Electrochemical approaches for the fabrication and/or characterization of pure and hybrid templated mesoporous oxide thin films: a review

Electrochemistry can be used for fabrication and characterization of mesoporous oxide films. First, this review provides insight into the methods used to prepare templated mesoporous thin films on an electrode surface, i.e., evaporation-induced self-assembly (EISA) and electrochemically assisted self-assembly (EASA). Electrochemical characterization of mass transport processes in pure and organically functionalized mesoporous oxide films is then discussed. The electrochemical response can be basically restricted by the electron/mass transfer reaction at the electrode–film interface and diffusion through mesopore channels. The contributions of cyclic voltammetry, hydrodynamic voltammetry, electrochemical impedance spectroscopy, and scanning electrochemical microscopy to the characterization of films with distinct mesostructures are finally described, with special emphasis on identification of conditions that can affect the electrochemical response recorded with such modified electrodes.

Strong improvement of interfacial properties can result from slight structural modifications of proteins: the case of native and dry-heated lysozyme

Identification of the key physicochemical parameters of proteins that determine their interfacial properties is still incomplete and represents a real stake challenge, especially for food proteins. Many studies have thus consisted in comparing the interfacial behavior of different proteins, but it is difficult to draw clear conclusions when the molecules are completely different on several levels. Here the adsorption process of a model protein, the hen egg-white lysozyme, and the same protein that underwent a thermal treatment in the dry state, was characterized. The consequences of this treatment have been previously studied: net charge and hydrophobicity increase and lesser protein stability, but no secondary and tertiary structure modification (Desfougères, Y.; Jardin, J.; Lechevalier, V.; Pezennec, S.; Nau, F. Biomacromolecules 2011, 12, 156-166). The present study shows that these slight modifications dramatically increase the interfacial properties of the protein, since the adsorption to the air-water interface is much faster and more efficient (higher surface pressure). Moreover, a thick and strongly viscoelastic multilayer film is created, while native lysozyme adsorbs in a fragile monolayer film. Another striking result is that completely different behaviors were observed between two molecular species, i.e., native and native-like lysozyme, even though these species could not be distinguished by usual spectroscopic methods. This suggests that the air-water interface could be considered as a useful tool to reveal very subtle differences between protein molecules.     

Photo-SRM: laser-induced dissociation improves detection selectivity of Selected Reaction Monitoring mode

Selected Reaction Monitoring (SRM) carried out on triple‐quadrupole mass spectrometers coupled to liquid chromatography has been a reference method to develop quantitative analysis of small molecules in biological or environmental matrices for years and is currently emerging as a promising tool in clinical proteomic. However, sensitive assays in complex matrices are often hampered by the presence of co‐eluted compounds that share redundant transitions with the target species. On‐the‐fly better selection of the precursor ion by high‐field asymmetric waveform ion mobility spectrometry (FAIMS) or increased quadrupole resolution is one way to escape from interferences. In the present work we document the potential interest of substituting classical gas‐collision activation mode by laser‐induced dissociation in the visible wavelength range to improve the specificity of the fragmentation step. Optimization of the laser beam pathway across the different quadrupoles to ensure high photo‐dissociation yield in Q2 without detectable fragmentation in Q1 was assessed with sucrose tagged with a push‐pull chromophore. Next, the proof of concept that photo‐SRM ensures more specific detection than does conventional collision‐induced dissociation (CID)‐based SRM was carried out with oxytocin peptide. Oxytocin was derivatized by the thiol‐reactive QSY® 7 C₅‐maleimide quencher on cysteine residues to shift its absorption property into the visible range. Photo‐SRM chromatograms of tagged oxytocin spiked in whole human plasma digest showed better detection specificity and sensitivity than CID, that resulted in extended calibration curve linearity. We anticipate that photo‐SRM might significantly improve the limit of quantification of classical SRM‐based assays targeting cysteine‐containing peptides. Copyright © 2011 John Wiley & Sons, Ltd.     

Measurement of the fundamental thermal noise limit in a cryogenic sapphire frequency standard using bimodal maser oscillations

We report observations of the Schawlow-Townes noise limit in a cryogenic sapphire secondary frequency standard. The effect causes a fundamental limit to the frequency stability, and was measured through the novel excitation of a bimodal maser oscillation of a Whispering Gallery doublet at 12.04 GHz. The beat frequency of 10 kHz between the oscillations enabled a sensitive probe for this measurement of fractional frequency instability of 10(-14) tau(-1/2) with only 0.5 pW of output power.     

焊接等离子体[82%Ar-18%CO2]-Fe净辐射系数的计算

净辐射系数是数值模拟中表征等离子体辐射属性最常用的参数。考虑了线谱、连续谱和分子带状谱等多种辐射机制,计算了3～25 kK不同Fe含量下[82%Ar-18%CO₂]-Fe等离子体的净辐射系数,为GMAW电弧(82%Ar-18%CO₂保护气,低合金钢焊丝)的数值模拟提供了完整的辐射属性数据。此外,通过分析发现,当Fe蒸汽加入到82%Ar-18%CO₂混合物中,即使Fe含量极低,等离子体净辐射系数也会显著增大。同时,由于Fe的加入,原本辐射贡献率较高的分子带状谱和连续谱辐射相对线谱辐射可忽略不计。     

Equation of state of boron subarsenide B12As2 to 47 GPa

Compressibility of boron subarsenide B₁₂As₂ has been studied by synchrotron X-ray diffraction up to 47?GPa at room temperature in a diamond anvil cell using Ne pressure transmitting medium. A fit of experimental p–V data by Vinet equation of state yielded the bulk modulus of 150(4) GPa and its first pressure derivative of 6.4(3). No pressure-induced phase transitions have been observed.     

Lateral Deprotometallation-Trapping Reactions on Methylated Pyridines,Quinolines and Quinoxalines Using Lithium Diethylamide

The functionalization of methylated azines and diazines has aroused the interest of chemists given the structural diversity that it affords. Hindered lithium dialkylamides have been used to deprotometallate these substrates chemoselectively. In contrast, it can be observed that, despite some promising work, lithium diethylamide has been used very little for this purpose. Our objective here is on the one hand to make an inventory of what reagents have been used to deprotometallate methylpyridines, -quinolines and -quinoxalines, and on the other hand to describe the results obtained by seeking to functionalize a series of substrates with lithium diethylamide (picolines, 2,4-lutidine, methylquinolines and 2-methylquinoxaline). Our efforts to take advantage of the use of an in-situ trap (a zinc chloride chelate) in these reactions are also described.     

An exponential lower bound for Zadeh’s pivot rule

Mathematical Programming - The question whether the Simplex Algorithm admits an efficient pivot rule remains one of the most important open questions in discrete optimization. While many natural,...