Improved design for high resolution electrospray ionization ion mobility spectrometry

An improved design for high resolution electrospray ionization ion mobility spectrometry (ESI-IMS) was developed by making some salient modifications to the IMS cell and its performance was investigated. To enhance desolvation of electrospray droplets at high sample flow rates in this new design, volume of the desolvation region was decreased by reducing its diameter and the entrance position of the desolvation gas was shifted to the end of the desolvation region (near the ion gate). In addition, the ESI source (both needle and counter electrode) was positioned outside of the heating oven of the IMS. This modification made it possible to use the instrument at higher temperatures, and preventing needle clogging in the electrospray process. The ion mobility spectra of different chemical compounds were obtained. The resolving power and resolution of the instrument were increased by about 15-30% relative to previous design. In this work, the baseline separation of the two adjacent ion peaks of morphine and those of codeine was achieved for the first time with resolutions of 1.5 and 1.3, respectively. These four ion peaks were well separated from each other using carbon dioxide (CO₂) rather than nitrogen as the drift gas. Finally, the analytical parameters obtained for ethion, metalaxyl, and tributylamine indicated the high performance of the instrument for quantitative analysis.     

Qualitative analysis of trace constituents by ion mobility increment spectrometer

Ion mobility increment spectrometry (IMIS) is a high sensitive selective ionization technology for detection and identification of ultra-trace constituents, including toxic compounds, CW-agents, drugs and explosives in ambient air or liquid sample. Like an ion mobility spectrometry (IMS), this technology rests on sampling air containing a mixture of trace constituents, its ionization, spatial separation of produced ions and separated ions detection. Unlike IMS, ions of different types in IMIS are separated by ion mobility increment, α. Value α, is a function of the parameters: electric field strength and form, atmospheric pressure. To exclude the influence of these parameters on an α, the method of explosives identification by a standard compound was suggested. As a standard compound iodine was used. The relationship among the mobility coefficient increments equal to the relationship among the compensation voltage α_i/α_iodine=U_i/U_iodine is determined, where i are ions of 1,3-dinitrobenzene, 1,3,5-trinitrobenzene, p-mononitrotoluene, 2,4-dinitrotoluene and 2,4,6-trinitrotoluene This relationship is practically independent of the above mentioned parameters in the range 25<E/N<90 Td. The limits of the relative error of this relationship are determined both from spectra of individual compounds and nitrocompound-iodine mixtures.     

The coupling of solid-phase microextraction/surface enhanced laser desorption/ionization to ion mobility spectrometry for drug analysis

The construction of a new solid-phase microextraction/surfaced enhanced laser desorption/ionization-ion mobility spectrometry (SPME/SELDI-IMS) device is reported here. A polypyrrole (PPY) coated SPME/SELDI fiber was employed as the extraction phase and SELDI surface to introduce analytes into the IMS. Analytes were directly ionized from the PPY coated fiber tip by a Nd:YAG laser without the addition of a matrix. Optimal experimental parameters, such as extraction conditions and laser parameters, were investigated. The use of a SPME/SELDI fiber simplified the sampling and sample preparation for IMS. Verapamil could be directly extracted from urine sample and analyzed by IMS without any further sample cleanup. This technique could be used for the analysis of drugs and other non-volatile compounds.     

Coupling of capillary electrophoresis with electrospray ionization multiplexing ion mobility spectrometry

In this work, ion mobility spectrometry (IMS) function as a detector and another dimension of separation was coupled with CE to achieve two‐dimensional separation. To improve the performance of hyphenated CE‐IMS instrument, electrospray ionization correlation ion mobility spectrometry is evaluated and compared with traditional signal averaging data acquisition method using tetraalkylammonium bromide compounds. The effect of various parameters on the separation including sample introduction, sheath fluid of CE and drift gas, data acquisition method of IMS were investigated. The experimental result shows that the optimal conditions are as follows: hydrodynamic sample injection method, the electrophoresis voltage is 10 kilo volts, 5 mmol/L ammonium acetate buffer solution containing 80% acetonitrile as both the background electrolyte and the electrospray ionization sheath fluid, the ESI liquid flow rate is 4.5 μL/min, the drift voltage is 10.5 kilo volts, the drift gas temperature is 383 K and the drift gas flow rate is 300 mL/min. Under the above conditions, the mixture standards of seven tetraalkylammoniums can be completely separated within 10 min both by CE and IMS. The linear range was 5–250 μg/mL, with LOD of 0.152, 0.204, 0.277, 0.382, 0.466, 0.623 and 0.892 μg/mL, respectively. Compared with traditional capillary electrophoresis detection methods, the developed CE‐ESI‐IMS method not only provide two sets of qualitative parameters including electrophoresis migration time and ion drift time, ion mobility spectrometer can also provide an additional dimension of separation and could apply to the detection ultra‐violet transparent compounds or none fluorescent compounds.     

