Search results for: Ullmann reaction

Authors: Tesfaye Tebeka Simur, Tian-Yu Peng, Yi-Feng Wang, Xiu-Wei Wu, Feng-Lian Zhang

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A boryl radical-promoted dehydroxylative alkylation of 3-hydroxy-oxindole derivatives is achieved. The reaction starts from addition of 4-dimethylaminopyridine (DMAP)-boryl radical to the amide carbonyl oxygen atom, which induces a spin-center shift process to promote the C−O bond cleavage. The elimination of a hydroxide anion from a free hydroxy group is also accomplished. Capture of the generated carbon radical with alkenes furnishes a variety of C-3 alkylated oxindoles. This method features a simple operation and broad substrate scope.

Keywords: boryl radical, C-O, C-F, C=C, C=N bond activation, spin center shift

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Authors: S. Limpattayanate, M. Hunsom

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A comparison of activity and stability of the as-formed Pt/C, Pt-Co, and Pt-Pd/C electrocatalysts, prepared by a combined approach of impregnation and seeding, was performed. According to the activity test in a single proton exchange membrane (PEM) fuel cell, the oxygen reduction reaction (ORR) activity of the Pt-M/C electro catalyst was slightly lower than that of Pt/C. The j0.9 V and E10 mA/cm2 of the as-prepared electrocatalysts increased in the order of Pt/C>Pt-Co/C>Pt-Pd/C. However, in the medium-to-high current density region, Pt-Pd/C exhibited the best performance. With regard to their stability in a 0.5 M H2SO4 electrolyte solution, the electro chemical surface area decreased as the number of rounds of repetitive potential cycling increased due to the dissolution of the metals within the catalyst structure. For long-term measurement, Pt-Pd/C was the most stable than the other three electrocatalysts.

Keywords: ORR activity, stability, Pt-based electrocatalysts, PEM fuel cell

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Authors: Branislav Kovačević, Andrej Pilipović, Zoran Novčić, Marina Milović, Lazar Kesić, Milan Drekić, Saša Pekeč, Leopold Poljaković Pajnik, Saša Orlović

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Poplars present one of the most important tree species used for phytoremediation in the northern hemisphere. They can be used either as direct “cleaners” of the contaminated soils or as buffer zones preventing the contaminant plume to the surrounding environment. In order to produce appropriate planting material for this purpose, there is a long process of the breeding of the most favorable candidates. Although the development of the poplar propagation technology has been evolving for decades, white poplar nursery production, as well as the establishment of short-rotation coppice plantations, still considerably depends on the success of hardwood cuttings’ survival. This is why easy rooting is among the most desirable properties in white poplar breeding. On the other hand, there are many opportunities for the optimization of the technological procedures in order to meet the demands of particular genotype (clonal technology). In this study the effect of the term of hardwood cuttings’ preparation of four white poplar clones on their survival and further growth of rooted cuttings in nursery conditions were tested. There were three terms of cuttings’ preparation: the beginning of February (2nd Feb 2023), the beginning of March (3rd Mar 2023) and the end of March (21nd Mar 2023), which is regarded as the standard term. The cuttings were stored in cool chamber at 2±2°C. All cuttings were planted on the same date (11th Apr 2023), in soil prepared with rotary tillage, and then cultivated by usual nursey procedures. According to the results obtained after the bud set (29th Sept 2023) there were significant differences in the survival and growth of rooted cuttings between examined terms of cutting preparation. Also, there were significant differences in the reaction of examined clones on terms of cutting preparation. In total, the best results provided cuttings prepared at the first term (2nd Feb 2023) (survival rate of 39.4%), while performance after two later preparation terms was significantly poorer (20.5% after second and 16.5% after third term). These results stress the significance of dormancy preservation in cuttings of examined white poplar clones for their survival, which could be especially important in context of climate change. Differences in clones’ reaction to term of cutting preparation suggest necessity of adjustment of the technology to the needs of particular clone i.e. design of clone specific technology.

Keywords: rooting, Populus alba, nursery, clonal technology

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Authors: Boris Barbolyas, Kristina Buckova, Tomas Volensky, Cyril Belavy, Ladislav Dedik

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Background: Based on statokinezigram, the human balance control is often studied. Approach to human postural reaction analysis is based on a combination of stabilometry output signal with retroreflective marker data signal processing, analysis, and understanding, in this study. The study shows another original application of Method of Developed Statokinesigram Trajectory (MDST), too. Methods: In this study, the participants maintained quiet bipedal standing for 10 s on stabilometry platform. Consequently, bilateral vibration stimuli to Achilles tendons in 20 s interval was applied. Vibration stimuli caused that human postural system took the new pseudo-steady state. Vibration frequencies were 20, 60 and 80 Hz. Participant's body segments - head, shoulders, hips, knees, ankles and little fingers were marked by 12 retroreflective markers. Markers positions were scanned by six cameras system BTS SMART DX. Registration of their postural reaction lasted 60 s. Sampling frequency was 100 Hz. For measured data processing were used Method of Developed Statokinesigram Trajectory. Regression analysis of developed statokinesigram trajectory (DST) data and retroreflective marker developed trajectory (DMT) data were used to find out which marker trajectories most correlate with stabilometry platform output signals. Scaling coefficients (λ) between DST and DMT by linear regression analysis were evaluated, too. Results: Scaling coefficients for marker trajectories were identified for all body segments. Head markers trajectories reached maximal value and ankle markers trajectories had a minimal value of scaling coefficient. Hips, knees and ankles markers were approximately symmetrical in the meaning of scaling coefficient. Notable differences of scaling coefficient were detected in head and shoulders markers trajectories which were not symmetrical. The model of postural system behavior was identified by MDST. Conclusion: Value of scaling factor identifies which body segment is predisposed to postural instability. Hypothetically, if statokinesigram represents overall human postural system response to vibration stimuli, then markers data represented particular postural responses. It can be assumed that cumulative sum of particular marker postural responses is equal to statokinesigram.

