The understanding of structure-activity relationships at the atomic level has played a profound role in heterogeneous catalysis, providing valuable insights into designing suitable heterogeneous catalysts. However, uncovering the detailed roles of how such active species' structures affect their catalytic performance remains a challenge owing to the lack of direct structural information on a specific active species. Herein, we deposited molybdenum(VI), an active species in oxidation reactions, on the Zr6 node of a mesoporous zirconium-based metal-organic framework (MOF) NU-1200, using solvothermal deposition in MOFs (SIM). Due to the high crystallinity of the NU-1200 support, the precise structure of the resulting molybdenum catalyst, Mo-NU-1200, was characterized through single-crystal X-ray diffraction (SCXRD). Two distinct anchoring modes of the molybdenum species were observed one mode (Mo1), displaying an octahedral geometry, coordinated to the node through one terminal oxygen atom and the other mode (Mo of an active species' structural evolution from metal installation to subsequent catalytic reaction. As a result, these subtle structural changes in catalyst binding motifs led to distinct differences in catalytic activities, providing a compelling strategy for elucidating structure-activity relationships.Potassium periodate (PI, KIO4) was readily activated by Fe(II) under acidic conditions, resulting in the enhanced abatement of organic contaminants in 2 min, with the decay ratios of the selected pollutants even outnumbered those in the Fe(II)/peroxymonosulfate and Fe(II)/peroxydisulfate processes under identical conditions. Both 18O isotope labeling techniques using methyl phenyl sulfoxide (PMSO) as the substrate and X-ray absorption near-edge structure spectroscopy provided conclusive evidences for the generation of high-valent iron-oxo species (Fe(IV)) in the Fe(II)/PI process. Density functional theory calculations determined that the reaction of Fe(II) with PI followed the formation of a hydrogen bonding complex between Fe(H2O)62+ and IO4(H2O)-, ligand exchange, and oxygen atom transfer, consequently generating Fe(IV) species. More interestingly, the unexpected detection of 18O-labeled hydroxylated PMSO not only favored the simultaneous generation of · OH but also demonstrated that ·OH was indirectly produced through the self-decay of Fe(IV) to form H2O2 and the subsequent Fenton reaction. In addition, IO4- was not transformed into the undesired iodine species (i.e., HOI, I2, and I3-) but was converted to nontoxic iodate (IO3-). This study proposed an efficient and environmental friendly process for the rapid removal of emerging contaminants and enriched the understandings on the evolution mechanism of ·OH in Fe(IV)-mediated processes.Iatrogenic extrahepatic bile duct injury remains a dreaded complication while performing cholecystectomy. Although X-ray based cholangiography could reduce the incidence of biliary tract injuries, the deficiencies including radiation damage and expertise dependence hamper its further clinical application. The effective strategy for intraoperative cholangiography is still urgently required. Herein, a fluorescence-based imaging approach for cholangiography in the near-infrared IIb window (1500-1700 nm) using TT3-oCB, a bright aggregation-induced emission luminogen with large π-conjugated planar unit, is reported. In phantom studies, TT3-oCB nanoparticles exhibit high near-infrared IIb emission and show better image clarity at varying penetrating depths. When intrabiliary injected into the gallbladder or the common bile duct of the rabbit, TT3-oCB nanoparticles enable the real-time imaging of the biliary structure with deep penetrating capability and high signal-to-background ratio. Moreover, the tiny iatrogenic biliary injuries and the gallstones in established disease models could be precisely diagnosed by TT3-oCB nanoparticle assisted near-infrared IIb imaging. In summary, we reported a feasible application for aggregation-induced emission dots as biliary contrast agent and realized high-quality cholangiography in the near-infrared IIb window with precise diagnostic ability and nonradioactive damage, which could possibly be applied for intraoperative diagnosis.Inhibition of herpes simplex virus type 1 (HSV-1) binding to the host cell surface by highly sulfated architectures is among the promising strategies to prevent virus entry and infection. https://www.selleckchem.com/products/ms-275.html However, the structural flexibility of multivalent inhibitors plays a major role in effective blockage and inhibition of virus receptors. In this study, we demonstrate the inhibitory effect of a polymer scaffold on the HSV-1 infection by using highly sulfated polyglycerols with different architectures (linear, dendronized, and hyperbranched). IC50 values for all synthesized sulfated polyglycerols and the natural sulfated polymer heparin were determined using plaque reduction infection assays. Interestingly, an increase in the IC50 value from 0.03 to 374 nM from highly flexible linear polyglycerol sulfate (LPGS) to less flexible scaffolds, namely, dendronized polyglycerol sulfate and hyperbranched polyglycerol sulfate was observed. The most potent LPGS inhibits HSV-1 infection 295 times more efficiently than heparin, and we show that LPGS has a much reduced anticoagulant capacity when compared to heparin as evidenced by measuring the activated partial thromboplastin time. Furthermore, prevention of infection by LPGS and the commercially available drug acyclovir were compared. All tested sulfated polymers do not show any cytotoxicity at concentrations of up to 1 mg/mL in different cell lines. We conclude from our results that