A 14N nuclear quadrupole resonance study of phase transitions and molecular dynamics in hydrogen bonded organic antiferroelectrics 55DMBP-H2ca and 1,5-NPD-H2ca

The temperature dependence of the (14)N NQR frequencies has been measured in antiferroelectric and paraelectric 55DMBP-H(2)ca and 1,5-NPD-H(2)ca. In both compounds we observe two non-equivalent nitrogen positions (N(+)-H···O(-) and N···H-O) in the antiferroelectric phase. The two nitrogen positions become equivalent (N···H···O) in the paraelectric phase. The critical exponent of the local antiferroelectric order parameter has been determined from the NQR data. The principal values of the quadrupole coupling tensor correlate in both compounds. The correlation diagrams clearly show how a proton migrates from the antiferroelectric position towards the paraelectric position in the bifurcated hydrogen bond on increasing the temperature. A slow motion has been observed in 55DMBP-H(2)ca by the (1)H and (14)N spin-lattice relaxation. An analysis of the spin-lattice relaxation data suggests a slow exchange between two non-planar conformations of the bipyridine molecule.     

Nitroxide-fluorophore double probes: a potential tool for studying membrane heterogeneity by ESR and fluorescence

A serious drawback of ESR, particularly in its application to cells, is the lack of information on the location of spin probes in the system. In order to realize real time tracking, a spin probe was combined with a fluorophore in a new kind of nitroxide-fluorophore double probe which, in addition to information about lipid dynamics, enables visualization by fluorescence microscopy. The two sets of probes synthesized are based on an amino-alkyne-functionalized sugar that serves as a central polar group and as a linker between the 7-nitrobenz-2-oxa-1,3-diazol-4-yl (NBD) fluorophore and the derivative of the spin labelled fatty acid. In this setting, the location of the fluorophore is restricted to the water-lipid interface, while the nitroxide is located deep in the lipid bilayer. Preliminary tests on cells show preferential localization of both probes in the plasma membrane, with a relatively slow redistribution to other membranes of the cell. We believe that such double probes would be particularly useful for studies of plasma membrane heterogeneity and associated cellular processes.     

1-(2-Picolyl)-substituted 1,2,3-triazole as novel chelating ligand for the preparation of ruthenium complexes with potential anticancer activity

The 1,4-disubstituted 1,2,3-triazole ligand prepared by click chemistry 1-(2-picolyl)-4-phenyl-1H-1,2,3-triazole (ppt) was investigated as novel chelating ligand for Ru(II) complexes with potential antitumor activity. The preparation and structural characterization, mainly by NMR spectroscopy in solution and by X-ray crystallography in the solid state, of four new Ru(II) complexes is reported: two isomeric Ru-dmso compounds, trans,cis-[RuCl(2)(dmso-S)(2)(ppt)] (1) and cis,cis-[RuCl(2)(dmso-S)(2)(ppt)] (2), and two half-sandwich Ru-[9]aneS(3) coordination compounds, [Ru([9]aneS(3))(dmso-S)(ppt)][CF(3)SO(3)](2) (3) and [Ru([9]aneS(3))Cl(ppt)][CF(3)SO(3)] (4). In all compounds ppt firmly binds to ruthenium in a bidentate fashion through the pyridyl nitrogen atom and the triazole N2, thus forming a puckered six-membered ring. The chemical behavior in aqueous solution of the water-soluble complexes 3 and 4 was studied by UV-Vis and NMR spectroscopy and compared to that of the previously described organometallic analogue [Ru(η(6)-p-cymene)Cl(ppt)][Cl] (5) in view of their potential antitumor activity. Compounds 3-5 were tested also in vitro for cytotoxic activity against two human cancer cell lines, one sensitive and one resistant to cisplatin, in comparison with cisplatin. Compound 4, the one that aquates faster, was found to be more cytotoxic than cisplatin against human lung squamose carcinoma cell line (A-549).     

Phonon-driven proton transfer in 3,5-pyridine dicarboxylic acid studied by 2H, 14N, and 17O nuclear quadrupole resonance

Hydrogen bonding in crystalline 3,5-pyridine dicarboxylic acid has been studied by (2)H, (14)N, and (17)O nuclear quadrupole resonance. The (2)H and (17)O data show the presence of two distinct hydrogen bonds, a "normal" O-H···O bond and a short, strong N···H···O bond, with significantly different NQR parameters. In the latter, the temperature variation of the (14)N nuclear quadrupole resonance (NQR) parameters is related to the phonon-driven proton transfer in the N···H···O hydrogen bond. The temperature dependence of the N···H and H···O distances in the N···H···O hydrogen bond is extracted from the (14)N NQR data.     

