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Taking a critical stand on contemporary trends in psychoanalysis regarding trauma, the author addresses the problem of psychic trauma mainly in terms of how it affects the patient’s status as a subject. After reexamining the notions of subject and subjectivity, the author illustrates the usefulness of the notion of “subjectality,” defined as a critical moment of subjectivity, necessary for processing the consequences of trauma. A clinical illustration is provided.

Background Tranexamic acid (TXA), an antifibrinolytic drug, is usually administered intravenously; however, intra-articular administration has recently been proven to be as effective as intravenous administration. Limited information regarding the pharmacokinetics (PK) of TXA after intra-articular administration has been reported. Aims The aim of this study was to develop a population PK model of TXA administered as a single intra-articular dose and as two intravenous doses, and to study the sources of interindividual variability (IIV) in the PK processes of TXA. The developed model was used to simulate PK profiles of TXA at different dosage regimens and in patients with renal impairment. Methods Patients who underwent primary unilateral total knee replacement (TKR) received 1 g/10 mL (concentration of 100 mg/mL) of TXA applied directly to the surgical field before wound closure, or 2 g (two doses of 1 g) of intravenous TXA. A population PK model was developed using a nonlinear mixed-effects approach and sources of IIV, such as sex, age, body weight, height, body mass index (BMI), preoperative haemoglobin, preoperative haematocrit, and creatinine clearance. Results Twenty-four patients were included, 12 in each group. Twenty patients were female, mean age (standard deviation) was 73.7 years (5.6). The disposition of TXA was best described as a two-compartment model with clearance dependent on creatinine clearance. Bootstrap results indicated that the model was stable and robust. The estimated bioavailability for intra-articular administration was 81%. Simulations indicated that 100% of patients would have plasma concentrations associated with partial fibrinolysis at 8 h post-administration with the dosages and routes of administration used in the present study. Intra-articular administration would produce complete inhibition of fibrinolysis in only 12% of patients compared with 72.5% with intravenous administration. No adverse events were reported. Conclusions This population PK model demonstrated that a single dose of high-concentration, low-volume intra-articular TXA can achieve antifibrinolytic plasma concentrations of the drug for 8 h, providing both local and systemic effects in patients undergoing TKR. TXA administration to the surgical field could be an alternative to the intravenous; route for patients undergoing TKR; however, clinical studies are needed to assess the toxic local effects of TXA.

Previous studies have shown the association of triglyceride glucose (TyG) index with metabolic syndrome (MetS), cardiovascular disease (CVD) and long-term adverse cardiovascular outcomes. However, to best our knowledge, the relation between the TyG index and in-hospital adverse cardiovascular outcomes in acute coronary syndrome (ACS) has not yet been reported. Hence, in this study, we aimed to evaluate the role of the TyG index in predicting in-hospital adverse cardiovascular outcomes in ACS and to compare its performance with the Global Acute Coronary 3Department of XXX, University of XXX, XXX Training and Research Hospital, City, Country Events Register (GRACE) risk score. 170 patients diagnosed with ACS and underwent coronary angiography were analyzed retrospectively. The 4Department of XXX, Faculty of XXX, City, Country TyG index was calculated using the following formula: ln [fasting triglycerides (mg/dL)×fasting blood glucose (mg/dL)/2]. Receiver operating characteristics (ROC) curve analysis was used to evaluate the performance of the TyG index and GRACE risk score in predicting in-hospital adverse cardiovascular outcomes. A binary logistic regression model was applied to determine the independent predictors for in-hospital adverse cardiovascular outcomes. At the initial analysis, patients with adverse cardiovascular outcomes had higher TyG index and GRACE risk score (p=0.011, p

Mitochondrial neurogastrointestinal encephalomyopathy (MNGIE) is an ultra-rare disorder caused by mutations in TYMP, leading to a deficiency in thymidine phosphorylase and a subsequent systemic accumulation of thymidine and 2'-deoxyuridine. Erythrocyte-encapsulated thymidine phosphorylase (EE-TP) is under clinical development as an enzyme replacement therapy for MNGIE. Bioanalytical methods were developed according to regulatory guidelines for the quantification of thymidine and 2'-deoxyuridine in plasma and urine using liquid chromatography-tandem mass spectrometry (LC-MS/MS) for supporting the pharmacodynamic evaluation of EE-TP. Samples were deproteinized with 5% perchloric acid (v/v) and the supernatants analyzed using a Hypercarb column (30 x 2.1 mm, 3 mu m), with mobile phases of 0.1% formic acid in methanol and 0.1% formic acid in deionized water. Detection was conducted using an ion-spray interface running in positive mode. Isotopically labelled thymidine and 2'-deoxyuridine were used as internal standards. Calibration curves for both metabolites showed linearity (r > 0.99) in the concentration ranges of 10-10,000 ng/mL for plasma, and 1-50 mu g/mL for urine, with method analytical performances within the acceptable criteria for quality control samples. the plasma method was successfully applied to the diagnosis of two patients with MNGIE and the quantification of plasma metabolites in three patients treated with EE-TP., Medical Research CouncilMedical Research Council UK (MRC) [MR/K025406/1]; Orphan Technologies, Ltd. [2016/22506-1]; Sao Paulo Research Foundation (FAPESP)Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP), This work was supported by the Medical Research Council [grant number MR/K025406/1] in partnership with Orphan Technologies, Ltd. N.J.A was in receipt of scholarship Grant n. 2016/22506-1, Sao Paulo Research Foundation (FAPESP).

Recently, there has been a major shift in the field of psychiatry towards the exploration of complex relationships between blood-based biomarkers and the pathophysiology of psychiatric and neuropsychiatric disorders. However, issues with study reproducibility, validity and reliability have hindered progress towards the identification of clinically relevant biomarkers for psychiatry. The achievement of laboratory validity is a crucial first step for the posterior development of clinical validity. There is evidence that the variability observed in blood-based research studies may be minimised with the implementation of standardised pre-analytical methods and uniform clinical protocols (i.e., pre-venipuncture). It has been documented that errors made in the pre-analytical phase account for 46–68.2% of laboratory testing errors. Thus, standardising clinical assessment, ethical procedures and pre-analytical phase of clinical research is essential for the reproducibility, validity and reliability of blood marker assessment, and reducing the risk of invalid test results. Various other areas of research have already moved towards guidelines for the standardised collection of blood-based biomarkers. Here we aim to provide a set of guidelines that we believe would improve biomarker research: (1) pre-venipuncture information and documentation, (2) ethics of participant consent and (3) pre-analytical methods. Ultimately, we hope this will assist study planning and will improve data comparison across studies allowing for the discovery of biomarkers in psychiatry with both laboratorial and clinical validity.

