1-(2-噻唑)-3-(8-(5-对磺酸基苯基偶氮)喹啉)-三氮烯的合成及其与铜(Ⅱ)的显色反应

合成了新试剂1-(2-噻唑)-3-(8-(5-对磺酸基苯基偶氮)喹啉-三氮烯(TCPQT),并研究了其与Cu2+的显色反应。结果表明:在pH 7.5的磷酸盐缓冲溶液中,TCPQT与Cu2+形成摩尔比为1:1的紫红色络合物,该络合物在606.5nm处有一最大吸收峰,其表观摩尔吸光系数为3.36×105L.mol-1.cm-1,Cu2+的质量浓度在0～0.4μg/mL范围内符合比尔定律,相关系数r=0.9993。方法已用于测定食品中的微量铜。     

新型硫酮基哌嗪荧光探针的合成及其对铜(Ⅱ)的识别性能

以苯胺和三氟乙酰乙酸乙酯为原料,经环合反应制得4-三氟甲基-2(1H)喹啉酮(1);1与劳森试剂反应生成4-(三氟甲基)喹啉-2(1H)-硫酮(2);2与间隔基反应合成中间体2-[(3-氯丙基)硫基]-4-(三氟甲基)喹啉(3);将3连接到识别基团哌嗪上合成了一个新型的双荧光侧臂的探针化合物——1,4-二【3-{2-[4-(三氟甲基)喹啉]硫基}丙基】哌嗪(4),其结构经1H NMR和LC-MS表征。UV-Vis和FL研究结果表明,4的发射波长在396 nm;对Cu2+具有良好的识别作用,在1.0×10-7mol·L-1~1.0×10-4mol·L-1内可定量检测Cu2+含量。     

四-α-(2-甲基-8-喹啉氧基)酞菁金属配合物的合成、表征及光敏活性研究

利用DBU催化法合成得到4种两亲性的四-α-(2-甲基-8-喹啉氧基)酞菁金属配合物[金属＝Co(II), Ni(II), Cu(II), Zn(II)], 同时分别进行了元素分析、质谱、UV-Vis、IR光谱表征. 测定了它们在670 nm光激发下产生单线态氧的速率及光动力氧化氨基酸底物的速率常数, 探讨了它们光敏活性的构效关系.     

新试剂1-（2-苯并噻唑）-3-（8-（5-对磺酸基苯基偶氮）)喹啉三氮烯（BTSPQT）的合成及其测定铜（Ⅱ）的研究

以2-氨基苯并噻唑和5-对磺酸基苯基偶氮-8-氨基喹啉为原料,合成了一种新的三氮烯试剂1-(2-苯并噻唑)-3-(8-(5-对磺酸基苯基偶氮))喹啉三氮烯(BTSPQT),并研究了该试剂与Cu2+的显色反应。结果表明,在含有0.3%Triton X-100的Na2B4O7-HCl缓冲体系(pH 8.0)中,BTSPQT与Cu2+在室温下可形成摩尔比为2∶1的紫红色配合物,该配合物的稳定常数为(2.59±0.40)×109,最大吸收波长位于610 nm。基于此反应,建立了一种测定Cu2+的光度分析新方法,其表观摩尔吸光系数为3.61×105L.mol-1.cm-1,线性范围为0.025～0.40 mg/L,且浓度在2.5 mg/L以下的常见离子均不干扰0.40 mg/L Cu2+的测定。将该方法用于面粉和茶叶中铜的直接测定,回收率为96%～103%,相对标准偏差均小于4.0%。     

二[4,4,4-三氟-1-(2-噻吩基)丁二酮-1,3]合铜-二喹啉配合物的合成和晶体结构

用X射线衍射法测定标题化合物的晶体结构.晶体空间群为P1,Cu(Ⅱ)与2个4,4,4-三氟-1-(2-噻吩基)丁二酮-1,3中的4个氧原子组成正方形,在正方形的轴向上。2个喹啉分子的氮原子与Cu(Ⅱ)配位,形成了六配位的八面体配合物.研究了配合物的热谱、红外光谱.     

