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Human health and the environment are negatively affected by endocrine-disrupting chemicals (EDCs), such as bisphenol A. Therefore, developing appropriate remediation methods is essential for efficiently removing phenolic compounds from aqueous solutions. Enzymatic biodegradation is a potential biotechnological approach for responsibly addressing water pollution. With its high catalytic efficiency and few by-products, laccase is an eco-friendly biocatalyst with significant promise for biodegradation. Herein, two novel supporting materials (NH2-PMMA and NH2-PMMA-Gr) were fabricated via the functionalization of poly(methylmethacrylate) (PMMA) polymer using ethylenediamine and reinforced with graphene followed by glutaraldehyde activation. NH2-PMMA and NH2-PMMA-Gr were utilized for laccase immobilization with an immobilization yield (IY%) of 78.3% and 82.5% and an activity yield (AY%) of 81.2% and 85.9%, respectively. Scanning electron microscope (SEM) and Fourier-transform infrared (FTIR) were used to study the characteristics of fabricated material supports. NH2-PMMA-Gr@laccase exhibited an optimal pH profile from 4.5 to 5.0, while NH2-PMMA@laccase exhibited optimum pH at 5.0 compared to a value of 4.0 for free form. A wider temperature ranges of 40-50 °C was noted for both immobilized laccases compared to a value of 40 °C for the free form. Additionally, it was reported that immobilized laccase outperformed free laccase in terms of substrate affinity and storage stability. NH2-PMMA@laccase and NH2-PMMA-Gr@laccase improved stability by up to 3.9 and 4.6-fold when stored for 30 days at 4 °C and preserved up to 80.5% and 86.7% of relative activity after ten cycles of reuse. Finally, the degradation of BPA was achieved using NH2-PMMA@laccase and NH2-PMMA-Gr@laccase. After five cycles, NH2-PMMA@laccase and NH2-PMMA-Gr@laccase showed that the residual degradation of BPA was 77% and 84.5% using 50 µm of BPA. This study introduces a novel, high-performance material for organic pollution remediation in wastewater that would inspire further progress.
Assuntos
Grafite , Nanoestruturas , Humanos , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Lacase/química , Lacase/metabolismo , Polimetil Metacrilato , Concentração de Íons de HidrogênioRESUMO
A sensitive and selective phenothiazine-based sensor (PTZ) has been successfully synthesized. The sensor PTZ displayed specific identification of CN- 'turn-off' fluorescence responses with a quick reaction and strong reversibility in an acetonitrile:water (90:10, V/V) solution. The sensor PTZ for detecting CN- exhibits the marked advantages of quenching the fluorescence intensity, fast response time (60 s), and low value of the detection limit. The concentration that is authorized for drinking water by the WHO (1.9 µM) is far higher than the detection limit, which was found to be 9.11 × 10-9 . The sensor displays distinct colorimetric and spectrofluorometric detection for CN- anion due to the addition of CN- anion to the electron-deficient vinyl group of PTZ, which reduces intramolecular charge transfer efficiencies. The 1:2 binding mechanism of PTZ with CN- was validated by fluorescence titration, Job's plot, HRMS, 1 H NMR, FTIR analysis, and density functional theory (DFT) investigations, among other methods. Additionally, the PTZ sensor was successfully used to precisely and accurately detect cyanide anions in actual water samples.
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Cianetos , Água Potável , Cianetos/química , Ânions/química , Água Potável/análise , Espectrofotometria , Colorimetria/métodosRESUMO
Lipases are extensively utilized industrial biocatalysts that play an important role in various industrial and biotechnological applications. Herein, polyacrylonitrile (PAN) was treated with hexamethylene diamine (HMDA) and activated by glutaraldehyde, then utilized as a carrier support for Candida rugosa lipase. In this regard, the morphological structure of modified PAN before and after the immobilization process was evaluated using FTIR and SEM analyses. The immobilized lipase exhibited the highest activity at pH 8.0, with an immobilization yield of 81% and an activity of 91%. The optimal pH and temperature for free lipase were 7.5 and 40 °C, while the immobilized lipase exhibited its optimal activity at a pH of 8.0 and a temperature of 50 °C. After recycling 10 times, the immobilized lipase maintained 76% of its activity and, after 15 reuses, it preserved 61% of its activity. The lipase stability was significantly improved after immobilization, as it maintained 76% of its initial activity after 60 days of storage. The calculated Km values were 4.07 and 6.16 mM for free and immobilized lipase, and the Vmax values were 74 and 77 µmol/mL/min, respectively. These results demonstrated that synthetically modified PAN is appropriate for immobilizing enzymes and has the potential for commercial applications.
