From Sample Processing to Quantification: A Full Electrochemical Approach for Neutral Analyte Derivatization, Capillary Electrophoresis Separation, and Contactless Conductivity Detection

A thin-layer electrochemical flow cell coupled to capillary electrophoresis with contactless conductivity detection (EC-CE-(CD)-D-4) was applied for the first time to the derivatization and quantification of neutral species using aliphatic alcohols as model compounds. The simultaneous electrooxidation of four alcohols (ethanol, 1-propanol, 1-butanol, and 1-pentanol) to the corresponding carboxylates was carried out on a platinum working electrode in acid medium. The derivatization step required 1 min at 1.6 V vs. Ag/AgCl under stopped flow conditions, which was preceded by a 10 s activation at 0 V. The solution close to the electrode surface was then hydrodynamically injected into the capillary, and a 2.5 min electrophoretic separation was carried out. The fully automated flow system operated at a frequency of 12 analyses per hour. Simultaneous determination of the four alcohols presented detection limits of about 5 x 10(-5) mol As a practical application with a complex matrix, ethanol concentrations were determined in diluted pale lager beer and in nonalcoholic beer. No statistically significant difference was observed between the EC-CE-(CD)-D-4 and gas chromatography with flame ionization detection (GC-FID) results for these samples. The derivatization efficiency remained constant over several hours of continuous operation with lager beer samples (n = 40).

Multifocal pattern electroretinography for the detection of neural loss in eyes with permanent temporal hemianopia or quadrantanopia from chiasmal compression

Aims To evaluate the ability of multifocal transient pattern electroretinography (mfPERG) to detect neural loss and assess the relationship between mfPERG and visual-field (VF) loss in eyes with chiasmal compression. Methods 23 eyes from 23 patients with temporal VF defects and band atrophy of the optic nerve and 21 controls underwent standard automated perimetry and mfPERG using a stimulus pattern of 19 rectangles, each consisting of 12 squares. The response was determined for the central rectangle, for the nasal and temporal hemifields (eight rectangles each) and for each quadrant (three rectangles) in both patients and controls. Comparisons were made using variance analysis. Correlations between VF and mfPERG measurements were verified by linear regression analysis. Results Mean +/- SD mfPERG amplitudes from the temporal hemifield (0.50 +/- 0.17 and 0.62 +/- 0.32) and temporal quadrants (superior 0.42 +/- 0.21 and 0.52 +/- 0.35, inferior 0.51 +/- 0.23 and 0.74 +/- 0.40) were significantly lower in eyes with band atrophy than in controls (0.78 +/- 0.24, 0.89 +/- 0.28, 0.73 +/- 60.26, 0.96 +/- 0.36, 0.79 +/- 0.26 and 0.91 +/- 0.31, respectively). No significant difference was observed in nasal hemifield measurements. Significant correlations (0.36-0.73) were found between VF relative sensitivity and mfPERG amplitude in different VF sectors. Conclusions mfPERG amplitude measurements clearly differentiate eyes with temporal VF defect from controls. The good correlation between mfPERG amplitudes and the severity of VF defect suggests that mfPERG may be used as an indicator of ganglion cell dysfunction.

Triagem auditiva neonatal: motivos da evasão das famílias no processo de detecção precoce

OBJETIVO: Analisar os motivos da evasão familiar no programa de triagem auditiva neonatal realizado em um hospital público e correlacioná-los com a distribuição demográfica das famílias e as características do programa. MÉTODOS: Participaram 132 famílias, de um total de 739 contatadas, cujos filhos nasceram em uma maternidade no interior do estado de São Paulo de outubro/2003 a dezembro/2005 e que não haviam comparecido para a realização do teste ou reteste da triagem auditiva neonatal. Foi aplicado um questionário de levantamento das causas de evasão, contendo perguntas relacionadas à triagem auditiva, nível de escolaridade e profissão dos pais e também sobre a audição e o desenvolvimento de linguagem da criança. RESULTADOS: Realizou-se a aplicação do questionário com 132 famílias (17,86%); com as demais não foi obtido contato. Deste total, 82 haviam faltado na primeira etapa da triagem auditiva (teste) e 50 não haviam retornado para realização do reteste. Os motivos mais frequentes para justificar a evasão foram o desinteresse e a dificuldade em conciliar o agendamento com a rotina familiar. Não houve associação entre os motivos da evasão e o nível de escolaridade e ocupação dos pais, nem com o profissional que realizou a orientação acerca da triagem auditiva. Não foi referido nenhum caso de alteração auditiva, nem de atraso significativo no desenvolvimento da linguagem. CONCLUSÃO: Os motivos da evasão familiar independem de variáveis voltadas à família e à dinâmica do programa de triagem auditiva.

