Search results for: hydrogen bond

Authors: Lee A. Browne, K. Rumbold

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The first fluorinating enzyme, 5'-fluoro-5'-deoxyadenosine synthase (fluorinase) was isolated from the soil bacterium Streptomyces cattleya. Such an enzyme, with the ability to catalyze a C-F bond, presents great potential as a biocatalyst. Naturally fluorinated compounds are extremely rare in nature. As a result, the number of fluorinases identified remains relatively few. The field of fluorination is almost completely synthetic. However, with the increasing demand for fluorinated organic compounds of commercial value in the agrochemical, pharmaceutical and materials industries, it has become necessary to utilize biologically based methods such as biocatalysts. A key step in this crucial process is the large-scale production of the fluorinase enzyme in considerable quantities for industrial applications. Thus, this study aimed to optimize expression of the fluorinase enzyme in both prokaryotic and eukaryotic expression systems in order to obtain high protein yields. The fluorinase gene was cloned into the pET 41b(+) and pPinkα-HC vectors and used to transform the expression hosts, E.coli BL21(DE3) and Pichia pastoris (PichiaPink™ strains) respectively. Expression trials were conducted to select optimal conditions for expression in both expression systems. Fluorinase catalyses a reaction between S-adenosyl-L-Methionine (SAM) and fluoride ion to produce 5'-fluorodeoxyadenosine (5'FDA) and L-Methionine. The activity of the enzyme was determined using HPLC by measuring the product of the reaction 5'FDA. A gradient mobile phase of 95:5 v/v 50mM potassium phosphate buffer to a final mobile phase containing 80:20 v/v 50mM potassium phosphate buffer and acetonitrile were used. This resulted in the complete separation of SAM and 5’-FDA which eluted at 1.3 minutes and 3.4 minutes respectively. This proved that the fluorinase enzyme was active. Optimising expression of the fluorinase enzyme was successful in both E.coli and PichiaPink™ where high expression levels in both expression systems were achieved. Protein production will be scaled up in PichiaPink™ using fermentation to achieve large-scale protein production. High level expression of protein is essential in biocatalysis for the availability of enzymes for industrial applications.

Keywords: biocatalyst, expression, fluorinase, PichiaPink™

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Authors: Ketaki D. Belsare, Nicholas F. Polizzi, Lior Shtayer, William F. DeGrado

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Nature utilizes metalloproteins to perform chemical transformations with activities and selectivities that have long been the inspiration for design principles in synthetic and biological systems. The chemical reactivities of metalloproteins are directly linked to local environment effects produced by the protein matrix around the metal cofactor. A complete understanding of how the protein matrix provides these interactions would allow for the design of functional metalloproteins. The de novo computational design of proteins have been successfully used in design of active sites that bind metals like di-iron, zinc, copper containing cofactors; however, precisely designing active sites that can bind small molecule ligands (e.g., substrates) along with metal cofactors is still a challenge in the field. The de novo computational design of a functional metalloprotein that contains a purposefully designed substrate binding site would allow for precise control of chemical function and reactivity. Our research strategy seeks to elucidate the design features necessary to bind the cofactor protoporphyrin IX (hemin) in close proximity to a substrate binding pocket in a four helix bundle. First- and second-shell interactions are computationally designed to control orientation, electronic structure, and reaction pathway of the cofactor and substrate. The design began with a parameterized helical backbone that positioned a single histidine residue (as an axial ligand) to receive a second-shell H-bond from a Threonine on the neighboring helix. The metallo-cofactor, hemin was then manually placed in the binding site. A structural feature, pi-bulge was introduced to give substrate access to the protoporphyrin IX. These de novo metalloproteins are currently being tested for their activity towards hydroxylation and epoxidation. The de novo designed protein shows hydroxylation of aniline to 4-aminophenol. This study will help provide structural information of utmost importance in understanding de novo computational design variables impacting the functional activities of a protein.

Keywords: metalloproteins, protein design, de novo protein, biocatalysis

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Authors: Victor Igwemezie, Ali Mehmanparast

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The correct knowledge of corrosion fatigue mechanism in marine steel is very important. This is because it enables the design, selection, and use of steels for offshore applications. It also supports realistic corrosion fatigue life prediction of marine structures. A study has been conducted to increase the understanding of corrosion fatigue mechanism in marine steels. The materials investigated are normalized and advanced S355 Thermomechanical control process (TMCP) steels commonly used in the design of offshore wind turbine support structures. The experimental study was carried out by conducting corrosion fatigue tests under conditions pertinent to offshore wind turbine operations, using the state of the art facilities. A careful microstructural study of the crack growth path was conducted using metallurgical optical microscope (OM), scanning electron microscope (SEM) and Energy Dispersive X-Ray Spectroscopy (EDX). The test was conducted on three subgrades of S355 steel: S355J2+N, S355G8+M and S355G10+M and the data compared with similar studies in the literature. The result shows that the ferrite-pearlite morphology primarily controls the corrosion-fatigue crack growth path in marine steels. A corrosion fatigue mechanism which relies on the hydrogen embrittlement of the grain boundaries and pearlite phase is used to explain the crack propagation behaviour. The crack growth trend in the Paris region of the da/dN vs. ΔK curve is used to explain the dependency of the corrosion-fatigue crack growth rate on the ferrite-pearlite morphology.

Keywords: corrosion-fatigue mechanism, fatigue crack growth rate, ferritic-pearlitic steel, microstructure, phase morphology

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Authors: Jyotsna Gupta, S. Ghosh, S. Aravindan

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The requirement of artificial prostheses (such as hip and knee joints) has increased with time. Many researchers are working to develop new implants with improved properties such as excellent biocompatibility with no tissue reactions, corrosion resistance in body fluid, high yield strength and low elastic modulus. Further, the morphological properties of the artificial implants should also match with that of the human bone so that cell adhesion, proliferation and transportation of the minerals and nutrition through body fluid can be obtained. Present study attempts to make porous Ti6Al15Mo alloys through powder metallurgy route using space holder technique. The alloy consists of 6wt% of Al which was taken as α phase stabilizer and 15wt% Mo was taken as β phase stabilizer with theoretical density 4.708. Ammonium hydrogen carbonate is used as a space holder in order to generate the porosity. The porosity of these fabricated porous alloys was controlled by adding the 0, 50, 70 vol.% of the space holder content. Three phases were found in the microstructure: α, α_2 and β phase of titanium. Kirkendall pores are observed to be decreased with increase of holding time during sintering and parallelly compressive strength and elastic modulus value increased slightly. Compressive strength and elastic modulus of porous Ti-6Al-15Mo alloy (1.17 g/cm3 density) is found to be suitable for cancellous bone. Released ions from Ti-6Al-15Mo alloy are far below from the permissible limits in human body.

