Study of a microwave induced plasma as a universal ion source for inorganic and organic mass spectrometry.

A proof-of-concept study of the utilization of a single mass spectrometer for qualitative molecular analysis as well as for quantitative metal determination is described. This was performed with an argon microwave plasma as the ion source coupled to an ion trap mass spectrometer. A microwave induced plasma with tuneable power and gas flow rate was loaded with dried nebulized sample solutions. The commercially available plasma torch was slightly modified to allow the introduction of the sample in different regions of the plasma. Using soft settings, organic compounds introduced in the plasma plume could be detected as protonated molecular ions. Under harsher conditions, elemental analysis was demonstrated for several metals. Lead could be determined with a limit of detection of 150 nM. Minor on-the-fly adjustments of the power, flow rate and sampling distance allowed a mild fragmentation of organic compounds. Ionization differences observed were rationalized by emission spectroscopy, and excitation and rotational temperatures were determined. Simultaneous determination of elemental and molecular information was demonstrated for a rubidium-crown-ether complex. The maximum argon gas consumption for these tasks was below 2 L min-1 and the maximal power used was 90 W.

Electrospray Ion Mobility Spectrometer Based on Flexible Printed-Circuit Board Electrodes with Improved Resolving Power.

An easily built drift tube instrument with ring electrodes made of rolled-up flexible printed circuit boards is reported. Its resolving power was maximized by careful attention to the drift tube geometry and the response time of the detector amplifier and by employing a high separation field strength. The separation of singly charged aliphatic quaternary ammonium ions introduced by electrospray was performed, and the measured resolving power was between 86 and 97% of the theoretical limit for three different drift tube lengths investigated. For the longest drift length of 30 cm, a resolving power of up to 228 was obtained. Three benzalkonium chlorides were also separated with resolving powers of over 210. The tristate injection scheme can also be used, with only a small loss of the separation performance compared to the two-state injection.

Determination of tobramycin in eye drops with an open-source hardware ion mobility spectrometer.

The analysis of tobramycin was demonstrated successfully as an example for electrospray ionization on an open-source hardware ion mobility spectrometer. This instrument was assembled inexpensively in-house, and required only very few purpose-made components. The quantitative determination of tobramycin required 20 s for a reading. The calibration curve for the range from 50 to 200 µM was found to be linear with a correlation coefficient of r = 0.9994. A good reproducibility was obtained (3% relative standard deviation) and the limit of detection was determined as 8 µM. As the concentration of the active ingredient in the eye drops (ophthalmic solutions) is too high for the sensitivity of the instrument, the samples had to be diluted appropriately.

Determination of Binary Gas Mixtures by Measuring the Resonance Frequency in a Piezoelectric Tube.

The composition of gas mixtures may be determined via changes of the speed of sound. As this affects the resonance frequency of the gas inside a tube, indirect measurements through a frequency analysis are also possible. It is demonstrated that this may be carried out with unprecedented simplicity by the novel employment of a piezoelectric tube which serves at the same time as a resonance tube and as transducer into the electronic domain. Experiments were run using a simple diecast aluminum box as the measuring cell, inside which the piezoelectric tube made from lead zirconium titanate with 30-mm length and 5.35-mm inner diameter was suspended. A small loudspeaker placed into the cell served for excitation of the resonance. Peak frequencies between 3910 and 14,590 Hz (for pure CO2 and He, respectively) were obtained. Two component mixtures of O2/N2, CO2/N2, and He/N2 at various composition were tested. A linear frequency change from 4790 to 5100 Hz was observed when going from pure O2 to pure N2.

Methionine oxidation of proteins analyzed by affinity capillary electrophoresis in presence of silver(I) and gold(III) ions.

Oxidative damage of biopharmaceuticals during manufacturing and storage is a key concern throughout pharmaceutical development. However, few simple and robust analytical methods are available for the determination of oxidation sites. Here, the potential of affinity capillary electrophoresis (ACE) in the separation of proteins with oxidized methionine (Met) residues is shown. Silver(I) and gold(I) ions have the attribute to selectively form complexes with thioethers over sulfoxides. The addition of these ions to the BGE leads to a selective complexation of Met residues and, thus, to a change of charge allowing separation of species according to the different oxidation states of Met. The mechanisms of these interactions are discussed and binding constants for peptides containing Met with silver(I) are calculated. Additionally, the proposed method can be used as an indicator of oxidative stress in large proteins. The presented technique is easily accessible, economical, and has rapid analysis times, adding new approaches to the analytical toolbox of Met sulfoxide detection.

Low-cost automated capillary electrophoresis instrument assembled from commercially available parts.

