Search

We report on the irradiation of gold rod–sphere assemblies with ultrashort laser pulses, producing structures that are very difficult to obtain by other methods. The optical response of these assemblies displays several peaks arising from the interaction of the plasmon modes of the individual particles, offering thus great flexibility to control the energy deposited on the individual particles. Judicious selection of the wavelength and fluence of the laser pulses allow fine control over the changes produced: the particles can be melted, welded and/or the organic links cleaved. In this way, it is possible to generate structures “à la carte” with a degree of control unmatched by other synthetic protocols. The method is exemplified with gold nanoparticles, but it can be easily implemented on particles composed of different metals, widening considerably the range of possibilities. The final structures are excellent candidates for surface-enhanced spectroscopies or plasmonic photothermal therapy as they have a very intense electric field located outside the structure, not in the gaps.

An essential element in the synthesis of nanomaterials based on gold nanoparticles comprises the control over parameters such as size, shape and composition, due to their strong influence on the properties of the particles. However, it is the coating material which often plays the primary role in tuning the size, morphology, and even plasmon resonance wavelength or mode multiplicity, as well as colloidal stability and functional versatility, ultimately determining the physical, chemical, optical, electronic and catalytic properties of the nanoparticles. Therefore, it is utterly important to select the adequate wet chemistry synthetic approach with the most suitable coating material for the preparation of gold nanoparticles with the desired requirements. Within this context, this review is focused on describing various types of organic and inorganic coating materials for gold nanoparticles that may notably affect their optical properties by either directly influencing the synthesis procedure or by changing their chemical and physical properties upon post-synthetic modifications, such that they exhibit novel and useful optical properties.

Wood is considered the most important renewable resource for a future sustainable bioeconomy. It is traditionally used in the building sector, where it has gained importance in recent years as a sustainable alternative to steel and concrete. Additionally, it is the basis for the development of novel bio-based functional materials. However, wood's sustainability as a green resource is often diminished by unsustainable processing and modification techniques. They mostly rely on fossil-based precursors and yield inseparable hybrids and composites that cannot be reused or recycled. In this article, we discuss the state of the art of environmental sustainability in wood science and technology. We give an overview of established and upcoming approaches for the sustainable production of wood-based materials. This comprises wood protection and adhesion for the building sector, as well as the production of sustainable wood-based functional materials. Moreover, we elaborate on the end of lifetime perspective of wood products. The concept of wood cascading is presented as a possibility for a more efficient use of the resource to increase its beneficial impact on climate change mitigation. We advocate for a holistic approach in wood science and technology that not only focuses on the material's development and production but also considers recycling and end of lifetime perspectives of the products. This article is part of the theme issue 'Bio-derived and bioinspired sustainable advanced materials for emerging technologies (part 1)'.

The splashing of liquid drops onto a solid surface is important for a wide range of applications, including combustion and spray coating. As the drop hits the solid surface, the liquid is ejected into a thin horizontal sheet expanding radially over the substrate. Above a critical impact velocity, the liquid sheet is forced to separate from the solid surface by the ambient air, and breaks up into smaller droplets. Despite many applications involving complex fluids, their effects on splashing remain mostly unexplored. Here we show that the splashing of a nanoparticle dispersion can be suppressed at higher impact velocities by the interactions of the nanoparticles with the solid surface. Although the dispersion drop first shows the classical transition from deposition to splashing when increasing the impact velocity, no splashing is observed above a second higher critical impact velocity. This result goes against the commonly accepted understanding of splashing, that a higher impact velocity should lead to even more pronounced splashing. Our findings open new possibilities to deposit large amount of complex liquids at high speeds.

Superstructures of gold nanospheres offer augmented surface-enhanced Raman scattering (SERS) activities beyond the limits of their individual building blocks. However, for application as reliable and quantitative colloidal SERS probes, some key aspects need to be considered to combine efficiency and robustness with respect to hotspot excitation, analyte adsorption, signal stability, and colloidal stability. For this purpose, we studied core/satellite superstructures with spherical cores as a simple optically isotropic model system. Superstructures of different core sizes were assembled using bovine serum albumin (BSA), which serves as a non-specific biomacromolecular linker and provides electrosteric stabilization. We show that the "noisy" spectral footprint of the protein coating may serve as an internal standard, which allows accurate monitoring of the adsorption kinetics of analytes. The SERS activity was quantified using 4-mercaptobenzoic acid (MBA) as an aromatic low-molecular-weight model analyte. The molar SERS efficiency was studied by variation of the particle (Au 0 ) and analyte concentrations with a limit of detection of 10 -7 M MBA. The practical importance of colloidal stability for robust measurement conditions was demonstrated by comparing the superstructures with their citrate-stabilized or protein-coated building blocks. We explain the theoretical background of hotspot formation by a leader/follower relationship of asymmetric control between the core and the satellites and give practical guidelines for robust colloidal SERS sensing probes.

