Titanium-immobilized Layered HUS-7 Silicate as a Catalyst for Photocatalytic CO2 Reduction.

Utilizing photocatalytic CO2 reduction presents a promising avenue for combating climate change and curbing greenhouse gas emissions. However, maximizing its potential hinges on the development of materials that not only enhance efficiency but also ensure process stability. Here, we introduce Hiroshima University Silicate-7 (HUS-7) with immobilized Ti species as a standout contender. Our study demonstrates the remarkable photocatalytic activity of HUS-7 in CO2 reduction, yielding substantially higher carbonaceous product yields compared to conventional titanium-based catalysts TS-1 and P25. Through thorough characterization, we elucidate that their boosted photocatalytic performance is attributed to the incorporation of isolated Ti species within the silica-based precursor, serving as potent photoinduced active sites. Moreover, our findings underscore the crucial role of the Ligand-to-Metal Charge Transfer (LMCT) process in facilitating the photoactivation of CO2 molecules, shedding new light on key mechanisms underlying photocatalytic CO2 reduction.

Third-generation taxanes SB-T-121605 and SB-T-121606 are effective in pancreatic ductal adenocarcinoma.

Pancreatic cancer is a severe malignancy with increasing incidence and high mortality due to late diagnosis and low sensitivity to treatments. Search for the most appropriate drugs and therapeutic regimens is the most promising way to improve the treatment outcomes of the patients. This study aimed to compare (1) in vitro efficacy and (2) in vivo antitumor effects of conventional paclitaxel and the newly synthesized second (SB-T-1216) and third (SB-T-121605 and SB-T-121606) generation taxanes in KRAS wild type BxPC-3 and more aggressive KRAS G12V mutated Paca-44 pancreatic cancer cell line models. In vitro, paclitaxel efficacy was 27.6 ± 1.7 nM, while SB-Ts showed 1.7-7.4 times higher efficacy. Incorporation of SB-T-121605 and SB-T-121606 into in vivo therapeutic regimens containing paclitaxel was effective in suppressing tumor growth in Paca-44 tumor-bearing mice at small doses (≤3 mg/kg). SB-T-121605 and SB-T-121606 in combination with paclitaxel are promising candidates for the next phase of preclinical testing.

Role of lamp type in conventional batch and micro-photoreactor for photocatalytic hydrogen production.

The use of an irradiation source with a homogeneous distribution of irradiation in the volume of the reaction mixture belongs to the essential aspects of heterogeneous photocatalysis. First, the efficacy of six lamps with various radiation intensity and distribution characteristics is contrasted. The topic of discussion is the photocatalytic hydrogen production from a methanol-water solution in the presence of a NiO-TiO2 photocatalyst. The second section is focused on the potential of a micro-photoreactor system-the batch reactor with a micro-reactor with a circulating reaction mixture, in which the photocatalytic reaction takes place using TiO2 immobilized on borosilicate glass. Continuous photocatalytic hydrogen generation from a methanol-water solution is possible in a micro-photoreactor. This system produced 333.7 ± 21.1 µmol H2 (252.8 ± 16.0 mmol.m-2, the hydrogen formation per thin film area) in a reproducible manner during 168 h.

Versatile application of BiVO4/TiO2 S-scheme photocatalyst: Photocatalytic CO2 and Cr(VI) reduction.

Herein, the synthesis, characterization, and reduction properties of 2D TiO2 aerogel powder decorated with BiVO4 (TiO2/BiVO4) were investigated for versatile applications. First, 2D TiO2 was prepared via lyophilization and subsequently modified with BiVO4 using a wet impregnation method. The morphology, structure, composition, and optical properties were evaluated using transmission electron microscopy (TEM), X-ray diffractometry (XRD), laser-induced breakdown spectroscopy (LIBS), and diffuse reflectance spectroscopy (DRS), respectively. Significantly enhanced photocurrent densities (by 3-15 times) were obtained for TiO2/BiVO4 compared to those of pure TiO2 and BiVO4. The reduction of toxic Cr(VI) to Cr(III) was assessed, including the effect of pH on overall photocatalytic efficiency. Under acidic conditions (pH âˆ¼ 2), Cr(VI) reduction efficiency reached 100% within 2 h. For photocatalytic CO2 reduction, the highest yields of CH4 and CO were obtained using TiO2/BiVO4. A higher efficiency for both applications was achieved because of the better separation of the electron-hole pairs in TiO2/BiVO4. The excellent stability of TiO2/BiVO4 over repeated runs highlights its potential for use in versatile environmental applications. The efficiency of TiO2/BiVO4 is due to the interplay of the structure, morphology, composition, and photoelectrochemical properties that favour the material for the presented herein photocatalytic applications.

