Coordination Confined Thermolysis Synthesis of the Ni Single Atom Catalyst on the N-Doped Commercial Carbon for the Production of Syngas.

The electrochemical conversion of CO2 into controllable syngas (CO/H2) over a wide potential range is challenging. The main electrocatalysts are based on the noble metals Au (Ag) or heavy metal Pb. The development of alternative nonprecious catalysts is of paramount importance for practice. In this work, a simple coordination confined thermal pyrolysis method has been developed for the synthesis of Ni single-atom catalyst loaded onto nitrogen-doped commercial carbon. The catalyst is in the form of NiN3-C, which exhibits a high-performance electrocatalytic reduction of CO2 toward producing syngas with Faraday efficiencies of 62.28% of CO and 36.7% of H2. The Gibbs free energies of COOH* and H* on the NiN3-C structure were estimated by using density functional theory (DFT). The formation of COOH* intermediate is the speed-limiting step in the process, with ΔG COOH* being 0.7 eV, while H* is the speed-limiting step in the hydrogen evolution, respectively. This work provides a feasible method for the achievement of nonprecious catalysts for the resourceful use of CO2.

Single-cluster Functionalized TiO2 Nanotube Array for Boosting Water Oxidation and CO2 Photoreduction to CH3OH.

Solar-driven CO2 reduction and water oxidation to liquid fuels represents a promising solution to alleviate energy crisis and climate issue, but it remains a great challenge for generating CH3OH and CH3CH2OH dominated by multi-electron transfer. Single-cluster catalysts with super electron acceptance, accurate molecular structure, customizable electronic structure and multiple adsorption sites, have led to greater potential in catalyzing various challenging reactions. However, accurately controlling the number and arrangement of clusters on functional supports still faces great challenge. Herein, we develop a facile electrosynthesis method to uniformly disperse Wells-Dawson- and Keggin-type polyoxometalates on TiO2 nanotube arrays, resulting in a series of single-cluster functionalized catalysts P2M18O62@TiO2 and PM12O40@TiO2 (M=Mo or W). The single polyoxometalate cluster can be distinctly identified and serves as electronic sponge to accept electrons from excited TiO2 for enhancing surface-hole concentration and promote water oxidation. Among these samples, P2Mo18O62@TiO2-1 exhibits the highest electron consumption rate of 1260 µmol g-1 for CO2-to-CH3OH conversion with H2O as the electron source, which is 11 times higher than that of isolated TiO2 nanotube arrays. This work supplied a simple synthesis method to realize the single-dispersion of molecular cluster to enrich surface-reaching holes on TiO2, thereby facilitating water oxidation and CO2 reduction.

Rapid Identification of Seven Common ABO Alleles by Two-Dimensional Polymerase Chain Reaction Technology.

Introduction: The molecular biology detection technology of the human ABO blood group system makes up for the limitations in many aspects compared with conventional serological typing technology. This study aimed to establish a new method to identify seven common ABO alleles (ABO*A1.01, ABO*A1.02, ABO*A2.01, ABO*B.01, ABO*O.01.01, ABO*O.01.02, and ABO*O.02.01) by two-dimensional polymerase chain reaction (2D PCR). 2D PCR can identify multiple target genes in a closed test tube by labeling specific primers with tags homologous to the sequence of fluorescently labeled probes, and melting curve analysis is performed after the fluorescent probes are hybridized with tag complementary sequences in PCR-specific products. In this study, 2D PCR and PCR sequence-specific primer (PCR-SSP) were combined to discriminate different alleles in a single reaction, which has the characteristics of high throughput, and compared with other typing techniques; the typing results can be obtained without additional operations. Methods: The ABO*A1.01 allele genetic sequence was used as the reference sequence. The specific sense and antisense primers for seven common ABO alleles were designed on exons 6 and 7 according to the principle of 2D PCR and PCR-SSP. Single nucleotide polymorphism sites for identifying seven alleles were detected in FAM and HEX channels, respectively. Two hundred sixty DNA samples were enrolled for rapid ABO genotyping by 2D PCR, and 95 of them were selected for Sanger sequencing. The Kappa test was used to analyze the agreement of the methodologies. Results: These 7 alleles each had four characteristic melting valleys at different single nucleotide polymorphism loci. A total of 15 genotypes were detected, including ABO*A1.01/A1.02, ABO*A1.01/O.01.01, ABO*A1.01/O.01.02, ABO*A1.02/A1.02, ABO*A1.02/O.01.01, ABO*A1.02/O.01.02, ABO*B.01/B.01, ABO*B.01/O.01.01, ABO*B.01/O.01.02, ABO*O.01.01/O.01.01, ABO*O.01.01/O.01.02, ABO*O.01.02/O.01.02, ABO*A1.01/B.01, ABO*A1.02/B.01, and ABO*B.01/O.01. v (containing a rare ABO*O allele, based on the sequencing results). The Kappa test showed completely consistent results for 2D PCR and Sanger sequencing (Kappa = 1). Conclusion: The 2D PCR technique could be used for molecular typing of the ABO blood group, which was efficient, rapid, accurate, and economical.

