Chemically Triggered Synthesis, Remodeling, and Degradation of Soft Materials.

Polymer topology dictates dynamic and mechanical properties of materials. For most polymers, topology is a static characteristic. In this article, we present a strategy to chemically trigger dynamic topology changes in polymers in response to a specific chemical stimulus. Starting with a dimerized PEG and hydrophobic linear materials, a lightly cross-linked polymer, and a cross-linked hydrogel, transformations into an amphiphilic linear polymer, lightly cross-linked and linear random copolymers, a cross-linked polymer, and three different hydrogel matrices were achieved via two controllable cross-linking reactions: reversible conjugate additions and thiol-disulfide exchange. Significantly, all the polymers, before or after topological changes, can be triggered to degrade into thiol- or amine-terminated small molecules. The controllable transformations of polymeric morphologies and their degradation herald a new generation of smart materials.

Enhanced catalytic activity and stability of lactate dehydrogenase for cascade catalysis of D-PLA by rational design.

Serving as a vital medical intermediate and an environmentally-friendly preservative, D-PLA exhibits substantial potential across various industries. In this report, the urgent need for efficient production motivated us to achieve the rational design of lactate dehydrogenase and enhance catalytic efficiency. Surprisingly, the enzymatic properties revealed that a mutant enzyme, LrLDHT247I/D249A/F306W/A214Y (LrLDH-M1), had a viable catalytic advantage. It demonstrated a 3.3-fold increase in specific enzyme activity and approximately a 2.08-fold improvement of Kcat. Correspondingly, molecular docking analysis provided a supporting explanation for the lower Km and higher Kcat/Km of the mutant enzyme. Thermostability analysis exhibited increased half-lives and the deactivation rate constants decreased at different temperatures (1.47-2.26-fold). In addition, the mutant showed excellent resistance abilities in harsh environments, particularly under acidic conditions. Then, a two-bacterium (E. coli/pET28a-lrldh-M1 and E. coli/pET28a-ladd) coupled catalytic system was developed and realized a significant conversion rate (77.7%) of D-phenyllactic acid, using 10 g/L L-phenylalanine as the substrate in a two-step cascade reaction.

Bioremediation of microplastics in freshwater environments: A systematic review of biofilm culture, degradation mechanisms, and analytical methods.

Microplastics, defined as particles <5 mm in diameter, are emerging environmental pollutants that pose a threat to ecosystems and human health. Biofilm degradation of microplastics may be an ecologically friendly approach. This review systematically summarises the factors affecting biofilm degradation of microplastics and proposes feasible methods to improve the efficiency of microplastic biofilm degradation. Environmentally insensitive microorganisms were screened, optimized, and commercially cultured to facilitate the practical application of this technology. For strain screening, technology should focus on microorganisms/strains that can modify the hydrophobicity of microplastics, degrade the crystalline zone of microplastics, and metabolise additives in microplastics. The biodegradation mechanism is also described; microorganisms secreting extracellular oxidases and hydrolases are key factors for degradation. Measuring the changes in molecular weight distribution (MWD) enables better analysis of the biodegradation behaviour of microplastics. Biofilm degradation of microplastics has relatively few applications because of its low efficiency; however, enrichment of microplastics in freshwater environments and wastewater treatment plant tailwater is currently the most effective method for treating microplastics with biofilms.

Visualizing Drug Release from a Stimuli-Responsive Soft Material Based on Amine-Thiol Displacement.

In this research, we developed a photoluminescent platform using amine-coupled fluorophores, generated from a single conjugate acceptor containing bis-vinylogous thioesters. Based on the experimental and computational results, the fluorescence turn-on mechanism was proposed to be charge separated induced energy radiative transition for the amine-coupled fluorophore, while the sulfur-containing precursor was not fluorescent since the energy internal conversion occurred through vibrational 2RS- (R represents alkyl groups) as energy acceptor(s). Further utilizing the conjugate acceptor, we establish a new fluorogenic approach via a highly cross-linked soft material to selectively detect cysteine under neutral aqueous conditions. Turn-on fluorescence emission and macroscopic degradation occurred in the presence of cysteine as the stimuli, which can be visually tracked due to the generation of an optical indicator and the cleavage of linkers within the matrix. Furthermore, a novel drug delivery system was constructed, achieving controlled release of sulfhydryl drug (6-mercaptopurine) which was tracked by photoluminescence and high-performance liquid chromatography. The photoluminescent molecules developed herein are suitable for visualizing polymeric degradation, making them suitable for additional "smart" material applications.

