Silica coated noble metal nanoparticle hydrosols as supported catalyst precursors

Synthesis of well-defined nanoparticles has been intensively pursued not only for their fundamental scientific interest, but also for many technological applications. One important development of the nanomaterial is in the area of chemical catalysis. We have now developed a new aqueous-based method for the synthesis of silica encapsulated noble metal nanoparticles in controlled dimensions. Thus, colloid stable silica encapsulated approximately 5 nm platinum nanoparticle is synthesized by a multi-step method. The thickness of the silica coating could be controlled using a different amount of silica precursor. These particles supported on a high surface area alumina are also demonstrated to display a superior hydrogenation activity and stability against metal sintering after thermal activation.     

Complete phase transfer of hydrophobic magnetic nanocrystals into aqueous phase

The effective phase transfer of hydrophobic nanocrystals synthesized in nonpolar solvents into polar solvents remains great challenge for their nanomedicinal applications. To resolve this issue, the exsiting strategies for phase transfer of nanocrystals in organic solvents use amphiphilic compounds or lipids as imperative moieties by ligand exchange and encapsulations. Ligand exchange involves by exchanging the hydrophobic molecules with bifunctional compounds and small size of molecules is coordinated with functional molecules to increase the steric repulsion forces between boundary of water and nanoparticles. However, the yield of phase transferred nanocrystals from hydrophobic nonpolar to hydrophilic polar phase is exceptionally low, and sometime irreversible desorption of replaced ligands leads to agglomeration and aggregation. Also, their intrinsic physiochemical properties are easily influenced by surrounding ion species or pH when the particles are suspended in phosphate saline buffer (PBS). Moreover, conjugation of bioactive molecules often leads to colloidal instability in PBS because of the hydrodynamic nature of the amphiphilic molecules on the surfaces of nanoparticles. Here we report a robust and simple post-synthetic surface modification procedure of hydrophobic nanoparticles to remove the original surface-bound carboxylic acid and increase the water-solubility for nanomedicinal applications.     

Formation of crystalline aluminum silicate hydroxide layer during deposition of amorphous alumina coatings by electron beam evaporation

Aluminum oxide films were deposited on fused silica and borosilicate glass substrates by electron beam evaporation, without any substrate heating. Grazing incidence X-ray diffraction measurements found that a layer of crystalline aluminum silicate hydroxide was formed at the interface of the substrate and the amorphous alumina film, the latter transformed to γ-alumina phase on heat treatment at 800 °C. The aluminum silicate hydroxide layer was produced by the chemical reaction between condensing Al and Al–O species, OH⁻ from the residual water vapors in the chamber and Si atoms from the underlying silica and borosilicate glass substrates.     

Hybrid Organic–Inorganic Colloidal Composite ‘Sponges’ via Internal Crosslinking

An effective method for the generation of hybrid organic–inorganic nanocomposite microparticles featuring controlled size and high structural stability is presented. In this process, an oil‐in‐water Pickering emulsion is formed using hydrophilic amine‐functionalized silica nanoparticles. Covalent modification using a hydrophobic maleic anhydride copolymer then alters nanoparticle wettability during crosslinking, causing a core‐shell to nanocomposite structural reorganization of the assemblies. The resulting porous nanocomposites maintain discrete microparticle structures and retain payloads in their oil phase even when incubated in competitive solvents such as ethanol.     

Reversible, reagentless solubility changes in phosphatidylcholine-stabilized gold nanoparticles

Phosphatidylcholine (PC) is a versatile ligand for synthesizing gold nanoparticles that are soluble in either organic or aqueous media. Here we report a novel route to organic-soluble, PC-stabilized gold nanoparticles that can be re-suspended in water after removal of the organic solvent. Similarly, we show that PC-stabilized gold nanoparticles synthesized in water can be re-suspended in organic solvents after complete removal of water. Without complete removal of the solvent, the nanoparticles retain their original solubility and do not phase transfer. This change in solvent preference from organic to aqueous and vice versa without the use of an additional phase transfer reagent is novel, visually striking, and of utility for synthetic modification of nanoparticles. This approach allows chemical reactions to be performed on nanoparticles in organic solvents followed by conversion of the products to water-soluble materials. A narrow distribution of PC-stabilized gold nanoparticles was obtained after phase transfer to water as characterized by UV-visible (UV-vis) spectroscopy and transmission electron microscopy (TEM), demonstrating that the narrow distribution obtained from the organic synthesis is retained after transfer to water. This method produces water-soluble nanoparticles with a narrower dispersity than is possible with direct aqueous synthesis.     

