Search results for: organometallic complexes

Authors: Tianjiao Chu, Carla Rios Luci, Christy Maksoudian, Ara Sargsian, Bella B. Manshian, Stefaan J. Soenen

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Nanomaterials have gained high interest in their use as potent anticancer agents. Apart from delivering chemotherapeutic agents in order to reduce off-target effects, molecular agents have also been widely explored. The advances in our understanding of cell biology and cell death mechanisms1 has generated a broad library of potential therapeutic targets by siRNA, mRNA, or pDNA complexes. In the present study, we explore the ability of pDNA-polyplexes to induce tumor-specific necroptosis. This results in a cascade of effects, where immunogenic cell death potentiates anti-tumor immune responses and results in an influx of dendritic cells and cytotoxic T cells, rendering the tumor more amenable to immune checkpoint inhibition. This study aims to explore whether the induction of necroptosis in a subpopulation of tumor cells can be used to potentiate immune checkpoint inhibition studies.

Keywords: nanoparticle, MLKL, necroptosis, immunotherapy

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Authors: Khusboo Agrawal, S. Saraf

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Quercetin, a flavonol provides a cellular protection against UV induced oxidative damages due to its excellent free radical scavenging activity and direct pro-apoptopic effect on tumor cells. However, its topical use is limited due to its unfavorable physicochemical properties. The present study was aimed to evaluate the potential of mesoporous silica nanoparticles as topical carrier system for quercetin delivery. Complexes of quercetin with mesoporous silica was prepared with different weight ratios and characterized by thermo gravimetric analysis, X-ray diffraction, high resolution TEM, FT-IR spectroscopy, zeta potential measurements and differential scanning calorimetry The protective effect of this vehicle on UV-induced degradation of the quercetin was investigated revealing a certain positive influence of the inclusion on the photostability over time. Epidermal accumulation and transdermal permeation of this molecule were ex vivo evaluated by using Franz diffusion cells. The immobilization of Quercetin in mesoporous silica nanoparticles (MSNs) increased the stability without undermining the antioxidant efficacy.

Keywords: cancer, MSNs, quercetin, topical delivery

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Authors: Jin Yue

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Fresh produces especially fruits, vegetables, meats and aquatic products have limited shelf life and are highly susceptible to deterioration. Essential oils (EOs) extracted from plants have excellent antioxidant and broad-spectrum antibacterial activities, and they can play as natural food preservatives. But EOs are volatile, water insoluble, pungent, and easily decomposing under light and heat. Many approaches have been developed to improve the solubility and stability of EOs such as polymeric film, coating, nanoparticles, nano-emulsions and nanofibers. Construction of active packaging film which can incorporate EOs with high loading efficiency and controlled release of EOs has received great attention. It is still difficult to achieve accurate release of antibacterial compounds at specific target locations in active packaging. In this research, a relative humidity-responsive packaging material was designed, employing the electrospinning technique to fabricate a nanofibrous film loaded with a 4-terpineol/β-cyclodextrin inclusion complexes (4-TA/β-CD ICs). Functioning as an innovative food packaging material, the film demonstrated commendable attributes including pleasing appearance, thermal stability, mechanical properties, and effective barrier properties. The incorporation of inclusion complexes greatly enhanced the antioxidant and antibacterial activity of the film, particularly against Shewanella putrefaciens, with an inhibitory efficiency of up to 65%. Crucially, the film realized controlled release of 4-TA under 98% high relative humidity conditions by inducing the plasticization of polymers caused by water molecules, swelling of polymer chains, and destruction of hydrogen bonds within the cyclodextrin inclusion complex. This film with a long-term antimicrobial effect successfully extended the shelf life of Litopenaeus vannamei shrimp to 7 days at 4 °C. To further improve the loading efficiency and long-acting release of EOs, we synthesized the γ-cyclodextrin-metal organic frameworks (γ-CD-MOFs), and then efficiently anchored γ-CD-MOFs on chitosan-cellulose (CS-CEL) composite film by in situ growth method for controlled releasing of carvacrol (CAR). We found that the growth efficiency of γ-CD-MOFs was the highest when the concentration of CEL dispersion was 5%. The anchoring of γ-CD-MOFs on CS-CEL film significantly improved the surface area of CS-CEL film from 1.0294 m2/g to 43.3458 m2/g. The molecular docking and 1H NMR spectra indicated that γ-CD-MOF has better complexing and stabilizing ability for CAR molecules than γ-CD. In addition, the release of CAR reached 99.71±0.22% on the 10th day, while under 22% RH, the release pattern of CAR was a plateau with 14.71 ± 4.46%. The inhibition rate of this film against E. coli, S. aureus and B. cinerea was more than 99%, and extended the shelf life of strawberries to 7 days. By incorporating the merits of natural biopolymers and MOFs, this active packaging offers great potential as a substitute for traditional packaging materials.

Keywords: active packaging, antibacterial activity, controlled release, essential oils, food quality control

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Authors: Muzammil Dar

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The confluence of trans-national interests and divergent approaches followed by multiple actors has surrounded the Indo-Pacific region with myriad of strategic complexes- Geo-Political, Geo-economic, and security. This paper has thus made a humble attempt to understand the Indo-Pacific strategic predicament from Asia-Pacific perspective. The portmanteau of Indo-Pacific strategic gamble has multiple actors from global powers to regional actors. On the indo-pacific waters, not only flow trade relations, but the tides of conflicts and controversies are striking these actors against each other. The alliance formation and infrastructure building has built-in threat perceptions from rivals vice-versa. The assertiveness of China as a reality and India’s ideological doctrine of peace and friendship, as well as American rebalancing against China, could be seen as clear and bright on the Indo-Pacific strategic portmanteau. ASEAN and Japan, too, have oscillating posturing in the strategic dilemma. The aim and objective of the paper are to sketch out the prospectus and prejudices of Indo-pacific strategic complex.

