Search results for: microRNA precursor

Authors: Ashish Bohre, Blaž Likozar, Saikat Dutta, Dionisios G. Vlachos, Basudeb Saha

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Graphene oxide, decorated with surface oxygen functionalities, has emerged as a sustainable alternative to precious metal catalysts for many reactions. Herein, we report for the first time that graphene oxide becomes super active for C-C coupling upon incorporation of multilayer crystalline features, highly oxidized surface, Brønsted acidic functionalities and defect sites on the surface and edges via modified oxidation. The resulting improved graphene oxide (IGO) demonstrates superior activity to commonly used framework zeolites for upgrading of low carbon biomass furanics to long carbon chain aviation fuel precursors. A maximum 95% yield of C15 fuel precursor with high selectivity is obtained at low temperature (60 C) and neat conditions via hydroxyalkylation/alkylation (HAA) of 2-methylfuran (2-MF) and furfural. The coupling of 2-MF with carbonyl molecules ranging from C3 to C6 produced the precursors of carbon numbers 12 to 21. The catalyst becomes inactive in the 4th cycle due to the loss of oxygen functionalities, defect sites and multilayer features; however, regains comparable activity upon regeneration. Extensive microscopic and spectroscopic characterization of the fresh and reused IGO is presented to elucidate high activity of IGO and to establish a correlation between activity and surface and structural properties. Kinetic Monte Carlo (KMC) and density functional theory (DFT) calculations are presented to further illustrate the surface features and the reaction mechanism.

Keywords: methacrylic acid, itaconic acid, biomass, monomer, solid base catalyst

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Authors: Laura Frydel, Piotr M. Slomkiewicz, Beata Szczepanik

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Triclosan has been used as a disinfectant in many medical products, such as: hand disinfectant soaps, creams, mouthwashes, pastes and household cleaners. Due to its strong antimicrobial activity, triclosan is becoming more and more popular and the consumption of disinfectants with triclosan in it is increasing. As a result, this compound increasingly finds its way into waters and soils in an unchanged form, pollutes the environment and may have a negative effect on organisms. The aim of this study was to investigate the synthesis of cellulose-based halloysite-carbon adsorbent and perform its characterization. The template in the halloysite-carbon adsorbent was halloysite nanotubes and the carbon precursor was microcrystalline cellulose. Scanning electron microscope (SEM) images were obtained and the elementary composition (qualitative and quantitative) of the sample was determined by energy dispersion spectroscopy (EDS). The identification of the crystallographic composition of the halloysite nanotubes and the sample of the halloysite-carbon composite was carried out using the X-ray powder diffraction (XRPD) method. The FTIR spectra were acquired before and after the adsorption process in order to determine the functional groups on the adsorbent surface and confirm the interactions between adsorbent and adsorbate molecules. The parameters of the porous structure of the adsorbent, such as the specific surface area (Brunauer-Emmett-Teller method), the total pore volume and the volume of mesopores and micropores were determined. Total carbon and total organic carbon were also determined in the samples. A cellulose-based halloysite-carbon adsorbent was used to remove triclosan from water. The degree of removal of triclosan from water was approximately 90%. The results indicate that the halloysite-carbon composite can be successfully used as an effective adsorbent for removing triclosan from water.

Keywords: Adsorption, cellulose, halloysite, triclosan

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Authors: Omkar More, Isha Saini, Gracy Mathai

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To study whether there is any clinical correlation between pterygium and dry eye and to evaluate the status of the tear film in patients with pterygium. Methods: 100 eyes with pterygium were compared with 100 control eyes without pterygium. Patients between 20 – 70 years were included in the study. A detailed history was taken and Schirmer’s test and TBUT were performed on all to evaluate the status of dry eye. Schirmer’s test ˂ 10 mm and TBUT ˂10 seconds was considered abnormal. Results: Maximum number (52) of patients affected by dry eye in both the groups were in the age group 31-40 years which statistically showed age as a significant factor of association for both pterygium and dry eye (P < 0.01).Schirmer’s test was slightly reduced in patients with pterygium(18.73±5.69 mm). TBUT was significantly reduced in the case group (12.26±2.24sec).TBUT decreased maximally in 51-60 yrs age group (13.00±2.77sec) with pterygium showing a tear film instability. On comparison of pterygia and controls with normal and abnormal tear film, Odd’s Ratio was 1.14 showing a risk of dry eye in pterygia patients to be 1.14 times higher than controls. Conclusion: Whether tear dysfunction is a precursor to pterygium growth or pterygium causes tear dysfunction is still not clear. Research and clinical evidence, however, suggest that there is a relationship between the two. This study is, therefore, undertaken to investigate the correlation between pterygium and dry eye. The patients with pterygia were compared with normals to evaluate their status regarding dryness. A close relationship exists between ocular irritation symptoms and functional evidence of tear instability. Schirmer’s test and TBUT should routinely be used in the outpatient department to diagnose dry eye in patients with pterygium and these patients should be promptly treated to prevent any sight-threatening complications.

Keywords: footfall, nursing assessment, quality improvement, six sigma

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Authors: C. Busuioc, G. Voicu, S. I. Jinga

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The field of tissue engineering brings new challenges in terms of proposing original solutions for ongoing medical issues, improving the biological performances of existing clinical systems and speeding the healing process for a faster recovery and a more comfortable life as patient. In this context, we propose the obtaining of 3D porous scaffolds of mineral nature, dedicated to bone repairing and regeneration purposes or employed as bioactive filler for bone cements. Thus, bacterial cellulose - calcium phosphates composite materials have been synthesized by successive immersing of the polymeric membranes in the precursor solution containing Ca2+ and [PO4]3- ions. The mineral phase deposited on the surface of biocellulose fibers was varied as amount through the number of immersing cycles. The intermediary composites were subjected to thermal treatments at different temperatures in order to remove the organic part and provide the formation of a self-sustained 3D architecture. The resulting phase composition consists of common phosphates, while the morphology largely depends on the preparation parameters. Thus, the aspect of the 3D mineral scaffolds can be tuned from a loose microstructure composed of large grains connected via monocrystalline nanorods to a trabecular pattern crossed by parallel internal channels, just like the natural bone. The bioactivity and biocompatibility of the obtained materials have been also assessed, with encouraging results in the clinical use direction. In conclusion, the compositional, structural, morphological and biological characterizations sustain the suitability of the reported biostructures for integration in hard tissue engineering applications.