more flexible polyglycerol sulfates are superior to less flexible sulfated polymers with respect to inhibition of HSV-1 infection and may constitute an alternative to the current antiviral treatments of this ubiquitous pathogen.A lariat anthraquinone macrocycle functionalized with catechol (H2L) was synthesized via the Mannich reaction. The Mannich base H2L can be partially decomposed into L1·3H2O and HL1·NO3·2H2O in the presence of tetrabutylammonium hydroxide/Al(NO3)3·9H2O in dimethyl sulfoxide (DMSO). Free L1·3H2O is essentially coplanar, while protonated HL1·NO3·2H2O is highly distorted. Dark-green FeCl3·H2L·2H2O powder and Fe2(HL)2Cl4 crystal can be isolated from ethanol (C2H5OH) in high/low H2L concentration. Anthraquinone in H2L is essentially coplanar but distorted in Fe2(HL)2Cl4. The Fe(III) ion in Fe2(HL)2Cl4 adopts a less common five-coordination with three catecholate O and two Cl atoms in the dimer. The distortion of inbound C═O is much higher than that of outbound C═O in anthraquinone in all of these compounds. H2L responds to chlorides of Li+, Na+, K+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+, Fe3+, Cu2+, Zn2+, and Al3+ in a DMSO solution, which can be observed by differential pulse voltammetry, UV-vis, and 1H NMR. All of these mean C2H5OH solution in the presence of OH-.Low-cost, highly active, and highly stable catalysts are desired for the generation of hydrogen and oxygen using water electrolyzers. To enhance the kinetics of the oxygen evolution reaction in an acidic medium, it is of paramount importance to redesign iridium electrocatalysts into novel structures with organized morphology and high surface area. Here, we report on the designing of a well-defined and highly active hollow nanoframe based on iridium. The synthesis strategy was to control the shape of nickel nanostructures on which iridium nanoparticles will grow. After the growth of iridium on the surface, the next step was to etch the nickel core to form the NiIr hollow nanoframe. The etching procedure was found to be significant in controlling the hydroxide species on the iridium surface and by that affecting the performance. The catalytic performance of the NiIr hollow nanoframe was studied for oxygen evolution reaction and shows 29 times increased iridium mass activity compared to commercially available iridium-based catalysts. Our study provides novel insights to control the fabrication of iridium-shaped catalysts using 3d transition metal as a template and via a facile etching step to steer the formation of hydroxide species on the surface. These findings shall aid the community to finally create stable iridium alloys for polymer electrolyte membrane water electrolyzers, and the strategy is also useful for many other electrochemical devices such as batteries, fuel cells, sensors, and solar organic cells.Single-molecule experiments have been helping us to get deeper inside biological phenomena by illuminating how individual molecules actually work. Digital bioassay, in which analyte molecules are individually confined in small compartments to be analyzed, is an emerging technology in single-molecule biology and applies to various biological entities (e.g., cells and virus particles). However, digital bioassay is not compatible with multiconditional and multiparametric assays, hindering in-depth understanding of analytes. This is because current digital bioassay lacks a repeatable solution-exchange system that keeps analytes inside compartments. To address this challenge, we developed a digital bioassay platform with easy solution exchanges, called multidimensional (MD) digital bioassay. We immobilized single analytes in arrayed femtoliter (10-15 L) reactors and sealed them with airflow. The solution in each reactor was stable and showed no cross-talk via solution leakage for more than 2 h, and over 30 rounds of perfect solution exchanges were successfully performed. With multiconditional assays based on our system, we could quantitatively determine inhibitor sensitivities of single influenza A virus particles and single alkaline phosphatase (ALP) molecules, which has never been achieved with conventional digital bioassays. Further, we demonstrated that ALPs from two origins can be precisely distinguished by a single-molecule multiparametric assay with our system, which was also difficult with conventional digital bioassays. Thus, MD digital bioassay is a versatile platform to gain in-depth insight into biological entities in unprecedented resolution.Point defect engineering in Cu2ZnSnSe4 (CZTSe) thin films is the main issue to improve its device performance. This study reveals the correlation between the reaction pathway and the point defects in the CZTSe film. The reaction pathway from a metallic precursor (Mo/Zn/Sn/Cu) to a kesterite CZTSe film is varied by changing the annealing process. The synthesized CZTSe films under different reaction pathways induce different device performances with different defect energy levels, although all CZTSe films have similar structural and optical properties (Eg ∼ 1.0 eV). The admittance spectroscopy demonstrates the correlations between point defect types (VZn, ZnSn, ZnCu, CuZn, and VCu) and the reaction pathways for the formation of CZTSe films. The different growth rates of binary selenides, such as ZnSe and/or Sn-Se phases, during the annealing process are especially strongly related to the formation of point defects, leading to the different open-circuit voltages (396-451 mV) and fill factors (51-65%). The results of this study suggest that controlling the reaction pathway is an effective approach to adjust the formation of defects in the kesterite CZTSe film as well as to fabricate high-performance solar cell devices.