Indicator displacement-based colorimetric assay for dibutyl phthalate in pharmaceutical products with titanium(IV)-pyridylazo resorcinol (PAR).

Taking advantage of the competitive binding affinity towards Ti(IV) between 4-(2-pyridylazo) resorcinol (PAR) and phthalate, a simple indicator displacement (ID)-based colorimetric assay was designed for indirect determination of a well-known phthalic acid ester, dibutyl phthalate (DBP). The indicator PAR and Ti(IV) formed a purplish-red-colored Ti(IV)-PAR complex (λmax = 540 nm) at a 1:1 ratio. In the presence of pre-hydrolyzed DBP, colorless complex formation of phthalate ion (emerging from alkaline hydrolysis of DBP) with Ti(IV) resulted in a hypsochromic shift in absorbance maximum, accompanying a color change from purplish-red to yellowish-orange (λmax = 390 nm) by the release of PAR from Ti(IV)-PAR system. Based on this mechanism, the linear response range of the system for DBP was found to lie between 0.16 and 0.37 mmol L-1 with an experimental detection limit of 11.6 µmol L-1. The recommended Ti(IV)-PAR system was successfully applied to DBP-containing pharmaceutical products (as real sample) after a simple clean-up process for removing possible water-soluble interferents. The analytical results obtained from the recommended method (by applying the standard addition approach) and the reference liquid chromatography-tandem mass spectrometric (LC-MS/MS) method were statistically compared using DBP-extract of the drug samples. Consequently, a simple and selective colorimetric ID strategy was proposed for the analysis of DBP in pharmaceuticals for the first time.

Effect of Nitrogen Doping on the Photocatalytic Properties and Antibiofilm Efficacy of Reduced TiO2 Nanoparticles.

Nanomaterial-mediated antibacterial photodynamic therapy (aPDT) emerges as a promising treatment against antibiotic-resistant bacterial biofilms. Specifically, titanium dioxide nanoparticles (TiO2 NPs) are being investigated as photosensitizers in aPDT to address biofilm related diseases. To enhance their photocatalytic performance in the visible spectral range for biomedical applications, various strategies have been adopted, including reduction of TiO2 NPs. However, despite improvements in visible-light photoactivity, reduced TiO2 NPs have yet to reach their expected performance primarily due to the instability of oxygen vacancies and their tendency to reoxidize easily. To address this, we present a two-step approach to fabricate highly visible-light active and stable TiO2 NP photocatalysts, involving nitrogen doping followed by a magnesium-assisted reductive annealing process. X-ray photoelectron spectroscopy analysis of the synthesized reduced nitrogen-doped TiO2 NPs (H:Mg-N-TiO2 NPs) reveals that the presence of nitrogen stabilizes oxygen vacancies and reduced Ti species, leading to increased production of reactive oxygen species under visible-light excitation. The improved aPDT efficiency translates to a 3-fold enhancement in the antibiofilm activity of nitrogen-doped compared to undoped reduced TiO2 NPs against both Gram-positive (Streptococcus mutans) and Gram-negative (Porphyromonas gingivalis, Fusobacterium nucleatum) oral pathogens. These results underscore the potential of H:Mg-N-TiO2 NPs in aPDT for combating bacterial biofilms effectively.

Impact of the spatial orientation of the patient's head, metal artifact reduction, and tube current on cone-beam computed tomography artifact expression adjacent to a dental implant: A laboratory study using a simulated surgical guide.

Purpose: The aim of this study was to evaluate image artifacts in the vicinity of dental implants in cone-beam computed tomography (CBCT) scans obtained with different spatial orientations, tube current levels, and metal artifact reduction algorithm (MAR) conditions. Materials and Methods: One dental implant and 2 tubes filled with a radiopaque solution were placed in the posterior region of a mandible using a surgical guide to ensure parallel alignment. CBCT scans were acquired with the mandible in 2 spatial orientations in relation to the X-ray projection plane (standard and modified) at 3 tube current levels: 5, 8, and 11 mA. CBCT scans were repeated without the implant and were reconstructed with and without MAR. The mean voxel and noise values of each tube were obtained and compared using multi-way analysis of variance and the Tukey test (α=0.05). Results: Mean voxel values were significantly higher and noise values were significantly lower in the modified orientation than in the standard orientation (P<0.05). MAR activation and tube current levels did not show significant differences in most cases of the modified spatial orientation and in the absence of the dental implant (P>0.05). Conclusion: Modifying the spatial orientation of the head increased brightness and reduced spatial orientation noise in adjacent regions of a dental implant, with no influence from the tube current level and MAR.

