Theoretical Study on Heavy Metal Carbonyls

金属羰基化合物不仅是一类独特的无机化合物，也在有机化学中有多种重要用途，例如作为均相有机合成中的催化剂或是催化剂前驱体，也可以是合成其它金属有机化合物的前驱物，因而自问世起一直备受关注。然而，对含重金属特别是锕系和镧系金属羰基化合物的关注度却极低。本论文中，我们采用密度泛函理论方法对一系列八配位前锕系和镧系金属羰基化合物以及金羰基化合物进行理论研究，结果归纳如下： 1.八配位锕系和镧系金属羰基化合物M(CO)8q(q=0，+1;M=U，Pa，Th，Nd，Pr，Ce)的基态均为立方或准立方结构，其中心金属原子取fd3sp3杂化且因配位而发生从最外围的ns到次内层的(n-1)d或(n-2)f层的...Metal carbonyls, a unique class of inorganic that exhibits diverse applications in organic chemistry, e.g., either as catalysts or catalyst precursors in homogeneous catalysis or as precursors for the preparation of other organometallic complexes, have attracted continuous and extensive interest ever since their discovery. Yet, little attention has been paid to such heavy-metal carbonyls as lantha...学位：理学硕士院系专业：化学化工学院_物理化学(含化学物理)学号：2052010115159

Dicarboxylate-controlled three Zn(II) coordination polymers incorporating flexible 1,2-bis(imidazol-1 '-yl)ethane ligand: Syntheses, structures, thermal stabilities and photoluminescent properties

通讯作者地址: Sun, D (通讯作者),Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 地址: 1. Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 电子邮件地址: [email protected]; [email protected] mixed-ligand Zn(II) coordination polymers (CPs) of the formula {[Zn-2(bime)(2)(adiP)(2)]center dot(H2O)(5)}(n) (1), {[Zn(bime)(ipa)]center dot(H2O)3}(n) (2), {[Zn(bime)(tpa)]center dot(H2O)center dot(CH3OH)](n) (3) (bime = 1,2-bis(imidazol-1'-yl)ethane, H(2)adip = adipic acid, H(2)ipa = isophthalic acid and H(2)tpa = terephthalic acid) were synthesized. All CPs have been characterized by element analysis, powder X-ray diffraction (PXRD), IR and X-ray single-crystal diffraction. Complexes 1 and 2 exhibit similar wavy two-dimensional (2D) sheets with 4(4)-sql topology. Compared tot, complex 2 contains a larger window owing to the different conformation of bime ligand. In both 1 and 2, we observed 1D water chain filling in the 44-sql net. In 3, the bime acts as a bidentate ligand and the tpa adopts a mu(2)-eta(1),eta(1) coordinated mode which links the Zn(II) ions to form a 2D 6(3)-hcb net. The results suggest that the dicarboxylates play crucial roles in the formation of the different structures. In addition, the thermal stabilities and the photoluminescence properties of them were also investigated. (C) 2012 Elsevier B.V. All rights reserved.National Natural Science Foundation of China 20721001 MSTC 2007CB815301 Independent Innovation Foundation of Shandong University 2011GN030 Special Fund for Post-doctoral Innovation Program of Shandong Province 20110100

A novel one-dimensional mixed ligands silver(I) coordination polymer containing two different chains

