Anti Human Immunodeficiency Virus-1 (HIV-1) Agents 1. Discovery of Benzyl Phenyl Ethers as New HIV-1 Inhibitors in Vitro

Ten single benzyl phenyl ethers were synthesized and evaluated as human immunodeficiency virus-1 (HIV-1) inhibitors in vitro for the first time. Among these compounds, especially 4-nitrobenzyl phenyl ether (3h) exhibited the highest anti-HIV-1 activity wi

Polychlorinated dibenzo-p-dioxin and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs) monitored by tree bark in an E-waste recycling area

To investigate the environmental levels and profiles of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), tree bark samples (n = 22) were collected from Luqiao, an E-waste recycling area, in east China in July 11-13, 2006. The average concentrations of PCDD/Fs, PBDEs, and PCBs determined by isotope dilution-high resolution gas chromatography (HRGC) coupled with high resolution mass spectrometer (HRMS) were 0.1 +/- 0.0, 1.4 +/- 0.2, and 6.5 +/- 0.8 lg g (1) lipid weight, respectively. PCDD/F-toxic equivalent (TEQ, WHO-1998), PCB-TEQs, and total dioxin-like TEQs were 1.3 +/- 0.1, 0.5 +/- 0.0, and 1.8 +/- 0.2 ng g (1) lipid weight, respectively. The profiles of these pollutants in the tree bark were also discussed. Tetra-CDFs, deca-BDE and tri-CBs were the main homologues and accounted for 47% of total PCDD/Fs, 79.3% of total PBDEs, and 33.2% of total PCBs, respectively; As for TEQs, 2,3,4,7,8-PeCDF and PCB126 were the main contributors and accounted for 36% of the total PCDD/F-TEQs and 81.2% of the total PCB-TEQs, respectively. High accumulation of PCDD/Fs, PBDEs, and PCBs detected in the tree bark indicated heavy contaminations of these pollutants in Luqiao area. (C) 2008 Elsevier Ltd. All rights reserved.

Elevated levels of urinary 8-hydroxy-2'-deoxyguanosine in male electrical and electronic equipment dismantling workers exposed to high concentrations of polychlorinated dibenzo-p-dioxins and dibenzofurans, polybrominated diphenyl ethers, and polychlorinated biphenyls

To investigate the occupational exposure levels to polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs), polybrominated diphenyl ethers (PBDEs), and polychlorinated biphenyls (PCBs), indoor dust (n = 3) in workshops and hair samples from male workers (n = 64) were collected at two electrical and electronic equipment waste (E-waste) dismantling factories located in the LQ area in east China in July 11-13, 2006. Pre- and postworkshift urines (64 of each) were also collected from the workers to study oxidative damage to DNA using 8-hydroxy-2'-deoxyguanosine (8-OHdG) as a biomarker. The concentrations of PCDD/Fs, PCDD/F-WHO-TEQs, PBDEs, PCBs and PCB-WHO-TEQs were (50.0 +/- 8.1) x 10(3), 724.1 +/- 249.6, (27.5 +/- 5.8) x 10(6), (1.6 +/- 0.4) x 10(9), (26.2 +/- 3.0) x 10(3) pg/g dry weight (dw) in dust, and (2.6 +/- 0.6) x 10(3), 42.4 +/- 9.3, (870.8 +/- 205.4) x 10(3), (1.6 +/- 0.2) x 10(6), 41.5 +/- 5.5 pg/g dw in hair, respectively. The homologue and congener profiles in the samples demonstrated that high concentrations of PCDD/Fs, PBDEs, and PCBs were originated from open burning of E-waste. The 8-OHdG levels were detected at 6.40 +/- 1.64 mu mol/mol creatinine in preworkshift urines. However, the levels significantly increased to 24.55 +/- 5.96 mu mol/mol creatinine in postworkshift urines (p < 0.05). Then, it is concluded that there is a high cancer risk originated from oxidative stress indicated by the elevated 8-OHdG levels in the E-waste dismantling workers exposed to high concentrations of PCDD/Fs, PBDEs, and PCBs.

Detection of polybrominated diphenyl ethers in tilapia (Oreochromis mossambicus) from O'ahu, Hawai'i

Polybrominated diphenyl ethers (PBDEs) have been detected for the first time at a range from 231.58 to 685.61 ng g(-1) lipid weight in the muscles of tilapia ( Oreochromis mossambicus) collected from O'ahu, an island of the geographically isolated Hawaiian archipelago.

