Polymerization-induced chiral self-assembly(PICSA)is an efficient strategy that not only allows the construction of the supramolecular chiral assemblies in a controlled manner but also can regulate the morphology in situ.Herein,a series of azobenzene-containing block copolymer(Azo-BCP)assemblies with tunable morphologies and supramolecular chirality were obtained through the PICSA strategy.The supramolecular chirality of Azo-BCP assemblies could be regulated by carbon dioxide(CO2)stimulus,and completely recovered by bubbling with Ar.A reversible morphology transformation and chiroptical switching process could also be achieved by the alternative 365 nm UV light irradiation and heatingcooling treatment.Moreover,the supramolecular chirality is thermo-responsive and a reversible chiral-achiral switching was successfully realized,which can be reversibly repeated for at least five times.This work provides a feasible strategy for constructing triple stimuli-responsive supramolecular chiral nano-objects in situ. 相似文献
The nanoparticles composed of polystyrene core and poly[2-(diethylamino)ethyl methacrylate] (PDEA) hairy shell were used as colloidal templates for in situ silica mineralization, allowing the well-controlled synthesis of hybrid silica core–shell nanoparticles with raspberry-like morphology and hollow silica nanoparticles by subsequent calcination. Silica deposition was performed by simply stirring a mixture of the polymeric core–shell particles in isopropanol, tetramethyl orthosilicate (TMOS) and water at 25 °C for 2.5 h. No experimental evidence was found for nontemplated silica formation, which indicated that silica deposition occurred exclusively in the PDEA shell and formed PDEA–silica hybrid shell. The resulting hybrid silica core–shell particles were characterized by transmission electron microscopy (TEM), thermogravimetry, aqueous electrophoresis, and X-ray photoelectron spectroscopy. TEM studies indicated that the hybrid particles have well-defined core–shell structure with raspberry morphology after silica deposition. We found that the surface nanostructure of hybrid nanoparticles and the composition distribution of PDEA–silica hybrid shell could be well controlled by adjusting the silicification conditions. These new hybrid core–shell nanoparticles and hollow silica nanoparticles would have potential applications for high-performance coatings, encapsulation and delivery of active organic molecules. 相似文献
Polystyrene‐core–silica‐shell hybrid particles were synthesized by combining the self‐assembly of nanoparticles and the polymer with a silica coating strategy. The core–shell hybrid particles are composed of gold‐nanoparticle‐decorated polystyrene (PS‐AuNP) colloids as the core and silica particles as the shell. PS‐AuNP colloids were generated by the self‐assembly of the PS‐grafted AuNPs. The silica coating improved the thermal stability and dispersibility of the AuNPs. By removing the “free” PS of the core, hollow particles with a hydrophobic cage having a AuNP corona and an inert silica shell were obtained. Also, Fe3O4 nanoparticles were encapsulated in the core, which resulted in magnetic core–shell hybrid particles by the same strategy. These particles have potential applications in biomolecular separation and high‐temperature catalysis and as nanoreactors. 相似文献
Polypeptide-coated silica nanoparticles represent an interesting class of organic-inorganic hybrids since the ordered secondary structure of the polypeptide grafts imparts functional properties to these nanoparticles. The synthesis of a poly-l-glutamic acid (PLGA) silica nanoparticle hybrid by employing N-carboxyanhydride (NCA) polymerization to synthesize the polypeptide chains and Cu catalyzed azide alkyne cycloaddition reaction to graft these chains onto the silica surface is reported. This methodology enables the synthesis of well-defined polypeptide chains that are attached onto the silica surface at high surface densities. The PLGA-silica conjugate particles are well dispersed in water, and have been thoroughly characterized using multinuclear ((13)C, (29)Si) solid state NMR, thermogravimetric analysis, Fourier transform infrared, dynamic light scattering, and transmission electron microscopy. The pH-dependent reversible aggregation of the PLGA-silica particles, driven by the change in PLGA structure, has also been studied. Preliminary results on the use of aqueous dispersions of silica-PLGA for the preparation of three-dimensional macroporous structures with oriented pores by ice templating methodology are also demonstrated. These macroporous materials, comprising a biocompatible polymer shell covalently attached to rigid inorganic cores, adopts an interesting lamellar structure with fishbone-type architecture. 相似文献
