Key Strategies for Enhancing H2 Production in Transition Metal Oxide Based Photocatalysts.

Transition metal oxides (TMOs) were one of the first photocatalysts used to produce hydrogen from water using solar energy. Despite the emergence of many other genres of photocatalysts over the years, TMO photocatalysts remain dominant due to their easy synthesis and unique physicochemical properties. Various strategies have been developed to enhance the photocatalytic activity of TMOs, but the solar-to-hydrogen (STH) conversion efficiency of TMO photocatalysts is still very low (<2 %), which is far below the targeted STH of 10 % for commercial viability. This article provides a comprehensive analysis of several widely used strategies, including oxygen defects control, doping, establishing interfacial junctions, and phase-facet-morphology engineering, that have been adopted to improve TMO photocatalysts. By critically evaluating these strategies and providing a roadmap for future research directions, this article serves as a valuable resource for researchers, students, and professionals seeking to develop efficient energy materials for green energy solutions.

Surgical Management of Temporomandibular Joint Ankylosis with Mersilene Mesh Interpositional Arthroplasty: A Case Series Study.

Ankylosis of the temporomandibular joint (TMJ) is one of the most prevalent TMJ disorders in patients who have experienced trauma. Due to the high risk of recurrence, gap arthroplasty without interpositional material has been gradually discontinued as a treatment for TMJ ankylosis. After arthroplasty surgery, various interposition materials have been used to prevent a recurrence. Reporting on the effectiveness of TMJ bony ankylosis treatment using Mersilene mesh interpositional arthroplasty is the purpose of this study.This was a retrospective study carried out on five patients of TMJ ankylosis. All patients were treated through a Mersilene mesh interpositional arthroplasty procedure from January 2016 to April 2022 in Dr. Soetomo General Hospital and Universitas Airlangga General Hospital and evaluated 3 months postoperatively for the functional stability of TMJ. The result is preoperative mouth opening ranged between 0.7 and 13 mm. The patients achieved the interincisal opening between 27 and 40 mm postoperatively and had no complications for 3 months. In conclusion, Mersilene mesh interpositional arthroplasty is a very effective surgical treatment for TMJ bony ankylosis to achieve maximum mouth opening and avoid recurrences. The prevention of ankylosis recurrence necessitates thorough rehabilitation.

Insight into the role of reduced graphene oxide in enhancing photocatalytic hydrogen evolution in disordered carbon nitride.

Compared to crystalline carbon nitride, the performance of disordered carbon nitride (d-CN) as a hydrogen production photocatalyst is extremely poor. Owing to its disordered atomic orientation, it is prone to numerous defect states. These energy states are potential sites for trapping and recombination of photogenerated charge carriers. As a result, rapid recombination of photogenerated charge carriers places a fundamental photophysical challenge in charge separation and transport, which inhibits its photocatalytic activity. In the presence of reduced graphene oxide (rGO), d-CN shows enhanced photocatalytic production of hydrogen. However, photophysical insight into the tacit role of rGO is not well understood which limits the rational design of d-CN as a photocatalyst. Particularly, understanding of the early time-scale (in fs to ps) recombination mechanism and the charge transport kinetics has not yet been achieved. With the help of ultrafast transient absorption spectroscopy, femtosecond time-resolved photoluminescence spectroscopy and transient photocurrent measurements, this article deciphers the ultrafast dynamics of the separation and transport of photogenerated charge carriers in d-CN facilitated by rGO. It is found that rGO substantially suppresses the bimolecular and trap-assisted recombination and enables a faster separation of charge carriers. As a result, it increases the lifetime of the charge carriers to be transported to the surface catalytic sites, and therefore, augments the rate of hydrogen production almost by an order of magnitude. Our findings therefore offer a proof-of-concept for overcoming the trap-mediated recombination problems in disordered carbon nitride.

Hole utilization in solar hydrogen production.

In photochemical production of hydrogen from water, the hole-mediated oxidation reaction is the rate-determining step. A poor solar-to-hydrogen efficiency is usually related to a mismatch between the internal quantum efficiency of photon-induced hole generation and the apparent quantum yield of hydrogen. This waste of photogenerated holes is unwanted yet unavoidable. Although great progress has been made, we are still far away from the required level of dexterity to deal with the associated challenges of wasted holes and its consequential chemical effects that have placed one of the greatest bottlenecks in attaining high solar-to-hydrogen efficiency. A critical assessment of the hole and its related phenomena in solar hydrogen production would, therefore, pave the way moving forward. In this regard, we focus on the contextual and conceptual understanding of the dynamics and kinetics of photogenerated holes and its critical role in driving redox reactions, with the objective of guiding future research. The main reasons behind and consequences of unused holes are examined and different approaches to improve overall efficiency are outlined. We also highlight yet unsolved research questions related to holes in solar fuel production.

