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A new binuclear cobalt complex with electron-donating group (–OCH3) accelerates the visible-light-driven conversion of CO2 to CO in a water-containing system.

We report here a high-nuclear 3d–4f heterometallic Cu12Dy14 nanocluster featuring a centipede-like shape, as well as its possible assembly mechanism.

Oxidative stress is crucial to the biology of tumors. Oxidative stress’ potential predictive significance in colorectal cancer (CRC) has not been studied; nevertheless here, we developed a forecasting model based on oxidative stress to forecast the result of CRC survival and enhance clinical judgment. The training set was chosen from the transcriptomes of 177 CRC patients in GSE17536. For validation, 65 samples of colon cancer from GSE29621 were utilized. For the purpose of choosing prognostic genes, the expression of oxidative stress-related genes (OXEGs) was found. Prognostic risk models were built using multivariate Cox regression analysis, univariate Cox regression analysis, and LASSO regression analysis. The outcomes of the western blot and transcriptome sequencing tests were finally confirmed. ATF4, CARS2, CRP, GPX1, IL1B, MAPK8, MRPL44, MTFMT, NOS1, OSGIN2, SOD2, AARS2, and FOXO3 were among the 14 OXEGs used to build prognostic characteristics. Patients with CRC were categorized into low-risk and high-risk groups according on their median risk scores. Cox regression analysis using single and multiple variables revealed that OXEG-related signals were independent risk factors for CRC. Additionally, the validation outcomes from western blotting and transcriptome sequencing demonstrated that OXEGs were differently expressed. Using 14 OXEGs, our work creates a predictive signature that may be applied to the creation of new prognostic models and the identification of possible medication candidates for the treatment of CRC.

Gastric cancer is among the most common gastrointestinal malignancies. Recent studies have suggested that bone morphogenetic protein-2 (BMP2) is related to the development and progression of various cancers. Meanwhile, evidence suggests that BMP2 might lead to epigenetic changes in gastric cancer. Thus, we investigated whether BMP2 plays a role in the development of gastric cancer via epigenetic regulation. Cell viability, colony formation, and cell cycle assays were performed to assess the effect of recombinant human BMP2 (rhBMP2) in gastric cancer cells. LDN-193189 and Noggins were used as antagonists of the canonical BMP-SMAD signaling pathway. The protein levels were determined using a western blot analysis. Lentiviral vectors with EZH2 shRNA or EZH2 overexpression were used to mediate the role of EZH2 and the relationship between BMP2 and EZH2 in gastric cancer. We found that rhBMP2 inhibits cell proliferation by arresting the cell cycle in HGC-27 and SNU-216 gastric cancer cells. Neither LDN-193189 nor Noggins, antagonists of the canonical BMP-SMAD signaling pathway, can reverse the effect of rhBMP2 on gastric cancer. Molecularly, rhBMP2 downregulates the expression of EZH2 and H3K27me3, leading to increases in P16 and P21 and decreases in CDK2, CDK4, and CDK6. Altogether, in this study, we demonstrate that BMP2 serves as a tumor suppressor in gastric cancer cells by downregulating EZH2 and H3K27me3 through the non-SMAD BMP pathway, suggesting that BMP2 might be a new therapeutic target for gastric cancer treatment.bAbbreviations:/bBMP: bone morphogenetic protein; TGF-β: transforming growth factor-beta; EZH2: enhancer of zeste homolog 2; H3K27me3: trimethylation histone H3 lysine 27; HRECs: human retinal endothelial cells; PcG: polycomb group; PRC: polycomb repressive complexes.

