Advances on carbon nanomaterials and their applications in medical diagnosis and drug delivery.

Carbon nanomaterials are indispensable due to their unique properties of high electrical conductivity, mechanical strength and thermal stability, which makes them important nanomaterials in biomedical applications and waste management. Limitations of conventional nanomaterials, such as limited surface area, difficulty in fine tuning electrical or thermal properties and poor dispersibility, calls for the development of advanced nanomaterials to overcome such limitations. Commonly, carbon nanomaterials were synthesized by chemical vapor deposition (CVD), laser ablation or arc discharge methods. The advancement in these techniques yielded monodispersed carbon nanotubes (CNTs) and allows p-type and n-type doping to enhance its electrical and catalytic activities. The functionalized CNTs showed exceptional mechanical, electrical and thermal conductivity (3500-5000 W/mK) properties. On the other hand, carbon quantum dots (CQDs) exhibit strong photoluminescence properties with high quantum yield. Carbon nanohorns are another fascinating type of nanomaterial that exhibit a unique structure with high surface area and excellent adsorption properties. These carbon nanomaterials could improve waste management by adsorbing pollutants from water and soil, enabling precise environmental monitoring, while enhancing wastewater treatment and drug delivery systems. Herein, we have discussed the potentials of all these carbon nanomaterials in the context of innovative waste management solutions, fostering cleaner environments and healthier ecosystems for diverse biomedical applications such as biosensing, drug delivery, and environmental monitoring.

Selective fluoride sensing by a novel series of lanthanide-based one-dimensional coordination polymers through intramolecular proton transfer.

A novel series of one-dimensional coordination polymers (CPs) is achieved via a facile one-pot synthesis strategy employing the nitrate salts of trivalent lanthanides, a pentadentate chelating ligand, and triphenylphosphine oxide at a controlled stoichiometry under ambient conditions. All the CPs are characterized comprehensively using spectroscopic, X-ray crystallographic and magnetometric studies. The CPs are found to be thermally stable up to a significantly high temperature and resistant to water for an indefinite time. They are photoactive and exhibit selective fluoride ion (F-) sensing with excellent efficiency both colorimetrically and fluorimetrically in the solid-state as well as in solution. The presence of F- concomitantly sensitizes the photoluminescence enhancement and visual decolourization of the CPs in solution owing to the ground-state intra-molecular proton transfer. The photophysical response of the CPs to F- in solution was found to be instantaneous (<30 s). The sensitivity of detection is observed to be significantly high over a wide range of F- concentrations, covering the beneficial and detrimental domains of F- concentrations in drinking water. The limit of detection (LoD) under ambient conditions was found to be in the micromolar (µM) range-the best being 0.22 µM found using UV-vis spectrometry and 7.5 µM using fluorimetry. In comparison, the USEPA standard cut-off for the upper limit of F- concentration in drinking water is 211 µM, and the LoD of measuring F- concentration using the USEPA standard method using a fluoride-selective electrode is 26.3 µM. The CPs display markedly high selectivity toward F- with negligible-to-no interference from the commonly abundant ions (Cl-, Br-, I-, CH3CO2-, CO32-, SO42-, HPO42-, NH4+, Na+, K+, Mg2+, and Ca2+) in terms of UV-vis spectral change. Moreover, they also exhibit solid-state IR-spectrometric sensitivity towards F- under ambient conditions.

Autonomous Atmospheric Water Harvesting over a Wide RH Range Enabled by Super Hygroscopic Composite Aerogels.

Sorption-based atmospheric water harvesting (SAWH) offers a sustainable strategy to address the global freshwater shortage. However, obtaining sorbents with excellent performance over a wide relative humidity (RH) range and devices with fully autonomous water production remains challenging. Herein, magnesium chloride (MgCl2) is innovatively converted into super hygroscopic magnesium complexes(MC), which can effectively solve the problems of salt deliquescence and agglomeration. The MC are then integrated with photothermal aerogels composed of sodium alginate and carbon nanotubes (SA/CNTs) to form composite aerogels, which showed high water uptake over a wide RH range, reaching 5.43 and 0.27 kg kg-1 at 95% and 20% RH, respectively. The hierarchical porous structure enables the as-prepared SA/CNTs/MC to exhibit rapid absorption/desorption kinetics with 12 cycles per day at 70% RH, equivalent to a water yield of 10.0 L kg-1 day-1. To further realize continuous and practical freshwater production, a fully solar-driven autonomous atmospheric water generator is designed and constructed with two SA/CNTs/MC-based absorption layers, which can alternately conduct the water absorption/desorption process without any other energy consumption. The design provides a promising approach to achieving autonomous, high-performance, and scalable SAWH.

