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Repeating Unit (repeating + unit)
Kinds of Repeating Unit Selected AbstractsSynthesis of the Trisaccharide Repeating Unit of the Atypical O-Antigen Polysaccharide from Danish Helicobacter pylori Strains Employing the 2,-Carboxybenzyl Glycoside.CHEMINFORM, Issue 7 2005Yong Tae Kwon No abstract is available for this article. [source] An Expedient Synthesis of the Repeating Unit of the Acidic Polysaccharide of the Bacteriolytic Complex of Lysoamidase,CHEMISTRY - A EUROPEAN JOURNAL, Issue 3 2005Remy E. J. N. Litjens Abstract The first synthesis of the trisaccharide repeating unit of the acidic polysaccharide of the bacteriolytic complex of lysoamidase is presented. The construction is based on a linear glycosylation strategy that starts from the reducing end and employs thio- and selenoglycosides in a highly stereoselective manner by a single set of activation conditions. The thus-formed trisaccharide is selectively deprotected and oxidised, after which a final deprotection step furnishes the desired repeating unit. [source] Structural Studies of the O-Chain Polysaccharide from Plesiomonas shigelloides Strain 302,73 (Serotype O1)EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 18 2008Giuseppina Pieretti Abstract Plesiomonas shigelloides is a Gram-negative bacterium belonging to the Enterobacteriaceae family. It has been found in an aquatic environment in the tropical and subtropical regions and is responsible for many gastrointestinal infections in humans, which take place from drinking untreated water or eating uncooked shellfish. Plesiomonas shigelloides has also been reported to provoke extraintestinal infections such as meningitis and bacteremia in immunocompromised adults and neonates. Despite the emerging importance of this pathogenic microorganism, only three different O-antigens have been characterised so far. The structure of the O-chain of the lipopolysaccharide (LPS) from Plesiomonasshigelloides strain 302,73 (serotype O1) was determined by chemical analysis, 1D and 2D NMR spectroscopy and MALDI-TOF mass spectrometry. The polysaccharide was constituted by a linear pentasaccharidic repeating unit as follows: ,3)-,- L -PneNAc4OAc(1,4)-,- L -FucNAc(1,4)-,- L -FucNAc(1,4)-,- L -FucNAc(1,3)-,- D -QuiNAc4NHb(1, (PneNAc = 2-acetamido-2,6-dideoxy-talose, Hb = (S)-3-hydroxybutanoyl) PneNAc O -acetylation was not stoichiometric and was found to be about 75,%. The position of the O -acetyl group and the amount of acetylation were deduced by NMR spectroscopic analysis. All the monosaccharides included in the repeating unit were deoxyamino sugars, which most probably, together with the presence of O -acetyl groups, were responsible for the recovery of the LPS in the phenol layer of the phenol/water extract of dried bacteria cells.(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008) [source] Structural Determination of the O-Chain Polysaccharide from the Lipopolysaccharide of the Haloalkaliphilic Halomonas pantelleriensis Bacterium,EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, Issue 7 2006M. Michela Corsaro Abstract The structural determination of the O-chain repeating unit of the lipopolysaccharide from the haloalkaliphilic Halomonas pantelleriensis bacterium is described. The structure of the repeating unit was suggested on the basis of chemical analysis and NMR and MS data. The 4- O -[(S)-1-carboxyethyl]- D -GlcA residue has been found for the first time in a lipopolysaccharide, being previously only found in capsular polysaccharides. A comparison of the O-chain structures of Halomonas magadiensis and H. pantelleriensis is also reported. The results show that both bacteria present lipopolysaccharides containing a high number of carboxylate groups whose salification might determine a protective buffer effect on bacterium against extreme life conditions. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006) [source] Structure of the O-polysaccharide from Proteus myxofaciensFEBS JOURNAL, Issue 15 2003Classification of the bacterium into a new Proteus O-serogroup The O-polysaccharide (O-antigen) was obtained from the lipopolysaccharide of Proteus myxofaciens, a Proteus strain producing copious amounts of slime, which was isolated from the gypsy moth larvae. The structure of the polysaccharide was studied by chemical analysis and 1H and 13C NMR spectroscopy, including 2D COSY, TOCSY, ROESY and H-detected 1H,13C HMQC experiments. It was found that the polysaccharide contains an amide of glucuronic acid (GlcA) with an unusual ,-linked amino acid, N, -[(R)-1-carboxyethyl]- l -lysine (2S,8R -alaninolysine, 2S,8R -AlaLys), and has a linear tetrasaccharide repeating unit of the following structure: This structure is unique among known bacterial polysaccharide structures. On the basis of these and serological data, it is proposed that P. myxofaciens be classified into a new Proteus serogroup, O60, of which this strain is the single representative. Structural and serological relatedness of P. myxofaciens to other AlaLys-containing O-antigens of Proteus and Providencia is