Oxygen Atoms Research Articles

Efficient UV-Vis-NIR Responsive CO2 Reduction Photocatalyst with Black Pinecone-Shaped Carbon Nitride Loaded with Lanthanum Oxide.

Photothermal catalysis combines the advantages of photocatalysis and thermal activation, which provides a new research angle for CO2 catalytic reduction. In this study, Black carbon nitride with a three-dimensional (3D) pinecone-shaped structure (BPCN) was prepared by a simple solvothermal method using melamine as a precursor without the aid of a template. Lanthanum oxide doping on the BPCN catalysts (BPCN-La) was achieved by ultrasonic impregnation. This unique pinecone-shaped structure consists of self-assembled and interlaced carbon nitride rods (by SEM). The lanthanum element was distributed on the surface of the CN framework in the form of La2O3 (by XPS). The chemical structures of the samples were characterized by solid-state 13C nuclear magnetic resonance (13C NMR) and elaborated by density functional theory (DFT) analysis. This black carbon nitride expanded the light absorption band edge into the near-infrared (NIR) (300-1400 nm, by UV-vis absorption spectra) and had excellent photothermal conversion activity. La atom doping can significantly boost photogenerated electron excitation (by photocurrent test) and promote carrier separation and transfer (by PL). Upon incorporation of La atoms into BPCN, the highest occupied molecular orbital (HOMO) orbital is more concentrated on the oxygen atoms of La2O3. BPCN-La considerably narrowed the band gap width, exhibited an exceptional photothermal effect, and provided a large surface area, which significantly enhanced the photocatalytic reduction of CO2 reactions. The yields of CO reached 58.2 and 104.9 μmol·h-1·g-1 for BPCN and BPCN-La, respectively, with GCN as the control (6.3 μmol·h-1·g-1). Theoretical reaction pathways and selectivity for the photoreduction of CO2 on BPCN and BPCN-La were studied by DFT simulation. This work provides a new vision for the design of photothermal synergistic without extra-thermal input and full spectral response photocatalysts with high efficiency.

The molecular structure, electronic properties, and decomposition mechanism of FOX-7 under external electric field were calculated based on density functional theory.

Based on the density functional theory (DFT), we analyzed the changes of the FOX-7 molecule under external electric field (EEF) from multiple perspectives, including molecular structure, electronic structure, decomposition mechanism, frontier molecular orbitals (FMOs), and density of states (DOS). The results revealed that as the intensity of the positive EEF increased, the detonation performance of the FOX-7 molecule was significantly enhanced, while its thermal stability was also improved. This discovery challenges the traditional concept that explosives are inherently dangerous under external electric fields and provides new insights for research in related fields. To further explore the impact of EEF on the thermal stability of FOX-7, we conducted a thorough analysis of the mechanism by which EEF affects the decomposition process. Our findings indicate that applying a positive EEF significantly increases the energy required to overcome intramolecular hydrogen transfer and C-NO2 bond rupture, while having a relatively minor effect on the nitro isomerization process. This observation further demonstrates that the appropriate application of a positive EEF can enhance the detonation performance of FOX-7 without compromising its thermal stability. Further research revealed that as the intensity of the positive EEF increased, the electronegativity of the nitro group gradually enhanced, leading to an increase in the electronegativity of the oxygen atoms within it. This made the oxygen atoms more prone to participating in chemical reactions. This phenomenon also explains why the energy barrier required for nitro isomerization in FOX-7 gradually decreases as the intensity of the positive EEF increases. Based on the density functional theory (DFT), the structural optimizations were performed both under applied EEF and without EEF at the B3LYP/6-311G (d, p) level. All optimized results were converged and exhibited no imaginary frequencies. Based on the optimized structures, single-point energy calculations were further conducted at the B3LYP/def2-TZVPP level. Subsequently, analyses of molecular structure, electronic structure, decomposition mechanism, frontier molecular orbitals, and density of states were carried out.

