Synthesis of Novel Covalent-linked Linear Porphyrin-Thiophene Copolymers

0　IntroductionTheconstructionofmacro molecularsystemcontainingmul tipleredoxcentersorphotosensitizersisanimportantsub jectinthedesignofmolecularelectronicdevices[1 ,2 ] .Forsuchobjectives,systematizationofdonor (redoxcenter) acceptortriadmoleculesintolargemolecularsystemsisoneofthemostfeasibleapproaches,becausetheexquisiteincorporationofthephotosensi tizersandsuitableelectrondonorsand /oracceptorsintoapoly mericchainisusefulforvariousmolecularsystembasedonphoto inducedelectrontransfer[3 ,4] …     

In situ simultaneous determination of trace elements, U-Pb and Lu-Hf isotopes in zircon and baddeleyite

This paper describes a combined method of simultaneously measuring U-Pb and Lu-Hf isotopes as well as trace elements in Phalaborwa baddeleyite and 91500, GJ-1, TEMORA-1 and SK10-2 zircons by means of Neptune MC-ICPMS and Agilent Q-ICPMS connected to a 193 nm excimer laser ablation system. Material ablated by laser was carried in different proportions into Q-ICPMS for U-Pb isotopic and trace elemental and MC-ICPMS for Lu-Hf isotopic compositions. Experiments indicate that different proportions of ablated material for the Q-ICPMS and MC-ICPMS （6：4, 5：5 and 4：6 respectively） do not show any bias for the zircon/baddeleyite U-Pb age, Lu-Hf isotope and trace elemental compositions within analytical errors. Using 40-60 μm spot size, the obtained U-Pb ages of Phalaborwa baddeleyite, 91500, GJ-1, TEMORA and SK10-2 zircons are 2065±15 （2σ, n=20）, 1063±6 （2σ, n=-19）, 613±6 （2σ, n=20）, 416±5 （2σ, n=20） and 32.6±0.5 （2σ, n=20） Ma, respectively. The ^176Hf/^177Hf ratios are 0.281231±24 （2SD, n=20）, 0.282310±35 （2SD, n=19）, 0.282028±34 （2SD, n=20）, 0.282687±34 （2SD, n=20） and 0.282752±53 （2SD, n=20）, respectively. The obtained trace elemental compositions are identical to the reference values. Therefore, this kind of technique makes it possible to simultaneously obtain the U-Pb age, Lu-Hf isotopes and trace elemental compositions of zircon and baddeleyite, which could be an important tool in solving problems in earth sciences.     

Studies on syntheses of biscrown ether compounds

Multi-ester type biscrown ether compound(I) was prepared by the reaction of 6-bromoacetacetic ester dibenzo-16-crown-5(7) with phenyl-methyl ether-2,6-diformic acid potassium salt in anhydrous DMF at refluxed temperature, and color biscrown ether compound(II) was prepared by the reaction of 4′-aminobenzo-15-crown-5(12) with 2,2′(O-formoyl naphthyl)ethyl ether (9) in anhydrous ethanol at 40 C under N₂. New compounds(I, II) were characterized by IR,¹H NMR, MS and elemental analysis. Supported by the National Natural Science Foundation of China Niu Changrong: born in December, 12, 1938, Professor     

基于植酸锆/普鲁士蓝复合膜的电催化行为研究

通过层层自组装技术,构建植酸锆/普鲁士蓝(Zr-IP_6/PB)多层结构膜.基于普鲁士蓝(PB)对双氧水(H_2O_2)有很高的电催化性能,加之5层植酸锆/普鲁士蓝膜多孔结构有利于传质过程,该H_2O_2传感器具有高灵敏度和高选择性.实验结果显示:修饰电极对H_2O_2响应的物质的量浓度范围为2.00×10~(-5)～1.76×10~(-3) mol·L~(-1),线性相关系数R=0.998 9.     

