Optimization of electron transfer dissociation via informed selection of reagents and operating parameters

Electron transfer dissociation (ETD) has improved the mass spectrometric analysis of proteins and peptides with labile post-translational modifications and larger intact masses. Here, the parameters governing the reaction rate of ETD are examined experimentally. Currently, due to reagent injection and isolation events as well as longer reaction times, ETD spectra require significantly more time to acquire than collision-induced dissociation (CID) spectra (>100 ms), resulting in a trade-off in the dynamic range of tandem MS analyses when ETD-based methods are compared to CID-based methods. Through fine adjustment of reaction parameters and the selection of reagents with optimal characteristics, we demonstrate a drastic reduction in the time taken per ETD event. In fact, ETD can be performed with optimal efficiency in nearly the same time as CID at low precursor charge state (z = +3) and becomes faster at higher charge state (z > +3).     

Designing training for process control simulators: a review of empirical findings and current practices

Although simulators have been widely used as training environments in different industries (e.g. oil and nuclear power), there is little rigorous empirical work evaluating the effectiveness of the training methods employed. This article examines the use of simulator training in process control environments. The results of an exploratory field study are reported and the current practices of simulator training are described. The study revealed that simulator training varied considerably across organisations, often with little theoretical or empirical work to guide training design. To evaluate the utility and effectiveness of different methods of simulator training in process control environments, the article also presents a literature review of the research on laboratory- and field-based training. Several training methods are identified as having particular potential for temporal and adaptive transfer and are to be empirically tested in future studies.     

Improving lactic acid melt polycondensation: The role of co‐catalyst

A study on lactic acid polycondensation under melt conditions was carried out and a preliminary assessment revealed tin powder as a very good catalyst for poly(lactic acid) (PLA) synthesis by melt polycondensation while confirming previous information on SnCl₂ good performance. However, these catalysts also promoted side reactions leading to racemization and yellowing of the final polymer. The use of p‐toluenesulphonic acid (p‐TSA) or triphenylphosphine (PPh₃) as co‐catalysts proved to be very effective hindering colour formation and allowing synthesizing PLA samples with enhanced properties. The addition of these compounds to neat tin powder increased the PLA optical purity, whereas their addition to SnCl₂ speeded up the polymerization. A significant increase in molecular weight, from 32,500 to 52,000 g mol^?1, was recorded, with the new catalytic system SnCl₂/PPh₃ showing catalytic activity comparable with the one reported in the literature for SnCl₂/p‐TSA. Several characterization techniques were used for assessing polymer samples: the molecular weights were determined by SEC, thermal behavior measured by DSC, and racemization extent calculated from specific rotation measurements. UV/vis spectroscopy was confirmed as a powerful technique for evaluating yellowing of final polymers. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Multipole shimming of permanent magnets using harmonic corrector rings

Shimming systems are required to provide sufficient field homogeneity for high resolution nuclear magnetic resonance (NMR). In certain specialized applications, such as rotating-field NMR and mobile ex situ NMR, permanent magnet-based shimming systems can provide considerable advantages. We present a simple two-dimensional shimming method based on harmonic corrector rings which can provide arbitrary multipole order shimming corrections. Results demonstrate, for example, that quadrupolar order shimming improves the linewidth by up to an order of magnitude. An additional order of magnitude reduction is in principle achievable by utilizing this shimming method for z-gradient correction and higher order xy gradients.     

新古典主义建筑在中国和西方

该文首先提出与古典主义相对应的新古典主义概念,接着对在中国和西方发生的四次新古典主义建筑现象从时间,社会背景,建筑风格,建筑类型,当时的社会需求和社会意义等方面进行分析比较,最后通过时间上的纵向比较和空间上的横向比较得出结论。从而对时下流行的“新古典主义”一词,进行全面的理解和把握。     

Surface functionalization of mesoporous antimony doped tin oxide by metalorganic reaction

Electrically conducting mesoporous antimony doped tin oxide was functionalized by the metalorganic reaction with several Grignard reagents. This fast and efficient grafting approach enables a direct connection of the metal atoms with the organic functionalities avoiding the formation of insulating Si–O linkers, which is of special interest for the interfacial charge transfer processes. Using this approach we introduced vinyl, allyl and phenyl groups into the pores of mesoporous ATO, which was confirmed by IR spectroscopy, TGA and nitrogen sorption measurements. We obtained a high loading of organic groups corresponding to about 50–60% of the monolayer surface coverage. The obtained mesoporous inorganic–organic hybrids can serve as a platform for incorporation of electrochemically active species.     

