Quadruple Mass Spectrometer Research Articles

Phenolic profile of pollen collected from different ‘Oblačinska’ sour cherry (Prunus cerasus L.) clones

The presence of pollinators in orchards is crucial to obtain high fruit set and yields of fruits. Despite the fact that sour cherry cultivars are mainly autogamous, insect visits are still of great importance for their propagation. In order to attract and reward pollinators, flowers have to provide adequate nourishment to them. Besides nectar, bees gather pollen, which are a prerequisite for normal colony growth and development of their broods. ‘Oblacinska’ sour cherry (Prunus cerasus L.), an autochthonous cultivar, is the most highly planted cultivar in Serbian commercial orchards. Since the cultivar is actually a mixture of different clones, variability in numerous traits and, particularly, its yields has been reported. Since phenolic compounds are considered to be fundamental pollen chemicals, the aim of this study was to determine the phenolic compounds profile in pollen collected from 15 ‘Oblacinska’ sour cherry clones with varying productivity levels. Solid phase extraction (SPE), combined with ultra-high-performance liquid chromatography coupled with a diode array detector and a triple quadruple mass spectrometer (UHPLC DAD-MS/MS), was used to analyse the polyphenolic profile of pollen. Among 23 components quantified, rutin was the most abundant phenolic compound. It ranged from 98.49 (clone V/P) to 358.83 mg kg(-1) (clone III/9) and was observed to contribute, on average, 56% of the total phenolic compounds in pollen as quantified in different ‘Oblacinska’ sour cherry clones. In addition to this compound, clones contained significant amounts of chlorogenic acid (12.92%), astragalin (8.19%), and hyperoside (5.59%) as well. Cluster analysis grouped pollen clones in four different clusters, which showed that clones III/9, IV/8, and V/P had unique phenolic profiles. Despite the significant differences among the studied clones, the contents of chlorogenic acid, rutin, naringin, hyperoside, astralgin, and phlorizin were distinguishable between the clusters.

Needle lost in the haystack: multiple reaction monitoring fails to detect Treponema pallidum candidate protein biomarkers in plasma and urine samples from individuals with syphilis

Background: Current syphilis diagnostic strategies are lacking a sensitive manner of directly detecting Treponema pallidum antigens. A diagnostic test that could directly detect T. pallidum antigens in individuals with syphilis would be of considerable clinical utility, especially for the diagnosis of reinfections and for post-treatment serological follow-up. Methods: In this study, 11 candidate T. pallidum biomarker proteins were chosen according to their physiochemical characteristics, T. pallidum specificity and predicted abundance. Thirty isotopically labelled proteotypic surrogate peptides (hPTPs) were synthesized and incorporated into a scheduled multiple reaction monitoring assay. Protein extracts from undepleted/unenriched plasma (N = 18) and urine (N = 4) samples from 18 individuals with syphilis in various clinical stages were tryptically digested, spiked with the hPTP mixture and analysed with a triple quadruple mass spectrometer. Results: No endogenous PTPs corresponding to the eleven candidate biomarkers were detected in any samples analysed. To estimate the Limit of Detection (LOD) of a comparably sensitive mass spectrometer (LTQ-Orbitrap), two dilution series of rabbit cultured purified T. pallidum were prepared in PBS. Polyclonal anti- T. pallidum antibodies coupled to magnetic Dynabeads were used to enrich one sample series; no LOD improvement was found compared to the unenriched series. The estimated LOD of MS instruments is 300 T. pallidum/ml in PBS. Conclusions: Biomarker protein detection likely failed due to the low (femtomoles/liter) predicted concentration of T. pallidum proteins. Alternative sample preparation strategies may improve the detectability of T. pallidum proteins in biofluids.

