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Given the inherent performance limitations of intercalation‐based lithium‐ion batteries, solid‐state conversion batteries are promising systems for future energy storage. A high specific capacity and natural abundancy make iron disulfide (FeS2) a promising cathode‐active material. In this work, FeS2 nanoparticles were prepared solvothermally. By adjusting the synthesis conditions, samples with average particle diameters between 10 nm and 35 nm were synthesized. The electrochemical performance was evaluated in solid‐state cells with a Li‐argyrodite solid electrolyte. While the reduction of FeS2 was found to be irreversible in the initial discharge, a stable cycling of the reduced species was observed subsequently. A positive effect of smaller particle dimensions on FeS2 utilization was identified, which can be attributed to a higher interfacial contact area and shortened diffusion pathways inside the FeS2 particles. These results highlight the general importance of morphological design to exploit the promising theoretical capacity of conversion electrodes in solid‐state batteries., Particle‐size reduction of iron sulfide nanoparticles improves its performance as an active material in solid‐state conversion cathodes: For reduced particle dimensions, the electrochemical utilization of FeS2 is increased. The potential of FeS2 as an electrode in solid‐state batteries is highlighted and the importance of the morphological design of battery materials is underscored.

Localized surface plasmon resonance properties in unconventional materials like metal oxides or chalcogenide semiconductors have been studied for use in signal detection and analysis in biomedicine and photocatalysis. We devised a selective synthesis of the tungsten oxides WO3-x and (NH4)xWO3 with tunable plasmonic properties. We selectively synthesized WO3-x nanorods with different aspect ratios and hexagonal tungsten bronzes (NH4)xWO3 as truncated nanocubes starting from ammonium metatungstate (NH4)6H2W12O40·xH2O. Both particles form from the same nuclei at temperatures >200 °C; monomer concentration and surfactant ratio are essential variables for phase selection. (NH4)xWO3 was the preferred reaction product only for fast heating rates (25 K min-1), slow stirring speeds (∼150 rpm) and high precursor concentrations. A proton nuclear magnetic resonance (1H-NMR) spectroscopic study of the reaction mechanism revealed that oleyl oleamide, formed from oleic acid and oleylamine upon heating, is a key factor for the selective formation of WO3-x nanorods. Since oleic acid and oleylamine are standard surfactants for the wet chemical synthesis of many metal and oxide nanoparticles, the finding that oleyl oleamide acts as a chemically active reagent above 250 °C may have implications for many nanoparticle syntheses. Oriented attachment of polyoxotungstate anions is proposed as a model to rationalize phase selectivity. Magic angle spinning (MAS) 1H-NMR and powder X-ray diffraction (PXRD) studies of the bronze after annealing under (non)inert conditions revealed an oxidative phase transition. WO3-x and (NH4)xWO3 show a strong plasmon absorption for near infra-red light between 800 and 3300 nm. The maxima of the plasmon bands shift systematically with the nanocrystal aspect ratio.

Thermal decomposition is a promising route for the synthesis of metal oxide nanoparticles because size and morphology can be tuned by minute control of the reaction variables. We synthesized CoO nanooctahedra with diameters of ∼48 nm and a narrow size distribution. Full control over nanoparticle size and morphology could be obtained by controlling the reaction time, surfactant ratio, and reactant concentrations. We show that the particle size does not increase monotonically with time or surfactant concentration but passes through minima or maxima. We unravel the critical role of the surfactants in nucleation and growth and rationalize the observed experimental trends in accordance with simulation experiments. The as-synthesized CoO nanooctahedra exhibit superior electrocatalytic activity with long-term stability during oxygen evolution. The morphology of the CoO particles controls the electrocatalytic reaction through the distinct surface sites involved in the oxygen evolution reaction.

Preventing bacterial adhesion on materials surfaces is an important problem in marine, industrial, medical and environmental fields and a topic of major medical and societal importance. A defense strategy of marine organisms against bacterial colonization relies on the biohalogenation of signaling compounds that interfere with bacterial communication. These reactions are catalyzed by haloperoxidases, a class of metal-dependent enzymes, whose activity can be emulated by ceria nanoparticles. The enzyme-like activity of ceria was enhanced by a factor of 3 through bismuth substitution (Ce1−xBixO2−δ). The solubility of Bi3+ in CeO2 is confined to the range 0 < x < 0.25 under quasi-hydrothermal conditions. The Bi3+ cations are located close to the nanoparticle surface because their ionic radii are larger than those of the tetravalent Ce4+ ions. The synthesis of Ce1−xBixO2−δ (0 < x < 0.25) nanoparticles was upscaled to yields of ∼50 g. The halogenation activity of Ce1−xBixO2−δ was demonstrated with phenol red assays. The maximum activity for x ≈ 0.2 is related to the interplay of the ζ-potential of surface-engineered Ce1−xBixO2−δ nanoparticles and their BET surface area. Ce0.80Bi0.20O1.9 nanoparticles with optimized activity were incorporated in polyethersulfone beads, which are typical constituents of water filter membrane supports. Although Ce1−xBixO2−δ nanoparticles are not bactericidal on their own, naked Ce1−xBixO2−δ nanoparticles and polyethersulfone/Ce1−xBixO2−δ nanocomposites showed a strongly reduced bacterial coverage. We attribute the decreased adhesion of the Gram-negative soil bacterium Pseudomonas aeruginosa and of Phaeobacter gallaeciensis, a primary bacterial colonizer in marine biofilms, to the formation of halogenated signaling compounds. No biocides are needed, H2O2 (formed in daylight) and halide are the only substrates required. The haloperoxidase-like activity of Ce1−xBixO2−δ may be a promising starting point for the development of environmentally friendly, “green” nanocomposites, when the use of conventional biocides is prohibited.

