Polymeric pH-Responsive Metal-Supramolecular Nanoparticles for Synergistic Chemo-Photothermal Therapy.

Stimuli-responsive drug delivery carriers, particularly those exhibiting pH sensitivity, have attracted significant scholarly interest due to their promising potential in anticancer therapeutic applications. This phenomenon can primarily be ascribed to the inherently acidic nature of tumor microenvironments. However, pH-responsive carriers frequently require the incorporation of functional groups or materials sensitive to pH changes. Given the pH-sensitive characteristics of metal coordination with natural small-molecule drugs, organometallic supramolecules present a facile and effective strategy for integrating pH-responsive behavior into these systems. Meanwhile, utilizing the natural compound luteolin in conjunction with iron ions (Fe3+) through the advanced engineering technique of flash nanoprecipitation (FNP) results in the synthesis of stable, highly loaded nanoparticles (NPs) exhibiting a supramolecular photothermal effect. Our experimental findings substantiate that the photothermal effect persists over time, even after the pH-responsive release phase has ended. Consequently, these polymeric pH-responsive metallic supramolecular nanoparticles integrate chemotherapy and photothermal therapy, creating a synergistic approach to cancer treatment. This bifunctional platform, which exhibits both pH-responsive and photothermal properties, presents a highly promising avenue for biomedical applications, particularly in the area of tumor therapies. Its dual function offers a potentially efficacious approach to tumor treatment.

Optimization and Deep Learning Modeling of the Yield and Properties of Baobab-Derived Biodiesel Catalyzed by Waste Banana Bunch Stalk Biochar.

The integration of optimization techniques and deep learning models, which offer a promising avenue for improving the efficiency and sustainability of biodiesel production processes from baobab seed oil (BSO), is rare. This study utilized a multi-input-multioutput (MIMO) deep learning technique and the most recent central composite design (CCD) optimization tool to model and optimize the yield and properties of biodiesel produced from BSO. First, the baobab seed oil was extracted using a solvent extraction method. BSO was subsequently analyzed and converted to biodiesel by reacting CH3OH catalyzed by waste banana bunch stalk biochar activated by KOH. Multiobjective optimization and prediction of the biodiesel yield (Y) and several key fuel properties, including the cetane number (CN), kinematic viscosity (VS), and purity (P), were achieved. With better correlation coefficients of 0.9709, 0.9464, and 0.9714 for response training, response testing, and response validation, respectively, and a root-mean-square error of 0.00755, the MIMO model on the logsig transfer function accurately predicted the biodiesel yield and properties more than did the MISO and response surface methodology models. The optimum Y (96 wt %), CN (48), VS (3.3 mm2/s), and P (98.3%) were concurrently accomplished at a reaction temperature of 56 °C, a reaction time of 115 min, a CH3OH/BSO molar ratio of 15:1, a catalyst dosage of 6 wt %, and a stirring speed of 400 rpm with 98% optimal validation accuracy. CCD sensitivity analysis revealed that the CH3OH/BSO ratio was the most sensitive (50.9%) input predictor among the other input variables studied.

One pot application of a green chemistry-based finish for cotton fabric, providing hydrophobic, flame retardant, and antimicrobial properties.