Development of oil spill detection techniques for satellite optical sensors and their application to monitor oil spill discharge in Mediterranean sea

Satellite remote sensing has proved to be an effective support in timely detection and monitoring of marine oil pollution, mainly due to illegal ship discharges. In this context, we have developed a new methodology and technique for optical oil spill detection, which make use of MODIS L2 and MERIS L1B satellite top of atmosphere (TOA) reflectance imagery, for the first time in a highly automated way. The main idea was combining wide swaths and short revisit times of optical sensors with SAR observations, generally used in oil spill monitoring. This arises from the necessity to overcome the SAR reduced coverage and long revisit time of the monitoring area. This can be done now, given the MODIS and MERIS higher spatial resolution with respect to older sensors (250-300 m vs. 1 km), which consents the identification of smaller spills deriving from illicit discharge at sea. The procedure to obtain identifiable spills in optical reflectance images involves removal of oceanic and atmospheric natural variability, in order to enhance oil-water contrast; image clustering, which purpose is to segment the oil spill eventually presents in the image; finally, the application of a set of criteria for the elimination of those features which look like spills (look-alikes). The final result is a classification of oil spill candidate regions by means of a score based on the above criteria.

Detection and Modeling of Boundary Layer Height

This thesis tackles the problem of the automated detection of the atmospheric boundary layer (BL) height, h, from aerosol lidar/ceilometer observations. A new method, the Bayesian Selective Method (BSM), is presented. It implements a Bayesian statistical inference procedure which combines in an statistically optimal way different sources of information. Firstly atmospheric stratification boundaries are located from discontinuities in the ceilometer back-scattered signal. The BSM then identifies the discontinuity edge that has the highest probability to effectively mark the BL height. Information from the contemporaneus physical boundary layer model simulations and a climatological dataset of BL height evolution are combined in the assimilation framework to assist this choice. The BSM algorithm has been tested for four months of continuous ceilometer measurements collected during the BASE:ALFA project and is shown to realistically diagnose the BL depth evolution in many different weather conditions. Then the BASE:ALFA dataset is used to investigate the boundary layer structure in stable conditions. Functions from the Obukhov similarity theory are used as regression curves to fit observed velocity and temperature profiles in the lower half of the stable boundary layer. Surface fluxes of heat and momentum are best-fitting parameters in this exercise and are compared with what measured by a sonic anemometer. The comparison shows remarkable discrepancies, more evident in cases for which the bulk Richardson number turns out to be quite large. This analysis supports earlier results, that surface turbulent fluxes are not the appropriate scaling parameters for profiles of mean quantities in very stable conditions. One of the practical consequences is that boundary layer height diagnostic formulations which mainly rely on surface fluxes are in disagreement to what obtained by inspecting co-located radiosounding profiles.

Detection and identification of 700 drugs by multi-target screening with a 3200 Q TRAP LC-MS/MS system and library searching

The multi-target screening method described in this work allows the simultaneous detection and identification of 700 drugs and metabolites in biological fluids using a hybrid triple-quadrupole linear ion trap mass spectrometer in a single analytical run. After standardization of the method, the retention times of 700 compounds were determined and transitions for each compound were selected by a "scheduled" survey MRM scan, followed by an information-dependent acquisition using the sensitive enhanced product ion scan of a Q TRAP hybrid instrument. The identification of the compounds in the samples analyzed was accomplished by searching the tandem mass spectrometry (MS/MS) spectra against the library we developed, which contains electrospray ionization-MS/MS spectra of over 1,250 compounds. The multi-target screening method together with the library was included in a software program for routine screening and quantitation to achieve automated acquisition and library searching. With the help of this software application, the time for evaluation and interpretation of the results could be drastically reduced. This new multi-target screening method has been successfully applied for the analysis of postmortem and traffic offense samples as well as proficiency testing, and complements screening with immunoassays, gas chromatography-mass spectrometry, and liquid chromatography-diode-array detection. Other possible applications are analysis in clinical toxicology (for intoxication cases), in psychiatry (antidepressants and other psychoactive drugs), and in forensic toxicology (drugs and driving, workplace drug testing, oral fluid analysis, drug-facilitated sexual assault).

