Sample evaporation in conventional split/splitless GC injectors. Part 3: Retaining the liquid in the vaporizing chamber

As most sample liquids tend to pass through an empty injector insert at a speed which is too high to enable complete evaporation, movement of the liquid must be arrested before it reaches the column entrance. Stopping the liquid means deposition on to a surface; this, however, is possible only after the temperature of the surface has been cooled to (or below) the boiling point of the liquid (solvent). The performance of different means of stopping the liquid has been tested visually (by the method described in Part 2). Baffles on the wall of the injector insert had hardly any effect on evaporation: the band of liquid leaving the syringe needle performed a perfect slalorn around them. The inverted cup proved more efficient, but the best performance was obtained from a light plug of glass wool: owing to its low thermal mass, the first fibers to be met by the liquid are immediately cooled to the solvent boiling point, allowing the liquid to wet it. The sample liquid is sucked up by the glass wool, from where the sample evaporates relatively slowly, often over a period of several seconds.     

Density of states due to donor-pair molecules in three- and two-dimensional semiconductor systems

The density of states is calculated for a random distribution of donor-pairs of hydrogenlike impurities in three- and two-dimensional systems. Recent investigations of the hydrogen molecule in the alternant–molecular–orbital approximation are here extended. We found that the lowest excited state ¹Σu (i.e., H⁺H^?), which is optically connected to the ground state, plays a relevant role in the absorption spectra of semiconductor systems.     

Does CH prefer a C2v rather than a Cs structure?

The closely related C_s ( 1 ) and C_2v ( 3 ) structures of CH have been reinvestigated at many ab initio levels using MP2/6-31G** and MP2/6-311 + + G(2df, 2pd) geometries. The largest basis sets employed were 6-311G(3df, 2p), 6-311 + + G(3df, 3pd), and the Dunning “correlation consistent” polarized triple-split valence basis set (cc-pVTZ). Electron correlation was probed at the MP4 level, but the QCISD method was also used with the largest basis sets. While electron correlation favors 3 over 1 by about 2 kcal/mol, the correlated relative energies with all basis sets employed range from 0.36–1.03 kcal/mol in favor of 1 . The best estimate of this difference, 0.86 kcal/mol, is essentially identical with the (scaled) zero-point energy difference, 0.84 kcal/mol, favoring 3 over 1 . These results indicate that 1 and 3 have almost exactly the same energy at 0 K. Our best value for the dissociation energy of CH is 42.0 kcal/mol [QCISD(T)/6-311 + + G(3df, 3pd)//MP2(fu)/6-311 + + G(2df, 2pd), corrected to 298 K], which agrees very well with the experimental value. © 1992 by John Wiley & Sons, Inc.     

Influence of response factors on determining equilibrium association constants of non-covalent complexes by electrospray ionization mass spectrometry

A method for determining the equilibrium association constant of a complexation reaction A + B left harpoon over right harpoon AB by electrospray ionization mass spectrometry is described. The method consists in measuring the relative intensities of the peaks corresponding to A and to AB in equimolar A-B solutions at different concentrations C(0). The results are fitted by a non-linear least-squares procedure, with the two variable parameters being the equilibrium association constant K(a) and a factor R, defined by I(AB)/I(A) = R x [AB]/[A]. The factor R is the ratio between the response factors of AB and A, and corrects for the relative electrospray responses of the complex and the free substrate A, mass discrimination of instrumental origin and/or moderate in-source dissociation. The method is illustrated with the following two systems: complexes between a double-stranded 12-base pair oligonucleotide and minor groove binders, and cyclodextrin complexes with alpha,omega-dicarboxylic acids. For the oligonucleotide complexes, it is found that the response of the complex is not dramatically different to the response of the free oligonucleotide duplex, as the double helix conformation is disturbed by the drug only to a minor extent. In the case of cyclodextrin complexes, these complexes were found to have a much higher response than free cyclodextrin. This may be due to the fact that cyclodextrin is neutral in solution, whereas the complex is charged, but it can also stem from the fact that a significant proportion of the complex is in a non-inclusion geometry. The present method requires the exact determination of the concentrations of the reactants and is applicable to 1 : 1 complexes.     

