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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.

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.