Search results for: cerebrovascular reactivity

Authors: Teruya Goto, Hokuto Chiba, Tatsuhiro Takahashi

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Carbon fiber reinforced thermoplastic resin using short carbon fiber has been produced by melt mixing and the improvement of mechanical properties has been frequently reported up to now. One of the most frequently reported enhancement has been seen in carbon fiber / polypropylene (PP) composites by adding small amount of maleic anhydride grafted polypropylene (MA-g-PP) into PP matrix. However, the further enhancement of tensile strength and tensile modules has been expected for lightning the composite more. Our present research aims to improve the mechanical property by using a highly reactive monolayer polymer, which can react with both COOH of carbon fiber surface and maleic anhydride of MA-g-PP in the matrix, on carbon fiber for PP/CF composite. It has been known that oxazoline has much higher reactivity with COOH without catalysts, compared with amine group and alcohol OH group. However, oxazoline group has not been used for the interface. To achieve the purpose, poly-2-vinyl-2-oxazoline (Pvozo), having highly reactivity with COOH and maleic anhydride, has been originally synthesized through radical polymerization using 2-vinyl-2-oxazoline as a monomer, resulting in the Mw around 140,000. Monolayer Pvozo chemically reacted on CF was prepared in 1-methoxy-2-propanol solution of Pvozo by heating at 100oC for 3 hours. After this solution treatment, unreacted Pvozo was completely washed out by methanol, resulting the uniform formation of the monolayer Pvozo on CF. Monolayer Pvozo coated CF was melt mixed by with PP and a small amount of MA-g-PP for the preparation of the composite samples using a batch type melt mixer. With performing the tensile strength tests of the composites, the tensile strength of CF/MA-g-PP/PP showed 40% increase, compared to that of CF/PP. While, that of Pvozo coated CF/MA-g-PP/PP exhibited 80% increase, compared to that of CF/PP. To get deeper insight of the dramatic increase, the weight percentage of chemically grafted polymer based on CF was evaluated by dissolving and removing the matrix polymer by xylene using by thermos gravimetric analysis (TGA). The chemically grafted remained polymer was found to be 0.69wt% in CF/PP, 0.98wt% in CF/MA-g-PP/PP, 1.51wt% in Pvozo coated CF/MA-g-PP/PP, suggesting that monolayer Pvozo contributed to the increase of the grafted polymer amount. In addition, the very strong adhesion by Pvozo was confirmed by observing the fractured cross-sectional surface of the composite by scanning electron micrograph (SEM). As a conclusion, the effectiveness of a highly reactive monolayer Pvozo on CF for the enhancement of the mechanical properties of CF/PP composite was demonstrated, which can be interpreted by the clear evidence of the increase of the grafting polymer on CF.

Keywords: CFRTP, interface, oxazoline, polymer graft, mechanical property

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Authors: Sun Il Yu, Jung Hyun Joo, Hwa Sung Shin

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Astrocytes are known as dominant cells in CNS and play a role as a supporter of CNS activity and regeneration. Recently, three-dimensional culture of astrocytes were actively applied to understand in vivo astrocyte works. Electrospun nanofibers are attractive for 3D cell culture system because they have a high surface to volume ratio and porous structure, and have already been used for 3D astrocyte cultures. In this research, the stiffness of cellulose acetate (CA) nanofiber was controlled by heat treatment. As stiffness increased, astrocyte cell viability and adhesion increased. Reactivity of astrocyte was also upregulated in stiffer CA nanofiber in terms of GFAP, an intermediate filament protein. Finally, we demonstrated that stiffness-controllable CA is attractive for astrocyte tissue engineering.

Keywords: astrocyte, cellulose acetate, nanofiber, tissue scaffold

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Authors: G. S. Sudha, Smita Mohanty, S. K. Nayak

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Epoxidized oils can replace petroleum derived materials in numerous industrial applications, because of their respectable oxirane oxygen content and high reactivity of oxirane ring. Epoxidized castor oil (ECO) has synthesized in the presence of a sulphonated polystyrene type cation exchange resin. The formation of the oxirane ring was confirmed by Fourier Transform Infrared Spectroscopy (FTIR) analysis. The epoxidation reaction was evaluated by Nuclear Magnetic Resonance (NMR) studies. ECO is used as a toughening phase to increase the toughness of petroleum-based epoxy resin.

Keywords: epoxy resin, epoxidized castor oil, sulphonated polystyrene type cation exchange resin, petroleum derived materials

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Authors: Asad Hanif, Pavithra Parthasarathy, Zongjin Li