L-(8-羟基-5-甲基喹啉)半胱氨酸修饰电极的制备及其对汞离子选择性检测

利用Shifft碱反应将L-半胱氨酸和5-甲酰基-8-羟基喹啉一步合成L-(8-羟基-5-甲基喹啉)半胱氨酸,通过金-硫键将L-(8-羟基-5-甲基喹啉)半胱氨酸自组装到金电极表面制备L-(8-羟基-5-甲基喹啉)修饰金电极。L-(8-羟基-5-甲基喹啉)半胱氨酸分子中的羟基氧和氮可与Hg2+形成稳定的五元环配合物,因此该修饰电极能选择性吸附Hg2+,结合方波伏安法用于Hg2+电化学检测。在0.01mol/L HCl中,富集时间为160s,Hg2+浓度在1.0×10-9~1.0×10-8 mol/L、1.0×10-8~1.0×10-7 mol/L浓度范围内与方波伏安峰电流分段呈现良好的线性关系,检出限为0.92×10-9 mol/L。     

(E)-N-芳基-3-[2-(8-羟基喹啉基)-乙烯基]咔唑的合成、抗氧化活性及促进鼠骨髓间质干细胞增殖的研究

设计合成了3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲苯基咔唑(8)和3-[2-(8-羟基喹啉基)-乙烯基]-N-对甲氧苯基咔唑(9)两个新的化合物, 用IR, MS, 1H NMR和元素分析确认其结构. 并利用DPPH•方法, 超氧阴离子自由基( )法, 羟基自由基HO•法和噻唑蓝比色法(MTT法)分别测定了目标产物的抗氧化活性和调控鼠骨髓间质干细胞(MSCs)的作用. 结果表明, 这两种化合物对DPPH•自由基、超氧阴离子自由基和羟基自由基具有较强的抗氧化活性, 化合物9在低浓度时对鼠骨髓间质干细胞增殖有很好的促进作用.     

8-氨基喹啉取代苯甲酰胺衍生物对汞离子和铜离子的识别

设计合成了可识别金属离子的荧光传感分子8-氨基喹啉取代苯甲酰胺衍生物,通过核磁共振谱和质谱表征其结构;利用其光谱性质研究了该系列物质对过渡金属离子Cu2+,Hg2+,Pb2+,Zn2+,Ni2+和Cd2+的识别性质,初步探讨了其识别机理。实验表明:在乙腈中,8-氨基喹啉苯甲酰胺的吸收光谱在509nm处对Cu2+有响应,溶液由无色变成红色;而其荧光光谱对Hg2+和Cu2+有良好的选择性,荧光增强倍率分别高达368和192,与金属离子形成结合比为1:1配合物。     

4-(1,2-亚乙二氧基)环己酮及其2-甲醛和2-羧酸酯的烯胺和烯醇反应的研究

4-(1,2-亚乙二氧基)环己酮及其2-甲醛和2-羧酸酯的烯胺和烯醇与丙烯酸型的和丙二酸型的试剂反应,获得了与6-(1,2-亚乙二氧基)-5,6,7,8-四氢-2(1H)-喹啉酮很相近的四个化合物(5、11、18、19)和六个其它化合物(4、7、8、9、16、17)。探讨了这十个均未见于文献的新化合物的生成机理,并得到一个制备5-四氢萘胺衍生物的新方法。     

聚合反应制备键合型纤维素-三(4-甲基苯基甲酸酯)衍生物类手性固定相

合成了带有甲基丙烯酰基的纤维素-三(4-甲基苯基甲酸酯)衍生物(CTMB),并通过聚合反应将其键合在具有双键的硅胶表面,得到手性固定相(CSP)。用所得到的CSP对9种对映体化合物(丁苯酞、酮基布洛芬、反-2,3-二苯环氧乙烷、安息香、安息香类似物、托葛尔碱、华法令、4,4′-二甲氧基-5,6,5′,6′-二次甲二氧基-2,2′-羰甲基甲酯联苯、4,4′-二甲氧基-5,6,5′,6′-二次甲二氧基-2-羰甲基甲酯-2′-羰甲基乙酯联苯)进行了拆分。考察了CSP制备过程中甲基丙烯酰氯的用量、键合方式以及硅胶     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von vier bindungsisomeren Trichlorotrirhodanoosmaten(IV)

