Characterization of Alkali Induced Formation of Lanthionine, Trisulfides, and Tetrasulfides from Peptide Disulfides using Negative Ion Mass Spectrometry

Peptide disulfides are unstable under alkaline conditions, resulting in the formation of products containing lanthionine and polysulfied linkages. Electrospray ionization mass spectrometry has been used to characterize major species obtained when cyclic and acyclic peptide disulfides are exposed to alkaline media. Studies on a model cyclic peptide disulfide (Boc - Cys - Pro - Leu - Cys - NHMe) and an acyclic peptide, oxidized glutathione, bis ((gamma)Glu Cys - Gly - COOH), are described. Disulfide cleavage reactions are initiated by the abstraction of (CH)-H-alpha or (CH)-H-beta protons of Cys residues, with Subsequent elimination of H2S or H2S2. The buildup of reactive thiol species which act on intermediates containing dehydroalanine residues, rationalizes the formation of lanthionine and polysulfide products. In the case of the cyclic peptide disulfide, the formation of cyclic products is facilitated by the intramolecular nature of the Michael addition reaction of thiols to the dehydroalanine residue. Mass spectral evidence for the intermediate species is presented by using alkylation of thiol groups as a trapping method. Mass spectral fragmentation in the negative ion mode of the peptides derived from trisulfides and tetrasulfides results in elimination of S-2. (J Am Soc Mass Spectrom 2009, 20, 783-791) (C) 2009 American Society for Mass Spectrometry.

Re-Conceptualizing Value-Creation From Industrial Business Logic to Service Business Logic

There is an urgent interest in marketing to move away from neo-classical value definitions suggesting that value creation is a process of exchanging goods for money. In the present paper, value creation is conceptualized as an integration of two distinct, yet closely coupled processes. First, actors co-create what this paper calls an underlying basis of value. This is done by interactively re-configuring resources. By relating and combining resources, activity sets, and risks across actor boundaries in novel ways actors create joint productivity gains – a concept very similar to density (Normann, 2001). Second, actors engage in a process of signification and evaluation. Signification implies co-constructing the meaning and worth of joint productivity gains co-created through interactive resource re-configuration, as well as sharing those gains through a pricing mechanism as value to involved actors. The conceptual framework highlights an all-important dynamics associated with ´value creation´ and ´value´ - a dynamics the paper claims has eluded past marketing research. The paper argues that the framework presented here is appropriate for the interactive service perspective, where value and value creation are not objectively given, but depend on the power of involved actors´ socially constructed frames to mobilize resources across actor boundaries in ways that ´enhance system well-being´ (Vargo et al., 2008). The paper contributes to research on Service Logic, Service-Dominant Logic, and Service Science.

Deformation and failure of a film/substrate system subjected to spherical indentation: Part 1. Experimental validation of stresses and strains derived using Hankel transform technique in an elastic film/substrate system

Our concern here is to rationalize experimental observations of failure modes brought about by indentation of hard thin ceramic films deposited on metallic substrates. By undertaking this exercise, we would like to evolve an analytical framework that can be used for designs of coatings. In Part I of the paper we develop an algorithm and test it for a model system. Using this analytical framework we address the issue of failure of columnar TiN films in Part II [J. Mater. Res. 21, 783 (2006)] of the paper. In this part, we used a previously derived Hankel transform procedure to derive stress and strain in a birefringent polymer film glued to a strong substrate and subjected to spherical indentation. We measure surface radial strains using strain gauges and bulk film stresses using photo elastic technique (stress freezing). For a boundary condition based on Hertzian traction with no film interface constraint and assuming the substrate constraint to be a function of the imposed strain, the theory describes the stress distributions well. The variation in peak stresses also demonstrates the usefulness of depositing even a soft film to protect an underlying substrate.

Average lattices and aperiodic structures

Statistically averaged lattices provide a common basis to understand the diffraction properties of structures displaying deviations from regular crystal structures. An average lattice is defined and examples are given in one and two dimensions along with their diffraction patterns. The absence of periodicity in reciprocal space corresponding to aperiodic structures is shown to arise out of different projected spacings that are irrationally related, when the grid points are projected along the chosen coordinate axes. It is shown that the projected length scales are important factors which determine the existence or absence of observable periodicity in the diffraction pattern more than the sequence of arrangement.