Assuntos
Enzimas Imobilizadas , Lipase , Lipase/metabolismo , Enzimas Imobilizadas/química , Estabilidade Enzimática , Candida , Temperatura , Concentração de Íons de HidrogênioRESUMO
To explore high efficiency dye-sensitized solar cells (DSSCs), two experimentally derived (single fence and double fence porphyrins) and two theoretically designed zinc porphyrin molecules with D-D-π-A-A configurations were studied. Density functional theory and time-dependent density functional theory were employed to simulate these two experimental dyes and dye@TiO2 systems to understand why the double fence porphyrin molecule exhibits better photovoltaic performance than the single fence porphyrin molecule. For the short-circuit current (JSC), the various parameters that affected the experimental magnitude of JSC were analyzed from different aspects of absorption, charge transfer and chemical parameters as well as an electron injection process. The almost equal open-circuit voltages (VOC) in the experiment were predicted by theoretical VOC calculations. Our model predicted power conversion efficiencies (PCEs) of 1.993% and 10.866% for the single and double fence molecules, respectively, which are in accordance with the experimental values of 3.48% and 10.69%, respectively. In addition, one designed two new molecules based on the double fence porphyrin molecule with a 2-methyl-2H-benzo[d][1,2,3]triazole (BTA) unit bearing one fluorine and two fluorine atoms as the guest acceptor, respectively. Compared to the original molecules, the engineered molecules significantly improved the photovoltaic parameters, JSC and VOC, thereby causing excellent PCEs. The most outstanding designed molecule reached a PCE of 12.155%, and is considered a candidate dye for high-efficiency DSSC. This study provides insights into the photoelectric properties of single and double fence porphyrins. It also demonstrated that the strong electron-withdrawing ability of fluorine atoms would enhance the photovoltaic performance and provide a guideline for the further design of double fence porphyrins.
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A new typical phenothiazine compound functionalized with thienyl-indandione derivative (PTZTID) was synthesized and characterized using spectral analysis (ultraviolet-visible (UV-vis) light, infrared (IR), 1 H nuclear magnetic resonance (NMR) and 13 C NMR tools). The UV-vis absorption spectra of the PTZTID solution in 1,4-dioxane showed two absorption bands attributed to localized aromatic π-π* transitions of conjugated aromatic moieties and intramolecular charge transfer with the characteristics of a π-π* transition. The fluorescence spectra exhibited a maximum emission wavelength at 580 nm. The effect of concentration on photophysical properties took the form of a minor hypsochromic shift, which was attributed to some extent to the occurrence of H-type aggregation of the PTZTID derivative. Binary solvent effects on the spectroscopic behaviour of PTZTID were measured at different H2 O/1,4-dioxane ratios. Similarly, when increasing the water content, a hypsochromic shift was observed that resulted from H-type aggregation. Furthermore, geometry and electronic configurations of PTZTID were studied at density functional theory /B3LYP level and indicated that the compound had a nonplanar (butterfly structure).
