Ion mobility spectrometry in scientific literature and in the International Journal for Ion Mobility Spectrometry (1998–2007)

Starting in 1998 the International Society for Ion Mobility Spectrometry, organising the annual conferences on ion mobility spectrometry, began to issue the International Journal for Ion Mobility Spectrometry. Now, in the 11th year the journal will be the first year together with SPRINGER. Therefore, the article focusses on the history of IMS providing an up to date account based on a systemetic search using the Web-of-Science and SciFinder search engines.     

Signatures of Mechanically Interlocked Topology of Lasso Peptides by Ion Mobility–Mass Spectrometry: Lessons from a Collection of Representatives

Lasso peptides are characterized by a mechanically interlocked structure, where the C-terminal tail of the peptide is threaded and trapped within an N-terminal macrolactam ring. Their compact and stable structures have a significant impact on their biological and physical properties and make them highly interesting for drug development. Ion mobility - mass spectrometry (IM-MS) has shown to be effective to discriminate the lasso topology from their corresponding branched-cyclic topoisomers in which the C-terminal tail is unthreaded. In fact, previous comparison of the IM-MS data of the two topologies has yielded three trends that allow differentiation of the lasso fold from the branched-cyclic structure: (1) the low abundance of highly charged ions, (2) the low change in collision cross sections (CCS) with increasing charge state and (3) a narrow ion mobility peak width. In this study, a three-dimensional plot was generated using three indicators based on these three trends: (1) mean charge divided by mass (ζ), (2) relative range of CCS covered by all protonated molecules (ΔΩ/Ω) and (3) mean ion mobility peak width (δΩ). The data were first collected on a set of twenty one lasso peptides and eight branched-cyclic peptides. The indicators were obtained also for eight variants of the well-known lasso peptide MccJ25 obtained by site-directed mutagenesis and further extended to five linear peptides, two macrocyclic peptides and one disulfide constrained peptide. In all cases, a clear clustering was observed between constrained and unconstrained structures, thus providing a new strategy to discriminate mechanically interlocked topologies.

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Metal–ligand Lability and Ligand Mobility Enables Framework Transformation via Ligand Release in a Family of Crystalline 2D Coordination Polymers

A family of seven silver(I)-perfluorocarboxylate-quinoxaline coordination polymers, [Ag₄(O₂CR_F)₄(quin)₄] 1 – 5 (R_F=(CF₂)_n-1CF₃)₄, n=1 to 5); [Ag₄(O₂C(CF₂)₂CO₂)₂(quin)₄] 6 ; [Ag₄(O₂CC₆F₅)₄(quin)₄] 7 (quin=quinoxaline), denoted by composition as 4 : 4 : 4 phases, was synthesised from reaction of the corresponding silver(I) perfluorocarboxylate with excess quinoxaline. Compounds 1 – 7 adopt a common 2D layered structure in which 1D silver-perfluorcarboxylate chains are crosslinked by ditopic quinoxaline ligands. Solid-state reaction upon heating, involving loss of one equivalent of quinoxaline, yielding new crystalline 4 : 4 : 3 phases [Ag₄(O₂C(CF₂)_n-1CF₃)₄(quin)₃]_n ( 8 – 10 , n=1 to 3), was followed in situ by PXRD and TGA studies. Crystal structures were confirmed by direct syntheses and structure determination. The solid-state reaction converting 4 : 4 : 4 to 4 : 4 : 3 phase materials involves cleavage and formation of Ag−N and Ag−O bonds to enable the structural rearrangement. One of the 4 : 4 : 3 phase coordination polymers ( 10 ) shows the remarkably high dielectric constant in the low electric field frequency range.     

How Hot are Your Ions in TWAVE Ion Mobility Spectrometry?

Effective temperatures of ions during traveling wave ion mobility spectrometry (TWIMS) analysis were measured using singly protonated leucine enkephalin dimer as a chemical thermometer by monitoring dissociation of the dimer into monomer, as well as the subsequent dissociation of monomer into a-, b-, and y-ions, as a function of instrumental parameters. At fixed helium cell and TWIMS cell gas flow rates, the extent of dissociation does not vary significantly with either the wave velocity or wave height, except at low (<500 m/s) wave velocities that are not commonly used. Increasing the flow rate of nitrogen gas into the TWIMS cell and decreasing the flow rate of helium gas into the helium cell resulted in greater dissociation. However, the mobility distributions of the fragment ions formed by dissociation of the dimer upon injection into the TWIMS cell are nearly indistinguishable from those of fragment ions formed in the collision cell prior to TWIMS analysis for all TWIMS experiments. These results indicate that heating and dissociation occur when ions are injected into the TWIMS cell, and that the effective temperature subsequently decreases to a point at which no further dissociation is observed during the TWIMS analysis. An upper limit to the effective ion temperature of 449 K during TWIMS analysis is obtained at a helium flow rate of 180 mL/min, TWIMS flow rate of 80 mL/min, and traveling wave height of 40 V, which is well below previously reported values. Effects of ion heating in TWIMS on gas-phase protein conformation are presented.     