Vitamin D Improves the Effect of Glucocorticoids on Attenuating Lipopolysaccharide-Induced IL-6 Production via TLR4/NF-κB Pathway in Human Respiratory Epithelial Cells.

BACKGROUND: Glucocorticoid (GC) resistance results in unsatisfactory outcomes in chronic rhinosinusitis with nasal polyps (CRSwNP) patients. Previous studies have shown that calcitriol, the active form of vitamin D, alone or in combination with corticosteroids, exerts crucial immunomodulatory effects on inflammatory responses. However, whether vitamin D can improve the effect of GCs to attenuate inflammation in the epithelium of CRSwNP remains unclear. METHODS: A human bronchial epithelial cell line (Beas-2B) and primary human nasal epithelial cells (HNECs) obtained from 10 patients with CRSwNP were exposed to lipopolysaccharide (LPS) for 24 h to establish an inflammation model. LPS-stimulated HNECs and Beas-2B cells were treated with/without dexamethasone in the presence or absence of calcitriol pretreatment for 24 h. The expression levels of interleukin-6 (IL-6) mRNA and protein were determined by quantitative real-time polymerase chain reaction and enzyme-linked immunosorbent assay, respectively. Toll-like receptor 4 (TLR4)/NF-κB pathway related markers were examined by western blotting. One-way ANOVA or the Kruskal-Wallis test with post hoc analysis were used for multiple comparisons among groups. RESULTS: The production of IL-6 in Beas-2B cells and primary HNECs after LPS stimulation was significantly increased, which could be inhibited by dexamethasone or calcitriol alone. However, significant inhibition of IL-6 production was observed in the calcitriol plus dexamethasone group. Further analysis showed that calcitriol could enhance the effect of dexamethasone in inhibiting LPS-induced overexpression of TLR4, Myd88, and phosphorylation of p65. CONCLUSION: Our findings demonstrated that vitamin D could improve the effect of GCs to alleviate the level of IL-6 induced by LPS via the TLR4/NF-κB pathway in human respiratory epithelial cells.

Microenvironment Regulation of {Co4IIO4} Cubane for Syngas Photosynthesis.

It is a great challenging task for selectivity control of both CO2 photoreduction and water splitting to produce syngas via precise microenvironment regulation. Herein, a series of UiO-type Eu-MOFs (Eu-bpdc, Eu-bpydc, Rux-Eu-bpdc, and Rux-Eu-bpydc) with different surrounding confined spaces were designed and synthesized. These photosensitizing Rux-Eu-MOFs were used as the molecular platform to encapsulate the [CoII4(dpy{OH}O)4(OAc)2(H2O)2]2+ (Co4) cubane cluster for constructing Co4@Rux-Eu-MOF (x = 0.1, 0.2, and 0.4) heterogeneous photocatalysts for efficient CO2 photoreduction and water splitting. The H2 and CO yields can reach 446.6 and 459.8 µmol·g-1, respectively, in 10 h with Co4@Ru0.1-Eu-bpdc as the catalyst, and their total yield can be dramatically improved to 2500 µmol·g-1 with the ratio of CO/H2 ranging from 1:1 to 1:2 via changing the photosensitizer content in the confined space. By increasing the N content around the cubane, the photocatalytic performance drops sharply in Co4@Ru0.1-Eu-bpydc, but with an enhanced proportion of CO in the final products. In the homogeneous system, the Co4 cubane was surrounding with Ru photosensitizers via week interactions, which can drive water splitting into H2 with >99% selectivity. Comprehensive structure-function analysis highlights the important role of microenvironment regulation in the selectivity control via constructing homogeneous and heterogeneous photocatalytic systems. This work provides a new insight for engineering a catalytic microenvironment of the cubane cluster for selectivity control of CO2 photoreduction and water splitting.

