Recent advances in visible light-activated photocatalysts for degradation of dyes: A comprehensive review.

The rapid development in industrialization and urbanization coupled with an ever-increasing world population has caused a tremendous increase in contamination of water resources globally. Synthetic dyes have emerged as a major contributor to environmental pollution due to their release in large quantities into the environment, especially owing to their high demand in textile, cosmetics, clothing, food, paper, rubber, printing, and plastic industries. Photocatalytic treatment technology has gained immense research attention for dye contaminated wastewater treatment due to its environment-friendliness, ability to completely degrade dye molecules using light irradiation, high efficiency, and no generation of secondary waste. Photocatalytic technology is evolving rapidly, and the foremost goal is to synthesize highly efficient photocatalysts with solar energy harvesting abilities. The current review provides a comprehensive overview of the most recent advances in highly efficient visible light-activated photocatalysts for dye degradation, including methods of synthesis, strategies for improving photocatalytic activity, regeneration and their performance in real industrial effluent. The influence of various operational parameters on photocatalytic activity are critically evaluated in this article. Finally, this review briefly discusses the current challenges and prospects of visible-light driven photocatalysts. This review serves as a convenient and comprehensive resource for comparing and studying the fundamentals and recent advancements in visible light photocatalysts and will facilitate further research in this direction.

Easy-handling semi-floating TiO2-based aerogel for solar photocatalytic water depollution.

One of the capital issues of photocatalytic technology is how to use photocatalytic materials in real world conditions. Suspension photocatalysts are the most effective, while the handling and recovery of nanoparticles are very challenging and costly. Herein, we report the design of semi-floating aerogel TiO2-based photocatalyst for the oxidation of dyes and photoreduction of Cr(VI). TiO2 aerogel-based photocatalyst was fabricated through in situ polymerization using borax, poly(vinyl alcohol) and polyvinylidene in the presence of H2O2 as a catalyst. Cubic TiO2 aerogel of few centimetres was designed for the photocatalytic tests under solar light irradiation. TiO2 aerogel showed a good photoactivity against the oxidation of three types of dyes and Cr(VI) photoreduction. In terms of dyes, the kinetics of methylene blue oxidation was the fastest as compared to rhodamine B and methyl red, while, a total reduction of Cr(VI) at 10 ppm was obtained within 30 min after the addition of tartaric acid as hole scavenger. TiO2 aerogel can be easily recovered, washed and recycled. TiO2 aerogel can move freely from the top to the deep solution. The semi-floating property could be an advantage to enhance the mass transfer along with bulk solution, as compared to totally floating-based photocatalysts.

Current knowledge of the degradation products of tattoo pigments by sunlight, laser irradiation and metabolism: a systematic review.

The popularity of tattooing has increased significantly over recent years. This has raised concerns about the safety of tattoo inks and their metabolites/degradation products. The photolytic and metabolic degradation of tattoo pigments may result in the formation of toxic compounds, with unforeseen health risks. A systematic literature review was undertaken to determine the current state of knowledge of tattoo pigments' degradation products when irradiated with sunlight, laser light or metabolised. The review demonstrates that there is a lack of knowledge regarding tattoo pigment degradation/metabolism, with only eleven articles found pertaining to the photolysis of tattoo pigments and two articles on the metabolism of tattoo pigments. The limited research indicates that the photolysis of tattoo pigments could result in many toxic degradation products, including hydrogen cyanide and carcinogenic aromatic amines.

Photoacoustic imaging of elevated glutathione in models of lung cancer for companion diagnostic applications.

Companion diagnostics (CDx) are powerful tests that can provide physicians with crucial biomarker information that can improve treatment outcomes by matching therapies to patients. Here, we report a photoacoustic imaging-based CDx (PACDx) for the selective detection of elevated glutathione (GSH) in a lung cancer model. GSH is abundant in most cells, so we adopted a physical organic chemistry approach to precisely tune the reactivity to distinguish between normal and pathological states. To evaluate the efficacy of PACDx in vivo, we designed a blind study where photoacoustic imaging was used to identify mice bearing lung xenografts. We also employed PACDx in orthotopic lung cancer and liver metastasis models to image GSH. In addition, we designed a matching prodrug, PARx, that uses the same SNAr chemistry to release a chemotherapeutic with an integrated PA readout. Studies demonstrate that PARx can inhibit tumour growth without off-target toxicity in a lung cancer xenograft model.

