Combined Electron Transfer Dissociation-Collision-Induced Dissociation Fragmentation in the Mass Spectrometric Distinction of Leucine, Isoleucine, and Hydroxyproline Residues in Peptide Natural Products

Distinctions between isobaric residues have been a major challenge in mass spectrometric peptide sequencing. Here, we propose a methodology for distinction among isobaric leucine, isoleucine, and hydroxyproline, a commonly found post-translationally modified amino acid with a nominal mass of 113 Da, through a combined electron transfer dissociation-collision-induced dissociation approach. While the absence of c and z(center dot) ions, corresponding to the Yyy-Xxx (Xxx = Leu, Ile, or Hyp) segment, is indicative of the presence of hydroxyproline, loss of isopropyl (Delta m = 43 Da) or ethyl radicals (Delta m = 29 Da), through collisional activation of z(center dot) radical ions, are characteristic of leucine or isoleucine, respectively. Radical migration processes permit distinctions even in cases where the specific e ions, corresponding to the Yyy-Leu or -Ile segments, are absent or of low intensity. This tandem mass spectrometric (MSn) method has been successfully implemented in a liquid chromatography MSn platform to determine the identity of 23 different isobaric residues from a mixture of five different peptides. The approach is convenient for distinction of isobaric residues from any crude peptide mixture, typically encountered in natural peptide libraries or proteomic analysis.

Electrical breakdown of carbon nanotube devices and the predictability of breakdown position

We have investigated electrical transport properties of long (>10 mu m) multiwalled carbon nanotubes (NTs) by dividing individuals into several segments of identical length. Each segment has different resistance because of the random distribution of defect density in an NT and is corroborated by Raman studies. Higher is the resistance, lower is the current required to break the segments indicating that breakdown occurs at the highly resistive segment/site and not necessarily at the middle. This is consistent with the one-dimensional thermal transport model. We have demonstrated the healing of defects by annealing at moderate temperatures or by current annealing. To strengthen our mechanism, we have carried out electrical breakdown of nitrogen doped NTs (NNTs) with diameter variation from one end to the other. It reveals that the electrical breakdown occurs selectively at the narrower diameter region. Overall, we believe that our results will help to predict the breakdown position of both semiconducting and metallic NTs. Copyright 2012 Author(s). This article is distributed under a Creative Commons Attribution 3.0 Unported License. http://dx.doi.org/10.1063/1.4720426]

Synthetic studies toward geranylated PPAP natural products oblongifolin A, oblongifolin D, and enervosanone

A concise approach of general utility toward mono- and di-geranylated PPAP frameworks employing `reconstructive aldol cyclization' as the key step is delineated. (C) 2012 Elsevier Ltd. All rights reserved.

Enantioselective syntheses of bioactive epoxyquinone natural products (+)-harveynone and (-)-asperpentyn

Stereo- and enantioselective syntheses of (+)-harveynone and (-)-asperpentyn are reported. (C) 2012 Elsevier Ltd. All rights reserved.

Model synthetic studies toward jiadifenin and majucin type seco-prezizaane natural products via a stereo- and enantioselective approach

A concise stereo- and enantioselective approach to seco-prezizaane sesquiterpenoids, leading to the acquisition of two bicyclic fragments, is delineated. (c) 2012 Elsevier Ltd. All rights reserved.

Physically Based, Hydrologic Model Results Based on Three Precipitation Products

The main objective of the study is to examine the accuracy of and differences among simulated streamflows driven by rainfall estimates from a network of 22 rain gauges spread over a 2,170 km2 watershed, NEXRAD Stage III radar data, and Tropical Rainfall Measuring Mission (TRMM) 3B42 satellite data. The Gridded Surface Subsurface Hydrologic Analysis (GSSHA), a physically based, distributed parameter, grid-structured, hydrologic model, was used to simulate the June-2002 flooding event in the Upper Guadalupe River watershed in south central Texas. There were significant differences between the rainfall fields estimated by the three types of measurement technologies. These differences resulted in even larger differences in the simulated hydrologic response of the watershed. In general, simulations driven by radar rainfall yielded better results than those driven by satellite or rain-gauge estimates. This study also presents an overview of effects of land cover changes on runoff and stream discharge. The results demonstrate that, for major rainfall events similar to the 2002 event, the effect of urbanization on the watershed in the past two decades would not have made any significant effect on the hydrologic response. The effect of urbanization on the hydrologic response increases as the size of the rainfall event decreases.

