This paper reports the synthesis of two-dimensional, hierarchical, porous, and (001)-faceted metal (Ag, Zn, and Al)-doped TiO2 nanostructures (TNSs) and the study of their photocatalytic activity. Two-dimensional metal-doped TNSs were synthesized using the hydrolysis of ammonium hexafluorotitanate in the presence of hexamethylenetetramine and metal precursors. Typical morphology of metal-doped TNSs is a hierarchical nanosheet that is composed of randomly stacked nanocubes (dimensions of up to 5 μm and 200 nm in edge length and thickness, respectively) and has dominant (001) facets exposed. Raman analysis and X-ray photoelectron spectroscopy results indicated that the Ag doping, compared to Zn and Al, much improves the crystallinity degree and at the same time dramatically lowers the valence state binding energy of the TNS and provides an additional dopant oxidation state into the system for an enhanced electron-transfer process and surface reaction. These are assumed to enhance the photocatalytic of the TNS. In a model of photocatalytic reaction, that is, rhodamine B degradation, the AgTNS demonstrates a high photocatalytic activity by converting approximately 91% of rhodamine B within only 120 min, equivalent to a rate constant of 0.018 m-1 and ToN and ToF of 94 and 1.57 min-1, respectively, or 91.1 mmol mg-1 W-1 degradation when normalized to used light source intensity, which is approximately 2 times higher than the pristine TNS and several order higher when compared to Zn- and Al-doped TNSs. Improvement of the crystallinity degree, decrease in the defect density and the photogenerated electron and hole recombination, and increase of the oxygen vacancy in the AgTNS are found to be the key factors for the enhancement of the photocatalytic properties. This work provides a straightforward strategy for the preparation of high-energy (001) faceted, two-dimensional, hierarchical, and porous Ag-doped TNSs for potential use in photocatalysis and photoelectrochemical application.
A sonication of graphite in polysaccharide (pullulan, chitosan and alginate) is one of the viable methods for the preparation of few-layer graphene. However, the effect of these adsorbed polysaccharides on the electrical performance of the produced graphene so far is not yet clear. In order to investigate the present effect of pullulan, chitosan and alginate on the electrical characteristic of resulted graphene, we have produced few-layer graphene using bath sonication of graphite in pullulan, chitosan and alginate medium for the application as electrical conductive ink in strain-sensitive. Data from the TEM reveals the appearance of folded few-layer graphene flakes after sonication for 150 min while the XPS data shows that the chitosan-based graphene possesses the highest carbon-oxygen ratio of 7.2 as compared to that of the pullulan and alginate-based graphene. By subjecting the produced graphene as the ink for paper-based strain sensor, we have discovered that the chitosan-graphene has the best resistivity value (1.66 × 10-3 Ω⋅cm) and demonstrate the highest sensitivity towards strain (GF: 18.6). This result interestingly implies the potential of the reported chitosan-based conductive ink as a strain-sensitive material for future food packaging.
Catalysts prepared from industrial wastes rich in Fe, Ca, Si, and Al were used in catalytic upgrading of pyrolysis vapour derived from durian shell and their effect on product yield and properties were compared. With same silica-to-alumina ratio, catalyst prepared from oil palm ash (AS-OPA) with lower Fe and Ca contents gave higher liquid yield (8.32 wt%) with alcohols (28.90%), hydrocarbons (46.00%), and nitrogen-containing compounds (21.46%) while catalyst prepared from electric arc furnace slag (AS-EAF) with higher Fe and Ca contents produced lower liquid yield (50.21 wt%) with high amount of esters (25.80%) and hydrocarbons (72.82%). The presence of AS-OPA and AS-EAF catalysts enhanced deoxygenation degree of bio-oil to 81.13% and 85.49%, respectively. The catalytic performance of AS-EAF at different temperatures (400-600 °C) and AS-EAF/durian shell ratios (1:30, 2:30, 3:30) was investigated. Increasing catalytic temperature enhanced production of bio-oil, reduced oxygenates and enhanced formation of esters. The liquid yield and yield of esters decreased with increasing catalyst loading. Hydrocarbons (mainly neopentane) were the major chemical compounds found in bio-oil produced over AS-EAF. Besides that, AS-EAF showed good deoxygenation performance with highest selectivity of hydrocarbons at 500 °C and AS-EAF/durian shell ratio of 2:30. Catalytic fast pyrolysis of durian shell using waste-derived catalysts is an effective waste management strategy as the bio-oil produced can be a potential alternative source of energy or chemical feedstocks.
