The affinity of zeolite nanoparticles (diameter of 8-12 nm) possessing high surface area and high pore volume towards human plasma proteins has been investigated. The protein composition (corona) of zeolite nanoparticles has been shown to be more dependent on the plasma protein concentrations and the type of zeolites than zeolite nanoparticles concentration. The number of proteins present in the corona of zeolite nanoparticles at 100% plasma (in vivo state) is less than with 10% plasma exposure. This could be due to a competition between the proteins to occupy the corona of the zeolite nanoparticles. Moreover, a high selective adsorption for apolipoprotein C-III (APOC-III) and fibrinogen on the zeolite nanoparticles at high plasma concentration (100%) was observed. While the zeolite nanoparticles exposed to low plasma concentration (10%) exhibited a high selective adsorption for immunoglobulin gamma (i.e. IGHG1, IGHG2 and IGHG4) proteins. The zeolite nanoparticles can potentially be used for selectively capture of APOC-III in order to reduce the activation of lipoprotein lipase inhibition during hypertriglyceridemia treatment. The zeolite nanoparticles can be adapted to hemophilic patients (hemophilia A (F-VIII deficient) and hemophilia B (F-IX deficient)) with a risk of bleeding, and thus might be potentially used in combination with the existing therapy.
EMT-type zeolite nanoparticles (EMT NPs) with particle size of 10-20 nm and external surface area of 200 m2/g have shown high selective affinity toward plasma protein (fibrinogen). Besides, the EMT NPs have demonstrated no adverse effect on blood coagulation hemostasis. Therefore, it was envisioned that the EMT NPs could inhibit possible β-amyloid (Aβ)-fibrinogen interactions that result in the formation of structurally abnormal clots, which are resistant to lysis, in cerebral vessels of patients with Alzheimer disease (AD). To evaluate this hypothesis, the clot formation and degradation of Aβ-fibrinogen in the presence and absence of the EMT zeolite NPs were assessed. The results clearly showed that the delay in clot dissolution was significantly reduced in the presence of zeolite NPs. By formation of protein corona, the EMT NPs showed a negligible reduction in their inhibitory strength. Docking of small molecules (Aβ-fibrinogen) introduced a novel potential inhibitory candidate. The zeolite NPs showed similar inhibitory effects on binding of fibrinogen to both Aβ(25-35) and/or Aβ(1-42). This indicates that the inhibitory strength of these NPs is independent of Aβ sequence, and it is suggested that the zeolite NPs adsorb fibrinogen and specifically obstruct their Aβ binding sites. Therefore, the zeolite NPs can be the safe and effective inhibitors in preventing Aβ-fibrinogen interaction and consequent cognitive damage.
Zeolite Linde Type L (LTL) crystals with different length, diameter and particle size (nanosized LTL, rod LTL, cylinder LTL and needle LTL) were synthesized, characterized and were used as sorbent in the micro-solid phase extraction of ochratoxin A (OTA) before the high performance liquid chromatography detection. Under the optimized conditions, the detection limits of OTA for coffee and cereal were 0.09 ng g(-1) and 0.03 ng g(-1), respectively, while the quantification limits were 0.28 ng g(-1) and 0.08 ng g(-1), respectively. The recoveries of OTA of coffee and cereal spiked at 0.5, 10 and 25 ng g(-1) ranged from 91.7 to 101.0%. The proposed method was applied to forty-five samples of coffee and cereal. The presence of OTA was found in twenty-five samples, ranging from 0.28 to 9.33 ng g(-1).
Biofertilizers encompass microorganisms that can be applied to plants, subsequently establishing themselves within the plant's rhizosphere or internal structures. This colonization stimulates plant development by enhancing nutrient absorption from the host. While there is growing literature documenting the applications of microalgae-based and bacterial-based biofertilizers, the research focusing on the effectiveness of consortia formed by these microorganisms as short-term plant biofertilizers is notably insufficient. This study seeks to assess the effectiveness of microalgae-bacterial biofertilizers in promoting plant growth and their potential contribution to the circular economy. The review sheds light on the impact of microalgae-bacterial biofertilizers on plant growth parameters, delving into factors influencing their efficiency, microalgae-bacteria interactions, and effects on soil health. The insights from this review are poised to offer valuable guidance to stakeholders in agriculture, including farmers, environmental technologists, and businesses. These insights will aid in the development and investment in more efficient and sustainable methods for enhancing crop yields, aligning with the Sustainable Development Goals and principles of the circular economy.
