Bottom-up Synthesis Strategy of a Two-dimensional {Fe5} Cluster-Based Coordination Polymer: Stepwise Formation of {Fe5} Cluster and Its Dimension Augmentation

Sophisticated aggregation assembly is challenging in assembly chemistry. Monitoring the assembly process helps to understand the assembly mechanism and the create new building blocks. A two-dimensional (2D) cluster-based coordination polymer...

Self-Assembly of Discrete Porphyrin/Calix[4]tube Complexes Promoted by Potassium Ion Encapsulation

The pivotal role played by potassium ions in the noncovalent synthesis of discrete porphyrin-calixarene nanostructures has been examined. The flattened-cone conformation adopted by the two cavities of octa-cationic calix[4]tube C4T was found to prevent the formation of complexes with well-defined stoichiometry between this novel water-soluble calixarene and the tetra-anionic phenylsulfonate porphyrin CuTPPS. Conversely, preorganization of C4T into a C4v-symmetrical scaffold, triggered by potassium ion encapsulation (C4T@K+), allowed us to carry out an efficient hierarchical self-assembly process leading to 2D and 3D nanostructures. The stepwise formation of discrete CuTPPS/C4T@K+ noncovalent assemblies, containing up to 33 molecular elements, was conveniently monitored by UV/vis spectroscopy by following the absorbance of the porphyrin Soret band.

SYNTHESIS AND CHARACTERIZATION OF CHITOSAN/SODIUM ALGINATE BLEND MEMBRANE FOR APPLICATION IN AN ELECTROCHEMICAL CAPACITOR

In this work, we report a stepwise formation method of a chitosan/sodium alginate polyelectrolyte complex (CS/SA PEC) membrane. The proposed method aiming at the utilization of the ultrasonic treatment of chitosan and sodium alginate solution allowed us to obtain a highly homogeneous hybrid membrane for electrochemical usage. The CS/SA PEC membrane saturated in a 2 M Li2SO4 aqueous solution was used in electrochemical double layer capacitor (EDLC) cell to study its applicability as quasi-solid electrolyte. Electrochemical characteristic of EDLC cells was determined by electrochemical impedance spectroscopy, cyclic voltammetry and galvanostatic charge/discharge methods. The results show that the EDLC cell with CS/SA PEC quasi-solid electrolyte exhibit a comparable specific capacitance (102 F g-1 for 0–0.8 V) to CS reference (100 F g-1 for 0–0.8 V) and commercial separator (99 F g-1 for 0–0.8 V) cells. Thus, the CS/SA PEC membrane can be considered as an alternative modification for chitosanbased materials of electrochemical purpose.

Synthesis of Coumarins via [4+2] Cyclization of Siloxy Alkynes and Salicylaldehydes

A new approach for the synthesis of coumarins from siloxy alkynes and salicylaldehydes is disclosed. Unlike the previous benzannulation reactions of siloxy alkynes that all proceed by electron-inversed Diels–Alder mechanism, this process represents a new [4+2] cyclization. In the presence of the superior HNTf2 catalyst, a wide range of coumarins were efficiently synthesized. This process was also extended to the synthesis of 2-quinolones. The polarized electron-rich triple bond might react sequentially with the aldehyde and hydroxy group by polarity switching in the stepwise formation of the C–C and C–O bonds. Control experiments provided insights into the mechanistic understanding.

Rubisco accumulation factor 1 (Raf1) plays essential roles in mediating Rubisco assembly and carboxysome biogenesis

Carboxysomes are membrane-free organelles for carbon assimilation in cyanobacteria. The carboxysome consists of a proteinaceous shell that structurally resembles virus capsids and internal enzymes including ribulose 1,5-bisphosphate carboxylase/oxygenase (Rubisco), the primary carbon-fixing enzyme in photosynthesis. The formation of carboxysomes requires hierarchical self-assembly of thousands of protein subunits, initiated from Rubisco assembly and packaging to shell encapsulation. Here we study the role of Rubisco assembly factor 1 (Raf1) in Rubisco assembly and carboxysome formation in a model cyanobacterium,Synechococcus elongatusPCC7942 (Syn7942). Cryo-electron microscopy reveals that Raf1 facilitates Rubisco assembly by mediating RbcL dimer formation and dimer–dimer interactions. Syn7942 cells lacking Raf1 are unable to form canonical intact carboxysomes but generate a large number of intermediate assemblies comprising Rubisco, CcaA, CcmM, and CcmN without shell encapsulation and a low abundance of carboxysome-like structures with reduced dimensions and irregular shell shapes and internal organization. As a consequence, the Raf1-depleted cells exhibit reduced Rubisco content, CO2-fixing activity, and cell growth. Our results provide mechanistic insight into the chaperone-assisted Rubisco assembly and biogenesis of carboxysomes. Advanced understanding of the biogenesis and stepwise formation process of the biogeochemically important organelle may inform strategies for heterologous engineering of functional CO2-fixing modules to improve photosynthesis.