compact Riemannian manifolds. In addition to proving the statements related to homological connectivity, the methods we develop in this paper can be used as a framework for translating results for random geometric graphs and complexes from the Euclidean setting into the more general Riemannian one.     

A Pseudo-Pareto Distribution and Concomitants of Its Order Statistics

Pareto distributions are very flexible probability models with various forms and kinds. In this paper, a new bivariate Pseudo-Pareto distribution and its properties are presented and discussed. Main variables, order statistics and concomitants of this distribution are studied and their importance for risk and reliability analysis is explained. Joint and marginal distributions, complementing cumulative distributions and hazard functions of the variables are derived. Numerical illustrations, graphical displays and interpretations for the obtained distributions and derived functions are provided. An implementation example on defaultable bonds is performed.     

A sharp threshold for minimum bounded-depth and bounded-diameter spanning trees and Steiner trees in random networks

In the complete graph on n vertices, when each edge has a weight which is an exponential random variable, Frieze proved that the minimum spanning tree has weight tending to ζ(3) = 1/1³ + 1/2³ + 1/3³ +… as n → ∞. We consider spanning trees constrained to have depth bounded by k from a specified root. We prove that if k ≥ log₂ logn+ω(1), where ω(1) is any function going to ∞ with n, then the minimum bounded-depth spanning tree still has weight tending to ζ(3) as n → ∞, and that if k < log₂ logn, then the weight is doubly-exponentially large in log₂ logn ? k. It is NP-hard to find the minimum bounded-depth spanning tree, but when k≤log₂ logn?ω(1), a simple greedy algorithm is asymptotically optimal, and when k ≥ log₂ logn+ω(1), an algorithm which makes small changes to the minimum (unbounded depth) spanning tree is asymptotically optimal. We prove similar results for minimum bounded-depth Steiner trees, where the tree must connect a specified set of m vertices, and may or may not include other vertices. In particular, when m=const×n, if k≥log₂ logn+ω(1), the minimum bounded-depth Steiner tree on the complete graph has asymptotically the same weight as the minimum Steiner tree, and if 1 ≤ k ≤ log₂ logn?ω(1), the weight tends to $(1 - 2^{ - k} )\sqrt {8m/n} \left[ {\sqrt {2mn} /2^k } \right]^{1/(2^k - 1)}$ in both expectation and probability. The same results hold for minimum bounded-diameter Steiner trees when the diameter bound is 2k; when the diameter bound is increased from 2k to 2k+1, the minimum Steiner tree weight is reduced by a factor of $2^{1/(2^k - 1)}$ .