Revealing the Indispensable Role of In Situ Electrochemically Reconstructed Mn(II)/Mn(III) in Improving the Performance of Lithium-Carbon Dioxide Batteries.

Li-CO2 batteries are regarded as promising high-energy-density energy conversion and storage devices, but their practicability is severely hindered by the sluggish CO2 reduction/evolution reaction (CORR/COER) kinetics. Due to the various crystal structures and unique electronic configuration, Mn-based cathode catalysts have shown considerable competition to facilitate CORR/COER. However, the specific active sites and regulation principle of Mn-based catalysts remain ambiguous and limited. Herein, this work designs novel Mn dual-active sites (MOC) supported on N-doped carbon nanofibers and conduct a comprehensive investigation into the underlying relationship between different Mn active sites and their electrochemical performance in Li-CO2 batteries. Impressively, this work finds that owing to the in situ generation and stable existence of Mn(III), MOC undergoes obvious electrochemical reconstruction during battery cycling. Moreover, a series of characterizations and theoretical calculations demonstrate that the different electronic configurations and coordination environments of Mn(II) and Mn(III) are conducive to promoting CORR and COER, respectively. Benefiting from such a modulating behavior, the Li-CO2 batteries deliver a high full discharge capacity of 10.31 mAh cm-2, and ultra-long cycle life (327 cycles/1308 h). This fundamental understanding of MOC reconstruction and the electrocatalytic mechanisms provides a new perspective for designing high-performance multivalent Mn-integrated hybrid catalysts for Li-CO2 batteries.

Highly Electrically Conductive Polyiodide Ionic Liquid Cathode for High-Capacity Dual-Plating Zinc-Iodine Batteries.

Zinc-iodine batteries are one of the most intriguing types of batteries that offer high energy density and low toxicity. However, the low intrinsic conductivity of iodine, together with high polyiodide solubility in aqueous electrolytes limits the development of high-areal-capacity zinc-iodine batteries with high stability, especially at low current densities. Herein, we proposed a hydrophobic polyiodide ionic liquid as a zinc-ion battery cathode, which successfully activates the iodine redox process by offering 4 orders of magnitude higher intrinsic electrical conductivity and remarkably lower solubility that suppressed the polyiodide shuttle in a dual-plating zinc-iodine cell. By the molecular engineering of the chemical structure of the polyiodide ionic liquid, the electronic conductivity can reach 3.4 × 10-3 S cm-1 with a high Coulombic efficiency of 98.2%. The areal capacity of the zinc-iodine battery can achieve 5.04 mAh cm-2 and stably operate at 3.12 mAh cm-2 for over 990 h. Besides, a laser-scribing designed flexible dual-plating-type microbattery based on a polyiodide ionic liquid cathode also exhibits stable cycling in both a single cell and 4 × 4 integrated cell, which can operate with the polarity-switching model with high stability.

Bridging molecular photosensitizer and catalyst on carbon nanotubes toward enhanced selectivity and durability for CO2 photoreduction.

Homogenous molecular photocatalysts for CO2 reduction, especially metal complex-based photosensitizer‒catalyst assemblages, have been attracting extensive research interests due to their efficiency and customizability. However, their low durability and recyclability limit practical applications. In this work, we immobilized the catalysts of metal terpyridyl complexes and the photosensitizer of [Ru(bpy)3]Cl2 onto the surface of carbon nanotubes through covalent bonds and electrostatic interactions, respectively, transforming the homogeneous system into a heterogeneous one. Our characterizations prove that these metal complexes are well dispersed on CNTs with a high loading (ca. 12 wt.%). Photocatalytic measurements reveal that catalytic activity is remarkably enhanced when the molecular catalysts are anchored, which is three times higher than that of homogeneous molecular catalysts. Moreover, when the photosensitizer of [Ru(bpy)3]Cl2 is immobilized, the side reaction of hydrogen evolution is completely suppressed and the selectivity for CO production reaches 100%, with its durability also significantly improved. This work provides an effective pathway for constructing heterogeneous photocatalysts based on rational assembly of efficient molecular photosensitizers and catalysts.

The effects of electrodeposition temperature on morphology and corrosion resistance of calcium phosphorus coatings on magnesium alloy: comparative experimental and molecular dynamics simulation studies.