High resolution electrospray ionization ion mobility spectrometry

Current commercially available ion mobility spectrometers are intended for the analysis of chemicals in the gas phase. Sample introduction methods, such as direct air sampling, a GC injector or a thermal desorber, are commonly an integral part of these instruments. This paper describes an electrospray ionization ion mobility spectrometer system that allows direct introduction samples in solution phase. This allows direct analysis of non-volatile organic and biological samples, and avoids decomposition of thermally liable samples, providing reliable chemical identification. In addition, the new ion mobility spectrometer allows mobility analysis with high resolving power. Commonly used commercial IMS systems provide resolving powers between 10 and 30; this new ion mobility spectrometer has resolving power greater than 60 for routine analysis. A high resolution instrument is necessary for many applications where a complex mixture needs to be separated and quantified. This paper demonstrates the advantages of using a high resolution ion mobility spectrometer and an electrospray ionization source for the analysis of non-volatile pharmaceuticals as well as dissolved explosive in solution phase.     

Characterization of a distributed plasma ionization source (DPIS) for ion mobility spectrometry and mass spectrometry

A recently developed atmospheric pressure ionization source, a distributed plasma ionization source (DPIS), was characterized and compared to commonly used atmospheric pressure ionization sources with both mass spectrometry (MS) and ion mobility spectrometry (IMS). The source consisted of two electrodes of different sizes separated by a thin dielectric. Application of a high RF voltage across the electrodes generated plasma in air yielding both positive and negative ions. These reactant ions subsequently ionized the analyte vapors. The reactant ions generated were similar to those created in a conventional point-to-plane corona discharge ion source. The positive reactant ions generated by the source were mass identified as being solvated protons of general formula (H₂O)_nH⁺ with (H₂O)₂H⁺ as the most abundant reactant ion. The negative reactant ions produced were mass identified primarily as CO₃⁻, NO₃⁻, NO₂⁻, O₃⁻ and O₂⁻ of various relative intensities. The predominant ion and relative ion ratios varied depending upon source construction and supporting gas flow rates. A few compounds including drugs, explosives and amines were selected to evaluate the new ionization source. The source was operated continuously for 3 months and although surface deterioration was observed visually, the source continued to produce ions at a rate similar that of the initial conditions.     

Spectroscopic characterization of a microplasma used as ionization source for ion mobility spectrometry

We report a miniaturized excitation source for soft ionization of molecules based on a dielectric barrier discharge. An atmospheric plasma is established at the end of a 500 μm diameter capillary using He as buffer gas. The plasma jet which comes out of the capillary is dependent on the gas flow rate. The mechanism of the production of N₂⁺ outside the capillary, which is relevant for the protonation of molecules and sustains the production of primary ions, is investigated by spatially resolved spectroscopic measurements throughout the plasma. Possible application of such miniaturized plasmas is the ionization of gaseous compounds under atmospheric pressure as an alternative to traditional APCI (atmospheric pressure chemical ionization). The miniaturized plasma was applied as ionization source for ion mobility spectrometry where the common sources are radioactive, thus limiting the place of installation. First measurements of gaseous compounds with such a plasma ion mobility spectrometer with promising results showed detection limits comparable or even better than those obtained using common radioactive ionization sources.     

