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Sample records for 4-phenylethynylphthalic anhydride pepa

  1. Characterization of the Structure-Processing-Performance Relations of Phenylethynyl Phthalic Anhydride Crosslinked Fluorinated Polyimides (AFR-PEPA-N) and Their Carbon Fiber Composites

    DTIC Science & Technology

    2007-04-12

    FA9550-04-1-0137 Relations of Phenylethynyl Phthalic Anhydride Crosslinked Fluorinated Polyimides (AFR-PEPA-N) and Their Carbon Fiber Composites 5b. GRANT...structure-processing-performance relations of phenylethynyl phthatic anhydride crosslinked fluorinated polyimides (AFR-PEPA-N) and their carbon fiber...composites for applications for future Air Force vehicles and associated propulsion systems . The technical areas that were primarily pursued and

  2. Phenylethynyl Phthalic Anhydride

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Smith, Joseph G., Jr. (Inventor)

    1997-01-01

    Controlled molecular weight PhenylEthynyl Terminated Imide oligomers (PETIs) have been prepared by the cyclodehydration of precursor phenylethynyl terminated amic acid oligomers. Amino terminated amic acid oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and subsequently endcapped with PhenylEthynyl Phthalic Anhydride(s) (PEPA). The polymerizations are carried out in polar aprotic solvents such as N-methyl-2pyrrolidinone or N N-dimethylacetamide under nitrogen at room temperature. The amic acid oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. Direct preparation of PETIs from the reaction of dianhydride(s) with an excess of diamine(s) and endcapped with phenylethynyl phthalic anhydride(s) has been performed in m-cresol. Phenylethynyl phthalic anhydrides are synthesized by the palladium catalyzed reaction of phenylacetylene with bromo substituted phthalic anhydrides in triethylamine. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

  3. Low Viscosity Imides Based on Asymmetric Oxydiphthalic Anhydride

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Criss, Jim M., Jr.; Mintz, Eric A.; Scheiman, Daniel A.; Nguyen, Baochau N.; McCorkle, Linda S.

    2008-01-01

    A series of low-melt viscosity imide resins were prepared from asymmetric oxydiphthalic dianhydride (a-ODPA) and 4-phenylethynylphthalic anhydride as the endcap, along with 3,4' - oxydianiline (3,4' -ODA), 3,4' -methylenedianiline (3,4' -MDA), 3,3' -methylenedianiline (3,3' - MDA) and 3,3'-diaminobenzophenone (3,3'-DABP), using a solvent-free melt process. These imide oligomers displays low-melt viscosities (2-15 poise) at 260-280 C, which made them amenable to low-cost resin transfer molding (RTM) process. The a-ODPA based RTM resins exhibits glass transition temperatures (Tg's) in the range of 265-330 C after postcure at 343 C. The mechanical properties of these polyimide/carbon fiber composites fabricated by RTM will be discussed.

  4. Maleic anhydride

    Integrated Risk Information System (IRIS)

    Maleic anhydride ; CASRN 108 - 31 - 6 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  5. Phthalic anhydride

    Integrated Risk Information System (IRIS)

    Phthalic anhydride ; CASRN 85 - 44 - 9 Human health assessment information on a chemical substance is included in the IRIS database only after a comprehensive review of toxicity data , as outlined in the IRIS assessment development process . Sections I ( Health Hazard Assessments for Noncarcinogenic

  6. Imide Oligomers Endcapped with Phenylethynl Phthalic Anhydrides and Polymers Therefrom

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Smith, Joseph G., Jr. (Inventor)

    1998-01-01

    Controlled molecular weight phenylethynyl terminated imide oligomers (PETIs) have been prepared by the cyclodehydration of precursor phenylethynyl terminated amic acid oligomers. Amino terminated amic acid oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and subsequently endcapped with phenylethynyl phthalic anhydride(s) (PEPA). The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N.N-dimethylacetamide under nitrogen at room temperature. The amic acid oligomers are subsequently cyclodehydrated either thermally or cheznicauy to the corresponding imide oligomers. Direct preparation of PETIs from the reaction of dianhydxide(s) with an excess of diamine(s) and endcapped with phenylethynyl phthalic anhydride(s) has been performed in m-cresol. Phenylethynyl phthalic anhydrides are synthesized by the palladium catalyzed reaction of phenylacetylene with bromo substituted phthalic anhydrides in triethylamine. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

  7. Imide oligomers endcapped with phenylethynyl phthalic anhydrides and polymers therefrom

    NASA Technical Reports Server (NTRS)

    Hergenrother, Paul M. (Inventor); Smith, Jr., Joseph G. (Inventor)

    1996-01-01

    Controlled molecular weight phenylethynyl terminated imide oligomers (PETIs) have been prepared by the cyclodehydration of precursor phenylethynyl terminated amic acid oligomers. Amino terminated amic acid oligomers are prepared from the reaction of dianhydride(s) with an excess of diamine(s) and subsequently endcapped with phenylethynyl phthalic anhydride(s) (PEPA). The polymerizations are carried out in polar aprotic solvents such as N-methyl-2-pyrrolidinone or N,N-dimethylacetamide under nitrogen at room temperature. The amic acid oligomers are subsequently cyclodehydrated either thermally or chemically to the corresponding imide oligomers. Direct preparation of PETIs from the reaction of dianhydride(s) with an excess of diamine(s) and endcapped with phenylethynyl phthalic anhydride(s) has been performed in m-cresol. Phenylethynyl phthalic anhydrides are synthesized by the palladium catalyzed reaction of phenylacetylene with bromo substituted phthalic anhydrides in triethylamine. These new materials exhibit excellent properties and are potentially useful as adhesives, coatings, films, moldings and composite matrices.

  8. PEPA-1* genotype affects return rate for hatchery steelhead

    USGS Publications Warehouse

    Reisenbichler, R.R.; Hayes, M.C.; Rubin, S.P.; Wetzel, L.A.; Baker, B.M.

    2006-01-01

    Allozymes continue to be useful as genetic markers in a variety of studies; however, their utility often hinges on the selective neutrality of the allelic variation. Our study tested for neutrality between the two most common alleles (*100 and *110) at the cytosol nonspecific dipeptidase locus (PEPA-1*) in steelhead Oncorhynchus mykiss from Dworshak National Fish Hatchery in Idaho. We tested for differential growth and survival among fish with the * 100/100, *100/ 110, and *110/110 genotypes rearing in a hatchery or a natural stream. We repeated the study for two year-classes, using heterozygous (*100/110) adults to make the experimental crosses. This design avoided differences in family contribution among genotypes because each cross produced all three genotypes. We divided the progeny from each family into two groups. One group was reared in a hatchery for 1 year and then released for migration to the sea and subsequent return to the hatchery as adults. The other group was released into a natural stream and monitored for 3 years. We found no significant differences in size or survival among PEPA-1* genotypes for either the naturally reared fish or the hatchery-reared fish immediately prior to release as smolts. For females, survival to returning adult also was similar among genotypes; however, hatchery-reared males with the *110/110 genotype returned at a higher rate than did males with the *100/ 100 genotype; heterozygous males were intermediate. These results indicate that selection occurs at the PEPA-1* locus or at one or more loci tightly linked to it. The finding of nearly equal frequencies for these two alleles in the source population suggests that selection differentials among genotypes reverse or vary from year to year; otherwise, steady directional selection would drive the *100 allele to low frequencies or extinction. Locus PEPA-1* seems inappropriate for genetic marks in studies of steelhead that span the full life cycle and probably should be avoided

  9. Novel PEPA-functionalized graphene oxide for fire safety enhancement of polypropylene

    PubMed Central

    Xu, Jia You; Liu, Jie; Li, Kai Dan; Tanemura, Sakae

    2015-01-01

    Polypropylene (PP) is a general-purpose plastic, but some applications are constrained by its high flammability. Thus, flame retardant PP is urgently demanded. In this article, intumescent flame retardant PP (IFRPP) composites with enhanced fire safety were prepared using 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (PEPA) functionalized graphene oxide (PGO) as synergist. The PGO was prepared through a mild chemical reaction by the covalent attachment of a caged-structure organic compound, PEPA, onto GO nanosheets using toluene diisocynate (TDI) as the intermediary agent. The novel PEPA-functionalized graphene oxide not only improves the heat resistance of GO but also converts GO and PEPA from hydrophobic to hydrophilic materials, which leads to even distribution in PP. In our case, 7 wt% addition of PGO as one of the fillers for IFRPP composites significantly reduces its inflammability and fire hazards when compared with PEPA, by the improvement of first release rate peak (PHRR), total heat release, first smoke release rate peak (PSRR) and total smoke release, suggesting its great potential as the IFR synergist in industry. The reason is mainly attributed to the barrier effect of the unburned graphene sheets, which protects by the decomposition products of PEPA and TDI, promotes the formation of graphitized carbon and inhibits the heat and gas release. PMID:27877775

  10. Novel PEPA-functionalized graphene oxide for fire safety enhancement of polypropylene.

    PubMed

    Xu, Jia You; Liu, Jie; Li, Kai Dan; Miao, Lei; Tanemura, Sakae

    2015-04-01

    Polypropylene (PP) is a general-purpose plastic, but some applications are constrained by its high flammability. Thus, flame retardant PP is urgently demanded. In this article, intumescent flame retardant PP (IFRPP) composites with enhanced fire safety were prepared using 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (PEPA) functionalized graphene oxide (PGO) as synergist. The PGO was prepared through a mild chemical reaction by the covalent attachment of a caged-structure organic compound, PEPA, onto GO nanosheets using toluene diisocynate (TDI) as the intermediary agent. The novel PEPA-functionalized graphene oxide not only improves the heat resistance of GO but also converts GO and PEPA from hydrophobic to hydrophilic materials, which leads to even distribution in PP. In our case, 7 wt% addition of PGO as one of the fillers for IFRPP composites significantly reduces its inflammability and fire hazards when compared with PEPA, by the improvement of first release rate peak (PHRR), total heat release, first smoke release rate peak (PSRR) and total smoke release, suggesting its great potential as the IFR synergist in industry. The reason is mainly attributed to the barrier effect of the unburned graphene sheets, which protects by the decomposition products of PEPA and TDI, promotes the formation of graphitized carbon and inhibits the heat and gas release.

  11. Novel PEPA-functionalized graphene oxide for fire safety enhancement of polypropylene

    NASA Astrophysics Data System (ADS)

    You Xu, Jia; Liu, Jie; Li, Kai Dan; Miao, Lei; Tanemura, Sakae

    2015-04-01

    Polypropylene (PP) is a general-purpose plastic, but some applications are constrained by its high flammability. Thus, flame retardant PP is urgently demanded. In this article, intumescent flame retardant PP (IFRPP) composites with enhanced fire safety were prepared using 1-oxo-4-hydroxymethyl-2,6,7-trioxa-1-phosphabicyclo [2.2.2] octane (PEPA) functionalized graphene oxide (PGO) as synergist. The PGO was prepared through a mild chemical reaction by the covalent attachment of a caged-structure organic compound, PEPA, onto GO nanosheets using toluene diisocynate (TDI) as the intermediary agent. The novel PEPA-functionalized graphene oxide not only improves the heat resistance of GO but also converts GO and PEPA from hydrophobic to hydrophilic materials, which leads to even distribution in PP. In our case, 7 wt% addition of PGO as one of the fillers for IFRPP composites significantly reduces its inflammability and fire hazards when compared with PEPA, by the improvement of first release rate peak (PHRR), total heat release, first smoke release rate peak (PSRR) and total smoke release, suggesting its great potential as the IFR synergist in industry. The reason is mainly attributed to the barrier effect of the unburned graphene sheets, which protects by the decomposition products of PEPA and TDI, promotes the formation of graphitized carbon and inhibits the heat and gas release.

  12. Isomeric oxydiphthalic anhydride polyimides

    NASA Technical Reports Server (NTRS)

    Gerber, Margaret K.; Pratt, J. Richard; Stclair, Terry L.

    1988-01-01

    Much of the polyimide research at Langley Research Center has focused on isomeric modification of the diamine component; polyimides having considerably improved processability and adhesion have resulted. The present structure-property study was designed to investigate how isomeric attachment of the three oxydiphthalic anhydride (ODPA) polyimides affects their properties. Each dianhydride, 3,4,3',4'-oxydiphthalic anhydride (4,4'-OPDA,I), 2,3,2',3'-oxydiphthalic anhydride (3,3'-ODPA,II), and 2,3,3',4'-oxydiphthalic anhydride (3,4'-OPDA,III), was reacted with p-phenylenediamine, 4,4'-oxydianiline, 3,3'-diaminodiphenylsulfone, 3,3'-diaminobenzophenone, and 4,4'-bis(3-aminophenoxy)benzophenone in DMAc. The inherent viscosities of the resulting poly(amic acids) were determined. Thermally imidized films were studied for their creasability and solubility, as well as by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA) and wide angle X-ray scattering (WAXS). A comparison of these properties will be made.

  13. Succinic anhydrides from epoxides

    DOEpatents

    Coates, Geoffrey W.; Rowley, John M.

    2013-07-09

    Catalysts and methods for the double carbonylation of epoxides are disclosed. Each epoxide molecule reacts with two molecules of carbon monoxide to produce a succinic anhydride. The reaction is facilitated by catalysts combining a Lewis acidic species with a transition metal carbonyl complex. The double carbonylation is achieved in single process by using reaction conditions under which both carbonylation reactions occur without the necessity of isolating or purifying the product of the first carbonylation.

  14. Unexpected Diversity of pepA Genes Encoding Leucine Aminopeptidases in Sediments from a Freshwater Lake

    PubMed Central

    Tsuboi, Shun; Yamamura, Shigeki; Imai, Akio; Iwasaki, Kazuhiro

    2016-01-01

    We herein designed novel PCR primers for universal detection of the pepA gene, which encodes the representative leucine aminopeptidase gene, and investigated the genetic characteristics and diversity of pepA genes in sediments of hypereutrophic Lake Kasumigaura, Japan. Most of the amino acid sequences deduced from the obtained clones (369 out of 370) were related to PepA-like protein sequences in the M17 family of proteins. The developed primers broadly detected pepA-like clones associated with diverse bacterial phyla—Alpha-, Beta-, Gamma-, and Deltaproteobacteria, Acidobacteria, Actinobacteria, Aquificae, Chlamydiae, Chloroflexi, Cyanobacteria, Firmicutes, Nitrospirae, Planctomycetes, and Spirochetes as well as the archaeal phylum Thaumarchaeota, indicating that prokaryotes in aquatic environments possessing leucine aminopeptidase are more diverse than previously reported. Moreover, prokaryotes related to the obtained pepA-like clones appeared to be r- and K-strategists, which was in contrast to our previous findings showing that the neutral metalloprotease gene clones obtained were related to the r-strategist genus Bacillus. Our results suggest that an unprecedented diversity of prokaryotes with a combination of different proteases participate in sedimentary proteolysis. PMID:26936797

  15. Unexpected Diversity of pepA Genes Encoding Leucine Aminopeptidases in Sediments from a Freshwater Lake.

    PubMed

    Tsuboi, Shun; Yamamura, Shigeki; Imai, Akio; Iwasaki, Kazuhiro

    2016-01-01

    We herein designed novel PCR primers for universal detection of the pepA gene, which encodes the representative leucine aminopeptidase gene, and investigated the genetic characteristics and diversity of pepA genes in sediments of hypereutrophic Lake Kasumigaura, Japan. Most of the amino acid sequences deduced from the obtained clones (369 out of 370) were related to PepA-like protein sequences in the M17 family of proteins. The developed primers broadly detected pepA-like clones associated with diverse bacterial phyla-Alpha-, Beta-, Gamma-, and Deltaproteobacteria, Acidobacteria, Actinobacteria, Aquificae, Chlamydiae, Chloroflexi, Cyanobacteria, Firmicutes, Nitrospirae, Planctomycetes, and Spirochetes as well as the archaeal phylum Thaumarchaeota, indicating that prokaryotes in aquatic environments possessing leucine aminopeptidase are more diverse than previously reported. Moreover, prokaryotes related to the obtained pepA-like clones appeared to be r- and K-strategists, which was in contrast to our previous findings showing that the neutral metalloprotease gene clones obtained were related to the r-strategist genus Bacillus. Our results suggest that an unprecedented diversity of prokaryotes with a combination of different proteases participate in sedimentary proteolysis.

  16. Maleic anhydride from normal butane

    SciTech Connect

    Cooley, S.D.; Doshi, B.

    1987-01-01

    Worldwide about one billion pounds of maleic anhydride is used annually in the manufacture of a number of commercially valuable products, including unsaturated polyester resins, agricultural chemicals, and lubricating oil additives. Maleic anhydride is not found in nature. It was first prepared in 1834 by heating malic acid (hydroxy-succinic acid, a compound found in apples and many other fruits). Maleic anhydride was not available commercially until ca. 1930 when the catalytic air oxidation of benzene was begun by National Aniline and Chemical on an industrial scale. The estimated worldwide production in 1985 was 1023 million pounds coming from more than 35 plants varying in capacity from 6 million pounds to 170 million pounds annually.

  17. Positional Enrichment by Proton Analysis (PEPA): A One-Dimensional (1) H-NMR Approach for (13) C Stable Isotope Tracer Studies in Metabolomics.

    PubMed

    Vinaixa, Maria; Rodríguez, Miguel A; Aivio, Suvi; Capellades, Jordi; Gómez, Josep; Canyellas, Nicolau; Stracker, Travis H; Yanes, Oscar

    2017-03-20

    A novel metabolomics approach for NMR-based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of (13) C-satellite peaks using 1D-(1) H-NMR spectra. In comparison with (13) C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of (13) C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high-throughput of (1) H-NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D-NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts.

  18. Positional Enrichment by Proton Analysis (PEPA): A One‐Dimensional 1H‐NMR Approach for 13C Stable Isotope Tracer Studies in Metabolomics

    PubMed Central

    Rodríguez, Miguel A.; Aivio, Suvi; Capellades, Jordi; Gómez, Josep; Canyellas, Nicolau; Stracker, Travis H.

    2017-01-01

    Abstract A novel metabolomics approach for NMR‐based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of 13C‐satellite peaks using 1D‐1H‐NMR spectra. In comparison with 13C‐NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of 13C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high‐throughput of 1H‐NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D‐NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts. PMID:28220994

  19. 21 CFR 177.1820 - Styrene-maleic anhydride copolymers.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ... maleic anhydride monomer content. Residual maleic anhydride monomer content shall be determined by a gas chromatographic method titled “Determination of Residual Maleic Anhydride in Polymers by Gas...

  20. Solvent free low-melt viscosity imide oligomers and thermosetting polymide composites

    NASA Technical Reports Server (NTRS)

    Chuang, Chun-Hua (Inventor)

    2012-01-01

    .[.This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280.degree. C. When the imide oligomer melt is cured at about 371.degree. C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T.sub.g) equal to and above 310.degree. C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280.degree. C. (450-535.degree. F.) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343.degree. C. (550-650.degree. F.) high temperature performance capability..]. .Iadd.This invention relates to compositions and a solvent-free reaction process for preparing imide oligomers and polymers specifically derived from effective amounts of dianhydrides such as 2,3,3',4'-biphenyltetracarboxylic dianhydride (a-BPDA), at least one aromatic polyamine and an end-cap such as 4-phenylethynyphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260.degree. C.-280.degree. C..Iaddend.

  1. The novel silicon-containing epoxy/PEPA phosphate flame retardant for transparent intumescent fire resistant coating

    NASA Astrophysics Data System (ADS)

    Shi, Yanchao; Wang, Guojian

    2016-11-01

    A series of novel silicon-containing epoxy/PEPA phosphate flame retardants (EPPSi) were synthesized by polyphosphoric acid (PPA), caged bicyclic phosphate 1-oxo-4-hydroxymethyl-2,6,7-trioxa-L-phosphabicyclo [2.2.2] octane (PEPA), and different ratios of silicon-containing epoxy 1,1,3,3-tetramethyl-1,3-bis(3-(oxiran-2-ylmethoxy)propyl)disiloxane (TMSEP) to 1,4-butanediol diglycidyl ether (BDE). The chemical structure of EPPSi was confirmed by Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance spectroscopy (1H NMR). Afterwards, the transparent intumescent fire resistant coatings were prepared by mixing EPPSi and melamine formaldehyde resin. The influence of silicon on the fire protection of coatings was intensively investigated by fire protection test, intumescence ratio, scanning electron microscope (SEM), compressive strength test, X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA) and real-time FTIR. It was found that the fire resistant coatings obtained the best fire protection when the ratio of TMESP/BDE was 20/100, while excessive TMSEP made the fire protection of coatings deceased sharply. The intumescence ratio, compressive strength test and SEM result showed that a synergistic effect existed between phosphorus and silicon, which improved the foam structure and compressive strength of the char layer significantly. XPS result proved the out-migration effect of silicon. The high concentration silicon on surface played an important protecting role for the inner char residue and improved the fire protection of the coatings. TGA result demonstrated that silicon enhanced the thermo-oxidation resistance of coatings efficiently. Furthermore, real-time FTIR revealed the intumescent process of the fire resistant coatings according to the chemical structure changes of char residue.

  2. 21 CFR 177.1820 - Styrene-maleic anhydride copolymers.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... maleic anhydride monomer content shall be determined by a gas chromatographic method titled “Determination of Residual Maleic Anhydride in Polymers by Gas Chromatography,” which is incorporated...

  3. 21 CFR 177.1820 - Styrene-maleic anhydride copolymers.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... maleic anhydride monomer content shall be determined by a gas chromatographic method titled “Determination of Residual Maleic Anhydride in Polymers by Gas Chromatography,” which is incorporated...

  4. 21 CFR 177.1820 - Styrene-maleic anhydride copolymers.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... maleic anhydride monomer content shall be determined by a gas chromatographic method titled “Determination of Residual Maleic Anhydride in Polymers by Gas Chromatography,” which is incorporated...

  5. 21 CFR 177.1820 - Styrene-maleic anhydride copolymers.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... 21 Food and Drugs 3 2011-04-01 2011-04-01 false Styrene-maleic anhydride copolymers. 177.1820... Basic Components of Single and Repeated Use Food Contact Surfaces § 177.1820 Styrene-maleic anhydride copolymers. Styrene-maleic anhydride copolymers identified in paragraph (a) of this section may be...

  6. Improved zein articles using polyethylenemaleic anhydride

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Developing corn protein (zein) articles with improved physical properties and solvent resistance will have a beneficial impact on companies that use corn. The effect of using the crosslinking reagent polyethylenemaleic anhydride (PEMA) on the properties and solubility of zein articles were studied. ...

  7. Cloning, expression, crystallization and preliminary X-ray crystallographic analysis of leucine aminopeptidase (LAP) from the pepA gene of Xanthomonas oryzae pv. oryzae.

    PubMed

    Huynh, Kim-Hung; Natarajan, Sampath; Choi, Jeongyoon; Song, Na-Hyun; Kim, Jeong-Gu; Lee, Byoung-Moo; Ahn, Yeh-Jin; Kang, Lin-Woo

    2009-09-01

    Xanthomonas oryzae pv. oryzae (Xoo) causes the serious disease bacterial blight in rice. The pepA (Xoo0834) gene from Xoo is one of around 100 genes that have been selected for the design of antibacterial drugs. The pepA gene encodes leucine aminopeptidase (LAP), an exopeptidase that catalyzes the hydrolysis of leucine residues from the N-terminus of a protein or peptide. This enzyme was expressed in Escherichia coli, purified and crystallized, and preliminary X-ray structural studies have been carried out. The LAP crystal diffracted to 2.6 A resolution and belonged to the cubic space group P2(1)3. The unit-cell volume of the crystal was compatible with the presence of two monomers in the asymmetric unit.

  8. Preparation of poly(glycidylmethacrylate-divinylbenzene) weak acid cation exchange stationary phases with succinic anhydride, phthalic anhydride, and maleic anhydride for ion chromatography.

    PubMed

    Liu, Junwei; Wang, Yong; Wu, Shuchao; Zhang, Peimin; Zhu, Yan

    2016-08-01

    In this work, poly(glycidylmethacrylate-divinylbenzene) microspheres were prepared and applied for the preparation of weak acid cation exchange stationary phases. Succinic anhydride, phthalic anhydride, and maleic anhydride were selected as carboxylation reagents to prepare three weak acid cation exchangers by direct chemical derivatization reaction without solvent or catalyst. The diameters and dispersity of the microspheres were characterized by scanning electron microscopy; the amount of accessible epoxy groups and mechanical stability were also measured. The weak acid cation exchangers were characterized by Fourier transform infrared spectroscopy; the content of carboxyl groups was measured by traditional acid base titration method. The chromatographic properties were characterized and compared by separating alkali, alkaline earth metal ions and ammonium and polar amines. The separation properties enhanced in the order of succinic anhydride, phthalic anhydride, and maleic anhydride modified poly(glycidylmethacrylate-divinylbenzene) cation exchangers.

  9. Dicarboxylic acid anhydride condensation with compounds containing active methylene groups. 4: Some 4-nitrophthalic anhydride condensation reactions

    NASA Technical Reports Server (NTRS)

    Oskaja, V.; Rotberg, J.

    1985-01-01

    By 4-nitrophthalic anhydride condensation with acetoacetate in acetic anhydride and triethylamine solution with subsequent breakdown of the intermediate condensation product, 5-nitroindanedione-1,3 was obtained. A 4-nitrophthalic anhydride with acetic anhydride, according to reaction conditions, may yield two products: in the presence of potassium acetate and at high temperatures 4-(or 5-)-nitro-2-acetylbenzoic acid is formed: in the presence of triethylamine and at room temperature 5-( or 6-)-nitrophthalic acetic acid is isolated. A 4-nitrophthalic anhydride and malonic acid in pyridine solution according to temperature yield either 5-( or 6-)-nitrophthalic acetic acid or 4-(or 5-)-nitro-2-acetylbenzoic acid.

  10. Solvent Free Low-Melt Viscosity Imide Oligomers And Thermosetting Polyimide Composites

    NASA Technical Reports Server (NTRS)

    Chuang, CHun-Hua (Inventor)

    2006-01-01

    This invention relates to the composition and a solvent-free process for preparing novel imide oligomers and polymers specifically formulated with effective amounts of a dianhydride such as 2,3,3',4-biphenyltetra carboxylic dianydride (a-BPDA), at least one aromatic diamine' and an endcapped of 4-phenylethynylphthalic anhydride (PEPA) or nadic anhydride to produce imide oligomers that possess a low-melt viscosity of 1-60 poise at 260-280" C. When the imide oligomer melt is cured at about 371 C. in a press or autoclave under 100-500 psi, the melt resulted in a thermoset polyimide having a glass transition temperature (T(sub g)) equal to and above 310 C. A novel feature of this process is that the monomers; namely the dianhydrides, diamines and the endcaps, are melt processable to form imide oligomers at temperatures ranging between 232-280 C. (450-535 F) without any solvent. These low-melt imide oligomers can be easily processed by resin transfer molding (RTM), vacuum-assisted resin transfer molding (VARTM) or the resin infusion process with fiber preforms e.g. carbon, glass or quartz preforms to produce polyimide matrix composites with 288-343C (550-650 F) high temperature performance capability.

  11. Condensation of anhydrides or dicarboxylic acids with compounds containing active methylene groups. Part 19: Condensation of phthalic and substituted phthalic anhydrides with benzoylacetic ester

    NASA Technical Reports Server (NTRS)

    Rotberg, Y. T.; Oshkaya, V. P.

    1985-01-01

    Phthalylbenzoylacetic ester and its nitro and halogen derivatives were prepared through condensation of phthalic anhydride, nitrophthalic anhydride, and phthalic halide anhydride with benzoylacetic ester in a solution of acetic anhydride and triethylamine. The condensation of hemipinic acid anhydride proceeds similarly, but under more drastic conditions. Derivatives of indan-1,3-dione are also formed, with a small yield, in the reaction of nitrophthalic anhydrides with benzoylacetic ester in the presence of increased quantities of triethylamine.

  12. Chemicals from coal - The Eastman experience. [Anhydride

    SciTech Connect

    Larkins, T.H.

    1986-03-01

    Tennessee Eastman Company is a major producer of chemicals, fibers and plastics. It is located in Kingsport, Tennessee, headquarters for the Eastman Chemicals Division of Eastman Kodak Company. Eastman Companies employ a total of 12,250 people in Kingsport. Other domestic Eastman Chemicals Division plants are located in Texas, South Carolina, Arkansas and New York. The authors began to witness a flow of products from one of the most highly technical and sophisticated chemical processes in operation in the world. The Eastman ''Chemicals-from-Coal'' facility is not a sunfuel plant. To be sure, we are producing syngas from coal, but the syngas is used to produce acetic anhydride. Acetic anhydride is very important to Eastman. This chemical intermediate eventually finds its way into such diverse products as aspirin, cigarette filters, tool handles, and photographic film. It also is used to make other chemical intermediates such as cellulose esters, anhydrides, triacetin, and acetate ester solvents, all of which have a variety of end uses. The chemicals-from-coal project had its inception in the late 1960's when Eastman stepped up its program of energy conservation and began a search for lower cost chemical feedstocks. Our concern started before the national concern caused by a ten-fold increase in petroleum prices during the past decade.

  13. Optimize energy usage in phthalic anhydride units

    SciTech Connect

    de Virgiliis, A.; Gerunda, A.

    1982-05-01

    By maximizing the air to o-xylene ratios, Ftalital has developed a phthalic anhydride (PA) unit completely energy self-sufficient, generating its own electric power without affecting export steam. In the improved version of the production schemes a single-train synthesis reactors with 15,500 tubes each are used. These reactors have a production capacity of 35,000 metric tpy each and have operated with catalyst developed for high o-xylene-to-air ratios. Economic considerations are included.

  14. 78 FR 76567 - Tall Oil, Polymer With Polyethylene Glycol and Succinic Anhydride Monopolyisobutylene Derivs...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-12-18

    ... AGENCY 40 CFR Part 180 Tall Oil, Polymer With Polyethylene Glycol and Succinic Anhydride... oil, polymer with polyethylene glycol and succinic anhydride monopolyisobutylene derivs. (CAS Reg. No... residues of tall oil, polymer with polyethylene glycol and succinic anhydride monopolyisobutylene...

  15. Preparation of .alpha., .beta.-unsaturated carboxylic acids and anhydrides

    DOEpatents

    Spivey, James Jerry; Gogate, Makarand Ratnakav; Zoeller, Joseph Robert; Tustin, Gerald Charles

    1998-01-01

    Disclosed is a process for the preparation of .alpha.,.beta.-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

  16. Preparation of {alpha}, {beta}-unsaturated carboxylic acids and anhydrides

    DOEpatents

    Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Tustin, G.C.

    1998-01-20

    Disclosed is a process for the preparation of {alpha},{beta}-unsaturated carboxylic acids and anhydrides thereof which comprises contacting formaldehyde or a source of formaldehyde with a carboxylic anhydride in the presence of a catalyst comprising mixed oxides of vanadium, phosphorus and, optionally, a third component selected from titanium, aluminum or, preferably silicon.

  17. Synthesis and Characterization of Poly(maleic Anhydride)s Cross-linked Polyimide Aerogels

    NASA Technical Reports Server (NTRS)

    Guo, Haiquan; Meador, Mary Ann B.

    2015-01-01

    With the development of technology for aerospace applications, new thermal insulation materials are required to be flexible and capable of surviving high heat flux. For instance, flexible insulation is needed for inflatable aerodynamic decelerators which are used to slow spacecraft for entry, descent and landing (EDL) operations. Polyimide aerogels have low density, high porosity, high surface area, and better mechanical properties than silica aerogels and can be made into flexible thin films, thus they are potential candidates for aerospace needs. The previously reported cross-linkers such as octa(aminophenyl)silsesquioxane (OAPS) and 1,3,5-triaminophenoxybenzene (TAB) are either expensive or not commercially available. Here, we report the synthesis of a series of polyimide aerogels cross-linked using various commercially available poly(maleic anhydride)s, as seen in Figure 1. The amine end capped polyimide oligomers were made with 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA) and diamine combinations of dimethylbenzidine (DMBZ) and 4, 4-oxydianiline (ODA). The resulting aerogels have low density (0.12 gcm3 to 0.16 gcm3), high porosity (90) and high surface area (380-554 m2g). The effect of the different poly(maleic anhydride) cross-linkers and polyimide backbone structures on density, shrinkage, porosity, surface area, mechanical properties, moisture resistance and thermal properties will be discussed.

  18. PETIs as High-Temperature Resin-Transfer-Molding Materials

    NASA Technical Reports Server (NTRS)

    Connell, John N.; Smith, Joseph G., Jr.; Hergenrother, Paul M.

    2005-01-01

    Compositions of, and processes for fabricating, high-temperature composite materials from phenylethynyl-terminated imide (PETI) oligomers by resin-transfer molding (RTM) and resin infusion have been developed. Composites having a combination of excellent mechanical properties and long-term high-temperature stability have been readily fabricated. These materials are particularly useful for the fabrication of high-temperature structures for jet-engine components, structural components on highspeed aircraft, spacecraft, and missiles. Phenylethynyl-terminated amide acid oligomers that are precursors of PETI oligomers are easily made through the reaction of a mixture of aromatic diamines with aromatic dianhydrides at high stoichiometric offsets and 4-phenylethynylphthalic anhydride (PEPA) as an end-capper in a polar solvent such as N-methylpyrrolidinone (NMP). These oligomers are subsequently cyclodehydrated -- for example, by heating the solution in the presence of toluene to remove the water by azeotropic distillation to form low-molecular-weight imide oligomers. More precisely, what is obtained is a mixture of PETI oligomeric species, spanning a range of molecular weights, that exhibits a stable melt viscosity of less than approximately 60 poise (and generally less than 10 poise) at a temperature below 300 deg C. After curing of the oligomers at a temperature of 371 deg C, the resulting polymer can have a glass-transition temperature (Tg) as high as 375 C, the exact value depending on the compositions.

  19. Method for epoxy foam production using a liquid anhydride

    DOEpatents

    Celina, Mathias [Albuquerque, NM

    2012-06-05

    An epoxy resin mixture with at least one epoxy resin of between approximately 50 wt % and 100 wt %, an anhydride cure agent of between approximately 0 wt % and approximately 50 wt %, a tert-butoxycarbonyl anhydride foaming agent of between proximately 0.1-20 wt %, a surfactant and an imidazole or similar catalyst of less than approximately 2 wt %, where the resin mixture is formed from at least one epoxy resin with a 1-10 wt % tert-butoxycarbonyl anhydride compound and an imidazole catalyst at a temperature sufficient to keep the resin in a suitable viscosity range, the resin mixture reacting to form a foaming resin which in the presence of an epoxy curative can then be cured at a temperature greater than 50.degree. C. to form an epoxy foam.

  20. β-Functionalization of carboxylic anhydrides with β-alkyl substituents through carbene organocatalysis.

    PubMed

    Jin, Zhichao; Chen, Shaojin; Wang, Yuhuang; Zheng, Pengcheng; Yang, Song; Chi, Yonggui Robin

    2014-12-01

    The first NHC-catalyzed functionalization of carboxylic anhydrides is described. In this reaction, the β carbon behaves as a nucleophilic carbon and undergoes asymmetric reactions with electrophiles. Anhydrides with challenging β-alkyl substituents work effectively.

  1. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols...

  2. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols...

  3. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols...

  4. 40 CFR 721.10038 - Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Trimellitic anhydride, polymer with... Trimellitic anhydride, polymer with substituted glycol, alkyl phenols and ethoxylated nonylphenol (generic... identified generically as trimellitic anhydride, polymer with substituted glycol, alkyl phenols...

  5. IDENTIFYING AIRWAY SENSITIZERS: MRNA CYTOKINE PROFILES INDUCED BY VARIOUS ANHYDRIDES

    EPA Science Inventory

    Abstract:
    Exposure to low molecular weight (LMW) chemicals in the workplace has been linked to a variety of respiratory effects. Within the LMW chemicals, one of the major classes involved in these effects are the acid anhydrides. The immunological basis of respiratory hyp...

  6. Rheological studies on the reaction of zein with polyethylenemaleic anhydride

    Technology Transfer Automated Retrieval System (TEKTRAN)

    There continues to be interest in developing solvent-resistant articles from biobased renewable materials to successfully complete with petro-chemical products. It was previously shown that reaction of zein with polyethylenemaleic anhydride (PEMA) provides articles that are solvent-resistant. The ge...

  7. Nickel-catalyzed decarboxylative carboamination of alkynes with isatoic anhydrides.

    PubMed

    Yoshino, Yasufumi; Kurahashi, Takuya; Matsubara, Seijiro

    2009-06-10

    An intermolecular nickel-catalyzed addition reaction in which isatoic anhydrides react with alkynes to afford substituted quinolones has been developed. A mechanistic rationale is proposed, implying oxidative addition of Ni(0) to a carbamate, which allows intermolecular addition to alkynes via decarboxylation.

  8. Condensation of anhydrides or dicarboxylic acids with compounds containing active methylene groups. Part 1: Condensation of phthalic anhydride with acetoacetic and malonic ester

    NASA Technical Reports Server (NTRS)

    Oshkaya, V. P.; Vanag, G. Y.

    1985-01-01

    Phthalic anhydride was condensed with acetoacetic ester in acetic anhydride and triethylamine solution, and when phthalyl chloride was reacted with sodium acetoacetic ester compounds were formed of the phthalide and indandione series: phthalylacetoacetic ester and a derivative of indan-1,3-dione which after boiling with hydrochloric acid yielded indan-1,3-dione. Phthalylmalonic ester was obtained from phthalic anhydride and malonic ester in the presence of triethylamine.

  9. Substituted isatoic anhydrides: selective inactivators of trypsin-like serine proteases.

    PubMed

    Gelb, M H; Abeles, R H

    1986-04-01

    Derivatives of isatoic anhydride were prepared and tested as inhibitors of serine proteases. A number of isatoic anhydrides with positively charged substituents irreversibly inactivated several trypsin-like enzymes and preferentially inactivated trypsin over chymotrypsin. Further selectivity was obtained by introduction of an aromatic group on the N-1 position of isatoic anhydride. 7-(Aminomethyl)-1-benzylisatoic anhydride was prepared and was a selective inactivator of thrombin; thus it is possible to prepare derivatives of isatoic anhydride that are highly enzyme selective without attaching peptide recognition structures.

  10. Low Melt Viscosity Resins for Resin Transfer Molding

    NASA Technical Reports Server (NTRS)

    Harris, Frank W.

    2002-01-01

    In recent years, resin transfer molding (RTM) has become one of the methods of choice for high performance composites. Its cost effectiveness and ease of fabrication are major advantages of RTM. RTM process usually requires resins with very low melt viscosity (less than 10 Poise). The optimum RTM resins also need to display high thennal-oxidative stability, high glass transition temperature (T(sub g)), and good toughness. The traditional PMR-type polyimides (e.g. PMR-15) do not fit this requirement, because the viscosities are too high and the nadic endcap cures too fast. High T(sub g), low-melt viscosity resins are highly desirable for aerospace applications and NASA s Reusable Launch Vehicle (RLV) program. The objective of this work is to prepare low-melt viscosity polyimide resins for RTM or resin film infusion (RFI) processes. The approach involves the synthesis of phenylethynyl-terminated imide oligomers. These materials have been designed to minimize their melt viscosity so that they can be readily processed. During the cure, the oligomers undergo both chain extension and crosslinking via the thermal polymerization of the phenylethynyl groups. The Phenylethynyl endcap is preferred over the nadic group due to its high curing temperature, which provides broader processing windows. This work involved the synthesis and polymerization of oligomers containing zig-zag backbones and twisted biphenyl structures. Some A-B type precursors which possessed both nitro and anhydride functionality, or both nitro and amine functionality, were also synthesized in order to obtain the well defined oligomers. The resulting zig-zag structured oligomers were then end-capped with 4-phenylethynylphthalic anhydride (PEPA) for further cure. The properties of these novel imide oligomers are evaluated.

  11. Relationship of airborne trimellitic anhydride concentrations to trimellitic anhydride--induced symptoms and immune responses

    SciTech Connect

    Bernstein, D.I.; Roach, D.E.; McGrath, K.G.; Larsen, R.S.; Zeiss, C.R.; Patterson, R.

    1983-12-01

    Eighteen workers exposed to trimellitic anhydride (TMA) powder were evaluated in 1979. Twelve of these workers were available for longitudinal study until 1982. Annual clinical evaluations and serum radioimmunoassays for total antibody binding and specific IgE binding to /sup 125/I-TM-HSA were performed. In 1979, five workers had antibody against TM-HSA. Of these, three workers were diagnosed with the late respiratory systemic syndrome (LRSS) and one worker with TMA-induced allergic rhinitis. The LRSS workers had significantly elevated total antibody binding of /sup 125/I-TM-HSA and the worker with rhinitis had significantly elevated specific IgE binding of /sup 125/I-TM-HSA per milliliter of serum. Although TMA handling was intermittent throughout the year, average airborne dust concentrations from 1974 to 1978 at job stations of the two heaviest TMA-exposed occupations, operator and assistant operator, were 2.1 and 0.82 mg/m3, respectively. After local exhaust ventilation had been improved, average airborne dust concentrations of TMA at the two latter job stations fell to levels of 0.03 and 0.01 mg/m3, respectively, in 1982. The decrease in TMA exposure coincided with a gradual fall in total antibody binding of /sup 125/I-TM-HSA per milliliter in 1982 and symptomatic improvement in the three individuals with the LRSS. The continuous low-level exposure of the worker with TMA rhinitis was sufficient to elicit a rise in specific IgE against TM-HSA from 1.1 ng of 125I-TM-HSA bound per milliliter in 1979 to 2.12 in 1982.

  12. Delayed and immediate allergy caused by methylhexahydrophthalic anhydride.

    PubMed

    Kanerva, L; Hyry, H; Jolanki, R; Hytönen, M; Estlander, T

    1997-01-01

    Epoxy resin compounds (ERC) include a large number of chemicals, such as epoxy resins (ER), reactive diluents and hardeners. Many hardeners, e.g., aliphatic polyamines, are well-known sensitizers. Another type of ER hardeners are the phthalic anhydrides, such as methylhexahydrophthalic anhydride (MHHPA) and methyltetrahydrophthalic anhydride (MTHPA), which have been reported as causing immunologically-mediated respiratory diseases and contact urticaria, but not allergic contact dermatitis. Here, we present a horizontal boring-machine worker who developed allergic contact dermatitis, as well as allergic rhinitis and an immediate contact skin reaction from MHHPA. Patch testing with a dilution series of MHHPA in pet. elicited the following results: 2%, 1% and 0.5%, +2; 0.25% and 0.125%, + (3- to 6-day readings). An immunohistochemical and electron microscopic study also indicated that the patch test reactions were conventional-delayed allergic reactions. Interleukin 8 was observed in the epidermal cells, whereas interleukin 4 immunoreactivity was detected in the dermal cells. Immunoreactivity to-interleukin 5, granulocyte/macrophage-colophony stimulating factor (GM-CSF) or eosinophil cationic protein was not seen. In conclusion, the patient developed both Type I and Type IV allergy to MHHPA. The clinical data, patch test results, immunohistochemical and electron microscopic observations indicated that the MHHPA allergy detected by the patch test reaction was a conventional delayed-type hypersensitivity reaction. The patient also had an allergic patch test reaction to para-phenylenediamine and diaminodiphenylmethane, possibly representing occupational sensitization.

  13. Experimental and Computational Thermochemistry of 3- and 4-Nitrophthalic Anhydride.

    PubMed

    García-Castro, Miguel Ángel; Amador, Patricia; Hernández-Pérez, Julio Manuel; Medina-Favela, Adrián Eduardo; Flores, Henoc

    2014-05-08

    In order to understand the influence that the position of the nitro group on the aromatic ring has on the relative stability of two isomers, the standard enthalpies of formation of 3- and 4-nitrophthalic anhydride in the gaseous phase, at T = 298.15 K, were obtained by experimental thermochemistry and theoretical studies. The standard enthalpies of formation in the crystalline phase, at T = 298.15 K, were obtained by combustion calorimetry and the enthalpies of sublimation by the Knudsen method. For the theoretical calculations, a standard ab initio molecular orbital method at the G3 level was used. The enthalpies of formation in the gaseous phase were obtained from atomization and isodesmic reactions. A theoretical study of the molecular and electronic structures of these compounds was also performed. Differences of -9.7 kJ•mol-1, for 3-nitrophthalic anhydride, and -2.6 kJ•mol-1 for 4-nitrophthalic anhydride, were found from a comparison between our theoretical and experimental results.

  14. Chain-length-dependent autocatalytic hydrolysis of fatty acid anhydrides in polyethylene glycol.

    PubMed

    Cao, Cao; Wang, Qing-Biao; Tang, Lin-Jun; Ge, Bing-Qiang; Chen, Zhong-Xiu; Deng, Shao-Ping

    2014-03-27

    Autocatalytic hydrolysis of fatty acid anhydrides induced by the spontaneously formed vesicles has been studied for years. However, whether the reaction autocatalyzed by vesicles formed in diluted solutions applies also to macromolecular crowded conditions remains unknown. The aim of this study is to characterize hydrolysis behavior of fatty acid anhydrides and formation of vesicles in crowded media. Inert macromolecular crowding agents such as polyethylene glycol (PEG) and Dextran were used to probe the impact of external crowding on the autocatalytic hydrolysis of fatty acid anhydrides with varied hydrophobic chain length. Under stringent conditions of crowding, hydrolysis rates of octanoic anhydride, nonanoic anhydride, and decanoic anhydride were found to decrease, but the rates of lauric anhydride and oleic anhydride increased. These results suggest that the effect of the crowding agent on the hydrolysis of fatty acid anhydrides was chain-length-dependent. Characterization of the size and polydispersity of vesicles formed from hydrolyzed fatty acid anhydrides in crowding revealed that long-chain fatty acids formed monodisperse vesicles easier at lower concentrations of PEG. Measurement of the critical aggregation concentration of ionized fatty acid in the presence of PEG showed that crowding media promoted vesicle formation from long-chain fatty acids but inhibited those from fatty acids with fewer carbon atoms. Further investigation of the diffusion property of ionized fatty acids in crowding agents suggested that PEG might create more hydrophobic areas for long-chain fatty acids anhydrides, which subsequently promoted the unreacted anhydride in the aqueous phase to be solubilized in the formed vesicles. This research provides information for understanding the autocatalytic reaction accompanied by self-producing aggregates and the behavior of fatty acids in crowding media.

  15. Are isatin and isatoic anhydride antiaromatic and aromatic respectively? A combined experimental and theoretical investigation.

    PubMed

    Matos, M Agostinha R; Miranda, Margarida S; Morais, Victor M; Liebman, Joel F

    2003-07-21

    This paper reports the results of our thermochemical/calorimetric determination of the enthalpies of combustion, phase change, and formation of isatin, isatoic anhydride, and N-methylisatin. The density functional calculations accompanied by vibrational and thermal corrections were also performed for these compounds and N-methylisatoic anhydride. Through a combination of theoretical calculations and associated isodesmic reactions, we have deduced that isatin has some antiaromatic character and isatoic anhydride enjoys some aromatic stabilization.

  16. Tall oil fatty acid anhydrides as corrosion inhibitor intermediates

    SciTech Connect

    Fischer, E.R.; Parker, J.E. III

    1995-12-01

    Electrochemical corrosion of carbon steel tubulars in producing oil wells causes lost production and necessitates costly repairs. Corrosive environments exists where hydrocarbons and an aqueous phase are being extracted from producing wells. Tubing life has been extended four fold with the development of organic corrosion inhibitors and concentric configuration treatment. Anhydrides derived from tall oil fatty acids offer enhanced corrosion inhibition properties as compared to traditional dimer/trimer acids. The chemistry of this intermediate and its use in corrosion inhibition for down hole applications, as well as the synthesis of novel oil and water-soluble derivatives will be discussed.

  17. Thermoplastic adhesives based on 4,4'-isophthaloyldiphthalic anhydride (IDPA)

    NASA Technical Reports Server (NTRS)

    Progar, Donald J.; Stclair, Terry L.; Pratt, J. Richard

    1988-01-01

    Thermoplastic polyimides were prepared and evaluated as adhesives. These materials are based on 4,4'-isophthaloyldiphathalic anhydride (IDAP) and either metaphenylene diamine (MPD) or 3,3'-diaminobenzophenone (DBAP). Both polymers exhibit excellent adhesive properties; however, the IDPA-MPD is the more attractive system because of a combination of high mechanical and physical properties as well as being made from commercially attractive monomers. The IDPA-MPD is an isomeric form of the commercially available adhesive and matrix resin, LARC-TPI and both systems have the same glass transition temperature and exhibit similar adhesive properties.

  18. The energetics of isomeric benzoxazine diones: isatoic anhydride revisited.

    PubMed

    Matos, M Agostinha R; Miranda, Margarida S; Morais, Victor M F; Liebman, Joel F

    2004-06-07

    The standard (p(o) = 0.1 MPa) molar enthalpy of formation of crystalline 2H-1,3-benzoxazine-2,4(3H)dione was measured, at T= 298.15 K, by static bomb calorimetry and the standard molar enthalpy of sublimation, at T= 298.15 K, was obtained using Calvet microcalorimetry. These values were used to derive the standard molar enthalpy of formation in the gaseous phase, T= 298.15 K, of -(401.0 +/- 3.5) kJ mol(-1). The standard molar enthalpy of sublimation of isatoic anhydride was recalculated, and our recommended experimental value for the standard molar enthalpy of formation in the gaseous phase, T= 298.15 K, is -(406.2 +/- 3.4) kJ mol(-1). Density functional calculations for the two isomers 2H-1,3-benzoxazine-2,4(3H)dione and isatoic anhydride, in which the ring nitrogen and oxygen have been transposed, confirm the experimental evidence of nearly identical thermochemical stability for these isomers.

  19. Synthesis and hydrolysis behaviour of poly(ester anhydrides) from polylactone precursors containing alkenyl moieties.

    PubMed

    Korhonen, Harri; Hakala, Risto A; Helminen, Antti O; Seppälä, Jukka V

    2006-07-14

    Hydroxyl-group functional polylactones were prepared and converted to acid- terminated polyesters in a reaction with a series of alkenylsuccinic anhydrides containing 8, 12, or 18 carbons in their alkenyl chains. These polyester precursors were then linked into higher molecular weight poly(ester anhydrides) containing alkenyl moieties in their polyester blocks. The hydrolysis behaviour of the poly(ester anhydrides) was found to depend on the thermal properties of the polyester precursors. For poly(ester anhydrides) prepared from low molecular weight prepolymers with thermal transitions below 37 degrees C, the presence of hydrophobic alkenyl chains in the polyester precursors slowed the rate of weight loss. Poly(ester anhydrides) prepared from higher molecular weight prepolymers showed the opposite weight-loss behaviour; i.e., the crystallinity and thermal transitions of the alkenyl chain-containing poly(ester anhydrides) were low, and the weight loss was faster than for poly(ester anhydrides) without the alkenyl chains. The differences in length of the alkenyl chain, as such, had little effect on the hydrolysis behaviour and thermal properties of the poly(ester anhydrides).

  20. Initiation precursors and initiators in laser-induced copolymerization of styrene and maleic anhydride in acetone

    NASA Technical Reports Server (NTRS)

    Miner, Gilda A.; Meador, Willard E.; Chang, C. Ken

    1990-01-01

    The initiation step of photopolymerized styrene/maleic anhydride copolymer was investigated at 365 nm. UV absorption measurements provide decisive evidence that the styrene/maleic anhydride charge transfer complex is the sole absorbing species; however, key laser experiments suggest intermediate reactions lead to a monoradical initiating species. A mechanism for the photoinitiation step of the copolymer is proposed.

  1. Palladium-catalyzed carbonylation of o-iodoanilines for synthesis of isatoic anhydrides.

    PubMed

    Gao, Sha; Chen, Ming; Zhao, Mi-Na; Du, Wei; Ren, Zhi-Hui; Wang, Yao-Yu; Guan, Zheng-Hui

    2014-05-02

    A novel palladium-catalyzed oxidative double carbonylation of o-iodoanilines for the synthesis of isatoic anhydrides has been developed. The reaction employs readily available o-iodoanilines as the starting materials and proceeds under mild conditions. For extension, palladium-catalyzed oxidative carbonylation of anthranilic acids was developed for the synthesis of substituted isatoic anhydrides in high to excellent yields.

  2. 40 CFR 721.9270 - Reaction product of epoxy with anhydride and glycerol and glycol.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Reaction product of epoxy with... Significant New Uses for Specific Chemical Substances § 721.9270 Reaction product of epoxy with anhydride and... substance identified generically as reaction product of epoxy with anhydride and glycerol and glycol (PMN...

  3. 40 CFR 721.9270 - Reaction product of epoxy with anhydride and glycerol and glycol.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Reaction product of epoxy with... Significant New Uses for Specific Chemical Substances § 721.9270 Reaction product of epoxy with anhydride and... substance identified generically as reaction product of epoxy with anhydride and glycerol and glycol (PMN...

  4. 40 CFR 721.9270 - Reaction product of epoxy with anhydride and glycerol and glycol.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Reaction product of epoxy with... Significant New Uses for Specific Chemical Substances § 721.9270 Reaction product of epoxy with anhydride and... substance identified generically as reaction product of epoxy with anhydride and glycerol and glycol (PMN...

  5. 40 CFR 721.9270 - Reaction product of epoxy with anhydride and glycerol and glycol.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Reaction product of epoxy with... Significant New Uses for Specific Chemical Substances § 721.9270 Reaction product of epoxy with anhydride and... substance identified generically as reaction product of epoxy with anhydride and glycerol and glycol (PMN...

  6. 40 CFR 721.9270 - Reaction product of epoxy with anhydride and glycerol and glycol.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Reaction product of epoxy with... Significant New Uses for Specific Chemical Substances § 721.9270 Reaction product of epoxy with anhydride and... substance identified generically as reaction product of epoxy with anhydride and glycerol and glycol (PMN...

  7. TRIMELLITIC ANHYDRIDE-INDUCED EOSINOPHILIA IN A MURINE MODEL OF OCCUPATIONAL ASTHMA

    EPA Science Inventory

    TRIMELLITIC ANHYDRIDE-INDUCED EOSINOPHILIA IN A MURINE MODEL OF OCCUPATIONAL ASTHMA. J F Regal, ME Mohrman, E Boykin and D Sailstad. Dept. of Pharmacology, University of Minnesota, Duluth, MN, USA and NHEERL, ORD, US EPA, RTP, NC, USA.
    Trimellitic anhydride (TMA) is a small m...

  8. Modification of wheat starch with succinic acid/acetic anhydride and azelaic acid/acetic anhydride mixtures I. Thermophysical and pasting properties.

    PubMed

    Subarić, Drago; Ačkar, Durđica; Babić, Jurislav; Sakač, Nikola; Jozinović, Antun

    2014-10-01

    The aim of this research was to investigate the influence of modification with succinic acid/acetic anhydride and azelaic acid/acetic anhydride mixtures on thermophysical and pasting properties of wheat starch. Starch was isolated from two wheat varieties and modified with mixtures of succinic acid and acetic anhydride, and azelaic acid and acetic anhydride in 4, 6 and 8 % (w/w). Thermophysical, pasting properties, swelling power, solubility and amylose content of modified starches were determined. The results showed that modifications with mixtures of afore mentioned dicarboxylic acids with acetic anhydride decreased gelatinisation and pasting temperatures. Gelatinisation enthalpy of Golubica starch increased, while of Srpanjka starch decreased by modifications. Retrogradation after 7 and 14 day-storage at 4 °C decreased after modifications of both starches. Maximum, hot and cold paste viscosity of both starches increased, while stability during shearing at high temperatures decreased. % setback of starches modified with azelaic acid/acetic anhydride mixture decreased. Swelling power and solubility of both starches increased by both modifications.

  9. Risk factors for sensitisation and respiratory symptoms among workers exposed to acid anhydrides: a cohort study

    PubMed Central

    Barker, R. D.; van Tongeren, M. J.; Harris, J. M.; Gardiner, K.; Venables, K. M.; Newman, T

    1998-01-01

    OBJECTIVES: To examine the relation between exposure to acid anhydrides and the risk of developing immediate skin prick test responses to acid anhydride human serum albumin (AA-HSA) conjugates or work related respiratory symptoms; to assess whether these relations are modified by atopy or smoking. METHODS: A cohort of 506 workers exposed to phthalic (PA), maleic (MA), and trimellitic anhydride (TMA) was defined. Workers completed questionnaires relating to employment history, respiratory symptoms, and smoking habits. Skin prick tests were done with AA-HSA conjugates and common inhalant allergens. Exposure to acid anhydrides was measured at the time of the survey and a retrospective exposure assessment was done. RESULTS: Information was obtained from 401 (79%) workers. Thirty four (8.8%) had new work related respiratory symptoms that occurred for the first time while working with acid anhydrides and 12 (3.2%) were sensitised, with an immediate skin prick test reaction to AA-HSA conjugates. Sensitisation to acid anhydrides was associated with work related respiratory symptoms and with smoking at the time of exposure to acid anhydride. When all subjects were included and all three acid anhydrides were taken into account there was no consistent evidence for an exposure-response relation, but with the analysis restricted to a factory where only TMA was in use there was an increased prevalence of sensitisation to acid anhydrides and work related respiratory symptoms with increasing full shift exposure. This relation was apparent within the current occupational exposure standard of 40 micrograms.m-3 and was not modified significantly by smoking or atopy. CONCLUSIONS: Intensity of exposure and cigarette smoking may be risk factors for sensitisation to acid anhydrides. Exposure is also a risk factor for respiratory symptoms. As there was evidence for sensitisation to TMA at full shift exposures within the occupational exposure standard this standard should be reviewed.

  10. 40 CFR 721.6183 - Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow alkyl amines...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... - maleic anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine... Substances § 721.6183 Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow... anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine (PMN...

  11. 40 CFR 721.6183 - Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow alkyl amines...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... - maleic anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine... Substances § 721.6183 Amides, from ammonium hydroxide - maleic anhydride polymer and hydrogenated tallow... anhydride polymer and hydrogenated tallow alkyl amines, sodium salts, compds. with ethanolamine (PMN...

  12. Acetylation of barnyardgrass starch with acetic anhydride under iodine catalysis.

    PubMed

    Bartz, Josiane; Goebel, Jorge Tiago; Giovanaz, Marcos Antônio; Zavareze, Elessandra da Rosa; Schirmer, Manoel Artigas; Dias, Alvaro Renato Guerra

    2015-07-01

    Barnyardgrass (Echinochloa crus-galli) is an invasive plant that is difficult to control and is found in abundance as part of the waste of the paddy industry. In this study, barnyardgrass starch was extracted and studied to obtain a novel starch with potential food and non-food applications. We report some of the physicochemical, functional and morphological properties as well as the effect of modifying this starch with acetic anhydride by catalysis with 1, 5 or 10mM of iodine. The extent of the introduction of acetyl groups increased with increasing iodine levels as catalyst. The shape of the granules remained unaltered, but there were low levels of surface corrosion and the overall relative crystallinity decreased. The pasting temperature, enthalpy and other gelatinisation temperatures were reduced by the modification. There was an increase in the viscosity of the pastes, except for the peak viscosity, which was strongly reduced in 10mM iodine.

  13. Evaluation of copolymer conformation states of vinylchloride-maleic anhydride

    NASA Astrophysics Data System (ADS)

    Ivanov, A. A.

    2016-11-01

    The quantum-chemical analysis and experimental study of alternating vinylchloride-maleic anhydride (VC-MA) copolymer macromolecules with polymerization degree 600 have been carried out. The VC-MA copolymer in solvents of different nature undergoes cycloanhydride-enol tautomerism and the macromolecules take the form of corrugated sticks according to viscometric measurements. The computer simulation has shown that the segment with polymerization degree n < 18 (model compound) is not a helix and rolls while if n = 18 the conformations get distorted. The model molecule optimal structure comprising a random sequence of alternating units of comonomers and their enol tautomers with minimal system total energy has been found by the semiempirical parametric method PM3.

  14. Perylenetetracarboxylic anhydride as a precursor of fluorescent carbon nanoonion rings

    NASA Astrophysics Data System (ADS)

    Baldoví, Herme G.; Herance, José Raul; Manuel Víctor, Víctor; Alvaro, Mercedes; Garcia, Hermenegildo

    2015-07-01

    Thermal annealing at 400 °C of perylenetetracarboxylic anhydride in low molecular mass PEG gives rise to the formation of well defined nanoobjects of 2.5 nm height and size distribution from 10 to 65 nm (average 40 nm) after purification of the raw mixture with silicagel chromatography. TEM reveals that the flat nanoobjects are constituted of concentric graphenic rings (0.34 nm interlayer distance). The morphology of the nanoparticles resembles onion rings of nanometric dimensions (nanoonion rings C-NOR). C-NOR particles have an excitation dependent emission with λem from 430 to 570 nm and a maximum emission quantum yield of 0.49. C-NOR particles can be internalized into Hep3B human hepatoma cells as determined by confocal fluorescence microscopy and are remarkably biocompatible affecting slightly cell viability according to the MTT test.

  15. Carboxy terminated rubber based on natural rubber grafted with acid anhydrides and its adhesion properties

    NASA Astrophysics Data System (ADS)

    Klinpituksa, P.; Kongkalai, P.; Kaesaman, A.

    2014-08-01

    The chemical modification of natural rubber by grafting of various polar functional molecules is an essential method, improving the versatility of rubber in applications. This research investigated the preparation of natural rubber-graft-citraconic anhydride (NR-g-CCA), natural rubber-graft-itaconic anhydride (NR-g-ICA), and natural rubber-graft-maleic anhydride (NR-g-MA), with the anhydrides grafted to natural rubber in toluene using benzoyl peroxide as an initiator. Variations of monomer content, initiator content, temperature and reaction time of the grafting copolymerization were investigated. The maximum degrees of grafting were 1.06% for NR-g-CCA, 4.66% for NR-g-ICA, and 5.03% for NR-g-MA, reached using 10 phr citraconic anhydride, 10 phr of itaconic anhydride, or 8 phr of maleic anhydride, 3 phr benzoyl peroxide, at 85, 80 and 80°C for 2, 2 and 3 hrs, respectively. Solvent-based wood adhesives were formulated from these copolymers with various contents of wood resin in the range 10-40 phr. The maximal 289 N/in cleavage peel and 245.7 KPa shear strength for NR-g-MA (5.03% grafting) were obtained at 40 phr wood resin.