The effects and possible mechanism of action of apolipoprotein M on the growth of breast cancer cells.

BACKGROUND: To investigate the effects and mechanism of action of apolipoprotein M (ApoM) on the growth of breast cancer (BC) cells. METHODS AND RESULTS: Bioinformatics, cell experiments and animal experiments were used to verify the effect of ApoM on breast cancer cell lines and breast tumor growth in vivo. ApoM expression was significantly reduced in BC tissues, and patients with lower ApoM mRNA expression had a poorer prognosis (P < 0.0001). Besides, ApoM can partially inhibit the proliferative, migratory and invasive processes of BC cells. In vivo, the difference between ApoM-OE and NC groups was no significant. The level of vitamin D receptor (VDR) protein in MDA-MB-231 cells was increased by overexpression of ApoM (P < 0.05), while in MCF-7 cells, VDR levels decreased (P < 0.05). CONCLUSIONS: ApoM can partially inhibit the growth of BC cells. VDR may play a role, but is not the main pathway.

Switching Excited State Distribution of Metal-Organic Framework for Dramatically Boosting Photocatalysis.

Photosensitization associated with electron/energy transfer represents the central science of natural photosynthesis. Herein, we proposed a protocol to dramatically improve the sensitizing ability of metal-organic frameworks (MOFs) by switching their excited state distribution from 3 MLCT (metal-to-ligand charge transfer) to 3 IL (intraligand). The hierarchical organization of 3 IL MOFs and Co/Cu catalysts facilitates electron transfer for efficient photocatalytic H2 evolution with a yield of 26 844.6 µmol g-1 and CO2 photoreduction with a record HCOOH yield of 4807.6 µmol g-1 among all the MOF photocatalysts. Systematic investigations demonstrate that strong visible-light-absorption, long-lived excited state and ingenious multi-component synergy in the 3 IL MOFs can facilitate both interface and intra-framework electron transfer to boost photocatalysis. This work opens up an avenue to boost solar-energy conversion by engineering sensitizing centers at a molecular level.

Feeding Carbonylation with CO2 via the Synergy of Single-Site/Nanocluster Catalysts in a Photosensitizing MOF.

Solar-driven carbonylation with CO2 replacing toxic CO as a C1 source is of considerable interest; however it remains a great challenge due to the inert CO2 molecule. Herein, we integrate cobalt single-site and ultrafine CuPd nanocluster catalysts into a porphyrin-based metal-organic framework to construct composite photocatalysts (Cu1Pd2)z@PCN-222(Co) (z = 1.3, 2.0, and 3.0 nm). Upon visible light irradiation, excited porphyrin can concurrently transfer electrons to Co single sites and CuPd nanoclusters, providing the possibility for coupling CO2 photoreduction and Suzuki/Sonogashira reactions. This multicomponent synergy in (Cu1Pd2)1.3@PCN-222(Co) can not only replace dangerous CO gas but also dramatically promote the photosynthesis of benzophenone in CO2 with over 90% yield and 97% selectivity under mild condition. Systematic investigations clearly decipher the function and collaboration among different components in these composite catalysts, highlighting a new insight into developing a sustainable protocol for carbonylation reactions by employing greenhouse gas CO2 as a C1 source.

H-Bond-Mediated Selectivity Control of Formate versus CO during CO2 Photoreduction with Two Cooperative Cu/X Sites.

It is highly desirable to achieve solar-driven conversion of CO2 to valuable fuels with controlled selectivity. The existing catalysts are mainly explored for CO production but rarely for formate generation. Herein, highly selective photoreduction of CO2 to formate (99.7%) was achieved with a high yield of 3040 µmol g-1 in 10 h by hierarchical integration of photosensitizers and monometallic [bpy-Cu/ClX] (X = Cl or adenine) catalysts into a stable Eu-bpy metal-organic framework. However, replacing X with pyridine in [bpy-CuCl/X] significantly reduced formate production while increasing the CO yield to 960 µmol g-1. Systematic investigations revealed that the catalytic process is mediated by the H-bond synergy between Cu-bound X and CO2-derived species, and the selectivity of HCOO- can be controlled by simply replacing the coordination ligands. This work provides a molecularly precise structural model to provide mechanistic insights for selectivity control of CO2 photoreduction.