Grain Floatation During Equiaxed Solidification of an Al-Cu Alloy in a Side-Cooled Cavity: Part II-Numerical Studies

In this article, a single-phase, one-domain macroscopic model is developed for studying binary alloy solidification with moving equiaxed solid phase, along with the associated transport phenomena. In this model, issues such as thermosolutal convection, motion of solid phase relative to liquid and viscosity variations of the solid-liquid mixture with solid fraction in the mobile zone are taken into account. Using the model, the associated transport phenomena during solidification of Al-Cu alloys in a rectangular cavity are predicted. The results for temperature variation, segregation patterns, and eutectic fraction distribution are compared with data from in-house experiments. The model predictions compare well with the experimental results. To highlight the influence of solid phase movement on convection and final macrosegregation, the results of the current model are also compared with those obtained from the conventional solidification model with stationary solid phase. By including the independent movement of the solid phase into the fluid transport model, better predictions of macrosegregation, microstructure, and even shrinkage locations were obtained. Mechanical property prediction models based on microstructure will benefit from the improved accuracy of this model.

Location and conformation of pantothenate and its derivatives in Mycobacterium tuberculosis pantothenate kinase: insights into enzyme action

Previous studies of complexes of Mycobacterium tuberculosis PanK (MtPanK) with nucleotide diphosphates and non-hydrolysable analogues of nucleoside triphosphates in the presence or the absence of pantothenate established that the enzyme has dual specificity for ATP and GTP, revealed the unusual movement of ligands during enzyme action and provided information on the effect of pantothenate on the location and conformation of the nucleotides at the beginning and the end of enzyme action. The X-ray analyses of the binary complexes of MtPanK with pantothenate, pantothenol and N-nonylpantothenamide reported here demonstrate that in the absence of nucleotide these ligands occupy, with a somewhat open conformation, a location similar to that occupied by phosphopantothenate in the `end' complexes, which differs distinctly from the location of pantothenate in the closed conformation in the ternary `initiation' complexes. The conformation and the location of the nucleotide were also different in the initiation and end complexes. An invariant arginine appears to play a critical role in the movement of ligands that takes place during enzyme action. The work presented here completes the description of the locations and conformations of nucleoside diphosphates and triphosphates and pantothenate in different binary and ternary complexes, and suggests a structural rationale for the movement of ligands during enzyme action. The present investigation also suggests that N-alkylpantothenamides could be phosphorylated by the enzyme in the same manner as pantothenate.

Boxicity of Circular Arc Graphs

A k-dimensional box is a Cartesian product R(1)x...xR(k) where each R(i) is a closed interval on the real line. The boxicity of a graph G, denoted as box(G), is the minimum integer k such that G can be represented as the intersection graph of a collection of k-dimensional boxes. That is, two vertices are adjacent if and only if their corresponding boxes intersect. A circular arc graph is a graph that can be represented as the intersection graph of arcs on a circle. We show that if G is a circular arc graph which admits a circular arc representation in which no arc has length at least pi(alpha-1/alpha) for some alpha is an element of N(>= 2), then box(G) <= alpha (Here the arcs are considered with respect to a unit circle). From this result we show that if G has maximum degree Delta < [n(alpha-1)/2 alpha] for some alpha is an element of N(>= 2), then box(G) <= alpha. We also demonstrate a graph having box(G) > alpha but with Delta = n (alpha-1)/2 alpha + n/2 alpha(alpha+1) + (alpha+2). For a proper circular arc graph G, we show that if Delta < [n(alpha-1)/alpha] for some alpha is an element of N(>= 2), then box(G) <= alpha. Let r be the cardinality of the minimum overlap set, i.e. the minimum number of arcs passing through any point on the circle, with respect to some circular arc representation of G. We show that for any circular arc graph G, box(G) <= r + 1 and this bound is tight. We show that if G admits a circular arc representation in which no family of k <= 3 arcs covers the circle, then box(G) <= 3 and if G admits a circular arc representation in which no family of k <= 4 arcs covers the circle, then box(G) <= 2. We also show that both these bounds are tight.

Gold(I)-selenolate complexes: Synthesis, characterization and ligand exchange reactions

In this paper, the synthesis and characterization of some imidazole-based gold-selenolates are described. This study indicates that the nature of selenolate plays an important role in ligand exchange reactions in gold(I) selenolates. Furthermore, the reactivity of imidazole-based gold(I) selenolates toward nucleophiles such as selenols and phosphines is strikingly different from that of the N,N-dimethylaminobenzylamine-based gold(I) complexes. The presence of Se ... N non-bonded interactions in N,N-dimethylaminobenzylamine-based gold(I) complexes modulates the reactivity of Au(I) centre towards incoming nucleophiles.