Electric mobility is a key element in the transition to a more sustainable transport system. Already today Li-ion batteries (LIB) are used in many stationary and mobile applications. If electric vehicles (EV) based on LIB reach a strong market penetration the recycling of lithium from growing numbers of automotive batteries will be decisive for future availability of this resource. However, the amount that EV battery recycling can contribute to lithium availability is unclear since the ability of secondary lithium to be reused in batteries is uncertain. Here we assess the trend in demand for lithium and the possible effects of automotive battery recycling by applying dynamic material flow analysis to the global lithium cycle. We found that lithium recovery from EV battery recycling could result in a significant oversupply of secondary material if its quality is not high enough to allow for reprocessing in battery production. In this case the application of secondary lithium would be limited to other use sectors and thus also restrict the possible savings of this resource. If secondary lithium only substitutes a relatively small quantity of virgin material whereas total lithium demand keeps rising, the production of primary raw materials will have to increase strongly. The findings of our work reveal the challenge that might result from a quality problem of recycled battery materials and thereby emphasize the importance of developing cost-effective recycling technologies with efficient material recovery processes for traction batteries as well as the timely development of a functioning recycling infrastructure.

The enantioresolution of pentedrone and methylone was carried out at a multi-milligram scale by liquid chromatography on a Chiralpak AS® stationary phase. The excellent enantioresolution using this column allowed to collect highly pure enantiomeric fractions, achieving enantiomeric ratios higher than 98%. An overall recovery of 72% was achieved for pentedrone enantiomers and 80% for methylone. Furthermore, the absolute configuration of the enantiomers of both cathinones was determined for the first time by electronic circular dichroism (ECD) spectroscopy, with the aid of theoretical calculations, as (+)‑(S) and (−)‑(R)-pentedrone, and (−)‑(S) and (+)‑(R)‑methylone. © 2018 Elsevier This research was partially supported by the Strategic Funding UID/Multi/04423/2013 through national funds provided by FCT – Foundation for Science and Technology and European Regional Development Fund (ERDF), in the framework of the programme PT2020, and also with funding from PTDC/MAR-BIO/4694/2014 project. Bárbara Silva thanks the Universidade do Porto /FMUP through FSE-Fundo Social Europeu, NORTE2020 -Programa Operacional Regional do Norte, no âmbito da operação NORTE-08-5369-FSE-000011-Programas Doutorais for her PhD grant.

The applicability of radon emanation to determine radium levels in (TE)NORM after EDTA-mediated sample dissolution has been investigated by means of a closed recirculating air loop radon monitoring system. Regarding radium determination in gypsum samples after EDTA-mediated dissolution the method presents excellent linearity (up to 2000 mBq), good resolution (75 mBq g−1) and detection limits (40 mBq g−1). The radioanalytical method presented here has been successfully applied to phosphogypsum samples and the radium levels obtained have been validated with gamma-spectroscopy. Evaluation of the experimental data indicate the robustness, selectivity and cost-effectiveness of this alternative radium analysis approach. © 2015, Akadémiai Kiadó, Budapest, Hungary. 306 2 445 449 Cited By :1

There are still unmet needs in finding new technologies for biomedical diagnostic and industrial applications. A technology allowing the analysis of size and sequence of short peptide molecules of only few molecular copies is still challenging. The fast, low-cost and label-free single-molecule nanopore technology could be an alternative for addressing these critical issues. Here, we demonstrate that the wild-type aerolysin nanopore enables the size-discrimination of several short uniformly charged homopeptides, mixed in solution, with a single amino acid resolution. Our system is very sensitive, allowing detecting and characterizing a few dozens of peptide impurities in a high purity commercial peptide sample, while conventional analysis techniques fail to do so., Existing methods used for peptide analysis suffer from low sensitivity and specificity. Here the authors demonstrate the nanopore-based size-discrimination and purity analysis of short homopolymeric peptides with a single amino acid resolution.

Surface heterogeneities, including roughness, significantly affect the adsorption, motion and interactions of particles at fluid interfaces. However, a systematic experimental study, linking surface roughness to particle wettability at a microscopic level, is currently missing. Here we synthesize a library of all-silica microparticles with uniform surface chemistry, but tuneable surface roughness and study their spontaneous adsorption at oil–water interfaces. We demonstrate that surface roughness strongly pins the particles’ contact lines and arrests their adsorption in long-lived metastable positions, and we directly measure the roughnessinduced interface deformations around isolated particles. Pinning imparts tremendous contact angle hysteresis, which can practically invert the particle wettability for sufficient roughness, irrespective of their chemical nature. As a unique consequence, the same rough particles stabilize both water-in-oil and oil-in-water emulsions depending on the phase they are initially dispersed in. These results both shed light on fundamental phenomena concerning particle adsorption at fluid interfaces and indicate future design rules for particle-based emulsifiers., Nature Communications, ISSN:2041-1723

Background:When subjected to time-dependent blood pressure, human arteries undergo large deformations, exhibiting mainly nonlinear hyperelastic type of response. The mechanical response of arteries depends on the health of tissues that comprise the artery walls. Typically, healthy arteries exhibit convex strain hardening under tensile loads, atherosclerotic parts exhibit stiffer response, and aneurysmatic parts exhibit softening response. In reality, arterial dynamics is the dynamics of a propagating pulse, originating in heart ventricle, propagating along aorta, bifurcating,etc. Artery as a whole cannot be simulated as a lump ring, however its cross section can be simulated as a vibrating ring having a phase lag with respect to the other sections, creating a running pressure wave. A full mathematical model would require fluid-solid interaction modeling continuity of blood flow in a compliant vessel and a momentum equation. On the other hand, laboratory testing often uses small-length arteries, the response of which is covered by the present work. In this way, material properties that change along the artery length can be investigated.Objective:The effect of strain hardening on the local dynamic response of human arteries (excluding the full fluid-structure interaction) is examined through appropriate hyperelastic models related to the health condition of the blood vessel. Furthermore, this work aims at constituting a basis for further investigation of the dynamic response of arteries accounting for viscosity.Method:The governing equation of motion is formulated for three different hyperelastic material behaviors, based on the constitutive law proposed by Skalaket al., Hariton, and Mooney-Rivlin, associated with the hardening behavior of healthy, atherosclerotic, and aneurysmatic arteries, respectively. The differences between these modelling implementations are caused by physiology, since aneurysmatic arteries are softer and often sclerotic arteries are stiffer than healthy arteries. The response is investigated by proper normalization of the involved material parameters of the arterial walls, geometry of the arteries, load histories, time effects, and pre-stressing. The effect of each problem parameter on the arterial response has been studied. The peak response of the artery segment is calculated in terms of radial displacements, principal elongations, principal stresses, and strain-energy density. The validity of the proposed analytical models is demonstrated through comparison with previous studies that investigate the dynamic response of arterial models.Results:Important metrics that can be useful to vascular surgery are the radial deformation and the maximum strain-energy density along with the radial resonance frequencies. These metrics are found to be influenced heavily by the nonlinear strain-hardening characteristics of the model and the longitudinal pre-stressing.Conclusion:The proposed formulation permits a systematic and generalizable investigation, which, together with the low computational cost of analysis, makes it a valuable tool for calculating the response of healthy, atherosclerotic, and aneurysmatic arteries. The radial resonance frequencies can explain certain murmures developed in stenotic arteries.

