Hybrid peptide hairpins containing alpha- and omega-amino acids: Conformational analysis of decapeptides with unsubstituted beta-, gamma-, and delta-residues at positions 3 and 8

The effects of inserting unsubstituted omega-amino acids into the strand segments of model beta-hairpin peptides was investigated by using four synthetic decapeptides, Boc-Lcu-Val-Xxx-Val-D-Pro-Gly-Leu-Xxx-Val-Val- OMe: pepticle 1 (Xxx=Gly), pepticle 2 (Xxx=beta Gly=beta hGly=homoglycine, beta-glycine), pepticle 3 (Xxx=gamma Abu=gamma-aminobutyric acid), pepticle 4 (Xxx= delta Ava=delta-aminovaleric acid). H-1 NMR studies (500 MHz, methanol) reveal several critical cross-strand NOEs, providing evidence for P-hairpin conformations in peptides 2-4. In peptide 3, the NMR results support the formation of the nucleating turn, however, evidence for cross-strand registry is not detected. Single-crystal X-ray diffraction studies of peptide 3 reveal a beta-hairpin conformation for both molecules in the crystallographic asymmetric unit, stabilized by four cross-strand hydrogen bonds, with the gamma Abu residues accommodated within the strands. The D-Pro-Gly segment in both molecules (A,B) adopts a type II' beta-turn conformation. The circular dichroism spectrum for peptide 3 is characterized by a negative CD band at 229 rim, whereas for peptides 2 and 4, the negative band is centered at 225 nm, suggesting a correlation between the orientation of the amide units in the strand segments and the observed CD pattern.

Omega-Hydroxylation of acyclic monoterpene alcohols by rat lung microsomes

Rat lung microsomes were shown to �-hydroxylate acyclic monoterpene alcohols in the presence of NADPH and O2. NADH could neither support hydroxylation efficiently nor did it show synergistic effect. The hydroxylase activity was greater in microsomes prepared from β-naphthoflavone (BNF)-treated rats than from phenobarbital (PB)-treated or control microsomal preparations. Hydroxylation was specific to the C-8 position in geraniol and has a pH optimum of 7.8. The inhibition of the hydroxylase activity by SKF-525A, CO, N-ethylmaleimide, ellipticine, α-naphthoflavone, cyt. Image and p-CMB indicated the involvement of the cyt. P-450 system. However, NaN3 stimulated the hydroxylase activity to a significant level. Rat kidney microsomes were also capable of �-hydroxylating geraniol although the activity was lower than that observed with lungs.

3-D kinematical conservation laws (KCL): Evolution of a surface in R-3 - in particular propagation of a nonlinear wavefront

3-D KCL are equations of evolution of a propagating surface (or a wavefront) Omega(t), in 3-space dimensions and were first derived by Giles, Prasad and Ravindran in 1995 assuming the motion of the surface to be isotropic. Here we discuss various properties of these 3-D KCL.These are the most general equations in conservation form, governing the evolution of Omega(t) with singularities which we call kinks and which are curves across which the normal n to Omega(t) and amplitude won Omega(t) are discontinuous. From KCL we derive a system of six differential equations and show that the KCL system is equivalent to the ray equations of 2, The six independent equations and an energy transport equation (for small amplitude waves in a polytropic gas) involving an amplitude w (which is related to the normal velocity m of Omega(t)) form a completely determined system of seven equations. We have determined eigenvalues of the system by a very novel method and find that the system has two distinct nonzero eigenvalues and five zero eigenvalues and the dimension of the eigenspace associated with the multiple eigenvalue 0 is only 4. For an appropriately defined m, the two nonzero eigenvalues are real when m > 1 and pure imaginary when m < 1. Finally we give some examples of evolution of weakly nonlinear wavefronts.

Omega-hydroxylation of acyclic monoterpene alcohols by rat lung microsomes

Rat lung microsomes were shown to ω-hydroxylate acyclic monoterpene alcohols in the presence of NADPH and O2. NADH could neither support hydroxylation efficiently nor did it show synergistic effect. The hydroxylase activity was greater in microsomes prepared from β-naphthoflavone (BNF)-treated rats than from phenobarbital (PB)-treated or control microsomal preparations. Hydroxylation was specific to the C-8 position in geraniol and has a pH optimum of 7.8. The inhibition of the hydroxylase activity by SKF-525A, CO, N-ethylmaleimide, ellipticine, α-naphthoflavone, cyt. Image and p-CMB indicated the involvement of the cyt. P-450 system. However, NaN3 stimulated the hydroxylase activity to a significant level. Rat kidney microsomes were also capable of ω-hydroxylating geraniol although the activity was lower than that observed with lungs.