Multifunctional water and oil repellent and antimicrobial properties of finished cotton: influence of sol–gel finishing procedure

Cotton fabric was treated with two-component water- and oil-repellent antimicrobial coatings consisting of the commercial aqueous organic–inorganic hybrid precursors fluoroalkyl-functional siloxane (FAS) and 3-(trimethoxysilyl)-propyldimethyloctadecyl ammonium chloride (SiQAC) of different concentrations. Two different application procedures were used: a one-step treatment (S1) by a sol mixture consisting of both precursors [coating FAS-SiQAC (S1)] and a two-step treatment (S2) by SiQAC sol and then FAS sol [coating SiQAC + FAS (S2)]. The functional properties of the coatings were determined from liquid contact angle measurements and antimicrobial activity, as well as FTIR and XPS analyses. Although both treatments gave the cotton fabric superhydrophobic and oleophobic properties at a sufficient sol concentration, procedure S1 was found to be more effective than procedure S2. The antibacterial properties of the SiQAC + FAS (S2) coating were superior to those of the FAS-SiQAC (S1) coating. For both two-component coatings, the active bacteriostatic activity of SiQAC was enhanced by the passive antibacterial activity of FAS. Two-component coatings did not provide significant antifungal protection. Repetitive washing gradually deteriorated both coatings but the coating applied by procedure S2 seemed to be slightly more durable than that applied by S1. The two-component coatings caused an increase in the flexibility and a slight decrease in the fabric breaking strength and air permeability of the cotton sample.     

Parallel‐ProBiS: Fast parallel algorithm for local structural comparison of protein structures and binding sites

The ProBiS algorithm performs a local structural comparison of the query protein surface against the nonredundant database of protein structures. It finds proteins that have binding sites in common with the query protein. Here, we present a new parallelized algorithm, Parallel‐ProBiS, for detecting similar binding sites on clusters of computers. The obtained speedups of the parallel ProBiS scale almost ideally with the number of computing cores up to about 64 computing cores. Scaling is better for larger than for smaller query proteins. For a protein with almost 600 amino acids, the maximum speedup of 180 was achieved on two interconnected clusters with 248 computing cores. Source code of Parallel‐ProBiS is available for download free for academic users at http://probis.cmm.ki.si/download . © 2012 Wiley Periodicals, Inc.     

NQR investigation and characterization of cocrystals and crystal polymorphs

The application of ¹⁴N NQR to the study of cocrystals and crystal polymorphs is reviewed. In ferroelectric and antiferroelectric organic cocrystals ¹⁴N NQR is used to determine proton position in an N-H...O hydrogen bond and proton displacement below T_C. In cocrystal isonicitinamide – oxalic acid (2:1) ¹⁴N NQR is used to distinguish between two polymorphs and to determine the type of the hydrogen bond (N^?...H-O). The difference in the ¹⁴N NQR spectra of cocrystal formers and cocrystal is investigated in case of carbamazepine, saccharin and carbamazepine - saccharin (1:1). The experimental resolution allows an unambiguous distinction between the ¹⁴N NQR spectrum of the cocrystal and the ¹⁴N NQR spectra of the cocrystal formers. The possibility of application of NQR and double resonance for the determination of the inhomogeneity of the sample and for the study of the life time of an unstable polymorph is discussed.     

Two-dimensional measurements of laser-induced breakdown in air by high-speed two-frame shadowgraphy

We present two-dimensional measurements of the laser-induced plasma development and shock wave evolution in air. The breakdown is induced by a Q-switched Nd:YAG laser (λ=1064 nm) with a pulse duration of 4 ns. To study these fast laser-induced phenomena, we have developed a high-speed, two frame shadowgraph method. It enables 2D visualization of a laser-induced event in two time instances, which are delayed by an arbitrary time interval in the range from 300 ps to 30 ns. The established method is based on 30 ps, green (λ=532 nm), and linearly polarized laser pulse, which is split into two orthogonally polarized illumination pulses for direct and delayed illumination of the breakdown area. Exploiting polarization of the probe pulses, we capture two temporally and spatially separated frames with two CCD cameras. Special attention is given to the subsequent data processing, especially to the minimization of the systematic error due to alignment of both images, and to the determination of 2D velocity distribution from the captured image pairs.     

Interferometric determination of the high-intensity laser-pulse-material interaction site

We developed a method that accurately determines an unknown position of the high-intensity laser-pulse-material interaction site on the front side of a plate. It is based on interferometric measurements of a normal displacement at known positions on the plate’s rear side. The displacement is caused by reflections of various pulsed-laser-induced mechanical waves. We have superseded the long-established time-of-flight approach with the improved, triple-echo method. To accurately locate the origin of the laser-induced ultrasound on the plate with a known thickness, we only need to detect the arrivals of the first three consecutive mode unconverted waves. Our method works without knowing the propagation velocities of various ultrasonic waves and additionally solves some time-related drawbacks of the conventional time-of-flight approach. The relative uncertainty of the measured source-receiver separations obtained with the presented method is less than 0.01.     

Unique structural features of interconverting monomeric and dimeric G-quadruplexes adopted by a sequence from the intron of the N-myc gene

A multidimensional heteronuclear NMR study has demonstrated that a guanine-rich DNA oligonucleotide originating from the N-myc gene folds into G-quadruplex structures in the presence of K(+), NH(4)(+), and Na(+) ions. A monomeric G-quadruplex formed in K(+) ion containing solution exhibits three G-quartets and flexible propeller-type loops. The 3D structure with three single nucleotide loops represents a missing element in structures of parallel G-quadruplexes. The structural features together with the high temperature stability are suggestive of the specific biological role of G-quadruplex formation within the intron of the N-myc gene. An increase in K(+) ion and oligonucleotide concentrations resulted in transformation of the monomeric G-quadruplex into a dimeric form. The dimeric G-quadruplex exhibits six stacked G-quartets, parallel strand orientations, and propeller-type loops. A link between the third and the fourth G-quartets consists of two adenine residues that are flipped out to facilitate consecutive stacking of six G-quartets.