Search results for: four quadrant detector
Commenced in January 2007
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Edition: International
Paper Count: 432

Search results for: four quadrant detector

12 Hydrogen Purity: Developing Low-Level Sulphur Speciation Measurement Capability

Authors: Sam Bartlett, Thomas Bacquart, Arul Murugan, Abigail Morris

Abstract:

Fuel cell electric vehicles provide the potential to decarbonise road transport, create new economic opportunities, diversify national energy supply, and significantly reduce the environmental impacts of road transport. A potential issue, however, is that the catalyst used at the fuel cell cathode is susceptible to degradation by impurities, especially sulphur-containing compounds. A recent European Directive (2014/94/EU) stipulates that, from November 2017, all hydrogen provided to fuel cell vehicles in Europe must comply with the hydrogen purity specifications listed in ISO 14687-2; this includes reactive and toxic chemicals such as ammonia and total sulphur-containing compounds. This requirement poses great analytical challenges due to the instability of some of these compounds in calibration gas standards at relatively low amount fractions and the difficulty associated with undertaking measurements of groups of compounds rather than individual compounds. Without the available reference materials and analytical infrastructure, hydrogen refuelling stations will not be able to demonstrate compliance to the ISO 14687 specifications. The hydrogen purity laboratory at NPL provides world leading, accredited purity measurements to allow hydrogen refuelling stations to evidence compliance to ISO 14687. Utilising state-of-the-art methods that have been developed by NPL’s hydrogen purity laboratory, including a novel method for measuring total sulphur compounds at 4 nmol/mol and a hydrogen impurity enrichment device, we provide the capabilities necessary to achieve these goals. An overview of these capabilities will be given in this paper. As part of the EMPIR Hydrogen co-normative project ‘Metrology for sustainable hydrogen energy applications’, NPL are developing a validated analytical methodology for the measurement of speciated sulphur-containing compounds in hydrogen at low amount fractions pmol/mol to nmol/mol) to allow identification and measurement of individual sulphur-containing impurities in real samples of hydrogen (opposed to a ‘total sulphur’ measurement). This is achieved by producing a suite of stable gravimetrically-prepared primary reference gas standards containing low amount fractions of sulphur-containing compounds (hydrogen sulphide, carbonyl sulphide, carbon disulphide, 2-methyl-2-propanethiol and tetrahydrothiophene have been selected for use in this study) to be used in conjunction with novel dynamic dilution facilities to enable generation of pmol/mol to nmol/mol level gas mixtures (a dynamic method is required as compounds at these levels would be unstable in gas cylinder mixtures). Method development and optimisation are performed using gas chromatographic techniques assisted by cryo-trapping technologies and coupled with sulphur chemiluminescence detection to allow improved qualitative and quantitative analyses of sulphur-containing impurities in hydrogen. The paper will review the state-of-the art gas standard preparation techniques, including the use and testing of dynamic dilution technologies for reactive chemical components in hydrogen. Method development will also be presented highlighting the advances in the measurement of speciated sulphur compounds in hydrogen at low amount fractions.

Keywords: gas chromatography, hydrogen purity, ISO 14687, sulphur chemiluminescence detector

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11 Raman Spectroscopy of Fossil-like Feature in Sooke #1 from Vancouver Island

Authors: J. A. Sawicki, C. Ebrahimi

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The first geochemical, petrological, X-ray diffraction, Raman, Mössbauer, and oxygen isotopic analyses of very intriguing 13-kg Sooke #1 stone covered in 70% of its surface with black fusion crust, found in and recovered from Sooke Basin, near Juan de Fuca Strait, in British Columbia, were reported as poster #2775 at LPSC52 in March. Our further analyses reported in poster #6305 at 84AMMS in August and comparisons with the Mössbauer spectra of Martian meteorite MIL03346 and Martian rocks in Gusev Crater reported by Morris et al. suggest that Sooke #1 find could be a stony achondrite of Martian polymict breccia type ejected from early watery Mars. Here, the Raman spectra of a carbon-rich ~1-mm² fossil-like white area identified in this rock on a surface of polished cut have been examined in more detail. The low-intensity 532 nm and 633 nm beams of the InviaRenishaw microscope were used to avoid any destructive effects. The beam was focused through the microscope objective to a 2 m spot on a sample, and backscattered light collected through this objective was recorded with CCD detector. Raman spectra of dark areas outside fossil have shown bands of clinopyroxene at 320, 660, and 1020 cm-1 and small peaks of forsteritic olivine at 820-840 cm-1, in agreement with results of X-ray diffraction and Mössbauer analyses. Raman spectra of the white area showed the broad band D at ~1310 cm-1 consisting of main mode A1g at 1305 cm⁻¹, E2g mode at 1245 cm⁻¹, and E1g mode at 1355 cm⁻¹ due to stretching diamond-like sp3 bonds in diamond polytype lonsdaleite, as in Ovsyuk et al. study. The band near 1600 cm-1 mostly consists of D2 band at 1620 cm-1 and not of the narrower G band at 1583 cm⁻¹ due to E2g stretching in planar sp2 bonds that are fundamental building blocks of carbon allotropes graphite and graphene. In addition, the broad second-order Raman bands were observed with 532 nm beam at 2150, ~2340, ~2500, 2650, 2800, 2970, 3140, and ~3300 cm⁻¹ shifts. Second-order bands in diamond and other carbon structures are ascribed to the combinations of bands observed in the first-order region: here 2650 cm⁻¹ as 2D, 2970 cm⁻¹ as D+G, and 3140 cm⁻¹ as 2G ones. Nanodiamonds are abundant in the Universe, found in meteorites, interplanetary dust particles, comets, and carbon-rich stars. The diamonds in meteorites are presently intensely investigated using Raman spectroscopy. Such particles can be formed by CVD process and during major impact shocks at ~1000-2300 K and ~30-40 GPa. It cannot be excluded that the fossil discovered in Sooke #1 could be a remnant of an alien carbon organism that transformed under shock impact to nanodiamonds. We trust that for the benefit of research in astro-bio-geology of meteorites, asteroids, Martian rocks, and soil, this find deserves further, more thorough investigations. If possible, the Raman SHERLOCK spectrometer operating on the Perseverance Rover should also search for such objects in the Martian rocks.

