Spontaneous self-assembly of metal-organic cationic nanocages to form monodisperse hollow vesicles in dilute solutions

In this communication we report the unprecedented spontaneous self-assembly of cationic nanoporous metal-organic coordination cages (nanocages) into giant hollow vesicle-like structures in polar solvents. Such highly soluble nanocages (macrocations) have separated hydrophobic regions. However, their assembly is not due to hydrophobic interactions but the counterion-mediated attractions, very similar to the unique self-assembly of polyoxometalate macroanions into single-layer, spherical blackberry structures, as characterized by laser light scattering and TEM studies. This is the first study on the solution behavior of metal-organic nanocages and also the first report on the self-assembly of soluble macrocations. Therefore, the blackberry structure is likely to be a universal type of self-assembly for soluble macroions. In addition, the self-assembled nanocages can provide blackberry structures a wide range of organic functionalities that are impossible to reach with purely inorganic systems, which may open the door to many types of applications.     

Conversion of Cu2O nanocrystals into hollow Cu2-xSe nanocages with the preservation of morphologies

With the use of PVP (polyvinylpyrrolidone) as capping reagent, cubic, octahedral and spherical Cu2O nanocrystals were obtained in aqueous media when different reducing agents were applied. After adding selenium sources at room temperature, these nanocrystals could be converted (based on the Kirkendall effect) into hollow Cu2-xSe nanocages that keep their corresponding orignial morphologies.     

Easy synthesis of hollow core, bimodal mesoporous shell carbon nanospheres and their application in supercapacitor

Hollow core, mesoporous shell carbon nanospheres (HCMSs) with large bimodal mesopores (6.4 and 3.1 nm) and high surface area (1704 m(2) g(-1)) have been synthesized by a triconstituent surface co-assembly of monodisperse silica nanospheres method. The resulted HCMS show a high specific capacity of 251 F g(-1) at 50 mV s(-1) in 2 M H(2)SO(4) and long cyclic life.     

The synthesis of ZnS hollow nanospheres with nanoporous shell

ZnS hollow nanospheres with nanoporous shell were successfully synthesized through the evolvement of ZnO nanospheres which were synthesized by hydrothermal method with poly (sodium-p-styrene sulfonate) (PSS) as surfactant at low temperature. The as-synthesized samples were characterized with X-ray diffraction (XRD), transmission electron microscopy (TEM), field emission scanning electron microscopy (FESEM), UV/vis spectrum and N₂ adsorption. The results showed that the shell of as-synthesized ZnS hollow structure was composed of many fine crystallites and had a nanoporous structure with pore diameter about 4 nm demonstrated by N₂ adsorption/desorption isotherm. The sample possessed efficiency of photocatalytic degradation on X-containing (X=Cl, Br, I) organic pollutants.     

Fabrication of hollow titania microspheres with tailored shell thickness

Submicron hollow spheres are an interesting class of materials that receive significant attention nowadays. Closed and mechanically robust homogeneous hollow titania microspheres with as much shell thickness as 130 nm were fabricated by coating polystyrene beads with titania nanoparticles using sol–gel chemistry and subsequently removing the core either via heating or a chemical dissolution process. The thickness of the titania shell deposited on polystyrene core was finely tuned between 100 and 130 nm by varying the concentration of titania precursor, i.e., Ti(OEt)₄ salt from 0.5 to 2 mM during the coating process. The obtained hybrid core–shell particles and hollow microspheres were characterized by scanning electron microscopy, transmission electron microscopy, infrared spectroscopy, X-ray diffraction, and thermo-gravimetric analysis. The approach employed is well suited to the preparation of titania-coated polystyrene hybrid particles and hollow titania spheres, which can find their applications as novel building blocks with unique optical properties for fabrication of advanced materials, catalyst, and drug delivery system.     

Controlling the chirality of DNA nanocages

Playing DNA Twister: By using asymmetric DNA building blocks, self-assembled DNA nanocages that are chiral on the nanoscale have been designed. The resulting DNA nanocages have been characterized with a variety of methods. Such chiral control could be useful for tuning the photonic/optical properties of DNA-templated nanostructures.     

Sub-nanometre sized metal clusters: from synthetic challenges to the unique property discoveries

Sub-nanometre sized metal clusters, with dimensions between metal atoms and nanoparticles, have attracted more and more attention due to their unique electronic structures and the subsequent unusual physical and chemical properties. However, the tiny size of the metal clusters brings the difficulty of their synthesis compared to the easier preparation of large nanoparticles. Up to now various synthetic techniques and routes have been successfully applied to the preparation of sub-nanometre clusters. Among the metals, gold clusters, especially the alkanethiolate monolayer protected clusters (MPCs), have been extensively investigated during the past decades. In recent years, silver and copper nanoclusters have also attracted enormous interest mainly due to their excellent photoluminescent properties. Meanwhile, more structural characteristics, particular optical, catalytic, electronic and magnetic properties and the related technical applications of the metal nanoclusters have been discovered in recent years. In this critical review, recent advances in sub-nanometre sized metal clusters (Au, Ag, Cu, etc.) including the synthetic techniques, structural characterizations, novel physical, chemical and optical properties and their potential applications are discussed in detail. We finally give a brief outlook on the future development of metal nanoclusters from the viewpoint of controlled synthesis and their potential applications.     