Construction of Low-Cost Z-Scheme Heterostructure Cu2 O/PCN for Highly Selective CO2 Photoreduction to Methanol with Water Oxidation.

Solar-driven CO2 reaction with water oxidation into alcohols represents a promising approach to achieve real artificial photosynthesis. However, rapid recombination of photogenerated carriers seriously restricts the development of artificial photosynthesis. Herein, a facile method is explored to construct low-cost Z-Scheme heterostructure Cu2 O/polymeric carbon nitride (PCN) by in situ growth of Cu2 O hollow nanocrystal on PCN. The protective PCN layer and Z-schematic charge flow can make robust Cu2 O/PCN photocatalysts, and the spatial separation of electrons and holes with high redox potentials of ECB (-1.15 eV) and EVB (1.65 eV) versus NHE can efficiently drive CO2 photoreduction to methanol in pure water, which is further confirmed by DFT calculation. The Z-scheme heterostructure Cu2 O/PCN exhibits a high methanol yield of 276 µmol g-1 in 8 h with ca. 100% selectivity, much superior to that of isolated Cu2 O and PCN, and all the reported Cu2 O-based heterostructures. This work provides a unique strategy to efficiently and selectively promote the conversion of CO2 and H2 O into high-value chemicals by constructing a low-cost Z-scheme heterostructure.

Downregulation of RPS14 inhibits the proliferation and metastasis of estrogen receptor-positive breast cancer cells.

Ribosomal protein S14 (RPS14) is a component of the 40S ribosomal subunit and is considered to be indispensable for ribosomal biogenesis. Previously, we found that RPS14 was significantly downregulated in estrogen receptor-positive (ER+) breast cancer cells following treatment with 4-hydroxytamoxifen (4-OH-TAM). However, its role in breast cancer remains poorly understood. In the present study, we sought to demonstrate, for the first time, that RPS14 is highly expressed in ER+ breast cancer tissues and its downregulation can significantly inhibit the proliferation, cycle, and metastasis of ER+ breast cancer cells, as well as induce cell apoptosis. Quantitative RT-PCR and western blotting were used to determine the expression of target genes. Herein, lentivirus-mediated small hairpin RNA (shRNA) targeting RPS14 was designed to determine the impact of RPS14 knockdown on ER+ breast cancer cells. Further, bioinformatics analysis was used to reveal the significance of differentially expressed genes in RPS14 knockdown breast cancer cells. RPS14 was highly expressed in ER+ breast cancer tissues compared to ER- tissues. The downregulation of RPS14 in two ER+ breast cancer cell lines suppressed cell proliferation, cell cycle and metastasis, and induced apoptosis. Based on bioinformatics analysis, the expression level of several significant genes, such as ASNS, Ret, and S100A4, was altered in breast cancer cells after RPS14 downregulation. Furthermore, the BAG2 and interferon signaling pathways were identified to be significantly activated. The downregulation of RPS14 in ER+ breast cancer cells can inhibit their proliferation and metastasis.

Risk factors for mortality in patients over 70 years old with COVID-19 in Wuhan at the early break: retrospective case series.

BACKGROUND: Elderly patients with COVID-19 were shown to have a high case-fatality rate. We aimed to explore the risk factors associated with death in patients over 70 years old (yr). METHODS: In this retrospective study, we enrolled consecutively hospitalized patients over 70 yr with COVID-19 between January 20 and February 15, 2020 in Renmin Hospital of Wuhan University. Epidemiological, demographic, and clinical data were collected. Clinical subtypes, including mild, moderate, severe, and critical types, were used to evaluate the severity of disease. Patients were classified into two groups: survivor and non-survivor groups. Clinical data were compared between the two groups. Univariable and multivariable Cox regression methods were used to explore the risk factors. RESULTS: A total of 147 patients were enrolled. The case-fatality rate was 28.6%. Multivariable Cox proportional hazard regression showed that clinical subtypes, including the severe type (HR = 2.983, 95% CI: 1.231-7.226, P = 0.016) and the critical type (HR = 3.267, 95%CI: 1.009-10.576, P = 0.048), were associated with increasing risk of death when compared with the general type. Blood urea nitrogen greater than 9.5 mmol/L (HR = 2.805, 95% CI: 1.141-6.892, P = 0.025) on admission was an independent risk factor for death among laboratory findings. CONCLUSION: The patients over 70 yr with COVID-19 had a high case-fatality rate. The risk factors, including clinical subtypes and blood urea nitrogen greater than 9.5 mmol/L, could help physicians to identify elderly patients with poor clinical outcomes at an early stage.