Using phosphorus doped hydrogenated silicon oxycarbide film as a window layer on the light entrance side of silicon heterojunction solar cells: The role of phase separation on electron transport

The phosphorus doped hydrogenated nanocrystalline silicon oxycarbide (n-nc-SiCO:H) layer can be used as a window layer on the light incident side of silicon heterojunction solar cells (HJT). The chemical composition, structural organization and properties of the n-nc-SiCO:H layer deposited from plasma enhanced chemical vapor deposition (PECVD) method can be easily manipulated via radio frequency power density tuned. Phase separation is observed in the n-nc-SiCO:H layer in which nanoscale silicon crystallites were embedded in amorphous silicon oxycarbide matrix. The optical properties of the n-nc-SiCO:H layer are depended on oxygen and carbon atoms incorporation ratio. The conductivity of the n-nc-SiCO:H layer is dominated by activated phosphorus concentration and the phase separation. The activated phosphorus atoms which play an important role on electron transportation are distributed in both crystalline silicon phase and amorphous silicon phase. Both activated phosphorus concentration and band gap value for oxygen rich amorphous silicon oxycarbide layer are determined by incorporation ratio of O atoms. The interplay effects of optical and electrical properties of the n-nc-SiCO:H layers on HJT cells electric performance variation are revealed out in this report. An average efficiency (across ∼120 cells) of 26.3 % was achieved in cells with optimized power density for the n-nc-SiCO:H layer. The results demonstrate that phase separation in the n-nc-SiCO:H layer plays a critical role on electron transportation.

Internal Electron-Donation Allocation Design for Intrinsic Solubilization of Lithium Nitrate in Ester Electrolyte for Stable Lithium Metal Batteries.

Lithium metal batteries (LMBs) have become a hot topic in the research of next-generation advanced battery technology due to their high specific energy. However, the high reaction activity between lithium metal and electrolyte is considered one of the key bottlenecks limiting large-scale applications of LMBs. As a classic electrolyte additive, LiNO3 significantly improves the stability of lithium metal in ether-based electrolytes. However, its solubility in carbonate-based electrolytes widely used in lithium-ion batteries is extremely low, and its protective effect on lithium metal is limited, which has become a key obstacle to the commercial application of lithium metal batteries. Here, we enhanced the local negative charge density of carbonyl oxygen atoms in carbonate molecules by introducing electron donors, making it easier for them to coordinate with Li+, thereby weakening the interaction between Li+ and NO3-, and significantly increasing the solubility of LiNO3 in ester electrolytes. The modified ester solvent promotes the derivatization and decomposition of salt anions, leading to the formation of a dense SEI layer rich in LiF and LiNxOy. This significantly improves the stability of lithium metal in ester-based electrolytes. The assembled Li||Li symmetric battery shows excellent cycling performance of over 4000 hours.

P-Orbital Ferromagnetism Arising from Unconventional O- Ionic State in a New Semiconductor Sr2AlO4 with Insufficiently Bonded Oxygen.

Oxygen in solids usually exists in an O2- ionic state. As a result, it loses its magnetic nature of a single atom, wherein two unpaired electrons exist in its outer 2p orbitals. Here, it is shown that an unconventional stable ionic state of O- is realized in a new semiconductor material Sr2AlO4, leading to an intrinsic p-orbital ferromagnetism stable until ≈900K. Experimental and theoretical investigations have clarified that one-fourth of the oxygen atoms in Sr2AlO4 are insufficiently bonded in the crystal structure, resulting in a unique O--state and p-orbital ferromagnetism. To date, the O- state is reported to exist only in non-equilibrium conditions, and p-orbital magnetism is only suggested in impurity bands with small ferromagnetic moments. The present work provides a new route for creating ferromagnetism in semiconductors and exploring new p-orbital physics and chemistry. In addition, the material shows elastic-mechanoluminescence that may enable unprecedented mechano-photonic-spintronics.

Enhancement of the quality of mc-Si ingot grown by vacuum directional solidification furnace with growth rate increase reducing the cost of the wafer for PV application: Carbon and oxygen analysis

In this paper, we propose a numerical model to investigate the dissolution of oxygen atoms from the porous silica crucible, SiO gas formation, back diffusion of CO gas and segregation of carbon and oxygen during the growth of multi-crystalline silicon (mc-Si) by vacuum directional solidification (VDS) at different growth rates (3, 6 and 9 mm/h) by silt valve opening rate. The dissolution of oxygen decreases during the rapid growth of ingot because the reaction between the molten silicon and the porous silica crucible is constrained. This limitation on oxygen dissolution from the porous silica crucible further diminishes chemical reaction inside the VDS furnace. Consequently, the segregation pattern of the carbon and oxygen is affected at higher growth rate. During the VDS mc-Si growth, a growth rate of 9mm/h yields better quality of the VDS grown mc-Si ingots compared to other growth rates, this rate reduces SiC precipitation and SiO2 cluster formation due to lower concentration of carbon and oxygen. The obtained carbon concentration minimizes the wire saw defects. Based on these numerical results (9 mm/h), we have implemented experimental work. Prepared samples are analyzed using FTIR spectra and minority carrier lifetime measurements. The effect of oxygen concentration in the samples is analyzed in the minority carrier lifetime measurements. The oxygen and carbon concentrations are calculated by FTIR spectra and their results are compared with the numerical simulation.

