Characteristics and origins of common chemical noise ions in negative ESI LC-MS

Ionic chemical background noise in LC-MS has been one of the major problems encountered in trace analysis. In this study, the typical negative background ions in ESI LC-MS are investigated exemplarily. It was carried out using tandem mass spectrometry to study the products and precursors of the major background ions to examine their structures and structure relationship. Various typical LC eluents with different compositions and additives such as ammonium formate/formic acid and ammonium acetate/acetic acid have been studied. Several types of negative noise ions are concluded, which include the cluster chemical background ions only from mobile phase components and additives. Furthermore, there are also abundant clusters resulting from the solvation of some typical individual contaminants (e.g. additives and degradation products from tubing, impurities in the mobile phase, etc.), accompanied by some minor contribution from contaminants. The elemental composition of some selected ions was confirmed using the FT-ICR accurate mass measurement. This work provides us insight into information about the structures and types of common negative background ions and will help to understand their formation and origins. More importantly, it will guide us to prevent chemical noise interference in practice and also contribute to develop methods for noise reduction based on selective ion-molecule reactions.     

Higher order elliptic and parabolic systems with variably partially BMO coefficients in regular and irregular domains

The solvability in Sobolev spaces is proved for divergence form complex-valued higher order parabolic systems in the whole space, on a half-space, and on a Reifenberg flat domain. The leading coefficients are assumed to be merely measurable in one spacial direction and have small mean oscillations in the orthogonal directions on each small cylinder. The directions in which the coefficients are only measurable vary depending on each cylinder. The corresponding elliptic problem is also considered.     

Zero distribution of solutions of complex linear differential equations determines growth of coefficients

It is shown that the exponent of convergence λ(f) of any solution f of with entire coefficients A₀(z), …, A_k?2(z), satisfies λ(f) ? λ ∈ [1, ∞) if and only if the coefficients A₀(z), …, A_k?2(z) are polynomials such that for j = 0, …, k ? 2. In the unit disc analogue of this result certain intersections of weighted Bergman spaces take the role of polynomials. The key idea in the proofs is W. J. Kim’s 1969 representation of coefficients in terms of ratios of linearly independent solutions. © 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim     

具多时滞的二阶非线性差分方程解的振动性

研究了一类具有多个时滞的二阶非线性差分方程,利用数学归纳法和Lebesgue控制收敛定理得出了其有界解振动的充分必要条件及其任一解与解的差分振动的充分条件,所得结果包含和推广了已有的结果.     

二阶非线性时滞差分方程解的振动性

研究了二阶非线性时滞差分方程△(α_n(△(x_n+p_nx_(n-r)))~γ)+bn(△(x_n+p_nx_(n-T)))~γ+f(n,x_(n-σ))=0给出方程振动的充分条件,推广和改进了中立时滞差分方程的许多结果.     

Surfactant addition and alternating current electrophoretic oscillation during size fractionation of nanoparticles in channels with two or three different height segments

An array of parallel planar nanochannels containing two or three segments with varying inner heights was fabricated and used for size fractionation of inorganic and biological nanoparticles. A liquid suspension of the particles was simply drawn through the nanochannels via capillary action. Using fluorescently labeled 30 nm polyacrylonitrile beads, different trapping behaviors were compared using nanochannels with 200-45 nm and 208-54-30 nm height segments. Addition of sodium dodecyl sulfate (SDS) surfactant to the liquid suspension and application of an AC electric field were shown to aid in the prevention of channel clogging. After initial particle trapping at the segment interfaces, significant particle redistribution occurred when applying a sinusoidal 8V peak-to-peak oscillating voltage with a frequency of 150 Hz and DC offset of 4V. Using the 208-54-30 nm channels, 30 nm hepatitis B virus (HBV) capsids were divided into three fractions. When the AC electric field was applied to this trapped sample, all of the virus particles passed through the interfaces and accumulated at the channel ends.     

