Measurement of Large Dipolar Couplings of a Liquid Crystal with Terminal Phenyl Rings and Estimation of the Order Parameters

NMR spectroscopy is a powerful means of studying liquid-crystalline systems at atomic resolutions. Of the many parameters that can provide information on the dynamics and order of the systems, H-1-C-13 dipolar couplings are an important means of obtaining such information. Depending on the details of the molecular structure and the magnitude of the order parameters, the dipolar couplings can vary over a wide range of values. Thus the method employed to estimate the dipolar couplings should be capable of estimating both large and small dipolar couplings at the same time. For this purpose, we consider here a two-dimensional NMR experiment that works similar to the insensitive nuclei enhanced by polarization transfer (INEPT) experiment in solution. With the incorporation of a modification proposed earlier for experiments with low radio frequency power, the scheme is observed to enable a wide range of dipolar couplings to be estimated at the same time. We utilized this approach to obtain dipolar couplings in a liquid crystal with phenyl rings attached to either end of the molecule, and estimated its local order parameters.

Exploring the Consequences of a Representative ``Disallowed'' Conformation of Aib on a 3(10)-Helical Fold

The structural effects of a representative ``disallowed'' conformation of Aib on the 3(10)-helical fold of an octapeptidomimetic are explored. The 1D (H-1, C-13) & 2D NMR, FT-IR and CD data reveal that the octapeptide 1, adopts a 3(10)- helical conformation in solution, as it does in its crystal structure. The C-terminal methyl carboxylate (CO2Me) of 1 was modified into an 1,3-oxazine (Oxa) functional group in the peptidomimetic 2. This modification results in the stabilization of the backbone of the C-terminal Aib (Aib(star)-Oxa) of 2, in a conformation (phi, psi = 180, 0) that is natively disallowed to Aib. Consequent to the presence of this natively disallowed conformation, the 3(10)- helical fold is not disrupted in the body of the peptidomimetic 2. But the structural distortions that do occur in 2 are primarily in residues in the immediate vicinity of the natively disallowed conformation, rather than in the whole peptide body. Non-native electronic effects resulting from modifications in backbone functional groups can be at the origin of stabilizing residues in natively disallowed conformations. (C) 2014 Wiley Periodicals, Inc. Biopolymers

Exploring the Consequences of a Representative ``Disallowed'' Conformation of Aib on a 3(10)-Helical Fold

The structural effects of a representative ``disallowed'' conformation of Aib on the 3(10)-helical fold of an octapeptidomimetic are explored. The 1D (H-1, C-13) & 2D NMR, FT-IR and CD data reveal that the octapeptide 1, adopts a 3(10)- helical conformation in solution, as it does in its crystal structure. The C-terminal methyl carboxylate (CO2Me) of 1 was modified into an 1,3-oxazine (Oxa) functional group in the peptidomimetic 2. This modification results in the stabilization of the backbone of the C-terminal Aib (Aib(star)-Oxa) of 2, in a conformation (phi, psi = 180, 0) that is natively disallowed to Aib. Consequent to the presence of this natively disallowed conformation, the 3(10)- helical fold is not disrupted in the body of the peptidomimetic 2. But the structural distortions that do occur in 2 are primarily in residues in the immediate vicinity of the natively disallowed conformation, rather than in the whole peptide body. Non-native electronic effects resulting from modifications in backbone functional groups can be at the origin of stabilizing residues in natively disallowed conformations. (C) 2014 Wiley Periodicals, Inc. Biopolymers

Self-assembly of Metallamacrocycles Employing a New Benzil-based Organometallic Bisplatinum(II) Acceptor