Risk Factors of Coronavirus Disease 2019-Related Mortality and Optimal Treatment Regimens: A Retrospective Study.

BACKGROUND Coronavirus disease 2019 (COVID-19) is spreading rapidly worldwide, and scientists are trying to find a way to overcome the disease. We explored the risk factors that influence patient outcomes, including treatment regimens, which can provide a reference for further treatment. MATERIAL AND METHODS A retrospective cohort study analysis was performed using data from 97 patients with COVID-19 who visited Wuhan Union Hospital from February 2020 to March 2020. We collected data on demographics, comorbidities, clinical manifestations, laboratory tests, treatment methods, outcomes, and complications. Patients were divided into a recovered group and a deceased group. We compared the differences between the 2 groups and analyzed risk factors influencing the treatment effect. RESULTS Seventy-six patients recovered and 21 died. The average age and body mass index (BMI) of the deceased group were significantly higher than those of the recovered group (69.81±6.80 years vs 60.79±11.28 years, P<0.001 and 24.95±3.14 kg/m² vs 23.09±2.97 kg/m², P=0.014, respectively). The combination of antiviral drugs and supportive therapy appears to be associated with the lowest mortality (P<0.05). Multivariate Cox regression analysis revealed that age, BMI, H-CRP, shock, and acute respiratory distress syndrome (ARDS) were independent risk factors for patients with COVID-19 (P<0.05). CONCLUSIONS Elderly patients and those with a high BMI, as well as patients who experience shock and ARDS, may have a higher risk of death from COVID-19. The combination of antiviral drugs and supportive therapy appears to be associated with lower mortality, although further research is needed.

The value of the neutrophil-to-lymphocyte ratio and platelet-to-lymphocyte ratio as complementary diagnostic tools in the diagnosis of rheumatoid arthritis: A multicenter retrospective study.

BACKGROUND: The neutrophil-to-lymphocyte ratio (NLR) and platelet-to-lymphocyte ratio (PLR) have drawn attention in recent years as novel non-specific inflammatory markers; however, only a few studies have been conducted to investigate their value in RA. OBJECTIVE: To investigate the value of the neutrophil-to-lymphocyte ratio (NLR) and the platelet-to-lymphocyte ratio (PLR) as complementary diagnostic tools in rheumatoid arthritis (RA). METHOD: This study included 1009 patients with RA, 170 patients with other rheumatic diseases, and 245 healthy individuals from four medical centers. The patients' general data, including complete blood count, C-reactive protein (CRP), erythrocyte sedimentation rate (ESR), and rheumatoid factor (RF), were retrospectively analyzed, and the NLR and PLR were calculated. Potential effective indicators were screened by logistic regression analysis, and a receiver operating characteristic (ROC) curve was plotted to evaluate their diagnostic value for RA. RESULTS: (a) The NLR and PLR were significantly higher in the RA group than in the non-RA group and the control group (P < .05). (b) Spearman's Rho showed that the NLR was positively correlated with the PLR (r = .584, P < .05), RF (r = .167, P < .01), and CRP (r = .280, P < .01) but was not significantly correlated with ESR (r = .100, P > .05). The PLR was positively correlated with RF (r = .139, P < .01), CRP (r = .297, P < .01), and ESR (r = .262, P < .05). (c) Logistic analysis showed that RF, CRP, ESR, and the NLR had diagnostic value for RA. (d) For the NLR, the area under the curve (AUC) of the ROC curve was 0.831; at the cutoff value of 2.13, the diagnostic sensitivity, specificity, accuracy, and Youden index were 76.7%, 75.9%, 76.4%, and 0.5424, respectively. CONCLUSION: The NLR was less effective than CRP and RF but was superior to ESR in the diagnosis of RA. The NLR can thus be used as a complementary diagnostic indicator in the diagnosis of RA.

