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Zinc‐air batteries (ZABs) have the advantages of high energy density and rich zinc raw materials. It is a low‐cost, green and sustainable energy storage device. At present, one of the key technologies that hinder the large‐scale application of ZABs is the design and fabrication oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) bifunctional catalysts with excellent performance, especially the non‐platinum‐based catalysts. Here N‐doped carbon‐coated Fe‐based selenium oxide catalyst Fe2O(SeO3)2/Fe3C@NC with high performance has been fabricated by a one‐step pyrolysis and then the electrochemical oxidization. The experimental results confirmed that the existence of Fe−O−Se bonds in Fe2O(SeO3)2 crystal phase of Fe2O(SeO3)2/Fe3C@NC, and the Fe−O−Se bonds could obviously enhance ORR and OER catalytic performance of Fe2O(SeO3)2/Fe3C@NC. Density functional theoretical calculations (DFT) confirmed that the Fe2O(SeO3)2 in Fe2O(SeO3)2/Fe3C@NC had a higher d‐band center of Fe atom and a lower p‐orbital coupling degree with its own lattice O atom than Fe2O3, which leads to Fe site of Fe2O(SeO3)2 being more likely to adsorb external oxygen intermediates. The Fe−O−Se bonds in Fe2O(SeO3)2 results in the modification of coordination environment of Fe atoms and optimizes the adsorption energy of Fe site for oxygen intermediates. Compared with Fe2O3/Fe3C@NC, the Fe2O(SeO3)2/Fe3C@NC showed the obvious enhancements of ORR/OER catalytic activities with a half‐wave potential of 0.91 V for ORR in 0.1 M KOH electrolyte and a low overpotential of 345 mV for OER at 10 mA cm−2 in a 1.0 M KOH electrolyte. The peak power density and specific capacity of Fe2O(SeO3)2/Fe3C@NC‐based ZABs are higher than those of Pt/C+RuO2‐ZABs. The above results demonstrate that the asymmetrical Fe−O−Se bonds in Fe2O(SeO3)2 plays a key role in improving the bifunctional catalytic activities of ORR/OER for ZABs. [ABSTRACT FROM AUTHOR]

Axially chiral tetrasubstituted alkenes are of increasing value and interest in chemistry‐related areas. However, their catalytic asymmetric synthesis remains elusive, owing to the high steric repulsion and relatively low conformational stability. Herein, we disclose the straightforward construction of atropisomeric tetrasubstituted alkenes by effective enantiocontrol in a reaction with vinyl cation intermediates. This copper‐catalyzed enantioselective C(sp2)‐H functionalization of sterically hindered (hetero)arenes with vinyl cations enables the efficient and atom‐economical preparation of axially chiral acyclic tetrasubstituted styrenes and pyrrolyl ethylenes with high atroposelectivities. Importantly, this reaction represents the first example of the assembly of axially chiral alkenes via vinyl cations. Computational mechanistic studies reveal the reaction mechanism, origin of regioselectivity, Z/E selectivity and enantioselectivity. The synthetic utility has been demonstrated by diverse product derivatizations, chiral organocatalyst synthesis, as well as further applications in asymmetric catalysis. [ABSTRACT FROM AUTHOR]

Three‐way catalysis represents a pivotal technology for converting automobile exhaust pollutants into non‐toxic gases. Substituting some noble metals with transition metals is considered a promising way to reduce catalyst costs. Herein, we have investigated the catalytic potential of different configurations of Pd−Cu catalysts prepared by impregnation (PdCu/MA), sol‐gel (PdCu‐MA), impregnation with physical mixing (Pd/Cu/MA) and sol‐gel with physical mixing (Pd/Cu‐MA) to modify the interaction of Pd/Cu and MgAl1.82Ce0.18O4 (MA) spinel in this comparative study. The different structures in these catalysts lead to different catalytic performances. PdCu/MA exhibits the best three‐way catalytic performance, which owe to the small‐sized PdCu particles with high Pd2+ content (45.3 %) and optimal interaction of Pd/Cu particles and MgAl1.82Ce0.18O4 support. Furthermore, comprehensive CO‐DRIFTS, H2‐TPR, and O2‐TPD analyses discover that the metal‐support interaction is beneficial to enhance the catalytic performance in three‐way catalysis. Overall, we demonstrated that the interaction between PdCu bimetals and support can regulate the electronic state of Pd, thereby enhancing the use and efficiency of noble metals. [ABSTRACT FROM AUTHOR]

BACKGROUND: Giant salamander protein peptide is a peptide with rich functional properties. Giant salamander protein peptide KGEYNK (KK‐6) is a peptide with both antioxidant and anti‐inflammatory properties. The antioxidant and anti‐inflammatory mechanisms of KK‐6 are still unclear. When we studied the functional mechanism of KK‐6, we found that the antioxidant property of KK‐6 has a synergistic and promoting effect on anti‐inflammatory properties. RESULTS: KK‐6 enhances cellular resistance to LPS via the MAPK/NF‐κB signaling pathway, leading to increased levels of inflammatory factors: interleukin‐1β (764.81 ng mL−1), interleukin‐6 (1.06 ng mL−1) and tumor necrosis factor‐α (4440.45 ng mL−1). KK‐6 demonstrates potent antioxidant properties by activating the Nrf2 signaling pathway, resulting in elevated levels of antioxidant enzymes (glutathione peroxidase: 0.03 μg mL−1; superoxide dismutase: 0.589 μg mL−1) and a reduction in the concentration of the oxidative product malondialdehyde (967.05 μg mL−1). CONCLUSION: Our findings highlight the great potential of KK‐6, a peptide extracted from giant salamander protein, as a remedy for intestinal inflammation. Through its dual role as an antioxidant and anti‐inflammatory agent, KK‐6 offers a promising avenue for alleviating inflammation‐related damage and oxidative stress. This study lays the foundation for further exploration of giant salamander products and highlights their importance in health and novel food development. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