The predicted global cancer burden is expected to surpass 20 million new cancer cases by 2025. Despite recent advancement in tumor therapy, a successful cancer treatment remains challenging. The emerging field of nanotechnology offers great opportunities for diagnosis, imaging, as well as treatment of cancer. Zinc oxide nanoparticles (ZnO NP) were shown to exert selective cytotoxicity against tumor cells via a yet unknown mechanism, most likely involving the generation of reactive oxygen species (ROS). These nanoparticles are a promising therapeutic opportunity as zinc is a nontoxic trace element and its application in medically-related products is considered to be safe. We could show that ZnO NP can exert cytotoxic effects on several human tumor cell lines. There can be found ZnO NP concentrations which selectively damage tumor cells while human fibroblasts do not sustain lasting damage. Cytotoxicity is attributable to the release of zinc ions from the nanoparticles outside the cells as well as to a direct cell-nanoparticle interaction. This involves uptake of the particles into the tumor cells. With a silica shell the cytotoxicity can be delayed which can help in the future for a safe transport in the blood stream. Cellular damage finally cumulates in apoptotic cell death via zinc overload within 48 h after treatment with ZnO NP. A therapeutical perspective could be the targeted accumulation of ZnO NP at the tumor side to induce local zinc overload that substantially damages the tumor cells with no or low side effects. We suggest further studies to explore the potential of ZnO NP as an innovative anti-tumor agent.

Cerium oxide nanoparticles (CeNPs) have been shown to exhibit antioxidant capabilities, but their efficiency in scavenging reactive oxygen species (ROS) and the underlying mechanisms are not yet well understood. In this study, cerium dioxide nanoparticles (CeNPs) and nanorods (CeNRs) were found to exhibit much stronger scavenging activity than ·OH generation in phosphate buffered saline (PBS) and surrogate lung fluid (SLF). The larger surface area and higher defect density of CeNRs may lead to higher ·OH scavenging activity than for CeNPs. These insights are important to understand the redox activity of cerium nanomaterials and provide clues to the role of CeNPs in biological and environmental processes.

Plant extract of Pulicaria undulata (L.) was used as both reducing agent and stabilizing ligand for the rapid and green synthesis of gold (Au), silver (Ag), and gold&ndash, silver (Au&ndash, Ag) bimetallic (phase segregated/alloy) nanoparticles (NPs). These nanoparticles with different morphologies were prepared in two hours by stirring corresponding metal precursors in the aqueous solution of the plant extracts at ambient temperature. To infer the role of concentration of plant extract on the composition and morphology of NPs, we designed two different sets of experiments, namely (i) low concentration (LC) and (ii) high concentration (HC) of plant extract. In the case of using low concentration of the plant extract, irregular shaped Au, Ag, or phase segregated Au&ndash, Ag bimetallic NPs were obtained, whereas the use of higher concentrations of the plant extract resulted in the formation of spherical Au, Ag, and Au&ndash, Ag alloy NPs. The as-prepared Au, Ag, and Au&ndash, Ag bimetallic NPs showed morphology and composition dependent catalytic activity for the reduction of 4-nitrophenol (4-NPh) to 4-aminophenol (4-APh) in the presence of NaBH4. The bimetallic Au&ndash, Ag alloy NPs showed the highest catalytic activity compared to all other NPs.

A facile and chemical specific method to synthesize highly reduced graphene oxide (HRG) and Pd (HRG@Pd) nanocomposite is presented. The HRG surfaces are tailored with amine groups using 1-aminopyrene (1-AP) as functionalizing molecules. The aromatic rings of 1-AP sit on the basal planes of HRG through π–π interactions, leaving amino groups outwards (similar like self-assembled monolayer on 2D substrates). The amino groups provide the chemically specific binding sites to the Pd nucleation which subsequently grow into nanoparticles. HRG@Pd nanocomposite demonstrated both uniform distribution of Pd nanoparticles on HRG surface as well as excellent physical stability and dispersibility. The surface functionalization was confirmed using, ultraviolet–visible (UV–Vis), Fourier transform infra-red and Raman spectroscopy. The size and distribution of Pd nanoparticles on the HRG and crystallinity were confirmed using high-resolution transmission electron microscopy and powder X-ray diffraction and X-ray photoelectron spectroscopy. The catalytic efficiency of highly reduced graphene oxide-pyrene-palladium nanocomposite (HRG-Py-Pd) is tested towards the Suzuki coupling reactions of various aryl halides. The kinetics of the catalytic reaction (Suzuki coupling) using HRG-Py-Pd nanocomposite was monitored using gas chromatography (GC).

The importance of zinc as a trace metal in the human body has long been overlooked. We now gradually discover that the impact of zinc on the health of our body might be as far-reaching as that of iron. Concurrently, nanomaterials containing zinc, in particular zinc oxide nanoparticles (ZnO NPs), are becoming increasingly attractive as innovative agents for medical applications. Zinc oxide is characterized by a good biocompatibility which allows the exploitation of its antibacterial, antifungal, antiviral, and anti-cancer qualities in a therapeutic setting. This perspective outlines the current state of knowledge concerning the interaction of zinc oxide nanoparticles with eukaryotic cells and the human body. Furthermore, it sheds light on the importance of zinc under physiological conditions. This helps to place the in vivo behavior of zinc oxide nanoparticles in the proper context. We evaluate the potential of zinc oxide nanoparticles as innovative anti-tumor agents by summarizing important results of current studies in this field and discuss the proposed mechanisms that give zinc oxide nanoparticles a selective toxicity for tumor cells.

Biomimetic materials have been gaining increasing importance for use as bone biomaterials, because they may provide regenerative alternatives for the use of autologous tissues for bone regeneration. We demonstrate a promising alternative for the use of biomimetic materials based on a biodegradable PEG hydrogel loaded with vaterite nanoparticles as mineral storage. Vaterite, the least stable CaCO3 polymorph, is stable enough to ensure the presence of a potential ion buffer for bone regeneration, but still has sufficient reactivity for the transformation from CaCO3 to hydroxyapatite (HA). A combination of powder X-ray diffraction (PXRD), electron microscopy, and Fourier-transform infrared (FT-IR) and Raman spectroscopy showed the transformation of vaterite nanoparticles incorporated in a PEG-acetal-DMA hydrogel to hydroxycarbonate apatite (HCA) crystals upon incubation in simulated body fluid at human body temperature within several hours. The transformation in the PEG-acetal-DMA hydrogel scaffold in simulated body fluid or phosphate saline buffer proceeded significantly faster than for free vaterite. The vaterite-loaded hydrogels were free of endotoxin and did not exhibit an inflammatory effect on endothelial cells. These compounds may have prospects for future applications in the treatment of bone defects and bone degenerative diseases.