Lipid Metabolism and Cardiovascular Morbidity and Mortality in Hemodialysis Patients: Role of Factors Modulating Cytosolic Calcium

Animal studies indicate that insulin resistance and glucose intolerance leading to dyslipidemia in uremic rats are associated with increased cytosolic calcium ([Ca⁺⁺ i]). The resistance and intolerance are reversed with verapamil, but recur after its discontinuation. This finding suggests that hyperparathyroid‐induced [Ca ⁺⁺ i] increase is responsible for the metabolic derangement. We retrospectively examined, over a 12‐year period, the effects of factors that lower [Ca ⁺⁺i] on total serum cholesterol and triglycerides in 332 hemodialysis (HD) patients. Because the study was retrospective, detailed lipid profiles were not available. We therefore relied on morbidity and mortality outcomes related to atherosclerotic vascular disease. Patients with diabetes mellitus were excluded, because their dyslipidemia and vascular disease are mediated via a different mechanism. Four groups emerged: group I [high parathormone (PTH) in the absence of calcium channel blockers (CCBs), n = 107], representing the highest [Ca⁺⁺ i]; group II (high PTH in the presence of CCBs, n = 76) and group III (lower PTH in the absence of CCBs, n = 66), representing intermediate [Ca ⁺⁺ i]; and group IV (lower PTH in the presence of CCBs, n = 83) representing the lowest [Ca ⁺⁺i]. The theoretically lower [Ca ⁺⁺ i] was achieved via CCB therapy or lower PTH, or both. The mean serum cholesterol in group I was 322 ± 24 mg/dL and the level of triglycerides was 398 ± 34 mg/dL. Group II had mean serum cholesterol of 196 ± 16 mg/dL and triglycerides of 157 ± 17 mg/dL. Group III had a mean serum cholesterol of 202 ± 19 mg/dL and triglycerides of 160 ± 15 mg/dL. Group IV had a mean serum cholesterol of 183 ± 9 mg/dL and triglycerides of 94 ± 6 mg/dL. The differences in cholesterol and triglyceride levels among four groups were significant (p < 0.001) by one‐way analysis of variance (ANOVA). The incidence of cardiovascular morbidity and mortality events was 61% in group I, 24% in group II, 28% in group III, and 18% in group IV (χ ² = 47.7, p < 0.001). We conclude that, in non diabetic HD patients, hyperparathyroidism, especially in the absence of CCBs, is associated with severe dyslipidemia and increased risk of cardiovascular morbidity and mortality. Dyslipidemia may be related to a hyperparathyroid‐induced increase in cytosolic calcium [Ca⁺⁺i]. Lowering [Ca⁺⁺i] by decreasing PTH or by blocking calcium entry into cells (via CCBs), or both, is associated with less dyslipidemia and improved long‐term cardiovascular morbidity and mortality. Prospective randomized studies, with actual measurement of [Ca ⁺⁺i], are needed to verify the results of this study.     

Illumination-induced properties of highly ordered mesoporous TiO2 layers with controlled crystallinity

The evaporation-induced self-assembly method using a novel diblock (poly(ethylene-co-butylene)-b-poly(ethylene oxide)) copolymer (KLE) provides fully crystalline mesoporous layers of TiO₂ exhibiting high thermal stability up to 700 °C, high photocatalytic activity in the decomposition of methyl stearate and facile transformation into a substantially stable superhydrophilic state by 1 mW/cm² UV-illumination.     

Supramolecular host–guest systems constructed of pyrrole derivatives and 3D-coordination polymers

Pyrrole derivatives have been shown to be completely or partially oxidized within the expandable channels of the 3D-coordination polymers [(R₃Sn)₃Fe(CN)₆] _n and [(R₃Sn)(R₃^′Sn)₂Fe(CN)₆] _n , R and R′ = Me, n-Bu, or Ph, to give novel class of supramolecular host–guest systems. The structures and physical properties of these host–guest systems depend on the reaction time, nature of the host and guest, the space empty within the network of the 3D-coordination polymers. Pyrrole undergoes oxidative polymerization in the channels of the 3D-coordination polymers to form semiconducting diamagnetic supramolecular host–guest systems. Whereas N-methylpyrrole and 2,5-dimethylpyrrole are not polymerized under these experimental conditions, but give paramagnetic charge transfer (CT) supramolecular host–guest systems.     

Highly crystalline WO3 thin films with ordered 3D mesoporosity and improved electrochromic performance

WO3 thin layers with nanometer-scale periodicity were prepared by evaporation-induced self-assembly (EISA) using a novel amphiphilic block-copolymer template (poly(ethylene-co-butylene)-block-poly(ethylene oxide)). The evolution of the mesoporous ordered network and the crystallinity of the framework were monitored by 2D-SAXS, WAXS, SEM, XPS, and porosimetry. By annealing the films, the pore-wall crystallinity is adjusted between fully amorphous and highly crystalline without mesostructural degradation. Thus, the crystalline-film framework is composed of phase-pure monoclinic WO3 nanoparticles (12-14 nm in size). Furthermore, heat treatment transforms the originally spherical mesopores into ellipsoids, resulting in a unidirectionally shrunken, but still well-defined and fully accessible bcc mesopore architecture. The influence of mesoporosity and crystallinity on electrochemical/electrochromic characteristics was addressed by monitoring electrochemical features and the absorption changes during Li insertion/extraction (repetitive potentiostatic cycling). Both the amorphous and crystalline mesoporous films possess electrochromic response times on the order of only seconds, which are attributable to the facilitated insertion of guest ions due to shortening of the diffusion path lengths. Also, the insertion/extraction reversibility of crystalline WO3 layers with 3D mesoporosity is improved compared to amorphous ones and reaches values close to 100%.