Preparation and optical properties of ZnO@PPEGMA nanoparticles

The poly(poly(ethylene glycol) methyl ether monomethacrylate) (PPEGMA) grafted zinc oxide (ZnO) nanoparticles were successfully prepared via the surface-initiated atom transfer radical polymerizations (ATRP) from the surfaces functionalized ZnO nanoparticles. The 2-bromoisobutyrate (BIB) was immobilized onto the surface of the ZnO nanoparticles through the reaction between 2-bromoisobutyryl bromide (BIBB) and the hydroxyl groups on nanoparticles, serving as the initiator to induce the ATRP of poly(ethylene glycol) monomethacrylate (PEGMA). Well-defined polymer chains were grown from the surfaces to yield hybrid nanoparticles comprised of ZnO cores and PPEGMA polymer shells having multifunctional end groups. The structure and morphology of the nanoparticles were characterized using Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS), thermogravimetric analysis (TGA), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The optical properties of the nanoparticles were investigated by UV-vis absorption spectroscopy and photoluminescence spectroscopy (PL). The results showed that the dispersion and near-band edge (NBE) emission of ZnO nanoparticles could be improved by the grafted PPEGMA polymer segments.     

Grafting of PMMA brushes on titania nanoparticulate surface via surface-initiated conventional radical and “controlled” radical polymerization (ATRP)

Stable dispersion of titania nanoparticles in organic solvents are obtained by grafting poly(methyl methacrylate) layer on to the surface. Titania nanoparticles are synthesized through the hydrolysis of titanium (IV) isopropoxide. The average size of the titania particles is found to be 15 ± 2 nm. The polymer layer was introduced onto the surface by immobilizing the initiating moiety. Azo initiator moiety required for surface-initiated conventional free radical polymerization and a tertiary bromide initiator moiety required for ATRP are attached covalently to the titania nanoparticulate surface through the surface hydroxyl groups. The “encapsulation” of PMMA layer results in the steric stabilization of the titania nanoparticles. Another important finding is that it is possible to grow polymer layer in a controlled fashion.     

A versatile method for the preparation of end-functional polymers onto SiO2 nanoparticles by a combination of surface-initiated ATRP and Huisgen [3 + 2] cycloaddition

A versatile method was developed for the chain-end functionalization of the grafted polymer chains for surface modification of nanoparticles with functionalized groups through a combination of surface-initiated atom-transfer radical polymerization (ATRP) and Huisgen [3 + 2] cycloaddition. First, the surface of SiO₂ nanoparticles was modified with poly(methyl methacrylate) (PMMA) brushes via the “grafting from” approach. The terminal bromides of PMMA-grafted SiO₂ nanoparticles were then transformed into an azide function by nucleophilic substitution. These azido-terminated PMMA brushes on the nanoparticle surface were reacted with alkyne-terminated functional end group via Huisgen [3 + 2] cycloaddition. FTIR and ¹H NMR spectra indicated quantitative transformation of the chain ends of PMMA brushes onto SiO₂ nanoparticles into the desired functional group. And, the dispersibility of the end-functional polymer-grafted SiO₂ nanoparticles was investigated with a transmission electron microscope (TEM).     

Anti-fouling poly(2-hydoxyethyl methacrylate) surface coatings with specific bacteria recognition capabilities

Poly(2-hydroxyethyl methacrylate), PHEMA, brushes were prepared by surface-initiated atom transfer radical polymerization (SI-ATRP) on silanized glass slides bearing grafted initiators. High resolution X-ray photoelectron spectroscopy (XPS) highlighted the surface chemical changes of the glass slides upon silanization and surface-confined ATRP of HEMA. Particularly, the initiator sites from the silane were detected by their bromine Br3d core electron peak whilst the O/C atomic ratios and the high resolution C1s region of the glass–PHEMA hybrids are comparable to those of pure PHEMA, thus confirming that the PHEMA chains have indeed attached to the surface. The glass–PHEMA hybrids were found to behave as anti-fouling ultrathin coatings as they resisted non-specific Salmonella typhimurium bacterial adhesion. This behaviour is driven by the hydrophilic properties of the glass–PHEMA hybrids which were assessed by contact angle measurements. In contrast, after activation of PHEMA brushes by S. typhimurium antibodies through the trichlorotriazine coupling procedure, the bacteria specifically and strongly attached to the PHEMA-coated glass slides as judged from optical microscope observation.     