Analysis of explosives using electrospray ionization/ion mobility spectrometry (ESI/IMS)

The analysis of explosives with ion mobility spectrometry (IMS) directly from aqueous solutions was shown for the first time using an electrospray ionization technique. The IMS was operated in the negative mode at 250°C and coupled with a quadrupole mass spectrometer to identify the observed IMS peaks. The IMS response characteristics of trinitrotoluene (TNT), 2,4-dinitrotoluene (2,4-DNT), 2-amino-4,6-dinitrotoluene (2-ADNT), 4-nitrotoluene (4-NT), trinitrobenzene (TNB), cyclo-1,3,5-trimethylene-2,4,6-trinitramine (RDX), cyclo-tetramethylene-tetranitramine (HMX), dinitro-ethyleneglycol (EGDN) and nitroglycerine (NG) were investigated. Several breakdown products, predominantly NO₂⁻ and NO₃⁻, were observed in the low-mass region. Nevertheless, all compounds with the exception of NG produced at least one ion related to the intact molecule and could therefore be selectively detected. For RDX and HMX the [M+Cl⁻]⁻ cluster ion was the main peak and the signal intensities could be greatly enhanced by the addition of small amounts of sodium chloride to the sprayed solutions. The reduced mobility constants (K₀) were in good agreement with literature data obtained from experiments where the explosives were introduced into the IMS from the vapor phase. The detection limits were in the range of 15–190 μg l⁻¹ and all calibration curves showed good linearity. A mixture of TNT, RDX and HMX was used to demonstrate the high separation potential of the IMS system. Baseline separation of the three compounds was attained within a total analysis time of 6.4 s.     

Atmospheric-pressure ionization studies and field dependence of ion mobilities of isomeric hydrocarbons using a miniature differential mobility spectrometer

The ionization pathways and ion mobility were determined for sets of structural isomeric and stereoisomeric non-polar hydrocarbons (saturated and unsaturated cyclic hydrocarbons and aromatic hydrocarbons) using a novel miniature differential mobility spectrometer with atmospheric-pressure photoionization (APPI) to assess how structural and stereochemical differences influence ion formation and ion mobility. The analytical results obtained using the differential mobility spectrometry (DMS) were compared with the reduced mobility values measured using conventional time-of-flight ion mobility spectrometry (IMS) with the same ionization technique.The majority of differences in DMS ion mobility spectra observed among isomeric cyclic hydrocarbons can be explained by the formation of different product ions. Comparable differences in ion formation were also observed using conventional IMS and by investigations using the coupling of ion mobility spectrometry with mass spectrometry (APPI-IMS-MS) and APPI-MS. Using DMS, isomeric aromatic hydrocarbons can in the majority of cases be distinguished by the different behavior of product ions in the strong asymmetric radio frequency (rf) electric field of the drift channel. The different peak position of product ions depending on the electric field amplitude permits the differentiation between most of the investigated isomeric aromatics with a different constitution; this stands in contrast to conventional IMS in which comparable reduced mobility values were detected for the isomeric aromatic compounds.     

Micro-plasma: a novel ionisation source for ion mobility spectrometry

Ion mobility spectrometry is an analytical method for identification and quantification of gas-phase analytes in the ppb_v-ppt_v range. Traditional ionisation methods suffer from low sensitivity (UV light), lack of long-term stability (partial discharge), or legal restrictions when radioactive sources are used. A miniaturised helium plasma was applied as ionisation source in an ion mobility spectrometer (IMS). Experiments were carried out to compare plasma IMS with β-radiation IMS. It could be demonstrated that the plasma IMS is characterised by higher sensitivity and selectivity than β-radiation ionisation. Plasma IMS is approximately 100 times more sensitive than the β-radiation IMS. Furthermore, variable sensitivity can be achieved by variation of the helium flow and the electric field of the plasma, and variable selectivity can be achieved by changing the electric field of the IMS. The experimental arrangement, optimisation of relevant conditions, and a typical application are presented in detail. Figure Micro-plasma used in ion mobility spectrometry     

Towards metals analysis using corona discharge ionization ion mobility spectrometry

For the first time, the capability of corona discharge ionization ion mobility spectrometry (CD-IMS) in the determination of metal complex was evaluated. The extreme simplicity of dispersive liquid–liquid microextraction (DLLME) coupled to the high sensitivity of CD-IMS measurement could make this combination really useful for simple, rapid, and sensitive determination of metals in different samples. In this regard, mercury, as a model metal, was complexed with diethyldithiocarbamate (DEDTC), and then extracted into the carbon tetrachloride using DLLME. Some parameters affecting the extraction efficiency, including the type and volume of the extraction solvent, the type and volume of the disperser solvent, the concentration of the chelating agent, salt addition and, pH were exhaustively investigated. Under the optimized condition, the enrichment factor was obtained to be 142. The linear range of 0.035–10.0 μg mL⁻¹ with r² = 0.997 and the detection limit of 0.010 μg mL⁻¹ were obtained. The relative standard deviation values were calculated to be lower than 4% and 8% for intra-day and inter-day, respectively. Finally, the developed method was successfully applied for the extraction and determination of mercury in various real samples. The satisfactory results revealed the capability of the proposed method in trace analysis without tedious derivatization or hydride generation.     

