Search results for: graded photonic crystal

Authors: Wael M. Rabeh, Cesar Carrasco-Lopez, Juliana C. Ferreira, Pance Naumov

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Bioluminescence, the emission of light from a biological process, is found in various living organisms including bacteria, fireflies, beetles, fungus and different marine organisms. Luciferase is an enzyme that catalyzes a two steps oxidation of luciferin in the presence of Mg2+ and ATP to produce oxyluciferin and releases energy in the form of light. The luciferase assay is used in biological research and clinical applications for in vivo imaging, cell proliferation, and protein folding and secretion analysis. The luciferase enzyme consists of two domains, a large N-terminal domain (1-436 residues) that is connected to a small C-terminal domain (440-544) by a flexible loop that functions as a hinge for opening and closing the active site. The two domains are separated by a large cleft housing the active site that closes after binding the substrates, luciferin and ATP. Even though all insect luciferases catalyze the same chemical reaction and share 50% to 90% sequence homology and high structural similarity, they emit light of different colors from green at 560nm to red at 640 nm. Currently, the majority of the structural and biochemical studies have been conducted on green-emitting firefly luciferases. To address the color emission mechanism, we expressed and purified two luciferase enzymes with blue-shifted green and red emission from indigenous Brazilian species Amydetes fanestratus and Phrixothrix, respectively. The two enzymes naturally emit light of different colors and they are an excellent system to study the color-emission mechanism of luciferases, as the current proposed mechanisms are based on mutagenesis studies. Using a vapor-diffusion method and a high-throughput approach, we crystallized and solved the crystal structure of both enzymes, at 1.7 Å and 3.1 Å resolution respectively, using X-ray crystallography. The free enzyme adopted two open conformations in the crystallographic unit cell that are different from the previously characterized firefly luciferase. The blue-shifted green luciferase crystalized as a monomer similar to other luciferases reported in literature, while the red luciferases crystalized as an octamer and was also purified as an octomer in solution. The octomer conformation is the first of its kind for any insect’s luciferase, which might be relate to the red color emission. Structurally designed mutations confirmed the importance of the transition between the open and close conformations in the fine-tuning of the color and the characterization of other interesting mutants is underway.

Keywords: bioluminescence, enzymology, structural biology, x-ray crystallography

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Authors: Muhammad Yasir Tarar

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Background: Intraarticular steroid injections are an effective option in alleviating the symptoms of conditions like osteoarthritis, rheumatoid arthritis, crystal arthropathy, and rotator cuff tendinopathy. Most of these injections are conducted in the elderly who are on polypharmacy, including anticoagulants at times. Up to 6% of patients aged 80-84 years have been reported to be taking Warfarin. The literature availability on safety quotient for patients undergoing intraarticular injections on Warfarin is scarce. It has remained debatable over the years which approach is safe for these patients. Continuing warfarin has a theoretical bleeding risk, and stopping it can lead to even severe life-threatening thromboembolic events in high-risk patients. Objectives: To evaluate the risk of bleeding complications in patients on warfarin undergoing intraarticular injections or arthrocentesis. Study Design & Methods: A literature search of MEDLINE (1946 to present), EMBASE (1974 to present), and Cochrane CENTRAL (1988 to present) databases were conducted using any combination of the keywords, Injection, Knee, Shoulder, Joint, Intraarticular, arthrocentesis, Warfarin, and Anticoagulation in November 2020 for articles published in any language with no publication year limit. The study inclusion criteria included reporting on the rate of bleeding complications following injection of the knee or shoulder in patients on warfarin treatment. Randomized control trials and prospective and retrospective study designs were included. An electronic standardized Performa for data extraction was made. The Preferred Reporting Items for Systematic Review and Meta-Analyses (PRISMA) the methodology was used. The articles were appraised using the methodological index for nonrandomized studies. The Cochrane Risk of Bias Tool used to assess the risk of bias in included RCTs and the MINORS tool for assessment of bias in observational studies. Results: The search of databases resulted in a total of 852 articles. Relevant articles as per the inclusion criteria were shortlisted, 7 articles deemed suitable to be include. A total of 1033 joints sample size was undertaken with specified knee and shoulder joints of a total of 820. Only 6 joints had bleeding complications, 5 early bleeding at the time of injection or aspiration, and one late bleeding complication with INR of 5, additionally, 2 patients complained of bruising, 3 of pain, and 1 managed for infection. Conclusions: The results of the metanalysis show that it is relatively safe to perform intraarticular injections in patients on Warfarin regardless of the INR range.

Keywords: arthrocentesis, warfarin, bleeding, injection

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Authors: Ramin Hosseinnezhad, Iurii Vozniak, Andrzej Galeski

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Shear-induced crystallization, originated from orientation of chains along the flow direction, is an inevitable part of most polymer processing technologies. It plays a dominant role in determining the final product properties and is affected by many factors such as shear rate, cooling rate, total strain, etc. Investigation of the shear-induced crystallization process become of great importance for preparation of nanocomposite, which requires crystallization of nanofibrous sheared inclusions at higher temperatures. Thus, the effects of shear time, shear rate, and also thermal condition of cooling on crystallization of two aliphatic-aromatic copolyesters have been investigated. This was performed using Linkam optical shearing system (CSS450) for both Ecoflex® F Blend C1200 produced by BASF and synthesized copolyester of butylene terephthalate and a mixture of butylene esters: adipate, succinate, and glutarate, (PBASGT), containing 60% of aromatic comonomer. Crystallization kinetics of these biodegradable copolyesters was studied at two different conditions of shearing. First, sample with a thickness of 60µm was heated to 60˚C above its melting point and subsequently subjected to different shear rates (100–800 sec-1) while cooling with specific rates. Second, the same type of sample was cooled down when shearing at constant temperature was finished. The intensity of transmitted depolarized light, recorded by a camera attached to the optical microscope, was used as a measure to follow the crystallization. Temperature dependencies of conversion degree of samples during cooling were collected and used to determine the half-temperature (Th), at which 50% conversion degree was reached. Shearing ecoflex films for 45 seconds with a shear rate of 100 sec-1 resulted in significant increase of Th from 56˚C to 70˚C. Moreover, the temperature range for the transition of molten samples to crystallized state decreased from 42˚C to 20˚C. Comparatively low shift of 10˚C in Th towards higher temperature was observed for PBASGT films at shear rate of 600 sec-1 for 45 seconds. However, insufficient melt flow strength and non-laminar flow due to Taylor vortices was a hindrance to reach more elevated Th at very high shear rates (600–800 sec-1). The shift in Th was smaller for the samples sheared at a constant temperature and subsequently cooled down. This may be attributed to the longer time gap between cessation of shearing and the onset of crystallization. The longer this time gap, the more possibility for crystal nucleus to re-melt at temperatures above Tm and for polymer chains to recoil and relax. It is found that the crystallization temperature, crystallization induction time and spherulite growth of aliphatic-aromatic copolyesters are dramatically influenced by both the cooling rate and the shear imposed during the process.

Keywords: induced crystallization, shear rate, aliphatic-aromatic copolyester, ecoflex

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Authors: Nidhi Sharotri, Dhiraj Sud

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Water pollution by pesticides constitutes a serious ecological problem due to their potential toxicity and bioaccumulation. The widespread use of pesticides in industry and agriculture along with their resistance to natural decomposition, biodegradation, chemical and photochemical degradation under typical environmental conditions has resulted in the emergence of these chemicals and their transformed products in natural water. Among AOP’s, heterogeneous photocatalysis using TiO2 as photocatalyst appears as the most emerging destructive technology for mineralization of the pollutant in aquatic streams. Among the various semiconductors (TiO2, ZnO, CdS, FeTiO3, MnTiO3, SrTiO2 and SnO2), TiO2 has proven to be the most efficient photocatalyst for environmental applications due to its biological and chemical inertness, high photo reactivity, non-toxicity, and photo stability. Semiconductor photocatalysts are characterized by an electronic band structure in which valence band and conduction band are separated by a band gap, i.e. a region of forbidden energy. Semiconductor based photocatalysts produces e-/h+ pairs which have been employed for degradation of organic pollutants. The present paper focuses on modification of TiO2 photocatalyst in order to shift its absorption edge towards longer wavelength to make it active under natural light. Semiconductor TiO2 photocatalysts was prepared by doping with anion (N), cation (Mn) and double doped (Mn, N) using greener approach. Titanium isopropoxide is used as titania precursor and ethanedithiol, hydroxyl amine hydrochloride, manganous chloride as sulphur, nitrogen and manganese precursors respectively. Synthesized doped TiO2 nanomaterials are characterized for surface morphology (SEM, TEM), crystallinity (XRD) and optical properties (absorption spectra and band gap). EPR data confirms the substitutional incorporation of Mn2+ in TiO2 lattice. The doping influences the phase transformation of rutile and anatase phase crystal and thereby the absorption spectrum changes were observed. The effect of variation of reaction parameters such as solvent, reaction time and calcination temperature on the yield, surface morphology and optical properties was also investigated. The TEM studies show the particle size of nanomaterials varies from 10-50 nm. The calculated band gap of nanomaterials varies from 2.30-2.60 eV. The photocatalytic degradation of organic pollutant organophosphate pesticide (Quinalphos) has been investigated by studying the changes in UV absorption spectrum and the promising results were obtained under visible light. The complete mineralization of quinalphos has occurred as no intermediates were recorded after 8 hrs of degradation confirmed from the HPLC studies.