Application of stable isotope dimethyl labeling for MRM based absolute antigen quantification of influenza vaccine

Determining the precursor/product ion pair and optimal collision energy are the critical steps for developing a multiple reaction monitoring (MRM) assay using triple quadruple mass spectrometer for protein quantitation. In this study, a platform consisting of stable isotope dimethyl labeling coupled with triple-quadruple mass spectrometer was used to quantify the protein components of the influenza vaccines. Dimethyl labeling of both the peptide N-termini and the ϵ-amino group of lysine residues was achieved by reductive amination using formaldehyde and sodium cyanoborohydrate. Dimethylated peptides are known to exhibit dominant a1 ions under gas phase fragmentation in a mass spectrometer. These a1 ions can be predicted from the peptide N-terminal amino acids, and their signals do not vary significantly across a wide range of collision energies, which facilitates the determination of MRM transition settings for multiple protein targets. The intrinsic a1 ions provide sensitivity for acquiring MRM peaks that is superior to that of the typical b/y ions used for native peptides, and they also provided good linearity (R2 ≥ 0.99) at the detected concentration range for each peptide. These features allow for the simultaneous quantification of hemagglutinin and neuraminidase in vaccines derived from either embryo eggs or cell cultivation. Moreover, the low abundant ovalbumin residue originated from the manufacturing process can also be determined. The results demonstrate that the stable isotope dimethyl labeling coupled with MRM Mass spectrometry screening of a1 ions (i.e., SIDa-MS) can be used as a high-throughput platform for multiple protein quantification of vaccine products.

An HPLC-MS/MS method for the simultaneous determination of luteolin and its major metabolites in rat plasma and its application to a pharmacokinetic study.

A selective and accurate HPLC-MS/MS method was established to simultaneously quantify luteolin and its active metabolites (diosmetin, chryseriol, and luteolin-7-O-glucuronide) in rat plasma. The analytes were separated on a C18 column with a mobile phase of water containing 0.5% formic acid and acetonitrile under gradient elution to shorten the total chromatographic run time and increase the resolution of diosmetin and chryseriol. A triple quadruple mass spectrometer coupled with an electrospray ionization source in the negative ion mode was used to detect the analytes. The multiple reaction monitoring transitions were of m/z 284.9→132.9 for luteolin, m/z 298.9→283.9 for diosmetin and chryseriol, m/z 461.1→284.9 for luteolin-7-O-glucuronide, and m/z 300.9→150.9 for the internal standard. The method was linear within the concentration ranges of 0.06-90 μg/mL for luteolin, 0.03-12 μg/mL for diosmetin, 0.015-4.8 μg/mL for chryseriol, and 0.06-60 μg/mL for luteolin-7-O-glucuronide. The intra- and interday precisions were all within 6.0%. Accuracy ranged from -3.2 to 6.4%. The matrix effect and instability were not observed during bioanalysis. This method was used to study the pharmacokinetic characteristics of luteolin and its metabolites in rats after treatment with luteolin.

MWCNTs-solid phase extraction combined with ultra-high performance liquid chromatography-tandem mass spectrometry for the determination of eleven organophosphorus pesticides in river water

ABSTRACTA method for simultaneous determination of 11 organophosphorus pesticides residues in river water by MWCNTs-solid phase extraction combined with ultra-high performance liquid chromatography/tandem mass spectrometry was developed. After centrifugation and filtration, the target pesticides were enriched with MWCNTs-SPE cartridge. Then the pesticides adsorbed on MWCNTs were eluted with ethyl acetate and dichloromethane, the eluent was dried-up under nitrogen flow and the residue was dissolved in methanol-water (1:1, v/v) as sample solution. The separation was accomplished on a C18 column with the mobile phase consisting of methanol and 0.1% formic acid at 0.20 mL/min in gradient elution. The pesticides were detected in multiple reaction monitoring mode by a triple quadruple mass spectrometer. Good linearities were obtained within 1–200 ng/L, with the correlation coefficients greater than 0.998. The detection and quantification limits were in the ranges of 0.02–1.00 ng/L and 0.07–3.33 ng/L, respectively. The recoveries and relative standard deviations were in the range of 88.3–124.9% and 0.12–20.5%, respectively. The method has been successfully applied to the detection of 34 urban river water samples from Chengdu, China and 7 organophosphorus pesticides were detected with the concentrations of 0.32–211 ng/L.

