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Developing cost-effective monolith catalyst with superior low-temperature activity is critical for oxidative efficacious removal of industrial volatile organic compounds (VOCs). However, the complexity of the industrial flue gas conditions demands the need for high moisture tolerance, which is challenging. Herein, CoMn-Metal Organic Framework (CoMn-MOF) was in situ grown on Ni foam (NiF) at room temperature to synthesize the cost-effective monolith catalyst. The optimized catalyst, Co1Mn1/NiF, exhibited excellent performance in toluene oxidation (T 90  = 239 °C) due to the substitution of manganese into the cobalt lattice. This substitution weakened the Co-O bond strength, creating more oxygen vacancies and increasing the active oxygen species content. Additionally, experimentally and computationally evidence revealed that the mutual inhibiting effect of three typical aromatic hydrocarbons (benzene, toluene and m-xylene) over the Co1Mn1/NiF catalyst was attributed to the competitive adsorption occurring on the active site. Furthermore, the Co1Mn1/NiF catalyst also presents outstanding water resistance, particularly at a concentration of 3 vol%, where the activity is even enhanced. This was attributed to the lower water adsorption and dissociation energy derived from the interaction between the bimetals. Results demonstrate that the dissociation of water vapor enables more reactive oxygen species to participate in the reaction which reduces the formation of intermediates and facilitates the reaction. This investigation provides new insights into the preparation of oxygen vacancy-rich monolith catalysts with high water resistance for practical applications., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Inc. All rights reserved.)

Oxygenated volatile organic compounds (OVOCs), emitted in large quantities by the chemical industry, are a major contributor to the formation of ozone and subsequent particulate matter. For the efficient catalytic oxidation of OVOCs, the challenges of molecular activation and intermediate inhibition remain. The construction of bifunctional active sites with specific structures offers a promising way to overcome these problems. Here, the Pd@Layered-CoO x /MFI bifunctional catalyst with core-shell active sites was rationally fabricated though a two-step ligand pyrolysis method, which exhibits a superb oxidation efficiency toward ethyl acetate (EA). Over this, 13.4% of EA (1000 ppm) can be oxidized at just 140 °C with a reaction rate of 13.85 mmol·g Pd -1 ·s -1 , around 176.7 times higher than that of the conventional Pd-CoO x /MFI catalyst. The electronic coupling of the Pd-Co pair promotes the electron back-donation from Pd nanoparticles to the layered CoO x shell and facilitates the formation of Pd 2+ species, which greatly enhances the adsorption and activation of the electron-rich C═O bond of the EA molecules. In addition, the synergy of these core-shell Pd@Layered-CoO x sites accelerates the activation and transformation of *O species, which inhibit the formation of acetaldehyde and ethanol byproducts, ensuring the rapid total oxidation of EA molecules via the Mars-van Krevelen mechanism. This work established a solid foundation for exploring robust bifunctional catalysts for deep OVOC purification.

Herein we report the discovery of an azabicyclo[2.1.1]hexane piperazinium methanesulfonate salt from an unexpected rearrangement reaction in the preparation of ligand-directed degraders (LDDs). This bench-stable compound was found to be a versatile electrophile in a ring-opening reaction with various types of nucleophiles. Its utility as a versatile medicinal chemistry building block is further demonstrated in the synthesis of an LDD compound targeting degradation of the androgen receptor.

Two-dimensional (2D) van der Waals materials are increasingly seen as potential catalysts due to their unique structures and unmatched properties. However, achieving precise synthesis of these remarkable materials and regulating their atomic and electronic structures at the most fundamental level to enhance their catalytic performance remain a significant challenge. In this study, we synthesized single-crystal bulk PtTe crystals via chemical vapor transport and subsequently produced atomically thin, large PtTe nanosheets (NSs) through electrochemical cathode intercalation. These NSs are characterized by a significant presence of Te vacancy pairs, leading to undercoordinated Pt atoms on their basal planes. Experimental and theoretical studies together reveal that Te vacancy pairs effectively optimize and enhance the electronic properties (such as charge distribution, density of states near the Fermi level, and d -band center) of the resultant undercoordinated Pt atoms. This optimization results in a significantly higher percentage of dangling O-H water, a decreased energy barrier for water dissociation, and an increased binding affinity of these Pt atoms to active hydrogen intermediates. Consequently, PtTe NSs featuring exposed and undercoordinated Pt atoms demonstrate outstanding electrocatalytic activity in hydrogen evolution reactions, significantly surpassing the performance of standard commercial Pt/C catalysts.

C-C linked glutarimide-containing structures with direct utility in the preparation of cereblon-based degraders (PROTACs, CELMoDs) can be assessed in a single step from inexpensive, commercial α-bromoglutarimide through a unique Brønsted-acid assisted Ni-electrocatalytic approach. The reaction tolerates a broad array of functional groups that are historically problematic and can be applied to the simplified synthesis of dozens of known compounds that have only been procured through laborious, wasteful, multi-step sequences. The reaction is scalable in both batch and flow and features a trivial procedure wherein the most time-consuming aspect of reaction setup is weighing out the starting materials., (© 2024 Wiley‐VCH GmbH.)

Introduction: Hematopoietic progenitor kinase 1 (HPK1), a 97-kDa serine/threonine Ste20-related protein kinase, functions as an intracellular negative regulator, primarily in hematopoietic lineage cells, where it regulates T cells, B cells, dendritic cells, and other immune cells. Loss of HPK1 kinase activity results in exacerbated cytokine secretion, enhanced T cell signaling, improved viral clearance, and thus increased restraint of tumor growth. These findings highlight HPK1 as a promising target for immuno-oncology treatments, culminating in the advancement of candidate compounds targeting HPK1 to clinical trials by several biotech enterprises., Areas Covered: Through searching PubMed, Espacenet-patent search, and clinicaltrials.gov, this review provides a comprehensive analysis of HPK1, encompassing its structure and roles in various downstream signaling pathways, the consequences of constitutive activation of HPK1, and potential therapeutic strategies to treat HPK1-driven malignancies. Moreover, the review outlines the patents issued for small molecule inhibitors and clinical investigations of HPK1., Expert Opinion: To enhance the success of tumor immunotherapy in clinical trials, it is important to develop protein degraders, allosteric inhibitors, and antibody-drug conjugates based on the crystal structure of HPK1, and to explore combination therapy approaches. Although several challenges remain, the development of HPK1 inhibitors display promising in preclinical and clinical studies.

Light alkanes (LAs), typical VOCs existing in both stationary and mobile sources, pose significant environmental concerns. Although noble metal catalysts demonstrate strong C-H bond activation, their effectiveness in degrading LAs is hindered by inherent challenges, including poor chemical stability and water resistance. Here, from a new perspective, we propose a feasible strategy that adjusting the metal bond lengths within Pd clusters through partial substitution of smaller radius 3d transition metals (3dTMs) to prioritize the activation of low-energy C-C bonds within LAs. Benefiting from this, PdCo/CeO 2 exhibits exceptional catalytic performance in propane degradation due to their high capacity for C-C cleavage stemming from the shorter Pd-Co length (2.51 Å) and lower coordination number (1.73), boosting the activation of α-H and β-H of propane simultaneously and accelerating the mobility of postactivated oxygen species to prevent Pd center deep oxidation. The presence of 3dTMs on Pd clusters improves the redox and charge transfer ability of catalysts, resulting in an amplified generation of oxygen vacancies and facilitating the adsorption and activation of reactants. Mechanistic studies and DFT calculations suggest that the substitution of 3dTMs significantly accelerate C-C bond cleavage within C3 intermediates to generate the subsequent C2 and C1 intermediates, suppressing the generation of harmful byproducts.

