Isolation, spectra, structure, and ring-opening polymerization of strained macrocyclic aryl(ether ketone) dimer

Macrocyclic arylene ether ketone dimer was isolated from a mixture of cyclic oligomers obtained by the nucleophilic substitution reaction of bisphenol A and 4,4'-difluorobenzophenone and easily polymerized to high molecular weight linear poly(ether ketone). The cyclic compound was characterized by FTIR, H-1- and C-13-NMR, and single-crystal x-ray diffraction. Analysis of the spectral and crystal structure reveals extreme distortions of he phenyl rings attached to the isopropylidene center and of the turning points of the molecular polygons. The release of the ring strain on ring-opening combined with entropical difference between the linear polymer chain and the more rigid macrocycle at temperatures of polymerization may be the proposed motivating factors in the polymerization of this precursor to high molecular weight poly(ether ketone). (C) 1997 John Wiley & Sons, Inc.

Efficient synthesis and facile polymerization of some cyclic bisphenol o-phthalates

A series of new macrocyclic aromatic esters have been efficiently synthesized from o-phthaloyl dichloride and various bisphenols, and unambiguously characterized by a combination of GPC, MS(FAB), FTIR and NMR. These macrocyclic oligomers undergo facile ring-opening polymerization in the presence of anionic initiators to give high molecular weight polyarylates.

Morphology and mechanical properties of PP/HMWPE blends

Mechanical properties and morphology of blends of polypropylene (PP) with high molecular weight polyethylene (HMWPE) prepared by coprecipitation from xylene solution are investigated. Compared to blends of PP with commercial high-density polyethylene (HDPE), the mechanical properties of the blends of PP/HMWPE are much superior to those of PP/HDPE blends. Not only is the tensile strength stronger, but also the elongation at break is much higher than that of the PP/HDPE blends of the same composition. These differences increase with increasing HMWPE and HDPE content. Scanning electron microscopy of the fracture surface resulting from the tensile tests shows that the compatibility in PP/HMWPE blends is much better than that in PP/HDPE blends. This is most likely attributable to the enhanced chain entanglement of HMWPE with the PP in the amorphous phase due to the lower crystallinity, owing to the high molecular weight of the HMWPE, and a much more flexible chain. The thermal behavior and spherulite morphology of both blends are also investigated.

MODIFICATION OF PP/HDPE BLENDS BY PP-PE SEQUENTIAL POLYMERIZATION PRODUCT

The morphology and mechanical properties of polypropylene/high-density polyethylene (PP/HDPE) blends in a wide range of compositions modified by a sequential Ziegler-Natta polymerization product (PP-PE) have been investigated. PP-PE contains multiple components such as PP, ethylene-propylene copolymer (EPC), and high molecular weight polyethylene (HMWPE). The effects of PP-PE on the mechanical properties and morphology of the PP/HDPE blends are the aggregative results of all its individual components. Addition of PP-PE to the blends not only improved the tensile strength of the blends, but the elongation at break increased linearly while the moduli were nearly unchanged. Morphological studies show that the adhesion between the two phases in all the blends of different compositions is enhanced and the dispersed domain sizes of the blends are reduced monotonously with the increment of the content of PP-PE. PP-PE has been demonstrated to be a more effective compatibilizer than EPC. Based on these results, it can be concluded that the tensile strength of the blends depends most on the adhesion between the two phases and the elongation at break depends most on the domain size of the dispersed component. (C) 1995 John Wiley & Sons, Inc.

RING-OPENING POLYMERIZATION OF TETRAHYDROFURAN WITH RARE EARTH-CONTAINED CATALYSTS

Rare earth trifluoroacetates, Ln(CF3CO2)(3) (Ln = thirteen rare earth elements), combined with R(n)AlH(3-n) (R = methyl, octyl, n = 3; R = ethyl, i-Butyl, n = 2, 3) were used as catalysts for the polymerization of tetrahydrofuran (THF). The activity increased by adding propylene oxide (PO), as a promoter, to the polymerization system, producing high molecular weight polytetrahydrofuran (PTHF). The effects of Ln, PO/Ln, and Al/Ln, and others on the polymerization of THF were also studied. (C) 1993 John Wiley & Sons, Inc.

