Copper nanoclusters-doped novel carrier with synergistic adsorption-catalytic active sites to enable high-performance dye removal.

Enhancing the synergistic interplay between adsorption and catalytic oxidation to amplify Fenton-like effects remains a pivotal challenge in advancing water pollution remediation strategies. In this study, a suite of novel carriers (SH) composed of silica (SiO2) and hydroxyapatite (HAp) in different ratios were synthesized through an amalgamation of the sol-gel and co-precipitation techniques. Notably, various forms of copper (Cu) species, including Cu2+ ions and Cu nanoclusters (Cu NCs), could be stably incorporated onto the SH surface via meticulous loading and doping techniques. This approach has engendered a new class of Fenton-like catalysts (Cu NCs-SH1-5) characterized by robust acid-base tolerance stability and remarkable recyclability. Compared with the previously reported Cu NCs-HAp, this catalyst with lower Cu species content could achieve better performance in adsorbing and degrading dyes under the aid of hydrogen peroxide (H2O2). The catalyst's dual action sites, specifically the adsorption sites (SiOH, POH, slit pores) and catalytic centers (multivalent Cu species), had clear division of labor and collaborate with each other. Further, reactive oxygen species (ROS) identification and astute electrochemical testing have unveiled the mechanism underpinning the cooperative degradation of dyes by three types of ROS, spawned through electron transfer between the Fenton-like catalyst (Cu NCs-SH) and H2O2. From these insights, the mechanism of synergistic adsorption-catalytic removal was proposed.

Hydrothermal Growth of an Al-Doped α-Ga2O3 Nanorod Array and Its Application in Self-Powered Solar-Blind UV Photodetection Based on a Photoelectrochemical Cell.

Herein, we successfully fabricated an Al-doped α-Ga2O3 nanorod array on FTO using the hydrothermal and post-annealing processes. To the best of our knowledge, it is the first time that an Al-doped α-Ga2O3 nanorod array on FTO has been realized via a much simpler and cheaper way than that based on metal-organic chemical vapor deposition, magnetron sputtering, molecular beam epitaxy, and pulsed laser deposition. And, a self-powered Al-doped α-Ga2O3 nanorod array/FTO photodetector was also realized as a photoanode at 0 V (vs. Ag/AgCl) in a photoelectrochemical (PEC) cell, showing a peak responsivity of 1.46 mA/W at 260 nm. The response speed of the Al-doped device was 0.421 s for rise time, and 0.139 s for decay time under solar-blind UV (260 nm) illumination. Compared with the undoped device, the responsivity of the Al-doped device was ~5.84 times larger, and the response speed was relatively faster. When increasing the biases from 0 V to 1 V, the responsivity, quantum efficiency, and detectivity of the Al-doped device were enhanced from 1.46 mA/W to 2.02 mA/W, from ~0.7% to ~0.96%, and from ~6 × 109 Jones to ~1 × 1010 Jones, respectively, due to the enlarged depletion region. Therefore, Al doping may provide a route to enhance the self-powered photodetection performance of α-Ga2O3 nanorod arrays.

Wet-chemistry synthesis of two-dimensional Pt- and Pd-based intermetallic electrocatalysts for fuel cells.

Two-dimensional (2D) noble-metal-based nanomaterials have attracted tremendous attention and have widespread promising applications as a result of their unique physical, chemical, and electronic properties. Especially, 2D Pt- and Pd-based intermetallic nanoplates (IMNPs) and nanosheets (IMNSs) are widely studied for fuel cell (FC)-related reactions, including the cathodic oxygen reduction reaction (ORR) and anodic formic acid, methanol and ethanol oxidation reactions (FAOR, MOR and EOR). Wet-chemistry synthesis is a powerful strategy to prepare metallic nanocrystals with well-controlled dispersity, size, and composition. In this review, a fundamental understanding of the FC-related reactions is firstly elaborated. Subsequently, the current wet-chemistry synthesis pathways for 2D Pt- and Pd-based IMNPs and IMNSs are briefly summarized, as well as their electrocatalytic applications including in the ORR, FAOR, MOR, and EOR. Finally, we provide an overview of the opportunities and current challenges and give our perspectives on the development of high-performance 2D Pt- and Pd-based intermetallic electrocatalysts towards FCs. We hope this review offers timely information on the synthesis of 2D Pt- and Pd-based IMNPs and IMNSs and provides guidance for the efficient synthesis and application of them.

MOF-templated synthesis of photoluminescent MoS2 QDs.