Chemotherapeutic resistance of head and neck squamous cell carcinoma is mediated by EpCAM induction driven by IL-6/p62 associated Nrf2-antioxidant pathway activation.

Overexpression of epithelial cell adhesion molecule (EpCAM) has been associated with chemotherapeutic resistance, leads to aggressive tumor behavior, and results in an adverse clinical outcome. The molecular mechanism by which EpCAM enrichment is linked to therapeutic resistance via Nrf2, a key regulator of antioxidant genes is unknown. We have investigated the link between EpCAM and the Nrf2 pathway in light of therapeutic resistance using head and neck squamous cell carcinoma (HNSCC) patient tumor samples and cell lines. We report that EpCAM was highly expressed in Nrf2-positive and HPV-negative HNSCC cells. In addition, cisplatin-resistant tumor cells consisted of a higher proportion of EpCAMhigh cells compared to the cisplatin sensitive counterpart. EpCAMhigh populations exhibited resistance to cisplatin, a higher efficiency in colony formation, sphere growth and invasion capacity, and demonstrated reduced reactive oxygen species (ROS) activity. Furthermore, Nrf2 expression was significantly higher in EpCAMhigh populations. Mechanistically, expression of Nrf2 and its target genes were most prominently observed in EpCAMhigh populations. Silencing of EpCAM expression resulted in the attenuation of expressions of Nrf2 and SOD1 concomitant with a reduction of Sox2 expression. On the other hand, silencing of Nrf2 expression rendered EpCAMhigh populations sensitive to cisplatin treatment accompanied by the inhibition of colony formation, sphere formation, and invasion efficiency and increased ROS activity. The molecular mechanistic link between EpCAM expression and activation of Nrf2 was found to be a concerted interaction of interleukin-6 (IL-6) and p62. Silencing of p62 expression in EpCAMhigh populations resulted in the attenuation of Nrf2 pathway activation suggesting that Nrf2 pathway activation promoted resistance to cisplatin in EpCAMhigh populations. We propose that therapeutic targeting the Nrf2-EpCAM axis might be an excellent approach to modulate stress resistance and thereby survival of HNSCC patients enriched in EpCAMhigh populations.

Widespread expression of Sonic hedgehog (Shh) and Nrf2 in patients treated with cisplatin predicts outcome in resected tumors and are potential therapeutic targets for HPV-negative head and neck cancer.

BACKGROUND: Sonic hedgehog (Shh) and Nrf2 play a critical role in chemotherapeutic resistance. These two genes have been found to be dysregulated in head and neck squamous cell carcinomas (HNSCC). The purpose of this study was to analyze the expression, function and clinical prognostic relationship of Shh and Nrf2 in HNSCC in the context of therapeutic resistance and cancer stem cells (CSCs). METHODS: We analyzed a cohort of patients with HNSCC to identify potential therapeutic biomarkers correlating with overall survival (OS) as well as disease-free survival (DFS) from our own data and validated these results using The Cancer Genome Atlas dataset. Expression of Shh and Nrf2 was knocked down by siRNA and cell growth, sphere growth and chemotherapeutic resistance were evaluated. RESULTS: Widespread abundant expression of Shh and Nrf2 proteins were associated with shorter OS and DFS. The combination of Shh and Nrf2 expression levels was found to be a significant predictor of patient DFS. The tumor stromal index was correlated with Shh expression and inversely associated with shorter OS and DFS. Inhibition of Shh by siRNA or cyclopamine resulted in the attenuation of resistant CSC self-renewal, invasion, clonogenic growth and re-sensitization to the chemotherapeutic agents. Concomitant upregulation of Shh and Nrf2 proved to be an independent predictor of poor OS and DFS in patients with HNSCC. CONCLUSIONS: These findings suggest that Shh and Nrf2 could serve as therapeutic targets as well as promising dual prognostic therapeutic biomarkers for HNSCC.

Carbon Nitride Transforms into a High Lithium Storage Capacity Nitrogen-Rich Carbon.

