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21.
W E May S N Chesler S P Cram B H Gump H S Hertz D P Enagonio S M Dyszel 《Journal of chromatographic science》1975,13(11):535-540
The low concentration of hydrocarbons anticipated in pollution baseline studies necessitates the development of analytical techniques sensitive at the sub-microgram per kilogram concentration level. The method of analysis developed in this laboratory involves dynamic headspace sampling for volatile hydrocarbon components of the sample, followed by coupled-column liquid chromatography for the non-volatile components. These techniques require minimal sample handling, reducing the risk of sample component loss and/or sample contamination. Volatile sample components are separated from the matrix in a closed system and concentrated on a TENAX-GC packed pre-column, free from large amounts of solvent and ready for GC/GC-MS analysis. Non-volatile compounds, such as the benzpyrenes, may be extracted from large volumes of water and concentrated on a Bondapak C18 packed pre-column for coupled-column liquid chromatographic separation and analysis. Results of the application of these techniques to the analysis of samples from sites of known low level hydrocarbon contamination are presented and discussed. 相似文献
22.
The ionic product of water, pK(w) = - log[H(+)][OH(-)] has been determined in aqueous solutions of tetramethylammonium chloride over the concentration range of 0.1-5.5 M at 25 degrees C using high-precision glass electrode potentiometric titrations. pK(w) data relating to aqueous potassium and sodium chlorides at ionic strengths up to 5 M are markedly lower than the tetramethylammonium chloride results. These differences are almost certainly due to weak associations between potassium and (especially) sodium and hydroxide ions. 相似文献
23.
May JP Ting R Lermer L Thomas JM Roupioz Y Perrin DM 《Journal of the American Chemical Society》2004,126(13):4145-4156
A DNAzyme, synthetically modified with both primary amines and imidazoles, is found to act as a M2+ -independent AP lyase-endonuclease. In the course of the cleavage reaction, this DNAzyme forms a covalent Schiff base intermediate with an abasic site on a complementary oligodeoxyribonucleotide. This intermediate, which is inferred from NaCNBH3 trapping as well as cyanide inhibition, does not evidently accumulate because the second step, dehydrophosphorylative elimination, is fast compared to Schiff base formation. The 5'-product that remains linked to the catalyst hydrolyzes slowly to regenerate free catalyst. The use of duly modified DNAzymes to perform Schiff base catalysis demonstrates the value of modified nucleotides for enhancing the catalytic repertoire of nucleic acids. This work suggests that DNAzymes will be capable of catalyzing aldol condensation reactions. 相似文献
24.
trans-1,2,3,4,4a,5,6,10b-Octahydrophenanthridine, the 9-methoxy analog, and 5-methyl derivatives ( 6a,6b ) of each have been synthesized from trans-phenylcyclohexylamines ( 2a,2b ) and ethyl chloroformate followed by cyclization and reduction or by cyclization, N-methylation and reduction. The oximes ( la,1b ) of 2-phenylcyclohexanone and the m-methoxy relative, a mixture of the syn and anti isomers, were reduced to 2a and 2b with sodium and ethanol. Hydrogenation (platinum oxide-acetic acid) of 1a gave in addition to 2a , a small yield of 2-cyclohexylcyclohexyl-amine. Similar hydrogenation of 1b gave only this fully reduced compound. 相似文献
25.
Belz J Cousins RD Diwan MV Eckhause M Ecklund KM Hancock AD Highland VL Hoff C Hoffmann GW Irwin GM Kane JR Kettell SH Klein JR Kuang Y Lang K Martin R May M McDonough J Molzon WR Riley PJ Ritchie JL Schwartz AJ Trandafir A Ware B Welsh RE White SN Witkowski MT Wojcicki SG Worm S 《Physical review letters》1996,76(18):3277-3280
26.
Erich Königsberger Lan-Chi Königsberger Glenn Hefter Peter M. May 《Journal of solution chemistry》2007,36(11-12):1619-1634
Isopiestic measurements of mixed electrolyte solutions involving sodium hydroxide and other components of Bayer liquors were performed at 50?°C and 100?°C. Most of the systems studied obey Zdanovskii’s rule exactly or very closely. However, those with sodium chloride as one of their components show deviations from Zdanovskii’s rule, which are well predicted by our thermodynamic modelling software based on Pitzer’s equations. 相似文献
27.