A CE instrument that can be assembled from commercially available components with minimal construction effort is described. Except for the electronic control circuitry no specially made parts are required. It is based on a flexible design of microfluidic, electropneumatic, and electronic sections and different configurations can easily be implemented. Automated injection into the capillary is performed hydrodynamically by the application of a pressure for a controlled length of time. The performance of the device was tested with a contactless conductivity detector by separating different metal ions. In addition, nine metal cations related to the quality of honey were separated in 2.3 min and four honey samples were analysed quantitatively to demonstrate the applicability of the method.

Low-cost and versatile analytical tool with purpose-made capillary electrophoresis coupled to contactless conductivity detection: Application to antibiotics quality control in Vietnam.

In this study, the development of our purpose-made capacitively coupled contactless conductivity detection (C4 D) for CE is reported. These systems have been employed as a simple, versatile, and cost-effective analytical tool. CE-C4 D devices, whose principle is based on the control of the ion movements under an electrical field, can be constructed even with a modest financial budget and limited infrastructure. A featured application was developed for quality control of antimicrobial drugs using CE-C4 D, with most recent work on determination of aminoglycoside and glycopeptide antibiotics being communicated. For aminoglycosides, the development of CE-C4 D methods was adapted to two categories. The first one includes drugs (liquid or powder form) for intravenous injection, containing either amikacin, streptomycin, kanamycin A, or kanamycin B. The second one covers drugs for eye drops (liquid or ointment form), containing either neomycin, tobramycin, or polymyxin. The CE-C4 D method development was also made for determination of some popular glycopeptide antibiotics in Vietnam, including vancomycin and teicoplanin. The best detection limit achieved using the developed CE-C4 D methods was 0.5 mg/L. Good agreement between results from CE-C4 D and the confirmation method (HPLC- Photometric Diode Array ) was achieved, with their result deviations less than 8% and 13% for aminoglycoside and glycopeptide antibiotics, respectively.

Dual-Purpose Photometric-Conductivity Detector for Simultaneous and Sequential Measurements in Flow Analysis.

This work presents a new dual-purpose detector for photometric and conductivity measurements in flow-based analysis. The photometric detector is a paired emitter-detector diode (PEDD) device, whilst the conductivity detection employs a capacitively coupled contactless conductivity detector (C4D). The flow-through detection cell is a rectangular acrylic block (ca. 2 × 2 × 1.5 cm) with cylindrical channels in Z-configuration. For the PEDD detector, the LED light source and detector are installed inside the acrylic block. The two electrodes of the C4D are silver conducting ink painted on the PEEK inlet and outlet tubing of the Z-flow cell. The dual-purpose detector is coupled with a sequential injection analysis (SIA) system for simultaneous detection of the absorbance of the orange dye and conductivity of the dissolved oral rehydration salt powder. The detector was also used for sequential measurements of creatinine and the conductivity of human urine samples. The creatinine analysis is based on colorimetric detection of the Jaffé reaction using the PEDD detector, and the conductivity of the urine, as measured by the C4D detector, is expressed in millisiemens (mS cm-1).

Contactless conductivity detection for analytical techniques: Developments from 2016 to 2018.

The publications concerning capacitively coupled contactless conductivity detection for the 2-year period from mid-2016 to mid-2018 are covered in this update to the earlier reviews of the series. Relatively few reports on fundamental investigations or new designs have appeared in the literature in this time interval, but the development of new applications with the detection method has continued strongly. Most often, contactless conductivity measurements have been employed for the detection of inorganic or small organic ions in conventional capillary electrophoresis, less often in microchip electrophoresis. A number of other uses, such as detection in chromatography or the gauging of bubbles in streams have also been reported.

Injection system for fast capillary electrophoresis based on pressure regulation with flow restrictors.

A fast automated system for rapid electrophoretic separations in short conventional capillaries employing contactless conductivity detection is presented. The instrument is based on pneumatic pressurization and does not require a conventional pump. The required pressures and flow rates for the different steps of the injection and flushing processes are produced with the help of two flow restrictors. The device is implemented on a microfluidic breadboard with dimensions of ca. 13 × 20 cm and employs miniature valves. Nine inorganic cations, namely NH4+, K+ , Na+ , Ca2+ , Mg2+ , Mn2+ , Sr2+ , Li+ , and Ba2+ , could be separated in a capillary of 10 µm inner diameter and 6 cm effective length within 25 s. Following a reduction of the effective length to 4 cm, still five inorganic cations could be separated in a time span of 12 s. The repeatability of peak areas was better than 3.1 % and limits of detection between 3.5 and 5.5 µM were achieved.

Flow Injection Analysis with Direct UV Detection Following Electric Field Driven Membrane Extraction.