K波段CMOS反射负载型无源移相器

研究应用于K波段相控阵收发系统的差分反射负载型无源移相器的设计方法.基于TSMC 90 nm CMOS工艺实现了一个5 bit移相器,其反射负载由电感和变容二极管并联组成.测试结果表明,该移相器的移相误差在23~25 GHz频带内小于6°,在22~26 GHz频带内小于15°.又基于相同工艺提出了一个改进的6 bit移相器,采用品质因数相对较高的叉指电容阵列替代传统的变容二极管,通过开关控制实现电容值的改变.仿真结果表明,改进版移相器的移相误差在23~25 GHz频带内小于4°,在22~26 GHz频带内小于8°.      

基于人体生物力学的颈椎动力外骨骼的设计与运动学分析

针对神经根型与交感神经型颈椎病,基于颈椎牵引、前屈/后伸、左/右侧屈及旋转运动康复治疗方式,设计了一种基于6-SPS/CS型并联机构的可穿戴式颈椎动力外骨骼.首先,基于人体生物力学进行外骨骼机构设计与颈椎运动分析,采用空间坐标变换方程和闭环矢量法对外骨骼等效并联机构进行运动学逆解分析;其次,利用ADAMS软件对外骨骼等...     

Study on mimetic peroxidase and molecular recognition of phenols with inclusion complex of ironporphyrin immobilized by β-CD polymer

β-Cyclodextrin (β-CD) and its cross-linked polymer (β-CDP) were known as the mimetic models. Metalloporphyrin had been widely used in the enzymatic method of analysis and molecular recognition. In present work, it was investigation that supramolecular recognition for halogenated phenols, three crosols, three nitrophenols and three aminophenols, served respectively as the substrate of the mimetic receptor, iron-5, 10, 15, 20-tetrakis (sulforphenyl)-21H, 23H-porphine (FeTPPS) or FeTPPS-β-CDP. Supramolecular complex, FeTPPS-β-CDP with function of mult i-recognition and induced-fit, was a advanced kind of mimetic peroxidase; Methyl phenol or polyphenol was the substitute of chlorophenic acid, while aminophenols and other phenols were suggested not to be utilized to enzymatic assay of H₂O₂. Being a mimetic enzyme mimicking the space structure of overall proteinase, beaimed by immobilized mimetic enzyme with a large number of β-CD interior cavities, chlorophenol was identified optimal substrate in the system tested. Foundation item: Supported by the National Natural Science Foundation of China Biography: MAO Lu-yuan(1959-), male, Associate Professor, Postdoctor.     

Approach to synthesis of novel chiral 3-chloro-2(5H)-furanone and its application in asymmetric reactions

The synthetic method of the novel chiral synthon, 5-l-menthyloxy-3-chloro-2-(5H)-furanone 5a and its application in asymmetric reactions were investigated. 5a is easily obtained in highly optical purity, and acts as a stable acceptor of Michael addition with oxygen nucleophiles in tandem double Michael addition / internal nucleophilic substitution to offer the spiro-cyclopropane derivative containing four stereogenic centers 8, which it is difficult to obtain by routine methods. The synthetic methods for 5a and 8 are reported in detail and the new compounds are identified on the basis of their analytical data and spectroscopic data, such as UV, IR,¹H NMR,¹³C NMR, MS and elementary analysis. The absolute configuration of the interesting spiro-cyclopropanes, spiro [1-chloro-4-(l-menthyloxy)-5-oxo-6-oxa-biscyclo[3.1.0]hexane-2,3′-(4′-/-menthyloxy-5′-l-menthyloxybutyrolactone)] 8 was established by X-ray crystallography. This result can provide important synthetic strategy in synthesis of some complex molecules containing spiro-cyclopropane skeleton with multiple chiral centers.     

ICP-MS分析复方甘草口服溶液中15种元素

建立电感耦合等离子体质谱(ICP-MS)法测定复方甘草口服溶液中15种元素(Cr、Mn、Co、Ni、Cu、Zn、As、Cd、Sn、Sb、Ba、Hg、Pb、Al、Fe)。样品经微波消解后,根据待测元素的质量数选择相应元素作为内标,采用碰撞模式(氦模式)进行测定。结果显示,15种元素线性关系良好,相关系数均大于0.999,各元素的检出限在0.08～38.00ng·mL~(-1),回收率在88.57%～107.10%(n=6)。该方法操作简便,分析速度快,灵敏度高,线性范围宽,可同时测定多种元素,适用于复方甘草口服溶液中元素的测定。     