A benzil-based semi-rigid dinuclear organometallic acceptor 4,4'-bistrans-Pt(PEt3)(2)(NO3)(ethynyl)]benzil (bisPt-NO3) containing a Pt-ethynyl functionality was synthesized in good yield and characterized by multinuclear NMR (H-1, P-31, and C-13), electrospray ionization mass spectrometry (ESI-MS), and single-crystal X-ray diffraction analysis of the iodide analogue bisPt-I. The stoichiometric (1:1) combination of the acceptor bisPt-NO3 separately with four different ditopic donors (L-1-L-4; L-1 = 9-ethyl-3,6-di(1H-imidazol-1-yl)-9H-carbazole, L-2 = 1,4-bis((1H-imidazol-1-yl)methyl)benzene, L-3 = 1,3-bis((1H-imidazol-1-yl)methyl)benzene and L-4 = 9,10-bis((1H-imidazol-1-yl) methyl)anthracene) yielded four 2 + 2] self-assembled metallacycles M-1-M-4 in quantitative yields, respectively. All these newly synthesized assemblies were characterized by various spectroscopic techniques (NMR, IR, ESI-MS) and their sizes/shapes were predicted through geometry optimization employing the PM6 semi-empirical method. The benzil moiety was introduced in the backbone of the acceptor bisPt-NO3 due to the interesting structural feature of long carbonyl C-C bond (similar to 1.54 angstrom), which enabled us to probe the role of conformational flexibility on size and shapes of the resulting coordination ensembles.

Spectral characterizations and photophysical properties of one-step synthesized blue fluorescent 4 `-aryl substituted 2,2 `:6 `,2 `'-terpyridine for OLEDs application

We have synthesized a series of 4'-aryl substituted 2,2':6',2 `'-terpyridine (terpy) derivatives, namely 4'-(4-methylphenyl)-2,2':6',2 `'-terpyridine (C-1), 4'-(2-furyl)-2,2':6'2 `'-terpyridine (C-2), and 4'-(3,4,5-trimethoxyphenyl)-2,2':6',2 `'-terpyridine (C-3). The synthesized terpy compounds were characterized by elemental analyses, FTIR, NMR (H-1 and C-13), and ESI-Mass spectrometry. Photophysical, electrochemical and thermal properties of terpy compounds were systematically studied. Maximum excitation band was observed between 240 and 330 nm using UV-visible spectra, and maximum emission peaks from PL spectra were observed at 385, 405 and 440 nm for C-1, C-2 and C-3 respectively. Fluorescence lifetime (tau) of the fluorophores was found to be 035 and 1.55 ns at the excitation wavelength of 406 nm for C-1 and C-2 respectively, and tau value for C-3 was found to be 0.29 ns at the excitation wavelength of 468 nm. We noticed that the calculated values of HOMO energy levels were increased from 5.96 (C-1) to 6.08 (C-3) eV, which confirms that C-3 derivative is more electrons donating in nature. The calculated electrochemical band gaps were 2.95, 2.82 and 3.02 eV for C-1, C-2 and C-3 respectively. These blue fluorescent emitter derivatives can be used as an electron transport and electroluminescent material to design the blue fluorescent organic light emitting diode (OLED) applications. (C) 2015 Elsevier B.V: All rights reserved.

A new synthesis of Entacapone and report on related studies

A new synthesis of the catechol-O-methyltransferase (COMT) inhibitor, entacapone (E-isomer) has been achieved under mild conditions by amine-mediated demethylation of the precursor 2-Cyano-3-(3- hydroxy-4-methoxy-5-nitrophenyl) prop-2-eneamide, wherein the methoxyl group adjacent to a nitro group gets demethylated under nucleophilic attack. Similar demethylation was achieved on ethyl 2-cyano-3-(3, 4-dimethoxy-5-nitrophenyl) prop-2-enoate, 2-cyano-3-(3,4-dimethoxy-5-nitrophenyl)-N,N-diethylprop-2-enamide, ethyl 2-cyano-3-(3-hydroxy-4-methoxy-5-nitrophenyl) prop-2-enoate and ethyl 2-cyano-3-(4-methoxy-3-nitrophenyl) prop-2-enoate. The scope of demethylation has been studied. Analogues of ethyl 2-cyano-3-(3, 4-dimethoxy-5-nitrophenyl) prop-2-enoate wherein a methoxyl group is not adjacent to a NO (2) group are unaffected and phenolic derivatives yield the amine salts. Entacapone has been converted to salts with organic bases. The crystal structure of the isomer of entacapone (Z-isomer), a significant human metabolite of E-isomer has been established. NMR methods for deriving E and Z geometry and other similar molecules have been successfully established, mainly by studying the proton coupled C-13 spectra. Preliminary studies reveal in vitro activity for some compounds against tuberculosis (TB) and dengue.