Stereochemistry of peptides and polypeptides containing omega amino acids

The omega amino acids have a larger degree of conformational variability than the alpha amino acids, leading to a greater diversity of backbone structures in peptides and polypeptides. The synthetic accessibility of chiral beta-amino acids and the recent observation of novel helical folds in oligomers of cyclic beta-amino acids has led to renewed interest in the stereochemistry of omega-amino acid containing peptides. This review focuses on the conformational characteristics of the polymethylene chain in omega-amino acid segments and surveys structural features in peptides established by X-ray diffraction. The literature on polymers of achiral omega-amino acids (nylon derivatives) and chiral, substituted derivatives derived from trifunctional alpha-amino acids, reveals that while sheet-like, intermolecular hydrogen bonded structures are formed by the former, folded helices appear favoured by the latter. omega-Amino acids promise to expand the repertoire of peptide folds.

Effect of pulse profile variations on measurement of eccentricity in orbits of Cen X-3 and SMC X-1

It has long been argued that better timing precision allowed by satellites like Rossi X-ray Timing Explorer (RXTE) will allow us to measure the orbital eccentricity and the angle of periastron of some of the bright persistent high-mass X-ray binaries (HMXBs) and hence a possible measurement of apsidal motion in these system. Measuring the rate of apsidal motion allows one to estimate the apsidal motion constant of the mass losing companion star and hence allows for the direct testing of the stellar structure models for these giant stars present in the HMXBs. In the present paper, we use the archival RXTE data of two bright persistent sources, namely Cen X-3 and SMC X-1, to measure the very small orbital eccentricity and the angle of periastron. We find that the small variations in the pulse profiles of these sources, rather than the intrinsic time resolution provided by RXTE, limit the accuracy with which we can measure arrival time of the pulses from these sources. This influences the accuracy with which one can measure the orbital parameters, especially the very small eccentricity and the angle of periastron in these sources. The observations of SMC X-1 in the year 2000 were taken during the high-flux state of the source and we could determine the orbital eccentricity and omega using this data set.

An Application of 3-D Kinematical Conservation Laws: Propagation of a 3-D Wavefront

Three-dimensional (3-D) kinematical conservation laws (KCL) are equations of evolution of a propagating surface Omega(t) in three space dimensions. We start with a brief review of the 3-D KCL system and mention some of its properties relevant to this paper. The 3-D KCL, a system of six conservation laws, is an underdetermined system to which we add an energy transport equation for a small amplitude 3-D nonlinear wavefront propagating in a polytropic gas in a uniform state and at rest. We call the enlarged system of 3-D KCL with the energy transport equation equations of weakly nonlinear ray theory (WNLRT). We highlight some interesting properties of the eigenstructure of the equations of WNLRT, but the main aim of this paper is to test the numerical efficacy of this system of seven conservation laws. We take several initial shapes for a nonlinear wavefront with a suitable amplitude distribution on it and let it evolve according to the 3-D WNLRT. The 3-D WNLRT is a weakly hyperbolic 7 x 7 system that is highly nonlinear. Here we use the staggered Lax-Friedrichs and Nessyahu-Tadmor central schemes and have obtained some very interesting shapes of the wavefronts. We find the 3-D KCL to be suitable for solving many complex problems for which there presently seems to be no other method capable of giving such physically realistic features.

Identifying N60D mutation in omega subunit of Escherichia coli RNA polymerase by bottom-up proteomic approach

Escherichia coli RNA polymerase is a multi-subunit enzyme containing alpha(2)beta beta'omega sigma, which transcribes DNA template to intermediate RNA product in a sequence specific manner. Although most of the subunits are essential for its function, the smallest subunit omega (average molecular mass similar to 10,105 Da) can be deleted without affecting bacterial growth. Creating a mutant of the omega subunit can aid in improving the understanding of its role. Sequencing of rpoZ gene that codes for omega subunit from a mutant variant suggested a substitution mutation at position 60 of the protein: asparagine (N) -> aspartic acid (D). This mutation was verified at the protein level by following a typical mass spectrometry (MS) based bottom-up proteomic approach. Characterization of in-gel trypsin digested samples by reverse phase liquid chromatography (LC) coupled to electrospray ionization (ESI)-tandem mass spectrometry (MS/MS) enabled in ascertaining this mutation. Electron transfer dissociation (ETD) of triply charged (M + 3H)(3+)] tryptic peptides (residues 53-67]), EIEEGLINNQILDVR from wild-type and EIEEGLIDNQILDVR from mutant, facilitated in unambiguously determining the site of mutation at residue 60.

