Open Linear Polymer Host-Guest Interactions Sensed by Luminescent Silver Nanodots.

The selectivity of the linear polymer chain toward its binding moieties has been considered negligible; thus, a clear demonstration showing the best-fit binding of a linear polymer to its guest counterpart is still unknown. Luminescent poly(acrylic acid) (PAA)-stabilized silver nanodots (PAA-AgNDs) have been applied as a turn-on sensor to monitor the interaction between the PAA chain and its binding cations. The binding of cations ions to the PAA chain may cross-link the linear PAA chain via coordination with carboxylate, which increases the rigidity of the polymer chain, retards the nonradiative decay of PAA-AgNDs, and consequently enhances the emission of silver nanodots while inducing a blue-shift of its emission spectrum. For the first time, we have demonstrated that a linear polymer chain can act as an open host to selectively bind to its best-matching cations. Specifically, among Group 2 cations (Mg2+, Ca2+, Sr2+, Ba2+), calcium ions show the strongest bonding to the PAA polymer chain. Our research suggests that, with extra rigidity, the polymer improves its chemical stability as calcium ions cross-linked the linear polymer. Meanwhile, it has also been demonstrated that luminescent silver nanodots can be excellent probes for the detection of polymer activities with straightforward and simple visualization methods.

Carbon sequestration for high-quality sludge-based carbon preparation via K/Na bi-molten salts pyrolysis.

Pyrolysis carbonization of sewage sludge is employed to achieve carbon sequestration and access carbon resources, while the quality of the obtained sludge-based carbon (SBC) is poor due to high ash contents and volatile organic matter. Here, carbonization in KOH/Na2CO3 (K/Na) bi-molten salts was developed for SBC preparation, improvement of carbon exploitation from biomass, and to reduce the contents of ash and volatile organic matter. The results showed that the surface area and pore volume of SBC under optimized conditions reached 1631 m2 g-1 and 1.312 cm3 g-1 at 700 °C, respectively, with a K/Na bi-molten salts/sludge ratio of 2:1 (K:Na = 5:5). Moreover, over fivefold the higher surface area and 43.61% amount of carbon element could be obtained, with a decrease in the mass loss rate for sludge pyrolysis of 25%. The mechanism behind the higher surface area of the SBC was identified and divided into three stages: intense dehydration and dehydrogenation caused by molten salt-enhanced polycondensation of protein and polysaccharide (200-400 °C), strongly reduced carbon-oxygen structure after deoxygenation reactions (400-600 °C), aromatization and cyclization of long-chain fatty acids triggered by deamidation of tar catalyzed by molten salts (600-900 °C). Eventually, 14.63% carbon was sequestered for the high-surface-area SBC prepared by K/Na bi-molten salts system.

Tuning the fast generation of luminescent silver nanodots on a surface.

Silver nanodots, predominantly a near-IR emitter, can be instantly generated on a surface by silver cluster transfer. Kinetic trapping of ssDNA molecules on the surface limits the reorganization of the resulting silver nanodots for other silver nanodot emitters. Adjusting the freedom of the adsorbed ssDNA can tune the generation of various silver nanodots on the surface.

In Situ Generated Silver Nanodot Förster Resonance Energy Transfer Pair Reveals Nanocage Sizes.

Characterizing nanocages in macromolecules is one of the keys to understanding various biological activities and further utilizing nanocages for novel materials synthesis. However, fast and straightforward detection of the nanocage size remains challenging. Here, we present a new approach to detect the diameter of a nanocage by Förster resonance energy transfer (FRET) of luminescent silver nanodot pairs with reverse micelles as a model. Silver nanodot FRET pairs can be generated in situ from a single silver nanodot species with critical energy transfer distances, R0, of 4.8-6.5 nm. We have applied this approach to clarify the size variation of the water nanocage in nonionic surfactant Triton X-100-based reverse micelles. FRET efficiency decreases as more water is added, indicating that the size of the reverse micelles continuously expands with water content. The silver element in the nanocage also enhances the visualization of the nanocage under cryo-TEM imaging. The diameter of the water nanocage measured with the above approach is consistent with that obtained by cryo-TEM, demonstrating that the FRET measurement of silver nanodots can be a fast and accurate tool to detect nanocage dimensions. The above demonstration allows us to apply our strategy to other protein-based nanocages.

Hygroscopy-induced nanoparticle reshuffling in ionic-gold-residue-stabilized gold suprananoparticles.

Polyethyleneimine (PEI)-stabilized gold nanoparticles were used as a model to understand the roles of ionic precursors in the formation of nanoparticles and the impact of their presence on the nanoparticle properties. The low availability of elemental gold and the stabilization of the just-generated gold nanoparticles by the excess gold ions contributed to the production of ultra-small nearly neutral gold nanoparticles, resulting in properties significantly different from those prepared by conventional methods. The cross-linking between gold ions/PEI/nanoparticles further led to the assembly of these small gold nanoparticles into suprananoparticles that were stable in water. The hygroscopic Au(iii) residues in the suprananoparticles absorbed moisture to form a micro-water pool and the nanoparticles in the new aqueous solution reshuffled to generate larger nanoparticles, leading to significant changes in their optical properties. Such a phenomenon was formulated into a fast, sensitive and straightforward method for the detection of water content in organic solvents.