One-pot green bio-assisted synthesis of highly active catalytic palladium nanoparticles in porcine gastric mucin for environmental applications.

In this work, palladium nanoparticles were synthesized using one-pot synthesis utilizing porcine gastric mucin glycoproteins as reducing and capping agents. It is shown that the particles exhibited noticeable catalytic activity through both nitrophenol reduction and Suzuki-Miyaura coupling reactions. The catalytic performance was demonstrated with exceptionally high product yield, a fast reaction rate, and low catalyst use. The palladium-mucin composites obtained could be used in particle solution and as hydrogel catalysts to increase their reusability for at least ten reaction cycles with minimum loss in their catalytic effectiveness.

Unidirectional rotation of micromotors on water powered by pH-controlled disassembly of chiral molecular crystals.

Biological and synthetic molecular motors, fueled by various physical and chemical means, can perform asymmetric linear and rotary motions that are inherently related to their asymmetric shapes. Here, we describe silver-organic micro-complexes of random shapes that exhibit macroscopic unidirectional rotation on water surface through the asymmetric release of cinchonine or cinchonidine chiral molecules from their crystallites asymmetrically adsorbed on the complex surfaces. Computational modeling indicates that the motor rotation is driven by a pH-controlled asymmetric jet-like Coulombic ejection of chiral molecules upon their protonation in water. The motor is capable of towing very large cargo, and its rotation can be accelerated by adding reducing agents to the water.

Characterization of Atomic Structures of Nanosized Intermetallic Compounds Using Electron Diffraction Methods.

In metallurgy, many intermetallic compounds crystallize as nanosized particles in metallic matrices. These particles influence dramatically the physical properties of engineering materials such as alloys and steels. Since properties and crystal structure are intimately linked, characterization of the atomic model of these intermetallides is crucial for the development of new alloys. However, this structural information usually cannot be attained using traditional X-ray diffraction methods, limited by the small volume and size of the precipitates. In these cases, electron diffraction (ED) is the most suitable method. In the last few decades, ED has experienced a tremendous leap forward. Many structures, including intermetallides, are solved using these methods. The class of intermetallides should be discussed independently since these phases do not comprise regular polyhedrals; moreover, the interatomic distances and angles vary drastically even in the same compositional system. These facts point to difficulties that have to be overcome during the solution path. Furthermore, intermetallic compounds can be of high complexity-possessing hundreds of atoms in the unit cell. Here, this topic is expanded with an emphasis on novel developments in the field.

Radiation Resistance of the U(Al, Si)3 Alloy: Ion-Induced Disordering.

During the exploitation of nuclear reactors, various U-Al based ternary intermetallides are formed in the fuel-cladding interaction layer. Structure and physical properties of these intermetallides determine the radiation resistance of cladding and, ultimately, the reliability and lifetime of the nuclear reactor. In current research, U(Al, Si)3 composition was studied as a potential constituent of an interaction layer. Phase content of the alloy of an interest was ordered U(Al, Si)3, structure of which was reported earlier, and pure Al (constituting less than 20 vol % of the alloy). This alloy was investigated prior and after the irradiation performed by Ar ions at 30 keV. The irradiation was performed on the transmission electron microscopy (TEM, JEOL, Japan) samples, characterized before and after the irradiation process. Irradiation induced disorder accompanied by stress relief. Furthermore, it was found that there is a dose threshold for disordering of the crystalline matter in the irradiated region. Irradiation at doses equal or higher than this threshold resulted in almost solely disordered phase. Using the program "Stopping and Range of Ions in Matter" (SRIM), the parameters of penetration of Ar ions into the irradiated samples were estimated. Based on these estimations, the dose threshold for ion-induced disordering of the studied material was assessed.

Assembly of mesoscale helices with near-unity enantiomeric excess and light-matter interactions for chiral semiconductors.