表面离化源工作参数对离子迁移率谱的影响

根据表面离化过程中样品分子在离化材料表面直接离化的特点,设计了一种样品离化和离子注入一步完成的面-网结构表面离化源.以金属钼为离化材料,三乙胺为测试样品,研究了离化源温度、离子门开门脉冲宽度和高度对离子谱图的影响.结果表明,离子流信号强度随离化温度升高迅速增强但离化源寿命缩短,理想的离化温度约为400℃；增加开门脉冲宽...     

Filament temperature stabilizer for a thermal ionization mass spectrometer

A major enhancement in temperature stabilization of a filament has recently been achieved by means of the Halas–Kami ski bridge, in which the reference resistance of one leg is directly proportional to the filament temperature. In this article we describe a novel version of this type of electronic circuit which feeds dc power voltage to the filament via a switching transistor. The switching frequency is regulated by means of a triangular waveform generator incorporated into the system. The duration of the heating peak (square wave) is automatically adjusted properly once at each break between two subsequently appearing heating peaks, which is the interval when the bridge imbalance signal is measured. At the end of each break the bridge imbalance signal is kept on the output of the sample-and-hold amplifier. This signal compared with the generator output voltage provides the square wave for the switching transistor. The application of this circuit for a thermal ionization mass spectrometry is simple and straightforward. The filament temperature is set by two decade low-ohm resistors. Long-term variance of the ion current is approximately 5 times lower than that obtained by use of a commercial voltage stabilizer for the filament supply. It is shown theoretically that stabilization of the filament resistance results in the lowest possible variance of temperature.     

Selective ionization for elemental analysis with an ion trap mass spectrometer

The ion storage capacity (<10⁶) of ion trap mass spectrometers (ITMS) can sometimes limit the ability to analyze trace components in complex mixtures. We demonstrate here that resonant laser ablation (RLA) can offer a degree of selectivity in the ionization process, thus allowing the preferential accumulation of analyte ions in the trap. Selectivities of 75 and 50, for chromium and iron, respectively, are reported here for RLA of stainless steel in an ITMS. We offer suggestions to improve both the selectivity and the ionization efficiency, relative to the results reported here.     

Separation of benzodiazepines by electrospray ionization ion mobility spectrometry-mass spectrometry

Benzodiazepines are a commonly abused class of drugs; requiring analytical techniques that can separate and detect the drugs in a rapid time period. In this paper, the two-dimensional separation of five benzodiazepines was shown by electrospray ionization (ESI) ion mobility spectrometry (IMS)-mass spectrometry (MS). In this study, both the two dimensions of separation (m/z and mobility) and the high resolution of our IMS instrument enabled confident identification of each of the five benzodiazepines studied. This was a significant improvement over previous IMS studies that could not separate many of the analytes due to low instrumental resolution. The benzodiazepines that contain a hydroxyl group in their molecular structure (lorazepam and oxazepam) were found to form both the protonated molecular ion and dehydration product as predominant ions. Experiments to isolate the parametric reasons for the dehydration ion formation showed that it was not the result of corona discharge processes or the potential applied to the needle. However, the potential difference between the needle and first drift ring did influence both the relative intensity ratios of the two ions and the ion sensitivity.     

Malathion detection method using microhotplate-based preconcentrator and ion mobility spectrometer

A simple and rapid method using a microhotplate-based preconcentrator and an ion mobility spectrometer (IMS) is proposed for the detection of malathion in water. The preconcentrator is prepared by micro-electro-mechanical system (MEMS) process. Coated with Polydimethylsiloxane (PDMS), it has the advantages of solvent-less, low energy cost, self-heating and ease to combine with IMS. The operating conditions of the preconcentrator-IMS system, such as extraction time, extraction temperature, agitation speed and desorption temperature, were optimised. Using the preconcentrator, the sampling procedure can be simplified and the detection limit of the system can be decreased. A linear relationship between the IMS response and the concentration of the analyte solution was verified. The malathion detection limit based on 3 times the baseline noise is 0.43?µg?L^?1 and the total analysis time is less than 30?minutes.     

