To further our understanding on the antibacterial activity of single-walled carbon nanotubes (SWCNTs), high purity SWCNTs with average diameter of 0.83 nm and (7,5) chirality as dominate (n,m) structure were dispersed in a biocompatible surfactant solution. Ultraviolet-visible-near-infrared radiation absorption spectroscopy was employed to monitor the aggregation of SWCNTs. The results demonstrated that individually dispersed SWCNTs were more toxic than SWCNT aggregates toward bacteria (gram-negative Escherichia coli, Pseudomonas aeruginosa, and gram-positive Staphylococcus aureus, Bacillus subtilis). Individually dispersed SWCNTs can be visualized as numerous moving "nano darts" in the solution, constantly attacking the bacteria; thereby, degrading the bacterial cell integrity and causing the cell death. Controlled experimental results suggested that inhibiting cell growth and oxidative stress were not the major causes responsible for the death of cells. Furthermore, the detrimental effects of Co metal residues (up to 1 mug/mL) on SWCNT samples can be ruled out. Atomic force microscope study conducted in suspension proved that the death rates of bacteria were strongly correlated with their mechanical properties; soft cells were more vulnerable to SWCNT piercing. The antibacterial activity of SWCNTs can be remarkably improved by enhancing the SWCNT physical puncture on bacteria in the following ways: (1) dispersing SWCNTs individually to sharpen the nano darts; (2) increasing SWCNT concentration to raise the population density of nano darts; and (3) elevating the shaking speed of incubation to speed up the nano darts. This study elucidated several factors controlling the antibacterial activity of pristine SWCNTs and it provided an insight in developing strategies that can maximize the SWCNT application potentials while minimizing the health and environment risks.
The first N-Heterocyclic Carbene (NHC) mediated activation of stable carboxylate esters to generate enolate intermediates is disclosed. The catalytically generated arylacetic ester enolates undergo enantioselective reactions with α,β-unsaturated imines.
A carbene-catalyzed
reductive coupling reaction of carboxylic esters
and substituted Hantzsch esters is disclosed. Key steps of this reaction
include one-electron reduction of a carbene catalyst-bound acyl azolium
intermediate to generate the corresponding radical intermediate for
subsequent alkylation reactions. The reaction is promoted by irradiation
with visible light without the involvement of transition-metal photocatalysts.
Mechanistic studies suggest that direct photoexcitation of the in
situ formed acyl azolium intermediate is likely responsible for this
light-induced one-electron-reduction process. Photoexcitation converts
the acyl azolium intermediate to a single-electron oxidant, enabling
single-electron oxidation of Hantzsch esters to generate radical intermediates.
Our reactions work well for a broad range of aryl carboxylic ester
and Hantzsch ester substrates. Sophisticated structures, including
those present in medicines, can be incorporated into ketone molecules
using our approach via very mild conditions that tolerate various
functional groups.
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