Keywords: achondrite, nanodiamonds, lonsdaleite, raman spectra

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10 Concentration and Stability of Fatty Acids and Ammonium in the Samples from Mesophilic Anaerobic Digestion

Authors: Mari Jaakkola, Jasmiina Haverinen, Tiina Tolonen, Vesa Virtanen

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These process monitoring of biogas plant gives valuable information of the function of the process and help to maintain a stable process. The costs of basic monitoring are often much lower than the costs associated with re-establishing a biologically destabilised plant. Reactor acidification through reactor overload is one of the most common reasons for process deterioration in anaerobic digesters. This occurs because of a build-up of volatile fatty acids (VFAs) produced by acidogenic and acetogenic bacteria. VFAs cause pH values to decrease, and result in toxic conditions in the reactor. Ammonia ensures an adequate supply of nitrogen as a nutrient substance for anaerobic biomass and increases system's buffer capacity, counteracting acidification lead by VFA production. However, elevated ammonia concentration is detrimental to the process due to its toxic effect. VFAs are considered the most reliable analytes for process monitoring. To obtain accurate results, sample storage and transportation need to be carefully controlled. This may be a challenge for off-line laboratory analyses especially when the plant is located far away from the laboratory. The aim of this study was to investigate the correlation between fatty acids, ammonium, and bacteria in the anaerobic digestion samples obtained from an industrial biogas factory. The stability of the analytes was studied comparing the results of the on-site analyses performed in the factory site to the results of the samples stored at room temperature and -18°C (up to 30 days) after sampling. Samples were collected in the biogas plant consisting of three separate mesofilic AD reactors (4000 m³ each) where the main feedstock was swine slurry together with a complex mixture of agricultural plant and animal wastes. Individual VFAs, ammonium, and nutrients (K, Ca, Mg) were studied by capillary electrophoresis (CE). Longer chain fatty acids (oleic, hexadecanoic, and stearic acids) and bacterial profiles were studied by GC-MSD (Gas Chromatography-Mass Selective Detector) and 16S rDNA, respectively. On-site monitoring of the analytes was performed by CE. The main VFA in all samples was acetic acid. However, in one reactor sample elevated levels of several individual VFAs and long chain fatty acids were detected. Also bacterial profile of this sample differed from the profiles of other samples. Acetic acid decomposed fast when the sample was stored in a room temperature. All analytes were stable when stored in a freezer. Ammonium was stable even at a room temperature for the whole testing period. One reactor sample had higher concentration of VFAs and long chain fatty acids than other samples. CE was utilized successfully in the on-site analysis of separate VFAs and NH₄ in the biogas production site. Samples should be analysed in the sampling day if stored in RT or freezed for longer storage time. Fermentation reject can be stored (and transported) at ambient temperature at least for one month without loss of NH₄. This gives flexibility to the logistic solutions when reject is used as a fertilizer.