Supramolecular chirality, generated by the asymmetric assembly of chiral or achiral molecules, has attracted intense study owing to its potential to offer insights into natural biological structures and its crucial roles in advanced materials. The optical activity and stacking pathway of building molecules both greatly determine the chirality of the whole supramolecular structure. The flexibility of supramolecular structures makes their chirality easy to modulate through abundant means. Adjustment of the molecular structure or packing mode, or external stimuli that act like a finger gently pushing toy bricks, can greatly change the chirality of supramolecular assemblies. The dynamic regulation of chiral nanostructures on the intramolecular, intermolecular, and external levels could be regarded as the modulatory essence in numerous strategies, however, this perspective is ignored in most reviews in the literature. Herein, therefore, we focus on the ingenious dynamic modulation of chiral nanostructures by these factors. Through dynamic modulation with changes in chiroptical spectroscopy and electron microscopy, the mechanism of formation of supramolecular chirality is also elaborated. 相似文献
We demonstrate a facile wet chemical approach for fabricating spherical metal/metal-oxide core@mesoporous silica shell hybrid nanoparticles with different core and shell thicknesses. Vertically aligned mesoporous silica (mSiO(2) ) shells were fabricated over the pre-synthesized spherical SiO(2) nanoparticles through a three-step strategy: 1)?synthesis of core materials, 2)?covering the core with an organic-inorganic composite layer, and 3)?removing the organic template through calcinations in air. The mechanisms of hybrid structure formation are proposed. The multifunctional nature of the hybrid structures could be induced by incorporating guest ions/molecules, such as Ag, Mn, and TiO(2) , into the pores of an mSiO(2) shell. Mn and TiO(2) cluster- incorporated composite structures have been tested to be antioxidizing agents and effective photocatalysts through electron spin resonance, radical scavenging tests, and the photocatalytic degradation of rhodamine B. The possibility of incorporating several hetero-element guest clusters in these mesoporous composite particles makes them highly attractive for multifunctional applications. 相似文献
Antipodal twisted helical ribbons with lamellar bilayer structure were obtained by self-assembly of chiral amphiphilic molecules in water and water/ethanol. The handedness inversion of the molecular arrangement in these antipodal helical ribbons was investigated by using chiroptical spectroscopy and molecular probes in their antipodal mesoporous silica assemblies synthesized through pairing interaction between the head group of the chiral amphiphilic molecules and a co-structure-directing agent. The supramolecular chirality is imprinted in the pore surface through the organic group of the co-structure-directing agent. The mirror-image diffuse-reflectance circular dichroism spectra of the conjugated discotic probing molecule introduced into their supramolecular chiral imprinted mesoporous silica demonstrated the origin of inverse chirality from the antipodal helical stacking of the molecules. 相似文献
We report on a single-step coating process and the resulting colloidal stability of silica-coated spindle-type hematite nanoparticles (NPs) decorated with a layer of poly(acrylic acid) (PAA) polyelectrolyte chains that are partially incorporated into the silica shell. The stability of PAA coated NPs as a function of pH and salt concentration in water was compared to bare hematite particles and simple silica-coated hematite NPs, studying their electrophoretic mobility and the hydrodynamic radius by dynamic light scattering. Particles coated with this method were found to be more stable upon the addition of salt at pH 7, and their aggregation at the pH of the isoelectric point is reversible. The hybrid coating appears to increase the colloidal stability in aqueous media due to the combination of the decrease of the isoelectric point and the electrosteric stabilization. This coating method is not limited to hematite particles but can easily be adapted to any silica-coatable particle. 相似文献
