Peptide-induced patterning of gold nanoparticle thin films

In this work, the use of patterned proteins and peptides for the deposition of gold nanoparticles on several substrates with different surface chemistries is presented. The patterned biomolecule on the surface acts as a catalyst to precipitate gold nanoparticles from a precursor solution of HAuCl₄ onto the substrate. The peptide patterning on the surfaces was accomplished by physical adsorption or covalent attachment. It was shown that by using covalent attachment with a linker molecule, the influence of the surface properties from the different substrates on the biomolecule adsorption and subsequent nanoparticle deposition could be avoided. By adjusting the reaction conditions such as pH or HAuCl₄ concentration, the sizes and morphologies of deposited gold nanoparticle agglomerates could be controlled. Two biomolecules were used for this experiment, 3XFLAG peptide and bovine serum albumin (BSA). A micro-transfer molding technique was used to pattern the peptides on the substrates, in which a pre-patterned poly(dimethylsiloxane) (PDMS) mold was used to deposit a lift-off pattern of polypropylmethacrylate (PPMA) on the various substrates. The proteins were either physically adsorbed or covalently attached to the substrates, and an aqueous HAuCl₄ solution was applied on the substrates with the protein micropatterns, causing the precipitation of gold nanoparticles onto the patterns. SEM, AFM, and Electron Beam Induced Current (EBIC) were used for characterization.     

Functionalization of magnetic gold/iron-oxide composite nanoparticles with oligonucleotides and magnetic separation of specific target

Magnetic composite nanoparticles of gold and iron-oxide synthesized with gamma-rays or ultrasonics were functionalized with thiol-modified oligonucleotides. The amount of oligonucleotides bound to the functionalized nanoparticle probes via hybridization was quantified with fluorescently-labeled target oligonucleotides. Our composite nanoparticles magnetically separated the specific target oligonucleotides without the non-specific adsorption.     

Grafting poly(ethylene glycol) monomethacrylate onto Fe3O4 nanoparticles to resist nonspecific protein adsorption

Magnetic nanoparticles grafted with poly(poly(ethylene glycol) monomethacrylate) (P(PEGMA)) were prepared by reversible addition-fragmentation chain transfer (RAFT) polymerization. In this approach, S-benzyl S′-trimethoxysilylpropyltrithiocarbonate, used as a chain transfer agent for RAFT, was first immobilized onto the magnetic nanoparticle surface, and then PEGMA was grafted onto the surface of magnetic nanoparticle via RAFT polymerization. The results showed that P(PEGMA) chains grew from magnetic nanoparticles by surface-induced RAFT polymerization. The grafted P(PEGMA) chains can decrease the nonspecific adsorption of proteins on the surface of Fe₃O₄ nanoparticles.     

Adsorption of surface functionalized silica nanoparticles onto mineral surfaces and decane/water interface

The adsorption of silica nanoparticles onto representative mineral surfaces and at the decane/water interface was studied. The effects of particle size (the mean diameters from 5 to 75?nm), concentration and surface type on the adsorption were studied in detail. Silica nanoparticles with four different surfaces [unmodified, surface modified with anionic (sulfonate), cationic (quaternary ammonium (quat)) or nonionic (polyethylene glycol (PEG)) surfactant] were used. The zeta potential of these silica nanoparticles ranges from ?79.8 to 15.3?mV. The shape of silica particles examined by a Hitachi-S5500 scanning transmission electron microscope (STEM) is quite spherical. The adsorption of all the nanoparticles (unmodified or surface modified) on quartz and calcite surfaces was found to be insignificant. We used interfacial tension (IFT) measurements to investigate the adsorption of silica nanoparticles at the decane/water interface. Unmodified nanoparticles or surface modified ones with sulfonate or quat do not significantly affect the IFT of the decane/water interface. It also does not appear that the particle size or concentration influences the IFT. However, the presence of PEG as a surface modifying material significantly reduces the IFT. The PEG surface modifier alone in an aqueous solution, without the nanoparticles, yields the same IFT reduction for an equivalent PEG concentration as that used for modifying the surface of nanoparticles. Contact angle measurements of a decane droplet on quartz or calcite plate immersed in water (or aqueous nanoparticle dispersion) showed a slight change in the contact angle in the presence of the studied nanoparticles. The results of contact angle measurements are in good agreement with experiments of adsorption of nanoparticles on mineral surfaces or decane/water interface. This study brings new insights into the understanding and modeling of the adsorption of surface-modified silica nanoparticles onto mineral surfaces and water/decane interface.     