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Thermal insulating composites help to reduce the total power consumption in a building by creating a barrier between external and internal environment. Such composites can be used in the roofing tiles or wall panels for exterior surfaces. This study purposes to develop lightweight cement-based composites for thermal insulating applications. Waste materials like silica fume (an industrial by-product) and fly ash cenosphere (FAC) (hollow micro-spherical shells obtained as a waste residue from coal fired power plants) were used as partial replacement of cement and lightweight filler, respectively. Moreover, aerogel, a nano-porous material made of silica, was also used in different dosages for improved thermal insulating behavior, while poly vinyl alcohol (PVA) fibers were added for enhanced toughness. The raw materials including binders and fillers were characterized by X-Ray Diffraction (XRD), X-Ray Fluorescence spectroscopy (XRF), and Brunauer–Emmett–Teller (BET) analysis techniques in which various physical and chemical properties of the raw materials were evaluated like specific surface area, chemical composition (oxide form), and pore size distribution (if any). Ultra-lightweight cementitious composites were developed by varying the amounts of FAC and aerogel with 28-day unit weight ranging from 1551.28 kg/m³ to 1027.85 kg/m³. Excellent mechanical and thermal insulating properties of the resulting composites were obtained ranging from 53.62 MPa to 8.66 MPa compressive strength, 9.77 MPa to 3.98 MPa flexural strength, and 0.3025 W/m-K to 0.2009 W/m-K as thermal conductivity coefficient (QTM-500). The composites were also tested for peak temperature difference between outer and inner surfaces when subjected to heating (in a specially designed experimental set-up) by a 275W infrared lamp. The temperature difference up to 16.78 ^oC was achieved, which indicated outstanding properties of the developed composites to act as a thermal barrier for building envelopes. Microstructural studies were carried out by Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray Spectroscopy (EDS) for characterizing the inner structure of the composite specimen. Also, the hydration products were quantified using the surface area mapping and line scale technique in EDS. The microstructural analyses indicated excellent bonding of FAC and aerogel in the cementitious system. Also, selective reactivity of FAC was ascertained from the SEM imagery where the partially consumed FAC shells were observed. All in all, the lightweight fillers, FAC, and aerogel helped to produce the lightweight composites due to their physical characteristics, while exceptional mechanical properties, owing to FAC partial reactivity, were achieved.

Keywords: aerogel, cement-based, composite, fly ash cenosphere, lightweight, sustainable development, thermal conductivity

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Authors: E. Petrakis, V. Karmali, K. Komnitsas

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In this study grinding experiments were performed in a laboratory ball mill using Polish ferronickel slag in order to study the effect of the particle size on alkali activation and the properties of the produced alkali activated materials (AAMs). In this regard, the particle size distribution and the specific surface area of the grinding products in relation to grinding time were assessed. The experimental results show that products with high compressive strength, e.g. higher than 60 MPa, can be produced when the slag median size decreased from 39.9 μm to 11.9 μm. Also, finer fractions are characterized by higher reactivity and result in the production of AAMs with lower porosity and better mechanical properties.

Keywords: alkali activation, compressive strength, grinding time, particle size distribution, slag, structural integrity

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Authors: Sonu Gandhi, Neena Capalash, Prince Sharma, C. Raman Suri

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A sensitive chemiluminescence immunoassay (CIA) for heroin and its major metabolites is reported. The method is based on the competitive reaction of horseradish peroxidase (HRP)-labeled anti-MAM antibody and free drug in spiked urine samples. A hapten-protein conjugate was synthesized by using acidic derivative of monoacetyl morphine (MAM) coupled to carrier protein BSA and was used as an immunogen for the generation of anti-MAM (monoacetyl morphine) antibody. A high titer of antibody (1:64,0000) was obtained and the relative affinity constant (Kaff) of antibody was 3.1×107 l/mol. Under the optimal conditions, linear range and reactivity for heroin, mono acetyl morphine (MAM), morphine and codeine were 0.08, 0.09, 0.095 and 0.092 ng/mL respectively. The developed chemiluminescence inhibition assay could detect heroin and its metabolites in standard and urine samples up to 0.01 ng/ml.

Keywords: heroin, metabolites, chemiluminescence immunoassay, horse radish peroxidase

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Authors: Craig Jantzen, Tim Abram, Dirk Engelberg, Hugues Lambert, Daniel Cooper

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Molten salts are of high interest for use as coolants in nuclear reactors due to favourable high temperature and thermodynamic properties. The corrosive behaviour of molten salts however pose a materials integrity challenge. Three Ni / Ni-Fe based and two Mo based alloys have been exposed to molten eutectics (LiCl-KCl at 59.5:40.5 mol% and KCl-MgCl2 at 68:32 mol%) at 600°C and 800°C for durations up to 500hrs. Corrosion was observed to preferentially attack alloy constituents in order of their reactivity, with chromium the most vulnerable and depleted element. Alloy weight-loss per unit area was calculated to give linear corrosion rates, discounting any initial rapid corrosion of impurities. Further analysis was carried out using ICP-MS, SEM and EDX techniques to give a more detailed view of the corrosion mechanisms.

Keywords: molten salt, salt, corrosion, high temperature, licl, KCL, MgCl, molybdenum, nickel, superalloys

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Authors: Ozlem Uguz, Ali Demirci, Hanzade Haykiri-Acma, Serdar Yaman

