Probing the role of the C-H center dot center dot center dot O hydrogen bond stabilized polypeptide chain reversal at the C-terminus of designed peptide helices. Structural characterization of three decapeptides

The structural characterization in crystals of three designed decapeptides containing a double D-segment at the C-terminus is described. The crystal structures of the peptides Boc-Leu-Aib-Val-Xxx-Leu-Aib-Val- (D)Ala-(D)Leu-Aib-OMe, (Xxx = Gly 2, (D)Ala 3, Aib 4) have been determined and compared with those reported earlier for peptide 1 (Xxx = Ala) and the all L analogue Boc-Leu-Aib-Val-Ala-Leu-Aib-Val-Ala-Leu-Aib-OMe, which yielded a perfect right-handed a-helical structure. Peptides 1 and 2 reveal a right-handed helical segment spanning residues 1 to 7, ending in a Schellman motif with Ala(8) functioning as the terminating residue. Polypeptide chain reversal occurs at residue 9, a novel feature that appears to be the consequence of a C-(HO)-O-... hydrogen bond between residue 4 (CH)-H-alpha and residue 9 CO groups. The structures of peptides 3 and 4, which lack the pro R hydrogen at the C-alpha atom of residue 4, are dramatically different. Peptide 3 adopts a right-handed helical conformation over the 1 to 7 segment. Residues 8 and 9 adopt at conformations forming a C-terminus type I' beta-turn, corresponding to an incipient left-handed twist of the polypeptide chain. In peptide 4, helix termination occurs at Aib(6), with residues 6 to 9 forming a left-handed helix, resulting in a structure that accommodates direct fusion of two helical segments of opposite twist. Peptides 3 and 4 provide examples of chiral residues occurring in the less favored sense of helical twist; (D)Ala(4) in peptide 3 adopts an alpha(R) conformation, while (L)Val(7) in 4 adopts an alpha(L) conformation. The structural comparison of the decapeptides reported here provides evidence for the role of specific C-(HO)-O-... hydrogen bonds in stabilizing chain reversals at helix termini, which may be relevant in aligning contiguous helical and strand segments in polypeptide structures.

Softening and dynamic recrystallization in magnesium single crystals during c-axis compression

Commercial purity (99.8%) magnesium single crystals were subjected to plane strain compression (PSC) along the c-axis at 200 and 370 degrees C and a constant strain rate of 10(-3) s(-1). Extension was confined to the < 1 1 (2) over bar 0 > direction and the specimens were strained up to a logarithmic true strain of -1. The initial rapid increase in flow stress was followed by significant work softening at different stresses and comparable strains of about -0.05 related to macroscopic twinning events. The microstructure of the specimen after PSC at 200 degrees C was characterized by a high density of {1 0 (1) over bar 1} and {1 0 (1) over bar 3} compression twins, some of which were recrystallized. After PSC at 370 degrees C, completely recrystallized twin bands were the major feature of the observed microstructure. All new grains in these bands retained the same c-axis orientation of their compression twin hosts. The basal plane in these grains was randomly rotated around the c-axis, forming a fiber texture component. The obtained results are discussed with respect to the mechanism of recrystallization, the specific character of the boundaries between new grains and the initial matrix, and the importance of the dynamically recrystallized bands for strain accommodation in these deformed magnesium single crystals. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Branching out at C-2 of septanosides. Synthesis of 2-deoxy-2-C-alkyl/aryl septanosides from a bromo-oxepine

This paper deals with the synthesis of 2-deoxy-2-C-alkyl/aryl septanosides. A range of such septanoside derivatives was synthesized by using a common bromo-oxepine intermediate, involving C-C bond forming organometallic reactions. Unsaturated, seven-membered septanoside vinyl bromides or bromo-oxepines, obtained through a ring expansion methodology of the cyclopropane derivatives of oxyglycals, displayed a good reactivity towards several acceptor moieties in C-C bond forming Heck, Suzuki and Sonogashira coupling reactions, thus affording 2-deoxy-2-C-alkyl/aryl septanosides. Whereas Heck and Sonogashira coupling reactions afforded 2-deoxy-2-C-alkenyl and -alkynyl derivatives, respectively, the Suzuki reaction afforded 2-deoxy-2-C-aryl septanosides. Deprotection and reduction of the 2-deoxy-2-alkenyl derivative afforded the corresponding 2-deoxy-2-C-alkyl septanoside free of protecting groups. The present study illustrates the reactivity of bromo-oxepine in the synthesis of hitherto unknown septanosides, branching out at C-2, through C-C bond formation with alkyl and aryl substituents.

