Iraklii I. Ebralidze

Simple direct formation of self-assembled N-heterocyclic carbene monolayers on gold and their application in biosensing

The formation of organic films on gold employing N-heterocyclic carbenes (NHCs) has been previously shown to be a useful strategy for generating stable organic films. However, NHCs or NHC precursors typically require inert atmosphere and harsh conditions for their generation and use. Herein we describe the use of benzimidazolium hydrogen carbonates as bench stable solid precursors for the preparation of NHC films in solution or by vapour-phase deposition from the solid state. The ability to prepare these films by vapour-phase deposition permitted the analysis of the films by a variety of surface science techniques, resulting in the first measurement of NHC desorption energy (158±10 kJ mol−1) and confirmation that the NHC sits upright on the surface. The use of these films in surface plasmon resonance-type biosensing is described, where they provide specific advantages versus traditional thiol-based films.

Characterization of TLR4/MD-2-modified Au sensor surfaces towards the detection of molecular signatures of bacteria

Lipopolysaccharides (LPSs), also known as endotoxins, can be fatal even at low concentrations. As a result, the development of novel methodologies for LPS detection has been continuously in the focus of research. Biosensors, which employ a bio-recognition element on a transducer surface, are on the cutting edge of these novel technologies. In this report, Au surfaces modified with TLR4/MD-2 through Lip-NHS linkers with an ultimate potential application as biosensors for LPS detection have been characterized and investigated using X-ray photoelectron spectroscopy, quartz crystal microbalance and electrochemical techniques. Also the interaction between TLR4/MD-2 immobilized on Au surfaces with LPSs has been studied to evaluate the possibility of LPS detection.

Characterization of hydroxyphenol-terminated alkanethiol self-assembled monolayers: interactions with phosphates by chemical force spectrometry.

Tannins and humic substances, commonly referred to as natural organic matter (NOM), constitute an important component of natural water and soil systems. These species contain numerous hydroxyl and carboxyl functional groups whose reactivity is strongly dependent on both the quantity and location of these moieties on the aromatic ring. In the present study, self-assembled monolayers (SAMs) of 4-(12-mercaptododecyl)benzene-1,2-diol (o-hydroxyphenol-terminated); 5-(12-mercaptododecyl)benzene-1,3-diol (m-hydroxyphenol-terminated); bis(11-thioundecyl) hydrogen phosphate (monoprotic phosphate); and 11-thioundecyl dihydrogen phosphate (diprotic phosphate) were prepared and characterized using X-ray photoelectron spectroscopy (XPS), attenuated total reflectance infrared spectroscopy (ATR-IR), and water contact angle measurements. The interactions between phenolic groups with phosphates were examined as a function of pH using the chemical force spectrometry (CFS) technique. The observations are discussed in the context of hydrogen bonding and electrostatic repulsion interaction between corresponding species. Adhesion force profiles of hydroxyphenol isomers interacting with monoprotic phosphate are dominated by ionic H-bonding; however the strength of o-hydroxyphenol interactions is significantly higher. The difference in location of hydroxyl groups on the interface also results in significantly different force-distance profiles for the isomeric hydroxyphenols when interacting with diprotic phosphate.

A fuel cell catalyst support based on doped titanium suboxides with enhanced conductivity, durability and fuel cell performance

An entirely carbon-free multifunctional titanium suboxide doped with two metals has been developed as a novel fuel cell catalyst support. The co-functional Ti3O5Mo0.2Si0.4 (TOMS) support shows remarkably high electronic conductivity for a metal oxide. A Pt/TOMS catalyst was prepared and found to show excellent activity towards the oxygen reduction reaction (ORR). This enhanced activity is attributed to a strong electronic interaction between the Pt nanoparticles and the TOMS support. Furthermore, this Pt/TOMS catalyst shows extraordinary durability in accelerated stress tests, losing only 10% of its active surface area over the 5000 cycle accelerated stress test. The fuel cell performance testing of the Pt/TOMS catalyst shows that practical fuel cell devices can be readily fabricated and achieve high performance, exceeding those of commercial catalysts. Thus, the proposed Pt/TOMS has the potential to be a viable carbon-free support that could be deployed in PEMFC technology as a near-term solution.

Hemoglobin-driven iron-directed assembly of gold nanoparticles

The ability to form complex 3D architectures using nanoparticles (NPs) as the building blocks and complex macromolecules that direct these assemblies remains a challenging objective for nanotechnology. Here we report results in which the partial substitution of classical Turkevich citrate-capped gold NPs by a novel, heteroaromatic ligand (L) results in NPs able to form coordination-driven assemblies mediated by free or protein-bound iron ions. The morphology of these assemblies can be tuned depending on the source of iron. To prove the concept, classical citrate and novel NPs were reacted with iron-containing protein hemoglobin (Hb). To diminish the influence of possible electrostatic interactions of native Hb and gold NPs, the reaction was performed at the isoelectric point of Hb. Moreover, thiol groups of Hb were protected with p-quinone to exclude thiol–gold bond formation. As expected, citrate-capped gold NPs are well dispersed in functionalized Hb, while L-functionalized NPs form assemblies. The blue shift of the Soret band of the functionalized Hb, when reacted with novel NPs, unambiguously confirms the coordination of a NP-anchored heteroaromatic ligand with the heme moiety of Hb. Coarse-grained molecular dynamics of this system were performed to gain information about aggregation dynamics and kinetics of iron- and hemoglobin-templated assemblies of L–NPs. A multi-scale simulation approach was employed to extend this model to longer time scales. The application of this model towards novel coordination-based assemblies can become a powerful tool for the development of new nanomaterials.

Ligand Impact on Monolayer Electrochromic Material Properties

In this study, we present a range of efficient highly durable electrochromic materials that demonstrate excellent redox and lifetime stability, sufficient coloration contrast ratios, and the best-in-class electron-transfer constants. The materials were formed by anchoring as little as a monolayer of predefined iron complexes on a surface-enhanced conductive solid support. The thickness of the substrate was optimized to maximize the change in optical density. We demonstrate that even a slight change in molecular sterics and electronics results in materials with sufficiently different properties. Thus, minor changes in the ligand design give access to materials with a wide range of color variations, including green, purple, and brown. Moreover, ligand architecture dictates either orthogonal or parallel alignment of corresponding metal complexes on the surface due to mono- or bis-quaternization. We demonstrate that monoquaternization of the complexes during anchoring to the surface-bound template layer results in redshifts of the photoabsorption peak. The results of in-solution bis-methylation supported by density functional theory calculations show that the second quaternization may lead to an opposite blueshift (in comparison with monomethylated analogs), depending on the ligand electronics and the environmental change. It is shown that the variations of the photoabsorption peak position for different ligands upon attachment to the surface can be related to the calculated charge distribution and excitation-induced redistribution. Overall, the work demonstrates a well-defined method of electrochromic material color tuning via manipulation of sterics and electronics of terpyridine-based ligands.