Novel sodium sulfonate-functionalized poly(ether ether ketone)s derived from 4,4 '-thiodiphenol

Novel sodium sulfonate-functionalized poly(ether ether ketone)s derived from 4,4'-thiodiphenol with degree of sulfonation up to 2.0 were synthesized by nucleophilic polycondensation of various amount of 5,5 '-carbonylbis(2-fluorobenzenesulfonate) (1) and 4,4'-difluorobenzophenone (2) with 4,4'-thiodipheno (3). Component and structure of the polymers were confirmed by TR, NMR and elemental analysis. Wide angle X-ray diffraction patterns indicated an amorphous structure of the polymers. All the polymers showed excellent thermal stability and poor solubility in water. (C) 2001 Elsevier Science Ltd. All rights reserved.

Bright green organic electroluminescent devices based on a novel thermally stable terbium complex

A navel thermally stable terbium carboxylate complex, Tb(MTP)(3)(phen) (MTP=monotetradecyl phthalate, phen=1,10-phehanthroline), was synthesized and characterized. The device structure of glass substrate/indium-tin-oxide/poly(p-phenylenevinylene) (PPV)/poly (N-vinycarbazole) (PVK):Tb(MTP)(3)(phen): 1,3,4-oxadizole derivative (PBD)/tris(8-hydroxyquinoline) (Alq(3))/aluminum (Al) was employed to study the electroluminescent properties of Tb(MTP)(3)(phen). A green emission with extremely sharp spectral band of less than 10 nm at 544 nm peak wavelength was observed. A maximum luminance of 152 cd/m(2) and an external quantum efficiency of 0.017% were achieved at a drive voltage of 24 V. A possible mechanism of energy transfer based on the polymer doped with lanthanide organic complex was also proposed.

Syntheses and structures of Na-2[Zn-II(ida)(2)].7H(2)O and Na-4[Hg-II(nta)(2)].7H(2)O

The title complexes were synthesized and the crystal structures of their salts were determined by single-crystal X-ray structure analyses. Na-2[Zn-I(ida)(2)]. 7H(2)O: Triclinic, P1, a=0.523 4(2) nm, b=0.897 10(10) nm, c=1.069 10(10) nm, alpha=85.910(10)degrees, beta= 76.380(10)degrees, gamma=83.52(2)degrees, V=0.484 2(2) nm(3), Z=1. The complex anion [Zn-I (ida)(2)](2-) has a pseudo-octahedral structure in which the two N atoms: are in a trans configuration. Na-4[Hg-I(nta)(2)]. 7H(2)O: Monoclinic, C-c, a = 1.795 0(4) nm, b = 0.892 9(2)nm, c = 1.575 4(2) nm, beta = 92.78 (3)degrees, V = 2.526 2(9) nm(3), Z = 4. The complex anion [Hg-I (nta)(2)](4-) has a pseudo-bicapped-octahedral structure in which the two N atoms are in a trans configuration.

The bond ionicity in RBa2Cu3O7 (R=Pr, Sm, Eu, Gd, Dy, Y, Ho, Er, Tm)

RBa2Cu3O7 (R = Pr, Sm, Eu, Gd, Dy, Y, Ho, Er, Tm) has been studied using complex chemical bond theory. The results indicated that with the decreasing of R radius, the ionicities for all considered types of bond decrease. This is in good agreement with the experimental fact that T-c decreases with the decreasing of R radius. PrBa2Cu3O7 with no Ba-site Pr in this calculation is also predicted to be a superconductor. This supports the conclusion obtained by Blackstead et al. The ionicity for each bond obeys the following order: Ba-O > R-O > Cu(2)-O(1) > Cu(2)-O(2,3) > Cu(1)-O(4) similar to Cu(1)-O(1).

Bright blue electroluminescent devices utilizing poly (N-vinylcarbazole) doped with fluorescent dye

Bright blue electroluminescent devices have been fabricated using poly (N-vinylcarbazole) (PVK) doped with perylene as the emissive layer, poly(p-phenylenevinylene) (PPV) as the hole-transporting layer, 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (PBD), tris(8-hydroxyquinoline)aluminum (Alq(3)) as the electron-transporting layer, and Al as the cathode. A luminance of 700 cd/m(2) and a luminescent efficiency of 0.8% are achieved at a drive voltage of 36 V. In the experiment, it is found that the introduction of electron-transporting layer PBD has a great effect on the emissive color of the electroluminescent devices prepared by PVK doped with perylene. Yellow-green emission is observed from the device structure of glass substrate/indium-tin-oxide/PVK:perylene/Al. The possible emissive mechanisms are given. The effect of the transporting layer on the electroluminescence is also discussed. (C) 1997 Elsevier Science S.A.