Keywords: center of pressure (CoP), method of developed statokinesigram trajectory (MDST), model of postural system behavior, retroreflective marker data

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Authors: N. Touj, M. Sauthier, L. Mansour, N. Hamdi

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The palladium NHC complexes are one of the most interesting and widely investigated complexes in different catalytic transformations, especially C–C bond. Thus, the use of N-heterocyclic carbenes associated with palladium has been reported as efficient catalysts for the carbonyl coupling under mild and varied conditions. Herein, we report the synthesis, characterization, and cytotoxic activities of two new families of benzimidazolium salts. Then we studied the use of this class of benzimidazolium salts as a ligand in the carbonylative cross-coupling of 2-bromopyridine with different boronic acids under CO atmosphere to form unsymmetrical arylpyridine ketones.

Keywords: NHC-Pd(II) catalysts, carbonylative Suzuki cross-coupling reaction, arylboronic acids, 2-bromopyridine, unsymmetrical arylpyridine ketones

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Authors: Tobias Schnabel

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Naphthalene and naphthalene similar compounds are a common problem in the indoor air of buildings from the 1960s and 1970s in Germany. Often tar containing roof felt was used under the concrete floor to prevent humidity to come through the floor. This tar containing roof felt has high concentrations of PAH (Polycyclic aromatic hydrocarbon) and naphthalene. Naphthalene easily evaporates and contaminates the indoor air. Especially after renovations and energetically modernization of the buildings, the naphthalene concentration rises because no forced air exchange can happen. Because of this problem, it is often necessary to change the floors after renovation of the buildings. The MFPA Weimar (Material research and testing facility) developed in cooperation a project with LEJ GmbH and Reichmann Gebäudetechnik GmbH. It is a technical solution for the disintegration of naphthalene in naphthalene, similar compounds in indoor air with photocatalytic reforming. Photocatalytic systems produce active oxygen species (hydroxyl radicals) through trading semiconductors on a wavelength of their bandgap. The light energy separates the charges in the semiconductor and produces free electrons in the line tape and defect electrons. The defect electrons can react with hydroxide ions to hydroxyl radicals. The produced hydroxyl radicals are a strong oxidation agent, and can oxidate organic matter to carbon dioxide and water. During the research, new titanium oxide catalysator surface coatings were developed. This coating technology allows the production of very porous titan oxide layer on temperature stable carrier materials. The porosity allows the naphthalene to get easily absorbed by the surface coating, what accelerates the reaction of the heterogeneous photocatalysis. The photocatalytic reaction is induced by high power and high efficient UV-A (ultra violet light) Leds with a wavelength of 365nm. Various tests in emission chambers and on the reformer itself show that a reduction of naphthalene in important concentrations between 2 and 250 µg/m³ is possible. The disintegration rate was at least 80%. To reduce the concentration of naphthalene from 30 µg/m³ to a level below 5 µg/m³ in a usual 50 ² classroom, an energy of 6 kWh is needed. The benefits of the photocatalytic indoor air treatment are that every organic compound in the air can be disintegrated and reduced. The use of new photocatalytic materials in combination with highly efficient UV leds make a safe and energy efficient reduction of organic compounds in indoor air possible. At the moment the air cleaning systems take the step from prototype stage into the usage in real buildings.

Keywords: naphthalene, titandioxide, indoor air, photocatalysis

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Authors: K. Thiel, P. Patrikainen, C. Nagy, D. Fitzpatrick, E.-M. Aro, P. Kallio

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Photosynthetic cyanobacteria have been recognized as potential future biotechnological hosts for the direct conversion of CO₂ into chemicals of interest using sunlight as the solar energy source. However, in order to develop commercially viable systems, the flux of electrons from the photosynthetic light reactions towards specified target chemicals must be significantly improved. The objective of the study was to investigate whether the autotrophic production efficiency of specified end-metabolites can be improved in engineered cyanobacterial cells by rescuing excited electrons that are normally lost to molecular oxygen due to the cyanobacterial flavodiiron protein Flv1/3. Natively Flv1/3 dissipates excess electrons in the photosynthetic electron transfer chain by directing them to molecular oxygen in Mehler-like reaction to protect photosystem I. To evaluate the effect of flavodiiron inactivation on autotrophic production efficiency in the cyanobacterial host Synechocystis sp. PCC 6803 (Synechocystis), sucrose was selected as the quantitative reporter and a representative of a potential end-product of interest. The concept is based on the native property of Synechocystis to produce sucrose as an intracellular osmoprotectant when exposed to high external ion concentrations, in combination with the introduction of a heterologous sucrose permease (CscB from Escherichia coli), which transports the sucrose out from the cell. In addition, cell growth, photosynthetic gas fluxes using membrane inlet mass spectrometry and endogenous storage compounds were analysed to illustrate the consequent effects of flv deletion on pathway flux distributions. The results indicate that a significant proportion of the electrons can be lost to molecular oxygen via Flv1/3 even when the cells are grown under high CO₂ and that the inactivation of flavodiiron activity can enhance the photosynthetic electron flux towards optionally available sinks. The flux distribution is dependent on the light conditions and the genetic context of the Δflv mutants, and favors the production of either sucrose or one of the two storage compounds, glycogen or polyhydroxybutyrate. As a conclusion, elimination of the native Flv1/3 reaction and concomitant introduction of an engineered product pathway as an alternative sink for excited electrons could enhance the photosynthetic electron flux towards the target endproduct without compromising the fitness of the host.