Geographical distribution of perfluorooctanesulfonate and perfluorooctanoate in selected rivers from Nigeria

Global concern on emerging pollutants such as perfluorooctanesulfonate (PFOS) and perfluorooctanoate (PFOA) are well documented. Unfortunately, information is either scarce or non-existing on the presence of these chemicals in most developing nations like Nigeria. The current study examined the distribution pattern and trend of PFOS and PFOA in surface water, porewater (PW) and sediments collected from three geopolitical zones with different levels of industrialization in Nigeria. PFOS and PFOA were concentrated using solid-phase extraction, identified and quantified by high performance liquid chromatography interfaced to a triple quadruple mass spectrometer. Detection of both PFOS and PFOA in all samples suggested wide distribution across Nigeria. Generally, PFOS dominated aqueous concentrations ranging from 3.9 to 10.1 ng L−1 in surface water, 10.9 to 20.4 ng L−1 in PW and 5.1 to 10.4 ng g−1 in bottom sediment. Field-based partition coefficients (Kd) for both PFOS and PFOA were significantly correlated with salinity (r2 = 0.84 and 0.78 respectively, p < 0.01); The Kd values increased exponentially as a function of salinity. The enrichment of both PFOS and PFOA on sediment increased with increasing organic matter while in water with increasing salinity. The detection of these chemicals across all samples suggested urgent attention in their risk assessment.

Core–shell indium (III) sulfide@metal-organic framework nanocomposite as an adsorbent for the dispersive solid-phase extraction of nitro-polycyclic aromatic hydrocarbons

A core–shell discoid shaped indium (III) sulfide@metal-organic framework (MIL-125(Ti)) nanocomposite was synthesized by a solvothermal method and explored as an adsorbent material for dispersive solid-phase extraction (d-SPE). The as-synthesized sorbent was characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, powder X-ray diffraction, N2 adsorption–desorption analysis, and Fourier transform infrared spectroscopy. The extraction performance was evaluated by the d-SPE of 16 nitro-polycyclic aromatic hydrocarbons (NPAHs) from water samples. The analysis was carried out by gas chromatography (GC) coupled with triple quadruple mass spectrometer in negative chemical ionization (NCI) mode. The selected ion monitoring (SIM) was used in the quantification of the target NPAHs. Extraction factors affecting the d-SPE, including the ionic strength, extraction temperature, and extraction time were optimized by the response surface methodology. The developed d-SPE method showed good linear correlations from 10 to 1000 ng L−1 (r > 0.99), low detection limits (2.9–83.0 ng L−1), satisfactory repeatability (relative standard deviation of <10%, n = 6), and acceptable recoveries (71.3%–112.2%) for water samples. The developed method was used for the food and environmental sample analysis. The results demonstrated that the method could be used for sample preparation of trace NPAHs in real samples.

Determination of short-chain chlorinated paraffins in multiple matrices of Arctic using gas chromatography-electron capture negative ion-low resolution mass spectrometry

Gas chromatography-electron capture negative ion-low resolution mass spectrometry (GC-ECNI-MS) was used for the quantification of short-chain chlorinated paraffins (SCCPs) in multiple matrices of Arctic. Samples were spiked with surrogate standards (13C10-trans-chlordane) and extracted with dichloromethane and hexane (1:1, v/v) using accelerated solvent extraction (ASE). The extract was cleaned using a multilayer Silica-Florisil column and e-HCH was added before instrument analysis. The SCCPs were analyzed using a gas chromatograph (GC) in electron capture negative ion (ECNI) mode coupled with a 7000B triple quadruple mass spectrometer (MS) in single quad mode. The calibration is performed using three commercial standards (chlorine contents of 51.5%, 55.5%, and 63.0%). A reasonable linear correlation for commercial standards was found between chlorine content and total response factor (R2?=?0.96). To ensure instrument sensitivity, the SCCP congeners were divided into four groups by the optimized combinations (C10, C11, C12 and C13) and subjected to analysis by four individual injections. This method is suited to analyse the total concentration of SCCPs and individual SCCP congener groups in the environmental analysis.• Accelerated solvent extraction offers a lower cost of time for per sample and reducing solvent consumption.• The presented quantification procedure makes the quantification of SCCPs independent from the chlorine content of the used standard mixtures.• The samples were subjected to analysis by four individual injections for the instrument sensitivity, and the total concentration of SCCPs and CP congener groups can be obtained at the same time.