This work presents the development and characterization of a thermodenuder for the study and interpretation of aerosol volatility. Thermodenuder measurements are further combined with a continuous-flow streamwise thermal gradient CCN counter to obtain the corresponding aerosol hygroscopicity. The thermodenuder response function is characterized with monodisperse aerosol of variable volatility and hygroscopicity. The measurements are then interpreted with a comprehensive instrument model embedded within an optimization framework to retrieve aerosol properties with constrained uncertainty. Special attention is given to the interpretation of the size distribution of the thermodenuded aerosol, deconvoluting the effects of impurities and multiple charging, and to simplifications on the treatment of thermodenuder geometry, temperature, the cooling section, and the effects of curvature and accommodation coefficient on inferred particle volatility. Retrieved vapor pressures are consistent with published literature and shown to be most sensitive to uncertainty in the accommodation coefficient. Copyright © 2014 American Association for Aerosol Research.

Membrane raft size measurements are crucial to understanding the stability and functionality of rafts in cells. The challenge of accurately measuring raft size is evidenced by the disparate reports of domain sizes, which range from nanometers to microns for the ternary model membrane system sphingomyelin (SM)/1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC)/cholesterol (Chol). Using Förster resonance energy transfer (FRET) and differential scanning calorimetry (DSC), we established phase diagrams for porcine brain SM (bSM)/dioleoyl-sn-glycero-3-phosphocholine (DOPC)/Chol and bSM/POPC/Chol at 15 and 25 C. By combining two techniques with different spatial sensitivities, namely FRET and small-angle neutron scattering (SANS), we have significantly narrowed the uncertainty in domain size estimates for bSM/POPC/Chol mixtures. Compositional trends in FRET data revealed coexisting domains at 15 and 25 C for both mixtures, while SANS measurements detected no domain formation for bSM/POPC/Chol. Together these results indicate that liquid domains in bSM/POPC/Chol are between 2 and 7 nm in radius at 25 C: that is, domains must be on the order of the 2-6 nm Förster distance of the FRET probes, but smaller than the ~ 7 nm minimum cluster size detectable with SANS. However, for palmitoyl SM (PSM)/POPC/Chol at a similar composition, SANS detected coexisting liquid domains. This increase in domain size upon replacing the natural SM component (which consists of a mixture of chain lengths) with synthetic PSM, suggests a role for SM chain length in modulating raft size in vivo. © 2012 Elsevier B.V. All rights reserved.

Objectives: The IFCC Committee on Reference Intervals and Decision Limits coordinated a global multicenter study on reference values (RVs) to explore rational and harmonizable procedures for derivation of reference intervals (Rls) and investigate the feasibility of sharing RIs through evaluation of sources of variation of RVs on a global scale. Methods: For the common protocol, rather lenient criteria for reference individuals were adopted to facilitate harmonized recruitment with planned use of the latent abnormal values exclusion (LAVE) method. As of July 2015, 12 countries had completed their study with total recruitment of 13,386 healthy adults. 25 analytes were measured chemically and 25 immunologically. A serum panel with assigned values was measured by all laboratories. Rls were derived by parametric and nonparametric methods. Results: The effect of LAVE methods is prominent in analytes which reflect nutritional status, inflammation and muscular exertion, indicating that inappropriate results are frequent in any country. The validity of the parametric method was confirmed by the presence of analyte-specific distribution patterns and successful Gaussian transformation using the modified Box-Cox formula in all countries. After successful alignment of RVs based on the panel test results, nearly half the analytes showed variable degrees of between-country differences. This finding, however, requires confirmation after adjusting for BMI and other sources of variation. The results are reported in the second part of this paper. Conclusion: The collaborative study enabled us to evaluate rational methods for deriving Rls and comparing the RVs based on real-world datasets obtained in a harmonized manner. Ministry of Education, Culture, Sports, Science and Technology, Japan (MEXT) Japan Society for the Promotion of Science - 24256003

We demonstrate the synthesis of GaN nanocrystals (NCs) with the sizes of less than the doubled exciton Bohr radius leading quantum confinement effects via a single-step technique. The generation of colloidal GaN nanoparticles (NPs) in organic solution through nanosecond (ns) and femtosecond (fs) pulsed laser ablation (PLA) of GaN powder was carried out. Ns PLA in ethanol and polymer matrix resulted in amorphous GaN-NPs with the size distribution of 12.4 +/- 7.0 and 6.4 +/- 2.3 nm, respectively, whereas fs PLA in ethanol produced colloidal GaN-NCs with spherical shape within 4.2 +/- 1.9 nm particle size distribution. XRD and selected area electron diffraction analysis of the product via fs PLA revealed that GaN-NCs are in wurtzite structure. Moreover, X-ray photoelectron spectroscopy measurements also confirm the presence of GaN nanomaterials. The colloidal GaN-NCs solution exhibits strong blue shift in the absorption spectrum compared to that of the GaN-NPs via ns PLA in ethanol. Furthermore, the photoluminescence emission behavior of fs PLA-generated GaN-NCs in the 295-400 nm wavelength range is observed with a peak position located at 305 nm showing a strong blue shift with respect to the bulk GaN.

cited By 7; International audience; In this paper, we develop a methodological approach combining macro-X-ray fluorescence and synchrotron radiation-based techniques (μXRF, full-field XANES and μXRD) to determine the composition and microstructure of underglaze decors of Qinghua porcelains (Ming dynasty). Various transition metal elements (Fe, Mn, Co) are present in the blue decoration of these ceramics and the approach proposed allows for establishing the feature of each. Thus it shows that Fe ions are distributed homogeneously over the whole glaze without any significant difference in blue and white parts. They do not play a significant role in the color. In contrast, Co ions exhibit a heterogeneous distribution with CoAl2O4 particles close to the body/glaze interphase. These particles play a key role in the blue color and, the hue variations seem in greater part to link to their density and repartition. Co dispersed in the glassy matrix is also bivalent and mainly in tetragonal coordination, leading also to a blue color. Mn ion distribution is similar to the one of Co but without presenting local high concentrations associated to Mn based particles. Mn affects the darkness of the color and for the sample without CoAl2O4 particle; it is the main color contribution. The presence of CoAl2O4 crystals was confirmed by μXRD, which revealed, in addition, a variation of cell parameters certainly linking to a Co partial substitution.