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of four Linkage Isomeric Trichlorotrirhodanoosmates(IV) By treatment of fac-[OsCl₃I₃]^2? with (SCN)₂ in dichloromethane the linkage isomers fac-[OsCl₃(NCS)₃]^2? ( 1 ), mer-[OsCl₃(NCS)₂^c(SCN)]^2? ( 2 ), mer-[OsCl₃(NCS)(SCN)₂^t]^2? ( 3 ), and mer-[OsCl₃(NCS)(SCN)₂^c]^2? ( 4 ) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. X-Ray structure determinations have been performed on single crystals of fac-(Ph₄As)₂[OsCl₃(NCS)₃] (triclinic, space group P1 , a = 12.142(5), b = 13.233(5), c = 19.300(5) Å, α = 98.642(5)º, β = 100.509(5)º, γ = 112.514(5)º, Z = 2), mer-(Ph₄As)₂[OsCl₃(NCS)₂^c (SCN)] · acetone (triclinic, space group P1 , a = 11.707(5), b = 13.238(5), c = 19.048(5) Å, α = 75.960(5)º, β = 88.981(5)º, γ = 69.999(5)º, Z = 2), mer-(Ph₄As)₂[OsCl₃(NCS)(SCN)₂ ^t] (triclinic, space group P1, a = 10.6861(12), b = 11.6587(5), c = 12.5232(5) Å, α = 112.069(8)º, β = 95.052(8)º, γ = 92.559(7)º, Z = 1) and mer-(Ph₄As)₂[OsCl₃(NCS)(SCN)₂ ^c] · 2acetone (triclinic, space group P1 , a = 11.444(5), b = 14.661(5), c = 15.830(5) Å, α = 75.790(5)º, β = 80.273(5)º, γ = 75.205(5)º, Z = 2). The complex anions are completely ordered. The via N or S coordinated thiocyanate groups are located nearly direct above one of the cis-positioned Cl ligands with Os? N? C angles of 169.1º, 171.5º, 175.7º ( 1 ), 175.6º, 178.6º ( 2 ), 172º ( 3 ), and 173.1º ( 4 ) and Os? S? C angles of 106.2º ( 2 ), 106.1º, 106.6º ( 3 ), 105.1º, and 108.2º ( 4 ). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salts of all four linkage isomers have been assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(OsN) = 1.71 ( 1 ), 1.46 and 1.62 ( 2 ), 1.69 ( 3 ), and 1.61 ( 4 ), f_d(OsS) = 1.27 ( 2 ), 1.36 ( 3 ), 1.32, and 1.49 mdyn/Å ( 4 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved.     

Darstellung,Kristallstrukturen, Schwingungsspektren und Normalkoordinatenanalyse von vier bindungsisomeren Tetrachlorodirhodanoosmaten(IV)

Preparation, Crystal Structures, Vibrational Spectra, and Normal Coordinate Analysis of Four Linkage Isomeric Tetrachlorodirhodanoosmates(IV) By treatment of cis- or trans-[OsCl₄I₂]^2? with (SCN)₂ in dichloromethane the linkage isomers cis-[OsCl₄(NCS)₂]^2? ( 1 ), trans-[OsCl₄(NCS)(SCN)]^2? ( 2 ), cis-[OsCl₄(NCS)(SCN)]^2? ( 3 ) and trans-[OsCl₄(SCN)₂]^2? ( 4 ) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X-Ray structure determinations on single crystals of cis-(Ph₄As)₂[OsCl₄(NCS)₂] (triclinic, space group P1 , a = 10.019(5), b = 11.702(5), c = 21.922(5) Å, α = 83.602(5)°, β = 85.718(5)°, γ = 73.300(5)°, Z = 2), trans-(Ph₄As)₂[OsCl₄ · (NCS)(SCN)] (monoclinic, space group P2₁/c, a = 18.025(5), b = 11.445(5), c = 23.437(5) Å, β = 94.208(5)°, Z = 4), cis-(Ph₄As)₂[OsCl₄(NCS)(SCN)] (triclinic, space group P1 , a = 10.579(5), b = 11.682(5), c = 22.557(5) Å, α = 81.073(5)°, β = 85.807(5)°, γ = 87.677(5)°, Z = 2) and trans-(Ph₄As)₂ · [OsCl₄(SCN)₂] (triclinic, space group P1 , a = 10.615(5), b = 11.691(5), c = 11.907(5) Å, α = 111.314(5)°, β = 96.718(5)°, γ = 91.446(5)°, Z = 1) reveal the complete ordering of the complex anions. The via N or S coordinated thiocyanate groups are located nearly direct above one of the cis-positioned Cl ligands with Os? N? C angles of 171.2° and 174.3° ( 1 ), 162.3° ( 2 ), 172° ( 3 ) and Os? S? C angles of 108.3° ( 2 ), 105.7° ( 3 ) and 105.5° ( 4 ). Using the molecular parameters of the X-Ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu₄N) salts of all four linkage isomers are assigned by normal coordinate analyses based on a modified valence force field. The valence force constants are f_d(OsN) = 1.59 ( 1 ), 1.67 ( 2 ), 1.60 ( 3 ) and f_d(OsS) = 1.27 ( 2 ), 1.31 ( 3 ) and 1.32 mdyn Å^?1 ( 4 ). Taking into account increments of the trans influence a good agreement between observed and calculated frequencies is achieved.     