Keywords: quinalphos, doped-TiO2, mineralization, EPR

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Authors: Crystal Hoole

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Employee well-being has become an area of concern for top executives and organizations worldwide. In developing countries such as South Africa, and especially in the educational sector, employees have to deal with anxiety, stress, fear, student protests, political and economic turmoil and excessive work demands on a daily basis. Research has shown that workplaces with higher resilience and better well-being strategies also report higher productivity, increased innovation, better employee retention and better employee engagement. Many organisations offer standard employee assistance programs and once-off short interventions. However, most of these well-being initiatives are perceived as ineffective. Some of the criticism centers around a lack of holistic well-being approaches, no proof of the success of well-being initiatives, not being part of the organization’s strategies and a lack of genuine leadership support. This study attempts to illustrate how a holistic well-being intervention, over a period of 100 days, is far more effective in impacting organizational outcomes. A quasi-experimental design, with a pre-test and pro-test design with a randomization strategy, will be used. Measurements of organizational outcomes are taken at three-time points throughout the study, before, middle and after. The constructs that will be measured are employee engagement, psychological well-being, organizational culture and trust, and perceived stress. The well-being is imitative follows a salutogenesis approach and is aimed at building resilience through focusing on six focal areas, namely sleep, mindful eating, exercise, love, gratitude and appreciation, breath work and mindfulness, and finally, purpose. Certain organizational constructs, including employee engagement, psychological well-being, organizational culture and trust and perceived stress, will be measured at three-time points during the study, namely before, middle and after. A quasi-experimental, pre-test and post-test design will be applied, also using a randomization strategy to limit potential bias. Repeated measure ANCOVA will be used to determine whether any change occurred over the period of 100 days. The study will take place in a Higher Education institution in South Africa. The sample will consist of academic and administrative staff. Participants will be assigned to a test and control group. All participants will complete a survey measuring employee engagement, psychological well-being, organizational culture and trust, and perceived stress. Only the test group will undergo the well-being intervention. The study envisages contributing on several levels: Firstly, the study hopes to find a positive increase in the various well-being indicators of the participants who participated in the study and secondly to illustrate that a longer more holistic approach is successful in improving organisational success (as measured in the various organizational outcomes).

Keywords: wellbeing, resilience, organizational success, intervention

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Authors: Ram Mohan, Mahendran Samykano, Shyam Aravamudhan

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Metallic nanowires with sub-micron and hundreds of nanometer diameter have a diversity of applications in nano/micro-electromechanical systems (NEMS/MEMS). Characterizing the mechanical properties of such sub-micron and nano-scale metallic nanowires are tedious; require sophisticated and careful experimentation to be performed within high-powered microscopy systems (scanning electron microscope (SEM), atomic force microscope (AFM)). Also, needed are nanoscale devices for placing the nanowires; loading them with the intended conditions; obtaining the data for load–deflection during the deformation within the high-powered microscopy environment poses significant challenges. Even picking the grown nanowires and placing them correctly within a nanoscale loading device is not an easy task. Mechanical characterizations through experimental methods for such nanowires are still very limited. Various techniques at different levels of fidelity, resolution, and induced errors have been attempted by material science and nanomaterial researchers. The methods for determining the load, deflection within the nanoscale devices also pose a significant problem. The state of the art is thus still at its infancy. All these factors result and is seen in the wide differences in the characterization curves and the reported properties in the current literature. In this paper, we discuss and present our experimental method, results, and discussions of uniaxial tensile loading and the development of subsequent stress–strain characteristics curves for Nickel nanowires. Nickel nanowires in the diameter range of 220–270 nm were obtained in our laboratory via an electrodeposition method, which is a solution based, template method followed in our present work for growing 1-D Nickel nanowires. Process variables such as the presence of magnetic field, its intensity; and varying electrical current density during the electrodeposition process were found to influence the morphological and physical characteristics including crystal orientation, size of the grown nanowires1. To further understand the correlation and influence of electrodeposition process variables, associated formed structural features of our grown Nickel nanowires to their mechanical properties, careful experiments within scanning electron microscope (SEM) were conducted. Details of the uniaxial tensile characterization, testing methodology, nanoscale testing device, load–deflection characteristics, microscopy images of failure progression, and the subsequent stress–strain curves are discussed and presented.

Keywords: uniaxial tensile characterization, nanowires, electrodeposition, stress-strain, nickel

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Authors: Belen Montero, Carmen Ramirez, Maite Rico, Rebeca Bouza, Irene Derungs

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Starch is a promising polymer for producing biocomposite materials because it is renewable, completely biodegradable and easily available at a low cost. Thermoplastic starches (TPS) can be obtained after the disruption and plasticization of native starch with a plasticizer. In this work, the solvent casting method was used to obtain TPS films from wheat starch plasticized with glycerol and reinforced with nanocellulose (CNC). X-ray diffraction analysis was used to follow the evolution of the crystallinity. The native wheat starch granules have shown a profile corresponding to A-type crystal structures typical for cereal starches. When TPS films are analyzed a high amorphous halo centered on 19º is obtained, indicating the plasticization process is completed. SEM imaging was made in order to analyse the morphology. The image from the raw wheat starch granules shows a bimodal granule size distribution with some granules in large round disk-shape forms (A-type) and the others as smaller spherical particles (B-type). The image from the neat TPS surface shows a continuous surface. No starch aggregates or swollen granules can be seen so, the plasticization process is complete. In the surfaces of reinforced TPS films aggregates are seen as the CNC concentration in the matrix increases. The CNC influence on the mechanical properties of TPS films has been studied by dynamic mechanical analysis. A direct relation exists between the storage modulus values, E’, and the CNC content in reinforced TPS films: higher is the content of nanocellulose in the composite, higher is the value of E’. This reinforcement effect can be explained by the appearance of a strong and crystalline nanoparticle-TPS interphase. Thermal stability of films was analysed by TGA. It has not observed any influence on the behaviour related to the thermal degradation of films with the incorporation of the CNC. Finally, the resistance to the water absorption films was analysed following the standard UNE-EN ISO 1998:483. The percentage of water absorbed by the samples at each time was calculated. The addition of 5 wt % of CNC to the TPS matrix leads to a significant improvement in the moisture resistance of the starch based material decreasing their diffusivity. It has been associated to the formation of a nanocrystal network that prevents swelling of the starch and therefore water absorption and to the high crystallinity of cellulose compared to starch. As a conclusion, the wheat film reinforced with 5 wt % of cellulose nanocrystals seems to be a good alternative for short-life applications into the packaging industry, because of its greatest rigidity, thermal stability and moisture sorption resistance.

Keywords: biocomposites, nanocellulose, starch, wheat

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Authors: Michalina Aniola, Andrzej Katrusiak

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4,4-Bipyridine is an important compound often used in chemical practice and more recently frequently applied for designing new metal organic framework (MoFs). Here we present a systematic high-pressure study of its hydrobromide salt. 4,4-Bipyridine hydrobromide monohydrate, 44biPyHBrH₂O, at ambient-pressure is orthorhombic, space group P212121 (phase a). Its hydrostatic compression shows that it is stable to 1.32 GPa at least. However, the recrystallization above 0.55 GPa reveals a new hidden b-phase (monoclinic, P21/c). Moreover, when the 44biPyHBrH2O is heated to high temperature the chemical reactions of this compound in methanol solution can be observed. High-pressure experiments were performed using a Merrill-Bassett diamond-anvil cell (DAC), modified by mounting the anvils directly on the steel supports, and X-ray diffraction measurements were carried out on a KUMA and Excalibur diffractometer equipped with an EOS CCD detector. At elevated pressure, the crystal of 44biPyHBrH₂O exhibits several striking and unexpected features. No signs of instability of phase a were detected to 1.32 GPa, while phase b becomes stable at above 0.55 GPa, as evidenced by its recrystallizations. Phases a and b of 44biPyHBrH2O are partly isostructural: their unit-cell dimensions and the arrangement of ions and water molecules are similar. In phase b the HOH-Br- chains double the frequency of their zigzag motifs, compared to phase a, and the 44biPyH+ cations change their conformation. Like in all monosalts of 44biPy determined so far, in phase a the pyridine rings are twisted by about 30 degrees about bond C4-C4 and in phase b they assume energy-unfavorable planar conformation. Another unusual feature of 44biPyHBrH2O is that all unit-cell parameters become longer on the transition from phase a to phase b. Thus the volume drop on the transition to high-pressure phase b totally depends on the shear strain of the lattice. Higher temperature triggers chemical reactions of 44biPyHBrH2O with methanol. When the saturated methanol solution compound precipitated at 0.1 GPa and temperature of 423 K was required to dissolve all the sample, the subsequent slow recrystallization at isochoric conditions resulted in disalt 4,4-bipyridinium dibromide. For the 44biPyHBrH2O sample sealed in the DAC at 0.35 GPa, then dissolved at isochoric conditions at 473 K and recrystallized by slow controlled cooling, a reaction of N,N-dimethylation took place. It is characteristic that in both high-pressure reactions of 44biPyHBrH₂O the unsolvated disalt products were formed and that free base 44biPy and H₂O remained in the solution. The observed reactions indicate that high pressure destabilized ambient-pressure salts and favors new products. Further studies on pressure-induced reactions are carried out in order to better understand the structural preferences induced by pressure.