The Structural Characterization of Folded Peptides Containing the Conformationally Constrained beta-Amino Acid Residue beta(2,2)Ac(6)c

Backbone alkylation has been shown to result in a dramatic reduction in the conformational space that is sterically accessible to a-amino acid residues in peptides. By extension, the presence of geminal dialkyl substituents at backbone atoms also restricts available conformational space for beta and ? residues. Five peptides containing the achiral beta 2,2-disubstituted beta-amino acid residue, 1-(aminomethyl)cyclohexanecarboxylic acid (beta 2,2Ac6c), have been structurally characterized in crystals by X-ray diffraction. The tripeptide Boc-Aib-beta 2,2Ac6c-Aib-OMe (1) adopts a novel fold stabilized by two intramolecular H-bonds (C11 and C9) of opposite directionality. The tetrapeptide Boc-Aib-beta 2,2Ac6c]2-OMe (2) and pentapeptide Boc-Aib-beta 2,2Ac6c]2-Aib-OMe (3) form short stretches of a hybrid a beta C11 helix stabilized by two and three intramolecular H-bonds, respectively. The structure of the dipeptide Boc-Aib-beta 2,2Ac6c-OMe (5) does not reveal any intramolecular H-bond. The aggregation pattern in the crystal provides an example of an extended conformation of the beta 2,2Ac6c residue, forming a polar sheet like H-bond. The protected derivative Ac-beta 2,2Ac6c-NHMe (4) adopts a locally folded gauche conformation about the C beta?Ca bonds (?=-55.7 degrees). Of the seven examples of beta 2,2Ac6c residues reported here, six adopt gauche conformations, a feature which promotes local folding when incorporated into peptides. A comparison between the conformational properties of beta 2,2Ac6c and beta 3,3Ac6c residues, in peptides, is presented. Backbone torsional parameters of H-bonded a beta/beta a turns are derived from the structures presented in this study and earlier reports.

Investigations on micro-blast wave assisted metal foil forming for biomedical applications

The deformation dynamics of metal foils (<0.25 mm thick) subjected to micro-blast wave are presented in this paper. The energy of micro-blast wave emanating from the open end of a polymer tube is used to deliver micro-particles for bio-medical applications. In these experiments metal foils are used to transfer the energy of the micro-blast wave to the micro-particles. Using cubic root scaling law the over pressure of the blast wave at the open end of the polymer tube is estimated and using this peak plate over pressure is estimated. The finite element analysis is used to estimate the velocity profile of the deforming metal foils. The finite element analysis results are compared with experimental results for the maximum deformation and deformed shape. Based on the deformation velocity, metal foil to be used for experiments is selected. Among the materials investigated 0.1 mm thick brass foil has the maximum velocity of 205 m/s and is used in the experiments. It is found from finite element analysis that the particles deposited within a radius of 0.5 mm will leave the foil with nearly equal velocity (error < 5%). The spray cone angle which is the angle of deviation of the path of particles from the axis of the polymer tube is also estimated and found to be less than 7 degrees up to a radius of 0.75 mm. Illustrative experiments are carried out to deliver micro particles (0.7 mu m diameter tungsten) into plant tissues. Particle penetration depth up to 460 mu m was achieved in ground tissue of potato tuber. (C) 2012 Elsevier Ltd. All rights reserved.

Influence of tool rotation speed and feed rate on the forming limit of friction stir welded AA6061-T6 sheets

In this study, the influence of tool rotation speed and feed rate on the forming limit of friction stir welded Al 6061-T651 sheets has been investigated. The forming limit curve was evaluated by limit dome height test performed on all the friction stir welded sheets. The welding trials were conducted at a tool rotation speed of 1300 and 1400 r/min and feed rate of 90 and 100 mm/min. A third trial of welding was performed at a rotational speed of 1500 r/min and feed rate 120 mm/min. It is found that with increase in the tool rotation speed, from 1300 to 1400 r/min, for a constant feed rate, the forming limit of friction stir welded blank has improved and with increase in feed rate, from 90 to 100 mm/min, for a constant tool rotation speed, it has decreased. The forming limit of friction stir welded sheets is better than unwelded sheets. The thickness gradient after forming is severe in the cases of friction stir welded blanks made at higher feed rate and lower rotation speed. The strain hardening exponent of weld (n) increases with increase in tool rotation speed and it decreases with increase in feed rate. It has been demonstrated that the change in the forming limit of friction stir welded sheets with respect to welding parameters is due to the thickness distribution severity and strain hardening exponent of the weld region during forming. There is not much variation in the dome height among the friction stir welded sheets tested. When compared with unwelded sheets, dome height of friction stir welded sheets is higher in near-plane-strain condition, but it is lesser in stretching strain paths.

