A novel approach to produce monodisperse hollow pure silica spheres

In this work, we report an efficient method to produce pure hollow silica spheres (HSS) using phenyltrimethoxysilane (PTMS) compound. The production of HSS was carried out via hydrolysis of PTMS in the aqueous media and followed by a condensation reaction to form silica spheres with phenyl groups. The product was then calcined to remove phenyl groups and obtain pure silica spheres with >95% fine structure. The chemical nature of pure silica was confirmed by Fourier transforms infrared spectroscopy. The calcined HSS were stable beyond the temperature of 900 °C as confirmed by thermal gravimetric analysis (TGA). The calcined spheres preserved their spherical appearance and hollow core as shown by SEM and TEM micrographs. Interestingly, the average size of the spheres was reduced significantly after calcination from 760 to 510 nm, confirming further the removal of phenyl groups. The calcined HSS offered much higher surface area (A_s) when analysed by BET; A_s for calcined product was ～406 and mere ～4.8 m²/g for uncalcined HSS. Finally, drug release study of cisplatin/HSS showed over 45% of steady cumulative release for 72 h. The prepared HSS can be dispersed in water opening the possibility of many novel bio/non-bio applications.     

Porous carbon and carbon composite hollow spheres

In this communication, we propose a template approach toward synthesis of carbon hollow spheres by direct carbonization of highly crosslinked sulfonated polystyrene gel hollow spheres (sPS). The sulfonic acid group can facilitate carbonization. Moreover, the acid group can also induce a favorable growth of other materials within the sPS gel-forming carbon-based composite shell such as bi-continuous C/SiO₂ and their derivative ceramic SiC. Release of small molecules during polymers decomposition results porous shell.     

Direct synthesis of uniform hollow carbon spheres by a self-assembly template approach

Hollow carbon spheres (50-100 nm) have been synthesized by a self-assembly approach using hexachlorobenzene and Na. NaCl which generated during the reaction has been successfully exploited as a template for the direct synthesis of porous carbon materials, which can be subsequently removed from carbon product by annealing above 1400 degrees C.     

Architecture of micron-scale hollow spheres composed of silica nanoparticles and approach to luminescent spheres

Micron-scale hollow spheres were successfully constructed with silica nanoparticles by templating of polymer spheres. Subsequently, the use of 3-aminopropyltriethoxysilane (APTES) introduces carbon and oxygen defects in the silica nanoparticles resulting from calcination of the aminopropyl group. In this approach, the template of micron-scale polymer spheres was prepared from dispersion polymerization. Subsequent St?ber process results in the formation of a silica layer attached to the polymer sphere surfaces. After calcination, the obtained micron-scale hollow silica spheres were then studied on the relationship between the particle diameter and the surface morphology. The luminescence of hollow spheres was prepared through using APTES in St?ber process, and which of related the appearance of luminescence to the APTES concentration and calcination temperature. The results of this study can provide useful information for the structure of micron-scale hollow spheres and their application to luminescent materials.     

A novel method for the fabrication of monodisperse hollow silica spheres

In this paper, we report a novel method for the fabrication of small monodisperse hollow silica spheres. In this approach, when silica shells were coated on polystyrene particles by the sol-gel method, the polystyrene cores were dissolved subsequently, even synchronously, in the same medium to form monodisperse hollow spheres. Neither additional dissolution nor a calcination process was needed to remove the polystyrene cores. Transmission electron microscopy, scanning electron microscopy, and porosity measurements were used to characterize the monodisperse hollow silica spheres.     

Direct and initiated halogenation of carbon nanomaterials at low temperatures

Cryochemical reactions of the direct and initiated (by photolysis and radiolysis) halogenation of carbon nanomaterials (C₆₀ fullerene, nanotubes, and nanofibers) at 77–240 K were investigated by the ESR, IR spectroscopy, and elemental analysis techniques. A high reactivity of C₆₀ in reactions with fluorine and chlorine with the formation of corresponding derivatives was shown. High concentrations of radical intermediates indicating the radical chain halogenation of C₆₀ were detected (the kinetic chain length for the chlorination process reaches 10⁴–10⁶ units). The amount of chlorine attached to fullerene is ～35% and practically does not depend on the initiation mode (UV or γ-irradiation at doses up to 350 kGy). The mechanism of the cryochemical halogenation of C₆₀ is considered within the limits of the model of multicenter synchronous transitions in a molecular complex consisting of several reactant molecules including molecular fluorine or chlorine and ensuring a net exothermic effect. The amount of chlorine added to nanotubes and nanofibers did not exceed 2.5–8%, thereby indicating a low reactivity of these materials under cryogenic conditions.     

