Stacking textured films on lattice-mismatched transparent conducting oxides via matched Voronoi cell of oxygen sublattice.

Transparent conducting oxides are a critical component in modern (opto)electronic devices and solar energy conversion systems, and forming textured functional films on them is highly desirable for property manipulation and performance optimization. However, technologically important materials show varied crystal structures, making it difficult to establish coherent interfaces and consequently the oriented growth of these materials on transparent conducting oxides. Here, taking lattice-mismatched hexagonal α-Fe2O3 and tetragonal fluorine-doped tin oxide as the example, atomic-level investigations reveal that a coherent ordered structure forms at their interface, and via an oxygen-mediated dimensional and chemical-matching manner, that is, matched Voronoi cells of oxygen sublattices, [110]-oriented α-Fe2O3 films develop on fluorine-doped tin oxide. Further measurements of charge transport characteristics and photoelectronic effects highlight the importance and advantages of coherent interfaces and well-defined orientation in textured α-Fe2O3 films. Textured growth of lattice-mismatched oxides, including spinel Co3O4, fluorite CeO2, perovskite BiFeO3 and even halide perovskite Cs2AgBiBr6, on fluorine-doped tin oxide is also achieved, offering new opportunities to develop high-performance transparent-conducting-oxide-supported devices.

Revealing *OOH key intermediates and regulating H2O2 photoactivation by surface relaxation of Fenton-like catalysts.

Hydrogen peroxide (H2O2) molecules play important roles in many green chemical reactions. However, the high activation energy limits their application efficiency, and there is still huge controversy about the activation path of H2O2 molecules over the presence of *OOH intermediates. Here, we confirmed the formation of the key species *OOH in the heterogeneous system, via in situ shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS), isotope labeling, and theoretical calculation. In addition, we found that compared with *H2O2, *OOH was more conducive to the charge transfer behavior with the catalyst and the activation of an O-O bond. Furthermore, we proposed to improve the local coordination structure and electronic density of the YFeO3 catalyst by regulating the surface relaxation with Ti modification so as to reduce the activation barrier of H2O2 and to improve the production efficiency of •OH. As a result, the kinetics rates of the Fenton-like (photo-Fenton) reaction had been significantly increased several times. The •OH free radical activity mechanism and molecular transformation pathways of 4-chloro phenol (4-CP) were also revealed. This may provide a clearer vision for the further study of H2O2 activation and suggest a means of designing catalysts for efficient H2O2 activation.

Improved Conductivity and in Situ Formed Heterojunction via Zinc Doping in CuBi2O4 for Photoelectrochemical Water Splitting.

As a photocathode with a band gap of about 1.8 eV, copper bismuthate (CuBi2O4) is a promising material for photoelectrochemical (PEC) water splitting. However, weak charge transfer capability and severe carrier recombination suppress the PEC performance of CuBi2O4. In this paper, the conductivity and carriers transport of CuBi2O4 are improved via introducing Zn2+ into the synthesis precursor of CuBi2O4, driving a beneficial 110 mV positive shift of onset potential in photocurrent. Detailed investigations demonstrate that the introduction of an appropriate amount of zinc leads to in situ segregation of ZnO which serves as an electron transport channel on the surface of CuBi2O4, forming heterojunctions. The synergistic effect of heterojunctions and doping simultaneously promotes the charge transfer and the carrier concentration. OCP experiment proves that ZnO/Zn-CuBi2O4 possesses better charge separation; the Mott-Schottky curve shows that the doping of Zn significantly enhances the carrier concentration; carrier lifetime calculated from time-resolved photoluminescence confirms faster extraction of carriers.

Hydrophilic Modification of Polylactic Acid Fiber and the Usage of Natural Dye for Multi-Levered Improvement of the Fabric Staining Depth and the Stability Effect.

