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61.
An automated, continuous-flow system is utilized to determine specific conductance and pH simultaneously in natural waters. A direct electrometric procedure is used to determine values in the range pH 4–9. The specific conductance measurements are made with an electronically modified, commercially available conductivity meter interfaced to a separate module containing the readout control devices and printer. The system is designed to switch ranges automatically to accommodate optimum analysis of widely varying conductances ranging from a few μmhos cm-1 to 15,000 μmho cm-1. Thirty samples per hour can be analyzed. Comparison of manual and automated procedures for 40 samples showed that the average differences were 1.3% for specific conductance and 0.07 units for pH. The relative standard deviation for 25 replicate values for each of five samples was significantly less than 1% for the specific conductance determination; the standard deviation for the pH determination was ? 0.06 pH units. 相似文献
62.
A new method to compute intermolecular energies in non-bonding regions is presented. It is based on the assumption that in such regions molecules can be reviewed as the sum of distorted, possibly overlapping, and electron exchanging atoms. The intermolecular energy change at a given distance is due to the sum of the atomic energy changes caused by these distortions. The energy change of any particular atom is computed in a Hartree—Fock model in which the effect of the other atom is represented by an effective potential. This potential in turn is computed from a calculation at a slightly larger intermolecular distance of the potential seen by an external electron in the field of the “other” atom. This potential computed in the RPA approximation and involves the distorted Hartree—Fock orbitals of the other atom (computed in a similar manner to the above) and the RPA response function of the other distorted atom. 相似文献
63.
Wong KL Bitter M Hammett GW Heidbrink W Hendel H Kaita R Scott S Strachan JD Tait G Bell MG Budny R Bush C Chan A Coonrod J Efthimion PC England AC Eubank HP Fredrickson E Furth HP Goldston RJ Grek B Grisham L Hawryluk RJ Hill KW Johnson D Kamperschroer J Kugel H Ma C Mansfield D Manos D McCune DC McGuire K Medley SS Mueller D Nieschmidt E Owens DK Paré VK Park H Ramsey A Rasmussen D Roquemore AL Schivell J Sesnic S Taylor G Williams MD Zarnstorff MC 《Physical review letters》1985,55(23):2587-2590
64.
65.
It is shown that a simple expression for the partial widths in a multichannel decay problem can be readily obtained from a Siegert wavefunction. 相似文献
66.
Startin JR Sykes MD Taylor JC Hird SJ Jackson K Fussell RJ Hill AR 《Journal of AOAC International》2000,83(3):735-741
A method was developed for the simultaneous determination of residues of pirimicarb (I) and its desmethylformamido (II) and desmethyl (III) metabolites in plums, peas, green beans, broad beans, carrots, and swedes. The compounds were extracted with ethyl acetate and determined, without cleanup, by reversed-phase liquid chromatography and electrospray mass spectrometry (MS). MS and MS/MS were used concurrently to monitor the protonated molecules and their common collision-induced dissociation product. The limit of detection (signal-to-noise ratio of >3) was 1 ng/mL, corresponding to crop concentrations of <0.0015 mg/kg. All 3 compounds were determined in plums, broad beans, and green beans by MS without interference. Interferences which affected the determination of desmethylformamido-pirimicarb in peas, and to a lesser extent in carrots and swedes, were eliminated by MS/ MS. Recoveries for all 3 compounds, at 0.05 mg/kg for plums and 0.005 mg/kg for other commodities, were in the range 83-124%. No interconversion of I, II and III, occurred during extraction, and the compounds were stable in extracts for > or = 7 days under appropriate conditions. 相似文献
67.
Alan W. Duff Peter B. Hitchcock Michael F. Lappert Richard G. Taylor John A. Segal 《Journal of organometallic chemistry》1985,293(3):271-283
n-Heptane-soluble “di-butylmagnesium” (I) (a commercially available material, prepared by addition of LiBus to MgBunCl, and subsequent addition of ca. 5% MgOct2n) has been found to be a useful starting material for obtaining numerous organic magnesium compounds. This is illustrated by its reaction with a number of protic compounds HA to give in good yields Mg(C5H5)2, Mg(C5H4Me)2, or the new compounds MgA2: IV (A = C5H4SiMe3), V [A = C5H3(SiMe3)2], VII (A = OC6H2Bu2t-2,6-Me-4), and X [A2 = N(SiMe3)C6H4N(SiMe3)-o(OEt2)]. The value of such compounds MgA2 as mild ligand transfer reagents is illustrated by the synthesis of Zr(C5H3X2)Cl3 (X = H or SiMe3). Compound X was isolated from OEt2 solution as the crystalline dimer with two o-(SiMe3)C6H4(SiMe3) ligands bridging two magnesium atoms and a terminal OEt2 ligand completing a distorted tetrahedral environment around each Mg. Some key parameters are: MgNt 1.997(7), MgNb 2.083(8), MgO 2.041(7) Å; OMgNt 112.1(3), OMgNb 119.7(3), and NtMgNb 118.5(3)°. 相似文献
68.
Fisher KA Huddersman KD Taylor MJ 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(23):5873-5878
The uptake of the three species of the drug model fluorescein (fluorescein sodium salt (FNa), fluorescein free acid (F), and fluorescein diacetate (FDA)) by zeolite NaX and the mesoporous zeotype MCM-41 was investigated as well as their release rates into solutions at pH 7 and pH 4.5. UV/Vis analysis was carried out at a wavelength of 490 nm. Uptakes of the sodium salt of 9 % for zeolite X and 14 % for MCM suggest little penetration of the pores. The use of ethanol as the loading solvent for F resulted in little uptake for both zeolitic materials due to the successful competition of the ethanol for binding sites. Use of acetone (weaker proton acceptor) as loading solvent significantly improved the uptake of F to 17 % and 12 % for zeolite X and MCM, respectively, whilst the uptake of FDA in acetone increased still further to 22 % and 17 % for zeolite X and MCM, respectively. Generally there was a large initial release of the fluorescein analogues from the surface of the zeolites with very little further increase over time. The prescence of an esterase enzyme in the release medium of FDA tripled the release from MCM to 15 % but left the release from zeolite X unaffected at 6 %. The results obtained show that uptake of fluorescein and its analogues is dependent on the loading solvent used, the amount released is influenced by not only the solvent but the pH and the presence of enzymes in the release medium. 相似文献
69.
The products of hydrolysis of C60F48 (which contains six isolated double bonds) by either aq. acetone or aq. THF show that no more than twelve fluorines are replaced through nucleophilic substitution, as predicted by the recently identified S(N)2' mechanism. Subsequent HF elimination gives fragments containing a maximum of six epoxide oxygens. Calculated heats of formation of models for the possible initial hydroxy derivatives indicate that there is little energetic discrimination between them, so that a complex mixture is likely to be formed. Overall the data show that hydrolytic degradation of fluorofullerenes is less severe than believed previously, requires a specific motif, and explains the low susceptibility of C60F18 towards hydrolysis and the high stability of trannulenes. 相似文献
70.
We present formulas for the evaluation of molecular integrals over basis functions with an explicit Gaussian dependence on
interelectronic coordinates. These formulas use expansions in Hermite Gaussian functions and represent an extension to the
work of McMurchie and Davidson to two-electron basis functions. Integrals that depend on the coordinates of up to four electrons
are discussed explicitly. A key feature of this approach is that it allows full exploitation of the shell structure of the
orbital part of the basis.
Received: 24 February 1997 / Accepted: 4 March 1997 相似文献