Preliminary hazard assessment of polychlorinated biphenyls, polybrominated diphenyl ethers, and polychlorinated dibenzo-p-dioxins and dibenzofurans to Yangtze finless porpoise in Dongting Lake, China

Yangtze finless porpoise (Neophocaena phocaenoides asiaeorientalis), a protected endangered species, is the sole freshwater subspecies of finless porpoise, living only in the middle and lower reaches of the Yangtze River, China, and its appended lakes. Its population has decreased sharply to 1,400 because of human activities, including environmental contamination. In the present study, polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) were determined in the blubber, liver, kidney, stomach, small intestine, and brains of five individual Yangtze finless porpoises collected from 1998 to 2004. The results showed PCB concentrations ranged from 0.06 to 1.89 mu g/g lipid weight in the organs and consisted mainly of penta-, hexa-. and decachlorinated biphenyls. The PBDE concentrations were between 5.32 and 72.76 ng/g lipid weight. Tetra-, penta-, and hexabrominated diphenyl ethers were the major homologues. The PCDD/F concentrations ranged from 65 to 1,563 pg/g lipid weight, and their predominant homologues were penta- and hexachlorinated dibenzofurans and hepta- and octachlorinated dibenzo-p-dioxins. The hazard quotients (HQs) based on toxic equivalency were determined to be greater than one in all individuals for PCBs, for PCDD/Fs, and for PCBs and PCDD/Fs In addition, HQs would be higher if PBDEs were included. The results suggest that reduction of environmental contamination may contribute greatly to protecting this highly endangered species.

Headspace solid-phase microextraction with novel sol-gel permethylated-beta-cyclodextrin/hydroxyl-termination silicone oil fiber for determination of polybrominated diphenyl ethers by gas chromatography-mass spectrometry in soil

A simple, sensitive, and accurate method for determination of polybrominated diphenyl ethers (PBDEs) in soil has been developed based on headspace solid-phase microextraction (HS-SPME) followed by gas chromatography-mass spectrometry (GC-MS). Permethylated-beta-cyclodextrin/hydroxyl-termination silicone oil (PM-beta-CD/OH-TSO) fiber was first prepared by sol-gel technology and employed in SPME procedure. By exploiting the superiorities of sot-gel coating technique and the advantages of the high hydrophobic doughnut-shaped cavity of PM-beta-CD, the novel fiber showed desirable operational stability and extraction ability. After optimization on extraction conditions like water addition, extraction temperature, extraction time, salts effect, and solvents addition, the method was validated in soil samples, achieving good linearity (r>0.999), precision (R.S.D. < 10%), accuracy (recovery>78%), and detection limits (S/N =3) raging from 13.0 to 78.3 pg/g. (c) 2007 Published by Elsevier B.V.

Synthesis and metallophilic properties of troponoid thiocrown ethers

A new class of ionophores with troponoid and thiocrown ether units was prepared. Cation-binding properties of troponoid dithiocrown ethers were characterized using UV and NMR spectroscopies. They have affinity with metal ions; in particular, they showed high affinity with Hg2+. Transport of Hg2+ through a CHCl3 liquid membrane with troponoid dithiocrown ethers was examined in a U-type cell. From an aqueous solution of HgCl2 and CuCl2, Hg2+ is transferred selectively and smoothly, while the Cu2+ remained quantitatively in the original solution. The cavity size of dithiocrown ethers is one of the requirements for effective extraction and transport of Hg2+. However, derivatives with a smaller cavity still extract and transport Hg2+. A polymer-supported troponoid dithiocrown ether was prepared to transport Hg2+ effectively and repeatedly. Comparing the troponoid dithiocrown ether with the benzenoid dithiocrown ether with a similar cavity size, the former was more effective for the transport of Hg2+. It is proposed that the tropone ring assisted the release of Hg2+ from the complex by Coulomb repulsion between the protonated tropone ring and Hg2+.

Miscibility studies of the blends of chitosan with some cellulose ethers

The polymeric films have been prepared based on blends of chitosan with two cellulose ethers-hydroxypropylmethylcellulose and methylcellulose by casting from acetic acid solutions. The films were transparent and brittle in a dry state but an immersion of the samples in deionized water for over 24 h leads to their disintegration or partial dissolution. The miscibility of the polymers in the blends has been assessed by infrared spectroscopy, wide-angle X-ray diffraction, scanning electron microscopy and thermal gravimetric analysis. It was shown that although weak hydrogen bonding exists between the polymer functional groups the blends are not fully miscible in a dry state.