Darstellung und Kristallstruktur von (n-Bu4N)3[Ir(NCS)(SCN)5]

Preparation and Crystal Structure of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] The evaporated ethanolic extrakt of the reaction product of K₃[IrCl₆] and HNO₃, refluxed with an aqueous KSCN solution yields a mixture of the linkage isomers [Ir(NCS)_n(SCN)_6?-n]^3?, n = 0? 2, and small amounts of linkage isomeric chloropentarhodanoiridates(III), from which [Ir(NCS)(SCN)₅]^3? has been isolated by ion exchange chromatography on DEAE-cellulose. The X-Ray structure determination on a single crystal of (n-Bu₄N)₃[Ir(NCS)(SCN)₅] (monoclinic, space group P 2₁/a, a = 17.513(5), b = 32.607(5), c = 23.661(5) Å, β = 94.757(5)°, Z = 8) confirms the existance of a heteroleptic hexakis(thiocyanato(N)-thiocyanato(S))iridate(III) with an Ir? N distance of 2.03 Å and Ir? S bond lengths between 2.29 and 2.38 Å. The SCN groups with angles between 166 and 175° are nearly linear with Ir? S? C angles from 99.9 to 109.4°. The Ir? N? C angles of the two crystallographic independent anions are 166 and 174°.     

Comparative Thermogravimetric Studies of Poly(ether-ketone/sulfone) Imides and Their Parent Polymers: I. Poly(ether-ketone/sulfone) ethylimide

Thermogravimetry (TG) was employed to study the thermal degradation kinetics of poly(etherketone/sulfone)ethylimide (PEK-IE and PES-IE). The corresponding decomposition activation energies and reaction orders were obtained and the comparison was made with their parent polymerspoly(ether-ketone/sulfone) with Cardo group (PEK-C and PES-C). The results show that the degradation activation energies of PEK-IE and PES-IE were lower than that of PEK-C and PES-C; and two stages of the degradation process were found for all the four polymers. For PEK-IE and PES-IE, the activation energies in the first decomposition stage are much lower than that in the second stage and the two stages can be taken as slow induction and fast degradation, whereas for PEK-C and PES-C the activation energies in the first decomposition stage are larger than that in the second stage, and the two stages can both be taken as two fast degradation stages. The decomposition mechanism of the two stages was also speculated.This revised version was published online in November 2005 with corrections to the Cover Date.     

SYNTHESIS AND CHARACTERIZATION OF METAL COMPLEXES WITH AMPICILLIN

Abstract

The reaction, in water, of Co(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions with sodium ampicillinate at room temperature has allowed isolation of dimers with the following general formula [M(amp)Cl]₂ × nH₂O (n = 1.5?3.2). The complexes were characterized by elemental analyses, conductivity measurements, magnetic susceptibilities and spectroscopic methods (IR, Raman, EPR and UV-Visible). A dinuclear structure based on octahedrally coordinated metal ions is proposed.     