Achieving an efficient and stable heterogeneous Fenton reaction over a wide pH range is of great significance for wastewater treatment. Here, a pollen-derived biochar catalyst with a unique honeycomb-like structure, coupled with the dispersion of magnetic Fe 3 O 4 /FeS (Fe/S) nanoparticles, was synthesized by simple impregnation precursor, followed by pyrolysis. The prepared Fe/S-biochar catalyst demonstrated outstanding phenol degradation efficiency across a wide pH range, with 98% of which eliminated even under neutral conditions (pH 7.0). The high catalytic activity was due to the multilevel porous structure of pollen-derived biochar provided enough active sites and allowed for better electron transfer, then increases oxidation ability to promote the reaction. Moreover, the acid microenvironment formed by SO 4 2- group from Fe/S composite extended the pH range for Fenton reaction, and S 2-  facilitated the conversion of Fe 3+ to Fe 2+ , resulting in remarkable degradation efficiency. Further, biochar can effectively promote cycling stability by limiting Fe leaching. This work may provide a general strategy for designing 3D framework biochar-based Fe/S catalysts with excellent performance for heterogeneous Fenton reactions., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022. Published by Elsevier B.V.)

The widespread presence of formaldehyde (HCHO) pollutant has aroused significant environmental and health concerns. The catalytic oxidation of HCHO into CO 2 and H 2 O at ambient temperature is regarded as one of the most efficacious and environmentally friendly approaches; to achieve this, however, accelerating the intermediate formate species formation and decomposition remains an ongoing obstacle. Herein, a unique tandem catalytic system with outstanding performance in low-temperature HCHO oxidation is proposed on well-structured Pd/Mn 3 O 4 -MnO catalysts possessing bifunctional catalytic centers. Notably, the optimized tandem catalyst achieves complete oxidation of 100 ppm of HCHO at just 18 °C, much better than the Pd/Mn 3 O 4 (30%) and Pd/MnO (27%) counterparts as well as other physical tandem catalysts. The operando analyses and physical tandem investigations reveal that HCHO is primarily activated to gaseous HCOOH on the surface of Pd/Mn 3 O 4 and subsequently converted to H 2 CO 3 on the Pd/MnO component for deep decomposition. Theoretical studies disclose that Pd/Mn 3 O 4 exhibits a favorable reaction energy barrier for the HCHO → HCOOH step compared to Pd/MnO; while conversely, the HCOOH → H 2 CO 3 step is more facilely accomplished over Pd/MnO. Furthermore, the nanoscale intimacy between two components enhances the mobility of lattice oxygen, thereby facilitating interfacial reconstruction and promoting interaction between active sites of Pd/Mn 3 O 4 and Pd/MnO in local vicinity, which further benefits sustained HCHO tandem catalytic oxidation. The tandem catalysis demonstrated in this work provides a generalizable platform for the future design of well-defined functional catalysts for oxidation reactions.

Light alkanes extensively presented in industrial exhausts have led tremendous harm to the atmospheric environment and human health. However, the catalytic destruction of light alkanes generally operates at elevated temperatures and the consequent reaction by-products are inevitably produced. It is therefore of great significance to engineer catalysts with superior thermal stability, internal activity and selectivity. Herein, we developed a Pd cluster/CeO 2 catalyst (Pd n /CeO 2 ) by a scalable deposition precipitation strategy, which demonstrates unexpected activity and thermal stability in the presence of 5% H 2 O attributing to abundant unsaturated Pd metal sites and excellent oxygen dissociation performance. Pd n /CeO 2 possesses a highly efficient C-C cleavage capability due to the persistent formation of a large number of oxygen vacancies. In comparison, the Pd 1 /CeO 2 catalyst, which is preferential for C-H bond cleavage and inactive for C-C bond cracking, produces remarkable hazardous organic by-products such as propyne and propylene, inhibiting the continuous decomposition of propane. The present study sheds critical insights into engineering efficient and stable catalysts for light alkane destruction., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

A kind of adsorbent (Hydrogel-I) derived from sodium alginate and modified alkaline lignin (MAL) has been proved to possess a good adsorption performance for Pb(II)-loaded wastewater based on batch experiments. However, practical removal of Pb(II)-loaded-wastewater is a continuous and dynamic process. Herein, Hydrogel-I was further evaluated by packing it into a fixed-bed column. The breakthrough curves were established under different inflow rates (0.159-0.318 L/min), inflow directions (down-inflow mode and top-inflow mode), initial concentrations (5-20 mg/L) of Pb(II), and bed depths (20-60 cm). The results indicated that the slower inflow rate (0.159 L/min), down-inflow mode, lower initial concentration (5 mg/L), and higher bed depth (60 cm) prolonged breakthrough times ( t b ) and saturation times ( t s ). Compared to the top-inflow mode, the down-inflow mode guaranteed enough contact between Hydrogel-I and Pb(II). The values of adsorption capacity at t b , t s, and the removal efficiency under the down-inflow mode were higher than that under top-inflow mode by 2.33, 0.78, and 0.07 times, respectively. Hydrogel-I beads exhibited better adsorption performance than other adsorbents by comparing the rate constant ( k AB ) and the adsorption capacity ( N 0 ). The k AB and N 0 of Hydrogel-I beads were calculated to be 0.0034 L/(mg·min -1 ) and 678 mg/L. Hydrogel-I beads showed good regeneration ability in a three-adsorption-desorption cycle. Meanwhile, FT-IR analysis showed that the groups of -NH/-NH 2 , C=S, and C-S were proved to be the adsorption sites. This study could prove valuable insight into the practical application of Hydrogel-I for dynamic removal of Pb(II) in an inflow-through column.

Amorphousness effectively improves the electron transfer rate of zero-valent iron. In this study, a novel kaolinite loading amorphous zero-valent iron composite (K-AZVI) was prepared and applied to the remediation of soils with cadmium (Cd) pollution concentrations of 20, 50, and 100 mg/kg respectively. The results showed that the application of K-AZVI increased the pH and cation exchange capacity (CEC) of soil, and decreased the dissolved organic carbon (DOC) and organic matter (OM) of soil, thus indirectly promoting the adsorption of Cd in the soil. After 28 days of stabilization, the stabilizing efficiency of K-AZVI on the water-soluble Cd content in soil reached 98.72 %. Under the amendment of 0.25 %-1.0 % (w/w), the available Cd content in 20-100 mg/kg contaminated soil decreased by 46.47 %-62.23 %, 24.10 %-41.52 %, and 16.09 %-30.51 % respectively compared with CK. More importantly, the addition of K-AZVI promoted the transformation of 33.18 %-48.42 % exchangeable fraction (EXC) to 10.09 %-20.14 % residual fraction (RES), which increased the abundance and diversity of soil bacterial communities. Comprehensive risk assessment showed that adding 1.0 % K-AZVI provided the best remediation on contaminated soil. In addition, the results of scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS) of K-AZVI before and after the reaction showed that the stabilization mechanism of K-AZVI to Cd in soil is mainly the stable metal species (Cd(OH) 2 , CdO and CdFe 2 O 4 ) formed by the direct complexation and coprecipitation of a large number of iron oxides formed by the rapid corrosion of amorphous zero-valent iron (AZVI). Overall, this work provides a promising approach to the remediation of Cd-contaminated soil using K-AZVI composites., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier B.V. All rights reserved.)

