Synthesis and characterization of novel poly(aryl ether)s containing naphthyl moieties

Two poly（aryl ether）s containing naphthyl moieties were prepared from bis（3,5-dimethyl-4-hydroxyphenyl）naphthyl methane （monomer 1） via nucleophilic aromatic substitution polycondensation with bis（4-fluorophenyl） ketone and bis（4-fluorophenyl） sulfone. The structures of these polymers were confirmed by 1H NMR. The Mn values of the two polymers were 96,200 and 88,600, respectively. The polymers exhibited good thermal stabilities with 5% mass loss at T 〉 400 and high glass-transition temperature （Ts） of T 〉 250 ℃. Moreover, the resultant polymers were amorphous determined by wide angle X-ray diffraction （WAXD）. ？2009 Lei Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All fights reserved.

NMR STUDY ON THE CONFORMATION CHANGE IN THE AGGREGATION PROCESSES OF 1，3－DI（α－NAPHTHYL）PROPANE AND DI（α－NAPHTHYLMETHYL）ETHER

NMR study on the conformation change in the aggregation process of the titled compounds is reported in this letter.

COMPLEX OF MESO-TETRA-(1-NAPHTHYL)TETRABENZOPORPHYRIN WITH HOLMIUM ACETYLACETONATE

Complex of meso-tetra-(1-naphthyl)tetrabenzo-porphyrin with holmium acetylacetonate,Ho(TNTBP)acac(TNTBP:meso-tetra-(1-naphthyl) tetrabenzoporphyrin.Hacac:acetylacetone)have been prepared and char- acterized by elemental analyses,ultra-violet visible spectra and in- frared spectra.

Synthesis, Crystal Structure and Herbicide Activity of Three Phenyl-naphthyl Methanone Derivatives

Three phenyl-naphthyl methanone derivatives have been designed and synthesized through alkylation and Friedel-Crafts acylation reactions.All the compounds were characterized by IR,1H NMR,13C NMR and H RMS.The single crystal structure of the compounds has been further determined by X-ray diffraction.(4-Ethoxynaphthalen-1-yl)(2-methylphenyl)methanone(3a)crystallizes in monoclinic system,P21/c space group with a=13.144(3),b=11.041(2),c=11.320(2)?,β=106.65(3)°,V=1573.7(5)?3,Dc=1.225 Mg/m3,Z=4,F(000)=616,μ(MoKα)=0.078 mm-1,R=0.0928 and wR=0.1556.(4-Ethoxynaphthalen-1-yl)(2-hydroxyphenyl)methanone(3b)belongs to the monoclinic system,P21/c space group with a=9.985(2),b=10.814(2),c=14.353(3)?,β=105.49(3)°,V=1493.6(5)?3,Dc=1.300 Mg/m3,Z=4,F(000)=616,μ(MoKα)=0.087 mm-1,R=0.0568 and wR=0.1262.(4-Methoxynaphthalen-1-yl)(4-methylphenyl)methanone(3c)crystallizes in monoclinic system,P21/c space group with a=7.6130(15),b=15.068(3),c=12.880(3)?,β=100.63(3)°,V=1452.1(5)?3,Dc=1.264 Mg/m3,Z=4,F(000)=584,μ(MoKα)=0.081 mm-1,R=0.0804 and wR=0.1349.The presence of van der Waals forces leads to the stability of the compounds.Especially,compounds 3a^c showed herbicidal activity against the monocotyledon plant barnyard grass(Echinochloa crus-galli).At the concentration of 0.75 mmol/m^2,compound 3b(Ct=0.436±0.116 mg/g)exhibited better activity than pyrazoxyfen(Ct=0.537±0.073 mg/g).