Breakdown of the Stokes-Einstein relation in two, three, and four dimensions

The breakdown of the Stokes-Einstein (SE) relation between diffusivity and viscosity at low temperatures is considered to be one of the hallmarks of glassy dynamics in liquids. Theoretical analyses relate this breakdown with the presence of heterogeneous dynamics, and by extension, with the fragility of glass formers. We perform an investigation of the breakdown of the SE relation in 2, 3, and 4 dimensions in order to understand these interrelations. Results from simulations of model glass formers show that the degree of the breakdown of the SE relation decreases with increasing spatial dimensionality. The breakdown itself can be rationalized via the difference between the activation free energies for diffusivity and viscosity (or relaxation times) in the Adam-Gibbs relation in three and four dimensions. The behavior in two dimensions also can be understood in terms of a generalized Adam-Gibbs relation that is observed in previous work. We calculate various measures of heterogeneity of dynamics and find that the degree of the SE breakdown and measures of heterogeneity of dynamics are generally well correlated but with some exceptions. The two-dimensional systems we study show deviations from the pattern of behavior of the three-and four-dimensional systems both at high and low temperatures. The fragility of the studied liquids is found to increase with spatial dimensionality, contrary to the expectation based on the association of fragility with heterogeneous dynamics.

Feasibility of laser-induced breakdown spectroscopy for the study of the temporal distribution of trace elements trapped in snow collected from greater himalayan range

The potential merit of laser-induced breakdown spectroscopy (LIBS) has been demonstrated for detection and quantification of trace pollutants trapped in snow/ice samples. In this technique, a high-power pulsed laser beam from Nd:YAG Laser (Model no. Surelite III-10, Continuum, Santa Clara, CA, USA) is focused on the surface of the target to generate plasma. The characteristic emissions from laser-generated plasma are collected and recorded by a fiber-coupled LIBS 2000+ (Ocean Optics, Santa Clara, CA, USA) spectrometer. The fingerprint of the constituents present in the sample is obtained by analyzing the spectral lines by using OOI LIBS software. Reliable detection of several elements like Zn, Al, Mg, Fe, Ca, C, N, H, and O in snow/ice samples collected from different locations (elevation) of Manali and several snow samples collected from the Greater Himalayan region (from a cold lab in Manali, India) in different months has been demonstrated. The calibration curve approach has been adopted for the quantitative analysis of these elements like Zn, Al, Fe, and Mg. Our results clearly demonstrate that the level of contamination is higher in those samples that were collected in the month of January in comparison to those collected in February and March.

Naphthalene Carbohydrazone Based Dizinc(II) Chemosensor for a Pyrophosphate Ion and Its DNA Assessment Application in Polymerase Chain Reaction Products

A new naphthalene carbohydrazone based dizinc(II) complex has been synthesized and investigated to act as a highly selective fluorescence and visual sensor for a pyrophosphate ion with a quite low detection limit of 155 ppb; this has also been used to detect the pyrophosphate ion released from polymerase-chain-reaction.

Chromium isotope variations (delta Cr-53/52) in mantle-derived sources and their weathering products: Implications for environmental studies and the evolution of delta Cr-53/52 in the Earth's mantle over geologic time