As a generally existing component in industrial streams, H 2 O usually inhibits the catalytic degradation efficiency of volatile organic compounds (VOCs) greatly. Here, we propose a novel strategy that accelerates the H 2 O dissociation and facilitates positive feedbacks during VOC oxidation by fabricating citric acid (CA)-assisted Pt(K)-Mn 2 O 3 /SiO 2 (Pt-Mn/KS- x CA). Results reveal that the complexation of carboxyl groups of citric acid with Mn cations leads to the formation of small Mn 2 O 3 (4.1 ± 0.2 nm) and further enhances the Mn-O-Pt interaction (strengthened by the Si-O-Mn interaction), which can transfer more electrons from Pt-Mn/KS-6CA to H 2 O, thus facilitating its breaking of covalent bonds. It subsequently produces abundant surface hydroxyl groups, improving the adsorption and activation abilities of acetone reactant and ethanol intermediate. Attributing to these, the acetone turnover frequency value of Pt-Mn/KS-6CA is 1.8 times higher than that of Pt-Mn/KS at 160 °C, and this multiple changes to 6.3 times in the presence of H 2 O. Remarkably, acetone conversion over Pt-Mn/KS-6CA increases by up to 14% in the presence of H 2 O; but it decreases by up to 26% for Pt-Mn/KS due to its weak dissociation ability and high adsorption capacity toward H 2 O. This work sheds new insights into the design of highly efficient catalytic materials for VOC degradation under humid conditions.

Recently, atomically precise metal nanoclusters (NCs) become a new class of photosensitizer for light energy conversion in metal-cluster-sensitized semiconductor (MCSS) system. However, fundamental understanding for the suitable combination of NCs and semiconductor is still unclear. Aside from aspects of light harvesting, energy level alignment and catalytic activity, interfacial interaction behavior at NCs/semiconductor interface is also crucial due to its important influence in charge transportation. In this work, the interface interaction between Au NCs and TiO 2 is examined by precise transformation of Au NCs from Au 22 (SG) 18 to Au 18 (SG) 14 , as well as its effect on photocatalytic hydrogen production activity. From the optical, charge transport and solid-states spectroscopy analyses, it is able to display that precisely tuning the number of core atoms from Au 22 (SG) 18 to Au 18 (SG) 14 results in the strong interface interaction between Au NCs and TiO 2 , reflecting in high difference of work function and modified surface band bending of TiO 2 , therefore promoting the injection of electrons from NCs to TiO 2 and reducing interfacial charges recombination. As a result, Au 18 (SG) 14 /TiO 2 shows higher hydrogen generation rate than Au 22 (SG) 18 /TiO 2 under light irradiation. This work would provide new insights into rational combination of metal NCs with semiconductor and highlights the overlooked effect of interfacial interaction behavior on light energy conversion., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 Elsevier Inc. All rights reserved.)

Light alkanes make up a class of widespread volatile organic compounds (VOCs), bringing great environmental hazards and health concerns. However, the low-temperature catalytic destruction of light alkanes is still a great challenge to settle due to their high reaction inertness and weak polarity. Herein, a Co 3 O 4 sub-nanometer porous sheet (Co 3 O 4 -SPS) was fabricated and comprehensively compared with its bulk counterparts in the catalytic oxidation of C 3 H 8 . Results demonstrated that abundant low-coordinated Co atoms on the Co 3 O 4 -SPS surface boost the activation of adsorbed oxygen and enhance the catalytic activity. Moreover, Co 3 O 4 -SPS has better surface metal properties, which is beneficial to electron transfer between the catalyst surface and the reactant molecules, promoting the interaction between C 3 H 8 molecules and dissociated O atoms and facilitating the activation of C-H bonds. Due to these, Co 3 O 4 -SPS harvests a prominent performance for C 3 H 8 destruction, 100% of which decomposed at 165 °C (apparent activation energy of 49.4 kJ mol -1 ), much better than the bulk Co 3 O 4 (450 °C and 126.9 kJ mol -1 ) and typical noble metal catalysts. Moreover, Co 3 O 4 -SPS also has excellent thermal stability and water resistance. This study deepens the atomic-level insights into the catalytic capacity of Co 3 O 4 -SPS in light alkane purification and provides references for designing efficacious catalysts for thermocatalytic oxidation reactions., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Amorphous zerovalent iron (AZVI) has gained considerable attention due to its remarkable reactivity, but there is limited research on sulfidated amorphous zerovalent iron (SAZVI) and the influence of different sulfur precursors on its reactivity remains unclear. In this study, SAZVI materials with an amorphous structure were synthesized using various sulfur precursors, resulting in significantly increased specific surface area and hydrophobicity compared to AZVI. The Cr(VI) removal efficiency of SAZVI-Na 2 S, which exhibited the most negative free corrosion potential (-0.82 V) and strongest electron transfer ability, was up to 8.5 times higher than that of AZVI. Correlation analysis revealed that the water contact angle ( r = 0.87), free corrosion potential ( r = -0.92), and surface Fe(II) proportion ( r = 0.98) of the SAZVI samples played crucial roles in Cr(VI) removal. Furthermore, the enhanced elimination ability of SAZVI-Na 2 S was analyzed, primarily attributed to the adsorption of Cr(VI) by the FeS x shell, followed by the rapid release of internal electrons to reduce Cr(VI) to Cr(III). This process ultimately led to the precipitation of FeCr 2 O 4 and Cr 2 S 3 on the surface of SAZVI-Na 2 S, resulting in their removal from the water. This study provides insights into the influence of sulfur precursors on the reactivity of SAZVI and offers a new strategy for designing highly active AZVI for efficient Cr(VI) removal.

Background: The risk factors for the recurrent choledocholithiasis after endoscopic retrograde cholangiopancreatography (ERCP) have not been well studied. The aim of this study was to explore the risk factors of recurrent choledocholithiasis., Methods: We carried out a retrospective analysis of data collected between January 1, 2010 and January 1, 2020. Univariate analysis and multivariate analysis were used to explore the independent risk factors of recurrent choledocholithiasis following therapeutic ERCP., Results: In total, 598 patients were eventually selected for analysis, 299 patients in the recurrent choledocholithiasis group and 299 patients in the control group. The overall rate of recurrent choledocholithiasis was 6.91%. Multivariate analysis showed that diabetes [odds ratio (OR) = 3.677, 95% confidence interval (CI): 1.875-7.209; P < 0.001], fatty liver (OR = 4.741, 95% CI: 1.205-18.653; P = 0.026), liver cirrhosis (OR = 3.900, 95% CI: 1.358-11.201; P = 0.011), history of smoking (OR = 3.773, 95% CI: 2.060-6.908; P < 0.001), intrahepatic bile duct stone (OR = 4.208, 95% CI: 2.220-7.976; P < 0.001), biliary stent (OR = 2.996, 95% CI: 1.870-4.800; P < 0.001), and endoscopic papillary balloon dilation (EPBD) (OR = 3.009, 95% CI: 1.921-4.715; P < 0.001) were independent risk factors of recurrent choledocholithiasis. However, history of drinking (OR = 0.183, 95% CI: 0.099-0.337; P < 0.001), eating light food frequently (OR = 0.511, 95% CI: 0.343-0.760; P = 0.001), and antibiotic use before ERCP (OR = 0.315, 95% CI: 0.200-0.497; P < 0.001) were independent protective factors of recurrent choledocholithiasis., Conclusions: Patients with the abovementioned risk factors are more likely to have recurrent CBD stones. Patients who eat light food frequently and have a history of drinking are less likely to present with recurrent CBD calculi., (Copyright © 2022 First Affiliated Hospital, Zhejiang University School of Medicine in China. Published by Elsevier B.V. All rights reserved.)

