Top-down protein sequencing by CID and ECD using desorption electrospray ionisation (DESI) and high-field FTICR mass spectrometry

We report high resolution spectra for the medium molecular weight proteins myoglobin and cytochrome-c obtained using a custom desorption electrospray ionisation (DESI) source coupled to a Bruker Daltonics 12 T Apex Qe Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS). The DESI source was designed for accurate alignment and reproduction of critical geometric variables. A two axis motorised stage was included to enable automated rastering of the sample under the DESI plume. Spectra for the intact proteins have been obtained under single-acquisition conditions and a top-down analysis of cytochrome-c was performed using both collision induced dissociation (CID) and electron capture dissociation (ECD) of the isolated [M+15H]¹⁵⁺ charge state. The sequence coverage is comparable to that obtained using electrospray ionisation, demonstrating the utility of top-down protein analysis by DESI FTICR-MS.     

Power generation using an activated carbon and metal mesh cathode in a microbial fuel cell

An inexpensive activated carbon (AC) air cathode was developed as an alternative to a platinum-catalyzed electrode for oxygen reduction in a microbial fuel cell (MFC). AC was cold-pressed with a polytetrafluoroethylene (PTFE) binder to form the cathode around a Ni mesh current collector. This cathode construction avoided the need for carbon cloth or a metal catalyst, and produced a cathode with high activity for oxygen reduction at typical MFC current densities. Tests with the AC cathode produced a maximum power density of 1220 mW/m² (normalized to cathode projected surface area; 36 W/m³ based on liquid volume) compared to 1060 mW/m² obtained by Pt catalyzed carbon cloth cathode. The Coulombic efficiency ranged from 15% to 55%. These findings show that AC is a cost-effective material for achieving useful rates of oxygen reduction in air cathode MFCs.     

X—射线荧光光谱法分析保护渣中元素

保护渣元素的定量分析一般采用传统的湿法化学分析 ,化学分析虽然准确度好 ,但难以做到快速且劳动量大。利用 X-射线荧光光谱法分析保护渣中各元素含量是一种快速、准确的分析方法 ,在国外已得到广泛应用。本文从现场分析的实际出发 ,选择融样条件、最佳仪器参数 ,用基准物质合成标准样品 ,绘制标准工作曲线 ,曲线线性良好 ,用化学分析法对荧光分析值进行验证 ,结果符合化学允许差。1　试验部分1 .1　仪器设备、试剂及工作条件MXF2 1 0 0 - X-射线荧光光谱仪TR- AUTO- BEAD- 1 0 0 0 S/W熔融炉混合熔剂 :4g四硼酸钠 +4g四硼酸锂 +0 .…     

宽波段多步激发K_2-系统产生的钾原子高位态辐射

本文首次报道以690.0～715.0nm宽波段范围内任何波长的脉冲染料激光激发K_2—K系统,由高位钾分子与钾原子碰撞以及分子-原子的混合激发等过程而产生钾原子404.4,404.7和470.05～590.0nm波段内高位态辐射的实验结果,并对激发机制进行了探讨.     

Invariants de Maslov équivariants

We construct two cohomological invariants associated to pairs of Lagrangian sub-bundles of a symplectic bundle on a compact manifold upon which a compact Lie group is acting. The first invariant, which we call the classical equivariant Maslov H-invariant, provides an obstruction to Lagrangian transversality and lives in the Borel cohomology. The second invariant, which we call the equivariant Maslov U-invariant, generalises the author's results in K-Theory 13 (1998), 347–361 to the equivariant context and provides a necessary and sufficient condition for equivariant Lagrangian transversality, up to homotopic stability, and lives in the U-theory (intermediate between the real complex K-theories). As an application, we show that two Lagrangian sub-bundles of a symplectic bundle on a homogeneous space are always stably transverse.     

A Hyland-Bernstein approach to the digital control of Pritchard-Salamon systems

In this paper we consider the fixed finite-order digital linear-quadraticcontrol of Pritchard-Salamon infinite-dimensional systems withunbounded input and output operators under gaussian disturbances.A set of necessary conditions is given in terms of the solvabilityof a discrete-time Hyland-Bernstein system of equations (twomodified Riccati equations and two modified Lyapunov equationscoupled by an projection operator).     

State‐of‐the‐art all‐silicon sub‐bandgap photodetectors at telecom and datacom wavelengths

Silicon‐based technologies provide an ideal platform for the monolithic integration of photonics and microelectronics. In this context, a variety of passive and active silicon photonic devices have been developed to operate at telecom and datacom wavelengths, at which silicon has minimal optical absorption ‐ due to its bandgap of 1.12 eV. Although in principle this transparency window limits the use of silicon for optical detection at wavelengths above 1.1 μm, in recent years tremendous advances have been made in the field of all‐silicon sub‐bandgap photodetectors at telecom and datacom wavelengths. By taking advantage of emerging materials and novel structures, these devices are becoming competitive with the more well‐established technologies, and are opening new and intriguing perspectives. In this paper, a review of the state‐of‐the‐art is presented. Devices based on defect‐mediated absorption, two‐photon absorption and the internal photoemission effect are reported, their working principles are elucidated and their performance discussed and compared.

     

Polymeric cross-linked surface treatments for controlling block copolymer orientation in thin films

The orientation of cylinder-forming poly(styrene-block-methyl methacrylate) [P(S-b-MMA)] was investigated on two sets of polymeric surface treatments: 10 para-substituted polystyrene derivatives with <10 mol % poly(4-vinylbenzyl azide) and a series of poly(styrene-random-4-vinylbenzyl azide) [P(S-r-VBzAz)] copolymers with 5-100 mol % poly(4-vinylbenzyl azide). The copolymers were spin-coated to form thin films and then cross-linked by heating. The resulting films exhibited a range of surface tensions from 21 to 45 dyn/cm. Perpendicular orientation of P(S-b-MMA) cylinders was achieved with poly(p-bromostyrene) and all the [P(S-r-VBzAz)] copolymer surface treatments, most notably the homopolymer of poly(4-vinylbenzyl azide). Films made from these simple copolymers are as effective as random terpolymer alignment layers commonly made from both block monomers and a cross-linkable monomer.     

Mapping a Noncovalent Protein–Peptide Interface by Top-Down FTICR Mass Spectrometry Using Electron Capture Dissociation

Noncovalent protein–ligand and protein–protein complexes are readily detected using electrospray ionization mass spectrometry (ESI MS). Furthermore, recent reports have demonstrated that careful use of electron capture dissociation (ECD) fragmentation allows covalent backbone bonds of protein complexes to be dissociated without disruption of noncovalent protein–ligand interactions. In this way the site of protein–ligand interfaces can be identified. To date, protein–ligand complexes, which have proven tractable to this technique, have been mediated by ionic electrostatic interactions, i.e., ion pair interactions or salt bridging. Here we extend this methodology by applying ECD to study a protein–peptide complex that contains no electrostatics interactions. We analyzed the complex between the 21 kDa p53-inhibitor protein anterior gradient-2 and its hexapeptide binding ligand (PTTIYY). ECD fragmentation of the 1:1 complex occurs with retention of protein–peptide binding and analysis of the resulting fragments allows the binding interface to be localized to a C-terminal region between residues 109 and 175. These finding are supported by a solution-phase competition assay, which implicates the region between residues 108 and 122 within AGR2 as the PTTIYY binding interface. Our study expands previous findings by demonstrating that top-down ECD mass spectrometry can be used to determine directly the sites of peptide–protein interfaces. This highlights the growing potential of using ECD and related top-down fragmentation techniques for interrogation of protein–protein interfaces.