Biopebble Containers: DNA‐Directed Surface Assembly of Mesoporous Silica Nanoparticles for Cell Studies

The development of methods for colloidal self‐assembly on solid surfaces is important for many applications in biomedical sciences. Toward this goal, described is a versatile class of mesoporous silica nanoparticles (MSN) that contain on their surface various types of DNA molecules to enable their self‐assembly into micropatterned surface architectures useful for cell studies. Monodisperse dye‐doped MSN are synthesized by biphase stratification and functionalized with an aptamer oligonucleotide that serves as gatekeeper for the triggered release of encapsulated molecular cargo, such as fluorescent dye rhodamine B or the anticancer drug doxorubicin. One or two additional types of oligonucleotides are installed on the MSN surface to enable DNA‐directed immobilization on solid substrates bearing patterns of complementary capture oligonucleotides. It is demonstrated that this strategy can be used for efficient self‐assembly of microstructured surface architectures, which not only promote the adhesion and guidance of cells but also are capable of affecting the fate of adhered cells through triggered release of their cargo. It is believed that this approach is useful for diverse applications in tissue engineering and nanobio sciences.     

Composite formation of Thiol-capped Au nanoparticles and mesoporous silica prepared by a sol-gel method

We have previously reported the fabrication of a nanocomposite from dodecanethiol-capped Au nanoparticles (average diameter 2.6 nm) and a silica aerogel. It was found that the Au particles were efficiently adsorbed on a silica wet-gel in organic solvents. In this paper, surface analysis of the silica surface and evaluation of adsorption rates for various solvents, performed to elucidate the nature of the interaction between the capped nanoparticles and the silica gel, are described. These observations indicate that dipole-induced dipole interaction between OH groups on the silica surface and metal cores of the nanoparticles is probably important for the adsorption. It was demonstrated that, by changing the solvent polarity, spatial distribution of the nanoparticles inside the gel can be controlled.     

Development of organic dye-doped silica nanoparticles for bioanalysis and biosensors

The combination of two silica precursors, tetraethylorthosilicate and phenyltriethoxysilane, were utilized to synthesize organic dye-doped silica nanoparticles. The hydrophobic nature of phenyltriethoxysilane keeps the organic dye in the silica matrix, whereas the hydrophilic tetraethylorthosilicate-formed silica allows the resulting nanoparticles to be dispersed in aqueous solutions. Characterization of the nanoparticles showed that they could be synthesized in the nanometer range with high photostability and minimal dye leakage. The silica matrix of the nanoparticles allows different routes of surface biomolecular modification for biosensor and bioanalysis applications. We have shown different applications of the nanoparticles in bioanalysis and in biosensing. Biotin interaction of avidin-coated nanoparticles can be used for the determination of biotinylated bovine serum albumin, and the immobilization of glutamate dehydrogenase on the nanoparticle surfaces enables the nanoparticles to be used as biosensors for glutamate determination.     

Glycogen as a Building Block for Advanced Biological Materials

Biological nanoparticles found in living systems possess distinct molecular architectures and diverse functions. Glycogen is a unique biological polysaccharide nanoparticle fabricated by nature through a bottom-up approach. The biocatalytic synthesis of glycogen has evolved over time to form a nanometer-sized dendrimer-like structure (20–150 nm) with a highly branched surface and a dense core. This makes glycogen markedly different from other natural linear or branched polysaccharides and particularly attractive as a platform for biomedical applications. Glycogen is inherently biodegradable, nontoxic, and can be functionalized with diverse surface and internal motifs for enhanced biofunctional properties. Recently, there has been growing interest in glycogen as a natural alternative to synthetic polymers and nanoparticles in a range of applications. Herein, the recent literature on glycogen in the material-based sciences, including its use as a constituent in biodegradable hydrogels and fibers, drug delivery vectors, tumor targeting and penetrating nanoparticles, immunomodulators, vaccine adjuvants, and contrast agents, is reviewed. The various methods of chemical functionalization and physical assembly of glycogen nanoparticles into multicomponent nanodevices, which advance glycogen toward a functional therapeutic nanoparticle from nature and back again, are discussed in detail.     

Interfacial assembly of partially hydrophobic silica nanoparticles induced by ultrasonic treatment

A sonochemical approach has effectively been applied to prepare aqueous dispersions of air-filled nanostructured quartz silica shells from surface-engineered amorphous silica nanoparticles. The non-equilibrium nature of the cavitation process and high temperature and pressure in the cavitation microbubble can lead to partial crystallization of the amorphous silica nanoparticles producing the quartz phase and a high degree of interconnection between the silica nanoparticles in the microsphere shells. The very high stability of the silica shells against collapse and aggregation is determined by the hydrophobic nature of the silica nanoparticles. Because of the shell thickness and its high density caused by sintering of the silica nanoparticles, the gas (liquid) permeability through the shell is limited thus prolonging the life time of the air-filled nanostructured silica shells.     

