Size‑, Mass‑, and Density-Controlled Preparation of TiO₂ Nanoparticles in a Spherical Coordination Template

TiO₂ nanoparticles were prepared with strict control of the size, molecular mass (PDI = 1.02), and mass density by hydrolyzing a precursor, Ti­(acac)₂(biphen), in the presence of a well-defined hollow Pd₁₂L₂₄ spherical endotemplate. The formation of highly monodisperse TiO₂ nanoparticles was confirmed by ¹H NMR spectroscopy, MALDI–TOF mass spectrometry, transmission electron microscopy, and atomic force microscopy. The template was easily removed by treating the sphere with a metal scavenger followed by calcination to give crystalline TiO₂ nanoparticles (2.0 ± 0.2 nm in diameter), which showed photocatalytic activity

Noncovalent Tailoring of the Binding Pocket of Self-Assembled Cages by Remote Bulky Ancillary Groups

The binding properties of a self-assembled coordination cage were subtly tuned by ancillary groups on the metal corners of the cage. Since the bulky mesityl groups of the ligand hang over the cage cavity, the effective cavity volume is reduced. Due to the tighter guest packing inside the shrunken cavity, smaller guests were efficiently bound and guest motion was restricted even at high temperatures

Noncovalent Tailoring of the Binding Pocket of Self-Assembled Cages by Remote Bulky Ancillary Groups

The binding properties of a self-assembled coordination cage were subtly tuned by ancillary groups on the metal corners of the cage. Since the bulky mesityl groups of the ligand hang over the cage cavity, the effective cavity volume is reduced. Due to the tighter guest packing inside the shrunken cavity, smaller guests were efficiently bound and guest motion was restricted even at high temperatures

Simulation of Metal–Ligand Self-Assembly into Spherical Complex M₆L₈

Molecular dynamics simulations were performed to study the self-assembly of a spherical complex through metal–ligand coordination interactions. M₆L₈, a nanosphere with six palladium ions and eight pyridine-capped tridentate ligands, was selected as a target system. We successfully observed the spontaneous formation of spherical shaped M₆L₈ cages over the course of our simulations, starting from random initial placement of the metals and ligands. To simulate spontaneous coordination bond formations and breaks, the cationic dummy atom method was employed to model nonbonded metal–ligand interactions. A coarse-grained solvent model was used to fill the gap between the time scale of the supramolecular self-assembly and that accessible by common molecular dynamics simulation. The simulated formation process occurred in the distinct three-stage (assembly, evolution, fixation) process that is well correlated with the experimental results. We found that the difference of the lifetime (or the ligand exchange rate) between the smaller-sized incomplete clusters and the completed M₆L₈ nanospheres is crucially important in their supramolecular self-assembly

Enhanced yet Inverted Effects of π‑Extension in Self-Assembly of Curved π‑Systems with Helicity

A sextuple helix molecule possessing four cove regions of helicene and two axes of biaryls was synthesized. The entropy-driven self-assembly in solution was determined by concentration- and temperature-dependent NMR spectra, which also revealed unique dynamics of isomerization involving structural changes at the cove regions. Unexpectedly, the assembly retarded the isomerization in solution, and the sextuple helix structure was rigidified

Noncovalent Tailoring of the Binding Pocket of Self-Assembled Cages by Remote Bulky Ancillary Groups

The binding properties of a self-assembled coordination cage were subtly tuned by ancillary groups on the metal corners of the cage. Since the bulky mesityl groups of the ligand hang over the cage cavity, the effective cavity volume is reduced. Due to the tighter guest packing inside the shrunken cavity, smaller guests were efficiently bound and guest motion was restricted even at high temperatures

Stereodivergent Synthesis and Configurational Assignment of the C1–C15 Segment of Amphirionin‑5

The relative configuration of the C3–C12 portion of amphirionin-5, a novel marine polyketide with potent cell proliferation-promoting activity, was established by the stereodivergent synthesis of six diastereomeric model compounds and comparison of their NMR spectroscopic data with those reported for the natural product. This study led to the elucidation of the relative configuration between C4/C5 and C9/C12 and to the reassignment of the proposed configuration of the C9 position of amphirionin-5

A diagnosis of environmental awareness in sport and sport policy

This article sheds light on the problematic, but urgent, relation between sport and its environmental effects by focusing on the development of internal policies in the Swedish sport movement as well as on external normative pressures for a sustainable environmental development. The materials in this study portray a passive (and blind) governance in relation to an official environmental policy at macro and meso levels, regardless of the manifestations of individual environmental projects in everyday sport practices. The analysis shows that the ideology of the autonomy of sport and the emphasis on self- regulation, regularly upheld by the Swedish Sports Confederation, is obsolete