Fluorinated and formaldehyde-based compounds impart excellent hydrophobicity and flame-retardant properties to cotton fabrics. However, they come with various health and environmental risks. A novel hydrophobic, flame retardant, and antimicrobial finishing agent free from fluorine and formaldehyde was synthesized. The diammonium phosphate octadecyl citrate (DAPOC) was synthesized by using stearic acid (octadecanoic acid), citric acid (propane-1,2,3-tricarboxylic acid), and diammonium hydrogen phosphate. It was grafted onto the cotton fabrics by employing the conventional pad-dry-cure method. The results indicated that this newly developed finish could be chemically bonded to cotton fabrics through C-O-C covalent bonds. The contact angle of the cotton fabric finished with a 12% concentration of the finishing agent reached 151.9°. Additionally, the finished cotton fabrics displayed evident flame-retardant properties. After undergoing 20 laundering cycles, DAPOC maintained strong hydrophobic and flame-retardant characteristics, demonstrating its durability. The chemical structure of DAPOC was verified by nuclear magnetic resonance spectroscopy (1H-NMR). The thermogravimetric analysis confirmed the flame-retardant nature of the treated cotton fabric samples. Scanning electron microscopy (SEM), Energy dispersive X-ray analysis (EDX), and Fourier-transform infrared spectroscopy (FTIR) results demonstrated the successful grafting of the newly created finish onto the cotton fiber. X-ray diffraction (XRD) spectra depicted that the crystalline structure of finished cotton fabric remained mostly unaltered. Furthermore, the finished cotton fabric exhibited commendable antimicrobial properties due to the inclusion of citric acid.

Deposition and water repelling of temperature-responsive nanopesticides on leaves.

Pesticides are widely used to increase agricultural productivity, however, weak adhesion and deposition lead to low efficient utilization. Herein, we prepare a nanopesticide formulation (tebuconazole nanopesticides) which is leaf-adhesive, and water-dispersed via a rapid nanoparticle precipitation method, flash nanoprecipitation, using temperature-responsive copolymers poly-(2-(dimethylamino)ethylmethylacrylate)-b-poly(ε-caprolactone) as the carrier. Compared with commercial suspensions, the encapsulation by the polymer improves the deposition of TEB, and the contact angle on foliage is lowered by 40.0°. Due to the small size and strong van der Waals interactions, the anti-washing efficiency of TEB NPs is increased by 37% in contrast to commercial ones. Finally, the acute toxicity of TEB NPs to zebrafish shows a more than 25-fold reduction as compared to commercial formulation indicating good biocompatibility of the nanopesticides. This work is expected to enhance pesticide droplet deposition and adhesion, maximize the use of pesticides, tackling one of the application challenges of pesticides.

Hydrothermal Carbonization of Cellulose with Ammonium Sulfate and Thiourea for the Production of Supercapacitor Carbon.

Doping with heteroatoms is the main method used to enhance energy storage with carbon materials, and polyatomic doping is one of the main challenges. Hydrothermal carbonization of cellulose was performed at 240 °C for 1 h. Ammonium sulfate and thiourea dopants were selected as the sources of inorganic nitrogen and organic nitrogen in the preparation of supercapacitor carbon. The effects of boric acid on the properties of the resulting hydrochar after KOH activation were examined. The results showed that the proportion of functional groups and the specific surface area of the activated hydrochar were reduced by the addition of boric acid, and the formation of micropores was inhibited. The hydrochar obtained from the reaction of cellulose and organic nitrogen compounds had a better pore size distribution and electrochemical properties after activation. The largest specific surface area (952.27 m2/g) was obtained when thiourea was used as the sole dopant. In a three-electrode system, the specific capacitance of the activated hydrochar reached 235.8 F/g at a current density of 1 A/g. After 20,000 charging and discharging cycles at a current density of 10 A/g, the capacitance retention rate was 99.96%. Therefore, this study showed that supercapacitor carbon with good electrochemical properties was obtained by the direct reactions of cellulose with organic nitrogen compounds.

Solution processed high performance perovskite solar cells based on a silver nanowire-titanium dioxide hybrid top electrode.

