Oxygen Generation Rate Research Articles

Synthesis and photophysical properties of symmetrical tetraaryltetranaphtho[2,3]porphyrin derivatives

The discovery of new photosensitizers with strong absorption near-infrared region, obvious fluorescence emission, and high reactive oxygen generation ability has attracted great attention as optical agents in life science and material industry. Herein a series of meso-tetraaryltetranaphtho[2,3]porphyrins (Ar 4TNPs) with different substitutions were designed and synthesized. They had strong absorptions at ∼730 nm and fluorescence emission at ∼760 nm after excitation with ∼503 nm light. All compounds possessed excellent reactive oxygen species (ROS) generation ability. The singlet oxygen generation rate of compound 10m (meso-5,10,15,20-tetra[2-(2-hydroxyethoxy)ethylbenzoate]tetrana-phthoporphyrin) is 0.1898 s−1 with a Φ△ value of 0.73, which is significantly higher than that of verteporfin. Therefore, Ar4TNPs have great potential as an effective optical material, bio-tracker, and photodynamic drug candidate.

Computational modelling of the therapeutic outputs of photodynamic therapy on spheroid-on-chip models

Photodynamic therapy (PDT) is a medical radio chemotherapeutic method that uses light, photosensitizing agents, and oxygen to produce cytotoxic compounds, which eliminate malignant cells. Recently, Microfluidic systems have been used to analyse photosensitizers (PSs) due to their potential to replicate in vivo environments. While prior studies have established a strong correlation between reacted singlet oxygen concentration and PDT-induced cellular death, the effects that the ambient fluid flow might have on the concentration of oxygen and PS have been disregarded in many, which limits the reliability of the results. Herein, we coupled the transport of oxygen and PS throughout the ambient medium and within the spheroidal multicellular aggregate to initially study the profiles of oxygen and PS concentration alongside PDT-induced cellular death throughout the spheroid before and after radiation. The attained results indicate that the PDT-induced cellular death initiates on the surface of the spheroids and subsequently spreads to the neighbouring regions, which is in great accordance with experimental results. Afterward, the effects that drug-light interval (DLI), fluence rate, PS composition, microchannel height, and inlet flow rate have on the therapeutic outcomes are studied. The findings show that adequate DLI is critical to ensure uniform distribution of PS throughout the medium, and a value of 5 h was found to be sufficient. The composition of PS is critical, as ALA-PpIX induces earlier cell death but accelerates oxygen consumption, especially in the outer layers, depriving the inner layers of oxygen necessary for PDT, which in turn disrupts and prolongs the exposure time compared to mTHPC and Photofrin. Despite the fluence rate directly influencing the singlet oxygen generation rate, increasing the fluence rate by 189 mW/cm2 would not significantly benefit us. Microwell height and inlet flow rate involve competing phenomena—increasing height or decreasing flow reduces oxygen supply and increases PS “washout” and its concentration.

Post-synthetic modification of near-infrared absorbing cyclodextrin-encapsulated cyanine dyes for controlling absorption wavelength, stability, and singlet oxygen generation

Abstract In this study, near-infrared absorbing rotaxane-type cyanine dyes exhibit high tolerance to various chemical reactions, which is attributed to the encapsulation effect of their cyclic molecules. As a result, rotaxane dyes can be post-modified on the host α-cyclodextrin or guest cyanine skeleton to adjust their solubility, absorption wavelength, stability, and singlet oxygen generation ability. The guest modification product obtained via the Heck reaction demonstrates a red shift of its absorption wavelength owing to the extended conjugation system. Moreover, the products of host modification through the methylation and benzylation of all cyclodextrin hydroxyl groups not only become lipophilic and show extended absorption, but also exhibit higher photooxidation tolerance, lower singlet oxygen generation rate, and increased singlet oxygen tolerance, indicating their potential applicability as highly durable dyes. Furthermore, the outstanding singlet oxygen tolerance of these dyes enables their use in long-life singlet oxygen generators, in which the total amount of singlet oxygen increases. This work demonstrates that an intrinsically unstable near-infrared cyanine dye can be used as a synthetic intermediate by stabilizing it via α-cyclodextrin encapsulation, allowing the post-modification of various properties of cyanine dyes toward the higher-order near-infrared-absorbing materials with complex functionalities and diverse utilities.

