Solution structure of zinc-seamed C-alkylpyrogallol[4]arene dimeric nanocapsules

Solid-state core geometry of zinc-seamed C-propylpyrogallol[4]arene dimers is retained in solution; however, external ligands exchange with solvent molecules.

Aromatic amine-assisted pseudo-solution-phase ligand exchange in CsPbI3 perovskite quantum dot solar cells

Here, a pseudo-solution-phase ligands exchange (p-SPLE) strategy is developed for fabricating CsPbI3 quantum dot (QD) solar cell. Using short organic aromatic ligands to partly replace the long-chain ligands at QD...

Zinc Complexes with Nitrogen Donor Ligands as Anticancer Agents

The search for anticancer metal-based drugs alternative to platinum derivatives could not exclude zinc derivatives due to the importance of this metal for the correct functioning of the human body. Zinc, the second most abundant trace element in the human body, is one of the most important micro-elements essential for human physiology. Its ubiquity in thousands of proteins and enzymes is related to its chemical features, in particular its lack of redox activity and its ability to support different coordination geometries and to promote fast ligands exchange. Analogously to other trace elements, the impairment of its homeostasis can lead to various diseases and in some cases can be also related to cancer development. However, in addition to its physiological role, zinc can have beneficial therapeutic and preventive effects on infectious diseases and, compared to other metal-based drugs, Zn(II) complexes generally exert lower toxicity and offer few side effects. Zinc derivatives have been proposed as antitumor agents and, among the great number of zinc coordination complexes which have been described so far, this review focuses on the design, synthesis and biological studies of zinc complexes comprising N-donor ligands and that have been reported within the last five years.

Synthesis of Organic–Inorganic Hybrid Nanocomposites via a Simple Two-Phase Ligands Exchange

The surface of nanocrystals (NCs) was precisely engineered with bifunctional ligands via a simple yet effective two-phase ligand exchange strategy where the introduction of bifunctional ligands and displacement of insulating aliphatic ligands are simultaneously occurred. This is advantageous compared to conventional ligands exchange procedure where the desired ligands are often introduced through two-step processes after treating NC surface with short mobile ligands such as pyridine or short amines. In this study, 4-azidobenzoic acid possessing carboxylic acid for binding with NCs and azide group for chemical coupling was utilized as bifunctional ligands. A correlation between the concentration and the efficiency of ligands replacement was corroborated by Fourier transform infrared (FTIR) spectroscopy and nuclear magnetic resonance (1H NMR) spectroscopy measurement. Lastly, organic–inorganic nanocomposites were crafted via click coupling between 1-octyne and azidobenzoic acid capped CdSe NCs. The success of coupling was substantiated by FTIR and 1H NMR.

Tunnel engineering to accelerate product release for better biomass-degrading abilities in lignocellulolytic enzymes

Background For enzymes with buried active sites, transporting substrates/products ligands between active sites and bulk solvent via access tunnels is a key step in the catalytic cycle of these enzymes. Thus, tunnel engineering is becoming a powerful strategy to refine the catalytic properties of these enzymes. The tunnel-like structures have been described in enzymes catalyzing bulky substrates like glycosyl hydrolases, while it is still uncertain whether these structures involved in ligands exchange. Till so far, no studies have been reported on the application of tunnel engineering strategy for optimizing properties of enzymes catalyzing biopolymers. Results In this study, xylanase S7-xyl (PDB: 2UWF) with a deep active cleft was chosen as a study model to evaluate the functionalities of tunnel-like structures on the properties of biopolymer-degrading enzymes. Three tunnel-like structures in S7-xyl were identified and simultaneously reshaped through multi-sites saturated mutagenesis; the most advantageous mutant 254RL1 (V207N/Q238S/W241R) exhibited 340% increase in specific activity compared to S7-xyl. Deconvolution analysis revealed that all three mutations contributed synergistically to the improved activity of 254RL1. Enzymatic characterization showed that larger end products were released in 254RL1, while substrate binding and structural stability were not changed. Dissection of the structural alterations revealed that both the tun_1 and tun_2 in 254RL1 have larger bottleneck radius and shorter length than those of S7-xyl, suggesting that these tunnel-like structures may function as products transportation pathways. Attributed to the improved catalytic efficiency, 254RL1 represents a superior accessory enzyme to enhance the hydrolysis efficiency of cellulase towards different pretreated lignocellulose materials. In addition, tunnel engineering strategy was also successfully applied to improve the catalytic activities of three other xylanases including xylanase NG27-xyl from Bacillus sp. strain NG-27, TSAA1-xyl from Geobacillus sp. TSAA1 and N165-xyl from Bacillus sp. N16-5, with 80%, 20% and 170% increase in specific activity, respectively. Conclusions This study represents a pilot study of engineering and functional verification of tunnel-like structures in enzymes catalyzing biopolymer. The specific activities of four xylanases with buried active sites were successfully improved by tunnel engineering. It is highly likely that tunnel reshaping can be used to engineer better biomass-degrading abilities in other lignocellulolytic enzymes with buried active sites.