Innovative technology for ammonia abatement from livestock buildings using advanced oxidation processes.

The feasibility of using advanced oxidation processes (AOPs) for abatement of ammonia from livestock buildings was examined in a series of pilot plant experiments. In this study, all the experiments were conducted in a two-step unit containing a dry photolytic reactor (UV185/UV254/O3) and a photochemical scrubber (UV254/H2O2). The unit efficiency was tested for two initial ammonia concentrations (20 and 35 ppmv) and three different air flows (150, 300 and 450 m3·h-1). While the first step removes mainly organic pollutants that are often present together with ammonia in the air and ammonia only partially, the second step removes around 90% of ammonia emissions even at the highest flow rate of 450 m3·h-1. Absorbed ammonia in the aqueous phase can be effectively removed without adjusting the pH (i.e. without the addition of other additives) using UV and ozone. Complete removal of ammonia was achieved after 15 h of irradiation. In order to assess the price efficiency of the suggested technology and to be able to compare it with other methods the figures-of-merit were determined. The price needed for lowering ammonia emission by one order of magnitude is 0.002 € per cubic meter of treated air at the highest flow rate of 450 m3·h-1 and for initial ammonia concentrations of 20 ppmv. These findings demonstrate that AOPs are a promising method for ammonia abatement from livestock buildings which are rarely using any waste air treatment method.

Continuous-Flow Chemistry and Photochemistry for Manufacturing of Active Pharmaceutical Ingredients.

An active pharmaceutical ingredient (API) is any substance in a pharmaceutical product that is biologically active. That means the specific molecular entity is capable of achieving a defined biological effect on the target. These ingredients need to meet very strict limits; chemical and optical purity are considered to be the most important ones. A continuous-flow synthetic methodology which utilizes a continuously flowing stream of reactive fluids can be easily combined with photochemistry, which works with the chemical effects of light. These methods can be useful tools to meet these strict limits. Both of these methods are unique and powerful tools for the preparation of natural products or active pharmaceutical ingredients and their precursors with high structural complexity under mild conditions. This review shows some main directions in the field of active pharmaceutical ingredients' preparation using continuous-flow chemistry and photochemistry with numerous examples of industry and laboratory-scale applications.

Synthesis of vacant graphitic carbon nitride in argon atmosphere and its utilization for photocatalytic hydrogen generation.

Graphitic carbon nitride (C3N4) was synthesised from melamine at 550 °C for 4 h in the argon atmosphere and then was reheated for 1-3 h at 500 °C in argon. Two band gaps of 2.04 eV and 2.47 eV were observed in all the synthetized materials. Based on the results of elemental and photoluminescence analyses, the lower band gap was found to be caused by the formation of vacancies. Specific surface areas of the synthetized materials were 15-18 m2g-1 indicating that no thermal exfoliation occurred. The photocatalytic activity of these materials was tested for hydrogen generation. The best photocatalyst showed 3 times higher performance (1547 µmol/g) than bulk C3N4 synthetized in the air (547 µmol/g). This higher activity was explained by the presence of carbon (VC) and nitrogen (VN) vacancies grouped in their big complexes 2VC + 2VN (observed by positron annihilation spectroscopy). The effect of an inert gas on the synthesis of C3N4 was demonstrated using Graham´s law of ammonia diffusion. This study showed that the synthesis of C3N4 from nitrogen-rich precursors in the argon atmosphere led to the formation of vacancy complexes beneficial for hydrogen generation, which was not referred so far.

Reductive Modification of Carbon Nitride Structure by Metals-The Influence on Structure and Photocatalytic Hydrogen Evolution.

