Synthesis, Characterization and Fluorescence of Rare earth Nitrate Complexes with Triaza-crown Ether Derivative

Four new complexes of rare earths with a triaza crown ether (L) derived from N 3O 2 macro cycle 1,12,15 triaza 3, 4: 9,10 dibenzo 5, 8 dioxacycloheptadecane were synthesized and characterized by elemental analysis, IR, molar conductance, TG DTA analysis and fluorescence spectra. The composition of the complexes determined as [RE(NO 3) 3L·3H 2O]·H 2O (RE=Sm, Eu, Tb and Dy). It is found that Sm 3+ , Eu 3+ , Tb 3+ and Dy 3+ complexes all show strong fluorescence emission in the solid state. Among these complexes, Tb 3+ complex has the strongest luminescence intensity. It shows that the ligand L triplet state energy matches 5D 4 energy level of Tb 3+ . In the Eu 3+ complex, η ( 5D 0→ 7F 2/ 5D 0→ 7F 1) is 2.6, which indicates that Eu 3+ locates at the asymmetric coordination field.

BF₃.OEt₂-Mediated Benzylation of Arenes and Heteroarenes with Benzyl Ether Derivatives

An efficient BF3.OEt2-promoted benzylation of arenes and heteroarenes with various benzyl ether derivatives has been developed. This method provided alternative access to valuable diarylmethane in good yields under mild conditions via an easy work-up procedure.

Synthesis and Photophysics of a Flavone Derivative with Lariat Ether as a Fluoroionophore

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Synthesis and Thermal Crosslinking Behavior of Poly(aryl ether ketone)s Containing 1,4-Naphthalene Moieties

A new monomer, 1,4-bis(4-fluorobenzoyl) naphthalene(compound 2) was synthesized via a two-step reaction. 1,4-Naphthalenedicarboxylic acid chloride(compound 1) was prepared by using the acyl chlorization reaction of 1,4-naphthalenedicarboxylic acid with thionyl chloride. The Friedel-Crafts acylation of compound 1 with fluorobenzene afforded compound 2 in a 80% yield. The polycondensation of compound 2 with various bisphenols in tetramethylene sulfone(TMS) in the presence of excess potassium carbonate as a condensation reagent was carried out at 210 ℃ to quantitatively afford the corresponding poly(aryl ether ketone)s(compounds 3_8) containing 1,4-naphthalene moieties. Thermal analyses showed that the polymers have T g values ranging from 496 to 500 K and are thermally stable in air with initial mass loss above 500 ℃. These novel polymers exhibited an excellent solubility in organic solvents including NMP, DMAc, and chloroform, etc. In addition, the glass transition temperatures of these polymers increased and the polymers became insoluble in chloroform after treated at 260 ℃, indicating the occurrence of a thermal crosslinking reaction.

Synthesis and Properties of Poly(aryl ether ketone) Copolymers Containing 2,7-Naphthalene Moieties

Poly（ aryl ether ketone） copolymers containing 2,7-naphthylene and hydroquinone（HQ） moieties with various compositions were prepared by the reaction of 4,4＇-difluorobenzophenone（DFB） 2,7-naphthylene and hydroquinone in the presence of sodium carbonate and potassium carbonate （ 19： 1, mass ratio） in diphenyl sulfone （DPS）. The thermal analysis results of the copolymers show that the glass transition temperatures（Tgs） increase, while the melting temperatures（Tra） and tile 5.0% weight loss temperatures （ Td ） decrease with the increase of the 2,7-naphthalene moieties. For the copolymers synthesized at a molar fraction of 2,7-naphthalene in the difluoro monomers being over 0.30, no peaks corresponding to the cold crystallization temperature and the melting temperature could be detected, indicating that these copolymers are almost amorphous. The crystal structures of the copolymers with a molar fraction of 2,7-naphthalene being less than 0. 30 are rhombic.

