Rhodium(III)-Catalyzed C-H Cascade Annulation of Arylhydrazines with 2-Diazo-1,3-indandiones for the Synthesis of Tetracyclic Indeno[1,2-b]indoles.

An efficient approach for the preparation of tetracyclic indeno[1,2-b]indoles via Rh(III)-catalyzed C-H cascade annulation between arylhydrazines and diazo indan-1,3-diones has been established. In addition, a series of indeno[1,2-b]indoles were obtained in up to 96% yield with a wide range of substrates and high functional group tolerance. Finally, the diverse transformations of the desired products demonstrate the synthetic utility and utilization of this protocol.

Rhodium(III)-catalyzed C-H alkylation of arylhydrophthalazinediones with α-Cl ketones as sp3-carbon alkylated agents.

A Rh(III)-catalyzed C-H bond direct alkylation between 2-arylphthalazine-1,4-diones and α-Cl ketones, which are sp3-carbon synthons, under mild conditions has been disclosed. The corresponding phthalazine derivatives are readily obtained in moderate to excellent yields with a wide range of substrates and high functional group tolerance. The practicality and utility of this method are demonstrated by the derivatization of the product.

Boosting the Photocatalysis of Plasmonic Au-Cu Nanocatalyst by AuCu-TiO2 Interface Derived from O2 Plasma Treatment.

Plasmonic gold (Au) and Au-based nanocatalysts have received significant attention over the past few decades due to their unique visible light (VL) photocatalytic features for a wide variety of chemical reactions in the fields of environmental protection. However, improving their VL photocatalytic activity via a rational design is prevalently regarded as a grand challenge. Herein we boosted the VL photocatalysis of the TiO2-supported Au-Cu nanocatalyst by applying O2 plasma to treat this bimetallic plasmonic nanocatalyst. We found that O2 plasma treatment led to a strong interaction between the Au and Cu species compared with conventional calcination treatment. This interaction controlled the size of plasmonic metallic nanoparticles and also contributed to the construction of AuCu-TiO2 interfacial sites by forming AuCu alloy nanoparticles, which, thus, enabled the plasmonic Au-Cu nanocatalyst to reduce the Schottky barrier height and create numbers of highly active interfacial sites. The catalyst's characterizations and density functional theory (DFT) calculations demonstrated that boosted VL photocatalytic activity over O2 plasma treated Au-Cu/TiO2 nanocatalyst arose from the favorable transfer of hot electrons and a low barrier for the reaction between CO and O with the construction of large numbers of AuCu-TiO2 interfacial sites. This work provides an efficient approach for the rational design and development of highly active plasmonic Au and Au-based nanocatalysts and deepens our understanding of their role in VL photocatalytic reactions.

Impaired AT2 to AT1 cell transition in PM2.5-induced mouse model of chronic obstructive pulmonary disease.

BACKGROUND: Particular matter 2.5 (PM2.5) is one of the most important air pollutant, and it is positively associated with the development of chronic obstructive pulmonary disease (COPD). However, the precise underlying mechanisms through which PM2.5 promotes the development of COPD remains largely unknown. METHODS: Mouse alveolar destruction were determined by histological analysis of lung tissues and lung function test. Alveolar type II cells (AT2) to alveolar type I cells (AT1) transition in PM2.5-induced COPD mouse model was confirmed via immunofluorescence staining and qPCR analysis. The differentially expressed genes in PM2.5-induced COPD mouse model were identified by RNA-sequencing of alveolar epithelial organoids and generated by bioinformatics analysis. RESULTS: In this study, we found that 6 months exposure of PM2.5 induced a significantly decreased pulmonary compliance and resulted in pulmonary emphysema in mice. We showed that PM2.5 exposure significantly reduced the AT2 to AT1 cell transition in vitro and in vivo. In addition, we found a reduced expression of the intermediate AT2-AT1 cell process marker claudin 4 (CLDN4) at day 4 of differentiation in mouse alveolar organoids treated with PM2.5, suggesting that PM2.5 exposure inhibited AT2 cells from entering the transdifferentiation process. RNA-sequencing of mouse alveolar organoids showed that several key signaling pathways that involved in the AT2 to AT1 cell transition were significantly altered including the Wnt signaling, MAPK signaling and signaling pathways regulating pluripotency of stem cells following PM2.5 exposure. CONCLUSIONS: In summary, these data demonstrate a critical role of AT2 to AT1 cell transition in PM2.5-induced COPD mouse model and reveal the signaling pathways that potentially regulate AT2 to AT1 cell transition during this process. Our findings therefore advance the current knowledge of PM2.5-induced COPD and may lead to a novel therapeutic strategy to treat this disease.