  16. Diastereoselective Synthesis of γ- and δ-Lactams from Imines and Sulfone-Substituted Anhydrides

    PubMed Central

    2015-01-01

    Sulfone-substituted γ- and δ-lactams have been prepared in a single step with high diastereoselectivity. Sulfonylglutaric anhydrides produce intermediates that readily decarboxylate to provide δ-lactams with high diastereoselectivity. Substituents at the 3- or 4-position of the glutaric anhydride induce high levels of stereocontrol. Sulfonylsuccinic anhydrides produce intermediate carboxylic acids that can be trapped as methyl esters or allowed to decarboxylate under mild conditions. This method has been applied to a short synthesis of the pyrrolizidine alkaloid (±)-isoretronecanol. PMID:24552208

  17. 21 CFR 872.3500 - Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium...

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. 872.3500 Section 872.3500...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. (a) Identification... adhesive is a device composed of polyvinylmethylether maleic anhydride, acid copolymer,...

  18. Poly(butylene succinate-co-butylene adipate)/cellulose nanocrystal composites modified with phthalic anhydride.

    PubMed

    Zhang, Xuzhen; Zhang, Yong

    2015-12-10

    As a kind of biomass nanofiller for polymers, cellulose nanocrystal (CNC) has good mechanical properties and reinforcing capability. To improve the compatibility of poly(butylene succinate-co-butylene adipate) (PBSA)/CNC composites, phthalic anhydride was used as a compatilizer during melt mixing, leading to the significant improvement of the mechanical properties and thermal stability of the composites, which is related to the better dispersion of CNC in the composites. The addition of phthalic anhydride could accelerate the crystallization of PBSA component as evidenced by the curves of isothermal crystallization of the composites, but had little effect on the crystalline polymorphs of PBSA component. The addition of phthalic anhydride could strongly improve the hydrophobicity of the composites. The good mechanical properties, fast crystallization and improved hydrophobicity of PBSA/CNC composites with phthalic anhydride are favor to their practical commercial utilization.

  19. 21 CFR 872.3500 - Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium...

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. 872.3500 Section 872.3500...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. (a) Identification. Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium (NACMC)...

  20. 21 CFR 872.3500 - Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium...

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. 872.3500 Section 872.3500...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. (a) Identification. Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium (NACMC)...

  1. 21 CFR 872.3500 - Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium...

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. 872.3500 Section 872.3500...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. (a) Identification. Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium (NACMC)...

  2. Highly efficient peptide formation from N-acetylaminoacyl-AMP anhydride and free amino acid

    NASA Technical Reports Server (NTRS)

    Mullins, D. W., Jr.; Lacey, J. C., Jr.

    1983-01-01

    The kinetics of formation of the N-blocked dipeptide, N-acetylglycylglycine, from N-acetylglycyl adenylate anhydride and glycine in aqueous solution at 25 C, and at various PH's are reported. The reaction is of interest in that over a physiologically relevant pH range (6-8), peptide synthesis proceeds more rapidly than hydrolysis, even at those pH's at which this compound becomes increasingly susceptible to base-catalyzed hydrolysis. Under similar conditions, the corresponding unblocked aminoacyl adenylate anhydrides are considerably more unstable, and undergo appreciable hydrlysis in the presence of free amino acid. Because N-blocked aminoacyl adenylate anhydrides serve as model compounds of peptidyl adenylate anhydrides, these results suggest that primitive amino acid polymerization systems may have operated by cyclic reactivation of the peptidyl carboxyl group, rather than that of the incoming amino acid.

  3. 21 CFR 872.3500 - Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium...

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. 872.3500 Section 872.3500...), acid copolymer, and carboxymethylcellulose sodium (NACMC) denture adhesive. (a) Identification. Polyvinylmethylether maleic anhydride (PVM-MA), acid copolymer, and carboxymethylcellulose sodium (NACMC)...

  4. Low molecular weight chemicals, hypersensitivity, and direct toxicity: the acid anhydrides.

    PubMed Central

    Venables, K M

    1989-01-01

    The acid anhydrides are a group of reactive chemicals used widely in alkyd and epoxy resins. The major hazards to health are mucosal and skin irritation and sensitisation of the respiratory tract. Most occupational asthma caused by acid anhydrides appears to be immunologically mediated. Immunological mechanisms have been proposed to explain an influenza-like syndrome and pulmonary haemorrhage, but direct toxicity may also be important in the aetiology of these conditions. PMID:2653411

  5. Chirally selective, intramolecular interaction observed in an aminoacyl adenylate anhydride

    NASA Technical Reports Server (NTRS)

    Lacey, J. C., Jr.; Hall, L. M.; Mullins, D. W., Jr.; Watkins, C. L.

    1985-01-01

    The interaction between amino acids and nucleotide bases is studied. The proton NMR spectrum of N-acetylphenylalanyl-AMP-anhydride is analyzed H8 and H2 signals, two upfield signals of equal size, and five phenylalanine ring proton signals are observed in the spectrum; the upfield movement of the proton and the racemization of the N-acetyl L-phenylalanine material are examined. The differences in the position of the signals due to the diastereoisomers are investigated. The separation of the D and L amino acyl adenylates using HPLC is described. H-1 NMR spectra of the isomers are examined in order to determine which isomer displays the strongest interaction between the phenyl ring and the adenine ring. The spectra reveal that the L isomer shows the highest upfield change of both H8 and H2 signals. It is noted that the phenyl ring lies over C2 of the adenine ring with the phenyl meta and para protons extended past the adenine ring and the phenyl ortho protons.

  6. Convergence of Biological Nitration and Nitrosation via Symmetrical Nitrous Anhydride

    PubMed Central

    Vitturi, Dario A.; Minarrieta, Lucia; Salvatore, Sonia R.; Postlethwait, Edward M.; Fazzari, Marco; Ferrer-Sueta, Gerardo; Lancaster, Jack R.; Freeman, Bruce A.; Schopfer, Francisco J.

    2015-01-01

    Current perspective holds that the generation of secondary signaling mediators from nitrite (NO2−) requires acidification to nitrous acid (HNO2) or metal catalysis. Herein, the use of stable isotope-labeled NO2− and LC-MS/MS analysis of products revealed that NO2− also participates in fatty acid nitration and thiol S-nitrosation at neutral pH. These reactions occur in the absence of metal centers and are stimulated by nitric oxide (•NO) autoxidation via symmetrical dinitrogen trioxide (nitrous anhydride, symN2O3) formation. While theoretical models have predicted physiological symN2O3 formation, its generation is now demonstrated in aqueous reaction systems, cell models and in viv, with the concerted reactions of •NO and NO2− shown to be critical for symN2O3 formation. These results reveal new mechanisms underlying the NO2− propagation of •NO signaling and the regulation of both biomolecule function and signaling network activity via NO2−-dependent nitrosation and nitration reactions. PMID:26006011

  7. Hydrolytic properties of phenylalanyl- and N-acetylphenylalanyl adenylate anhydrides

    NASA Technical Reports Server (NTRS)

    Lacey, J. C., Jr.; Mullins, D. W., Jr.; Senaratne, N.

    1984-01-01

    The hydrolysis of phenylalynyl- and N-acetylephenylalanyl adenylate anhydrides (AcPhe-AMP) is studied experimentally using a new spectrophotometric method. The hydrolysis process was analyzed at low concentrations (0.0001 M), constant temperature of 25 C, constant buffer concentration (0.05 M), and as a function of pH. It is found that while Phe-AMP is susceptible to attack by OH(-), AcPhe-AMP is susceptible to acid decomposition as well. At a pH of 4 to 8, Phe-AMP hydolyzes faster than AcPhe-AMP, but at pH less than four or greater than eight, the blocked form hydrolyzes faster. Both forms are attacked by H2O at the same rate. The rate laws for the various hydrolytic mechanisms and the activation energies for the hydrolyses at pH 7.1 are given in a table, and the possible relevance of the findings to the origin and evolution of the process of protein synthesis is discussed.

  8. Biocompatibility of polysebacic anhydride microparticles with chondrocytes in engineered cartilage

    PubMed Central

    Ponnurangam, Sathish; O'Connell, Grace D.; Hung, Clark T.; Somasundaran, Ponisseril

    2015-01-01

    One of main challenges in developing clinically relevant engineered cartilage is overcoming limited nutrient diffusion due to progressive elaboration of extracellular matrix at the periphery of the construct. Macro-channels have been used to decrease the nutrient path-length; however, the channels become occluded with matrix within weeks in culture, reducing nutrient diffusion. Alternatively, microparticles can be imbedded throughout the scaffold to provide localized nutrient delivery. In this study, we evaluated biocompatibility of polysebacic anhydride (PSA) polymers and the effectiveness of PSA-based microparticles for short-term delivery of nutrients in engineered cartilage. PSA-based microparticles were biocompatible with juvenile bovine chondrocytes for concentrations up to 2mg/mL; however, cytotoxicity was observed at 20mg/mL. Cytotoxicity at high concentrations is likely due to intracellular accumulation of PSA degradation products and resulting lipotoxicity. Cytotoxicity of PSA was partially reversed in the presence of bovine serum albumin. In conclusion, the findings from this study demonstrate concentration-dependent biocompatibility of PSA-based microparticles and potential application as a nutrient delivery vehicle that can be imbedded in scaffolds for tissue engineering. PMID:26398146

  9. Allergy to methyltetrahydrophthalic anhydride in epoxy resin workers.

    PubMed Central

    Nielsen, J; Welinder, H; Horstmann, V; Skerfving, S

    1992-01-01

    One hundred and forty four current and 26 former workers in a plant producing barrels for rocket guns from an epoxy resin containing methyltetrahydrophthalic anhydride (MTHPA; time weighted average air concentration up to 150 micrograms/m3) were studied. They showed higher frequencies of work related symptoms from the eyes (31 v 0%; p < 0.001), nose (53 v 9%; p < 0.001), pharynx (26 v 6%; p < 0.01), and asthma (11 v 0%; p < 0.05) than 33 controls. Also they had higher rates of positive skin prick test to a conjugate of MTHPA and human serum albumin (16 v 0%; p < 0.01), and more had specific IgE and IgG serum antibodies (18 v 0%; p < 0.01 and 12 v 0%; p < 0.05 respectively). There were statistically significant exposure-response relations between exposure and symptoms from eyes and upper airways, dry cough, positive skin prick test, and specific IgE and IgG antibodies. There was a non-significant difference in reaction to metacholine between exposed workers and non-smoking controls. In workers with and without specific IgE antibodies, differences existed in frequency of nasal secretion (54 v 23%; p < 0.05) and dry cough (38 v 12%; p < 0.05). Workers with specific IgG had more dry cough (38 v 12%; p < 0.05), but less symptoms of non-specific bronchial hyperreactivity (0 v 26%; p < 0.05). Atopic workers sneezed more than non-atopic workers (65 v 30%; p < 0.01). In a prospective study five sensitised workers who left the factory became less reactive to metacholine, and became symptom free. In 41 workers who stayed, there was no improvement, despite a 10-fold reduction in exposure. The results show the extreme sensitising properties of MTHPA. PMID:1463677

  10. Surface modification of cell culture carriers: routes to anhydride functionalization of polystyrene.

    PubMed

    Nitschke, Mirko; Ricciardi, Serena; Gramm, Stefan; Zschoche, Stefan; Herklotz, Manuela; Rivolo, Paola; Werner, Carsten

    2012-02-01

    Physico-chemical and topographical cues allow to control the behavior of adherent cells. Towards this goal, commercially available cell culture carriers can be finished with a laterally microstructured biomolecular functionalization. As shown in a previous study [Biomacromolecules 4 (2003) 1072], the anhydride moiety facilitates a simple and versatile way to protein binding. The present work addresses the technical issue of anhydride surface functionalization of polystyrene, the most common material for cell culture ware. Different approaches based on low pressure plasma, electron beam and ultraviolet light techniques (i.e. maleic anhydride plasma reactions; plasma, electron beam and UV immobilization of functional polymer thin films; grafting of functional polymers to plasma activated surfaces) are introduced and briefly illustrated with examples. Results are characterized by Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS) and ellipsometry. The different routes are compared in terms of technical feasibility and achievable surface properties.

  11. Crystal structure of 2,3-di-methyl-maleic anhydride: continuous chains of electrostatic attraction.

    PubMed

    Wiscons, Ren A; Zeller, Matthias; Rowsell, Jesse L C

    2015-08-01

    In the crystal structure of 2,3-di-methyl-maleic anhydride, C6H6O3, the closest non-bonding inter-molecular distances, between the carbonyl C and O atoms of neighboring mol-ecules, were measured as 2.9054 (11) and 3.0509 (11) Å, which are well below the sum of the van der Waals radii for these atoms. These close contacts, as well as packing motifs similar to that of the title compound, were also found in the crystal structure of maleic anhydride itself and other 2,3-disubstituted maleic anhydrides. Computational modeling suggests that this close contact is caused by strong electrostatic inter-actions between the carbonyl C and O atoms.

  12. Collagen functionalized with unsaturated cyclic anhydrides-interactions in solution and solid state.

    PubMed

    Potorac, S; Popa, M; Picton, L; Dulong, V; Verestiuc, L; Le Cerf, D

    2014-03-01

    Maleic anhydride (CMA) and itaconic anhydride modified collagen (CITA) were prepared as precursors for production of interpenetrated polymer networks (IPN). Calculated values for Huggins coefficient in aqueous diluted and semi-diluted solutions of modified collagen indicated a slightly tendency of aggregation for itaconic anhydride-modified collagen. In semi-diluted solution collagen (Coll) and CMA present slightly differences in the thixotropic behavior, while CITA has a pronounced thixotropic behavior. Flow and oscillatory measurements revealed an elastic behavior of the collagen solutions, pure and modified with MA or ITA, as the storage modulus (G') has always a superior value compared with the loss modulus (G″). The denaturation temperature (Td) of unmodified collagen increased from 34°C to 40°C for CMA and to 39°C for CITA respectively, by formation of covalent bonds that stabilize the triple helix.

  13. Solvothermal process for grafting maleic anhydride onto poly(ethylene 1-octene)

    NASA Astrophysics Data System (ADS)

    Liu, Qiaochu; Qi, Rongrong; Shen, Yanhan; Zhou, Chixing

    2007-11-01

    Solvothermal process was developed to graft maleic anhydride (MAH) onto poly(ethylene 1-octene) (POE). Fourier transform infrared spectra (FT-IR) and 1H NMR spectra confirmed that maleic anhydride was successfully grafted onto the POE. The influences of MAH content, initiator concentration, POE concentration, reaction temperature, reaction time and solvents on the graft copolymerization were investigated through both of the grafting degree (GD) and gel content (GC). The results demonstrated that high grafting degree (up to 10.85%) could be obtained while the gel content was still low. Further studies revealed that POE-g-MAH could also be achieved in poor solvents of POE through this method.

  14. Synthesis of mixed acid anhydrides from methane and carbon dioxide in acid solvents.

    PubMed

    Zerella, Mark; Mukhopadhyay, Sudip; Bell, Alexis T

    2003-09-04

    [reaction: see text] The reaction of CH(4) with CO(2) has been performed in anhydrous acids using VO(acac)(2) and K(2)S(2)O(8) as promoters. NMR analysis establishes that the primary product is a mixed anhydride of acetic acid and the acid solvent. In sulfuric acid, the overall reaction is CH(4) + CO(2) + SO(3) --> CH(3)C(O)-O-SO(3)H. Hydrolysis of the mixed anhydride produces acetic acid and the solvent acid. When trifluoroacetic acid is the solvent, acetic acid is primarily formed via the reaction CH(4) + CF(3)COOH --> CH(3)COOH + CHF(3).

  15. Nano-encapsulation of coenzyme Q10 using octenyl succinic anhydride modified starch

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Octenyl succinic anhydride modified starch (OSA-ST) was used to encapsulate Coenzyme Q10 (CoQ10). CoQ10 was dissolved in rice bran oil (RBO), and incorporated into an aqueous OSA-ST solution. High pressure homogenization (HPH) of the mixture was conducted at 170 MPa for 5-6 cycles. The resulting ...

  16. Effect of Phthalic Anhydride Modified Soy Protein on Viscoelastic Properties of Polymer Composites

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Phthalic anhydride (PA) modified soy protein isolates (SPI), both hydrolyzed and un-hydrolyzed, are investigated as reinforcement fillers in styrene-butadiene (SB) composites. The modification of SPI by PA increases the number of carboxylic acid functional groups on the protein surface and therefor...

  17. Technical note: Tall oil fatty acid anhydrides as corrosion inhibitor intermediates

    SciTech Connect

    Fischer, E.R.; Parker, J.E. III

    1997-01-01

    Anhydrides derived from tall oil fatty acids offer enhanced corrosion inhibition properties compared to traditional dimer/trimer acids. The chemistry of this intermediate, its use in corrosion inhibition for downhole applications, and the synthesis of novel oil- and water-soluble derivatives were studied.

  18. A green synthesis of isatoic anhydrides from isatins with urea-hydrogen peroxide complex and ultrasound.

    PubMed

    Deligeorgiev, Todor; Vasilev, Aleksey; Vaquero, Juan J; Alvarez-Builla, Julio

    2007-07-01

    The oxidation of isatins at room temperature, using the cheap and environmentally friendly urea-hydrogen peroxide complex and ultrasonic irradiation, has been investigated. The ultrasonic irradiation dramatically reduces the reaction time. With easy and reproducible reaction procedures, different isatoic anhydrides were obtained in excellent yield and with high purity.

  19. SELECTIVE HYDROGENATION OF ANHYDRIDES TO LACTONES UNDER SUPERCRITICAL CARBON DIOXIDE MEDIUM

    EPA Science Inventory

    Selective Hydrogenation of Anhydrides to Lactones Under Supercritical Carbon Dioxide Medium

    Endalkachew Sahle-Demessie Unnikrishnan R Pillai
    U.S. EPA , 26 W. Martin Luther King Dr. Cincinnati, OH 45268 Phone: 513-569-7739
    Fax: 513-569-7677
    Abstract:
    Hydrogenat...

  20. TRIMELLITIC ANHYDRIDE-INDUCED EOSINOPHILLA IN A MOUSE MODEL OF OCCUPATIONAL ASTHMA

    EPA Science Inventory

    Trimellitic anhydride (TMA) is a low molecular weight chemical known to cause occupational asthma. The present study was designed to determine if TMA could elicit eosinophil infiltration into the lung of a sensitized mouse similarly to previous studies with the protein allergen ...

  1. Formation and stability of Vitamin E enriched nanoemulsions stabilized by Octenyl Succinic Anhydride modified starch

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Vitamin E (VE) is highly susceptible to autoxidation; therefore, it requires systems to encapsulate and protect it from autoxidation.In this study,we developed VE delivery systems, which were stabilized by Capsul® (MS), a starch modified with octenyl succinic anhydride. Influences of interfacial ten...

  2. Microwave synthesis and thermal properties of polyacrylate derivatives containing itaconic anhydride moieties

    PubMed Central

    2012-01-01

    Background Microwave irradiation as an alternative heat source is now a well-known method in synthetic chemistry. Microwave heating has emerged as a powerful technique to promote a variety of chemical reactions, offering reduced pollution, low cost and offer high yields together with simplicity in processing and handling. On the other hand, copolymers containing both hydrophilic and hydrophobic segments are drawing considerable attention because of their possible use in biological systems. Various copolymer compositions can produce a very large number of different arrangements, producing materials of varying chemical and physical properties. Thus, the hydrophilicity of copolymers can be modified by changing the amount of incorporated itaconic anhydride. Results A series of methyl methacrylate (MMA) and acrylamide (AA) copolymers containing itaconic anhydride (ITA) were synthesized by microwave irradiation employing a multimode reactor (Synthos 3000 Aton Paar, GmbH, 1400 W maximum magnetron) as well as conventional method. The thermal properties of the copolymers were evaluated by different techniques. Structure-thermal property correlation based on changing the itaconic anhydride ratio was demonstrated. Results revealed that the incorporation of itaconic anhydride into the polymeric backbone of all series affect the thermal stability of copolymers. In addition, the use of the microwave method offers high molecular weight copolymers which lead eventually to an increase in thermal stability. Conclusions Microwave irradiation method showed advantages for the produced copolymers compared to that prepared by conventional method, where it can offer a copolymer in short time, high yield, more pure compounds and more thermally stable copolymers, rather than conventional method. Also, microwave irradiation method gives higher molecular weight due to prevention of the chain transfer. Moreover, as the itaconic anhydride content increases the thermal stability and Tg increase

  3. [The working environment control of anhydride hardeners from an epoxy resin system].

    PubMed

    Matsumoto, Naomi; Yokota, Kozo; Johyama, Yasushi; Takakura, Toshiyuki

    2003-07-01

    Epoxy resins are widely used in adhesives, coatings, materials for molds and composites, and encapsulation. Acid anhydrides such as methyltetrahydrophthalic anhydride are being used as curing agents for epoxy resins. The anhydride hardeners are well-known industrial inhalant allergens, inducing predominantly type I allergies. In the electronic components industry, these substances have been consumed in large quantities. Therefore, safe use in the industry demands control of the levels of exposure causing allergic diseases in the workshop. We conducted a prospective survey of two electronics plants to clarify how to control the atmospheric level of the anhydrides in the work environment. Measurements of the levels of the anhydrides in air started according to the Working Environment Measurement Standards (Ministry of Labour Notification No. 46, 1976) in April 2000, along with improvements in the work environment. A value of 40 micrograms/m3 was adopted as the administrative control level to judge the propriety of the working environment control. A total of 2 unit work areas in both plants belonged to Control Class III. The exposure originated from manual loading, casting, uncured hot resins, and leaks in an impregnating-machine or curing ovens. In order to achieve the working environment control, complete enclosure of the source, installation of local exhaust ventilation, and improvement or maintenance of the local exhaust ventilation system were performed on the basis of the results of the working environment measurement, with the result that the work environment was improved (Control Class I). It became evident that these measures were effective just like other noxious substances.

  4. Ruthenium-catalyzed decarbonylative addition reaction of anhydrides with alkynes: a facile synthesis of isocoumarins and α-pyrones.

    PubMed

    Prakash, Rashmi; Shekarrao, Kommuri; Gogoi, Sanjib; Boruah, Romesh C

    2015-06-21

    A novel ruthenium catalyzed straightforward and efficient synthesis of isocoumarin and α-pyrone derivatives has been accomplished by the decarbonylative addition reaction of anhydrides with alkynes under thermal conditions.

  5. Preparation and Mechanical Properties of Chitosan-graft Maleic Anhydride Reinforced with Montmorillonite

    NASA Astrophysics Data System (ADS)

    Fajrin, A.; Sari, L. A.; Rahmawati, N.; Saputra, O. A.; Suryanti, V.

    2017-02-01

    The research aims to develop biodegradable composites as bio-based plastics from chitosan. The composites were prepared via solution casting method by introducing the maleic anhydride (MAH) as grafting agent and montmorillonite (MMt) as reinforcement. The grafting process of chitosan was conducted by varying concentrations of MAH which were 10, 20, and 30% w/w. It was observed that the chitosan-graft-maleic anhydride (Cs-g-MAH) containing 10% w/w of MAH increased its tensile strength by 70%. Reinforcement material was added to the Cs-g-MAH by varying MMt concentrations, e.g. 3, 6, 9 and 12% w/w. It was noted that the presence of 9% w/w of MMt in the Cs-g-MAH gave the best mechanical properties of the Cs-g-MAH/MMt composite.

  6. Enhanced activity of immobilized dimethylmaleic anhydride-protected poly- and monoclonal antibodies.

    PubMed

    Hadas, E; Koppel, R; Schwartz, F; Raviv, O; Fleminger, G

    1990-06-27

    The effect of reversible protection of the free amino groups of poly- and monoclonal antibodies by dimethylmaleic anhydride on their binding activity following immobilization onto various carriers was studied. The treatment with dimethylmaleic anhydride resulted in a 1.6-1.8-fold increase in the activity of immobilized goat anti-mouse immunoglobulin antibody immobilized onto different epoxy containing carriers and a 3-10.7-fold increase in the activity of immobilized monoclonal antibodies specific for carboxypeptidase A. The increase in activity was most pronounced at low antigen to carrier loads and over a wide range of modifier to protein ratios. The application of reversible protection of antibodies may permit the development of highly active immobilized antibody preparations for use in immunoaffinity purification.

  7. Formic Sulfuric Anhydride: a New Chemical Species with Possible Implications for Atmospheric Aerosol

    NASA Astrophysics Data System (ADS)

    Mackenzie, Becca; Dewberry, Chris; Leopold, Ken

    2015-06-01

    Aerosols are important players in the Earth's atmosphere, affecting climate, cloud formation, and human health. In this work, we report the discovery of a previously unknown molecule, formic sulfuric anhydride (FSA), that may influence the formation and composition of atmospheric aerosol particles. Five isotopologues of FSA have been observed by microwave spectroscopy and further characterized using DFT calculations. The system has dipole moment components along all three inertial axes, and indeed a, b, and c-type transitions have been observed. A π2 + π2 + σ2 cycloaddition reaction between SO3 and HCOOH is proposed as a possible mechanism for the formation of FSA and calculations indicate that the transformation is effectively barrierless. Facile formation of the anhydride followed by hydrolysis in small water-containing clusters or liquid droplets may provide a mechanism of incorporating volatile organics into atmospheric aerosol. We suggest that FSA and its derivatives be considered in future atmospheric and climate models.

  8. Electron paramagnetic resonance and FT-IR spectroscopic studies of glycine anhydride and betaine hydrochloride

    NASA Astrophysics Data System (ADS)

    Halim Başkan, M.; Kartal, Zeki; Aydın, Murat

    2015-12-01

    Gamma irradiated powders of glycine anhydride and betaine hydrochloride have been investigated at room temperature by electron paramagnetic resonance (EPR). In these compounds, the observed paramagnetic species were attributed to the R1 and R2 radicals, respectively. It was determined that the free electron interacted with environmental protons and 14N nucleus in both radicals. The EPR spectra of gamma irradiated powder samples remained unchanged at room temperature for two weeks after irradiation. Also, the Fourier Transform Infrared (FT-IR), FT-Raman and thermal analyses of both compounds were investigated. The functional groups in the molecular structures of glycine anhydride and betaine hydrochloride were identified by vibrational spectroscopies (FT-IR and FT-Raman).

  9. Evidence of glass transition in thin films of maleic anhydride derivatives: Effect of the surfactant coadsorption

    NASA Astrophysics Data System (ADS)

    López-Dıaz, D.; Velázquez, M. M.

    2008-08-01

    The glass transition temperature of poly (maleic anhydride-alt-1-octadecen) and poly (styrene-co-maleic anhydride) cumene-terminated thin films has been measured by mechanical relaxation of Langmuir films of these polymers. The dynamical properties show glass-like features (non-Arrhenius relaxation times and non-Debye mechanical response) interpreted by the coupling model. The glass transition temperature values determined by a mechanical relaxation experiment (step-compression) agree very well with those obtained by surface potential measurements. It is found that the glass transition temperature values in thin films decrease by about 100K as compared with those corresponding to the bulk polymers. The coadsorption of the water-insoluble surfactant DODAB decreases the glass transition temperature.

  10. Wheat Gluten Blends with Maleic Anhydride-Functionalized Polyacrylate Cross-Linkers for Improved Properties.

    PubMed

    Diao, Cheng; Xia, Hongwei; Parnas, Richard S

    2015-10-14

    A family of polyacrylate-based cross-linkers was synthesized to maximize the toughness of high Tg, high modulus wheat gluten blends in the glassy state. Mechanical testing and damping measurements were conducted to provide an example where the work of fracture and strength of the blend substantially exceeds polystyrene while maintaining flexure stiffness in excess of 3 GPa. The new rubbery cross-linkers, polymethyl acrylate-co-maleic anhydride and polyethyl acrylate-co-maleic anhydride, improve WG mechanical properties and reduce water absorption simultaneously. MDSC, FTIR, HPLC, and NMR data confirmed the cross-linking reaction with wheat gluten. Flexural, DMA, and water absorption testing were carried out to characterize the property improvements. DMA was conducted to investigate the relationship between energy damping and mechanical property improvement. If the cross-linker damping temperature is close to the testing temperature, the entire sample exhibits high damping, toughness, and strength.

  11. Salicylic acid (SA) bioaccessibility from SA-based poly(anhydride-ester).

    PubMed

    Rogers, Michael A; Yan, Yim-Fan; Ben-Elazar, Karen; Lan, Yaqi; Faig, Jonathan; Smith, Kervin; Uhrich, Kathryn E

    2014-09-08

    The bioaccessibility of salicylic acid (SA) can be effectively modified by incorporating the pharmacological compound directly into polymers such as poly(anhydride-esters). After simulated digestion conditions, the bioaccessibility of SA was observed to be statistically different (p < 0.0001) in each sample: 55.5 ± 2.0% for free SA, 31.2 ± 2.4% the SA-diglycolic acid polymer precursor (SADG), and 21.2 ± 3.1% for SADG-P (polymer). The release rates followed a zero-order release rate that was dependent on several factors, including (1) solubilization rate, (2) macroscopic erosion of the powdered polymer, (3) hydrolytic cleavage of the anhydride bonds, and (4) subsequent hydrolysis of the polymer precursor (SADG) to SA and diglycolic acid.

  12. Effect of impurities in polybutene on the quality of alkenylsuccinic anhydrides

    SciTech Connect

    Yarmolyuk, B.M.; Pustovit, V.E.; Bereza, L.I.; Antonov, V.N.; Shablii, V.I.; Vititneva, L.A.

    1984-03-01

    Synthesis of alkenylsuccini anhydrides (ASAs) was carried out in thermostable ampules at 230/sup 0/C in the course of 12 hours at an MA:PB molar ratio of 1.3:1 in a medium of prepurified petroleum xylene (30%). Freshly distilled maleic anhydride and industrial specimens of polybutene were used in the experiments. It was established that the main impurities which are formed in the production of polybutene and in its processing are ions of sodium, peroxide compounds and products of decomposition of the polymerization catalyst. The concentration of sodium ion was determined by an atomic adsorption method on an A-3000 instrument, the concentration of peroxides was determined by iodometry (3), and the concentration of catalyst decomposition products was determined from the amount of mechanical impurities.

  13. Biomaterial properties evaluation of poly(vinyl acetate- alt-maleic anhydride)/chitosan nanocapsules

    NASA Astrophysics Data System (ADS)

    Raţă, Delia Mihaela; Popa, Marcel; Chailan, Jean-François; Zamfir, Carmen Lăcrămioara; Peptu, Cătălina Anişoara

    2014-08-01

    Nanocapsules with diameter around 100 nm based on a natural polymer (chitosan) and a synthetic polymer poly(vinyl acetate- alt-maleic anhydride) [poly(MAVA)] by interfacial condensation method were prepared. The present study proposes a new type of biocompatible nanocapsules based on poly(vinyl acetate- alt-maleic anhydride-chitosan) (MCS) able to become a reliable support for inclusion and release of drugs. The spherical shape of the nanocapsules was evidenced by scanning electron microscopy. Nanocapsules presented a good Norfloxacin loading and release capacity. Haemocompatibility tests have demonstrated that the nanocapsules present a low toxicity and a good compatibility with sanguine medium. The biocompatibility properties of the nanocapsules after their intraperitoneal administration in rats were evidenced by histopathological examination of different organs (brain, liver, kidney, and lung). The results are encouraging and the nanocapsules can be used as controlled drug delivery systems.

  14. Stereocontrol in Asymmetric γ-Lactam Syntheses from Imines and Cyanosuccinic Anhydrides

    PubMed Central

    Pattawong, Ommidala; Tan, Darlene Q.; Fettinger, James C.; Shaw, Jared T.; Cheong, Paul Ha-Yeon

    2014-01-01

    Computations (SCS-MP2//B3LYP) reveal that the asymmetric synthesis of highly substituted γ-lactams with three stereogenic centers, including one quaternary center, proceeds through a Mannich reaction between the enol form of the anhydride and the E-imine, followed by a transannular acylation. This new mechanistic picture accounts for both the observed reactivity and stereoselectivity. CH-O and hydrogen bonding interactions in the Mannich step and torsional steering effects in the acylation step are responsible for stereocontrol. It is demonstrated that this new mechanistic picture applies to the related reactions of homophthalic anhydrides with imines and presents new vistas for the design of a new reaction to access complex molecular architectures. PMID:24070216

  15. On the Formation of Maleic Anhydride on a Vanadyl Pyrophosphate Surface: A Theoretical Study of the Mechanism

    DTIC Science & Technology

    1990-05-25

    synthesis of maleic anhydride from n - butane over a vanadium phosphorous oxide surface in the presence of molecular oxygen [equation ( 1 )]. 7 / • 3.5 0 2 (g...active vanadium phosphorous oxide phase in the oxidation of n - butane has been disputed in the literature. 7 0, 0 Generally, it is agreed that the presence...mechanism for the selective oxidation of n - butane to maleic anhydride. Satsuma et al. have described the surface structure in terms of the number of

  16. Palladium-catalyzed regioselective carbonylation of C-H bonds of N-alkyl anilines for synthesis of isatoic anhydrides.

    PubMed

    Guan, Zheng-Hui; Chen, Ming; Ren, Zhi-Hui

    2012-10-24

    A Pd-catalyzed regioselective C-H bond carbonylation of N-alkyl anilines for the synthesis of isatoic anhydrides has been developed. The key Pd-catalyst intermediate has been isolated and characterized. This novel Pd-catalyzed carbonylation reaction tolerates a wide range of functional groups and is a reliable method for the rapid elaboration of readily available N-alkyl anilines into a variety of substituted isatoic anhydrides under mild conditions.

  17. 1,3-Dipolar cycloaddition-decarboxylation reactions of an azomethine ylide with isatoic anhydrides: formation of novel benzodiazepinones.

    PubMed

    D'Souza, Asha M; Spiccia, Nadia; Basutto, Jose; Jokisz, Pawel; Wong, Leon S-M; Meyer, Adam G; Holmes, Andrew B; White, Jonathan M; Ryan, John H

    2011-02-04

    A nonstabilized azomethine ylide reacts with a wide range of substituted isatoic anhydrides to afford novel 1,3-benzodiazepin-5-one derivatives, which are generally isolated in high yield. The transformations involve 1,3-dipolar cycloaddition reactions of the ylide with the anhydrides to give transient, and in a representative case spectroscopically observable, oxazolidine intermediates that undergo ring-opening-decarboxylation-ring-closing reaction cascades to yield the 1,3-benzodiazepin-5-one products.

  18. Triamine-Modified Polyimides Having Improved Processability and Low Melt Flow Viscosity

    NASA Technical Reports Server (NTRS)

    Meador, Michael A. (Inventor); Nguyen, Baochan N. (Inventor); Eby, Ronald K. (Inventor)

    2001-01-01

    Addition-cured polyimides that contain the reaction product of an aromatic triamine or trianhydride analogue thereof, a reactive end group such as 5-norbornene-2, 3-dicarboxylic acid, ester derivatives of 5-norbornene-2, 3-dicarboxylic acid, anhydride derivatives of 5-norbornene-2, 3-dicarboxylic acid, or 4-phenylethynylphthalic anhydride, an aromatic diamine, and a dialkyl ester of an aromatic tetracarboxylic acid. The resultant starlike polyimides; exhibit lower melt flow viscosity than its linear counterparts, providing for improved processability of the polyimide. Also disclosed are methods for the synthesis of these polyimides as well as composite structures formed using these polyimides.

  19. Palladium-catalyzed decarboxylative coupling of isatoic anhydrides with arylboronic acids.

    PubMed

    Lu, Wei; Chen, Jiuxi; Liu, Miaochang; Ding, Jinchang; Gao, Wenxia; Wu, Huayue

    2011-11-18

    The decarboxylative coupling of isatoic anhydrides with arylboronic acids was realized for the first time in the presence of Pd(2)(dba)(3) and DPEphos, achieving aryl o-aminobenzoates with yields ranging from moderate to good. The efficiency of this procedure was demonstrated by good compatibility with fluoro, chloro, bromo, nitro, cyano, trifluoromethyl, formacyl, acetyl, thienyl, and naphthyl groups. Preliminary mechanistic experiments using deuterium labeling showed that the oxygen atom was derived from dioxygen.

  20. Preparation of hydrophilic styrene maleic anhydride copolymer fibers for use in papermaking

    DOEpatents

    Rave, Terence W.

    1979-01-01

    Hydrophilic fibers may be prepared by discharging a heated and pressurized dispersion of a styrene-maleic anhydride copolymer into a zone of reduced temperature and pressure, and then modifying the fibers so produced by treatment with an aqueous admixture of selected cationic and anionic water-soluble, nitrogen-containing polymers. Blends of the hydrophilic fibers with wood pulp provide paper products having improved physical properties.

  1. Novel synthetic method for the preparation of amphiphilic hyaluronan by means of aliphatic aromatic anhydrides.

    PubMed

    Huerta-Angeles, Gloria; Bobek, Martin; Příkopová, Eva; Šmejkalová, Daniela; Velebný, Vladimír

    2014-10-13

    The present work describes a novel and efficient method of synthesis of amphiphilic hyaluronan (HA) by esterification with alkyl fatty acids. These derivatives were synthesized under mild aqueous and well controlled conditions using mixed aliphatic aromatic anhydrides. These anhydrides characterized by the general formula RCOOCOC6H2Cl3 can be easily prepared by the reaction of the corresponding fatty acid (R) with 2,4,6-trichlorobenzoyl chloride (TCBC) in the presence of triethylamine. The aliphatic aromatic anhydrides RCOOCOC6H2Cl3 then react with the polysaccharide and enable the synthesis of aliphatic acid esters of HA in good yields. No hydrolytic degradation of hyaluronic acid could be observed. Parameters controlling the degree of esterification were systematically studied. Fatty acids with different chain lengths can be introduced applying this methodology. The degree of substitution was decreasing with increasing length of hydrophobic chain. The reaction products were fully characterized by Fourier transform infrared spectroscopy (FT-IR), nuclear magnetic resonance (NMR), SEC-MALLS and chromatographic analyses. Although the esterified HA products exhibited aggregation in solution as demonstrated by NMR, microscopy and rheology, they were still water-soluble.

  2. Study on oil absorbency of succinic anhydride modified banana cellulose in ionic liquid.

    PubMed

    Shang, Wenting; Sheng, Zhanwu; Shen, Yixiao; Ai, Binling; Zheng, Lili; Yang, Jingsong; Xu, Zhimin

    2016-05-05

    Banana cellulose contained number of hydrophilic hydroxyl groups which were succinylated to be hydrophobic groups with high oil affinity. Succinic anhydride was used to modify banana cellulose in 1-allyl-3-methylimidazolium chloride ionic liquid in this study. The modified banana cellulose had a high oil absorption capacity. The effects of reaction time, temperature, and molar ratio of succinic anhydride to anhydroglucose on the degree of substitution of modified banana cellulose were evaluated. The optimal reaction condition was at a ratio of succinic anhydride and anhydroglucose 6:1 (m:m), reaction time 60min and temperature 90°C. The maximum degree of acylation reaction reached to 0.37. The characterization analysis of the modified banana cellulose was performed using X-ray diffractometer, Fourier transform infrared spectrometer, scanning electron microscopy and thermogravimetry. The oil absorption capacity and kinetics of the modified banana cellulose were evaluated at the modified cellulose dose (0.025-0.3g), initial oil amount (5-30g), and temperature (15-35°C) conditions. The maximum oil absorption capacity was 32.12g/g at the condition of the cellulose dose (0.05g), initial oil amount (25g) and temperature (15°C). The kinetics of oil absorption of the cellulose followed a pseudo-second-order model. The results of this study demonstrated that the modified banana cellulose could be used as an efficient bio-sorbent for oil adsorption.

  3. Reevaluation of Tetrahydrophthalic Anhydride as an End Cap for Improved Oxidation Resistance in Addition Polyimides

    NASA Technical Reports Server (NTRS)

    Meador, Mary Ann B.; Frimer, Aryeh A.; Johnston, J. Christopher

    2003-01-01

    Several substituted 1,2,3,6-tetrahydrophthalic anhydride end caps - including the 3-phenyl, 3-methoxy, 3-trimethylsilyloxy, and 3,6-diphenyl analogs - were synthesized via the Diels-Alder condensation of the corresponding butadienes and maleic anhydride. These anhydrides, as well as the commercially available 3-hydro and 4-methyl analogs, were each ground together with methylenedianiline in a 2:1 ratio and heated gradually from 204 C to 371 C, with the thermolysis followed by NMR. Generally speaking, a transformation via monoimide to bisimide was observed in the lower temperature range, followed by competition between crosslinking and aromatization. We believe that this competition produces a substantial percentage of aromatic product, with the concomitant lowering of the relative amount of crosslinking and is responsible for improving both thermal oxidative stability of tetrahydrophthalic end capped polyimides and their substantial frangibility. The thermolysis of the tetrahydrophthalimides under inert atmosphere dramatically lowers the amount of aromatization hence, the mechanism for aromatization is an oxidative one.

  4. Prognostic value of clinical variables at presentation in patients with non-ST-segment elevation acute coronary syndromes: results of the Proyecto de Estudio del Pronóstico de la Angina (PEPA).

    PubMed

    López de Sá, Esteban; López-Sendón, José; Anguera, Ignasi; Bethencourt, Armando; Bosch, Xavier

    2002-11-01

    Patients with suspected non-ST-segment elevation acute coronary syndromes (NSTEACS) constitute a heterogeneous population with variable outcomes. Risk stratification in this population of patients is difficult due to the complexity in patient risk profile. We conducted this study to characterize the value of clinical and electrocardiographic variables for risk stratification in an unselected population of consecutive patients with NSTEACS on admission. Thirty-five clinical and electrocardiographic variables at presentation in the emergency room of 18 hospitals were prospectively analyzed in 4,115 patients with NSTEACS and related with the outcomes at 90 days. We also developed a risk score using the variables found to be independent predictors of ischemic events to facilitate risk stratification. Cardiovascular mortality was 4.3% and the rate for the outcome of either cardiovascular death or nonfatal myocardial infarction was 6.9%. The only independent predictors of mortality were age, diabetes, peripheral vascular disease, postinfarction angina, Killip class > or = 2, ST-segment depression, and elevation of cardiac markers. A risk profile using the variables found to be independent predictors of events was calculated for cardiovascular mortality and for the combination of either death or nonfatal myocardial infarction. Event rates increased significantly in all subgroups of patients based on the number of independent risk factors as the risk score increased. Using these factors, 90-day mortality ranged from as low as 0.4% in patients with no risk factors to 21.1% for those with more than 4 risk factors. In conclusion, simple clinical and electrocardiographic data obtained at hospital admission allow an accurate risk stratification of patients with NSTEACS. In the PEPA registry, simple variables easy to obtain at admission appear to be a valuable tool in discerning between patients at very low and very high risk according to the cluster of factors for each patient

  5. Orientation and bonding of benzoic acid, phthalic anhydride and pyromellitic dianhydride on Cu(110)

    NASA Astrophysics Data System (ADS)

    Frederick, B. G.; Ashton, M. R.; Richardson, N. V.; Jones, T. S.

    1993-07-01

    The interaction of the polyimide precursor pyromellitic dianhydride (PMDA), and the related compounds benzoic acid and phthalic anhydride, with Cu(110) has been studied by high resolution electron energy loss spectroscopy (HREELS). For benzoic acid, deprotonation of the carboxylic acid group occurs on adsorption leading to the formation of a surface benzoate species (C 6H 5COO-). Bonding to the surface occurs through a carboxylate linkage via two equivalent oxygen atoms. The HREEL spectrum is characterised by an intense dipole active band, the symmetric OCO stretching vibration, at ˜ 1420 cm -1. The plane of the carboxylate group is aligned perpendicular to the surface as is the plane of the benzene ring. A similar species is found following exposure of Cu(110) to phthalic anhydride. The carboxylate linkage results from disruption of the anhydride ring with loss of the CO character (C 6H 4COO-). In the case of the dianhydride species PMDA, only one of the anhydride units is used in bonding to the surface; the second unit points away from the surface and is characterised by the symmetric anhydride stretch at 1255 cm -1 and weak OO stretching vibrations at ˜ 1850 cm -1. In both cases, changes in the intensity of some of the bands compared with benzoic acid suggest that the carboxylate group is tilted away from the surface normal due to an interaction between one of the carbons of the aromatic ring and the copper surface. This implies that the plane of the aromatic ring is now twisted out of the plane of the carboxylate group and, although still perpendicular to the surface, the axis is tilted to allow one of the β-carbon atoms to interact with the surface. In all cases, off-specular measurements at a primary electron energy of ˜ 8 eV are dominated by the intense CH stretching vibration. Measurements of the intensity of this mode, in the surface benzoate species, as a function of incident electron energy suggest that excitation of this mode occurs via

  6. 40 CFR 721.3635 - Octadecanoic acid, ester with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ...-propanediol, phosphate, anhydride with silicic acid (H4SiO4). 721.3635 Section 721.3635 Protection of..., ester with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4). (a) Chemical substance and... with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4) (PMN P-96-1520; CAS No....

  7. 40 CFR 721.3635 - Octadecanoic acid, ester with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ...-propanediol, phosphate, anhydride with silicic acid (H4SiO4). 721.3635 Section 721.3635 Protection of..., ester with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4). (a) Chemical substance and... with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4) (PMN P-96-1520; CAS No....

  8. 40 CFR 721.3635 - Octadecanoic acid, ester with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ...-propanediol, phosphate, anhydride with silicic acid (H4SiO4). 721.3635 Section 721.3635 Protection of..., ester with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4). (a) Chemical substance and... with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4) (PMN P-96-1520; CAS No....

  9. XPS depth profiling of derivatized amine and anhydride plasma polymers: Evidence of limitations of the derivatization approach

    NASA Astrophysics Data System (ADS)

    Manakhov, Anton; Michlíček, Miroslav; Felten, Alexandre; Pireaux, Jean-Jacques; Nečas, David; Zajíčková, Lenka

    2017-02-01

    The quantitative analysis of the chemistry at the surface of functional plasma polymers is highly important for the optimization of their deposition conditions and, therefore, for their subsequent applications. The chemical derivatization of amine and carboxyl-anhydride layers is a well-known technique already applied by many researchers, notwithstanding the known drawback of the derivatization procedures like side or uncomplete reactions that could lead to "unreliable" results. In this work, X-ray photoelectron spectroscopy (XPS) combined with depth profiling with argon clusters is applied for the first time to study derivatized amine and carboxyl-anhydride plasma polymer layers. It revealed an additional important parameter affecting the derivatization reliability, namely the permeation of the derivatizing molecule through the target analysed layer, i.e. the composite effect of the probe molecule size and the layer porosity. Amine-rich films prepared by RF low pressure plasma polymerization of cyclopropylamine were derivatized with trifluoromethyl benzaldehide (TFBA) and it was observed by that the XPS-determined NH2 concentration depth profile is rapidly decreasing over top ten nanometers of the layer. The anhydride-rich films prepared by atmospheric plasma co-polymerization of maleic anhydride and C2H2 have been reacted with, parafluoroaniline and trifluoroethyl amine. The decrease of the F signal in top surface layer of the anhydride films derivatized by the "large" parafluoroaniline was observed similarly as for the amine films but the derivatization with the smaller trifluoroethylamine (TFEA) led to a more homogenous depth profile. The data analysis suggests that the size of the derivatizing molecule is the main factor, showing that the very limited permeation of the TFBA molecule can lead to underestimated densities of primary amines if the XPS analysis is solely carried out at a low take-off angle. In contrast, TFEA is found to be an efficient

  10. Drawbacks in the use of unconventional hydrophobic anhydrides for histone derivatization in bottom-up proteomics PTM analysis

    PubMed Central

    Sidoli, Simone; Yuan, Zuo-Fei; Lin, Shu; Karch, Kelly; Wang, Xiaoshi; Bhanu, Natarajan; Arnaudo, Anna M.; Britton, Laura-Mae; Cao, Xing-Jun; Gonzales-Cope, Michelle; Han, Yumiao; Liu, Shichong; Molden, Rosalynn C.; Wein, Samuel; Afjehi-Sadat, Leila; Garcia, Benjamin A.

    2015-01-01

    Mass spectrometry (MS)-based proteomics has become the most utilized tool to characterize histone post-translational modifications (PTMs). Since histones are highly enriched in lysine and arginine residues, lysine derivatization has been developed to prevent the generation of short peptides (3-6 residues) during trypsin digestion. One of the most adopted protocols applies propionic anhydride for derivatization. However, the propionyl group is not sufficiently hydrophobic to fully retain the shortest histone peptides in reversed-phase liquid chromatography, and such procedure also hampers the discovery of natural propionylation events. In this work we tested 12 commercially available anhydrides, selected based on their safety and hydrophobicity. Performance was evaluated in terms of yield of the reaction, MS/MS fragmentation efficiency and drift in retention time by using the following samples: (i) a synthetic unmodified histone H3 tail, (ii) synthetic modified histone peptides and (iii) a histone extract from cell lysate. Results highlighted that 7 of the selected anhydrides increased peptide retention time as compared to propionic, and several anhydrides such as benzoic and valeric led to high MS/MS spectra quality. However, propionic anhydride derivatization still resulted in our opinion as the best protocol to achieve high MS sensitivity and more even ionization efficiency among the analyzed peptides. PMID:25641854

  11. Reactive Additives for Phenylethynyl-Containing Resins

    NASA Technical Reports Server (NTRS)

    Connell, John W.; Smith, Joseph G., Jr.; Hergenrother, Paul M.; Rommel, Monica L.

    2005-01-01

    ,4'-oxydianiline (3,4'-ODA), 1,3-bis(3-aminophenoxy) benzene (1,3-APB), and 4-phenylethynylphthalic anhydride (PEPA). PERA-1 was made from 3,5-diamino- 4.-phenylethynylbenzophenon and equimolar amounts of phthalic anhydride and PEPA. To make PERA-1 in the imide form, the aforementioned ingredients were processed by refluxing in glacial acetic acid. To make the amide form of PERA-1, the ingredients were reacted in N-methyl-2-pyrrolidinone (NMP) under nitrogen at a temperature of 23 C (see figure). On the basis of the processability and other properties, a blend comprising 20 weight percent of PERA-1 and 80 weight percent PETI-5 was selected for further evaluation. Relative to neat PETI-5, the blend exhibited an increase in Tg; improved processability; and comparable values of shear strength in adhesion to titanium panels, open-hole compressive properties, compression properties after impact, and resistance to microcracking.

  12. Heterogeneous catalyst for the production of ethylidene diacetate from acetic anhydride

    DOEpatents

    Ramprasad, Dorai; Waller, Francis Joseph

    1998-01-01

    This invention relates to a process for producing ethylidene diacetate by the reaction of acetic anhydride, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled without loss in activity.

  13. Space charge behaviour in maleic anhydride grafted polyethylene/ethylene - vinyl - acetate copolymer laminates

    NASA Astrophysics Data System (ADS)

    Lee, Seung Hyung; Park, Jung Ki; Han, Jae Hong; Suh, Kwang S.

    1997-01-01

    Charge distributions in maleic anhydride (MAH) grafted polyethylene (g-PE)/ethylene - vinyl - acetate (EVA) copolymer laminates have been measured with materials of different composition. All laminates showed interfacial charge, the polarity and the magnitude of which are explained by interfacial polarization. It was found that the interfacial charge increased with the increase of MAH content in the g-PE, whereas it decreased with the increase of vinyl - acetate content in the EVA. This feature was attributed to the differences in electrical conductivity of the materials. Details of the experimental results are described.

  14. Design and Synthesis of Fast-Degrading Poly(anhydride-esters)

    PubMed Central

    Carbone, Ashley L.

    2009-01-01

    Fast-degrading, salicylate-based poly(anhydride-esters) were designed to degrade and release the active component, salicylic acid (SA), within 1 week. The polymer degradation was enhanced by using shorter or oxygen-containing aliphatic chains. A copolymer of diglycolic acid was also made with a salicylate-based diacid for comparison of polymer properties, including SA release. Both methods resulted in polyanhydrides with molecular weights ranging from 14 500 to 27 800 Da and displayed glass transition temperatures near physiological conditions, namely 33–40°C. the homo- and copolymers completely degraded within one week releasing the chemically incorporated SA. PMID:20161638

  15. Perfluoroalkylation of Unactivated Alkenes with Acid Anhydrides as the Perfluoroalkyl Source.

    PubMed

    Kawamura, Shintaro; Sodeoka, Mikiko

    2016-07-18

    An efficient perfluoroalkylation of unactivated alkenes with perfluoro acid anhydrides was developed. Copper salts play a crucial role as a catalyst to achieve allylic perfluoroalkylation with the in situ generated bis(perfluoroacyl) peroxides. Furthermore, carboperfluoroalkylation of alkene bearing an aromatic ring at an appropriate position on the carbon side chain was found to proceed under metal-free conditions to afford carbocycles or heterocycles bearing a perfluoroalkyl group. This method, which makes use of readily available perfluoroalkyl sources, offers a convenient and powerful tool for introducing a perfluoroalkyl group onto an sp(3) carbon to construct synthetically useful skeletons.

  16. Electrospun mats from styrene/maleic anhydride copolymers: modification with amines and assessment of antimicrobial activity.

    PubMed

    Ignatova, Milena; Stoilova, Olya; Manolova, Nevena; Markova, Nadya; Rashkov, Iliya

    2010-08-11

    New antimicrobial microfibrous electrospun mats from styrene/maleic anhydride copolymers were prepared. Two approaches were applied: (i) grafting of poly(propylene glycol) monoamine (Jeffamine® M-600) on the mats followed by formation of complex with iodine; (ii) modification of the mats with amines of 8-hydroxyquinoline or biguanide type with antimicrobial activity. Microbiological screening against S. aureus, E. coli and C. albicans revealed that both the formation of complex with iodine and the covalent attachment of 5-amino-8-hydroxyquinoline or of chlorhexidine impart high antimicrobial activity to the mats. In addition, S. aureus bacteria did not adhere to modified mats.

  17. Langmuir and Langmuir-Blodgett films of a maleic anhydride derivative: effect of subphase divalent cations.

    PubMed

    Martín-García, B; Velázquez, M Mercedes; Pérez-Hernández, J A; Hernández-Toro, J

    2010-09-21

    We report the study of the equilibrium and dynamic properties of Langmuir monolayers of poly(styrene-co-maleic anhydride) partial 2-buthoxyethyl ester cumene terminated polymer and the effect of the Mg(NO(3))(2) addition in the water subphase on the film properties. Results show that the polymer monolayer becomes more expanded when the electrolyte concentration in the subphase increases. Dense polymer films aggregate at the interface. The aggregates are transferred onto silicon wafers using the Langmuir-Blodgett methodology and the morphology is observed by AFM. The structure of aggregates depends on the subphase composition of the Langmuir film transferred onto the silicon wafer.

  18. Heterogeneous catalyst for the production of ethylidene diacetate from acetic anhydride

    DOEpatents

    Ramprasad, D.; Waller, F.J.

    1998-06-16

    This invention relates to a process for producing ethylidene diacetate by the reaction of acetic anhydride, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled without loss in activity.

  19. Adsorption of alkenyl succinic anhydride from solutions in carbon tetrachloride on a fine magnetite surface

    NASA Astrophysics Data System (ADS)

    Balmasova, O. V.; Ramazanova, A. G.; Korolev, V. V.

    2016-06-01

    The adsorption of alkenyl succinic anhydride from a solution in carbon tetrachloride on a fine magnetite surface at a temperature of 298.15 K is studied using fine magnetite, which forms the basis of magnetic fluids, as the adsorbent. An adsorption isotherm is recorded and interpreted in terms of the theory of the volume filling of micropores (TVFM). Adsorption process parameters are calculated on the basis of the isotherm. It is shown that at low equilibrium concentrations, the experimental adsorption isotherm is linear in the TVFM equation coordinates.

  20. The modification and characterization of maleic anhydride-styrene-methyl metacrylate terpolymer by poly(ethylene adipate)

    NASA Astrophysics Data System (ADS)

    Boztuğ, Ali; Basan, Satilmiş

    2007-03-01

    In this study, the functionality of maleic anhydride was utilized in the maleic anhydride-styrene-methyl metacrylate (MAStMMA) terpolymer. First, the polyester of poly(ethylene adipate), PEA, polycondensation copolymer was synthesized from ethylene glycol and adipic acid monomers. PEA was then modified on its maleic anhydride units in the MAStMMA terpolymer which has been synthesized previously. This modified copolymer was characterized by FTIR (Fourier Transform Infrared spectroscopy). The viscosimetric and thermomechanical characterization of MAStMMA terpolymer and its modified copolymer were also performed and the results were compared. The modified copolymer obtained was found to be more elastic and more soluble, and had lower viscosity and density.

  1. Characterization and in vitro degradation of salicylate-derived poly(anhydride-ester microspheres).

    PubMed

    Yeagy, Brian A; Prudencio, Almudena; Schmeltzer, Robert C; Uhrich, Kathryn E; Cook, Thomas J

    2006-09-01

    The aim of this study was to investigate how glass transition temperature (Tg) influenced polymer microsphere formation and degradation of three chemically, similar novel salicylatebased poly(anhydride-esters): poly[1,6-bis(o-carboxyphenoxy)hexanoate] (CPH), Tg = 59 degrees C; poly[1,8-bis(o-carboxyphenoxy)octanoate] (CPO), Tg = 30 degrees C; and poly[1,10-bis(ocarboxyphenoxy) decanoate] (CPD), Tg = 27 degrees C. Microspheres of these polymers were prepared using a modified oil-in-water solvent evaporation method and processed by either resuspension or washed by centrifugation. The morphology of the microspheres determined by scanning electron microscopy (SEM) revealed that an extra washing step appears to increase aggregation as the Tg decreases; whereas only limited aggregation occurred in the polymer with the lowest Tg, CPD, in those not washed by centrifugation. Residual polyvinyl alcohol apparently affected the drug release rates from the microspheres by a stabilization process that produced an 8 h lag time and a 5% decrease in the amount of drug released over a 7 day period compared to microspheres washed free of PVA. These results demonstrate that salicylate-based poly(anhydride-esters) with sufficiently high Tgs, can be processed into microspheres that release salicylate over a time period amenable for drug delivery applications.

  2. Preparation, characterization and antibacterial activity of octenyl succinic anhydride modified inulin.

    PubMed

    Zhang, Xiaoyun; Zhang, Ye-Wang; Zhang, Hongyin; Yang, Qiya; Wang, Haiying; Zhang, Guochao

    2015-01-01

    Octenyl succinic anhydride modified inulin (In-OSA) was synthesized via chemical modification of inulin with octenyl succinic anhydride (OSA). The esterification of inulin with OSA was confirmed by Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), and degree of substitution (DS) calculation. Antibacterial activity of In-OSA against Staphylococcus aureus and Escherichia coli was investigated by minimum inhibitory concentration (MIC) and inhibition rate determination. The results showed that inhibition rates against both E.coli and S. aureus increased with the increase of the In-OSA concentration. And the MICs against E. coli and S. aureus were 1% and 0.5% (w/v), respectively. The antibacterial mechanism was analyzed with the results of the proteins and nucleic acids leakage, SEM and negative staining transmission electron microscopy (TEM). Both the leakages of proteins and nucleic acids increased with the increase of the In-OSA concentration. The leakage occurred mainly in the early stage which indicated that cell membrane and wall were destroyed by In-OSA quickly. The images of SEM and negative staining TEM suggested that the cell membranes and cell walls of S. aureus were damaged more severely and even destroyed completely; but only pores appeared on the surface of E. coli.

  3. Catalytic behavior of Sn/Bi metal powder in anhydride-based epoxy curing.

    PubMed

    Jang, Keon-Soo; Eom, Yong-Sung; Moon, Jong-Tae; Oh, Yong-Soo; Nam, Jae-Do

    2009-12-01

    In this paper, we report the catalytic activity of the Sn/Bi alloy beads and its acceleration of the exothermic epoxy curing reactions in various thermal conditions and bead compositions. As being used as low-melting solder balls in electronic interconnection processes with various epoxy systems, it was found that the Sn/Bi beads substantially lowered the exothermic peak temperature of the diglycidyl ether of bisphenol A (DGEBA)/anhydride systems in up to ca. 140 degrees C depending on different types of anhydride curing agents. The catalytic activation of Sn/Bi powder was initiated with a small amount of Sn/Bi powder, for example, lowering ca. 50 degrees C of the exothermic peak temperature by adding only 0.1 vol% of Sn/Bi powder. The catalytic capability of the powder was increased by using smaller sized beads corresponding to larger catalytic surface area at the same volume fraction. Exhibiting a latent catalytic effect, the catalytic activity of Sn/Bi powder was remained latent at temperatures lower than 100 degrees C in isothermal conditions.

  4. Flexible Polyimide Aerogel Cross-linked by Poly(maleic Anhydride-alt-alkylene)

    NASA Technical Reports Server (NTRS)

    Guo, Haiquan; Meador, Mary Ann B.; Wilkewitz, Brittany Marie

    2014-01-01

    Aerogels are potential materials for aerospace applications due to their lower thermal conductivity, lighter weight, and low dielectric constant. However, silica aerogels are restricted due to their inherent fragility, hygroscopic nature, and poor mechanical properties, especially in extreme aerospace environments. In order to fit the needs of aerospace applications, developing new thermal insulation materials that are flexible, and moisture resistant is needed. To this end, we fabricated a series of polyimide aerogels crosslinked with different poly(maleic anhydride-alt-alkylene)s as seen in Scheme 1. The polyimide oligomers were made with 3,3,4,4-biphenyltetracarboxylic dianhydride (BPDA), and different diamines or diamine combinations. The resulting aerogels have low density (0.06 gcm3 to 0.16 gcm3) and high surface area (240-440 m2g). The effect of the different backbone structures on density, shrinkage, porosity, surface area, mechanical properties, moisture resistance and thermal properties will be discussed. These novel polyalkylene-imide aerogels may be potential candidates for applications such as space suit insulation for planetary surface missions, insulation for inflatable structures for habitats, inflatable aerodynamic decelerators for entry, descent and landing (EDL) operations, and cryotank insulation for advance space propulsion systems. Scheme 1. Network of polyimide aerogels crosslinked with deifferent poly(maleic anhydride).