Stability analysis for the phytoplankton-zooplankton model with depletion of dissolved oxygen and strong Allee effects

The photosynthetic activity of phytoplankton in the seas is responsible for an estimated 50–80 % of the world's oxygen generation. Both phytoplankton and zooplankton require some of this synthesized oxygen for cellular respiration. This study aims to better understand how the oxygen-phytoplankton dynamics are altered due to the Allee effect in phytoplankton development, particularly when considering the time-dependent oxygen generation rate. The dynamic analysis of the model is dedicated to finding the possible equilibrium points. The analysis reveals that three equilibrium points can be obtained. The stability study demonstrates that one of the equilibrium points is always stable. The remaining equilibrium points are stable under specific conditions. We also identify bifurcations originating from these equilibrium points, including transcritical, pitchfork, and Hopf bifurcation. We derive conditions for stable limit cycles (supercritical Hopf bifurcation) and, in some cases, establish the non-existence of solutions. Numerical simulations are performed to validate our theoretical findings. Furthermore, it is noted that the Allee threshold for the phytoplankton population (k0) significantly influences the overall dynamics of the system. When k0≤0.001, the population of plankton is at risk of extinction. On the other hand, when 0.001<k0≤0.01, the population of zooplankton is at risk of extinction. When 0.01<k0≤2, the solution reaches a stable condition of coexistence. Conversely, when k0≥2.1, the solution exhibits periodic attractor behaviour.

Photocatalytic Oxygen Evolution under Visible Light Mediated by Molecular Heterostructures.

Due to their structural and property tunability, semiconductive conjugated polymers (CPs) have emerged as promising candidates for photocatalytic water splitting. Compared with inorganic materials, the photocatalytic performance of mono-component polymers was limited by the fast recombination of photoexcited charge carriers, and they always needed to catch up to expectations. To this end, researchers established molecular donor-acceptor heterostructures, which could notably promote oxygen production efficiency due to their more effective charge carrier separation. In this work, easy Schiff base reactions between side-chain -CHO groups and terminal -NH2 groups were used to introduce benzene and perylene diimide (PDI) into the molecular heterostructure to serve as electron donors (D) and electron acceptors (A). In particular, for the first time, we employed the molecular heterostructures of CPs to promote photocatalytic O2 production. One prepared molecular heterostructure was demonstrated to improve oxygen generation rate (up to 0.53 mmol g-1 h-1) through visible light-driven water splitting. Interestingly, based on the photoelectric properties, a stepwise two-electron/two-electron pathway constituted the photocatalytic mechanism for oxygen production with the molecular heterostructure. These results provide insights into designing and fabricating high-performance molecular heterostructures for photocatalytic oxygen production.

Biofilm bioactivity affects nitrogen metabolism in a push-flow microalgae-bacteria biofilm reactor during aeration-free greywater treatment

Non-aeration microalgae-bacteria biofilm has attracted increasing interest for its application in low cost wastewater treatment. However, it is unclear the quantified biofilm characteristics dynamics and how biofilm bioactivity affects performance and nitrogen metabolisms during wastewater treatment. In this work, a push-flow microalgae-bacteria biofilm reactor (PF-MBBfR) was developed for aeration-free greywater treatment. Comparatively, organic loading at 1.27 ± 0.10 kg COD/(m3⋅d) gave the highest biofilm concentration, density, specific oxygen generation (SOGR) and consumption rates (SOCR), and pollutants removal rates. Contributed to low residual linear alkylbenzene sulfonates and bioactivity, reactor downstream showed low bacteria and protein concentrations and SOCR (12.8 mg O2/g TSS·h), but high microalgae, carbohydrate, biofilm density, SOGR (49.4 mg O2/g TSS·h) and pollutants removal rates. Dissolved organic nitrogen (DON) showed higher molecular weight, CHONS and fraction with 4 atoms of N in reactor upstream. Most of nitrogen was fixed to newly synthesized biomass during assimilation process by related functional enzymes, minor contributed to denitrification due to low N2 emission. High nitrogen assimilation by microalgae showed high SOGR, which favored efficient multiple pollutants removal and reduced DON emission. Our findings favor the practical application of PF-MBBfR based on biofilm bioactivity, enhancing efficiency and reducing DON emission for low- energy-input wastewater treatment.