Sustainable wastewater treatment necessitates the application of natural and green material in the approach. Thus, selecting a natural coagulant in leachate treatment is a crucial step in landfill operation to prevent secondary environmental pollution due to residual inorganic coagulant in treated effluent. Current study investigated the application of guar gum in landfill leachate treatment. Central composite design in response surface methodology was used to optimize the performance of Chemical Oxygen Demand (COD) removal. Quadratic model developed indicated the optimum COD removal 22.57% at guar gum dosage of 44.39 mg/L, pH 8.56 (natural pH of leachate) and mixing speed 79.27 rpm. Scanning electron microscopy showed that floc was compact and energy-dispersive-x-ray analysis showed that guar gum was capable to adsorb multiple ions from the leachate. Structural characterization using Fourier Transform Infrared analysis demonstrated that hydrogen bonding between guar and pollutant particles was involved in coagulation and flocculation process. Therefore, guar gum coagulant present potential to be an alternative in leachate treatment where pH requirement is not required during treatment. Simultaneously, adsorption by guar gum offers added pollutant removal advantage.
Algal biomass is known as a promising sustainable feedstock for the production of biofuels and other valuable products. However, since last decade, massive amount of interests have turned to converting algal biomass into biochar. Due to their high nutrient content and ion-exchange capacity, algal biochars can be used as soil amendment for agriculture purposes or adsorbents in wastewater treatment for the removal of organic or inorganic pollutants. This review describes the conventional (e.g., slow and microwave-assisted pyrolysis) and newly developed (e.g., hydrothermal carbonization and torrefaction) methods used for the synthesis of algae-based biochars. The characterization of algal biochar and a comparison between algal biochar with biochar produced from other feedstocks are also presented. This review aims to provide updated information on the development of algal biochar in terms of the production methods and the characterization of its physical and chemical properties to justify and to expand their potential applications.
Offretite zeolite synthesis in the presence of cetyltrimethylammonium bromide (CTABr) is reported. The offretite crystals were synthesized with a high crystallinity and hexagonal prismatic shape after only 72 h of hydrothermal treatment at 180 °C. The CTABr has dual-functions during the crystallization of offretite, viz. as structure-directing agent and as mesoporogen. The resulting offretite crystals, with a Si/Al ratio of 4.1, possess more acid sites than the conventional offretite due to their high crystallinity and hierarchical structure. The synthesized offretite is also more reactive than its conventional counterpart in the acylation of 2-methylfuran for biofuel production under non-microwave instant heating condition, giving 83.5% conversion with 100% selectivity to the desired product 2-acetyl-5-methylfuran. Hence, this amphiphile synthesis approach offers another cost-effective and alternative route for crystallizing zeolite materials that require expensive organic templates.
Microbial lipases are popular biocatalysts due to their ability to catalyse diverse reactions such as hydrolysis, esterification, and acidolysis. Lipases function efficiently on various substrates in aqueous and non-aqueous media. Lipases are chemo-, regio-, and enantio-specific, and are useful in various industries, including those manufacturing food, detergents, and pharmaceuticals. A large number of lipases from fungal and bacterial sources have been isolated and purified to homogeneity. This success is attributed to the development of both conventional and novel purification techniques. This review highlights the use of these techniques in lipase purification, including conventional techniques such as: (i) ammonium sulphate fractionation; (ii) ion-exchange; (iii) gel filtration and affinity chromatography; as well as novel techniques such as (iv) reverse micellar system; (v) membrane processes; (vi) immunopurification; (vi) aqueous two-phase system; and (vii) aqueous two-phase floatation. A summary of the purification schemes for various bacterial and fungal lipases are also provided.