Eolian sand deposition and its environmental significance in the northeastern margin of the Qinghai-Xizang Plateau

The dry climate which appeared about 8#x2013;7 Ma ago in South Asia has been interpreted as results of the intensification of Asian monsoon caused by the uplift of the Qinghai-Xizang Plateau at its maximum altitude around that time. Whether it is or not, it is a critical problem. A total of 55 samples were taken from the Tertiary red earth and Quaternary lacustrine deposits and loess in the Linxia Basin which is located in the northeastern margin of the Qinghai-Xizang Plateau, for the analysis of quartz types and contents using electron probe microanalyzer. The results indicate that the eolian sands have existed since 15Ma and reached its maximum content at 8 and 6#x2013;5 Ma, respectively. This means that the climate was very dry during 8-5 Ma period in western China, which was regarded as the result of global climatic change at that time. Mean size of quartz sand grains was about 0.4 mm during 15#x2013;3.6/2.6 Ma period and dropped to 0.1–0.07 mm dramatically after 3.6–2.6 Ma. This demonstrates that the local eolian deposition was decreased significantly and even disappeared since Late Pliocene and was replaced by dust deposits from distal source, suggesting the uplift of Qinghai-Xizang Plateau and the change of air circulation after 3.6–2.6 Ma.     

电力输电杆塔用Q235钢聚硅氧烷复合涂层的大气腐蚀行为

采用喷涂法在Q235钢表面涂覆聚硅氧烷复合涂层,在重工业污染区、人口密集区、一般工业区、乡村定居区4个220kV变电站大气环境中自然暴露15个月,采用伏安法、交流阻抗法等研究其腐蚀行为。结果表明,重工业污染区变电站的腐蚀电流密度从3.849 5×10~(-12) A/cm~2增加到15个月的2.257 2×10~(-10) A/cm~2;而人口密集区变电站的腐蚀电流密度值先从1.640 1×10~(-10) A/cm~2降低到6个月的5.736 5×10~(-11) A/cm~2,后增加到15个月的3.929 9×10~(-10) A/cm~2。结合自腐蚀电位和涂层阻抗,聚硅氧烷复合涂层在不同环境中耐蚀性顺序为:人口密集区乡村定居区一般工业区重工业污染区。     

Synthesis and light-emitting properties of organic electroluminescent compounds and their metal complexes

Several organic electroluminescent (EL) compounds, 2,2‘-(1,4-phenylenedivinylene)bis-3,3-dimethyl-indolenine (1), 2,2‘-(1,4-phenylenedivinylene)bis-benzoxazole (2), 2,2‘-(1,4-phenylenedivinylene)bis-benzothiazole (3), 4,4‘-(1,4-phenylenedivinylene)bis-quinoline (4), 2,2‘-(1,4-phenylene divinylene)bis-quinoline (5), 2,2‘-(1,4-phenylenedivinylene)bis-1,3,3-trimethyl-indolenine dichlo ride (6), 2,2‘-(1,4-phenylene-divinylene)bis-1-hydro-3,3-dimethyl-indolenine dichloride (7), 2,2‘-(1,4-phenylenedivinylene)bis-8-acetoxy-quinoline (8), 2,2‘-(1,4-phenylenedivinylene)bis-8-hydroxyquinoline (9) and metal complexes of 9, Al(PHQ) (10) and Zn(PHQ) (11), have been synthesized and characterized. The crystal structure of 6 was determined. Light emitting properties of the prepared compounds have been investigated. 1 produces an orange-yellow emission (λmax=575nm). The cation, 6, gives a red emission (λmax=607nm), which is shifted 32 nm to the red compared to 1.8 produces a yellow emission (λmax=567nm). The metal complex 10 gives a red emission (λmax=610nm), which is a red shift of 43 nm compared to 8. The change in structure in the prepared compound caused a change in the electron distribution in the compounds, which induces a large wavelength shift of the emitted-light. Thermal analysis showed that the decomposition temperatures of the metal complexes (10, 11) were higher than those for the smaller organic molecular compounds (1-9). Therefore, metal complexes (10, 11) can be used as EL materials over a larger temperature range.     