Catalysts often undergo changes during the process of catalytic reactions, which makes the whole catalytic reaction system complicated and brings about much difficulty for the exploration of catalytic mechanism. Herein, we report that an octahedral metal organic cage (MOC) with stress was directionally transformed into two-dimensional nanoarrays maintaining the structure of precursor and new soluble low-nuclear complexes during the electrocatalytic oxygen evolution reaction (OER). The in-situ generated miscible electrocatalyst exhibits an overpotential as low as 197 mV at 10 mA cm−2, with a high electrochemical stability up to 5 hours. Notably, the miscible catalyst can be used as bifunctional electrocatalyst for OER and hydrogen evolution reaction (HER) and exhibits an ultra-low overpotential of 293 mV, even achieve overall water splitting under the voltage provided by a 1.5 V AA battery. As revealed by density functional theory simulations, the position of SO42− in MOC heterogeneous catalyst is regulated by the soluble low-nuclear complexes to reduce the activation energy of the reaction, leading to an optimization of the OER activity for the reaction system. This work provides a new strategy for the rational design of high-efficiency electrocatalytic system.

The tuning of slow magnetic relaxation of six-coordinated Dy(iii) complexes was achieved through chloride and bis-Schiff bases bearing different spacers.

Aim: To elucidate the potential function and prognostic value of chromatin regulators (CRs) in colon cancer. Materials & methods: A comprehensive analysis of CR RNA expression data from public databases was conducted. Results: The authors successfully established and validated a 17 CR-based signature using public databases. Ten CRs of the signature were eventually verified at the protein level using the Human Protein Atlas database. Functional enrichment showed that CRs were significantly enriched in cancer-related pathways. This signature was remarkably relevant to immune cell infiltration, immune checkpoints, tumor immune dysfunction and exclusion (TIDE) score and drug sensitivity. Conclusion: The authors identified a novel, reliable prognostic signature for colon cancer. The study provided new insights into the function of CRs and has important clinical implications for immunotherapy for colon cancer.

Background Vascular mimicry is emerging as a potential target for anti-tumorigenesis.It involves the formation of microvascular channels composed of tumor cells. However, the mechanism of how tumor cells build into microvascular channels is not clear.The existence of a relationship between EMT and VM has been reported in the literature but the exact regulatory mechanism is unclear. Whether EMT regulates VM formation and its specific mechanism need to be further verified in NPC Materials and Methods We detected the relationship between EMT indicators and VM by immunohistochemical experiments. Also, the relationship between EMT indexes and VM indexes and clinical staging was analyzed. Cellular assays and immunoprotein blotting assays were used to detect EMT and VM changes in cells after addition of EGFR inhibitors. VM and EMT indices were examined after EGFR-targeted drug treatment in a subcutaneous tumorigenesis assay in nude mice. Conclusion EGFR-regulated EMT is a driver of vasculogenic mimicry in Nasopharyngeal Carcinoma.

The reactions of cis-Pt(DMSO)2Cl2 and tropolone (HL) with 8-hydroxyquinoline (HQ) or 2-methyl-8-hydroxyquinoline (HMQ) gave [Pt(Q)(L)] (1) and [Pt(MQ)(L)] (2), which present mononuclear structures with their Pt(II) ions four-coordinated in square planar geometries. Their in vitro biological properties were evaluated by MTT assay, which showed a remarkable cytotoxic activity on the cancer cell lines. 1 shows higher cytotoxic activities on tumor cells such as T24, HeLa, A549, and NCI-H460 than complex 2 and cisplatin, with IC50 values

A superb alkali-resistant single-molecule-magnet (SMM) material with the molecular formula [Dy2Ni4(L)8(CH3COO)4(NO3)2] (1) (HL = 8-hydroxyquinoline) has been structurally and magnetically characterized. Single-crystal X-ray diffraction revealed that 1 possesses a hexanuclear [DyIII2NiII4] cluster, which is built by two triangular [DyIIINiII2] cores double-bridged through two CH3COO- ions. Interestingly, 1 can keep its original structure in dilute acid and common basic solutions (e.g., triethylamine and NaOH). More importantly, 1 is still stable after treatment with a 20 M NaOH aqueous solution for 1 month at room temperature. Magnetic measurements uncovered that 1 is an SMM under zero applied field with Ueff = 7.43 K. To the best of our knowledge, 1 is the first example of a 3d-4f SMM with such extreme alkali resistance. This work will broaden the vision of preparing SMM materials with excellent chemical stability.