Keywords: bacterial cellulose, bone reconstruction, calcium phosphates, mineral scaffolds

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Authors: Alireza Rahimi, Abdolreza Farhadian, Arash Tajik, Elaheh Sadeh, Avni Berisha, Esmaeil Akbari Nezhad

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Although natural polymers have been shown to have some inhibitory properties on sour corrosion, they are not considered very effective green corrosion inhibitors. Accordingly, effective corrosion inhibitors should be developed based on natural resources to mitigate sour corrosion in the oil and gas industry. Here, Arabic gum was employed as an eco-friendly precursor for the synthesis of innovative polyurethanes designed as highly efficient corrosion inhibitors for sour oilfield solutions. A comprehensive assessment, combining experimental and computational analyses, was conducted to evaluate the inhibitory performance of the inhibitor. Electrochemical measurements demonstrated that a concentration of 200 mM of the inhibitor offered substantial protection to mild steel against sour corrosion, yielding inhibition efficiencies of 98% and 95% at 25 ºC and 60 ºC, respectively. Additionally, the presence of the inhibitor led to a smoother steel surface, indicating the adsorption of polyurethane molecules onto the metal surface. X-ray photoelectron spectroscopy results further validated the chemical adsorption of the inhibitor on mild steel surfaces. Scanning Kelvin probe microscopy revealed a shift in the potential distribution of the steel surface towards negative values, indicating inhibitor adsorption and corrosion process inhibition. Molecular dynamic simulation indicated high adsorption energy values for the inhibitor, suggesting its spontaneous adsorption onto the Fe (110) surface. These findings underscore the potential of Arabic gum as a viable resource for the development of polyurethanes under mild conditions, serving as effective corrosion inhibitors for sour solutions.

Keywords: environmental effect, Arabic gum, corrosion inhibitor, sour corrosion, molecular dynamics simulation

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Authors: Si Yin Tee

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Bimetallic nanostructures have received tremendous interests as a new class of nanomaterials which may have better technological usefulness with distinct properties from those of individual atoms and molecules or bulk matter. They excelled over the monometallic counterparts because of their improved electronic, optical and catalytic performances. The properties and the applicability of these bimetallic nanostructures not only depend on their size and shape, but also on the composition and their fine structure. These bimetallic nanostructures are potential candidates for bio-applications such as biosensing, bioimaging, biodiagnostics, drug delivery, targeted therapeutics, and tissue engineering. Herein, gold-incorporated copper (Cu/Au) nanostructures were synthesized through the controlled disproportionation of Cu⁺-oleylamine complex at 220 ºC to form copper nanowires and the subsequent reaction with Au³⁺ at different temperatures of 140, 220 and 300 ºC. This is to achieve their synergistic effect through the combined use of the merits of low-cost transition and high-stability noble metals. Of these Cu/Au nanostructures, Cu/Au nanotubes display the best performance towards electrochemical non-enzymatic glucose sensing, originating from the high conductivity of gold and the high aspect ratio copper nanotubes with high surface area so as to optimise the electroactive sites and facilitate mass transport. In addition to high sensitivity and fast response, the Cu/Au nanotubes possess high selectivity against interferences from other potential interfering species and excellent reproducibility with long-term stability. By introducing gold into copper nanostructures at a low level of 3, 1 and 0.1 mol% relative to initial copper precursor, a significant electrocatalytic enhancement of the resulting bimetallic Cu/Au nanostructures starts to occur at 1 mol%. Overall, the present fabrication of stable Cu/Au nanostructures offers a promising low-cost platform for sensitive, selective, reproducible and reusable electrochemical sensing of glucose.

Keywords: bimetallic, electrochemical sensing, glucose oxidation, gold-incorporated copper nanostructures

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Authors: Eyob Belew Abebe

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Nickel-rich layered oxide cathode materials having a Ni content of ≥ 90% have great potential for use in next-generation lithium-ion batteries (LIBs), due to their high energy densities and relatively low cost. They suffer, however, from poor cycling performance and rate capability, significantly hampering their widespread applicability. In this study we synthesized a Ni-rich precursor through a co-precipitation method and added different amounts of Li-excess on the precursors using a solid-state method to obtain sintered Li1+x(Ni0.9Co0.05Mn0.05)1–xO2 (denoted as L1+x-NCM; x = 0.00, 0.02, 0.04, 0.06, and 0.08) transition metal (TM) oxide cathode materials. The L1+x-NCM cathode having a Li-excess of 4% exhibited a discharge capacity of ca. 216.17 mAh g–1 at 2.7–4.3 V, 0.1C and retained 95.7% of its initial discharge capacity (ca. 181.39 mAh g–1) after 100 cycles of 1C charge/discharge which is the best performance as compared with stoichiometric Li1+x(Ni0.9Co0.05Mn0.05)1-xO2 (i.e. x=0, Li:TM = 1:1). Furthermore, a high-rate capability of ca. 162.92 mAh g–1 at a rate of 10C, led to the 4% Li-excess optimizing the electrochemical performance, relative to the other Li-excess samples. Ex/in-situ X-ray diffraction, scanning electron microscopy, and X-ray photoelectron spectroscopy revealed that the 4% Li-excess in the Ni-rich NCM90 cathode material: (i). decreased the Li+/Ni2+ disorder by increasing the content of Ni3+ in the TM slab, (ii). increased the crystallinity, and (iii). accelerated Li+ ion transport by widening the Li-slab. Furthermore, electrochemical impedance spectroscopy and cyclic voltammetry confirmed that the appropriate Li-excess lowered the electrochemical impedance and improved the reversibility of the electrochemical reaction. Therefore, our results revealed that NCM90 cathode materials featuring an optimal Li-excess are potential candidates for use in next-generation Li-ion batteries.

Keywords: LiNi₀.₉Co₀.₀₉Mn₀.₀₉O₂, li-excess, cation mixing, structure change, cycle stability, electrochemical properties

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Authors: Jing Ma, Guotong Qin

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We reported electro-confinement desalination (ECMD), a desalination method combining electric field effects and confinement effects using nanoporous carbon membranes as electrode. A carbon membrane with average pore size of 8.3 nm was prepared by organic sol-gel method. The precursor of support was prepared by curing porous phenol resin tube. Resorcinol-formaldehyde sol was coated on porous tubular resin support. The membrane was obtained by carbonisation of coated support. A well-combined top layer with the thickness of 35 μm was supported by macroporous support. Measurements of molecular weight cut-off using polyethylene glycol showed the average pore size of 8.3 nm. High salt rejection can be achieved because the water molecules need not overcome high energy barriers in confined space, while huge inherent dehydration energy was required for hydrated ions to enter the nanochannels. Additionally, carbon membrane with additional electric field can be used as an integrated membrane electrode combining the effects of confinement and electric potential gradient. Such membrane electrode can repel co-ions and attract counter-ions using pressure as the driving force for mass transport. When the carbon membrane was set as cathode, the rejection of SO₄²⁻ was 94.89%, while the removal of Na⁺ was less than 20%. We set carbon membrane as anode chamber to treat the effluent water from the cathode chamber. The rejection of SO₄²⁻ and Na⁺ reached to 100% and 88.86%, respectively. ECMD will be a promising energy efficient method for salt rejection.