Coupling of solid phase microextraction with electrospray ionization ion mobility spectrometry and direct analysis of venlafaxine in human urine and plasma

The capability of electrospray ionization-conventional ion mobility spectrometry (ESI–IMS) for direct analysis of the samples extracted by solid phase microextraction (SPME) was investigated and evaluated for the first time. To that end, an appropriate new desorption chamber was designed and constructed, resulting in the possibility of direct exposure of the SPME fiber to the electrospray solvent flow. Two different elution methods in dynamic and static modes were exhaustively investigated. The results indicated that the interface could help us to have an accurate and sensitive analysis without disturbing the electrospray process, in static elution method. Venlafaxine as a test compound was extracted from human urine and plasma by a convenient headspace SPME method. The positive ion mobility spectrum of the extracted drug was obtained and the analyte responses were calculated. The coupled method of SPME–ESI–IMS was comprehensively validated in terms of sensitivity, dynamic range, and recovery percentage. Finally, various real samples of human urine and plasma were analyzed, all verifying the feasibility and success of the proposed method for the easy routine analysis.     

Selective separation and determination of primidone in pharmaceutical and human serum samples using molecular imprinted polymer-electrospray ionization ion mobility spectrometry (MIP-ESI-IMS)

Application of electrospray ionization ion mobility spectrometry (ESI-IMS) as the detection technique for separation method based on molecular imprinted polymer (MIP) was investigated and evaluated. The method is exhaustively validated, including sensitivity, selectivity, recovery, reproducibility, and column capacity. The linear dynamic range of 0.02-2.00 μg mL⁻¹ was obtained for primidone analysis with ESI-IMS. The recovery of drug analyzed was calculated to be above 90% and the relative standard deviation (RSD), was below 3% for all experiments. Various real samples were analyzed with the coupled techniques, and the results obtained revealed the efficient clean-up of the samples using MIP separation before the analysis by ESI-IMS as a detection technique.     

High‐performance liquid chromatography with electrospray ionization ion mobility spectrometry: Characterization,data management,and applications

The combination of high‐performance liquid chromatography and electrospray ionization ion mobility spectrometry facilitates the two‐dimensional separation of complex mixtures in the retention and drift time plane. The ion mobility spectrometer presented here was optimized for flow rates customarily used in high‐performance liquid chromatography between 100 and 1500 μL/min. The characterization of the system with respect to such parameters as the peak capacity of each time dimension and of the 2D spectrum was carried out based on a separation of a pesticide mixture containing 24 substances. While the total ion current chromatogram is coarsely resolved, exhibiting coelutions for a number of compounds, all substances can be separately detected in the 2D plane due to the orthogonality of the separations in retention and drift dimensions. Another major advantage of the ion mobility detector is the identification of substances based on their characteristic mobilities. Electrospray ionization allows the detection of substances lacking a chromophore. As an example, the separation of a mixture of 18 amino acids is presented. A software built upon the free mass spectrometry package OpenMS was developed for processing the extensive 2D data. The different processing steps are implemented as separate modules which can be arranged in a graphic workflow facilitating automated processing of data.     

Ribonucleotide and ribonucleoside determination by ambient pressure ion mobility spectrometry

Detection limits and reduced mobilities for 12 ribonucleotides and 4 ribonucleosides were measured by ambient pressure electrospray ionization-ion mobility spectrometry (ESI-IMS). With the instrument used in this study it was possible to separate some of these compounds within mixtures. Detection limits reported for ribonucleotides and ribonucleosides ranged from 15 to 300 pmol and the reduced mobilities ranged from 41 to 56 suggesting that ambient pressure ESI-IMS may be used for their rapid and sensitive separation and detection. This report demonstrates that it was possible to use ion mobility spectrometry (IMS) to obtain a spectrum for the separation of nucleotides and nucleosides in less than 1 min. The application holds great promise for nucleotide analysis in the area of separating DNA fragments in genome sequencing and also for forensics DNA typing examinations used for the identification of blood stains in crime scenes and paternity testing.