STUDY ON THE RADIATION-INDUCED COPOLYMERIZATION OF ACRYLAMIDE WITH SODIUM ACRYLATE IN AQUEOUS-SOLUTION

In the present work, the mechanism of radiation-induced copolymerization of acrylamide (AM) with sodium acrylate (AANa) in aqueous solution was studied. A method to protect the copolymerization system from the crosslinking and a carbon-carbon mechanism to form gel in copolymerization reaction have been proposed. The condition to prepare the products with different molecular weight, especially with very high molecular weight were found.

STATISTICAL THERMODYNAMICS OF POLYDISPERSE POLYMERS

A statistical thermodynamics theory of polydisperse polymers based on a lattice model of fluids is formulated. Pure polydisperse polymer can be completely characterized by three scale factors and the molecular weight distribution of the system. The equation of state does not satisfy a simple corresponding-states principle, except for a polymer fluid of sufficiently high molecular weight. The relationships between thermal expansion coefficient alpha and isothermal compressibility beta with reduced variables are also predicted.

STATISTICAL THERMODYNAMICS OF A LATTICE FLUID - PURE POLYMER

A statistical thermodynamics theory of a polydisperse polymer based on a lattice model of a fluid is formulated. The pure polydisperse polymer is completely characterized by three scale factors and the distribution law of the system. The equation of state does not satisfy a simple corresponding state principle, except for the polymer fluid with sufficiently high molecular weight.

COMPARISON OF THE BEHAVIOR OF CYCLIC AND LINEAR POLYSTYRENE IN DILUTE-SOLUTION

Using a low angle laser light scattering photometer, the second virial coefficients (A2) of both cyclic and linear polystyrene were determined in cyclohexane, toluene and methyl ethyl ketone (MEK) solutions. From the data obtained in cyclohexane solution the theta-temperature of cyclic polystyrene was determined to be 30-degrees-C. In toluene solution A2 of cyclic polystyrene is smaller than that of linear polystyrene with the same molecular weight, but in MEK the values are similar.

One century record of contamination by polycyclic aromatic hydrocarbons and polychlorinated biphenyls in core sediments from the southern Yellow Sea

Sixteen polycyclic aromatic hydrocarbons (PAHs) and 28 polychlorinated biphenyls (PCBs) were measured at a 2-cm interval in a core sample from the middle of the southern Yellow Sea for elucidating their historical variations in inflow and sources. The chronology was obtained using the Pb-210 method. PAHs concentrations decreased generally with depth and two climax values occurred in 14-16 cm and 20-22 cm layers, demonstrating that the production and usage of PAHs might reach peaks in the periods of 1956-1962 and 1938-1944. The booming economy and the navy battles of the Second World War might explain why the higher levels were detected in the two layers. The result of principal component analysis (PCA) revealed that PAHs were primarily owing to the combustion product. Down-cored variation of PCB concentrations was complex. Higher concentrations besides the two peaks being the same as PAHs were detected from 4 to 8 cm, depositing from 1980 to 1992, which probably resulted from the disposal of the out-dated PCB-containing equipment. The average Cl percentage of PCBs detected was similar to that of the mixture of Aroclor 1254 and 1242, suggesting they might origin from the dielectrical and heat-transfer fluid. The total organic carbon (TOC) content played a prevalent role in the adsorption of high molecular weight PAHs (>= 4-ring), while no obvious relationship among total PCBs, the concentration of congeners, and TOC was found.

