Search results for: chiral amines

Authors: Littlelet N. Scarlet, Kamaluddin Abdur-Rashid, Paul T. Maragh, Tara Dasgupta

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Aminophosphines are a privileged class of ancillary ligands with emerging importance in homogeneous catalysis. The unique combination of soft phosphorus (P) and hard nitrogen (N) centres affords a variety of transition metal complexes as potential pre-catalysts for synthetically useful reactions. Herein three ligand systems will be reported; two bidentate ligands - (S)-8-(diphenyl-phosphino)-1,2,3,4-tetrahydronaphthalen-1-amine, (S)THNANH2, and (Rc)-1-((Sp)-2-diphenylphosphino) ferrocenylethylamine, (RcSp)PPFNH2 - and a tridentate (Rc)-1-((Sp)-2-diphenylphosphino) ferrocenylimino-pyridine, (RcSp)PPFNNH2 ligand; the latter prepared from the condensation of selected ferrocene aminophosphines with pyridine-2-carboxaldehyde. Suitable combinations of these aminophosphine ligands with ruthenium precursors have afforded highly efficient systems for the asymmetric hydrogenation and transfer hydrogenation of selected ketones in 2-propanol. The Ru-(S)THNANH2 precatalyst was the most efficient in the asymmetric hydrogenation of selected ketones with 100% conversions within 4 hours at a catalyst loading of 0.1 mol%. The Ru-(RcSp)PPFNNH2 precatalyst was the most efficient in the asymmetric transfer hydrogenation of the ketones with conversions as high as 98% with 0.1 mol% catalyst. However, the enantioselectivities were generally low.

Keywords: aminophosphine, asymmetric hydrogenation, homogeneous catalysis, ruthenium (II), transfer hydrogenation

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Authors: Z. Miao, Y. Chu, Y. Zhang

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The unique cholesteric phase liquid crystals obtained by mixing nematic liquid crystals with chiral dopants have gained valuable applications in the display field for their selective reflection and circular dichroism properties. The periodic arrangement of the helical structure of cholesteric liquid crystals makes it possible to produce Bragg reflection of circularly polarized light irradiated perpendicularly to the liquid crystals and, therefore, to acquire semi- or fully reflective surfaces or films. If the polymer-liquid crystal composites are combined with polymeric monomers, commercialized reflective broadband films can be fabricated. In this study, the polymer-liquid crystal composites reflecting visible light region (wavelength centered at 550 nm) were studied to analyze the effects of AC electric field at different voltages and frequencies on the optical texture of the composites, as well as the effects of polymerization temperature and ultraviolet (UV) intensity on the polymerization reaction and reflection bandwidth. The optimal sample was finally obtained at 100Hz, 120V, 30℃, 1.00 mW/cm², which provides a research suggestion to solve the influencing factors of visible light reflection bandwidths.

Keywords: cholesteric liquid crystal, reflection bandwidths, negative dielectric anisotropy, planar texture

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Authors: Isam M. Arafa, Mazin Y. Shatnawi, Yaser A. Yousef, Batool Zaid Al-Momani

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The present work describes the preparation, characterization, and luminescence of a series of fluorenone (FL) based luminophores grafted onto modified cellulose microfibers. The FL is condensed onto cellulose aldehyde using three diamine spacers (H₂N-NH₂, H₂N(CH₂)₂NH₂ and H₂N(CH₂)₃NH₂) to afford Cell=Spacer=FL. The obtained products were characterized by spectroscopic (FT-IR, UV–Vis), thermal gravimetric analysis (TGA), and microscopic (Optical, SEM) techniques. The UV-Vis spectra of the FL=N(CH₂)ₓNH₂ (x = 0, 2, 3) moieties show that they are transparent in the 375- 800 nm region while they exhibit intense absorption band below 350 nm attributed to n-π* and π-π* transitions. The solid-state photoluminescence (PLs-s) of the cold-pressed pellets of the FL=N(CH₂)ₓNH₂ and Cell=Spacer=FL placed in a quartz cuvette show strong emission in the 500-550 nm region upon irradiation with Xe lamp light (λex = 320 nm). The PLs-s green emission of the grafted Cell=Spacer=FL was evaluated relative to that of the FL-based precursor. These grafted conjugated products have the potential to be used as analyte sensors for typical nitroaromatics/aromatic amines and be further extended to immunoassay studies for aromatic amino acids such as phenylalanine and histidine.

Keywords: luminescence, cellulose, fluorenone, grafting, solid state

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Authors: Amanda C. Evans

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Enabling technologies such as continuous processing (CP) approaches can provide the tools needed to control and manipulate reactivities and transform chemical reactions into micro-controlled in-flow processes. Traditional synthetic approaches can be radically transformed by the application of CP, facilitating the pairing of chemical methodologies with technologies from other disciplines. CP supports sustainable processes that controllably generate reaction specificity utilizing supramolecular interactions. Continuous photochemical processing is an emerging field of investigation. The use of light to drive chemical reactivity is not novel, but the controlled use of specific and tunable wavelengths of light to selectively generate molecular structure under continuous processing conditions is an innovative approach towards chemical synthesis. This investigation focuses on the use of circularly polarized (cp) light as a sustainable catalyst for the CP generation of asymmetric molecules. Chiral photolysis has already been achieved under batch, solid-phase conditions: using synchrotron-sourced cp light, asymmetric photolytic selectivities of up to 4.2% enantiomeric excess (e.e.) have been reported. In order to determine the optimal wavelengths to use for irradiation with cp light for any given molecular building block, CD and anisotropy spectra for each building block of interest have been generated in two different solvents (water, hexafluoroisopropanol) across a range of wavelengths (130-400 nm). These spectra are being used to support a series of CP experiments using cp light to generate enantioselectivity.

Keywords: anisotropy, asymmetry, flow chemistry, active pharmaceutical ingredients

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Authors: Szymon Kugler, Krzysztof Kowalczyk, Tadeusz Spychaj

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An addition of carbon nanotubes (CNT) can simultaneously improve many features of epoxy coatings, i.e. electrical, mechanical, functional and thermal. Unfortunately, this nanofiller negatively affects visual properties of the coatings, such as transparency and gloss. The main reason for the low visual performance of CNT-modified epoxy coatings is the lack of compatibility between CNT and popular amine curing agents, although epoxy resins based on bisphenol A are indisputable good CNT dispersants. This is a serious obstacle in utilization of the coatings in advanced applications, demanding both high transparency and electrical conductivity. The aim of performed investigations was to find amine curing agents exhibiting affinity for CNT, and ensuring good performance of epoxy coatings with them. Commercially available CNT was dispersed in epoxy resin, as well as in different aliphatic, cycloaliphatic and aromatic amines, using one of two dispergation methods: ultrasonic or mechanical. The CNT dispersions were subsequently used in the preparation of epoxy coating compositions and coatings on a transparent substrate. It was found that amine derivative of bio-based cardanol, as well as modified o-tolylbiguanide exhibit significant CNT, dispersing properties, resulting in improved transparent/electroconductive performance of epoxy coatings. In one of prepared coating systems just 0.025 wt.% (250 ppm) of CNT was enough to obtain coatings with semi conductive properties, 83% of transparency as well as perfect chemical resistance to methyl-ethyl ketone and improved thermal stability. Additionally, a theory of the influence of amine chemical structure on CNT dispersing properties was proposed.

