From colloidal Co/CoO core/shell nanoparticles to arrays of metallic nanomagnets: surface modification and magnetic properties.

The magnetic properties of nanoparticles can be subject to strong variations as the chemical composition of the particle surface is modified. To study this interrelation of surface chemistry and magnetism, self-assembled layers of colloidal 9.5 nm Co/CoO core/shell nanoparticles were exposed to mild reactive hydrogen and oxygen plasmas. The consecutive oxygen/hydrogen plasma treatment transforms the particle layer into an array of metallic nanomagnets with complete reduction of the oxide and removal of the organic surfactants. The original arrangement of the particle array and the number of Co atoms per particle remains unchanged within the experimental error, and thus this is a possible route for the fabrication of ultrahigh-density magnetic bit structures from colloidal dispersions. The magnetic properties can be tuned by controlling the thickness of the surface oxide layer, which magnetically hardens the particles, as evidenced by element-specific magnetic hysteresis loops.     

Quantitative determination of surface silanol groups in silicagel by deuterium exchange combined with infrared spectroscopy and chemometrics

Concentration of silanol groups on silica gel surface has been quantitatively determined using the deuterium exchange method. Simple and effective procedures have been used in pre-sample drying, deuterium exchange and extraction of resulting isotopic mixture from the exchange reaction. Each of four silica gel samples with varying surface area has been subjected to pre-drying to remove adsorbed water and then quantitatively mixed with deuterium oxide in a steel bomb for isotopic exchange. The resulting D(2)O/water mixture was then extracted by applying high pressure using infrared pellet press. The infrared spectrum of the isotopic mixture was measured and the composition was then determined by a multivariate calibration model established between infrared profiles of water in D(2)O standard mixtures and their composition. The results show that the silanol group concentration determined agrees with the values reported in the literature.     

Small angle neutron scattering studies on nonaqueous dispersions of calcium carbonate Part 2. Determination of the form factor for concentric spheres

Colloidal dispersions of calcium carbonate, stabilised primarily by a surface active agent, in both toluene and dodecane have been examined by small angle neutron scattering. A model has been developed to simulate the scattering behaviour of the particles and is based on the idea of a concentric sphere with a homogeneous layer of adsorbed material surrounding a core particle. Computations based on the model show a wide variation of scattering behaviour with variation of the coherent scattering length of the dispersion medium. These predictions were confirmed by experiment. A method is described for analysis of the experimental data which leads to a determination of the thickness of the adsorbed layer, the radius of the core particle and the standard deviation of core particle radius.     

Preparation of ultrathin coating layers using surface modified silica nanoparticles

Silica nanoparticles are used in various applications including catalysts, paints and coatings. To reach an optimal performance via stability and functionality, in most cases, the surface properties of the particles are altered using complex procedures. Here we describe a simple method for surface modification of silica nanoparticles (SNP) using sequential adsorption of oppositely charged components. First, the SNPs were made cationic by adsorption of a cationic polyelectrolyte. Poly(allylamine hydrochloride) (PAH) and polyethyleneimine (PEI) were chosen as polycations to investigate the difference between a linear and a branched polyelectrolyte. Next, the dispersion of cationic SNPs was combined with an anionic alkyl ketene dimer (AKD) emulsion. Using this approach cationic, hydrophobic silica particle dispersions were produced. Dynamic light scattering, contact angle measurements and atomic force microscopy (AFM) were used for analyzing the particle and coating layer properties. The chosen polyelectrolyte affected the structure of the dispersion. The layer build-up was studied in detail using a quartz crystal microbalance with dissipation monitoring (QCM-D). The adsorption and layer properties of the cationic polyelectrolytes adsorbed on silica as well as the affinity of AKD to this layer were explored. The application possibilities of the modified particle dispersions were demonstrated by preparing paper and silica surfaces with tailored properties, such as elevated surface hydrophobicity, using an ultrathin coating layer.     