Preparation and spectroscopic, and thermal decomposition kinetic studies of europium(Ⅲ) complex [Eu(HNBD)_3] (HNBD: 1-(6-hydroxy-1-naphthyl)-1,3-butanedione)

The complex of Eu（IH） with 1-（6-hydroxy- 1-naphthyl）- 1,3-butanedione （HNBD） was prepared for the first time and characterized by elemental analysis, IR, UV, fluorescence spectrum, and DTA-TG-DTG techniques. The IR and UV-visible spectra showed that Eu（Ⅲ） ion was coordinated to the HNBD ligand. The fluorescence spectrum showed the presence of Eu^3＋ characteristic emission. The TG-DTA-DTG curves showed that the thermal decomposition of the anhydrous complex was a two-stage process and the final residue was Eu2O3. The thermal decomposition kinetic parameters of the complex were evaluated from TG-DTG data by using three kinds of integral methods （Coat-Redfem equation, Horowitz and Metzger equation, Madhusudanan-Krishnan-Ninan equation）. The kinetic parameters of the first stage are E^＊ = 164.02 kJ.moll, A = 1.31 × 10^15 s^-l, AS^＊= 42.27 J·K^-l·mol^-l, △H^＊ = 159.51 kJ·mol^-l, △G^＊= 136.54 kJ·mol^-l, and n = 3.1, those of the second stage are E^＊= 128.52 kJ·mol^-l, A = 1.44× 106 s^-1, △S^＊= - 136.89 J·K^-l·mol^-l, △H^＊ = 120.41 kJ·mol^-l, △G^＊= 283.85 kJ·mol^-l, and n = 1.1.

Stereoselective Synthesis and Crystal Structure Analysis of N-Naphthyl-2-deoxy-α-D-ribopyranosylamine

A new compound N-naphthyl-2-deoxy-α-D-ribopyranosylamine was synthesized and structurally determined. It crystallizes in the orthorhombic system, space group P212121 with a = 8.361（2）, b = 12.432（3）, c = 12.791（4） A^°, Z= 4, V= 1329.6（6） A^°^3, Dc= 1.295 g/cm^3, F（000） = 552, Cl5H17NO3 and Mr= 259.30. All the active hydrogen atoms are involved in the formation of hydrogen bonds in the molecule.

Synthesis and Crystal Structure of 4,4'-(4-(1-Naphthyl)-4-phenyl-1,3-butadienylidene)-bis[N,N-diethylbenzenamine]

The title compound （C40H42N2） has been synthesized by the reaction of l-（l- naphthyl）-l-phenyl-3-chloropropylene and bis（4-（diethylamino） phenyl）methanone, and characterized by IR, ^1H NMR, MS and X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 17.047（3）, b = 10.807（2）, c = 18.494（4） A, β = 105.727（4）°, V= 3279.4（11） A^3, Mr = 550.76, Z = 4, Dc = 1.115 g/cm^3,μ（MoKa） = 0.085 mm^-1, F（000） = 1184, the final R = 0.0625 and wR = 0.1384 for 2276 observed reflections （1 〉 2σ（I））. X-ray analysis reveals that the butadiene fragment adopts a planar cisiod conformation and makes a dihedral angel of 69.4（2）° with the naphthalene ring.

Synthesis and Structure-Antitumor Activity of 4,6-Diamino-1,2-Dihydro-2 ,2-Dimethyl-1-(Substituted-Naphthyl- 2)-1,3,5-Triazines

Introduction 4,6-Diamino-1,2-dihydro-2,2-dimethyl-1-substituted-1,3,5-triazines (Ⅰ) are dihydrofolate reductase(DHFR) inhibitors, hence they possess the inhibition to the growth of bacteria and cancer cells. Baker’s antifolate (Ⅱ) has shown promise as an antitumor agertt in clinical trials. The study of the structure-activity relationships of I shows that the inhibition to vertebrate DHFR is significantly influenced by the hydrophobicity of 1-substituent, i.e., the stronger the hydrophobicity of the 1-substituent, the more potent the inhibition of the compound to vertebrate DHFR.

