N, N'-二芳基己二酰双偶氮化合物的合成及其结构表征

以N, N'-二芳基己二酰二肼类化合物为原料,用Fe(NO3)3·9H2O作氧化剂,在室温无溶剂条件下将N, N'-二芳基己二酰二肼类化合物氧化脱氢为N, N'-二芳基己二酰双偶氮化合物.产物结构经元素分析、IR、 1H NMR确证,原料的IR谱中在3200～3400cm-1出现的2个N-H吸收峰在氧化产物中消失,但在1455cm-1附近有-N=N-吸收峰;1H NMR谱中在δ7.3～10.5之间的2个N-H化学位移在氧化产物中也消失;产物的元素分析结果与理论值基本相符.收率80%～94%.     

特定条件下的定向ZnO纳米棒的制备及表征

采用改进的溶胶凝胶和化学溶液生长两步法, 并控制特定条件在镀银载玻片上制备出定向ZnO纳米棒. 利用X射线衍射(XRD)、扫描电镜(SEM)、透射电镜(TEM)、选区电子衍射(SAED)、能谱(EDS)及傅里叶红外吸收光谱(FTIR)对纳米棒的表面形貌、结构、组分进行分析. XRD和SEM结果表明该ZnO纳米棒具有六角纤锌矿结构, 结晶质量良好, 垂直衬底生长. TEM和SAED结果表明该ZnO纳米棒形状规则, 为单晶结构. FTIR谱中的位于418 和541 cm^－1的吸收峰对应于棒状ZnO结构的伸缩振动吸收峰, 1384 和1636 cm^－1对应于六方纤锌矿ZnO晶体的Zn—O伸缩振动吸收峰. 利用负离子配位四面体生长理论初步解释ZnO纳米棒的生长过程.     

带树枝状侧链聚苯乙炔的合成与结构表征

合成了带树枝状聚苯甲醚修饰基团的苯乙炔单体,在Rh[(nbd)Cl2]2催化剂的作用下得到了侧链带聚苯甲醚树枝的新型聚苯乙炔衍生物,用红外吸收光谱、核磁共振谱、紫外可见吸收光谱和凝胶渗透色谱表征了聚合物的结构.发现聚合物的重均分子量达到了57300,在氯仿、N,N-二甲基甲酰胺、四氢呋喃等有机溶剂中有良好的溶解性能.由于侧链上聚苯甲醚树枝体积庞大,聚合物主链采取立构规整的顺-顺式构象,紫外可见吸收光谱在440nm附近出现了显著的共轭主链的吸收肩峰;立构规整的顺-顺式构象使树枝状侧链形成了对主链保护的"夹套效应",聚合物热分解温度从聚苯乙炔母体的225℃提高到295℃.     

三唑并嘧啶磺酰胺类除草剂的定性鉴别

采用红外吸收光谱,核磁共振氢谱,超高效液相色谱-四极杆飞行时间质谱对3种三唑并嘧啶磺酰胺类除草剂进行分析。红外吸收谱图表明:3 360~3 180,1 630,1 540,1 500,1 300,1 150cm~(-1)附近的峰是此类除草剂的特征吸收,根据嘧啶环上取代基的不同引起的波数变化可加以区分鉴别;氢核磁共振谱图表明:δ_H7.46~9.38,δ_H10.82~11.91分别为嘧啶环氢和磺酰胺基氢特征位移,根据嘧啶环上取代基不同引起的化学位移的差异可加以区分鉴别;超高效液相色谱-四极杆飞行时间质谱图表明:磺酰胺基桥链是最容易断裂的基团,并产生相应特征离子碎片。3种谱图联用可对此类化合物定性鉴别。     

依碳氯替泼诺的结构分析研究

对依碳氯替泼诺的红外光谱(IR)、紫外光谱(UV)、质谱(MS)、氢-氢相关谱(^1H-^1HCOSY)、碳谱(DEPT-45、DEPT-90、DEPT-135)、碳氢相关谱(HMQC)数据和解析进行了全面的报道。对所有的^1H NMR、^17C NMR谱的信号进行了归属，讨论了质谱的主要碎片离子的可能裂解方式和红外所对应的官能团的振动吸收形式、紫外特征吸收峰所对应的不饱和共轭体系电子跃迁能量。     

银催化端炔的砜胺化反应

正Angew.Chem.Int.Ed.2017,56,13805~13808炔烃是基础的化学化工原料,炔烃的活化与转化一直是有机化学研究的核心内容之一.东北师范大学化学学院毕锡和课题组在非活化端炔双官能化方向取得重要研究进展.自由基参与的炔烃双官能化反应是制备官能化烯烃的直接途径,一般来说,自由基物种首先进攻炔烃碳碳叁键,生成烯基自由基中间体,然后再与其它物种偶联生成官     

