Rhombicuboctahedral Ag100: Four‐Layered Octahedral Silver Nanocluster Adopting the Russian Nesting Doll Model

Precise atomic structure of metal nanoclusters (NCs) is fundamental for elucidating the structure–property relationships and the inherent size‐evolution principles. Reported here is the largest known FCC‐based (FCC=face centered cubic) silver nanocluster, [Ag₁₀₀(SC₆H₃^3,4F₂)₄₈(PPh₃)₈]^?: the first all‐octahedral symmetric nesting Ag nanocluster with a four‐layered Ag₆@Ag₃₈@Ag₄₈S₂₄@Ag₈S₂₄P₈ structure, consistent symmetry elements, and a unique rhombicuboctahedral morphology distinct from theoretical predictions and previously reported FCC‐based Ag clusters. DFT studies revealed extensive interlayer interactions and degenerate frontier orbitals. The FCC‐based Russian nesting doll model constitutes a new platform for the study of the size‐evolution principles of Ag NCs.     

Glycoconjugated Metallohelices have Improved Nuclear Delivery and Suppress Tumour Growth In Vivo

Monosaccharides are added to the hydrophilic face of a self‐assembled asymmetric Fe^II metallohelix, using CuAAC chemistry. The sixteen resulting architectures are water‐stable and optically pure, and exhibit improved antiproliferative selectivity against colon cancer cells (HCT116 p53^+/+) with respect to the non‐cancerous ARPE‐19 cell line. While the most selective compound is a glucose‐appended enantiomer, its cellular entry is not mainly glucose transporter‐mediated. Glucose conjugation nevertheless increases nuclear delivery ca 2.5‐fold, and a non‐destructive interaction with DNA is indicated. Addition of the glucose units affects the binding orientation of the metallohelix to naked DNA, but does not substantially alter the overall affinity. In a mouse model, the glucose conjugated compound was far better tolerated, and tumour growth delays for the parent compound (2.6 d) were improved to 4.3 d; performance as good as cisplatin but with the advantage of no weight loss in the subjects.     

Non‐Lithography Hydrodynamic Printing of Micro/Nanostructures on Curved Surfaces

A key issue of micro/nano devices is how to integrate micro/nanostructures with specified chemical components onto various curved surfaces. Hydrodynamic printing of micro/nanostructures on three‐dimensional curved surfaces is achieved with a strategy that combines template‐induced hydrodynamic printing and self‐assembly of nanoparticles (NPs). Non‐lithography flexible wall‐shaped templates are replicated with microscale features by dicing a trench‐shaped silicon wafer. Arising from the capillary pumped function between the template and curved substrates, NPs in the colloidal suspension self‐assemble into close‐packed micro/nanostructures without a gravity effect. Theoretical analysis with the lattice Boltzmann model reveals the fundamental principles of the hydrodynamic assembly process. Spiral linear structures achieved by two kinds of fluorescent NPs show non‐interfering photoluminescence properties, while the waveguide and photoluminescence are confirmed in 3D curved space. The printed multiconstituent micro/nanostructures with single‐NP resolution may serve as a general platform for optoelectronics beyond flat surfaces.     

Method development and validation for the determination of biogenic amines in soy sauce using supercritical fluid chromatography coupled with single quadrupole mass spectrometry

Biogenic amines have been reported in many foods such as fish, meat, and soy sauce. The consumption of foods containing high concentrations of biogenic amines has been associated with health hazards. In this study, a green and efficient method using supercritical fluid chromatography coupled with single quadrupole mass spectrometry was developed for determination of biogenic amines in soy sauce. The chromatographic and mass spectrometry conditions were systematically optimized in terms of selectivity and peak shape. Nine biogenic amines were well separated within 25 min on a Cosmosil 5HP column using 5% (v/v) water and 0.2% (v/v) ammonia solution in methanol as mobile phase additives at a backpressure of 120 bar and temperature of 40°C. The established method was fully validated regarding the linearity, sensitivity, precision, and accuracy. The limits of detection and limits of quantification ranged from 0.03 to 10.50 μg/mL and 0.10 to 23.1 μg/mL, respectively. The relative standard deviations for intra‐ and interday precisions were all lower than 9.36% and the recoveries ranged from 75.82 to 99.63% and 80.10 to 99.89% for two levels of standards spiked in soy sauce, respectively. Finally, the established method was successfully applied to the quantitative analysis of biogenic amines in soy sauce.     

