Negative Cooperativity and High Affinity in Chitooligosaccharide Binding by a Mycobacterium smegmatis Protein Containing LysM and Lectin Domains

LysM domains have been recognized in bacteria and eukaryotes as carbohydrate-binding protein modules, but the mechanism of their binding to chitooligosaccharides has been underexplored. Binding of a Mycobacterium smegmatis protein containing a lectin (MSL) and one LysM domain to chitooligosaccharides has been studied using isothermal titration calorimetry and fluorescence titration that demonstrate the presence of two binding sites of nonidentical affinities per dimeric MSL-LysM molecule. The affinity of the molecule for chitooligosaccharides correlates with the length of the carbohydrate chain. Its binding to chitooligosaccharides is characterized by negative cooperativity in the interactions of the two domains. Apparently, the flexibility of the long linker that connects the LysM and MSL domains plays a facilitating role in this recognition. The LysM domain in the MSL-LysM molecule, like other bacterial domains but unlike plant LysM domains, recognizes equally well peptidoglycan fragments as well as chitin polymers. Interestingly, in the case presented here, two LysM domains are enough for binding to peptidoglycan in contrast to the three reportedly required by the LysM domains of Bacillus subtilis and Lactococcus lactis. Also, the affinity of the MSL-LysM molecule for chitooligosaccharides is higher than that of LysM-chitooligosaccharide interactions reported so far.

Outstanding dielectric constant and piezoelectric coefficient in electrospun nanofiber mats of PVDF containing silver decorated multiwall carbon nanotubes: assessing through piezoresponse force microscopy

In order to enhance the piezoelectric b-phase, PVDF was electrospun from DMF solution. The enhanced b-phase was discerned by comparing the electrospun fibers against the melt mixed samples. While both the processes resulted in phase transformation of a-to electroactive b-polymorph in PVDF, the fraction of b-phase was strongly dependent on the adopted process. Two different nanoscopic particles: carboxyl functionalized multiwall carbon nanotubes (CNTs) and silver (Ag) decorated CNTs were used to further enhance the piezoelectric coefficient in the electrospun fibers. Fourier transform infrared spectroscopy (FTIR) and wide-angle X-ray diffraction (XRD) supports the development of piezoelectric b-phase in PVDF. It was concluded that electrospinning was the best technique for inducing the b-polymorph in PVDF. This was attributed to the high voltage electrostatic field that generates extensional forces on the polymer chains that aligns the dipoles in one direction. The ferroelectric and piezoelectric measurement on electrospun fibers were studied using piezo-response force microscope (PFM). The Ag-CNTs filled PVDF electrospun fibers showed the highest piezoelectric coefficient (d(33) = 54 pm V-1) in contrast to PVDF/CNT fibers (35 pm V-1) and neat PVDF (30 pm V-1). This study demonstrates that the piezoelectric coefficient can be enhanced significantly by electrospinning PVDF containing Ag decorated nanoparticles.

Crystal structure of a tripeptide containing aminocyclododecane carboxylic acid: a supramolecular twisted parallel -sheet in crystals

The crystal structure of a tripeptide Boc-Leu-Val-Ac(12)c-OMe (1) is determined, which incorporates a bulky 1-aminocyclododecane-1-carboxylic acid (Ac(12)c) side chain. The peptide adopts a semi-extended backbone conformation for Leu and Val residues, while the backbone torsion angles of the C-,C--dialkylated residue Ac(12)c are in the helical region of the Ramachandran map. The molecular packing of 1 revealed a unique supramolecular twisted parallel -sheet coiling into a helical architecture in crystals, with the bulky hydrophobic Ac(12)c side chains projecting outward the helical column. This arrangement resembles the packing of peptide helices in crystal structures. Although short oligopeptides often assemble as parallel or anti-parallel -sheet in crystals, twisted or helical -sheet formation has been observed in a few examples of dipeptide crystal structures. Peptide 1 presents the first example of a tripeptide showing twisted -sheet assembly in crystals. Copyright (c) 2016 European Peptide Society and John Wiley & Sons, Ltd.

Dielectric investigation of high-k yttrium copper titanate thin films

We report on the first dielectric investigation of high-k yttrium copper titanate thin films, which were demonstrated to be very promising for nanoelectronics applications. The dielectric constant of these films is found to vary from 100 down to 24 (at 100 kHz) as a function of deposition conditions, namely oxygen pressure and film thickness. The physical origin of such variation was investigated in the framework of universal dielectric response and Cole-Cole relations and by means of voltage dependence studies of the dielectric constant. Surface-related effects and charge hopping polarization processes, strictly dependent on the film microstructure, are suggested to be mainly responsible for the observed dielectric response. In particular, the bulky behaviour of thick films deposited at lower oxygen pressure evolves towards a more complex and electrically heterogeneous structure when either the thickness decreases down to 50 nm or the films are grown under high oxygen pressure.

