Separation of glycosidic catiomers by TWIM‐MS using CO2 as a drift gas

Traveling wave ion mobility mass spectrometry (TWIM‐MS) is shown to be able to separate and characterize several isomeric forms of diterpene glycosides stevioside (Stv) and rebaudioside A (RebA) that are cationized by Na⁺ and K⁺ at different sites. Determination and characterization of these coexisting isomeric species, herein termed catiomers, arising from cationization at different and highly competitive coordinating sites, is particularly challenging for glycosides. To achieve this goal, the advantage of using CO₂ as a more massive and polarizable drift gas, over N₂, was demonstrated. Post‐TWIM‐MS/MS experiments were used to confirm the separation. Optimization of the possible geometries and cross‐sectional calculations for mobility peak assignments were also performed. Copyright © 2015 John Wiley & Sons, Ltd.     

On two-photon excited gas drift under a train of ultrashort laser pulses

A theoretical analysis has been carried out of the light-induced drift (LID) of gases which is two-photon-excited by a mode-locked laser radiation. The mode-locking is shown to ensure a 10²–10³ times increase of the LID-effect estimated under typical experimental conditions.     

Homogeneous Bose gas of dipolar molecules in the mean field approximation

We present a mean field analysis of the effects of molecular rotation on the excitation spectrum and stability of ultracold dipolar gases. For an unpolarized homogeneous gas interacting with a pure dipole-dipole interaction, we find that for the rotational state L = 1 the dipole-dipole interaction causes a splitting of the translation-rotation energy levels into a single M = 0 and a doubly degenerate M = ±1 excitation. For all other rotational states, the dipole-dipole interaction does not lead to coupling of translations and rotations and therefore has no effect on the rotational degeneracy of the excitations. The addition of arbitrarily small electric fields is found to introduce instabilities similar to those known to arise in the fully polarized dipolar gas. As in the case of a fully polarized gas, addition of a large enough short range repulsive potential is seen to stabilize the system, with the critical value of the repulsive interaction required for stabilization being larger when rotations are included.     

Synthesis of a dipolar nanocar

The synthesis of a nanocar with a built-in strong net dipole is disclosed. The synthesis was executed to explore a more effective handle on electric-field-induced rolling of nanocars.     

Identity confirmation of drugs and explosives in ion mobility spectrometry using a secondary drift gas

This work demonstrated the potential of using a secondary drift gas of differing polarizability from the primary drift gas for confirmation of a positive response for drugs or explosives by ion mobility spectrometry (IMS). The gas phase mobilities of response ions for selected drugs and explosives were measured in four drift gases. The drift gases chosen for this study were air, nitrogen, carbon dioxide and nitrous oxide providing a range of polarizability and molecular weights. Four other drift gases (helium, neon, argon and sulfur hexafluoride) were also investigated but design limitations of the commercial instrument prevented their use for this application. When ion mobility was plotted against drift gas polarizability, the resulting slopes were often unique for individual ions, indicating that selectivity factors between any two analytes varied with the choice of drift gas. In some cases, drugs like THC and heroin, which are unresolved in air or nitrogen, were well resolved in carbon dioxide or nitrous oxide.     

A novel ion detector aiming at the homogeneous of drift gas

In standalone ion mobility spectrometry (IMS) instruments, the effect of drift gas turbulence reduces the sensitivity and resolution of the instrument. A traditional ion detector constructed with a Faraday plate and used to detect ions in an IMS is positioned at the end of the drift region. Drift gas flowing through this detector may introduce turbulence near the detector, possibly affecting the sensitivity and resolution of the device. To address this problem, a novel Faraday detector with a double layer structure was constructed. A number of dense and staggered holes were created on each layer of the detector. This design enabled the drift gas to pass through the holes of the detector, and the staggered nature of holes in the detector ensured that the ions could be detected. Theoretical simulations were conducted using the finite element method to obtain velocity distributions for both a standard Faraday detector and the modified Faraday detector. The results indicated that the novel ion detector created a homogenous gas under at high inlet flow rate while turbulence was still evident for the traditional Faraday detector. When the inlet flow rate was 1000 mL/min, the range of the unstable region of the drift gas in the axis of the drift tube with the novel ion detector was reduced by 97% relative to that for the traditional detector. The data suggests that due to such gains, sensitivity and resolution may be improved for standalone IMS instruments.     