四-4-(烷氧基-羰基)酞菁铜(Ⅱ)的合成、结构及其成膜性

本文合成了两种新型取代酞菁铜(Ⅱ)配合物:四-4-(戊氧基-羰基)酞菁铜(Ⅱ)(A)和四-4-(癸氧基-羰基)酞菁铜(Ⅱ)(B),并通过元素分析、ESR、~1H-NMR和FT-IR进行了表征.用可见光谱研究了它们在氯仿溶液中的聚集形式;用X-ray粉末衍射方法研究了配合物的固相堆积排列结构.两种配合物的氯仿溶液在亚相(水)上的π-A曲线表明,它们均有明显的“气”“液”“固”变化过程;并能在不同的表面压力区间形成较好的单分子层和多分子层膜.

CRYSTAL-STRUCTURE OF 1, 10-DECANEDIAMMONIUM TETRACHLOROZINCATE

The crystal structure of the title compound has been determined from single crystal X-ray diffraction. The complex crystallizes in the triclinic space group P1 with Z=2. Lattice parameters are: a = 0.7296(1), b = 1.0110(3), c = 1.2814(4) nm; alpha = 90.84(2), beta = 101.17(2), gamma = 92.52(2)-degrees. Intensity data were collected on a Nicolet R3M/E four-circle diffractometer using MoK alpha (lambda = 0.071073 nm) radiation. The structure was solved by Patterson and Fourier techniques and refined by least-squares techniques to R = 0.065. The structure of the complex consists of tetrahedral ZnCl42- anions which form a two-dimensional sheets. Tetrahedral ZnCl42- anions are sandwiched between two hydrocarbon layers which consist of [NH3(CH2)10NH3]2+ cations. Each [NH3(CH2)10NH3]2+ group is in a gauche bond between C atoms near NH3 polar heads.

四氯合锌酸1,10-癸二铵配合物的晶体结构

合成了[NH_3(CH_2)_(10)NH_3]ZnCl_4配合物(简称DDAZn),用X射线衍射法研究了它的晶体结构,晶体属三斜晶系,空间群为P1,晶胞参数为:α=0.7296(1),b=1.0110(3),c=1.2814(4)nm;α=90.84(2),β=101.17(2),γ=92.52(2)°;Z=2.该配合物为层型结构.由单个四面体阴离子ZnCl_4~(2-)构成的阴离子层被夹在烷基铵阳离子层之间,形成“夹心面包”型体系.在层之间的烷基铵链在垂直于层的方向上倾斜排列.

稀土-其它过渡金属混合催化剂用于共轭双烯烃的聚合——Ⅳ.(NdCl_3+FeCl_3)·nphen-HAI(i-Bu)_2体系对异戊二烯的聚合

本文报道由(NdCl_3+FeCl_3)·nphen-HAl(i-Bu)_2催化体系引发异戊二烯聚合的结果。在适当Nd/Pe比下,该体系对异戊二烯聚合的活性可超过单一钕或铁催化剂的活性,同时随催化剂中钕和铁含量的不同,所得产物的微观结构变化很大,当体系中钕含量由100％→0时,产物的顺-1,4结构含量由94.4％→22.1％,而3,4结构含量由5.6％→77.9％。Al/M(N=Nd+Fe)比、单体浓度和聚合温度不仅对聚合活性有影响,对产物的微观结构影响也较大。事实表明,该聚合体系中存在着两种过渡金属(Nd和Fe)活性中心,它们按各自的机理进行异戊二烯的聚合。

STUDY ON MEASUREMENT OF DIFFUSION-COEFFICIENT OF LI ATOM IN LIQUID ALUMINUM

The tess potential-concentration curve was first applied to measure the concentration of an alloy. Attempt to use the V-c curve of Al-Li alloy in measuring the diffusion coeffictent of Li atom in liquid aluminium with anode chronopotentiometry at 720℃, was made and D_(Li/Al=4.94×10~(-5)cm~2·s~(-1) was obtained. The value is well consistent wish the theoretical value, D_(Li/Al)=4.85×10~(-5)cm~2·s~(-1) in terms of Stokes-Einstein equation.