Gastric cancer is a common malignant tumor of the human digestive system. Currently, the treatment of gastric cancer is still dominated by radiotherapy, chemotherapy and surgery. Although the treatment is very effective, we are also trying to find new treatment methods. Traditional Chinese Medicine (TCM) may play an important role in the treatment of gastric cancer.The aim of this study is to explore the effects of naringin on the proliferation, migration, invasion and apoptosis of gastric cancer and its potential mechanisms.MGC803 and MKN45 viability were detected by MTT assay. The effects of naringin on cell cloning, migration and invasion were determined by colony formation assay, cell scratch test and transwell assay (ThermoFisher Scientific™, Waltham, Massachusetts USA), respectively. Cell cycle and apoptosis were assayed by flow cytometry. Associated proteins were measured using Western blot and immunohistochemistry (IHC). The experimental results were further verified in nude mice.This study was carried out in Department of Experimental Animal Center of Xi'an Jiaotong University and the Translation Medicine Center of the First Affiliated Hospital of Xi'an Jiaotong University in China.Cells remained mainly in G0/G1 phase and apoptosis was increased. The nude mouse model showed that naringin treatment could inhibit the growth of tumors in nude mice. Cell scratch tests and transwell assay showed that the invasion and migration abilities of the gastric cancer cell line were significantly reduced after naringin treatment. Western blot showed that the expression of Vimentin, Zeb1 and P-AKT was downregulated and that E-cadherin was upregulated after naringin treatment.Naringin can block the cell-cycle, induce cancer cell apoptosis, and inhibit the epithelial mesenchymal transition (EMT) process by inhibiting the PI3K-AKT/Zeb1 pathway in gastric cancer cells. Therefore, naringin can inhibit the development of gastric cancer.

Purpose Systemic immune-inflammation index (SII) has been demonstrated to be closely associated with the poor prognosis of nasopharyngeal carcinoma (NPC). However, the role of SII during treatment of NPC has not been reported. This study aimed to determine the prognostic value of SII during treatment for NPC patients. Methods A total of 759 patients diagnosed with NPC were included in this retrospective study (393 in training cohort and 366 in validation cohort). The correlation between variables was analyzed by the chi-squared test, the Fisher’s exact test or the likelihood test. Kaplan–Meier method and log-rank test were used to analyze progression-free survival (PFS) and overall survival (OS). The independent prognostic factors were determined by multivariate analysis of Cox proportional hazards regression model. The uncontrolled risk was analyzed by Logistic regression. Receiver operating characteristic (ROC) curves were used to assess prognostic value. Results The optimal cut-off point for the SII during treatment was 937.32. High SII during treatment group had higher uncontrolled risk than low SII during treatment group (p = 0.008). In multivariate Cox proportional hazard models analysis, SII during treatment was an independent prognostic factor for 5-year PFS (p p Conclusions The SII during treatment is a promising indicator of predicting the survival in NPC patients, especially the risk of uncontrolled occurrence. By monitoring the SII during treatment, it is possible to better evaluate the treatment effect and formulate personalized treatment.

