Well defined carbazole-based hole-transporting amorphous molecular materials

Monodisperse carbazole-based oligomers have been synthesized via C-N bonds formation by the modified Ullmann reaction. The full characterization of their structure is presented. These derivatives are highly thermally stable amorphous compounds with glass transition temperatures of 167-171 degrees C and thermal decomposition temperatures of ca. 400 degrees C. Amorphous films of the materials were fabricated and their hole-transporting properties were tested in a light emitting device with Alq(3) as an electroluminescent and electron-transporting material.

REDOX THERMODYNAMICS OF CYTOCHROME-C AT THE BARE GLASSY-CARBON ELECTRODE

Investigation of the redox thermodynamics of horse heart cytochrome c at bare glassy carbon electrodes has been performed using cyclic voltammetry with a nonisothermal electrochemical cell. The thermodynamic parameters of the electron-transfer reaction of cytochrome c have been estimated in different component buffer solutions. The change DELTAS(re)-degrees in reaction center entropy and the formal potential E-degrees' (at 25-degrees-C, vs. standard hydrogen electrode (SHE)) for cytochrome c are found to be -64.1 J K-1 mol-1 and 0.251 V in phosphate buffer, -64.8 J K-1 mol-1 and 0.257 V in Tris + HCl buffer, -65.6 J K-1 mol-1 and 0.261 V in Tris+CH3COOH buffer (pH 7.0, ionic strength 100 mM). The temperature dependence of the formal potential obtained in phosphate buffer with or without NaCl in the range 5-55-degrees-C shows biphase characteristics in an alkaline solution with an intersection point at ca. 44-degrees-C or 42-degrees-C, which should be due to a structural change in the protein moiety of cytochrome c. However, in acidic and neutral solutions only a monotonic relationship between E-degrees' and temperature is observed. The effect of the buffer component on E-degrees' for cytochrome c is also discussed.

影响C4草本植物C���N比值变化的因素与土壤有机C���累的关系

文章对采自贵州从低海拔的东部到高海拔的西部且大致平行的石灰岩和砂岩两地带均生长的3种C4草本植物，即巴茅(Miscanthus floridulus)、白茅(Imperata cylindrica)和类芦(Neyraudia reynaudiana)，以及相对应的土壤表层样品，进行了营养元素和C���位素组成分析；研究营养元素含量随着海拔的不同而出现的变化趋势，以及这些元素之间的相互协变作用，尤其是Ca���N之间的相互协变作用对植物的N含量、C���N比值和δ^13C���的影响，以了解植物的C���N比值(指示植物残留物质量的一种标志)与土壤有机C���累的关系。研究结果表明，植物的N含量和δ^13C���具有随海拔的上升而显著增大趋势，而植物的C���N比值在砂岩地区虽有减小的趋势，在石灰岩地带则没有。对所研究的C4草本植物来说，在土壤pH值为5．8的中性条件下显示出Ca���最大吸收，因此，Ca���其他营养元素之间的协变模式在两种土壤类型中表现出相反的倾向，并存在土壤交换性Ca���边界浓度：当土壤可交换性Ca���含量为2．24mg／g，相应土壤的pH值在5．8以下时，随着土壤可交换性Ca���度的增大，植物的N含量上升，而植物的C���N比值会显著降低；当Ca���边界浓度以上时，随着土壤可交换性Ca���度的增大，植物的N含量下降，而植物的C���N比值有增加的趋势。由此可见，植物残留物的N含量和C���N比值受Ca���素含量的相互协变作用的影响。在砂岩地区，随着植物C���N比值的增高，土壤有机质的含量却随之下降，而在石灰岩地区则没有这种倾向。因此得出结论：植物的C���N比值的增大对土壤有机碳积累的影响主要取决于土壤的性质，尤其是取决于土壤可交换性Ca���含量。