Measurement of Ion Mobilities of Selected Amines by Ion Mobility Spectrometry

IlltIoduchontIonmobilityspectrometry(IMS)isagasphaseelectTophoreticandlyticaltechniqueinwhichionsatahaosphericpressureareallowedtodrift,separateandcollectbasedontheirdoferentmobilitiesinanelectricfield.ThequalitativeandquantitativeinformationoftheanalytescanbeacquiredfromthereducedmobilitiesandrelativeintensihesoftheirpeaksinIMSspectTa.IMSwasdevelopedtobeanewtecndqueinfieldapplications[1J.Thereducedmobility(Ko)iscalculatedaccordingtothefollowingequation:h=(L/Et)(P/7so)(2=s/nwhereListhed…     

The IR Absorption Spectra of Aqueous Solutions of Dimethylsulfoxide over the Frequency Range 50–300 cm−1 and the Mobility of Water Molecules

The IR absorption spectra of aqueous solutions of dimethylsulfoxide (DMSO) with concentrations from 100% H₂O to 100% DMSO were recorded over the frequency range 50–500 cm^?1. The absorption spectra were described using the theoretical scheme of hindered rotators. A model was developed according to which orientation relaxation in solution was related to separate rotations of H₂O and DMSO molecules through fixed small and (or) large angles in a unified network of H-bonds consisting of several subsystems ordered to various degrees. The calculated absorption spectra were in agreement with the experimental data in the far IR region. Elementary motions of molecules were found to slow down in the passage from pure dimethylsulfoxide to its aqueous solutions. The special features of the hydrophilic and hydrophobic hydration of DMSO polar and nonpolar groups were considered.     

High Charge Mobility of a Perylene Bisimide Dye with Hydrogen-bond Formation Group

Charge carrier mobility is one of the most important parameters concerning the performance of organic electronic devices1.High mobility usually leads to high calculation speed in computer and high short-circuit current in organic solar cells.Unfortunately,the intrinsic charge mobilities for organic semiconductors are of orders of magnitude lower than amorphous silicon.As a promising n-type organic semiconductor,N,N′-n-alkyl-perylene bisimides have shown their electron mobility to be up to10-…     

Synthesis and Ion Mobility in Glasses of ZrF<Subscript>4</Subscript>–BiF<Subscript>3</Subscript>–Rb(Cs)F Fluoride Systems

A new procedure has been suggested for the synthesis of bismuth fluorozirconate glasses in the ZrF₄–BiF₃–MF systems (M = Rb, Cs), which is based on the use of the relatively moisture-resistant Rb₂ZrF₆ and Cs₂ZrF₆ fluorides rather than extremely hygroscopic rubidium and cesium fluorides. The types of ion motions, trends in ion mobility dynamics, and factors determining this dynamics as a function of the glass composition have been elucidated. A rather high ionic conductivity of glasses above 470 K, σ ≥ 10^–4 S/cm, makes them promising candidates for use in design of functional materials.     

Formation of Poly（L-lactide） Mesophase and Its Chain Mobility Dependent Kinetics

In the present work, the PLLA mesophase formation and its kinetics at the advent of a chain mobility accelerator （polyethylene glycol （PEG）） are investigated by wide angle X-ray diffraction （WAXD） and time-resolved Fourier transform infrared spectroscopy （FTIR）. It is interestingly found that the presence of PEG could accelerate the formation of PLLA mesophase notably due to the enhanced chain mobility, giving rise to a substantially reduced half time （t0.5） of PLLA mesophase formation from 129 min to 8 min. The Avrami exponents （n） for the kinetics of mesophase formation are -0.5 for neat PLLA and 1 for PLLA/PEG, respectively, indicating that 1D-rod growth through heterogeneous nucleation occurs during formation of PLLA mesophase. Tensile testing demonstrates that PLLA mesophase could increase the tensile strength and modulus but decrease the elongation at break.     

