ABSTRACT
The inactivation of natural enzymes by radiation poses a great challenge to their applications for radiotherapy. Single-atom nanozymes (SAzymes) with high structural stability under such extreme conditions become a promising candidate for replacing natural enzymes to shrink tumors. Here, we report a CuN3-centered SAzyme (CuN3-SAzyme) that exhibits higher peroxidase-like catalytic activity than a CuN4-centered counterpart, by locally regulating the coordination environment of single copper sites. Density functional theory calculations reveal that the CuN3 active moiety confers optimal H2O2 adsorption and dissociation properties, thus contributing to high enzymatic activity of CuN3-SAzyme. The introduction of X-ray can improve the kinetics of the decomposition of H2O2 by CuN3-SAzyme. Moreover, CuN3-SAzyme is very stable after a total radiation dose of 500 Gy, without significant changes in its geometrical structure or coordination environment, and simultaneously still retains comparable peroxidase-like activity relative to natural enzymes. Finally, this developed CuN3-SAzyme with remarkable radioresistance can be used as an external field-improved therapeutics for enhancing radio-enzymatic therapy in vitro and in vivo. Overall, this study provides a paradigm for developing SAzymes with improved enzymatic activity through local coordination manipulation and high radioresistance over natural enzymes, for example, as sensitizers for cancer therapy.
Subject(s)
Copper , Hydrogen Peroxide , Peroxidase , Radiation Tolerance , Copper/chemistry , Animals , Humans , Hydrogen Peroxide/chemistry , Hydrogen Peroxide/metabolism , Peroxidase/metabolism , Peroxidase/chemistry , Mice , Cell Line, Tumor , Catalysis/radiation effects , KineticsABSTRACT
Many emerging and re-emerging infectious diseases are prevalent, and the number of patients with allergies is increasing. Therefore, the importance of purifying the living environment is increasing. Photocatalysts undergo extreme redox reactions and decompose organic matter upon exposure to the excitation light. In contrast to ultraviolet light and disinfectants, which are standard methods for inactivating viruses and eliminating microorganisms, photocatalysts can decompose toxic substances, such as endotoxins and allergens, rendering them harmless to the human body. Photocatalysts have attracted significant attention as potential antiviral and antimicrobial agents. This review outlines the antiviral, antimicrobial, and anti-allergenic effects of photocatalysts. Especially, we have discussed the inactivation of SARS-CoV-2 in liquids and aerosols, elimination of Legionella pneumophila in liquids, decomposition of its endotoxin, decomposition of cat and dog allergens, and elimination of their allergenicity using photocatalysts. Furthermore, we discuss future perspectives on how photocatalysts can purify living environments, and how photocatalytic technology can be applied to companion animals and the livestock industry.
Subject(s)
Allergens , Allergens/immunology , Allergens/chemistry , Animals , Humans , SARS-CoV-2/immunology , SARS-CoV-2/radiation effects , Catalysis/radiation effects , Disinfection/methods , Photochemical Processes , Legionella pneumophila/immunology , Legionella pneumophila/radiation effectsABSTRACT
Biotic-abiotic hybrid photocatalytic system is an innovative strategy to capture solar energy. Diversifying solar energy conversion products and balancing photoelectron generation and transduction are critical to unravel the potential of hybrid photocatalysis. Here, we harvest solar energy in a dual mode for Cu2-xSe nanoparticles biomineralization and seawater desalination by integrating the merits of Shewanella oneidensis MR-1 and biogenic nanoparticles. Photoelectrons generated by extracellular Se0 nanoparticles power Cu2-xSe synthesis through two pathways that either cross the outer membrane to activate periplasmic Cu(II) reduction or are directly delivered into the extracellular space for Cu(I) evolution. Meanwhile, photoelectrons drive periplasmic Cu(II) reduction by reversing MtrABC complexes in S. oneidensis. Moreover, the unique photothermal feature of the as-prepared Cu2-xSe nanoparticles, the natural hydrophilicity, and the linking properties of bacterium offer a convenient way to tailor photothermal membranes for solar water production. This study provides a paradigm for balancing the source and sink of photoelectrons and diversifying solar energy conversion products in biotic-abiotic hybrid platforms.
