Search results for: chitin nanocrystals

Authors: A. Altomi, A. Alhebshi, M. Rasm, B. Osman

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This study explored the application of chitin nanocrystals (ChiNCs), derived from a renewable and environmentally friendly material, as stabilizers for oil-in-water (O/W) emulsions. O/W emulsions are commonly used in various applications but are prone to instability and degradation over time. Instability can occur due to factors such as flocculation, coalescence, and gravitational separation, including creaming and sedimentation, either independently or simultaneously. To produce ChiNCs, chitin powder underwent acid hydrolysis. Transmission electron microscopy (TEM) analysis revealed that ChiNCs exhibited a needle-like morphology, with lengths ranging from 200 to 800 nm and widths ranging from 20 to 80 nm. The surface charge of ChiNCs was negative at pH values above 7 and positive at pH values below 7. The rheological properties of O/W emulsions stabilized by ChiNCs were compared to those stabilized by synthetic surfactants, namely Tween 80 and CTAB. The emulsions stabilized by ChiNCs demonstrated higher yield stress and lower shear viscosity compared to those stabilized by synthetic surfactants. This indicates that ChiNC-stabilized emulsions are more stable and less prone to breakdown. Based on these findings, ChiNCs show promise as an alternative to synthetic surfactants for stabilizing O/W emulsions.

Keywords: chitin nanocrystals, colloidal pickering, emulsion rheology, oil-in-water, synthetic surfactant

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Authors: Azhar Alhasawi, Vasu D. Appanna

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Chitin, the second most abundant bio-polymer in nature after cellulose, composed of β (1→4) linked N-acetylglucosamine (GlcNAc), is a major structural component in the cell walls of fungi and the shells of crustaceans. Chitin and its derivatives are gaining importance of economic value due to its biological activity and its industrial and biomedical applications. There are several methods to hydrolyze chitin to NAG, but they are typically expensive and environmentally unfriendly. Chitinase which catalyzes the breakdown of chitin to NAG has received much attention owing to its various applications in biotechnology. The presented research examines the ability of the versatile soil microbe, Pseudomonas fluorescens grown in chitin medium to produce chitinase and a variety of value-added products under abiotic stress. We have found that with high pH, Pseudomonas fluorescens enable to metabolize chitin more than with neutral pH and the overexpression of chitinase was also increased. P-dimethylaminobenzaldehyde (DMAB) assay for NAG production will be monitored and a combination of sodium dodecyl polyacrylamide gels will be used to monitor the proteomic and metabolomic changes as a result of the abiotic stress. The bioreactor of chitinase will also be utilized.

Keywords: Pseudomonas fluorescens, chitin, DMAB, chitinase

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Authors: Diana G. Ramirez-Wong, Marius Ramirez, Regina Sanchez-Leija, Adriana Rugerio, R. Araceli Mauricio-Sanchez, Martin A. Hernandez-Landaverde, Arturo Carranza, John A. Pojman, Josue D. Mota-Morales, Gabriel Luna-Barcenas

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Chitin films were prepared using alpha-chitin from shrimp shells as raw material and a simple method of precipitation-evaporation. Choline chloride: urea Deep Eutectic Solvent (DES) was used to disperse chitin and compared against hexafluoroisopropanol (HFIP). A careful analysis of the chemical and crystalline structure was followed along the synthesis of the films, revealing crystalline-phase transitions. The full conversion of alpha- to beta-, or alpha- to gamma-chitin structure were detected by XRD and NMR on the films. The synthesis of highly crystalline monophasic gamma-chitin films was achieved using a DES; whereas HFIP helps to promote the beta-phase. These results are encouraging to continue in the study of DES as good processing media to control the final properties of chitin based materials.

Keywords: chitin, deep eutectic solvent, polymorph, phase transformation

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Authors: Keyur Raval, Steffen Krohn, Bruno Moerschbacher

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Chitin, the biopolymer of the N-acetylglucosamine, is the most abundant biopolymer on the planet after cellulose. Industrially, chitin is isolated and purified from the shell residues of shrimps. A deacetylated derivative of chitin i.e. chitosan has more market value and applications owing to it solubility and overall cationic charge compared to the parent polymer. This deacetylation on an industrial scale is performed chemically using alkalis like sodium hydroxide. This reaction not only is hazardous to the environment owing to negative impact on the marine ecosystem. A greener option to this process is the enzymatic process. In nature, the naïve chitin is converted to chitosan by chitin deacetylase (CDA). This enzymatic conversion on the industrial scale is however hampered by the crystallinity of chitin. Thus, this enzymatic action requires the substrate i.e. chitin to be soluble which is technically difficult and an energy consuming process. We in this project wanted to address this shortcoming of CDA. In lieu of this, we have modeled a fusion protein with CDA and an auxiliary protein. The main interest being to increase the accessibility of the enzyme towards crystalline chitin. A similar fusion work with chitinases had improved the catalytic ability towards insoluble chitin. In the first step, suitable partners were searched through the protein data bank (PDB) wherein the domain architecture were sought. The next step was to create the models of the fused product using various in silico techniques. The models were created by MODELLER and evaluated for properties such as the energy or the impairment of the binding sites. A fusion PCR has been designed based on the linker sequences generated by MODELLER and would be tested for its activity towards insoluble chitin.

