高纯锗探测器的广泛应用和自主研制进展

以目前国际上极为活跃开展的暗物质探测、无中微子双 衰变研究为例,评述了高纯锗探测器的重要性及其广泛的应用前景。介绍了己开展的高纯锗单晶、探测器制备的关键技术研究进展:合作单位已研制出了用于高纯锗单晶材料制备的区熔炉、单晶炉;并制备出直径为20  50 cm、纯度为12N(< 41011  atoms/cm3)、位错< 5000 atoms/cm2 的锗单晶;掌握了高纯锗探测器(平面型、同轴型)制备的关键技术,用进口高纯锗单晶材料制备出的同轴型高纯锗探测器对射线的能量分辨率及探测效率均达到进口产品指标,使用自制的12N 高纯锗单晶材料己制备出平面型高纯锗探测器。呼吁加速高纯锗研制的自主创新步伐,尽早实现其国产化目标。The article reviews importance and wide applications of HPGe detector, especially the application on the dark matter search experiment and double beta decay experiment. The research progress on the Highpurity germanium single crystal and HPGe detector in China has been introduced. The cooperation partner developed new type zone-refining furnace and single crystal furnace. The ultra-purity germanium single crystal with 20~50 cm, purity up to 12N(net impurity concentration is less than 41011 atoms/cm3), and dislocation less than 5 000 /cm3 was prepared. The key technologies for preparing planar and coaxial HPGe detector were mastered. The coaxial detector, which has been made of imported ultra-purity germanium single crystal has excellent energy resolution and efficiency as the imported commercial detector. The planar detector using selfmade germanium single crystal was also successfully manufactured. The research group appeals for speeding up the pace of independent innovation on the high-purity germanium, and achieving the high-purity germanium localization as soon as possible.     

Ion transport in tumors under electrochemical treatment: in vivo, in vitro and in silico modeling

The electrochemical treatment of cancer (EChT) consists in the passage of a direct electric current through two or more electrodes inserted locally in the tumor tissue. The extreme pH changes induced have been proposed as the main tumor destruction mechanism. Here, we study ion transport during EChT through a combined modeling methodology: in vivo modeling with BALB/c mice bearing a subcutaneous tumor, in vitro modeling with agar and collagen gels, and in silico modeling using the one-dimensional Nernst-Planck and Poisson equations for ion transport in a four-ion electrolyte. This combined modeling approach reveals that, under EChT modeling, an initial condition with almost neutral pH evolves between electrodes into extreme cathodic alkaline and anodic acidic fronts moving towards each other, leaving the possible existence of a biological pH region between them; towards the periphery, the pH decays to its neutral values. pH front tracking unveils a time scaling close to t(1/2), signature of a diffusion-controlled process. These results could have significant implications in EChT optimal operative conditions and dose planning, in particular, in the way in which the evolving EChT pH region covers the active cancer cells spherical casket.     

OH, HO2, and ozone gaseous diffusion coefficients

The diffusion of OH, HO2, and O3 in He, and of OH in air, has been investigated using a coated-wall flow tube reactor coupled to a chemical ionization mass spectrometry. The diffusion coefficients were determined from measurements of the loss of the reactive species to the flow tube wall as a function of pressure. On the basis of the experimental results, D(OH-He) = 662 +/- 33 Torr cm2 s-1, D(OH-air) = 165 +/- 20 Torr cm2 s-1, D(HO2-He) = 430 +/- 30 Torr cm2 s-1, and D(O3-He) = 410 +/- 25 Torr cm2 s-1 at 296 K. We show that the measured values for OH and HO2 are in better agreement with measured values of their polar analogues (H2O and H2O2) compared with measured values of their nonpolar analogues (O and O2). The measured value for OH in air is 25% smaller than that for O (the nonpolar analogue). The difference between the measured value for HO2 and O2 (the nonpolar analogue) in air is expected to be even larger. Also we show that calculations of the diffusion coefficients based on Lennard-Jones potentials are in excellent agreement with the measurements. This gives further confidence that these calculations can be used to estimate accurate diffusion coefficients for conditions where laboratory data currently do not exist.     

