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61.
P. G. Mendoza Jr D. D. Jackson T. M. Niemczyk 《Journal of Radioanalytical and Nuclear Chemistry》1990,141(2):357-371
The uranium spectrophotometric measurement using the uranylnitrate-quaternaryamine solvent extraction method is investigated to identify factors that affect precision and accuracy of the uranium determination. The inherent spectrophotometric precision was measured with neutral density filters in the sample light path and was found to be <0.1% relative standard deviation (RSD). Under selected experimental conditions, temperature instability has a –0.02% effect on the extraction, and a –0.4% effect on the absorbance of the uranium extract in 2-nitropropane (2-NP) or methyl isobutyl ketone (MIBK) solvents. Under optimum conditions at the 10 mg uranium level, RSDs of 0.1% resulted. 相似文献
62.
Difficulties in carrying out the free-radical addition of trialkylsilanes (as opposed to trichlorosilane) to alkene CC bonds are partly due to telomerization competing with the radical transfer step. This can be overcome by the use of a large excess of trialkylsilane, when good yields of adduct are obtained from mono-substituted and 1,2-disubstituted alkenes. 相似文献
63.
Targeted cellular delivery of drugs to specific tissues is an important goal in biomedical chemistry. Achieving this requires harnessing and applying molecular-level recognition events prevalent in (or specific to) the desired tissue type. Tissues rich in estrogen receptors (ERs), which include many types of breast cancer, accumulate molecules that have high binding affinities for these receptors. Therefore, molecules that (i) bind to the ER, (ii) have favorable cellular transport properties, and (iii) contain a second functionality (such as a center that may be used for diagnostic imaging or medical therapy) are exciting synthetic targets in the field of drug delivery. To this end, we have prepared a range of metallo-estrogens based on 17alpha-ethynylestradiol and examined their binding to the ER both as isolated receptor and in whole cell assays (ER positive MCF-7 cells). Estrogens functionalized with metal binding units are prepared by palladium-catalyzed cross-coupling reactions and a wide range of metal centers introduced readily. All the compounds prepared and tested exhibit effective binding to the estrogen receptor and are delivered across the cell membrane into MCF-7 cells. In the whole cell assays, despite their monocationic nature, the palladium and platinum complexes prepared exhibit similar (and even enhanced) receptor binding affinities compared to their corresponding neutral free ligands. It is unprecedented for a higher ER binding affinity to be observed for a cationic complex than for its metal-free ligand. 相似文献
64.
Alexander Orahovats Barry Jackson Heinz Heimgartner Hans Schmid 《Helvetica chimica acta》1973,56(6):2007-2011
Irradiation of 2-azido-3-phenyl-propene ( 5 ) in pentane or benzene solution with a high pressure lamp (pyrex filter) yields 3-benzyl-2H-azirin ( 6 ), which on further irradiation behind quartz or vycor in the presence of trifluoroacetic acid methylester or carbon dioxide yields 4-benzyl-5-methoxy-5-trifluoromethyl-3-oxazolin ( 8 ) and 4-benzyl-3-oxazolin-5-one ( 9 ), respectively (scheme 2). A small amount of 3-phenylacetonitrile is also formed. 相似文献
65.
A review is presented detailing the development and use of suppression devices for the conductimetric detection of inorganic ions by ion chromatography (IC). An overview of the general response equation for conductivity detection is also given. Topics of discussion include the role and function of suppressors, the development of early suppressors including packed column and membrane devices from 1975 to 1990 and the subsequent progression towards present day commercially available suppressors and recent innovations. Post-suppression devices for signal enhancement are also discussed. 相似文献
66.
Jackson P Srinivas R Blanksby SJ Schroder D Schwarz H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2000,6(7):1236-1242
The cation [Si,C,O]+ has been generated by 1) the electron ionisation (EI) of tetramethoxysilane and 2) chemical ionisation (CI) of a mixture of silane and carbon monoxide. Collisional activation (CA) experiments performed for mass-selected [Si,C,O]+, generated by using both methods, indicate that the structure is not inserted OSiC+; however, a definitive structural assignment as Si(+)-CO, Si(+)-OC or some cyclic variant is impossible based on these results alone. Neutralisation-reionisation (+NR+) experiments for EI-generated [Si,C,O]+ reveal a small peak corresponding to SiC+, but no detectable SiO+ signal, and thus establishes the existence of the Si(+)-CO isomer. CCSD(T)@B3LYP calculations employing a triple-zeta basis set have been used to explore the doublet and quartet potential-energy surfaces of the cation, as well as some important neutral states. The results suggest that both Si(+)-CO and Si(+)-OC isomers are feasible; however, the global minimum is 2 pi SiCO+. Isomeric 2 pi SiOC+ is 12.1 kcal mol-1 less stable than 2 pi SiCO+, and all quartet isomers are much higher in energy. The corresponding neutrals Si-CO and Si-OC are also feasible, but the lowest energy Si-OC isomer (3A") is bound by only 1.5 kcal mol-1. We attribute most, if not all, of the recovery signal in the +NR+ experiment to SiCO+ survivor ions. The nature of the bonding in the lowest energy isomers of Si(+)-(CO,OC) is interpreted with the aid of natural bond order analyses, and the ground state bonding of SiCO+ is discussed in relation to classical analogues such as metal carbonyls and ketenes. 相似文献
67.