Pt, Ru, and Ir were introduced onto the surface of graphitic carbon nitride (g-C3N4) using the wet impregnation method. A reduction of these photocatalysts with hydrogen causes several changes, such as a significant increase in the specific surface area, a C/N atomic ratio, a number of defects in the crystalline structure of g-C3N4, and the contribution of nitrogen bound to the amino and imino groups. According to the X-ray photoelectron spectroscopy results, a transition layer is formed at the g-C3N4/metal nanoparticle interphase, which contains metal at a positive degree of oxidation bonded to nitrogen. These structural changes significantly enhanced the photocatalytic activity in the production of hydrogen through the water-splitting reaction. The activity of the platinum photocatalyst was 24 times greater than that of pristine g-C3N4. Moreover, the enhanced activity was attributed to significantly better separation of photogenerated electron-hole pairs on metal nanoparticles and structural distortions of g-C3N4.

Photocatalytic Reduction of Carbon Dioxide on TiO2 Heterojunction Photocatalysts-A Review.

The photocatalytic reduction of carbon dioxide to renewable fuel or other valuable chemicals using solar energy is attracting the interest of researchers because of its great potential to offer a clean fuel alternative and solve global warming problems. Unfortunately, the efficiency of CO2 photocatalytic reduction remains not very high due to the fast recombination of photogenerated electron-hole and small light utilization. Consequently, tremendous efforts have been made to solve these problems, and one possible solution is the use of heterojunction photocatalysts. This review begins with the fundamental aspects of CO2 photocatalytic reduction and the fundamental principles of various heterojunction photocatalysts. In the following part, we discuss using TiO2 heterojunction photocatalysts with other semiconductors, such as C3N4, CeO2, CuO, CdS, MoS2, GaP, CaTiO3 and FeTiO3. Finally, a concise summary and presentation of perspectives in the field of heterojunction photocatalysts are provided. The review covers references in the years 2011-2021.

Polymorphonuclear Cells Show Features of Dysfunctional Activation During Fatal Sepsis.

Sepsis and septic shock remain leading causes of morbidity and mortality for patients in the intensive care unit. During the early phase, immune cells produce various cytokines leading to prompt activation of the immune system. Polymorphonuclear leukocytes (PMNs) respond to different signals producing inflammatory factors and executing their antimicrobial mechanisms, resulting in the engulfment and elimination of invading pathogens. However, excessive activation caused by various inflammatory signals produced during sepsis progression can lead to the alteration of PMN signaling and subsequent defects in their functionality. Here, we analyzed samples from 34 patients in septic shock, focusing on PMNs gene expression and proteome changes associated with septic shock. We revealed that, compared to those patients who survived longer than five days, PMNs from patients who had fulminant sepsis were characterized by a dysfunctional hyper-activation, show altered metabolism, and recent exit from the cell cycle and signs of cellular lifespan. We believe that this multi-omics approach, although limited, pinpoints the alterations in PMNs' functionality, which may be rescued by targeted treatments.

Physico-Chemical Characterization and Antimicrobial Properties of Hybrid Film Based on Saponite and Phloxine B.

This research was aimed at the preparation of a hybrid film based on a layered silicate saponite (Sap) with the immobilized photosensitizer phloxine B (PhB). Sap was selected because of its high cation exchange capacity, ability to exfoliate into nanolayers, and to modify different surfaces. The X-ray diffraction of the films confirmed the intercalation of both the surfactant and PhB molecules in the Sap film. The photosensitizer retained its photoactivity in the hybrid films, as shown by fluorescence spectra measurements. The water contact angles and the measurement of surface free energy demonstrated the hydrophilic nature of the hybrid films. Antimicrobial effectiveness, assessed by the photodynamic inactivation on hybrid films, was tested against a standard strain and against methicillin-resistant bacteria of Staphylococcus aureus (MRSA). One group of samples was irradiated (green LED light; 2.5 h) and compared to nonirradiated ones. S. aureus strains manifested a reduction in growth from 1-log10 to over 3-log10 compared to the control samples with Sap only, and defects in S. aureus cells were proven by scanning electron microscopy. The results proved the optimal photo-physical properties and anti-MRSA potential of this newly designed hybrid system that reflects recent progress in the modification of surfaces for various medical applications.

Multiscale Analysis of Extracellular Matrix Remodeling in the Failing Heart.