Keywords: Indo Pacific, Asia Pacific, security and growth for all in the region, SAGAR, ASEAN China

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Authors: Rafayel Azizyan, Valeri Arakelyan, Aram Gevorgyan, Varduhi Balayan, Emil Gevorgyan

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Currently, mathematical and computer modeling are widely used in different biological studies to predict or assess behavior of such complex systems as biological ones. This study deals with mathematical and computer modeling of bi-substrate enzymatic reactions, which play an important role in different biochemical pathways. The main objective of this study is to represent the results from in silico investigation of bi-substrate enzymatic reactions in the presence of uncompetitive inhibitors, as well as to describe in details the inhibition effects. Four models of uncompetitive inhibition were designed using different software packages. Particularly, uncompetitive inhibitor to the first [ES1] and the second ([ES1S2]; [FS2]) enzyme-substrate complexes have been studied. The simulation, using the same kinetic parameters for all models allowed investigating the behavior of reactions as well as determined some interesting aspects concerning influence of different cases of uncompetitive inhibition. Besides that shown, that uncompetitive inhibitors exhibit specific selectivity depending on mechanism of bi-substrate enzymatic reaction.

Keywords: mathematical modeling, bi-substrate enzymatic reactions, reversible inhibition

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Authors: Heba M. Saad Eldien, Ola Abdel-Tawab Hussein, Ahmed Yassein Nassar

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Background: Indomethacin is a non-steroidal anti inflammatory drug. Indomethacin induces an injury to gastrointestinal mucosa in experimental animals and humans and their use is associated with a significant risk of hemorrhage, erosions and perforation of both gastric and intestinal ulcers. The anti-inflammatory action of copper complexes is an important activity of their anti-ulcer effect achieved by their intermediary role as a transport form of copper that allow activation of the several copper-dependent enzymes. Therefore, several copper complexes were synthesized and investigated as promising alternative anti-ulcer therapy. Aim of the work: The purpose of this study was to evaluate a copper chelating complex consisting of egg albumin and copper as one of the copper peptides that can be used as anti-inflammatory agent and effective in ameliorates the hazards of the indomethacin on the histological structure of the fundus of the stomach that could be added to raise the efficacy of the currently used simple and cheap gastric anti-inflammatory drug mucogel. Material &methods: This study was carried out on 40 adult male albino rats,divided equally into 4 groups;Group I(control group) received distilled water,Group II(indomethacin treated group) received (25 mg/kg body weight, oral intubation) once, Group III (mucogel treated group)2 mL/rat once daily, oral incubation, Group IV(copper complex group) 1 mL /rat of 30 gm of copper albumin complex was mixed uniformly with mucogel to 100 mL. Treatment has been started six hour after Induction of Ulcers and continued till the 3rd day. The animals sacrificed and was processed for light, transmission electron microscopy(TEM) and immunostaining for inducible nitric oxide synthase(iNOS). Results: Fundic mucosa of group II, showed exfoliation of epithelial cells lining the gland, discontinuity of surface epithelial cells (ulcer formation), vacuolation and detachment of cells, eosinophilic infiltration and congestion of blood vessels in the lamina propria and submucosa. There was thickening and disarrangement of mucosa, weak positive reaction for PAS and marked increase in the collagen fibers lamina propria and the submucosa of the fundus. TEM revealed degeneration of cheif and parietal cells.Marked increase positive reactive of iNOS in all cells of the fundic gland. Group III showed reconstruction of gastric gland with cystic dilatation and vacuolation, moderate decrease of collagen fibers, reduced the intensity of iNOS while in Group IV healthy mucosa with normal surface lining epithelium and fundic glands, strong positive reaction for PAS, marked decrease of collagen fibers and positive reaction for iNOS. TEM revealed regeneration of cheif and parietal cells. Conclusion: Co treatment of copper-albumin complex seems to be useful for gastric ulcer treatment and ameliorates most of hazards of indomethacin.

Keywords: copper complex, gastric ulcer, indomethacin, rat

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Authors: Anahita Mortazavi Manesh, Mojtaba Bagherzadeh

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Metalloporphyrins are well known to mimic the activity of monooxygenase enzymes. In this regard, metalloporphyrin complexes have been largely employed as valuable biomimetic catalysts, owing to the critical roles they play in oxygen transfer processes in catalytic oxidation reactions. Investigating in this area is based on different strategies to design selective, stable and high turnover catalytic systems. Immobilization of expensive metalloporphyrin catalysts onto supports appears to be a good way to improve their stability, selectivity and the catalytic performance because of the support environment and other advantages with respect to recovery, reuse. In other words, supporting metalloporphyrins provides a physical separation of active sites, thus minimizing catalyst self-destruction and dimerization of unhindered metalloporphyrins. Furthermore, heterogeneous catalytic oxidations have become an important target since their process are used in industry, helping to minimize the problems of industrial waste treatment. Hence, the immobilization of these biomimetic catalysts is much desired. An attractive approach is the preparation of the heterogeneous catalyst involves immobilization of complexes on silica coated magnetic nano-particles. Fe3O4@SiO2 magnetic nanoparticles have been studied extensively due to their superparamagnetism property, large surface area to volume ratio and easy functionalization. Using heterogenized homogeneous catalysts is an attractive option to facile separation of catalyst, simplified product work-up and continuity of catalytic system. Homogeneous catalysts immobilized on magnetic nanoparticles (MNPs) surface occupy a unique position due to combining the advantages of both homogeneous and heterogeneous catalysts. In addition, superparamagnetic nature of MNPs enable very simple separation of the immobilized catalysts from the reaction mixture using an external magnet. In the present work, an efficient heterogeneous catalyst was prepared by immobilizing manganese porphyrin on functionalized magnetic nanoparticles through the amino propyl linkage. The prepared catalyst was characterized by elemental analysis, FT-IR spectroscopy, X-ray powder diffraction, atomic absorption spectroscopy, UV-Vis spectroscopy, and scanning electron microscopy. Application of immobilized metalloporphyrin in the oxidation of various organic substrates was explored using Gas chromatographic (GC) analyses. The results showed that the supported Mn-porphyrin catalyst (Fe3O4@SiO2-NH2@MnPor) is an efficient and reusable catalyst in oxidation reactions. Our catalytic system exhibits high catalytic activity in terms of turnover number (TON) and reaction conditions. Leaching and recycling experiments revealed that nanocatalyst can be recovered several times without loss of activity and magnetic properties. The most important advantage of this heterogenized catalytic system is the simplicity of the catalyst separation in which the catalyst can be separated from the reaction mixture by applying a magnet. Furthermore, the separation and reuse of the magnetic Fe3O4 nanoparticles were very effective and economical.

