Parallel Operation of Electron Ionization and Chemical Ionization for GC-MS Using a Single TOF Mass Analyzer.

This work describes a novel mass spectrometer coupled to gas chromatography (GC-MS) that simultaneously displays the mass spectral information of electron (EI)- and chemical ionization (CI)-generated ion populations for a single chromatographic peak. After GC separation, the eluent is equally split and supplied in parallel to an EI and a novel CI source, both operating continuously. Precise switching of the ion optics provides the exact timing to consecutively extract the respective ion population from both sources and transfer them into a time-of-flight (TOF) mass analyzer. This technique enables the acquisition of complementary information from both ion populations (EI and CI) within a single chromatographic run and with sufficient data points to retain the chromatographic fidelity. The carefully designed GC transfer setup, fast ion optical switching, and synchronized TOF data acquisition system provide an automatic and straightforward spectral alignment of two ion populations. With an eluent split ratio of about 50% between the two ion sources, instrument detection limits of <40 fg on the column (octafluoronaphthalene) for the EI and <2 pg (benzophenone) for the CI source were obtained. The system performance and the additional analytical value for compound identification are demonstrated by means of different common GC standard mixtures and a commercial perfume sample of unknown composition.

Hydrogen Plasma-Based Medium Pressure Chemical Ionization Source for GC-TOFMS.

The construction, critical evaluation, and performance assessment of a medium-pressure (2-13 mbar), high-temperature chemical ionization (CI) source for application in GC-MS is described. The ion source is coupled to a commercial time-of-flight (TOF) mass analyzer. Reagent ions are generated in a two staged process. The first stage uses a filament free, helical resonator plasma (HRP) driven ion source for H3+ generation. Reagent gases, for example, nitrogen, isobutane, and methane are added in a second stage to the H3+ stream, which leads to the formation of final protonation reagents. The GC effluent is added subsequently to the reagent ion gas stream. Designed for the hyphenation with gas chromatography, this GC-CI-TOFMS combination produces GC limited Gaussian peak shapes even for high boiling point compounds. Limits of detection for the compounds investigated are determined as 0.4-1.2 pg on column with nitrogen, 0.6-12.6 pg with isobutane, and 2 pg to >25 pg with methane as reagent gas, respectively. An EPA 8270 LCS mix containing 78 main EPA pollutants is used to evaluate the selectivity of the different reagent ions. Using nitrogen as reagent gas, 74 of 78 compounds are detected. In comparison, 41 of 78 compounds and 62 of 78 compounds are detected with isobutane or methane as CI reagent gas, respectively.

Nucleophilic Aromatic Substitution Between Halogenated Benzene Dopants and Nucleophiles in Atmospheric Pressure Photoionization.

In a preceding work with dopant assisted-atmospheric pressure photoionization (DA-APPI), an abundant ion at [M + 77](+) was observed in the spectra of pyridine and quinoline with chlorobenzene dopant. This contribution aims to reveal the identity and route of formation of this species, and to systematically investigate structurally related analytes and dopants. Compounds containing N-, O-, and S-lone pairs were investigated with APPI in the presence of fluoro-, chloro-, bromo-, and iodobenzene dopants. Computational calculations on a density functional theory (DFT) level were carried out to study the reaction mechanism for pyridine and the different halobenzenes. The experimental and computational results indicated that the [M + 77](+) ion was formed by nucleophilic aromatic ipso-substitution between the halobenzene radical cation and nucleophilic analytes. The reaction was most efficient for N-heteroaromatic compounds, and it was weakened by sterical effects and enhanced by resonance stabilization. The reaction was most efficient with chloro-, bromo-, and iodobenzenes, whereas with fluorobenzene the reaction was scarcely observed. The calculated Gibbs free energies for the reaction between pyridine and the halobenzenes were shown to increase in the order I < Br < Cl < F. The reaction was found endergonic for fluorobenzene due to the strong C-F bonding, and exergonic for the other halobenzenes. For fluoro- and chlorobenzenes the reaction was shown to proceed through an intermediate state corresponding to [M + dopant](+), which was highly stable for fluorobenzene. For the bulkier bromine and iodine, this intermediate did not exist, but the halogens were shown to detach already during the approach by the nucleophile.

Design Study of an Atmospheric Pressure Photoionization Interface for GC-MS.

This contribution reports on the development of an atmospheric pressure photoionization (APPI) source interfacing a gas chromatograph (GC) with a bench-top Orbitrap high resolution mass spectrometer (MS). We present efforts on method development aiming at high temperature stability (325°C), constant low impurity levels upon prolonged source operation, and efficient reaction volume irradiation combined with minimum peak broadening. The performance throughout each iterative development step was carefully assessed. The final GC-APPI-MS setup demonstrated femtogram-on-column sensitivity and chromatographic peaks of Gaussian shape with base peak widths <2 s for even the highest boiling compounds present in different EPA standard mixtures. Graphical Abstract ᅟ.

The envoy® totally implantable hearing system, st. Croix medical.

The Totally Implantable Envoy® System is currently undergoing clinical trials in both the United States and Europe. The fully implantable hearing device is intended for use in patients with sensorineural hearing loss. The device employs piezoelectric transducers to sense ossicle motion and drive the stapes. Programmable signal processing parameters include amplification, compression, and variable frequency response. The fully implantable attribute allows users to take advantage of normal external ear resonances and head-related transfer functions, while avoiding undesirable earmold effects. The high sensitivity, low power consumption, and high fidelity attributes of piezoelectric transducers minimize acoustic feedback and maximize battery life (Gyo, 1996; Yanagihara, (1987) and 2001). The surgical procedure to install the device has been accurately defined and implantation is reversible.

