New Perspectives for Old Clusters: Anderson–Evans Anions as Building Blocks of Large Polyoxometalate Frameworks in a Series of Heterometallic 3 d–4 f Species

A series of nine [Sb₇W₃₆O₁₃₃Ln₃M₂(OAc)(H₂O)₈]^17? heterometallic anions ( Ln₃M₂ ; Ln=La–Gd, M=Co; Ln=Ce, M=Ni and Zn) have been obtained by reacting 3 d metal disubstituted Krebs‐type tungstoantimonates(III) with early lanthanides. Their unique tetrameric structure contains a novel {MW₉O₃₃} capping unit formed by a planar {MW₆O₂₄} fragment to which three {WO₂} groups are condensed to form a tungstate skeleton identical to that of a hypothetical trilacunary derivative of the ?‐Keggin cluster. It is shown, for the first time, that classical Anderson–Evans {MW₆O₂₄} anions can act as building blocks to construct purely inorganic large frameworks. Unprecedented reactivity in the outer ring of these disk‐shaped species is also revealed. The Ln₃M₂ anions possess chirality owing to a {Sb₄O₄} cluster being encapsulated in left‐ or right‐handed orientations. Their ability to self‐associate in blackberry‐type vesicles in solution has been assessed for the Ce₃Co₂ derivative.     

Modification of the Solution Behavior of Pd12L24 Metal–Organic Nanocages via PEGylation

The dilute solutions behaviors of Pd₁₂L₂₄ metal–organic nanocage and its two PEGylated derivatives are explored. The basic nanocages can self‐assemble into vesicle‐like blackberry structures in polar solvents via counterion‐mediated attraction, whereas the PEGylated nanocages always stay as discrete ions under the same conditions, demonstrating that the PEGylation can improve the stability of the single nanocages. In addition, larger nanocages are found to self‐assemble in less polar solvents.     

Abnormal Association between Metal−Organic Cages and Counterions Regulated by the Hydration Shells

A unique trend in the binding affinity between cationic metal−organic cages (MOCs) and external counteranions in aqueous media was observed. Similar to many macroions, two MOCs, sharing similar structures but carrying different number of charges, self-assembled into hollow spherical single-layered blackberry-type structures through counterion-mediated attraction. Dynamic and static light scattering and isothermal titration calorimetry measurements confirm the stronger interactions among less charged MOCs and counteranions than that of highly charged MOCs, leading to larger assembly sizes. DOSY NMR measurements suggest the significance of thick hydration shells of highly charged MOCs, inhibiting the MOC-counterion binding and weakening the interaction between them. This study demonstrates that the greater role played by hydration shell on ion-pair formation comparing with charge density of MOCs.     

Tunable magnetophoretic method for distinguishing and separating wear debris particles in an Fe-PDMS-based microfluidic chip

Wear debris analysis provides an early warning of mechanical transmission system aging and wear fault diagnosis, which has been widely used in machine health monitoring. The ability to detect and distinguish the ferromagnetic and nonmagnetic debris in oil is becoming an effective way to assess the health status of machinery. In this work, an Fe-poly(dimethylsiloxane) (PDMS)-based magnetophoretic method for the continuous separation of ferromagnetic iron particles by diameter and the isolation of ferromagnetic particles and nonmagnetic particles with similar diameter by type is developed. The particles experience magnetophoretic effects when passing through the vicinity of the Fe-PDMS where the strongest gradient of the magnetic fields exists. By choosing a relatively short distance between the magnet and the sidewall of the horizontal main channel and the length of Fe-PDMS with controlled particles flow rate, the diameter-dependent separation of ferromagnetic iron particles, that is, smaller than 7 µm, in the range of 8–12 µm, and larger than 14 µm, and the isolation of ferromagnetic iron particles and nonmagnetic aluminum particles based on opposite magnetophoretic behaviors by types are demonstrated, providing a potential method for the detection of wear debris particles with a high sensitivity and resolution and the diagnostic of mechanical system.     