Keywords: Fe3O4 nanoparticle, immobilized metalloporphyrin, magnetically separable nanocatalyst, oxidation reactions

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Authors: Yuping Liu, Li Tao, Yin Lu

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Accumulating evidence has been shown that diallyl trisulfide (DATS) from garlic may reduce the risk of developing several types of cancer. In view of the dynamic crosstalk interplayed by tumor cells and platelets in hematogenous metastasis, we demonstrate the effectiveness of DATS on the metastatic behaviors of MDA-MB-435s human breast cancer cell line co-incubated with activated platelets. Indeed, our data identified that DATS significantly blocked platelets fouction induced by PAF, followed by the decreased production of TXB2. DATS was found to dose-dependently suppressed MDA-MB-435s cell migration and invasion in presence of activated platelets by PAF in vitro. Furthermore, the expression, secretion and enzymatic activity of matrix metalloproteinase (MMP)-2/9, as well as the luciferase activity of upstream regulator NF-κB in MDA-MB-435s, were obviously diminished by DATS. In parallel, DATS blocked upstream NF-κB activation signaling complexes composed of extracellular signal-related kinase (ERK) as assessed by measuring the levels of the phosphorylated forms.

Keywords: DATS, ERK, metastasis, MMPs, NF-κB, platelet

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Authors: Sh. Gofurov, O. Ismailova, U. Makhmanov, A. Kokhkharov

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The refractometric method has been used to determine optical properties of concentration features of aqueous solutions of ethanol, tetrahydrofuran and dimethylformamide at the room temperature. Changes in dielectric permittivity of aqueous solutions of ethanol, tetrahydrofuran and dimethylformamide in a wide range of concentrations (0÷1.0 molar fraction) have been studied using molecular dynamics method. The curves depending on the concentration of experimental data on excess refractive indices and excess dielectric permittivity were compared. It has been shown that stable heteromolecular complexes in binary solutions are formed in the concentration range of 0.3÷0.4 mole fractions. The real and complex part of dielectric permittivity was obtained from dipole-dipole autocorrelation functions of molecules. At the concentrations of C = 0.3 / 0.4 m.f. the heteromolecular structures with hydrogen bonds are formed. This is confirmed by the extremum values of excessive dielectric permittivity and excessive refractive index of aqueous solutions.

Keywords: refractometric method, aqueous solution, molecular dynamics, dielectric constant

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Authors: Anitha Kandasamy, Thirumurugan Ramaiah

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Interestingly, organic materials exhibit large optical nonlinearity with quick responses and having the flexibility of molecular tailoring using computational modelling and favourable synthetic methodologies. Pyridine based organic compounds and carboxylic acid contained aromatic compounds play a crucial role in crystal engineering of NCS complexes that displays admirable optical nonlinearity with fast response and favourable physicochemical properties such as low dielectric constant, wide optical transparency and large laser damage threshold value requires for optoelectronics device applications. Based on these facts, it was projected to form an acentric molecule of π-conjugated system interaction with appropriately replaced electron donor and acceptor groups for achieving higher SHG activity in which quinoline-2-carboyxlic acid is chosen as an electron acceptor and capable of acting as an acid as well as a base molecule, while 2-amino-4-methylpyridine is used as an electron donor and previously employed in numerous proton transfer complexes for synthesis of NLO materials for optoelectronic applications. 2-amino-4-mehtylpyridinium quinoline-2-carboxylate molecular complex (2AQ) is having π-donor-acceptor groups in which 2-amino-4-methylpyridine donates one of its electron to quinoline -2-carboxylic acid thereby forming a protonated 2-amino-4-methyl pyridinium moiety and mono ionized quinoline-2-carboxylate moiety which are connected via N-H…O intermolecular interactions with non-centrosymmetric crystal packing arrangement at microscopic scale is accountable to the enhancement of macroscopic second order NLO activity. The 2AQ crystal was successfully grown by a slow evaporation solution growth technique and its structure was determined in orthorhombic crystal system with acentric, P212121, space group. Hirshfeld surface analysis reveals that O…H intermolecular interactions primarily contributed with 31.0 % to the structural stabilization of 2AQ. The molecular structure of title compound has been confirmed by 1H and 13C NMR spectral studies. The vibrational modes of functional groups present in 2AQ have been assigned by using FTIR and FT-Raman spectroscopy. The grown 2AQ crystal exhibits high optical transparency with lower cut-off wavelength (275 nm) within the region of 275-1500 nm. The laser study confirmed that 2AQ exhibits high SHG efficiency of 12.6 times greater than that of KDP. TGA-DTA analysis revealed that 2AQ crystal had a thermal stability of 223 °C. The low dielectric constant and low dielectric loss at higher frequencies confirmed good crystalline nature with fewer defects of grown 2AQ crystal. The grown crystal exhibits soft material and positive photoconduction behaviour. Mulliken atomic distribution and FMOs analysis suggested that the strong intermolecular hydrogen bonding which lead to the enhancement of NLO activity. These properties suggest that 2AQ crystal is a suitable material for optoelectronic and laser frequency conversion applications.

Keywords: crystal growth, NLO activity, proton transfer complex, quantum chemical investigation

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Authors: Mohammad Reza Ghaani, Michele Catti

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The reduction of CoO/Fe₂O₃ oxides supported on carbon xerogels was studied to elucidate the effect of nano-size distribution of the catalyst in carbon matrices. Resorcinol formaldehyde xerogels were synthesized, impregnated with iron and cobalt nitrates, and subsequently heated to obtain the oxides. The mechanism of oxide reduction to metal was investigated by in-situ synchrotron X-ray diffraction in dynamic, non-isothermal conditions. Kinetic profiles of the reactions were obtained by plotting the diffraction intensities of selected Bragg peaks vs. temperature. The extracted Temperature-Programmed-Reduction (TPR) diagrams were analyzed by appropriate kinetic models, leading to best results with the Avrami-Erofeev model for all reduction reactions considered. The activation energies for the two-step reduction of iron oxide were 65 and 37 kJmol⁻¹, respectively. The average value for the reduction of CoO to Co was found to be around 21 kJ mol⁻¹. Such results may contribute to develop efficient and inexpensive non-noble metal-based catalysts in element form, e.g., Fe, Co, via heterogenization of metal complexes on mesoporous supports.