A method for on-line matrix elimination to enable selective quantification of ultraviolet absorbing analytes by a flow-injection analysis procedure is described. Selectivity is achieved by electric field driven extraction across a polymer inclusion membrane. The method was demonstrated on the example of the determination of naproxen from spiked human urine. Membranes of 10 µm thickness were employed which consisted of 7.5 mg cellulose triacetate as base polymer, 5 mg of o-nitrophenyl octyl ether as plasticizer and 7.5 mg of Aliquat 336 as cationic carrier. Ten µL of sample was introduced into a continuous stream of background solution consisting of 100 µM aqueous NaClO4 with a flow rate of 2 µL/min while applying a voltage of 150 V to the extraction cell. The target ion was electrokinetically transported across the membrane and enriched in 1.5 µL of a stagnant acceptor solution. This was subsequently pumped past a flow-through UV detector for quantification. The method showed a linear range from 5 to 200 µM with a correlation coefficient of 0.9978 and a reproducibility of typically 7% (n = 8). The detection limit of the method for naproxen was 2 µM.

Contactless conductivity detection for analytical techniques- Developments from 2014 to 2016.

The development of capacitively coupled contactless conductivity detection for the two-year period from mid-2014 to mid-2016 is covered in this review. This includes a survey of fundamental studies and further developments of the measuring technique reported as well as a discussion of new applications. These mostly concern capillary electrophoresis carried out in conventional capillaries as well as on microchip electrophoresis devices. The main focus is on the determination of small non-UV-absorbing organic ions and inorganic ions in different types of samples of clinical, nutritional or environmental interest. Outside of electrophoresis contactless conductivity detection is finding uses in detection in column chromatography, flow-injection analysis and industrial applications.

Background conductivity independent counter flow preconcentration method for capillary electrophoresis.

A preconcentration method for anions is presented, which relies on a trap created by applying an electric field against a hydrodynamic flow of the sample. The trapping zone is created in front of a cation exchange membrane that allows the isolation of the electrode and thus prevents any interference by electrolysis products. Preconcentration factors of up to 20 were demonstrated for nitrate and formate as model analyte ions and were linearly related to the sample volume passed through the trap. A discrimination between the ions was found possible by adjustment of the hydrodynamic flow velocity. The method was also found to be suitable for the preconcentration of an anion (nitrate at 100 µM) in presence of a second anion at a very high concentration (50 mM formate). The detection limits for the four anions chloride, nitrate, perchlorate, and formate could be lowered from 4, 4.3, 4.2, and 7.2 µM obtained without trapping respectively to 127, 142, 139, and 451 nM with trapping.

A Case of Specific Language Impairment in a Deaf Signer of American Sign Language.

This article describes the case of a deaf native signer of American Sign Language (ASL) with a specific language impairment (SLI). School records documented normal cognitive development but atypical language development. Data include school records; interviews with the child, his mother, and school professionals; ASL and English evaluations; and a comprehensive neuropsychological and psychoeducational evaluation, and they span an approximate period of 7.5 years (11;10-19;6) including scores from school records (11;10-16;5) and a 3.5-year period (15;10-19;6) during which we collected linguistic and neuropsychological data. Results revealed that this student has average intelligence, intact visual perceptual skills, visuospatial skills, and motor skills but demonstrates challenges with some memory and sequential processing tasks. Scores from ASL testing signaled language impairment and marked difficulty with fingerspelling. The student also had significant deficits in English vocabulary, spelling, reading comprehension, reading fluency, and writing. Accepted SLI diagnostic criteria exclude deaf individuals from an SLI diagnosis, but the authors propose modified criteria in this work. The results of this study have practical implications for professionals including school psychologists, speech language pathologists, and ASL specialists. The results also support the theoretical argument that SLI can be evident regardless of the modality in which it is communicated.

Microfluidic Breadboard Approach to Capillary Electrophoresis.

A breadboard approach for electrophoretic separations with contactless conductivity detection is presented. This is based on miniature off-the-shelf components such as syringe pumps, valves, and pressure controllers which could be set up in a very compact overall arrangement. It has a high flexibility for different tasks at hand, and the common operations of hydrodynamic injection and capillary flushing are automated. For demonstration of the versatility of the proposition, several very diverse configurations and modes of electrophoresis were successfully implemented, namely, standard capillary zone electrophoresis, pressure assisted zone electrophoresis, the simultaneous separation of cations and anions by dual-capillary zone electrophoresis, the separation of cationic amino acids by isotachophoresis, as well as the separation of small carboxylic acids by gradient elution moving boundary electrophoresis. The system also allows fast separations, as demonstrated by the analysis of six inorganic cations within 35 s. The approach addresses respective limitations of either conventional capillary electrophoresis instruments as well as electrophoretic lab-on-chip devices, while maintaining a performance in terms of detection limits and reproducibility comparable to standard instrumentation.

Validation of CE modeling with a contactless conductivity array detector.