Enzymes are often immobilized on solid supports to enable their recovery from reaction solutions, facilitate their reuse and hence increase cost-effectiveness in their application. Immobilized enzymes may even be used for flow-through applications in continuous processes. However, the synthesis of traditional immobilization scaffolds and immobilization techniques lack sustainability as they are often based on fuel-based materials and tedious synthesis- and immobilization approaches. Here, we present the natural material wood as a green alternative for enzyme immobilization. Its natural structure provides a mechanically stable porous scaffold with a high inner surface area that allows for directional flow-through of liquids. Enzymes were immobilized by nanoparticle-mediated adsorption, a simple, versatile and completely water-based process. The resulting wood-enzyme hybrids were intensely investigated for the model enzyme laccase. Reaction kinetics, as well as catalytic activities at various pH-values, temperatures, and ionic strengths were determined. The wood-enzyme hybrids could quickly and completely be removed from the reaction solution. Hence, they allow for multifold reusability. We show a series of 25 consecutive reaction cycles with a remaining activity in the last cycle of 90% of the maximal activity. Moreover, the anisotropic porosity of wood enabled the application of the hybrid material as a biocatalytic flow-through reactor. Flow-rate dependent productivity of a single-enzyme reaction was determined. Moreover, we show a two-step reaction cascade in continuous flow by the immobilization of the enzymes glucose oxidase and horseradish peroxidase. Therefore, the natural material wood proved to be a promising material for application in continuous-flow biocatalysis., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

In this study, we investigated charge inversion of protein-coated Au nanoparticles caused by the addition of metal ions. The addition of hydrolyzable metal ions (Lewis acids) can induce drastic pH changes and depending on this pH, the metal ions (e.g. M3+) are readily converted into the hydrolyzed species (MOH2+, M(OH)2+) or even into hydroxides (M(OH)3). Adsorbed metal hydroxides were identified to cause the charge inversion of the NPs by using a combination of cryo-TEM, EFTEM and ζ-potential measurements.

Silver nanomaterials (AgNMs) are released into sewers and consequently find their way to sewage treatment plants (STPs). The AgNMs are transformed en route, mainly into silver sulfide (Ag 2 S), which is only sparingly soluble in water and therefore potentially less harmful than the original AgNMs. Here we investigated the toxicity and fate of different sulfidized AgNMs using an exposure scenario involving the application of five different test materials (NM-300K, AgNO 3 , Ag 2 S NM-300K, Ag 2 S NM and bulk Ag 2 S) into a simulated STP for 10 days. The sewage sludge from each treatment was either dewatered or anaerobically digested for 35 days and then mixed into soil. We then assessed the effect on soil microorganisms over the next 180 days. After 60 days, a subsample of each test soil was used to assess chronic toxicity in oat plants (Avena sativa L) and a potential uptake into the plants. The effect of each AgNM on the most sensitive test organism was also tested without the application of sewage sludge. Although Ag sulfidized species are considered poorly soluble and barely bioavailable, we observed toxic effects on soil microorganisms. Furthermore, whether or not the AgNM was sulfidized before or during the passage through the STP, comparable effects were observed on ammonium oxidizing bacteria after sewage sludge application and incubation for 180 days. We observed the uptake of Ag into oat roots following the application of all test substances, confirming their bioavailability. The oat shoots generally containing less Ag than the roots., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