Keywords: chitin deacetylase, modeling, chitin binding domain, chitinases

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Authors: Numfon Rakkhumkaew, Takeru Kawasaki, Makoto Fujie, Takashi Yamada

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Chlorella viruses or chloroviruses contain a gene that encodes a function for chitin synthesis, which is expressed early in viral infection to produce chitin polysaccharide, a polymer of β-1, 4-linked GlcNAc, on the outside of Chlorella cell wall. Interestingly, chlorovirus system is an eco-friendly system which converses CO2 and solar energy from the environment into useful materials. However, infected Chlorella cells are lysed at the final stage of viral infection, and this phenomenon is caused the breaking down of polysaccharide. To postpone the lysing period and prolong the synthesis of chitin polysaccharide on cells, the slow growing virus incorporated with aphidicolin treatment, an inhibitor of DNA synthesis, was investigated. In this study, a total of 25 virus isolates from water samples in Japan region were analyzed for CHS (the gene for CH synthase) gene by PCR (polymerase chain reaction). The accumulation and appearance of chitin polysaccharide on infected cells were detected by biotinylated chitin-binding proteins WGA (wheat germ agglutinin)-biotin for chitin in conjunction with avidin-Cy 2 or Cy 3 and investigated by fluorescence microscopy, observed as green or yellow fluorescence over the cell surface. Among all chlorovirus isolates, cells infected with CNF1 revealed the accumulation of chitin over the cell surface within 30 min p.i. and continued to accumulate on cells until 4 h p.i. before cell lyses which was 1.6 times longer accumulation period than cells infected with CVK2 (prototype virus). Furthermore, addition of aphidicolin could extend the chitin accumulation on cells infected with CNF1 until 8 h p.i. before cell lyses. Whereas, CVK2-infected cells treated with aphidicolin could prolong the chitin synthesis only for 6 h p.i. before cell lyses. Therefore, chitin synthesis by Chlorella-virus system could be prolonged by using slow-growing viral isolates and with aphidicolin.

Keywords: chitin, chlorovirus, Chlorella virus, aphidicolin

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Authors: Maycon dos Santos, Marivane Turim Koschevic, Karina Sayuri Ueda, Marcello Lima Bertuci, Farayde Matta Fackhouri, Silvia Maria Martelli

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The use of cellulose nanocrystals as reinforcing agents in polymer nanocomposites is promising. In this study, we tested four different methods of mercerization were divided into two stages. The sample was treated in 5% NaOH solution for 30 minutes at 50 ° C in the first stage and 30vol H2O2 for 2 hours at 50 ° C in the second step, which showed better results. For the extraction of the sample obtained nanocrystals positive result was that the solution was treated with H2SO4 60% (w / w) for 1 hour at 50 ° C. The results were positive and showed that it is possible to extract CNC at low temperatures.

Keywords: soy pods, cellulose nanocrystals, temperature, acid concentration

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Authors: Randy Molejona Jr., Elaine Nicole Saquin

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The area around the Ajuy river in Iloilo, Philippines, is currently being mined for manganese ore, and river water samples exceed the maximum manganese contaminant level set by US-EPA. At the same time, the surplus of local bivalve waste is another environmental concern. Synthetic chemical treatment compromises water quality, leaving toxic residues. Therefore, an alternative treatment process is biosorption or using the physical and chemical properties of biomass to adsorb heavy metals in contaminated water. The study aims to extract crude chitin from shell wastes of Bractechlamys vexillum, Perna viridis, and Placuna placenta and determine its adsorption capacity on manganese in simulated and actual mine water. Crude chitin was obtained by pulverization, deproteinization, demineralization, and decolorization of shells. Biosorption by flocculation followed 5 g: 50 mL chitin-to-water ratio. Filtrates were analyzed using MP-AES after 24 hours. In both actual and simulated mine water, respectively, B. vexillum yielded the highest adsorption percentage of 91.43% and 99.58%, comparable to P. placenta of 91.43% and 99.37%, while significantly different to P. viridis of -57.14% and 31.53%, (p < 0.05). FT-IR validated the presence of chitin in shells based on carbonyl-containing functional groups at peaks 1530-1560 cm⁻¹ and 1660-1680 cm⁻¹. SEM micrographs showed the amorphous and non-homogenous structure of chitin. Thus, crude chitin from B. vexillum and P. placenta can be bio-sorbents for water treatment of manganese-impacted effluents, and promote appropriate waste management of local bivalves.

Keywords: biosorption, chitin, FT-IR, mine effluents, SEM

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Authors: Ben Amar Cheba, Taha Ibrahim Zaghloul, Mohamad Hisham El-Massry, Ahmad Rafik El-Mahdy

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Seventy two bacterial strains with ability to degrade chitin were isolated during a screening program. One of the most potent isolates (strain R2) was identified as Bacillus sp. using conventional methods as well as 16S rRNA technique and submitted in the Gen Bank sequence database as Bacillus sp. R2 with a given accession number DQ 923161. This strain was able to produce high levels of extracellular chitinase. The chitinase of Bacillus sp. R2 hydrolyzed several chitinous substrates preferentially and showed a maximum activity toward the β chitin such as Calmar pen and squid bone chitins with the folds 1.47 and 1.23 respectively. The enzyme also exhibited a substrate binding capacity of more than 70% for squid chitin, shrimp shell colloidal chitin, chitosan and prawn shell chitin. The chitinase showed a moderate antifungal activity against many phytopathogenic fungi such as Aspergillus niger, A. flavus, Penicillium degitatum and Fusarium calmorum.This strain could be a suitable candidate for chitinase production on an industrial scale for using as promising antifungal biopestecide.