A broadband optical transparent InGaAs semiconductor layer production of micron thicknesses was produced in only 75 s by thermionic vacuum arc (TVA) method at the first time. The optical and surface properties of the produced layers have been investigated. InGaAs structure is using in electronics and optoelectronics devices. The main advantage of TVA method is its fast deposition rate, without any loss in the quality of the films. Doping is a very simple and fast according to common production methods. InGaAs is an alloy of indium arsenide (InAs) and gallium arsenide (GaAs). InAs with (220) crystallographic direction and GaAs with (024)/(022) crystallographic directions were detected using by XRD analysis. GaAs and InAs are in the cubic and zinc blende crystal system, respectively. According to the transmittance spectra, sample has a broadband transparency in the range of 1000–3300 nm. According to results, defined TVA method for In doping to GaAs is proper fast and friendly method. SCANNING 38:297–302, 2016. © 2015 Wiley Periodicals, Inc. © Wiley Periodicals, Inc.

WOS: 000386404600009, In this study, an improved synthesis of 1,5-bis(2-formylphenyl)-1,5-dithiapentane(3) has been performed according to the literature in a high yield. 1,5-Bis (2-benzyl alcohol)-1,5-dithia pentane (4) was prepared by the reduction reaction of precursor compound in high yield via solvent-free conditions. Treatment of substituted benzylic alcohol with bromotrimethylsilane in dry acetonitrile in the presence of NaI resulted the formation of desired iodine derivative (5) in very high yield. 7,8-dihydro-6H, 14H, 19H-dibenzo[bj] [1,12,5,8]tetradithiacyclopentadecine-16,17-dicarbonitrile (7) was synthesized by the reaction of compound 7 and dithiomaleonitrile disodium salt. Magnesium porphyrazine carrying symmetrically four 15 membered tetrathia macro-cycles has been synthesized by the cyclotetramerization reaction of dicarbodinitrile compound (7) in the presence of magnesium butoxide according to the Linstead procedure. We focused on the prediction of the geometry optimization, normal mode frequencies, UV absorption spectra, chemical shifts and electronic properties of the compound by using B3LYP method with 6-31G(d) basis set. These novel compounds were characterized by a combination of elemental analysis, H-1, C-13 NMR, FTIR, UV vis and MS spectral data. An X-ray crystal structure of dicarbodinitrile compound (7) is also presented. The computed results are very close to the obtained experimental results by spectroscopic techniques, TUBITAK, The numerical calculations reported in this paper were partially performed at TUBITAK ULAKBIM, High Performance and Grid Computing Center (TRUBA resources). One of the author (B.Y) is also indepted to TUBITAK for financial support as scholarship. We are also grateful to Gebze Technical University X-Ray Center for the X-Ray data they provided.

Harmful Algal Bloom species are ubiquitous and their blooms occur in the Arabian Gulf. In this study, two cruises were performed in 2012 and 2013 to collect phytoplankton samples from 4 sites in the Arabian Gulf. Toxin analyses of phytoplankton samples for 32 algal toxins from 5 different toxin groups were conducted on the samples using both enzyme linked immunosorbent assay (ELISA) and liquid chromatography–tandem mass spectrometry (LC-MS/MS). Results demonstrated, for the first time, the presence of paralytic shellfish toxins (PSTs), diarrhetic shellfish toxin (DST), amnesic shellfish toxin (AST), cyclic imines (CIs) and polyether-lactone toxins in freeze-dried phytoplankton samples. Four Vulcanodinium rugosum cultures were established from field samples and these proved to contain between 603 and 981 ng pinnatoxin (PnTx) H per mg dry weight in addition to being positive for portimine. These strains from Qatar clustered with strains from Japan and Florida based on large subunit rRNA and rRNA internal transcribed spacer gene sequences.

Cervical samples were evaluated for human papillomavirus (HPV) presence using the hybrid capture-2 (HC2) assay and the polymerase chain reaction (PCR) with three different primer sets (GP5+/6+, MY09/11 and pU1M/2R). PCR results were compared to HC2 and results of all assays were compared to cytological and colposcopy findings. Post-test probability was assessed in individual assays and test combinations. HPV-DNA prevalence was 36.5% with HC2 and 55.2% with PCR. MY09/11 detected HPV-DNA in 38% of samples, GP5+/6+ in 19.1% and pU1M/2R in 16.4%. pU1M/2R and HC2 had the highest concordance (75.31%, k= 0.39 in the whole population; 74.1%, k= 0.5 in women with abnormal cytology). pU1M/2R had the best diagnostic performance, including optimal post-test probabilities and cervical abnormality detection (individually or in a panel of tests). Women positive for pU1M/2R may be at higher risk of disease progression; the assay performance when combined with a Pap smear in cervical cancer screening programs should be evaluated. © 2012 Elsevier B.V..

Two analytical approaches for the rapid measurement of hydrogen sulfide (H(2)S) have been compared to a reference method for their potential application as a rapid procedure for the quantification of H(2)S formed during alcoholic fermentations. In one case, silver nitrate, lead acetate, and mercuric chloride selective detector tubes for the analysis of H(2)S in air were investigated. In the other case, a commercially available kit for the diagnosis of nitrogen starvation in wine fermentations, which is based on the detection of H(2)S, was investigated. Both methods exhibited excellent linearity of response, but the mercuric chloride tube was found to suffer from interferences due to the concomitant presence of mercaptans, which resulted in erroneous H(2)S quantification. A comparative study between the two methods studied and the cadmium hydroxide/methylene blue reference method commonly used to monitor H(2)S indicate that the two new methods displayed better recoveries at low H(2)S concentrations, besides being more rapid and economical. The two new methods were successfully used to quantify production of H(2)S in different grape juice fermentations. The suitability of each method for the study of specific aspects of H(2)S production during fermentation is discussed.

Lateral flow assays (LFAs) are a widely-used point-of care diagnostic format, but suffer from limited analytical sensitivity, especially when read by eye. It has recently been reported that LFA performance can be improved by using magnetic reporter particles and an external magnetic field applied at the test line. The mechanism of sensitivity/performance enhancement was suggested to be concentration/retardation of reporter particles at the test line. Here we demonstrate an additional mechanism of particle relocation where reporter particles from the lower depths of the translucent LFA strip relocate to more-visible locations nearer to the top surface, producing a more visible signal. With a magnetic field we observed an improvement in sensitivity of human chorionic gonadotropin (hCG) detection from 1.25 ng/mL to 0.31 ng/mL. We also observed an increase of the color intensity per particle in test lines when the magnetic field was present. © 2018 Jacinto et al. This is an open access article distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited.