Keywords: bone implant, powder metallurgy, sintering time, Ti-6Al-15Mo

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Authors: Obinna K. Ihesiulor, Krishna Shankar, Paul Smith, Alan Fien

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Excessive fretting wear at the taper-trunnion junction (trunnionosis) apparently contributes to the high failure rates of hip implants. Implant wear and corrosion lead to the release of metal particulate debris and subsequent release of metal ions at the taper-trunnion surface. This results in a type of metal poisoning referred to as metallosis. The consequences of metal poisoning include; osteolysis (bone loss), osteoarthritis (pain), aseptic loosening of the prosthesis and revision surgery. Follow up after revision surgery, metal debris particles are commonly found in numerous locations. Background: A stable connection between the femoral ball head (taper) and stem (trunnion) is necessary to prevent relative motions and corrosion at the taper junction. Hence, the importance of component assembly cannot be over-emphasized. Therefore, the aim of this study is to determine the influence of head-stem junction assembly by press fitting and the subsequent disengagement/disassembly on the connection strength between the taper ball head and stem. Methods: CoCr femoral heads were assembled with High stainless hydrogen steel stem (trunnion) by Push-in i.e. press fit; and disengaged by Pull-out test. The strength and stability of the two connections were evaluated by measuring the head pull-out forces according to ISO 7206-10 standards. Findings: The head-stem junction strength linearly increases with assembly forces.

Keywords: wear, modular hip prosthesis, taper head-stem, force assembly and disassembly

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Authors: Sonam Chorol, Sharvan Kumar, Pritam Mukhopadhyay

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In biology, supramolecular systems require the use of chemical fuels to stay in sustained nonequilibrium steady states termed dissipative self-assembly in contrast to synthetic self-assembly. Biomimicking these natural dynamic systems, some studies have demonstrated artificial self-assembly under nonequilibrium utilizing various forms of energies (fuel) such as chemical, redox, and pH. Naphthalene diimides (NDIs) are well-known organic molecules in supramolecular architectures with high electron affinity and have applications in controlled electron transfer (ET) reactions, etc. Herein, we report the endergonic ET from tetraphenylborate to highly electron-deficient phosphonium NDI²+ dication to generate NDI•+ radical. The formation of radicals was confirmed by UV-Vis-NIR absorption spectroscopy. Electron-donor and electron-acceptor energy levels were calculated from experimental electrochemistry and theoretical DFT analysis. The HOMO of the electron donor locates below the LUMO of the electro-acceptor. This indicates that electron transfer is endergonic (ΔE°ET = negative). The endergonic ET from NaBPh₄ to NDI²+ dication was achieved thermodynamically by the formation of coupled biphenyl product confirmed by GC-MS analysis. NDI molecule bearing octyl phosphonium at the core and H-bond forming imide moieties at the axial position forms a gel. The rheological properties of purified radical ion NDI⦁+ gels were evaluated. The atomic force microscopy studies reveal the formation of large branching-type networks with a maximum height of 70-80 nm. The endergonic ET from NaBPh₄ to NDI²+ dication was used to design the assembly and disassembly redox reaction cycle using reducing (NaBPh₄) and oxidizing agents (Br₂) as chemical fuels. A part of NaBPh₄ is used to drive assembly, while a fraction of the NaBPh₄ is dissipated by forming a useful product. The system goes back to the disassembled NDI²+ dication state with the addition of Br₂. We think bioinspired dissipative self-assembly is the best approach to developing future lifelike materials with autonomous behavior.

Keywords: Ionic-gel, redox-cycle, self-assembly, useful product

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Authors: A. Pascual Ramsay

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Accounts of the management of the economic and euro crisis in Spain have been dominated by an emphasis on external constraints. However, this approach leaves unanswered important questions about the role of domestic political factors. Using systematic qualitative primary research and employing elite interviewing and process tracing, this paper aims to fill this gap for the period of the Partido Socialista Obrero Español (PSOE) administration. The paper shows that domestic politics played a crucial role in the management of the crisis, most importantly by determining the shape of the measures undertaken. In its three distinct stages – downplaying/inaction, reaction/stimulus, and austerity/reform – the PSOE's response was certainly constrained by external factors, most notably EMU membership and the actions of sovereign-bond investors, the ECB and Germany. Yet while these external constraints forced the government to act, domestic political factors fundamentally shaped the content of key measures: the fiscal stimulus, the labour, financial and pension reforms, the refusal to accept a bailout or the reform of the Constitution. Seven factors were particularly influential: i) electoral and political cost, ii) party and partisanship, iii) organised interests, iv) domestic institutions, v) ideological preferences, vi) ineffective decision-making, and vii) judgement and personal characteristics of decision-makers. In conclusion, domestic politics played an important role in the management of the crisis, a role that has been underestimated by dominant approaches focusing on external constraints and weak domestic policy autonomy. The findings provide empirical evidence to support research agendas that identify significant state discretion in the face of international economic integration and an important role for domestic political factors such as institutions, material interests, partisanship and ideology in shaping economic outcomes.

Keywords: economic crisis, Euro, PSOE, Spain

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Authors: Kinga Mylkie, Pawel Nowak, Marta Z. Borowska

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The most important proteins in human serum responsible for drug binding are human serum albumin (HSA) and α1-acid glycoprotein (AGP). The AGP molecule is a glycoconjugate containing a single polypeptide chain composed of 183 amino acids (the core of the protein), and five glycan branched chains (sugar part) covalently linked by an N-glycosidic bond with aspartyl residues (Asp(N) -15, -38, -54, -75, - 85) of polypeptide chain. This protein plays an important role in binding alkaline drugs, a large group of drugs used in psychiatry, some acid drugs (e.g., coumarin anticoagulants), and neutral drugs (steroid hormones). The main goal of the research was to obtain magnetic nanoparticles coated with biopolymers in a chemically modified form, which will have highly reactive functional groups able to effectively immobilize the glycoprotein (acid α1-glycoprotein) without losing the ability to bind active substances. The first phase of the project involved the chemical modification of biopolymer starch. Modification of starch was carried out by methods of organic synthesis, leading to the preparation of a polymer enriched on its surface with aldehyde groups, which in the next step was coupled with 3-aminophenylboronic acid. Magnetite nanoparticles coated with starch were prepared by in situ co-precipitation and then oxidized with a 1 M sodium periodate solution to form a dialdehyde starch coating. Afterward, the reaction between the magnetite nanoparticles coated with dialdehyde starch and 3-aminophenylboronic acid was carried out. The obtained materials consist of a magnetite core surrounded by a layer of modified polymer, which contains on its surface dihydroxyboryl groups of boronic acids which are capable of binding glycoproteins. Magnetic nanoparticles obtained as carriers for plasma protein immobilization were fully characterized by ATR-FTIR, TEM, SEM, and DLS. The glycoprotein was immobilized on the obtained nanoparticles. The amount of mobilized protein was determined by the Bradford method.