STUDY ON ETHERIFICATION OF TERMINAL HYDROXY GROUP OF POLYETHYLENE GLYCOL MONOALKYL ETHERS

In this paper etherification of the terminal hydroxy group of polyethy-lene glycol monoalkyl ethers is studied and a convenient method for the preporation ofpolyethylene glycol dialkyl ethers is propused. Nine methyl , butyl and benzyl deriva-tives are obtained by using Williamson synthetie method. The effect of reaction pa-rameters on the protective ratio is examined by using the optimum seeking method.The protective efficiency is evaluated by cumporing the variation of hydroxy value.The best reaction conditions are found by experiment.It is also found that the protec-tive ratio of methylation is higher than that of butylation while the protective ratio ofbenzylation is the lowest. The protective ratio of AEO9 is equivalant to OP8 and theprotective ratio of AFO3 is much lower.

Synthesis of Crown Ether-tethered b-Cyclodextrin and Fabrication of Its Self-assembled Monolayer on Gold Surface

A novel b-cyclodextrin derivative 6 bearing a crown ether moiety has been synthesized by a convenient method in 9.4% yield. Its self-assembled monolayer (SAM) was fabricated on the gold surface, which was characterized by using surface-enhanced Raman spectra.

Bibracchial Lariat Ethers(Ⅰ)——The Synthesis and Crystal Structure of the N,N'-bis(2-Methoxy-1-Naphthylmethyl)-4,13-Diaza-18-Crown-6 Sodium Iodide Complex

Diaza Crown ethers are versatile complexing reagents, their complexing abilities are dramatically modified by the electron donating atoms on substituents attached to the nitrogen if they can give a three-dimensional cavity as in cryptates. Hence the synthesis and characterization of bibracchial lariat ethers (BIBLES) have received much attention. In the preparation of new BIBLES, a complex Ⅱ was unexpectedly obtained.

Formation of Hybrid Ring Structure of Cyanurate/Isocyanurate in the Reaction be-tween 2,4,6-Tris(4-Phenyl-Phenoxy)-1, 3,5-Triazine and Phenyl Glycidyl Ether

Reaction products of 2,4,6-tris(4-phenyl-phenoxy)-1,3,5-triazine derived from 4-phenylphenol cyanate ester and phenyl glycidyl ether were analyzed. In addition to an isocyanurate compound and an oxazolidone compound which were well known as reaction products of cyanate esters and epoxy resins, compounds with hybrid ring structure of cyanurate/isocyanurate were determined. Gibbs free energies of the compound having hybrid ring structure of cyanurate/isocyanurate with two isocyanurate moiety were found to be lower than that of the compound with cyanurate ring structure through calculations. Calculation data supported the existence of hybrid ring structure of cy-anurate/isocyanurate. It was revealed that isomerization from cyanurate to isocyanurate occurs via hybrid ring structure of cyanurate/isocyanurate in the reaction of aryl cyanurate and epoxy.

Syntheses and Insecticidal Activity of Spirocyclic Tetronic Acid Derivatives Containing Oxime Ether Moiety

In order to develop novel spirocyclic tetronic acid lead compounds,a series of new spirocyclic tetronic acid derivatives containing oxime ether moiety was synthesized and bioassayed.The stmctures of 16 target compounds were characterized by lH NMR spectra,13C NMR spectra and high-resolution mass spectrometer(HRMS).Preliminary bioassays indicated that most of the title compounds displayed excellent insecticidal activity against Aphis fabae and Nilapmyata lugens at 100 mg/L.In particular,compound 6k showed the similar activity(LC50=6.87 mg/L)against A.fabae as the spirotetramat(LC50=4.56 mg/L)and had better efIects(LC50=l.64 mg/L)against N.lugens in comparison with spirotetramat(LC5o=7.90 mg/L).The study showed that compound 6k exhibited more promising and broad-spectrum insecticide activity and may serve as a new insecticidal agent for sucking pests.