Molecular Engineering Design of Enhanced Donor-Acceptor Therapeutic Reagent for Efficient Image-Guided Photodynamic Therapy.

The greatest barrier to the further development and clinical application of tumor image-guided PDT, is the inconsistency between the fluorescence intensity and the singlet oxygen generation yield of the photosensitizer under light excitation. Here, a novel donor-acceptor (D-A) system wa s designed from the point of molecular selection by wrapping a classical porphyrin molecule (H2 TPP) as an acceptor into conjugated polymer (ADS254BE) as a donor through fluorescence resonance energy transfer mechanism, which exhibits bright red emission centered at 650nm (Quantum yield, 0.12), relatively large Stoke shift of 276nm, enhanced singlet oxygen generation rate of 0.73, and excellent photostability. The investigations on distribution and killing effect of nanomaterials in cancer cells revealed that ADS254BE/H2 TPP NPs can accumulate in the cytoplasm for imaging while simultaneously producing a large amount of singlet oxygen to remarkably kill cancer cells, which could be used for real-time image-guided PDT. In the xenograft tumor model, real-time imaging and long-term tracing in tumor tissue with ADS254BE/H2 TPP NPs disclosed that the growth of lung cancer in mice could be effectively inhibited during in-situ imaging. From the standpoint of molecular engineering design, this work provides a feasible strategy for novel D-A systems to improve the development of image-guided PDT. This article is protected by copyright. All rights reserved.

Photosensitizing Metasurface Empowered by Enhanced Magnetic Field of Toroidal Dipole Resonance.

Photochemical reaction exploiting an excited triplet state (T1 ) of a molecule requires two steps for the excitation, i.e., electronic transition from the ground (S0 ) to singlet excited (S1 ) states and intersystem crossing to the T1 state. A dielectric metasurface coupled with photosensitizer that enables energy efficient photochemical reaction via the enhanced S0 →T1 magnetic dipole transition is developed. In the direct S0 →T1 transition, the photon energy of several hundreds of meV is saved compared to the conventional S0 → S1 →T1 transition. To maximize the magnetic field intensity on the surface, a silicon (Si) nanodisk array metasurface with toroidal dipole resonances is designed. The surface of the metasurface is functionalized with ruthenium (Ru(II)) complexes that work as a photosensitizer for singlet oxygen generation. In the coupled system, the rate of the direct S0 →T1 transition of Ru(II) complexes is 41-fold enhanced at the toroidal dipole resonance of a Si nanodisk array. The enhancement of a singlet oxygen generation rate is observed when the toroidal dipole resonance of a Si nanodisk array is matched with the direct S0 →T1 transition wavelength of Ru(II) complexes.

Natural versus synthetic curcuminoids as photosensitizers: Photobleaching and antimicrobial photodynamic therapy evaluation

Antimicrobial photodynamic therapy (aPDT) has been studied as an alternative to combat bacterial resistance to the commonly used antibiotics. aPDT requires the use of a photosensitizer and curcumin is one of the more promising, though the usage of natural curcumin can be inconsistent in certain biomedical uses due to differences in soil condition and turmeric age, besides a large quantity of the plant is necessary to obtain useful amounts of the actual molecule. As such, a synthetic analogue is preferred as it is pure, and its components are better characterized. The present work studied photophysical differences in both natural and synthetic curcumin using photobleaching experiments and searched for whether differences existed in aPDT studies against Staphylococcus aureus. The results showed a faster O2 consumption and a singlet oxygen's generation rate lower by the synthetic curcumin, in comparison with the natural derivative. However, no statistical difference was observed when inactivating S. aureus and these results were following a concentration-based pattern. Thus, the use of synthetic curcumin is indicated, as it can be obtained in controlled amounts and with less environmental impact. Although there are small changes in a photophysical context comparing natural versus synthetic curcumins, we did not observe statistical differences in the photoinactivation of S.aureus bacteria, and reproducibility in biomedical contexts is better achieved with the synthetic analogue.