Silica nanoparticle crystals and ordered coatings using lys-sil and a novel coating device

Silica nanoparticles with a narrow particle size distribution and controlled diameters of 10-20 nm are synthesized via hydrolysis and hydrothermal aging of tetraethylorthosilicate in an aqueous L-lysine solution. Cryo-transmission electron microscopy (cryo-TEM) reveals that the silica nanoparticles assemble to form close-packed nanoparticle crystals over short length scales on carbon-coated grids. Evaporative drying of the same sols results in nanoparticle stability and remarkable long-range facile ordering of the silica nanoparticles over scales greater than 10 microm. Whereas small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS) discount the possibility of a core (silica)-shell (lysine) structure, the possibility remains for lysine occlusion within the silica nanoparticles and concomitant hydrogen bonding effects driving self-assembly. Facile ordering of the silica nanoparticles into multilayer and monolayer coatings over square-centimeter areas by evaporation-induced self-assembly is demonstrated using a novel dip-coating device.     

Elastic light scattering from nanoparticles by monochromatic vacuum-ultraviolet radiation

Elastic light scattering is reported using monochromatic vacuum-ultraviolet radiation to study free, spherical silica nanoparticles prepared by approaches from colloidal chemistry, with diameters between 100 and 240 nm. The colloidal nanoparticles of defined size are transferred from an aqueous solution into the gas phase using a particle beam experiment. After focusing of the particle beam by an aerodynamic lens, the scattered light from monochromatic synchrotron radiation is measured. Angle-resolved elastically scattered light is detected, showing a strong forward-scattering component. Additional evidence for the detection of elastically scattered light comes from plotting the scattered light intensity as a function of the dimensionless parameter qR, where q is the magnitude of the scattering wave vector and R is the particle radius. This yields different power-law regimes that are assigned to scattering from the surface and the bulk of the nanoparticles. Furthermore, there is evidence for modulations in the scattered light intensity as a function of scattering angle, which is clearly distinguished from the forward-scattering component. The experimental results are compared to Mie scattering simulations for isolated particles, yielding general agreement with the experimental results. Deviations from Mie simulations are observed for samples consisting of significant amounts of aggregates. The present results indicate that the optical properties of free nanoparticles are sensitively probed by vacuum-ultraviolet radiation.     

Improving hydrogen/deuterium exchange mass spectrometry by reduction of the back-exchange effect

The measurement of deuterium incorporation kinetics using hydrogen/deuterium (H/D) exchange experiments is a valuable tool for the investigation of the conformational dynamics of biomolecules in solution. Experiments consist of two parts when using H/D exchange mass spectrometry to analyse the deuterium incorporation. After deuterium incorporation at high D(2)O concentration, it is necessary to decrease the D(2)O concentration before the mass analysis to avoid deuterium incorporation under artificial conditions of mass spectrometric preparation and measurement. A low D(2)O concentration, however, leads to back-exchange of incorporated deuterons during mass analysis. This back-exchange is one of the major problems in H/D exchange mass spectrometry and must be reduced as much as possible. In the past, techniques using electrospray ionization (ESI) had the lowest back-exchange values possible in H/D exchange mass spectrometry. Methods for the measurement of H/D exchange by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) that have been developed since 1998 have some significant advantages, but they could not achieve the back-exchange minima of ESI methods. Here, we present a protocol for H/D exchange MALDI-MS which allows for greater minimization of back-exchange compared with H/D exchange ESI-MS under similar conditions.     