Synthesis of Tetrahydrocarbazol-4-ones via Rh(III)-Catalyzed C-H Activation/Annulation of Arylhydrazines with Iodonium Ylides.

The rhodium(III)-catalyzed C-H activation followed by intramolecular annulation reactions between arylhydrazines and iodonium ylides under suitable conditions has been described. Tetrahydrocarbazol-4-ones are readily achieved with moderate to excellent yields. The synthetic protocol features a wide range of substrates with high functional group tolerance. The gram-scale reaction and derivatization of the product demonstrate the synthetic practicality and utilization of this method.

One-Step versus Two-Step Valence Tautomeric Transitions in Tetraoxolene-Bridged Dinuclear Cobalt Compounds.

The syntheses of valence tautomeric compounds with multistep transitions using new redox-active ligands are the long-term goal of the field of bistable materials. The redox-active tetraoxolene ligand, 2,7-di-tert-butylpyrene-4,5,9,10-tetraone (pyreneQ-Q), is now developed to synthesize a pair of dinuclear compounds {[CoL2]2(pyreneSq-Sq)}[Co(CO)4]2·xCH2Cl2·2C6H5CH3 (1, x = 2, L = 1,10-phenanthroline, phen; 2, x = 1.5, L = 2,2'-bipyridine, bpy). Variable-temperature magnetic susceptibilities and single-crystal X-ray diffraction measurements indicate a partial one-step valence tautomeric transition for 1 and a rare two-step valence tautomeric transition for 2, respectively. DFT calculation results are consistent with the experimental data, revealing the correlation between thermodynamic parameters and the one-step/two-step valence tautomeric behaviors.

MoO3 Nanobelt-Modified HMCM-49 Zeolite with Enhanced Dispersion of Mo Species and Catalytic Performance for Methane Dehydro-Aromatization.

The methane dehydro-aromatization reaction (MDA) is a promising methane valorization process due to the conversion of methane to value-added aromatics (benzene, toluene and naphthalene). However, one of the major disadvantages of utilizing zeolite in MDA is that the catalyst is rapidly inactivated due to coke formation, which eventually causes the activity and aromatic selectivity to decrease. Consequently, the process is not conducive to large-scale industrial applications. The reasonable control of Mo site distribution on the zeolite surface is the key factor for partially inhibiting the coking of the catalyst and improving stability. Here, MoO3 nanobelts can be used for alternative Mo precursors to prepare MDA catalysts. Catalysts modified with MoO3 nanobelts present higher activity (13.4%) and benzene yield (9.2%) than those catalysts loaded with commercial MoO3.

Multi-Nuclear Rare-Earth-Implanted Tartaric Acid-Functionalized Selenotungstates and Their Fluorescent and Magnetic Properties.

A family of multinuclear rare-earth (RE)-implanted H2tart2--functionalized selenotungstates (STs) [H2N(CH3)2]13H{[W2O5(OH)2(H2tart)2](H2tart){[W3O6RE2(H2O)6][SeW9O33]2}2}·31H2O [RE = Eu3+ (1), Tb3+ (2), Dy3+ (3), Ho3+ (4), Y3+ (5); H4tart = d-tartaric acid] have been afforded by a simple one-pot aqueous reaction and were structurally characterized. Intriguingly, their isomorphous organic-inorganic hybrid anion {[W2O5(OH)2(H2tart)2](H2tart){[W3O6RE2(H2O)6][SeW9O33]2}2}14- includes two sandwich-type {[W3O6[RE2(H2O)6][SeW9O33]2}4- dimeric units with a W-O-RE heterometal core, which are further joined by two H2tart2--decorated dinuclear tungsten-oxo {W2O5(OH)2(H2tart)2} clusters and a bridging H2tart2- ligand, contributing to a surprising Mobius band-like configuration. It is worth emphasizing that three H2tart2- ligands coordinate with tungsten centers rather than RE cations. For all we know, 1-5 delegate the infrequent RE-implanted STs functionalized by triplicate H2tart2- bridges. Furthermore, fluorescent performances of 1-4 as well as magnetic properties of 2-4 have been surveyed. The solid-state fluorescence emission spectra prove that each of them undoubtedly shows the characteristic emission peaks of RE cores, while alternating-current susceptibility measurements suggest field-induced single-molecule magnetic behavior in 3.