To investigate the interaction of zinc oxide nanoparticles (ZnO NPs) with fly ash soil (FAS) for the reduction of metals from FAS by Parthenium hysterophorus were studied. The average accumulation of metals by P. hysterophorus stem were Fe 79.6%; Zn 88.5%; Cu 67.5%; Pb 93.6%; Ni 43.5% and Hg 39.4% at 5.5 g ZnO NP. The concentration of ZnO NP at 1.5 g did not affect the metals accumulation, however at 5.5 g ZnO NP showed highest metal reduction was 96.7% and at 10.5-15.5 g ZnO NP of 19.8%. The metal reduction rate was R max for Fe 16.4; Zn 21.1; Pb 41.9; Hg 19.1 was higher than Ni 6.4 and Cu 11.3 from the FAS at 5.5 g ZnO NP whereas, the reduction rate of Pb showed highest. With doses of 5.5 g ZnO NP the biomass increased upto 78%; the metal reduced upto 98.7% with the share of 100% ZnO NP from FAS. Further investigation with phytotoxicity the plant reactive oxygen species (ROS) production were affected due was mainly due to the recovery of metals from FAS (R2 = 0.99).
The tunability of semi-conductivity in SrTiO3 single crystal substrates has been realized by a simple encapsulated annealing method under argon atmosphere. This high temperature annealing-induced property changes are characterized by the transmission spectra, scanning electron microscopy (SEM) and synchrotron-based X-ray absorption (XAS). We find the optical property is strongly influenced by the annealing time (with significant decrease of transmittance). A sub gap absorption at ~427 nm is detected which is attributed to the introduction of oxygen vacancy. Interestingly, in the SEM images, annealing-induced regularly rectangle nano-patterns are directly observed which is contributed to the conducting filaments. The XAS of O K-edge spectra shows the changes of electronic structure by annealing. Very importantly, resistance switching response is displayed in the annealed SrTiO3 single crystal. This suggests a possible simplified route to tune the conductivity of SrTiO3 and further develop novel resistance switching materials.
Salinity expressed as total dissolved solids (TDS), is the most challenging parameter in bioremediation of produced water which may inhibit the microbial activities and cause sedimentation problems. The present study explores the feasibility of using walnut shell as an inexpensive and accessible adsorbent-carrier for the immobilization of isolated halophilic microorganisms for treatment of synthetic oilfield produced water. The moving bed biofilm reactor (MBBR) was examined with influent chemical oxygen demand (COD) concentrations from 900 to 3600 mg L-1, TDS concentrations from 35,000-200,000 mg L-1, and cycle times from 24 to 72 h. Comparison of the MBBR with the conventional sequencing batch reactor (SBR) indicated that both systems operated at lower influent COD and TDS concentrations satisfactorily; but at higher TDSs (above 150,000 mg L-1) the MBBR was more resistant to the shocks of toxicity (salinity) and organic load relative to the SBR. Also, the effluent turbidity was lower and the free sludge settling property was more favorable in the MBBR with average sludge volume index (SVI) of 38.8 mL g-1 compared to the SBR with SVI of 98.09 mL g-1. Microbial identification confirmed the presence of eight dominant halophilic species which were hydrocarbon degraders and/or denitrifiers.
