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.

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.

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.

Genotype characterization of tetrahydrobiopterin deficiency in two Tibetan children.

Background: Tetrahydrobiopterin (BH4) deficiency is a rare cause of hyperphenylalaninemia (HPA). The incidence of this condition varies based on region and ethnicity. In the early stages, patients typically do not exhibit any symptoms, and HPA is identified only through newborn screening for diseases. It is important to distinguish BH4 deficiency from phenylketonuria (PKU, MIM # 261600). Timely diagnosis and treatment of BH4 deficiency are crucial for the prognosis of patients. Case presentation: We present two rare cases of Chinese Tibetan children with BH4D, diagnosed through biochemical tests and genetic sequencing. Case 1 is a male infant, 2 months old, with a newborn screening (NBS) Phe level of 1212 µmol/L (reference range <120 µmol). The biopterin(B) level was 0.19 mmol/molCr (reference range: 0.42-1.92 mmol/molCr), with a B% of 5.67% (reference range: 19.8%-50.3%). Gene sequencing revealed a homozygous missense variant [NM_000317.3 (PTS): c.259C > T (p.Pro87Ser), rs104894276, ClinVar variation ID: 480]. The patient was treated with a Phe-reduced diet and oral sapropterin, madopar and is currently 3 years and 4 months old, showing mild global developmental delay. Case 2 is a 40-day-old female infant with a Phe level of 2442.11 µmol/L and dihydropteridine reductase (DHPR) activity of 0.84 nmol/(min. 5 mm disc) (reference range: 1.02-3.35 nmol/min.5 mm disc. Gene sequencing revealed a compound heterozygous genotype [NM_000320.3(QDPR): c.68G > A (p.Gly23Asp), rs104893863, ClinVar Variation ID: 490] and [NM_000320.3(QDPR) c.419C > A (p. Ala140Asp), ClinVar ID: 2444501]. The patient was treated with a Phe-reduced diet and oral madopar, 5-hydroxytryptophan. At the age of 1 year, she exhibited severe global developmental delay with seizures. Conclusion: We identified and treated two cases of BH4D in Tibetan populations in China, marking the first confirmed instances. Our report emphasizes the significance of conducting differential diagnosis tests for BH4D.

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.

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.

Targeting Erbin-mitochondria axis in platelets/megakaryocytes promotes B cell-mediated antitumor immunity.

The roles of platelets/megakaryocytes (MKs), the key components in the blood system, in the tumor microenvironment and antitumor immunity are unclear. In patients with colorectal cancer, the number of platelets was significantly increased in patients with metastasis, and Erbin expression was highly expressed in platelets from patients with metastases. Moreover, Erbin knockout in platelets/MKs suppressed lung metastasis in mice and promoted aggregations of platelets. Mechanistically, Erbin-deficient platelets have increasing mitochondrial oxidative phosphorylation and secrete lipid metabolites like acyl-carnitine (Acar) by abolishing interaction with prothrombotic protein ESAM. Notably, Acar enhanced the activity of mitochondrial electron transport chain complex and mitochondrial oxidative phosphorylation in B cells by acetylation of H3K27 epigenetically. Targeting Erbin in platelets/MKs by a nanovesicle system dramatically attenuated lung metastasis in mice in vivo. Our study identifies an Erbin-mitochondria axis in platelets/MKs, which suppresses B cell-mediated antitumor immunity, suggesting a new way for the treatment of metastasis.

Laser additive manufacturing of shape memory biopolymer bone scaffold: 3D conductive network construction and electrically driven mechanism.

INTRODUCTION: The electro-actuated shape memory polymer scaffold has gained increasing attentions on the utilization of minimally invasive surgery for bone defect repair, which requires to construct an efficient conductive network to accomplish electrical-to-thermal conversion from conductive fillers to the entire matrix evenly. OBJECTIVES: In this study, multiwall carbon nanotube (MWCNT) was convective self-assembled on the ZnO tetrapod (t-ZnO) template, where MWCNT was controlled to disperse uniformly and regulated to contact with each other effectively due to the immersion capillary force during the evaporation loss of the convective self-assembly process, leading to an interwoven layer on the t-ZnO surface. METHODS: The prepared t-ZnO@MWCNT assembly was embedded in the poly(L-lactic acid)/thermoplastic polyurethane (PLLA/TPU) scaffold fabricated via selective laser sintering to construct a 3D conductive MWCNT network for improving the electro-actuated shape memory properties. RESULTS: It was observed that the interconnected MWCNT formed a 3D conductive network in the matrix without significant aggregation, which boosted the electrical-to-thermal properties of the scaffold, and the scaffold containing t-ZnO@MWCNT assembly possessed better electro-actuated shape memory properties with shape fixity of 98.0% and shape recovery of 98.8%. CONCLUSION: The scaffold exhibited improved electro-actuated shape memory properties and mechanical properties and the osteogenic inductivity was promoted with the combined effect of t-ZnO and electrical stimulation.

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.

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.

A new benzofuran compound from the resinous exudates of Commiphora myrrha.

A new benzofuran derivative, identified as myrrhain A (1), was isolated from the resinous exudates of Commiphora myrrha, together with the four known compounds: commipharane (2), myrrhterpeniod (3), myrrhone (4), and 9-methoxymyrrhone (5). All structures were elucidated by NMR and MS analyses. DPPH assay of compounds 1-5 revealed for the first time that all of them possess moderate antioxidative activity.

Interface Formation of Medium-Thick AA6061 Al/AZ31B Mg Dissimilar Submerged Friction Stir Welding Joints.