Keywords: conformation, high-pressure, negative area compressibility, polymorphism

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Authors: Martyna Ekiert, Natalia Grzechnik, Joanna Karbowniczek, Urszula Stachewicz, Andrzej Mlyniec

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Tendon grafting is a common procedure performed to treat tendon rupture. Before the surgical procedure, tissues intended for grafts (i.e., Achilles tendon) are stored in ultra-low temperatures for a long time and also may be subjected to unfavorable conditions, such as repetitive freezing (F) and thawing (T). Such storage protocols may highly influence the graft mechanical properties, decrease its functionality and thus increase the risk of complications during the transplant procedure. The literature reports on the influence of multiple F/T cycles on internal structure and mechanical properties of tendons stay inconclusive, confirming and denying the negative influence of multiple F/T at the same time. An inconsistent research methodology and lack of clear limit of F/T cycles, which disqualifies tissue for surgical graft purposes, encouraged us to investigate the issue of multiple F/T cycles by the mean of biomechanical tensile tests supported with Scanning Electron Microscope (SEM) imaging. The study was conducted on male bovine Achilles tendon-derived from the local abattoir. Fresh tendons were cleaned of excessive membranes and then sectioned to obtained fascicle bundles. Collected samples were randomly assigned to 6 groups subjected to 1, 2, 4, 6, 8 and 12 cycles of freezing-thawing (F/T), respectively. Each F/T cycle included deep freezing at -80°C temperature, followed by thawing at room temperature. After final thawing, thin slices of the side part of samples subjected to 1, 4, 8 and 12 F/T cycles were collected for SEM imaging. Then, the width and thickness of all samples were measured to calculate the cross-sectional area. Biomechanical tests were performed using the universal testing machine (model Instron 8872, INSTRON®, Norwood, Massachusetts, USA) using a load cell with a maximum capacity of 250 kN and standard atmospheric conditions. Both ends of each fascicle bundle were manually clamped in grasping clamps using abrasive paper and wet cellulose wadding swabs to prevent tissue slipping while clamping and testing. Samples were subjected to the testing procedure including pre-loading, pre-cycling, loading, holding and unloading steps to obtain stress-strain curves for representing tendon stretching and relaxation. The stiffness of AT fascicles bundle samples was evaluated in terms of modulus of elasticity (Young’s modulus), calculated from the slope of the linear region of stress-strain curves. SEM imaging was preceded by chemical sample preparation including 24hr fixation in 3% glutaraldehyde buffered with 0.1 M phosphate buffer, washing with 0.1 M phosphate buffer solution and dehydration in a graded ethanol solution. SEM images (Merlin Gemini II microscope, ZEISS®) were taken using 30 000x mag, which allowed measuring a diameter of collagen fibrils. The results confirm a decrease in fascicle bundles Young’s modulus as well as a decrease in the diameter of collagen fibrils. These results confirm the negative influence of multiple F/T cycles on the mechanical properties of tendon tissue.

Keywords: biomechanics, collagen, fascicle bundles, soft tissue

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Authors: Soma Banerjee, Aamen Talukdar, Argha Mandal, Dipankar Chaudhuri

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Japanese Encephalitis is a major infectious disease with nearly half the world’s population living in areas where it is prevalent. Currently, treatment for it involves only supportive care and symptom management through vaccination. Due to the lack of antiviral drugs against Japanese Encephalitis Virus (JEV), the quest for such agents remains a priority. For these reasons, simulation studies of drug targets against JEV are important. Towards this purpose, docking experiments of the kinase inhibitors were done against the chosen target NS3 helicase as it is a nucleoside binding protein. Previous efforts regarding computational drug design against JEV revealed some lead molecules by virtual screening using public domain software. To be more specific and accurate regarding finding leads, in this study a proprietary software Schrödinger-GLIDE has been used. Druggability of the pockets in the NS3 helicase crystal structure was first calculated by SITEMAP. Then the sites were screened according to compatibility with ATP. The site which is most compatible with ATP was selected as target. Virtual screening was performed by acquiring ligands from databases: KinaseSARfari, KinaseKnowledgebase and Published inhibitor Set using GLIDE. The 25 ligands with best docking scores from each database were re-docked in XP mode. Protein structure alignment of NS3 was performed using VAST against MMDB, and similar human proteins were docked to all the best scoring ligands. The low scoring ligands were chosen for further studies and the high scoring ligands were screened. Seventy-three ligands were listed as the best scoring ones after performing HTVS. Protein structure alignment of NS3 revealed 3 human proteins with RMSD values lesser than 2Å. Docking results with these three proteins revealed the inhibitors that can interfere and inhibit human proteins. Those inhibitors were screened. Among the ones left, those with docking scores worse than a threshold value were also removed to get the final hits. Analysis of the docked complexes through 2D interaction diagrams revealed the amino acid residues that are essential for ligand binding within the active site. Interaction analysis will help to find a strongly interacting scaffold among the hits. This experiment yielded 21 hits with the best docking scores which could be investigated further for their drug like properties. Aside from getting suitable leads, specific NS3 helicase-inhibitor interactions were identified. Selection of Target modification strategies complementing docking methodologies which can result in choosing better lead compounds are in progress. Those enhanced leads can lead to better in vitro testing.

Keywords: antivirals, docking, glide, high-throughput virtual screening, Japanese encephalitis, ns3 helicase

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Authors: Dong Zhao

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Even though the recent claim of room temperature superconductivity by LK-99 was confirmed an unsuccessful attempt, this work reawakened people’s century striving to get applicable superconductors with Tc of room temperature or higher and under ambient pressure. One of the efforts was focusing on exploring the thorium salts. This is because certain thorium compounds revealed an unusual property of having both high electrical conductivity and diamagnetism or the so-called “coexistence of high electrical conductivity and diamagnetism.” It is well known that this property of the coexistence of high electrical conductivity and diamagnetism is held by superconductors because of the electron pairings. Consequently, the likelihood for these thorium compounds to have superconducting properties becomes great. However, as a surprise, these thorium salts possess this property at room temperature and atmosphere pressure. This gives rise to solid evidence for these thorium compounds to be room-temperature superconductors without a need for external pressure. Among these thorium compound superconductors claimed in that work, thorium di-iodide (ThI₂) is a unique one and has received comprehensive discussion. ThI₂ was synthesized and structurally analyzed by the single crystal diffraction method in the 1960s. Its special property of coexistence of high electrical conductivity and diamagnetism was revealed. Because of this unique property, a special molecular configuration was sketched. Except for an ordinary oxidation of +2 for the thorium cation, the thorium’s oxidation state in ThI₂ is +4. According to the experimental results, ThI₂‘s actual molecular configuration was determined as an unusual one of [Th4+(e-)2](I-)2. This means that the ThI₂ salt’s cation is composed of a [Th4+(e-)2]2+ cation core. In other words, the cation of ThI₂ is constructed by combining an oxidation state +4 of the thorium atom and a pair of electrons or an electron lone pair located on the thorium atom. This combination of the thorium atom and the electron lone pair leads to an oxidation state +2 for the [Th4+(e-)2]2+ cation core. This special construction of the thorium cation is very distinctive, which is believed to be the factor that grants ThI₂ the room temperature superconductivity. Actually, the key for ThI₂ to become a room-temperature superconductor is this characteristic electron lone pair residing on the thorium atom along with the formation of a network constructed by the thorium atoms. This network specializes in a way that allows the electron lone pairs to hop over it and, thus, to generate the supercurrent. This work will discuss, in detail, the special electrical and magnetic properties of ThI₂ as well as its structural features at ambient conditions. The exploration of how the electron pairing in combination with the structurally specialized network works together to bring ThI₂ into a superconducting state. From the experimental results, strong evidence has definitely pointed out that the ThI₂ should be a superconductor, at least at room temperature and under atmosphere pressure.

Keywords: co-existence of high electrical conductivity and diamagnetism, electron lone pair, room temperature superconductor, special molecular configuration of thorium di-iodide ThI₂

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Authors: Yakup Ulusu, Numan Eczacıoğlu, İsa Gökçe, Helen Waller, Jeremy H. Lakey

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Besides having the appropriate amino acid sequence to perform the function of proteins, it is important to have correct conformation after this sequence to process. To consist of this conformation depends on the amino acid sequence at the primary structure, hydrophobic interaction, chaperones and enzymes in charge of folding etc. Misfolded proteins are not functional and tend to be aggregated. Cysteine originating disulfide cross-links make stable this conformation of functional proteins. When two of the cysteine amino acids come side by side, disulfide bond is established that forms a cystine bridge. Due to this feature cysteine plays an important role on the formation of three-dimensional structure of many proteins. There are two cysteine amino acids (C44, C69) in the Tol-A-III protein. Unlike protein disulfide bonds from within his own, any non-specific cystine bridge causes a change in the three dimensional structure of the protein. Proteins can be expressed in various host cells as directly or fusion (chimeric). As a result of overproduction of the recombinant proteins, aggregation of insoluble proteins in the host cell can occur by forming a crystal structure called inclusion body. In general fusion proteins are produced for provide affinity tags to make proteins more soluble and production of some toxic proteins via fusion protein expression system like pTolT. Proteins can be modified by using a site-directed mutagenesis. By this way, creation of non-specific disulfide crosslinks can be prevented at fusion protein expression system via the present cysteine replaced by another amino acid such as serine, glycine or etc. To do this, we need; a DNA molecule that contains the gene that encodes for the target protein, required primers for mutation to be designed according to site directed mutagenesis reaction. This study was aimed to be replaced cysteine encoding codon TGT with serine encoding codon AGT. For this sense and reverse primers designed (given below) and used site-directed mutagenesis reaction. Several new copy of the template plasmid DNA has been formed with above mentioned mutagenic primers via polymerase chain reaction (PCR). PCR product consists of both the master template DNA (wild type) and the new DNA sequences containing mutations. Dpn-l endonuclease restriction enzyme which is specific for methylated DNA and cuts them to the elimination of the master template DNA. E. coli cells obtained after transformation were incubated LB medium with antibiotic. After purification of plasmid DNA from E. coli, the presence of the mutation was determined by DNA sequence analysis. Developed this new plasmid is called PtolT-δ.