Construction of self-enhanced photoelectrochemical platform for L-cysteine detection via electron donor-acceptor type coumarin 545 aggregates.

Self-enhanced electron donor-acceptor type coumarin 545 aggregates prepared via an anionic surfactant-assisted reprecipitation method provide an underlying approach for the photoelectrochemical detection of L-cysteine, which can be employed in aqueous solution without the addition of electron donors.

Facile production of three-dimensional chitosan fiber embedded with zinc oxide as recoverable photocatalyst for organic dye degradation.

Herein we report on a facile and green strategy for continuous production of chitosan-zinc oxide fibers and then compare their photodegradation performance against three organic dyes (i.e., methylene blue (MB), methyl orange (MO) and Rhodamine B, respectively) under different lights. Chitosan-zinc hydrogel fibers (CS/Zn) with different zinc loadings are obtained by direct mixing of chitosan and zinc acetate solutions using a double-syringe injection device. The as-prepared CS/Zn fibers are then immersed into glutaraldehyde (GA) and sodium hydroxide solutions, respectively, and dried at T = 50 °C. The resultant CS/ZnO/GA fibers of ca. 617 µm in diameter are characterized using X-ray diffraction (XRD), thermogravimetric analysis and field emission scanning electron microscope (FE-SEM). XRD and FE-SEM data confirm that the CS/ZnO/GA fibers consist of a large amount of hexagonal wurtzite ZnO nanorods up to 550 nm in length, and exhibit three-dimensional interconnected macroporous architecture. Photodegradation results clearly show that the CS/ZnO/GA fibers are effective for the removal of organic dyes upon UV irradiation and can be easily recovered and reused for at least 6 consecutive cycles. Unlike most reported CS/ZnO nanocomposites, the current CS/ZnO/GA fiber shows a higher adsorption of cationic MB rather than anionic MO, the mechanism of which is proposed.

Imaging studies of photodegradation and self-healing in anthraquinone derivative dye-doped PMMA.

We study photodegradation and self-healing of nine different anthraquinone-derivatives doped into PMMA using transmission imaging microscopy in search of structure-property relationships of the underlying mechanisms. We find that seven of the nine anthraquinone derivatives display partially reversible photodegradation, with 1,8-dihydroxyanthraquinone (Dantron/Chrysazin) having the best photostability and recovery characteristics of all dyes tested in this study. Based on these measurements we predict that a sample of 1,8-dihydroxyanthraquinone doped into PMMA with a concentration of 9 g l-1 will have a record setting irreversible inverse quantum efficiency of Bε = 4.56 × 109. Additionally, by considering the performance of the different anthraquinone derivatives and their structures, we develop three rules-of-thumb to qualitatively predict the photostability and recovery characteristics of anthraquinone derivatives. These rules-of-thumb will help guide future experiments and molecular modeling in discerning the underlying mechanisms of reversible photodegradation. Finally, we compare our results for disperse orange 11 dye-doped PMMA to the extended Correlated Chromophore Domain Model (eCCDM). While the eCCDM correctly predicts the behavior of the reversible decay component, it fails to correctly predict the behavior of the irreversible degradation component. This implies further modifications to the eCCDM are required.

Chemical approaches to artificial photosynthesis: A molecular, dye-sensitized photoanode for O2 production prepared by layer-by-layer self-assembly.

