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1.
Richard Kotek Kyeong Pang Ben Schmidt Alan Tonelli 《Journal of Polymer Science.Polymer Physics》2004,42(23):4247-4254
Poly(ethylene isophthalate) (PEI) was synthesized for this research with essentially a condensation polymerization of isophthalic acid and ethylene glycol catalyzed by zinc acetate and antimony trioxide. Several samples were obtained, and their characteristics were observed and compared with poly(ethylene terephthalate) (PET). The synthesized PEI samples were chemically identified by 1H NMR. Thermal analysis with differential scanning calorimetry (DSC) yielded results that indicate the samples were primarily amorphous, with a glass‐transition temperature of 55–60 °C. Molecular weights of these PEI samples were also obtained through intrinsic viscosity measurements (Mark–Houwink equation). Molecular weights varied with conditions of the polymerization, and the highest molecular weight achieved was 21,000 g/mol. Finally, the diffusion coefficient, solubility, and permeability of CO2 gas in PEI were measured and found to be substantially lower than in PET, as anticipated from their isomeric chemical structures. This is because in PET the phenyl rings are substituted in the para (1,4) positions, which allows for their facile flipping, effectively permitting gases to pass through. However, the meta‐substituted phenyl rings in PEI do not permit such ring flipping, and thus PEI may be more suitable for barrier applications. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 4247–4254, 2004 相似文献
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Derivatization of a variety of peptides by a method known to enhance anhydride formation is demonstrated by mass spectrometry to yield ions that have elemental composition and fragmentation properties identical to [b(n-1) + OH + H]+ ions formed by gas-phase rearrangement and fragmentation. The [b(n-1) + OH + H]+ ions formed by gas-phase rearrangement and fragmentation and the solution-phase [b(n-1) + OH + H]+ ion structural analogs formed by derivatization chemistry show two different forms of dissociation using multiple-collision CAD in a quadrupole ion trap and unimolecular decomposition in a TOF-TOF; one group yields identical product ions as a truncated form of the peptide with a free C-terminal carboxylic acid and fragments at the same activation energy; the other group fragments differently from the truncated peptide, being more resistant to fragmentation than the truncated peptide and yielding primarily the [b(n-2) + OH + H]+ product ion. Nonergodic electron capture dissociation MS/MS suggests that any structural differences between the specific-fragmenting [b(n-1) + OH + H]+ ions and the truncated peptide is at the C-terminus of the peptide. The specific-fragmentation can be readily observed by MS(n) experiments to occur in an iterative fashion, suggesting that the C-terminal structure of the original [b(n-1) + OH + H]+ ion is maintained after subsequent rearrangement and fragmentation events in peptides which fragment specifically. A mechanism for the formation of specific-fragmenting and nonspecific-fragmenting [b(n-1) + OH + H]+ ions is proposed. 相似文献
4.
Ronald L. Cerny Kenneth B. Tomer Michael L. Gross 《Journal of mass spectrometry : JMS》1986,21(10):655-660
Combining desorption ionization with tandem mass spectrometry overcomes the disadvantage of limited fragmentation accompanying desorption and permits mixtures of closely related substances to be investigated directly. These features of the combination are illustrated by completing the structure-proof of a minor component of an ornithine-containing lipid mixture isolated from Thiobacillus thiooxidans. The minor component is a homolog of the major constituent and differs from the principal component owing to the presence of a double bond in lieu of a cyclopropyl ring in one of the constituent fatty acids. Another feature of the combined method is the potentially complementary nature of collision-activated dissociation spectra of protonated and cationized biomolecules. This is illustrated by the differences in the collision-activated dissociations of the [M + Na]+ of sucrose, desorbed by field desorption, and [M + H]+, desorbed by fast atom bombardment. A third illustration is the application of field desorption and tandem mass spectrometry to an organometallic compound. The combined approach allows the ligands to be identified and the relative ligand binding energies to be approximated. 相似文献
5.
The method reported for the determination of calcium in silicate rocks involves titration with ethyleneglycol-bis(2-aminoethylether)tetraacetic acid (EGTA) to a potentiometric end-point. A Crytur calcium-selective electrode is used; the selectivity constants (Kca,x) are less than 10-3 for Mg, Ba, Sr, K and Na. The method can be used for calcium contents of 2% or higher (and exceptionally for lower contents), in the presence of up to 60% Mg, 33% AI, 17% Fe, 5% Ba, 5% Ti, and 2.5% Mn. Al, Fe and Ti are masked with sulphosalicylic acid, barium is precipitated as its sulphate, and manganese is bound as its cyanide complex. If the magnesium content is less than that of calcium, EDTA can be used as titrant, magnesium being masked with acetylacetone. 相似文献
6.
The mass spectra of a group of m- and p-substituted acetanilides were measured to determine the effect of the substituents, if any, on the rate of C2H2O expulsion (rearrangement) vs. the rate of [CH3CO]+ formation (simple cleavage). Our results agree with observations of others in that substituents which raise the ionization potential of the aromatic ring appear to localize, on the average, less charge density on this locus, and conversely. The atomic composition of the substituent, however, irrespective of its position, seems to determine the relative rates of the competing reaction. Although in several cases Zm/Zp values were close to unity, rearrangement of isomeric molecular ions to a common species is shown not to occur. 相似文献
7.