An ion-exchanger with polyanionic molecular brushes was synthesized by a "grafting from" route based on "surface-controlled reversible addition-fragmentation chain transfer polymerization" (RAFT). The RAFT agent, PhC(S)SMgBr was covalently attached to monodisperse-porous poly(dihydroxypropyl methacrylate-co-ethylene dimethacrylate), poly(DHPM-co-EDM) particles 5.8 µm in size. The monomer, 3-sulfopropyl methacrylate (SPM), was grafted from the surface of poly(DHPM-co-EDM) particles with an immobilized chain transfer agent by the proposed RAFT protocol. The degree of polymerization of SPM (i. e. the molecular length of the polyanionic ligand) on the particles was controlled by varying the molar ratio of monomer/RAFT agent. The particles carrying polyanionic molecular brushes with different lengths were tested as packing material in the separation of proteins by ion exchange chromatography. The columns packed with the particles carrying relatively longer polyanionic ligands exhibited higher separation efficiency in the separation of four proteins. Plate heights between 130-200 µm were obtained. The ion-exchanger having poly-(SPM) ligand with lower degree of polymerization provided better peak-resolutions on applying a salt gradient with higher slope. The molecular length and the ion-exchanger group content of polyionic ligand were adjusted by controlling the degree of polymerization and the grafting density, respectively. This property allowed control of the separation performance of the ion-exchanger packing. © 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ojectives To assess quality of life among Turkish immigrants in Sweden by using the WHOQOL-100 scale and to evaluate the domains' contribution to explain the variance in the quality of life of the immigrants. Our hypothesis was QOL among Turkish immigrants in Sweden are better than Turkish people who are living in their home country. Materials and methods This study was performed in the districts of Stockholm where Turkish immigrants have mostly settled. With the help and guidance of the Turkish Association, a sample of 520 participants was selected. We collected the demographic data by printed questionnaires, and to measure the quality of life, we used the WHOQOL-100 scale Turkish version. For analysis, we used the SPSS V.13.0 and R package programs, variance analyses, and Bayesian regression. Results The quality of life among the sample of Turkish immigrants was found to be moderate, but higher than the sample of the Turkish population. The quality of life of male immigrants was found to be higher than for females. Swedish-born Turks had better quality of life perceptions. Conclusions Turkish immigrants' quality of life perceptions were better than those of the Turkish sample. The best scores were received from the third generation. The first generation and female immigrants need attention in order to receive higher quality of life perceptions.

Objective: This study is based on whether the self-management program choices For Better Bone Health is effective to promote behavioral strategies for improving bone health, life quality, pain perception, physical function, and balance in osteoporotic subjects. Design: In this single-blind, randomized controlled study, a total of 50 sedentary women with postmenopausal and idiopathic osteoporosis were selected from the outpatients of AtatUrk Balneotherapy and Rehabilitation Center according to their physical activity level and T scores of dual-energy x-ray absorptiometry as the inclusion criteria. Fifty sedentary women with BM D T scores of -2.5 or lower were randomized into two groups (self-management group: group 1; and control group: group 2) and enrolled in a 6-mo study. Participants attended self-management class once a week for 5 wks. Evaluations were done at baseline, at the end of the fifth week, and at the sixth month. Pain-intensity evaluation by Visual Analogue Scale (VAS), life-quality assessments by SF-36, balance testing by Sensitized Romberg Test (SRT), and functional assessment by Timed Sit to Stand test (TSS) and a simple questionnaire were the outcome measures. Results: When the groups were compared by change scores and percentages of change, improvements observed in pain intensity by VAS (P < 0.001), SF-36 Physical Function (P < 0.001), SF-36 Physical Role Limitations (P < 0.001), SF-36 Social Function (P < 0.001), SF-36 Mental Health (P < 0.001), SF-36 Vitality (P < 0.01), SF-36 Pain (P < 0.001), SF-36 General Health Perceptions (P < 0.05), SF-36 Emotional Role Limitations (P < 0.01), SIRT eyes open (P < 0.001), SRT eyes closed (P < 0.001), and TSS (P < 0.001) were determined to be superior in group 1 at the end of the sixth month. Seventy-four percent of patients in group 1 engaged in regular physical activities, and 92% of them declared that they understood the purpose and benefits of medications and dietary calcium intake. Fifty-seven percent of them formed personal plans for preventing traumas, whereas 8% of the subjects in group 2 experienced new falls but no fractures. Conclusion: It is determined that the self-management class led to improvements in functional, balance, and life-quality outcomes and to reductions in pain perception.

A fast gas chromatography/mass spectrometry method was developed and validated for the analysis of the potential endocrine disrupters octinoxate and oxybenzone in swimming pool water samples based on the solvent-free solid-phase microextraction technique. The low-pressure gas chromatography/mass spectrometry method used for the fast identification of UV filter substances was compared to a conventional method in terms of sensitivity and speed. The fast method proposed resulted in 2 min runs, leading to an eightfold decrease in the total analysis time and a sevenfold improvement in detection limits. The main parameters affecting the solid-phase microextraction process were also studied in detail and the optimized conditions were as follows: fiber coating, polyacrylate; extraction mode, direct immersion; extraction temperature, 25 degrees C; sample volume, 5 mL; extraction time 45 min; pH 6.5. Under the optimized conditions, a linear response was obtained in the concentration range of 0.5-25 mu g/L with correlation coefficients in the range 0.990-0.999. The limits of detection were 0.17-0.29 mu g/L, and the recoveries were 80-83%. Combined method uncertainty was assessed and found to be less than 7% for both analytes for concentrations equal to or higher than 5 mu g/L. Pool water samples were analyzed to demonstrate the applicability of the proposed method. Neither octinoxate nor oxybenzone were detected in the swimming pool water samples at concentrations above the respective limits of detection.

Field experiments were devised to mimic the entrapment conditions under the rubble of collapsed buildings aiming to investigate the evolution of volatile organic compounds (VOCs) during the early dead body decomposition stage. Three pig carcasses were placed inside concrete tunnels of a search and rescue (SAR) operational field terrain for simulating the entrapment environment after a building collapse. The experimental campaign employed both laboratory and on-site analytical methods running in parallel. The current work focuses only on the results of the laboratory method using thermal desorption coupled to comprehensive two-dimensional gas chromatography with time-of-flight mass spectrometry (TD-GC × GC-TOF MS). The flow-modulated TD-GC × GC-TOF MS provided enhanced separation of the VOC profile and served as a reference method for the evaluation of the on-site analytical methods in the current experimental campaign. Bespoke software was used to deconvolve the VOC profile to extract as much information as possible into peak lists. In total, 288 unique VOCs were identified (i.e., not found in blank samples). The majority were aliphatics (172), aromatics (25) and nitrogen compounds (19), followed by ketones (17), esters (13), alcohols (12), aldehydes (11), sulfur (9), miscellaneous (8) and acid compounds (2). The TD-GC × GC-TOF MS proved to be a sensitive and powerful system for resolving the chemical puzzle of above-ground "scent of death". © 2015 Elsevier B.V.. 883 99 108 Cited By :12