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Lignitic coal holds its position as Turkey’s most important indigenous energy source to generate energy in thermal power plants. Hence, efficient and environmental-friendly use of lignite in electricity generation is of great importance. Thus, clean coal technologies have been planned to mitigate emissions and provide more efficient burning in power plants. In this context, oxygen enriched combustion (oxy-combustion) is regarded as one of the clean coal technologies, which based on burning with oxygen concentrations higher than that in air. As it is known that the most of the Turkish coals are low rank with high mineral matter content, unburnt carbon trapped in ash is, unfortunately, high, and it leads significant losses in the overall efficiencies of the thermal plants. Besides, the necessity of burning huge amounts of these low calorific value lignites to get the desired amount of energy also results in the formation of large amounts of ash that is rich in unburnt carbon. Oxygen enriched combustion technology enables to increase the burning efficiency through the complete burning of almost all of the carbon content of the fuel. This also contributes to the protection of air quality and emission levels drop reasonably. The aim of this study is to investigate the unburnt carbon content and the burning reactivities of several different lignite samples under oxygen enriched conditions. For this reason, the combined effects of temperature and oxygen/nitrogen ratios in the burning atmosphere were investigated and interpreted. To do this, Turkish lignite samples from Adıyaman-Gölbaşı and Kütahya-Tunçbilek regions were characterized first by proximate and ultimate analyses and the burning profiles were derived using DTA (Differential Thermal Analysis) curves. Then, these lignites were subjected to slow burning process in a horizontal tube furnace at different temperatures (200ºC, 400ºC, 600ºC for Adıyaman-Gölbaşı lignite and 200ºC, 450ºC, 800ºC for Kütahya-Tunçbilek lignite) under atmospheres having O₂+N₂ proportions of 21%O₂+79%N₂, 30%O₂+70%N₂, 40%O₂+60%N₂, and 50%O₂+50%N₂. These burning temperatures were specified based on the burning profiles derived from the DTA curves. The residues obtained from these burning tests were also analyzed by proximate and ultimate analyses to detect the unburnt carbon content along with the unused energy potential. Reactivity of these lignites was calculated using several methodologies. Burning yield under air condition (21%O₂+79%N₂) was used a benchmark value to compare the effectiveness of oxygen enriched conditions. It was concluded that oxygen enriched combustion method enhanced the combustion efficiency and lowered the unburnt carbon content of ash. Combustion of low-rank coals under oxygen enriched conditions was found to be a promising way to improve the efficiency of the lignite-firing energy systems. However, cost-benefit analysis should be considered for a better justification of this method since the use of more oxygen brings an unignorable additional cost.

Keywords: coal, energy, oxygen enriched combustion, reactivity

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Authors: Ridvan Yamanoglu

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In the current study, titanium based composites reinforced by hard nickel alloy particles were produced. Powder metallurgical hot pressing technique was used for the fabrication of composite materials. The composites containing different ratio of hard nickel particles were sintered at 900 oC for 15 and 30 minutes under 50 MPa pressure. All titanium based composites were obtained under a vacuum atmosphere of 10-4 mbar to prevent of oxidation of titanium due to its high reactivity to oxygen. The microstructural characterization of the composite samples was carried out by optical and scanning electron microscopy. The mechanical properties of the samples were determined by means of hardness and wear tests. The results showed that when the nickel particle content increased the mechanical properties of the composites enhanced. The results are discussed in detail and optimum nickel particle content were determined.

Keywords: titanium, composite, nickel, hot pressing

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Authors: Young Cheol Choi, Eun-Jin Moon, Sung-Won Yoo, Sang-Hwa Jung, In-Hwan Yang

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Stainless steel slag (STS) is a by-product generated from the stainless steel refining process. The recycling of STS produced in Korea for construction applications is limited due to its poor hydraulic properties. On the other hand, STS has high carbonation reactivity to CO2 as it contains gamma-C2S content. This material is ideal for mineral carbonation which is one of the techniques proposed for carbon emission reduction. The objective of this study is to investigate the feasibility of developing a zero-cement STS binder activated by carbonation as alternative cementitious material. The quantitative analyses for CO2 uptake of STS powder and STS blended cement were investigated using thermogravimetric analysis (TGA), X-ray diffraction (XRD). In addition, the compressive strength and microstructure of STS pastes after CO2 curing were evaluated. Test results showed that STS can be activated by carbonation to gain a sufficient strength as alternative cementitious material.

Keywords: gamma-C2S, CO2 uptake, carbonation, stainless steel slag

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Authors: Hiroshi Nakayama, Yuji Ito

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Synthetic cannabinoids have attracted much public attention recently in Japan. 1-pentyl-3-(1-naphthoyl)-indole (JWH-018), 1-pentyl-2-methyl-3-(1-naphthoyl) indole (JWH-015), 1-(5-fluoropentyl)-3- (1-(2,2,3,3- tetramethylcyclopropyl)) indole (XLR-11) and 1-methyl-3- (1-admantyl) indole (JWH-018 adamantyl analog) are known as synthetic cannabinoids and are also considered dangerous illegal drugs in Japan. It has become necessary to develop sensitive and useful methods for detection of synthetic cannabinoids. We produced two monoclonal antibodies (MAb) against synthetic cannabinoids, named NT1 (IgG1) and NT2 (IgG1), using Hybridoma technology. The cross-reactivity of these produced MAbs was evaluated using a competitive enzyme-linked immunosorbent assay (ELISA). In the results, we found both of these antibodies recognize many kinds of synthetic cannabinoids analog. However, neither of these antibodies recognizes naphtoic acid, 1-methyl-indole and indole known as a raw material of synthetic cannabinoid. Thus, the MAbs produced in this study could be a useful tool for the detection of synthetic cannabinoids.