Study of photophysical properties of capped CdS nanocrystals

Here, we have examined the role of capping agent on the optical properties of CdS nanoparticles by steady-state and time-resolved photoluminescence (PL) spectroscopy. The estimated particles sizes are 3.45, 2.5 and 2.39 nm for uncapped, capped with silica (SiO₂) and thiosalicylic acid (TSA), respectively. The absorption and emission spectra show a clear blue shift to shorter wavelengths in presence of TSA- and SiO₂-capped nanoparticles. It is found that the average decay time 〈τ〉 are 6.24, 4.54 and 2.84 ns for uncapped, capped with SiO₂ and TSA nanoparticles, respectively. Our analysis suggests that the hole or the electron is trapped on thiol molecule of TSA or hydroxyl group of SiO₂, then radiative recombination of the electron and hole is delayed, resulting in strong quenching of PL efficiency.     

Synthesis and properties of magnetic and luminescent Fe3O4/SiO2/Dye/SiO2 nanoparticles

A simple and reproducible method was developed to synthesize a novel class of Fe₃O₄/SiO₂/dye/SiO₂ composite nanoparticles. As promising candidates for use in bioassays, the obtained nanoparticles have an average diameter of 30 nm, and the thickness of the outer shell of silica could be tuned by changing the concentration of the silicon precursor tetraethyl orthosilicate during the synthesis. These multifunctional nanoparticles were found to be highly luminescent, photostable and superparamagnetic. The luminescence intensity of the nanoparticles was increased as the dye concentration was increased in the preparation process. The color of the luminescence was successfully tuned by incorporating different dyes into the nanoparticles. The measurements of the emission spectra indicated that relative to the dye molecules dissolved in ethanol, the emission of the dye-doped nanoparticles exhibited either a red shift or a blue shift, to which a tentative explanation was given.     

Preparation of MPS (mercaptopropyltrimethoxysilane)-coated SiO2 nanoparticle and its effect on mechanical properties of surface treated SiO2/EVA nanocomposite

SiO₂ nanoparticles were synthesized from different three precursors, namely, TEOS (tetraethyl orthosilicate), sodium metasilicate and sodium silicate. First, SiO₂ nanoparticles were prepared by a controlled hydrolysis of TEOS. In another method, SiO₂nanoparticles were prepared by precipitation in an emulsion medium from sodium metasilicate and hydrochloric acid solution. Finally, SiO₂ nanoparticles were also synthesized from sodium silicate by an emulsion method. In this study, we concentrated on dispersion and compatibility between nanosized SiO₂ particles and EVA (ethylene vinyl acetate). Therefore, surface modification of synthesized SiO₂ nanoparticles was accomplished with MPS (3-mercaptopropyl trimethoxysilane) to enhance homogeneous dispersion and compatibility between the obtained SiO₂ nanoparticles and EVA. Finally, nanocomposites of surface treated SiO₂ nanoparticles and EVA were prepared. By inserting the MPS-coated SiO₂ nanoparticles into EVA, abrasion resistance and hardness were increased remarkably. On the other hand, insertion of SiO₂ nanoparticles barely decreased original tensile strength and elongation of EVA. Consequently, MPS-coated SiO₂/EVA nanocomposite can have an improved abrasion resistance and hardness compared with raw EVA, without decrease tensile strength and elongation. The characterization of synthesized SiO₂ nanoparticles and their nanocomposite with EVA was conducted by TEM, SEM, FTIR photography and mechanical property tests such as abrasion, hardness, tensile strength and elongation.     