In this study, CaP coatings were prepared on the surface of an AZ31B magnesium alloy using electroplating in order to slow down the degradation rate of magnesium alloy in the simulated physiological environment. The effect of plating temperature on the properties of CaP coatings was investigated by combining experimental techniques with molecular dynamics (MD) simulation. The surface morphology of CaP coatings changed from dendritic lamellar to granular structure with the increase of plating temperature, but the main structure of CaP coatings prepared at all temperatures was CaHPO4·2H2O. The CaP coatings prepared at 60 °C have higher corrosion resistance compared to coatings prepared at other temperatures. The MD simulation revealed the DCPD/Mg interfacial binding mechanism, and DCPD/Mg could form a stable interfacial layer at different temperatures because the binding energy was negative. HPO42- and H2O groups in the DCPD structure acted as riveting groups in the interfacial layer and formed Mg-HPO42- and Mg-H2O dipole pairs with Mg respectively through electrostatic interaction and van der Waals forces. The interfacial bonding energy between DCPD/Mg reached its lowest at 60 °C and the relative contents of HPO42- and H2O in the interface layer were the highest at this temperature, which may explain the high corrosion resistance and high bonding force of CaP coatings prepared at this temperature.

Evaluation of creatine kinase (CK)-MB to total CK ratio as a diagnostic biomarker for primary tumors and metastasis screening.

Objective: Creatine kinase (CK) and its myocardial band isoenzyme (CK-MB) were considered important diagnostic indicators for identifying suspected acute myocardial infarction. However, the serum level of CK-MB is frequently exaggerated in some pathological states without cardiogenic damage, like cancer. Sometimes, the CK-MB level is even greater than the total CK. This study intended to investigate the association between malignancy and an abnormally high ratio of CK-MB to total CK (CK-MB/CK) and to assess the diagnostic relevance of this ratio as a biomarker for cancer. Methods: Patients hospitalized between September 2019 and September 2022 at Shandong Provincial Qianfoshan Hospital (Jinan, Shandong, China) with serum CK-MB activity greater than total CK activity (CK-MB/CK > 1.0) were recruited as research subjects. Then the demographic and clinical characteristics of these patients were systemically analyzed. The correlation between clinical characteristics (such as cancer types, tumor locations, and tumor metastasis) and laboratory test results (such as serum CK-MB activity, total CK activity, and the CK-MB/CK ratio) was also investigated. Results: We found that over 44% of the patients with CK-MB/CK > 1.0 were diagnosed with malignancies, and the CK-MB/CK ratio in malignancies patients was significantly higher than in non-malignancies patients. The increase of CK-MB/CK ratio was most obvious in patients with colorectal carcinoma and prostatic carcinoma. Additionally, extremely elevated CK-MB/CK ratios were observed in individuals with metastatic neoplasms, especially in those who suffered from numerous sites of metastasis. Conclusions: The serum CK-MB/CK ratio can be utilized as a readily accessible supplement diagnostic biomarker in screening for primary and metastatic cancers.

Gold-silver alloy hollow nanoshells-based lateral flow immunoassay for colorimetric, photothermal, and SERS tri-mode detection of SARS-CoV-2 neutralizing antibody.

Although many approaches have been developed for the quick assessment of SARS-CoV-2 infection, few of them are devoted to the detection of the neutralizing antibody, which is essential for assessing the effectiveness of vaccines. Herein, we developed a tri-mode lateral flow immunoassay (LFIA) platform based on gold-silver alloy hollow nanoshells (Au-Ag HNSs) for the sensitive and accurate quantification of neutralizing antibodies. By tuning the shell-to-core ratio, the surface plasmon resonance (SPR) absorption band of the Au-Ag HNSs is located within the near infrared (NIR) region, endowing them with an excellent photothermal effect under the irradiation of optical maser at 808 nm. Further, the Raman reporter molecule 4-mercaptobenzoic acid (MBA) was immobilized on the gold-silver alloy nanoshell to obtain an enhanced SERS signal. Thus, these Au-Ag HNSs could provide colorimetric, photothermal and SERS signals, with which, tri-mode strips for SARS-CoV-2 neutralizing antibody detection were constructed by competitive immunoassay. Since these three kinds of signals could complement one another, a more accurate detection was achieved. The tri-mode LFIA achieved a quantitative detection with detection limit of 20 ng/mL. Moreover, it also successfully detected the serum samples from 98 vaccinated volunteers with 79 positive results, exhibiting great application value in neutralizing antibody detection.

Nomogram for predicting the prognosis of sudden sensorineural hearing loss patients based on clinical characteristics: a retrospective cohort study.