Aim: The current study was undertaken to evaluate the clinical efficacy of end-threaded intramedullary pinning for management of various long bone fractures in canines., Materials and Methods: This study was conducted in two phases, managing 25 client-owned dogs presented with different fractures. The technique of application of end-threaded intramedullary pinning in long bone fractures was initially standardized in 6 clinical patients presented with long bone fractures. In this phase, end-threaded pins of different profiles, i.e., positive and negative, were used as the internal fixation technique. On the basis of results obtained from standardization phase, 19 client-owned dogs clinically presented with different fractures were implanted with end-threaded intramedullary positive profile screw ended self-tapping pin in the clinical application phase., Results: The patients, allocated randomly in two groups, when evaluated postoperatively revealed slight pin migration in Group-I (negative profile), which resulted in disruption of callus site causing delayed union in one case and large callus formation in other two cases whereas no pin migration was observed in Group-II (positive profile). Other observations in Group-I was reduced muscle girth and delayed healing time as compared to Group-II. In clinical application, phase 21 st and 42 nd day post-operative radiographic follow-up revealed no pin migration in any of the cases, and there was no bone shortening or fragment collapse in end-threaded intramedullary positive profile screw ended self-tapping pin., Conclusion: The end-threaded intramedullary positive profile screw ended self-tapping pin used for fixation of long bone fractures in canines can resist pin migration, pin breakage, and all loads acting on the bone, i.e., compression, tension, bending, rotation, and shearing to an extent with no post-operative complications.

Within the last two decades, the field of nanomedicine has not developed as successfully as has widely been hoped for. The main reason for this is the immense complexity of the biological systems, including the physico-chemical properties of the biological fluids as well as the biochemistry and the physiology of living systems. The nanoparticles' physicochemical properties are also highly important. These differ profoundly from those of freshly synthesized particles when applied in biological/living systems as recent research in this field reveals. The physico-chemical properties of nanoparticles are predefined by their structural and functional design (core and coating material) and are highly affected by their interaction with the environment (temperature, pH, salt, proteins, cells). Since the coating material is the first part of the particle to come in contact with the environment, it does not only provide biocompatibility, but also defines the behavior (e.g. colloidal stability) and the fate (degradation, excretion, accumulation) of nanoparticles in the living systems. Hence, the coating matters, particularly for a nanoparticle system for biomedical applications, which has to fulfill its task in the complex environment of biological fluids, cells and organisms. In this review, we evaluate the performance of different coating materials for nanoparticles concerning their ability to provide colloidal stability in biological media and living systems., (Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.)

Enzyme-catalyzed controlled radical polymerization represents a powerful approach for the polymerization of a wide variety of water-soluble monomers. However, in such an enzyme-based polymerization system, the macromolecular catalyst (i.e., enzyme) has to be separated from the polymer product. Here, we present a compelling approach for the separation of the two macromolecular species, by taking the catalyst out of the molecular domain and locating it in the colloidal domain, ensuring quasi-homogeneous catalysis as well as easy separation of precious biocatalysts. We report on gold nanoparticles coated with horseradish peroxidase that can catalyze the polymerization of various monomers (e.g., N -isopropylacrylamide), yielding thermoresponsive polymers. Strikingly, these biocatalyst-coated nanoparticles can be recovered completely and reused in more than three independent polymerization cycles, without significant loss of their catalytic activity., Competing Interests: The authors declare no competing financial interest.

We present a bottom-up assembly route for a large-scale organization of plasmonic nanoparticles (NPs) into three-dimensional (3D) modular assemblies with core/satellite structure. The protein-assisted assembly of small spherical gold or silver NPs with a hydrophilic protein shell (as satellites) onto larger metal NPs (as cores) offers high modularity in sizes and composition at high satellite coverage (close to the jamming limit). The resulting dispersions of metal/metal nanoclusters exhibit high colloidal stability and therefore allow for high concentrations and a precise characterization of the nanocluster architecture in dispersion by small-angle X-ray scattering (SAXS). Strong near-field coupling between the building blocks results in distinct regimes of dominant satellite-to-satellite and core-to-satellite coupling. High robustness against satellite disorder was proved by UV/vis diffuse reflectance (integrating sphere) measurements. Generalized multiparticle Mie theory (GMMT) simulations were employed to describe the electromagnetic coupling within the nanoclusters. The close correlation of structure and optical property allows for the rational design of core/satellite nanoclusters with tailored plasmonics and well-defined near-field enhancement, with perspectives for applications such as surface-enhanced spectroscopies.