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性

PMDA-BPDA-HAB聚苯并噁唑的合成及耐热性;均苯四甲酸二酐;联苯四羧酸二酐;二羟基联苯胺;聚酰亚胺;聚苯并噁唑;耐热性     

Thermal Degradation of Poly(ε-caprolactone), Poly(L-lactic acid) and their Blends with Poly(3-hydroxy-butyrate) Studied by TGA/FT-IR Spectroscopy

Summary: The thermal degradation behavior of poly(ε-caprolactone) (PCL) and poly(L-lactic acid) (PLA) have been studied in different environment. It was found that these polymers undergo completely different degradation processes in nitrogen and oxygen atmosphere. In oxygen environment PCL and PLA mainly decompose to CO₂, CO, water and short-chain acids. In nitrogen atmosphere PCL releases 5-hexenioc acid, CO₂, CO and ε-caprolactone, whereas PLA decomposes to acetaldehyde, CO₂, CO and lactide. The polymer blends of poly(3-hydroxybutyrate) (PHB) with PCL and PLA decompose similar to the individual homopolymers with crotonic acid as the initial decomposition product of PHB.     

Energy relationship and the polarization of C_(60) cage in the endohedral complexes (X@C_(60))

In this paper, we carry out the calculation on the system (X@C60)(X=Li, Na, K, Kb, Cs; F, Cl, Br, I), where the position of X changes along 5 typical symmetry directions. For the calculation of quantum chemistry we use EHMO/ASED method, for the calculation of molecular mechanics we use Buckingham potential (exp-6-1) function, and for the calculation of thermo-chemical cycle we use individually isolating the processes such as the structure variation, charge transfer and charge distribution, and their interactions etc. The calculation results show that (1) In the region of radius r≈0.2 nm of the Ceo cage, the potential field is nearly spherical; (2) Except for Li and Na, the systems are the most stable with minimum energies at the center of C60 cage. For Li and Na, the systems are the most stable with minimum energies at r≈0.16 nm and r≈0.13 nm, respectively. In view of the interactive region of chemical bonds, the interactions between X and the C60 cage do not belong to the classical chemical bonds; (     

铜在3%NaCl溶液中腐蚀行为的光电化学研究

Cu以其优异的导电性、导热性和易加工性广泛用于工农业生产中．自然Cu的腐蚀和防腐成为人们很关注的问题．人们已经注意到，Cl-对Cu的腐蚀有影响，并进行过一些研究．但目前使用光电化学方法研究这一问题的文章尚不多见，特别是利用测量开路光电压及其瞬态波形这一现场的、无损的、灵敏的监测方法研究户对Cu电极腐蚀全过程的文章尚未见到．本文正是利用如上方法及XPS，AES方法，研究了Cl-对Cu电极腐蚀的全过程，取得了一些有意义的结果．1实验方法Cu电极用99．99％（质量分数）的Cu制成，面积约为39mm2；电极底部由Cu导线焊接引出，…     

On the morphological behavior of ABC miktoarm stars containing poly(cis 1,4-isoprene), poly(styrene), and poly(2-vinylpyridine)

Fundamental understanding of microphase separation in ABC miktoarm copolymers is vital to access a plethora of nonconventional morphologies. Miktoarm stars based on poly(cis 1,4-isoprene) (I), poly(styrene) (S), and poly(2-vinylpyridine) (V) are model systems, which allow systematic studies of the effects of composition, chemical microstructure, and temperature on the thermodynamics of microphase separation. Eleven ISV-x (I:S:V = 1:1:x, v:v:v) miktoarm copolymers were synthesized by anionic polymerization affording well-defined copolymers with a variable V arm. Equilibrium bulk morphologies of all samples, as evidenced by small-angle X-ray scattering, transmission electron microscopy (TEM), and self-consistent field theory, showed a systematic transition from lamellae (x ≈ 0–0.2) to [8.8.4] tiling (x ≈ 0.6–0.9) to cylinders in undulating lamellae (x ≈ 2–4) and, finally, to hexagonally packed core–shell cylinders (x ≈ 5–8). Chemical microstructure of the I arm [poly(cis 1,4-isoprene)] versus poly(3,4-isoprene) is shown to play important role in affecting morphological behavior. To reconcile differences between ISV-x star morphologies reported in the literature and those reported herein, even for the same composition, effects of the microstructure of I arm on the Flory–Huggins parameter between I and V arms were taken into account in a qualitative manner. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2018 , 56, 1491–1504