Hydrazine borane (HB) is a chemical hydrogen storage material with high gravimetric hydrogen density of 15.4 wt%, containing both protic and hydridic hydrogen. However, its limitation is the formation of unfavorable gaseous by-products, such as hydrazine (N2H4) and ammonia (NH3), which are poisons to fuel cell catalyst, upon pyrolysis. Previous studies proved that confinement of ammonia borane (AB) greatly improved the dehydrogenation kinetics and thermodynamics. They function by reducing the particle size of AB and establishing bonds between silica functional groups and AB molecules. In current study, we employed the same strategy using MCM-41 and silica aerogel to investigate the effect of nanosizing towards the hydrogen storage properties of HB. Different loading of HB to the porous supports were investigated and optimized. The optimized loading of HB in MCM-41 and silica aerogel was 1:1 and 0.25:1, respectively. Both confined samples demonstrated great suppression of melting induced sample foaming. However, by-products formation was enhanced over dehydrogenation in an open system decomposition owing to the presence of extensive Si-O···BH3(HB) coordination that further promote the B-N bond cleavage to release N2H4. The Si-OH···N(N2H4) hydrogen bonding may further promote N-N bond cleavage in the resulting N2H4, facilitating the formation of NH3. As temperature increases, the remaining N-N-B oligomeric chains in the porous silica, which are lacking the long-range structure may further undergo intramolecular B-N or N-N cleavage to release substantial amount of N2H4 or NH3. Besides open system decomposition, we also reported a closed system decomposition where complete utilization of the N-H from the released N2H4 and NH3 in the secondary reaction can be achieved, releasing mainly hydrogen upon being heated up to high temperatures. Nanosizing of HB particles via PMMA encapsulation was also attempted. Despite the ester functional group that may favor multiple coordination with HB molecules, these interactions did not impart significant change towards the decomposition of HB selectively towards dehydrogenation.
Fibrinogen is one of the key proteins that participate in the protein corona composition of many types of nanoparticles (NPs), and its conformational changes are crucial for activation of immune systems. Recently, we demonstrated that the fibrinogen highly contributed in the protein corona composition at the surface of zeolite nanoparticles. Therefore, understanding the interaction of fibrinogen with zeolite nanoparticles in more details could shed light of their safe applications in medicine. Thus, we probed the molecular interactions between fibrinogen and zeolite nanoparticles using both experimental and simulation approaches. The results indicated that fibrinogen has a strong and thermodynamically favorable interaction with zeolite nanoparticles in a non-cooperative manner. Additionally, fibrinogen experienced a substantial conformational change in the presence of zeolite nanoparticles through a concentration-dependent manner. Simulation results showed that both E- and D-domain of fibrinogen are bound to the EMT zeolite NPs via strong electrostatic interactions, and undergo structural changes leading to exposing normally buried sequences. D-domain has more contribution in this interaction and the C-terminus of γ chain (γ377-394), located in D-domain, showed the highest level of exposure compared to other sequences/residues.
Micro- and macroscopic studies of nucleation and growth processes of MnAlPO-5 nanosized crystals under ionothermal synthesis conditions are reported herein. The samples treated at 150 °C were extracted from the reaction mixture at various stages of crystallization, and characterized by XRD; SEM; thermogravimetric analysis (TGA); (31)P and (27)Al solid-state magic angle spinning (MAS) NMR, Raman, UV/Vis, and X-ray fluorescence spectroscopy (XRF). The starting raw materials (alumina, manganese, and phosphorous) were dissolved completely in the ionic liquid and transformed into an amorphous solid after 5 h of ionothermal treatment. This amorphous solid then undergoes structural changes over the following 5-25 h, which result in an intermediate phase that consists of octahedral Al species linked to the manganese and phosphate species. The first MnAlPO-5 nuclei on the surface of the intermediate can be observed after 50 h ionoheating. These nuclei further grow, as the surface of the intermediate is in full contact with the ionic liquid, to give crystalline MnAlPO-5 nanoparticles with a mean diameter of 80 nm. The crystals become fully detached from the intermediate and are then liberated as discrete particles after 90 h heating. The transformation process from amorphous to intermediate and then to the crystalline MnAlPO-5 nanoparticles shows that nucleation starts at the solid-liquid interface and continues through surface-to-core reversed-growth until the entire amorphous solid is transformed into discrete nanocrystals.
It is known that carbon nanotubes show desirable physical and chemical properties with a wide array of potential applications. Nonetheless, their potential has been hampered by the difficulties in acquiring high purity, chiral-specific tubes. Considerable advancement has been made in terms of the purification of carbon nanotubes, for instance chemical oxidation, physical separation, and myriad combinations of physical and chemical methods. The aqueous two-phase separation technique has recently been demonstrated to be able to sort carbon nanotubes based on their chirality. The technique requires low cost polymers and salt, and is able to sort the tubes based on their diameter as well as metallicity. In this review, we aim to provide a review that could stimulate innovative thought on the progress of a carbon nanotubes sorting method using the aqueous two-phase separation method, and present possible future work and an outlook that could enhance the methodology.