Layered double hydroxide (LDH) nanosheets as one type of two‐dimensional materials have garnered increasing attention in the field of oxygen evolution reaction (OER) in recent decades. To address the challenges associated with poor conductivity and limited electron and charge transfer capability in LDH materials, we have developed a straightforward one‐pot synthesis method to successfully fabricate a composite material with a microstructure resembling cabbage, which encompasses NiFe‐LDH and nanocarbon (referred as NiFe‐LDH@C). Atomic force microscopy (AFM) and high‐resolution transmission electron microscopy (HRTEM) revealed that the monolayer NiFe‐LDH with a height of ~0.5–0.8 nm is uniformly distributed and closely bonded to the carbon support, leading to a significant enhancement in conductivity and facilitating faster electron and charge transfer. Moreover, the NiFe‐LDH@C exhibits a substantial number of surface defect sites, which enhances the interaction with oxygen species. This dual enhancement in charge transfer and oxygen species‐mediated transfer greatly improves the catalytic OER performance, which is further corroborated by theoretical calculations. Notably, the Ni10Fe6‐LDH@C with the highest concentration of surface oxygen vacancies demonstrated superior water oxidation performance, surpassing commercially available RuO2 catalysts; an OER overpotential of 231 mV@10 mA cm−2 with a Tafel slope of 71 mV dec−1 was achieved. [ABSTRACT FROM AUTHOR]

Compared to Ir, Ru‐based catalysts often exhibited higher activity but suffered significant and rapid activity loss during the challenging oxygen evolution reaction (OER) in a corrosive acidic environment. Herein, we developed a hybrid MnRuOx catalyst in which the RuO2 microcrystalline regions serve as a supporting framework, and the amorphous MnRuOx phase fills the microcrystalline interstices. In particular, the MnRuOx‐300 catalyst from an annealing temperature of 300 °C contains an optimal amorphous/crystalline heterostructure, providing substantial defects and active sites, facilitating efficient adsorption and conversion of OH−. In addition, the heterostructure leads to a relative increase of the d‐band center close to the Fermin level, thus accelerating electron transfer with reduced charge transfer resistance at the active interface between crystalline and amorphous phases during the OER. The catalyst was further thoroughly evaluated under various operating conditions and demonstrated exceptional activity and stability for the OER, representing a promising solution to replace Ir in water electrolyzers. [ABSTRACT FROM AUTHOR]

Surgical excision is the first choice for clinical cancer therapy. However, major challenges, such as postoperative tumor recurrence and unsatisfactory wound healing after surgery, remain. In this study, an adhesive hydrogel is developed as a multifunctional platform for antitumor chemoimmunotherapy and postoperative wound treatment. The hydrogel adheres firmly to diverse tissues and degrades within 4 weeks in vivo with good histocompatibility. The immune‐stimulating hydrogel ((DOX+R837@HN)@Gel) is fabricated by encapsulating doxorubicin (DOX) and imiquimod‐loaded HSA nanoparticles (R837@HNs) into the hydrogel. When combined with immune checkpoint blockade (ICB) therapy, intratumorally administering (DOX+R837@HN)@Gel exhibits markedly enhanced systemic antitumor efficacy and strengthened antitumor immunity. For tumor surgical resection, (DOX+R837@HN)@Gel can adhere to the wounds and effectively prevents tumor recurrence and achieves long‐term immune memory with ICB therapy. Moreover, the hydrogel achieves rapid hemostasis and promotes wound healing after treating surgical wound models. Therefore, this multifunctional hydrogel has great significance for clinical postsurgical cancer treatment. [ABSTRACT FROM AUTHOR]

A group of new iridium(III) complexes were rationally designed and synthesized with 2‐phenylbenzo[d]oxazole (bo), 2‐phenylbenzo[d]thiazole (bt), 2‐(thiophen‐2‐yl)benzo[d]thiazole (thbt), and 2‐(selenophen‐2‐yl)benzo[d]thiazole (sebt) as C^N ligands and bis(diphenylthiophosphoryl)amide (S‐tpip) as ancillary ligand. They are phosphorescent in a wide region of green to red with short lifetimes around 0.31–0.98 μs and quantum yields up to 64.7%. The detailed photophysical properties were investigated by experiment and further supported by density functional theory (DFT) calculation. These research results show that the spectroscopic properties are tuned by the replacement between oxygen, sulfur, and selenium or the change in aromatic ring. It has been demonstrated that the lowest energy‐level absorption and emission are dominated apparently by C^N ligands, and are ascribed to metal‐to‐ligand charge transfer (MLCT) and intra‐ligand charge transfer (ILCT) characters. [ABSTRACT FROM AUTHOR]

A series of new pbt‐based Ir(III) complexes containing N−H derivatives ancillary ligands (piz/pbiz) were designed and synthesized rationally, naming [(CH3Opbt)2Ir(piz)][PF6] (Ir1), [(CF3pbt)2Ir(piz)][PF6] (Ir2), [(Fpbt)2Ir(piz)][PF6] (Ir3), [(CH3Opbt)2Ir(pbiz)][PF6] (Ir4), [(CF3pbt)2Ir(pbiz)][PF6] (Ir5) and [(Fpbt)2Ir(pbiz)][PF6] (Ir6) (where pbt=2‐phenylbenzothiazole, piz=2‐(1H‐imidazol‐2‐yl)pyridine, and pbiz=2‐(pyridin‐2‐yl)‐1H‐benzoimidazole). Combined with photophysical properties and theoretical calculations, their structure‐property relationships were systematically researched. These iridium(III) complexes are phosphorescent in the green and yellow‐green region with quantum yields of 14.1–28.7 % and lifetimes of 0.35–0.88 μs. Considering the relatively high quantum yield and imidazole group on ancillary ligands, [(CF3pbt)2Ir(pbiz)][PF6] (Ir5) was preliminary explored as the phosphorescent sensor toward F− ions. The results showed that the addition of fluoride ions to complex Ir5 in dichloromethane solution induced a red shift of the emission color, along with an enhancement in the luminescent intensity. Theoretical calculations were carried out to understand the mechanism, and the results reveal that the hydrogen bonding interaction of N−H bond with F− influence the electron transfer processes of the lowest energy absorption and emission, leading to a significant change in the photophysical properties. [ABSTRACT FROM AUTHOR]