Fabricating MoS2 QDs using porous metal-organic frameworks (MOFs) as templates remains a great challenge, because the MOF structure is prone to collapse during solvothermal reactions, resulting in a loss of the function of the template. In the present work, the production of homogeneous photoluminescent MoS2 QDs was achieved by using the structurally stable MOF MIL-101 as limited nanoreactors. The process developed opens up a new route for fabricating other photoluminescent QDs and their derived nanomaterials.

Intermetallic Nanocrystals: Seed-Mediated Synthesis and Applications in Electrocatalytic Reduction Reactions.

In recent years, intermetallic nanocrystals (IMNCs) have attracted extensive attention in the field of electrocatalysis. However, precise control over the size, shape, composition, structure, and exposed crystal facet of IMNCs seems to be a challenge to the traditional method of high-temperature annealing although these parameters have a significant effect on the electrocatalytic performance. Controllable synthesis of IMNCs by the wet chemistry method in the liquid phase shows great potential compared with the traditional high-temperature annealing method. In this Review, we attempt to summarize the preparation of IMNCs by the seed-mediated synthesis in the liquid phase, as well as their applications in electrocatalytic reduction reactions. Several representative examples are purposely selected for highlighting the huge potential of the seed-mediated synthesis approach in chemical synthesis. Specifically, we personally perceive the seed-mediated synthesis approach as a promising tool in the future for precise control over the size, shape, composition, structure, and exposed crystal facet of IMNCs.

Dioscin inhibits SCC15 cell proliferation via the RASSF1A/MST2/YAP axis.

Dioscin, an extract from traditional Chinese herbal plants, displays various biological and pharmacological effects on tumors, including inhibition of cell proliferation and induction of DNA damage. However, the effects of dioscin on oral squamous cell carcinoma (OSCC) cells are not completely understood. The present study aimed to evaluate the impact of dioscin on OSCC cell proliferation. Cell Counting Kit­8 and 5­ethynyl­2'­deoxyuridine incorporation assays were performed to assess cell proliferation. Flow cytometry was conducted to detect alterations in the cell cycle and cell apoptosis. Western blotting and coimmunoprecipitation were performed to determine protein expression levels. In SCC15 cells, dioscin treatment significantly induced cell cycle arrest, increased apoptosis and inhibited proliferation compared with the control group. Mechanistically, the tumor suppressor protein Ras association domain­containing protein 1A (RASSF1A) was activated and oncoprotein yes­associated protein (YAP) was phosphorylated by dioscin. Furthermore, YAP overexpression and knockdown reduced and enhanced the inhibitory effects of dioscin on SCC15 cells, respectively. In summary, the results demonstrated that, compared with the control group, dioscin upregulated RASSF1A expression in OSCC cells, which resulted in YAP phosphorylation, thus weakening its transcriptional coactivation function, enhancing cell cycle arrest and apoptosis, and inhibiting cell proliferation. The present study indicated that dioscin may serve as a therapeutic agent for OSCC.

Metformin inhibits mTOR and c-Myc by decreasing YAP protein expression in OSCC cells.

Metformin is an antidiabetic drug that has been reported to have an inhibitory effect on different types of cancers, including oral squamous cell carcinoma (OSCC). However, few studies have explored the role of Yes­associated protein (YAP), a vital factor contributing to OSCC biology, in metformin­induced anticancer activity in OSCC cells. Thus, the purpose of the present study was to investigate the molecular relationship between metformin and YAP in OSCC cells. CAL27 and SCC25 cell lines were treated with various concentrations of metformin for 24 h. Cell proliferation was detected by Cell Counting Kit­8 (CCK­8) and flow cytometric assays. Cell apoptosis was analyzed using flow cytometry. The intracellular protein levels of target genes were determined by western blotting. It was demonstrated that metformin affected the cell cycle and apoptosis of CAL27 and SCC25 cells. Alteration of YAP protein expression affected metformin­mediated changes in the cell cycle and apoptosis of CAL27 and SCC25 cells. In addition, compared to the control treatment, metformin treatment decreased the protein levels of YAP, mTOR, p­mTOR and c­Myc. The overexpression of YAP alleviated the inhibitory effect of metformin on the protein expression of mTOR, p­mTOR and c­Myc. The combination of metformin and verteporfin markedly enhanced the effects of metformin on the protein expression of mTOR, p­mTOR and c­Myc. Therefore, the results of the present study suggest that metformin suppresses OSCC by inhibiting YAP protein expression and by suppressing the YAP­mediated effects of metformin on the protein expression of mTOR and c­Myc.

