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101.
In recent years capillary chromatography has gained popularity for trace analyses. Most often UV or electrochemical detection is employed because the small peak volumes make post-column derivatization challenging. We have developed a simple method based on flow injection for determining contributions to peak broadening from post-column reactors. The only requirement for application of our methodology is that diffusion be in the Taylor regime so that radial concentration gradients are relaxed enabling mixing purely by diffusion. 相似文献
102.
R. B. King 《Russian Chemical Bulletin》1993,42(8):1283-1291
Methods derived from topology and graph theory indicate that the deltahedral boranes B
n
H
n
2– and the corresponding carboranes C2Bn–2H
n
(6 n 12) may be regarded as three-dimensional delocalized aromatic systems in which surface bonding and core bonding correspond to -bonding and -bonding, respectively, in planar polygonal two-dimensional hydrocarbons CinnH
n
(n–6)+ (n=5/7). The two extreme types of topologies which may be used to model core bonding in deltahedral boranes and carboranes are the deltahedral (D
n
) topology based on the skeleton of the underlying deltahedron and the complete (K
n
) topology based on the corresponding complete graph. Analyses of the Hoffmann-Lipscomb LCAO extended Hückel computations, the Armstrong—Perkins—Stewart self-consistent molecular orbital computations, and SCF MOab initio GAUSSIAN-82 computations on B6H6
2– indicate that the approximation of the atomic orbitals by the sum of the molecular orbitals, as is typical in modernab initio computations, leads to significantly weaker apparent core bonding approximated more closely by deltahedral (D
n
) topology than by complete (K
n
) topology.This work was presented at the Workshop The Modern Problems of Heteroorganic Chemistry sponsored by the A. N. Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences (May 8–13, 1993).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1353–1360, August, 1993. 相似文献
103.
Zeng W Wang AQ Fisher AL Musson DG 《Rapid communications in mass spectrometry : RCM》2003,17(22):2475-2482
A generic high-throughput liquid chromatography (HTLC) tandem mass spectrometry (MS/MS) assay for the determination of compound I in human urine and dialysate (hemodialysis) was developed and validated. By using the HTLC on-line extraction technique, sample pretreatment was not necessary. The sample was directly injected onto a narrow bore large particle size extraction column (50 x 1.0 mm, 60 microm) where the sample matrix was rapidly washed away using a high flow rate (5 mL/min) aqueous mobile phase while analytes were retained. The analytes were subsequently eluted from the extraction column onto an analytical column using an organic-enriched mobile phase prior to mass spectrometric detection. The analytes were then eluted from the analytical column to the mass spectrometer for the determination. The linear dynamic range was 2.0-6000 ng/mL for the urine assay and 0.1-300 ng/mL for the dialysate assay. Intraday accuracy and precision were evaluated by analyzing five replicates of calibration standards at all concentrations used to construct the standard curve. For the urine assay, the precision (RSD%, n=5) ranged from 1.9 to 8.0% and the accuracy ranged from 87.8 to 105.2% of nominal value. For the dialysate assay, the precision (RSD%, n=5) ranged from 1.1 to 10.0% and the accuracy from 94.5 to 105.2% of nominal value. In-source fragmentation of the acyl glucuronide metabolite (compound III) did not interfere with the determination of parent compound I. The developed HTLC/MS/MS methodology was specific for compound I in the presence of compound III. Column life-time is increased and sample analysis time is decreased over traditional reversed-phase methods when direct injection assays for urine and dialysate are coupled with the technology of HTLC. 相似文献
104.
R. B. King 《Journal of mathematical chemistry》1991,7(1):69-84
Most chiral molecules can be dissected into a collection of ligands attached to an underlying skeleton. Application of permutation group theory and group representation theory to such a model can lead to chirality functions which can be used to approximate pseudoscalar measurements such as optical rotation or circular dichroism. Such chirality functions have been tested experimentally for the following skeletons: (1) The polarized triangle of phosphines and phosphine oxides; (2) the tetrahedron of methane derivatives; (3) the disphenoid of allene and 2, 2-spirobiindane derivatives; (4) the polarized rectangle of [2, 2]-metacyclophanes; (5) the polarized pentagon of heterodisubstituted ferrocenes. The success of this method is fair to good for the polarized triangle, tetrahedron, and disphenoid skeletons but deteriorates rapidly for the polarized rectangle and polarized pentagon skeletons, in accord with the greater group-theoretical complexity of the latter skeletons. 相似文献
105.
The 60 even permutations of the ligands in the five-coordinate complexes, ML
5, form the alternating group A
5, which is isomorphic with the icosahedral pure rotation group I. Using this idea, it is shown how a regular icosahedron can be used as a topological representation for isomerizations of the five-coordinate complexes, ML
5, involving only even permutations if the five ligands L correspond either to the five nested octahedra with vertices located at the midpoints of the 30 edges of the icosahedron or to the five regular tetrahedra with vertices located at the midpoints of the 20 faces of the icosahedron. However, the 120 total permutations of the ligands in five-coordinate complexes ML
5 cannot be analogously represented by operations in the full icosahedral point group I
h, since I
his the direct product I×C2 whereas the symmetric group S
5 is only the semi-direct product A
5S2. In connection with previously used topological representations on isomerism in five-coordinate complexes, it is noted that the automorphism groups of the Petersen graph and the Desargues-Levi graph are isomorphic to the symmetric group S
5 and to the direct product S
5×S
2, respectively. Applications to various fields of chemistry are briefly outlined. 相似文献
106.