Adsorption of firefly luciferase at interfaces studied by total internal reflection fluorescence spectroscopy

The adsorption of luciferase onto silica surfaces was studied by total internal reflection fluorescence (TIRF) spectroscopy. Two model surfaces were used: hydrophilic and hydrophobic silica. Luciferase adsorbed differently on these two surfaces. Initial kinetics of luciferase adsorption onto the hydrophilic surface showed that luciferase adsorbs over an adsorption energy barrier of 3 kT The quantum yield of luciferase fluorescence decreased at the hydrophilic silica surface, which indicated that the protein conformation was altered during adsorption. Luciferase adsorption onto the hydrophobic silica surface proceeded with a small adsorption energy barrier and the fluorescence efficiency of adsorbed protein remained unchanged after adsorption. The affinity of luciferase for luciferin was measured using quenching of luciferase fluorescence with luciferin. The binding constant of the adsorbed luciferase-luciferin complex at the hydrophilic silica surface was two orders of magnitude smaller than the respective binding constant in the solution. Adsorbed luciferase showed an absence of ATP-dependent visible luminescence, indicating that the adsorbed enzyme was not active at either of the two silica surfaces.     

Surface Modification of Magnetic Nanoparticles Using Gum Arabic

Magnetite nanoparticles were synthesized and functionalized by coating the particle surfaces with gum arabic (GA) to improve particle stability in aqueous suspensions (i.e. biological media). Particle characterization was performed using transmission electron microscopy (TEM) and dynamic light scattering (DLS) to analyze the morphology and quantify the size distribution of the nanoparticles, respectively. The results from DLS indicated that the GA-treated nanoparticles formed smaller agglomerates as compared to the untreated samples over a 30-h time frame. Thermogravimetric analyses indicated an average weight loss of 23%, showing that GA has a strong affinity toward the iron oxide surface. GA most likely contributes to␣colloid stability via steric stabilization. It was determined that the adsorption of GA onto magnetite exhibits Langmuir behavior.     

Self-assembled and fluorescence enhancement of semiconductor nanoparticles induced by surfactant adsorption

When semiconductor colloidal CdS nanoparticles and nonylphenol are mixed together in dimethyl sulfoxide at room temperature, a self-assembling process is induced. In the course, the size tunable properties of CdS nanoparticles are amplified. A blue shift in the emission spectrum and a strong photoluminescence enhancement are observed without significant change in the absorption features of the colloidal nanoparticles. These results are attributed to the adsorption of nonylphenol onto the nanoparticles surface and to the association process of the surfactant molecules. The surfactant adsorption process provides a nanoparticle surface passivation and induces an associative phase that enlarges the photoluminescence stability. This strategy opens the possibility to improve simultaneously physicochemical and photoluminescence properties of nanocrystals in solution as well as to control their deposition on two-dimensional surfaces.     

Functionalization of magnetic nanoparticles with 3-aminopropyl silane

Superparamagnetic maghemite nanoparticles were functionalized with 3-aminopropyl triethoxy silane (APS). The influence of the different experimental parameters (temperature, pH, and reactant concentration) on the efficiency of the APS bonding directly to the maghemite nanoparticles or after their coating with a thin layer of silica was systematically studied. The functionalization was followed with measurements of the ζ-potential and direct measurements of the surface APS concentration on the nanoparticles. The surface concentration of the APS was much higher in the case when the APS was bonded to the silica-coated nanoparticles compared to bonding directly to the surfaces of the iron-oxide nanoparticles.     

Surface functionalization of silica-coated magnetic nanoparticles for covalent attachment of cholesterol oxidase