Preparation of 1,3,5-thiadiazine-2-thione derivatives of chitosan and their potential antioxidant activity in vitro

Three new kinds of 1,3,5-thiadiazine-2-thi one derivatives of chitosan with two different molecular weight (SATTCS1, SATTCS2, TITTCS1, TITTCS2, CITTCS1 and CITTCS2) have been prepared. Their structures were characterized by IR spectroscopy. The substitution degree of derivatives calculated by elemental analyses was 0.47, 0.42, 0.41, 0.38, 0.41 and 0.36, respectively. The result shows that substitution degree of derivatives was higher with lower molecular weight. The antioxidant activity was studied using an established system, such as bydroxyl radical scavenging, superoxide radical scavenging and reducing power. Antioxidant activity of the 1,3,5-thiadiazine-2-thione derivatives of chitosan were stronger than that of chitosans and antioxiclant activity of low molecular weight derivatives were stronger than that of high molecular weight derivatives. It is a potential antioxidant in vitro. (c) 2007 Elsevier Ltd. All rights reserved.

Simulation chamber studies of the atmospheric degradation of naphthalene, 1-nitronaphthalene and phthaldialdehyde

A detailed series of simulation chamber experiments has been performed on the atmospheric degradation pathways of the primary air pollutant naphthalene and two of its photooxidation products, phthaldialdehyde and 1-nitronaphthalene. The measured yields of secondary organic aerosol (SOA) arising from the photooxidation of naphthalene varied from 6-20%, depending on the concentrations of naphthalene and nitrogen oxides as well as relative humidity. A range of carbonyls, nitro-compounds, phenols and carboxylic acids were identified among the gas- and particle-phase products. On-line analysis of the chemical composition of naphthalene SOA was performed using aerosol time-of-flight mass spectrometry (ATOFMS) for the first time. The results indicate that enhanced formation of carboxylic acids may contribute to the observed increase in SOA yields at higher relative humidity. The photolysis of phthaldialdehyde and 1-nitronaphthalene was investigated using natural light at the European Photoreactor (EUPHORE) in Valencia, Spain. The photolysis rate coefficients were measured directly and used to confirm that photolysis is the major atmospheric loss process for these compounds. For phthaldialdehyde, the main gas-phase products were phthalide and phthalic anhydride. SOA yields in the range 2-11% were observed, with phthalic acid and dihydroxyphthalic acid identified among the particle phase products. The photolysis of 1-nitronaphthalene yielded nitric oxide and a naphthoxy radical which reacted to form several products. SOA yields in the range 57-71% were observed, with 1,4-naphthoquinone, 1-naphthol and 1,4-naphthalenediol identified in the particle phase. On-line analysis of the SOA generated in an indoor chamber using ATOFMS provided evidence for the formation of high-molecular-weight products. Further investigations revealed that these products are oxygenated polycyclic compounds most likely produced from the dimerization of naphthoxy radicals. These results of this work indicate that naphthalene is a potentially large source of SOA in urban areas and should be included in atmospheric models. The kinetic and mechanistic information could be combined with existing literature data to produce an overall degradation mechanism for naphthalene suitable for inclusion in photochemical models that are used to predict the effect of emissions on air quality.

Multivalent benzoboroxole functionalized polymers as gp120 glycan targeted microbicide entry inhibitors.

Microbicides are women-controlled prophylactics for sexually transmitted infections. The most important class of microbicides target HIV-1 and contain antiviral agents formulated for topical vaginal delivery. Identification of new viral entry inhibitors that target the HIV-1 envelope is important because they can inactivate HIV-1 in the vaginal lumen before virions can come in contact with CD4+ cells in the vaginal mucosa. Carbohydrate binding agents (CBAs) demonstrate the ability to act as entry inhibitors due to their ability to bind to glycans and prevent gp120 binding to CD4+ cells. However, as proteins they present significant challenges in regard to economical production and formulation for resource-poor environments. We have synthesized water-soluble polymer CBAs that contain multiple benzoboroxole moieties. A benzoboroxole-functionalized monomer was synthesized and incorporated into linear oligomers with 2-hydroxypropylmethacrylamide (HPMAm) at different feed ratios using free radical polymerization. The benzoboroxole small molecule analogue demonstrated weak affinity for HIV-1BaL gp120 by SPR; however, the 25 mol % functionalized benzoboroxole oligomer demonstrated a 10-fold decrease in the K(D) for gp120, suggesting an increased avidity for the multivalent polymer construct. High molecular weight polymers functionalized with 25, 50, and 75 mol % benzoboroxole were synthesized and tested for their ability to neutralize HIV-1 entry for two HIV-1 clades and both R5 and X4 coreceptor tropism. All three polymers demonstrated activity against all viral strains tested with EC(50)s that decrease from 15000 nM (1500 microg mL(-1)) for the 25 mol % functionalized polymers to 11 nM (1 microg mL(-1)) for the 75 mol % benzoboroxole-functionalized polymers. These polymers exhibited minimal cytotoxicity after 24 h exposure to a human vaginal cell line.