Molecular squares with paramagnetic diruthenium corners: synthetic and crystallographic challenges

The reaction of Ru(2)(mu-O(2)CMe)(4)Cl with approximately 2.5 equiv of HDAniF (HDAniF = N,N'-di(p-anisyl)formamidine) in refluxing THF resulted in the synthesis of cis-Ru(2)(mu-DAniF)(2)(mu-O(2)CMe)(2)Cl (1). This Ru(2)(5+)complex, which has two labile acetate groups occupying two equatorial cisoid positions, was used for the construction of discrete paramagnetic supramolecular arrays. Subsequent reactions of 1 with HO(2)C-CO(2)H (oxalic acid) and 1,4-HO(2)C-C(6)H(4)-CO(2)H (terephthalic acid) followed by recrystallization from 1,2-C(2)H(4)Cl(2)/hexanes solutions containing wet MeCN or 4-Bu(t)py (4-tert-butylpyridine) gave crystals of [[is-Ru(2)(mu-DAniF)(2)Cl(H(2)O)]mu-oxalate)](4).MeCN.2(C(6)H(14)).12(H(2)O) (2) and [[is-Ru(2)(mu-DAniF)(2)Cl(0.646)(4-Bu(t)py)(1.354)]mu-terephthlate)](4)Cl(1.414).17(1,2-C(2)H(4)Cl(2)).C(6)H(14) (3), respectively. These are the first polygonal supramolecular assemblies consisting of paramagnetic M(2) units at each apex, where M(2) = Ru(2)(5+). Compounds 2 and 3 have been structurally characterized, and their electrochemistry and magnetic properties have been studied. These studies have confirmed that oxalate linkers are better than the terephthalate linkers in effecting electronic and magnetic coupling.     

Facile route to Zn-based II-VI semiconductor spheres, hollow spheres, and core/shell nanocrystals and their optical properties

A convenient chemical conversion method that allows the direct preparation of nanocrystalline ZnE (E = O, S, Se) semiconductor spheres and hollow spheres as well as their core/shell structures is reported. By using monodisperse ZnO nanospheres as a starting reactant and in situ template, ZnS, ZnSe solid and hollow nanospheres, and ZnO/ZnS and ZnO/ZnSe core/shell nanostructures have been obtained through an ultrasound-assisted solution-phase conversion process. The formation mechanism of these nanocrystals is connected with the sonochemical effect of ultrasound irradiation. The photoluminescence and electrogenerated chemiluminescence properties of the as-prepared nanocrystals were investigated.     

Development of synthetic double helical polymers and oligomers

There is growing interest in the design and synthesis of artificial helical polymers and oligomers, in connection with biological importance as well as development of novel chiral materials. Since the discovery of the helical structure of isotactic polypropylene, a significant advancement has been achieved for synthetic polymers and oligomers with a single helical conformation for about half a century. In contrast, the chemistry of double helical counterparts is still premature. This short review highlights the recent advances in the synthesis, structures, and functions of double helical polymers and oligomers, featuring an important role of supramolecular chemistry in the design and synthesis of double helices. Although the artificial double helices reported to date are still limited in number, recent advancement of supramolecular chemistry provides plenty of structural motifs for new designs. Therefore, artificial double helices hold great promise as a new class of compounds. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5195–5207, 2009     

Preparation of hollow polymer particles with a single hole in the shell by SaPSeP

The influence of sodium dodecyl sulfate (SDS) on the shell formation of hollow polymer particles prepared by the SaPSeP method, which was proposed by the authors for the preparation of micrometer-sized hollow polymer particles, was investigated. A single hole was observed in the shell of the hollow particles prepared by seeded polymerization of micrometer-sized, monodisperse divinylbenzene/p-xylene droplets in aqueous medium in the presence of SDS at concentrations above 43.3 mM, which were prepared by the dynamic swelling method. The fraction of the hollow particles having a single hole in the shell and the area of the hole increased with the SDS concentration.     