Silica/potassium ferrite nanocomposite: Structural,morphological, magnetic,thermal and in vitro cytotoxicity analysis

The coating of silica on potassium ferrite (KFeO₂) nanoparticles has been reported in the present study. The X-ray diffraction pattern revealed the formation of orthorhombic structure of bare potassium ferrite nanoparticles, which was also retained after the silica coating, along with a broad band near 2θ ∼ 20–25° pertaining to the presence of amorphous silica. The size of bare and coated potassium ferrite nanoparticles was found to be 4–8 nm and 10–22 nm, respectively, as observed from transmission electron microscope. The presence of silica was also revealed by the Fourier transform infrared spectrum and high resolution transmission electron microscope. In vibrating sample magnetometer analysis, both bare as well as coated potassium ferrite nanoparticles exhibited superparamagnetic behaviour with magnetic saturation values, 49.01 and 21.17 emu/g, respectively. Dose-dependent cellular toxicity was observed in the in vitro MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide, a tetrazole) – assay study on Jurkat cells, where both bare as well as silica coated nanoparticles exhibited non-toxicity below 250 μg/ml. An augmentation of cell viability was observed in case of silica coated potassium ferrite nanoparticles. The nanosize, superparamagnetic behaviour and enhanced cell viability make silica coated potassium ferrite nanoparticles a potential claimant for biomedical applications.     

FeNi@SiO2磁性纳米复合粒子的制备及磁热性能

大量制备磁热性能优异的磁性纳米粒子对磁热疗和组织复温的生物学应用具有理论价值.本研究通过高温电弧法制备FeNi磁性纳米颗粒,通过超声-沉降分级筛分得到平均粒径为80 nm的FeNi纳米颗粒,通过溶胶-凝胶法得到平均粒径为100 nm,SiO2壳层厚度为15～20 nm的FeNi@SiO2纳米复合粒子.超导量子干涉仪测定...     

用于表面增强拉曼散射的石墨烯/纳米粒子复合基底材料的研究现状

表面增强拉曼散射(Surface enhanced Raman scattering,SERS)自从被发现以来在单分子检测、生物医学体系、环境科学、纳米材料以及传感器等领域获得了广泛的应用,而其SERS增强因子、物质吸附能力等性能的好坏主要取决于SERS的基底材料及结构。相比于纳米粒子的SERS基底,石墨烯/纳米粒子复合材料的SERS基底由于石墨烯额外的化学增强作用、表面分子富集和荧光淬灭等功能而受到各国研究人员的重视。首先分析了石墨烯/纳米粒子复合材料的SERS增强机理,然后从材料制备和基底结构两个方面综述了石墨烯/纳米粒子复合材料在SERS上的研究现状,最后对其未来的发展方向进行了展望。     

Effects of organic solvents on hyaluronic acid nanoparticles obtained by precipitation and chemical crosslinking

Hyaluronic acid is a hydrophilic mucopolysaccharide composed of alternating units of D-glucuronic acid and N-acetylglucosamine. It is used in many medical, pharmaceutical, and cosmetic applications, as sponges, films, or particle formulations. Hyaluronic acid nanoparticles can be synthesized free of oil and surfactants by nanoprecipitation in organic solvents, followed by chemical crosslinking. The organic solvent plays an important role in particles size and structure. Therefore, this study aimed to investigate the influence of acetone, ethanol, and isopropyl alcohol on the synthesis and physico-chemical properties of hyaluronic acid nanoparticles. Particles were crosslinked with adipic hydrazide and chloride carbodiimide under controlled conditions. The nanoparticles obtained with all three studied solvents were moderately electrostatically stable. Experiments with acetone produced the smallest particle size (120.44 nm) and polydispersity (0.27). The size and polydispersity of hyaluronic acid nanoparticles correlated with the surface tension between water and the organic solvents, not with the thermodynamic affinity of water for the organic solvents.     

Two‐Dimensional Nanomaterials for Biomedical Applications: Emerging Trends and Future Prospects

Two‐dimensional (2D) nanomaterials are ultrathin nanomaterials with a high degree of anisotropy and chemical functionality. Research on 2D nanomaterials is still in its infancy, with the majority of research focusing on elucidating unique material characteristics and few reports focusing on biomedical applications of 2D nanomaterials. Nevertheless, recent rapid advances in 2D nanomaterials have raised important and exciting questions about their interactions with biological moieties. 2D nanoparticles such as carbon‐based 2D materials, silicate clays, transition metal dichalcogenides (TMDs), and transition metal oxides (TMOs) provide enhanced physical, chemical, and biological functionality owing to their uniform shapes, high surface‐to‐volume ratios, and surface charge. Here, we focus on state‐of‐the‐art biomedical applications of 2D nanomaterials as well as recent developments that are shaping this emerging field. Specifically, we describe the unique characteristics that make 2D nanoparticles so valuable, as well as the biocompatibility framework that has been investigated so far. Finally, to both capture the growing trend of 2D nanomaterials for biomedical applications and to identify promising new research directions, we provide a critical evaluation of potential applications of recently developed 2D nanomaterials.     