To seek an effective anti‐lung cancer drug, a total of 14 derivatives were synthesized and characterized. The anti‐lung cancer effect of peiminine derivatives were evaluated in vitro and in vivo. The results of MTT and cell apoptosis assays showed that in comparison with peiminine and its other derivatives, compound 1c (indole‐3‐acetic acid‐peiminine ester) exhibited the highest activity with an IC50 value of 12.78 ± 0.64 μM. Compound 1c (10 μM) significantly reduced the levels of IL‐6, TNF‐α, and IL‐1β in A549 cells. In addition, the qRT‐PCR results showed that compound 1c (10 μM) reduced the mRNA levels of TNF‐α, mTOR, Bcl‐2, Akt1, PI3K, and p65 and increased those of Bax and caspase‐9. Next, the anti‐lung cancer activity of compound 1c (5 mg/kg) was evaluated in A549‐bearing nude mice. It was revealed that the tumor size and weight were significantly inhibited after treatment with compound 1c. And the levels of IL‐6, TNF‐α, and IL‐1β were decreased in mouse tumors. Finally, the latent mechanism of compound 1c was explored by western blot analysis. It was revealed that compound 1c could decrease the expressions of NF‐κB, Bcl‐2, PI3K, Akt, and mTOR and increase the expressions of Bax and caspase‐9 abundance. In conclusion, compound 1c exhibits an inhibitory effect on lung cancer, which was found to occur via inhibition of the PI3K/AKT/mTOR/NF‐κB signaling pathway, thus representing a potential new lead compound for application in lung cancer therapy. [ABSTRACT FROM AUTHOR]

Alzheimer's disease (AD) continues to be a major global health challenge, and the recent approval of Aduhelm and Leqembi has opened new avenues for its treatment. Small‐molecule inhibitors targeting Aβ aggregation hold promise as an alternative to monoclonal antibodies. In this study, we evaluated the ability of berbamine hydrochloride (BBMH), a member of the bisbenzylisoquinoline alkaloids, to reduce Aβ aggregation and cytotoxicity. Thioflavin T kinetics, circular dichroism spectroscopy, and atomic force microscopy results indicated that BBMH effectively inhibited Aβ aggregation. Surface plasmon resonance and molecular docking results further revealed that BBMH could bind to Aβ fibrils, thereby hindering the aggregation process. This physical picture has been confirmed in a quantitative way by chemical kinetics analysis, which showed BBMH tends to bind with the fibril ends and thus prevents the transition from protofibrils to mature fibrils as well as the elongation process. Additionally, our MTT results showed that BBMH was able to reduce the cytotoxicity of Aβ40 on N2a cells. Our results demonstrate, for the first time, the potential of BBMH to inhibit Aβ aggregation and cytotoxicity, offering a promising direction for further research and drug development efforts in the fight against Alzheimer's disease. [ABSTRACT FROM AUTHOR]

Background: Composition of high‐density lipoproteins (HDL) is emerging as an important determinant in the development of microvascular complications in type 2 diabetes mellitus (T2DM). Dutch South Asian (DSA) individuals with T2DM display an increased risk of microvascular complications compared with Dutch white Caucasian (DwC) individuals with T2DM. In this study, we aimed to investigate whether changes in HDL composition associate with increased microvascular risk in this ethnic group and lead to new lipoprotein biomarkers. Materials and Methods: Using 1H nuclear magnetic resonance spectroscopy and Bruker IVDr Lipoprotein Subclass Analysis (B.I.LISA) software, plasma lipoprotein changes were determined in 51 healthy individuals (30 DwC, 21 DSA) and 92 individuals with T2DM (45 DwC, 47 DSA) in a cross‐sectional, case‐control study. Differential HDL subfractions were investigated using multinomial logistic regression analyses, adjusting for possible confounders including BMI and diabetes duration. Results: We identified HDL compositional differences between healthy and diabetic individuals in both ethnic groups. Specifically, levels of apolipoprotein A2 and HDL‐4 subfractions were lower in DSA compared with DwC with T2DM. Apolipoprotein A2 and HDL‐4 subfractions also negatively correlated with waist circumference, waist‐to‐hip ratio, haemoglobin A1c, glucose levels and disease duration in DSA with T2DM, and associated with increased incidence of microvascular complications. Conclusion: While HDL composition differed between controls and T2DM in both ethnic groups, the lower levels of lipid content in the smallest HDL subclass (HDL‐4) in DSA with T2DM appeared to be more clinically relevant, with higher odds of having diabetes‐related pan‐microvascular complications such as retinopathy and neuropathy. These typical differences in HDL could be used as ethnicity‐specific T2DM biomarkers. [ABSTRACT FROM AUTHOR]

The giant Yulong porphyry Cu (‐Mo‐Au) deposit was formed in a post‐collisional setting in eastern Tibet, which is associated with Eocene potassic to ultrapotassic felsic intrusive rocks. The origin of the Yulong potassic intrusion remains highly disputed. Hence, we present new zircon U–Pb ages, whole‐rock geochemistry and zircon Lu‐Hf isotopes for the Yulong intrusion. Zircon U–Pb dating from the porphyritic monzogranite and porphyritic quartz monzonite yield ages of 41.1 ± 0.2, 40.8 ± 0.1 and 40.5 ± 0.2 Ma, respectively. Samples from the Yulong intrusion exhibit high K2O (4.13–4.85%), and high K2O/Na2O (1.00–1.25), [La/Yb]n (30.37–40.37) and Sr/Y (57.86–87.68) ratios, low Mg#, MgO, Ni, and Cr contents, enrichment in light rare earth elements (LREEs) and depletion of high‐field‐strength elements (HFSEs, e.g., Nb, Ta, and Ti). Zircon grains from this study have mostly positive εHf(t) values (+1.6 to +2.9), and crustal model ages (TDMC) of 0.90–1.19 Ga. These features suggest that the Yulong intrusion is derived from a thickened juvenile lower crust. During the Permian to late Triassic, Jinshajiang‐Ailaoshan Palaeo‐Tethyan oceanic subduction from the eastern margin of the North Qiangtang produced metasomatic domains within the continental lithospheric mantle and lower crust. During the late Eocene, the continuing India‐Asia continental collision may have preferentially overthickened the crust. Convective removals in the lower part of the thickened lithosphere resulted in the hot asthenosphere upwelling along the Jinshajiang‐Ailaoshan Suture, which induced the partial melting of the residual metasomatized lithospheric mantle, as well as the thickened lower crust in the Eocene, which formed the Yulong intrusion. [ABSTRACT FROM AUTHOR]