  5. Interaction and release of catechin from anhydride maleic-grafted polypropylene films.

    PubMed

    López de Dicastillo, Carol; Castro-López, Maria Del Mar; Lasagabaster, Aurora; López-Vilariño, Jose M; González-Rodríguez, M Victoria

    2013-04-24

    In this paper, investigations were carried out on catechin-loaded maleic anhydride (MAH)-modified polypropylenes (PP). Two maleic-modified polypropylenes (PPMAH) with different maleic concentrations have been blended with PP and catechin to obtain composites of improved catechin retention with the aim of studying the possible interactions between these grafted polymers with antioxidants, and a secondary interest in developing an active antioxidant packaging. Composite physicochemical properties were measured by thermal analysis (thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and oxidation induction time (OIT)) and infrared spectroscopy studies. Catechin release profiles into food simulants were obtained by HPLC-PDA-QqQ, following European legislation. Antiradical activity of composites was analyzed by the ABTS and DPPH method. The formation of intermolecular hydrogen bonds between catechin and functionalized PP has been confirmed by Fourier transform infrared (FTIR) studies. Besides, a small fraction of ester bonds, formed as a result of a chemical reaction between a fraction of the hydrolyzed anhydride and the catechin hydroxyl groups, is not discarded. OIT results also showed an increase in antioxidant effectiveness caused by the presence of catechin- and maleic-modified PPMAH in the blend formulations. Incorporation of MAH-grafted PP increased substantially the retention rate of catechin, being dependent on the MAH content of the grafted polypropylene. The described interactions between catechin and maleic groups, together with changes in PP morphology in comparison with reference PP explained lower antioxidant release. Besides formulation, antioxidant release was dependent on the type of food, the temperature, and the time.

  6. Dual-Functional Hydrazide-Reactive and Anhydride-Containing Oligomeric Hydrogel Building Blocks.

    PubMed

    Kascholke, Christian; Loth, Tina; Kohn-Polster, Caroline; Möller, Stephanie; Bellstedt, Peter; Schulz-Siegmund, Michaela; Schnabelrauch, Matthias; Hacker, Michael C

    2017-03-13

    Biomimetic hydrogels are advanced biomaterials that have been developed following different synthetic routes. Covalent postfabrication functionalization is a promising strategy to achieve efficient matrix modification decoupled of general material properties. To this end, dual-functional macromers were synthesized by free radical polymerization of maleic anhydride with diacetone acrylamide (N-(1,1-dimethyl-3-oxobutyl)acrylamide) and pentaerythritol diacrylate monostearate. Amphiphilic oligomers (Mn < 7.5 kDa) with anhydride contents of 7-20% offered cross-linking reactivity to yield rigid hydrogels with gelatinous peptides (E = 4-13 kPa) and good cell adhesion properties. Mildly reactive methyl ketones as second functionality remained intact during hydrogel formation and potential of covalent matrix modification was shown using hydrazide and hydrazine model compounds. Successful secondary dihydrazide cross-linking was demonstrated by an increase of hydrogel stiffness (>40%). Efficient hydrazide/hydrazine immobilization depending on solution pH, hydrogel ketone content as well as ligand concentration for bioconjugation was shown and reversibility of hydrazone formation was indicated by physiologically relevant hydrazide release over 7 days. Proof-of-concept experiments with hydrazido-functionalized hyaluronan demonstrated potential for covalent aECM immobilization. The presented dual-functional macromers have perspective as reactive hydrogel building blocks for various biomedical applications.

  7. Stereocomplexes of enantiomeric lactic acid and sebacic acid ester-anhydride triblock copolymers.

    PubMed

    Slivniak, Raia; Domb, Abraham J

    2002-01-01

    A systematic study on the synthesis, characterization, degradation, and drug release of d-, l-, and dl-poly(lactic acid) (PLA)-terminated poly(sebacic acid) (PSA) and their stereocomplexes is reported. PLA-terminated sebacic acid polymers were synthesized by melt condensation of the acetate anhydride derivatives of PLA oligomers and sebacic anhydride oligomers to yield ABA triblock copolymers of molecular weights between 3000 and 9000 that melt at temperatures between 35 and 80 degrees C. Pairs of the corresponding enantiomeric ABA copolymers composed of l-PLA-PSA-l-PLA and d-PLA-PSA-d-PLA were solvent mixed to form stereocomplexes. The formed stereocomplexes exhibited higher crystalline melting temperature than the enantiomeric polymers, which indicate stereocomplex formulation. The PLA terminals had a significant effect on the polymer degradation and drug release rate. PSA with up to 20% w/w of PLA terminals degraded and released the incorporated drug for more than 3 weeks as compared with 10 days for PSA homopolymer.

  8. Pomelo peel modified with acetic anhydride and styrene as new sorbents for removal of oil pollution.

    PubMed

    Chai, Wenbo; Liu, Xiaoyan; Zou, Junchen; Zhang, Xinying; Li, Beibei; Yin, Tiantian

    2015-11-05

    Pomelo peel (PP), as one of the well-known agricultural wastes, is cost-effective and environmentally friendly. Based on PP, two new kinds of oil sorbents were prepared by using acetic anhydride and styrene. The structures of raw pomelo peel (RP), acetic anhydride-treated pomelo peel (AP) and styrene-treated pomelo peel (SP) were characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM), contact-angle (CA) measurements. The optimum reaction conditions for preparation of AP and SP were also investigated. The resulting products exhibited better oil sorption capacity than that of RP for diesel and lubricating oil, also SP had better oil sorption capacity than AP, while the oil sorption capacities of SP for diesel and lubricating oil reached 18.91 and 26.36 g/g, respectively. Adsorption kinetics was well described by the pseudo-second-order model. The results indicated that AP and SP, especially SP could be used as the substitute for non-biodegradable oil sorption materials.

  9. Effect of reagent access on the reactivity of coals. Final report. [Maleic anhydride; dialkylmaleates

    SciTech Connect

    Larsen, J.W.

    1983-04-01

    The objective of this work is to determine the extent to which the mass transport of reagents into solid coals limits the reactivity of those coals. The purpose of task one is to determine the effect of reagent access on the acid catalyzed depolymerization of coals using phenols and/or alkyl phenyl ethers. For task two, the purpose is to determine the effect of coal swelling on its rate of reaction with a dienophile. Work on depolymerization of coals in hot, acidic phenol has been completed. The conclusion is that due to incomplete depolymerization, the complications of competing Friedel-Crafts alkylation, and the condensation reactions of the solvent, the depolymerization of coals in hot, acidic phenol is not a useful technique for solubilizing coals for structural investigations. In task two, the rate of the Diels-Alder reaction between bituminous coals and maleic anhydride was found to be diffusion controlled. The observations of simple Fickian diffusion and reaction rate constants much slower than the Diels-Alder reaction of maleic anhydride and anthracene have no other reasonable explanation than rate limiting mass transport. The diffusion rates were found to be independent of the degree of solvent swelling of the coal. In addition, the dependence of the observed rates on temperature and the size of the dienophile were measured. Results obtained using a series of dialkylmaleates are presented. Size was found to play only a small role as long as the reagent is planar. 2 tables.

  10. Grafting of poly (lactic acid) with maleic anhydride using supercritical carbon dioxide

    NASA Astrophysics Data System (ADS)

    Khankrua, R.; Pivsa-Art, S.; Hiroyuki, H.; Suttiruengwong, S.

    2015-07-01

    The aim of this work was to modify poly lactic acid (PLA) via free radical grafting with maleic anhydride (MA) by using supercritical carbon dioxide (SCCO2). Benzoyl peroxide (BPO) was used as an initiator. The solubility of MA in SCCO2 was first determined to estimate the suitable grafting conditions and equilibrium. From the solubility study of MA in SCCO2, it was found that the solubility of MA in SCCO2 increased with the increasing pressure and dissolution time. PLA films were first prepared by compression molding. The ratio of MA to BPO was 2:1. The reaction temperature and pressure were 70°C and 100 bar respectively. The grafting reaction and the degree of grafting were characterized by nuclear magnetic resonance (NMR) spectroscopy and titration, respectively. Scanning electron microscope (SEM) technique and contact angle were used to confirm the changes in physical properties of PLA film grafted MA. NMR spectrum indicated that the grafting of MA onto PLA was successively achieved. Degree of grafting by using SCCO2 was as high as 0.98%. This provided rather high grafting degree compared with other processes. SEM pictures showed the rough surface structure on modified PLA film. In addition, contact angle results showed an improvement of the hydrophilicity by maleic anhydride grafting onto polymers.

  11. Efficient photochemical generation of peroxycarboxylic nitric anhydrides with ultraviolet light-emitting diodes

    NASA Astrophysics Data System (ADS)

    Rider, N. D.; Taha, Y. M.; Odame-Ankrah, C. A.; Huo, J. A.; Tokarek, T. W.; Cairns, E.; Moussa, S. G.; Liggio, J.; Osthoff, H. D.

    2015-07-01

    Photochemical sources of peroxycarboxylic nitric anhydrides (PANs) are utilized in many atmospheric measurement techniques for calibration or to deliver an internal standard. Conventionally, such sources rely on phosphor-coated low-pressure mercury (Hg) lamps to generate the UV light necessary to photo-dissociate a dialkyl ketone (usually acetone) in the presence of a calibrated amount of nitric oxide (NO) and oxygen (O2). In this manuscript, a photochemical PAN source in which the Hg lamp has been replaced by arrays of ultraviolet light-emitting diodes (UV-LEDs) is described. The output of the UV-LED source was analyzed by gas chromatography (PAN-GC) and thermal dissociation cavity ring-down spectroscopy (TD-CRDS). Using acetone, diethyl ketone (DIEK), diisopropyl ketone (DIPK), or di-n-propyl ketone (DNPK), respectively, the source produces peroxyacetic (PAN), peroxypropionic (PPN), peroxyisobutanoic (PiBN), or peroxy-n-butanoic nitric anhydride (PnBN) from NO in high yield (> 90 %). Box model simulations with a subset of the Master Chemical Mechanism (MCM) were carried out to rationalize product yields and to identify side products. The present work demonstrates that UV-LED arrays are a viable alternative to current Hg lamp setups.

  12. A self-crosslinking thermosetting monomer with both epoxy and anhydride groups derived from Tung oil fatty acids: Synthesis and properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A self-crosslinking compound with epoxy groups and anhydride groups (GEMA) has been successfully synthesized from Tung oil fatty acid by reacting with maleic anhydride via the Diels-Alder reaction. GEMA has very good storage stability and can be cured with trace amounts of tertiary amine. This advan...

  13. A self-crosslinking thermosetting monomer with both epoxy and anhydride groups derived from tung oil fatty acids: Synthesis and properties

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A self-crosslinking compound with epoxy groups and anhydride groups (GEMA) has been successfully synthesized from tung oil fatty acid by reacting with maleic anhydride via the Diels-Alder reaction. GEMA has very good storage stability and could be cured with trace amounts of tertiary amine. This ad...

  14. Soluble Synthetic Analogs of Malaria Pigment: Structure of Mesohematin Anhydride [FeIII(MP-IX)]2 and Solution Interaction with Chloroquine

    SciTech Connect

    D Bohle; E Dodd; A Kosar; L Sharma; P Stephens; L Suarez; D Tazoo

    2011-12-31

    Changing the vinyl groups of hematin anhydride to either ethyl or hydrogen groups results in increased solubility (Por=porphyrin). Determination of the weak binding constants of the antimalarial drug chloroquine to dimers of these hematin anhydride analogues suggests that solution-phase heme/drug interactions alone are unlikely to be the origin of the action of the drug.

  15. SELECTIVE HYDROGENATION OF MALEIC ANHYDRIDE TO Y-BUTYROLACTONE OVER PD/AL(2)O(3) CATALYST USING SUPERCRITICAL CO(2) AS SOLVENT

    EPA Science Inventory

    A selective hydrogenation of maleic anhydride to either y-butyrolactone or succinic anhydride over simple Pd/Al(2)O(3) catalyst under supercritical CO(2) medium is described for the first time which has considerable promise for obht lab-scale as well as industrial selective hydro...

  16. Organocatalytic Lewis base functionalisation of carboxylic acids, esters and anhydrides via C1-ammonium or azolium enolates.

    PubMed

    Morrill, Louis C; Smith, Andrew D

    2014-09-07

    This tutorial review highlights the organocatalytic Lewis base functionalisation of carboxylic acids, esters and anhydrides via C1-ammonium/azolium enolates. The generation and synthetic utility of these powerful intermediates is highlighted through their application in various methodologies including aldol-lactonisations, Michael-lactonisations/lactamisations and [2,3]-rearrangements.

  17. Tetrahydrophthalic Anhydrides as Addition Curing Polyimide End Caps: Thermal Isomerization of Methylendianiline 3,6-Diphenyltetrahydrophthalic Bisimides

    NASA Technical Reports Server (NTRS)

    Frimer, Aryeh A.; Gilinsky-Sharon, Pessia; Gottlieb, Hugo E.; Meador, Mary Ann B.; Johnston, J. Christopher

    2005-01-01

    In depth NMR studies confirm that heating a 1:2 mixture of cis, cis, cis 3,6-diphenyltetrahydrophthalic anhydride (end cap 9c) with methylenedianiline at 316 C initially yields the corresponding highly congested cis, cis, cis 3,6-diphenyltetrahydrophthalic bisimide 11, which is converted at this temperature to the observed product, the less hindered trans, cis, trans isomer 12.

  18. RAFT copolymerization of itaconic anhydride and 2-methoxyethyl acrylate: a multifunctional scaffold for preparation of "clickable" gold nanoparticles.

    PubMed

    Javakhishvili, Irakli; Kasama, Takeshi; Jankova, Katja; Hvilsted, Søren

    2013-05-25

    RAFT copolymerization of 2-methoxyethyl acrylate and itaconic anhydride - a monomer derived from renewable resources - is carried out in a controlled fashion. The copolymer allows preparation of gold nanoparticles with abundant surficial carboxyl and alkyne functional groups that are dendronized via Cu(I)-mediated "click" reaction.

  19. Evolutionary Importance of the Intramolecular Pathways of Hydrolysis of Phosphate Ester Mixed Anhydrides with Amino Acids and Peptides

    PubMed Central

    Liu, Ziwei; Beaufils, Damien; Rossi, Jean-Christophe; Pascal, Robert

    2014-01-01

    Aminoacyl adenylates (aa-AMPs) constitute essential intermediates of protein biosynthesis. Their polymerization in aqueous solution has often been claimed as a potential route to abiotic peptides in spite of a highly efficient CO2-promoted pathway of hydrolysis. Here we investigate the efficiency and relevance of this frequently overlooked pathway from model amino acid phosphate mixed anhydrides including aa-AMPs. Its predominance was demonstrated at CO2 concentrations matching that of physiological fluids or that of the present-day ocean, making a direct polymerization pathway unlikely. By contrast, the occurrence of the CO2-promoted pathway was observed to increase the efficiency of peptide bond formation owing to the high reactivity of the N-carboxyanhydride (NCA) intermediate. Even considering CO2 concentrations in early Earth liquid environments equivalent to present levels, mixed anhydrides would have polymerized predominantly through NCAs. The issue of a potential involvement of NCAs as biochemical metabolites could even be raised. The formation of peptide–phosphate mixed anhydrides from 5(4H)-oxazolones (transiently formed through prebiotically relevant peptide activation pathways) was also observed as well as the occurrence of the reverse cyclization process in the reactions of these mixed anhydrides. These processes constitute the core of a reaction network that could potentially have evolved towards the emergence of translation. PMID:25501391

  20. Evolutionary Importance of the Intramolecular Pathways of Hydrolysis of Phosphate Ester Mixed Anhydrides with Amino Acids and Peptides

    NASA Astrophysics Data System (ADS)

    Liu, Ziwei; Beaufils, Damien; Rossi, Jean-Christophe; Pascal, Robert

    2014-12-01

    Aminoacyl adenylates (aa-AMPs) constitute essential intermediates of protein biosynthesis. Their polymerization in aqueous solution has often been claimed as a potential route to abiotic peptides in spite of a highly efficient CO2-promoted pathway of hydrolysis. Here we investigate the efficiency and relevance of this frequently overlooked pathway from model amino acid phosphate mixed anhydrides including aa-AMPs. Its predominance was demonstrated at CO2 concentrations matching that of physiological fluids or that of the present-day ocean, making a direct polymerization pathway unlikely. By contrast, the occurrence of the CO2-promoted pathway was observed to increase the efficiency of peptide bond formation owing to the high reactivity of the N-carboxyanhydride (NCA) intermediate. Even considering CO2 concentrations in early Earth liquid environments equivalent to present levels, mixed anhydrides would have polymerized predominantly through NCAs. The issue of a potential involvement of NCAs as biochemical metabolites could even be raised. The formation of peptide-phosphate mixed anhydrides from 5(4H)-oxazolones (transiently formed through prebiotically relevant peptide activation pathways) was also observed as well as the occurrence of the reverse cyclization process in the reactions of these mixed anhydrides. These processes constitute the core of a reaction network that could potentially have evolved towards the emergence of translation.

  1. Evolutionary importance of the intramolecular pathways of hydrolysis of phosphate ester mixed anhydrides with amino acids and peptides.

    PubMed

    Liu, Ziwei; Beaufils, Damien; Rossi, Jean-Christophe; Pascal, Robert

    2014-12-11

    Aminoacyl adenylates (aa-AMPs) constitute essential intermediates of protein biosynthesis. Their polymerization in aqueous solution has often been claimed as a potential route to abiotic peptides in spite of a highly efficient CO2-promoted pathway of hydrolysis. Here we investigate the efficiency and relevance of this frequently overlooked pathway from model amino acid phosphate mixed anhydrides including aa-AMPs. Its predominance was demonstrated at CO2 concentrations matching that of physiological fluids or that of the present-day ocean, making a direct polymerization pathway unlikely. By contrast, the occurrence of the CO2-promoted pathway was observed to increase the efficiency of peptide bond formation owing to the high reactivity of the N-carboxyanhydride (NCA) intermediate. Even considering CO2 concentrations in early Earth liquid environments equivalent to present levels, mixed anhydrides would have polymerized predominantly through NCAs. The issue of a potential involvement of NCAs as biochemical metabolites could even be raised. The formation of peptide-phosphate mixed anhydrides from 5(4H)-oxazolones (transiently formed through prebiotically relevant peptide activation pathways) was also observed as well as the occurrence of the reverse cyclization process in the reactions of these mixed anhydrides. These processes constitute the core of a reaction network that could potentially have evolved towards the emergence of translation.

  2. Kinetics of Hydrolysis of Acetic Anhydride by In-Situ FTIR Spectroscopy: An Experiment for the Undergraduate Laboratory

    ERIC Educational Resources Information Center

    Haji, Shaker; Erkey, Can

    2005-01-01

    A reaction kinetics experiment for the chemical engineering undergraduate laboratory course was developed in which in-situ Fourier Transfer Infrared spectroscopy was used to measure reactant and product concentrations. The kinetics of the hydrolysis of acetic anhydride was determined by experiments carried out in a batch reactor. The results…

  3. Aggregate structure and effect of phthalic anhydride modified soy protein on the mechanical properties of styrene-butadiene copolymer

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The aggregate structure of phthalic anhydride (PA) modified soy protein isolate (SPI) was investigated by estimating its fractal dimension from the equilibrated dynamic strain sweep experiments. The estimated fractal dimensions of the filler aggregates were less than 2, indicating that these partic...

  4. Effects of Amine and Anhydride Curing Agents on the VARTM Matrix Processing Properties

    NASA Technical Reports Server (NTRS)

    Grimsley, Brian W.; Hubert, Pascal; Song, Xiaolan; Cano, Roberto J.; Loos, Alfred C.; Pipes, R. Byron

    2002-01-01

    To ensure successful application of composite structure for aerospace vehicles, it is necessary to develop material systems that meet a variety of requirements. The industry has recently developed a number of low-viscosity epoxy resins to meet the processing requirements associated with vacuum assisted resin transfer molding (VARTM) of aerospace components. The curing kinetics and viscosity of two of these resins, an amine-cured epoxy system, Applied Poleramic, Inc. VR-56-4 1, and an anhydride-cured epoxy system, A.T.A.R.D. Laboratories SI-ZG-5A, have been characterized for application in the VARTM process. Simulations were carried out using the process model, COMPRO, to examine heat transfer, curing kinetics and viscosity for different panel thicknesses and cure cycles. Results of these simulations indicate that the two resins have significantly different curing behaviors and flow characteristics.

  5. Preparation and Characterization of Octenyl Succinic Anhydride Modified Taro Starch Nanoparticles

    PubMed Central

    Jiang, Suisui; Dai, Lei; Qin, Yang; Xiong, Liu; Sun, Qingjie

    2016-01-01

    The polar surface and hydrophilicity of starch nanoparticles (SNPs) result in their poor dispersibility in nonpolar solvent and poor compatibility with hydrophobic polymers, which limited the application in hydrophobic system. To improve their hydrophobicity, SNPs prepared through self-assembly of short chain amylose debranched from cooked taro starch, were modified by octenyl succinic anhydride (OSA). Size via dynamic light scattering of OSA-SNPs increased compared with SNPs. Fourier transform infrared spectroscopy data indicated the OSA-SNPs had a new absorption peak at 1727 cm-1, which was the characteristic peak of carbonyl, indicating the formation of the ester bond. The dispersibility of the modified SNPs in the mixture of water with nonpolar solvent increased with increasing of degree of substitution (DS). OSA-SNPs appear to be a potential agent to stabilize the oil-water systems. PMID:26918568

  6. Stability of a salicylate-based poly(anhydride-ester) to electron beam and gamma radiation

    PubMed Central

    Rosario-Meléndez, Roselin; Lavelle, Linda; Bodnar, Stanko; Halperin, Frederick; Harper, Ike; Griffin, Jeremy; Uhrich, Kathryn E.

    2011-01-01

    The effect of electron beam and gamma radiation on the physicochemical properties of a salicylate-based poly(anhydride-ester) was studied by exposing polymers to 0 (control), 25 and 50 kGy. After radiation exposure, salicylic acid release in vitro was monitored to assess any changes in drug release profiles. Molecular weight, glass transition temperature and decomposition temperature were evaluated for polymer chain scission and/or crosslinking as well as changes in thermal properties. Proton nuclear magnetic resonance and infrared spectroscopies were also used to determine polymer degradation and/or chain scission. In vitro cell studies were performed to identify cytocompatibility following radiation exposure. These studies demonstrate that the physicochemical properties of the polymer are not substantially affected by exposure to electron beam and gamma radiation. PMID:21909173

  7. Stereodynamic control of star-epoxy/anhydride crosslinking actuated by liquid-crystalline phase transitions.

    PubMed

    Pin, Jean-Mathieu; Mija, Alice; Sbirrazzuoli, Nicolas

    2017-03-08

    The epoxy/anhydride copolymerization kinetics of an original star-epoxy monomer (TriaEP) was explored in dynamic heating mode using a series of isoconversional methods. Negative values of the apparent activation energy (Eα) related to an anti-Arrhenius behavior were observed. The transition from Arrhenius to anti-Arrhenius behavior and vice versa depending on the Eα of polymerization was correlated with the dynamics of mesophasic fall-in/fall-out events, physically induced transition (PIT) and chemically induced transition (CIT). This self-assembly phenomenon induces the generation of an anisotropic crosslinked architecture exhibiting both nematic discotic (ND) and nematic columnar (NC) organization. Particular emphasis was placed on evaluating the juxtaposition/contribution of the liquid-crystalline transitions to crosslinking, considering both the reaction dynamics and the macromolecular vision.

  8. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOEpatents

    Ramprasad, Dorai; Waller, Francis Joseph

    1999-01-01

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  9. Preparation and Characterization of Octenyl Succinic Anhydride Modified Taro Starch Nanoparticles.

    PubMed

    Jiang, Suisui; Dai, Lei; Qin, Yang; Xiong, Liu; Sun, Qingjie

    2016-01-01

    The polar surface and hydrophilicity of starch nanoparticles (SNPs) result in their poor dispersibility in nonpolar solvent and poor compatibility with hydrophobic polymers, which limited the application in hydrophobic system. To improve their hydrophobicity, SNPs prepared through self-assembly of short chain amylose debranched from cooked taro starch, were modified by octenyl succinic anhydride (OSA). Size via dynamic light scattering of OSA-SNPs increased compared with SNPs. Fourier transform infrared spectroscopy data indicated the OSA-SNPs had a new absorption peak at 1727 cm-1, which was the characteristic peak of carbonyl, indicating the formation of the ester bond. The dispersibility of the modified SNPs in the mixture of water with nonpolar solvent increased with increasing of degree of substitution (DS). OSA-SNPs appear to be a potential agent to stabilize the oil-water systems.

  10. "Push-pull" 1,8-naphthalic anhydride with multiple triphenylamine groups as electron donor

    NASA Astrophysics Data System (ADS)

    Wang, Limin; Shi, Yan; Zhao, Yingyuan; Liu, Heyuan; Li, Xiyou; Bai, Ming

    2014-01-01

    In this paper, the "push-pull" molecules consisting of different number of triphenylamino groups and 1,8-naphthalic anhydride ring were designed and synthesized. The UV-vis absorption and emission spectra of these compounds were recorded. Along with the increase on the number of the electron donating triphenylamino groups, both the absorption and emission bands show significant red shift. More importantly, the fluorescence quantum yields drop sharply along with the increase on the number of triphenylamino groups. The molecular structure, the frontier molecular orbital energies and the energy gaps between the highest occupied molecular orbital (HOMO) and the lowest un-occupied molecular orbital (LUMO) were calculated with DFT method. The calculated results indicate that the connection of more electron donating triphenylamino groups in molecule caused a change for the first excited state from an intramolecular charge transfer (ICT) state to an intramolecular electron transfer state (ET). This change on the first excited state has led to the fluorescence quenching.

  11. Role of Cellulose Nanocrystals on the Microstructure of Maleic Anhydride Plasma Polymer Thin Films.

    PubMed

    Brioude, Michel M; Roucoules, Vincent; Haidara, Hamidou; Vonna, Laurent; Laborie, Marie-Pierre

    2015-07-01

    Recently, it was shown that the microstructure of a maleic anhydride plasma polymer (MAPP) could be tailored ab initio by adjusting the plasma process parameters. In this work, we aim to investigate the ability of cellulose nanocrystals (CNCs) to induce topographical structuration. Thus, a new approach was designed based on the deposition of MAPP on CNCs model surfaces. The nanocellulosic surfaces were produced by spin-coating the CNC suspension on a silicon wafer substrate and on a hydrophobic silicon wafer substrate patterned with circular hydrophilic microsized domains (diameter of 86.9 ± 4.9 μm), resulting in different degrees of CNC aggregation. By depositing the MAPP over these surfaces, it was possible to observe that the surface fraction of nanostructures increased from 20% to 35%. This observation suggests that CNCs can act as nucleation points resulting in more structures, although a critical density of the CNCs is required.

  12. Preparation of extruded polyethylene/chitosan blends compatibilized with polyethylene-graft-maleic anhydride.

    PubMed

    Quiroz-Castillo, J M; Rodríguez-Félix, D E; Grijalva-Monteverde, H; Del Castillo-Castro, T; Plascencia-Jatomea, M; Rodríguez-Félix, F; Herrera-Franco, P J

    2014-01-30

    Novel films of polyethylene and chitosan were obtained using extrusion. These polymers have interesting properties, and processing them with methods that are of high use in the industry, such as the extrusion method, can have a significant effect on the potential applications of these materials. The individual materials were thermally characterized; after this, extruded films of low density polyethylene and chitosan mixtures were prepared with the addition of polyethylene-graft-maleic anhydride as a compatibilizer for the blends, and glycerol, as a plasticizer for chitosan. The use of compatibilizer and plasticizer agents improved the processability and compatibility of the mixtures, as well as their mechanical properties, as revealed by mechanical property measurements and scanning electron microscopy. It was possible to prepare blends with a maximum chitosan content of 20 wt%. The material stiffness increased with the increase of chitosan in the sample. FTIR studies revealed the existence of an interaction between the compatibilizer and chitosan.

  13. Mechanism of highly improved electrical properties in polypropylene by chemical modification of grafting maleic anhydride

    NASA Astrophysics Data System (ADS)

    Zhou, Yao; Hu, Jun; Dang, Bin; He, Jinliang

    2016-10-01

    This paper reports excellent electrical properties in polypropylene grafted with maleic anhydride (PP-g-MAH) and a related mechanism of the enhanced electrical properties. The chemical structure of PP-g-MAH was analyzed and its effect on space charge accumulation, electrical breakdown strength and DC conductivity was studied. Compared with pure PP, the PP-g-MAH exhibits remarkably suppressed space charge accumulation, enhanced electrical breakdown strength and reduced conduction current. The mechanism enhancing the electrical properties was studied by measuring the trap level distribution. It can be explained that abundant deep traps are introduced in PP-g-MAH with the introduction of polar groups in MAH, which reduces the charge mobility and raises the charge injection barrier so as to suppress space charge accumulation. This investigation would contribute to propose a new material modification strategy for designing high-voltage direct current insulation material in addition to the inclusion of nanoparticles.

  14. Improved removal of malachite green from aqueous solution using chemically modified cellulose by anhydride.

    PubMed

    Zhou, Yanmei; Min, Yinghao; Qiao, Han; Huang, Qi; Wang, Enze; Ma, Tongsen

    2015-03-01

    Cellulose modified with maleic (M) and phthalic (P) anhydride, to be named CMA and CPA, were tested as feasible adsorbents for the removal of malachite green from aqueous solution. At the same time, the uptake ability of natural cellulose was also studied for comparison. The structure of material was characterized by FT-IR and XRD. The effects of solution pH, initial dye concentration, contact time and temperature were investigated in detail by batch adsorption experiments. The kinetic and isotherm studies suggested that the adsorption followed the pseudo-second-order model and Langmuir isotherm. The maximum adsorption capacity on CMA and CPA were 370 mg g(-1) and 111 mg g(-1), respectively. Furthermore, the thermodynamics studies indicated the spontaneous nature of adsorption of malachite green on adsorbents. All the studied results showed that the modified cellulose could be used as effective adsorption material for the removal of malachite green from aqueous solutions.

  15. Poly(anhydride-esters) Comprised Exclusively of Naturally Occurring Antimicrobials and EDTA: Antioxidant and Antibacterial Activities

    PubMed Central

    2015-01-01

    Carvacrol, thymol, and eugenol are naturally occurring phenolic compounds known to possess antimicrobial activity against a range of bacteria, as well as antioxidant activity. Biodegradable poly(anhydride-esters) composed of an ethylenediaminetetraacetic acid (EDTA) backbone and antimicrobial pendant groups (i.e., carvacrol, thymol, or eugenol) were synthesized via solution polymerization. The resulting polymers were characterized to confirm their chemical composition and understand their thermal properties and molecular weight. In vitro release studies demonstrated that polymer hydrolytic degradation was complete after 16 days, resulting in the release of free antimicrobials and EDTA. Antioxidant and antibacterial assays determined that polymer release media exhibited bioactivity similar to that of free compound, demonstrating that polymer incorporation and subsequent release had no effect on activity. These polymers completely degrade into components that are biologically relevant and have the capability to promote preservation of consumer products in the food and personal care industries via antimicrobial and antioxidant pathways. PMID:24702678

  16. Phenolic acid-based poly(anhydride-esters) as antioxidant biomaterialsa

    PubMed Central

    Prudencio, Almudena; Faig, Jonathan J.; Song, MinJung

    2015-01-01

    Poly(anhydride-esters) comprised of naturally occurring, non-toxic phenolic acids, namely syringic and vanillic acid, with antioxidant properties were prepared via solution polymerization methods. Polymer and polymer precursor physiochemical properties were characterized, including polymer molecular weight and thermal properties. In vitro release studies illustrated that polymer hydrolytic degradation was influenced by relative hydrophobicity and degree of methoxy substitution of the phenolic acids. Further, the released phenolic acids were found to maintain antioxidant potency relative to free phenolic acid controls as determined by a 2,2-diphenyl-1-picrylhydrazyl assay. Polymer cytotoxicity was assessed with L929 fibroblasts in polymer-containing media; appropriate cell morphology and high fibroblast proliferation were obtained for the polymers at the lower concentrations. These polymers deliver non-cytotoxic levels of naturally occurring antioxidants, which could be efficacious in topical delivery of antioxidant therapies. PMID:26425923

  17. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOEpatents

    Ramprasad, D.; Waller, F.J.

    1999-04-06

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  18. Ionic liquids as novel solvents for biosynthesis of octenyl succinic anhydride-modified waxy maize starch.

    PubMed

    Li, Dandan; Zhang, Xiwen; Tian, Yaoqi

    2016-05-01

    Biosynthesis of octenyl succinic anhydride (OSA) starch was investigated using ionic liquids (ILs) as reaction media. Waxy maize starch was pretreated in 1-butyl-3-methylimidazolium chlorine and then esterified with OSA in 1-octyl-3-methylimidazolium nitrate by using Novozyme 435 as catalyst. The degree of substitution of OSA starch reached 0.0130 with 5 wt% starch concentration and 1 wt% lipase dosage based on ILs weight at 50 °C for 3h. The formation of OSA starch was confirmed by fourier transform infrared spectroscopy. Scanning electron microscopy and X-ray diffraction revealed that the morphology and crystal structure of starch were significantly destroyed. Thermogravimetric analysis showed that esterification decreased the thermal stability of starch. The successful lipase-catalyzed synthesis of OSA starch in ILs suggests that ILs are potential replacement of traditional organic solvents for starch ester biosynthesis.

  19. Poly(anhydride-esters) comprised exclusively of naturally occurring antimicrobials and EDTA: antioxidant and antibacterial activities.

    PubMed

    Carbone-Howell, Ashley L; Stebbins, Nicholas D; Uhrich, Kathryn E

    2014-05-12

    Carvacrol, thymol, and eugenol are naturally occurring phenolic compounds known to possess antimicrobial activity against a range of bacteria, as well as antioxidant activity. Biodegradable poly(anhydride-esters) composed of an ethylenediaminetetraacetic acid (EDTA) backbone and antimicrobial pendant groups (i.e., carvacrol, thymol, or eugenol) were synthesized via solution polymerization. The resulting polymers were characterized to confirm their chemical composition and understand their thermal properties and molecular weight. In vitro release studies demonstrated that polymer hydrolytic degradation was complete after 16 days, resulting in the release of free antimicrobials and EDTA. Antioxidant and antibacterial assays determined that polymer release media exhibited bioactivity similar to that of free compound, demonstrating that polymer incorporation and subsequent release had no effect on activity. These polymers completely degrade into components that are biologically relevant and have the capability to promote preservation of consumer products in the food and personal care industries via antimicrobial and antioxidant pathways.

  20. Synthesis and paste properties of octenyl succinic anhydride modified early Indica rice starch.

    PubMed

    Song, Xiao-yan; Chen, Qi-he; Ruan, Hui; He, Guo-qing; Xu, Qiong

    2006-10-01

    Octenyl succinic anhydride (OSA) modified early Indica rice starch was prepared in aqueous slurry systems using response surface methodology. The paste properties of the OSA starch were also investigated. Results indicated that the suitable parameters for the preparation of OSA starch from early Indica rice starch were as follows: reaction period 4 h, reaction temperature 33.4 degrees C, pH of reaction system 8.4, concentration of starch slurry 36.8% (in proportion to water, w/w), amount of OSA 3% (in proportion to starch, w/w). The degree of substitution was 0.0188 and the reaction efficiency was 81.0%. The results of paste properties showed that with increased OSA modification, the starch derivatives had higher paste clarity, decreased retrogradation and better freeze-thaw stability.

  1. Effects of hydrothermal pretreatment on subsequent octenylsuccinic anhydride (OSA) modification of cornstarch.

    PubMed

    Chen, Xu; He, Xiaowei; Huang, Qiang

    2014-01-30

    Cornstarch granules were hydrothermally pretreated and then esterified with octenylsuccinic anhydride (OSA). The physicochemical properties of cornstarch and hydrothermally pretreated OS-starch (H-OS-starch) were investigated. Results showed that hydrothermal pretreatments significantly increased the degree of substitution (DS) and reaction efficiency (RE) of H-OS-starch compared with the control. The higher the pretreatment temperature was, the more the OSA could go deep into the internal starch granules. The optimal pretreatment temperature for the OSA modification was 60°C. In addition, the OS groups appeared to be distributed throughout the OS-starch granules, especially on the surface, as shown by confocal laser scanning microscopy (CLSM). H-OS-starch had a slightly higher peak viscosity (Pv) and break down (BD) values, but lower pasting temperature (Tp) compared with the control OS-starch.

  2. Enhanced Activity of Nanocrystalline Beta Zeolite for Acylation of Veratrole with Acetic Anhydride.

    PubMed

    Aisha Mahmood Abdulkareem, Al-Turkustani; Selvin, Rosilda

    2016-04-01

    Friedel-Craft acylation of veratrole using homogeneous acid catalysts such as AlCl3, FeCl3, ZnCl2, and HF etc. produces acetoveratrone, (3',4'-dimethoxyacetophenone), which is the intermediate for synthesis of papavarine alkaloids. The problems associated with these homogeneous catalysts can be overcome by using heterogeneous solid catalysts. Since acetoveratrone is a larger molecule, large pore Beta zeolites with smaller particle sizes are beneficial for the liquid-phase acylation of veratrole, for easy diffusion of reactants and products. The present study aims in the acylation of veratrole with acetic anhydride using nanocrystalline Beta Zeolite catalyst. A systematic investigation of the effects of various reaction parameters was done. The catalysts were characterized for their structural features by using XRD, TEM and DLS analyses. The catalytic activity of nanocrystalline Beta zeolite was compared with commercial Beta zeolite for the acylation and was found that nanocrystalline Beta zeolite possessed superior activity.

  3. Structure and physicochemical properties of octenyl succinic anhydride modified starches: a review.

    PubMed

    Sweedman, Michael C; Tizzotti, Morgan J; Schäfer, Christian; Gilbert, Robert G

    2013-01-30

    Starches modified with octenyl succinic anhydride (OSA) have been used in a range of industrial applications, particularly as a food additive, for more than half a century. Interest in these products has grown in recent years as a result of new methods and applications becoming available. Due to a combination of OSA's hydrophobic and steric contribution and starch's peculiar highly branched macromolecular structure, these starch derivatives display useful stabilizing, encapsulating, interfacial, thermal, nutritional and rheological properties. We review the synthesis procedures, structural characterization methods and physico-chemical properties, and the influences of the botanical origins and structural parameters of OSA starches on physico-chemical properties. A better understanding of these features has the potential to lead to products with targeted macromolecular structures and optimized properties for specific applications.

  4. Crystal structures of alkylperoxo and anhydride intermediates in an intradiol ring-cleaving dioxygenase

    SciTech Connect

    Knoot, Cory J.; Purpero, Vincent M.; Lipscomb, John D.

    2014-12-29

    Intradiol aromatic ring-cleaving dioxygenases use an active site, nonheme Fe3+ to activate O2 and catecholic substrates for reaction. The inability of Fe3+ to directly bind O2 presents a mechanistic conundrum. The reaction mechanism of protocatechuate 3,4-dioxygenase is investigated in this paper using the alternative substrate 4-fluorocatechol. This substrate is found to slow the reaction at several steps throughout the mechanistic cycle, allowing the intermediates to be detected in solution studies. When the reaction was initiated in an enzyme crystal, it was found to halt at one of two intermediates depending on the pH of the surrounding solution. The X-ray crystal structure of the intermediate at pH 6.5 revealed the key alkylperoxo-Fe3+ species, and the anhydride-Fe3+ intermediate was found for a crystal reacted at pH 8.5. Intermediates of these types have not been structurally characterized for intradiol dioxygenases, and they validate four decades of spectroscopic, kinetic, and computational studies. In contrast to our similar in crystallo crystallographic studies of an Fe2+-containing extradiol dioxygenase, no evidence for a superoxo or peroxo intermediate preceding the alkylperoxo was found. This observation and the lack of spectroscopic evidence for an Fe2+ intermediate that could bind O2 are consistent with concerted formation of the alkylperoxo followed by Criegee rearrangement to yield the anhydride and ultimately ring-opened product. Finally, structural comparison of the alkylperoxo intermediates from the intra- and extradiol dioxygenases provides a rationale for site specificity of ring cleavage.

  5. Crystal structures of alkylperoxo and anhydride intermediates in an intradiol ring-cleaving dioxygenase

    DOE PAGES

    Knoot, Cory J.; Purpero, Vincent M.; Lipscomb, John D.

    2014-12-29

    Intradiol aromatic ring-cleaving dioxygenases use an active site, nonheme Fe3+ to activate O2 and catecholic substrates for reaction. The inability of Fe3+ to directly bind O2 presents a mechanistic conundrum. The reaction mechanism of protocatechuate 3,4-dioxygenase is investigated in this paper using the alternative substrate 4-fluorocatechol. This substrate is found to slow the reaction at several steps throughout the mechanistic cycle, allowing the intermediates to be detected in solution studies. When the reaction was initiated in an enzyme crystal, it was found to halt at one of two intermediates depending on the pH of the surrounding solution. The X-ray crystalmore » structure of the intermediate at pH 6.5 revealed the key alkylperoxo-Fe3+ species, and the anhydride-Fe3+ intermediate was found for a crystal reacted at pH 8.5. Intermediates of these types have not been structurally characterized for intradiol dioxygenases, and they validate four decades of spectroscopic, kinetic, and computational studies. In contrast to our similar in crystallo crystallographic studies of an Fe2+-containing extradiol dioxygenase, no evidence for a superoxo or peroxo intermediate preceding the alkylperoxo was found. This observation and the lack of spectroscopic evidence for an Fe2+ intermediate that could bind O2 are consistent with concerted formation of the alkylperoxo followed by Criegee rearrangement to yield the anhydride and ultimately ring-opened product. Finally, structural comparison of the alkylperoxo intermediates from the intra- and extradiol dioxygenases provides a rationale for site specificity of ring cleavage.« less

  6. Crystal structures of alkylperoxo and anhydride intermediates in an intradiol ring-cleaving dioxygenase

    PubMed Central

    Knoot, Cory J.; Purpero, Vincent M.; Lipscomb, John D.

    2015-01-01

    Intradiol aromatic ring-cleaving dioxygenases use an active site, nonheme Fe3+ to activate O2 and catecholic substrates for reaction. The inability of Fe3+ to directly bind O2 presents a mechanistic conundrum. The reaction mechanism of protocatechuate 3,4-dioxygenase is investigated here using the alternative substrate 4-fluorocatechol. This substrate is found to slow the reaction at several steps throughout the mechanistic cycle, allowing the intermediates to be detected in solution studies. When the reaction was initiated in an enzyme crystal, it was found to halt at one of two intermediates depending on the pH of the surrounding solution. The X-ray crystal structure of the intermediate at pH 6.5 revealed the key alkylperoxo-Fe3+ species, and the anhydride-Fe3+ intermediate was found for a crystal reacted at pH 8.5. Intermediates of these types have not been structurally characterized for intradiol dioxygenases, and they validate four decades of spectroscopic, kinetic, and computational studies. In contrast to our similar in crystallo crystallographic studies of an Fe2+-containing extradiol dioxygenase, no evidence for a superoxo or peroxo intermediate preceding the alkylperoxo was found. This observation and the lack of spectroscopic evidence for an Fe2+ intermediate that could bind O2 are consistent with concerted formation of the alkylperoxo followed by Criegee rearrangement to yield the anhydride and ultimately ring-opened product. Structural comparison of the alkylperoxo intermediates from the intra- and extradiol dioxygenases provides a rationale for site specificity of ring cleavage. PMID:25548185

  7. Crystal structures of alkylperoxo and anhydride intermediates in an intradiol ring-cleaving dioxygenase.

    PubMed

    Knoot, Cory J; Purpero, Vincent M; Lipscomb, John D

    2015-01-13

    Intradiol aromatic ring-cleaving dioxygenases use an active site, nonheme Fe(3+) to activate O2 and catecholic substrates for reaction. The inability of Fe(3+) to directly bind O2 presents a mechanistic conundrum. The reaction mechanism of protocatechuate 3,4-dioxygenase is investigated here using the alternative substrate 4-fluorocatechol. This substrate is found to slow the reaction at several steps throughout the mechanistic cycle, allowing the intermediates to be detected in solution studies. When the reaction was initiated in an enzyme crystal, it was found to halt at one of two intermediates depending on the pH of the surrounding solution. The X-ray crystal structure of the intermediate at pH 6.5 revealed the key alkylperoxo-Fe(3+) species, and the anhydride-Fe(3+) intermediate was found for a crystal reacted at pH 8.5. Intermediates of these types have not been structurally characterized for intradiol dioxygenases, and they validate four decades of spectroscopic, kinetic, and computational studies. In contrast to our similar in crystallo crystallographic studies of an Fe(2+)-containing extradiol dioxygenase, no evidence for a superoxo or peroxo intermediate preceding the alkylperoxo was found. This observation and the lack of spectroscopic evidence for an Fe(2+) intermediate that could bind O2 are consistent with concerted formation of the alkylperoxo followed by Criegee rearrangement to yield the anhydride and ultimately ring-opened product. Structural comparison of the alkylperoxo intermediates from the intra- and extradiol dioxygenases provides a rationale for site specificity of ring cleavage.

  8. Controlled delivery of paclitaxel from stent coatings using novel styrene maleic anhydride copolymer formulations.

    PubMed

    Richard, Robert; Schwarz, Marlene; Chan, Ken; Teigen, Nikolai; Boden, Mark

    2009-08-01

    The controlled release of paclitaxel (PTx) from stent coatings comprising an elastomeric polymer blended with a styrene maleic anhydride (SMA) copolymer is described. The coated stents were characterized for morphology by scanning electron microscopy (SEM) and atomic force microscopy (AFM), and for drug release using high-performance liquid chromatography (HPLC). Differential scanning calorimetry (DSC) was used to measure the extent of interaction between the PTx and polymers in the formulation. Coronary stents were coated with blends of poly(b-styrene-b-isobutylene-b-styrene) (SIBS) and SMA containing 7% or 14% maleic anhydride (MA) by weight. SEM examination of the stents showed that the coating did not crack or delaminate either before or after stent expansion. Examination of the coating surface via AFM after elution of the drug indicated that PTx resides primarily in the SMA phase and provided information about the mechanism of PTx release. The addition of SMA altered the release profile of PTx from the base elastomer coatings. In addition, the presence of the SMA enabled tunable release of PTx from the elastomeric stent coatings, while preserving mechanical properties. Thermal analysis reveled no shift in the glass transition temperatures for any of the polymers at all drug loadings studied, indicating that the PTx is not miscible with any component of the polymer blend. An in vivo evaluation indicated that biocompatibility and vascular response results for SMA/SIBS-coated stents (without PTx) are similar to results for SIBS-only-coated and bare stainless steel control stents when implanted in the non-injured coronary arteries of common swine for 30 and 90 days.

  9. Development of Highly Active and Regioselective Catalysts for the Copolymerization of Epoxides with Cyclic Anhydrides: An Unanticipated Effect of Electronic Variation.

    PubMed

    DiCiccio, Angela M; Longo, Julie M; Rodríguez-Calero, Gabriel G; Coates, Geoffrey W

    2016-06-08

    Recent developments in polyester synthesis have established several systems based on zinc, chromium, cobalt, and aluminum catalysts for the ring-opening alternating copolymerization of epoxides with cyclic anhydrides. However, to date, regioselective processes for this copolymerization have remained relatively unexplored. Herein we report the development of a highly active, regioselective system for the copolymerization of a variety of terminal epoxides and cyclic anhydrides. Unexpectedly, electron withdrawing substituents on the salen framework resulted in a more redox stable Co(III) species and longer catalyst lifetime. Using enantiopure propylene oxide, we synthesized semicrystalline polyesters via the copolymerization of a range of epoxide/anhydride monomer pairs.

  10. Water-soluble metal working fluids additives derived from the esters of acid anhydrides with higher alcohols for aluminum alloy materials.

    PubMed

    Yamamoto, Syutaro; Tomoda, Hideyuki; Watanabe, Shoji

    2007-01-01

    Water-soluble metal working fluids are used for processing of aluminum alloy materials. This short article describes properties of new additives in water-soluble metal working fluids for aluminum alloy materials. Many half esters or diesters were prepared from the reactions of higher alcohols with acid anhydrides. Interestingly, diesters of PTMG (tetrahydrofuran oligomer, MW = 650 and 1000) and polybutylene oxide (MW = 650) with maleic anhydride and succinic anhydride showed both of an excellent anti-corrosion property for aluminum alloy and a good hard water tolerance. The industrial soluble type processing oils including these additives also showed anti-corrosion property and hard water tolerance.

  11. Composite Properties of RTM370 Polyimide Fabricated by Vacuum Assisted Resin Transfer Molding (VARTM)

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Criss, James M.; Mintz, Eric A.; Shonkwiler, Brian; McCorkle, Linda S.

    2011-01-01

    RTM370 imide resin based on 2,3,3?,4?-biphenyl dianhydride (a-BPDA), 3,4'-oxydianinline (3,4'-ODA) with the 4-phenylethynylphthalic (PEPA) endcap has been shown to exhibit a high cured T(sub g) (370 C) and low melt viscosity (10-30 poise) at 280 C with a pot-life of 1-2 h. Previously, RTM370 resin has been successfully fabricated into composites reinforced with T650-35 carbon fabrics by resin transfer molding (RTM). RTM370 composites exhibit excellent mechanical properties up to 327?C (620?F), and outstanding property retention after aging at 288?C (550?F) for 1000 h. In this work, RTM370 composites were fabricated by vacuum assisted resin transfer molding (VARTM), using vacuum bags on a steel plate. The mechanical properties of RTM370 composites fabricated by VARTM are compared to those prepared by RTM.

  12. RTM370 Polyimide Braided Composites: Characterization and Impact Testing

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Revilock, Duane M.; Ruggeri, Charles R.; Criss, Jim M., Jr.; Mintz, Eric A.

    2013-01-01

    RTM370 imide oligomer based on 2,3,3',4'-biphenyl dianhydride (a-BPDA), 3,4'-oxydianiline (3,4'-ODA) and terminated with the 4-phenylethynylphthalic (PEPA) endcap has been shown to exhibit a low melt viscosity (10-30 poise) at 280 C with a pot-life of 1-2 h and a high cured glass transition temperature (Tg) of 370 C. RTM370 resin has been successfully fabricated into composites reinforced with T650-35 carbon fabrics by resin transfer molding (RTM). RTM370 composites display excellent mechanical properties up to 327 C (620 F), and outstanding property retention after aging at 288degC (550 F) for 1000 h, and under hot-wet conditions. In ballistic impact testing, RTM370 triaxial braided T650-35 carbon fiber composites exhibited enhanced energy absorption at 288 C (550 F) compared to ambient temperature.

  13. Polyimide Composites Properties of RTM370 Fabricated by Vacuum Assisted Resins Transfer Molding (VARTM)

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Criss, Jim M.; Mintz, Eric A.

    2011-01-01

    RTM370 imide resin based on 2,3,3 ,4 -biphenyl dianhydride ( a-BPDA), 3,4 -oxydianinline (3,4 -ODA) with 4-phenylethynylphthalic (PEPA) endcap has shown to exhibit high Tg (370 C) and low melt viscosity (10-30 poise) at 280 C with a pot-life of 1-2 h. Previously, RTM370 resin has been fabricated into composites with T650-35 carbon fabrics by resin transfer molding (RTM) successfully. RTM370 composites exhibit excellent mechanical properties up to 327 C (620 F), and outstanding property retention after aging at 288 C (550 F) for 1000 hrs. In this presentation, RTM 370 composites will be fabricated by vacuum assisted resins transfer molding (VARTM), using vacuum bags without mold. The mechanical properties of RTM370 composites fabricated by VARTM will be compared to those of RTM370 made by RTM.

  14. A biotin-conjugated pyridine-based isatoic anhydride, a selective room temperature RNA-acylating agent for the nucleic acid separation.

    PubMed

    Ursuegui, S; Yougnia, R; Moutin, S; Burr, A; Fossey, C; Cailly, T; Laayoun, A; Laurent, A; Fabis, F

    2015-03-28

    Isatoic anhydride derivatives, including a biotin and a disulfide linker were specifically designed for nucleic acid separation. 2'-OH selective RNA acylation, capture of biotinylated RNA adducts by streptavidin-coated magnetic beads and disulfide chemical cleavage led to isolation of highly enriched RNA samples from an initial 9/1 DNA-RNA mixture. Starting from the parent compound N-methylisatoic anhydride A which was used at 65 °C, we improved the extraction process by designing a new generation of isatoic anhydrides that are able to react under smoother conditions. Among them, a pyridine-based isatoic anhydride derivative 15f was found to be reactive at room temperature, leading to enhance the efficiency and selectivity of the extraction process by significantly reducing DNA side extraction. The extracted and purified RNAs can then be detected by RT-PCR.

  15. Modular access to vicinally functionalized allylic (thio)morpholinonates and piperidinonates by substrate-controlled annulation of 1,3-azadienes with hexacyclic anhydrides.

    PubMed

    Braunstein, Hannah; Langevin, Spencer; Khim, Monique; Adamson, Jonathan; Hovenkotter, Katie; Kotlarz, Lindsey; Mansker, Brandon; Beng, Timothy K

    2016-09-21

    A modular substrate-controlled hexannulation of inherently promiscuous 1,3-azadienes with hexacyclic anhydrides, which affords versatile vicinally functionalized allylic lactams, in high yields, regio- and stereoselectivities is described.

  16. Kinetics of the reactions of the acid anhydrides with aromatic amines in aprotic solvents. M.S. Thesis. Final Report

    NASA Technical Reports Server (NTRS)

    Sugg, E.; Mason, J. G.

    1983-01-01

    Work has revealed that diamine derivatives of diphenylmethane (IV), diphenyl ether (V), benzophenone (IV), fluorene (VII), and fluorenone (VIII) polymerizations with pyromellitic dianhydride in DMA were dependent on the basicity of the amine compound. The correlation between the basicity of the amine and its reactivity with phthalic anhydride was determined. Basicity measurements were made by potentiometric titration of each amine in an acetonitrile-water solvent system, from which the pKa of the amine could be determined. Reactivity was defined in terms of the second order rate constant derived form spectrophotometric examination of the reaction between each amine and phthalic anhydride in DMA. This reaction was expected to proceed in either one (for a monoamine) or two (for a diamine) stages.

  17. Methylol polyesters of C12-C22 hydrocarbon substituted succinic anhydride or acid, their preparation and use as additives for lubricants and fuels

    SciTech Connect

    Gutierrez, A.; Ryer, J.; Shaub, H.; Winans, E.D.

    1980-06-24

    Methylol polyester derivatives of C12-C22 hydrocarbon substituted succinic anhydride or acid which are the equimolar reaction products of said C12-C22 hydrocarbon substituted succinic anhydride or acid and a cyclic poly(Methylol) compound provide activity: in fuels as rust inhibitors; in automatic transmission fluids as copper corrosion inhibitors; and, in automotive, industrial and lubricating oils as sludge dispersants , rust-inhibitors, friction reducers (Lubricity agents) and copper alloy corrosion inhibitors.

  18. Application of palladium-catalyzed carboxyl anhydride-boronic acid cross coupling in the synthesis of novel bile acids analogs with modified side chains.

    PubMed

    Mayorquín-Torres, Martha C; Flores-Álamo, Marcos; Iglesias-Arteaga, Martin A

    2015-09-01

    Palladium-catalyzed cross coupling of 4-methoxycarbonyl phenyboronic acid with acetylated bile acids in which the carboxyl functions was activated by formation of a mixed anhydride with pivalic anhydride afforded the cross coupled compounds, which were converted in novel side chain modified bile acids by one pot carbonyl reduction/removal of the protecting acetyl groups by Wolff-Kishner reduction. Unambiguous assignments of the NMR signals and crystal characterization of the heretofore unknown compounds are provided.

  19. Ring-opening copolymerization of maleic anhydride with epoxides: a chain-growth approach to unsaturated polyesters.

    PubMed

    DiCiccio, Angela M; Coates, Geoffrey W

    2011-07-20

    We report the ring-opening copolymerization of maleic anhydride with a variety of epoxides catalyzed by a chromium(III) salen complex. Quantitative isomerization of the cis-maleate form of all polymers affords the trans-fumarate analogues. Addition of chain transfer reagents yields low M(n), narrow PDI polymer samples. This method provides access to a range of new unsaturated polyesters with versatile functionality, as well as the first synthesis of high molecular weight poly(propylene fumarate).

  20. Ficusmicrochlorin A-C, two new methoxy lactone chlorins and an anhydride chlorin from the leaves of Ficus microcarpa.

    PubMed

    Lin, Huan-You; Chiu, Hsi-Lin; Lu, Te-Ling; Tzeng, Chih-Ying; Lee, Tzong-Huei; Lee, Ching-Kuo; Shao, Yi-Yuan; Chen, Chiy-Rong; Chang, Chi-I; Kuo, Yueh-Hsiung

    2011-01-01

    Two new methoxy lactone chlorins ficusmicrochlorin A (1) and ficusmicrochlorin B (2), and one new anhydride chlorin ficusmicrochlorin C (3), along with eight known pheophytins were isolated from the leaves of Ficus microcarpa. Their structures were determined by the extensive 1D- and 2D-NMR techniques. New pheophytin compound was rarely obtained from natural sources. In the past ten years, only three new natural pheophytins were characterized.

  1. Tunable drug release profiles from salicylate-based poly(anhydride-ester) matrices using small molecule admixtures

    PubMed Central

    Ouimet, Michelle A; Snyder, Sabrina S; Uhrich, Kathryn E

    2013-01-01

    Poly(anhydride-esters) with salicylic acid, a nonsteroidal anti-inflammatory drug, chemically incorporated into the polymer backbone provide high inherent drug loading. These poly(anhydride-esters) hydrolytically degrade to release salicylic acid over extended time periods (>30 days); however, an initial lag period of no salicylic acid release is observed. This lag period could be unfavorable in applications where immediate salicylic acid release is desired. Poly(anhydride-esters) with short (2 days) and long (11 days) lag periods were admixed with various small molecules as a means to shorten or eliminate the lag period. Salicylic acid, larger salicylic acid prodrugs, and 1:1 combinations of the two were physically admixed, each at 1%, 5%, and 10% (w/w). All admixtures resulted in immediate salicylic acid release and a decrease in glass transition temperatures compared to polymer alone. By varying the amounts of salicylic acid and salicylic acid prodrugs incorporated into the polymer matrix, immediate and constant salicylic acid release profiles over varied time periods were achieved. PMID:24078768

  2. Mixed Anhydride Intermediates in the Reaction of 5(4H)‐Oxazolones with Phosphate Esters and Nucleotides

    PubMed Central

    Liu, Ziwei; Rigger, Lukas; Rossi, Jean‐Christophe; Sutherland, John D.

    2016-01-01

    Abstract 5(4H)‐Oxazolones can be formed through the activation of acylated α‐amino acids or of peptide C termini. They constitute potentially activated intermediates in the abiotic chemistry of peptides that preceded the origin of life or early stages of biology and are capable of yielding mixed carboxylic‐phosphoric anhydrides upon reaction with phosphate esters and nucleotides. Here, we present the results of a study aimed at investigating the chemistry that can be built through this interaction. As a matter of fact, the formation of mixed anhydrides with mononucleotides and nucleic acid models is shown to take place at positions involving a mono‐substituted phosphate group at the 3’‐ or 5’‐terminus but not at the internal phosphodiester linkages. In addition to the formation of mixed anhydrides, the subsequent intramolecular acyl or phosphoryl transfers taking place at the 3’‐terminus are considered to be particularly relevant to the common prebiotic chemistry of α‐amino acids and nucleotides. PMID:27534830

  3. Sensitive detection of proteins in polyacrylamide gel via isatoic anhydride derivatization: Introduction of a low-cost fluorescent prelabeling procedure.

    PubMed

    Asadollahi, Kazem; Rafiee, Saharnaz; Riazi, Gholamhossein

    2016-10-01

    Here, we introduce isatoic anhydride as a sensitive and commodious fluorescent prelabel for detection of proteins in one-dimensional polyacrylamide gels. High reactivity of isatoic anhydride with nucleophiles in mild alkaline environments makes it an appropriate tag for labeling of biomolecules. In this study, we show that preelectrophoresis labeling of proteins with isatoic anhydride for few minutes at room temperature allows detection of 2-4 ng of standard proteins, BSA and lysozyme, per band. Proteins were successfully labeled in the presence of a wide range of common biological reagents and in crude cell extract. The labeled proteins have the same electrophoretic migration in comparison to unlabeled proteins; however the application of saturation labeling method results in slight band broadening. Compatibility of the method with downstream processes was assessed by tryptic digestion of labeled proteins and study of peptide mixture using gel electrophoresis which revealed partial digestion of labeled proteins due to lysine modification. The present procedure is sensitive, rapid, and inexpensive and is a promising alternative for current protein staining procedures, where downstream processes are not desired.

  4. Mixed Anhydride Intermediates in the Reaction of 5(4H)-Oxazolones with Phosphate Esters and Nucleotides.

    PubMed

    Liu, Ziwei; Rigger, Lukas; Rossi, Jean-Christophe; Sutherland, John D; Pascal, Robert

    2016-10-10

    5(4H)-Oxazolones can be formed through the activation of acylated α-amino acids or of peptide C termini. They constitute potentially activated intermediates in the abiotic chemistry of peptides that preceded the origin of life or early stages of biology and are capable of yielding mixed carboxylic-phosphoric anhydrides upon reaction with phosphate esters and nucleotides. Here, we present the results of a study aimed at investigating the chemistry that can be built through this interaction. As a matter of fact, the formation of mixed anhydrides with mononucleotides and nucleic acid models is shown to take place at positions involving a mono-substituted phosphate group at the 3'- or 5'-terminus but not at the internal phosphodiester linkages. In addition to the formation of mixed anhydrides, the subsequent intramolecular acyl or phosphoryl transfers taking place at the 3'-terminus are considered to be particularly relevant to the common prebiotic chemistry of α-amino acids and nucleotides.