Preparation of novel porous carbon spheres from corn starch

Irregular porous carbon spheres were successfully prepared from Na₂SnO₃ coated corn porous starch by carbonization. The product was characterized with X-ray diffraction and scanning electron microscope (SEM). It is verified that the irregular porous carbon spheres are composed of disordered carbon, and the skeleton and pores of the corn porous starch was well preserved after carbonization. The pore size of the irregular porous carbon spheres is almost the same, which is similar to that of the porous starch. And the pore size decreases from about 0.91 μm to 0.53 μm measured from the SEM pictures. The texture of the irregular porous carbon spheres is mainly determined by that of porous starch.     

A microemulsion-template-interfacial-reaction route to copper sulfide hollow spheres

CuS hollow spheres have been successfully synthesized through a facile microemulsion-template-interfacial-reaction route using copper naphthenate as metal precursor and thioacetamide as the source of S(2-). In this way, hollow spheres could be obtained directly since the reaction of two reactants respectively dissolved in two different phases of an oil-in-water (o/w) microemulsion only occurs at the oil/water interface. Therefore, it is a key for forming hollow spheres to optimize the interfacial reaction rate by controlling reaction conditions. Furthermore, the size of the hollow spheres can be tailored by changing the content of oil phase. In this study, the average diameter of the CuS hollow spheres can be adjusted from 110 to 280 nm by changing the content of oil phase from 0.5 ml to 1.5 ml. In addition, the reaction temperature is a very important factor for forming CuS hollow spheres and the appropriate reaction temperature is about 50 °C.     

A novel approach to polymeric hollow nanospheres with stabilized structure

Polymeric hollow nanospheres with stabilized structure have been realized by self-assembly of crosslinkable rigid poly(amic acid) ester (PAE) oligomer and coil-like poly(4-vinylpyridine) (PVPy) via hydrogen bonding in their common solvent and subsequent photo-crosslinking of the PAE.     

A novel approach to 4-benzylisoouinolines

The reaction of quinone methides with 3.4-dihydroisoquinoline or isoquinoline leads to benzylisoquinoline derivatives. NMR and ms investigations as well as chemical degradation prove that benzylation takes place at C-4 of the isoquinoline nucleus. Spectroscopic data are given for all new compounds.     

A novel approach to automation of dynamic hollow fiber liquid-phase microextraction

An automated dynamic two-phase hollow fiber microextraction apparatus combined with high-performance liquid chromatography was developed for extraction and determination of chlorophenoxy acid (CPA) herbicides from environmental samples. The extraction device, called TT-extractor, consists of a polypropylene hollow fiber mounted inside a stainless steel tube by means of two tee-connectors in flow system. An organic solvent, which fills the lumen and the pores of the hydrophobic fiber, is pumped through the fiber repeatedly and the sample is pumped along the outer side of the fiber. The factors affecting the dynamic hollow fiber liquid-phase microextraction (DHF-LPME) of target analytes were investigated and the optimal extraction conditions were established. To test the applicability of the designed instrument, CPAs were extracted from environmental aqueous samples. The limits of detection (LODs) as low as 0.5 μg/L, linear dynamic range in the range of 1-100 μg/L and the relative standard deviations of <7% were obtained. The developed method can provide perconcentration factors as large as 230. A hollow fiber membrane can be used at least 20 times with neither loss in the efficiency nor carryover of the analytes between runs. The system is cheap and convenient and requires minimal manual handling.     

