Search results for: cerebrovascular reactivity

Authors: Carlos Alberto Ríos Reyes

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Traditionally, clays have been considered as one of the main problems in the flow of fluids in hydrocarbon reservoirs. However, there is not known the significance of zeolites formed from the reactivity of clays and their effect not only on the costs of operations carried out by the oil industry in the world but also on production. The present work focused on understanding the interaction between clay minerals with brines and alkaline solutions used in the oil industry. For this, a comparative study was conducted where the reaction of sedimentary rocks under laboratory conditions was examined. Original and treated rocks were examined by X-ray powder diffraction (XRPD) and Scanning Electron Microscopy (SEM) to determine the changes that these rocks underwent upon contact with fluids of variable chemical composition. As a result, zeolite Linde Type A (LTA), sodalite (SOD), and cancrinite (CAN) can be formed after experimental work, which coincided with the dissolution of kaolinite and smectite. Results reveal that the Oil Industry should invest efforts and focus its gaze to understand at the pore scale the problem that could arise as a consequence of the clay-fluid interaction in hydrocarbon reservoir rocks due to the presence of clays in their porous system, as well as the formation of zeolites, which are better hydrocarbon absorbents. These issues could be generating losses in world production. We conclude that there is a critical situation that may be occurring in the stimulation of hydrocarbon reservoirs, where real solutions are necessary not only for the formulation of more efficient and effective injection fluids but also to contribute to the improvement of production and avoid considerable losses in operating costs.

Keywords: clay minerals, zeolites, rock-fluid interaction, experimental work, reactivity

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Authors: Asmaa M. Fahim

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In this elucidation, we synthesized different heterocyclic compounds attached to Benzene sulfonamide moiety via (E)-N-(4-(3-(4-bromophenyl)acryloyl)phenyl)-4-methyl benzene sulfonamide which is obtained from Nucleophilic substitution reaction between 4-methylbenzene sulfonyl chloride and 1-(4-aminophenyl)ethan-1-one in pyridine to get N-(4-acetyl phenyl)-4-methyl benzenesulfonamide which reacted 4-bromobenzal dehyde undergoes aldol condensation in NaOH to afford the corresponding chalchone 4. Moreover, the reactivity of chalchone 4 showed several active methylene derivatives utilized the pressurized microwave irradiation as a green energy resource. Chalcone 4 was allowed to react with ethyl cyanoacetate and acetylacetone, respectively, at 70 °C with pressure under microwave reaction condition to afford the 5-cyano-6-oxo-1,2,5,6-tetrahydropyridin-2-yl)-4-methylbenzenesulfonamide 6 and N-(4'-acetyl-4''-bromo-5'-oxo-2',3',4',5'-tetrahydro-[1,1':3',1''-terphenyl]-4-yl)-4-methylbenzenesulfonamide 8 derivatives. Moreover, the reactivity of this sulphonamide chalchone with NH2NH2 in EtOH and acetic acid, which gave 2,5-dihydro-1H-imidazol-4-yl)-4-methyl benzenesulfonamide, 1H-pyrazol-3-yl)-4-methyl and reactivity with NH2OH.HCl gave isoxazol-3-yl)-4-methylbenzenesulfonamide derivatives. The synthesized compounds were screened for their ADME properties and directed to antitumor activity on HepG2 hepatocellular carcinoma and MCF-7 breast cancer and exhibited excellent behavior against standard drugs; these results were confirmed through molecular simulations with different proteins. Additionally, the Density Functional Theory analysis of optimized structures investigated their physical descriptors, FMO, ESP and MEP, which correlated with biological evaluation.

Keywords: synthesis, green chemistry, antitumor activity, DFT study

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Authors: Ameur Soukaina, Zeroual Abdellah, Mazoir Noureddine

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Molecular Electron Density Theory (MEDT) elucidates the regioselectivity of the [4+2] cycloaddition reaction between 3-aroylpyrrolo[1,2-α]quinoxaline-1,2,4(5H)-trione and butyl vinyl ether Regioselectivity and stereoselectivity. The regioselectivity mechanisms of these reactions were investigated by evaluating potential energy surfaces calculated for cycloaddition processes and DFT density-based reactivity indices. These methods have been successfully applied to predict preferred regioisomers for different method alternatives. Reactions were monitored by performing transition state optimizations, calculations of intrinsic reaction coordinates, and activation energies. The observed regioselectivity was rationalized using DFT-based reactivity descriptors such as the Parr function. Solvent effects were also investigated in 1,4-dioxane solvent using a field model for self-consistent reactions. The results were compared with experimental data to find good agreement.

Keywords: cycloaddition, DFT, ELF, MEDT, parr, stereoselectivité

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Authors: I. S. Gandhi, D. N. Patel, M. Johnson, A. R. Hirsch

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Although distortion of taste perception following a cerebrovascular event may seem to be a frivolous consequence of a classic stroke presentation, altered taste perception places patients at an increased risk for malnutrition, weight loss, and depression, all of which negatively impact the quality of life. Impaired taste perception can result from a wide variety of cerebrovascular lesions to various locations, including pons, insular cortices, and ventral posteromedial nucleus of the thalamus. Wallenberg syndrome, also known as a lateral medullary syndrome, has been described to impact taste; however, specific sweet to bitter taste dysgeusia from a territory infarction is an infrequent event; as such, a case is presented. One year prior to presentation, this 64-year-old right-handed woman, suffered a right posterior inferior cerebellar artery aneurysm rupture with resultant infarction, culminating in a ventriculoperitoneal shunt placement. One and half months after this event, she noticed the gradual onset of lack of ability to taste sweet, to eventually all sweet food tasting bitter. Since the onset of her chemosensory problems, the patient has lost 60-pounds. Upon gustatory testing, the patient's taste threshold showed ageusia to sucrose and hydrochloric acid, while normogeusia to sodium chloride, urea, and phenylthiocarbamide. The gustatory cortex is made in part by the right insular cortex as well as the right anterior operculum, which are primarily involved in the sensory taste modalities. In this model, sweet is localized in the posterior-most along with the rostral aspect of the right insular cortex, notably adjacent to the region responsible for bitter taste. The sweet to bitter dysgeusia in our patient suggests the presence of a lesion in this localization. Although the primary lesion in this patient was located in the right medulla of the brainstem, neurodegeneration in the rostal and posterior-most aspect, of the right insular cortex may have occurred due to diaschisis. Diaschisis has been described as neurophysiological changes that occur in remote regions to a focal brain lesion. Although hydrocephalus and vasospasm due to aneurysmal rupture may explain the distal foci of impairment, the gradual onset of dysgeusia is more indicative of diaschisis. The perception of sweet, now tasting bitter, suggests that in the absence of sweet taste reception, the intrinsic bitter taste of food is now being stimulated rather than sweet. In the evaluation and treatment of taste parageusia secondary to cerebrovascular injury, prophylactic neuroprotective measures may be worthwhile. Further investigation is warranted.