RATIONALE: Cardiac ECM (extracellular matrix) comprises a dynamic molecular network providing structural support to heart tissue function. Understanding the impact of ECM remodeling on cardiac cells during heart failure (HF) is essential to prevent adverse ventricular remodeling and restore organ functionality in affected patients. OBJECTIVES: We aimed to (1) identify consistent modifications to cardiac ECM structure and mechanics that contribute to HF and (2) determine the underlying molecular mechanisms. METHODS AND RESULTS: We first performed decellularization of human and murine ECM (decellularized ECM) and then analyzed the pathological changes occurring in decellularized ECM during HF by atomic force microscopy, 2-photon microscopy, high-resolution 3-dimensional image analysis, and computational fluid dynamics simulation. We then performed molecular and functional assays in patient-derived cardiac fibroblasts based on YAP (yes-associated protein)-transcriptional enhanced associate domain (TEAD) mechanosensing activity and collagen contraction assays. The analysis of HF decellularized ECM resulting from ischemic or dilated cardiomyopathy, as well as from mouse infarcted tissue, identified a common pattern of modifications in their 3-dimensional topography. As compared with healthy heart, HF ECM exhibited aligned, flat, and compact fiber bundles, with reduced elasticity and organizational complexity. At the molecular level, RNA sequencing of HF cardiac fibroblasts highlighted the overrepresentation of dysregulated genes involved in ECM organization, or being connected to TGFß1 (transforming growth factor ß1), interleukin-1, TNF-α, and BDNF signaling pathways. Functional tests performed on HF cardiac fibroblasts pointed at mechanosensor YAP as a key player in ECM remodeling in the diseased heart via transcriptional activation of focal adhesion assembly. Finally, in vitro experiments clarified pathological cardiac ECM prevents cell homing, thus providing further hints to identify a possible window of action for cell therapy in cardiac diseases. CONCLUSIONS: Our multiparametric approach has highlighted repercussions of ECM remodeling on cell homing, cardiac fibroblast activation, and focal adhesion protein expression via hyperactivated YAP signaling during HF.

Efficiencies Evaluation of Photocatalytic Paints Under Indoor and Outdoor Air Conditions.

The removal of indoor and outdoor air pollutants is crucial to prevent environmental and health issues. Photocatalytic building materials are an energy-sustainable technology that can completely oxidize pollutants, improving in situ the air quality of contaminated sites. In this work, different photoactive TiO2 catalysts (anatase or modified anatase) and amounts were used to formulate photocatalytic paints in replacement of the normally used TiO2 (rutile) pigment. These paints were tested in two different experimental systems simulating indoor and outdoor environments. In one, indoor illumination conditions were used in the photoreactor for the oxidation of acetaldehyde achieving conversions between 37 and 55%. The other sets of experiments were performed under simulated outdoor radiation for the degradation of nitric oxide, resulting in conversions between 13 and 35%. This wide range of conversions made it difficult to directly compare the paints. Thus, absorption, photonic, and quantum efficiencies were calculated to account for the paints photocatalytic performance. It was found that the formulations containing carbon-doped TiO2 presented the best efficiencies. The paint with the maximum amount of this photocatalyst showed the highest absorption and photonic efficiencies. On the other hand, the paint with the lowest amount of carbon-doped TiO2 presented the highest value of quantum efficiency, thus becoming the optimal formulation in terms of energy use.

Influence of High Temperature Synthesis on the Structure of Graphitic Carbon Nitride and Its Hydrogen Generation Ability.

Graphitic carbon nitride (g-C3N4) was obtained by thermal polymerization of dicyandiamide, thiourea or melamine at high temperatures (550 and 600 °C), using different heating rates (2 or 10 °C min-1) and synthesis times (0 or 4 h). The effects of the synthesis conditions and type of the precursor on the efficiency of g-C3N4 were studied. The most efficient was the synthesis from dicyandiamide, 53%, while the efficiency in the process of synthesis from melamine and thiourea were much smaller, 26% and 11%, respectively. On the basis of the results provided by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), infrared spectroscopy (FTIR), ultraviolet-visible spectroscopy (UV-vis), thermogravimetric analysis (TGA), elemental analysis (EA), the best precursor and the optimum conditions of synthesis of g-C3N4 were identified to get the product of the most stable structure, the highest degree of ordering and condensation of structure and finally the highest photocatalytic activity. It was found that as the proton concentration decreased and the degree of condensation increased, the hydrogen yields during the photocatalytic decomposition of water-methanol solution were significantly enhanced. The generation of hydrogen was 1200 µmol g-1 and the selectivity towards hydrogen of more than 98%.

