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21.
A microchip structure etched on a glass substrate for packed column solid-phase extraction (SPE) and capillary electrochromatography (CEC) is described. A 200 microm long, octadecylsilane (ODS) packed column was secured using two different approaches: solvent lock or polymer entrapment. The former method was utilized for SPE while the latter approach was applied for CEC. In SPE, the ODS packed chamber gave a detection limit of 70 fM for a nonpolar BODIPY (493/503) dye when concentrated for 3 min at an electroosmotic flow rate of 4.14 nL/min, compared to 30 pM for this detector without the SPE step. SPE beds showed reproducible, linear calibration curves (R(2) = 0.9989) between 1 and 100 pM BODIPY at fixed preconcentration times. Breakthrough curves for the 330 pL (ODS-packed) bed indicated a capacity for BODIPY dye of 8.1 x 10(-14) mmol, or 0.25 mmol dye per liter of bed. The ODS-chamber could also be used to analyze dilute amino acid and peptide solutions. In the CEC format, two neutral dyes (BODIPY and acridine orange) were baseline-separated in an isocratic run with a theoretical plate count of 84 (420 000 plates/m) and a reduced plate height of about 1. A labeled peptide was also analyzed by CEC, using the acidic eluent (84% acetonitrile, and 26% aqueous trifluoroacetic acid (0.05%)) preferred for peptide separations on ODS-coated silica particles. 相似文献
22.
(13)C spin-lattice relaxation studies on bis(2-ethylhexyl) adipate (DOA) plasticized poly(vinylchloride) (PVC) membranes are reported for plasticization levels ranging from 25 to 100 wt% plasticizer. The interaction between DOA and PVC molecules in these membranes appears to involve an entrapment of the plasticizer molecule within the polymer matrix. This is based on the constancy of the characteristic segmental motions of the plasticizer chains throughout the concentration range studied. The segmental mobility of the plasticizer component is modified by water absorption in the membrane. The pattern of characteristic segmental motions of the plasticizer is altered, the effect depending on the amount of added salt in the membrane. The results show water has a weak influence on the microviscosity of the membrane matrix. 相似文献
23.
S. W. Harrison S. Swaminathan David L. Beveridge Robert Ditchfield 《International journal of quantum chemistry》1978,14(3):319-327
An analytical potential function for the pairwise interaction of methane and water is reported. The function is representative of 225 ab initio quantum-mechanical calculations of the intermolecular interaction using 6–31G self-consistent-field molecular-orbital theory. The statistical parameters of the curve fitting are given and isoenergy contour maps of the interaction energy are presented and discussed. 相似文献
24.
The H2 and CH4 chemical ionization mass spectra of a series of series of substituted benzoic acids and substituted benzyl alcohols have been determined. For the benzoic acids the major fragmentation reactions of the protonated molecule involve elimination of H2O or elimination of CO2, the latter reaction involving migration of the carboxylic hydrogen to the aromatic ring. For the benzyl alcohols the major fragmentation reactions of [MH]+ involve loss of H2O or CH2O, analogous to the CO2 elimination reaction for the benzoic acids. It is shown that the CO2 and CH2O elimination reactions occur only when a conjugated aromatic ring system is present, and that for the carboxylic acid systems, methyl groups and, to a lesser extent, phenyl groups are capable of migrating. The only discernible effect of substituents on the fragmentation of [MH]+ is an enhancement of the H2O loss reaction in the benzoic acid system when an amino, hydroxyl, or halogen substituent is ortho to the carboxyl function. This ‘ortho’ effect, which differs in scope from that observed in electron impact mass spectra, is attributed to an intramolecular catalysis by the ortho substituent of the 1,3 hydrogen migration in the carbonyl protonated acid followed by H2O elimination. Apparently, this route is favoured over the direct elimination of H2O from the carbonyl protonated acid, since the latter has a high activation energy barrier because of unfavourable orbital symmetry restrictions. 相似文献
25.
The H2, N2/H2, CO2/H2, N2O/H2, CO/H2 and CH4 chemical ionization mass spectra of thirteen C8 to C11 alkylbenzenes are reported. Characteristic hydride and alkide ion abstraction reactions are observed with all reagent gases. The major fragmentation reactions of [MH]+ are olefin elimination to form a protonated arene and arene elimination to form an alkyl ion. From the effect of structure and protonation exothermicity it is concluded that rearrangement of primary alkyl groups to the more stable secondary or tertiary structure occurs prior to alkyl ion formation. A detailed fragmentation mechanism for protonated arenes is proposed. The ‘effective’ proton affinity of the methane-derived reagent system is estimated to be ~556 kJ mol?1. 相似文献
26.
