Dinuclear half-sandwich complexes containing bridging 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolato ligands. Molecular structures of Cp2Fe2(CO)(3)[mu-Se2C2(B10H10)], Cp2Ru2[mu-S2C2(B10H10)](2), and CP*Ru-2(2)(mu-Se)[mu-Se2C2(B10H10)].

Three prototypes of dinuclear complexes were obtained from the reactions of dilithium 1,2-dicarbacloso-dodecaborane-1,2-dichalcogenolates, (B10H10)C-2-(ELi)(2) (E = S, Se), with CpFe(CO)(2)Cl (1), CpRu(PPh3)(2)Cl (2), or [Cp*RuCl2](2) (3), respectively, and their structures have been determined by X-ray crystallography.

Syntheses and characterization of half-sandwich zirconium complexes with dichalcogenolate o-carborane ligands

Metallocene complex (Cp2ZrCl2)-Zr-tt (Cp-tt = eta(5)-1,3-(Bu2C5H3)-Bu-t) (1) has been prepared from the reaction of LiCptt with ZrCl4 in good yield. Reactions of 1 with dilithium dichalcogenolate o-carboranes afforded new type of half-sandwich compounds with dichalcogenolate o-carboranyl ligands [Li(THF)(4)][(CpZr)-Zr-tt(E2C2B10H10)(2)] (E = S, 2a; E = Se, 2b) in which only one cyclopentadienyl ring ligand existed. Complexes 1 and 2a were structurally characterized by X-ray analyses. In complex 2a, the Zr(IV) ion is eta(5)-bound to one 1,3-di-tert-cyclopentadienyl ring and a-bound to four mu(2)-sulfur atoms of two dithio-carboranes. The zirconium atom and four sulfur atoms form a distorted pyramid. The coordination sphere around the zirconium atom resembles in a piano stool structure with four legs of sulfur atoms and the fulcrum at the zirconium atom.

Synthesis and structural characterization of organolanthanide complexes with 1,2-dicarba-closo-dodecaborane-1,2-dichalcogenolate ligands

Reactions of anhydrous LnCl(3) (Ln = Nd, Gd, Dy, Er, Yb) with 2 equiv of LiCp' in THF afford the lanthanocene complexes Of CP'(2)Ln(mu-Cl)(2)Li(THF)(2) (CP' = eta(5)-t-BuC5H4, Ln = Nd (1), Gd (2), Dy (3), Er (4), Yb (5); Cp'= 1,3-eta(5)-t-Bu2C5H3, Ln = Nd (6), Gd (7), Dy (8), Er (9), Yb (10)). The molecular structures of 7 and 8 were characterized by X-ray crystallographic analysis. In these complexes, two Cp' ring centroids and two it-bridging chloride atoms around the lanthanide atoms form a distorted tetrahedron. The insertion of elemental chalcogen E (E = S, Se) into Li-C bonds of dilithium o-carborane in THF solution afforded dimers of dilithium. dichalcogenolate carboranes, [(THF)(3)LiE2C2B10H10Li(THF)](2) (E = S (12a), Se (12b)), which were confirmed by a crystal structure analysis. Reactions Of Cp'(2)Ln(mu-Cl)(2)Li(THF)(2) (1-10) with 12a or 12b gave dinuclear complexes of the formula [Li(THF)(4)](2)[Cp'(2)LnE(2)C(2)B(10)H(10)](2) (Cp'= eta(5)-t-BuC5H4, E = S, Ln = Nd (13a), Gd (14a), Dy (15a), Er (16a), Yb (17a); E = Se, Ln = Nd (13b), Gd (14b), Dy (15b), Er (16b), Yb (17b); Cp'= 1,3-eta(5)-t-Bu2C5H3 E = S, Ln = Nd (18a), Gd (19a), Dy (20a), Er (21a), Yb (22a); E = Se, Ln = Nd (18b), Gd (19b), Dy (20b), Er (21b), Yb (22b)). According to the X-ray structure analyses, the dianions of 13a and 13b contain two o-carborane dichalcogenolate bridges, and each CP'2Ln fragment is attached to one terminal and two bridging chalcogen ligands. The central Ln(2)E(2) four-membered ring is not planar, and the direct metal-metal interaction is absent.