Keywords: non-isothermal kinetics, carbon aerogel, in-situ synchrotron X-ray diffraction, reduction mechanisms

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Authors: Amita Barik, Ranjit Prasad Bahadur

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We investigate the role of water molecules in 89 protein-RNA complexes taken from the Protein Data Bank. Those with tRNA and single-stranded RNA are less hydrated than with duplex or ribosomal proteins. Protein-RNA interfaces are hydrated less than protein-DNA interfaces, but more than protein-protein interfaces. Majority of the waters at protein-RNA interfaces makes multiple H-bonds; however, a fraction does not make any. Those making Hbonds have preferences for the polar groups of RNA than its partner protein. The spatial distribution of waters makes interfaces with ribosomal proteins and single-stranded RNA relatively ‘dry’ than interfaces with tRNA and duplex RNA. In contrast to protein-DNA interfaces, mainly due to the presence of the 2’OH, the ribose in protein-RNA interfaces is hydrated more than the phosphate or the bases. The minor groove in protein-RNA interfaces is hydrated more than the major groove, while in protein-DNA interfaces it is reverse. The strands make the highest number of water-mediated H-bonds per unit interface area followed by the helices and the non-regular structures. The preserved waters at protein-RNA interfaces make higher number of H-bonds than the other waters. Preserved waters contribute toward the affinity in protein-RNA recognition and should be carefully treated while engineering protein-RNA interfaces.

Keywords: h-bonds, minor-major grooves, preserved water, protein-RNA interfaces

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Authors: Zuzana Tatarkova, Ivana Pilchova, Michal Cibulka, Martin Kolisek, Peter Racay, Peter Kaplan

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Introduction: Normal functioning of mitochondria is crucial for cardiac performance. Mitochondria undergo mitophagy and biogenesis, and mitochondrial proteins are subject to extensive post-translational modifications. The state of mitochondrial homeostasis reflects overall cellular fitness and longevity. Perturbed mitochondria produce less ATP, release greater amounts of reactive molecules, and are more prone to apoptosis. Therefore mitochondrial turnover is an integral aspect of quality control in which dysfunctional mitochondria are selectively eliminated through mitophagy. Currently, the progressive deterioration of physiological functions is seen as accumulation of modified/damaged proteins with limiting regenerative ability and disturbance of such affected protein-protein communication throughout aging in myocardial cells. Methodologies: For our study was used immunohistochemistry, biochemical methods: spectrophotometry, western blotting, immunodetection as well as more sophisticated 2D electrophoresis and mass spectrometry for evaluation protein-protein interactions and specific post-translational modification. Results and Discussion: Mitochondrial stress response to reactive species was evaluated as electron transport chain (ETC) complexes, redox-active molecules, and their possible communication. Protein-protein interactions revealed a strong linkage between age and ETC protein subunits. Redox state was strongly affected in senescent mitochondria with shift in favor of more pro-oxidizing condition within cardiomyocytes. Acute myocardial ischemia and ischemia-reperfusion (IR) injury affected ETC complexes I, II and IV with no change in complex III. Ischemia induced decrease in total antioxidant capacity, MnSOD, GSH and catalase activity with recovery in some extent during reperfusion. While MnSOD protein content was higher in IR group, activity returned to 95% of control. Nitric oxide is one of the biological molecules that can out compete MnSOD for superoxide and produce peroxynitrite. This process is faster than dismutation and led to the 10-fold higher production of nitrotyrosine after IR injury in adult with higher protection in senescent ones. 2D protein profiling revealed 140 mitochondrial proteins, 12 of them with significant changes after IR injury and 36 individual nitrotyrosine-modified proteins further identified by mass spectrometry. Linking these two groups, 5 proteins were altered after IR as well as nitrated, but only one showed massive nitration per lowering content of protein after IR injury in adult. Conclusions: Senescent cells have greater proportion of protein content, which might be modulated by several post-translational modifications. If these protein modifications are connected to functional consequences and protein-protein interactions are revealed, link may lead to the solution. Assume all together, dysfunctional proteostasis can play a causative role and restoration of protein homeostasis machinery is protective against aging and possibly age-related disorders. This work was supported by the project VEGA 1/0018/18 and by project 'Competence Center for Research and Development in the field of Diagnostics and Therapy of Oncological diseases', ITMS: 26220220153, co-financed from EU sources.

Keywords: aging heart, mitochondria, proteomics, redox state

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Authors: Hee Sun (Sunny) Choi, Gerhard Bruyns, Wang Zhang, Sky Cheng, Saijal Sharma

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This research addresses the need for a comprehensive framework that can guide the design and assessment of multi-level public spaces and public realms and their impact on the built environment. The study aims to understand and measure the neural mechanisms involved in this process. By doing so, it can lay the foundation for vertical and volumetric urbanism and ensure consistency and excellence in the field while also supporting scientific research methods for urban design with cognitive neuroscientists. To investigate these aspects, the paper focuses on the neighborhood scale in Hong Kong, specifically examining multi-level public spaces and quasi-public spaces within both commercial and residential complexes. The researchers use predictive Artificial Intelligence (AI) as a methodology to assess and comprehend the applicability of the urban design framework for vertical and volumetric urbanism. The findings aim to identify the factors that contribute to successful public spaces within a vertical living environment, thus introducing a new typology of public spaces.