Many developing countries, mostly situated in the tropical region, have incorporated a biological nitrogen removal process into their wastewater treatment plants (WWTPs). Existing wastewater characteristic data suggested that the soluble chemical oxygen demand (COD) in tropical wastewater is not sufficient for denitrification. Warm wastewater temperature (30 °C) in the tropical region may accelerate the hydrolysis of particulate settleable solids (PSS) to provide slowly-biodegradable COD (sbCOD) for denitrification. This study aimed to characterize the different fractions of COD in several sources of low COD-to-nitrogen (COD/N) tropical wastewater. We characterized the wastewater samples from six WWTPs in Malaysia for 22 months. We determined the fractions of COD in the wastewater by nitrate uptake rate experiments. The PSS hydrolysis kinetic coefficients were determined at tropical temperature using an oxygen uptake rate experiment. The wastewater samples were low in readily-biodegradable COD (rbCOD), which made up 3-40% of total COD (TCOD). Most of the biodegradable organics were in the form of sbCOD (15-60% of TCOD), which was sufficient for complete denitrification. The PSS hydrolysis rate was two times higher than that at 20 °C. The high PSS hydrolysis rate may provide sufficient sbCOD to achieve effective biological nitrogen removal at WWTPs in the tropical region.
Synthetic plastics are severely detrimental to the environment because non-biodegradable plastics do not degrade for hundreds of years. Nowadays, these plastics are very commonly used for food packaging. To overcome this problem, food packaging materials should be substituted with "green" or environmentally friendly materials, normally in the form of natural fiber reinforced biopolymer composites. Thermoplastic starch (TPS), polylactic acid (PLA) and polybutylene succinate (PBS) were chosen for the substitution, because of their availability, biodegradability, and good food contact properties. Plasticizer (glycerol) was used to modify the starch, such as TPS under a heating condition, which improved its processability. TPS films are sensitive to moisture and their mechanical properties are generally not suitable for food packaging if used alone, while PLA and PBS have a low oxygen barrier but good mechanical properties and processability. In general, TPS, PLA, and PBS need to be modified for food packaging requirements. Natural fibers are often incorporated as reinforcements into TPS, PLA, and PBS to overcome their weaknesses. Natural fibers are normally used in the form of fibers, fillers, celluloses, and nanocelluloses, but the focus of this paper is on nanocellulose. Nanocellulose reinforced polymer composites demonstrate an improvement in mechanical, barrier, and thermal properties. The addition of compatibilizer as a coupling agent promotes a fine dispersion of nanocelluloses in polymer. Additionally, nanocellulose and TPS are also mixed with PLA and PBS because they are costly, despite having commendable properties. Starch and natural fibers are utilized as fillers because they are abundant, cheap and biodegradable.
Lack of suitable auto/allografts has been delaying surgical interventions for the treatment of numerous disorders and has also caused a serious threat to public health. Tissue engineering could be one of the best alternatives to solve this issue. However, deficiency of oxygen supply in the wounded and implanted engineered tissues, caused by circulatory problems and insufficient angiogenesis, has been a rate-limiting step in translation of tissue-engineered grafts. To address this issue, we designed oxygen-releasing electrospun composite scaffolds, based on a previously developed hybrid polymeric matrix composed of poly(glycerol sebacate) (PGS) and poly(ε-caprolactone) (PCL). By performing ball-milling, we were able to embed a large percent of calcium peroxide (CP) nanoparticles into the PGS/PCL nanofibers able to generate oxygen. The composite scaffold exhibited a smooth fiber structure, while providing sustainable oxygen release for several days to a week, and significantly improved cell metabolic activity due to alleviation of hypoxic environment around primary bone-marrow-derived mesenchymal stem cells (BM-MSCs). Moreover, the composite scaffolds also showed good antibacterial performance. In conjunction to other improved features, such as degradation behavior, the developed scaffolds are promising biomaterials for various tissue-engineering and wound-healing applications.
This paper reviews the related literature reported in 2019 about various types of wastewaters associated with chemical and allied products. The subjects comprise wastewaters produced from various activities in agricultural, chemical, dye, petrochemical, and pharmaceutical. PRACTITIONER POINTS: Bioflocculant chitosan was used for sludge dewatering and the treatment of water and wastewater, and polishing of sanitary landfill leachate. Alkaline lignin-based flocculants were used to achieve excellent color removal for paper mill sludge. Powdered activated coke was used to remove COD (chemical oxygen demand) from chemical industry wastewater effluents.