The aggregation and formation of heterometallic nanoclusters usually involves a variety of complex self-assembly processes; thus, the exploration of their assembly mechanisms through process tracking is more challenging than that for homometallic nanoclusters. We explored here the effect of solvent on the formation of heterometallic clusters, which gave two heterometallic nanoclusters, [Dy2Co8(μ3-OCH3)2(L)4(HL)2(OAc)2(NO3)2(CH3CN)2]·CH3CN·H2O (1) and [Dy4Co6(L)4(HL)2(OAc)6(OCH2CH2OH)2(HOCH2CH2OH)(H2O)]·9CH3CN (2), with the H3L ligand formed from the in situ condensation reaction of 3-amino-1,2-propanediol with 2-hydroxy-1-naphthaldehyde in the presence of Co(OAc)2·4H2O and Dy(NO)3·6H2O. It is worth noting that the skeleton of cluster 1 has a high stability under high-resolution electrospray ionization mass spectrometry (HRESI-MS) conditions with a gradually increasing energy of the ion source. Cluster 2 underwent a multistep fragmentation even under a zero ion-source voltage for the measurement of HRESI-MS. Further analysis showed that cluster 2 underwent a possible fragmentation mechanism of Dy4Co6L6 → Dy2Co6L5/DyL → DyCo2L3/DyCo2L → DyL/Co2L2. Most notably, the species emerging in the formation process of cluster 1 were tracked using time-dependent HRESI-MS, from which we proposed its possible formation mechanism of H2L → Co2L2 → Co2DyL2/Co3L2 → Co3DyL2 → Co4DyL2 → Co5Dy2L4 → Co8Dy2L6. As far as we know, it is the first time to track the formation process of Dy-Co heterometallic clusters through HRESI-MS with the proposed assembly mechanism. The magnetic properties of the two titled DyIIIxCoII10-x (x = 2, 4) clusters were studied. Both of them exhibit slow magnetic relaxation, and 1 is a single-molecule magnet at zero direct-current field.

Constructing multicomponent hybrid materials is a common and effective method to achieve high-performance anode materials for sodium ion batteries (SIBs). In this work, hierarchical nanorods compos...

Two new [Dy4]-based coordination clusters [Dy4(L1)2(L2)4(NO3)2(EtOH)4]·2MeOH (1) (H3L1 = 2-(β-naphthalideneamino)-2-(hydroxylmethyl)-1-propanol, HL2 = 2-hydroxy-1-naphthaldehyde) and [Dy4(μ4-O)(HL3)4(H2L3)2]·3H2O·EtOH·CH3CN (2) (H3L3 = 3-(((2-hydroxynaphthaen-1-yl)methylene)amino)-propane-1,2-diol) with planar and butterfly-like skeletons, respectively, were synthesized and characterized. This revealed that 1 is a field-induced single-molecule magnet with an effective barrier of Ueff = 6.1 K under a dc field of 800 Oe and 2 shows slow magnetic relaxation behaviour with Ueff = 2.6 K under zero dc field. The magnetic dilution method was applied to further investigate the magnetic relaxation behaviors of 1 and 2; as a result, slow magnetic relaxation behaviors of 1 and 2 were mostly attributed to the single Dy3+ ions, which was also confirmed by the result of ab initio calculation. Interestingly, both of them possess excellent stability in water and common organic solvents, as well as in acid and base solutions with a wide pH range (2.5–14). Surprisingly, 2 is stable even in 18 M NaOH aqueous solutions, which is rarely reported in 0D coordination compounds and is a breakthrough for paramagnetic metal clusters in stability. It helps to develop chemically stable single-molecule magnets for their application in moisture and acidic/alkaline media.

Manganese(II) acetate was reacted with indane-1,2,3-trione-1,2-dioxime (H2L), producing three new MnIII complexes containing a MnIII3O unit. Complex 1 is a zero-dimensional (0D) trinuclear manganese(III) cluster. Complexes 2 and 3 show different two-dimensional (2D) structures with their trinuclear manganese(III) units bridged through Na(I) ions. A study of the magnetic properties manifests that antiferromagnetic coupling is clearly dominant in complexes 1 and 2. In contrast, complex 3 is a single-molecule magnet with dominant ferromagnetic couplings between its metal ions. The Na(I) ions adjust the topologies of these complexes, which thus tunes the magnetic-related parameters such as the Mn–O–N–Mn dihedral angle and finally leads to the achievement of single-molecule magnets.