Keywords: bio-based cardanol, carbon nanotubes, epoxy coatings, tolylbiguanide

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Authors: Baki Cicek, Umit Calisir

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Carbazoles have been replaced lots of studies from 1960's to present and also still continues. In 1987, the first diode device had been developed. Thanks to that study, light emitting devices have been investigated and developed and also have been used on commercial applications. Nowadays, OLED (Organic Light Emitting Diodes) technology is using on lots of electronic screen such as (mobile phone, computer monitors, televisions, etc.) Carbazoles were subject a lot of study as a semiconductor material. Although this technology is used commen and widely, it is still development stage. Metal complexes of these compounds are using at pigment dyes because of colored substances, polymer technology, medicine industry, agriculture area, preparing rocket fuel-oil, determine some of biological events, etc. Becides all of these to preparing of schiff base synthesis is going on intensely. In this study, some of novel carbazole schiff bases were synthesized starting from carbazole. For that purpose, firstly, carbazole was alkylated. After purification of N-substituted-carbazole was nitrated to sythesized 3-nitro-N-substituted and 3,6-dinitro-N-substituted carbazoles. At next step, nitro group/groups were reduced to amines. Purified with using a type of silica gel-column chromatography. At the last step of our study, with sythesized 3,6-diamino-N-substituted carbazoles and 3-amino-N-substituted carbazoles were reacted with aldehydes to condensation reactions. 3-(imino-p-hydroxybenzyl)-N-isobutyl -carbazole, 3-(imino-2,3,4-trimethoxybenzene)-N-butylcarbazole, 3-(imino-3,4-dihydroxybenzene)-N-octylcarbazole, 3-(imino-2,3-dihydroxybenzene)-N-octylkarbazole and 3,6-di(α-imino-β-naphthol) -N-hexylcarbazole compounds were synthesized. All of synthesized compounds were characterized with FT-IR, 1H-NMR, 13C-NMR, and LC-MS.

Keywords: carbazole, carbazol schiff base, condensation reactions, OLED

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Authors: Devadrita Dey Sarkar

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Oxidosqualene cyclase is a membrane bound enzyme in which helps in the formation of steroid scaffold in higher organisms. In a highly selective cyclization reaction oxidosqualene cyclase forms LANOSTEROL with seven chiral centres starting from the linear substrate 2,3-oxidosqualene. In humans OSC in cholesterol biosynthesis it represents a target for the discovery of novel anticholesteraemic drugs that could complement the widely used statins. The enzyme oxidosqualene: lanosterol cyclase (OSC) represents a novel target for the treatment of hypercholesterolemia. OSC catalyzes the cyclization of the linear 2,3-monoepoxysqualene to lanosterol, the initial four-ringed sterol intermediate in the cholesterol biosynthetic pathway. OSC also catalyzes the formation of 24(S), 25-epoxycholesterol, a ligand activator of the liver X receptor. Inhibition of OSC reduces cholesterol biosynthesis and selectively enhances 24(S),25-epoxycholesterol synthesis. Through this dual mechanism, OSC inhibition decreases plasma levels of low-density lipoprotein (LDL)-cholesterol and prevents cholesterol deposition within macrophages. The recent crystallization of OSC identifies the mechanism of action for this complex enzyme, setting the stage for the design of OSC inhibitors with improved pharmacological properties for cholesterol lowering and treatment of atherosclerosis. While studying and designing the inhibitor of oxidosqulene cyclase, I worked on the pdb id of 1w6k which was the most worked on pdb id and I used several methods, techniques and softwares to identify and validate the top most molecules which could be acting as an inhibitor for oxidosqualene cyclase. Thus, by partial blockage of this enzyme, both an inhibition of lanosterol and subsequently cholesterol formation as well as a concomitant effect on HMG-CoA reductase can be achieved. Both effects complement each other and lead to an effective control of cholesterol biosynthesis. It is therefore concluded that 2,3-oxidosqualene cyclase plays a crucial role in the regulation of intracellular cholesterol homeostasis. 2,3-Oxidosqualene cyclase inhibitors offer an attractive approach for novel lipid-lowering agents.

Keywords: anticholesteraemic, crystallization, statins, homeostasis

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Authors: Anita K. Kovacs, Peter Hegyes, Zsolt Bozso, Gabor Toth

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Fluorination has been used extensively by the pharmaceutical industry as a strategy to improve the pharmacokinetics of drugs due to its effectiveness in increasing the potency of antimicrobial peptides (AMPs). Multiple-fluorinated indole-ring-containing tryptophan derivatives have the potential of having better antimicrobial activity than the widely used mono-fluorinated indole-ring containing tryptophan derivatives, but they are not available commercially. Therefore, our goal is to synthesize multiple-fluorinated indole-ring containing tryptophan derivatives to incorporate them into AMPs to enhance their antimicrobial activity. During our work, we are trying several methods (classical organic synthesis, enzymic synthesis, and solid phase peptide synthesis) for the synthesis of the said compounds, with mixed results. With classical organic synthesis (four different routes), we did not get the desired results. The reaction of serin with substituted indole in the presence of acetic anhydride led to racemic tryptophane; with the reaction of protected serin with indole in the presence of nickel complex was unsuccessful; the reaction of serin containing protected dipeptide with disuccinimidyl carbonate we achieved a tryptophane containing dipeptide, its chiral purity is being examined; the reaction of alcohol with substituted indole in the presence of copper complex was successful, but it was only a test reaction, we could not reproduce the same result with serine. The undergoing tryptophan-synthase method has shown some potential, but our work has not been finished yet. The successful synthesis of the desired multiple-fluorinated indole-ring-containing tryptophan will be followed by solid phase peptide synthesis in order to incorporate it into AMPs to enhance their antimicrobial activity. The successful completion of these phases will mean the possibility of manufacturing new, effective AMPs.

Keywords: halogenation, fluorination, tryptophan, enhancement of antimicrobial activity

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Authors: G. De Matteis, L. Martina, V. Turco

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The work is focused on determining and comparing special nonlinear static configurations in cholesteric liquid crystals (CLCs), confined between two parallel plates and in the presence of an external static electric/magnetic field. The solutions are stabilised by topological and non-topological conservation laws since they are described in terms of integrable or partially integrable nonlinear boundary value problems. In cholesteric liquid crystals which are subject to geometric frustration; anchoring conditions at boundaries, i.e., homeotropic conditions, are incompatible with the cholesteric twist. This aspect turns out to be essential in the admissible classes of solutions, allowing also for disclination type singularities. Within the framework of Frank-Oseen theory, we study the static configurations for CLCs. First, we find numerical solutions for isolated axisymmetric states in confined CLCs with weak homeotropic anchoring at the boundaries. These solutions describe 3-dimensional modulations, namely spherulites or cholesteric bubbles, actually observed in these systems, of standard baby skyrmions. Relations with well-known nonlinear integrable systems are found and are used to explore the asymptotic behavior of the solutions. Then we turn our attention to extended periodic static configurations called Helicoids or cholesteric fingers, described by an elliptic sine-Gordon model with appropriate boundary conditions, showing how their period and energies are determined by both the thickness of the cell and the intensity of the external electric/magnetic field. We explicitly show that helicoids with π or 2π of rotations of the molecular director are different in many aspects and are not simply algebraically related. The behaviour of the solutions, their energy and the properties of the associated disclinations are discussed in detail, both analytically and numerically.