Synthesis and characterization of novel lanthanocene complexes with dichalcogenolate o-carboranyl ligands

Reactions of [ Cp(2)Ln(mu-Cl)](2) (Cp = eta(5)-C5H5, Ln = Nd, Yb, Dy, Gd, Er) with an equivalent of [ (THF)(3)LiE2C2B10H10Li. (TT-IF) (THF)](2) (E = S, Se) in THF afforded the dinuclear sandwich complexes of formula[Cp(2)LnE(2)C(2)B(10)H(10)](2)[Li(THF)(4)](2) [E = S, Ln = Nd (1a), Yb (2a), Dy (3a), Gd (4a), Er (5a); E = Se, Ln = Nd (1b), Yb (2b), Dy (3b), Gd (4b), Er (5b)]. The molecular structures of complexes la, 2a and 2b were determined by the single crystal X-ray structure analyses. Two lanthanide atoms are connected by a pair chalcogen (eta(1), eta(2)-E2C2B10H10) bridging ligands and the central Ln(2)E(2) four membered ring is not planar.

Synthesis and structure of iron complex with 1,2-dithiolate-1,2-dicarba-closo-dodecaborane [Li(THF)(4)][Fe(S2C2B10H10)(2)(THF)]

The crystal of complex [Li(THF)(4)][Fe(S2C2B10H10)(2)(THF)] 3 belongs to monoclinic, space group P2(1) with a = 11.964(2), b = 16.527(3), c = 12.554(3) Angstrom,beta = 108.70(3)degrees, V= 2351.3(8) Angstrom(3), Z = 2, M-r = 835.95, D-c = 1.181 g/cm(3), mu (MoKalpha) = 5.30 cm(-1), f(000) = '874, R = 0.0622 and Rw 0.1538 for 1641 observed reflections with I > 2sigma(I). The ionic complex,of 3 contains the square pyramidal anion of [Fe(S2C2B10H10)(2)(THF)](-) and the tetrahedral cation of [Li(THF)(4)](+). The iron is 5-coordinated and located in the square pyramidal configuration. The iron atom and the four sulfur atoms are almost coplanar. The Lithium atom is coordinated with four oxygen atoms of four THF molecules and located in a tetrahedral configuration.

C_1桥联的茂金属化合物(Cp)CR_1R_2(Flu)MCl_2的合成及其催化烯烃聚合活性

合成了 6种单碳桥联的含芴 (Flu)茂 (Cp)基 B族茂金属催化剂 ,研究了它们催化烯烃聚合的能力 .通过 IR,1H NMR,EI-MS和元素分析对化合物进行了表征 .用所合成的茂金属化合物与 MAO所组成的催化体系对乙烯、丙烯的聚合进行了研究 .其中金属为 Ti的催化剂没有聚合活性或活性极低 .金属为 Zr的催化剂有一定的催化活性 ,用不同的催化剂得到的聚合物性质有一定的差异