Background and Aims: Non‐alcoholic fatty liver disease (NAFLD) is characterized by the pathological accumulation of triglycerides in hepatocytes and is associated with insulin resistance, atherogenic dyslipidaemia and cardiometabolic diseases. Thus far, the extent of metabolic dysregulation associated with hepatic triglyceride accumulation has not been fully addressed. In this study, we aimed to identify metabolites associated with hepatic triglyceride content (HTGC) and map these associations using network analysis. Methods: To gain insight in the spectrum of metabolites associated with hepatic triglyceride accumulation, we performed a comprehensive plasma metabolomics screening of 1363 metabolites in apparently healthy middle aged (age 45–65) individuals (N = 496) in whom HTGC was measured by proton magnetic resonance spectroscopy. An atlas of metabolite–HTGC associations, based on univariate results, was created using correlation‐based Gaussian graphical model (GGM) and genome scale metabolic model network analyses. Pathways associated with the clinical prognosis marker fibrosis 4 (FIB‐4) index were tested using a closed global test. Results: Our analyses revealed that 118 metabolites were univariately associated with HTGC (p‐value <6.59 × 10−5), including 106 endogenous, 1 xenobiotic and 11 partially characterized/uncharacterized metabolites. These associations were mapped to several biological pathways including branched amino acids (BCAA), diglycerols, sphingomyelin, glucosyl‐ceramide and lactosyl‐ceramide. We also identified a novel possible HTGC‐related pathway connecting glutamate, metabolonic lactone sulphate and X‐15245 using the GGM network. These pathways were confirmed to be associated with the FIB‐4 index as well. The full interactive metabolite‐HTGC atlas is provided online: https://tofaquih.github.io/AtlasLiver/. Conclusions: The combined network and pathway analyses indicated extensive associations between BCAA and the lipids pathways with HTGC and the FIB‐4 index. Moreover, we report a novel pathway glutamate‐metabolonic lactone sulphate‐X‐15245 with a potential strong association with HTGC. These findings can aid elucidating HTGC metabolomic profiles and provide insight into novel drug targets for fibrosis‐related outcomes. [ABSTRACT FROM AUTHOR]

Axially chiral biaryls widely exist in natural products and pharmaceuticals and are used as chiral ligands and catalysts in asymmetric synthesis. Compared to the well‐established axially chiral 6‐membered biaryl skeletons, examples of 5‐membered biaryls have been quite scarce, and mono‐substituted 3‐arylpyrrole atropisomers have not been reported. Here, we disclose a copper‐catalyzed atroposelective diyne cyclization for the construction of a range of axially chiral arylpyrrole biaryls in good to excellent yields with generally excellent enantioselectivities via oxidation and X−H insertion of vinyl cations. Importantly, this protocol not only represents the first synthesis of mono‐substituted 3‐arylpyrrole atropisomers, but also constitutes the first example of atroposelective diyne cyclization and the first atropisomer construction via vinyl cations. Theoretical calculations further support the mechanism of vinyl cation‐involved cyclization and elucidate the origin of enantioselectivity. [ABSTRACT FROM AUTHOR]

Introduction: Sciatica causes intense pain. No satisfactory therapeutic drugs exist to treat sciatica. This study aimed to probe the potential mechanism of ferulic acid in sciatica treatment. Methods: Thirty-two SD rats were randomly divided into 4 groups: sham operation, chronic constriction injury (CCI), mecobalamin, and ferulic acid. We conducted RNA sequencing, behavioral tests, ELISA, PCR, western blotting, and immunofluorescence analysis. TAK-242 and JSH23 were administered to RSC96 and GMI-R1 cells to explore whether ferulic acid can inhibit apoptosis and alleviate inflammation. Results: RNA sequencing showed that TLR4/NF-κB pathway is involved in the mechanism of sciatica. CCI induced cold and mechanical hyperalgesia; destroyed the sciatic nerve structure; increased IL-1β, IL-6, TNF-α, IL-8, and TGF-β protein levels and IL-1β, IL-6, TNF-α, TGF-β, TLR4, and IBA-1 mRNA levels; and decreased IL-10 and INF-γ protein levels and IL-4 mRNA levels. Immunohistochemistry showed that IBA1, CD32, IL-1β, iNOS, nNOS, COX2, and TLR4 expression was increased while S100β and Arg-1 decreased. CCI increased TLR4, IBA-1, IL-1β, iNOS, Myd88, p-NF-κB, and p-p38MAPK protein levels. Treatment with mecobalamin and ferulic acid reversed these trends. Lipopolysaccharide (LPS) induced RSC96 cell apoptosis by reducing Bcl-2 and Bcl-xl protein and mRNA levels and increasing Bax and Bad mRNA and IL-1β, TLR4, Myd88, p-NF-κB, and p-p38MAPK protein levels, while ferulic acid inhibited cell apoptosis by decreasing IL-1β, TLR4, Myd88, p-NF-κB, and p-p38MAPK levels and increasing Bcl-2 and Bcl-xl levels. In GMI-R1 cells, Ferulic acid attenuated LPS-induced M1 polarization by decreasing the M1 polarization markers IL-1β, IL-6, iNOS, and CD32 and increasing the M2 polarization markers CD206, IL-4, IL-10 and Arg-1. After LPS treatment, IL-1β, iNOS, TLR4, Myd88, p-p38MAPK, and p-NF-κB levels were obviously increased, and Arg-1 expression was reduced, while ferulic acid reversed these changes. Conclusion: Ferulic acid can promote injured sciatic nerve repair by reducing neuronal cell apoptosis and inflammatory infiltration though the TLR4/NF-κB pathway. [ABSTRACT FROM AUTHOR]

[2,3]‐Sigmatropic rearrangement reaction involving sulfonium ylide (Doyle–Kirmse reaction) generated from metal carbenes represents one of the powerful methods for the construction of C(sp3)−S and C−C bonds. Although significant advances have been achieved, the asymmetric versions via the generation of sulfonium ylides from metal carbenes have been rarely reported to date, and they have so far been limited to diazo compounds as metal carbene precursors. Here, we describe a copper‐catalyzed enantioselective Doyle–Kirmse reaction via azide‐ynamide cyclization, leading to the practical and divergent assembly of an array of chiral [1,4]thiazino[3,2‐b]indoles bearing a quaternary carbon stereocenter in generally moderate to excellent yields and excellent enantioselectivities. Importantly, this protocol represents a unique catalytic asymmetric Doyle–Kirmse reaction via a non‐diazo approach and an unprecedented asymmetric [2,3]‐sigmatropic rearrangement via α‐imino metal carbenes. [ABSTRACT FROM AUTHOR]