Crystal structure of a tripeptide containing aminocyclododecane carboxylic acid: a supramolecular twisted parallel -sheet in crystals

The crystal structure of a tripeptide Boc-Leu-Val-Ac(12)c-OMe (1) is determined, which incorporates a bulky 1-aminocyclododecane-1-carboxylic acid (Ac(12)c) side chain. The peptide adopts a semi-extended backbone conformation for Leu and Val residues, while the backbone torsion angles of the C-,C--dialkylated residue Ac(12)c are in the helical region of the Ramachandran map. The molecular packing of 1 revealed a unique supramolecular twisted parallel -sheet coiling into a helical architecture in crystals, with the bulky hydrophobic Ac(12)c side chains projecting outward the helical column. This arrangement resembles the packing of peptide helices in crystal structures. Although short oligopeptides often assemble as parallel or anti-parallel -sheet in crystals, twisted or helical -sheet formation has been observed in a few examples of dipeptide crystal structures. Peptide 1 presents the first example of a tripeptide showing twisted -sheet assembly in crystals. Copyright (c) 2016 European Peptide Society and John Wiley & Sons, Ltd.

Dielectric investigation of high-k yttrium copper titanate thin films

We report on the first dielectric investigation of high-k yttrium copper titanate thin films, which were demonstrated to be very promising for nanoelectronics applications. The dielectric constant of these films is found to vary from 100 down to 24 (at 100 kHz) as a function of deposition conditions, namely oxygen pressure and film thickness. The physical origin of such variation was investigated in the framework of universal dielectric response and Cole-Cole relations and by means of voltage dependence studies of the dielectric constant. Surface-related effects and charge hopping polarization processes, strictly dependent on the film microstructure, are suggested to be mainly responsible for the observed dielectric response. In particular, the bulky behaviour of thick films deposited at lower oxygen pressure evolves towards a more complex and electrically heterogeneous structure when either the thickness decreases down to 50 nm or the films are grown under high oxygen pressure.

Photocytotoxic ternary copper(II) complexes of histamine Schiff base and pyridyl ligands

Ternary copper(Il) complexes of salicylaldehyde-histamine Schiff base (HL) and pyridyl ligands, viz. Cu(bpy)(L)](ClO4) (1) and Cu(dppz)(L)](C104) (2), where bpy is 2,2'-bipyridine (in 1) and dppz is dipyrido3,2-a:2',3'-c]phenazine (in 2), were synthesized, characterized and their DNA binding, photo-activated DNA cleavage activity and photocytotoxicity studied. The 1:1 electrolytic one-electron paramagnetic complexes showed a d-d band near 670 nm in aqueous DMF (1:1 v/v). The crystal structure of complex 1 showed the metal in CuN4O distorted square-pyramidal geometry. Complex 2 intercalatively binds to calf-thymus (ct) DNA with a binding constant (K-b) of similar to 10(5) M-1. It exhibited moderate chemical nuclease activity but excellent DNA photocleavage activity in red light of 647 nm forming (OH)-O-center dot radicals. It showed remarkable photocytotoxicity in human cervical cancer cells (HeLa) giving IC50 of 1.6 mu M in visible light (400-700 nm) with low dark toxicity. The photo-induced cell death is via generation of oxidative stress by reactive oxygen species.

Effect of current density on the microstructure and corrosion properties of plasma electrolytic oxidation (PEO) coatings on AM50 Mg alloy produced in an electrolyte containing clay additives

Plasma electrolytic oxidation coatings were produced on AM50 Mg alloy in alkaline phosphate based electrolyte with montmorillonite clay additives employing current densities of 30, 60, and 120 mA/cm(2). The effect of current density on the microstructure and corrosion properties of the coating was investigated. The clay additives got melted and reactively incorporated into the coating forming an amorphous phase, at all the current densities. However, the coating was predominantly amorphous only at 30 mA/cm(2) and with increasing current density, increasing fractions of crystalline phases were formed. Higher current densities resulted in increased thickness of the coating, but reduced the compactness of the coatings. Electrochemical impedance spectroscopy tests in 0.5 wt.% (0.08 M) and 3.5 wt.% (0.6 M) NaCl solution revealed that the coatings processed at 30 mA/cm(2) exhibited a relatively better initial corrosion resistance owing to its relatively defect-free barrier layer and compactness of the coating. However, the presence of amorphous phases in significant amounts and lack of MgO in the coating resulted in increased rate of dissolution of the coatings and degradation of corrosion resistance. Coatings produced at higher current densities exhibited initial inferior corrosion resistance due to a more defective barrier layer and increased porosity in pore band and outer porous layer. However, the increased amount of crystalline phases and an increased amount of MgO, which resisted dissolution, counterbalanced the negative effects of defective barrier and increased porosity resulting in a relatively lower rate of the degradation of the corrosion resistance. Thus, the corrosion resistance of all the coatings continuously decreased with time and became similar after prolonged immersion in NaCl solution. Increasing current density, therefore, did not prove to be beneficial for the improvement of the corrosion performance of the PEO coatings. (C) 2016 Elsevier B.V. All rights reserved.