discussed. [source] Structural determination of the O-chain polysaccharide from Agrobacterium tumefaciens, strain DSM 30205FEBS JOURNAL, Issue 12 2002Cristina De Castro Agrobacterium tumefaciens is a Gram-negative, phytopathogenic bacterium and is characterized by an unique mode of action on dicotyledonous plants: it is able to genetically modify the host, and because of this feature, it is used as a tool for transgenic plants. Many experiments have demonstrated that lipopolysaccharides (LPSs) play an important role for the disease development, as they are involved in the adhesion process of the bacterium on the plant cell wall. Despite the wealth of information on the role of LPS on phytopathogenesis, the present paper appears as the first report on the molecular primary structure of the O-chain produced from Agrobacterium. Its repeating unit was determined by means of chemical and spectroscopical analysis, and has the following structure: (3)-,- d -Araf -(1,3)-,- l -Fucp -(1,. [source] Structural studies on the core and the O-polysaccharide repeating unit of Pseudomonas aeruginosa immunotype 1 lipopolysaccharideFEBS JOURNAL, Issue 8 2002Olga V. Bystrova The structure of the lipopolysaccharide (LPS) of Pseudomonas aeruginosa immunotype 1 was studied after mild acid and strong alkaline degradations by MS and NMR spectroscopy. Three types of LPS molecules were found, including those with an unsubstituted glycoform 1 core (A) or an isomeric glycoform 2 core substituted with one O-polysaccharide repeating unit (B) or with a long-chain O-polysaccharide. Therefore, of two core glycoforms, only glycoform 2 accepts the O-polysaccharide. In the structures A and B, Kdo, Hep, Hep7Cm, GalNAcAN3Ac, GalNFoAN, QuiNAc, GalNAla represent 3-deoxy- d - manno -octulosonic acid, l - glycero - d - manno -heptose, 7- O- carbamoyl- l - glycero - d - manno -heptose, 2-acetamido-3- O -acetyl-2-deoxygalacturonamide, 2-formamido-2-deoxygalacturonamide, 2-acetamido-2,6-dideoxyglucose and 2-(l -alanylamino)-2-deoxygalactose, respectively; all sugars are in the pyranose form and have the d configuration unless otherwise stated. One or more phosphorylation sites may be occupied by diphosphate groups. In a minority of the LPS molecules, an O-acetyl group is present in the outer core region at unknown position. The site and the configuration of the linkage between the O-polysaccharide and the core and the structure of the O-polysaccharide repeating unit were defined in P. aeruginosa immunotype 1. The QuiNAc residue linked to the Rha residue of the core was found to have the , configuration, whereas in the interior repeating units of the O-polysaccharide this residue is in the ,-configuration. The data obtained are in accordance with the initiation of biosynthesis of the O-polysaccharide of P. aeruginosa O6, which is closely related to immunotype 1, by transfer of d -QuiNAc-1- P to undecaprenyl phosphate followed by synthesis of the repeating O-antigen tetrasaccharide. [source] Structures of two cell wall-associated polysaccharides of a Streptococcus mitis biovar 1 strainFEBS JOURNAL, Issue 24 2000A unique teichoic acid-like polysaccharide, the group O antigen which is a C-polysaccharide in common with pneumococci The cell wall of Streptococcus mitis biovar 1 strain SK137 contains the C-polysaccharide known as the common antigen of a closely related species Streptococcus pneumoniae, and a teichoic acid-like polysaccharide with a unique structure. The two polysaccharides are different entities and could be partially separated by gel chromatography. The structures of the two polysaccharides were determined by chemical methods and by NMR spectroscopy. The teichoic acid-like polymer has a heptasaccharide phosphate repeating unit with the following structure: The structure neither contains ribitol nor glycerol phosphate as classical teichoic acids do, thus we have used the expression teichoic acid-like for this polysaccharide. The following structure of the C-polysaccharide repeating unit was established: where AAT is 2-acetamido-4-amino-2,4,6-trideoxy- d -galactose. It has a carbohydrate backbone identical to that of one of the two structures of C-polysaccharide previously identified in S. pneumoniae. C-polysaccharide of S. mitis is characterized by the presence, in each repeating unit, of two residues of phosphocholine and both galactosamine residues in the N-acetylated form. Immunochemical analysis showed that C-polysaccharide constitutes the Lancefield group O antigen. Studies using mAbs directed against the backbone and against the phosphocholine moiety of the C-polysaccharide revealed several different patterns of these epitopes among 95 S. mitis and Streptococcus oralis strains tested and the exclusive presence of the group O antigen in the majority of S. mitis biovar 1 strains. [source] The identity of the O-specific polysaccharide structure of Citrobacter strains from serogroups O2, O20 and O25 and immunochemical characterisation of C. youngae PCM 1507 (O2a,1b) and related strainsFEMS IMMUNOLOGY & MEDICAL MICROBIOLOGY, Issue 1-2 2003gorzata Miesza Abstract Serological studies using SDS,PAGE