Controlling the morphology of noble-metal nanoparticles is mandatory to tune specific properties such as catalytic and optical behavior. Heterodimers consisting of two noble metals have been synthesized, so far mostly in aqueous media using selective surfactants or chemical etching strategies. We report a facile synthesis for Au@Pd and Pd@Au heterodimer nanoparticles (NPs) with morphologies ranging from segregated domains (heteroparticles) to core-shell structures by applying a seed-mediated growth process with Au and Pd seed nanoparticles in 1-octadecene (ODE), which is a high-boiling organic solvent. The as-synthesized oleylamine (OAm) functionalized Au NPs led to the formation of OAm-Au@Pd heteroparticles with a "windmill" morphology, having an Au core and Pd "blades". The multiply twinned structure of the Au seed particles (⌀ ≈ 9-11 nm) is associated with a reduced barrier for heterogeneous nucleation. This leads to island growth of bimetallic Au@Pd heteroparticles with less-regular morphologies. The reaction process can be controlled by tuning the surface chemistry with organic ligands. Functionalization of Au NPs (Ø ≈ 9-11 nm) with 1-octadecanethiol (ODT) led to the formation of ODT-Au@Pd NPs with a closed Pd shell through a strong ligand-metal binding, which is accompanied by a redistribution of the electron density. Experiments with varied Pd content revealed surface epitaxial growth of Pd on Au. For OAm-Pd and ODT-Pd seed particles, faceted, Au-rich domain NPs and impeded core-shell NPs were obtained, respectively. This is related to the high surface energy of the small Pd seed particles (⌀ ≈ 5-7 nm). The metal distribution of all bimetallic NPs was analyzed by extended (aberration-corrected) transmission electron microscopy (HR-TEM, HAADF-STEM, EDX mapping, ED). The Au and Pd NPs, as well as the ODT-Au@Pd and OAm-Pd@Au heteroparticles, catalyze the reduction of 4-nitrophenol to 4-aminophenol with borohydride. The catalytic activity is dictated by the particle structure. OAm-Au@Pd heteroparticles with faceted Au domains had the highest activity because of a mixed Au-Pd surface structure, while ODT-Au@Pd NPs, where the active Au core is covered by a Pd shell, had the lowest activity.

Surface functionalization of nanoparticles (NPs) plays a crucial role in particle solubility and reactivity. It is vital for particle nucleation and growth as well as for catalysis. This raises the quest for functionalization efficiency and new approaches to probe the degree of surface coverage. We present an (in situ) proton nuclear magnetic resonance (1H NMR) study on the ligand exchange of oleylamine by 1-octadecanethiol as a function of the particle size and repeated functionalization on Au NPs. Ligand exchange is an equilibrium reaction associated with Nernst distribution, which often leads to incomplete surface functionalization following “standard” literature protocols. Here, we show that the surface coverage with the ligand depends on the (i) repeated exchange reactions with large ligand excess, (ii) size of NPs, that is, the surface curvature and reactivity, and (iii) molecular size of the ligand. As resonance shifts and extensive line broadening during and after the ligand exchange impede the ev...

Multicomponent nanostructures containing purely organic or inorganic as well as hybrid organic–inorganic components connected through a solid interface are, unlike conventional spherical particles, able to combine different or even incompatible properties within a single entity. They are multifunctional and resemble molecular amphiphiles, like surfactants or block copolymers, which makes them attractive for the self-assembly of complex structures, drug delivery, bioimaging, or catalysis. We have synthesized Pd@FexO heterodimer nanoparticles (NPs) to fabricate a macroporous, hydrophobic, magnetically active, three-dimensional (3D), and template-free hybrid foam capable of repeatedly separating oil contaminants from water. The Pd domains in the Pd@FexO heterodimers act as nanocatalysts for the hydrosilylation of polyhydrosiloxane and tetravinylsilane, while the FexO component confers magnetic properties to the final functional material. Pd@FexO heterodimers were synthesized by heterogeneous nucleation and g...

Layered transition metal dichalcogenides contain a number of crystal defects which significantly change their properties may be beneficial or detrimental for a specific application. We have prepared defect-rich multiwalled WS2 nanotubes by reductive sulfidization of W18O49 nanowires that were obtained solvothermally from tungsten chloride in different alcohols. The synthesis of the W18O49 nanowires was monitored and their morphological characteristics (e. g. length, rigidity and aspect ratio) are described in detail. The effect of morphology of the nanowires on the synthesis of WS2 nanotubes was investigated in order to obtain WS2 nanotubes that are highly solvent dispersible. Dispersions of the WS2 nanotubes in organic solvents were very stable for several days. The nanotubes could easily be functionalized with noble metals, metal oxides and Janus-type metal@metal oxide nanoparticles. The synthesis of nanowires and nanotubes and the immobilization of the nanoparticles is demonstrated by transmission electron microscopy (TEM), high resolution transmission electron microscopy (HRTEM) combined with energy dispersive X-ray spectroscopy (EDX), electron diffraction, X-ray diffraction (XRD) and Raman spectroscopy.

Here, we present the surface functionalization of anisotropic in form ferri-magnetic Fe3O4-nanorods (NRs) with a diblock copolymer, having a PMMA- or PDEGMEMA-block, for solubilization, and a dopamine anchor block. These polymers were synthesized through RAFT polymerization via a macro-initiator approach. The successful surface functionalization, performed via a grafting-to method, was monitored using TGA, IR and TEM measurements. The NRs were very soluble in organic solvents after functionalization. Afterwards, the liquid crystalline (LC) behavior was investigated. During solvent evaporation, birefringent domains were formed. The self-assembly into lyotropic LC structures could be observed with PEG 400 as a non-evaporating solvent. Thereby the anisotropic in form NRs aligned themselves along a director without the loss of mobility, as observed in POM, TEM and SEM images. Magnetic fields have a strong influence on the LC phases formed. They not only lead to macroscopic orientation, but also to phase separation into highly concentrated LC phases and an isotropic phase, mostly free of NRs. This can be reversed by demagnetizing the nanoparticles. We also investigated PDEGMEMA-functionalized NRs with excess PDEGMEMA polymer as solvent, and liquid crystalline phases were also observed.