A 5th and 7th order harmonic suppression scheme using capacitive filtering for 2-level VSI fed IM drive

In this paper, a 5th and 7th harmonic suppression technique for a 2-level VSI fed IM drive, by using capacitive filtering is proposed. A capacitor fed 2-level inverter is used on an open-end winding induction motor to suppress all 5th and 7th order harmonics. A PWM scheme that maintains the capacitor voltage, while suppressing the harmonics is also proposed. The proposed scheme is valid for the entire modulation range, including overmodulation and six-step mode of operation of the main inverter.

GHG footprint of major cities in India

Concentration of greenhouse gases (GHG) in the atmosphere has been increasing rapidly during the last century due to ever increasing anthropogenic activities resulting in significant increases in the temperature of the Earth causing global warming. Major sources of GHG are forests (due to human induced land cover changes leading to deforestation), power generation (burning of fossil fuels), transportation (burning fossil fuel), agriculture (livestock, farming, rice cultivation and burning of crop residues), water bodies (wetlands), industry and urban activities (building, construction, transport, solid and liquid waste). Aggregation of GHG (CO2 and non-CO2 gases), in terms of Carbon dioxide equivalent (CO(2)e), indicate the GHG footprint. GHG footprint is thus a measure of the impact of human activities on the environment in terms of the amount of greenhouse gases produced. This study focuses on accounting of the amount of three important greenhouses gases namely carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) and thereby developing GHG footprint of the major cities in India. National GHG inventories have been used for quantification of sector-wise greenhouse gas emissions. Country specific emission factors are used where all the emission factors are available. Default emission factors from IPCC guidelines are used when there are no country specific emission factors. Emission of each greenhouse gas is estimated by multiplying fuel consumption by the corresponding emission factor. The current study estimates GHG footprint or GHG emissions (in terms of CO2 equivalent) for Indian major cities and explores the linkages with the population and GDP. GHG footprint (Aggregation of Carbon dioxide equivalent emissions of GHG's) of Delhi, Greater Mumbai, Kolkata, Chennai, Greater Bangalore, Hyderabad and Ahmedabad are found to be 38,633.2 Gg, 22,783.08 Gg, 14,812.10 Gg, 22,090.55 Gg, 19,796.5 Gg, 13,734.59 Gg and 91,24.45 Gg CO2 eq., respectively. The major contributors sectors are transportation sector (contributing 32%, 17.4%, 13.3%, 19.5%, 43.5%, 56.86% and 25%), domestic sector (contributing 30.26%, 37.2%, 42.78%, 39%, 21.6%, 17.05% and 27.9%) and industrial sector (contributing 7.9%, 7.9%, 17.66%, 20.25%, 1231%, 11.38% and 22.41%) of the total emissions in Delhi, Greater Mumbai, Kolkata, Chennai, Greater Bangalore, Hyderabad and Ahmedabad, respectively. Chennai emits 4.79 t of CO2 equivalent emissions per capita, the highest among all the cities followed by Kolkata which emits 3.29 t of CO2 equivalent emissions per capita. Also Chennai emits the highest CO2 equivalent emissions per GDP (2.55 t CO2 eq./Lakh Rs.) followed by Greater Bangalore which emits 2.18 t CO2 eq./Lakh Rs. (C) 2015 Elsevier Ltd. All rights reserved.

Endoplasmic reticulum targeting tumour selective photocytotoxic oxovanadium(IV) complexes having vitamin-B6 and acridinyl moieties

Oxovanadium(IV) complexes of vitamin-B6 Schiff base, viz., VO(HL1/L-2/L-3)(B)] Cl (1-4), where B is 2,2'-bipyridine (bpy in 1 and 2), 11-(9-acridinyl)dipyrido3,2-a:2',3'-c]phenazine (acdppz in 3 and 4), H2L1 center dot HCl is 3-hydroxy-5-(hydroxymethyl)-4-(((2-hydroxyphenyl)imino)methyl)-2-methylp yridin-1-ium chloride (in 1 and 4), HL2 is 2-(((2-(1H-imidazol-4-yl)ethyl) imino)methyl) phenol (in 2) and HL3 is 4-(((2-(1H-imidazol-4- yl)ethyl)imino)methyl)-5-(hydroxymethyl)-2-methylpyridin-3-ol (in 3) were synthesized, characterized and their cellular uptake, photo-activated cytotoxicity and intracellular localization were studied. Complexes 1a, as the perchlorate salt of 1, and 2a, as the hexafluorophosphate salt of 2, were structurally characterized. Vitamin-B6 transporting membrane carrier (VTC) mediated entry into tumour cells in preference to the normal ones seems to be responsible for the higher cellular uptake of the complexes into HeLa and MCF-7 cells over MCF-10A cells. Complexes 3 and 4 having acdppz as the photosensitizer exhibit remarkable photocytotoxicity in these cancer cells giving IC50 of < 0.9 mu M. The complexes remain non-toxic in the dark. The complexes show photo-induced apoptotic cell death via singlet oxygen (O-1(2)) generation. Fluorescence microscopy reveals specific localization of complex 4 to endoplasmic reticulum (ER) and generation of O-1(2) possibly leads to apoptotic cell death by triggering ER stress response (ERSR).

