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Facile Fabrication of Ordered Component-Tunable Heterobimetallic Self-Assembly Nanosheet for Catalyzing "Click" Reaction.

ABSTRACT: How to maximize the number of desirable active sites on the surface of the catalyst and minimize the number of sites promoting undesirable side reactions is currently an important research topic. In this study, a new way based on the synergism to achieve the successful fabrication of an ordered heterobimetallic self-assembled monolayer (denoted as BMSAM) with a controlled composition and an excellent orientation of metals in the monolayer was developed. BMSAM consisting of phenanthroline and Schiff-base groups was prepared, and its novel heterobimetallic (Cu and Pd) self-assembled monolayer anchored in silicon (denoted as Si-Fmp-Cu-Pd BMSAM) with a controlled composition and a fixed position was fabricated and characterized by UV, cyclic voltammetry, Raman, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray diffraction (XRD), inductively coupled plasma atomic emission spectroscopy (ICP-AES), and water-drop contact angle (WDCA) analyses. The effects of Si-Fmp-Cu-Pd BMSAM on its catalytic properties were also systematically investigated using "click" reaction as a template by WDCA, XPS, SEM, XRD, ICP-AES and in situ Fourier transform infrared analyses in a heterogeneous system. The results showed that the excellent catalytic characteristic could be attributed to the partial (ordered or proper distance) isolation of active sites displaying high densities of specific atomic ensembles. The catalytic reaction mechanism of the click reaction interpreted that the catalytic process mainly occurred on the surface of the monolayer, internal active site (Pd) and rationalized that the Cu(I) species and Pd(0) reduced from the Cu(II) and Pd(II) catalyst were active species, which had a proper distance between two different metals. The cuprate-triazole intermediate and the palladium intermediate, whose production is the key step, should lie in a proper position between the copper and active palladium sites, with which the reaction rate of transmetalation would be improved to increase the amount of the undesired Sonogashira coupling product.

SUBMITTER: Gu X

PROVIDER: S-EPMC6644525 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature

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Facile Fabrication of Ordered Component-Tunable Heterobimetallic Self-Assembly Nanosheet for Catalyzing "Click" Reaction.

Gu Xiang X Bi Sa S Guo Linna L Zhao Yaqing Y Li Tiesheng T Liu Minghua M Chen Penglei P Wu Yangjie Y

ACS omega 20170905 9

How to maximize the number of desirable active sites on the surface of the catalyst and minimize the number of sites promoting undesirable side reactions is currently an important research topic. In this study, a new way based on the synergism to achieve the successful fabrication of an ordered heterobimetallic self-assembled monolayer (denoted as <b>BMSAM</b>) with a controlled composition and an excellent orientation of metals in the monolayer was developed. <b>BMSAM</b> consisting of phenanth ...[more]

PMID: 31457810

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Project description:The scope, chemoselectivity, and utility of the click-like tyrosine labeling reaction with 4-phenyl-3H-1,2,4-triazoline-3,5(4H)-diones (PTADs) is reported. To study the utility and chemoselectivity of PTAD derivatives in peptide and protein chemistry, we synthesized PTAD derivatives possessing azide, alkyne, and ketone groups and studied their reactions with amino acid derivatives and peptides of increasing complexity. With proteins we studied the compatibility of the tyrosine click reaction with cysteine and lysine-targeted labeling approaches and demonstrate that chemoselective trifunctionalization of proteins is readily achieved. In particular cases, we noted that PTAD decomposition resulted in formation of a putative isocyanate byproduct that was promiscuous in labeling. This side reaction product, however, was readily scavenged by the addition of a small amount of 2-amino-2-hydroxymethyl-propane-1,3-diol (Tris) to the reaction medium. To study the potential of the tyrosine click reaction to introduce poly(ethylene glycol) chains onto proteins (PEGylation), we demonstrate that this novel reagent provides for the selective PEGylation of chymotrypsinogen, whereas traditional succinimide-based PEGylation targeting lysine residues provided a more diverse range of PEGylated products. Finally, we applied the tyrosine click reaction to create a novel antibody-drug conjugate. For this purpose, we synthesized a PTAD derivative linked to the HIV entry inhibitor aplaviroc. Labeling of the antibody trastuzumab with this reagent provided a labeled antibody conjugate that demonstrated potent HIV-1 neutralization activity demonstrating the potential of this reaction in creating protein conjugates with small molecules. The tyrosine click linkage demonstrated stability to extremes of pH, temperature, and exposure to human blood plasma indicating that this linkage is significantly more robust than maleimide-type linkages that are commonly employed in bioconjugations. These studies support the broad utility of this reaction in the chemoselective modification of small molecules, peptides, and proteins under mild aqueous conditions over a broad pH range using a wide variety of biologically acceptable buffers such as phosphate buffered saline (PBS) and 2-amino-2-hydroxymethyl-propane-1,3-diol (Tris) buffers as well as others and mixed buffered compositions.

Dataset Information

Facile Fabrication of Ordered Component-Tunable Heterobimetallic Self-Assembly Nanosheet for Catalyzing "Click" Reaction.

Publications

Facile Fabrication of Ordered Component-Tunable Heterobimetallic Self-Assembly Nanosheet for Catalyzing "Click" Reaction.

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