Nanostructures of functionalized gold nanoparticles prepared by particle lithography with organosilanes

Periodic arrays of organosilane nanostructures were prepared with particle lithography to define sites for selective adsorption of functionalized gold nanoparticles. Essentially, the approach for nanoparticle lithography consists of procedures with two masks. First, latex mesospheres were used as a surface mask for deposition of an organosilane vapor, to produce an array of holes within a covalently bonded, organic thin film. The latex particles were readily removed with solvent rinses to expose discrete patterns of nanosized holes of uncovered substrate. The nanostructured film of organosilanes was then used as a surface mask for a second patterning step, with immersion in a solution of functionalized nanoparticles. Patterned substrates were fully submerged in a solution of surface-active gold nanoparticles coated with 3-mercaptopropyltrimethoxysilane. Regularly shaped, nanoscopic areas of bare substrate produced by removal of the latex mask provided sites to bind silanol-terminated gold nanoparticles, and the methyl-terminated areas of the organosilane film served as an effective resist, preventing nonspecific adsorption on masked areas. Characterizations with atomic force microscopy demonstrate the steps for lithography with organosilanes and functionalized nanoparticles. Patterning was accomplished for both silicon and glass substrates, to generate nanostructures with periodicities of 200-300 nm that match the diameters of the latex mesospheres of the surface masks. Nanoparticles were shown to bind selectively to uncovered, exposed areas of the substrate and did not attach to the methyl-terminal groups of the organosilane mask. Billions of well-defined nanostructures of nanoparticles can be generated using this high-throughput approach of particle lithography, with exquisite control of surface density and periodicity at the nanoscale.     

Ru(bpy)3]2+-doped silica nanoparticles within layer-by-layer biomolecular coatings and their application as a biocompatible electrochemiluminescent tag material

[Ru(bpy)3]2+-doped silica (RuSi) nanoparticles were synthesized by using a water/oil microemulsion method. Stable electrochemiluminescence (ECL) was obtained when the RuSi nanoparticles were immobilized on a glassy carbon electrode by using tripropylamine (TPA) as a coreactant. Furthermore, the ECL of the RuSi nanoparticles with layer-by-layer biomolecular coatings was investigated. Squential self-assembly of the polyelectrolytes and biomolecules on the RuSi nanoparticles gave nanocomposite suspensions, the ECL of which decreased on increasing the number of bilayers. Moreover, factors that affected the assembly and ECL signals were investigated. The decrease in ECL could be assigned to steric hindrance and limited diffusion of the coreactant molecules in the silica matrix after they were attached to the biomolecules. Since surface modification of the RuSi nanoparticles can improve their biocompatibility and prevent leaking of the [Ru(bpy)3]2+ ions, the RuSi nanoparticles can be readily used as efficient and stable ECL tag materials in immunoassay and DNA detection.     

Single crystalline ordered silicon wire/Pt nanoparticle hybrids for solar energy harvesting

In this work, we developed a method combining lithography and metal-catalyzed Si etching to fabricate highly ordered Si wire arrays with uniform coverage over an entire 4 in. wafer. The wire periodicity and dimensions depend on the lithography and the etching conditions. Photoelectrochemical measurements show that the as-prepared Si wire samples are photoactive owing to surface enhancement and become especially effective in solar-to-electrical conversion and water splitting after surface modification with Pt nanoparticles.     

Nanostructures for magnetically triggered release of drugs and biomolecules

Specific targeting and controlled release are crucial factors in the administration of drugs and therapeutic biomolecules. It has been shown that drug delivery systems can significantly benefit of the introduction of superparamagnetic nanoparticles in terms of both targeting and controlled release. Magnetic gradients can be used to target therapeutics to specific regions, while alternating magnetic fields produce frequency-dependent effects at the nanoparticle level. This review reports on the latest developments of multifunctional systems based on magnetic nanoparticles where the release of drugs and/or biomolecules is triggered by the application of an external magnetic field. The potentials of these systems are presented through examples in the fields of surface functionalized magnetic nanoparticles, magnetic polymer nanocomposites and magnetoliposomes. Recent results suggest the importance of integrating multiple functions within a single nanostructured device in order to successfully transport, localize and release drugs and biomolecules.     