通讯作者地址: Sun, D (通讯作者),Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 地址: 1. Shandong Univ, Sch Chem & Chem Engn, Jinan 250100, Shandong, Peoples R China 2. Xiamen Univ, Dept Chem, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Fujian, Peoples R China 电子邮件地址: [email protected]; [email protected] mixed-ligand coordination polymer (CP) of the formula {[Ag-3(bmimb)(2) (ndca)(1.5)]center dot H2O}(n) (1) (where bmimb = 1,4-bis(2-methylimidazol-1-ylmethyl)benzene and H(2)ndca = naphthalene-1,4-dicarboxylic acid) was synthesized by reaction of Ag2O and bmimb ligand with H(2)ndca under the ammoniacal condition. It has been structurally characterized by element analysis, IR and X-ray single-crystal diffraction. The bmimb acts as bidentate ligand, and the ndca ligand adopts two different coordination modes in 1, which are mu(4)-eta(1):eta(1):eta(1):eta(1) and mu(2)-eta(1):eta(0):eta(1):eta(0), respectively. Coordination of Ag(I) ions with bmimb and ndca ligands produces two different 1D chains, which is attributed to the different coordination modes of the ndca ligand, indicating the ndca ligand plays an important role in the formation of the diverse 1D chains. The complex 1 exhibits photoluminescent emission in the solid state at room temperature. (C) 2012 Elsevier B.V. All rights reserved.National Natural Science Foundation of China 21021061 21071118 MSTC 2007CB815301 Independent Innovation Foundation of Shandong University 2011GN030 Special Fund for Postdoctoral Innovation Program of Shandong Province 20110100

High LUMO energy level C60(OCH3)4 derivatives:Electronic acceptors for photovoltaiccellswithhigheropen-circuitvoltage

E-mail Addresses: [email protected] regioselective C-60(OCH3)(4) derivatives, C-60(OCH3)(4)-PCBM (a methanofullerene derivative of C-60(OCH3)(4), PCBM=[6,6]-phenyl-C-61-butyric acid methyl ester) and C-60(OCH3)(4)-APCBM (an aziridinofullerene derivative of C-60(OCH3)(4)) were synthesized from C60Cl6 and used as acceptor for polymer solar cells. Revealed by cyclic voltammetry, the LUMO energy levels of C-60(OCH3)4-APCBM and C-60(OCH3)(4)-PCBM are 0.2 and 0.3 eV higher than that of PCBM, respectively. For the polymer photovoltaic cells with fullerene (PCBM, C-60(OCH3)(4)-APCBM or C-60(OCH3)(4)-PCBM) acceptor in combination with poly(3-hexylthiophene) (P3HT) donor, the open-circuit voltage is increased from 0.58 V (for PCBM) to 0.63 V (for C-60(OCH3)(4)-APCBm) and 0.72 V (for C-60(OCH3)(4)-PCBM). The higher open-circuit voltages are reasonably attributed to the higher LUMO levels of the C-60(OCH3)(4) derivatives because of four electron-donating methoxy groups attached. The photovoltaic performance of C-60(OCH3)(4)-PCBMbased device is higher than that involving C-60(OCH3)(4)-APCBM, largely due to the structural changeability of C-60(OCH3)(4)-APCBM resulting from the rotatable N-C bond bridge therein. This work demonstrates that fullerene derivatives with higher LUMO level can be functionalized from multiaddition of electron-donating groups, and exemplifies that photovoltaic performances of fullerene-based solar cells are sensitive even to trivial bridge between functional group and fullerene core. (C) 2012 Elsevier B.V. All rights reserved .National Nature Science Foundation of China U1205111 21031004 21021061 J1210014 20923004 National Basic Research 973 Program of China 2011CB93590

Six low-dimensional silver(I) coordination complexes derived from 2-aminobenzonitrile and carboxylates