Subject(s)
Biomineralization , Copper , Seawater , Shewanella , Solar Energy , Shewanella/metabolism , Copper/chemistry , Copper/metabolism , Seawater/microbiology , Seawater/chemistry , Salinity , Water Purification/methods , Nanoparticles/chemistry , Catalysis/radiation effectsABSTRACT
A lack of eco-friendly, highly active photocatalyst for peroxymonosulfate (PMS) activation and unclear environmental risks are significant challenges. Herein, we developed a double S-scheme Fe2O3/BiVO4(110)/BiVO4(010)/Fe2O3 photocatalyst to activate PMS and investigated its impact on wheat seed germination. We observed an improvement in charge separation by depositing Fe2O3 on the (010) and (110) surfaces of BiVO4. This enhancement is attributed to the formation of a dual S-scheme charge transfer mechanism at the interfaces of Fe2O3/BiVO4(110) and BiVO4(010)/Fe2O3. By introducing PMS into the system, photogenerated electrons effectively activate PMS, generating reactive oxygen species (ROS) such as hydroxyl radicals (·OH) and sulfate radicals (SO4·-). Among the tested systems, the 20% Fe2O3/BiVO4/Vis/PMS system exhibits the highest catalytic efficiency for norfloxacin (NOR) removal, reaching 95% in 40 min. This is twice the catalytic efficiency of the Fe2O3/BiVO4/PMS system, 1.8 times that of the Fe2O3/BiVO4 system, and 5 times that of the BiVO4 system. Seed germination experiments revealed that Fe2O3/BiVO4 heterojunction was beneficial for wheat seed germination, while PMS had a significant negative effect. This study provides valuable insights into the development of efficient and sustainable photocatalytic systems for the removal of organic pollutants from wastewater.
Subject(s)
Bismuth , Ferric Compounds , Light , Norfloxacin , Peroxides , Vanadates , Vanadates/chemistry , Vanadates/radiation effects , Bismuth/chemistry , Norfloxacin/chemistry , Norfloxacin/radiation effects , Catalysis/radiation effects , Ferric Compounds/chemistry , Peroxides/chemistry , Photochemical Processes , Triticum/chemistry , Triticum/radiation effectsABSTRACT
Photosynthetic inorganic biohybrid systems (PBSs) combining an inorganic photosensitizer with intact living cells provide an innovative view for solar hydrogen production. However, typical whole-cell biohybrid systems often suffer from sluggish electron transfer kinetics during transmembrane diffusion, which severely limits the efficiency of solar hydrogen production. Here, a unique biohybrid system with a quantum yield of 8.42% was constructed by feeding bismuth-doped carbon dots (Bi@CDS) to Escherichia coli (E. coli). In this biohybrid system, Bi@CDS can enter the cells and transfer the electrons upon light irradiation, greatly reducing the energy loss and shortening the distance of electron transfer. More importantly, the photocatalytic hydrogen production of the E. coli-Bi@CDs biohybrid system reached up to 0.95 mmol within 3 h under light irradiation (420-780 nm, 2000 W m-2), which is 1.36 and 2.38 times higher than that in the E. coli-CDs biohybrid system and the E. coli system, respectively. In addition, the mechanism of enhanced hydrogen production was further explored. It was found that the accelerated decomposition of glucose, the accelerated production of pyruvate, the inhibition of lactic acid, and the increase of formic acid were the reasons for the increase of hydrogen production. This work provides a novel strategy for improving the hydrogen production in photosynthetic inorganic biohybrid systems.