The formation of heterometallic clusters usually involves a much more complex self-assembly process than that of homometallic clusters. Thus the tracking of their assembly mechanism is challenging. To achieve this task, we designed one OH-containing Schiff base ligand of 1-[[(2-hydroxyethyl)imino]methyl]-2-naphthalenol (H2L) with coordination pockets facile for selective coordination with CoII/NiII and 4f metal ions. Its reactions with the corresponding metal ions gave two new isostructural dodecanuclear complexes [Dy4Co8(μ3-OH)8(L)8(OAc)4(H2O)4]·3EtOH·3CH3CN·H2O (1) and [Dy4Ni8(μ3-OH)8(L)8(OAc)4(H2O)4]·3.5EtOH·0.5CH3CN·5H2O (2), which feature a vertex-sharing tetracubane cyclic skeleton with the four DyIII ions wrapped by the eight 3d metal ions. High-resolution electrospray mass spectrometry (HRESI-MS) tests showed that the skeletons of clusters 1 and 2 have high stability even under gradually increasing energy of the ion source. Most notably, the intermediates formed in the reaction courses for clusters 1 and 2 were tracked using time-dependent HRESI-MS, which gave different proposed assembly mechanisms for 1 (H2L → DyL → DyCoL → Dy2CoL → Dy3CoL → Dy4CoL2 → Dy4Co2L3 → Dy4Co4L4 → Dy4Co8L8) and 2 (H2L → NiL → Dy2NiL2 → Dy3NiL2 → Dy4NiL2 → Dy4Ni2L3 → Dy4Ni4L3 → Dy4Ni6L4 → Dy4Ni8L8), respectively. This is the first time that different assembly mechanisms for isostructural heterometallic complexes are shown. Detailed magnetic studies revealed the absence of slow magnetic relaxation for 1 and the presence of slow magnetic relaxation for 2 with an energy barrier of 7.66 K and a pre-exponential factor of 1.45 × 10−6 s. The different magnetic performances of the two title complexes might be caused by the different metal ions of Co(II) and Ni(II).

In this study, two novel organic ligands, bis(salicylaldehyde)pyrazino-1,10-phenanthroline-7,10-dicarbohydrazide (L) and bis(salicylaldehyde)-1,10-phenanthroline-7,10-dicarbohydrazide (L1), were synthesized. These ligands were used to react with lanthanide(iii) acetate to obtain complexes 1-6, namely, [Dy5(L)2(CH3COO)5(CH3OH)(μ3-OH)(μ2-OH)(H2O)]·2CH3OH (1), [Tb5(L)2(CH3COO)5(CH3OH)(μ3-OH)(μ2-OH)(H2O)]·3CH3OH (2), [Gd5(L)2(CH3COO)5(CH3OH)(μ3-OH)(μ2-OH)(H2O)]·3CH3OH (3), [Dy5(L1)2(μ2-OH)(μ3-OH)(CH3COO)5(CH3OH)(H2O)2]·2H2O (4), [Dy5(L1)2(μ3-OH)(CH3COO)6(CH3OH)3]·CH3OH (5), and [Dy5(L1)2(μ2-OH)2(μ3-OH)(CH3COO)4(CH3OH)(H2O)2]·CH3OH (6). Fluorescence studies demonstrated that complexes 1-6 show appreciable fluorescence in the yellow-green region. In vitro antitumor screening revealed that complex 1 exhibits better inhibitory activities than the commercial anticancer drug cisplatin against SK-OV-3 and A549 tumor cell lines, with IC50 values of 8.09 ± 1.25 and 13.26 ± 0.39 μM, respectively. All six complexes showed low cytotoxicity toward normal human liver HL-7702 cells compared with cisplatin. Complexes 1 and 3 induced the highest apoptosis rate of SK-OV-3/DDP cells. They also bind to DNA via an intercalative mode with the binding constant Kq values of 1.6 × 104 and 1.19 × 104 L mol-1, respectively. Confocal fluorescence imaging ascertained that complexes 1 and 3 are primarily localized in the mitochondria. Further studies revealed that these complexes trigger SK-OV-3/DDP cell apoptosis via a mitochondrial dysfunction pathway, which is probably caused by the reduction of the mitochondrial membrane potential and the induction of reactive oxygen species production.

