Well-Defined Colloidal 2‑D Layered Transition-Metal Chalcogenide Nanocrystals via Generalized Synthetic Protocols

While interesting and unprecedented material characteristics of two dimensionality (2-D) layered nanomaterials are emerging, their reliable synthetic methodologies are not well developed. In this study we demonstrate general applicability of synthetic protocols to a wide range of colloidal 2-D layered transition-metal chalcogenide (TMC) nanocrystals. As distinctly different from other nanocrystals, we discovered that 2-D layered TMC nanocrystals are unstable in the presence of reactive radicals from elemental chalcogen during the crystal formation. We first introduce the synthesis of titanium sulfide and selenide where well-defined single crystallinity and lateral size controllability are verified, and then such synthetic protocols are extended to all of group IV and V transition-metal sulfide (TiS₂, ZrS₂, HfS₂, VS₂, NbS₂, and TaS₂) and selenide (TiSe₂, ZrSe₃, HfSe₃, VSe₂, NbSe₂, and TaSe₂) nanocrystals. The use of appropriate chalcogen source is found to be critical for the successful synthesis of 2-D layered TMC nanocrystals. CS₂ is an efficient chalcogen precursor for metal sulfide nanocrystals, whereas elemental Se is appropriate for metal selenide nanocrystals. We briefly discuss the effects of reactive radical characteristics of elemental S and Se on the formation of 2-D layered TMC nanocrystals

Transformative Two-Dimensional Layered Nanocrystals

Regioselective chemical reactions and structural transformations of two-dimensional (2D) layered transition-metal chalcogenide (TMC) nanocrystals are described. Upon exposure of 2D TiS2 nanodiscs to a chemical stimulus, such as Cu ion, selective chemical reaction begins to occur at the peripheral edges. This edge reaction is followed by ion diffusion, which is facilitated by interlayer nanochannels and leads to the formation of a heteroepitaxial TiS2–Cu2S intermediate. These processes eventually result in the generation of a single-crystalline, double-convex toroidal Cu2S nanostructure. Such 2D regioselective chemical reactions also take place when other ionic reactants are used. The observations made and chemical principles uncovered in this effort indicate that a general approach exists for building various toroidal nanocrystals of substances such as Ag2S, MnS, and CdS

Ultrathin Zirconium Disulfide Nanodiscs

We present a colloidal route for the synthesis of ultrathin ZrS2 (UT-ZrS2) nanodiscs that are ∼1.6 nm thick and consist of approximately two unit cells of S–Zr–S. The lateral size of the discs can be tuned to 20, 35, or 60 nm while their thickness is kept constant. Under the appropriate conditions, these individual discs can self-assemble into face-to-face-stacked structures containing multiple discs. Because the S–Zr–S layers within individual discs are held together by weak van der Waals interactions, each UT-ZrS2 disc provides spaces that can serve as host sites for intercalation. When we tested UT-ZrS2 discs as anodic materials for Li+ intercalation, they showed excellent nanoscale size effects, enhancing the discharge capacity by 230% and greatly improving the stability in comparison with bulk ZrS2. The nanoscale size effect was especially prominent for their performance in fast charging/discharging cycles, where an 88% average recovery of reversible capacity was observed for UT-ZrS2 discs with a lateral diameter of 20 nm. The nanoscale thickness and lateral size of UT-ZrS2 discs are critical for fast and reliable intercalation cycling because those dimensions both increase the surface area and provide open edges that enhance the diffusion kinetics for guest molecules