SYNTHESIS OF POLYSTYRENE-BLOCK-POLYCAPROLACTAM WITH 1,1-BIS-(1′-NAPHTHYL) ETHYLENE AS A DEACTIVATING AGENT

The insertion of 1,1-bis (1′-naphthyl) ethylene monomer unit into the active polystyrene chain end greatly decreased the reactivity of the active chain end to the carbonyl group, and allowed the polymeric chain end to react only with the double bond in N-methacryloyl caprolactam, resulting in N-acylcaprolactam functionalized polystyrene in 100% conversion. New diblock copolymer of polystyrene with polycaprolactam was synthesized by direct reaction of the functionalized polymer with caprolactam without adding additional alkali metal or their caprolactam salts.

芴基、酰亚胺基和萘基聚合物气体分离膜的研究进展

聚合物链间距和链刚度是影响聚合物膜对气体渗透性能的决定因素,刚性基团(如芴基、酰亚胺基及萘基)引入聚合物链中,基于其大体积和扭曲结构能够有效阻碍分子链堆积,从而降低分子链堆积密度,使聚合物具有较高的自由体积,能有效改善膜对气体的渗透选择性。本文综述了近5年含芴基、酰亚胺基和萘基聚合物在气体分离中的研究,按结构分类,详细介绍了三类聚合物的合成以及膜对气体的选择性,分析了影响气体选择性的主要因素。最后,综合现有刚性聚合物的特点,从改性高气体渗透性低选择性材料、改性生物基材料及制备复合混合基质膜等角度出发,展望了此类材料的未来发展趋势,为制备高性能气体分离膜提供参考。

Synthesis of aza-BODIPY dyes bearing the naphthyl groups at 1,7-positions and application for singlet oxygen generation

Using 2-vinylnaphthalene,aza-BODIPYs with the naphthyl groups at 1,7-positions were prepared and their photophysical properties were characterized.Due to attachment of the naphthyl groups at1,7-positions,aza-BODIPYs show long-wavelength absorption and emission in the near-infrared region.The singlet oxygen generation of the dibromo substituted aza-BODIPY with the naphthyl groups at1,7-positions as a photosensitizer was more effective than that of the corresponding aza-BODIPY with the phenyl groups at 1,7-positions.No photobleaching of the naphthyl-containing aza-BODIPY was observed and such NIR aza-BODIPY could be used for the singlet oxygen generation.

Ligand Steric Effects on Naphthyl-α-diimine Nickel Catalyzed α-Olefin Polymerization

Naphthyl-α-diimine nickel complexes with systematically varied ligand sterics, activated by modified methylaluminoxane（MMAO）, were tested in the polymerization of higher α-olefin（1-hexene, 1-decene and 1-hexadecene） under suitable conditions. The polymerization results indicated the possibility of precise microstructure control, depending on catalyst structure, polymerization temperature, monomer concentration and types of monomers, which in turn strongly affects the resultant polymer properties. Naphthyl-α-diimine nickel complex bearing chiral bulky sec-phenethyl groups in the o-naphthyl position showed good catalytic activity, and resulted in branched polymers（42-88/1000 C） with high molecular weights（Mn：（4.3-15.2） × 10^4 g·mol^-1） and narrow molecular weight distribution（Mw/Mn = 1.13-1.29, RT）, which suggested a living polymerization. The increasing steric hindrance of catalyst leads to enhance insertion for 2,1-insertion of α-olefin and the chain-walking reaction.

Determination of organophosphorus pesticide residues in vegetables by an enzyme inhibition method using α-naphthyl acetate esterase extracted from wheat flour

The widespread use of organophosphorus pesticides(OPs) poses a great threat to human health and has made the detection of OP residues in food an important task,especially in view of the fact that easy and rapid detection methods are needed.Because OPs have inhibitory effects on the activity of α-naphthyl acetate esterase(ANAE) in plants,in this work we evaluated the possibility of detecting OPs in vegetables with ANAE extracted from commercial flour.The limits of detection(LODs) obtained for methamidophos,dichlorvos,phoxim,dimethoate,and malathion in lettuce samples with crude ANAE were 0.17,0.11,0.11,0.96,and 1.70 mg/kg,respectively.Based on the maximum residue limits(MRLs) for OPs in food stipulated by Chinese laws which are 0.05,0.20,0.05,1.00,and 8.00 mg/kg for methamidophos,dichlorvos,phoxim,dimethoate,and malathion,respectively,the esterase inhibition method with crude ANAE had sufficient sensitivity to detect the residues of dichlorvos,dimethoate,and malathion in lettuce,but it could not be used to guarantee the safety of the same samples if methamidophos or phoxim residue was present.The sensitivity of the method was improved by the use of esterase purified by ammonium sulfate salting-out.The LODs obtained for methamidophos and phoxim with purified esterase were lower than the MRLs for these OPs in food.This is a very promising method for the detection of OP residues in vegetables using crude or purified esterase because of its cheapness,sensitivity,and convenience.