Keywords: antifungal activity, Bacillus sp. R2, chitinase, substrate specificity

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Authors: Innocent O. Arukalam, Emeka E. Oguzie

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Interest in the development of eco-friendly anti-corrosion coatings using bio-based renewable materials is gaining momentum recently. To this effect, chitin biopolymer, which is non-toxic, biodegradable, and inherently possesses anti-microbial property, was successfully synthesized from snail shells and used as a filler in the preparation of epoxy coating. The chitin particles were characterized with contact angle goniometer, scanning electron microscope (SEM), Fourier transform infrared (FTIR) spectrophotometer, and X-ray diffractometer (XRD). The performance of the coatings was evaluated by immersion and electrochemical impedance spectroscopy (EIS) tests. Electronic structure properties of the coating ingredients and molecular level interaction of the corrodent and coated Q235 steel were appraised by quantum chemical computations (QCC) and molecular dynamics (MD) simulation techniques, respectively. The water contact angle (WCA) measurement of chitin particles was found to be 129.3o while that of chitin particles modified with amino trimethoxy silane (ATMS) was 149.6o, suggesting it is highly hydrophobic. Immersion and EIS analyses revealed that epoxy coating containing silane-modified chitin exhibited lowest water absorption and highest barrier as well as anti-corrosion performances. The QCC showed that quantum parameters for the coating containing silane-modified chitin are optimum and therefore corresponds to high corrosion protection. The high negative value of adsorption energies (Eads) for the coating containing silane-modified chitin indicates the coating molecules interacted and adsorbed strongly on the steel surface. The observed results have shown that silane-modified epoxy-chitin coating would perform satisfactorily for surface protection of metal structures in saline environment.

Keywords: chitin, EIS, epoxy coating, hydrophobic, molecular dynamics simulation, quantum chemical computation

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Authors: Hamad R. Jappor, Zeyad Adnan Saleh, Mudar A. Abdulsattar

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The ab initio restricted Hartree-Fock method is used to simulate the electronic structure of indium phosphide (InP) nanocrystals (NCs) (216-738 atoms) with sizes ranging up to about 2.5 nm in diameter. The calculations are divided into two parts, surface, and core. The oxygenated (001)-(1×1) facet that expands with larger sizes of nanocrystals is investigated to determine the rule of the surface in nanocrystals electronic structure. Results show that lattice constant and ionicity of the core part show decreasing order as nanocrystals grow up in size. The smallest investigated nanocrystal is 1.6% larger in lattice constant and 131.05% larger in ionicity than the converged value of largest investigated nanocrystal. Increasing nanocrystals size also resulted in an increase of core cohesive energy (absolute value), increase of core energy gap, and increase of core valence. The surface states are found mostly non-degenerated because of the effect of surface discontinuity and oxygen atoms. Valence bandwidth is wider on the surface due to splitting and oxygen atoms. The method also shows fluctuations in the converged energy gap, valence bandwidth and cohesive energy of core part of nanocrystals duo to shape variation. The present work suggests the addition of ionicity and lattice constant to the quantities that are affected by quantum confinement phenomenon. The method of the present model has threefold results; it can be used to approach the electronic structure of crystals bulk, surface, and nanocrystals.

Keywords: InP, nanocrystals core, ionicity, Hartree-Fock method, large unit cell

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Authors: Z. V. P. Murthy, Preeti Arunachalam, Sangeeta Balram

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Removal of metal ions from different wastewaters has become important due to their effects on living beings. Cadmium is one of the heavy metals found in different industrial wastewaters. There are many conventional methods available to remove heavy metals from wastewaters like adsorption, membrane separations, precipitation, electrolytic methods, etc. and all of them have their own advantages and disadvantages. The present work deals with the use of natural biosorbents (chitin and chitosan) to separate cadmium ions from aqueous solutions. The adsorption data were fitted with different isotherms and kinetics models. Amongst different adsorption isotherms used to fit the adsorption data, the Freundlich isotherm showed better fits for both the biosorbents. The kinetics data of adsorption of cadmium showed better fit with pseudo-second order model for both the biosorbents. Chitosan, the derivative from chitin, showed better performance than chitin. The separation results are encouraging.

Keywords: chitin, chitosan, cadmium, isotherm, kinetics

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Authors: Reshma Jolly, Mohammad Shakir, Mohammad Shoeb Khan, Noor E. Iram

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A nanocomposite system integrating hydroxyapatite, chitin and starch (n-HA/CT/ST) has been synthesized via co-precipitation approach at room temperature, addressing the issues of biocompatibility, mechanical strength and cytotoxicity required for Bone tissue engineering. The interactions, crystallite size and surface morphology against n-HA/CT (nano-hydroxyapatite/chitin) nanocomposite have been obtained by correlating and comparing the results of FTIR, SEM, TEM and XRD. The comparative study of the bioactivity of n-HA/CT and n-HA/CT/ST nanocomposites revealed that the incorporation of starch as templating agent improved these properties in n-HA/CT/ST nanocomposite. The rise in thermal stability in n-HA/CT/ST nanocomposite as compared to n-HA/CT has been observed by comparing the TGA results. The comparison of SEM images of both the scaffolds indicated that the addition of ST influenced the surface morphology of n-HA/CT scaffold which appeared to be rougher and porous. The MTT assay on murine fibroblast L929 cells and in-vitro bioactivity of n-HA/CT/ST matrix referred superior non-toxic property of n-HA/CT/ST nanocomposite and higher possibility of osteo-integration in-vivo, respectively.