TAZ promotes the proliferation and osteogenic differentiation of human periodontal ligament stem cells via the p-SMAD3.

OBJECTIVE: This study aims to offer insights about the biological influence of TAZ, which is a transcriptional coactivator containing a PDZ-binding motif, upon the apoptosis, proliferation, and osteogenic differentiation of human periodontal ligament stem cells (h-PDLSCs). METHODS: We used the green fluorescence protein lentivirus infection system to knockdown or overexpress TAZ in h-PDLSCs. 5-ethynyl-2'-deoxyuridine (EdU) staining detected the proliferative activity, and h-PDLSC apoptosis was analyzed by Annexin V-APC staining. TAZ knockdown or overexpression was performed to determine the osteogenic differentiation function of TAZ during the osteogenic induction of h-PDLSCs. The molecular mechanism of TAZ in the promotion of h-PDLSC osteogenesis was also explored. The chemical inhibitor of SMAD2/3 SIS3 HCL was used to identify the effects in vitro osteogenic differentiation and bone formation in h-PDLSCs overexpressing TAZ. RESULTS: TAZ overexpression resulted in enhanced cell rapid multiplication, which increased the expression of messenger RNA in stemness-related genes. By comparison, TAZ knockdown reduced proliferative activity and increased the apoptosis of h-PDLSCs. After the 7-day osteogenic induction period, alkaline phosphatase activity in the TAZ-overexpression group was significantly increased, and mineralized nodules increased significantly after osteogenic induction for 21 days. Similarly, osteoblast differentiation of h-PDLSCs was impaired after TAZ knockdown. However, the osteogenic potential of the group exposed to the p-SMAD3 inhibitor was restored to its original level. CONCLUSION: Hippo/TAZ plays a positive role inside the proliferation, stemness maintenance, and osteogenic specialization of h-PDLSCs, and the specific downstream factor of osteogenic differentiation is SMAD3.

Effect of YAP on an Immortalized Periodontal Ligament Stem Cell Line.

OBJECTIVE: To establish an immortalized human periodontal ligament stem cell line (hPDLSC) and investigate whether and how YAP mediates the establishment of the stem cell line. METHODS: Primary hPDLSCs were cultured and transfected with lentivirus containing the telomerase reverse transcriptase (TERT) gene. The expression of TERT was detected via the polymerase chain reaction (PCR) and real-time quantitative PCR (RT-PCR). Flow cytometry was employed to detect surface markers of hPDLSCs and TERT-hPDLSCs. The cell counting kit-8 (CCK-8) and 5-ethynyl-2'-deoxyuridine (EdU) methods were used to examine the proliferation ability of the cells. Flow cytometry and TUNEL staining were employed to examine the cell apoptosis rate. The ß-galactosidase staining assay was used to assess the rate of cell senescence. The osteogenic differentiation ability of the cells was detected via alkaline phosphatase (ALP) staining and Alizarin red staining assays. BALB/c mice were employed to determine the tumorigenicity of TERT-hPDLSCs. The expression levels of YAP and other proteins in the Hippo signaling pathway were detected by Western blotting. Verteporfin was used to inhibit the binding of YAP to the downstream target gene TEAD. RESULTS: TERT-hPDLSCs showed stable high expression of TERT, even at the thirtieth passage after transfection with lentivirus containing the TERT gene. Compared with primary hPDLSCs, TERT-hPDLSCs exhibited a stronger proliferation ability and lower cell apoptosis and senescence rates while maintaining the same osteogenetic differentiation ability as primary hPDLSCs. The transfection of hPDLSCs with lentivirus containing the TERT gene did not lead to tumorigenesis in nude mice. The Hippo signaling pathway was inactivated in TERT-hPDLSCs compared to hPDLSCs. When treated with verteporfin, the proliferation of TERT-hPDLSCs decreased, while the apoptosis and senescence rates of these cells increased. However, TERT-hPDLSCs still showed a stronger proliferation ability and lower cell apoptosis and senescence rates than hPDLSCs treated with verteporfin at the same concentration. CONCLUSIONS: Overexpression of TERT in hPDLSCs resulted in the successful establishment of an immortalized periodontal ligament stem cell line. TERT may regulate the biological characteristics of hPDLSCs through the Hippo/YAP signaling pathway. hPDLSCs could be a feasible resource for stem cell research and a promising resource for stem cell therapy.

Epigallocatechin-3-gallate affects the proliferation, apoptosis, migration and invasion of tongue squamous cell carcinoma through the hippo-TAZ signaling pathway.