The Haemophilus influenzae HMW1C protein is a glycosyltransferase that transfers hexose residues to asparagine sites in the HMW1 adhesin.

The Haemophilus influenzae HMW1 adhesin is a high-molecular weight protein that is secreted by the bacterial two-partner secretion pathway and mediates adherence to respiratory epithelium, an essential early step in the pathogenesis of H. influenzae disease. In recent work, we discovered that HMW1 is a glycoprotein and undergoes N-linked glycosylation at multiple asparagine residues with simple hexose units rather than N-acetylated hexose units, revealing an unusual N-glycosidic linkage and suggesting a new glycosyltransferase activity. Glycosylation protects HMW1 against premature degradation during the process of secretion and facilitates HMW1 tethering to the bacterial surface, a prerequisite for HMW1-mediated adherence. In the current study, we establish that the enzyme responsible for glycosylation of HMW1 is a protein called HMW1C, which is encoded by the hmw1 gene cluster and shares homology with a group of bacterial proteins that are generally associated with two-partner secretion systems. In addition, we demonstrate that HMW1C is capable of transferring glucose and galactose to HMW1 and is also able to generate hexose-hexose bonds. Our results define a new family of bacterial glycosyltransferases.

IN SITU AND IN VITRO IMMUNOLOCALIZATION OF OVIDUCTIN BINDING SITES ON HAMSTER UTERINE EPITHELIAL CELLS AND DETECTION OF A HAMSTER OVIDUCTIN HOMOLOGUE IN THE FEMALE RAT REPRODUCTIVE TRACT

Oviductin is an oviduct-specific and high-molecular-weight glycoprotein that has been suggested to play important roles in the early events of reproduction. The present study was undertaken to localize the oviductin binding sites in the uterine epithelial cells of the golden hamster (Mesocricetus auratus) both in situ and in vitro, and to detect a hamster oviductin homologue in the female rat reproductive tract. Immunohistochemical localization of oviductin in the hamster uterus revealed certain uterine epithelial cells reactive to the monoclonal anti-hamster oviductin antibody. In order to study the interaction between hamster oviductin and the endometrium in vitro, a method for culturing primary hamster uterine epithelial cells has been established and optimized. Study with confocal microscopy of the cell culture system showed a labeling pattern similar to what was observed using immunohistochemistry. Pre-embedding immunolabeling of cultured uterine epithelial cells also showed gold particles associated with the plasma membrane and microvilli. These results demonstrated that hamster oviductin can bind to the plasma membrane of certain hamster uterine epithelial cells, suggesting the presence of a putative oviductin receptor on the uterine epithelial cell surface. In the second part of the present study, using the monoclonal anti-hamster oviductin antibody that cross-reacts with the rat tissue, we have been able to detect an oviduct-specific glycoprotein, with a molecular weight of 180~300kDa, in the female rat reproductive tract. Immunohistochemical labeling of the female rat reproductive tract revealed a strong immunolabeling in the non-ciliated oviductal epithelial cells and a faint immunoreaction on the cell surface of some uterine epithelial cells. Ultrastructurally, immunogold labeling was restricted to the secretory granules, Golgi apparatus, and microvilli of the non-ciliated secretory cells of the oviduct. In the uterus, immunogold labeling was observed on the cell surface of some uterine epithelial cells. Furthermore, electron micrographs of ovulated oocytes showed an intense immunolabeling for rat oviductin within the perivitelline space surrounding the ovulated oocytes. The findings of the present study demonstrated that oviductin is present in the rat oviduct and uterus, and it appears that, in the rat, oviductin is secreted by the non-ciliated secretory cells of the oviduct.