Keywords: anaerobic digestion, capillary electrophoresis, ammonium, bacteria

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9 A Novel Concept of Optical Immunosensor Based on High-Affinity Recombinant Protein Binders for Tailored Target-Specific Detection

Authors: Alena Semeradtova, Marcel Stofik, Lucie Mareckova, Petr Maly, Ondrej Stanek, Jan Maly

Abstract:

Recently, novel strategies based on so-called molecular evolution were shown to be effective for the production of various peptide ligand libraries with high affinities to molecular targets of interest comparable or even better than monoclonal antibodies. The major advantage of these peptide scaffolds is mainly their prevailing low molecular weight and simple structure. This study describes a new high-affinity binding molecules based immunesensor using a simple optical system for human serum albumin (HSA) detection as a model molecule. We present a comparison of two variants of recombinant binders based on albumin binding domain of the protein G (ABD) performed on micropatterned glass chip. Binding domains may be tailored to any specific target of interest by molecular evolution. Micropatterened glass chips were prepared using UV-photolithography on chromium sputtered glasses. Glass surface was modified by (3-aminopropyl)trietoxysilane and biotin-PEG-acid using EDC/NHS chemistry. Two variants of high-affinity binding molecules were used to detect target molecule. Firstly, a variant is based on ABD domain fused with TolA chain. This molecule is in vivo biotinylated and each molecule contains one molecule of biotin and one ABD domain. Secondly, the variant is ABD domain based on streptavidin molecule and contains four gaps for biotin and four ABD domains. These high-affinity molecules were immobilized to the chip surface via biotin-streptavidin chemistry. To eliminate nonspecific binding 1% bovine serum albumin (BSA) or 6% fetal bovine serum (FBS) were used in every step. For both variants range of measured concentrations of fluorescently labelled HSA was 0 – 30 µg/ml. As a control, we performed a simultaneous assay without high-affinity binding molecules. Fluorescent signal was measured using inverse fluorescent microscope Olympus IX 70 with COOL LED pE 4000 as a light source, related filters, and camera Retiga 2000R as a detector. The fluorescent signal from non-modified areas was substracted from the signal of the fluorescent areas. Results were presented in graphs showing the dependence of measured grayscale value on the log-scale of HSA concentration. For the TolA variant the limit of detection (LOD) of the optical immunosensor proposed in this study is calculated to be 0,20 µg/ml for HSA detection in 1% BSA and 0,24 µg/ml in 6% FBS. In the case of streptavidin-based molecule, it was 0,04 µg/ml and 0,07 µg/ml respectively. The dynamical range of the immunosensor was possible to estimate just in the case of TolA variant and it was calculated to be 0,49 – 3,75 µg/ml and 0,73-1,88 µg/ml respectively. In the case of the streptavidin-based the variant we didn´t reach the surface saturation even with the 480 ug/ml concentration and the upper value of dynamical range was not estimated. Lower value was calculated to be 0,14 µg/ml and 0,17 µg/ml respectively. Based on the obtained results, it´s clear that both variants are useful for creating the bio-recognizing layer on immunosensors. For this particular system, it is obvious that the variant based on streptavidin molecule is more useful for biosensing on glass planar surfaces. Immunosensors based on this variant would exhibit better limit of detection and wide dynamical range.

Keywords: high affinity binding molecules, human serum albumin, optical immunosensor, protein G, UV-photolitography

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8 Identifying Risk Factors for Readmission Using Decision Tree Analysis

Authors: Sıdıka Kaya, Gülay Sain Güven, Seda Karsavuran, Onur Toka

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This study is part of an ongoing research project supported by the Scientific and Technological Research Council of Turkey (TUBITAK) under Project Number 114K404, and participation to this conference was supported by Hacettepe University Scientific Research Coordination Unit under Project Number 10243. Evaluation of hospital readmissions is gaining importance in terms of quality and cost, and is becoming the target of national policies. In Turkey, the topic of hospital readmission is relatively new on agenda and very few studies have been conducted on this topic. The aim of this study was to determine 30-day readmission rates and risk factors for readmission. Whether readmission was planned, related to the prior admission and avoidable or not was also assessed. The study was designed as a ‘prospective cohort study.’ 472 patients hospitalized in internal medicine departments of a university hospital in Turkey between February 1, 2015 and April 30, 2015 were followed up. Analyses were conducted using IBM SPSS Statistics version 22.0 and SPSS Modeler 16.0. Average age of the patients was 56 and 56% of the patients were female. Among these patients 95 were readmitted. Overall readmission rate was calculated as 20% (95/472). However, only 31 readmissions were unplanned. Unplanned readmission rate was 6.5% (31/472). Out of 31 unplanned readmission, 24 was related to the prior admission. Only 6 related readmission was avoidable. To determine risk factors for readmission we constructed Chi-square automatic interaction detector (CHAID) decision tree algorithm. CHAID decision trees are nonparametric procedures that make no assumptions of the underlying data. This algorithm determines how independent variables best combine to predict a binary outcome based on ‘if-then’ logic by portioning each independent variable into mutually exclusive subsets based on homogeneity of the data. Independent variables we included in the analysis were: clinic of the department, occupied beds/total number of beds in the clinic at the time of discharge, age, gender, marital status, educational level, distance to residence (km), number of people living with the patient, any person to help his/her care at home after discharge (yes/no), regular source (physician) of care (yes/no), day of discharge, length of stay, ICU utilization (yes/no), total comorbidity score, means for each 3 dimensions of Readiness for Hospital Discharge Scale (patient’s personal status, patient’s knowledge, and patient’s coping ability) and number of daycare admissions within 30 days of discharge. In the analysis, we included all 95 readmitted patients (46.12%), but only 111 (53.88%) non-readmitted patients, although we had 377 non-readmitted patients, to balance data. The risk factors for readmission were found as total comorbidity score, gender, patient’s coping ability, and patient’s knowledge. The strongest identifying factor for readmission was comorbidity score. If patients’ comorbidity score was higher than 1, the risk for readmission increased. The results of this study needs to be validated by other data–sets with more patients. However, we believe that this study will guide further studies of readmission and CHAID is a useful tool for identifying risk factors for readmission.

