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We have developed a protocol for insertion of alkylidene carbenes into the B-H bonds of amine-borane adducts, enabling, for the first time, the construction of C(sp2)-B bonds by means of carbene-insertion reactions. Various acyclic and cyclic alkenyl borane-amine adducts were prepared from readily accessible starting materials in good to high yields and were subsequently subjected to a diverse array of functional group transformations. The unprecedented spiro B-N heterocycles prepared in this study have potential utility as building blocks for the synthesis of pharmaceuticals. Preliminary mechanistic studies suggest that insertion of the alkylidene carbenes into the B-H bonds of the amine-borane adducts proceeds via a concerted process involving a three-membered-ring transition state.

Creating highly branched plasmonic superparticles can effectively induce broadband light absorption and convert light to heat regardless of the light wavelength, angle, and polarization. However, their direct synthesis in a controllable manner remains a significant challenge. In this work, we propose a strain modulation strategy to produce branched Au nanostructures that promotes the growth of Au on Au seeds in the Volmer-Weber (island) mode instead of the typical Frank-van der Merwe (layer-by-layer) mode. The key to this strategy is to continuously deposit polydopamine formed in situ on the growing surface of the seeds to increase the chemical potential of the subsequent deposition of Au, thus achieving continuous heterogeneous nucleation and growth. The branched Au superparticles exhibit a photothermal conversion efficiency of 91.0% thanks to their small scattering cross-section and direction-independent absorption. Even at a low light power of 0.5 W/cm2 and a low dosage of 25 ppm, these particles show an excellent efficacy in photothermal cancer therapy. This work provides the fundamental basis for designing branched plasmonic nanostructures and expands the application scope of the plasmonic photothermal effect.

A supramolecular polymeric adhesive was prepared from non-viscous, non-polymeric materials by water-participant hydrogen bonds. Pt-pyridine coordination and water-crown ether hydrogen bonding combine to effect the supramolecular polymerization. The supramolecular polymeric adhesive displays strong, reversible adhesion to hydrophilic surfaces, a property that forecasts the application of hydrogen bonding in advanced supramolecular materials.

Although the gelation process and lower critical solution temperature (LCST) behavior are well acknowledged in polymer systems, low-molecular-weight gelators (LMWGs) rarely display LCST behavior during supramolecular gelation. Herein, we report an LMWG system with LCST-type thermoresponsiveness and an LCST-triggered supramolecular gelation process. Temperature plays a crucial role in this system, not only affecting the LCST phase separation but also triggering the gelation process. The backbones (three-dimensional structures) of the resulting hydrogel are the hierarchical assemblies of the LMWG undergoing the LCST phase separation. Hence, the gelation of the LMWG is only realized when the gelation temperature is above the critical transition temperature (Tcloud) of the LCST behavior, which is different from many supramolecular or polymeric hydrogel systems.

The development of activatable nanoplatforms to simultaneously improve diagnostic and therapeutic performances while reducing side effects is highly attractive for precision cancer medicine. Herein, we develop a one-pot, dopamine-mediated biomineralization method using a gas diffusion procedure to prepare calcium carbonate-polydopamine (CaCO3–PDA) composite hollow nanoparticles as a multifunctional theranostic nanoplatform. Because of the high sensitivity of such nanoparticles to pH, with rapid degradation under a slightly acidic environment, the photoactivity of the loaded photosensitizer, i.e., chlorin e6 (Ce6), which is quenched by PDA, is therefore increased within the tumor under reduced pH, showing recovered fluorescence and enhanced singlet oxygen generation. In addition, due to the strong affinity between metal ions and PDA, our nanoparticles can bind with various types of metal ions, conferring them with multimodal imaging capability. By utilizing pH-responsive multifunctional nanocarriers, effec...

The poor stability of CsPbX3 (X = Cl, Br, I) nanocrystals (NCs) has severely impeded their practical applications. Although there are some successful examples on encapsulating multiple CsPbX3 NCs into an oxide or polymer matrix, it has remained a serious challenge for the surface modification/encapsulation using oxides or polymers at a single particle level. In this work, monodisperse CsPbX3/SiO2 and CsPbBr3/Ta2O5 Janus nanoparticles were successfully prepared by combining a water-triggered transformation process and a sol–gel method. The CsPbBr3/SiO2 NCs exhibited a photoluminescence quantum yield of 80% and a lifetime of 19.8 ns. The product showed dramatically improved stability against destruction by air, water, and light irradiation. Upon continuous irradiation by intense UV light for 10 h, a film of the CsPbBr3/SiO2 Janus NCs showed only a slight drop (2%) in the PL intensity, while a control sample of unmodified CsPbBr3 NCs displayed a 35% drop. We further highlighted the advantageous features of t...