Experimental investigation of forming limit, void coalescence and crystallographic textures of aluminum alloy 8011 sheet annealed at various temperatures

In this work, a combined forming and fracture limit diagram, fractured void coalescence and texture analysis have been experimentally evaluated for the commercially available aluminum alloy Al 8011 sheet annealed at different temperatures viz. 200 degrees C, 250 degrees C, 300 degrees C and 350 degrees C. The sheets were examined at different annealing temperatures on microstructure, tensile properties, formability and void coalescence. The fractured surfaces of the formed samples were examined using scanning electron microscope (SEM) and these images were correlated with fracture behavior and formability of sheet metals. Formability of Al 8011 was studied and examined at various annealing temperatures using their bulk X-ray crystallographic textures and ODF plots. Forming limit diagrams, void coalescence parameters and crystallographic textures were correlated with normal anisotropy of the sheet metals annealed at different temperatures. (C) 2013 Politechnika Wroclawska. Published by Elsevier Urban & Partner Sp. z o.o. All rights reserved.

Fragility correlates thermodynamic and kinetic properties of glass forming liquids

In our earlier communication we proposed a simple fragility determining function, (NBO]/(VmTg)-T-3), which we have now used to analyze several glass systems using available thermal data. A comparison with similar fragility determining function, Delta C-p/C-p(1), introduced by Chryssikos et al. in their investigation of lithium borate glasses has also been performed and found to be more convenient quantity for discussing fragilities. We now propose a new function which uses both Delta C-p and Delta T and which gives a numerical fragility parameter, F whose value lies between 0 and 1 for glass forming liquids. F can be calculated through the use of measured thermal parameters Delta C-p, C-p(1), T-g and T-m. Use of the new fragility values in reduced viscosity equation reproduces the whole range of viscosity curves of the Angell plot. The reduced viscosity equation can be directly compared with the Adam-Gibbs viscosity equation and a heat capacity function can be formulated which reproduces satisfactorily the Delta C-p versus In(T-r) curves and hence the configurational entropy. (C) 2014 Elsevier Ltd. All rights reserved.

Fragility correlates thermodynamic and kinetic properties of glass forming liquids

In our earlier communication we proposed a simple fragility determining function, (NBO]/(VmTg)-T-3), which we have now used to analyze several glass systems using available thermal data. A comparison with similar fragility determining function, Delta C-p/C-p(1), introduced by Chryssikos et al. in their investigation of lithium borate glasses has also been performed and found to be more convenient quantity for discussing fragilities. We now propose a new function which uses both Delta C-p and Delta T and which gives a numerical fragility parameter, F whose value lies between 0 and 1 for glass forming liquids. F can be calculated through the use of measured thermal parameters Delta C-p, C-p(1), T-g and T-m. Use of the new fragility values in reduced viscosity equation reproduces the whole range of viscosity curves of the Angell plot. The reduced viscosity equation can be directly compared with the Adam-Gibbs viscosity equation and a heat capacity function can be formulated which reproduces satisfactorily the Delta C-p versus In(T-r) curves and hence the configurational entropy. (C) 2014 Elsevier Ltd. All rights reserved.

GBNV encoded movement protein (NSm) remodels ER network via C-terminal coiled coil domain

Plant viruses exploit the host machinery for targeting the viral genome-movement protein complex to plasmodesmata (PD). The mechanism by which the non-structural protein m (NSm) of Groundnut bud necrosis virus (GBNV) is targeted to PD was investigated using Agrobacterium mediated transient expression of NSm and its fusion proteins in Nicotiana benthamiana. GFP:NSm formed punctuate structures that colocalized with mCherry:plasmodesmata localized protein la (PDLP la) confirming that GBNV NSm localizes to PD. Unlike in other movement proteins, the C-terminal coiled coil domain of GBNV NSm was shown to be involved in the localization of NSm to PD, as deletion of this domain resulted in the cytoplasmic localization of NSm. Treatment with Brefeldin A demonstrated the role of ER in targeting GFP NSm to PD. Furthermore, mCherry:NSm co-localized with ER-GFP (endoplasmic reticulum targeting peptide (HDEL peptide fused with GFP). Co-expression of NSm with ER-GFP showed that the ER-network was transformed into vesicles indicating that NSm interacts with ER and remodels it. Mutations in the conserved hydrophobic region of NSm (residues 130-138) did not abolish the formation of vesicles. Additionally, the conserved prolines at positions 140 and 142 were found to be essential for targeting the vesicles to the cell membrane. Further, systematic deletion of amino acid residues from N- and C-terminus demonstrated that N-terminal 203 amino acids are dispensable for the vesicle formation. On the other hand, the C-terminal coiled coil domain when expressed alone could also form vesicles. These results suggest that GBNV NSm remodels the ER network by forming vesicles via its interaction through the C-terminal coiled coil domain. Interestingly, NSm interacts with NP in vitro and coexpression of these two proteins in planta resulted in the relocalization of NP to PD and this relocalization was abolished when the N-terminal unfolded region of NSm was deleted. Thus, the NSm interacts with NP via its N-terminal unfolded region and the NSm-NP complex could in turn interact with the ER membrane via the C-terminal coiled coil domain of NSm to form vesicles that are targeted to PD and there by assist the cell to cell movement of the viral genome complex. (C) 2015 Elsevier Inc. All rights reserved.

