Anti HIV-1 agents 5: Synthesis and anti-HIV-1 activity of some N-arylsulfonyl-3-acetylindoles in vitro

In continuation of our program aimed at the discovery and development of compounds with superior anti-human immunodeficiency virus type 1 (HIV-1) activity, 21N-arylsulfonyl-3-acetylindole analogs (2a-u) were synthesized and preliminarily evaluated as HIV-1 inhibitors in vitro. Among of all the analogs, several compounds exhibited significant anti-HIV-1 activity, especially N-phenylsulfonyl-3-acetyl-6-methylindole (2j) and N-(p-ethyl)phenylsulfonyl-3-acetyl-6-methylindole (2n) showed the most potent anti-HIV-1 activity with EC50 values of 0.36 and 0.13 mu g/mL, and TI values of >555.55 and 791.85, respectively. It demonstrated that introduction of the acetyl group at the 3-position of N-arylsulfonyl-6-methylindoles could generally lead to the more potent analogs. (C) 2010 Elsevier Ltd. All rights reserved.

Rare-earth-metal mixed hydride/aryloxide complexes bearing mono(cyclopentadienyl) ligands. Synthesis, CO2 fixation, and catalysis on copolymerization of CO2 with cyclohexene oxide

Hydrogenolysis of mono(cyclopentadienyl)-ligated rare-earth-metal bis(alkyl) complexes Cp'Ln-(CH2SiMe3)2(THF) (Ln = Y (1a), Dy (1b), Lu (1c); Cp' = C5Me4SiMe3) with PhSiH3 afforded the mixed hydride/alkyl complexes [Cp'Ln(mu-H)(CH2SiMe3)(THF)](2) (Ln = Y (2a), Dy (2b), Lu (2c)). The overall structure of complexes 2a-c is a C-2-symmetric dimer containing a planar symmetric Ln(2)H(2) core at the center of the molecule. Deprotonation of ArOH (Ar = C6H2-Bu-t(2)-2,6-Me-4) by the metal alkyl group of 2a-c led to formation of the mixed hydride/aryloxide derivatives [Cp'Ln(mu-H)(OAr)](2) (Ln = Y (3a), Dy (3b), Lu (3c)), which adopt the dimeric structure through hydride bridges with trans-accommodated terminal aryloxide groups.

Synthesis and Aqueous Solution Properties of Hydrophobically Modified Anionic Acrylamide Copolymers

In this investigation, hydrophobically modified polyacrylamide with low amounts of anionic long-chain alkyl was synthesized by the free radical polymerization in deionized water. This water-soluble copolymerization method is more convenient compared with the traditional micellar copolymerization methods. The copolymers were characterized using Fourier transform infrared, H-1 NMR, and the molecular weight and polydispersity were determined using gel permeation chromatography. The solution behavior of the copolymers was studied as a function of composition, pH, and added electrolytes. As NaCl was added to solutions of AM/C(11)AM copolymers or pH was lowered, the shielding or elimination of electrostatic repulsions between carboxylate groups of the C(11)AM unit lead to coil shrinkage.

Efficient synthesis of highly substituted pyrrolin-4-ones via PIFA-mediated cyclization reactions of enaminones

A convenient and efficient synthesis of highly substituted pyrrolin-4-ones is developed via the PIFA-mediated cyclization reactions of readily available enaminones, and a mechanism involving sequential cleavage of N-C bond, formation of new N-C bond, intramolecular addition reaction, and benzilic acid type rearrangement is proposed.

Synthesis and morphology of polyethylene chains grafted onto the surface of crosslinked polystyrene microspheres

The bifunctional comonomer 4-(3-butenyl) styrene was used to synthesize crosslinked polystyrene microspheres (c-PS) with pendant butenyl groups on their surface via suspension copolymerization. Polyethylene chains were grafted onto the surface of c-PS microspheres (PS-g-PE) via ethylene copolymerizing with the pendant butenyl group on the surface of the c-PS microspheres under the catalysis of metallocene catalyst. The composition and morphology of the PS-g-PE microspheres were characterized by means of Fourier transform infrared spectroscopy, Fourier transform Raman spectroscopy, X-ray photoelectron spectroscopy, and field-emission scanning electron microscopy. It is possible to control the content of PE grafted onto the surface of c-PS microspheres by varying the polymerization time or the initial quantity of pendant butenyl group on the surface of c-PS microspheres. Investigation on the morphology and crystallization behavior of grafted PE chains showed that different surface patterns could be formed under various crystallization conditions. Moreover, the crystallization temperature of PE chains grafted on the surface of c-PS microspheres was 6 degrees C higher than that of pure PE. The c-PS microspheres decorated by PE chains had a better compatibility with PE matrix.