Keywords: bioactive, chitin, hyroxyapatite, nanocomposite

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Authors: Tsutomu Iwayama, Takayuki Hama

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Si ion implantation was widely used to synthesize specimens of SiO2 containing supersaturated Si and subsequent high temperature annealing induces the formation of embedded luminescent Si nanocrystals. In this work, the potentialities of excimer UV-light (172 nm, 7.2 eV) irradiation and rapid thermal annealing (RTA) to enhance the photoluminescence and to achieve low temperature formation of Si nanocrystals have been investigated. The Si ions were introduced at acceleration energy of 180 keV to fluence of 7.5 x 1016 ions/cm2. The implanted samples were subsequently irradiated with an excimer-UV lamp. After the process, the samples were rapidly thermal annealed before furnace annealing (FA). Photoluminescence spectra were measured at various stages at the process. We found that the luminescence intensity is strongly enhanced with excimer-UV irradiation and RTA. Moreover, effective visible photoluminescence is found to be observed even after FA at 900 oC, only for specimens treated with excimer-UV lamp and RTA. We also prepared specimens of Si nanocrystals embedded in a SiO2 by reactive pulsed laser deposition (PLD) in an oxygen atmosphere. We will make clear the similarities and differences with the way of preparation.

Keywords: Ion implantation, photoluminescence, pulsed laser deposition, rapid thermal anneal, Si nanocrystals

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Authors: Farramae Francisco, Rhoda Mae Simora, Sharon Nunal

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Deproteination and demineralization efficiencies of shrimp waste using two Lactobacillus species treated with different carbohydrate sources for chitin production, its chemical conversion to chitosan and the quality of chitin and chitosan produced were determined. Using 5% glucose and 5% cassava starch as carbohydrate sources, pH slightly increased from the initial pH of 6.0 to 6.8 and 7.2, respectively after 24 h and maintained their pH at 6.7 to 7.3 throughout the treatment period. Demineralization (%) in 5 % glucose and 5 % cassava was highest during the first day of treatment which was 82% and 83%, respectively. Deproteination (%) was highest in 5% cassava starch on the 3rd day of treatment at 84.4%. The obtained chitin from 5% cassava and 5% glucose had a residual ash and protein below 1% and solubility of 59% and 44.3%, respectively. Chitosan produced from 5% cassava and 5% glucose had protein content below 0.05%; residual ash was 1.1% and 0.8%, respectively. Chitosan solubility and degree of deacetylation were 56% and 33% in 5% glucose and 48% and 29% in 5% cassava, respectively. The advantage this alternative technology offers over that of chemical extraction is large reduction in chemicals needed thus less effluent production and generation of a protein-rich liquor, although the demineralization process should be improved to achieve greater degree of deacetylation.

Keywords: alternative carbon source, bioprocessing, lactic acid bacteria, waste utilization

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Authors: Marivane Turim Koschevic, Maycon dos Santos, Marcello Lima Bertuci, Farayde Matta Fakhouri, Silvia Maria Martelli

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Natural fibers are rich raw materials in cellulose and abundant in the world, its use for the cellulose nanocrystals extraction is promising as an example cited is the cattail, macrophyte native weed in South America. This study deals with the pre-treatment cattail of crushed fibers, at six different methods of mercerization, followed by the use of bleaching. As a result, have found The positive effects of treating fibers by means of optical microscopy and spectroscopy, Fourier transform (FTIR). The sample selected for future testing of cellulose nanocrystals extraction was treated in 2.5% NaOH for 2 h, 60 °C in the first stage and 30vol H2O2, NaOH 5% in the proportion 30/70% (v/v) for 1 hour 60 °C, followed by treatment at 50/50% (v/v) 15 minutes, 50°C, with the same constituents of the solution.

Keywords: cellulose nanocrystal, chemical treatment, mercerization, natural fibers

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Authors: R. Karmouch

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A thin gold metal layer was deposited on the top of silicon oxide films containing embedded Si nanocrystals (Si-nc). The sample was annealed in gas containing nitrogen, and subsequently characterized by photoluminescence. We obtained 3-fold enhancement of photon emission from the Si-nc embedded in silicon dioxide covered with a Gold layer as compared with an uncovered sample. We attribute this enhancement to the increase of the spontaneous emission rate caused by the coupling of the Si-nc emitters with the surface plasmons (SP). The evolution of PL emission with laser irradiated time was also collected from covered samples, and compared to that from uncovered samples. In an uncovered sample, the PL intensity decreases with time, approximately with two decay constants. Although the decrease of the initial PL intensity associated with the increase of sample temperature under CW pumping is still observed in samples covered with a gold layer, this film significantly contributes to reduce the permanent deterioration of the PL intensity. The resistance to degradation of light-emitting silicon nanocrystals can be increased by SP coupling to suppress the permanent deterioration. Controlling the permanent photodeterioration can allow to perform a reliable optical gain measurement.