Keywords: cholesteric liquid crystals, geometric frustration, helicoids, skyrmions

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Authors: G. A. Ravishankar, A. Ramakrishna

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Melatonin (MEL) and Serotonin (SER), also known as [5-Hydroxytryptamine (5-HT)] are reported to be in a range of plant types which are edible. Their occurrence in plants species appears to be ubiquitous. Their presence in high quantities in plants assumes significance owing to their physiological effects upon consumption by human beings. MEL is a well known animal hormone mainly released by the pineal gland known to influence circadian rhythm, sleep, apart from immune enhancement. Similarly, SER is a neurotransmitter that regulates mood, sleep and anxiety in mammals. It is implicated in memory, behavioral changes, scavenging reactive oxygen species, antipsychotic, etc. Similarly Role of SER and MEL in plant morphogenesis, and various physiological processes through intense research is beginning to unfold. These molecules are in common foods viz banana, pineapple, plum, nuts, milk, grape wine. N- Feruloyl serotonin and p-coumaroyl serotonin found in certain seeds are found to possess antioxidant, anti-inflammatory, antitumor, antibacterial, and anti-stress potential apart from reducing depression and anxiety. MEL is found in Mediterranean diets, nuts, cherries, tomato berries, and olive products. Consumption of foods rich in MEL is known to increase blood MEL levels which have been implicated in protective effect against cardiovascular damage, cancer initiation and growth. MEL is also found in wines, green tea, beer, olive oil etc. Moreover, presence of SER and MEL in Coffee beans (green and roasted beans) and decoction has been reported us. In this communication we report the occurrence of indole amines in edible plants and their implications in human health.

Keywords: serotonin, melatonin, edible plants, neurotransmitters, physiological effects

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Authors: J. E. O. Hernandez

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In the next 20 years, energy production by burning fuels will increase and so will the atmospheric concentration of CO2 and its well-known threats to life on Earth. The technologies available for capturing CO2 are still dubious and this keeps fostering an interest in bio-inspired approaches. The leading one is the application of carbonic anhydrase (CA) –a superfast biocatalyst able to convert up to one million molecules of CO2 into carbonates in water. However, natural CA underperforms when applied to real smoky CO2 in chimneys and, so far, the efforts to create superior CAs in the lab rely on screening methods running under pristine conditions at the micro level, which are far from resembling those in chimneys. For the evolution of man-made enzymes, selection rather than screening would be ideal but this is challenging because of the need for a suitable artificial environment that is also sustainable for our society. Herein we present the stepwise design and construction of a bioprocess (from bench-scale to semi-pilot) for evolutionary selection experiments. In this bioprocess, reaction and adsorption took place simultaneously at atmospheric pressure in a spray tower. The scrubbing solution was fed countercurrently by reusing municipal pressure and it was mainly prepared with water, carbonic anhydrase and calcium chloride. This bioprocess allowed for the enzymatic carbonation of smoky CO2; the reuse of process water and the recovery of solid carbonates without cooling of smoke, pretreatments, solvent amines and compression of CO2. The average yield of solid carbonates was 0.54 g min-1 or 12-fold the amount produced in serum bottles at lab bench scale. This bioprocess could be used as a tailor-made environment for driving the selection of superior CAs. The bioprocess and its match CA could be sustainably used to reduce global warming by CO2 emissions from exhausts.

Keywords: biological carbon capture and sequestration, carbonic anhydrase, directed evolution, global warming

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Authors: Omoruyi Gold Idemudia, Alexander P. Sadimenko

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The synthesis of N-heterocycles with novel properties, having broad spectrum biological activities that may become alternative medicinal drugs, have been attracting a lot of research attention due to the emergence of medicinal drug’s limitations such as disease resistance and their toxicity effects among others. Acylpyrazolones have been employed as pharmaceuticals as well as analytical reagent and their application as coordination complexes with transition metal ions have been well established. By way of a condensation reaction with amines acylpyrazolone ketones form a more chelating and superior group of compounds known as azomethines. 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one was reacted with phenylhydrazine to get a new phenylhydrazone which was further reacted with aqueous solutions of palladium and platinum salts, in an effort towards the discovery of transition metal based synthetic drugs. The compounds were characterized by means of analytical, spectroscopic, thermogravimetric analysis TGA, as well as x-ray crystallography. 4-propyl-3-methyl-1-phenyl-2-pyrazolin-5-one phenylhydrazone crystallizes in a triclinic crystal system with a P-1 (No. 2) space group based on x-ray crystallography. The bidentate ON ligand formed a square planar geometry on coordinating with metal ions based on FTIR, electronic and NMR spectra as well as magnetic moments. Reported compounds showed antibacterial activities against the nominated bacterial isolates using the disc diffusion technique at 20 mg/ml in triplicates. The metal complexes exhibited a better antibacterial activity with platinum complex having an MIC value of 0.63 mg/ml. Similarly, ligand and complexes also showed antioxidant scavenging properties against 2, 2-diphenyl-1-picrylhydrazyl DPPH radical at 0.5mg/ml relative to ascorbic acid (standard drug).

Keywords: acylpyrazolone, antibacterial studies, metal complexes, phenylhydrazone, spectroscopy

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Authors: Adrien Cornille, Sylvain Caillol, Bernard Boutevon

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The development of polyurethanes began in 1937 at I. G. Farbenindustrie where Bayer with coworkers discovered the addition polymerization reaction between diisocyanates and diols. Since their discovery, the demand in PU has continued to increase and it will attain in 2016 a production of 18 million tons. However, isocyanates compounds are harmful to human and environment. Methylene diphenyl 4,4’-diisocyanate (MDI) and toluene diisocyanate (TDI), the most widely used isocyanates in PU industry, are classified as CMR (Carcinogen, Mutagen, and Reprotoxic). In order to design isocyanate-free materials, an interesting alternative is the use of Polyhydroxyurethanes (PHUs) by reaction between cyclic carbonate and polyfunctional amines. The main problem concerning PHUs synthesis relates to the low reactivity of carbonate/amine reaction. To solve this issue, many studies in the literature have been conducted to design PHU from more reactive cyclic-carbonates, bearing electro-withdrawing substituent or by using six-membered, seven-membered or thio-cyclic carbonate. The main drawback of all these systems remains the low molar masses obtained for the synthesized PHUs, which hinders their use for material applications. Therefore, we developed another strategy to afford new hybrid PHU with high conversion. This very innovative two-step approach consists in the first step in the synthesis of aminotelechelic PHU oligomers with different chain length from bis-cyclic carbonate with different excess of primary amine functions. In the second step, these aminotelechelic PHU oligomers were used in formulation with biobased epoxy monomers (from cashew nut shell liquid and tannins) to synthesize hybrid polyepoxyurethane polymers. These materials were then characterized by thermal and mechanical analyses.

