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.

Mass Distribution Studies in Effervescent Sprays

An experimental study on liquid mass distribution in effervescent sprays using water and air as working fluids is presented in this paper. Optical patternation and techniques of image processing are employed for analyzing the spray. The flow regime inside the effervescent atomizer largely dictates the mass distribution patterns. The patterns are seen to vary from concentrated, poorly atomized liquid lumps to uniformly distributed, fine droplets as the flow regime changes from bubbly flow to annular flow. A large variety of instantaneous spray patterns are observed in bubbly flow regime indicating a highly unsteady atomization process. However, relatively better consistency in spray patterns is observed at higher gas flow rates. Thus, the degree of unsteadiness gradually diminishes as gas flow rate is increased. The axial evolution of the spray in annular mode shows good mixing of liquid and gas across the interface.

Mass of highly magnetized white dwarfs exceeding the Chandrasekhar limit: An analytical view

In recent years a number of white dwarfs have been observed with very high surface magnetic fields. We can expect that the magnetic field in the core of these stars would be much higher (similar to 10(14) G). In this paper, we analytically study the effect of high magnetic field on relativistic cold electron, and hence its effect on the stability and the mass-radius relation of a magnetic white dwarf. In strong magnetic fields, the equation of state of the Fermi gas is modified and Landau quantization comes into play. For relatively very high magnetic fields (with respect to the average energy density of matter) the number of Landau levels is restricted to one or two. We analyze the equation of states for magnetized electron degenerate gas analytically and attempt to understand the conditions in which transitions from the zeroth Landau level to first Landau level occurs. We also find the effect of the strong magnetic field on the star collapsing to a white dwarf, and the mass-radius relation of the resulting star. We obtain an interesting theoretical result that it is possible to have white dwarfs with mass more than the mass set by Chandrasekhar limit.

Large mass splittings for fourth generation fermions allowed by LHC Higgs boson exclusion

In the context of the standard model with a fourth generation, we explore the allowed mass spectra in the fourth-generation quark and lepton sectors as functions of the Higgs mass. Using the constraints from unitarity and oblique parameters, we show that a heavy Higgs allows large mass splittings in these sectors, opening up new decay channels involving W emission. Assuming that the hints for a light Higgs do not yet constitute an evidence, we work in a scenario where a heavy Higgs is viable. A Higgs heavier than similar to 800 GeV would in fact necessitate either a heavy quark decay channel t' -> b'W/b' -> t'W or a heavy lepton decay channel tau' -> nu'W as long as the mixing between the third and fourth generations is small. This mixing tends to suppress the mass splittings and hence the W-emission channels. The possibility of the W-emission channel could substantially change the search strategies of fourth-generation fermions at the LHC and impact the currently reported mass limits.

An invariant subspace-based approach to the random eigenvalue problem of systems with clustered spectrum

The repeated or closely spaced eigenvalues and corresponding eigenvectors of a matrix are usually very sensitive to a perturbation of the matrix, which makes capturing the behavior of these eigenpairs very difficult. Similar difficulty is encountered in solving the random eigenvalue problem when a matrix with random elements has a set of clustered eigenvalues in its mean. In addition, the methods to solve the random eigenvalue problem often differ in characterizing the problem, which leads to different interpretations of the solution. Thus, the solutions obtained from different methods become mathematically incomparable. These two issues, the difficulty of solving and the non-unique characterization, are addressed here. A different approach is used where instead of tracking a few individual eigenpairs, the corresponding invariant subspace is tracked. The spectral stochastic finite element method is used for analysis, where the polynomial chaos expansion is used to represent the random eigenvalues and eigenvectors. However, the main concept of tracking the invariant subspace remains mostly independent of any such representation. The approach is successfully implemented in response prediction of a system with repeated natural frequencies. It is found that tracking only an invariant subspace could be sufficient to build a modal-based reduced-order model of the system. Copyright (C) 2012 John Wiley & Sons, Ltd.