Keywords: decision tree, hospital, internal medicine, readmission

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7 Implementation of Synthesis and Quality Control Procedures of ¹⁸F-Fluoromisonidazole Radiopharmaceutical

Authors: Natalia C. E. S. Nascimento, Mercia L. Oliveira, Fernando R. A. Lima, Leonardo T. C. do Nascimento, Marina B. Silveira, Brigida G. A. Schirmer, Andrea V. Ferreira, Carlos Malamut, Juliana B. da Silva

Abstract:

Tissue hypoxia is a common characteristic of solid tumors leading to decreased sensitivity to radiotherapy and chemotherapy. In the clinical context, tumor hypoxia assessment employing the positron emission tomography (PET) tracer ¹⁸F-fluoromisonidazole ([¹⁸F]FMISO) is helpful for physicians for planning and therapy adjusting. The aim of this work was to implement the synthesis of 18F-FMISO in a TRACERlab® MXFDG module and also to establish the quality control procedure. [¹⁸F]FMISO was synthesized at Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN/Brazil) using an automated synthesizer (TRACERlab® MXFDG, GE) adapted for the production of [¹⁸F]FMISO. The FMISO chemical standard was purchased from ABX. 18O- enriched water was acquired from Center of Molecular Research. Reagent kits containing eluent solution, acetonitrile, ethanol, 2.0 M HCl solution, buffer solution, water for injections and [¹⁸F]FMISO precursor (dissolved in 2 ml acetonitrile) were purchased from ABX. The [¹⁸F]FMISO samples were purified by Solid Phase Extraction method. The quality requirements of [¹⁸F]FMISO are established in the European Pharmacopeia. According to that reference, quality control of [¹⁸F]FMISO should include appearance, pH, radionuclidic identity and purity, radiochemical identity and purity, chemical purity, residual solvents, bacterial endotoxins, and sterility. The duration of the synthesis process was 53 min, with radiochemical yield of (37.00 ± 0.01) % and the specific activity was more than 70 GBq/µmol. The syntheses were reproducible and showed satisfactory results. In relation to the quality control analysis, the samples were clear and colorless at pH 6.0. The spectrum emission, measured by using a High-Purity Germanium Detector (HPGe), presented a single peak at 511 keV and the half-life, determined by the decay method in an activimeter, was (111.0 ± 0.5) min, indicating no presence of radioactive contaminants, besides the desirable radionuclide (¹⁸F). The samples showed concentration of tetrabutylammonium (TBA) < 50μg/mL, assessed by visual comparison to TBA standard applied in the same thin layer chromatographic plate. Radiochemical purity was determined by high performance liquid chromatography (HPLC) and the results were 100%. Regarding the residual solvents tested, ethanol and acetonitrile presented concentration lower than 10% and 0.04%, respectively. Healthy female mice were injected via lateral tail vein with [¹⁸F]FMISO, microPET imaging studies (15 min) were performed after 2 h post injection (p.i), and the biodistribution was analyzed in five-time points (30, 60, 90, 120 and 180 min) after injection. Subsequently, organs/tissues were assayed for radioactivity with a gamma counter. All parameters of quality control test were in agreement to quality criteria confirming that [¹⁸F]FMISO was suitable for use in non-clinical and clinical trials, following the legal requirements for the production of new radiopharmaceuticals in Brazil.