Gas-phase ion - Molecule reactions of neutral C-60 with the plasmas of alkyl methyl ethers and primary alcohols

The gas-phase ion-molecule reactions of C-60 with the methoxymethyl ion [CH3O=CH2](+) and the 1-hydroxyethyl ion [CH3CH=OH](+) generated under the self-chemical-ionization (self-CI) conditions of alkyl methyl ethers and primary alcohols were studied in the ion source of a mass spectrometer. The adduct ions [C60C2H5O](+) and protonated molecules [C60H](+) were observed as the major products of C-60 with the plasma of alkyl methyl ethers. On the contrary, the reactions of C-60 With the plasmas of primary alcohols produced few corresponding adduct ions. The AM1 semiempirical molecular orbital calculations were carried out on 14 possible structures. The calculated results showed that the most stable structure among the possible isomers of [C60C2H5O](+) is the [3+2] cycloadduct. According to experimental and theoretical results, the pathway for the formation of the adduct was presented.

Gas-phase ion-molecule reactions of C-60 with methyl ethers CH3OCnH2n+1

Gas-phase ion-molecule reactions of buckminsterfullerene (C-60) with the ion systems generated from the self-chemical-ionization of alkyl methyl ethers(CH3OCnH2n+1, n =2 , 3, 4) were studied in the ion source of a mass spectrometer. The adduct cation [C60C2H5O](+) and protonated molecular ion [C60H](+) were observed as the major products, The former was produced by the reactions.of C-60 with the methoxymethyl ion [CH3O = CH2](+) , the latter corresponded to the proton transfer reactions from the protonated alkyl methyl ethers to C60 It is suggested that the [3+2] cycloadduct is the most favorable structure among the probable isomers with special chemical properties, Our investigation provides the guidance for the synthesis of this compound in condensed phase.

Gas-phase ion-molecule reactions of neutral C-60 with alkyl methyl ethers under chemical ionization conditions

Gas-phase ion-molecule reactions of buckminsterfullerene (C-60) with the ion systems generated from the self-chemical ionization of alkyl methyl ethers (CH3OR, R = n-C2H5, n-C3H7, n-C4H9) were studied in the ion source of a mass spectrometer. The adduct cation [C60C2H5O](+) and protonated molecule [C60H](+) were observed as the major products. The former adduct ion was produced by the reactions of C-60 with the methoxymethyl ion [CH3OCH2](+), and the latter resulted from the proton transfer reactions from protonated alkyl methyl ethers to C-60 It is suggested that the [3+2] cycloadduct to a 6-6 bond of C-60 (a C-C bond common to two annulated six-membered rings) is the most favorable structure among the probable isomers of [C60C2H5O](+). (C) 1998 John Wiley & Sons, Ltd.

STUDY ON OPTICAL-ROTATORY OF HELIX POLYMER POLY(TRIPHENYLMETHYL METHACRYLATE)

The optical rotatory of helix polymer poly(triphenylmethyl methacrylate) (PTrMA) has been studied. The specific rotation of PTrMA is related with the length of helical chain linearly, while P(n)BAR<6 and P(n)BAR greater-than-or-equal-to 15. When P(n)BAR greater-than-or-equal-to 15, [alpha]D/20 = 1.6 P(n)BAR + 290-degrees. The contribution of each repeating unit to [alpha]D/20 is 1.6-degrees. In the 300-600 nm region, the ORD of PTrMA obeys both the Drude equation and Moffitt equation. The relationship between the [alpha]D of PTrMA and the solvent, concentration and temperature has also been investigated.

CONFORMATION OF PHENYL RINGS IN THE HELICAL CHAIN POLYMER POLY(TRIPHENYLMETHYL METHACRYLATE)

The conformation of phenyl rings in the side groups of the helical chain polymer poly(tripenyl-methyl methacrylate) (1) in solution was studied by spectroscopic methods. According to the Raman spectrum the phenyl rings of 1 and triphenylmethyl methacrylate in solution have the same depolarization ratio at 1002 cm-1. The electronic spectra (ultraviolet and fluorescence) of 1 are similar to those of model substances, except for the "red shift" of the spectra of about 5 nm. It was concluded that the phenyl rings can rotate around the phenyl-C bond.