Polylactic acid (PLA) fiber is a degradable material with good environmental friendliness for textile applications. However, the main problems of difficult dyeing of PLA fibers were: high crystallinity to the adsorption of dyes, more ester and methyl groups producing non-hydrophilic problems, long chains making dyes difficult to penetrate, and producing a low dyeing rate. Here, we attempted to change the crystallinity of the PLA fiber to a lower degree from hydrophobic to hydrophilicity property variation, destroy the long chain structure to grant more staining sites, and improve the PLA fiber staining depth and the resilience dyeing effect with deep eutectic solvent (DES) treatment and natural dyes. We discovered that a controlled DES treatment process could make PLA fibers less crystallized, help amorphous areas form, and break up long chains, which lead to more dye sites. After DES treatment, the crystallinity decreased from 56.12 to 29.86%, and the instantaneous water contact angle decreased from 108.79 to 64.39°. The DES-treated PLA fabric exhibited a higher K/S value of 15.14 for natural dyes under specific conditions. The fabric, which had remarkable fastness characteristics and wash resistance, could endure frequent laundering and fulfill the demands of everyday use. Moreover, the fabric had good antimicrobial activity against Escherichia coli, Staphylococcus aureus, and Candida albicans and possessed a certain level of biocompatibility with fibroblasts. This DES treatment and natural dye combination method offered a new strategy for improving PLA fabric staining depth and color fastness, making it a promising option for low-carbon environmental protection in the textile industry.

Lattice Oxygen in Photocatalytic Gas‒Solid Reactions: Participator vs. Dominator.

Lattice-oxygen activation has emerged as a popular strategy for optimizing the performance and selectivity of oxide-based thermocatalysis and electrolysis. However, the significance of lattice oxygen in oxide photocatalysts has been ignored, particularly in gas‒solid reactions. Here, using methane oxidation over a Ru1@ZnO single-atom photocatalyst as the prototypical reaction and via 18O isotope labelling techniques, we found that lattice oxygen can directly participate in gas‒solid reactions. Lattice oxygen played a dominant role in the photocatalytic reaction, as determined by estimating the kinetic constants in the initial stage. Furthermore, we discovered that dynamic diffusion between O2 and lattice oxygen proceeded even in the absence of targeted reactants. Finally, single-atom Ru can facilitate the activation of adsorbed O2 and the subsequent regeneration of consumed lattice oxygen, thus ensuring high catalyst activity and stability. The results provide guidance for next-generation oxide photocatalysts with improved activities and selectivities.

Intratumoral immune heterogeneity of prostate cancer characterized by typing and hub genes.

Discordant abundances of different immune cell subtypes is regarded to be an essential feature of tumour tissue. Direct studies in Prostate cancer (PC) of intratumoral immune heterogeneity characterized by immune cell subtype, are still lacking. Using the single sample gene set enrichment analysis (ssGSEA) algorithm, the abundance of 28 immune cells infiltration (ICI) were determined for PC. A NMF was performed to determine tumour-sample clustering based on the abundance of ICI and PFS information. Hub genes of clusters were identified via weighted gene co-expression network analysis (WGCNA). The multivariate dimensionality reduction analysis of hub genes expression matrix was carried out via principal component analysis (PCA) to obtain immune score (IS). We analysed the correlation between clustering, IS and clinical phenotype. We divided the 495 patients into clusterA (n = 193) and clusterB (n = 302) on the basis of ICI and PFS via NMF. The progression-free survival (PFS) were better for clusterA than for clusterB (p < 0.001). Each immune cell subtypes was more abundant in clusterA than in clusterB (p < 0.001). The expression levels of CTAL-4 and PD-L1 were lower in clusterB than in clusterA (p < 0.001 and p = 0.006). We obtained 103 hub genes via WGCNA. In the training and validation cohorts, the prognosis of high IS group was worse than that of the low IS group (p < 0.05). IS had good predictive effect on 5-year PFS. The expression of immune checkpoint genes was higher in the low IS group than in the high IS group (p < 0.01). Patients with low IS and receiving hormone therapy had better prognosis than other groups. The combination of IS and clinical characteristics including lymph node metastasis and gleason score can better differentiate patient outcomes than using it alone. IS was a practical algorithm to predict the prognosis of patients. Advanced PC patients with low IS may be more sensitive to hormone therapy. CXCL10, CXCL5, MMP1, CXCL12, CXCL11, CXCL2, STAT1, IL-6 and TLR2 were hub genes, which may drive the homing of immune cells in tumours and promote immune cell differentiation.