Surface tailoring of SiO2 nanoparticles by mechanochemical method based on simple milling

An appropriate modifying agent is obviously important with regard to the surface treatment of nanoparticles. Moreover, a right physical mixer that can provide enough energy to break up the secondary structure (aggregate and agglomerate) of nanoparticles is absolutely critical to the modification as well. However, it is not easy to give consideration to both of them during the process of modification. As is often the case, we tend to take care of the modifying agent but lose sight of the physical mixer. In this paper, hybrid particles of SiO₂/2,4-Diisocyanatotoluene (SiO₂/TDI) and SiO₂/2,4-Diisocyanatotoluene/hydroxyl silicone oil (SiO₂/TDI/(PDMS-OH)) were fabricated by mechanochemical method based on simple milling. The prepared hybrid particles (SiO₂/TDI and SiO₂/TDI/(PDMS-OH)) were characterized by infrared spectroscopy (FT-IR), static contact angle (CA), water sorption measurement, thermal analysis (TGA and DSC) and transmission electron microscopy (TEM). FT-IR spectra and thermal analysis (DSC) results demonstrate that TDI together with PDMS-OH is chemically anchored to the surface of nano-SiO₂. TGA results show that the grafting density of TDI is as high as 2.62 TDI/nm², while the grafting density of PDMS-OH is 0.0156 PDMS-OH/nm². Deduced from static contact angle (CA) and water sorption measurement, both hybrid particles exhibit strong hydrophobic (140^o for SiO₂/TDI and 144^o for SiO₂/TDI/(PDMS-OH)) after modification. TEM images reveal that hybrid particles (SiO₂/TDI and SiO₂/TDI/(PDMS-OH)) prepared by ball milling method exhibit much better miscibility and dispersibility in PDMS matrix when compared with those particles prepared by a common mixing device.     

Surface-initiated atom transfer radical polymerization from TiO2 nanoparticles

Two kinds of hydrophilic polymers, poly(oxyethylene methacrylate) (POEM) and poly(styrene sulfonic acid) (PSSA), were grafted from TiO₂ nanoparticles via the surface-initiated atom transfer radical polymerization (ATRP) technique. Chlorine modified TiO₂ nanoparticles (TiO₂-Cl), the ATRP initiators, were synthesized by the reaction of -OH in TiO₂ with 2-chloropropionyl chloride (CPC). FT-IR, UV-vis spectroscopy and X-ray photoelectron spectroscopy (XPS) clearly showed that the polymer chains were successfully grafted from the surface of TiO₂ nanoparticles. The hydrophilically modified TiO₂ nanoparticles have a better dispersion in alcohol than unmodified nanoparticles, as revealed by transmission electron microscopy (TEM). It was also found that the polymer grafting did not significantly alter the crystalline structure of the TiO₂ nanoparticles according to the X-ray diffraction (XRD) patterns. Grafting amounts were 10% of the weight for both TiO₂-POEM and TiO₂-PSSA nanoparticles, as determined by thermogravimetric analysis (TGA).     

Core/shell structured ZnO/SiO2 nanoparticles: Preparation, characterization and photocatalytic property

ZnO nanoparticles were prepared by a simple chemical synthesis route. Subsequently, SiO₂ layers were successfully coated onto the surface of ZnO nanoparticles to modify the photocatalytic activity in acidic or alkaline solutions. The obtained particles were characterized by Fourier transform infrared spectroscopy (FT-IR), X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectrometry (EDS) and zeta potential. It was found that ultrafine core/shell structured ZnO/SiO₂ nanoparticles were successfully obtained. The photocatalytic performance of ZnO/SiO₂ core/shell structured nanoparticles in Rhodamine B aqueous solution at varied pH value were also investigated. Compared with uncoated ZnO nanoparticles, core/shell structured ZnO/SiO₂ nanoparticles with thinner SiO₂ shell possess improved stability and relatively better photocatalytic activity in acidic or alkaline solutions, which would broaden its potential application in pollutant treatment.     