Keywords: cyanobacterial engineering, flavodiiron proteins, redirecting electron flux, sucrose

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Authors: Josine Beek, S. Agten, R. Del Pozo, B. Balis

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The objective of the present study was to compare the safety of intramuscular administration of Zuprevo® (tildipirosin, 40 mg/mL) with Draxxin® (tulathromycin, 100 mg/mL) in the treatment of swine respiratory disease at weaning age. The trial was carried out in two farrow-to-finish farms with 300 sows (farm A) and 500 sows (farm B) in a batch-production system. Farm A had no history of respiratory problems, whereas farm B had a history of respiratory outbreaks with increased mortality ( > 2%) in the nursery. Both farms were positive to Pasteurella multocida, Bordetella bronchiseptica, Actinobacillus pleuropneumoniae and Haemophilus parasuis. From each farm, one batch of piglets was included (farm A: 644 piglets; farm B: 963 piglets). One day before weaning (day 0; 18-21 days of age), piglets were identified by an individual ear tag and randomly assigned to a treatment group. At day 0, Group 1 was treated with a single intramuscular injection with Zuprevo® (tildipirosin, 40 mg/mL; 1 mL/10 kg) and group 2 with Draxxin® (tulathromycin, 100 mg/mL; 1 mL/40 kg). For practical reasons, dosage of the product was adjusted according to three weight categories: < 4 kg, 4-6 kg and > 6 kg. Within each farm, piglets of both groups were comingled at weaning and subsequently managed and located in the same facilities and with identical environmental conditions. Our study involved the period from day 0 until 10 weeks of age. Safety of treatment was evaluated by 1) visual examination for signs of discomfort directly after treatment and after 15 min, 1 h and 24 h and 2) mortality rate within 24 h after treatment. Efficacy of treatment was evaluated based on mortality rate from day 0 until 10 weeks of age. Each piglet that died during the study period was necropsied by the herd veterinarian to determine the probable cause of death. Data were analyzed using binary logistic regression and differences were considered significant if p < 0.05. The pig was the experimental unit. In total, 848 piglets were treated with tildipirosin and 759 piglets with tulathromycin. In farm A, one piglet with retarded growth ( < 1 kg at 18 days of age) showed an adverse reaction after injection of tildipirosin: lateral recumbence and dullness for ± 30 sec. The piglet recovered after 1-2 min. This adverse reaction was probably due to overdosing (12 mg/kg). No adverse effect of treatment was observed in any other piglet. There was no mortality within 24 h after treatment. No significant difference was found in mortality rate between both groups from day 0 until 10 weeks of age. In farm A, overall mortality rate was 0.3% (2/644). In farm B, mortality rate was 0.2% (1/502) in group 1 (tildipirosin) and 0.9% (4/461) in group 2 (tulathromycin)(p=0.60). The necropsy of piglets that died during the study period revealed no macroscopic lesions of the respiratory tract. In conclusion, Zuprevo® (tildipirosin, 40 mg/mL) was shown to be a safe and efficacious alternative to Draxxin® (tulathromycin, 100 mg/mL) for the early treatment of swine respiratory disease at weaning age.

Keywords: antibiotic treatment, safety, swine respiratory disease, tildipirosin

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Authors: Ramdas Sonawane, Mahaveer Gadiya

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The control problem associated with nuclear dynamics is represented by nonlinear integro-differential equation with additive controls. To control chain reaction, certain amount of neutrons is added into (or withdrawn out of) chamber as and when required. It is not realistic. So, we can think of controlling the reactor dynamics by bilinear control, which enters the system as coefficient of state. In this paper, we study the approximate and exact controllability of parabolic integro-differential equation controlled by bilinear control with non-homogeneous boundary conditions in bounded domain. We prove the existence of control and propose an explicit control strategy.

Keywords: approximate control, exact control, bilinear control, nuclear dynamics, integro-differential equations

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Authors: Yalçın Kılıç, İbrahim Kani

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The conversion of hydrocarbons to carbonyl compounds by oxidation reaction is one of the most important reactions in the synthesis of fine chemicals. As a result of the oxidation of hydrocarbons containing aliphatic sp3-CH groups in their structures, aldehydes, ketones or carboxylic acids can be obtained. In this study, OSSO-type 2,2'-[1,4-butanedylbis(thio)]bis-benzoic acid (tsabutH2) ligand and [Zn(µ-tsabut)(phen)]n complex (where phen = 1,10-phenantroline) were synthesized and their structures were characterized by single crystal x-ray diffraction method. The catalytic efficiency of the complex in the catalytic oxidation studies of organic compounds such as cyclohexane, ethylbenzene, diphenylmethane, and p-xylene containing sp3-C-H in its structure was investigated.

Keywords: metal complex, OSSO-type ligand, catalysis, oxidation

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Authors: Sarah Triller, Ferdi Schüth

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The challenges encountered in upscaling the mechanochemical synthesis of high surface area α-alumina are investigated in this study. After lab-scale experiments in shaker mills and planetary ball mills, the optimization of reaction parameters of the conversion in the smallest vessel of a scalable mill, named Simoloyer, was developed. Furthermore, the future perspectives by scaling up the conversion in several steps are described. Since abrasion from the steel equipment can be problematic, the process was transferred to a ceramically lined mill, which solved the contamination problem. The recovered alpha-alumina shows a high specific surface area in all investigated scales.

Keywords: mechanochemistry, scale-up, ball milling, ceramic lining

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Authors: Sayantan Saha, Sambit Supriya Dash, Vinayak Malhotra

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Efficient propulsive systems development is an area of major interest and concern in aerospace industry. Combustion forms the most reliable and basic form of propulsion for ground and space applications. The generation of large amount of energy from a small volume relates mostly to the flaming combustion. This study deals with instabilities associated with flaming combustion. Combustion is always accompanied by acoustics be it external or internal. Chemical propulsion oriented rockets and space systems are well known to encounter acoustic instabilities. Acoustic brings in changes in inter-energy conversion and alter the reaction rates. The modified heat fluxes, owing to wall temperature, reaction rates, and non-linear heat transfer are observed. The thermoacoustic instabilities significantly result in reduced combustion efficiency leading to uncontrolled liquid rocket engine performance, serious hazards to systems, assisted testing facilities, enormous loss of resources and every year a substantial amount of money is spent to prevent them. Present work attempts to fundamentally understand the mechanisms governing the thermoacoustic combustion in liquid rocket engine using a simplified experimental setup comprising a butane cylinder and an impinging acoustic source. Rocket engine produces sound pressure level in excess of 153 Db. The RL-10 engine generates noise of 180 Db at its base. Systematic studies are carried out for varying fuel flow rates, acoustic levels and observations are made on the flames. The work is expected to yield a good physical insight into the development of acoustic devices that when coupled with the present propulsive devices could effectively enhance combustion efficiency leading to better and safer missions. The results would be utilized to develop impinging acoustic devices that impinge sound on the combustion chambers leading to stable combustion thus, improving specific fuel consumption, specific impulse, reducing emissions, enhanced performance and fire safety. The results can be effectively applied to terrestrial and space application.