Background: Diffuse intrinsic pontine gliomas (DIPGs) are rare and fatal pediatric brainstem gliomas with no cure. Chimeric antigen receptor (CAR)-engineered natural killer (NK) cells have been proven effective in treating glioblastoma (GBM) in preclinical studies. However, there are no relevant studies on the CAR-NK treatment for DIPG. Our study is the first to evaluate the anti-tumor activity and safety of GD2-CAR NK-92 cells treatment for DIPG., Methods: Five patient-derived DIPG cells and primary pontine neural progenitor cell (PPC) were used to access disialoganglioside GD2 expression. Cell killing activity of GD2-CAR NK-92 cells was analyzed by in vitro cytotoxicity assays. Two DIPG patient-derived xenograft models were established to detect the anti-tumor efficacy of GD2-CAR NK-92 cells in vivo ., Results: Among the five patient-derived DIPG cells, four had high GD2 expression, and one had low GD2 expression. In in vitro assays, GD2-CAR NK-92 cells could effectively kill DIPG cells with high GD2 expression while having limited activity against DIPG cells with low GD2 expression. In in vivo assays, GD2-CAR NK-92 cells could inhibit tumor growth in TT150630 DIPG patient-derived xenograft mice (high GD2 expression) and prolong the overall survival of the mice. However, GD2-CAR NK-92 showed limited anti-tumor activity for TT190326DIPG patient-derived xenograft mice (low GD2 expression)., Conclusion: Our study demonstrates the potential and safety of GD2-CAR NK-92 cells for adoptive immunotherapy of DIPG. The safety and anti-tumor effect of this therapy need to be further demonstrated in future clinical trials., Competing Interests: Author XZ is/was employed by Yufan Biotechnology Beijing Co., LTD, Beijing, China. The remaining authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2023 Zuo, Li, He, Wang, Zheng, Liu, Wu, Zhang, Liao and Zhang.)

A concise total synthesis of the complex guanidinium toxin KB343 is reported traversing through an unusual sequence of chemoselective transformations and strategic skeletal reorganization. The absolute configuration is confirmed through an enantioselective route, and the structures of all key intermediates and the natural product itself are unassailably confirmed through X-ray crystallographic analysis.

The total syntheses of nine grayanane diterpenoids, namely, GTX-II ( 1 ), GTX-III ( 2 ), rhodojaponin III ( 3 ), GTX-XV ( 4 ), principinol D ( 5 ), iso-GTX-II ( 6 ), 1,5-seco-GTX-Δ 1,10 -ene (7), and leucothols B ( 8 ) and D ( 9 ), that belong to five distinct subtypes, were disclosed in a divergent manner. Among them, six members were accomplished for the first time. The concise synthetic approach features three key transformations: (1) an oxidative dearomatization-induced [5 + 2] cycloaddition/pinacol rearrangement cascade to assemble the bicyclo[3.2.1]octane carbon framework (CD rings); (2) a photosantonin rearrangement to build up the 5/7 bicycle (AB rings) of 1- epi -grayanoids; and (3) a Grob fragmentation/carbonyl-ene process to access four additional subtypes of grayanane skeletons. Density functional theory calculations were performed to elucidate the mechanistic origins of the crucial divergent transformation, which combined with late-stage synthetic findings provided insights into the biosynthetic relationships between these diverse skeletons.

Amorphous zero-valent iron (AZVI) has attracted wide attention due to its high-efficiency reduction ability. However, the effect of different EDA/Fe(II) molar ratios on the physicochemical properties of the synthesized AZVI requires further investigation. Herein, series of AZVI samples were prepared by changing the molar ratio of EDA/Fe(II) to 1/1 (AZVI@1), 2/1 (AZVI@2), 3/1 (AZVI@3), and 4/1 (AZVI@4). When the EDA/Fe(II) ratio increased from 0/1 to 3/1, the Fe 0 proportion on the AZVI surface increased from 26.0 to 35.2% and the reducing ability was enhanced. As for AZVI@4, the surface was severely oxidized to form a large amount of Fe 3 O 4 , and the Fe 0 content was only 74.0%. Moreover, the removal ability of Cr(VI) was in the order AZVI@3 > AZVI@2 > AZVI@1 > AZVI@4. The isothermal titration calorimetry results revealed that the increase of the molar ratio of EDA/Fe(II) would lead to the stronger complexation of EDA with Fe(II), which resulted in the gradual decrease of the yield of AZVI@1 to AZVI@4 and the gradual deterioration of water pollution after the synthesis. Therefore, based on the evaluation of all indicators, AZVI@2 was the optimal material, not only because its yield was as high as 88.7% and the secondary water pollution level was low, but most importantly, the removal efficiency of Cr(VI) by AZVI@2 was excellent. Furthermore, the actual Cr(VI) wastewater with the concentration of 14.80 mg/L was treated with AZVI@2, and the removal rate of 97.0% was achieved after only a 30 min reaction. This work clarified the effect of different ratios of EDA/Fe(II) on the physicochemical properties of AZVI, which provided insights for guiding the reasonable synthesis of AZVI and is also conducive to investigating the reaction mechanism of AZVI in Cr(VI) remediation.

Volatile organic amines are a category of typical volatile organic compounds (VOCs) extensively presented in industrial exhausts causing serious harm to the atmospheric environment and human health. Monometallic Pd and Cu-based catalysts are commonly adopted for catalytic destruction of hazardous organic amines, but their applications are greatly limited by the inevitable production of toxic amide and NO x byproducts and inferior low-temperature activity. Here, a CuO/Pd@SiO 2 core-shell-structured catalyst with diverse functionalized active sites was creatively developed, which realized the total decomposition of n -butylamine at 260 °C with a CO 2 yield and N 2 selectivity reaching up to 100% and 98.3%, respectively (obviously better than those of Pd@SiO 2 and CuO/SiO 2 ), owing to the synergy of isolated Pd and Cu sites in independent mineralization of n -butylamine and generation of N 2 , respectively. The formation of amide and short-chain aliphatic hydrocarbon intermediates via C-C bond cleavage tended to occur over Pd sites, while the C-N bond was prone to breakage over Cu sites, generating NH 2 · species and long free-N chain intermediates at low temperatures, avoiding the production of hazardous amide and NO x . The SiO 2 channel collapse and H + site production resulted in the formation of N 2 O via suppressing NH 2 · diffusion. This work provides critical guidance for a rational fabrication of catalysts with high activity and N 2 selectivity for environmentally friendly destruction of nitrogen-containing VOCs.

The evaluation of the poisoning effect of complex components in practical gas on DCM (dichloromethane) catalytic ozonation is of great significance for enhancing the technique's environmental flexibility. Herein, Ca, Pb, As, and NO/SO 2 were selected as a typical alkaline-earth metal, heavy metal, metalloid, and acid gas, respectively, to evaluate their interferences on catalytic behaviors and surface properties of an optimized urchin-like CuMn catalyst. Ca/Pb loading weakens the formation of oxygen vacancies, oxygen mobility, and acidity due to the fusion of Mn-Ca/Pb-O, leading to their inferior catalytic performance with poor CO 2 selectivity and mineralization rate. Noticeably, the presence of As induces excessively strong acidity, facilitating the inevitable formation of byproducts. Catalytic co-ozonation of NO/DCM is achieved with stoichiometric ozone addition. Unfortunately, SO 2 introduction brings irreversible deactivation due to strong competition adsorption and the loss of active sites. Unexpectedly, Ca loading protects active sites from an attack by SO 2 . The formation of unstable sulfites and the released Mn-O structure offset the negative effect from SO 2 . Overall, the catalytic ozonation of DCM exhibits a distinctive priority in the antipoisoning of metals with the maintenance of DCM conversion. The construction of more stable acid sites should be the future direction of catalyst design; otherwise, catalytic ozonation should be arranged together with post heavy metal capture and a deacidification system.

In order to enhance the catalytic activity and improve the stability of Mn-Al oxides in acetone oxidation, it is interesting to have found that modulating and accelerating the rate-limiting step by Al substitution rather than just mixing of Mn and Al is crucial for hydrocarbon efficient catalytic destruction. Here, a series of Mn-Al oxides with different Al substitution ratios were prepared by a scalable and facile hydrothermal-redox strategy. The reaction rate, selectivity, and stability of the representative α-MnO 2 catalyst in acetone oxidation can be remarkably promoted by simple replacing of the partial framework Mn with Al, which changes the rate-limiting step from acetic acid dissociation to ethanol decomposition accelerated by H 2 O molecules. Among them, MnAl 0.5 displays the best catalytic performance with 90% of acetone converted at just 165 °C and a remarkable CO 2 yield. DFT results suggest that the p y and p x orbitals of the O element take part in the formation of the carbonyl group when the intermediate of removing H* from ethanol reacts with the hydroxyl group of H 2 O. The d xz orbital of Mn with p-electron of Al plays a vital role in the rate-limiting step. The work provides new insights into engineering catalysts for industrial VOC efficient and economical mineralization.

