Absorption-Based Rapid Acquisition of Single-Molecule Kinetics from Unstable Enzymes in Microdroplets.

Single-molecule catalysis reflects the heterogeneity of each molecule, providing a unique insight into the complex catalytic mechanism through the statistics of stochastic individuals. However, the present study methods for single-molecule catalysis are either complicated or have low throughput, limiting their rapid acquisition of single-molecule reaction kinetics with statistical significance. Here, a label-free imaging method is developed for the study of single-molecule catalysis in microdroplets with high throughput based on the absorption of the reaction molecules. A wide distribution of the catalytic reaction rate constant value of 238-2026 molecules s-1 is observed from 68 single enzymes. Interestingly, an exponential decayed distribution of the enzyme activity can be clearly observed due to the rapid denaturation of the enzymes. The denaturation mechanism of the Horse Radish Peroxidase (HRP) enzyme is clarified. It is revealed that the denaturation of each enzyme goes through a gradual decay rather than a truncated turn-off process from a single molecule point of view. This absorption-based method can be applied to most of the catalytic reactions with high throughput, which offers an indispensable route for the rapid statistical analysis of various single-molecule catalytic reactions, making it particularly suitable for the acquisition of catalytic kinetics from highly unstable enzymes.

Pt-Loaded Nb─W Metal Composite Oxide for Selective Cleavage of Secondary C─O Bonds.

Selective hydrogenolysis of glycerol to 1,3-propanediol (1,3-PDO) is recognized as one of the most promising reactions for the valorization of biomass. Precise activation of C─O bonds of glycerol molecule is the key step to realize the high yield of catalytic conversion. Here, a Pt-loaded Nb-W composite oxides with crystallographic shear phase for the precise activation and cleavage of secondary C─O (C(2)─O) bonds are first reported. The developed Nb14 W3 O44 with uniform structure possesses arrays of W-O-Nb active sites that totally distinct from individual WOx or NbOx species, which is superior to the adsorption and activation of C(2)─O bonds. The Nb14 W3 O44 support with rich reversible redox couples also promotes the electron feedback ability of Pt and enhances its interaction with Pt nanoparticles, resulting in high activity for H2 dissociation and hydrogenation. All these favorable factors confer the Pt/Nb14 W3 O44 excellent performance for selective hydrogenolysis of glycerol to 1,3-PDO with the yield of 75.2% exceeding the record of 66%, paying the way for the commercial development of biomass conversion. The reported catalysts or approach can also be adopted to create a family of Nb-W metal composite oxides for other catalytic reactions requiring selective C─O bond activation and cleavage.

Cadmium ions mediated turn-on electrogenerated chemiluminescence of ZnS nanoparticles for highly selective cadmium detection in seafood.

Cd2+ is one of the most toxic heavy metal ions that can be easily accumulated in human body via food chain. Thus, the onsite detection of Cd2+ in food is very important. However, present methods for Cd2+ detection either require the use of large equipment, or suffer from the severe interference from other analogical metal ions. This work establishes a facile Cd2+ mediated turn-on ECL method for highly selective detection of Cd2+ via cation exchanging with the nontoxic ZnS nanoparticles, owing to the unique surface-state ECL properties of CdS nanomaterials. The linear range of the calibration curve is from 7.0 × 10-8 to 1.0 × 10-6 M, while other analogical metal ions do not interfere, facilitating the selective detection of Cd2+ in oyster samples. The result agrees well with that obtained using atomic emission spectroscopy, indicating the potential for wider application of this approach.

Label-free single-particle imaging approach for ultra-rapid detection of pathogenic bacteria in clinical samples.

Rapid detection of pathogenic bacteria within a few minutes is the key to control infectious disease. However, rapid detection of pathogenic bacteria in clinical samples is quite a challenging task due to the complex matrix, as well as the low abundance of bacteria in real samples. Herein, we employ a label-free single-particle imaging approach to address this challenge. By tracking the scattering intensity variation of single particles in free solution, the morphological heterogeneity can be well identified with particle size smaller than the diffraction limit, facilitating the morphological identification of single bacteria from a complex matrix in a label-free manner. Furthermore, the manipulation of convection in free solution enables the rapid screening of low-abundance bacteria in a small field of view, which significantly improves the sensitivity of single-particle detection. As a proof of concept demonstration, we are able to differentiate the group B streptococci (GBS)-positive samples within 10 min from vaginal swabs without using any biological reagents. This is the most rapid and low-cost method to the best of our knowledge. We believe that such a single-particle imaging approach will find wider applications in clinical diagnosis and disease control due to its high sensitivity, rapidity, simplicity, and low cost.

Constructing highly porous carbon materials from porous organic polymers for superior CO2 adsorption and separation.

The increase in atmospheric carbon dioxide (CO2) concentration has led to numerous problems related to our living environment, seeking an efficient carbon capture and storage (CCS) strategy associated with low energy consumption and expenditures is highly desirable. Here, we demonstrate a facile approach to synthesize a series of highly porous carbon materials derived from porous organic polymers synthesized from three low-cost isomers of triphenyl using chemical activation with KOH at different temperatures. Compared with the precursor porous organic polymers, the porosity of the prepared porous carbon materials is significantly enhanced with surface areas as high as 3367 m2 g-1 and pore volumes up to 1.224 cm3 g-1. Notably, such porous carbon materials deliver an exceptionally high CO2 adsorption capacity of 7.78 mmol g-1 at 273 K and 1 bar, a value that is superior to most of the previously reported adsorbents. In addition, these porous organic polymers and derived porous carbon materials exhibit high CO2/N2 selectivity at ambient conditions. Therefore, the facile construction of highly porous carbon materials from porous organic polymers may offer an efficient strategy for CO2 adsorption and separation and further mitigates greenhouse effect.

Enhanced flux and fouling resistance forward osmosis membrane based on a hydrogel/MOF hybrid selective layer.

Although forward osmosis (FO) technology has been widely adopted for water treatment, it still faces great challenges, including low permeability and fouling problem. Herein, a novel forward osmosis membrane was developed with a stable, uniform and defect-free polyvinyl alcohol/polydopamine coated zeolitic imidazolate framework (PVA/PDA@ZIF-8) hybrid selective layer to simultaneously enhance its transport property and fouling resistance. The prepared FO membrane exhibits improved water flux without losing the selectivity, since the PDA@ZIF-8 provide additional preferential passageway for water transporting while hinder the diffusion of salt. The optimized membrane shows a higher water flux than pristine PVA membrane (14.2 vs. 8.7 L m-2 h-1 in FO mode, 24.3 vs. 14.8 L m-2 h-1 in PRO mode) with a reasonable selectivity considering as Js/Jw value (0.44 vs. 0.4 g L-1 in FO mode, 0.38 vs. 0.33 g L-1). Moreover, the dynamic fouling experiments with organic foulants (protein and polysaccharide) indicate that the prepared membrane exhibits strong antifouling property and excellent permeation recovery ability (>95.0%) due to the optimized surface property. This study opens a new avenue for treatment wastewater by developing a forward osmosis membrane based on a hydrogel/MOF hybrid selective layer.