Recent trend to recover value-added products from wastewater calls for more effective pre-treatment technology. Conventional landfill leachate treatment is often complex and thus causes negative environmental impacts and financial burden. In order to facilitate downstream processing of leachate wastewater for production of energy or value-added products, it is pertinent to maximize leachate treatment performance by using simple yet effective technology that removes pollutants with minimum chemical added into the wastewater that could potentially affect downstream processing. Hence, the optimization of coagulation-flocculation leachate treatment using multivariate approach is crucial. Central composite design was applied to optimize operating parameters viz. Alum dosage, pH and mixing speed. Quadratic model indicated that the optimum COD removal of 54% is achieved with low alum dosage, pH and mixing speed of 750 mgL-1, 8.5 and 100 rpm, respectively. Optimization result showed that natural pH of the mature landfill leachate sample is optimum for alum coagulation process. Hence, the cost of pH adjustment could be reduced for industrial application by adopting optimized parameters. The inherent mechanism of pollutant removal was elucidated by FTIR peaks at 3853 cm-1 which indicated that hydrogen bonds play a major role in leachate removal by forming well aggregated flocs. This is concordance with SEM image that the floc was well aggregated with the porous linkages and amorphous surface structure. The optimization of leachate treatment has been achieved by minimizing the usage of alum under optimized condition.
A relationship is proposed for the interfacial partitioning of protein in poly(ethylene glycol) (PEG)-phosphate aqueous two-phase system (ATPS). The relationship relates the natural logarithm of interfacial partition coefficient, ln G to the PEG concentration difference between the top and bottom phases, Δ[PEG], with the equation ln G=AΔ[PEG]+B. Results showed that this relationship provides good fits to the partition of bovine serum albumin (BSA) in ATPS which is comprised of phosphate and PEG of four different molecular weight 1450g/mol, 2000g/mol, 3350g/mol and 4000g/mol, with the tie-line length (TLL) in the range of 44-60% (w/w) at pH 7.0. The decrease of A values with the increase of PEG molecular weight indicates that the correlation between ln G and Δ[PEG] decreases with the increase in PEG molecular weight and the presence of protein-polymer hydrophobic interaction. When temperature was increased, a non-linear relationship of ln G inversely proportional to temperature was observed. The amount of proteins adsorbed at the interface increased proportionally with the amount of BSA loaded whereas the partition coefficient, K remained relatively constant. The relationship proposed could be applied to elucidate interfacial partitioning behaviour of other biomolecules in polymer-salt ATPS.
The efficiency of zeolite X nanocrystals (FAU-type framework structure) containing different extra-framework cations (Li(+), Na(+), K(+), and Ca(2+)) in slowing the thermal oxidation of palm oil is reported. The oxidation study of palm oil is conducted in the presence of zeolite nanocrystals (0.5 wt %) at 150 °C. Several characterization techniques such as visual analysis, colorimetry, rheometry, total acid number (TAN), FT-IR spectroscopy, (1)H NMR spectroscopy, and Karl Fischer analyses are applied to follow the oxidative evolution of the oil. It was found that zeolite nanocrystals decelerate the oxidation of palm oil through stabilization of hydroperoxides, which are the primary oxidation product, and concurrently via adsorption of the secondary oxidation products (alcohols, aldehydes, ketones, carboxylic acids, and esters). In addition to the experimental results, periodic density functional theory (DFT) calculations are performed to elucidate further the oxidation process of the palm oil in the presence of zeolite nanocrystals. The DFT calculations show that the metal complexes formed with peroxides are more stable than the complexes with alkenes with the same ions. The peroxides captured in the zeolite X nanocrystals consequently decelerate further oxidation toward formation of acids. Unlike the monovalent alkali metal cations in the zeolite X nanocrystals (K(+), Na(+), and Li(+)), Ca(2+) reduced the acidity of the oil by neutralizing the acidic carboxylate compounds to COO(-)(Ca(2+))1/2 species.
Acetylation of glycerol to yield monoacetin (MAT), diacetin (DAT), and triacetin (TAT) over NiO-supported CeO2 (xNiO/CeO2) catalysts is reported. The catalysts were synthesized utilizing a sol-gel technique, whereby different quantities of NiO (x = 9, 27, and 45 wt%) were supported onto the CeO2 substrate, and hexadecyltrimethylammonium bromide (CTABr) served as a porogen. The utilization of EDX elemental mapping analysis confirmed the existence of evenly distributed Ni2+ ion and octahedral NiO nanoparticles on the CeO2 surface through the DRS UV-Vis spectroscopy. The most active catalyst is 27NiO/CeO2 based on TAT selectivity in the glycerol acetylation with ethanoic acid, attaining 97.6% glycerol conversion with 70.5% selectivity to TAT at 170 °C with a 1:10 glycerol/ethanoic acid molar ratio for 30 min using a non-microwave instant heating reactor. The 27NiO/CeO2 is reusable without significant decline in catalytic performance after ten consecutive reaction cycles, indicating high structure stability with accessible active acidity.