Synthesis and crystal structure of [Nd(eta(6)-1,3,5-C6H3Me3)(AlCl4)(3)]( C6H6) and structural comparison of Ln(eta(6)-arene)(AlCl4)(3)

Reaction of NdCl3, with AlCl3 and mesitylene in benzene gives complex [Nd(eta (6)-1,3,5-C6H3Me3) (AlCl4)(3)] (C6H6) (1) which was characterized by elemental analysis, IR spectra, MS and X-lay diffractions. The X-ray determination indicates that 1 has a distorted pentagonal bipyramidal geometry and crystallizes in the monoclinic, space group P2(1)/n with a = 0.9586(2), b = 1.1717(5), c = 2.8966(7) nm, beta = 90.85 (2)degrees, V = 3.2529(6) nm(3), D-c = 1.573 g/cm(3), Z = 4. A comparison of bond parameters for all the reported Ln(eta (6)-Ar) (AlCl4)(3) complexes indicates that the bond distance of Ln-C is shortened with the increasing of methyl group on benzene and with the decreasing of radius of lanthanide ions.

Synthesis and spectroscopic studies of endohedral metallofullerenes Tb@C-2n

Endohedral metallofullerenes Tb@C-2n were synthesized and extracted with high-yield by K-H carbon-are evaporation and an effective pyridine extraction technique at high-temperature high-pressure. Laser-desorption-ionization time-of-flight (LD-TOF) mass spectrometry, X-ray photoelectron spectroscopy (XPS), solid-state fluorescent emission spectroscopy and gas phase derivation reaction with the self-chemical ionization mass spectrometric ion system of vinyl acetate were employed for studying the electronic structures, fluorescent properties and gas phase reactivities of metallofullerenes Tb@C-2n. The experimental results suggest that endohedral metallofullerenes Tb@C-2n would have the approximate structures of Tb3+@C-2n(3-) similar to other metallofullerenes, good fluorescent emission properties and active reactivities in gas phase ion-molecular reactions.

Localization and distribution of tissue type and urokinase type plasminogen activators and their inhibitors type 1 and 2 in human and rhesus monkey fetal membranes

Fetal membranes consist of 10 distinct layers including components of amnion, chorion and decidua, the latter being of maternal origin. They form mechanically integrated sheets capable of retaining amniotic fluid and play an essential role in protecting fetal growth and development in the pregnant uterus. The extracellular matrix, substrate for plasminogen activators (PAs), is an important supportive framework of the fetal membranes. :Fetal membranes from women with preterm premature rupture of membranes may differ in their protease activity compared with normal membranes. To identify the presence of PAs and their inhibitors (PAI) and their possible role in the process of fetal membrane rupture, this study in investigated the distribution and localization of both protein and mRNA for tissue (t) and urokinase (u) PA and their inhibitors type 1 (PAI-1) and type 2 (PAI-2) in amniochorion of human and rhesus monkey using conventional and. confocal immunofluorescence microscopy. In situ hybridization analysis showed that the distribution and localization of mRNAs for tPA, uPA, PAI-I and PAI-2 were similar in the fetal membranes of human and rhesus monkey; no obvious species difference was observed. Evidence of tPA mRNA was detected in amniotic epithelium, trophoblast cells and nearly all cells of the decidual layer. Strong expression of uPA mRNA was noted in the decidual cells which increased in intensity as the abscission point was approached. Weak staining in chorion laeve trophoblast was also detected. In situ hybridization experiments showed PAI-1 mRNA to be concentrated mainly in the decidual cells, some of which were interposed into the maternal-facing edge of the chorion laeve. Maximal labelling of the decidua occurred towards the zone of abscission. Weak expression of PAI-1 mRNA nas also noted in some cells of the chorion laeve. The distribution of PAI-2 mRNA in amniochorion was also concentrated in the cells of the decidual layer, maximum expression of the mRNA was in the level of abscission. No detectable amount of mRNAs for tPA, uPA, PAI-1 and PAI-2 was found in the fibroblast, reticular and spongy layers. Distribution of the proteins of tPA, uPA and PAI-1 in the fetal membranes of these two species was consistent with the distribution of their mRNA. Anti-PAI-2 immunofluorescence was found to be strongly concentrated in the amniotic epithelium, but PAI-2 mRNA was negative in this layer, suggesting that the epithelium-associated PAI-2 is not of epithelial origin. These findings suggest that a local fibrinolysis in fetal membranes generated by precisely balanced expression of PAs and their inhibitors via paracrine or autocrine mechanisms may play an essential role in fetal membrane development, maturation and in membrane rupture. Following an analysis of the distribution and synthesis of activators and inhibitors it was found that they may play a role in abscission during the third stage of labour. (C) 1998 W. B. Saunders Company Ltd.