Subject(s)
Bismuth , Carbon , Escherichia coli , Hydrogen , Quantum Dots , Escherichia coli/metabolism , Escherichia coli/drug effects , Hydrogen/metabolism , Hydrogen/chemistry , Bismuth/chemistry , Carbon/chemistry , Quantum Dots/chemistry , Light , Catalysis/radiation effectsABSTRACT
The ubiquity and impact of pharmaceuticals and pesticides, as well as their residues in environmental compartments, particularly in water, have raised human and environmental health concerns. This emphasizes the need of developing sustainable methods for their removal. Solar-driven photocatalytic degradation has emerged as a promising approach for the chemical decontamination of water, sparking intensive scientific research in this field. Advancements in photocatalytic materials have driven the need for solar reactors that efficiently integrate photocatalysts for real-world water treatment. This study reports preliminary results from the development and evaluation of a solar system for TiO2-based photocatalytic degradation of intermittently flowing water contaminated with doxycycline (DXC), sulfamethoxazole (SMX), dexamethasone (DXM), and carbendazim (CBZ). The system consisted of a Fresnel-type UV solar concentrator that focused on the opening and focal point of a parabolic trough concentrator, within which tubular quartz glass reactors were fixed. Concentric springs coated with TiO2, arranged one inside the other, were fixed inside the quartz reactors. The reactors are connected to a raw water tank at the inlet and a check valve at the outlet. Rotating wheels at the collector base enable solar tracking in two axes. The substances (SMX, DXC, and CBZ) were dissolved in dechlorinated tap water at a concentration of 1.0 mg/L, except DXM (0.8 mg/L). The water underwent sequential batch (~ 3 L each, without recirculation) processing with retention times of 15, 30, 60, 90, and 120 min. After 15 min, the degradation rates were as follows: DXC 87%, SMX 35.5%, DXM 32%, and CBZ 31.8%. The system processed 101 L of water daily, simultaneously removing 870, 355, 256, and 318 µg/L of DXC, SMX, DXM, and CBZ, respectively, showcasing its potential for real-world chemical water decontamination application. Further enhancements that enable continuous-flow operation and integrate highly effective adsorbents and photocatalytic materials can significantly enhance system performance.
Subject(s)
Photochemistry , Solar Energy , Water Pollutants, Chemical , Water Purification , Water , Catalysis/radiation effects , Water/chemistry , Water Purification/instrumentation , Water Purification/methods , Humans , Water Pollutants, Chemical/chemistry , Water Pollutants, Chemical/isolation & purification , Doxycycline/chemistry , Doxycycline/isolation & purification , Sulfamethoxazole/chemistry , Sulfamethoxazole/isolation & purification , Dexamethasone/chemistry , Dexamethasone/isolation & purification , Quartz , Chromatography , Temperature , Time Factors , Animals , Water SupplyABSTRACT
The installation of gem-difluoromethylene groups into organic structures remains a daunting synthetic challenge despite their attractive structural, physical, and biochemical properties. A very efficient retrosynthetic approach would be the functionalization of a single C-F bond from a trifluoromethyl group. Recent advances in this line of attack have enabled the C-F activation of trifluoromethylarenes, but limit the accessible motifs to only benzylic gem-difluorinated scaffolds. In contrast, the C-F activation of trifluoroacetates would enable their use as a bifunctional gem-difluoromethylene synthon. Herein, we report a photochemically mediated method for the defluorinative alkylation of a commodity feedstock: ethyl trifluoroacetate. A novel mechanistic approach was identified using our previously developed diaryl ketone HAT catalyst to enable the hydroalkylation of a diverse suite of alkenes. Furthermore, electrochemical studies revealed that more challenging radical precursors, namely trifluoroacetamides, could also be functionalized via synergistic Lewis acid/photochemical activation. Finally, this method enabled a concise synthetic approach to novel gem-difluoro analogs of FDA-approved pharmaceutical compounds.
Subject(s)
Acetamides/chemistry , Esters/chemical synthesis , Fluoroacetates/chemistry , Alkenes/chemistry , Alkylation , Catalysis/radiation effects , Ketones/chemistry , Ketones/radiation effects , Molecular StructureABSTRACT
Although organic artificial enzymes have been reported as biomimetic oxidation catalysts and are widely used for colorimetric biosensors, developing organic artificial enzymes with high enzymatic activity is still a challenge. Two-dimensional (2D) covalent organic frameworks (COFs) have shown superior potential in biocatalysts because of their periodic π-π arrays, tunable pore size and structure, large surface area, and thermal stability. The interconnection of electron acceptor and donor building blocks in the 2D conjugated COF skeleton can lead to narrower band gaps and efficient charge separation and transportation and thus is helpful to improve catalytic activity. Herein, a donor-acceptor 2D COF was synthesized using tetrakis(4-aminophenyl)pyrene (Py) as an electron donor and thieno[3,2-b]thiophene-2,5-dicarbaldehyde (TT) as an electron acceptor. Under visible light irradiation, the donor-acceptor 2D COF exhibited superior enzymatic catalytic activity, which could catalyze the oxidation of chromogenic substrates such as 3,3',5,5'-tetramethylbenzidine (TMB) by the formation of superoxide radicals and holes. Based on the above property, the photoactivated donor-acceptor 2D COF with enzyme-like catalytic properties was designed as a robust colorimetric probe for cheap, highly sensitive, and rapid colorimetric detection of glutathione (GSH); the corresponding linear range of GSH was 0.4-60 µM, and the limit of detection was 0.225 µM. This study not only presents the construction of COF-based light-activated nanozymes for environmentally friendly colorimetric detection of GSH but also provides a smart strategy for improving nanozyme activity.
