Scheme 1. Schematic illustration of the fabrication of the 3D NNCNTAs water oxidation electrode by means of electro-deposition.

Parallel studies of the preparation of Re and (99m)Tc agents aid in interpreting the nature of tracer (99m)Tc radiopharmaceuticals. Aqueous solutions of the fac-[(99m)Tc(CO)(3)(H(2)O)(3)](+) cation are gaining wide use and are readily prepared, but such solutions of the fac-[Re(CO)(3)(H(2)O)(3)](+) cation (1) are not so easily accessible. Herein we describe a new, reliable, and straightforward preparation of aqueous solutions of 1, characterized by HPLC and ESI-MS. Treatment of solutions of 1 with thioether-bearing amino acids, AAH = S-methyl-l-cysteine (MECYSH), S-propyl-l-cysteine (PRCYSH), and methionine (METH), gave high yields of fac-Re(CO)(3)AA complexes. X-ray crystallographic and NMR analyses indicated that MECYS(-), PRCYS(-), and MET(-) were bound in fac-Re(CO)(3)AA complexes as tridentate monoanionic ligands through amino, thioether, and alpha-carboxyl groups. In CD(3)OD, (1)H NMR spectra have broad signals but have two sets of signals at -10 degrees C, consistent with two isomers with different configurations at the pyramidal sulfur; these interconvert slowly on the NMR time scale at low temperatures. Indeed, the crystal structure of the fac-Re(CO)(3)(PRCYS) reveals a mixture of the two possible diastereoisomers. S-(Carboxymethyl)-l-cysteine (CCMH(2)) and 1 gave two products, 5A (kinetically favored) and 5B (thermodynamically favored). X-ray crystallographic analyses of a crystal of 5B and of a 1:1 cocrystal of 5A and 5B showed that 5A and 5B are diastereoisomers with the CCMH(-) alpha-carboxyl group dangling. In addition to the amino and thioether groups, the S-(carboxymethyl) carboxyl group is coordinated, a feature that slows interconversion of diastereoisomers relative to the other fac-Re(CO)(3)AA complexes because interconversion can now occur only after the rupture of Re-ligand bonds. These N, O, and S tridentate adducts are quite stable, and the grouping has promise in (99m)Tc(CO)(3) tracer development.

Among the Mo-and W-based two-dimensional (2D) transition metal dichalcogenides, MoTe 2 is particularly interesting for phase-engineering applications, because it has the smallest free energy difference between the semiconducting 2H phase and metallic 1T′ phase. In this work, we reveal that, under the proper circumstance, Mo and Te atoms can rearrange themselves to transform from a polycrystalline 1T′ phase into a single-crystalline 2H phase in a large scale. We manifest the mechanisms of the solid-to-solid transformation by conducting density functional theory calculations, transmission electron microscopy, energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy, and Raman spectroscopy. The phase transformation is well described by the time−temperature−transformation diagram. By optimizing the kinetic rates of nucleation and crystal growth, we have synthesized a single-crystalline 2H-MoTe 2 domain with a diameter of 2.34 mm, a centimeter-scale 2H-MoTe 2 thin film with a domain size up to several hundred micrometers, and a seamless 1T′−2H MoTe 2 coplanar homojunction. The 1T′−2H MoTe 2 homojunction provides an elegant solution for ohmic contact of 2D semiconductors. The controlled solid-to-solid phase transformation in 2D limit provides a new route to realize wafer-scale single-crystalline 2D semiconductor and coplanar heterostructure for 2D circuitry.

The integration of two-dimensional (2D) van der Waals semiconductors into silicon electronics technology will require the production of large-scale, uniform, and highly crystalline films. We report a route for synthesizing wafer-scale single-crystalline 2H molybdenum ditelluride (MoTe2) semiconductors on an amorphous insulating substrate. In-plane 2D-epitaxy growth by tellurizing was triggered from a deliberately implanted single seed crystal. The resulting single-crystalline film completely covered a 2.5-centimeter wafer with excellent uniformity. The 2H MoTe2 2D single-crystalline film can use itself as a template for further rapid epitaxy in a vertical manner. Transistor arrays fabricated with the as-prepared 2H MoTe2 single crystals exhibited high electrical performance, with excellent uniformity and 100% device yield.

Here, we demonstrated systematic experiments to understand the microscopic origin of laser irradiation induced controllable 2H-to-1T’ phase transition in few-layer MoTe2.

Tungsten ditelluride (WTe2) is a semi-metallic layered transition metal dichalcogenide with a stable distorted 1T phase. The reduced symmetry of this system leads to in-plane anisotropy in various materials properties. We have systemically studied the in-plane anisotropy of Raman modes in few-layer and bulk WTe2 by angle-dependent and polarized Raman spectroscopy (ADPRS). Ten Raman modes are clearly resolved. Their intensities show periodic variation with sample rotating. We identify the symmetries of the detected modes by quantitatively analyzing the ADPRS results based on the symmetry selection rules. Material absorption effect on the phonon modes with high vibration frequencies is investigated by considering complex Raman tensor elements. We also provide a rapid and nondestructive method to identify the crystallographic orientation of WTe2. The crystallographic orientation is further confirmed by the quantitative atomic-resolution force image. Finally, we find that the atomic vibrational tendency and complexity of detected modes are also reflected in the shrinkage degree defined based on ADPRS, which is confirmed by corresponding density functional calculation. Our work provides a deep understanding of the interaction between WTe2 and light, which will benefit in future studies about the anisotropic physical properties of WTe2 and other in-plane anisotropic materials.

The group IV-VI compound tin selenide (SnSe) has recently attracted particular interest due to its unexpectedly low thermal conductivity and high power factor and shows great promise for thermoelectric applications. With an orthorhombic lattice structure, SnSe displays intriguing anisotropic properties due to the low symmetry of the puckered in-plane lattice structure. When thermoelectric materials, such as SnSe, have decreased dimensionality, their thermoelectric conversion efficiency may be improved due to increased power factor and decreased thermal conductivity. Therefore, it is necessary to elucidate the complete optical and electrical anisotropies of SnSe nanostructures in realizing the material's advantages in high-performance devices. Here, we synthesize single-crystal SnSe nanoplates (NPs) using the chemical vapor deposition method. The SnSe NPs' polarized Raman spectra exhibit an angular dependence that reveals the crystal's anomalous anisotropic light-matter interaction. The Raman's anisotropic response has a dependence upon the incident light polarization, photon, and phonon energy, arising from the anisotropic electron-photon and electron-phonon interactions in the SnSe NPs. Finally, angle-resolved charge-transport measurements indicate strong anisotropic conductivity of the SnSe NPs, fully elucidating the anisotropic properties necessary for ultrathin SnSe in electronic, thermoelectric, and optoelectronic devices.

Enzyme works for plasmonic nanostructure: an interesting enzyme-responsive hybrid Ag/Au-GOx bimetallic nanoshell (NS) system is reported, in which control over the enzyme reaction of glucose oxidase (GOx) can automatically fine-tune the morphology (from complete NS to porous NS) and optical properties of the hybrid nanostructure. The phenomenon is further exploited as a new platform for sensitive optical glucose sensing.