and immunoblotting revealed that from five strains that are ascribed to Citrobacter serogroup O2, four strains, PCM 1494, PCM 1495, PCM 1496 and PCM 1507, are reactive with specific anti- Citrobacter O2 serum. In contrast, strain PCM 1573 did not react with anti- Citrobacter O2 serum and, hence, does not belong to serogroup O2. The LPS of Citrobacter youngae O2a,1b (strain PCM 1507) was degraded under mild acidic conditions and the O-specific polysaccharide (OPS) released was isolated by gel chromatography. Sugar and methylation analyses along with 1H- and 13C-NMR spectroscopy, including two-dimensional 1H,1H COSY, TOCSY, NOESY and 1H,13C HSQC experiments, showed that the repeating unit of the OPS has the following structure: NMR spectroscopic studies demonstrated that Citrobacter werkmanii O20 and C. youngae O25 have the same OPS structure as C. youngae O2. Sugar and methylation analyses of the core oligosaccharide fractions demonstrated structural differences in the lipopolysaccharide core regions of these strains, which may substantiate their classification in different serogroups. [source] Radical Polymers for Organic Electronic Devices: A Radical Departure from Conjugated Polymers?ADVANCED MATERIALS, Issue 22 2009Kenichi Oyaizu Abstract Radical polymers are aliphatic or nonconjugated polymers bearing organic robust radicals as pendant groups per repeating unit. A large population of the radical redox sites allows the efficient redox gradient-driven electron transport through the polymer layer by outer-sphere self-exchange reactions in electrolyte solutions. The radical polymers are emerging as a new class of electroactive materials useful for various kinds of wet-type energy storage, transport, and conversion devices. Electric-field-driven charge transport by hopping between the densely populated radical sites is also a remarkable aspect of the radical polymers in the solid state, which leads to many dry-type devices such as organic memories, diodes, and switches. [source] Influence of azobenzene units on imidization kinetic of novel poly(ester amic acid)s and polymers properties before and after cyclodehydrationJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2010Ewa Schab-Balcerzak Abstract In this article, the imidization reaction kinetic of novel poly(ester amic acid)s with azobenzene units as side groups was studied by dynamic experiments by means of differential scanning calorimetry. Polymers differ in the number of chromophore moieties in their repeating unit and position in which azobenzene group is attached to the polymer chain. The kinetic parameters of poly(ester amic acid)s conversion to poly(ester imide)s was compared with data calculated for parent polymer, that is, without azobenzene groups. For the first time to our knowledge, the imidization kinetic of polymers with side azobenzene groups was studied. Kinetic parameters, such as the activation energy and frequency factor were estimated with the by Ozawa model [(E(O) and A(O)), respectively] and Kissinger model [(E(K) and A(K), respectively]. The values of activation energy determined with both models were in the range 167.1,198.3 kJ/mol. The lowest activation energy of imidization reaction exhibited polymer in which azobenzene units were placed between amide linkages. Polymers were characterized by FTIR, 1H-NMR, X-ray, and UV,vis methods. The glass transition temperature of resultant poly(ester imide)s was in the range of 217,237°C. The presence of chromophore units slightly decreased Tg and significantly improved their solubility and optical properties. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010 [source] Synthesis, characterization, and comparison of properties of novel fluorinated poly(imide siloxane) copolymersJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2008Anindita Ghosh Abstract Four new poly(imide siloxane) copolymers were prepared by a one-pot solution imidization method at a reaction temperature of 180°C in ortho -dichlorobenzene as a solvent. The polymers were made through the reaction of o -diphthaleic anhydride with four different diamines,4,4,-bis(p -aminophenoxy-3,3,-trifluoromethyl) terphenyl, 4,4,-bis(3,-trifluoromethyl- p -aminobiphenyl ether)biphenyl, 2,6-bis(3,-trifluoromethyl- p -aminobiphenyl ether)pyridine, and 2,5-bis(3,-trifluoromethyl- p -aminobiphenylether)thiopene,and aminopropyl-terminated poly dimethylsiloxane as a comonomer. The polymers were named 1a, 1b, 1c, and 1d, respectively. The synthesized polymers showed good solubility in different organic solvents. The resulting polymers were well characterized with gel permeation chromatography, IR, and NMR techniques. 1H-NMR indicated that the siloxane loading was about 36%, although 40 wt % was attempted. 29Si-NMR confirmed that the low siloxane incorporation was due to a disproportionation reaction of the siloxane chain that resulted in a lowering of the siloxane block length. The films of these polymers showed low water absorption of 0.02% and a low dielectric constant of 2.38 at 1 MHz. These polyimides showed good thermal stability with decomposition temperatures (5% weight loss) up to 460°C in nitrogen. Transparent, thin films of these poly(imide siloxane)s exhibited tensile strengths up to 30 MPa and elongations at break up to 103%, which depended on the structure of the repeating unit. The rheological properties showed ease of processability for these polymers with no change in the melt viscosity with the temperature. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Hydrophilic functionalization of syndiotactic polystyrene via a combination of electrophilic bromination and Suzuki,Miyaura reactionJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 19 2010Jihoon Shin Abstract Postfunctionalization of high-molecular-weight syndiotactic polystyrene (sPS) was achieved via combination of electrophilic bromination at the para-position of the polymer aromatic ring and subsequent Suzuki,Miyaura cross-coupling reactions with functionalized phenylboronic acids. The concentration of brominated styrene repeating unit in sPS was conveniently controlled by changing the ratio of added bromine relative to the polymer repeating unit. Brominated sPS (8.5 mol %) was converted quantitatively to other polar functional groups via Suzuki,Miyaura cross-coupling reactions with various functional group-substituted phenylboronic acids. The surface properties of functionalized sPS were studied by measuring water contact angles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 4335,4343, 2010 [source] Phase behavior and photo-responsive studies of photoactive liquid crystalline hyperbranched polyethers containing benzylidene moietyJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 11 2009V. Srinivasa Rao Abstract Two sets of hyperbranched polyether epoxies were synthesized to study the effect of substituent, rigidity, and nature of photoactive unit on the thermal and photoresponsive properties. Each set was comprised of one molecule with an acyclic moiety in the repeating unit, and two molecules with a cyclic moiety of varying rigidity (cycle size) in the repeating unit. Two substituents on aromatic rings in the repeating unit were present in one set, and other set was without a substituent. The mesogenic and photoresponsive properties were studied and correlated to the varied structural parameters. The effects of varied molecular structural parameters on phase behavior and photoresponsive properties were very prominent. Out of six monomeric diols, only four have exhibited liquid crystalline phase while the polymers corresponding to all monomeric diols revealed mesophase. The findings in photoresponsive properties were further supported by molecular modeling studies. The changes in refractive index, photoviscosity, and fluorescence intensity with irradiation time substantiated the spectral pattern observed in UV-Vis spectroscopy. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2774,2786, 2009 [source] Linear polyurethanes made from naturally occurring tartaric acidJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2009Romina Marín Abstract Naturally occurring tartaric acid was used as raw material for the synthesis of novel linear polyurethanes (PURs) bearing two carboxylate side-groups in the repeating unit. Aliphatic and aromatic PURs were obtained by reaction in solution of alkyl and benzyl tartrates with hexamethylene diisocyanate and 4,4,-methylene-bis(phenyl isocyanate), respectively. All the novel PURs were thermally stable and optically active. The aliphatic carboxylate-containing PURs had Mw in the 40,70 kDa range, with PD between 2.1 and 2.5; all were semicrystalline polymers with melting temperatures between 100 and 150 °C and Tg in the 50,80 °C range. The aromatic PURs were amorphous materials with molecular weights between 18 kDa and 25 kDa and Tg above 130 °C. Hydrogenolysis of the PUR made from hexamethylene diisocyanate and benzyl tartrate yielded PURs containing up to 40% of free carboxylic side-groups. The tartrate-derived PURs displayed enhanced sensitivity to hydrolysis compared with their unsubstituted 2,6-PUR homologs. The PURs bearing free carboxylic groups were unique in being degraded by water upon incubation under physiological conditions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 2391,2407, 2009 [source] Acyclic diene metathesis polymerization of 2,5-dialkyl-1,4-divinylbenzene with molybdenum or ruthenium catalysts: Factors affecting the precise synthesis of defect-free, high-molecular-weight trans -poly(p -phenylene vinylene)sJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 23 2005Kotohiro Nomura Abstract Factors affecting the syntheses of high-molecular-weight poly(2,5-dialkyl-1,4-phenylene vinylene) by the acyclic diene metathesis polymerization of 2,5-dialkyl-1,4-divinylbenzenes [alkyl = n -octyl (2) and 2-ethylhexyl (3)] with a molybdenum or ruthenium catalyst were explored. The polymerizations of 2 by Mo(N -2,6-Me2C6H3) (CHMe2 Ph)[OCMe(CF3)2]2 at 25 °C was completed with both a high initial monomer concentration and reduced pressure, affording poly(p -phenylene vinylene)s with low polydispersity index values (number-average molecular weight = 3.3,3.65 × 103 by gel