通讯作者地址: Huang, RB (通讯作者),Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 地址: 1. Xiamen Univ, Coll Chem & Chem Engn, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China 2. Xiamen Univ, Coll Chem & Chem Engn, Dept Chem, Xiamen 361005, Peoples R China 电子邮件地址: [email protected] new Ag(I) coordination complexes, [Ag(abn)(4-cba)](2) (1), [Ag(abn)(3-cba)](2) (2), [Ag(abn)(fba)](2) (3), [Ag(abn)(3-mba)](2) (4), [Ag(abn)(moba)](2) (5), [Ag(abn)(2)(4-mba)](n) (6), (abn = 2-aminobenzonitrile, 4-cbaH = 4-chlorobenzoic acid, 3-cbaH = 3-chlorobenzoic acid, Hfba = 3-fluorobenzoic acid, 3-mbaH = 3-methylbenzoic acid, Hmoba = 2-methoxybenzoic acid and 4-mbaH = 4-methylbenzoic acid), have been synthesized and characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Complexes 1-4 are similar discrete binuclear Ag(I) motif containing monodentate mu(1)-N-amino abn and mu(2)-eta(1):eta(1) carboxylates. The complementary N-amino-H center dot center dot center dot N-cyano hydrogen bonds link the binuclear motifs into 1D chain which is further extended into 2D supramolecular sheet by N-amino-H center dot center dot center dot O-carboxyl hydrogen bonds. Notably, the electronic effect of substituents in 1-4 has deeply influence on the Ag center dot center dot center dot Ag interaction. Complex 5 is also a discrete binuclear Ag(I) motif but contains a monodentate mu(1)-N-cyano abn ligand. The 1D chain was observed in complex 6 where two different abn ligands with mu(1)-N-cyano and mu(2)-N-cyano, N-amino coordination modes coexist and 4-mba is a chelating mu(1)-eta(1):eta(1) ligand. The results show that the different structures are predominantly attributed to the various ancillary carboxylate ligands and diverse coordination modes of abn ligand. Moreover, the emissive behaviors of them are discussed. (C) 2012 Elsevier B.V. All rights reserved.National Natural Science Foundation of China 21021061 21071118 MSTC 2007CB81530

中国物理海洋学研究70年：发展历程、学术成就概览

本文概略评述新中国成立70年来物理海洋学各分支研究领域的发展历程和若干学术成就。中国物理海洋学研究起步于海浪、潮汐、近海环流与水团,以及以风暴潮为主的海洋气象灾害的研究。随着国力的增强,研究领域不断拓展,涌现了大量具有广泛影响力的研究成果,其中包括:提出了被国际广泛采用的"普遍风浪谱"和"涌浪谱",发展了第三代海浪数值模式;提出了"准调和分析方法"和"潮汐潮流永久预报"等潮汐潮流的分析和预报方法;发现并命名了"棉兰老潜流",揭示了东海黑潮的多核结构及其多尺度变异机理等,系统描述了太平洋西边界流系;提出了印度尼西亚贯穿流的南海分支(或称南海贯穿流);不断完善了中国近海陆架环流系统,在南海环流、黑潮及其分支、台湾暖流、闽浙沿岸流、黄海冷水团环流、黄海暖流、渤海环流,以及陆架波方面均取得了深刻的认识;从大气桥和海洋桥两个方面对太平洋–印度洋–大西洋洋际相互作用进行了系统的总结;发展了浅海水团的研究方法,基本摸清了中国近海水团的分布和消长特征与机制,在大洋和极地水团分布及运动研究方面也做出了重要贡献;阐明了南海中尺度涡的宏观特征和生成机制,揭示了中尺度涡的三维结构,定量评估了其全球物质与能量输运能力;基本摸清了中国近海海洋锋的空间分布和季节变化特征,提出了地形、正压不稳定和斜压不稳定等锋面动力学机制;构建了"南海内波潜标观测网",实现了对内波生成–演变–消亡全过程机理的系统认识;发展了湍流的剪切不稳定理论,提出了海流"边缘不稳定"的概念,开发了海洋湍流模式,提出了湍流混合参数化的新方法等;在海洋内部混合机制和能量来源方面取得了新的认识,并阐述了混合对海洋深层环流、营养物质输运等过程的影响;研发了全球浪–潮–流耦合模式,推出一系列海洋与气候模式;发展了可同化主要海洋观测数据的海洋数据同化系统和用于ENSO预报的耦合同化系统;建立了达到国际水准的非地转(水槽/水池)和地转(旋转平台)物理模型实验平台;发展了ENSO预报的误差分析方法,建立了海洋和气候系统年代际变化的理论体系,揭示了中深层海洋对全球气候变化的响应;初步建成了中国近海海洋观测网;持续开展南北极调查研究;建立了台风、风暴潮、巨浪和海啸的业务化预报系统,为中国气象减灾提供保障;突破了国外的海洋技术封锁,研发了万米水深的深水水听器和海洋光学特性系列测量仪器;建立了溢油、危险化学品漂移扩散等预测模型,为伴随海洋资源开发所带来的风险事故的应急处理和预警预报提供科学支撑。文中引用的大量学术成果文献(每位第一作者优选不超过3篇)显示,经过70年的发展,中国物理海洋学研究培养了一支实力雄厚的科研队伍,这是最宝贵的成果。这支队伍必将成为中国物理海洋学研究攀登新高峰的主力军