丙烯酰胺改性魔芋葡甘聚糖絮凝性能研究

为了制备一种具备高效处理污水能力的新型絮凝剂,以丙烯酰胺为醚化剂,在碱性条件下通过迈克尔加成反应合成了魔芋葡甘聚糖醚类衍生物(AMKGM)。以傅里叶变换红外光谱、核磁共振氢谱、X射线衍射、热分析仪和扫描电子显微镜对AMKGM的结构和形貌进行表征。并以AMKGM为新型絮凝剂,研究其对蒙脱土溶液的絮凝性能,考察了絮凝剂的质量分数、絮凝时间、絮凝温度和pH值等主要因素的影响。研究结果表明:成功制备了AMKGM絮凝剂,当絮凝时间为90 min,絮凝剂质量分数为0.75%时,在酸性和碱性条件下,AMKGM都表现了良好的絮凝效果,最高絮凝效率为98%,重现性好,且实验温度范围内对AMKGM的絮凝性能没有显著的影响。

糠醛肟醚衍生物的合成及抑菌活性

进一步探究呋喃环在农药研究领域的应用,以糠醛为原料设计合成了13个糠醛肟醚衍生物,并通过核磁共振氢谱、核磁共振碳谱、高分辨质谱对其结构进行表征确证。生物活性测试结果表明:部分目标化合物对柑橘溃疡病菌和水稻白叶枯病菌具有一定抑制活性。其中,2-呋喃甲醛-0-(3-三氟甲基苄基)(31)的抑制率较为突出。在质量浓度为50和100μg/mL时,对柑橘溃疡病菌的抑制率分别为56.0%和74.0%,其EC_(50)为35.1μg/mL优于对照药剂噻唑锌(63.7μg/mL)。化合物31具有进一步研究的价值。

肟醚衍生物的生物活性研究进展

肟醚是一类含有N=O双键的重要有机化合物,近年来该类化合物在农药、医药等领域的研究中受到广大研究者的青睐。在农药研究中肟醚衍生物表现出优良的杀虫、杀菌、除草、抗植物病毒活性,在医药研究中具有抗菌、抗肿瘤和消炎等作用。本文对含有肟醚结构的衍生物在农药及医药领域的生物活性研究情况进行了概述,并展望了肟醚衍生物的设计方向和研究重点。

Studies on the reactions of silyl enol ether with perfluoroorganic compounds——Ⅲ.Synthesis of perfluoroalkylated α,β-unsaturated aldehydes and their derivatives

Per-and poly-fluoroalkylated α,β-unsaturated alkenals were synthesized by the reaction of silyl enol ether of alkanals with per-and poly-fluoroalkyl iodide initiated by Na_2S_2_O4 conveniently in high yield.Their corresponding alkenol and 2,4-dinitrophenylhydrazone were also synthesized.

光动力疗法治疗鲜红斑痣1216例临床分析

目的 分析比较血啉甲醚 (HMME)与血卟啉衍生物 (HpD)为光敏剂行光动力治疗 (PDT)鲜红斑痣的临床疗效及副反应。材料与方法 鲜红斑痣患者 12 16例 ,粉红型 13 2 % ,紫红型 6 8 3% ,增厚型 18 4%。静脉注射HpD或HMME 3～ 7mg/kg后给予铜蒸气激光、KTD/ 5 32激光或氩离子激光照射 ,功率密度 5 0～ 10 0mW/cm2 ,能量密度 90～ 5 40J/cm2 ,随访观察。结果 HMME PDT和HpD PDT对各型鲜红斑痣均能有效地消除病变颜色 ,所随访的 16 32个病灶在 2个月至 9年的随访期内未见复发。治疗后反应有 :局部水肿 5～ 7天 ,部分患者有结痂或一过性色素沉着 ,皮肤暂时性光过敏反应。HpD PDT组避光期 30～ 90天 ,HMME PDT组避光期 7～ 14天。与HpD PDT相比 ,HMME PDT具有反应轻、愈合快、不良反应少、安全度大、避光期短、色素沉着轻、护理容易、重复治疗间隔期短的特点。结论 HMME PDT与HpD PDT都能有效治疗各型鲜红斑痣 ,但HMME PDT具有不良反应少、安全度大、避光期短、护理容易。

吡啶衍生物研究(X):2-仲丁氨基-5-(2-芳氧吡啶-4-基)-1,3,4-噻二唑的合成及除草活性

为了研究2-仲丁氨基-5-（2-氯吡啶-4-基）-1,3,4-噻二唑（BCPT）的结构-活性关系和开发活性更高的新型除草剂,以BCPT为先导化合物,依据活性亚结构连接法,在吡啶环2-位上引入二芳醚类除草剂的典型结构单元——芳醚,设计并合成了一系列新的芳氧吡啶噻二唑类化合物,其结构经元素分析和^1H NMR确证。初步除草活性测定结果表明,在500mg/L剂量下,所有化合物的除草活性（抑制率0-45%）远低于先导化合物（抑制率72%-87%）,说明吡啶环2-位上的氯原子可能对维持该类化合物的除草活性是必需的。