A 7-year review of clinical characteristics, predisposing factors and outcomes of post-keratoplasty infectious keratitis: the Nottingham infectious keratitis study.

Background/objectives: Post-keratoplasty infectious keratitis (PKIK) is a unique sight-threatening clinical entity which often poses significant therapeutic challenges. This study aimed to examine the clinical presentation, risk factors, management, and clinical outcomes of PKIK. Methods: This was a retrospective study of all patients who presented to the Queen's Medical Centre, Nottingham, with PKIK between September 2015 and August 2022 (a 7-year period). Relevant data on types of keratoplasty, clinical presentations, causative microorganisms, management, and outcome were analyzed. Results: Forty-nine PKIK cases, including four cases of interface infectious keratitis, were identified during the study period. The most common graft indications for PKP, DALK and EK were failed grafts (9, 37.5%), keratoconus (6, 54.5%) and Fuchs endothelial corneal dystrophy (FECD; 8, 57.1%), respectively. Staphylococcus spp. were the most commonly identified organisms (15, 50.0%). Bullous keratopathy (18, 36.7%), ocular surface disease (18, 36.7%), and broken/loose sutures (15, 30.6%) were the most common risk factors. Concurrent use of topical steroids was identified in 25 (51.0%) cases. Of 31 functioning grafts at presentation, 12 (38.7%) grafts failed at final follow-up with 15 (48.4%) patients retaining a CDVA of ≥1.0 logMAR. The overall estimated 5-year survival rate post-PKIK was 55.9% (95% CI, 35.9%-75.9%), with DALK having the highest survival rate [63.6% (95% CI, 28.9%-98.3%)], followed by EK [57.1% (95% CI, 20.4%-93.8%)] and PKP [52.7% (95% CI, 25.1%-80.3%)], though no statistical difference was observed (p=0.48). Conclusions: PKIK represents an important cause of IK and graft failure. Bullous keratopathy, OSD and suture-related complications are the commonest risk factors, highlighting the potential benefit of prophylactic topical antibiotics (for unhealthy ocular surface) and early suture removal (where possible) in reducing the risk of PKIK. Graft survival may be higher in lamellar keratoplasty following PKIK but larger studies are required to elucidate this observation.

An Asymmetric Hygroscopic Structure for Moisture-Driven Hygro-Ionic Electricity Generation and Storage.

The interactions between moisture and materials give rise to the possibility of moisture-driven energy generation (MEG). Current MEG materials and devices only establish this interaction during water sorption in specific configurations, and conversion is eventually ceased by saturated water uptake. This paper reports an asymmetric hygroscopic structure (AHS) that simultaneously achieves energy harvesting and storage from moisture absorption. The AHS is constructed by the asymmetric deposition of a hygroscopic ionic hydrogel over a layer of functionalized carbon. Water absorbed from the air creates wet-dry asymmetry across the AHS and hence an in-plane electric field. The asymmetry can be perpetually maintained even after saturated water absorption. The absorbed water triggers the spontaneous development of an electrical double layer (EDL) over the carbon surface, which is termed a hygro-ionic process, accounting for the capacitive properties of the AHS. A peak power density of 70 µW cm-3  was realized after geometry optimization. The AHS shows the ability to be recharged either by itself owing to a self-regeneration effect or via external electrical means, which allows it to serve as an energy storage device. In addition to insights into moisture-material interaction, AHSs further shows potential for electronics powering in assembled devices.

Plasmonic protein electricity generator.

Interest in acquiring green energy from sunlight is driving research into the incorporation of biological photosynthetic materials into biohybrid devices. A potential way to enhance solar energy conversion by photosynthetic proteins is to couple them to plasmonic nanomaterials to enhance absorption of incident radiation. In this work, a variety of plasmonic nanoparticles were used to boost the photocurrent output of a Protein Electricity Generator (PEG). Mixing gold nanoparticles (NPs) of five different architectures into the photoprotein/electrolyte contents of the cell was found to increase device performance, the most effective being ∼120 nm diameter star-shaped clusters that caused a ∼six-fold increase in photocurrent at the optimum dopant level. In addition, high-resolution electrohydrodynamic printing was used to create parallel line and square lattice patterns of silver nanoparticle ink on the tungsten rear electrode of the cells. Patterns with a 700 nm spacing between lines boosted photocurrents by up to three-fold and the effects of the gold and silver nanoparticles were additive, such that the ideal combination produced a ∼19-fold increase in photocurrent and device efficiency. We attribute the elevated performance to plasmonic enhancement of absorbance and scattering effects that increase the path length for photons in the device. Use of rear electrodes with silver nanoparticle lines and grids at 1100 nm spacing did not increase photocurrents, highlighting the importance of precision printing of nanostructures for the enhancement of device performance.