Cephalometric evaluation of skeletal stability and pharyngeal airway changes after mandibular setback surgery: Bioabsorbable versus titanium plate and screw fixation.

Purpose: This study compared sequential changes in skeletal stability and the pharyngeal airway following mandibular setback surgery involving fixation with either a titanium or a bioabsorbable plate and screws. Materials and Methods: Twenty-eight patients with mandibular prognathism undergoing bilateral sagittal split osteotomy by titanium or bioabsorbable fixation were randomly selected in this study. Lateral cephalometric analysis was conducted preoperatively and at 1 week, 3-6 months, and 1 year postoperatively. Mandibular stability was assessed by examining horizontal (BX), vertical (BY), and angular measurements including the sella-nasion to point B angle and the mandibular plane angle (MPA). Pharyngeal airway changes were evaluated by analyzing the nasopharynx, uvula-pharynx, tongue-pharynx, and epiglottis-pharynx (EOP) distances. Mandibular and pharyngeal airway changes were examined sequentially. To evaluate postoperative changes within groups, the Wilcoxon signed-rank test was employed, while the Mann-Whitney U test was used for between-group comparisons. Immediate postoperative changes in the airway were correlated to surgical movements using the Spearman rank test. Results: Significant changes in the MPA were observed in both the titanium and bioabsorbable groups at 3-6 months post-surgery, with significance persisting in the bioabsorbable group at 1 year postoperatively (2.29°±2.28°; P<0.05). The bioabsorbable group also exhibited significant EOP changes (-1.21±1.54 mm; P<0.05) at 3-6 months, which gradually returned to non-significant levels by 1 year postoperatively. Conclusion: Osteofixation using bioabsorbable plates and screws is comparable to that achieved with titanium in long-term skeletal stability and maintaining pharyngeal airway dimensions. However, a tendency for relapse exists, especially regarding the MPA.

Efficacy of plasma treatment for surface cleansing and osseointegration of sandblasted and acid-etched titanium implants.

PURPOSE: This study was conducted to evaluate the effects of plasma treatment of sandblasted and acid-etched (SLA) titanium implants on surface cleansing and osseointegration in a beagle model. MATERIALS AND METHODS: For morphological analysis and XPS analysis, scanning electron microscope and x-ray photoelectron spectroscopy were used to analyze the surface topography and chemical compositions of implant before and after plasma treatment. For this animal experiment, twelve SLA titanium implants were divided into two groups: a control group (untreated implants) and a plasma group (implants treated with plasma). Each group was randomly located in the mandibular bone of the beagle dog (n = 6). After 8 weeks, the beagle dogs were sacrificed, and volumetric analysis and histometric analysis were performed within the region of interest. RESULTS: In morphological analysis, plasma treatment did not alter the implant surface topography or cause any physical damage. In XPS analysis, the atomic percentage of carbon at the inspection point before the plasma treatment was 34.09%. After the plasma treatment, it was reduced to 18.74%, indicating a 45% reduction in carbon. In volumetric analysis and histometric analysis, the plasma group exhibited relatively higher mean values for new bone volume (NBV), bone to implant contact (BIC), and inter-thread bone density (ITBD) compared to the control group. However, there was no significant difference between the two groups (P > .05). CONCLUSION: Within the limits of this study, plasma treatment effectively eliminated hydrocarbons without changing the implant surface.

Light-Induced Transformation of Virus-Like Particles on TiO2.

Titanium dioxide (TiO2) shows significant potential as a self-cleaning material to inactivate severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) and prevent virus transmission. This study provides insights into the impact of UV-A light on the photocatalytic inactivation of adsorbed SARS-CoV-2 virus-like particles (VLPs) on a TiO2 surface at the molecular and atomic levels. X-ray photoelectron spectroscopy, combined with density functional theory calculations, reveals that spike proteins can adsorb on TiO2 predominantly via their amine and amide functional groups in their amino acids blocks. We employ atomic force microscopy and grazing-incidence small-angle X-ray scattering (GISAXS) to investigate the molecular-scale morphological changes during the inactivation of VLPs on TiO2 under light irradiation. Notably, in situ measurements reveal photoinduced morphological changes of VLPs, resulting in increased particle diameters. These results suggest that the denaturation of structural proteins induced by UV irradiation and oxidation of the virus structure through photocatalytic reactions can take place on the TiO2 surface. The in situ GISAXS measurements under an N2 atmosphere reveal that the virus morphology remains intact under UV light. This provides evidence that the presence of both oxygen and UV light is necessary to initiate photocatalytic reactions on the surface and subsequently inactivate the adsorbed viruses. The chemical insights into the virus inactivation process obtained in this study contribute significantly to the development of solid materials for the inactivation of enveloped viruses.