Integrated fixed-film activated sludge (IFAS) process is considered as one of the leading-edge processes that provides a sustainable solution for wastewater treatment. IFAS was introduced as an advancement of the moving bed biofilm reactor by integrating the attached and the suspended growth systems. IFAS offers advantages over the conventional activated sludge process such as reduced footprint, enhanced nutrient removal, complete nitrification, longer solids retention time and better removal of anthropogenic composites. IFAS has been recognized as an attractive option as stated from the results of many pilot and full scales studies. Generally, IFAS achieves >90% removals for combined chemical oxygen demand and ammonia, improves sludge settling properties and enhances operational stability. Recently developed IFAS reactors incorporate frameworks for either methane production, energy generation through algae, or microbial fuel cells. This review details the recent development in IFAS with the focus on the pilot and full-scale applications. The microbial community analyses of IFAS biofilm and floc are underlined along with the special emphasis on organics and nitrogen removals, as well as the future research perspectives.
Prostate cancer has become the second leading cancer in men worldwide. Androgen plays an important role in normal functioning, development, and differentiation of the prostate, and thus is considered to be the most powerful candidate that mediates reactive oxygen species (ROS) balance in the prostate. The elevation of ROS has been associated with the progression and development of this disease. Conventional therapy has shown a high cure rate in patients with localized prostate cancer. Despite the patients respond favorably initially, this therapy fails to response in the advanced stage of the diseases even in the absence of androgens. Indeed, the onset and progression of prostate cancer could be prevented by changing dietary habits. Much information indicates that oxidative stress and prostate cancer can be modulated by dietary components rich in antioxidants. While there is substantial evidence to suggest an association between prostate cancer risk and ROS-mediated oxidative stress; therefore, the interactions and mechanisms of this phenomenon are worth to discuss further. This review aimed to discuss the mechanisms of action of oxidative stress involved in the progression of prostate cancer. We also highlighted how some of the vital dietary components dampen or exacerbate inflammation, oxidative stress, and prostate cancer. Overall, the reported information would provide a useful approach to the prevention of prostate cancer.
Alzheimer's disease (AD) is a fatal neurodegenerative disease that requires immediate attention. Oxidative stress that leads to the generation of reactive oxygen species is a contributing factor to the disease progression by promoting synthesis and deposition of amyloid-β, the main hallmark protein in AD. It has been previously demonstrated that nanoyttria possesses antioxidant properties and can alleviate cellular oxidative injury in various toxicity and disease models. This review proposed that nanoyttria could be used for the treatment of AD. In this paper, the evidence on the antioxidant potential of nanoyttria is presented and its prospects on AD therapy are discussed.
Defect engineering is increasingly recognized as a viable strategy for boosting the performance of photoelectrochemical (PEC) water splitting using metal oxide-based photoelectrodes. However, previously developed methods for generating point defects associated with oxygen vacancies are rather time-consuming. Herein, high density oxygen deficient α-Fe2O3 with the dominant (110) crystal plane is developed in a very short timescale of 10 minutes by employing aerosol-assisted chemical vapor deposition and pure nitrogen as a gas carrier. The oxygen-defective film exhibits almost 8 times higher photocurrent density compared to a hematite photoanode with a low concentration of oxygen vacancies which is prepared in purified air. The existence of oxygen vacancies improves light absorption ability, accelerates charge transport in the bulk of films, and promotes charge separation at the electrolyte/semiconductor interface. DFT simulations verify that oxygen-defective hematite has a narrow bandgap, electron-hole trapped centre, and strong adsorption energy of water molecules compared to pristine hematite. This strategy might bring PEC technology another step further towards large-scale fabrication for future commercialization.
Mohammad Anwar Mohamed Iqbal, Muhammad Zulhelmi Nazri, Mohammad Norazmi Ahmad, Erna Normaya Abdullah, Umie Fatihah Mohamad Haziz, Mohd Rizal Razali, et al.
