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Spherical Ti-MCM-41, synthetized by co-condensation method, presented very promising activity in catalytic and photocatalytic oxidation of diphenyl sulfide with H2O2 to obtain diphenyl sulfoxide and diphenyl sulfone. Mesoporous silica materials with various titanium content were analyzed with respect to chemical composition (inductively coupled plasma optical emission spectrometry), structure properties (X-ray diffraction), textural properties (low-temperature N2 adsorption–desorption), morphology (scanning electron microscopy), forms and aggregation introduced titanium species (diffuse reflectance spectroscopy, Raman spectroscopy), and surface acidity (NH3-TPD). Titanium introduced in the samples was present mainly in the form of highly dispersed species, presenting catalytic and photocatalytic activities in diphenyl sulfide oxidation with H2O2. Efficiency of the reaction increased with an increase in titanium loading in the samples and was significantly intensified under UV irradiation. The role of various Ti species in diphenyl sulfide oxidation was presented and discussed.

Recent development in photocatalysis is increasingly focused on transforming organic compounds toward producing fine chemicals. Simple, non-selective oxidation reactions (degradation of pollutants) and very demanding solar-to-chemical energy conversion processes (production of solar fuels) face severe economic limitations influenced by still low efficiency and insufficient stability of the systems. Synthesis of fine chemicals, including reductive and oxidative selective transformations, as well as C-C and C-N coupling reactions, can utilise the power of photocatalysis. Herein, we present the recent progress in photocatalytic systems designed to synthesise fine chemicals. In particular, we discuss the factors influencing the efficiency and selectivity of the organic transformations, dividing them into intrinsic (related to individual properties of photocatalysts) and extrinsic (originating from the reaction environment). A rational design of the photocatalytic systems, based on a deep understanding of these factors, opens new perspectives for applied photocatalysis., (© 2024 Wiley-VCH GmbH.)

Advances in the research of nanoparticles (NPs) with controlled charge and size are driven by their potential application in the development of novel technologies and innovative therapeutics. This work reports the synthesis, characterization, and comprehensive biological evaluation of AgNPs functionalized by N , N , N -trimethyl-(11-mercaptoundecyl) ammonium chloride (TMA) and trisodium citrate (TSC). The prepared AgNPs were well characterized in terms of their morphological, spectroscopic and functional properties and biological activities. The implementation of several complementary techniques allowed not only the estimation of the average particle size (from 3 to 40 nm depending on the synthesis procedure used) but also the confirmation of the crystalline nature of the NPs and their round shape. To prove the usefulness of these materials in biological systems, cellular uptake and cytotoxicity in microbial and mammalian cells were determined. Positively charged 10 nm Ag@TMA2 revealed antimicrobial activity against Gram-negative bacteria with a minimum inhibitory concentration (MIC) value of 0.17 μg/mL and complete eradication of Escherichia coli (7 logs) for Ag@TMA2 at a concentration of 0.50 μg/mL, whereas negatively charged 10 nm Ag@TSC1 was effective against Gram-positive bacteria (MIC = 0.05 μg/mL), leading to inactivation of Staphylococcus aureus at relatively low concentrations. In addition, the largest 40 nm Ag@TSC2 was shown to exhibit pronounced anticancer activity against murine colon carcinoma (CT26) and murine mammary gland carcinoma (4T1) cells cultured as 2D and 3D tumor models and reduced toxicity against human HaCaT keratinocytes. Among the possible mechanisms of AgNPs are their ability to generate reactive oxygen species, which was further evaluated in vitro and correlates well with cellular accumulation and overall activity of AgNPs. Furthermore, we confirmed the anticancer efficacy of the most potent Ag@TSC2 in hiPSC-derived colonic organoids and demonstrated that the NPs are biocompatible and applicable in vivo . A pilot study in BALB/c mice evidenced that the treatment with Ag@TSC2 resulted in temporary (>60 days) remission of CT26 tumors.