Citrate-stabilized gold nanoparticles (AuNP) agglomerate in the presence of hemoglobin (Hb) at acidic pH. The extent of agglomeration strongly depends on the concentration ratio [Hb]/[AuNP]. Negligible agglomeration occurs at very low and very high [Hb]/[AuNP]. Full agglomeration and precipitation occur at [Hb]/[AuNP] corresponding to an Hb monolayer on the AuNP. Ratios above and below this value lead to the formation of an unexpected phase: stable, microscopic AuNP-Hb agglomerates. We investigated the kinetics of agglomeration with dynamic light scattering and the adsorption kinetics of Hb on planar gold with surface-acoustic wave-phase measurements. Comparing agglomeration and adsorption kinetics leads to an explanation of the complex behavior of this nanoparticle-protein mixture. Agglomeration is initiated either when Hb bridges AuNP or when the electrostatic repulsion between AuNP is neutralized by Hb. It is terminated when Hb has been depleted or when Hb forms multilayers on the agglomerates that stabilize microscopic clusters indefinitely.

Copolymers of di(ethylene glycol) methyl ether methacrylate (x = MeO2MA) and oligo(ethylene glycol) methyl ether methacrylate (y = OEGMA) display lower critical solution phenomena in aqueous systems that are tunable by the copolymer ratio (x:y), ionic strength, and temperature. These properties enable tuning the hydrophobicity of macromolecular systems by variation of (x:y). For nanoparticles stabilized with these macromolecules, this provides a systematic approach to understanding the impact of surface chemistry, specifically hydrophobicity, on the equilibrium and transport properties of nanomaterials in biphasic systems. We synthesized a homologous series of gold nanoparticles capped by these copolymers, Au@(MeO2MA(x)-co-OEGMA(y)). By varying the copolymer 95:5 < (x:y) < 80:20 ratio, we studied the effect of surface hydrophobicity on the nanoparticle equilibrium adsorption isotherm and phase transfer at the aqueous-toluene interface. The increase in hydrophobicity from (x:y) = 80:20 to (x:y) = 95:5 is accompanied by an increase in the fractional coverage of the aqueous-toluene interface from f = 0.3 to f > 1, or multilayer adsorption and an increase in the characteristic adsorption timescale from τ(D) = 31 to τ(D) = 450 seconds. The equilibrium partition coefficient for the aqueous/toluene systems, K(T/W) is also a strong function of (x:y), increasing from K(T/W) (80:20) = 0.7 to K(T/W) (95:5) = 9.8. We also observed an increase in cellular uptake for increasing (x:y) suggesting that surface chemistry alone plays a significant role in intercellular transport processes.

In this work, we investigate the ligand exchange of cetyltrimethylammonium bromide (CTAB) with bovine serum albumin for gold nanorods. We demonstrate by surface-enhanced Raman scattering measurements that CTAB, which is used as a shape-directing agent in the particle synthesis, is completely removed from solution and particle surface. Thus, the protein-coated nanorods are suitable for bioapplications, where cationic surfactants must be avoided. At the same time, the colloidal stability of the system is significantly increased, as evidenced by spectroscopic investigation of the particle longitudinal surface plasmon resonance, which is sensitive to aggregation. Particles are stable at very high concentrations (cAu 20 mg/mL) in biological media such as phosphate buffer saline or Dulbecco's Modified Eagle's Medium and over a large pH range (2-12). Particles can even be freeze-dried (lyophilized) and redispersed. The protocol was applied to gold nanoparticles with a large range of aspect ratios and sizes with main absorption frequencies covering the visible and the near-IR spectral range from 600 to 1100 nm. Thus, these colloidally stable and surfactant-free protein-coated nanoparticles are of great interest for various plasmonic and biomedical applications.

We demonstrate the large-scale organisation of anisotropic nanoparticles into linear assemblies displaying optical anisotropy on macroscopic areas. Monodisperse gold nanorods with a hydrophilic protein shell are arranged by dip-coating on wrinkled surfaces and subsequently transferred to indium tin oxide (ITO) substrates by capillary transfer printing. We elucidate how tuning the wrinkle amplitude enables us to precisely adjust the assembly morphology and fabricate single, double and triple nanorod lines. For the single lines, we quantify the order parameter of the assemblies as well as interparticle distances from scanning electron microscopy (SEM) images. We find an order parameter of 0.97 and a mean interparticle gap size of 7 nm. This combination of close to perfect uni-axial alignment and close-packing gives rise to pronounced macroscopic anisotropic optical properties due to strong plasmonic coupling. We characterise the optical response of the assemblies on ITO-coated glass via UV/vis/NIR spectroscopy and determine an optical order parameter of 0.91. The assemblies are thus plasmonic metamaterials, as their periodicity and building block sizes are well below the optical wavelength. The presented approach does not rely on lithographic patterning and provides access to functional materials, which could have applications in subwavelength waveguiding, photovoltaics, and for large-area metamaterial fabrication.