Background: Based on the clinical characteristics of patients, a nomogram predicting the prognosis of patients suffering from sudden sensorineural hearing loss (SSNHL) was constructed, which could aid in personalized treatment. Methods: Data on the clinical characteristics of patients with SSNHL were collected and statistically analyzed. A nomogram for predicting the hearing prognosis of SSNHL patients were then constructed. Results: A total of 356 patients were included in this study, including 227 and 129 in the recovery group (63.76%) and non-recovery group (36.24%), respectively. Univariable logistic regression demonstrated that age, gender, body mass index (BMI), marital, Audiogram curve, vertigo, hearing loss degree, and time to initial treatment were associated with hearing outcomes. Multivariate logistic models showed that age [odds ratio (OR): 0.479, 95% confidence interval (CI): 0.301-0.748, P<0.001], descending (OR: 0.116, 95% CI: 0.047-0.275, P<0.001) and flat audiogram curves (OR: 0.397, 95% CI: 0.159-0.979, P=0.045), profound hearing loss (OR: 0.047, 95% CI: 0.013-0.152, P<0.001), and treatment initiation after 1 week (8-14 days: OR: 0.047, 95% CI: 0.013-0.152, P<0.001; >14 days: OR: 0.131, 95% CI: 0.039-0.413) were risk factors for the hearing recovery. Logistic regression analyses were conducted to construct the prognostic nomogram. As estimated by the area under the receiver operating characteristic curve (ROC), the model had an accuracy of 0.867 (95% CI: 0.709-0.747). The validation analysis confirmed the high accuracy of the nomogram, and the decision curve showed that the model has potential clinical application value. Conclusions: This study demonstrated that age, descending and flat audiogram curves, profound hearing loss, and initiating treatment after 1 week of SSNHL onset were independent risk factors associated with a worse hearing recovery prognosis. Using these factors, a nomogram with a high prediction accuracy was developed to predict the hearing recovery rate of SSNHL patients.

Enhancing the durability of Au clusters in CO2 photoreduction via encapsulation in Cu-based metal-organic frameworks.

Here, we report the encapsulation of Au25 nanoclusters in a Cu3(BTC)2 metal-organic framework (Au25@Cu-BTC), which can achieve CO2 photoreduction for selective CO production in a gas-solid reaction system at low-concentration CO2 atmospheres (even to 0.1%), with remarkably enhanced durability up to at least 48 h.

Rationally Designed Matrix-Free Carbon Dots with Wavelength-Tunable Room-Temperature Phosphorescence.

We report the rational design of the matrix-free carbon dots (C-dots) with long wavelength and wavelength-tunable room-temperature phosphorescence (RTP). Taking advantage of microwave-assisted heating treatment, three RTP C-dots in boric acid (BA) composites are synthesized by using diethylenetriaminepentakis (methylphosphonic acid) as a multiple-sites crosslink agent, a moderately acid catalyst and P source; phenylenediamines (either o-PD, m-PD, or p-PD, respectively) as building block while BA as a carbonization-retardant matrix. After the water-soluble BA matrix is removed by dialysis, three matrix-free C-dots are obtained with RTP emission at 540, 550 and 570 nm under an excitation wavelength of 365 nm. Alterations of RTP emission of three matrix-free C-dots are ascribed to the difference in their particle size and band gap from n-π* transition. Furthermore, the application of three matrix-free C-dots are successfully performed in information encryption and decryption.

Identification of competing endogenous RNA network in laryngeal squamous cell carcinoma.

OBJECTIVE: This study was conducted to investigate key long noncoding RNAs (lncRNAs) involved in competitive endogenous RNA (ceRNA) network associated with laryngeal squamous cell carcinoma (LSCC). MATERIALS AND METHODS: Three mRNA datasets, two miRNA datasets, and one lncRNA dataset of LSCC were downloaded from GEO database. Following the identification of differentially expressed mRNAs (DEmRNAs), (microRNAs) miRNAs (DEmiRNAs), and lncRNAs (DElncRNAs) in LSCC compared with adjacent tissues, functional enrichment of DEmRNAs was performed. Then, construction of the ceRNA (DElncRNA-DEmiRNA-DEmRNA) regulatory network and functional analyses of all DEmRNAs in ceRNA regulatory network were conducted. Quantitative real-time polymerase chain reactions (qRT-PCR) were used to detect the expression levels of selected DEmRNAs, DEmiRNAs, and DElncRNAs. RESULTS: A total of 3449 DEmRNAs, 40 DEmiRNAs, and 100 DElncRNAs were identified in LSCC. The ceRNA networks, which contained 132 DElncRNA-DEmiRNA pairs and 287 DEmiRNA-DEmRNA pairs, involving 44 lncRNAs, 3 miRNAs, and 271 mRNAs, were obtained. DEmRNAs in ceRNA regulatory networks were significantly enriched in pathways in cancer, prostate cancer, and aldosterone-regulated sodium reabsorption. Except for HCG22 and hsa-miR-1246, expressions of the others in the qRT-PCR results played the same pattern with that in our integrated analysis, generally. CONCLUSIONS: We concluded that HCG22/EGOT-hsa-miR-1275-FAM107A and HCG22/EGOT-hsa-miR-1246-Glycerol-3-phosphate dehydrogenase 1 like interaction pairs may play a central role in LSCC.