Sensitive Liquid Chromatography-Tandem Mass Spectrometry Method for the Determination of Olanzapine in Human Urine

A sensitive and selective liquid chromatographic-tandem mass spectrometric (LC-MS-MS) method was developed to determine olanzapine (OLZ) in human urine. After solid-phase extraction with SPE cartridge, the urine sample was analysed on a C-18 column (Symmetry 3.5 mu m, 50 x 4.6 mm i.d) interfaced with a triple quadrupole tandem mass spectrometer. Positive electrospray ionization was employed as the ionization source. The mobile phase consisted of ammonium acetate (pH 7.8)-acetonitrile (10:90, v/v). The method was linear over a concentration range of 1-100 ngml(-1). The lower limit of quantitation was 1 ngml(-1). The intra-day and inter-day relative standard deviation across three validation runs over the entire concentration range was < 11.5 %. The accuracy determined at three concentrations (8.0, 50.0 and 85.0 ngml(-1) OLZ) was within +/- 1.21 % in terms of relative errors.

Strongly magnetized cold degenerate electron gas: Mass-radius relation of the magnetized white dwarf

We consider a relativistic, degenerate electron gas at zero temperature under the influence of a strong, uniform, static magnetic field, neglecting any form of interactions. Since the density of states for the electrons changes due to the presence of the magnetic field (which gives rise to Landau quantization), the corresponding equation of state also gets modified. In order to investigate the effect of very strong magnetic field, we focus only on systems in which a maximum of either one, two, or three Landau level(s) is/are occupied. This is important since, if a very large number of Landau levels are filled, it implies a very low magnetic field strength which yields back Chandrasekhar's celebrated nonmagnetic results. The maximum number of occupied Landau levels is fixed by the correct choice of two parameters, namely, the magnetic field strength and the maximum Fermi energy of the system. We study the equations of state of these one-level, two-level, and three-level systems and compare them by taking three different maximum Fermi energies. We also find the effect of the strong magnetic field on the mass-radius relation of the underlying star composed of the gas stated above. We obtain an exciting result that it is possible to have an electron-degenerate static star, namely, magnetized white dwarfs, with a mass significantly greater than the Chandrasekhar limit in the range 2.3-2.6M(circle dot), provided it has an appropriate magnetic field strength and central density. In fact, recent observations of peculiar type Ia supernovae-SN 2006gz, SN 2007if, SN 2009dc, SN 2003fg-seem to suggest super-Chandrasekhar-mass white dwarfs with masses up to 2.4-2.8M(circle dot) as their most likely progenitors. Interestingly, our results seem to lie within these observational limits.

Lepton masses and flavor violation in the Randall-Sundrum model

Lepton masses and mixing angles via localization of 5-dimensional fields in the bulk are revisited in the context of Randall-Sundrum models. The Higgs is assumed to be localized on the IR brane. Three cases for neutrino masses are considered: (a) The higher-dimensional neutrino mass operator (LH.LH), (b) Dirac masses, and (c) Type I seesaw with bulk Majorana mass terms. Neutrino masses and mixing as well as charged lepton masses are fit in the first two cases using chi(2) minimization for the bulk mass parameters, while varying the O(1) Yukawa couplings between 0.1 and 4. Lepton flavor violation is studied for all the three cases. It is shown that large negative bulk mass parameters are required for the right-handed fields to fit the data in the LH.LH case. This case is characterized by a very large Kaluza-Klein (KK) spectrum and relatively weak flavor-violating constraints at leading order. The zero modes for the charged singlets are composite in this case, and their corresponding effective 4-dimensional Yukawa couplings to the KK modes could be large. For the Dirac case, good fits can be obtained for the bulk mass parameters, c(i), lying between 0 and 1. However, most of the ``best-fit regions'' are ruled out from flavor-violating constraints. In the bulk Majorana terms case, we have solved the profile equations numerically. We give example points for inverted hierarchy and normal hierarchy of neutrino masses. Lepton flavor violating rates are large for these points. We then discuss various minimal flavor violation schemes for Dirac and bulk Majorana cases. In the Dirac case with minimal-flavor-violation hypothesis, it is possible to simultaneously fit leptonic masses and mixing angles and alleviate lepton flavor violating constraints for KK modes with masses of around 3 TeV. Similar examples are also provided in the Majorana case.

