Selective Covalent Modification of Layered Double Hydroxide Nanoparticles with Tripodal Ligands on Outer and Interlayer Surfaces.

Layered double hydroxides (LDHs) have occupied an important place in the fields of catalysts, electrocatalysts, and fillers, and their applicability can be greatly enhanced by interlayer organic modifications. In contrast to general organic modification based on noncovalent modification using ionic organic species, this study has clarified in situ interlayer covalent modification of LDH nanoparticles (LDHNPs) with the tripodal ligand tris(hydroxymethyl)aminomethane (Tris-NH2). Interlayer-modified CoAl LDHNPs were obtained by a one-pot hydrothermal treatment of an aqueous solution containing metal salts and Tris-NH2 at 180 °C for 24 h. Tris-NH2 was covalently bonded on the interlayer surface of LDHNPs. Interlayer-modified NiAl LDHNPs were also similarly synthesized. Some comparative experiments under different conditions indicate that the important parameters for interlayer modification are the number of bonding sites per a modifier, the electronegativity of a constituent divalent metal element, and the concentration of a modifier; this is because these parameters affect the hydrolytic stability of alkoxy-metal bonds between a modifier and a layer of LDHNPs. The synthesis of interlayer-modified MgAl LDHNPs was achieved by adjusting these parameters. This achievement will enable new potential applications because modification of only the outer surface has been achieved until now. Interlayer-modified LDHNPs possessing CO32- in the interlayer space were delaminated into monolayers under ultrasonication in water. The proposed method provides a rational approach for interlayer modification and facile delamination of LDHNPs.

Detection and destruction of HER2-positive cancer cells by Ultra Quenchbody-siRNA complex.

Ultra Quenchbody (UQ-body) is a biosensor that utilizes the quenching behavior of the fluorescent dye linked to the antibody V region. When the corresponding antigen is bound to the UQ-body, the fluorescence is restored and allows the detection of target molecules easily and sensitively. In this paper, we constructed UQ-bodies to sensitively detect the human epidermal growth factor receptor 2 (HER2) cancer marker in solution or on cancer cells, which was further used to kill the cancer cells. A synthetic Fab fragment of anti-HER2 antibody Fab37 with many Trp residues at hypervariable region was prepared and labeled with fluorescent dyes to obtain the UQ-bodies. The UQ-body could detect HER2 in solution at concentrations as low as 20 pM with an EC50 of 0.3 nM with a fourfold response. Fluorescence imaging of HER2-positive cells was successfully performed without any washing steps. To deliver small interfering RNA (siRNA) to cancer cells, a modified UQ-body with C-terminal 9R sequence was also prepared. HER2-positive cancer cells were effectively killed by polo-like kinase 1 siRNA intracellularly delivered by the UQ-body-9R. The novel approach employing siRNA-empowered UQ-body could detect and image the HER2 antigen easily and sensitively, and effectively kill the HER2-positive cancer cells.

Precise size control of layered double hydroxide nanoparticles through reconstruction using tripodal ligands.

Precise size control of layered double hydroxide nanoparticles (LDHNPs) is crucial for their applications in anion exchange, catalysis, and drug delivery systems. Here, we report the synthesis of LDHNPs through a reconstruction method, using tripodal ligands (e.g., tris(hydroxymethyl)aminomethane; THAM). We found that the mechanism of reconstruction at least includes a dissolution-recrystallization process rather than topotactic transformation. THAM is immobilized on the surface of recrystallized LDHNPs with tridentate linkages, suppressing their crystal growth especially in lateral directions. The particle size of the LDHNPs is precisely controlled by the concentration of THAM regardless of the synthetic routes, such as coprecipitation and reconstruction. It is suggested that the particle size is controlled on the basis of Ostwald ripening which is governed by the equilibrium of the surface modification reaction.

Preparation of Mesoporous Basic Oxides through Assembly of Monodispersed Mg-Al Layered Double Hydroxide Nanoparticles.

Mesoporous basic Mg-Al mixed metal oxides (MMOs) with a high surface area and large pore size have been prepared through the assembly of monodispersed layered double hydroxide nanoparticles (LDHNPs) with block copolymer templates. The particle sizes of the LDHNPs were mainly controlled by varying the concentration of tris(hydroxymethyl)aminomethane (THAM), which was used as a surface stabilizing agent. LDHNPs and micelles of a block copolymer (Pluronic F127) were assembled to form a composite. The composites were calcined to transform them into mesoporous MMOs and to remove the templates. The Brunauer-Emmett-Teller surface areas, mesopore sizes, and pore volumes increased as a result of using the templates. Moreover, the pore sizes of the mesoporous MMOs could be controlled by using LDHNPs of different sizes. The mesoporous MMOs prepared from the LDHNPs showed much higher catalytic activity than a conventional MMO catalyst for the Knövenagel condensation of ethyl cyanoacetate with benzaldehyde. The mesoporous MMO catalyst prepared using the smallest LDHNPs, about 12 nm in size, showed the highest activity. Therefore, the use of monodispersed LDHNPs and templates is effective for preparing highly active mesoporous solid base catalysts.