We present ensembles of surface-ordered nanoparticle arrangements, which are formed by template-assisted self-assembly of monodisperse, protein-coated gold nanoparticles in wrinkle templates. Centimeter-squared areas of highly regular, linear assemblies with tunable line width are fabricated and their extinction cross sections can be characterized by conventional UV/vis/NIR spectroscopy. Modeling based on electrodynamic simulations shows a clear signature of strong plasmonic coupling with an interparticle spacing of 1-2 nm. We find evidence for well-defined plasmonic modes of quasi-infinite chains, such as resonance splitting and multiple radiant modes. Beyond elementary simulations on the individual chain level, we introduce an advanced model, which considers the chain length distribution as well as disorder. The step toward macroscopic sample areas not only opens perspectives for a range of applications in sensing, plasmonic light harvesting, surface enhanced spectroscopy, and information technology but also eases the investigation of hybridization and metamaterial effects fundamentally.

Anisotropic and hierarchical structures are bound in nature and highly desired in engineered materials, due to their outstanding functions and performance. Mimicking such natural features with synthetic materials and methods has been a highly active area of research in the last decades. Unlike these methods, we use the native biomaterial wood, with its intrinsic anisotropy and hierarchy as a directional scaffold for the incorporation of magnetic nanoparticles inside the wood material. Nanocrystalline iron oxide particles were synthesized in situ via coprecipitation of ferric and ferrous ions within the interconnected pore network of bulk wood. Imaging with low-vacuum and cryogenic electron microscopy as well as spectral Raman mapping revealed layered nanosize particles firmly attached to the inner surface of the wood cell walls. The mineralogy of iron oxide was identified by XRD powder diffraction and Raman spectroscopy as a mixture of the spinel phases magnetite and maghemite. The intrinsic structural architecture of native wood entails a three-dimensional assembly of the colloidal iron oxide which results in direction-dependent magnetic features of the wood-mineral hybrid material. This superinduced magnetic anisotropy, as quantified by direction-dependent magnetic hysteresis loops and low-field susceptibility tensors, allows for directional lift, drag, alignment, (re)orientation, and actuation, and opens up novel applications of the natural resource wood.

Functionalized nanoparticles can assist in stabilizing fluid-fluid interfaces; however, developing and applying the appropriate surface modification presents a challenge because successful application of these nanomaterials for biotechnological, food processing, and environmental applications requires their long-term stability in elevated ionic strength media. This work studies stimulus responsive polymeric materials based on random copolymers of di(ethylene glycol) methyl ether methacrylate (x = MeO2MA) and oligo(ethylene glycol) methyl ether methacrylate (y= OEGMA) which, when grafted to gold nanoparticles, show significant, tunable, colloidal stability. The nanoparticles Au@(MeO2MAx-co-OEGMAy) display tunable, reversible aggregation that is highly dependent on the (x:y) ratio and ionic strength. Effects of these parameters on the initial rate constant of aggregation (k11) are studied by time-resolved dynamic light scattering (TR-DLS) experiments. At the same nanoparticle concentration, a strong sensitivity to salt concentration is observed. Over less than 300 mM increase in NaCl concentration, we observed a two-order of magnitude increase in aggregation rate constants, 4.2 × 10(-20) < k11 < 1.8 × 10(-18) m(3)s(-1). Additionally, for the same gold nanoparticles, a higher fraction of OEGMA requires a higher salt concentration to induce aggregation. A linear relationship between the critical NaCl coagulation concentration (CCC) and the copolymer composition is observed. Analysis of the experimental data with an extended Derjaguin-Landau-Verwey-Overbeek (xDLVO) theory that includes hydration and osmotic forces is used to explain the stability of these systems. We find the hydration pressure, 2.4 < P(h,0) < 7.2 MPa, scales linearly both with the osmotic pressure and the OEGMA monomer concentration (5 < y < 20%). Specific knowledge of P(h,0)(y, C(NaCl)) enables design of both aggregation kinetics and stability as a function of the copolymer ratio and external stimuli.