Spatial Decoupling of Redox Chemistry for Efficient and Highly Selective Amine Photoconversion to Imines.

Light-driven primary amine oxidation to imines integrated with H2 production presents a promising means to simultaneous production of high-value-added fine chemicals and clean fuels. Yet, the effectiveness of this strategy is generally limited by the poor charge separation of photocatalysts and uncontrolled hydrogenation of imines to secondary amines. Herein, a spatial decoupling strategy is proposed to isolate redox chemistry at distinct sites of photocatalysts, and CoP core-ZnIn2S4 shell (CoP@ZnIn2S4) coaxial nanorods are assembled as the proof-of-concept photocatalyst. Directional and ultrafast carrier separation occurs between the CoP core and the ZnIn2S4 shell, as confirmed by in situ X-ray photoelectron spectroscopy, surface photovoltage spectroscopy, and transient absorption spectroscopy analyses. Toward the photoconversion of model substrate benzylamine to N-benzylbenzaldimine, CoP@ZnIn2S4 exhibits a 48-time higher production rate and >99% selectivity when compared to ZnIn2S4 (ca. 20% selectivity), and the detailed reaction mechanism has been verified by in situ diffuse reflectance infrared Fourier transform spectroscopy.

[Clinical study on the treatment of premature ejaculation with Nailifu Spray].

OBJECTIVE: To observe the effect of Nailifu Spray on the treatment of premature ejaculation. METHODS: A total of 90 patients were included in this study from January 1, 2022 to January 1, 2023. Nailifu spray was used to spray the surface of penile skin once a day, 2 sprays per session for 4 weeks.And the patients' premature ejaculation diagnostic tool (PEDT) scores, intravaginal ejaculation latency time (IELT), and international index of erectile function-5 (IIEF-5) scores were collected before and after treatment, respectively. RESUTS: The median (P25,P75) PEDT scores was 16.0(15.0,18.0) scores before treatment and 10.0(10.0,10.0) scores after treatment. The median (P25,P75) of IELT was 20.0 (10.0,30.0) s before treatment and 240.0 (180.0,300.0) s after treatment. The median (P25,P75) of IIEF-5 scores was 21.0 (21.0,22.0) scores before treatment and 21.0 (21.0,21.0) scores after treatment. Compared with baseline levels, IELT was significantly longer and PEDT scores were significantly lower, with statistically significant differences. No significant changes in IIEF-5 scores were seen. CONCLUSION: Nailifu spray treatment of premature ejaculation is accurate and effective, worthy of clinical promotion.

Dihydroartemisinin ameliorates chronic nonbacterial prostatitis and epithelial cellular inflammation by blocking the E2F7/HIF1α pathway.

OBJECTIVE: Chronic nonbacterial prostatitis (CNP) has remained one of the most prevalent urological diseases, particularly in older men. Dihydroartemisinin (DHA) has been identified as a semi-synthetic derivative of artemisinin that exhibits broad protective effects. However, the role of DHA in inhibiting CNP inflammation and prostatic epithelial cell proliferation remains largely unknown. MATERIALS AND METHODS: CNP animal model was induced by carrageenan in C57BL/6 mouse. Enzyme linked immunosorbent assay (ELISA), Real-time quantitative polymerase chain reaction (RT-qPCR) and Western blot were used to examine inflammatory cytokines and proliferation genes expression. Immunofluorescence and immunochemistry staining were used to detect and E2F7 expression. Human prostatic epithelial cells (HPECs) and RWPE-1 was induced by lipopolysaccharide (LPS) to mimic CNP model in vitro. Cell proliferation was determined using MTS assay. RESULTS: DHA significantly alleviated the rough epithelium and inhibited multilamellar cell formation in the prostatic gland cavity and prostatic index induced by carrageenan. In addition, DHA decreased the expression of TNF-α and IL-6 inflammatory factors in prostatitis tissues and in LPS-induced epithelial cells. Upregulation of transcription factor E2F7, which expression was inhibited by DHA, was found in CNP tissues, human BPH tissues and LPS-induced epithelial cells inflammatory response. Mechanically, we found that depletion of E2F7 by shRNA inhibited epithelial cell proliferation and LPS-induced inflammation while DHA further enhance these effects. Furthermore, HIF1α was transcriptional regulated by E2F7 and involved in E2F7-inhibited CNP and cellular inflammatory response. Interestingly, we found that inhibition of HIF1α blocks E2F7-induced cell inflammatory response but does not obstruct E2F7-promoted cell growth. CONCLUSION: The results revealed that DHA inhibits the CNP and inflammation by blocking the E2F7/HIF1α pathway. Our findings provide new evidence for the mechanism of DHA and its key role in CNP, which may provide an alternative solution for the prevention and treatment of CNP.

