Gold Nanoparticles Stabilized by Single Tripodal Ligands

In order to coat the entire surface of gold nanoparticles (AuNPs) by a single ligand, tripodal macromolecules comprising benzylic thioethers coordinating to the AuNP surface are synthesized and their abilities to stabilize AuNPs are investigated. Out of the five studied ligands 1 – 5 , the tetraphenylmethane‐based oligomers 4 and 5 display excellent AuNP coating features. Both ligand structures are able to control the dimensions of the AuNPs by stabilizing particles of narrow size distributions during their syntheses (1.05 ± 0.28 nm for Au‐4 , and 1.15 ± 0.34 nm for Au‐5 ). Closer inspection of these AuNPs by transmission electron microscopy and thermogravimetric analyses suggests that single ligands 4 and 5 are able to stabilize entire AuNPs. These particles Au‐4 and Au‐5 are obtained in good yields and display promising thermal stabilities (110 °C for Au‐4 , and 95 °C for Au‐5 ), making them interesting nanoscale inorganic–organic building blocks for further functionalization/processing by wet chemistry.     

Essential Amino Acid–Enabled Lead Bromide Perovskite Nanocrystals with High Stability

This work reports the first synthesis of MAPbBr₃ perovskite nanocrystals (PNCs) using amino acids as the ligand with excellent optical properties. A variety of amino acids are used to optimize the luminescence properties. A mechanochemical approach has taken lead over conventional colloidal chemistry during synthesis. All morphological and optical studies are performed to characterize the synthesized perovskite nanoparticles. Later, stability studies are investigated through thermogravimetric analysis, temperature‐dependent photoluminescence, time‐dependent X‐ray diffraction, as well as X‐ray photoelectron spectroscopy. In an application, interestingly, these perovskites show high luminescence upon scratching on flexible conducting plates and on plain paper surface. These results suggest that the amino acid–ligated perovskite nanocrystals can be potential materials for optoelectronic application including light‐emitting diodes and imaging.     

Synchrotron PEEM and ToF‐SIMS study of oxidized heterogeneous pentlandite,pyrrhotite and chalcopyrite

Synchrotron‐based photoemission electron microscopy (PEEM; probing the surface region) and time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS; probing the uppermost surface layer) have been used to image naturally heterogeneous samples containing chalcopyrite (CuFeS₂), pentlandite [(Ni,Fe)₉S₈] and monoclinic pyrrhotite (Fe₇S₈) both freshly polished and exposed to pH 9 KOH for 30 min. PEEM images constructed from the metal L₃ absorption edges were acquired for the freshly prepared and solution‐exposed mineral samples. These images were also used to produce near‐edge X‐ray absorption fine‐structure spectra from regions of the images, allowing the chemistry of the surface of each mineral to be interrogated, and the effect of solution exposure on the mineral surface chemistry to be determined. The PEEM results indicate that the iron in the monoclinic pyrrhotite oxidized preferentially and extensively, while the iron in the chalcopyrite and pentlandite underwent only mild oxidation. The ToF‐SIMS data gave a clearer picture of the changes happening in the uppermost surface layer, with oxidation products being observed on all three minerals, and significant polysulfide formation and copper activation being detected for pyrrhotite.     

A solid phospholipid-bile salts-mixed micelles based on the fast dissolving oral films to improve the oral bioavailability of poorly water-soluble drugs

Magnetic iron oxide nanoparticles surface covered with oleic acid layer followed by a second layer of hydrophobized oxidized dextran aldehyde were prepared and tested for physico-chemical properties and ligand- and cell-specific binding. It was demonstrated that oleic acid–iron oxide nanoparticles coated with an additional layer of hydrophobized oxidized dextran were dispersible in buffer solutions and possess surface aldehyde active groups available for further binding of ligands or markers via imine or amine bond formation. Hydrophobized dextrans were synthesized by periodate oxidation and conjugation of various alkanamines to oxidized dextran by imination. Physico-chemical properties, as separation using magnetic field, magnetite concentration, and particle diameter, of the prepared magnetic samples are reported. The biotin-binding protein, neutravidin, was coupled to the particle surface by a simple reductive amination procedure. The particles were used for specific cell separation with high specificity.     