In vivo Monitoring of Organ-Selective Distribution of CdHgTe/SiO2 Nanoparticles in Mouse Model

CdHgTe/SiO₂ nanoparticles were prepared by SiO₂ capping on the surface of CdHgTe QDs. The characteristics, such as optical spectra, photostability, size and cell toxicity were investigated. The dynamic distribution of CdHgTe/SiO₂ nanoparticles was in vivo monitored by near infrared fluorescence imaging system. CdHgTe/SiO₂ nanoparticles acted as a novel fluorescence probe have a maximum fluorescence emission of 785 nm and high photo-stability. The hydrodynamic diameter of CdHgTe/SiO₂ nanoparticles could be adjusted to 122.3 nm. Compared to CdHgTe QDs, inhibitory effects of CdHgTe/SiO₂ nanoparticles on proliferation of HCT116 cells decreased to a certain extent. CdHgTe/SiO₂ nanoparticles had their specific dynamic distribution behavior, which provided new perspectives for bio-distribution of nanoparticles.     

Surface-initiated atom transfer radical polymerization of poly(4-vinylpyridine) from magnetite nanoparticle

Surface modification of magnetite nanoparticles (MNP) with a covalently bonded poly(4-vinylpyridine) (P4VP) by surface-initiated atom transfer radical polymerization (ATRP) is reported in this article. MNP was first prepared via thermal decomposition of Fe(acac)₃ and grafted with an ATRP initiator on its surface. ATRP of 4-vinylpyridine was then initiated from the MNP surface in the presence of CuBr/PMDETA (1,1,4,7,7-pentamethyldiethylenetriamine) catalytic complex in dioxane. FTIR in combination with photocorrelation spectroscopy (PCS), thermogravimetric analysis (TGA), and vibrating sample magnetometry (VSM) techniques indicated the growth of P4VP on the particle surface with increasing ATRP reaction time. Transmission electron microscopy (TEM) disclosed that the average particle size was 8 nm in diameter with some nanoaggregation observed. The PCS results revealed that decreasing the solution pH enhanced the particle dispersibility because of the positive charge repulsion of the protonated P4VP on the particle surface. TGA was also performed to elucidate the composition of P4VP shell and magnetite core in the hybrid material.     

Synthesis and Optical Properties of SiO2-Coated CeO2 Nanoparticles

Silica (SiO₂)-coated ceria (CeO₂) nanoparticles were prepared using water-in-oil microemulsion. Polyoxyethylene (15) cetylether and cyclohexane were used as a surfactant and organic solvent. SiO₂-coated CeO₂ nanoparticles were obtained by hydrolysis of metal alkoxide (tetraethylorthosilicate, TEOS) in the solution containing CeO₂ precursor nanoparticles. The effects of CeO₂ sources (Ce metal salt) and CeO₂ particle-forming agents on the morphology of SiO₂–CeO₂ particles were investigated. Observation via transmission electron microscopy revealed that the type of particle-forming agent affected the nanoparticles' morphology and that CeO₂ nanoparticles were spherically coated with SiO₂ when using oxalic acid ((COOH)₂) as a particle-forming agent of CeO₂. Furthermore, the transmittance of the particles was high in the visible region (above 400 nm) and decreased in the ultraviolet region.     

Synthesis and photoluminescent properties of silica-coated LaCeF<Subscript>3</Subscript>:Tb nanocrystals

La_0.45Ce_0.45F₃:Tb (10 mol% Tb) nanoparticles was synthesized via sonochemical method and then coated with silica (SiO₂) shells through a microemulsion process, resulting in the formation of core/shell structured LaCeF₃:Tb/SiO₂ nanoparticles. The obtained core/shell LaCeF₃:Tb/SiO₂ nanoparticles are spherical and uniform in size (average size about 60 nm), strongly fluorescent, and long fluorescence lifetime (1.87 ms). This kind of nanoparticles was water-soluble, which could be applied in biological labeling and other fields.     

