Accelerated sonochemical fabrication of MIn2S4 (M = Zn, Mg, Ni, Co) for ultra-high photocatalytic hydrogen peroxide production.

Ternary metal sulfide (MIn2S4) by virtue of large extinction coefficient, suitable band gap and stability, has been proposed as a candidate for photocatalytic synthesis hydrogen peroxide (H2O2). However, MIn2S4 is conventionally synthesized by solvothermal method that is generally characterized by tedious operational steps and long reaction time. In this work, four sonoMIn2S4 (M = Zn, Mg, Ni, Co) were successfully prepared by sonochemical method within 2 h. These as-synthesized sonoMIn2S4 delivered much high-efficient photocatalytic H2O2 generation. Particularly, the sonoZnIn2S4 presented H2O2 production rate of 21295.5 µmol∙g-1∙h-1 in water/benzylalcohol system, which is 3.0 times that of ZnIn2S4 prepared by solvothermal method. The remarkably improved photocatalytic performance of sonoZnIn2S4 might be due to the multiple defects and fast electron-hole pair separation caused by ultrasound cavitation effect. Other metal sulfide photocatalysts with high performance were efficiently fabricated by facile sonochemical technology as well. The sonochemical method realized the rapid preparation of metal sulfide photocatalysts and efficient production of H2O2, which benefits to meet the United Nations Sustainable Development Goals (SDGs) including SDG-7 and SDG-12.

Switching the Cofactor Preference of Formate Dehydrogenase to Develop an NADPH-Dependent Biocatalytic System for Synthesizing Chiral Amino Acids.

Efficient formate dehydrogenase (FDH)-based cofactor regeneration systems are widely used for biocatalytic processes due to their ready availability, low reduction potential, and production of only benign byproducts. However, FDHs are usually specific to NAD+, and NADPH regeneration with formate is challenging. Herein, an FDH with a preference for NAD+ from Azospirillum palustre (ApFDH) was selected owing to its high activity. By static and dynamic structural analyses, a beneficial substitution, D222Q, was identified for cofactor-preference switching. However, its total activity was substantially decreased by 90% owing to the activity-specificity trade-off. Subsequently, a semirational library was designed and screened, which yielded a variant ApFDHD222Q+A199G+H380S with satisfactory activity and NADP+ specificity. Our analysis of dynamical cross-correlations revealed a substitution combination that brought balance to the dynamical correlation network. This combination successfully overcame the activity-specificity-stability trade-off and resulted in a beneficial outcome. The substitution combination (D222Q-A199G/H380S-C256A/C146S) enabled the simultaneous improvement of activity, specificity, and stability and was successfully applied to other 17 FDHs. Finally, by employing engineered ApFDH, an NADPH regeneration system was developed, optimized, and utilized for the asymmetric biosynthesis of l-phosphinothricin.

[Formate dehydrogenase and its application in biomanufacturing of chiral chemicals].

The redox biosynthesis system has important applications in green biomanufacturing of chiral compounds. Formate dehydrogenase (FDH) catalyzes the oxidation of formate into carbon dioxide, which is associated with the reduction of NAD(P)+ into NAD(P)H. Due to this property, FDH is used as a crucial enzyme in the redox biosynthesis system for cofactor regeneration. Nevertheless, the application of natural FDH in industrial production is hampered by low catalytic efficiency, poor stability, and inefficient coenzyme utilization. This review summarized the structural characteristics and catalytic mechanism of FDH, as well as the advances in protein engineering of FDHs toward improved enzyme activity, catalytic efficiency, stability and coenzyme preference. The applications of using FDH as a coenzyme regeneration system for green biomanufacturing of chiral compounds were summarized.

Electrospinning of calixarene-functionalized polyacrylonitrile nanofiber membranes and application as an adsorbent and catalyst support.

Polyacrylonitrile (PAN) nanofiber membranes functionalized with calix[8]arenes (C[8]) were successfully prepared by electrospinning of PAN solutions with addition of various calixarenes. Uniform electrospun C[8]/PAN nanofibers were obtained by incorporating three types of calix[8]arenes into the PAN matrix and characterized by scanning electron microscopy (SEM), attenuated total reflection Fourier transform infrared (ATR-FTIR), thermal gravimetric analysis (TGA), and X-ray powder diffraction (XRD). The SEM results showed that the addition of calix[8]arenes resulted in a decrease in the diameter of PAN nanofibers. Static adsorption behavior was studied by using C[8]/PAN nanofibers as an adsorbent and Congo red and Neutral red as model dye molecules. The adsorption of Congo red onto Amide-Cal[8]-15/PAN nanofibers fitted the second-order kinetic model, and the apparent adsorption rate constant was 1.1 × 10(-3) g·mg(-1)·min(-1) at 25 °C. Then, by virtue of electrostatic attraction, as-prepared Au nanoparticles were immobilized on Amide-Cal[8]/PAN nanofibers to form Au/Amide-Cal[8]/PAN composite nanofibers. The catalytic activity of the as-prepared Au/Amide-Cal[8]/PAN composite nanofibers was investigated by monitoring the reduction of Congo red in the presence of NaBH4. The reduction kinetics was explained by the assumption of a pseudo-first-order reaction with regard to Congo red. Au/Amide-Cal[8]/PAN composite nanofibers exhibited high catalytic activity, excellent stability, and convenient recycling.

Facile fabrication of hierarchically porous CuFe2O4 nanospheres with enhanced capacitance property.

In this work, CuFe2O4 nanospheres with hierarchically porous structure have been synthesized via a facile solvothermal procedure. The superstructures consist of the textured aggregations of nanocrystals with high specific surface area, pore volume, and uniform pore size distribution.To figure out the formation mechanism, we discussed in detail the effects of a series of experimental parameters, including the concentrations of the precipitation agent, stabilizer agent, and reaction temperature and time on the size and morphology of the resulting products. Furthermore, the electrochemical properties of CuFe2O4 nanospheres were evaluated by cyclic voltammetry and galvanostatic charge-dischrge studies. The results demonstrate that the as-prepared CuFe2O4 nanospheres are excellent electrode material in supercapacitor with high specific capacitance and good retention. The hierarchically CuFe2O4 nanospheres show the highest capacitance of 334F/g, and 88% of which can still be maintained after 600 charge-discharge cycles.