Photocatalytic overall water splitting hydrogen production over ZnCdS by spatially-separated WP and Co3O4 cocatalysts

Loading suitable oxidation and reduction cocatalysts on sulfide semiconductor photocatalysts for H 2 and O 2 production reaction still remain a great challenge. Herein, we present a simple physical mixing strategy to load reduction cocatalyst WP and oxidation cocatalyst Co 3 O 4 co-modification ZnCdS (WP–Co/ZCS) with excellent photocatalytic water splitting activity. The co-modification of the double auxiliary catalysts can efficiently accelerate the separation of photocarriers, enhance the reaction kinetics and significantly advance the photocatalytic activity. The maximum hydrogen evolution rate of 21.44 mmol g -1 h -1 is attained over 10% WP-Co/ZCS photocatalyst, which is about 6.5 folds higher than bare ZnCdS, and a high photostability is also obtained. Meanwhile, a notable quantum efficiency of 27.6% at 420 nm and solar-hydrogen conversion efficiency (STH) of 1.57% are achieved, which is significantly surpassing many reported ZnCdS-based photocatalysts. Remarkably, an efficient and stable photocatalytic overall water splitting activity are achieved with hydrogen and oxygen generation rates of 61 μmol g -1 h -1 and 32.5 μmol g -1 h -1 for 10% WP-Co/ZCS, respectively. This work provides a new idea for designing oxidation and reduction dual-catalysts on ZnCdS nanoparticles to advance photocatalytic hydrogen generation performance and achieve pure water splitting. An efficient WP/Co 3 O 4 /ZnCdS dual cocatalysts photocatalytic system was constructed for overall water splitting. The highest photocatalytic H 2 production rate of 21.44 mmol g -1 h -1 is achieved over 10% WP-Co/ZnCdS with a high AQE of 27.6% at 420 nm. And the solar-hydrogen conversion efficiency (STH) is up to 1.57% for 10% WP-Co/ZnCdS. Remarkably, an efficient and stable photocatalytic overall water splitting activity are achieved with hydrogen and oxygen generation rates of 61 μmol g -1 h -1 and 32.5 μmol g -1 h -1 for 10% WP-Co/ZCS, respectively. • An efficient WP/Co 3 O 4 /ZnCdS dual cocatalysts photocatalytic system was constructed. • Photocatalytic H 2 production rate of 21.44 mmol g -1 h -1 is achieved over 10% WP-Co/ZnCdS with a high AQE of 27.6% at 420 nm. • The solar-hydrogen conversion efficiency (STH) is 1.57% for 10% WP-Co/ZnCdS. • Matching of HER/OER via WP and Co 3 O 4 can actualize the overall water splitting. • Photocatalytic overall water splitting for H 2 /O 2 generation rates are 61/32.5 μmol g -1 h -1 over 10% WP-Co/ZCS.

Carbon capture and biocatalytic oxygen production of photosystem II from thylakoids and microalgae on nanobiomaterials

Enhanced carbon capture and oxygen production via water splitting was observed by controlling the plasmon-induced resonance energy transfer (PIRET) for photosystem II (PSII) in thylakoid extracts and spirulina assembled on gold nanoparticle (AuNP) dimer arrays. The two types of vertical (V) and horizontal (H) AuNP dimer arrays were uniformly inserted inside pore diameter-controlled templates. Based on the theoretical calculations, the longitudinal mode of the H AuNP dimer array was found to be sensitive to the nanogap distances between the two AuNPs in resonance with the absorption at P680 of the PSII. The longitudinal modes that interacted with P680 of PSII increased from the V to the H conformer. The optical properties from the H AuNP dimer array caused overlapping absorbance and photoluminescence with PSII, and the H AuNP dimer arrays exhibited a significant increase in carbon capture and oxygen generation rates in comparison with those of the bare PSII protein complex under light irradiation via the controlled PIRET process.

Performance evaluation and multi-objective optimization of an innovative solar-assisted multigeneration energy storage system for freshwater/O2/H2 generation

A novel multigeneration energy system encompassing a two-stage water purification unit, high-temperature solid oxide electrolysis cell (SOEC), heliostat solar field, and power generation cycles including organic and two-stage steam Rankine cycles is introduced in this study. The two-stage desalination system comprises humidification, dehumidification, and reverse osmosis units. A thermoelectric generator is also utilized to convert dissipated heat into electricity. The proposed system is comprehensively analyzed from energy, exergy, economic, and sustainability standpoints. The effect of design parameters such as heliostat concentration ratio, view factor, desalination mass flow ratio, SOEC operating temperature, and current density on the hydrogen, oxygen and freshwater generation rate, sustainability index, total cost rate, and overall performance of the energy system are discussed. Further, multi-objective optimization based on non-dominated sorting genetic algorithm (NSGA-II) is implemented to identify the optimal operating state of the system. Comparative assessment of the system in the actual condition in the Middle East region showed that the plant has higher performance in June compared to December. Also, optimization revealed that by choosing C = 988, P7 = 1500 kPa, P8 = 300 kPa, MFD = 2.5 and Tcell = 1250 K, the highest obtainable exergy efficiency and minimum total cost rate in the optimal operating state would be 11.32 % and 78.18 $/h, respectively.