Development and validation of an LC–MS/MS method for quantification of NC-8 in rat plasma and its application to pharmacokinetic studies

ent-16-Oxobeyeran-19-N-methylureido (NC-8) is a recently synthesized derivative of isosteviol that showed anti-hepatitis B virus (HBV) activity by disturbing replication and gene expression of the HBV and by inhibiting the host toll-like receptor 2/nuclear factor-κB signaling pathway. To study its pharmacokinetics as a part of the drug development process, a highly sensitive, rapid, and reliable liquid chromatography tandem mass spectrometry (LC–MS/MS) method was developed and validated for determining NC-8 in rat plasma. After protein precipitation extraction, the chromatographic separation of the analyte and internal standard (IS; diclofenac sodium) was performed on a reverse-phase Luna C18 column coupled with a Quattro Ultima triple quadruple mass spectrometer in the multiple-reaction monitoring mode using the transitions, m/z 347.31 → 75.09 for NC-8 and m/z 295.89 → 214.06 for the IS. The lower limit of quantitation was 0.5 ng/mL. The linear scope of the standard curve was between 0.5 and 500 ng/mL. Both the precision (coefficient of variation; %) and accuracy (relative error; %) were within acceptable criteria of <15%. Recoveries ranged from 104% to 113.4%, and the matrix effects (absolute) were non-significant (CV ≤ 6%). The validated method was successfully applied to investigate the pharmacokinetics of NC-8 in male Sprague–Dawley rats. The present methodology provides an analytical means to better understand the preliminary pharmacokinetics of NC-8 for investigations on further drug development.

Ground and Airborne U.K. Measurements of Nitryl Chloride: An Investigation of the Role of Cl Atom Oxidation at Weybourne Atmospheric Observatory

AbstractNitryl chloride (ClNO2) measurements from the Weybourne Atmospheric Observatory (WAO) are reported from March to April 2013 using a quadruple chemical ionization mass spectrometer with the I− ionization scheme. WAO is a rural coastal site with generally low NOx concentrations, a type of location poorly studied for ClNO2 production. Concentrations of ClNO2 exceeded that of the limit of detection (0.8 ppt) on each night of the campaign, as did concentrations of N2O5, which was also measured simultaneously with the Cambridge Broadband Cavity Enhanced Absorption Spectrometer. A peak concentration of 65 ppt of ClNO2 is reported here. Vertical profiles of ClNO2 from early‐ to middle‐morning flights in close proximity to WAO are also reported, showing elevated concentrations at low altitude. The photolysis of observed ClNO2 and a box model utilizing the Master Chemical Mechanism modified to include chlorine chemistry was used to calculate Cl atom concentrations. This model utilized numerous VOCs from the second Tropospheric Organic Chemistry project in 2004, at the same location and time of year. From this the relative importance of the oxidation of three groups of measured VOCs (alkanes, alkenes, and alkynes) by OH radicals, Cl atoms, and O3 is compared. Cl atom oxidation was deemed generally insignificant at this time and location for total oxidation due to the much lower concentration of ClNO2 observed, even following the night of greatest ClNO2 production.

Simultaneous quantification of imatinib and its main metabolite N-demethyl-imatinib in human plasma by liquid chromatography-tandem mass spectrometry and its application to therapeutic drug monitoring in patients with gastrointestinal stromal tumor.

The aim of this study was to improve and validate a more stable and less time-consuming method based on liquid chromatography and tandem mass spectrometry (LC- MS/MS) for the quantitative measurement of imatinib and its metabolite N-demethyl-imatinib (NDI) in human plasma. Separation of analytes was performed on a Waters XTerra RP18 column (50 × 2.1 mm i.d., 3.5 μm) with a mobile phase consisting of methanol-acetonitrile-water (65:20:15, v/v/v) with 0.05% formic acid at a flow-rate of 0.2 mL/min. The Quattro MicroTM triple quadruple mass spectrometer was operated in the multiple-reaction-monitoring mode via positive electrospray ionization interface using the transitions m/z 494.0 → 394.0 for imatinib, m/z 479.6 → 394.0 for NDI and m/z 488.2 → 394.0 for IS. The method was linear over 0.01-10 μg/mL for imatinib and NDI. The intra- and inter-day precisions were all <15% in terms of relative standard deviation, and the accuracy was within ±15% in terms of relative error for both imatinib and NDI. The lower limit of quantification was identifiable and reproducible at 10 ng/mL. The method was sensitive, specific and less time-consuming and it was successfully applied in gastrointestinal stromal tumor patients treated with imatinib.