Chronic exposure to TiO2 micro- and nano particles: A biochemical and histopathological experimental study.

The aim of this work was to analyze the effects of long-term exposure to titanium dioxide (TiO2) micro- (MPs) and nanoparticles (NPs) (six and 12 months) on the biochemical and histopathological response of target organs using a murine model. Male Wistar rats were intraperitoneally injected with a suspension of TiO2 NPs (5 nm; TiO2-NP5 group) or MPs (45 µm; TiO2-NP5 group); the control group was injected with saline solution. Six and 12 months post-injection, titanium (Ti) concentration in plasma and target organs was determined spectrometrically (ICP-MS). Blood smears and organ tissue samples were evaluated by light microscopy. Liver and kidney function was evaluated using serum biochemical parameters. Oxidative metabolism was assessed 6 months post-injection (determination of superoxide anion by nitroblue tetrazolium (NBT) test, superoxide dismutase (SOD) and catalase (CAT), lipid peroxidation, and paraoxonase 1). Titanium (Ti) concentration in target organs and plasma was significantly higher in the TiO2-exposed groups than in the control group. Histological evaluation showed the presence of titanium-based particles in the target organs, which displayed no structural alterations, and in blood monocytes. Oxidative metabolism analysis showed that TiO2 NPs were more reactive over time than MPs (p < .05) and mobilization of antioxidant enzymes and membrane damage varied among the studied organs. Clearance of TiO2 micro and nanoparticles differed among the target organs, and lung clearance was more rapid than clearance from the lungs and kidneys (p < .05). Conversely, Ti concentration in plasma increased with time (p < .05). In conclusion, neither serum biochemical parameters nor oxidative metabolism markers appear to be useful as biomarkers of tissue damage in response to TiO2 micro- and nanoparticle deposits at chronic time points.

TiO2-based photocatalysts from type-II to S-scheme heterojunction and their applications.

Photocatalysis is a promising sustainable technology to remove organic pollution and convert solar energy into chemical energy. Titanium dioxide has drawn extensive attention in this field owing to its high activity under UV light, good chemical stability, large availability, low price and low toxicity. However, the poor quantum efficiency derived from fast electron/hole recombination, the limited utilization of sunlight, and a weak reducing ability still hinder its practical application. Among the modification strategies of TiO2 to enhance its performance, the construction of heterojunctions with other semiconductors is a powerful and versatile way to maximise the separation of photogenerated charge carriers and steer their transport toward enhanced efficiency and selectivity. Here, the research progress and current status of TiO2 modification are reviewed, focusing on heterojunctions. A rapid evolution of the understanding of the different charge transfer mechanisms is witnessed from traditional type II to the recently conceptualised S-scheme. Particular attention is paid to different synthetic approaches and interface engineering methods designed to improve and control the interfacial charge transfer, and several cases of TiO2 heterostructures with metal oxides, metal sulfides and carbon nitride are discussed. The application hotspots of TiO2-based photocatalysts are summarized, including hydrogen generation by water splitting, solar fuel production by CO2 conversion, and the degradation of organic water pollutants. Hints about less studied and emerging processes are also provided. Finally, the main issues and challenges related to the sustainability and scalability of photocatalytic technologies in view of their commercialization are highlighted, outlining future directions of development.

Novel approach for characterizing clinical load application of superelastic orthodontic wires.

