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1.
Charles E. Carraher D'Orsay Winthers Frank Millich 《Journal of polymer science. Part A, Polymer chemistry》1969,7(10):2763-2773
The stirred interfacial polycondensation of phenylphosphonic dichloride and 1,6-hexanediamine has been studied as a function of several reaction variables. The reaction is rapid, being completed in less than 1 min. When organic solvent is varied and reactant molar ratio is varied with an excess of the acid chloride, yield is constant. When reactant molar ratio is varied polymer yield increases with increase in amine concentration. When reactant concentration is increased yield increases. With the addition of a soluble salt in the aqueous phase yield is increased. The above indicates that the diffusion of the amine to the reaction zone is of primary importance in determining polymerization rate and that the diffusion of the acid chloride is relatively unimportant. Polymer yield was found to be dependent on the pH of the amine in the aqueous phase. The observed trend is related to the apparent solubility of the amine in the aqueous phase such that the greater the apparent solubility of the amine, the less the polymer yield. Polymer molecular weight is found to be independent of reaction variables tested. Polymer was also formed from the condensation of phenylphosphonic dichloride with p-phenylenediamine, H2N-D-NH2 (where D is a 36-carbon hydrocarbon chain), 1,3-di-4-piperidylpropane, and 4-aminomethylpiperidine; phenyl phosphorodichloridate with 1,6-hexanediamine; chloromethyl phosphonic dichloride with 1,6-hexanediamine. 相似文献
2.
Colm Crean John F. Gallagher Albert C. Pratt 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(1):o36-o38
The title complex, C17H9N5·C6H4S4, contains π‐deficient bis(dinitrile) and TTF molecules stacked alternately in columns along the a‐axis direction; the interplanar angle between the TTF molecule and the isoindolinyl C4N[C(CN)2]2 moiety is 1.21 (4)°. The N‐allyl moiety in the TCPI molecule is oriented at an angle of 87.10 (10)° with respect to the five‐membered C4N ring, and the four C[triple‐bond]N bond lengths range from 1.134 (3) to 1.142 (3) Å, with C—C[triple‐bond]N angles in the range 174.3 (3)–176.9 (2)°. In the TTF system, the S—C bond lengths are 1.726 (3)–1.740 (3) and 1.751 (2)–1.763 (2) Å for the external S—C(H) and internal S—C(S) bonds, respectively. 相似文献
3.
PHOTOLYSIS OF PHOSPHODIESTER BONDS IN PLASMID DNA BY HIGH INTENSITY UV LASER IRRADIATION 总被引:1,自引:0,他引:1
David T. Choke Werner Blau Colm Ohuigin John M. Kelly David J. Mcconnell 《Photochemistry and photobiology》1988,47(4):527-536
Abstract— The cleavage of phosphodiester bonds in DNA exposed to high intensity UV laser pulses in aerated aqueous solution has been investigated using a krypton fluoride excimer laser (248 nm) and bacterial plasmid DNA. The dependence of strand breakage on fluence and intensity has been studied in detail and shows that the process is non-linear with respect to intensity. The relationship between the quantum yield for strand breakage and intensity shows that the strand breakage reaction involves two-photon excitation of DNA bases. The quantum yield rises with intensity from a lower value of 7 times 10-5 until a maximum value of 4.5 times 10-4 is attained at intensities of 1011 W m-2 and above. This value is approximately fifty-fold higher than the quantum yield for strand breakage induced by exposure to low density UV irradiation (254 nm, 12 W m-2 ). DNA sequencing experiments have shown that strand breakage occurs by the specific cleavage of the phosphodiester bond which lies immediately 3' to guanine residues in the DNA, leaving some alkali-labile remnant attached to the terminal phosphate. A mechanism for DNA strand breakage which involves the generation of guanine radical cations is proposed. 相似文献
4.
Charles E. Carraher Jr. George F. Peterson John E. Sheats Ted Kirsch 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):1009-1022
The synthesis of oligomeric tin poly(cobalticinium esters) is presented as a function of the particular reaction variables stirring rate, pH and amount of added base, mole ratio of reactants, concentration of reactants, and volume of organic phase. Factors which decrease the solubility of the stannane apparently act to increase the yield of polyester. The thermal characterization of I was carried out via DSC and TGA. The products generally exhibit endotherms below 150 to 200[ddot]C which may be related to Tg. Above 200[ddot]C, degradation occurs in air by an oxidative mode. 相似文献
5.
Charles E. Carraher Jr. Van R. Foster H. Michael Molloy Michael L. Taylor Thomas O. Tiernan Jack A. Schroeder 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(1):231-241
The synthesis of polymers derived from the condensation of dipyridine manganese II dichloride with 1,3-di-4-piperidylpro-pane is described. Structural analysis of the polyamines is detailed utilizing results based on infrared, thermal, elemental and solution analyses. 相似文献
6.
Charles E. Carraher JR. 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(8):1293-1356
This review emphasizes the breadth of metallic and metallic-like polymers evaluated as to thermal properties. Techniques usefully applied to particular systems are noted with the aim of suggesting their application to other systems. 相似文献
7.
Charles E. Carraher JR. 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(6):1237-1261
Prior to 1940 there was little or no education directed toward polymer chemistry. With the contributions of Carothers and others that transformed the practice of polymers into a science-and the leadership of Herman Mark and others in formal graduate and postgraduate education-polymer education took root but rapid expansion and general acceptance by more traditionally oriented academic institutions was slowed by many barriers. Only since 1974 has there been a concerted effort to include education in the basic concepts of polymer chemistry into the undergraduate curriculum. Emphasis is on the development of polymer education in the United States. 相似文献
8.
9.
Colm Browne Tanya K. Ronson Jonathan R. Nitschke 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(40):10877-10881
The reaction of 2,6‐diformylpyridine with diverse amines and PdII ions gave rise to a variety of metallosupramolecular species, in which the PdII ion is observed to template a tridentate bis(imino)pyridine ligand. These species included a mononuclear complex as well as [2+2] and [3+3] macrocycles. The addition of pyridine‐containing macrocyclic capping ligands allows for topological complexity to arise, thereby enabling the straightforward preparation of structures that include a [2]catenane, a [2]rotaxane, and a doubly threaded [3]rotaxane. 相似文献
10.
The Origin of Shape Sensitivity in Palladium‐Catalyzed Suzuki–Miyaura Cross Coupling Reactions 下载免费PDF全文
Dr. Gillian Collins Michael Schmidt Dr. Colm O'Dwyer Prof. Justin D. Holmes Dr. Gerard P. McGlacken 《Angewandte Chemie (International ed. in English)》2014,53(16):4142-4145
The shape sensitivity of Pd catalysts in Suzuki–Miyaura coupling reactions is studied using nanocrystals enclosed by well‐defined surface facets. The catalytic performance of Pd nanocrystals with cubic, cuboctahedral and octahedral morphologies are compared. Superior catalytic reactivity is observed for Pd NCs with {100} surface facets compared to {111} facets. The origin of the enhanced reactivity associated with a cubic morphology is related to the leaching susceptibility of the nanocrystals. Molecular oxygen plays a key role in facilitating the leaching of Pd atoms from the surface of the nanocrystals. The interaction of O2 with Pd is itself facet‐dependent, which in turn gives rise to more efficient leaching from {100} facets, compared to {111} facets under the reaction conditions. 相似文献