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11.
The temperature dependence of the NMR chemical shift of129Xe dissolved in liquid alkanes is examined in the context of the reaction field model. An essential feature of the theory is the inclusion of the temperature dependence of the density of thesolvent. The theory of free volume for liquids is incorporated into the reaction field model to account for this temperature dependence. Comparison of the theory with previously reported measurements indicates the sensitivity of the129Xe chemical shift to the free volume of liquids. Incorporation of free volume improves the agreement between measurement and theory for branched alkane solvents, and resolves the origin of the 62 ppm intercept in the plot of reaction field as a function of129Xe chemical shift for the n-alkanes. 相似文献
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13.
Poly (n-butylisocyanate)-benzene solutions prepared by solubilization at 45°C, followed by aging at room temperature were found to be metastable for months, although, eventually, they separated into a birefringent polymer-rich phase and an isotropic solution. These metastable solutions, as well as isothermally phase-separated biphasic samples, flowed and exhibited dynamic moduli indicative of low polymer connectivity. By contrast samples prepared by a freeze-thaw cycle were uniformly and highly birefringent and showed network (gel) behavior at room temperature. The mechanism of gel formation is most likely the exclusion of the polymer from the benzene crystal during crystallization, forcing the polymer to align and exist at grain boundaries. Films formed from solutions have different moduli than those formed from gels, and are consistent with the proposed mechanism. 相似文献
14.
Hiroshi Ito Masaki Okazaki Dolores C. Miller 《Journal of polymer science. Part A, Polymer chemistry》2004,42(6):1478-1505
Radical copolymerizations of electron‐deficient 2‐trifluoromethylacrylic (TFMA) monomers, such as 2‐trifluoromethylacrylic acid and t‐butyl 2‐trifluoromethylacrylate (TBTFMA), with electron‐rich norbornene derivatives and vinyl ethers with 2,2′‐azobisisobutyronitrile as the initiator were investigated in detail through the analysis of the kinetics in situ with 1H NMR and through the determination of the monomer reactivity ratios. The norbornene derivatives used in this study included bicyclo[2.2.1]hept‐2‐ene (norbornene) and 5‐(2‐trifluoromethyl‐1,1,1‐trifluoro‐2‐hydroxylpropyl)‐2‐norbornene. The vinyl ether monomers were ethyl vinyl ether, t‐butyl vinyl ether, and 3,4‐dihydro‐2‐H‐pyran. Vinylene carbonate was found to copolymerize with TBTFMA. Although none of the monomers underwent radical homopolymerization under normal conditions, they copolymerized readily, producing a copolymer containing 60–70 mol % TFMA. The copolymerization of the TFMA monomer with norbornenes and vinyl ethers deviated from the terminal model and could be described by the penultimate model. The copolymers of TFMA reported in this article were evaluated as chemical amplification resist polymers for the emerging field of 157‐nm lithography. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 1478–1505, 2004 相似文献
15.
We give several new constructions for moderate rank elliptic curves over Q(T). In particular we construct infinitely many rational elliptic surfaces (not in Weierstrass form) of rank 6 over Q using polynomials of degree two in T. While our method generates linearly independent points, we are able to show the rank is exactly 6 without having to verify the points are independent. The method generalizes; however, the higher rank surfaces are not rational, and we need to check that the constructed points are linearly independent. 相似文献
16.
The synthesis of chiral oxazolidinedione derived bicalutamide analogs has been discussed. 相似文献
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18.
Peter D. Verhaert Maria C. Prieto Conaway Tonya M. Pekar Ken Miller 《International journal of mass spectrometry》2007,260(2-3):177
Direct tissue imaging was performed on dissected insect tissue using a MALDI ion trap to visualize endogenous neuropeptides. Coupling tissue imaging to tandem MSn allows for the identification of previously known species and the ability to identify new ones by de novo sequencing, as searchable databases for insects are sparse. Direct tissue imaging is an attractive technique for the study of neuropeptides as minimal sample preparation is required prior to mass spectrometry. We successfully identified neuropeptides present in the corpora cardiaca and allata of Acheta domesticus (the house cricket). Diagnostic fragments at low m/z were used to distinguish between lipids and neuropeptides. The distribution of peptides appears to be more differentially localized than that of phospholipids, which seem to be more evenly distributed within the tissue. 相似文献
19.
Problems associated with interferences in the analysis of serum for polychlorinated biphenyls 总被引:2,自引:0,他引:2
V W Burse M P Korver P C McClure J S Holler D M Fast S L Head D T Miller D J Buckley J Nassif R J Timperi 《Journal of chromatography. A》1991,566(1):117-125
During a recent survey to determine serum concentrations of polychlorinated biphenyls (PCBs) among people living around New Bedford, MA, U.S.A., an unidentified contaminant precluded the quantification of some early eluting Webb and McCall peaks. Loss of data is estimated to have reduced reported serum levels by 12%. Efforts to identify the contaminant by gas chromatography with an electron-capture detector, a Hall electrolytic condutivity detector, and mass spectrometer were not successful. Researchers ascertained, however, that the contaminant is not a PCB, it does not contain halogens, but it may contain phthalates. Vacutainer tubes and closures for serum storage bottles are suspected sources of contamination. 相似文献
20.
This paper reviews the properties of the cathode ion flux generated in the vacuum arc. The structure and distribution of mass erosion from individual cathode spots and the characteristics of current carriers from the cathode region at moderate arc currents are described. An appreciable ion flux (~10% of total arc current) is emitted from the cathode of a vacuum arc. This ion flux is strongly peaked in the direction of the anode, though some ion flux may be seen even at angles below the plane of the cathode surface. The observed spatial distribution of the ion flux is expressed quite well as an exponential function of solid angle. The ion flux is quite energetic, with average ion potentials much larger than the arc voltage, and generally contains a considerable fraction of multiply-charged ions. The average ion potential and ion multiplicity increase significantly for cathode materials with higher arc voltages, but decrease with increasing arc current for a particular material. The main theories concerning ion acceleration in cathode spots are the potential hump theory (PH), which assumes that all ions are created at the same potential, and the gas dynamic theory (GD), which assumes that all ions are created with the same flow velocity. Experimental data on the potentials and energies of individual ions indicates that these theories in their original forms are not quite correct, however extensions or modifications of the PH and GD theories seem very likely to be able to predict correct values for the charge states, potentials, and energies of individual ions. 相似文献