Ultra-Performance Liquid Chromatography-Triple Quadruple Mass Spectrometry (UPLC-TQ/MS) for Evaluation of Biogenic Amines in Wine

In this study, a fast, simple, and sensitive analytical method for direct determination of biogenic amines tryptamine, putrescine, histamine, phenylethylamine, tyramine, cadaverine, spermine, and spermidine in wine has been developed and validated. Detection of analytes was performed with ultra-performance liquid chromatography (UPLC) coupled to triple quadruple mass spectrometer (TQ/MS). The calibration curves of all amines were linear with correlation coefficients (R 2) ranging from 0.9906 for putrescine to 0.9998 for histamine and 2-phenyethylamine. The accuracy of the method was checked with a standard addition method, showing good accuracy, repeatability, and reproducibility (RSD < 10%). The limit of detection (LOD) and limit of quantification (LOQ) ranged from 0.50 to 30 μg/L and 1.50 to 90 μg/L, respectively, for all amines. The validated method was applied to detect and quantify biogenic amines in Macedonian red and white wines. Higher concentration of amines was observed in red wines (5797 μg/L, on average) compared to the white wines (1485 μg/L, on average).

Volatiles profiling in Ceratonia siliqua (Carob bean) from Egypt and in response to roasting as analyzed via solid-phase microextraction coupled to chemometrics

Ceratonia siliqua is a legume tree of considerable commercial importance for the flavor and sweets industry cultivated mostly for its pods nutritive value and or several health benefits. Despite extensive studies on C. siliqua pod non-volatile metabolites, much less is known regarding volatiles composition which contributes to the flavor of its many food products. To gain insight into C. siliqua aroma, 31 volatile constituents from unroasted and roasted pods were profiled using headspace solid-phase micro extraction (HD-SPME) analyzed via quadruple mass spectrometer followed by multivariate data analyses. Short chain fatty acids amounted for the major volatile class at ca. (71–77%) with caproic acid (20%) and pentanoic acid (15–25%) as major components. Compared to ripe pod, roasted ripe pod was found less enriched in major volatile classes i.e., short chain fatty acids and aldehydes, except for higher pyranone levels. Volatiles mediating for unheated and hot carob fruit aroma is likely to be related to its (E)-cinnamaldehyde and pyranone content, respectively. Such knowledge is expected to be the key for understanding the olfactory and taste properties of C. siliqua and its various commercial food products.

Patulin and patulin producing Penicillium spp. occurrence in apples and apple-based products including baby food.

Patulin has raised the international attention because of its health risk. In fact, it has mutagenic, neurotoxic, immunotoxic, genotoxic and gastrointestinal effects in animals. In the present work, patulin and patulin-producing Penicillium spp. in apple and apple-based products marketed in Qatar were analysed. Sampling was carried out using apple fruits and apple-based products. Fungi were isolated from undamaged apples, apple juice and baby apple food. DNA extraction was carried out with DNeasy Plant Mini Kit (QIAGEN, Valencia, USA). The molecular identification of fungal isolates was carried out using ITS1-ITS4 PCR. PCR products were sequenced and blasted. Patulin was extracted and analyzed by LC/MS/MS, then quantified using Agilent 1290UHPLC coupled to 6460 triple quadruple mass spectrometer. Forty-five samples of undamaged fresh apple fruits, apple juice and apple-based baby food products sold in different markets in Qatar were surveyed for both fungal and patulin contamination using Liquid Chromatography Tandem Mass Spectrometery (LC/MS/MS). Twenty-five Penicillium spp. isolates were selected, including 23 P. expansum and one isolate each of P. brevicompactum and P. commune. All the tested Penicillium spp. isolates produced patulin in vitro (from 40 to 100 μg/g on Malt Yeast Extract agar medium). Patulin was detected in 100% of apple juice samples at levels ranging from 5.27 to 82.21 µg/kg. Only 5 samples contained patulin levels higher than European Union recommended limit (50 µg/kg). The average patulin contamination was 30.67 µg/kg and 10.92 µg/kg in baby apple juice and in baby apple compote, respectively.