Knockout of two BnaMAX1 homologs by CRISPR/Cas9-targeted mutagenesis improves plant architecture and increases yield in rapeseed (Brassica napus L.).

Plant height and branch number are essential components of rapeseed plant architecture and are directly correlated with its yield. Presently, improvement of plant architecture is a major challenge in rapeseed breeding. In this study, we first verified that the two rapeseed BnaMAX1 genes had redundant functions resembling those of Arabidopsis MAX1, which regulates plant height and axillary bud outgrowth. Therefore, we designed two sgRNAs to edit these BnaMAX1 homologs using the CRISPR/Cas9 system. The T0 plants were edited very efficiently (56.30%-67.38%) at the BnaMAX1 target sites resulting in homozygous, heterozygous, bi-allelic and chimeric mutations. Transmission tests revealed that the mutations were passed on to the T1 and T2 progeny. We also obtained transgene-free lines created by the CRISPR/Cas9 editing, and no mutations were detected in potential off-target sites. Notably, simultaneous knockout of all four BnaMAX1 alleles resulted in semi-dwarf and increased branching phenotypes with more siliques, contributing to increased yield per plant relative to wild type. Therefore, these semi-dwarf and increased branching characteristics have the potential to help construct a rapeseed ideotype. Significantly, the editing resources obtained in our study provide desirable germplasm for further breeding of high yield in rapeseed.

Three BnaIAA7 homologs are involved in auxin/brassinosteroid-mediated plant morphogenesis in rapeseed (Brassica napus L.).

KEY MESSAGE: BnaIAA7 crosstalk with BR signaling is mediated by the interaction between BnaARF8 and BnaBZR1 to regulate rapeseed plant morphogenesis. Auxin (indole-3-acetic acid, IAA) and brassinosteroids (BRs) are essential regulators of plant morphogenesis. However, their roles in rapeseed have not been reported. Here, we identified an extremely dwarf1 (ed1) mutant of rapeseed that displays reduced stature, short hypocotyls, as well as wavy and curled leaves. We isolated ED1 by map-based cloning, and found that it encodes a protein homologous to AtIAA7. ED1 acts as a repressor of IAA signaling, and IAA induces its degradation through its degron motif. A genomic-synteny analysis revealed that ED1 has four homologs in rapeseed, but two were not expressed. Analyses of transcriptomes and of various mutant BnaIAA7s in transgenic plants revealed that the three expressed BnaIAA7 homologs had diverse expression patterns. ED1/BnaC05.IAA7 predominantly functioned in stem elongation, BnaA05.IAA7 was essential for reproduction, while BnaA03.IAA7 had the potential to reduce plant height. Physical interaction assays revealed that the three BnaIAA7 homologs interacted in different ways with BnaTIRs/AFBs and BnaARFs, which may regulate the development of specific organs. Furthermore, BnaARF8 could directly interact with the BnaIAA7s and BnaBZR1. We propose that BnaIAA7s interact with BR signaling via BnaARF8 and BnaBZR1 to regulate stem elongation in rapeseed.

First Dimethyltin-Functionalized Rare-Earth Incorporated Tellurotungstates Consisting of {B-α-TeW7O28} and {W5O18} Mixed Building Units.