Aza analogs of kainoids by dipolar cycloaddition

The 1,3-dipolar cycloadditions of diazoalkanes with trans-diethyl glutaconate yield 1-pyrazolines, which isomerize to 2-pyrazolines or are oxidized to pyrazoles. The 2-pyrazolines may serve as precursors to novel glutamate analogs or aza analogs of kainoids. The regioselectivity of the 1,3-dipolar cycloadditions of diazoalkanes and trans-diethyl glutaconate and isomerization of the 1-pyrazolines to 2-pyrazolines are evaluated.     

Mixed-metal metallocryptands. Short metal-metal separations strengthened by a dipolar interaction

The deep-red, air-stable mixed-metal metallocryptands, [AuPdTl(P2phen)3](PF6)2, 1.(PF6)2, and [AuPtTl(P2phen)3](PF6)2, 2.(PF6)2, are easily prepared in good yield (60-70%) by reacting 3 equiv of P2phen with 1 equiv of Au(THT)Cl, excess thallous acetate, and the appropriate amount of either Pd2(dba)3 for 1 or Pt(dba)2 for 2 in acetonitrile where P2phen is 2,9-bis(diphenylphosphino)-1,10-phenanthroline, THT is tetrahydrothiophene, and dba is dibenzylidineacetone. Compared to the more symmetrical bimetallic metallocryptands, these trimetallic species show shorter than expected Au(I)-Tl(I), Pt(0)-Tl(I), and Pd(0)-Tl(I) separations. The enhanced bonding interaction is attributed to the incorporation of the dissimilar capping metals introducing dipole moments that strengthen the dispersion forces responsible for maintaining the metallophilic interactions.     

Separation of isomeric disaccharides by traveling wave ion mobility mass spectrometry using CO2 as drift gas

The use of CO₂ as a massive and polarizable drift gas is shown to greatly improve peak‐to‐peak resolution (R_p‐p), as compared with N₂, for the separation of disaccharides in a Synapt G2 traveling wave ion mobility cell. Near or baseline R_p‐p was achieved for three pairs of sodiated molecules of disaccharide isomers, that is, cellobiose and sucrose (R_p‐p = 0.76), maltose and sucrose (R_p‐p = 1.04), and maltose and lactose (R_p‐p = 0.74). Ion mobility mass spectrometry using CO₂ as the drift gas offers therefore an attractive alternative for fast and efficient separation of isomeric disaccharides. Copyright © 2012 John Wiley & Sons, Ltd.     

Fabrication of dipolar colloid particles by microcontact printing

A novel technique for preparation of dipolar colloid particles has been developed which is based on microcontact printing of films of water-insoluble ionic surfactants onto monolayers of colloid particles of opposite surface charge.     

Improving solid-state NMR dipolar recoupling by optimal control

We present the first solid-state NMR experiments developed using optimal control theory. Taking heteronuclear dipolar recoupling in magic-angle-spinning NMR as an example, it proves possible to significantly improve the efficiency of the experiments while introducing robustness toward instrumental imperfections such as radio frequency inhomogeneity. The improvements are demonstrated by numerical simulations as well as practical experiments on a 13Calpha,15N-labeled powder of glycine. The experiments demonstrate a gain of 53% in the efficiency for 15N to 13Calpha coherence transfer relative to the typically double-cross-polarization experiments.     

Protein alignment by a coexpressed lanthanide-binding tag for the measurement of residual dipolar couplings

A protein fusion construct of human ubiquitin with an N-terminal lanthanide binding tag (LBT) enables observation of long-range orientational restraints in solution NMR from residual dipolar couplings (RDCs) due to paramagnetic alignment of the protein. The paramagnetic lanthanide ions Tb3+, Dy3+, and Tm3+ are shown to bind to the LBT and induce different alignment tensors, in agreement with theory. RDCs, measured relative to the diamagnetic Lu3+, range from -7.6 to 5.5 Hz for Tb3+ and -6.6 to 6.1 Hz for Dy3+, while an opposite alignment tensor is observed for Tm3+ (4.5 to -2.9 Hz) at 800 MHz. Experimental RDCs are in excellent agreement with those predicted on the basis of the X-ray structure of the protein.     

Structure and dynamics in a monolayer of dipolar spheres

The structure and dynamics in a monolayer of dipolar soft spheres have been investigated using molecular dynamics simulations. This is a basic model of colloidal ferrofluid monolayers, and other magnetic liquids in planar geometries, which can exhibit self-assembled chainlike aggregates due to strong dipole-dipole interactions. The effects of such chaining on the structure, single-particle translational and rotational motions, and the collective rotational motions are examined. The signatures of aggregation in the various structural and dynamical functions considered in this study could prove useful in experimental investigations of strongly dipolar materials.     