Cardiogoniometric parameters for detection of coronary artery disease at rest as a function of stenosis localization and distribution

Cardiogoniometry (CGM), a spatiotemporal electrocardiologic 5-lead method with automated analysis, may be useful in primary healthcare for detecting coronary artery disease (CAD) at rest. Our aim was to systematically develop a stenosis-specific parameter set for global CAD detection. In 793 consecutively admitted patients with presumed non-acute CAD, CGM data were collected prior to elective coronary angiography and analyzed retrospectively. 658 patients fulfilled the inclusion criteria, 405 had CAD verified by coronary angiography; the 253 patients with normal coronary angiograms served as the non-CAD controls. Study patients--matched for age, BMI, and gender--were angiographically assigned to 8 stenosis-specific CAD categories or to the controls. One CGM parameter possessing significance (P < .05) and the best diagnostic accuracy was matched to one CAD category. The area under the ROC curve was .80 (global CAD versus controls). A set containing 8 stenosis-specific CGM parameters described variability of R vectors and R-T angles, spatial position and potential distribution of R/T vectors, and ST/T segment alterations. Our parameter set systematically combines CAD categories into an algorithm that detects CAD globally. Prospective validation in clinical studies is ongoing.

Detection of regional blood perfusion changes in epileptic seizures with dynamic brain perfusion CT--a pilot study

BACKGROUND AND PURPOSE: Perfusion CT (P-CT) is used for acute stroke management, not, however, for evaluating epilepsy. To test the hypothesis that P-CT may identify patients with increased regional cerebral blood flow during subtle status epilepticus (SSE), we compared P-CT in SSE to different postictal conditions. METHODS: Fifteen patients (mean age 47 years, range 21-74) underwent P-CT immediately after evaluation in our emergency room. Asymmetry indices between affected and unaffected hemispheres were calculated for regional cerebral blood volume (rCBV), regional cerebral blood flow (rCBF), and mean transit time (MTT). Regional perfusion changes were compared to EEG findings. RESULTS: Three patients in subtle status epilepticus (group 1) had increased regional perfusion with electro-clinical correlate. Six patients showed postictal slowing on EEG corresponding to an area of regional hypoperfusion (group 2). CT and EEG were normal in six patients with a first epileptic seizure (group 3). Cluster analysis of asymmetry indices separated SSE from the other two groups in all three parameters, while rCBF helped to distinguish between chronic focal epilepsies and single events. CONCLUSION: Preliminary results indicate that P-CT may help to identify patients with SSE during emergency workup. This technique provides important information to neurologists or emergency physicians in the difficult clinical differential diagnosis of altered mental status due to subtle status epilepticus.

Novel mutation in OTC gene causes neonatal death in twin brothers

Ornithine transcarbamylase (OTC) deficiency is the most common inborn error of the urea cycle. OTC locus is located in the short arm of X-chromosome. Authors report a case of a woman who gave birth to monozygotic male twins who later died because of severe neonatal-onset hyperammonaemic encephalopathy caused by a novel mutation of OTC gene. Post-mortem liver biopsy was taken from the second twin; afterwards, blood was drawn from the mother for examination. DNA sequence data showed that the mother was a carrier of the same novel mutation that was previously detected in the case of her son. In OTC deficiency, detection of female carriers is important for genetic counselling and eventual prenatal diagnosis.