Solar-Driven Gas-Phase Moisture to Hydrogen with Zero Bias.

Band structure engineering offers a perfect route to tune the transport properties of electrons and holes independently, especially in semiconductors for water splitting. Here, we explore the possibility of achieving a bias-free single-step solar to chemical energy conversion using gas-phase moisture as the reactant while generating hydrogen as the reaction product. A metal-based superhygroscopic hydrogel scavenges moisture from the ambient environment and serves as the water source. The FeOOH/BiVO4 heterojunction works as the photoanode wherein the interface allows the transport of electrons to the outer layer, resulting in an upward band bending. Concomitantly, the negative charges will accumulate on the Cu2O surface in the FeOOH/Cu2O photocathode, inducing a downward band bending. With the use of the hydrogel, photoanode, and photocathode, a device for directly splitting the moisture absorbed from the ambient air is realized, generating a photocurrent of 0.75 mA cm-2 under the one-sun intensity of cool daylight without any additional bias. The solar-cell-assisted device can split 6 mg of moisture in 10 h, and the hydrogel can absorb more than 30 mg of moisture in the same period.

Shadow enhanced self-charging power system for wave and solar energy harvesting from the ocean.

Hybrid energy-harvesting systems that capture both wave and solar energy from the oceans using triboelectric nanogenerators and photovoltaic cells are promising renewable energy solutions. However, ubiquitous shadows cast from moving objects in these systems are undesirable as they degrade the performance of the photovoltaic cells. Here we report a shadow-tribo-effect nanogenerator that hybrids tribo-effect and shadow-effect together to overcome this issue. Several fiber-supercapacitors are integrated with the shadow-tribo-effect nanogenerator to form a self-charging power system. To capture and store wave/solar energy from oceans, an energy ball based on the self-charging power system is demonstrated. By harnessing the shadow-effect, i.e. the shadow of the moving object in the energy ball, the charging time shortens to 253.3 s to charge the fiber-supercapacitors to the same voltage (0.3 V) as using pure tribo-effect. This cost-effective method to harvest and store the wave/solar energy from the oceans in this work is expected to inspire next-generation large-scale blue energy harvesting.

Unsaturated and Benzannulated N-Heterocyclic Carbene Complexes of Titanium and Hafnium: Impact on Catalysts Structure and Performance in Copolymerization of Cyclohexene Oxide with CO2.

Tridentate, bis-phenolate N-heterocyclic carbenes (NHCs) are among the ligands giving the most selective and active group 4-based catalysts for the copolymerization of cyclohexene oxide (CHO) with CO2. In particular, ligands based on imidazolidin-2-ylidene (saturated NHC) moieties have given catalysts which exclusively form polycarbonate in moderate-to-high yields even under low CO2 pressure and at low copolymerization temperatures. Here, to evaluate the influence of the NHC moiety on the molecular structure of the catalyst and its performance in copolymerization, we extend this chemistry by synthesizing and characterizing titanium complexes bearing tridentate bis-phenolate imidazol-2-ylidene (unsaturated NHC) and benzimidazol-2-ylidene (benzannulated NHC) ligands. The electronic properties of the ligands and the nature of their bonds to titanium are studied using density functional theory (DFT) and natural bond orbital (NBO) analysis. The metal-NHC bond distances and bond strengths are governed by ligand-to-metal σ- and π-donation, whereas back-donation directly from the metal to the NHC ligand seems to be less important. The NHC π-acceptor orbitals are still involved in bonding, as they interact with THF and isopropoxide oxygen lone-pair donor orbitals. The new complexes are, when combined with [PPN]Cl co-catalyst, selective in polycarbonate formation. The highest activity, albeit lower than that of the previously reported Ti catalysts based on saturated NHC, was obtained with the benzannulated NHC-Ti catalyst. Attempts to synthesize unsaturated and benzannulated NHC analogues based on Hf invariably led, as in earlier work with Zr, to a mixture of products that include zwitterionic and homoleptic complexes. However, the benzannulated NHC-Hf complexes were obtained as the major products, allowing for isolation. Although these complexes selectively form polycarbonate, their catalytic performance is inferior to that of analogues based on saturated NHC.

Carbon Nanotube Reinforced Strong Carbon Matrix Composites.