Keywords: polyurethane, polyhydroxyurethane, aminotelechelic NIPU oligomers, carbonates, epoxy, amine, epoxyurethane polymers, hybrid polymers

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Authors: Ajay Krishnamurthy, Mariyappan Mahesh Kumar, Sellamuthu Periyar Selvam

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Fruits are considered as functional foods due to the presence of various bioactive compounds available such as polyphenols, which are beneficial to health when consumed as part of our diet. The primary objective of this study was to analyze the various functional groups present in ethanolic extracts of Hylocereus undatus and Garcinia indica and also measure their antibacterial and antioxidant potential respectively thereby affirming its nutraceutical potential. To fulfill our objective, a Fourier - transform Infrared Spectroscopy (FTIR) was conducted for functional group analysis, Total Phenolic Content and DPPH free radical scavenging activity for measuring it anti-oxidant potential and agar-well diffusion assay for antibacterial potential. On careful observation and analysis of the spectrum it was found that both the fruit extracts contain similar compounds viz. Phenols, Alkanes, Alkenes, Aldehydes, Ketones, Carboxylic Acid and Amines. Total phenolic content of H.undatus and G.indica was estimated to be (26.85 ± 1.84 mg GAE/100g) and (32.84 ± 1.63 mg GAE/100g) respectively which corresponds to an inhibition of 84% and 81% respectively. H.undatus shows an inhibition of (3.4 ± 2.1mm) in gram-positive and (4.2 ± 2.24mm) in gram-negative organism on the other hand G.indica shows (2.1 ± 0.98mm) in gram-positive and (3.1 ± 1.44mm) in gram negative. The presence of such diverse compounds in the fruits helps us to understand the necessity for the inclusion of fruits in our daily diet and also helps the pharmaceutical industry in realizing the importance of exotic fruits as a potential nutraceutical.

Keywords: DPPH, fourier-transform infrared spectroscopy (FTIR), Hylocereus undatus, Garcinia indica

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Authors: Debajyoti Bose

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Chitosan has received much attention as a functional biopolymer for diverse applications, especially in pharmaceutics and medicine. Chitosan is a positively charged natural biodegradable and biocompatible polymer. It is a linear polysaccharide consisting of β-1,4 linked monomers of glucosamine and N-acetylglucosamine. Chitosan can be mainly obtained from fungal sources during large fermentation process. In this study,three different fungal strains Aspergillus niger NCIM 1045, Aspergillus oryzae NCIM 645 and Mucor indicus MTCC 3318 were used for the production of chitosan. The growth mediums were optimized for maximum fungal production. The produced chitosan was characterized by determining degree of deacetylation. Chitosan possesses one reactive amino at the C-2 position of the glucosamine residue, and these amines confer important functional properties to chitosan which can be exploited for biofabrication to generate various chemically modified derivatives and explore their potential for pharmaceutical field. Chitosan nanoparticles were prepared by ionic cross-linking with tripolyphosphate (TPP). The major effect on encapsulation and release of protein (e.g. enzyme diastase) in chitosan-TPP nanoparticles was investigated in order to control the loading and release efficiency. It was noted that the chitosan loading and releasing efficiency as a nanocapsule, obtained from different fungal sources was almost near to initial enzyme activity(12026 U/ml) with a negligible loss. This signify, chitosan can be used as a polymeric drug as well as active component or protein carrier material in dosage by design due to its appealing properties such as biocompatibility, biodegradability, low toxicity and relatively low production cost from abundant natural sources. Based upon these initial experiments, studies were also carried out on modification of chitosan based nanocapsules incorporated with physiologically important enzymes and nutraceuticals for target delivery.

Keywords: fungi, chitosan, enzyme, nanocapsule

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Authors: Hlaing Zaw Oo, N. Kostromina, V. Osipchik, T. Kravchenko, K. Yakovleva

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The process of modification of ed-20 epoxy resin synthesized by vinyl-containing compounds is considered. It is shown that the introduction of vinyl-containing compounds into the composition based on epoxy resin ED-20 allows adjusting the technological and operational characteristics of the binder. For improvement of the properties of epoxy resin, following modifiers were selected: polyvinylformalethyl, polyvinyl butyral and composition of linear and aromatic amines (Аramine) as a hardener. Now the big range of hardeners of epoxy resins exists that allows varying technological properties of compositions, and also thermophysical and strength indicators. The nature of the aramin type hardener has a significant impact on the spatial parameters of the mesh, glass transition temperature, and strength characteristics. Epoxy composite materials based on ED-20 modified with polyvinyl butyral were obtained and investigated. It is shown that the composition of resins based on derivatives of polyvinyl butyral and ED-20 allows obtaining composite materials with a higher complex of deformation-strength, adhesion and thermal properties, better water resistance, frost resistance, chemical resistance, and impact strength. The magnitude of the effect depends on the chemical structure, temperature and curing time. In the area of concentrations, where the effect of composite synergy is appearing, the values of strength and stiffness significantly exceed the similar parameters of the individual components of the mixture. The polymer-polymer compositions form their class of materials with diverse specific properties that ensure their competitive application. Coatings with high performance under cyclic loading have been obtained based on epoxy oligomers modified with vinyl-containing compounds.

Keywords: epoxy resins, modification, vinyl-containing compounds, deformation, strength properties

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Authors: Lucia Steenkamp, Chris V. D. Westhuyzen, Kgama Mathiba

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Ambergris, and more specifically its oxidation product (–)-ambrafuran, is a scarce, valuable, and sought-after perfumery ingredient. The material is used as a fixative agent to stabilise perfumes in formulations by reducing the evaporation rate of volatile substances. Ambergris is a metabolic product of the sperm whale (Physeter macrocephatus L.), resulting from intestinal irritation. Chemically, (–)-ambrafuran is produced from the natural product sclareol in eight synthetic steps – in the process using harsh and often toxic chemicals to do so. An overall yield of no more than 76% can be achieved in some routes, but generally, this is lower. A new 'green' route has been developed in our laboratory in which sclareol, extracted from the Clary sage plant, is converted to (–)-ambrafuran in two steps with an overall yield in excess of 80%. The first step uses a microorganism, Hyphozyma roseoniger, to bioconvert sclareol to an intermediate diol using substrate concentrations up to 50g/L. The yield varies between 90 and 67% depending on the substrate concentration used. The purity of the diol product is 95%, and the diol is used without further purification in the next step. The intermediate diol is then cyclodehydrated to the final product (–)-ambrafuran using a zeolite, which is not harmful to the environment and is readily recycled. The yield of the product is 96%, and following a single recrystallization, the purity of the product is > 99.5%. A preliminary LC-MS study of the bioconversion identified several intermediates produced in the fermentation broth under oxygen-restricted conditions. Initially, a short-lived ketone is produced in equilibrium with a more stable pyranol, a key intermediate in the process. The latter is oxidised under Norrish type I cleavage conditions to yield an acetate, which is hydrolysed either chemically or under lipase action to afford the primary fermentation product, an intermediate diol. All the intermediates identified point to the likely CYP450 action as the key enzyme(s) in the mechanism. This invention is an exceptional example of how the power of biocatalysis, combined with a mild, benign chemical step, can be deployed to replace a total chemical synthesis of a specific chiral antipode of a commercially relevant material.