Novel synthetic route for covalent coupling of biomolecules on super‐paramagnetic hybrid nanoparticles

The immobilization of biomolecules on magnetic nanoparticles is an issue with high potential in different fields. We describe herein a new strategy to immobilize biomolecules on super‐paramagnetic nanoparticles based on the reactivity of vinyl sulfone groups with naturally occurring functional groups present in biomolecules (amine and thiol). A new monomer containing a polymerizable methacryloyl group and a secondary amine group was synthesized and used to prepare super‐paramagnetic hybrid nanoparticles (SP‐HNPs) by two‐step miniemulsion polymerization. The Michael addition reaction of divinyl sulfone (DVS) to the secondary amine groups localized on the nanoparticles surface allows the introduction of the vinyl sulfone function in the SP‐HNPs (SP‐HNPs‐VS). The morphology of the functionalized SP‐HNPs was characterized by transmission electron microscopy (TEM), high‐resolution transmission electron microscopy (HRTEM), dynamic light scattering, and magnetic susceptibility. The capacity of SP‐HNPs‐VS for the immobilization of biomolecules was evaluated with three model proteins: avidin, invertase, and horseradish peroxidase (HRP). The model proteins were successfully immobilized in mild aqueous conditions compatible with the biological nature of the enzymes. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Biosensing using silver nanoparticles and surface enhanced resonance Raman scattering

Silver nanoparticles can be used to provide excellent surface enhanced resonance Raman scattering. Control of the surface chemistry and the use of appropriate protocols enables effective sensing of biomolecules.     

Gold nanoparticle patterning of silicon wafers using chemical e-beam lithography

This paper demonstrates a novel facile method for fabrication of patterned arrays of gold nanoparticles on Si/SiO2 by combining electron beam lithography and self-assembly techniques. Our strategy is to use direct-write electron beam patterning to convert nitro functionality in self-assembled monolayers of 3-(4-nitrophenoxy)-propyltrimethoxysilane to amino functionality, forming chemically well-defined surface architectures on the 100 nm scale. These nanopatterns are employed to guide the assembly of citrate-passivated gold nanoparticles according to their different affinities for amino and nitro groups. This kind of nanoparticle assembly offers an attractive new option for nanoparticle patterning a silicon surface, as relevant, for example, to biosensors, electronics, and optical devices.     

Bio-friendly synthesis of ZnO nanoparticles in aqueous solution at near-neutral pH and low temperature

ZnO nanoparticles are synthesized using a new bio-friendly method. The experimental conditions are very mild: aqueous solution at near-neutral pH and 37 degrees C. The as-obtained nanoparticles show the stable wurtzite structure without the need of annealing. The two reagents used are aqueous solutions of zinc nitrate and buffer tris(hydroxymethyl)aminomethane. This is a standard nontoxic buffer and inert to a wide variety of chemicals and biomolecules, therefore extremely satisfactory for biochemical reactions. Furthermore, this is a polydentade ligand which adsorbs strongly on one or more surfaces of ZnO inhibiting its crystal growth and yielding nearly spherical ZnO nanoparticles. Our objective is to use the crystallization method described here for further incorporation of biomolecules as additives in the reaction solution, aiming at the formation of ZnO with new physical properties.     

Solution-phase, triangular ag nanotriangles fabricated by nanosphere lithography

A novel method to produce solution-phase triangular silver nanoparticles is presented. Ag nanoparticles are prepared by nanosphere lithography and are subsequently released into solution. The resulting nanoparticles are asymmetrically functionalized to produce either single isolated nanoparticles or dimer pairs. The structural and optical properties of Ag nanoparticles have been characterized. Mie theory and the Discrete Dipole Approximation method (DDA) have been used to model and interpret the optical properties of the released Ag nanoparticles.     

Au-Ag hybrid nanoparticle patterns of tunable size and density on glass and polymeric supports

This paper describes a method to pattern surfaces with Au-Ag hybrid nanoparticles. We used block copolymer micelle lithography of Au nanoparticles and electroless deposition of Ag. The combination of these two methods enables independent tuning of nanoparticle spacing and Ag-shell size. For this purpose, 8 nm large patterned Au nanoparticle seeds served as nuclei for the electroless deposition of silver that is based on a modified Tollens process with glucose. By adjusting the reaction conditions, specific growth of Ag on top of the Au seeds has been accomplished and analyzed by SEM, HRTEM, XEDS, and UV-vis spectroscopy. We could show that this versatile and green method is feasible on glass as well as on biomedical-relevant polymers like poly(ethylene glycol) hydrogels and amorphous Teflon. In conclusion, this method provides a new route to pattern glass and polymeric surfaces with Au-Ag hybrid nanoparticles. It will have many uses in applications such as surface enhanced Raman spectroscopy (SERS) or antimicrobial coatings for which hybrid nanoparticle density, size, and morphology are important.     