Keywords: site directed mutagenesis, Escherichia coli, pTolT, protein expression

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Authors: Taro Komori, Toshiki Gushi, Akihito Anzai, Taku Hirose, Kaoru Toko, Shinji Isogami, Takashi Suemasu

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Ferrimagnetic antiperovskite Mn₄₋ₓNiₓN thin film exhibits both small saturation magnetization and rather large perpendicular magnetic anisotropy (PMA) when x is small. Both of them are suitable features for application to current induced domain wall motion devices using spin transfer torque (STT). In this work, we successfully grew antiperovskite 30-nm-thick Mn₄₋ₓNiₓN epitaxial thin films on MgO(001) and STO(001) substrates by MBE in order to investigate their crystalline qualities and magnetic and magneto-transport properties. Crystalline qualities were investigated by X-ray diffraction (XRD). The magnetic properties were measured by vibrating sample magnetometer (VSM) at room temperature. Anomalous Hall effect was measured by physical properties measurement system. Both measurements were performed at room temperature. Temperature dependence of magnetization was measured by VSM-Superconducting quantum interference device. XRD patterns indicate epitaxial growth of Mn₄₋ₓNiₓN thin films on both substrates, ones on STO(001) especially have higher c-axis orientation thanks to greater lattice matching. According to VSM measurement, PMA was observed in Mn₄₋ₓNiₓN on MgO(001) when x ≤ 0.25 and on STO(001) when x ≤ 0.5, and MS decreased drastically with x. For example, MS of Mn₃.₉Ni₀.₁N on STO(001) was 47.4 emu/cm³. From the anomalous Hall resistivity (ρAH) of Mn₄₋ₓNiₓN thin films on STO(001) with the magnetic field perpendicular to the plane, we found out Mr/MS was about 1 when x ≤ 0.25, which suggests large magnetic domains in samples and suitable features for DW motion device application. In contrast, such square curves were not observed for Mn₄₋ₓNiₓN on MgO(001), which we attribute to difference in lattice matching. Furthermore, it’s notable that although the sign of ρAH was negative when x = 0 and 0.1, it reversed positive when x = 0.25 and 0.5. The similar reversal occurred for temperature dependence of magnetization. The magnetization of Mn₄₋ₓNiₓN on STO(001) increases with decreasing temperature when x = 0 and 0.1, while it decreases when x = 0.25. We considered that these reversals were caused by magnetic compensation which occurred in Mn₄₋ₓNiₓN between x = 0.1 and 0.25. We expect Mn atoms of Mn₄₋ₓNiₓN crystal have larger magnetic moments than Ni atoms do. The temperature dependence stated above can be explained if we assume that Ni atoms preferentially occupy the corner sites, and their magnetic moments have different temperature dependence from Mn atoms at the face-centered sites. At the compensation point, Mn₄₋ₓNiₓN is expected to show very efficient STT and ultrafast DW motion with small current density. What’s more, if angular momentum compensation is found, the efficiency will be best optimized. In order to prove the magnetic compensation, X-ray magnetic circular dichroism will be performed. Energy dispersive X-ray spectrometry is a candidate method to analyze the accurate composition ratio of samples.

Keywords: compensation, ferrimagnetism, Mn₄N, PMA

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Authors: Armin Solemanifar, Arthur Wilkinson, Kinjalkumar Patel

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Carbon fibre (CF) - polymer laminate composites have very low densities (approximately 40% lower than aluminium), high strength and high stiffness but in terms of toughness properties they often require modifications. For example, adding rubbers or thermoplastics toughening agents are common ways of improving the interlaminar fracture toughness of initially brittle thermoset composite matrices. The main aim of this project was to toughen CF-epoxy resin laminate composites using hybrid CF-fabrics incorporating Innegra™ a commercial highly-oriented polypropylene (PP) fibre, in which more than 90% of its crystal orientation is parallel to the fibre axis. In this study, the damage tolerance of hybrid (carbon-Innegra, CI) composites was investigated. Laminate composites were produced by resin-infusion using: pure CF fabric; fabrics with different ratios of commingled CI, and two different types of pure Innegra fabrics (Innegra 1 and Innegra 2). Dynamic mechanical thermal analysis (DMTA) was used to measure the glass transition temperature (Tg) of the composite matrix and values of flexural storage modulus versus temperature. Mechanical testing included drop-weight impact, compression-after-impact (CAI), and interlaminar (short-beam) shear strength (ILSS). Ultrasonic C-Scan imaging was used to determine the impact damage area and scanning electron microscopy (SEM) to observe the fracture mechanisms that occur during failure of the composites. For all composites, 8 layers of fabrics were used with a quasi-isotropic sequence of [-45°, 0°, +45°, 90°]s. DMTA showed the Tg of all composites to be approximately same (123 ±3°C) and that flexural storage modulus (before the onset of Tg) was the highest for the pure CF composite while the lowest were for the Innegra 1 and 2 composites. Short-beam shear strength of the commingled composites was higher than other composites, while for Innegra 1 and 2 composites only inelastic deformation failure was observed during the short-beam test. During impact, the Innegra 1 composite withstood up to 40 J without any perforation while for the CF perforation occurred at 10 J. The rate of reduction in compression strength upon increasing the impact energy was lowest for the Innegra 1 and 2 composites, while CF showed the highest rate. On the other hand, the compressive strength of the CF composite was highest of all the composites at all impacted energy levels. The predominant failure modes for Innegra composites observed in cross-sections of fractured specimens were fibre pull-out, micro-buckling, and fibre plastic deformation; while fibre breakage and matrix delamination were a major failure observed in the commingled composites due to the more brittle behaviour of CF. Thus, Innegra fibres toughened the CF composites but only at the expense of reducing compressive strength.

Keywords: hybrid composite, thermoplastic fibre, compression strength, damage tolerance

Procedia PDF Downloads 269

Authors: M. Kowalik, J. Masternak, K. Kazimierczuk, O. V. Khavryuchenko, B. Kupcewicz, B. Barszcz

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Recently, the growing interest of chemists in metal-organic coordination polymers (MOCPs) is primarily derived from their intriguing structures and potential applications in catalysis, gas storage, molecular sensing, ion exchanges, nonlinear optics, luminescence, etc. Currently, we are devoting considerable effort to finding the proper method of synthesizing new coordination polymers containing S- or N-heteroaromatic carboxylates as linkers and characterizing the obtained Pb(II) compounds according to their structural diversity, luminescence, and thermal properties. The choice of Pb(II) as the central ion of MOCPs was motivated by several reasons mentioned in the literature: i) a large ionic radius allowing for a wide range of coordination numbers, ii) the stereoactivity of the 6s2 lone electron pair leading to a hemidirected or holodirected geometry, iii) a flexible coordination environment, and iv) the possibility to form secondary bonds and unusual non-covalent interactions, such as classic hydrogen bonds and π···π stacking interactions, as well as nonconventional hydrogen bonds and rarely reported tetrel bonds, Pb(lone pair)···π interactions, C–H···Pb agostic-type interactions or hydrogen bonds, and chelate ring stacking interactions. Moreover, the construction of coordination polymers requires the selection of proper ligands acting as linkers, because we are looking for materials exhibiting different network topologies and fluorescence properties, which point to potential applications. The reaction of Pb(NO₃)₂ with 1H-pyrrole-2-carboxylic acid (2prCOOH) leads to the formation of a new four-nuclear Pb(II) polymer, [Pb4(2prCOO)₈(H₂O)]ₙ, which has been characterized by CHN, FT-IR, TG, PL and single-crystal X-ray diffraction methods. In view of the primary Pb–O bonds, Pb1 and Pb2 show hemidirected pentagonal pyramidal geometries, while Pb2 and Pb4 display hemidirected octahedral geometries. The topology of the strongest Pb–O bonds was determined as the (4·8²) fes topology. Taking the secondary Pb–O bonds into account, the coordination number of Pb centres increased, Pb1 exhibited a hemidirected monocapped pentagonal pyramidal geometry, Pb2 and Pb4 exhibited a holodirected tricapped trigonal prismatic geometry, and Pb3 exhibited a holodirected bicapped trigonal prismatic geometry. Moreover, the Pb(II) lone pair stereoactivity was confirmed by DFT calculations. The 2D structure was expanded into 3D by the existence of non-covalent O/C–H···π and Pb···π interactions, which was confirmed by the Hirshfeld surface analysis. The above mentioned interactions improve the rigidity of the structure and facilitate the charge and energy transfer between metal centres, making the polymer a promising luminescent compound.

Keywords: coordination polymers, fluorescence properties, lead(II), lone electron pair stereoactivity, non-covalent interactions

Procedia PDF Downloads 120

Authors: Andrey A. Lipovskii, Alexey V. Redkov, Vyacheslav V. Rusan, Dmitry K. Tagantsev, Valentina V. Zhurikhina

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The presented research is related to the development of recently proposed technique of the formation of composite materials, like optical glass-ceramics, with predetermined structure and properties of the crystalline component. The technique is based on the control of the size and concentration of the crystalline grains using the phenomenon of glass-ceramics decrystallization (vitrification) induced by ion-exchange. This phenomenon was discovered and explained in the beginning of the 2000s, while related theoretical description was given in 2016 only. In general, the developed theory enables one to model the process and optimize the conditions of ion-exchange processing of glass-ceramics, which provide given properties of crystalline component, in particular, profile of the average size of the crystalline grains. The optimization is possible if one knows two dimensionless parameters of the theoretical model. One of them (β) is the value which is directly related to the solubility of crystalline component of the glass-ceramics in the glass matrix, and another (γ) is equal to the ratio of characteristic times of ion-exchange diffusion and crystalline grain dissolution. The presented study is dedicated to the development of experimental technique and simulation which allow determining these parameters. It is shown that these parameters can be deduced from the data on the space distributions of diffusant concentrations and average size of crystalline grains in the glass-ceramics samples subjected to ion-exchange treatment. Measurements at least at two temperatures and two processing times at each temperature are necessary. The composite material used was a silica-based glass-ceramics with crystalline grains of Li2OSiO2. Cubical samples of the glass-ceramics (6x6x6 mm3) underwent the ion exchange process in NaNO3 salt melt at 520 oC (for 16 and 48 h), 540 oC (for 8 and 24 h), 560 oC (for 4 and 12 h), and 580 oC (for 2 and 8 h). The ion exchange processing resulted in the glass-ceramics vitrification in the subsurface layers where ion-exchange diffusion took place. Slabs about 1 mm thick were cut from the central part of the samples and their big facets were polished. These slabs were used to find profiles of diffusant concentrations and average size of the crystalline grains. The concentration profiles were determined from refractive index profiles measured with Max-Zender interferometer, and profiles of the average size of the crystalline grains were determined with micro-Raman spectroscopy. Numerical simulation were based on the developed theoretical model of the glass-ceramics decrystallization induced by ion exchange. The simulation of the processes was carried out for different values of β and γ parameters under all above-mentioned ion exchange conditions. As a result, the temperature dependences of the parameters, which provided a reliable coincidence of the simulation and experimental data, were found. This ensured the adequate modeling of the process of the glass-ceramics decrystallization in 520-580 oC temperature interval. Developed approach provides a powerful tool for fine tuning of the glass-ceramics structure, namely, concentration and average size of crystalline grains.