Keywords: ELISA, monoclonal antibody, sensor, synthetic cannabinoid

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Authors: Sameh M. Osman, El-Refaie Kenawy, Zeid A. Al-Othman, Mohamed H. El-Newehy, El-Saied A. Aly, Sherine N. Khattab, Ayman El-Faham

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Recently, there has been a huge interest in using cyanuric chloride in a wide range of functional group transformations, as Cyanuric chloride has temperature-dependent differential reactivity for displacement of chlorides with various nucleophiles In the present work, some copolymers based on s-triazine Unit were prepared by microwave-assisted synthesis. For comparison study, the copolymers were synthesized by the conventional method. Synthesized Copolymers were characterized by MP, IR, TGA, DSC and GPC. The result indicated that copolymers are thermally stable and in good in composition and yield. Further studies that involve the test for selected removal of transition elements such as Cu (II), Zn (II) and Mn (II). Moreover, the effects of the polymeric triazine derivatives containing different functional groups which expected to have a good thermal stability and char formation ability on thermal degradation and flame retardancy.

Keywords: flame retardants, heavy metals, microwave-assisted synthesis, s-triazine

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Authors: Naveed Ejaz, Liaqat Ali, Amer Nusair

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Thermal barrier coatings (TBCs) serve as thermal barriers against the high temperature of the hot regions of the aircraft turbine engines keeping the surface of the turbine blades, vanes and combustion chamber at comparatively lower temperature. The life of these coatings depends on many in-service environmental factors. Among these factors, the behavior of the bond coat as well as the top coat at high temperature aggravated by the corrosive environments having S, V, Na and Cl plays a key role. The incorporation of the 5-15% CaZrO3 in YSZ coatings was studied after hot corrosion in vanadium oxide environment. It was observed that the reactivity of the V gradually switched from Y to Ca making CaV2O4 instead of YVO4; the percentage of CaV2O4 increased with the increase of CaZrO3 in YSZ. It eventually prevented leaching out of the Y from YSZ leaving the YSZ without any harmful phase change. The thermal insulation was found to be improved in case of CaZrO3 incorporated YSZ coatings as compared to only YSZ coating.

Keywords: hot corrosion, thermal barrier coatings, yttria stabilized zirconia, calcium zirconate

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Authors: Babu Shersad, Partha Banerjee

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Reduction in haemoglobin levels has been implicated to be a cause for reduced exercise tolerance and cardiovascular complications of chronic renal diseases. Trends of hemoglobin levels in patients on haemodialysis could be an indicator of efficacy of hemodialysis and an indicator of quality of life in haemodialysis patients. In the UAE, the rate of growth (of patients on dialysis) is 10 to 15 per cent per year. The primary mode of haemodialysis in the region is based on in-patient hospital-based hemodialysis units. The increase in risk of cardiovascular and cerebrovascular morbidity as well as mortality in pre-dialysis Chronic Renal Disease has been reported. However, data on the health burden on haemodialysis in standalone dialysis facilities is very scarce. This is mainly due to the paucity of ambulatory centres for haemodialysis in the region. AMSA is the first center to offer standalone dialysis in the UAE and a study over a one year period was performed. Patient data was analyzed using a questionnaire for 45 patients with an average of 2.5 dialysis sessions per week. All patients were on chronic haemodialysis as outpatients. The trends of haemoglobin levels as an independent variable were evaluated. These trends were interpreted in comparison with other parameters of renal function (creatinine, uric acid, blood pressure and ferritin). Trends indicate an increase in hemoglobin levels with increased supplementation of iron and erythropoietin over time. The adequacy of hemodialysis shows improvement concomitantly. This, in turn, correlates with better patient outcomes and has a direct impact on morbidity and mortality. This study is a pilot study and further studies are indicated so that objective parameters can be studied and validated for hemodialysis in the region.

Keywords: haemodialysis, haemoglobin in haemodialysis, haemodialysis parameters, erythropoietic agents in haemodialysis

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Authors: Atef Youssef, Marwa Mostafa Moharam

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The effects of poly pyrrole (PP) addition on LiFePO4 have been studied by electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV), and galvanostatic measurements. PP was prepared with LiFePO₄ in different ways, such as chemically dispersion, insinuation polymerization, and electrochemically polymerization. The EIS results showed that the charge transfer resistance (Rct) of LiFePO₄ was decreased by adding 10% PP polymerized in a situation to 153 vs. 1660  for bare LiFePO₄. The CV curves show that 10% PP added LiFePO₄ had higher electrochemical reactivity for lithium insertion and extraction than the un-doped material. The mean redox potential is E1/2 = 3.45 V vs. Li+/Li. The first discharge curve of the 10% poly pyrrole doped LiFePO₄ showed a mainly flat voltage plateau over the 3.45–3.5 V range, indicating the lithium extraction and insertion reactions between LiFePO₄ and FePO₄. A specific discharge capacity of cells prepared from in-situ 10% PP added LiFePO4to was about 210 vs. 65 mAhg-1 for bare LiFePO₄.

Keywords: liFePO₄, poly pyrrole addition, positive electrode, lithium battery

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Authors: Ali Ashjaran

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Graphene is undoubtedly emerging as one of the most promising materials because of its unique combination of superb properties, which opens a way for its exploitation in a wide spectrum of applications ranging from electronics to optics, sensors, and biodevices. In addition, Graphene-based nanomaterials have many promising applications in energy-related areas. Graphene a single layer of carbon atoms, combines several exceptional properties, which makes it uniquely suited as a coating material: transparency, excellent mechanical stability, low chemical reactivity, Optical, impermeability to most gases, flexibility, and very high thermal and electrical conductivity. Graphene is a material that can be utilized in numerous disciplines including, but not limited to: bioengineering, composite materials, energy technology and nanotechnology, biological engineering, optical electronics, ultrafiltration, photovoltaic cells. This review aims to provide an overiew of graphene structure, properties and some applications.