Synthesis, characterization, and biological applications of multifluorescent silica nanoparticles

Multifluorescent silica nanoparticles were synthesized by the St?ber method using conjugates of (3-aminopropyl)triethoxysilane and fluorescent dye-N-hydroxysuccinimide esters. The nanoparticles containing the fluorescent dyes were well dispersed and showed high, stable, and tunable fluorescence intensities. In addition, we prepared multifluorescent silica nanoparticles containing two kinds of fluorescent dyes and used the nanoparticles in biological applications. Flow cytometry analysis showed high and tuned fluorescence and multiple fluorescences from single nanoparticles with diameters of approximately 400 nm. Fluorescence microscopy analysis also showed high and tuned fluorescence, as well as multiple fluorescences from single nanoparticles and from cells labeled with multifluorescent silica nanoparticles. The intracellular distribution of nanoparticles was evaluated by confocal microscopy and electron microscopy. We discuss the advantages and demonstrate the usefulness of our nanoparticles in relation to commercially available fluorescent nanoparticles including quantum dots.     

Liquid‐Phase Transmission Electron Microscopy for Studying Colloidal Inorganic Nanoparticles

For the past few decades, nanoparticles of various sizes, shapes, and compositions have been synthesized and utilized in many different applications. However, due to a lack of analytical tools that can characterize structural changes at the nanoscale level, many of their growth and transformation processes are not yet well understood. The recently developed technique of liquid‐phase transmission electron microscopy (TEM) has gained much attention as a new tool to directly observe chemical reactions that occur in solution. Due to its high spatial and temporal resolution, this technique is widely employed to reveal fundamental mechanisms of nanoparticle growth and transformation. Here, the technical developments for liquid‐phase TEM together with their application to the study of solution‐phase nanoparticle chemistry are summarized. Two types of liquid cells that can be used in the high‐vacuum conditions required by TEM are discussed, followed by recent in situ TEM studies of chemical reactions of colloidal nanoparticles. New findings on the growth mechanism, transformation, and motion of nanoparticles are subsequently discussed in detail.     

Recent Advances in Chemical Synthesis,Self‐Assembly,and Applications of FePt Nanoparticles

This paper reviews recent advances in chemical synthesis, self‐assembly, and potential applications of monodisperse binary FePt nanoparticles. After a brief introduction to nanomagnetism and conventional processes of fabricating FePt nanoparticles, the paper focuses on recent developments in solution‐phase syntheses of monodisperse FePt nanoparticles and their self‐assembly into nanoparticle superlattices. The paper further outlines the surface, structural, and magnetic properties of the FePt nanoparticles and gives examples of three potential applications in data storage, permanent magnetic nanocomposites, and biomedicine.     

Auger study of interfacial reaction between sputter-deposited NiTi films and a glass substrate containing titanium oxide

The interfacial reaction between magnetron sputter-deposited NiTi films and various glass substrates, namely silica glass, borosilicate glass and borosilicate glass containing titanium oxide, were studied. It was found that the glass substrate containing titanium oxide showed a broad transition region (20–30 nm) in which the titanium-to-nickel and silicon-to-oxygen ratios varied markedly with depth. In accordance with the existence of a broad transition region, the shapes of O KLL Auger lines showed a continuous change in the oxide species through the transition region. In contrast, the interface between NiTi films and borosilicate and silica glasses showed only a narrow transition region indicating that no interfacial interaction occured during or after the sputter deposition. These facts suggest that titanium oxide dissolved in borosilicate glass plays an important role. The results are discussed on the basis of the thermodynamics for oxide formation. It is shown that the existence of various oxidation state for titanium and a single oxidation state for silicon and boron are responsible for the difference in the widths of the transition regions observed in the three different substrates.     

Synthesis of crystalline metal nitride and metal carbide nanostructures by sol–gel chemistry

Attention toward nanosized metal nitrides and carbides is rapidly increasing thanks to their chemical characteristics that make them as valid and sustainable alternatives to noble metals in catalysis and to air-sensitive metals or oxides for applications under harsh conditions. They are mostly used as bulk phase or micron sized powders, due to an intrinsic difficulty to synthesize them as nanoparticles in a systematic and scalable fashion. However, nanosized metal nitrides and carbides could exhibit improved performances, e.g. in catalysis due to a higher surface area, and can be shaped more easily than corresponding larger grains for further specific applications. Recently, sol–gel chemistry has closed this gap and now enables the simple, cheap, and sustainable production of metal nitride and carbide nanoparticles.In the present review we give an overview on recent sol–gel based pathways for the synthesis of metal nitride and carbide nanoparticles, believing that a better knowledge of the potentialities of these still hardly touched materials stimulates research interest and applications.