Keywords: glycoproteins, immobilization, magnetic nanoparticles, polysaccharides

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Authors: Y. A. Prada, Fanny Guzman, Rafael Cabanzo, John J. Castillo, Enrique Mejia-Ospino

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In this work, we show the important results about of synthesis of photoluminiscents gold nanoclusters using a small peptide as template for biosensing applications. Interestingly, we design one peptide (NBC2854) homologue to conservative domain from 215 250 residue of a galactolectin protein which can recognize the proteophosphoglycans (PPG) from Leishmania. Peptide was synthetized by multiple solid phase synthesis using FMoc group methodology in acid medium. Finally, the peptide was purified by High-Performance Liquid Chromatography using a Vydac C-18 preparative column and the detection was at 215 nm using a Photo Diode Array detector. Molecular mass of this peptide was confirmed by MALDI-TOF and to verify the α-helix structure we use Circular Dichroism. By means of the methodology used we obtained a novel fluorescents gold nanoclusters (AuNC) using NBC2854 as a template. In this work, we described an easy and fast microsonic method for the synthesis of AuNC with ≈ 3.0 nm of hydrodynamic size and photoemission at 630 nm. The presence of cysteine residue in the C-terminal of the peptide allows the formation of Au-S bond which confers stability to Peptide-based gold nanoclusters. Interactions between the peptide and gold nanoclusters were confirmed by X-ray Photoemission and Raman Spectroscopy. Notably, from the ultrafine spectra shown in the MALDI-TOF analysis which containing only 3-7 KDa species was assigned to Au₈-₁₈[NBC2854]₂ clusters. Finally, we evaluated the Peptide-gold nanocluster as an optical biosensor based on fluorescence spectroscopy and the fluorescence signal of PPG (0.1 µg-mL⁻¹ to 1000 µg-mL⁻¹) was amplified at the same wavelength emission (≈ 630 nm). This can suggest that there is a strong interaction between PPG and Pep@AuNC, therefore, the increase of the fluorescence intensity can be related to the association mechanism that take place when the target molecule is sensing by the Pep@AuNC conjugate. Further spectroscopic studies are necessary to evaluate the fluorescence mechanism involve in the sensing of the PPG by the Pep@AuNC. To our best knowledge the fabrication of an optical biosensor based on Pep@AuNC for sensing biomolecules such as Proteophosphoglycans which are secreted in abundance by parasites Leishmania.

Keywords: biosensing, fluorescence, Leishmania, peptide-gold nanoclusters, proteophosphoglycans

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Authors: Mona Alharbi

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Melioidosis has emerged as a lethal disease. Unfortunately, the molecular mechanisms of virulence and pathogenicity of Burkholderia pseudomallei remain unknown. However, proteomics research has selected putative targets in B. pseudomallei that might play roles in the B. pseudomallei virulence. BPSL 2418 putative protein has been predicted as a free methionine sulfoxide reductase and interestingly there is a link between the level of the methionine sulfoxide in pathogen tissues and its virulence. Therefore in this work, we describe the cloning expression, purification, and crystallization of BPSL 2418 and the solution of its 3D structure using X-ray crystallography. Also, we aimed to identify the substrate binding and reduced forms of the enzyme to understand the role of BPSL 2418. The gene encoding BPSL2418 from B. pseudomallei was amplified by PCR and reclone in pETBlue-1 vector and transformed into E. coli Tuner DE3 pLacI. BPSL2418 was overexpressed using E. coli Tuner DE3 pLacI and induced by 300μM IPTG for 4h at 37°C. Then BPS2418 purified to better than 95% purity. The pure BPSL2418 was crystallized with PEG 4000 and PEG 6000 as precipitants in several conditions. Diffraction data were collected to 1.2Å resolution. The crystals belonged to space group P2 21 21 with unit-cell parameters a = 42.24Å, b = 53.48Å, c = 60.54Å, α=γ=β= 90Å. The BPSL2418 binding MES was solved by molecular replacement with the known structure 3ksf using PHASER program. The structure is composed of six antiparallel β-strands and four α-helices and two loops. BPSL2418 shows high homology with the GAF domain fRMsrs enzymes which suggest that BPSL2418 might act as methionine sulfoxide reductase. The amino acids alignment between the fRmsrs including BPSL 2418 shows that the three cysteines that thought to catalyze the reduction are fully conserved. BPSL 2418 contains the three conserved cysteines (Cys⁷⁵, Cys⁸⁵ and Cys¹⁰⁹). The active site contains the six antiparallel β-strands and two loops where the disulfide bond formed between Cys⁷⁵ and Cys¹⁰⁹. X-ray structure of free methionine sulfoxide binding and native forms of BPSL2418 were solved to increase the understanding of the BPSL2418 catalytic mechanism.

Keywords: X-Ray Crystallography, BPSL2418, Burkholderia pseudomallei, Melioidosis

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Authors: Yuri S. Djikaev

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A large subset of aqueous aerosols can be initially (immediately upon formation) coated with various organic amphiphilic compounds whereof the hydrophilic moieties are attached to the aqueous aerosol core while the hydrophobic moieties are exposed to the air thus forming a hydrophobic coating thereupon. We study the thermodynamics of water condensation on such an aerosol whereof the hydrophobic organic coating is being concomitantly processed by chemical reactions with atmospheric reactive species. Such processing (chemical aging) enables the initially inert aerosol to serve as a nucleating center for water condensation. The most probable pathway of such aging involves atmospheric hydroxyl radicals that abstract hydrogen atoms from hydrophobic moieties of surface organics (first step), the resulting radicals being quickly oxidized by ubiquitous atmospheric oxygen molecules to produce surface-bound peroxyl radicals (second step). Taking these two reactions into account, we derive an expression for the free energy of formation of an aqueous droplet on an organic-coated aerosol. The model is illustrated by numerical calculations. The results suggest that the formation of aqueous cloud droplets on such aerosols is most likely to occur via Kohler activation rather than via nucleation. The model allows one to determine the threshold parameters necessary for their Kohler activation. Numerical results also corroborate previous suggestions that one can neglect some details of aerosol chemical composition in investigating aerosol effects on climate.