Gas drilling technology is an effective method to protect low permeability tight sandstone reservoirs from damage. However, using this technology to drill high-pressure fractured reservoirs, the fluid flow characteristics are extremely complex, leading to drilling safety challenges. Therefore, based on the conservation equations of mass, momentum, and energy, a new transient coupled flow model in matrix-fracture is established for high-pressure gas reservoirs opened by gas drilling, considering convection term and energy equation, to research the pressure and flow velocity transient behaviors. This model is solved by Shaher Momani's algorithm and CyabJiBe format, and the type curves of the pressure and flow velocity are plotted. The three flow stages are developed, and the impact of parameters and equation terms on the transient flow behavior is analyzed and discussed, such as the energy equation, the matrix permeability (k), the fracture aperture ( L f ), and the fracture outlet pressure. It is found that the energy equation term of the model has a great influence on the transient characteristics such as velocity and pressure, which cannot be ignored. In the first flow stage, the flow velocity characteristics are not affected by the matrix parameters being extremely unstable, but in the second and third stages, the influence of the gas supplied to fracture cannot be ignored. The proposed transient coupled flow model provides a new understanding of the transient flow behavior in matrix-fracture for high-pressure reservoirs during gas drilling, which can be used to interpret the characteristics of pressure and velocity more realistically, to provide support for safe drilling of gas drilling. [ABSTRACT FROM AUTHOR]

Fluoroelastomer (FKM) has been widely used in aerospace and some particular fields, whose aging is a key problem to influence the service life of the systems. The aging behaviors of FKM in the lubricating oil have been investigated in our previous study. In this work, the influence of intentionally aged or oxidized lubricating oil (A‐O) on the aging process of FKM is reported for the first time comparing with the situation in the fresh oil (F‐O). As the oil medium aged at 200°C for different time, its color, acid number and contact angle with FKM change evidently indicating possible oxidation might occur although the Fourier transform infrared spectrometer (FTIR) has little change. Then, the influence of aged oil medium on the aging behaviors of FKM was further examined. Compared with F‐O, the aging process of FKM in A‐O was significantly accelerated as evidenced by FTIR, tensile strength, mass change, DMA, and macroscopic observation. With the increase of aging temperature from 150 to 200°C, the contrast between A‐O and F‐O conditions become more prominent. Specifically, at 200°C, the crosslinking density and tensile strength of FKM in A‐O decreased by 2.2 × 10−4 mol/cm3 and 2.5 MPa compared to that in F‐O, and the mass change reached to 3.8%, which might be due to the higher amount of oil medium by diffusion into the FKM matrix. [ABSTRACT FROM AUTHOR]

A series of heteroleptic phosphorescent iridium(III) complexes [Ir(C^N)2(O^O)] (C^N = 2‐(thiophen‐2‐yl)pyrimidine (tppm), 2‐(benzo[b]thiophen‐2‐yl)pyrimidine (btppm), 2‐(thiophen‐2‐yl)‐4‐(trifluoromethyl)pyridine (cf3thp), 2‐(benzo[b]thiophen‐2‐yl)‐4‐(trifluoromethyl)pyridine (cf3btp); O^O = acetylacetonate (acacH)) have been synthesized and characterized, and their photophysical properties are reported. All of these complexes emit yellow‐red color in the spectral range of 558–647 nm in CH2Cl2 solution at room temperature with quantum yields of 20.1–50.9% and emission lifetimes of 0.23–0.33 μs. Density functional theory (DFT) and time‐dependent‐DFT (TD‐DFT) calculations on these complexes facilitate a detailed assignment of the excited states involved in the absorption and emission processes, that is, metal‐to‐ligand and ligand‐centered charge‐transfer (MLCT/LC) transitions. These charge‐transfer‐type bands are dominated by C^N ligands more than O^O ligand. [ABSTRACT FROM AUTHOR]

The English grain aphid (Sitobion avenae F.) causes significant yield and quality losses in wheat (Triticum aestivum L.) worldwide, and the use of insect‐resistant wheat cultivars reduces the loss level. The present study aimed to identify quantitative trait loci (QTL) and perform putative candidate gene evolutionary analysis for English grain aphid resistance in 261 F2:5 recombinant inbred lines (RILs) derived from the cross Amigo/XN1376. The RIL population and parents were genotyped with the Wheat 55K single nucleotide polymorphism (SNP) array. A total of 14,694 polymorphic SNPs were used to construct a genetic linkage map. One major effect of QTL was detected in F2:5 RILs and was located on chromosome 3DL, explained 19.33% phenotypic variance, temporarily designated as QSa3.haust‐3D. It was located in a 2.73 Mb, flanked by markers AX‐109429351 and AX‐110834100, from 550.25 to 552.98 Mb according to Chinese Spring reference genome. This region contained 39 annotated genes. Eight putative candidate genes for resistance to English grain aphid were identified among these genes. The QTL with closely linked SNP markers could be useful for marker‐assisted selection for resistance to English grain aphid for wheat breeding. Core Ideas: A QTL controlling wheat resistance to English grain aphid was found on chromosome 3DL.QSa3.haust‐3D was located near the centromere of 3DL‐2, and the physical interval was 2.73 Mb.QSa3.haust‐3D was found that the loci may have evolved from Tausch's goatgrass (Aegilops tauschii). [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Better understanding the determining factors of dynamic magnetic relaxation in polynuclear lanthanide based single‐molecule magnets (SMMs) remains a challenge due to the complexity of such architectures involving interactions between the magnetic centers. To address this issue, two structurally related heterometal DyIII2ZnII2 SMMs, [Zn2Dy2(L)4(Ac)2(DMF)(CH3OH)]·CH3OH·2H2O (1) and [Zn2Dy2(L)4(Ac)2(DMF)2]·4CH3CN (2) (H2L = (E)‐2‐((2‐hydroxy‐3‐methoxybenzylidene)amino)‐4‐methyphenol, DMF = N,N‐dimethylformamide), are introduced and investigated. Through modifying the auxiliary ligands on one DyIII site while retaining that on the other DyIII, the intramolecular magnetic interactions and relaxation dynamics in these two heterometallic‐DyIII2ZnII2 SMMs can be tuned, demonstrating a dramatic change in the magnet relaxation behavior with energy barrier changing from a negligible value for 1 to 305 K for 2. Ab initio calculations reveal that changing the coordination geometries on the DyIII sites can significantly affect the magnetic interactions as well as single‐ion anisotropy. [ABSTRACT FROM AUTHOR]