Keywords: photodeterioration, silicon nanocrystals, ion implantation, photoluminescence, surface plasmons

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Authors: Lopamudra Ray, Malla Padma, Dibya Bhol, Samir Ranjan Mishra, A. N. Panda, Gurdeep Rastogi, T. K. Adhya, Ajit Kumar Pattnaik, Mrutyunjay Suar, Vishakha Raina

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Chilika Lake is the largest coastal estuarine brackish water lagoon in Asia situated on the east coast of India and is a designated Ramsar site. In the current study, several chitinolytic microorganisms were isolated and screened by appearance of clearance zone on 0.5% colloidal chitin agar plate. A strain designated as RC 1830 displayed maximum colloidal chitin degradation by release of 112 μmol/ml/min of N-acetyl D-glucosamine (GlcNAc) in 48h. The strain was taxonomically identified by polyphasic approach based on a range of phenotypic and genotypic properties and was found to be a novel species named Streptomyces chilikensis RC1830. The organism was halophilic (12% NaCl w/v), alkalophilic (pH10) and was capable of hydrolyzing chitin, starch, cellulose, gelatin, casein, tributyrin and tween 80. The partial purification of chitinase enzymes from RC1830 was performed by DEAE Sephacel anion exchange chromatography which revealed the presence of a very low molecular weight chitinase(10.5kD) which may be a probable chitobiosidase enzyme. The study reports the presence of a low MW chitinase (10.5kD) and a chitin decaetylase from a novel Streptomyces strain RC1830 isolated from Chilika Lake. Previously chitinases less than 20.5kD have not been reported from any other Streptomyces species. The enzymes was characterized with respect to optimum pH, temperature, and substrate specificity and temperature stability.

Keywords: chitinases, chitobiosidase, Chilika Lake, India

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Authors: Mohammad Shakir, Reshma Jolly, Mohammad Shoeb Khan, Noor-E-Iram

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A nanocomposite system incorporating dextrin into nano-hydroxyapatite/chitin matrix (n-HA/DX/CT) has been successfully synthesized via co-precipitation route at room temperature for the application in bone tissue engineering by investigating biocompatibility, cytotoxicity and mechanical properties. The FTIR spectra of n-HA/DX/CT nanocomposite indicated a considerable intermolecular interaction between the various components of the system. The results of XRD, TEM and TGA/DTA revealed that the crystallinity, size and thermal stability of the n-HA/DX/CT scaffold has decreased and increased respectively. The result of SEM image of the n-HA/DX/CT scaffold indicated that the incorporation of dextrin affected the surface morphology while considerable in-vitro bioactivity has been observed in n-HA/DX/CT based on SBF study, referring a step towards possibility of making direct bond to living bone if implanted. Moreover, MTT assay suggested the non-toxic nature of n-HA/DX/CT to murine fibroblast L929 cells. The swelling study of n-HA/DX/CT scaffold indicated the low swelling rate for n-HADX/CT. All these results have paved the way for n-HA/DX/CT to be used as a competent material for bone tissue engineering.

Keywords: autograft, chitin, dextrin, nanocomposite

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Authors: Savita, Pargam Vashishtha, Govind Gupta, Ankush Vij, Anup Thakur

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The ligand field dependent visible as well as NIR emission of the Cr³+dopant in spinel hosts has attracted immense attention in tuning the color emitted by the material. In this research, Mg1-xCrxAl₂O₄(x=0.5, 1, 3, 5, and 10 mol%) nanocrystals have been synthesizedby solution combustion method. The synthesized nanocrystals possessed a single phase cubic structure. The strong absorption by host lattice defects (antisite defects, F centres) andd-d transitions of Cr³+ ions lead to radiative emission in the visible and NIR region, respectively. The red-NIR emission in photoluminescence spectra inferred the octahedral symmetry of Cr³+ ions and anticipated the site distortion by the presence ofCr³+ clusters and antisite defects in the vicinity of Cr³+ ions. The thermoluminescence response of UV and γ-irradiated Cr doped MgAl2O4 samples revealed the formation of various shallow and deep defects with doping Cr³+ions. The induced structural cation disorder with an increase in doping concentration caused photoluminescence quenching beyond 3 mol% Cr³+ doping. The color tuning exhibited by Cr doped MgAl₂O₄ nanocrystals by varying Cr³+ ion concentration and excitation wavelength find its applicability in solid state lighting.

Keywords: antisite defects, cation disorder, color tuning, combustion synthesis

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Authors: Riya Bose, Ashok Bera, Manas R. Parida, Anirudhha Adhikari, Basamat S. Shaheen, Erkki Alarousu, Jingya Sun, Tom Wu, Osman M. Bakr, Omar F. Mohammed

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This work reports visualization of charge carrier dynamics on the surface of copper indium gallium selenide (CIGSe) nanocrystals in real space and time using four-dimensional scanning ultrafast electron microscopy (4D S-UEM) and correlates it with the optoelectronic properties of the nanocrystals. The surface of the nanocrystals plays a key role in controlling their applicability for light emitting and light harvesting purposes. Typically for quaternary systems like CIGSe, which have many desirable attributes to be used for optoelectronic applications, relative abundance of surface trap states acting as non-radiative recombination centre for charge carriers remains as a major bottleneck preventing further advancements and commercial exploitation of these nanocrystals devices. Though ultrafast spectroscopic techniques allow determining the presence of picosecond carrier trapping channels, because of relative larger penetration depth of the laser beam, only information mainly from the bulk of the nanocrystals is obtained. Selective mapping of such ultrafast dynamical processes on the surfaces of nanocrystals remains as a key challenge, so far out of reach of purely optical probing time-resolved laser techniques. In S-UEM, the optical pulse generated from a femtosecond (fs) laser system is used to generate electron packets from the tip of the scanning electron microscope, instead of the continuous electron beam used in the conventional setup. This pulse is synchronized with another optical excitation pulse that initiates carrier dynamics in the sample. The principle of S-UEM is to detect the secondary electrons (SEs) generated in the sample, which is emitted from the first few nanometers of the top surface. Constructed at different time delays between the optical and electron pulses, these SE images give direct and precise information about the carrier dynamics on the surface of the material of interest. In this work, we report selective mapping of surface dynamics in real space and time of CIGSe nanocrystals applying 4D S-UEM. We show that the trap states can be considerably passivated by ZnS shelling of the nanocrystals, and the carrier dynamics can be significantly slowed down. We also compared and discussed the S-UEM kinetics with the carrier dynamics obtained from conventional ultrafast time-resolved techniques. Additionally, a direct effect of the state trap removal can be observed in the enhanced photoresponse of the nanocrystals after shelling. Direct observation of surface dynamics will not only provide a profound understanding of the photo-physical mechanisms on nanocrystals’ surfaces but also enable to unlock their full potential for light emitting and harvesting applications.