OBJECTIVE: Current standardized in vitro bending experiments for orthodontic archwires cannot capture friction conditions and load sequencing during multi-bracket treatment. This means that clinically relevant forces exerted by superelastic wires cannot be predicted. To address these limitations, this study explored a novel test protocol that estimates clinical load range. METHODS: The correction of a labially displaced maxillary incisor was simulated using an in vitro model with three lingual brackets. Deflection force levels derived from four different protocols were designed to explore the impact of friction and wire load history. These force levels were compared in nickel-titanium (NiTi) archwires with three commonly used diameters. The unloading path varied between protocols, with single or multiple sequences and different load orders and initial conditions. RESULTS: Deflection forces from the new protocol, employing multiple continuous load/unload cycles (CCincr), consistently exceeded those from the conventional protocol using a single continuous unloading path (CUdecr). Mean differences in plateau force ranged from 0.54 N (Ø 0.014" wire) to 1.19 N (Ø 0.016" wire). The CCinr protocol also provided average force range estimates of 0.47 N (Ø 0.012" wire), 0.89 N (Ø 0.014" wire), and 1.15 N (Ø 0.016" wire). SIGNIFICANCE: Clinical orientation towards CUdecr carries a high risk of excessive therapeutic forces because clinical loading situations caused by friction and load history are underestimated. Physiological tooth mobility using NiTi wires contributes decisively to the therapeutic load situation. Therefore, only short unloading sequences starting from the maximum deflection in the load history, as in CCincr, are clinically meaningful.

Titanium-Coated Polyetheretherketone Cages Vs Full Titanium Cages for Stand-Alone 1- or 2-Level Anterior Cervical Discectomy and Fusion: A Comparative Study.

BACKGROUND: Anterior cervical discectomy and fusion (ACDF) for the surgical treatment of cervical degenerative disease often includes an intervertebral cage, which restores disc height and lordosis while promoting fusion . Cage materials include titanium (TTN) or polyetheretherketone (PEEK). Controversy in material selection stems from higher fusion rates with TNN, despite a higher subsidence rate, while PEEK cages demonstrate superior preservation of interspace height. Combining the advantages of both materials, TTN-coated PEEK (TCPEEK) cages were developed, featuring a PEEK core with similar stiffness to the bone, enveloped with a TTN coat, improving osteointegration. However, the potential superiority of TCPEEK over TTN cages has not been investigated. This study aimed to compare clinical and radiographic outcomes following single- or double-level ACDF using either TTN or TCPEEK cages. METHODS: This retrospective single-center study included patients undergoing single- or double-level ACDF between 2017 and 2019. Clinical outcomes included the Neck Disability Index and revision surgery incidence. Radiographic parameters included cervical and segmental lordosis, C2 to C7 sagittal vertical axis, fusion, subsidence, and adjacent segment degeneration at a minimum 12-month follow-up. RESULTS: A total of 45 patients (16 TTN; 29 TCPEEK) and 58 cervical levels (21 TTN; 37 TCPEEK) were included. Both cages significantly improved Neck Disability Index scores (TTN -10.0; TCPEEK -14.1) without significant differences. Two single-level TCPEEK patients required revision surgery due to non-union. In the radiological assessments, no significant difference was found for subsidence rates (TTN 52.4%; TCPEEK 56.8%), adjacent segment degeneration, cervical and segmental lordosis, and changes in C2 to C7 sagittal vertical axis. Though not statistically significant, fusion rates trended slightly higher with TTN (90.5%) vs TCPEEK cages (86.5%). CONCLUSION: TTN and TCPEEK cages achieve satisfactory clinical and radiological outcomes in single- or double-level ACDF. This finding suggests that the choice between them can be based on other factors, such as surgeon preference or availability, rather than specific material properties. CLINICAL RELEVANCE: This study found that the selection of ACDF cage material did not affect clinical outcomes.

Enhancing Laser-Induced Graphene via Integration of Gold Nanoparticles and Titanium Dioxide for Sensing and Robotics Applications.

Laser-induced graphene (LIG) is a promising material for various applications due to its unique properties and facile fabrication. However, the electrochemical performance of LIG is significantly lower than that of pure graphene, limiting its practical use. Theoretically, integrating other conductive materials with LIG can enhance its performance. In this study, we investigated the effects of incorporating gold nanoparticles (AuNPs) and titanium dioxide (TiO2) into LIG on its electrochemical properties using ReaxFF molecular dynamics (MD) simulations and experimental validation. We found that both AuNPs and TiO2 improved the work function and surface potential of LIG, resulting in a remarkable increase in output voltage by up to 970.5% and output power density by 630% compared to that of pristine LIG. We demonstrated the practical utility of these performance-enhanced LIG by developing motion monitoring devices, self-powered sensing systems, and robotic hand platforms. Our work provides new insights into the design and optimization of LIG-based devices for wearable electronics and smart robotics, contributing to the advancement of sustainable technologies.

Atomic Layer Growth of Rutile TiO2 Films with Ultrahigh Dielectric Constants via Crystal Orientation Engineering.