Background: Exact roles of many metabolic regulators in rheumatoid arthritis (RA) are to be clarified. This study aimed to further characterize the impacts of silent information regulator 1 (SIRT1) status changes on this disease., Methods: Fluctuation pattern of SIRT1 expression in adjuvant-induced arthritis (AIA) rats was monitored using periodically collected white blood cells. Another bath of AIA rats were treated by SIRT1 agonist resveratrol. Blood from these rats was used to separate monocytes and plasma, which were subjected to polymerase chain reaction (PCR), enzyme linked immunosorbent assay (ELISA), and biochemical analyses. Clinical implication of SIRT1 activation was verified by treating AIA rat monocytes with SIRT1 agonist and overexpression vector in vitro., Results: SIRT1 deficiency occurred in AIA rats, which was accompanied with down-regulation of interleukin 10 (IL-10) and arginase-1 (ARG-1). Resveratrol eased oxidative stress and increased IL-10 production in vivo. Results of ELISA analysis demonstrated that resveratrol attenuated AIA severity in rats. Furthermore, it restored the altered levels of triglyceride, lactate and pyruvate in blood. Resveratrol promoted IL-10 production, and suppressed glycolysis of AIA monocytes cultured in vitro. SIRT1 overexpression similarly reshaped differentiation profile of AIA monocytes, evidenced by changes in metabolism indicators, IL-10 production and AMP-activated protein kinase (AMPK) pathway status. Although overexpressing SIRT1 in normal cells did not affect glycolysis significantly, it attenuated AMPK antagonist-caused abnormality., Conclusion: SIRT1 deficiency is implicated in AIA-related immune abnormality and metabolism alteration. Activating this signaling with resveratrol would impair the inflammatory polarization of monocytes, and consequently ease the severity of RA., Competing Interests: The authors report no declarations of interest., (© 2022 Wang et al.)

A modular total synthesis of kibdelomycin is disclosed that should enable structure-activity relationship (SAR) studies of this interesting class of antibiotics. The route uses simple building blocks and addresses lingering questions about its structural assignment and relationship to amycolamicin, a recently described natural product reported to have a similar structure. Initial antibacterial assays reveal that both C-22 epimers (the N-glycosidic linkage) of the natural product have similar activity while structurally truncated analogs lose activity., (© 2022 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Morinda officinalis oligosaccharides (MOO) are an oral drug approved in China for the treatment of depression in China. However, MOO is hardly absorbed so that their anti-depressant mechanism has not been elucidated. Here, we show that oral MOO acted on tryptophan → 5-hydroxytryptophan (5-HTP) → serotonin (5-HT) metabolic pathway in the gut microbiota. MOO could increase tryptophan hydroxylase levels in the gut microbiota which accelerated 5-HTP production from tryptophan; meanwhile, MOO inhibited 5-hydroxytryptophan decarboxylase activity, thus reduced 5-HT generation, and accumulated 5-HTP. The raised 5-HTP from the gut microbiota was absorbed to the blood, and then passed across the blood-brain barrier to improve 5-HT levels in the brain. Additionally, pentasaccharide, as one of the main components in MOO, exerted the significant anti-depressant effect through a mechanism identical to that of MOO. This study reveals for the first time that MOO can alleviate depression via increasing 5-HTP in the gut microbiota., (© 2022 Chinese Pharmaceutical Association and Institute of Materia Medica, Chinese Academy of Medical Sciences. Production and hosting by Elsevier B.V.)

The development of highly active single-atom catalysts (SACs) and identifying their intrinsic active sites in oxidizing industrial hazardous hydrocarbons are challenging prospects. Tuning the electronic metal-support interactions (EMSIs) is valid for modulating the catalytic performance of SACs. We propose that the modulation of the EMSIs in a Pt 1 -CuO SAC significantly promotes the activity of the catalyst in acetone oxidation. The EMSIs promote charge redistribution through the unified Pt-O-Cu moieties, which modulates the d-band structure of atomic Pt sites, and strengthens the adsorption and activation of reactants. The positively charged Pt atoms are superior for activating acetone at low temperatures, and the stretched Cu-O bonds facilitate the activation of lattice oxygen atoms to participate in subsequent oxidation. We believe that this work will guide researchers to engineer efficient SACs for application in hydrocarbon oxidation reactions., (© 2022 Wiley-VCH GmbH.)

The first enantioselective decarboxylative Negishi-type alkylations of α-oxy carboxylic acids are reported via the intermediacy of redox-active esters (RAEs). This transformation enables a radical-based retrosynthesis of seemingly trivial enantiopure dialkyl carbinols. This article includes a discussion of the history of such couplings, the retrosynthetic ramifications of such a coupling, the development of general conditions, and an extensive series of applications that vividly demonstrate how it can simplify synthesis.

Wheat is one of the most important food crops worldwide. Even though wheat yields have increased considerably in recent years, future wheat production is predicted to face enormous challenges due to global climate change and new versions of diseases. CRISPR/Cas technology is a clean gene technology and can be efficiently used to target genes prone to biotic stress in wheat genome. Herein, the published research papers reporting the genetic factors corresponding to stripe rust, leaf rust, stem rust, powdery mildew, fusarium head blight and some insect pests were critically reviewed to identify negative genetic factors (Susceptible, S genes) in bread wheat. Out of all reported genetic factors related to these disease, 33 genetic factors (S genes) were found as negative regulators implying that their down-regulation, deletion or silencing improved disease tolerance/resistance. The results of the published studies provided the concept of proof that these 33 genetic factors are potential targets for CRISPR/Cas knockdowns to improve genetic tolerance/resistance against these diseases in wheat. The sequences of the 33 genes were retrieved and re-mapped on the latest wheat reference genome IWGSC RefSeq v2.1. Phylogenetic analysis revealed that pathogens causing the same type of disease had some common conserved motifs and were closely related. Considering the significance of these disease on wheat yield, the S genes identified in this study are suggested to be disrupted using CRISPR/Cas system in wheat. The knockdown mutants of these S genes will add to genetic resources for improving biotic stress resistance in wheat crop., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2022 Taj, Sajjad, Li, Yasmeen, Mubarik, Kaniganti and He.)

Developing economic and applicable catalysts with elegant chlorine resistance and organic byproduct inhibition capability is of great significance for chlorinated volatile organic compounds (Cl-VOCs) eco-friendly purification. Here, ternary Ce x Sr 1- x TiO 3 catalysts with tunable surface acidity and oxygen species mobility were creatively fabricated using the hollow tubular-structured fruit hair of Platanus (FHP; a widespread greenery waste) as the scaffolding biotemplate. It is shown that the oxygen vacancy (O v ) triggered by the presence of Ce can optimize the synergy between the Lewis acid sites (LAS) and Brønsted acid sites (BAS). High concentration of O v and BAS promotes the C-Cl cleavage of chlorobenzene (CB) and accelerates the desorption of Cl • radicals as inorganic chlorine. Simultaneously, the strong electron transfer within Ti-Ce-Sr linkage increases the acidity of LAS, resulting in the superior reducibility of Ce 0.4 Sr 0.6 TiO 3 and facilitating the deep oxidation of dechlorination intermediates. Additionally, the spatial confinement of the tubular structure remarkably accelerates the CB flow rate and reduces the residence time of byproducts over the prepared catalysts. Owing to these, CB can be efficiently destructed over Ce 0.4 Sr 0.6 TiO 3 with selectivity of CO 2 and inorganic chlorine dramatically enhanced, respectively, approximately 16 and 21 times at 275 °C compared to those of pure SrTiO 3 . The present work provides a feasible and promising strategy for engineering efficient catalysts for heterogeneous thermocatalytic reactions for industrial-scale Cl-CVOC destruction.