Nitrate reduction is considered to be a minor microbial pathway in the oxidation of mangrove-derived organic matter due to a limited supply of nitrate in mangrove soils. At a limited availability of this electron acceptor compared to the supply of degradable carbon, nitrate ammonification is thought to be the preferential pathway of nitrate reduction. Mangrove forest mutually differ in their productivity, which may lead to different available carbon to nitrate ratios in their soil. Hence, nitrate ammonification is expected to be of more importance in high- compared to low-productive forests. The hypothesis was tested in flow-through reactors that contain undisturbed mangrove soils from high-productive Avicennia germinans and Rhizophora mangle forests in Florida and low-productive Avicennia marina forests in Saudi Arabia. Nitrate was undetectable in the soils from both regions. It was assumed that a legacy of nitrate ammonification would be reflected by a higher ammonium production from these soils upon the addition of nitrate. Unexpectedly, the soils from the low-productive forests in Saudi Arabia produced considerably more ammonium than the soils from the high-productive forests in Florida. Hence, other environmental factors than productivity must govern the selection of nitrate ammonification or denitrification. A rather intriguing observation was the 1:1 production of nitrite and ammonium during the consumption of nitrate, more or less independent from sampling region, location, sampling depth, mangrove species and from the absence or presence of additional degradable carbon. This 1:1 ratio points to a coupled production of ammonium and nitrite by one group of nitrate-reducing microorganisms. Such a production of nitrite will be hidden by the presence of active nitrite-reducing microorganisms under the nitrate-limited conditions of most mangrove forest soils.

cited By 4; International audience; A wide range of human sex hormone-binding globulin (hSHBG) affinity constants for testosterone (KAₕSHBG) has been reported in literature. To bring new insight on the KAₕSHBG value, we implemented a study of the molecular interactions occurring between testosterone and its plasma transport proteins by using surface plasmon resonance. The immobilization on the sensorchip of a testosterone derivative was performed by an oligoethylene glycol linker. For different plasmas with hSHBG concentrations, an assessment of the KAₕSHBG was obtained from a set of sensorgrams and curve-fitting these data. We observed that KAₕSHBG decreased, from at least two decades, when the plasma hSHBG concentration increased from 4.4 to 680 nmol/L. Our study shows a wide biological variability of KAₕSHBG that is related to the hSHBG concentration. These unexpected results may have a physiological significance and question the validity of current methods that are recommended for calculating free testosterone concentrations to evaluate androgen disorders in humans. © 2014 Elsevier Ireland Ltd.

The kinetic parameters of 1%, 2%, 3% and 4% La-doped ZnB2O4 phosphors (i.e. ZnB2O4:0.01La, ZnB2O4:0.02La, ZnB2O4:0.03La and ZnB2O4:0.04La) synthesized by nitric acid method have been calculated. Thermoluminescence (TL) glow curves of ZnB2O4:La phosphors after beta-irradiation showed a very well defined main peak having the maximum temperature at around 200 degrees C and a shoulder peak at around 315 degrees C with a constant heating rate of 5 degrees C/s. The kinetic parameters of ZnB2O4:La phosphors TL glow peaks (i.e. order of kinetics (b), activation energies (E-a) and frequency factors (s)) have been determined and evaluated by Computerized Glow Curve Deconvolution (CGCD), and Peak Shape (PS) methods using the glow curve data. From the results, it can conclude that the values of E-a obtained with these methods for ZnB2O4:La phosphors are consistent with each other, but the s values differ considerably.

Sulfate dry deposition increases the deteriorating effects on environment. Sulfate can be deposited from atmosphere to water via both particulate (SO4 2 :sulfate)and a gas(SO 2:sulfurdioxide)form.In this research, the fluxes of gaseous(SO 2)and particulate(SO 4 2)species were measured employing a water surface sampler(WSS)and glass fiber filters(GFFs)ontheknife−edge surrogate surface(KSSs)in the campus of Uludag University and the city of Bursa, Turkey.Sampling program was conducte dinter mittently between September2004and March2005.Average to talsulfate fluxes measured with the WS Satthe Uludag University campus and in the city of Bursa were58 ± 41and235 ± 43 mgm −2 d −1, respectively.The to talsulfate fluxe smeasure dat Bursa were highe rand this was probably due to greater sulfur containing species in it satmosphere.The dry deposition of gas eous SO 2 flux was calculated by sub tracting the particulate flux collected with the KSS s from the total flux(particulate sulfate plus SO 2 flux)obtained by the WSS.Anautomatic SO 2 analyzer was used concurrently to measure the ambient concentration of gas eous SO 2. The average SO2 gas fluxes and ambient SO 2 concentrations were18 ± 28and54 ± 48 mgm ⊟2 day ⊟1 and11 ± 7and49 ± 14 μgm ⊟3 for the campus and the city, respectively.The measured gaseous SO 2 fluxes and ambient concentrations were used to calculate the mass transfer coefficient.The calculated MTC values for the campus and the city were0.8 ± 1.0and1.2 ± 1.1 cms ⊟1, respectively.The sevalues wereinag reement with previously reported dry deposition velocities for SO 2.

The Aotus monkey has been of great value in the pre-clinical study of malaria vaccine candidates. Several components of this primate's immune system have been studied and they display great similarity to their human counterparts. Cloning and sequencing studies have revealed extensive sequence polymorphisms in Aotus MHC-DRB with very high similarities to several human allelic lineages, grouping at least nine distinct MHC-DRB lineages. As the efficacy of peptide vaccines in this animal model may be strongly influenced by exon 2 MHC-DRB polymorphism, the availability of a reliable and rapid MHC-DRB typing method for three species of Aotus (Aotus nancymaae, Aotus vociferans and Aotus nigriceps) is necessary. Reference strand conformational analysis (RSCA) was used here for differentiating the distinctive Aotus MHC-DRB sequences' mobility using five fluorescently labelled references proved to be very useful for resolving closely related sequences, establishing the number of sequences transcribed in a particular monkey and their identity. The RSCA method's reliability in terms of identifying Aotus MHC-DRB sequences will facilitate evaluating individual responsiveness to vaccines and prompt studies associating susceptibility/ resistance to infectious agents or auto-immune disease, for which Aotus monkeys may be considered to be an appropriate animal model. © Springer-Verlag 2006.