Longer silver nanowires (AgNWs) > 50 µm and even 90 µm in length have been produced via a polyol method by just changing the stirring speed at a temperature of 130 °C. As-synthesized longer AgNWs are further utilized to construct transparent conductive AgNWs films by a facile drop-casting technique that attained a sheet resistance of 14.5 Ω sq-1 and transmittance over 85%, which is higher than ITO film. The use of a AgNWs/TiO2 hybrid electrode decreases the sheet resistance to 8.3 Ω sq-1, which is attributed to the enhancement of connections between AgNWs by filling the empty spaces between nanowires and TiO2 nanoparticles. Transparent perovskite solar cells (PSCs) on the basis of these AgNWs and AgNWs/TiO2 hybrid top electrodes were made and examined. Due to the light scattering nature of TiO2 nanoparticles, optical transmittance of the AgNWs/TiO2 hybrid electrode enhances to some extent after the coating of a TiO2 layer. Both cell efficiencies and stability of the PSCs are enhanced by using the AgNWs/TiO2 top electrode. A power conversion efficiency (PCE) of 10.65% was attained for perovskite devices based on only the AgNW electrode with a sheet resistance of 14.5 Ω sq-1. A PCE of 14.53% was achieved after coating with TiO2 nanoparticles, indicating the layer effect of TiO2 coating.

Correction: Solution processed high performance perovskite solar cells based on a silver nanowire-titanium dioxide hybrid top electrode.

[This corrects the article DOI: 10.1039/D2RA06778A.].

Comparative study of ozonation and ozonation catalyzed by Fe-loaded biochar as catalyst to remove methylene blue from aqueous solution.

Ozone-based processes gained much attention in recent years. However, due to low oxidative stability and utilization rate, single ozonation process (SOP) is insufficient for complete mineralization of pollutants. As a result, the single ozonation process is performed in the presence of a catalyst, a process known as catalytic ozonation process (COP). A promising catalyst (Fe/BC) was prepared by impregnating iron on biochar surface to remove methylene blue from aqueous solution via heterogeneous catalytic ozonation process (HCOP). The prepared Fe/BC features were characterized using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM) and Brunauer-Emmett-Teller method (BET) before and after HCOP. Furthermore, the effect of various operating parameters such as ozone dose, catalyst dose, initial dye concentration, initial pH on the efficiency of SOP and HCOP were compared. In comparison to single ozonation process, the experimental study found that heterogeneous catalytic ozonation process has the highest efficiency. At pH 7.0, approximately 76% of methylene blue is removed during single ozonation process in 60 min. Heterogeneous catalytic ozonation process showed 95% methylene blue elimination from aqueous solution. The efficiency of heterogeneous catalytic ozonation process was decreased by 52% in the presence of hydroxyl radical (●OH) scavenger, indicating that hydroxyl is the major oxidant during heterogeneous catalytic ozonation process for the removal of methylene blue from aqueous solution. Fe/BC catalyst appears to have a lot of industrial promise, as well as the ability to remove methylene blue from aqueous solution via heterogeneous catalytic ozonation process.

Metallic nanoparticles for catalytic reduction of toxic hexavalent chromium from aqueous medium: A state-of-the-art review.

The ever increasing concentration of toxic and carcinogenic hexavalent chromium (Cr (VI)) in various environmental mediums including water-bodies due to anthropogenic activities with rapid civilization and industrialization have become the major issue throughout the globe during last few decades. Therefore, developing new strategies for the treatment of Cr(VI) contaminated wastewaters are in great demand and have become a topical issue in academia and industry. To date, various techniques have been used for the remediation of Cr(VI) contaminated wastewaters including solvent extraction, adsorption, catalytic reduction, membrane filtration, biological treatment, coagulation, ion exchange and photo-catalytic reduction. Among these methods, the transformation of highly toxic Cr(VI) to benign Cr(III) catalyzed by metallic nanoparticles (M-NPs) with reductant has gained increasing attention in the past few years, and is considered to be an effective approach due to the superior catalytic performance of M-NPs. Thus, it is a timely topic to review this emerging technique for Cr(VI) reduction. Herein, recent development in synthesis of M-NPs based non-supported, supported, mono-, bi- and ternary M-NPs catalysts, their characterization and performance for the reduction of Cr(VI) to Cr(III) are reviewed. The role of supporting host to stabilize the M-NPs and leading to enhance the reduction of Cr(VI) are discussed. The Cr(VI) reduction mechanism, kinetics, and factors affecting the kinetics are overviewed to collect the wealthy kinetics data. Finally, the challenges and perspective in Cr(VI) reduction catalyzed by M-NPs are proposed. We believe that this review will assist the researchers who are working to develop novel M-NPs catalysts for the reduction of Cr(VI).