Minimizing UV noise in supercritical fluid chromatography. I. Improving back pressure regulator pressure noise

Pressure fluctuations and resulting refractive index changes, induced by the back pressure regulator (BPR) can be a significant source of UV detector noise in supercritical fluid chromatography (SFC). The refractive index (RI) of pure carbon dioxide (CO(2)) changes ≈0.2%/bar at the most commonly used conditions in supercritical fluid chromatography (SFC) (40 °C and 100 bar), compared to 0.0045%/bar for water (CO(2) IS 44× worse). Changes in RI cause changes in the focal length of the detector cell which results in changes in UV intensity entering the detector. The change in RI (ΔRI/bar) of CO(2) decreases 8-fold at 200 bar, compared to 100 bar. A new back pressure regulator (BPR) design representing an order of magnitude improvement in the state of the art is shown to produce peak to peak pressure noise (PN(p-p)) as low as 0.1 bar, at 200 bar, and 20Hz, compared to older equipment that attempted to maintain PN(p-p)<1bar, at <5Hz. With this lower PN(p-p), changes in baseline UV offsets could be measured as a function of very small changes in pressure. A pressure change of ±1 bar at 100 bar, common with some older BPR's, produced a UV baseline offset >0.5 mAU. A pressure change of ±0.5 bar representing the previous state-of-the-art, resulted in a UV offset of 0.3m AU. Baseline noise <0.05 is required to validate methods for trace analysis. The new BPR, with a PN(p-p) of 0.1 bar, demonstrated UV peak to peak noise (N(p-p))<0.02 mAU with a >0.03 min (10Hz) electronic filter under some conditions. This new low noise level makes it possible to validate SFC methods for the first time.     

Kinetic performance limits of constant pressure versus constant flow rate gradient elution separations. Part I: theory

We report on a general theoretical assessment of the potential kinetic advantages of running LC gradient elution separations in the constant-pressure mode instead of in the customarily used constant-flow rate mode. Analytical calculations as well as numerical simulation results are presented. It is shown that, provided both modes are run with the same volume-based gradient program, the constant-pressure mode can potentially offer an identical separation selectivity (except from some small differences induced by the difference in pressure and viscous heating trajectory), but in a significantly shorter time. For a gradient running between 5 and 95% of organic modifier, the decrease in analysis time can be expected to be of the order of some 20% for both water–methanol and water–acetonitrile gradients, and only weakly depending on the value of V_G/V₀ (or equivalently t_G/t₀). Obviously, the gain will be smaller when the start and end composition lie closer to the viscosity maximum of the considered water-organic modifier system. The assumptions underlying the obtained results (no effects of pressure and temperature on the viscosity or retention coefficient) are critically reviewed, and can be inferred to only have a small effect on the general conclusions. It is also shown that, under the adopted assumptions, the kinetic plot theory also holds for operations where the flow rate varies with the time, as is the case for constant-pressure operation. Comparing both operation modes in a kinetic plot representing the maximal peak capacity versus time, it is theoretically predicted here that both modes can be expected to perform equally well in the fully C-term dominated regime (where H varies linearly with the flow rate), while the constant pressure mode is advantageous for all lower flow rates. Near the optimal flow rate, and for linear gradients running from 5 to 95% organic modifier, time gains of the order of some 20% can be expected (or 25–30% when accounting for the fact that the constant pressure mode can be run without having to leave a pressure safety margin of 5–10% as is needed in the constant flow rate mode).     

Quantum chemical studies on the structure and detonation properties of the fused polynitrodiazoles: New high energy density molecules

In this study, we explore the possibility that fused polynitrodiazoles act as high energy density materials. Density functional theory calculations at the B3LYP/aug‐cc‐pVDZ level were performed to predict the structure, energy of explosion (≈1.68 kcal g^?1), density (≈1.98 g cm^?3), detonation velocity (≈9.50 km s^?1), and detonation pressure (≈41.50 GPa) of model molecules. The predicted properties have been found to be promising compared with 3,4,5‐trinitro‐1H‐pyrazole, 1,3,5‐trinitro‐1,3,5‐triazinane, and octahydro‐1,3,5,7‐tetranitro‐l,3,5,7‐tetraazocane. The nature of azoles of the molecule presumably determines the geometry, stability, sensitivity, density, and detonation performance. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011