A Surface Study of Ultrathin Ceria Nanoparticles Decorated with Transition‐Metal Ions

A wide range of nanoparticle properties can be tuned by changing their surface characteristics, especially when dealing with ultrathin nanomaterials. Surface modification with transition‐metal ions may affect a variety of the nanoparticles' properties including the surface charge, the electronic structure, and the electrical and optical characteristics. In this work, a surface study of ceria nanoparticles modified by attachment of various transition‐metal ions to their surface is conducted. Characterization of the decorated particles as well as of the modifying transition‐metal ion is carried out using zeta potential in organic solution, UV–Vis absorption, and electron paramagnetic resonance measurements, together with isothermal titration calorimetry, X‐ray photoelectron spectroscopy, and energy dispersive X‐ray spectroscopy. All measurements confirm the attachment of the cation to the surface of ceria, both in solid state and in colloidal suspension. It is suggested that the modifying ion‐complex attaches to ceria both via chemical or strong physical interactions and weak physical interactions, demonstrated by a case‐study modification of ceria using a copper‐oleylamine complex. The metalization has a significant effect on the surface charge of the nanoparticles by shifting the zeta potential to more positive values and on the optical properties of the modifying transition‐metal ions by red‐shifting their absorption peak.     

Structure and Stability of PEG‐ and Mixed PEG‐Layer‐Coated Nanoparticles at High Particle Concentrations Studied In Situ by Small‐Angle X‐Ray Scattering

Ligand‐layer structure and stability of gold nanoparticles (AuNP) coated with α‐methoxypoly(ethylene glycol)‐ω‐(11‐mercaptoundecanoate) (PEGMUA) layers and mixed layers of PEGMUA and 11‐mercaptoundecanoic acid (MUA) at high AuNP concentrations are studied in situ by small‐angle X‐ray scattering (SAXS). The thickness of the ligand layer is modified by the molecular weight of the PEG‐ligands (2 and 5 kDa), and the PEG‐grafting density is decreased by coadsorption of MUA. The response of the conjugates to a pressure of up to 4 kbar is probed. The results indicate strongly hydrated PEG layers at high grafting densities. The stability of the mixed ligand‐layer conjugates is lower. This is most probably due to enhanced interparticle PEG–PEG interactions at lower grafting densities. The presented study demonstrates that a detailed structural characterization of polymer ligand layers in situ and in response to external stimuli is possible with SAXS.     

Exchange‐Biased Fe3−xO4‐CoO Granular Composites of Different Morphologies Prepared by Seed‐Mediated Growth in Polyol: From Core–Shell to Multicore Embedded Structures

Magnetically contrasted granular hetero‐nanostructures are prepared by seed‐mediated growth in polyol, properly combining two oxide phases with different magnetic order, ferrimagnetic (F) partially oxidized magnetite Fe_3−xO₄ and antiferromagnetic (AF) cobalt oxide. Spinel Fe_3−xO₄ nanoparticles are first synthesized and then used as seeds for rock salt CoO nanocrystals growth. Three different hetero‐nanostructure designs are realized, acting on the content ratio between the seeds and the deposit's precursors during the synthesis. For all of them, the spinel and the rock salt phases are confirmed by X‐ray diffraction and high‐resolution transmission electron microscopy. Both phases are obtained in high‐crystalline quality with a net epitaxial relationship between the two crystallographic lattices. Mössbauer spectrometry confirms the cobalt cation diffusion into the spinel seeds, giving favorable chemical interfacing with the rock salt deposit, thus prevailing its heterogeneous nucleation and consequently offering the best condition for exchange‐bias (EB) onset. Magnetic measurements confirm EB features. The overall magnetic properties are found to be a complex interplay between dipolar interactions, exchange anisotropy at the F/AF interface, and magnetocrystalline anisotropy enhancement in the F phase, due to Co²⁺ diffusion into iron oxide's crystalline lattice. These results underline the powerfulness of colloidal chemistry for functional granular hetero‐nanostructured material processing.     

Control Synthesis of Air‐Stable Morphology Tunable Pb‐Free Cs2SnI6 Perovskite Nanoparticles and Their Photodetection Properties

Pb‐free Cs₂SnI₆ perovskite nanoparticles with different morphologies are synthesized using hot injection process and precise control of ligand chemistry. Size dependent band gap variation is studied to evaluate quantum‐confinement effect in the system. Stable and fast photodetector with high current gain is fabricated by using the nanoparticles as colloidal ink.     