Keywords: nanoporous carbon membrane, confined effect, electric field, desalination, membrane reactor

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Authors: Shari Ann S. Botin, Ruziel Larmae T. Gimpaya, Rembrant Rockwell Gamboa, Rinlee Butch M. Cervera

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In recent years, demand for the use of solid electrolytes as alternatives to liquid electrolytes has increased due to recurring battery safety and stability issues, in addition to an increase in energy density requirement which can be made possible by using solid electrolytes. Among the solid electrolyte systems, Li7La3Zr2O12 (LLZ) is one of the most promising as it exhibits good chemical stability against Li metal and has a relatively high ionic conductivity. In this study, pure and doped LLZ were synthesized via conventional solid state reaction. The precursor chemicals (such as LiOH, La2O3, Ga2O3 and ZrO2) were ground and then calcined at 900 °C, pressed into pellets and finally sintered at 1000 °C to 1200 °C. The microstructure and ionic conductivity of the obtained samples have been investigated. Results show that for pure LLZ, sintering at lower temperature (1000 °C) produced tetragonal LLZ while sintering at higher temperatures (≥ 1150 °C) produced cubic LLZ based from the XRD results. However, doping with Ga produces an easier formation of LLZ with cubic structure at lower sintering duration. On the other hand, the lithium conductivity of the samples was investigated using electrochemical impedance spectroscopy at room temperature. Among the obtained samples, Ga-doped LLZ sintered at 1150 °C obtained the highest ionic conductivity reaching to about 1x10⁻⁴ S/cm at room temperature. In addition, fabrication and initial investigation of an all-solid state Lithium Battery using the synthesized LLZ sample with the use of commercial cathode materials have been investigated.

Keywords: doped LLZ, lithium-ion battery, pure LLZ, solid electrolytes

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Authors: Mohaya Farzin, Shahin Hassanpour, Morteza Zendehdel, Bita Vazir, Ahmad Asghari

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Aim: There are several differences between birds and mammals in terms of food intake regulation. Therefore, this study aimed to investigate the effects of the intracerebroventricular (ICV) injection of spexin and its interaction with nitric oxide, serotonin, and corticotropin receptors on central food intake regulation in broiler chickens. Materials and Methods: In experiment 1, chickens received ICV injection of saline, PCPA (p-chlorophenyl alanine,1.25 µg), spexin, and PCPA+spexin. In experiments 2-7, 8-OH-DPAT (5-HT1A agonist, 15.25 nmol), SB-242084 (5-HT2C receptor antagonist, 1.5µg), L-arginine (Precursor of nitric oxide, 200 nmol), L-NAME (nitric oxide synthetase inhibitor, 100 nmol), Astressin-B (CRF1/CRF2 receptor antagonist, 30 µg) and Astressin2-B (CRF2 receptor antagonist, 30 µg) were injected to chickens instead of the PCPA. Then, food intake was measured until 120 minutes after the injection. Results: Spexin significantly decreased food consumption (P<0.05). Concomitant injection of SB-242084+spexin attenuated spexin-induced hypophagia (P<0.05). Co-injection of L-arginine+spexin enhanced spexin-induced hypophagia, and this effect was reversed by L-NAME (P<0.05). Also, concomitant injection of Astressin-B + spexin or Astressin2-B + spexin enhanced spexin-induced hypophagia (P<0.05). Conclusions: Based on these observations, spexin-induced hypophagia may be mediated by nitric oxide and 5-HT2C, CRF1, and CRF2 receptors in neonatal broiler chickens.

Keywords: spexin, serotonin, corticotropin, nitric oxide, food intake, chicken

Procedia PDF Downloads 49

Authors: C. F. Glover, J. Marinaccio, A. Barnes, I. Mabbett, G. Williams

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The aim of the current study is to optimise formulations, in terms of charging efficiency, of a printed Ni(OH)2 precursor coating of a battery anode. Through the assessment of the current densities during charging, the efficiency of a range of formulations are compared. The Scanning vibrating electrode technique (SVET) is used extensively in the field of corrosion to measure area-averaged current densities of freely-corroding metal surfaces when fully immersed in electrolyte. Here, a Ni(OH)2 electrode is immersed in potassium hydroxide (30% w/v solution) electrolyte and charged using a range of applied currents. Samples are prepared whereby multiple coatings are applied to one substrate, separated by a non-conducting barrier, and charged using a constant current. With a known applied external current, electrode efficiencies can be calculated based on the current density outputs measured using SVET. When fully charged, a green Ni(OH)2 is oxidised to a black NiOOH surface. Distinct regions displaying high current density, and hence a faster oxidising reaction rate, are located using the SVET. This is confirmed by a darkening of the region upon transition to NiOOH. SVET is a highly effective tool for assessing homogeneity of electrodes during charge/discharge. This could prove particularly useful for electrodes where there are no visible surface appearance changes. Furthermore, a scanning Kelvin probe technique, traditionally used to assess underfilm delamination of organic coatings for the protection of metallic surfaces, is employed to study the change in phase of oxides, pre and post charging.

Keywords: battery, electrode, nickel hydroxide, SVET, printed

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Authors: Anit S. Malhotra, Ajay Duseja, Neelam Chadha

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Endothelial dysfunction is a precursor to atherosclerosis, and flow-mediated dilatation (FMD) in the brachial artery is the commonest method to evaluate endothelial function in humans. Non-alcoholic fatty liver disease (NAFLD) is one of the most common liver disorders encountered in clinical practice. An earlier meta-analysis had quantitatively assessed the degree of endothelial dysfunction using FMD. However, the largest study investigating the relation of FMD with NAFLD was published after that meta-analysis. In addition, that meta-analysis did not include some studies, including one from our centre. Therefore, an updating the previous meta-analysis was considered important. We searched PubMed, Cochrane Library, Embase, Scopus, SCI, Google Scholar, conference proceedings, and references of included studies till June 2017 to identify observational studies evaluating endothelial function using FMD in patients with non-alcoholic fatty liver disease. Data was analyzed using MedCalc. Fourteen studies were found eligible for inclusion in the meta-analysis. Patients with NAFLD had lower brachial artery FMD as compared to controls, standardized mean difference (random effects model) being –1.279%; 95% confidence interval (CI), –1.478 to –0.914. The effect size became smaller after addition of the recent study with the largest sample size was included compared with the earlier meta-analysis. In conclusion, patients with NAFLD had low FMD values indicating that they are at a higher risk of cardiovascular disease although our results suggest the effect size is not as large as reported previously.