苯乙炔聚合反应的研究

研究了用苯甲酰过氧化物作引发剂的苯乙炔的聚合作用。当引发剂的用量为单体的1克分子％以下时,在60°,聚合作用很少进行,当引发剂的用量为2—4克分子％时,聚合作用明显地发生。当温度由60°升高到130°时,聚合速度显著地增加。所得聚合物的平均分子量为600—1500。红外光谱显示聚合物分子中有C_6H_5COO—端基的存在。在160°聚合产物的红外光谱中,C=O和C—O键的特征吸收基本上消失。 苯乙炔的热聚合在100°以下很少发生,在100—160°,聚合速度随温度升高而迅速增加。 三氟化硼不论在室温或较低温度可以引起苯乙炔的急骤聚合,所得聚苯乙炔的平均分子量在2000以上。 测定了几种聚苯乙炔样品的红外光谱,其中除引发聚合产物显示的苯甲酰氧基的C=O与C—O键的特征吸收外,其余均颇类似。与Okamoto等报导的聚苯乙炔的红外光谱相比较,只是在770—700厘米~(-1)区域内有微小的差异,而光谱的绝大部分是十分类似。因此可以认为,本文中报导的用几种不同的方法所得到的聚苯乙炔很可能具有相同的键结构:     

利用点击化学反应修饰聚氨酯

合成了2,2-丙炔基-1,3-丙二醇(DPPD),将其作为扩链剂引入聚氨酯(PU)主链分子中,获得了一种主链带有炔基的可降解聚氨酯材料,并通过叠氮基团与炔基间的点击化学反应,将模型分子引入到聚氨酯分子链上.1H NMR图谱中δ2.03的峰及红外图谱中2138 cm-1处的峰证实炔基引入了聚氨酯分子链;1H NMR图谱δ7.91处的峰表明采用点击化学方法将苄基叠氮分子引入了聚氨酯分子主链.当扩链系数分别为1,0.7和1[70%DPPD+30%1,3-丙二醇(PDO)]时,最终产物中炔基含量分别为0.396,0.235和0.197 mmol/g.细胞毒性实验结果表明,炔基的引入对细胞活性没有影响.     

trans—PtHX（AsPh3）2配合物的合成及核磁共振研究

合成了 trans-PtHX(AsPh_3)_2(X=Cl~-、Br~-、I~-、SCN~-)四个配合物,除 trars-PtHCl(AsPh_3)_2外,其余三个为新配合物。用 NMR 和 IR 谱鉴定了结构和 trans-PtHSCN(AsPh_3)_2 的键合异构。研究了配体(X)对铂-氢化学位移(δ_H)和铂-氢偶合常数(J_(Pt-H))的影响、铂-氢键键长与铂-氢化学位移(δ_H)的关系以及铂-氢化学位移(δ_H)与铂-氢伸展振动频率的相关性。发现 trans-PtHCl(AsPh_3)_2 在不同溶剂中的重结晶产物,其 Pt-H 键的红外伸展振动频率不同,而 ~1HNMR 谱(在 CDCl_3 中)完全一样。     

室温合成羟异丙基保护炔基的一阶苯炔dendrimer

在室温下,使用Sonogashira交叉偶联反应体系,以均三炔苯为核,以较高的收率合成了一种重要的新型芳炔功能单体——羟异丙基保护炔基的一阶间位苯乙炔dendrimer,并用核磁共振氢谱对产物进行了结构鉴定.     

Hybridization of thiol-functionalized poly(phenylacetylene) with cadmium sulfide nanorods: improved miscibility and enhanced photoconductivity

Molecules of a thiol-functionalized phenylacetylene derivative were assembled on the CdS nanorod surface and copolymerized with phenylacetylene, affording an inorganic semiconductor-conjugated polymer hybrid with excellent solubility and high photoconductivity.     

Simultaneous Electrochemical Determination of Hydroquinone and Catechol at MWNTs and Cobalt(II) Tetrakisphenylporphyrin Modified Electrode

A multi-wall carbon nanotubes (MWNTs) and cobalt(II) tetrakisphenylporphyrin (Co(II)TPP) modified glassy carbon electrode (MWNTs/Co(II)TPP/GCE) has been prepared. It can be used for individual or simultaneous determination of hydroquinone (HQ) and catechol (CC). The anodic peaks of HQ and CC can be separated well. Owing to the unique properties of MWNTs and special synergistic effect of MWNTs and Co(II)TPP, the modified electrode exhibited a remarkable and stable current response for CC and HQ. The linear ranges for CC and HQ were 1.0–450.0 µmol L^?1 and 0.8–400.0 µmol L^?1 with detection limits of 0.8 µmol L^?1 and 0.5 µmol L^?1, respectively. Furthermore, Co(II)TPP, MWNTs, and Co(II)TPP/MWNTs composite were also used to construct modified electrodes and the electrochemical performances were studied.     