拟南芥有性生殖模式和叶片特性对大气CO2浓度变化的响应

预计到本世纪末，大气CO2浓度将会增加到540～970ppm，大气CO2浓度升高所引起的全球气候变化已经受到广泛的关注。植物生长依赖CO2，并且对大气CO2浓度升高在结构和生理上产生响应。目前已有大量报道，从生态系统、群落、种群、个体、器官、组织、生理以及生化等水平上研究高浓度CO2所对植物产生的影响。但是有关高浓度CO2对植物有性生殖影响的报道却很少，同时多数实验均建立在短期的生殖响应，忽视了植物在长期高CO2浓度下具有的反馈作用和CO2浓度变化对植物的驯化作用。植物有性生殖与其生态适应性和农作物籽粒产量的关系极为密切;同时，植物有性生殖特性的变化，也可作为预测植物对全球气候变化响应的重要指标之一。为此，利用高浓度CO2对植物进行长期选择实验将很有必要。研究结果将为预测未来大气CO2浓度增加的条件下陆地生态系统的演变趋势、全球变化对植物有性生殖响应的方式和机制提供新的思路和有效方法。 　　在本研究中，我们以模式植物拟南芥(Arabidopsis thaliana)作为实验材料，利用370和700ppm CO2对其进行连续8个世代处理，首先研究高浓度CO2对每一个世代的拟南芥有性生殖特性的影响，然后比较各个世代中各种生殖特性指标变化的规律，从细胞、组织和个体尺度上揭示拟南芥有性生殖对全球变化的响应模式。此外，在700ppm CO2处理下，我们对拟南芥叶片生理、生化以及结构的变化进行了相关研究。两部分研究结果及主要结论如下： 　　首先，在每一个世代中，与370ppm CO2相比较，700ppm CO2处理显著促进了拟南芥开花，缩短生长周期，增加花、角果及种子等生殖的产量，降低种子N含量，提高种子C/N比、种子千粒重以及生殖生物量所占总生物量的比例等，而对种子萌发率、角果所含种子数目以及角果长度则无显著影响。但是， 通过对相同CO2浓度处理条件下，不同世代之间的研究结果比较发现，不同世代之间相关的生殖生物学指标并无显著差异。 　　其次，高浓度CO2显著降低叶片气孔密度、气孔指数、气孔导度以及蒸腾速率。在高浓度CO2处理下，叶肉细胞中叶绿体数目、叶绿体宽度和表观面积、淀粉粒大小和数量、叶片和细胞壁厚度等都显著增加，但是基粒内囊体膜的数量却显著下降。叶片中碳水化合物如可溶性总糖、淀粉以及纤维素含量在高浓度CO2下分别显著增加71.9%、78.7% 和 22.3%。此外，在高浓度CO2处理下，叶片中多数激素如如吲哚乙酸(indole-3-acetic acid, IAA)、赤霉素(gibberellin, GA)、玉米素核苷(zeatin riboside, ZR)、二氢玉米素核苷(dihydrozeatin riboside, DHZR)和异戊烯基腺苷(isopentenyl adenosine, iPA)均都显著地增加，而脱落酸(abscisic acid, ABA)含量却有所下降。最后，叶片中各种矿物质元素含量如N、P、K、Ca���Mg等含量在高浓度CO2处理下也都显著下降，而C/N比增加24.8％。 　　以上结果表明： 　　(1) 在每一个世代中，700ppm CO2处理对拟南芥各种有性生殖特性具有显著的影响，但是高浓度CO2处理对植物所引起的效应在多个世代以内并不能够传递给后代，所以在多个有性生殖世代内，高浓度CO2处理对植物生长、生殖没有驯化作用。 　　(2) 在高浓度CO2处理下，拟南芥叶片中叶绿体超微结构的变化，可能主要是由于叶绿体中淀粉粒数量和体积大小显著增加而引起。 　　(3) 在高浓度CO2处理下，由于拟南芥叶片内与促进细胞分裂与伸长的激素含量显著增加，从而对拟南芥植株生长发育速率的提高起了重要的作用。 　　(4) 拟南芥生长在高浓度CO2条件下，其叶片中各种矿质元素含量（如N、P、K、Ca���Mg）均显著降低，究其原因可能是，第一由于叶片中碳水化合物含量的显著增加而对矿物质元素具有稀释作用;第二由于蒸腾速率下降，引起矿质元素从根部随着蒸腾流运输到地上部分的含量相应减少。 　　

Synthesis, photoluminescence, and theoretical studies of novel Cu(I) complex

A novel diimine Cu(I)complex [Cu(ABPQ)(DPEphos)]BF4 [ABPQ and DPEphos are acenaphtho[1,2-b]bipyrido[2,3-h:3,2-f]quinoxaline and bis(2-(diphenylphosphanyl)phenyl) ether, respectively] is synthesized, and its photophysical properties are experimentally and theoretically characterized. The emission bands centered at ca. 400/470 and 550 nm of [Cu(ABPQ)(DPEphos)]BF4 are attributed to the ligand-centered pi -> pi* transition and the metal-to-ligand charge transfer d pi(Cu) -> pi*(N-N) transition, respectively. The luminescence quantum yield of [Cu(ABPQ)(DPEphos)]BF4 in CHCl3 is found to be about five times higher than that of [Cu(Phen)(DPEphos)]BF4.