Cervical cancer (CC) is a common malignancy in gynecology. Emerging evidence has demonstrated that circular RNAs (circRNAs) act as vital mediators in CC. However, the roles of circRNA ring finger protein 121 (circRNF121) in CC are largely unknown. Herein, we focused on the exact function and underlying mechanism of circRNF121 in CC development. Our results showed that circRNF121 was highly expressed in CC tissues and cells. Knockdown of circRNF121 suppressed cell growth, metastasis, epithelial-mesenchymal transition (EMT), autophagy, and wnt/β-catenin pathway in CC cells in vitro and blocked tumor formation in vivo. For mechanism investigation, circRNF121 could affect activating transcription factor 2 (ATF2) expression by decoying miR-153-3p, thereby accelerating CC cell development. In conclusion, circRNF121 exerted the tumor-suppressive role in CC progression by altering miR-153-3p/ATF2 axis. These results suggested that circRNF121 might be a possible circ-targeted therapy for patients with CC., (© 2022 Wiley Periodicals LLC.)

Though the highest CO 2 capture capacity belongs to liquid amine-solutions, solid matters capable of CO 2 capture are also highly sought, providing that, they offer at least analogous CO 2 adsorption capacity and CO 2 /N 2 selectivity. Herein, a surprisingly high-performance Ni-based metal-organic framework for CO 2 adsorption, namely MOF-74(Ni), was synthesized by a facile condensation reflux approach. It was found that the structure and CO 2 adsorption isosteric heat of MOF-74(Ni) could tune upon varying the synthesis duration under various temperatures. The optimized MOF-74(Ni)-24-140 (synthesized at 140 °C for 24 h) displays outstanding CO 2 adsorption capacity of 8.29/6.61 mmol/g at 273/298 K under normal pressure of 1.0 bar, several times higher than previously reported MOF-74-Ni (2.0/2.1 times), UTSA-16 (1.5/1.6 times), and DA-CMP-1 (3.6/4.9 times) under similar conditions. The excellent CO 2 capture capacity is associated to the abundant adsorption sites (mainly arising from the cationic Ni 2+ ions) and narrow micropore channels (mainly arising from the cage structure of Ni 2+ ions coordinated with organic linkers). Offering a high CO 2 selectivity (CO 2 /N 2  = 49) and a well-tuned isosteric heat of CO 2 adsorption (27-52 kJ/mol) besides its decent CO 2 capture capacity, MOF-74(Ni) strongly stands out as an efficient and strong CO 2 capturing material with industrial scale applicability., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Realizing the simultaneous adsorption and activation of O 2 and reactants over supported noble metal catalysts is crucial for the oxidation of organic hydrocarbons. Herein, we report a facile one-step ethylene glycol reduction method to synthesize difunctional Au(OH)K x sites, which were anchored on a hierarchical hollow MFI support and adopted for acetone decomposition. The alkali ion-associated adjacent surface hydroxyl groups were coordinated with Au nanoparticles, resulting in partially oxidized Au 1+ sites with improved dispersion. The results obtained from exclusive ex situ and in situ experiments illustrated that the proper content of K and hydroxyl groups significantly enhanced the adsorption of surface O 2 and acetone molecules around the Au sites simultaneously, whereas the excess K species inhibited the catalytic performance by blocking the pore structure and decreasing the acidity of catalysts. The Au(OH)K 0.7 /h-MFI catalyst exhibited the highest efficiency for acetone oxidation, over which 1500 ppm acetone can be completely oxidized at just 280 °C with an extremely low activation energy of 32.5 kJ mol -1 . The carbonate species were detected as the main intermediates during acetone decomposition over the difunctional Au(OH)K x sites through a Langmuir - Hinshelwood (L - H) mechanism. This finding paves the way for designing and constructing efficient functional active sites for the complete oxidation of hydrocarbons., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

NO x and toluene have been identified as the dominant air pollutants in solid wasted combustion, and it is of great importance to remove these two pollutants simultaneously. Here, we found that Mn/CeO 2 and Mn/TiO 2 exhibited a bifunctional property in both NO reduction and toluene oxidation, and both of which could achieve 80% of conversion rate in NO reduction and toluene oxidation processes. However, the activity of both Mn/CeO 2 and Mn/TiO 2 decreased in simultaneous removal of NO x and toluene compared with separate NO x reduction and toluene oxidation. This indicates that there is a mutual inhibition between NO x reduction and toluene oxidation in simultaneous removal process over Mn-based catalysts, attributing to the competitive adsorption and utilization of active oxygen. In detail, the adsorption of toluene occupied the Lewis acid sites and restrained the NH 3 adsorption. Meanwhile, the competitive utilization of active oxygen by NH 3 /NO x inhibited toluene oxidation to CO 2 by active oxygen species as the reaction between NH 3 /NO x and active oxygen species would occur more easily., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Zeolite-confined metal nanoparticles (NPs) have attracted much attention owing to their superior sintering resistance and broad applications for thermal and environmental catalytic reactions. However, the pore size of the conventional zeolites is usually below 2 nm, and reactants are easily blocked to access the active sites. Herein, a facile in situ mesoporogen-free strategy is developed to design and synthesize palladium (Pd) NPs enveloped in a single-crystalline zeolite (silicalite-1, S-1) with intra-mesopores (termed Pd@IM-S-1). Pd@IM-S-1 exhibited remarkable light alkanes deep oxidation performances, and it should be attributed to the confinement and guarding effect of the zeolite shell and the improvement in mass-transfer efficiency and active metal sites accessibility. The Pd-PdO interfaces as a new active site can provide active oxygen species to the first C-H cleavage of light alkanes. This work exemplifies a promising strategy to design other high-performance intra-crystalline mesoporous zeolite-confined metal/metal oxide catalysts for high-temperature industrial thermal catalysis., (© 2022. This is a U.S. Government work and not under copyright protection in the US; foreign copyright protection may apply.)

Achieving excellent efficiency to mineralize volatile organic compounds (VOCs) under nonthermal plasma catalysis (NTP-catalysis) systems tremendously relies on the catalyst design. Herein, we report a dual-template strategy for synthesizing a core-shell structured nitrogen-enriched hollow hybrid carbon (N-HHC) by a facile pyrolysis of a Mn-ZIF-8@polydopamine core-shell precursor. N-HHC exhibits a remarkable plasma synergy effect and superior degradation efficiency for toluene (up to 90% with a specific input energy of 281 J/L), excellent CO 2 selectivity (>45%), and byproduct-inhibiting capability. Such outstanding functionality of the developed N-HHC is uniquely attributed to its hollow multistage and channeling structure, high concentration of O 3 -decomposing species (pyrrolic and oxide pyridinic-N), and abundant ZnO active sites. Shedding light on an efficient synthetic strategy for designing an advanced nanocatalyst with enhanced VOC destruction in the NTP-catalysis system, the present results could be extended to design other N-doped metal/metal oxide-decorated hollow porous carbons for environment-related applications.

Photochromic materials coupled with photoswitchable luminescence functionalities are of particular interest due to their potential applications in switches and optical memory devices. However, the construction of such materials, especially those with two-color emission states, is still challenging. In this context, a rare Zn 7 cluster-based host-guest MOF material, (bbmp)[Zn 7 (IPA) 6 (OH) 4 (H 2 O) 2 ] (1) (H 2 IPA = isophthalic acid, bbmp·2I = 4,4'-([1,1'-biphenyl]-4,4'-diyl)bis(1-methylpyridin-1-ium) diiodide), was prepared by encapsulating an organic cation into an anionic MOF produced from zinc cations and isophthalic acid ligands, which exhibits reversible naked detectable photochromic properties varying from yellow to green upon UV-Vis light irradiation. The photoactive guest bbmp 2+ and the short O⋯N + distances between the oxygen atoms of the carboxylate groups and the pyridine ring play a crucial role in the photochromism of this compound. More interestingly, the luminescence color of this cluster-based host-guest material can be reversibly switched from green to blue upon irradiation, exhibiting photoswitchable luminescence properties.