Keywords: endothelial dysfunction, flow-mediated dilatation, meta-analysis, non-alcoholic fatty liver disease

Procedia PDF Downloads 175

Authors: Mahmoud M. Zakaria, Omnia F. Elmoursi, Mahmoud M. Gabr, Camelia A. AbdelMalak, Mohamed A. Ghoneim

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Many protocols were publicized for differentiation of human mesenchymal stem cells (MSCS) into insulin-producing cells (IPCs) in order to excrete insulin hormone ingoing to treat diabetes disease. Our aim is to evaluate relative gene expression for each independent protocol. Human bone marrow cells were derived from three volunteers that suffer diabetes disease. After expansion of mesenchymal stem cells, differentiation of these cells was done by three different protocols (the one-step protocol was used conophylline protein, the two steps protocol was depending on trichostatin-A, and the three-step protocol was started by beta-mercaptoethanol). Evaluation of gene expression was carried out by real-time PCR: Pancreatic endocrine genes, transcription factors, glucose transporter, precursor markers, pancreatic enzymes, proteolytic cleavage, extracellular matrix and cell surface protein. Quantitation of insulin secretion was detected by immunofluorescence technique in 24-well plate. Most of the genes studied were up-regulated in the in vitro differentiated cells, and also insulin production was observed in the three independent protocols. There were some slight increases in expression of endocrine mRNA of two-step protocol and its insulin production. So, the two-step protocol was showed a more efficient in expressing of pancreatic endocrine genes and its insulin production than the other two protocols.

Keywords: mesenchymal stem cells, insulin producing cells, conophylline protein, trichostatin-A, beta-mercaptoethanol, gene expression, immunofluorescence technique

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Authors: Abubakar Dahiru Shuaibu, Atif Saeed Alzahrani, Md. Abdul Aziz

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Construction of eco-benign, cost effective, and high-performance supercapacitors with improved electrolytes and hierarchical porous electrodes is necessary for effective energy storage. In this study, a gel type organic redox electrolyte made of polyvinyl alcohol (PVA)-H2SO4 and an organic redox molecule, anthraquinone (PVA-H2SO4-AQ), was prepared by simple solution casting method and was used to construct a symmetric supercapacitor (SSC) with a high BET surface area (1612 m²/g) using activated carbon made from date stones (DSAC). The DSAC was synthesized by simple carbonization method followed by activation with potassium hydroxide. The SSC exhibit a high specific capacitance of 126.5 F/g at 0.5 A/g, as well as a high energy density of 17.5 Wh/kg at a power density of 250 W/kg with high capacitance retention (87%) after 1000 GCD cycles. The present research suggests that adding anthraquinone to a PVA-H2SO4 gel electrolyte improves the performance of the fabricated device significantly as compared to using pristine PVA-H₂SO₄ or 1M H₂SO₄ electrolytes. The research also presents a promising approach for the development of sustainable and eco-benign materials for energy storage applications. The use of date stone waste as a precursor material for activated carbon electrodes presents an opportunity for cost-effective and sustainable energy storage. Overall, the findings of this research have important implications for the future design and fabrication of high-performance and cost-effective supercapacitors

Keywords: date stone, activated carbon, anthraquinone, redox gel-electrolyte, supercapacitor

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Authors: Ghadeer Jalloul, Nour Hijazi, Cassia Boyadjian, Hussein Awala, Mohammad N. Ahmad, ‎Ahmad Albadarin

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In this study, we applied Fe-sensitized TiO₂ supported over embryonic Beta zeolite (BEA) zeolite ‎for the photocatalytic degradation of Tetracycline (TC) antibiotic under visible light. Four different ‎samples having 20, 40, 60, and 100% w/w as a ratio of TiO₂/BEA were prepared. The ‎immobilization of solgel TiO₂ (33 m²/g) over BEA (390 m²/g) increased its surface area to (227 ‎m²/g) and enhanced its adsorption capacity from 8% to 19%. To expand the activity of TiO₂ ‎photocatalyst towards the visible light region (λ>380 nm), we explored two different metal ‎sensitization techniques with Iron ions (Fe³⁺). In the ion-exchange method, the substitutional cations ‎in the zeolite in TiO₂/BEA were exchanged with (Fe³⁺) in an aqueous solution of FeCl₃. In the ‎doping technique, solgel TiO₂ was doped with (Fe³⁺) from FeCl₃ precursor during its synthesis and ‎before its immobilization over BEA. (Fe-TiO₂/BEA) catalysts were characterized using SEM, XRD, ‎BET, UV-VIS DRS, and FTIR. After testing the performance of the various ion-exchanged catalysts ‎under blue and white lights, only (Fe-TiO₂/BEA 60%) showed better activity as compared to pure ‎TiO₂ under white light with 100 ppm initial catalyst concentration and 20 ppm TC concentration. As ‎compared to ion-exchanged (Fe-TiO₂/BEA), doped (Fe-TiO₂/BEA) resulted in higher photocatalytic ‎efficiencies under blue and white lights. The 3%-Fe-doped TiO₂/BEA removed 92% of TC ‎compared to 54% by TiO₂ under white light. The catalysts were also tested under real solar ‎irradiations. This improvement in the photocatalytic performance of TiO₂ was due to its higher ‎adsorption capacity due to BEA support combined with the presence of Iron ions that enhance the ‎visible light absorption and minimize the recombination effect by the charge carriers. ‎

Keywords: Tetracycline, photocatalytic degradation, immobilized TiO₂, zeolite, iron-doped TiO₂, ion-exchange

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Authors: Andile Mkhohlakali, Tien-Chien Jen, James Tshilongo, Happy Mabowa

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Among different parameters, oxygen is one of the most important analytes of interest, dissolved oxygen (DO) concentration is very crucial and significant for various areas of physical, chemical, and environmental monitoring. Herein we report oxygen-sensitive luminophores -based lanthanum(III) trifluoromethanesulfonate), [La]³⁺ was encapsulated into SiO₂-based xerogel matrix. The nanosensor is composed of organically modified silica nanoparticles, doped with the luminescent oxygen–sensitive lanthanum(III) trifluoromethanesulfonate complex. The precursor materials used for sensing film were triethyl ethoxy silane (TEOS) and (3-Mercaptopropyltriethoxysilane) (MPTMS- TEOS) used for SiO2-baed matrices. Brunauer–Emmett–Teller (BET), and BJH indicate that the SiO₂ transformed from microporous to mesoporous upon the addition of La³⁺ luminophore with increased surface area (SBET). The typical amorphous SiO₂ based xerogels were revealed with X-Ray diffraction (XRD) and Selected Area Electron Diffraction (SAED) analysis. Scanning electron microscope- (SEM) and transmission electron microscope (TEM) showed the porous morphology and reduced particle for SiO₂ and La-SiO₂ xerogels respectively. The existence of elements, siloxane networks, and thermal stability of xerogel was confirmed by energy dispersive spectroscopy (EDS), Fourier-transform infrared spectroscopy (FTIR), and Thermographic analysis (TGA). UV-Vis spectroscopy and photoluminescence (PL) have been used to characterize the optical properties of xerogels. La-SiO₂ demonstrates promising characteristic features of an active sensing film for dissolved oxygen in the water. Keywords: Sol-gel, ORMOSILs, encapsulation, Luminophores quenching, O₂-sensing

