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1.
Jamie M. Messman Robson F. Storey 《Journal of polymer science. Part A, Polymer chemistry》2006,44(23):6817-6835
Ethylene glycol (EG) initiated, hydroxyl‐telechelic poly(L ‐lactide) (PLLA) was employed as a macroinitiator in the presence of a stannous octoate catalyst in the ring‐opening polymerization of 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) with the goal of creating A–B–A‐type block copolymers having polycarbonate outer blocks and a polyester center block. Because of transesterification reactions involving the PLLA block, multiblock copolymers of the A–(B–A)n–B–A type were actually obtained, where A is poly(5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one), B is PLLA, and n is greater than 0. 1H and 13C NMR spectroscopy of the product copolymers yielded evidence of the multiblock structure and provided the lactide sequence length. For a PLLA macroinitiator with a number‐average molecular weight of 2500 g/mol, the product block copolymer had an n value of 0.8 and an average lactide sequence length (consecutive C6H8O4 units uninterrupted by either an EG or MBC unit) of 6.1. For a PLLA macroinitiator with a number‐average molecular weight of 14,400 g/mol, n was 18, and the average lactide sequence length was 5.0. Additional evidence of the block copolymer architecture was revealed through the retention of PLLA crystallinity as measured by differential scanning calorimetry and wide‐angle X‐ray diffraction. Multiblock copolymers with PLLA crystallinity could be achieved only with isolated PLLA macroinitiators; sequential addition of MBC to high‐conversion L ‐lactide polymerizations resulted in excessive randomization, presumably because of residual L ‐lactide monomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6817–6835, 2006 相似文献
2.
Ly A Bandong SL Tran NQ Sullivan KJ Milligan JR 《The journal of physical chemistry. B》2005,109(27):13368-13374
Guanine bases are the most easily oxidized sites in DNA. Electron-deficient guanine species are major intermediates produced in DNA by the direct effect of ionizing radiation (ionization of the DNA itself) because of preferential hole migration within DNA to guanine bases. By using thiocyanate ions to modify the indirect effect (ionization of the solvent), we are able to produce these single-electron-oxidized guanine radical species in dilute aqueous solutions of plasmid DNA where the direct effect is negligible. The guanyl radical species produce stable modified guanine products. They can be detected in the plasmid by converting them to strand breaks after incubation with a DNA repair enzyme. If a phenol is present during irradiation, the yield of modified guanines is decreased. The mechanism is reduction of the guanine radical species by the phenol. It is possible to derive a rate constant for the reaction of the phenol with the guanyl radical. The pH dependence shows that phenolate anions are more reactive than their conjugate acids, although the difference for guanyl radicals is smaller than with other single-electron-oxidizing agents. At physiological pH values, the reduction of a guanyl radical entails the transfer of a proton in addition to the electron. The relatively small dependence of the rate constant on the driving force implies that the electron cannot be transferred before the proton. These results emphasize the potential importance of acidic tyrosine residues and the intimate involvement of protons in DNA repair. 相似文献
3.
Jasminka Mizdrak Peter G. Hains Danuta Kalinowski Michael J. Davies Joanne F. Jamie 《Tetrahedron》2007,63(23):4990-4999
4-(2-Aminophenyl)-4-oxobutanoic acid, 4-(2-amino-3-hydroxyphenyl)-4-oxobutanoic acid and glutathionyl-kynurenine have been identified as novel metabolites in normal and cataractous human lenses following total synthesis and comparison with authentic human lens samples. Their structures are consistent with those derived from the major human lens UV filters kynurenine and 3-hydroxykynurenine, and it is proposed that these compounds also play a role as UV filters. These metabolites were isolated in pmol/mg levels (dry mass) in lenses. 4-(2-Amino-3-hydroxyphenyl)-4-oxobutanoic acid and glutathionyl-kynurenine were found to be unstable at physiological pH. Other potential metabolites, glutathionyl-3-hydroxykynurenine, kynurenine yellow and 3-hydroxykynurenine yellow, were not detected in either normal or cataractous lenses. 相似文献
4.