Polymerizable Ligands as Stabilizers for Nanoparticles

Monomers bearing functional groups that can get chemisorbed on nanoparticles to form polymerizable monolayers have emerged as an interesting class of stabilizer ligands for various nanoparticles. High‐surface coverage, their ability to modify the properties of underlying nanoparticles, capability to form polymers of different molecular weights and possibility to make structural modifications make them attractive for their use as stabilizer ligands for nanoparticles. Both in situ and post‐synthesis grafting methods for attaching polymerizable ligands to nanoparticles are frequently used. The advantage of grafting polymerizable stabilizer on the surface of nanoparticles is that initially the polymerizable molecule acts as a proper stabilizer for the nanoparticles and later their surface polymerization or co‐polymerization with another suitable monomer can be carried out to generate the desired polymer scaffold around the nanoparticles, which ensures the increased stability of the resulting core‐polymerized shell nanoparticles. This review discusses interesting reports from recent literature on grafting of polymerizable ligands and their polymerization on gold, silver, silica, and iron oxide nanoparticles.     

Characterisation of Sonochemically Produced PdO Nanoparticles by X‐ray Absorption Near Edge Structure Spectroscopy

Brij‐35 [polyoxyethylene(23) lauryl ether] stabilised palladium nanoparticles, obtained on attempted sonochemical reduction of PdCl₂ by sodium sulfite in water under Argon, instantaneously oxidized to PdO. The particles obtained were stable and have narrow size distribution with an average size of 10 nm diameter. PdO nanoparticles were reduced to Pd nanoparticles in an autoclave by treatment with 50 bar hydrogen at 140 °C. The catalytic behaviour of Pd nanoparticles, thus obtained, is unusual in comparison with conventional Pd catalysts. The nanoparticles were characterized by UV‐Vis spectroscopy, TEM and their X‐ray Absorption Near Edge Structure (XANES) at the Pd‐L‐III edge.     

Internal Structure and Magnetic Properties in Cobalt Ferrite Nanoparticles: Influence of the Synthesis Method

The design of novel nanostructured magnetic materials requires a good understanding of the variation in the magnetic properties due to different synthesis conditions. In this work, four different procedures for fabricating Co‐ferrite nanoparticles with similar sizes between 7 and 10 nm are compared by studying their structural and magnetic properties. Non‐aqueous methods based on the thermal decomposition of metal acetylacetonates at high temperatures, either with or without surfactants, provide highly crystalline nanoparticles with large saturation magnetization values and a coherent reversal of the magnetic moment. However, variations in the density of defects and in the shape of the nanocrystals determine the distribution of switching fields and the effective magnetic anisotropy, which reaches up to ≈1 × 10⁷ erg cm^?3 for oleic acid‐capped 9 nm nanoparticles. It is shown that the saturation magnetization values for nanoparticles produced by different methods are in the range between 49 and 95 emu g^?1 due to differences in the stoichiometry, in the cation occupancy, in the magnetic disorder and in the spin canting of the magnetic sub‐lattices, the latter evaluated by in‐field Mössbauer spectroscopy.     

Large specific absorption rates in the magnetic hyperthermia properties of metallic iron nanocubes

We report on the magnetic hyperthermia properties of chemically synthesized ferromagnetic 11 and 16 nm Fe(0) nanoparticles of cubic shape displaying the saturation magnetization of bulk iron. The specific absorption rate measured on 16 nm nanocubes is 1690±160 W/g at 300 kHz and 66 mT. This corresponds to specific losses-per-cycle of 5.6 mJ/g, largely exceeding the ones reported in other systems. A way to quantify the degree of optimization of any system with respect to hyperthermia applications is proposed. Applied here, this method shows that our nanoparticles are not fully optimized, probably due to the strong influence of magnetic interactions on their magnetic response. Once protected from oxidation and further optimized, such nano-objects could constitute efficient magnetic cores for biomedical applications requiring very large heating power.     

Encapsulation of SnO2/Sn Nanoparticles into Mesoporous Carbon Nanowires and its Excellent Lithium Storage Properties

A peculiar nanostructure of encapsulation of SnO₂/Sn nanoparticles into mesoporous carbon nanowires (CNWs) has been successfully fabricated by a facile strategy and confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), high‐resolution TEM (HRTEM), X‐ray diffraction (XRD), BET, energy‐dispersive X‐ray (EDX) spectrometer, and X‐ray photoelectron spectroscopy (XPS) characterizations. The 1D mesoporous CNWs effectively accommodate the strain of volume change, prevent the aggregation and pulverization of nanostructured SnO₂/Sn, and facilitate electron and ion transport throughout the electrode. Moreover, the void space surrounding SnO₂/Sn nanoparticles also provides buffer spaces for the volumetric change of SnO₂/Sn during cycling, thus resulting in excellent cycling performance as potential anode materials for lithium‐ion batteries. Even after 499 cycles, a reversible capacity of 949.4 mAh g^?1 is retained at 800 mA g^?1. Its unique architecture should be responsible for the superior electrochemical performance.     

