Establishing an effective metal-free photocatalyst for sustainable applications remains a huge challenge. Herein, we developed ultrathin oxygen-doped g-C3N4 nanosheets with carbon defects (OCvN) photocatalyst via a facile gas bubble template-assisted thermal copolymerization method. A series of OCvN with different dopant amounts ranging from 0 to 10% were synthesized and used as photocatalysts under illumination of low-power (2 × 18 W, 0.18 mW/cm2) and commercially available energy-saving light bulbs. Upon testing for photocatalytic Escherichia coli inactivation, the best-performing sample, OCvN-3, demonstrated an astonishing disinfection activity of over 7-log reduction after 3 h of illumination, boasting an 18-fold improvement in its antibacterial activity compared to that of pristine g-C3N4. The enhanced performance was attributed to the synergistic effects of increased surface area, extended visible light harvesting, improved electronic conductivity, and ultralow resistance to charge transfer. This study successfully introduced a green photocatalyst that demonstrates the most effective disinfection performance ever recorded among metal-free g-C3N4 materials. Its disinfection capabilities are comparable to those of metal-based photocatalysts when they are exposed to low-power light.
Immobilization can be used to improve the stability of lipases and enhances lipase recovery and reusability, which increases its commercial value and industrial applications. Nevertheless, immobilization frequently causes conformational changes of the lipases, which decrease lipase catalytic activity. in the present work, we synthesized UIO-66 and grafted UIO-66 crystals with proline for immobilization of Candida rugosa lipase (CRL). As indicated by steady-state fluorescence microscopy, grafting of proline onto UIO-66 crystals induced beneficial conformational change in CRL. CRL immobilized on UIO-66/Pro (CRL@UIO-66/Pro) demonstrated higher enzyme activity and better recyclability than that immobilized on UIO-66 (CRL@UIO-66) in both hydrolysis (CRL@UIO-66/Pro: 0.34 U; CRL@UIO-66: 0.15 U) and transesterification (CRL@UIO-66/Pro: 0.93 U; CRL@UIO-66: 0.25 U) reactions. The higher values of kcat and kcat/Km of CRL@UIO-66/Pro also showed that it had better catalytic efficiency as compared to CRL@UIO-66. It is also worth noting that CRL@UIO-66/Pro (0.93 U) demonstrated a much higher transesterification activity as compared to free CRL (0.11 U), indicating that UIO-66/Pro has increased the solvent stability of CRL. Both CRL@UIO-66 and CRL@UIO-66/Pro were also used for the fabrication of biosensors for nitrofen with a wide linear range (0-100 μM), lower limit of detection, and good recovery rate.
The synthesis of nanocomposite with controlled surface morphology plays a key role for pollutant removal from aqueous environments. The influence of the molecular size of the polyelectrolyte in synthesizing silica-iron oxide core-shell nanocomposite with open shell structure was investigated by using dynamic light scattering, atomic force microscopy, and quartz crystal microbalance with dissipation (QCM-D). Here, poly(diallydimethylammonium chloride) (PDDA) was used to promote the attachment of iron oxide nanoparticles (IONPs) onto the silica surface to assemble a nanocomposite with magnetic and catalytic bifunctionality. High molecular weight PDDA tended to adsorb on silica colloid, forming a more extended conformation layer than low molecular weight PDDA. Subsequent attachment of IONPs onto this extended PDDA layer was more randomly distributed, forming isolated islands with open space between them. By taking amoxicillin, an antibiotic commonly found in pharmaceutical waste, as the model system, better removal was observed for silica-iron oxide nanocomposite with a more extended open shell structure.