粘土矿物及无机絮凝剂对有害赤潮的治理研究

在害赤潮作为一种全球性的海洋灾害，给海洋环境、水产养殖业和人类健康造成巨大危害，研究赤潮的发生规律，探索新的、经济有效的赤潮的防治方法具有重要的科学意义和应用前景。本文针对中国沿海常见赤潮生物种，研究了粘土矿物双赤潮生物基本生理指标的影响，进一步探讨了粘土矿物的控制赤潮机制；并针对粘土矿物去除效率不高的特点，制备出具有较高絮凝胶效率的改性粘土；此外，本文还首次将无机高分子絮凝效率的改性粘土；此外，本文还首次将无机高分子絮凝剂MMH（混合金属氢氧化物正电胶体）和PSMS（聚硅酸金属盐）用于赤潮治理研究中，并探索了上述赤潮防治剂的环境生态效应，主要成果与内容有：1、粘土矿物的筛选 采集国内外近30种粘土矿物，分别考察了它们对中国沿海常见赤潮生物种赤潮异弯藻（Heterosigma akashiwo）和塔玛亚历山大藻（Alexandrium tamarense）的去除效果。结果表明，不同粘土矿物对赤潮生物的絮凝能力有显著差别，实验筛选出去除效果较好的几种粘土，分别为来自美国的Chemically treated kaolin、WHOI土、江苏吴县高岭土及苏州特号土等。通过絮凝实验得到上述几种粘土矿物对两种赤潮生物的絮凝曲线，发现不同粘土矿物对赤潮生物的最大去除率及达到最大去除率所需的粘土浓度有较大差别，同一粘土矿物对不同赤潮生物的去除效果也不相同。塔玛亚历山大藻较赤潮异变藻更易被粘土矿物去除。2、粘土矿物对赤潮生物的生理效应 研究了高岭土对赤潮异弯藻和塔玛来历山大藻生长繁殖、叶绿素a含量、光合作用以及呼吸作用的影响。结果表明，高岭土对赤潮生物生长、叶绿素a含量及光合作用均有抑制作用，表现为随粘土浓度的增加及作用时间的延长，抑制作用增强，并认为这可能与粘土的加入导致光照效应降低及藻类生长的营养环境改变有关。实验同时发现高岭土对不同赤潮生物的抑制程度不同，塔玛亚历山大藻上述各项生理指标比赤潮异弯藻更易受粘土影响。3、无机絮凝剂的制备及絮凝作用研究 主要考察了无机高分子絮凝剂MMH及PSMS（聚硅酸金属盐），包括聚硅酸氯化铝（PSAC）和聚硅酸硫酸铝（PSAS）的合成及对赤潮生物的絮凝作用。在MMH的合成过程中，考察了镁铝摩尔比及制备温度对MMH絮凝赤潮异弯藻的影响，认为镁铝摩尔比为2的条件下制备的MMH具有较好的絮凝和沉降性能，其絮凝赤潮异弯藻的最佳用量为1.5mmolAl/L。在PSAS的合成中采用三因子三水平的正交试验设计，得到PSAS的最佳制备条件为：SiO_2浓度 = 2%， Al~(3+)/SiO_2 = 1, pH = 4。絮凝实验结果表明，PSAS对赤潮生物的絮凝效果优于传统絮凝剂AS（硫酸铝），同时PSAS对不同赤潮生物的絮凝效果也不同，认为这主要与不同赤潮生物的形态结构、运动性及胞外分泌物有关。4、粘土矿物表面改性及机理研究 为提高粘土矿物去除赤潮生物的效率，分别用插入法和表面吸附法制备改性粘土。实验得出插入法的最佳制备条件为：制备温度70 ℃，镁离子浓度2mol/L；表面吸附法中粘土和MMH（混合金属氢氧化物胶体）的适宜配比为：粘土/MMH=10。改性后粘土去除赤潮异弯藻的效率较改性前提高2-3倍。相关分析表明，改性粘土去除赤潮生物的效率与改性后表面电位呈正相关，两种情况下R~2均大于0.8，说明表面电位是影响粘土矿物去除赤潮生物的一个重要因素。5、赤潮治理的现场模拟实验及环境生态效应 在1999年夏季胶州湾中肋骨条藻（Skeletonema costatum）赤潮的发生现场进行了改性粘土及PSAS对藻类去除率、悬浮物、DO、COD、pH等指标的影响研究。结果表明，改性粘土及PSAS对现场中肋骨条藻有较高的去除率，1g/L的改性高岭土和改性蒙脱土对中肋骨条藻的去除率分别可达77%和93%，1ml/L的PSAS去除率达90%以上。DO的含量轻微下降，不致影响其他生物的生长，COD下降幅度较大，达50-80%。6、赤潮防治剂对中国对虾的毒性研究 进行了粘土、次氯酸钙、氯化铝和氯化铁对中国对虾的毒性试验，结果表明，1g/L的高岭土对虾基本无毒性；次氯酸钙在低浓度下对对虾无毒，在高浓度下对对虾有急性毒性效应，安全使用浓度为0.5ml/L游离氯；氯化铝和氯化铁在对虾体内有一定的积累，其长期的毒性效应有待于进一步的分析。上述几种试剂均可用于粘土矿物的改性处理中，是比较安全的赤潮防治剂。