Graphene Oxide-Enhanced Nucleation and Growth of Calcium-Silicate-Hydrate Gel at Nanoscale: A Molecular Dynamics Study.

Graphene oxide (GO) enhances the performance of cement-based materials by optimizing the microstructure of calcium-silicate-hydrate (C-S-H). However, the influence of GO on the nucleation and growth of C-S-H gel at nanoscale is unexplored. This study investigates this mechanism by molecular dynamics simulation at nano scale. Results show that GO can reduce the activation energy during the polymerization reaction of silicon oxide tetrahedra during the reaction process, and can increase the content of polymer Q3 and Q4. The influence of GO with epoxy (-O-), hydroxyl (-OH) and carboxyl (-COOH) groups on the radial distribution function (RDF), mean square displacement (MSD), and atomic spatial distribution of monomers are studied. Results show that GO-OH exhibits excellent performance, with the highest number of bridging oxygen atoms (about 0.6), the lowest Q0 monomer content (just 26.8%), the highest RDF (27.18), and the highest MSD (calcium and silicon content around 20,000 Å2). This paper elucidates the nucleation and growth mechanism of C-S-H influenced by GO to develop high performance cement.

Kinetic Studies on MB Adsorption by Graphene like Material from Coconut Shell Charcoal

Coconut shell (CS) activated carbon is widely used for water purification, but its adsorption capacity is inferior compare to graphene oxide (GO). GO has oxygen functional groups so it can effectively bind pollutants like methylene blue (MB). In this study we synthesized graphene-like material from CS charcoal using the modified Hummers method by varying its oxidation times. The XRD decomposition results for H-CS3.2 show a structural composition similar to GO material. The diffraction peak at 10.7° (3.04%) falls within GO's characteristic range of 8°-11°, supported by a Raman ID/IG ratio of 0.95. In contrast, H-CS3.1 material does not exhibit GO's structural composition, with a diffraction peak at 13.9° (1.09%). An increasing of oxidation time, enhanced adsorption capacity in the equilibrium state of H-CS3.2 (22.368 mg/g) surpassing H-CS3.1 (17.079 mg/g). The heightened adsorption was linked to an increased O/C ratio or higher % of atomic oxygen (0.04 for H-CS3.1 and 0.17 for H-CS3.2). The pseudo second-order Ho (PSO) adsorption kinetic model demonstrated the adsorption mechanism, with active sites (oxygen functional groups) such as carbonyl (C = O) and epoxy (C – O) at basal plane carbon. Steric hindrance caused by hydroxyl functional groups (C – OH) led to a reduction in π-π interactions and decreased adsorption ability of the H-CS3.1 material. Desorption of H-CS3.1 material was influenced by MB detachment through interface diffusion.

Mn-Fe Dual-Metal Assemblages on Carbon-Coated Al2O3 Spheres for Catalytic Ozonation Oxidation: Structure, Performance, and Reaction Mechanism.

Catalysts with high catalytic activity and low production cost are important for industrial application of heterogeneous catalytic ozonation (HCO). In this study, we designed a carbon-coated aluminum oxide carrier (C-Al2O3) and reinforced it with Mn-Fe bimetal assemblages to prepare a high-performance catalyst Mn-Fe/C-Al2O3. The results showed that the carbon embedding significantly improved the abundance of surface oxygen functional groups, conductivity, and adsorption capacity of γ-Al2O3, while preserving its exceptional mechanical strength as a carrier. The prepared Mn-Fe/C-Al2O3 catalyst exhibited satisfactory catalytic ozonation activity and stability in the degradation of p-nitrophenol (PNP). Electron paramagnetic resonance (EPR) and quenching experiments reveal that radical ( ⋅ OH and ⋅ O2 ⋅ ) and nonradical oxidation (1O2) dominated the PNP degradation process. Theoretical calculations corroborated that the anchored atomic Fe and Mn sites regulated the local electronic structure of the catalyst. This modulation effectively promoted the activation of O3 molecules, resulting in the generation of atomic oxygen species (AOS) and reactive oxygen species (ROS). The economic analysis on Mn-Fe/C-Al2O3 revealed that it was a cost-competitive catalyst for HCO. This study not only deepens the understanding on the reaction mechanism of HCO with transition metal/carbon composite catalysts, also provides a high-performance and cost-competitive ozone catalyst for prospective application.