The medium-thick Al/Mg dissimilar friction stir welding (FSW) joint has serious groove and cavity defects due to uneven thermal distribution in the thickness direction. The submerged friction stir welding (SFSW) was employed to decrease the peak temperature of the joint and control the thermal gradient of the thickness direction, which were beneficial in suppressing the coarsening of the intermetallic compounds (IMCs) layer and improving the weld formation. According to the SEM results, the thickness value of the IMC layer in the nugget zone and shoulder affect zone decreased from 0.78 µm and 1.31 µm in FSW process to 0.59 µm and 1.21 µm in SFSW process at the same parameter, respectively. Compared with the FSW process, SFSW improves the thermal accumulation during the process, which inhibits the formation of the IMCs and facilitates the material flow to form a mechanical interlocking structure. This firm interface formation elevates the effective contact area of the whole joint interface and provides a strong connection between the dissimilar metals. Thus, the ultimate strength of the 6 mm thick Al/Mg dissimilar SFSW joints was enhanced to 171 MPa, equivalent to 71.3% of AZ31B Mg alloys strength.

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.

Corrigendum: Exercise and/or Cold Exposure Alters the Gene Expression Profile in the Fat Body and Changes the Heart Function in Drosophila.

[This corrects the article DOI: 10.3389/fendo.2022.790414.].

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.

A Facile Fabrication of CdSe/ZnS QDs-Block Copolymer Brushes-Modified Graphene Oxide Nanohybrid with Temperature-Responsive Behavior.

In this paper, we described a straightforward one-step chemical method for the synthesis of semiconductor quantum dots(QDs)-block copolymer brushes functionalized graphene oxide(GO) fluorescence nanohybrids. The azobenzene-terminated block copolymer poly(N-isopropylacrylamid)-b-poly(styrene-co-5-(2-methacryoylethyloxymethyl)-8-quinolinol)(PNIPAM-b-P(St-co-MQ)) was modified on the surface of GO sheets via host-guest interactions between ß-cyclodextrin-modified GO and azobenzene moieties, and simultaneously CdSe/ZnS QDs were integrated on the block copolymer brushes through the coordination between 8-hydroxyquinoline units in the polymer brushes and CdSe/ZnS QDs. The resulting fluorescence nanohybrid exhibited dual photoluminescence at 620 nm and 526 nm, respectively, upon excitation at 380 nm and LCST-type thermo-responsive behavior which originated from the change in the PNIPAM conformation in the block copolymer brushes of GO sheets.

A Facile Method for the Fabrication of Luminescent Eu3+-Doped SiO2 Nanowires.

Europium trivalent ion (Eu3+)-doped silica nanowires were prepared, and the positioning of Eu3+ in the silicon dioxide nanowire matrix was researched. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction analysis (XRD) and energy-dispersive X-ray spectroscope analysis (EDX) were used to characterize the product's morphology and structure. The representation of Fourier transform infrared spectra (FT-IR) and X-ray photoelectron spectroscopy (XPS) were indicative of the presence of a covalent Eu-O-Si bond. The results suggest that Eu3+ was successfully doped into amorphous silica. Furthermore, a sol-gel inorganic-organic co-assembly mechanism model was proposed to illuminate the formation of the rare-earth ion-doped nanowires. In addition, photoluminescent emission of europium ions in a silica matrix was further discussed. It was demonstrated that a 10% content of Eu3+ resulted in a quenching effect and after annealing at 650 °C, the europium ions in the nanowires had a high luminescence intensity due to the silica network structure.

Exercise and/or Cold Exposure Alters the Gene Expression Profile in the Fat Body and Changes the Heart Function in Drosophila.

The major reason of human morbidity and mortality is obesity and related diseases. Brown adipose tissue (BAT) is associated with low total adipose tissue content and a lower risk of type 2 diabetes mellitus. Studies have shown that exercise and cold expose may induce browning. In this study, we verified (1) whether exercise and/or cold exposure can improve the expression level of ucp4c, serca, ampkα, camkII, sirt1, octß3r, and hamlet; (2) if these interventions can save cardiac dysfunction induced by a high-fat diet (HFD) in Drosophila. w1118 (wild-type) virgin female flies collected within 8 h after eclosion were divided into eight groups: the normal feed control group (NFD-C), the normal feed exercise group (NFD-E), the normal feed cold exposure group (NFD-CA), the normal feed exercise/cold exposure group (NFD-EC), the HFD control group (HFD-C), the HFD exercise group (HFD-E), the HFD cold exposure group (HFD-CA), and the HFD exercise/cold exposure group (HFD-EC). After exercise and/or cold exposure for 7 days, the mRNA expression levels of ucp4c, serca, ampkα, camk II, sirt1, octß3r, and hamlet were tested by qRT-PCR, and m-mode was used to assess cardiac function. In addition, we assessed the triacylglycerol (TAG) levels, motor ability, fat mass (by Oil Red O [ORO] staining), and morphological features. The results of TAG, ORO staining, and morphological features all indicate that after interventions, body size of Drosophila was smaller compared with the control group, irrespective of the feeding patterns. The mRNA expression levels of ucp4c, serca, octß3r, hamlet, ampkα, camkII, and sirt1 were changed to varying degrees under different intervention states (exercise and/or cold exposure). Cold exposure and exercise/cold exposure partly improved cardiac function and the normal fruit flies' cardiac function and exercise ability. However, after exercise intervention, exercise ability and heart function were improved in both HFD and normal-fat diet (NFD) fruit flies. In conclusion, different intervention states (exercise and/or cold exposure) can change the mRNA expression levels of ucp4c, serca, octß3r, hamlet, ampkα, camkII, and sirt1. Exercise is the most effective way to restore HFD-induced cardiac dysfunction.

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.