This work deals with the toughening effect of inorganic, fullerene-like WS2 (IF-WS2) nanoparticles (NPs) on epoxy. It has been hypothesized that this toughening effect depends on the epoxy’s cross-link density, its molecular defect fraction or its reference fracture toughness K Ic . Seven different epoxy systems were filled with 0.5% laboratory-made IF-WS2 NPs by mass and investigated in order to analyze which material properties are determining the toughening effect. These NPs were similar to commercially available IF-WS2 NPs, but their agglomerates could not be broken up as successfully and they yielded less toughening effect. The cross-link density of the epoxies measured via dynamic-mechanical thermal analysis agreed reasonably well qualitatively with the theoretical estimation. The glass-transition temperature and the compressive yield stress were not affected significantly by the IF-WS2 NPs. The toughening effect of IF-WS2 depended entirely on the curing agent type and quantity. Polyetheramine-cured epoxies behaved differently from the others in their yielding behavior, but also in the IF-WS2 NPs’ toughening effect: While some of the investigated material properties correlate strongly with the toughening effect for polyetheramine-cured epoxies, the correlation for all investigated epoxies is rather low. Thus, none of the mentioned hypotheses could be clearly confirmed.

Polymers with nanoparticle inclusions are attractive materials because physical properties can be tuned by varying size and volume fraction range. However, elastic behavior can degrade at higher inclusion fractions when particle-particle contacts become important, and sophisticated measurement techniques are required to study this crossover. Here, we report on the mechanical properties of materials with BaTiO3 nanoparticles (diameters

A general method to carry out the fluorination of metal oxides with poly(tetrafluoroethylene) (PTFE, Teflon) waste by spark plasma sintering (SPS) on a minute scale with Teflon is reported. The potential of this new approach is highlighted by the following results. i) The tantalum oxyfluorides Ta3 O7 F and TaO2 F are obtained from plastic scrap without using toxic or caustic chemicals for fluorination. ii) Short reaction times (minutes rather than days) reduce the process time the energy costs by almost three orders of magnitude. iii) The oxyfluorides Ta3 O7 F and TaO2 F are produced in gram amounts of nanoparticles. Their synthesis can be upscaled to the kg range with industrial sintering equipment. iv) SPS processing changes the catalytic properties: while conventionally prepared Ta3 O7 F and TaO2 F show little catalytic activity, SPS-prepared Ta3 O7 F and TaO2 F exhibit high activity for photocatalytic oxygen evolution, reaching photoconversion efficiencies up to 24.7% and applied bias to photoconversion values of 0.86%. This study shows that the materials properties are dictated by the processing which poses new challenges to understand and predict the underlying factors.

In our present work we developed a novel graphene wrapping approach of Ni@Fe2O3 superparticles, which can be extended as a concept approach for other nanomaterials as well. It uses sulfonated reduced graphene oxide, but avoids thermal treatments and use of toxic agents like hydrazine for its reduction. The modification of graphene oxide is achieved by the introduction of sulfate groups accompanied with reduction and elimination reactions, due to the treatment with oleum. The successful wrapping of nanoparticles is proven by energy dispersive X-ray spectroscopy, high-resolution transmission electron microscopy and Raman spectroscopy. The developed composite material shows strongly improved performance as anode material in lithium-ion batteries (compared to unwrapped Ni@Fe2O3) as it offers a reversible capacity of 1051 mA h g−1 after 40 cycles at C/20, compared with 460 mA h g−1 for unwrapped Ni@Fe2O3. The C rate capability is also improved by the wrapping approach, as specific capacities for wrapped particles are about twice of those offered by unwrapped particles. Additionally, the benefit for the use of the advanced superparticle morphology is demonstrated by comparing wrapped Ni@Fe2O3 particles with wrapped Fe2O3 nanorice.

Superoxide radicals are associated with the development of many severe diseases, such as cancer. Under nonpathogenic conditions, the natural enzyme superoxide dismutase (SOD) regulates the intracellular superoxide concentrations, but nearly all tumor tissues show reduced SOD levels. Selective imaging in early progression stages remains a key requirement for efficient cancer diagnosis and treatment. Magnetic resonance imaging (MRI) as a noninvasive tool with high spatial resolution may offer advantages here, but MRI contrast agents exhibiting a redox-triggered change in the image contrast towards superoxide radicals have not been reported so far. Here we show that manganese oxide (MnO) nanoparticles (NPs) exhibit an intrinsic SOD-like activity, which is higher than that of the native Mn-dependent SOD. In addition, MnO NPs significantly enhance the MRI contrast when exposed to superoxide radicals, making them responsive MRI contrast agents for the treatment and imaging of cancer cells with reduced SOD levels.

Proteins show remarkable versatility as multifunctional materials for therapeutic applications. They can be easily modified with the toolkit of bioorganic chemistry and are particularly attractive because of their degradability and biocompatibility. Herein, we evaluate different methods for the attachment of multiple PEG chains on the surface of the enzyme lysozyme. For this, we activated standard 2 kDa mPEG chains with four different electrophilic groups and tested their ability to react with different amino acids on the surface of our model protein. The aim was to find an effective and at the same time mild modification method that preserves the native structure and activity of the enzyme. The amphiphilic properties of PEG induce a solubility switch of the protein material which allows the formation of nanoparticles using a nano-emulsion technique in the size range of 100–130 nm. We found that, even though all produced materials are soluble in organic solvents, the amount of introduced PEG chains and the enzyme activity significantly vary depending on the chosen PEGylation method.

A longstanding goal of biomimetic chemistry is the design and synthesis of functional enzyme mimics. The past three decades have seen a wide variety of materials, including metal complexes, polymers and other biomolecules, that mimic the structures and functions of naturally occurring enzymes. Among these, inorganic nanoparticles offer huge potential, because they are more stable than their natural counterparts, while having large surface areas and sizes comparable to those of natural enzymes. Therefore, a considerable number of “artificial enzymes” derived from inorganic nanomaterials have been reported. This microreview highlights the recent progress in the field of enzymatically active inorganic nanomaterials, including mimics of peroxidases, haloperoxidases, superoxide dismutases and sulfite oxidases, along with selected biotechnological applications and their future prospects.