Keywords: vertical urbanism, scientific research methods, spatial cognition, urban design guideline

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Authors: Igor N. Kosenko

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The present contribution is an analysis of more than 300 specimens of Upper Jurassic to Lower Cretaceous oysters collected by V.A. Zakharov during the 1960s and currently stored in the Trofimuk Institute of Geology and Geophysics SB RAS (Novosibirsk, Russia). They were sampled in the northwestern bounder of Western Siberia (Yatriya, Maurynia, Tol’ya and Lopsiya rivers) and the north of Eastern Siberia (Boyarka, Bolshaya Romanikha and Dyabaka-Tari rivers). During the last five years, they were examined with taxonomical and palaeoecological purposes. Based on carbonate material of oyster’s shells were performed isotopic analyses and associated palaeotemperatures. Taxonomical study consists on classical morphofunctional and biometrical analyses. It is completed by another large amount of Cretaceous oysters from Crimea as well as modern Pacific oyster - Crassostrea gigas. Those were studied to understand the range of modification variability between different species. Oysters previously identified as Liostrea are attributed now to four genera: Praeexogyra and Helvetostrea (Flemingostreidae), Pernostrea (Gryphaeidae) and one new genus (Gryphaeidae), including one species “Liostrea” roemeri (Quenstedt). This last is characterized by peculiar ethology, being attached to floating ammonites and morphology, outlined by a beak-shaped umbo on the right (!) valve. Endemic Siberian species from the Pernostrea genus have been included into the subgenus Boreiodeltoideum subgen. nov. Pernostrea and Deltoideum genera have been included into the tribe Pernostreini n. trib. from the Gryphaeinae subfamily. Model of phylogenetic relationships between species of this tribe has been proposed. Siberian oyster complexes were compared with complexes from Western Europe, Poland and East European Platform. In western Boreal and Subboreal Realm (England, northern France and Poland) two stages of oyster’s development were recognized: Jurassic-type and Cretaceous-type. In Siberia, Jurassic and Lower Cretaceous oysters formed a unique complex. It may be due to the isolation of the Siberian Basin toward the West during the Early Cretaceous. Seven oyster’s shells of Pernostrea (Pernostrea) uralensis (Zakharov) from the Jurassic/Cretaceous Boundary Interval (Upper Volgian – Lower Ryazanian) of Maurynia river were used to perform δ13C and δ18O isotopic analyses. The preservation of the carbonate material was controlled by: cathodoluminescence analyses; content of Fe, Mn, Sr; absence of correlation between δ13C and δ18O and content of Fe and Mn. The obtained δ13C and δ18O data were compared with isotopic data based on belemnites from the same stratigraphical interval of the same section and were used to trace palaeotemperatures. A general trend towards negative δ18O values is recorded in the Maurynia section, from the lower part of the Upper Volgian to the middle part of the Ryazanian Chetaites sibiricus ammonite zone. This trend was previously recorded in the Nordvik section. The higher palaeotemperatures (2°C in average) determined from oyster’s shells indicate that belemnites likely migrated laterally and lived part of their lives in cooler waters. This work financially supported by the Russian Foundation for Basic Researches (grant no. 16-35-00003).

Keywords: isotopes, oysters, Siberia, taxonomy

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Authors: Sucharat Limsitthichaikoon, Kedsarin Saodaeng, Aroonsri Priprem, Teerasak Damrongrungruang

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Complexation of anthocyanins to mimic natural copigmentation process was investigated. Cyanidin-rich extracts from Zea mays L. CeritinaKulesh. anddelphinidin-rich extracts from ClitoriaternateaL. were used to form 4 anthocyanin complexes, AC1, AC2, AC3, and AC4, in the presence of several polyphenols and a trace metal. Characterizations of the ACs were conducted by UV, FTIR, DSC/TGA and morphological observations. Bathochromic shifts of the UV spectra of 4 formulas of ACs were observed at peak wavelengths of about 510-620 nm by 10 nm suggesting complex formation.FTIR spectra of the ACs indicate shifts of peaks from 1,733 cm-1 to 1,696 cm-1 indicating interactions and a decrease in the peak areas within the wavenumber of 3,400-3,500 cm-1 indicating changes in hydrogen bonding.Thermal analysis of all of the ACs suggests increases in melting temperature after complexation. AC with the highest melting temperature was morphologically observed by SEM and TEM to be crystal-like particles within a range of 50 to 200 nm. Particle size analysis of the AC by laser diffraction gave a range of 50-600 nm, indicating aggregation. This AC was shown to have no cytotoxic effect on cultured HGEPp0.5 and HGF (all p> 0.05) by MTT. Therefore, complexation of anthocyanins was simple and self-assembly process, potentially resulting in nanosized particles of anthocyanin complex.

Keywords: anthocyanins, complexation, purple corn cops, butterfly pea, physicochemical characteristics, cytotoxicity

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Authors: Chuanxiang Cheng, Tiantian Min, Jin Yue

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Antimicrobial active packaging enables extensive biological effects to improve food safety. However, the efficacy of antimicrobial packaging hinges on factors including the diffusion rate of the active agent toward the food surface, the initial content in the antimicrobial agent, and the targeted food shelf life. Among the possibilities of antimicrobial packaging design, an interesting approach involves the incorporation of volatile antimicrobial agents into the packaging material. In this case, the necessity for direct contact between the active packaging material and the food surface is mitigated, as the antimicrobial agent exerts its action through the packaging headspace atmosphere towards the food surface. However, it still remains difficult to achieve controlled and precise release of bioactive compounds to the specific target location with required quantity in food packaging applications. Remarkably, the development of stimuli-responsive materials for electrospinning has introduced the possibility of achieving controlled release of active agents under specific conditions, thereby yielding enduring biological effects. Relative humidity (RH) for the storage of food categories such as meat and aquatic products typically exceeds 90%. Consequently, high RH can be used as an abiotic trigger for the release of active agents to prevent microbial growth. Hence, a novel RH - responsive polyvinyl alcohol/chitosan (PVA/CS) composite nanofibrous film incorporated with 4-terpineol/β-cyclodextrin inclusion complexes (4-TA@β-CD ICs) was engineered by electrospinning that can be deposited as a functional packaging materials. The characterization results showed the thermal stability of the films was enhanced after the incorporation due to the hydrogen bonds between ICs and polymers. Remarkably, the 4 wt% 4-TA@β-CD ICs/PVA/CS film exhibited enhanced crystallinity, moderate hydrophilic (Water contact angle of 81.53°), light barrier property (Transparency of 1.96%) and water resistance (Water vapor permeability of 3.17 g mm/m2 h kPa). Moreover, this film also showed optimized mechanical performance with a Young’s modulus of 11.33 MPa, a tensile strength of 19.99 MPa and an elongation at break of 4.44 %. Notably, the antioxidant and antibacterial properties of this packaging material were significantly improved. The film demonstrated the half-inhibitory concentrations (IC50) values of 87.74% and 85.11% for scavenging 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2, 2′-azinobis (3-ethylbenzothiazoline-6-sulfonic) (ABTS) free radicals, respectively, in addition to an inhibition efficiency of 65% against Shewanella putrefaciens, the characteristic bacteria in aquatic products. Most importantly, the film achieved controlled release of 4-TA under high 98% RH by inducing the plasticization of polymers caused by water molecules, swelling of polymer chains, and destruction of hydrogen bonds within the cyclodextrin inclusion complex. Consequently, low relative humidity is suitable for the preservation of nanofibrous film, while high humidity conditions typical in fresh food packaging environments effectively stimulated the release of active compounds in the film. This film with a long-term antimicrobial effect successfully extended the shelf life of Litopenaeus vannamei shrimp to 7 days at 4 °C. This attractive design could pave the way for the development of new food packaging materials.