Fe-zeolite catalyst for ozonation of pulp and paper wastewater for sustainable water resources.

The pulp and paper industry consumes enormous quality of freshwater, leading to wastewater. It must be treated to remove pollutants, particularly residual dyestuffs, before releasing them to water bodies to avoid adverse environmental effects. The traditional wastewater treatment methods used for the pulp and paper industry are less efficient in colour and chemical oxygen demand (COD) removal. The current study is aimed at developing a novel catalyst for the catalytic ozonation of pulp and paper wastewater with better colour and COD removal for sustainable resources of clean water. The proposed catalyst is impregnated by iron on natural zeolites. Various parameters such as catalyst dose, pH, ozone dose, initial COD concentration, and reaction time are studied and optimized. The performance was evaluated by comparing the results with the single ozonation process (SOP) and catalytic ozonation process (COP). The highest COD and colour reduction efficiencies have been achieved, i.e., 71%, and 88% at a natural pH of 6.8. The proposed process achieved higher COD and colour efficiencies than the single ozonation process and catalytic ozonation process using raw zeolites. The improvement in efficiencies are 23% and 29% for SOP and 17% and 19% for COP, respectively. Hence, the results proposed the sustainability and applicability of COP to treat paper and pulp sector effluent.

Overview of Feedstocks for Sustainable Biodiesel Production and Implementation of the Biodiesel Program in Pakistan.

The energy demand of the world is skyrocketing due to the exponential economic growth and population expansion. To meet the energy requirement, the use of fossil fuels is not a good decision, causing environmental pollution such as CO2 emissions. Therefore, the use of renewable energy sources like biofuels can meet the energy crisis especially for countries facing oil shortages such as Pakistan. This review describes the comparative study of biodiesel synthesis for various edible oils, non-edible oils, and wastes such as waste plastic oil, biomass pyrolysis oil, and tyre pyrolysis oil in terms of their oil content and extraction, cetane number, and energy content. The present study also described the importance of biodiesel synthesis via catalytic transesterification and its implementation in Pakistan. Pakistan is importing an extensive quantity of cooking oil that is used in the food processing industries, and as a result, a huge quantity of waste cooking oil (WCO) is generated. The potential waste oils for biodiesel synthesis are chicken fat, dairy scum, WCO, and tallow oil that can be used as potential substrates of biodiesel. The implementation of a biodiesel program as a replacement of conventional diesel will help to minimize the oil imports and uplift the country's economy. Biodiesel production via homogeneous and heterogeneous catalyzed transesterification is more feasible among all transesterification processes due to a lesser energy requirement and low cost. Therefore, biodiesel synthesis and implementation could minimize the imports of diesel by significantly contributing to the overall Gross Domestic Product (GDP). Although, waste oil can meet the energy needs, more available cultivation land should be used for substrate cultivation. In addition, research is still needed to explore innovative solvents and catalysts so that overall biodiesel production cost can be minimized. This would result in successful biodiesel implementation in Pakistan.

Evaluation of renewable pH-responsive starch-based flocculant on treating and recycling of highly saline textile effluents.