Resonance Raman intensity analysis of the excited state proton transfer dynamics of 2-nitrophenol in the charge-transfer band absorption

Resonance Raman spectra were obtained for 2-nitrophenol in cyclohexane solution with excitation wavelengths in resonance with the charge-transfer (CT) proton transfer band absorption. These spectra indicate that the Franck-Condon region photodissociation dynamics have multidimensional character with motion along more than 15 normal modes: the nominal CCH bend+CC stretch nu(12) (1326 cm(-1)), the nominal CCC bend nu(23) (564 cm(-1)), the nominal CO stretch+NO stretch+CC stretch nu(14) (1250 cm(-1)), the nominal CCH bend+CC stretch+COH bend nu(15) (1190 cm(-1)); the nominal CCH bend+CC stretch nu(17) (1134 cm(-1)), the nominal CCC bend+CC stretch nu(22) (669 cm(-1)), the nominal CCN bend nu(27) (290 cm(-1)), the nominal NO(2) bend+CC stretch nu(21) (820 cm(-1)), the nominal CCO bend+CNO bend nu(25) (428 cm(-1)), the nominal CC stretch nu(7) (1590 cm(-1)), the nominal NO stretch nu(8) (1538 cm(-1)), the nominal CCC bend+NO(2) bend nu(20) (870 cm(-1)), the nominal CC stretch nu(6) (1617 cm(-1)), the nominal COH bend+CC stretch nu(11) (1382 cm(-1)), nominal CCH bend+CC stretch nu(9) (1472 cm(-1)). A preliminary resonance Raman intensity analysis was done and the results for 2-nitrophenol were compared to previously reported results for nitrobenzene, p-nitroaniline, and 2-hydroxyacetophenone. The authors briefly discuss the differences and similarities in the CT-band absorption excitation of 2-nitrophenol relative to those of nitrobenzene, p-nitroaniline, and 2-hydroxyacetophenone.     

Electrochemical behavior of levodopa at multi-wall carbon nanotubes-quantum dots modified glassy carbon electrodes.

A multi-wall carbon nanotubes (MWNTs)-quantum dots (QDs) composite-modified glassy carbon electrode (GCE) was prepared. The complex was characterized by transmission electron microscopy (TEM). The electrochemical behavior of levodopa at MWNTs and QDs-modified GCEs (MWNTs-QDs/GCE) was studied by cyclic voltammetry (CV) and chronocoulometry (CC). It was found that its electrochemical behavior was a two-charge-two-proton process. The modified electrode had high electrocatalytic activity for levodopa with a standard heterogeneous rate constant of 0.595 cm s(-1), which was greatly increased compared with the values for bare GCE and individual MWNTs modified GCE. The better electrocatalytic activity for levodopa at MWNTs-QDs/GCE may due to a synergistic effect between MWNTs and QDs. This result provides a novel way to promote research on biomicromolecules at nano-dimensions.     

二(三)丁基锡烯基(炔基)膦酸酯的合成与表征

合成了12个新的二(三)丁基锡烯基(炔基)膦酸酯[(n-C4H9)nSn]n-1O2P(0)R,并用元素分析,红外光谱,核磁共振氢谱和TG-DTA对其组成和结构进行了表征,初步生物活性测试表明,有些化合物具有较强的杀螨和杀菌活性。     

聚乙烯基吡咯烷酮修饰多壁碳纳米管的研究

采用超声波辅助技术,研究了两亲性聚合物聚乙烯基吡咯烷酮(PVP)修饰多壁碳纳米管(MWNTs)的效果、作用机理及影响因素.研究结果表明在适合的条件下两亲性聚合物PVP可以被引入到多壁碳纳米管表面,修饰后的MWNTs在DMF、乙醇和水等溶剂中具有良好的分散性.通过红外光谱(FTIR)和拉曼光谱(Raman)分析表明,两亲性聚合物与MWNTs之间产生了化学接枝作用,高分辨透射电镜分析表明两亲性聚合物不均匀地存在于MWNTs的表面和端部.两亲性聚合物的浓度对接枝量的影响不大,但超声波作用时间对MWNTs表面两亲性聚合物PVP的接枝量有较大的影响,在超声时间为4h时接枝量最大.两亲性聚合物修饰效果不同于表面活性剂,采用表面活性剂十二烷基苯磺酸钠(SDBS)修饰的MWNTs经过洗涤过滤后,不能重新溶于水中,而两亲性聚合物PVP修饰的MWNTs可以重新溶解.     