2D High-Entropy Hydrotalcites.

High-entropy materials (HEMs) with unique configuration and physicochemical properties have attracted intensive research interest. However, 2D HEMs have not been reported yet. To find out unique properties of combining 2D materials and HEMs, a series of 2D high-entropy hydrotalcites (HEHs) is created by coprecipitation method, including quinary, septenary, and even novenary metallic elements. It is found that the fast synthetic kinetics of coprecipitation process conquers the thermodynamically solubility limitation of different elements, which is the prerequisite condition to form HEHs. As the oxygen evolution reaction (OER) electrocatalysts, HEHs show significantly decreased apparent activation energy compared with low-entropy hydrotalcites (LEHs) due to the lattice distortion induced by the multimetallic character of HEHs. This work opens up a new avenue for the development of 2D HEMs, which broadens the family of HEMs and presents a most promising platform for exploring the unknown properties of HEMs.

New insight into the roles of oxygen vacancies in hematite for solar water splitting.

Oxygen vacancies play an important role in the performance improvement of oxide semiconductors as photoanodes for water splitting, such as TiO2, WO3, and Fe2O3. Conductivity improvement due to the presence of oxygen vacancies was reported to be the main reason for the enhanced performance. However, oxygen vacancies may also affect light absorption and charge transfer through the solid/electrolyte interface. The roles of oxygen vacancies have not been thoroughly discussed in the past. Herein, with hematite as an example, the effects of oxygen vacancies on bulk charge transport and surface catalysis are quantitatively analyzed by decoupling photon absorption, interfacial charge transfer and charge separation processes. Oxygen vacancies improve the charge separation of both pristine and Ti-doped hematite. However, opposite observations are found in the charge transfer process for pristine and Ti-doped hematite: the positive effect in pristine hematite but the negative effect in the Ti-doped one. An electrochemical technique is used to analyze the different influences on pristine and Ti-doped hematite to unravel the mechanism of the opposite observations caused by oxygen vacancies. The current study sheds lights on how oxygen vacancies affect various aspects of important factors behind PEC performance, which is helpful to the development of more efficient photoanodes in the future.

Theoretical study on the surface stabilities, electronic structures and water adsorption behavior of the Ta3N5(110) surface.

A recent experiment revealed that the Ta3N5 semiconductor with orientation along the (110) surface exhibited improved photoelectrochemical activities, but the role of the (110) surface in the improved photoelectrochemical activity remains unclear. In this study, density functional theory calculations were performed to investigate the surface stabilities, surface electronic structures and water splitting behavior of the Ta3N5(110) surface with and without oxygen impurities. The results showed that, on the clean and oxygen impurity containing (110) surfaces, the energy barriers of water splitting were as low as 0.05 and 0.06 eV, respectively, suggesting that the Ta3N5(110) surface is a promising candidate for water splitting. The lower energy barriers of water splitting on the Ta3N5(110) surface may be ascribed to the easy migration of the H atom from the surface Ta atom to the nearby N atom. Furthermore, the surface energies and surface electronic structures revealed that the Ta3N5(110) surface contained less oxygen impurities, which is in accordance with the experimental observations.

Effects of oxygen impurities and nitrogen vacancies on the surface properties of the Ta3N5 photocatalyst: a DFT study.