Herein, we report a novel renewable pH-responsive starch-based flocculant (CIAT-ST) via etherifying 2-chloro-4,6-isopropylamino-[1,3,5]-triazine (CIAT) onto the starch backbones for decontamination and reuse of highly saline effluents. The obtained CIAT-ST shows a unique pH-sensibility and reversibility in response to a subtle pH change due to a pH-controllable surface charge density of polymer chains. The level of residual CIAT-ST in the solution can be facilely monitored by using UV-vis detection. The dye flocculation performance of CIAT-ST was evaluated by using a batch experiment. The results exhibited that the dye removal was highly dependent on the solution pH (optimal pH was 2), the flocculation equilibrium can be achieved within 5 min, and the maximum flocculation capacity of CIAT-ST for K-2BP and KN-B5 were calculated to be 2452.6 ± 23.9 and 792.7 ± 14.1 mg/g, respectively. The multiple flocculation mechanisms, including charge neutralization, bridging and charge patching, may participate in the flocculation process. Adjustment in pH-mediated hydrophilicity-hydrophobicity switch of flocculant facilitates readily recovery and then sequentially reused three times while retaining satisfying flocculation efficiency. A significant contribution was also confirmed that the highly saline effluents after flocculation and sedimentation were reused in three successive dyeing processes without sacrificing fabric quality (ΔE* < 1) due to relatively low polymer residuals, and the efficiency of salt reuse for consecutive regeneration processes could be achieved above 85%. The present work could provide alternative thoughts for the reutilization of spent flocculant and clarified saline wastewater, which is also an efficient and sustainable strategy for textile wastewater management.

Impacts of non-oxidative torrefaction conditions on the fuel properties of indigenous biomass (bagasse).

Biomass is considered as the largest renewable energy source in the world. However, some of its inherent properties such as hygroscopicity, lower energy content, low mass density and bio-degradation on storage hinder its extensive application in energy generation processes. Torrefaction, a thermochemical process carried out at 200-300°C in a non-oxidative environment, can address these inherent problems of the biomass. In this work, torrefaction of bagasse was performed in a bench-scale tubular reactor at 250°C and 275°C with residence times of 30, 60 and 90 mins. The effects of torrefaction conditions on the elemental composition, mass yield, energy yield, oxygen/carbon (O/C) and hydrogen/carbon (H/C) ratios, higher heating values and structural composition were investigated and compared with the commercially available 'Thar 6' and 'Tunnel C' coal. Based on the targeted mass and energy yields of 80% and 90% respectively, the optimal process conditions turned out to be 250°C and 30 mins. Torrefaction of the bagasse conducted at 275°C and 90 min raised the carbon content in bagasse to 58.14% and resulted in a high heating value of 23.84 MJ/kg. The structural and thermal analysis of the torrefied bagasse indicates that the moisture, non-structural carbohydrates and hemicellulose were reduced, which induced the hydrophobicity in the bagasse and enhanced its energy value. These findings showed that torrefaction can be a sustainable pre-treatment process to improve the fuel and structural properties of biomass as a feedstock for energy generation processes.

Enhancement of fuel characteristics of rice husk via torrefaction process.

Torrefaction, is a pretreatment process in the conversion of various biomass feedstocks into an efficient solid fuel. In the present research, rice husk was torrefied at 200°C, 250°C, and 300°C for 10, 30, 90, and 150 minutes under a non-oxidative environment. The energy yield and mass yield of torrefied solid residues ranged from 51.3% to 96.8%, and 49.1% to 95.1%, respectively, under torrefaction conditions. Increasing the residence time and temperature of thermal treatment causes a rise in carbon content from 32.45% to 48.5%, and raises the calorific value from 16.48 MJ/kg to 19.82 MJ/kg. The torrefaction process also reduced the swelling tendency of the biomass in water from its initial value of 308% to 92% only. Various other characterizations including Fourier transform infrared radiation, thermogravimetric analysis (TGA) and scanning electron microscopy were performed to analyze the structural and textural aspects of torrefied biomass. The TGA and derivative thermogravimetric analysis curves indicated that torrefaction affected the hemicellulose fraction of biomass significantly. The surface morphology of thermolyzed samples revealed the rupture of the surface induced by the torrefaction process. Overall, the torrefaction process has not only improved the fuel characteristics of the rice husk but also enhanced its hydrophobicity.