Comparison of voxel-based 3-D MRI analysis and subtraction ictal SPECT coregistered to MRI in focal epilepsy

While voxel-based 3-D MRI analysis methods as well as assessment of subtracted ictal versus interictal perfusion studies (SISCOM) have proven their potential in the detection of lesions in focal epilepsy, a combined approach has not yet been reported. The present study investigates if individual automated voxel-based 3-D MRI analyses combined with SISCOM studies contribute to an enhanced detection of mesiotemporal epileptogenic foci. Seven consecutive patients with refractory complex partial epilepsy were prospectively evaluated by SISCOM and voxel-based 3-D MRI analysis. The functional perfusion maps and voxel-based statistical maps were coregistered in 3-D space. In five patients with temporal lobe epilepsy (TLE), the area of ictal hyperperfusion and corresponding structural abnormalities detected by 3-D MRI analysis were identified within the same temporal lobe. In two patients, additional structural and functional abnormalities were detected beyond the mesial temporal lobe. Five patients with TLE underwent epileptic surgery with favourable postoperative outcome (Engel class Ia and Ib) after 3-5 years of follow-up, while two patients remained on conservative treatment. In summary, multimodal assessment of structural abnormalities by voxel-based analysis and SISCOM may contribute to advanced observer-independent preoperative assessment of seizure origin.

EXPLORATION OF THE MTSAT2 SATELLITE CAPABILITIES FOR REAL TIME DETECTION AND CHARACTERIZATION OF VOLCANIC EMISSIONS

In this report, we attempt to define the capabilities of the infrared satellite remote sensor, Multifunctional Transport Satellite-2 (MTSAT-2) (i.e. a geosynchronous instrument), in characterizing volcanic eruptive behavior in the highly active region of Indonesia. Sulfur dioxide data from NASA's Ozone Monitoring Instrument (OMI) (i.e. a polar orbiting instrument) are presented here for validation of the processes interpreted using the thermal infrared datasets. Data provided from two case studies are analyzed specifically for eruptive products producing large thermal anomalies (i.e. lava flows, lava domes, etc.), volcanic ash and SO2 clouds; three distinctly characteristic and abundant volcanic emissions. Two primary methods used for detection of heat signatures are used and compared in this report including, single-channel thermal radiance (4-µm) and the normalized thermal index (NTI) algorithm. For automated purposes, fixed thresholds must be determined for these methods. A base minimum detection limit (MDL) for single-channel thermal radiance of 2.30E+05 Wm- 2sr-1m-1 and -0.925 for NTI generate false alarm rates of 35.78% and 34.16%, respectively. A spatial comparison method, developed here specifically for use in Indonesia and used as a second parameter for detection, is implemented to address the high false alarm rate. For the single-channel thermal radiance method, the utilization of the spatial comparison method eliminated 100% of the false alarms while maintaining every true anomaly. The NTI algorithm showed similar results with only 2 false alarms remaining. No definitive difference is observed between the two thermal detection methods for automated use; however, the single-channel thermal radiance method coupled with the SO2 mass abundance data can be used to interpret volcanic processes including the identification of lava dome activity at Sinabung as well as the mechanism for the dome emplacement (i.e. endogenous or exogenous). Only one technique, the brightness temperature difference (BTD) method, is used for the detection of ash. Trends of ash area, water/ice area, and their respective concentrations yield interpretations of increased ice formation, aggregation, and sedimentation processes that only a high-temporal resolution instrument like the MTSAT-2 can analyze. A conceptual model of a secondary zone of aggregation occurring in the migrating Kelut ash cloud, which decreases the distal fine-ash component and hazards to flight paths, is presented in this report. Unfortunately, SO2 data was unable to definitively reinforce the concept of a secondary zone of aggregation due to the lack of a sufficient temporal resolution. However, a detailed study of the Kelut SO2 cloud is used to determine that there was no climatic impacts generated from this eruption due to the atmospheric residence times and e-folding rate of ~14 days for the SO2. This report applies the complementary assets offered by utilizing a high-temporal and a high-spatial resolution satellite, and it demonstrates that these two instruments can provide unparalleled observations of dynamic volcanic processes.

A paradoxical rise of neonatal seizures after treatment with vitamin B6

We report the case of a newborn with intractable epileptic seizures developing a paradoxical rise of seizure frequency and electroencephalogram alterations after administration of vitamin B6. We have been unable to determine the aetiology of this disorder. In a newborn presenting with drug-resistant epileptic seizures, the first therapeutic option remains the application of intravenous pyridoxine, but the physician should be aware of the risk of an increase in seizure frequency.

