Electrochemically promoted thio-Michael addition of N-substituted maleimides to thiols in an aqueous medium.

A stable and practical electrochemical method was developed to promote the thio-Michael addition of N-substituted maleimides to various thiols in an aqueous medium. This protocol was found to be excellent in terms of facile scale-up, oxidant- and catalyst-free conditions, broad substrate scopes, good functional group tolerance, and easily available substrates. Notably, a plausible reaction mechanism was derived from the results of a series of control experiments and CV studies, which indicated that a radical pathway might speed up the thio-Michael addition under constant current.

Structural Modulation of Covalent Organic Frameworks for Efficient Hydrogen Peroxide Electrocatalysis.

The electrochemical production of hydrogen peroxide (H2O2) using metal-free catalysts has emerged as a viable and sustainable alternative to the conventional anthraquinone process. However, the precise architectural design of these electrocatalysts poses a significant challenge, requiring intricate structural engineering to optimize electron transfer during the oxygen reduction reaction (ORR). Herein, we introduce a novel design of covalent organic frameworks (COFs) that effectively shift the ORR from a four-electron to a more advantageous two-electron pathway. Notably, the JUC-660 COF, with strategically charge-modified benzyl moieties, achieved a continuous high H2O2 yield of over 1200 mmol g-1 h-1 for an impressive duration of over 85 hours in a flow cell setting, marking it as one of the most efficient metal-free and non-pyrolyzed H2O2 electrocatalysts reported to date. Theoretical computations alongside in-situ infrared spectroscopy indicate that JUC-660 markedly diminishes the adsorption of the OOH* intermediate, thereby steering the ORR towards the desired pathway. Furthermore, the versatility of JUC-660 was demonstrated through its application in the electro-Fenton reaction, where it efficiently and rapidly removed aqueous contaminants. This work delineates a pioneering approach to altering the ORR pathway, ultimately paving the way for the development of highly effective metal-free H2O2 electrocatalysts.

Comprehensive analysis of hub biomarkers associated with immune and oxidative stress in Hashimoto's thyroiditis.

Hashimoto's thyroiditis (HT) is a type of autoimmune disorder with a complex interplay between immune disorder and oxidative stress (OS). This research aimed to discover biomarkers and potential treatment targets associated with immune and OS dysregulation in HT through integrated bioinformatics analysis and clinical validations. Differential gene expression analysis of GSE138198 dataset from the GEO database identified 1490 differentially expressed genes (DEGs) in HT, including 883 upregulated and 607 downregulated genes. Weighted gene co-expression network analysis explored module genes associated with HT. Overlapping the differentially expressed module genes with immune-related and OS-related genes identified eight differentially expressed module genes associated with immune and OS (DEIOGs) in HT. Protein-protein interaction network analysis identified five hub genes (TNFAIP3, FOS, PTK2B, STAT1, and MMP9). We confirmed four hub genes (TNFAIP3, PTK2B, STAT1 and MMP9) in GSE29315 dataset and clinical thyroid samples, which showed high diagnostic accuracy (AUC >0.7) for HT. The expression of these four genes was positively correlated with serum thyroid peroxidase antibody, thyroglobulin antibody levels, and inflammatory infiltration scores in clinical thyroid samples. Immune profiling revealed distinct profiles in HT, such as B cells memory, monocytes and macrophages. Additionally, all hub genes were inversely associated with monocytes. Further, miRNA-mRNA network analysis was conducted, and a regulatory network comprising four hub genes, 238 miRNAs and 32 TFs was established. These findings suggest that immune cells play a crucial role in the development of HT, and the hub genes TNFAIP3, PTK2B, STAT1, and MMP9 may be key players in HT through immune- and OS-related signaling pathways. Our results may provide valuable insights into the pathogenesis and therapeutic monitoring of HT.

The combination of skeleton-engineering and periphery-engineering: a design strategy for organic doublet emitters.