Keywords: combustion instability, fire safety, improved performance, liquid rocket engines, thermoacoustics

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Authors: Zahra Yadollahi, Marjan Motiei, Natalia Kazantseva, Petr Saha

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Chitosan (CS)-whey protein isolate (WPI) core-shell nanoparticles were synthesized through self-assembly of whey protein isolated polyanions and chitosan polycations in the presence of tripolyphosphate (TPP) as a crosslinker. The formation of this type of nanostructures with narrow particle size distribution is crucial for developing delivery systems since the functional characteristics highly depend on their sizes. To achieve this goal, the nanostructure was optimized by varying the concentrations of WPI, CS, and TPP in the reaction mixture. The chemical characteristics, surface morphology, and particle size of the nanoparticles were evaluated.

Keywords: whey protein isolated, chitosan, nanoparticles, delivery system

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Authors: Mingchuan Zhou, Haitao Zhang, Hongfang Ma, Weiyong Ying

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Alumina supported platinum and tin catalysts with different loadings of Pt and Sn were prepared and characterized by low temperature N₂ adsorption/desorption, H₂-temperature programed reduction and CO pulse chemisorption. Pt and Sn below 1% loading were suitable for acetic acid hydrogenation. The best performance over 0.75Pt1Sn/Al₂O₃ can reach 87.55% conversion of acetic acid and 47.39% selectivity of ethanol. The operating conditions of acetic acid hydrogenation over 1Pt1Sn/Al₂O₃ were investigated. High reaction temperature can enhance the conversion of acetic acid, but it decreased total selectivity of ethanol and acetyl acetate. High pressure and low weight hourly space velocity were beneficial to both conversion of acetic acid and selectivity to ethanol.

Keywords: acetic acid, hydrogenation, operating condition, PtSn

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Authors: Magdalena Diaka, Paweł Mazierski, Joanna Żebrowska, Michał Winiarski, Tomasz Klimczuk, Adriana Zaleska-Medynska

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During the last years, TiO2 nanotubes have been widely studied due to their unique highly ordered array structure, unidirectional charge transfer and higher specific surface area compared to conventional TiO2 powder. These photoactive materials, in the form of thin layer, can be activated by low powered and low cost irradiation sources (such as LEDs) to remove VOCs, microorganism and to deodorize air streams. This is possible due to their directly growth on a support material and high surface area, which guarantee enhanced photon absorption together with an extensive adsorption of reactant molecules on the photocatalyst surface. TiO2 nanotubes exhibit also lots of other attractive properties, such as potential enhancement of electron percolation pathways, light conversion, and ion diffusion at the semiconductor-electrolyte interface. Pure TiO2 nanotubes were previously used to remove organic compounds from the gas phase as well as in water splitting reaction. The major factors limiting the use of TiO2 nanotubes, which have not been fully overcome, are their relatively large band gap (3-3,2 eV) and high recombination rate of photogenerated electron–hole pairs. Many different strategies were proposed to solve this problem, however titania nanostructures containing incorporated metal oxides like Ag2O shows very promising, new optical and photocatalytic properties. Unfortunately, there is still very limited number of reports regarding application of TiO2/MxOy nanostructures. In the present work, we prepared TiO2/Ag2O nanotubes obtained by anodization of Ti-Ag alloys containing 5, 10 and 15 wt. % Ag. Photocatalysts prepared in this way were characterized by X-ray diffraction spectroscopy (XRD), scanning electron microscopy (SEM), luminescence spectroscopy and UV-Vis spectroscopy. The activities of new TiO2/Ag2O were examined by photocatalytic degradation of toluene in gas phase reaction and phenol in aqueous phase using 1000 W Xenon lamp (Oriel) and light emitting diodes (LED) as a irradiation sources. Additionally efficiency of bacteria (Pseudomonas aeruginosa) removal from the gas phase was estimated. The number of surviving bacteria was determined by the serial twofold dilution microtiter plate method, in Tryptic Soy Broth medium (TSB, GibcoBRL).

Keywords: photocatalysis, antibacterial properties, titania nanotubes, new TiO2/MxOy nanostructures

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Authors: Siti Nur Syazni Mohd Zuki, Tan Ling Ling, Nina Suhaity Azmi, Chong Kwok Feng, Lee Yook Heng

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Nitrite (NO2-) ion is used prevalently as a preservative in processed meat. Elevated levels of nitrite also found in edible bird’s nests (EBNs). Consumption of NO2- ion at levels above the health-based risk may cause cancer in humans. Spectrophotometric Griess test is the simplest established standard method for NO2- ion detection, however, it requires careful control of pH of each reaction step and susceptible to strong oxidants and dyeing interferences. Other traditional methods rely on the use of laboratory-scale instruments such as GC-MS, HPLC and ion chromatography, which cannot give real-time response. Therefore, it is of significant need for devices capable of measuring nitrite concentration in-situ, rapidly and without reagents, sample pretreatment or extraction step. Herein, we constructed a microspheres-based microbial optode for visual quantitation of NO2- ion. Raoutella planticola, the bacterium expressing NAD(P)H nitrite reductase (NiR) enzyme has been successfully extracted by microbial technique from EBN collected from local birdhouse. The whole cells and the lipophilic Nile Blue chromoionophore were physically absorbed on the photocurable poly(n-butyl acrylate-N-acryloxysuccinimide) [poly (nBA-NAS)] microspheres, whilst the reduced coenzyme NAD(P)H was covalently immobilized on the succinimide-functionalized acrylic microspheres to produce a reagentless biosensing system. Upon the NiR enzyme catalyzes the oxidation of NAD(P)H to NAD(P)+, NO2- ion is reduced to ammonium hydroxide, and that a colour change from blue to pink of the immobilized Nile Blue chromoionophore is perceived as a result of deprotonation reaction increasing the local pH in the microspheres membrane. The microspheres-based optosensor was optimized with a reflectance spectrophotometer at 639 nm and pH 8. The resulting microbial bio-optode membrane could quantify NO2- ion at 0.1 ppm and had a linear response up to 400 ppm. Due to the large surface area to mass ratio of the acrylic microspheres, it allows efficient solid state diffusional mass transfer of the substrate to the bio-recognition phase, and achieve the steady state response as fast as 5 min. The proposed optical microbial biosensor requires no sample pre-treatment step and possesses high stability as the whole cell biocatalyst provides protection to the enzymes from interfering substances, hence it is suitable for measurements in contaminated samples.