Magnetic anisotropy and magnetization dynamics of Fe nanoparticles embedded in Cr and Ag matrices

Static and dynamical magnetic properties of Fe nanoparticles (NPs) embedded in non-magnetic (Ag) and antiferromagnetic (Cr) matrices with a volume filling fraction (VFF) of 10% have been investigated. In both Fe@Ag and Fe@Cr nanocomposites, the Fe NPs have a narrow size distribution, with a mean particle diameter around 2 nm. In both samples, the saturation magnetization reaches that of Fe bulk bcc, suggesting the absence of alloying with the matrices. The coercivity at 5 K is much larger in Fe@Cr than in Fe@Ag as a result of the strong interaction between the Fe NPs and the Cr matrix. Temperature-dependent magnetization and ac-susceptibility measurements point out further evidence of the enhanced interparticle interaction in the Fe@Cr system. While the behaviour of Fe@Ag indicates the presence of weakly interacting magnetic monodomain particles with a wide distribution of blocking temperatures, Fe@Cr behaves like a superspin glass produced by the magnetic interactions between NPs.     

Magnetic Properties of Iron/Graphite Core-shell Structured Nanoparticles Prepared by Annealing of Fe-C-N Nanocomposite

We are reporting the core-shell structured iron/graphite nanoparticles formed during annealing of a nanopowder prepared by laser pyrolysis of gas phase reactants. The originally synthesized Fe-C-N nanocomposite powder has been characterized by TEM, XRD and magnetic measurements. Nanopowder was heated up to 800 °C at ～ 1 Pa vacuum. Presence of iron nanoparticles with mean diameter 40 nm in the annealed state of nanopowder was proved by XRD and TEM analyses. Mössbauer spectroscopy was used for characterization of synthesized/annealed nanopowder to confirm the qualitative change in phase composition.     

Discovering the Determining Parameters for the Photocatalytic Activity of TiO2 Colloids Based on an Anomalous Dependence on the Specific Surface Area

The photocatalytic (PC) performance of titanium dioxide (TiO₂) nanoparticles strongly depends on their specific surface, the presence of crystal defects, their crystal phase, and the exposed crystal facets. In order to understand which of these factors contributes most significantly to the PC activity of TiO₂ colloids, all of them have to be individually analyzed. This study entails the synthesis of five anatase nanocrystal samples. By maintaining the same reactant ratios as well as hydrothermal sol–gel synthesis route and only varying the autoclaving time or temperature, different crystallite sizes are obtained under comparable experimental conditions. A decrease in PC performance with increase in specific surface area is found. Such an unexpected counterintuitive result establishes the basis for a better understanding of the crucial factors that ultimately determine the PC activity. These are investigated by studying nanocrystals bulk and surface structure and morphology using a selection of complementary analysis methods (X‐ray photoelectron spectroscopy (XPS), X‐ray absorption fine structure (XAFS), X‐ray diffraction (XRD)…). It is found that a change in the nanocrystal morphology from an equilibrium state truncated tetragonal bipyramid to a more elongated rod‐like structure accompanied by an increase in oxygen vacancies is responsible for an augmented PC activity of the TiO₂ nanocrystals.     

Colloidal Flower‐Shaped Iron Oxide Nanoparticles: Synthesis Strategies and Coatings

The assembly of magnetic cores into regular structures may notably influence the properties displayed by a magnetic colloid. Here, key synthesis parameters driving the self‐assembly process capable of organizing colloidal magnetic cores into highly regular and reproducible multi‐core nanoparticles are determined. In addition, a self‐consistent picture that explains the collective magnetic properties exhibited by these complex assemblies is achieved through structural, colloidal, and magnetic means. For this purpose, different strategies to obtain flower‐shaped iron oxide assemblies in the size range 25–100 nm are examined. The routes are based on the partial oxidation of Fe(OH)₂, polyol‐mediated synthesis or the reduction of iron acetylacetonate. The nanoparticles are functionalized either with dextran, citric acid, or alternatively embedded in polystyrene and their long‐term stability is assessed. The core size is measured, calculated, and modeled using both structural and magnetic means, while the Debye model and multi‐core extended model are used to study interparticle interactions. This is the first step toward standardized protocols of synthesis and characterization of flower‐shaped nanoparticles.     