Successful Immobilization of Lanthanides Doped TiO2 on Inert Foam for Repeatable Hydrogen Generation from Aqueous Ammonia.

We describe the successful possibility of the immobilization of a photocatalyst on foam, which is beneficial from a practical point of view. An immobilized photocatalyst is possible for use in a continuous experiment and can be easily separated from the reactor after the reaction concludes. Parent TiO2, La/TiO2, and Nd/TiO2 photocatalysts (containing 0.1 wt.% of lanthanide) were prepared by the sol-gel method and immobilized on Al2O3/SiO2 foam (VUKOPOR A) by the dip-coating method. The photocatalysts were investigated for the photocatalytic hydrogen generation from an aqueous ammonia solution under UVA light (365 nm). The evolution of hydrogen was compared with photolysis, which was limited to zero. The higher hydrogen generation was observed in the presence of 0.1 wt.% La/TiO2 than in 0.1 wt.% Nd/TiO2. This is, besides other things, related to the higher level of the conduction band, which was observed for 0.1 wt.% La/TiO2. The higher conduction band's position is more effective for hydrogen production from ammonia decomposition.

Degradation of ammonia from gas stream by advanced oxidation processes.

The reduction of ammonia emissions from air was experimentally investigated by advanced oxidation processes (AOPs) utilizing the combination of ultraviolet irradiation with ozone. The influence of operating conditions such as initial ammonia concentration and flow rate of gas on the reduction of ammonia concentration was investigated in homemade photochemical unit. The conversion of ammonia decreased with increasing initial concentration of ammonia and with increasing flow rate of air (decreasing retention time). The highest conversion of ammonia (97%) was achieved under lower initial concentration of ammonia (30 ppm) and lower flow rate of air (28 m3/h). The energy per order was evaluated for the advanced oxidation process too. The energy consumption was about 0.037 kWh/m3/order for the 97% ammonia conversion at 30 ppm of initial ammonia concentration and 28 m3/h flow rate of air. Based on the results, the advanced oxidation process combining the UV irradiation and ozone was effective for mitigation of ammonia concentration and presents a promising technology for the reduction of odor emissions from livestock buildings. Moreover, the AOPs are suitable for application for high flow rate of air, especially for ammonia abatement from livestock buildings, where very high efficiency is expected.

The Role of Fluorine in F-La/TiO2 Photocatalysts on Photocatalytic Decomposition of Methanol-Water Solution.

F-La/TiO2 photocatalysts were studied in photocatalytic decomposition water-methanol solution. The structural, textural, optical, and electronic properties of F-La/TiO2 photocatalysts were studied by combination of X-ray powder diffraction (XRD), nitrogen physisorption, Ultraviolet-visible diffuse reflectance spectroscopy (UV-Vis DRS), Electrochemical impedance spectroscopy (EIS), and X-ray fluorescence (XPS). The production of hydrogen in the presence of 2.8F-La/TiO2 was nearly up to 3 times higher than in the presence of pure TiO2. The photocatalytic performance of F-La/TiO2 increased with increasing photocurrent response and conductivity originating from the higher amount of fluorine presented in the lattice of TiO2.

α-Fe2O3 Nanoparticles/Vermiculite Clay Material: Structural, Optical and Photocatalytic Properties.