Subject(s)
Glutathione/blood , Metal-Organic Frameworks/chemistry , Nanostructures/chemistry , Benzidines/chemistry , Catalysis/radiation effects , Chromogenic Compounds/chemistry , Colorimetry/methods , Density Functional Theory , Glutathione/chemistry , Humans , Light , Limit of Detection , Metal-Organic Frameworks/chemical synthesis , Metal-Organic Frameworks/radiation effects , Models, Chemical , Nanostructures/radiation effects , Oxidation-Reduction , Pyrenes/chemical synthesis , Pyrenes/chemistry , Pyrenes/radiation effects , Thiophenes/chemical synthesis , Thiophenes/chemistry , Thiophenes/radiation effectsABSTRACT
Control over the stereochemistry of excited-state photoreactions remains a significant challenge in organic synthesis. Recently, it has become recognized that the photophysical properties of simple organic substrates can be altered upon coordination to Lewis acid catalysts, and that these changes can be exploited in the design of highly enantioselective catalytic photoreactions. Chromophore activation strategies, wherein simple organic substrates are activated towards photoexcitation upon binding to a Lewis acid catalyst, rank among the most successful asymmetric photoreactions. Herein, we show that chiral Brønsted acids can also catalyze asymmetric excited-state photoreactions by chromophore activation. This principle is demonstrated in the context of a highly enantio- and diastereoselective [2+2] photocycloaddition catalyzed by a chiral phosphoramide organocatalyst. Notably, the cyclobutane products arising from this method feature a trans-cis stereochemistry that is complementary to other enantioselective catalytic [2+2] photocycloadditions reported to date.
Subject(s)
Cycloaddition Reaction/methods , Light , Catalysis/radiation effects , Molecular Structure , StereoisomerismABSTRACT
In this study, we introduced four "claw-like" units of dipicolylamine (DPA) to a tetraphenylethylene (TPE)-based organic molecular cage (DPA-TPE-Cage). Coordinated with Zn2+ ions, the obtained ZnDPA-TPE-Cage exhibited aggregation induced emission (AIE) effects and oxidase-like properties, which endowed it with the ability to selectively image and kill Gram-positive bacteria S. aureus efficiently.
Subject(s)
Anti-Bacterial Agents/pharmacology , Fluorescent Dyes/pharmacology , Nanoparticles/chemistry , Amines/chemistry , Amines/pharmacology , Amines/radiation effects , Anti-Bacterial Agents/chemistry , Anti-Bacterial Agents/radiation effects , Catalysis/radiation effects , Cell Membrane/drug effects , Fluorescent Dyes/chemistry , Fluorescent Dyes/radiation effects , Light , Microbial Sensitivity Tests , Nanoparticles/radiation effects , Picolinic Acids/chemistry , Picolinic Acids/pharmacology , Picolinic Acids/radiation effects , Reactive Oxygen Species/metabolism , Staphylococcus aureus/drug effects , Stilbenes/chemistry , Stilbenes/pharmacology , Stilbenes/radiation effects , Zinc/chemistry , Zinc/pharmacology , Zinc/radiation effectsABSTRACT
Light-driven polymerization, such as photoinduced electron/energy transfer-reversible addition-fragmentation chain transfer (PET-RAFT) polymerization, enables biological benign conditions and versatile functional polymer structure design, which is readily used in protein-polymer bioconjugates. However, conventional metalloporphyrinic homogeneous catalysts for PET-RAFT polymerization suffer from limited aqueous solubility and tedious purification. Here we demonstrate the design of PET-RAFT photocatalyst from the reticular assembled Zr-porphyrinic metal-organic frameworks (MOFs), along with a biomacromolecule-based chain transfer agent, as efficient bioconjugation tools in water. Our methodology offers manufacturing advantages on bioconjugates under mild conditions such that MTT (3-[4,5-dimethylthiazol-2-yl]-2,5 diphenyl tetrazolium bromide) and cytotoxicity assays have shown the preservation of the protein integrity, bioactivity, and high cell viability after PET-RAFT polymerization. We find that the fast kinetics are benefiting from the ultrahigh loading of metalloporphyrins in MOF-525-Zn. This heterogeneous catalyst also allows us to maintain living characteristics to incorporate myriads of monomers into block copolymers. Other advantages like easy postreaction purification, reusability, and high oxygen tolerance even in an open system are demonstrated. This study provides a tool of highly efficient heterogeneous photocatalysts for polymer-protein bioconjugation in aqueous media and paves the road for biological applications.