4-羟基苯基卟吩的合成和分离方法改进

对单羟基苯基卟吩[ 5- ( 4- 羟基苯基) - 10, 15, 20- 三苯基- 21H, 23H- 卟吩( H2TPPOH) ] 和多羟基苯基卟吩[ 5, 10- 二( 4- 羟基苯基) - 15, 20- 二苯基- 21H, 23H- 卟吩(H²TPP( OH) ₂) 、 5- 苯基- 10, 15, 20- 三( 4- 羟基苯基) - 21H,23H- 卟吩( H₂TPP( OH) ₃) ] 的分离方法作了改进.实验表明, 分离各种羟基苯基卟吩, 产物纯度高,分离效果好,并可节省大量洗脱剂,缩短了柱分离时间
同时,还考察了配料比, 吡咯溶液的滴加速度和操作方式对合成各种羟基苯基卟吩产率的影响采用3:1.05:4( 苯甲醛:对羟基苯甲醛: 吡咯,摩尔比) , 3 min 滴完吡咯溶液,强烈的电动搅拌, 可提高H₂TPPOH 的收率.     

Electrocatalytic oxidation of H<Subscript>2</Subscript>O<Subscript>2</Subscript> at a carbon paste electrode modified with a nickel (II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(Diethylcarbamoylmethoxy) calix[4] arene complex and its application

Electrochemical behavior of a carbon paste electrode (CPE) modified with nickel(II)-5, 11, 17, 23-tetra-tert-butyl-25, 27-bis(diethylcarbamoylmethoxy) calix[4]arene (Ni (II)-L) complex and its electrocatalytic activity towards the oxidation of hydrogen peroxide were investigated by cyclic voltammetric technique in a 5.0×10⁻² mol/L NaClO₄+1.0×10⁻³ mol/L NaOH solution. It was found that Ni(II)-L acts as an effective catalyst for the oxidation of hydrogen peroxide. The modified electrode exhibited a linear response over a hydrogen peroxide concentrations in the range of 2.0×10⁻⁵−1.0×10⁻⁴ mol/L with a detection limit as low as 1.0×10⁻⁶ mol/L. The relative standard deviation was 3.5% for 5 successive determinations of H₂O₂ at 1.0×10⁻⁵ mol/L. The modified electrode was used successfully in rainwater analysis. Foundation item: Supported by the Natural Science Foundation of Hubei Province (98J040). Biography: Li Chun ya(1972-), Ph. D. candidate, research direction: electroanalysis and electrosynthesis.     

Diatom-based reconstruction of Holocene environmental changes in Angren Lake, Southern Tibet

Based on the diatom analysis the climatic sequence between 11 000 and 6 000 aBP in Angren, southern Tibet is established, i.e. cold period (11 095-9 970 aBP)→temperate period (9 970-9 870 aBP)→Anathermal (9 870-9 770 aBP)→cool-dry period (9 770-8 740 aBP) →super-megathermal (8 740-8 590 aBP)→Megathermal (8 590-5 970 aBP). And the opinion that the reaction of diatom to temperature change is more sensitive than to other ecological factors has been pointed out and certified.     

Spectrofluorimetric determination of magnesium (II) with 7-(8-Hydroxy-3, 6-disulfonaphthylazo)-8-hydroxyquinoline-5-sulfonic acid

A new fluorescent reagent, 7-(8-hydroxy-3, 6-disulfonaphthylazo)-8-hydroxyquinoline-5-sulfonic acid (HDNHQ) for the determination of magnesium has been developed. It reacted with magnesium to form a 1∶1 fluorescent complex withλ _ex/λ _em immediately at room temperature in ammonia-ammonium chloride buffer (pH 10.7). A linear relationship was obtained in the magnesium concentration range of 0–160 ng·mL⁻¹ with the detection limit of 0.04 ng·mL⁻¹. The proposed method was simple, rapid and sensitive. It has been successfully applied to the determination of trace magnesium in blood serum with recoveries of 103.75% and 98.16%, respectively. Foundation item: Supported by the Zi-Qiang Foundation of Wuhan University Biography: Zhang Xian (1975-), female, Ph. D candidant, research direction: organic reagent synthesis and analysis.     