pcDNA3.1-HIF-1α重组质粒的构建及其初步鉴定

目的探讨HIf-1α与前列腺癌发病机制之间相关性提供研究工具。方法采用TrIzOl法裂解细胞,提取HIf-1α且以该rnA为模板逆转录为CdnA,然后行PCr处理扩增HIf-1α基因功能片段区域,克隆至真核表达载体PCdnA3.1上,转化至大肠杆菌dH-5α,小提质粒,酶切凝胶电泳鉴定,序列测定,经鉴定为正确序列后中抽质粒,采用fugEnE试剂转染至前列腺癌细胞PC-3,经g418筛选,建立稳定表达HIf-1α的前列腺癌细胞系PCdnA3.1-HIf-1α-PC-3,采用WESTErn印迹鉴定重组质粒的表达。结果 PCr扩增基因片段大小为2.89 kb,克隆至真核载体PCdnA3.1,酶切凝胶电泳可见两个条带,大小大约为5.3 kb和2.89 kb,与预期的大小相符合,序列测定与gEnbAnk公布的一致,WESTErn印迹验证其在细胞内能表达。结论重组质粒PCdnA3.1-HIf-1α能够在前列腺癌PC-3表达,构建成功,为研究HIf-1α与前列腺癌提供了一个工具。厦门市科技局科研基金资助(No.3502Z20084002

蓝藻Anabaena sp.strainPCC7120中一种可诱导的CO2浓缩机制（CCM）

为了探讨蓝藻Ａｎａｂａｅｎａ ｓｐ．ｓｔｒａｉｎＰＣＣ７１２０在外源无机碳浓度变化时，其光合作用对ＣＯ２和ＨＣＯ３的利用特性，制备了高ＣＯ适应细胞，Ａｎａｂａｅｎａ ｓｐ．ｓｔｒａｉｎＰＣＣ７１２０ＨＣＧ细胞的生长速率高于ＬＣＧ细胞，即在空气中生长的细胞，当ＨＣＧ细胞从５％ＣＯ２转换到空气中时，其碳酸酐酶活性升高；它对外源无机碳的表观光合作用亲合力明显提高，说明它的ＣＣＭ活性被诱导，ＨＣＧ与ＬＣ