  5. Separation of maleic anhydride grafted polypropylene using multidimensional high-temperature liquid chromatography.

    PubMed

    Prabhu, K N; Macko, T; Brüll, R; Remerie, K; Tacx, J; Garg, P; Ginzburg, A

    2016-04-08

    Functionalization addresses a property gap of polyolefins and opens new perspectives due to improved surface properties in applications like composites (e.g., glass fiber reinforced polypropylene) and anti-corrosive coatings for metals. Various techniques have been developed to characterize functionalized polyolefins, yet no analytical approach addressing their chemical heterogeneity exists. Using High Temperature Size Exclusion Chromatography (HT-SEC) coupled to infrared spectroscopy we could show for two model samples of polypropylene grafted maleic anhydride (PP-g-MA), differing in their nominal MA content, that the grafting density increases with decreasing molar mass. Crystallization Analysis Fractionation (CRYSTAF) does not enable to separate these samples according to their composition to the extent required. Yet, when using High Temperature High Performance Liquid Chromatography (HT-HPLC), with either silica gel or Mica as stationary phase and a gradient mobile phase, a deformulation into a grafted and a non-grafted fraction could be achieved. This was confirmed by analyzing the eluted fractions by infrared spectroscopy. Hyphenating the separation according to composition with a separation according to molar mass (HT-HPLC x HT-SEC) enabled for the first time to reveal the bivariate distribution of PP-g-MA with regard to the molar mass and composition. Using on-line infrared detection quantitative information on the compositional and molar mass parameters of the individual fractions could be obtained.

  6. Four-year evaluation of workers exposed to trimellitic anhydride. A brief report

    SciTech Connect

    McGrath, K.G.; Roach, D.; Zeiss, C.R.; Patterson, R.

    1984-09-01

    In a four-year clinical, immunologic, and environmental study of trimellitic anhydride (TMA) exposure in a single plant, 20 workers exposed to TMA powder were evaluated in 1979 and a total of 32 workers were evaluated from 1979 to 1983. Two distinct groups emerged before and after workplace control improvements were made in 1979. Seventeen of the original 20 workers were available for longitudinal study through 1983. Annual clinical evaluations and serum radioimmunoassays for total antibody binding and specific IgE binding to 125I TM-HSA (human serum albumin) were performed on all 32 workers. In 1979, six workers had antibody against TM-HSA, three had the late respiratory systemic syndrome, and two had TMA-induced allergic rhinitis or allergic rhinitis and asthma. One worker had antibody against TM-HSA without illness. Fifteen additional workers were evaluated longitudinally after institution of several workplace control measures. Four of these 15 workers had TMA exposure prior to environmental improvement and joined the study in 1982. The remaining 11 workers joined the study in 1982 and had at least two years of TMA exposure in the modified workplace. None of these 11 workers developed a TMA-induced immunologic syndrome or significant total or specific IgE antibody binding to 125I TM-HSA.

  7. Effect of maleic anhydride on the damping property of magnetorheological elastomers

    NASA Astrophysics Data System (ADS)

    Fan, Y. C.; Gong, X. L.; Jiang, W. Q.; Zhang, W.; Wei, B.; Li, W. H.

    2010-05-01

    In this study, maleic anhydride (MA) was selected as the compatibilizer to modify the interfaces of magnetorheological elastomers (MREs) for improving the damping property. Several samples of MREs with different contents of MA were prepared. The content of bound-rubber was measured by the extraction method. The microstructures were observed by using an environmental scanning electron microscope (SEM). The dynamic performances of these samples, including shear storage modulus, loss factor and MR effect were measured with a modified dynamic mechanical analyzer (DMA). The tensile strength was tested by using an electronic tensile machine. The experimental results indicate that both the content of bound-rubber and the compatibility between the magnetic particles and rubber matrix were enhanced with the increase of MA. The enhancement of the bond between the two phases resulted in different mechanical properties: the increase of shear storage modulus; the reduction of the loss factor; the stability improvement of the loss factor; the enhancement of the tensile strength; and the reduction of the MR effect.

  8. Cantharidin and its anhydride-modified derivatives: relation of structure to insecticidal activity.

    PubMed

    Sun, Wenbo; Liu, Zhongyi; Zhang, Yalin

    2012-12-20

    Cantharidin is a natural compound of novel structure with ideal insecticidal activity. However, the relationship of structure to insecticidal activity of cantharidin and its derivatives has not been ever clarified. To explore what determines the insecticidal activity structurally of cantharidin-related compounds, two series target compounds 6 and 7 were synthesized by replacing the anhydride ring of norcantharidin with an aromatic amine or fatty amine with different electron density, respectively. The structures of these compounds were characterized by 1H NMR, 13C NMR and HRMS-ESI. A bioassay showed that compounds 6 (a-m) lacked any larvicidal activity against Plutella xylostella; whereas their ring-opened partners 7 (a-m) provided a variety of larvicidal activities against P. xylostella, and compound 7f indicated the highest larvicidal activity with LC(50) value of 0.43 mM. The present work demonstrated that the form of the compound (cyclic or ring-opened) or their ability to hydrolyze facilely was the key to determine whether it exhibits larvicidal activity. Moreover, it revealed that the improvement of insecticidal activity required a reasonable combination of both aliphatic amide and aromatic amide moieties, and the type of substituent Y on the aniline ring was critical.

  9. Effect of maleic anhydride treatment on the mechanical properties of sansevieria fiber/vinyl ester composites

    NASA Astrophysics Data System (ADS)

    Pradipta, Rangga; Mardiyati, Steven, Purnomo, Ikhsan

    2017-03-01

    Sanseviera trifasciata commonly called mother-in-law tongue also known as snake plant is native to Indonesia, India and Africa. Sansevieria is a new fiber in composite research and has showed promising properties as reinforcement material in polymer matrix composites. Chemical treatment on reinforcing fiber is crucial to reduce hydrophilic tendency and thus improve compatibility with the matrix. In this study, effect of maleic anhydride as chemical treatment on the mechanical properties of Sansevieria fiber/vinyl ester composite was investigated. Sansevieria fibers were immersed by using NaOH 3% for two hours at 100°C and then treated by using maleic anhydrate for two hours at 120°C. Composites were prepared by solution casting with various volume fractions of fiber; 0%, 2.5%, 5%, 7.5% and 10%. Actual density, volume fraction of void and mechanical properties of composite were conducted according to ASTM standard testing methods D792, D3171 and D3039. It was found that mechanical properties of composites increased as volume fractions of fiber was increased. The highest tensile strength and modulus of elasticity of composites were 57.45 MPa and 3.47 GPa respectively, obtained from composites with volume fraction of fiber 10%.

  10. Oral delivery of insulin loaded poly(fumaric-co-sebacic) anhydride microspheres.

    PubMed

    Furtado, Stacia; Abramson, Danielle; Burrill, Roxanne; Olivier, Gloria; Gourd, Celinda; Bubbers, Emily; Mathiowitz, Edith

    2008-01-22

    The bioadhesive polymer, poly(fumaric-co-sebacic) anhydride, p(FASA), was used to fabricate small diameter insulin microspheres and evaluate their in vivo performance in a type 1 diabetic rat as well as a type 1 diabetic dog model. The process of phase inversion nanoencapsulation was used to fabricate p(FASA) microspheres containing insulin. Using laser diffraction spectrometry, 90% of the microspheres used in the fed double dose rat experiments were found to have a volumetric diameter of 5.9 microm or smaller. In comparison, 90% of the microspheres used in fed single dose rat experiments were found to have a volumetric diameter of 2.6 microm or smaller while the microspheres used in the diabetic dog experiments were found to have a volumetric diameter of 1.2 microm or smaller. Insulin microspheres administered to diabetic rats in the fed double dose experiment produced a relative bioavailability (RB) of 23.3% while insulin microspheres administered to diabetic rats in the fed single dose experiment produced a RB of 5.5+/-1.7%. Insulin microspheres administered to fasted diabetic dogs produced a RB of 5.5+/-3.4%.

  11. Structural properties of pepsin-solubilized collagen acylated by lauroyl chloride along with succinic anhydride.

    PubMed

    Li, Conghu; Tian, Zhenhua; Liu, Wentao; Li, Guoying

    2015-10-01

    The structural properties of pepsin-solubilized calf skin collagen acylated by lauroyl chloride along with succinic anhydride were investigated in this paper. Compared with native collagen, acylated collagen retained the unique triple helix conformation, as determined by amino acid analysis, circular dichroism and X-ray diffraction. Meanwhile, the thermostability of acylated collagen using thermogravimetric measurements was enhanced as the residual weight increased by 5%. With the temperature increased from 25 to 115 °C, the secondary structure of native and acylated collagens using Fourier transform infrared spectroscopy measurements was destroyed since the intensity of the major amide bands decreased and the positions of the major amide bands shifted to lower wavenumber, respectively. Meanwhile, two-dimensional correlation spectroscopy revealed that the most sensitive bands for acylated and native collagens were amide I and II bands, respectively. Additionally, the corresponding order of the groups between native and acylated collagens was different and the correlation degree for acylated collagen was weaker than that of native collagen, suggesting that temperature played a small influence on the conformation of acylated collagen, which might be concluded that the hydrophobic interaction improved the thermostability of collagen.

  12. Dodecenylsuccinic anhydride derivatives of gum karaya (Sterculia urens): preparation, characterization, and their antibacterial properties.

    PubMed

    Padil, Vinod Vellora Thekkae; Senan, Chandra; Černík, Miroslav

    2015-04-15

    Esterifications of the tree-based gum, gum karaya (GK), using dodecenylsuccinic anhydride (DDSA) were carried out in aqueous solutions. GK was deacetylated using alkali treatment to obtain deacetylated gum karaya (DGK). The DGK and its DDSA derivative were characterized using gel permeation chromatography/multiangle laser light scattering (GPC/MALLS), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), scanning electron microscopy (SEM), proton nuclear magnetic resonance spectroscopy ((1)H NMR), thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) analysis, and rheological studies. The degree of substitution was found to be 10.25% for DGK using (1)H NMR spectroscopy. The critical aggregation concentration of DDSA-DGK was determined using dye solubilization and surface tension methods. The antibacterial activity of the DDSA-DGK derivative was then investigated against Gram-negative Escherichia coli and Pseudomonas aeruginosa and Gram-positive Staphylococcus aureus. The DDSA-DGK derivative has the potential for use as a stabilizing agent in food and nonfood applications. It can also be developed as an antibacterial agent.

  13. Effect of Persimmon Leaf Extract on Phthalic Anhydride-induced Allergic Response in Mice

    PubMed Central

    Mok, Ji Ye; Jeon, In Hwa; Cho, Jung-Keun; Park, Ji Min; Kim, Hyeon Soo; Kang, Hyun Ju; Kim, Hyung Soon; Jang, Seon Il

    2012-01-01

    The purpose of this study was to investigate the anti-allergy activities of persimmon leaf extract (PLE) on a phthalic anhydride (PA)-induced allergic mouse model. A human leukemic mast cell line (HMC-1) was used to examine the inhibitory activity of PLE on the histamine release by human leukemic mast cells. PLE inhibited histamine release from HMC-1 cells in response to cross-linkage of high-affinity IgE receptor-α (FcεRIα). Additionally, a PA-induced allergic mouse model was used to investigate the effects of PLE in vivo. Mice were orally administrated with or without PLE of single dose (250 mg/kg/day) for 31 days. Oral intake of PLE significantly inhibited passive cutaneous reactions. Oral administration of PLE to PA-induced allergic mice also led to a striking suppression of the development of contact dermatitis, ear swelling and lymph node weight. In addition, PA-specific IL-4 production of draining lymph node cells was markedly diminished by PLE oral administration, but not IFN-γ. Furthermore, PLE treatment suppressed PA-induced thymus and activation-regulated chemokine (CCL17) and cutaneous T cell-attracting chemokine (CCL27) expressions in ear tissues. Based on these results, we suggest that PLE may have therapeutic potential as an effective material for management of irritant contact dermatitis or related inflammatory diseases. PMID:24471058

  14. Immobilization of modified papain with anhydride groups on activated cotton fabric.

    PubMed

    Xue, Yong; Nie, Huali; Zhu, Limin; Li, Shubai; Zhang, Haitao

    2010-01-01

    Papain (EC 3.4.22.2) has been chemically modified using two novel reagents including different anhydrides of 1,2,4-benzenetricarboxylic and pyromellitic acids. Then, the modified papain was immobilized on the activated cotton fabric by a two-step method. The number of free amino groups in the modified protein was investigated through the 2,4,6-trinitrobenzenesulfonic acid method. Energy dispersive spectrometer was used to characterize papain immobilization. Some parameters of both modified and native papain immobilized on cotton fabric, such as optimum temperature, optimum pH, and the stabilities for reservation in various detergents were studied and compared. The resultant papain had its optimum pH shifted from 6.0 to 9.0. Compared with immobilized native papain, the thermal stability and the resistance to alkali and washing detergent of immobilized modified enzyme were improved considerably. When the concentration of detergent was 20 mg/ml, the activity of the immobilized pyromellitic papain retained about 40% of its original activity, whereas the native papain was almost inhibited. This work demonstrated that the cotton fabric immobilized modified papain has potential applications in the functional textiles field.

  15. Locally delivered salicylic acid from a poly(anhydride-ester): impact on diabetic bone regeneration.

    PubMed

    Wada, Keisuke; Yu, Weiling; Elazizi, Mohamad; Barakat, Sandrine; Ouimet, Michelle A; Rosario-Meléndez, Roselin; Fiorellini, Joseph P; Graves, Dana T; Uhrich, Kathryn E

    2013-10-10

    Diabetes mellitus (DM) involves metabolic changes that can impair bone repair, including a prolonged inflammatory response. A salicylic acid-based poly(anhydride-ester) (SA-PAE) provides controlled and sustained release of salicylic acid (SA) that locally resolves inflammation. This study investigates the effect of polymer-controlled SA release on bone regeneration in diabetic rats where enhanced inflammation is expected. Fifty-six Sprague-Dawley rats were randomly assigned to two groups: diabetic group induced by streptozotocin (STZ) injection or normoglycemic controls injected with citrate buffer alone. Three weeks after hyperglycemia development or vehicle injection, 5mm critical sized defects were created at the rat mandibular angle and treated with SA-PAE/bone graft mixture or bone graft alone. Rats were euthanized 4 and 12weeks after surgery, then bone fill percentage in the defect region was assessed by micro-computed tomography (CT) and histomorphometry. It was observed that bone fill increased significantly at 4 and 12weeks in SA-PAE/bone graft-treated diabetic rats compared to diabetic rats receiving bone graft alone. Accelerated bone formation in normoglycemic rats caused by SA-PAE/bone graft treatment was observed at 4weeks but not at 12weeks. This study shows that treatment with SA-PAE enhances bone regeneration in diabetic rats and accelerates bone regeneration in normoglycemic animals.

  16. Cantharidin and Its Anhydride-Modified Derivatives: Relation of Structure to Insecticidal Activity

    PubMed Central

    Sun, Wenbo; Liu, Zhongyi; Zhang, Yalin

    2013-01-01

    Cantharidin is a natural compound of novel structure with ideal insecticidal activity. However, the relationship of structure to insecticidal activity of cantharidin and its derivatives has not been ever clarified. To explore what determines the insecticidal activity structurally of cantharidin-related compounds, two series target compounds 6 and 7 were synthesized by replacing the anhydride ring of norcantharidin with an aromatic amine or fatty amine with different electron density, respectively. The structures of these compounds were characterized by 1H NMR, 13C NMR and HRMS-ESI. A bioassay showed that compounds 6 (a–m) lacked any larvicidal activity against Plutella xylostella; whereas their ring-opened partners 7 (a–m) provided a variety of larvicidal activities against P. xylostella, and compound 7f indicated the highest larvicidal activity with LC50 value of 0.43 mM. The present work demonstrated that the form of the compound (cyclic or ring-opened) or their ability to hydrolyze facilely was the key to determine whether it exhibits larvicidal activity. Moreover, it revealed that the improvement of insecticidal activity required a reasonable combination of both aliphatic amide and aromatic amide moieties, and the type of substituent Y on the aniline ring was critical. PMID:23344017

  17. Dinuclear Zinc Salen Catalysts for the Ring Opening Copolymerization of Epoxides and Carbon Dioxide or Anhydrides.

    PubMed

    Thevenon, Arnaud; Garden, Jennifer A; White, Andrew J P; Williams, Charlotte K

    2015-12-21

    A series of four dizinc complexes coordinated by salen or salan ligands, derived from ortho-vanillin and bearing (±)-trans-1,2-diaminocyclohexane (L1) or 2,2-dimethyl-1,3-propanediamine (L2) backbones, is reported. The complexes are characterized using a combination of X-ray crystallography, multinuclear NMR, DOSY, and MALDI-TOF spectroscopies, and elemental analysis. The stability of the dinuclear complexes depends on the ligand structure, with the most stable complexes having imine substituents. The complexes are tested as catalysts for the ring-opening copolymerization (ROCOP) of CO2/cyclohexene oxide (CHO) and phthalic anhydride (PA)/CHO. All complexes are active, and the structure/activity relationships reveal that the complex having both L2 and imine substituents displays the highest activity. In the ROCOP of CO2/CHO its activity is equivalent to other metal salen catalysts (TOF = 44 h(-1) at a catalyst loading of 0.1 mol %, 30 bar of CO2, and 80 °C), while for the ROCOP of PA/CHO, its activity is slightly higher than other metal salen catalysts (TOF = 198 h(-1) at a catalyst loading of 1 mol % and 100 °C). Poly(ester-block-carbonate) polymers are also afforded using the most active catalyst by the one-pot terpolymerization of PA/CHO/CO2.

  18. Water absorption of poly(methyl methacrylate) containing 4-methacryloxyethyl trimellitic anhydride.

    PubMed

    Unemori, Masako; Matsuya, Yoko; Matsuya, Shigeki; Akashi, Akane; Akamine, Akifumi

    2003-04-01

    The amount of water absorption of poly(methyl methacrylate) (PMMA) containing 0, 1, 3 and 5 wt% of an adhesive monomer, 4-methacryloxyethyl trimellitic anhydride (4-META), was measured at 7 degrees C, 37 degrees C and 60 degrees C. After the water uptake reached equilibrium in specimens, they were desorbed to obtain a constant value and the absorption process was repeated. Mass changes in the second desorption were recorded for the storage temperatures of 37 degrees C and 60 degrees C. Multiple regression analyses were conducted on three independent variables, 4-META concentration, storage temperature and absorption-desorption cycle. A statistically significant relationship was found between the maximum water uptake and 4-META concentration, while there was no relationship between the maximum water uptake and diffusion coefficient obtained using the Fick's law. The negative relationship in the latter did not support the free space theory. The significant and positive relationship between the maximum water uptake and 4-META concentration demonstrates that water molecules diffuse through the formation of a hydrogen bond at polar sites. The maximum water uptake was not influenced by temperature, while the diffusion coefficient increased with the rise in temperature. The activation energy was 41-47 and 50-53 kJ/mol in the first and second absorption tests, respectively.

  19. Position of modifying groups on starch chains of octenylsuccinic anhydride-modified waxy maize starch.

    PubMed

    Bai, Yanjie; Kaufman, Rhett C; Wilson, Jeff D; Shi, Yong-Cheng

    2014-06-15

    Octenylsuccinic anhydride (OSA)-modified starches with a low (0.018) and high (0.092) degree of substitution (DS) were prepared from granular native waxy maize starch in aqueous slurry. The position of OS substituents along the starch chains was investigated by enzyme hydrolysis followed by chromatographic analysis. Native starch and two OS starches with a low and high DS had β-limit values of 55.9%, 52.8%, and 34.4%, respectively. The weight-average molecular weight of the β-limit dextrin from the OS starch with a low DS was close to that of the β-limit dextrin from native starch but lower than that of the β-limit dextrin from the OS starch with a high DS. Debranching of OS starches was incomplete compared with native starch. OS groups in the OS starch with a low DS were located on the repeat units near the branching points, whereas the OS substituents in the OS starch with a high DS occurred both near the branching points and the non-reducing ends.

  20. Granular size of potato starch affects structural properties, octenylsuccinic anhydride modification and flowability.

    PubMed

    Wang, Chan; Tang, Chuan-He; Fu, Xiong; Huang, Qiang; Zhang, Bin

    2016-12-01

    Native potato starch (PS) granules were separated into three size fractions: larger than 30μm (P-L), 15-30μm (P-M), and smaller than 15μm (P-S). The morphological and crystalline structure of fractionated potato starches were investigated by light and scanning electron microscopy (SEM), X-ray diffraction (XRD) and differential scanning calorimetry (DSC). The P-L fraction showed ellipsoidal shape and B-type X-ray pattern, whereas the P-S fraction had spherical shape and A-type pattern. The fluorophore-assisted capillary electrophoresis data showed that the P-L fraction had more B2 chains and less short A and B1 chains than the P-S counterparts. Smaller granules with larger specific surface area had higher degree of substitution when reacted with octenylsuccinic anhydride (OSA), and showed more uniform distribution of octenylsuccinate substituents. Both OSA modified and unmodified P-S samples showed higher flowability compared with the P-L counterparts.

  1. Highly carbonylated cellulose nanofibrous membranes utilizing maleic anhydride grafting for efficient lysozyme adsorption.

    PubMed

    Ma, Juncheng; Wang, Xueqin; Fu, Qiuxia; Si, Yang; Yu, Jianyong; Ding, Bin

    2015-07-22

    Construction of adsorptive materials for simple, efficient, and high-throughput adsorption of proteins is critical to meet the great demands of highly purified proteins in biotechnological and biopharmaceutical industry; however, it has proven extremely challenging. Here, we report a cost-effective strategy to create carbonyl groups surface-functionalized nanofibrous membranes under mild conditions for positively charged protein adsorption. Our approach allows maleic anhydride to in situ graft on cellulose nanofibrous membranes (CMA) to construct adsorptive membranes with large surface area and tortuous porous structure. Thereby, the resultant CMA membranes exhibited high adsorption capacity of 160 mg g(-1), fast equilibrium within 12 h, and good reversibility to lysozyme. Moreover, the dynamic adsorption was performed under low pressure-drops (750 Pa), with a relatively high saturation adsorption amount of 118 mg g(-1), which matched well with the requirements for proteins purification. Considering the excellent adsorption performance of the as-prepared adsorptive membranes, this simple and intriguing approach may pave a way for the design and development of robust and cost-effective adsorption membranes to meet the great demands for fast and efficient adsorption of positively charged proteins.

  2. Reaction of octenylsuccinic anhydride with a mixture of granular starch and soluble maltodextrin.

    PubMed

    Bai, Yanjie; Shi, Yong-Cheng

    2013-11-06

    The reaction of octenylsuccinic anhydride (OSA) with a mixture of granular waxy maize starch and soluble maltodextrin was investigated. OSA was reacted with a 1:1 (w/w) mixture of the granular starch and maltodextrin at OSA levels of 1.5, 3, 9, and 15% (wt% based on starch weight). After the first 0.5h of the reaction, degree of substitution (DS) on maltodextrin reached 0.021, 0.030, 0.080, and 0.10 for 1.5, 3, 9, and 15% OSA, respectively, whereas DS for granular starch was only 0.0020, 0.0087, 0.014, and 0.016. At 2h of the reaction, the bound OS ratio of maltodextrin to granular starch was 10.8 when OSA concentration was 1.5% and the ratio decreased to ca. 5 at higher OSA concentrations. OSA preferred to react with maltodextrin than semi-crystalline granular starch when both existed in the system. OSA reacted with maltodextrin at a much faster rate and to a greater extent than with granular starch, but a significant amount of OSA reacted with granular starch at 3-15% OSA concentrations.

  3. Effect of the degree of substitution of octenyl succinic anhydride-banana starch on emulsion stability.

    PubMed

    Bello-Pérez, Luis A; Bello-Flores, Christopher A; Nuñez-Santiago, María del Carmen; Coronel-Aguilera, Claudia P; Alvarez-Ramirez, J

    2015-11-05

    Banana starch was esterified with octenylsuccinic anhydride (OSA) at different degree substitution (DS) and used to stabilize emulsions. Morphology, emulsion stability, emulsification index, rheological properties and particle size distribution of the emulsions were tested. Emulsions dyed with Solvent Red 26 showed affinity for the oil phase. Backscattering light showed three regions in the emulsion where the emulsified region was present. Starch concentration had higher effect in the emulsification index (EI) than the DS used in the study because similar values were found with OSA-banana and native starches. However, OSA-banana presented greater stability of the emulsified region. Rheological tests in emulsions with OSA-banana showed G'>G" values and low dependence of G' with the frequency, indicating a dominant elastic response to shear. When emulsions were prepared under high-pressure conditions, the emulsions with OSA-banana starch with different DS showed a bimodal distribution of particle size. The emulsion with OSA-banana starch and the low DS showed similar mean droplet diameter than its native counterpart. In contrast, the highest DS led to the highest mean droplet diameter. It is concluded that OSA-banana starch with DS can be used to stabilize specific emulsion types.

  4. Studies in iridoid synthesis. Chemoselective transformations of cis-1,2,4,6-tetrahydrophthalic anhydride.

    PubMed

    Stevens, Anne T; Bull, James R; Chibale, Kelly

    2008-02-07

    In the course of synthetic studies towards the development of diastereoselective routes to secoiridoid aglycones, cis-1,2,4,6-tetrahydrophthalic anhydride was transformed into the corresponding lactone cis-3a,4,7,7a-tetrahydro-3H-isobenzofuran-1-one, which served as a key precursor for a variety of chemoselective synthetic manipulations. Unsuccessful formylation of an ester intermediate resulted in a (E/Z) mixture of vinyl alcohols which were protected as acetates and as a single p-methoxybenzyl (PMB) ether (E) isomer. Dihydroxylation of the cyclohexene motif using OsO(4) led to the unexpected deprotection of the PMB ether. On the other hand, successful formylation of a suitably silyl protected lactonised intermediate was achieved using tert-butoxybis(dimethylamino)methane, or Bredereck's reagent. Tetrabutylammonium fluoride (TBAF) deprotection of a methoxyethoxymethyl (MEM)-ether intermediate serendipitously afforded an approximately 1 : 1 mixture of pyrano-pyranones, which are products of a seldom encountered intramolecular Michael addition, using an oxygen donor, to the terminus of an alpha,beta-unsaturated system, followed by beta-elimination of the MEM moiety.

  5. Nano-encapsulation of coenzyme Q10 using octenyl succinic anhydride modified starch.

    PubMed

    Cheuk, Sherwin Y; Shih, Frederick F; Champagne, Elaine T; Daigle, Kim W; Patindol, James A; Mattison, Christopher P; Boue, Stephen M

    2015-05-01

    Octenyl succinic anhydride modified starch (OSA-ST) was used to encapsulate coenzyme Q10 (CoQ10). CoQ10 was dissolved in rice bran oil and incorporated into an aqueous OSA-ST solution. High pressure homogenisation of the mixture was conducted at 170 MPa for 56 cycles. The resulting emulsion had a particle size range of 200-300 nm and the absolute zeta potential varied between 8.4 and 10.6 mV. CoQ10 retention of the emulsion and freeze dried products, determined by a hexane rinse, was 98.2%. Reconstitution of the freeze dried product in Mcllvaine citrate-phosphate buffers with pH values of 3-5 and temperatures at 4 and 25 °C had very little effect on the range and distribution of the nanoparticles' size. The inflection point of the zeta potential and pH plot occurred at the first pKa of succinic acid (pH 4.2), indicating succinate as the main influence over zeta potential.

  6. Difructose anhydride III enhances bioavailability of water-insoluble iron in anemic Vietnamese women.

    PubMed

    Nakamori, Masayo; Hien, Vu Thi Thu; Khan, Nguyen Cong; Lam, Nguyen Thi; Dung, Nguyen Tri; Uotsu, Nobuo; Shiomi, Takuya; Okuhara, Yasuhide; Kise, Mitsuo; Shigematsu, Norihiro; Yamamoto, Shigeru

    2010-01-01

    Difructose anhydride III (DFAIII) is an indigestible disaccharide and has been shown to enhance iron absorption in animal studies; however, the effect has not been investigated in anemic subjects. We investigated the efficacy of co-administration of DFAIII with water-insoluble iron in the treatment of iron deficiency anemia in Vietnamese women. One hundred sixty-eight moderately anemic women (80 g/L

  7. Therapeutic effects of fermented soycrud on phenotypes of atopic dermatitis induced by phthalic anhydride

    PubMed Central

    Sung, Ji-Eun; Kwak, Moon-Hwa; Kim, Ji-Eun; Lee, Young-Ju; Kim, Ro-Ui; Kim, Eun-Ah; Lee, Ga-Young; Kim, Dong-Seob

    2013-01-01

    Atopic dermatitis (AD), which is known as the most common pruritic skin disease, is caused by epidermal barrier dysfunction, allergies, microwave radiation, histamine intolerance, and genetic defects. To investigate the therapeutic effects of fermented soycrud (FSC) on AD pathology, alteration of AD phenotypes induced by phthalic anhydride (PA) treatment was assessed by ear thickness analysis, measurement of immune-related organ weights, ELISA, and histological and pathological analyses of ICR mice after FSC treatment for 2 weeks. Except for water content, the concentrations of most major components were lower in FSC compared to common tofu (CMT). Thymus and lymph node weights were significantly reduced in ICR mice treated with PA+CMT or PA+FSC, whereas spleen and body weights were maintained. Elevation of ear thickness induced by PA treatment was rapidly diminished in the CMT- and FSC-treated groups, although there was no significant difference between the two groups. Furthermore, significant reduction of epidermal thickness was detected in both the PA+CMT- and PA+FSC-treated groups. However, IgE concentration and dermal thickness were reduced only by PA+FSC treatment, whereas PA+CMT treatment maintained levels comparable to PA+vehicle treatment. The number of infiltrated mast cells was higher in the PA+vehicle-treated group compared to the untreated control. Following CMT or FSC treatment, mast cell infiltration was slightly reduced, although the CMT-treated group showed greater cell numbers. These results indicate that FSC may significantly relieve the phenotypes of AD induced by PA treatment and should be considered as a potential candidate for AD therapy. PMID:23825483

  8. Involvement of inflammatory mediators in the airway responses to trimellitic anhydride in sensitized guinea-pigs.

    PubMed Central

    Hayes, J. P.; Lotvall, J. O.; Barnes, P. J.; Newman Taylor, A. J.; Chung, K. F.

    1992-01-01

    1. We examined the effect of various pharmacological agents on the acute bronchoconstrictor response and airway microvascular leakage in a model of guinea-pig sensitization to trimellitic anhydride (TMA) a cause of low molecular weight occupational asthma in man. 2. Guinea-pigs were given intradermal injections of 0.1 ml of 0.3% TMA in corn oil; 21-28 days later, anaesthetized guinea-pigs were challenged with TMA conjugated to guinea-pig albumin by tracheal instillation. Changes in lung resistance were measured and airway microvascular leakage was quantified by measuring the extravasation of Evans blue dye into the airway tissue. 3. Sensitized guinea-pig (n = 9 in each group) were pretreated with chlorpheniramine (2.5 mg kg-1, i.v.), WEB 2086 (10 micrograms kg-1, i.v.), BW 4AC (50 mg kg-1, i.p.), nedocromil sodium (2% aerosol for 60 s) or vehicle alone. 4. Pretreatment with chlorpheniramine inhibited both the acute bronchoconstrictor response and the increase in airway microvascular leakage. WEB 2086 and nedocromil sodium partially inhibited the bronchoconstrictor response but had no significant effect on airway microvascular leakage. BW 4AC caused a non-significant reduction of the bronchoconstrictor response and airway microvascular leakage. 5. These results indicate that both the bronchoconstrictor response and the airway microvascular response in this model of sensitization is mediated to a large extent by histamine. PAF but not 5-lipoxygenase products also partially mediates the bronchoconstrictor response but not the airway microvascular leakage. Nedocromil sodium partially inhibits the bronchoconstrictor response only. PMID:1382788

  9. Trimellitic anhydride-conjugated serum albumin activates rat alveolar macrophages in vitro

    PubMed Central

    Valstar, Dingena L; Schijf, Marcel A; Stelekati, Erietta; Nijkamp, Frans P; Bloksma, Nanne; Henricks, Paul AJ

    2006-01-01

    Background Occupational exposure to airborne low molecular weight chemicals, like trimellitic anhydride (TMA), can result in occupational asthma. Alveolar macrophages (AMs) are among the first cells to encounter these inhaled compounds and were previously shown to influence TMA-induced asthma-like symptoms in the Brown Norway rat. TMA is a hapten that will bind to endogenous proteins upon entrance of the body. Therefore, in the present study we determined if TMA and TMA conjugated to serum albumin induced the production of the macrophage mediators nitric oxide (NO), tumour necrosis factor (TNF), and interleukin 6 (IL-6) in vitro using the rat AM cell line NR8383 and primary AMs derived from TMA-sensitized and naïve Brown Norway rats. Methods Cells were incubated with different concentrations of TMA, TMA conjugated to bovine serum albumin (BSA), and BSA as a control for 24 h and the culture supernatant was analyzed for mediator content. Results TMA alone was not able to induce the production of mediators by NR8383 cells and primary AMs from sensitized and sham-treated rats. TMA-BSA, on the contrary, dose-dependently stimulated the production of NO, TNF, and IL-6 by NR8383 cells and of NO and TNF, but not IL-6, by primary AMs independent of sensitization. Conclusion Results suggest that although TMA is a highly reactive compound, conjugation to a suitable protein is necessary to induce mediator production by AMs. Furthermore, the observation that effects of TMA-BSA were independent of sensitization suggests involvement of an immunologically non-specific receptor. In the discussion it is argued that a macrophage scavenger receptor is a likely candidate. PMID:16796737

  10. Evaporative Derivatization of Phenols with 2-Sulfobenzoic Anhydride for Detection by MALDI-MS

    PubMed Central

    Yao, Yuanyuan; Wang, Poguang; Giese, Roger

    2014-01-01

    RATIONALE Phenols are an important class of analytes, for example as bioactive environmental contaminants. Towards a goal of improving their detection by MALDI-TOF-MS or MALDI-TOF/TOF-MS, we studied their derivatization with 2-sulfobenzoic anhydride (SBA). We chose SBA for this purpose since it is commercially available, inexpensive, and forms an anionic derivative. METHODS In selected conditions developed here for phenols, a reaction mixture of one or more of such compounds in acetonitrile containing SBA and 4-dimethylaminopyridine (DMAP) is evaporated to a solid, heated at 60°C for 1 h, redissolved in 50% acetonitrile containing matrix, spotted onto a MALDI target, and subjected to negative ion MALDI-TOF/TOF-MS. RESULTS While conventional (solution-phase) reaction of 4-phenylphenol (model analyte) with SBA and DMAP only gave a 47% yield of SBA-tagged 4-phenylphenol, evaporative derivatization as above gave a 96% yield, and 25 pmol (4.3 ng) of 4-phenylphenol could be detected in this way by MALDI-TOF/TOF-MS at S/N = 260, whereas even 1 nmol of the nonderivatized phenol was not detected in the absence of derivatization. A wide range of responses was observed when a mixture of 15 phenols was derivatized, with the higher responses coming from phenols with a pKa value above 9. Without derivatization, phenols with pKa values below 5 were the most readily detected. CONCLUSION Evaporative derivatization with SBA (a convenient reagent) can improve the detection of phenols with relatively high pKa values (above 9) by negative ion MALDI-TOF-MS, and accomplish this in the absence of post-derivatization reaction cleanup. PMID:24519828

  11. Role of mast cell in the late phase of contact hypersensitivity induced by trimellitic anhydride

    PubMed Central

    Chai, Ok Hee

    2015-01-01

    Mast cells are known as effector cells of IgE-mediated allergic responses, but role of mast cells in contact hypersensitivity (CHS) has been considered controversial. In this study, we investigated role of mast cell in trimellitic anhydride (TMA)-induced CHS. The mice were sensitized to TMA on the back and repeatedly challenged with TMA on the left ear at 1-week intervals. The ear after challenge showed biphasic responses. The repetition of TMA challenge shifted in time course of ear response and enlarged the extent of early and late phase reactions in proportion to the frequency of TMA challenges in C57BL/6 mice. In late phase reaction, peak of ear response by single challenge showed at 24 hours after challenge, but the peak by repeat challenges at 8 hours after the last challenge. Number of mast cells and eosinophils per unit area increased in proportion to frequency of TMA challenges. However, mast cell-deficient WBB6F1/J-KitW/KitW-v mice developed the late phase reaction without the early phase reaction. The repetition of TMA challenge shifted in time course of ear response and enlarged the extent of ear response and the infiltration of eosinophils. The magnitude of these responses observed according to the frequency of the TMA challenge in mast cell-deficient WBB6F1/J-KitW/KitW-v mice was significantly lower than that in C57BL/6 mice. Also TMA elicited mast cell degranulation and histamine release from rat peritoneal mast cells in a concentration-dependent manner. Conclusively, TMA induces the early and late phase reactions in CHS, and mast cells may be required for TMA-induced CHS. PMID:26770872

  12. Elucidation of substituted ester group position in octenylsuccinic anhydride modified sugary maize soluble starch.

    PubMed

    Ye, Fan; Miao, Ming; Huang, Chao; Lu, Keyu; Jiang, Bo; Zhang, Tao

    2014-12-03

    The octenylsuccinic groups in esterification-modified sugary maize soluble starches with a low (0.0191) or high (0.0504) degree of substitution (DS) were investigated by amyloglucosidase hydrolysis followed by a combination of chemical and physical analysis. The results showed the zeta-potential remained at approximately the same value regardless of excessive hydrolysis. The weight-average molecular weight decreased rapidly and reached 1.22 × 10(7) and 1.60 × 10(7) g/mol after 120 min for low-DS and high-DS octenylsuccinic anhydride (OSA) modified starch, respectively. The pattern of z-average radius of gyration as well as particle size change was similar to that of Mw, and z-average radius of gyration decreased much more slowly, especially for high-DS OSA starch. Compared to native starch, two characteristic absorption peaks at 1726.76 and 1571.83 cm(-1) were observed in FT-IR spectra, and the intensity of absorption peaks increased with increasing DS. The NMR results showed that OSA starch had several additional peaks at 0.8-3.0 ppm and a shoulder at 5.56 ppm for OSA substituents, which were grafted at O-2 and O-3 positions in soluble starch. The even distribution of OSA groups in the center area of soluble starch particle has been directly shown under CLSM. Most substitutions were located near branching points of soluble starch particles for a low-DS modified starch, whereas the substituted ester groups were located near branching points as well as at the nonreducing ends in OSA starch with a high DS.

  13. Therapeutic effect of ethyl acetate extract from Asparagus cochinchinensis on phthalic anhydride-induced skin inflammation

    PubMed Central

    Sung, Ji-Eun; Lee, Hyun-Ah; Kim, Ji-Eun; Go, Jun; Seo, Eun-Ji; Yun, Woo-Bin; Kim, Dong-Seob; Son, Hong-Joo; Lee, Chung-Yeoul; Lee, Hee-Seob

    2016-01-01

    Asparagus cochinchinensis has been used to treat various diseases including fever, cough, kidney disease, breast cancer, inflammatory disease and brain disease, while IL-4 cytokine has been considered as key regulator on the skin homeostasis and the predisposition toward allergic skin inflammation. However, few studies have investigated its effects and IL-4 correlation on skin inflammation to date. To quantitatively evaluate the suppressive effects of ethyl acetate extracts of A. cochinchinensis (EaEAC) on phthalic anhydride (PA)-induced skin inflammation and investigate the role of IL-4 during their action mechanism, alterations in general phenotype biomarkers and luciferase-derived signals were measured in IL-4/Luc/CNS-1 transgenic (Tg) mice with PA-induced skin inflammation after treatment with EaEAC for 2 weeks. Key phenotype markers including lymph node weight, immunoglobulin E (IgE) concentration, epidermis thickness and number of infiltrated mast cells were significantly decreased in the PA+EaEAC treated group compared with the PA+Vehicle treated group. In addition, expression of IL-1β and TNF-α was also decreased in the PA+EaEAC cotreated group, compared to PA+Vehicle treated group. Furthermore, a significant decrease in the luciferase signal derived from IL-4 promoter was detected in the abdominal region, submandibular lymph node and mesenteric lymph node of the PA+EaEAC treated group, compared to PA+Vehicle treated group. Taken together, these results suggest that EaEAC treatment could successfully improve PA-induced skin inflammation of IL-4/Luc/CNS-1 Tg mice, and that IL-4 cytokine plays a key role in the therapeutic process of EaEAC. PMID:27051441

  14. Biocompatible photocrosslinked poly(ester anhydride) based on functionalized poly(epsilon-caprolactone) prepolymer shows surface erosion controlled drug release in vitro and in vivo.

    PubMed

    Mönkäre, J; Hakala, R A; Vlasova, M A; Huotari, A; Kilpeläinen, M; Kiviniemi, A; Meretoja, V; Herzig, K H; Korhonen, H; Seppälä, J V; Järvinen, K

    2010-09-15

    Star-shaped poly(epsilon-caprolactone) oligomers functionalized with succinic anhydride were used as prepolymers to prepare photocrosslinked poly(ester anhydride) to evaluate their in vivo drug delivery functionality and biocompatibility. Thus, in this work, erosion, drug release and safety of the photocrosslinked poly(ester anhydride) were examined in vitro and in vivo. A small water-soluble drug, propranolol HCl (M(w) 296 g/mol, solubility 50 mg/ml), was used as the model drug in an evaluation of the erosion controlled release. Drug-free and drug-loaded (10-60% w/w) poly(ester anhydride) discoids eroded in vitro (pH 7.4 buffer, +37 degrees C) linearly within 24-48 h. A strong correlation between the polymer erosion and the linear drug release in vitro was observed, indicating that the release had been controlled by the erosion of the polymer. Similarly, in vivo studies (s.c. implantation of discoids in rats) indicated that surface erosion controlled drug release from the discoids (drug loading 40% w/w). Oligomers did not decrease cell viability in vitro and the implanted discoids (s.c., rats) did not evoke any cytokine activity in vivo. In summary, surface erosion controlled drug release and the safety of photocrosslinked poly(ester anhydride) were demonstrated in this study.

  15. A New Process for Maleic Anhydride Synthesis from a Renewable Building Block: The Gas-Phase Oxidehydration of Bio-1-butanol.

    PubMed

    Pavarelli, Giulia; Velasquez Ochoa, Juliana; Caldarelli, Aurora; Puzzo, Francesco; Cavani, Fabrizio; Dubois, Jean-Luc

    2015-07-08

    We investigated the synthesis of maleic anhydride by oxidehydration of a bio-alcohol, 1-butanol, as a possible alternative to the classical process of n-butane oxidation. A vanadyl pyrophosphate catalyst was used to explore the one-pot reaction, which involved two sequential steps: 1) 1-butanol dehydration to 1-butene, catalysed by acid sites, and 2) the oxidation of butenes to maleic anhydride, catalysed by redox sites. A non-negligible amount of phthalic anhydride was also formed. The effect of different experimental parameters was investigated with chemically sourced 1-butanol, and the results were then confirmed by using genuinely bio-sourced 1-butanol. In the case of bio-1-butanol, however, the purity of the product remarkably affected the yield of maleic anhydride. It was found that the reaction mechanism includes the oxidation of butenes to crotonaldehyde and the oxidation of the latter to either furan or maleic acid, both of which are transformed to produce maleic anhydride.

  16. Determination of amines as pentafluoropropionic acid anhydride derivatives in biological samples using liquid chromatography and tandem mass spectrometry.

    PubMed

    Marand, Asa; Karlsson, Daniel; Dalene, Marianne; Skarping, Gunnar

    2004-06-01

    Determination of amines in biological samples as markers of exposure to the amines or the corresponding isocyanates is an important tool for industrial exposure assessment. In this study, a liquid chromatography and tandem mass spectrometry (LC-MS/MS) method for determination of amines in biological samples as perfluorofatty amides derivatives is presented. The method enables determination of diamines such as methylene diamine (MDA), toluene diamine (TDA), naphthalene diamine (NDA), hexamethylene diamine (HDA), isophorone diamine (IPDA), methylenedi(cyclohexylamine)(HMDA) and 4,4'-methylene-(2-chloroaniline)(MOCA) in human urine and plasma. The work-up procedure included hydrolysis of the biological samples with 3 M H(2)SO(4) at 100 degrees C for 16 h and extraction of the amines into toluene, where derivatisation of the amines with perfluorofatty acid anhydride was performed. Following removal of excess reagent and the acid formed and an exchange of solvent, the derivatives were analysed using gradient elution with an acetonitrile/water mobile phase composition and electrospray ionisation (ESI) with multiple reaction monitoring (MRM) of [M - H](-)-->[M - H - 120](-) or [119](-). Several perfluorofatty acid anhydrides were evaluated as derivatisation reagents, but the LC chromatographic properties of the pentafluoropropionic acid anhydride (PFPA) derivatives were favourable. Quantification of amine-PFPA derivatives was performed using deuterium labelled amine-PFPA derivatives as internals standards with good precision and linearity in the investigated range of 0-20 ng ml(-1) urine. The instrumental detection limits for the amine-PFPA derivatives were 0.2-3 fmol for MRM of [M - H](-)-->[119](-) and 0.3-8 fmol for [M - H](-)-->[M - H - 120](-). In 10 urine and 6 plasma samples from workers exposed to isocyanates, determination of TDA and MDA as PFPA derivatives was performed using LC-MS/MS and a reference GC-MS method. No significant difference between the two

  17. Synthesis of comb-like copolymers from renewable resources: Itaconic anhydride, stearyl methacrylate and lactic acid

    NASA Astrophysics Data System (ADS)

    Shang, Shurui

    The synthesis and properties of comb-like copolymers and ionomers derived from renewable resources: itaconic anhydride (ITA), stearyl methacrylate (SM) and lactic acid (LA) are described. The copolymers based on ITA and SM (ITA-SM) were nearly random with a slight alternating tendency. The copolymers exhibited a nanophase-separated morphology, with the stearate side-chains forming a bilayer, semi-crystalline structure. The crystalline side-chains suppressed molecular motion of the main-chain, so that a glass transition temperature (Tg) was not resolved unless the ITA concentration was sufficiently high so that Tg > the melting point (Tm). The softening point and modulus of the copolymers increased with the increasing ITA concentration, but the thermal stability decreased. The ITA moiety along the main chain of the copolymers was neutralized with metal acetates to produce Na-, Ca- and Zn- random ionomers with comb-like architectures. In general, the incorporation of the ionic groups increased the Tg and suppressed the crystallinity of the side-chain packing. Ionomers with high SM side-chain density had two competing driving forces for self-assembled nano-phase separation: ionic aggregation and side-chain crystalline packing. Upon neutralization, a morphological transition from semi-crystalline lamella to spherical ionic aggregation was observed by small angle X-ray scattering (SAXS) analysis and transmission electron microscopy (TEM). Thermomechanical analysis revealed an increasing resistance to penetration deformation with an increasing degree of neutralization and an apparent rubbery plateau was observed above Tg. A controlled transesterification of PLA in glassware was an effective way to prepare a methacrylate functionalized PLA macromonomer with controlled molecular weight, which was used to synthesize a variety of copolymers. The copolymerization of this functionalized PLA macromonomer with ITA totally suppressed the side-chain crystallinity for the PLA chain

  18. Autoimmune response in MRL+/+ mice following treatment with dichloroacetyl chloride or dichloroacetic anhydride

    SciTech Connect

    Cai Ping; Koenig, Rolf; Khan, M. Firoze; Qiu, Suimin; Kaphalia, Bhupendra S.; Ansari, G.A.S. . E-mail: sansari@utmb.edu

    2006-10-15

    Dichloroacetyl chloride (DCAC) is formed from trichloroethene (TCE), which is implicated in inducing/accelerating autoimmune response. Due to its potent acylating activity, DCAC may convert proteins to neo-antigens and thus could induce autoimmune responses. Dichloroacetic anhydride (DCAA), which is a similar acylating agent, might also induce autoimmune responses. To evaluate if chloroacylation plays a role in the induction of autoimmunity, we have measured the autoimmune responses following treatment with DCAC or DCAA in autoimmune-prone MRL+/+ mice. Five-week-old female mice were injected intraperitoneally (twice weekly) with 0.2 mmol/kg of DCAC or DCAA in corn oil for 6 weeks. Total serum IgG, IgG1, and IgE levels were significantly increased in DCAC-treated mice as compared to controls. These increases corresponded with increases in DCAC-specific IgG and IgG1 levels. Total serum IgM was decreased in both DCAC- and DCAA-treated mice. Antinuclear antibodies, measured as an indication of systemic autoimmune responses, were increased in both DCAC- and DCAA-treated mice. Of eight Th1/Th2 cytokines measured in the serum, only IL-5 was significantly decreased in both treatment groups. The cytokine secretion patterns of splenic lymphocytes after stimulation with antibodies against CD3 (T cell receptor-mediated signal) and CD28 (costimulatory signal) differed between treatment and control groups. Levels of IL-1, IL-3, IL-6, IFN-{gamma}, G-CSF, and KC were higher in cultures of stimulated splenocytes from either DCAC- or DCAA-treated mice than from controls. The level of IL-17 was only increased in cultures from DCAC-treated mice. Increased lymphocytic populations were found in the red pulp of spleens following treatment with either DCAC or DCAA. In addition, thickening of the alveolar septa in the lungs of DCAC- or DCAA-treated mice was observed. The lung histopathology in exposed mice was consistent with the symptomology observed in welders exposed to DCAC

  19. Alternating copolymerization of propylene oxide with biorenewable terpene-based cyclic anhydrides: a sustainable route to aliphatic polyesters with high glass transition temperatures.

    PubMed

    Van Zee, Nathan J; Coates, Geoffrey W

    2015-02-23

    The alternating copolymerization of propylene oxide with terpene-based cyclic anhydrides catalyzed by chromium, cobalt, and aluminum salen complexes is reported. The use of the Diels-Alder adduct of α-terpinene and maleic anhydride as the cyclic anhydride comonomer results in amorphous polyesters that exhibit glass transition temperatures (Tg ) of up to 109 °C. The polymerization conditions and choice of catalyst have a dramatic impact on the molecular weight distribution, the relative stereochemistry of the diester units along the polymer chain, and ultimately the Tg of the resulting polymer. The aluminum salen complex exhibits exceptional selectivity for copolymerization without transesterification or epimerization side reactions. The resulting polyesters are highly alternating and have high molecular weights and narrow polydispersities.

  20. Modelling of crystal structure of cis-1,2,3,6 and 3,4,5,6-tetrahydrophthalic anhydrides using lattice energy calculations.

    PubMed

    Fredj, A Ben; Day, G M

    2015-08-01

    Lattice energy calculations using a model potential were performed to model the crystal structures of cis-1,2,3,6- and 3,4,5,6-tetrahydrophthalic (THP) anhydrides. The optimized molecular models using the DFT method at the B3LYP/6-31G** level were found consistent with the available experimental evidence and allowed all differences observed in crystal packing between cis-1,2,3,6- and 3,4,5,6-THP anhydrides to be reproduced. Calculations provide evidence for the presence of dipole-dipole C=O⋯C=O intermolecular interactions and support the idea that the molecules distort from their ideal geometries, improving packing in both crystals. The search for minima in the lattice energy of both crystals amongst the more common space groups with Z' = 1, using a simulated annealing crystal structure prediction procedure followed by lattice energy minimization showed that the observed structure of 3,4,5,6-THP anhydride (Z' = 2) is the thermodynamically most stable, and allowed us to justify why 3,4,5,6-THP anhydride crystallizes in such a complex structure with 16 molecules in the unit cell. The computational model was successful in predicting the second observed form at 173 K for cis-1,2,3,6-THP anhydride as a polymorph, and could predict several hypothetical structures with Z' = 1 that appear competitive with the observed structures. The results of phonon estimates of zero point intermolecular vibrational energy and entropy suggest that crystal structures of cis-1,2,3,6-THP anhydride cannot be predicted solely on the basis of lattice energy; factors other than thermodynamics favor the observed structures.

  1. Increased oral bioavailability of paclitaxel by its encapsulation through complex formation with cyclodextrins in poly(anhydride) nanoparticles.

    PubMed

    Agüeros, M; Zabaleta, V; Espuelas, S; Campanero, M A; Irache, J M

    2010-07-01

    The aim of this work was to study the oral bioavailability in rats of paclitaxel (PTX) when encapsulated as a complex with cyclodextrins in poly(anhydride) nanoparticles (NP). For this purpose three different cyclodextrins were selected: beta-cyclodextrin (CD), 2-hydroxypropyl-beta-cyclodextrin (HPCD) and 6-monodeoxy-6-monoamino-beta-cyclodextrin (NHCD). A single dose of 10mg paclitaxel per kg body weight as PTX-cyclodextrin nanoparticles was used. Plasma curves were characterised by a plateau of paclitaxel concentration close to the C(max) from T(max) till 24h post-administration. For PTX-CD NP and PTX-HPCD NP, these sustained levels of the anticancer drug were found to be between 27 and 33-fold higher than the reported value of drug activity whereas the relative oral bioavailability of paclitaxel was calculated to be higher than 80%. These facts would be directly related with a synergistic effect obtained by the combination of the bioadhesive properties of poly(anhydride) nanoparticles and the inhibitory effect of cyclodextrins on the activity of P-glycoprotein and cythocrome P450.

  2. The properties of poly(lactic acid)/starch blends with a functionalized plant oil: tung oil anhydride.

    PubMed

    Xiong, Zhu; Li, Chao; Ma, Songqi; Feng, Jianxian; Yang, Yong; Zhang, Ruoyu; Zhu, Jin

    2013-06-05

    Bio-sourced polymers, polylactide (PLA) and starch, have been melt-blended by lab-scale co-extruder with tung oil anhydride (TOA) as the plasticizer. The ready reaction between the maleic anhydride on TOA and the hydroxyl on starch led TOA molecules to accumulate on starch and increased the compatibility of PLA/starch blends, which was confirmed by FT-IR analyses and SEM. The TOA could change the mechanical properties and physical behaviors of PLA/starch blends. DSC and DMA analysis show that the TOA layer on starch has an effect on the thermal behavior of PLA in the ternary blend. The enrichment of TOA on starch improves the toughness and impact strength of the PLA/starch blends. The adding amount of TOA in PLA/starch blends primarily determined the compatibility and mechanical properties of the resulted ternary blends. The tensile and impact fracture modes of the PLA/starch blend with or without TOA has also been investigated by SEM analysis.

  3. Anhydride functionalised calcium ferrite nanoparticles: a new selective magnetic material for enrichment of lead ions from water and food samples.

    PubMed

    Pirouz, Mojgan Jafari; Beyki, Mostafa Hossein; Shemirani, Farzaneh

    2015-03-01

    In this research a sonochemistry route for manufacture of uniform nanocrystalline CaFe2O4 and its anhydride functionalisation were reported. The potential of raw and modified material as a magnetically separable sorbent in selective enrichment of lead ions from water and food samples is outlined. This material was characterised using FT-IR, XRD, SEM and VSM techniques. The SEM and VSM results indicated that the calcium ferrite nanoparticles are sphere-like particles possessing superparamagnetic properties with an average diameter of 40 nm. Various analytical parameters, including pH, contact time, type and concentration of eluent, adsorption capacity, sample volume and interference of ions, were optimised. Following a modification by anhydride, calcium ferrite selectivity toward lead ions was raised more than twofold compared to the unmodified nanoparticles. Finally a pre-concentration procedure was applied for determination of trace Pb(II) in canned tuna fish, canned tomato paste, parsley, milk and well-water samples with satisfactory results.

  4. Efficacy of measures of hygiene in workers sensitised to acid anhydrides and the influence of selection bias on the results

    PubMed Central

    Drexler, H.; Schaller, K. H.; Nielsen, J.; Weber, A.; Weihrauch, M.; Welinder, H.; Skerfving, S.

    1999-01-01

    OBJECTIVES: Organic acid anhydrides are potential sensitisers and cause occupational airway diseases. In an intervention study the efficacy of measures of hygiene at the workplace and possible selection bias were investigated. METHODS: A first investigation with 110 workers exposed to hexahydrophthalic acid anhydride (HHPA) and methyltetrahydrophthalic acid anhydride (MTHPA) was carried out in July 1991. The results (skin prick test, specific serum IgE) showed that 20 people were sensitised, and in a challenge test the clinical relevance of the sensitisation was confirmed in six subjects. In December 1991, the hygiene conditions at the plant were improved. In November 1995 a second investigation of 84 people was performed (anamnesis, skin prick test, specific IgE, spirometry, and ambient and biological monitoring). The 27 people who had left the plant in the meantime were asked their reasons for leaving. RESULTS: The relative risk of people sensitised in 1991 of leaving the plant between 1991 and 1995 was 2.6 (95% confidence interval (95% CI) 1.4 to 4.9) compared with people without any sign of sensitisation. The percentage of people identified as sensitised in 1991, who were still working at the plant and came to the second investigation, was higher than for people without evidence of sensitisation (10/10 v 47/73; p < 0.05). In all the 10 sensitised people in 1991 the findings of the first investigation were confirmed in 1995. The rate of sensitisation in 1995 was 21%. None of the six people employed after 1991 showed evidence of sensitisation. Of the six people with clinically relevant sensitisation confirmed by a challenge test in 1991, five were still at their workplace. From 1991 they were only exposed to MTHPA at a reduced concentration (< 0.5-36 micrograms/m3 in 1995). All of them reported fewer symptoms than in 1991. No signs of bronchial obstruction were detected by spirometry at the workplace. CONCLUSIONS: In cross sectional studies there is a selection

  5. Morphology and phase controlled cobalt nanostructures in magnetic polypropylene nanocomposites: the role of alkyl chain-length in maleic anhydride grafted polypropylene.

    PubMed

    He, Qingliang; Yuan, Tingting; Luo, Zhiping; Haldolaarachchige, Neel; Young, David P; Wei, Suying; Guo, Zhanhu

    2013-04-04

    A novel function of maleic anhydride grafted polypropylene (PP) with different backbone chain-lengths was demonstrated, i.e., in controlling the cobalt morphologies (dispersed polyhedral vs. assembled chain nanostructure), crystalline structures (ε- vs. β-phase), and magnetic property (242 vs. 808 Oe) in the synthesized magnetic PP nanocomposites.

  6. 40 CFR 721.3635 - Octadecanoic acid, ester with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4).

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Octadecanoic acid, ester with 1,2..., ester with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as octadecanoic acid,...

  7. 40 CFR 721.3635 - Octadecanoic acid, ester with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4).

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Octadecanoic acid, ester with 1,2..., ester with 1,2-propanediol, phosphate, anhydride with silicic acid (H4SiO4). (a) Chemical substance and significant new uses subject to reporting. (1) The chemical substance identified as octadecanoic acid,...

  8. An atom-economic approach to carboxylic acids via Pd-catalyzed direct addition of formic acid to olefins with acetic anhydride as a co-catalyst.

    PubMed

    Wang, Yang; Ren, Wenlong; Shi, Yian

    2015-08-21

    An effective Pd-catalyzed hydrocarboxylation of olefins using formic acid with acetic anhydride as a co-catalyst is described. A variety of carboxylic acids are obtained in good yields with high regioselectivities under mild reaction conditions without the use of toxic CO gas.

  9. Is the 2,3-carbon-carbon bond of indole really inert to oxidative cleavage by Oxone?--synthesis of isatoic anhydrides from indoles.

    PubMed

    Nelson, Amber C; Kalinowski, Emily S; Czerniecki, Nikolas J; Jacobson, Taylor L; Grundt, Peter

    2013-11-21

    A recent report has indicated that the oxidizing agent Oxone does not possess the ability to cleave the 2,3-carbon-carbon bond of indole. Work in our laboratory shows that this is not the case. Indole and a variety of aryl ring substituted derivatives readily react to form synthetically important isatoic anhydrides.

  10. Biotin-conjugated N-methylisatoic anhydride: a chemical tool for nucleic acid separation by selective 2'-hydroxyl acylation of RNA.

    PubMed

    Ursuegui, S; Chivot, N; Moutin, S; Burr, A; Fossey, C; Cailly, T; Laayoun, A; Fabis, F; Laurent, A

    2014-06-01

    An isatoic anhydride derivative conjugated to a biotin and a disulfide linker was specifically designed for the separation of nucleic acids. Starting from a DNA-RNA mixture, a selective 2'-hydroxyl acylation of RNAs followed by capture with streptavidin-coated magnetic beads and cleavage of the disulfide led to elution of RNAs.

  11. Characterization of maleic acid/anhydride copolymer films by low-rate dynamic liquid-fluid contact angle measurements using axisymmetric drop shape analysis.

    PubMed

    Uhlmann, Petra; Skorupa, Sebastian; Werner, Carsten; Grundke, Karina

    2005-07-05

    Thin films of alternating maleic acid/anhydride copolymers (poly(octadecene-alt-maleic acid/anhydride), POMA; poly(propene-alt-maleic acid/anhydride), PPMA; poly(styrene-alt-maleic acid/anhydride), PSMA) were studied to unravel the influence of the comonomer characteristics in the backbone on the surface-energetic properties of the copolymer films in the dry state and in contact with aqueous solutions. Water contact angle measurements revealed a graduation of the wettability of the dry hydrolyzed and annealed copolymer films that was dependent on the comonomer unit. It ranged from moderately hydrophilic (PPMA, annealed gamma(sv) = 39.9 mJ/m2) to very hydrophobic (POMA, annealed, gamma(sv) = 18.4 mJ/m2) surfaces. Liquid-fluid contact angle measurements using captive air bubbles were performed in different aqueous media (pure water, phosphate-buffered saline, and 10(-)(3) M KCl of two different pH values (pH = 3 and pH = 10) to study the copolymer films in their hydrated states relevant for biointerfacial phenomena. It was found that the graduation of the wettability of the copolymer films in the dry state is overall maintained upon immersion in aqueous solutions. The dependence of the wettability on the pH value of the aqueous medium could be related to the (de)protonation of the carboxylic groups.

  12. Asymmetric synthesis of the HMG-CoA reductase inhibitor atorvastatin calcium: an organocatalytic anhydride desymmetrization and cyanide-free side chain elongation approach.

    PubMed

    Chen, Xiaofei; Xiong, Fangjun; Chen, Wenxue; He, Qiuqin; Chen, Fener

    2014-03-21

    An efficient asymmetric synthesis of atorvastatin calcium has been achieved from commercially available diethyl 3-hydroxyglutarate through a novel approach that involves an organocatalytic enantioselective cyclic anhydride desymmetrization to establish C(3) stereogenicity and cyanide-free assembly of C7 amino type side chain via C5+C2 strategy as the key transformations.

  13. SELECTIVE HYDROGENATION OF MALEIC ANHYDRIDE TO Y-BUTROLACTONE OVER PD/AL2O3 CATALYST USING SUPERCRITICAL CARBON DIOXIDE MEDIUM

    EPA Science Inventory

    Hydrogenation of maleic anhydride to g-butyrolactone over Pd/Al2O3 catalyst under supercritical carbondioxide medium

    Unnikrishnan R. Pillai and Endalkachew Sahle-Demessie
    National Risk Management Research laboratory (NRMRL), Clean Processes Branch, MS 443, United States...