We describe here the preparation of a family of photoanodes for water oxidation that incorporate an electron acceptor-chromophore-catalyst in single molecular assemblies on nano-indium tin oxide (nanoITO) electrodes on fluorine-doped tin oxide (FTO). The assemblies were prepared by using a layer-by-layer, Atomic Layer Deposition (ALD), self-assembly approach. In the procedure, addition of an electron acceptor viologen derivative followed by a RuII(bpy) chromophore and a pyridyl derivative of the water oxidation catalyst [Ru(bda) (L)2] (bda = 2,2'-bipyridine-6,6'-dicarboxylate)2, were linked by ALD by addition of the bridge precursors TiO2, ZrO2, and Al2O3 as the bridging groups giving the assemblies, FTO|nanoITO|-MV2+-ALD MO2-RuP2 2+-ALD M'O2-WOC. In a series of devices, the most efficient gave water oxidation with an incident photon to current efficiency of 2.2% at 440 nm. Transient nanosecond absorption measurements on the assemblies demonstrated that the slow step in the intra-assembly electron transfer is the electron transfer from the chromophore through the viologen bridge to the nanoITO electrode.

Treatments of a phthalocyanine-based green ink for tattoo removal purposes: generation of toxic fragments and potentially harmful morphologies.

Since tattoos became overwhelmingly fashionable worldwide, the demand for removal has proportionally increased, Nd:YAG Q-switch laser being the most commonly used tool for the purpose. In this framework we investigated the composition and products of laser treatment of green tattoo ink, the Green Concentrate from Eternal. The ink characterization has been carried out by IR, UV-Vis, EDX spectroscopies, and SEM imaging. It revealed the presence of the pigment PG7, rather than PG36 as reported on the bottle label, along with non-fully halogenated analogues. The morphology is an extended sheath with embedded grains. Subsequent laser treatments were performed on both dried and extracted inks, dispersed either in water or in propan-2-ol, chosen for their different polarities, as it is the case in the skin layers. The products were analyzed by gas chromatography-mass spectrometry, UV-Vis spectroscopy, SEM imaging, and dynamic light scattering. The outcome is a complex fragmentation pattern that depends both on the solvent and on the initial aggregation state. The fragment compounds are toxic at various degrees according to the Classification Labelling and Packaging regulations. Several shapes of aggregates are produced as an effect of both downsizing and re-aggregation, with potentially harmful aspect ratios.

Impact of binding to the multidrug resistance regulator protein LmrR on the photo-physics and -chemistry of photosensitizers.

Light activated photosensitizers generate reactive oxygen species (ROS) that interfere with cellular components and can induce cell death, e.g., in photodynamic therapy (PDT). The effect of cellular components and especially proteins on the photochemistry and photophysics of the sensitizers is a key aspect in drug design and the correlating cellular response with the generation of specific ROS species. Here, we show the complex range of effects of binding of photosensitizer to a multidrug resistance protein, produced by bacteria, on the formers reactivity. We show that recruitment of drug like molecules by LmrR (Lactococcal multidrug resistance Regulator) modifies their photophysical properties and their capacity to induce oxidative stress especially in 1O2 generation, including rose bengal (RB), protoporphyrin IX (PpIX), bodipy, eosin Y (EY), riboflavin (RBF), and rhodamine 6G (Rh6G). The range of neutral and charged dyes with different exited redox potentials, are broadly representative of the dyes used in PDT.

Aggregation-Dependent Photoreactive Hemicyanine Assembly as a Photobactericide.

Organic materials that show substantial reactivity under visible light have received considerable attention due to their wide applications in chemical and biological systems. Hemicyanine pigments possess a strong intramolecular donor-acceptor structure and thereby display intense absorption in the visible spectral region. However, most excitons are consumed via the twisted intramolecular charge-transfer (TICT) process, making hemicyanines generally inert to light. Herein, we describe the development of an amphiphilic hemicyanine dye whose aggregation could be easily regulated using salt or counterions. More importantly, its intrinsic photoreactivity was successfully induced by steric restriction and cofacial arrangement within the H-aggregate, thus creating an effective photobactericide. This strategy could be extended to the development of photocatalysts for photosynthesis and a photosensitizer for photodynamic therapy.

Pyridine-Embedded Phenothiazinium Dyes as Lysosome-Targeted Photosensitizers for Highly Efficient Photodynamic Antitumor Therapy.