Photocatalysis is increasingly becoming a center of interest due to its wide use in environmental remediation. Hematite (α-Fe2O3) is one promising candidate for photocatalytic applications. Clay materials as vermiculite (Ver) can be used as a carrier to accommodate and stabilize photocatalysts. Two different temperatures (500 °C and 700 °C) were used for preparation of α-Fe2O3 nanoparticles/vermiculite clay materials. The experimental methods used for determination of structural, optical and photocatalytic properties were X-ray fluorescence (ED-XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM) with energy dispersive X-ray spectrometry (EDS), N2 adsorption method (BET), diffuse reflectance UV-Vis spectroscopy (DRS), photoluminescence spectroscopy (PL) and photocatalytic reduction of CO2, respectively. The data from XRD were confronted with molecular modeling of the material arrangement in the interlayer space of vermiculite structure and the possibility of anchoring the α-Fe2O3 nanoparticles to the surface and edge of vermiculite. Correlations between structural, textural, optical and electrical properties and photocatalytic activity have been studied in detail. The α-Fe2O3 and α-Fe2O3/Ver materials with higher specific surface areas, a smaller crystallite size and structural defects (oxygen vacancies) that a play crucial role in photocatalytic activity, were prepared at a lower calcination temperature of 500 °C.

Photocatalytic Decomposition of N2O Over Ceramics Cordierite/CeO2 Nanoparticles.

The study is focused on the testing of the photocatalytic ability to decompose nitrous oxide (N2O) over cordierite/CeO² nanoparticles ceramic photocatalysts. The activity of ceramic materials was compared with the activity of industrially produced TiO² (Evonik photocatalyst). Photocatalytic decomposition of N2O over the ceramic samples and the TiO² Evonik was performed in annular batch reactor illuminated with 8 W Hg lamp (λ ═ 254 nm wavelength). Reaction kinetics was well described by pseudo 1st rate law. Photocatalytic activity of cordierite/CeO² was better in comparison with TiO² Evonik P25. The highest N2O conversion (56%) after 20 h of irradiation in inert gas was achieved over the sample with higher amount of CeO². This photocatalyst sample was examined for photocatalytic activity in the decomposition of N2O in the three various gaseous feed mixtures. The gaseous feed mixtures were: N2O enriched with O² (6.5 mol.%); N2O enriched with H2O(25 mol.%) and N2O enriched with mixture of O² and H2O(6.5 mol.% and 25 mol.%, respectively). It is assumed that the reduced conversion of N2O (47%) observed in the flow of the mixture of N2O and H2Ocould be affected by the sorption of water vapor on/onto the photocatalyst "active sites" causing less penetration of light and thus reducing the efficiency of photocatalytic decomposition of N2O. The presence of oxygen in the N2O mixture had only little effect to photocatalytic decomposition of N2O.

TiO2 and Nitrogen Doped TiO2 Prepared by Different Methods; on the (Micro)structure and Photocatalytic Activity in CO2 Reduction and N2O Decomposition.

TiO2 as nanostructured powders were prepared by (1) sol-gel process and (2) hydrothermal method in combination with (A) the processing by pressurized hot water and methanol or (B) calcination. The subsequent synthesis step was the modification of prepared nanostructured TiO2 with nitrogen using commercial urea. Textural, structural, surface and optical properties of prepared TiO2 and N/TiO2 were characterized by nitrogen physisorption, powder X-ray diffraction, X-ray photoelectron spectroscopy and DR UV-vis spectroscopy. It was revealed that TiO2 and N/TiO2 processed by pressurized fluids showed the highest surface areas. Furthermore, all prepared materials were the mixtures of major anatase phase and minor brookite phase, which was in nanocrystalline or amorphous (as nuclei) form depending on the applied preparation method. All the N/TiO2 materials exhibited enhanced crystallinity with a larger anatase crystallite-size than undoped parent TiO2. The photocatalytic activity of the prepared TiO2 and N/TiO2 was tested in the photocatalytic reduction of CO2 and the photocatalytic decomposition of N2O. The key parameters influencing the photocatalytic activity was the ratio of anatase-to-brookite and character of brookite. The optimum ratio of anatase-to-brookite for the CO2 photocatalytic reduction was determined to be about 83 wt.% of anatase and 17 wt.% of brookite (amorphous-like) (TiO2-SG-C). The presence of nitrogen decreased a bit the photocatalytic activity of tested materials. On the other hand, TiO2-SG-C was the least active in the N2O photocatalytic decomposition. In the case of N2O photocatalytic decomposition, the modification of TiO2 crystallites surface by nitrogen increased the photocatalytic activity of all investigated materials. The maximum N2O conversion (about 63 % after 18 h of illumination) in inert gas was reached over all N/TiO2.