Metal oxide-organic hybrid semiconductors exhibit specific properties depending not only on their composition but also on the synthesis procedure, and particularly on the functionalization method, determining the interaction between the two components. Surface adsorption is the most common way to prepare organic-modified metal oxides. Here a simple sol-gel route is described as an alternative, finely controlled strategy to synthesize titanium oxide-based materials containing organic molecules coordinated to the metal. The effect of the molecular structure of the ligands on the surface properties of the hybrids is studied using three enediols able to form charge transfer complexes: catechol, dopamine, and ascorbic acid. For each system, the process conditions driving the transition from the sol to chemical, physical, or particulate gels are explored. The structural, optical, and photoelectrochemical characterization of the amorphous hybrid materials shows analogies and differences related to the organic component. In particular, electron paramagnetic resonance (EPR) spectroscopy at room temperature reveals the presence of organic radical species with different evolution and stability, and photocurrent measurements prove the effective photosensitization of TiO 2 in the visible range induced by interfacial ligand-to-metal charge transfer.

In this paper, we describe the role of anatase and rutile crystal phases on diphenyl sulphide (Ph 2 S) catalytic and photocatalytic oxidation. The highly selective and efficient synthesis of diphenyl sulfoxide (Ph 2 SO) and diphenyl sulfone (Ph 2 SO 2 ) at titanium dioxide was demonstrated. Ph 2 S oxidation in the presence of hydrogen peroxide at anatase-TiO 2 can take place both as a catalytic and photocatalytic reaction, while at rutile-TiO 2 only photocatalytic oxidation is possible. The reaction at anatase leads mainly to Ph 2 SO 2 , whereas, in the presence of rutile a complete conversion to Ph 2 SO is achieved after only 15 min (nearly 100% selectivity). Studies on the mechanistic details revealed a dual role of H 2 O 2 . It acts as a substrate in the reaction catalysed only by anatase, but it also plays a key role in alternative photocatalytic oxidation pathways. The presented study shows the applicability of photocatalysis in efficient and selective sulfoxide and sulfone production., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Photocatalytic artificial fixation of N 2 to NH 3 occurs over NaYF 4 :Yb,Tm (NYF) upconversion nanoparticles (NPs) decorated carbon nitride nanotubes with nitrogen vacancies (NYF/NV-CNNTs) in water under near-infrared (NIR) light irradiation. NYF NPs with a particle size of ca. 20 nm were uniformly distributed on the surface of NV-CNNTs. The NYF/NV-CNNTs with 15 wt % NYF exhibited the highest NH 3 production yield of 1.72 mmol L -1 g cat -1 , corresponding to an apparent quantum efficiency of 0.50% under NIR light illumination, and about three times higher the activity of the bare CNNTs under UV-filtered solar light. 15 N isotope-labeling NMR results confirm that the N source of ammonia originates from the photochemical N 2 reduction. The spectroelectrochemical measurements reveal that NVs can greatly facilitate the photogenerated electron transfer without energy loss, while the presence of NYF NPs shifts both the deep trap state and the edge of conduction band toward a lower potential. Moreover, NYF NPs endow the photocatalyst with a NIR light absorption via the fluorescence resonance energy transfer process, and NVs have the ability to enhance the active sites for a stronger adsorption of N 2 and decrease the surface quenching effect of NYF NPs, which thus can promote the energy migration within the heterojunctions. This work opens the way toward full solar spectrum photocatalysis for sustainable ammonia synthesis under aqueous system.

The diffuse reflectance spectroelectrochemistry (SE-DRS) and reversed double-beam photoacoustic spectroscopy (RDB-PAS) provide unique, complementary information on the density of electronic states (DOS) in the vicinity of the conduction band bottom. The measurements are performed under quite different conditions, representing the solid/liquid and solid/gas interfaces in SE-DRS and RDB-PAS, respectively. DOS profiles obtained from both types of measurements can be considered as unique "fingerprints" of the tested materials. The analysis of DOS profiles recorded for 16 different TiO 2 samples confirms that both methods similarly describe the shapes of DOS profiles around the conduction band edges. The states characterized by energy higher than VBT (valence-band top) + E g can be considered as electronic states within the conduction band. Recognition of the potential of the conduction band bottom allows one to classify the electronic states as deep or shallow electron traps or conduction band states, which play different roles in photocatalysis. The comparative analysis shows that both methods provide very useful information which can be used in understanding and predicting the photo(electro)catalytic reactivity of semiconductors.