Subject(s)
Acrylamides/chemistry , Metal-Organic Frameworks/chemistry , Serum Albumin, Bovine/chemistry , Acrylamides/chemical synthesis , Animals , Catalysis/radiation effects , Cattle , Light , Metal-Organic Frameworks/radiation effects , Metalloporphyrins/chemistry , Metalloporphyrins/radiation effects , Polymerization , Zirconium/chemistry , Zirconium/radiation effectsABSTRACT
A novel composite material was prepared by blending graphene oxide into polyethyleneimine grafted sodium alginate. The synthesized material was investigated as adsorbent and photocatalyst for the removal of hexavalent chromium (Cr (VI)) from aqueous solutions. The composite material has shown remarkable removal efficiency for Cr (VI) in high initial concentration solutions as the removal rate reached 86.16% and 99.92% for adsorption and photoreduction, respectively. We discovered experimentally that the adsorption was dominated via electrostatic interaction while the blending of GO could contribute in stimulating electrons for the photoreduction process. Moreover, the photoreduction can alter the surface charge of chromium species, thus electrostatic repulsion could regenerating the active sites of composite spontaneously. The conduction band energy was calculated as -2.04 eV, which proved that blending GO can narrow the bandgap of the composite material, thus enhance the light response and the photoreduction ability towards Cr (VI).
Subject(s)
Alginates/chemistry , Chromium/isolation & purification , Graphite/chemistry , Light , Water Pollutants, Chemical/isolation & purification , Adsorption , Catalysis/radiation effects , Hydrogen-Ion Concentration , Kinetics , Oxidation-Reduction/radiation effects , Photoelectron Spectroscopy , Spectrophotometry, Ultraviolet , Spectroscopy, Fourier Transform Infrared , Temperature , Time FactorsABSTRACT
The aim of this research was to fabricate active nanocomposite films by incorporation of nickel oxide nanoparticles (NiONPs) (3, 6 and 9% w/w) into the chitosan-based films. The NiONPs were synthesized by solution combustion method and the films were prepared by solvent casting method. The formation of new interactions and increasing of films' crystallinity were confirmed by FT-IR and XRD analyses. Uniform dispersion of NiONPs at lower concentrations and their aggregation at level of 9% was confirmed by FE-SEM observations. Water barrier properties, tensile strength, thermal properties and surface hydrophobicity of films enhanced by addition of 6% NiONPs. Photocatalytic activity of nanocomposites was confirmed by absorption of 72% of methyl orange during 270 min under UV irradiation. The nanocomposite films exhibited good antibacterial activity against gram-positive (S. aureus) and gram-negative (S. typhimurium) bacteria. Therefore, the chitosan-NiONPs nanocomposite films could be used for active food packaging applications and photodecolorization purposes.