The facile one-step assembly reaction of Na2WO4·2H2O, Sn(CH3)2Cl2, RE(NO3)3·6H2O and K2TeO3 in the presence of dimethylamine hydrochloride as an organic solubilizing agent in acidic aqueous solution resulted in a family of dimethyltin-functionalized rare-earth (RE) incorporated tellurotungstates consisting of {B-α-TeW7O28} and {W5O18} mixed building units [H2N(CH3)2]8Na4H2[RE2(OH)(B-α-TeW7O28)Sn2(CH3)4(W5O18)]2·18H2O [RE = ErIII (1), YbIII (2), HoIII (3), YIII (4)]. The most striking structural characteristic of 1-4 is that they all contain a novel tetrameric S-shaped [RE2(OH)(B-α-TeW7O28)Sn2(CH3)4(W5O18)]214- moiety simultaneously including two pentavacant Keggin [B-α-TeW7O28]12- and two monovacant Lindqvist [W5O18]6- fragments connected by RE and dimethyltin linkers. To the best of our knowledge, such dimethyltin-functionalized RE-containing tellurotungstates have not been reported before. The visible or NIR solid-state emission spectra of 1 and 3 display the characteristic emission bands arising from ErIII and HoIII centers. Moreover, various 1-Er/Yb co-doped samples were prepared by controlling different mass ratio of Er(NO3)3·6H2O/Yb(NO3)·6H2O in the range of 0.96:0.04-0.02:0.98. In the visible region, the emission intensity of the 1-Er0.40/Yb0.60 co-doped sample reaches the maximum at the mass ratio of Er(NO3)3·6H2O/Yb(NO3)·6H2O being 0.40:0.60, and this observation is mainly derived from the fact that the Yb3+ ions can sensitize the Er3+ ions to enhance the emission intensity in the visible region. However, no such phenomenon for the 1-Er/Yb co-doped samples is seen in the NIR region. Besides, the upconversion spectra of the 1-Er/Yb co-doped samples were first observed. In addition, the thermal stabilities of 1-4 were also investigated on the crystalline samples and the thermal decomposition process of 1 has been deeply studied.

Evolutionary and Functional Analysis of Membrane-Bound NAC Transcription Factor Genes in Soybean.

Functional divergence is thought to be an important evolutionary driving force for the retention of duplicate genes. We reconstructed the evolutionary history of soybean (Glycine max) membrane-bound NAC transcription factor (NTL) genes. NTLs are thought to be components of stress signaling and unique in their requirement for proteolytic cleavage to free them from the membrane. Most of the 15 GmNTL genes appear to have evolved under strong purifying selection. By analyzing the phylogenetic tree and gene synteny, we identified seven duplicate gene pairs generated by the latest whole-genome duplication. The members of each pair were shown to have variously diverged at the transcriptional (organ specificity and responsiveness to stress), posttranscriptional (alternative splicing), and protein (proteolysis-mediated membrane release and transactivation activity) levels. The dormant (full-length protein) and active (protein without a transmembrane motif) forms of one pair of duplicated gene products (GmNTL1/GmNLT11) were each separately constitutively expressed in Arabidopsis (Arabidopsis thaliana). The heteroexpression of active but not dormant forms of these proteins caused improved tolerance to abiotic stresses, suggesting that membrane release was required for their functionality. Arabidopsis carrying the dormant form of GmNTL1 was more tolerant to hydrogen peroxide, which induces its membrane release. Tolerance was not increased in the line carrying dormant GmNTL11, which was not released by hydrogen peroxide treatment. Thus, NTL-release pattern changes may cause phenotypic divergence. It was concluded that a variety of functional divergences contributed to the retention of these GmNTL duplicates.

Structural Transformation from Dimerization to Tetramerization of Serine-Decorated Rare-Earth-Incorporated Arsenotungstates Induced by the Usage of Rare-Earth Salts.

Three types of serine-decorated rare- earth-containing arsenotungstate [H2 N(CH3 )2 ]6 NaH[RE2 W4 O10 (H2 O)8 (Ser)2 (B-α-AsW9 O33 )2 ]⋅30 H2 O (RE3+ =Eu3+ , Gd3+ , Tb3+ , Dy3+ , Ho3+ , Er3+ , Tm3+ , Yb3+ , and Y3+ ; 1), [H2 N(CH3 )2 ]6 Na6-x REx H4-2 x [RE4 W8 O19 (H2 O)10+y (OH)2 (Ser)2 (B-α-AsW9 O33 )4 ]⋅n H2 O (RE3+ =Tb3+ , x=1, y=2, n=36; RE3+ =Dy3+ , Ho3+ , Er3+ , Yb3+ , Y3+ , x=0, y=0, n=38; RE3+ = Tm3+ , x=1, y=0, n=38; Ser=serine; 2), and [H2 N(CH3 )2 ]6-2 x Na2+3 x REx H10-6 x+y [RE4 W8 O19 (H2 O)8 (OH)2 (Ser)4 (B-α-AsW9 O33 )4 ]⋅Cly ⋅n H2 O (RE3+ =Ce3+ , Pr3+ , x=1, y=0, n=65; RE3+ =Nd3+ , Sm3+ , x=0, y=0, n=65; RE3+ =Eu3+ , Gd3+ , x=1, y=2, n=45; 3) were synthesized with the participation of the organic solubilizers dimethylamine hydrochloride and l-serine and were structurally characterized. The use of different amounts of rare-earth salts results in the structural transformation from dimerization to tetramerization of types 1-3. Type 1 is a dimeric sandwich-type assembly of a dual-Ser-participating [RE2 W4 O10 (H2 O)8 (Ser)2 ]10+ entity sandwiched by two [B-α-AsW9 O33 ]9- moieties, whereas types 2 and 3 have a tetrameric square structure formed by four [B-α-AsW9 O33 ]9- moieties that anchor a dual/tetra- Ser-participating [RE4 W8 O19 (H2 O)10+y (OH)2 (Ser)2 ]20+ or [RE4 W8 O19 (H2 O)8 (OH)2 (Ser)4 ]20+ core. The solid-state luminescence properties and lifetime-decay behaviors of these compounds were investigated. The chromaticity coordinates, dominant wavelengths, color purities, and correlated color temperatures were also calculated.