Copper-thioguanine metallodrug with self-reinforcing circular catalysis for activatable MRI imaging and amplifying specificity of cancer therapy

For chemotherapy, drug delivery systems often suffer from the inefficient drug loading capability, which usually cause systems toxicity and extra burden to excrete carrier itself. Moreover, the cancer therapeutic efficacy is also greatly limited by the specificity of tumor microenvironment for reactive oxygen species(ROS) based cancer therapeutic strategy(e.g., chemodynamic therapy). Herein, we have developed metal-drug coordination nanoplatform that can not only be responsive to tumor microenvironment but also modulate it, so as to achieve efficient treatment of cancer. Excitingly, by employing small molecule drug(6-thioguanine) as ligand copper ions, we achieve a high drug loading rate(60.1%) and 100% of utilization of metal-drug coordination nanoplatform(Cu-TG). Interestingly, Cu-TG possessed high-efficiently horseradish peroxidase-like, glutathione peroxidase-like and catalase-like activity. Under the tumor microenvironment, Cu-TG exhibited the self-reinforcing circular catalysis that is able to amplify the cellular oxidative stress, inducing notable cancer cellular apoptosis. Moreover, Cu-TG could be activated with glutathione(GSH) and facilitated for GSH triggered 6-TG release, higher selective therapeutic effect toward cancer cells, and GSH activated T_1 weight-magnetic resonance imaging. Based on the above properties, Cu-TG exhibited magnetic resonance imaging(MRI) guiding, efficient and synergistic combination of chemodynamic and chemotherapy with self-reinforcing therapeutic outcomes in vivo.     

Molybdenum Carbide‐Embedded Multichannel Hollow Carbon Nanofibers as Bifunctional Catalysts for Water Splitting

With the environmental pollution and non‐renewable fossil fuels, it is imperative to develop eco‐friendly, renewable, and highly efficient electrocatalysts for sustainable energy. Herein, a simple electrospinning process used to synthesis Mo₂C‐embedded multichannel hollow carbon nanofibers (Mo₂C‐MCNFs) and followed by the pyrolysis process. As prepared lotus root‐like nanoarchitecture could offer rich porosity and facilitate the electrolyte infiltration, the Mo₂C‐MCNFs delivered favourable catalytic activity for HER and OER. The resultant catalysts exhibit low overpotentials of 114 mV and 320 mV at a current density of 10 mA cm^?2 for HER and OER, respectively. Furthermore, using the Mo₂C‐MCNFs catalysts as a bifunctional electrode toward overall water splitting, which only needs a small cell voltage of 1.68 V to afford a current density of 10 mA cm^?2 in the home‐made alkaline electrolyzer. This interesting work presents a simple and effective strategy to further fabricating tunable nanostructures for energy‐related applications.     

Nonlinear vibration isolation via an innovative active bionic variable stiffness adapter (ABVSA)

Nonlinear Dynamics - During the process of spacecraft launch, the extreme vibration environment is the major influence factor that induces the failure of the mission. Inspired by the smooth motions...     

Comparative study of free energies of solvation of phenylimidazole inhibitors of cytochrome P450cam by free energy simulation,AMSOL, and Poisson Boltzmann methods

Free energies of solvation of phenylimidazole inhibitors of cytochrome P450cam were determined using (1) free energy simulation, (2) AMSOL-SM2 semiempirical methods, and (3) Poisson-Boltzmann methods. The goals of this study were threefold: (1) to compare the results obtained from the three different methods, (2) to investigate the effect of inclusion of intraperturbed group interactions on free energy simulation estimates of solvation free energy differences, and (3) to investigate to what extent differences in free energies of solvation among three of these inhibitors could account for observed differences in their enzyme binding free energies. In general, relative solvation free energies obtained from the free energy simulations and AMSOL-SM2 methods give comparable results (i.e., the same rank ordering and similar quantitative results, differing significantly from results obtained using Poisson-Boltzmann methods). The free energy simulation studies suggest that the neglect of intraperturbed group interactions had little effect on rank order of free energies of solvation of the polar phenylimidazoles. The relative desolvation free energies of the three inhibitors of P450cam—1-phenylimidazole (1-PI), 2-phenylimidazole (2-PI), and 4-phenylimidazole (4-PI)—with known enzyme bound X-ray structures parallel that of their known binding affinities and could account for most of the differences in the free energies of binding of these three inhibitors to P450cam. The origin of the difference of the free energies of solution of these three inhibitors is primarily the additional interaction between solvent and N(SINGLE BOND)H group in the imidazole ring of 2- and 4-phenylimidazole that is absent in the 1-phenylimidazole isomer. This hypothesis is substantiated by a second comparison of the relative solvation free energies of 4-phenylimidazole with its methylated derivative, 3-methyl-4-phenylimidazole, also lacking an N(SINGLE BOND)H group. © 1996 by John Wiley & Sons, Inc.     

Syndioselective propylene polymerizations by ansa-zirconocenium catalyst

The effect of reaction conditions, including catalyst concentration, temperature, and immobilization on support, have been investigated for syndioselective propylene polymerization by the “bare” zirconocenium ion generated from 1,1-diphenyl-methylidene(1-η⁵-cyclopentadienyl)(9-η⁵-fluorenyl)zirconium-dichloride precursor (2). Neither variation of the catalyst concentration nor immobilization of 2 on silica support affect the syndiospecificity of polymerization. The stereoregularity of the syndiotactic polypropylene, as judged from the melting transition temperature and homosteric r-pentad population by ¹³C-NMR, were found to be proportional to polymer molecular weight. These behaviors are compared with a typical isoselective catalyst ethylenebis(4,5,6,7-tetrahydroindenyl) Zr precursor (4). They are in close resemblance in the case of the S-enantiomeric complex of 4, but the racemic mixture of 4 is markedly inferior. The origins of stereo- and regio-errors are discussed. © 1996 John Wiley & Sons, Inc.