High-Throughput Two-Dimensional Polymerase Chain Reaction Technology.

Polymerase chain reaction (PCR) is a very powerful tool for clinical gene detection. Multiplex PCR especially improves the throughput of this technology. However, it is often necessary to employ techniques such as electrophoresis, mass spectrometry, or sequencing after multiplex PCR amplification for product identification, which requires additional equipment and has high risks of contamination. In this work, we developed a high-throughput two-dimensional (2D) PCR technology that can identify multiple target genes simultaneously in just one closed tube and within a relatively short time by using both fluorescence and the melting temperature (Tm). As an example, a method detecting 9 human papillomavirus (HPV) subtypes and reference genes in a single tube was successfully established using 2D PCR. If designed properly, 2D PCR is believed to have the capability to identify more than 30 genes in one closed tube at a time. This method is particularly suitable for distinguishing microorganisms, single-nucleotide polymorphisms, and the methylation of genes and will be of great help to clinical work.

Development and validation of a survival model for lung adenocarcinoma based on autophagy-associated genes.

BACKGROUND: Given that abnormal autophagy is involved in the pathogenesis of cancers, we sought to explore the potential value of autophagy-associated genes in lung adenocarcinoma (LUAD). METHODS: RNA sequencing and clinical data on tumour and normal samples were acquired from The Cancer Genome Atlas (TCGA) database and randomly assigned to training and testing groups. Differentially expressed autophagy-associated genes (AAGs) were screened. Within the training group, Cox regression and Lasso regression analyses were conducted to screen five prognostic AAGs, which were used to develop a model. Kaplan-Meier (KM) and receiver operating characteristic (ROC) curves were plotted to determine the performance of the model in both groups. Immunohistochemistry was used to demonstrate the differential expression of AAGs in tumour and normal tissues at the protein level. Gene Ontology (GO) functional annotation and Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway enrichment analyses were utilized to further elucidate the roles of AAGs in LUAD. RESULTS: The data from the TCGA database included 497 tumour and 54 normal samples, within which 30 differentially expressed AAGs were screened. Using Cox regression and Lasso regression analyses for the training group, 5 prognostic AAGs were identified and the prognostic model was constructed. Patients with low risk had better overall survival (OS) in the training group (3-year OS, 73.0% vs 48.0%; 5-year OS, 45.0% vs 33.8%; P = 1.305E-04) and in the testing group (3-year OS, 66.8% vs 41.2%; 5-year OS, 31.7% vs 25.8%; P = 1.027E-03). The areas under the ROC curves (AUC) were significant for both the training and testing groups (3-year AUC, 0.810 vs 0.894; 5-year AUC, 0.792 vs 0.749). CONCLUSIONS: We developed a survival model for LUAD and validated the performance of the model, which may provide superior outcomes for the patients.

Low-complexity equalizer with a hybrid decision scheme for 50 Gb/s/λ PAM4-PON using a low-cost 10 G receiver.

In this Letter, we experimentally demonstrate a 50Gb/s/λ four-level pulse amplitude modulation-based passive optical network system with a 10 G class receiver. A memory polynomial equalizer (MPE) combined with a decision feedback equalizer (DFE) is applied to eliminate channel distortions in the system. To further improve the performance of the MPE-DFE, for the first time, to the best of our knowledge, a low-complexity hybrid decision scheme (HDS) is proposed, which consists of single-symbol decision (SSD) and multi-symbol decision (MSD). The SSD is exactly the conventional hard decision based on minimum Euclidean distance, whereas MSD is based on a simplified maximum likelihood detection principle with M-algorithm. In terms of complexity, MSD requires 19.1% more multiplications than SSD, but the symbol number of MSD only accounts for less than 20% of the total signal frame when the received optical power is greater than -27dBm. Experimental results show that the proposed MPE-DFE with HDS achieves a 0.7 dB and 1.3 dB sensitivity gain compared with conventional SSD, and up to 35.4 dB and 31.4 dB link power budget, regarding the forward error correction threshold of 10-2 and 10-3, respectively.