Conformationally driven gas-phase H/D exchange of dinucleotide negative ions

Gas-phase hydrogen/deuterium exchange of six deprotonated dinucleotides with CD(3)OD was performed in the second hexapole of a Fourier transform ion-cyclotron resonance (FTICR) mass spectrometer. To complete these experiments, dynamic simulations were carried out to investigate the different conformations adopted by the dinucleotides. In the experimental conditions and in integrating the experimental and theoretical results, H/D exchange was shown to be controlled by hydrogen accessibility and not by the chemical nature of the heteroatom bearing the exchangeable hydrogen. A model including simultaneous H/D exchanges at the experimental time scale was used to reproduce the dinucleotide H/D exchange kinetic plots. The relay mechanism was not relevant for dinucleotides. This allowed the H/D exchange rates to be directly linked to conformations.     

功能性硅烷在纳米氧化硅表面的自组装

在分散体系中,两种功能性硅烷,甲基丙烯酰氧丙基三甲基硅烷(MPTES)和氨丙基三甲基硅烷(APTES)在纳米氧化硅表面形成自组装单分子层,用XPS 和FTIR对所得自组装单分子层进行了表征.元素分析结果表明,所得功能性纳米氧化硅中的功能基含量分别为1.03 mmol/g甲基丙烯酰氧基/丙烯酰氧丙基纳米氧化硅(MPSN)和3.34 mmol/g氨基/氨丙基纳米氧化硅(APSN).LSS 分析结果表明,未修饰纳米氧化硅、 MPSN和APSN在甲苯分散体系中的平均流体力学直径大约分别为240、 45和560 nm.     

In situ small-angle X-ray scattering studies during the formation of polymer/silica nanocomposite particles in aqueous solution

This study is focused on the formation of polymer/silica nanocomposite particles prepared by the surfactant-free aqueous emulsion polymerization of 2,2,2-trifluoroethyl methacrylate (TFEMA) in the presence of 19 nm glycerol-functionalized aqueous silica nanoparticles using a cationic azo initiator at 60 °C. The TFEMA polymerization kinetics are monitored using ¹H NMR spectroscopy, while postmortem TEM analysis confirms that the final nanocomposite particles possess a well-defined core–shell morphology. Time-resolved small-angle X-ray scattering (SAXS) is used in conjunction with a stirrable reaction cell to monitor the evolution of the nanocomposite particle diameter, mean silica shell thickness, mean number of silica nanoparticles within the shell, silica aggregation efficiency and packing density during the TFEMA polymerization. Nucleation occurs after 10–15 min and the nascent particles quickly become swollen with TFEMA monomer, which leads to a relatively fast rate of polymerization. Additional surface area is created as these initial particles grow and anionic silica nanoparticles adsorb at the particle surface to maintain a relatively high surface coverage and hence ensure colloidal stability. At high TFEMA conversion, a contiguous silica shell is formed and essentially no further adsorption of silica nanoparticles occurs. A population balance model is introduced into the SAXS model to account for the gradual incorporation of the silica nanoparticles within the nanocomposite particles. The final PTFEMA/silica nanocomposite particles are obtained at 96% TFEMA conversion after 140 min, have a volume-average diameter of 216 ± 9 nm and contain approximately 274 silica nanoparticles within their outer shells; a silica aggregation efficiency of 75% can be achieved for such formulations.

SAXS is used to study the formation of polymer/silica nanocomposite particles prepared by surfactant-free aqueous emulsion polymerization of 2,2,2-trifluoroethyl methacrylate in the presence of silica nanoparticles using a azo initiator at 60 °C.     

ADSORPTION OF PROTEIN ON NANOPARTICLES

The adsorption of protein on nanoparticles was studied by using dynamic light scattering tomeasure the hydrodynamic size of both pure protein and nanoparticles adsorbed with differentamounts of protein. The thickness of the adsorbed protein layer increases as proteinconcentration, but decreases as the initial size of nanoparticles. After properly scaling thethickness with the initial diameter, we are able to fit all experimental data with a single mastercurve. Our experimental results suggest that the adsorbed proteins form a monolayer on thenanoparticle surface and the adsorbed protein molecules are attached to the particle surface atmany points through a possible hydrogen-bonding. Our results also indicate that as proteinconcentration increases, the overall shape of the adsorbed protein molecule continuously changesfrom a flat layer on the particle surface to a stretched coil extended into water. During thechange, the hydrodynamic volume of the adsorbed protein increases linearly with proteinconcentration.     