The emergence and development of radical luminescent materials is a huge breakthrough toward high-performance organic light-emitting diodes (OLEDs) without spin-statistical limits. Herein, we design a series of radicals based on tris(2,4,6-trichlorophenyl)methyl (TTM) by combining skeleton-engineering and periphery-engineering strategies, and present some insights into how different chemical modifications can modulate the chemical stability and luminescence properties of radicals by quantum chemistry methods. Firstly, through the analysis of the geometric structure changes from the lowest doublet excited state (D1) to the doublet ground state (D0) states, the emission energy differences between the BN orientation isomers are explained, and it is revealed that the radical with a smaller dihedral angle difference can more effectively suppress the geometric relaxation of the excited states and bring a higher emission energy. Meanwhile, a comparison of the excited state properties in different radicals can help us to disclose the luminescence behavior, that is, the enhanced luminescent intensity of the radical is caused by the intensity borrowing between the charge transfer (CT) state and the dark locally excited (LE) state. In addition, an efficient algorithm for calculating the internal conversion rate (kIC) is introduced and implemented, and the differences in kIC values between designed radicals are explained. More specifically, the delocalization of hole and electron wave functions can reduce nonadiabatic coupling matrix elements (NACMEs), thus hindering the non-radiative decay process. Finally, the double-regulation of chemical stability and luminescence properties was realized through the synergistic effect of skeleton-engineering and periphery-engineering, and to screen the excellent doublet emitter (BN-41-MPTTM) theoretically.

Determining the electronic performance limitations in top-down-fabricated Si nanowires with mean widths down to 4 nm.

Silicon nanowires have been patterned with mean widths down to 4 nm using top-down lithography and dry etching. Performance-limiting scattering processes have been measured directly which provide new insight into the electronic conduction mechanisms within the nanowires. Results demonstrate a transition from 3-dimensional (3D) to 2D and then 1D as the nanowire mean widths are reduced from 12 to 4 nm. The importance of high quality surface passivation is demonstrated by a lack of significant donor deactivation, resulting in neutral impurity scattering ultimately limiting the electronic performance. The results indicate the important parameters requiring optimization when fabricating nanowires with atomic dimensions.

Superior End-Group Stacking Promotes Simultaneous Multiple Charge-Transfer Mechanisms in Organic Solar Cells with an All-Fused-Ring Nonfullerene Acceptor.

The all-fused-ring acceptor (AFRA) is a success for nonfullerene materials and has attracted considerable attention as its high optical and chemical stability expected to reduce energy loss, and power conversion efficiency (PCE) approaching 15% in constructed all-small-molecule organic solar cells (OSCs). Herein, the intrinsic role of the structure of AFRA F13 and the reason for its high PCE were revealed by comparison with those of typical fused acceptors IDT-IC and Y6. An increased degree of conjugation in F13 leads to broader and red-shifted absorption peaks, facilitating enhancement of the short-circuit current. Multiple charge-transfer mechanisms are mainly attributed to the higher Frenkel exciton (FE) state due to the multiple transition ways for acceptors in the C1-CN:F13 system. The increased number of atoms contributing to the charge-transfer (CT) state facilitated the existence of more superior stacking patterns with easy formation of CT and FE/CT states and a high charge separation rate. It was found using the AFRA is an effective strategy to enhance end-group stacking, enhancing the borrowing of oscillator strength to promote multiple CT mechanisms in the complexes, explaining the high performance of this OSC device. This work is promising to guide designing an efficient AFRA in the future.

Plasma-induced oxygen defects in titanium dioxide to address the long-term stability of pseudocapacitive MnO2 anode for lithium ion batteries.

In this work, we developed Manganese and Titanium based oxide composites with oxygen defects (MnOx@aTiOy) via plasma processing as anodes of lithium ion batteries. By appropriately adjusting the defect concentration, the ion transport kinetics and electrical conductivity of the electrodes are significantly improved, showing stable capacity retention. Furthermore, the incremental capacity is further activated and long-term stable cycling performance is achieved, with a specific capacity of 829.5 mAh/g at 1 A/g after 2000 cycles. To scrutinize the lithium migration paths and energy barriers in MnO2 and Mn2O3, the density functional theory (DFT) calculations is performed to explore the lithium migration paths and energy barriers. Although the transformation of MnO2 into Mn2O3 through oxygen defects was initially surmised to inhibit Li ions along their standard routes, our results indicate quite the contrary. In fact, the composite's lithium diffusion rate saw a substantial increase. This can be accredited to the pronounced enhancement of conductivity and ion transport efficiency in the amorphous and porous TiOy.

Transcription factor ZNF488 accelerates cervical cancer progression through regulating the MEK/ERK signaling pathway.