A spring-mass-lever model, stiffness and inertia maps for single-input, single-output compliant mechanisms

A spring-mass-lever (SML) model is introduced in this paper for a single-input-single-output compliant mechanism to capture its static and dynamic behavior. The SML model is a reduced-order model, and its five parameters provide physical insight and quantify the stiffness and inertia(1) at the input and output ports as well as the transformation of force and displacement between the input and output. The model parameters can be determined with reasonable accuracy without performing dynamic or modal analysis. The paper describes two uses of the SML model: computationally efficient analysis of a system of which the compliant mechanism is a part; and design of compliant mechanisms for the given user-specifications. During design, the SML model enables determining the feasible parameter space of user-specified requirements, assessing the suitability of a compliant mechanism to meet the user-specifications and also selecting and/or re-designing compliant mechanisms from an existing database. Manufacturing constraints, material choice, and other practical considerations are incorporated into this methodology. A micromachined accelerometer and a valve mechanism are used as examples to show the effectiveness of the SML model in analysis and design. (C) 2012 Published by Elsevier Ltd.

Postcards from oases in the desert: phenomenology of SUSY with intermediate scales

The presence of new matter fields charged under the Standard Model gauge group at intermediate scales below the Grand Unification scale modifies the renormalization group evolution of the gauge couplings. This can in turn significantly change the running of the Minimal Supersymmetric Standard Model parameters, in particular the gaugino and the scalar masses. In the absence of new large Yukawa couplings we can parameterise all the intermediate scale models in terms of only two parameters controlling the size of the unified gauge coupling. As a consequence of the modified running, the low energy spectrum can be strongly affected with interesting phenomenological consequences. In particular, we show that scalar over gaugino mass ratios tend to increase and the regions of the parameter space with neutralino Dark Matter compatible with cosmological observations get drastically modified. Moreover, we discuss some observables that can be used to test the intermediate scale physics at the LHC in a wide class of models.

On the height of fall of dropping mass in SASW measurements for asphaltic road pavements

A number of spectral analysis of surface waves (SASW) tests were performed on asphaltic road pavements by dropping a metallic 6.5 kg sphere, from a height (H) ranging from 1 to 3 m. Various combinations of source to first receiver distance (S) and receiver spacing (X) were employed. By increasing the height of the fall of the dropping mass, the maximum wavelength (lambda(max)), up to which the shear wave velocity profile can be predicted with the usage of the SASW measurements, was found to increase continuously. The height of fall of the dropping mass also seems to affect the admissible range of the wavelength for given combinations of X and S. Irrespective of different chosen combinations of S, X and H, a unique combined dispersion curve was generated in all the cases for a given pavement site as long as the threshold minimum value of the coherence function is greater than 0.90.

Variation of Snowline and Mass Balance of Glaciers of Warwan and Bhut Basins of Western Himalaya Using Remote Sensing Technique

Glaciers are natural reservoirs of fresh water in frozen state and sensitive indicators of climate change. Among all the mountainous glaciated regions, glaciers of Himalayas form one of the largest concentrations of ice outside the Polar Regions. Almost all the major rivers of northern India originate from these glaciers and sustain perennial flow. Therefore, in view of the importance and role of the glaciers in sustaining the life on the Earth, monitoring the health of glaciers is necessary. Glacier's health is monitored in two ways (i) by mapping the change in extent of glaciers (ii) by finding variation in the annual mass balance. This paper has been discussed the later approach for monitoring the health of glaciers of Warwan and Bhut basins. Mass balance of glaciers of these two basins was determined based on the extraction of snow line at the end of ablation season. A series of satellite images of AWiFS sensor were analysed for extraction of snowline on the glaciers for the period of 2005, 2006 and 2007. The snow line at the end of ablation season is used to compute accumulation area ratio (AAR = Accumulation area/Glacier area) for each glacier of basins. An approach based on relationship of AAR to specific mass balance (computed in field) for glaciers of Basapa basin was employed in the present study. Mean of specific mass balance of individual glacier for the year 2005, 2006 and 2007 of Warwan basin was found to be -ve 0.19 m, -ve 0.27 m and -ve 0.2 m respectively. It is 0.05 m, -ve 0.11 m and -ve 0.19 m for Bhut basin. The analysis suggests a loss of 4.3 and 0.83 kmA(3) of glacier in the monitoring period of 3 years for Warwan and Bhut basins respectively. The overall results suggest that the glaciers of Warwan basin and Bhut basins have suffered more loss of ice than gain in the monitoring period of 3 years.