Determination of azoxystrobin residues in grapes, musts and wines with a multicommuted flow-through optosensor implemented with photochemically induced fluorescence

In this paper, the conversion of azoxystrobin in a strongly fluorescent degradation product by UV irradiation with quantitative purposes and its fluorimetric determination are reported for the first time. A multicommuted flow injection-solid phase spectroscopy (FI-SPS) system combined with photochemically-induced fluorescence (PIF) is developed for the determination of azoxystrobin in grapes, must and wine. Grape samples were homogenized and extracted with methanol and further cleaned-up by solid-phase extraction on C₁₈ silica gel. Wine samples were solid-phase extracted on C₁₈ sorbent using dichloromethane as eluent. Recoveries of azoxystrobin from spiked grapes (0.5-2.0 mg Kg⁻¹), must (0.5-2.0 μg mL⁻¹) and wine (0.5-2.0 μg mL⁻¹) were 84.0-87.6%, 95.5-105.9% and 88.5-111.2%, respectively. The quantification limit for grapes was 0.021 mg Kg⁻¹, being within European Union regulations, and 18 μg L⁻¹ and 8 μg L⁻¹ for must and wine, respectively.     

Electroactive thiazole derivatives capped with ferrocenyl units showing charge-transfer transition and selective ion-sensing properties: a combined experimental and theoretical study

The synthesis, optical and electrochemical properties, and X-ray characterization of two thiazole derivatives capped by ferrocenyl groups (5 and 7) and their model compounds with one ferrocenyl, either at 2 or 5 position of the mono- or bis-thiazolyl rings (3, 9, 11, and 14), are presented. Bisferrocenyl thiazole 5 forms the mixed-valence species 5*+ by partial oxidation which, interestingly, shows an intramolecular electron-transfer phenomenon. Moreover, the reported heteroaromatic compounds show selective ion-sensing properties. Thus, ferrocenylthiazoles linked across the 5 position of the heteroaromatic ring are selective chemosensors for Hg2+ and Pb2+ metal ions; 5-ferrocenylthiazole 3 operates through two channels, optical and redox, for Hg2+ and only optical for Pb2+, whereas 1,1'-bis(thiazolyl)ferrocene 14 is only an optical sensor for both metal ions. Moreover, complex 3 behaves as an electrochemically induced switchable chemosensor because of the low metal-ion affinity of the oxidized 3*+ species. On the other hand, ferrocenylthiazole 9, in which the heterocyclic ring and the ferrocene group are linked across the 2 position, is a selective redox sensor for Hg2+ metal ions, and it responds optically, as does bis(thiazolyl)ferrocene 11, to a narrow range of cations (Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+). Finally, bis(ferrocenyl)thiazole 5 is a dual optical and redox sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+, whereas bis(ferrocenyl) compound 7, bearing a bis(thiazole) unit as a bridge, is only a chromogenic sensor for Zn2+, Cd2+, Hg2+, Ni2+, and Pb2+. The experimental data and conclusions about both the electronic and ion-sensing properties are supported by DFT calculations which show, in addition, an unprecedented intramolecular electron-transfer reorganization after the first one-electron oxidation of compound 5.     

Multilinear Operator Ideals Associated to Saphar Type (<Emphasis Type="Italic">n</Emphasis> + 1)-tensor Norms

We study an (n + 1)-tensor norm generalizing Saphar’s classic norm to (n+1)-fold tensor products.We characterize the maps in the minimal and maximal multilinear operator ideals related to in the sense of Defant and Floret. Partially supported by the MEC and FEDER project MTM2004-02262 and AVCIT group 03/050.     

烷基锌与亚胺不对称加成反应的研究进展

综述了烷基锌与亚胺不对称加成反应的最新进展。参考文献31篇。     

手性Schiff Base-Ti(OR)4配合物催化醛的不对称硅腈化反应

设计合成了新型手性Salen-Ti(OR)₄配合物催化剂,用其催化一系列醛的不对称硅腈化反应,得到了e.e.值为22.4%～87.1%的氰醇.催化剂中抗衡离子的Lewis碱强烈地影响催化活性,但对反应的对映选择性影响很小,并探讨了其不对称催化反应机理.     

离子基碳-氧键断裂能量的研究(Ⅱ)──负离子基的键能

合成了3个系列芳香类含碳一氧键的化合物,用循环伏安法测定了相关的氧化还原电势,通过热力学循环首次估测了负离子基的碳-氧键的断裂能量(ΔH_cleav[C-O]^·-).结果表明:得到1个电子形成负离子基可以活化碳-氧键。这与具有相同结构的正离子基的情况是一致的,但其活化程度略小。相关分析表明:ΔH_cleav[C-O]^·-vs(ΔE_red[C-O]+ΔpK_a[HA])和ΔH_cleav[C-O]^·+vs.(ΔBDE-ΔE_ox[C-O])均呈线性。讨论了负离子基和正离子基及其母体化合物中键的特征,并与文献中有关的键能数据进行了比较。