Periodically modulated systems with parity symmetry have been extensively investigated in recent years and exhibited various novel phenomena and potential applications in quantum technologies. In this study, a pump‐probe structure is used to observe the influence of generalized parity on the alignment spectra of magnetic resonance in a periodically biharmonic modulated warm atomic cesium ensemble. The alignment spectra are symmetric when the generalized parity of modulated Floquet atomic ensemble is present. The breaking of spectral symmetry is accompanied by the absence of generalized parity. The influence of generalized parity on atomic alignment polarization distribution is analyzed based on the perspective of the angular‐momentum probability surface. A necessary and sufficient condition for generalized parity to maintain spectral symmetry is verified experimentally and theoretically, providing a new perspective to investigative complex periodic modulation system. The results are universally applicable to atomic and solid‐state systems. [ABSTRACT FROM AUTHOR]

Aiming at the cracking phenomenon of an aeolian sand-modified soil roadbed in an actual project near Tongliao city in eastern Inner Mongolia, Northeast China, an in situ test was conducted. Temperature-compensated fiber Bragg grating (FBG) strain sensors and moisture sensors were embedded into the test roadbed to monitor and observe the relationships between the temperature, moisture, and deformation of the roadbed with respect to variations in climate conditions in such a cold region. For the core issues of roadbed soil deformation and impact on the project, two climate conditions, namely, temperature and rainfall, were taken as external factors, while the temperature and moisture of the roadbed soil were taken as internal factors controlling the deformation and failure of the roadbed soil. A correlation analysis of the test roadbed monitoring data showed that the roadbed soil moisture was weakly affected by environmental conditions. The roadbed soil temperature was independent of the rainfall but was significantly related to air temperature variation (the correlation coefficient ranged from 0.6301 to 0.8926). Limited by the boundary conditions of the roadbed, the response of the variation in the roadbed soil temperature to the air temperature variation gradually weakened from the shallow surface to the deeper parts and the lag in the roadbed soil temperature variation relative to the air temperature variation became more evident. A correlation analysis of the monitoring data of the roadbed soil deformation, soil temperature, and soil moisture showed that the roadbed soil moisture had a weak correlation with the roadbed soil temperature. The roadbed soil deformation was independent of the soil moisture but was strongly related to the roadbed soil temperature. Therefore, the strain of the test roadbed could reflect the roadbed deformation as temperature deformation. The temperature deformation of the roadbed superficial soil was significantly greater than that of the deep soil. [ABSTRACT FROM AUTHOR]

Co‐doping of ceria with Cu and Cr forming a ternary CuCrCeOx solid solution enhances N2‐selectivity as well as NO and CO conversions compared to the corresponding singly doped ceria, CuCeOx and CrCeOx, and pristine ceria, in the absence as well as presence of water and oxygen. The comparative study of these solid‐solution catalysts indicates that the doping of ceria results in the coupling of different transition metal redox cycles, which has a strong effect on the surface population of oxygen vacancies. The temperature required to reach 95 % N2‐selectivity is shown to be nearly linearly correlated to the concentration of oxygen vacancy defects. The oxygen defect population is highest for the ternary CuCrCeOx solid solution, which exhibits the best catalytic performance, reaching 100 % N2‐selectivity at around 100 °C. Three redox cycles (CrVI/CrIII, CuII/CuI, and CeIV/CeIII) have been identified in this catalyst leading to a synergistic effect. The ternary CuCrCeOx catalyst exhibits good water tolerance and long‐term stability while the SO2 tolerance is limited due to selective blocking of the active surface oxygen defects forming SO32− species, resulting in catalyst deactivation. [ABSTRACT FROM AUTHOR]

Dimethyl carbonate (DMC) is a commonly used and environmentally sustainable chemical compound and intermediate in a variety of industrial applications. To date, several large‐scale industrial DMC synthesis routes have been developed, including methanol phosgenation, transesterification, and oxidative carbonylation of methanol. However, these manufacturing routes have several disadvantages, such as the use of hypertoxic phosgene as raw material, costly processing, and explosion risks. The most encouraging and ecofriendly path is the green production of DMC from CO2 and methanol. Various catalytic materials have been examined concerning their suitability for DMC synthesis. The issues of low yield and difficulty in tests have not been resolved fundamentally, which is caused by the inherent problems of the synthetic pathway and limitations imposed by thermodynamics. The search for more efficient production routes has driven the activation of CO2 via electro‐assisted synthesis as well as membrane reactors, which can isolate products in real‐time to maximize DMC yield. The green synthesis of dimethyl carbonate catalyzed by different catalysts including Zr/Ce/Cu‐based nanocomposites, organometallic compounds, heteropoly acid, ionic liquid, metal‐organic frameworks, etc, is discussed in detail. Further, the structure–activity relationships and insights into molecular activation and catalytic mechanisms, as well as the identification of active sites on catalysts are addressed. [ABSTRACT FROM AUTHOR]

The measurement of anisotropic residual dipolar couplings (RDCs) parameters for the structure elucidation of organic molecules relies on suitable alignment media. Employment of self‐assembled liquid crystalline systems to create anisotropic alignment can be an effective way to realize aligned samples and acquire RDCs. This Mini‐review highlights the recent advances on amino acid‐based helical polymers and supramolecular oligomers forming rigid, rod‐like structures that aggregate into ordered liquid crystalline phases, including amino acid‐based helical polyisocyanides, polyacetylenes, polypeptides, and oligopeptides assembled alignment media. The methodology for the determination of anisotropic liquid crystals is briefly discussed, and a summary of recent research progress in the enantiodifferentiation of helical polymers aligned media is followed. In addition, the self‐assembled mechanism of oligopeptides and their RDCs structural analysis are also described. [ABSTRACT FROM AUTHOR]

Protein kinases are involved in almost all biological activities. The activities of different kinases reflect the normal or abnormal status of the human body. Therefore, detecting the activities of different kinases is important for disease diagnosis and drug discovery. Fluorescent probes offer opportunities for studying kinase behaviors at different times and spatial locations. In this review, we summarize different kinds of fluorescent chemosensors that have been used to detect the activities of many different kinases. [ABSTRACT FROM AUTHOR]

Medium‐sized N,S‐heterocycles have received tremendous interest due to their biological activities and potential medical applications. However, asymmetric synthesis of these compounds are extremely rare. Described herein is a catalyst‐dependent [3,3]‐sigmatropic rearrangement of sulfoxide‐ynamides, enabling divergent and atom‐economic synthesis of a series of valuable medium‐sized N,S‐heterocycles in moderate to good yields with broad substrate scope. Importantly, excellent enantioselectivities have been achieved via an unprecedented chirality‐transfer. Moreover, theoretical calculations are employed to elucidate the origins of the catalyst‐dependent stereospecific [3,3]‐rearrangement. [ABSTRACT FROM AUTHOR]