Keywords: 4D scanning ultrafast microscopy, charge carrier dynamics, nanocrystals, optoelectronics, surface passivation, trap states

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Authors: Asiya Rezzouq, Mehdi El Bouchti, Omar Cherkaoui, Sanaa Majid, Souad Zyade

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In recent years, there has been a steady increase in the exploration of new renewable and non-conventional sources for the production of biodegradable nanomaterials. Nature harbours valuable cellulose-rich materials that have so far been under-exploited and can be used to create cellulose derivatives such as cellulose microfibres (CMFs) and cellulose nanocrystals (CNCs). These unconventional sources have considerable potential as alternatives to conventional sources such as wood and cotton. By using agricultural waste to produce these cellulose derivatives, we are responding to the global call for sustainable solutions to environmental and economic challenges. Responsible management of agricultural waste is increasingly crucial to reducing the environmental consequences of its disposal, including soil and water pollution, while making efficient use of these untapped resources. In this study, the main objective was to extract cellulose nanocrystals (CNC) from melon plant residues using methods that are both efficient and sustainable. To achieve this high-quality extraction, we followed a well-defined protocol involving several key steps: pre-treatment of the residues by grinding, filtration and chemical purification to obtain high-quality (CMF) with a yield of 52% relative to the initial mass of the melon plant residue. Acid hydrolysis was then carried out using phosphoric acid and sulphuric acid to convert (CMF) into cellulose nanocrystals. The extracted cellulose nanocrystals were subjected to in-depth characterization using advanced techniques such as transmission electron microscopy (TEM), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction. The resulting cellulose nanocrystals have exceptional properties, including a large specific surface area, high thermal stability and high mechanical strength, making them suitable for a variety of applications, including as reinforcements for composite materials. In summary, the study highlights the potential for recovering agricultural melon waste to produce high-quality cellulose nanocrystals with promising applications in industry, nanotechnology, and biotechnology, thereby contributing to environmental and economic sustainability.

Keywords: cellulose, melon plant residues, cellulose nanocrystals, properties, applications, composite materials

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Authors: Hinda Berghiche, Hamida Benradia, Noureddine Soltani

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Pesticides are widely used in crop production and are known to induce a major contamination of ecosystems especially in aquatic environments. The leaching of a large amount of pollutants derived from agricultural activities (fertilizers, pesticides) might contaminate rivers which diverse into the likes and estuarine and coastal environments affecting several organisms such as crustacean species. In this context, there is searched for new selective insecticides with minimal toxic effects on the environment and human health such as growth insect regulators (GIRs). The current study aimed to examine the impact of novaluron (CE 20%), a potent benzoylphenylurea derivative insecticide on mosquito larvae, against non-target shrimp, Palaemon adspersus (Decapoda, Palaemonidae). The compound was tested at two concentrations (0.91 mg/L and 4.30 mg/L) corresponding respectively to the LC50 and LC90 determined against fourth-instar larvae of Culiseta longiareolata (Diptera, Culicidae). The molting hormone titer was determined in the haemolymph by an enzyme-immunoassay, while chitin was measured in peripheral integument at different stages during the molting cycle. Under normal conditions, the haemolymphatic ecdysteroid concentrations increased during the molting cycle to reach peak at stage D. In the treated series, we note absence of the peak at stage D and an increase at stages B, C and D as compared to the controls. Concerning the chitin amounts, we observe an increase from stage A to stage C followed by a decrease at stage D. Exposition of shrimps to novaluron resulted in a significant decrease of values at all molting stages with a dose-response effect. Thus, the insecticide can present secondary effects on this non-target arthropod species.

Keywords: toxicology, novaluron, crustacean, palaemon adspersus, ecdysteroids, cuticle, chitin

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Authors: Laribi-Habchi Hasiba, Bouanane-Darenfed Amel, Drouiche Nadjib, Pausse André, Mameri Nabil