The increasing use of silver (Ag) nanoparticles (NPs) in daily-life applications, electronics, or catalysis calls for green and cost-efficient synthetic methods. Ag NPs are used especially in biomedicine because of their antibacterial, antifungal, or anticancer properties. Chemical synthesis allows tuning the particle morphology, size, and crystallinity, but requires toxic and hazardous chemicals. Bioinspired synthetic protocols have shown promise to minimize environmental impact, but biological protocols for the synthesis of Ag NPs lack control on the morphology and crystallinity. This review briefly compiles the chemical synthesis of Ag NPs and contrasts it with "green" protocols based on lessons learnt from chemical synthesis. The synthesis of Ag NPs with different plant extracts and the associated phytomolecules, their chemical and biological effects, and their effect on particle synthesis are described and put into perspective to improve green protocols. The surface functionalization of Ag NPs by phytomolecules and the mechanisms of their biomedical applications are summarized.

Despite the great progress in the synthesis of iron oxide nanoparticles (NPs) using a thermal decomposition method, the production of NPs with low polydispersity index is still challenging. In a thermal decomposition synthesis, oleic acid (OAC) and oleylamine (OAM) are used as surfactants. The surfactants bind to the growth species, thereby controlling the reaction kinetics and hence playing a critical role in the final size and size distribution of the NPs. Finding an optimum molar ratio between the surfactants oleic OAC/OAM is therefore crucial. A systematic experimental and theoretical study, however, on the role of the surfactant ratio is still missing. Here, we present a detailed experimental study on the role of the surfactant ratio in size distribution. We found an optimum OAC/OAM ratio of 3 at which the synthesis yielded truly monodisperse (polydispersity less than 7%) iron oxide NPs without employing any post synthesis size-selective procedures. We performed molecular dynamics simulations and showed that the binding energy of oleate to the NP is maximized at an OAC/OAM ratio of 3. The optimum OAC/OAM ratio of 3 is allowed for the control of the NP size with nanometer precision by simply changing the reaction heating rate. The optimum OAC/OAM ratio has no influence on the crystallinity and the superparamagnetic behavior of the Fe

We describe elementary concepts, up-to-date developments, and perspectives of the emerging field of nanoparticle enzyme mimics (so-called "nanozymes") at the interface of chemistry, biology, materials, and nanotechnology. The design and synthesis of functional enzyme mimics is a long-standing goal of biomimetic chemistry. Metal complexes, polymers and engineered biomolecules capturing the structure of natural enzymes or their active centers have been made to achieve high rates and enhanced selectivities. Still, the design of new "artificial enzymes" that are not related to proteins but with capacity of production and stability at industrial level, remains a goal. Inorganic nanoparticles bear this potential. Although it seems counterintuitive to compare nanoparticles and natural enzymes because they appear very different they share many common features: nano-size, irregular shape, and rich surface chemistry. These features enable nanomaterials to mimic reactions of natural enzymes. Representative examples with biomedical and environmental applications are given.

Thermal decomposition is a promising route for the synthesis of highly monodisperse magnetite nanoparticles. However, the apparent simplicity of the synthesis is counterbalanced by the complex interplay of the reagents with the reaction variables that determine the final particle size and dispersity. Here, we present a combined experimental and theoretical study on the influence of the heating rate on crystal growth, size, and monodispersity of iron oxide nanoparticles. We synthesized monodisperse nanoparticles with sizes varying from 6.3 to 27 nm simply by controlling the heating rate of the reaction. The nanoparticles show size-dependent superparamagnetic behavior. Using numerical calculations based on the classical nucleation theory and growth model, we identified the relative time scales associated with the heating rate and precursor-to-monomer (growth species) conversion rate as a decisive factor influencing the final size and dispersity of the nanoparticles.

CuInS2 nanoparticles as the visible (wurtzite, 1.67 eV) or near infrared (chalcopyrite, 1.50 eV) light absorbing material in thin film solar cells, were synthesized using facile, one step heating up method by dissolving of CuCl, InCl3 and SC(NH2)2 as precursors in oleylamine (OLA) alone or in combination with oleic acid (OA) and 1-octadecene (ODE) as solvent. The phase, size, morphology, and size distribution were controlled by the coordination ability between solvent molecules and metal precursors, reaction temperature and time. The presence of higher amounts of thiourea or OA to OLA led to the formation of chalcopyrite phase in comparison to wurtzite structure. Also, higher reaction temperatures (>240 °C) resulted in favour of more chalcopyrite phase and higher crystallinity but the nanoparticles got agglomerated. As synthesized nanoparticles was characterized by transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, high resolution-transmission electronic microscopy, ultraviolet–visible-near infrared, photoluminescence. The high resolution TEM confirmed the existence of chalcopyrite structure along with wurtzite structure in the nanocrystal (polytypism). Well controlled chalcopyrite CuInS2 triangular pyramidal shape with an average size ranging from ~10–20 nm size was obtained by using 20 ml OLA or 20 ml OLA along with 4 ml OA and ODE, respectively, with 210 °C heating up and 4 h annealing time.

Heteronanoparticles represent a new class of nanomaterials exhibiting multifunctional and collective properties, which could find applications in medical imaging and therapy, catalysis, photovoltaics, and electronics. This present work demonstrates the intrinsic heteroepitaxial linkage in heterodimer nanoparticles to enable interaction of the individual components across their interface. It revealed distinct differences between Au@MnO and Au@Fe3O4 regarding the synthetic procedure and growth kinetics, as well as the properties to be altered by the variation of the electronic structure of the metal oxides. The chemically related metal oxides differ concerning their band gap; while MnO is a Mott-Hubbard insulator with a large band gap, Fe3O4 is a semimetal with thermally activated conductivity. The fluorescence dynamics indicate a prolonged relaxation time (>2 ns) for electrons of the conduction band of the Au nanoparticles after interfacing to Fe3O4. Here, the semiconductor is not depleted and forms an ohm...

Many natural materials are complex composites whose mechanical properties are often outstanding considering the weak constituents from which they are assembled. Nacre, made of inorganic (CaCO 3 ) and organic constituents, is a textbook example because of its strength and toughness, which are related to its hierarchical structure and its well-defi ned organic–inorganic interface. Emulating the construction principles of nacre using simple inorganic materials and polymers is essential for understanding how chemical composition and structure determine biomaterial functions. A hard multilayered nanocomposite is assembled based on alternating layers of TiO 2 nanoparticles and a 3-hydroxytyramine (DOPA) substituted polymer (DOPA-polymer), strongly cemented together by chelation through infi ltration of the polymer into the TiO 2 mesocrystal. With a Young’s modulus of 17.5 ± 2.5 GPa and a hardness of 1.1 ± 0.3 GPa the resulting material exhibits high resistance against elastic as well as plastic deformation. A key feature leading to the high strength is the strong adhesion of the DOPA-polymer to the TiO 2 nanoparticles.