Surface defects and impurities play important roles in the photocatalytic performance of semiconductors. In this study, DFT calculations are performed to investigate the effects of oxygen impurities and nitrogen vacancies on the surface stability and electronic structures of Ta3N5(100), (010) and (001) low-index surfaces. The results show that, for each surface, the oxygen impurities and nitrogen vacancies are beneficial and harmful, respectively, to the surface stability of Ta3N5. The oxygen impurities and nitrogen vacancies have mainly two effects on the surface electronic structures of Ta3N5. One is saturating surface states on the clean surface, and the other is inducing the downshift of conduction band minimum. In addition, the Ta3N5(100) surface with oxygen impurities is expected to have the strongest reduction ability in practice, providing useful guidance for further investigations of Ta3N5 in the photocatalytic hydrogen evolution.

Unraveling the mechanism of 720 nm sub-band-gap optical absorption of a Ta3N5 semiconductor photocatalyst: a hybrid-DFT calculation.

The Ta3N5 semiconductor photocatalyst possesses a 720 nm (about 1.72 eV) sub-band-gap optical absorption but the mechanism of this optical absorption is still controversial. In this study, the hybrid density functional theory calculations are performed to unravel the mechanism of 720 nm sub-band-gap optical absorption of Ta3N5. By studying the possible optical absorption initiated by the ON impurity and the VN defect, we find that the 720 nm sub-band-gap optical absorption of Ta3N5 may be ascribed to the electron transition from V(·)(N) to V(···)(N). In addition, we propose that the 720 nm sub-band-gap optical absorption can be used to qualitatively evaluate the photocatalytic water splitting ability of Ta3N5.

Ge-mediated modification in Ta3N5 photoelectrodes with enhanced charge transport for solar water splitting.

Ta3 N5 is a promising photoanode candidate for photoelectrochemical water splitting, with a band gap of about 2.1 eV and a theoretical solar-to-hydrogen efficiency as high as 15.9 % under AM 1.5 G 100 mW cm(-2) irradiation. However, the presently achieved highest photocurrent (ca. 7.5 mA cm(-2) ) on Ta3 N5 photoelectrodes under AM 1.5 G 100 mW cm(-2) is far from the theoretical maximum (ca. 12.9 mA cm(-2) ), which is possibly due to serious bulk recombination (poor bulk charge transport and charge separation) in Ta3 N5 photoelectrodes. In this study, we show that volatilization of intentionally added Ge (5 %) during the synthesis of Ta3 N5 promotes the electron transport and thereby improves the charge-separation efficiency in bulk Ta3 N5 photoanode, which affords a 320 % increase of the highest photocurrent comparing with that of pure Ta3 N5 photoanode under AM 1.5 G 100 mW cm(-2) simulated sunlight.

Role of oxygen impurity on the mechanical stability and atomic cohesion of Ta3N5 semiconductor photocatalyst.

Oxygen is a natural impurity in the Ta3N5 semiconductor photocatalyst and very difficult to be completely eliminated in different growth conditions. In this study, density functional theory calculations are performed to unravel the cause of natural existence of oxygen impurity in Ta3N5 from the perspectives of mechanical stability and atomic cohesion. The elastic properties calculations show that the oxygen impurity in Ta3N5 is able to remedy the weakened mechanical stability induced by the nitrogen vacancy in Ta3N5. The atomic cohesion calculations show that the oxygen impurity in Ta3N5 enlarges the valence band width of Ta3N5, suggesting that the oxygen impurity is able to strengthen the atomic cohesion of Ta3N5. Based on our calculation results, we propose that the charge-compensation codoping is a promising strategy to improve the water splitting ability of Ta3N5 and simultaneously maintain the mechanical stability and enhanced atomic cohesion of Ta3N5.

MnO2 nanolayers on highly conductive TiO(0.54)N(0.46) nanotubes for supercapacitor electrodes with high power density and cyclic stability.