permeation chromatography vs polystyrene standards, weight-average molecular weight/number-average molecular weight = 1.1,1.2), but the polymerization of 3 was not completed under the same conditions. The synthesis of structurally regular (all- trans), defect-free, high-molecular-weight 2-ethylhexyl substituted poly(p -phenylene vinylene)s [poly3; degree of monomer repeating unit (DPn) = ca. 16,70 by 1H NMR] with unimodal molecular weight distributions (number-average molecular weight = 8.30,36.3 × 103 by gel permeation chromatography, weight-average molecular weight/number-average molecular weight = 1.6,2.1) and with defined polymer chain ends (as a vinyl group, CHCH2) was achieved when Ru(CHPh)(Cl)2(IMesH2)(PCy3) or Ru(CH-2-OiPr-C6H4)(Cl)2(IMesH2) [IMesH2 = 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene] was employed as a catalyst at 50 °C. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 6166,6177, 2005 [source] Stereocontrolled anionic alternating copolymerization of ethylphenylketene with benzaldehyde by a bisoxazoline ligandJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 21 2004Daisuke Nagai Abstract Anionic copolymerization of ethylphenylketene with benzaldehyde with butyllithium or diethylzinc as the initiator proceeded in a perfect 1:1 alternating manner to produce the corresponding polyester, whose repeating unit had two adjacent chiral centers. The relative stereochemistry between these two chiral centers was successfully controlled by the addition of (S,S)-(-)-2,2,-isopropylidenebis(4- tert -butyl-2-oxazoline), producing the corresponding polyester that had excellent diastereoselectivity (erythro -configuration : threo -configuration = 4:96). The diastereomeric ratio was determined by high-performance liquid chromatography analysis of the diol, which was obtained by reductive degradation of the polyester while maintaining the configuration of the repeating unit. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5384,5388, 2004 [source] Structure,property correlations of sulfonated polyimides.JOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 14 2004Abstract A series of six-membered sulfonated polyimides were synthesized using 1,4,5,8-naphthalenetetracarboxylic dianhydride, 4,4,-diaminobiphenyl 2,2,-disulfonic acid as the sulfonated diamine, and various nonsulfonated diamine monomers having different bridging groups. These bulky bridging groups have the capacity to increase hydrolytic stability and proton conductivity. Polyimides with bulky bridging groups showed increased solubility but exhibited lower thermal stability. The ion exchange capacity and water uptake reduced with increase in the bulkiness of the bridging group. This was attributed to the increase in the molecular weight of the repeating unit and hence effectively reduced the sulfonic acid content. In low temperatures, the conductivity was lower than Nafion®115 and, with increase in temperature, the conductivity rapidly increased and exhibited better conductivity than Nafion®115. Polyimides with bulky bridging groups 4-amino phenyl sulfone, and 2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane showed higher conductivity than other polyimides and Nafion®115 despite low ion exchange capacity. The hydrolytic stability of the polyimides with bulky bridging groups was higher than the polyimides with less bulky atoms because of the imparted flexibility. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3612,3620, 2004 [source] Synthesis of new crosslinkable polymers by chemoselective polymerizations of 2-(1-aziridinyl)ethyl methacrylateJOURNAL OF POLYMER SCIENCE (IN TWO SECTIONS), Issue 9 2003Takashi Ishizone The anionic vinyl polymerization of 2-(1-aziridinyl)ethyl methacrylate (1) quantitatively proceeded with diphenylmethylpotassium in the presence of diethylzinc in tetrahydrofuran at ,78 °C for 12 h to form a polymethacrylate (2) with an aziridine ring in each repeating unit. The resulting polymer 2 possessed the predicted molecular weight and narrow molecular weight distribution (weight-average molecular/number-average molecular weight < 1.1) and became readily insoluble by treatment with adipic acid via the crosslinking of the pendant aziridinyl moiety. A poly(ethylene imine) bearing methacryloyl pendant groups was obtained with triethyloxonium tetrafluoroborate via the cationic ring-opening polymerization of 1 in heptane/dichloromethane at 0 °C for 2 h. [source] Polymers from Multifunctional Isocyanates, 15,MACROMOLECULAR CHEMISTRY AND PHYSICS, Issue 8 2007A Novel Alternating Copolymer Containing an Isocyanate, a Cyanate Group in the Repeating Unit Abstract N -(4-cyanatophenyl)maleimide and 2-isocyanato propene were copolymerised to give an alternating copolymer, which is the first example of a polymer having an isocyanate as well as a cyanate reactive functional group in the repeating unit. The polymer analogous reaction with methanol proceeded selectively at the isocyanate groups. Crosslinking of the cyanate-urethane copolymers by cyclotrimerisation of cyanate groups occurred at elevated temperature. Reaction with dibutylamine at 