The cadmium oxidotellurates(IV) Cd5(TeO3)4(NO3)2 and Cd4Te5O14

Monoclinic single crystals of Cd5(TeO3)4(NO3)2 (space group P21/c), pentacadmium tetrakis[oxidotellurate(IV)] dinitrate, and of Cd4Te5O14 (space group C2/c), tetracadmium pentaoxidotellurate(IV), were obtained under the same hydrothermal conditions. Whereas the crystal structure of Cd5(TeO3)4(NO3)2 is distinctively layered, that of Cd4Te5O14 exhibits a tri-periodic framework. In Cd5(TeO3)4(NO3)2, the three CdII atoms have coordination numbers (CN) of 7, 6 and 6. The two types of [CdO6] and the [CdO7] polyhedra [bond lengths range from 2.179 (3) to 2.658 (2) Å] share corners and edges, resulting in layers extending parallel to (100). Both TeIV atoms are coordinated by three oxygen atoms in a trigonal–pyramidal shape. The oxygen atoms of the isolated [TeO3] groups [bond lengths range from 1.847 (3) to 1.886 (3) Å] all are part of the cadmium–oxygen layer. The electron lone pairs ψ of the TeIV atoms are directed away from the layer on both sides. The available interlayer space is co-occupied by the nitrate group, which is directly connected with two of its O atoms to the layer whereas the third O atom is solely bonded to the N atom and points towards the adjacent layer. In Cd4Te5O14, all three unique CdII atoms are coordinated by six oxygen atoms, considering Cd—O distances from 2.235 (2) to 2.539 (2) Å. By edge- and corner-sharing, the distorted [CdO6] polyhedra form an open framework that is partially filled with three different stereochemically active TeIV atoms. All of them exhibit a CN of 4, with Te—O bonds in a range from 1.859 (2) to 2.476 (2) Å. The corresponding [TeO4] units are linked to each other by corner- and edge-sharing, forming infinite helical 1 ∞[Te10O28] chains extending parallel to [203]. The connectivity in the chains can be described as (...–⋄–⋄=⋄–⋄–⋄–⋄–⋄=⋄–⋄–⋄–...) n where ‘⋄’ denotes a [TeO4] unit, ‘–’ a linkage via corners and ‘=’ a linkage via edges. Such a structural motif is unprecedented in the crystal chemistry of oxidotellurate(IV) compounds.

Crystal structure and Hirshfeld surface analysis of bis(benzoylacetonato)(ethanol)dioxidouranium(VI)

A new uranium metal–organic complex salt, [U(C10H9O2)2O2(C2H6O)], with benzoyl acetone, namely, bis(benzoylacetonato)(ethanol)dioxidouranium(VI), was synthesized. The compound has monoclinic P21/n symmetry. The geometry of the seven-coordinate U atom is pentagonal bipyramidal, with the uranyl oxygen atoms in apical positions. In the complex, the ligands bind to the metal through oxygen atoms. Additional weak O—H...O contacts between the cations and anions consolidate the three-dimensional arrangement of the structure. On the Hirshfeld surface, the largest contributions come from the short contacts such as van der Waals forces, including H...H, O...H and C...H. Interactions including C...C and O...C contacts were also observed; however, their contribution to the overall cohesion of the crystal structure is minor. A packing analysis was performed to check the strength of the crystal packing.