Can a single oxidant with two spin states masquerade as two different oxidants? A study of the sulfoxidation mechanism by cytochrome p450

Density functional calculations were performed on the sulfoxidation reaction by a model compound I (Cpd I) of cytochrome P450. By contrast to previous alkane hydroxylation studies, which exhibit a dominant low-spin (LS) pathway, the sulfoxidation follows a dominant high-spin (HS) reaction. Thus, competing hydroxylation and sulfoxidation processes as observed for instance by Jones et al. (Volz, T. J.; Rock, D. A.; Jones, J. P. J. Am. Chem. Soc. 2002, 124, 9724) are the result of a two-state reactivity scenario, whereby the hydroxylation originates from the LS pathway and the sulfoxidation from the HS pathway. In this manner, two spin states of a single oxidant (Cpd I) can be disguised as two different oxidants. The calculations rule out the possibility that a second oxidant (the ferric peroxide, Cpd 0 species) interferes in the observed results of Jones et al.     

A multi-technique surface study of the mercury(II) chalcogenide ion-selective electrode in saline media

X-ray photoelectron spectroscopy (XPS), secondary ion mass spectrometry (SIMS), rotating disc electrode-electrochemical impedance spectroscopy (RDE-EIS) and synchrotron radiation-grazing incidence X-ray diffraction (SR-GIXRD) have been used to study the response mechanism of the mercury(II) chalcogenide ion-selective electrode (ISE) in saline media. XPS and SIMS have shown that the chalcogenide surface is poisoned by silver chloride, or a mixture of silver halides, on continuous exposure to synthetic and real seawater. Significantly, the in-situ SR-GIXRD study demonstrated that electrode fouling in synthetic seawater is linked to the formation of poorly crystalline or amorphous silver chloride, and that the low level of free mercury(II) in a calibration buffer (i.e., 10(-14) M) is able to undergo metathesis with silver(II) sulfide in the membrane generating mercury(II) sulfide. Significantly, the results of this detailed surface study have shown that silver chloride fouling of the electrode is ameliorated in real seawater comprising natural organic ligands, and this has been attributed to the peptization of silver chloride by the surfactant-like nature of seawater ligands at pH 8. RDE-EIS aging studies have revealed that the chalcogenide membrane experiences a sluggish charge transfer reaction in seawater, and contrary to a previous report for a static electrode, the seawater matrix does not passivate the RDE. The results of this XPS, SIMS, RDE-EIS and SR-GIXRD study have elucidated the response mechanism of the mercury(II) ISE in saline media.     

Entropic barriers in nanoscale adhesion studied by variable temperature chemical force microscopy

Intermolecular interactions drive the vast majority of condensed phase phenomena from molecular recognition to protein folding to particle adhesion. Complex energy barriers encountered in these interactions include contributions from van der Waals forces, hydrogen bonding, and solvent medium. With the spectacular exception of hydrophobic interactions, contributions from the medium are usually considered secondary. We report a variable temperature force microscopy study of the interactions between several hydrogen bonds in different solvents that challenges this point of view. Surprisingly, we observed an increase in the strength of the interaction between carboxylic acid groups in ethanol as the temperature increased. Moreover, when we switched to a nonpolar solvent we observed the opposite behavior: The binding force decreased as the temperature increased. Kinetic model of bond dissociation provided quantitative interpretation of our measurements. We attributed the observed phenomena to a large entropic contribution from the ordered solvent layers that are forming on the probe and sample surfaces upon detachment. The observed reversal in the force vs temperature trend is a manifestation of a transition between thermodynamic and kinetic regimes of unbinding predicted by the model. Our results indicate that entropic barriers dominated by the interactions of solvent molecules with the surface exist in a much wider variety of systems than previously thought.     

Hyperlayer hollow-fiber flow field-flow fractionation of cells

Interest in low-cost, analytical-scale, highly efficient and sensitive separation methods for cells, among which bacteria, is increasing. Particle separation in hollow-fiber flow field-flow fractionation (HF FlFFF) has been recently improved by the optimization of the HF FIFFF channel design. The intrinsic simplicity and low cost of this HF FlFFF channel allows for its disposable usage. which is particularly appealing for analytical bio-applications. Here, for the first time, we present a feasibility study on high-performance, hyperlayer HF FIFFF of micrometer-sized bacteria (Escherichia coli) and of different types of cells (human red blood cells, wine-making yeast from Saccharomyces cerevisiae). Fractionation performance is shown to be at least comparable to that obtained with conventional, flat-channel hyperlayer FIFFF of cells, at superior size-based selectivity and reduced analysis time.