Keywords: controlled release, electrospinning, nanofibrous film, relative humidity–responsive, shrimp preservation

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Authors: S. Forel, F. Bouanis, L. Catala, I. Florea, V. Huc, F. Fossard, A. Loiseau, C. Cojocaru

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Single wall carbon nanotubes are seen as excellent candidate for application on nanoelectronic devices because of their remarkable electronic and mechanical properties. These unique properties are highly dependent on their chiral structures and the diameter. Therefore, structure controlled growth of SWNTs, especially directly on final device’s substrate surface, are highly desired for the fabrication of SWNT-based electronics. In this work, we present a new approach to control the diameter of SWNTs and eventually their chirality. Because of their potential to control the SWNT’s chirality, bi-metalics nanoparticles are used to prepare alloy nanoclusters with specific structure. The catalyst nanoparticles are pre-formed following a previously described process. Briefly, the oxide surface is first covered with a SAM (self-assembled monolayer) of a pyridine-functionalized silane. Then, bi-metallic (Fe-Ru, Co-Ru and Ni-Ru) complexes are assembled by coordination bonds on the pre-formed organic SAM. The resultant alloy nanoclusters were then used to catalyze SWNTs growth on SiO2/Si substrates via CH4/H2 double hot-filament chemical vapor deposition (d-HFCVD). The microscopy and spectroscopy analysis demonstrate the high quality of SWNTs that were furthermore integrated into high-quality SWNT-FET.

Keywords: nanotube, CVD, device, transistor

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Authors: Farideh Azimi, Sam Vahedi Tafreshi

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This research tries to study the residential buildings in Ahvaz, the common materials used, and the impact of passive methods of energy storage (as one of the most effective ways to reduce energy consumption in residential complexes) in order to achieve patterns for construction of residential buildings in Ahvaz conditions to reduce energy consumption. In this research, after studying Ahvaz conditions, the components of an existing building were simulated in Energy Plus software, and the climatic data of Ahvaz station was introduced to software. Then to achieve the most optimal conditions of energy consumption in Ahvaz conditions, each of the residential building elements was optimized. The results of simulation showed that using inactive materials and design including double glass, outside wall insulation, inverted roof, etc. in the buildings can reduce energy consumption in the hot and dry climate of Ahvaz. Among the parameters investigated, the inverted roof was the most effective energy saving pattern. According to the results of simulation of the entire building with the most optimal parameters, energy consumption can be saved by a mean of 12.51% in buildings of Ahvaz, and the obtained pattern can also be used in similar climates.

Keywords: residential buildings, thermal comfort, energy storage, Energy Plus software, Ahvaz

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Authors: hassan gheisari

Abstract:

Ferro silicate calcium nano particles are prepared through the sol-gel method using polyvinyl alcohol (PVA) as a chelating agent. The powder, as prepared, is annealed at three different temperatures (900 ºC, 1000 ºC, and 1100 ºC) for 3 h. The XRD patterns of the samples indicate broad peaks, and the full width at half maximum decreased with increasing annealing temperature. FTIR spectra of the samples confirm the presence of metal - oxygen complexes within the structure. The average particle size obtained from PSA curve demonstrates ultrafine particles. SEM micrographs indicate the particles synthesized have spherical morphology. The saturation magnetization (Ms) and remnant magnetization (Mr) of the samples show dependence on particle size and crystallinity of the samples. The highest saturation magnetization is achieved for the sample annealed at 1100 ºC having maximum average particle size. The high saturation magnetization of the samples suggests the present method is suitable for obtaining nano particles magnetic ferro bioceramic, which is desirable for practical applications such as hyperthermia bone cancer therapy.

Keywords: hyperthermia, bone cancer, bio ceramic; magnetic materials; sol– gel, silicate calcium

Procedia PDF Downloads 46

Authors: Hassan Gheisari

Abstract:

Ferro silicate calcium nano particles are prepared through the sol-gel method using polyvinyl alcohol (PVA) as a chelating agent. The powder as prepared is annealed at three different temperatures (900 ºC, 1000 ºC and 1100 ºC) for 3 h. The XRD patterns of the samples indicate broad peaks and the full width at half maximum decreased with increasing annealing temperature. FTIR spectra of the samples confirm the presence of metal - oxygen complexes within the structure. The average particle size obtained from PSA curve demonstrates ultrafine particles. SEM micrographs indicate the particles synthesized have spherical morphology. The saturation magnetization (Ms) and remnant magnetization (Mr) of the samples show dependence on particle size and crystallinity of the samples. The highest saturation magnetization is achieved for the sample annealed at 1100 ºC having maximum average particle size. The high saturation magnetization of the samples suggests the present method is suitable for obtaining nano particles magnetic ferro bioceramic which is desirable for practical applications such as hyperthermia bone cancer therapy.

Keywords: hyperthermia, bone cancer, bio ceramic, magnetic materials, sol– gel, silicate calcium

Procedia PDF Downloads 285

Authors: Anupama Sekhar, Preeti Saryan, Vinita Gowda

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Plants, due to their sedentary lifestyle, have evolved mechanisms to synthesize a huge diversity of complex, specialized chemical metabolites, a majority of them being volatile organic compounds (VOCs). These VOCs are heavily involved in their biotic and abiotic interactions. Since chemical composition could be under the same selection processes as other morphological characters, we test if VOCs can be used to taxonomically distinguish species in the well-studied, fragrant ginger genus -Hedychium (Zingiberaceae). We propose that variations in the volatile profiles are suggestive of adaptation to divergent environments, and their presence could be explained by either phylogenetic conservatism or ecological factors. In this study, we investigate the volatile chemistry within Hedychium, which is endemic to Asian palaeotropics. We used an unsupervised clustering approach which clearly distinguished most taxa, and we used ancestral state reconstruction to estimate phylogenetic signals and chemical trait evolution in the genus. We propose that taxonomically, the chemical composition could aid in species identification, especially in species complexes where taxa are not morphologically distinguishable, and extensive, targeted chemical libraries will help in this effort.