Self-Supported Nanoporous Au3 Cu Electrode with Enriched Gold on Surface for Efficient Electrochemical Reduction of CO2.

The key to the electrochemical conversion of CO2 lies in the development of efficient electrocatalysts with ease of operation, good conductivity, and rich active sites that fulfil the desired reaction direction and selectivity. Herein, an oxidative etching of Au20 Cu80 alloy is used for the synthesis of a nanoporous Au3 Cu alloy, representing a facile strategy for tuning the surface electronic properties and altering the adsorption behavior of the intermediates. HRTEM, XPS, and EXAFS results reveal that the curved surface of the synthesized nanoporous Au3 Cu is rich in gold with unsaturated coordination conditions. It can be used directly as a self-supported electrode for CO2 reduction, and exhibits high Faradaic efficiency (FE) of 98.12 % toward CO at a potential of -0.7 V versus the reversible hydrogen electrode (RHE). The FE is 1.47 times that over the as-made single nanoporous Au. Density functional theory reveals that *CO has a relatively long distance on the surface of nanoporous Au3 Cu, making desorption of CO easier and avoiding CO poisoning. The Hirshfeld charge distribution shows that the Au atoms have a negative charge and the Cu atoms exhibit a positive charge, which separately bond to the C atom and O atom in the *COOH intermediate through a bidentate mode. This affords the lowest *COOH adsorption free energy and low desorption energy for CO molecules.

Encapsulation of Single Iron Sites in a Metal-Porphyrin Framework for High-Performance Photocatalytic CO2 Reduction.

Efficient CO2 reduction with earth-abundant photocatalysts is a highly attractive but very challenging process for chemists. Herein, we synthesized an indium-porphyrin framework, In(H2TCPP)(1-n)[Fe(TCPP)(H2O)](1-n)[DEA](1-n) (In-FenTCPP-MOF; H2TCPP = tetrakis(4-benzoic acid)porphyrine; DEA = diethylamine), with a porphyrin ring supporting the single-site iron for the high-performance visible-light-driven conversion of CO2 to CO. A high CO yield of 3469 µmol g-1 can be achieved by a 24 h photocatalytic reaction with a high CO selectivity (ca. 99.5%). This activity was much higher than that of its cobalt analogues or the Fe-free indium-based metal-organic framework (MOF). Systematic experimental and theoretical studies indicate that the porphyrin-supported iron centers in the MOF matrix serve as efficient active sites, which can accept electrons from the photoexcited MOFs in order to mediate CO2 reduction.

Metastasis-associated protein 1, modulated by miR-30c, promotes endometrial cancer progression through AKT/mTOR/4E-BP1 pathway.

OBJECTIVE: Though metastasis-associated protein 1 (MTA1) is widely overexpressed in human cancers and is associated with advanced clinicopathological characteristics and survival in related diseases, the association between MTA1 and endometrial cancer (EC) is little known and needs to be studied. METHODS: Western blot and immunohistochemistry were used to analyze protein expression level of cells and tissues, while real-time PCR was used for RNA detection. Bioinformatics tool analysis revealed the relationship between MTA1 and clinicopathological characteristics and survival. CCK-8 assay, colony-formation assay, cell scratch assay, and Transwell assay were performed to determine cell proliferation, migration and invasion abilities, respectively. RESULTS: The expression level of MTA1 was significantly higher in human EC tissues than in normal endometrium. MTA1 expression was correlated positively with lymph nodes metastasis and poor survival rate in EC. Experimentally overexpressed MTA1 could promote cell proliferation, migration and invasion abilities of EC cell lines Ishikawa, HEC-1B, and RL-952, while reduction of MTA1 inhibited these cell biological behaviors. Moreover, MTA1 could also reverse the negative effect of miR-30c, a direct modulator of MTA1, on EC cells. Our research also revealed that overexpression of MTA1 contributed to EC tumor growth, while knockdown of MTA1 resulted in tumor growth inhibition. Additionally, the phosphorylation levels of mTOR (S2448) and 4E-BP1 (T37/46) changed significantly along with AKT (T308) under regulation of MTA1, both in vivo and vitro. CONCLUSION: Our results showed that MTA1, as a downstream target of miR-30c, might promote EC progression via AKT/mTOR/4E-BP1 pathway, which indicated the potential therapy target of MTA1 in EC.