Interaction between blood plasma proteins and magnetite nanoparticles

Spin label EPR spectroscopy and dynamic and Rayleigh light scattering are employed to study the interaction between magnetite nanoparticles with a diameter of 17 nm and plasma proteins (fibrinogen and albumin). Protein molecules are shown to be adsorbed on nanoparticle surface with the formation of multilayer shells. When a buffer solution (pH 8.5) contains 0.01 vol % nanoparticles, 90–100 fibrinogen molecules are adsorbed per one particle and the thickness of an adsorbed layer is 30–40 nm. For albumin, the layer thickness is 10–15 nm. In a constant magnetic field, large linear microsized aggregates oriented parallel to field lines are formed in dispersions of nanoparticles covered with adsorbed protein molecules. The study of fibrin gel formation resulting from the action of thrombin enzyme on fibrinogen suggests that, in the presence of nanoparticles, the rate of gelation decreases by a factor of approximately two, while the ratio between the average mass and average length of fibrin polymer fibers rises.     

Biphasic synthesis of Au@SiO2 core-shell particles with stepwise ligand exchange

We report the synthesis of well-dispersed core-shell Au@SiO(2) nanoparticles with minimal extraneous silica particle growth. Agglomeration was suppressed through consecutive exchange of the stabilizing ligands on the gold cores from citrate to L-arginine and finally (3-mercaptopropyl)triethoxysilane. The result was a vitreophilic, stable gold suspension that could be coated with silica in a biphasic mixture through controlled hydrolysis of tetraethoxysilane under L-arginine catalysis. Unwanted condensation of silica particles without gold cores was limited by slowing the transfer across the liquid-liquid interface and reducing the concentration of the L-arginine catalyst. In-situ dynamic light scattering and optical transmission spectroscopy revealed the growth and dispersion states during synthesis. The resulting core-shell particles were characterized via dynamic light scattering, optical spectroscopy, and electron microscopy. Their cores were typically 19 nm in diameter, with a narrow size distribution, and could be coated with a silica shell in multiple steps to yield core-shell particles with diameters up to 40 nm. The approach was sufficiently controllable to allow us to target a shell thickness by choosing appropriate precursor concentrations.     

Isomeric differentiation of green tea catechins using gas-phase hydrogen/deuterium exchange reactions

Hydrogen/deuterium exchange reactions in a quadrupole ion trap mass spectrometer are used to differentiate galloylated catechin stereoisomers (catechin gallate and epicatechin gallate; gallocatechin gallate and epigallocatechin gallate) and the nongalloylated analogs (catechin and epicatechin, gallocatechin and epigallocatechin). Significant differences in the hydrogen/deuterium exchange behavior of the four pairs of deprotonated catechin stereoisomers are observed upon reaction with D(2)O. Interestingly, the nongalloylated catechins undergo H/D exchange to a much greater extent than the galloylated species, incorporating deuterium at both aromatic/allylic and active phenolic sites. Nongalloylated catechin isomers are virtually indistinguishable by their H/D exchange kinetics over a wide range of reaction times (0.05 to 10 s). Our experimental results are explained using high-level ab initio calculations to elucidate the subtle structural variations in the catechin stereoisomers that lead to their differing H/D exchange kinetics.     

