Single-Site Ni-Grafted TiO2 with Diverse Coordination Environments for Visible-Light Hydrogen Production.

Solar hydrogen production at a high efficiency holds the significant importance in the age of energy crisis, while the micro-environment manipulation of active sites on photocatalysts plays a profound role in enhancing the catalytic performance. In this work, a series of well-defined single-site Ni-grafted TiO2 photocatalysts with unique and specific coordination environments, 2,2'-bipyridine-Ni-O-TiO2 (T-Ni Bpy) and 2-Phenylpyridine-Ni-O-TiO2 (T-Ni Phpy), were constructed with the methods of surface organometallic chemistry combined with surface ligand exchange for visible-light-induced photocatalytic hydrogen evolution reaction (HER). A prominent rate of 33.82 µmol ⋅ g-1 ⋅ h-1 and a turnover frequency of 0.451 h-1 for Ni are achieved over the optimal catalyst T-Ni Bpy for HER, 260-fold higher than those of Ni-O-TiO2 . Fewer electrons trapped oxygen vacancies and a larger portion of long-lived photogenerated electrons (>3 ns, ~52.9 %), which were demonstrated by the electron paramagnetic resonance and femtosecond transient IR absorption, correspond to the photocatalytic HER activity over the T-Ni Bpy. The number of long-lived free electrons injected from the Ni photoabsorber to the conduction band of TiO2 is one of the determining factors for achieving the excellent HER activity.

Surface crafting and entrapment of CsPbBr3 perovskite QDs in ZIF-8 for ammonia recognition.

The substantial optical features of perovskite quantum dots (PQD) lead to rapid growth in the investigation of their surface and lattice doping for optoelectronic and biochemical sensor advancements. Herein, we have used the surface ligand crafting model of PQD by ammonia and its optimum response to recognise ammonia in the sensing cellulose paper. The PQD with acetyl amine and octanoic acid capped were synthesized and entrapped in zeolites imidazole framework to delay the instant quenching and envisaged response to ammonia with high sensitivity. The hybrid perovskite quantum dots and Zeolite imidazolate framework-8 (PQD@ZIF-8) materials were further immersed in cellulose paper for solid-state sensor fabrication for the detection of ammonia by naked-eye and a Xiaomi Note-5 mobile camera. The ammonia was measured with high sensitivity at ambient conditions, with a detection limit of 16 ppm and a linear detection range of 1 to 500 ppm. This research provides a new platform for designing sensor selectivity and sensitivity, which could be used to further develop fluorescent nanomaterials-based sensors for small molecule detection.

Nanoparticle Ligand Exchange and Its Effects at the Nanoparticle-Cell Membrane Interface.

The nanoparticle (nano)-cell membrane interface is one of the most important interactions determining the fate of nanoparticles (NPs), which can stimulate a series of biological events, allowing theranostic and other biomedical applications. So far, there remains a lack of knowledge about the mechanisms governing the nanoparticle-cell membrane interface, especially the impact of ligand exchange, in which molecules on the nanosurface become replaced with components of the cell membrane, resulting in unique interfacial phenomena. Herein, we describe a family of gold nanoparticles (AuNPs) of the same core size (∼13 nm core), modified with 12 different kinds of surface ligands, and the effects of their exchangeable ligands on both nanoparticle-supported lipid bilayers (SLBs) and nanoparticle-natural cell membrane interfaces. The ligands are categorized according to their molecular weight, charge, and bonding modes (physisorption or chemisorption). Importantly, we found that, depending on the adsorption affinity and size of ligand molecules, physisorbed ligands on the surface of NPs can be exchanged with lipid molecules. At a ligand exchange-dominated interface, the AuNPs typically aggregated into an ordered monolayer in the lipid bilayers, subsequently affecting cell membrane integrity, NP uptake efficiency, and the NP endocytosis pathways. These findings advance our understanding of the underlying mechanisms of the biological effects of nanoparticles from a new point of view and will aid in the design of novel, safe, and effective nanomaterials for biomedicine.

Surface grafting of rare-earth ions doped hydroxyapatite nanorods (HAp:Ln(Eu/Tb)) with hydrophilic copolymers based on ligand exchange reaction: Biological imaging and cancer treatment.

Rare-earth ions doped hydroxyapatite nanoparticles (HAp:Ln NPs) have demonstrated to be very promising candidates for biological imaging applications owing to their small size and chemical compositions similar to bone. However, these HAp:Ln NPs with controllable size and morphology should be prepared under hydrothermal treatment with hydrophobic molecules as the protective layers. The hydrophobic nature of these luminescent HAp:Ln NPs largely impeded their applications in biomedical fields. In this study, a novel and effective strategy has been developed for the surface modification of HAp:Ln nanorods through the combination of surface ligand exchange reaction and reversible-addition fragmentation chain transfer (RAFT) polymerization using 2-methacryloyloxyethyl phosphorylcholine (MPC) and itaconic acid (IA) as the monomers. Herein, a small molecule adenosine 5'-monophosphate disodium salt (AMP) that contains a phosphate group and two hydroxyl groups was used to displace the hydrophobic oleic acid on pristine HAp NPs through surface ligand exchange reaction owing to its stronger interaction with HAp NPs. On the other hand, the MPC and IA were introduced on HAp NPs through RAFT polymerization after the chain transfer agent was immobilized on the HAp NPs through the esterification reaction. The poly(IA-MPC) could not only endow the high water dispersibility but also be used for loading anticancer agent cisplatin (CDDP) through coordination interaction. To evaluate their potential biomedical applications, the cell uptake behavior, drug loading capacity and release behavior as well as cell viability of HAp:Ln-AMP-poly(IA-MPC) polymeric composites were examined. We demonstrated that the method developed in this work is very effective for introduction of functional polymers onto HAp:Ln nanorods. The HAp:Ln-AMP-poly(IA-MPC) composites are promising for cell imaging and controlled delivery of CDDP.