STUDY ON OXO-CENTERED HETEROTRINULEAR TRANSITION METAL CARBOXYLATE COMPLEXES: Ⅱ. CRYSTAL STRUC TURES OF COMPOUNDS [Fe_2MnO(O_2CCH_3)_6Py]·Py AND [Fe_2CoO (O_2CCH_3)_6Py3]·Py

<正> The title compounds are isomorphous, they belong to trigonal space group R32, with crystallographic parameters: [Fe2MnO(O2CCH3)6Py3] ·Py: Mr = 853. 31, a = 17. 609(3), c=11. 056(3)(?), V = 2968. 9(?)3, Z = 3, Dc=1. 43 gcm-3, μ(MoKα) = 10. 9 cm-1, F (000) = 1317; [Fe2CoO(O2CCH3)6Py3]·Py: Mr = 857. 30, a = 17. 542(3), c=11. 049(2)(?), V = 2944. 8(?)3, Z = 3, Dc=1. 45 gem-3, μ (MoKα) = 12. 07 cm-1, F (000) = 1323. The structure of [Fe2MnO (O2CCH3)6Py3]·Py has been determined with the final R = 0. 042 for 663 reflections. The three crystallographically equivalent metal atoms form an equilateal triangle with side of 3. 324(?). The central oxygen aotm is on the three - fold axis with M - O distance 1. 919(?). The planar M3O core is normal to the three -fold axis and also to the solvate pyridine, which is dynamically disordered round this axis and is sandwiched by two Fe2MnO(O2CCH3)6Py3 molecules.     

磺化间规聚苯乙烯的表征

间规聚苯乙烯(sPS)是一种新型结晶性工程塑料,熔点达270℃,具有结晶速度快、耐热性好、耐化学腐蚀性优良等特点,可广泛用于汽车、电子、机械等行业,极具开发意义,但是由于sPS脆性大,抗冲击性差,故通过化学改性在sPS的苯环上引入极性基团,用于制成共混合金与复合材料,是提高材料韧性,开拓sPS用途的重要途径。     

Synthesis and charge/discharge properties of polyacetylenes carrying 2,2,6,6-tetramethyl-1-piperidinoxy radicals

The 2,2,6,6-tetramethyl-1-piperidinoxy (TEMPO)-containing acetylenic monomers HC[triple bond]CC(6)H(3)-p,m-(CONH-4-TEMPO)(2) (1), HC[triple bond]CC(6)H(3)-p,m-(COO-4-TEMPO)(2) (2), (S,S,S,S)-HC[triple bond]CC(6)H(3)-p,m-[CO-NHCH{COO-(4-TEMPO)}CH(2)COO-(4-TEMPO)](2) (3), (S,S)-HC[triple bond]CC(6)H(4)CO-NHCH{COO-(4-TEMPO)}CH(2)COO-(4-TEMPO) (4), HC[triple bond]CC(6)H(4)-p-OCO-4-TEMPO (5), HC[triple bond]CCH(2)C(CH(3))(CH(2)OCO-4-TEMPO)(2) (6), HC[triple bond]CCH(2)NHCO-4-TEMPO (7), and HC[triple bond]CCH(2)OCO-4-TEMPO (8) were polymerized to afford novel polymers containing the TEMPO radical at high densities. Monomers 1, 3-6, and 8 provided polymers with average molecular weights of 10 000-136 500 in 62-99 % yield in the presence of a rhodium catalyst, whereas monomers 2 and 7 gave insoluble polymers in 100 % yield. The formed polymers were thermally stable up to approximately 274 degrees C according to thermogravimetric analysis (TGA). All the TEMPO-containing polymers demonstrated reversible charge/discharge processes, whose discharge capacities were 21.3-108 A h kg(-1). In particular, the capacity of poly(1)-, poly(4)-, and poly(5)-based cells reached 108, 96.3, and 89.3 A h kg(-1), respectively, which practically coincided with their theoretical values.     

Ab initio/GIAO-CCSD(T) study of propenoyl (H2C=CH-CO+) and isopentenoyl ((CH3)2C=CH-CO+) cations and their superelectrophilic protonated dications

Structures of superelectrophilic protonated propenoyl (H2C=CH-COH2+) and isopentenoyl ((CH3)2C=CH-COH2+) dications and their parent cations were calculated using ab initio methods at the MP2/6-311+G and MP2/cc-pVTZ levels. Energies were calculated using Gaussian-2 (G2) theory. The alpha-carbon (Calpha) protonated 3 and 7 were found to be the global minima for protonated propenoyl and isopentenoyl dications, respectively. 13C NMR chemical shifts of the cations were also calculated using the GIAO-CCSD(T), GIAO-MP2 and GIAO-SCF methods. 13C NMR chemical shifts of the related tert-butyl cation ((CH3)3C+) and protonated tert-butyl dication ((CH3)2CCH4(2+)) were also computed at the same level to compare and explore the effect of the additional charge in dications.