Iron-oxide-modified nanosized diamond: preparation, characterization, and catalytic properties in methanol decomposition

Nanosized diamond (UDD), obtained by a detonation procedure, was modified with iron from the corresponding acetylacetonate precursor under various pretreatment conditions. Nitrogen physisorption, X-ray diffraction, temperature-programmed reduction, and FTIR and M?ssbauer spectroscopy were used for their characterization. The samples' catalytic behavior in methanol decomposition was also studied. The physicochemical and catalytic properties of the obtained materials (Fe/UDD) were compared with those of other iron-oxide-modified mesoporous supports with different nature and functionality (MCM-48 silica and CMK-1 carbon). The highest catalytic activity and stability was achieved with air-pretreated Fe/UDD.     

A new strategy utilizing electrospray ionization-quadrupole ion trap mass spectrometry for the qualitative determination of GnRH peptides

Numerous forms of the neurotransmitter GnRH have been discovered in vertebrates and invertebrates. Methods used for identification of these peptides are laborious and often require the application of multiple, confirmatory techniques. In this study, we investigate whether HPLC-MS/MS and de novo sequencing techniques applied to whole peptide analysis can provide a simpler approach to GnRH characterization. Experiments were performed with six GnRH forms (chicken I, chicken II, lamprey III, mammalian, salmon and seabream) to determine whether MS/MS spectra would be dominated by proline-directed fragmentation to the detriment of obtaining sufficient fragmentation for sequencing. While the expected b8 fragment was prominent, sufficient ion series were obtained for the six GnRH peptides to provide sequence identification. On the basis of the patterns observed for six model peptides, similar fragmentation patterns are expected for other GnRH forms. To confirm the applicability of the method, extracts from Sprague-Dawley rat brains were examined. These experiments confirm the presence of mammalian GnRH and a posttranslationally modified form of mammalian GnRH, hydroxyproline9 GnRH, in Sprague-Dawley rat brains and demonstrate that ESI-MS/MS techniques provide a valuable addition to existing qualitative methods.     

用于下一代传感和光源的新型材料、光纤及器件

制造技术与复杂模型、设计工具的进步使微纳结构光学器件的实现成为可能。微纳结构光学器件可用于导光与光的相互作用,液态或气态新型光源和传感器件。IPAS致力于新型光学材料研究与开发,将玻璃工艺和光纤开发有机结合,重点研究微纳结构光纤,光纤表面功能处理和器件开发。介绍了IPAS的研究实力和近年的发展概况,其中包括中红外光学材料、纳米粒子嵌入玻璃材料、新型化学和生物传感器(适用于超低量样本及/或体内样本)、激光器件,以及用于光数据处理的新型高非线性光纤。     

The role of the surfactant head group in the emulsification process: Single surfactant systems

To clarify the effect of the surfactant head group on the emulsification process, dilute dodecane in water emulsions were prepared in a small flow-through cell with three surfactants which had the same hydrocarbon tail length but different head groups. The different surfactants types were (a) a nonionic, hexa(ethyleneglycol) mono n-dodecyl ether (C12E6), (b) an anionic, sodium dodecyl sulfate (SDS), and (c) a cationic, n-dodecyl pyridinium chloride (DPC), and the emulsions were prepared under the same conditions. From dynamic light scattering measurements, it was shown that the mean steady state droplet size of the emulsions (obtained after 20 min dispersion) could be related to the interfacial tension at concentrations in the region of the cmc. This result was in agreement with laminar and turbulent viscous flow theory. However, the particle size versus surface tension data for the different surfactant systems did not fall on a single line. This behavior suggested that the surfactant played a secondary role in defining the droplet size (in addition to reducing the interfacial tension) possibly through diffusion and relaxation, during deformation of the interface. In addition, it was found that the values of the equilibrium "surfactant packing densities" of the different surfactants at the oil/water interface were almost equal near the cmc, but the mean droplet size and the interfacial tension at the cmc decreased following the order DPC>SDS>C12E6 .     

Metalorganic vapor phase epitaxy and characterizations of nearly-lattice-matched AlInN alloys on GaN/sapphire templates and free-standing GaN substrates

The epitaxy optimization studies of high-quality n-type AlInN alloys with different indium contents grown on two types of substrates by metalorganic vapor phase epitaxy (MOVPE) were carried out. The effect of growth pressure and V/III molar ratio on growth rate, indium content, and surface morphology of these MOVPE-grown AlInN thin films were examined. The surface morphologies of the samples were characterized by scanning electron microscopy and atomic force microscopy. By varying the growth temperatures from 860 °C to 750 °C, the indium contents in AlInN alloys were increased from 0.37% up to 21.4% as determined by X-ray diffraction (XRD) measurements. The optimization studies on the growth conditions for achieving nearly-lattice-matched AlInN on GaN templates residing on sapphire and free-standing GaN substrates were performed, and the results were analyzed in a comparative way. Several applications of AlInN alloy for thermoelectric and light-emitting diodes are also discussed.     