Nanocomposite latex particles, with a silica nanoparticle as core and crosslinked poly(tert‐butylmethacrylate) as shell, were prepared in this work. Silica nanoparticles were first synthesized by a sol‐gel process, and then modified by 3‐(trimethoxysilyl)propyl methacrylate (MPS) to graft C?C groups on their surfaces. The MPS‐modified silica nanoparticles were characterized by elemental analysis, FTIR, and 29Si NMR and 13C‐NMR spectroscopy; the results showed that the C?C groups were successfully grafted on the surface of the silica nanoparticles and the grafted substance was mostly the oligomer formed by the hydrolysis and condensation reaction of MPS. Silica/poly(tert‐butylmethacrylate) core/shell nanocomposite latex particles were prepared via seed emulsion polymerization using the MPS‐modified silica nanoparticle as seed, tert‐butylmethacrylate as monomer and ethyleneglycol dimethacrylate as crosslinker. Their core/shell nanocomposite structure and chemical composition were characterized by means of TEM and FTIR, respectively, and the results indicated that silica/poly(tert‐butylmethacrylate) core/shell nanocomposite latex particles were obtained. 相似文献
In this paper, we present a novel strategy for fabricating polyoxometalate (POM)-based photochromic silica hybrid films. To combine metal nanoparticles (NPs) into the POMs embedded silica matrix, furthermore, we realized the controllable in situ synthesis of metal NPs in the film by utilizing the reduction property of POMs existing in the reduced state. Through electrostatic encapsulation with hydroxyl-terminated surfactants, the POMs with good redox property can be covalently grafted onto a silica matrix by means of a sol-gel approach, and stable silica sol-gel thin films containing surfactant-encapsulated POMs can be obtained. The functional hybrid film exhibits both the transparent and easily processible properties of silica matrix and the stable and reversible photochromism of POMs. In addition, well-dispersed POMs in a hydrophobic microenvironment within the hybrid film can be used as reductants for the in situ synthesis of metal NPs. More significantly, the size and location of NPs can be tuned by controlling the adsorption time of metal ions and mask blocking the surface. The hybrid film containing both POMs and metal NPs with patterned morphology can be obtained, which has potential applications in optical display, memory, catalysis, microelectronic devices and antibacterial materials. 相似文献
We present the preparation and the characterization of the solution behavior and functional properties of superparamagnetic and/or fluorescent, thermo-responsive inorganic/organic hybrid particles with an intermediate protective silica shell and a smart polymer corona. These well-defined multifunctional nanogels were prepared via two consecutive encapsulation processes of superparamagnetic Fe(2)O(3) nanoparticles (NPs) and/or fluorescent CdSe(ZnS) semiconductor nanocrystals with a silica layer and a crosslinked poly(N-isopropylacrylamide) (PNIPAAm) polymer shell. First, the different NPs were entrapped into a silica shell using a microemulsion process. Therein, the precise adjustment of the conditions allows to entrap either several particles or single ones and to tailor the thickness of the silica shell in the range of 20-60 nm. In a second step, a polymer coating, i.e. thermosensitive PNIPAAm, was attached onto the surface of the multifunctional core-shell particles via free radical precipitation polymerization, furnishing multifunctional core-shell-corona hybrid nanogels. Analyses of the functional properties, i.e. optical brightness and magnetic moments, along with transmission electron microscopy reveal near monodisperse hybrid nanoparticles that retain the intrinsic properties of the original nanocrystals. Additionally, we demonstrate the drastically increased chemical stability due to the barrier properties of the intermediate silica layer that protects and shields the inner functional nanocrystals and the responsive character of the smart PNIPAAm shell. 相似文献
Magnetically separable mesostructured silica with an unobstructed pore system was fabricated through the deposition of cobalt nanoparticles on the outer surface of the submicron-sized silica particles. These cobalt nanoparticles were further protected by a nanometer-thick carbon shell against acid erosion. Due to the fact that the magnetic particles are grafted on the outer surface of the porous silica, the pores are still accessible for further modification, which could widen the application range of porous silica. 相似文献