血啉甲醚与血卟啉衍生物对鸡冠皮肤光敏损伤特点的比较研究

目的 采用形态学方法观察比较国产新型光敏剂———血啉甲醚 (HMME)与传统光敏剂———血卟啉衍生物 (HpD)对鸡冠表皮层、真皮乳头层毛细血管网、乳头下网状层和真皮深层组织的光敏损伤特点。方法 成年莱亨鸡 2 34只 ,随机分为对照组 42只 ,实验组 192只。实验组动物静脉注射HMME或HpD 1、5、10或 2 0mg/kg ,于给药后即刻、1、2、3或 4h对鸡冠进行激光照射 ,波长为 488 0和 5 14 5、5 10 6、5 78 2或 6 2 7 8nm ,功率密度为 5 0、10 0或 15 0mW/cm2 ,能量密度为 30、6 0、90、12 0、15 0、180或 2 70J/cm2 ,于照射后即刻、1、3、7、14和 2 8天取材 ,进行大体和光镜观察。结果 PDT作用区的红色鸡冠完全变白 ,乳头层毛细血管网内皮细胞 (EC)坏死、管壁破坏及血管数量减少 ,其作用程度与光敏剂给药量和激光照射量相关。HMME和HpD对乳头层毛细血管网的损伤程度相似 ;HMME组未见表皮及乳头下各层损伤 ,而部分HpD组见表皮基底细胞层有局灶性坏死、乳头下网状层有微血管及结缔组织损伤和淋巴细胞浸润。结论 HMME和HpD对鸡冠真皮乳头层毛细血管网的损伤程度相似 ,但HMME的组织选择性优于HpD。

杯芳烃衍生物的合成和性质的研究(Ⅴ)

通过对特丁基杯[4]芳烃的酚羟基的选择性醚化制备了一系列—烃基,1,3-二烃基和四烃基醚,烃基分别含有缩醛、酰胺、氨基等活泼官能团。醚化反应的区域选择性主要取决于使用的碱的种类和反应时间的长短。

纤维素醚的特点、制备及在工业中的应用

综述了纤维素醚的种类、制备方法、性能和特点,以及纤维素醚在石油、建筑、造纸、纺织、医药、食品、光电材料及日化工业中的应用,介绍了一些具有发展前景的纤维素醚类衍生物的新品种并展望其应用前景。

光动力疗法治疗鲜红斑痣的基础研究——血啉甲醚与血卟啉衍生物吸收特性的比较

目的 观察新型光敏剂———血啉甲醚 (HMME)在鸡冠皮肤组织和血管内皮细胞 (EC)的吸收特点。方法 莱亨鸡 12只 ,分为HMME组和血卟啉衍生物 (HpD)组 ,每组 6只。分别静脉注射HMME或HpD10mg kg ,每隔 10min取血 2 5ml和鸡冠皮肤组织 2 5g。培养新生儿脐带EC ,培养液中加入HMME或HpD ,孵育浓度分别为 2 0、40、6 0、80和 10 0μg ml,孵育时间为即刻、15、30、6 0、12 0、180和 2 40min。采用荧光分析法测定光敏剂含量 ,并绘制EC吸收光敏剂的浓度—含量和时间—含量关系曲线。结果 静脉注射HMME或HpD后 ,其血清浓度的峰值出现在注射后 10min ,以后随时间迅速下降 ,二者的曲线形态基本一致。HMME在鸡冠组织中的含量于注射后 10min显著高于HpD(P <0 0 1) ,以后虽然下降速率较快 ,但在注射后 80min仍显著高于HpD(P <0 0 5 )。培养EC可迅速吸收HMME和HpD ,30min达峰值的 89%以上 ;其吸收量与孵育浓度呈线性关系 ,对HMME的吸收量显著高于HpD(P <0 0 1)。结论 HMME较HpD更容易被皮肤微血管EC摄取 。