The charge excitation and decay pathways of two-dimensional heteroatomic quantum dots (QDs) are affected by the quantum confinement effect, bandgap structure and strong exciton binding energy. Recently, semiconducting transition metal dichalcogenides (TMDs) have been intensively studied; however, the charge dynamics of metallic phase QDs (mQDs) of TMDs remain relatively unknown. Herein, we investigate the photophysical properties of TMD-mQDs of two sizes, where the TMD-mQDs show different charge excitation and decay pathways that are mainly ascribed to the defect states and valence band splitting, resulting in a large Stokes shift and two excitation bands for maximum photoluminescence (PL). Interestingly, the dominant excitation band redshifts as the size increases, and the time-resolved PL peak redshifts at an excitation wavelength of 266 nm in the smaller QDs. Additionally, the lifetime is shortened in the larger QDs. From the structural and theoretical analysis, we discuss that the charge decay pathway in the smaller QDs is predominantly affected by edge oxidation, whereas the vacancies play an important role in the larger QDs.

Self-healing, an autonomous repairing process stimulated by damage, has recently attracted a great deal of attention in the field of medical and mechanical engineering as well as from scientists, due to its valuable potential applications. However, as the self-healing process is mediated by specific functional materials, practical applications have been limited. Here, we introduce a healable homopolymer microcapsule that can self-heal a crack or cleaved part through a photochemical [2 + 2] cycloaddition process. Microcapsules were prepared through photopolymerization and suspension polymerization, each containing 1,1,1-tris (cinnamoyloxymethyl) ethane (TCE) and 1,1-di (cinnamoyloxymethyl) ethane (DCE) monomers, which act as healing materials. TCE and DCE monomers were polymerized into poly (TCE-co-DCE) without a photoinitiator under illumination. The epoxy specimen embedded with microcapsules showed obvious healing performance during illumination after cracking. From the FT-IR spectra for each step of the healing process, the specimen could be repeatedly self-healed through the reversible process of cyclobutane cross-links to the original cinnamate and vice versa. This work shows an alternative approach using homopolymer microcapsules to accomplish the repeatable self-healing of a crack without interface discontinuity, which could be adopted as a healing substance in various paints.

We experimentally demonstrate the simultaneous enhancement of Raman and photoluminescence (PL) of core-shell hybrid nanoparticles consisting of Ag (core) and polydiacetylene (PDA, shell) through the assistance of localized surface plasmon (LSP) effect for the effective biosensor. Core-shell nanoparticles (NPs) are fabricated in deionized water through a sequential process of reprecipitation and self-assembly. The Raman signal of PDA on core-shell NPs is enhanced more than 100 times. Also, highly enhanced photoluminescence is observed on Ag/PDA hybrid NPs after coupling of the complementary t-DNA with p-DNA which are immobilized on PDA shell. This indicates that the core Ag affects the Raman and PL of PDA through the LSP resonance, which can be caused by the energy and/or charge transfer caused by the LSP coupling and the strong electromagnetic field near Ag NP surface. Only electrons present on the surface interact with the PDA shell, not involving the electrically neutral part of the electrons inside the Ag NP. Furthermore, this work shows that as prepared Ag/PDA NPs functionalized by probe DNA can sense the target DNA with an attomolar concentration (100 attomole).

Metallic-phase transition metal dichalcogenide quantum dots (TMDs-mQDs) have been reported in recent years. However, a dominant mechanism for modulating their intrinsic exciton behaviors has not been determined yet as their size is close to the Bohr radius. Herein, we demonstrate that the oxidation effect prevails over quantum confinement on metallic-phase tungsten dichalcogenide QDs (WX₂-mQDs; X = S, Se) when the QD size becomes larger than the exciton Bohr radius. WX₂-mQDs with a diameter of ~12 nm show an obvious change in their photophysical properties when the pH of the solution changes from 2 to 11 compared to changing the size from ~3 nm. Meanwhile, we found that quantum confinement is the dominant function for the optical spectroscopic results in the WX₂-mQDs with a size of ~3 nm. This is because the oxidation of the larger WX₂-mQDs induces sub-energy states, thus enabling excitons to migrate into the lower defect energy states, whereas in WX₂-mQDs with a size comparable to the exciton Bohr radius, protonation enhances the quantum confinement.

Development of eco-friendly polymer foams is an urgent research topic because of the serious environmental pollution caused by trash heaps and the time-release of harmful gases. Polymer PVC foam using azodicarbonamide as a chemical foaming agent has been highly requested for further improvement due to the residual ammonia gas that continuously leaks out. Here, we demonstrate an effective and costless process for the reduction of releasing ammonia from PVC foams using the overcoat technology of deodorants. We have selected four candidate materials, gelite, zeolite, terra alba, and fumed silica as original materials for the deodorant of ammonia, and they showed an ammonia deodorization rate (ADR) of over 80% without any treatment except the fumed silica. When we over-coated the UV-curing agent mixed deodorants on the PVC foams (thickness ~300 µm), the ADR of the terra alba and zeolite complex foams was remarkably higher than 90%, however, the specific gravity and chromaticity were not changed within 20%. This indicates that our developed process using deodorant layer for ammonia reduction has a high potential for the production of eco-friendly polymer foams.