R. G. Harrison 《Chemical physics letters》1980,70(3):555-559
The absorption characteristics of cyclobutanone vapour irradiated with a pulsed CO2 TEA laser at fluences of 0.5–1.5 J cm−2have been studied over the pressure range 0.3 to 20 Torr using both joulemeter and opto-acoustic measurements of the absorbed energy. Under these conditions the product concentration for the two subsequent decomposition channels into ethene + ketene and cyclopropane + CO were determined. Above ≈ 3 Torr the results are consistent with a thermally equilibrated system whereas at lower pressures a distinct enhancement of the lower energy pathway to ethene occurs, indicative of a non-Boltzmann energy distribution. 相似文献
27.
Iminodiacetate resorc[4]arene is shown to produce gels that are pH-reversible. The gels formed are clear and stable to inversion. (The gels are not stable above a certain temperature, which varies with concentration.) When the pH of an iminodiacetate resorc[4]arene solution (concentration > 7.6 mM) is lowered to below 2.5, which is near one of the Ka values of the molecule, the dissolved molecules aggregate and cause gelation of water. 1H NMR showed that at the pH of gelation a change occurs in the chemical environment of the iminodiacetate group. Scanning electron microscopy showed that the gel is composed of long strands that interweave and create a molecular mesh. 相似文献
28.
The type 1 copper sites of cupredoxins typically have a His(2)Cys equatorial ligand set with a weakly interacting axial Met, giving a distorted tetrahedral geometry. Natural variations to this coordination environment are known, and we have utilized paramagnetic (1)H NMR spectroscopy to study the active-site structure of umecyanin (UMC), a stellacyanin with an axial Gln ligand. The assigned spectra of the Cu(II) UMC and its Ni(II) derivative [Ni(II) UMC] demonstrate that this protein has the typical His(2)Cys equatorial coordination observed in other structurally characterized cupredoxins. The NMR spectrum of the Cu(II) protein does not exhibit any paramagnetically shifted resonances from the axial ligand, showing that this residue does not contribute to the singly occupied molecular orbital (SOMO) in Cu(II) UMC. The assigned paramagnetic (1)H NMR spectrum of Ni(II) UMC demonstrates that the axial Gln ligand coordinates in a monodentate fashion via its side-chain amide oxygen atom. The alkaline transition, a feature common to stellacyanins, influences all of the ligating residues but does not alter the coordination mode of the axial Gln ligand in UMC. The structural features which result in Cu(II) UMC possessing a classic type 1 site as compared to the perturbed type 1 center observed for other stellacyanins do not have a significant influence on the paramagnetic (1)H NMR spectra of the Cu(II) or Ni(II) proteins. 相似文献
29.
Andreas Manz Elisabeth Verpoorte Carlo S. Effenhauser Norbert Burggraf Daniel E. Raymond D. Jed Harrison H. Michael Widmer 《Journal of separation science》1993,16(7):433-436
Miniaturization of separation columns implies equally reduced vol- umes of injectors, detectors, and the connecting channels. Planar chip technology provides a powerful means for the fabrication of micron-sized structures such as channels. This is demonstrated by two examples. An optical absorbance detector chip exhibits the expected behavior of a 1 mm optical path length cell despite its volume of 1 nL. A capillary electrophoresis device allows integrated injections of 100 pL samples, efficiencies of 70,000 to 160,000 theoretical plates in 10 to 20 seconds, and external laser-induced fluorescence detection at any capillary length of choice between 5 and 50 mm. 相似文献
30.
The kinetics of the binding of the neurotoxin acrylamide to the cysteine residue of glutathione has been studied. At 37 °C and pH 7.3 the second order rate constant has been determined to be 0.72 ± 0.06 mol?1 dm3 min?1 by thermospray mass spectrometry. The critical energy at pH 11.5 measured over the temperature range 10–37°C by fast atom bombardment mass spectrometry was measured as 24.6 kJ mol?1. 相似文献