The inhibition of mild steel corrosion in 1 M hydrochloric acid solutions by triazole derivative

The title compound 1-(4,5-dihydro-3-phenylpyridine-1-yl)-2-(1H-1,2,4-triazole-1-yl)ethyl ketone (DTE) was synthesized and its inhibiting action on the corrosion of mild steel in 1 M hydrochloric acid solutions was investigated by means of weight loss, potentiodynamic polarization, electrochemical impedance spectroscopy (EIS) and scanning electronic microscope (SEM). Results obtained revealed that DIE performed excellently as a corrosion inhibitor for mild steel in 1 M hydrochloric acid media and its efficiency attains more than 90.9% at 1.0 x 10(-3) M at 298 K. Polarization curves indicated that the inhibitor behave mainly as mixed-type inhibitor. EIS showed that the charge transfer controls the corrosion process in the uninhibited and inhibited solutions. Adsorption of the inhibitor on the mild steel surface followed Langmuir adsorption isotherm. And the values of the free energy of adsorption Delta G(ads) indicated that the adsorption of DTE molecule was a spontaneous process and was typical of chemisorption. (c) 2008 Elsevier B.V. All rights reserved.

晚中新世以来中国北方风成沉积的磁性地层学和沉积学研究

The past two decades have witnessed an unprecedented growth of interest in the palaeoenvironmental significance of the Pleistocene loess deposits in northern China. However, it is only several years ago that the Tertiary red clay sequence underlying Pleistocene loess attracted much attention. One of the major advances in recent studies of eolian deposits on the Loess Plateau is the verification of the eolian origin for the Tertiary red clay sediments. The evidence of the eolian origin for the red clay is mainly from geochemical and sedimentological studies. However, sedimentological studies of the red clay deposits are still few compared with those of the overlying loess sediments. To date, the red clay sections located near Xifeng, Baoji, Lantian, Jiaxian, and Lingtai have been studied, with an emphasis on magnetostratigraphy. These sections have a basal age ranging from ～4.3 Ma to ～7.0 Ma. The thickness of the sections varies significantly, depending perhaps on the development of local geomorphological conditions and the drainage system. Although the stratigraphy of the red clay sections has been recorded in some detail, correlation of the red clay sequences has not yet been undertaken. Geological records (Sun J. et al., 1998) have shown that during glacial periods of the Quaternary the deserts in northem China were greatly expanded compared with modern desert distribution. During interglacial periods, desert areas contracted and retreated mostly to northwestern China because of the increase in inland penetration of monsoonal precipitation. According to pedogenic characteristics of the red clay deposits, the climatic conditions of the Loess Plateau is warmer and wetter generally in the Neogene than in the late Pleistocene. Panicle analyses show that grain size distribution of the red clay sequence is similar to that of the paleosols in the Pleistocene loess record, thus implying a relatively remote provenance of the red clay materials. However, the quantitative or semiquantitative estimates of the distance from the source region to the Loess Plateau during the red clay development remains to be investigated. In this study, magnetostratigraphic and sedimentological studies are conducted at two thick red clay sequences-Jingchuan and Lingtai section. The objectives of these studies are focused on further sedimentological evidence for the eolian origin of the red clay, correlation of red clay sequences, provenance of the red clay, and the palaeoclimate reconstruction in the Neogene. Paleomagnetic studies show that the Jingchuan red clay has a basal age of 8.0 