Here, we explore the use of two- and three-dimensional scaffolds of multiwalled-carbon nanotubes (MWNTs) for hepatocyte cell culture. Our objective is to study the use of these scaffolds in liver tissue engineering and drug discovery. In our experiments, primary rat hepatocytes, the parenchymal (main functional) cell type in the liver, were cultured on aligned nanogrooved MWNT sheets, MWNT yarns, or standard 2-dimensional culture conditions as a control. We find comparable cell viability between all three culture conditions but enhanced production of the hepatocyte-specific marker albumin for cells cultured on MWNTs. The basal activity of two clinically relevant cytochrome P450 enzymes, CYP1A2 and CYP3A4, are similar on all substrates, but we find enhanced induction of CYP1A2 for cells on the MWNT sheets. Our data thus supports the use of these substrates for applications including tissue engineering and enhancing liver-specific functions, as well as in in vitro model systems with enhanced predictive capability in drug discovery and development.
Shape memory polymers (SMPs) are smart and adaptive materials able to recover their shape through an external stimulus. This functionality, combined with the good biocompatibility of polymers, has garnered much interest for biomedical applications. In this review, we discuss the design considerations critical to the successful integration of SMPs for use in vivo. We also highlight recent work on three classes of SMPs: shape memory polymers and blends, shape memory polymer composites, and shape memory hydrogels. These developments open the possibility of incorporating SMPs into device design, which can lead to vast technological improvements in the biomedical field.
Broadening light absorption and improving charge carrier separation are very critical to boost the water splitting efficiency in photoelectrochemical (PEC) systems. We herein reported a heterostructured photoanode consisting of BiVO4 and eco-friendly, near-infrared (NIR) CuInSeS@ZnS core-shell quantum dots (QDs) for PEC water oxidation. The decoration of core-shell QDs concurrently extends the absorption range of BiVO4 from the ultraviolet-visible to NIR region and promotes the effective separation and transfer of photo-excited electrons and holes. Without any sacrificial agents and co-catalysts, the as-fabricated NIR core-shell QDs/BiVO4 heterostructured photoanodes exhibit an approximately fourfold higher photocurrent density than that of the bare BiVO4, up to 3.17 mA cm-2 at 1.23 V versus the reversible hydrogen electrode. It is revealed that both a suitable band alignment and an intimate interfacial junction between QDs and BiVO4 are the main factors that result in enhanced charge separation and transfer efficiencies. We also highlight that the NIR CISeS QDs passivated with a ZnS shell can suppress the non-radiative recombination and enhance the stability of the QD photoanodes for optimized PEC performance. This work provides a facile and effective approach to boost the water oxidation efficiency of semiconductor photoanodes via utilizing NIR core-shell QDs as a light sensitizer and charge carrier separator.
Highly efficient and remarkable selective acetone conversion to isopropanol has been achieved via a heterogeneous catalytic hydrogenation of acetone by NaBH4 in the presence of semihollow palladium nanoparticles (PdNPs) grown on ITO substrate. PdNPs with high surface defect grown on an indium tin oxide (ITO) surface were prepared via a simple immersion of the substrate into a solution containing K2PdCl6, sodium dodecyl sulphate (SDS), and formic acid for 2 h at room temperature. The sample showed remarkably high heterogeneous catalytic efficiency by producing 99.8% of isopropanol within 6 min using only 0.28 μg of PdNPs on the ITO surface. The present system exhibits heterogenenous catalytic hydrogenation efficiency 1 × 10(6) time higher than using the conventional Raney Ni system.
This paper reports a facile, solution-phase approach to synthesizing a one-dimensional amorphous face-centered-cubic (fcc) platinum (a-Pt) nanostructure (nanofibers) directly on an indium-tin oxide (ITO) substrate. The electron microscopy analysis result shows that the a-Pt nanofiber has a diameter and length of approximately 50 nm and 1 μm, respectively, and is grown in high density on the entire surface of the ITO substrate. The X-ray photoelectron spectroscopy analysis result further reveals that the a-Pt nanofibers feature metallic properties with highly reactive surface chemistry, promising novel performance in electrochemistry, catalysis, and sensors. A synergetic interplay between the formic acid reducing agent and the hexamethylenetetramine surfactant in the reduction of Pt ions is assumed as the driving force for the formation of the amorphous phase in the Pt nanostructure. The catalytic properties of a-Pt were examined in the acetone hydrogenation reaction under microwave irradiation. a-Pt shows excellent heterogeneous catalytic properties for converting acetone to isopropyl alcohol with turnover number and frequency as high as 400 and 140 min(-1), respectively. The preparation and formation mechanism of the a-Pt nanofibers will be discussed in detail in this paper.