Subject(s)
Anti-Infective Agents/pharmacology , Chemical Phenomena , Chitosan/chemistry , Light , Nanocomposites/chemistry , Nanoparticles/chemistry , Nickel/chemistry , Catalysis/radiation effects , Color , Coloring Agents/isolation & purification , Humidity , Microbial Sensitivity Tests , Nanoparticles/ultrastructure , Permeability , Salmonella/drug effects , Solubility , Spectroscopy, Fourier Transform Infrared , Staphylococcus aureus , Steam , Temperature , Thermogravimetry , Water/chemistry , X-Ray DiffractionABSTRACT
Engineering of biological pathways with man-made materials provides inspiring blueprints for sustainable drug production. (R)-1-[3,5-Bis(trifluoromethyl)phenyl]ethanol [(R)-3,5-BTPE], as an important artificial chiral intermediate for complicated pharmaceutical drugs and biologically active molecules, is often synthesized through a hydrogenation reaction of 3,5-bis(trifluoromethyl)acetophenone (3,5-BTAP), in which enantioselectivity and sufficient active hydrogen are the key to restricting the reaction. In this work, a biohybrid photocatalytic hydrogenation system based on an artificial cross-linked enzymes (CLEs)-TiO2-Cp*Rh(bpy) photoenzyme is developed through a bottom-up engineering strategy. Here, TiO2 nanotubes in the presence of Cp*Rh(bpy) are used to transform NADP+ to NADPH during the formation of chiral alcohol intermediates from the catalytic reduction of a ketone substrate by alcohol dehydrogenase CLEs. Hydrogen and electrons, provided by water and photocatalytic systems, respectively, are transferred to reduce NADP+ to NADPH via [Cp*Rh(bpy)(H2O)]2+. With the resulting NADPH, [(R)-3,5-BTPE] is synthesized using our efficient CLEs obtained from the cell lysate by nonstandard amino acid modification. Through this biohybrid photocatalytic system, the photoenzyme-catalyzed combined reductive synthesis of [(R)-3,5-BTPE] has a yield of 41.2% after reaction for 24 h and a very high enantiomeric excess value (>99.99%). In the case of reuse, this biohybrid system retained nearly 95% of its initial catalytic activity for synthesizing the above chiral alcohol. The excellent reusability of the CLEs and TiO2 nanotubes hybrid catalytic materials highlights the environmental friendliness of (R)-3,5-BTPE production.
Subject(s)
Alcohol Dehydrogenase/chemistry , Nanotubes/chemistry , Phenylethyl Alcohol/analogs & derivatives , Titanium/chemistry , Bacterial Proteins/chemistry , Catalysis/radiation effects , Coordination Complexes/chemistry , Coordination Complexes/radiation effects , Hydrogenation , Lactobacillus/enzymology , Light , NADP/chemical synthesis , Nanotubes/radiation effects , Phenylethyl Alcohol/chemical synthesis , Rhodium/chemistry , Rhodium/radiation effects , Stereoisomerism , Titanium/radiation effects , Water/chemistryABSTRACT
In this report, chitosan/zinc oxide (CS/ZnO) nanocomposite was synthesized using Sida acuta and assessed their antibacterial and photocatalytic properties. The formation of CS/ZnO nanocomposite was preliminary confirmed by colour change and UV-visible spectroscopy. The crystalline peaks related to CS and ZnO in CS/ZnO nanocomposite were demonstrated by XRD. Morphological analysis through FE-SEM and TEM showed a rod like appearance for ZnO NPs and agglomerated grains with rod shaped morphology was observed for the CS/ZnO nanocomposite. The peaks around 400-800 cm-1 in the IR spectrum of nanocomposite indicated the vibrations of metal-oxygen (ZnO), whereas bands at 1659 cm-1 and 1546 cm-1 indicated the presence of amine groups, which confirms the CS in the synthesized CS/ZnO nanocomposite. The CS/ZnO nanocomposite exhibited remarkable growth inhibition activity against B. subtilis and E. coli with 22 ± 0.3 and 16.5 ± 0.5 mm zone of inhibitions. In addition, CS/ZnO nanocomposite treated cotton fabrics also exhibited antibacterial activity against B. subtilis and E. coli. Furthermore, the ZnO NPs and nanocomposite showed time depended photodegradation activity and revealed 76% and 91% decomposition of CR under sunlight irradiation. In conclusion, our study revealed that the functionalization of biopolymer CS to the inorganic ZnO enhances the bio and catalytic properties.