  14. Synthesis of both enantiomers of hemiesters by enantioselective methanolysis of meso cyclic anhydrides catalyzed by alpha-amino acid-derived chiral thioureas.

    PubMed

    Manzano, Rubén; Andrés, José M; Muruzábal, María-Dolores; Pedrosa, Rafael

    2010-08-06

    Both ureas and thioureas derived from L- or D-valine act as bifunctional organocatalysts able to induce the enantioselective alcoholysis of mono-, bi-, and tricyclic meso anhydrides. The desymmetrization occurs in near quantitative yields and excellent enantiomeric ratios (up to >99:<1) under low catalyst loading. Both enantiomers of the hemiesters can be directly obtained by changing the configuration of the catalyst.

  15. Reaction of dimethoxycarbene-DMAD zwitterion with 1,2-diones and anhydrides: a novel synthesis of highly substituted dihydrofurans and spirodihydrofurans.

    PubMed

    Nair, Vijay; Deepthi, Ani; Poonoth, Manojkumar; Santhamma, Bindu; Vellalath, Sreekumar; Babu, Beneesh Pattoorpady; Mohan, Resmi; Suresh, Eringathodi

    2006-03-17

    The zwitterion formed by the reaction of dimethoxycarbene and DMAD adds efficiently to one of the carbonyl groups of 1,2-dicarbonyl compounds and anhydrides to generate dihydrofurans and spirodihydrofurans in good yields. In many cases, the carbene inserts into the C-C bond of the dione to yield masked vicinal tricarbonyl systems.

  16. Formulation of salicylate-based poly(anhydride-ester) microspheres for short- and long-term salicylic acid delivery

    PubMed Central

    Rosario-Meléndez, Roselin; Ouimet, Michelle A.; Uhrich, Kathryn E.

    2013-01-01

    The formulation of salicylate-based poly(anhydride-ester) (PAE) microspheres was optimized by altering polymer concentration and homogenization speed to improve the overall morphology. The microspheres were prepared using three salicylate-based PAEs with different chemical compositions comprised of either a heteroatomic, linear aliphatic, or branched aliphatic moiety. These PAEs broadened the range of complete salicylic acid release to now include days, weeks and months. The molecular weight (Mw), polydispersity index (PDI) and glass transition temperature (Tg) of the formulated polymers were compared to the unformulated polymers. In general, the Mw and PDI exhibited decreased and increased values, respectively, after formulation, whereas the Tg changes did not follow a specific trend. Microsphere size and morphology were determined using scanning electron microscopy. These microspheres exhibited smooth surfaces, no aggregation, and size distributions ranging from 2-34 m in diameter. In vitro release studies of the chemically incorporated salicylic acid displayed widely tunable release profiles. PMID:23420391

  17. The effect of chemical modification with pyromellitic anhydride on structure, function, and thermal stability of horseradish peroxidase.

    PubMed

    Hassani, Leila

    2012-06-01

    The stability of enzymes remains a critical issue in biotechnology. Compared with the strategies for obtaining stable enzymes, chemical modification is a simple and effective technique. In the present study, chemical modification of horseradish peroxidase (HRP) was carried out with pyromellitic anhydride. HRP has achieved a prominent position in the pharmaceutical, chemical, and biotechnological industries. In this study, the effect of chemical modification on thermal stability, structure, and function of the enzyme was studied by fluorescence, circular dichroism, and absorbance measurements. The results indicated a decrease in compactness of the structure and a considerable enhancement in thermal stability of HRP below 60 °C. It seems the charge replacement and introduction of the bulky group bring about the observed structural and the functional changes.

  18. New polymers for 193-nm single-layer resists based on substituted cycloolefins/maleic anhydride resins

    NASA Astrophysics Data System (ADS)

    Rushkin, Ilya L.; Houlihan, Francis M.; Kometani, Janet M.; Hutton, Richard S.; Timko, Allen G.; Reichmanis, Elsa; Nalamasu, Omkaram; Gabor, Allen H.; Medina, Arturo N.; Slater, Sydney G.; Neisser, Mark O.

    1999-06-01

    A series of new polymers for 193 nm single layer resist based on maleic anhydride/cycloolefin systems with minimum amount of acrylate units were synthesized. In order to minimize the acrylate content, the cycloolefin moiety of the polymers was functionalized with side groups designed to either promotes adhesion to silicon substrate and/or impart the imaging functionality. All polymers were prepared by free-radical polymerization in moderate to high yields and were characterized by variety of techniques. The initial lithographic evaluation of the new resists was carried out. It was found that acrylates can be successfully replaced with appropriately substituted cycloolefins to provide good resolution. The etch resistance of the new materials generally improves with increase in cycloolefin content. The Onishi and Kunz type plots will be discussed.

  19. Recovery of uranium(VI) from aqueous solution by 2-picolylamine functionalized poly(styrene-co-maleic anhydride) resin.

    PubMed

    Liu, Shudi; Yang, Ying; Liu, Tonghuan; Wu, Wangsuo

    2017-07-01

    A 2-picolylamine functionalized poly(styrene-co-maleic anhydride) resin was synthesized and characterized by FT-IR, elemental analysis, SEM and XPS. To recover uranium from aqueous solution, the influence factors such as pH values, contact time, temperature and initial uranium concentration were optimized. Adsorption kinetics fitted well with the pseudo-second-order model, whereas adsorption isotherm matched well with the Langmuir isothermal adsorption model, with the maximum sorption capacity of 518.39mgg(-1) at pH 5.30 and 298K. The uptake of uranium could be implied in 0.01M coexisted ions environment. Besides, the resin could be regenerated by 0.1M HNO3 and repeatedly utilized in circles. The study proved that the resin has potential application prospects for disposal of uranium(VI).

  20. Biodegradable Ferulic Acid-containing Poly(anhydride-ester): Degradation Products with Controlled Release and Sustained Antioxidant Activity

    PubMed Central

    Ouimet, Michelle A.; Griffin, Jeremy; Carbone-Howell, Ashley L.; Wu, Wen-Hsuan; Stebbins, Nicholas D.; Di, Rong; Uhrich, Kathryn E.

    2013-01-01

    Ferulic acid (FA) is an antioxidant and photoprotective agent used in biomedical and cosmetic formulations to prevent skin cancer and senescence. Although FA exhibits numerous health benefits, physicochemical instability leading to decomposition hinders its efficacy. To minimize inherent decomposition, a FA-containing biodegradable polymer was prepared via solution polymerization to chemically incorporate FA into a poly(anhydride-ester). The polymer was characterized using nuclear magnetic resonance and infrared spectroscopies. The molecular weight and thermal properties were also determined. In vitro studies demonstrated that the polymer was hydrolytically degradable, thus providing controlled release of the chemically incorporated bioactive with no detectable decomposition. The polymer degradation products were found to exhibit antioxidant and antibacterial activity comparable to free FA and in vitro cell viability studies demonstrated that the polymer is non-cytotoxic towards fibroblasts. This renders the polymer a potential candidate for use as a controlled release system for skin care formulations. PMID:23327626

  1. Chitosan: poly( N-vinylpyrrolidone- alt-itaconic anhydride) nanocapsules—a promising alternative for the lung cancer treatment

    NASA Astrophysics Data System (ADS)

    Raţă, Delia Mihaela; Chailan, Jean-François; Peptu, Cătălina Anişoara; Costuleanu, Marcel; Popa, Marcel

    2015-07-01

    This study reports the preparation of novel polymeric nanocapsules based on a natural polymer, chitosan and a synthetic one, poly( N-vinylpyrrolidone- alt-itaconic anhydride) [(poly(NVPAI)] using an interfacial condensation technique. The infrared spectroscopy studies confirmed the crosslinking through the presence of amide bonds, formed between the two polymers chains. The diameter of nanocapsules was found in the range of 126-214 nm and it was determined by dynamic light scattering method. Morphological characterization demonstrated their nano size, the spherical shape of the nanocapsules and the formation of hollow particles. The nanocapsules presented good swelling capacity in aqueous solutions. 5-Fluorouracil (5-FU) loading and release capacity was studied, the processes being controlled by the drug diffusion through the polymeric membrane. The obtained results were encouraging, showing that 5-FU-loaded nanocapsules had 70 % higher apoptotic effect on A549 tumour cells than the drug in free state or mixed with the nanocapsules.

  2. Biodegradable ferulic acid-containing poly(anhydride-ester): degradation products with controlled release and sustained antioxidant activity.

    PubMed

    Ouimet, Michelle A; Griffin, Jeremy; Carbone-Howell, Ashley L; Wu, Wen-Hsuan; Stebbins, Nicholas D; Di, Rong; Uhrich, Kathryn E

    2013-03-11

    Ferulic acid (FA) is an antioxidant and photoprotective agent used in biomedical and cosmetic formulations to prevent skin cancer and senescence. Although FA exhibits numerous health benefits, physicochemical instability leading to decomposition hinders its efficacy. To minimize inherent decomposition, a FA-containing biodegradable polymer was prepared via solution polymerization to chemically incorporate FA into a poly(anhydride-ester). The polymer was characterized using nuclear magnetic resonance and infrared spectroscopies. The molecular weight and thermal properties were also determined. In vitro studies demonstrated that the polymer was hydrolytically degradable, thus providing controlled release of the chemically incorporated bioactive with no detectable decomposition. The polymer degradation products were found to exhibit antioxidant and antibacterial activity comparable to that of free FA, and in vitro cell viability studies demonstrated that the polymer is noncytotoxic toward fibroblasts. This renders the polymer a potential candidate for use as a controlled release system for skin care formulations.

  3. Modification of pineapple peel fibre with succinic anhydride for Cu2+, Cd2+ and Pb2+ removal from aqueous solutions.

    PubMed

    Hu, Xiuyi; Zhao, Mouming; Song, Guosheng; Huang, Huihua

    2011-01-01

    Research on chemical modification of pineapple peel fibre with succinic anhydride was carried out to create a novel adsorbent for Cu2+, Cd2+ and Pb2+ removal from aqueous solution. After pretreatment with iso-propyl alcohol and NaOH, pineapple peel fibre was modified via reaction with succinic anhydride for introduction of carboxylic functional groups. The modified pineapple peel fibre was characterized with Fourier transform infrared (FTIR) spectroscopy and evaluated for its adsorptive ability for Cu2+, Cd2+ and Pb2+ from synthetic metal solutions. The FTIR analysis proved the introduction of carboxylic functional groups in the backbone of the modified pineapple peel fibre. The modified pineapple peel fibre showed higher adsorptive capacity for Cu2+, Cd2+ and Pb2+ compared with raw pineapple peel and pineapple peel fibre pretreated with iso-propyl alcohol. The adsorption of Cu2+, Cd2+ and Pb2+ on the modified pineapple peel fibre depended on solution pH value, adsorption time and initial metal concentration. The maximum adsorption capacities of the modified fibre were observed at pH 5.4 for Cu2+ (27.68 +/- 0.83 mg g(-1) or 0.44 mmol g(-1)), at pH 7.5 for Cd2+ (34.18 +/- 1.02 mg g(-1) or 0.30 mmol g(-1)) and at pH 5.6 for Pb2+ (70.29 +/- 2.11 mg g(-1) or 0.34 mmol g(-1)) respectively. The adsorption followed the pseudo-second-order kinetics model and the experimental data coincided well with the Langmuir model.

  4. Improved lithographic performance for resists based on polymers having a vinyl ether-maleic anhydride (VEMA) backbone

    NASA Astrophysics Data System (ADS)

    Kim, Hyun-Woo; Choi, Sang-Jun; Jung, Dong-Won; Lee, Sook; Lee, Sung-Ho; Kang, Yool; Woo, Sang-Gyun; Moon, Joo-Tae; Kavanagh, Robert J.; Barclay, George G.; Orsula, George W.; Mattia, Joe; Caporale, Stefan; Adams, Timothy G.; Tanaka, Tsutomu; Kang, Doris

    2001-08-01

    ArF lithography, in combination with chemically amplified resists, has been investigated as one of the most promising technologies for producing patterns below 100 nm. In considering the polymer matrix for 193 nm photoresist applications, factors such as sensitivity, transparency to 193 nm radiation, adhesion to substrate, dry etch resistance, ease of synthesis, and availability of monomers are very critical. In these respects, remarkable progress has been made in development of ArF resist material. Polymers of acrylic and methacrylic esters show good imaging performance at 193 nm, but have insufficient dry-etch resistance under oxide or nitride etch condition. On the other hand, cyclic olefin-maleic anhydride (COMA) alternating copolymers exhibit good dry etch resistance, but have poor resolution capability. We previously reported a new platform, based on a vinyl ether-maleic anhydride (VEMA) alternating polymer system, that demonstrated both good resolution and high dry etch resistance. In this paper, VEMA systems with improved lithographic performance are presented. The new platform (VEMA) showed good performance in resolution, depth of focus (DOF), iso-dense bias, and post-etch roughness. With conventional illumination (NA=0.6, sigma=0.7), 120 nm dense line/space patterns with 0.4 (mu) M DOF were resolved. And 90 nm L/S patterns 0.6 (mu) M DOF were resolved with off-axis illumination (NA=0.63). Another important factor to be considered for the dry-etch process is post-etch roughness. In the case of VEMA system a clean surface was observed after etch under oxide, nitride, and poly conditions. The VEMA resist system is regarded as one of the most production-worthy material for real device manufacture.

  5. Rapid microwaves synthesis of CoSi{sub x}/CNTs as novel catalytic materials for hydrogenation of phthalic anhydride

    SciTech Connect

    Zhang, Liangliang; Chen, Xiao; Jin, Shaohua; Guan, Jingchao; Williams, Christopher T.; Peng, Zhijian; Liang, Changhai

    2014-09-15

    CoSi{sub x}/CNTs catalysts with different CoSi{sub x} phases (CoSi, CoSi{sub 2}) have been rapidly synthesized via a microwave-assisted route and applied for the liquid phase hydrogenation of phthalic anhydride. The synthesized catalysts were analyzed and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy-energy dispersive X-ray spectroscopy, thermogravimetric/derivative thermogravimetric analysis. The reaction progress of cobalt silicides and the ratio of Co:Si were monitored at different microwave irradiation times by XRD, giving insight into the formation mechanism. Compared to the Co/CNTs catalyst, all the prepared CoSi{sub x}/CNTs catalysts exhibited excellent activity and good selectivity to phthalide under mild reaction conditions (180–220 °C and 4.0 MPa H{sub 2}). This novel methodology can be applied to the synthesis of other transition metal silicides such as FeSi, Ni{sub 2}Si, and Cu{sub 4}Si. - Graphical abstract: CoSi{sub x}/CNTs catalysts with different CoSi{sub x} phases (CoSi{sub 2}, CoSi) have been rapidly synthesized via microwave-assisted route, which involves the vaporization of CoCl{sub 2} and subsequent reaction of CoCl{sub 2} with Si. - Highlights: • CoSi{sub x}/CNTs catalysts have been rapid synthesized via microwave-assisted route. • The phases of CoSi{sub x} were controlled by varying microwave time and Co:Si ratio. • FeSi, Ni{sub 2}Si and Cu{sub 4}Si were also synthesized via microwave-assisted route. • CoSi{sub x}/CNTs catalysts can be applied in hydrogenation of phthalic anhydride.

  6. Polyimides Derived from Novel Asymmetric Benzophenone Dianhydrides

    NASA Technical Reports Server (NTRS)

    Chuang, Chun-Hua (Inventor)

    2015-01-01

    This invention relates to the composition and processes for preparing thermoset polyimides derived from an asymmetric dianhydride, namely 2,3,3',4'-benzophenone dianhydride (a-BTDA) with at least one diamine, and a monofunctional terminal endcaps. The monofunctional terminating groups include 4-phenylethynylphthalic anhydride ester-acid derivatives, phenylethyl trimellitic anhydride (PETA) and its ester derivatives as well as 3-phenylethynylaniline. The process of polyimide composite comprises impregnating monomer reactants of dianhydride or its ester-acid derivatives, diamine and with monofunctional reactive endcaps into glass, carbon, quartz or synthetic fibers and fabrics, and then stack up into laminates and subsequently heated to between 150-375.degree. C. either at atmosphere or under pressure to promote the curing and crosslinking of the reactive endcaps to form a network of thermoset polyimides.

  7. Phenylethynyl Containing Reactive Additives

    NASA Technical Reports Server (NTRS)

    Connell, John W. (Inventor); Smith, Joseph G., Jr. (Inventor); Hergenrother, Paul M. (Inventor)

    2002-01-01

    Phenylethynyl containing reactive additives were prepared from aromatic diamines containing phenylethynyl groups and various ratios of phthalic anhydride and 4-phenylethynylphthalic anhydride in glacial acetic acid to form the imide in one step or in N-methyl-2-pyrrolidi none to form the amide acid intermediate. The reactive additives were mixed in various amounts (10% to 90%) with oligomers containing either terminal or pendent phenylethynyl groups (or both) to reduce the melt viscosity and thereby enhance processability. Upon thermal cure, the additives react and become chemically incorporated into the matrix and effect an increase in crosslink density relative to that of the host resin. This resultant increase in crosslink density has advantageous consequences on the cured resin properties such as higher glass transition temperature and higher modulus as compared to that of the host resin.

  8. Synthesis and cure mechanism characterization of phenylethynyl-terminated imide oligomers

    NASA Astrophysics Data System (ADS)

    Back, Susanna Branion

    Polymer matrix composites (PMC) are being investigated by the Air Force for use in engine applications, which are comprised of an intermediate carbon fiber-reinforced high temperature phenylethynyl-terminated fluorinated polyimide resin. The high-temperature phenylethynyl-terminated fluorinated polyimide resin is prepared from 4-(phenylethynyl)phthalic anhydride (4-PEPA), p-phenylenediamine (p-PDA), and hexafluoroisopropylidene bisphthalic dianhydride (6FDA). In order for these materials to be exploited to their full potential, many fundamental aspects of the polymer system need to be better understood. For this study, the high-temperature cure mechanism, the chemical structures of cure reaction products, and the effect of physical properties of impurities in the 4-PEPA monomer were investigated. A phenylethynyl-terminated imide model compound, N-(3-phenoxybenzene)-4-phenylethynylphthalimide (N-PBPEP), was prepared using both industrial 4-PEPA and recrystallized 4-PEPA. The thermal cure of this low molecular weight compound was studied using a variety of analytical techniques including differential scanning calorimetry, Fourier transform infrared spectroscopy (FTIR), nuclear magnetic resonance spectroscopy (NMR), and mass spectrometry (MS). N-PBPEP made from industrial 4-PEPA begins curing 25°C later than N-PBPEP made from recrystallized 4-PEPA, indicating that thermal cure is affected by the purity of the 4-PEPA starting material. Also, both versions form an 830 g/mol dimer with three possible mechanistic pathways.

  9. 54 FR 38044: National Emission Standards for Hazardous Air Pollutants; Benzene Emissions From Maleic Anhydride Plants, Ethylbenzene/Styrene Plants, Benzene Storage Vessels, Benzene Equipment Leaks, and Coke By- Product Recovery Plants

    EPA Pesticide Factsheets

    Final Rule on National Emission Standards for Hazardous Air Pollutants; Benzene Emissions From Maleic Anhydride Plants, Ethylbenzene/Styrene Plants, Benzene Storage Vessels, Benzene Equipment Leaks, and Coke By-Product Recovery Plants.

  10. Mixed anhydrides (phosphoric-carboxyl) are also formed in the esterification of 5'-amp with n-acetylaminoacyl imidazolides - Implications regarding the origin of protein synthesis

    NASA Technical Reports Server (NTRS)

    Wickramasinghe, Nalinie S. M. D.; Lacey, James C., Jr.

    1992-01-01

    Procedure for the formation of aminoacyl esters of monoribonucleotides with aminoacyl imidazolides were first reported by Gottikh et al. (1970) and summarized in 1970. This reaction has been widely used by us and numbers of other workers as a convenient means of preparing aminoacyl esters of nucleotides. We have previously reported that, under conditions of excess imidazolide, large amounts of bis 2', 3' esters are formed in addition to the monoesters. However, to our knowledge, no one has reported that in addition to the esters, relatively large amounts of the mixed anhydride, with the amino acid carboxyl attached to the phosphate, are also formed at short reaction times. We report here on the relative amounts of anhydride and esters formed in this reaction of racemic mixtures of eleven N-acetyl amino acid imidazolides with 5'-AMP and discuss the relevance of the findings to the origin of protein synthesis.

  11. Electronic Effects of Aluminum Complexes in the Copolymerization of Propylene Oxide with Tricyclic Anhydrides: Access to Well-Defined, Functionalizable Aliphatic Polyesters.

    PubMed

    Van Zee, Nathan J; Sanford, Maria J; Coates, Geoffrey W

    2016-03-02

    The synthesis of well-defined and functionalizable aliphatic polyesters remains a key challenge in the advancement of emerging drug delivery and self-assembly technologies. Herein, we investigate the factors that influence the rates of undesirable transesterification and epimerization side reactions at high conversion in the copolymerization of tricyclic anhydrides with excess propylene oxide using aluminum salen catalysts. The structure of the tricyclic anhydride, the molar ratio of the aluminum catalyst to the nucleophilic cocatalyst, and the Lewis acidity of the aluminum catalyst all influence the rates of these side reactions. Optimal catalytic activity and selectivity against these side reactions requires a careful balance of all these factors. Effective suppression of undesirable transesterification and epimerization was achieved even with sterically unhindered monomers using a fluorinated aluminum salph complex with a substoichiometric amount of a nucleophilic cocatalyst. This process can be used to synthesize well-defined block copolymers via a sequential addition strategy.

  12. One-pot synthesis of 2-amino-4(3H)-quinazolinones via ring-opening of isatoic anhydride and palladium-catalyzed oxidative isocyanide-insertion.

    PubMed

    Ji, Fei; Lv, Mei-Fang; Yi, Wen-Bin; Cai, Chun

    2014-08-14

    An efficient and practical two-step process has been developed for the synthesis of 2-amino-4(3H)-quinazolinones via ring-opening of isatoic anhydride and palladium-catalyzed oxidative isocyanide-insertion in one pot. This regioselective procedure could construct a wide range of 2-amino-4(3H)-quinazolinones in moderate to excellent yields. Furthermore, the methodology also had distinct advantages of easily accessible starting materials and operational simplicity.

  13. [Influence of low concentration of sulphuric anhydride on metabolic status of peripheral blood lymphocytes in guinea pigs sensibilised with a biological allergen].

    PubMed

    Dolgushin, M V; Sosedova, L M

    2005-01-01

    The influence of sulphuric anhydride (2-4 mg/m3) on the metabolic status of peripheral blood lymphocytes of sensibilised guinea pigs with different sequence of biological (allergenic) and chemical exposure has been studied. The metabolic state was evaluated by histochemical assay of succinate and lactate dehydrogenases and acid phosphatase. The changes in activities of dehydrogenases were found to indicate a definite relationship with specific responses of combined effects of different factors.

  14. Effect of hydrostatic pressure, temperature, and solvent on the rate of the Diels-Alder reaction between 9,10-anthracenedimethanol and maleic anhydride

    NASA Astrophysics Data System (ADS)

    Kiselev, V. D.; Kornilov, D. A.; Anikin, O. V.; Latypova, L. I.; Konovalov, A. I.

    2017-03-01

    The rate of the reaction between 9,10-anthracenedimethanol and maleic anhydride in 1,4-dioxane, acetonitrile, trichloromethane, and toluene is studied at 25, 35, 45°C in the pressure range of 1-1772 bar. The rate constants, enthalpies, entropies and activation volumes are determined. It is shown that the rate of reaction with 9,10-anthracenedimethanol is approximately one order of magnitude higher than with 9-anthracenemethanol.

  15. Properties of polyethylene films with incorporated benzoic anhydride and/or ethyl and propyl esters of 4-hydroxybenzoic acid and their suitability for food packaging.

    PubMed

    Dobiás, J; Chudackova, K; Voldrich, M; Marek, M

    2000-12-01

    Benzoic anhydride and ethyl and propyl esters of 4-hydroxybenzoic acid (ETP and PRP, respectively, also termed parabens) incorporated into low density polyethylene (LDPE) film were studied with regard to migration into food and food simulants at 6 degrees C and 25 degrees C, and changes in selected properties of the film were investigated. Antimicrobials were incorporated into polymer film in concentrations of 5 g/kg and 10 g/kg. The addition of parabens into the polymer was more difficult than benzoic anhydride due to their volatility. For benzoic anhydride, 30-40% and 10-20% of the added amount was found to leach from the film into aqueous and olive oil food simulants, respectively. The migration into both water and olive oil followed a very similar course in the case of parabens. Migration levels over 90% and in the range of 70% to 80%, relative to the amount of agent in the film, were determined for ETP and PRP respectively. The incorporation of antimicrobials into the film significantly changed the functional characteristics of the packaging material, i.e. permeability of oxygen, carbon dioxide and water vapour, tensile strength, coefficient of friction, sealing strength and transparency. Shelf life tests with packaged cheese and toasted bread demonstrated the efficiency of the film containing 10 g/kg of BA against mould growth on the food surface during storage at 6 degrees C.

  16. In Vivo Evaluation of Nerve Guidance Conduits Comprised of a Salicylic Acid-based Poly(anhydride-ester) Blend

    NASA Astrophysics Data System (ADS)

    Lee, Yong Soo

    Unlike the central nervous system, peripheral nervous system can regenerate from injury. However, without surgical intervention, the results are often poor. Autologous nerve grafting is the golden standard for repairing peripheral nerve injury; but limited donor availability and donor site morbidity led researchers to seek alternative methods. Among the many alternative treatment options, synthetic nerve guidance conduits (NGCs) have been most actively developed. The goal of NGCs is to serve as a physical scaffold that aids the axonal regeneration process while preventing scar tissue formation that interferes with regeneration. Biocompatible and biodegradable NGCs would provide additional benefits: minimize foreign body reaction and avoid secondary surgeries to remove NGCs. We developed a unique NGC that incorporated the characteristics described above and can release an anti-inflammatory drug, salicylic acid. In this work, in vivo assays were performed to evaluate NGCs fabricated from a poly(anhydride-ester) blend. To further assist in the regeneration process, bovine native collagen type I hydrogel were inserted into the NGCs lumen which was then implanted in femoral nerve of mice for up to 16 weeks. These studies demonstrated in vivo biodegradability, biocompatibility, and axonal regeneration following an injury to the peripheral nerve. These studies provide greater insights into the importance of designing NGCs and how they aid in regeneration and functional recovery of subjects.

  17. Separator Membrane from Crosslinked Poly(Vinyl Alcohol) and Poly(Methyl Vinyl Ether-alt-Maleic Anhydride)

    PubMed Central

    Rohatgi, Charu Vashisth; Dutta, Naba K.; Choudhury, Namita Roy

    2015-01-01

    In this work, we report separator membranes from crosslinking of two polymers, such as poly vinyl alcohol (PVA) with an ionic polymer poly(methyl vinyl ether-alt-maleic anhydride) (PMVE-MA). Such interpolymer-networked systems were extensively used for biomedical and desalination applications but they were not examined for their potential use as membranes or separators for batteries. Therefore, the chemical interactions between these two polymers and the influence of such crosslinking on physicochemical properties of the membrane are systematically investigated through rheology and by critical gel point study. The hydrogen bonding and the chemical interaction between PMVE-MA and PVA resulted in highly cross-linked membranes. Effect of the molecular weight of PVA on the membrane properties was also examined. The developed membranes were extensively characterized by studying their physicochemical properties (water uptake, swelling ratio, and conductivity), thermal and electrochemical properties using differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), thermo-gravimetric analysis (TGA) and electrochemical impedance spectroscopy (EIS). The DSC study shows the presence of a single Tg in the membranes indicating compatibility of the two polymers in flexible and transparent films. The membranes show good stability and ion conductivity suitable for separator applications. PMID:28347019

  18. Intranasal Administration of Maleic Anhydride-Modified Human Serum Albumin for Pre-Exposure Prophylaxis of Respiratory Syncytial Virus Infection

    PubMed Central

    Sun, Zhiwu; Wang, Qian; Jia, Ran; Xia, Shuai; Li, Yuan; Liu, Qi; Xu, Wei; Xu, Jin; Du, Lanying; Lu, Lu; Jiang, Shibo

    2015-01-01

    Respiratory syncytial virus (RSV) is the leading cause of pediatric viral respiratory tract infections. Neither vaccine nor effective antiviral therapy is available to prevent and treat RSV infection. Palivizumab, a humanized monoclonal antibody, is the only product approved to prevent serious RSV infection, but its high cost is prohibitive in low-income countries. Here, we aimed to identify an effective, safe, and affordable antiviral agent for pre-exposure prophylaxis (PrEP) of RSV infection in children at high risk. We found that maleic anhydride (ML)-modified human serum albumin (HSA), designated ML-HSA, exhibited potent antiviral activity against RSV and that the percentages of the modified lysines and arginies in ML- are correlated with such anti-RSV activity. ML-HSA inhibited RSV entry and replication by interacting with viral G protein and blocking RSV attachment to the target cells, while ML-HAS neither bound to F protein, nor inhibited F protein-mediated membrane fusion. Intranasal administration of ML-HSA before RSV infection resulted in significant decrease of the viral titers in the lungs of mice. ML-HSA shows promise for further development into an effective, safe, affordable, and easy-to-use intranasal regimen for pre-exposure prophylaxis of RSV infection in children at high risk in both low- and high-income countries. PMID:25690799

  19. Preparation, characterization and luminescent properties of dense nano-silica hybrids loaded with 1,8-naphthalic anhydride.

    PubMed

    Wang, Jinpeng; Sun, Jihong; Li, Yuzhen; Wang, Feng

    2014-03-01

    Novel luminescent dense nano-silica hybrid materials (DNSS) modified with different amounts of (3-aminopropyl)triethoxysilane (APTES) and 1,8-naphthalic anhydride (NA) were successfully synthesized via two steps combined with post-grafting methods. Powder X-ray diffraction (XRD), N2-sorption analysis, Fourier transform infrared (FT-IR) spectroscopy, transmission electron microscopy (TEM), thermogravimetric analysis (TGA), photoluminescence (PL) spectroscopy and elemental analysis, as well as time-resolved decays were employed to characterize the resultant hybrid materials. The results revealed that luminescent organic molecules had been successfully loaded onto the amine-modified surface of nano-silica spheres. In addition, their fluorescence intensity and characteristic peak of emission spectra changed with increasing amount of APTES and NA additive. In particular, the characteristic peak showed a red shift from 390 to 450 nm, however, this was inconsistent with results calculated on the basis of the elemental analysis data, most probably because of the dispersion behaviors of NA molecules from the aggregating to the monolayer state. These observations demonstrated the existence of a quantum confinement effectiveness of NA-DNSS samples, and therefore a possible mechanism was put forward.

  20. In vitro release of clomipramine HCl and buprenorphine HCl from poly adipic anhydride (PAA) and poly trimethylene carbonate (PTMC) blends.

    PubMed

    Dinarvand, Rassoul; Alimorad, Mohammed Massoud; Amanlou, Massoud; Akbari, Hamid

    2005-10-01

    Controlled drug-delivery technology is concerned with the systematic release of a pharmaceutical agent to maintain a therapeutic level of the drug in the body for modulated and/or prolonged periods of time. This may be achieved by incorporating the therapeutic agent into a degradable polymer vehicle, which releases the agent continuously as the matrix erodes. In this study, poly trimethylene carbonate (PTMC), an aliphatic polycarbonate, and poly adipic anhydride (PAA), an aliphatic polyanhydride, were synthesized via melt condensation and ring-opening polymerization of trimethylene carbonate and adipic acid, respectively. The release of clomipramine HCl and buprenorphine HCl from discs prepared with the use of PTMC-PAA blends in phosphate buffer (pH 7.4) are also described. Clomipramine HCl and buprenorphine HCl were both used as hydrophilic drug models. Theoretical treatment of the data with the Peppas model revealed that release of clomipramine HCl (5%) in devices containing 70% PTMC or more followed a Fickian diffusion model. However, the releases of buprenorphine HCl (5%) in the same devices were anomalous. For devices containing 50% and more PAA, surface erosion may play a significant role in the release of both molecules.

  1. Thermal decomposition behaviors and kinetic properties of 1,8-naphthalic anhydride loaded dense nano-silica hybrids

    NASA Astrophysics Data System (ADS)

    Wang, Jinpeng; Sun, Jihong; Wang, Feng; Ren, Bo

    2013-06-01

    A certain amount of (3-aminopropyl)triethoxysilane (APTES) and various capacity of 1,8-naphthalic anhydride (NA) were employed to modify and then graft onto the surface of the dense nano-silica spheres (DNSS) via a post-grafting method, and thereby, a novel luminescent density nano-silica hybrid materials have been successfully synthesized. Meanwhile, the structures and properties of obtained hybrid DNSS were characterized by XRD, TEM, N2 sorption, FT-IR, and TG analysis. Furthermore, the thermal stability of before and after modification were demonstrated by using both Kissinger methods and Ozawa-Flynn-Wall methods. Particularly, the thermal decomposition behaviors of amino-modified groups and NA-grafted organic molecules were emphasized based on the TG and DTG analysis and then the related mechanism was put forward according to Coats and Redfern methods. Finally, as a comparison, the obtained results and the proposed decomposition mechanism of hybrid DNSS with non-pores were discussed with that of mesopores silicas in details.

  2. Study of yellow luminescence of binary terbium complexes based on 3,3',4,4'-biphthalic anhydride.

    PubMed

    Lin, Meijuan; Wang, Xiaoping; Tang, Qiang; An, Qi; Zeng, Huijuan; Ling, Qidan

    2014-01-20

    Three novel binary Tb(III) complexes (TbL2, TbL, and Tb2L; L=3,3',4,4'-biphenyl tetracarboxylic ligand) were synthesized by changing the molar ratio of Tb(III) to 3,3',4,4'-biphthalic anhydride (BPDA) (1∶2, 1∶1, and 2∶1, respectively). IR spectra indicate that there are two coordination modes of the carboxylate ligands with Tb3+ ions in the complexes. Most of them are in bridging mode; the others are in chelating mode. These complexes all have good thermal stability. The photophysical properties of these complexes are studied in detail using UV absorption spectra, fluorescence spectra, and transient fluorescence spectra. The results indicate that the photoluminescence properties of the complexes depend strongly on the molar ratio of Tb(III) to BPDA. When the molar ratio of Tb(III) to BPDA is 1∶1, complex TbL exhibits the strongest yellow light emission among the three Tb(III) complexes. However, complex Tb2L exhibits a weaker yellowish-green light emission when the molar ratio of Tb(III) to BPDA is 2∶1. The phenomenon of the yellow emission from terbium complexes is rarely reported.

  3. Olefin-maleic-anhydride copolymer based additives: a novel approach for compatibilizing blends of waste polyethylene and crumb rubber.

    PubMed

    Tóth, Balázs; Varga, Csilla; Bartha, László

    2015-04-01

    In our work processing conditions and mechanical properties of waste polyethylene (PE)/crumb rubber (CR) blends have been improved by new types of compatibilizing additives synthesized from experimental olefin-maleic-anhydride copolymers at our laboratory. Compatibilizing additives have been introduced into the PE/CR blends in 0.2 wt% while CR concentration has been varied between 10 and 50 wt%. For comparison of the effects commercially available MA-g-PO type compatibilizing additives have also been applied. Tensile and Charpy impact tests of the compression moulded samples have been carried out. Several experimental additives have enhanced properties of the PE/CR blends either from the point of view of tensile or Charpy impact strength while commercial additives have had improving effects only on one of the abovementioned mechanical properties but not for both of them simultaneously. Since good mechanical properties could be achieved by our experimental compatibilizers good adhesion in the waste PE/CR samples have been considered and was proven by SEM graphs either.

  4. Anhydride-functional silane immobilized onto titanium surfaces induces osteoblast cell differentiation and reduces bacterial adhesion and biofilm formation.

    PubMed

    Godoy-Gallardo, Maria; Guillem-Marti, Jordi; Sevilla, Pablo; Manero, José M; Gil, Francisco J; Rodriguez, Daniel

    2016-02-01

    Bacterial infection in dental implants along with osseointegration failure usually leads to loss of the device. Bioactive molecules with antibacterial properties can be attached to titanium surfaces with anchoring molecules such as silanes, preventing biofilm formation and improving osseointegration. Properties of silanes as molecular binders have been thoroughly studied, but research on the biological effects of these coatings is scarce. The aim of the present study was to determine the in vitro cell response and antibacterial effects of triethoxysilypropyl succinic anhydride (TESPSA) silane anchored on titanium surfaces. X-ray photoelectron spectroscopy confirmed a successful silanization. The silanized surfaces showed no cytotoxic effects. Gene expression analyses of Sarcoma Osteogenic (SaOS-2) osteoblast-like cells cultured on TESPSA silanized surfaces reported a remarkable increase of biochemical markers related to induction of osteoblastic cell differentiation. A manifest decrease of bacterial adhesion and biofilm formation at early stages was observed on treated substrates, while favoring cell adhesion and spreading in bacteria-cell co-cultures. Surfaces treated with TESPSA could enhance a biological sealing on implant surfaces against bacteria colonization of underlying tissues. Furthermore, it can be an effective anchoring platform of biomolecules on titanium surfaces with improved osteoblastic differentiation and antibacterial properties.

  5. Development of a guided bone regeneration device using salicylic acid-poly(anhydride-ester) polymers and osteoconductive scaffolds.

    PubMed

    Mitchell, Ashley; Kim, Brian; Cottrell, Jessica; Snyder, Sabrina; Witek, Lukasz; Ricci, John; Uhrich, Kathryn E; O'Connor, J Patrick

    2014-03-01

    Successful repair of craniofacial and periodontal tissue defects ideally involves a combined therapy that includes inflammation modulation, control of soft tissue infiltration, and bone regeneration. In this study, an anti-inflammatory polymer, salicylic acid-based poly(anhydride-ester) (SAPAE) and a three-dimensional osteoconductive ceramic scaffold were evaluated as a combined guided bone regeneration (GBR) system for concurrent control of inflammation, soft tissue ingrowth, and bone repair in a rabbit cranial defect model. At time periods of 1, 3, and 8 weeks, five groups were compared: (1) scaffolds with a solid ceramic cap (as a GBR structure); (2) scaffolds with no cap; (3) scaffolds with a poly(lactide-glycolide) cap; (4) scaffolds with a slow release SAPAE polymer cap; and (5) scaffolds with a fast release SAPAE polymer cap. Cellular infiltration and bone formation in these scaffolds were evaluated to assess inflammation and bone repair capacity of the test groups. The SAPAE polymers suppressed inflammation and displayed no deleterious effect on bone formation. Additional work is warranted to optimize the anti-inflammatory action of the SAPAE, GBR suppression of soft tissue infiltration, and stimulation of bone formation in the scaffolds and create a composite device for successful repair of craniofacial and periodontal tissue defects.

  6. Estimating regio and stereoselectivity in [4+2] cycloadditions of vinyl-substituted cyclic dienes with maleic anhydride.

    PubMed

    Gayatri, Gaddamanugu; Sastry, G Narahari

    2009-10-29

    Density functional theory calculations are performed to examine the regio and stereoselective preferences in [4+2] cycloaddition reactions of vinyl cyclopentadiene (1 and 2) and vinyl heterocyclic (1-N, 1-O, 1-S, 2-N, 2-O and 2-S) systems with maleic anhydride. Stepwise and concerted pathways of model systems 1 and 2 as dienes with ethylene as dienophile reveal that the reactions proceed through asynchronous and concerted pathway. 3-Vinyl systems (2) are predicted to be more reactive compared to 2-vinyl systems (1). The regio and stereoselective preferences are evaluated based on activation energies, reaction energies, density functional based descriptors and atoms in molecules analysis. In all cases, extra-annular cycloadducts are more feasible compared to intra-annular cycloadducts. Stereoselectivity depends on the favorable secondary orbital interactions. Solvents such as water, tetrahydrofuran, acetone, and dimethyl sulphoxide are employed to understand the effects of solvents on the cycloadduct formation. The computational results thus obtained are compared with the earlier experimental observations that are available.

  7. Slow digestion property of octenyl succinic anhydride modified waxy maize starch in the presence of tea polyphenols.

    PubMed

    Peng, Shanli; Xue, Lei; Leng, Xue; Yang, Ruobing; Zhang, Genyi; Hamaker, Bruce R

    2015-03-18

    The in vivo slow digestion property of octenyl succinic anhydride modified waxy corn starch (OSA-starch) in the presence of tea polyphenols (TPLs) was studied. Using a mouse model, the experimental results showed an extended and moderate postprandial glycemic response with a delayed and significantly decreased blood glucose peak of OSA-starch after cocooking with TPLs (5% starch weight base). Further studies revealed an increased hydrodynamic radius of OSA-starch molecules indicating an interaction between OSA-starch and TPLs. Additionally, decreased gelatinization temperature and enthalpy and reduced viscosity and emulsifiability of OSA-starch support their possible complexation to form a spherical OSA-starch-TPLs (OSAT) complex. The moderate and extended postprandial glycemic response is likely caused by decreased activity of mucosal α-glucosidase, which is noncompetitively inhibited by tea catechins released from the complex during digestion. Meanwhile, a significant decrease of malondialdehyde (MDA) and increased DPPH free radical scavenging activity in small intestine tissue demonstrated the antioxidative functional property of the OSAT complex. Thus, the complex of OSAT, acting as a functional carbohydrate material, not only leads to a flattened and prolonged glycemic response but also reduces the oxidative stress, which might be beneficial to health.

  8. Inhaled multiwalled carbon nanotubes modulate the immune response of trimellitic anhydride-induced chemical respiratory allergy in brown Norway rats.

    PubMed

    Staal, Yvonne C M; van Triel, Jos J; Maarschalkerweerd, Thérèse V P; Arts, Josje H E; Duistermaat, Evert; Muijser, Hans; van de Sandt, Johannes J M; Kuper, C Frieke

    2014-10-01

    The interaction between exposure to nanomaterials and existing inflammatory conditions has not been fully established. Multiwalled carbon nanotubes (MWCNT; Nanocyl NC 7000 CAS no. 7782-42-5; count median diameter in atmosphere 61 ± 5 nm) were tested by inhalation in high Immunoglobulin E (IgE)-responding Brown Norway (BN) rats with trimellitic anhydride (TMA)-induced respiratory allergy. The rats were exposed 2 days/week over a 3.5-week period to a low (11 mg/m(3)) or a high (22 mg/m(3)) concentration of MWCNT. Nonallergic animals exposed to MWCNT and unexposed allergic and nonallergic rats served as controls. At the end of the exposure period, the allergic animals were rechallenged with TMA. Histopathological examination of the respiratory tract showed agglomerated/aggregated MWCNT in the lungs and in the lung-draining lymph nodes. Frustrated phagocytosis was observed as incomplete uptake of MWCNT by the alveolar macrophages and clustering of cells around MWCNT. Large MWCNT agglomerates/aggregates were found in granulomas in the allergic rats, suggesting decreased macrophage clearance in allergic rats. In allergic rats, MWCNT exposure decreased serum IgE levels and the number of lymphocytes in bronchoalveolar lavage. In conclusion, MWCNT did not aggravate the acute allergic reaction but modulated the allergy-associated immune response.

  9. Modification of bovine heart succinate dehydrogenase with ethoxyformic anhydride and rose bengal: evidence for essential histidyl residues protectable by substrates.

    PubMed

    Hederstedt, L; Hatefi, Y

    1986-06-01

    Purified and membrane-bound succinate dehydrogenase (SDH) from bovine heart mitochondria was inhibited by the histidine-modifying reagents ethoxyformic anhydride (EFA) and Rose Bengal in the presence of light. Succinate and competitive inhibitors protected against inhibition, and decreased the number of histidyl residues modified by EFA. The essential residue modified by EFA was not the essential thiol of SDH, but modification of the essential thiol abolished the protective effect of malonate against inhibition of SDH by EFA. The EFA inhibition was reversed by hydroxylamine nearly completely when the inhibition was less than or equal to 35%, and only partially when the inhibition was more extensive. The uv spectrum of EFA-modified SDH before and after hydroxylamine treatment suggested that extensive inhibition of SDH with EFA may result in ethoxyformylation at both imidazole nitrogens of histidyl residues. Such a modification is not reversed by hydroxylamine. Succinate dehydrogenases and fumarate reductases from several different sources have similar compositions, and the two enzymes from Escherichia coli have considerable homology in the amino acid composition of their respective flavoprotein and iron-sulfur protein subunits. In the former, there is a short stretch containing conserved histidine, cysteine, and arginine residues. These residues, if also conserved in the bovine enzyme, may be the essential active site residues suggested by this work (histidine) and previously (cysteine, arginine).

  10. Microencapsulation of white champaca (Michelia alba D.C.) extract using octenyl succinic anhydride (OSA) starch for controlled release aroma.

    PubMed

    Samakradhamrongthai, Rajnibhas; Thakeow, Prodpran; Kopermsub, Phikunthong; Utama-Ang, Niramon

    2016-12-01

    The objective of the study was to optimise the encapsulation of Michelia alba D.C. (MAD) extract using octenyl succinic anhydride (OSA) starch. The MAD extract (5-10 g/100 g of dry starch) and the OSA starch (25-100 g/100 ml of water) was used in microcapsule preparation and analysed for the physicochemical and encapsulation properties. The optimised formula using the MAD extract and the OSA starch were 15.00 g/100 g of dry starch and 96.32 g/100 g water, which provided the highest in yield recovery (40.65% ± 0.99) and encapsulation efficiency (68.91% ± 1.50), with the lowest moisture content (3.19% ± 0.06) and water activity (0.236 ± 0.004). The aroma release from the optimum encapsulated powder in simulated artificial saliva fluid (SSF) suggested that linalool retention in microcapsules was higher than verbenone and 2-methyl butanoic acid. This study shows that the optimised formulation of MAD encapsulated flavour powder was found to be effective for controlling the aroma release.

  11. Experimental and theoretical study on the reaction of N3-phenyl-(pyridin-2-yl)carbohydrazonamide with itaconic anhydride

    NASA Astrophysics Data System (ADS)

    Modzelewska-Banachiewicz, Bożena; Paprocka, Renata; Mazur, Liliana; Saczewski, Jarosław; Kutkowska, Jolanta; Stępień, Dorota K.; Cyrański, Michał

    2012-08-01

    Two new 1,2,4-triazole-containing alkenoic acid derivatives were obtained from the reaction of N-phenyl-(pyridin-2-yl)carbohydrazonamide with itaconic anhydride, depending on the reaction conditions. The structures of 2-((4-phenyl-5-(pyridin-2-yl)-4H-1,2,4-triazol-3-yl)methyl)acrylic acid or (E)-2-methyl-3(4-phenyl-5-(pyridine-2-yl)-4H-1,2,4-triazol-3-yl)acrylic acid were confirmed by means of 1D and 2D NMR spectroscopic data as well as by single-crystal X-ray diffraction analysis. The experiential 1H and 13C chemical shifts were compared with those calculated with B3LYP, EDF1, and EDF2 density functional theories. The theoretical study of the observed terminal-to-internal alkene isomerization was performed with density functional (DFT) B3LYP/6-31+G∗ method using SM8 water and DMF solvation models. Antimicrobial activities of the newly prepared alkenoic acid derivatives were verified experimentally by a broth microdilution method.

  12. Interface-mediated inactivation of pancreatic lipase by a water-reactive compound: 2-sulfobenzoic cyclic anhydride.

    PubMed

    Moulin, A; Fourneron, J D; Piéroni, G; Verger, R

    1989-07-25

    2-Sulfobenzoic cyclic anhydride (SBA) rapidly and selectively inactivates porcine pancreatic lipase (PPL) only when added during the hydrolysis of an emulsified ester such as tributyrin or dodecyl acetate. The present data suggest that the inactivation of PPL occurs preferentially at the oil/water interface and not in the aqueous phase, since colipase and bile salt were found to adversely affect the inhibition process. Moreover, it is shown that at a molar ratio of SBA to pure PPL of 1, 40% of the lipase activity was already irreversibly lost. Complete inactivation was observed at SBA to pure PPL molar ratios of 120. A 60% inactivation occurred when 0.5 mol of 3H-labeled SBA was attached per mole of PPL. The SBA-inactivated PPL competes for binding to the dodecyl acetate/water interface as efficiently as the native enzyme. Larger SBA concentrations are required when crude lipase preparations are used as well as with pure PPL in the presence of bile salts and colipase. Lipases were found to have variable sensitivities to SBA inactivation, depending on their origin. In the presence of bile salts and tributyrin at pH 6.0, human gastric lipase activity was not affected by the presence of a 10(6) molar excess of SBA.

  13. Processable Polyimides Containing APB and Reactive End Caps

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J.

    2003-01-01

    Imide copolymers that contain 1,3- bis(3-aminophenoxy)benzene (APB) and other diamines and dianhydrides and that are terminated with appropriate amounts of reactive end caps have been invented. The reactive end caps investigated thus far include 4-phenylethynyl phthalic anhydride (PEPA), 3- aminophenoxy-4-phenylethynylbenzop henone (3-APEB), maleic anhydride (MA), and 5-norbornene-2,3-dicarboxylic anhydride [also known as nadic anhydride (NA)]. The advantage of these copolyimides terminated with reactive groups, relative to other polyimides terminated with reactive groups, is a combination of (1) higher values of desired mechanical-property parameters and (2) greater ease of processing into useful parts.

  14. Evaluation of methods for measuring relative permeability of anhydride from the Salado Formation: Sensitivity analysis and data reduction

    SciTech Connect

    Christiansen, R.L.; Kalbus, J.S.; Howarth, S.M.

    1997-05-01

    This report documents, demonstrates, evaluates, and provides theoretical justification for methods used to convert experimental data into relative permeability relationships. The report facilities accurate determination of relative permeabilities of anhydride rock samples from the Salado Formation at the Waste Isolation Pilot Plant (WIPP). Relative permeability characteristic curves are necessary for WIPP Performance Assessment (PA) predictions of the potential for flow of waste-generated gas from the repository and brine flow into repository. This report follows Christiansen and Howarth (1995), a comprehensive literature review of methods for measuring relative permeability. It focuses on unsteady-state experiments and describes five methods for obtaining relative permeability relationships from unsteady-state experiments. Unsteady-state experimental methods were recommended for relative permeability measurements of low-permeability anhydrite rock samples form the Salado Formation because these tests produce accurate relative permeability information and take significantly less time to complete than steady-state tests. Five methods for obtaining relative permeability relationships from unsteady-state experiments are described: the Welge method, the Johnson-Bossler-Naumann method, the Jones-Roszelle method, the Ramakrishnan-Cappiello method, and the Hagoort method. A summary, an example of the calculations, and a theoretical justification are provided for each of the five methods. Displacements in porous media are numerically simulated for the calculation examples. The simulated product data were processed using the methods, and the relative permeabilities obtained were compared with those input to the numerical model. A variety of operating conditions were simulated to show sensitivity of production behavior to rock-fluid properties.

  15. Alveolar macrophages have a dual role in a rat model for trimellitic anhydride-induced occupational asthma

    SciTech Connect

    Valstar, Dingena L.; Schijf, Marcel A.; Nijkamp, Frans P.; Storm, Gert; Arts, Josje H.E.; Kuper, C. Frieke; Bloksma, Nanne; Henricks, Paul A.J. . E-mail: p.a.j.henricks@pharm.uu.nl

    2006-02-15

    Occupational exposure to low molecular weight chemicals, like trimellitic anhydride (TMA), can result in occupational asthma. Alveolar macrophages (AMs) are among the first cells to encounter inhaled compounds. These cells can produce many different mediators that have a putative role in asthma. In this study, we examined the role of AMs in lung function and airway inflammation of rats exposed to TMA. Female Brown Norway rats were sensitized by dermal application of TMA or received vehicle alone on days 0 and 7. One day before challenge, rats received intratracheally either empty or clodronate-containing liposomes to deplete the lungs of AMs. On day 21, all rats were challenged by inhalation of TMA in air. Lung function parameters were measured before, during, within 1 h after, and 24 h after challenge. IgE levels and parameters of inflammation and tissue damage were assessed 24 h after challenge. Sensitization with TMA led to decreased lung function parameters during and within 1 h after challenge as compared to non-sensitized rats. AM depletion alleviated the TMA-induced drop in lung function parameters and induced a faster recovery compared to sham-depleted TMA-sensitized rats. It also decreased the levels of serum IgE 24 h after challenge, but did not affect the sensitization-dependent increase in lung lavage fluid IL-6 and tissue TNF-{alpha} levels. In contrast, AM depletion augmented the TMA-induced tissue damage and inflammation 24 h after challenge. AMs seem to have a dual role in this model for TMA-induced occupational asthma since they potentiate the immediate TMA-induced decrease in lung function but tended to dampen the TMA-induced inflammatory reaction 24 h later.

  16. Chemical modification with phthalic anhydride and chitosan: Viable options for the stabilization of raw starch digesting amylase from Aspergillus carbonarius.

    PubMed

    Nwagu, Tochukwu Nwamaka; Okolo, Bartholomew; Aoyagi, Hideki; Yoshida, Shigeki

    2017-06-01

    The raw starch digesting type of amylase (RSDA) presents greater opportunities for process efficiency at cheaper cost and shorter time compared to regular amylases. Chemical modification is a simple and rapid method toward their stabilization for a wider application. RSDA from Aspergillus carbonarius was modified with either phthalic anhydride (PA) or chitosan. Activity retention was 87.3% for PA-modified and 80.9% for chitosan-modified RSDA. Optimum pH shifted from 5 to 7 after PA-modification. Optimum temperature changed from 30°C (native) to 30-40°C and 60°C for PA-modified and chitosan-modified, respectively. Activation energy (kJmol(-1)) for hydrolysis was 13.5, 12.7, and 10.2 while the activation energy for thermal denaturation was 32.8, 80.3, 81.9 for free, PA-modified and chitosan-modified, respectively. The specificity constants (Vmax/Km) were 73.2 for PA-modified, 63.1 for chitosan-modified and 77.1 for native RSDA. The half-life (h) of the RSDA at 80°C was increased from 6.1 to 25.7 for the PA-modified and 138.6 for the chitosan derivative. Modification also led to increase in D value, activation enthalpy and Gibbs free energy of enzyme deactivation. Fluorescence spectra showed that center of spectral mass decreased for the PA-modified RSDA but increased for chitosan modified RSDA.

  17. Novel 4-arm poly(ethylene glycol)-block-poly(anhydride-esters) amphiphilic copolymer micelles loading curcumin: preparation, characterization, and in vitro evaluation.

    PubMed

    Lv, Li; Shen, Yuanyuan; Li, Min; Xu, Xiaofen; Li, Mingna; Guo, Shengrong; Huang, Shengtang

    2013-01-01

    A novel 4-arm poly(ethylene glycol)-block-poly(anhydride-esters) amphiphilic copolymer (4-arm PEG-b-PAE) was synthesized by esterization of 4-arm poly(ethylene glycol) and poly(anhydride-esters) which was obtained by melt polycondensation of α -, ω -acetic anhydride terminated poly(L-lactic acid). The obtained 4-arm PEG-b-PAE was characterized by (1)H-NMR and gel permeation chromatography. The critical micelle concentration of 4-arm PEG-b-PAE was 2.38 μg/mL. The curcumin-loaded 4-arm PEG-b-PAE micelles were prepared by a solid dispersion method and the drug loading content and encapsulation efficiency of the micelles were 7.0% and 85.2%, respectively. The curcumin-loaded micelles were spherical with a hydrodynamic diameter of 151.9 nm. Curcumin was encapsulated within 4-arm PEG-b-PAE micelles amorphously and released from the micelles, faster in pH 5.0 than pH 7.4, presenting one biphasic drug release pattern with rapid release at the initial stage and slow release later. The hemolysis rate of the curcumin-loaded 4-arm PEG-b-PAE micelles was 3.18%, which was below 5%. The IC50 value of the curcumin-loaded micelles against Hela cells was 10.21 μg/mL, lower than the one of free curcumin (25.90 μg/mL). The cellular uptake of the curcumin-loaded micelles in Hela cell increased in a time-dependent manner. The curcumin-loaded micelles could induce G2/M phase cell cycle arrest and apoptosis of Hela cells.

  18. Non-woven fibrous materials with antibacterial properties prepared by tailored attachment of quaternized chitosan to electrospun mats from maleic anhydride copolymer.

    PubMed

    Ignatova, Milena; Petkova, Zhanina; Manolova, Nevena; Markova, Nadya; Rashkov, Iliya

    2012-01-01

    In order to impart antibacterial properties to microfibrous electrospun materials from styrene/maleic anhydride copolymers, quaternized chitosan derivatives (QCh) containing alkyl substituents of different chain lengths are covalently attached to the mats. A complete inhibition of the growth of bacteria, S. aureus (Gram-positive) and E. coli (Gram-negative), for a contact time of 30–120 min or a decrease of the bacterial titer by 2–3 log units is observed depending on the quaternization degree, the chain length of the alkyl substituent, and the molar mass of QCh. The modified mats are also effective in suppressing the adhesion of pathogenic S. aureus bacteria.

  19. Poly(anhydride-ester) and poly(N-vinyl-2-pyrrolidone) blends: salicylic acid-releasing blends with hydrogel-like properties that reduce inflammation.

    PubMed

    Ouimet, Michelle A; Fogaça, Renata; Snyder, Sabrina S; Sathaye, Sameer; Catalani, Luiz H; Pochan, Darrin J; Uhrich, Kathryn E

    2015-03-01

    Polymers such as poly(N-vinyl-2-pyrrolidone) (PVP) have been used to prepare hydrogels for wound dressing applications but are not inherently bioactive. For enhanced healing, PVP was blended with salicylic acid-based poly(anhydride-esters) (SAPAE) and shown to exhibit hydrogel properties upon swelling. In vitro release studies demonstrated that the chemically incorporated drug (SA) was released from the polymer blends over 3-4 d in contrast to 3 h, and that blends of higher PVP content displayed greater swelling values and faster SA release. The polymer blends significantly the inflammatory cytokine, TNF-α, in vitro without negative effects.

  20. Solubilization and purification of recombinant modified C-reactive protein from inclusion bodies using reversible anhydride modification.

    PubMed

    Potempa, Lawrence A; Yao, Zhen-Yu; Ji, Shang-Rong; Filep, János G; Wu, Yi

    . Herein, we describe a method using anhydride reagents to effectively solubilize rmCRP and allow for chromatographic purification in high yield and free of contaminating endotoxin. Furthermore, the purified rmCRP reagent represents an excellent comparable protein to the biologically produced mCRP and as a distinctive reagent from pCRP. Deciphering the true function of CRP in both health and disease requires a knowledge, understanding, and reliable supply of each of its structures so to define the distinctive effects of each on the body's response to tissue damaging events.

  1. Adhesive and Composite Properties of a New Phenylethynyl Terminated Imide

    NASA Technical Reports Server (NTRS)

    Thompson, C. M.; Connell, J. W.; Hergenrother, P. M.

    2002-01-01

    A relatively new phenylethynyl terminated imide oligomer (PETI) from the reaction of 2,3,',4'- biphenyltetracarboxylic dianhydride, 4,4'-oxydianiline and endcapped with 4- phenylethynylphthalic anhydride at a calculated number average molecular weight of 5000 g/mole was evaluated as an adhesive and composite matrix. The asymmetric dianhydride imparts a low melt viscosity to the oligomer and a high glass transition temperature to the cured resin. Preliminary adhesive work with titanium (6Al-4V) adherend gave good room temperature (RT) tensile shear strengths and excellent retention of RT strength at 260 C. Preliminary composite work using unsized IM7 carbon fiber provided moderate to high mechanical properties. The chemistry, mechanical, and physical properties of the new PETI in neat resin, adhesive and composite form are presented.

  2. High Temperature Transfer Molding Resins: Preliminary Composite Properties of PETI-375

    NASA Technical Reports Server (NTRS)

    Connell, J. W.; Smith, J. G., Jr.; Hergenrother, P. M.; Criss, J. M., Jr.

    2004-01-01

    As part of an ongoing effort to develop materials for resin transfer molding (RTM) of high performance/high temperature composites, a new phenylethynyl containing imide designated as PETI-375 has been under evaluation. PETI-375 was prepared using 2,3,3 ,4 - biphenyltetracarboxylic dianhydride (a-BPDA), 1,3-bis(4-aminophenoxy)benzene and 2,2 - bis(trifluoromethyl)benzidine and endcapped with 4-phenylethynylphthalic anhydride. This material exhibited a stable melt viscosity of 0.1-0.4 Pa sec at 280 C. High quality, void-free laminates were fabricated by high temperature RTM using unsized T-650 carbon fabric and evaluated. After curing for 1 hour at 371 C, the laminates exhibited a glass transition temperature of approx. 375 C by thermomechanical analysis. The laminates were essentially void and microcrack free as evidenced by optical microscopic examination. The chemistry, physical, and composite properties of PETI-375 will be discussed.

  3. Low-melt Viscosity Polyimide Resins for Resin Transfer Molding (RTM) II

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Criss, Jim M.; Mintz, Eric A.; Scheiman, Daniel A.; Nguyen, Baochau N.; McCorkle, Linda S.

    2007-01-01

    A series of polyimide resins with low-melt viscosities in the range of 10-30 poise and high glass transition temperatures (Tg s) of 330-370 C were developed for resin transfer molding (RTM) applications. These polyimide resins were formulated from 2,3,3 ,4 -biphenyltetracarboxylic dianhydride (a-BPDA) with 4-phenylethynylphthalic anhydride endcaps along with either 3,4 - oxyaniline (3,4 -ODA), 3,4 -methylenedianiline, (3,4 -MDA) or 3,3 -methylenedianiline (3,3 -MDA). These polyimides had pot lives of 30-60 minutes at 260-280 C, enabling the successful fabrication of T650-35 carbon fiber reinforced composites via RTM process. The viscosity profiles of the polyimide resins and the mechanical properties of the polyimide carbon fiber composites will be discussed.

  4. Energy filtering transmission electron microscopy immunocytochemistry and antigen retrieval of surface layer proteins from Tannerella forsythensis using microwave or autoclave heating with citraconic anhydride.