The biological activities of 5,15-diaryl-10,20-dihalogeno porphyrins for photodynamic therapy.

Esophageal cancer is the most common gastrointestinal tumor and is difficult to be eradicated with conventional treatment. Porphyrin-based photosensitizers (PSs) mediated photodynamic therapy (PDT) could kill tumor cells with less damage to normal cells. As the most widely used porphyrin-based photosensitizer in clinics, Photofrin II has excellent anti-tumor effect. However, it has some disadvantages such as weak absorption at near infrared region, the complexity of components and prolonged skin photosensitivity. Here series novel 5,15-diaryl-10,20-dihalogeno porphyrin derivatives were afforded and evaluated to develop more effective and safer photosensitizers for tumor therapy. The photophysical properties and singlet oxygen generation rates of 5,15-diaryl-10,20-dihalogeno porphyrins (I1-6, II1-4) were tested. The cytotoxicity of I1-6 and II1-4 were measured by MTT assay. The pathway of cell death was studied by flow cytometry. In vivo photodynamic efficacy of I3 and II2-4 in Eca-109 tumor-bearing BABL/c nude mice were measured and histopathological analysis were examined. 5,15-Diaryl-10,20-dihalogeno porphyrins I1-6 and II1-4 were synthesized. The longest absorption wavelength of these halogenated porphyrins (λmax = 660nm) displayed a red shift around 30nm compared to the unhalogenated porphyrins PS1 (λmax = 630nm). The singlet oxygen generation rates of I1-6 and II1-4 were significantly higher than PS1 and HMME. All PSs mediated PDT showed obvious cytotoxic effect against Eca-109 cells compared to HMME in vitro and in vivo. Among these PSs, II4 exhibited appropriate absorption in the phototherapeutic window, higher 1O2 generation rate (k = 0.0061s-1), the strongest phototoxicity (IC50 = 0.4μM), lower dark toxicity, high generation of intracellular ROS in Eca-109 cells and excellent photodynamic anti-tumor efficacy in vivo. Besides, cell necrosis was induced by compound II4 mediated PDT. All new compounds have obvious photodynamic anti-esophageal cancer effects. Among them, the photosensitizer II4 showed excellent efficacy in vitro and in vivo, which has the potential to become a photodynamic anti-tumor drug.

Probing multifunctional azure B conjugated gold nanoparticles with serum protein binding properties for trimodal photothermal, photodynamic, and chemo therapy: Biophysical and photophysical investigations

Multimodal or combination therapy has been considered as a powerful approach for treatment of complex diseases like cancer. The fascinating physicochemical and optoelectronic properties of gold nanoparticles make them potential candidate for cancer therapeutic and diagnostic applications. Herein, we design a multifunctional nanosystem by conjugating a photosensitizer, Azure B (AB) with citrate reduced gold nanoparticles (CI-Au NPs) through non-covalent interactions. The conjugation of AB with CI-Au NPs was confirmed through UV–Visible absorption spectroscopy and Fourier Transform Infra-red (FT-IR) spectroscopy. The morphology, size, and charge of the prepared nano-conjugates (AB@CI-Au NPs) were determined by transmission electron microscopy (TEM), Dynamic light scattering (DLS), and zeta potential measurements. The proficiency of AB@CI-Au NPs for cancer photo-therapies was demonstrated by evaluating their potential for photothermal heating and singlet oxygen generation in solution upon Visible laser (635 nm, 500 mW/cm2) irradiation. The AB@CI-Au NPs display superior heating efficiency than CI-Au NPs alone or free AB, and offer better photostability as well as singlet oxygen generation rate compared to free photosensitizer. The interaction of AB@CI-Au NPs with Calf thymus DNA (Ct-DNA) and transport protein Bovine Serum Albumin (BSA) were studied using various biophysical techniques including Circular dichroism, UV–Visible and fluorescence spectroscopic studies. AB@CI-Au NPs show intercalative binding with Ct-DNA by inducing local perturbations in double helical structure and hence can exert chemotherapeutic action by targeting DNA. AB@CI-Au NPs also display moderate binding with BSA without any adverse effect on BSA structure, which is desirable for significant biodistribution and pharmacokinetics of AB@CI-Au NPs. Also, in vitro cytotoxicity of the AB@CI-Au NPs with and without laser irradiation (635 nm, 500 mW/cm2) was demonstrated using the hepatocellular carcinoma (HepG2) cell lines. Our findings through photophysical and biophysical studies strongly recommend the exploitation of AB@CI-Au NPs nanoconjugates as a multifunctional probe for trimodal anticancer therapy.