Dewetting process of Au films on SiO2 nanowires: Activation energy evaluation

SiO₂ nanowires gain scientific and technological interest in application fields ranging from nano-electronics, optics and photonics to bio-sensing. Furthermore, the SiO₂ nanowires chemical and physical properties, and so their performances in devices, can be enhanced if decorated by metal nanoparticles (such Au) due to local plasmonic effects.In the present paper, we propose a simple, low-cost and high-throughput three-steps methodology for the mass-production of Au nanoparticles coated SiO₂ nanowires. It is based on (1) production of the SiO₂ nanowires on Si surface by solid state reaction of an Au film with the Si substrate at high temperature; (2) sputtering deposition of Au on the SiO₂ nanowires to obtain the nanowires coated by an Au film; and (3) furnace annealing processes to induce the Au film dewetting on the SiO₂ nanowires surface. Using scanning electron microscopy analyses, we followed the change of the Au nanoparticles mean versus the annealing time extracting values for the characteristic activation energy of the dewetting process of the Au film on the SiO₂ nanowires surface. Such a study can allow the tuning of the nanowires/nanoparticles sizes for desired technological applications.     

The effect of SiO2 and TiO2 nanoparticles on physical properties of SrFe12O19 nanoparticle

In order to obtain SrFe₁₂O₁₉ nanoparticles, thermal treatment method was employed, and afterwards SiO₂ and TiO₂ nanoparticles were embedded in SrFe₁₂O₁₉ matrix SrFe₁₂O₁₉ nanoparticles. The SiO₂ and TiO₂ nanoparticles' effects were set in SrFe₁₂O₁₉ matrix and experimental techniques which include, transmission electron microscopy (TEM), x-ray diffraction (XRD), fourier transform infrared spectroscopy (FT-IR), x-ray analysis (EDX) and field emission scanning electron microscope (FESEM) were used in studying the physical properties of the prepared nanoparticles. The precise DASF method (derivation of absorption spectrum fitting) was employed in examining the optical properties. The addition of SiO₂ and TiO₂ nanoparticles to SrFe₁₂O₁₉ matrix resulted in the reduction of energy band gap values in compare with the SrFe₁₂O₁₉ nanoparticles. The chemical analysis of SrFe₁₂O₁₉/SiO₂, SrFe₁₂O₁₉ nanoparticles, and SrFe₁₂O₁₉/TiO₂ nanocomposites was carried out using energy dispersion X-ray analysis (EDX). Ferromagnetic behaviors were demonstrated by SrFe₁₂O₁₉ nanoparticles, SrFe₁₂O₁₉/SiO₂ and SrFe₁₂O₁₉/TiO₂ nanocomposites, and the behaviors were validated through the use of a vibrating sample magnetometer (VSM). A wasp-waist was observed through hysteresis loop of SrFe₁₂O₁₉/SiO₂ nanocomposites, implying the presence of the two magnetic phases; soft and hard ferromagnetic.     

Preparation of functional composite grafted particles PDMAEMA/SiO2 and preliminarily study on functionality

Micron-sized silica gel particles were first surface-modified with coupling agent, γ-methacryloylpropyl trimethoxysilane (MPS), and the polymerizable double bonds were introduced onto the surfaces of silica gel particles, forming the modified particles MPS-SiO₂. Subsequently, N,N-dimethylaminoethyl methacrylate (DMAEMA) was graft-polymerized on the surfaces of particles MPS-SiO₂ in the manner of “grafting through”, resulting in the grafted particles PDMAEMA/SiO₂. The grafted particles PDMAEMA/SiO₂ were fully characterized with several means. The graft polymerization process of DMAEMA on particles MPS-SiO₂ was studied in detail, and the optimal reaction conditions were determined. Thereafter, the adsorption properties of the grafted particles PDMAEMA/SiO₂ for chromate anion and Cu²⁺ ion were preliminarily examined respectively. The experimental results indicate that the PDMAEMA grafting degree on PDMAEMA/SiO₂ particles is limited because an enwinding polymer layer as a kinetic barrier on the surfaces of silica gel particles will be formed during the graft polymerization, and blocks the graft polymerization. In order to enhance PDMAEMA grafting degree, reaction time and temperature, and the used amount of initiator as well as the monomer concentration should be effectively controlled. The preliminary adsorption tests show that the grafted particles PDMAEMA/SiO₂ are multi-functional. They possess very strong adsorption ability for CrO₄²⁻ anion by right of strong electrostatic interaction, and have also adsorption action towards heavy metal ion by dint of complexing action.     