Keywords: diffusion, glass-ceramics, ion exchange, vitrification

Procedia PDF Downloads 244

Authors: Kim Katherine Castillo, Nelson John Datubatang, Terrence Phillip Dy, Norelie Hampac, Reichen Crismark Martinez, Nina Faith Pantinople, Jose Dante Santos II, Marchel Ann Santos, Sophia Abigail Santiago, Zyrill Xsar San Juan, Aira Mae Tagao, Crystal Kylla Viagedor

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The Work Immersion Program was implemented to help students gain abundant work-related experiences while on-site; additionally, the program aims to help students improve their competencies and interpersonal skills as they are given the option to join the workforce if they ever choose to do so after senior high school. The work immersion experience posed diverse challenges for students, spanning personal, financial, engagement, environmental, and equipment-related domains. These included the need for assistance in time management, transportation expenses, and procurement of materials. Furthermore, students faced difficulties in independent task completion and encountered suboptimal work environments. Addressing these multifaceted obstacles is crucial to optimize the educational outcomes of work immersion programs. In addition to the challenges, several other issues have been identified, including the absence of standardized work immersion programs across schools and industries, the challenges in securing appropriate work immersion placements, the necessity for enhanced monitoring and evaluation of program effectiveness, and the limited availability of field programs aligned with students' chosen courses. Furthermore, there is a lack of comprehensive information regarding the attitudes of Senior High School students toward work immersion programs within their respective schools. This study aims to investigate the attitudes of senior high school students at Nazareth School of National University towards work immersion programs, with a focus on identifying factors that influence their perception and participation, including collegiality and expectations. By exploring the students' attitudes, the research endeavors to enhance the school's work immersion programs and contribute to the overall educational experience of the students. This study addresses challenges related to work immersion programs, focusing on six subtopics: Work Immersion, Work Immersion in the Philippines, Students' Attitudes, Factors Affecting Students' Attitudes, Effectiveness of Work Immersion for Senior High School Students, and Students' Perception and Willingness to Participate. Using a descriptive research design, the study examines the attitudes of senior high school students at Nazareth School of National University in Manila. Data was collected from 100 students, representing different academic strands, through a 35-item researcher-made survey. Descriptive statistics, including measures of central tendency and variability, will be used to analyze the data using JASP, providing valuable insights into the students' attitudes toward work immersion.

Keywords: attitudes, challenges, educational outcomes, work immersion programs

Procedia PDF Downloads 60

Authors: Abouchouaib Belahmira, Joerg W. Schneider, Hafid Saber, Sara Akboub

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The lithofacies analyzed herein were reported from the interbedded fluvial and lacustrine deposits of the Oued Issene and El Menizla formations. These formations are part of the sedimentary fill of the Carboniferous (Stephanian) submontaneous Souss basin. The latter is situated in the western High Atlas Mountains, south-central Morocco, about 50km east of Agadir. The Souss basin started as a single basin but was separated into sub-basins called Ida Ou Zal and Ida Ou Ziki by sinistral displacement along the west branch of the Tizi N'Test Fault during the end of the Mauritanid phase of the Variscan orogeny in Morocco, after the early Stephanian (Kasimovian) and before the late middle Permian (Capitanian). The studied succession is a monotonous finning-upward sequence of 1800 m thick. It consists of fine-grained sandstone, finely bedded siltstone and thinly laminated claystone, and black shale. Herein we provide a detailed characterization of lithofacies of the upper El Menizla and Oued Issène formations, with a focus on the prevailing overbank to flood plain fine-grained lithofacies. The studied facies are capping the Stephanian alluvial fan basal clast-supported conglomerates that are intercalated bedded coarse-grained sandstones of Ikhourba Formation in the Ou Zal subbasin and Tajgaline Formation in the Ida Ou Ziki subbasin, respectively. Within the fluvial elements, only two main facies have been observed. It comprises channel-fill and channel-bar deposits, mostly occur as lenticular –shape sand bodies or sheet-like sand greenish to gray fine-to medium (Fm), massive internally structureless, or very locally exhibits a medium to large scale trough-cross bedding medium to coarse sandstone (St), observable in relatively thicker bed. These facies are laterally extensive, with a thickness varying from a few to several meters. Finer-grained sediments such as mud can be present as drapes over bedforms. Whilst the fluvial association FA1, the overbank elements are represented by a relatively wide range of 5 facies. This exhibit mostly a cm scale horizontally bedded greenish fine- to medium sand and silt, and mm scale fossiliferous thinly laminated dark gray- black Corganic-rich clays to siltstone associated with black shale. Thus, FA2 includes flood plain fines (Fh, R) associated with the paleosols and back swamp coaly clay facies (C). The floodplain lake element comprises only laminated organic-rich dark gray facies of claystone, black shale, and graded siltstone. Bedsets are dm to several meters thick (typically < 1 m thick). They are intercalated between several m-thick fluvial sandstone, extend over a few meters, and are poorly bioturbated. The lacustrine facies described in this study have been divided into two sub-facies (Fl, B) based on field observations that indicate differing environmental conditions of formation. Thus, the thorough analysis of the lithofacies of the Souss basin units allows us to reconstruct the original environment that was interpreted as a typical fluvial-dominated braided to anastomosing wide distributary channel system and surrounding deep to shallow freshwater floodplain lakes and back swamps.

Keywords: Souss, carboniferous, facies, depositional setting

Procedia PDF Downloads 61

Authors: Veronica Caprai, Katrin Schollbach, Miruna V. A. Florea, H. J. H. Brouwers

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Nowadays MSWI (Municipal Solid Waste Incineration) bottom ash (BA) produced by Waste-to-Energy (WtE) plants represents the majority of the solid residues derived from MSW incineration. Once processed, the BA is often landfilled resulting in possible environmental problems, additional costs for the plant and increasing occupation of public land. In order to limit this phenomenon, European countries such as the Netherlands aid the utilization of MSWI BA in the construction field, by providing standards about the leaching of contaminants into the environment (Dutch Soil Quality Decree). Commonly, BA has a particle size below 32 mm and a heterogeneous chemical composition, depending on its source. By washing coarser BA, an MSWI sludge is obtained. It is characterized by a high content of heavy metals, chlorides, and sulfates as well as a reduced particle size (below 0.25 mm). To lower its environmental impact, MSWI sludge is filtered or centrifuged for removing easily soluble contaminants, such as chlorides. However, the presence of heavy metals is not easily reduced, compromising its possible application. For lowering the leaching of those contaminants, the use of MSWI residues in combination with cement represents a precious option, due to the known retention of those ions into the hydrated cement matrix. Among the applications, the European standard for common cement EN 197-1:1992 allows the incorporation of up to 5% by mass of a minor additional constituent (MAC), such as fly ash or blast furnace slag but also an unspecified filler into cement. To the best of the author's knowledge, although it is widely available, it has the appropriate particle size and a chemical composition similar to cement, FC has not been investigated as possible MAC in cement production. Therefore, this paper will address the suitability of MSWI FC as MAC for CEM I 52.5 R, within a 5% maximum replacement by mass. After physical and chemical characterization of the raw materials, the crystal phases of the pastes are determined by XRD for 3 replacement levels (1%, 3%, and 5%) at different ages. Thereafter, the impact of FC on mechanical and environmental performances of cement is assessed according to EN 196-1 and the Dutch Soil Quality Decree, respectively. The investigation of the reaction products evidences the formation of layered double hydroxides (LDH), in the early stage of the reaction. Mechanically the presence of FC results in a reduction of 28 days compressive strength by 8% for a replacement of 5% wt., compared with the pure CEM I 52.5 R without any MAC. In contrast, the flexural strength is not affected by the presence of FC. Environmentally, the Dutch legislation for the leaching of contaminants for unshaped (granular) material is satisfied. Based on the collected results, FC represents a suitable candidate as MAC in cement production.

Keywords: environmental impact evaluation, Minor additional constituent, MSWI residues, X-ray diffraction crystallography

Procedia PDF Downloads 123

Authors: Shivani Dhande, Sanjiv Choudhary, Adarshlata Singh

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Introduction: Early age of onset of baldness has marked psychological impact on personality. Combination therapies have better efficacy than monotherapy in androgenetic alopecia. Although medical, surgical treatment and cosmetic aids are available for treatment of pattern baldness, medical is first preferred the line of treatment. Although only 5% topical minoxidil is USFDA approved, 10% is available in India since 2007. Efficacy of tablet finasteride is well established in male pattern baldness. 5% topical minoxidil is effective and safe in female pattern baldness. There is a role of saw palmetto in regrowth of scalp hair. With this background research was undertaken to study efficacy and safety of topical minoxidil 10% + tab. Finesteride (1mg) + dermaroller in male pattern baldness and topical minoxidil 5% + cap. Saw palmetto (320 mg) + dermaroller in female pattern baldness. Methods and Materials: It was a randomized uncontrolled evaluator blind study consisting of total 21 patients, 15 of male pattern baldness and 6 of female pattern baldness within 20-35 yrs of age were enrolled. Male patients had Hamilton grade 2-4 MPB and females had Ludwig grade 2 FPB. Male patients were treated with Tab Finesteride 1mg once daily + 10% topical Minoxidil 1ml twice daily for 6 months. Female patients were treated with Cap. Saw palmetto 320 mg once daily + 5% topical Minoxidil twice daily for 6 months. In both male & female patients dermaroller therapy was used once in 10 days for 4 sittings followed by once in 15 days for next 5 months. Blood pressure and possible side effects were monitored in every follow up visits. Pre and post treatment photographs were taken. Assessment of hair growth was done at baseline and at the end of 6 months. Patients satisfactory grading scale and Physician assessment of hair growth scale were used to assessing the results. Trichoscan was done for assessment of hair-shaft diameter and density. Pre and post treatment photographs and Trichoscan hair growth analysis (by diameter and density) was done by physician (dermatologist) not directly involved in this study (evaluator blind). Result: This combination therapy showed moderate response in female pattern alopecia and good to excellent results in male pattern alopecia at the end of 6 months. During therapy none of the patients showed side effects like hypotension, headache and loss of libido, hirsuitism. Mild irritation due to crystal deposition was noted by 3 patients. Conclusion: Effective and early treatment using combination therapy with higher percent of Minoxidil for rapid hair growth is necessary in initial period since it will boost up the self-confidence in patients leading to better treatment compliance. Subsequent maintenance of hair growth can be done with lower concentration. No significant side effects with treatment are observed in both group of patients.