Keywords: diaschisis, dysgeusia, stroke, taste

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Authors: Yousef M. Alammari, Mahmoud A. Gaddoury, Reem A. Almohaini, Sara A. Alharbi, Lena S. Alsaleem, Lujain H. Allowaihiq, Maha H. Alrashid, Abdullah H. Alghamdi, Abdullah A. Alaryni

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Objective: The goal of this study was to establish the prevalence of neuropsychiatric symptoms in systemic lupus erythematosus (NPSLE) patients in Saudi Arabia and the variables that are linked to it. Methods: During June 2021, this cross-sectional study was carried out among SLE patients in Saudi Arabia. The Saudi Rheumatism Association exploited social media platforms to provide a self-administered online questionnaire to SLE patients. All data analyses were performed using the Statistical Packages for Social Sciences (SPSS) version 26. Results: Two hundred and five SLE patients participated in the study (females 91.3 % vs. males 8.7 %). In addition, 13.5 % of patients had a family history of SLE, and 26% had SLE for one to three years. Alteration or loss of sensation (53.4%), Fear (52.4%), and headache (48.1%) were the most prevalent signs of neuropsychiatric symptoms in systemic lupus erythematosus (NPSLE) patients. The prevalence of patients with NPSLE was 40%. In a multivariate regression model, fear, altered sensations, cerebrovascular illness, sleep disruption, and diminished interest in routine activities were identified as independent risk variables for NPSLE. Conclusion: Nearly half of SLE patients demonstrated NP manifestations, with significant symptoms including fear, alteration of sensation, cerebrovascular disease, sleep disturbance, and reduced interest in normal activities. To detect the pathophysiology of NPSLE, it is necessary to understand the relationship between neuropsychiatric morbidity and other relevant rheumatic disorders in the SLE population.

Keywords: neuropsychiatric, systemic lupus erythematosus, NPSLE, prevalence, SLE patients

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Authors: Eman G. Alayad, Mazen G. Aleyad, Mohammed Alshahrani, Ibrahim Alnaami

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Introduction: Cerebral venous thrombosis (CVT) is a rare type of cerebrovascular disease that can occur at any age. Patients with CVT commonly present with headache, focal neurological deficit, decreased level of consciousness and seizures. Many etiologic risk factors have been reported for CVT, high altitude and oral contraceptive pill some of them. Case Presentation: A 37-year-old woman living in Abha city in the southeastern area of Saudi Arabia. (about 10,000 feet-3000 m) over the sea. complaining acute onset of severe diffuse headache and generalized tonic clonic convulsions. Followed by loss of consciousness. She was on contraceptive pills for the last 3 years. No significant Medical or surgical history. Brain CT revealed subarachnoid hemorrhage, with MRI findings showing thrombosis in transvers sinus. There was no vascular malformations such as aneurysm, arteriovenous malformation (AVM), or dural arteriovenous fistula. A CVT with subarachnoid hemorrhage was our final diagnosis based on clinical presentation and radiographic findings. Discussion: Patients with CVT had evidence of cortical SAH by 10 of 233, others found 3% of SAH was caused by CVT, indicating that the presence of cortical SAH without involvement of the basal cisterns may provide an early sign of underlying CVT. However, what is more interesting in this case, is the relationship of high altitude with CVT and SAH, which previously undescribed. Conclusion: High-altitude climbing per se was described as a risk factor for the development of CVT, though its occurrence was probably rare. Whether it is primary in etiology due to high altitude induced hypercoagulable state of unknown origin or due to cerebrovascular disturbances there is a need for further investigation especially at this unusual presentation of subarachnoid hemorrhage.

Keywords: cerebral venous thrombosis, high-altitude, subarachnoid hemorrhage, stroke

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Authors: D. S. Gomes, A. T. Silva

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Analysis of the uncertainty quantification related to nuclear safety margins applied to the nuclear reactor is an important concept to prevent future radioactive accidents. The nuclear fuel performance code may involve the tolerance level determined by traditional deterministic models producing acceptable results at burn cycles under 62 GWd/MTU. The behavior of nuclear fuel can simulate applying a series of material properties under irradiation and physics models to calculate the safety limits. In this study, theoretical predictions of nuclear fuel failure under transient conditions investigate extended radiation cycles at 75 GWd/MTU, considering the behavior of fuel rods in light-water reactors under reactivity accident conditions. The fuel pellet can melt due to the quick increase of reactivity during a transient. Large power excursions in the reactor are the subject of interest bringing to a treatment that is known as the Fuchs-Hansen model. The point kinetic neutron equations show similar characteristics of non-linear differential equations. In this investigation, the multivariate logistic regression is employed to a probabilistic forecast of fuel failure. A comparison of computational simulation and experimental results was acceptable. The experiments carried out use the pre-irradiated fuels rods subjected to a rapid energy pulse which exhibits the same behavior during a nuclear accident. The propagation of uncertainty utilizes the Wilk's formulation. The variables chosen as essential to failure prediction were the fuel burnup, the applied peak power, the pulse width, the oxidation layer thickness, and the cladding type.

Keywords: logistic regression, reactivity-initiated accident, safety margins, uncertainty propagation

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Authors: Ji Hoon Kim, Jong Man Kim, Hyung Woo Lee, Soo Hyung Kim

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The applications of nanoenergetic materials (nEMs) could be extended by developing more convenient and reliable ignition methods. However, the underwater ignition of nEMs is a significant challenge because water perturbs the reactants prior to ignition and also quenches the subsequent combustion reaction of nEMs upon ignition. In this study, we developed flash and laser-ignitable nEMs for underwater explosion. This was achieved by adding various carbon nanotubes (CNTs) as the optical igniter into an nEM matrix, composed of Al/CuO nanoparticles. The CNTs absorb the irradiated optical energy and rapidly convert it into thermal energy, and then the thermal energy is concentrated to ignite the core catalysts and neighboring nEMs. The maximum burn rate was achieved by adding 1 wt% CNTs into the nEM matrix. The burn rate significantly decreased with increasing amount of CNTs (≥ 2 wt%), indicating that the optical ignition and controlled-explosion reactivity of nEMs are possible by incorporating an appropriate amount of CNTs.