Development of new photosensitizers (PSs) with high photodynamic efficacy and minimal side effects is of great interest in photodynamic therapy (PDT). In this work, we reported several pyridine-embedded phenothiazinium (pyridophenothiazinium) dyes, which could be conveniently synthesized in a few short steps and acted as highly efficient and potent PSs to selectively localize to lysosomes and photosensitively kill cancer cells. Among them, compound 5, which possessed the ability of promoting intracellular reactive oxygen species (ROS) upon light irradiation by almost 40-fold higher than that of methylene blue (MB, a general phenothiazinium-based PS), exhibited a remarkable phototherapeutic index (PI = 53.8) against HT29 cancer cells, leading to eradication of large solid tumors (∼300 mm3) in a xenograft mouse model without apparent side effects. These results suggest that the pyridophenothiazinium dyes developed herein, especially compound 5, may serve as promising lysosome-targeted PSs for efficient photodynamic antitumor therapy.

A sequential targeting nanoplatform for anaplastic thyroid carcinoma theranostics.

Effective accumulation of nanoparticles (NPs) in tumor regions is one of the major motivations in nanotechnology research and that the establishment of an efficient targeting nanoplatform for the treatment of malignant tumors is urgently needed for theranostic applications. In this study, we engineered multifunctional sequential targeting NPs for achieving synergistic antiangiogenic photothermal therapy (PTT) and multimodal imaging-guided diagnosis for anaplastic thyroid carcinoma (ATC) theranostics. Antibody bevacizumab with an affinity towards vascular endothelial growth factor (VEGF) on the tumor cell surface was conjugated onto the surface of polymer NPs for VEGF targeting and antiangiogenic therapy. Encapsulated IR825 was employed as a photothermal agent (PTA) with a mitochondrial targeting capability, which further cascades NPs into mitochondria to enhance hyperthermic efficiency in the ablation of tumor cells. Importantly, the combination of bevacizumab and IR825 in a single nanosystem achieved desirable accumulations of NPs and that sequential targeted PTT combined with antiangiogenesis significantly promoted the therapeutic efficiency in eradicating tumors by near-infrared (NIR) laser irradiation. Furthermore, these NPs are extraordinary contrast agents for photoacoustic, ultrasound and fluorescence imaging applications, providing multimodal imaging capabilities for therapeutic monitoring and a precise diagnosis. Therefore, this multifunctional nanoplatform provides a promising theranostic strategy for extremely malignant ATC. STATEMENT OF SIGNIFICANCE: Anaplastic thyroid carcinoma (ATC), with extremely aggressive behavior, lacks a satisfactory therapeutic method and a comprehensive early diagnostic strategy. Herein, we successfully synthesized a sequential targeting nanoplatform (IR825@Bev-PLGA-PFP NPs) with theranostic function, which specifically binds to VEGF on the tumor cell surface and further cascades into mitochondria to achieve effective accumulation of NPs in the tumor regions. As a result, it solves the urgent demand for ATC detection and therapy. By breaking the limitation of traditional target, such as low efficacy and frequent recurrence as the results of low accumulation, sequential targeting combined with synergistic antiangiogenic PTT completely eradicates tumors without any residual tissue and side effect. Therefore, this strategy paves a solid way for further investigation in the theranostic progressing of ATC.

Integration of plasmonic effect into MIL-125-NH2: An ultra-efficient photocatalyst for simultaneous removal of ternary system pollutants.

Industrial effluents often contain mixed metal ions and dyes, and it is difficult to efficiently remove both types of contaminants simultaneously. Here, MIL-125-NH2@Ag/AgCl composites were for the first time developed through a facile deposition-photoreduction method for simultaneously removing Cr(VI)/Rhodamine B (RhB)/Malachite Green (MG) ternary system pollutants under visible-light irradiation. The capacities of Cr(VI) reduction dramatically increased to 98.4% in the coexistence of RhB and MG compared to that of binary (Cr(VI)/RhB (69.6%) or Cr(VI)/MG (67.5%)) and single Cr(VI) (29%) systems. In the meantime, the degradation efficiencies of dyes especially RhB in the ternary system were also improved compared to that of their individual systems. On the grounds of all the experimental results, it can be concluded that the efficient light-harvesting and electrons migration in MIL-125-NH2@Ag/AgCl and the synergistic effect of redox reactions between Cr(VI) and dyes hinder the recombination of photo-induced electron-hole pairs, which are responsible for their high photocatalytic activity to eliminate the mixed pollutants. This study provides a new route to construct high-performance photocatalysts for the practical treatment of wastewater containing mixed pollutants.