Magnetic nanoparticles have emerged as important players in current research in modern medicine since they can be used in medicine for diagnosis and/or therapeutic treatment of diseases. Among many therapeutic applications of iron-based nanoparticles, drug delivery and photothermal therapy are of particular interest. At cellular level their uptake has been studied and the mechanism by which nanoparticles enter into the cell has important implication not only for their fate but also for their impact on the biological systems. We present here a dynamic investigation of interaction of biocompatible iron oxide nanoparticles coated with L-3,4-dihydroxyphenylalanine and labeled with tetra-methylrhodamine-5/6-isothiocyanate with lung epithelial cells. Our data show that after macropinocytosis-mediated internalization, nanoparticles in form of vesicles approach the nucleus and converge in the more acidic compartments of the cells in a microtubule-dependent manner. During progression the nanoparticles aggregate. Finally, we have demonstrated that a converging laser radiation on the cells, causes the increase in the local temperature and thus damages the cells, suggesting that these nanoparticles may be applied for photothermal therapy studies.

Here, we present a new microparticle system for the selective detection and magnetic removal of bacteria from contaminated solutions. The novelty of this system lies in the combination of a biocompatible scaffold reducing unspecific interactions with high capacity for bacteria binding. We apply highly porous poly(ethylene glycol) (PEG) microparticles and functionalize them, introducing both sugar ligands for specific bacteria targeting and cationic moieties for electrostatic loading of superparamagnetic iron oxide nanoparticles. The resulting magnetic, porous, sugar-functionalized (MaPoS) PEG microgels are able to selectively bind and discriminate between different strains of bacteria Escherichia coli . Furthermore, they allow for a highly efficient removal of bacteria from solution as their increased surface area can bind three times more bacteria than nonporous particles. All in all, MaPoS particles represent a novel generation of magnetic beads introducing for the first time a porous, biocompatible and easy to functionalize scaffold and show great potential for various biotechnological applications.

Polymer brushes on thiol-modified gold surfaces were synthesized by using terminal thiol groups for the surface-initiated free radical polymerization of methacrylic acid and dimethylaminoethyl methacrylate, respectively. Atomic force microscopy shows that the resulting poly(methacrylic acid) (PMAA) and poly(dimethylaminoethyl methacrylate) (PDMAEMA) brushes are homogeneous. Contact angle measurements show that the brushes are pH-responsive and can reversibly be protonated and deprotonated. Mineralization of the brushes with calcium phosphate at different pH yields homogeneously mineralized surfaces, and preosteoblastic cells proliferate on both the nonmineralized and mineralized surfaces. The number of living cells on the mineralized hybrid surfaces is ca. 3 times (PDMAEMA) and 10 times (PMAA) higher than on the corresponding nonmineralized brushes.

Insulin-capped gold nanoparticles (Au@insulin NPs) are highly sensitive towards pH and heavy metals, due to the protein coating. Au@insulin NPs aggregate and disaggregate reversibly with pH and in the presence of various heavy metal ions, which can be monitored through reversible changes in their optical properties. The sensitivity of the NPs towards different metal ions is dissimilar and depends on the coordinative properties of each specific metal ion, its valence number, concentration, and reaction time (kinetics), representing a simple tool for studying fundamental metal-protein interactions. Moreover, Au@insulin NPs are biocompatible and highly stable at high ionic strengths, due to their robust protein coating., (Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