Keywords: aqueous aerosols, organic coating, chemical aging, cloud condensation nuclei, Kohler activation, cloud droplets

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Authors: Nacera Baali, Zahia Belloum, Souad Ameddah, Fadila Benayache, Samir Benayache, Chantal Wrutniak-Cabello

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Allurement of herbs as health beneficial foods and as a source material for the development of new drugs, has led to greater furtherance in the study of herbal medicines during recent years. In the present study, in vitro antioxidant, free radical scavenging capacity, and hepatoprotective activity of butanolic extract from Genista quadriflora Munby (G.quadriflora) were evaluated using established in vitro models such as DPPH radical and hydrogen peroxide radical scavenging activities and antilipidperoxidation ability. Interestingly, the extract showed considerable in vitro antioxidant and free radical scavenging activities in a dose-dependent manner when compared to the standard antioxidant which verified the presence of antioxidant compound in extract tested. The hepatoprotective potential of G.quadriflora extract was also evaluated in male Wistar rats against paracetamol (APAP) induced liver damage. Therapy of G.quadriflora showed the liver protective effect on biochemical and histopathological alterations. Moreover, histological studies also supported the biochemical finding, that is, the maximum improvement in the histoarchitecture of the liver. Results revealed that G.quadriflora extract could protect the liver against APAP-induced oxidative damage by possibly increasing the antioxidant protection mechanism in rats. These findings are of great importance in view of the availability of the plant and its observed possible diverse applications in medicine and nutrition.

Keywords: genista quadriflora munby, antioxidant, liver, paracetamol, oxidative stress

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Authors: D. Shehu, Z. Alias

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Glutathione S-transferases (GSTs) are family of enzymes that function in the detoxification of variety of electrophilic substrates. In the present work, we report a novel zeta-like GST (designated as KKSG9) from the biphenyl/polychlorobiphenyl degrading organism Acidovorax sp. KKS102. KKSG9 possessed low sequence similarity but similar biochemical properties to zeta class GSTs. The gene for KKSG9 was cloned, purified and biochemically characterized. Functional analysis showed that the enzyme exhibits wider substrate specificity compared to most zeta class GSTs by reacting with 1-chloro-2,4-dinitrobenzene (CDNB), p-nitrobenzyl chloride (NBC), ethacrynic acid (EA), hydrogen peroxide, and cumene hydroperoxide (CuOOH). The enzyme also displayed dehalogenation function against dichloroacetate (a common substrate for zeta class GSTs) in addition to permethrin, and dieldrin. The functional role of Tyr12 was also investigated by site-directed mutagenesis. The mutant (Y12C) displayed low catalytic activity and dehalogenation function against all the substrates when compared with the wild type. Kinetic analysis using NBC and GSH as substrates showed that the mutant (Y12C) displayed a higher affinity for NBC when compared with the wild type, however, no significant change in GSH affinity was observed. These findings suggest that the presence of tyrosine residue in the motif might represent an evolutionary trend toward improving the catalytic activity of the enzyme. The enzyme as well could be useful in the bioremediation of various types of organochlorine pollutants.

Keywords: Acidovorax sp. KKS102, bioremediation, glutathione s-transferase, site-directed mutagenesis, zeta

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Authors: Rajani Kant Rai, Jayakrishnan Athipet

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There have been several attempts to prepare polymers with antimicrobial properties by doping with various N-halamines. Hydantoins (Cyclic N-halamine) is of importance due to their stability rechargeable chloroamide function, broad-spectrum anti-microbial action and ability to prevent resistance to the organisms. Polymerizable hydantoins are synthesized by tethering vinyl moieties to 5,5,-dialkyl hydantoin sacrificing the imide hydrogen in the molecule thereby restricting the halogen capture only to the amide nitrogen that results in compromised antibacterial activity. In order to increase the activity of the antimicrobial polymer, we have developed a scheme to maximize the attachment of chlorine to the amide and the imide moieties of hydantoin. Vinyl hydantoin monomer, (Z)-5-(4-((3-methylbuta-1,3-dien-2-yl)oxy)benzylidene)imidazolidine-2,4-dione (MBBID) was synthesized and copolymerized with a commercially available monomer, methyl methacrylate, by free radical polymerization. The antimicrobial activity of hydantoin is strongly dependent on their surface area and hence their microbial activity increases when incorporated in microspheres or nanoparticles as compared to their bulk counterpart. In this regard, smooth and rough surface microsphere of the vinyl monomer (MBBID) with commercial monomer was synthesized. The oxidative chlorine content of the copolymer ranged from 1.5 to 2.45 %. Further, to demonstrate the water purification potential, the thin column was packed with smooth or rough microspheres and challenged with simulated contaminated water that exhibited 6 log kill (total kill) of the bacteria in 20 minutes of exposure with smooth (25 mg/ml) and rough microsphere (15.0 mg/ml).

Keywords: cyclic N-halamine, vinyl hydantoin monomer, rough surface microsphere, simulated contaminated water

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Authors: Natesan Balasubramanian, Palpandi Pounpandi, Venkatraman Thamil Priya, Vellasamy Shanmugaiah, Karubbiah Balakrishnan, Mandayam Anandam Thirunarayan

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Streptococcus agalactiae is commonly known as Group B Streptococcus (GBS) and it is the most common cause of life-threatening bacterial infection. GBS first considered as a veterinary pathogen causing mastitis in cattle later becomes a human pathogen for severe neonatal infections. In this present study, a total of 20 new clinical isolates of S. agalactiae were collected from male (6) and female patient (14) with different age group. The isolates were from Urinary tract infection (UTI), blood, pus and eye ulcer. All the 20 S. agalactiae isolates has clear hemolysis properties on blood agar medium and were identified by serogrouping and MALTI-TOF-MS analysis. Antibiotic susceptibility/resistance test was performed for 20 S. agalactiae isolates, further phenotypic resistance pattern was observed for tetracycline, vancomycin, ampicillin and penicillin. Genotypically we found two antibiotic resistance genes such as Betalactem antibiotic resistance gene (Tem) (70%) and tetracycline resistance gene Tet(O) 15% in our isolates. Six virulence factors encoding genes were performed by PCR in twenty GBS isolates, cfb gene (100%), followed by, cylE(90.47%), lmp(85.7%), bca(71.42%), rib (38%) and low frequency in bac gene (4.76%) were determined. Most of the S. agalactiae isolates produced strong biofilm in the polystyrene surface (hydrophobic), and low-level biofilm formation was found in glass tube (hydrophilic) surface. lytR is secreted protein and localized in bacterial cell wall, extra cellular membrane, and cytoplasm. In silico docking studies were performed for lytR protein with four antibiofilm compounds, including a peptide (PR39) with the docking study showed peptide has strong interaction followed by ellagic acid and interaction length is 2.95, 2.97 and 2.95 A°. In ligand EGCGO10 and O11 two atoms intract with lytR (Leu271), with binding bond affinity length is 3.24 and 3.14. The aminoacid Leu 271 is act as an impartant aminoacid, since ellagic acid and EGCG interact with same aminoacid.