Keywords: nanoenergetic materials, carbon nanotubes, optical ignition, tunable explosion

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Authors: Geeta Kumari, Prabu Vairakannu

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Underground coal gasification (UCG) technology is an efficient and an economic in-situ clean coal technology, which converts unmineable coals into calorific valuable gases. This technology avoids ash disposal, coal mining, and storage problems. CO₂ gas can be a potential gasifying medium for UCG. CO₂ is a greenhouse gas and, the liberation of this gas to the atmosphere from thermal power plant industries leads to global warming. Hence, the capture and reutilization of CO₂ gas are crucial for clean energy production. However, the reactivity of high ash Indian coals with CO₂ needs to be assessed. In the present study, two varieties of Indian coals (low ash and high ash) are used for thermogravimetric analyses (TGA). Two low ash north east Indian coals (LAC) and a typical high ash Indian coal (HAC) are procured from the coal mines of India. Low ash coal with 9% ash (LAC-1) and 4% ash (LAC-2) and high ash coal (HAC) with 42% ash are used for the study. TGA studies are carried out to evaluate the activation energy for pyrolysis and gasification of coal under N₂ and CO₂ atmosphere. Coats and Redfern method is used to estimate the activation energy of coal under different temperature regimes. Volumetric model is assumed for the estimation of the activation energy. The activation energy estimated under different temperature range. The inherent properties of coals play a major role in their reactivity. The results show that the activation energy decreases with the decrease in the inherent percentage of coal ash due to the ash layer hindrance. A reverse trend was observed with volatile matter. High volatile matter of coal leads to the estimation of low activation energy. It was observed that the activation energy under CO₂ atmosphere at 400-600°C is less as compared to N₂ inert atmosphere. At this temperature range, it is estimated that 15-23% reduction in the activation energy under CO₂ atmosphere. This shows the reactivity of CO₂ gas with higher hydrocarbons of the coal volatile matters. The reactivity of CO₂ with the volatile matter of coal might occur through dry reforming reaction in which CO₂ reacts with higher hydrocarbon, aromatics of the tar content. The observed trend of Ea in the temperature range of 150-200˚C and 400-600˚C is HAC > LAC-1 >LAC-2 in both N₂ and CO₂ atmosphere. At the temperature range of 850-1000˚C, higher activation energy is estimated when compared to those values in the temperature range of 400-600°C. Above 800°C, char gasification through Boudouard reaction progressed under CO₂ atmosphere. It was observed that 8-20 kJ/mol of activation energy is increased during char gasification above 800°C compared to volatile matter pyrolysis between the temperature ranges of 400-600°C. The overall activation energy of the coals in the temperature range of 30-1000˚C is higher in N₂ atmosphere than CO₂ atmosphere. It can be concluded that higher hydrocarbons such as tar effectively undergoes cracking and reforming reactions in presence of CO₂. Thus, CO₂ gas is beneficial for the production of high calorific value syngas using high ash Indian coals.

Keywords: clean coal technology, CO₂ gasification, activation energy, underground coal gasification

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Authors: Raj Raghupathy

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Recurrent Spontaneous Miscarriage (RSM) is a common form of pregnancy loss, 50% of which are due to ‘unexplained’ causes. Evidence exists to suggest that RSM may be caused by immunologic factors such as cytokines which are critical molecules of the immune system, with an impressive array of capabilities. An association appears to exist between Th2-type reactivity (mediated by Th2 or anti-inflammatory cytokines) and normal, successful pregnancy, and between unexplained RSM and Th1 cytokine dominance. If pro-inflammatory cytokines are indeed associated with pregnancy loss, the suppression of these cytokines, and thus the ‘redirection’ of maternal reactivity, may help prevent cytokine-mediated pregnancy loss. The objective of this study was to explore the possibility of modulating cytokine production using Dydrogesterone (Duphaston®), an orally-administered progestogen. Peripheral blood mononuclear cells from 34 women with a history of at least 3 unexplained recurrent miscarriages were stimulated in vitro with a mitogen (to elicit cytokine production) in the presence and absence of dydrogesterone. Levels of selected pro- and anti-inflammatory cytokines produced by peripheral blood mononuclear cells were measured after exposure to these progestogens. Dydrogesterone down-regulates the production of pro-inflammatory cytokines and up-regulates the production of anti-inflammatory cytokines. The ratios of Th2 to Th1 cytokines are markedly elevated in the presence of dydrogesterone, indicating a shift from potentially harmful maternal Th1 reactivity to a more pregnancy-conducive Th2 profile. We used a progesterone receptor antagonist to show that this cytokine-modulating effect of dydrogesterone is mediated via the progesterone receptor. Dydrogesterone also induces the production of the Progesterone-Induced Blocking Factor (PIBF); lymphocytes exposed to PIBF produce higher levels of Th2 cytokines, affecting a Th1 → Th2 cytokine shift which could be favourable to the success of pregnancy. We conclude that modulation of maternal cytokine production profiles is possible with dydrogesterone which has the merits that it can be administered orally and that it is safe.

Keywords: cytokines, dydrogesterone, progesterone, recurrent spontaneous miscarriage

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Authors: Erin M. Durke, Monica L. McEntee, Meilu He, Suresh Dhaniyala

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Aerosols are one of the most important and significant surfaces in the atmosphere. They can influence weather, absorption, and reflection of light, and reactivity of atmospheric constituents. A notable feature of aerosol particles is the presence of a surface charge, a characteristic imparted via the aerosolization process. The existence of charge can complicate the interrogation of aerosol particles, so many researchers remove or neutralize aerosol particles before characterization. However, the charge is present in real-world samples, and likely has an effect on the physical and chemical properties of an aerosolized material. In our studies, we aerosolized different materials in an attempt to characterize the charge imparted via the aerosolization process and determine what impact it has on the aerosolized materials’ properties. The metal oxides, TiO₂ and SiO₂, were aerosolized expulsively and then characterized, using several different techniques, in an effort to determine the surface charge imparted upon the particles via the aerosolization process. Particle charge distribution measurements were conducted via the employment of a custom scanning mobility particle sizer. The results of the charge distribution measurements indicated that expulsive generation of 0.2 µm SiO₂ particles produced aerosols with upwards of 30+ charges on the surface of the particle. Determination of the degree of surface charging led to the use of non-traditional techniques to explore the impact of additional surface charge on the overall reactivity of the metal oxides, specifically TiO₂. TiO₂ was aerosolized, again expulsively, onto a gold-coated tungsten mesh, which was then evaluated with transmission infrared spectroscopy in an ultra-high vacuum environment. The TiO₂ aerosols were exposed to O₂, H₂, and CO, respectively. Exposure to O₂ resulted in a decrease in the overall baseline of the aerosol spectrum, suggesting O₂ removed some of the surface charge imparted during aerosolization. Upon exposure to H₂, there was no observable rise in the baseline of the IR spectrum, as is typically seen for TiO₂, due to the population of electrons into the shallow trapped states and subsequent promotion of the electrons into the conduction band. This result suggests that the additional charge imparted via aerosolization fills the trapped states, therefore no rise is seen upon exposure to H₂. Dosing the TiO₂ aerosols with CO showed no adsorption of CO on the surface, even at lower temperatures (~100 K), indicating the additional charge on the aerosol surface prevents the CO molecules from adsorbing to the TiO₂ surface. The results observed during exposure suggest that the additional charge imparted via aerosolization impacts the interaction with each probe gas.