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Corantes Fluorescentes/química , Indanos/química , Fenotiazinas/química , Teoria da Densidade Funcional , Corantes Fluorescentes/síntese química , Estrutura Molecular , Fenotiazinas/síntese química , Processos Fotoquímicos , Espectrometria de FluorescênciaRESUMO
A novel phenothiazine derivative conjugated with vinylcyclohexenyl-malononitrile (PTZ-CDN) was synthesized through the Knoevenagel reaction of 10-octyl-10H-phenothiazine-3,7-dicarbaldehyde with 2-(3,5,5-trimethylcyclohex-2-en-1-ylidene)-malononitrile and fully characterized. The UV-vis absorption spectra of PTZ-CDN in different solvents showed a λmax band at 497-531 nm with a high molar extinction coefficient attributed to intramolecular charge transfer (ICT) with the characteristics of a π-π* transition. Increasing the solvent polarity resulted in a bathochromic shift of λmax . The PTZ-CDN fluorescence emission spectra were more sensitive to increasing the solvent polarity than the absorption spectra; they displayed a blue shift of λem by 85 nm. To understand the behaviour of the PTZ-CDN derivative, Stokes' shift ( Δ ν ¯ ) with respect to the solvent polarity, Lippert-Mataga and linear solvation-energy relationship (LSER) models were applied in which the LSER showed better regression than the Lippert-Mataga plots (r2 = 0.9627). Finally, the TD-density functional theory (DFT) electronic transition spectra in dioxane and dimethyl formamide (DMF) were calculated. The DFT data showed that λmax resulted from the support of the highest occupied molecular orbital to the lowest unoccupied molecular orbital transition with 74% and 99% in dioxane and DMF, respectively.
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Nitrilas , Fenotiazinas , Teoria da Densidade Funcional , SolventesRESUMO
Based on reported results for the potential medicinal impact of phenothiazine core, as well as the chalcone skeleton that is widely present in many natural products, together with their reported bioactivities, the present work was aimed at combining both moieties in one molecular skeleton and to synthesize and characterize a novel series of chalone-based phenothiazine derivatives. For this purpose, 2-acetylphenothiazine was N-alkylated, followed by the Claisen-Schmidt reaction to produce the chalcones with good yield. Antioxidant activity, as evaluated by 2,2-diphenyl-1-picrylhydrazyl (DPPH) free radical scavenging, was assessed to determine if their antioxidant potential was comparable with ascorbic acid, and attributable to the phenothiazine core. Screening anticancer activities of the synthesized chalone-based phenothiazine derivatives against human breast cancer cell line MCF-7 cells, and human hepatocellular carcinoma HepG-2 cells, compared with standard drugs cisplatin and doxorubicin, was evaluated. The results revealed that compounds 4a, 4b, 4d, 4h, 4j, 4k, 4m, 4o, and 4p were good against human hepatocellular carcinoma HepG-2 cells, and among these compounds 4b and 4k were the most effective compounds, with IC50 values of 7.14 µg/mL and 7.6 1 µg/mL, respectively. On the other hand, compounds 4a, 4b, 4k, and 4m were good against human breast cancer cell line MCF-7 cells and, among these compounds, 4k and 4b were the most effective compounds, with IC50 values of 12 µg/mL and 13. 8 µg/mL, respectively. The overall results suggest that these compounds could, potentially, be further modified for the formation of more potent antioxidant and anticancer agents.
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Antineoplásicos/química , Antioxidantes/química , Chalconas/química , Fenotiazinas/química , Antineoplásicos/farmacologia , Antioxidantes/farmacologia , Proliferação de Células/efeitos dos fármacos , Sobrevivência Celular/efeitos dos fármacos , Células Hep G2 , Humanos , Células MCF-7RESUMO
A Schiff base supramolecular 4-[(4-(hexyloxy)phenylimino)methyl]benzoic acid and a new series of Schiff base/ester linkages named 4-substitutedphenyl 4-[(4-(hexyloxy)phenylimino)methyl]benzoate liquid crystals were synthesized. The thermal stability, mesomorphic, and optical behavior of the prepared compounds were characterized by differential scanning calorimetry (DSC), Thermogravemetric analysis (TGA), polarized optical microscopy (POM), and UV spectroscopy. FT-IR, 1H-NMR, 13C-NMR, and elemental analyses were carried out to elucidate and confirm the molecular structures of the synthesized compounds. The investigated series comprising different sized terminal polar groups changed between CH(CH3)2, H, I, and F. It was found that the supramolecular imino acid dimer is enantiotropic dimorphic, with a wide SmA phase and a good N phase range. The other series of terminally substituted Schiff base/esters are mesomorphic with a high thermal stable SmA phase, except the iodo derivative, which showed dimorphic SmA and N phases. The effect of the position and the orientation of the cores, as well as the terminal substituent of the type and the stability of the mesophase, were studied. A computational theoretical study of the effects of the van der Waal's volume, the Hammett substituent coefficient, the inductive sigma constant, and other geometrical parameters were discussed. The study revealed that the planarity of the two phenyl rings attached with an imino linking group impacted the resonance effect of the terminal substituents rather than their inductive effect. A detailed study on the effect of the estimated thermal parameters, as well as their geometrical planarity with the type and stability of the formed mesophase, was discussed.