The purpose of the present study was to investigate the mechanism by which epigallocatechin­3­gallate (EGCG) inhibits the biological behaviors of the tongue squamous cell carcinoma (TSCC) through the Hippo­tafazzin (TAZ) signaling pathway and to provide insights into molecular targeted therapy in TSCC. CAL27 and SCC15 cells were treated with different concentrations of EGCG for 24 h. Cell proliferation was determined using Cell­Counting Kit­8 and EdU assays. Cell apoptosis was evaluated by flow cytometry. Cell migration and invasion were measured using scratch and Transwell assays, respectively. Furthermore, protein levels of associated target genes were detected using a western blot assay. It was demonstrated that EGCG affected biological behaviors of CAL27 and SCC15 cells in concentration­ and time­dependent manners. In addition, EGCG decreased the protein levels of TAZ, LATS1, MOB1 and JNK. Overexpression of TAZ alleviated the effect of EGCG on CAL27 cells. Furthermore, the combination of EGCG and simvastatin inhibited the proliferation, migration and invasion, and promoted apoptosis significantly compared with single treatment in CAL27 cells. The results of the present study suggested that EGCG affects proliferation, apoptosis, migration and invasion of TSCC through the Hippo­TAZ signaling pathway.

C-MYC and BCL-2 mediate YAP-regulated tumorigenesis in OSCC.

Transcriptional co-activator Yes-associated protein (YAP) is a key oncogene in mammalian cells. The present understanding of YAP in oral squamous cells carcinoma (OSCC) remains unclear. The purpose of this study is to investigate the effects of YAP on proliferation and apoptosis in OSCC and the molecular mechanism. The results showed the expression level of YAP was higher in OSCC tissues than that in adjacent normal tissues. Knockdown of YAP in CAL27 cell lines prohibited cell proliferation while augmented apoptosis. Conversely, overexpression of YAP protected cells from apoptosis and promoted cell proliferation. Moreover, C-MYC and BCL-2 mRNA and protein levels were altered due to the differential expression of YAP. Subsequent Verteporfin treatment in CAL27 cells revealed that the transcription and translation of BCL-2 and C-MYC both decreased. In a tumor xenograft model, knockdown of YAP suppressed tumor growth of CAL27 in vivo, while YAP overexpression promoted the tumor growth. These results suggest that YAP is a crucial regulator that exerts pro-proliferation and anti-apoptosis effects in OSCC through actions affecting the cell cycle and intrinsic apoptotic signaling. Thus YAP could potentially serve as a valuable molecular biomarker or therapeutic target in the treatment of OSCC.

Electropolymerized surface ion imprinting films on a gold nanoparticles/single-wall carbon nanotube nanohybrids modified glassy carbon electrode for electrochemical detection of trace mercury(II) in water.

Electrochemical detection of Hg(II) using a electropolymerized ion imprinting poly(2-mercaptobenzothiazole) films at the surface of gold nanoparticles/single-walled carbon nanotube nanohybrids modified glassy carbon electrode (PMBT/AuNPs/SWCNTs/GCE) is described for the first time. The Hg(II)-imprinted PMBT/AuNPs/SWCNTs/GCE sensor exhibits larger binding to functionalized capacity, larger affinity, faster binding kinetics and higher selectivity to template Hg(II). The differential pulse anodic stripping voltammetry (DPASV) response of the Hg(II)-imprinted PMBT/AuNPs/SWCNTs/GCE sensor to Hg(II) is ca. 3.7- and 10.5-fold higher than that at the non-imprinted PMBT/AuNPs/SWCNTs/GCE and the imprinted PMBT/AuNPs/GCE, respectively, and the detection limit for Hg(II) is 0.08 nM (S/N=3, which is well below the guideline value given by the World Health Organization) and a sensitivity of 0.749 µA nM(-1) was obtained. Excellent wide linear range (0.4-96.0 nM) and good repeatability (relative standard deviation of 2.6%) were obtained for Hg(II). The interference experiments show that Ag(I), Pb(II), Cd(II), Zn(II) and Cu(II) had little or no influence on the Hg(II) signal. These values, particularly the high sensitivity and excellent selectivity in contrast to the values reported previously in the area of electrochemical Hg(II) detection, demonstrate the analytical performance of the Hg(II)-imprinted PMBT/AuNPs/SWCNTs/GCE toward Hg(II) is superior to the existing electrodes and could be used for efficient determination of Hg(II) in natural water samples.

Adsorption of lead(II) on O2-plasma-oxidized multiwalled carbon nanotubes: thermodynamics, kinetics, and desorption.