Keywords: automatic radiosynthesis, hypoxic tumors, pharmacopeia, positron emitters, quality requirements

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6 Epigastric Pain in Emergency Room: Median Arcuate Ligament Syndrome

Authors: Demet Devrimsel Dogan, Ecem Deniz Kirkpantur, Muharrem Dogan, Ahmet Aykut, Ebru Unal Akoglu, Ozge Ecmel Onur

Abstract:

Introduction: Median Arcuate Ligament Syndrome (MALS) is a rare cause of chronic abdominal pain due to external compression of the celiac trunk by a fibrous arch that unites diaphragmatic crura on each side of the aortic hiatus. While 10-24% of the population may suffer from compression of celiac trunk, it rarely causes patients to develop symptoms. The typical clinical triad of symptoms includes postprandial epigastric pain, weight loss and vomiting. The diagnosis can be made using thin section multi-detector computed tomography (CT) scans which delineate the ligament and the compressed vessel. The treatment of MALS is aimed at relieving the compression of the celiac artery to restore adequate blood flow through the vessel and neurolysis to address chronic pain. Case: A 68-year-old male presented to our clinic with acute postprandial epigastric pain. This was patients’ first attack, and the pain was the worst pain of his life. The patient did not have any other symptoms like nausea, vomiting, chest pain or dyspnea. In his medical history, the patient has had an ischemic cerebrovascular stroke 5 years ago which he recovered with no sequel, and he was using 75 mg clopidogrel and 100 mg acetylsalicylic acid. He was not using any other medication and did not have a story of cardiovascular disease. His vital signs were stable (BP:113/72 mmHg, Spo2:97, temperature:36.3°C, HR:90/bpm). In his electrocardiogram, there was ST depression in leads II, III and AVF. In his physical examination, there was only epigastric tenderness, other system examinations were normal. Physical examination through his upper gastrointestinal system showed no bleeding. His laboratory results were as follows: creatinine:1.26 mg/dL, AST:42 U/L, ALT:17 U/L, amylase:78 U/L, lipase:26 U/L, troponin:10.3 pg/ml, WBC:28.9 K/uL, Hgb:12.7 gr/dL, Plt:335 K/uL. His serial high-sensitive troponin levels were also within normal limits, his echocardiography showed no segmental wall motion abnormalities, an acute myocardial infarction was excluded. In his abdominal ultrasound, no pathology was founded. Contrast-enhanced abdominal CT and CT angiography reported ‘thickened diaphragmatic cruras are compressing and stenosing truncus celiacus superior, this is likely compatible with MALS’. The patient was consulted to general surgery, and they admitted the patient for laparoscopic ligament release. Results: MALS is a syndrome that causes postprandial pain, nausea and vomiting as its most common symptoms. Affected patients are normally young, slim women between the ages of 30 and 50 who have undergone extensive examinations to find the source of their symptoms. To diagnose MALS, other underlying pathologies should initially be excluded. The gold standard is aortic angiography. Although diagnosis and treatment of MALS are unclear, symptom resolution has been achieved with multiple surgical modalities, including open, laparoscopic or robotic ligament release as well as celiac ganglionectomy, which often requires celiac artery revascularisation.

Keywords: differential diagnosis, epigastric pain, median arcuate ligament syndrome, celiac trunk

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5 Predicting and Obtaining New Solvates of Curcumin, Demethoxycurcumin and Bisdemethoxycurcumin Based on the Ccdc Statistical Tools and Hansen Solubility Parameters

Authors: J. Ticona Chambi, E. A. De Almeida, C. A. Andrade Raymundo Gaiotto, A. M. Do Espírito Santo, L. Infantes, S. L. Cuffini

Abstract:

The solubility of active pharmaceutical ingredients (APIs) is challenging for the pharmaceutical industry. The new multicomponent crystalline forms as cocrystal and solvates present an opportunity to improve the solubility of APIs. Commonly, the procedure to obtain multicomponent crystalline forms of a drug starts by screening the drug molecule with the different coformers/solvents. However, it is necessary to develop methods to obtain multicomponent forms in an efficient way and with the least possible environmental impact. The Hansen Solubility Parameters (HSPs) is considered a tool to obtain theoretical knowledge of the solubility of the target compound in the chosen solvent. H-Bond Propensity (HBP), Molecular Complementarity (MC), Coordination Values (CV) are tools used for statistical prediction of cocrystals developed by the Cambridge Crystallographic Data Center (CCDC). The HSPs and the CCDC tools are based on inter- and intra-molecular interactions. The curcumin (Cur), target molecule, is commonly used as an anti‐inflammatory. The demethoxycurcumin (Demcur) and bisdemethoxycurcumin (Bisdcur) are natural analogues of Cur from turmeric. Those target molecules have differences in their solubilities. In this way, the work aimed to analyze and compare different tools for multicomponent forms prediction (solvates) of Cur, Demcur and Biscur. The HSP values were calculated for Cur, Demcur, and Biscur using the chemical group contribution methods and the statistical optimization from experimental data. The HSPmol software was used. From the HSPs of the target molecules and fifty solvents (listed in the HSP books), the relative energy difference (RED) was determined. The probability of the target molecules would be interacting with the solvent molecule was determined using the CCDC tools. A dataset of fifty molecules of different organic solvents was ranked for each prediction method and by a consensus ranking of different combinations: HSP, CV, HBP and MC values. Based on the prediction, 15 solvents were selected as Dimethyl Sulfoxide (DMSO), Tetrahydrofuran (THF), Acetonitrile (ACN), 1,4-Dioxane (DOX) and others. In a starting analysis, the slow evaporation technique from 50°C at room temperature and 4°C was used to obtain solvates. The single crystals were collected by using a Bruker D8 Venture diffractometer, detector Photon100. The data processing and crystal structure determination were performed using APEX3 and Olex2-1.5 software. According to the results, the HSPs (theoretical and optimized) and the Hansen solubility sphere for Cur, Demcur and Biscur were obtained. With respect to prediction analyses, a way to evaluate the predicting method was through the ranking and the consensus ranking position of solvates already reported in the literature. It was observed that the combination of HSP-CV obtained the best results when compared to the other methods. Furthermore, as a result of solvent selected, six new solvates, Cur-DOX, Cur-DMSO, Bicur-DOX, Bircur-THF, Demcur-DOX, Demcur-ACN and a new Biscur hydrate, were obtained. Crystal structures were determined for Cur-DOX, Biscur-DOX, Demcur-DOX and Bicur-Water. Moreover, the unit-cell parameter information for Cur-DMSO, Biscur-THF and Demcur-ACN were obtained. The preliminary results showed that the prediction method is showing a promising strategy to evaluate the possibility of forming multicomponent. It is currently working on obtaining multicomponent single crystals.

