New family of highly emissive,soluble poly(1,4‐fluorenylenevinylene) derivatives: Synthesis and characterization

A new poly(arylene vinylene) derivative, poly(1,4‐fluorenylenevinylene), with the advantages of poly(p‐phenylene vinylene) and polyfluorene (PF), was designed, synthesized, and characterized. The polymer showed a defect‐free structure and a number‐average molecular weight of 32,600. The resulting polymer was thermally stable with a high glass‐transition temperature (200 °C) and was readily soluble in common organic solvents. The polymer film showed a maximum emission at 515 nm and had a photoluminescence quantum yield of 58 ± 5%. A cyclic voltammetry study revealed that the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of the polymer were 2.9 and 5.51 eV, respectively. The double‐layer light‐emitting‐diode devices fabricated from the polymer emitted bright green light with a maximum around 515 nm. The device showed a maximum luminous efficiency of 0.13 cd/A and a maximum luminance value of 600 cd/m² at 17 V. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6515–6523, 2005     

Synthesis and Antibacterial and Antifungal Properties of Novel S-, N-, N,S-, and S,O-Substituted 1,4-Naphthoquinone Derivatives

Abstract

A novel series of substituted 1,4-naphthoquinone derivatives were synthesized and evaluated for their antibacterial and antifungal activity. The structures of the novel products were characterized by spectroscopic methods. Among the tested compounds, 2,2′,3,3′-alkoxy substituted naphthoquinones, S,O-substituted naphthoquinone, and N,S-substituted naphthoquinone derivatives are the most potent antifungals against C. tenuis. 2,3-Thio-2′,3′-alkoxy substituted naphthoquinones are the most effective antifungal compounds against A. niger.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

基于二芳炔硫醚的2,6-二芳基-1,4-二噻烯的合成

描述了一种基于二芳炔硫醚(Ar—C≡C—S—C≡C—Ar)底物合成2,6-二芳基-1,4-二噻烯的方法.将二芳炔硫醚和Na2S·9H2O在C2H5OH/C2H5ONa体系中回流反应,以80%~96%的产率合成了一系列2,6-二芳基-1,4-二噻烯化合物.该方法反应条件温和、产率高并且表现出很好的选择性.反应机理涉及硫负离子对底物分子的两个C≡C键的选择性亲核加成,即硫负离子(包括S2-和中间体B硫负离子)总是选择性地加到芳基一侧的炔碳上形成1,4-二噻烯.对化合物1a进行了X线晶体结构解析.分子中的六元杂环呈"船式"构型.C(1)—C(2)和C(1A)—C(2A)具有典型的双键性质,S(1)—C(2)和S(2)—C(1)的键长数则比一般C—S单键稍短,显示硫原子上的孤对电子与C(1)=C(2)双键上的π电子存在一定程度的共轭作用.1a的晶体学参数:属正交晶系,Pnma空间群,a=10.1330(11),b=27.318(3),c=5.5402(6),α=90.00°,β=90.00°,γ=90.00°,V=1533.6(3)3,Z=4,ρcalcd=1.422 g/cm3.最终偏离因子R=0.038,Rw=0.102。     

Comparative study on 2-amino-1,4-naphthoquinone derived ligands as indium (III) selective PVC-based sensors

The three different ligands (Q₂ to Q₄) based on 2-amino-1,4-naphthoquinone (Q₁), have been synthesized and explored as neutral ionophores for preparing polyvinyl chloride-based membrane sensors selective to indium (III). The addition of potassium tetrakis(4-chlorophenyl) borate and various plasticizers, viz., o-NPOE, DBP, DBBP, DOP and CN has been found to substantially improve the performance of the sensors. The best performance was obtained with the sensor no. 16 having membrane of ligand (Q₂) with composition (%, w/w) ionophore Q₂ (3.0%):PVC (30.0%):o-NPOE (63.0%):KTpClPB (4.0%). This sensor exhibits Nernstian response with slope 19.8 mV/decade of activity in the concentration range 2.5 × 10⁻⁷ to 1.0 × 10⁻² M indium (III), performs satisfactorily over wide pH range of (2.5-7.5) with a fast response time (10 s). The sensor was also found to work satisfactorily in partially non-aqueous media up to 20% (v/v) content of acetonitrile, ethanol and methanol. The proposed sensor can be used over a period of 3.5 months without significant drift in potentials. The quantitative application of sensor was also evaluated by comparative analysis of artificially made sea water with AAS.     