A deficiency in the photoelectrical dynamics at the interface due to the surface traps of the TiO2 electron transport layer (ETL) has been the critical factor for the inferiority of the power conversion efficiency (PCE) in the perovskite solar cells. Despite its excellent energy level alignment with most perovskite materials, its large density of surface defect as a result of sub lattice vacancies has been the critical hurdle for an efficient photovoltaic process in the device. Here, we report that atoms thick 2D TiS2 layer grown on the surface of a (001) faceted and single-crystalline TiO2 nanograss (NG) ETL have effectively passivated the defects, boosting the charge extractability, carrier mobility, external quantum efficiency, and the device stability. These properties allow the perovskite solar cells (PSCs) to produce a PCE as high as 18.73% with short-circuit current density (Jsc), open-circuit voltage (Voc), and fill-factor (FF) values as high as 22.04 mA/cm2, 1.13 V, and 0.752, respectively, a 3.3% improvement from the pristine TiO2-NG-based PSCs. The present approach should find an extensive application for controlling the photoelectrical dynamic deficiency in perovskite solar cells.
Chemotherapeutic cytotoxic agents such as paclitaxel (PTX) are considered essential for the treatment of various cancers. However, PTX injection is associated with severe systemic side effects and high rates of patient noncompliance. Micelle formulations (MFs) are nano-drug delivery systems that offer a solution to these problems. Herein, we report an advantageous carrier for the transdermal delivery of PTX comprising a new MF that consists of two biocompatible surfactants: cholinium oleate ([Cho][Ole]), which is a surface-active ionic liquid (SAIL), and sorbitan monolaurate (Span-20). A solubility assessment confirmed that PTX was readily solubilized in the SAIL-based micelles via multipoint hydrogen bonding and cation-π and π-π interactions between PTX and SAIL[Cho][Ole]. Dynamic light scattering (DLS) and transmission electron microscopy revealed that in the presence of PTX, the MF formed spherical PTX-loaded micelles that were well-distributed in the range 8.7-25.3 nm. According to DLS, the sizes and size distributions of the micelle droplets did not change significantly over the entire storage period, attesting to their physical stability. In vitro transdermal assessments using a Franz diffusion cell revealed that the MF absorbed PTX 4 times more effectively than a Tween 80-based formulation and 6 times more effectively than an ethanol-based formulation. In vitro and in vivo skin irritation tests revealed that the new carrier had a negligible toxicity profile compared with a conventional ionic liquid-based carrier. Based on these findings, we believe that the SAIL[Cho][Ole]-based MF has potential as a biocompatible nanocarrier for the effective transdermal delivery of poorly soluble chemotherapeutics such as PTX.
The postsynthetic modification of metal-organic frameworks (MOFs) has opened up a promising area to widen their water treatment application. However, their polycrystalline powdery state still restricts their widespread industrial-scale applications. Herein, the magnetization of UiO-66-NH2 is reported as a promising approach to facilitate the separation of the used MOFs after water treatment. A two-step postmodification procedure employing 2,4,6-trichloro-1,3,5-triazine (TCT) and 5-phenyl-1H-tetrazole (PTZ) agents was introduced to level up the adsorption performance of the magnetic nanocomposite. Despite a decrement in porosity and specific surface area of the designed MOFs (m-UiO-66-TCT) compared to neat UiO-66-NH2, it outweighs in adsorption capacity. It was observed that m-UiO-66-TCT has an adsorption capacity of ≈298 mg/g for methyl orange (MO) with facile MOF separation using an external magnet. Pseudo-second-order kinetic model and Freundlich isotherm models suitably interpret the experimental data. Thermodynamic studies showed that MO removal using m-UiO-66-TCT is spontaneous and thermodynamically favorable at higher temperatures. The m-UiO-66-TCT composite exhibited easy separation, high adsorption capacity, and good recyclability, rendering it an attractive candidate for the adsorptive removal of MO dye from aqueous environments.