Resistance of microorganisms to antibiotics has led to research on various therapeutic strategies with different mechanisms of action, including photodynamic inactivation (PDI). In this work, we evaluated a cationic, neutral, and anionic meso -tetraphenylporphyrin derivative's ability to inactivate the Gram-negative and Gram-positive bacteria in a planktonic suspension under blue light irradiation. The spectroscopic, physicochemical, redox properties, as well as reactive oxygen species (ROS) generation capacity by a set of photosensitizers varying in lipophilicity were investigated. The theoretical calculations were performed to explain the distribution of the molecular charges in the evaluated compounds. Moreover, logP partition coefficients, cellular uptake, and phototoxicity of the photosensitizers towards bacteria were determined. The role of a specific microbial efflux pump inhibitor, verapamil hydrochloride, in PDI was also studied. The results showed that E. coli exhibited higher resistance to PDI than S. aureus (3-5 logs) with low light doses (1-10 J/cm 2 ). In turn, the prolongation of irradiation (up to 100 J/cm 2 ) remarkably improved the inactivation of pathogens (up to 7 logs) and revealed the importance of photosensitizer photostability. The PDI potentiation occurs after the addition of KI (more than 3 logs extra killing). Verapamil increased the uptake of photosensitizers (especially in E. coli ) due to efflux pump inhibition. This effect suggests that PDI is mediated by ROS, the electrostatic charge interaction, and the efflux of photosensitizers (PSs) regulated by multidrug-resistance (MDR) systems. Thus, MDR inhibition combined with PDI gives opportunities to treat more resistant bacteria.

Hydrogen production by photocatalytic water splitting is one of the most promising sustainable routes to store solar energy in the form of chemical bonds. To obtain significant H 2 evolution rates (HERs) a variety of defective TiO 2 catalysts were synthesized by means of procedures generally requiring highly energy-consuming treatments, e.g. hydrogenation. Even if a complete understanding of the relationship between defects, electronic structure and catalytic active sites is far from being achieved, the band gap narrowing and Ti 3+ -self-doping have been considered essential to date. In most reports a metal co-catalyst (commonly Pt) and a sacrificial electron donor (such as methanol) are used to improve HERs. Here we report the synthesis of TiO 2 /C bulk heterostructures, obtained from a hybrid TiO 2 -based gel by simple heat treatments at 400 °C under different atmospheres. The electronic structure and properties of the grey or black gel-derived powders are deeply inspected by a combination of classical and less conventional techniques, in order to identify the origin of their photoresponsivity. The defective sites of these heterostructures, namely oxygen vacancies, graphitic carbon and unpaired electrons localized on the C matrix, result in a remarkable visible light activity in spite of the lack of band gap narrowing or Ti 3+ -self doping. The materials provide HER values ranging from about 0.15 to 0.40 mmol h -1 g cat -1 , under both UV- and visible-light irradiation, employing glycerol as sacrificial agent and without any co-catalyst., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In this study, the protocol of a single-step L-cysteine functionalized silver nanoparticle synthesis was described. Particle size distribution was determined. The crystallinity and chemical properties were investigated using XRD, HR-TEM, and XPS methods. Acute toxicity and irritant properties of obtained nanoparticles were studied using mice and rats as an animal model. The results showed that thanks to the applied protocol, it was possible to synthesize silver nanoparticles with narrow particle size distribution. Moreover, the concentration of final product was extremely high in comparison to other known methods. These nanoparticles showed neither irritant properties nor acute toxicity.