Silver (I) dicyanonitrosomethanide, Ag[ONC(CN)2] represent a 3D interwoven coordination polymer organization in which all the donor atoms of the functional groups of ONC(CN)2- are coordinated to the Ag(I). Oxidation of styrene utilizing H2O2 as an oxidant in acetonitrile (CH3CN) was used as a model reaction to investigate the catalytic potential of the Ag (I) complex. The CH3CN was chosen as the solvent based on the data collected from Conductor like Screening Model for Real Solvents (COSMO-RS) study. The data indicate that the Ag [ONC(CN)2] complex was compatible and soluble in CH3CN. Different parameters such as styrene:H2O2 molar ratio, reaction time, catalyst mass, and reaction temperature were studied. Highest styrene conversion (36%) with 100% selectivity towards benzaldehyde (BZ) was achieved when 25 mg catalyst, 1:1 styrene to H2O2 molar ratio were used. The reaction was carried out at 303 K for 3 h. The catalytic conversion of styrene to BZ is proposed to take place via [Ag-H2O2] adduct with styrene oxide (StO) as an intermediate. Molecular Electrostatic Potential (MEP) shows that the Ag atom has the highest probability to coordinate with the oxygen atom of H2O2. The MEP data confirms the proposed mechanism.
The skin is the first line of defense against pathogen and other environmental pollutant. The body is constantly exposed to reactive oxygen species (ROS) that stimulates inflammatory process in the skin. Many studies have linked ROS to various inflammatory skin diseases. Patients with skin diseases face various challenges with inefficient and inappropriate treatment in managing skin diseases. Overproduction of ROS in the body will result in oxidative stress which will lead to various cellular damage and alter normal cell function. Multiple signaling pathways are seen to have significant effects during ROS-mediated oxidative stress. In this review, microalgae have been selected as a source of natural-derived antioxidant to combat inflammatory skin diseases that are prominent in today's society. Several studies have demonstrated that bioactive compounds isolated from microalgae have anti-inflammation and anti-oxidative properties that can help remedy various skin diseases. These compounds are able to inhibit production of pro-inflammatory cytokines and reduce the expression of inflammatory genes. Bioactive compounds from microalgae work in action by altering enzyme activities, regulating cellular activities, targeting major signaling pathways related to inflammation.
Crack formation in concrete is one of the main reasons for concrete degradation. Calcium alginate capsules containing biological self-healing agents for cementitious materials were studied for the self-healing of cement paste and mortars through in vitro characterizations such as healing agent survivability and retention, material stability, and biomineralization, followed by in situ self-healing observation in pre-cracked cement paste and mortar specimens. Our results showed that bacterial spores fully survived the encapsulation process and would not leach out during cement mixing. Encapsulated bacteria precipitated CaCO3 when exposed to water, oxygen, and calcium under alkaline conditions by releasing CO32- ions into the cement environment. Capsule rupture is not required for the initiation of the healing process, but exposure to the right conditions are. After 56 days of wet-dry cycles, the capsules resulted in flexural strength regain as high as 39.6% for the cement mortar and 32.5% for the cement paste specimens. Full crack closure was observed at 28 days for cement mortars with the healing agents. The self-healing system acted as a biological CO32- pump that can keep the bio-agents retained, protected, and active for up to 56 days of wet-dry incubation. This promising self-healing strategy requires further research and optimization.