Keywords: acrylic microspheres, microbial bio-optode, nitrite ion, reflectometric

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Authors: Ali Bahri Lubis

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Tryptophan oxidation by Heme-dioxygenase enzyme is initial important stepTryptophan oxidation by Heme-dioxygenase enzyme is initial important step in kynurenine pathway implicating to several severe diseases such as Parkinson’s Disease, Huntington Disease, poliomyelitis and cataract. It is crucial to comprehend the oxidation mechanism with the hope to find decent treatment upon abovementioned diseases. The mechanism has been debatable since no one has been yet proved the mechanism obviously. In this research we have attempted to prove mechanistic steps of tryptophan oxidation via human indoleamine dioxygenase (h-IDO) using various substrates: L-tryptophan, L-tryptophan (indole-ring-2-13C), L-fully-labelled13C-tryptophan, L-N-methyl-tryptophan, L-tryptophan and 2-amino-3-(benzo(b)thiophene-3-yl) propanoic acid. All enzyme assay experiments were measured using a UV-Vis spectrophotometer, LC-MS, 1H-NMR, and HSQC. We also successfully synthesized enzyme products as our control in NMR measurements. The result exhibited that the distinct substrates produced N-formyl kynurenine (NFK) and hydroxypyrrolloindoleamine carboxylate acid (HPIC) in different concentrations and isomers, correlated to the proposal of considered mechanism reaction in kynurenine pathway implicating to several severe diseases such as Parkinson’s Disease, Huntington Disease, poliomyelitis and cataract. It is crucial to comprehend the oxidation mechanism with the hope to find decent treatment for the abovementioned diseases. The mechanism has been debatable since no one has yet proven the mechanism obviously. In this research we have attempted to prove mechanistic steps of tryptophan oxidation via human indoleamine dioxygenase (h-IDO) using various substrates: L-tryptophan, L-tryptophan (indole-ring-2-13C), L-fully-labelled13C-tryptophan, L-N-methyl-tryptophan, L-tryptophan and 2-amino-3-(benzo(b)thiophene-3-yl) propanoic acid. All enzyme assay experiments were measured using a UV-Vis spectrophotometer, LC-MS, 1H-NMR and HSQC. We also successfully synthesized enzyme products as our control in NMR measurements. The result exhibited that the distinct substrates produced N-formyl kynurenine (NFK) and hydroxypyrrolloindoleamine carboxylate acid (HPIC) in different concentrations and isomers, correlated to the proposal of considered mechanism reaction.

Keywords: heme-dioxygenase enzyme, tryptophan oxidation, kynurenine pathway, n-formyl kynurenine

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Authors: Tassadit Tabouche

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Water sprays pattern, and water droplets size (different droplets diameter) are a key factors in the success of the suppression by water spray. The effects of the two important factors are investigated in this study. However, the fire extinguishing mechanism in such devices is not well understood due to the complexity of the physical and chemical interactions between water spray and fire plume. in this study, 3D, unsteady, two phase flow CFD simulation approach is introduced to provide a quantitative analysis of the complex interactions occurring between water spray and fire plume. Lagrangian Discrete Phase Model (DPM) was used for water droplets and a global one-step reaction mechanism in combustion model was used for fire plume.

Keywords: droplets, water spray, water droplets size, 3D

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Authors: Sima Shakoorjavan, Mahdieh Eskafi, Dawid Stawski, Somaye Akbari

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In this study, poly (amidoamine) dendritic material (PAMAM) and poly (acrylic acid) (PAA) as polycation and polyanion were deposited on surface charged polylactide (PLA) nonwoven to study the relationship of dye absorption capacity of layered-PLA with the number of deposited layers. To produce negatively charged-PLA, acrylic acid (AA) was grafted on the PLA surface (PLA-g-AA) through a chemical redox reaction with the strong oxidizing agent. Spectroscopy analysis, water contact measurement, and FTIR-ATR analysis confirm the successful grafting of AA on the PLA surface through the chemical redox reaction method. In detail, an increase in dye absorption percentage by 19% and immediate absorption of water droplets ensured hydrophilicity of PLA-g-AA surface; and the presence of new carbonyl bond at 1530 cm-¹ and a wide peak of hydroxyl between 3680-3130 cm-¹ confirm AA grafting. In addition, PLA as linear polyester can undergo aminolysis, which is the cleavage of ester bonds and replacement with amid bonds when exposed to an aminolysis agent. Therefore, to produce positively charged PLA, PAMAM as amine-terminated dendritic material was introduced to PLA molecular chains at different conditions; (1) at 60 C for 0.5, 1, 1.5, 2 hours of aminolysis and (2) at room temperature (RT) for 1, 2, 3, and 4 hours of aminolysis. Weight changes and spectrophotometer measurements showed a maximum in weight gain graph and K/S value curve indicating the highest PAMAM attachment at 60 C for 1 hour and RT for 2 hours which is considered as an optimum condition. Also, the emerging new peak around 1650 cm-1 corresponding to N-H bending vibration and double wide peak at around 3670-3170 cm-1 corresponding to N-H stretching vibration confirm PAMAM attachment in selected optimum condition. In the following, regarding the initial surface charge of grafted-PLA, lbl deposition was performed and started with PAA or PAMAM. FTIR-ATR results confirm chemical changes in samples due to deposition of the first layer (PAA or PAMAM). Generally, spectroscopy analysis indicated that an increase in layer number costed dye absorption capacity. It can be due to the partial deposition of a new layer on the previously deposited layer; therefore, the available PAMAM at the first layer is more than the third layer. In detail, in the case of layer-PLA starting lbl with negatively charged, having PAMAM as the first top layer (PLA-g-AA/PAMAM) showed the highest dye absorption of both cationic and anionic model dye.