20,°C led to complete reaction of both the cyanate and isocyanate moieties in a non-selective manner. [source] Synthesis of Optically Active Polymer with P-Stereogenic Phosphine UnitsMACROMOLECULAR RAPID COMMUNICATIONS, Issue 19 2010Yasuhiro Morisaki Abstract Optically active polymer containing P-stereogenic bisphosphine as a repeating unit in the main was successfully synthesized. A coordinated borane on the phosphorus atom could be completely removed by an organic base under mild condition, and the successive reaction with Pd afforded the corresponding polymer complex. The chirality of P-stereogenic centers was transferred to the m-phenylene-ethynylene linkers by complexation because of the prohibition of the rotary motion of the bisphosphine-Pd unit. [source] QSPR Analysis of Copolymers by Recursive Neural Networks: Prediction of the Glass Transition Temperature of (Meth)acrylic Random CopolymersMOLECULAR INFORMATICS, Issue 8-9 2010Carlo Giuseppe Bertinetto Abstract The glass transition temperature (Tg) of acrylic and methacrylic random copolymers was investigated by means of Quantitative Structure-Property Relationship (QSPR) methodology based on Recursive Neural Networks (RNN). This method can directly take molecular structures as input, in the form of labelled trees, without needing predefined descriptors. It was applied to three data sets containing up to 615 polymers (340 homopolymers and 275,copolymers). The adopted representation was able to account for the structure of the repeating unit as well as average macromolecular characteristics, such as stereoregularity and molar composition. The best result, obtained on a data set focused on copolymers, showed a Mean Average Residual (MAR) of 4.9,K, a standard error of prediction (S) of 6.1,K and a squared correlation coefficient (R2) of 0.98 for the test set, with an optimal rate with respect to the training error. Through the treatment of homopolymers and copolymers both as separated and merged data sets, we also showed that the proposed approach is particularly suited for generalizing prediction of polymer properties to various types of chemical structures in a uniform setting. [source] Structural analysis of a novel anionic polysaccharide from Porphyromonas gingivalis strain W50 related to Arg-gingipain glycansMOLECULAR MICROBIOLOGY, Issue 3 2005Nikolay Paramonov Summary The Arg-gingipains (RgpsA and B) of Porphyromonas gingivalis are a family of extracellular cysteine proteases and are important virulence determinants of this periodontal bacterium. A monoclonal antibody, MAb1B5, which recognizes an epitope on glycosylated monomeric RgpAs also cross-reacts with a cell-surface polysaccharide of P. gingivalis W50 suggesting that the maturation pathway of the Arg-gingipains may be linked to the biosynthesis of a surface carbohydrate. We report the purification and structural characterization of the cross-reacting anionic polysaccharide (APS), which is distinct from both the lipopolysaccharide and serotype capsule polysaccharide of P. gingivalis W50. The structure of APS was determined by 1D and 2D NMR spectroscopy and methylation analysis, which showed it to be a phosphorylated branched mannan. The backbone is built up of ,-1,6-linked mannose residues and the side-chains contain ,-1,2-linked mannose oligosaccharides of different lengths (one to two sugar residues) attached to the backbone via 1,2-linkage. One of the side-chains in the repeating unit contains Man,1-2Man,1-phosphate linked via phosphorus to a backbone mannose at position 2. De- O -phosphorylation of APS abolished cross-reactivity suggesting that Man,1-2Man,1-phosphate fragment forms part of the epitope recognized by MAb1B5. This phosphorylated branched mannan represents a novel polysaccharide that is immunologically related to the post-translational additions of Arg-gingipains. [source] Synthesis and NMR characterization of 6-Phenyl-6-deoxy-2,3-di- O -methylcellulose,POLYMERS FOR ADVANCED TECHNOLOGIES, Issue 6 2002Dr Navzer (Nozar) D. Sachinvala Abstract Cellulose (1) was converted for the first time to 6-phenyl-6-deoxy-2,3-di- O -methylcellulose (6) in 33% overall yield. Intermediates in the five-step conversion of 1 to6 were: 6- O -tritylcellulose (2), 6- O -trityl-2,3-di- O -methylcellulose (3), 2,3-di- O -methylcellulose (4); and 6-bromo-6-deoxy-2,3-di- O -methylcellulose (5). Elemental and quantitative carbon-13 analyses were concurrently used to verify and confirm the degrees of substitution in each new polymer. Gel permeation chromotography (GPC) data were generated to monitor the changes in molecular weight (DPw) as the synthesis progressed, and the compound average decrease in cellulose DPw was , 27%. Differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA) were used to characterize the decomposition of all polymers. The degradation temperatures (,°C) and percent char at 500,°C of cellulose derivatives 2 to 6 were 308.6 and 6.3%, 227.6,°C and 9.7%, 273.9,°C and 30.2%, 200.4,°C and 25.6%, and 207.2,°C and 27.0%, respectively. The glass transition temperature (Tg) of6- O -tritylcellulose by dynamic mechanical analysis (DMA) occurred at 126.7,°C and the modulus (E,, Pa) dropped 8.9 fold in the transition from ,150,°C to,+,180,°C (6.6,×,109 to 7.4,×,108 Pa). Modulus at 20,°C was 3.26,×,109 Pa. Complete proton and carbon-13 chemical shift assignments of the repeating unit of the title polymer were made by a combination of the HMQC and COSY NMR methods. Ultimate non-destructive proof of carbon,carbon bond formation at C6 of the anhydroglucose moiety was established by generating correlations between resonances of CH26 (anhydroglucose) and C1,, H2,, and H6, of the attached aryl ring using the heteronuclear multiple-bond correlation (HMBC) method. In this study, we achieved three major objectives: (a) new methodologies for the chemical modification of cellulose were developed; (b) new cellulose derivatives were designed, prepared and characterized; (c) unequivocal structural proof for carbon,carbon bond formation with cellulose was derived non-destructively by use of one- and two-dimensional NMR methods. Copyright © 2002 John Wiley & Sons, Ltd. [source] Matrix-assisted laser desorption/ionisation mass spectrometry for the direct analysis of enzymatically digested kappa - iota - and hybrid iota/nu -carrageenans,RAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 16 2005Aristotelis Antonopoulos Enzymatically digested oligosaccharides of kappa -, iota - and hybrid iota/nu -carrageenans were analysed using matrix-assisted laser desorption/ionisation time-of-flight mass spectrometry in the negative-ion mode. nor -Harmane was used as matrix. Depending on the stock concentration and the laser intensity applied, the oligosaccharides exhibited losses of sulphate units (neutralised by the Na+ ion, and thus non-stable), leaving the primary backbone structure in most cases with only the deprotonated sulphate groups (carrying the negative charge, stable). This meant that kappa - and iota -oligosaccharides could not be easily distinguished from one another since they share the same primary backbone structure. However, for the hybrid iota/nu -oligosaccharides the primary backbone structure could be identified since the nu -carrageenan repeating unit differs from that of the kappa/iota -carrageenan unit. For all types of oligosaccharides, the results indicated cleavage of an anhydrogalactose unit from the non-reducing end. Specifically, for the hybrid oligosaccharides of iota/nu -carrageenans, this type of fragmentation means that the nu -carrageenan unit is not positioned on the non-reducing end of the hybrid oligosaccharides. Dehydration reactions, and exchange reactions of Na+ with K+ and Ca2+, were also observed. Copyright © 2005 John Wiley & Sons, Ltd. [source] Electrospray mass spectrometry studies of macromolecules containing 1,3-oxazolidine moietiesRAPID COMMUNICATIONS IN MASS SPECTROMETRY, Issue 22 2004J. Ma, ska-Solich The polycondensation of terephthalaldehyde with 2-amino-2-methyl-1,3-propanediol using acidic catalysts leads to the formation of linear polymers and macrocyclic compounds with 2-(1,,4,-phenylene)-5-methyl-1-aza-3,7-dioxabicyclo[3.3.0]octane as the repeating unit in all compounds. The structure of the polymer was determined by 1H- and 13C-NMR spectroscopy, and electrospray ionization mass spectrometric (ESI-MS) analysis. ESI-MS measurements were used to study the details of the polymer structure and support the equimolar alternating nature of bicyclo- O,N -acetals of terephthaldehyde in these macromolecules. Copyright © 2004 John Wiley & Sons, Ltd. [source] Effects of an exopolysaccharide (kefiran) on lipids, blood pressure, blood glucose, and constipationBIOFACTORS, Issue 1-4 2004Hiroaki Maeda Abstract Lactobacillus kefiranofaciens was reported to produce an exopolysaccharide named kefiran. In the present study, we developed a new medium, rice hydrolyzate (RH) medium, for the culture of L. kefiranofaciens. Structural analyses revealed that the exopolysaccharide produced by L. kefiranofaciens from RH medium was composed of a hexasaccharide repeating unit, and essentially identical to the kefiran reported in previous studies. A study on the effects of kefiran in animals demonstrated that kefiran significantly suppressed increase of blood pressure and reduced the serum cholesterol levels in SHRSP/Hos rats when subjects consumed excessive dietary cholesterol. Kefiran supplementation demonstrated the ability to significantly lower blood glucose in KKAy mice. In addition, the administration of kefiran in constipated SD rats caused an obvious improvement in the levels of fecal moisture and wet weights of feces. These results suggest that kefiran could be used as a functional food to prevent some commonly occurring diseases. [source] Solvent-dependent conformation of amylose tris(phenylcarbamate) as deduced from scattering and viscosity dataBIOPOLYMERS, Issue 9 2009Taichi Fujii Abstract The z -average mean-square radius of gyration ,S2,z, the particle scattering function P(k), the second virial coefficient, and the intrinsic viscosity [,] have been determined for amylose tris(phenylcarbamate) (ATPC) in methyl acetate (MEA) at 25°C, in ethyl acetate (EA) at 