Keywords: chemotaxonomy, dynamic headspace sampling, floral fragrance, floral volatile evolution, gingers, Hedychium

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Authors: N. Belhadj, M. Hadj Youcef, T. Benabdallah, Belbachir Ibtissem, N. Boceiri

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This work deals with the synthesis, the structural elucidation and the exploration the extracting properties of a series of ortho-hydroxy Schiff base in sulfate medium. After the synthesis and characterization of their structures, the study of their behavior in solution was carried out by pH-metric titration in different media homogeneous and heterogeneous solution. This allowed to explore and to quantify in each of these media, some of their properties in solution such as, their acid-base behavior (determination and comparison of pKa), their distribution powers (determination and comparison of logKd), and their thermodynamic constants (determining ∆H°, ΔS° and ∆G°moy) by optimizing both the temperature and ionic strength. Study of the extraction of nickel (II) and cobalt(II) separately was undertaken in the aqueous-organic system, chloroform-water. Different extraction parameters have been thus optimized such, the pH, the concentration of extractant and the ionic strength, and the extraction constants established in each case. The extracted metal complexes have been isolated and their spatial configurations elucidated. The selective extraction of the couple cobalt (II)/nickel (II) was finally performed by our series of Schiff base in the chloroforme/water.

Keywords: selective extraction, Schiff base, distribution, cobalt(II), nickel(II)

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Authors: Lukas Stiburek, Jana Cesnekova, Josef Houstek, Jiri Zeman

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Cellular function depends on mitochondrial function and integrity that is therefore maintained by several classes of proteins possessing chaperone and/or proteolytic activities. In this work, we focused on characterization of LACE1 (lactation elevated 1) function in mitochondrial protein homeostasis maintenance. LACE1 is the human homologue of yeast mitochondrial Afg1 ATPase, a member of SEC18-NSF, PAS1, CDC48-VCP, TBP family. Yeast Afg1 was shown to be involved in mitochondrial complex IV biogenesis, and based on its similarity with CDC48 (p97/VCP) it was suggested to facilitate extraction of polytopic membrane proteins. Here we show that LACE1, which is a mitochondrial integral membrane protein, exists as part of three complexes of approx. 140, 400 and 500 kDa and is essential for maintenance of fused mitochondrial reticulum and lamellar cristae morphology. Using affinity purification of LACE1-FLAG expressed in LACE1 knockdown background we show that the protein physically interacts with mitochondrial inner membrane protease YME1L. We further show that human LACE1 exhibits significant pro-apoptotic activity and that the protein is required for normal function of the mitochondrial respiratory chain. Thus, our work establishes LACE1 as a novel factor with the crucial role in mitochondrial homeostasis maintenance.

Keywords: LACE1, mitochondria, apoptosis, protease

Procedia PDF Downloads 281

Authors: Maryam Mirabediny, Tsz Tin Yu, Jun Sun, Matthew Lee, Denis M. O’Carroll, Michael J. Manefield, Björn Akermark, Biswanath Das, Naresh Kumar

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Branched perfluorooctane sulfonic acid (PFOS) is recognized as a threatening environmental pollutant due to its high persistence and bioaccumulation in various environmental matrices as well as for its toxic effects on humans and wildlife, even at very low concentrations. This study reports the first investigation of branched PFOS defluorination catalyzed by metal phthalocyanines. The reaction conditions were optimized using the different reductants and temperatures. Cobalt phthalocyanine, when combined with Ti citrate as a reducing agent, was able to defluorinate 10.9% of technical PFOS within 8 hours. In contrast, vitamin B12 only showed 2.4% defluorination during the same period under similar conditions. The defluorination mediated by cobalt phthalocyanine and Ti citrate system corresponds to 54.5% of all branched PFOS isomers (br-PFOS isomers). Isomer-specific degradation was also investigated via high-resolution LC-orbitrap, followed by their relative rates. The difference in catalytic efficacy of various phthalocyanine complexes is rationalized by their structures and electrochemical response. Lastly, a new defluorination mechanism is proposed based on the newly detected degradation products after the phthalocyanines treatment and the previous studies.

Keywords: branched isomers, catalyst, reductive defluorination, water remediation

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Authors: M. Bouhoun Ali, A. Y. Badjah Hadj Ahmed, M. Attou, A. Elias, M. A. Didi

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The extraction of uranium(VI) from aqueous solutions has been investigated using 1-hydroxyhexadecylidene-1,1-diphosphonic acid (HHDPA) and 1-hydroxydodecylidene-1,1-diphosphonic acid (HDDPA), which were synthesized and characterized by elemental analysis and by FT-IR, 1H NMR, 31P NMR spectroscopy. In this paper, we propose a tentative assignment for the shifts of those two ligands and their specific complexes with uranium(VI). We carried out the extraction of uranium(VI) by HHDPA and HDDPA from [carbon tetrachloride + 2-octanol (v/v: 90%/10%)] solutions. Various factors such as contact time, pH, organic/aqueous phase ratio and extractant concentration were considered. The optimum conditions obtained were: contact time= 20 min, organic/aqueous phase ratio = 1, pH value = 3.0 and extractant concentration = 0.3M. The extraction yields are more significant in the case of the HHDPA which is equipped with a hydrocarbon chain, longer than that of the HDDPA. Logarithmic plots of the uranium(VI) distribution ratio vs. pHeq and the extractant concentration showed that the ratio of extractant to extracted uranium(VI) (ligand/metal) is 2:1. The formula of the complex of uranium(VI) with the HHDPA and the DHDPA is UO2(H3L)2 (HHDPA and DHDPA are denoted as H4L). A spectroscopic analysis has showed that coordination of uranium(VI) takes place via oxygen atoms.