Zusammenfassung In der vorliegenden Arbeit wird das Sedimentations-gleichgewicht des Systems Na6[H2W12O40]-NaClO4-H2O bei 25 °C untersucht. Die scheinbare Ladungszahl des Natriummetawolframats wird als Funktion der NaClO4-MolalitätmNaClO4 ermittelt. Aus dieser Abhängigkeit kann für die summarische Dissoziation des NatriummetawolframatsNa2[H2W12O4o] 6Na+ + [H2W12O40]6– die DissoziationskonstanteK in Gegenwart von NaClO4 als Fremdelektrolyt zuK=0,08 mol6·kg–6 bestimmt werden.Der Kreuzdifferentialquotient
(
PXz
, ist der Trace-Aktivitätskoeffizient des Natriummetawolframats) wird ebenfalls als Funktion der NaClO4-Molalität ermittelt.Die Konzentrationsabhängigkeit des Trace-Aktivitätskoeffizienten zeigt einen Verlauf, wie er unseres Wissens nach noch nicht von anderen Autoren beobachtet wurde.
Mit 5 Abbildungen und 1 Tabelle 相似文献
Summary An ultracentrifugal study of the sedimentation equilibrium of the system Na2[H2W12O40]-NaClO4-H2Oat 25 °C is presented. The dependency of the apparent charge of the sodium metatungstate on NaClO4-molality is investigated. From these data the dissociation constant for the dissociation of the sodium metatungstate in the presence of NaClO4 according to the equationNa[H2W12O40] 6Na+ + [H2W12O40]6– is calculated toK=0.08 mol6·kg–6. The cross differential quotient ( PXz is the trace activity coefficient of the sodium metatungstate) shows a behavior in its dependence on NaClO4-molality which to our knowledge has not yet been reported by other authors.
Mit 5 Abbildungen und 1 Tabelle 相似文献
28.
Kaishuo Yang Ehsan Sadeghi Pouya Libin Liu Dr. Ming Li Dr. Xiaoxian Yang Dr. Neil Robinson Prof. Eric F. May Prof. Michael L. Johns 《Chemphyschem》2022,23(4):e202100794
Understanding the behaviour of short-chain hydrocarbons confined to porous solids informs the targeted extraction of natural resources from geological features, and underpins rational developments in separation, storage and catalytic conversion processes. Herein, we report the application of low-field (12.7 MHz) 1H nuclear magnetic resonance (NMR) relaxation measurements to characterise ethane dynamics within mesoporous silica materials exhibiting mean pore diameters between 6 and 50 nm. Our measurements provide NMR-based adsorption isotherms within the range 25–50 bar and at ambient temperature, incorporating the ethane condensation point (40.7 bar at our experimental temperature of 23.6 °C). The quantitative nature of the acquired data is validated via a direct comparison of NMR-derived excess adsorption capacities with ex situ gravimetric ethane adsorption measurements, which are demonstrated to agree to within 0.2 mmol g−1 of the observed ethane capacity. NMR relaxation time distributions are further demonstrated as a means to decouple interparticle and mesopore dominated adsorption phenomena, with unexpectedly rapid relaxation rates associated with interparticle ethane gas confirmed via a direct comparison with NMR self-diffusion analysis. 相似文献
29.
30.
Using the multiexciton density matrix theory of excitation energy transfer in chromophore complexes developed in a foregoing paper [J. Chem. Phys. 118, 746 (2003)], the computation of ultrafast transient absorption spectra is presented. Beside static disorder and standard mechanisms of excitation energy dissipation the theory incorporates exciton exciton annihilation (EEA) processes. To elucidate signatures of EEA in intensity dependent transient absorption data the approach is applied to the B850 ring of the LH2 found in rhodobacter sphaeroides. As main indications for two-exciton population and resulting EEA we found (i) a weakening of the dominant single-exciton bleaching structure in the transient absorption, and (ii) an intermediate suppression of long-wavelength and short-wavelength shoulders around the bleaching structure. The suppression is caused by stimulated emission from the two-exciton to the one-exciton state and the return of the shoulders follows from a depletion of two-exciton population according to EEA. The EEA-signature survives as a short-wavelength shoulder in the transient absorption if orientational and energetic disorder are taken into account. Therefore, the observation of the EEA-signatures should be possible when doing frequency resolved transient absorption experiments with a sufficiently strongly varying pump-pulse intensity. 相似文献