Intrinsic Chemical Drivers of Organic Aerosol Volatility: From Experimental Insights to Model Predictions

AbstractAccurately predicting the volatilities of molecules in aerosols is challenging but crucial for understanding the atmospheric effects of aerosols. We used negative and positive ion electrospray ionization Fourier‐transform ion cyclotron resonance mass spectrometry (FT‐ICR MS) to identify differences in the molecular compositions of gas and particle phase samples from urban atmosphere. We aimed to identify intrinsic chemical parameters that determine and predict the organic aerosol volatility. We found higher average molecular weights, carbon mass percentages, and double bond equivalents (DBE) but lower average O/C ratios and oxygen mass percentages in the particle phase than the gas phase. We identified DBE, which display a significant negative correlation with volatility, as a key parameter. We proposed to improve the previous model for predicting organic aerosol volatility by incorporating DBE as a new variant; and the result showed that this subsequently improved the accuracy of the model, particularly for compounds with minimal or no heteroatoms (0–2) such as hydrocarbons (CH). The revised model offers insights into the contributions of DBE, carbon, nitrogen, oxygen, and sulfur atoms to the volatilities of diverse organic molecules in aerosols and could be applied to improve our understanding of the phase distributions of volatile organic compounds in the ambient air.

Aqueous Electrocatalytic Hydrogenation Depolymerization of Lignin β-O-4 Linkage via Selective Caryl-O(C) Bond Cleavage: The Regulation of Adsorption.

The cleavage of the benzene-oxygen (Caryl-O(C)) bond of the lignin β-O-4 linkage is expected to relieve condensation of the degradation product and improve the product value. Nevertheless, the electrochemical breaking of the Caryl-O(C) bond has not been achieved yet due to the high dissociation energy (∼409 kJ mol-1) and the easy over-reduction of aromatic compounds. Here, we report an aqueous electrochemical reduction strategy for breaking Caryl-O(C) bonds via the regulation of molecular adsorption. The density functional theory (DFT) calculations and quartz crystal microbalance (QCM) measurements reveal that the residual Cu(I) in the CuO electrocatalyst enhances the adsorption of the 2-phenoxy-1-phenylethyl alcohol (PPE) by the Caryl-O(C) bond and lowers the energy barrier of the protons attacking the oxygen atom in the β-O-4 linkage. Thus, compared to the Cu electrocatalyst (with a hydroquinone yield of 47.4% and a benzyl alcohol yield of 24.8%), the CuO nanorod exhibits a much higher yield of hydroquinone (95.3%) and benzyl alcohol (88.6%) at a potential of -0.4 V vs reversible hydrogen electrode (RHE) in an undivided cell. Moreover, the reaction pathway and the cleavage of the Caryl-O(C) bond are identified through a combination of in situ synchrotron-radiation Fourier transformed infrared spectroscopy (SR-FTIR) and DFT calculations. This effective method is utilized for poplar lignin electrolysis, yielding 10.9 wt % of guaiacylglycerol, with an outstanding selectivity of >63.0%. This work provides an efficient and mild method of cleavage of Caryl-O(C) bonds in lignin valorization.

Transport properties of high Mach number hypersonic air plasmas

Abstract The collisional and transport properties of hypersonic plasmas have been simulated by an air plasma chemistry model, which includes collisions with electrons, ions and neutral species, elastic scattering, vibrational relaxation and a transport model. Species and thermal fluxes at the surface of the vehicle have been investigated as a function of post-shock gas temperature and species sticking coefficient for a fixed altitude of 50 km. At temperatures below about 5,000 K, the leading species are vibrationally excited nitrogen molecules, while at higher temperatures the molecular nitrogen and atomic oxygen dominate. Large fluxes of oxygen atoms have been observed in the simulations, on the order of 10^20 cm^-2s^ -1, which may lead to high rates of surface oxidation. Another subject of this study is temperature equilibration. For electrons, equilibration takes tens of microseconds, while the vibrational temperature equilibration time vary widely; from a few microseconds to hundreds of microseconds, depending on the gas temperature. Finally, the adiabatic parameter  was calculated for post-shock gas temperatures 5,000 K and 10,000 K and total gas density 1.2×10^17 cm^(-3). For post-shock gas temperature 5,000 K, only a slight reduction of gamma from the ideal gas value of ~1.4 is observed, while for 10,000 K it drops to ~1.26, which has a considerable impact on plasma properties. It was further established that the vibrational kinetics plays a leading role. While a single excited vibrational level of the N2 molecule captures the salient properties of the plasma, a detailed vibration kinetics is required for high-fidelity simulations.