Keywords: aerosols, charge, reactivity, infrared

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Authors: Caroline Alice Rouget-Virbel, F. Dean Toste

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Heterobimetallic systems have been precedented in a wide array of bioinorganic and heterogeneous catalytic settings, in which cooperative bond-breaking and bond-forming events mediated by neighboring metal sites have been proposed but are challenging to study and characterize. Heterodinuclear transition-metal catalysis has recently emerged as a promising strategy to tackle challenging chemical transformations, including C−C and C−X couplings as well as small molecule activation. It has been shown that these reactions can traverse nontraditional mechanisms, reactivities, and selectivities when homo- and heterobimetallic systems are employed. Moreover, stoichiometric studies of transmetallation from gold complexes have demonstrated that R transfer from PPh3–Au(I)R to Cp- and Cp*-ligated group 8/9 complexes is a viable elementary step. With these considerations in mind, we hypothesized that heterobimetallic Au–M complexes could serve as a viable and tunable catalyst platform to explore mechanisms and reactivity. In this work, heterobimetallic complexes containing Au(I) centers tethered to Ir(III) and Rh(III) piano stool moieties were synthesized and characterized. Preliminary application of these complexes to a catalytic allylic arylation reaction demonstrates bimetallic cooperativity relative to their monomeric metal components.

Keywords: heterobimetallic, catalysis, gold, rhodium

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Authors: Tom S. Owens, Tom A. Calverley, Benjamin S. Stacey, Christopher J. Marley, George Rose, Lewis Fall, Gareth L. Jones, Priscilla Williams, John P. R. Williams, Martin Steggall, Damian M. Bailey

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Introduction and aims: Sports-related concussion (SRC) represents a significant and growing public health concern in rugby union, yet remains one of the least understood injuries facing the health community today. Alongside increasing SRC incidence rates, there is concern that prior recurrent concussion may contribute to long-term neurologic sequelae in later-life. This may be due to an accelerated decline in cerebral perfusion, a major risk factor for neurocognitive decline and neurodegeneration, though the underlying mechanisms remain to be established. The present study hypothesised that recurrent concussion in current professional rugby union players would result in elevated systemic oxidative-nitrosative stress, reflected by a free radical-mediated reduction in nitric oxide (NO) bioavailability and impaired cerebrovascular and cognitive function. Methodology: A longitudinal study design was adopted across the 2017-2018 rugby union season. Ethical approval was obtained from the University of South Wales Ethics Committee. Data collection is ongoing, and therefore the current report documents result from the pre-season and first half of the in-season data collection. Participants were initially divided into two subgroups; 23 professional rugby union players (aged 26 ± 5 years) and 22 non-concussed controls (27 ± 8 years). Pre-season measurements were performed for cerebrovascular function (Doppler ultrasound of middle cerebral artery velocity (MCAv) in response to hypocapnia/normocapnia/hypercapnia), cephalic venous concentrations of the ascorbate radical (A•-, electron paramagnetic resonance spectroscopy), NO (ozone-based chemiluminescence) and cognition (neuropsychometric tests). Notational analysis was performed to assess contact in the rugby group throughout each competitive game. Results: 1001 tackles and 62 injuries, including three concussions were observed across the first half of the season. However, no associations were apparent between number of tackles and any injury type (P > 0.05). The rugby group expressed greater oxidative stress as indicated by increased A•- (P < 0.05 vs. control) and a subsequent decrease in NO bioavailability (P < 0.05 vs. control). The rugby group performed worse in the Ray Auditory Verbal Learning Test B (RAVLT-B, learning, and memory) and the Grooved Pegboard test using both the dominant and non-dominant hands (visuomotor coordination, P < 0.05 vs. control). There were no between-group differences in cerebral perfusion at baseline (MCAv: 54 ± 13 vs. 59 ± 12, P > 0.05). Likewise, no between-group differences in CVRCO2Hypo (2.58 ± 1.01 vs. 2.58 ± 0.75, P > 0.05) or CVRCO2Hyper (2.69 ± 1.07 vs. 3.35 ± 1.28, P > 0.05) were observed. Conclusion: The present study identified that the rugby union players are characterized by impaired cognitive function subsequent to elevated systemic-oxidative-nitrosative stress. However, this appears to be independent of any functional impairment in cerebrovascular function. Given the potential long-term trajectory towards accelerated cognitive decline in populations exposed to SRC, prophylaxis to increase NO bioavailability warrants consideration.

Keywords: cognition, concussion, mild traumatic brain injury, rugby

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Authors: Suresh Vanguri, Suresh Palla, K. V. Kalyani, S. K. Chaturvedi, B. N. Mohapatra

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Enhancing the fly ash utilization in the manufacture of cement is identified as one of the key areas to mitigate the Green House Gas emissions from the cement industry. Though increasing the fly ash content in cement has economic and environmental benefits, it results in a decrease in the compressive strength values, particularly at early ages. Quality of clinker and fly ash were identified as predominant factors that govern the extent of absorption of fly ash in the manufacturing of cement. This paper presents systematic investigations on the effect of clinker and fly ash quality on the properties of resultant cement. Since mechanical activation alters the physicochemical properties such as particle size distribution, surface area, phase morphology, understanding the variation of these properties with activation is required for its applications. The effect of mechanical activation on fly ash surface area, specific gravity, flow properties, lime reactivity, comparative compressive strength (CCS), reactive silica and mineralogical properties were also studied. The fineness of fly ash was determined by Blaine’s method, specific gravity, lime reactivity, CCS were determined as per the method IS 1727-1967. The phase composition of fly ash was studied using the X-ray Diffraction technique. The changes in the microstructure and morphology with activation were examined using the scanning electron microscope. The studies presented in this paper also include evaluation of Portland Pozzolana Cement (PPC), prepared using high volume fly ash. Studies are being carried out using clinker from cement plants located in different regions/clusters in India. Blends of PPC containing higher contents of activated fly ash have been prepared and investigated for their chemical and physical properties, as per Indian Standard procedures. Changes in the microstructure of fly ash with activation and mechanical properties of resultant cement containing high volumes of fly ash indicated the significance of optimization of the quality of clinker and fly ash fineness for better techno-economical benefits.