Cu2-xO@TiO2-y Z-scheme heterojunctions for sonodynamic-chemodynamic combined tumor eradication

It is urgent to develop high-efficacy nanosonosensitizers with enhanced charge transfer and tumor microenvironment regulation capabilities for sonodynamic therapy (SDT). A novel heterojunction nanosonosensitizer Cu2-xO@TiO2-y was designed from core-shell oxide semiconductors with narrow bandgaps (2.1–2.2 eV) using positively charged Cu2-xO nanodots and negatively charged TiO2-y nanosheets as components. The ultrasound (US) triggered singlet oxygen (1O2) and hydroxyl radicals (•OH) generation rates notably increased compared with single components, which can be ascribed to a direct Z-scheme charge transfer mechanism that greatly improved spatial separation dynamics of US-generated electron-hole pairs. Moreover, the Cu+-Cu2+ redox cycle not only catalyzed the Fenton like reaction to generate •OH from tumor endogenous H2O2 but also depleted endogenous glutathione (GSH). Human osteosarcoma models showed complete tumor eradication by single drug injection and single US irradiation. This work highlights non-stoichiometric oxide heterostructures with the Z-scheme charge transfer mechanism for chemodynamic-sonodynamic combined therapy.

The improvement of biocompatibility by incorporating porphyrins into carbon dots with photodynamic effects and pH sensitivities.

Photodynamic therapy (PDT) is a promising new treatment for cancer; however, the hydrophobic interactions and poor solubility in water of photosensitizers limit the use in clinic. Nanoparticles especially carbon dots have attracted the attention of the world's scientists because of their unique properties such as good solubility and biocompatibility. In this paper, we integrated carbon dots with different porphyrins to improve the properties of porphyrins and evaluated their efficacy as PDT drugs. The spectroscopic characteristics of porphyrins nano-conjugates were studied. Singlet oxygen generation rate and the light- and dark-induced toxicity of the conjugates were studied. Our results showed that the covalent interaction between CDs and porphyrins has improved the biocompatibility. The synthesized conjugates also inherit the pH sensitivity of the carbon dots, while the conjugation also decreases the hemolysis ratio making them a promising candidate for PDT. The incorporation of carbon dots into porphyrins improved their biocompatibility by reducing toxicity.

Nitrogen and phosphorus removal efficiency and algae viability in an immobilized algae and bacteria symbiosis system with pink luminescent filler

Abstract In this study, an immobilized algae and bacteria symbiotic biofilm reactor (ABSBR) with pink luminescent filler (PLF) was constructed. The effects of PLF addition in the construction of an algae and bacteria symbiotic biofilm system on the nitrogen and phosphorus removal efficiencies and algae viability were evaluated. Our results showed that for influent TN and TP concentrations of 40 ± 5 and 5 ± 0.8 mg/L, respectively, the pollutant removal rates (PRRs) of TN and TP by the ABSBR can reach up to 74.74% and 88.36%, respectively. The chlorophyll-a (chl-a) concentration on the PLF reaches approximately 5,500 μg/L with a specific oxygen generation rate (SOGR) of 65.48 μmolO2 mg−1Chl-a h−1. These results indicate that the adding PLF into algae and bacteria symbiosis systems can effectively improve the nitrogen and phosphorus removal efficiencies of the sewage as well as increase biomass and viability of the algae in the system.