Stability study of saturated red polymer light-emitting diodes

Saturated red polymer light-emitting diodes have been fabricated with a single emitting polymer blend layer of poly[2-(2-ethylhexyloxy)-5-methoxy-1,4-phenylenevinylene] (MEH-PPV) and poly[9,9-dioc- tylfluorene-co-4,7-di-2-thienyl-2,1,3-benzothiadiazole] (PFO-DBT15). Saturated red emission with the Commission Internationale de l’Eclairage (CIE) coordinates of (0.67, 0.33) was obtained. The device stability was investigated. The results showed that energy transfer occurred from MEH-PPV to PFO-DBT15, and MEH-PPV improved the hole injection and transportation.     

Mechanisms of sodium and potassium ions transfer facilitated by dibenzo-15-crown-5 across the water /1,2-dichloroethane interface using micropipettes

The transfer of sodium and potassium ions facilitated by dibenzo-15-crown-5 (DB15C5) has been studied at the micro-water/1,2-dichloroethane (water/DCE) interface supported at the tip of a micropipette. Cyclic voltammetric measurements were performed in two limiting conditions: the bulk concentration of Na+ or K+ in the aqueous phase is much higher than that of DB15C5 in the organic phase (DB15C5 diffusion controlled process) and the reverse condition (metal ion diffusion controlled process). The mechanisms of the facilitated Na+ transfer by DB15C5 are both transfer by interfacial complexation (TIC) with 1∶1 stoichiometry under these two conditions, and the corresponding association constants were determined at log β1 = 8.97 ( 0.05 or log β1 = 8.63 ( 0.03. However, the transfers of K+ facilitated by DB15C5 show different behavior. In the former case it is a TIC process and its stoichiometry is 1∶2, whereas in the latter case two peaks during the forward scan were observed, the first of which was confirmed as the formation of K+(DB15C5)2 at the interface by a TIC mechanism, while the second one may be another TIC process with 1∶1 stoichiometry in the more positive potential. The relevant association constants calculated for the complexed ion, K+(DB15C5)2, in the organic phase in two cases, logβ2, are 13.64 ( 0.03 and 11.34 ( 0.24, respectively.     

Study on synthesis and biological activities of novel water-soluble metalloporphyrins

The synthesis and characterization of a series of metal porphyrins, M^II(Por), {Por=dianionic of 5, 10, 15, 20-tetrakis [4-(4′-bromobutyloxy) phenyl]porphyrinato and 5, 10, 15, 20-tetrakis [4-(4′-butyloxypyridine bromide)phenyl]porphyrinato, M=Zn, Cu, Mn, Co, Ni, Ru-CO} were described. The complexes 3a-3e were prepared from the reactions of compound 2 with metal acetates in chloroform, and the treatment of 3a-3f with excess of pyridine gave corresponding complexes 4a-4f. These new compounds were identified by absorption spectroscopies,¹H-NMR and elemental analyses. The results of biological activity testing for 4a-4f revealed that 4a and 4c had stronger inhibiting action on the growth metabolism ofEsche richia coli. Foundation item: Supported by the National Natural Science Foundation of China (No: 29972035) and the Zi-Qiang Science Foundation of Wuhan University, 2000 Biography: Li Zao-ying (1949-), famale, Professor, research interests, study on synthesis and biological activities of metalloprphrins.     

Synthesis of novel polymer-bonded water-soluble metal porphyrins

The reaction of 5, 10, 15, 20-tetra-(4-pyridyl) porphyrin 1 with triruthenium dodecacarbonyl [Ru₃(CO)₁₂], zinc(II) acetate, copper(II) acetate, cobalt(II) acetate afforded complexes 2a−2d respectively. Treatment of 2a−2d with Merrifield’s peptide resin obtained 3a−3d. The compounds 3a−3d reacted with methyl iodide respectively gave 4a−4d. New complexes 4a−4d have been identified by IR, UV-visible spectra, and AES. Foundation item: Supported by the Natural Science Foundation of Hubei Province Biography: LI Zao-ying (1949-), female, Associate professor.