Development of H, D, T Simultaneous TDS Measurement System and H, D, T Retention Behavior for DT Gas Exposed Tungsten Installed in LHD Plasma Campaign

All the hydrogen isotope (H, D, T) simultaneous TDS (Thermal desorption spectroscopy) measurement system (HI-TDS system) was newly designed to evaluate all hydrogen isotope desorption behavior in materials. The present HI-TDS system was operated under Ar purge gas and the H and D desorptions were observed by a quadruple mass spectrometer equipped with an enclosed ion source, although T desorption was evaluated by an ionization chamber or proportional counters. Most of the same TDS spectra for D and T were derived by optimizing the heating rate of 0.5 K s−1 with Ar flow rate of 13.3 sccm.Using this HI-TDS system, D and T desorption behaviors for implanted or DT gas exposed tungsten samples installed in LHD (Large Helical Device) at NIFS (National Institute for Fusion Science) was evaluated. It was found that major hydrogen desorption stages consisted of two temperature regions, namely 700 K and 900 K, which was consistent with the previous hydrogen plasma campaign and most of hydrogen would be trapped by the carbon-dominated mixed-material layer. By implantation, major D desorption was found at ~900 K with a narrow peak due to energetic ion implantation. For gas exposure, H was preferentially replaced by D and T with a lower trapping energy. In addition, T replacement rate by additional H2 gas exposure was evaluated. This fact indicates that the hydrogen replacement mechanism would be clearly changed by exposure methods.

Determination of Riluzole in Human Plasma by Ultra Performance Liquid Chromatography-Tandem Mass Spectrometry (UPLC-MS/MS) and its Application to a Pharmacokinetic Study

A rapid, sensitive and selective ultra-performance liquid chromatography–tandem mass spectrometric (UPLC–MS/MS) method was developed and validated for the estimation of Riluzole in human plasma using Olanzapine as an internal standard. Riluzole and Internal standard were extracted from 0.5 mL plasma by solid phase extraction method. The analytical separation was carried out in a reverse liquid chromatography by using C18 (50 x 4.6mm 1.8,) 10mMAmmonium Acetate: Methanol (10:90) v/v at 0.5 mL/min at isocratic mode . The detection was performed on a triple quadruple tandem mass spectrometer by multiple reactions monitoring (MRM) mode via electro spray ionization (ESI) source. Analytes were monitored in multiple reactions monitoring mode using the respective [M+H] +ions, m/z 234.84/137.63 for Riluzole and m/z 313.15/256.14 for the internal standard, respectively. The proposed method was validated with linear range of 5 -1000ng/ml for Riluzole with a runtime 2.5 minutes. The %R.S.D of intra-day and inter-day assay was lower than 15%. For its sensitivity and reliability, the proposed method is particularly suitable for pharmacokinetic studies.

Diclofenac in Arabidopsis cells: Rapid formation of conjugates

Pharmaceutical and personal care products (PPCPs) are continuously introduced into the soil-plant system, through practices such as agronomic use of reclaimed water and biosolids containing these trace contaminants. Plants may accumulate PPCPs from soil, serving as a conduit for human exposure. Metabolism likely controls the final accumulation of PPCPs in plants, but is in general poorly understood for emerging contaminants. In this study, we used diclofenac as a model compound, and employed 14C tracing, and time-of-flight (TOF) and triple quadruple (QqQ) mass spectrometers to unravel its metabolism pathways in Arabidopsis thaliana cells. We further validated the primary metabolites in Arabidopsis seedlings. Diclofenac was quickly taken up into A. thaliana cells. Phase I metabolism involved hydroxylation and successive oxidation and cyclization reactions. However, Phase I metabolites did not accumulate appreciably; they were instead rapidly conjugated with sulfate, glucose, and glutamic acid through Phase II metabolism. In particular, diclofenac parent was directly conjugated with glutamic acid, with acyl-glutamatyl-diclofenac accounting for >70% of the extractable metabolites after 120-h incubation. In addition, at the end of incubation, >40% of the spiked diclofenac was in the non-extractable form, suggesting extensive sequestration into cell matter. The rapid formation of non-extractable residue and dominance of diclofenac-glutamate conjugate uncover previously unknown metabolism pathways for diclofenac. In particular, the rapid conjugation of parent highlights the need to consider conjugates of emerging contaminants in higher plants, and their biological activity and human health implications.

