The deselenization of selenocysteine selectively removes the selenol group to give alanine under anaerobic conditions or serine under aerobic conditions (oxygen saturation).
The human body contains 25 selenoproteins, but challenges in their preparations have prevented biological characterizations thus far. Here we report the first total chemical syntheses of two human selenoproteins, selenoprotein M (SELM) and selenoprotein W (SELW).
N-heterocyclic carbenes (NHCs) have been widely utilized for the formation of self-assembled monolayers (SAMs) on various surfaces. The main methodologies for preparation of NHCs-based SAMs either requires inert atmosphere and strong base for deprotonation of imidazolium precursors or the use of specifically-synthesized precursors such as NHC(H)[HCO3] salts or NHC–CO2 adducts. Herein, we demonstrate an electrochemical approach for surface-anchoring of NHCs which overcomes the need for dry environment, addition of exogenous strong base or restricting synthetic steps. In the electrochemical deposition, water reduction reaction is used to generate high concentration of hydroxide ions in proximity to a metal electrode. Imidazolium cations were deprotonated by hydroxide ions, leading to carbenes formation that self-assembled on the electrode’s surface. SAMs of NO2-functionalized NHCs and dimethyl-benzimidazole were electrochemically deposited on Au films. SAMs of NHCs were also electrochemically deposited on Pt, Pd and Ag films, demonstrating the wide metal scope of this deposition technique.
Monitoring of nanoparticles (NPs) in air and aquatic environments is an unmet challenge accentuated by the rising exposure to anthropogenic or engineered NPs. The inherent heterogeneity in size, shape, and the stabilizing shell of NPs makes their selective recognition a daunting task. Thus far, only a few technologies have shown promise in detecting NPs; however, they are cumbersome, costly, and insensitive to the NPs morphology or composition. Herein, we apply an approach termed nanoparticle-imprinted matrices (NAIM), which is based on creating voids in a thin layer by imprinting NPs followed by their removal. The NAIM was formed on an interdigitated electrode (IDE) and used for the size-selective detection of silica NPs. Three-and 5-fold increases in capacitance were observed for the reuptake of NPs with similar diameter, compared to smaller or larger NPs, in air and liquid phase, respectively. En masse, the proposed approach lays the foundation for the emergence of field-effective, inexpensive, real-life applicable sensors that will allow online monitoring of NPs in air and liquids.
Studying nanoparticle (NP)–electrode interactions
in single
nanoparticle collision events is critical to understanding dynamic
processes such as nanoparticle motion, adsorption, oxidation, and
catalytic activity, which are abundant on electrode surfaces. Herein,
NP–electrode electrostatic interactions are studied by tracking
the oxidation of AgNPs at Au microelectrodes functionalized with charged
self-assembled monolayers (SAMs). Tuning the charge of short alkanethiol-based
monolayers and selecting AgNPs that can be partially or fully oxidized
upon impact enabled probing the influence of attractive and repulsive
NP–electrode electrostatic interactions on collision frequency,
electron transfer, and nanoparticle sizing. We find that repulsive
electrostatic interactions lead to a significant decrease in collision
frequency and erroneous nanoparticle sizing. In stark difference,
attractive electrostatic interactions dramatically increase the collision
frequency and extend the sizing capability to larger nanoparticle
sizes. Thus, these findings demonstrate how NP–monolayer interactions
can be studied and manipulated by combining nanoimpact electrochemistry
and functionalized SAMs.
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