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.     

“One‐step” Preparation of Thiol‐Ene Clickable PEG‐Based Thermoresponsive Hyperbranched Copolymer for In Situ Crosslinking Hybrid Hydrogel

A well‐defined poly(ethylene glycol) based hyperbranched thermoresponsive copolymer with high content of acrylate vinyl groups was synthesized via a “one‐pot and one‐step” deactivation enhanced atom transfer radical polymerization approach, which provided an injectable and in situ crosslinkable system via Michael‐type thiol‐ene reaction with a thiol‐modified hyaluronan biopolymer. The hyperbranched structure, molecular weight, and percentage of vinyl content of the copolymer were characterized by gel permeation chromatography and ¹H NMR. The lower critical solution temperature of this copolymer is close to body temperature, which can result in a rapid thermal gelation at 37 °C. The scanning electron microscopy analysis of crosslinked hydrogel showed the network formation with porous structure, and 3D cell culture study demonstrated the good cell viability after the cells were embedded inside the hydrogel. This injectable and in situ crosslinking hybrid hydrogel system offers great promise as a new class of hybrid biomaterials for tissue engineering.     

Sums and products along sparse graphs

In their seminal paper from 1983, Erdős and Szemerédi showed that any n distinct integers induce either n ^1+ɛ distinct sums of pairs or that many distinct products, and conjectured a lower bound of n ^2−o(1). They further proposed a generalization of this problem, in which the sums and products are taken along the edges of a given graph G on n labeled vertices. They conjectured a version of the sum-product theorem for general graphs that have at least n ^1+ɛ edges.     

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.     

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 $2^{1/(2^k - 1)}$ .     

Influence of nano-material on the expansive and shrinkage soil behavior

One-dimensional nanoribbons, thickness of which is smaller than width, exhibit special confinement and edge effects far from uniform in the cross-section. By means of density functional theory, we investigated the influence of the edges and doping positions on the electronic structure of Ag-doped ZnO armchair nanoribbons (ZnOANRs). Ag doping in monolayer and bilayer ZnOANRs (m- and b-ZnOANRs) have all been examined. The results indicated that there is no significant difference on the stability of Ag doping in different positions of both m- and b-ZnOANRs, but exhibits very different electronic properties directly related to the different doping positions. The depth of the acceptor states has essential relationship with the interaction between host O 2p and Ag 4d states in the acceptor. Ag substituting Zn atoms at the inner region of m-ZnOANRs could create shallow acceptors with small hole effective masses, benefit for p-type conduction. Ag doping in the inner region of b-ZnOANRs would create shallow acceptors but larger hole effective masses. The difficulty of hole mobility could be improved by increasing the Ag doping concentration in b-ZnOANRs. The discussion about the mechanism and the suggestion about the achievement in the experiment are interesting and timely.     

Manipulation of magnetic nanostructures through low temperature metal–oxygen chemistry: Co/CoO exchange biased nanodonuts and Co nanotips

Dense nanodonut and nanotip type morphologies are shown to self-evolve in ultrathin cobalt films during growth under vacuum, depending on the level of oxygen incorporation and temperature. The nanodonut morphology forms at room temperature and the corresponding magnetic hysteresis shows exchange bias (～35 Oe shift along the field axis), which is attributed to the presence of CoO and its exchange coupling with cobalt. The morphology evolves into nanotip features with increase of growth temperature, with concurrent elimination of the oxide component and exchange bias.