Insight into growth of Au–Pt bimetallic nanoparticles: an in situ XAS study

Au–Pt bimetallic nanoparticles have been synthesized through a one‐pot synthesis route from their respective chloride precursors using block copolymer as a stabilizer. Growth of the nanoparticles has been studied by simultaneous in situ measurement of X‐ray absorption spectroscopy (XAS) and UV–Vis spectroscopy at the energy‐dispersive EXAFS beamline (BL‐08) at Indus‐2 SRS at RRCAT, Indore, India. In situ XAS spectra, comprising both X‐ray near‐edge structure (XANES) and extended X‐ray absorption fine‐structure (EXAFS) parts, have been measured simultaneously at the Au and Pt L₃‐edges. While the XANES spectra of the precursors provide real‐time information on the reduction process, the EXAFS spectra reveal the structure of the clusters formed in the intermediate stages of growth. This insight into the formation process throws light on how the difference in the reduction potential of the two precursors could be used to obtain the core–shell‐type configuration of a bimetallic alloy in a one‐pot synthesis method. The core–shell‐type structure of the nanoparticles has also been confirmed by ex situ energy‐dispersive spectroscopy line‐scan and X‐ray photoelectron spectroscopy measurements with in situ ion etching on fully formed nanoparticles.     

Fluorescence imaging of reactive oxygen species by confocal laser scanning microscopy for track analysis of synchrotron X‐ray photoelectric nanoradiator dose: X‐ray pump–optical probe

Bursts of emissions of low‐energy electrons, including interatomic Coulomb decay electrons and Auger electrons (0–1000 eV), as well as X‐ray fluorescence produced by irradiation of large‐Z element nanoparticles by either X‐ray photons or high‐energy ion beams, is referred to as the nanoradiator effect. In therapeutic applications, this effect can damage pathological tissues that selectively take up the nanoparticles. Herein, a new nanoradiator dosimetry method is presented that uses probes for reactive oxygen species (ROS) incorporated into three‐dimensional gels, on which macrophages containing iron oxide nanoparticles (IONs) are attached. This method, together with site‐specific irradiation of the intracellular nanoparticles from a microbeam of polychromatic synchrotron X‐rays (5–14 keV), measures the range and distribution of OH radicals produced by X‐ray emission or superoxide anions () produced by low‐energy electrons. The measurements are based on confocal laser scanning of the fluorescence of the hydroxyl radical probe 2‐[6‐(4′‐amino)phenoxy‐3H‐xanthen‐3‐on‐9‐yl] benzoic acid (APF) or the superoxide probe hydroethidine‐dihydroethidium (DHE) that was oxidized by each ROS, enabling tracking of the radiation dose emitted by the nanoradiator. In the range 70 µm below the irradiated cell, radicals derived mostly from either incident X‐ray or X‐ray fluorescence of ION nanoradiators are distributed along the line of depth direction in ROS gel. In contrast, derived from secondary electron or low‐energy electron emission by ION nanoradiators are scattered over the ROS gel. ROS fluorescence due to the ION nanoradiators was observed continuously to a depth of 1.5 mm for both oxidized APF and oxidized DHE with relatively large intensity compared with the fluorescence caused by the ROS produced solely by incident primary X‐rays, which was limited to a depth of 600 µm, suggesting dose enhancement as well as more penetration by nanoradiators. In conclusion, the combined use of a synchrotron X‐ray microbeam‐irradiated three‐dimensional ROS gel and confocal laser scanning fluorescence microscopy provides a simple dosimetry method for track analysis of X‐ray photoelectric nanoradiator radiation, suggesting extensive cellular damage with dose‐enhancement beyond a single cell containing IONs.     

57Fe Mössbauer spectroscopy and X-ray diffraction study of complex metamict minerals. Part II

The magnetic behaviour of the nanocrystalline Ni_0.5Cu_0.5Fe₂O₄, synthesized by the co-precipitation method has been studied. The X-ray diffraction patterns confirm the formation of cubic spinel structure. The dc magnetization measurements show that the samples are superparamagnetic above the blocking temperatures and the blocking temperature increases with particle size. The reduction in saturation magnetization in the case of nanoparticles as compared to their bulk counterpart has been explained on the basis that the magnetic moments in the surface layers of a nanoparticle are in a state of frozen disorder. The hump in ZFC curve progressively shift to a lower temperature with increasing field and broader curves at higher field, suggests the spin-glass nature of the system.