Single Electrospun PLLA and PCL Polymer Nanofibers: Increased Molecular Orientation with Decreased Fiber Diameter.

Electrospinning has become a widely-used method for fabricating polymer nanofibers for various applications including filtration, drug delivery, and tissue engineering. Due to the high extensional forces during the electrospinning process, and the rapid crystallization and solidification during solvent evaporation, molecular orientation may develop within the resulting fibers. The properties of electrospun fibers are expected to be sensitive to level of orientation in the fibers. Various reports have shown an increased modulus with decreased fiber diameter, and molecular orientation has been used to explain this trend. However, there have been relatively few studies of the detailed relationship between fiber diameter and molecular orientation, especially at the single fiber level. Here we report a quantitative study of the orientation in individual electrospun poly(caprolactone) (PCL) and poly(L-lactic acid) (PLLA) fibers using low-dose electron microscopy and diffraction techniques. Our results confirmed that for electrospun fibers of PCL and PLLA processed under similar experimental conditions, the molecular orientation decreased as the fiber diameter increased. The extent of orientation remained high for quite large fiber diameters, with azimuthal orientation of 20 degrees seen up to ~500 nm for PCL and ~2000 nm for PLLA.

The novel non-fully-fused ring small molecule acceptors: End-capped modification investigation.

End-capped modification is an efficacious strategy for developing high-performance acceptor materials. In this paper, the experimentally synthesized A-D-A'-D-A type non-fully-fused ring acceptor IDTBT-4F (R) was used as a reference molecule, and five small molecule acceptors for R1-R5 were investigated by changing R's terminal functional groups. By using DFT/B3PW91/6-31G (d,p) method, the ground-state structures of all molecules were studied. The absorption spectra of these acceptors were gained by the TD-DFT/MPW1PW91/6-31G (d,p) approach. Meanwhile, the charge density difference and transition density matrix were analyzed effectively. It can be observed that, compared to the R molecule, all developed molecules exhibited narrower energy gaps, larger absorption wavelengths, more red-shifted absorption spectra, lower excitation energies, higher dipole moment and greater electron-accepting capacity. The strategy of functional group substitution is superior to halogen substitution in improving the aforementioned parameters. Both terminal π-extension and end-group chlorination strategies can synergistically enhance molecular performance. In addition, we also calculated the electron mobility of the dimers constructed by all the molecules, among which R1 and R4 molecules designed with -COOCH3 functional group substitution and R2 molecule with terminal chlorination achieved superior electron mobility compared to R molecule due to their significant electronic coupling. Overall, the study shows that the designed molecules can be highly effective candidates for applications of organic solar cells.

TRA-ACGAN: A motor bearing fault diagnosis model based on an auxiliary classifier generative adversarial network and transformer network.

Motor bearing fault diagnosis is essential to guarantee production efficiency and avoid catastrophic accidents. Deep learning-based methods have been developed and widely used for fault diagnosis, and these methods have proven to be very effective in accurately diagnosing bearing faults. In this paper, study the application of generative adversarial networks (GANs) in motor bearing fault diagnosis to address the practical issue of insufficient fault data in industrial testing. Focus on the auxiliary classifier generative adversarial network (ACGAN), and the data expansion is carried out for small datasets. This paper present a novel transformer network and auxiliary classifier generative adversarial network (TRA-ACGAN) for motor bearing fault diagnosis, where the TRA-ACGAN combines an ACGAN with a transformer network to avoid the traditional iterative and convolutional structures. The attention mechanism is fully utilized to extract more effective features, and the dual-task coupling problem encountered in classical ACGANs is avoided. Experimental results with the CWRU dataset and the PU dataset in the field of motor bearing fault diagnosis demonstrate the suitability and superiority of the TRA-ACGAN.