Cervical cancer (CC) is one of the most common gynecological malignancies worldwide. Zinc Finger Protein 488 (ZNF488) has been identified as an oncogene in nasopharyngeal carcinoma. However, its biological role and potential mechanism in CC remain to be elucidated. In the present study, upregulation of ZNF488 expression in human CC tissues was found in clinical samples and analyzed in The Cancer Genome Atlas (TCGA) dataset, which was associated with clinical staging and lymph node metastasis. Quantitative real time polymerase chain reaction (PCR) and western blot assays indicated that the expression of ZNF488 was up-regulated in CC cells. Cell colony formation and cell cycle analysis assays suggested that ZNF488 promoted CC cell proliferation and cycle progression. Knockdown of ZNF488 inhibited tumor growth of xenograft tumor mice in vivo, in agreement with the levels of ZNF488 and Ki-67. Moreover, transwell and western assays demonstrated that ZNF488 enhanced CC cell migration and invasion. Additionally, knockdown of ZNF488 also inhibited lung metastasis of CC cells in vivo. Further mechanism analysis implied that ZNF488 promoted the MEK/ERK signaling pathway. ERK inhibitor PD98059 significantly weakened the proliferation and epithelial-mesenchymal transformation (EMT) promotion effect of ZNF488. Collectively, ZNF488 exerts its oncogene function partially through modulating MEK/ERK signaling pathway in CC, indicating that ZNF488 may provide a promising therapeutic target for the treatment of CC.

Awareness of Hospice Care Among Community-Dwelling Elderly Participants.

Background and Purpose: The main goal of hospice care is to improve the quality of life for people who are at the end-of-life phase. However, investigations on the awareness of hospice care among community-dwelling elderly participants are limited. This work aimed to reveal the awareness status of hospice care and explore the factors influencing the awareness rate among elderly participants. Methods: A questionnaire survey was conducted among individuals aged 60 years and above. Results: A total of 4,969 individuals aged 60 years and above were randomly selected from 48 primary medical institutions in Handan. The awareness rate of hospice care in the baseline survey was 19.3% (n = 959). All included individuals were divided into two groups in accordance with their awareness of hospice care. The awareness of hospice care among participants with low educational level, living alone, and afraid of talking about death was low (p < .05). Implications for Practice: The level of awareness of hospice care among community-dwelling elderly participants is low. The influencing factors included educational level, living status, and fear of talking about death. The community-dwelling elderly participants' awareness of hospice care must be improved. It is recommended that public medical education and training should be enhanced to improve knowledge and awareness of hospice care among community-dwelling elderly residents with low educational level, living alone, and afraid of talking about death.

Urothelial tumor initiation requires deregulation of multiple signaling pathways: implications in target-based therapies.

Although formation of urothelial carcinoma of the bladder (UCB) requires multiple steps and proceeds along divergent pathways, the underlying genetic and molecular determinants for each step and pathway remain undefined. By developing transgenic mice expressing single or combinatorial genetic alterations in urothelium, we demonstrated here that overcoming oncogene-induced compensatory tumor barriers was critical for urothelial tumor initiation. Constitutively active Ha-ras (Ras*) elicited urothelial hyperplasia that was persistent and did not progress to tumors over a 10 months period. This resistance to tumorigenesis coincided with increased expression of p53 and all pRb family proteins. Expression of a Simian virus 40 T antigen (SV40T), which disables p53 and pRb family proteins, in urothelial cells expressing Ras* triggered early-onset, rapidly-growing and high-grade papillary UCB that strongly resembled the human counterpart (pTaG3). Urothelial cells expressing both Ras* and SV40T had defective G(1)/S checkpoint, elevated Ras-GTPase and hyperactivated AKT-mTOR signaling. Inhibition of the AKT-mTOR pathway with rapamycin significantly reduced the size of high-grade papillary UCB but hyperactivated mitogen-activated protein kinase (MAPK). Inhibition of AKT-mTOR, MAPK and STAT3 altogether resulted in much greater tumor reduction and longer survival than did inhibition of AKT-mTOR pathway alone. Our studies provide the first experimental evidence delineating the combinatorial genetic events required for initiating high-grade papillary UCB, a poorly defined and highly challenging clinical entity. Furthermore, they suggest that targeted therapy using a single agent such as rapamycin may not be highly effective in controlling high-grade UCB and that combination therapy employing inhibitors against multiple targets are more likely to achieve desirable therapeutic outcomes.