Metallic monoboronyl compounds: Prediction of their structure and comparison with the cyanide analogues

A theoretical study of monoboronyls of different metals has been carried out. We have chosen Mg as representative of s‐block elements, Al for the p‐block, and Group 11 metals (Cu, Ag, and Au) for the d‐block. Different behaviors are observed: bonding through the oxygen atom is preferred in the case of Al, for all Group 11 monoboronyls bonding through the boron atom prevails and both interactions give rise to almost isoenergetic compounds in the case of Mg. Predictions for the spectroscopic parameters relevant for rotational and vibrational spectroscopy of the different competitive species are provided. Al and Group 11 boronyls have relatively high dissociation energies, whereas Mg boronyl has moderate dissociation energy. The molecular structure of metal boronyls has been rationalized through an analysis of the bonding. The similarities and differences between metal boronyls and their isoelectronic cyanide analogues have been discussed. © 2017 Wiley Periodicals, Inc.     

Preparation of hollow silica microspheres with controlled shell thickness in supercritical fluids

This article presents a novel route to prepare hollow silica microspheres with well-defined wall thickness by using cross-linked polystyrene (PS) microspheres as templates with the assistance of supercritical carbon dioxide (SC-CO₂). In this approach, the cross-linked PS templates can be firstly prepared via emulsifier-free polymerization method by using ethylene glycol dimethacrylate or divinylbenzene as cross-linkers. Then, the silica shell from the sol–gel process of tetraethyl orthosilicate (TEOS) which was penetrated into the PS template with the assistance of SC-CO₂ was obtained. Finally, the hollow silica spheres were generated after calcinations at 600 °C for 4 h. The shell thickness of the hollow silica spheres could be finely tuned not only by adjusting the TEOS/PS ratio, which is the most frequently used method, but also by changing the pressure and aging time of the SC-CO₂ treatment. Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscope were used to characterize these hollow silica spheres.     

α-Haloenolates: their preparation and synthetic applications

α-Haloenolates have been prepared by halogen—metal or hydrogen—metal interchange. Rearrangement of β-oxido carbenoids offers another useful route, whereas β-alkoxycarbenoids decompose via α- or β-elimination. Cu^I promotes the preparation of α-halomagnesium enolates. These organometallics undergo useful reactions as nucleophiles, but can also behave as electrophiles.     

Synthesis of novel tantalum oxide sub-micrometer hollow spheres with tailored shell thickness

Sub-micrometer-sized hollow tantalum oxide (Ta2O5) spheres with tunable shell thickness and void size have been fabricated exploiting beta-diketone-functionalized polystyrene (PS) beads as sacrificial templates in a sol-gel process. First, a controlled precipitation of Ta2O5 nanoparticles was carried out on the template surface by hydrolyzing tantalum ethoxide (Ta(OEt)5) at room temperature, and subsequently, the polymer core was removed either via chemical treatment with toluene or calcination at 650 degrees C. The thickness of the tantala shell precipitated on the PS core during the coating process was tuned between 100 and 142 nm by varying the concentration of tantala precursor in the reaction media. The obtained Ta2O5-coated PS particles and hollow microspheres were characterized by scanning electron microscopy, transmission electron microscopy, infrared spectroscopy, X-ray diffraction, and thermogravimetric analysis. Due to the unique optical and dielectric properties, these nanostructured materials are envisaged to be used in applications such as novel building blocks for the fabrication of advanced materials, surface coatings, catalysts, and drug delivery systems.     

The effect of shell side hydrodynamics on the performance of axial flow hollow fibre modules

Fluid flow and mass transfer experiments have been performed on axial flow hollow fibre modules of varying packing density (32 to 76%). Shell-side pressure drop was found to be proportional to (flowrate)ⁿ, where n varied from about 1.1 at high packing density to 1.5 at low packing density, for shellside Reynolds numbers < 350. Assuming an Ergun-type pressure drop relationship it was found that for packing densities < about 50% the inertial (turbulent) losses exceeded the viscous (laminar) losses. Inspection of cross-sections taken from the middle of modules revealed non-uniform fibre packing with regions of high and low packing density. The cross-sections also change along the length of the module. It is inferred that, in addition to axial flow along fibres, there is also a degree of stream splitting which provides transverse flow across fibres as fluid continuously seeks preferential paths through regions of lower packing density. The presence of transverse flow would explain the higher than expected velocity exponent. Mass transfer experiments involving the removal of oxygen from water flowing through the shell to a sweep gas in the fibre lumens produced higher than expected shell-side mass transfer coefficients. The results are correlated within ± 15% by Sh = (0.53 − 0.58φ)Re^0.53Sc^0.33. The exponent on Re is consistent with entry region conditions, caused by repeated stream splitting and transverse flow. Compared with mass transfer predicted for axial flow through a uniformly packed shell the experimental results are up to 2× higher, with the most significant enhancement at the lower packing densities. The implication of this work is that module design requires a more sophisticated approach than the traditional assumption of laminar flow through parallel axial ducts.