    PubMed

    Moriguchi, K; Mitamura, Y; Iwami, J; Hasegawa, Y; Higuchi, N; Murakami, Y; Maeda, H; Yoshimura, F; Nakamura, H; Ohno, N

    2012-11-01

    Tannerella forsythensis (Bacteroides forsythus), an anaerobic Gram-negative species of bacteria that plays a role in the progression of periodontal disease, has a unique bacterial protein profile. It is characterized by two unique protein bands with molecular weights of more than 200 kDa. It also is known to have a typical surface layer (S-layer) consisting of regularly arrayed subunits outside the outer membrane. We examined the relationship between high molecular weight proteins and the S-layer using electron microscopic immunolabeling with chemical fixation and an antigen retrieval procedure consisting of heating in a microwave oven or autoclave with citraconic anhydride. Immunogold particles were localized clearly at the outermost cell surface. We also used energy-filtering transmission electron microscopy (EFTEM) to visualize 3, 3'-diaminobenzidine tetrahydrochloride (DAB) reaction products after microwave antigen retrieval with 1% citraconic anhydride. The three-window method for electron spectroscopic images (ESI) of nitrogen by the EFTEM reflected the presence of moieties demonstrated by the DAB reaction with horseradish peroxidase (HRP)-conjugated secondary antibodies instead of immunogold particles. The mapping patterns of net nitrogen were restricted to the outermost cell surface.

  5. Effects of Secondary Polymer Covalently Attached to Monodisperse, Poly(maleic anhydride-styrene)-Modified Colloidal Silica on Dispersibility in Organic Solvent.

    PubMed

    Yoshinaga; Shimada; Nishida; Komatsu

    1999-06-15

    Effects of surface-grafted polymer on the dispersibility of polymer-silica composite particles in ethyl acetate-methanol cosolvent were investigated. The composite particles were prepared by a two-step modification of monodisperse colloidal silica (120 nm in diameter). Modifications were carried out by first reacting the surface silanol of the colloidal silica with maleic anhydride-styrene copolymer silane coupling agent to prevent aggregation and then grafting, in acetone or tetrahydrofuran, amino group-terminated poly(methyl acrylate), poly(methyl methacrylate), or polystyrene to the maleic anhydride moiety on the surface. For poly(methyl acrylate) and poly(methyl methacrylate) graftings, composite particles with long polymer chains aggregated in methanol-rich cosolvent due to insoluble secondary polymer chain interaction among the particles. Particles with a small amount of relatively low-molecular-weight secondary polymer were dispersible in the methanol content range from 0 to 90 vol%. Polystyrene-modified particles never aggregated, even in 90 vol% methanol solution. An ESR study of the suspension in ethyl acetate-hexane cosolvent suggested that the dispersibility of these composite particles in ethyl acetate-rich solution is attributable to steric repulsion between solvated and expanded secondary polymer chains among the particles. The dispersibility of the composite particles in methanol-rich solution was controlled by a delicate balance between the electrostatic repulsion and the interparticle attraction due to the desolvated and insoluble polymer chain interaction among the particles. Copyright 1999 Academic Press.

  6. A highly efficient green synthesis of N-alkyl 2-[(2-oxo-2-aryl ethyl) amino] benzamide derivatives from reaction of isatoic anhydride, primary amines and 2-bromoacethophenone.

    PubMed

    Sabbaghan, Maryam; Hossaini, Zinatossadat

    2012-11-01

    N-alkyl 2-[(2-oxo-2-aryl ethyl)amino] benzamide derivatives have been synthesized in high yields. This involves three-component reaction of isatoic anhydride, primary amines in the presence of 2-bromoacethophenone derivatives. The reaction workup is simple and the products can be easily separated from the reaction mixture.

  7. Effect of pre-irradiation PPO-grafted maleic anhydride on structure and properties of PPO-g-MAH/PA66 blends

    NASA Astrophysics Data System (ADS)

    Li, Wenfei; Yao, Zhanhai; Yao, Ruixiang; Li, Xuan; Liu, Shumei

    2014-04-01

    The pre-irradiation polyphenylene oxide (PPO)-graft-maleic anhydride (PPO-g-MAH) was carried out by reactive extrusion. The chemical structure of PPO-g-MAH was characterized by means of Fourier-transform infrared spectroscopy. The wettability of PPO-g-MAH was characterized by the contact angle method. The blends of PPO-g-MAH/polyamide 66 (PA66) were prepared. Compared with the PPO/PA66 blends, mechanical properties of PPO-g-MAH/PA66 blends were distinctly improved. Smaller dispersed particle sizes with narrower distribution were found in PPO-g-MAH/PA66 blends, via field-emitted scanning electron microscopy. Rheological properties of PPO-g-MAH/PA66 blends were studied with a rotational rheometer.

  8. Carbon-13 cross-polarization magic-angle-spinning nuclear magnetic resonance investigation of the interactions between maleic anhydride grafted polypropylene and wood polymers.

    PubMed

    Rude, Erica; Laborie, Marie-Pierre G

    2008-05-01

    The chemical interactions between maleic anhydride grafted polypropylene (MAPP) and wood were studied with solid-state carbon-13 cross-polarization magic-angle-spinning nuclear magnetic resonance ((13)C CPMAS NMR) spectroscopy. MAPP was synthesized with 100% (13)C enrichment at the C(1) and C(4) carbons to allow detection of the [1,4-(13)C(2)]MAPP functional groups and was melt blended with cellulose, lignin, and maple wood. In the cellulose/MAPP blend, changes in (13)C CPMAS NMR corrected signal intensities for the anhydride and dicarboxylic maleic acid functionalities suggested that esterification may have occurred predominantly from the more numerous diacid carbons. A single proton longitudinal relaxation in the rotating frame, (H)T(1rho), for the MAPP and the cellulose carbons in the blend suggested that they were spin coupled, i.e., homogeneous on a 10-200 Angstrom scale. Esterification was also suggested in the lignin/MAPP blend. Furthermore, the more significant changes in the intensities of the carbonyl signals and (H)T(1rho) values suggested that lignin may be more reactive to MAPP than cellulose. Finally, when maple was melt blended with MAPP, the same trends in the (13)C CP-MAS NMR spectra and (H)T(1rho) behavior were observed as when MAPP was blended with cellulose or lignin. This study therefore clarifies that during melt compounding of wood with MAPP, esterification occurs with wood polymers, preferentially with lignin. Understanding the interactions of MAPP with wood is of significance for the development of natural-fiber-reinforced thermoplastic composites.

  9. Enhancement of mechanical and thermal properties of oil palm empty fruit bunch fiber poly(butylene adipate-co-terephtalate) biocomposites by matrix esterification using succinic anhydride.

    PubMed

    Siyamak, Samira; Ibrahim, Nor Azowa; Abdolmohammadi, Sanaz; Yunus, Wan Md Zin Bin Wan; Rahman, Mohamad Zaki Ab

    2012-02-16

    In this work, the oil palm empty fruit bunch (EFB) fiber was used as a source of lignocellulosic filler to fabricate a novel type of cost effective biodegradable composite, based on the aliphatic aromatic co-polyester poly(butylene adipate-co-terephtalate) PBAT (Ecoflex™), as a fully biodegradable thermoplastic polymer matrix. The aim of this research was to improve the new biocomposites' performance by chemical modification using succinic anhydride (SAH) as a coupling agent in the presence and absence of dicumyl peroxide (DCP) and benzoyl peroxide (BPO) as initiators. For the composite preparation, several blends were prepared with varying ratios of filler and matrix using the melt blending technique. The composites were prepared at various fiber contents of 10, 20, 30, 40 and 50 (wt %) and characterized. The effects of fiber loading and coupling agent loading on the thermal properties of biodegradable polymer composites were evaluated using thermal gravimetric analysis (TGA). Scanning Electron Microscopy (SEM) was used for morphological studies. The chemical structure of the new biocomposites was also analyzed using the Fourier Transform Infrared (FTIR) spectroscopy technique. The PBAT biocomposite reinforced with 40 (wt %) of EFB fiber showed the best mechanical properties compared to the other PBAT/EFB fiber biocomposites. Biocomposite treatment with 4 (wt %) succinic anhydride (SAH) and 1 (wt %) dicumyl peroxide (DCP) improved both tensile and flexural strength as well as tensile and flexural modulus. The FTIR analyses proved the mechanical test results by presenting the evidence of successful esterification using SAH/DCP in the biocomposites' spectra. The SEM micrograph of the tensile fractured surfaces showed the improvement of fiber-matrix adhesion after using SAH. The TGA results showed that chemical modification using SAH/DCP improved the thermal stability of the PBAT/EFB biocomposite.

  10. Hydrogen-bonding in 2-aminobenzoyl-alpha-chymotrypsin formed by acylation of the enzyme with isatoic anhydride: IR and mass spectroscopic studies.

    PubMed

    Goodall, Jonathan J; Booth, Victoria K; Ashcroft, Alison E; Wharton, Christopher W

    2002-01-04

    The acyl-enzyme formed upon acylation of alpha-chymotrypsin with isatoic anhydride has been characterised by infrared spectroscopy. Acylation at pH 7 to yield the 2-aminobenzoyl-enzyme is rapid (k = 5.57x 10(-2)s(-1)), while deacylation is much slower (k =3.7 x 10(-5)10(-2) (s-). The [1C=O]-labelled form of isatoic anhydride has been synthesised, to allow construction of [72C=O]- minus [13C=O]difference spectra; these highlight the carbonyl absorbance of the ligand and eliminate spectral effects that arise from protein perturbation. The ester carbonyl band of the acyl-enzyme absorbs at a wavenumber of 1695cm(-1) and has been shown by deconvolution analysis to represent a single, well-defined conformation. Model studies of ethyl 2-aminobenzoate in a range of solvents show that its carbonyl group is in a hexane-like environment (that is, very nonpolar). It is proposed that the low wavenumber of the carbonyl absorbance arises from the presence of an internal hydrogen bond between the 2-amino group and the ester carbonyl oxygen; this leads to polarisation of the carbonyl group both in the enzyme and in nonpolar solvents. However, in view of the slow deacylation, it is clear that the acyl group is in a nonproductive conformation, with no interaction with the oxyanion hole, and that deacylation occurs from this form or from a minor, invisible form. The infrared data have been supported by kinetic electrospray mass spectroscopic measurements, which demonstrate that the acyl-enzyme is that previously anticipated, and by molecular modelling of 2-aminobenzoyl-alpha-chymotrypsin. It is concluded from pH-dependence measurements that general base catalysis by the 2-amino group is not involved in deacylation.

  11. Solvent effects in acid-catalyzed dehydration of the Diels-Alder cycloadduct between 2,5-dimethylfuran and maleic anhydride

    NASA Astrophysics Data System (ADS)

    Salavati-fard, Taha; Caratzoulas, Stavros; Doren, Douglas J.

    2017-03-01

    Dehydration of the cycloadduct produced from the Diels-Alder reaction between 2,5-dimethylfuran and maleic anhydride to 3,6-dimethylphthalic anhydride exemplifies an important step in producing platform chemicals from biomass. The mechanisms of dehydration and catalytic effects of Lewis and Brønsted acids are investigated with density functional theory. The uncatalyzed reaction has a very high activation barrier (68.7 kcal/mol) in the gas phase and it is not significantly affected by solvation. With a Lewis acid catalyst, modeled as an alkali ion, the activation barriers are reduced, but intermediates are also stabilized. The net effect in vacuum is that the energetic span, or apparent activation energy of the catalytic cycle, is 77.9 kcal/mol, even higher than the barrier in the uncatalyzed case. In solution, however, the energetic span is reduced by as much as 20 kcal/mol, due to differences in the solvation energy of the transition states and intermediates. In the case of a Brønsted acid catalyst, modeled as a proton, the gas phase transition state energies are reduced even more than in the Lewis acid case, and there is no strong stabilization of the intermediates. The energetic span in vacuum is only 13.8 kcal/mol and is reduced even further in solution. Brønsted acid catalysis appears to be the preferred mechanism for dehydration of this cycloadduct. Since the Diels-Alder reaction that produced the molecule has previously been shown to be catalyzed by Brønsted acids, this suggests that a single catalyst could be used to accelerate both steps.

  12. Evaluation of RTM370 Polyimide Composites by Resin Film Infusion (RFI)

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Yip, Thomas A.; Kollmansberger, Ronald B.; Tsotsis, Thomas K.

    2014-01-01

    RTM370 imide oligomer based on 2,3,3',4'-biphenyl dianhydride (a-BPDA), 3,4'-oxydianiline (3,4'-ODA) and terminated with the 4-phenylethynylphthalic (PEPA) endcap has been shown to exhibit a low melt viscosity (10-30 poise) at 280 C with a pot-life of 1-2 h and a high cured glass-transition temperature (Tg) of 370 C. RTM370 resin has been successfully infused into fiberglass-stitched T650-35 carbon-fabric preforms (ranged from 3- to 6-mm thick) by resin film infusion (RFI). The resulting composite panels were inspected by ultrasonic C-scan and by photomicrographs before and after post-curing as a quality control. Mechanical tests such as unnotched compression (UNC), open-hole compression (OHC), and short-beam shear strength (SBS) at ambient and elevated temperatures were performed before and after isothermal aging at 288 C for 1000 h to assess high-temperature performance. Thermal cycling of RTM370 stitched composites was also conducted from -54 C to 288 C for up to 1600 cycles to evaluate the microcrack resistance of RTM370 polyimide composites fabricated by RFI.

  13. Synthesis of 2,3-dihydroquinazolin-4(1H)-ones by three-component coupling of isatoic anhydride, amines, and aldehydes catalyzed by magnetic Fe(3)O(4) nanoparticles in water.

    PubMed

    Zhang, Zhan-Hui; Lü, Hong-Yan; Yang, Shu-Hong; Gao, Jian-Wu

    2010-09-13

    A simple and efficient protocol for one-pot three-component coupling of isatoic anhydride, amines, and aldehydes in water using magnetically recoverable Fe(3)O(4) nanoparticles is reported. This methodology results in the synthesis of a variety of 2,3-dihydroquinazolin-4(1H)-ones in high yields. The catalyst can be recovered and recycled without a significant loss in the catalytic activity.

  14. A medusa-like β-cyclodextrin with 1-methyl-2-(2'-carboxyethyl) maleic anhydrides, a potential carrier for pH-sensitive drug delivery.

    PubMed

    Kang, Sunyoung; Park, Euddeum; Kim, Youngeun; Lee, Seonju; Kwon, Jiwoong; Cho, Hyungdo; Lee, Yan

    2014-08-01

    We developed a new pH-sensitive drug delivery carrier based on β-cyclodextrin (β-CD) and 1-methyl-2-(2'-carboxyethyl) maleic anhydrides (MCM). The primary hydroxyl groups of β-CD were successfully attached to MCM residues to produce a medusa-like β-CD-MCM. The MCM residue was conjugated with cephradine (CP) with high efficiency ( > 90%). More importantly, β-CD-MCM-CP responded to the small pH drop from 7.4 to 5.5 and released greater than 80% of the drugs within 0.5 h at pH 5.5. In addition, the inclusion complex between β-CD-MCM-CP and the adamantane derivative was formed by simple mixing to show the possibility of introducing multi-functionality. Based on these results, β-CD-MCM can target weakly acidic tissues or organelles, such as tumours, inflammatory tissues, abscesses or endosomes, and be easily modified with various functional moieties, such as ligands for cell binding or penetration, enabling more efficient and specific drug delivery.

  15. 2, 3-Dimethylmaleic anhydride (3, 4-Dimethyl-2, 5-furandione): A plant derived insecticidal molecule from Colocasia esculenta var. esculenta (L.) Schott

    PubMed Central

    Rajashekar, Yallappa; Tonsing, Ngaihlun; Shantibala, Tourangbam; Manjunath, Javagal R.

    2016-01-01

    The phasing out of methyl bromide as a fumigant, resistance problems with phosphine and other fumigants in stored product beetles, and serious concern with human health and environmental safety have triggered the search for alternative biofumigants of plant origin. Despite the identification of a large number of plants that show insecticidal activity, and the diversity of natural products with inherent eco-friendly nature, newer biofumigants of plant origin have eluded discovery. Using a bioassay driven protocol, we have now isolated a bioactive molecule from the root stock of Colocasia esculenta (L.) and characterized it as 2, 3-dimethylmaleic anhydride (3, 4-dimethyl-2, 5-furandione) based on various physico-chemical and spectroscopic techniques (IR, 1H NMR, 13C NMR and Mass). The molecule proved to be an efficient biofumigant which is highly toxic to insect pests for stored grains even at very low concentration, but has no adverse effect on seed germination. We finally address the potential for this molecule to become a, effective biofumigant. PMID:26837840

  16. 2, 3-Dimethylmaleic anhydride (3, 4-Dimethyl-2, 5-furandione): A plant derived insecticidal molecule from Colocasia esculenta var. esculenta (L.) Schott.

    PubMed

    Rajashekar, Yallappa; Tonsing, Ngaihlun; Shantibala, Tourangbam; Manjunath, Javagal R

    2016-02-03

    The phasing out of methyl bromide as a fumigant, resistance problems with phosphine and other fumigants in stored product beetles, and serious concern with human health and environmental safety have triggered the search for alternative biofumigants of plant origin. Despite the identification of a large number of plants that show insecticidal activity, and the diversity of natural products with inherent eco-friendly nature, newer biofumigants of plant origin have eluded discovery. Using a bioassay driven protocol, we have now isolated a bioactive molecule from the root stock of Colocasia esculenta (L.) and characterized it as 2, 3-dimethylmaleic anhydride (3, 4-dimethyl-2, 5-furandione) based on various physico-chemical and spectroscopic techniques (IR, (1)H NMR, (13)C NMR and Mass). The molecule proved to be an efficient biofumigant which is highly toxic to insect pests for stored grains even at very low concentration, but has no adverse effect on seed germination. We finally address the potential for this molecule to become a, effective biofumigant.

  17. Plasma-enhanced CVD of functional coatings in Ar/maleic anhydride/C2H2 homogeneous dielectric barrier discharges at atmospheric pressure

    NASA Astrophysics Data System (ADS)

    Zajíčková, Lenka; Jelínek, Petr; Obrusník, Adam; Vodák, Jiří; Nečas, David

    2017-03-01

    In this contribution, we focus on the general problems of plasma-enhanced chemical vapor deposition in atmospheric pressure dielectric barrier discharges, i.e. deposition uniformity, film roughness and the formation of dust particles, and demonstrate them on the example of carboxyl coatings prepared by co-polymerization of acetylene and maleic anhydride. Since the transport of monomers at atmospheric pressure is advection-driven, special attention is paid to the gas dynamics simulations, gas flow patterns, velocity and residence time. By using numerical simulations, we design an optimized gas supply geometry capable of synthesizing uniform layers. The selection of the gas mixture containing acetylene was motivated by two of its characteristics: (i) suppression of filaments in dielectric barrier discharges, and (ii) improved film cross-linking, keeping the amount of functional groups high. However, acetylene discharges are prone to the formation of nanoparticles that can be incorporated into the deposited films, leading to their high roughness. Therefore, we also discuss the role of the gas composition, the spatial position of the substrate with respect to gas flow and the deposition time on the topography of the deposited films.

  18. Letrozole dispersed on poly (vinyl alcohol) anchored maleic anhydride grafted low density polyethylene: a controlled drug delivery system for treatment of breast cancer.

    PubMed

    Siddiqa, Akhtar Jahan; Chaudhury, Koel; Adhikari, Basudam

    2014-04-01

    The present work focuses on the design of a drug delivery system for systemic, controlled release of the poorly soluble breast cancer drug, letrozole. The drug delivery system was prepared in two steps: a low density polyethylene (LDPE) substrate surface was grafted with maleic anhydride (MA) via solution grafting technique. Next, the grafted substrate was used to anchor a hydrophilic polymeric drug release system consisting of poly (vinyl alcohol) (PVA). The PVA anchored MA grafted LDPE (PVA/MA-g-LDPE) drug release system was used for the controlled release of letrozole. This system was characterized using ATR-FTIR spectrophotometry, surface profilometry, and scanning electron microscopy. Biocompatibility studies were also carried out. In vitro release studies of letrozole from the system were performed in distilled water and phosphate buffer saline (PBS) at 37°C. Release of ∼90% letrozole from hydrophilic PVA matrix was observed within a period of 35 days. A high correlation coefficient (R(2)=0.99) was seen between the release of letrozole in distilled water and PBS. Cytotoxicity studies using MTT colorimetric assay suggested that all samples were biocompatible. It is concluded that the letrozole delivery system appears to overcome the limitations associated with letrozole by providing enhanced drug dissolution rate, controlled release and improved bioavailability of the incorporated drug and, therefore, seems to have extended therapeutic effects.

  19. Sub-micronic capsules based on gelatin and poly(maleic anhydride-alt-vinyl acetate) obtained by interfacial condensation with potential biomedical applications.

    PubMed

    Iurea, Delia Mihaela; Peptu, Cătălina Anişoara; Chailan, Jean-François; Carriere, Pascal; Popa, Marcel

    2013-06-01

    New sub-micronic capsules based on a copolymer of maleic anhydride-alt-vinyl acetate and a natural polymer (gelatin) using an interfacial condensation method were obtained. Sub-micronic capsules were characterized by Fourier Transform infrared spectroscopy (FTIR), dynamic light scattering (DLS) method, zeta-potential, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The thermal properties were investigated by thermogravimetric analysis (TGA). According to some parameters of the synthesis reaction (polymer weight ratio, acetone/water ratio, surfactant concentration), the mean diameter of the sub-micronic capsules can be tuned from 200 to 760 nm. The sub-micronic capsules show a higher agglomeration tendency as the amount of gelatin in their composition increases. The swelling capacity in aqueous solutions is dependent on the composition and size of the sub-micronic capsules, decreasing with their diameter and gelatin composition. The drug loading and release capacity was studied using Penicillin G (sodium salt) (PG), and it has been proved that it is influenced by the sub-micronic capsules morphology induced by preparation parameters. Encapsulation and controlled release of small molecule were successfully carried out, demonstrating the potential biomedical applications of these new easily obtained sub-micronic capsules.

  20. Deposition of antibacterial of poly(1,3-bis-(p-carboxyphenoxy propane)-co-(sebacic anhydride)) 20:80/gentamicin sulfate composite coatings by MAPLE

    NASA Astrophysics Data System (ADS)

    Cristescu, R.; Popescu, C.; Socol, G.; Visan, A.; Mihailescu, I. N.; Gittard, S. D.; Miller, P. R.; Martin, T. N.; Narayan, R. J.; Andronie, A.; Stamatin, I.; Chrisey, D. B.

    2011-04-01

    We report on thin film deposition of poly(1,3-bis-(p-carboxyphenoxy propane)-co-sebacic anhydride)) 20:80 thin films containing several gentamicin concentrations by matrix assisted pulsed laser evaporation (MAPLE). A pulsed KrF* excimer laser was used to deposit the polymer-drug composite thin films. Release of gentamicin from these MAPLE-deposited polymer conjugate structures was assessed. Fourier transform infrared spectroscopy was used to demonstrate that the functional groups of the MAPLE-transferred materials were not changed by the deposition process nor were new functional groups formed. Scanning electron microscopy confirmed that MAPLE may be used to fabricate thin films of good morphological quality. The activity of gentamicin-doped films against Escherichia coli and Staphylococcus aureus bacteria was demonstrated using disk diffusion and antibacterial drop test. Our studies indicate that deposition of polymer-drug composite thin films prepared by MAPLE is a suitable technique for performing controlled drug delivery. Antimicrobial thin film coatings have several medical applications, including use for indwelling catheters and implanted medical devices.

  1. Uptake and phytotoxicity of the herbicide metsulfuron methyl in corn root tissue in the presence of the safener 1,8-naphthalic anhydride. [Zea mays L

    SciTech Connect

    Milhomme, H.; Bastide, J. )

    1990-06-01

    Growth of Zea mays L. cv Potro roots was inhibited by the herbicide metsulfuron methyl (MSM) at the lowest concentration tested: 5 nanomoles per liter. Pretreatment of corn seeds with commercial 1,8-naphthalic anhydride (NA) at 1% (w/w) partially reversed MSM-induced root growth inhibition. MSM at a concentration of 52 nanomoles per liter was taken up rapidly by roots and accumulated in the corn tissue to concentrations three times those in the external medium; the safener NA increased MSM uptake up to 48 hours. The protective effect of NA was related to the ability of the safener to increase the metabolism of MSM; ten-fold increases in the metabolic rates of MSM were observed in NA-pretreated corn seedlings grown for 48 hours on 52 nanomolar ({sup 14}C)MSM solution. DNA synthesis determined by measurement of ({sup 3}H)thymidine incorporation into DNA was inhibited by root MSM applications; after a 6-hour application period, 13 nanomolar MSM solution reduced DNA synthesis by 64%, and the same reduction was also observed with NA-treated seedlings. Pretreatment of corn seeds with safener NA did not increase the acetolactate synthase activity in the roots and did not change, up to 13 micromoles per liter, the in vitro sensitivity of roots to MSM.

  2. Inactivation of arginine esterase E-I of Bitis gabonica venom by irreversible inhibitors including a water-soluble carbodiimide, a chloromethyl ketone and isatoic anhydride.

    PubMed

    Gravett, P S; Viljoen, C C; Oosthuizen, M M

    1991-01-01

    1. Esterase E-I from Bitis gabonica was inactivated with irreversible inhibitors which included studies with a water-soluble carbodiimide, an affinity labelling peptide and a mechanism-based inactivator. 2. The reaction with 1-ethyl-3(3-dimethylaminopropyl)-carbodiimide was biphasic and the dominant part followed saturation kinetics. At pH 5.5 a rate constant of 0.4 min-1 for inactive enzyme formation was calculated and a dissociation constant (Ki) of 0.2 M for the enzyme-inhibitor complex. 3. Inactivation with D-Phe-Pro-Arg-chloromethyl ketone indicated a two-step mechanism, for which the reaction parameters at pH 8.0 were determined. The Ki value was 0.2 microM and the inactivation rate was 2.5 min-1. 4. With isatoic anhydride pseudo-first-order kinetics was observed. At pH 8.0 a rate constant of 0.9 min-1 and a Ki of 2.0 mM were obtained. The inactivation of the enzyme was found to be governed by a group in the enzyme showing a pK value of 7.3.

  3. Rheological Analysis of Polymer Interactions and Ageing of Poly(Methylvinylether-Co-Maleic Anhydride)/Poly(Vinyl Alcohol) Binary Networks and Their Effects on Mucoadhesion.

    PubMed

    Andrews, Gavin P; Laverty, Thomas P; Jones, David S

    2015-12-01

    Polymer blends of poly(vinylalcohol, PVA) and poly(methylvinylether-co-maleic anhydride, PMVE/MA) were formulated and their viscoelastic and mucoadhesive properties characterised. The viscoelastic and mucoadhesive properties were dependent on polymer concentration, molecular weight of PVA and PVA:PMVE/MA ratio. Alteration of these properties allowed platforms to be designed to offer defined rheological and mucoadhesive properties, properties that could not be achieved using monopolymeric platforms. A strong correlation was noted between the modulus of the polymeric blends and mucoadhesion. After storage, the polymeric blends underwent rheological structuring (ageing) with an attendant enhancement of mucoadhesion. In certain blends containing the highest molecular weight of PVA (146-186 kDa), storage ultimately resulted in an increase and then a significant decrease in the rheological and mucoadhesive properties, the latter phenomenon being accredited to polymer recrystallisation. Ageing of the rheological and mucoadhesive properties was modelled using an exponential growth model, allowing predictions of the storage period associated with the maxima in viscoelastic and mucoadhesive properties. These observations highlight the possible implications whenever interactive polymeric blends are employed in drug delivery. Caution is therefore urged whenever a formulation strategy based on interactive polymer blends is employed to ensure that ageing is fully understood and mathematically characterised.

  4. Preparation and characterization of poly(methyl methacrylate) and poly(maleic anhydride-co-diallyl phthalate) grafted carbon black through γ-ray irradiation

    NASA Astrophysics Data System (ADS)

    Bo, Yang; Cui, Jiayang; Cai, Yangben; Xu, Shiai

    2016-02-01

    In this study, the grafting polymerization of methyl methacrylate (MMA) monomer and maleic anhydride/diallyl phthalate (MAH/DAP) co-monomer onto the surface of carbon black (CB) were carried out at room temperature and normal pressure by γ-ray irradiation. The surface chemistry of grafted CBs were characterized by infrared spectroscopy (IR), thermo-gravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). The results show that there are some remanent polymers on the surface of modified CBs after extract for 48 h, indicating that poly(methyl methacrylate) (PMMA) and poly(MAH-co-DAP) have been successfully grafted onto the surface of CB without using initiator due to the high energy of γ-ray irradiation. Dynamic light scattering (DLS), scanning electron microscopy (SEM) and transmission electron microscopy (TEM) reveal that the grafted CBs have smaller average aggregate size and better dispersibility than that of CB in absolute ethanol. In addition, it was found that the amount of oxygen groups and the irradiation doses/dose rates have little effect on the grafting degree of CB.

  5. Aluminum–phthalocyanine chloride associated to poly(methyl vinyl ether-co-maleic anhydride) nanoparticles as a new third-generation photosensitizer for anticancer photodynamic therapy

    PubMed Central

    Muehlmann, Luis Alexandre; Ma, Beatriz Chiyin; Longo, João Paulo Figueiró; Almeida Santos, Maria de Fátima Menezes; Azevedo, Ricardo Bentes

    2014-01-01

    Photodynamic therapy is generally considered to be safer than conventional anticancer therapies, and it is effective against different kinds of cancer. However, its clinical application has been significantly limited by the hydrophobicity of photosensitizers. In this work, a system composed of the hydrophobic photosensitizer aluminum–phthalocyanine chloride (AlPc) associated with water dispersible poly(methyl vinyl ether-co-maleic anhydride) nanoparticles is described. AlPc was associated with nanoparticles produced by a method of solvent displacement. This system was analyzed for its physicochemical characteristics, and for its photodynamic activity in vitro in cancerous (murine mammary carcinoma cell lineage 4T1, and human mammary adenocarcinoma cells MCF-7) and noncancerous (murine fibroblast cell lineage NIH/3T3, and human mammary epithelial cell lineage MCF-10A) cell lines. Cell viability and the elicited mechanisms of cell death were evaluated after the application of photodynamic therapy. This system showed improved photophysical and photochemical properties in aqueous media in comparison to the free photosensitizer, and it was effective against cancerous cells in vitro. PMID:24634582

  6. Investigation of the formation of benzoyl peroxide, benzoic anhydride, and other potential aerosol products from gas-phase reactions of benzoylperoxy radicals

    NASA Astrophysics Data System (ADS)

    Strollo, Christen M.; Ziemann, Paul J.

    2016-04-01

    The secondary organic aerosol (SOA) products of the reaction of benzaldehyde with Cl atoms and with OH radicals in air in the absence of NOx were investigated in an environmental chamber in order to better understand the possible role of organic peroxy radical self-reactions in SOA formation. SOA products and authentic standards were analyzed using mass spectrometry and liquid chromatography, and results show that the yields of benzoyl peroxide (C6H5C(O)OO(O)CC6H5) and benzoic anhydride (C6H5C(O)O(O)CC6H5), two potential products from the gas-phase self-reaction of benzoylperoxy radicals (C6H5C(O)OO·), were less than 0.1%. This is in contrast to results of recent studies that have shown that the gas-phase self-reactions of β-nitrooxyperoxy radicals formed from reactions of isoprene with NO3 radicals form dialkyl peroxides that contribute significantly to gas-phase and SOA products. Such reactions have also been proposed to explain the gas-phase formation of extremely low volatility dimers from autooxidation of terpenes. The results obtained here indicate that, at least for benzoylperoxy radicals, the self-reactions form only benzoyloxy radicals. Analyses of SOA composition and volatility were inconclusive, but it appears that the SOA may consist primarily of oligomers formed through heterogeneous/multiphase reactions possibly involving some combination of phenol, benzaldehyde, benzoic acid, and peroxybenzoic acid.

  7. Cross-coupling of diarylborinic acids and anhydrides with arylhalides catalyzed by a phosphite/N-heterocyclic carbene co-supported palladium catalyst system.

    PubMed

    Chen, Xiaofeng; Ke, Haihua; Chen, Yao; Guan, Changwei; Zou, Gang

    2012-09-07

    A highly efficient cross-coupling of diarylborinic acids and anhydrides with aryl chlorides and bromides has been effected by using a palladium catalyst system co-supported by a strong σ-donor N-heterocyclic carbene (NHC), N,N'-bis(2,6-diisopropylphenyl) imidazol-2-ylidene, and a strong π-acceptor phosphite, triphenylphosphite, in tert-BuOH in the present of K(3)PO(4)·3H(2)O. Unsymmetrical biaryls with a variety of functional groups could be obtained in good to excellent yields using as low as 0.01, 0.2-0.5, and 1 mol % palladium loadings for aryl bromides and activated and deactivated aryl chlorides, respectively, under mild conditions. A ligand synergy between the σ-donor NHC and the π-acceptor phosphite in the Pd/NHC/P(OPh)(3) catalytic system has been proposed to be responsible for the high efficacy to arylchlorides in the cross-coupling. A scalable and economical process has therefore been developed for synthesis of Sartan biphenyl from the Pd/NHC/P(OPh)(3) catalyzed cross-coupling of di(4-methylphenyl)borinic acid with 2-chlorobenzonitrile.

  8. Simultaneous efficient adsorption of Pb2+ and MnO4- ions by MCM-41 functionalized with amine and nitrilotriacetic acid anhydride

    NASA Astrophysics Data System (ADS)

    Chen, Feiyun; Hong, Mingzhu; You, Weijie; Li, Chong; Yu, Yan

    2015-12-01

    A novel adsorbent NH2/MCM-41/NTAA, capable of simultaneous adsorption of cations and anions from aqueous solution, was prepared by immobilization of amine and nitrilotriacetic acid anhydride (NTAA) onto MCM-41. The structures and properties before and after surface modification were systematically investigated through X-ray diffraction (XRD), transmission electron microscope (TEM) and scanning electron microscope (SEM), nitrogen adsorption-desorption, and infrared spectroscopy (FTIR), thermogravimetry (TGA) and X-ray photoelectron spectroscopy (XPS). They together confirm that the amine and NTAA group were chemically bonded to the internal surface of the mesoporous. The NH2/MCM-41/NTAA were used to adsorb Pb2+ and MnO4- in an aqueous solution in a batch system, and the maximum adsorption efficiency was found to occur at pH 5.0 and 3.0, respectively. NH2/MCM-41/NTAA exhibit preferable removal of Pb2+ through electrostatic interactions and chelation, whereas it captures MnO4- by means of electrostatic interactions. The experimental data are fitted the Langmuir isotherm model reasonably well, with the maximum adsorption capacity of 147 mg/g for Pb2+ and of 156 mg/g for MnO4-. The adsorption rates of both Pb2+ and MnO4- are found to follow the pseudo-second order kinetics. Furthermore, the NH2/MCM-41/NTAA adsorbent performs good recyclability and reusability for 5 cycles use. This study indicates a potential applicability of NH2/MCM-41/NTAA as new absorbents for effective simultaneous adsorption of hazardous metal ions and anions from wastewater.

  9. Copolymerization and terpolymerization of carbon dioxide/propylene oxide/phthalic anhydride using a (salen)Co(III) complex tethering four quaternary ammonium salts

    PubMed Central

    Jeon, Jong Yeob; Eo, Seong Chan; Varghese, Jobi Kodiyan

    2014-01-01

    Summary The (salen)Co(III) complex 1 tethering four quaternary ammonium salts, which is a highly active catalyst in CO2/epoxide copolymerizations, shows high activity for propylene oxide/phthalic anhydride (PO/PA) copolymerizations and PO/CO2/PA terpolymerizations. In the PO/PA copolymerizations, full conversion of PA was achieved within 5 h, and strictly alternating copolymers of poly(1,2-propylene phthalate)s were afforded without any formation of ether linkages. In the PO/CO2/PA terpolymerizations, full conversion of PA was also achieved within 4 h. The resulting polymers were gradient poly(1,2-propylene carbonate-co-phthalate)s because of the drift in the PA concentration during the terpolymerization. Both polymerizations showed immortal polymerization character; therefore, the molecular weights were determined by the activity (g/mol-1) and the number of chain-growing sites per 1 [anions in 1 (5) + water (present as impurity) + ethanol (deliberately fed)], and the molecular weight distributions were narrow (M w/M n, 1.05–1.5). Because of the extremely high activity of 1, high-molecular-weight polymers were generated (M n up to 170,000 and 350,000 for the PO/PA copolymerization and PO/CO2/PA terpolymerization, respectively). The terpolymers bearing a substantial number of PA units (f PA, 0.23) showed a higher glass-transition temperature (48 °C) than the CO2/PO alternating copolymer (40 °C). PMID:25161738

  10. Synthesis, characterisation, and evaluation of a cross-linked disulphide amide-anhydride-containing polymer based on cysteine for colonic drug delivery.

    PubMed

    Lim, Vuanghao; Peh, Kok Khiang; Sahudin, Shariza

    2013-12-18

    The use of disulphide polymers, a low redox potential responsive delivery, is one strategy for targeting drugs to the colon so that they are specifically released there. The objective of this study was to synthesise a new cross-linked disulphide-containing polymer based on the amino acid cysteine as a colon drug delivery system and to evaluate the efficiency of the polymers for colon targeted drug delivery under the condition of a low redox potential. The disulphide cross-linked polymers were synthesised via air oxidation of 1,2-ethanedithiol and 3-mercapto-N-2-(3-mercaptopropionamide)-3-mercapto propionic anhydride (trithiol monomers) using different ratio combinations. Four types of polymers were synthesised: P10, P11, P151, and P15. All compounds synthesised were characterised by NMR, IR, LC-MS, CHNS analysis, Raman spectrometry, SEM-EDX, and elemental mapping. The synthesised polymers were evaluated in chemical reduction studies that were performed in zinc/acetic acid solution. The suitability of each polymer for use in colon-targeted drug delivery was investigated in vitro using simulated conditions. Chemical reduction studies showed that all polymers were reduced after 0.5-1.0 h, but different polymers had different thiol concentrations. The bacterial degradation studies showed that the polymers were biodegraded in the anaerobic colonic bacterial medium. Degradation was most pronounced for polymer P15. This result complements the general consensus that biodegradability depends on the swellability of polymers in an aqueous environment. Overall, these results suggest that the cross-linked disulphide-containing polymers described herein could be used as coatings for drugs delivered to the colon.

  11. Vibrationally-resolved spectroscopic studies of electronically excited states of 1,8-naphthalic anhydride and 1,8-naphthalimide: a delicate interplay between one ππ* and two nπ* states.

    PubMed

    Maltseva, Elena; Amirjalayer, Saeed; Buma, Wybren Jan

    2017-02-22

    The spectroscopic and dynamic properties of the lower electronically excited states of 1,8-naphthalic anhydride and 1,8-naphthalimide have been studied in supersonically cooled molecular beams using nanosecond Resonance Enhanced MultiPhoton Ionization (REMPI) spectroscopic techniques in combination with quantum chemical calculations. The excitation spectra of these compounds show near - and even below - the apparent 0-0 transition to a strongly allowed electronic state, previously assigned as the S1(2(1)A1(ππ*)) state, a plethora of vibronic transitions that cannot simply be rationalized in terms of the Franck-Condon vibronic activity of that particular state. Instead, it is shown that the (1)B1(nπ*) state, which was previously reported to be S3 for vertical excitation, is adiabatically the lowest excited singlet state. Interactions between this 'dark' state and the 'bright' 2(1)A1(ππ*) state lead to intensity borrowing of transitions to 'dark' state levels that thus show up in the excitation spectra. A complicating factor is that, apart from the coupling of these two singlet states, a relatively strong spin-orbit coupling between the 2(1)A1(ππ*) and (3)B1(nπ*) states is also present. We show that the latter state has a slightly higher adiabatic excitation energy than the former state in 1,8-naphthalic anhydride but lies energetically below the 2(1)A1(ππ*) state in 1,8-naphthalimide. Concurrently, we find that the decay dynamics of the excited states of 1,8-naphthalimide are entirely dominated by intersystem crossing, while in 1,8-naphthalic anhydride both internal conversion to the ground state and intersystem crossing occur, albeit the former loses importance once the excitation energy exceeds that of the (3)B1(nπ*) state.

  12. A convenient synthesis of 1,1-disubstituted 1,2,3,4-tetrahydroisoquinolines via Pictet-Spengler reaction using titanium(IV) isopropoxide and acetic-formic anhydride.

    PubMed

    Horiguchi, Yoshie; Kodama, Hirokazu; Nakamura, Masayoshi; Yoshimura, Tsuyoshi; Hanezi, Kaori; Hamada, Hiroko; Saitoh, Toshiaki; Sano, Takehiro

    2002-02-01

    A synthesis of 1,1-disubstituted 1,2,3,4-tetrahydroisoquinolines (6) was achieved in a highly efficient manner via Pictet-Spengler reaction of arylethylamines (1) and acyclic and cyclic ketones (2) using titanium (IV) isopropoxide and acetic-formic anhydride. The cyclization of the in situ formed acyliminium ion (4) to N-formyl 1,2,3,4-tetrahydroisoquinoline (5) was greatly facilitated by using trifluoroacetic acid as an additional reagent. The Pictet-Spengler reaction was carried out by one pot procedure, providing a convenient and effective method for preparing various 1,2,3,4-tetrahydroisoquinolines.

  13. beta-2,2-Amino Acid N-Carboxy Anhydrides Relying on Sequential Enantioselective C(4)-Functionalization of Pyrrolidin-2,3-diones and Regioselective Baeyer-Villiger Oxidation.

    PubMed

    Palomo, Claudio; Mielgo, Antonia; Olaizola, Iurre; Vázquez, Ana; Badiola, Eider; Vera, Silvia

    2017-02-28

    A catalytic enantioselective entry to beta-2,2-amino acids enabling their direct coupling with nucleophiles is described. The approach is based upon an effective bifunctional Brønsted base catalyzed construction of a quaternary carbon stereocenter at C4 position of pyrrolidin-2,3-diones. Subsequent regioselective Baeyer-Villiger oxidation of the resultant adducts gives beta-2,2-amino acid N-carboxy anhydrides as the reactive species, which can further react with nucleophiles. Following this strategy both, 2,2-amino acid derivatives with different functionalities at the newly created stereocenter, and spirocyclic structures can be efficiently prepared.

  14. [2 + 2] Cycloadditions of fullerenes. Synthesis and characterization of C{sub 62}O{sub 3} and C{sub 72}O{sub 3}, the first fullerene anhydrides

    SciTech Connect

    Zhang, X.; Foote, C.S.

    1995-04-19

    [2 + 2] Cycloaddition of C{sub 60} with N,N,N{prime},N{prime}-tetraethylethynediamine (1a) and N,N-diethyl-2-ethylthioethyneamine (1b) gave the stable, 1,2-dihydrofullerene[60]-1,2-cyclobutenediamine 2a and thioenamine 2b, respectively, in good yield. Self-sensitized photooxygenation of 2a and 2b produced 1,2-dihydrofullerene[60]-1,2-diamide 3a and thioester amide 3b, from which 1,2-dihydrofullerene[60]-1,2-dicarboxylic acid anhydride (C{sub 62}O{sub 3}) was readily prepared. Similarly, C{sub 70} reacted with 1a (regiospecifically at the 1,9-bond) to give 1,9-dihydrofullerene[70]-1,9-cyclobutenediamine 5 or 1,9:61,62-biscyclobutenediamine 6 in good yields. In contrast to 2a, self-sensitized photooxygenation of 5 regenerated C{sub 70} and the oxidized ynamine. 1,9-Dihydrofullerene[70]-1,9-dicarboxylic acid anhydride (C{sub 72}O{sub 3}) was prepared from a tert-butylthioester amide 10 in one pot by reaction of N,N-diethyl-2-tert-butylthioethyneamine (1c) with C{sub 70} and photooxygenation of the resultant cycloadduct. 52 refs.

  15. Application of gas-liquid chromatography and high-performance liquid chromatography to the analysis of trace amounts of salicylic acid, acetylsalicylic anhydride and acetylsalicylsalicylic acid in aspirin samples and aspirin formulations.

    PubMed

    Ali, S L

    1976-11-03

    The gas-liquid chromatographic (GLC) determination of salicylic acid (SA) in 12 commercial acetylsalicylic acid (aspirin, ASA) samples and 12 ASA formulations is reported. The GLC determination of SA as an impurity in ASA, utilising methylation with methyl iodide in the presence of potassium carbonate, requires a column chromatographic separation of SA prior to derivatization. Trace amounts of SA in ASA have also been determined by high-performance liquid chromatography (HPLC) on a Sil-X-I adsorption column using light petroleum-ethyl acetate-acetic acid as the mobile phase. Acetylsalicylic anhydride (ASN) and acetylsalicylsalicylic acid (ASSA) were determined by HPLC on a reversed-phase C18 column with water-methanol mixtures as the mobile phase. GLC was also applied to the determination of ASN as an impurity in ASA formulations.

  16. Theoretical problems associated with the use of acetic anhydride as a co-solvent for the non-aqueous titration of hydrohalides of organic bases and quaternary ammonium salts.

    PubMed

    Völgyi, Gergely; Béni, Szabolcs; Takács-Novák, Krisztina; Görög, Sándor

    2010-01-05

    A potentiometric titration study of organic base hydrohalides and quaternary ammonium salts using perchloric acid as the titrant and a mixture of acetic anhydride and acetic acid as the solvent was carried out and the titration mixture was analysed by NMR in order to clarify the chemistry of the reactions involved. It was found that in contrast to the general belief the formation of acetyl halides and titratable free acetate ion does not take place prior to the titration but NMR spectra proved the formation of acetyl halides in the course of the titration. This observation and the fact that the shape of the titration curves depends on the nature of the hydrohaloic acid bound to the base or of the anion in the quaternary ammonium salts led to the conclusion that the titrating agent is acetyl perchlorate formed in situ during the titration. Equations of the reactions involved in the titration process are shown in the paper.

  17. A preliminary study on the dynamic-mechanical behaviour of compression moulded polypropylene/carbon fiber composites interfacially modified by a succinic anhydride grafted atactic polypropylene from polymer wastes

    NASA Astrophysics Data System (ADS)

    García-Martínez, Jesús María; Areso, Susana; Collar, Emilia P.

    2016-05-01

    Present communication is devoted to the study of the effect of a novel interfacial agent in polypropylene/carbon fibre composites. The interfacial agent used is a succinic anhydride grafted atactic polypropylene containing both succinic bridges and side grafts (aPP-SASA) and with 5.6% (5.6.10-4g/mol) of grafting content obtained at the GIP labs. The study considers the study dynamic-mechanical behaviour with temperature at a frequency of 1 hz to ascertain the differences in the interfacial activity. The samples were compression molded in order to isolate as far as possible the effect of the solely aPP-SASA in absence of those synergetic effects due to the preferential orientation of the fibres.

  18. Modelling Biological Clocks with Bio-PEPA: Stochasticity and Robustness for the Neurospora crassa Circadian Network

    NASA Astrophysics Data System (ADS)

    Akman, Ozgur E.; Ciocchetta, Federica; Degasperi, Andrea; Guerriero, Maria Luisa

    Circadian clocks are biochemical networks, present in nearly all living organisms, whose function is to regulate the expression of specific mRNAs and proteins to synchronise rhythms of metabolism, physiology and behaviour to the 24 hour day/night cycle. Because of their experimental tractability and biological significance, circadian clocks have been the subject of a number of computational modelling studies.

  19. Study on thermal properties and crystallization behavior of electron beam irradiated ethylene vinyl acetate (EVA)/waste tyre dust (WTD) blends in the presence of polyethylene graft maleic anhydride (PEgMAH)

    SciTech Connect

    Ramli, Syuhada; Ahmad, S. H.; Ratnam, C. T.; Athirah, Nurul

    2013-11-27

    The aim of this article is to show the effects of the electron beam irradiation dose and presence of a compatibiliser on the thermal properties and crystallinity of EVA/WTD blends. The purpose of applying electron beam radiation with doses range 50 to 200 kGy and adding a compatibiliser was to enhance the compatibility of the studied blends and at the same time to investigate the possibility of using this technique in the process of recycling polymeric materials. As the compatibilisers, the polyethylene grafted maleic anhydride (PEgMAH) was utilized, they were added at the amounts of 1-5 phr respectively. The enhancement of thermal properties was accompanied by the following effects, discussed in this article: i) an irradiated EVA/WTD blend at 200kGy was found to improve the thermal properties of EVA, ii) the addition of PEgMAH in EVA/WTD blends and the subsequent irradiation allowed prevention of degradation mechanism. iii) the ΔH{sub f} and crystallinity percentage decrease at higher PEgMAH content.

  20. Study on thermal properties and crystallization behavior of electron beam irradiated ethylene vinyl acetate (EVA)/waste tyre dust (WTD) blends in the presence of polyethylene graft maleic anhydride (PEgMAH)

    NASA Astrophysics Data System (ADS)

    Ramli, Syuhada; Ratnam, C. T.; Ahmad, S. H.; Athirah, Nurul

    2013-11-01

    The aim of this article is to show the effects of the electron beam irradiation dose and presence of a compatibiliser on the thermal properties and crystallinity of EVA/WTD blends. The purpose of applying electron beam radiation with doses range 50 to 200 kGy and adding a compatibiliser was to enhance the compatibility of the studied blends and at the same time to investigate the possibility of using this technique in the process of recycling polymeric materials. As the compatibilisers, the polyethylene grafted maleic anhydride (PEgMAH) was utilized, they were added at the amounts of 1-5 phr respectively. The enhancement of thermal properties was accompanied by the following effects, discussed in this article: i) an irradiated EVA/WTD blend at 200kGy was found to improve the thermal properties of EVA, ii) the addition of PEgMAH in EVA/WTD blends and the subsequent irradiation allowed prevention of degradation mechanism. iii) the ΔHf and crystallinity percentage decrease at higher PEgMAH content.

  1. Anionic chlorido(triphenyl)tin(IV) bearing N-phthaloylglycinato or 1,2,4-benzenetricarboxylato 1,2-anhydride ligands: potential cytotoxic and apoptosis-inducing agents against several types of cancer.

    PubMed

    Hübner, Denise; Kaluđerović, Milena R; Gómez-Ruiz, Santiago; Kaluđerović, Goran N

    2017-04-01

    Two ionic triphenyltin(IV) chloride carboxylate compounds of the formula [NHEt3 ][Ph3 SnCl(L)] [LH = N-phthaloylglycine (P-GlyH), 1; 1,2,4-benzenetricarboxylic 1,2-anhydride (BTCH), 2] were tested for the in vitro activity against 518A2 (melanoma), FaDu (head and neck carcinoma), HT-29 (colon cancer), MCF-7 (breast carcinoma), and SW1736 (thyroid cancer) cell lines. The ammonium salts of the carboxylic acids are found to be not active, while anionic [Ph3 SnCl(L)](-) exhibited high cytotoxicity in nM range, both higher activity and selectivity than cisplatin. Compounds 1 and 2 are inducing apoptosis, which was proved with the morphological and biochemical features such as membrane blebbing, translocation of phosphatidylserine, and DNA fragmentation. Thus, accumulation of cells in sub-G1 phase is observed. Both anionic organotin(IV) compounds showed potent cytotoxic and apoptotic properties against five cancer cell lines of various histogenetic origin.

  2. Disproportionation of bromous acid HOBrO by direct O-transfer and via anhydrides O(BrO)2 and BrO-BrO2. An ab initio study of the mechanism of a key step of the Belousov-Zhabotinsky oscillating reaction.

    PubMed

    Glaser, Rainer; Jost, Mary

    2012-08-16

    The results are reported of an ab initio study of the thermochemistry and of the kinetics of the HOBrO disproportionation reaction 2HOBrO (2) ⇄ HOBr (1) + HBrO(3) (3), reaction ( R4' ), in gas phase (MP2(full)/6-311G*) and aqueous solution (SMD(MP2(full)/6-311G*)). The reaction energy of bromous acid disproportionation is discussed in the context of the coupled reaction system R2-R4 of the FKN mechanism of the Belousov-Zhabotinsky reaction and considering the acidities of HBr and HOBrO(2). The structures were determined of ten dimeric aggregates 4 of bromous acid, (HOBrO)(2), of eight mixed aggregates 5 formed between the products of disproportionation, (HOBr)(HOBrO(2)), and of four transition states structures 6 for disproportionation by direct O-transfer. It was found that the condensation of two HOBrO molecules provides facile access to bromous acid anhydride 7, O(BrO)(2). A discussion of the potential energy surface of Br(2)O(3) shows that O(BrO)(2) is prone to isomerization to the mixed anhydride 8, BrO-BrO(2), and to dissociation to 9, BrO, and 10, BrO(2), and their radical pair 11. Hence, three possible paths from O(BrO)(2) to the products of disproportionation, HOBr and HOBrO(2), are discussed: (1) hydrolysis of O(BrO)(2) along a path that differs from its formation, (2) isomerization of O(BrO)(2) to BrO-BrO(2) followed by hydrolysis, and (3) O(BrO)(2) dissociation to BrO and BrO(2) and their reactions with water. The results of the potential energy surface analysis show that the rate-limiting step in the disproportionation of HOBrO consists of the formation of the hydrate 12a of bromous acid anhydride 7 via transition state structure 14a. The computed activation free enthalpy ΔG(act)(SMD) = 13.6 kcal/mol for the process 2·2a → [14a](‡) → 12a corresponds to the reaction rate constant k(4) = 667.5 M(-1) s(-1) and is in very good agreement with experimental measurements. The potential energy surface analysis further shows that anhydride 7 is

  3. Hydrogen bonding in cyclic imides and amide carboxylic acid derivatives from the facile reaction of cis-cyclohexane-1,2-carboxylic anhydride with o- and p-anisidine and m- and p-aminobenzoic acids.

    PubMed

    Smith, Graham; Wermuth, Urs D

    2012-09-01

    The structures of the open-chain amide carboxylic acid rac-cis-2-[(2-methoxyphenyl)carbamoyl]cyclohexane-1-carboxylic acid, C(15)H(19)NO(4), (I), and the cyclic imides rac-cis-2-(4-methoxyphenyl)-3a,4,5,6,7,7a-hexahydroisoindole-1,3-dione, C(15)H(17)NO(3), (II), chiral cis-3-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)benzoic acid, C(15)H(15)NO(4), (III), and rac-cis-4-(1,3-dioxo-3a,4,5,6,7,7a-hexahydroisoindol-2-yl)benzoic acid monohydrate, C(15)H(15)NO(4)·H(2)O, (IV), are reported. In the amide acid (I), the phenylcarbamoyl group is essentially planar [maximum deviation from the least-squares plane = 0.060 (1) Å for the amide O atom] and the molecules form discrete centrosymmetric dimers through intermolecular cyclic carboxy-carboxy O-H···O hydrogen-bonding interactions [graph-set notation R(2)(2)(8)]. The cyclic imides (II)-(IV) are conformationally similar, with comparable benzene ring rotations about the imide N-C(ar) bond [dihedral angles between the benzene and isoindole rings = 51.55 (7)° in (II), 59.22 (12)° in (III) and 51.99 (14)° in (IV)]. Unlike (II), in which only weak intermolecular C-H···O(imide) hydrogen bonding is present, the crystal packing of imides (III) and (IV) shows strong intermolecular carboxylic acid O-H···O hydrogen-bonding associations. With (III), these involve imide O-atom acceptors, giving one-dimensional zigzag chains [graph-set C(9)], while with the monohydrate (IV), the hydrogen bond involves the partially disordered water molecule which also bridges molecules through both imide and carboxy O-atom acceptors in a cyclic R(4)(4)(12) association, giving a two-dimensional sheet structure. The structures reported here expand the structural database for compounds of this series formed from the facile reaction of cis-cyclohexane-1,2-dicarboxylic anhydride with substituted anilines, in which there is a much larger incidence of cyclic imides compared to amide carboxylic acids.

  4. Bis(phenyl-phospho-nic) anhydride.

    PubMed

    Li, Yang; Hua, Guoxiong; Slawin, Alexandra M Z; Woollins, J Derek

    2009-10-03

    The asymmetric unit of the title compound, C(12)H(12)O(5)P(2), contains four independent mol-ecules, generating two dimers via pairs of inter-molecular O-H⋯O hydrogen bonds, forming R(2) (2)(8) rings. The two aryl rings of each mol-ecule form dihedral angles of 108.6 (1), 103.2 (1), 12.5 (2) and 8.1 (2)° in the four mol-ecules.

  5. Critical behavior of anhydride cured epoxies

    NASA Astrophysics Data System (ADS)

    Trappe, V.; Richtering, W.; Burchard, W.

    1992-07-01

    Critical behavior was studied with a crosslinking system obtained by living anionic polymerization, where the primary chain length was kept constant and the crosslinking density was varied. Gelation was found at a critical ratio of crosslinker per chain X_c=0.884± 0.004. Different samples from the pre gel region were studied by dynamic and static light scattering in dilute solution and oscillatory rheology in melt. The exponents γ = 1.75± 0.38 and ν = 0.98± 0.19, determined from M_w and R_g dependence on (X_c-X), are in accordance with three dimensional percolation theory. The distribution of diffusion coefficients obtained by inverse Laplace transformation of the time correlation function shows power law behavior in a limited interval, from which an exponent tau = 2.17± 0.03 is derived. Rheological measurements show a systematic change of G^{prime}(ω) and G''(ω) from typical liquid to the critical gel behavior, where tan δ = G''(ω)/G^{prime}(ω) becomes frequency independent.

  6. DIMETHYLITHIOARSINIC ANHYDRIDE: A STANDARD FOR ARSENIC SPECIATION

    EPA Science Inventory

    Recently, sulfar analogs of well know arsenicals have been identfied in biolgical, dietary and environmental matrices. These discoveries have generated a need for stable species-specific standards. This presentation will forcus on the isolation and characterization of a standar...

  7. DIMETHYLTHIOARSINIC ANHYDRIDE: A STANDARD FOR ARSENIC SPECIATION

    EPA Science Inventory

    Dimethylthioarsinic acid (DMTAV) has recently been identified in biological, dietary and environmental matrices. The relevance of this compound to the toxicity of arsenic in humans is unknown and further exposure assessment and metabolic studies are difficult to conduct because ...

  8. Curing chemistry of phenylethynyl-terminated imide oligomers: Model compounds, carbon-13 labeling and cure analysis

    NASA Astrophysics Data System (ADS)

    Roberts, Christopher Chad

    1998-11-01

    Phenylethynyl-terminated imide oligomers (PETI) are currently considered the state-of-the-art high performance resins for aerospace applications. The processing of these resins is more facile because of their low molecular weight, but PETI's cure to form a tough, solvent-resistant material. However, the final cure structure was a complete mystery. Hence, the present study was set forth with three essential goals. The determination of the final structure of the crosslinked polymer is of obvious importance. Second, the crosslinking mechanism and controlling factors is also of interest. Lastly, the final structure of the crosslinked polymers was correlated with mechanical and thermal properties, thereby helping to establish the structure-processing-properties relationships for PETI resins. These goals were accomplished by using a combination of synthesis of model compounds synthesis and proposed cure products, sp{13}C labeling of the ethynyl endgroup in PETI's, monitoring of the thermal cure using solid state sp{13}C NMR and ESR and molecular modeling techniques. Phenylethynyl endcapping agents, 4-(phenylethynyl)phthalic anhydride (PEPA) and 3-(phenylethynyl)aniline (3PEA), were synthesized via the palladium-catalyzed coupling of phenylacetylene with 4-bromophthalic anhydride or 3-iodonitrobenzene followed by reduction to 3PEA, respectively. Isolated yields of 41 and 86% for 3PEA and PEPA were obtained, respectively. Model compounds were synthesized from 3PEA and PEPA by reacting with them the appropriate aniline or phthalic anhydride derivative. Model compounds included N-pentafluorophenyl-4-(phenylethynyl)phthalimide (PEPA/F5An), N-(4-trifluoromethyl-phenyl)4-(phenylethynyl)phthalimide (PEPA/F3CAn), N-lbrack 3-(phenylethynyl)phenylrbrack\\ phthalimide (3PEA/PA), N-phenyl-4-(phenylethynyl)phthalimide (PEPA/An), N-(4-phenoxyphenyl)4-(phenylethynyl)phthalimide (PEPA/POAn), and N-(1-naphthyl)-4-(phenylethynyl)phthalimide (PEPA/Anaph). Proposed cure products such as

  9. High Temperature VARTM with LaRC Polyimides

    NASA Technical Reports Server (NTRS)

    Cano, Roberto J.; Grimsley, Brian W.; Jensen, Brian J.; Kellen, Charles B.

    2004-01-01

    Recent work at NASA Langley Research Center (LaRC) has concentrated on developing new polyimide resin systems for advanced aerospace applications that can be processed without the use of an autoclave. Polyimide composites are very attractive for applications that require a high strength to weight ratio and thermal stability. Vacuum assisted resin transfer molding (VARTM) has shown potential to reduce the manufacturing cost of composite structures. In VARTM, the fibrous preform is infiltrated on a rigid tool surface contained beneath a flexible vacuum bag. Both resin injection and fiber compaction are achieved under pressures of 101.3 KPa or less. Recent studies have demonstrated the feasibility of the VARTM process for fabrication of void free structures utilizing epoxy resin systems with fiber volume fractions approaching 60%. In this work, the VARTM process has been extended to the fabrication of composite panels from polyimide systems developed at the Langley Research Center. This work has focused on processing LARC(trademark) PETI-8 (Langley Research Center Phenylethynyl Terminated Imide- 8), an aromatic polyimide based on 3,3',4,4' -biphenyltetracarboxylic dianhydride, a 50:50 molar ratio of 3,4'-oxydianiline and 1,3-bis(3-aminophenoxy)benzene, with 4-phenylethynylphthalic anhydride as the endcapping agent. Various molecular weight versions were investigated to determine their feasibility of being processed by VARTM at elevated temperatures. An injection temperature of approximately 280 C was required to achieve the necessary viscosity (<5 Poise) for flow at VARTM pressures. Laminate quality and initial mechanical properties are presented for LARC(trademark) PETI-8 and 6k IM7 uniweave fabric.