MECHANICALLY AND THERMALLY STABLE BLENDS OF POLY(STYRENE-BUTADIENE-STYRENE) WITH CONDUCTING POLY(THIOUREA-AZO-NAPHTHYL)

A new aromatic azo-polymer, poly（thiourea-azo-naphthyl） （PTAN）, has been synthesized using 1-（5- thiocarbamoylaminonaphthyl）thiourea and diazonium salt solution of 2,6-diaminopyridine. PTAN was easily processable using polar solvents and had high molar mass 57 × 10^3 g/mol. Electrically conducting, mechanically and thermally stable rubbery blends of poly（styrene-butadiene-styrene） （SBS） triblock copolymer and PTAN were produced by solution blending technique. FESEM of SBS/PTAN blends revealed nano-scale dispersion of the conducting filler showing good adhesion between the matrix and PTAN. Remarkable effects of azo-content on the conductivity of SBS-based blends have been observed. Accordingly, PTAN loading from 10 to 60 wt% increased the conductivity from 1.24 to 1.66 S/cm. Relationship between PTAN loading and thermal stability of the materials was also investigated. With increasing the PTAN content, 10% gravimetric loss was increased from 484 to 500 ℃, while glass transition was enhanced from 119 to 126 ℃. Thermal and conducting data of the blend showed better results relative to pure elastomer but were lower than those of the conducting filler. Similarly, the tensile strength （57.35-62.33 MPa） of SBS/PTAN was improved relative to there of SBS. Fine balance of properties renders new materials fairly better than the existing elastomeric blends used in a number of applications.

Photochemical naphthylation at(α-carbon atom of carbonyl and its equivalences

The photostimulated reaction of halonaphthalene with a series of carbanions derived from, propionic acid derivatives in liquid ammonia led to the naphthylation at a-carbon of the carbanions in an isolated yield ranging from 25％ to 86％.In all cases,the dehalonaphthalenes were found to, be by-products and the reaction was inhibited by p-dinitrobenzere.An electron transfer from the carbanion to the halonaphthalene followed by ejection of halogen led to naphtbyl radical,as predicted by comparing the LUMOs of the carbanions and the halonaphthalenes,was involved in the process. Absence of the alkylnaphthalene and 1,2-dinaphthylalkane in the products indicates the smooth electron transfer between(Naph-Nu)^+ and Naph-X.C-vs.O-naphthylation is fully addressed in terms of MNDO calculations and acid-base principle.

Synthesis of (+) or (-)-2-(8′-Diphenylphosphino-1′-naphthyl)oxazoline Ligands and Their Application in Pd-Catalyzed Allylic Alkylation Reaction

We synthesized optically active 2-(8′-diphenylphosphino-1′-naphthyl)oxazoline ligands by palladium-catalyzed coupling reactions of (trimethylsilyl)diphenylphosphine with 2-(8′-bromo-1′-naphthyl)oxazolines, which, in turn, were prepared from 8-bromo-1-naphthoyl chloride by the reaction with natural optical active amino alcohols. Pd-Catalyzed allylic alkylation reaction induced by these chiral ligands gave the allylic substituted products in high yields and moderate ee values.