Synthesis and structure of N-(4-dialkylaminophenyl)hexafluoro-1,4-naphthoquinone 4-imines

The reaction of heptafluoro-1-naphthol with N,N-dialkyl-p-nitrosoanilines or N,N-dialkyl-p-phenylenediamines in the presence of HIO₃ gave the corresponding polyfluorinated N-aryl-1,4-naphthoquinone 4-imine derivatives which exist in solution as equilibrium mixtures of Z and E isomers. 2,3,5,6,7,8-Hexafluoro-N-(4-dimethylaminophenyl)-1,4-naphthoquinone 4-imine in crystal has exclusively the Z-isomer structure.     

Synthesis,cytotoxicity and anti‐metastatic properties of new pyridyl–thiazole arene ruthenium(II) complexes

A series of novel ruthenium(II)–cymene complexes ( 1 – 8 ) containing substituted pyridyl–thiazole ligands, [Ru(η⁶‐p‐cymene)(L)Cl]Cl (L = N,N‐chelating derivatives), have been synthesized and characterized using elemental analysis, infrared, ¹H NMR and ¹³C NMR spectroscopies and mass spectrometry. All these complexes not only display marked cytotoxicity in vitro against three different human cancer cell lines (HeLa, A549 and MDA‐MB‐231), but also exhibit promising anti‐metastatic activity at sub‐cytotoxic concentrations. Cell cycle analysis shows that the ruthenium(II) complex‐induced growth inhibition was mainly caused by S‐phase cell cycle arrest. Further protein level analysis suggests that compound 5 may exert antitumor activity via a p53‐independent mechanism.     

Novel amino- and thio(substituted)-1,4-naphthoquinone (NQ) compounds: Synthesis and characterization

Abstract

Synthesis of new 1,4-naphthoquinone derivatives is important in terms of searching new biologically active substances. In particular, compounds with piperazine and thiol moiety in their structure, show a wide range of pharmacological activity such as anti-inflammatory, anticancer, anti-fungal, anti-bacterial, anti-allergic, apoptosis and radical scavenging activities. In this study, new amino- and thio(substituted) naphthoquinone derivatives were synthesized by the reaction of thiols and thioalcohols with four naphthoquinone compounds which were used as starting materials. The new compounds were purified by column chromatography. The structure of the compounds was confirmed by different spectroscopic techniques.     

Synthesis and characterization of poly(d,l-lactide-co-glycolide) modified by maleic anhydride and 1,4-butanediamine

Bone tissue engineering is sought to apply strategies for bone defects healing biodegradable porous scaffolds without limitations and shortcomings. In this work, we have developed a novel maleic anhydride (MAH) and 1,4-butanediamine modified poly(lactide-co-glycolide) polymer (BMPLGA). The synthesized polymer was characterized by Fourier transform infrared spectrometry (FTIR), Nuclear magnetic resonance spectra (¹H NMR), gel permeation chromatography (GPC) and contact angle measurements. In addition, cell morphologies in the extracts and cell cytotoxity were also studied. The results showed that the BMPLGA was successfully obtained by introducing MAH and 1,4-butanediamine into PLGA in bulk. The introduction of anhydride and amino groups improved the hydrophilicity of PLGA. Fibroblastic cells showed normal morphologies in BMPLGA extracts, and the BMPLGA materials showed no cell cytotoxicity. The synthetic BMPLGA material may have potentials for biomedical applications due to improving hydrophilicity.     