Subject(s)
Anti-Bacterial Agents/pharmacology , Chitosan/chemical synthesis , Light , Nanocomposites/chemistry , Zinc Oxide/chemical synthesis , Bacteria/drug effects , Catalysis/drug effects , Catalysis/radiation effects , Chitosan/chemistry , Crystallization , Microbial Sensitivity Tests , Photolysis/drug effects , Photolysis/radiation effects , Spectrophotometry, Ultraviolet , Spectroscopy, Fourier Transform Infrared , X-Ray Diffraction , Zinc Oxide/chemistryABSTRACT
NOx emission heavily affects our environment and human health. Photocatalytic denitrification (deNOx) attracted much attention because it is low-cost and nonpolluting, but undesired nitrite and nitrate were produced in reality, instead of harmless N2. Unveiling the active sites and the photocatalytic mechanism is very important to improve the process. Herein, we have employed a combinational scenario to investigate the reaction mechanism of NO2 and H2O on anatase TiO2(101). On the one hand, a polaron-corrected GGA functional (GGA + Lany-Zunger) was applied to improve the description of electronic states in photoassisted processes. On the other hand, a reaction phase diagram (RPD) was established to understand the (quasi) activity trend over both perfect and defective surfaces. It was found that a perfect surface is more active via the Eley-Rideal mechanism without NO2 adsorption, while the activity on defective surfaces is limited by the sluggish recombinative desorption. A photogenerated hole can weaken the OH* adsorption energies and circumvents the scaling relation of the dark reaction, eventually enhancing the deNOx activity significantly. The insights gained from our work indicate that tuning the reactivity by illumination-induced localized charge and diverse reaction pathways are two methods for improving adsorption, dissociation, and desorption processes to go beyond the conventional activity volcano plot limit of dark conditions.
Subject(s)
Nitrogen Dioxide/chemistry , Titanium/chemistry , Adsorption , Catalysis/radiation effects , Kinetics , Models, Chemical , Thermodynamics , Titanium/radiation effects , Ultraviolet Rays , Water/chemistryABSTRACT
Loading a photocatalytic TiO2 to organic carriers has been desired for volumetric TiO2 incorporation, facile retrieval, and sustainable utilization. Traditionally, suspended TiO2 nanoparticles or its thin film on two-dimensional substrate are popularly fabricated for pollutants decomposition without carriers; due to poor thermomechanical properties of the organic carriers. Herein, a combination of the chitin nanofiber carrier and atomic layer deposition proves relevance for formation of anatase TiO2 thin layer so that photocatalytic decomposition in three-dimensional surface. Moreover, chitin nanofiber is capable of holding the TiO2 nanoparticles for multiple cycles of photocatalysis. Those types of TiO2 show characteristic degradation performance for gaseous (acetaldehyde) and aqueous pollutants (4-chlorophenol and rhodamine B). After catalytic reaction, chitin/TiO2 is retrievable owing to carrier's robustness even in water without TiO2 aggregation and loss. This work suggests that chitin-based photocatalyst is applicable to numerous pollutants through chitin's relatively high chemical resistance and stably wedged TiO2 during photocatalytic reaction.
Subject(s)
Air Pollutants/chemistry , Chitin/chemistry , Metal Nanoparticles/chemistry , Nanofibers/chemistry , Titanium/chemistry , Water Pollutants, Chemical/chemistry , Acetaldehyde/chemistry , Animals , Catalysis/radiation effects , Chitin/toxicity , Chlorophenols/chemistry , Light , Metal Nanoparticles/radiation effects , Metal Nanoparticles/toxicity , Mice , NIH 3T3 Cells , Nanofibers/radiation effects , Nanofibers/toxicity , Oxidation-Reduction , Rhodamines/chemistry , Titanium/radiation effects , Titanium/toxicityABSTRACT
Carbene-based macromolecules are an emerging new stimuli-sensitive class of biomaterials that avoid the impediments of free radical polymerization but maintain a rapid liquid-to-biorubber transition. Activation of diazirine-grafted polycaprolactone polyol (CaproGlu) is limited to UVA wavelengths that have tissue exposure constraints and limited light intensities. For the first time, UVA is circumvented with visible light-emitting diodes at 445 nm (blue) to rapidly activate diazirine-to-carbene covalent cross-linking. Iridium photocatalysts serve to initiate diazirine, despite having little to no absorption at 445 nm. CaproGlu's liquid organic matrix dissolves the photocatalyst with no solvents required, creating a light transparent matrix. Considerable differences in cross-linking chemistry are observed in UVA vs visible/photocatalyst formulations. Empirical analysis and theoretical calculations reveal a more efficient conversion of diazirine directly to carbene with no diazoalkane intermediate detected. Photorheometry results demonstrate a correlation between shear moduli, joules light dose, and the lower limits of photocatalyst concentration required for the liquid-to-biorubber transition. Adhesion strength on ex vivo hydrated tissues exceeds that of cyanoacrylates, with a fixation strength of up to 20 kg·f·cm2. Preliminary toxicity assessment on leachates and materials directly in contact with mammalian fibroblast cells displays no signs of fibroblast cytotoxicity.
