用热聚法固定指示剂的光纤氧气传感器研究

采用热聚法将甲叉双丙烯酰胺（MBBA）聚合并共价交联在硅烷化的玻璃微珠上 ，同时将指示剂Ru（Ⅱ）-邻啡咯啉配合物物理包埋于聚合物中，研制了一种基于 荧光猝灭原理的光纤氧气传感器，采用NaHSO_3-O_2-MnSO_4体系引发MBBA水溶液热 聚合后应，通过确定NaHSO_3,MnSO_4,MBBA和Ru(phen)_3Cl_2的最佳反应浓度以及 玻璃微珠的尺寸，优化了聚合反应条件，改善了指示剂的固定效果，制备了性能较 好的传感器探头，该传感器的检测下限为5×10~(-6)(V/V)，响应时间为10s该传感 器连续工作50min,重复性标准偏差为±1%。     

Influence of response factors on determining equilibrium association constants of non-covalent complexes by electrospray ionization mass spectrometry

A method for determining the equilibrium association constant of a complexation reaction A + B left harpoon over right harpoon AB by electrospray ionization mass spectrometry is described. The method consists in measuring the relative intensities of the peaks corresponding to A and to AB in equimolar A-B solutions at different concentrations C(0). The results are fitted by a non-linear least-squares procedure, with the two variable parameters being the equilibrium association constant K(a) and a factor R, defined by I(AB)/I(A) = R x [AB]/[A]. The factor R is the ratio between the response factors of AB and A, and corrects for the relative electrospray responses of the complex and the free substrate A, mass discrimination of instrumental origin and/or moderate in-source dissociation. The method is illustrated with the following two systems: complexes between a double-stranded 12-base pair oligonucleotide and minor groove binders, and cyclodextrin complexes with alpha,omega-dicarboxylic acids. For the oligonucleotide complexes, it is found that the response of the complex is not dramatically different to the response of the free oligonucleotide duplex, as the double helix conformation is disturbed by the drug only to a minor extent. In the case of cyclodextrin complexes, these complexes were found to have a much higher response than free cyclodextrin. This may be due to the fact that cyclodextrin is neutral in solution, whereas the complex is charged, but it can also stem from the fact that a significant proportion of the complex is in a non-inclusion geometry. The present method requires the exact determination of the concentrations of the reactants and is applicable to 1 : 1 complexes.     

The crystal structure of the molybdenum cementite Mo12Fe22C10 (ξ-phase)

The crystal structure of molybdenum cementite Mo₁₂Fe₂₂C₁₀ (-phase) has been determined by means of a single crystal x-ray diffraction study of crystal fragments. The lattice parameters were found to be:a=10.865 (3),b=7.767 (2),c=6.559 (2) Å and =120.13 (2)°, space group C2/m;Z=1. From the analysis ofPatterson maps and differenceFourier analysis the atomic parameters were derived, yielding a residual ofR=0.059. The crystal structure contains octahedral and triangular prismatic groups which accommodate the carbon atoms in their voids, as is usually found in interstitial compounds. The octahedral building group consists of four Mo- and two Fe-atoms, the triangular prism is built up by four Fe-and two Mo-atoms. The mode of filling of the metal polyhedra is discussed.

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Die Kristallstruktur von Molybdän-Zementit, Mo₁₂Fe₂₂C₁₀ (-Phase)

Zusammenfassung Die Kristallstruktur von Molybdän-Zementit, Mo₁₂Fe₂₂C₁₀ (-Phase) wird auf Grund von Einkristall-Beugungsaufnahmen unter Anwendung vonPatterson-and DifferentialFourier-Analysen bestimmt. In der monoklinen Elementarzelle (a=1.870;b=7.67;c=6.563 Å, =120.1°) Raumgruppe C 2/m befindet sich eine Formeleinheit Mo₁₂Fe₂₂C₁₀ (oderZ=2, Mo₆Fe₁₁C₅). DerR-Wert von 6% für 1200 Reflexe unterstreicht die Richtigkeit der Struktur, die aus oktaedrischen und trigonal prismatischen Gruppen aufgebaut ist. Die Oktaedergruppe besteht aus 4 Mo- und 2-Fe-Atomen, die trigonal prismatische Gruppe aus 4 Fe- und 2 Mo-Atomen. Die Kohlenstoffatome füllen die Lücken dieser Bauelemente, wie es für typische Einlagerungscarbide (Komplexcarbide) erwartet werden kann.

     

First‐principles study of metal/nitride polar interfaces: Ti/TiN

We have examined the optimal interface structure, ideal work of adhesion and bonding character of polar Ti(110)/TiN(111) interfaces by first‐principles density‐functional plane‐wave pseudopotential calculations. Both Ti‐ and N‐terminated interfaces, including six different interface structures, were calculated. The interface structure for each termination, continuing the TiN crystal structure across the interface, has the largest work of adhesion. Although both terminations yield substantial adhesion energies in the range 3–7 J m^?2, the N‐terminated interface is ～4 J m^?2 stronger than the Ti‐terminated interface. Analysis of the interfacial electronic structure shows that the Ti‐terminated interface is a mixed strong, metallic and weak covalent character, whereas the N‐terminated interface is a polar covalent bond similar to the Ti/TiC interface. Further study of the separation of the optimal interface shows that the cleavages will never fracture at the interface due to the strong bonding, which is consistent with the experimental results. Copyright © 2003 John Wiley & Sons, Ltd.     