Keywords: antibiotics, biofilms, clinical isolates, S. agalactiae, virulence

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Authors: Avinashkumar Karre

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Sulfur recovery unit, most commonly called as Claus process, is very significant gas desulfurization process unit in refinery and gas industries. Explorations of new natural gas fields, refining of high-sulfur crude oils, and recent crude expansion projects are needing capacity expansion of Claus unit for many companies around the world. In refineries, the sulphur recovery units take acid gas from amine regeneration units and sour water strippers, converting hydrogen sulfide to elemental sulfur using the Claus process. The Claus process is hydraulically limited by mass flow rate. Reducing the pressure drop across control valves, flow meters, lines, knock-out drums, and packing improves the capacity. Oxygen enrichment helps improve the capacity by removing nitrogen, this is more commonly done on all capacity expansion projects. Typical upgrades required due to oxygen enrichment are new burners, new refractory in thermal reactor, resizing of 1st condenser, instrumentation changes, and steam/condensate heat integration. Some other capacity expansion options typically considered are tail gas compressor, replacing air blower with higher head, hydrocarbon minimization in the feed, water removal, and ammonia removal. Increased capacity related upgrades in sulfur recovery unit also need changes in the tail gas treatment unit, typical changes include improvement to quench tower duty, packing area upgrades in quench and absorber towers and increased amine circulation flow rates.

Keywords: Claus process, oxygen enrichment, sulfur recovery unit, tail gas treatment unit

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Authors: Cagla Gul Guldiken, Levent Akyalcin, Hasan Ferdi Gercel

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Fuel cells are electrochemical devices which convert the chemical energy of hydrogen into the electricity. Among the types of fuel cells, polymer electrolyte membrane fuel cells (PEMFCs) are attracting considerable attention as non-polluting power generators with high energy conversion efficiencies in mobile applications. Polymer electrolyte membrane (PEM) is one of the essential components of PEMFCs. Perfluorosulfonic acid based membranes known as Nafion® is widely used as PEMs. Nafion® membranes water dependent proton conductivity which limits the operating temperature below 100ᵒC. At higher temperatures, proton conductivity and mechanical stability of these membranes decrease because of dehydration. Polybenzimidazole (PBI), which has good anhydrous proton conductivity after doped with acids, as well as excellent thermal stability, shows great potential in the application of high temperature PEMFCs. In the present study, PBI polymers were synthesized by solution polycondensation at 190 and 210ᵒC. The synthesized polymers were characterized by FTIR, 1H NMR, and TGA. Phosphoric acid doped PBI membranes were prepared and tested in a PEMFC. The influences of reaction temperature on structural properties of synthesized polymers were investigated. Mechanical properties, acid-doping level, proton conductivity, and fuel cell performances of prepared phosphoric acid doped PBI membranes were evaluated. The maximum power density was found as 32.5 mW/cm² at 120ᵒC.

Keywords: fuel cell, high temperature polymer electrolyte membrane, polybenzimidazole, proton exchange membrane fuel cell

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Authors: Wang Huiwen

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Since its release, Toni Morrison's novel Beloved has garnered significant international recognition, and its adaptation of a historical account has profoundly affected readers and scholars, evoking a visceral understanding of the suffering endured by black slaves. The ecofeminist approach has garnered more attention in recent times. The emergence of ecofeminism may be attributed to the feminist movement, which has subsequently evolved into several branches, including cultural ecofeminism, social ecofeminism, and socialist ecofeminism, each of which is developing its own specific characteristics. The many branches hold differing perspectives, yet they all converge on a key principle: the interconnectedness between the subjugation of women and the exploitation of nature can be traced back to a common underlying cognitive framework. Scholarly investigations into the novel Beloved have primarily centered on the cultural interpretations around the emancipation of African American women, with a predominant lens rooted in cultural ecofeminism. This thesis aims to analyze Morrison's feminist beliefs in the novel Beloved by integrating socialist and cultural ecofeminist perspectives, which seeks to challenge the limitations of essentialism within ecofeminism while also proposing a strategy to address exploitation and dismantle oppressive structures depicted in Beloved. This thesis examines the white patriarchal oppression system underlying the relationships between men and women, blacks and whites, and man and nature as shown in the novel. What the black women have been deprived of compared with the black men, white women and white men is a main clue of this research, while nature is a key complement of each chapter for their loss. The attainment of spiritual redemption and ultimate freedom is contingent upon the social revolution that enables bodily emancipation, both of which are indispensable for black women. The weighty historical pains, traumatic recollections, and compromised sense of self prompted African slaves to embark on a quest for personal redemption. The restoration of the bond between black men and women, as well as the relationship between black individuals and nature, is a clear and undeniable pathway towards the final freedom of black women in the novel Beloved.

Keywords: beloved, ecofeminism, black women, nature, essentialism

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Authors: A. Q. Sobia, M. S. Hamidah, I. Azmi, S. F. A. Rafeeqi

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Fibre-reinforced polymer (FRP) strengthened reinforced concrete (RC) structures are susceptible to intense deterioration when exposed to elevated temperatures, particularly in the incident of fire. FRP has the tendency to lose bond with the substrate due to the low glass transition temperature of epoxy; the key component of FRP matrix.  In the past few decades, various types of high performance cementitious composites (HPCC) were explored for the protection of RC structural members against elevated temperature. However, there is an inadequate information on the influence of elevated temperature on the ultra high performance fibre-reinforced cementitious composites (UHPFRCC) containing ground granulated blast furnace slag (GGBS) as a replacement of high alumina cement (HAC) in conjunction with hybrid fibres (basalt and polypropylene fibres), which could be a prospective fire resisting material for the structural components. The influence of elevated temperatures on the compressive as well as flexural strength of UHPFRCC, made of HAC-GGBS and hybrid fibres, were examined in this study. Besides control sample (without fibres), three other samples, containing 0.5%, 1% and 1.5% of basalt fibres by total weight of mix and 1 kg/m³ of polypropylene fibres, were prepared and tested. Another mix was also prepared with only 1 kg/m³ of polypropylene fibres. Each of the samples were retained at ambient temperature as well as exposed to 400, 700 and 1000 °C followed by testing after 28 and 56 days of conventional curing. Investigation of results disclosed that the use of hybrid fibres significantly helped to improve the ambient temperature compressive and flexural strength of UHPFRCC, which was found to be 80 and 14.3 MPa respectively. However, the optimum residual compressive strength was marked by UHPFRCC-CP (with polypropylene fibres only), equally after both curing days (28 and 56 days), i.e. 41%. In addition, the utmost residual flexural strength, after 28 and 56 days of curing, was marked by UHPFRCC– CP and UHPFRCC– CB2 (1 kg/m³ of PP fibres + 1% of basalt fibres) i.e. 39% and 48.5% respectively.