Site-specific crosslinking of annexin proteins by 1,4-benzoquinone: a novel crosslinker for the formation of protein dimers and diverse protein conjugates

Annexin V (1) specifically binds to phosphatidylserine on apoptotic and necrotic cells as well as certain cancer cells, making it an attractive vehicle for the delivery of therapeutically-relevant conjugates to such sites. The wild-type protein possesses a single thiol at Cys316, which is difficultly accessible to site-specific labeling by simple maleimides. By contrast, 1,4-benzoquinone site-specifically labels annexin V in minutes. The resulting conjugate (5) serves as an intermediate for crosslinking annexin molecules, which can be accomplished within hours either directly for linking annexin V-128 (19), or via an extended sequence involving the crosslinking of two units of (5) by the symmetrical α,ω-dithiol (20). Besides its ability to mediate protein dimer formation while retaining annexin V's ability to bind phosphatidylserine, (5) possesses classic 1,4-benzoquinone reactivity. Various nucleophiles and Diels-Alder dienes form adducts with (5) in reactions that may have general utility for the synthesis of novel biologically active entities. The present work presents the first example of thiol-specific crosslinking of proteins by 1,4-quinone-based methodology designed to exploit the reactivity of this versatile chemical entity.     

Parallel Symmetric Attack on NTRU using Non-Deterministic Lattice Reduction

Currently, the most efficient passive attack on the NTRU public-key cryptosystem, proposed by Coppersmith and Shamir [1], is based on finding a short enough vector in an integral lattice. An NTRU lattice possesses a cyclic automorphism group whose symmetry may be exploited. We have designed methods for reducing bases of NTRU integral lattices based on this symmetry. In addition to these methods, we use hill-descending techniques to combine new and proposed lattice-reduction algorithms. This approach includes deterministic and non-deterministic components which may be efficiently parallelized.     

Reversible reduction drives anion ejection and C60 binding within an FeII4L6 cage

Fe^II₄L₆ tetrahedral cage 1 was prepared from a redox-active dicationic naphthalenediimide (NDI) ligand. The +20 charge of the cage makes it a good host for anionic guests, with no binding observed for neutral aromatic molecules. Following reduction by Cp₂Co, the cage released anionic guests; subsequent oxidation by AgNTf₂ led to re-uptake of anions. In its reduced form, however, 1 was observed to bind neutral C₆₀. The fullerene guest was subsequently ejected following cage re-oxidation. The guest release process was found to be facilitated by anion-mediated transport from organic to aqueous solution. Cage 1 thus employs electron transfer as a stimulus to control the uptake and release of both neutral and charged guests, through distinct pathways.

Fe^II₄L₆ cage 1 binds anionic guests but not neutral guests. In its reduced form, the cage can bind neutral C₆₀. Reduction and oxidation of the cage could thus be used as a stimulus to control the uptake and release of both neutral and charged guests.     

A kinetic and mechanistic study of the reactions of OH radicals and Cl atoms with 3,3,3-trifluoropropanol under atmospheric conditions

Product distribution studies of the OH radical and Cl atom initiated oxidation of CF3CH2CH2OH in air at 1 atm and 298 +/- 5 K have been carried out in laboratory and outdoor atmospheric simulation chambers in the presence and absence of NOx. The results show that CF3CH2CHO is the only primary product and that the aldehyde is fairly rapidly removed from the system. In the absence of NOx the major degradation product of CF3CH2CHO is CF3CHO, and the combined yields of the two aldehydes formed from CF3CH2CH2OH are close to unity (0.95 +/- 0.05). In the presence of NOx small amounts of CF3CH2C(O)O2NO2 were also observed (<15%). At longer reaction times CF3CHO is removed from the system to give mainly CF2O. The laser photolysis-laser induced fluorescence technique was used to determine values of k(OH + CF3CH2CH2OH) = (0.89 +/- 0.03) x 10(-12) and k(OH + CF3CH2CHO) = (2.96 +/- 0.04) x 10(-12) cm3 molecule(-1) s(-1). A relative rate method has been employed to measure the rate coefficients k(OH + CF3CH2CH2OH) = (1.08 +/- 0.05) x 10(-12), k(OH + C6F13CH2CH2OH) = (0.79 +/- 0.08) x 10(-12), k(Cl + CF3CH2CH2OH) = (22.4 +/- 0.4) x 10(-12), and k(Cl + CF3CH2CHO) = (25.7 +/- 0.4) x 10(-12) cm3 molecule(-1) s(-1). The results from this investigation are discussed in terms of the possible importance of emissions of fluorinated alcohols as a source of fluorinated carboxylic acids in the environment.