Understanding Flexdispersion: Structure-Function Relationship Studies of Organic Amphiphilic Ligands.

Since inorganic nanoparticles have unique properties that differ from those of bulk materials, their material applications have attracted attention in various fields. In order to utilize inorganic nanoparticles for functional materials, they must be dispersed without agglomeration. Therefore, the surfaces of inorganic nanoparticles are typically modified with organic ligands to improve their dispersibility. Nevertheless, the relationship between the tail group structure in organic ligands and the dispersibility of inorganic nanoparticles in organic solvents remains poorly understood. We previously developed amphiphilic ligands that consist of ethylene glycol chains and alkyl chains to disperse inorganic nanoparticles in a variety of organic solvents. However, the structural requirements for amphiphilic ligands to "flexibly" disperse nanoparticles in less polar to polar solvents are still unclear. Here, we designed and synthesized several phosphonic acid ligands for structure-function relationship studies of flexdispersion. Dynamic light scattering analysis and visible light transmittance measurements revealed that the ratio of alkyl/ethylene glycol chains in organic ligands alone does not determine the dispersibility of the nanoparticles in organic solvents, but the arrangement of the individual chains also has an effect. From a practical application standpoint, it is preferable to design ligands with ethylene glycol chains on the outside relative to the particle surface.

Dispersibility of TiO2 Nanoparticles in Less Polar Solvents: Role of Ligand Tail Structures.

Nanoparticles (NPs) are inherently prone to aggregation and loss of their size-derived properties, thus it is essential to enhance their dispersibility for applications. In less polar solvents, organic ligands containing oleyl groups are known as good dispersants due to their inefficient shell packing and inhibition of chain-chain crystallization as well as interdigitation between adjacent NPs. However, reagents with oleyl structures, such as oleic acid and oleylamine, can contain trans double bonds and saturated impurities, which might affect the chemical and/or physical properties of the NPs. Nevertheless, the effect of slight differences in surface ligand structure, including isomers, on the dispersibility of NPs has been little studied. We have synthesized five phosphonic acid ligands to investigate the structure-dispersibility relationship in detail. Dynamic light scattering and visible light transmittance revealed that not only regio- but also the stereochemistries of the C=C double bond in the ligand molecule, as well as the choice of solvent, are key factors in enhancing dispersibility.

Colloidal Stability of TiO2 Nanoparticles: The Roles of Phosphonate Ligand Length and Solution Temperature.

Invited for the cover of this issue are Dr. Shohei Yamashita, Tatsuya Sudo, Prof. Dr. Hidehiro Kamiya, and Prof. Dr. Yohei Okada at Tokyo University of Agriculture and Technology. The image depicts the role of phosphonate ligand length in the colloidal stability of TiO2 nanoparticles. Read the full text of the article at 10.1002/chem.202201560.

Colloidal Stability of TiO2 Nanoparticles: The Roles of Phosphonate Ligand Length and Solution Temperature.

Surface ligands are essential tools for the stabilization of colloidal nanoparticles (NPs) in solvents. However, knowledge regarding the effects of the ligand shell, especially the ligand length, is insufficient and controversial. Here we demonstrate solution-based experiments on n-alkylphosphonate-capped TiO2 NPs to investigate the effects of ligand length and solution temperature on colloidal stability. A robust ligand-exchange process is achieved that draws free ligands and impurities away from the colloidal solution. In the case of 8 nm anatase NPs in toluene, the dodecylphosphonate ligand provided better colloidal stability than all the other n-alkylphosphonate ligands. In addition, relaxation studies suggested there is kinetic hysteresis in the dispersion/agglomeration transition. The proposed method is applicable to a wide range of surface ligands designed to maximize the colloidal stability of NPs.

Cell death in neural precursor cells and neurons before neurite formation prevents the emergence of abnormal neural structures in the Drosophila optic lobe.

Programmed cell death is a conserved strategy for neural development both in vertebrates and invertebrates and is recognized at various developmental stages in the brain from neurogenesis to adulthood. To understand the development of the central nervous system, it is essential to reveal not only molecular mechanisms but also the role of neural cell death (Pinto-Teixeira et al., 2016). To understand the role of cell death in neural development, we investigated the effect of inhibition of cell death on optic lobe development. Our data demonstrate that, in the optic lobe of Drosophila, cell death occurs in neural precursor cells and neurons before neurite formation and functions to prevent various developmental abnormalities. When neuronal cell death was inhibited by an effector caspase inhibitor, p35, multiple abnormal neuropil structures arose during optic lobe development-e.g., enlarged or fused neuropils, misrouted neurons and abnormal neurite lumps. Inhibition of cell death also induced morphogenetic defects in the lamina and medulla development-e.g., failures in the separation of the lamina and medulla cortices and the medulla rotation. These defects were reproduced in the mutant of an initiator caspase, dronc. If cell death was a mechanism for removing the abnormal neuropil structures, we would also expect to observe them in mutants defective for corpse clearance. However, they were not observed in these mutants. When dead cell-membranes were visualized with Apoliner, they were observed only in cortices and not in neuropils. These results suggest that the cell death occurs before mature neurite formation. Moreover, we found that inhibition of cell death induced ectopic neuroepithelial cells, neuroblasts and ganglion mother cells in late pupal stages, at sites where the outer and inner proliferation centers were located at earlier developmental stages. Caspase-3 activation was observed in the neuroepithelial cells and neuroblasts in the proliferation centers. These results indicate that cell death is required for elimination of the precursor cells composing the proliferation centers. This study substantiates an essential role of early neural cell death for ensuring normal development of the central nervous system.