Synthesis, characterization, and self-assembly of protein lysozyme monolayer-stabilized gold nanoparticles

Lysozyme monolayer-protected gold nanoparticles (Au NPs) which are hydrophilic and biocompatible and show excellent colloidal stability at low temperature, ca. 4 degrees C, were synthesized in aqueous medium by chemical reduction of HAuCl4 with NaBH4 in the presence of a familiar small enzyme, lysozyme. UV-vis spectra, transmission electron microscopy (TEM), atomic force microscopy, and X-ray photoelectron spectroscopy characterization of the as prepared nanoparticles revealed the formation of well-dispersed An NPs of ca. 2 nm diameter. Moreover, the color change of the An NP solution as well as UV-vis spectroscopy and TEM measurements have also demonstrated the occurrence of Ostwald ripening of the nanoparticles at low temperature. Further characterization with Fourier transform infrared spectroscopy (FTIR) and dynamic light scattering indicated the formation of a monolayer of lysozyme molecules on the particle surface. FTIR data also indicated the intactness of the protein molecules coated on An NPs. All the characterization results showed that the monodisperse An NPs are well-coated directly with lysozyme. Driven by the dipole-dipole attraction, the protein-stabilized Au NPs self-assembled into network structures and nanowires upon aging under ambient temperature.

Calculation of chemical bond parameters in La1-xCaxCrO3 (0.0 <= x <= 0.3)

The chemical bond parameters, that is, bond covalency, bond susceptibility, and macroscopic linear susceptibility of La1-xCaxCrO3 (x = 0.0, 0.1, 0.2, 0.3) has been calculated using a semiempirical method. This method is the generalization of the dielectric description theory proposed by Phillips, Van Vechten, Levine, and Tanaka (PVLT). In the calculation of bond valence, two schemes were adopted. One is the bond valence sums (BVS) scheme, and the other is the equal-valence scheme. Both schemes suggest that for the title compounds bond covalency and bond susceptibility are mainly influenced by bond valence and are insensitive to the Ca doping level or structural change. Larger bond valences usually result in higher bond covalency and bond susceptibility. The macroscopic linear susceptibility increases (only slightly for BVS scheme) with the increasing Ca doping level. (C) 1999 John Wiley & Sons, Inc.

电感耦合等离子体光谱和质谱法分析贻贝标准物质

采用电感耦合等离子体光谱和质谱法分析了贻贝标准物质,光谱法测定K、Na���ca���Mg、P、Al、Fe、Zn、Nn和Sr,质谱法测定As、B、Cd、Co、Cr、Cu、Ca���Ce、Mn、Mo、Ni、Pb、Se、Sr、U和V。在优化的工作条件下,测定了来自基体元素K、Na���Ca���P、Cl和C���多原子离子~(39)K~(16)O、~(39)K_2、~(40)Ar~(23)Na���~(43)Ca~(16)O、~(42)Ca~(16)O、~(44)Ca~(16)O、~(31)P~(16)O_2、~(40)Ar~(37)Cl、~(35)Cl~(16)O、~(37)Cl~(16)O和~(40)Ar~(12)C���~(55)Mn、~(78)Se、~(63)Cu、~(59)Co、~(58)Ni、~(60)Ni、~(75)As、~(77)Se、~(51)V、~(53)Cr和~(52)Cr的干扰系数以及HNO_3+H_2O_2(3+2)、HNO_3+HClO_4(3+0.5)和HNO_3+H_2SO_4(3+0.5)等3种样品消解方法在一些生物重要元素的同位素处产生的表观浓度。光谱法的检出限0.001～0.75mg/L;质谱法的检出限0....