利用DSC和EPR技术研究杜仲种子的贮藏条件

种子贮藏稳定性对于种质资源的长期保存具有重要意义，目前关于种子贮藏的最新理论为玻璃态理论，该理论认为种子的玻璃化有利于种子的长期贮藏。当种子处于玻璃态时，玻璃化物质的高度粘滞性降低了种子细胞内分子流动性，阻止了细胞质中分子的扩散，从而减少老化过程中细胞结构的损伤和化学组分的变化，延缓种子老化劣变反应速率，延长贮藏寿命。评价玻璃态的一个重要指标是玻璃化转变温度，当种子贮藏于玻璃化温度或以下10℃～30℃范围内时，种子具有最佳的贮藏稳定性。因此，检测种子的玻璃化转变温度对于种子的长期有效贮藏具有重要指导意义。 本研究将差示量热扫描技术（DSC）与电子顺磁共振波谱仪技术（EPR）应用于杜仲种子玻璃化转变温度方面的研究。在DSC方法中，选用4.4%～31.6%含水量范围的杜仲种胚分别进行了DSC图谱扫描。EPR方法选用3-羧基-2,2,5,5-四甲基吡咯烷-1-氧（3-carboxy-2,2,5,5-tetramethylpyrrolidine-1-oxyl，CP）和2,2,6,6-四甲基哌啶（4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy，TEMPO）作为探针标记杜仲种胚， 利用EPR技术测定不同含水量杜仲种胚的分子运动，通过对EPR图谱参数的分析计算，最终确定不同含水量杜仲种胚的玻璃化转变温度。 DSC实验结果显示，含水量为22.3%、28.0%、31.6%的杜仲种胚在0℃ 左右出现了一个水的熔融峰。该熔融峰的面积代表了自由水含量的多少，随着种胚含水量的降低该熔融峰面积减小。4.4%～31.6%含水量范围的杜仲种胚在-28℃左右还出现了一个熔融峰，推测此峰为杜仲种胚中某类物质熔融所形成的熔融峰。然而在此曲线上我们未观察到标志玻璃化转变的“台阶”出现。 CP-EPR实验的结果表明，利用EPR测定得到含水量为4.4%～11.6%的杜仲种胚在-110℃～20℃温度范围内，同一含水量的杜仲种胚随着温度的升高，分子运动速率加快;在同一温度条件下，高含水量的种胚比低含水量种胚的分子运动速率快。通过CP-EPR波谱两外缘峰最大距离（2Azz）的测定和数据统计分析，得到含水量为4.4%、5.7%、8.6%、10.3%、11.6%杜仲种胚的玻璃化转变温度分别约为44℃、25℃、4℃、-31℃、-43℃。可以把测定的杜仲种胚的这几个含水量的玻璃化转变温度与杜仲种子贮藏相结合，用于指导杜仲种子的贮藏。 TEMPO-EPR实验测定分析得到含水量为2.1%、3.4%、4.8%、8.3%、11.2% 的杜仲种胚的玻璃化转变温度分别为-21℃、-18℃、-24℃、-20℃、-27℃，玻璃化转变温度随含水量升高其变化的规律不明显，这与CP-EPR实验测得的结果有着较明显的差别。通过分析，认为对于脂质含量较高的杜仲种胚，随着含水量的降低，作为标记化合物的TEMPO随着脱水进入脂相，从而不能真实反映出不同含水量种胚的分子运动情况。与TEMPO标记相比，CP标记可能能够更真实地反映不同含水量杜仲种胚细胞质分子运动的情况，根据其分子运动情况得到的玻璃化转变温度更准确。

固化反应程度对热固性聚合物热物理性能的影响

以示差扫描量热仪 (DSC)为主要研究手段 ,研究了环氧封端聚芳醚酮 (E- PEK)、双酚 A型环氧树脂 (E- 44 )的玻璃化转变温度 (Tg)和比热 (Cp)与温度和反应程度的关系。采用基团贡献法对上述材料的 Tg 和 Cp 进行了预测 ,引入端基和固化剂的影响对基团贡献法进行了修正。

SZJ-12机器人通用控制器系统

本文介绍了一种通用的机器人二级控制系统,该机器人控制器已成功地用于四种不同类型的机器人本体,完成了各种PTP和CP控制功能.