Here we report chromium isotope compositions, expressed as delta Cr-53/ 52 in per mil (&) relative to NIST 979, measured in selected Cr-rich minerals and rocks formed by the primary magmatic as well as the secondary metamorphic and weathering processes. The main objectives of this study were: (i) to further constrain the isotope composition of the Earth's mantle Cr inventory and its possible variation during geological history, based on the analysis of globally distributed and stratigraphically constrained mantle-derived chromites; and (ii) to investigate the magnitude and systematics of Cr isotope fractionation during oxidative weathering and secondary alteration (i. e., hydration, serpentinization) of the magmatic Cr sources. Specifically, we analyzed delta Cr-53/ 52 in a set of globally distributed mantle-derived chromites (FeMgCr2O4, n = 30) collected from various locations in Europe, Asia, Africa and South America, and our results confirm that a chromite-hosted Earth's mantle Cr inventory is uniform at - 0.079 +/- 0.129& (2SD), which we named here as a ` canonical' mantle d 53/ 52 Cr signature. Furthermore our dataset of stratigraphically constrained chromites, whose crystallization ages cover most of the Earth's geological history, indicate that the bulk Cr isotope composition of the chromite-hosted mantle inventory has remained uniform, within about +/- 0.100&, since at least the Early Archean times (similar to 3500 million years ago, Ma). To investigate the systematics of Cr isotope fractionation associated with alteration processes we analyzed a number of secondary Cr-rich minerals and variably altered ultramafic rocks (i. e., serpentinized harzburgites, lherzolites) that revealed large positive delta Cr-53/ 52 anomalies that are systematically shifted to higher values with an increasing degree of alteration and serpentinization. The degree of aqueous alteration and serpentinization was quantified by the abundances of fluid-mobile (Rb, K) elements, and by the Loss On Ignition (LOI) parameter, which determines the amount of structurally bound water (OH/ H2O) present in secondary hydrated minerals like serpentine. Overall, we observed that altered ultramafic rocks that yielded the highest LOI values, and the lowest amounts of fluid mobile elements, also yielded the heaviest delta Cr-53/ 52 signatures. Therefore, we conclude that secondary alteration (i.e., hydration, serpentinization) of ultramafic rocks in near-surface oxidative environments tend to shift the bulk Cr isotope composition of the weathered products to isotopically heavier values, pointing to a dynamic redox cycling of Cr in the Earth's crustal and near-surface environments. Hence, if validated by future

Calibration Curve with Improved Limit of Detection for Cadmium in Soil: An Approach to Minimize the Matrix Effect in Laser-Induced Breakdown Spectroscopic Analysis

The present article describes a working or combined calibration curve in laser-induced breakdown spectroscopic analysis, which is the cumulative result of the calibration curves obtained from neutral and singly ionized atomic emission spectral lines. This working calibration curve reduces the effect of change in matrix between different zone soils and certified soil samples because it includes both the species' (neutral and singly ionized) concentration of the element of interest. The limit of detection using a working calibration curve is found better as compared to its constituent calibration curves (i.e., individual calibration curves). The quantitative results obtained using the working calibration curve is in better agreement with the result of inductively coupled plasma-atomic emission spectroscopy as compared to the result obtained using its constituent calibration curves.

Transition in vortex breakdown modes in a coaxial isothermal unconfined swirling jet

This paper reports first observations of transition in recirculation pattern from an open-bubble type axisymmetric vortex breakdown to partially open bubble mode through an intermediate, critical regime of conical sheet formation in an unconfined, co-axial isothermal swirling flow. This time-mean transition is studied for two distinct flow modes which are characterized based on the modified Rossby number (Ro(m)), i.e., Ro(m) <= 1 and Ro(m) > 1. Flow modes with Ro(m) <= 1 are observed to first undergo cone-type breakdown and then to partially open bubble state as the geometric swirl number (S-G) is increased by similar to 20% and similar to 40%, respectively, from the baseline open-bubble state. However, the flow modes with Ro(m) > 1 fail to undergo such sequential transition. This distinct behavior is explained based on the physical significance associated with Ro(m) and the swirl momentum factor (xi). In essence, xi represents the ratio of angular momentum distributed across the flow structure to that distributed from central axis to the edge of the vortex core. It is observed that xi increases by similar to 100% in the critical swirl number band where conical breakdown occurs as compared to its magnitude in the S-G regime where open bubble state is seen. This results from the fact that flow modes with Ro(m) <= 1 are dominated by radial pressure gradient due to swirl/rotational effect when compared to radial pressure deficit arising from entrainment (due to the presence of co-stream). Consequently, the imparted swirl tends to penetrate easily towards the central axis causing it to spread laterally and finally undergo conical sheet breakdown. However, the flow modes with Ro(m) > 1 are dominated by pressure deficit due to entrainment effect. This blocks the radial inward penetration of imparted angular momentum thus preventing the lateral spread of these flow modes. As such these structures fail to undergo cone mode of vortex breakdown which is substantiated by a mere 30%-40% rise in xi in the critical swirl number range. (C) 2014 AIP Publishing LLC.