Keywords: androgenetic alopecia, dermaroller, finasteride, minoxidil, saw palmetto

Procedia PDF Downloads 227

Authors: Bastian Waduge Naveen Harindu Hemasiri, Jae-Kwan Kim, Ji-Myon Lee

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Indium tin oxide (ITO) remains the industrial standard transparent conducting oxides with better performances. Recently, graphene becomes as a strong material with unique properties to replace the ITO. However, graphene/ITO hybrid composite material is a newly born field in the electronic world. In this study, the graphene/ITO composite bi-film was synthesized by a two steps process. 10 wt.% tin-doped, ITO thin films were produced by an environmentally friendly aqueous sol-gel spin coating technique with economical salts of In(NO3)3.H2O and SnCl4 without using organic additives. The wettability and surface free energy (97.6986 mJ/m2) enhanced oxygen plasma treated glass substrates were used to form voids free continuous ITO film. The spin-coated samples were annealed at 600 0C for 1 hour under low vacuum conditions to obtained crystallized, ITO film. The crystal structure and crystalline phases of ITO thin films were analyzed by X-ray diffraction (XRD) technique. The Scherrer equation was used to determine the crystallite size. Detailed information about chemical composition and elemental composition of the ITO film were determined by X-ray photoelectron spectroscopy (XPS) and energy dispersive X-ray spectroscopy (EDX) coupled with FE-SEM respectively. Graphene synthesis was done under chemical vapor deposition (CVD) method by using Cu foil at 1000 0C for 1 min. The quality of the synthesized graphene was characterized by Raman spectroscopy (532nm excitation laser beam) and data was collected at room temperature and normal atmosphere. The surface and cross-sectional observation were done by using FE-SEM. The optical transmission and sheet resistance were measured by UV-Vis spectroscopy and four point probe head at room temperature respectively. Electrical properties were also measured by using V-I characteristics. XRD patterns reveal that the films contain the In2O3 phase only and exhibit the polycrystalline nature of the cubic structure with the main peak of (222) plane. The peak positions of In3d5/2 (444.28 eV) and Sn3d5/2 (486.7 eV) in XPS results indicated that indium and tin are in the oxide form only. The UV-visible transmittance shows 91.35 % at 550 nm with 5.88 x 10-3 Ωcm specific resistance. The G and 2D band in Raman spectroscopy of graphene appear at 1582.52 cm-1 and 2690.54 cm-1 respectively when the synthesized CVD graphene on SiO2/Si. The determined intensity ratios of 2D to G (I2D/IG) and D to G (ID/IG) were 1.531 and 0.108 respectively. However, the above-mentioned G and 2D peaks appear at 1573.57 cm-1 and 2668.14 cm-1 respectively when the CVD graphene on the ITO coated glass, the positions of G and 2D peaks were red shifted by 8.948 cm-1 and 22.396 cm-1 respectively. This graphene/ITO bi-film shows modified electrical properties when compares with sol-gel derived ITO film. The reduction of sheet resistance in the bi-film was 12.03 % from the ITO film. Further, the fabricated graphene/ITO bi-film shows 88.66 % transmittance at 550 nm wavelength.

Keywords: chemical vapor deposition, graphene, ITO, Raman Spectroscopy, sol-gel

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Authors: Victoria Molina, Wendy Franco, Sergio Benavides, José M. Troncoso, Ricardo Luna, Jose R. PéRez-Correa

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Emamectin Benzoate (EB) is a crystal antiparasitic that belongs to the avermectin family. It is one of the most common treatments used in Chile to control Caligus rogercresseyi in Atlantic salmon. However, the sea lice acquired resistance to EB when it is exposed at sublethal EB doses. The low solubility rate of EB and its degradation at the acidic pH in the fish digestive tract are the causes of the slow absorption of EB in the intestine. To protect EB from degradation and enhance its absorption, specific microencapsulation technologies must be developed. Amorphous Solid Dispersion techniques such as Spray Drying (SD) and Ionic Gelation (IG) seem adequate for this purpose. Recently, Soluplus® (SOL) has been used to increase the solubility rate of several drugs with similar characteristics than EB. In addition, alginate (ALG) is a widely used polymer in IG for biomedical applications. Regardless of the encapsulation technique, the quality of the obtained microparticles is evaluated with the following responses, yield (Y%), encapsulation efficiency (EE%) and loading capacity (LC%). In addition, it is important to know the percentage of EB released from the microparticles in gastric (GD%) and intestinal (ID%) digestions. In this work, we microencapsulated EB with SOL (EB-SD) and with ALG (EB-IG) using SD and IG, respectively. Quality microencapsulation responses and in vitro gastric and intestinal digestions at pH 3.35 and 7.8, respectively, were obtained. A central composite design was used to find the optimum microencapsulation variables (amount of EB, amount of polymer and feed flow). In each formulation, the behavior of these variables was predicted with statistical models. Then, the response surface methodology was used to find the best combination of the factors that allowed a lower EB release in gastric conditions, while permitting a major release at intestinal digestion. Two approaches were used to determine this. The desirability approach (DA) and multi-objective optimization (MOO) with multi-criteria decision making (MCDM). Both microencapsulation techniques allowed to maintain the integrity of EB in acid pH, given the small amount of EB released in gastric medium, while EB-IG microparticles showed greater EB release at intestinal digestion. For EB-SD, optimal conditions obtained with MOO plus MCDM yielded a good compromise among the microencapsulation responses. In addition, using these conditions, it is possible to reduce microparticles costs due to the reduction of 60% of BE regard the optimal BE proposed by (DA). For EB-GI, the optimization techniques used (DA and MOO) yielded solutions with different advantages and limitations. Applying DA costs can be reduced 21%, while Y, GD and ID showed 9.5%, 84.8% and 2.6% lower values than the best condition. In turn, MOO yielded better microencapsulation responses, but at a higher cost. Overall, EB-SD with operating conditions selected by MOO seems the best option, since a good compromise between costs and encapsulation responses was obtained.

Keywords: microencapsulation, multiple decision-making criteria, multi-objective optimization, Soluplus®

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Authors: Syed Asif Hassan, Tabrej Khan

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Tuberculosis (TB) caused by bacillus Mycobacterium tuberculosis (Mtb) continues to take a disturbing toll on human life and healthcare facility worldwide. The global burden of TB remains enormous. The alarming rise of multi-drug resistant strains of Mycobacterium tuberculosis calls for an increase in research efforts towards the development of new target specific therapeutics against diverse strains of M. tuberculosis. Therefore, the discovery of new molecular scaffolds targeting new drug sites should be a priority for a workable plan for fighting resistance in Mycobacterium tuberculosis (Mtb). Mtb non-acylated lipoprotein LprG (Rv1411c) has a Toll-like receptor 2 (TLR2) agonist actions that depend on its association with triacylated glycolipids binding specifically with the hydrophobic pocket of Mtb LprG lipoprotein. The detection of a glycolipid carrier function has important implications for the role of LprG in Mycobacterial physiology and virulence. Therefore, considering the pivotal role of glycolipids in mycobacterial physiology and host-pathogen interactions, designing competitive antagonist (chemotherapeutics) ligands that competitively bind to glycolipid binding domain in LprG lipoprotein, will lead to inhibition of tuberculosis infection in humans. In this study, a unified approach involving ligand-based virtual screening protocol USRCAT (Ultra Shape Recognition) software and molecular docking studies using Auto Dock Vina 1.1.2 using the X-ray crystal structure of Mtb LprG protein was implemented. The docking results were further confirmed by DSX (DrugScore eXtented), a robust program to evaluate the binding energy of ligands bound to the Ligand binding domain of the Mtb LprG lipoprotein. The ligand, which has the higher hypothetical affinity, also has greater negative value. Based on the USRCAT, Lipinski’s values and molecular docking results, [(2R)-2,3-di(hexadecanoyl oxy)propyl][(2S,3S,5S,6R)-3,4,5-trihydroxy-2,6-bis[[(2R,3S,4S,5R,6S)-3,4,5-trihydroxy-6 (hydroxymethyl)tetrahydropyran-2-yl]oxy]cyclohexyl] phosphate (XPX) was confirmed as a promising drug-like lead compound (antagonist) binding specifically to the hydrophobic domain of LprG protein with affinity greater than that of PIM2 (agonist of LprG protein) with a free binding energy of -9.98e+006 Kcal/mol and binding affinity of -132 Kcal/mol, respectively. A further, in vitro assay of this compound is required to establish its potency in inhibiting molecular evasion mechanism of MTB within the infected host macrophages. These results will certainly be helpful in future anti-TB drug discovery efforts against Multidrug-Resistance Tuberculosis (MDR-TB).