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Cristais Líquidos/química , Bases de Schiff/química , Varredura Diferencial de Calorimetria , Espectroscopia de Ressonância Magnética , Microscopia de Polarização , Espectroscopia de Infravermelho com Transformada de Fourier , TermogravimetriaRESUMO
Quality and biochemical changes of 'Hindi-Besennara' mangoes in response to chitosan, gallic acid (GA) and chitosan gallate (CG) postharvest dipping were studied during 2 weeks of storage at 20 ± 2 °C and 60-70% RH. Both GA and CG lowered decay and weight loss during storage. Chitosan and GA at high level and CG at both level maintained higher membrane stability index of peel than control. Fruits treated only CG and GA at high level and chitosan at both levels retained higher acidity and vitamin C but lower pH and total soluble solids (TSS) than control. All treatments resulted with fruits with higher flesh firmness and lower TSS/acid ratio than untreated fruits. GA at both rates gave lower total phenols after 1 week of storage than control. Both levels of GA and low level of chitosan resulted with fruits with higher antioxidant capacity (lower IC50 values) after 1 week of storage than control. All treatments decreased α-amylase activity of fruit peel compared to control. CG and GA at high level and chitosan at low level increased peroxidase activity compared to control. It was concluded that CG and GA dipping delayed ripening and maintained quality of 'Hindi-Besennara' mangoes during 2 weeks of shelf life.
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The effect of postharvest chitosan, gallic acid (GA) and chitosan gallate (CG) dipping treatments at different concentrations on quality parameters, antioxidant compounds, free radical scavenging capacity (FRSC) and enzymes activities of 'Sukkari' bananas were studied during storage (ripening) at 20 ± 2 °C and 60-70% RH for 13 days. Weight loss and peel color index (the change from green to yellow) increased while, membrane stability index of peel tissues, pulp firmness and acidity decreased during storage. CG and GA treatments slowed down the changes in these parameters compared to control. Total soluble solids (TSS) concentration increased during storage and was lower at CG than other treatments. TSS/acid ratio increased during storage and showed higher value after storage than initial. This ratio was lower at 1% chitosan, 0.075% GA and CG treatments than control. Both vitamin C and total flavonoids concentrations decreased during storage and were not affected by the applied treatments. Total phenols concentration decreased during storage and was higher at acetic acid and the high rate of chitosan, GA and CG treatments than control. FRSC (DPPH IC50 values) of fruit peel ranged from 2.54 to 4.19 µg phenolics concentration among the treatments. FRSC was not affected by the applied treatments but increased (lower IC50 value) during shelf life. The possible relations of these biochemical changes with the activities of the enzymes α-amylase, xylanase, polygalacturonase, peroxidase and polyphenoloxidase were discussed. It is concluded that postharvest CG and GA treatments delayed ripening and maintained better quality parameters of 'Sukkari' bananas during 13 days of shelf life than control.