Two novel {Dy2}-based one dimensional chain compounds {[Dy2(H3L)4(OAc)6]·2MeOH}n (1) and {[Dy2(H3L)4(OAc)4(NCS)2]·2MeOH}n (2) (H3L = 1,3-bis(2-hydroxynaphthalenemethyleneamino)-propan-2-ol) have been prepared under solvothermal conditions. Crystal structure analyses indicate that 1 and 2 feature similar 1D chain structures bearing dinuclear secondary building units. The difference between these two structures is that one chelated acetate ligand of Dy(III) ion in 1 is replaced by one monodentate coordinated NCS− ion in 2, leading to their different coordination numbers and geometry configurations to Dy(III) ion. Magnetic properties indicate that 1 and 2 display slow magnetic relaxation behavior with an effective energy barrier of 16.44(2) K in 1 and 8.02(2) K in 2, respectively, which is maybe attributed to the subtle crystal field perturbation of Dy(III) ions.

The development of metal complexes of Schiff base has attracted much attention due to their DNA binding properties and extensive biological activities. We reported here five copper(II) complexes [Cu(L1)] (1), [Cu(L2)] (2), [Cu(L3)] (3), [Cu2(L4)(OAc)] (4), and [Cu2(L5)(HCOO)] (5) bearing the bis-Schiff base ligands of bis(5-chlorosalicylidene)-1,3-propanediamine (H2L1), bis(5-chlorosalicylidene)-2-methyl-1,3-propanediamine (H2L2), bis(5-bromosalicylidene)-2-methyl-1,3-propanediamine (H2L3), bis(5-chlorosalicylidene)-2-hydroxyl-1,3-propanediamine (H3L4), and bis(5-bromosalicylidene)-2-hydroxyl-1,3-propanediamine (H3L5), respectively. The single crystal X-ray diffraction analysis results revealed that complexes 1–3 present mononuclear structures and complexes 4 and 5 show dinuclear structures. It was also shown that all of these complexes are stable under physiological conditions. The in vitro antitumor activities of the five complexes were evaluated. Anticancer selectivity was also found for complex 2 on different cell lines with the lowest IC50 value on Hela cells. Further mechanistic studies showed that the three mononuclear Cu(II) complexes can induce apoptosis through the mitochondrial pathway by decreasing mitochondrial membrane potential and increasing the reactive oxygen species (ROS) and Ca2+ levels. They can activate caspase-3 and caspase-9, and can also regulate the expression of pro-apoptotic protein and anti-apoptotic protein in cells. All of these results showed that complex 2 is a potential anticancer drug.

In recent years, the mechanical dashboard of automobile has evolved into an all-digital one, which has brought the innovation of content display mode and the improvement of related functions. This is because in the transformation of the automotive industry, users have become more focused on the driving experience than before, and they have shifted their focus on car styling and interior design to the human-machine interaction (HMI). As a result, automobile brands on the market have introduced many distinctive HMI designs for dashboard. The author previously cooperated with WM Motor Technology Co., Ltd. to launch a commercial in-vehicle application, which allows the appearance of dashboard to be changed according to the user's emotion and preferences, catering to the individual needs. Nevertheless, in the process of cooperation between the enterprise and designers, the design principles of traditional dashboard are still followed, and there is a lack of suitable design methods of personalized HMI for digital dashboard. Therefore, this paper attempts to create a design method that provides guidance for the aforesaid process. Based on the emotional design theory, it puts forward the principles of aesthetic, usability and experience, and guides designers on how to design and what to avoid from the perspective of user experience. Besides, it also proposes some new ideas for the development of personalized theme design of dashboard, such as customized design service, multi-sensory experience, etc. This paper aims to get more designers and developers involved in the co-creation of dashboard theme design and strive to improve the users’ experience. Additionally, the design thinking method described in this paper can also provide reference for the design of other products.