Synthesis and electrical conductivity of poly(1,4-phenylenevinylene-co-2-nitro-1,4-phenylenevinylene)

A series of PPV copolymers containing 2-nitro-1,4-phenylenevinylene (NO₂-PV) units were prepared via the water-soluble precursor route. They were obtained in film form and were doped with I₂ and FeCl₃. Doping increased the electrical conductivities to maximum values of about 3×10^?2 and 3×10^?1 s cm^?1, respectively, for the two dopants. Conductivity depended strongly on the composition of the copolymers; it reached a maximum value at ca. 1–2 mol % of NO₂-PV units in the copolymers and then dropped rapidly with further increase in NO₂-PV content. Electronic effects of the substituent and morphological changes induced by copolymerization appear to interplay intricately, resulting in the occurrence of a maximum conducting composition. © 1993 John Wiley & Sons, Inc.     

Investigations on the antioxidant activity of 5,8-dihydroxy-1,4-dihydro-1,4-methanonaphthalene (DDMN)

5,8-dihydroxy-1,4-dihydro-1,4-methanonaphthalene (DDMN), a substituted phenol, is synthesized by the reduction of a cyclic dione, 1,4,4a,8a-tetrahydro-endo-1,4-methano-naphtha-5,8-dione (THMND). The pulse radiolysis technique has been employed to understand the nature of transient species formed by the reaction of radiolytic species of water radiolysis with DDMN. ^•OH radicals were observed to react with DDMN with a bimolecular rate constant of 1.5 × 10¹⁰ dm³ mol⁻¹ s⁻¹. The inhibition of radiation-induced lipid-peroxidation by DDMN was studied in rat liver microsomes by assessing the formation of thiobarbituric acid reactive substances (TBARS). It was found to be strongly inhibitory. The results suggest that DDMN has very good antioxidant activity and may possibly emerge as a good radio-protector. Dr. Hari Mohan: since deceased.     

Synthesis and characterization of new poly(N-1-adamantylmaleimide) and poly(N-1-diamantylmaleimide)

N-l-Diamantylmaleimide was synthesized by reaction of maleic anhydride with 1-aminodiamantane, followed by dehydration with acetic anhydride and sodium acetate. Poly(N-1-adamantylmaleimide) ( IIa ) and poly(N-l-diamantylmaleimide) ( IIb ) were polymerized using 2,2′-azobisisobutyronitrile (AIBN) as an initiator under different experimental conditions such as various initiator concentrations, solvents, polymerization temperatures, and polymerization times. Polymerizations of N-l-adamantylmaleimide in benzene at 60°C or in bulk gave polymers with molecular weights (2000–9500). The experimental results indicated that the propagation may be interrupted by steric hindrance of bulky and rigid substituents such as the adamantyl or diamantyl groups. In addition, the effect of chain transfer to monomer contributes to the relatively low activation energy. The glass transition temperatures of Ia and Ib were 204 and 216°C, respectively. The temperatures at 5% weight loss of the polymers IIa and IIb were above 412°C. © 1996 John Wiley & Sons, Inc.     

Synthesis and Spectroscopic Evaluation of Novel N-, S-, and O-Substituted 1,4-Naphthoquinone Derivatives

Abstract

Novel O- S,O- S,S- N,N- and N,S-substituted naphthoquinone compounds were prepared by reaction of 2,3-dichloro-1,4-naphthoquinone and the corresponding nucleophiles in the presence of chloroform and triethylamine or ethanol solution of Na₂CO₃. The structures of the novel naphthoquinone compounds were characterized by micro analysis, FT-IR, UV/Vis, ¹H NMR, ¹³C NMR, MS, and fluorescence spectroscopy.