The synthesis of statistical and block copolymers based on polyacrylonitrile, as a source for carbonaceous materials, and thiol-containing repeating units as inorganic nanoparticle anchoring groups is reported. These polymers are used to coat Au@ZnO multipod heteroparticles with polymer brushes. IR spectroscopy and transmission electron microscopy prove the successful binding of the polymer onto the inorganic nanostructures. Thermogravimetric analysis is applied to compare the binding ability of the block and statistical copolymers. Subsequently, the polymer coating is transformed into a carbonaceous (partially graphitic) coating by pyrolysis. The obtained carbon coating is characterized by Raman spectroscopy and energy-dispersive X-ray (EDX) spectroscopy. The benefit of the conformal carbon coating of the Au@ZnO multipods regarding its application as lithium-ion anode material is revealed by performing galvanostatic cycling, showing a highly enhanced and stabilized electrochemical performance of the carbon-coated particles (still 831 mAh g(-1) after 150 cycles) with respect to the uncoated ones (only 353 mAh g(-1) after 10 cycles).

The potential toxicity of nanoparticles has currently provoked public and scientific discussions, and attempts to develop generally accepted handling procedures for nanoparticles are under way. The investigation of the impact of nanoparticles on human health is overdue and reliable test systems accounting for the special properties of nanomaterials must be developed. Nanoparticular zinc oxide (ZnO) may be internalised through ambient air or the topical application of cosmetics, only to name a few, with unpredictable health effects. Therefore, we analysed the determinants of ZnO nanoparticle (NP) genotoxicity. ZnO NPs (15-18 nm in diameter) were investigated at concentrations of 0.1, 10 and 100 μg mL(-1) using the cell line A549. Internalised NPs were only infrequently detectable by TEM, but strongly increased Zn(2+) levels in the cytoplasm and even more in the nuclear fraction, as measured by atom absorption spectroscopy, indicative of an internalised zinc and nuclear accumulation. We observed a time and dosage dependent reduction of cellular viability after ZnO NP exposure. ZnCl2 exposure to cells induced similar impairments of cellular viability. Complexation of Zn(2+) with diethylene triamine pentaacetic acid (DTPA) resulted in the loss of toxicity of NPs, indicating the relevant role of Zn(2+) for ZnO NP toxicity. Foci analyses showed the induction of DNA double strand breaks (DSBs) by ZnO NPs and increased intracellular reactive oxygen species (ROS) levels. Treatment of the cells with the ROS scavenger N-acetyl-l-cysteine (NAC) resulted in strongly decreased intracellular ROS levels and reduced DNA damage. However, a slow increase of ROS after ZnO NP exposure and reduced but not quashed DSBs after NAC-treatment suggest that Zn(2+) may exert genotoxic activities without the necessity of preceding ROS-induction. Our data indicate that ZnO NP toxicity is a result of cellular Zn(2+) intake. Subsequently increased ROS-levels cause DNA damage. However, we found evidence for the assumption that DNA-DSBs could be caused by Zn(2+) without the involvement of ROS.

Thermal decomposition is a promising route for the synthesis of magnetic nanoparticles. The simplicity of the synthesis method is counterbalanced by the complex chemistry of the system such as precursor decomposition and surfactant–reducing agent interactions. Control over nanoparticle size is achieved by adjusting the reaction parameters, namely, the precursor concentration. The results, however, are conflicting as both an increase and a decrease in nanoparticle size, as a function of increasing concentration, have been reported. Here, we address the issue of size-controlled synthesis via the precursor concentration. We synthesized iron oxide nanoparticles with sizes from 6 nm to 24 nm with narrow size distributions. We show that the size does not monotonically increase with increasing precursor concentration. After an initial increase, the size reaches a maximum and then shows a decrease with increasing precursor concentration. We argue that the observation of two different size regimes is closely related to the critical role of the amount of surfactant. We confirm the effect of surfactant amount on nucleation and growth and explain the observed trend. Furthermore, we show that the nanoparticles show size-dependent but superior superparamagnetic properties at room temperature.

A one-pot method was used to synthesize CuInxGa1–xS2 nanoparticles by substituting In3+ with Ga3+. The samples with composition of gallium ranging from 0% to 100% were synthesized by solving copper chloride, indium trichloride, gallium acetylacetonate, and thiourea as precursors in 1-octadecene, oleylamine, and oleic acid as noncoordinating, coordinating, and capping agent solvents, respectively. Depending on the chemical composition and synthesis conditions, the morphology of the as-synthesized nanoparticles obtained was trigonal, semitrigonal, hexagonal, and quasi-spherical. X-ray photoelectron spectroscopy and X-ray diffraction confirmed that Ga3+ substituted In3+ without any segregation over a wide range. The as-synthesized CuInxGa1–xS2 nanoparticles showed narrow size distribution across the entire composition range (x = 0–1) and band gap tuned in the range from 1.44 to 2.28 eV. The morphology, structure, and optical properties of the synthesized nanoparticles were characterized using transmission el...

The physical properties of asymmetric Janus particles are highly promising for future biomedical applications. However, only a few data is available on their biological impact on human cells. We investigated the biological impact of different Au@Fe3O4 Janus particle formulations in vitro to analyse specific uptake modalities and their potential cytotoxic effects on human cells of the blood regarding intravenous injection. We demonstrate that Au@Fe3O4 Janus particles exhibit a similar or even better biocompatibility compared to the well-studied spherical iron oxide nanoparticles. The impact of Janus particles on cells depends mainly on three factors. (1) Surface functionalization: NH2-functionalization of the Au or iron oxide domain induces a pronounced reduction of cell viability in contrast to non-functionalized variants which is caused by the damage of intracellular membranes. (2) The nature of the metal oxide component, greatly affects cell viability, as shown by a comparison with Au@MnO Janus particles. (3) The overall surface charge and the size of nanoparticles have a higher impact on internalization and cellular metabolism than the Janus character per se. Interestingly, Janus particle associated DNA damage is independent of the effects on the cellular ATP level. However, not only the structure and functionalization of the Janus particle surface determines the particle's adhesion and intracellular fate, but also the constitution of the cell surface as shown by different modification experiments. The multifactorial in vitro approach presented in this study demonstrated the high capability of the Janus particles. Especially Au@Fe3O4 Janus particles bear great potential for applications in vivo.