Keywords: flow properties, fly ash enhancement, lime reactivity, microstructure, mineralogy

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Authors: Sylvain Caillol, Ghislain David

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Phenolic resins are industrially used in a wide range of applications from commodity and construction materials to high-technology aerospace industry. They are mainly produced from the reaction between phenolic compounds and formaldehyde. Nevertheless, formaldehyde is a highly volatile and hazardous compound, classified as a Carcinogenic, Mutagenic and Reprotoxic chemical (CMR). Vanillin is a bio-based and non-toxic aromatic aldehyde compound obtained from the abundant lignin resources. Also, its aromaticity is very interesting for the synthesis of phenolic resins with high thermal stability. However, because of the relatively low reactivity of its aldehyde function toward phenolic compounds, it has never been used to synthesize phenolic resins. We developed innovative functionalization reactions and designed new bio-based aromatic aldehyde compounds from vanillin. Those innovative compounds present improved reactivity toward phenolic compounds compared to vanillin. Moreover, they have target structures to synthesize highly cross-linked phenolic resins with high aromatic densities. We have obtained phenolic resins from substituted vanillin, thus without the use of any aldehyde compound classified as CMR. The analytical tests of the cured resins confirmed that those bio-based resins exhibit high levels of performance with high thermal stability and high rigidity properties

Keywords: phenolic resins, formaldehyde-free, vanillin, bio-based, non-toxic

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Authors: Wisit Wichitkosoom

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Objective:The majority of the hisk-risk patients (ST-elevation myocardial infarction (STEMI), Acute cerebrovascular accident, Sepsis, Acute Traumatic patient ) are admitted to district or lacal hospitals (average 1-1.30 hr. from Udonthani general hospital, Northeastern province, Thailand) without proper facilities. The referral system was support to early care and early management at pre-hospital stage and prepare for the patient data to higher hospital. This study assessed the reduction in treatment delay achieved by pre-hospital diagnosis and referral directly to Udonthani General Hospital. Methods and results: Four district or local hospitals without proper facilities for treatment the very high-risk patient were serving the study region. Pre-hospital diagnoses were established with the simple technology such as LINE, SMS, telephone and Fax for concept of LEAN process and then the telemedicine, by ambulance monitoring (ECG, SpO2, BT, BP) in both real time and snapshot mode was administrated during the period of transfer for safety transfer concept (inter-hospital stage). The standard treatment for patients with STEMI, Intracranial injury and acute cerebrovascular accident were done. From 1 October 2012 to 30 September 2013, the 892 high-risk patients transported by ambulance and transferred to Udonthani general hospital were registered. Patients with STEMI diagnosed pre-hospitally and referred directly to the Udonthani general hospital with telemedicine closed monitor (n=248). The mortality rate decreased from 11.69% in 2011 to 6.92 in 2012. The 34 patients were arrested on the way and successful to CPR during transfer with the telemedicine consultation were 79.41%. Conclusion: The proper innovation could apply for health care system. The very high-risk patients must had the closed monitoring with two-way communication for the “safety transfer period”. It could modified to another high-risk group too.

Keywords: safety transfer, telemedicine, critical patients, medical and health sciences

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Authors: Brian J. Graham, Ronald T. Raines

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The presence of a nearly vacant p orbital on boron endows boronic acids with unique abilities as a catalyst and ligand. An organocatalytic process has been developed for the conversion of biomass-derived sugars to 5-hydroxymethylfurfural, which is a platform chemical. Specifically, 2-carboxyphenylboronic acid (2-CPBA) has been shown to be an optimal catalyst for this process, promoting the desired transformation in the absence of metals. The attributes of 2-CPBA as a catalyst led to additional investigations of its structure and reactivity. 2-CPBA was found to exist as a cyclized benzoxaborolone adduct rather than a free carboxylic acid. This cyclization has profound consequences for the oxidative stability of the boronic acid. Stereoelectronic effects within the oxaborolone ring destabilize the oxidation transition state by reducing electron donation from the cyclic oxygen to the developing p orbital on boron. That leads to a 10,000-fold increase in oxidative stability while maintaining the normal reactivity of boronic acids toward diols (e.g., carbohydrates) and nucleophiles in proteins while also presenting numerous hydrogen-bond accepting and donating groups. Thus, benzoxaborolones are useful in catalysis, chemical biology, medicinal chemistry, and allied fields.

Keywords: bioisosteres, boronic acid, catalysis, oxidative stability, pharmacophore, stereoelectronic effects

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Authors: Martin Juckel

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Probably no other field of inorganic chemistry has undergone such a rapid development in the past two decades than the low oxidation state chemistry of main group elements. This rapid development has only been possible by the development of new bulky ligands. In case of our research group, super-bulky monodentate amido ligands and β-diketiminate ligands have been used to a great success. We first synthesized the unprecedented magnesium(I) dimer [ᴹᵉˢNacnacMg]₂ (ᴹᵉˢNacnac = [(ᴹᵉˢNCMe)₂CH]-; Mes = mesityl, which has since been used both as reducing agent and also for the synthesis of new metal-magnesium bonds. In case of the zinc bromide precursor [L*ZnBr] (L*=(N(Ar*)(SiPri₃); (Ar* = C₆H₂{C(H)Ph₂}₂Me-2,6,4, the reduction with [ᴹᵉˢNacnacMg]₂ led to such a metal-magnesium bond. This [L*ZnMg(ᴹᵉˢNacnac)] compound can be seen as an ‘inorganic Grignard reagent’, which can be used to transfer the metal fragment onto other functional groups or other metal centers; just like the conventional Grignard reagent. By simple addition of (TBoN)GeCl (TBoN = N(SiMe₃){B(DipNCH)₂) to the aforesaid compound, we were able to transfer the amido-zinc fragment to the Ge center of the germylene starting material and to synthesize the first example of a germanium(II)-zinc bond: [:Ge(TBoN)(ZnL*)]. While these reactions typically led to complex product mixture, [:Ge(TBoN)(ZnL*)] could be isolated as dark blue crystals in a good yield. This new compound shows interesting reactivity towards small molecules, especially dihydrogen gas. This is of special interest as dihydrogen is one of the more difficult small molecules to activate, due to its strong (BDE = 108 kcal/mol) and non-polar bond. In this context, the interaction between H₂ σ-bond with the tetrelylene p-Orbital (LUMO), with concomitant donation of the tetrelylene lone pair (HOMO) into the H₂ σ* orbital are responsible for the activation of dihydrogen gas. Accordingly, the narrower the HOMO-LUMO gap of tertelylene, the more reactivity towards H₂ it typically is. The aim of a narrow HOMO-LUMO gap was reached by transferring electropositive substituents respectively metal substituents with relatively low Pauling electronegativity (zinc: 1.65) onto the Ge center (here: the zinc-amido fragment). In consideration of the unprecedented reactivity of [:Ge(TBoN)(ZnL*)], a computational examination of its frontier orbital energies was undertaken. The energy separation between the HOMO, which has significant Ge lone pair character, and the LUMO, which has predominantly Ge p-orbital character, is narrow (40.8 kcal/mol; cf.∆S-T= 24.8 kcal/mol), and comparable to the HOMO-LUMO gaps calculated for other literature known complexes). The calculated very narrow HOMO-LUMO gap for the [:Ge(TBoN)(ZnL*)] complex is consistent with its high reactivity, and is remarkable considering that it incorporates a π-basic amide ligand, which are known to raise the LUMO of germylenes considerably.