Keywords: surface modification, layer-by-layer technique, dendritic materials, PAMAM, dye absorption capacity, PLA nonwoven

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Authors: El Hatka Hicham, Hafidi Youssef, Saghiri Khalid, Ittobane Najim

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Flexible polyurethane foam (FPUF) is a low-density cellular material generally used as a cushioning material in many applications such as furniture, bedding, packaging, etc. It is commercially produced during a continuous process, where a reactive mixture of foam chemicals is poured onto a moving conveyor. FPUFs are produced by the catalytic balancing of two reactions involved, the blowing reaction (isocyanate-water) and the gelation reaction (isocyanate-polyol). The microstructure of FPUF is generally composed of soft phases (polyol phases) and rigid domains that separate into two domains of different sizes: the rigid polyurea microdomains and the macrodomains (larger aggregates). The morphological features of FPUF are strongly influenced by the phase separation morphology that plays a key role in determining the global FPUF properties. This phase-separated morphology results from a thermodynamic incompatibility between soft segments derived from aliphatic polyether and hard segments derived from the commonly used aromatic isocyanate. In order to improve the properties of FPUF against the different stresses faced by this material during its use, we report in this work a study of the phase separation phenomenon in FPUF that has been examined using SAXS WAXS and FTIR. Indeed, we have studied with these techniques the effect of water, isocyanates, and alkaline chlorides on the phase separation behavior. SAXS was used to study the morphology of the microphase separated, WAXS to examine the nature of the hard segment packing, and FTIR to investigate the hydrogen bonding characteristics of the materials studied. The prepared foams were shown to have different levels of urea phase connectivity; the increase in water content in the FPUF formulation leads to an increase in the amount of urea formed and consequently the increase of the size of urea aggregates formed. Alkali chlorides (NaCl, KCl, and LiCl) incorporated into FPUF formulations show that is the ability to prevent hydrogen bond formation and subsequently alter the rigid domains. FPUFs prepared by different isocyanate structures showed that urea aggregates are difficult to be formed in foams prepared by asymmetric diisocyanate, while are more easily formed in foams prepared by symmetric and aliphatic diisocyanate.

Keywords: flexible polyurethane foam, hard segments, phase separation, soft segments

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Authors: Chia-Ling Li

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The scope of this article includes the production of 10,000 metric tons of non-phthalate per annum. The production process will include hydrogenation, separation, purification, and recycling of unprocessed feedstock. Based on experimental data, conversion and selectivity were chosen as reaction model parameters. The synthesis and separation processes of non-phthalate and phthalate were established by using Aspen Plus software. The article will be divided into six parts: estimation of physical properties, integration of production processes, purification case study, utility consumption, economic feasibility study and identification of bottlenecks. The purities of products was higher than 99.9 wt. %. Process parameters have important guiding significance to the commercialization of hydrogenation of phthalate.

Keywords: economic analysis, hydrogenation, non-phthalate, process simulation

Procedia PDF Downloads 277

Authors: Ketevan Janashia, Tamar Tsibadze, Levan Tvildiani, Nikoloz Invia, Elguja Kubaneishvili, Vasili Kukhianidze, George Ramishvili

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This study considers the possible effects of geomagnetic activity (GMA) on humans situated on Earth by performing experiments concerning specific sensitive reactions in humans in both: natural conditions during different GMA and by the simulation of different GMA in the lab. The measurements of autonomic nervous system (ANS) responses to different GMA via measuring the heart rate variability (HRV) indices and stress index (SI) and their comparison with the K-index of GMA have been presented and discussed. The results of experiments indicate an intensification of the sympathetic part of the ANS as a stress reaction of the human organism when it is exposed to high level of GMA as natural as well as in simulated conditions. Aim: We tested the hypothesis whether the GMF when disturbed can have effects on human ANS causing specific sensitive stress-reactions depending on the initial type of ANS. Methods: The study focuses on the effects of different GMA on ANS by comparing of HRV indices and stress index (SI) of n= 78, 18-24 years old healthy male volunteers. Experiments were performed as natural conditions on days of low (K= 1-3) and high (K= 5-7) GMA as well as in the lab by the simulation of different GMA using the device of geomagnetic storm (GMS) compensation and simulation. Results: In comparison with days of low GMA (K=1-3) the initial values of HRV shifted towards the intensification of the sympathetic part (SP) of the ANS during days of GMSs (K=5-7) with statistical significance p-values: HR (heart rate, p= 0.001), SDNN (Standard deviation of all Normal to Normal intervals, p= 0.0001), RMSSD (The square root of the arithmetical mean of the sum of the squares of differences between adjacent NN intervals, p= 0.0001). In comparison with conditions during GMSs compensation mode (K= 0, B= 0-5nT), the ANS balance was observed to shift during exposure to simulated GMSs with intensities in the range of natural GMSs (K= 7, B= 200nT). However, the initial values of the ANS resulted in different dynamics in its variation depending of GMA level. In the case of initial balanced regulation type (HR > 80) significant intensification of SP was observed with p-values: HR (p= 0.0001), SDNN (p= 0.047), RMSSD (p= 0.28), LF/HF (p=0.03), SI (p= 0.02); while in the case of initial parasympathetic regulation type (HR < 80), an insignificant shift to the intensification of the parasympathetic part (PP) was observed. Conclusions: The results indicate an intensification of SP as a stress reaction of the human organism when it is exposed to high level of GMA in both natural and simulated conditions.