Harvey DJ Martin RL Jackson KA Sutton CW 《Rapid communications in mass spectrometry : RCM》2004,18(24):2997-3007
N-Linked glycans were ionized from several matrices with a Shimadzu-Biotech AXIMA-QIT matrix-assisted laser desorption/ionization quadrupole ion trap time-of-flight mass spectrometer. [M+Na]+ ions were produced from all matrices and were accompanied by varying amounts of in-source fragmentation products. The least fragmentation was produced by 2,5-dihydroxybenzoic acid and the most by alpha-cyano-4-hydroxycinnamic acid and 6-aza-2-thiothymine. Sialic acid loss was extensive but could be prevented by formation of methyl esters. Fragmentation produced typical low-energy-type spectra dominated by ions formed by glycosidic cleavages. MS(n) spectra (n = 3 and 4) were used to probe the pathways leading to the major diagnostic ions. Thus, for example, an ion that was formed by loss of the core GlcNAc residues and the 3-antenna was confirmed as being formed by a B/Y rather than a C/Z mechanism. The proposed structures of several cross-ring cleavage ions were confirmed and it was shown that MS3 spectra could be obtained from as little as 10 fmol of glycan. 相似文献
68.
Jeffrey C. Evans Simon K. Jackson Christopher C. Rowlands Martin D. Barratt 《Analytica chimica acta》1986
The covalent binding of 35S-chloramine-T to human resum albumin (HSA) and ovalbumin is described. At pH 6.5, up to 24 chloramine-T molecules were found to be covalently bound per molecule of HSA; with ovalbumin the binding was only 5–7 molecule per protein molecule. Binding was accompanied by extensive modification of methionine, cysteine, histidine, tyrosine and lysine. Three new peaks appeared in the amino acid profiles of the modified proteins; two were identified as 1-aminoadipic acid (oxidation of lysine) and 3-chlorotyrosine. The most sites for covalent binding are lysine residues. 相似文献
69.
The thermodynamic functions Gibbs energy, enthalpy and entropy of solution, mixing and solvation of acetaminophen in propylene
glycol (PG) + ethanol (EtOH) cosolvent mixtures were evaluated from solubility data measured at several temperatures, using
the van't Hoff and Gibbs equations. The solubility was greater at 50% m/m of PG at 20.0^C, while it was greater at 80% of
PG at 40.0 ^C where m/m refers to mass percent. The solvation of this drug is appreciably greater in the mixtures than in
the pure solvents. By means of an enthalpy–entropy compensation analysis, complex behavior was found for the solution. From
0 up to 20% of PG and from 60 up to 100% of PG the solution process is enthalpy driven, whereas from 20 up to 60% of PG it
is entropy driven. These facts can be explained in terms of a decrease in the energy required for cavity formation in the
solvent for mixtures containing 20–60% of PG. 相似文献
70.
NMR SPDE measurements are reported for the lamellar (dispersions and multibilayer stacks) and hexagonal phases of sodium octanoate/octanol/D2O mixtures. In the lamellar Lβ and Lγ (gel) phases the octyl chains are rigid and perfectly ordered, while in the lamellar Lα and hexagonal phases they are flexible and disordered. In particular, the measurements show that in the fluid lamellar Lα phase, there is a marked discontinuity in the octyl chain flexibility at the C5-C6 segment; this behaviour is identical to that previously reported for the alkyl end-chains in smectic 4,4′-di-n-octyloxyazoxybenzene. In contrast, in the hexagonal phase, there is an effectively continuous flexibility gradient along the whole length of the octyl chain as in nematic 4,4′-di-n-octyloxyazoxybenzene. The behaviour in the lamellar phase is attributed to interference between cooperative conformational modes and localized random thermal fluctuations. 相似文献