A systematic approach towards the fabrication of highly functionalized silica shell magnetic nanoparticles, presently used for enzyme immobilization, is herein fully presented. The synthesis of bare maghemite (γ-Fe₂O₃) nanoparticles was accomplished by thermal co-precipitation of iron ions in ammonia alkaline solution at harsh reaction conditions, respectively. Primary surface engineering of maghemite nanoparticles was successfully performed by the proper deposition of silica onto nanoparticles surface under strictly regulated reaction conditions. Next, the secondary surface functionalization of the particles was achieved by coating the particles with organosilane followed by glutaraldehyde activation in order to enhance protein immobilization. Covalent immobilization of cholesterol oxidase was attempted afterwards. The structural and magnetic properties of magnetic silica nanocomposites were characterized by TEM and vibrating sample magnetometer (VSM) instruments. X-ray diffraction measurements confirmed the spinel structure and average size of uncoated maghemite nanoparticles to be around 20 nm in diameter. SEM-EDS spectra indicated a strong signal for Si, implying the coating procedure of silica onto the particles surface to be successfully accomplished. Fourier transform infrared (FT-IR) spectra analysis confirmed the binding of amino silane molecules onto the surface of the maghemite nanoparticles mediated Si-O-Si chemical bonds. Compared to the free enzyme, the covalently bound cholesterol oxidase retained 50% of its activity. Binding of enzyme onto chemically modified magnetic nanoparticles via glutaraldehyde activation is a promising method for developing biosensing components in biomedicine.     

Surface functionalization of chitosan-coated magnetic nanoparticles for covalent immobilization of yeast alcohol dehydrogenase from Saccharomyces cerevisiae

A novel and efficient immobilization of yeast alcohol dehydrogenase (YADH, EC1.1.1.1) from Saccharomyces cerevisiae has been developed by using the surface functionalization of chitosan-coated magnetic nanoparticles (Fe₃O₄/KCTS) as support. The magnetic Fe₃O₄/KCTS nanoparticles were prepared by binding chitosan alpha-ketoglutaric acid (KCTS) onto the surface of magnetic Fe₃O₄ nanoparticles. Later, covalent immobilization of YADH was attempted onto the Fe₃O₄/KCTS nanoparticles. The effect of various preparation conditions on the immobilized YADH process such as immobilization time, enzyme concentration and pH was investigated. The influence of pH and temperature on the activity of the free and immobilized YADH using phenylglyoxylic acid as substrate has also been studied. The optimum reaction temperature and pH value for the enzymatic conversion catalyzed by the immobilized YADH were 30 °C and 7.4, respectively. Compared to the free enzyme, the immobilized YADH retained 65% of its original activity and exhibited significant thermal stability and good durability.     

Producing ultra-thin silica coatings on iron-oxide nanoparticles to improve their surface reactivity

The reactivity of the relatively inert surfaces of iron-oxide magnetic nanoparticles can be significantly improved by coating the surfaces with silica. Unfortunately, however, this nonmagnetic silica layer tends to dilute the magnetic properties of the nanoparticles. Therefore, the silica layer should be as continuous, homogeneous, and as thin as possible.In this investigation we coated superparamagnetic maghemite nanoparticles by hydrolysis and the polycondensation of tetraethyl orthosilicate (TEOS), with the ethanol solution of TEOS being added to a stable suspension of citric acid-coated nanoparticles. The influences of the various parameters of the procedure on the quality of the coatings were systematically evaluated. The quality of the silica layer was characterized using electron microscopy and by performing leaching of the nanoparticles in HCl, while the surface reactivity was tested by grafting (3-aminopropyl) triethoxysilane (APS) onto the nanoparticles. We observed that the surface concentration of the grafted APS strongly increased when the nanoparticles were coated with a silica layer. The choice of experimental conditions for the coating procedure that favors the heterogeneous nucleation of silica on the surfaces of the nanoparticles enabled the preparation of very thin silica layers, less than 2 nm thick. By decreasing the amount of added TEOS to correspond to a monolayer of -Si-OH at the nanoparticles' surfaces, their surface reactivity could be very much improved, and with a reduction in their magnetization of only ∼10%.     

Effect of the number of iron oxide nanoparticle layers on the magnetic properties of nanocomposite LbL assemblies

Aqueous colloidal suspension of iron oxide nanoparticles has been synthesized. Z-potential of iron oxide nanoparticles stabilized by citric acid was −35±3 mV. Iron oxide nanoparticles have been characterized by the light scattering method and transmission electron microscopy. The polyelectrolyte/iron oxide nanoparticle thin films with different numbers of iron oxide nanoparticle layers have been prepared on the surface of silicon substrates via the layer-by-layer assembly technique. The physical properties and chemical composition of nanocomposite thin films have been studied by atomic force microscopy, magnetic force microscopy, magnetization measurements, Raman spectroscopy. Using the analysis of experimental data it was established, that the magnetic properties of nanocomposite films depended on the number of iron oxide nanoparticle layers, the size of iron oxide nanoparticle aggregates, the distance between aggregates, and the chemical composition of iron oxide nanoparticles embedded into the nanocomposite films. The magnetic permeability of nanocomposite coatings has been calculated. The magnetic permeability values depend on the number of iron oxide nanoparticle layers in nanocomposite film.     