Keywords: graphene, carbon, anti corrosion, optical and electrical properties, sensors

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Authors: Shyh-Ming Chern, Hung-Chi Tu

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One way to utilize biomass is to thermochemically convert it into gases and chemicals. For conversion of biomass, glucose is a particularly popular model compound for cellulose, or more generally for biomass. The present study takes a different approach by employing lactic acid as the model compound for cellulose. Since lactic acid and glucose have identical elemental composition, they are expected to produce similar results as they go through the conversion process. In the current study, lactic acid was thermochemically converted to assess its reactivity and reaction mechanism in subcritical and supercritical water, by using a 16-ml autoclave reactor. The major operating parameters investigated include: The reaction temperature, from 673 to 873 K, the reaction pressure, 10 and 25 MPa, the dosage of oxidizing agent, 0 and 0.5 chemical oxygen demand, and the concentration of lactic acid in the feed, 0.5 and 1.0 M. Gaseous products from the conversion were generally found to be comparable to those derived from the conversion of glucose.

Keywords: lactic acid, subcritical water, supercritical water, thermochemical conversion

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Authors: Akram Alfantazi, Tirdad Nickchi

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Magnesium galvanic corrosion plays an important role in the commercialization of Mg alloys in the automobile industry. This study aims at visualizing the electrochemical activity of the magnesium surface being coupled with pure iron in sulfate-chloride solutions. Scanning electrochemical microscopy was used to monitor the chemical activity of the surface and the data was compared with the conventional corrosion results such as potentiodynamic polarization, linear polarization, and immersion tests. The SECM results showed that the chemical reactivity of Mg is higher than phosphate-permanganate-coated Mg. Regions in the vicinity of the galvanic couple boundary are very active in the magnesium phase and fully protected in the iron phase. Scanning electrochemical microscopy results showed that the conversion coating provided good corrosion resistance for magnesium in the short-term but fails at long-term testing.

Keywords: corrosion, galvanic corrosion, magnesium, scanning electrochemical microscopy

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Authors: Binyamien Ibrahim Rasoul

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Controlled burning of rice husk can produce amorphous rice husk ash (RHA) with high silica content which can significantly enhance the properties of concrete. This study has been undertaken to investigate the relationship between the incineration temperatures and time to produce RHA with ultimate reactivity. The rice husk samples were incinerated in an electrical muffle furnace at 350°C, 400°C, 425°C 450°C, 475°C, and 500°C for 60 and 90 minutes, respectively. The silica structure in the Rice Husk Ash (RHA) was determined using X-Ray diffraction analysis, while chemical properties obtained using X-Ray Fluorescence. The results show that RHA appeared to be the totally amorphous when the husk incineration up to 425°C for 60 and even at 90 minutes. However, with increased temperature to 450°C, 475°C and 500°C, traces of crystalline silica (quartz) were detected. However, cannot be taken into account as it does not affect on the ash structure. In conclusion, the result gives an idea of the temperature and the time required to produce ash from rice husk with totally amorphous form.

Keywords: rice husk ash, silica, compressive strength, tensile strength, X-Ray diffraction, X-R florescence, pozzolanic activity

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Authors: Bai-Jing Peng, Shyh-Chyun Yang

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Organic reactions in water have recently attracted much attention, not only because unique reactivity is often observed in water but also because water is a safe and economical substitute for conventional organic solvents. Thus, development of environmental safe, atom-economical reactions in water is one of the most important goals of synthetic chemistry. The recent paper has documented renewed interest in the use of allylic substrates in the synthesis of new C−C, C−N, and C−O bonds. We have reported our attempts and some successful applications of a process involving the C-O bond cleavage catalyzed by palladium or platinum complexes in water. Because of the importance of heterocycle indole derivatives, much effort has been directed toward the development of methods for functionalization of the indole nucleus at N1 site. In our research, the palladium-catalyzed 2,3-disubstitued indoles with allylic alcohols was investigated under different conditions. Herein, we will establish a simple, convenient, and efficient method, which affords high yields of allylated indoles.

Keywords: palladium-catalyzed, allylic alcohols, indoles, water, allylation

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Authors: Anna Kolanowska, Anna Kuziel, Sławomir Boncel