Lynch CL Hale JJ Budhu RJ Gentry AL Finke PE Caldwell CG Mills SG MacCoss M Shen DM Chapman KT Malkowitz L Springer MS Gould SL DeMartino JA Siciliano SJ Cascieri MA Carella A Carver G Holmes K Schleif WA Danzeisen R Hazuda D Kessler J Lineberger J Miller M Emini E 《Organic letters》2003,5(14):2473-2475
[reaction: see text] A novel approach to alpha,alpha-disubstituted-beta-amino acids (beta(2,2)-amino acids) was employed in the synthesis of a series of 3-(pyrrolidin-1-yl)propionic acids possessing high affinity for the CCR5 receptor and potent anti-HIV activity. The rat pharmacokinetics for these new analogues featured higher bioavailabilities and lower rates of clearance as compared to cyclopentane 1. 相似文献
107.
108.
The reagent 4-sulfophenyl isothiocyanate (SPITC) is an effective, stable, and inexpensive alternative to commercially available reagents used in the N-terminal sulfonation of peptides for enhanced postsource decay (PSD) in matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOFMS) analyses. However, suppression of ionization of sulfonated peptides due to sample and matrix contaminants such as sodium can be a problem when using prestructured MALDI target sample supports, such as the Bruker Daltonics AnchorChip. We show that use of the salt-tolerant matrix 2,4,6-trihydroxyacetophenone containing diammonium citrate (THAP/DAC) as an alternative to alpha-cyanohydroxycinnamic acid (HCCA) reduces the need for extensive washing of ZipTip-bound peptides or additional on-target sample clean-up steps. Use of the THAP/DAC matrix results in selective ionization of sulfonated peptides with greater peptide coverage, as well as detection of higher mass derivatized peptides, than was observed for HCCA or THAP alone. The THAP/DAC matrix is quite tolerant of sodium contamination, with SPITC-peptides detectable in preparations containing up to 50 mM NaCl. In addition, THAP/DAC matrix was found to promote efficient PSD fragmentation of sulfonated peptides. We demonstrated the utility of using the THAP/DAC MALDI matrix for peptide sequencing with DNA polymerase beta tryptic peptide mixture, as well as tryptic peptides derived from Xiphophorus maculatus brain extract proteins previously separated by two-dimensional polyacrylamide gel electrophoresis (2D-PAGE). 相似文献
109.
P-Nitrosophosphates, such as 9, react as N-O heterodienophiles with 1,3-dienes to form highly functionalized cycloadducts that can be directly transformed into allylic phosphoramidates. The in situ periodate oxidation of the unstable N-hydroxyphosphoramidate precursors provides an efficient preparation of these new reactive intermediates. P-Nitrosophosphate (9) regioselectively reacts with 1-methoxy-1,3-butadiene to provide cycloadduct 16. P-Nitrosophosphate (9) also reacts with 9,10-dimethylanthracene to give cycloadduct 17, which undergoes retro Diels-Alder dissociation to re-form 9. In the absence of a 1,3-diene, the decomposition of 17 produces nitrous oxide, evidence for nitroxyl, the one-electron-reduced form of nitric oxide. An asymmetric P-nitrosophosphate reacted with 1,3-cyclohexadiene to form a mixture of diastereomeric cycloadducts (19 and 20) in a 1.6:1 ratio. These results identify P-nitrosophosphates as new species that react similarly to acyl nitroso compounds, making them useful synthetic intermediates and potential nitroxyl delivery agents. 相似文献
110.
Brunsvold AL Garton DJ Minton TK Troya D Schatz GC 《The Journal of chemical physics》2004,121(23):11702-11714
Crossed molecular beams experiments and classical trajectory calculations have been used to study the dynamics of Ar+ethane collisions at hyperthermal collision energies. Experimental time-of-flight and angular distributions of ethane molecules that scatter into the backward hemisphere (with respect to their original direction in the center-of-mass frame) have been collected. Translational energy distributions, derived from the time-of-flight distributions, reveal that a substantial fraction of the collisions transfer abnormally large amounts of energy to internal excitation of ethane. The flux of the scattered ethane molecules increased only slightly from directly backward scattering to sideways scattering. Theoretical calculations show angular and translational energy distributions which are in reasonable agreement with the experimental results. These calculations have been used to examine the microscopic mechanism for large energy transfer collisions ("supercollisions"). Collinear ("head-on") or perpendicular ("side-on") approaches of Ar to the C-C axis of ethane do not promote energy transfer as much as bent approaches, and collisions in which the H atom is "sandwiched" in a bent Ar...H-C configuration lead to the largest energy transfer. The sensitivity of collisional energy transfer to the intramolecular potential energy of ethane has also been examined. 相似文献