Keywords: fibre reinforced polymer materials (FRP), ground granulated blast furnace slag (GGBS), high-alumina cement, hybrid, fibres

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Authors: Shu-Jen Chen, Yi-Chien Wan, Ruey-Chi Wang

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Hydroxyapatite (Ca10(PO4)6(OH)2, HAp) can be applied to the fabrication of bone replacement materials, the composite of dental filling, and the adsorption of biomolecules and dyes. The integration of HAp and magnetic materials would offer several advantages for bio-separation process because the magnetic adsorbents is capable of recovered by applied magnetic field. C-phycocyanin (C-PC) and Allophycocyanin (APC), isolated from Spirulina platensis, can be used in fluorescent labeling probes, health care foods and clinical diagnostic reagents. Although the purification of C-PC and APC are reported by HAp adsorption, the adsorption of C-PC and APC by magnetic HAp composites was not reported yet. Therefore, the fabrication of HAp with magnetic silica nanoparticles for proteins adsorption was investigated in this work. First, the magnetic silica particles were prepared by covering silica layer on Fe3O4 nanoparticles with a reverse micelle method. Then, the Fe3O4@SiO2 nanoparticles were mixed with calcium carbonate to obtain magnetic silica/calcium carbonate composites (Fe3O4@SiO2/CaCO3). The Fe3O4@SiO2/CaCO3 was further reacted with K2HPO4 for preparing the magnetic silica/hydroxyapatite composites (Fe3O4@SiO2/HAp). The adsorption experiments indicated that the adsorption capacity of Fe3O4@SiO2/HAp toward C-PC and APC were highest at pH 6. The adsorption of C-PC and APC by Fe3O4@SiO2/HAp could be correlated by the pseudo-second-order model, indicating chemical adsorption dominating the adsorption process. Furthermore, the adsorption data showed that the adsorption of Fe3O4@SiO2/HAp toward C-PC and APC followed the Langmuir isotherm. The isoelectric points of C-PC and APC were around 5.0. Additionally, the zeta potential data showed the Fe3O4@SiO2/HAp composite was negative charged at pH 6. Accordingly, the adsorption mechanism of Fe3O4@SiO2/HAp toward C-PC and APC should be governed by hydrogen bonding rather than electrostatic interaction. On the other hand, as compared to C-PC, the Fe3O4@SiO2/HAp shows higher adsorption affinity toward APC. Although the Fe3O4@SiO2/HAp cannot recover C-PC and APC from Spirulina platensis homogenate, the Fe3O4@SiO2/HAp can be applied to separate C-PC and APC.

Keywords: hydroxyapatite, magnetic, C-phycocyanin, allophycocyanin

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Authors: Camila Freire Barrios, Gonzalo Rivera Talavera

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The importance of public spaces has been shown for many years, and in different disciplines, with one example being their ability for developing a sustainable social environment, especially in mega cities like Lima. The aim of this study was to explore the process of space appropriation that occurs in the Peripheral Library of the district El Agustino in Lima, Peru. Space appropriation is a process by which people develop a link with a place within a specific sociocultural context. This process has been related to positive outcomes, such as: participation and in the development of compassionate behaviors with these places. To achieve the purpose of the research, a qualitative design was selected because this will allowed exploring in deep the process in an specific context. The study interviewed six adults, all of whom were deliberately chosen to have the longest residence time in the district and also utilized the library the most. In a complementary manner, two children and one adolescent were interviewed. Likewise, two observations were made on a weekday and weekend, and public documentation information was collected. As a result, five categories linked to this process were identified. It was found that the process of space appropriation begins with the needs of the people who arrive at the library, which provides benefits to these people by fulfilling them. Next in the process, through the construction of meanings, the library is then valued as a pleasant, productive, safe and regulated place; as a result, people become identified with the library. The identification generated is subsequently reflected in the level of participation that the person has in the library, which may go in a continuum from no participating at all to a more direct involvement in the library activities, as well as voluntary and altruistic work. Finally, this process leads to the library becoming part of the neighborhood. This study allows having a better understanding of how sociospatial processes work in a Latinamerican context and in cities like Lima, where the third of the country’s population lives. Also, Lima has grown in the past 50 years in a excessively way and with lack of planification. Therefore, these results brings new research questions and highlights the importance of learning how to design public spaces in order to promote these processes to develop.

Keywords: bond with the place, place identity, public spaces, space appropriation

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Authors: Srinivasa Reddy Mallampati, Chi-Hyeon Lee, Nguyen Thanh Truc, Byeong-Kyu Lee

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Organic polymeric materials (plastics) are widely used in our daily life and various industrial fields. The separation of waste plastics is important for its feedstock and mechanical recycling. One of the major problems in incineration for thermal recycling or heat melting for material recycling is the polyvinyl chloride (PVC) contained in waste plastics. This is due to the production of hydrogen chloride, chlorine gas, dioxins, and furans originated from PVC. Therefore, the separation of PVC from waste plastics is necessary before recycling. The separation of heavy polymers (PVC 1.42, PMMA 1.12, PC 1.22 and PET 1.27 g/cm3 ) from light ones (PE and PP 0.99 g/cm3) can be achieved on the basis of their density. However it is difficult to separate PVC from other heavy polymers basis of density. There are no simple and inexpensive techniques to separate PVC from others. If hydrophobic the PVC surface is selectively changed into hydrophilic, where other polymers still have hydrophobic surface, flotation process can separate PVC from others. In the present study, the selective surface hydrophilization of polyvinyl chloride (PVC) by microwave treatment after alkaline/acid washing and with activated carbon was studied as the pre-treatment of its separation by the following froth flotation. In presence of activated carbon as absorbent, the microwave treatment could selectively increase the hydrophilicity of the PVC surface (i.e. PVC contact angle decreased about 19o) among other plastics mixture. At this stage, 100% PVC separation from other plastics could be achieved by the combination of the pre- microwave treatment with activated carbon and the following froth floatation. The hydrophilization of PVC by surface analysis would be due to the hydrophilic groups produced by microwave treatment with activated carbon. The effect of optimum condition and detailed mechanism onto separation efficiency in the froth floatation was also investigated.