Characterization of protein-conjugating kinetics based on localized surface plasmon resonance of the gold nanoparticle

The gold nanoparticle exhibits optical property of localized surface plasmon resonance (LSPR), which dynamically alters as the surface adsorbs new ligands. We carried out a semi-quantitative analysis with the method of multivariate curve resolution, observing that the adsorption of serum albumin on gold nanoparticle was best deciphered as two-mode competitive kinetics. Interestingly, for human serum albumin, the slower mode contributed considerably to the LSPR response of protein-conjugated surfaces, while in the case of bovine serum albumin the faster mode overwhelmed the slower one at high protein concentrations. The kinetic patterns were rationalized with diversity of biomolecular orientations on the nanoparticle surface. The simple but efficient protocol supports semi-quantitative analysis combining UV-vis spectroscopy with chemometrics method for distinguishing conjugation kinetics of different types of proteins on the surface of nanoparticles at nanomolar concentration.     

Sonochemical preparation of composite nanoparticles of Au/gamma-Fe2O3 and magnetic separation of glutathione

We prepared Au/gamma-Fe2O3 composite nanoparticles by sonochemically reducing Au(III) ions employing no stabilizer in the aqueous solution to form stable Au nanoparticles and allowing them to attach onto the surface of gamma-Fe2O3 particles with an average size of 21 nm. Size of the formed Au nanoparticle depended on the initial concentration of Au(III) ions. The number of the Au nanoparticles, supported on each gamma-Fe2O3 particle was controlled by changing the relative amounts of Au(III) ions and gamma-Fe2O3 particles. The composite nanoparticles exhibited a high affinity with glutathione, a tripeptide with mercapto group so that separation and manipulation of glutathione in aqueous solutions could be performed by application of external magnetic field. Because the surfaces of the Au nanoparticles were not shielded by any stabilizers, or naked, sonochemically prepared Au/gamma-Fe2O3 composite nanoparticles seemed to show stronger affinity to the glutathione than those by the radiochemical method.     

Towards Nanoscale Biomedical Devices in Medicine: Biofunctional and Spectroscopic Characterization of Superparamagnetic Nanoparticles

Medical interest in nanotechnology originates from a belief that nanoscale therapeutic devices can be constructed and directed towards its target inside the human body. Such nanodevices can be engineered by coupling superparamagnetic nanoparticle to biomedically active proteins. We hereby report the immobilization of a PhEst, a S-formylglutathione hydrolase from the psychrophilic P. haloplanktis TAC125 onto the gold coated surface of modified superparamagnetic core-shell nanoparticles (Fe₃O₄@Au). The synthesis of the nanoparticles is also reported. S-formylglutathione hydrolases constitute a family of ubiquitous enzymes which play a key role in formaldehyde detoxification both in prokaryotes and eukaryotes. PhEst was originally annotated as a putative feruloyl esterase, an enzyme that releases ferulic acid (an antioxidant reactive towards free radicals such as reactive oxygen species) from polysaccharides esters. Dynamic light scattering, scanning electron microscopy with energy dispersive X-ray spectroscopy, UV–visible absorption spectroscopy, fluorescence spectroscopy, magnetic separation technique and enzyme catalytic assay confirmed the chemical composition of the gold covered superparamagnetic nanoparticles, the binding and activity of the enzyme onto the nanoparticles. Activity data in U/ml confirmed that the immobilized enzyme is approximately 2 times more active than the free enzyme in solution. Such particles can be directed with external magnetic fields for bio-separation and focused towards a medical target for therapeutical as well as bio-sensor applications.     

Deactivation of photocatalytically active ZnO nanoparticle and enhancement of its compatibility with organic compounds by surface-capping with organically modified silica

Tetraethyl orthosilicate (TEOS) and dimethyldiethoxysilane (DEDMS) were used as co-precursors to prepare organically modified silica (ormosil) via sol-gel process. The resultant ormosil was adopted for surface-capping of ZnO nanoparticle, where methyl (organic functional group) and silica (inorganic component) were simultaneously introduced onto the surface of the nanoparticles for realizing dual surface-modification. The ormosil-capped ZnO nanoparticle showed strong hydrophobicity and good compatibility with organic phases, as well as effectively decreased photocatalytic activity and almost unchanged ultraviolet (UV)-shielding ability. More importantly, the comprehensive properties of ormosil-capped ZnO nanoparticle could be manipulated by adjusting the molar ratio of TEOS to DEDMS during sol-gel process. This should help to open a wider window to better utilizing the unique and highly attractive properties such as high UV-shielding ability and high-visible light transparency of ZnO nanoparticle in sunscreen cosmetics.     