Keywords: antagonist, agonist, binding affinity, chemotherapeutics, drug-like, multi drug resistance tuberculosis (MDR-TB), RV1411c protein, toll-like receptor (TLR2)

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Authors: Xiaoling Ren, Guidong Yang

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Ammonia, as one of the largest-volume industrial chemicals, is mostly produced by century-old Haber-Bosch process with extreme conditionsand high-cost. Under the circumstance, researchersarededicated in finding new ways to replace the Haber-Bosch process. Photocatalytic nitrogen fixation is a promising sustainable, clear and green strategy for ammonia synthesis, butit is still a big challenge due to the high activation energy for nitrogen. It is essential to develop an efficient photocatalyst for making this approach industrial application. Constructing chemisorption active sites through defect engineering can be defined as an effective and reliable means to improve nitrogen activation by forming the extraordinary coordination environment and electronic structure. Besides, the construction of three-dimensionally orderdmacroporous (3DOM) structured photocatalyst is considered to be one of effectivestrategiesto improve the activity due to it canincrease the diffusion rate of reactants in the interior, which isbeneficial to the mass transfer process of nitrogen molecules in photocatalytic nitrogen reduction. Herein, Fe doped 3DOM WO₃(Fe-3DOM WO₃) without noble metal cocatalysts is synthesized by a polystyrene-template strategy, which is firstly used for photocatalytic nitrogen fixation. To elucidate the chemical nature of the dopant, the X-ray diffraction (XRD) analysiswas conducted. The pure 3DOM WO₃ has a monoclinic type crystal structure. And no additional peak is observed in Fe doped 3DOM WO₃, indicating that the incorporation of Fe atoms did not result in a secondary phase formation. In order to confirm the morphologies of Fe-3DOM WO₃and 3DOM WO₃, scanning electron microscopy (SEM) was employed. The synthesized Fe-3DOM WO₃and 3DOM WO₃ both exhibit a highly ordered three dimensional inverse opal structure with interconnected pores. From high-resolution TEM image of Fe-3DOM WO₃, the ordered lattice fringes with a spacing of 3.84 Å can be assigned to the (001) plane of WO₃, which is consistent with the XRD results. Finally, the photocatalytic nitrogen reduction performance of 3DOM WO₃ and Fe doped 3DOM WO₃with various Fe contents were examined. As a result, both Fe-3DOM WO₃ samples achieve higher ammonia production rate than that of pure 3DOM WO₃, indicating that the doped Fe plays a critical role in the photocatalytic nitrogen fixation performance. To verify the reaction process upon N2 reduction on the Fe-3DOM WO₃, in-situ diffuse reflectance infrared Fourier-transform spectroscopy was employed to monitor the intermediates. The in-situ DRIFTS spectra of Fe-3DOM WO₃ exhibit the increased signals with the irradiation time from 0–60min in the N2 atmosphere. The above results prove that nitrogen is gradually hydrogenated to produce ammonia over Fe-3DOM WO₃. Thiswork would enrich our knowledge in designing efficient photocatalystsfor photocatalytic nitrogen reduction.

Keywords: ammonia, photocatalytic, nitrogen fixation, Fe doped 3DOM WO₃

Procedia PDF Downloads 136

Authors: Nikolai A. Khlebnikov, Vladimir N. Krasilnikov, Evgenii V. Polyakov, Anastasia A. Maltceva

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Carbon materials with advanced surfaces are widely used both in modern industry and in environmental protection. The physical-chemical nature of these materials is determined by the morphology of primary atomic and molecular carbon structures, which are the basis for synthesizing the following materials: zero-dimensional (fullerenes), one-dimensional (fiber, tubes), two-dimensional (graphene) carbon nanostructures, three-dimensional (multi-layer graphene, graphite, foams) with unique physical-chemical and functional properties. Experience shows that the microscopic morphological level is the basis for the creation of the next mesoscopic morphological level. The dependence of the morphology on the chemical way and process prehistory (crystallization, colloids formation, liquid crystal state and other) is the peculiarity of the last called level. These factors determine the consumer properties of carbon materials, such as specific surface area, porosity, chemical resistance in corrosive environments, catalytic and adsorption activities. Based on the developed ideology of thin precursor synthesis, the authors discuss one of the approaches of the porosity control of carbon-containing materials with a given aggregates morphology. The low-temperature thermolysis of precursors in a gas environment of a given composition is the basis of the above-mentioned idea. The processes of carbothermic precursor synthesis of two different compounds: tungsten carbide WC:nC and zinc oxide ZnO:nC containing an impurity phase in the form of free carbon were selected as subjects of the research. In the first case, the transition metal (tungsten) forming carbides was the object of the synthesis. In the second case, there was selected zinc that does not form carbides. The synthesis of both kinds of transition metals compounds was conducted by the method of precursor carbothermic synthesis from the organic solution. ZnO:nC composites were obtained by thermolysis of succinate Zn(OO(CH2)2OO), formate glycolate Zn(HCOO)(OCH2CH2O)1/2, glycerolate Zn(OCH2CHOCH2OH), and tartrate Zn(OOCCH(OH)CH(OH)COO). WC:nC composite was synthesized from ammonium paratungstate and glycerol. In all cases, carbon structures that are specific for diamond- like carbon forms appeared on the surface of WC and ZnO particles after the heat treatment. Tungsten carbide and zinc oxide were removed from the composites by selective chemical dissolution preserving the amorphous carbon phase. This work presents the results of investigating WC:nC and ZnO:nC composites and carbon nanopowders with tubular, tape, plate and onion morphologies of aggregates that are separated by chemical dissolution of WC and ZnO from the composites by the following methods: SEM, TEM, XPA, Raman spectroscopy, and BET. The connection between the carbon morphology under the conditions of synthesis and chemical nature of the precursor and the possibility of regulation of the morphology with the specific surface area up to 1700-2000 m2/g of carbon-structured materials are discussed.

Keywords: carbon morphology, composite materials, precursor synthesis, tungsten carbide, zinc oxide

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Authors: Ružica Tomičić, Zorica Tomičić, Peter Raspor

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An abundant growth of unwanted yeasts in food processing plants can lead to problems in quality and safety with significant financial losses. Candida and Pichia are the genera mainly involved in spoilage of products in the food and beverage industry. These contaminating microorganisms can form biofilms on food contact surfaces, being difficult to eradicate, increasing the probability of microbial survival and further dissemination during food processing. It is well known that biofilms are more resistant to antimicrobial agents compared to planktonic cells and this makes them difficult to eliminate. Among the strategies used to overcome resistance to antifungal drugs and preservatives, the use of natural substances such as plant extracts has shown particular promise, and many natural substances have been found to exhibit antifungal properties. This study aimed to investigated the impact of growth medium (Malt Extract broth (MEB) or Yeast Peptone Dextrose (YPD) broth) and temperatures (7°C, 37°C, 43°C for Candida strains and 7°C, 27°C, 32°C for Pichia strains) on the adhesion of Candida spp. and Pichia spp. to stainless steel (AISI 304) discs with different degrees of surface roughness (Ra = 25.20 – 961.9 nm), a material commonly used in the food industry. We also evaluated the antifungal and antiadhesion activity of plant extracts such as Humulus lupulus, Alpinia katsumadai and Evodia rutaecarpa against C. albicans, C glabrata and P. membranifaciens and investigated whether these plant extracts can interfere with biofilm formation. The adhesion was assessed by the crystal violet staining method, while the broth microdilution method CLSI M27-A3 was used to determine the minimum inhibitory concentration (MIC) of plant extracts. Our results indicated that the nutrient content of the medium significantly influenced the amount of adhered cells of the tested yeasts. The growth medium which resulted in a higher adhesion of C. albicans and C. glabrata was MEB, while for C. parapsilosis and C. krusei was YPD. In the case of P. pijperi and P. membranifaciens, YPD broth was more effective in promoting adhesion than MEB. Regarding the effect of temperature, C. albicans strain adhered to stainless steel surfaces in significantly higher level at a temperature of 43°C, while on the other hand C. glabrata, C. parapsilosis and C. krusei showed a different behavior with significantly higher adhesion at 37°C than at 7°C and 43°C. Further, the adherence ability of Pichia strains was highest at 27°C. Based on the MIC values, all plant extracts exerted significant antifungal effects with MIC values ranged from 100 to 400 μg/mL. It was observed that biofilm of C. glabrata were more resistance to plant extracts as compared to C. albicans. However, extracts of A. katsumadai and E. rutaecarpa promoted the growth and development of the preformed biofilm of P. membranifaciens. Thus, the knowledge of how these microorganisms adhere and which factors affect this phenomenon is of great importance in order to avoid their colonization on food contact surfaces.

Keywords: adhesion, Candida spp., Pichia spp., plant extracts

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Authors: Biswaranjan D. Mohapatra, Ipsha Hota, Swarna P. Mantry, Nibedita Behera, Kumar S. K. Varadwaj

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Designing highly active and low-cost oxygen evolution (2H₂O → 4H⁺ + 4e⁻ + O₂) electrocatalyst is one of the most active areas of advanced energy research. Some precious metal-based electrocatalysts, such as IrO₂ and RuO₂, have shown excellent performance for oxygen evolution reaction (OER); however, they suffer from high-cost and low abundance which limits their applications. Recently, layered double hydroxides (LDHs), composed of layers of divalent and trivalent transition metal cations coordinated to hydroxide anions, have gathered attention as an alternative OER catalyst. However, LDHs are insulators and coupled with carbon materials for the electrocatalytic applications. Graphene covalently doped with nitrogen has been demonstrated to be an excellent electrocatalyst for energy conversion technologies such as; oxygen reduction reaction (ORR), oxygen evolution reaction (OER) & hydrogen evolution reaction (HER). However, they operate at high overpotentials, significantly above the thermodynamic standard potentials. Recently, we reported remarkably enhanced catalytic activity of benzoate or 1-pyrenebutyrate functionalized N-doped graphene towards the ORR in alkaline medium. The molecular and heteroatom co-doping on graphene is expected to tune the electronic structure of graphene. Therefore, an innovative catalyst architecture, in which LDHs are anchored on aromatic acid functionalized ‘N’ doped graphene may presumably boost the OER activity to a new benchmark. Herein, we report fabrication of Co₂Fe-LDH on aromatic acid (AA) functionalized ‘N’ doped reduced graphene oxide (NG) and studied their OER activities in alkaline medium. In the first step, a novel polyol method is applied for synthesis of AA functionalized NG, which is well dispersed in aqueous medium. In the second step, Co₂Fe LDH were grown on AA functionalized NG by co-precipitation method. The hybrid samples are abbreviated as Co₂Fe LDH/AA-NG, where AA is either Benzoic acid or 1, 3-Benzene dicarboxylic acid (BDA) or 1, 3, 5 Benzene tricarboxylic acid (BTA). The crystal structure and morphology of the samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and transmission electron microscope (TEM). These studies confirmed the growth of layered single phase LDH. The electrocatalytic OER activity of these hybrid materials was investigated by rotating disc electrode (RDE) technique on a glassy carbon electrode. The linear sweep voltammetry (LSV) on these catalyst samples were taken at 1600rpm. We observed significant OER performance enhancement in terms of onset potential and current density on Co₂Fe LDH/BTA-NG hybrid, indicating the synergic effect. This exploration of molecular functionalization effect in doped graphene and LDH system may provide an excellent platform for innovative design of OER catalysts.