Keywords: autonomic nervous system, device of magneto compensation/simulation, geomagnetic storms, heart rate variability

Procedia PDF Downloads 142

Authors: Mouna Mesbahi, M. Loutfi Benkhedir

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In CZTS films solar cell, the preferable reaction between Cu and sulfur vapor was likely to be induced by out diffusion of the bottom Cu component to the surface; this would lead to inhomogeneous distribution of the Cu component to form the Cu2SnS3 secondary phase and formation of many voids and crevices in the resulting CZTS film; which is also the cause of the decline in performance. In this work we study the electronic and optical properties of Cu2SnS3. For this purpose we used the Wien2k code based on the theory of density functional theory (DFT) with the modified Becke-Johnson exchange potential mBJ and the Hubbard potential individually or combined. We have found an energy gap 0.92 eV. The results are in good agreement with experimental results.

Keywords: Cu2SnS3, DFT, electronic and optical properties, mBJ+U, WIEN2K

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Authors: Łukasz Mazur, Kamil Domaradzki, Bartosz Kamecki, Justyna Ignaczak, Sebastian Molin, Aleksander Gil, Tomasz Brylewski

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The rising global power consumption necessitates the development of new energy storage solutions. Prospective technologies include solid oxide electrolyzer cells (SOECs), which convert surplus electrical energy into hydrogen. An electrolyzer cell consists of a porous anode, and cathode, and a dense electrolyte. Power output is increased by connecting cells into stacks using interconnects. Interconnects are currently made from high-chromium ferritic steels – for example, Crofer 22 APU – which exhibit high oxidation resistance and a thermal expansion coefficient that is similar to that of electrode materials. These materials have one disadvantage – their area-specific resistance (ASR) gradually increases due to the formation of a Cr₂O₃ scale on their surface as a result of oxidation. The chromia in the scale also reacts with the water vapor present in the reaction media, forming volatile chromium oxyhydroxides, which in turn react with electrode materials and cause their deterioration. The electrochemical efficiency of SOECs thus decreases. To mitigate this, the interconnect surface can be modified with protective-conducting coatings of spinel or other materials. The high prices of SOEC components -especially the Crofer 22 APU- have prevented their widespread adoption. More inexpensive counterparts, therefore, need to be found, and their properties need to be enhanced to make them viable. Candidates include the Nirosta 4016/1,4016 low-chromium ferritic steel with a chromium content of just 16.3 wt%. This steel's resistance to high-temperature oxidation was improved by depositing Gd₂O₃ nanoparticles on its surface via either dip coating or electrolysis. Modification with CeO₂ or Ce₀.₉Y₀.₁O₂ nanoparticles deposited by means of spray pyrolysis was also tested. These methods were selected because of their low cost and simplicity of application. The aim of this study was to investigate the oxidation kinetics of Nirosta 4016/1,4016 modified using the afore-mentioned methods and to subsequently measure the obtained samples' ASR. The samples were oxidized for 100 h in the air as well as air/H₂O and Ar/H₂/H₂O mixtures at 1073 K. Such conditions reflect those found in the anode and cathode operating space during real-life use of SOECs. Phase and chemical composition and the microstructure of oxidation products were determined using XRD and SEM-EDS. ASR was measured over the range of 623-1073 K using a four-point, two-probe DC technique. The results indicate that the applied nanoparticles improve the oxidation resistance and electrical properties of the studied layered systems. The properties of individual systems varied significantly depending on the applied reaction medium. Gd₂O₃ nanoparticles improved oxidation resistance to a greater degree than either CeO₂ or Ce₀.₉Y₀.₁O₂ nanoparticles. On the other hand, the cerium-containing nanoparticles improved electrical properties regardless of the reaction medium. The ASR values of all surface-modified steel samples were below the 0.1 Ω.cm² threshold set for interconnect materials, which was exceeded in the case of the unmodified reference sample. It can be concluded that the applied modifications increased the oxidation resistance of Nirosta 4016/1.4016 to a level that allows its use as SOEC interconnect material. Acknowledgments: Funding of Research project supported by program "Excellence initiative – research university" for the AGH University of Krakow" is gratefully acknowledged (TB).

Keywords: cerium oxide, ferritic stainless steel, gadolinium oxide, interconnect, SOEC

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Authors: A. M. Tahsini

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Computational study of two dimensional supersonic reacting hydrogen-air flows is performed to investigate the nitrogen effects on ignition delay time for premixed and diffusion flames. Chemical reaction is treated using detail kinetics and the advection upstream splitting method is used to calculate the numerical inviscid fluxes. The results show that only in the stoichiometric condition for both premixed and diffusion flames, there is monotone dependency of the ignition delay time to the nitrogen addition. In other situations, the optimal condition from ignition viewpoint should be found using numerical investigations.

Keywords: diffusion flame, ignition delay time, mixing layer, numerical simulation, premixed flame, supersonic flow

Procedia PDF Downloads 463

Authors: Ž. Vaštag, Lj. Popović, S. Popović

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After cold pressing of pumpkin oil, the defatted oil cake (PUOC) was utilized as raw material for processing of bio-functional hydrolysates. In this study, the in vitro bioactivity of an alcalase (AH) and a pepsin hydrolysate (PH) prepared from the major pumpkin 12S globulin (cucurbitin) are compared. The hydrolysates were produced at optimum reaction conditions (temperature, pH) for the enzymes, during 60min. The bioactivity testing included antioxidant and angiotensin I converting enzyme inhibitory activity assays. The hydrolysates showed high potential as natural antioxidants and possibly antihypertensive agents in functional food or nutraceuticals. Additionally, preliminary studies have shown that both hydrolysates could exhibit modest α-amylase inhibitory activity, which indicates on their hypoglycemic potential.