GRAPHICAL ABSTRACT      

Synthesis and properties of new polyamides derived from 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene and aromatic dicarboxylic acids

The diamine 1,4-bis(4-aminophenoxy)-2,5-di-tert-butylbenzene, containing symmetric, bulky di-tert-butyl substituents and a flexible ether unit, was synthesized and used to prepare a series of polyamides by the direct polycondensation with various aromatic dicarboxylic acids in N-methyl-2-pyrrolidinone (NMP) using triphenyl phosphite and pyridine as condensing agents. All the polymers were obtained in quantitative yields with inherent viscosities of 0.32–1.27 dL g⁻¹. Most of these polyamides, except II _a , II _d , and II _e , showed an amorphous nature and dissolved in polar solvents and less polar solvents. Polyamides derived from 4,4′-sulfonyldibenzoic acid, 4,4′-(hexafluoro-isopropylidene)dibenzoic acid, and 5-nitroisophthalic acid were even soluble in a common organic solvent such as THF. Most polyamide films could be obtained by casting from their N,N-dimethylacetamide (DMAc) solutions. The polyamide films had a tensile strength range of 49–78 MPa, an elongation range at break of 3–5%, and a tensile modulus range of 1.57–2.01 GPa. These polyamides had glass transition temperatures ranging between 253 and 276°C, and 10% mass loss temperatures were recorded in the range 402–466°C in nitrogen atmosphere. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1069–1074, 1998     

Methods for the Synthesis of Heteroaryl-substituted 1,4-Benzo- and 1,4-Naphthoquinones. (Review)

Methods for the synthesis of heteroaryl-substituted 1,4-benzo- and 1,4-naphthoquinones with a C-C bond between the heterocycle and quinone fragments are reviewed. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 803–833, June, 2005.     

Synthesis and properties of polyimides derived from 1,4-bis(4-aminophenoxy)2,5-di-tert-butylbenzene

Novel aromatic polyimides containing symmetric, bulky di-tert-butyl substituents unit were synthesized from 1,4-bis(4-aminophenoxy)2,5-di-tert-butylbenzene (BADTB) and various aromatic tetracarboxylic dianhydrides by the conventional two-stage procedure that included ring-opening polyaddition in a polar solvent such as N,N-dimethylacetamide to give poly(amic acid)s, followed by cyclodehydration to polyimides. The diamine was prepared through the nucleophilic displacement of 2,5-di-tert-butylhydroquinone with p-chloronitrobenzene in the presence of K₂CO₃, followed by catalytic reduction. Depending on the dianhydrides used, the poly(amic acid)s obtained had inherent viscosities of 0.83–1.88 dL g⁻¹. Most of the polyimides formed transparent, flexible, and tough films. Tensile strength and elongation at break of the BADTB-based polyimide films ranged from 68–93 MPa and 7–11%, respectively. The polyimide derived from 4,4′-hexafluoro-isopropylidenebisphathalic anhydride had better solubility than the other polyimides. These polyimides had glass transition temperatures between 242–298°C and 10% mass loss temperatures were recorded in the range of 481–520°C in nitrogen. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 1527–1534, 1997     

1，4-苯二硫乙酸配体构筑的锌(Ⅱ)及镉(Ⅱ)配合物的合成、晶体结构及荧光性质

基于1,4-苯二硫乙酸(H2L)及中性含氮配体,水热法合成了两个新的d10金属配合物[ZnClL0.5(bpp)](1)和[Cd2L(phen)4(H2O)2].L.2.78H2O(2)(bpp=1,3-di(4-pyridyl)propane,phen=1,10-phenanthroline),并通过单晶X-射线衍射、元素分析、红外光谱和热重对其结构进行了表征。结构分析表明,在配合物1中,Zn(Ⅱ)呈现四配位的扭曲四面体构型,进一步连接形成一维双链状结构。在配合物2中,Cd(Ⅱ)呈现六配位的扭曲八面体构型,并通过可能存在的氢键及π-π堆积作用,形成最终的三维超分子结构。同时,讨论了两种配合物的固体荧光性质。     