Intramolecular energy transfer between chromophores separated by a rigid steroid bridge——Ⅰ.Singlet and triplet energy transfer in 3β(1-naphthyl)acetoxy-⊿~5-androsten-17-one

Intramolecular transfer of both singlet and triplet electronic excitation between the naphthalene moiety and the carbonyl group in 3β-(1-naphthyl)acetoxy-⊿~5-androsten-17-one was studied.Irradiation with 280 nm light selectively leads to excitation of the naphthalene moiety. Transfer of the singlet excitation from the naphthalene moiety to the carbonyl group occurs by dipole- dipole resonance interaction.The measured rates for such energy transfer in several solvents agree with that calculated from Frster equation.After efficient intersystem crossing,the carbonyl group transfers triplet excitation back to the naphthalene moiety via electron exchange mechanism.The combination of singlet and triplet energy transfer with the high efficiency of intersystcm crossing of carbonyl group results in the phosphorescence enhancement of naphthalene moiety.

黄芪多糖对急性肝内胆汁淤积性肝损伤大鼠模型的影响

探究黄芪多糖对急性肝内胆汁淤积性肝损伤大鼠血清丙氨酸氨基转移酶(alanine transaminase,ALT)、天冬氨酸氨基转移酶(Aspartate transaminase,AST)、肿瘤坏死因子a(tumornecrosisfactor-a,TNF-a)、白细胞介素6(interleukin6,IL-6)水平的影响。将雄性健康SD大鼠54只随机分为空白组、实验组(模型组、熊去氧胆酸组及黄芪多糖低、中、高剂量组),每组9只。除空白组、模型组外,其余四组大鼠均给予熊去氧胆酸溶液及黄芪多糖低、中、高(0.2、0.4、0.8 g/kg)溶液,1次/d,共7 d。于第5 d,实验组给予1%α-萘异硫氰酸酯(ANIT)油溶液灌胃建立模型,空白组给予等容积橄榄油。观察大鼠一般情况,采用全自动生化分析仪检测血清ALT、AST含量,采用ELISA法检测血清中炎性因子TNF-α、IL-6表达水平。与空白组相比,模型组ALT、AST、TNF-α、IL-6均升高,具有显著性差异(P<0.01)。与模型组相比,熊去氧胆酸组及黄芪多糖低剂量组、中剂量组、高剂量组均降低,具有显著性差异(P<0.01)。与熊去氧胆酸组相比,黄芪高剂量组效果最为显著,ALT、AST、TNF-α、IL-6均降低,具有显著性差异(P<0.01)。黄芪多糖可以缓解ANIT诱导的急性肝内胆汁淤积性肝损伤并降低ALT、AST、TNF-α、IL-6水平。

电子级萘基环氧树脂的制备及其构效关系研究

通过一步法合成、降氯和分子蒸馏等工艺,制备了三种不同位点的高纯电子级萘基环氧树脂,分别为1,5-二羟基萘缩水甘油醚(1,5-DNGE)、1,6-二羟基萘缩水甘油醚(1,6-DNGE)和2,7-二羟基萘缩水甘油醚(2,7-DNGE)。通过控制环氧值、固化剂和固化程序一致性,分析了萘环上不同位点结构与性能的关系。选择聚醚胺(D230)和4-甲基六氢苯酐(MEHHPA)两种固化剂,研究了三种萘基环氧树脂的固化动力学,探究了萘环上不同位点的反应活性。研究结果表明:制备的三种不同位点的双官能度高纯萘基环氧树脂,三者纯度接近100%,总氯、水解氯和无机氯含量分别低于1000、200和1 ppm,适用于电子级环氧树脂的要求;在D230体系中,1,6-DNGE活化能最低,而在MEHHPA体系中,2,7-DNGE活化能最低。由于1,5-DNGE和2,7-DNGE的分子结构更对称,交联度高,所以玻璃化转变温度、橡胶弹性模量、交联密度、线膨胀系数、介电和热失重数据都较1,6-DNGE更优异;1,6-DNGE却具有最高的储能模量[E’(50℃)>2600 MPa]、损耗模量(tanδ>1.1)和韧性,加工性能更好,非常适合制备综合性能优异的复合材料,为电子封装行业提供了综合性能优异的高纯电子级萘基环氧树脂和应用价值。