Conformational properties of hybrid peptides containing alpha and omega-amino acids

This review briefly surveys the conformational properties of guest omega-amino acid residues when incorporated into host alpha-peptide sequences. The results presented focus primarily on the use of beta- and gamma-residues in alphaomega sequences. The insertion of additional methylene groups into peptide backbones enhances the range of accessible conformations, introducing additional torsional variables. A nomenclature system, which permits ready comparisons between alpha-peptides and hybrid sequences, is defined. Crystal structure determination of hybrid peptides, which adopt helical and beta-hairpin conformations permits the characterization of backbone conformational parameters for beta- and gamma-residues inserted into regular alpha-polypeptide structures. Substituted beta- and gamma-residues are more limited in the range of accessible conformation than their unsubstituted counterparts. The achiral beta,beta-disubstituted gamma-amino acid, gabapentin, is an example of a stereochemically constrained residue in which the torsion angles about the C-beta-C-gamma (theta(1)) and C-alpha-C-beta (theta(2)) bonds are restricted to the gauche conformation. Hybrid sequences permit the design of novel hydrogen bonded rings in peptide structures.

Dielectric and Impedance Studies on 0.5Li(2)O-0.5K(2)O-2B(2)O(3) Glasses

Transparent glasses in the system 0.5Li(2)O-0.5K(2)O-2B(2)O(3) (LKBO) were fabricated via the conventional melt quenching technique. Amorphous and glassy nature of the samples was confirmed by X-ray diffraction and differential scanning calorimetry (DSC) respectively. Complex dielectric and impedance studies were conducted on the samples at different temperatures in the 100 Hz-10 MHz frequency range. ac conductivity was calculated from the dielectric data and the conductivity relaxation was found to obey the Jonscher's law. The Nyquist's plots (Z `'(omega) vs. Z'(omega)) showed single suppressed semicircles at all the temperatures under study indicating the non ideal Debye type relaxation process to be active. Activation energies for conduction and relaxation process were calculated using the Arrhenius relation. The UV-visible optical transmission spectra was shown a wide transmission window and calculated optical band gap was found to be 5.67 eV.

The effect of host glass on optical absorption and fluorescence of Nd3+ in xNa(2)O-(30-x)K2O-70B(2)O(3) glasses

The effect of host glass composition on the optical absorption and fluorescence spectra of Nd3+ has been studied in mixed alkali borate glasses of the type xNa(2)O-(30-x)K2O-69.5B(2)O(3)-0.5Nd(2)O(3) (X = 5,10,15,20 and 25). Various spectroscopic parameters such as Racah (E-1, E-2 and E-3), spin-orbit (xi(4f)) and configuration interaction (alpha, beta) parameters have been calculated. The Judd-Ofelt intensity parameters (Omega(lambda)) have been calculated and the radiative transition probabilities (A(rad)), radiative lifetimes (tau(r)), branching ratios (beta) and integrated absorption cross sections (Sigma) have been obtained for certain excited states of the Nd3+, ion and are discussed with respect to x. From the fluorescence spectra, the effective fluorescence line widths (Deltalambda(eff)) and stimulated emission cross sections (sigma(p)) have been obtained for the three transitions F-4(3/2) --> I-4(9/2), F-4(3/2) --> I-4(11/2) and F-4(3/2) --> I-4(13/2) of Nd3+. The stimulated emission cross section (sigma(p)) values are found to be in the range (2.0-4.8) x 10(-2)0 cm(2) and they are large enough to indicate that the mixed alkali borate glasses could be potential laser host materials.