Keywords: Hydrophilic, PVC, contact angle, additive, microwave, froth floatation, waste plastics

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Authors: Hanan F. Aly, Fateheya M. Metwally, Hanaa H. Ahmed

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The current study is undertaken to elucidate a possible neuroprotective role of dehydroepiandrosterone (DHEA) against the development of Alzheimer’s disease in experimental rat model. Alzheimer’s disease was produced in young female ovariectomized rats by intraperitoneal administration of AlCl3 (4.2 mg/kg body weight) daily for 12 weeks. Half of these animals also received orally DHEA (250 mg/kg body weight, three times weekly) for 18 weeks. Control groups of animals received either DHAE alone, or no DHEA, or were not ovariectomized. After such treatment the animals were analyzed for oxidative stress biomarkers such as hydrogen peroxide, nitric oxide and malondialdehyde, total antioxidant capacity, reduced glutathione, glutathione peroxidase, glutathione reductase, superoxide dismutase and catalase activities, antiapoptotic marker Bcl-2 and brain derived neurotrophic factor. Also, brain cholinergic markers (acetylcholinesterase and acetylcholine) were determined. The results revealed significant increase in oxidative stress parameters associated with significant decrease in the antioxidant enzyme activities in Al-intoxicated ovariectomized rats. Significant depletion in brain Bcl-2 and brain-derived neurotrophic factor levels were also detected. Moreover, significant elevations in brain acetylcholinesterase activity accompanied with significant reduction in acetylcholine level were recorded. Significant amelioration in all investigated parameters was detected as a result of treatment of Al-intoxicated ovariectomized rats with DHEA. These results were confirmed by histological examination of brain sections. These results clearly indicate a neuroprotective effect of DHEA against Alzheimer’s disease.

Keywords: Alzheimer’s disease, oxidative stress, apoptosis, dehydroepiandrosterone

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Authors: Ezana Haddis Weldeghebrael

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Addis Ababa City Administration is engaged in a massive facelift of the inner-city. The paper, therefore, aims to analyze the challenges of the current urban regeneration effort by paying special attention to Lideta and Basha Wolde Chilot projects. To this end, the paper has adopted a documentary research strategy to collect the data and Institutionalist perspective as well as the concept of urban regeneration to analyze the data. The sources were selected based on relevance and recency. Academic research outputs were used primarily. However, where much scholastic publications are not available institutional reports, newspaper articles, and expert presentations were used. The major findings of the research revealed that although the second generation of urban redevelopment projects have attempted to involve affected groups and succeeded in designing better neighborhoods, they are riddled with three major drawbacks. The first one is institutional constraints, i.e. absence of urban redevelopment strategy as well as housing policy, broad definition of ‘public purpose’, little regard for informal businesses, limitation on rights groups, negotiation power not devolved at sub-city level and no plan for groups that cannot afford to pay the down payment for low-cost apartments. The second one is planning limitation, i.e. absence of genuine affected group participation as well as consultative level of public engagement. The third one is implementation failure, i.e. no regard to maintaining social bond, non-participatory and ill-informed resettlement, interference from senior government officials, failure to protect the poor from speculators, corruption and disregard to heritage buildings. Based on the findings, the paper concluded that the current inner-city redevelopment has failed to be socially sustainable and calls for enactment of housing policy as well as redevelopment strategy, affected group participation, on-site resettlement, empowering the Sub-city to manage the project and allowing housing rights groups to advocate for the poor slum dwellers.

Keywords: participation, redevelopment, planning, implementation, consultation

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Authors: Muhammad A. Muhammad

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Butenafine (N-4-tert-butyl benzyl-N-methyl-1-naphthylene methylamine hydrochloride) is a benzylamine antimycotic (antifungal) agent that has a broad spectrum of action. The quest for improved antimycotic action brought about many research on the structure-activity properties of butenafine in relation to other antifungal agents. Of all those research, only little or no effort was recorded on the substituents attached to the aromatic systems in butenafine. In this research, N-(4-(tert-butyl) benzyl)-1-(4-tert-butyl) phenyl)-N-methyl methanaminium chloride, which is a butenafine analogue was synthesised from tert-butyl benzyl derivatives, by reductive amination using various solvents through a direct approach, where 1,2-dichloroethane gave the best solvent action at 40 °C (Yield: 75%) and of all the reducing agents used, sodium borohydride was found to give the best reducing action in the presence of silica chloride at room temperature (Yield: 50%). Characterization of the compound by 1H NMR showed a singlet peak of 18 hydrogen atoms with a chemical shift at 1.3-1.5 ppm for the presence of 6 methyl groups in the two tert-butyl substituents, the 13C NMR also indicated the presence of the two tert-butyl substituents by the peak with a chemical shift at 31-32 ppm for the six methyl carbon atoms, the IR indicated the presence of a tertiary ammonium ion by a strong band at 2460 cm-1 and finally the EIS-MS confirmed the molar mass of the compound by a mass to charge ratio of 324.2693. These results suggested that the target molecule was actually synthesised and therefore, 1,2-dichloroethane is a good solvent for this synthesis, and the most suitable reducing agent is sodium borohydride.

Keywords: antimicrobial agents, antimycotic agents, butenafine, chemotherapeutic agents, semisynthetic agents

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Authors: Héctor González Espinosa, Ricardo Ivan Cordova Chávez, Alejandra Contreras Ramos, Itzia Irene Padilla Martínez, José Guadalupe Trujillo Ferrara, Marvin Antonio Soriano Ursúa

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Boronic acids are able to create diester bonds with carbohydrates because of their hydroxyl groups; in nature, there are some organoborates with these characteristics, such as the calcium fructoborate, formed by the union of two fructose molecules and a boron atom, synthesized by plants. In addition, it has been observed that, in animal cells only the compounds with cis-diol functional groups are capable of linking to boric or boronic acids. The formation of these organoboron compounds could impair the physical and chemical properties of the precursors, even their acute toxicity. In this project, two carbohydrate-derived boron-containing compounds from D-fructose and D-arabinose and phenylboronic acid are analyzed by different spectroscopy techniques such as Raman, Infrared with Fourier Transform Infrared (FT-IR), Nuclear Magnetic Resonance (NMR) and X-ray diffraction crystallography to describe their chemical characteristics. Also, an acute toxicity test was performed to determine their LD50 using the Lorke’s method. It was confirmed by multiple spectra the formation of the adducts by the generation of the diester bonds with a β-D-pyranose of fructose and arabinose. The most prominent findings were the presence of signals corresponding to the formation of new bonds, like the stretching of B-O bonds, or the absence of signals of functional groups like the hydroxyls presented in the reagents used for the synthesis of the adducts. The NMR spectra yielded information about the stereoselectivity in the synthesis reaction, observed by the interaction of the protons and their vicinal atoms in the anomeric and second position carbons; but also, the absence of a racemic mix by the finding of just one signal in the range for the anomeric carbon in the 13C NMR spectra of both adducts. The acute toxicity tests by the Lorke’s method showed that the LD50 value for both compounds is 1265 mg/kg. Those results let us to propose these adducts as highly safe agents for further biological evaluation with medical purposes.