岩石圈伸展对粤北下庄矿田铀成矿的制约机制研究

地球动力学与成矿关系的研究是地球科学研究的前沿领域，而陆内岩石圈伸展与成矿的关系的研究则是该领域相对比较薄弱的环节。 华南地区于白垩—古近纪发生了岩石圈强烈的伸展减薄事件，且岩石圈伸展减薄与该区同时期形成的众多金属和非金属矿床有密切的成因联系，尤其是华南地区的花岗岩型热液铀矿床，显示了与该区岩石圈伸展作用可能有多方面的成因联系。粤北下庄铀矿田位于位于南岭铀-多金属成矿带的南部，是华南地区典型的花岗岩型热液铀矿区，本次研究在深入细致的野外地质工作的基础上，运用流体包裹体地球化学、元素地球化学、同位素地球化学等方法手段，开展了对下庄铀矿田成矿流体性质、成矿过程中元素的活动规律、成矿流体来源及演化等方面的系统研究，初步探讨了岩石圈伸展对该区铀成矿的制约机制，并建立了可能的矿床成因模式。通过研究，本次工作获得了以下几点主要认识： （1）通过对下庄铀矿田部分铀矿床流体包裹体显微测温、激光拉曼光谱及液相成分分析研究，查明了下庄矿田铀矿床矿前期热液属中高温（200℃~350℃）、低盐度（0.72%~5.95%NaCl）、密度中等（0.703~0.830g/cm3）、活动深度较深（2.29km~5.74km）、富∑CO2、相对还原性质的流体；成矿期热液属中低温（主要为154℃ ~250℃）、低盐度（0~1.83%NaCl）、密度中等（0.628~0.867g/cm3）、活动深度较浅（0.19km~1.62km）、富F-、相对氧化性质的流体。 （2）矿石矿矿物电子探针测试分析及岩、矿石的微量元素地球化学分析研研究表明，本区铀矿床主要的原生铀矿物为沥青铀矿、铀石、钛铀矿，铀矿物的形成与Si、Ca���W等元素有密切的关系，而其它金属元素未显示明显地富集。矿石、脉石矿物部分继承了原岩的稀土元素组成，且在原岩基础上又有高度的演化。 （3）进行了矿区内碳酸盐的C���O同位素和黄铁矿的He、Ar稀有气体同位素的分析研究。研究表明，矿化剂∑CO2主要为幔源，大量的He、Ar等稀有气体也来自于地幔。矿区发育的深大断裂构造可能控制了幔源挥发份的加入。 （4）脉石矿物碳酸盐和萤石的Sr、Nd同位素地球化学研究显示，成矿流体中的这些元素主要源于地壳，南区矿床（338、339）的Sr、Nd组成则为富含壳源Sr、Nd的流体与幔源基性脉岩不同程度的水—岩反应所致。另外，碳酸盐铅同位素研究显示，下庄矿区成矿物质铀可能来自帽峰式后期流体交代的花岗岩体。 （5）岩石圈伸展与下庄矿田铀成矿有关系密切：下庄矿田铀矿床明显受伸展构造控制，伸展构造既为导矿构造，又为储矿构造；岩石圈伸展导致的地温梯度升高，大地热流平均值加大，驱动热液流体的流动，为铀成矿提供了主要的热驱动力；岩石圈伸展产生的深大断裂导通了壳幔间的联系，使幔源脱气成因挥发份（主要为∑CO2）沿断裂上升，加入壳源热水循环系统，从而参与了铀成矿。 （6）初步建立了下庄矿田“岩石圈伸展体系下大陆热水系统铀矿床成因模式”。模式认为，华南地区白垩—古近纪岩石圈伸展作用引发区内热水流体的大规模循环，且伸展引起的幔源脱气作用产生的挥发份（主要为ΣCO2）加入了贫铀、贫矿化剂的循环的地下热水中，形成了富矿化剂热水。富矿化剂热水从富铀花岗岩中浸出铀（氧化作用），变为富矿化剂、富铀热液流体，这种热液流体在伸展引起的热驱动下沿构造上升，热液流体上升到浅部时，由于地球化学障、流体压力释放等因素的影响，U被还原沉淀，并在有利部位富集成矿。

Thermal, structural and optical properties of NiOx thin films deposited by reactive dc-magnetron sputtering

The NiOx thin films were deposited by reactive dc-magnetron sputtering from a nickel metal target in Ar + O-2 with the relative O-2 content 5%. The as-deposited NiOx, thin films could represent a two-component system comprising crystalline NiO particles dispersed in an amorphous Ni2O3. Decomposition temperature of the as-deposited NiO, thin films was at about 263 degrees C. After annealed at 400 degrees C for 30 min in air, the surface morphology of the films became very rough due to the decomposition of the Ni2O3, leading to the changes of the optical properties of the NiO, thin films. The reflectivity of the films annealed at 400 degrees C was lower than that of the as-deposited one and the optical contrast was 52% at 405 nm. (c) 2006 Elsevier B.V. All rights reserved.