Metal-Organic-Framework-Derived Nitrogen-Doped Carbon-Matrix-Encapsulating Co0.5Ni0.5 Alloy as a Bifunctional Oxygen Electrocatalyst for Zinc-Air Batteries.

The development of low-cost, high-performance oxygen electrocatalysts is of great significance for energy conversion and storage. As a potential substitute for precious metal electrocatalysts, the construction of efficient and cost-effective oxygen electrocatalysts is conducive to promoting the widespread application of zinc-air batteries. Herein, CoxNiyMOF nanoparticles encapsulated within a carbon matrix were synthesized and employed as cathode catalysts in zinc-air batteries. Co0.5Ni0.5MOF exhibits superior oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) performance and durability. The zinc-air battery assembled with Co0.5Ni0.5MOF as the air cathode exhibits a maximum power density of 138.6 mW·cm-2. These improvements are mainly attributed to the optimized metal composition of the cobalt-nickel alloy, which increases the specific surface area of the material and optimizes its pore structure. Significantly, the optimization of the electronic structure and active sites within the material has led to amplified ORR/OER activity and better zinc-air battery performance. This study underscores the immense promise of Co0.5Ni0.5MOF catalysts as feasible substitutes for commercial Pt/C catalysts in zinc-air batteries.

Laponite-activated AIE supramolecular assembly with modulating multicolor luminescence for logic digital encryption and perfluorinated pollutant detection.

Recently, the non-covalently activated supramolecular scaffold method has become a prominent research area in the field of intelligent materials. Here, the inorganic clay (LP) promoted the AIE properties of 4,4',4″,4‴-(ethene-1,1,2,2-tetrayltetrakis(benzene-4,1-diyl))tetrakis(1-ethylpyridin-1-ium) (P-TPE), showing an astonishing 42-fold enhancement of the emission intensity of the yellow-green luminescence and a 34-fold increase of the quantum yield via organic-inorganic supramolecular strategy as well as the efficient light-harvesting properties (energy transfer efficiency up to 33 %) after doping with the dye receptor Rhodamine B. Furthermore, the full-color spectral regulation, including white light, was achieved by adjusting the ratio of the donor to the acceptor component and co-assembling with the carbon dots (CD). Interestingly, this TPE-based non-covalently activated full-color supramolecular light-harvesting system (LHS) could be achieved not only in aqueous media but also in the hydrogel and the solid state. More importantly, this panchromatic tunable supramolecular LHS exhibited the multi-mode and quadruple digital logic encryption property as well as the specific detection ability towards the perfluorobutyric acid and the perfluorobutanesulfonic acid, which are harmful to human health in drinking water. This result develops a simple, convenient and effective approach for the intelligent anti-counterfeiting and the pollutant sensing.

Dysfunctional circadian clock accelerates cancer metastasis by intestinal microbiota triggering accumulation of myeloid-derived suppressor cells.

Circadian homeostasis in mammals is a key intrinsic mechanism for responding to the external environment. However, the interplay between circadian rhythms and the tumor microenvironment (TME) and its influence on metastasis are still unclear. Here, in patients with colorectal cancer (CRC), disturbances of circadian rhythm and the accumulation of monocytes and granulocytes were closely related to metastasis. Moreover, dysregulation of circadian rhythm promoted lung metastasis of CRC by inducing the accumulation of myeloid-derived suppressor cells (MDSCs) and dysfunctional CD8+ T cells in the lungs of mice. Also, gut microbiota and its derived metabolite taurocholic acid (TCA) contributed to lung metastasis of CRC by triggering the accumulation of MDSCs in mice. Mechanistically, TCA promoted glycolysis of MDSCs epigenetically by enhancing mono-methylation of H3K4 of target genes and inhibited CHIP-mediated ubiquitination of PDL1. Our study links the biological clock with MDSCs in the TME through gut microbiota/metabolites in controlling the metastatic spread of CRC, uncovering a systemic mechanism for cancer metastasis.