Synthesis, Spectroscopy and Biological Studies of Copper and Silver Complexes Derived from 2-Substituted Amino Propanoic Acid

Synthesis of copper and silver complexes were prepared from novel Schiff base ligand. These synthesized ligand and their metal complexes were characterized by elemental analysis, FT-IR, 1H NMR, UV-Vis and Mass spectrometry. The coordination of amino nitrogen, phenolic oxygen, and carboxylato oxygen atoms is shown by the infrared spectra.The Schiff bases and its complexes were screened for their in vitro antibacterial and antifungal studies against the bacteria Pseudomonas Aeruginosa (PA, Gram -ve), Bacillus Cirroflagellosus (BC, Gram +ve), Penicillium Notatium (PN) and Aspergillus Niger (AN) strains. The results of the antibacterial investigation show that the copper and silver complexes possess more potent bactericide and fungicide properties than the ligand.

Systematic study on the hydrogen abstraction reactions from oxygenated compounds by H and HO2

AbstractTo extend the rule‐based approach for hydrogen abstraction reactions from oxygenated compounds, a systematic investigation was performed to examine the reactivity of gas‐phase hydrogen abstraction reactions from alkyl groups (methyl and ethyl groups) bound to oxygen atoms in five types of oxygenated compounds (alcohols, ethers, formate esters, acetate esters, and carbonate esters) by H atoms and HO2 radicals comprehensively considering rotational conformers. Quantum chemical calculations were conducted at the CBS‐QB3 level for stationary points. Rate constants were determined employing conventional transition state theory (TST). For hydrogen abstraction reactions by H, the rotational conformer distribution partition function was employed to approximate partition functions, owing to the similarity in vibrational energy‐level structures among conformers. In hydrogen abstraction reactions by HO2, the vibrational structures of transition‐state (TS) conformers varied significantly due to the hydrogen bonding, leading to an inappropriate evaluation of rate constants when using the lowest‐energy conformer as a representative. Therefore, the rate constants were calculated by the multi‐structural TST. It was revealed that the differences in functional groups containing O atoms mainly affect the bond dissociation energies of the C–H bonds and the activation energies of hydrogen abstraction reactions only when the C atoms are adjacent to the O atoms. Additionally, it was found that hydrogen bonds formed in the TSs show minor effect on rate parameters for the overall rate constants, apart from the reduction of the pre‐exponential factors for the H‐abstraction reactions from the methylene position of ethyl groups. The comparison with the rate constants from previous studies showed reasonable results, indicating that the rate constants in this study, which thoroughly consider rotational conformers, can be the current best estimates.

Coordination Modes of Ortho-Substituted Benzoates Towards Divalent Copper Centres in the Presence of Diimines

The coordination modes of several ortho-substituted benzoates towards the copper(II) centre are investigated. The coordination environment of the metal ion includes nitrogen atoms from 2,2′-bipyridine (bipy) or 1,10-phenanthroline (phen) and occasionally oxygen atoms from coordinated water, ethanol molecules, or nitrate ions. The compounds are investigated by a variety of spectroscopic methods and by single-crystal X-ray diffraction. Although the reaction scheme involved equimolar amounts of the reactants, cationic dinuclear compounds with a metal/benzoate/diimine ratio of 2:3:2 have been realized, cationic in nature regardless of the counter anion used. Furthermore, the carboxylate moieties display a range of twisting relative to the orientation of the benzene ring to which they are attached.

Kinetic Modeling of Brilliant Blue Discoloration by Ozonation

This paper presents the results of investigations on the kinetic modeling of Brilliant Blue FCF (BB) discoloration reactions in aqueous solutions with different ozone concentrations and pH conditions. Kinetic studies involve knowledge of the structure and properties of dye and ozone, as well as of the experimental conditions. In general, scientists admit that the predominant oxidation pathway is direct (by free oxygen atoms) or indirect (by free hydroxyl radicals); this will depend on influencing factors such as the physicochemical properties of the dye, the pH of the aqueous solution, ozone concentration, reaction time, and the contact mode with/without stirring. In this experimental research, two pathways were chosen following CBB = f(t)—1. a constant dye concentration and different ozone concentrations, in the concentration range of 100–250 mg/L, in three pH media (acidic, neutral, and basic), with and without stirring; 2. a constant concentration of ozone and different dyes in the concentration range of 2.5–10 mg/L, under the conditions of point 1. With the obtained experimental data, the curves CBB = f(t) were drawn and processed according to the integral method of classical kinetics, based on first- and second-order equations. Unfortunately, this simple procedure did not give any results for the pH values studied. The rate constants were negative, and/or the reaction order depended on the initial conditions. Due to its structure, the BB dye has several chromophore groups, and thus multiple attack centers, resulting in several oxidation by-products, which is why the 1H-NMR spectrum was recorded for the discoloration of BB with ozone. Since the stoichiometry of the overall oxidation reaction, as well as the relationship between the rate constant and the reaction conditions mentioned above, is not known, a kinetic model based on mass transfer coupled with a chain reaction in the bulk liquid phase was proposed and successfully tested at pH = 7. This research approach also involves the consolidation of the theoretical bases of the ozonation process through the kinetic study carried out, as well as the proposal of a kinetic model. These systematics lead to results that are applicable to other aqueous systems that are impure with dyes, allowing for generalizations and the development of the field, ensuring the sustainability of the research.