Differential Ion Mobility Separations in up to 100 % Helium Using Microchips

The performance of differential IMS (FAIMS) analyzers is much enhanced by gases comprising He, especially He/N₂ mixtures. However, electrical breakdown has limited the He fraction to ~50 %–75 %, depending on the field strength. By the Paschen law, the threshold field for breakdown increases at shorter distances. This allows FAIMS using chips with microscopic channels to utilize much stronger field intensities (E) than “full-size” analyzers with wider gaps. Here we show that those chips can employ higher He fractions up to 100 %. Use of He-rich gases improves the resolution and resolution/sensitivity balance substantially, although less than for full-size analyzers. The optimum He fraction is ~80 %, in line with first-principles theory. Hence, one can now measure the dependences of ion mobility on E in pure He, where ion-molecule cross section calculations are much more tractable than in other gases that form deeper and more complex interaction potentials. This capability may facilitate quantitative modeling of high-field ion mobility behavior and, thus, FAIMS separation properties, which would enable a priori extraction of structural information about the ions.

Use of Solid Phase Microextraction (SPME) with Ion Mobility Spectrometry∗

Abstract

We report the use of solid phase microextraction (SPME) combined with ion mobility spectrometry (IMS) for sampling, screening and identification of organic compounds that are readily detected by IMS. This is a new SPME application. SPME has emerged recently as an excellent sample preparation technique for gas chromatography (GC) and high performance liquid chromatography (HPLC). We have found that SPME can be used very conveniently with IMS. An example of SPME-IMS is described using SPME headspace sampling at room temperature with 0.1 mL vials containing 1.0 microgram or less of either cocaine freebase or cocaine hydrochloride. This is followed by analysis using IMS. A hole, drilled in the IMS sample ticket holder, serves as the SPME-IMS interface.

     

Correlation between Molecular Structures and Relative Electrophoretic Mobility in Capillary Electrophoresis:Alkylpyridines

Introduction　　Highperformancecapillaryelectrophoresis (HPCE)hasnowbeenwidelyusedtoseparateanddetermineana lytesfromsmallinorganicandorganicionstomacromolec ularspeciessuchasDNAandproteins .Overthepastfewyears ,therehavebeenconsiderableinterestsinthedevel opingmethodsusingcapillaryelectrophoresistoseparatesmallorganicmolecules ,asacomplementarymethodtoHPLCseparations .1 3Electrophoreticmobility (μ)isthemostimportantparametergoverningtheseparationofso lutesincapillaryzoneelectrophoresis (…     

Electrochemical reactivity of Li–Mn–O and Li–Fe–Mn–O spinels

Electrochemical reductive dissolution of Li–Mn–O and Li–Fe–Mn–O spinels and Li⁺ extraction/insertion in these oxides were performed using voltammetry of microparticles. Both electrochemical reactions are sensitive to the Fe/(Fe+Mn) ratio, specific surface area, Li content in tetrahedral positions, and Mn valence, and can be used for electrochemical analysis of the homogeneity of the elemental and phase composition of synthetic samples. The peak potential (E _P) of the reductive dissolution of the Li–Mn–O spinel is directly proportional to the logarithm of the specific surface area. E _P of Li–Fe–Mn–O spinels is mainly controlled by the Fe/(Fe+Mn) ratio. Li⁺ insertion/extraction can be performed with Mn-rich Li–Fe–Mn–O spinels in aqueous solution under an ambient atmosphere and it is sensitive to the regularity of the spinel structure, in particularly to the amount of Li in tetrahedral positions and the Mn valence. Electronic Publication     

Bubble points of hydrogen chloride–water–isopropanol and hydrogen chloride–water–isopropanol–benzene systems and liquid–liquid equilibria of hydrogen chloride–water–benzene and hydrogen chloride–water–isopropanol–benzene systems

Bubble points of the HCl–water–isopropanol and the HCl–water–isopropanol–benzene systems and liquid–liquid equilibria (LLE) of the HCl–water–benzene and the HCl–water– isopropanol–benzene systems were measured at 25–85°C and 30–70°C, respectively. The electrolyte nonrandom two-liquid model proposed by Chen et al. [C.-C. Chen, H.I. Britt, J.F. Boston, L.B. Evans, AIChE J. 28 (1982) 588–596] can satisfactorily correlate bubble points and liquid–liquid equilibria of the present mixed-solvent electrolyte systems over the entire range of temperature and concentrations using only binary adjustable parameters.     

On hydrolysis of Ba–Bi–O and K–Ba–Bi–O oxide systems

Fundamentally different behavior of Ba–Bi–O (Ba : Bi = 11 : 4, 1 : 1, 2: 3, and 1 : 5 mol/mol) and K_nBa_mBi_m+nO_y (m = n = 1, 2,...; exhibiting superconducting properties with T_c = 28–32 K) oxides and BaO₂ in hydrolysis reactions has been revealed by means of potentiometry and chemical analysis. Products of the oxides treatment with water do not contain H₂O₂, evidencing the absence of peroxide ions in their structure. The perovskite-type barium-bismuth(III) oxides are completely hydrolyzed into Ba(OH)₂ and Bi₂O₃ at room temperature.     