The interfacial properties of Fe(3)O(4)@MEO(2)MA(90)-co-OEGMA(10) NPs, recently developed and described as promising nanotools for biomedical applications, have been investigated at the air/water interface. These Fe(3)O(4) NPs, capped with catechol-terminated random copolymer brushes of 2-(2-methoxyethoxy) ethyl methacrylate (MEO(2)MA) and oligo(ethylene glycol) methacrylate (OEGMA), with molar fractions of 90% and 10%, respectively, proved to be surface active. Surface tension measurements of aqueous dispersions of the NPs showed that the adsorption of the NPs at the air/water interface is time- and concentration-dependent. These NPs do not behave as classical amphiphiles. Once adsorbed at the air/water interface, they do not exchange with NPs in bulk, but they are trapped at the interface. This means that all NPs from the bulk adsorb to the interface until reaching maximum coverage of the interface, which corresponds to values between 6 × 10(-4) and 8 × 10(-4) mg/cm(2) and a critical equilibrium surface tension of ∼47 mN/m. Moreover, Langmuir layers of Fe(3)O(4)@MEO(2)MA(90)-co-OEGMA(10) NPs have been investigated by measuring surface pressure-area compression-expansion isotherms and in situ X-ray fluorescence spectra. The compression-expansion isotherms showed a plateau region above a critical surface pressure of ∼25 mN/m and a pronounced hysteresis. By using a special one-barrier Langmuir trough equipped with two surface pressure microbalances, we have shown that the NPs are squeezed out from the interface into the aqueous subphase, and they readsorb on the other side of the barrier. The results have been supported by TEM as well as AFM experiments of transferred Langmuir-Schaefer films on solid supports. This study shows the ability of Fe(3)O(4)@MEO(2)MA(90)-co-OEGMA(10) NPs to transfer from hydrophilic media (an aqueous solution) to the hydrophobic/hydrophilic interface (air/water interface) and back to the hydrophilic media. This behavior is very promising, opening studies of their ability to cross biological membranes.

Gold nanoparticles coated with oppositely charged polyelectrolytes, such as polyallylamine hydrochloride and polystyrenesulfonate, were examined for potential inhibition of prion protein aggregation and prion (PrPSc) conversion and replication. Different coatings, finishing with a positive or negative layer, were tested, and different numbers of layers were investigated for their ability to interact and reduce the accumulation of PrPSc in scrapie prion infected ScGT1 and ScN2a cells. The particles efficiently hampered the accumulation of PrPSc in ScN2a cells and showed curing effects on ScGT1 cells with a nanoparticle concentration in the picomolar range. Finally, incubation periods of prion-infected mice treated with nanomolar concentrations of gold nanoparticles were significantly longer compared to untreated controls.

The use of magnetic nanoparitilces for biological and biomedical applications such as protein separation, targeted drug delivery, hyperthermia treatment, use as contrast agents of magnetic resonance imaging, biosensing, magnetic fluids environmental remediation is one of the most attractive fields of nanotechnology today because of their unique magnetic properties and the potential to function at cellular and molecular level of biological interactions. To apply them in biological fluids or aqueous environment it is essential to modulate the chemical nature of magnetic nanoparticle surfaces to increase their water solubility and colloidal stability in aqueous medium. By employing different coating technologies they cannot only be rendered longterm stable in biological fluids but also functionalized to fulfill different tasks, like molecular targeting or linking of therapeutic agents. To achieve this goal different polymeric coatings are applied to provide solubility and stability in aqueous solution and additional functional groups for attachment. Taken together the versatile modifications described in this review improved the ability to specifically tailor the features and properties of magnetic nanoparticles for biomedical applications.

The self-organization of random copolymers composed of a nucleobase monomer (either 1-(4-vinylbenzyl)thymine or 9-(4-vinylbenzyl)adenine) and dodecyl methacrylate (DMA) was studied in dilute chloroform solutions. The balance between the molar fractions of the nucleobase monomer (leading to intermolecular H-bonding) and DMA (soluble moiety in chloroform) in the polymer chains was found to be the parameter that principally influences the self-organization. DMA-rich copolymers are molecularly soluble in chloroform, whereas nucleobase-rich copolymers are insoluble in this solvent. Copolymers possessing an equimolar comonomer composition self-assemble into micrometer-sized particles physically cross-linked by intermolecular H-bonds (either thymine-thymine or adenine-adenine interactions, depending on the studied copolymer). Nevertheless, when mixed together, thymine- and adenine-based colloids fuse into thermodynamically stable microspheres cross linked by adenine-thymine interactions.

Since the layer-wise polyelectrolyte deposition offers the opportunity to modify surfaces for biomedical applications, interactions and toxicity between polyelectrolytes and living cells become interesting. The aim of the present work is to determine the different factors such as contact area, charge, and transplantation site that influence the cell reaction to a specific polymer. We found that toxicity is influenced by all these factors and cannot be tested easily in a model.