Influence of thermal annealing on optical properties and surface morphology of NiOx thin films

NiOx thin films were deposited by reactive DC-magnetron sputtering from a nickel metal target in Ar + O-2 with the relative O-2 content of 5%. Thermal annealing effects on optical properties and surface morphology of NiOx, films were investigated by X-ray photoelectron spectroscopy, thermogravimetric analysis, scanning electron microscope and optical measurement. The results showed that the changes in optical properties and surface morphology depended on the temperature. The surface morphology of the films changed obviously as the annealing temperature increased due to the reaction NiOx -> NiO + O-2 releasing O-2. The surface morphology change was responsible for the variation of the optical properties of the films. The optical contrast between the as-deposited films and 400 degrees C annealed films was about 52%. In addition, the relationship of the optical energy band gap with the variation of annealing temperature was studied. (c) 2006 Elsevier B.V. All rights reserved.

Write-once medium with Fe-Doped BiOx thin films for blue laser recording

Fe:BiOx films are fabricated on K9 glass substrates by rf-magnetron sputtering of a BiFeO target under argon atmosphere with increasing sputtering power from 80 to 200 W at room temperature. It is found that the thin films grown at the sputtering power of 160W can be formed at an appropriate deposition rate and have an improved surface morphology. The XPS result reveals that the films investigated are comprised of Bi, Fe and O elements. A typical XRD pattern shows that no phase transition occurs in the films up to 400 degrees C. The results of the blue laser recording test demonstrate that the Fe:BiOx films have good writing sensitivity for blue laser beam (406.7 nm) and good stability after reading 10000 times. The recording marks of 200nm or less are obtained. These results indicate that the introduction of Fe into BiOx films can reduce the mark size and improve the stability of the films.

Influence of phosphate precursors on the structures of sodium aluminophosphate sols, gels and glasses

Transparent and homogeneous aluminophosphate gels and glasses have been widely synthesized through an aqueous sol-gel route, extending significantly the glass-forming range compared to that accessible via the melt-cooling route. Different phosphorus precursors, sodium polyphosphate (NaPO3) and orthophosphate species (NaH2PO4 and/or H3PO4) were compared with regard to the macroscopic properties and the microscopic structure of the resultant gels and glasses as characterized by extensive high-resolution liquid- and solid-state NMR. Sodium polyphosphate solution results in a substantially wider composition range of homogenous gel formation than orthophosphate solutions, and the two routes produce significant structural differences in the sol and xerogel states. Nevertheless, the structures of the glasses obtained upon gel annealing above 400 degrees C are independent of the P-precursors used. (c) 2007 Elsevier B.V. All rights reserved.

Structural, morphological and optical properties of ZnO thin films grown on gamma-LiAlO2 substrate by pulsed laser deposition

ZnO thin films were deposited on the substrates of (100) gamma-LiAlO2 at 400, 550 and 700 degrees C using pulsed laser deposition (PLD) with the fixed oxygen pressure of 20 Pa, respectively. When the substrate temperature is 400 degrees C, the grain size of the film is less than 1 mu m observed by Leitz microscope and measured by X-ray diffraction (XRD). As the substrate temperature increases to 550 degrees C, highly-preferred c-orientation and high-quality ZnO film can be attained. While the substrate temperature rises to 700 degrees C, more defects appears on the surface of film and the ZnO films become polycrystalline again possibly because more Li of the substrate diffused into the ZnO film at high substrate temperature. The photoluminescence (PL) spectra of ZnO films at room temperature show the blue emission peaks centered at 430 nm. We suggest that the blue emission corresponds to the electron transition from the level of interstitial Zn to the valence band. Meanwhile, the films grown on gamma-LiAlO2 (LAO) exhibit green emission centered at 540 nm, which seemed to be ascribed to excess zinc and/or oxygen vacancy in the ZnO films caused by diffusion of Li. from the substrates into the films during the deposition.

Spray combustion synthesis of nanocrystalline Y2O3 and its thermodynamical and morphological study

Nano Y2O3 particles with a spherical shape and narrow size distribution have been prepared by a novel spray combustion method. The experimental procedure is briefly described and the thermodynamical process of the post-heat treatment is investigated in this paper. The precursor fully crystallized when treated at as low as 400 degrees C. Prepared particles showed spherical shape and well dispersibility under different treating conditions. Narrow size distribution of particles was achieved even when the precursor was treated at 1373 K. (C) 2007 Elsevier B.V. All rights reserved.