Keywords: acute toxicity, adduct, boron, carbohydrate, diester bond

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Authors: Aidan Battison, Neliswa Mama

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Environmental pollution by ionic species has been identified as one of the biggest challenges to the sustainable development of communities. The widespread use of organic and inorganic chemical products and the release of toxic chemical species from industrial waste have resulted in a need for advanced monitoring technologies for environment protection, remediation and restoration. Some of the disadvantages of conventional sensing methods include expensive instrumentation, well-controlled experimental conditions, time-consuming procedures and sometimes complicated sample preparation. On the contrary, the development of fluorescent chemosensors for biological and environmental detection of metal ions has attracted a great deal of attention due to their simplicity, high selectivity, eidetic recognition, rapid response and real-life monitoring. Coumarin derivatives S1 and S2 (Scheme 1) containing 1,2,3-triazole moieties at position -3- have been designed and synthesized from azide and alkyne derivatives by CuAAC “click” reactions for the detection of metal ions. These compounds displayed a strong preference for Fe3+ ions with complexation resulting in fluorescent quenching through photo-induced electron transfer (PET) by the “sphere of action” static quenching model. The tested metal ions included Cd2+, Pb2+, Ag+, Na+, Ca2+, Cr3+, Fe3+, Al3+, Cd2+, Ba2+, Cu2+, Co2+, Hg2+, Zn2+ and Ni2+. The detection limits of S1 and S2 were determined to be 4.1 and 5.1 uM, respectively. Compound S1 displayed the greatest selectivity towards Fe3+ in the presence of competing for metal cations. S1 could also be used for the detection of Fe3+ in a mixture of CH3CN/H¬2¬O. Binding stoichiometry between S1 and Fe3+ was determined by using both Jobs-plot and Benesi-Hildebrand analysis. The binding was shown to occur in a 1:1 ratio between the sensor and a metal cation. Reversibility studies between S1 and Fe3+ were conducted by using EDTA. The binding site of Fe3+ to S1 was determined by using 13 C NMR and Molecular Modelling studies. Complexation was suggested to occur between the lone-pair of electrons from the coumarin-carbonyl and the triazole-carbon double bond.

Keywords: chemosensor, "click" chemistry, coumarin, fluorescence, static quenching, triazole

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Authors: Farzad Doostishoar, Abdolreza Hasanzadeh, Seyed Amin Ayatolahi Mousavi

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Introduction and Goals: Deuterium has different action from its isotopes hydrogen in chemical reactions and biochemical processes. It is not a significant difference in heavier atoms between the behavior of heavier isotope and the lighter One but for very lighter atoms it is significant . According to that most of the weight of all creatures body is water natural rate can be significant. In this article we want to study the effect of reduced deuterium on the fungus cell. If we saw the dependence of deuterium concentration of environment on the cells growth we can test this in invivo models too. Methods: First we measured deuterium concentration of the distillated water this analyze was operated by Arak’s heavy water company. Then the deuterium was diluted to ½ ¼ 1/8 1/16 by adding water free of deuterium for making media. In tree of samples the deuterium concentration was increased by adding D2O up to 10,50,100 times more concentrated. For candida albicans growth we used sabor medium and for aspergillus fomigatis growth we used sabor medium containing chloramphenicol. After culturing the funguses species we put the mediums for each species in the shaker incubator for 10 days in 25 centigrade. In different days and times the plates were studied morphologically and some microscopic characteristics were studied too. This experiments and cultures were repeated 3 times. Results: Statistical analyzes by paired-sample T test showed that aspergilus fomigatoos growth was decreased in concentration of 72 ppm( half deuterium concentration of negative control) significantly. In deuterium concentration reduction the growth reduce into the negative control significantly. The project results showed that candida albicans was sensitive to reduce and decrease of the deuterium in all concentrations.

Keywords: deuterium, cancer cell, growth, candida albicans

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Authors: Kefale W. Yizengaw, Delele Worku Ayele, Jyh-Chiang Jiang

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The catalytic co-conversion of CO₂ and CH₄ to value-added compounds has become one of the promising approaches to addressing global climate change by having valuable fossil fuels. Thedirect co-conversion of CO₂ and CH₄ to value-added compounds is attractive but tremendously challenging because of both molecules' thermodynamic stability and kinetic inertness. In the present study, a single iridium atom doped and a single oxygen atom defect hematite (110)surface model catalyst, which can comprehend direct C–O coupling based on simultaneous activation of CO2 and CH4 was studied using density functional theory plus U (DFT + U)calculations. The presence of dual active sites on the Ir/Fe₂O₃(110)-OV surface catalyst enablesCO₂ activation on the Ir site and CH₄ activation at the defect site. The electron analysis for the theco-adsorption of CO₂ and CH₄ deals with the electron redistribution on the surface and clearly shows the synergistic effect for simultaneous CO₂ and CH₄ activation on Ir/α- Fe₂O₃(110)-OVsurface. The microkinetic analysis shows that the dissociation of CH4 to CH3 * and H* plays an excellent role in the C–O coupling. The coverage analysis for the intermediate products of the microkinetic simulation results indicates that C–O coupling is the reaction limiting step. Finally, after the CH₃O* intermediate product species is produced, the radical hydrogen species spontaneously diffuse to the CH3O* intermediate product to form methanol at around 490 [K]. The present work provides mechanistic and kinetic insights into the direct C–O coupling of CO₂and CH₄, which could help design more-efficient catalysts.

Keywords: co-conversion, C–O coupling, doping, oxygen vacancy, microkinetic

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Authors: Matthias Banholzer, Hagen Müller, Michael Pfitzner

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Gas internal combustion engines are widely used as propulsion systems or in power plants to generate heat and electricity. While there are different types of injection methods including the manifold port fuel injection and the direct injection, the latter has more potential to increase the specific power by avoiding air displacement in the intake and to reduce combustion anomalies such as backfire or pre-ignition. During the opening process of the injector, multiple flow regimes occur: subsonic, transonic and supersonic. To cover the wide range of Mach numbers a compressible pressure-based solver is used. While the standard Pressure Implicit with Splitting of Operators (PISO) method is used for the coupling between velocity and pressure, a high-resolution non-oscillatory central scheme established by Kurganov and Tadmor calculates the convective fluxes. A blending function based on the local Mach- and CFL-number switches between the compressible and incompressible regimes of the developed model. As the considered operating points are well above the critical state of the used fluids, the ideal gas assumption is not valid anymore. For the real gas thermodynamics, the models based on the Soave-Redlich-Kwong equation of state were implemented. The caloric properties are corrected using a departure formalism, for the viscosity and the thermal conductivity the empirical correlation of Chung is used. For the injector geometry, the dimensions of a diesel injector were adapted. Simulations were performed using different nozzle and needle geometries and opening curves. It can be clearly seen that there is a significant influence of all three parameters.

Keywords: high pressure gas injection, hybrid solver, hydrogen injection, needle opening process, real-gas thermodynamics

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