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Carbon nanotubes (CNTs) represent a combination of lightness and nanoscopic size with high tensile strength, excellent thermal and electrical conductivity. By now, CNTs have been used as a support in heterogeneous catalysis (CuCl anchored to pre-functionalized CNTs) in the Ullmann-type coupling with aryl halides toward formation of C-N and C-O bonds. The results indicated that the stability of the catalyst was much improved and the elaborated catalytic system was efficient and recyclable. However, CNTs have not been considered as the substrate itself in the Ullmann-type reactions. But if successful, this functionalization would open new areas of CNT chemistry leading to enhanced in-solvent/matrix nanotube individualization. The copper-catalyzed Ullmann-type reaction is an attractive method for the formation of carbon-heteroatom and carbon-carbon bonds in organic synthesis. This condensation reaction is usually conducted at temperature as high as 200 oC, often in the presence of stoichiometric amounts of copper reagent and with activated aryl halides. However, a small amount of organic additive (e.g. diamines, amino acids, diols, 1,10-phenanthroline) can be applied in order to increase the solubility and stability of copper catalyst, and at the same time to allow performing the reaction under mild conditions. The copper (pre-)catalyst is prepared by in situ mixing of copper salt and the appropriate chelator. Our research is focused on the application of Ullmann-type reaction for the covalent functionalization of CNTs. Firstly, CNTs were chlorinated by using iodine trichloride (ICl3) in carbon tetrachloride (CCl4). This method involves formation of several chemical species (ICl, Cl2 and I2Cl6), but the most reactive is the dimer. The fact (that the dimer is the main individual in CCl4) is the reason for high reactivity and possibly high functionalization levels of CNTs. This method, indeed, yielded a notable amount of chlorine onto the MWCNT surface. The next step was the reaction of CNT-Cl with three substrates: aniline, iodobenzene and phenol for the formation C-N, C-C and C-O bonds, respectively, in the presence of 1,10-phenanthroline and cesium carbonate (Cs2CO3) as a base. As the CNT substrates, two multi-wall CNT (MWCNT) types were used: commercially available Nanocyl NC7000™ (9.6 nm diameter, 1.5 µm length, 90% purity) and thicker MWCNTs (in-house) synthesized in our laboratory using catalytic chemical vapour deposition (c-CVD). In-house CNTs had diameter ranging between 60-70 nm and length up to 300 µm. Since classical Ullmann reaction was found as suffering from poor yields, we have investigated the effect of various solvents (toluene, acetonitrile, dimethyl sulfoxide and N,N-dimethylformamide) on the coupling of substrates. Owing to the fact that the aryl halides show the reactivity order of I>Br>Cl>F, we have also investigated the effect of iodine presence on CNT surface on reaction yield. In this case, in first step we have used iodine monochloride instead of iodine trichloride. Finally, we have used the optimized reaction conditions with p-bromophenol and 1,2,4-trihydroxybenzene for the control of CNT dispersion.

Keywords: carbon nanotubes, coupling reaction, functionalization, Ullmann reaction

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Authors: Jitendra Jain, Cassandra Hidajat, Hansraj Riteesh Bookun

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Graft patency underpins long-term prognosis after coronary artery bypass grafting surgery (CABG). The benefits of the combined use of only the left internal mammary artery and radial artery, referred to as total arterial revascularisation (TAR), on long-term clinical outcomes and quality of life are relatively unknown. The aim of this study was to identify whether there were differences in long term clinical outcomes between recipients of TAR compared to a cohort of mostly arterial revascularization involving the left internal mammary, at least one radial artery and at least one saphenous vein graft. A retrospective analysis was performed on all patients who underwent TAR or were re-vascularized with supplementary saphenous vein graft from February 1996 to December 2004. Telephone surveys were conducted to obtain clinical outcome parameters including major adverse cardiac and cerebrovascular events (MACCE) and Short Form (SF-36v2) Health Survey responses. A total of 176 patients were successfully contacted to obtain postop follow up results. The mean follow-up length from time of surgery in our study was TAR 12.4±1.8 years and conventional 12.6±2.1. PCS score was TAR 45.9±8.8 vs LIMA/Rad/ SVG 44.9±9.2 (p=0.468) and MCS score was TAR 52.0±8.9 vs LIMA/Rad/SVG 52.5±9.3 (p=0.723). There were no significant differences between groups for NYHA class 3+ TAR 9.4% vs. LIMA/Rad/SVG 6.6%; or CCS 3+ TAR 2.35% vs. LIMA/Rad/SVG 0%.

Keywords: CABG; MACCEs; quality of life; total arterial revascularisation

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Authors: Nathalia Andrea Calderon Lesmes, Eduardo Barragan Parada, Diego Fernando Villegas Bermudez

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Spasticity in the plantiflexor muscles as a product of stroke (CVA-Cerebrovascular accident) restricts the mobility and independence of the affected people. Commonly, physiotherapists are in charge of manually performing the rehabilitation therapy known as Sustained Mechanical Stretching, rotating the affected foot of the patient in the sagittal plane. However, this causes a physical wear on the professional because it is a fatiguing movement. In this article, a mechanical device is developed to implement this rehabilitation therapy more efficiently. The device consists of a worm-crown mechanism that is driven by a crank to gradually rotate a platform in the sagittal plane of the affected foot, in order to achieve dorsiflexion. The device has a range of sagittal rotation up to 150° and has velcro located on the footplate that secures the foot. The design of this device was modeled by using CAD software and was checked structurally with a general purpose finite element software to be sure that the device is safe for human use. As a measurement system, a goniometer is used in the lateral part of the device and load cells are used to measure the force in order to determine the opposing torque exerted by the muscle. Load cells sensitivity is 1.8 ± 0.002 and has a repeatability of 0.03. Validation of the effectiveness of the device is measured by reducing the opposition torque and increasing mobility for a given patient. In this way, with a more efficient therapy, an improvement in the recovery of the patient's mobility and therefore in their quality of life can be achieved.

