Water Dispersal and Functionalization of Hydrophobic Iron Oxide Nanoparticles with Lipid-Modified Poly(amidoamine) Dendrimers

A novel and facile method for water dispersal of hydrophobic iron oxide nanoparticles based on the amphiphilic PAMAM-C₁₂ dendrimer is described. Stable and highly concentrated water dispersions of multifunctional magnetic nanoparticles were obtained with this single-step approach, and showed interesting relaxometric properties for MRI applications. Importantly, this method does not require substitution of the native hydrophobic capping under nonmild reaction conditions, thus preserving the structural and magnetic properties of the nanoparticles, and extending the possibility of conjugation with thermally labile groups

Mechanochemical Synthesis and Three-Dimensional Electron Diffraction Structure Solution of a Novel Cu-Based Protocatechuate Metal–Organic Framework

Mechanochemical synthesis is a powerful approach to obtain new materials, limiting costs, and times. However, defected and submicrometrical-sized crystal products make critical their characterization through classical single-crystal X-ray diffraction. A valid alternative is represented by three-dimensional (3D) electron diffraction, in which a transmission electron microscope is used, like a diffractometer. This work matches a green water-based mechanochemical synthesis and 3D electron diffraction to obtain and characterize a Cu-based protocatechuate metal–organic framework (PC-MOF). Its structure has been fully refined through dynamical diffraction theory, and free water molecules could be detected in the channels of the framework. Thermal characterization, focused on the dehydration profile determination, leads to the formation of a novel high-temperature 2D coordination polymer, fully solved with 3D electron diffraction data. At last, the strong activity of the PC-MOF against cationic dyes like methylene blue has been reported

Conducting Shrinkable Nanocomposite Based on Au-Nanoparticle Implanted Plastic Sheet: Tunable Thermally Induced Surface Wrinkling

A thermally shrinkable and conductive nanocomposite material is prepared by supersonic cluster beam implantation (SCBI) of neutral Au nanoparticles (Au NPs) into a commercially available thermo-retractable polystyrene (PS) sheet. Micronanowrinkling is obtained during shrinking, which is studied by means of SEM, TEM and AFM imaging. Characteristic periodicity is determined and correlated with nanoparticle implantation dose, which permits us to tune the topographic pattern. Remarkable differences emerged with respect to the well-known case of wrinkling of bilayer metal–polymer. Wrinkled composite surfaces are characterized by a peculiar multiscale structuring that promises potential technological applications in the field of catalytic surfaces, sensors, biointerfaces, and optics, among others

Texture and Phase Recognition Analysis of β‑NaYF₄ Nanocrystals

Texture and phase recognition analysis (TPRA) based on electron nanodiffraction technique is used to characterize the geometry of up-conversion nanocrystals (UCNCs) synthesized by the common thermal-decomposition protocol in the presence of a stoichiometric amount of NH₄F. Here, we confirmed experimentally that despite the apparently different shapes of samples (hexagons, rods, and cubes), all the nanocrystals are actually β-phase hexagonal prisms. This is of relevance since many biological features of nanostructures, such as cellular internalization and cytotoxicity, are governed by their geometry. In addition, reproducibility in biological experiments is paramount

Eu Incorporation into Sol–Gel Silica for Photonic Applications: Spectroscopic and TEM Evidences of α‑Quartz and Eu Pyrosilicate Nanocrystal Growth

The problem of Eu incorporation into silica as dispersed dopants, clusters, separate-phase nanoparticles, or nanocrystals, which is of key importance for applications in the fields of lasers and scintillators, is faced by applying to sol–gel silica doped with nine different Eu³⁺ concentrations (0.001–10 mol % range) various spectroscopic techniques, including crystal field and vibrational mode analysis by means of Fourier transform absorption and microreflectivity (in the 200–6000 cm^–1 and 9–300 K ranges), radioluminescence, and Raman scattering studies at 300 K. The variety of methods revealed the following concordant results: (1) amorphous Eu clusters grow when the Eu concentration is increased up to 3 mol % and (2) Si–OH groups are completely removed and ordered phase separation occurs at 10 mol % doping, as suggested by the remarkable narrowing of the spectral lines. Comparison with polycrystalline Eu oxide, Eu silicates, and α-quartz spectra allowed the unequivocal identification of Eu₂Si₂O₇ pyrosilicate and α-quartz as the main components of nanocrystals in 10 mol % Eu-doped silica. Such conclusions were brilliantly confirmed by transmission electron microscopy and electron diffraction analysis. Phonon coupling and anharmonicity were analyzed and are discussed for a few vibrational modes of nanocrystals