This study investigates the release mechanism of a hydrophilic drug (caffeine) from hydrophobic matrix tablets composed of starch acetate. Different particle size fractions of starch acetate were mixed with caffeine (22% V/V) to obtain various mixture organisations in the powder, as 14 well as in the final tablet. The organisation of powder mixtures was calculated by the carrier payload of starch acetate particles, while the pore size distributions in tablets were measured by mercury intrusion porosimetry. A carrier payload below I indicated the existence of a free starch acetate particle surface, while numbers greater than 1 pointed to a complete occupation of the starch acetate particle surface area by caffeine particles. The carrier payload calculations gave a good prediction for the existence of a starch acetate matrix in the tablet structures. Caffeine matrices in tablets compressed from the mixtures could be detected by mercury intrusion porosimetry measurements. The existence of different matrices, as well as different pore networks, determined the physical changes of the tablets and the release mechanism of caffeine during dissolution tests. When a tablet contained only a caffeine matrix, rapid tablet disintegration and immediate release of the total amount of caffeine occurred. A single matrix of starch acetate resulted in tablets that remained intact, although cracks were formed. The co-existence of matrices of both materials created surface erosion of the tablet. The caffeine release profiles of tablets that remained intact or showed erosion were fitted by an equation containing both diffusional and relaxational factors to describe the effect of tablet porosity on drug release. (c) 2005 Elsevier B.V. All rights reserved.

A reliable method for the determination of patulin in apple juice, apple puree and apples was developed using two clean-up steps and high performance liquid chromatography and diode array (HPLC-DAD) analysis. Baseline separation from hydroxymethyl furfural (HMF) was obtained. The performance characteristics of the method were determined at four concentration levels in two matrices and fulfill the requirements of the European Commission (EC) for this type of samples. The level of quantification was set to 25 μg/l or 25 μg/kg, the RSD for repeatability at this level is 11% for apple juice and 17% for apples, the recovery is 87% for apple juice and 63% for apples. The reproducibility was determined in apples and is 11% (at a level of 200 μg/kg). The method was used for determination of patulin in 63 commercial apple products available on the Dutch market. With the exception of one sample, the level of patulin was lower than the detection limit in all the samples. No statistically significant difference was found between conventional and organic samples. © 2004 Elsevier Ltd. All rights reserved.

A preliminary investigation on the possibility of using volatile organic compounds (VOCs) determination of expired air, blood and urine, for the early location of entrapped people in earthquakes, has been carried out. A group of 15 healthy subjects has been sampled. The identification of a common "core" of substances might provide indications of human presence that can be used for the development of a real time field analytical method for the on site detection of entrapped people. Expired air samples have been analyzed by thermal desorption GC/MS and VOCs from blood and urine by headspace SPME-GC/MS. Acetone was the only compound found common in all three matrices. Isoprene was found in both expired air and blood samples. Acetone and isoprene along with a number of saturated hydrocarbons were among the major constituents identified in expired air analysis. Various ketones (2-pentanone, 4-heptanone, 2-butanone) were also determined over urine specimens. Using the techniques and methods of field analytical chemistry and technology appears to be the proper approach for applying the results of the present study in real situations. © 2005 Elsevier B.V. All rights reserved. 822 1-2 112 117 Cited By :43

Motivation: Datasets resulting from metabolomics or metabolic profiling experiments are becoming increasingly complex. Such datasets may contain underlying factors, such as time (time-resolved or longitudinal measurements), doses or combinations thereof. Currently used biostatistics methods do not take the structure of such complex datasets into account. However, incorporating this structure into the data analysis is important for understanding the biological information in these datasets. Results: We describe ASCA, a new method that can deal with complex multivariate datasets containing an underlying experimental design, such as metabolomics datasets. It is a direct generalization of analysis of variance (ANOVA) for univariate data to the multivariate case. The method allows for easy interpretation of the variation induced by the different factors of the design. The method is illustrated with a dataset from a metabolomics experiment with time and dose factors. Availability: M-files for MATLAB for the algorithm used in this research are available at: http://www-its.chem.uva.nl/research/pac/Software/ or at http://www.bdagroup.nl Contact: asmilde@science.uva.nl

Proton binding plays a critical role in protein structure and function. We report pKa calculations for three aspartates in two proteins, using a linear response approach, as well as a "standard" Poisson-Boltzmann approach. Averaging over conformations from the two endpoints of the proton-binding reaction, the protein's atomic degrees of freedom are explicitly modeled. Treating macroscopically the protein's electronic polarizability and the solvent, a meaningful model is obtained, without adjustable parameters. It reproduces qualitatively the electrostatic potentials, proton-binding free energies, Marcus reorganization free energies, and pKa shifts from explicit solvent molecular dynamics simulations, and the pKa shifts from experiment. For thioredoxin Asp-26, which has a large pKa upshift, we correctly capture the balance between unfavorable carboxylate desolvation and favorable interactions with a nearby lysine similarly for RNase A Asp-14, which has a large pKa downshift. For the unshifted thioredoxin Asp-20, desolvation by the protein cavity is overestimated by 2.9 pKa units several effects could explain this. "Standard" Poisson-Boltzmann methods sidestep this problem by using a large, ad hoc protein dielectric but protein charge-charge interactions are then incorrectly downscaled, giving an unbalanced description of the reaction and a large error for the shifted pKa values of Asp-26 and Asp-14. © 2005 by the Biophysical Society. 88 6 3888 3904 Cited By :56

cited By 44; International audience; The electrochemical oxidation of lutetium bis(tetra-tert- butylphthalocyaninato) (LBPC) and decamethylferrocene (DMFC), as well as the reduction of LBPC, lutetium bis(phthalocyaninato) (LPC), and lutetium (tetra-tert-butylphthalocyaninato hexadecachlorphthalocyaninato) (LB-PCl), has been studied in a thin nitrobenzene (NB) film deposited on the surface of a graphite electrode (GE) by means of square-wave voltammetry (SWV). The organic film-modified electrode was immersed in an aqueous (W) electrolyte solution and used in a conventional three-electrode configuration. When the aqueous phase contains ClO4-, NO3-, or Cl - (ClO4-, or NO3- only, in the case of DMFC), both LBPC and DMFC are oxidized to stable monovalent cations in the organic phase. The electron transfer at the GE | NB interface is accompanied by a simultaneous anion transfer across the W | NB interface to preserve the electroneutrality of the organic phase. LBPC, LPC, and LBPCl are reduced to stable monovalent anions accompanied by expulsion of the anion of the electrolyte from the organic into the aqueous phase. In all cases, the overall electrochemical process comprises simultaneous electron and ion transfer across two separate interfaces. Under conditions of SWV, the overall electrochemical process is quasireversible, exhibiting a well-formed "quasireversible maximum" that is an intrinsic property of electrode reactions occurring in a limiting diffusion space. For all the redox compounds that have been studied, the kinetics of the overall electrochemical process is controlled by the rate of the ion transfer across the liquid | liquid interface. Based on the quasireversible maximum, a novel and simple methodology for measuring the rate of ion transfer across the liquid liquid interface is proposed. A theoretical background explaining the role of the ion-transfer kinetics on the overall electrochemical process at the thin organic film modified electrode under conditions of SWV is presented. Comparing the positions of the theoretical and experimental quasireversible maximums, the kinetics of ClO4 -, NO3-, and Cl- across the W | NB interface was estimated. The kinetics of the overall process at the thin organic film modified electrode, represented by the second-order standard rate constant, is 91 ± 8, 90 ± 4, and 133 ± 10 cm4 s-1 mol-1, for the transfer of ClO4 -, NO3-, and Cl- respectively. © 2005 American Chemical Society.