Keywords: π-π functionalization, layered double hydroxide, oxygen evolution reaction, reduced graphene oxide

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Authors: Jan Masak, Eva Kvasnickova, Vladimir Scholtz, Olga Matatkova, Marketa Valkova, Alena Cejkova

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Microbial colonization of medical instruments, catheters, implants, etc. is a serious problem in the spread of nosocomial infections. Biofilms exhibit enormous resistance to environment. The resistance of biofilm populations to antibiotic or biocides often increases by two to three orders of magnitude in comparison with suspension populations. Subjects of interests are substances or physical processes that primarily cause the destruction of biofilm, while the released cells can be killed by existing antibiotics. In addition, agents that do not have a strong lethal effect do not cause such a significant selection pressure to further enhance resistance. Non-thermal plasma (NTP) is defined as neutral, ionized gas composed of particles (photons, electrons, positive and negative ions, free radicals and excited or non-excited molecules) which are in permanent interaction. In this work, the effect of NTP generated by the cometary corona with a metallic grid on the formation and stability of biofilm and metabolic activity of cells in biofilm was studied. NTP was applied on biofilm populations of Staphylococcus epidermidis DBM 3179, Pseudomonas aeruginosa DBM 3081, DBM 3777, ATCC 15442 and ATCC 10145, Escherichia coli DBM 3125 and Candida albicans DBM 2164 grown on solid media on Petri dishes and on the titanium alloy (Ti6Al4V) surface used for the production joint replacements. Erythromycin (for S. epidermidis), polymyxin B (for E. coli and P. aeruginosa), amphotericin B (for C. albicans) and ceftazidime (for P. aeruginosa) were used to study the combined effect of NTP and antibiotics. Biofilms were quantified by crystal violet assay. Metabolic activity of the cells in biofilm was measured using MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) colorimetric test based on the reduction of MTT into formazan by the dehydrogenase system of living cells. Fluorescence microscopy was applied to visualize the biofilm on the surface of the titanium alloy; SYTO 13 was used as a fluorescence probe to stain cells in the biofilm. It has been shown that biofilm populations of all studied microorganisms are very sensitive to the type of used NTP. The inhibition zone of biofilm recorded after 60 minutes exposure to NTP exceeded 20 cm², except P. aeruginosa DBM 3777 and ATCC 10145, where it was about 9 cm². Also metabolic activity of cells in biofilm differed for individual microbial strains. High sensitivity to NTP was observed in S. epidermidis, in which the metabolic activity of biofilm decreased after 30 minutes of NTP exposure to 15% and after 60 minutes to 1%. Conversely, the metabolic activity of cells of C. albicans decreased to 53% after 30 minutes of NTP exposure. Nevertheless, this result can be considered very good. Suitable combinations of exposure time of NTP and the concentration of antibiotic achieved in most cases a remarkable synergic effect on the reduction of the metabolic activity of the cells of the biofilm. For example, in the case of P. aeruginosa DBM 3777, a combination of 30 minutes of NTP with 1 mg/l of ceftazidime resulted in a decrease metabolic activity below 4%.

Keywords: anti-biofilm activity, antibiotic, non-thermal plasma, opportunistic pathogens

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Authors: Zubair Ahmed, Andrea Barbieri

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The need to reduce energy consumption has prompted a considerable research effort for developing alternative energy-efficient lighting systems to replace conventional light sources (i.e., incandescent and fluorescent lamps). Organic light emitting device (OLED) technology offers the distinctive possibility to fabricate large area flat devices by vacuum or solution processing. Lanthanide β-diketonates complexes, due to unique photophysical properties of Ln(III) ions, have been explored as emitting layers in OLED displays and in solid-state lighting (SSL) in order to achieve high efficiency and color purity. For such applications, the excellent photoluminescence quantum yield (PLQY) and stability are the two key points that can be achieved simply by selecting the proper organic ligands around the Ln ion in a coordination sphere. Regarding the strategies to enhance the PLQY, the most common is the suppression of the radiationless deactivation pathways due to the presence of high-frequency oscillators (e.g., OH, –CH groups) around the Ln centre. Recently, a different approach to maximize the PLQY of Ln(β-DKs) has been proposed (named 'Escalate Coordination Anisotropy', ECA). It is based on the assumption that coordinating the Ln ion with different ligands will break the centrosymmetry of the molecule leading to less forbidden transitions (loosening the constraints of the Laporte rule). The OLEDs based on such complexes are available, but with low efficiency and stability. In order to get efficient devices, there is a need to develop some new Ln complexes with enhanced PLQYs and stabilities. For this purpose, the Ln complexes, both visible and (NIR) emitting, of variant coordination structures based on the various fluorinated/non-fluorinated β-diketones and O/N-donor neutral ligands were synthesized using a one step in situ method. In this method, the β-diketones, base, LnCl₃.nH₂O and neutral ligands were mixed in a 3:3:1:1 M ratio in ethanol that gave air and moisture stable complexes. Further, they were characterized by means of elemental analysis, NMR spectroscopy and single crystal X-ray diffraction. Thereafter, their photophysical properties were studied to select the best complexes for the fabrication of stable and efficient OLEDs. Finally, the OLEDs were fabricated and investigated using these complexes as emitting layers along with other organic layers like NPB,N,N′-Di(1-naphthyl)-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (hole-transporting layer), BCP, 2,9-Dimethyl-4,7-diphenyl-1,10-phenanthroline (hole-blocker) and Alq3 (electron-transporting layer). The layers were sequentially deposited under high vacuum environment by thermal evaporation onto ITO glass substrates. Moreover, co-deposition techniques were used to improve charge transport in the devices and to avoid quenching phenomena. The devices show strong electroluminescence at 612, 998, 1064 and 1534 nm corresponding to ⁵D₀ →⁷F₂(Eu), ²F₅/₂ → ²F₇/₂ (Yb), ⁴F₃/₂→ ⁴I₉/₂ (Nd) and ⁴I1₃/₂→ ⁴I1₅/₂ (Er). All the devices fabricated show good efficiency as well as stability.

Keywords: electroluminescence, lanthanides, paramagnetic NMR, photoluminescence

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Authors: Mustapha A. Tijjani, Fanna I. Abdulrahman, Irfan Z. Khan, Umar K. Sandabe, Cong Li

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Air dried sample V. doniana after collection and identification was extracted with ethanol and further partition with chloroform, ethyl acetate and n-butanol. Ethanolic extract (11.9g) was fractionated on a silica gel accelerated column chromatography using solvents such as n-hexane, ethyl acetate and methanol. Each eluent fractions (150ml aliquots) were collected and monitored with thin layer chromatography. Fractions with similar Rf values from same solvents system were pooled together. Phytochemical test of all the fractions were performed using standard procedure. Complete elution yielded 48 fractions (150ml/fraction) which were pooled to 24 fractions base on the Rf values. It was further recombined and 12 fractions were obtained on the basis on Rf values and coded Vd1 to Vd12 fractions. Vd8 was further eluted with ethylacetate and methanol and gave fourteen sub fractions Vd8-a, -Vd8-m. Fraction Vd8-a (56mg) gave a white crystal compound coded V1. It was further checked on TLC and observed under ultraviolet lamp and was found to give a single spot. The Rf values were calculated to be 0.433. The melting point was determined using Gallenkamp capillary melting point apparatus and found to be 241-243°C uncorrected. Characterization of the isolated compound coded V1 was done using FT-infra-red spectroscopy, HNMR, 13CNMR(1and 2D) and HRESI-MS. The IR spectrum of compound V1 shows prominent peaks that corresponds to OHstr (3365cm-1) and C=0 (1652cm-1) etc. This spectrum suggests that among the functional moiety in compound V1 are the carbonyl and hydroxyl group. The 1H NMR (400 MHz) spectrum of compound V1 in DMSO-d6 displayed five singlet signals at δ 0.72 (3H, s, H-18), 0.79 (3H, s, H-19), 1.03 (3H, s, H-21), 1.04 (3H, s, H-26), 1.06 (3H, s, H-27) each integrating for three protons indicating the five methyl functional groups present in the compound. It further showed a broad singlet at δ 5.58 integrated for 1 H due to an olefinic H-atom adjacent to the carbonyl carbon atom. Three signals at δ 3.10 (d, J = 9.0 Hz, H-22), 3.59 (m, 1H, 2H-a) and 3.72 (m, 1H, 3H-e), each integrating for one proton is due to oxymethine protons indicating that three oxymethine H-atoms are present in the compound. These all signals are characteristic to the ecdysteroid skeletons. The 13C-NMR spectrum showed the presence of 27 carbon atoms, suggesting that may be steroid skeleton. The DEPT-135 experiment showed the presence of five CH3, eight CH2, and seven CH groups, and seven quaternary C-atoms. The molecular formula was established as C27H44O7 by high resolution electron spray ionization-mass spectroscopy (HRESI-MS) positive ion mode m/z 481.3179. The signals in mass spectrum are 463, 445, and 427 peaks corresponding to losses of one, two, three, or four water molecules characteristic for ecdysterone skeleton reported in the literature. Based on the spectral analysis (HNMR, 13CNMR, DEPT, HMQC, IR, HRESI-MS) the compound V1 is thus concluded to have ecdysteriod skeleton and conclusively conforms with 2β, 3β 14α, 20R, 22R, 25-hexahydroxy-5 β cholest-7-ene-6- one, or 2, 3, 14, 20, 22, 25 hexahydroxy cholest-7-ene-6-one commonly known as 20-hydroxyecdysone.

Keywords: vitex, phytochemical, purification, isolation, chromatography, spectroscopy

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