Keywords: activation of dihydrogen gas, narrow HOMO-LUMO gap, first germanium(II)-zinc bond, inorganic Grignard reagent

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Authors: S. U. Khan, T. Ayub, N. Shafiq

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The properties of locally produced metakaolin (MK) as cement replacing material and the comparison of reactivity with commercially available micro-silica have been investigated. Compressive strength, splitting tensile strength, and load-deflection behaviour under bending are the properties that have been studied. The amorphous phase of MK with micro-silica was compared through X-ray diffraction (XRD) pattern. Further, interfacial transition zone of concrete with micro-silica and MK was observed through Field Emission Scanning Electron Microscopy (FESEM). Three mixes of concrete were prepared. One of the mix is without cement replacement as control mix, and the remaining two mixes are 10% cement replacement with micro-silica and MK. It has been found that MK, due to its irregular structure and amorphous phase, has high reactivity with portlandite in concrete. The compressive strength at early age is higher with MK as compared to micro-silica. MK concrete showed higher splitting tensile strength and higher load carrying capacity as compared to control and micro-silica concrete at all ages respectively.

Keywords: metakaolin, compressive strength, splitting tensile strength, load deflection, interfacial transition zone

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Authors: Fu-Chien Hung, Chi‐Wen Liang

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Background: People who suffer from chronic fatigue syndrome (CFS) frequently complain about continuous tiredness, weakness or lack of strength, but without apparent organic etiology. The prevalence rate of the CFS is nearly from 3% to 20%, yet more than 80% go undiagnosed or misdiagnosed as depression. The biopsychosocial model has suggested the associations among the CFS, depressive syndrome, and stress. This study aimed to investigate the difference between individuals with the CFS and with the depressive syndrome on psychophysiological responses under stress. Method: There were 23 participants in the CFS group, 14 participants in the depression group, and 23 participants in the healthy control group. All of the participants first completed the measures of demographic data, CFS-related symptoms, daily life functioning, and depressive symptoms. The participants were then asked to perform a stressful cognitive task. The participants’ psychophysiological responses including the HR, BVP and SC were measured during the task. These indexes were used to assess the reactivity and recovery rates of the automatic nervous system. Results: The stress reactivity of the CFS and depression groups was not different from that of the healthy control group. However, the stress recovery rate of the CFS group was worse than that of the healthy control group. Conclusion: The results from this study suggest that the CFS is a syndrome which can be independent from the depressive syndrome, although the depressive syndrome may include fatigue syndrome.

Keywords: chronic fatigue syndrome, depression, stress response, misdiagnosis

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Authors: Masoumeh Ghorbania, Falk Liebnerb, Hendrikus W.G. van Herwijnenc, Johannes Konnertha

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Phenol formaldehyde (PF) resins are widely used as wood adhesives for variety of industrial products such as plywood, laminated veneer lumber and others. Lignin as a main constituent of wood has become well-known as a potential substitute for phenol in PF adhesives because of their structural similarity. During the last decades numerous research approaches have been carried out to substitute phenol with pulping-derived lignin, whereby the lower reactivity of resins synthesized with shares of lignin seem to be one of the major challenges. This work reports about a systematic screening of different types of lignin (plant origin and pulping process) for their suitability to replace phenol in phenolic resins. Lignin from different plant sources (softwood, hardwood and grass) were used, as these should differ significantly in their reactivity towards formaldehyde of their reactive phenolic core units. Additionally a possible influence of the pulping process was addressed by using the different types of lignin from soda, kraft, and organosolv process and various lignosulfonates (sodium, ammonium, calcium, magnesium). To determine the influence of lignin on the adhesive performance beside others the rate of viscosity development, bond strength development of varying hot pressing time and other thermal properties were investigated. To evaluate the performance of the cured end product, a few selected properties were studied at the example of solid wood-adhesive bond joints, compact panels and plywood. As main results it was found that lignin significantly accelerates the viscosity development in adhesive synthesis. Bonding strength development during curing of adhesives decelerated for all lignin types, while this trend was least for pine kraft lignin and spruce sodium lignosulfonate. However, the overall performance of the products prepared with the latter adhesives was able to fulfill main standard requirements, even after exposing the products to harsh environmental conditions. Thus, a potential application can be considered for processes where reactivity is less critical but adhesive cost and product performance is essential.

Keywords: phenol formaldehyde resin, lignin phenol formaldehyde resin, ABES, DSC

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Authors: Kamsiah Jaarin, Yusof Kamisah, Faizah Othman Nurul Akmal Muhammad, Zakiah Jubri, Qodriyah Mohd Saad, Srijit Das

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Forty (40) normotensive adult male Sprague-Dawley rats aged three months weighing 180-200 g were divided into 4 groups with 10 rats per group: (1) normotensive control; (2) hypertensive rats; (3) hypertensive rats treated with Nigella sativa (2.5 ml/kg/day); and (4) hypertensive rats treated with nicardipine (5 mg/kg/day). After acclimatization, the hypertensive rats of the group 2, 3 and 4 were induced to be hypertensive by giving NW–nitro-L-arginine methyl ester (L-NAME; 30 mg/kg/day) in their drinking water for consecutive 7 days. After one week, rats in the group 3 were given a daily oral dose of 2.5 ml/kg/day of Nigella sativa (NS) by oral gavage. Rats in the group 4 were given nicardipine (5 mg/kg/day) via oral gavages. All rats in this study received L-NAME continuously throughout the treatment duration. The blood pressure will be measured pre-treatment and weekly for 8 weeks using power lab. Blood was taken before and at the end of study for measurement of nitric oxide. At the end of 8 weeks, the rats are sacrificed and descending thoracic aorta was disserted for measurement of vascular reactivity, and intracellular adhesion molecules (ICAM-1) and vascular cell adhesion molecules (VCAM-1). Nigella sativa reduced both systolic and diastolic BP compared to control and L-name group. The BP lowering effect of NS was comparable to nicardipine a calcium antagonist. The blood pressure lowering effect of NS was accompanied with an increasing relaxation response to nitroprusside and acetylcholine and reducing vasoconstriction response to epinephrine. L-NAME and nicardipine on the other hand, reduced plasma nitric oxide concentration. In contrast, NS increased NO concentration. However, Nigella sativa had no significant effect on aortic VCAM- 1 and ICAM-1 expression. In conclusion; Nigella sativa oil reduces both systolic and diastolic blood pressure in L-NAME treated rats. The antihypertensive effect of NS was comparable to nicardipine. The BP lowering effect may be mediated via stimulating nitric oxide release from vascular endothelium.