Diamond formation by reduction of carbon dioxide at low temperatures

This Communication reports a low-temperature diamond synthesis technique, in which diamonds (10-250 mum) can form at a temperature as low as 440 degrees C by reduction of dense CO2 with metallic Na. The X-ray diffraction pattern of a powder sample shows three reflection peaks, indexed with 111, 220, and 311, corresponding unambiguously to cubic diamond. The Raman spectrum of the product exhibits an intense first-order peak at 1332 cm-1, which is the characteristic signature of the cubic diamond, indicating the formation of well-crystallized diamond. Carbon dioxide is a nontoxic low-energy molecule, abundant on earth. This novel reduction method could allow studies of large-size diamond growth using CO2 as the carbon source.     

A novel and effective approach to 4-fluoropyrimidines

A series of 4-fluoropyrimidine 1-oxides, obtained via three-component heterocyclization, was studied under various reduction conditions. An effective preparative method for the synthesis of 4-fluoropyrimidines from readily available starting materials was elaborated. 4-Fluoro-substituted tetrahydroquinazolines and tetrahydroquinazoline N-oxides were demonstrated to be highly reactive in aromatic nucleophilic substitution.     

A self-assembly template approach for preparing hollow carbon microspheres

Hollow carbon microspheres (HCMs) are prepared in a sealed quartz tube via the reaction between ferrocene and ammonium bromide. The morphology and microstructure of the product are characterized by X-ray diffraction, Raman spectroscopy, scanning electron microscopy, focused ion beam workstation, transmission electron microscopy, and differential scanning calorimetry analysis. The diameter of the HCMs ranges from 1 to 13 μm and the thickness of shells ranges from 70 nm to 450 nm. It is concluded that the self-generated spherical droplets of iron amine bromide serve as the core templates for the formation of HCMs.     

A simple method to synthesize sea urchin-like polyaniline hollow spheres

Oxidative polymerization of aniline diffusing out from polystyrene hollow spheres with ferric chloride results in the formation of sea urchin-like polyaniline composite hollow spheres, which provide a simple chemical way to assemble conducting polymer nanofibers into complex structure under mild condition.     

Compression stress relaxation in carbon black reinforced HNBR at low temperatures

Findings of a study of stress relaxation behaviour of hydrogenated nitrile butadiene rubber (HNBR) at nominal compressive strains up to 0.4 and temperatures above and below the glass transition temperature T_g are reported. Two formulations of a model HNBR with 36% acrylonitrile content and carbon black (CB) loading of 0 and 50 phr were investigated. The relaxation function of HNBR is found to be independent of strain at temperatures right above the T_g or at times longer than 10⁻³ s for the deformations employed. CB imparts higher long-term stiffness and also larger relaxation strength at times longer than 10⁻⁴ s to the HNBR, but it does not affect the relaxation behaviour of the rubber in the time span from 10⁻³ – 10⁴ s. In addition, the relationship between the strain energy function of HNBR and temperature is demonstrated to have a complex concave-downward shape which is affected by two competing contributions of entropy elasticity and the stress relaxation.     

Preparation of hollow carbon nanospheres at low temperature via new reaction route

Hollow carbon nanospheres were obtained at 200 °C via a new reaction route, by using magnesium, hexachloroethane and aluminum trichloride as starting materials and benzene as solvent. The products were characterized with X-ray diffraction pattern, transmission electron microscope, high-resolution transmission electron microscope images and Raman spectrum. The reaction conditions are easy to be maintained and controlled. They may provide a new method to produce other carbonaceous materials. A possible mechanism of reaction was proposed.     

A novel and facile preparation method of hollow silica spheres containing small SiO2 cores

This article presents a novel and facile preparation method of hollow silica spheres with loading small silica inside. In this approach, positively charged SiO₂/polystyrene core‐shell composite particles were synthesized first, when the silica shells from the sol‐gel process of tetraethoxysilane were then coated on the surfaces of composite particles via electrostatic interaction, the polystyrene was dissolved subsequently even synchronously in the same medium to form hollow silica spheres with small silica cores. TEM, SEM, and FTIR measurements were used to characterize these composite spheres. Based on this study, some inorganic or organic compounds could be loaded into these hollow silica spheres. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3431–3439, 2007