中学生自我状态现状及其与亲子沟通、心理健康的关系研究

The communication between parents and children is one of the focuses in adolescence research area. However，the ego states in communication were seldom referred to. In present research, the relationship among high school students’ ego states, parent-child communication status and mental health level was explored. Study1: Ego State Questionnaire (ESQ) was revised according to 400 high school students from both rural and urban areas. Study2: Revised Ego State Questionnaire was administered to 450 high school students. Data was analyzed by cluster analysis. Study3: The relationship among ego states, parent-child communication status and mental health level was researched systematically according to 450 high school students. The main results of the thesis were as follows: 1) The five factors of Johu Dusy’s ego states were confirmed. 2) The revised RESQ had good reliability and validity, and could be used in researching middle school students ego states and related area. 3) Gender differences: Girls’ NP score was higher than boys’. Boys’ Adult and AC score was higher than girls. 4)School difference: students’ A and FC from key high school scored higher than students form normal high school. 5) The students were divided into two groups according to parental education level. The split point was high school. Students whose parents’ education level was above high school scored higher in NP than the other group of students. 6) The students were clustered into 4 groups according to cluster analysis: adapted、rational、contradictory、self-centered。 7) adapted、self-centered students’SCL-90 score was lower than average level, contradictory students’ score was higher than average level, rational students’score was equal to average level. 8) Both NP and Adult ego states had significant negative correlation with SCL total score, CP ego states had significant postive correlation SCL total score. 9) NP, A ego states had significant postive correlation with family communication atmosphere, father-son, father-daughter, mother-son, mother-daughter communication status . CP had significant negative correlation with above variables. AC had significant negative correlation with family communication atmosphere . 10) The stepwise regression showed that Adult ，Control Parent ego states and communication between parents and children score had prevented from mental health significantly. Adult ego states impacted mental health through communication between parents and children.

1, 2-Bis (diphenylphosphino) etane bridged dinuclear copper (I) complexes: Investigations of solid state and solution structures by CP/MAS31P NMR spectroscopy, X-ray crystallography, IR spectroscopy and solution 31P NMR and 63Cu NMR spectroscopy

Three different complexes of copper (I) with bridging 1, 2-bis(diphenylphosphino)ethane (dppe), namely [Cu2 (mu-dppe) (CH3CN)6] (ClO4)2 (1), [Cu2 (mu-dppe)2 (CH3 CN)2] (ClO4)2 (2), and [Cu2 (mu-dppe) (dppe)2 (CH3CN)2] (ClO4)2 (3) have been prepared. The structure of [Cu2 (mu-dppe) (dPPe)2 (CH3CH)2] (ClO4)2 has been determined by X-ray crystallography. It crystallizes in the space group PT with a=12.984(6) angstrom, b=13.180(6) angstrom, c=14.001(3) angstrom, alpha=105.23(3), beta=105.60(2), gamma=112.53 (4), V=1944 (3) angstrom3, and Z=1. The structure was refined by least-squares method with R=0.0365; R(w)=0.0451 for 6321 reflections with F0 greater-than-or-equal-to 3 sigma (F0). The CP/MAS P-31 and IR spectra of the complexes have been analysed in the light of available crystallographic data. IR spectroscopy is particularly helpful in identifying the presence of chelating dppe. P-31 chemical shifts observed in solid state are very different from those observed in solution, and change significantly with slight changes in structure. In solution, complex 1 remains undissociated but complexes 2 and 3 undergo extensive dissociation. With a combination of room temperature H-1, Cu-63, and variable temperature P-31 NMR spectra, it is possible to understand the various processes occurring in solution.

The NMR-spectroscopic and X-ray crystal-structural characterization of two Cp*Ir halfsandwich complexes containing the 1,2-dicarba-closo-dodecaborane-1,2-diselenolato ligand

The reaction of [Cp*IrCl2](2) with dilithium 1,2-orthocarborane-1,2-diselenolate 3 leads to the green 16-electron diselenolene complex [Cp*Ir{Se2C2(B10H10)}] (4) which takes up two-electron ligands such as trimethylphosphane to give the 18-electron diselenolate derivative [Cp*Ir(PMe3)-{Se2C2(B10H10)}] (5). The molecular structures of 4 and 5 were determined by X-ray crystal structure analysis. The Se-77-nuclear shielding in 4 is lower by almost 500 ppm relative to that in 5.