Ma, which is 1 million years older than the previously studied Lingtai section. The Lingtai red clay sequence was divided into five units on the basis of pedogenica characteristics (Ding et al., 1999a). The Jingchuan red clay sequence, however, can be lithologically divided into six units according to field observations. The upper five units of the Jingchuan red clay can generally correlate well with the five units of the Lingtai red clay. Comparison of magnetic susceptibility and color reflectance records of four red clay sections suggests that the Lingtai red clay sequence can be the type-section of the Neogene red clay deposits in northern China. Pleistocene loess and modem dust deposits have a unimodal grain-size distribution. The red clay sediments at Jingchuan and Lingtai also have a unimodal grain-size distribution especially similar to the paleosols in the Pleistocene loess record. Sedimentological studies of a north-south transect of loess deposits above S2 on the Loess Plateau show that loess deposits had distinct temporal and spatial sedimentary differentiation. The characteristics of such sedimentary differentiation can be well presented in a triangular diagram of normalized median grain size, normalized skewness, and normalized kurtosis. The triangular diagrams of the red clay-loess sequence at Lingtai and Jingchuan indicate that loess-paleosol-red clay may be transported and sorted by the same agent wind, thus extending the eolian record in the Loess Plateau from 2.6 Ma back to about 8.0 Ma. It has been recognized that during the last glacial maximum (LGM) the deserts in northern China had a distribution similar to the present, whereas during the Holocene Optimum the deserts retreated to the area west of the Helan Mountains. Advance-retreat cycles of the deserts will lead to changes in the distance of the Loess Plateau to the dust source regions, thereby controlling changes in grain size of the loess deposited in a specific site. To observe spatial changes in sedimentological characteristics of loess during the last glacial-interglacial cycle, the texture of loess was measured along the north-south transect of the Loess Plateau. Since the southern margin of the Mu Us desert during the LGM is already known, several models of grain size parameters versus the minimum distance from the source region to depositional areas were developed. According to these semiquantitative models, the minimum distance from the source region to Lingtai and Jingchuan areas is about 600 km during the Neogene. Therefore the estimated provenance of the Tertiary red clay deposits is the areas now occupied by the Badain Jaran desert and arid regions west of it. The ratio of the free iron to total iron concentration attests to being a good proxy indicator for the summer monsoon evolution. The Lingtai Fe_20_3 ratio record shows high values over three time intervals: 4.8-4.1 Ma, 3.4-2.6 Ma, and during the interglacial periods of the past 0.5 Ma. The increase in summer monsoon intensity over the three intervals also coincides with the well-developed soil characteristics. It is therefore concluded that the East-Asia summer monsoon has experienced a non-linear evolution since the late Miocene. In general, the East Asia summer monsoon was stronger in Neogene than in Quaternary and the strongest East Asia summer monsoon may occur between 4.1 and 4.8 Ma. The relatively small ice volume and high global temperature may be responsible for the strong summer monsoon during the early Pliocene.

CAS-1模拟月壤

模拟月壤是与月球月壤具有相似的矿物组成、化学成分和物理力学性质的地球物质,是月球样品的地球化学复制品.长白山龙岗火山群金龙顶子火山喷发的四海火山渣具有与阿波罗14号采集的月球样品相似的化学和矿物组成,并含有20%～40 %的玻璃物质.以四海火山渣为初始物质,研制成功CAS-1模拟月壤,并测量了CAS-1模拟月壤的主量和微量元素组成、矿物组成、密度、颗粒形态、粒度分布、抗剪性和复介电常数等参数.结果表明,CAS-1模拟月壤与Apollo 14号采集的月球样品具有相似的化学成分、矿物组成和物理力学性质,是一种理想的低钛玄武岩质模拟月壤.