Multifunctional linear (CA-linPG) and hyperbranched polyglycerols (CA-hbPG) bearing a single catechol unit were synthesized by use of an acetonide-protected catechol initiator for the anionic polymerization of ethoxyethyl glycidyl ether (EEGE) and glycidol, respectively. A key feature for the synthesis of the hyperbranched structures was a selective, partial acetal deprotection step. The single catechol unit among a large number of aliphatic 1,2- and 1,3-diol moieties (i.e., the “needle in the haystack”) in both linear and hyperbranched polyglycerols permits dispersion of transition metal oxide nanoparticles in brine, as demonstrated for manganese oxide (MnO) nanoparticles. Molecular weights of the single catechol bearing PGs ranged from 950 to 2350 g·mol–1 for CA-linPG and from 3750 to 5750 g·mol–1 for CA-hbPG with narrow and monomodal molecular weight distributions (Mw/Mn < 1.23 for linPG and Mw/Mn = 1.22–1.48 for hbPG). Both C-linPGs and C-hbPGs are suitable hydrophilic capping agents to generate highl...

The controlled radical polymerization (RAFT polymerization) of semiconducting polymers based on poly(4,4′-dimethyl-triphenylamine) is described. These polymers are afterward end-functionalized with a photocleavable group and an anchor unit (catechol) for oxidic nanoparticles (NPs). Serving as a reference, polystyrene oligomers with the same end groups are also synthesized. Using these polymers allows functionalization of the TiO2-NPs, leading to an improved solubility and miscibility in organic solvents or polymer matrices. Irradiation in the UV region is used to split the photocleavable group and remove the polymer chains from the NPs, which leads to their aggregation.

Nanoparticular FeSb2 was prepared in solution from cyclopentadienyl iron(ii) dicarbonyl dimer [Fe(Cp(CO)2)]2 and antimony nanoparticles. Spark plasma sintering was used as consolidation method to maintain the particle size. The thermoelectric performance of FeSb2 is limited by its high thermal conductivity. In this work, the thermal conductivity was suppressed by nearly 80% compared to the bulk value by introducing grain boundary scattering of phonons on the nanoscale. The thermoelectric properties of the consolidated FeSb2 emphasize the possibility of altering thermal transport of promising thermoelectric compounds by phonon scattering by engineering the interfaces at the nanoscale.

In this investigation, monodisperse CuGaS2 nanoparticles intended for use as visible-light-absorbing materials were synthesized using a facile one-step heating method that involved dissolving the precursors copper chloride, gallium acetylacetonate, and thiourea in a solvent consisting of either oleylamine alone or a combination of oleylamine, oleic acid, and 1-octadecene. The shapes of the resulting nanoparticles were either elongated, polygonal, or a mixture of both, depending on whether the crystal structure of the nanoparticles was predominantly wurtzite, predominantly chalcopyrite, or a more balanced mixture of both wurtzite and chalcopyrite (i.e., the nanoparticles were polytypic: both wurtzite and chalcopyrite phases were present). The crystal structure of the synthesized nanoparticles was found to be influenced by the temperature and the solvent applied during synthesis. X-ray diffraction data for the nanoparticles indicated that applying a temperature of 270 °C or using oleylamine, oleic acid solvent, and 1-octadecene during synthesis tended to yield a chalcopyrite phase, whereas applying a somewhat lower temperature (210 °C) or using oleylamine alone during synthesis tended to result in a wurtzite phase. The chemical states of the compounds obtained at different temperatures and using various solvents, as well as their crystal structures, morphologies, and optical properties were characterized via X-ray photoelectron spectroscopy, X-ray diffraction, transmission electron microscopy, ultraviolet–visible spectroscopy, and photoluminescence. Optical absorbance spectrum (red line) and photoluminescence spectrum (black line) of a CuGaS2 solid solution, and applications of this material in optoelectronics (photos below the spectra)

Phonons are exquisitely sensitive to finite length scale effects in a wide variety of materials. To investigate confinement in combination with strong magnetoelastic interactions, we measured the infrared vibrational properties of CoFe(2)O(4) nanoparticles and compared our results to trends in the coercivity over the same size range and to the response of the bulk material. Remarkably, the spectroscopic response is sensitive to the size-induced crossover to the superparamagnetic state, which occurs between 7 and 10 nm. A spin-phonon coupling analysis supports the core-shell model. Moreover, it provides an estimate of the magnetically disordered shell thickness, which increases from 0.4 nm in the 14 nm particles to 0.8 nm in the 5 nm particles, demonstrating that the associated local lattice distortions take place on the length scale of the unit cell. These findings are important for understanding finite length scale effects in this and other magnetic oxides where magnetoelastic interactions are important.

Monodisperse FePt@MnO nano-heteroparticles with different sizes and morphologies were prepared by a seed-mediated nucleation and growth technique. Both size and morphology of the individual domains could be controlled by adjustment of the synthetic parameters. As a consequence, different particle constructs, including dimers, dumbbell-like particles, and flowerlike particles, could be obtained by changing the polarity of the solvent. The FePt@MnO nano-heteroparticles were thoroughly characterized by high resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) analyses and superconducting quantum interference device (SQUID) magnetometry. Due to a sufficient lattice match, the MnO nanoparticles (NPs) preferentially grow on the (111) surfaces of the fcc-FePt seeds. Furthermore, the surface spins of the antiferromagnetic MnO domains pin the magnetic moments of the ferromagnetic FePt NPs, which leads to an exchanged biased magnetic hysteresis.

Nanostructured tin dioxide was synthesized by making use of the catalytic activity of silicatein-α. TEM, HRTEM, and XRD revealed the formation of cassiterite SnO2. Surface bound silicatein retains its biocatalytic activity. This was demonstrated by immobilizing silicatein on glass surfaces using a histidine-tag chelating anchor. The subsequent deposition of SnO2 on glass was monitored by quartz crystal microbalance (QCM) measurements and scanning electron microscopy (SEM). This new aspect of silicatein activity toward the formation of metal oxides other than SiO2, TiO2, and BaTiO3 opens up new vistas in composite material synthesis.