Preparation of biocompatible nano-ZnO/chitosan microspheres with multi-functions of antibacterial, UV-shielding and dye photodegradation.

Nano-ZnO (nZnO) has been widely used as antibacterial, UV-shielding and photocatalysis materials, but limited by its contentious biosafety. In this paper, chitosan (CS) was introduced to enhance the biocompatibility. To solve the problem that nZnO reacts with the CS acid solution, alternate-feed spray drying was adopted to fabricate nZnO/CS composite microspheres. It was showed that nZnO remained the hexagonal phase, dispersed and embedded into CS microspheres. Based on the results of cytotoxicity and hemolysis test, biosafety was improved obviously. Further, the antibacterial activity of nZnO/CS was notably better than either of CS and nZnO individually. UV-shielding property and photocatalytic degradation test were estimated. In a word, alternate-feed spray drying presents a novel and cost-efficient method to fabricate multifunctional nZnO/CS microspheres with enhanced biosafety.

Solar assisted photocatalytic degradation of organic pollutants in the presence of biogenic fluorescent ZnS nanocolloids.

The main aim of this study was to ascertain the photocatalytic degradation of organic pollutants present in aqueous phase using fluorescent biogenic ZnS nanocolloids produced from an endophytic fungus Aspergillus flavus. The degradation studies were carried out using different organic pollutants such as methyl violet (MV), 2,4-dichlorophenoxyacetic acid (2,4-D) and paracetamol (PARA) for 120 min, 270 min and 240 min, respectively, at pH varying from 3.0 to 11.0. The results from this study indicate that the degradation efficiency of ZnS nanocolloids for MV, 2,4-D and PARA were 87%, 33% and 51%, respectively, at the optimum concentration of 100 mg/L of the tested organic pollutants. At different time intervals, the samples were analyzed for their chemical oxygen demand (COD) and total organic carbon (TOC) contents. The reduction of COD and TOC were 78% and 74% for MV at 120 min; 55.5% and 57.2% for 2,4-D at 270 min and 47.6% and 44.5% for PARA at 240 min, respectively. The degradation pathway was determined based on the mass spectrum and the intermediates formed; in addition, the interaction between organic pollutants and nanocolloids was also elucidated based on atomic force microscopy (AFM) and fluorescence spectrum.

Interactive Fe2O3/porous SiO2 nanospheres for photocatalytic degradation of organic pollutants: Kinetic and mechanistic approach.

A uniformly distributed mesoporous silica nanospheres has been successfully synthesized. Silica nanospheres have been loaded with different content of Fe2O3 nanoparticles synthesized by the sol-gel process followed by calcination to form the Fe2O3 supported on silica nanospheres composite. The as-synthesized photocatalyst has been characterized for crystal structure, morphology, stability, surface area and also surface composition was determined. The photocatalytic oxidation ability of the composite photocatalyst was evaluated by degrading aqueous solutions of Methylene Blue and Congo red dyes under visible light having intense absorption in the wavelength range between 550 and 560 nm. The prime significance of silica is to act as catalyst support for uniform distribution of hematite particles for enhanced catalytic reactivity. Highest degradation has been achieved with 20 wt % loading of hematite nanoparticles indicating the less agglomeration and availability of more catalytic sites. Furthermore, colorless organic pollutants 2-chlorophenol and 2, 4-dichlorophenol have been degraded with high efficiency in the presence of H2O2 oxidizer. The scavenger experiments confirmed that hydroxyl radicals are the majorly participating species in this catalytic system. The composite system also shows good recyclability of the materials and advocates the promising nature of the designed system for multiple hazardous environmental contaminants.

Photocatalytic degradation of synthetic dyes using iron (III) oxide nanoparticles (Fe2O3-Nps) synthesised using Rhizophora mucronata Lam.