Structural characterization and in vitro biomedical activities of sulfated chitosan from Sepia pharaonis

A low molecular weight sulfated chitosan (SP-LMWSC) was isolated from the cuttlebone of Sepia pharaonis. Elemental analysis established the presence of C, H and N. The sulfation of SP-LMWSC was confirmed by the presence of characteristic peaks in FT-IR and FT-Raman spectra. The thermal properties of SP-LMWSC were studied by thermogravimetric analysis and differential scanning calorimetry. Electrolytic conductivity of SP-LMWSC was measured by cyclic voltammetry and the molecular weight was determined by MALDI-TOF/MS. The molecular structure and sulfation sites of SP-LMWSC were unambiguously confirmed using H-1,C-13, 2D COSY and 2D HSQC NMR spectroscopy. SP-LMWSC exhibited increased anticoagulant activity in avian blood by delaying coagulation parameters and displayed cytostatic activity by inhibiting the migration of avian leucocytes. SP-LMWSC demonstrated avian antiviral activity by binding to Newcastle disease virus receptors at a low titer value of 1/64. These findings suggested that SP-LMWSC isolated from an industrial discard holds immense potentials as carbohydrate based pharmaceuticals in future. (C) 2015 Elsevier B.V. All rights reserved.

Iso-specific Ziegler-Natta polymerization of α-olefins with a single-component organoyttrium catalyst

The synthesis of a sterically tailored ligand array (M)_2((C_5H_2-2-Si(CH_3)_3-4-C(CH_3)_3)S_2i(CH_3)_2]("M_2Bp") (M = Li, 16; K, 19) is described. Transmetallation of Li_2Bp with YCl_3(THF)_3 affords exclusively the C_2 symmetric product rac-[BpY(µ_2-Cl)_2Li(THF)_2], 20. A X-ray crystal structure of 20 has been determined; triclinic, P1, a= 13.110 (8), b = 17.163 (15), c = 20.623 (14) Å, α = 104.02 (7), β = 99.38 (5), γ = 100.24 (6)° , Z = 4, R = 0.056. Transmetallation of K_2Bp with YCl_3(THF)_3 affords the halide free complex rac-BpYCl, 23. The corresponding rac-BpLaCl, 28, is prepared in an anlogous manner. In all cases the achiral meso isomer is not obtained since only for the racemic isomers are the unfavorable steric interactions between the Si(CH3)_3 groups in the narrow portion of the [Cp-M'-Cp] wedge avoided. Alkylation of 20 or 23 with LiCH(Si(CH_3)_3)_2 affords rac-BpYCH(Si(CH_3)_3)_2, 26 in good yield. Alkylation of 28 with LiCH(Si(CH_3)_3)_2 affords rac-BpLaCH(Si(CH_3)_3)_2 29. Hydrogenation of 26 cleanly affords the bridging hydride species [BpY(µ_2-H)]_2, 27, as the homochiral (R,R) and (S,S) dimeric pairs. 26 is an efficient initiator for the polymerization of ethylene to high molecular weight linear polyethylene. 27 catalyzes the polymerization of propylene (25% v/v in methylcyclohexane) and neat samples of 1-butene, 1-pentene, 1-hexene to moderately high molecular weight polymers: polypropylene (M_n = 4,200, PDI 2.32, T_m 157 °C); poly-1-butene (M_n = 8,500, PDI 3.44, T_m 105 °C); poly-1-pentene (M_n = 20,000, PDI 1.99, T_m 73 °C); poly-1-hexene (M_n = 24,000, PDI 1.75, T_m < 25 °C). ^(13)C NMR spectra at the pentad analysis level indicates that the degree of isotacticity is 99% mmmm for all polymer samples. 27 is the first single component iso-specific α-olefin polymerization catalyst. The presumed origins of the high isospecificity are presented.