Heart rate variability (HRV) is a useful tool for the detection of sympathetic-parasympathetic balance of autonomic nervous system in patients at risk of sudden death (SD). SD is more common in patients with epilepsy and the exact mechanisms of SD are unknown. Autonomic nervous system involvement in patients with epilepsy has rarely been studied and has shown conflicting results. Our purpose was to determine if HRV showed any changes in patients with epilepsy in comparison with normal population. A short period analysis of HRV was performed for both the frequency and time domain in 43 epilepsy patients who had generalized tonic-clonic seizures (GTCS) and who were not taking any medications and also in 43 age and sex matched controls. In the time domain analysis, patients displayed higher SDNN (standard deviation of all R-R intervals), SDANN (standard deviation of mean NN intervals in 5 min recordings) and HRV triangular index than did healthy subjects (p < 0.0001). Patients tended to display higher pNN50 (number of R-R intervals differed by >50 ms from adjacent interval divided by the total number of all R-R intervals) and RMSSD (root-mean-square of successive differences) values than did healthy subjects, but the differences were not statistically significant (p > 0.05). In the frequency domain analysis, the spectral measures of HRV showed a reduction of high frequency (HF) values (is a marker of parasympathetic activity) and an increase of low frequency (LF) values (is a measure of sympathetic activity); as a result, the ratio between low and high frequencies (LF/HF) was significantly increased (p < 0.0001, p < 0.0001 and p < 0.001, respectively). Our data suggests an increase in the sympathetic control of the heart rate in epilepsy patients who have GTCS. This increased sympathetic activity could play a key role in the development of ventricular tachyarrhythmias in patients with epilepsy and may be related to the higher incidence of sudden death in this disorder as compared to controls. © 2005 Elsevier B.V. All rights reserved.

A general method is presented for combining mass spectrometry-based metabolomics data. Such data are becoming more and more abundant, and proper tools for fusing these types of data sets are needed. Fusion of metabolomics data leads to a comprehensive view on the metabolome of an organism or biological system. The ideas presented draw upon established techniques in data analysis. Hence, they are also widely applicable to other types of X-omics data provided there is a proper pretreatment of the data. These issues are discussed using a real-life metabolomics data set from a microbial fermentation process. © 2005 American Chemical Society.

The interactions of Sc3+ and Y3+ ions with disodium 1,2-dihydroxybenzene-3,5-disulfonate (Na2H2L, where H2L2- = Tiron) were investigated in aqueous solution by means of potentiometric and spectroscopic methods. The coordination of Tiron to Sc3+ and Y3+ takes place through two phenolic oxygen atoms of catecholate ion in different stoichiometries. Thus, the binding of Tiron to Sc3+ occurs either in 1 : 1 or 1 : 2 molar ratios; they have resulted by the formation of [ScL](-) and [ScL2](5-) type complexes, respectively. On the other hand, Y3+ ion behaves like Th4+ and Ln(3+) ions toward Tiron. It forms [YL](-) type complex in 1 : 1 molar ratio; but in 1 : 2 or in higher molar ratios, only unique [Y2L3](6-) type complex formation takes place. The formation constants of [ScL](-), [ScL2](5-), [YL](-), and [Y2L3](6-) complexes were determined by analysis of the potentiometric data in ionic medium of 0.1 M KNO3 or NaClO4 at 25degreesC. The hydrolytic reactions of Sc(III) and Y(III) complexes with Tiron were determined from potentiometric data and the formation constants of [ScL(OH)](2-) and [YL(OH)](2-) were also calculated.

Spectroscopy is a fast and rich analytical tool. On many occasions, spectra are acquired of two or more sets of samples that differ only slightly. These data sets then need to be compared and analyzed, but sometimes it is difficult to find the differences. We present a simple and effective method that detects and extracts new spectral features in a spectrum coming from one set with respect to spectra of another set on the basis of the fact that these new spectral features are essentially positive quantities. The proposed procedure (i) characterizes the spectra of the reference set by a component model and (ii) uses asymmetric least squares (ASLS) to find differences with respect to this component model. It should be stressed that the method only focuses on new features and does not trace relative changes of spectral features that occur in both sets of spectra. A comparison is made with the conventional ordinary least squares (OLS) approach. Both methods (OLS and ASLS) are illustrated with simulations and are tested for size-exclusion chromatography with infrared detection (SEC-IR) of mixtures of polymer standards. Both methods are able to provide information about new spectral features. It is shown that the ASLS-based procedure yields the best recovery of new features in the simulations and in the SEC-IR experiments. Band positions and band shapes of new spectral features are better retrieved with the ASLS than with the OLS method, even those which could hardly be detected visually. Depending on the spectroscopic technique used, the ASLS-based method facilitates identification of the new chemical compounds. © 2005 American Chemical Society.

PLD-118 is a novel, oral antifungal drug, under development for the treatment of Candida infections. Possible metabolism of PLD-118 by rat, dog and human S9 liver homogenates and inhibition of human cytochrome P450 (CYP) enzymes were investigated. PLD-118 (10 and 100 μm) incubated for 0-60 min with S9 fractions and NADPH was determined by HPLC, using the Waters AccQ.Tag method after derivatization of amino acids to stable, fluorescent derivatives. CYP assays were performed using pooled human liver microsomes with substrates, selective towards human CYP1A2, CYP2A6, CYP2B6, CYP2C9, CYP2C19, CYP2D6, CYP2E1 and CYP3A, incubated at concentrations around the Km. Incubation mixtures were preincubated with PLD-118 (0.1-100 μM) or control inhibitor for 5 min. No metabolism of PLD-118 was detected with rat and dog S9 fractions. A small (8%) decrease in PLD-118 at 100 μM (not detected at 10 μM) with human microsomes was considered to be biologically irrelevant. PLD-118 did not inhibit any of the tested CYPs. PLD-118, at concentrations up to 100 μM, is not metabolized by rat, dog or human liver S9 homogenates and does not inhibit human CYPs in vitro, suggesting little likelihood for interaction of PLD-118 with drugs metabolized by these enzymes. Copyright © 2004 John Wiley & Sons, Ltd.