Keywords: sol-gel, ORMOSILs, luminophores quenching, O₂-sensing

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Authors: Mirriam M. Moleko, Sekanse A. Ntsala

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Language in mathematics instruction enables the teacher to communicate mathematical knowledge to the learners with precision. It also enables the learner to deal with mathematical activities effectively. This scholarly piece was motivated by the fact that mathematics performance in the South African primary classrooms has not been satisfactory, and English, which is a Language of Learning and Teaching (LoLT) for the majority of the learners, has been singled out as one of the major impediments. This is not only on the part of the learners, but also on the part of the teachers as well. The study thus focused on the lack of competency in English among the primary school teachers as one of the possible causes of poor performance in mathematics in primary classrooms. The qualitative processes, which were premised on the social interaction theory as a lens, sourced the narratives of 10 newly qualified primary school mathematics teachers from the disadvantaged schools on the matter. This was achieved through the use of semi-structured interviews and focus group discussions. The data, which were analyzed thematically, highlighted the actuality that the challenges cut across the pre-service stage to the in-service stage. The findings revealed that the undergraduate mathematics courses in the number of the institutions neglect the importance of language. The study further revealed that the in-service mathematics teachers lack adequate linguistic command, thereby finding it difficult to successfully teach some mathematical concepts, or even to outline instructions clearly. The study thus suggests the need for training institutions to focus on improving the teachers’ English language competency. The need for intensive in-service training targeting the problem areas was also highlighted. The study thus contributes to the body of knowledge by providing suggestions on how the mathematics teachers’ language incompetency can be mitigated.

Keywords: Competency, English language proficiency, language of learning and teaching, primary mathematics teachers

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Authors: H. H. Lee, D. Y. Kim, S. W. Lee, J. H. Kim, J. H. Kim, W. Z. Oh, S. J. Choi

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In recent years, carbon nanotubes (CNTs) have been widely employed as a sorbent for the removal of various metal ions from water due to their unique properties such as large surface area, light mass density, high porous and hollow structure, and strong interaction between the pollutant molecules and CNTs. To apply CNTs to the sorption of Cs+ from aqueous solutions, they must first be functionalized to increase their hydrophilicity and therefore, enhance their applicability to the sorption of polar and relatively low-molecular-weight species. The objective of this study is to investigate the preparation of magnetically separable multi-walled carbon nanotubes (MWCNTs-m) as a sorbents for the removal of Cs+ from aqueous solutions. The MWCNTs-m was prepared using pristine MWCNTs and iron precursor Fe(acac)3. For the selective removal of Cs+ from aqueous solutions, the MWCNTs-m was functionalized with zinc hexacyanoferrate (MWCNTs-m-ZnFC). The physicochemical properties of the synthesized sorbents were characterized with various techniques, including transmission electron microscopy (TEM), specific surface area analysis, Fourier transform-infrared (FT-IR) spectroscopy, and vibrating-sample magnetometer. The MWCNTs-m-ZnFC was found to be easily separated from aqueous solutions by using magnetic field. The MWCNTs-m-ZnFC exhibited a high capacity for sorbing Cs+ from aqueous solutions because of their strong affinity for Cs+ and specific surface area. The sorption ability of the MWCNTs-m-ZnFC for Cs+ was maintained even in the presence of co-existing ions (Na+). Considering these results, the CNT-m-ZnFCs have great potential for use as an effective sorbent for the selective removal of radioactive Cs+ ions from aqueous solutions.

Keywords: multi-walled carbon nanotubes, magnetic materials, cesium, zinc hexacyanoferrate, sorption

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Authors: Seung-Min Yang, Seong-Han Park, Sang-Hoon Lee, Seung-Wan Yoo, Chan-Soo Kim, Nong-Moon Hwang

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The theory of charged nanoparticles suggested that in many Chemical Vapour Depositions (CVD) processes, Charged Nanoparticles (CNPs) are generated in the gas-phase and become a building block of thin films and nanowires. Recently, the nanoparticle-based crystallization has become a big issue since the growth of nanorods or crystals by the building block of nanoparticles was directly observed by transmission electron microscopy observations in the liquid cell. In an effort to confirm charged gas-phase nuclei, that might be generated under conventional processing conditions of thin films and nanowires during CVD, we performed an in-situ measurement using differential mobility analyser and particle beam mass spectrometer. The size distribution and number density of CNPs were affected by process parameters such as precursor flow rate and working temperature. It was shown that many films and nanostructures, which have been believed to grow by individual atoms or molecules, actually grow by the building blocks of such charged nuclei. The electrostatic interaction between CNPs and the growing surface induces the self-assembly into films and nanowires. In addition, the charge-enhanced atomic diffusion makes CNPs liquid-like quasi solid. As a result, CNPs tend to land epitaxial on the growing surface, which results in the growth of single crystalline nanowires with a smooth surface.

Keywords: chemical vapour deposition, charged nanoparticle, electrostatic force, nanostructure evolution, differential mobility analyser, particle beam mass spectrometer

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Authors: Chia-Ting Chang, Chia-Yu Lin

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We report on the decisive role of iron phosphate (FePO₄), formed in-situ during the electrochemical characterization, played in the electrocatalytic activity, especially its oxygen tolerance of iron oxides towards H₂O₂ reduction. Iron oxides studied including, Nanorod arrays (NRs) of β-FeOOH, γ-Fe₂O₃, α-Fe₂O₃, α-Fe₂O₃ nanosheets (α-Fe₂O₃NS), α-Fe₂O₃ nanoparticles (α-Fe₂O₃NP), were synthesized using chemical bath deposition. The nanostructure was controlled simply by adjusting the composition of precursor solution and reaction duration for CBD process, whereas the crystal phase was controlled by adjusting the annealing temperature. It was found that iron phosphate (FePO₄) was deposited in-situ onto the surface of this nanostructured α-Fe₂O₃ during the electrochemical pretreatment in the phosphate electrolyte, and both FePO₄ and α-Fe₂O₃ showed the activity in catalysing the electrochemical reduction of H₂O₂. In addition, the interaction/compatibility between deposited FePO₄ and iron oxides has a decisive effect on the overall electrocatalytic activity of the resultant electrodes; FePO₄ only showed synergetic effect on the overall electrocatalytic activity of α-Fe₂O₃NR and α-Fe2O₃NS. Both α-Fe₂O₃NR and α-Fe₂O₃NS showed two reduction peaks in phosphate electrolyte containing H₂O₂, one being pH-dependent and related to the electrocatalytic properties of FePO₄, and the other one being pH-independent and only related to the intrinsic electrocatalytic properties of α-Fe₂O₃NR and α-Fe₂O₃NS. However, all iron oxides showed only one pH-independent reductive peak in non-phosphate electrolyte containing H₂O₂. The synergesitic catalysis exerted by FePO₄ with α-Fe₂O₃NR or α-Fe₂O₃NS providing additional oxygen-insensitive active site for H₂O₂ reduction, which allows their applications to electrochemical detection of H₂O₂ without the interference of O₂ involving in oxidase-catalyzed chemical processes.