Endoplasmic reticulum targeting tumour selective photocytotoxic oxovanadium(IV) complexes having vitamin-B6 and acridinyl moieties

Oxovanadium(IV) complexes of vitamin-B6 Schiff base, viz., VO(HL1/L-2/L-3)(B)] Cl (1-4), where B is 2,2'-bipyridine (bpy in 1 and 2), 11-(9-acridinyl)dipyrido3,2-a:2',3'-c]phenazine (acdppz in 3 and 4), H2L1 center dot HCl is 3-hydroxy-5-(hydroxymethyl)-4-(((2-hydroxyphenyl)imino)methyl)-2-methylp yridin-1-ium chloride (in 1 and 4), HL2 is 2-(((2-(1H-imidazol-4-yl)ethyl) imino)methyl) phenol (in 2) and HL3 is 4-(((2-(1H-imidazol-4- yl)ethyl)imino)methyl)-5-(hydroxymethyl)-2-methylpyridin-3-ol (in 3) were synthesized, characterized and their cellular uptake, photo-activated cytotoxicity and intracellular localization were studied. Complexes 1a, as the perchlorate salt of 1, and 2a, as the hexafluorophosphate salt of 2, were structurally characterized. Vitamin-B6 transporting membrane carrier (VTC) mediated entry into tumour cells in preference to the normal ones seems to be responsible for the higher cellular uptake of the complexes into HeLa and MCF-7 cells over MCF-10A cells. Complexes 3 and 4 having acdppz as the photosensitizer exhibit remarkable photocytotoxicity in these cancer cells giving IC50 of < 0.9 mu M. The complexes remain non-toxic in the dark. The complexes show photo-induced apoptotic cell death via singlet oxygen (O-1(2)) generation. Fluorescence microscopy reveals specific localization of complex 4 to endoplasmic reticulum (ER) and generation of O-1(2) possibly leads to apoptotic cell death by triggering ER stress response (ERSR).

Accelerating method of moments based package-board 3D parasitic extraction using FPGA

In this article, a Field Programmable Gate Array (FPGA)-based hardware accelerator for 3D electromagnetic extraction, using Method of Moments (MoM) is presented. As the number of nets or ports in a system increases, leading to a corresponding increase in the number of right-hand-side (RHS) vectors, the computational cost for multiple matrix-vector products presents a time bottleneck in a linear-complexity fast solver framework. In this work, an FPGA-based hardware implementation is proposed toward a two-level parallelization scheme: (i) matrix level parallelization for single RHS and (ii) pipelining for multiple-RHS. The method is applied to accelerate electrostatic parasitic capacitance extraction of multiple nets in a Ball Grid Array (BGA) package. The acceleration is shown to be linearly scalable with FPGA resources and speed-ups over 10x against equivalent software implementation on a 2.4GHz Intel Core i5 processor is achieved using a Virtex-6 XC6VLX240T FPGA on Xilinx's ML605 board with the implemented design operating at 200MHz clock frequency. (c) 2016 Wiley Periodicals, Inc. Microwave Opt Technol Lett 58:776-783, 2016

氮化钛沉积膜的摩擦性能研究

采用等离子电弧沉积法在9Cr18钢表面制备了厚约0.5 μm的TiN薄膜，通过显微硬度测试以及纳米压痕和纳米划痕试验，对比考察了9Cr18钢及其表面TiN薄膜的机械和摩擦性能。结果表明，9Cr18钢及其表面TiN沉积膜的纳米硬度分别为8GPa和38GPa，弹性模量分别为250GPa和580 GPa，9Cr18、TiN和有机薄膜的摩擦系数分别为0.40、0.12和、0.10；TiN沉积膜可显著提高基体钢的承载和耐磨能力。