基于知识迁移的数据驱动迭代学习模型预测控制

迭代学习模型预测控制(iterative learning model predictive control, ILMPC) 作为一种广泛应用于批次生产过程的数据驱动智能控制策略, 能够在沿批次逐步提高跟踪性能的同时沿时间不断抑制实时干扰. 现有ILMPC算法的点对点学习机制依赖于批次运行工况的强一致性,以此保证当前批次与历史批次间的有效信息传递. 然而,生产需求和生产环境的变化通常会导致各批次的操作轨迹和操作周期存在差异,从而使得历史批次提供的先验知识对于后续批次呈现出不精确性和不完整性. 为了提高ILMPC在变运行工况条件下的适应性和灵活性,本文提出了一种具有知识迁移机制的数据驱动ILMPC 策略. 建立自适应深度神经网络(deep neural network, DNN) 沿批次学习 ILMPC 控制行为, 实现历史控制经验在当前批次工况下的全面转换.为抑制DNN前期估计误差的影响,在知识迁移机制下进一步构建Tube 控制结构下的ILMPC算法, 保证ILMPC 系统的时域稳定性和迭代域收敛性. 针对非线性注塑过程的仿真实验验证了在操作轨迹和操作周期同时变化时,所提方法在跟踪精度和收敛速度方面具有明显优势. Iterative learning model predictive control (ILMPC) has become an excellent data-driven intelligent control strategy for batch manufacturing, featured by progressively improving tracking performance along trials while persistently rejecting stochastic disturbance along time. The point-to-point learning mechanism of the existing ILMPCs generally relies on the strict identity of operating conditions along trials to guarantee the integrity and accuracy of historical data. However, the variation of production requirements and environments usually leads to trial-varying reference trajectories and operating durations, resulting in incomplete and inaccurate historical information for the iterative learning of subsequent trials. To promote the adaptability and flexibility of ILMPC under unconformable prior information, this paper proposes an innovative data-driven ILMPC based on knowledge transfer. The control actions of ILMPC are imitated along trials by an adaptive deep neural network (DNN), based on which the prior operation data are transformed to accommodate the condition of each current trial. Under this knowledge transfer mechanism, the tube control scheme is further integrated into ILMPC to restrain the influence of the considerable DNN approximation error in the early trials, which ensures the time-domain stability and iteration-domain convergence of the ILMPC system. Simulations on the nonlinear injection molding process verify that the proposed method has noticeable advantages in the aspects of tracking accuracy and convergence rate when faced with significant changes of operating reference and duration. © 2024 Science China Press. All rights reserved

Construction of Expression Vector for RNA Interference of Hypoxia-inducible Factor 1α and Its Function in the Study of Prostatic Carcinoma Cell Line PC-3

本研究根据PSuPEr.rETrO.PurO载体的特有结构,构建缺氧诱导因子1α(HIf-1α)的rnA干扰(rnAI)表达载体,将其与gfP共转染前列腺癌PC-3细胞36 H后转染效率为(87.15±2.36)%;通过与对照组的比较,质粒转染PC-3细胞48 H后可显著降低胞内HIf-1αMrnA及蛋白的表达;利用重组质粒的嘌呤霉素的抗药性,加药筛选2周,可观察到单克隆生成;收集稳定转染得到的PSuPEr-SIHIf-1α/PC-3细胞株,再次通过WEST blOT检测到PC-3细胞的HIf-1α蛋白表达亦显著降低。结果表明,利用rnAI技术可成功构建抑制前列腺癌HIf-1α表达的SI rnA重组表达载体,为研究HIf-1α在前列腺癌发病机理及增殖、转移中的功能奠定了基础,同时可以用于其在其他肿瘤的功能研究。According to the specific construction of the pSUPER.retro.puro vector,RNA interfering with the hypoxia-inducible factor 1α(HIF-1α) plasmid was constructed in this research programme.The efficiency was(87.15±2.36)% and green fluorescent protein was observed after 36 hours when the constructed plasmid co-transformed into the prostatic carcinoma cell line PC-3;compared with the control groups,this constructed plasmid could reduce the expression of total RNA and protein in PC-3 cells significantly after 48 hours.The cells were checked out by the plasmid resistance against the puromycin biotin,the clones of which were selected and enlarged for two weeks,then the cell strain of pSUPER-siHIF-1α/PC-3 was collected.The HIF-1α protein expression of the pSUPER-siHIF-1α/PC-3 cells of also decreased significantly.The results showed that the RNA interference could be used in the construction of expression vector of constructed siRNA inhibiting the expression of HIF-1α with PC-3 cells,which is the basis of researching the pathology,multiplication,and metastasis of HIF-1α in the prostatic carcinoma and other cancers.厦门市科技局科研基金资助项目(3502Z20084002