Keywords: H₂O₂ reduction, Iron oxide, iron phosphate, O₂ tolerance

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Authors: P. Acosta-Santamaría, A. Ibatá-Soto, A. López-Vásquez

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Organic compounds in wastewaters coming from textile and pharmaceutical industry generated multiple harmful effects on the environment and the human health. One of them is the methyl orange (MeO), an azoic dye considered to be a recalcitrant compound. The heterogeneous photocatalysis emerges as an alternative for treating this type of hazardous compounds, through the generation of OH radicals using radiation and a semiconductor oxide. According to the author’s knowledge, catalysts such as TiO₂ doped with metals show high efficiency in degrading MeO; however, this presents economic limitations on industrial scale. Black sand can be considered as a naturally doped catalyst because in its structure is common to find compounds such as titanium, iron and aluminum oxides, also elements such as zircon, cadmium, manganese, etc. This study reports the photocatalytic activity of the mineral black sand used as semiconductor in the discoloration of MeO by oxidation and reduction photocatalytic techniques. For this, magnetic composites from the mineral were prepared (RM, M1, M2 and NM) and their activity were tested through MeO discoloration while TiO₂ was used as reference. For the fractions, chemical, morphological and structural characterizations were performed using Scanning Electron Microscopy with Energy Dispersive X-Ray (SEM-EDX), X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF) analysis. M2 fraction showed higher MeO discoloration (93%) in oxidation conditions at pH 2 and it could be due to the presence of ferric oxides. However, the best result to reduction process was using M1 fraction (20%) at pH 2, which contains a higher titanium percentage. In the first process, hydrogen peroxide (H₂O₂) was used as electron donor agent. According to the results, black sand mineral can be used as natural semiconductor in photocatalytic process. It could be considered as a photocatalyst precursor in such processes, due to its low cost and easy access.

Keywords: black sand mineral, methyl orange, oxidation, photocatalysis, reduction

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Authors: G. C. Santini, C. Potrich, L. Lunelli, L. Vanzetti, S. Marasso, M. Cocuzza, C. Pederzolli

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The relevance of circulating miRNAs as non-invasive biomarkers for several pathologies is nowadays undoubtedly clear, as they have been found to have both diagnostic and prognostic value able to add fundamental information to patients’ clinical picture. The availability of these data, however, relies on a time-consuming process spanning from the sample collection and processing to the data analysis. In light of this, strategies which are able to ease this procedure are in high demand and considerable effort have been made in developing Lab-on-a-chip (LOC) devices able to speed up and standardise the bench work. In this context, a very promising polydimethylsiloxane (PDMS)-based microdevice which integrates the processing of the biological sample, i.e. purification of extracellular miRNAs, and reverse transcription was previously developed in our lab. In this study, we aimed at the improvement of the miRNA extraction performances of this micro device by increasing the ability of its surface to absorb extracellular miRNAs from biological samples. For this purpose, we focused on the modulation of two properties of the material: roughness and charge. PDMS surface roughness was modulated by casting with several templates (terminated with silicon oxide coated by a thin anti-adhesion aluminum layer), followed by a panel of curing conditions. Atomic force microscopy (AFM) was employed to estimate changes at the nanometric scale. To introduce modifications in surface charge we functionalized PDMS with different mixes of positively charged 3-aminopropyltrimethoxysilanes (APTMS) and neutral poly(ethylene glycol) silane (PEG). The surface chemical composition was characterized by X-ray photoelectron spectroscopy (XPS) and the number of exposed primary amines was quantified with the reagent sulfosuccinimidyl-4-o-(4,4-dimethoxytrityl) butyrate (s-SDTB). As our final end point, the adsorption rate of all these different conditions was assessed by fluorescence microscopy by incubating a synthetic fluorescently-labeled miRNA. Our preliminary analysis identified casting on thermally grown silicon oxide, followed by a curing step at 85°C for 1 hour, as the most efficient technique to obtain a PDMS surface roughness in the nanometric scaleable to trap miRNA. In addition, functionalisation with 0.1% APTMS and 0.9% PEG was found to be a necessary step to significantly increase the amount of microRNA adsorbed on the surface, therefore, available for further steps as on-chip reverse transcription. These findings show a substantial improvement in the extraction efficiency of our PDMS microdevice, ultimately leading to an important step forward in the development of an innovative, easy-to-use and integrated system for the direct purification of less abundant circulating microRNAs.

Keywords: circulating miRNAs, diagnostics, Lab-on-a-chip, polydimethylsiloxane (PDMS)

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Authors: Aleksandra Szunke

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Monetary policy is an important pillar of the economy, directly affecting on the condition of banking sector. Depending on the strategy may both support functioning of banking institutions, as well as limit their excessively risky activities. The literature studies indicate a large number of publications, which include characteristics of initiatives, implemented by central banks during the global financial crisis and the potential effects of the use of non-standard monetary policy instruments. However, the empirical evidence about their effects and real consequences for the financial markets are still not final. Even before the escalation of instability, Bernanke, Reinhart, and Sack (2004) analyzed the effectiveness of various unconventional monetary tools in lowering long-term interest rates in the United States and Japan. The obtained results largely confirmed the effectiveness of the zero-interest-rate policy and Quantitative Easing (QE) in achieving the goal of reducing long-term interest rates. Japan, considered as the precursor of QE policy, also conducted research about the consequences of non-standard instruments, implemented to restore financial stability of the country. Although the literature about the effectiveness of Quantitative Easing in Japan is extensive, it does not uniquely specify whether it brought permanent effects. The main aim of the study is to identify the implications of non-standard monetary policy, implemented by selected central banks (the Federal Reserve System, Bank of England and European Central Bank), paying particular attention to the consequences into three areas: the size of money supply, financial markets, and the real economy.