First-principles study on the Ni@Pt12 Ih core-shell nanoparticles: A good catalyst for oxygen reduction reaction

The adsorption, diffusion and dissociation properties of O₂ on the icosahedron (Ih) Ni@Pt12 core-shell nanoparticle were investigated using the ab initio density functional theory calculations. It is found that, compared with the Pt(111) surface, the Ih Ni@Pt12 core-shell nanoparticle can enhance the adsorption, diffusion and dissociation of O₂, as well as the adsorption and diffusion of the atomic O (the dissociation product of O₂), and therefore serve as a good catalyst for oxygen reduction reaction. Our study gives a reasonable theoretical explanation to the high catalytic activity of the Ni@Pt core-shell nanoparticles for the oxygen reduction reaction.     

Nanoparticles: Implication of Ligand Choice on Surface Properties,Crystal Structure,and Magnetic Properties of Iron Nanoparticles (Part. Part. Syst. Charact. 3/2013)

The behavior of iron nanoparticles is heavily influenced by their highly reactive surfaces. A better understanding of organic ligand/particle interactions must be achieved in order to synthesize iron nanoparticles with magnetic saturations (σ _sat) equivalent to bulk iron. Even when synthesized using careful, air‐free chemistry techniques and ligands more weakly interacting than those often reported in the literature, the magnetic saturation of iron nanoparticles generally only approaches, but not equals, the magnetic saturation of bulk iron. Here, iron nanoparticles are synthesized using Schlenk line chemistry methods and two different weakly interacting ligands: 2,4‐pentanedione and hexaethylene glycol monododecylether. These particles have saturation magnetizations slightly lower than bulk iron, which is believed to be caused by interactions between the passivating ligands and the surface of the nanoparticles. Using X‐ray absorption fine structure studies, it is shown that oxidized species of iron exist at the nanoparticles’ surface and can be attributed to iron/ligand interaction. The percentage of oxidized species scales with the surface to volume ratio of the nanoparticles, and therefore appears limited to the nanoparticle surface. X‐ray absorption fine structure analysis also shows that the nanoparticles have an expanded crystalline lattice, which can further impact their magnetic properties.     

Aerosol processing for nanomanufacturing

Advances in nanoparticle synthesis are opening new opportunities for a broad variety of technologies that exploit the special properties of matter at the nanoscale. To realize this potential will require the development of new technologies for processing nanoparticles, so as to utilize them in a manufacturing context. Two important classes of such processing technologies include the controlled deposition of nanoparticles onto surfaces, and the application of chemically specific coatings onto individual nanoparticles, so as to either passivate or functionalize their surfaces. This paper provides an overview of three technologies related to these objectives, with an emphasis on aerosol-based methods: first, the deposition of nanoparticles by hypersonic impaction, so as so spray-coat large areas with nanoparticles; second, the use of aerodynamic lenses to produce focused beams of nanoparticles, with beam widths of a few tens of microns, so as to integrate nanoparticle-based structures into microelectromechanical systems; and third, the coating of individual nanoparticles by means of photoinduced chemical vapor deposition (photo-CVD), driven by excimer lamps. We also discuss the combination of these technologies, so that nanoparticle synthesis, together with multiple processing steps, can be accomplished in a single flow stream.     

Covalent immobilization of invertase on PAMAM-dendrimer modified superparamagnetic iron oxide nanoparticles

In this study, polyamidoamine (PAMAM) dendrimer was synthesized on the surface of superparamagnetite nanoparticles to enhance invertase immobilization. The amount of immobilized enzyme on the surface-hyperbranched magnetite nanoparticle was up to 2.5 times (i.e., 250%) as much as that of magnetite nanoparticle modified with only amino silane. Maximum reaction rate (V _max) and Michaelis–Menten constant (K _m) were determined for the free and immobilized enzymes. Various characteristics of immobilized invertase such as; the temperature activity, thermal stability, operational stability, and storage stability were evaluated and results revealed that stability of the enzyme is improved upon immobilization.