In vivo characterization of piezoelectric transducers for implantable hearing AIDS.

BACKGROUND: Piezoelectric bimorph transducers may be used at the input stage of implantable hearing aids to convert ossicle vibrations into electrical waveforms, and at the output stage to convert electrical signals into mechanical motion that drives the ossicles. This study assessed transducer performance in anesthetized, acutely implanted cats using computer-averaged, laser-Doppler vibrometer measures and cochlear potentials. METHODS: Measures of output linearity and distortion for a transducer placed on the umbo were obtained from averaged laser-Doppler vibrometer outputs. Frequency response and equivalent sound pressure level for transducers placed against the stapes were estimated by comparing compound action potentials and cochlear microphonics elicited preoperatively by acoustic signals with responses elicited postoperatively by signals presented through transducers. RESULTS: The transducer placed on the umbo exhibited an effective bandwidth that exceeded 8 kHz, linear response behavior for driving voltages up to 2 Vrms, and harmonic distortion of -40 dB or better at all frequencies greater than 250 Hz. Except for a shorter latency, transducer-elicited cochlear potentials were indistinguishable from acoustically elicited responses. Frequency response varied widely across transducers, ranging from reasonably flat to possessing a bandpass characteristic with a peak at 2 to 4 kHz; 1-Vrms signals applied to transducers with various geometries yielded equivalent intensities of 62 to 108 dB sound pressure level at 4 kHz, 51 to 98 dB sound pressure level at 2 kHz, and 55 to 80 dB sound pressure level at 1 kHz. Differences in frequency response and equivalent sound pressure level stemmed from different resonance frequencies in transducers with dissimilar lengths and, more importantly, from variation in transducer-stapes contact force. CONCLUSIONS: Appropriately designed piezoelectric transducers can provide the cochlea with high-fidelity, wide-bandwidth signals. However, using them in implantable hearing aids requires that geometry and contact force be optimized to reduce variability in output level. Recording cochlear potentials is a cost-effective means of assessing transducer performance intraoperatively, but care must be exercised to take into account any temporary, drill-induced sensitivity loss.

Initial human feasibility study of DC ablation as a treatment for benign prostatic hyperplasia: 6 month follow-up data.

Direct current (DC) ablation is a novel non-thermal technology that causes focused coagulative necrosis in the lateral lobes of the prostate to treat benign prostatic hyperplasia (BPH). The necrosis is caused by a zone of non-physiologic pH which is created in a predictable pattern around each electrode in which a direct current is applied during treatment. The objective of this study was to optimize treatment parameters and assess treatment tolerability using transurethral DC ablation as an office-based treatment for BPH.

Direct current ablation destroys multi-stage fibrosarcomas in rats.

INTRODUCTION: Direct current (DC) ablation offers the potential for precise targeting of tumors and stimulation of the immune system, but has not achieved widespread use. This study was conducted to evaluate the impact on tumor size and subject survival of combining a main ablation treatment with a low-current pretreatment, to assess potential immune system activation, and to assess stimulation-related parameters. METHODS AND RESULTS: Twenty-six female Fischer 344 rats were injected with methylcholanthrene-induced fibrosarcoma cells to create primary tumors and again in the contralateral flank when primary tumors reached 700 mm(3) (contralateral tumors were proxies for metastases). There were four treatment groups: two control animals received no treatment; six control plus placebo animals had electrodes implanted but received no stimulation; eight received high-current stimulation (80 coulombs (C) of charge at 20 milliamperes (mA), over 66 minutes); and eight received high-current treatment one day after a low-current pretreatment (10C, 10 mA, 16.6 min). Electrodes were inserted through the tumor base in a single plane, 4.0mm apart, alternating anode and cathode. Treatments commenced once primary tumors reached 700 mm(3). All control animals were sacrificed 55 days after primary tumor cell injection due to excessive tumor growth. Tumors disappeared from all 16 treated rats within eight days; retreatment was required in two animals. Pretreatment had no effect on tumor disappearance or survival. CONCLUSION: Direct current ablation provides highly effective tumor destruction in a rat model. Slower growth of contralateral tumors suggests a remote effect that may involve the immune system.

Medium voltage therapy for preventing and treating asystole and PEA in ICDs.

INTRODUCTION: Sudden cardiac death (SCD) takes up to 500,000 lives each year before a victim can even be treated. To address this the implantable cardioverter defibrillator (ICD) was developed to treat those identified at high risk of SCD. Unfortunately, there are a significant number of cases in which the ICD does not successfully return a victim to normal rhythm and effective perfusion of the blood. METHODS: The vast majority of cases that are not responsive to the ICD therapy require cardio-pulmonary resuscitation (CPR) according to current resuscitation guidelines. A novel electrical stimulus called medium voltage therapy (MVT) has shown efficacy in producing coronary and carotid blood flow during ventricular fibrillation. This report presents the case that the same stimulus may be effective and feasible for use in ICD patients that do not respond to their ICD therapy, or do not have a rhythm in which, an ICD shock is indicated. CONCLUSION: The inclusion of MVT technology in implantable devices may be effective in preparing the heart for successful defibrillation or in improving the metabolic condition of the heart to the extent that a pulsatile rhythm may spontaneously develop.