LiCs2PO4, a new deep-ultraviolet (UV) transparent material, was synthesized by the flux method. The material contains unusual edge-sharing LiO4-PO4 tetrahedra. It exhibits a very short absorption edge of λ = 174 nm and generates the largest powder second harmonic generation (SHG) response for deep-UV phosphates that do not contain additional anionic groups, i.e., 2.6 times that of KH2PO4 (KDP). First-principles electronic structure analyses confirm the experimental results and suggest that the strong SHG response may originate from the aligned nonbonding O-2p orbitals. The discovery and characterization of LiCs2PO4 provide a new insight into the structure-property relationships of phosphate-based nonlinear optical materials with large SHG responses and short absorption edges.

Supported Au nanocatalysts have attracted intensive interest because of their unique catalytic properties. Their poor thermal stability, however, presents a major barrier to the practical applications. Here we report an ultrastable Au nanocatalyst by localizing the Au nanoparticles (NPs) in the interfacial regions between the TiO2 and hydroxyapatite. This unique configuration makes the Au NP surface partially encapsulated due to the strong metal-support interaction and partially exposed and accessible by the reaction molecules. The strong interaction helps stabilizing the Au NPs while the partially exposed Au NP surface provides the active sites for reactions. Such a catalyst not only demonstrated excellent sintering resistance with high activity after calcination at 800 °C but also showed excellent durability that outperforms a commercial three-way catalyst in a simulated practical testing, suggesting great potential for practical applications.

A novel approach to chemically functionalize multiwalled carbon nanotubes (MWCNTs) for making advanced polymeric nanocomposites with liquid crystalline polymers (LCPs) is presented. In this approach, two types of chemical moieties (i.e., carboxylic and hydroxyl benzoic acid groups) are selectively introduced onto the sidewalls of the MWCNTs. Fourier transform IR and Raman spectroscopy are used to examine the interaction between the functionalized MWCNTs and the LCP. The strong interaction between the functionalized MWCNTs and the LCP greatly improved the dispersion of MWCNTs in the polymer matrix as well as the interfacial adhesion. The dispersion of the MWCNTs in the LCP matrix is observed by optical microscopy and field‐emission scanning electron microscopy. As a result, the addition of 1 wt% MWCNTs in the LCP resulted in the significant improvement (41 and 55%) in the tensile strength and modulus of the LCP.

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A novel strategy to improve the adhesion between printed layers of three-dimensional (3D) printed constructs is developed by exploiting the interaction between two oppositely charged hydrogels. Three anionic hydrogels [alginate, xanthan, and κ-carrageenan (Kca)] and three cationic hydrogels [chitosan, gelatin, and gelatin methacrylate (GelMA)] are chosen to find the optimal combination of two oppositely charged hydrogels for the best 3D printability with strong interface bonding. Rheological properties and printability of the hydrogels, as well as structural integrity of printed constructs in cell culture medium, are studied as functions of polymer concentration and the combination of hydrogels. Kca2 (2 wt % Kca hydrogel) and GelMA10 (10 wt % GelMA hydrogel) are found to be the best combination of oppositely charged hydrogels for 3D printing. The interfacial bonding between a Kca layer and a GelMA layer is proven to be significantly higher than that of the bilayered Kca or bilayered GelMA because of the formation of polyelectrolyte complexes between the oppositely charged hydrogels. A good cell viability of >96% is obtained for the 3D-bioprinted Kca-GelMA construct. This novel strategy has a great potential for 3D bioprinting of layered constructs with a strong interface bonding.

The coordination ability of ligands functionalized by azobenzene was manipulated, and two novel chelating ligands, (E)-4-(phenyldiazenyl)-N,N-bis(pyridin-2-ylmethyl) benzohydrazide (CHNO, PBPM) and (E)-4-((4-(dimethylamino)phenyl)diazenyl)-N,N-bis(pyridin-2-ylmethyl) benzohydrazide (CHNO, dmPBPM), were synthesized. The ligands can offer four coordinating atoms (one oxygen and three nitrogens) to act as tetradendate ligands, together with the two β-diketonates (4,4,4-trifluoro-1-phenylbutane-1,3-dionate, tfd), and the trifluoroacetate anion presented as a ligand and a counterion to form the quaternary units with lanthanide(III) ions (La, Eu, and Gd), [Ln(tfd)(PBPM)(CFCO)] (LnCHFNO) and [Ln(tfd)(dmPBPM)(CFCO)] (LnCHFNO), where the lanthanide(III) ions are nine coordinated with NO donor sets. All six complexes were structurally characterized, and four crystals were obtained and further analyzed by means of single-crystal X-ray diffraction. They all crystallized in the monoclinic P2/c space group with very similar lattice parameters, forming a monocapped twisted square antiprism. We successfully observed the photoluminescent properties of Eu(III) complexes at a wavelength of 614 nm in both solution and the solid state, as well as the trans-to-cis photoisomerization with the quantum yield (Φ = 10) of [Eu(tfd)(PBPM)(CFCO)] complex that was comparable to that of PBPM. Moreover, the trans-to-cis photoisomerization rates of complexes [Ln(tfd)(PBPM)(CFCO)] (La, Eu, Gd) (10-10 s ) were also at the same level as that of PBPM and much higher than azobenzene itself (10-10 s). With the aid of TD-DFT calculations, the luminescence of Eu(III) complexes was found to originate from the attenuation effect of β-diketonates. These features provide the foundation for the development of azobenzene-derived β-diketonates lanthanide(III) complexes with photoisomerization and photoluminescence dual functions.

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Novel azobenzene-derived β-diketonates (4,4,5,5,6,6,6-heptafluoro-1-azobenzene-1,3-hexanedione (LA), 4,4,5,5,6,6,6-heptafluoro-1-(4-dimethylamino)azobenzene-1,3-hexanedione (LB)) were designed and their complexes with lanthanide cations (La(3+), Eu(3+), Gd(3+), Yb(3+)) were prepared and characterized by (1)H NMR, FT-IR, and elemental analysis. Three of the complexes were crystallized successfully and identified by X-ray diffraction. It was significant to find that LA showed remarkably reversible trans-to-cis isomerization properties, however, LB, bearing an electron donor compared with LA, slowed down the isomerization to an extent. The presence of Ln(iii) enhanced the reversible trans-to-cis isomerization properties of both LA and LB a little upon photoirradiation in organic solvents, and amazingly increased the fatigue resistance. In addition, the complexes doped in polymethyl methacrylate (PMMA) films produced a similar phenomenon as well as when in solution. Theoretical calculations based on time dependent density functional theory (TD-DFT) were performed for geometry optimization and to determine the excitation energies of LA and LB to gain further insight into the electronic structure of the complexes, and the data were consistent with the experimental results. The excellent reversible photoisomerization properties of the newly designed Ln(iii) complexes can offer important advantages that will help with the further study of these materials to reach their full potential in applications such as molecular switching devices.