There are two types of abnormal hematopoiesis in solid tumor occurrence and treatment: pathological hematopoiesis, and myelosuppression induced by radiotherapy and chemotherapy. In this review we primarily focus on the abnormal pathological hematopoietic differentiation in cancer induced by tumor-released granulocyte colony-stimulating factor (G-CSF) and granulocyte-macrophage colony-stimulating factor (GM-CSF). As key factors in hematopoietic development, G-CSF/GM-CSF are well-known facilitators of myelopoiesis and mobilization of hematopoietic stem cells (HSCs). In addition, these two cytokines can also promote or inhibit tumors, dependent on tumor type. In multiple cancer types, hematopoiesis is greatly enhanced and abnormal lineage differentiation is induced by these two cytokines. Here, dysregulated hematopoiesis induced by G-CSF/GM-CSF in solid tumors and its mechanism are summarized, and the prognostic value of G-CSF/GM-CSF-associated dysregulated hematopoiesis for tumor metastasis is also briefly highlighted. [ABSTRACT FROM AUTHOR]

The integration of Fe dopant and interfacial FeOOH into Ni‐MOFs [Fe‐doped‐(Ni‐MOFs)/FeOOH] to construct Fe−O−Ni−O−Fe bonding is demonstrated and the origin of remarkable electrocatalytic performance of Ni‐MOFs is elucidated. X‐ray absorption/photoelectron spectroscopy and theoretical calculation results indicate that Fe‐O−Ni−O−Fe bonding can facilitate the distorted coordinated structure of the Ni site with a short nickel–oxygen bond and low coordination number, and can promote the redistribution of Ni/Fe charge density to efficiently regulate the adsorption behavior of key intermediates with a near‐optimal d‐band center. Here the Fe‐doped‐(Ni‐MOFs)/FeOOH with interfacial Fe−O−Ni−O−Fe bonding shows superior catalytic performance for OER with a low overpotential of 210 mV at 15 mA cm−2 and excellent stability with ≈3 % attenuation after a 120 h cycle test. This study provides a novel strategy to design high‐performance Ni/Fe‐based electrocatalysts for OER in alkaline media. [ABSTRACT FROM AUTHOR]

Bevacizumab (BV) has an inhibitory effect on tumor growth including lung adenocarcinoma. However, its efficacy is greatly affected by drug resistance. Astragaloside IV (AST‐IV) is effective in combination with other drugs is effective to treat cancer. This study aimed to investigate the effect of AST‐IV on enhancing the sensibility of lung adenocarcinoma cells to BV. A549 cells were treated by different concentrations of BV and AST‐IV. Cell viability, cell cycle, and apoptosis were detected by thiazolyl blue tetrazolium bromide (MTT) and flow cytometry, respectively. Quantitative reverse transcription‐polymerase chain reaction (qRT‐PCR) and western blotting were performed to detect the expression levels of autophagy‐ and apoptosis‐related proteins, protein kinase B (AKT), and mammalian target of rapamycin (mTOR). The results showed that BV or AST‐IV could inhibit the viability and promote the apoptosis of A549 cells in a concentration‐dependent manner. Moreover, BV or AST‐IV inhibited Bcl‐2 expression and increased the expressions of Bax and Cleaved caspase‐3, and promoted apoptosis. BV and AST‐IV in combination acted synergistically on viability and apoptosis of A549 cells. However, BV alone down‐regulated P62 expression, LC3I/LC3II level, the number of cells arrested at S phase and the phosphorylation levels of AKT and mTOR, but upregulated the number of cells arrested at G0/G1 phase and Beclin1 expression, whereas AST‐IV alone could reverse the effect of BV on autophagy‐related proteins, the phosphorylation levels of AKT and mTOR. This paper demonstrates that AST‐IV enhances the effect of BV on inhibiting proliferation and promoting apoptosis of lung adenocarcinoma cells through inhibiting autophagy pathway. [ABSTRACT FROM AUTHOR]

Objective: To investigate the efficacies of Femoral Neck System (FNS) and the three cannulated screws fixation (3CS) as therapeutic options for femoral neck fractures. Method: This was a retrospective study involving 69 patients (26 males and 43 females; mean age of 54.9 years (range, 28–66 years)) subjected to either FNS or 3CS for femoral neck fracture therapy. These patients were treated in our hospital from October 2019 to May 2020. Patient follow up was done at 1, 2, 3 and 6 months. During the short‐term (6 months) follow‐up period, surgical procedures for the two groups and incidences of complications were analyzed. Perioperative parameters were recorded and analyzed. Postoperative hip joint functions were measured and compared using the Harris score. The assessed perioperative parameters included surgical time, hemoglobin loss, fluoroscopy duration, hospitalization length and hospitalization cost. The main complications at last follow‐up (6 months) included varus tilting, femoral neck shortness, and implant removal. Results: Differences in the number of patients, age, Garden type of fracture and time from injury to surgery between the two groups were not significant (P > 0.05). With regards to perioperative parameters, compared to 3CS, FNS treatment performed better in surgical time (60.00 ± 12.44 vs 76.81 ± 13.10 min, P = 0.000), blood loss (13.67 ± 8.02 vs 16.58 ± 4.16 g/L, P = 0.059) and fluoroscopy time (39.73 ± 9.57 vs 58.14 ± 9.15 s, P = 0.000). Differences in hospitalization length and cost between the groups were not significant (P > 0.05). During the whole follow‐up period, all patients did not exhibit dysfunction, pulmonary embolism or even death as a result of long‐term immobilization of affected limbs. Surgical incisions for all patients healed well without infections. During the 6‐month follow‐up period, the FNS group exhibited a higher Harris score (84.61 ± 3.42 vs 78.67 ± 3.72, p = 0.000). In addition, treatment‐associated complications (FNS vs 3CS) included femoral neck varus tilt (3.03% vs 11.11%), femoral neck shortness (6.06% vs 13.89%), and implant removal (0% vs. 13.89%). Implant removal rate for the FNS group was significantly less than that of the 3CS group (P = 0.026). Differences in incidences of femoral neck varus tilt (P = 0.196) and femoral neck shortness (P = 0.282) between the two groups were not significant. However, the difference in number was significant (FNS group was less). Conclusion: FNS treatment is associated with a smaller surgical trauma, stronger stability, and reductions in post‐operative complication incidences, therefore, it is a potential therapeutic option for femoral neck fractures. [ABSTRACT FROM AUTHOR]