Keywords: curcumin, HSPs, prediction, solvates, solubility

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4 Solar and Galactic Cosmic Ray Impacts on Ambient Dose Equivalent Considering a Flight Path Statistic Representative to World-Traffic

Authors: G. Hubert, S. Aubry

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The earth is constantly bombarded by cosmic rays that can be of either galactic or solar origin. Thus, humans are exposed to high levels of galactic radiation due to altitude aircraft. The typical total ambient dose equivalent for a transatlantic flight is about 50 μSv during quiet solar activity. On the contrary, estimations differ by one order of magnitude for the contribution induced by certain solar particle events. Indeed, during Ground Level Enhancements (GLE) event, the Sun can emit particles of sufficient energy and intensity to raise radiation levels on Earth's surface. Analyses of GLE characteristics occurring since 1942 showed that for the worst of them, the dose level is of the order of 1 mSv and more. The largest of these events was observed on February 1956 for which the ambient dose equivalent rate is in the orders of 10 mSv/hr. The extra dose at aircraft altitudes for a flight during this event might have been about 20 mSv, i.e. comparable with the annual limit for aircrew. The most recent GLE, occurred on September 2017 resulting from an X-class solar flare, and it was measured on the surface of both the Earth and Mars using the Radiation Assessment Detector on the Mars Science Laboratory's Curiosity Rover. Recently, Hubert et al. proposed a GLE model included in a particle transport platform (named ATMORAD) describing the extensive air shower characteristics and allowing to assess the ambient dose equivalent. In this approach, the GCR is based on the Force-Field approximation model. The physical description of the Solar Cosmic Ray (i.e. SCR) considers the primary differential rigidity spectrum and the distribution of primary particles at the top of the atmosphere. ATMORAD allows to determine the spectral fluence rate of secondary particles induced by extensive showers, considering altitude range from ground to 45 km. Ambient dose equivalent can be determined using fluence-to-ambient dose equivalent conversion coefficients. The objective of this paper is to analyze the GCR and SCR impacts on ambient dose equivalent considering a high number statistic of world-flight paths. Flight trajectories are based on the Eurocontrol Demand Data Repository (DDR) and consider realistic flight plan with and without regulations or updated with Radar Data from CFMU (Central Flow Management Unit). The final paper will present exhaustive analyses implying solar impacts on ambient dose equivalent level and will propose detailed analyses considering route and airplane characteristics (departure, arrival, continent, airplane type etc.), and the phasing of the solar event. Preliminary results show an important impact of the flight path, particularly the latitude which drives the cutoff rigidity variations. Moreover, dose values vary drastically during GLE events, on the one hand with the route path (latitude, longitude altitude), on the other hand with the phasing of the solar event. Considering the GLE occurred on 23 February 1956, the average ambient dose equivalent evaluated for a flight Paris - New York is around 1.6 mSv, which is relevant to previous works This point highlights the importance of monitoring these solar events and of developing semi-empirical and particle transport method to obtain a reliable calculation of dose levels.