Stimuli and shape responsive `boron-containing' luminescent organic materials

Recent advancements of material science and its applications have been immensely influenced by the modern development of organic luminescent materials. Among all organic luminogens, boron containing compounds have already established their stature as one of the indispensable classes of luminescent dyes. Boron, in its various forms e. g. triarylboranes, borate dyes and boron clusters, has attracted considerable attention owing to its several unique and excellent photophysical features. In very recent times, beyond the realms of solution-state studies, luminescent boron-containing compounds have emerged as a large and versatile class of stimuli responsive materials. Based on several fundamental concepts of chemistry, researchers have come up with an admirable variety of boron-containing materials with AIE (aggregation-induced emission), mechano-responsive luminescence, thermoresponsive-luminescence as well as a number of purely organic phosphorescent materials and other standalone examples. The unique chemical as well as physical properties of boron-containing compounds are largely responsible for the development of such materials. In this review these new findings are brought together.

Remarkable photo-induced anticancer activity of vitamin-S6 Schiff base copper(II) complexes of pyridyl bases

Vitamin-B6 (VB6) Schiff base (H2L) copper(II) complexes of pyridyl bases, viz. Cu(bpy)(L)] (1), Cu(phen)(L)] (2) and Cu(dppz)(L)] (3), where bpy is 2,2'-bipyridine, phen is 1,10-phenanthroline and dppz is dipyrido3,2-a:2',3'c]phenazine are synthesized, characterized and their phto-induced anticancer activity studied. The non-electrolytic one electron paramagnetic complexes exhibit a d-d band near 700 nm in DMF. The dppz complex intercalatively binds to calf-thymus DNA with binding constant (K-b) values of similar to 10(6) M-1. This complex exhibits low chemical nuclease activity but excellent DNA photocleavage activity when irradiated with red light of 705 nm forming (OH)-O-center dot radical. It displays remarkable photocytotoxicity in human cervical cancer cells (HeLa) giving IC50 value of 0.9 mu M in visible light (400-700 nm) while being less toxic in darkness (IC50 : 23 mu M). The cellular uptake of the complexes seems to be via VB6 transporting membrane carrier mediated diffusion pathway. Photo-induced cell death follows apoptotic pathway involving photo-generated intracellular reactive oxygen species.

Formation of Fivefold Deformation Twins in Nanocrystalline Face-Centered-Cubic Copper Based on Molecular Dynamics Simulations

Fivefold deformation twins were reported recently to be observed in the experiment of the nanocrystalline face-centered-cubic metals and alloys. However, they were not predicted previously based on the molecular dynamics (MD) simulations and the reason was thought to be a uniaxial tension considered in the simulations. In the present investigation, through introducing pretwins in grain regions, using the MD simulations, the authors predict out the fivefold deformation twins in the grain regions of the nanocrystal grain cell, which undergoes a uniaxial tension. It is shown in their simulation results that series of Shockley partial dislocations emitted from grain boundaries provide sequential twining mechanism, which results in fivefold deformation twins. (c) 2006 American Institute of Physics.

Improving Nucleation in the Fabrication of High-Quality 3D Macro-Porous Copper Film through The Surface-Modification of A Polystyrene Colloid-Assembled Template

A new approach is developed to the fabrication of high-quality three-dimensional macro-porous copper films. A highly-ordered macroporous copper film is successfully produced on a polystyrene sphere (PS) template that has been modified by sodium dodecyl sulfate (SDS). It is shown that this procedure can change a hydrophobic surface of PS template into a hydrophilic surface. The present study is devoted to the influence of the electrolyte solution transport on the nucleation process. It is demonstrated that the permeability of the electrolyte solution in the nanochannels of the PS template plays an important role in the chemical electrodeposition of high-quality macroporous copper film. The permeability is drastically enhanced in our experiment through the surface modi. cation of the PS templates. The method could be used to homogeneously produce a large number of nucleations on a substrate, which is a key factor for the fabrication of the high-quality macroporous copper film.

Mechanism of nucleation and precipitation in Li containing Al-Zn-Mg-Cu alloys

Investigations on the aging hardening behavior of four Al-Li-Zn-Mg-Cu alloys were carried out using differential scanning calorimetry, transmission electron microscopy and hardness measurement. It is shown that the addition of Li inhibits the formation of Zn-rich G.P. zones in Al-Zn-Mg-Cu alloys. The dominant aging hardening precipitates is delta'(Al3Li) phase. Coarse T ((AlZn)(49)Mg-32) phase, instead of MgZn2, precipitates primarily on grain boundaries, and provides little strengthening. The multi-stop aging involving plastic deformation introduces in the matrix a high concentration of structural defects. These defects play different role on the nucleation of Zn-rich G.P. zones in different alloys. For the Li free alloy, structural defects act as vacancy sinks and tend to suppress the homogeneous precipitation of G.P. zones, while for the Li containing alloys, these defects promote the heterogeneous nucleation of G.P. zones and metastable MgZn2. A significant aging hardening effect is attained in deformed Li containing alloys due to the extra precipitation of fine MgZn2 in the matrix combined with deformation hardening.