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.

The Relationship Among the Reaction Product Colors of Non-specific Esterase by Alpha-naphthyl Acetate Method

The present work is concerned with the relationship of the different colors of NSE (non specific esterase) reaction product, in which alpha naphthyl acetate and diazotate of o dianisidine (Fast Blue B salt) were used as a substrate and a coupler respectively to describe the histochemical characteristics of NSE in chick embryonic mesonephros and metanephros. Our preliminary results throw light on the nature of NSE reaction produced colors, under light microscope, which were different in various sections for different air drying time length. The reaction product on the slices of the convoluted tubules of chick embryonic kidney was bright yellow after less than 30 min air drying time length, brown after 1.5～2 h air drying time length and black after more than 3 h of air drying. The color change process of NSE precipitates from bright yellow to black is progressive. The phenomennon has not been described previously.

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。

基于法尼醇X受体通路探讨壮药依山红对胆汁淤积大鼠的影响

目的探讨壮药依山红对α-萘异硫氰酸酯(alpha-naphtyl isothiocyanate,ANIT)诱导胆汁淤积大鼠的影响及其作用机制。方法采用120只SD大鼠,随机分成6组,分别为正常组、模型组、熊去氧胆酸组及壮药依山红高、中、低剂量组,每组20只。除正常组外,余用ANIT灌胃建立胆汁淤积大鼠模型。连续给药15天后,称量计算大鼠肝脾指数;血清生化法检测血清丙氨酸氨基转移酶(alanine aminotransferase,ALT)、门冬氨酸氨基转移酶(aspartate aminotransferase,AST)、碱性磷酸酶(alkaline phosphatase,AKP)等转氨酶指标,测定总胆红素(total bilirubin,TBIL)、直接胆红素(direct bilirubin,DBIL)、总胆汁酸(total bile acids,TBA)等胆红素指标;苏木素—伊红(hematoxylin-Eosin,HE)染色法评估肝组织病理学变化,油红O染色评估肝脏脂滴代谢情况;蛋白免疫印迹法及实时荧光定量聚合酶链式反应检测法尼醇X受体(farnesoid X receptor,FXR)、钠牛磺胆酸共转运肽(Na+-taurocholate co-transporting polypeptide,NTCP)、多药耐药相关蛋白2(multidrug resistance-associated protein 2,MRP2)、胆汁盐转运蛋白(bile salt export pump,BSEP)蛋白和mRNA表达水平。结果与正常组比,模型组大鼠肝脾指数、血清转氨酶(ALT、AST、AKP)及胆红素(TBIL、DBIL、TBA)显著升高(P<0.05),肝组织受损。壮药依山红各剂量及熊去氧胆酸显著降低这些指标(P<0.05),改善肝组织学病变,减少脂滴沉积,效果呈剂量依赖性。同时,依山红各剂量组大鼠肝组织中NTCP、MRP2蛋白的表达量均明显升高(P<0.05);高剂量组大鼠肝组织中BSEP蛋白相对表达量显著下降(P<0.05)。与模型组相比,依山红高、中剂量组大鼠肝组织中Fxr、Ntcp、Mrp2 mRNA的相对表达量显著升高(P<0.05);依山红低剂量组大鼠仅Mrp2 mRNA表达量显著升高(P<0.05);依山红各剂量大鼠肝组织中Bsep mRNA表达水平显著下降(P<0.05)。结论壮药依山红可通过调节FXR及其调控的胆汁转运相关蛋白的表达,对ANIT诱导胆汁淤积模型大鼠起到保肝利胆的作用。

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.

Interaction of cyclodextrins with 1,3-di(1-naphthyl)propane and the additive effects of ionic surfactants

The interaction between cyclodextrins (CDs) and 1,3-di(1-naphthyl)propane (1) in aqueous methanol (V: V=1:1) has been investigated by means of fluorescence emission and UV absorption. Fluorescence enhancement and absorption spectra reveal that β- or γ-CD can form inclusion complexes with 1, but α-CD cannot. One of these complexes is identified as ground state complex (2:1), i.e. the eclipsed conformer of 1 is included. Molecule 1 can be driven out of the CD cavity by sodium dodecylsulfate (SDS) molecule, but cannot by cetyltrimethylammonium bromide (CTAB) or sodium cetylsulfate (SCS) molecules due to their alkyl chain coiling.

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.