Catalyst Composition Tuning: The Key for the Growth of Straight Axial Nanowire Heterostructures with Group III Interchange

Au-catalyzed III–V nanowire heterostructures based on the group III interchange usually grow straight only in one of the two growth sequences, whereas the other sequence produces kinked geometries; thus, the realization of double heterostructures remains challenging. Here, we investigate the growth of Au-assisted InAs–GaAs and GaAs–InAs axial nanowire heterostructures. A detailed study of the heterostructure morphology as a function of growth parameters and chemical composition of the catalyst nanoparticle is performed by means of scanning electron microscopy, transmission electron microscopy, and energy-dispersive X-ray analysis. Our results clearly demonstrate that the nanoparticle composition, rather than other growth parameters, as postulated so far, controls the growth mode and the resulting nanowire morphology. Although GaAs easily grows straight on InAs, straight growth of InAs on GaAs is achieved only if the nanoparticle composition is properly tuned. We find that straight InAs segments on GaAs require high group III-to-Au ratios in the nanoparticle (greater than 0.8); otherwise, the droplet wets the sidewalls and the nanowire kinks. We discuss the observed behavior within a theoretical model that relates the nanoparticle stability to the group III-to-Au ratio. Based on this finding, we demonstrate the growth of straight nanowire heterostructures for both sequences. The proposed strategy can be extended to other III–V nanowire heterostructures based on the group III interchange, allowing for straight morphology regardless of the growth sequence, and ultimately for designing nanowire heterostructures with the required properties for different applications

Ionic Strength Responsive Sulfonated Polystyrene Opals

Stimuli-responsive photonic crystals (PCs) represent an intriguing class of smart materials very promising for sensing applications. Here, selective ionic strength responsive polymeric PCs are reported. They are easily fabricated by partial sulfonation of polystyrene opals, without using toxic or expensive monomers and etching steps. The color of the resulting hydrogel-like ordered structures can be continuously shifted over the entire visible range (405–760 nm) by changing the content of ions over an extremely wide range of concentration (from about 70 μM to 4 M). The optical response is completely independent from pH and temperature, and the initial color can be fully recovered by washing the sulfonated opals with pure water. These new smart photonic materials could find important applications as ionic strength sensors for environmental monitoring as well as for healthcare screening

<i>Ab Initio</i> Structure Determination of Cu_2–<i>x</i>Te Plasmonic Nanocrystals by Precession-Assisted Electron Diffraction Tomography and HAADF-STEM Imaging

We investigated pseudo-cubic Cu_2–<i>x</i>Te nanosheets using electron diffraction tomography and high-resolution HAADF-STEM imaging. The structure of this metastable nanomaterial, which has a strong localized surface plasmon resonance in the near-infrared region, was determined <i>ab initio</i> by 3D electron diffraction data recorded in low-dose nanobeam precession mode, using a new generation background-free single-electron detector. The presence of two different, crystallographically defined modulations creates a 3D connected vacancy channel system, which may account for the strong plasmonic response of this material. Moreover, a pervasive rotational twinning is observed for nanosheets as thin as 40 nm, resulting in a tetragonal pseudo-symmetry

Ultrafast Electron Diffraction Tomography for Structure Determination of the New Zeolite ITQ-58

In this work a new ultrafast data collection strategy for electron diffraction tomography is presented that allows reducing data acquisition time by one order of magnitude. This methodology minimizes the radiation damage of beam-sensitive materials, such as microporous materials. This method, combined with the precession of the electron beam, provides high quality data enabling the determination of very complex structures. Most importantly, the implementation of this new electron diffraction methodology is easily affordable in any modern electron microscope. As a proof of concept, we have solved a new highly complex zeolitic structure named ITQ-58, with a very low symmetry (triclinic) and a large unit cell volume (1874.6 ų), containing 16 silicon and 32 oxygen atoms in its asymmetric unit, which would be very difficult to solve with the state of the art techniques

An Advanced Lithium-Ion Battery Based on a Graphene Anode and a Lithium Iron Phosphate Cathode

We report an advanced lithium-ion battery based on a graphene ink anode and a lithium iron phosphate cathode. By carefully balancing the cell composition and suppressing the initial irreversible capacity of the anode in the round of few cycles, we demonstrate an optimal battery performance in terms of specific capacity, that is, 165 mAhg^–1, of an estimated energy density of about 190 Wh kg^–1 and a stable operation for over 80 charge–discharge cycles. The components of the battery are low cost and potentially scalable. To the best of our knowledge, complete, graphene-based, lithium ion batteries having performances comparable with those offered by the present technology are rarely reported; hence, we believe that the results disclosed in this work may open up new opportunities for exploiting graphene in the lithium-ion battery science and development