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The electronic absorption spectra, ground-state geometries and electronic structures of symmetric and asymmetric squaraine dyes (SQD1-SQD4) were investigated using density functional theory (DFT) and time-dependent (TD-DFT) density functional theory at the B3LYP/6-311++G** level. The calculated ground-state geometries reveal pronounced conjugation in these dyes. Long-range corrected time dependent density functionals Perdew, Burke and Ernzerhof (PBE, PBE1PBE (PBE0)), and the exchange functional of Tao, Perdew, Staroverov, and Scuseria (TPSSh) with 6-311++G** basis set were employed to examine optical absorption properties. In an extensive comparison between the optical data and DFT benchmark calculations, the BEP functional with 6-311++G** basis set was found to be the most appropriate in describing the electronic absorption spectra. The calculated energy values of lowest unoccupied molecular orbitals (LUMO) were 3.41, 3.19, 3.38 and 3.23 eV for SQD1, SQD2, SQD3, and SQD4, respectively. These values lie above the LUMO energy (-4.26 eV) of the conduction band of TiO2 nanoparticles indicating possible electron injection from the excited dyes to the conduction band of the TiO2 in dye-sensitized solar cells (DSSCs). Also, aromaticity computation for these dyes are in good agreement with the data obtained optically and geometrically with SQD4 as the highest aromatic structure. Based on the optimized molecular geometries, relative positions of the frontier orbitals, and the absorption maxima, we propose that these dyes are suitable components of photovoltaic DSSC devices.
Assuntos
Corantes/química , Ciclobutanos/química , Fenóis/química , Fontes de Energia Elétrica , Elétrons , Modelos Moleculares , Teoria Quântica , Energia Solar , Espectrofotometria UltravioletaRESUMO
BACKGROUND: In continuation of our previously interest in the saccharification of agriculture wastes by Bacillus megatherium in solid state fermentation (SSF), we wish to report an investigation and comparative evaluation among Trichoderma sp. for the saccharification of four alkali-pretreated agricultural residues and production of hydrolytic enzymes, carboxymethyl cellulase (CMCase), filter paperase (FPase), pectinase (PGase) and xylanase (Xylase) in SSF. The optimization of the physiological conditions of production of hydrolytic enzymes and saccharification content from Trichoderma virens using alkali-pretreated wheat bran was the last goal. METHODS: The physico-chemical parameters of SSF include incubation time, incubation temperature, moisture content of the substrate, incubation pH, supplementation with carbon and nitrogen sources were optimized. RESULTS: Saccharification of different solid state fermentation sources wheat bran, date's seeds, grass and palm leaves, were tested for the production of fermentable sugar by Trichoderma sp. The maximum production of hydrolytic enzymes CMCase, FPase, PGase and Xylase and saccharification content were obtained on wheat bran. Time course, moisture content, optimum temperature, optimum pH, supplementation with carbon and nitrogen sources were optimized to achieve the maximum production of the hydrolytic enzymes, protein and total carbohydrate of T. virens using alkali pre-treated wheat bran. The maximum production of CMCase, FPase, PGase, Xylase, protein and carbohydrate content was recorded at 72 h of incubation, 50-70 % moisture, temperature 25-35 °C and pH 5. The influence of supplementary carbon and nitrogen sources was studied. While lactose and sucrose enhanced the activity of PGase from 79.2 to 582.9 and 632.6 U/g, starch inhibited all other enzymes. This was confirmed by maximum saccharification content. Among the nitrogen sources, yeast extract and urea enhanced the saccharification content and CMCase, PGase and Xylase. CONCLUSIONS: The results of this study indicated that alkali pre-treated wheat bran was a better substrate for saccharification and production of hydrolytic enzymes CMCase, FPase, PGase and xylase by T. virens compared to other alkali-pretreated agricultural residues tested.