Semiconductors with chiral geometries at the nanoscale and mesoscale provide a rich materials platform for polarization optics, photocatalysis, and biomimetics. Unlike metallic and organic optical materials, the relationship between the geometry of chiral semiconductors and their chiroptical properties remains, however, vague. Homochiral ensembles of semiconductor helices with defined geometries open the road to understanding complex relationships between geometrical parameters and chiroptical properties of semiconductor materials. We show that semiconductor helices can be prepared with an absolute yield of ca 0.1% and an enantiomeric excess (e.e.) of 98% or above from cysteine-stabilized cadmium telluride nanoparticles (CdTe NPs) dispersed in methanol. This high e.e. for a spontaneously occurring chemical process is attributed to chiral self-sorting based on the thermodynamic preference of NPs to assemble with those of the same handedness. The dispersions of homochiral self-assembled helices display broadband visible and near-infrared (Vis-NIR) polarization rotation with anisotropy (g) factors approaching 0.01. Calculated circular dichroism (CD) spectra accurately reproduced experimental CD spectra and gave experimentally validated spectral predictions for different geometrical parameters enabling de novo design of chiroptical semiconductor materials. Unlike metallic, ceramic, and polymeric helices that serve predominantly as scatterers, chiroptical properties of semiconductor helices have nearly equal contribution of light absorption and scattering, which is essential for device-oriented, field-driven light modulation. Deconstruction of a helix into a series of nanorods provides a simple model for the light-matter interaction and chiroptical activity of helices. This study creates a framework for further development of polarization-based optics toward biomedical applications, telecommunications, and hyperspectral imaging.

Electrochemical Intercalation of Lithium Ions into NbSe2 Nanosheets.

Transition metal dichalcogenides (TMDCs) have been known for decades to have unique properties and recently attracted broad attention for their two-dimensional (2D) characteristics. NbSe2 is a metallic TMDC that has been studied for its charge density wave transition behavior and superconductivity but is still largely unexplored for its potential use in engineered devices with applications in areas such as electronics, optics, and batteries. Thus, we successfully demonstrate and present evidence of lithium intercalation in NbSe2 as a technique capable of modifying the material properties of NbSe2 for further study. We demonstrate successful intercalation of Li ions into NbSe2 and confirm this result through X-ray diffraction, noting a unit cell size increase from 12.57 to 13.57 Å in the c lattice parameter of the NbSe2 after intercalation. We also fabricate planar half-cell electrochemical devices using ultrathin NbSe2 from platelets to observe evidence of Li-ion intercalation through an increase in the optical transmittance of the material in the visible range. Using 550 nm wavelength light, we observed an increase in optical transmittance of 26% during electrochemical intercalation.

Addressing a "Black Box" of Bottom-Up Synthesis: Revealing the Structures of Growing Colloidal-Nanocrystal Nuclei.

In bottom-up synthesis, products from reactions of structural building units rapidly pass from soluble molecular complexes to nanoscale intermediates, whose solution-state structures defy elucidation by any routine method. To address this, electron diffraction is used to reveal the structures of cryogenically "trapped" colloidal nanocrystals.

New nanocrystalline materials: a previously unknown simple cubic phase in the SnS binary system.

We report a new phase in the binary SnS system, obtained as highly symmetric nanotetrahedra. Due to the nanoscale size and minute amounts of these particles in the synthesis yield, the structure was exclusively solved using electron diffraction methods. The atomic model of the new phase (a = 11.7 Å, P2(1)3) was deduced and found to be associated with the rocksalt-type structure. Kramers-Kronig analysis predicted different optical and electronic properties for the new phase, as compared to α-SnS.

Atomic structure solution of the complex quasicrystal approximant Al77Rh15Ru8 from electron diffraction data.

The crystal structure of the novel Al77Rh15Ru8 phase (which is an approximant of decagonal quasicrystals) was determined using modern direct methods (MDM) applied to automated electron diffraction tomography (ADT) data. The Al77Rh15Ru8 E-phase is orthorhombic [Pbma, a = 23.40 (5), b = 16.20 (4) and c = 20.00 (5) Å] and has one of the most complicated intermetallic structures solved solely by electron diffraction methods. Its structural model consists of 78 unique atomic positions in the unit cell (19 Rh/Ru and 59 Al). Precession electron diffraction (PED) patterns and high-resolution electron microscopy (HRTEM) images were used for the validation of the proposed atomic model. The structure of the E-phase is described using hierarchical packing of polyhedra and a single type of tiling in the form of a parallelogram. Based on this description, the structure of the E-phase is compared with that of the ε6-phase formed in Al-Rh-Ru at close compositions.

New ordered phase in the quasi-binary UAl3-USi3 system.