中国八种家鼠C-带核型的比较研究

对我国大陆八种家鼠的C-带核型进行了比较研究, 并将C-带差异数量化 进 行模糊聚类分析 结果表明: 八种家鼠的C-带核型相互间存在一定的差异, 通过 分析, 得到了八种家鼠的聚 类分析分支图, 分为二大组: 斯氏家鼠和环齿鼠为 一组 其余种类为另一组。图版1图1表4参23

蒺藜活性物质的研究

本文以确立蒺藜及其相关药物心脑舒通的质量标准为目的对蒺藜中甾体皂甙进行了系统的研究，在前人已分出20种甾体皂甙的基础上，我们又从中发现10种甾体皂甙，其中9种为新化合物，丰富了蒺藜的化学基础内容，对确立蒺藜及其相关药物的质量标准和弄清蒺藜药物的作用机理有较重要的意义。主要结果如下：1 探索出一套植物中甾体皂甙系统分离的简单而有效的方法。蒺藜果实依次经水提、乙醇沉淀、大孔吸附树脂柱层析、脱色树脂、反复硅胶柱层析和HPLC，可使其中甾体皂甙得到系统全面的分离，并且保持了甾体皂甙的原有存在形态。我们发现蒺藜果实中有不少于40种的呋甾皂甙，而茎叶中的数量更多，由于时间限制，我们只分离出其中的10种，其余留待进一步研究。我们同时还对蒺藜果实和茎叶中甾体皂甙的分布进行了比较，发现果实中甾体皂甙集中在极性较大的部位而茎叶中分布则比较均匀。2 根据显色反应和谱学方法，尤其是NMR，我们确定了分得的10种化合物的结构，其中II为从蒺藜中首次分出，其余为新化合物。以上化合物的结构鉴定过程表明~(13)C NMR是确定中等分子量甾体皂甙的有效手段。由于皂甙的甙元和糖链之间除连接部位外~(13)C化学位移影响不大，可分别进行归属。但文献报道的~(13)C NMR数据归属尚有一些不确之处，尤其是糖链部分谱峰的归属，这在通过比较确定新化合物结构时应加以注意。

