Covalent Linkages of Molecules and Proteins to Si-H Surfaces Formed by Disulfide Reduction.

Thiols and disulfide contacts have been, for decades, key for connecting organic molecules to surfaces and nanoclusters as they form self-assembled monolayers (SAMs) on metals such as gold (Au) under mild conditions. In contrast, they have not been similarly deployed on Si owing to the harsh conditions required for monolayer formation. Here, we show that SAMs can be simply formed by dipping Si-H surfaces into dilute solutions of organic molecules or proteins comprising disulfide bonds. We demonstrate that S-S bonds can be spontaneously reduced on Si-H, forming covalent Si-S bonds in the presence of traces of water, and that this grafting can be catalyzed by electrochemical potential. Cyclic disulfide can be spontaneously reduced to form complete monolayers in 1 h, and the reduction can be catalyzed electrochemically to form full surface coverages within 15 min. In contrast, the kinetics of SAM formation of the cyclic disulfide molecule on Au was found to be three-fold slower than that on Si. It is also demonstrated that dilute thiol solutions can form monolayers on Si-H following oxidation to disulfides under ambient conditions; the supply of too much oxygen, however, inhibits SAM formation. The electron transfer kinetics of the Si-S-enabled SAMs on Si-H is comparable to that on Au, suggesting that Si-S contacts are electrically transmissive. We further demonstrate the prospect of this spontaneous disulfide reduction by forming a monolayer of protein azurin on a Si-H surface within 1 h. The direct reduction of disulfides on Si electrodes presents new capabilities for a range of fields, including molecular electronics, for which highly conducting SAM-electrode contacts are necessary and for emerging fields such as biomolecular electronics as disulfide linkages could be exploited to wire proteins between Si electrodes, within the context of the current Si-based technologies

Intrinsic and well-defined second generation hot spots in gold nanobipyramids: Versus gold nanorods

An effective strategy for regioselective modification and directional assembly of anisotropic nanoparticles is demonstrated to explore the electric field enhancement in assembled gold nanobipyramids compared with gold nanorods. The well-defined secondary plasmonic hot spots between the coupled gold nanobipyramids exhibit the capability for single molecule detection

Recent advances in the molecular level modification of electrodes for bioelectrochemistry

Advances in the fabrication of bioelectrochemical interfaces has provide us with something close to molecular level control over both the immobilisation of biomolecules on an electrode and the environment around which they are immobilised. This control can be both lateral, by changing the ratio of components in a mixed monolayer, and vertical using rigid self-assembling molecules. The most important advances in the last few years are the development of methods that allow amperometric systems to operate in complex biological fluids and new methods of characterising the bioelectrochemical interfaces at the molecular level at which they are designed. The purpose of this Current Opinion review is to outline the advances in low impedance antifouling coatings on electrodes for bioelectrochemistry and the use of cutting edge fluorescence microscopy to characterise the function of these interfaces in the environments they are intended to be used in with high spatial resolution

Increasing the Formation of Active Sites on Highly Crystalline Co Branched Nanoparticles for Improved Oxygen Evolution Reaction Electrocatalysis

The electrocatalysis of the oxygen evolution reaction (OER) at the surface of oxidized metal electrocatalysts is highly dependent on the structure and composition of the surface oxide. Here, Au core- Co branched nanoparticles were synthesized using a cubic-core hexagonal-branch growth approach in a slow reductive solution synthesis, resulting in highly crystalline metallic hcp Co branches. Electrochemical surface oxidation of the Co branched nanoparticles resulted in formation of Co(OH)2 that enable the formation of a higher number of active sites under OER conditions compared to Co3O4. Differently from polycrystalline spherical Au−Co core-shell nanoparticles, the oxidized structure on the Co branched nanoparticle surface is retained with electrochemical cycling, resulting in improved OER activity and stability

Cesium compounds as interface modifiers for stable and efficient perovskite solar cells

The presented work demonstrates the development of highly stable low temperature processed Cesium compound incorporated ZnO electron transport layer (ETL) for perovskite solar cells (PSCs). Cesium compounds such as CA (cesium acetate) and CC (cesium carbonate) modified ETLs are employed for fabricating highly efficient (PCE: ~ 16.5%) mixed organic cation based MA0.6FA0.4PbI3 PSCs via restricted volume solvent annealing (RVSA) method. Here, CA ETL demonstrates a 50 meV upshift in Fermi level position with respect to CC ETL, contributing to higher n-type conductivity and lower electron injection barrier at the interface. Furthermore, CA ETL also exhibits profound influence on the perovskite microstructure leading to larger grain size and uniform distribution. Cesium acetate incorporated devices exhibit about 82% higher PCE compared to conventional CC devices. In addition to higher photovoltaic performance, CA devices exhibit mitigated photo-current hysteresis phenomena compared to CC devices, owing to suppressed electrode polarization phenomena. Besides, the stability of the CA devices are 400% higher than the conventional CC devices, retaining almost 90% of its initial PCE even after a month-long (30 days) systematic degradation study. The mechanism behind superior performance and stability is investigated and discussed comprehensively

Observing the Reversible Single Molecule Electrochemistry of Alexa Fluor 647 Dyes by Total Internal Reflection Fluorescence Microscopy

Alexa Fluor 647 is a widely used fluorescent probe for cell bioimaging and super-resolution microscopy. Herein, the reversible fluorescence switching of Alexa Fluor 647 conjugated to bovine serum albumin (BSA) and adsorbed onto indium tin oxide (ITO) electrodes under electrochemical potential control at the level of single protein molecules is reported. The modulation of the fluorescence as a function of potential was observed using total internal reflectance fluorescence (TIRF) microscopy. The fluorescence intensity of the Alexa Fluor 647 decreased, or reached background levels, at reducing potentials but returned to normal levels at oxidizing potentials. These electrochemically induced changes in fluorescence were sensitive to pH despite that BSA-Alexa Fluor 647 fluorescence without applied potential is insensitive to pH between values of 4–10. The observed pH dependence indicated the involvement of electron and proton transfer in the fluorescence switching mechanism