In situ EPR study of chemoselective hydrogenation of nitroarenes on Au/Al2O3 catalyst

1. Download high-res image (106KB)
2. Download full-size image

     

Morphology and composition of NiMoW/P-Al2O3 systems based on the modified support with varied P2O5 content

1. Download high-res image (146KB)
2. Download full-size image

     

Human serum albumin in electrospun PCL fibers: structure,release, and exposure on fiber surface

Human serum albumin (HSA) introduced to the fibers produced by electrospinning from HSA and polycaprolactone (PCL) solutions in hexafluoroisopropanol has been studied in terms of its structure, release from the fibers, stability of interaction with basic polymer, accessibility for protease attack, and cellular receptors, as well as dependence of the studied parameters on the protein concentration in fibers. A limited part of the protein leaves the fibers right after soaking with water, whereas the remaining protein stays tightly bound to fibers for a long time because protein nanoparticles are tightly integrated with PCL, as shown by small‐angle X‐ray scattering. As has been demonstrated, the proteins leave the fibers in complexes with PCL. X‐ray photoelectron spectroscopy demonstrates that the protein concentration on the fiber surface is higher than the concentration in electrospinning solution. The surface‐exposed protein is recognized by cell receptors and is partially hydrolyzed by proteinase K. The data on pulse protein release, presence of PCL in the protein released from matrixes, overrepresentation of the protein on the fiber surface, and tight interaction of protein with PCL may be useful for rational design of electrospun scaffolds intended for drug delivery and tissue engineering. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis,crystal, and molecular structure of coordination polymers constructed by self-assembly of NiN<Subscript>4</Subscript> cores with 2,2′-iminodibenzoate and nitroprusside ions

Two coordination compounds of compositions [Ni(L¹)(idba)(H₂O)]·1.5 H₂O (1) and [Ni(L²)Fe(CN)₅NO]·C₂H₅OH (2) where L¹ is N, N′-bis(3-aminopropyl)ethylenediamine, L² is 2,12-dimethyl-3,7,11,17-tetraazabicyclo[11.3.1]heptadeca-1(17),2,11,13,15-pentaene, and idba^2? is 2,2′-iminodibenzoate have been synthesized and characterized by elemental analysis, IR spectroscopy, thermal analysis, and single-crystal X-ray diffraction. Complex 1 crystallizes in the monoclinic space group P2₁/n (No. 14) with a=9.810(2) Å, b=10.230(2) Å, c=25.350(5) Å, V=2543.6(9) Å³, Z=4, and R=0.0727. The nickel atom is six-coordinated by four N atoms of amine and two O atoms of water and idba^2?. The molecular packing of the complex comprises of an infinite one-dimensional layered network in which the molecules in the crystal are held together by a system of hydrogen bonding. Complex 2, however, crystallizes in the space group C2/c (No. 15) of the monoclinic system with a=19.7990(4) Å, b=14.9440(3) Å, c=19.8800(3) Å, V=5115.90(17) Å³, Z=4, and R=0.0540. The Ni ion in compound 2 has a slightly distorted octahedral arrangement of the N₄ donor atoms of primary ligand L² and two N-donor atoms of the secondary nitroprusside ligand. The structure of 2 displays an extended one-dimensional network formed by linear [—Ni—NC—Fe—CN—] units. A cyclic voltammetric study shows that compound 1 undergoes a quasireversible oxidation attributable to Ni²⁺ → Ni³⁺ in the range 300–420 mV vs SCE.     

Density functional theory augmented with an empirical dispersion term. Interaction energies and geometries of 80 noncovalent complexes compared with ab initio quantum mechanics calculations

Standard density functional theory (DFT) is augmented with a damped empirical dispersion term. The damping function is optimized on a small, well balanced set of 22 van der Waals (vdW) complexes and verified on a validation set of 58 vdW complexes. Both sets contain biologically relevant molecules such as nucleic acid bases. Results are in remarkable agreement with reference high-level wave function data based on the CCSD(T) method. The geometries obtained by full gradient optimization are in very good agreement with the best available theoretical reference. In terms of the standard deviation and average errors, results including the empirical dispersion term are clearly superior to all pure density functionals investigated-B-LYP, B3-LYP, PBE, TPSS, TPSSh, and BH-LYP-and even surpass the MP2/cc-pVTZ method. The combination of empirical dispersion with the TPSS functional performs remarkably well. The most critical part of the empirical dispersion approach is the damping function. The damping parameters should be optimized for each density functional/basis set combination separately. To keep the method simple, we optimized mainly a single factor, s(R), scaling globally the vdW radii. For good results, a basis set of at least triple-zeta quality is required and diffuse functions are recommended, since the basis set superposition error seriously deteriorates the results. On average, the dispersion contribution to the interaction energy missing in the DFT functionals examined here is about 15 and 100% for the hydrogen-bonded and stacked complexes considered, respectively.     

Competition between Halogen,Hydrogen and Dihydrogen Bonding in Brominated Carboranes

Halogen bonds are a subset of noncovalent interactions with rapidly expanding applications in materials and medicinal chemistry. While halogen bonding is well known in organic compounds, it is new in the field of boron cluster chemistry. We have synthesized and crystallized carboranes containing Br atoms in two different positions, namely, bound to C‐ and B‐vertices. The Br atoms bound to the C‐vertices have been found to form halogen bonds in the crystal structures. In contrast, Br atoms bound to B‐vertices formed hydrogen bonds. Quantum chemical calculations have revealed that halogen bonding in carboranes can be much stronger than in organic architectures. These findings open new possibilities for applications of carboranes, both in materials and medicinal chemistry.     

Study of the determination of inorganic arsenic species by CE with capacitively coupled contactless conductivity detection

The determination of arsenic(III) and arsenic(V), as inorganic arsenite and arsenate, was investigated by CE with capacitively coupled contactless conductivity detection (CE-C(4)D). It was found necessary to determine the two inorganic arsenic species separately employing two different electrolyte systems. Electrolyte solutions consisting of 50 mM CAPS/2 mM L-arginine (Arg) (pH 9.0) and of 45 mM acetic acid (pH 3.2) were used for arsenic(III) and arsenic(V) determinations, respectively. Detection limits of 0.29 and 0.15 microM were achieved for As(III) and As(V), respectively by using large-volume injection to maximize the sensitivity. The analysis of contaminated well water samples from Vietnam is demonstrated.     

Hydroxyquinolines with extended fluorophores: arrays for turn-on and ratiometric sensing of cations

8-Hydroxyquinoline-based ligands with extended conjugated fluorophores were designed to provide turn-on and ratiometric signal output optimized for use in fluorescence-based sensor arrays, where the changes in blue and green channels of the RGB signal are used to distinguish between cationic analytes.