In general, the electronic and optical properties of oxide films can significantly benefit from highly textured crystallinity. However, oxide films grown by atomic layer deposition (ALD), a powerful technique for the synthesis of high-quality, nanoscale thin films, usually exhibit amorphous or randomly oriented polycrystalline phases. Here, we demonstrate the growth of highly textured rutile phase ALD TiO2 films through rational substrate design. Both a- and c-axis preferentially oriented TiO2 films are obtained by varying the lattice parameters of the initial ALD growth surface. Under optimized conditions, we find that it is possible to deposit high-quality, c-axis preferentially aligned TiO2 films with a bulk dielectric constant approaching 185, rivaling the single crystal limit. These films display a remarkably high dielectric constant of 117 despite thin thickness of 5.2 nm. Moreover, the addition of a single doping sequence of Al2O3 successfully suppresses leakage currents to levels compatible with modern dynamic random access memory cells, all the while maintaining the high bulk dielectric constant of 137. These results clearly highlight the prospect of utilizing crystal orientation engineering in ALD thin films for emerging semiconductor devices.

Comparison of Single or Double Titanium Mesh Cage for Anterior Reconstruction After Total En Bloc Spondylectomy for Thoracic and Lumbar Spinal Tumors.

OBJECTIVE: To compare the clinical efficacy of anterior column reconstruction using single or double titanium mesh cage (TMC) after total en bloc spondylectomy (TES) of thoracic and lumbar spinal tumors. METHODS: A retrospective cohort study was performed involving 39 patients with thoracic or lumbar spinal tumors. All patients underwent TES, followed by anterior reconstruction and screw-rod instrumentation via a posterior-only procedure. Twenty-two patients in group A were treated with a single TMC to reconstruct the anterior column, whereas 17 patients in group B were reconstructed with double TMCs. RESULTS: The overall follow-up is 20.5 ± 4.6 months. There is no significant difference between the 2 groups regarding age, sex, body mass index, tumor location, operative time, and intraoperative blood loss. The time for TMC placement was significantly shortened in the double TMCs group (5.2 ± 1.3 minutes vs. 15.6 ± 3.3 minutes, p = 0.004). Additionally, postoperative neural complications were significantly reduced with double TMCs (5/22 vs. 0/17, p = 0.046). The kyphotic Cobb angle and mean intervertebral height were significantly corrected in both groups (p ≤ 0.001), without obvious loss of correction at the last follow-up in either group. The bone fusion rates for single TMC and double TMCs were 77.3% and 76.5%, respectively. CONCLUSION: Using 2 smaller TMCs instead of a single large one eases the placement of TMC by shortening the time and avoiding nerve impingement. Anterior column reconstruction with double TMC is a clinically feasible, and safe alternative following TES for thoracic and lumbar tumors.

Nanofeatured surfaces in dental implants: contemporary insights and impending challenges.

Dental implant therapy, established as standard-of-care nearly three decades ago with the advent of microrough titanium surfaces, revolutionized clinical outcomes through enhanced osseointegration. However, despite this pivotal advancement, challenges persist, including prolonged healing times, restricted clinical indications, plateauing success rates, and a notable incidence of peri-implantitis. This review explores the biological merits and constraints of microrough surfaces and evaluates the current landscape of nanofeatured dental implant surfaces, aiming to illuminate strategies for addressing existing impediments in implant therapy. Currently available nanofeatured dental implants incorporated nano-structures onto their predecessor microrough surfaces. While nanofeature integration into microrough surfaces demonstrates potential for enhancing early-stage osseointegration, it falls short of surpassing its predecessors in terms of osseointegration capacity. This discrepancy may be attributed, in part, to the inherent "dichotomy kinetics" of osteoblasts, wherein increased surface roughness by nanofeatures enhances osteoblast differentiation but concomitantly impedes cell attachment and proliferation. We also showcase a controllable, hybrid micro-nano titanium model surface and contrast it with commercially-available nanofeatured surfaces. Unlike the commercial nanofeatured surfaces, the controllable micro-nano hybrid surface exhibits superior potential for enhancing both cell differentiation and proliferation. Hence, present nanofeatured dental implants represent an evolutionary step from conventional microrough implants, yet they presently lack transformative capacity to surmount existing limitations. Further research and development endeavors are imperative to devise optimized surfaces rooted in fundamental science, thereby propelling technological progress in the field.