  10. Method to Prepare Processable Polymides with Reactive Endgroups using 1,3-Bis (3-Aminophenoxy) Benzene

    NASA Technical Reports Server (NTRS)

    Jensen, Brian J. (Inventor)

    2000-01-01

    Polyimide copolymers were obtained containing 1,3-bis(3-aminophenoxy)benzene (APB) and other diamines and dianhydrides and terminating with the appropriate amount of reactive endcapper. The reactive endcappers studied include but should not be limited to 4-phenylethynyl phthalic anhydride (PEPA ), 3-aminophenoxy- 4'-phenylethynylbenzophenone (3-APEB), maleic anhydride (MA) and nadic anhydride (5-norbomene-2,3-dicarboxylic anhydride, NA). Homopolymers containing only other diamines and dianhydrides which are not processable under conditions described previously can be made processable by incorporating various amounts of APB, depending on the chemical structures of the diamines and dianhydrides used. By simply changing the ratio of APB to the other diamine in the polyimide backbone, a material with a unique combination of solubility, Tg, Tm, melt viscosity, toughness and elevated temperature mechanical properties can be prepared. The copolymers that result from using APB to enhance processability have a unique combination of properties that include low pressure processing (200 psi and below), long term melt stability (several hours at 300 C. for the phenylethynyl terminated polymers), high toughness, improved solvent resistance, improved adhesive properties, and improved composite mechanical properties. These copolyimides are eminently suitable as adhesives, composite matrices, moldings, films and coatings.

  11. A new approach to reducing the flammability of layered double hydroxide (LDH)-based polymer composites: preparation and characterization of dye structure-intercalated LDH and its effect on the flammability of polypropylene-grafted maleic anhydride/d-LDH composites.

    PubMed

    Kang, Nian-Jun; Wang, De-Yi; Kutlu, Burak; Zhao, Peng-Cheng; Leuteritz, Andreas; Wagenknecht, Udo; Heinrich, Gert

    2013-09-25

    Dye structure-intercalated layered double hydroxide (d-LDH) was synthesized using a one-step method, and its intercalated behaviors have been characterized by Fourier transform infrared spectroscopy (FTIR), wide angle X-ray scattering (WAXS), scanning electron microscopy, thermogravimetric analysis (TGA), etc. As a novel functional potential fire-retarding nanofiller, it was used to prepare a polypropylene-grafted maleic anhydride (PP-g-MA)/d-LDH composite by refluxing the mixture of d-LDH and PP-g-MA in xylene, aiming to investigate its effect on the flammability of the PP-g-MA composite. The morphological properties, thermal stability, and flame retardant properties of the PP-g-MA/d-LDH composite were determined by FTIR, WAXS, transmission electron microscopy, TGA, and microscale combustion calorimetry. Compared with NO3-LDH (unmodified LDH) and LDH intercalated by sodium dodecylbenzenesulfonate (conventional organo-modified LDH), d-LDH can significantly decrease the heat release rate and the total heat release of the PP-g-MA composite, offering a new approach to imparting low flammability to LDH-based polymer composites.

  12. Polyimide Composites Based on Asymmetric Dianhydrides (a-ODPA vs a-BPDA)

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Criss, Jim M., Jr.; Mintz, Eric A.

    2009-01-01

    Two series of low-melt viscosity imide resins (2-15 poise at 260-280 C) were formulated from either asymmetric oxydiphthalic anhydride (a-ODPA) or asymmetric biphenyl dianhydride (a- BPDA) with 4-phenylethynyl endcap (PEPA), along with 3,4'-oxydianiline, 3,4 - methylenedianiline, 3,3 -methylenedianiline or 3,3 -diaminobenzophenone, using a solvent-free melt process. These low-melt viscosity imide resins were fabricated into polyimide/T650-35 carbon fabric composites by resin transfer molding (RTM). Composites from a-ODPA based resins display better open-hole compression strength and short beam shear strength from room temperature to 288 C than that of the corresponding a-BPDA based resins. However, due to the lower Tg s of a-ODPA based resins (265-330 C), their corresponding composites do not possess 315 C use capability while the a-BPDA based composites do. In essence, RTM 370 (T g = 370 C), derived from a-BPDA and 3,4 -ODA and PEPA, exhibits the best overall property performance at 315 C (600 F).

  13. Reactive extrusion of zein with glyoxal and polyethylene maleic anhydride

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In order for zein, a potentially significant co-product of the bio-ethanol industry, to be used in new markets, improved zein based products are needed. These products need to be produced by the most economical means possible. In the traditional plastics industry, extrusion techniques are the most e...

  14. PLA branching with anhydrides and tri-functional aziridine

    NASA Astrophysics Data System (ADS)

    Gu, Liangliang; Xu, Yuewen; Naredla, Rajasekhar; Hoye, Thomas; Macosko, Christopher

    Branched PLA was prepared by melt blending with tri-functional aziridine (T-Az) and pyromellitic dianhydride (PMDA). 1HNMR, gel permeation chromatography (GPC) and rheology were used to characterize the topological structures of branched PLA. Fast reaction between PLA carboxyl end group and T-Az resulted in 3-arm stars and increased the molecular weight. However, the 3-arm stars did not show strain hardening behavior under extensional flow. After modifying PLA hydroxyl end group with PMDA, PLA can react with T-Az on both chain ends and form long chain branched structure, which showed strain hardening in extension. It was found that that only 10% of the PLA hydroxyl end groups reacted with PMDA. This work is supported by Center for Sustainable Polymers.

  15. Aminoacyl transfer from an adenylate anhydride to polyribonucleotides

    NASA Technical Reports Server (NTRS)

    Weber, A. L.; Lacey, J. C., Jr.

    1975-01-01

    Imidazole catalysis of phenylalanyl transfer from phenylalanine adenylate to hydroxyl groups of homopolyribonucleotides is studied as a possible chemical model of biochemical aminoacylation of transfer RNA (tRNA). The effect of pH on imidazole-catalyzed transfer of phenylalanyl residues to poly(U) and poly(A) double helix strands, the number of peptide linkages and their lability to base and neutral hydroxylamine, and the nature of adenylate condensation products are investigated. The chemical model entertained exhibits a constraint by not acylating the hydroxyl groups of polyribonucleotides in a double helix. The constraint is consistent with selective biochemical aminoacylation at the tRNA terminus. Interest in imidazole as a model of histidine residue in protoenzymes participating in prebiotic aminoacyl transfer to polyribonucleotides, and in rendering the tRNA a more efficient adaptor, is indicated.

  16. IM7/LARC(tm) MPEI-1 Polymide Composites

    NASA Technical Reports Server (NTRS)

    Hou, T. H.; Cano, R. J.; Jensen, B. J.

    1998-01-01

    LARC(Trademark) MPEI-1 (Langley Research Center(Trademark) modified phenylethynyl imide-1) phenylethynyl containing aromatic polymide, is based on the reaction of biphenyl dianhydride (BPDA), 3,4'-oxydianiline (3,4'-ODA), 1,3-bis(3-aminophenoxy)benzene (APB), 2,4,6-triaminopyrimidine (TAP) and 4-phenylethynyl phthalic anhydride (PEPA), presumably resulting in a mixture of linear, branched and star shaped phenylethynyl containing imides which was evaluated as a matrix for high-performance composites. The poly(amid acid) solution of MPEI-1 in N-methypyrrolidinone was synthesized at 35% and 42% solids. Unidirectional prepreg was fabricated from these solutions and Hercules IM7 carbon fiber utilizing NASA- Langley's multipurpose prepreg machine. The temperature-dependent volatile depletion rates, thermal crystallization behavior and resin theology were characterized. Based on this information, a composite molding cycle was developed which yielded well consolidated, void-free laminates. Composite mechanical properties such as short beam shear strength, longitudinal and transverse flexural strength and flexural modulus, longitudinal tensile strength and notched and unnotched compression strengths were measured at room temperature (RT) and elevated temperatures. These mechanical properties are compared with those of IM7/LARC(Trademark) PETI-5 composites.

  17. Evaluation of poly(styrene-alt-maleic anhydride)-ethanol as enteric coating material.

    PubMed

    Lai, Xiaolin; Sun, Chengdong; Tian, Hua; Zhao, Wenjun; Gao, Lin

    2008-03-20

    This study aims at evaluating the potential of SMA-ethanol as enteric coating polymer for erythromycin tablets. SMA-ethanol was synthesized and characterized for physicochemical properties, molecular weight and thermal analysis. Free films were prepared by adding different kinds and amounts of plasticizers, the film surface topography was determined by a SEM, the tensile strength, water vapor transmission rate and moisture absorption were also tested to choose the most promising film. DBP was proved to be the most suitable plasticizer with a best using amount of 20%, such polymer films had low vapor transmission rate and low moisture absorption which were very important to an enteric coating material. The polymer was further characterized for film coating by evaluating the release of erythromycin tablets in vitro, tablets coated with SMA-ethanol can satisfy the drug release requests of USP when the film weight gains were between 4 and 6%; tablets coated with both a subcoat and the polymer showed excellent gastro-resistance, less than 0.2% drug release occurred even with weight gains as less as 2% after 2h exposure to acid (pH 1), while over 90% drug release occurred in pH 6.8 sodium phosphate buffer within 45 min, regardless of weight gains of coating material, moreover, we confirmed that the application of a subcoat could decrease the amount of required coating polymer. In conclusion, the potential use of SMA-ethanol as enteric coating material was demonstrated.

  18. Hydrolysis study of organic acid anhydrides by differential thermal analysis-I Pyromellitic dianhydride.

    PubMed

    Rosenfeld, J M; Loncrini, D F; Murphy, C B

    1966-08-01

    A technique for following the hydrolysis of pyromellitic acid dianhydride (PMDA) by differential thermal analysis (DTA) is described. On exposure of PMDA to moisture, an endothennic peak is initiated between 190 and 200 degrees . As the degree of hydrolysis increases, this peak becomes more intense and shifts to higher temperatures. The formation of pyromellitic acid (PMA) during the hydrolysis of PMDA can be determined qualitatively by DTA.

  19. From epoxidized linseed oil to bioresin: an overall approach of epoxy/anhydride cross-linking.

    PubMed

    Pin, Jean-Mathieu; Sbirrazzuoli, Nicolas; Mija, Alice

    2015-04-13

    Biorenewable resources can be used as green monomers to design tailored structures for formulations that can play an important role as functional materials. The choice of optimal structures depends on the targeted properties and applications. This work focuses on the elaboration of biobased materials with toughened mechanical properties based on epoxidized linseed oil. This result was obtained by an overall approach of cross-linking process, that is, starting with the optimal choice of hardeners and finally favoring the side reactions of polymerization. Therefore, the anionic alternating copolymerization of epoxide with mono- and dianhydrides was investigated to tailor the parameters that led to maximal conversions and properties. The obtained highly cross-linked networks perform well, as demonstrated by good impact strengths, high glass transition temperatures, and excellent thermal stability, which opens up the possibility of using these emergent materials for industrial applications.

  20. Comparative Emulsifying Properties of Octenyl Succinic Anhydride (OSA)-Modified Starch: Granular Form vs Dissolved State

    PubMed Central

    Marefati, Ali; Gutiérrez, Gemma; Wahlgren, Marie; Rayner, Marilyn

    2016-01-01

    The emulsifying ability of OSA-modified and native starch in the granular form, in the dissolved state and a combination of both was compared. This study aims to understand mixed systems of particles and dissolved starch with respect to what species dominates at droplet interfaces and how stability is affected by addition of one of the species to already formed emulsions. It was possible to create emulsions with OSA-modified starch isolated from Quinoa as sole emulsifier. Similar droplet sizes were obtained with emulsions prepared at 7% (w/w) oil content using OSA-modified starch in the granular form or molecularly dissolved but large differences were observed regarding stability. Pickering emulsions kept their droplet size constant after one month while emulsions formulated with OSA-modified starch dissolved exhibited coalescence. All emulsions stabilized combining OSA-modified starch in granular form and in solution showed larger mean droplet sizes with no significant differences with respect to the order of addition. These emulsions were unstable due to coalescence regarding presence of free oil. Similar results were obtained when emulsions were prepared by combining OSA-modified granules with native starch in solution. The degree of surface coverage of starch granules was much lower in presence of starch in solution which indicates that OSA-starch is more surface active in the dissolved state than in granular form, although it led to unstable systems compared to starch granule stabilized Pickering emulsions, which demonstrated to be extremely stable. PMID:27479315

  1. 40 CFR 721.524 - Alcohols, C6-12, ethoxylated, reaction product with maleic anhydride.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Alcohols, C6-12, ethoxylated, reaction... New Uses for Specific Chemical Substances § 721.524 Alcohols, C6-12, ethoxylated, reaction product... chemical substance identified generically as alcohols, C6-12, ethoxylated, reaction product with...

  2. 40 CFR 721.524 - Alcohols, C6-12, ethoxylated, reaction product with maleic anhydride.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Alcohols, C6-12, ethoxylated, reaction... New Uses for Specific Chemical Substances § 721.524 Alcohols, C6-12, ethoxylated, reaction product... chemical substance identified generically as alcohols, C6-12, ethoxylated, reaction product with...

  3. 40 CFR 721.524 - Alcohols, C6-12, ethoxylated, reaction product with maleic anhydride.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Alcohols, C6-12, ethoxylated, reaction... New Uses for Specific Chemical Substances § 721.524 Alcohols, C6-12, ethoxylated, reaction product... chemical substance identified generically as alcohols, C6-12, ethoxylated, reaction product with...

  4. 40 CFR 721.524 - Alcohols, C6-12, ethoxylated, reaction product with maleic anhydride.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Alcohols, C6-12, ethoxylated, reaction... New Uses for Specific Chemical Substances § 721.524 Alcohols, C6-12, ethoxylated, reaction product... chemical substance identified generically as alcohols, C6-12, ethoxylated, reaction product with...

  5. 40 CFR 721.524 - Alcohols, C6-12, ethoxylated, reaction product with maleic anhydride.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Alcohols, C6-12, ethoxylated, reaction... New Uses for Specific Chemical Substances § 721.524 Alcohols, C6-12, ethoxylated, reaction product... chemical substance identified generically as alcohols, C6-12, ethoxylated, reaction product with...

  6. 40 CFR 721.10316 - Dicyclopentadiene polymer with maleic anhydride and alkyl alcohols (generic).

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Dicyclopentadiene polymer with maleic... Significant New Uses for Specific Chemical Substances § 721.10316 Dicyclopentadiene polymer with maleic.... (1) The chemical substance identified generically as dicyclopentadiene polymer with maleic...

  7. 40 CFR 721.10316 - Dicyclopentadiene polymer with maleic anhydride and alkyl alcohols (generic).

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Dicyclopentadiene polymer with maleic... Significant New Uses for Specific Chemical Substances § 721.10316 Dicyclopentadiene polymer with maleic.... (1) The chemical substance identified generically as dicyclopentadiene polymer with maleic...

  8. 40 CFR 721.10316 - Dicyclopentadiene polymer with maleic anhydride and alkyl alcohols (generic).

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Dicyclopentadiene polymer with maleic... Significant New Uses for Specific Chemical Substances § 721.10316 Dicyclopentadiene polymer with maleic.... (1) The chemical substance identified generically as dicyclopentadiene polymer with maleic...

  9. Salicylic acid-derived poly(anhydride-ester) electrospun fibers designed for regenerating the peripheral nervous system

    PubMed Central

    Griffin, Jeremy; Delgado-Rivera, Roberto; Meiners, Sally; Uhrich, Kathryn E.

    2011-01-01

    Continuous biomaterial advances and the regenerating potential of the adult human peripheral nervous system offer great promise for restoring full function to innervated tissue following traumatic injury via synthetic nerve guidance conduits. To most effectively facilitate nerve regeneration, a tissue engineering scaffold within a conduit must be similar to the linear microenvironment of the healthy nerve. To mimic the native nerve structure, aligned poly(lactic-co-glycolic acid)/bioactive polyanhydride fibrous substrates were fabricated through optimized electrospinning parameters with diameters of 600 ± 200 nm. Scanning electron microscopy images show fibers with a high degree of alignment. Schwann cells and dissociated rat dorsal root ganglia demonstrated elongated and healthy proliferation in a direction parallel to orientated electrospun fibers with significantly longer Schwann cell process length and neurite outgrowth when compared to randomly orientated fibers. Results suggest that an aligned polyanhydride fiber mat holds tremendous promise as a supplement scaffold for the interior of a degradable polymer nerve guidance conduit. Bioactive salicylic acid based polyanhydride fibers are not limited to nerve regeneration and offer exciting promise for a wide variety of biomedical applications. PMID:21442724

  10. Salicylic acid-based poly(anhydride-ester) nerve guidance conduits: Impact of localized drug release on nerve regeneration.

    PubMed

    Lee, Yong S; Griffin, Jeremy; Masand, Shirley N; Shreiber, David I; Uhrich, Kathryn E

    2016-04-01

    Nerve guidance conduits (NGCs) can serve as physical scaffolds aligning and supporting regenerating cells while preventing scar tissue formation that often interferes with the regeneration process. Numerous studies have focused on functionalizing NGCs with neurotrophic factors, for example, to support nerve regeneration over longer gaps, but few directly incorporate therapeutic agents. Herein, we fabricated NGCs from a polyanhydride comprised of salicylic acid (SA), a nonsteroidal anti-inflammatory drug, then performed in vitro and in vivo assays. In vitro studies included cytotoxicity, anti-inflammatory response, and NGC porosity measurements. To prepare for implantation, type I collagen hydrogels were used as NGC luminal fillers to further enhance the axonal regeneration process. For the in vivo studies, SA-NGCs were implanted in femoral nerves of mice for 16 weeks and evaluated for functional recovery. The SA-based NGCs functioned as both a drug delivery vehicle capable of reducing inflammation and scar tissue formation because of SA release as well as a tissue scaffold that promotes peripheral nerve regeneration and functional recovery.

  11. Chromic anhydride-3, 5-dimethylpyrazole complex: an efficient reagent for oxidation of steroidal estrogens to 6-oxo-derivatives.

    PubMed

    Garza, G A; Rao, P N

    1983-10-01

    An efficient procedure for the oxidation of steroidal estrogens to the corresponding 6-oxo-derivatives is described. The oxidative process involves the use of 3,5-dimethylpyrazole-chromium trioxide complex at low temperature (-20 degrees). Under these conditions, only the 6-oxo-derivative and the unreacted starting material were obtained and the latter could be subjected to oxidation once again to obtain additional amount of 6-oxo-derivative.

  12. Importance of Trimethylaluminum Diffusion in Three-Step ABC Molecular Layer Deposition Using Trimethylaluminum, Ethanolamine, and Maleic Anhydride

    DTIC Science & Technology

    2010-01-01

    I. Introduction Atomic layer deposition ( ALD ) is a thin film synthesis method for inorganic materials based on sequential, self-limiting surface...reactions.1-3 Because of its accurate control of thickness and high conformality, ALD is useful in nanofabrication and nanostruc- ture engineering.4...Molecular layer deposition (MLD) is an exten- sion of ALD to include films that contain organic molecular components.5,6 Entirely organic MLD systems that

  13. Analysis of the effect of anhydride of trifluoroacetanhydride in the working mixture composition on the operation of iodine photodissociation laser

    NASA Astrophysics Data System (ADS)

    Vinogradskii, L. M.; Polozov, A. A.; Khudikov, N. M.

    2015-12-01

    The effect of the (CF3CO)2O (trifluoroacetanhydride) buffer additive on the operation of an iodine photodissociation laser is studied experimentally. Comparative experiments for determining the laser energy of the iodine laser with the replacement of the working substance with this buffer additive and without it and with widely used buffer gas SF6 (sulfur hexafluoride) are carried out. Optical inhomogeneities in the working volume, emerging during pumping of working mixtures based on i-C3F7I (perfluoroalkyl iodide) with buffer additives (CF3CO)2O and C6F14 (perfluorohexane), are measured. The results of experiments are analyzed.

  14. National Center on Health, Physical Activity and Disability

    MedlinePlus

    ... View All Articles Inclusive PE/PA Video Contest Mar 31, 2017 View results and winning schools from the video contest! Additional Updates: Quiet Please Mar 31, 2017 Avoiding Food in Social Situations Mar ...

  15. Converting a Staphylococcus aureus toxin into effective cyclic pseudopeptide antibiotics.

    PubMed

    Solecki, Olivia; Mosbah, Amor; Baudy Floc'h, Michèle; Felden, Brice

    2015-03-19

    Staphylococcus aureus produces peptide toxins that it uses to respond to environmental cues. We previously characterized PepA1, a peptide toxin from S. aureus, that induces lytic cell death of both bacterial and host cells. That led us to suggest that PepA1 has an antibacterial activity. Here, we demonstrate that exogenously provided PepA1 has activity against both Gram-positive and Gram-negative bacteria. We also see that PepA1 is significantly hemolytic, thus limiting its use as an antibacterial agent. To overcome these limitations, we converted PepA1 into nonhemolytic derivatives. Our most promising derivative is a cyclic heptapseudopeptide with inconsequential toxicity to human cells, enhanced stability in human sera, and sharp antibacterial activity. Mechanistically, linear and helical PepA1 derivatives form pores at the bacterial and erythrocyte surfaces, while the cyclic peptide induces bacterial envelope reorganization, with insignificant action on the erythrocytes. Our work demonstrates that bacterial toxins might be an attractive starting point for antibacterial drug development.

  16. A Mechanistic Study of a-Amino Acid-N-Carboxy Anhydride Polymerization: Comparing Initiation and Termination Events in High Vacuum and Traditional Polymerization Techniques

    SciTech Connect

    Pickel, Deanna L; Politakos, Nikolaos; Avgeropoulos, Apostolos; Messman, Jamie M

    2009-01-01

    High-vacuum polymerization of -amino acid-N-carboxyanhydride (NCAs) affords polymers with controlled molecular weights and narrow polydispersities, however a comprehensive study of the end-group composition of the resulting poly(amino acid)s has not yet been performed. This reveals crucial information, as the end-groups are indicative of both the polymerization mechanism (i.e., initiation event) as well as the termination pathways. To this end, poly(O-benzyl-L-tyrosine) initiated by 1,6-diaminohexane was synthesized and subsequently characterized by MALDI-TOF MS, NALDI -TOF MS and 13C NMR spectroscopy to ascertain the end-group structure. Polymers were prepared by both high vacuum and glove box techniques in DMF/THF. Preparation of poly(O-benzyl-L-tyrosine) by high vacuum techniques yielded a polymer initiated exclusively by the normal amine mechanism, and termination by reaction with DMF was observed. In contrast, polymers prepared in the glove box were initiated by the normal amine and activated monomer mechanisms, and several termination products are evident. To our knowledge, this is the first rigorous and comparative analysis of the end-group structure, and it demonstrates the advantage of high vacuum techniques for polymerization of NCAs for the preparation of well-defined poly(amino acid)s with end-group fidelity.

  17. A turn-on fluorescent probe based on coumarin-anhydride for highly sensitive detection of hydrazine in the aqueous solution and gas states

    NASA Astrophysics Data System (ADS)

    Wu, Guangfu; Tang, Xin; Ji, Wengang; Chiu Lai, King Wai; Tong, Qingxiao

    2017-03-01

    In this paper, a new coumarin-based fluorescent probe for hydrazine was rationally designed and successfully synthesized based on the Gabriel reaction. This novel probe enabled highly sensitive and selective detection of hydrazine. The detection limit was 43.6 nM (1.49 ppb). It displayed distinct changes in the intensity of both absorption and emission spectra upon the addition of hydrazine and remarkable color changes can be visually observed. The sensing mechanism of this probe toward hydrazine was characterized by 1H NMR and mass spectroscopy. Moreover, with the help of theoretical calculations, the sensing capability of this probe for hydrazine detection was described: the electron structure was modulated by a three-substituted group of coumarin once upon the addition of hydrazine. In addition, a test paper experiment indicated its great potential in environment monitoring.

  18. Effects of fluid flow on elution of hydrophilic modifier from dialysis membrane surfaces.

    PubMed

    Matsuda, Masato; Sato, Mika; Sakata, Hiroki; Ogawa, Takahisa; Yamamoto, Ken-ichiro; Yakushiji, Taiji; Fukuda, Makoto; Miyasaka, Takehiro; Sakai, Kiyotaka

    2008-01-01

    When uremic blood flows through dialyzers during hemodialysis, dialysis membrane surfaces are exposed to shear stress and internal filtration, which may affect the surface characteristics of the dialysis membranes. In the present study, we evaluated changes in the characteristics of membrane surfaces caused by shear stress and internal filtration using blood substitutes: water purified by reverse osmosis and 6.7 wt% dextran70 solution. We focused on the levels of a hydrophilic modifier, polyvinylpyrrolidone (PVP), on the membrane surface measured by attenuated total reflectance Fourier transform infrared spectroscopy. Experiments involving 4 h dialysis, 0-144 h shear-stress loading, and 4 h dead-end filtration were performed using polyester-polymer alloy (PEPA) and polysulfone (PS) membranes. After the dialysis experiments with accompanying internal filtration, average PVP retention on the PEPA membrane surface was 93.7% in all areas, whereas that on the PS membrane surface was 98.9% in all areas. After the shear-stress loading experiments, PVP retention on the PEPA membrane surface decreased as shear-stress loading time and the magnitude of shear stress increased. However, with the PS membrane, PVP retention scarcely changed. After the dead-end filtration experiments, PVP retention decreased in all areas for both PEPA and PS membranes, but PVP retention on the PEPA membrane surface was lower than that on the PS membrane surface. PVP on the PEPA membrane surface was eluted by both shear stress and internal filtration, while that on the PS membrane surface was eluted only by internal filtration.

  19. Facilitating actions of an AMPA receptor potentiator upon extinction of contextually conditioned fear response in stressed mice.

    PubMed

    Yamada, Daisuke; Wada, Keiji; Sekiguchi, Masayuki

    2011-01-25

    Extinction of conditioned fear response is thought to be a biological process underlying exposure therapy for anxiety disorders. We have previously reported that an AMPA receptor potentiator, 4-[2-(phenylsulfonylamino)ethylthio]-2,6-difluorophenoxyacetamide (PEPA), facilitates extinction of fear memory formed through contextual fear conditioning in mice that had never been exposed to experimental stress. On the other hand, recent findings suggest that the fear extinction is impaired in stressed rats or mice. The purpose of the present study was to examine whether PEPA facilitates impaired extinction of fear in stressed mice. For this purpose, mice were applied stress (a 2h restraint, a 20min forced swim, and ether inhalation), and contextual fear conditioning was carried out 7 days later. After 1-3 days of conditioning, mice were re-exposed to the context for 6min, and behavioral freezing response was measured. The time mice spent frozen decreased following every extinction session, and the decrease was remarkably slower in the stressed mice than in control non-stressed mice. PEPA (3, 10, 30mg/kg body weight) or vehicle was intraperitoneally administered into stressed mice once before the first extinction session. The significant decrease of the freezing response in the extinction sessions was only seen in the 30mg/kg PEPA-administered stressed mice, compared with vehicle-administered stressed mice. A similar extent of decrease in the freezing response in the extinction sessions was observed in the PEPA-administered (30mg/kg) and d-cycloserine-administered (30mg/kg) mice. These results suggest that PEPA facilitates extinction of contextual fear in stressed mice.

  20. Piquing Student Interest with Pharmacology: An Interdisciplinary Program Helps High School Students Learn Biology and Chemistry Principles

    ERIC Educational Resources Information Center

    Halpin, Myra J.; Hoeffler, Leanne; Schwartz-Bloom, Rochelle D.

    2005-01-01

    To help students learn science concepts, Pharmacology Education Partnership (PEP)--a science education program that incorporates relevant topics related to drugs and drug abuse into standard biology and chemistry curricula was developed. The interdisciplinary PEP curriculum provides six modules to teach biology and chemistry principles within the…

  1. Note on the Honduras Radio Schools (ACPH--Accion Cultural Popular Hondureno). IEC Discussion Paper. Appendix 4.

    ERIC Educational Resources Information Center

    Young, Michael

    This report on the radio schools in Honduras, Central America, includes (1) an account of an afternoon session of the radio school's Primary Equivalence Programme (PEPA), including a testimonial of a student and a statement regarding the importance of the monitors; (2) information on the social background of Honduras; (3) an historical account of…

  2. The effect of packaging material and storage period on microwave-dried potato (Solanum tuberosum L.) cubes.

    PubMed

    Shakouri, Shahrzad; Ziaolhagh, Hamid Reza; Sharifi-Rad, Javad; Heydari-Majd, Mojtaba; Tajali, Rohallah; Nezarat, Somayeh; Teixeira da Silva, Jaime A

    2015-06-01

    The effect of three packaging materials (transparent biaxially oriented polypropylene laminate (BOPP); semi-transparent BOPP; polyethylene-polyamide (PE-PA) laminate) in three packaging conditions (vacuum, N2, natural atmosphere) and in two temperature treatments (blanching in hot water; steam) on microwave-dried potato (Solanum tuberosum L.; Solanaceae) cubes was studied. After storage for 60 and 120 days, the amount of ascorbic acid (AA), shrinkage and rehydration were determined. Dried potato cubes packaged under N2 atmosphere had the highest rehydration value (3.142 %). Since there is a direct relationship between the amount of water loss and shrinkage, samples packaged in PE-PA laminate packages under vacuum showed 4.947 % less shrinkage than transparent BOPP or semi-transparent BOPP due to low permeability of these packages. Potatoes stored for 120 days resulted in 7.89 % more shrinkage than those stored for 60 days. The least loss in AA occurred in PE-PA laminate packaging. The shelf-life of potato cubes can be increased and their quantitative and qualitative characteristics can be best preserved by package-drying in PE-PA laminate under vacuum conditions.

  3. A Novel Glutamyl (Aspartyl)-Specific Aminopeptidase A from Lactobacillus delbrueckii with Promising Properties for Application

    PubMed Central

    Stressler, Timo; Ewert, Jacob; Merz, Michael; Funk, Joshua; Claaßen, Wolfgang; Lutz-Wahl, Sabine; Schmidt, Herbert; Kuhn, Andreas; Fischer, Lutz

    2016-01-01

    Lactic acid bacteria (LAB) are auxotrophic for a number of amino acids. Thus, LAB have one of the strongest proteolytic systems to acquit their amino acid requirements. One of the intracellular exopeptidases present in LAB is the glutamyl (aspartyl) specific aminopeptidase (PepA; EC 3.4.11.7). Most of the PepA enzymes characterized yet, belonged to Lactococcus lactis sp., but no PepA from a Lactobacillus sp. has been characterized so far. In this study, we cloned a putative pepA gene from Lb. delbrueckii ssp. lactis DSM 20072 and characterized it after purification. For comparison, we also cloned, purified and characterized PepA from Lc. lactis ssp. lactis DSM 20481. Due to the low homology between both enzymes (30%), differences between the biochemical characteristics were very likely. This was confirmed, for example, by the more acidic optimum pH value of 6.0 for Lb-PepA compared to pH 8.0 for Lc-PepA. In addition, although the optimum temperature is quite similar for both enzymes (Lb-PepA: 60°C; Lc-PepA: 65°C), the temperature stability after three days, 20°C below the optimum temperature, was higher for Lb-PepA (60% residual activity) than for Lc-PepA (2% residual activity). EDTA inhibited both enzymes and the strongest activation was found for CoCl2, indicating that both enzymes are metallopeptidases. In contrast to Lc-PepA, disulfide bond-reducing agents such as dithiothreitol did not inhibit Lb-PepA. Finally, Lb-PepA was not product-inhibited by L-Glu, whereas Lc-PepA showed an inhibition. PMID:27003449

  4. Polyimides Based on Asymmetric Dianhydrides (II) (a-BPDA vs a-BTDA) for Resin Transfer Molding (RTM)

    NASA Technical Reports Server (NTRS)

    Chuang, Kathy C.; Criss, Jim M.; Mintz, Eric A.

    2010-01-01

    A new series of low-melt viscosity imide resins (10-20 poise at 280 C) were formulated from asymmetric 2,3,3',4' -benzophenone dianhydride (a-BTDA) and 4-phenylethynylphthalic endcaps, along with 3,4' -oxydianiline, 3,3' -methylenedianiline and 3,3'- diaminobenzophenone, using a solvent-free melt process. a-BTDA RTM resins exhibited higher glass transition temperatures (Tg's = 330-400 C) compared to those prepared by asymmetric 2,3,3',4' -biphenyl dianhydride, (a-BPDA, Tg's = 320-370 C). These low-melt viscosity imide resins were fabricated into polyimide/T650-35 carbon fiber composites by a RTM process. Composites properties of a-BTDA resins, such as open-hole compression and short-beam shear strength, are compared to those of composites made from a-BPDA based resin at room temperature, 288 C and 315 C. These novel, high temperature RTM imide resins exhibit outstanding properties beyond the performance of conventional RTM resins, such as epoxy and BMI resins which have use-temperatures around 177 C and 232 C for aerospace applications.

  5. 40 CFR 180.1035 - Pine oil; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... formulation with the bee repellent butanoic anhydride applied in an absorbent pad over the hive. Pine oil is... formulation with the bee repellent butanoic anhydride applied in an absorbent pad over the hive....

  6. 40 CFR 180.1035 - Pine oil; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... formulation with the bee repellent butanoic anhydride applied in an absorbent pad over the hive. Pine oil is... formulation with the bee repellent butanoic anhydride applied in an absorbent pad over the hive....

  7. 40 CFR 180.1035 - Pine oil; exemption from the requirement of a tolerance.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... formulation with the bee repellent butanoic anhydride applied in an absorbent pad over the hive. Pine oil is... formulation with the bee repellent butanoic anhydride applied in an absorbent pad over the hive....

  8. Synthesis of Hydroxy-Terminated Dinitropropyl Acrylate Polymers and Improved Characterization of Hydroxy-Terminated Prepolymers

    DTIC Science & Technology

    1983-03-01

    azelate polyesterdiol from Wittco PA Phthalic anhydride PCP Polycaprolactone diol from Union Carbide PDNPA Polydinitropropyl acrylate (our experimental... anhydride (AA) in the presence of N-methylimidazole (NMIM) (15)reported by Conners , and (b) phthalic anhydride (PA) in the presence of pyridine (PY...three meq sample of dried polymer was weighed into a 100 ml round bottom flask and 50 ml of phthalic anhydride stock solution (0.6 N) in anhydrous

  9. New polymer systems: Chain extension by dianhydrides

    NASA Technical Reports Server (NTRS)

    Rhein, R. A.; Ingham, J. D.

    1974-01-01

    Three anhydrides provide effective chain extension of hydroxy-terminated polyalkylene oxides and polybutadienes. Novel feature of these anhydride reactants is that they are difunctional as anhydrides, but they are tetrafunctional if conditions are selected that lead to total esterification or reaction of all carboxyl groups.

  10. Improved in vivo stability of actinium-225 macrocyclic complexes.

    PubMed

    Deal, K A; Davis, I A; Mirzadeh, S; Kennel, S J; Brechbiel, M W

    1999-07-29

    The favorable nuclear properties of actinium-225 ((225)Ac) have led to proposal of this isotope for use in radioimmunotherapy. In an effort to reduce the toxicity of free (225)Ac, a series of ligands were evaluated for stability in vivo. Loss of (225)Ac from acyclic chelating agents resulted in high liver uptake and poor whole body clearance. The macrocyclic ligands c-DOTA, PEPA, and HEHA were evaluated, and (225)Ac-HEHA showed exceptional stability in vivo. (225)Ac chelated with EDTA, DTPA, DOTA, or PEPA permitted substantial accumulation of the radionuclide to the liver, while the (225)Ac-HEHA complex was essentially excreted within minutes of administration. The preparation of the ligands and radiolabeled complexes and the biodistribution results will be discussed.

  11. GPS-Derived Precipitable Water Compared with the Air Force Weather Agency’s MM5 Model Output

    DTIC Science & Technology

    2002-03-26

    physics/index.htm]. Cucurull, Lidia, Jordi Vila , Pepa Sedo and Antonia Rius, October 2001: MASS/MM5 meteorological model validation and data...Commission, Document No. D01233, 72-84. Cucurull, L., B. Navascues, G. Ruffini, P. Elosegui, A. Rius and J. Vila , 2000: The use of GPS to...Pondeca, Manuel S.F.V., Xiaolei Zou, 2001: A case study of the variational assimilation of GPS zenith delay observations into a mesoscale model

  12. Cross-sectoral cancer care: views from patients and health care professionals regarding a personal electronic health record.

    PubMed

    Baudendistel, I; Winkler, E C; Kamradt, M; Brophy, S; Längst, G; Eckrich, F; Heinze, O; Bergh, B; Szecsenyi, J; Ose, D

    2017-03-01

    Cross-sectoral cancer care is complex and involves collaboration from health care professionals (HCPs) across multiple sectors. However, when health information exchange (HIE) is not adequate, it results in impeded coordination and continuity of care. A web-based personal electronic health record (PEPA) under patients' control, providing access to personal health data across sectors, is being developed. Aim of this study was to explore perceived benefits and concerns. Using a qualitative approach, 10 focus groups were performed collecting views of three prospective user groups: patients with colorectal cancer (n = 12), physicians (n = 17) and other HCPs (n = 16). Representatives from different health sectors across the Rhine-Neckar region (Germany) participated. Data were audio- and videotaped, transcribed verbatim and thematically analysed. Our study shows that patients and HCPs expected a PEPA to enhance cross-sectoral availability of information, cross-sectoral cooperation and facilitate data management. Quality of cancer care was expected to be improved. Concerns were expressed in terms of data protection and data security. Concepts like a PEPA offer the chance to support HIE and avoid gaps of information in cross-sectoral cancer care. This may lead to improvements in coordination and continuity of care. Issues concerning data security and protection have to be addressed.

  13. Rosen’s (M,R) system in process algebra

    PubMed Central

    2013-01-01

    Background Robert Rosen’s Metabolism-Replacement, or (M,R), system can be represented as a compact network structure with a single source and three products derived from that source in three consecutive reactions. (M,R) has been claimed to be non-reducible to its components and algorithmically non-computable, in the sense of not being evaluable as a function by a Turing machine. If (M,R)-like structures are present in real biological networks, this suggests that many biological networks will be non-computable, with implications for those branches of systems biology that rely on in silico modelling for predictive purposes. Results We instantiate (M,R) using the process algebra Bio-PEPA, and discuss the extent to which our model represents a true realization of (M,R). We observe that under some starting conditions and parameter values, stable states can be achieved. Although formal demonstration of algorithmic computability remains elusive for (M,R), we discuss the extent to which our Bio-PEPA representation of (M,R) allows us to sidestep Rosen’s fundamental objections to computational systems biology. Conclusions We argue that the behaviour of (M,R) in Bio-PEPA shows life-like properties. PMID:24237684

  14. Activation of AMPA receptor in the infralimbic cortex facilitates extinction and attenuates the heroin-seeking behavior in rats.

    PubMed

    Chen, Weisheng; Wang, Yiqi; Sun, Anna; Zhou, Linyi; Xu, Wenjin; Zhu, Huaqiang; Zhuang, Dingding; Lai, Miaojun; Zhang, Fuqiang; Zhou, Wenhua; Liu, Huifen

    2016-01-26

    Infralimbic cortex (IL) is proposed to suppress cocaine seeking after extinction, but whether the IL regulates the extinction and reinstatement of heroin-seeking behavior is unknown. To address this issue, the male SD rats were trained to self-administer heroin under a FR1 schedule for consecutive 14 days, then the rats underwent 7 daily 2h extinction session in the operant chamber. The activation of IL by microinjection PEPA, an allosteric AMPA receptor potentiator into IL before each of extinction session facilitated the extinction responding after heroin self-administration, but did not alter the locomotor activity in an open field testing environment. Other rats were first trained under a FR1 schedule for heroin self-administration for 14 days, followed by 14 days of extinction training, and reinstatement of heroin-seeking induced by cues was measured for 2h. Intra-IL microinjecting of PEPA at 15min prior to test inhibited the reinstatement of heroin-seeking induced by cues. Moreover, the expression of GluR1 in the IL and NAc remarkably increased after treatment with PEPA during the reinstatement. These finding suggested that activation of glutamatergic projection from IL to NAc shell may be involved in the extinction and reinstatement of heroin-seeking.

  15. Enhancing the water dispersibility of paclitaxel by complexation with hydrophobic peptides.

    PubMed

    Inada, Asuka; Oshima, Tatsuya; Baba, Yoshinari

    2015-11-01

    The complex between paclitaxel (Ptx) and a peptide mixture (Pep) was prepared to enhance of the water-dispersibility of Ptx. Pep was prepared by enzymatic hydrolysis of casein, followed by fractionation using ammonium sulfate precipitation and ultrafiltration. The Ptx and Pep complex (Ptx-Pep) was prepared by mixing an ethanol solution of Ptx and an aqueous solution of Pep followed by lyophilization. The water dispersibility test of Ptx-Pep prepared using different fractions of Pep demonstrated that a fraction (Pep-A), containing relatively hydrophobic peptides with high molecular weights, was effective in enhancing the water dispersibility of Ptx. The sequences of the major peptides in Pep-A were identified by matrix-assisted laser desorption/ionization time-of-flight/time-of-flight mass spectrometry with "LIFT" technique. The water dispersibility of the complex between Ptx and Pep-A (Ptx-Pep-A) was independent of pH, even though it is positively or negatively charged under strongly acidic and neutral conditions. As the particle size of Ptx-Pep-A in aqueous media was 147-215 nm, Ptx-Pep-A was present as a hydrocolloidal material in aqueous media.

  16. Molecular Analysis of Expression of the Lantibiotic Pep5 Immunity Phenotype

    PubMed Central

    Pag, Ulrike; Heidrich, Christoph; Bierbaum, Gabriele; Sahl, Hans-Georg

    1999-01-01

    The lantibiotic Pep5 is produced by Staphylococcus epidermidis 5. Within its biosynthetic gene cluster, the immunity gene pepI, providing producer self-protection, is localized upstream of the structural gene pepA. Pep5 production and the immunity phenotype have been found to be tightly coupled (M. Reis, M. Eschbach-Bludau, M. I. Iglesias-Wind, T. Kupke, and H.-G. Sahl, Appl. Environ. Microbiol. 60:2876–2883, 1994). To study this phenomenon, we analyzed pepA and pepI transcription and translation and constructed a number of strains containing various fragments of the gene cluster and expressing different levels of immunity. Complementation of a pepA-expressing strain with pepI in trans did not result in phenotypic immunity or production of PepI. On the other hand, neither pepA nor its product was found to be involved in immunity, since suppression of the translation of the pepA mRNA by mutation of the ATG start codon did not reduce the level of immunity. Moreover, homologous and heterologous expression of pepI from a xylose-inducible promoter resulted in significant Pep5 insensitivity. Most important for expression of the immunity phenotype was the stability of pepI transcripts, which in the wild-type strain, is achieved by an inverted repeat with a free energy of −56.9 kJ/mol, localized downstream of pepA. We performed site-directed mutagenesis to study the functional role of PepI and constructed F13D PepI, I17R PepI, and PepI 1-65; all mutants showed reduced levels of immunity. Western blot analysis indicated that F13D PepI and PepI 1-65 were not produced correctly or were partially degraded, while I17R PepI apparently was less efficient in providing self-protection than the wild-type PepI. PMID:9925587

  17. AGD Surface Modification on Nanofibers to Improve Dispersion and Interfacial Bonding

    DTIC Science & Technology

    2007-05-26

    VGCF and APT VGCF in the anhydride - cured epoxy matrix. However, tensile modulus and stregth of nanocomposites with solution blending method were lower...with the anhydride curing agent methyltetrahydrophthalic anhydride , MTHPA, Kukdo®, KBH- Vacuum Sample Sample Solution Metal mold Sample curing in...oven control by computer, 800C for 30 minutes and 1200C for 3 hours. 1089 (Kukdo Chemical). The mixing ratio of epoxy and curing agent was 100/90wt

  18. Stereoselective Synthesis of Tilivalline(1).

    PubMed

    Nagasaka, Tatsuo; Koseki, Yuji

    1998-10-02

    Tilivalline 1, a metabolite from Klebsiella pneumoniae var. ocytoca, was easily synthesized in five steps from (S)-proline and 3-(benzyloxy)isatoic anhydride 4g. This synthesis is based on modified Curtius reactions of 3-substituted phthalic anhydrides 11 to 3-substituted isatoic anhydrides 4, conversion of lactams 6 to the acyliminium precursors 7 and stereoselective introduction of indole from the less hindered side of 7.

  19. Proceedings of the International Conference on Stiff Computation, April 12-14, 1982, Park City, Utah. Volume II.

    DTIC Science & Technology

    1982-01-01

    phthalic anhydride reactor provides a real case with in- teresting mathematical results (3,4). This time the packed bed reactor is operated under...first case, the conversion of ortho-xylene to phthalic anhydride is well behaved and the temperature of the reactor remains within bounds. If the...temperature is raised just 10 K, though, the temperature rises very sharply, and all the phthalic anhydride is further reacted to form carbon dioxide. PAGE 8

  20. Theoretical investigation of the role of clay edges in prebiotic peptide bond formation. II - Structures and thermodynamics of the activated complex species

    NASA Technical Reports Server (NTRS)

    Collins, Jack R.; Loew, Gilda H.; Luke, Brian T.; White, David H.

    1988-01-01

    Molecular orbital calculations are used to study amino acid activation by anhydride formation in neutral phosphates and in tetrahedral silicate and aluminate sites on clay edges. The results agree with previous ab initio studies of Luke et al. (1984) on the reactant species. Relative heats of formation of the anhydrides indicate the extent of anhydride formation to be the greatest for Al and the least for phosphate, which is the same order as the stability of hydrolysis.

  1. Surface chemistry of polyimide precursors on Cu(111)

    NASA Astrophysics Data System (ADS)

    Ivanecky, J. E.; Child, C. M.; Campion, Alan

    1995-03-01

    We have investigated the bonding of the monomers pyromellitic dianhydride (PMDA) and oxydianiline (ODA) as well as model compounds, succinic anhydride, phthalic anhydride, and benzoic acid, on Cu(111) in ultrahigh vacuum. Unenhanced surface Raman spectroscopy was used to identify the adsorbed species. ODA was unreactive at 110 K; the surface vibrational features were identical to those in the condensed multilayer. In contrast, PMDA chemisorbed dissociatively to form a bidentate surface carboxylate. Succinic anhydride physisorbed at 110 K, whereas benzoic acid and phthalic anhydride both adsorbed dissociatively forming bridging surface carboxylates as was observed for PMDA. The surface Raman spectrum of PMDA showed resonance enhancement.

  2. Novel nonadride, heptadride and maleic acid metabolites from the byssochlamic acid producer Byssochlamys fulva IMI 40021 – an insight into the biosynthesis of maleidrides† †Electronic supplementary information (ESI) available: Details of any supplementary information available should be included here. See DOI: 10.1039/c5cc06988b Click here for additional data file.

    PubMed Central

    Szwalbe, Agnieszka J.; Williams, Katherine; O'Flynn, Daniel E.; Bailey, Andrew M.; Mulholland, Nicholas P.; Vincent, Jason L.; Willis, Christine L.

    2015-01-01

    The filamentous fungus Byssochlamys fulva strain IMI 40021 produces (+)-byssochlamic acid 1, its novel dihydroanalogue 2 and four related secondary metabolites. Agnestadrides A, 17 and B, 18 constitute a novel class of seven-membered ring, maleic anhydride-containing (hence termed heptadride) natural products. The putative maleic anhydride precursor 5 for both nonadride and heptadride biosynthesis was isolated as a fermentation product for the first time and its structure confirmed by synthesis. Acid 5 undergoes facile decarboxylation to anhydride 6. The generic term maleidrides is proposed to encompass biosynthetically-related compounds containing maleic anhydride moieties fused to an alicyclic ring, varying in size and substituents. PMID:26452099

  3. Use of fourier transform infrared spectroscopy to follow the heterocumulene aided thermal dehydration of phthalic and naphthalic acids.

    PubMed

    Rigout, Muriel L A; Lewis, David M

    2006-12-01

    Fourier transform infrared (FT-IR) spectroscopy has been successfully employed to follow the formation of phthalic anhydride and 1,8-naphthalic anhydride on heating their corresponding acids. The effects of three heterocumulenes, cyanamide, dicyandiamide, and sodium cyanate, on the temperature of formation of the anhydrides were also investigated using this method. It was found that the carbodiimides cyanamide and dicyandiamide dramatically lowered the temperature at which thermal dehydration of the acid led to anhydride formation. It was noted that cyanamide had a stronger catalytic effect than dicyandiamide, presumably due to the electron-withdrawing effect of the amidine group. Sodium cyanate was also found to promote the thermal dehydration of the acids to form the corresponding anhydrides. Under more severe conditions, phthalic acid anhydride formed is seen to react further, leading to the formation of phthalimide. The discrepancy between the products obtained with cyanamide and sodium cyanate leads to the conclusion that, unlike earlier claims, imide formation is not due to the reaction of the anhydride with the urea formed but with sodium cyanate itself. However, only the phthalic anhydride five-membered ring system is sufficiently reactive towards the CNO- nucleophile to form the imide; the six-membered 1,8-naphthalic anhydride system does not react in this way.

  4. Rubber Research. The Synthesis of Unsaturated Fluorocarbons.

    DTIC Science & Technology

    HALOGENATED HYDROCARBONS, SYNTHESIS(CHEMISTRY)), (*NITROSO COMPOUNDS, SYNTHESIS(CHEMISTRY)), FLUORINE COMPOUNDS, CHLORINE COMPOUNDS, ORGANIC SOLVENTS, ALKENES, IRON COMPOUNDS, PHOTOLYSIS, ACETIC ANHYDRIDE, ACETIC ACID

  5. Rubber Elasticity in Highly Crosslinked Polyesters.

    DTIC Science & Technology

    Esters, *Polymers, *Elastic properties, Rubber, Propylene glycol , Maleic acid, Anhydrides, Phthalic acids, Mechanical properties, Molecular structure, Crosslinking(Chemistry), Polymerization, Styrenes, Temperature, Transition temperature, Molecular weight

  6. Comparative Kinetic Study and Microwaves Non-Thermal Effects on the Formation of Poly(amic acid) 4,4′-(Hexafluoroisopropylidene)diphthalic Anhydride (6FDA) and 4,4′-(Hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline (BAPHF). Reaction Activated by Microwave, Ultrasound and Conventional Heating

    PubMed Central

    Tellez, Hugo Mendoza; Alquisira, Joaquín Palacios; Alonso, Carlos Rius; Cortés, José Guadalupe López; Toledano, Cecilio Alvarez

    2011-01-01

    Green chemistry is the design of chemical processes that reduce or eliminate negative environmental impacts. The use and production of chemicals involve the reduction of waste products, non-toxic components, and improved efficiency. Green chemistry applies innovative scientific solutions in the use of new reagents, catalysts and non-classical modes of activation such as ultrasounds or microwaves. Kinetic behavior and non-thermal effect of poly(amic acid) synthesized from (6FDA) dianhydride and (BAPHF) diamine in a low microwave absorbing p-dioxane solvent at low temperature of 30, 50, 70 °C were studied, under conventional heating (CH), microwave (MW) and ultrasound irradiation (US). Results show that the polycondensation rate decreases (MW > US > CH) and that the increased rates observed with US and MW are due to decreased activation energies of the Arrhenius equation. Rate constant for a chemical process activated by conventional heating declines proportionally as the induction time increases, however, this behavior is not observed under microwave and ultrasound activation. We can say that in addition to the thermal microwave effect, a non-thermal microwave effect is present in the system. PMID:22072913

  7. Comparative kinetic study and microwaves non-thermal effects on the formation of poly(amic acid) 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA) and 4,4'-(hexafluoroisopropylidene)bis(p-phenyleneoxy)dianiline (BAPHF). Reaction activated by microwave, ultrasound and conventional heating.

    PubMed

    Tellez, Hugo Mendoza; Alquisira, Joaquín Palacios; Alonso, Carlos Rius; Cortés, José Guadalupe López; Toledano, Cecilio Alvarez

    2011-01-01

    Green chemistry is the design of chemical processes that reduce or eliminate negative environmental impacts. The use and production of chemicals involve the reduction of waste products, non-toxic components, and improved efficiency. Green chemistry applies innovative scientific solutions in the use of new reagents, catalysts and non-classical modes of activation such as ultrasounds or microwaves. Kinetic behavior and non-thermal effect of poly(amic acid) synthesized from (6FDA) dianhydride and (BAPHF) diamine in a low microwave absorbing p-dioxane solvent at low temperature of 30, 50, 70 °C were studied, under conventional heating (CH), microwave (MW) and ultrasound irradiation (US). Results show that the polycondensation rate decreases (MW > US > CH) and that the increased rates observed with US and MW are due to decreased activation energies of the Arrhenius equation. Rate constant for a chemical process activated by conventional heating declines proportionally as the induction time increases, however, this behavior is not observed under microwave and ultrasound activation. We can say that in addition to the thermal microwave effect, a non-thermal microwave effect is present in the system.

  8. 21 CFR 172.275 - Synthetic paraffin and succinic derivatives.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... acid derivatives of isopropyl alcohol, polyethylene glycol, and polypropylene glycol. It consists of a... anhydride isopropyl half ester, dialkyl succinic anhydride polyethylene glycol half ester, and dialkyl... carbon atoms and the polyethylene and polypropylene glycols have molecular weights of 600 and...

  9. 21 CFR 172.275 - Synthetic paraffin and succinic derivatives.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... acid derivatives of isopropyl alcohol, polyethylene glycol, and polypropylene glycol. It consists of a... anhydride isopropyl half ester, dialkyl succinic anhydride polyethylene glycol half ester, and dialkyl... carbon atoms and the polyethylene and polypropylene glycols have molecular weights of 600 and...

  10. 21 CFR 172.275 - Synthetic paraffin and succinic derivatives.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... acid derivatives of isopropyl alcohol, polyethylene glycol, and polypropylene glycol. It consists of a... anhydride isopropyl half ester, dialkyl succinic anhydride polyethylene glycol half ester, and dialkyl... carbon atoms and the polyethylene and polypropylene glycols have molecular weights of 600 and...

  11. 21 CFR 172.275 - Synthetic paraffin and succinic derivatives.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... acid derivatives of isopropyl alcohol, polyethylene glycol, and polypropylene glycol. It consists of a... anhydride isopropyl half ester, dialkyl succinic anhydride polyethylene glycol half ester, and dialkyl... carbon atoms and the polyethylene and polypropylene glycols have molecular weights of 600 and...

  12. 21 CFR 172.275 - Synthetic paraffin and succinic derivatives.

    Code of Federal Regulations, 2014 CFR

    2014-04-01

    ..., polyethylene glycol, and polypropylene glycol. It consists of a mixture of the Fischer-Tropsch process paraffin... anhydride polyethylene glycol half ester, and dialkyl succinic anhydride polypropylene glycol half ester, where the alkane (alkyl) has a chain length of 30-70 carbon atoms and the polyethylene and...

  13. Polyurethanes from isosorbide-based diisocyanates.

    PubMed

    Zenner, Michael D; Xia, Ying; Chen, Jason S; Kessler, Michael R

    2013-07-01

    Benign building blocks: Stereochemically pure diisocyanates were prepared on a multigram scale from succinic anhydride and isosorbide or isomannide. Characterization of polyurethanes that were produced from these diisocyanates revealed low polydispersity, high thermal stability, and stereochemistry-dependent morphology. If biobased succinic anhydride is used, then no stoichiometric petroleum-derived reagents are required in the synthesis of these materials.

  14. 1,2,4-Butanetriol: Analysis and Synthesis

    DTIC Science & Technology

    1982-12-08

    ANHYDRIDE ........................41 CLEAVAGE OF CYCLIC ETHERS. .. ....... ......... 43 REFERENCES .. ... .......... .......... ......... 45... NOMENCLATURE .. ... .......... .......... ........ 49 1. iii/jy NSWC TR 82-380 ILLUSTRATIONS Figure Page I HYDROGENATION OF DIETHYLMALATE IN ETHANOL OVER NIKKI...of acetic acid, acetic anhydride , and sul Uric acid yielded 1,2,4-butanetriol triacetate. Subsequent methanolysis of the acetate produced BT. Wagaman

  15. 21 CFR 172.828 - Acetylated monoglycerides.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... molecular distillation or by steam stripping; or (2) The direct acetylation of edible monoglycerides with acetic anhydride without the use of catalyst or molecular distillation, and with the removal by vacuum distillation, if necessary, of the acetic acid, acetic anhydride, and triacetin. (b) The food additive has...

  16. 21 CFR 172.828 - Acetylated monoglycerides.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... molecular distillation or by steam stripping; or (2) The direct acetylation of edible monoglycerides with acetic anhydride without the use of catalyst or molecular distillation, and with the removal by vacuum distillation, if necessary, of the acetic acid, acetic anhydride, and triacetin. (b) The food additive has...

  17. 21 CFR 172.828 - Acetylated monoglycerides.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... molecular distillation or by steam stripping; or (2) The direct acetylation of edible monoglycerides with acetic anhydride without the use of catalyst or molecular distillation, and with the removal by vacuum distillation, if necessary, of the acetic acid, acetic anhydride, and triacetin. (b) The food additive has...

  18. 21 CFR 172.828 - Acetylated monoglycerides.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... molecular distillation or by steam stripping; or (2) The direct acetylation of edible monoglycerides with acetic anhydride without the use of catalyst or molecular distillation, and with the removal by vacuum distillation, if necessary, of the acetic acid, acetic anhydride, and triacetin. (b) The food additive has...

  19. Synthesis, characterization and nanocomposite formation of poly(glycerol succinate-co-maleate) with cellulose nanowhiskers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A novel biodegradable polymer based on glycerol, succinic anhydride and maleic anhydride, poly(glycerol succinate-co-maleate), poly(GlySAMA), was synthesized by melt polycondensation and tested as a matrix for composites with cellulose nanowhiskers. This glycerol-based polymer is thermally stable as...

  20. A Classroom Experiment on Phase Equilibria Involving Orientational Disordering in Crystals.

    ERIC Educational Resources Information Center

    Mjojo, C. C.

    1985-01-01

    Background information, procedures used, and results obtained are provided for an experiment in which a phase diagram is determined using a differential scanning calorimeter. Commercial samples of D-camphoric anhydride (Eastman Kodak) and D,L-camphoric anhydride (Aldrich) were used in the experiment. (JN)

  1. 78 FR 4792 - Epoxy Polymer; Exemption From the Requirement of a Tolerance

    Federal Register 2010, 2011, 2012, 2013, 2014

    2013-01-23

    ... AGENCY 40 CFR Part 180 Epoxy Polymer; Exemption From the Requirement of a Tolerance AGENCY: Environmental... requirement of a tolerance for residues of polymers of one or more diglycidyl ethers of bisphenol A...- cyclohexane-dicarboxylic anhydride and 1,2,3,6-tetrahydrophthalic anhydride; also referred to as epoxy...

  2. International Topical Workshop on Advances in Silicon-Based Polymer Science (2nd) Held in Makaha, Oahu, Hawaii on December 16-20, 1990

    DTIC Science & Technology

    1990-12-20

    monofunctional reagents such as phthalic anhydride and maleic anhydride , yielding nonreactive or potentially reactive endgroups, respectively...polymerization will be discussed, i.e., formation of ionic aggregates, interactions with monomer and polymer and complexes with nucleophilic additives. In the...pattern of the process. The second major discussed problem will be kinetics and mecha- nism of the formation of oligomers in the polymerization

  3. Understanding the optimal learning environment in palliative care.

    PubMed

    Connell, Shirley E; Yates, Patsy; Barrett, Linda

    2011-07-01

    The learning experiences of student nurses undertaking clinical placement are reported widely, however little is known about the learning experiences of health professionals undertaking continuing professional development (CPD) in a clinical setting, especially in palliative care. The aim of this study, which was conducted as part of the national evaluation of a professional development program involving clinical attachments with palliative care services (The Program of Experience in the Palliative Approach [PEPA]), was to explore factors influencing the learning experiences of participants over time. Thirteen semi-structured, one-to-one telephone interviews were conducted with five participants throughout their PEPA experience. The analysis was informed by the traditions of adult, social and psychological learning theories and relevant literature. The participants' learning was enhanced by engaging interactively with host site staff and patients, and by the validation of their personal and professional life experiences together with the reciprocation of their knowledge with host site staff. Self-directed learning strategies maximised the participants' learning outcomes. Inclusion in team activities aided the participants to feel accepted within the host site. Personal interactions with host site staff and patients shaped this social/cultural environment of the host site. Optimal learning was promoted when participants were actively engaged, felt accepted and supported by, and experienced positive interpersonal interactions with, the host site staff.

  4. The development of an application for data privacy by applying an audit repository based on IHE ATNA.

    PubMed

    Bresser, Laura; Köhler, Steffen; Schwaab, Christoph

    2014-01-01

    It is necessary to optimize workflows and communication between institutions involved in patients' treatment to improve quality and efficiency of the German healthcare. To achieve these in the Metropolregion Rhein-Neckar, a personal, cross-institutional patient record (PEPA) is used. Given the immense sensitivity of health-related information saved in the PEPA, it is imperative to obey the data protection regulations in Germany. One important aspect is the logging of access to personal health data and all other safety-related events. For gathering audit information, the IHE profile ATNA can be used, because it provides a flexible and standardized infrastructure. There are already existing solutions for gathering the audit information based on ATNA. In this article one solution (OpenATNA) is evaluated, which uses the method of evaluation defined by Peter Baumgartner. In addition, a user interface for a privacy officer is necessary to support the examination of the audit information. Therefore, we will describe a method to develop an application in Liferay (an OpenSource enterprise portal project) which supports examinations on the gathered audit information.

  5. RutR is the uracil/thymine-sensing master regulator of a set of genes for synthesis and degradation of pyrimidines.

    PubMed

    Shimada, Tomohiro; Hirao, Kiyo; Kori, Ayako; Yamamoto, Kaneyoshi; Ishihama, Akira

    2007-11-01

    Using the genomic SELEX, a total of six Escherichia coli DNA fragments have been identified, which formed complexes with transcription factor RutR. The RutR regulon was found to include a large number of genes encoding components for not only degradation of pyrimidines but also transport of glutamate, synthesis of glutamine, synthesis of pyrimidine nucleotides and arginine, and degradation of purines. DNase I footprinting indicated that RutR recognizes a palindromic sequence of TTGACCAnnTGGTCAA. The RutR box in P1 promoter of carAB encoding carbamoyl phosphate synthetase, a key enzyme of pyrimidine synthesis, overlaps with the PepA (CarP) repressor binding site, implying competition between RutR and PepA. Adding either uracil or thymine abolished RutR binding in vitro to the carAB P1 promoter. Accordingly, in the rutR-deletion mutant or in the presence of uracil, the activation in vivo of carAB P1 promoter was markedly reduced. Northern blot analysis of the RutR target genes indicated that RutR represses the Gad system genes involved in glutamate-dependent acid resistance and allantoin degradation. Altogether we propose that RutR is the pyrimidine sensor and the master regulator for a large set of the genes involved in the synthesis and degradation of pyrimidines.

