Stabilizing effect of electrostatic vs. aromatic interactions in diproline nucleated peptide beta-hairpins

The contribution of Tyr-His vs. Cys-His interacting pairs to the scaffold stability of (D)Pro-(L)Pro nucleated peptide beta-hairpins has been examined. We present direct evidence for the superiority of the Cys-His pairs, mediated by sulphur-imidazole interactions, as added stabilizing agents of the beta-hairpin scaffold.

A naturally occurring amino acid substitution in the voltage-dependent sodium channel selectivity filter affects channel gating

The pore of sodium channels contains a selectivity filter made of 4 amino acids, D/E/K/A. In voltage sensitive sodium channel (Nav) channels from jellyfish to human the fourth amino acid is Ala. This Ala, when mutated to Asp, promotes slow inactivation. In some Nav channels of pufferfishes, the Ala is replaced with Gly. We studied the biophysical properties of an Ala-to-Gly substitution (A1529G) in rat Nav1.4 channel expressed in Xenopus oocytes alone or with a beta 1 subunit. The Ala-to-Gly substitution does not affect monovalent cation selectivity and positively shifts the voltage-dependent inactivation curve, although co-expression with a beta 1 subunit eliminates the difference between A1529G and WT. There is almost no difference in channel fast inactivation, but the beta 1 subunit accelerates WT current inactivation significantly more than it does the A1529G channels. The Ala-to-Gly substitution mainly influences the rate of recovery from slow inactivation. Again, the beta 1 subunit is less effective on speeding recovery of A1529G than the WT. We searched Nav channels in numerous databases and noted at least four other independent Ala-to-Gly substitutions in Nav channels in teleost fishes. Thus, the Ala-to-Gly substitution occurs more frequently than previously realized, possibly under selection for alterations of channel gating.

Facial selectivities in the nucleophilic additions of 2,3-unsaturated 3-arylsulfinyl pyranosides

2,3-Unsaturated 3-arylsulfinyl pyranosides undergo nucleophilic additions at C-2, with facial selectivities depending on the nucleophile and the substituent on sulfinyl sulfur. The reactions of such sugar vinyl sulfoxides lead to the addition of nucleophile preferring an axial orientation at C-2, with concomitant formation of an allylic bond at C-3 to C-4. This trend in the addition pattern is observed for primary amine, carbon and sulfur nucleophiles, whereas secondary amines prefer an equatorial addition at C-2. The effect of p-tolylthio-versus (p-isopropylphenyl)thio vinyl sulfoxide is that the equatorial nucleophilic addition is preferred even more with the latter vinyl sulfoxide. (C) 2013 Published by Elsevier Ltd.

Tb3+ sensitization in a deoxycholate organogel matrix, and selective quenching of luminescence by an aromatic nitro derivative

In this article, we present the discovery of a metallo-organogel derived from a Tb3+ salt and sodium deoxycholate (NaDCh) in methanol. The gel was made luminescent through sensitization of Tb3+ by doping with 2,3-dihydroxynaphthalene (DHN) in micromolar concentrations. Rheological measurements of the mechanical properties of the organogel confirmed the characteristics of a true gel. Significant quenching of Tb3+ luminescence was observed in the deoxycholate gel matrix by 2,4,7-trinitrofluorenone (TNF), but not by several other polynitro aromatics. Microscopic studies (AFM, TEM and SEM) revealed a highly entangled fibrous network. The xerogels retained luminescent properties suggesting the possibility for application in coatings, etc.

Conformational Diversity in Contryphans from Conus Venom: cis-trans Isomerisation and Aromatic/Proline Interactions in the 23-Membered Ring of a 7-Residue Peptide Disulfide Loop

Conformational diversity or shapeshifting in cyclic peptide natural products can, in principle, confer a single molecular entity with the property of binding to multiple receptors. Conformational equilibria have been probed in the contryphans, which are peptides derived from Conus venom possessing a 23-membered cyclic disulfide moiety. The natural sequences derived from Conus inscriptus, GCV(D)LYPWC* (In936) and Conus loroisii, GCP(D)WDPWC* (Lo959) differ in the number of proline residues within the macrocyclic ring. Structural characterisation of distinct conformational states arising from cis-trans equilibria about Xxx-Pro bonds is reported. Isomerisation about the C2-P3 bond is observed in the case of Lo959 and about the Y5-P6 bond in In936. Evidence is presented for as many as four distinct species in the case of the synthetic analogue V3P In936. The Tyr-Pro-Trp segment in In936 is characterised by distinct sidechain orientations as a consequence of aromatic/proline interactions as evidenced by specific sidechain-sidechain nuclear Overhauser effects and ring current shifted proton chemical shifts. Molecular dynamics simulations suggest that Tyr5 and Trp7 sidechain conformations are correlated and depend on the geometry of the Xxx-Pro bond. Thermodynamic parameters are derived for the cis trans equilibrium for In936. Studies on synthetic analogues provide insights into the role of sequence effects in modulating isomerisation about Xxx-Pro bonds.