Precisely Tailoring Heterometallic Polyoxotitanium Clusters for the Efficient and Selective Photocatalytic Oxidation of Hydrocarbons.

Photocatalysis is a promising yet challenging approach for the selective oxidation of hydrocarbons to valuable oxygenated chemicals with O2 under mild conditions. In this work, we report an atomically precise material model to address this challenge. The key to our solution is the rational incorporation of Fe species into polyoxotitanium cluster to form a heterometallic Ti4 Fe1 cocrystal. This newly designed cocrystal cluster, which well governs the energy and charge transfer as evidenced by spectroscopic characterizations and theoretical calculations, enables the synergistic process involving C(sp3 )-H bond activation by photogenerated holes and further reactions by singlet oxygen (1 O2 ). Remarkably, the cocrystal Ti4 Fe1 cluster achieves efficient and selective oxidation of hydrocarbons (C5 to C16 ) into aldehydes and ketones with a conversion rate up to 12 860 µmol g-1 h-1 , 5 times higher than that of Fe-doped Ti3 Fe1 cluster. This work provides insights into photocatalyst design at atomic level enabling synergistic catalysis.

Nucleoside Triphosphate Hydrolases Assay in Toxoplasm gondii and Neospora caninum for High-Throughput Screening using a Robot Arm.

Protozoan parasites infect humans and many warm-blooded animals. Toxoplasma gondii, a major protozoan parasite, is commonly found in HIV-positive patients, organ transplant recipients and pregnant women, resulting in the severe health condition, Toxoplasmosis. Another major protozoan, Neospora caninum, which bears many similarities to Toxoplasma gondii, causes serious diseases in animals, as does Encephalomyelitis and Myositis-Polyradiculitis in dogs and cows, resulting in stillborn calves. All these exhibited similar nucleoside triphosphate hydrolases (NTPase). Neospora caninum has a NcNTPase, while Toxoplasma gondii has a TgNTPase-I. The enzymes are thought to play crucial roles in propagation and survival. In order to establish compounds and/or extracts preventing protozoan infection, we targeted these enzymes for drug discovery. The next step was to establish a novel, highly sensitive, and highly accurate assay by combining a conventional biochemical enzyme assay with a fluorescent assay to determine ADP content. We also validated that the novel assay fulfills the criteria to carry out high-throughput screening (HTS) in the two protozoan enzymes. We performed HTS, identified 19 compounds and six extracts from two synthetic compound libraries and an extract library derived from marine bacteria, respectively. In this study, a detailed explanation has been introduced on how to carry out HTS, including information about the preparation of reagents, devices, robot arm, etc.

Sunlight-Driven Highly Selective Catalytic Oxidation of 5-Hydroxymethylfurfural Towards Tunable Products.

Owing to the easy over-oxidation, it is a promising yet challenging task to explore renewable carbon resources to control the sunlight-driven selective catalytic oxidation of biomass-derived 5-hydroxymethylfurfural (HMF), producing important chemical feedstocks, namely, less-oxidized 2,5-diformylfuran (DFF) and 5-hydroxymethyl-2-furancarboxylic acid (HMFCA). Herein, we have developed a photocatalyst by anchoring a Ru complex on CdS quantum dots, which achieves selective oxidation of HMF toward DFF or HMFCA with high conversion (>81 %) and selectivity (>90 %), based on the controllable generation of two oxygen radicals under different atmospheres. Such selective conversion can also work well outside the laboratory by using natural sunlight. In particular, the selective production of HMFCA through photocatalytic HMF oxidation is achieved for the first time. More importantly, our photocatalyst is applicable for the selective oxidation of other compounds with hydroxyl and aldehyde groups.