Assuntos
Bacillus megaterium/metabolismo , Fermentação , Trichoderma/metabolismo , Álcalis/química , Bacillus megaterium/química , Carboidratos/química , Carbono/metabolismo , Fibras na Dieta/metabolismo , Concentração de Íons de Hidrogênio , Hidrólise , Nitrogênio , Poligalacturonase/metabolismo , Temperatura , Trichoderma/químicaRESUMO
The synthesis and characterization of different ether and ester derivatives of 8-hydroxyquinoline have been made. UV-visible and fluorescence spectra of these compounds have revealed spectral dependence on both solvent and O-substituent. The fluorescence intensity of ether derivatives revealed higher intensity for 8-octyloxyquinoline compared with 8-methoxyquinoline, whereas those of ester derivatives had less fluorescence than 8-hydroxyquinoline. Theoretical calculations based on Time-dependent density functional theory (TD-DFT) were carried out for the quinolin-8-yl benzoate (8-OateQ) compound to understand the effect of O-substituent on the electronic absorption of 8-hydroxyquinaline (8-HQ). The calculations revealed comparable results with those obtained from the experimental data. Optimized geometrical structure was calculated with DFT at B3LYP/6-311++G** level of theory. The results indicated that 8-OateQ is not a coplanar structure. The absorption spectra of the compound were computed in gas-phase and solvent using B3LYP and CAM-B3LYP methods with 6-311++G ** basis set. The agreement between calculated and experimental wavelengths was very good at CAM-B3LYP/6-311++G** level of theory.
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Modelos Químicos , Oxiquinolina/química , Quinolinas/química , Fluorescência , Modelos Moleculares , Espectrometria de FluorescênciaRESUMO
BACK GROUND: For enzyme production, the costs of solid state fermentation (SSF) techniques were lower and the production higher than submerged cultures. A large number of fungal species was known to grow well on moist substrates, whereas many bacteria were unable to grow under this condition. Therefore, the aim of this study was to isolate a highly efficient strain of Bacillus sp utilizing wheat bran in SSF and optimizing the enzyme production and soluble carbohydrates. RESULTS: A local strain Bacillus megatherium was isolated from dung sheep. The maximum production of pectinase, xylanase and α-amylase, and saccharification content (total soluble carbohydrates and reducing sugars) were obtained by application of the B. megatherium in SSF using wheat bran as compared to grasses, palm leaves and date seeds. All enzymes and saccharification content exhibited their maximum production during 12-24 h, at the range of 40-80% moisture content of wheat bran, temperature 37-45°C and pH 5-8. An ascending repression of pectinase production was observed by carbon supplements of lactose, glucose, maltose, sucrose and starch, respectively. All carbon supplements improved the production of xylanase and α-amylase, except of lactose decreased α-amylase production. A little increase in the yield of total reducing sugars was detected for all carbon supplements. Among the nitrogen sources, yeast extract induced a significant repression to all enzyme productivity. Sodium nitrate, urea and ammonium chloride enhanced the production of xylanase, α-amylase and pectinase, respectively. Yeast extract, urea, ammonium sulphate and ammonium chloride enhanced the productivity of reducing sugars. CONCLUSIONS: The optimization of enzyme production and sccharification content by B. megatherium in SSF required only adjustment of incubation period and temperature, moisture content and initial pH. Wheat bran supplied enough nutrients without any need for addition of supplements of carbon and nitrogen sources.
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Bacillus megaterium/metabolismo , Fibras na Dieta/metabolismo , Endo-1,4-beta-Xilanases/biossíntese , Fermentação , Poligalacturonase/biossíntese , alfa-Amilases/biossíntese , Bacillus megaterium/isolamento & purificação , Carboidratos/química , HidróliseRESUMO
Seven reactive dyes judiciously selected based on chemical structures and fixation mechanisms were applied at 2% of of shade on amidoximated acrylic fabrics. Amidoximated acrylic fabric has been obtained by a viable amidoximation process. The dyeability of these fabrics was evaluated with respect to the dye exhaustion, fixation, and colour strength under different conditions of temperature and dyeing time. Nucleophilic addition type reactive dyes show higher colour data compared to nucleophilic substitution ones. FTIR studies further implicate the binding of reactive dyes on these fabrics. A tentative mechanism is proposed to rationalize the high fixation yield obtained using nucleophilic addition type reactive dyes. Also, the levelling and fastness properties were evaluated for all dyes used. Excellent to good fastness and levelling properties were obtained for all samples irrespective of the dye used. The result of investigation offers a new method for a viable reactive dyeing of amidoximated acrylic fabrics.