O(2)-plasma-oxidized multiwalled carbon nanotubes (po-MWCNTs) have been used as an adsorbent for adsorption of lead(II) in water. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and Raman spectroscopy measurements show that the bulk properties of MWCNTs were not changed after O(2)-plasma oxidation. The adsorption capacity of MWCNTs for lead(II) was greatly enhanced after plasma oxidation mainly because of the introduction of oxygen-containing functional groups onto the surface of MWCNTs. The removal of lead(II) by po-MWCNTs occurs rather quickly, and the adsorption kinetics can be well described by the pseudo-second-order model. The adsorption isotherm of lead(II) onto MWCNTs fits the Langmuir isotherm model. The adsorption of lead(II) onto MWCNTs is strongly dependent upon the pH values. X-ray photoelectron spectroscopy analysis shows that the adsorption mechanism is mainly due to the chemical interaction between lead(II) and the surface functional groups of po-MWCNTs. The thermodynamic parameters (ΔH°, ΔS°, and ΔG°) calculated from the adsorption isotherms suggest that the adsorption of lead(II) onto MWCNTs is endothermic and spontaneous. The regeneration performance shows that lead(II) can be easily regenerated from po-MWCNTs by altering the pH values of the solution.

Stripping voltammetric detection of mercury(II) based on a surface ion imprinting strategy in electropolymerized microporous poly(2-mercaptobenzothiazole) films modified glassy carbon electrode.

This work reports a surface ion imprinting strategy in electropolymerized microporous poly(2-mercaptobenzothiazole) (MPMBT) films at the surface of glassy carbon electrode (GCE) for the electrochemical detection of Hg(II). The Hg(II)-imprinted MPMBT/GCE exhibits larger binding to functionalized capacity, faster binding kinetics and higher selectivity to template Hg(II) due to their high ratio of surface-imprinted sites, larger surface-to-volume ratios, the complete removal of Hg(II) templates and larger affinity to Hg(II). The square wave anodic stripping voltammetry (SW ASV) response of the Hg(II)-imprinted MPMBT/GCE to Hg(II) is ca. 3.0 and 5.9 times larger than that at the direct imprinted poly(2-mercaptobenzothiazole) modified GCE and non-imprinted MPMBT/GCE sensor, respectively; and the detection limit for Hg(II) is 0.1nM (which is well below the guideline value given by the World Health Organization). Excellent wide linear range (1.0-160.0nM) and good repeatability (relative standard deviation of 2.5%) were obtained for Hg(II). The interference experiments showed that mercury signal was not interfered in the presence of Pb(II), Cd(II), Zn(II), Cu(II) and Ag(I), respectively. These values, particularly the high sensitivity and excellent selectivity compared favorably with previously reported methods in the area of electrochemical Hg(II) detection, demonstrate the feasibility of using the prepared Hg(II)-imprinted MPMBT/GCE for efficient determination of Hg(II) in aqueous environmental samples.

Diaquabis(ethylenediamine)cadmium(II) bis(4-aminonaphthalene-1-sulfonate) dihydrate.

In the title compound, [Cd(C2H8N2)2(H2O)2](C10H8NO3S)2.2H2O, the CdII atom, located on an inversion centre, has a distorted octahedral coordination geometry formed by two ethylenediamine and two water molecules. 4-aminonaphthalene-1-sulfonate acts as a counter-ion to balance the charge, and two antiparallel anions showing strong pi-pi stacking interactions are linked by paired N-H...O(sulfonate) hydrogen bonds into an isolated R2(2)(16) dimer. The crystal structure is stabilized by the pi-pi stacking interactions and hydrogen bonds.

Poly[tetraaquadi-mu3-malonato-calcium(II)zinc(II)].

The title complex, [CaZn(C3H2O4)2(H2O)4]n, is a two-dimensional polymer and consists of CaO8 and ZnO6 polyhedra linked together by malonate ligands. The Ca(II) cation, lying on a twofold axis, is coordinated by two water molecules and six malonate O atoms. The Zn(II) cation, which lies on an inversion center in an octahedral environment, is coordinated by four malonate O atoms in an equatorial arrangement and two water molecules in axial positions. The Zn-O and Ca-O bond lengths are in the ranges 2.0445 (12)-2.1346 (16) and 2.3831 (13)-2.6630 (13) angstroms, respectively. The structure comprises alternating layers along the [101] plane, the shortest Zn...Zn distance being 6.8172 (8) angstroms. The whole three-dimensional structure is maintained and stabilized by the presence of hydrogen bonds.