Increasing agricultural irrigation to counteract a soil moisture deficit has resulted in the production of hazardous agricultural wastewater with high turbidity and chemical oxygen demand (COD). An innovative, sustainable, and effective solution is needed to overcome the pollution and water scarcity issues caused by the agricultural anthropogenic processes. This research focused on a sustainable solution that utilized a waste (broken lentil) as natural coagulant for turbidity and COD removal in agricultural wastewater treatment. The efficiency of the lentil extract (LE), grafted lentil extract (LE-g-DMC) and aluminium sulphate (alum) coagulants was optimized through the response surface methodology. Three-level Box-Behnken design was used to statistically visualize the complex interactions of pH, concentration of coagulants and settling time. LE achieved a significant 99.55% and 79.87% removal of turbidity and COD at pH 4, 88.46 mg/L of LE and 6.9 minutes of settling time, whereas LE-g-DMC achieved 99.83% and 80.32% removal of turbidity and COD at pH 6.7, 63.08 mg/L of LE-g-DMC and 5 minutes of settling time. As compared to alum, LE-g-DMC required approximately 30% less concentration. Moreover, LE and LE-g-DMC also required 75% and 65% less settling time as compared to the alum. Both LE and LE-g-DMC produced flocs with excellent settling ability (5.77 mg/L and 4.48 mL/g) and produced a significant less volume of sludge (10.60 mL/L and 8.23 mL/L) as compared with the alum. The economic analysis and assessments have proven the feasibility of both lentil-based coagulants in agricultural wastewater treatment.
Hypoxia, the result of disrupted vasculature, can be categorized in the main limiting factors for fracture healing. A lack of oxygen can cause cell apoptosis, tissue necrosis, and late tissue healing. Remedying hypoxia by supplying additional oxygen will majorly accelerate bone healing. In this study, biphasic calcium phosphate (BCP) scaffolds were fabricated by robocasting, an additive manufacturing technique. Then, calcium peroxide (CPO) particles, as an oxygen-releasing agent, were coated on the BCP scaffolds. Segmental radial defects with the size of 15 mm were created in rabbits. Uncoated and CPO-coated BCP scaffolds were implanted in the defects. The empty (control) group received no implantation. Repairing of the bone was investigated via X-ray, histological analysis, and biomechanical tests at 3 and 6 months postoperatively, with immunohistochemical examinations at 6 months after operation. According to the radiological observations, formation of new bone was augmented at the interface between the implant and host bone and internal pores of CPO-coated BCP scaffolds compared to uncoated scaffolds. Histomorphometry analysis represented that the amount of newly formed bone in the CPO-coated scaffold was nearly two times higher than the uncoated one. Immunofluorescence staining revealed that osteogenic markers, osteonectin and octeocalcin, were overexpressed in the defects treated with the coated scaffolds at 6 months of postsurgery, demonstrating higher osteogenic differentiation and bone mineralization compared to the uncoated scaffold group. Furthermore, the coated scaffolds had superior biomechanical properties as in the case of 3 months after surgery, the maximal flexural force of the coated scaffolds reached to 134 N, while it was 92 N for uncoated scaffolds. The results could assure a boosted ability of bone repair for CPO-coated BCP scaffolds implanted in the segmental defect of rabbit radius because of oxygen-releasing coating, and this system of oxygen-generating coating/scaffold might be a potential for accelerated repairing of bone defects.
Assessment of the treatment performance in the field-scale hybrid constructed wetland (CW) for ammonia manufacturing plant remains limited. After being in operations running on and off since 2014, the hybrid CW which treats effluent from the ammonia manufacturing plant in Peninsular, Malaysia has recently demonstrated the full clogging to the CW. It takes only 8 months to demonstrate a big deterioration of performance in 2019. Though the mechanism of clogging is not clear, which can be partially from inherent design problems or operational issues, nonetheless, it is important to evaluate how this clogging has impacted the effluent treatment performance and the continuous utilization of the CW. The purpose of this study is to evaluate the impact of the treatment performance on the ammoniacal nitrogen and COD removal when the CW is clogged. The result revealed that there is no impact on COD removal, but it has a substantial impact on the ammoniacal nitrogen removal. The ammoniacal nitrogen removal dropped to negative (outlet concentration is higher than inlet concentration) during the clogged period. Another observation is, the low removal rate also coincides with a high COD/N ratio, when the COD/N ratio increased to >2, the ammoniacal nitrogen removal rate dropped substantially, with the coefficient of determination, R2 of 40.5%. The root cause for the clogging to develop in a short period of time is unidentified. However, it is still worth noting that COD and ammoniacal nitrogen efficiency did not behave the same at the clogged CW.