低分子量聚苯胺及苯胺低聚体的合成与表征

对导电聚苯胺研究的深入，它的一些潜在的应用正在逐步实现。这些应用使对聚苯胺需求正在逐年增加，要求聚苯胺的合成工艺进一步得到改善和提高。本论文以此为目的找到了适合工业化生产的合成路线，并对由该方法合成的聚苯胺和常规合成的聚苯胺进行对比研究。在此基础上开展了苯胺低聚体的合成与表征工作。1．采用H_2O_2-Fe~(2+)催化氧化体系合成了聚苯胺。经过优化的反应条件：◇ 以Fe~(2+)或Fe~(3+)为催化剂，其用量为单体的1/500(摩尔比)：◇ 初始反应在冰浴中(温度为0℃)进行，随着反应的进行温度逐渐升至室温；共计反应24小时；◇ 体系中酸浓度控制在1 mol/L左右；单体浓度介于0.5-1.0mol/L；◇ 氧化剂摩尔用量为单体的1-1.5倍。在这一反应条件下制得的聚苯胺，产率可达到70%，电导率在10°S/cm(HCl掺杂，粉末压片测电导)。该材料具有低分子量(2000-10000)、高溶解性(NMP，DMF，DMSO)，低凝胶化等特点，对比研究了由该方法合成聚苯胺和利用(NH_4)_2S_O_8合成聚苯胺的光谱特征，结晶性和热稳定性。2．用开路电位和现场紫外的方法跟踪H_2O_2-Fe~(2+)体系苯胺的聚合过程，发现H_2O_2-Fe~(2+)体系与(NH_4)_2S_2O_8体系相比，苯胺的聚合过程存在一定的不同之处。如在该体系中不存在诱导期；氧化剂分解速度慢，聚合时间较长；氧化电位低，在反应过程中聚合物链趋向于中间氧化态：但是活性链的末端需处于高氧化态才能完成链增长过程。整个反应过程中放热不明显。根据实验结果给出H_2O_2-Fe~(2+)体系苯胺的聚合机理。3．利用化学氧化缩合和电化学方法合成了苯/胺封端的四聚体，对两种方法合成的苯胺四聚体进行光谱表征，证明了苯胺四聚体的结构。通过研究苯胺四聚体的~1H NMR，证明在中间氧化态的苯胺四聚体中存在三种位置异构体，异构体相对含量随溶剂的不同而不同。进一步研究~(13)C NMR，证明中间氧化态的苯胺四聚体结构中含有顺反异构体。这些异构体的存在使得四聚体的~(13)CNMR变得十分复杂，本论文尝试对中间氧化态的苯胺四聚体的~(13)C NMR进行季碳峰的归属。4．合成了还原态和氧化态苯封端二聚体、三聚体和四聚体。通过FTIR、UV-Vis和NMR表征了还原态和氧化态的苯封端低聚体，并对谱峰进行归属。氧化态低聚体分子在溶液中的构象影响紫外光谱可见区的吸收带。5．对掺杂态低聚体进行了UV-Vis和NMR谱的研究，UV-Vis光谱表明苯胺低聚体和聚苯胺掺杂过程具有相似的电荷转移方式和结构变化。而四聚体更具有代表性。NMR结果表明苯胺低聚体掺杂后主链上的电荷重新分布，环上的H原子上的电子被C原子吸引，电荷密度降低，在~1H NMR中谱峰向低场移动。C原子的谱峰也相应发生变化，醌环上电荷密度增加，全部C原子的峰向高场移动，与醌环相邻苯环受其影响季碳峰移向高场，非季碳峰移向低场。更远处的苯环也受到影响，但影响不大。这些变化表明苯胺低聚体的掺杂符合“BQ四环变体模型”。由此对“BQ四环变体模型”提供了新的证据。