Iron(III) bis-complexes of Schiff bases of S-methyldithiocarbazates: Synthesis,structure, spectral and redox properties and cytotoxicity

A series of iron(III) bis-complexes of the type [FeL₂]X 1-4 , X = OH⁻ ( 1 ), Cl^¯ ( 3 ), and FeCl₄^¯ ( 2 , 4 ), where LH is a tridentate (N,N,S) ligands such as N′-(1-pyridin-2-ylethylidene)-hydrazinecarbodithioic acid methyl ester ( HL1 ), N′-(phenylpyridin-2-ylmethylene)-hydrazinecarbodithioic acid methyl ester ( HL2 ), N′-quinolin-2-ylmethylene-hydrazinecarbodithioic acid methyl ester ( HL3 ), or N′-(1-methyl-1H-imidazol-2-yl-methylene)hydrazinecarbodithioic acid methyl ester ( HL4 ) has been isolated in moderate to good yields and completely characterized by elemental analyses, conductivity studies, and infrared and UV-visible spectral measurements. The single crystal X-ray structures of 1 , 2 and 4 revealed that two deprotonated tridentate (NNS) ligands are meridionally coordinated to constitute a distorted octahedral coordination geometry around iron(III). In acetonitrile solution, all the complexes show quasi-reversible Fe(III)/Fe(II) redox behavior. The in vitro cytotoxicity of the ligands HL1–HL4 (IC₅₀: HL1 , 64.5; HL2 , 51.0; HL3 , 124.0; HL4 , 45.0 μM at 24 h) and complexes 1–4 (IC₅₀: 1 , 84.5; 2 , 40.0; 3 , 168.5; 4 , 50.5 μM at 24 h) towards A549 lung cancer cell lines are similar to cisplatin (69.0 μM), revealing that free ligands cause cancer cell death with potency higher than the corresponding iron(III) complexes. Also, both the ligands and the complexes cause cell death mainly through apoptotic mode, as revealed by the observation of a higher percentage of apoptotic cells in acridine orange (AO)/ ethidium bromide (EB), and Annexin V-Cy3 stained cancer cells.     

Synthesis and cytotoxicity of pentacyclic triterpenes-aniline nitrogen mustard derivatives

To discover novel nitrogen mustards, the reported mustard pharmacophore was combined with natural pentacyclic triterpenes, which are characterized with pharmacological and structural diversity. Thus, six conjugates were synthesized with 1,2,3-triazole linking N,N-bis (2-chloroethyl)-1,4-phenylenediamine and oleanolic acid, ursolic acid, or glycyrrhetinic acid, and their biological activity was evaluated against tumor cell lines HeLa, BGC-823, BEL-7404, and NCI-H460 using the MTT assay. As a result, these conjugates showed some selective cytotoxicity to NCI-H460, though all their activity potency was moderate or weak in the four cell lines.     

Structural aspects of a trimetallic CuII derivative: cytotoxicity and anti-proliferative activity on human cancer cell lines

A trimetallic Cu^II derivative, [Cu₃(L)₂(CF₃COO)₂] (1) (where H₂L = N,N′-bis(salicylidene)-1,3-propanediamine), was prepared and characterized. In 1, the two terminal Cu^II ions are linked to the central Cu^II by trifluoroacetato and doubly bridging phenoxido. Both the square-pyramidal and octahedral geometries are observed among two different Cu^II centers in the linear arrangement of the trimetallic unit. Compound 1 is characterized by IR and UV-Vis spectra. Compound 1 has high cytotoxic activity in breast adenocarcinoma (MCF-7), colorectal carcinoma (HCT116) and particularly, in ovarian carcinoma (A2780) cell line compared to a lung adenocarcinoma cell line. The IC₅₀ in A2780 cells is 25 times lower than the respective value for normal human primary fibroblasts demonstrating 1 has higher cytotoxicity towards cancer cells. Additionally, combination of DOX with 1 induces a higher loss of HCT116 cell viability compared with each drug alone.