Keywords: biomechanics, mechanical device, plantiflexor muscles, rehabilitation, spastic hemiplegia, sustained mechanical stretching

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Authors: Rahma Tibigui, Ikram Hadj Said, Rachid Belkada, Dalila Hammoutene

Abstract:

The vulnerability of industrial facilities is highly concerned with multiple risks from corrosion. The commonly adopted solution is based on the use of organic inhibitors, which are gradually being replaced by environmentally friendly organic inhibitors. In our work, we carried out a quantum chemical study based on the Density Functional Theory (DFT) method at the B3LYP/6-311G (d,p) level of theory. The inhibitory performance of a derivative of the tetrazole molecule has been investigated and reported as a carbon steel-friendly corrosion inhibitor in hydrochloric acid (HCl) medium. The relationship is likely to exist between the molecular structure of this compound as well as its various global reactivity descriptors, and its corrosion inhibition efficiency, which was examined and then discussed. The results show low values of ΔE, which represent strong adsorption of the inhibitor on the steel surface. Moreover, the flat adsorption orientation confirmed the great ability to donate (accept) electrons to (from) steel, fabricating an anchored barrier to prevent steel from corrosion.

Keywords: eco-friendly, corrosion inhibitors, tetrazole, DFT

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Authors: Han-Bin Kim, Sooim Shin, Moonsung Choi

Abstract:

There is a growing interest in introducing a desired functional group on enzymes in the field of protein engineering. In here, various redox centers were newly created using histidine tag, which is widely used for protein purification, plus cobalt in one of cupredoxins, amicyanin. The coordination of Cobalt-His tag and reactivity of the Co²⁺ loaded His-tag also were characterized. 3xHis-tag, 6xHis-tag, and 9xHis-tag were introduced on amicyanin by site-directed mutagenesis, and then Co²⁺ was loaded on each His-tagged amicyanin. The spectral changes at 330 nm corresponding to cobalt binding on His-tag site indicated the binding ratio of 3xHis-tag, 6xHis-tag, and 9xHis-tag to cobalt as 1:1, 1:2, 1:3 respectively. Based on kinetic studies of binding cobalt to 3xHis-tag, 6xHis-tag, and 9xHis-tagged amicyanin, the nature of the sites was elucidated. In addition, internal electron transfer properties between Cu¹⁺ site and engineered site of amicyanin were determined. These results provide insight into improvement of metal coordination and alternation of the redox properties of metal as a new catalytic site on proteins.

Keywords: amicyanin, cobalt, histidine, protein engineering

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Authors: B. K. Kanungo, Monika Thakur, Minati Baral

Abstract:

8-hydroxyquinoline, (8HQ), experiences a renaissance due to its utility as a building block in metallosupramolecular chemistry and its versatile use of its derivatives in various fields of analytical chemistry, materials science, and pharmaceutics. It forms stable complexes with a variety of metal ions. Assembly of more than one such unit to form a polydentate chelator enhances its coordinating ability and the related properties due to the chelate effect resulting in high stability constant. Keeping in view the above, a nonadentate chelator N-[3,5-bis(8-hydroxyquinoline-2-amido)cyclohexyl]-8-hydroxyquinoline-2-carboxamide, (TACH2OX), containing a central cis,cis-1,3,5-triaminocyclohexane appended to three 8-hydroxyquinoline at 2-position through amide linkage is developed, and its solution thermodynamics, photophysical and Density Functional Theory (DFT) studies were undertaken. The synthesis of TACH2OX was carried out by condensation of cis,cis-1,3,5-triaminocyclohexane, (TACH) with 8‐hydroxyquinoline‐2‐carboxylic acid. The brown colored solid has been fully characterized through melting point, infrared, nuclear magnetic resonance, electrospray ionization mass and electronic spectroscopy. In solution, TACH2OX forms protonated complexes below pH 3.4, which consecutively deprotonates to generate trinegative ion with the rise of pH. Nine protonation constants for the ligand were obtained that ranges between 2.26 to 7.28. The interaction of the chelator with two trivalent metal ion Fe3+ and Al3+ were studied in aqueous solution at 298 K. The metal-ligand formation constants (ML) obtained by potentiometric and spectrophotometric method agree with each other. The protonated and hydrolyzed species were also detected in the system. The in-silico studies of the ligand, as well as the complexes including their protonated and deprotonated species assessed by density functional theory technique, gave an accurate correlation with each observed properties such as the protonation constants, stability constants, infra-red, nmr, electronic absorption and emission spectral bands. The nature of electronic and emission spectral bands in terms of number and type were ascertained from time-dependent density functional theory study and the natural transition orbitals (NTO). The global reactivity indices parameters were used for comparison of the reactivity of the ligand and the complex molecules. The natural bonding orbital (NBO) analysis could successfully describe the structure and bonding of the metal-ligand complexes specifying the percentage of contribution in atomic orbitals in the creation of molecular orbitals. The obtained high value of metal-ligand formation constants indicates that the newly synthesized chelator is a very powerful synthetic chelator. The minimum energy molecular modeling structure of the ligand suggests that the ligand, TACH2OX, in a tripodal fashion firmly coordinates to the metal ion as hexa-coordinated chelate displaying distorted octahedral geometry by binding through three sets of N, O- donor atoms, present in each pendant arm of the central tris-cyclohexaneamine tripod.