在辉光放电中八氟环丁烷聚合的研究

I 理论部分：对未知结构聚合物的ESCA谱进行表征，一是利用已知结构小分子化合物的ESCA谱中结合能值进行标定，二是运用电荷电位模型经量子化学计算对谱峰进行归属。由于所处化学环境不同，用小分子化合物的ESCA谱峰位对象合物标定不够准确，量子化学计算又太复杂。本工作提出了电负性经验公式，可计算ESCA谱中C_(1S)结合能位移值，与实测值作对照即可判断聚合物结构，方法简便，准确可靠。电负性经验公式表达如下：聚合物分子链上某碳原子1S电子结合能位移ΔEc可看作该碳原子与相邻基团间电负性差值和的函数，即ΔEc = K_c ∑ from i=1 to 4 1/(n_i) (X_i - 2.5) + b。聚合物分子链上各碳原子的实际电负性为X_c = (∑ form j=1 to 4 1/(n_j) X_j/∑ form j=1 to 4 1/(n_j) + 2.5)/2运用电负性经验公式计算了九个模型化合物中C_(1S)的ΔEc，推导出F作为α、β、γ位碳上的取代基的对α位碳上1s电子结合能位移影响产生的效应值，即，对于ΔEc = aα + bβ + cγ，有α = 3.018 (±0.007)，β = 0.2513 (±0.0007) γ = 0.0176 (±0.003)。此结果与ESCA谱实测值相符。本工作设计了十六种化合物模型，模型中具有含氟等离子体聚合物中可能存在的大部分基团，通过电负性经验公式计算求得化学环境不同的C_(1S)结合能位移值，把ESCA谱的实测值和计算值进行对照，可对象合物的求知结构作出大致判断。II 在辉光放电中八氟环丁烷的聚合与刻蚀反应：在碳氧化合物的辉光放电中同时存在聚合与刻蚀两种相反的过程，聚合与刻蚀竞争的结果对聚合速率，产物结构都有很大影响。本工作通过测定聚合速率、IR谱、ESCA谱研究了反应条件对八氟环丁烷等离子体聚合与刻蚀的影响，得到了一致的和半定量的结果。实验证实，随着功率的增大或压力的减小，刻蚀有增强的趋势，不同的等离子气体对聚合与刻蚀的竞争过程有不同的影响，刻蚀强弱的顺序为Ar>N_2>H_2>He，增加等离子气体对单体的比率，引起刻蚀增加。聚合速率不随功率的改变而变化的状态是由聚合与刻蚀间的平衡引起的。随着功率增大或压力减少，聚合产物支化程度增加，线性程度减小，F/C比相应减小。同样随等离子气体种类不同，聚合物支化程度大小的顺序是Ar>N_2>H_2>He，F/C比相应变化。总之，聚合产物支化程度的变化和聚合与刻蚀的竞争结果相一致。对等离子体聚合与刻蚀竞争过程的定量描述未见文献报导。III 八氟环丁烷等离子体聚合物的结构和表征：用IR和ESR谱测得OFCB等离子体聚合物中存在五种元素：C、F、O、N、Si，并对可能存在于结构中的基因作了分析。通过NaHSO_3的亲核双键加成反应，用IR和ESR谱证实了等离子体聚合物中存在的双键及其类型。类似工作未见文献报导。用CuSO_4·5H_2作标样，测出PPOFCB中的自由基浓度为10~(19)自旋数/克。在80、100、120、140 ℃考察PPOFCB中俘获自由基的衰减过程，证实此过程涉及两类不同的反应，一是自由基的复合反应，二是自由基的氧气的终止反应。对上述两类反应进行动力学处理，求出了自由基复合反应在不同温度时的速度常数，并得到反应治化能为374焦耳/摩尔或8.869千卡/摩尔。氧和自由基的终止反应中，氧气的扩散过程是决定反应速度的步骤，反应速度常数就是扩散速度常数，K = 5.3 * 10~(-23)自旋数~(-1)、克分~(-1)。根据VPO测出的PPOFCB的分子量和自由基浓度，算出每4.5个分子中有一个自由基。类似工作未见文献报导。PPOFCB的分子量随反应条件不同而变化，用VPO测出，在80W和40W功率，在Ar存在下制备的OFCB等离子体聚合物的分子量分别为2736和2003。用~(19)F-NMR谱对PPOFCB中的基团进行定量计算，得出在一个90W，He气中制备的聚合物分子中，CF_3-CF_2为6.1，CF_2为13.5，CF_3-CF为7.9，CF为17.5，CF_3-C为6.1，C为13.5。在用上述方法进行结构表征的基础上，提出了OFCB等离子体聚合物的结构模型。IV 八氟环丁烷等离子体聚合的反应历程：以Ar、N_2、H_2、He为等离子气体，分别对OFCB等离子体聚合的气体冷凝物进行GC-Mg、~(19)F-NMR和ESR测试，观察到在气相中，OFCB经历了等离子态反应。单体被打断的程度，和高能电子浓度有关。体系中电子浓度依赖于气体的第一电离势和气相内的化学反应类型。初级粒子二氟卡宾：CF_2和中间体六氟丙烯是气相中的主要产物。~(19)F-NMR证实气相中存在支化产物，表明聚合物在气相中发生了重排。ESR谱测得，在气相产物中存在高浓度的由二种以上组分混合而成的自由基，自由基间的复合反应是生成聚合物的主要增长过程，气相产物的分子量随放电功率的升高而增大。根据聚合物中存在的高含量CF_3基团，分析了CF_3基团对聚合过程的影响。CF_3基团产生了屏蔽效应，它既保护了聚合物不致被降解，也限制了生成高分子量产物。实验证实，CF_3基团的生长来自F的重排，同时未自支化气相产物的非均相增长。OFCB等离子体聚合物中俘获自由基主要是由高能电子轰击聚合物表面产生的，同时来自被固相吸附的带有自由基的气相产物。在碳氟化合物的等离子体聚合中，吸附是和聚合同样重要的过程，气相产物被吸附后，可继续再引发、增长、刻蚀等反应过程、直到成为固相内层分子为止。ESR谱证实，高能粒子的轰击在辉光放电中起主导作用，紫外辐射对含氟聚合物引发和脱氟作用微弱。在气相和表面反应历程讨论的基础上，提出了OFCB等离子体聚合的反应历程模型，解释了碳氢和碳氟两个等离子体象合体系遵循不同反应历程的原因。本部分工作的实验和反应历程解释基本未见文献报导。

