Chemistry Design Towards a Stable Sulfide‐Based Superionic Conductor Li4Cu8Ge3S12

Sulfide‐based superionic conductors with high ionic conductivity have been explored as candidates for solid‐state Li batteries. However, moisture hypersensitivity has made their manufacture complicated and costly and also impeded applications in batteries. Now, a sulfide‐based superionic conductor Li₄Cu₈Ge₃S₁₂ with superior stability was developed based on the hard/soft acid–base theory. The compound is stable in both moist air and aqueous LiOH aqueous solution. The electrochemical stability window was up to 1.5 V. An ionic conductivity of 0.9×10^?4 S cm with low activation energy of 0.33 eV was achieved without any optimization. The material features a rigid Cu‐Ge‐S open framework that increases its stability. Meanwhile, the weak bonding between Li⁺ and the framework promotes ionic conductivity. This work provides a structural configuration in which weak Li bonding in the rigid framework promotes an environment for highly conductive and stable solid‐state electrolytes.     

6,8-di-C-glycosyl flavones with β-furanoarabinose from Scutellaria baicalensis and their anti-inflammatory activities

Two flavone di-C-glycosides, a pair of isomers, were isolated from Scutellaria baicalensis. The structures of compounds 1 and 2 were elucidated by means of physical data, including 1D and 2D NMR and HR-ESI-MS. Supporting theoretical calculations of the compound conformational landscape has also been conducted for geometry optimization. This is the first report of the natural occurrence of β-furanoarabinoside. In addition, the effects of compounds 1 and 2 on NO, pro-inflammatory cytokines, PGE2 and COX-2 levels were measured in lipopolysaccharide (LPS)-stimulated RAW264.7 macrophage cells. The pair of isomers exhibited significant inhibitory effects on inflammation.     

Small-scale seismic inversion using surface waves extracted from noise cross correlation

Green's functions can be retrieved between receivers from the correlation of ambient seismic noise or with an appropriate set of randomly distributed sources. This principle is demonstrated in small-scale geophysics using noise sources generated by human steps during a 10-min walk in the alignment of a 14-m-long accelerometer line array. The time-domain correlation of the records yields two surface wave modes extracted from the Green's function between each pair of accelerometers. A frequency-wave-number Fourier analysis yields each mode contribution and their dispersion curve. These dispersion curves are then inverted to provide the one-dimensional shear velocity of the near surface.     

Syntheses of novel di- and trinucleating ligands having a triethylbenzene core with N,N-bidentate tethers: their complexation toward Pd and Rh organometallic fragments

A series of di- and trinucleating ligands with a 1,3,5-triethylbenzene core connected to N,N-bidentate tethers was synthesized. The ligands readily reacted with monuclear Rh and Pd precursors to give the corresponding di- and trinuclear complexes, which were characterized by using NMR and ESI mass spectroscopy. In the solid state, the trinuclear complexes with ligands having pyridylpyrazolyl tethers adopt the most stable ababab configuration, in which the organometallic fragments are on the same side of the benzene plane. On the other hand, in solution, the linker moieties between the benzene core and the metals are flexible enough to interconvert between other configurations, that is, they exhibit dynamic behavior, and the rotational barrier was dependent on the length of the linkers. From variable temperature (VT) 1H NMR measurements, the rotational barrier for a trinuclear Rh-CO complex with a ligand having methylene linkers was estimated to be approximately 12.6 kcal mol(-1). However, no spectral changes were observed for the ethylene derivative in the temperature range of -60 degrees C to 50 degrees C, indicating that the rotation was not frozen out on the 1H NMR timescale, even at -60 degrees C.     