Organic-inorganic hybrid ferrocene/AC as cathodes for wide temperature range aqueous Zn-ion supercapacitors.

Organic and inorganic materials have their own advantages and limitations, and new properties can be displayed in organic-inorganic hybrid materials by uniformly combining the two categories of materials at small scale. The objective of this study is to hybridize activated carbon (AC) with ferrocene to obtain a new material, ferrocene/AC, as the cathode for Zn-ion hybrid supercapacitors (ZHSCs). The optimized ferrocene/AC material owns fast charge transfer kinetics and can obtain pseudo-capacitance through redox reaction. Due to the introduction of ferrocene/AC, the ZHSCs exhibit remarkable electrochemical performances relative to that using ferrocene cathode, including high discharge specific capacity of 125.1 F g-1, high energy density (up to 44.8 Wh kg-1 at 0.1 A g-1) and large power density (up to 1839 W kg-1 at 5 A g-1). Meanwhile, the capacity retention rate remains 73.8% after 10 000 charge and discharge cycles. In particular, this cathode material can be used at low temperatures (up to -30 °C) with 60% capacity remained, which enlarges the application temperature range of ZHSCs. These results of this study can help understand new properties of organic-inorganic hybrid materials.

Morphologically and chemically regulated 3D carbon for Dendrite-free lithium metal anodes by a plasma processing.

For the high theoretical specific capacity and low redox potential, lithium (Li) metal is considered as one of the most promising anode materials for the next generation of rechargeable batteries. In this work, we have developed an effective and accurate plasma strategy to regulate the surface morphology and functional groups of three-dimensional nitrogen-containing carbon foam (CF) to control the Li nucleation and growth. Besides the rougher surface induced by oxygen (O2) plasma, the conversion of carbon-nitrogen chemical bond (CN), namely, change from the quaternary N to pyrrolic/pyridinic N was realized by the nitrogen (N2) plasma. This chemical regulation of nitrogen boosts the lithiophilicity of carbon foam, which is evidenced by lower overpotential obtained from the experiment and higher binding energy for Li ions (Li+) calculated by density functional theory (-1.43, -1.85, -2.41 and -2.45 eV for the amorphous C-, C-quaternary N-, C-pyrrolic N- and C-pyridinic N-, respectively). The electrochemical performance of the half cells and full cells based on this plasma regulated carbon foam collectors also proved the prominent effectiveness of this plasma strategy on guiding the uniform dispersion of Li+ and thus inducing the homogeneous Li nucleation, as well as suppressing the growth of Li dendrites.

Zn-doping Effects of Na-rich Na3+xV2-xZnx(PO4)3/C cathodes for Na-Ion Batteries: Lattice distortion induced by doping site and enhanced electrochemical performance.

To tackle the intrinsic inferior conductivity of the sodium ion batteries (SIBs) cathode Na3V2(PO4)3, transitional metal cation doping, and carbon frame design are employed for NASICON structural modification. Herein, a hard carbon skeleton Na3+xV2-xZnx(PO4)3 NASICON structure is proposed resorting to the combination of flimsy hard carbon slices coating and Zn2+ doping along with the introduction of spare Na+. The structural distortion caused by the insertion of Zn2+ and Na+ broadens the transfer channels and increases diffusion routes for Na+. At the same time, the anchoring effect for Na3+xV2-xZnx(PO4)3 nanoparticles brought by external hard carbon layers and pillar effect aroused by Zn2+ provide a stable and firm skeleton, which is conducive to structural stability and reversibility at high current density. Among various doping concentrations, Na3.03V1.97Zn0.03(PO4)3 performs a significantly enhanced rate performance with a reversible capacity up to 60 mAh·g-1 (40C) and ultra-long cycle life of 1000 cycles with a capacity retention of 92.6% at 5C.

Understanding of the Mechanism Enables Controllable Chemical Prelithiation of Anode Materials for Lithium-Ion Batteries.