Reaction of halfsandwich iridium polychalcogenide complexes with dimethyl acetylenedicarboxylate. Molecular structure of Cp*Ir[S2C2(COOMe)(2)]

The pentamethylcyclopentadienyl iridium complexes Cp*Ir(PMe3)(E-n) (E = S, n = 4, 5 or 6; E = Se, n = 2 or 4 E = Te, n = 2) react with dimethyl acetylenedicarboxylate to give Cp*Ir(PMe3)[E2C2(COOMe)(2)] compounds which tend to lose the trimethylphosphine ligand; the molecular structure of the dithiolene derivative, Cp*Ir[S2C2(COOMe)(2)], has been determined.

The use of half-sandwich iridium dithiolate and diselenolate complexes, Cp*Ir(L)(ER)(2) (L = CO, PMe3, PPh3; ER = SPh, SePh, SeMe), for the synthesis of heterodimetallic compounds. The molecular structure of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)]

Carbonyl-iridium half-sandwich compounds, Cp*Ir(CO)(EPh)(2) (E = S, Se), were prepared by the photo-induced reaction of Cp*Ir(CO)(2) with the diphenyl dichalcogenides, E2Ph2, and used as neutral chelating ligands in carbonylmetal complexes such as Cp*Ir(CO)(mu-EPh)(2)[Cr(CO)(4)], Cp*Ir(CO)(mu-EPh)(2)[Mo(CO)(4)] and Cp*Ir(CO)(mu-EPh)(2)[Fe(CO)(3)], respectively. A trimethylphosphane - iridium analogue, Cp*Ir(PMe3)(mu-SeMe)(2)[Cr(CO)(4)], was also obtained. The new heterodimetallic complexes were characterized by IR and NMR spectroscopy, and the molecular geometry of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)] has been determined by a single crystal X-ray structure analysis. According to the long Ir...Mo distance (395.3(1) Angstrom), direct metal-metal interactions appear to be absent. (C) 1998 Elsevier Science S.A. All rights reserved.

Fabrication of corrosion resistant, bioactive and antibacterial silver substituted hydroxyapatite/titania composite coating on Cp Ti

The present work is aimed at developing a bioactive, corrosion resistant and anti bacterial nanostructured silver substituted hydroxyapatite/titania (AgHA/TiO(2)) composite coating in a single step on commercially pure titanium (Cp Ti) by plasma electrolytic processing (PEP) technique. For this purpose 2.5 wt% silver substituted hydroxyapatite (AgHA) nanoparticles were prepared by microwave processing technique and were characterized by X-ray diffraction (XRD), Fourier-transform infrared (FT-IR) spectroscopy and transmission electron microscopy (TEM) methods. The as-synthesized AgHA particles with particle length ranging from 60 to 70 nm and width ranging from 15 to 20 nm were used for the subsequent development of coating on Cp Ti. The PEP treated Cp Ti showed both titania and AgHA in its coating and exhibited an improved corrosion resistance in 7.4 pH simulated body fluid (SBF) and 4.5 pH osteoclast bioresorbable conditions compared to untreated Cp Ti. The in vitro bioactivity test conducted under Kokubo SBF conditions indicated an enhanced apatite forming ability of PEP treated Cp Ti surface compared to that of the untreated Cp Ti. The Kirby-Bauer disc diffusion method or antibiotic sensitivity test conducted with the test organisms of Escherichia coli (E. coli) for 24 h showed a significant zone of inhibition for PEP treated Cp Ti compared to untreated Cp Ti. (C) 2011 Elsevier Ltd and Techna Group S.r.l. All rights reserved.