Microstructure and magnetic properties of tubular cobalt–silica nanocomposites

Co-based (Co and Co₃O₄) nanoparticles were self-integrated into SiO₂ nanotubes with a methodology based on the use of a Co salt as a template structure for the formation of SiO₂ nanotubes. Within the confinement of tubular matrix of SiO₂, the nanofibres of cobalt precursor, i.e., [Co(NH₃)₆](HCO₃)(CO₃)·2H₂O, were treated in a H₂ atmosphere with different parameters. With a sufficient reduction on the cobalt precursor, sphere-like Co-based nanoparticles are obtained, being well aligned in the interior space of the SiO₂ nanotubes. With an insufficient reduction, platelet-like Co-based nanoparticles are formed, being arranged in a random manner inside the SiO₂ nanotubes. The sufficiently reduced Co–SiO₂ nanocomposite exhibits an open hysteresis loop in the low field region (<3 kOe) and a paramagnetic response in high field (>3 kOe) at 300 K. An observed wide separation between the zero-field-cooling (ZFC) and field-cooling (FC) curves over the whole temperature region has demonstrated a characteristic feature of ferromagnetism with a magnetically anisotropic barrier diverting the easy axis from the axis of the applied field. The predominant factor leading to this anisotropic potential barrier is attributed to the shape anisotropy native to the one-dimensional arrangement of Co-based nanoparticles within the tubular matrix, i.e. SiO₂ nanotubes.     

Preparation and characterization of silicon oil based ferrofluid

Stable silicon oil based ferrofluid was prepared in the present investigation. Silicon oil surfactant ethoxy terminated polydimethylsiloxane was used to modify the Fe₃O₄ nanoparticles. The Fe₃O₄ nanoparticles were firstly coated with a SiO₂ layer by the hydrolysis of tetraethoxysilane. Then using the active hydroxyl groups on the surface of the SiO₂, silicon oil surfactant was covalently grafted onto the Fe₃O₄ nanoparticles surface. The ethoxy terminated polydimethylsiloxane has similar molecular chain structure and good compatibility with that of the carrier liquid, thus ensuring stable dispersion of modified Fe₃O₄ in the carrier silicon oil. The interaction between Fe₃O₄ and the modifier was characterized by IR and XPS. The crystal structure and the magnetic properties of the Fe₃O₄ nanoparticles were determined by XRD and VSM, respectively. The size and morphology of the particles were observed using TEM. The properties of the silicon oil based ferrofluid were characterized by Gouy magnetic balance. The results indicated that the ferrofluid had high magnetism and good stability. The rheological properties and thermostability of the ferrofluid were also investigated.     

Emulsion Combustion and Flame Spray Synthesis of Zinc Oxide/Silica Particles

Two flame spray methods, emulsion combustion method (ECM) and flame spray pyrolysis (FSP), were compared for synthesis of pure and mixed SiO₂ and ZnO nanoparticles. The effect of silicon precursor was investigated using liquid hexamethyldisiloxane (HMDSO) or SiO₂ sol, while for ZnO zinc acetate (ZA) was used. Gas phase reaction took place when using HMDSO as Si precursor, forming nanoparticles, whereas the SiO₂ sol used as Si source was not evaporated in the flame, creating large aggregates of the sol particles (e.g. 1 m). The FSP of ZA produced ZnO homogeneous nanoparticles. Lower flame temperatures in ECM than in FSP resulted in mixed gas and liquid phase reaction, forming ZnO particles with inhomogeneous sizes. The FSP of HMDSO and ZA led to intimate gas-phase mixing of Zn and Si, suppressing each other's particle growth, forming nanoparticles of 19 nm in BET-equivalent average primary particle diameter. Nucleation of ZnO and SiO₂ occurred independently by ECM of HMDSO and ZA as well as by FSP of the SiO₂ sol and ZA, creating a ZnO and SiO₂ mixture. The reaction of ZnO with SiO₂ was likely to be enhanced by ECM of the SiO₂ sol and ZA where both Zn and Si species were not evaporated completely, resulting in ZnO, -willemite and Zn_1.7SiO₄ mixed phase.