DIFFUSE X-RAY EMISSION FROM STAR-FORMING GALAXIES

We study the diffuse X-ray luminosity (L-X) of star-forming galaxies using two-dimensional axisymmetric hydrodynamical simulations and analytical considerations of supernovae-(SNe-) driven galactic outflows. We find that the mass loading of the outflows, a crucial parameter for determining the X-ray luminosity, is constrained by the availability of gas in the central star-forming region, and a competition between cooling and expansion. We show that the allowed range of the mass loading factor can explain the observed scaling of L-X with star formation rate (SFR) as L-X alpha SFR2 for SFR greater than or similar to 1 M-circle dot yr(-1), and a flatter relation at low SFRs. We also show that the emission from the hot circumgalactic medium (CGM) in the halo of massive galaxies can explain the large scatter in the L-X-SFR relation for low SFRs (less than or similar to few M-circle dot yr(-1)). Our results suggest that galaxies with small SFRs and large diffuse X-ray luminosities are excellent candidates for the detection of the elusive CGM.

Evaluation of live-attenuated Salmonella vaccines expressing Campylobacter antigens for control of C. jejuni in poultry

Campylobacter jejuni is a zoonotic bacterial pathogen of worldwide importance. It is estimated that 460,000 human infections occur in the United Kingdom per annum and these involve acute enteritis and may be complicated by severe systemic sequelae. Such infections are frequently associated with the consumption of contaminated poultry meat and strategies to control C. jejuni in poultry are expected to limit pathogen entry into the food chain and the incidence of human disease. Toward this aim, a total of 840 Light Sussex chickens were used to evaluate a Salmonella enterica serovar Typhimurium ΔaroA vaccine expressing the C. jejuni amino acid binding protein CjaA as a plasmid-borne fusion to the C-terminus of fragment C of tetanus toxin. Chickens were given the vaccine at 1-day-old and two weeks later by oral gavage, then challenged after a further two weeks with C. jejuni. Across six biological replicates, statistically significant reductions in caecal C. jejuni of c. 1.4 log10 colony-forming units/g were observed at three and four weeks post-challenge relative to age-matched unvaccinated birds. Protection was associated with the induction of CjaA-specific serum IgY and biliary IgA. Protection was not observed using a vaccine strain containing the empty plasmid. Vaccination with recombinant CjaA subcutaneously at the same intervals significantly reduced the caecal load of C. jejuni at three and four weeks post-challenge. Taken together these data imply that responses directed against CjaA, rather than competitive or cross-protective effects mediated by the carrier, confer protection. The impact of varying parameters on the efficacy of the S. Typhimurium ΔaroA vaccine expressing TetC-CjaA was also tested. Delaying the age at primary vaccination had little impact on protection or humoral responses to CjaA. The use of the parent strain as carrier or changing the attenuating mutation of the carrier to ΔspaS or ΔssaU enhanced the protective effect, consistent with increased invasion and persistence of the vaccine strains relative to the ΔaroA mutant. Expression in the ΔaroA strain of a TetC fusion to Peb1A, but not TetC fusions to GlnH or ChuA, elicited protection against intestinal colonisation by C. jejuni that was comparable to that observed with the TetC-CjaA fusion. Our data are rendered highly relevant by use of the target host in large numbers and support the potential of CjaA- and Peb1A-based vaccines for control of C. jejuni in poultry. © 2009 Elsevier Ltd. All rights reserved.

Synthesis of thick Ni66Cr5Mo4Zr6P15B4 amorphous alloy coating and large glass-forming ability by laser cladding

A thick amorphous alloy (a-alloy) coating was synthesized by laser cladding. The a-alloy had a multicomponent chemistry, i.e., Ni66Cr5MO4Zr6P15B4 (in atom%). The maximum thickness of the coating is 0.8 mm. The a-alloy coating had large glass-forming ability (GFA) with wide supercooled liquid region (SLR) ranging from 52 to 61 K through the coating. The reason for high GFA in the a-alloy coating was discussed. (C) 2002 Published by Elsevier Science B.V.