Measurement of the total reaction cross section for the mirror nuclei N-12 and B-12

The mirror nuclei N-12 and B-12 are separated by the Radioactive Ion Beam Line in Lanzhou (RIBLL) at HIRFL from the breakup of 78.6 MeV/u N-14 on a Be target. The total reaction cross-sections of N-12 at 34.9 MeV/u and B-12 at 54.4 MeV/u on a Si target have been measured by using the transmission method. Assuming N-12 consists of a C-11 core plus one halo proton, the excitation function of N-12 and B-12 on a Si target and a C target were calculated with the Glauber model. It can fit the experimental data very well. The characteristic halo structure for N-12 was found with a large diffusion of the protons density distribution.

Crosslinkable poly(propylene carbonate): High-yield synthesis and performance improvement

A crosslinking strategy was used to improve the thermal and mechanical performance of poly(propylene carbonate) (PPC): PPC bearing a small moiety of pendant C=C groups was synthesized by the terpolymerization of allyl glycidyl ether (AGE), propylene oxide (PO), and carbon dioxide (CO2). Almost no yield loss was found in comparison with that of the PO and CO2 copolymer when the concentration of AGE units in the terpolymer was less than 5 mol %. Once subjected to UV-radiation crosslinking, the crosslinked PPC film showed an elastic modulus 1 order of magnitude higher than that of the uncrosslinked one. Moreover, crosslinked PPC showed hot-set elongation at 65 degrees C of 17.2% and permanent deformation approaching 0, whereas they were 35.3 and 17.2% for uncrosslinked PPC, respectively. Therefore, the PPC application window was enlarged to a higher temperature zone by the crosslinking strategy.

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.

A study of the radical reaction of C-60 with n-Bu(3)SnH

The reaction of buckministerfullerene (C-60) with tri-n-blltyltin hydride(n-Bu(3)SnH) in toluene solution has been investigated. According to mass spectrometry analysis, the products of above reaction are C-60(BuH)(n)(n = 1 similar to 3) and Bu(x)Sn(y)H(x) (x = 3 similar to 8, y = 1 similar to 4,approximate to = 0 similar to 3). The reaction maybe provide a new method for the synthesis of alkylated fullerene derivatives. Where C-60 also takes a role of a catalysis of organtic-tin polymerization. The radical reaction mechanism has been discussed.

The complete mitochondrial genome of the large yellow croaker, Larimichthys crocea (Perciformes, Sciaenidae): Unusual features of its control region and the phylogenetic position of the Sciaenidae

To understand the systematic status of Larimichthys crocea in the Percoidei, we determined the complete mitochondrial (mt) genome sequence using 454 sequencing-by-synthesis technology. The complete mt genome is 16,466 bp in length including the typical structure of 22 tRNAs, 2 rRNAs, 13 protein-coding genes and the noncoding control region (CR). Further sequencing for the complete CR was performed using the primers Cyt b-F and 12S-R on six L crocea individuals and two L polyactis individuals. Interestingly, all seven CR sequences from L crocea were identical while the three sequences from L polyactis were distinct (including one from GenBank). Although the conserved blocks such as TAS and CSB-1, -2, and -3 are readily identifiable in the control regions of the two species, the typical central conserved blocks CSB-D, -E, and -F could not be detected, while they are found in Cynoscion acoupa of Sciaenidae and other Percoidei species. Phylogenetic analysis shows that L crocea is a relatively recently emerged species in Sciaenidae and this family is closely related to family Pomacanthidae within the Percoidei. L crocea, as the first species of Sciaenidae with complete mitochondrial genome available, will provide important information on the molecular evolution of the group. Moreover, the genus-specific pair of primers designed in this study for amplifying the complete mt control region will be very useful in studies on the population genetics and conservation biology of Larimichthys. (c) 2008 Elsevier B.V. All rights reserved.

Molecular cloning, characterization and expression of a serine protease with clip-domain homologue from scallop Chlamys farreri

Serine proteases play critical roles in a variety of invertebrate immune defense responses, including hemolymph coagulation, antimicrobial peptide synthesis, and melanization. The first mollusk serine protease with clip-domain (designated CFSP1) cDNA was obtained from the scallop Chlamys farreri challenged with Vibrio anguillarum by randomly sequencing a whole tissue cDNA library and rapid amplification of cDNA ends (RACE). The full-length cDNA of the C. farreri serine protease was 1211 bp, consisting of a 5-terminal untranslated region (UTR) of 72 bp, a 3'-terminal UTR of 77 bp with a canonical polyadenylation signal sequence AATAAA and a poly (A) tail, and an open reading frame of 1062 bp. The CFSP1 cDNA encoded a polypeptide of 354 amino acids with a putative signal peptide of 19 amino acids and a mature protein of 335 amino acids. The deduced amino acid sequence of CFSP1 contained an amino-terminal clip domain, a low complexity region, and a carboxyl-terminal serine protease domain. CFSP1 mRNA was mainly expressed constitutively in the hemocytes and was up-regulated and increased 2.9- and 1.9-fold at 16 h after injury and injection of bacteria. (c) 2006 Elsevier Ltd. All rights reserved.