Observation of the nuclear magnetic octupole moment of Yb-173 from precise measurements of the hyperfine structure in the P-3(2) state

We measure hyperfine structure in the metastable P-3(2) state of Yb-173 and extract the nuclear magnetic octupole moment. We populate the state using dipole-allowed transitions through the P-3(1) and S-3(1) states. We measure frequencies of hyperfine transitions of the P-3(2) -> S-3(1) line at 770 nm using a Rb-stabilized ring cavity resonator with a precision of 200 kHz. Second-order corrections due to perturbations from the nearby P-3(1) and P-1(1) states are below 30 kHz. We obtain the hyperfine coefficients as A = -742.11(2) MHz and B = 1339.2(2) MHz, which represent a two orders-of-magnitude improvement in precision, and C = 0.54(2) MHz. From atomic structure calculations, we obtain the nuclear moments quadrupole Q = 2.46(12) b and octupole Omega = -34.4(21) b x mu(N). DOI: 10.1103/PhysRevA.87.012512

High Proton Mobility, Solvent Induced Single Crystal to Single Crystal Structural Transformation, and Related Studies on a Family of Compounds Formed from Mn-3 Oxo-Clusters

The reaction between 4,4'-sulfonyldibenzoic acid (H(2)SDBA) and manganese under mild conditions resulted in the isolation of two new three-dimensional compounds, Mn-4(C14H8O6S)(4)(DMA)(2)]center dot 3DMA, I, and Mn-3(C14H8O6S)(3)(DMA)(2)(MeOH)]center dot DMA, IIa. Both structures have Mn-3 trimer oxo cluster units. While the Mn-3 oxoclusters are connected through octahedral manganese forming one-dimensional Mn-O-Mn chains in I, the Mn-3 units are isolated in IIa. The SDBA units connect the Mn-O-Mn chains and the Mn-3 clusters giving rise to the three-dimensional structure. Both compounds have coordinated and free solvent molecules. In IIa, two different solvent molecules are coordinated, of which one solvent can be reversibly exchanged by a variety of other similar solvents via a solvent-mediated single crystal to single crystal (SCSC) transformation. The free lattice DMA solvent molecules in I can be exchanged by water molecules resulting in hydrophilic channels. Proton conductivity studies on I reveals a high proton mobility with conductivity values of similar to 0.87 x 10(-3) Omega(-1) cm(-1) at 34 degrees C and 98% RH, which is comparable to some of the good proton conductivity values observed in inorganic coordination polymers. We have also shown structural transformation of I to IIa through a possible dissolution and recrystallization pathway. In addition, both I and IIa appear to transform to two other manganese compounds H3O]Mn-3(mu(3)-OH)(C14H8O6S)(3)(H2O)](DMF)(5) and H3O](2)Mn-7(mu 3-OH)(4)(C14H8O6S)(6)(H2O)(4)](H2O)(2)(DMF)(8) under suitable reaction conditions. We have partially substituted Co in place of Mn in the Mn-3 trimer clusters forming CoMn2(C14H8O6S)(3)(DMA)(2)(EtOH)]center dot DMA, III, a structure that is closely related to IIa. All the compounds reveal antiferromagnetic behavior. On heating, the cobalt substituted phase (compound III) forms a CoMn2O4 spinel phase with particle sizes in the nanometer range.

Cadmium Sulfide Nanocrystal Sensitized Vertically Aligned Titanium Dioxide Rods for Large Area Image Sensors on 3-D Substrates

We discuss here a semiconductors assembly comprising of titanium dioxide (TiO2) rods sensitized by cadmium sulfide (CdS) nanocrystals for potential applications in large area electronics on three dimensional (3-D) substrates. Vertically aligned TiO2 rods are grown on a substrate using a 150 degrees C process flow and then sensitized with CdS by SILAR method at room temperature. This structure forms an effective photoconductor as the photo-generated electrons are rapidly removed from the CdS via the TiO2 thereby permitting a hole rich CdS. Current-voltage characteristics are measured and models illustrate space charge limited photo-current as the mechanism of charge transport at moderate voltage bias. The stable assembly and high speed are achieved. The frequency response with a loading of 10 pF and 9 M Omega shows a half power frequency of 100 Hz. (C) 2015 The Electrochemical Society. All rights reserved.

Ethyl 1-(2-cyanoethyl)-3,5-dimethyl-1H-indole-2-carboxylate

The title compound, C16H18N2O2, is an important precursor in the synthesis of 1,2,3,4-tetrahydropyrazinoindoles, which show excellent antihistamine, antihypertensive and central nervous system depressant properties. The carbethoxy group attached to C2 and the planar cyanoethyl group attached to N1 make dihedral angles of 11.0(4) and 75.0(3)degrees, respectively, with the mean plane of the indole ring, The C-C=N chain is linear with a bond angle of 179.3 (4)degrees.