氧化铁磁性纳米粒子的制备、表面修饰及在分离和分析中的应用

氧化铁磁性纳米粒子通过表面化学修饰得到无机、有机或聚合物壳包覆在其表面。其中的壳结构既具有生物适应性,又具有可键合生物分子如细胞、蛋白质、酶、抗体和核酸的活性基团,而核具有磁性特性。本文总结了氧化铁磁性纳米粒子的制备方法,介绍了其表面化学修饰及在分离和分析应用的最新进展。     

New two-dimensional polymer-metal composites based on highly ordered ensembles of nanoparticles. Design and optical properties

A new method has been proposed for designing composite materials that represent highly ordered two-dimensional metal nanoparticles ensembles having variable geometric parameters and being embedded into the surface layer of a polymer matrix to a predetermined depth. The method is based on diblock copolymer micellar lithography and the effect of decreased glass-transition temperature of a polymer surface as compared with its bulk value. The possibility of independent variations in the depth of embedding of metal nanoparticles (by system annealing) and their size (by seeded growth) has resulted in the systematic study of the influence of the temperature and time of annealing on the kinetics of nanoparticle embedding into a polymer. For the first time, the plasmon-resonant properties of hexagonally ordered ensembles of gold nanoparticles located at a polymer-air interface have been experimentally studied. It has been established that the embedding of an ensemble of nanoparticles into a polymer is accompanied by a bathochromic shift of the maximum of its localized surface plasmon resonance due to a growth in the effective dielectric permittivity of the environment of the nanoparticles. An empirical equation has been proposed, which satisfactorily describes these experimental data.     

Chemically Organizable Nanosized Materials Preparation and Applications

We are interested in fabricating well-organized assemblies of nanosized materials with wet chemical approaches for the purpose of investigating various interfacial and mesoscopic phenomena. The paper describes how to use self-assembling techniques to prepare assemblies of colloidal nanoparticles and single walled carbon nanotubes on solid surfaces. Gold nanocolloids are taken as the model system, including preparation of functionalized nanoparticles, assembling on tailored substrates, surface reorganization, and 1D, 0D controlled assembling with the aid of scanning probe lithography. The typical work we have been doing using these elaborated nanoparticle assemblies includes, the quantitative investigations of die electromagnetic coupling of particle-particle and particle-substrate in surface enhanced Raman scattering (SERS), the single electron tunneling in nanoparticle assemblies measured with scanning probe microscopy (SPM) technique, the atomic force microscopy (AFM) lithography using the surface-confined gold nanoparticles as mask.     

The surface functionalisation of gold nanoparticles with metal complexes

The use of nanoparticles is now expanding well beyond the field of pure materials science. In particular, the modification of the surface functionality is playing a key role in catalysis, sensor applications and immobilisation of biomolecules. The use of coordinated metals on the outer surface of gold nanoparticles is the focus of this short article.     

Proteins conjugation with ZnO sol–gel nanopowders

The conjugation between probe biomolecules and inorganic nanoparticles has been studied. Three different and biologically relevant proteins, bovine serum albumin (BSA), lysozyme (LSZ) and Ribonuclease A (RNAseA), have been selected as model systems because of their difference in size and isoelectric point. Zinc oxide nanoparticles, synthesized via sol–gel, have been thoroughly characterized by X-ray Photoelectron Spectroscopy, Scanning Electron Microscopy and X-ray Diffraction, and subsequently used as platforms for immobilization of the biomolecules. The interaction of the three proteins with the ZnO surface was performed in phosphate buffer solutions at pH 7.2 in order to mimic physiological fluids and was investigated through fluorescence experiments. The obtained results indicate that conjugation of BSA, LZS and RNAseA on the oxide nanoparticles was mostly dictated by the overall charge of the different proteins. Electrostatic bonds dominate the formation of the protein/ZnO conjugates, whereas the size of the proteins seems to play a negligible role under the adopted experimental conditions.     