Keywords: ambrafuran, biocatalysis, fragrance, microorganism

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Authors: Naveeda Akhtar Qureshi, Wajiha

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Coccidiosis is a protozoan parasitic disease of genus Eimeria. It is an avian infection causing a great economic loss of 3 billion USD per year globally. A number of anticoccidial drugs are in use however many of them have side effects and cost effective. With increase in poultry demand throughout the world there is a need of more drugs and vaccines against coccidiosis. The present study is based upon the use of F. racemosa a medicinal plant to be a potential source of anticoccidial agents. The methanolic leaves extract was fractionated by column and thin layer chromatography and got nineteen fractions. Each fraction different concentrations was evaluated for its anticoccidial properties in an invitro experiment against E. tenella, E. necatrix and E. mitis. The anticoccidial active fractions were further characterized by spectroscopy (UV-Vis, FTIR) and GC-MS analysis. The in silico molecular docking of active fractions identified compounds were carried out. Among all fractions significantly maximum sporulation inhibition efficacy was shown by F-19 (67.11±2.18) followed by F-15 (65.21±1.34) at concentration of 30mg/ml against E. tenella. The significantly highest sporozoites viability inhibition was shown by F-19 (69.23±2.11) followed by F-15 (67.14±1.52) against E. necatrix at concentration 30mg/ml. Anticoccidial active fractions 15 and 19 showed peak spectrum at 207 and 202nm respectively by UV analysis. Their FTIR analysis confirmed the presence of carboxylic acid, amines, phenols, etc. Anticoccidial active compounds like Cyclododecane methanol, oleic acid, Octadecanoic acid, etc were identified by GC-MS analysis. Identified compounds in silico molecular docking study showed that cyclododecane methanol of F-19 and oleic acid of F-15 showed highest binding affinity with target S-Adenosylmethionine synthase. Hence for further authentication in vivo anticoccidial studies are recommended.

Keywords: ficus racemosa, cluster fig, column chromatography, anticoccidial fractions, GC-MS, molecular docking., s-adenosylmethionine synthase

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Authors: Ibrahim M. Labouta, Gina N. Tageldin, Salwa M. Fahmy, Hayam M. Ashour, Mounir A. Khalil, Tamer M. Ibrahim, Nefertiti A. El-Nikhely

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Bruton’s tyrosine kinase (BTK) is a critical effector molecule in B cell antigen receptor (BCR) signaling transduction. It regulates B cell proliferation, development and survival. Since BTK is widely expressed in many B cell leukaemias and lymphomas, targeting BTK by small molecules inhibitors became an attractive idea as new treatment modalities for B cell mediated hematologic malignancies. Ibrutinib is the 1st generation BTK inhibitor, approved by FDA for treatment of relapsed mantle cell lymphoma (MCL) and chronic lymphocytic leukemia (CLL). It binds irreversibly to the unique cysteine (Cys481) within the ATP-binding pocket of BTK. Besides ibrutinib, many irreversible covalent BTK inhibitors comprising pyrimidine nucleus such as spebrutinib (phase IIb) showed high selectivity and potency when compared to it. In this study, the designed compounds were based on 5-cyano-2-methylsulfanyl pyrimidine core and decorated with electrophilic warheads which are essential for the optimal activity for targeted covalent inhibition (TCI). However, modifications at pyrimidine C4 or C6 were made by introduction of substituted amines which are provided to behave differently. The synthesized derivatives were evaluated for their anticancer activity in leukemia cell lines (e.g. THP-1). Results showed that, some derivatives exhibited antiproliferative activity with IC50 ranged from 5-50 μM, The in vitro enzymatic inhibitory assay for these compounds against BTK is still under investigation. Nevertheless, we could conclude from the initial biological screening that, the synthesized 4 or 6-subsitituted aminopyrimidines represent promising and novel antileukemic agents. Meanwhile, further studies are still needed to attribute this activity through targeting BTK enzyme and inhibition of BCR signaling pathway.

Keywords: BTK inhibitors, hematologic malignancies, structure based drug design (SBDD), targeted covalent inhibitors (TCI)

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Authors: N. Harun, E. E. Masiren, W. H. W. Ibrahim, F. Adam

Abstract:

Amine absorption process is an approach for mitigation of CO2 from flue gas that produces from power plant. This process is the most common system used in chemical and oil industries for gas purification to remove acid gases. On the challenges of this process is high energy requirement for solvent regeneration to release CO2. In the past few years, mixed alkanolamines have received increasing attention. In most cases, the mixtures contain N-methyldiethanolamine (MDEA) as the base amine with the addition of one or two more reactive amines such as PZ. The reason for the application of such blend amine is to take advantage of high reaction rate of CO2 with the activator combined with the advantages of the low heat of regeneration of MDEA. Several experimental and simulation studies have been undertaken to understand this process using blend MDEA/PZ solvent. Despite those studies, the mechanism of CO2 absorption into the aqueous MDEA is not well understood and available knowledge within the open literature is limited. The aim of this study is to investigate the intermolecular interaction of the blend MDEA/PZ using Molecular Dynamics (MD) simulation. MD simulation was run under condition 313K and 1 atm using NVE ensemble at 200ps and NVT ensemble at 1ns. The results were interpreted in term of Radial Distribution Function (RDF) analysis through two system of interest i.e binary and tertiary. The binary system will explain the interaction between amine and water molecule while tertiary system used to determine the interaction between the amine and CO2 molecule. For the binary system, it was observed that the –OH group of MDEA is more attracted to water molecule compared to –NH group of MDEA. The –OH group of MDEA can form the hydrogen bond with water that will assist the solubility of MDEA in water. The intermolecular interaction probability of –OH and –NH group of MDEA with CO2 in blended MDEA/PZ is higher than using single MDEA. This findings show that PZ molecule act as an activator to promote the intermolecular interaction between MDEA and CO2.Thus, blend of MDEA with PZ is expecting to increase the absorption rate of CO2 and reduce the heat regeneration requirement.

Keywords: amine absorption process, blend MDEA/PZ, CO2 capture, molecular dynamic simulation, radial distribution function

Procedia PDF Downloads 261

Authors: Abdul Mutalib Md Jani, Abdul Hadi Mahmud, Mohd Tajuddin Mohd Ali

Abstract:

The rapid growth of interest in surface modification of nanostructures materials that exhibit improved structural and functional properties is attracting more researchers. The unique properties of highly ordered nanoporous anodic aluminium oxide (NAAO) membrane have been proposed as a platform for biosensing applications. They exhibit excellent physical and chemical properties with high porosity, high surface area, tunable pore sizes and excellent chemical resistance. In this study, NAAO was functionalized with 3-aminopropyltriethoxysilane (APTES) to prepared silane-modified NAAO. Amine functional groups are formed on the surface of NAAO during silanization and were characterized using Fourier Transform Infrared spectroscopy (FTIR). The synthesis of multi segment of peptide on NAAO surfaces can be realized by changing the surface chemistry of the NAAO membrane via click chemistry. By click reactions, utilizing alkyne terminated with amino group, various peptides tagged on NAAO can be envisioned from chiral natural or unnatural amino acids using standard coupling methods (HOBt, EDCI and HBTU). This strategy seemly versatile since coupling strategy of dipeptide with another amino acids, leading to tripeptide, tetrapeptide or pentapeptide, can be synthesized without purification. When an appropriate terminus is selected, multiple segments of amino acids can be successfully synthesized on the surfaces. The immobilized NAAO should be easily separated from the reaction medium by conventional filtration, thus avoiding complicated purification methods. Herein, we proposed to synthesize multi fragment peptide as a model for capturing and attaching various small biomolecules on NAAO surfaces and can be also applied as biosensing device, drug delivery systems and biocatalyst.