Spectroscopic, thermal and structural studies of new l-leucine and d-leucine complexes with chloranilic acid

New molecular complexes of l-leucine and d-leucine with chloranilic acid have been synthesized. Crystal structures of these crystals have been solved; they crystallize in non-centrosymmetric monoclinic P21 space group. In the crystal, leucine molecules exist in protonated form (C6NO2H14+) and chloranilic acid molecules in deprotonated form (C6HCl2O4−). Electronic (UV–Vis) and vibrational absorption (VA) spectra for both materials were collected. Circular dichroism methods such as electronic circular dichroism (ECD) and vibrational circular dichroism (VCD) were used to determine the absolute configuration of new complexes. In both methods a characteristic (−,+) Cotton patterns are observed. In ECD spectra absorption bands are observed at 212 nm for acetonitrile solution and at 202 nm for aqueous solution. VCD spectra (in DMSO-d6 solution) show (−,+) Cotton pattern with strong peaks at 1323 cm−1 (CH rocking mode). Differential scanning calorimetry (DSC) and thermogravimetric (TG) investigations were performed to explore thermal properties of new materials. In DSC curve the decomposition and combustion processes are observed in 220–227 °C. The decomposition process was described by use of TG method and quadruple mass spectrometer (QMS). NMR spectra of pure l-leucine and chloranilic acid as well as l-leucine – chloranilic acid complex in solutions (D2O and DMSO) and in solid state confirm the geometry of molecules in complex both in solution and in solid state.

Altered adrenal and gonadal steroids biosynthesis in patients with burn injury

IntroductionBurn injury inevitably leads to changes in the endogenous production of cytokines, as well as adrenal and gonadal steroids. Previous studies have reported gender-related differences in outcome following burn injury, which suggests that gonadal steroids may play a role. The aim of this study was to assess alterations in concentration of endogenous steroids in patients with burn injury. MethodsFor this single-center, prospective descriptive study, high-sensitivity liquid chromatography tandem mass spectrometry (LC-MS/MS)-based steroid quantification was used to determine longitudinal profiles of the concentrations of endogenous steroids in plasma from sixteen adult male patients with burn injury (14.5–72% of total body surface area). Steroids were extracted from plasma samples and analyzed using multiple reaction monitoring acquisition, with electrospray ionization on a triple quadruple mass spectrometer. Total protein concentration was measured in the samples using spectrophotometry. ResultsSteroid and total protein concentration distributions were compared to reference intervals characteristic of healthy adult men. Concentrations of the following steroids in plasma of burn injured patients were found to correlate positively to the area of the burn injury: cortisol (r=0.84), corticosterone (r=0.73), 11-deoxycortisol (r=0.72), androstenedione (r=0.72), 17OH-progesterone (r=0.68), 17OH-pregnenolone (r=0.64) and pregnenolone (r=0.77). Concentrations of testosterone decreased during the acute phase and were up to ten-times lower than reference values for healthy adult men, while concentrations of estrone were elevated. By day 21 after injury, testosterone concentrations were increased in younger, but not older, patients. The highest concentrations of estrone were observed on day 3 after the injury and then declined by day 21 to concentrations comparable to those observed on the day of the injury. ConclusionBurn injury alters endogenous steroid biosynthesis, with decreased testosterone concentrations and elevated estrone concentrations, during the first 21days after the injury. Concentrations of glucocorticoids, progestagens and androgen precursors correlated positively with the area of burn injury. The finding of increased estrone following burn injury needs to be confirmed in a larger hypothesis-driven study.

Laboratory characterization of an aerosol chemical speciation monitor with PM2.5measurement capability

ABSTRACTThe Aerodyne Aerosol Chemical Speciation Monitor (ACSM) is well suited for measuring non-refractory particulate matter up to approximately 1.0 µm in aerodynamic diameter (NR-sub-PM1). However, for larger particles the detection efficiency is limited by losses in the sampling inlet system and through the standard aerodynamic focusing lens. In addition, larger particles have reduced collection efficiency due to particle bounce at the vaporizer. These factors have limited the NR-sub-PM1 ACSM from meeting PM2.5 (particulate matter with aerodynamic diameter smaller than 2.5 µm) monitoring standards. To overcome these limitations, we have redesigned the sampling inlet, the aerodynamic lens, and particle vaporizer. Both the new lens and vaporizer are tested in the lab using a quadruple aerosol mass spectrometer (QAMS) system equipped with light scattering module. Our results show that the capture vaporizer introduces additional thermal decomposition of both inorganic and organic compounds, requiring modi...