Subject(s)
Adhesives/chemistry , Biocompatible Materials/chemistry , Coordination Complexes/chemistry , Diazomethane/analogs & derivatives , Animals , Catalysis/radiation effects , Collagen/chemistry , Coordination Complexes/radiation effects , Coordination Complexes/toxicity , Cross-Linking Reagents/chemistry , Iridium/chemistry , Iridium/radiation effects , Iridium/toxicity , Light , Mice , NIH 3T3 Cells , Polyesters/chemistry , SwineABSTRACT
Cellulose is well known as a biocompatible material or natural reducing material. In this study, As an eco-friendly and facile method, we prepared monodispersed silver nanoparticles (AgNPs) in cellulose-framework through photocatalytic reaction. and we fabricated electrospun fiber scaffolds with excellent antibacterial properties and biocompatibility. UV-irradiation causes the electrical change of the cellulose-framework, thereby converting Ag ions into Ag particles. We applied a three-electrode system to confirm the phenomenon. Through STEM and EDS, it was found that the synthesized AgNPs were monodisperse in the nanofibers, and antibacterial activity was confirmed using gram-negative and gram-positive bacteria. In addition, it was suggested that the gradual release of simvastatin contained in the nanofibers and excellent mineralization would be easy to apply to bone regeneration. Therefore, the manufactured composite electrospun fiber mat can be used not only in biomedical fields but also in various applications that need to prevent the accumulation of microorganisms.
Subject(s)
Anti-Bacterial Agents/pharmacology , Bone Density Conservation Agents/pharmacology , Cellulose/chemistry , Metal Nanoparticles/chemistry , Silver/pharmacology , Simvastatin/pharmacology , Animals , Anti-Bacterial Agents/chemistry , Bone Density Conservation Agents/chemistry , Bone Regeneration/drug effects , Catalysis/radiation effects , Cell Line , Drug Delivery Systems , Escherichia coli/drug effects , Mice , Microbial Sensitivity Tests , Nanofibers/chemistry , Osteogenesis/drug effects , Silver/chemistry , Simvastatin/chemistry , Staphylococcus aureus/drug effects , Tissue Scaffolds/chemistry , Ultraviolet RaysABSTRACT
In the present study, the novel Ag/cellulose nanocrystal (CNC)-doped CeO2 quantum dots (QDs) with highly efficient catalytic performance were synthesized using one pot co-precipitation technique, which were then applied in the degradation of methylene blue and ciprofloxacin (MBCF) in wastewater. Catalytic activity against MBCF dye was significantly reduced (99.3%) for (4%) Ag dopant concentration in acidic medium. For Ag/CNC-doped CeO2 vast inhibition domain of G-ve was significantly confirmed as (5.25-11.70 mm) and (7.15-13.60 mm), while medium- to high-concentration of CNC levels were calculated for G + ve (0.95 nm, 1.65 mm), respectively. Overall, (4%) Ag/CNC-doped CeO2 revealed significant antimicrobial activity against G-ve relative to G + ve at both concentrations, respectively. Furthermore, in silico molecular docking studies were performed against selected enzyme targets dihydrofolate reductase (DHFR), dihydropteroate synthase (DHPS), and DNA gyrase belonging to folate and nucleic acid biosynthetic pathway, respectively to rationalize possible mechanism behind bactericidal potential of CNC-CeO2 and Ag/CNC-CeO2.