By compensating the irreversible loss of lithium ions during the first cycle, prelithiations can solve the issue of insufficient initial Coulombic efficiency for various anodes. Recently, the chemical prelithiation using organolithium compounds has attracted increasing attention because of its uniform and fast reaction, safety, and easily adjustable degree of prelithiation. However, the nature and activity of organolithium involved in chemical prelithiations have not been deeply explored yet. Here, by monitoring the electrical conductivity change in the lithiation solution in the duration of its formation, we have demonstrated the essential role of lithium radical anions for chemical prelithiation and compared the prelithiation activity of dissociated species and aggregates of lithium radical anions. The mechanistic understanding of the nature of the lithiation solution leads to controllable chemical prelithiation, as demonstrated in full cells of prelithiated hard carbon and LiFePO4.

Bimetallic composite induced ultra-stable solid electrolyte interphase for dendrite-free lithium metal anode.

Lithium metal is the most promising anode materials for the next generation lithium ion battery. However, the electrode polarization leads to the formation of dendrites and "dead lithium", which degrades the performance of lithium metal batteries and induce a variety of security risk. The electrode polarization and lithium dendrites can be suppressed by lithium metal composite electrode. Herein, a simple and effective strategy is adopted to construct nickel and lithium bimetallic composite (NiLi-BC) electrode by a double roll process. The Ni framework inside the electrode can optimize the electric field and Li+ distribution at the electrode/electrolyte interface and induce the uniform lithium deposition. As a result, the NiLi-BC exhibits a lithium dendrite-free feature and stable cycling performance under a low overpotential (<15 mV throughout 2180 h at 1 mA cm-2 with a deposition capacity of 1 mAh cm-2). Moreover, the assembled NiLi-BC||LiFePO4 coin cell and pouch cell exhibit improved capability and stable cycling performance. Finally, the in-situ optical microscopy and in-situ Raman spectroscopy are employed to obtain a better understanding of the interfacial structure and chemical component during the Li plating and striping processes. The scheme of this study of the NiLi electrode has great practical application value.

Temporally and spatially controllable gene expression and knockout in mouse urothelium.

Urothelium that lines almost the entire urinary tract performs important functions and is prone to assaults by urinary microbials, metabolites, and carcinogens. To improve our understanding of urothelial physiology and disease pathogenesis, we sought to develop two novel transgenic systems, one that would allow inducible and urothelium-specific gene expression, and another that would allow inducible and urothelium-specific knockout. Toward this end, we combined the ability of the mouse uroplakin II promoter (mUPII) to drive urothelium-specific gene expression with a versatile tetracycline-mediated inducible system. We found that, when constructed under the control of mUPII, only a modified, reverse tetracycline trans-activator (rtTA-M2), but not its original version (rtTA), could efficiently trans-activate reporter gene expression in mouse urothelium on doxycycline (Dox) induction. The mUPII/rtTA-M2-inducible system retained its strict urothelial specificity, had no background activity in the absence of Dox, and responded rapidly to Dox administration. Using a reporter gene whose expression was secondarily controlled by histone remodeling, we were able to identify, colocalize with 5-bromo-2-deoxyuridine incorporation, and semiquantify newly divided urothelial cells. Finally, we established that, when combined with a Cre recombinase under the control of the tetracycline operon, the mUPII-driven rtTA-M2 could inducibly inactivate any gene of interest in mouse urothelium. The establishment of these two new transgenic mouse systems enables the manipulation of gene expression and/or inactivation in adult mouse urothelium at any given time, thus minimizing potential compensatory effects due to gene overexpression or loss and allowing more accurate modeling of urothelial diseases than previously reported constitutive systems.

Fluorescence enhancement of the silver nanoparticales--curcumin-cetyltrimethylammonium bromide-nucleic acids system and its analytical application.

It is found that silver nanoparticles (AgNPs) can further enhance the fluorescence intensity of curcumin (CU)-cetyltrimethylammonium bromide (CTAB)-nucleic acids and improve its anti-photobleaching activity. Under optimum conditions, the enhanced fluorescence intensity is proportion to the concentration of nucleic acids in the range of 2.0 x 10(-8)-1.0 x 10(-6) g mL(-1) for fish sperm DNA (fsDNA), 2.0 x 10(-8)-1.0 x 10(-6) g mL(-1) for calf thymus DNA (ctDNA), 1.0 x 10(-8)-1.0 x 10(-6) g mL(-1) for yeast RNA (yRNA), and their detection limits (S/N = 3) are 8.0 ng mL(-1), 10.5 ng mL(-1) and 5.8 ng mL(-1), respectively. This method is used for determining the concentration of DNA in actual sample with satisfactory results. The interaction mechanism is also studied.