聚L－谷氨酸－炔诺酮肟酯复合体的制备

合成了聚Ｌ－谷氨酸－炔诺酮肟酯的复合体，炔诺酮的接入量为２２．８％．体外释放时间约１５大。     

A Review on the Potential and Limitations of Recyclable Thermosets for Structural Applications

Abstract

The outstanding performance of conventional thermosets arising from their covalently cross-linked networks directly results in a limited recyclability. The available commercial or close-to-commercial techniques facing this challenge can be divided into mechanical, thermal, and chemical processing. However, these methods typically require a high energy input and do not take the recycling of the thermoset matrix itself into account. Rather, they focus on retrieving the more valuable fibers, fillers, or substrates. To increase the circularity of thermoset products, many academic studies report potential solutions which require a reduced energy input by using degradable linkages or dynamic covalent bonds. However, the majority of these studies have limited potential for industrial implementation. This review aims to bridge the gap between the industrial and academic developments by focusing on those which are most relevant from a technological, sustainable and economic point of view. An overview is given of currently used approaches for the recycling of thermoset materials, the development of novel inherently recyclable thermosets and examples of possible applications that could reach the market in the near future.     

Properties of 8-Cyano-5-phenyl-7-trifluoromethyl-2,3-dihydroimidazo[1,2-a]pyridines

The alkylation, acylation, halogenation, nitration, oxidation, and hydrolysis reactions of 8-cyano-5-phenyl-7-trifluoromethyl-2,3-dihydroimidazo[1,2-a]pyridine have been studied. It was found that the 6-halo derivatives add alcohol to give covalent solvates. X-ray analysis has been carried out on one of the solvates (6-chloro-8-cyano-7-ethoxy-5-phenyl-7-trifluoromethyl-1,2,3,7-tetrahydroimidazo[1,2-a]pyridine) as well as on 8-cyano-5-phenyl-7-trifluoromethyl-2,3-dihydroimidazo[1,2-a]pyridine trifluoroacetate.     

Room Temperature Solid State Reaction Involving Structural Transformation of Covalent Oxide Network

An interesting structural transformation from a two dimensional (2d) covalent oxide network with a layered structure to a three-dimensional (3d) network with a tunnel structure was found at room temperature in the mixture of hydrated alkali-metal molybdenum bronze and amorphous alkali-metal molybdate. From various experimental results it was concluded that the transformation was due to a room temperature solid state reaction.     

Ultrafine molybdenum carbide nanoparticles supported on nitrogen doped carbon nanosheets for hydrogen evolution reaction

Nitrogen doped carbon nanosheets supported molybdenum carbides nanoparticles (Mo_xC/NCS) have been synthesized by tuning the mass ratio of melamine and ammonia molybdate. The Mo₂C/NCS-10 exhibits superior electrocatalytic performance and stability for HER, which was attributed to N-doped carbon nanosheets, small particle size, mesoporous structure, and large electrochemical active surface area.     

Studies of the Reaction Behavior of Nitryl Compounds Towards Azides: Evidence for Tetranitrogen Dioxide,N4O2

The reaction behavior of NaN₃, AgN₃, and Me₃SiN₃ towards FNO₂, CINO₂, NO₂SbF₆, and NO₂BF₄ was investigated. At -30°C or below in a solvent-free system sodium azide did not react with CINO₂, NO₂BF₄, or NO₂SbF₆. Below -30°C silver azide did not react either with neat C1NO₂. Treatment of Me₃SiN₃ with pure C1NO₂ led to the formation of C1N₃, N₂O, and Me₃SiOSiMe₃. A mechanism for this reaction has been proposed. Pure chlorine azide was isolated by fractional condensation and identified by its low-temperature Raman spectrum (liquid state). The reaction of Cp₂Ti(N₃)₂ with C1NO₂ also yielded C1N₃ as the only azide-containing reaction product. Treatment of FNO₂ with NaN₃ at temperatures as low as -78°C always ended in an explosion which was probably due to the formation of FN₃ as one of the reaction products. The reaction of NO₂SbF₆ with NaN₃ in liquid CO₂ (-55°C· T· -35°C) as the solvent afforded a new azide species which was stable at low temperature in solution only and was investigated by means of low-temperature Raman spectroscopy. The obtained vibrational data give strong evidence for the presence of tetranitrogen dioxide, N₄O₂, which can be regarded as nitryl azide (NO₂N₃). The structure and vibrational frequencies of N₄O₂ were computed ab initio at correlated level (MP2/6-31 + G^*). In liquid xenon (-100°C· T· -60°C) NaN₃ did not react with NO₂SbF₆. A previous literature report on the preparation of N₄O₂ could not be established.