As an excellent candidate for lightweight structural materials and nonmetal electrical conductors, carbon nanotube reinforced carbon matrix (CNT/C) composites have potential use in technologies employed in aerospace, military, and defense endeavors, where the combinations of light weight, high strength, and excellent conductivity are required. Both polymer infiltration pyrolysis (PIP) and chemical vapor infiltration (CVI) methods have been widely studied for CNT/C composite fabrications with diverse focuses and various modifications. Progress has been reported to optimize the performance of CNT/C composites from broad aspects, including matrix densification, CNT alignment, microstructure control, and interface engineering, etc. Recent approaches, such as using resistance heating for PIP or CVI, contribute to the development of CNT/C composites. To deliver a timely and up-to-date overview of CNT/C composites, we have reviewed the most recent trends in fabrication processes, summarized the mechanical reinforcement mechanism, and discussed the electrical and thermal properties, as well as relevant case studies for high-temperature applications. Conclusions and perspectives addressing future routes for performance optimization are also presented. Hence, this review serves as a rundown of recent advances in CNT/C composites and will be a valuable resource to aid future developments in this field.

Self-powered all weather sensory systems powered by Rhodobacter sphaeroides protein solar cells.

Natural photosynthetic proteins can convert solar energy into electrical energy with close to 100% quantum efficiency, and there is increasing interest in their use for sustainable photoelectrochemical devices. The primary processes of photosynthesis remain operational and efficient down to extremely low temperatures, and natural photosystems exhibit a variety of self-healing mechanisms. Herein we demonstrate the use of an amphiphilic triblock copolymer, Pluronic F127, to fabricate a self-healing photosynthetic protein photoelectrochemical cell that operates optimally at sub-zero temperatures. A concentration of 30% (w/w) Pluronic F127 depressed the freezing point of an electrolyte comprising 50 mM ubiquinone-0 in aqueous buffer such that optimal device solar energy conversion was seen at -12 °C rather than at room temperature. Fabrication of the protein photoelectrochemical cells with flexible electrodes enabled the demonstration of self-healing of damage caused by repeated mechanical deformation. Multiple bending cycles caused a marked deterioration of the photocurrent response to around a third of initial levels due to damage to the gel phase of the electrolyte, but this could be restored to ~95% by simply cooling and rewarming the device. This self-recoverability of the electrolyte extended the operational life of the protein cell through a process that increased its photoelectrochemical output during the repair. Utility of the cells as components of a touch sensor operational across a wide temperature range, including freezing conditions, is demonstrated.

Hydro-Assisted Self-Regenerating Brominated N-Alkylated Thiophene Diketopyrrolopyrrole Dye Nanofibers-A Sustainable Synthesis Route for Renewable Air Filter Materials.

With rising global concerns over the alarming levels of particulate pollution, a sustainable air quality management is the need of the hour. Air filtration research has gained momentum in recent years. However, the research perspective is still blinkered toward formulating new fiber systems for the energy-intensive electrospinning process to fabricate high quality factor air filters. A holistic approach on sustainable air filtration models is still lacking. The air filter model presented in this work uses a simple process involving water-induced self-organization and self-regeneration of nanofibers, and an easy recycling route after the filter life that not only facilitates reuse of the microfibrous scaffold holding the nanofibers but also allows renewal of nanofibers. Three generations of air filters are fabricated and tested, all having high particulate matter (PM)-adsorbing tendency, high filtration efficiency (>95%), and high Young's modulus (≈5 GPa). The renewable air filters offer a sustainable alternative to the present cost-intensive electrospun air filters.

Portable Trilayer Photothermal Structure for Hybrid Energy Harvesting and Synergic Water Purification.

Many exciting developments have unfolded on the recently emerged research topic of solar-driven interfacial evaporation, which is a promising technology for water purification. However, the sole heat source, i.e., solar energy, has put a limit on the maximum achievable evaporation rate. Therefore, to boost the evaporation beyond the limit, we here in this work have put forth a new photothermal system with a trilayered structure (TLS) that is capable of simultaneously harvesting hybrid energy in addition to solar energy for enhanced evaporation. A carbon-based material with broad-band light absorption that can be facilely synthesized through dehydration effect is also reported. Demonstrations of TLS evaporator by recovering the free thermal energy from sources like ground surficial heat and waste heat from laboratory facility and building walls together with solar radiation have been carried out. A remarkable synergic evaporation rate exceeding 2.4 kg m-2 h-1 is achieved, and moreover, the hybrid heating makes evaporation independent of solar intermittency. Besides, a TLS integrated hybrid water-purification bottle with outstanding portability is further demonstrated, which is expected to be of great significance to the development of mobile water purification and safe water security in the future.