Amine-functionalized graphitic carbon nitride decorated with small-sized Au nanoparticles for photocatalytic CO2 reduction.

Amine-functionalized graphitic carbon nitride (g-C3N4) decorated with Au nanoparticles (CN/Au) was prepared by N2 plasma treatment of g-C3N4 powders impregnated with HAuCl4·3H2O. Well-dispersed Au nanoparticles with a small particle size were deposited on g-C3N4 nanosheets. In addition, the amino group was introduced into the CN/Au system. Without the addition of cocatalyst and sacrificial agent, CN/Au exhibited enhanced photocatalytic activity for CO2 reduction under visible-light irradiation. CO and CH4 evolution rates of CN/Au reached 28.3 and 1.3 µmol·h-1·g-1, which were 7.6 and 2.6 times higher than those of pristine g-C3N4 (CN-0), respectively. The enhanced activity can be explained by these factors. (1) The introduced amino group improved the adsorption capacity of CN/Au for CO2; (2) the hot electrons generated by Au nanoparticles activated the surrounding electrons through energy transfer and caused local temperature to rise, increasing the efficiency of the photoreduction reaction of CO2; (3) the Schottky junction between Au and g-C3N4 promoted the migration of electrons from g-C3N4 to Au nanoparticles, suppressing the recombination of the carriers. Time-of-flight secondary ion mass spectrometry confirmed the introduction of amino groups, and solid-state 13C nuclear magnetic resonance spectra provided a support for inferring the position of the amino group.

The fluorescence enhancement of quercetin-nucleic acid system and the analytical application.

Nucleic acid can greatly enhance the fluorescence intensity of quercetin in HMTA-HCl (pH 5.5) buffer. The enhanced intensity is in proportion to the concentration of nucleic acids in the range 5.0 x 10(-9) to 1.0 x 10(-6) g/mL for fsDNA, 5.0 x 10(-9) to 7.0 x 10(-7) g/mL for ctDNA and 5.0 x 10(-9) to 1.0 x 10(-6) g/mL for yRNA, and their detection limits (S/N = 3) are 3.5 x 10(-9), 7.8 x 10(-10) and 2.6 x 10(-9) g/mL, respectively. In comparison with most reported fluorescent probes for the determination of nucleic acids, the proposed probe has higher sensitivity and lower toxicity. The interaction investigation indicates that quercetin binds with double-strand DNA in groove binding mode, resulting in fluorescence enhancement of this system.

Interfacial modification of titanium dioxide to enhance photocatalytic efficiency towards H2 production.

Strong demand for affordable clean energy to support applications ranging from conventional energy supply to space propulsion places spotlight on advanced energy generation using photovoltaic and wind power. Yet, the intermittent nature of solar and wind sources drives the search for energy storage solutions that would permit the needed level of resilience and support further growth in the use of renewable sources of power. Hydrogen generation using sunlight is a promising pathway to decouple demand from supply. Herein, we show how exposure to reactive Ar-H2, Ar-H2-N2, and Ar-O2 plasma environments can notably enhance surface properties of photocatalytic TiO2 nanosheets used in advanced energy generation systems. Treatment using Ar-H2 plasmas produced highly hydrogenated, surface-disordered TiO2 nanosheets with oxygen vacancies, whereas exposure to Ar-H2-N2 plasmas resulted in N doping. Surprisingly, Ar-O2 plasma treatment did not change surface properties of TiO2. Optical emission spectroscopy was used to monitor transient species to further understand surface modification in plasma. Direct measurements demonstrated that among thus-produced samples, hydrogenated TiO2 nanosheets exhibit the highest photocatalytic H2-generation activity under visible-light irradiation, which is also greater than the activity of pure, untreated nanosheets. The mechanism of enhancing the visible-light photocatalytic H2-generation activity on hydrogenated TiO2 nanosheets is also proposed. The level of surface disorder and oxygen vacancies plays an important role in enhancing visible-light absorption and reducing the recombination of photogenerated electrons and holes.