Keywords: cucurbitin, alcalase, pepsin, protein hydrolysates, in vitro bioactivity

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Authors: S. Tayyebi, F. Mirjalili, H. Samadi, A. Nemati

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In this study, hydroxyapatite-Alumina nano composite powder, containing 15,20 and 25% weight percent of reinforced alumina were prepared by chemical precipitation from the reaction between calcium nitrate tetrahydrate and di-ammonium hydrogen phosphate with ratio of Ca / p = 1.67 and different percentage of aluminum nitrate nona hydrate in different pH of 9,10 and 11. The microstructure and thermal stability of samples were measured by X-ray diffraction (XRD), infrared spectroscopy (FT-IR) and transmission electron microscopy (TEM). The results showed that the presence of reinforced alumina phase reduced the degree of crystallinity of hydroxyapatite phase and increased its decomposition to tricalcium phosphate phase. Microstructural analysis showed that the hydroxyapatite-alumina nano composite powder was obtained with spherical shape and size of less than 100 nm.

Keywords: biomaterial, hydroxyapatite, alumina, nano composite, precipitation method

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Authors: A. Benhadji, M. Taleb Ahmed

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Among the various methods of treatment, advanced oxidation processes (AOP) are the most promising ones. In this study, Peroxi Electrocoagulation Process (PEP) was investigated for the treatment of detergent wastewater. The process was compared with electrooxidation treatment. The results showed that chemical oxygen demand (COD) was high 7584 mgO₂.L^-1, while the biochemical oxygen demand was low (250 mgO₂.L^-1). This wastewater was hardly biodegradable. Electrochemical process was carried out for the removal of detergent using a glass reactor with a volume of 1 L and fitted with three electrodes. A direct current (DC) supply was used. Samples were taken at various current density (0.0227 A/cm² to 0.0378 A/cm²) and reaction time (1-2-3-4 and 5 hour). Finally, the COD was determined. The results indicated that COD removal efficiency of PEP was observed to increase with current intensity and reached to 77% after 5 h. The highest removal efficiency was observed after 5 h of treatment.

Keywords: AOP, COD, detergent, PEP, wastewater

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Authors: Ioan Rusu

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Let us consider that the entire universe is composed of a single hydrogen atom within which the electron is moving around the proton. In this case, according to classical theories of physics, radiation and photons, respectively, should be absorbed by the electron. Depending on the number of photons absorbed, the electron radius of rotation around the proton is established. Until now, the principle of photon absorption by electrons and the electron transition to a new energy level, namely to a higher radius of rotation around the proton, is not clarified in physics. This paper aims to demonstrate that photons have mass and negative electrostatic charge similar to electrons but infinitely smaller. The experiments which demonstrate this theory are simple: thermal expansion, photoelectric effect and thermonuclear reaction.

Keywords: electrostatic, electron, photon, proton, radiation

Procedia PDF Downloads 396

Authors: Keshari Shrestha, Philip Vatterott

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Introduction: Drug reaction with eosinophilia and systemic symptoms (DRESS) syndrome is a rare and potentially fatal drug-related syndrome. DRESS classically presents with a diffuse maculopapular rash, fevers, and eosinophilia more than three weeks after drug exposure. DRESS can present with multi-organ involvement, with liver damage being the most common and severe. Pulmonary involvement is a less common manifestation and is associated with poor clinical outcomes. Chest imaging is often nonspecific, and symptoms can range from mild cough to acute respiratory distress syndrome (ARDS) . This is a case of a 49-year-old female with a history of recent clostridium difficile colitis status post treatment with oral vancomycin who presented with rash, acute liver and kidney failure, as well as diffuse nodular alveolar lung opacities concerning for DRESS syndrome with multi-organ involvement. Clinical Course: This patient initially presented to an outside hospital with clostridium difficile colitis, acute liver injury, and acute kidney injury. She developed a desquamating maculopapular rash in the setting of recent oral vancomycin, meloxicam, and furosemide initiation. She was hospitalized on two additional occasions with worsening altered mental status, liver injury, and acute kidney injury and was initiated on intermittent hemodialysis. Notably, she was found to have systemic eosinophilia (4100 cells/microliter) several weeks prior. She was transferred to this institution for further management where she was found to have encephalopathy, jaundice, lower extremity edema, and diffuse bilateral rhonchorous breath sounds on pulmonary examination. The patient was started on methylprednisolone for suspected DRESS syndrome. She underwent an evaluation for alternative causes of her organ failure. Her workup included a negative infectious, autoimmune, metabolic, toxic, and malignant work-up. Abdominal computed tomography (CT) and ultrasound were remarkable for evidence of hepatic steatosis and possible cirrhotic morphology. Additionally, a chest CT demonstrated diffuse and symmetric nodular alveolar lung opacities with peripheral sparing not consistent with acute respiratory distress syndrome or edema. Ultimately, her condition continued to decline, and she required intubation on several occasions. On hospital day 25 she succumbed to distributive shock in the setting of probable sepsis and multi-organ failure. Discussion: DRESS syndrome occurs in 1 in 1,000 to 10,000 patients with a mortality rate of around 10%. Anti-convulsant, anti-bacterial, anti-viral, and sulfonamide drugs are the most common drugs implicated in the development of DRESS syndrome; however, the list of offending agents is extensive . The diagnosis of DRESS syndrome is made after excluding other causes of disease such as infectious and autoimmune etiologies. The RegiSCAR scoring system is used to diagnose DRESS syndrome with 2-3 points indicating possible disease, 4-5 probable disease, and >5 definite disease. This patient scored a 7 on the RegiSCAR scale for eosinophilia, rash, organ involvement, and exclusion of other causes (infectious and autoimmune). While the pharmacologic trigger in this case is unknown, it is speculated to be caused by vancomycin, meloxicam, or furosemide due to the favorable timeline of initiation. Despite aggressive treatment, DRESS syndrome can often be fatal. Because of this, early diagnosis and treatment of patients with suspected DRESS syndrome is imperative.

Keywords: drug reaction with eosinophilia and systemic symptoms, multi-organ failure, pulmonary involvement, renal failure

Procedia PDF Downloads 171