Keywords: consequences of modern monetary policy, quantitative easing policy, banking sector instability, global financial crisis

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Authors: Ipsita Biswas, Arnab Sarkar, Ashikur Rahaman, Gopeswar Mukherjee, Subhrangsu Chatterjee, Shamee Bhattacharjee, Deba Prasad Mandal

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One of the major reasons for the high mortality rate of lung cancer is the substantial delays in disease detection at late metastatic stages. It is of utmost importance to understand the detailed molecular signaling and detect the molecular markers that can be used for the early diagnosis of cancer. Several studies explored the emerging roles of long noncoding RNAs (lncRNAs) in various cancers as well as lung cancer. A long non-coding RNA LINC00273 was recently discovered to promote cancer cell migration and invasion, and its positive correlation with the pathological stages of metastasis may prove it to be a potential target for inhibiting cancer cell metastasis. Comparing real-time expression of LINC00273 in various human clinical cancer tissue samples with normal tissue samples revealed significantly higher expression in cancer tissues. This long intergenic noncoding RNA was found to be highly expressed in human liver tumor-initiating cells, human gastric adenocarcinoma AGS cell line, as well as human non-small cell lung cancer A549 cell line. SiRNA and shRNA-induced knockdown of LINC00273 in both in vitro and in vivo nude mice significantly subsided AGS and A549 cancer cell migration and invasion. LINC00273 knockdown also reduced TGF-β induced SNAIL, SLUG, VIMENTIN, ZEB1 expression, and metastasis in A549 cells. Plenty of reports have suggested the role of microRNAs of the miR200 family in reversing epithelial to mesenchymal transition (EMT) by inhibiting ZEB transcription factors. In this study, hsa-miR-200a-3p was predicted via IntaRNA-Freiburg RNA tools to be a potential target of LINC00273 with a negative free binding energy of −8.793 kcal/mol, and this interaction was verified as a confirmed target of LINC00273 by RNA pulldown, real-time PCR and luciferase assay. Mechanistically, LINC00273 accelerated TGF-β induced EMT by sponging hsa-miR-200a-3p which in turn liberated ZEB1 and promoted prometastatic functions in A549 cells in vitro as verified by real-time PCR and western blotting. The similar expression patterns of these EMT regulatory pathway molecules, viz. LINC00273, hsa-miR-200a-3p, ZEB1 and TGF-β, were also detected in various clinical samples like breast cancer tissues, oral cancer tissues, lung cancer tissues, etc. Overall, this LINC00273 mediated EMT regulatory signaling can serve as a potential therapeutic target for the prevention of lung cancer metastasis.

Keywords: epithelial to mesenchymal transition, long noncoding RNA, microRNA, non-small-cell lung carcinoma

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Authors: Miroslava Rysová, Zdena Syrová, Tomáš Zajíc, Petr Exnar

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Currently, attention of tissue engineers has been attracted to novel nanofibrous materials having advanced properties and ability to mimic extracellular matrix (ECM) by structure which makes them interesting candidates for application in regenerative medicine as scaffolding and/or drug delivering material. Throughout the last decade, more than 200 synthetic and natural polymers have been successfully electrospun leading to the formation of nanofibres with a wide range of chemical, mechanical and degradation properties. In this family, inorganic nanofibres represent very specific group offering an opportunity to manufacture inert to body, well degradable and in properties tunable material. Aim of this work, was to reveal unique properties of silica (SiO2, CAS 7631-86-9) nanofibres and their potential in field of regenerative medicine. Silica nanofibres were prepared by sol-gel method from tetraethyl orthosilicate (TEOS, CAS 78-10-4) as a precursor and subsequently manufactured by needleless electrospinning on NanospiderTM device. Silica nanofibres thermally stabilized under 200°C were confirmed to be fully biodegradable and soluble in several simulated body fluids. In vitro cytotoxicity tests of eluate (ES ISO 10993-5:1999) and in direct contact (ES ISO 10993-5:2009) showed no toxicity - e.g. cell viabilities reached values exceeding 80%. Those results were obtained equally from two different cell lines (Vero, 3T3). Non-toxicity of silaca nanofibres´ eluate was additionally confirmed in real time by testing on xCelligence (ACEA Biosciences, Inc.) device. Both cell types also showed good adhesion to material. To conclude, all mentioned results lead to resumption that silica nanofibres have a potential as material for regenerative medicine which opens door to further research.

Keywords: cytotoxicity, electrospinning, nanofibres, silica, tissue engineering

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Authors: Olga Shapovalova, Vladimir Vinogradov

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Among many different sol – gel matrices only alumina can be successfully parenteral injected in the human body. And this is not surprising, because boehmite (aluminium oxyhydroxide) is the metal oxide approved by FDA and EMA for intravenous and intramuscular administrations, and also has been using for a longtime as adjuvant for producing of many modern vaccines. In our earlier study, it has been shown, that denaturation temperature of enzymes entrapped in sol-gel boehmite matrix increases for 30 – 60 °С with preserving of initial activity. It makes such matrices more attractive for long-term storage of non-stable drugs. In current work we present ultrasound-assisted sol-gel synthesis of nano-boehmite. This method provides bio-friendly, very stable, highly homogeneous alumina sol with using only water and aluminium isopropoxide as a precursor. Many parameters of the synthesis were studied in details: time of ultrasound treatment, US frequency, surface area, pore and nanoparticle size, zeta potential and others. Here we investigated the dependence of stability of colloidal sols and textural properties of the final composites as a function of the time of ultrasonic treatment. Chosen ultrasonic treatment time was between 30 and 180 minutes. Surface area, average pore diameter and total pore volume of the final composites were measured by surface and pore size analyzer Nova 1200 Quntachrome. It was shown that the matrices with ultrasonic treatment time equal to 90 minutes have the biggest surface area 431 ± 24 m2/g. On the other had such matrices have a smaller stability in comparison with the samples with ultrasonic treatment time equal to 120 minutes that have the surface area 390 ± 21 m2/g. It was shown that the stable sols could be formed only after 120 minutes of ultrasonic treatment, otherwise the white precipitate of boehmite is formed. We conclude that the optimal ultrasonic treatment time is 120 minutes.

Keywords: boehmite matrix, stabilisation, ultrasound-assisted sol-gel synthesis

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Authors: Jagadeshvaran P. L., Kamlesh Panwar, Indumathi Ramakrishnan, Suryasarathi Bose

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The surge in the usage of wireless electronics and communication devices has engendered a different form of pollution, viz. the electromagnetic (EM) pollution and yet another serious issue, electromagnetic interference (EMI). There is a legitimate need to develop strategies and materials to combat this issue, otherwise leading to dreadful consequences. Functional textiles have emerged as the modern materials to help attenuate EM waves due to the numerous advantages – flexibility being the most important. In addition to this, there is an inherent advantage of multiple interfaces in coated fabrics that can engender significant attenuation. Herein we report a coating having multifunctional properties – capable of blocking both UV and EM radiation (predominantly of the microwave frequencies) with flame-retarding properties. The layer described here comprises iron titanate(FT) synthesized from its sustainable precursor – ilmenite sand and carbon nanotubes (CNT) dispersed in waterborne polyurethane. It is worth noting that FT's use as a multifunctional material is being reported for the first time. It was observed that a single layer of coated fabric shows EMI shielding effectiveness of -40 dB translating to 99.99% attenuation and similarly a UV blocking of 99.99% in the wavelength ranging from 200-400 nm. The microwave shielding properties of the fabric were demonstrated using a Bluetooth module – where the coated fabric was able to block the incoming Bluetooth signals to the module from a mobile phone. Besides, the coated fabrics exhibited phenomenal enhancement in thermal stability - a five percent increase in the limiting oxygen index (LOI) was observed upon the application of the coating. Such exceptional properties complement cotton fabrics' existing utility, thereby extending their use to specialty applications.

