Imprinting of nanoparticles in thin films: Quo Vadis?

Nanomaterials, and especially nanoparticles, have been introduced to almost any aspect of our lives. This has caused increasing concern as to their toxicity and adverse effects on the environment and human health. The activity of nanoparticles, including their nanotoxicity, is not only a function of the material they are made of but also their size, shape, and surface properties. It is evident that there is an unmet need for simple approaches to the speciation of nanoparticles, namely to monitor and detect them based on their properties. An appealing method for such speciation involves the imprinting of nanoparticles in soft matrices. The principles of imprinting nanoparticles originate from the molecularly imprinted polymer (MIP) approach. This review summarizes the current status of this emerging field, which bridges between the traditional MIP approach and the imprinting of larger entities such as viruses and bacteria. The concepts of nanoparticle imprinting and the requirement of both physical and chemical matching between the nanoparticles and the matrix are discussed and demonstrated.

Influence of Charged Self-Assembled Monolayers on Single Nanoparticle Collision.

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.

Size-Selective Detection of Nanoparticles in Solution and Air by Imprinting.

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.

Electrochemical deposition of N-heterocyclic carbene monolayers on metal surfaces.

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.

Insights into the deselenization of selenocysteine into alanine and serine.

The development of native chemical ligation coupled with desulfurization has allowed ligation at several new ligation junctions. However, desulfurization also converts all cysteine residues in the protein sequence into alanine. Deselenization of selenocysteine, in contrast, selectively removes the selenol group to give alanine in the presence of unprotected cysteines. In this study we shed more light onto the deselenization mechanism of selenocysteine to alanine and provide optimized conditions for the reaction. The deselenization can be accomplished in one minute under anaerobic conditions to give alanine. Under aerobic conditions (oxygen saturation), selenocysteine is converted into serine.