Biosynthesis of nanoparticles through plant extracts is gaining attention due to the toxic free synthesis process. The environmental engineering applications of many metal oxide nanoparticles have been reported. In this study, iron oxide nanoparticles (Fe2O3-Nps) were synthesised using a simple biosynthetic method using a leaf extract of a mangrove plant Rhizophora mucronata through reduction of 0.01 M ferric chloride. Fe2O3-Np synthesis was revealed by a greenish colour formation with a surface plasmon band observed close to 368 nm. The stable Fe2O3-Np possessed excitation and emission wavelength of 368.0 and 370.5 nm, respectively. The Fourier-transform infrared spectral analysis revealed the changes in functional groups during formation of Fe2O3-Np. Agglomerations of nanoparticles were observed during scanning electron microscopic analysis and energy-dispersive X-ray spectroscopic analysis confirmed the ferric oxide nature. The average particle size of Fe2O3-Np based on dynamic light scattering was 65 nm. Based on transmission electron microscopic analysis, particles were spherical in shape and the crystalline size was confirmed by selected area electron diffraction pattern analysis. The synthesised Fe2O3-Np exhibited a good photodegradation efficiency with a reduction of 83 and 95% of phenol red and crystal violet under irradiation of sunlight and florescent light, respectively. This report is a facile synthesis method for Fe2O3-Np with high photodegradation efficiency.

High-throughput analysis of photocatalytic reactivity of differing TiO2 formulations using 96-well microplate reactors.

The rapid development of photocatalysts for water decontamination benefits from availability of sensitive platforms for screening photocatalytic reactivity. The standard approach typically involves quantifying the degradation of a single dye compound in a slurry system in individual beakers, which requires tedious photocatalyst separation and long operation time. We present a simple and efficient method for assessing the photocatalytic activity of different photocatalyst nanomaterials that eliminates the solid separation process. The 96-well microplate method demonstrated an improved applicability as a high-throughput screening method for photocatalytic reaction mechanisms using a wide range of chemical substrates (i.e., methyl orange, methylene blue, terephthalic acid, and ß-nicotinamide adenine dinucleotide coenzyme) and photocatalyst concentrations (1-100 mg/L). By employing photocatalysts at lower concentrations compared to the slurry system, rapid screening was accomplished through direct spectrophotometric or spectrofluorometric measurements. The mass-normalized rate constants of dye degradation were used to determine the photocatalytic reactivity of three commercial TiO2 nanomaterials, which followed an order of SRM TiO2 1898 ≈ Degussa TiO2 P90 > Food-grade TiO2 E171. The extent of hydroxyl radical involvement in methyl orange degradation was estimated to be ∼74% by using radical scavengers in the microplate reactor. Given the utilization of low-concentration photocatalyst, this protocol may be used for evaluating photocatalytic reactivity and oxidative stress caused by photocatalyst exposure in an aquatic environment. We further evaluated photocatalytic reaction kinetics with respect to energetic and photonic efficiency. The method could greatly facilitate comparisons across different laboratories when quantifying photocatalytic reactivity and efficiency, which would aid in standardizing bench-scale photocatalysis testing.

Photoreduction of CO2 with a Formate Dehydrogenase Driven by Photosystem II Using a Semi-artificial Z-Scheme Architecture.

Solar-driven coupling of water oxidation with CO2 reduction sustains life on our planet and is of high priority in contemporary energy research. Here, we report a photoelectrochemical tandem device that performs photocatalytic reduction of CO2 to formate. We employ a semi-artificial design, which wires a W-dependent formate dehydrogenase (FDH) cathode to a photoanode containing the photosynthetic water oxidation enzyme, Photosystem II, via a synthetic dye with complementary light absorption. From a biological perspective, the system achieves a metabolically inaccessible pathway of light-driven CO2 fixation to formate. From a synthetic point of view, it represents a proof-of-principle system utilizing precious-metal-free catalysts for selective CO2-to-formate conversion using water as an electron donor. This hybrid platform demonstrates the translatability and versatility of coupling abiotic and biotic components to create challenging models for solar fuel and chemical synthesis.