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Acrilatos/química , Corantes/química , Indústria Têxtil/métodos , Têxteis , Algoritmos , Cor , Concentração de Íons de Hidrogênio , Hidroxilamina/química , Estrutura Molecular , Oximas/química , Espectroscopia de Infravermelho com Transformada de Fourier , Temperatura , Fatores de TempoRESUMO
α-Amylase from Trichoderma harzianum was covalently immobilized on activated wool by cyanuric chloride. Immobilized α-amylase exhibited 75% of its initial activity after 10 runs. The soluble and immobilized α-amylases exhibited maximum activity at pH values 6.0 and 6.5, respectively. The immobilized enzyme was more thermally stable than the soluble one. Various substrates were hydrolyzed by immobilized α-amylase with high efficiencies compared to those of soluble α-amylase. The inhibition of the immobilized α-amylase by metal ions was low as compared with soluble enzyme. On the basis of the results obtained, immobilized α-amylase could be employed in the saccharification of starch processing.
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Enzimas Imobilizadas/química , Trichoderma/enzimologia , Lã/química , alfa-Amilases/química , Animais , Concentração de Íons de HidrogênioRESUMO
Immobilization of enzymes on suitable supports is a critical approach for enhancing enzyme stability, reusability, and overall catalytic efficiency. This study explores the immobilization of Candida rugosa lipase on zirconium-based 2-methylimidazole (ZrMI) nanoparticles, aiming to develop a stable and reusable biocatalyst. The ZrMI was produced via a solvothermal technique and analyzed using various characterization methods. Candida rugose lipase was immobilized using cross-linking agents, achieving an 87â¯% immobilization efficiency. The immobilized enzyme exhibited significantly enhanced thermal stability, broader pH tolerance, and increased catalytic efficiency compared to free C. rugose lipase. The ZrMI@lipase retained 69â¯% of its enzymatic activity following a 60-day storage period at 4⯰C. Notably, it displayed significant reusability, maintaining 65â¯% of its original activity after undergoing 15 catalytic cycles. Examination of the kinetics revealed that the immobilized enzyme possessed a heightened substrate affinity (Km of 4.1â¯mM) and maximal reaction rate (Vmax of 85.7⯵mol/mL/min) in comparison to the free enzyme (Km of 5.4â¯mM and Vmax of 69⯵mol/mL/min), indicating enhanced catalytic efficiency. Validation through zeta potential and hydrodynamic size assessments verified the successful binding of the enzyme and the consistent colloidal characteristics. These results suggest that ZrMI is a promising support for C. rugose lipase immobilization, offering improved stability and reusability for various industrial applications. The study highlights the potential of ZrMI@lipase as an efficient and durable biocatalyst, contributing to advancements in enzyme immobilization technology and sustainable industrial processes.
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A water-soluble indocarbocyanine dye was synthesized and its photophysics were studied for the first time on two solid hosts, microcrystalline cellulose and b-cyclodextrin, as well as in homogeneous media. The inclusion of the indocarbocyanine moiety onto microcrystalline cellulose increased the dye aggregation with both H and J aggregates being formed. Adsorption on b-cyclodextrin enhanced aggregation in a similar way. The fluorescence quantum yields were determined for the powdered samples of the cyanine dye on the two hosts and a significant increase was observed relative to homogeneous solution. A remarkable concentration dependence was also detected in both cases. A lifetime distribution analysis has shown that the indocarbocyanine dye mainly occupies the amorphous part of cellulose and is not entrapped in the crystalline part of this host. In the b-CD case, the adsorption occurs outside the host cavity. In both hosts a strong concentration quenching effect is observed and only monomers emit. Both adsorptions may be explained by stereochemical constraints imposed by the two long sulphoethyl tails linked to nitrogen atoms of the indocarbocyanine dye.