Background: To investigate the clinical characteristics of metachronous second primary malignancies (Met-SPMs) and its impact on prognosis in hypopharyngeal carcinoma (HPC). Methods: We reviewed 593 newly diagnosed HPC patients without invasive synchronous SPMs (Syn-SPMs) who were treated in our cancer center between 2009 and 2019. According to the status during follow-up, patients were classified into three groups: (a) without SPMs (No-SPMs, n = 440), (b) with tumors in situ in the esophagus or stomach (Tis, n = 80), or (c) with Met-SPMs (n = 73). Results: The median follow-up time for entire cohort (n = 593) was 66.7 months. Met-SPMs were present in 12.3% of the cohort (73/593). The predominant site of SPMs was esophagus, followed by lung, oral cavity, thyroid, stomach, and oropharynx. In Met-SPMs group, both index tumor and SPMs were the main causes of death. Tis group exhibited comparable 5-year overall survival (OS) and disease-specific survival (DSS) with that of No-SPMs group. The Met-SPMs group had similar 5-year OS rate and better 5-year DSS rate of 47.3% versus 43.6% (odds ratio [OR], 0.931; 95% confidence interval [CI], 0.681-1.274, p = 0.657) and 66.3% vs. 46.2% (OR, 0.600; 95% CI, 0.402-0.896, p = 0.012), respectively, compared with the No-SPMs group. Conclusion: The overall incidence of Met-SPMs in HPC was 12.3%. The occurrence of Met-SPMs does not jeopardize the survival outcome of HPC. Routine surveillance of Met-SPMs was requisite for patients with HPC. [ABSTRACT FROM AUTHOR]

A simple 4 × 4 beamforming network with spatial diversity and multiplexing reconfiguration is proposed in this paper. By analyzing and decomposing the simplified transmission matrix of the network, it is found that the 4 × 4 butler matrix can achieve spatial diversity and multiplexing reconfiguration by switching the operating modes of the four-port devices. Therefore, by designing a reconfigurable device with three modes among hybrid coupler, crossover, and transmission line, a simple 4 × 4 reconfigurable beamforming network is achieved. The proposed network can achieve orthogonal spatial diversity responses with equal amplitude and progressive phase distribution responses at the four output ports (State 1) and hybrid spatial diversity and multiplexing responses (State 2) with equal amplitude and progressive phase distribution responses at the two adjacent output ports. For the experimental validation, a particular version of the reconfigurable device and network which work at 4.9 GHz, have been designed, fabricated, and tested. Good results indicate the proposed network can be widely used in wireless communication networks for MIMO applications. [ABSTRACT FROM AUTHOR]

Poly‐ether‐ether‐ketone (PEEK) possesses excellent biocompatibility and similar elastic modulus as bones but suffers from poor osseointegration; usually, the addition of hydroxyapatite (HA) is considered as an effective way to improve the osseointegration of PEEK implant interface. To investigate the effect of HA content and particle size on the mechanical behaviors and osteogenesis in vitro of PEEK‐HA composites, the PEEK‐HA specimens with variable HA content and particle size have been fabricated by powder mixing‐heat press method and characterized by mechanical and biological tests. The results showed that the tensile/bending strength and elongation at break of PEEK‐HA are significantly impaired as the increasing HA amount, but the modulus improves. The compressive strength and modulus are improved as the increasing amount of HA. The PEEK‐HA with smaller HA particle size possesses higher‐performance tensile/bending and lower‐performance compressive properties. In osteogenesis tests in vitro, the results reveal that the cells amount attached on the substrate rises and the cells flatten more evenly with numerous cytoplasmic processes on greater area with the increasing HA content and decreasing particle size. The PEEK‐HA group that HA content is 20 wt% and particle size is 20 nm exhibits optimal‐performance osteogenesis in vitro, while maintaining sufficient mechanical properties. [ABSTRACT FROM AUTHOR]

Metal–organic frameworks (MOFs) with carboxylate ligands as co‐catalysts are very efficient for the oxygen evolution reaction (OER). However, the role of local adsorbed carboxylate ligands around the in‐situ‐transformed metal (oxy)hydroxides during OER is often overlooked. We reveal the extraordinary role and mechanism of surface‐adsorbed carboxylate ligands on bi/trimetallic layered double hydroxides (LDHs)/MOFs for OER electrocatalytic activity enhancement. The results of X‐ray photoelectron spectroscopy (XPS), synchrotron X‐ray absorption spectroscopy, and density functional theory (DFT) calculations show that the carboxylic groups around metal (oxy)hydroxides can efficiently induce interfacial electron redistribution, facilitate an abundant high‐valence state of nickel species with a partially distorted octahedral structure, and optimize the d‐band center together with the beneficial Gibbs free energy of the intermediate. Furthermore, the results of in situ Raman and FTIR spectra reveal that the surface‐adsorbed carboxylate ligands as Lewis base can promote sluggish OER kinetics by accelerating proton transfer and facilitating adsorption, activation, and dissociation of hydroxyl ions (OH−). [ABSTRACT FROM AUTHOR]

The oxidation of photocatalytic methanol into valuable chemicals is of considerable importance to the growth of the chemical industry. TiO2 has been proven to be a catalyst for methanol photocatalytic oxidation to valued chemicals (e. g. methyl formate and dimethoxymethane) at room temperature with an inferior activity. Recently, it has become a hot research topic due to its low interaction temperature with fewer by‐products. Further, the introduction of IB metal particles (i. e. Cu, Ag, and Au) upon the surface of titania can drastically enhance the catalytic activity in the photo‐oxidation, which is mainly due to metal nanoparticles can optimally enhance the efficiency of the isolation of photo‐generated holes and electrons as well as dissociate oxygen molecules. Herein, we review recent progress of the photocatalysis of methanol toward the production of chemicals over different photocatalysts (e. g., TiO2P25, M NPs/TiO2, where M=CuO, Ag2O, Au, PtO, etc). Moreover, we also glean an understanding of the catalytic mechanism and conversion pathway at play, which is confirmed by STM, in‐situ ATR‐IR, DFT simulations, etc. The reaction pathway of photo‐oxidation is different from that in the thermal process. A pivotal intermediate is absorbed formaldehyde (HCHO*), which is formed via an oxidative dehydrogenation over the redox sites of catalysts. Then the generated HCHO* directly reacts with neighboring methanol to give methyl formate (on redox sites) and dimethoxymethane (on acidic sites through a scrambling movement). [ABSTRACT FROM AUTHOR]