The present critical review reports on recent developments of optical nanoparticles based on the association of gold, silver, silica and quantum dots and calixarenes. These hybrid organic-inorganic compounds characterized by a thick organic layer self-assembled on the surface of a core of mineral surface atoms take advantage of the supramolecular recognition of luminescent calixarenes to fabricate nanodevices of nanoparticle size, capable of detecting metal cations, polyaromatic hydrocarbons and pesticides. Also presented is an explanation of the involvement of such nanoparticles in biochemical systems. This critical review provides an overview of their preparation, the manner in which they are characterized, and their use (108 references). 相似文献
Structured hybrid nanoparticles were synthesized via surface‐initiated atom transfer radical polymerization of MMA from ordered mesoporous silica (OMS) nanoparticles with various morphologies. The design of the OMS particles was adjusted to target either spherical core‐shell or cylindrical morphologies with a mean diameter below 400 nm. The polymer growth via ATRP from the silica surface was well‐controlled as demonstrated by the macromolecular characteristics of the grafted chains. Original hybrid multilayered nanoparticles composed of either a dense silica core or hollow core; an inner OMS shell showing radial orientation of the mesopores and an outer PMMA shell with controlled thickness were successfully prepared.
Molecular nanoparticles including polyoxometalates, proteins, fullerenes and polyhedral oligosiloxane (POSS) are nanosized objects with atomic precision, among which POSS derivatives are the smallest nanosilicas. Incorporation of molecular nanoparticles into chiral aggregates either by chiral matrices or self-assembly allows for the transfer of supramolecular chirality, yet the construction of intrinsic chirality with atomic precision in discrete molecules remains a great challenge. In this work, we present a molecular folding strategy to construct giant POSS molecules with inherent chirality. Ferrocenyl diamino acids are conjugated by two or four POSS segments. Hydrogen bonding-driven folding of diamino acid arms into parallel β-sheets facilitates the chirality transfer from amino acids to ferrocene and POSS respectively, disregarding the flexible alkyl spacers. Single crystal X-ray structures, density functional theory (DFT) calculations, circular dichroism and vibrational circular dichroism spectroscopy clearly verify the preferential formation of one enantiomer containing chiral molecular nanosilicas. The chiral orientation and chiroptical properties of POSS show pronounced dependence on the substituents of α-amino acids, affording an alternative way to control the folding behavior and POSS chirality in addition to the absolute configuration of amino acids. Through the kinetic nanoprecipitation protocol, one-dimensional aggregation enables chirality transfer from the molecular scale to the micrometer scale, self-assembling into helices in accordance with the packing propensity of POSS in a crystal phase. This work, by illustrating the construction of chiral molecular nanosilicas, paves a new way to obtain discrete chiral molecular nanoparticles for potential chiroptical applications.A molecular folding strategy is developed to construct ferrocenyl diamino acid conjugated polyhedral oligosiloxane molecules. Hydrogen bonding-driven folding facilitates the chirality transfer from the molecular scale to the micrometer scale.相似文献
Hierarchical supramolecular chiral liquid-crystalline (LC) polymer assemblies are challenging to construct in situ in a controlled manner. Now, polymerization-induced chiral self-assembly (PICSA) is reported. Hierarchical supramolecular chiral azobenzene-containing block copolymer (Azo-BCP) assemblies were constructed with π–π stacking interactions occurring in the layered structure of Azo smectic phases. The evolution of chirality from terminal alkyl chain to Azo mesogen building blocks and further induction of supramolecular chirality in LC BCP assemblies during PICSA is achieved. Morphologies such as spheres, worms, helical fibers, lamellae, and vesicles were observed. The morphological transition had a crucial effect on the chiral expression of Azo-BCP assemblies. The supramolecular chirality of Azo-BCP assemblies destroyed by 365 nm UV irradiation can be recovered by heating–cooling treatment; this dynamic reversible achiral–chiral switching can be repeated at least five times. 相似文献