Spatial structure of peptides determined by residual dipolar couplings analysis

The gated decoupled (13)C NMR spectra of a dipeptide (Glu-Trp) and a tetrapeptide (NAc-Ser-Phe-Val-Gly-OMe) were recorded in D(2)O and in a lyotropic alignment medium (pentaethylene glycol monododecyl ether/n-hexanol). The residual dipolar couplings were extracted as the differences between the observed couplings for the magnetic nuclei dissolved in the latter and former media. Using a computational optimization, the spatial structures of the compounds were calculated starting from their respective low energy conformations obtained on a semiempirical basis. The uniformity of each conformation was confirmed by the solid-state (13)C NMR spectra of powder samples. Differences between the starting structures and final ones, optimized when employing residual dipolar couplings, are discussed.     

Communication: The phoretic drift of a charged particle animated by a direct ionic current

A charged colloidal particle which is suspended in an electrolyte solution drifts due to an external voltage application. For direct currents, particle motion is affected by two separate mechanisms: electro-osmotic slip associated with the electric field and chemi-osmotic slip associated with the inherent salt concentration gradient in the solution. These two mechanisms are interrelated and are of comparable magnitude. Their combined effect is demonstrated for cation-exchange electrodes using a weak-current approximation. The linkage between the two mechanisms results in an effectively modified mobility, whose dependence on the particle zeta potential is nonlinear. At small potentials, the electro-osmotic mechanism dominates and the particle migrates according to the familiar Smoluchowski mobility, linear in the electric field. At large zeta potentials, chemiosmosis becomes dominant: for positively charged particles, it tends to arrest motion, leading to mobility saturation; for negatively charged particles, it enhances the drift, effectively leading to a shifted linear dependence of the mobility on the zeta potential, with twice the Smoluchowski slope.     

A convergent synthesis of substituted pyrrolidines by 1,3 dipolar cycloaddition

Thiazolium ylids $\text{2a}$ and $\text{2b}$ are converted to $\text{4}$ in 3 steps.     

Optimisation of piezoelectric injection of dopants and drift gas modifiers in transverse ion mobility spectrometry

Novel experimental methods are described for controlling the levels of dopant or drift gas modifier with piezoelectric actuation. The piezoelectric jetting of 2-butanol, acetone, 4-heptanone and dichloromethane was first optimised by applying a fractional factorial experimental design to the waveform required to actuate the dopants. The concentration of dopant entering a transverse ion mobility cell was dynamically controlled by a series of air flows at the interface between the actuator and the ion source, as well as the droplet injection frequency, as defined by the optimised waveform parameters. The optimisation methodology indicated that dwell time and dwell voltage were the most important factors in controlling the process. The optimised approach was then used to deliver varying levels of candidate dopants; 20.5 to 196.6 μg?m^?3 for 2-butanol, 35.4 to 164.3 μg?m^?3 for acetone, 17.8 to 58.2 μg?m^?3 for 4-heptanone and 27.6 to 270.2 μg?m^?3 for dichloromethane. The method enables reactant ion chemistry to be switched in the order of 3 to 5 sec, indicating the potential for introducing multiple dopants at varying concentrations into ion mobility spectrometers. The most volatile material dichloromethane was more difficult to control and the reproducibility and stability of the instrument responses to this compound was not as good as the other less volatile ones. The concept of extending this approach to mixtures and dual use formulations, doping and modification was proposed.     

呋喃西林代谢物荧光偏振免疫检测方法研究

利用新制备的抗体首次建立了呋喃西林代谢物氨基脲(SEM)的荧光偏振免疫分析(FPIA)方法.通过设计合成新的SEM半抗原CEPSEM(2-(4-((2-carbamoylhydrazono)methyl)phenoxy)acetic acid),偶联载体蛋白后免疫新西兰大白兔,制备了亲和力高、特异性好的多克隆抗体.结合新设计合成的荧光示踪物CEPSEM-HDF建立了SEM的FPIA方法.结果表明:在示踪物浓度为0.5 nmol/L,抗体稀释度为1/100的优化条件下,IC50为47.9 μg/L,检出限为8.3 μg/L,线性范围为15.8 ～145.7 μg/L.该方法特异性强(和其它相关兽药交叉反应小于0.1%),稳定性好(批内相对标准偏差小于2.5%,批间相对标准偏差小于6.3%).