Reversible uptake of water on NaCl nanoparticles at relative humidity below deliquescence point observed by noncontact environmental atomic force microscopy

The behavior of NaCl nanoparticles as a function of relative humidity (RH) has been characterized using non-contact environmental atomic force microscopy (e-AFM) to measure the heights of particles deposited on a prepared hydrophobic surface. Cubic NaCl nanoparticles with sides of 35 and 80 nm were found to take up water reversibly with increasing RH well below the bulk deliquescence relative humidity (DRH) of 75% at 23(°)C, and to form a liquid-like surface layer of thickness 2 to 5 nm, with measurable uptake (>2 nm increase in particle height) beginning at 70% RH. The maximum thickness of the layer increased with increasing RH and increasing particle size over the range studied. The liquid-like behavior of the layer was indicated by a reversible rounding at the upper surface of the particles, fit to a parabolic cross-section, where the ratio of particle height to maximum radius of curvature increases from zero (flat top) at 68% RH to 0.7 ± 0.3 at 74% RH. These observations, which are consistent with a reorganization of mass on the solid NaCl nanocrystal at RH below the DRH, suggest that the deliquescence of NaCl nanoparticles is more complex than an abrupt first-order phase transition. The height measurements are consistent with a phenomenological model that assumes favorable contributions to the free energy of formation of a liquid layer on solid NaCl due both to van der Waals interactions, which depend partly upon the Hamaker constant, A(film), of the interaction between the thin liquid film and the solid NaCl, and to a longer-range electrostatic interaction over a characteristic length of persistence, ξ; the best fit to the data corresponded to A(film)= 1 kT and ξ = 2.33 nm.     

A physico-chemical investigation of poly(ethylene oxide)-block-poly(L-lysine) copolymer adsorption onto silica nanoparticles

The adsorption behavior of poly(ethylene oxide)-b-poly(L-lysine) (PEO(113)-b-PLL(10)) copolymer onto silica nanoparticles was investigated in phosphate buffer at pH 7.4 by means of dynamic light scattering, zeta potential, adsorption isotherms and microcalorimetry measurements. Both blocks have an affinity for the silica surface through hydrogen bonding (PEO and PLL) or electrostatic interactions (PLL). Competitive adsorption experiments from a mixture of PEO and PLL homopolymers evidenced greater interactions of PLL with silica while displacement experiments even revealed that free PLL chains could desorb PEO chains from the particle surface. This allowed us to better understand the adsorption mechanism of PEO-b-PLL copolymer at the silica surface. At low surface coverage, both blocks adsorbed in flat conformation leading to the flocculation of the particles as neither steric nor electrostatic forces could take place at the silica surface. The addition of a large excess of copolymer favoured the dispersion of flocs according to a presumed mechanism where PLL blocks of incoming copolymer chains preferentially adsorbed to the surface by displacing already adsorbed PEO blocks. The gradual addition of silica particles to an excess of PEO-b-PLL copolymer solution was the preferred method for particle coating as it favoured equilibrium conditions where the copolymer formed an anchor-buoy (PLL-PEO) structure with stabilizing properties at the silica-water interface.     

A surface functional monomer-directing strategy for highly dense imprinting of TNT at surface of silica nanoparticles

This paper reports a surface functional monomer-directing strategy for the highly dense imprinting of 2,4,6-trinitrotoluene (TNT) molecules at the surface of silica nanoparticles. It has been demonstrated that the vinyl functional monomer layer of the silica surface can not only direct the selective occurrence of imprinting polymerization at the surface of silica through the copolymerization of vinyl end groups with functional monomers, but also drive TNT templates into the formed polymer shells through the charge-transfer complexing interactions between TNT and the functional monomer layer. The two basic processes lead to the formation of uniform core-shell TNT-imprinted nanoparticles with a controllable shell thickness and a high density of effective recognition sites. The high capacity and fast kinetics to uptake TNT molecules show that the density of effective imprinted sites in the nanoshells is nearly 5 times that of traditional imprinted particles. A critical value of shell thickness for the maximum rebinding capacity was determined by testing the evolution of rebinding capacity with shell thickness, which provides new insights into the effectiveness of molecular imprinting and the form of imprinted materials. These results reported here not only can find many applications in molecularly imprinting techniques but also can form the basis of a new strategy for preparing various polymer-coating layers on silica support.     

