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1.
Kochocki JA Allison WW Alner GJ Ambats I Ayres DS Balka LJ Barr GD Barrett WL Benjamin D Border P Brooks CB Cobb JH Cockerill DJ Coover K Courant H Dahlin B DasGupta U Dawson JW Edwards VW Fields TH Kirby-Gallagher LM Garcia-Garcia C Giles RH Goodman MC Heller K Heppelman S Hill N Hoftiezer JH Jankowski DJ Johns K Joyce T Kafka T Litchfield PJ Lopez FV Lowe M Mann WA Marshak ML May EN McMaster L Milburn RH Miller W Napier A Oliver WP Pearce GF Perkins DH Peterson EA Price LE Roback D Rosen DB 《Physical review D: Particles and fields》1990,42(9):2967-2973
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Biodegradable polyurethanes are an interesting alternative to many applications that involve plastics since they can minimize environmental problems caused by the low rates of natural degradation of synthetic polymers. In addition, since waterborne polyurethanes are based on aqueous dispersions, they restrict the use of organic solvents during processing and application of the polymer, thus contributing furthermore to reduce environmental damage. In this work, aqueous anionic polyurethane dispersions (PUD) with tailorable susceptibility for hydrolysis were synthesized by progressively replacing polypropylene glycol (PPG) with a biodegradable polycaprolactone diol (PCL) as soft segments. The hard segments were formed by extending isophorone diisocyanate (IPDI) with hydrazine (HZ). Dimethylol propionic acid (DMPA) was used as ionic center and triethyl amine (TEA) as neutralizer. The degree of phase separation was evaluated mainly by infrared spectroscopy (FTIR) and small angle X-ray scattering (SAXS). The results indicated that phase separation between hard and soft segments of poly(ester-urethane) is more significant than that of poly(ether-urethane). Data obtained from SAXS experiments indicated that phase separation within soft domains can also be present in samples containing both polyester and polyether soft segments. Hydrolytic degradation of the polymers in buffer solution of pH 7.4 and alkaline solution was performed as an initial test. The results showed that the fraction of polyester soft segments in the polyurethanes can be used to tailor the susceptibility of the materials to hydrolytic attack. Polyurethanes having higher contents of polyester were more promptly hydrolytically degraded than polyurethanes containing only polyether segments. 相似文献
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Ferreira AR de A Vilela GV Amorim MB Perry KP da Silva AJ Dias AG Costa PR 《The Journal of organic chemistry》2004,69(12):4013-4018
The conjugate addition of benzylic phenylsulfonyl carbanions (2a'-d') to enoates derived from d-(+)-mannitol (E- or Z-1a-c) was studied using THF and THF/HMPA as solvent. Under kinetic conditions (-78 degrees C), enoate E-1a,b led to a mixture of syn-(R,S) and anti-(S,S) adducts (55/45), and syn-(R,S) adducts were the main product obtained ( approximately 90/10) from enoate Z-1a. Under thermodynamic conditions (-78 degrees C to room temperature) syn-(R,S) adducts were also preferentially formed ( approximately 90/10), despite the geometry at the double bond in the acceptor. Enoate 1c (E/Z = 57/43), bearing an additional benzyl group at the alpha-position, also reacted with carbanions 2'a,b, under thermodynamic conditions, leading to syn-adducts in excellent de (control at the three newly generated stereogenic centers). The adducts were quantitatively transformed into the corresponding beta-gamma-disubstituted gamma-butyrolactones and alpha,beta,gamma-trisubstituted gamma-butyrolactones. (1)H NMR studies (NOE and J-coupling) of these lactones allowed us to determine their configuration at the newly generated chiral centers. The reduction of the C-S bond in adducts syn-(R,S) with Na/Hg, followed by treatment of the resulting products in aqueous acid media, led to enantioenriched beta-benzyl-gamma-hydroxymethyl-gamma-butyrolactones. The conformational equilibrium of enoates E- and Z-1b was evaluated by theoretical calculations (ab initio, MP2/6-31G), and a mechanistic rationale was proposed to explain the observed stereoselectivities. 相似文献
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P. J. Mendes J. M. Gil N. Ayres de Campos R. Peichl A. Weidinger 《Hyperfine Interactions》1983,16(1-4):791-794
The perturbation felt by181Hf probes in a181HfTa lattice loaded with 30 at% hydrogen was observed by PAC as a function of temperature. Three different interactions were identified: 1) ΝQ1=433 (6) MHz, η=0.45 2) ΝQ2=142 (9) MHz, η=0.9, and 3) ΝQ?0, σ=4–14 Μ?1 which are attributed to the Β?, ε? and α-phase in TaH system, respectively. 相似文献