Nickel (Ni) catalysts supported on mesoporous graphitic carbon nitride (mpg-C3N4) were synthesized through simple impregnation method with air and nitrogen calcination atmosphere for CO methanation. The effects of pretreatment gas on catalyst structure, surface characteristics, and Ni species reducibility were investigated. Under air-calcination condition, the increase in specific surface area of the catalyst can be ascribed to the creation of mesopores and exfoliation of bulk mpg-C3N4 to form thin sheets. However, excessive Ni content on the catalyst accelerated the decomposition of the mpg-C3N4 support during calcination. The catalysts calcined in nitrogen showed lower surface area and fewer number of pores compared to air-treatment. The Ni/mpg-C3N4 catalyst calcined in air with Ni loading 10% exhibited enhanced medium-temperature activity for CO methanation with 79.7% CO conversion and 73.9% CH4 selectivity. This finding can be explained by the formation of mpg-C3N4 thin sheets, which increased the number of catalyst active sites. The CO methanation performance of Ni/mpg-C3N4 catalysts calcined in air was superior to those calcined in nitrogen. Interestingly, CO2 formed by water-gas shift reaction at 320 °C also contributed to the overall methane formation through CO2 methanation. Therefore, mpg-C3N4 thin sheets can be an interesting support for nickel catalyst for CO x methanation.
High level of phosphotungstic acid (PWA) was self-immobilized on electrospun nylon nanofiberous sheet to fabricate highly selective methanol barrier layer for sandwich structured proton conducting membranes. Simple tuning for the assembly conditions of central layer and thickness of outer Nafion layers allowed obtaining different composite membranes with superior methanol barrier properties (namely, P=3.59×10(-8) cm2 s(-1)) coupled with proton conductivities reaching 58.6 mS cm(-1) at 30 °C. Comparable activation energy for proton transport and more than 20 times higher selectivity than Nafion 115 confirm the effectiveness of the central layer and resulting membranes for application in direct methanol fuel cells (DMFCs). When tested in DMFC single cell, the performance of hybrid membrane was far better than Nafion 115 especially at higher methanol concentrations.
Achieving a high energy density and long-cycle stability in energy storage devices demands competent electrochemical performance, often contingent on the innovative structural design of materials under investigation. This study explores the potential of transition metal selenide (TMSe), known for its remarkable activity, electronic conductivity, and stability in energy storage and conversion applications. The innovation lies in constructing hollow structures of binary metal selenide (CoNi-Se) at the surface of reduced graphene oxide (rGO) arranged in a three-dimensional (3D) morphology (CoNi-Se/rGO). The 3D interconnected rGO architecture works as a microcurrent collector, while porous CoNi-Se sheets originate the active redox centers. Electrochemical analysis of CoNi-Se/rGO based-electrode reveals a distinct faradic behavior, thereby resulting in a specific capacitance of 2957 F g-1 (1478.5 C g-1), surpassing the bare CoNi-Se with a value of 2149 F g-1 (1074.5 C g-1) at a current density of 1 A g-1. Both materials exhibit exceptional high-rate capabilities, retaining 83% of capacitance at 10 A g-1 compared to 1 A g-1. In a two-electrode coin cell system, the device achieves a high energy density of 73 Wh kg-1 at a power density of 1500 W kg-1, stating an impressive 90.4% capacitance retention even after enduring 20,000 cycles. This study underscores the CoNi-Se/rGO composite's promise as a superior electrode material for high-performance energy storage applications.