The development of activatable nanoplatforms to simultaneously improve diagnostic and therapeutic performances while reducing side effects is highly attractive for precision cancer medicine. Herein, we develop a one-pot, dopamine-mediated biomineralization method using a gas diffusion procedure to prepare calcium carbonate-polydopamine (CaCO

We demonstrate that anatase TiO2 nanocrystals composed of a nanocrystal core and nanorod antennas can be produced via a nonaqueous colloidal seed-mediated growth method. Anatase TiO2 nanocrystals with defined morphologies were first prepared as seeds, and then secondary anatase TiO2 nanorods were grown on the defined facets of the seeds under appropriate conditions. Systematic studies on the growth mechanism reveal that the formation of core-antenna nanocrystals involves an epitaxial growth process with specific orientational preference governed by both thermodynamic and kinetic factors. By manipulating the reaction conditions including the precursor amount and introduction rate, the epitaxial growth behavior can be well controlled. By further varying the morphology of seed nanocrystals, we have also been able to produce core-antenna anatase TiO2 nanocrystals with complex spatial configurations in a highly predictable manner. The high structural configurability and predictability offered by this seed-mediated growth method may provide great opportunities in enhancing the performance of TiO2-based nanostructures in many energy-related applications. As a demonstration, we show by simply manipulating the core-antenna structures that the photocatalytic activity of the anatase nanocrystals can be improved from the relatively less active seed nanocrystals or pure nanorods to the extent that exceeds the activity of the commercial P25 titania.

A method of preparing a metal nanorod. The method includes seeding a metal nanoparticle within the lumen of a nanotube, and growing a metal nanorod from the seeded metal nanoparticle to form a metal nanorod- nanotube composite. In some cases, the nanotube includes metal binding ligands attached to the inner surface. Growing of the metal nanorod includes incubating the seeded nanotube in a solution that includes: a metal source for the metal in the metal nanorod, the metal source including an ion of the metal; a coordinating ligand that forms a stable complex with the metal ion; a reducing agent for reducing the metal ion, and a capping agent that stabilizes atomic monomers of the metal. Compositions derived from the method are also provided.

An efficient method for the synthesis of heterogeneous gold catalysts has been developed. These catalysts were easily assembled from readily available silica materials and gold complexes. The heterogeneous catalysts exhibited superior reactivity in various reactions where protodeauration is the rate-limiting step. Dramatic enhancement in regio- and enantioselectivity was observed when compared to the homogeneous unsupported gold catalyst. The catalysts are easily recovered and recycled up to 11 times without loss of enantioselectivity.

In this work we have carried out systematic studies and identified the critical role of hydrogen peroxide instead of the generally believed citrate in the well-known chemical reduction route to silver nanoplates. This improved understanding allows us to develop consistently reproducible processes for the synthesis of nanoplates with high efficiency and yields. By harnessing the oxidative power of H(2)O(2), various silver sources including silver salts and metallic silver can be directly converted to nanoplates with the assistance of an appropriate capping ligand, thus significantly enhancing the reproducibility of the synthesis. Contrary to the previous conclusion that citrate is the key component, we have determined that the group of ligands with selective adhesion to Ag (111) facets can be expanded to many di- and tricarboxylate compounds whose two nearest carboxylate groups are separated by two or three carbon atoms. We have also found that the widely used secondary ligand polyvinylpyrrolidone can be replaced by many hydroxyl group-containing compounds or even removed entirely while still producing nanoplates of excellent uniformity and stability. In addition to the general understanding of NaBH(4) as a reducing agent, it has also been found to act as a capping agent to stabilize the silver nanoparticles, prolong the initiation time required for nanoplate nucleation, and contribute to the control of the thickness as well as the aspect ratio of silver nanoplates. The improved insight into the specific roles of the reaction components and significantly enhanced reproducibility are expected to help elucidate the formation mechanism of this interesting nanostructure.