Pseudo-capacitive MnO2 supercapacitors are attracting intense interest because of the theoretically high specific capacitance (1370 F g(-1)) and low cost of MnO2. For the practical application, the power density and the cyclic stability of MnO2-based supercapacitors are expected to be improved. Increasing the efficiency of the current collection is an effective method to improve the power density for a given supercapacitor. Here, the highly conductive and electrochemically stable material, titanium oxynitride (TiO0.54N0.46), is used as the current collector. Uniform amorphous MnO2 nanolayers were deposited on metal-phase TiO0.54N0.46 nanotube arrays using a modified electrochemical deposition method. The resulting MnO2 supercapacitors exhibited a high power density of 620 kW kg(-1) at an energy density of 9.8 W h kg(-1). This is comparable to high-performance carbon-based electrochemical double layer capacitors in aqueous electrolytes. The high electron transport was enhanced with a highly conductive TiO0.54N0.46 scaffold. Ion transport was promoted in the nanotube structures that had porous walls. In addition, the close interfacial connection between MnO2 and TiO0.54N0.46 contributed to the excellent cyclic stability (ca. 92.0% capacitance retention after 100 000 cycles). These results indicated that the highly conductive and electrochemically stable titanium oxynitride is an excellent candidate for use as an electrode material in high performance supercapacitors.

Preparative separation of crocins and geniposide simultaneously from gardenia fruits using macroporous resin and reversed-phase chromatography.

Gardenia fruits contain valuable natural food colorants including crocins (gardenia yellow) and geniposide. In this study, a process for the enrichment of crocins and geniposide simultaneously from gardenia fruits was developed using macroporous resin and RP chromatography. The performance of eight different types of macroporous resins was evaluated. Static absorption/desorption experiments revealed that LX60 possessed optimal separating capacity. Further dynamic absorption/desorption experiments on LX60 columns were conducted to obtain the optimal parameters. After one run treatment with LX60, the content of crocin-1 in gardenia yellow reached 29.6%, while geniposide in another fraction reached 83.4%. An extract of crocins was obtained from gardenia yellow in a second-stage separation using RP medium-pressure LC, with its color value to be 756 and the content of crocin-1 reaching 60.8%. The separation process was highly efficient, low cost, and compact, which may be informative for purifications of other natural products from complex plant extracts.

Theoretical study of water adsorption and dissociation on Ta3N5(100) surfaces.

Water adsorption and dissociation on the perfect, oxygen containing and nitrogen vacancy containing Ta3N5(100) surfaces are systematically studied by density functional theory calculations. The results show that the perfect Ta3N5(100) surface is very active for water dissociation because of the dangling bonds formed on the perfect Ta3N5(100) surface. The presence of oxygen on the surface is able to stabilize the Ta3N5(100) surface but not to facilitate water dissociation, which may be ascribed to the saturation of surface dangling bonds by oxygen. The presence of a nitrogen vacancy on the surface is able to facilitate water dissociation, but Ta3N5(100) surfaces with nitrogen vacancies are not stable. We found that keeping the impurity oxygen as less as possible is one effective approach to enhance the water splitting ability of Ta3N5. We propose that doping with foreign elements is one potential method to obtain a clean Ta3N5(100) surface, since the oxygen concentration may be adjusted by competition between oxygen and foreign elements.

Flavone C-glycosides from the flowers of Trollius chinensis and their anti-complementary activity.

Phytochemical investigation of ethanol extract from the flowers of Trollius chinensis Bunge resulted in the isolation of two new flavone C-glycosides (1-2), along with 10 known compounds (3-12). The structures of the new compounds were established as 6‴-(3-hydroxy-3-methylglutaroyl)-2″-O-ß-d-galactopyranosyl orientin (1) and 6‴-(3-hydroxy-3-methylglutaroyl)-2″-O-ß-d-galactopyranosyl vitexin (2) on the basis of various spectroscopic analysis (including different 1D and 2D NMR spectroscopies, high-resolution electrospray ionization mass spectrometry) and chemical evidences. Bioassay showed that eight flavonoids inhibited complement activation on the classic pathway in vitro, with their IC50 values ranging from 0.88 to 4.02 mM, which may contribute to the applications of the herb in treatment of acute respiratory distress syndrome, etc.