Gemcitabine (GEM) resistance is a major challenge for chemotherapy of pancreatic cancer. Previous studies have reported on the role of long noncoding RNA (lncRNA) in tumorigenesis of pancreatic cancer, however, the involvement of lncRNA in the development of GEM resistance of pancreatic cancer remains unclear. In the present study, we demonstrated that the antisense RNA1 of HIF1α (HIF1A-AS1) was significantly elevated in the GEM-resistant pancreatic cancer cells. Gain- and lost-of-function experiments validated that HIF1A-AS1 promoted GEM resistance of pancreatic cancer cells both in vitro and vivo . We further revealed that HIF1A-AS1 upregulated HIF1α expression and thus promoted glycolysis to enhance GEM resistance of pancreatic cancer cells. Mechanistically, HIF1A-AS1 facilitated the interaction between serine/threonine kinase AKT and Y-box-binding protein 1 (YB1), which promoted phosphorylation of YB1 (pYB1). Meanwhile, HIF1A-AS1 recruited pYB1 to HIF1α mRNA that consequently promoted translation of HIF1α. Furthermore, HIF1α promoted HIF1A-AS1 transcription by directly binding to the HIF1α response element in the promoter area of HIF1A-AS1 to form a positive feedback. Consistently, both HIF1A-AS1 and HIF1α were upregulated in pancreatic cancer tissues and associated with poor overall survival. Together, our results underline a reciprocal loop of HIF1A-AS1 and HIF1α that contributes to GEM resistance of pancreatic cancer and indicate that HIF1A-AS1 might serve as a novel therapeutic target for GEM resistance of pancreatic cancer. SIGNIFICANCE: These findings show that a reciprocal feedback of HIF1A-AS1 and HIF1α promotes gemcitabine resistance of pancreatic cancer, which provides an applicable therapeutic target., (©2021 American Association for Cancer Research.)

Oxygen vacancy plays an important role in adsorption and activation of oxygen species and therefore promotes the catalytic performance of materials in heterogeneous oxidation reactions. Here, a series of K-doped ɑ-MnO 2 materials with different K loadings were synthesized by a reproducible post processing process. Results show that the presence of K + enhances the reducibility and oxygen vacancy concentration of ɑ-MnO 2 due to the break of charge balance and the formation of low valence Mn species. 4-K/MnO 2 material exhibits the highest toluene oxidation activity and satisfied long-term stability and water resistance owing to its superior reducibility and abundant surface absorbed oxygen (O ads ). In situ DRIFTS demonstrate that O ads greatly accelerates toluene dehydrogenation rate and promotes benzoate formation, enhancing the activation and decomposition of toluene molecules. Moreover, the CC cleavage of benzene ring (forming maleic anhydride) is the rate-determining step of toluene oxidation, which can be easily occurred over 4-K/MnO 2 ., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Alkali metal potassium is conducive to structure promotion and electronic modulation in metal oxides. Here, K species was successfully introduced into α-MnO 2 via in situ synthesis (Pre-K/MnO 2 ) and hydrothermal impregnation method (Post-K/MnO 2 ) with target to boost the low-temperature reactivity and deep destruction efficiency for toluene oxidation. Results reveal that Post-K/MnO 2 possesses the highest catalytic activity with toluene (1000 ppm) totally mineralized at just 258 °C, achieving over 70 °C of temperature reduction than that of Pre-K/MnO 2 . K specie shows obvious charge transfer balance ability in MnO 2 , forming MnO 6 -K-MnO 6 bridging bond and leading to more uniform energy of Mn-O bonds. High electron density of K + can promote the activation of oxygen molecules, resulting in a better catalytic performance of toluene. Abundant Brønsted acid sites are beneficial for toluene adsorption and regeneration of hydroxyl on the surface, which promote the degradation of intermediates during toluene oxidation. Moreover, Post-K/MnO 2 shows satisfied catalytic performance under different space velocities and initial concentrations and humid condition. Density functional theory (DFT) calculation revealed the situation of oxygen vacancy and toluene/oxygen adsorption energy in catalysts with different K doping locations. Results showed that the adsorption energy is stronger when K located in large tunnel (0.46 × 0.46 nm), and it is easier to form oxygen vacancy while K entered the small tunnel (0.33 × 0.33 nm). The present work paves new insights into the designing of efficient transition metal oxide catalyst for VOC deep purification., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Background: The waiting time (WT) for a phlebotomy is directly related to patient satisfaction with a health service. However, the processing time varies widely depending on the type of patients. Monitoring of the WT alone may not enable an effective evaluation of the lean performance of the medical staff for patients with different characteristics. The objective of this study was to use process cycle efficiency (PCE) to assess the performance of an intelligent tube preparation system (ITPS) which automatically labeled test tubes and conducted patient rerouting for phlebotomy services, and to interpret the WT during peak hours., Methods: Three time periods were used. The baseline period was from 1 July to 31 July 2014. Phase 1 was after the establishment of the ITPS, with patients ≥80 years old being rerouted. In phase 2, patients ≥78 years old were rerouted. Those data were recorded with a calling system and ITPS, respectively., Results: PCE was significantly improved from 12.9% at baseline to 51.1% ( p < 0.001) in phase 1 and 53.0% ( p < 0.001) in phase 2. The WT of 16.9 min at baseline was reduced to 3.8 min in phase 1 ( p < 0.001), and 3.6 min in phase 2 ( p < 0.001). Moreover, the results showed that a WT < 10 min was consistent with a PCE ≥ 25%., Conclusions: Establishing an ITPS for phlebotomy can significantly increase PCE and shorten the WT. Furthermore, the PCE ≥ 25% could be a good assessment reference for the management of appropriate human resources for phlebotomy services, although it is a complex parameter.

The use of plasma-activated water (PAW) treatment is a promising technology that has many advantages, such as high efficiency, flexibility, environmental safety, and no residue. Thus, PAW has been applied in the agriculture industry to increase agricultural production. The application of PAW technology in agricultural production should emphasize its systematic nature, controllability, and operability, making it practical. This review systematically illustrates the production of PAW and the factors influencing it. The application of PAW in agriculture and its mechanism are discussed, including the effect on seed germination, the promotion of plant growth, and the control of plant diseases and pests. The implications of PAW for agriculture production and some of the related challenges are discussed. This review provides a deeper understanding of the viability of PAW technology in agriculture production. © 2021 Society of Chemical Industry., (© 2021 Society of Chemical Industry.)