Keywords: nanoporous anodic aluminium oxide, silanization, peptide synthesise, click chemistry

Procedia PDF Downloads 253

Authors: T. R. Bandara, H. Jaelani, G. J. Griffin

Abstract:

The conversion of lignocellulosic waste materials, such as sugar cane bagasse, to biofuels such as ethanol has attracted significant interest as a potential element for transforming transport fuel supplies to totally renewable sources. However, the refractory nature of the cellulosic structure of lignocellulosic materials has impeded progress on developing an economic process, whereby the cellulose component may be effectively broken down to glucose monosaccharides and then purified to allow downstream fermentation. Ionic liquid (IL) treatment of lignocellulosic biomass has been shown to disrupt the crystalline structure of cellulose thus potentially enabling the cellulose to be more readily hydrolysed to monosaccharides. Furthermore, conventional hydrolysis of lignocellulosic materials yields byproducts that are inhibitors for efficient fermentation of the monosaccharides. However, selective extraction of monosaccharides from an aqueous/IL phase into an organic phase utilizing a combination of boronic acids and quaternary amines has shown promise as a purification process. Hydrolysis of sugar cane bagasse immersed in an aqueous solution with IL (1-ethyl-3-methylimidazolium acetate) was conducted at different pH and temperature below 100 ºC. It was found that the use of a high concentration of hydrochloric acid to acidify the solution inhibited the hydrolysis of bagasse. At high pH (i.e. basic conditions), using sodium hydroxide, catalyst yields were reduced for total reducing sugars (TRS) due to the rapid degradation of the sugars formed. For purification trials, a supported liquid membrane (SLM) apparatus was constructed, whereby a synthetic solution containing xylose and glucose in an aqueous IL phase was transported across a membrane impregnated with phenyl boronic acid/Aliquat 336 to an aqueous phase. The transport rate of xylose was generally higher than that of glucose indicating that a SLM scheme may not only be useful for purifying sugars from undesirable toxic compounds, but also for fractionating sugars to improve fermentation efficiency.

Keywords: biomass, bagasse, hydrolysis, monosaccharide, supported liquid membrane, purification

Procedia PDF Downloads 225

Authors: Hanan. Al Chaghouri, Mohammad Azad Malik, P. John Thomas, Paul O’Brien

Abstract:

The process of assembling metal nanoparticles at the interface of two liquids has received a great interest over the past few years due to a wide range of important applications and their unusual properties compared to bulk materials. We present a low cost, simple and cheap synthesis of metal nanoparticles, core/shell structures and semiconductors followed by assembly of these particles between immiscible liquids. The aim of this talk is divided to three parts: firstly, to describe the achievement of a closed loop recycling for producing cadmium sulphide as powders and/or nanostructured thin films for solar cells or other optoelectronic devices applications by using a different chain length of commercially available secondary amines of dithiocarbamato complexes. The approach can be extended to other metal sulphides such as those of Zn, Pb, Cu, or Fe and many transition metals and oxides. Secondly, to synthesis significantly cheaper magnetic particles suited for the mass market. Ni/NiO nanoparticles with ferromagnetic properties at room temperature were among the smallest and strongest magnets (5 nm) were made in solution. The applications of this work can be applied to produce viable storage devices and the other possibility is to disperse these nanocrystals in solution and use it to make ferro-fluids which have a number of mature applications. The third part is about preparing and assembling of submicron silver, cobalt and nickel particles by using polyol methods and liquid/liquid interface, respectively. Noble metal like gold, copper and silver are suitable for plasmonic thin film solar cells because of their low resistivity and strong interactions with visible light waves. Silver is the best choice for solar cell application since it has low absorption losses and high radiative efficiency compared to gold and copper. Assembled cobalt and nickel as films are promising for spintronic, magnetic and magneto-electronic and biomedics.

Keywords: assembling nanoparticles, liquid/liquid interface, thin film, core/shell, solar cells, recording media

Procedia PDF Downloads 276

Authors: Julian Mehler, Marcus Fischer, Martin Hartmann, Peter S. Schulz

Abstract:

During the last two decades, the synthesis of metal-organic frameworks (MOFs) has gained ever increasing attention. Based on their pore size and shape as well as host-guest interactions, they are of interest for numerous fields related to porous materials, like catalysis and gas separation. Usually, MOF-synthesis takes place in an organic solvent between room temperature and approximately 220 °C, with mixtures of polyfunctional organic linker molecules and metal precursors as substrates. Reaction temperatures above the boiling point of the solvent, i.e. solvothermal reactions, are run in autoclaves or sealed glass vessels under autogenous pressures. A relatively new approach for the synthesis of MOFs is the so-called ionothermal synthesis route. It applies an ionic liquid as a solvent, which can serve as a structure-directing template and/or a charge-compensating agent in the final coordination polymer structure. Furthermore, this method often allows for less harsh reaction conditions than the solvothermal route. Here a variation of the ionothermal approach is reported, where the ionic liquid also serves as an organic linker source. By using 1-ethyl-3-methylimidazolium terephthalates ([EMIM][Hbdc] and [EMIM]₂[bdc]), the one-step synthesis of MIL-53(Al)/Boehemite composites with interesting features is possible. The resulting material is already formed at moderate temperatures (90-130 °C) and is stabilized in the usually unfavored ht-phase. Additionally, in contrast to already published procedures for MIL-53(Al) synthesis, no further activation at high temperatures is mandatory. A full characterization of this novel composite material is provided, including XRD, SS-NMR, El-Al., SEM as well as sorption measurements and its interesting features are compared to MIL-53(Al) samples produced by the classical solvothermal route. Furthermore, the syntheses of the applied ionic liquids and salts is discussed. The influence of the degree of ionicity of the linker source [EMIM]x[H(2-x)bdc] on the crystal structure and the achievable synthesis temperature are investigated and give insight into the role of the IL during synthesis. Aside from the synthesis of MIL-53 from EMIM terephthalates, the use of the phosphonium cation in this approach is discussed as well. Additionally, the employment of ILs in the preparation of other MOFs is presented briefly. This includes the ZIF-4 framework from the respective imidazolate ILs and chiral camphorate based frameworks from their imidazolium precursors.

Keywords: ionic liquids, ionothermal synthesis, material synthesis, MIL-53, MOFs

Procedia PDF Downloads 172

Authors: Delgado-Meza M., Minor-Pérez H.