Preparation of ZSM‐5 Coated on Monolithic Interconnected Macroporous Al2O3 Using Cheap n‐Butylamine as Template

Using cheap n‐butylamine as template, ZSM‐5 zeolites have been successfully synthesized and coated on monolithic interconnected macroporous Al₂O₃ by the secondary growth method. The use of cheap n‐butylamine could significantly reduce the synthesis cost. Hierarchical monolithic ZSM‐5 zeolites were prepared from synthetic mixtures with different H₂O/Na₂O or SiO₂/Al₂O₃ ratio. The synthesized samples were characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD), Fourier transform infrared spectroscopy (FT‐IR) and N₂ adsorption‐desorption. The results show that the hierarchical monolithic zeolites were obtained with cheap n‐butylamine template as template. During the hydrothermal reaction process, the morphology of the micrometer‐sized support was well maintained. The irregular crystals were formed in a wide range of the H₂O/Na₂O or SiO₂/Al₂O₃ ratio of synthetic mixtures and coated on monolithic Al₂O₃. The relative crystallinity of the zeolites was highest at H₂O/Na₂O=250 or SiO₂/Al₂O₃=160. This type of composites exhibited hierarchical porous structures and relatively high specific surface areas.     

Selective Permeability of Uranyl Peroxide Nanocages to Different Alkali Ions: Influences from Surface Pores and Hydration Shells

The precise guidance to different ions across the biological channels is essential for many biological processes. An artificial nanopore system will facilitate the study of the ion‐transport mechanism through nanosized channels and offer new views for designing nanodevices. Herein we reveal that a 2.5 nm‐sized, fullerene‐shaped molecular cluster Li_48+mK₁₂(OH)_m[UO₂(O₂)(OH)]_60?(H₂O)_n (m≈20 and n≈310) ( U₆₀ ) shows selective permeability to different alkali ions. The subnanometer pores on the water–ligand‐rich surface of U₆₀ are able to block Rb⁺ and Cs⁺ ions from passing through, while allowing Na⁺ and K⁺ ions, which possess larger hydrated sizes, to enter the interior space of U₆₀ . An interestingly high entropy gain during the binding process between U₆₀ and alkali ions suggests that the hydration shells of Na⁺/K⁺ and U₆₀ are damaged during the interaction. The ion selectivity of U₆₀ is greatly influenced by both the morphologies of the surface nanopores and the dynamics of the hydration shells.     

Inhomogeneous Distribution of Cationic Surfactants around Anionic Molecular Clusters

An interesting phenomenon is reported when uranyl peroxide nanoclusters U₆₀ (Li_48+mK₁₂(OH)_m[UO₂(O₂)(OH)]₆₀ (H₂O)_n, m≈20 and n≈310) interact with a small number of cationic surfactant molecules. Cationic surfactant molecules do not distribute evenly around the U₆₀ clusters during the interaction as expected. Instead, a small fraction of U₆₀ clusters attract almost all the surfactant molecules, leading to the self-assembly into supramolecular structures by using surfactant–U₆₀ complexes as building locks, and later further aggregate and precipitate based on hydrophobic interaction, whereas the rest of the clusters remained unbounded soluble macroions in bulk dispersion. This phenomenon nicely demonstrates a unique feature of macroion solutions. Considering that Debye–Hückel approximation is no longer valid in such solutions, the competition between the local electrostatic interaction and hydrophobic interaction becomes important to regulate the solution behaviors of macroions.     

An elementary proof for the representation theorem of analytic isotropic tensor functions of a second-order tensor

正following Cayley-Hamilton theorem:(1)where I1, I2, and I3denote the first, second, and third principal invariants of and N-dimensional space,(2)     

Mannose‐based graft polyesters with tunable binding affinity to concanavalin A

Glycopolymers have been widely used to understand the interactions between carbohydrates and lectins, which facilitate the diagnosis and detection of disease and pathogens as well as the development of vaccines. While studies have been focused on the correlation of glycopolymer structure and their binding to lectins, graft‐type glycopolyesters are uncommon. Herein, we report the design and synthesis of mannose‐based graft polyesters by “grafting‐from” method and investigate their interactions with Concanavalin A (Con A). As confirmed by ¹H NMR spectroscopy and sulfuric acid‐UV method, graft polyesters with different lengths of mannose graft were successfully synthesized. Our results from turbidimetry binding assay showed that graft polyesters with longer mannose graft exhibit higher initial binding rate (k_i). Isothermal titration calorimetry measurements of these graft polyesters with Con A showed that polymers exhibit higher binding affinity (k_a) with the number of side chain mannose. This study provides understanding of the interaction between Con A and mannose‐based graft polyesters, which can be employed for the development of glycopolymeric therapeutics. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3908–3917