Keywords: Nigella sativa, ICAM, VCAM, blood pressure, vascular reactivity

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Authors: Soraya Abtouche, Zeyneb Ghoualem, Syrine Daoudi, Lina Ouldmohamed, Xavier Assfeld

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This work reports density functional theory calculations of the optimized geometries, molecular reactivity, energy gap,and thermodynamic properties of the free base (H2P) and their Zn (II) metallated (ZnP), bearing one, two, or three carboxylic acid groups using the hybrid functional B3LYP, Cam-B3lYP, wb97xd with 6-31G(d,p) basis sets. When donating groups are attached to the molecular dye, the bond lengths are slightly decreased, which is important for the easy transfer of an electron from donating to the accepting group. For all dyes, the highest occupied molecular orbital/lowest occupied molecular orbital analysis results in positive outcomes upon electron injection to the semiconductor and subsequent dye regeneration by the electrolyte. The ionization potential increases with increasing conjugation; therefore, the compound dye attached to one carboxylic acid group has the highest ionization potential. The results show higher efficiencies of those sensitized with ZnP. These results have been explained, taking into account the electronic character of the metal ion, which acts as a mediator in the injection step, and, on the other hand, considering the number of anchoring groups to which it binds to the surface of TiO2.

Keywords: DSSC, porphyrin, TD-DFT, electronic properties, donor-acceptor groups

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Authors: Despina Vamvuka, Despina Pentari

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Forestry wastes are readily available in large quantities around the world. Based on European Green Deal for the deployment of renewable and decarbonized energy by 2050, as well as global energy crisis, energy recovery from such wastes reducing greenhouse gas emissions is very attractive. Gasification has superior environmental performance to combustion, producing a clean fuel gas utilized in internal combustion engines, gas turbines, solid oxide fuel cells, or for synthesis of liquid bio-fuels and value-added chemicals. In this work, pine needles, which are abundantly found in Mediterranean countries, were gasified by either steam or carbon dioxide via a two-step process to improve reactivity and eliminate tar, employing a fixed bed unit and a thermal analysis system. Solid, liquid and gaseous products from the whole process were characterized and their energy potential was determined. Thermal behaviour, reactivity, conversion and energy recovery were examined. The gasification process took place above 650°C. At 950°C conversion and energy recovery were 77% dry and 2 under a flow of steam and 85% dry and 2.9 under a flow of carbon dioxide, respectively. Organic matter was almost completely converted to syngas, the yield of which varied between 89% and 99%. The higher heating values of biochar, bio-oil and pyrolysis gas were 27.8 MJ/kg, 33.5 MJ/kg and 13.6 MJ/m3. Upon steam or carbon dioxide gasification, the higher heating value of syngas produced was 11.5 MJ/m3 and 12.7 MJ/m3, respectively.

Keywords: gasification, biomass, steam, carbon dioxide

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Authors: Hendrik Bernard Van Der Walt, Frik Van Niekerk

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Fuel models render a reduction in BOL when thorium is added to a reactor core. Thorium emulates the role of a fertile poison, and is beneficial for reducing beginning of cycle (BOC) excess reactivity. In spite of the build-up of 233U over the duration of a fuel cycle, the effects of fuel reloading have a significant impact on fuel viability, especially in the case of heterogeneous thorium-based fuels. The most common practice of compensating for the reduction of BOC reactivity is the addition of fissile isotopes (uranium fuel with increased enrichment or plutonium). This study introduces a heterogeneous thorium-based fuel with minimal fissile isotope additions. A pseudo reloading scheme was developed for numerical simulations of an infinite reactor based on the North-Anna 1 reactor operating in Virginia, USA. Use of this reloading pattern allows new thorium-based fuel to be loaded into the reactor model as part of a phasing in strategy at the end of any conventional reactor cycle. Results demonstrate the effects of thorium-based fuel on fuel cycle characteristics such as fuel cycle length, neutron economy and material matrix. Application of the above mentioned approach delivered promising results and presents a heterogeneous thorium-based fuel which could replace conventional fuel of typical, currently operating (or future) reactors without the need for expensive reactor redesign or fuel recycling strategies.

Keywords: nuclear fuel, nuclear characteristics, nuclear fuel cycle, thorium-based fuel, heterogeneous design, fuel reloading

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Authors: Adrien Cornille, Marine Blain, Bernard Boutevin, Sylvain Caillol

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Generally, linear polyurethanes (PUs) are obtained by the reaction between an oligomeric diol, a short diol as chain extender and a diisocyanate. However the use of diisocyanate should be avoided since they are generally very harmful for human health. Therefore the synthesis of NIPUs (non isocyanate PUs) from step growth polymerization of dicyclocarbonates and diamines should be favoured. This method is particularly interesting since no hazardous isocyanates are used. Thus, this reaction, extensively studied by Endo et al. is currently gaining a lot of attention as a substitution route for the synthesis of NIPUs, both from industrial and academic community. However, the reactivity of reaction between amine and cyclic carbonate is a major scientific issue, since cyclic carbonates are poorly reactive. Thus, our team developed several synthetic ways for the synthesis of various di-cyclic carbonates based on C5-, C6- and dithio- cyclic carbonates, from different biobased raw materials (glycerin isosorbide, vegetable oils…). These monomers were used to synthesize NIPUs with various mechanical and thermal properties for various applications. We studied the reactivity of reaction with various catalysts and find optimized conditions for room temperature reaction. We also studied the radical copolymerization of cyclic carbonate monomers in styrene-acrylate copolymers for coating applications. We also succeeded in the elaboration of biobased NIPU flexible foams. To the best of our knowledge, there is no report in literature on the preparation of non-isocyanate polyurethane foams.

Keywords: foam, nonisocyanate polyurethane, cyclic carbonate, blowing agent, scanning electron microscopy

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Authors: Karlee J. Hall, Mark Laylor, Jessy Varghese, Paula Polastri, Karen Van Ooteghem, William McIlroy

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Balance training is a common part of physiotherapy treatment and often involves a set of proprioceptive exercises which the patient carries out in the clinic and as part of their exercise program. Understanding all contributing factors to altered balance is of utmost importance to the clinical success of treatment of balance dysfunctions. A critical role for the autonomic nervous system (ANS) in the control of balance reactions has been proposed previously, with evidence for potential involvement being inferred from the observation of phasic galvanic skin responses (GSR) evoked by external balance perturbations. The current study explored whether the coupling between ANS reactivity and balance reactions would be observed during spontaneously occurring instability while standing, including standard positions typical of physiotherapy balance assessments. It was hypothesized that time-varying changes in GSR (ANS reactivity) would be associated with time-varying changes in the mediolateral center of pressure (ML-COP) (somatomotor reactivity). Nine individuals (5 females, 4 males, aged 19-37 years) were recruited. To induce varying balance demands during standing, the study compared ML-COP and GSR data across different task conditions varying the availability of vision and width of the base of support. Subjects completed 3, 30-second trials for each of the following stance conditions: standard, narrow, and tandem eyes closed, tandem eyes open, tandem eyes open with dome to shield visual input, and restricted peripheral visual field. ANS activity was evaluated by measures of GSR recorded from Ag-AgCl electrodes on the middle phalanges of digits 2 and 4 on the left hand; balance measures include ML-COP excursion frequency and amplitude recorded from two force plates embedded in the floor underneath each foot. Subjects were instructed to stand as still as possible with arms crossed in front of their chest. When comparing mean task differences across subjects, there was an expected increase in postural sway from tasks with a wide stance and no sensory restrictions (least challenging) to those with a narrow stance and no vision (most challenging). The correlation analysis revealed a significant positive relationship between ML-COP variability and GSR variability when comparing across tasks (r=0.94, df=5, p < 0.05). In addition, correlations coincided within each subject and revealed a significant positive correlation in 7 participants (r= 0.47, 0.57, 0.62, 0.62, 0.81, 0.64, 0.69 respectively, df=19, p < 0.05) and no significant relationship in 2 participants (r=0.36, 0.29 respectively, df=19, p > 0.05). The current study revealed a significant relationship between ML-COP and GSR during balance tasks, revealing the ANS reactivity associated with naturally occurring instability when standing still, which is proportional to the degree of instability. Understanding the link between ANS activity and control of COP is an important step forward in the enhancement of assessment of contributing factors to poor balance and treatment of balance dysfunctions. The next steps will explore the temporal association between the time-varying changes in COP and GSR to establish if the ANS reactivity phase leads or lags the evoked motor reactions, as well as exploration of potential biomarkers for use in screening of ANS activity as a contributing factor to altered balance control clinically.