A new variety of CdS/NiO core-shell p-n heterojunction is synthesized by in-situ chemically depositing NiO shell on single-crystal CdS nanorods for the first time. With this method, the range of NiO shell thickness can be accurately controlled within a few nanometers. The optimized CdS/NiO sample (CSN 0.5 ) with a NiO shell layer of 1.5 nm exhibits a highly efficient photocatalytic H 2 evolution rate of 731.7 μmol/h (corresponding to 243.9 mmol/g/h) without using co-catalyst, which is among the highest value of all the CdS-based photocatalysts. The apparent quantum efficiency (AQE) of CSN 0.5 at 365 nm wavelength reaches 28.19%. The remarkably enhanced photocatalytic performance can be attributed to a hydrogen spillover effect induced by ascorbic acid in CdS/NiO, which promotes the transmission of adsorbed H* from hydrogen-rich NiO (electron-poor region) to hydrogen-poor CdS (electron-rich region) where the adsorbed H* reacts in time with the photogenerated electron to produce H 2 , facilitating the H 2 evolution reaction. This work provides a method to promote the photocatalytic H 2 evolution reaction by using hydrogen spillover effect., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

Colorectal cancer (CRC) is the third most common cancer worldwide. Long non-coding RNA (lncRNA) small nucleolar RNA host gene 8 (SNHG8) acts as an oncogene in different types of cancer, including prostate, breast and ovarian cancer. SNHG8 promotes the tumorigenesis of CRC; however, its underlying molecular mechanism remains unclear. The present study aimed to explore the mechanism of SNHG8 on CRC development via various assays, including western blot, pull-down, PCR and immunofluorescence assays. The results of the present study demonstrated that SNHG8 expression was substantially upregulated in primary tumor tissues from The Cancer Genome Atlas dataset. Western blot and immunofluorescence analyses demonstrated that SNHG8 facilitated cell proliferation and autophagy in CRC cells. Notably, the function of SNHG8 in enhancing autophagy was dependent on autophagy-related gene 7 (ATG7). In addition, western blot analysis indicated that the effect of SNHG8 on autophagy in CRC cells was dependent on the miR-588/ATG7 axis. Taken together, the results of the present study suggest that SNHG8 promotes autophagy in CRC cells., Competing Interests: The authors declare that they have no competing interests., (Copyright © 2021, Spandidos Publications.)

The development of a versatile platform for the synthesis of 1,2-difunctionalized bicyclo[1.1.1]pentanes to potentially mimic ortho / meta -substituted arenes is described. The syntheses of useful building blocks bearing alcohol, amine, and carboxylic acid functional handles have been achieved from a simple common intermediate. Several ortho- and meta -substituted benzene analogs, as well as simple molecular matched pairs, have also been prepared using this platform. The results of in-depth ADME (absorption, distribution, metabolism, and excretion) investigations of these systems are presented, as well as computational studies which validate the ortho- or meta -character of these bioisosteres., Competing Interests: The authors declare no competing interest.

Fabricating of economical transitional metal oxide-based materials with satisfied low-temperature catalytic performance and application perspective is still a challenge in deep degradation of VOCs. Here, Mn-Cu bimetallic oxides were facilely prepared by one-step hydrothermal-redox method, which displayed much higher catalytic activity in toluene oxidation than those synthesized by hydrolysis-driven redox-precipitation or co-precipitation approach. It is shown that the lattice defect and oxygen vacancy concentration over prepared materials can be tuned by controlling Cu/Mn molar ratio. Amongst, spinel structured MnCu 0.5 exhibited the highest catalytic activity, superior durability and water resistance in toluene total oxidation owing to abundant surface adsorbed oxygen species, excellent low-temperature reducibility, and high amounts of Cu + and Mn 3+ . In detail, the reaction rate of MnCu 0.5 was over 9.0 times higher than that of MnCu 0.75 , MnCu 0.75 -P and MnCu 0.75 -H 2 O 2 at relative low temperature of 210 °C. The cyclic redox process with easier oxygen species mobility played a key role in the catalytic oxidation of toluene. Typical reaction intermediates as benzyl alcohol, benzaldehyde, benzene, phenol, and benzoquinone could be detected by PTR-MS, which further decomposed to acetone, ethanol, ketone, acetic acid, methanol, formaldehyde and acetaldehyde species by ring opening before total mineralization., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2021 Elsevier Inc. All rights reserved.)

The site-specific oxidation of strong C(sp 3 )-H bonds is of uncontested utility in organic synthesis. From simplifying access to metabolites and late-stage diversification of lead compounds to truncating retrosynthetic plans, there is a growing need for new reagents and methods for achieving such a transformation in both academic and industrial circles. One main drawback of current chemical reagents is the lack of diversity with regard to structure and reactivity that prevents a combinatorial approach for rapid screening to be employed. In that regard, directed evolution still holds the greatest promise for achieving complex C-H oxidations in a variety of complex settings. Herein we present a rationally designed platform that provides a step toward this challenge using N -ammonium ylides as electrochemically driven oxidants for site-specific, chemoselective C(sp 3 )-H oxidation. By taking a first-principles approach guided by computation, these new mediators were identified and rapidly expanded into a library using ubiquitous building blocks and trivial synthesis techniques. The ylide-based approach to C-H oxidation exhibits tunable selectivity that is often exclusive to this class of oxidants and can be applied to real-world problems in the agricultural and pharmaceutical sectors.

This paper reported when sulfamethazine (SMT) and antimony (Sb(V)) coexisted in aqueous solution at pH of 3.0, 5.0 and 7.0, the complexation between SMT and Sb(V) occurred. Such a complexation impeded the adsorption of Sb(V) on the black soil. The higher the solution pH value was, the more the amount of Sb(V) was prevented from adsorbing on the black soil. The maximum adsorption capacity (q m ) of Sb(V) at the presence of SMT under pH of 3.0, 5.0 and 7.0 was 5.28, 3.45 and 1.95 mg/g, respectively. -NH 2 , NH, SO and CN of pyrimidine ring carried by SMT acted as the complexation sites with Sb(V). The complexation constant K were - 3.15, -3.26 and - 3.48 at pH of 7.0, 5.0 and 3.0, respectively, indicating that the complexation strength between SMT and Sb(V) followed the order of pH 7.0 > pH 5.0 > pH 3.0. The binding energy between Sb(V) and the CN group of pyrimidine ring was the highest (1.42 eV), and then followed by the groups of -NH (1.37 eV), SO (0.66 eV) and -NH 2 (0.39 eV). Besides SO and CN, Sb(V) tends to complex with NH via coordination bond at pH of 7.0 while -NH 2 via cation-π interaction at pH 3.0 and 5.0. Compared to pH of 5.0, the strength of cation-π interaction at pH of 3.0 weakened according to the molecular electrostatic potential map. These results demonstrated that different from the situation where Sb(V) exists in aqueous solution alone, the coexistence of SMT with Sb(V) affected the adsorption behavior of Sb(V) in soil and solution pH was also an influence factor. These findings in this paper would be helpful for further understanding the mobility, bioavailability and other environmental behavior of Sb(V) in soil when Sb(V) coexists with antibiotics even other organic compounds., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Macrophages comprise the front line of defense against various pathogens. Classically activated macrophages (M1), induced by IFN-γ and LPS, highly express inflammatory cytokines and contribute to inflammatory processes. By contrast, alternatively activated macrophages (M2) are induced by IL-4 and IL-13, produce IL-10, and display anti-inflammatory activity. Adenylate kinase 4 (Ak4), an enzyme that transfers phosphate group among ATP/GTP, AMP, and ADP, is a key modulator of ATP and maintains the homeostasis of cellular nucleotides which is essential for cell functions. However, its role in regulating the function of macrophages is not fully understood. Here we report that Ak4 expression is induced in M1 but not M2 macrophages. Suppressing the expression of Ak4 in M1 macrophages with shRNA or siRNA enhances ATP production and decreases ROS production, bactericidal ability and glycolysis in M1 cells. Moreover, Ak4 regulates the expression of inflammation genes, including Il1b, Il6, Tnfa, Nos2, Nox2 , and Hif1a , in M1 macrophages. We further demonstrate that Ak4 inhibits the activation of AMPK and forms a positive feedback loop with Hif1α to promote the expression of inflammation-related genes in M1 cells. Furthermore, RNA-seq analysis demonstrates that Ak4 also regulates other biological processes in addition to the expression of inflammation-related genes in M1 cells. Interestingly, Ak4 does not regulate M1/M2 polarization. Taken together, our study uncovers a potential mechanism linking energy consumption and inflammation in macrophages., Competing Interests: The authors declare that the research was conducted in the absence of any commercial or financial relationships that could be construed as a potential conflict of interest., (Copyright © 2021 Chin, He, Chow, Yu, Lai and Miaw.)