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Ruthenium(III) reacts with 2,2′,2″-terpyridine in aqueous solution at pH 3.0–4.5, when heated at 85 °C for 2 min, giving a green cationic complex with an absorbance maximum at 690 nm. The color is stable for at least 25 h. The system conforms to Beer's law. The optimal range for measurement (1.00-cm optical path) is 2–10 p.p.m. Ru; the molar absorptivity is 8.3 ·103. Ruthenium(II) reacts with terpyridine at pH 5.5 to develop an amber cationic complex (absorption maximum at 475 nm) on heating at 95° C for 45 min. The color is apparently stable indefinitely. The system conforms to Beer's law; the optimal range is 1–5 p.p.m. Ru; the molar absorptivity is 1.45·104 l mol?1 cm?1. Common anions do not interfere; separation as RuO4 is necessary when iron and a few other transition cations are present. The green complex, a strong oxidant, is converted to the ruthenium(II) complex by oxidation of water, slowly at room temperature, or more quickly by longer heating and/or higher temperature, and by increase of pH. The Ru(II) complex can be converted to the Ru(III) complex by strong oxidants such as Ce(IV). In the amber complex, the reaction ratio is 1 Ru: 2 terpyridine, in which the ligand is tridentate, whereas in the green complex the reaction ratio is 1 Ru : 3 terpyridine, the latter acting only as a bidentate ligand. Short gentle warming of a mixture of ruthenium(III) and terpyridine first produces a transient unidentified blue-colored species (absorbance at 790 nm). 相似文献
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Patrícia Santiago de Oliveira Patricio Iaci Miranda Pereira Natália Cristina Ferreira da Silva Eliane Ayres Fabiano Vargas Pereira Rodrigo Lambert Oréfice 《European Polymer Journal》2013
Polyurethane waterborne synthesis was performed using a two-step method, commonly referred to as a prepolymer method. Nanocomposites based on waterborne polyurethane and cellulose nanocrystals were prepared by the prepolymer method by altering the mode and step in which the nanofillers were incorporated during the polyurethane formation. The morphology, structural, thermal, and mechanical properties of the resulting nanocomposite films were evaluated by Fourier transform infrared spectroscopy (FTIR), small angle X-ray scattering (SAXS), scanning electron microscopy (SEM), and tensile tests. FTIR results indicated that the degree of interaction between the nanofillers and the WPU through hydrogen bonds could be controlled by the method of cellulose nanocrystal incorporation. Data obtained from SAXS experiments showed that the cellulose nanocrystals as well as the step of the reaction in which they are added influenced the morphology of the polyurethane. The reinforcing effect of CNCs on the nanocomposites depends on their morphology. 相似文献
8.
Xiaoping Chen Neil Ayres 《Journal of polymer science. Part A, Polymer chemistry》2011,49(14):3030-3037
The synthesis of a molecular brush was accomplished by combining step‐growth polymerization and reversible addition fragmentation chain transfer (RAFT) polymerization in a “grafting from” methodology. A symmetrical N‐alkyl urea peptoid sixmer containing alkyne functional groups was prepared using a divergent strategy, and the structure of the product was confirmed using NMR spectroscopy and mass spectrometry. A step‐growth process was used to prepare a linear poly(N‐alkyl urea peptoid) by reacting the diamine‐functionalized N‐alkyl urea peptoid sixmer with a diisocyanate. RAFT chain transfer agents were coupled to the poly(N‐alkyl urea peptoid) backbone through a copper‐catalyzed azide/alkyne cycloaddition reaction. The afforded macro‐RAFT agent was used to sequentially polymerize styrene and tert‐butyl acrylate block copolymer arms from the poly(N‐alkyl urea peptoid) backbone. The tert‐butyl groups were removed using dilute trifluoroacetic acid affording hydrophilic polyacrylic acid segments. The molecular brushes were observed to generate micelles in aqueous solution. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011 相似文献
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Adamson P Auty DJ Ayres DS Backhouse C Barr G Bishai M Blake A Bock GJ Boehnlein DJ Bogert D Cavanaugh S Cherdack D Childress S Coelho JA Coleman SJ Corwin L Cronin-Hennessy D Danko IZ de Jong JK Devenish NE Diwan MV Dorman M Escobar CO Evans JJ Falk E Feldman GJ Frohne MV Gallagher HR Gomes RA Goodman MC Gouffon P Graf N Gran R Grant N Grzelak K Habig A Harris D Hartnell J Hatcher R Himmel A Holin A Huang X Hylen J Ilic J Irwin GM Isvan Z Jaffe DE James C Jensen D Kafka T Kasahara SM Koizumi G 《Physical review letters》2011,107(1):011802
Results are reported from a search for active to sterile neutrino oscillations in the MINOS long-baseline experiment, based on the observation of neutral-current neutrino interactions, from an exposure to the NuMI neutrino beam of 7.07×10(20) protons on target. A total of 802 neutral-current event candidates is observed in the Far Detector, compared to an expected number of 754 ± 28(stat) ± 37(syst) for oscillations among three active flavors. The fraction f(s) of disappearing ν(μ) that may transition to ν(s) is found to be less than 22% at the 90% C.L. 相似文献