Quantitative analysis of complex peptide mixtures using FTMS and differential mass spectrometry

Label-free LC-MS profiling is a powerful quantitative proteomic method to study relative peptide abundances between two or more biological samples. Here we demonstrate the use of a previously described comparative LC-MS method, differential mass spectrometry (dMS), to analyze high-resolution Fourier transform mass spectrometry (FTMS) data for detection and quantification of known peptide differences between two sets of complex mixtures. Six standard peptides were spiked into a processed plasma background at fixed ratios from 1.25:1 to 4:1 to make two sets of samples. The resulting mixtures were analyzed by microcapillary LC-FTMS and dMS. dMS successfully identified five out of the six peptides as statistically significant differences (p 相似文献   

Highly Extensible Bio‐Nanocomposite Fibers

Here, we show that a poly(ethylene oxide) polymer can be physically cross‐linked with silicate nanoparticles (Laponite) to yield highly extensible, bio‐nanocomposite fibers that, upon pulling, stretch to extreme lengths and crystallize polymer chains. We find that both, nanometer structures and mechanical properties of the fibers respond to mechanical deformation by exhibiting strain‐induced crystallization and high elongation. We explore the structural characteristics using X‐ray scattering and the mechanical properties of the dried fibers made from hydrogels in order to determine feasibility for eventual biomedical use and to map out directions for further materials development.

     

dc-Hydrogen plasma induced defects in bulk n-Ge

Bulk antimony doped germanium (n-Ge) has been exposed to a dc–hydrogen plasma. Capacitance–voltage depth profiles revealed extensive near surface passivation of the shallow donors as evidenced by ∼a 1.5 orders of magnitude reduction in the free carrier concentration up to depth of ∼3.2 μm. DLTS and Laplace-DLTS revealed a prominent electron trap 0.30 eV below the conduction (E_C –0.30 eV). The concentration of this trap increased with plasma exposure time. The depth profile for this defect suggested a uniform distribution up to 1.2 μm. Annealing studies show that this trap, attributed to a hydrogen-related complex, is stable up to 200 °C. Hole traps, or vacancy-antimony centers, common in this material after high energy particle irradiation, were not observed after plasma exposure, an indication that this process does not create Frenkel (V–I) pairs.     

The dependence of barrier height on temperature for Pd Schottky contacts on ZnO

Temperature dependent current-voltage (I-V) and capacitance-voltage (C-V) measurements have been performed on Pd/ZnO Schottky barrier diodes in the range 60-300 K. The room temperature values for the zero bias barrier height from the I-V measurements (Φ_I-V) was found to be 0.52 eV and from the C-V measurements (Φ_C-V) as 3.83 eV. From the temperature dependence of forward bias I-V, the barrier height was observed to increase with temperature, a trend that disagrees with the negative temperature coefficient for semiconductor material. The C-V barrier height decreases with temperature, a trend that is in agreement with the negative temperature coefficient of semiconductor material. This has enabled us to fit two curves in two regions (60-120 K and 140-300 K). We have attributed this behaviour to a defect observed by DLTS with energy level 0.31 eV below the conduction band and defect concentration of between 4×10¹⁶ and 6×10¹⁶ cm⁻³ that traps carriers, influencing the determination of the barrier height.     

Systematic errors in DFT calculations of haloalkane heats of formation

The B3LYP and B3PW91 density functionals were employed with a large [BS1 = 6-311+G(3df,2p)] and small [BS2 = 6-311G(d,p)] basis set to compute enthalpies of formation (at optimized MP2/6-31G(d) geometries and with scaled HF/6-31G(d) frequencies) in the following series of haloalkanes: (1) the 15 fluoro-, chloro-, and chlorofluoromethanes, (2) the 18 fluorinated and chlorinated ethanes. Similar to earlier higher level calculations on haloalkanes, the computed enthalpies exhibited very large, systematic deviations from experiment. It was found that these errors could be largely eliminated using a very simple Bond Additivity Correction (BAC) formula, Delta(f)H degrees (BAC) = Delta(f)H degrees (calc) - n(CX). Delta(CX) [X = F, Cl], in which the BAC parameters, Delta(CF) and Delta(CCl) were determined by fitting the equation to experimental data on the four fluoroethanes and chloroethanes, respectively. The resultant BAC corrected enthalpies of formation are in excellent agreement with experiment, with RMS deviations in the same range as quoted RMS errors in measured enthalpies. Therefore, this simple BAC procedure may be utilized to provide reliable semiquantitative estimates of enthalpies of formation in larger haloalkanes, for which higher level ab initio calculations are not feasible.     

An investigation of the Cr1−xMnxO2 series and the characterization of orthorhombic CrMnO4

Several members of the Cr_1?xMn_xO₂ series were prepared in the tetrahedral anvil press by the reaction of CrO₂ with MnO₂. The tetragonal, rutile-type products were single-phase and have been characterized by crystallographic and magnetic measurements. The results are consistent with the formulations Cr⁴⁺_1?2xCr³⁺ Mn⁵⁺O₂ for 0 ? x ? 0.5. At low manganese concentration, x < 0.20, the magnetic moments are consistent with ferromagnetic contribution from Mn⁵⁺. A two-phase product was noted at the composition x = 0.90. The CrMnO₄ composition was found to have a powder pattern similar to that of orthorhombic PtO₂.