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Chitin, a linear 1, 4-linked N-acetyl-d-glucosamine (GlcNAc) polysaccharide is the major structural component of fungal cell walls, insect exoskeletons and shells of crustaceans. It is one of the most abundant naturally occurring polysaccharides and has attracted tremendous attention in the fields of agriculture, pharmacology and biotechnology. Each year, a vast amount of chitin waste is released from the aquatic food industry, where crustaceans (prawn, crab, Shrimp and lobster) constitute one of the main agricultural products. This creates a serious environmental problem. This linear polymer can be hydrolyzed by bases, acids or enzymes such as chitinase. In this context an extracellular chitinase (ChiA-65) was produced and purified from a newly isolated LHH100. Pure protein was obtained after heat treatment and ammonium sulphate precipitation followed by Sephacryl S-200 chromatography. Based on matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-TOF/MS) analysis, the purified enzyme is a monomer with a molecular mass of 65,195.13 Da. The sequence of the 27 N-terminal residues of the mature ChiA-65 showed high homology with family-18 chitinases. Optimal activity was achieved at pH 4 and 75◦C. Among the inhibitors and metals tested p-chloromercuribenzoic acid, N-ethylmaleimide, Hg2+ and Hg + completelyinhibited enzyme activity. Chitinase activity was high on colloidal chitin, glycol chitin, glycol chitosane, chitotriose and chitooligosaccharide. Chitinase activity towards synthetic substrates in the order of p-NP-(GlcNAc) n (n = 2–4) was p-NP-(GlcNAc)2> p-NP-(GlcNAc)4> p-NP-(GlcNAc)3. Our results suggest that ChiA-65 preferentially hydrolyzed the second glycosidic link from the non-reducing end of (GlcNAc) n. ChiA-65 obeyed Michaelis Menten kinetics the Km and kcat values being 0.385 mg, colloidal chitin/ml and5000 s−1, respectively. ChiA-65 exhibited remarkable biochemical properties suggesting that this enzyme is suitable for bioconversion of chitin waste.

Keywords: Bacillus licheniformis LHH100, characterization, extracellular chitinase, purification

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Authors: J. Mrazek, R. Skala, S. Bysakh, Ivan Kasik

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Lanthanide-doped yttrium titanium oxides, which crystallize in a pyrochlore structure with general formula (RExY1-x)2Ti2O7 (RE=rare earth element), have been extensively investigated in recent years for their interesting physical and chemical properties. Despite that the pure pyrochlore structure does not present luminescence ability, the presence of yttrium ions in the pyrochlore structure significantly improves the luminescence properties of the RE. Moreover, the luminescence properties of pyrochlores strongly depend on the size of formed nanocrystals. In this contribution, we present a versatile sol-gel synthesis of nanocrystalline EuYTi2O7pyrochlore. The nanocrystalline powders and thin films were prepared by the condensation of titanium(IV)butoxide with europium(III) chloride followed by the calcination. The introduced method leads to the formation of the highly-homogenous nanocrystalline EuYTi2O7 with tailored grain size ranging from 20 nm to 200 nm. The morphology and the structure of the formed nanocrystals are linked to the luminescence properties of Eu3+ ions incorporated into the pyrochlore lattice. The results of XRD and HRTEM analysis show that the Eu3+ and Y3+ ions are regularly distributed inside the lattice. The lifetime of Eu3+ ions in calcinated powders is regularly decreasing from 140 us to 68 us and the refractive index of prepared thin films regularly increases from 2.0 to 2.45 according to the calcination temperature. The shape of the luminescence spectra and the decrease of the lifetime correspond with the crystallinity of prepared powders. The results present fundamental information about the effect of the size of the nanocrystals to their luminescence properties. The promising application of prepared nanocrystals in the field of lasers and planar optical amplifiers is widely discussed in the contribution.

Keywords: europium, luminescence, nanocrystals, sol-gel

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Authors: Mehrnaz Mostafavi

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Perovskite nanocrystals and quantum dots have emerged as leaders in the field of photovoltaic technologies, demonstrating exceptional light-harvesting abilities and stability. This study investigates the substantial progress and potential of these nano-sized materials in transforming solar energy conversion. The research delves into the foundational characteristics and production methods of perovskite nanocrystals and quantum dots, elucidating their distinct optical and electronic properties that render them well-suited for photovoltaic applications. Specifically, it examines their outstanding light absorption capabilities, enabling more effective utilization of a wider solar spectrum compared to traditional silicon-based solar cells. Furthermore, this paper explores the improved durability achieved in perovskite nanocrystals and quantum dots, overcoming previous challenges related to degradation and inconsistent performance. Recent advancements in material engineering and techniques for surface passivation have significantly contributed to enhancing the long-term stability of these nanomaterials, making them more commercially feasible for solar cell usage. The study also delves into the advancements in device designs that incorporate perovskite nanocrystals and quantum dots. Innovative strategies, such as tandem solar cells and hybrid structures integrating these nanomaterials with conventional photovoltaic technologies, are discussed. These approaches highlight synergistic effects that boost efficiency and performance. Additionally, this paper addresses ongoing challenges and research endeavors aimed at further improving the efficiency, stability, and scalability of perovskite nanocrystals and quantum dots in photovoltaics. Efforts to mitigate concerns related to material degradation, toxicity, and large-scale production are actively pursued, paving the way for broader commercial application. In conclusion, this paper emphasizes the significant role played by perovskite nanocrystals and quantum dots in advancing photovoltaic technologies. Their exceptional light-harvesting capabilities, combined with increased stability, promise a bright future for next-generation solar cells, ushering in an era of highly efficient and cost-effective solar energy conversion systems.