酸性磷（膦）酸酯萃取稀土、相关元素的机理及萃合物结构研究

本文研究了酸性磷（膦）酸酯对稀土及相关元素的萃取（包括协同萃取）机理，利用核磁共振（NMR）测试手段对HEH/EHP(III)、BTMPPA－Yb(III)的萃合物结构进行了~1H、~(13)C、~31P NMR谱的测定，获得了一些新的结构信息。

全球变化背景下科尔沁沙地生态系统C、N循环过程

工业革命以来，由于人口的快速增加和人类活动的强烈干扰（主要包括煤炭、石油等石化燃料的燃烧、化肥生产和使用）导致土地利用/覆被变化、大气CO2浓度升高、N沉降等一系列全球环境变化问题。有关陆地生态系统生物地球化学循环，尤其是陆地生态系统C、N循环及其耦合过程方面的研究成为全球变化科学研究领域的重要内容。 干旱/半干旱地区占地球陆地总面积的1/3。与湿润地区相比较，干旱/半干旱地区生态系统稳定性比较差，往往属于生态脆弱区。因此，全球变化对干旱/半干旱地区生态系统影响更加敏感。科尔沁沙地位于我国北方干旱/半干旱地区，是我国典型的农牧交错区和生态脆弱区。科尔沁沙地是世界上人口密度最高的干旱/半干旱地区之一，人类活动对其影响剧烈。然而，有关科尔沁沙地生态系统C、N元素生物地球化学循环过程对土地利用/覆被变化、N沉降等全球变化响应及其反馈机制的研究非常缺乏。因此，本文以科尔沁沙地退化沙质草地、农田、不同年龄樟子松和杨树人工林等生态系统为对象，开展了造林、模拟N沉降和凋落物管理对生态系统C、N元素循环过程影响的研究。 在科尔沁沙地东南缘，以退化沙质草地、樟子松（Pinus sylvestris var. mongolica）人工林（15、24和30年生）、杨树（Poplus xiaozhuanica）人工林（7、11和15年生）为对象，研究草地转变为林地对生态系统C、N储量影响；以退化草地、榆树疏林草地和32年生樟子松人工林为对象，比较草地造林对土壤C、N循环过程及其土壤微生物性状的影响；以农田和5、10、15年生杨树人工林为对象，研究退耕还林对生态系统C、N储量和循环过程影响；以35年生樟子松人工林为对象，模拟研究N沉降和凋落物管理对生态系统C、N循环过程影响。通过上述研究，得到以下主要结果： （1）草地生态系统总C储量为34.38 Mg ha-1，15、24和30年生樟子松人工林生态系统总C储量分别为43.56、60.45和66.59 Mg ha-1，7、11和15年生杨树人工林生态系统总C储量分别为34.54、48.26和78.77 Mg ha-1；与农田相比，退耕5年的杨树人工林生态系统总C库储量下降13%，而10年和15年杨树人工林分别增加了176%和5倍；随着人工林年龄的增加，地上植被生物量C库储量占生态系统总C库储量的比例逐渐增加，并主要分配在树干。草地生态系统总N库储量为2.54 Mg ha-1，15、24和30年生樟子松人工林生态系统总N库储量分别为1.96、2.10和2.19 Mg ha-1，7、11和15年生杨树人工林生态系统总N库储量分别为2.27、1.84和2.60 Mg ha-1；与农田相比，退耕5年的杨树人工林生态系统总N库储量下降32%，而10年和15年杨树人工林分别增加了47%和76%；农田和草地造林后生态系统N储量依然主要分配在土壤中。 （2）草地和农田造林后土壤C、N库储量的变化受多因子的影响，例如林龄、树种种类以及立地条件等。农田和草地造林初期，土壤C、N库储量表现出下降趋势，随着林龄的增加，土壤C、N储量逐渐恢复。草地营造樟子松人工林30年后，0–60 cm深度土壤C、N储量依然显著低于草地；与草地相比，15年生杨树人工林土壤C、N储量差异不显著。在立地条件较好的情况下，10年杨树人工林土壤C、N储量已显著高于农田；然而，在立地条件相对较差的情况下，15年杨树人工林土壤C、N储量仍然与农田相比差异不显著。 （3）土地利用变化能够强烈地改变土壤C、N循环过程。