含杯芳烃聚合物的合成与应用

杯芳烃在主客体化学中是继冠醚和环糊精之后被广泛关注的第三代主体分子,能够选择性地与客体分子或离子形成络合物。近年来,含杯芳烃聚合物逐渐受到人们的重视。结合聚合物稳定性好,易于加工的特性,含杯芳烃聚合物将有望被开发成为新型功能高分子材料。本文详细介绍了含杯芳烃聚合物的合成及其应用。     

An In Situ Investigation of the Protein Corona Formation Kinetics of Single Nanomedicine Carriers by Self-Regulated Electrochemiluminescence Microscopy

Protein coronas are present extensively at the bio-nano interface due to the natural adsorption of proteins onto nanomaterials in biological fluids. Aside from the robust property of nanoparticles, the dynamics of the protein corona shell largely define their chemical identity by altering interface properties. However, the soft coronas are normally complex and rapidly changing. To real-time monitor the entire formation, we report here a self-regulated electrochemiluminescence (ECL) microscopy based on the interaction of the Ru(bpy)₃³⁺ with the nanoparticle surface. Thus, the heterogeneity of the protein corona is in situ observed in single nanoparticle “cores” before and after loading drugs in nanomedicine carriers. The label-free, optical stable and dynamic ECL microscopy minimize misinterpretations caused by the variation of nanoparticle size and polydispersity. Accordingly, the synergetic actions of proteins and nanoparticles properties are uncovered by chemically engineered protein corona. After comparing the protein corona formation kinetics in different complex systems and different nanomedicine carriers, the universality and accuracy of this technique were well demonstrated via the protein corona formation kinetics curves regulated by competitive adsorption of Ru(bpy)₃³⁺ and multiple proteins on surface of various carriers. The work is of great significance for studying bio-nano interface in drug delivery and targeted cancer treatment.     

Accurate Geometry and Non-Covalent Interactions in 1-Phenylethanol and its Monohydrate: A Rotational Study

The pure rotational spectra of 1-phenylethanol and its monohydrate were measured by using a pulsed jet Fourier transform microwave spectrometer. One conformer of the 1-phenylethanol monomer with the trans form was observed in the pulsed jet. The experimental values of rotational constants of ten isotopologues, including eight mono-substituted ¹³C and one D isotopologues, allow an accurate structure determination of the skeleton of 1-phenylethanol. For its monohydrate, only one isomer has been observed, of which 1-phenylethanol adopts the trans form and binds with water through an O−H⋅⋅⋅O_w and an O_w−H⋅⋅⋅π hydrogen bond. Each rotational transition displays a doublet with a relative intensity ratio of 1 : 3, due to a hindered internal rotation of water around its C₂ axis. This study provides the information on accurate geometry of 1-phenylethanol (PE) and large amplitude motion of water in the PE monohydrate.     

Thermodynamic and kinetic properties of <Emphasis Type="Italic">cis</Emphasis>-diammineglycolatoplatinum in different water solvents

The dissolution behavior of cis-diammineglycolatoplatinum (nedaplatin) in saline, water and glucose were studied by a microcalorimetric method. The integral heats and differential heats of the dissolution were measured to establish the equation for the solute and the heats. The corresponding half-life, kinetic and thermodynamic properties of the nedaplatin solutions were determined. The results show that hydrogen bonds could be generated and the dissolution entropy of nedaplatin in different solvents is negative during the dissolution process, so as to enhance the drug stability, but there is an obvious difference in stability in different solvents.     

Option contracts: a solution for overloading problems in the delivery service supply chain

Owing to the limited service capacity of express delivery providers, most online retailers have to reject many orders during hot selling seasons. In this paper, we consider an express delivery service supply chain consisting of an express delivery provider and an online retailer whereby the selling season includes both regular periods and online sales periods. Utilizing a modified newsvendor model, we derive the express delivery provider’s optimal capacity decision and find that the overloading problem cannot be avoided because delivery service cannot be inventoried. To solve such a problem, we introduce an option contract to coordinate the supply chain. By allowing the online retailer to book the capacity, the express delivery provider can rent capacity from a third party in advance. Results show this approach can mitigate the problem significantly. We also extend our model to a supply chain consisting of a delivery provider and two retailers.