Keywords: autonomic nervous system, balance control, center of pressure, somatic nervous system

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Authors: Jaime R. Silva, Gabriel E. Reyes, Marianne Krause

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Background: The two-polarity model of the depressive personality argues that experience is organized around two axes: interpersonal relatedness and self-definition. Differential emphasis on one of these poles defines three types of depressive experience: Anaclitic, Introjective or Mixed pattern. On the one hand, Anaclitic pattern has been conceptually related with exaggerated biological stress sensitivity. On the other hand, the Introjective pattern was linked with anhedonic symptomatology. The general aim of the study was to find empirical support for this relationship. Methods: 101 non-clinical individuals participated in two experimental sessions. During the first session, the biological stress reactivity (cortisol concentration in saliva) and the subjective stress perceived (self-reported) during the Trier Social Stress Test (TSST), were investigated. In the second session, a visual discrimination task with a specific reward system, to study the reinforcement sensitivity (anhedonia), was performed. Results: Results evidenced that participants with Introjective depressive symptoms showed a higher interpersonal sensitivity and a diminished sensitivity to reinforcement. In addition, results also indicated that such a group has a poor psychological detection of its exacerbated reactivity to stress, which is the opposite pattern evidenced amongst the Anaclitic group. Conclusions: In perspective, these results empirically support the two-polarity of the depressive personality model. Clinical implications are discussed.

Keywords: depression, interpersonal stress, personality, trier social stress test

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Authors: Srinivasapriyan Vijayan

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Phenol is one of the most vital chemical in industry. Nowadays, phenol production is based upon the three-step cumene process, which involves a hazardous cumene hydroperoxide intermediate and produces nearly equimolar amounts of acetone as a coproduct. An attractive route in phenol production is the direct one-step selective hydroxylation of benzene using eco-friendly oxidants such as O2, N2O, and H2O2. In particular, the direct hydroxylation of benzene to form phenol with O2 has recently attracted extensive research attention because this process is green clean and eco-friendly. However, most of the catalytic systems involving O2 have a low rate of hydroxylation because the direct introduction of hydroxyl functionality into benzene is challenging. Almost all the developed catalytic systems require an elevated temperature and suffer from low conversion because of the notoriously low reactivity of aromatic C–H bonds. Moreover, increased reactivity of phenol relative to benzene makes the selective oxidation of benzene to phenol very difficult, especially under heating conditions. Hollow spheres, a very fascinating class of materials with good permeation and low density, highly monodisperse MOF hollow sandwich spheres have been rationally synthesized using monodisperse polystyrene (PS) nanoparticles as templates through a versatile step-by-step self-assembly strategy. So, our findings could pave the way toward highly efficient nonprecious catalysts for low-temperature oxidation reactions in heterogeneous catalysis. Because it is easy post-reaction separation, its cheap, green and recyclable.

Keywords: benzene hydroxylation, Fe-based metal organic frameworks, molecular oxygen, phenol

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Authors: Alexander Zotov, Ilkin Osmanov, Emil Sakharov, Oleg Shelest, Aleksander Troitskiy, Robert Khabazov

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Objective: Thoracoscopic surgical ablation of atrial fibrillation (AF) includes two technologies in performing of operation. 1st strategy used is the AtriCure device (bipolar, nonirrigated, non clamping), 2nd strategy is- the Medtronic device (bipolar, irrigated, clamping). The study presents a comparative analysis of clinical outcomes of two strategies in thoracoscopic ablation of AF using AtriCure vs. Medtronic devices. Methods: In 2 center study, 123 patients underwent thoracoscopic ablation of AF for the period from 2016 to 2020. Patients were divided into two groups. The first group is represented by patients who applied the AtriCure device (N=63), and the second group is - the Medtronic device (N=60), respectively. Patients were comparable in age, gender, and initial severity of the condition. Among the patients, in group 1 were 65% males with a median age of 57 years, while in group 2 – 75% and 60 years, respectively. Group 1 included patients with paroxysmal form -14,3%, persistent form - 68,3%, long-standing persistent form – 17,5%, group 2 – 13,3%, 13,3% and 73,3% respectively. Median ejection fraction and indexed left atrial volume amounted in group 1 – 63% and 40,6 ml/m2, in group 2 - 56% and 40,5 ml/m2. In addition, group 1 consisted of 39,7% patients with chronic heart failure (NYHA Class II) and 4,8% with chronic heart failure (NYHA Class III), when in group 2 – 45% and 6,7%, respectively. Follow-up consisted of laboratory tests, chest Х-ray, ECG, 24-hour Holter monitor, and cardiopulmonary exercise test. Duration of freedom from AF, distant mortality rate, and prevalence of cerebrovascular events were compared between the two groups. Results: Exit block was achieved in all patients. According to the Clavien-Dindo classification of surgical complications fraction of adverse events was 14,3% and 16,7% (1st group and 2nd group, respectively). Mean follow-up period in the 1st group was 50,4 (31,8; 64,8) months, in 2nd group - 30,5 (14,1; 37,5) months (P=0,0001). In group 1 - total freedom of AF was in 73,3% of patients, among which 25% had additional antiarrhythmic drugs (AADs) therapy or catheter ablation (CA), in group 2 – 90% and 18,3%, respectively (for total freedom of AF P<0,02). At follow-up, the distant mortality rate in the 1st group was – 4,8%, and in the 2nd – no fatal events. Prevalence of cerebrovascular events was higher in the 1st group than in the 2nd (6,7% vs. 1,7% respectively). Conclusions: Despite the relatively shorter follow-up of the 2nd group in the study, applying the strategy using the Medtronic device showed quite encouraging results. Further research is needed to evaluate the effectiveness of this strategy in the long-term period.

Keywords: atrial fibrillation, clamping, ablation, thoracoscopic surgery

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