The industrial importance of the U-Al-Si system stems from the fact that during processing the Al-based alloy (containing Si as impurity), used for the cladding of U (fuel in nuclear reactors), undergoes heat treatment which stimulates diffusion between the fuel and the cladding. One of the possible ways to represent the ternary U-Al-Si phase diagram is the construction of an UAl3-USi3 quasi-binary phase diagram. On the one hand, since the UAl3 and USi3 phases are isostructural, an isomorphous phase diagram is expected; on the other hand, some researchers observed a miscibility gap at lower temperatures. During our study of the UAl3-USi3 quasi-binary phase diagram, a new stable U(Alx,Si1 - x)3 phase was identified. The structure of this phase was determined, using a combination of electron crystallography and powder X-ray diffraction methods, as tetragonal [I4/mmm (No.139) space group], with lattice parameters a = b = 8.347 (1), c = 16.808 (96) Å. Its unit cell has 64 atoms and it can be described as an ordered variant of the U(Al,Si)3 solid solution. A Bärnighausen tree was constructed using the original U(Al,Si)3 structure as an aristotype.

Regioselective placement of alkanethiolate domains on tetrahedral and octahedral gold nanocrystals.

Electrostatically stabilized monolayer shells of metal-oxide cluster anions (polyoxometalates, or POMs) on the surfaces of ca. 8 nm tetrahedral and octahedral gold nanocrystals regioselectively direct water-soluble alkanethiolate ligands to the corners and edges of the gold polyhedra.

Orientations of polyoxometalate anions on gold nanoparticles.

Cryogenic transmission electron microscopy of polyoxometalate-protected gold nanoparticles reveals that the Preyssler ion, [NaP(5)W(30)O(110)](14-), lies "face down" with its C(5) axis perpendicular to the gold surface, while the Finke-Droege ion, [P(4)W(30)Zn(4)(H(2)O)(2)O(112)](16-), is "tilted", with its long axis close to 60° from the normal to the surface.

Polyoxometalate-directed assembly of water-soluble AgCl nanocubes.

"Out-of-pocket" association of Ag(+) to the tetradentate defect site of mono-vacant Keggin and Wells-Dawson polyoxometalate (POM) cluster-anions is used to direct the formation of water-soluble AgCl nanocubes.

Self-assembly and structure of directly imaged inorganic-anion monolayers on a gold nanoparticle.

Cryogenic "trapping" was used to obtain the first TEM images of self-assembled monolayers of inorganic anions on a gold nanoparticle. This unique structural information makes it possible to study the formation of a protecting-ligand shell at an unprecedented level of detail. The protecting ligands are polyoxometalates (POMs; alpha-X(n+)W(12)O(40)((8-n)-), X(n+) = Al(3+) and "2H(+)", and alpha-X(n+)W(11)O(39)((12-n)-), X(n+) = P(5+), Si(4+), and Al(3+)) with large negative charges for association with the gold surface and W atoms (Z = 74) for TEM imaging. The POM-anion shells were obtained by ligand exchange from citrate-protected 13.8 nm gold nanoparticles. Replacement of the organic (citrate) by inorganic (tungsten-oxide) ligand shells results in substantial changes in the surface plasmon resonance (SPR). By correlating cryo-TEM images with changes in the SPR, degrees of surface coverage were reliably quantified by UV-visible spectroscopy. Then, the kinetics and thermodynamics of ligand-shell formation were investigated by systematically varying POM structure and charge. Rates of POM association with the gold surface ("nucleation") are inhibited by the electric-potential barrier of the citrate-stabilized particles, while binding affinities increase linearly with the charges (from 5- to 9-) of structurally different POM anions, suggesting that no single orientation ("lattice matching") is required for monolayer self-assembly. Time-dependent cryo-TEM images reveal that monolayer growth occurs via "islands", a mechanism that points to cation-mediated attraction between bound POMs. Complete ligand shells comprised of 330 molecules of alpha-AlW(11)O(39)(9-) (1) possess small net charges (29e from zeta-potential measurements) and short Debye lengths (kappa(-1) = 1.0 nm), which indicate that approximately 99% of the 2970 K(+) counter cations lie within ca. 1.5 nm (approximately 3 hydrated K(+) ion diameters) from the outer surface of the POM shell. Energetic analysis of the 1.57 +/- 0.04 nm center-to-center distance between molecules of 1 further indicates that K(+) ions reside in the ca. 4.5 A spaces between the bound ligands. These findings reveal an important structural role for counter cations within POM ligand shells on gold nanoparticles, analogous to that for cations in the monolayer walls of hollow POM-macroanion vesicles.