Space exposure test of hardwood specimens in the International Space Station

To design a wooden satellite and select the appropriate wood species, we conducted a space exposure test of wood on the International Space Station (ISS). The space exposure test used the Japanese Experiment Module “Kibo” on the Exposed Experiment Bracket Attached on i-SEEP (ExBAS), which is connected to the exposed facility of the ISS. Three wood species considered candidates for the structure of a wooden satellite were used in the exposure test: honoki (Magnolia obovata), yamazakura (Cerasus jamasakura), and dakekanba (Betula ermanii). In the outgassing test conducted in preparation for the space exposure test, the collected volatile condensable materials (CVCM) of the three wood species were below the critical value; however, the total mass loss (TML) exceeded the critical value. However, this was not a problem, because most of the mass loss was due to water evaporation. A space exposure test was conducted for 10 months in 2022. Consequently, no change was observed in the weight of the exposed specimen, and no erosion due to atomic oxygen (AO) was observed. The exposure test was scheduled to be carried out in the forward direction of the ISS travel; however, owing to equipment trouble, it was installed in the opposite direction. This is because an insufficient AO flux collided with the specimen. In terms of wood color, the brightness of the three species decreased owing to space exposure, and saturation increased in two wood species, except for yamazakura. A thin-film layer was observed on the surface of the aluminum cover to which the exposed specimen was fixed, which may have also formed on the surface of the wood specimen, reducing its brightness. However, because the hue angle did not change significantly, only a slight deterioration of the surface layer owing to vacuum ultraviolet was observed. The results confirmed that the wood had hardly deteriorated in space for approximately 10 months.

Non‐Natural MUC1 Glycopeptide Homogeneous Cancer Vaccine with Enhanced Immunogenicity and Therapeutic Activity

AbstractGlycopeptides derived from the glycoprotein mucin‐1 (MUC1) have shown potential as tumor‐associated antigens for cancer vaccine development. However, their low immunogenicity and non‐selective conjugation to carriers present significant challenges for the clinical efficacy of MUC1‐based vaccines. Here, we introduce a novel vaccine candidate based on a structure‐guided design of an artificial antigen derived from MUC1 glycopeptide. This engineered antigen contains two non‐natural amino acids and has an α‐S‐glycosidic bond, where sulfur replaces the conventional oxygen atom linking the peptide backbone to the sugar N‐acetylgalactosamine. The glycopeptide is then specifically conjugated to the immunogenic protein carrier CRM197 (Cross‐Reactive Material 197), a protein approved for human use. Conjugation involves selective reduction and re‐bridging of a disulfide in CRM197, allowing the attachment of a single copy of MUC1. This strategy results in a chemically defined vaccine while maintaining both the structural integrity and immunogenicity of the protein carrier. The vaccine elicits a robust Th1‐like immune response in mice and generates antibodies capable of recognizing human cancer cells expressing tumor‐associated MUC1. When tested in mouse models of colon adenocarcinoma and pancreatic cancer, the vaccine is effective both as a prophylactic and therapeutic use, significantly delaying tumor growth. In therapeutic applications, improved outcomes were observed when the vaccine was combined with an anti‐programmed cell death protein 1 (anti‐PD‐1) checkpoint inhibitor. Our strategy reduces batch‐to‐batch variability and enhances both immunogenicity and therapeutic potential. This site‐specific approach disputes a prevailing dogma where glycoconjugate vaccines require multivalent display of antigens.