Lithium‐metal batteries (LMBs) with high energy densities are highly desirable for energy storage, but generally suffer from dendrite growth and side reactions in liquid electrolytes; thus the need for solid electrolytes with high mechanical strength, ionic conductivity, and compatible interface arises. Herein, a thiol‐branched solid polymer electrolyte (SPE) is introduced featuring high Li+ conductivity (2.26 × 10−4 S cm−1 at room temperature) and good mechanical strength (9.4 MPa)/toughness (≈500%), thus unblocking the tradeoff between ionic conductivity and mechanical robustness in polymer electrolytes. The SPE (denoted as M‐S‐PEGDA) is fabricated by covalently cross‐linking metal–organic frameworks (MOFs), tetrakis (3‐mercaptopropionic acid) pentaerythritol (PETMP), and poly(ethylene glycol) diacrylate (PEGDA) via multiple CSC bonds. The SPE also exhibits a high electrochemical window (>5.4 V), low interfacial impedance (<550 Ω), and impressive Li+ transference number (tLi+ = 0.44). As a result, Li||Li symmetrical cells with the thiol‐branched SPE displayed a high stability in a >1300 h cycling test. Moreover, a Li|M‐S‐PEGDA|LiFePO4 full cell demonstrates discharge capacity of 143.7 mAh g−1 and maintains 85.6% after 500 cycles at 0.5 C, displaying one of the most outstanding performances for SPEs to date.
Molecular simulations of the diffusion of EMIM(+) and TFSI(-) ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching ∼5 × 10(-9) m(2)/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Analysis of these results revealed that the fast (or slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. The molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.
Synthesis of cyclic peptides with novel Cβ–Ar crosslinks has been achieved by C(sp3)–H activation, and their biological properties have been evaluated for the first time.
Secondary metabolites from plants play key roles in human medicine and chemical industries. Due to limited accumulation of secondary metabolites in plants and their important roles, characterization of key enzymes involved in biosynthetic pathway will enable metabolic engineering or synthetic biology to improve or produce the compounds in plants or microorganisms, which provides an alternative for production of these valuable compounds.Salvia miltiorrhiza, containing tanshinones and phenolic acids as its active compounds, has been widely used for the treatment of cardiovascular and cerebrovascular diseases. The biosynthetic analysis of secondary metabolites in S. miltiorrhiza has made great progress due to the successful genetic transformation system, simplified hairy roots system, and
OPEN ACCESSMolecules 2015, 20 16236 high-throughput sequencing. The cloned genes in S. miltiorrhiza had provided references for functional characterization of the post-modification steps involved in biosynthesis of tanshinones and phenolic acids, and further utilization of these steps in metabolic engineering. The strategies used in these studies could provide solid foundation for elucidation of biosynthetic pathways of diterpenoids and phenolic acids in other species. The present review systematically summarizes recent advances in biosynthetic pathway analysis of tanshinones and phenolic acids as well as synthetic biology and metabolic engineering applications of the rate-limiting genes involved in the secondary metabolism in S. miltiorrhiza.
Understanding the dynamic charge storage in nanoporous electrodes with room-temperature ionic liquid electrolytes is essential for optimizing them to achieve supercapacitors with high energy and power densities. Herein, we report coarse-grained molecular dynamics simulations of the cyclic voltammetry of supercapacitors featuring subnanometer pores and model ionic liquids. We show that the cyclic charging and discharging of nanopores are governed by the interplay between the external field-driven ion transport and the sloshing dynamics of ions inside of the pore. The ion occupancy along the pore length depends strongly on the scan rate and varies cyclically during charging/discharging. Unlike that at equilibrium conditions or low scan rates, charge storage at high scan rates is dominated by counterions while the contribution by co-ions is marginal or negative. These observations help explain the perm-selective charge storage observed experimentally. We clarify the mechanisms underlying these dynamic phenomena and quantify their effects on the efficiency of the dynamic charge storage in nanopores.
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