与草地或疏林草地相比，32年生樟子松人工林土壤C、N、P含量显著降低；土壤C、N矿化过程发生显著变化，并且受季节变化的影响；在不同季节，土壤微生物量碳含量、代谢熵（qCO2）、微生物熵（MBC/TOC）以及土壤酶活性等在不同土地利用条件下表现出规律不一致。同样，农田退耕杨树人工林能够显著影响土壤C、N矿化过程，土壤无机氮（铵态氮+硝态氮）含量，土壤微生物量碳含量以及土壤微生物活性。草地造林在一定程度上导致土壤质量下降。而农田造林有利于土壤质量改善，尤其在在立地条件较好情况下。 （4）N添加增加对沙地樟子松人工林地上和地下C、N元素含量影响不大；N添加1年后，仅林下植被C、N含量显著增加，高氮处理（N15）凋落物N含量显著增加。N添加抑制了沙地樟子松人工林凋落物的早期分解和N、P元素释放。5、6、8和9月份土壤无机N含量均随着N输入增加表现出一定程度的增加，然而，7月份N添加导致土壤无机N含量降低。N添加对土壤潜在N矿化速率影响不显著。7和8月份N添加影响土壤C矿化速率，而其它月份影响不显著。低氮处理（N5）有利于增加土壤微生物量碳含量，而高氮处理（N15）在一定程度上降低土壤微生物量碳含量。 （5）凋落物输入变化（凋落物添加和凋落物移出）在一定程度上改变了35年生沙地樟子松人工林生态系统C、N循环过程。凋落物移出（C0）增加了林下植被C含量，降低了树木叶片N含量。凋落物移出抑制了凋落物分解和P元素的释放，而增加了C元素的早期释放速率，对N元素释放过程影响不显著。凋落物输入变化对不同月份土壤无机N含量和土壤N矿化过程影响均不显著。仅在6月份凋落物移出显著抑制了土壤C矿化速率，其它月份差异均不显著。凋落物管理对土壤微生物量碳含量影响不显著。 以上研究结果表明，土地利用变化、N沉降和凋落物输入改变等能够影响半干旱地区沙地生态系统C、N储量和循环过程。尤其是土地利用变化强烈改变沙地生态系统C、N储量、分配格局和循环过程，并且受到多因子的影响。科尔沁沙地樟子松人工林生态系统C、N元素生物地球化学循环存在密切的耦合关系。今后有必要进一步结合3S技术、同位素技术、模型模拟以及分子生物学技术等，从微观-宏观不同尺度上，研究半干旱地区沙地生态系统C、N循环过程对全球变化的响应及其反馈机制。

Molybdenum containing surface complex for olefin epoxidation

Silica-supported molybdenum surface complexes were prepared by the reaction between (N=) Mo(OtBu)(3) and silica via displacement of the tert-butoxy ligands for siloxyls from the silica surface. The structure of the surface molybdenum complexes was well defined by in-situ FT-IR, elemental analysis, H-1 NMR and C-13 CP/MAS NMR techniques. The surface complexes could undergo alcoholysis reaction with CD3OD and CH3OH in the same way as free (N =) Mo(OtBu)(3) and they show high catalytic activity and selectivity in olefin epoxidation. Initial rates up to 24.9 mmol epoxide (mmol Mo)(-1) min(-1) were achieved in the epoxidation of cyclohexene using TBHP as oxidant.