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Carbocianinas/química , Celulose/química , Corantes/química , Água/química , beta-Ciclodextrinas/química , SolubilidadeRESUMO
Modified polymer design has attracted significant attention for enzyme immobilization, offering promising applications. In this study, amine-terminated polymers were synthesized by incorporating functional groups into polyacrylonitrile using hexamethylenediamine. This work highlights the successful enzyme immobilization strategy using modified polymers, offering improved stability and expanded operational conditions for potential biotechnological applications. The resulting amino groups were utilized to capture silver ions, which were subsequently converted to silver nanoparticles (AgNPs). The obtained materials, AgNPs@TA-HMDA (acrylic textiles coated silver nanoparticles AgNPs) and Ag(I)@TA-HMDA (acrylic textiles coated with Ag ion) were employed as supports for ß-glucosidase enzyme immobilization. The highest immobilization yields (IY%) were achieved with AgNPs@TA-HMDA at 92%, followed by Ag(I)@TA-HMDA at 79.8%, resulting in activity yields (AY%) of 81% and 73%, respectively. Characterization techniques such as FTIR, FE-SEM, EDX, TG/DTG, DSC, and zeta potential were employed to investigate the structural composition, surface morphologies, elemental composition, thermal properties, and surface charge of the support materials. After 15 reuses, the preservation percentages decreased to 76% for AgNPs@TA-HMDA/ß-Glu and 65% for Ag(I)@TA-HMDA/ß-Glu. Storage stability revealed that the decrease in activity for the immobilized enzymes was smaller than the free enzyme. The optimal pH for the immobilized enzymes was broader (pH 5.5 to 6.5) compared to the free enzyme (pH 5.0), and the optimal temperature for the immobilized enzymes was 60 °C, slightly higher than the free enzyme's optimal temperature of 50 °C. The kinetic analysis showed a slight increase in Michaelis constant (Km) values for the immobilized enzymes and a decrease in maximum velocity (Vmax), turnover number (Kcat), and specificity constant (Kcat/Km) values compared to the free enzyme. Through extensive characterization, we gained valuable insights into the structural composition and properties of the modified polymer supports. This research significantly contributes to the development of efficient biotechnological processes by advancing the field of enzyme immobilization and offering valuable knowledge for its potential applications.
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An innovative approach for immobilizing α-amylase was used in this investigation. The acrylic fabric was first treated with hexamethylene diamine (HMDA) and then coated with copper ions that were later reduced to copper nanoparticles (CuNPs). The corresponding materials obtained, Cu(II)@HMDA-TA and CuNPs@HMDA-TA, were employed as carriers for α-amylase, respectively. The structural and morphological characteristics of the produced support matrices before and after immobilization were assessed using various techniques, including FTIR, SEM, EDX, TG/DTG, DSC, and zeta potential. The immobilized α-amylase exhibited the highest level of activity at pH 7.0, with immobilization yields observed for CuNPs@HMDA-TA (81.7 %) (60 unit/g support) followed by Cu(II)@HMDA-TA (71.7 %) (49 unit/g support) and 75 % and 61 % of activity yields, and 91.7 % and 85 % of immobilization efficiency, respectively. Meanwhile, biochemical characterizations of the activity of the soluble and immobilized enzymes were carried out and compared. Optimal temperature, pH, kinetics, storage stability, and reusability parameters were optimized for immobilized enzyme activity. The optimal pH and temperature were recorded as 6.0 and 50 °C for soluble α-amylase while the two forms of immobilized α-amylase exhibit a broad pH of 6.0-7.0 and optimal temperature at 60 °C. After recycling 15 times, the immobilized α-amylase on CuNPs@HMDA-TA and Cu(II)@HMDA-TA preserved 63 % and 52 % of their activities, respectively. The two forms of immobilized α-amylase displayed high stability when stored for 6 weeks and preserved 85 % and 76 % of their activities, respectively. Km values were calculated as 1.22, 1.39, and 1.84 mg/mL for soluble, immobilized enzymes on CuNPs@HMDA-TA, and Cu(II)@HMDA-TA, and Vmax values were calculated as 36.25, 29.68, and 21.57 µmol/mL/min, respectively. The total phenolic contents of maize kernels improved 1.4 ± 0.01 fold after treatment by two immobilized α-amylases.