中国一些河流离子组分初步研究

　　研究人类活动、全球变化对河流水质、离子化学特征及分布的影响具有重要意义。河流离子化学组成可以反映水系的区域岩性，物理化学风化特征。而对于控制河流离子化学自然因素的研究则有助于判别人类活动如农业灌溉施肥、矿山开采、工业生产等对河流的影响。同时，河流组分如NO3-、SO42-、As、Cd等的组成特征可以反映人类活动污染物输入程度。因此，河流水化学特征可以从一定程度上反映人类活动对水环境的影响。同时，研究河水离子化学特征及其分布规律也可以获得化学元素的生物地球化学循环、风化侵蚀及其在陆地—河流—海洋系统循环过程中的重要信息。此外，还有助于评价不同经济因素如人口密度等对河流离子的影响；有助于合理有效的利用河水的自净容量和环境效应，保护水资源；为水资源的开发利用、污染控制提供科学依据。 　　本文以中国南北方代表性流域—西江流域、长江中游（主要为汉水和乌江水系）、淮河上游及黄河下游流域河水为研究对象，通过对河水主要及微量金属离子的考察，结合基本水质理化参数，初步研究了我国南北方一些河流的离子化学特征及影响因素。通过此次研究，得出以下几点认识： 　　1. 西江流域河流pH均值为7.40，长江中游为8.11，黄河下游为8.34，淮河上游为7.95。西江流域河流DO含量均值为7.51 mg/l，低于黄河下游干流的8.27 mg/l；黄河下游支流DO含量显著低于干流。西江流域TDS经向分异显著，随经度增加逐渐降低。西江流域TDS平均值为152.78 mg/l，低于长江、黄河水系。 　　2. 西江流域、长江中游、淮河上游及黄河下游阴离子均以HCO3-平为主，各水系阴离子平均含量顺序均为HCO3- > SO42 -> Cl- > NO3-。研究区域水系中HCO3-平均含量以淮河上游为最高，西江流域最低；SO42 -、Cl-及NO3-平均含量则以黄河下游为最高，长江中游最低。研究区域水系阳离子均以Ca2+为主，西江流域及长江中游阳离子平均含量顺序为Ca2+ > Mg2+ > Na+ > K+，而淮河上游、黄河下游阳离子平均含量顺序则为Ca2+ > Na+ > Mg2+ > K+。 　　从长江中游到淮河上游、黄河下游，区域岩石风化是控制离子组成的主要因素，但蒸发结晶因素的贡献逐渐加强。其中，介于长江和黄河流域之间的淮河上游水系离子组成的过渡特征显著。研究区域水系中NO3-主要源于污染物排放，黄河干流污染较西江干流污染重。 　　3. 西江流域河流溶解态微量金属平均含量Zn>Cr>Cu>As>Al>Pb>Cd，其中Zn平均含量为37.72μg/l，Cd平均含量则仅为0.24μg/l。长江中游溶解态微量金属平均含量Zn>Cr>Pb>As>Cu=Al>Cd。淮河上游溶解态微量金属平均含量Zn>Cr>As>Pb>Al>Cu>Cd。黄河下游溶解态微量金属平均含量Zn>Cr>Cu>As >Al>Pb>Cd。研究区域河流中，西江流域溶解态Cu、Cr的平均含量分别为6.12μg/l和7.61μg/l，高于长江中游、淮河上游及黄河下游。长江中游溶解态Pb和Cd平均含量则高于西江流域、淮河上游及黄河下游。而研究区域中，黄河下游溶解态Al含量最高，达12.7 μg/l，淮河流域则体现出了Zn和Al的高含量特征。 　　化学风化过程在一定程度上导致了水体与风化壳之间不同化学元素的分异，使河水中溶解态Al和As相对于其它微量金属元素强烈富集，而Pb、Zn、Cu及Cr则相对亏损。河流溶解态As和Al除来源于矿物岩石风化外，也受外源输入—人类活动的影响。 　　4. 自然条件的区域差异是形成河流离子化学分异的主要因素，但人类活动对其影响逐步加深。工农业污染物输入在一定程度上改变了天然河流的离子化学组成，使河流组分NO3-、SO42-、As、Al等呈现富集趋势。化学元素在河流这一循环过程中间体中的地球化学行为越来越多地受人类活动影响。