Keywords: complexes, DFT, formation constant, TACH2OX

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Authors: John Rothrock

Abstract:

Background: The role of transthoracic echocardiography (TTE) in the diagnosis and management of patients with acute ischemic stroke remains controversial. While many stroke subspecialist reserve TTE for selected patients, others consider the procedure obligatory for most or all acute stroke patients. This study was undertaken to assess the cost vs. benefit of 'routine' TTE. Methods: We examined a consecutive series of patients who were admitted to a single institution in 2019 for acute ischemic stroke and underwent TTE. We sought to determine the frequency with which the results of TTE led to a new diagnosis of cardioembolism, redirected therapeutic cerebrovascular management, and at least potentially influenced the short or long-term clinical outcome. We recorded the direct cost associated with TTE. Results: There were 1076 patients in the study group, all of whom underwent TTE. TTE identified an unsuspected source of possible/probable cardioembolism in 62 patients (6%), confirmed an initially suspected source (primarily endocarditis) in an additional 13 (1%) and produced findings that stimulated subsequent testing diagnostic of possible/probable cardioembolism in 7 patients ( < 1%). TTE results potentially influenced the clinical outcome in a total of 48 patients (4%). With a total direct cost of $1.51 million, the mean cost per case wherein TTE results potentially influenced the clinical outcome in a positive manner was $31,375. Diagnostically and therapeutically, TTE was most beneficial in 67 patients under the age of 55 who presented with 'cryptogenic' stroke, identifying patent foramen ovale in 21 (31%); closure was performed in 19. Conclusions: The utility of TTE in the setting of acute ischemic stroke is modest, with its yield greatest in younger patients with cryptogenic stroke. Given the greater sensitivity of transesophageal echocardiography in detecting PFO and evaluating the aortic arch, TTE’s role in stroke diagnosis would appear to be limited.

Keywords: cardioembolic, cost-benefit, stroke, TTE

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Authors: Nurcan Tugrul, Funda Demir, Hilal Ozkan, Nur Olgun, Emek Derun

Abstract:

Geopolymers are aluminosilicate-containing materials. The raw materials of the geopolymerization can be natural material such as kaolinite, metakaolin (calcined kaolinite), clay, diatomite, rock powder or can also be industrial by-products such as fly ash, silica fume, blast furnace slag, rice-husk ash, mine tailing, red mud, waste slag, etc. Reactivity of raw materials in geopolymer production is very important for achieving high reaction grade. Fly ash used in geopolymer production has been calcined to obtain tetrahedral SiO₂ and Al₂O₃ structures. In this study, fly ash calcined at different temperatures (700, 800 and 900 °C), and Al₂O₃ addition (Al₂O₃ at min (0%) and max (100%)) were used to produce geopolymers. HCl dissolution method was applied to determine the geopolymerization percentage of samples and Fourier Transform Infrared (FTIR) Spectroscopy was used to find out the optimum calcination temperature for geopolymerization. According to obtained results, the highest geopolymerization percentage (0% alumina added geopolymer equal to 35.789%; 100% alumina added geopolymer equal to 40.546%) was obtained in samples using fly ash calcined at 800 °C.

Keywords: geopolymer, fly ash, Al₂O₃ addition, calcination

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Authors: Somayyeh Kalami, Mojgan Nejad

Abstract:

Based on the source (softwood, hardwood or annual crop) and isolation method (kraft, organosolv, sulfite or pre-enzymatic treatment), there are significant variations in lignin structure and properties. The first step in using lignin as biobased feedstock is to make sure that specific lignin is suitable for intended application. Complete characterization of lignin and measuring its chemical, physical and thermal properties can help to predict its suitability. To replace 100% phenol portion of phenolic adhesive, lignin should have high reactivity toward formaldehyde. Theoretically, lignins with closer backbone structure to phenol should be better candidate for this application. In this study, a number of different lignins were characterized and used to formulate phenolic adhesive. One of the main findings was that lignin sample with higher percentage of hydroxyl-phenyl units was better candidate than lignin with more syringyl units. This could be explained by the fact that hydroxyl-phenyl lignin units have two available ortho positions for reaction with formaldehyde while in syringyl units all ortho and para positions are occupied, and there is no available site in lignin structure to react with formaldehyde.

Keywords: lignin, phenolic adhesive, biobased, sustainable

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Authors: Heba Fouad, Tarek M. Madkour, Safwan A. Khedr

Abstract:

This paper investigates multiple factors that impact the formation of geopolymers and their compressive strength to be utilized in construction as an environmentally-friendly material. Bentonite and Kaolinite were thermally calcinated at 750 °C to obtain Metabentonite and Metakaolinite with higher reactivity. Both source materials were activated using a solution of sodium hydroxide (NaOH). Thereafter, samples were cured at different temperatures. The samples were analyzed chemically using a host of spectroscopic techniques. The bulk density and compressive strength of the produced Geopolymer pastes were studied. Findings indicate that the ratio of NaOH solution to source material affects the compressive strength, being optimal at 0.54. Moreover, controlled heat curing was proven effective to improve compressive strength. The existence of characteristic Fourier Transform Infrared Spectroscopy (FTIR) peaks at approximately 1020 cm-1 and 460 cm-1 which corresponds to the asymmetric stretching vibration of Si-O-T and bending vibration of Si-O-Si, hence, confirming the formation of the target geopolymer.

Keywords: calcination of metakaolinite, compressive strength, FTIR analysis, geopolymer, green cement

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