Keywords: multifunctional coatings, EMI shielding, UV blocking, iron titanate, CNT, waterborne polyurethane, cotton fabrics

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Authors: Samane Maroufi, Rasoul Khayyam Nekouei, Sajjad Mofarah

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Fabrication of the state-of-the-art portable pseudocapacitors with the desired transparency, mechanical flexibility, capacitance, and durability is challenging. In most cases, the fabrication of such devices requires critical elements which are either under the crisis of depletion or their extraction from virgin mineral ores have sever environmental impacts. This urges the use of secondary resources instead of virgin resources in fabrication of advanced devices. In this research, ultrathin films of defect-rich Mn1−x−y(CexLay)O2−δ with controllable thicknesses in the range between 5 nm to 627 nm and transmittance (≈29–100%) have been fabricated via an electrochemical chronoamperometric deposition technique using an aqueous precursor derived during the selective purification of rare earth oxide (REOs) isolated from end-of-life nickel-metal hydride (Ni-MH) batteries. Intercalation/de-intercalation of anionic O2− through the atomic tunnels of the stratified Mn1−x−y(CexLay)O2−δ crystallites was found to be responsible for outstanding areal capacitance of 3.4 mF cm−2 of films with 86% transmittance. The intervalence charge transfer among interstitial Ce/La cations and Mn oxidation states within the Mn1−x−y(CexLay)O2−δ structure resulted in excellent capacitance retention of ≈90% after 16 000 cycles. The synthesised transparent flexible Mn1−x−y(CexLay)O2−δ full-cell pseudocapacitor device possessed the energy and power densities of 0.088 μWh cm⁻² and 843 µW cm⁻², respectively. These values show insignificant changes under vigorous twisting and bending to 45–180° confirming these value-added materials are intriguing alternatives for size-sensitive energy storage devices. This research confirms the feasibility of utilisation of secondary waste resources for the fabrication of high-quality pseudocapacitors with engineered defects with the desired flexibility, transparency, and cycling stability suitable for size-sensitive portable electronic devices.

Keywords: pseudocapacitors, energy storage devices, flexible and transparent, sustainability

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Authors: Mannar R. Maurya, Bhawna Uprety, Fernando Avecilla, Pedro Adão, J. Costa Pessoa

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The reaction of the tripodal tetradentate dibasic ligand 6,6'–(2–(pyridin–2–yl)ethylazanediyl)bis(methylene)bis(2,4–di–tert–butylphenol), H2L1 I, with [VIVO(acac)2] in CH3CN gives the VVO–complex, [VVO(acac)(L1)] 1. Crystallization of 1 in CH3CN at ~0 ºC, gives dark blue crystals of 1, while at room temperature it affords dark green crystals of [{VVO(L1)}2µ–O] 3. Upon prolonged treatment of 1 in MeOH [VVO(OMe)(MeOH)(L1)] 2 is obtained. All three complexes are analyzed by single–crystal X–ray diffraction, depicting distorted octahedral geometry around vanadium. In the reaction of H2L1 with VIVOSO4 partial hydrolysis of the tripodal ligand results in elimination of the pyridyl fragment of L1 and the formation of H[VVO2(L2)] 4, containing the ONO tridentate ligand 6,6'–azanediylbis(methylene)bis(2,4–di–tert–butylphenol), H2L2 II. Compound 4, which was not fully characterized, undergoes dimerization in acetone yielding the hydroxido–bridged [{VVO(L2)}2µ–(HO)2] 5, having distorted octahedral geometry around each vanadium. In contrast, from a solution of 4 in acetonitrile, the dinuclear compound [{VVO(L2)}2µ–O] 6 is obtained, with trigonal bipyramidal geometry around each vanadium. The methoxido complex 2 is successfully employed as a functional catechol–oxidase mimic in the oxidation of catechol to o–quinone under air. The process is confirmed to follow a Michaelis–Menten type kinetics with respect to catechol, the Vmax and KM values obtained being 7.66×10–6 M min -1 and 0.0557 M, respectively, and the turnover frequency is 0.0541 min–1. Complex 2 is also used as a catalyst precursor for the oxidative bromination of thymol in aqueous medium. The selectivity shows quite interesting trends, namely when not using excess of primary oxidizing agent, H2O2 the para mono–brominated product corresponds to ~93 % of the products and no dibromo derivative is formed.

Keywords: oxidovanadium (V) complexes, tripodal ligand, crystal structure, catechol oxidase mimetic activity

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Authors: Ana Paula Mousinho, Ronaldo D. Mansano, Nelson Ordonez

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Carbon nanotubes are one of the main elements in nanotechnologies; their applications are in microelectronics, nano-electronics devices (photonics, spintronic), chemical sensors, structural material and currently in clean energy devices (supercapacitors and fuel cells). The use of magnetic particle decorated carbon nanotubes increases the applications in magnetic devices, magnetic memory, and magnetic oriented drug delivery. In this work, single-walled carbon nanotubes (CNTs) forest decorated with chromium were deposited at room temperature by high-density plasma chemical vapor deposition (HDPCVD) system. The CNTs forest was obtained using pure methane plasmas and chromium, as precursor material (seed) and for decorating the CNTs. Magnetron sputtering deposited the chromium on silicon wafers before the CNTs' growth. Scanning electron microscopy, atomic force microscopy, micro-Raman spectroscopy, and X-ray diffraction characterized the single-walled CNTs forest decorated with chromium. In general, the CNTs' spectra show a unique emission band, but due to the presence of the chromium, the spectra obtained in this work showed many bands that are related to the CNTs with different diameters. The CNTs obtained by the HDPCVD system are highly aligned and showed metallic features, and they can be used as photonic material, due to the unique structural and electrical properties. The results of this work proved the possibility of obtaining the controlled deposition of aligned single-walled CNTs forest films decorated with chromium by high-density plasma chemical vapor deposition system.

Keywords: CNTs forest, high density plasma deposition, high-aligned CNTs, nanomaterials

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