Dynamic computer simulation data are compared for the first time with CE data obtained with a laboratory made system comprising an array of 8 contactless conductivity detectors (C(4) Ds). The experimental setup featured a 50 µm id linear polyacrylamide (LPA) coated fused-silica capillary of 70 cm length and a purpose built sequential injection analysis manifold for fluid handling of continuous or discontinuous buffer configurations and sample injection. The LPA coated capillary exhibits a low EOF and the manifold allows the placement of the first detector at about 2.7 cm from the sample inlet. Agreement of simulated electropherograms with experimental data was obtained for the migration and separation of cationic and anionic analyte and system zones in CZE configurations in which EOF and other column properties are constant. For configurations with discontinuous buffer systems, including ITP, experimental data obtained with the array detector revealed that the EOF is not constant. Comparison of simulation and experimental data of ITP systems provided the insight that the EOF can be estimated with an ionic strength dependent model similar to that previously used to describe EOF in fused-silica capillaries dynamically double coated with Polybrene and poly(vinylsulfonate). For the LPA coated capillaries, the electroosmotic mobility was determined to be 17-fold smaller compared to the case with the charged double coating. Simulation and array detection provide means for quickly investigating electrophoretic transport and separation properties. Without realistic input parameters, modeling alone is not providing data that match CE results.

Thermostatted dual-channel portable capillary electrophoresis instrument.

A new portable CE instrument is presented. The instrument features the concurrent separation of anions and cations in parallel channels. Each channel has a separate buffer container to allow independent optimization of separation conditions. The microfluidics circuit is based on off-the-shelf parts, and can be easily replicated; only four valves are present in the design. The system employs a miniature automated syringe pump, which can apply both positive and negative pressures (-100 to 800 kPa). The application of negative pressure allows a semi-automatic mode of operation for introducing volume-limited samples. The separations are performed in a thermostatted compartment for improved reproducibility in field conditions. The instrument has a compact design, with all components, save for batteries and power supplies, arranged in a briefcase with dimensions of 52 × 34 × 18 cm and a weight of less than 15 kg. The system runs automatically and is controlled by a purpose-made graphical user interface on a connected computer. For demonstration, the system was successfully employed for the concurrent separation and analysis of inorganic cations and anions in sediment porewater samples from Lake Baldegg in Switzerland and of metal ions in a sample from the tailing pond of an abandoned mine in Argentina.

Response bias reveals enhanced attention to inferior visual field in signers of American Sign Language.

Deafness results in cross-modal plasticity, whereby visual functions are altered as a consequence of a lack of hearing. Here, we present a reanalysis of data originally reported by Dye et al. (PLoS One 4(5):e5640, 2009) with the aim of testing additional hypotheses concerning the spatial redistribution of visual attention due to deafness and the use of a visuogestural language (American Sign Language). By looking at the spatial distribution of errors made by deaf and hearing participants performing a visuospatial selective attention task, we sought to determine whether there was evidence for (1) a shift in the hemispheric lateralization of visual selective function as a result of deafness, and (2) a shift toward attending to the inferior visual field in users of a signed language. While no evidence was found for or against a shift in lateralization of visual selective attention as a result of deafness, a shift in the allocation of attention from the superior toward the inferior visual field was inferred in native signers of American Sign Language, possibly reflecting an adaptation to the perceptual demands imposed by a visuogestural language.

American Sign Language Comprehension Test: A Tool for Sign Language Researchers.

The American Sign Language Comprehension Test (ASL-CT) is a 30-item multiple-choice test that measures ASL receptive skills and is administered through a website. This article describes the development and psychometric properties of the test based on a sample of 80 college students including deaf native signers, hearing native signers, deaf non-native signers, and hearing ASL students. The results revealed that the ASL-CT has good internal reliability (α = 0.834). Discriminant validity was established by demonstrating that deaf native signers performed significantly better than deaf non-native signers and hearing native signers. Concurrent validity was established by demonstrating that test results positively correlated with another measure of ASL ability (r = .715) and that hearing ASL students' performance positively correlated with the level of ASL courses they were taking (r = .726). Researchers can use the ASL-CT to characterize an individual's ASL comprehension skills, to establish a minimal skill level as an inclusion criterion for a study, to group study participants by ASL skill (e.g., proficient vs. nonproficient), or to provide a measure of ASL skill as a dependent variable.

Contactless conductivity detection for analytical techniques-developments from 2012 to 2014.

The review covers the progress of capacitively coupled contactless conductivity detection over the 2 years leading up to mid-2014. During this period many new applications for conventional CE as well as for microchip separation devices have been reported; prominent areas have been clinical, pharmaceutical, forensic, and food analyses. Further progress has been made in the development of field portable instrumentation based on CE with contactless conductivity detection. Several reports concern the combination with sample pretreatment techniques, in particular electrodriven extractions. Accounts of arrays of contactless conductivity detectors have appeared, which have been created for quite different tasks requiring spatially resolved information. The trend of the use of contactless conductivity measurements for applications other than CE has continued.