Review: Trans-forming beef to provide healthier fatty acid profiles

[EN]Trans fatty acids are found naturally in foods, particularly in those derived from ruminant animals, such as beef and dairy cattle. Over the past few decades, human consumption of trans fatty acids has increased, but this has been mainly from products containing partially hydrogenated vegetable oils. The correlation of trans fatty acid consumption with diseases such as coronary heart disease has been cause for concern, and led to recommendations to reduce their consumption. Trans fatty acids, however, have differing effects on human health. Therefore, in foods produced from ruminant animals, it is important to know their trans fatty acid composition, and how to enrich or deplete fatty acids that have positive or negative health effects. This review will cover the analysis of trans fatty acids in beef, their origin, how to manipulate their concentrations, and give a brief overview of their health effects.

Carbon-carbon bond forming reactions from bis(carbene)-platinum(II) complexes and olefin polymerization and oligomerization using group 4 post-metallocene complexes

A long-standing challenge in transition metal catalysis is selective C–C bond coupling of simple feedstocks, such as carbon monoxide, ethylene or propylene, to yield value-added products. This work describes efforts toward selective C–C bond formation using early- and late-transition metals, which may have important implications for the production of fuels and plastics, as well as many other commodity chemicals.

The industrial Fischer-Tropsch (F-T) process converts synthesis gas (syngas, a mixture of CO + H₂) into a complex mixture of hydrocarbons and oxygenates. Well-defined homogeneous catalysts for F-T may provide greater product selectivity for fuel-range liquid hydrocarbons compared to traditional heterogeneous catalysts. The first part of this work involved the preparation of late-transition metal complexes for use in syngas conversion. We investigated C–C bond forming reactions via carbene coupling using bis(carbene)platinum(II) compounds, which are models for putative metal–carbene intermediates in F-T chemistry. It was found that C–C bond formation could be induced by either (1) chemical reduction of or (2) exogenous phosphine coordination to the platinum(II) starting complexes. These two mild methods afforded different products, constitutional isomers, suggesting that at least two different mechanisms are possible for C–C bond formation from carbene intermediates. These results are encouraging for the development of a multicomponent homogeneous catalysis system for the generation of higher hydrocarbons.

A second avenue of research focused on the design and synthesis of post-metallocene catalysts for olefin polymerization. The polymerization chemistry of a new class of group 4 complexes supported by asymmetric anilide(pyridine)phenolate (NNO) pincer ligands was explored. Unlike typical early transition metal polymerization catalysts, NNO-ligated catalysts produce nearly regiorandom polypropylene, with as many as 30-40 mol % of insertions being 2,1-inserted (versus 1,2-inserted), compared to <1 mol % in most metallocene systems. A survey of model Ti polymerization catalysts suggests that catalyst modification pathways that could affect regioselectivity, such as C–H activation of the anilide ring, cleavage of the amine R-group, or monomer insertion into metal–ligand bonds are unlikely. A parallel investigation of a Ti–amido(pyridine)phenolate polymerization catalyst, which features a five- rather than a six-membered Ti–N chelate ring, but maintained a dianionic NNO motif, revealed that simply maintaining this motif was not enough to produce regioirregular polypropylene; in fact, these experiments seem to indicate that only an intact anilide(pyridine)phenolate ligated-complex will lead to regioirregular polypropylene. As yet, the underlying causes for the unique regioselectivity of anilide(pyridine)phenolate polymerization catalysts remains unknown. Further exploration of NNO-ligated polymerization catalysts could lead to the controlled synthesis of new types of polymer architectures.

Finally, we investigated the reactivity of a known Ti–phenoxy(imine) (Ti-FI) catalyst that has been shown to be very active for ethylene homotrimerization in an effort to upgrade simple feedstocks to liquid hydrocarbon fuels through co-oligomerization of heavy and light olefins. We demonstrated that the Ti-FI catalyst can homo-oligomerize 1-hexene to C<sub>12 and C<sub>18 alkenes through olefin dimerization and trimerization, respectively. Future work will include kinetic studies to determine monomer selectivity by investigating the relative rates of insertion of light olefins (e.g., ethylene) vs. higher α-olefins, as well as a more detailed mechanistic study of olefin trimerization. Our ultimate goal is to exploit this catalyst in a multi-catalyst system for conversion of simple alkenes into hydrocarbon fuels.