Selective Tumor Inhibition Effect of Drug-Free Layered Double Hydroxide-Based Films via Responding to Acidic Microenvironment.

Nickel-titanium alloy stents are widely used in the interventional treatment of various malignant tumors, and it is important to develop nickel-titanium alloy stents with selective cancer-inhibiting and antibacterial functions to avoid malignant obstruction caused by tumor invasion and bacterial colonization. In this work, an acid-responsive layered double hydroxide (LDH) film was constructed on the surface of a nickel-titanium alloy by hydrothermal treatment. The release of nickel ions from the film in the acidic tumor microenvironment induces an intracellular oxidative stress response that leads to cell death. In addition, the specific surface area of LDH nanosheets could be further regulated by heat treatment to modulate the release of nickel ions in the acidic microenvironment, allowing the antitumor effect to be further enhanced. This acid-responsive LDH film also shows a good antibacterial effect against S. aureus and E. coli. Besides, the LDH film prepared without the introduction of additional elements maintains low toxicity to normal cells in a normal physiological environment. This work offers some guidance for the design of a practical nickel-titanium alloy stent for the interventional treatment of tumors.

Inhibiting dissolution strategy achieving high-performance sodium titanium phosphate hybrid anode in seawater-based dual-ion battery.

Aqueous sodium-ion batteries (ASIBs) show great promise as candidates for large-scale energy storage. However, the potential of ASIB is impeded by the limited availability of suitable anode types and the occurrence of dissolution side reactions linked to hydrogen evolution. In this study, we addressed these challenges by developing a Bi-coating modified anode based on a sodium titanium phosphate (NTP)-carbon fibers (CFs) hybrid electrode (NTP-CFs/Bi). The Bi-coating effectively mitigates the localized enrichment of hydroxyl anion (OH-) near the NTP surface, thus addressing the dissolution issue. Notably, the Bi-coating not only restricts the local abundance of OH- to inhibit dissolution but also ensures a higher capacity compared with other NTP-based anodes. Consequently, the NTP-CFs/Bi anode demonstrates an impressive specific capacity of 216.8 mAh/g at 0.2 mV/s and maintains a 90.7 % capacity retention after 1000 cycles at 6.3 A/g. This achievement sets a new capacity record among NTP-based anodes for sodium storage. Furthermore, when paired with a cathode composed of hydroxy nickel oxide directly grown on Ni foam, we assembled a seawater-based cell exhibiting high energy and power densities, surpassing the most recently reported ASIBs. This groundbreaking work lays the foundation for a potential method to develop long-life NTP-based anodes.

Dissecting the Photochemical Reactivity of Metal Ions during Atmospheric Nitrate Transformations on Photoactive Mineral Dust.

Dissecting the photochemical reactivity of metal ions is a significant contribution to understanding secondary pollutant formation, as they have a role to be reckoned with atmospheric chemistry. However, their photochemical reactivity has received limited attention within the active nitrogen cycle, particularly at the gas-solid interface. In this study, we delve into the contribution of magnesium ion (Mg2+) and ferric ion (Fe3+) to nitrate decomposition on the surface of photoactive mineral dust. Under simulated sunlight irradiation, the observed NOX production rate differs by an order of magnitude in the presence of Mg2+ (6.02 × 10-10 mol s-1) and Fe3+ (2.07 × 10-11 mol s-1). The markedly decreased fluorescence lifetime induced by Mg2+ and the change in the valence of Fe3+ revealed that Mg2+ and Fe3+ significantly affect the concentration of nitrate decomposition products by distinct photochemical reactivity with photogenerated electrons. Mg2+ promotes NOX production by accelerating charge transfer, while Fe3+ hinders nitrate decomposition by engaging in a redox cyclic reaction with Fe2+ to consume photogenerated carriers continuously. Furthermore, when Fe3+ coexists with other metal ions (e.g., Mg2+, Ca2+, Na+, and K+) and surpasses a proportion of approximately 12%, the photochemical reactivity of Fe3+ tends to be dominant in depleting photogenerated electrons and suppressing nitrate decomposition. Conversely, below this threshold, the released NOX concentration increases sharply as the proportion of Fe3+ decreases. This research offers valuable insights into the role of metal ions in nitrate transformation and the generation of reactive nitrogen species, contributing to a deep understanding of atmospheric photochemical reactions.

TNF-α-licensed exosome-integrated titaniumaccelerated T2D osseointegration by promoting autophagy-regulated M2 macrophage polarization.