Abstract:

Protease is the generic name of enzymes that hydrolyze proteins. These are classified in the subgroup EC3.4.11-99X of the classification enzymes. In food technology the proteolysis is used to modify functional and nutritional properties of food, and in some cases this proteolysis may cause food spoilage. In general, seafood and rainbow trout have accelerated decomposition process once it has done its capture, due to various factors such as the endogenous enzymatic activity that can result in loss of structure, shape and firmness, besides the release of amino acid precursors of biogenic amines. Some studies suggest the use of protease inhibitors from legume as biological regulators of proteolytic activity. The enzyme inhibitors are any substance that reduces the rate of a reaction catalyzed by an enzyme. The objective of this study was to evaluate the reduction of the proteolytic activity of enzymes in extracts of rainbow trout with protease inhibitors obtained from chickpea flour. Different proportions of rainbow trout enzyme extract (75%, 50% and 25%) and extract chickpea enzyme inhibitors were evaluated. Chickpea inhibitors were obtained by mixing 5 g of flour in 30 mL of pH 7.0 phosphate buffer. The sample was centrifuged at 8000 rpm for 10 min. The supernatant was stored at -15°C. Likewise, 20 g of rainbow trout were ground in 20 mL of phosphate buffer solution at pH 7.0 and the mixture was centrifuged at 5000 rpm for 20 min. The supernatant was used for the study. In each treatment was determined the specific enzymatic activity with the technique of Kunitz, using hemoglobin as substrate for the enzymes acid fraction and casein for basic enzymes. Also biuret protein was quantified for each treatment. The results showed for fraction of basic enzymes in the treatments evaluated, that were inhibition of endogenous enzymatic activity. Inhibition values compared to control were 51.05%, 56.59% and 59.29% when the proportions of endogenous enzymes extract rainbow trout were 75%, 50% and 25% and the remaining volume used was extract with inhibitors. Treatments with acid enzymes showed no reduction in enzyme activity. In conclusion chickpea flour reduced the endogenous enzymatic activity of rainbow trout, which may favor its application to increase the half-life of this food. The authors acknowledge the funding provided by the CONACYT for the project 131998.

Keywords: rainbouw trout, enzyme inhibitors, proteolysis, enzyme activity

Procedia PDF Downloads 377

Authors: Hanan. Al Chaghouri, Mohammad Azad Malik, P. John Thomas, Paul O’Brien

Abstract:

The process of assembling metal nanoparticles at the interface of two liquids has received a great deal of attention over the past few years due to a wide range of important applications and their unusual properties as compared to bulk materials. We present a low cost, simple and cheap synthesis of metal nanoparticles, core/shell structures and semiconductors followed by assembly of these particles between immiscible liquids. The aim of this talk is divided to three parts: Firstly, to describe the achievement of a closed loop recycling for producing cadmium sulfide as powders and/or nanostructured thin films for solar cells or other optoelectronic devices applications by using a different chain length of commercially available secondary amines of dithiocarbamato complexes. The approach can be extended to other metal sulfides such as those of Zn, Pb, Cu, or Fe and many transition metals and oxides. Secondly, to synthesis significantly cheaper magnetic particles suited for the mass market. Ni/NiO nanoparticles with ferromagnetic properties at room temperature were among the smallest and strongest magnets (5 nm) were made in solution. The applications of this work can be to produce viable storage devices and the other possibility is to disperse these nanocrystals in solution and use it to make ferrofluids which have a number of mature applications. The third part is about preparing and assembling of submicron silver, cobalt and nickel particles by using polyol methods and liquid/liquid interface, respectively. Coinage metals like gold, copper and silver are suitable for plasmonic thin film solar cells because of their low resistivity and strong interactions with visible light waves. Silver is the best choice for solar cell application since it has low absorption losses and high radiative efficiency compared to gold and copper. Assembled cobalt and nickel as films are promising for spintronic, magnetic and magneto-electronic and biomedics.

Keywords: metal nanoparticles, core/shell structures and semiconductors, ferromagnetic properties, closed loop recycling, liquid/liquid interface

Procedia PDF Downloads 439

Authors: Bagnoud-Velásquez Mariluz, Damergi Eya, Grandjean Dominique, Frédéric Vogel, Ludwig Christian

Abstract:

The sustainability of algae to biofuel processes is seriously affected by the energy intensive production of fertilizers. Large amounts of nitrogen and phosphorus are required for a large-scale production resulting in many cases in a negative impact of the limited mineral resources. In order to meet the algal bioenergy opportunity it appears crucial the promotion of processes applying a nutrient recovery and/or making use of renewable sources including waste. Hydrothermal (HT) conversion is a promising and suitable technology for microalgae to generate biofuels. Besides the fact that water is used as a “green” reactant and solvent and that no biomass drying is required, the technology offers a great potential for nutrient recycling. This study evaluated the possibility to treat the water HT effluent by the growth of microalgae while producing renewable algal biomass. As already demonstrated in previous works by the authors, the HT aqueous product besides having N, P and other important nutrients, presents a small fraction of organic compounds rarely studied. Therefore, extracted heteroaromatic compounds in the HT effluent were the target of the present research; they were profiled using GC-MS and LC-MS-MS. The results indicate the presence of cyclic amides, piperazinediones, amines and their derivatives. The most prominent nitrogenous organic compounds (NOC’s) in the extracts were carefully examined by their effect on microalgae, namely 2-pyrrolidinone and β-phenylethylamine (β-PEA). These two substances were prepared at three different concentrations (10, 50 and 150 ppm). This toxicity bioassay used three different microalgae strains: Phaeodactylum tricornutum, Chlorella sorokiniana and Scenedesmus vacuolatus. The confirmed IC50 was for all cases ca. 75ppm. Experimental conditions were set up for the growth of microalgae in the aqueous phase by adjusting the nitrogen concentration (the key nutrient for algae) to fit that one established for a known commercial medium. The values of specific NOC’s were lowered at concentrations of 8.5 mg/L 2-pyrrolidinone; 1mg/L δ-valerolactam and 0.5 mg/L β-PEA. The growth with the diluted HT solution was kept constant with no inhibition evidence. An additional ongoing test is addressing the possibility to apply an integrated water cleanup step making use of the existent hydrothermal catalytic facility.

Keywords: hydrothermal process, microalgae, nitrogenous organic compounds, nutrient recovery, renewable biomass

Procedia PDF Downloads 381

Authors: Manohar Salla, Mark S. Butler, Ruby Pelingon, Geraldine Kaeslin, Daniel E. Croker, Janet C. Reid, Jong Min Baek, Paul V. Bernhardt, Elizabeth M. J. Gillam, Matthew A. Cooper, Avril A. B. Robertson

Abstract:

MCC950 is a potent and selective inhibitor of the NOD-like receptor pyrin domain-containing protein 3 (NLRP3) inflammasome that shows early promise for treatment of inflammatory diseases. The identification of major metabolites of lead molecule is an important step during drug development process. It provides an information about the metabolically labile sites in the molecule and thereby helping medicinal chemists to design metabolically stable molecules. To identify major metabolites of MCC950, the compound was incubated with human liver microsomes and subsequent analysis by (+)- and (−)-QTOF-ESI-MS/MS revealed a major metabolite formed due to hydroxylation on 1,2,3,5,6,7-hexahydro-s-indacene moiety of MCC950. This major metabolite can lose two water molecules and three possible regioisomers were synthesized. Co-elution of major metabolite with each of the synthesized compounds using HPLC-ESI-SRM-MS/MS revealed the structure of the metabolite (±) N-((1-hydroxy-1,2,3,5,6,7-hexahydro-s-indacen-4-yl)carbamoyl)-4-(2-hydroxypropan-2-yl)furan-2-sulfonamide. Subsequent synthesis of individual enantiomers and coelution in HPLC-ESI-SRM-MS/MS using a chiral column revealed the metabolite was R-(+)- N-((1-hydroxy-1,2,3,5,6,7-hexahydro-s-indacen-4-yl)carbamoyl)-4-(2-hydroxypropan-2-yl)furan-2-sulfonamide. To study the possible cytochrome P450 enzyme(s) responsible for the formation of major metabolite, MCC950 was incubated with a panel of cytochrome P450 enzymes. The result indicated that CYP1A2, CYP2A6, CYP2B6, CYP2C9, CYP2C18, CYP2C19, CYP2J2 and CYP3A4 are most likely responsible for the formation of the major metabolite. The biological activity of the major metabolite and the other synthesized regioisomers was also investigated by screening for for NLRP3 inflammasome inhibitory activity and cytotoxicity. The major metabolite had 170-fold less inhibitory activity (IC50-1238 nM) than MCC950 (IC50-7.5 nM). Interestingly, one regioisomer had shown nanomolar inhibitory activity (IC50-232 nM). However, no evidence of cytotoxicity was observed with any of these synthesized compounds when tested in human embryonic kidney 293 cells (HEK293) and human liver hepatocellular carcinoma G2 cells (HepG2). These key findings give an insight into the SAR of the hexahydroindacene moiety of MCC950 and reveal a metabolic soft spot which could be blocked by chemical modification.

Keywords: Cytochrome P450, inflammasome, MCC950, metabolite, microsome, NLRP3

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Authors: Alexandra C. Blaga, Dan Caşcaval, Alexandra Tucaliuc, Madalina Poştaru, Anca I. Galaction

Abstract:

Amino acids are valuable chemical products used in in human foods, in animal feed additives and in the pharmaceutical field. Recently, there has been a noticeable rise of amino acids utilization throughout the world to include their use as raw materials in the production of various industrial chemicals: oil gelating agents (amino acid-based surfactants) to recover effluent oil in seas and rivers and poly(amino acids), which are attracting attention for biodegradable plastics manufacture. The amino acids can be obtained by biosynthesis or from protein hydrolysis, but their separation from the obtained mixtures can be challenging. In the last decades there has been a continuous interest in developing processes that will improve the selectivity and yield of downstream processing steps. The liquid-liquid extraction of amino acids (dissociated at any pH-value of the aqueous solutions) is possible only by using the reactive extraction technique, mainly with extractants of organophosphoric acid derivatives, high molecular weight amines and crown-ethers. The purpose of this study was to analyse the separation of nine amino acids of acidic character (l-aspartic acid, l-glutamic acid), basic character (l-histidine, l-lysine, l-arginine) and neutral character (l-glycine, l-tryptophan, l-cysteine, l-alanine) by reactive extraction with di-(2-ethylhexyl)phosphoric acid (D2EHPA) dissolved in butyl acetate. The results showed that the separation yield is controlled by the pH value of the aqueous phase: the reactive extraction of amino acids with D2EHPA is possible only if the amino acids exist in aqueous solution in their cationic forms (pH of aqueous phase below the isoeletric point). The studies for individual amino acids indicated the possibility of selectively separate different groups of amino acids with similar acidic properties as a function of aqueous solution pH-value: the maximum yields are reached for a pH domain of 2–3, then strongly decreasing with the pH increase. Thus, for acidic and neutral amino acids, the extraction becomes impossible at the isolelectric point (pHi) and for basic amino acids at a pH value lower than pHi, as a result of the carboxylic group dissociation. From the results obtained for the separation from the mixture of the nine amino acids, at different pH, it can be observed that all amino acids are extracted with different yields, for a pH domain of 1.5–3. Over this interval, the extract contains only the amino acids with neutral and basic character. For pH 5–6, only the neutral amino acids are extracted and for pH > 6 the extraction becomes impossible. Using this technique, the total separation of the following amino acids groups has been performed: neutral amino acids at pH 5–5.5, basic amino acids and l-cysteine at pH 4–4.5, l-histidine at pH 3–3.5 and acidic amino acids at pH 2–2.5.

Keywords: amino acids, di-(2-ethylhexyl) phosphoric acid, reactive extraction, selective extraction

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Authors: Rasha Al-Saedi, Anthony Meijer

Abstract:

The progress of new porous materials has increased rapidly over the past decade for use in applications such as catalysis, gas storage and removal of environmentally unfriendly species due to their high surface area and high thermal stability. In this work, a theoretical study of the zirconium-based metal organic framework (MOFs) were examined in order to determine their potential for gas adsorption of various guest molecules: CO2, N2, CH4 and H2. The zirconium cluster consists of an inner Zr6O4(OH)4 core in which the triangular faces of the Zr6- octahedron are alternatively capped by O and OH groups which bound to nine formate groups and three benzoate groups linkers. General formula is [Zr(μ-O)4(μ-OH)4(HCOO)9((phyO2C)3X))] where X= CH2OH, CH2NH2, CH2CONH2, n(NH2); (n = 1-3). Three types of adsorption sites on the Zr metal center have been studied, named according to capped chemical groups as the ‘−O site’; the H of (μ-OH) site removed and added to (μ-O) site, ‘–OH site’; (μ-OH) site removed, the ‘void site’ where H2O molecule removed; (μ-OH) from one site and H from other (μ-OH) site, in addition to no defect versions. A series of investigations have been performed aiming to address this important issue. First, density functional theory DFT-B3LYP method with 6-311G(d,p) basis set was employed using Gaussian 09 package in order to evaluate the gas adsorption performance of missing-linker defects in zirconium cluster. Next, study the gas adsorption behaviour on different functionalised zirconium clusters. Those functional groups as mentioned above include: amines, alcohol, amide, in comparison with non-substitution clusters. Then, dispersion-corrected density functional theory (DFT-D) calculations were performed to further understand the enhanced gas binding on zirconium clusters. Finally, study the water effect on CO2 and N2 adsorption. The small functionalized Zr clusters were found to result in good CO2 adsorption over N2, CH4, and H2 due to the quadrupole moment of CO2 while N2, CH4 and H2 weakly polar or non-polar. The adsorption efficiency was determined using the dispersion method where the adsorption binding improved as most of the interactions, for example, van der Waals interactions are missing with the conventional DFT method. The calculated gas binding strengths on the no defect site are higher than those on the −O site, −OH site and the void site, this difference is especially notable for CO2. It has been stated that the enhanced affinity of CO2 of no defect versions is most likely due to the electrostatic interactions between the negatively charged O of CO2 and the positively charged H of (μ-OH) metal site. The uptake of the gas molecule does not enhance in presence of water as the latter binds to Zr clusters more strongly than gas species which attributed to the competition on adsorption sites.

Keywords: density functional theory, gas adsorption, metal- organic frameworks, molecular simulation, porous materials, theoretical chemistry

Procedia PDF Downloads 154