Stimuli-responsive materials, such as thermochromics, have found mass usage and profitability in manufacturing and process control. Imparting charge-transfer-based functional supramolecular materials with tunable thermochromism emerges as an ideal strategy to construct optically responsive multifunctional assemblies. Herein, the authors report a new series of thermochromic charge-transfer-based supramolecular materials assembled in water. These assemblies are composed of a bis-bipyridinium-derived acceptor and a series of commercially available donorsnamely, the neurotransmitter melatonin and its analogue bioisosteres. When the chemical structure of the donors are tailored, the strength of the charge-transfer interactions can be tuned. Thermochromic aerogels and inks of these materials are prepared, with a large selection of colors, in environment-friendly solvents and demonstrate tunable thermochromic transition temperatures ranging from 45 to 105 °C. Favorable compatibility of these materials with commercial inks and inkjet printers afford excellent pattern quality with extended color options. Mechanistic studies reveal that the two types of water molecules were bound to the supramolecular complexes with differing strengths, and that the more weakly bound water is responsible for the thermochromic transitions.

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Modulation of hypoxia is an essential factor for enhancing the effects of antitumor therapies, especially sonodynamic therapy and chemotherapy. To improve the efficacy of combination therapy by reversing the hypoxic tumor microenvironment, we developed shell-core structured PPID-NPs, which were designed with a polymer shell onto the sonosensitizer and a chemotherapeutic drug were loaded and a perfluorocarbon core loaded with oxygen. The perfluorocarbon core provides sufficient oxygen not only for causing the sonosensitizer to produce more singlet oxygen to induce cell apoptosis but also for reducing drug resistance to enhance therapeutic efficacy. Furthermore, the release of chemotherapeutic drugs at the tumor site can be controlled. Thus, PPID-NPs can efficiently inhibit the growth of breast cancer by synergistic therapy under ultrasound exposure. We believe that our oxygen-sufficient nanoplatform could be an ideal therapeutic system for hypoxic tumors.

Developing a methodology to build target structures is one of the major themes of synthetic chemistry. However, it has proven to be immensely challenging to achieve multilevel elaborate molecular architectures in a predictable way. Herein, we describe the self-assembly of a series of pinwheel-shaped starlike supramolecules through three rationally preorganized metalloligands L1−L3. The key octa-uncomplexed terpyridine (tpy) metalloligand L3, synthesized with an 8-fold Suzuki coupling reaction to metal-containing complexes, has four different types of terpyridines connected with three ⟨tpy-Ru 2+ -tpy⟩ units, making this the most subunits known so far for a preorganized module. Based on the principle of geometric complementation and the high "density of coordination sites", these metalloligands were assembled with Zn 2+ ions to form a pinwheel-shaped star trigon P1, pentagram P2, and hexagram P3 with precisely controlled shapes in nearly quantitative yields. With molecular weights ranging from 16756 to 56053 Da and diameters of 6.7−13.6 nm, the structural composition, shape, and rigidity of these pinwheel-shaped architectures have been fully characterized by 1D and 2D (NMR), electrospray ionization mass spectrometry, traveling-wave ion mobility mass spectrometry, and transmission electron microscopy.

Poly(ethylene-co-vinyl acetate) (PEVAc) nanocomposites containing exfoliated α-zirconium phosphate (ZrP) have been prepared using a simple solution mixing method to improve their barrier and mechanical properties. ZrP was pre-exfoliated with a surfactant, followed by additional targeted surface functionalization and surfactant exchange to allow for hydrogen bonding of ZrP with the acetate functionality on PEVAc and to improve ZrP surface hydrophobicity. The solvent is found to play an important role in stabilizing ZrP exfoliation in the presence of PEVAc to retain full exfoliation and homogeneous dispersion upon the removal of the solvent. The PEVAc/ZrP nanocomposite exhibits greatly improved oxygen barrier, melt strength, and mechanical properties. The usefulness of the present study for the preparation of olefinic polymer nanocomposites is discussed.

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Electro-caloric (EC) properties of lead-free Ba 0.5 Na 0.5 TiO 3 -xBaTiO 3 (BNT-xBT) ceramics prepared by citrate method are investigated at temperatures of 30-250°C. Based on thermodynamics calculations, BNT-xBT (x00, 0.05, 0.06, 0.1, 0.25, 0.3) are found to show EC effects different with other lead-based or lead-free ferroelectric ceramics, i.e., they absorb heats (refrigeration effect) during the processes of field application while other ferroelectric ceramics show refrigeration effect during the processes of field removal. The EC temperature change of BNT-xBT can be as large as 2.1°C under an electric field of 60 kV/cm, which is larger than most of the lead-free ferroelectric bulk ceramics. When x is close to the morphotropic phase boundary (x~0.06-0.1), the EC temperature change of BNT-xBT shows a maximum near the ferroelectric to anti-ferroelectric transition temperature, which is characterized by dynamic mechanical analysis. This study suggests that these lead-free ferroelectric materials are promising in the practical application as EC coolers.

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