Visible-Light Activation of a Dissolved Organic Matter-TiO2 Complex Mediated via Ligand-to-Metal Charge Transfer.

Given the widespread use of TiO2, its release into aquatic systems and complexation with dissolved organic matter (DOM) are highly possible, making it important to understand how such interactions affect photocatalytic activity under visible light. Here, we show that humic acid/TiO2 complexes (HA/TiO2) exhibit photoactivity (without significant electron-hole activation) under visible light through ligand-to-metal charge transfer (LMCT). The observed visible-light activities for pollutant removal and bacterial inactivation are primarily linked to the generation of H2O2via the conduction band. By systematically considering molecular-scale interactions between TiO2 and organic functional groups in HA, we find a key role of phenolic groups in visible-light absorption and H2O2 photogeneration. The photochemical formation of H2O2 in river waters spiked with TiO2 is notably elevated above naturally occurring H2O2 generated from background organic constituents due to LMCT contribution. Our findings suggest that H2O2 generation by HA/TiO2 is related to the quantity and functional group chemistry of DOM, which provides chemical insights into photocatalytic activity and potential ecotoxicity of TiO2 in environmental and engineered systems.

Long-term and stable antimicrobial properties of immobilized Ni/TiO2 nanocomposites against Escherichia coli, Legionella thermalis, and MS2 bacteriophage.

Nickel has been extensively used as a high work function metal because of its abundance, low cost, relatively non-toxic nature, and environmentally benign characteristics. However, it has rarely been extended in a form of immobilized composite, which is a practical strategy applicable for photocatalytic antimicrobial activities. In this study, a composite of nickel and TiO2 (Ni/TiO2) was prepared using a photodeposition method, and its antibacterial properties were investigated using Escherichia coli (E. coli). To optimize Ni/TiO2 synthesis, the effect of various photodeposition conditions on antibacterial performance were investigated, such as the light irradiation time, metal content, TiO2 crystalline structure, and presence or absence of electron donors (i.e., methanol). The optimized 2 wt% Ni/TiO2 exhibited an antibacterial efficiency of 3.74 log within 7 min, which is more than 10-fold higher than that of pristine TiO2 (2.54 log). Based on this optimized weight ratio, Ni/TiO2 was immobilized on a steel mesh using an electrospray/thermal compression method, and its antibacterial performance was further assessed against E. coli, MS2 bacteriophage virus (MS2 phage), and a common pulmonary pathogen (Legionella thermalis, L. thermalis). Within 70 min, all target microorganisms achieved an inactivation that exceeded 4 log. Furthermore, the long-term stability and sustainable usability of the Ni/TiO2 mesh were confirmed by performing more than 50 antibacterial evaluation cycles using E. coli. The results of this study facilitate the successful utilization of immobilized Ni/TiO2 mesh in water disinfection applications.

Entropy-Driven Aggregation of Titanium Dioxide Nanoparticles in Aquatic Environments.

The aggregation process of engineered nanoparticles (ENPs) is important in assessing their fate and transport in the environment. Here, we present the application of isothermal titration calorimetry (ITC) in studying the thermodynamics of ENPs' aggregation in aqueous solutions containing monovalent (NaCl) and divalent (CaCl2) electrolytes, natural organic matter, and hematite natural NPs, which enables us to elucidate their interaction mechanism. The free energies for the aggregation of TiO2 at different solution conditions were dominated by large favorable entropy, presumably because of the expulsion of bound water molecules to the solution upon complexation. The copresence of humic acid and Ca2+ facilitated aggregation for both homo- and heterosystems through intra- or intermolecular bridging, leading to the formation of more compact aggregates. We believe that this ITC strategy can be successfully used to characterize the interaction details between ENPs and various environmental components in ambient water systems.

An Atelocollagen Injection Enhances the Healing of Nonoperatively Treated Achilles Tendon Tears: An Experimental Study in Rats.

Background: There is growing interest in nonoperative treatment for the management of Achilles tendon ruptures (ATRs). However, nonoperative treatment is limited by the risk of tendon reruptures and low satisfaction rates. Recently, atelocollagen injections have been reported to have beneficial effects on tendon healing. Purpose: To evaluate the beneficial effects of injected atelocollagen on Achilles tendon healing and investigate the mechanism of atelocollagen on tendon healing. Study Design: Controlled laboratory study. Methods: Percutaneous tenotomy of the right Achilles tendon in 66 rats was performed. The animals were equally divided into the noninjection group (NG) and the collagen injection group (CG). At 1, 3, and 6 weeks, the Achilles functional index, cross-sectional area, load to failure, stiffness, stress, and the modified Bonar score were assessed. Transmission electron microscopy, western blotting, and immunohistochemistry were also performed. Results: The Achilles functional index (-6.8 vs -43.0, respectively; P = .040), load to failure (42.1 vs 27.0 N, respectively; P = .049), and stiffness (18.8 vs 10.3 N/mm, respectively; P = .049) were higher in the CG than those in the NG at 3 weeks. There were no significant differences in histological scores between the 2 groups. Transmission electron microscopy analysis showed that the mean diameter of collagen fibrils in the CG was greater than that in the NG at 3 weeks (117.2 vs 72.6 nm, respectively; P < .001) and 6 weeks (202.1 vs 144.0 nm, respectively; P < .001). Western blot analysis showed that the expression of collagen type I in the CG was higher than that in the NG at 1 week (P = .005) and 6 weeks (P = .001). Conclusion: An atelocollagen injection had beneficial effects on the healing of nonoperatively treated Achilles tendon injuries. The Achilles tendon of CG rats exhibited better functional, biomechanical, and morphological outcomes compared with NG rats. The molecular data indicated that the mechanism of atelocollagen injections may be associated with an increased amount of collagen type I. Clinical Relevance: An atelocollagen injection might be a good adjuvant option for the nonoperative treatment of ATRs.

Thorn-like TiO2 nanoarrays with broad spectrum antimicrobial activity through physical puncture and photocatalytic action.

To overcome the conventional limitation of TiO2 disinfection being ineffective under light-free conditions, TiO2 nanowire films (TNWs) were prepared and applied to bacterial disinfection under dark and UV illumination. TNW exhibited much higher antibacterial efficiencies against Escherichia coli (E. coli) under dark and UV illumination conditions compared to TiO2 nanoparticle film (TNP) which was almost inactive in the dark, highlighting the additional contribution of the physical interaction between bacterial membrane and NWs. Such a physical contact-based antibacterial activity was related to the NW geometry such as diameter, length, and density. The combined role of physical puncture and photocatalytic action in the mechanism underlying higher bactericidal effect of TNW was systematically examined by TEM, SEM, FTIR, XPS, and potassium ion release analyses. Moreover, TNW revealed antimicrobial activities in a broad spectrum of microorganisms including Staphylococcus aureus and MS2 bacteriophage, antibiofilm properties, and good material stability. Overall, we expect that the free-standing and antimicrobial TNW is a promising agent for water disinfection and biomedical applications in the dark and/or UV illumination.