Modulating carbon dioxide activation on carbon nanotube immobilized salophen complexes by varying metal centers for efficient electrocatalytic reduction.

Electrocatalytic CO2 reduction (ECR) into valuable chemicals, especially driven by renewable energy, presents a promising pattern to realize carbon neutrality. Site-isolated metal complexes flourish in the area of ECR as single-atom-like catalysts because of their competent and tailorable activity. In this study, salophen-based metal (Fe, Co, Ni and Cu) complexes were anchored onto carbon nanotubes (CNTs) to construct efficient catalysts for electrochemically converting CO2 to CO. Both experimental and theoretical results verified that CO2 activation was the rate-determining step for the catalytic performance of these hybrid molecular catalysts. The coordinate activation ability can be manipulated by varying the metal centers. The as-synthesized Fe-salophen hybrid CNT (Fe-salophen/CNT) shows the best activity and selectivity of -13.24 mA·cm-2 current density with 86.8% Faradaic efficiency for generating CO (FECO) at -0.76 V vs. RHE in aqueous solution, whereas Cu-salophen/CNT only achieved a -2.22 mA·cm-2 current density and 57.9% FECO under the same reaction conditions. These distinct catalytic performances resulted from the different coordination activation abilities of CO2 on various metal centers.

Decreased expression of miR-3135b reduces sensitivity to 5-fluorouracil in colorectal cancer by direct repression of PIM1.

5-Fluorouracil (5-FU)-based chemotherapy is the conventional treatment approach for patients with colorectal cancer (CRC). However, de novo and acquired resistance to 5-FU are frequently observed during treatment, which eventually lead to patients succumbing to the disease. Accumulating data have revealed an association of CRC resistance to 5-FU with aberrant expression of microRNAs (miRs). In the present study, Cell Counting Kit-8 was performed to measure cell viability, flow cytometry was performed to detect cell apoptosis, reverse transcription-quantitative PCR was conducted to measure proviral integration site for Moloney murine leukemia virus 1 (PIM1) and miR-3135b expression, western blotting was conducted to measure PIM1 expression. Microarray data analysis indicated that the level of miR-3135b expression was decreased in patients with recurrent CRC that were treated with 5-FU when compared with non-recurrent cases. Overexpression of miR-3135b increased the sensitivity of CRC cells to 5-FU treatment. Moreover, PIM1 was identified as a target gene of miR-3135b using bioinformatics analysis, reverse transcription-quantitative PCR and western blotting. The direct interaction between these two targets was confirmed by luciferase reporter assays. Notably, PIM1 overexpression compensated the effect of miR-3135b in CRC cells. Furthermore, an inverse correlation between PIM1 mRNA expression levels and miR-3135b expression was observed in clinical samples. Therefore, the present study identified miR-3135b as a novel regulator of 5-FU sensitivity in CRC.

Sensitive detection of miRNA based on enzyme-propelled multiple photoinduced electron transfer strategy.

A method is presented that uses photoinduced electron transfer (PET) for the determination of microRNAs (miRNAs) in clinical serum samples and complicated cell samples by using a smartphone. miRNA-21 is adopted as a model analyte. A 3'-phosphorylated DNA probe containing AgNCs is synthesized and hybridized with miRNA-21. Subsequently, the probe is cleaved specifically by duplex-specific nuclease to form 3'-hydroxylated products, then extended by terminal deoxynucleotidyl transferase (TdT) with superlong G for G-quadruplex/hemin units fabrication. In this way, PET occurred between AgNCs and produced G-quadruplex/hemin units, leading to the fluorescence quenching of AgNCs. Notably, the fluorescence images can be captured and translated into digital information by smartphone, resulting in a direct quantitative determination of miRNA. As a result, our strategy for miRNA assay is achieved with a satisfactory detection limit of 1.43 pM. Interestingly, TdT-propelled G-quadruplex/hemin units as multiple electron acceptors promote the sensitivity of miRNA monitoring. Different miRNAs assays are realized by adjusting the complimentary sequences of DNA probe. These qualities not only broaden the practical application of PET-based strategy, but also provide a new insight into the nucleic acid detection. Schematic representation of AgNCs and enzyme-propelled photoinduced electron transfer strategy. It has been successfully applied for detection of miRNA by image analysis software. The method displays portability and accuracy for miRNA determination, meeting the potential for biochemical and clinical applications in resource-limited settings.