We describe here the metal-templated transformation of carbon nitride (C3N4) into nitrogen-containing carbons as anodes for Li-ion batteries (LIBs). Changing the template from the carbon- and nitrogen-immiscible Cu powder to the carbon- and nitrogen-miscible Fe powder yields different carbons; while Fe templating produces graphitized carbons of low (<10%) nitrogen content and moderate pore volume, Cu templating yields high defect-density carbons of high (32-24%) nitrogen content and larger pore volume. The Li+ storage capacity of the high nitrogen content and larger pore volume Cu-templated carbons exceeds that of the more graphitic Fe-templated carbons due to added contribution from Li+ insertion/extraction from pores and defects and to reversible faradaic Li+ reaction with nitrogen atoms. The Cu-templated carbon annealed at 750 °C delivers the highest specific capacity of 900 mAh g-1 at 0.1 A g-1 and 275 mAh g-1 at 20 A g-1, while also achieving a 96% capacity retention after 2000 cycles at 2 A g-1. The fabrication of higher mass loading electrodes (4.5 mg cm-2) provided a maximum areal capacity of 2.6 mAh cm-2 at 0.45 mA cm-2 (0.1 A g-1), comparable to the capacities of commercial LIB cells and favorable compared to other reported carbon materials.

Understanding Charge Transport in Carbon Nitride for Enhanced Photocatalytic Solar Fuel Production.

Photocatalytic solar fuel production, for example, production of hydrogen via water-splitting, is an effective means of chemical storage of solar energy and provides a potential option for achieving a zero-emissions energy system. Conveniently, hydrogen can be converted back to electricity either via fuel cells or through combustion in gas turbines, or it can be mixed in low concentrations with natural gas or biogas for combustion in existing power plants. The cornerstone of a practical solar fuel production process is a stable, efficient, and scalable photocatalyst (a semiconductor material that accommodates photon absorption, charge carrier generation and transport, and catalytic reactions). Therefore, the quest for suitable photocatalyst materials is an ongoing process. Recently, carbon nitride (CN) has attracted widespread interest as a metal-free, earth-abundant, and highly stable photocatalyst. However, the catalytic efficiency of CN is not satisfactory because of its poor charge transport attributes. There is a direct relation between the photocatalytic efficiency and charge transport because the basic principle of light-promoted overall photodecomposition of water into H2 and O2 molecules (or, generally speaking, photoredox reactions) relies on separation and subsequent transfer of excited-state electron-hole pairs to relative redox couples. However, the excited states last for a very short time, typically nanoseconds to microseconds in liquids, and unless they are separated within this time frame, the excited-state electron-hole pairs undergo recombination with release of the captured light energy as heat or photon emission. To utilize light in a form other than heat or emitted photons by avoiding the recombination of excited-state electron-hole pairs, charged excitons must be scavenged before the absorption of subsequent photons to sustain a multielectron photoredox reaction. Otherwise, the extraction of charges becomes more difficult. This imposes a potential efficiency-limiting factor. An enhancement in water to hydrogen conversion efficiency in CN therefore requires the use of precious-metal cocatalysts (e.g., Pt) and sacrificial electron donor/acceptors to facilitate multielectron/multiproton transfers to overcome the high kinetic barriers. The use of Pt and sacrificial agents is not consistent with the notion of low-cost and sustainable hydrogen production from water. CN must overcome this dependence to stand out as a truly scalable photocatalyst. To make progress, the foremost requirement is to attain an in-depth understanding of the fundamental charge transport phenomena needed for the rational design of CN-based photocatalysts. In this Account, therefore, our aim is to provide a synopsis of current understanding and progress regarding charge-transport-related phenomena (e.g., recombination, trapping, transfer of charge carriers, etc.) and to discuss the effects of charge transport in enhancing the apparent quantum yield of hydrogen production in CN. This understanding is necessary to broaden the scope of CN for other catalytic applications, for example, efficient CO2 reduction to methanol or methane, fixation of nitrogen to ammonia, and use as an active material in solar cells. We also identify research gaps and issues to be addressed for a more clear elucidation of charge-transport-related phenomena in CN. Thus, this Account may inspire new research opportunities for tuning the extrinsic/intrinsic photophysicochemical properties of CN by rational design to attain the most favorable properties for improved catalytic efficiency.

Tuning the Intrinsic Properties of Carbon Nitride for High Quantum Yield Photocatalytic Hydrogen Production.

The low quantum yield of photocatalytic hydrogen production in carbon nitride (CN) has been improved upon via the modulation of both the extrinsic and intrinsic properties of the material. Although the modification of extrinsic properties has been widely investigated in the past, recently there has been growing interest in the alteration of intrinsic properties. Refining the intrinsic properties of CN provides flexibility in controlling the charge transport and selectivity in photoredox reactions, and therefore makes available a pathway toward superior photocatalytic performance. An analysis of recent progress in tuning the intrinsic photophysical properties of CN facilitates an assessment of the goals, achievements, and gaps. This article is intended to serve this purpose. Therefore, selected techniques and mechanisms of the tuning of intrinsic properties of CN are critically discussed here. This article concludes with a recommendation of the issues that need to be considered for the further enhancement in the quantum efficiency of CN photocatalysts.