Fabricating protein immunoassay arrays on nitrocellulose using dip-pen lithography techniques

Advancements in lithography methods for printing biomolecules on surfaces are proving to be potentially beneficial for disease screening and biological research. Dip-pen nanolithography (DPN) is a versatile micro and nanofabrication technique that has the ability to produce functional biomolecule arrays. The greatest advantage, with respect to the printing mechanism, is that DPN adheres to the sensitive mild conditions required for biomolecules such as proteins. We have developed an optimised, high-throughput printing technique for fabricating protein arrays using DPN. This study highlights the fabrication of a prostate specific antigen (PSA) immunoassay detectable by fluorescence. Spot sizes are typically no larger than 8 μm in diameter and limits of detection for PSA are comparable with a commercially available ELISA kit. Furthermore, atomic force microscopy (AFM) analysis of the array surface gives great insight into how the nitrocellulose substrate functions to retain protein integrity. This is the first report of protein arrays being printed on nitrocellulose using the DPN technique and the smallest feature size yet to be achieved on this type of surface. This method offers a significant advance in the ability to produce dense protein arrays on nitrocellulose which are suitable for disease screening using standard fluorescence detection.     

Arrays of covalently bonded single gold nanoparticles on thiolated molecular assemblies

A simple approach to form arrays of covalently bonded single gold nanoparticles (AuNPs) is demonstrated. Asymmetric molecular assemblies composed of two layers of rigid aromatic molecules with different structures, arranged in hexagonal arrays on a template produced by edge-spreading lithography, are used to guide the assembly of AuNPs. Arrays of single AuNPs are achieved by taking advantage of the interplay of electrostatic interactions and covalent bonding in conjunction with the positional constraint on the template. Schiff base chemistry is highlighted in the surface chemical reaction to selectively modify nanoscale surface features with high yield.     

Biomolecule and nanoparticle transfer on patterned and heterogeneously wetted superhydrophobic silicon nanowire surfaces

We report on the use of patterned superhydrophobic silicon nanowire surfaces for the efficient, selective transfer of biological molecules and nanoparticles. Superhydrophilic patterns are prepared on superhydrophobic silicon nanowire surfaces using standard optical lithography. The resulting water-repellent surface allows material transfer and physisorption to the superhydrophilic islands upon exposure to an aqueous solution containing peptides, proteins, or nanoparticles.     

Bright luminescent, colloidal stable silica coated CdSe/ZnS nanocomposite by an in situ, one-pot surface functionalization

In this article, a systematic study of the design and development of surface-modification schemes for silica coated nanocomposite via an in situ, one-pot way is presented. Silica coated CdSe/ZnS nanoparticles were prepared in a water-in-oil microemulsion and subsequently surface modified via addition of various organosilane reagents to the microemulsion system. The resulting functionalized composite nanoparticles were characterized by different techniques like Transmission Electron Microscopy (TEM), photoluminescence spectroscopy and zeta-potential measurements. The results demonstrate that depending on the sequence of addition of silica precursors and organosilanes the product can show bright luminescence or considerable colloidal stability. The organosilanes molecules which are used here, act both as a stabilizer of the microemulsion system (regarding the charge compensation) and as a functional group the final product on top of silica shell. Using these surface-modification process, silica coated nanoparticles can be more readily conjugated with biomolecules and used as highly luminescent, sensitive, and reproducible labels in bioanalytical applications. Most importantly such surface functionalization could pave the way for controlled multi-mixed nanoparticles encapsulation (for example magnetic and QD nanoparticles).     

Magnetic iron oxide nanoparticles for biorecognition: evaluation of surface coverage and activity

Modifying the surfaces of magnetic nanoparticles (MNPs) by the covalent attachment of biomolecules will enable their implementation as contrast agents for magnetic resonance imaging or as media for magnetically assisted bioseparations. In this paper we report both the surface coverage and the activity of IgG antibodies on MNPs. The antibodies were immobilized on gamma-Fe2O3 nanoparticles by conventional methods using aminopropyltriethoxy silane and subsequent activation by glutaraldehyde. Novel fluorescence methods were used to provide a quantitative evaluation of this well-known approach. Our results show that surface coverage can be stoichiometrically adjusted with saturated surface coverage occurring at approximately 36% of the theoretical limit. The saturated surface coverage corresponds to 34 antibody molecules bound to an average-sized MNP (32 nm diameter). We also show that the immobilized antibodies retain approximately 50% of their binding capacity at surface-saturated levels.