Lactate dehydrogenase encapsulated in a metal-organic framework: A novel stable and reusable biocatalyst for the synthesis of D-phenyllactic acid.

In this study, we synthesized a novel biocatalyst by encapsulating lactate dehydrogenase (LDH) in the metal-organic framework ZIF-90 by one-pot embedding. It showed strong biological activity for efficient synthesis of D-phenyllactic acid (D-PLA). The morphology and structure of LDH@ZIF-90 was systematically characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectroscopy, confocal laser scanning microscopy (CLSM) and gas sorption. According to thermogravimetric analysis (TGA), the enzyme loading of the biocatalyst was 3 %. The Michaelis-Menten constant (Km) and maximal reaction rate (Vmax) of LDH@ZIF-90 were similar to those of free LDH, which proved that ZIF-90 had good biocompatibility to encapsulate LDH. At the same time, LDH@ZIF-90 exhibited enhanced tolerance to temperature, pH and organic solvents, and its reusability was greatly improved with 68 % of initial enzyme activity remaining after 7 rounds of recylcing. Overall, LDH encapsulated in ZIF-90 may be an economically competitive and environmentally friendly novel biocatalyst for the synthesis of D-PLA.

The adsorption characteristics of Cu(II) and Zn(II) on the sediments at the mouth of a typical urban polluted river in Dianchi Lake: taking Xinhe as an example.

This study is to determine the spatial distribution characteristics of Cu and Zn adsorption on the sediments of the estuary of Dianchi Lake, as well as the composite adsorption law of Cu and Zn on combinations of sediment organic matter, metal oxides, and organic-inorganic composites. The relationship between the adsorption contribution of each component of the substance. A static adsorption experiment was applied to the sediments in the estuary of Dianchi Lake. The relationship between adsorption capacity and sediment composition was analyzed through correlation analysis and redundant analysis. The results show that along the direction of the river flow and the vertical depth, the adsorption capacity presents a relatively obvious spatial distribution law; the change trend of sediment component content is not the same as the change trend of Cu and Zn adsorption capacity. The change trend of the sediment component content is not the same as the change trend of the adsorption amount of Cu and Zn, and the compound effect between the components affects the adsorption amount. The adsorption of Cu by the four groups of sediments after different treatments is more in line with the Freundlich isotherm adsorption model; When adsorbing Zn, the untreated and removed organic matter and iron-aluminum oxide group are in good agreement with the Freundlich model, while the organic matter-removed group and the iron-aluminum oxide removal group are more consistent with the Langmuir isotherm adsorption model; The adsorption contribution rate of organic-inorganic composites in sediments is not a simple addition of organic matter and iron-aluminum oxides, but a more complex quantitative relationship.

The osteogenesis performance of titanium modified via plasma-enhanced chemical vapor deposition: in vitro and in vivo studies.

Titanium (Ti) and its alloys are widely used in dental implants due to their favorable mechanical properties and biocompatibility. Surface characteristics, including physical and chemical properties, are crucial factors to enhance the osteogenesis performance of Ti. The aim of this study is to evaluate amino group surface modification to facilitate the osteogenic potential and bone repair of dental implants both in vitro and in vivo. Herein, amino group-modified Ti surfaces were constructed via the plasma-enhanced chemical vapor deposition (PECVD) technique with an allylamine monomer. The adhesion, proliferation, alkaline phosphate activity and osteogenesis-related genetic expression of MG-63 cells on the surfaces were performed in vitro and presented a significant increase in amino group-modified Ti compared with that in Ti. The in vivo study in miniature pigs was evaluated through micro-computed tomography analysis and histological evaluation, which exhibited enhanced new bone formation in amino group-modified Ti compared with that in Ti after implantation for 4, 8 and 12 weeks. Consequently, amino group surface modification with the PECVD technique may provide a promising modification method to enhance the osteogenesis performance of Ti implants.

Boronic Acid-Based Carbohydrate Sensing.

The covalent boron-diol interaction enables elaborate design of boronic acid-based saccharide sensors. Over the last decade, this research topic has been well developed thanks to the integration of boronic acid chemistry with a range of techniques, including supramolecular chemistry, materials chemistry, surface modification, and nanotechnology. New sensing strategies and platforms have been introduced and remarkable progress has been achieved to fully utilize the unique property of boron-diol interaction and to improve the binding affinity towards different targets, especially under physiological conditions. In this review, the latest progress over the past 30 months (from late 2012 to early 2015) is highlighted and discussed to shed light on this versatile and promising platform for saccharide sensing.