  6. Preparation of highly luminescent and color tunable carbon nanodots under visible light excitation for in vitro and in vivo bio-imaging

    DOE PAGES

    Zheng, Min; Li, Jing; Xie, Zhigang; ...

    2015-11-10

    Carbon nanodots (CDs) have generated enormous excitement because of their superiority in water solubility, chemical inertness, low toxicity, ease of functionalization and resistance to photobleaching. Here we report a facile thermal pyrolysis route to prepare CDs with high quantum yield (QY) using citric acid as the carbon source and ethylene diamine derivatives (EDAs) including triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and polyene polyamine (PEPA) as the passivation agents. We find that the CDs prepared from EDAs, such as TETA, TEPA and PEPA, show relatively high photoluminescence (PL) QY (11.4, 10.6, and 9.8%, respectively) at 1ex of 465 nm. The cytotoxicity of themore » CDs has been investigated through in vitro and in vivo bio-imaging studies. The results indicate that these CDs possess low toxicity and good biocompatibility. As a result, the unique properties such as the high PL QY at large excitation wave length and the low toxicity of the resulting CDs make them promising fluorescent nanoprobes for applications in optical bio-imaging and biosensing.« less

  7. Preparation of highly luminescent and color tunable carbon nanodots under visible light excitation for in vitro and in vivo bio-imaging

    SciTech Connect

    Zheng, Min; Li, Jing; Xie, Zhigang; Qu, Dan; Miao, Xiang; Jing, Xiabing; Sun, Zaicheng; Fan, Hongyou; Liu, Shi

    2015-11-10

    Carbon nanodots (CDs) have generated enormous excitement because of their superiority in water solubility, chemical inertness, low toxicity, ease of functionalization and resistance to photobleaching. Here we report a facile thermal pyrolysis route to prepare CDs with high quantum yield (QY) using citric acid as the carbon source and ethylene diamine derivatives (EDAs) including triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and polyene polyamine (PEPA) as the passivation agents. We find that the CDs prepared from EDAs, such as TETA, TEPA and PEPA, show relatively high photoluminescence (PL) QY (11.4, 10.6, and 9.8%, respectively) at 1ex of 465 nm. The cytotoxicity of the CDs has been investigated through in vitro and in vivo bio-imaging studies. The results indicate that these CDs possess low toxicity and good biocompatibility. As a result, the unique properties such as the high PL QY at large excitation wave length and the low toxicity of the resulting CDs make them promising fluorescent nanoprobes for applications in optical bio-imaging and biosensing.

  8. Study of Electron Delocalization in 1,2-, 1,3-, and 1,4-Azaborines Based on the Canonical Molecular Orbital Contributions to the Induced Magnetic Field and Polyelectron Population Analysis.

    PubMed

    Papadopoulos, Anastasios G; Charistos, Nickolas D; Kyriakidou, Katerina; Sigalas, Michael P

    2015-10-01

    The electron delocalization in 1,2-azaborine, 1,3-azaborine, and 1,4-azaborine is studied using canonical molecular orbital contributions to the induced magnetic field (CMO-IMF) method and polyelectron population analysis (PEPA). Contour maps of the out-of-plane component of the induced magnetic field (Bz(ind)) of the π system show that the three azaborines, in contrast with borazine, sustain much of benzene's π-aromatic character. Among them, 1,3-azaborine exhibits the strongest π delocalization, while 1,4-azaborine is the weakest. Contour maps of Bz(ind) for individual π orbitals reveal that the differentiation of the magnetic response among the three isomers originates from the π-HOMO orbitals, whose magnetic response is governed by rotational allowed transitions to unoccupied orbitals. The low symmetry of azaborines enables a paratropic response from HOMO to unoccupied orbitals excitations, with their magnitude depending on the shape of interacting orbitals. 1,3-Azaborine presents negligible paratropic contributions to Bz(ind) from HOMO to unoccupied orbitals transitions, where 1,2- and 1,4-azaborine present substantial paratropic contributions, which lead to reduced diatropic response. Natural bond orbital (NBO) analysis employing PEPA shows that only the 1,3-azaborine contains π-electron fully delocalized resonance structures.

  9. Environmentally friendly surface modification of silk fiber: Chitosan grafting and dyeing

    NASA Astrophysics Data System (ADS)

    Davarpanah, Saideh; Mahmoodi, Niyaz Mohammad; Arami, Mokhtar; Bahrami, Hajir; Mazaheri, Firoozmehr

    2009-01-01

    In this paper, the surface modification of silk fiber using anhydrides to graft the polysaccharide chitosan and dyeing ability of the grafted silk were studied. Silk fiber was degummed and acylated with two anhydrides, succinic anhydride (SA) and phthalic anhydride (PA), in different solvents (dimethyl sulfoxide (DMSO) and N, N-dimethyl formamide (DMF)). The effects of anhydrides, solvents, anhydride concentration, liquor ratio (L:R) and reaction time on acylation of silk were studied. The polysaccharide chitosan was grafted to the acylated silk fiber and dyed by acid dye (Acid Black NB.B). The effects of pH, chitosan concentration, and reaction time on chitosan grafting of acylated silk were investigated. The physical properties show sensible changes regardless of weight gain. Scanning electron microscopy (SEM) analysis showed the presence of foreign materials firmly attached to the surface of silk. FTIR spectroscopy provided evidence that chitosan was grafted onto the acylated silk through the formation of new covalent bonds. The dyeing of the chitosan grafted-acylated silk fiber indicated the higher dye ability in comparison to the acylated and degummed silk samples. The mechanism of chitosan grafting over degummed silk through anhydride linkage was proposed. The findings of this research support the potential production of new environmentally friendly textile fibers. It is worthwhile to mention that the grafted samples have antibacterial potential due to the antibacterial property of chitosan molecules.

  10. Soy protein polymers: Enhancing the water stability property

    NASA Astrophysics Data System (ADS)

    Srinivasan, Gowrishankar

    Soy protein based plastics have been processed in the past by researchers for various short-term applications; however a common issue is the high water sensitivity of these plastics. This work concentrates on resolving this water sensitivity issue of soy protein polymers by employing chemical and mechanical interaction at the molecular level during extrusion. The primary chemical interactions employed were anhydride chemistries such as maleic anhydride (MA), phthalic anhydride (PTA), and butylated hydroxyanisole (BHA). These were respectively used in conjunction with glycerol as a plasticizer to produce relatively water stable soy protein based plastics. Formulations with varying additive levels of the chemistries were extruded and injection molded to form the samples for characterization. The additive levels of anhydrides were varied between 3-10% tw/tw (total mass). Results indicated that phthalic anhydride formulations resulted in highest water stability. Plastic formulations with concentration up to 10% phthalic anhydride were observed to have water absorption as low as 21.5% after 24 hrs of exposure to water with respect to 250% for the control formulation. Fourier transform infrared spectroscopy (FTIR) was utilized to characterize and confirm the fundamental mechanisms of water stability achieved by phthalic and maleic anhydride chemistries. In addition, the anhydride formulations were modified by inclusion of cotton fibers and pretreated cotton powder in order to improve mechanical properties. The incorporation of cotton fibers improved the dry strength by 18%, but did not significantly improve the wet state strength of the plastics. It was also observed that the butylated-hydroxy anisole (BHA) formulation exhibited high extension values in the dry state and had inferior water absorption properties in comparison with anhydride formulations.

  11. Process for epoxy foam production

    DOEpatents

    Celina, Mathias C.

    2011-08-23

    An epoxy resin mixture with at least one epoxy resin of between approximately 60 wt % and 90 wt %, a maleic anhydride of between approximately 1 wt % and approximately 30 wt %, and an imidazole catalyst of less than approximately 2 wt % where the resin mixture is formed from at least one epoxy resin with a 1-30 wt % maleic anhydride compound and an imidazole catalyst at a temperature sufficient to keep the maleic anhydride compound molten, the resin mixture reacting to form a foaming resin which can then be cured at a temperature greater than 50.degree. C. to form an epoxy foam.

  12. Hydrocarbon fuel detergent

    SciTech Connect

    Meyer, G.R.; Lyons, W.R.

    1990-01-23

    This patent describes a hydrocarbon fuel composition comprising: a hydrocarbon fuel; and a detergent amount of a detergent comprising an alkenylsuccinimide prepared by reacting an alkenylsuccinic acid or anhydride with a mixture of amines, wherein at least 90 weight percent of the alkenyl substituent is derived from an olefin having a carbon chain of from 10 to 30 carbons or mixtures thereof, and wherein the alkenylsuccinic acid or anhydride is reacted with the mixture of amines at a mole ratio of 0.8 to 1.5 moles of the amines per mole of the alkenylsuccinic acid or anhydride.

  13. Study of ester crosslinking reactions on aluminum surfaces by infrared attenuated total reflectance spectrometry

    NASA Astrophysics Data System (ADS)

    Bhat, Sanmitra A.; Yang, Charles Q.; de Haseth, James A.

    1998-06-01

    Polycarboxylic acids are used as an alternative nonformaldehyde durable press finishing agents for cotton fabrics. Previous studies have shown that polycarboxylic acids esterify with cotton cellulose through intermediate formation of a cyclic anhydride. Cotton cellulose, due to the presence of hydroxyl groups, is a very active substrate. To understand the mechanism of ester formation, esterification reactions were studied on aluminum surfaces by infrared attenuated total reflectance (ATR) spectrometry. The infrared data showed that a five-membered cyclic anhydride is formed as an intermediate, that esterifies with the crosslinking agents. The data also demonstrated that formation of anhydride increases with temperature and also in the presence of a catalyst.

  14. Phosphorus-containing bisimide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1981-01-01

    The production of fire-resistant resins particularly useful for making laminates with inorganic fibers such as graphite fibers is discussed. The resins are by (1) condensation of an ethylenically unsaturated cyclic anhydride with a bis(diaminophenyl) phosphine oxide, and (2) by addition polymerization of the bisimide so obtained. Up to about 50%, on a molar basis, of benzophenonetetracarboxylic acid anhydride can be substituted for some of the cyclic anhydride to alter the properties of the products. Graphite cloth laminates made with these resins show 800 C char yields greater than 70% by weight in nitrogen. Limiting oxygen indexes of more than 100% are determined for these resins.

  15. Request for Correction 15003 - Information Quality Act request for Correction of the TSCA Work Plan

    EPA Pesticide Factsheets

    This RFC concerns the Information Quality Act request for correction of the TSCA Work Plan for Chemical Assessments: 20154 Update and the TSCA Work Plan Chemicals: Methods Document (February 2012) regarding assessment of phthalic anhydride

  16. Catalytic actions of alkaline salts in reactions between 1,2,3,4-butanetetracarboxylic acid and cellulose: II. Esterification.

    PubMed

    Ji, Bolin; Tang, Peixin; Yan, Kelu; Sun, Gang

    2015-11-05

    1,2,3,4-Butanetetracarboxylic acid (BTCA) reacts with cellulose in two steps with catalysis of alkaline salts such as sodium hypophosphite: anhydride formation and esterification of anhydride with cellulose. The alkali metal ions were found effective in catalyzing formation of BTCA anhydride in a previous report. In this work, catalytic functions of the alkaline salts in the esterification reaction between BTCA anhydride and cellulose were investigated. Results revealed that acid anions play an important role in the esterification reaction by assisting removal of protons on intermediates and completion of the esterification between cellulose and BTCA. Besides, alkaline salts with lower pKa1 values of the corresponding acids are more effective ones for the reaction since addition of these salts could lead to lower pH values and higher acid anion concentrations in finishing baths. The mechanism explains the results of FTIR and wrinkle recovery angles of the fabrics cured under different temperatures and times.

  17. Evaluation of Toxic Air Emissions

    DTIC Science & Technology

    1995-06-01

    108394 106445 98828 94757 3547044 334883 Calcium Cyanamide Caprolactam Captan Carbaryl Carbon disulfide Carbon Tetrachloride Carbonyl sulfide Catechol...Phosphorus Phthalic anhydride Polychlorinated biphenyls (Aroclors) 1,3-Propane sultone beta-Propiolactone Propionaldehyde Propoxur (Baygon) Propylene

  18. 21 CFR 177.1460 - Melamine-formaldehyde resins in molded articles.

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... of this chapter Dioctyl phthalate For use as lubricant. Hexamethylenetetramine For use only as polymerization reaction control agent. Phthalic acid anhydride Do. Zinc stearate For use as lubricant. (c)...

  19. 21 CFR 177.1460 - Melamine-formaldehyde resins in molded articles.

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... of this chapter Dioctyl phthalate For use as lubricant. Hexamethylenetetramine For use only as polymerization reaction control agent. Phthalic acid anhydride Do. Zinc stearate For use as lubricant. (c)...

  20. 21 CFR 177.1460 - Melamine-formaldehyde resins in molded articles.

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... of this chapter Dioctyl phthalate For use as lubricant. Hexamethylenetetramine For use only as polymerization reaction control agent. Phthalic acid anhydride Do. Zinc stearate For use as lubricant. (c)...

  1. 21 CFR 177.1460 - Melamine-formaldehyde resins in molded articles.

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... of this chapter Dioctyl phthalate For use as lubricant. Hexamethylenetetramine For use only as polymerization reaction control agent. Phthalic acid anhydride Do. Zinc stearate For use as lubricant. (c)...

  2. Detergent and corrosion inhibitor and motor fuel composition containing same

    SciTech Connect

    Kaufman, B.J.; Herbstman, S.; Levin, M.

    1983-09-13

    As a detergent and corrosion inhibiting fuel additive, the product is claimed resulting from reaction of trimellitic anhydride and a N- C/sub 10/-C/sub 25/-hydrocarbyl-1,3-diaminopropane and a fuel composition containing same.

  3. Aminoacyl-nucleotide reactions - Studies related to the origin of the genetic code and protein synthesis

    NASA Technical Reports Server (NTRS)

    Mullins, D. W., Jr.; Senaratne, N.; Lacey, J. C., Jr.

    1984-01-01

    In the present paper, a report is presented on the effect of pH and carbonate on the hydrolysis rate constants of N-blocked and free aminoacyl adenylate anhydrides. Whereas the hydrolysis of free aminoacyl adenylates seems principally catalyzed by OH(-), the hydrolysis of the N-blocked species is also catalyzed by H(+), giving this compound a U-shaped hydrolysis vs. pH curve. Furthermore, at pH's less than 8, carbonate has an extreme catalytic effect on the hydrolysis of free aminoacyl-AMP anhydride, but essentially no effect on the hydrolysis of N-blocked aminoacyl-AMP anhydride. Furthermore, the N-blocked aminoacyl-AMP anhydride is a very efficient generator of peptides using free glycine as acceptor. The possible significance of the observations to prebiological peptide synthesis is discussed.

  4. 55 FR 14037 Correction to the National Emission Standards for Hazardous Air Pollutants

    EPA Pesticide Factsheets

    Correction to the National Emission Standards for Hazardous Air Pollutants; Benzene Emissions From Maleic Anhydride Plants, Ethylbenzene/Styrene Plants, Benzene Storage Vessels, Benzene Equipment Leaks, and Coke Byproduct Recovery Plants.

  5. Polyolefin-based aerogels

    NASA Technical Reports Server (NTRS)

    Lee, Je Kyun (Inventor); Gould, Gerogle L. (Inventor)

    2010-01-01

    The present invention relates to cross-linked polyolefin aerogels in simple and fiber-reinforced composite form. Of particular interest are polybutadiene aerogels. Especially aerogels derived from polybutadienes functionalized with anhydrides, amines, hydroxyls, thiols, epoxies, isocyanates or combinations thereof.

  6. Purification of secondary recovery waterflood liquids

    SciTech Connect

    Hansen, G. D.

    1985-03-05

    Polysaccharide gums, such as guar gum, are removed from an aqueous liquid by agglomerating the gum with a low molecular weight, water-soluble copolymer of styrene and maleic anhydride and separating the agglomerate from the aqueous liquid.

  7. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  8. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  9. THE RATIO OF THE GLASS TEMPERATURE TO THE MELTING POINT IN POLYMERS.

    DTIC Science & Technology

    PLASTICS , MELTING POINT, TRANSITION TEMPERATURE, POLYETHYLENE PLASTICS , VINYL PLASTICS , BUTADIENES, FLUORINE COMPOUNDS, STYRENE PLASTICS , POLYMERS...NYLON, PHYSICAL PROPERTIES, MOLECULAR STRUCTURE, CARBONATES, ESTERS, ACRYLIC RESINS, PHENOLIC PLASTICS , ANHYDRIDES, CARBOXYLIC ACIDS, PHTHALATES, UNITED KINGDOM.

  10. Transacylation and Transamidation Reactions in Neat and Dissolved Systems.

    DTIC Science & Technology

    reaction of non-cyclic carboxy anhydrides with amides and specifically acetanilide has been studied. Preliminary results of the kinetic studies of the reaction of organic bromides with benzoin are reported. (Author)

  11. 40 CFR 60.667 - Chemicals affected by subpart NNN.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... alcohols, ethoxylated, mixed Linear alcohols, ethoxylated, and sulfated, sodium salt, mixed Linear alcohols, sulfated, sodium salt, mixed Linear alkylbenzene 123-01-3 Magnesium acetate 142-72-3 Maleic anhydride...

  12. TREATMENT OF AMMONIUM NITRATE SOLUTIONS

    DOEpatents

    Boyer, T.W.; MacHutchin, J.G.; Yaffe, L.

    1958-06-10

    The treatment of waste solutions obtained in the processing of neutron- irradiated uranium containing fission products and ammonium nitrate is described. The object of this process is to provide a method whereby the ammonium nitrate is destroyed and removed from the solution so as to permit subsequent concentration of the solution.. In accordance with the process the residual nitrate solutions are treated with an excess of alkyl acid anhydride, such as acetic anhydride. Preferably, the residual nitrate solution is added to an excess of the acetic anhydride at such a rate that external heat is not required. The result of this operation is that the ammonium nitrate and acetic anhydride react to form N/sub 2/ O and acetic acid.

  13. Determination of the Absolute Stereochemistry of Secondary Alcohols: An Advanced Organic Chemistry Experiment for Undergraduate Students.

    ERIC Educational Resources Information Center

    Bandaranayake, Wickramasinghe M.

    1980-01-01

    Describes experiments which can be completed in five four-hour laboratory sessions, including two synthesis (alpha-phenylbutyric and alpha-phenylbutyric acid anhydride) and determining the absolute stereochemistry of secondary alcohols using the synthetic products. (JN)

  14. NEW HYPOFLUORITES CONTAINING NITROGEN.

    DTIC Science & Technology

    ANHYDRIDES, SYNTHESIS(CHEMISTRY)), (*FLUOROAMINES, SYNTHESIS(CHEMISTRY)), (*SULFIDES, SYNTHESIS(CHEMISTRY)), FLUORINE COMPOUNDS, ACETIC ACID , SULFUR COMPOUNDS, CHLORIDES, ESTERS, SILANES, TIN COMPOUNDS, HALOGENATED HYDROCARBONS, NUCLEAR MAGNETIC RESONANCE, INFRARED SPECTRA, MASS SPECTRA

  15. 21 CFR 172.765 - Succistearin (stearoyl propylene glycol hydrogen succinate).

    Code of Federal Regulations, 2011 CFR

    2011-04-01

    ... additive is the reaction product of succinic anhydride, fully hydrogenated vegetable oil (predominantly C16... additive is used or intended for use as an emulsifier in or with shortenings and edible oils intended...

  16. 21 CFR 172.765 - Succistearin (stearoyl propylene glycol hydrogen succinate).

    Code of Federal Regulations, 2012 CFR

    2012-04-01

    ... additive is the reaction product of succinic anhydride, fully hydrogenated vegetable oil (predominantly C16... additive is used or intended for use as an emulsifier in or with shortenings and edible oils intended...

  17. 21 CFR 172.765 - Succistearin (stearoyl propylene glycol hydrogen succinate).

    Code of Federal Regulations, 2010 CFR

    2010-04-01

    ... additive is the reaction product of succinic anhydride, fully hydrogenated vegetable oil (predominantly C16... additive is used or intended for use as an emulsifier in or with shortenings and edible oils intended...

  18. 21 CFR 172.765 - Succistearin (stearoyl propylene glycol hydrogen succinate).

    Code of Federal Regulations, 2013 CFR

    2013-04-01

    ... additive is the reaction product of succinic anhydride, fully hydrogenated vegetable oil (predominantly C16... additive is used or intended for use as an emulsifier in or with shortenings and edible oils intended...

  19. Effects of the order of addition of reagents and alkali on modification of wheat starches.

    PubMed

    Sui, Zhongquan; Huber, Kerry C; BeMiller, James N

    2015-07-10

    The objective of this research was to determine if adding reactive reagents to wheat starch granules before addition of alkali (the TRF method) would produce products that are different than those obtained with the conventional procedure (adding alkali before addition of reagent). Laboratory-isolated (LI) and commercial (C) normal (NWS) and waxy (WWS) wheat starches were each reacted with 6 reagents (acetic-adipic mixed anhydride (AAMA), phosphoryl chloride (POCl3), sodium trimetaphosphate (STMP), acetic anhydride (AA), succinic anhydride (SA), octenylsuccinic anhydride (OSA)). Data obtained were similar to those previously obtained with maize starches (Sui, Huber, & BeMiller, 2013). Almost no starch polymer molecule modification occurred when the TRF method and AAMA or AA were used; less than a third as much reaction when SA was the reagent used, and about the same amount of reaction when POCl3, STMP, or OSA were the reagents used (for different reasons).

  20. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  1. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  2. 40 CFR 721.6477 - Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic...

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... with ethoxylated fatty alcohols, reaction products with maleic anhydride. 721.6477 Section 721.6477... Alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols, reaction products with maleic... identified generically as alkyl polycarboxylic acids, esters with ethoxylated fatty alcohols,...

  3. 77 FR 40033 - Certain New Chemicals; Receipt and Status Information

    Federal Register 2010, 2011, 2012, 2013, 2014

    2012-07-06

    ... CBI (G) Coating (G) Acid anhydride, additive. polymer with aromatic isocyanate and polyalkyleneglycol...) Dispersant (G) Octadecanoic for ink acid, 12-hydroxy-, formulations. polymer with formaldehyde- aromatic...) Polymer of tubing systems; aromatic injection dicarboxylic acid molding of and alkane diamine....

  4. 45 FR 380444

    EPA Pesticide Factsheets

    Federal Register notice of National Emission Standards for Hazardous Air Pollutants; Benzene Emissions From Maleic Anhydride Plants, Ethylbenzene/Styrene Plants, Benzene Storage Vessels, Benzene Equipment Leaks, and Coke By-Product Recovery Plants.

  5. New polymer systems: Chain extension by dianhydrides

    NASA Technical Reports Server (NTRS)

    Rhein, R. A.; Ingham, J. D.

    1972-01-01

    The results are presented for a systematic investigation on the use of anhydrides to prepare stable elastomeric materials for space use, under mild reaction conditions. The three anhydrides investigated were found to provide effective chain extension of hydroxy-terminated poly(alkylene oxides) and poly(butadienes). These were tetrahydrofuran tetracarboxylic dianhydride, pyromellitic dianhydride, and benzophenone tetracarboxylic diahydride. The most effective catalyst investigated was ferric acetylacetonate, which resulted in chain extension at 333 K (60 C). One feature of these anhydride reactants is that they are difunctional as anhydrides, but tetrafunctional if conditions are selected that lead to reaction of all carboxyl groups. Therefore, chain extension can be effected and then followed by crosslinking via the residual carboxyl groups.

  6. Polymeric foams stable at high temperatures

    NASA Technical Reports Server (NTRS)

    Riccitiello, S. R.; Harrison, E. S.; Delano, C. B.

    1976-01-01

    Crosslinked poly(N-arylenebenzimidazoles) are stable up to 370 C. Polymers are made by mixing appropriate stoichiometric amounts of tetramine and aromatic dicarboxylic acid anhydride with phenol or alkyl-substituted phenol.

  7. Synthesis and cure characterization of high temperature polymers for aerospace applications

    NASA Astrophysics Data System (ADS)

    Li, Yuntao

    The E-beam curable BMI resin systems and phenylethynyl terminated AFR-PEPA-4 oligomer together with an imide model compound N-phenyl-[4-(phenylethynyl) phthalimide] were synthesized and characterized. E-beam exposure cannot propagate the polymerization of BMI system until the temperature goes up to 100°C. However, a small amount of oligomers may be generated from solid-state cure reaction under low E-beam intensity radiation. Higher intensity E beam at 40 kGy per pass can give above 75% reaction conversion of BMI with thermal cure mechanism involved. NVP is a good reactive diluent for BMI resin. The cure extents of BMI/NVP increase with the increase of the dosage and applied dosage per pass. The reaction rate is much higher at the beginning of the E-beam cure and slows down after 2 dose passes due to diffusion control. Free radical initiator dicumyl peroxide can accelerate the reaction rate at the beginning of E-beam cure reaction but doesn't affect final cure conversion very much. According to the results from FT-IR, 200 kGy total dosage E-beam exposure at 10 kGy per pass can give 70% reaction conversion of BMI/NVP with the temperature rise no more than 50°C. The product has a Tg of 180°C. The predicted ultimate Tg of cured AFR-PEPA-4 polyimide is found to be 437.2°C by simulation of DSC Tg as a function of cure. The activation energy of thermal cure reaction of AFR-PEPA-4 oligomer is 142.6 +/- 10.0 kJ/mol with the kinetic order of 1 when the reaction conversion is less than 80%. The kinetics analysis of the thermal cure of N-phenyl-[4-(phenylethynyl) phthalimide] was determined by FT-IR spectroscopy by following the absorbance of the phenylethynyl triple bond and conjugated bonds. The thermal crosslinking of N-phenyl-[4-(phenylethynyl) phthalimide] through phenylethynyl addition reaction has a reaction order of 0.95 and an activation energy of 173.5 +/- 8.2 kJ/mol. The conjugated bond addition reactions have a lower reaction order of 0.94 and lower activation

  8. Identification of a novel calcium binding motif based on the detection of sequence insertions in the animal peroxidase domain of bacterial proteins.

    PubMed

    Santamaría-Hernando, Saray; Krell, Tino; Ramos-González, María-Isabel

    2012-01-01

    Proteins of the animal heme peroxidase (ANP) superfamily differ greatly in size since they have either one or two catalytic domains that match profile PS50292. The orf PP_2561 of Pseudomonas putida KT2440 that we have called PepA encodes a two-domain ANP. The alignment of these domains with those of PepA homologues revealed a variable number of insertions with the consensus G-x-D-G-x-x-[GN]-[TN]-x-D-D. This motif has also been detected in the structure of pseudopilin (pdb 3G20), where it was found to be involved in Ca(2+) coordination although a sequence analysis did not reveal the presence of any known calcium binding motifs in this protein. Isothermal titration calorimetry revealed that a peptide containing this consensus motif bound specifically calcium ions with affinities ranging between 33-79 µM depending on the pH. Microcalorimetric titrations of the purified N-terminal ANP-like domain of PepA revealed Ca(2+) binding with a K(D) of 12 µM and stoichiometry of 1.25 calcium ions per protein monomer. This domain exhibited peroxidase activity after its reconstitution with heme. These data led to the definition of a novel calcium binding motif that we have termed PERCAL and which was abundantly present in animal peroxidase-like domains of bacterial proteins. Bacterial heme peroxidases thus possess two different types of calcium binding motifs, namely PERCAL and the related hemolysin type calcium binding motif, with the latter being located outside the catalytic domains and in their C-terminal end. A phylogenetic tree of ANP-like catalytic domains of bacterial proteins with PERCAL motifs, including single domain peroxidases, was divided into two major clusters, representing domains with and without PERCAL motif containing insertions. We have verified that the recently reported classification of bacterial heme peroxidases in two families (cd09819 and cd09821) is unrelated to these insertions. Sequences matching PERCAL were detected in all kingdoms of life.

  9. Synthesis of 24-phenyl-24-oxo steroids derived from bile acids by palladium-catalyzed cross coupling with phenylboronic acid. NMR characterization and X-ray structures.

    PubMed

    Mayorquín-Torres, Martha C; Romero-Ávila, Margarita; Flores-Álamo, Marcos; Iglesias-Arteaga, Martin A

    2013-11-01

    Palladium-catalyzed cross coupling of phenyboronic acid with acetylated bile acids in which the carboxyl functions have been activated by formation of a mixed anhydride with pivalic anhydride afforded moderate to good yield of 24-phenyl-24-oxo-steroids. Unambiguous assignments of the NMR signals were made with the aid of combined 1D and 2D NMR techniques. X-ray diffraction studies confirmed the obtained structures.

  10. Phosphorus-containing imide resins

    NASA Technical Reports Server (NTRS)

    Varma, I. K.; Fohlen, G. M.; Parker, J. A. (Inventor)

    1984-01-01

    Flame-resistant reinforced bodies are disclosed which are composed of reinforcing fibers, filaments or fabrics in a cured body of bis- and tris-imide resins derived from tris(m-aminophenyl) phosphine oxides by reaction with maleic anhydride or its derivatives, or of addition polymers of such imides, including a variant in which a mono-imide is condensed with a dianhydride and the product is treated with a further quantity of maleic anhydride.

  11. Molecular Structure of Interphases between DGEBA/BTDA Adhesives and Silver Substances Using Surface-Enhanced Ram Scattering

    DTIC Science & Technology

    1990-06-01

    reacted with the silane to form amide and imide structures. Some evidence for formation of metal salts by reaction of the anhydride with the oxidized... salt in the interphase. The anhydride adsorbed onto the surface oxide of the 2024 aluminum substrates, which was mostly A1203, to form a surface...sulfimide (saccharin or BS), and cumene hydroperoxide (CHP) (9).. This adhesive is known to cure rapidly in the absence of oxygen and in the presence of

  12. The Role Culture Plays in China’s Illicit Drug/Chemical Foreign Policy

    DTIC Science & Technology

    2008-03-20

    trafficking of these chemicals that include acetic anhydride, ephedrine /pseudoephedrine, and steroids. To better understand China’s lack of cooperation...ACKNOWLEDGEMENTS v INTRODUCTION 1 CHlNA AND THE INTERNATIONAL DRUG TRADE 2 ACETIC ANHYDRIDE PRODUCTION 3 CHlNESE EPHEDRINE AND PSEUDOEPHEDRINE EXPORTS...essential to the production of a controlled substance and for which no substitution can be made. China is a major producer of licit ephedrine and

  13. In Vivo Cholinesterase Inhibitory Specificity of Organophosphorus Nerve Agents

    DTIC Science & Technology

    2005-10-26

    of the hydrolysis products of V-agents are presumably phoric acid anhydrides , and their structures are very simi- toxic. Also, V-agents may be...slowly with carboxylesterases and phospho- anhydrides . GF contains a cyclohexyl substituent. rylphosphatases than do G-agents [3]. The G-type nerve agents...USA). Tris(hydroxymethyl) 2.4. AChE analysis amino methane was purchased from Fischer Scientific (Fair Lawn, NJ, USA). The bicinchronic (BCA) protein

  14. An XPS (X-Ray Photoelectron Spectroscopy) Study of the Composition of Thin Polyimide Films Formed by Vapor Deposition.

    DTIC Science & Technology

    1987-07-15

    1985) 2857. 13. B. D. Silverman, J. W. Bartha, J. G. Clabes, P. S Ho and A. R. Rossi, J. Polym . Sci. Part A 24 (1986) 3325. 14. E. Cartier , P. Pfluger...Benzenetetracarboxylic anhydride (PMDA), imidization, polymer , in situ, X-ray Photoelectron Spectroscopy (XPS),Cu(111) 20. ABSTRACT (Continue an...ODA) and 1,2,4,5 Benzenetetracarboxylic anhydride (PMDA). The imidization reaction leading to polymer formation was followed in situ with X-ray

  15. An Experimental Study of a Pulsed Electromagnetic Plasma Accelerator

    NASA Technical Reports Server (NTRS)

    Thio, Y. C. Francis; Eskridge, Richard; Lee, Mike; Smith, James; Martin, Adam; Markusic, Tom E.; Cassibry, Jason T.; Rodgers, Stephen L. (Technical Monitor)

    2002-01-01

    Experiments are being performed on the NASA Marshall Space Flight Center (MSFC) pulsed electromagnetic plasma accelerator (PEPA-0). Data produced from the experiments provide an opportunity to further understand the plasma dynamics in these thrusters via detailed computational modeling. The detailed and accurate understanding of the plasma dynamics in these devices holds the key towards extending their capabilities in a number of applications, including their applications as high power (greater than 1 MW) thrusters, and their use for producing high-velocity, uniform plasma jets for experimental purposes. For this study, the 2-D MHD modeling code, MACH2, is used to provide detailed interpretation of the experimental data. At the same time, a 0-D physics model of the plasma initial phase is developed to guide our 2-D modeling studies.

  16. New amine-type inhibitors for protecting low-carbon steels in hydrogen sulfide-containing neutral media

    SciTech Connect

    Podobaev, N.I.; Atanasyan, T.K.; Lyashenko, L.F.; Isaev, M.G.; Sidorenko, G.V.

    1988-01-10

    The protecting action of polethylenepolyamine (PEPA) products was carried out by gravimetric and electrochemical methods in aerated and de-aerated 35 NaCl solutions and simulated waste water containing CaCl/sub 2/, NaCl, NaHCO/sub 3/, Na/sub 2/SO/sub 4/, and KBr, with addition of H/sub 2/S. Gravimetric and electrochemical measurements were carried out and results are presented. The influence on tanning agents on the physicomechanical and photographic properties of the positive emulsion Unibrom, Normal at thermostated aging for two days was shown. The results lead to the conclusion that the use of animals as tanning agents of the emulsion lead to improvement of the physicomechanical properties of the emulsion light sensitive layers.

  17. Comparison of 225actinium chelates: tissue distribution and radiotoxicity.

    PubMed

    Davis, I A; Glowienka, K A; Boll, R A; Deal, K A; Brechbiel, M W; Stabin, M; Bochsler, P N; Mirzadeh, S; Kennel, S J

    1999-07-01

    The biodistribution and tissue toxicity of intravenously administered 225-actinium (225Ac) complexed with acetate, ethylene diamine tetraacetic acid (EDTA), 1, 4, 7, 10, 13-pentaazacyclopentadecane-N, N', N", N"', N"-pentaacetic acid (PEPA), or the "a" isomer of cyclohexyl diethylenetriamine pentaacetic acid (CHX-DTPA), were examined. The percent of injected dose per organ and per gram of tissue for each chelate complex was determined. 225Ac-CHX-DTPA was evaluated further for radiotoxic effects. Mice receiving > or =185 kBq 225Ac-CHX-DTPA suffered 100% morbidity by 5 days and 100% mortality by 8 days postinjection, and all animals evaluated had significant organ damage. The in vivo instability of the 225Ac-CHX-DTPA complex likely allowed accumulation of free 225Ac in organs, which resulted in tissue pathology.

  18. A Personal Electronic Health Record: Study Protocol of a Feasibility Study on Implementation in a Real-World Health Care Setting

    PubMed Central

    Kunz, Aline; Pohlmann, Sabrina; Hofmann, Helene; Qreini, Markus; Krisam, Johannes; Uhlmann, Lorenz; Jacke, Christian; Winkler, Eva C; Salize, Hans-Joachim; Szecsenyi, Joachim

    2017-01-01

    Background A significant potential for patient empowerment is seen in concepts aiming to give patients access to their personal health information (PHI) and to share this PHI across different care settings and health systems. Personal health records (PHRs) and the availability of information through health information exchanges are considered to be key components of effective and efficient health care. With tethered PHRs, as often used in the United States, patients’ opportunities to manage their PHI are strongly restricted. Therefore, within the INFOPAT (information technology for patient oriented care) project (2012-2016) in Germany, funded by the Federal Ministry of Education and Research (BMBF), the development of a patient-controlled “personal electronic health record” (PEPA) was based on user requirements right from the beginning. Objective The overall objective of the study is to implement and evaluate a PEPA prototype for patients with colorectal cancer who are treated at the National Center for Tumor Diseases in Heidelberg. To achieve this aim, this study has 2 parts: a pre-implementation study (phase 1) and an implementation study (phase 2). The pre-implementation study will include a usability evaluation of the PEPA approach and the consideration of organizational preconditions for the implementation. With the implementation study, we will evaluate the process of implementation (eg, barriers or facilitators), the need for organizational change (eg, processes of communication), and the impact on outcomes (eg, self-efficacy, involvement in care). Methods The pre-implementation study is based on a mixed methods approach and comprises qualitative and quantitative element according to our research aim. We will use a think-aloud method for the usability analysis. Additionally, participants will be asked to evaluate their overall satisfaction based on a standardized questionnaire, the System Usability Scale. For the analysis of preconditions, we will

  19. Interactions between VTA orexin and glutamate in cue-induced reinstatement of cocaine seeking in rats

    PubMed Central

    Mahler, Stephen V.; Smith, Rachel J.

    2013-01-01

    Rationale Glutamate and orexin/hypocretin systems are involved in Pavlovian cue-triggered drug seeking. Objectives Here, we asked whether orexin and glutamate interact within ventral tegmental area (VTA) to promote reinstatement of extinguished cocaine seeking in a rat self-administration paradigm. Methods/results We first found that bilateral VTA micro-injections of the orexin 1 receptor (OX1R) antagonist SB-334867 (SB) or a cocktail of the AMPA and NMDA glutamate receptor antagonists CNQX/AP-5 reduced reinstatement of cocaine seeking elicited by cues. In contrast, neither of these microinjections nor systemic SB reduced cocaine-primed reinstatement. Additionally, unilateral VTA OX1R blockade combined with contralateral VTA glutamate blockade attenuated cue-induced reinstatement, indicating that VTA orexin and glutamate are simultaneously necessary for cue-induced reinstatement. We further probed the receptor specificity of glutamate actions in VTA, finding that CNQX, but not AP-5, dose-dependently attenuated cue-induced reinstatement, indicating that AMPA but not NMDA receptor transmission is required for this type of cocaine seeking. Given the necessary roles of both OX1 and AMPA receptors in VTA for cue-induced cocaine seeking, we hypothesized that these signaling pathways interact during this behavior. We found that PEPA, a positive allosteric modulator of AMPA receptors, completely reversed the SB-induced attenuation of reinstatement behavior. Intra-VTA PEPA alone did not alter cue-induced reinstatement, indicating that potentiating AMPA activity with this drug specifically compensates for OX1R blockade, rather than simply inducing or enhancing reinstatement itself. Conclusions These findings show that cue-induced, but not cocaine-primed, reinstatement of cocaine seeking is dependent upon orexin and AMPA receptor interactions in VTA. PMID:22411428

  20. TrpM, a Small Protein Modulating Tryptophan Biosynthesis and Morpho-Physiological Differentiation in Streptomyces coelicolor A3(2)

    PubMed Central

    Palazzotto, Emilia; Gallo, Giuseppe; Renzone, Giovanni; Giardina, Anna; Sutera, Alberto; Silva, Joohee; Vocat, Celinè; Botta, Luigi; Scaloni, Andrea; Puglia, Anna Maria

    2016-01-01

    In the model actinomycete Streptomyces coelicolor A3(2), small open reading frames encoding proteins with unknown functions were identified in several amino acid biosynthetic gene operons, such as SCO2038 (trpX) in the tryptophan trpCXBA locus. In this study, the role of the corresponding protein in tryptophan biosynthesis was investigated by combining phenotypic and molecular analyses. The 2038KO mutant strain was characterized by delayed growth, smaller aerial hyphae and reduced production of spores and actinorhodin antibiotic, with respect to the WT strain. The capability of this mutant to grow on minimal medium was rescued by tryptophan and tryptophan precursor (serine and/or indole) supplementation on minimal medium and by gene complementation, revealing the essential role of this protein, here named TrpM, as modulator of tryptophan biosynthesis. His-tag pull-down and bacterial adenylate cyclase-based two hybrid assays revealed TrpM interaction with a putative leucyl-aminopeptidase (PepA), highly conserved component among various Streptomyces spp. In silico analyses showed that PepA is involved in the metabolism of serine, glycine and cysteine through a network including GlyA, CysK and CysM enzymes. Proteomic experiments suggested a TrpM-dependent regulation of metabolic pathways and cellular processes that includes enzymes such as GlyA, which is required for the biosynthesis of tryptophan precursors and key proteins participating in the morpho-physiological differentiation program. Altogether, these findings reveal that TrpM controls tryptophan biosynthesis at the level of direct precursor availability and, therefore, it is able to exert a crucial effect on the morpho-physiological differentiation program in S. coelicolor A3(2). PMID:27669158

  1. Effects of acylation on the functional properties and in vitro trypsin digestibility of red kidney bean (Phaseolus vulgaris L.) protein isolate.

    PubMed

    Yin, Shou-Wei; Tang, Chuan-He; Wen, Qi-Biao; Yang, Xiao-Quan

    2009-01-01

    The effects of succinylation and acetylation on some functional properties and the in vitro trypsin digestibility of kidney bean protein isolate (KPI) were investigated. The extent of succinylation or acetylation progressively increased from 0% to 96% to 97%, as the anhydride-to-protein ratio increased from 0 to 1 g/g. Polyacrylamide gel electrophoresis (PAGE) and zeta potential analyses indicated that acylation, especially succinylation, considerably increased the net charge and hydrodynamic radius of the proteins in KPI, especially vicilin. Acylation treatment at various anhydride-to-protein ratios (0.05 to 1 g/g) remarkably improved the protein solubility (PS) and emulsifying activity index (EAI) at neutral pH, but the improvement by succinylation was much better than that by acetylation. Succinylation resulted in a marked decrease in mechanical moduli of heat-induced gels of KPI, while the mechanical moduli were, on the contrary, increased by acetylation. Additionally, in vitro trypsin digestibility was improved by the acylation in an anhydride-type and level-dependent manner. The results suggest that the functional properties of KPI could be modulated by the chemical acylation treatment, using succinic or acetic anhydride at appropriate anhydride-to-protein ratios.

  2. Green route to modification of wood waste, cellulose and hemicellulose using reactive extrusion.

    PubMed

    Vaidya, Alankar A; Gaugler, Marc; Smith, Dawn A

    2016-01-20

    A large volume of wood waste is produced in timber processing industry which traditionally used in low value applications. Here, value addition to the wood waste (Sander dust) and cellulose, hemicellulose isolated thereof by functionalisation using cyclic anhydrides in a solvent-free and green reactive extrusion process is reported. The effect of extrusion temperature, catalyst and different weight ratios of Sander dust (SD):succinic anhydride (SA) on the esterification reaction is evaluated. The esterified products were characterised by the acid value, degree of substitution (DS), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), solid state (13)C NMR and thermo-gravimetric analysis (TGA). Under optimum extrusion conditions, mixed esters are formed, with highest acid value obtained for succinylation of cellulose (0.122 g/g at DS of 0.350) which is two times higher compared to succinylated SD (0.059 g/g at a weight gain of 0.452) and hemicellulose (0.043 g/g at DS of 0.290). The reactivity trend for individual anhydride was: (1) SA-Cellulose>SD>hemicellulose; (2) maleic anhydride (MA)-SD>hemicellulose>cellulose and (3) dodecenyl succinic anhydride (DDSA)-SD ≈ cellulose ≫ hemicellulose. The pendant free carboxyl groups generated through functionalisation of wood waste, cellulose and hemicellulose without the presence of polymeric carriers will allow more tailored or targeted modification of wood-plastic composites.

  3. [Improved methodology for quantitative determination of thiabendazole].

    PubMed

    Furusho, Noriko; Otsuki, Noriko; Ohtsuki, Takashi; Tatebe-Sasaki, Chiye; Sato, Kyoko; Akiyama, Hiroshi; Kawamura, Yoko

    2012-01-01

    The method prescribed in the 8th edition of Japan's Specifications and Standards for Food Additives (JSSFA) for the quantitative analysis of thiabendazole was improved by eliminating the use of toxic reagents such as mercuric acetate and chromium trioxide. For exclusion of mercuric acetate, a nonaqueous titration was performed using four types of solvent systems, including acetic acid:acetic anhydride (1:5), acetic acid:acetic anhydride (3:7), acetic acid alone, and formic acid:acetic acid (1:10), that did not contain mercuric compounds. Because precipitates were formed in titrations using acetic acid alone and formic acid:acetic acid (1:10), we considered that it was difficult to determine the purity using these solvent systems. However, it was confirmed that the purity of thiabendazole dissolved in the two acetic acid:acetic anhydride solvent systems can be determined using either a visual indicator or potentiometry. Specifically, the purity of thiabendazole was determined to be 99.9% (relative standard deviation (RSD) = 0.07%) for acetic acid:acetic anhydride (1:5) and 99.7% (RSD = 0.13%) for acetic acid:acetic anhydride (3:7) With respect to chromium trioxide, it was determined that chromium trioxide can be excluded using acetic acid, which conforms to the JIS K8001 standard for nonaqueous titrations. Therefore, in this study, an improved method for the quantitative determination of thiabendazole was developed without the use of toxic reagents.

  4. Investigation of alternative compounds to poly(E-MA) as a polymeric surfactant for preparation of microcapsules by phase separation method.

    PubMed

    Yoshizawa, Hidekazu; Kamio, Eiji; Kobayashi, Eiji; Jacobson, Joseph; Kitamura, Yoshiro

    2007-06-01

    Various water-soluble polymers were used to examine an alternative emulsifier for poly(ethylene-alt-maleic anhydride), used in the preparation of crosslinked polyurea microcapsules. Microcapsules were successfully prepared by using the water-soluble polymers with large molecular weight alternating copolymers, namely poly(olefin-maleic anhydride), poly(olefin-maleic acid), and poly(acrylic acid). On the other hand, no microcapsule resulted from olefin-maleic acid with small molecular weight alternating copolymers. From these results, the following guidelines were obtained for the selection of polymeric surfactants suitable for crosslinked polyurea microcapsule. A polymeric surfactant must have maleic acid or a carboxyl group in order to form a crosslinked polyurea microcapsule membrane. Furthermore, to form a stronger capsule membrane it is desirable to have a maleic anhydride group. It is also important for membrane formation that the polymeric surfactant has a suitable molecular weight.

  5. Synthesis and biological evaluation of cyclic imides incorporating benzenesulfonamide moieties as carbonic anhydrase I, II, IV and IX inhibitors.

    PubMed

    Abdel-Aziz, Alaa A-M; Angeli, Andrea; El-Azab, Adel S; Abu El-Enin, Mohamed A; Supuran, Claudiu T

    2017-03-01

    A group of cyclic imides was synthesized by reaction of amino-substituted benzenesulfonamides with a series of acid anhydrides such as succinic, maleic, tetrahydrophthalic, pyrazine-2,3-dicarboxylic acid anhydride, and substituted phthalic anhydrides. The synthesized sulfonamides were evaluated as carbonic anhydrase (CA, EC 4.2.1.1) inhibitors against the human (h) isoforms hCA I, II, IV and IX, involved in a variety of diseases among which glaucoma, retinitis pigmentosa, etc. Some of these sulfonamides showed effective inhibitory action (in the nanomolar range) against the cytosolic isoform hCA II and the transmembrane, tumor-associated one hCA IX, making them interesting candidates for preclinical evaluation in glaucoma or various tumors in which the two enzymes are involved. hCA I and IV were on the other hand less inhibited by these sulfonamides, with inhibition constants in the micromolar range.

  6. Haze, oxidation, and corrosion resistant diesel engine lubricant

    SciTech Connect

    Sung, R.L.; Zoleski, B.H.; O'Rourke, R.L.

    1987-11-10

    This patent describes a haze, oxidation, and corrosion resistant diesel engine lubricant composition, particularly useful in marine and railway diesel engines, contains 0.1-5.0 weight percent of a reaction product additive. The reaction product additive is produced by first reacting substantially equimolar amounts of an anhydride compound which is either a dibasic acid anhydride or isatoic anhydride and a hydrocarbon-substituted mono primary amine or ether amine at a temperature range of 50/sup 0/C-150/sup 0/C to produce an intermediate reaction product. The intermediate reaction product is thereafter further reacted at an elevated temperature with a substantially equimolar amount of a heterocyclic azole or polyalkylene polyamine compound to form the final reaction product.

  7. Polyimide analysis using diffuse reflectance-FTIR. [Fourier Transform IR Spectroscopy

    NASA Technical Reports Server (NTRS)

    Young, P. R.; Chang, A. C.

    1985-01-01

    The thermal imidization of a number of polyimide precursors in the form of powders, films, and prepregs was examined by an in situ diffuse reflectance-FTIR technique where infrared spectra were determined while the material was being heated. An analysis of these spectra revealed that, with the exception of one water soluble adhesive, each precursor developed an anhydride band around 1850 cm/cu during imidization. This band diminished in intensity during final stages of cure. Efforts were made to quantify the amount of anhydride in several samples. Evidence obtained could be interpreted to mean that poly(amic acid) resins undergo an initial reduction in molecular weight during imidization before recombining to achieve their ultimate molecular weights as polyimides. Several reports in the literature are cited to support this interpretation. This report serves both to document anhydride formation during imidization and to increase our fundamental understanding of how polyimides cure.

  8. Studies on the oxidation of hexamethylbenzene 1: Oxidation of hexamethylbenzene with nitric acid

    NASA Technical Reports Server (NTRS)

    Chiba, K.; Tomura, S.; Mizuno, T.

    1986-01-01

    The oxidative reaction of hexamethylbenzene (HMB) with nitric acid was studied, and the hitherto unknown polymethylbenzenepolycarboxylic acids were isolated: tetramethylphthalic anhydride, tetramethylisophthalic acid, 1,3,5-, 1,2,4- and 1,2,3-trimethylbenzenetricarboxylic acids. When HMB was warmed with 50% nitric acid at about 80 C, tetramethylphthalic anhydride and tetramethylisophthalic acid were initially produced. The continued reaction led to the production of trimethylbenzenetricarboxylic acids, but only slight amounts of dimethylbenzenetetracarboxylic acids were detected in the reaction mixture. Whereas tetramethylphthalic anydride and tetramethylisophthalic acid were obtained, pentamethylbenzoic acid, a possible precursor of them, was scarcely produced. On the other hand, a yellow material extracted with ether from the initial reaction mixture contained bis-(nitromethyl)prehnitene (CH3)4C6(CH2NO2)2, which was easily converted into the phthalic anhydride.

  9. Liquid Crystals Derived from 2-phenyl-isoindoles: Synthesis and Characterization

    NASA Technical Reports Server (NTRS)

    Jow, Kenny G.; Dingemans, Theo J.; Bushnell, Dennis M. (Technical Monitor)

    2001-01-01

    2-Phenyl-isoindole was investigated as the rigid core unit in a series of asymmetric mesogenic molecules. When the 2-phenyl-isoindole core was terminated with a hexyl tail, no mesophase formation could be observed. When 4-n-(tridecafluorohexyl) was used, however, we observed both monotropic and enantiotropic phase behavior. We found that most functionalities at the anhydride 5-position results in the formation of smectic A (SmA) phases in the temperature range of 70-180 C. Functionalities at the anhydride 4-position suppress mesophase formation. Large substituents (-Br, -NO2) and symmetric substitution patterns (5,6-dichloro, 4,7-dichloro and 4,5,6,7-tetrachloro) on the anhydride moiety increase the melting point and destabilize the mesophase. Temperature dependent X-ray diffraction experiments suggest an interdigitated SmA packing for this family of compounds.

  10. Tough soluble aromatic thermoplastic copolyimides

    NASA Technical Reports Server (NTRS)

    Bryant, Robert G. (Inventor)

    2000-01-01

    Tough, soluble, aromatic, thermoplastic copolyimides were prepared by reacting 4,4'-oxydiphthalic anhydride, 3,4,3',4'-biphenyltetracarboxylic dianhydride and 3,4'-oxydianiline. Alternatively, these copolyimides may be prepared by reacting 4,4'-oxydiphthalic anhydride with 3,4,3',4'-biphenyltetracarboxylic dianhydride and 3,4'-oxydiisocyanate. Also, the copolyimide may be prepared by reacting the corresponding tetra acid and ester precursors of 4,4'-oxydiphthalic anhydride and 3,4,3',4'-biphenyltetracarboxylic dianhydride with 3,4'-oxydianiline. These copolyimides were found to be soluble in common amide solvents such as N,N'-dimethyl acetamide, N-methylpyrrolidinone, and dimethylformamide allowing them to be applied as the fully imidized copolymer and to be used to prepare a wide range of articles.

  11. Determination of naloxone and naltrexone as perfluoroalkyl ester derivatives by electron-capture gas-liquid chromatography.

    PubMed

    Sams, R A; Malspeis, L

    1976-10-13

    An electron-capture gas chromatographic method is described for the determination of naloxone and naltrexone as the perfluoroalkyl esters. Each compound serves as internal standard for determination of the other. The method permits quantitation of 2-100 ng of either compound. Conditions for derivatization with heptafluorobutyric anhydride (HFBA), pentafluoropropionic anhydride (PFPA), and trifluoroacetic anhydride (TFAA) have been investigated. When catalyzed with pyridine, derivatization with HFBA and PFPA at 70 degrees gives naloxone and naltrexone triesters. Evidence for triester formation was obtained from gas chromatography-methane chemical ionization mass spectrometry and infrared spectral analysis. It was found that both the HFB and PFP triesters are suitable for quantitation of the narcotic antagonists, the HFB derivatives having greater stability than the PFP derivatives. The TFA derivatives are substantially less stable.

  12. Skin sensitization and possible groupings for 'read across' for rosin based substances.

    PubMed

    Illing, H P A; Malmfors, T; Rodenburg, L

    2009-08-01

    A series of chemically modified rosin resins have been tested for their potential to cause skin sensitization using the mouse LLNA. Where direct comparative evidence is available, the results of the mouse LLNA are consistent with previously obtained data using the GPMT. Reactions with sufficient fumaric acid or maleic anhydride lead to maleopimaric acid anhydride (an acid anhydride), and give a clear response of a strong sensitizer that definitely requires classification. This sensitization is probably immunologically distinct from that claimed for oxidized rosin. Esterification will deactivate acid anhydrides formed from reacting rosin with maleic anhydride or fumaric acid. However, with maleic anhydride, there remains material capable of inducing a marginal (but classifiable under current criteria) immune response after the rosin had been maleinated and esterified. If proposed potency criteria are used these substances would not be considered 'strong sensitizers'. This response may be a function of a greater solubility in vehicle of the esterified maleinated (or fumarated) rosin over directly esterified material. Solubility limitations in the case of gum rosin directly esterified with pentaerythritol mean that it is not classifiable. Decarboxylated rosin and the glycerol ester of tall oil rosin are adequately soluble, and are not classifiable according to EU criteria. Polymers formed from rosin are also not classifiable as sensitizers. These studies confirm the value of grouping substances for 'read across' and the groupings chosen under the US EPA High Production Volume (HPV) Challenge Program. They also confirm the difficulties involved in dealing scientifically when examining the problem of skin sensitization associated with rosin related substances whilst still meeting current EU regulatory criteria.

  13. Mechanistic Investigation into the Decarboxylation of Aromatic Carboxylic Acids

    SciTech Connect

    Britt, P F; Buchanan, III, A C; Eskay, T P; Mungall, W S

    1999-08-22

    It has been proposed that carboxylic acids and carboxylates are major contributors to cross-linking reactions in low-rank coals and inhibit its thermochemical processing. Therefore, the thermolysis of aromatic carboxylic acids was investigated to determine the mechanisms of decarboxylation at temperatures relevant to coal processing, and to determine if decarboxylation leads to cross-linking (i.e., formation of more refractory products). From the thcrmolysis of simple and polymeric coal model compounds containing aromatic carboxylic acids at 250-425 °C, decarboxylation was found to occur primarily by an acid promoted ionic pathway. Carboxylate salts were found to enhance the decarboxylation rate, which is consistent with the proposed cationic mechanism. Thermolysis of the acid in an aromatic solvent, such as naphthalene, produced a small amount of arylated products (~5 mol%)), which constitute a low-temperature cross-link. These arylated products were formed by the rapid decomposition of aromatic anhydrides, which are in equilibrium with the acid. These anhydrides decompose by a free radical induced decomposition pathway to form atyl radicals that can add to aromatic rings to form cross-links or abstract hydrogen. Large amounts of CO were formed in the thennolysis of the anhydrides which is consistent with the induced decomposition pathway. CO was also formed in the thermolysis of the carboxylic acids in aromatic solvents which is consistent with the formation and decomposition of the anhydride. The formation of anhydride linkages and cross-links was found to be very sensitive to the reactions conditions. Hydrogen donor solvents, such as tetralin, and water were found to decrease the formation of arylated products. Silar reaction pathways were also found in the thermolysis of a polymeric model that contained aromatic carboxylic acids. In this case, anhydride formation and decomposition produced an insoluble polymer, while the O-methylated polymer and the non

  14. Synthesis of acrylates and methacrlyates from coal-derived syngas. Quarterly technical progress report, January 1, 1995--March 31, 1995

    SciTech Connect

    Tischer, R.E.; Spivey, J.J.

    1995-08-01

    The objective Task 1, Synthesis of Propionates, is to develop the technology for the synthesis of low-cost propionates. These propionates are the basic feedstock for the subsequent reaction with formaldehyde to produce the target molecule, methyl methacrylate (MMA). Eastman has explored several possible routes to the propionates and has concluded that the most promising is the synthesis of propionic anhydride from the reaction of propionic acid from and ethylene (and also hydrogen in some cases). The main advantage of the anhydride over the acid is that its subsequent reaction with formaldehyde does not produce water, which can lead to undesired byproducts. Bechtel is carrying out a cost analysis of the Eastman route to the anhydride to determine if it is potentially competitive with commercially practiced routes to the same molecule. The answer is expected next quarter. The objective Task 2, Condensation Catalysis to develop catalysts for the condensation of the propionate (propionic anhydride is our target molecule) with formaldehyde. This reaction produces methacrylic acid (MAA), which would then be reacted with methanol to produce MMA in the slurry reactor. We have synthesized a wide range of catalysts and the results show that there is substantial byproduct formation, including 3-pentanone and some propionic acid. Our results show the highest yields of MAA using an alkalized alumina (1%Na/{sub y}-AI{sub 2}O{sub 3}). Although the condensation of propionic acid with formaldehyde is well studied in the literature, little is reported on the condensation of the anhydride. Although it is likely that the same general types of acid/base catalysts that promote the acid condensation will also promote that of the anhydride, the strength and balance of the acid and base sites is likely to be different. We plan to explore the relationship of the catalyst properties and MMA yields using the Altamira system, due to be delivered this next quarter.

  15. Regenerable solid imine sorbents

    DOEpatents

    Gray, McMahan; Champagne, Kenneth J.; Fauth, Daniel; Beckman, Eric

    2013-09-10

    Two new classes of amine-based sorbents are disclosed. The first class comprises new polymer-immobilized tertiary amine sorbents; the second class new polymer-bound amine sorbents. Both classes are tailored to facilitate removal of acid anhydrides, especially carbon dioxide (CO.sub.2), from effluent gases. The amines adsorb acid anhydrides in a 1:1 molar ratio. Both classes of amine sorbents adsorb in the temperature range from about 20.degree. C. upwards to 90.degree. C. and can be regenerated by heating upwards to 100.degree. C.

  16. Detergent compositions, their manufacture and their use as additives for fuels

    SciTech Connect

    Cohen, C.; Maldonado, P.; Sillion, B.

    1983-03-08

    A nitrogen-containing composition, useful as a detergent for gasoline, is obtained by reacting at least one unsaturated anhydride with at least one olefin to convert 20-80% of the anhydride and thereafter reacting the resultant product with a polyamine of the general formula H/sub 2/n-((-CH/sub 2/-)-n NH)mR/sub 7/ wherein R/sub 7/ is a monovalent aliphatic radical of 6-30 carbon atoms, n is an integer from 2 to 5 and m is an integer.

  17. Tougher Addition Polyimides Containing Siloxane

    NASA Technical Reports Server (NTRS)

    St. Clair, T. L.; Maudgal, S.

    1986-01-01

    Laminates show increased impact resistances and other desirable mechanical properties. Bismaleamic acid extended by reaction of diaminosiloxane with maleic anhydride in 1:1 molar ratio, followed by reaction with half this molar ratio of aromatic dianhydride. Bismaleamic acid also extended by reaction of diaminosiloxane with maleic anhydride in 1:2 molar ratio, followed by reaction with half this molar ratio of aromatic diamine (Michael-addition reaction). Impact resistances improved over those of unmodified bismaleimide, showing significant increase in toughness. Aromatic addition polyimides developed as both matrix and adhesive resins for applications on future aircraft and spacecraft.

  18. Pulmonary hemorrhage due to inhalation of vapor containing pyromellitic dianhydride.

    PubMed

    Kaplan, V; Baur, X; Czuppon, A; Ruegger, M; Russi, E; Speich, R

    1993-08-01

    Pulmonary hemorrhage due to inhalation of fumes or powders containing trimellitic anhydride (TMA) is well known. We report pulmonary hemorrhage in a young man exposed to epoxy resin vapor containing pyromellitic dianhydride (PMDA). Serum IgG antibodies to PMDA could be detected. We conclude that the pulmonary hemorrhage was mediated by a reaction to PMDA in analogy to the TMA-induced disease. We suggest that exposure to any acid anhydride should be considered a possible cause of pulmonary hemorrhage since these compounds share structural and functional similarities.

  19. Pretreatment of solid carbonaceous material with dicarboxylic aromatic acids to prevent scale formation

    SciTech Connect

    Brunson, R.J.

    1982-06-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a pretreating agent selected from the group consisting of phthalic acid, phthalic anhydride, pyromellitic acid and pyromellitic anhydride. The pretreatment is believed to convert the scale-forming components to the corresponding phthalate and/or pyromellitate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 1 to about 2 atmospheres. Temperature during pretreatment will generally be within the range from about 5 to about 80/sup 0/ C.

  20. Pretreatment of solid carbonaceous material with dicarboxylic aromatic acids to prevent scale formation

    SciTech Connect

    Brunson, Roy J.

    1982-01-01

    Scale formation during the liquefaction of lower ranking coals and similar carbonaceous materials is significantly reduced and/or prevented by pretreatment with a pretreating agent selected from the group consisting of phthalic acid, phthalic anhydride, pyromellitic acid and pyromellitic anhydride. The pretreatment is believed to convert the scale-forming components to the corresponding phthalate and/or pyromellitate prior to liquefaction. The pretreatment is accomplished at a total pressure within the range from about 1 to about 2 atmospheres. Temperature during pretreatment will generally be within the range from about 5.degree. to about 80.degree. C.