Development and performance assessment of new solar and fuel cell-powered oxygen generators and ventilators for COVID-19 patients

In this study, a new solar-based fuel cell-powered oxygenation and ventilation system is presented for COVID-19 patients. Solar energy is utilized to operate the developed system through photovoltaic panels. The method of water splitting is utilized to generate the required oxygen through the operation of a proton exchange membrane water electrolyser. Moreover, the hydrogen produced during water splitting is utilized as fuel to operate the fuel cell system during low solar availability or the absence of solar irradiation. Transient simulations and thermodynamic analyses of the developed system are performed by accounting for the changes in solar radiation intensities during the year. The daily oxygen generation is found to vary between 170.4 kg/day and 614.2 kg/day during the year. Furthermore, the amount of daily hydrogen production varies between 21.3 kg/day and 76.8 kg/day. The peak oxygen generation rate attains a value of 18.6 g/s. Moreover, the water electrolysis subsystem entails daily exergy destruction in the range of 139.9–529.7 kWh. The maximum efficiencies of the developed system are found to be 14.3% energetically and 13.4% exergetically.

Amorphous Fe(OH)3 Passivating CeO2 Nanorods: A Noble-Metal-Free Photocatalyst for Water Oxidation.

Noble-metal-free composites with good photocatalytic property are of great interest. Here, CeO2 nanorods composites loaded with amorphous Fe(OH)3 cocatalyst were designed and prepared via a secondary water bath at 100 °C. The as-synthesized CeO2 /amorphous Fe(OH)3 composites exhibited superior light photocatalytic activities compared to pure CeO2 , especially the sample with a loading time of 60 min. The photocatalytic oxygen generation rate could reach to 357.2 μmol h-1 g-1 , and the average apparent quantum yield (AQY) was 24.67 %, which was a 5.5-fold increase compared to the CeO2 sample. The improvement of photocatalytic performance could be ascribed to three main reasons: First, loading the amorphous Fe(OH)3 enlarged the specific surface area and passivated the surface of the pristine CeO2 . Second, the amorphous Fe(OH)3 ,which acted as a cocatalyst, provided many active sites, and reduced the reaction activation energy. Thirdly, the maximum interface with intimate contact between CeO2 and amorphous Fe(OH)3 cocatalyst accelerated the photogenerated charge separation efficiency and thus improved the photocatalytic performance of CeO2 in photocatalytic water oxidation.

Studying the "Rigid-Flexible" Properties of Polymeric Micelle Core-Forming Segments with a Hydrophobic Phthalocyanine Probe Using NMR and UV Spectroscopy.

The aim of the performed studies was to thoroughly examine the internal structure of self-assembled nanocarriers (i.e., polymeric micelles—PMs) by means of a hydrophobic phthalocyanine probe in order to identify the crucial features that are required to enhance the photoactive probe stability and reactivity. PMs of hydrophilic poly(ethylene glycol) and hydrophobic poly(ε-caprolactone) (PCL) or poly(d,l-lactide) (PDLLA) were fabricated and loaded with tetra tert-butyl zinc(II) phthalocyanine (ZnPc-t-but4), a multifunctional spectroscopic probe with a profound ability to generate singlet oxygen upon irradiation. The presence of subdomains, comprising “rigid” and “flexible” regions, in the studied block copolymers’ micelles as well as their interactions with the probe molecules, were assessed by various high-resolution NMR measurements [e.g., through-space magnetic interactions by the 1D NOE effect, pulsed field gradient spin-echo, and spin–lattice relaxation time (T1) techniques]. The studies of the impact of the core-type microenvironment on the ZnPc-t-but4 photochemical performance also included photobleaching and reactive oxygen species measurements. ZnPc-t-but4 molecules were found to exhibit spatial proximity effects with both (PCL and PDLLA) hydrophobic polymer chains and interact with both subdomains, which are characterized by different rigidities. It was deduced that the interfaces between particular subdomains constitute an optimal host space for probe molecules, especially in the context of photochemical stability, photoactivity (i.e., for significant enhancement of singlet oxygen generation rates), and aggregation prevention. The present contribution proves that the combination of an appropriate probe, high-resolution NMR techniques, and UV–vis spectroscopy enables one to gain complex information about the subtle structure of PMs essential for their application as nanocarriers for photoactive compounds, for example, in photodynamic therapy, nanotheranostics, combination therapy, or photocatalysis, where the micelles constitute the optimal microenvironment for the desired photoreactions.