Keywords: cosmic ray, human dose, solar flare, aviation

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3 Microplastic Concentrations and Fluxes in Urban Compartments: A Systemic Approach at the Scale of the Paris Megacity

Authors: Rachid Dris, Robin Treilles, Max Beaurepaire, Minh Trang Nguyen, Sam Azimi, Vincent Rocher, Johnny Gasperi, Bruno Tassin

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Microplastic sources and fluxes in urban catchments are only poorly studied. Most often, the approaches taken focus on a single source and only carry out a description of the contamination levels and type (shape, size, polymers). In order to gain an improved knowledge of microplastic inputs at urban scales, estimating and comparing various fluxes is necessary. The Laboratoire Eau, Environnement et Systèmes Urbains (LEESU), the Laboratoire Eau Environnement (LEE) and the SIAAP (Service public de l’assainissement francilien) initiated several projects to investigate different urban sources and flows of microplastics. A systemic approach is undertaken at the scale of Paris Megacity, and several compartments are considered, including atmospheric fallout, wastewater treatments plants, runoff and combined sewer overflows. These investigations are carried out within the Limnoplast and OPUR projects. Atmospheric fallout was sampled during consecutive periods ranging from 2 to 3 weeks with a stainless-steel funnel. Both wet and dry periods were considered. Different treatment steps were sampled in 2 wastewater treatment plants (Seine-Amont for activated sludge and Seine-Centre for biofiltration) of the SIAAP, including sludge samples. Microplastics were also investigated in combined sewer overflows as well as in stormwater at the outlet suburban catchment (Sucy-en-Brie, France) during four rain events. Samples are treated using hydroperoxide digestion (H₂O₂ 30 %) in order to reduce organic material. Microplastics are then extracted from the samples with a density separation step using NaI (d=1.6 g.cm⁻³). Samples are filtered on metallic filters with a porosity of 14 µm between steps to separate them from the solutions (H₂O₂ and NaI). The last filtration was carried out on alumina filters. Infrared mapping analysis (using a micro-FTIR with an MCT detector) is performed on each alumina filter. The resulting maps are analyzed using a microplastic analysis software simple, developed by Aalborg University, Denmark and Alfred Wegener Institute, Germany. Blanks were systematically carried out to consider sample contamination. This presentation aims at synthesizing the data found in the various projects. In order to carry out a systemic approach and compare the various inputs, all the data were converted into annual microplastic fluxes (number of microplastics per year), and extrapolated to the Parisian agglomeration. PP, PE and alkyd are the most prevalent polymers found in storm water samples. Rain intensity and microplastic concentrations did not show any clear correlation. Considering the runoff volumes and the impervious surface area of the studied catchment, a flux of 4*107–9*107 MPs.yr⁻¹.ha⁻¹ was estimated. Samples of wastewater treatment plants and atmospheric fallout are currently being analyzed in order to finalize this assessment. The representativeness of such samplings and uncertainties related to the extrapolations will be discussed and gaps in knowledge will be identified. The data provided by such an approach will help to prioritize future research as well as policy efforts.

Keywords: microplastics, atmosphere, wastewater, urban runoff, Paris megacity, urban waters

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2 Phytochemical Profile and in Vitro Bioactivity Studies on Two Underutilized Vegetables in Nigeria

Authors: Borokini Funmilayo Boede

Abstract:

B. alba L., commonly called ‘Amunututu’ and Solanecio biafrae called ‘Worowo’ among the Yoruba tribe in the southwest part of Nigeria are reported to be of great ethnomedicinal importance but are among many underutilized green leafy vegetables in the country. Many studies have established the nutritional values of these vegetables, utilization are very poor and indepth information on their chemical profiles is scarce. The aqueous, methanolic and ethanolic extracts of these vegetables were subjected to phytochemical screening and phenolic profiles of the alcoholic extracts were characterized by using high-performance liquid chromatography coupled with diode array detector (HPLC-DAD). Total phenol and flavonoid contents were determined, antioxidant activities were evaluated using five in vitro assays to assess DPPH, nitric oxide and hydroxyl radical-scavenging abilities, as well as reducing power with ferric reducing antioxidant assay and phosphomolybdate method. The antibacterial activities of the extracts against Staphylococcus aureus, Pseudomonas aeruginosa, and Salmonella typhi were evaluated by using agar well diffusion method and the antifungal activity evaluated against food-associated filamentous fungi by using poisoned food technique with the aim of assessing their nutraceutical potentials to encourage their production and utilization. The results revealed the presence of saponnin, steroids, tannin, terpenoid and flavonoid as well as phenolic compounds: gallic acid, chlorogenic acid, caffeic acid, coumarin, rutin, quercitrin, quercetin and kaemferol. The vegetables showed varying concentration dependent reducing and radical scavenging abilities from weak to strong compared with gallic acid, rutin, trolox and ascorbic acid used as positive controls; the aqueous extracts which gave higher concentrations of total phenol displayed higher ability to reduce Fe (lll) to Fe (ll) and stronger inhibiting power against hydroxyl radical than the alcoholic extracts and in most cases exhibited more potency than the ascorbic acids used as positive controls, at the same concentrations, whereas, methanol and / or ethanol extracts were found to be more effective in scavenging 2, 2-diphenyl-1-picryl hydrazyl radical and showed higher ability to reduce Mo (VI) to Mo (V) in total antioxidant assay than the aqueous extracts. However, the inhibition abilities of all the extracts against nitric oxide were comparable with the ascorbic acid control at the same concentrations. There were strong positive correlations with total phenol (mg GAE/g) and total flavonoid (mg RE/g) contents in the range TFC (r=0.857- 0999 and r= 0.904-1.000) and TPC (r= 0.844- 0.992 and r= 0.900 -0.999) for Basella alba and Senecio biafrae respectively. Inhibition concentration at 50 % (IC50) for each extract to scavenge DPPH, OH and NO radicals ranged from 32.73 to 1.52 compared with control (0.846 - -6.42) mg/ml. At 0.05g/ml, the vegetables were found to exhibit mild antibacterial activities against Staphylococcus aureus, Pseudomonas aeruginosa and Salmonella typhi compared with streptomycin sulphate used as control but appreciable antifungi activities against (Trichoderma rubrum and Aspergillus fumigates) compared with bonlate antibiotic positive control. The vegetables possess appreciable antioxidant and antimicrobial properties for promoting good health, their cultivation and utilization should be encouraged especially in the face of increasing health and economic challenges and food insecurity in many parts of the world.