33°C, and in 4-methyl-2-pentanone (MIBK) at 25°C by light and small-angle X-ray scattering and viscometry as functions of the weight-average molecular weight in a range from 2 × 104 to 3 × 106. The first two solvents attain the theta state, whereas the last one is a good solvent for the amylose derivative. Analysis of the ,S2,z, P(k), and [,] data based on the wormlike chain yields h (the contour length or helix pitch per repeating unit) = 0.37 ± 0.02 and ,,1 (the Kuhn segment length) = 15 ± 2 nm in MEA, h = 0.39 ± 0.02 and ,,1 = 17 ± 2 nm in EA, and h = 0.42 ± 0.02 nm and ,,1 = 24 ± 2 nm in MIBK. These h values, comparable with the helix pitches (0.37,0.40 nm) per residue of amylose triesters in the crystalline state, are somewhat larger than the previously determined h of 0.33 ± 0.02 nm for ATPC in 1,4-dioxane and 2-ethoxyethanol, in which intramolecular hydrogen bonds are formed between the CO and NH groups of the neighbor repeating units. The slightly extended helices of ATPC in the ketone and ester solvents are most likely due to the replacement of those hydrogen bonds by intermolecular hydrogen bonds between the NH groups of the polymer and the carbonyl groups of the solvent. © 2009 Wiley Periodicals, Inc. Biopolymers 91: 729,736, 2009. This article was originally published online as an accepted preprint. The "Published Online" date corresponds to the preprint version. You can request a copy of the preprint by emailing the Biopolymers editorial office at biopolymers@wiley.com [source] A pH-Based High-Throughput Screening of Sucrose-Utilizing Transglucosidases for the Development of Enzymatic Glucosylation ToolsCHEMCATCHEM, Issue 8 2010Elise Champion Dr. Abstract Sucrose-utilizing transglucosidases are valuable enzymatic tools for the diversification of carbohydrate-based molecules. Among them, recombinant amylosucrase from Neisseria polysaccharea is a glucansucrase that naturally catalyzes the synthesis of an amylose-like polymer as well as the transglucosylation of exogenous hydroxylated acceptors. A semirational engineering approach was recently undertaken to redesign the enzyme active site and adapt it to the glucosylation of a nonnatural acceptor, allyl 2- N -acetyl-2-deoxy-,- D -glucopyranoside (,- D -GlcpNAcOAll), to produce a key building block in the chemoenzymatic synthesis of Shigella flexneri 1b,serotype O-antigen repeating unit. This prior work shows the beneficial effect of single amino acid mutations at two positions (228 and 290) on the recognition of the acceptor by amylosucrase. On the basis of these first results, a library of about 8000 amylosucrase variants combining mutations at these two positions is constructed by saturation mutagenesis. The library is prescreened using a novel pH-sensitive colorimetric screening method for the detection of sucrose-utilizing amylosucrase variants, thereby reducing by about 95,% the size of the library to be subsequently screened for acceptor glucosylation. Active clones (5,% of the initial library) are then screened for acceptor recognition, leading to the isolation of 20 variants of potential interest for the production of the target disaccharide ,- D -Glcp-(1,4)-,- D -GlcpNAc. [source] Cyclopolymerization and Copolymerization of Functionalized 1,6-Heptadienes Catalyzed by Pd Complexes: Mechanism and Application to Physical-Gel FormationCHEMISTRY - A EUROPEAN JOURNAL, Issue 29 2010Sehoon Park Dr. Abstract Cationic Pd complexes, prepared from [PdCl(ArNC12H6NAr)(Me)] and Na[B{3,5(CF3)2C6H3}4] (NaBARF), catalyze the cyclopolymerization of 4,4-disubstituted 1,6-heptadienes. The polymers produced contain a trans -fused five-membered ring in each repeating unit. NMR spectroscopy and FAB mass spectrometry of the polymers formed indicated that the initiation end of the chain contains either the cyclopentyl group derived from the preformed Pd,monomer complex or a hydrogen atom left on the Pd center by the chain-transfer reaction. The stable cyclopentylpalladium species are involved in both initiation and propagation steps and undergo isomerization into (cyclopentylmethyl)palladium species followed by the insertion of a CHCH2 bond of a new monomer molecule into the PdCH2 bond. Copolymerization of 1,6-heptadiene derivatives with ethylene, catalyzed by the Pd complexes, yields polymers that contain trans five-membered rings and branched oligoethylene units. Copolymerization of isopropylidene diallylmalonate with 1-hexene affords a polymer with 26,% diene incorporation. The copolymerization consumes 1-hexene more readily than isopropylidene diallylmalonate, although gel permeation chromatography and NMR spectroscopy of the polymers produced show the formation of copolymers rather than of a mixture of homopolymers. Polymerization of 1-hexene initiated with a Pd,barbiturate complex and terminated with 5-allyl-5-hexylpyrimidine-2,4,6(1H,3H,5H)-trione/Et3SiH leads to polyhexene with barbiturate moieties at both terminal ends. Addition of 5-hexyl-2,4,6-triaminopyrimidine to a toluene solution of the telechelic poly(1-hexene) converts the solution into gel. [source] | ||||||||||||||||||||||||||||||||||