Hydrogen and deuterium atoms in amorphous ZrNi alloys

The local environment of hydrogen and deuterium atoms dissolved in amorphous alloys with the composition ZrNi and Zr₂Ni was studied using neutron inelastic scattering and neutron diffraction techniques. The frequency distribution functions exhibit a broad peak at about 130 meV. Interatomic DNi and DZr correlations are observed in the radial distribution function curves at correlation lengths of 1.7 Å and 2.1 Å respectively for both alloy compositions. It is concluded that the majority of hydrogen and deuterium atoms in the amorphous alloys are trapped at holes in the tetrahedra which consist of three or four zirconium atoms. The maximum hydrogen content per metal atom can be explained by assuming a statistical configuration of the metal atoms.     

Adsorption of lipid liquid crystalline nanoparticles: effects of particle composition, internal structure, and phase behavior

Controlling the interfacial behavior and properties of lipid liquid crystalline nanoparticles (LCNPs) at surfaces is essential for their application for preparing functional surface coatings as well as understanding some aspects of their properties as drug delivery vehicles. Here we have studied a LCNP system formed by mixing soy phosphatidylcholine (SPC), forming liquid crystalline lamellar structures in excess water, and glycerol dioleate (GDO), forming reversed structures, dispersed into nanoparticle with the surfactant polysorbate 80 (P80) as stabilizer. LCNP particle properties were controlled by using different ratios of the lipid building blocks as well as different concentrations of the surfactant P80. The LCNP size, internal structure, morphology, and charge were characterized by dynamic light scattering (DLS), synchrotron small-ange X-ray scattering (SAXS), cryo-transmission electron microscopy (cryo-TEM), and zeta potential measurements, respectively. With increasing SPC to GDO ratio in the interval from 35:65 to 60:40, the bulk lipid phase structure goes from reversed cubic micellar phase with Fd3m space group to reversed hexagonal phase. Adding P80 results in a successive shift toward more disorganized lamellar type of structures. This is also seen from cryo-TEM images for the LCNPs, where higher P80 ratios results in more extended lamellar layers surrounding the inner, more dense, lipid-rich particle core with nonlamellar structure. When put in contact with a solid silica surface, the LCNPs adsorb to form multilayer structures with a surface excess and thickness values that increase strongly with the content of P80 and decreases with increasing SPC:GDO ratio. This is reflected in both the adsorption rate and steady-state values, indicating that the driving force for adsorption is largely governed by attractive interactions between poly(ethylene oxide) (PEO) units of the P80 stabilizer and the silica surface. On cationic surface, i.e., silica modified with 3-aminopropltriethoxysilane (APTES), the slightly negatively charged LCNPs give rise to a very significant adsorption, which is relatively independent of LCNP composition. Finally, the dynamic thickness measurements indicate that direct adsorption of intact particles occurred on the cationic surface, while a slow buildup of the layer thickness with time is seen for the weakly interacting systems.     

Electrochemical modeling of the silica nanoparticle-biomembrane interaction

The interaction of amorphous colloidal silica (SiO(2)) nanoparticles of well-defined sizes with a dioleoyl phosphatidylcholine (DOPC) monolayer on a mercury (Hg) film electrode has been investigated. It was shown using electrochemical methods and microcalorimetry that particles interact with the monolayer, and the electrochemical data shows that the extent of interaction is inversely proportional to the particle size. Scanning electron microscopy (SEM) images of the electrode-supported monolayers following exposure to the particles shows that the nanoparticles bind to the DOPC monolayer irrespective of their size, forming a particle monolayer on the DOPC surface. A one-parameter model was developed to describe the electrochemical results where the fitted parameter is an interfacial layer thickness (3.2 nm). The model is based on the adsorptive interactions operating within this interfacial layer that are independent of the solution pH and solution ionic strength. The evidence implies that the most significant forces determining the interactions are van der Waals in character.