Keywords: perovskite nanocrystals, quantum dots, photovoltaic technologies, light-harvesting, solar energy conversion, stability, device designs

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Authors: Dolly Gadhiya, Jayvadan Patel, Mihir Raval

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Lercanidipine hydrochloride is a calcium channel blockers used for treating angina pectoris and hypertension. Lercanidipine is a BCS Class II drug having poor aqueous solubility. Absolute bioavailability of Lercanidipine is very low and the main reason ascribed for this is poor aqueous solubility of the drug. Design and formulatation of nanocrystals by media milling method was main focus of this study. In this present study preliminary optimization was carried out with one factor at a time (OFAT) approach. For this different parameters like size of milling beads, amount of zirconium beads, types of stabilizer, concentrations of stabilizer, concentrations of drug, stirring speeds and milling time were optimized on the basis of particle size, polydispersity index and zeta potential. From the OFAT model different levels for above parameters selected for Plackett - Burman Design (PBD). Plackett-Burman design having 13 runs involving 6 independent variables was carried out at higher and lower level. Based on statistical analysis of PBD it was found that concentration of stabilizer, concentration of drug and stirring speed have significant impact on particle size, PDI, zeta potential value and saturation solubility. These experimental designs for preparation of nanocrystals were applied successfully which shows increase in aqueous solubility and dissolution rate of Lercanidipine hydrochloride.

Keywords: Lercanidipine hydrochloride, nanocrystals, OFAT, Plackett Burman

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Authors: Rahul Warmoota, Aditya Bhardwaj, Steffy Angural, Monika Rana, Sunena Jassal, Neena Puri, Naveen Gupta

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Seafood processing generates large volumes of waste products such as skin, heads, tails, shells, scales, backbones, etc. Pollution due to conventional methods of seafood waste disposal causes negative implications on the environment, aquatic life, and human health. Moreover, these waste products can be used for the production of high-value products which are still untapped due to inappropriate management. Paenibacillus sp. AD is known to act on chitinolytic and proteinaceous waste and was explored for its potential to degrade various types of seafood waste in solid-state fermentation. Effective degradation of seafood waste generated from a variety of sources such as fish scales, crab shells, prawn shells, and a mixture of such wastes was observed. 30 to 40 percent degradation in terms of decrease in the mass was achieved. Along with the degradation, chitinolytic and proteolytic enzymes were produced, which can have various biotechnological applications. Apart from this, value-added products such as chitin oligosaccharides and peptides of various degrees of polymerization were also produced, which can be used for various therapeutic purposes. Results indicated that Paenibacillus sp. AD can be used for the development of a process for the infield degradation of seafood waste.

Keywords: chitin, chitin-oligosaccharides, chitinase, protease, biodegradation, crab shells, prawn shells, fish scales

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Authors: Khamael M. Abualnaja, Lidija Šiller, Benjamin R. Horrocks

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Alkylated silicon nanocrystals (C11-SiNCs) were prepared successfully by galvanostatic etching of p-Si(100) wafers followed by a thermal hydrosilation reaction of 1-undecene in refluxing toluene in order to extract C11-SiNCs from porous silicon. Erbium trichloride was added to alkylated SiNCs using a simple mixing chemical route. To the best of our knowledge, this is the first investigation on mixing SiNCs with erbium ions (III) by this chemical method. The chemical characterization of C11-SiNCs and their mixtures with Er3+ (Er/C11-SiNCs) were carried out using X-ray photoemission spectroscopy (XPS). The optical properties of C11-SiNCs and their mixtures with Er3+ were investigated using Raman spectroscopy and photoluminescence (PL). The erbium-mixed alkylated SiNCs shows an orange PL emission peak at around 595 nm that originates from radiative recombination of Si. Er/C11-SiNCs mixture also exhibits a weak PL emission peak at 1536 nm that originates from the intra-4f transition in erbium ions (Er3+). The PL peak of Si in Er/C11-SiNCs mixture is increased in the intensity up to three times as compared to pure C11-SiNCs. The collected data suggest that this chemical mixing route leads instead to a transfer of energy from erbium ions to alkylated SiNCs.

Keywords: photoluminescence, silicon nanocrystals, erbium, Raman spectroscopy

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Authors: Tao Qu, Chandra Prakash, Vikas Tomar

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The interfaces between organic and inorganic phases in natural materials have been shown to be a key factor contributing to their high performance. This work analyzes crack propagation in a 2-ply laminate subjected to uniaxial tensile mode-I crack propagation loading that has laminate properties derived based on biological material constituents (marine exoskeleton- chitin and calcite). Interfaces in such laminates are explicitly modeled based on earlier molecular simulations performed by authors. Extended finite element method and cohesive zone modeling based simulations coupled with theoretical analysis are used to analyze crack propagation. Analyses explicitly quantify the effect that interface mechanical property variation has on the delamination as well as the transverse crack propagation in examined 2-ply laminates.

Keywords: chitin, composites, interfaces, fracture

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Authors: Laslouni Warda, M. Azzaz

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The intermetallic-based on transition metal compounds present interesting magnetic properties for the technological applications (permanent magnets, magnetic recording…). Cu70 Fe18Co12 and Cu70 Fe30 nanostructured with crystallite size vary from 10 a 12 nanometers have been developed by a mechanical milling method. For Cu-Fe samples, the iron and copper distribution was clear. The distribution showed a homogeneous distribution of iron and copper in a Cu-Fe obtained after 36 h milling. The structural properties have been performed with X-ray diffraction. With increasing milling times, Fe and Co diffuse into the Cu matrix, which accelerates the formation of the magnetic nanostructure Cu- Fe-Co and Cu-Fe alloys. The magnetic behavior is investigated using Vibrating Sample Magnetometer (VSM). The two alloys nanocrystals possess ferromagnetic character at room temperature

Keywords: Cu-Fe-Co, Cu-Fe, nanocrystals, SEM, hysteresis loops, VSM, anisotropy theory

Procedia PDF Downloads 332