Huang SY Anklin C Walls JD Lin YY 《Journal of the American Chemical Society》2004,126(49):15936-15937
With the growing use of high fields and ultrasensitive probes, radiation damping emerges as a significant feedback interaction in modern solution NMR. Motivated by recent observations of mysterious concentration-dependent frequency shifts, experiments carried out on a cryoprobe at 600 MHz have revealed a time-averaged frequency shift of up to +83/-81 Hz. The sizable frequency shifts arise from deviations in the phase of the radiation damping field from perfect orthogonality relative to the net transverse magnetization. The frequency shift is shown to depend on the longitudinal magnetization and probe tuning conditions through experiments and numerical simulations. Such unexpected shifts in the solvent precession frequency provide a physical explanation for the empirical practice of adjusting the irradiation frequency of the saturating B1 field in solvent presaturation to achieve optimal suppression. Additional applications of the radiation damping induced frequency shift to solvent suppression and NMR methodology are discussed. 相似文献
5.
Réka Mokrai Jamie Barrett Dr. David C. Apperley Dr. Andrei S. Batsanov Dr. Zoltán Benkő Dr. Dominikus Heift 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(16):4017-4024
To study pnictogen bonding involving bismuth, flexible accordion-like molecular complexes of the composition [P(C6H4-o-CH2SCH3)3BiX3], (X=Cl, Br, I) have been synthesised and characterised. The strength of the weak and mainly electrostatic interaction between the Bi and P centres strongly depends on the character of the halogen substituent on bismuth, which is confirmed by single-crystal X-ray diffraction analyses, DFT and ab initio computations. Significantly, 209Bi–31P through-space coupling (J=2560 Hz) is observed in solid-state 31P NMR spectra, which is so far unprecedented in the literature, delivering direct information on the magnitude of this pnictogen interaction. 相似文献
6.
Treatment of the tert-butyldimethylsilyl ethers 1a-f with Jones reagent gave the carboxylic acids 2a-f in excellent yield in the absence of potassium fluoride. 相似文献
7.
Rational design of methacrylate monomers containing oxadiazole moieties for single‐layer organic light emitting devices
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Bogdan Zdyrko Yuriy Bandera Volodymyr Tsyalkovsky Christopher F. Huebner Jamie A. Shetzline Parul Rungta Ryan D. Roeder Charles Tonkin Stephen E. Creager Stephen H. Foulger 《Journal of Polymer Science.Polymer Physics》2015,53(23):1663-1673
Methacrylate derived monomers functionalized with pendant oxadiazole moieties were synthesized and copolymerized with carbazole containing monomers to form polymers with electron and hole transporting fragments in the same molecule. Substituents on the oxidazole moiety were varied with the purpose of bandgap tuning and performance optimization when employed in single‐layer organic light emitting devices (OLED). Quantum mechanical calculations of the HOMO‐LUMO levels of the oxidazole derivatives were used to down‐select promising candidates for chemical synthesis and testing in single‐layer OLEDs. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2015 , 53, 1663–1673 相似文献
8.
9.
Ilana Perelshtein Yelena Ruderman Nina Perkas Jamie Beddow Gagandeep Singh Mircea Vinatoru Eadaoin Joyce Timothy J. Mason María Blanes Korina Mollá Aharon Gedanken 《Cellulose (London, England)》2013,20(3):1215-1221
Hospital-acquired nosocomial infections are a major health, and consequently financial issue, in the world healthcare system. The problem of bacterial infections in general, and in hospitals in particular, has led to extensive scientific and industrial efforts to fabricate antibacterial textiles. A sonochemical coating machine was developed and built and its ability to coat antibacterial nanoparticles (NPs) onto 40–50 meter length of materials on a roll to roll basis at a speed of 22 cm/min. Cotton coated sonochemically with copper oxide nanoparticles (CuO NPs) was found to maintain its antibacterial properties even after 65 cycles of washings according to hospital protocols of hygienic washing (75 °C). This demonstrates the good quality and high stability of this sonochemically produced NPs coating on textiles. Durable antibacterial textiles such as these may be suitable for wide spread use in future hospital environments where hygiene control is of paramount importance. 相似文献
10.
Combining Complementary Ligands into one Framework for the Construction of a Ferromagnetically Coupled [MnIII12] Wheel
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Dr. Sergio Sanz Jamie M. Frost Thayalan Rajeshkumar Dr. Scott J. Dalgarno Dr. Gopalan Rajaraman Dr. Wolfgang Wernsdorfer Prof. Jürgen Schnack Dr. Paul. J. Lusby Prof. Euan K. Brechin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(11):3010-3013
Phenolic oxime and diethanolamine moieties have been combined into one organic framework, resulting in the formation of a novel ligand type that can be employed to construct a rare and unusual dodecametallic Mn wheel, within which nearest neighbours are coupled ferromagnetically. 相似文献