Type 2 diabetes (T2D) is on a notable rise worldwide, which leads to unfavorable outcomes during implant treatments. Surface modification of implants and exosome treatment have been utilized to enhance osseointegration. However, there has been insufficient approach to improve adverse osseointegration in T2D conditions. In this study, we successfully loaded TNF-α-treated mesenchymal stem cell (MSC)-derived exosomes onto micro/nano-network titanium (Ti) surfaces. TNF-α-licensed exosome-integrated titanium (TNF-exo-Ti) effectively enhanced M2 macrophage polarization in hyperglycemic conditions, with increased secretion of anti-inflammatory cytokines and decreased secretion of pro-inflammatory cytokines. In addition, TNF-exo-Ti pretreated macrophage further enhanced angiogenesis and osteogenesis of endothelial cells and bone marrow MSCs. More importantly, TNF-exo-Ti markedly promoted osseointegration in T2D mice. Mechanistically, TNF-exo-Ti activated macrophage autophagy to promote M2 polarization through inhibition of the PI3K/AKT/mTOR pathway, which could be abolished by PI3K agonist. Thus, this study established TNF-α-licensed exosome-immobilized titanium surfaces that could rectify macrophage immune states and accelerate osseointegration in T2D conditions.

Mie Resonant Metal Oxide Nanospheres for Broadband Photocatalytic Enhancements.

Metal oxides are widely used in heterogeneous catalysis as supports to disperse catalytically active nanoparticles, isolated atomic sites, or even as catalysts themselves. Herein, we present a method to produce optically active metal oxide supports that exhibit size-dependent Mie resonances based on TiO2 nanospheres with tunable size, crystalline phase composition, and optical properties. Mie resonant TiO2 nanospheres were used as supports to disperse Au, Pt, and Pd nanoparticles. We have found up to a 50-fold enhancement of the electric field at the metal oxide/metal interface corresponding to wavelength-dependent multipolar resonances in the TiO2 structure. Using Au/TiO2 as a prototypical photocatalyst, we demonstrate broadband rate enhancements between 400 and 800 nm during CO oxidation, with a noticeable increase below 500 nm. This increased reactivity at higher photon energies is due to improved photon utilization and interband absorption in the gold that results in greater secondary electron generation through electron-electron scattering processes, thus leading to higher rates in conjunction with the Mie scattering TiO2 support. This study not only highlights the potential of Mie resonant TiO2 in broadband photocatalytic enhancements but also for developing various Mie resonant metal oxide supports, such as ZnO or Cu2O, which can improve photocatalytic performance for a number of critical reactions. As the chemical and energy industries move toward conversion technologies driven by renewable energy sources, the strategy of designing optical resonances into oxide supports that are already widely used could enable a straightforward adaptation of photochemical processing based on traditional heterogeneous catalysts.

Successful application of photocatalytic recycled TiO2-GO membranes for the removal of trace organic compounds from tertiary effluent.

Photocatalytic membranes are a promising technology for water and wastewater treatment. Towards circular economy, extending the lifetime of reverse osmosis (RO) membranes for as long as possible is extremely important, due to the great amount of RO modules discarded every year around the world. Therefore, in the present study, photocatalytic membranes made of recycled post-lifespan RO membrane (polyamide thin-film composite), TiO2 nanoparticles and graphene oxide are used in the treatment tertiary-treated domestic wastewater to remove trace organic compounds (TrOCs). The inclusion of dopamine throughout the surface modification process enhanced the stability of the membranes to be used as long as 10 months of operation. We investigated TrOCs removal by the membrane itself and in combination with UV-C and visible light by LED. The best results were obtained with integrated membrane UV-C system at pH 9, with considerable reductions of diclofenac (92%) and antipyrine (87%). Changes in effluent pH demonstrated an improvement in the attenuation of TrOCs concentration at higher pHs. By modifying membranes with nanocomposites, an increase in membrane hydrophilicity (4 degrees contact angle reduction) was demonstrated. The effect of the lamp position on the light fluence that reaches the membrane was assessed, and greater values were found in the middle of the membrane, providing parameters for process optimization (0.29 ± 0.10 mW cm-2 at the center of the membrane and 0.07 ± 0.03 mW cm-2 at the right and left extremities). Photocatalytic recycled TiO2-GO membranes have shown great performance to remove TrOCs and extend membrane lifespan, as sustainable technology to treat wastewater.