Triangle-programmed coulometric nanotitrations completed by continuous flow with potentiometric detection

Coulometric nanotitrations were realized in a microchannel system using a continuous-flow titration technique with a triangle current-time profile. Redox and acid-base titrations were carried out on Fe(II) and nitric acid samples, respectively, with the same nanotitrator device. A linear relation between the concentration and the coulometric current transferred to the solution was found. The advantages of this universally applicable nanotitrator are fast response, low sample volume, high sensitivity, and high reproducibility as well as the convenience of handling an automated analyzer of the flow-through type.

Detecting offsets in GPS time series: first results from the Detection of Offsets in GPS Experiment

The accuracy of Global Positioning System (GPS) time series is degraded by the presence of offsets. To assess the effectiveness of methods that detect and remove these offsets, we designed and managed the Detection of Offsets in GPS Experiment. We simulated time series that mimicked realistic GPS data consisting of a velocity component, offsets, white and flicker noises (1/f spectrum noises) composed in an additive model. The data set was made available to the GPS analysis community without revealing the offsets, and several groups conducted blind tests with a range of detection approaches. The results show that, at present, manual methods (where offsets are hand picked) almost always give better results than automated or semi‒automated methods (two automated methods give quite similar velocity bias as the best manual solutions). For instance, the fifth percentile range (5% to 95%) in velocity bias for automated approaches is equal to 4.2 mm/year (most commonly ±0.4 mm/yr from the truth), whereas it is equal to 1.8 mm/yr for the manual solutions (most commonly 0.2 mm/yr from the truth). The magnitude of offsets detectable by manual solutions is smaller than for automated solutions, with the smallest detectable offset for the best manual and automatic solutions equal to 5 mm and 8 mm, respectively. Assuming the simulated time series noise levels are representative of real GPS time series, robust geophysical interpretation of individual site velocities lower than 0.2–0.4 mm/yr is therefore certainly not robust, although a limit of nearer 1 mm/yr would be a more conservative choice. Further work to improve offset detection in GPS coordinates time series is required before we can routinely interpret sub‒mm/yr velocities for single GPS stations.

Incidence, etiology and risk factors of neonatal seizures Harris County, Texas, 1992--1994

This study was conducted to determine the incidence and etiology of neonatal seizures, and evaluate risk factors for this condition in Harris County, Texas, between 1992 and 1994. Potential cases were ascertained from four sources: discharge diagnoses at local hospitals, birth certificates, death certificates, and a clinical study of neonatal seizures conducted concurrent with this study at a large tertiary care center in Houston, Texas. The neonatal period was defined as the first 28 days of life for term infants, and up to 44 weeks gestation for preterm infants.^ There were 207 cases of neonatal seizures ascertained among 116,048 live births, yielding and incidence of 1.8 per 1000. Half of the seizures occurred by the third day of life, 70% within the first week, and 93% within the first 28 days of life. Among 48 preterm infants with seizures 15 had their initial seizure after the 28th day of life. About 25% of all seizures occurred after discharge from the hospital of birth.^ Idiopathic seizures occurred most frequently (0.5/1000 births), followed by seizures attributed to perinatal hypoxia/ischemia (0.4/1000 births), intracranial hemorrhage (0.2/1000 births), infection of the central nervous system (0.2/1000 births), and metabolic abnormalities (0.1/1000 births).^ Risk factors were evaluated based on birth certificate information, using univariate and multivariate analysis (logistic regression). Factors considered included birth weight, gender, ethnicity, place of birth, mother's age, method of delivery, parity, multiple birth and, among term infants, small birth weight for gestational age (SGA). Among preterm infants, very low birth weight (VLBW, $<$1500 grams) was the strongest risk factor, followed by birth in private/university hospitals with a Level III nursery compared with hospitals with a Level II nursery (RR = 2.9), and male sex (RR = 1.8). The effect of very low birth weight varied according to ethnicity. Compared to preterm infants weighing 2000-2999 grams, non-white VLBW infants were 12.0 times as likely to have seizures; whereas white VLBW infants were 2.5 times as likely. Among term infants, significant risk factors included SGA (RR = 1.8), birth in Level III nursery private/university hospitals versus hospitals with Level II nursery (RR = 2.0), and birth by cesarean section (RR = 2.2). ^