The Mobility of Threaded α-Cyclodextrins in PR Copolymer and Its Influences on Mechanical Properties

The methylated polyrotaxane(Me PR) copolymer was prepared via the methylation of hydroxyl of threaded α-cyclodextrin(α-CDs) in polyrotaxane(PR) copolymer by CH_3I/Na H. Its structure was characterized by GPC, IR and NMR. The WXRD and TGA measurements showed the destruction of channel-like crystalline structure in Me PR copolymer. The sliding of threaded α-CDs along PEG axis in PR and Me PR copolymers was demonstrated by their dielectric spectra that also evidenced the presence of rotating of threaded α-CDs around PEG axis in Me PR copolymer. The frequent and vigorous molecular mobility in Me PR and PR copolymers was also verified by dynamic mechanical analysis(DMA) and rheological measurement, which was possibly assigned to the sliding and rotating of threaded α-CDs. DMA and rheological results showed that the mobility of α-CDs could simultaneously strengthen and toughen PR copolymer proved by stress-stain curves. In this paper, we report the CD mobility in PR and Me PR copolymers. The macroscopic behaviors of PR copolymer, such as mechanical properties in solid state, were also found to be benefited from CD mobility.     

New Phase in the Bi–Sr–Ca–Cu–O System

Cooling a melt of a Bi–Sr–Ca–Cu–O system (Bi:Sr:Ca:Cu = 4:3:3:4 or 2:2:2:4) from 1000°C-1050°C yielded crystals of a new red-colored nonsuperconducting phase, accompanying the superconducting 2212 and 2201 phases. Based on the EPR spectra, it was concluded that copper is univalent in this compound. The new phase has a composition Bi_2.2Sr_1.6Ca_1.3Cu₂Ox. The X-ray diffraction pattern has been indexed, and the unit cell parameters of the phase have been determined: space group P2/m, a = 12.93, b = 4.55, c = 10.94 ; = 102.72°.     

BTATz–HNIW–CMDB propellants

The high nitrogen compound 3,6-bis(1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine and the high energy density material hexanitrohexaazaisowurtzitane (HNIW), were used as substitute of hexogen (RDX) in the composite modified double base (CMDB) propellant formulations, the propellant samples were prepared, the thermal behaviors, nonisothermal reaction kinetics, and thermal safety were carried out, and the eight important parameters were calculated and obtained as the self-accelerating decomposition temperature (T _SADT), thermal ignition temperature (T _TIT), critical temperatures of thermal explosion (T _b), critical temperature of hot-spot initiation (T _cr,hot-spot), characteristic drop height of impact sensitivity (H ₅₀), critical thermal explosion ambient temperature (T _acr), safety degree (S _d), and thermal explosion probability (P _TE). It shows that the content of HNIW has a large effect on the decomposition reaction mechanism of the CMDB propellant, when the content of HNIW is 10 %, the decomposition reaction are controlled by the random nucleation and subsequent growth (n = l), and the reaction mechanism obeys Mampel law; but when the content of HNIW is 20 %, the decomposition reaction are controlled by the chemical reaction (n = 1/4). The mechanism can not be changed by the catalysts, and they just make the apparent activation energy change slightly. For the sample, from BC01 to BC04, the values of T _SADT and T _TIT making an upward tendency, show the resistivity to heat: BC04 > BC03 > BC02 > BC01; the values of T _acr and S _d, BC01 are the maximum and BC02 are the minimum, show the heat sensitivity: BC01 > BC03 > BC04 > BC02. For the same radius, the thermal safety of the sphere sample is greater than that of the infinite cylinder one.     

Is the Reduction in Tracer Diffusivity under Nanoscopic Confinement Related to a Frustrated Segmental Mobility?

We developed an experimental method for the determination of the tracer diffusivity D_tr in ultrathin polymer films, and the changes in the segmental mobility of tracer molecules while they diffuse through matrices of different thickness and get adsorbed onto a target substrate. D_tr starts decreasing already at 120–150 nm and drops to 1% of its bulk value in films as thin as 7.5 nm. We discuss the results highlighting a strong decoupling between the reduction in mass transport at the nanoscale and the increase in the glass transition temperature determined via capacitive dilatometry together with a breakdown of the Stokes–Einstein relation between orientational and translational degrees of freedom.