Mixtures of peptides have been analyzed by capillary zone electrophoresis in conjunction with mass spectrometry (MS) using an on-line coaxial continuous-flow fast atom bombardment interface. MS and MS-MS spectra have been acquired in electrophoretic real time from femtomole levels of the peptides, while maintaining separation efficiencies in excess of 100,000 theoretical plates. 相似文献
8.
Kenneth B. Tomer 《Journal of mass spectrometry : JMS》1974,9(7):686-689
Ion cyclotron resonance spectrometry and deuterium labeling have been used to determine that nondecomposing \documentclass{article}\pagestyle{empty}\begin{document}${\rm (CH}_{\rm 3} {\rm)}_{\rm 2} \mathop {\rm N}\limits^{\rm + } {\rm = CH}_{\rm 2}$\end{document} ions do not isomerize to \documentclass{article}\pagestyle{empty}\begin{document}${\rm CH}_{\rm 3} {\rm CH = }\mathop {\rm N}\limits^{\rm + } {\rm HCH}_{\rm 3}$\end{document}. 相似文献
9.
Kotek J Lubal P Hermann P Císarová I Lukes I Godula T Svobodová I Táborský P Havel J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(1):233-248
In an aqueous solution at room temperature, 1,4,8,11-tetraazacyclotetradecane-1,8-bis(methylphosphonic acid) (H(4)L(1)) and Cu(I) (I) form a pentacoordinated (pc) complex, pc-[Cu(L(1))](2-), exhibiting conformation I of the cyclam ring. At high temperature, the complex isomerises to a hexacoordinated isomer, trans-O,O-[Cu(L(1))](2-), with a trans-III conformation of the cyclam ring. In pc-[Cu(L(1))](2-), four ring nitrogen atoms and one phosphonate oxygen atom are arranged around Cu(I) (I) in a structure that is half-way between a trigonal bipyramid and a tetragonal pyramid, with one phosphonic acid group uncoordinated. In the trans-O,O-[Cu(L(1))](2-) isomer, the nitrogen atoms form a plane and the phosphonic acid groups are in a mutually trans configuration. A structurally very similar ligand, 4-methyl-1,4,8,11-tetraazacyclotetradecane-1,8-bis(methylphosphonic acid) (H(4)L(2)), forms an analogous pentacoordinated complex, pc-[Cu(L(2))](2-), at room temperature. However, the complex does not isomerise to the octahedral complex analogous to trans-O,O-[Cu(L(1))](2-). Because of the high thermodynamic stability of pc-[Cu(L(1))](2-), (logbeta=25.40(4), 25 degrees C, I=0.1 mol dm(-3) KNO(3)) and the formation of protonated species, Cu(I) (I) is fully complexed in acidic solution (-log [H(+)] approximately 3). Acid-assisted decomplexation of both of the isomers of [Cu(H(2)L(1))] takes place only after protonation of both uncoordinated oxygen atoms of each phosphonate moiety and at least one nitrogen atom of the cycle. The exceptional kinetic inertness of both isomers is illustrated by their half-lives tau(1/2)=19.7 min for pc-[Cu(H(2)L(1))] and tau(1/2) about seven months for trans-O,O-[Cu(H(2)L(1))] for decomplexation in 5 M HClO(4) at 25 degrees C. The mechanism of formation of pc-[Cu(L(1))](2-) is similar to those observed for other macrocyclic complexes. 相似文献
10.
W. R. Krigbaum R. Kotek Y. Mihara J. Preston 《Journal of polymer science. Part A, Polymer chemistry》1985,23(7):1907-1916
We report a study of the conditions of the phosphorylation reaction for the preparation of aromatic polyamides using the Higashi reaction medium. For poly(p-phenylene terephthalamide) (PPD-T), the optimum conditions are: reaction temperature, 115°C; monomer concentration, C = 0.083 mol/L; and ratio of triphenyl phosphite (TPP) to monomer, 2.0. These optimum conditions produce PPD-T having ηinh = 6.2 dL/g. At temperatures of 120°C and above PPD-T precipitates from the reaction mixture, leading to lower molecular weights. At lower temperatures the reaction mixture gels, and the gel time decreases with increasing reaction temperature. However, polycondensation continues in the gel state. Monomer concentrations C = 0.10 mol/L and above produce precipitation and yield polyamides of lower molecular weight. For the preparation of poly(p-benzamide) (PBA), the optimum ratio of TPP to monomer is 0.6 for either p- aminobenzoic acid or N-4-(4′-aminobenzamido)benzoic acid. In the former case the inherent viscosity of polymer prepared at 115°C showed little dependence upon the concentration of the monomer. The highest value, ηinh = 1.8 dL/g, was obtained with C = 0.40 mol/L and a TPP/monomer ratio of 0.6. However, for the same TPP/monomer ratio, the monomer containing a preformed amide linkage, N-4-(4′-aminobenzamido)benzoic acid, gave PBA with ηinh = 4.6 dL/g when the monomer concentration is 0.33 mol/L. This is the highest value reported for PBA using the phosphorylation reaction. In A?A + B?B polycondensation, examples in which one of the monomers contained one or two preformed amide linkages produced polyamides having ηinh = 7.8 and 8.9 dL/g, respectively. 相似文献