This article presents the synthesis of novel hydroxypropylmethylcellulose (HPMC)-aspirin (ASP) conjugates, i.e. macromolecular prodrugs, through the reaction of HPMC with ASP after its in situ activation by 4-methylbenzenesulfonyl chloride. The highly pure ASP prodrugs obtained by this homogeneous and elegant esterification method were characterized using different spectroscopic and chromatographic techniques. Nanoparticulate drug design was successfully achieved by the conversion of free hydroxyls of the polymer into acetates. Transmission electron microscopy and scanning electron microscopy showed nanoparticle formation with the major population size distribution of around 450 nm. Nevertheless, the pharmacokinetics of the HPMC conjugates were studied using high performance liquid chromatography. The pharmacokinetic data indicated that a single dose of 132.6 mg of HPMC-ASP was well tolerated in animal studies without any adverse effects. The maximum plasma concentration (C max ) of HPMC-ASP was found to be 14.6 μg·L−1 with a t max of 1 h. The plasma half-life and clearance and the volume of HPMC-ASP distribution were 4.6 h, 3.23 L·h−1, and 21.8 L·kg−1, respectively. The elimination of HPMC-ASP followed first-order kinetics with r 2 of 0.9643. The results presented in this paper show the great potential of HPMCASP as a more effective, safe, and stable prodrug.

Understanding how solids form is a challenging task, and few strategies allow for elucidation of reaction pathways that are useful for designing the synthesis of solids. Here, we report a powerful solution-mediated approach for formation of nanocrystals of the thermoelectrically promising FeSb(2) that uses activated metal nanoparticles as precursors. The small particle size of the reactants ensures minimum diffusion paths, low activation barriers, and low reaction temperatures, thereby eliminating solid-solid diffusion as the rate-limiting step in conventional bulk-scale solid-state synthesis. A time- and temperature-dependent study of formation of nanoparticular FeSb(2) by X-ray powder diffraction and iron-57 Mössbauer spectroscopy showed the incipient formation of the binary phase in the temperature range of 200-250 °C.

Objectives The absorption of commonly used ferrous iron salts from intestinal segments at neutral to slightly alkaline pH is low, mainly because soluble ferrous iron is easily oxidized to poorly soluble ferric iron and ferrous iron but not ferric iron is carried by the divalent metal transporter DMT-1. Moreover, ferrous iron frequently causes gastrointestinal side effects. In iron(III)-hydroxide nanoparticles hundreds of ferric iron atoms are safely packed in nanoscaled cores surrounded by a solubilising carbohydrate shell, yet bioavailability from such particles is insufficient when compared with ferrous salts. To increase their intestinal uptake iron(III)-hydroxide nanoparticles were coupled in this study with the protoporphyrin hemin, which undergoes carrier-mediated uptake in the intestine. Methods Uptake of iron(III)-hydroxide nanoparticles with hemin covalently coupled by DCC reaction was measured in Caco-2 cells with a colorimetric assay and visualized by transmission electron microscopy. Key findings Nanoparticles were taken up by carrier-mediated transport, since uptake was temperature-dependent and increased with an increasing hemin substitution grade. Furthermore, uptake decreased with an increasing concentration of free hemin, due to competition for carrier-mediated uptake. Conclusions Hemin-coupled iron(III)-hydroxide nanoparticles were carried by a heme specific transport system, probably via receptor mediated endocytosis. It can be expected that this system shows improved absorption of iron compared with uncoupled iron(III)-hydroxide nanoparticles, which exist on the market today.

Engineering materials with specific physical properties has recently focused on the effect of nanoscopic inhomogeneities at the 10 nm scale. Such features are expected to scatter medium and long-wavelength phonons lowering thereby the thermal conductivity of the system without simultaneously decreasing the charge transport (phonon–glass electron–crystal concept). A new Zn1+xSb nanophase obtained by a wet chemical approach was densified by spark plasma sintering (SPS). Investigations on compounds subsumed as “Zn4Sb3” always suffer from its low thermal stability and the contamination of the nanoparticles with solvents and additives used in the synthesis. In order to gain insight into this compound's electronic properties we investigated a material free from remnants of the synthesis but contaminated with a small amount of well-characterized decomposition product, i.e., ZnSb. To investigate the influence of the sintering process on the densified samples, different SPS conditions were applied. Four different conditions were used with heating rates between 160° and 230 °C/min, sintering temperatures between 130 and 190 °C and sintering times between 3 and 6 min. Powders from the surface of the pellets were subject to powder X-ray diffraction (XRD) yielding information about the surface composition. Small pieces of the pellets were also characterized using high-energy synchrotron radiation scattering in order to reveal the phase compositions inside the pellets. Small changes in the sintering conditions of the samples were found to have a large influence on the resulting sample compositions. In addition, the phase compositions on the surface differ significantly from the ones inside the pellets which show a much higher grade of decomposition. The density and morphology of the obtained pellets have been investigated by means of laser microscopy and scanning electron microscopy (SEM). The low density and porosity of the different pellets is a result of the graphite pressing tool which has to be used to ensure the temperature control during the SPS process.

A directed self assembly of anisotropic nanostructures offers a possibility to provide unique functional materials, which are e.g., important in optoelectronic devices. We use the liquid crystalline behavior of polymer functionalized TiO2 and ZnO nanorods to apply methods well known for low molecular liquid crystals to achieve oriented thin films. Convective forces in the meniscus on a structured substrate obtain thin layers of oriented nanoparticles with a ordering parameter of S = 0.7. As another method we present the orientation of polystyrene covered ZnO nanorods under an applied electric field. The method offers a perpendicular alignment of the rods to the surface.

New synthetic approaches to MS 2 (M = Sn, Nb, Mo, W) chalcogenide nanostructures are highlighted. Most chalcogenide particles can be functionalized directly with inorganic nanoparticles such as Au, ZnO or MnO. Depending on the Pearson hardness of the metal involved, the functionalization may be reversible or irreversible. A covalent functionalization strategy is based on a steric shielding of the coordination sphere of transition metal atoms in such a way that only coordination sites are available for bonding to the chalcogenide surface. This allows the immobilization of fluorophors, redox active groups or proteins onto chalcogenide nanoparticle.