Vibrational spectra of fluorene, 1-methylfluorene and 1,8-dimethylfluorene

In this paper, we report the gas phase infrared spectra of fluorene and its methylated derivatives using a heated multipass cell and argon as a carrier gas. The observed spectra in the 4000-400 cm(-1) range have been fitted using the modified scaled quantum mechanical force field (SQMFF) calculation with the 6-311G** basis. The advantage of using the modified SQMFF method is that it scales the force constants to find the best fit to the observed spectral lines by minimizing the fitting error. In this way we are able to assign all the observed fundamental bands in the spectra. With consecutive methyl substitutions two sets of bands are found to shift in a systematic way. The set of four aromatic C-H stretching vibrations around 3000 cm(-1) shifts toward lower frequencies while the single most intense aromatic C-H out-of-plane bending mode around 750 cm(-1) shifts toward higher frequencies. The reason for shifting of aromatic C-H stretching frequency toward lower wave numbers with gradual methyl substitution has been attributed to the lengthening of the C-H bonds due to the +I effect of the methyl groups to the ring current as revealed from the calculations. While the unexpected shifting of the aromatic C-H out-of-plane bend toward higher wave numbers with increasing methyl substitution is ascribed to the lowering of the number of adjacent aromatic C-H bonds on the plane of the benzene ring with gradual methyl substitutions. (C) 2013 Elsevier B.V. All rights reserved.

Effect of zinc substitution on the nanocobalt ferrite powders for nanoelectronic devices

Zinc substituted cobalt ferrite powders {Co(1-x)ZnxFe2O4} (0.0 <= x <= 0.5) were prepared by the solution combustion method. The structural, morphological, magnetic and electrical properties of as synthesized samples were studied. Powder X-ray diffraction patterns reveals single phase, cubic spinel structure with space group No. Fd (3) over barm (227). As zinc concentration increases, the lattice constant increases and the crystallite size decreases. The minimum crystallite size of similar to 12 nm was observed for x = 0.5 composition. The synthesized ferrite compounds show ferrimagnetic behavior, with coercivity value of 10779 Oe (Hard ferrite) at 20 K and 1298 Oe (soft ferrite) at room temperature (RT). The maximum saturation magnetization recorded for the Co0.5Zn0.5Fe2O4 composition was 99.78 emu g(-1) and 63.83 emu g(-1) at 20 K and RT respectively. The dielectric parameters such as dielectric constant, loss tangent and AC conductivity were determined as a function of frequency at RT. The magnetic and dielectric properties of the samples illustrates that the materials were quite useful for the fabrication of nanoelectronic devices. (C) 2013 Elsevier B.V. All rights reserved.

Selective and Efficient Detection of Nitro-Aromatic Explosives in Multiple Media including Water, Micelles, Organogel, and Solid Support

Selective detection of nitro-aromatic compounds (NACs) at nanomolar concentration is achieved for the first time in multiple media including water, micelles or in organogels as well as using test strips. Mechanism of interaction of NACs with highly fluorescent p-phenylenevinylene-based molecules has been described as the electron transfer phenomenon from the electron-rich chromophoric probe to the electron deficient NACs. The selectivity in sensing is guided by the pK(a) of the probes as well as the NACs under consideration. TNP-induced selective gel-to-sol transition in THF medium is also observed through the reorganization of molecular self-assembly and the portable test trips are made successfully for rapid on-site detection purpose.

Phenotypic characters of rice landraces reveal independent lineages of short-grain aromatic indica rice

Rice landraces are lineages developed by farmers through artificial selection during the long-term domestication process. Despite huge potential for crop improvement, they are largely understudied in India. Here, we analyse a suite of phenotypic characters from large numbers of Indian landraces comprised of both aromatic and non-aromatic varieties. Our primary aim was to investigate the major determinants of diversity, the strength of segregation among aromatic and non-aromatic landraces as well as that within aromatic landraces. Using principal component analysis, we found that grain length, width and weight, panicle weight and leaf length have the most substantial contribution. Discriminant analysis can effectively distinguish the majority of aromatic from non-aromatic landraces. More interestingly, within aromatic landraces long-grain traditional Basmati and short-grain non-Basmati aromatics remain morphologically well differentiated. The present research emphasizes the general patterns of phenotypic diversity and finds out the most important characters. It also confirms the existence of very unique short-grain aromatic landraces, perhaps carrying signatures of independent origin of an additional aroma quantitative trait locus in the indica group, unlike introgression of specific alleles of the BADH2 gene from the japonica group as in Basmati. We presume that this parallel origin and evolution of aroma in short-grain indica landraces are linked to the long history of rice domestication that involved inheritance of several traits from Oryza nivara, in addition to O. rufipogon. We conclude with a note that the insights from the phenotypic analysis essentially comprise the first part, which will likely be validated with subsequent molecular analysis.