Nanoparticle Assemblies as Memristors

Recently a memristor (Chua, L. O. IEEE Trans. Circuit Theory 1971, 18, 507), the fourth fundamental passive circuit element, has been demonstrated as thin film device operations (Strukov, D. B.; Snider, G. S.; Stewart, D. R.; Williams, R. S. Nature (London) 2008, 453, 80; Yang, J. J.; Pickett. M. D.; Li, X.; Ohlberg, D. A. A.; Stewart, D. R.; Williams, R. S. Nat. Nanotechnol. 2008, 3, 429). A new addition to the memristor family can be nanoparticle assemblies consisting of an infinite number of monodispersed, crystalline magnetite (Fe3O4) particles. Assembly of nanoparticles that have sizes below 10 nm, exhibits at room temperature a voltage−current hysteresis with an abrupt and large bipolar resistance switching (ROFF/RON ≈ 20). Interestingly, observed behavior could be interpreted by adopting an extended memristor model that combines both a time-dependent resistance and a time-dependent capacitance. We also observed that such behavior is not restricted to magnetites; it is a general property of nanoparticle assemblies as it was consistently observed in different types of spinel structured nanoparticles with different sizes and compositions. Further investigation into this new nanoassembly system will be of importance to the realization of the next generation nanodevices with potential advantages of simpler and inexpensive device fabrications

Magnetic Properties of Annealed Core–Shell CoPt Nanoparticles

A precise control and understanding of the magnetization dynamics of nanostructures is an important topic in applied nanosciences. Herein, we perform such control by annealing crystalline (Co/core)–(Pt/shell) nanoparticles. Using electron tomography, temperature dependent electron microscopy and time-resolved magneto-optics, we establish a clear correlation between the magnetization dynamics and the crystalline structure of the nanoparticles. For a mild laser annealing (370 K) the Co–Pt nanoparticles keep their core–shell structure and remain superparamagnetic with a blocking temperature <i>T</i>_B = 66 K. Their time-resolved reflectivity shows that they are locally organized into a supra-crystalline ordered layer in the region of the laser spot. In contrast, a thermal annealing at higher temperatures (up to 700 K) modifies the structure of the individual nanoparticles into a CoPt crystalline ferromagnetic phase, with <i>T</i>_B,anneal = 347 K. Correspondingly, the magneto-crystalline anisotropy of the annealed CoPt nanoparticles increases and their magnetization dynamics displays a motion of precession, characteristic of ferromagnetic nanostructures and which is absent in the superparamagnetic Co–Pt core–shells

Nanoscale Magnetism Control via Surface and Exchange Anisotropy for Optimized Ferrimagnetic Hysteresis

With the aim of controlling nanoscale magnetism, we demonstrate an approach encompassing concepts of surface and exchange anisotropy while reflecting size, shape, and structural hybridization of nanoparticles. We visualize that cube has higher magnetization value than sphere with highest coercivity at 60 nm. Its hybridization into core–shell (CS) structure brings about a 14-fold increase in the coercivity with an exceptional energy conversion of magnetic field into thermal energy of 10600 W/g, the largest reported to date. Such capability of the CS-cube is highly effective for drug resistant cancer cell treatment

Negatively Charged Metal Oxide Nanoparticles Interact with the 20S Proteasome and Differentially Modulate Its Biologic Functional Effects

The multicatalytic ubiquitin–proteasome system (UPS) carries out proteolysis in a highly orchestrated way and regulates a large number of cellular processes. Deregulation of the UPS in many disorders has been documented. In some cases, such as carcinogenesis, elevated proteasome activity has been implicated in disease development, while the etiology of other diseases, such as neurodegeneration, includes decreased UPS activity. Therefore, agents that alter proteasome activity could suppress as well as enhance a multitude of diseases. Metal oxide nanoparticles, often developed as diagnostic tools, have not previously been tested as modulators of proteasome activity. Here, several types of metal oxide nanoparticles were found to adsorb to the proteasome and show variable preferential binding for particular proteasome subunits with several peptide binding “hotspots” possible. These interactions depend on the size, charge, and concentration of the nanoparticles and affect proteasome activity in a time-dependent manner. Should metal oxide nanoparticles increase proteasome activity in cells, as they do <i>in vitro</i>, unintended effects related to changes in proteasome function can be expected