Keywords: liquid-liquid extraction, uranium(vi), 1-hydroxyalkylidene-1, 1-diphosphonic acids, hhdpa, hddpa, aqueous solution

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Authors: M. S. Mrudula, M. R. Gopinathan Nair

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In order to utilize the natural rubber for developing new green polymeric materials for specialty applications, we have prepared natural rubber and polyethylene oxide based polymeric networks by two shot method. The polymeric networks thus formed have been used as chelating exchanger for metal ion binding. Chelating exchangers are, in general, coordinating copolymers containing one or more electron donor atoms such as N, S, O, and P that can form coordinate bonds with metals. Hydrogels are water- swollen network of hydrophilic homopolymer or copolymers. They acquire a great interest due to the facility of the incorporation of different chelating groups into the polymeric networks. Such polymeric hydrogels are promising materials in the field of hydrometallurgical applications and water purification due to their chemical stability. The current study discusses the swelling response of the polymeric networks as a function of time, temperature, pH and [NaCl] and sorption studies. Equilibrium swelling has been observed to depend on both structural aspects of the polymers and environmental factors. Metal ion sorption shows that these polymeric networks can be used for removal, separation, and enrichment of metal ions from aqueous solutions and can play an important role for environmental remediation of municipal and industrial wastewater.

Keywords: block copolymer, adsorption, chelating exchanger, swelling study, polymer, metal complexes

Procedia PDF Downloads 312

Authors: I. Nazari, B. Shaabani, P. Abaasifar

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In small quantities certain heavy metals are nutritionally essential for a healthy life. The heavy metals linked most often to human poisoning are lead, mercury, arsenic, and cadmium. Other heavy metals including copper, zinc and chromium are actually required by the body in small quantity but can also be toxic in large doses. Nowadays, we have contamination to this heavy metals in some untreated industrial waste waters and even in several populated cities drinking waters around the world. The contamination of ground and underground water sources to heavy metals can be concentrated and travel up to food chain by drinking water and agricultural products. In recent years, the need for safe and economical methods for removal of heavy metals from contaminated water has necessitated research interest towards the finding low-cost alternatives. Bio-adsorbents have emerged as low-cost and efficient materials for the removal of heavy metals from waste and ground waters. The bio-adsorbents have an affinity for heavy metals ions to form metal complexes or chelates due to having functional groups including carboxyl, hydroxyl, imidazole, and etc. The objective of this study is to review researches in less expensive adsorbents and their utilization possibilities for various low-cost bio-adsorbents such as coffee beans, rice husk, and saw dust for the removal of heavy metals from contaminated waters.

Keywords: heavy metals, water pollution, bio-adsorbents, low cost adsorbents

Procedia PDF Downloads 326

Authors: Andrea Dragu, Solen Kinayyigit, Valerie Colliere, Karin Karin Philippot, Camelia Bala, Vasile I. Parvulescu

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The production of transportation fuels from biomass has gained a growing attention due to diminishing fossil fuel reserves, rising petroleum prices and increasing concern about global warming. In recent years, renewable hydrocarbons that are completely fungible with fossil fuels have been suggested to be efficiently produced by catalytic deoxygenation of fatty acids and their derivatives viadecarboxylation / decarbonylation. Several triglycerides (tall oil fatty acids) and saturated/unsaturated fatty acids and their corresponding esters were used as feedstocks. Their impact together with the influence of the reaction conditions and the catalyst composition on the nature of the reaction pathways of the deoxygenation of vegetable oils and their derivatives were recently reviewed. Following this state of the art the aim of the present study was the investigation of Pd NPs deposited onto mesoporous carbon supports as active and stable catalysts for the deoxygenation of oleic acid. The catalysts were prepared by the deposition of Pd NPs synthesised following an organometallic route on mesoporous carbons with different characteristics. Experiments were carried out under both batch and flow conditions. They demonstrated that under batch conditions (200 atm; 573K), the extent of the reaction depended, firstly, on the Pd loading and then on the metal dispersion and the oxidation state of palladium, both influenced by the way the support has been treated before the NPs deposition and by the preparation/stabilization methodology of Pd NPs. No aromatic compounds were detected in the reaction products but octadecanol and octadecane were observed in large extents. Under flow conditions (4 atm; 573 K), the conversion of stearic acid was superior to that observed in batch conditions. The product mixture contained over 20% heptadecane. No octadecanol, octadecane, and aromatic compounds were detected. The maxima in performances are obtained after only 0.5 h. After that, the yields in heptadecane suffer from a severe decrease until 3h reaction time. However, at that time, stopping feeding the reactor with oleic acid and flushing the catalyst only with mesitylene recovered the activity and the selectivity of the catalysts. With the complete removal of H2, the analysis revealed the presence of heptadecene in high excess compared to heptadecane (almost 7 to 1), thus suggesting decarbonylation as the main route. ICP-OES measurements indicated no leaching of palladium and simple washing of catalysts with mesitylene allowed recycling without any change in conversion or product distribution. Noteworthy, mesitylene as solvent exhibited no effect in this reaction. In conclusion, this study demonstrates the feasibility of such catalysts for the green production of fuels from biomass.

Keywords: fuels from biomass, green catalyst, Pd nano-particles , recycble catalyst

Procedia PDF Downloads 279

Authors: Elias Akoury

Abstract:

Nuclear Magnetic Resonance (NMR) spectroscopy is an indispensable technique used in structure determination of small and macromolecules to study their physical properties, elucidation of characteristic interactions, dynamics and thermodynamic processes. Quantum mechanics defines the theoretical description of NMR spectroscopy and treatment of the dynamics of nuclear spin systems. The phenomenon of residual dipolar coupling (RDCs) has become a routine tool for accurate structure determination by providing global orientation information of magnetic dipole-dipole interaction vectors within a common reference frame. This offers accessibility of distance-independent angular information and insights to local relaxation. The measurement of RDCs requires an anisotropic orientation medium for the molecules to partially align along the magnetic field. This can be achieved by introduction of liquid crystals or attaching a paramagnetic center. Although anisotropic paramagnetic tags continue to mark achievements in the biomolecular NMR of large proteins, its application in small organic molecules remains unspread. Here, we propose a strategy for the synthesis of a lanthanide tag and the measurement of RDCs in organic molecules using paramagnetic lanthanide complexes.

Keywords: lanthanide tags, NMR spectroscopy, residual dipolar coupling, quantum mechanics of spin dynamics

Procedia PDF Downloads 157