Conformational Analysis of a 20-Membered Cyclic Peptide Disulfide from Conus virgo with a WPW Segment: Evidence for an Aromatic-Proline Sandwich

A novel peptide containing a single disulfide bond, CIWPWC (Vi804), has been isolated and characterised from the venom of the marine cone snail, Conus virgo. A precursor polypeptide sequence derived from complementary DNA, corresponding to the M-superfamily conotoxins, has been identified. The identity of the synthetic and natural peptide sequence has been established. A detailed analysis of the conformation in solution is reported for Vi804 and a synthetic analogue, (CIWPWC)-W-D ((D)W3-Vi804), in order to establish the structure of the novel WPW motif, which occurs in the context of a 20-membered macrocyclic disulfide. Vi804 exists exclusively in the cis W3P4 conformer in water and methanol, whereas (D)W3-Vi804 occurs exclusively as the trans conformer. NMR spectra revealed a W3P4 typeVI turn in Vi804 and a typeII turn in the analogue peptide, (D)W3-Vi804. The extremely high-field chemical shifts of the proline ring protons, together with specific nuclear Overhauser effects, are used to establish a conformation in which the proline ring is sandwiched between the flanking Trp residues, which emphasises a stabilising role for the aromatic-proline interactions, mediated predominantly by dispersion forces.

Effect of Zn substitution on the structural and magnetic properties of Ni-Co ferrites

A series of ferrite samples with the compositional formula, Ni0.5Co0.5-xZnxFe2O4 (0 <= x <= 0.5), was prepared using the citrate based sol gel method for the better understanding of zinc doping on the structural and magnetic properties. The Rietveld-refined X-ray diffraction data revealed that the samples are having cubic structure with the Fd-3m space group. The lattice parameter increased linearly with increasing Zn content. The surface morphology and stoichiometric ratio of the compositional elements were analyzed by scanning electron microscopy equipped with energy dispersive spectroscopy (EDS). EDS showed that the elemental ratios were stoichiometric. An examination of the magnetic properties revealed an increase in saturation magnetization with increasing Zn concentration up to x=0.3 and a decrease thereafter. These results could be explained using Neel's collinear two-sub-lattice model and three-sub-lattice non-collinear model suggested by Yafet and Kittel. The magnetic cubic anisotropy constant determined by the law of approach to saturation decreased with increasing Zn content. The underlying mechanism behind observed behavior was discussed qualitatively. (C) 2014 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Role of Cu2+ ions substitution in magnetic and conductivity behavior of nano-CoFe2O4

Cobalt copper ferrite nanopowders with composition Co1-xCu5Fe2O4 (0.0 <= x <= 0.5) was synthesized by solution combustion method. The powder X-ray diffraction studies reveal the formation of single ferrite phase with particle size of similar to 11-35 nm. Due to increase in electron density with in a material, X-ray density increase with increase of Cu2+ ions concentration. As Cu2+ ions concentration increases, saturation magnetization decreases from 38.5 to 26.7 emu g(-1). Further, the squareness ratio was found to be similar to 0.31-0.46 which was well below the typical value 1, which indicates the existence of single domain isolated ferrimagnetic samples. The dielectric and electrical modulus was studied over a frequency range of 1 Hz to 1 MHz at room temperature using the complex impedance spectroscopy technique. Impedance plots showed only one semi-circle which corresponds to the contributions of grain boundaries. The lower values of dielectric loss at higher frequency region may be quite useful for high frequency applications such as microwave devices. (C) 2014 Elsevier B.V. All rights reserved.

Remarkable isomer-selective gelation of aromatic solvents by a polymorph of a urea-linked bile acid-amino acid conjugate

We report an unusual, isomer-selective gelation of aromatic solvents by a polymorph of a urea-linked bile acid-amino acid conjugate. The gelator showed selectivity towards gelation of 1,2-disubstituted aromatic solvents.

Regioselective Synthesis of Vinyl Halides, Vinyl Sulfones, and Alkynes: A Tandem Intermolecular Nucleophilic and Electrophilic Vinylation of Tosylhydrazones

A diazo species is trapped in an intermolecular fashion by two independent ion species in tandem at the carbene center to install an electrophile and a nucleophile on the same carbon. This metal-free concept, which is unprecedented, has been illustrated by regioselective synthesis of a variety of vinyl halides, vinyl sulfones, and alkyne derivatives.

Evolution of Aromatic beta-Glucoside Utilization by Successive Mutational Steps in Escherichia coli

The bglA gene of Escherichia coli encodes phospho-beta-glucosidase A capable of hydrolyzing the plant-derived aromatic beta-glucoside arbutin. We report that the sequential accumulation of mutations in bglA can confer the ability to hydrolyze the related aromatic beta-glucosides esculin and salicin in two steps. In the first step, esculin hydrolysis is achieved through the acquisition of a four-nucleotide insertion within the promoter of the bglA gene, resulting in enhanced steady-state levels of the bglA transcript. In the second step, hydrolysis of salicin is achieved through the acquisition of a point mutation within the bglA structural gene close to the active site without the loss of the original catabolic activity against arbutin. These studies underscore the ability of microorganisms to evolve additional metabolic capabilities by mutational modification of preexisting genetic systems under selection pressure, thereby expanding their repertoire of utilizable substrates.