Keywords: antimicrobial, antioxidants, extracts, phytochemicals

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1 Physico-Chemical Characterization of Vegetable Oils from Oleaginous Seeds (Croton megalocarpus, Ricinus communis L., and Gossypium hirsutum L.)

Authors: Patrizia Firmani, Sara Perucchini, Irene Rapone, Raffella Borrelli, Stefano Chiaberge, Manuela Grande, Rosamaria Marrazzo, Alberto Savoini, Andrea Siviero, Silvia Spera, Fabio Vago, Davide Deriu, Sergio Fanutti, Alessandro Oldani

Abstract:

According to the Renewable Energy Directive II, the use of palm oil in diesel will be gradually reduced from 2023 and should reach zero in 2030 due to the deforestation caused by its production. Eni aims at finding alternative feedstocks for its biorefineries to eliminate the use of palm oil by 2023. Therefore, the ideal vegetable oils to be used in bio-refineries are those obtainable from plants that grow in marginal lands and with low impact on food-and-feed chain; hence, Eni research is studying the possibility of using oleaginous seeds, such as castor, croton, and cotton, to extract the oils to be exploited as feedstock in bio-refineries. To verify their suitability for the upgrading processes, an analytical protocol for their characterization has been drawn up and applied. The analytical characterizations include a step of water and ashes content determination, elemental analysis (CHNS analysis, X-Ray Fluorescence, Inductively Coupled Plasma - Optical Emission Spectroscopy, ICP– Mass Spectrometry), and total acid number determination. Gas chromatography coupled to flame ionization detector (GC-FID) is used to quantify the lipid content in terms of free fatty acids, mono-, di- and triacylglycerols, and fatty acids composition. Eventually, Nuclear Magnetic Resonance and Fourier Transform-Infrared spectroscopies are exploited with GC-MS and Fourier Transform-Ion Cyclotron Resonance to study the composition of the oils. This work focuses on the GC-FID analysis of the lipid fraction of these oils, as the main constituent and of greatest interest for bio-refinery processes. Specifically, the lipid component of the extracted oil was quantified after sample silanization and transmethylation: silanization allows the elution of high-boiling compounds and is useful for determining the quantity of free acids and glycerides in oils, while transmethylation leads to a mixture of fatty acid esters and glycerol, thus allowing to evaluate the composition of glycerides in terms of Fatty Acids Methyl Esters (FAME). Cotton oil was extracted from cotton oilcake, croton oil was obtained by seeds pressing and seeds and oilcake ASE extraction, while castor oil comes from seed pressing (not performed in Eni laboratories). GC-FID analyses reported that the cotton oil is 90% constituted of triglycerides and about 6% diglycerides, while free fatty acids are about 2%. In terms of FAME, C18 acids make up 70% of the total and linoleic acid is the major constituent. Palmitic acid is present at 17.5%, while the other acids are in low concentration (<1%). Both analyzes show the presence of non-gas chromatographable compounds. Croton oils from seed pressing and extraction mainly contain triglycerides (98%). Concerning FAME, the main component is linoleic acid (approx. 80%). Oilcake croton oil shows higher abundance of diglycerides (6% vs ca 2%) and a lower content of triglycerides (38% vs 98%) compared to the previous oils. Eventually, castor oil is mostly constituted of triacylglycerols (about 69%), followed by diglycerides (about 10%). About 85.2% of total FAME is ricinoleic acid, as a constituent of triricinolein, the most abundant triglyceride of castor oil. Based on the analytical results, these oils represent feedstocks of interest for possible exploitation as advanced biofuels.

Keywords: analytical protocol, biofuels, biorefinery, gas chromatography, vegetable oil

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