An extractive bioconversion with Bacillus cereus cyclodextrin glycosyltransferase (CGTase, EC 2.4.1.19) in aqueous two-phase system (ATPS) was investigated for the synthesis and recovery of cyclodextrins (CDs). Optimum condition for the extractive bioconversion of CDs was achieved in ATPS consisted of 7.7% (w/w) polyethylene glycol (PEG) 20,000 and 10.3% (w/w) dextran T500 with volume ratio (VR) of 4.0. Enzymatic conversion of starch occurred mainly in dextran-rich bottom phase whereas the product, CDs was transferred to top phase and a higher partition coefficient of CDs was achieved. Repetitive batch of CDs synthesis was employed by replenishment of the top phase components and addition of starch every 8h. An average total CDs concentration of 13.7 mg/mL, (4.77 mg/mLα-CD, 5.02 mg/mLβ-CD and 3.91 mg/mLγ-CD) was recovered in the top phase of PEG 20,000/dextran T500 ATPS. This study showed the effectiveness of ATPS application in extractive bioconversion of CDs synthesis with B. cereus CGTase.
An extractive bioconversion conducted on soluble starch with cyclodextrin glycosyltransferase (CGTase) enzyme in ethylene oxide-propylene oxide (EOPO)/potassium phosphates liquid biphasic system (LBS) to extract gamma-cyclodextrin (γ-CD) was examined. A range of EOPO (with potassium phosphates) molecular weights was screen to investigate the effect of the latter on the partioning efficency of CGTase and γ-CD. The results show that the optimal top phase γ-CD yield (74.4%) was reached in 35.0% (w/w) EOPO 970 and 10.0% (w/w) potassium phosphate with 2.0% (w/w) sodium chloride. A theoretical explanation for the effect of NaCl on γ-CD was also presented. After a 2 h bioconversion process, a total of 0.87 mg/mL concentration of γ-CD was produced in the EOPO/ phosphates LBS top phase. After the extraction of top phase from LBS, four continuous repetitive batches were successfully conducted with relative CGTase activity of 1.00, 0.86, 0.45, and 0.40 respectively.
Lubricant oils take significant part in current health and environmental considerations since they are an integral and indispensable component of modern technology. Antioxidants are probably the most important additives used in oils because oxidative deterioration plays a major role in oil degradation. Zeolite nanoparticles (NPs) have been proven as another option as green antioxidants in oil formulation. The anti-oxidative behavior of zeolite NPs is obvious; however, the phenomenon is still under investigation. Herein, a study of the effect of extra-framework cations stabilized on Linde Type L (LTL) zeolite NPs (ca. 20 nm) on inhibition of oxidation in palm oil-based lubricant oil is reported. Hydrophilic LTL zeolites with a Si/Al ratio of 3.2 containing four different inorganic cations (Li(+), Na(+), K(+), Ca(2+)) were applied. The oxidation of the lubricant oil was followed by visual observation, colorimetry, fourier transform infrared (FTIR) spectroscopy, (1)H NMR spectroscopy, total acid number (TAN), and rheology analyses. The effect of extra-framework cations to slow down the rate of oil oxidation and to control the viscosity of oil is demonstrated. The degradation rate of the lubricant oil samples is decreased considerably as the polarizability of cation is increased with the presence of zeolite NPs. More importantly, the microporous zeolite NPs have a great influence in halting the steps that lead to the polymerization of the oils and thus increasing the lifetime of oils.
Nanoporous materials such as Mobil composite material number 41 (MCM-41) are attractive for applications such as catalysis, adsorption, supports, and carriers. Green synthesis of MCM-41 is particularly appealing because the chemical reagents are useful and valuable. We report on the eco-friendly synthesis of MCM-41 nanoporous materials via multi-cycle approach by re-using the non-reacted reagents in supernatant as mother liquor after separating the solid product. This approach was achieved via minimal requirement of chemical compensation where additional fresh reactants were added into the mother liquor followed by pH adjustment after each cycle of synthesis. The solid product of each successive batch was collected and characterized while the non-reacted reagents in supernatant can be recovered and re-used to produce subsequent cycle of MCM-41. The multi-cycle synthesis is demonstrated up to three times in this research. This approach suggests a low cost and eco-friendly synthesis of nanoporous material since less waste is discarded after the product has been collected, and in addition, product yield can be maintained at the high level.