Electrochemical detection of 4(5)-methylimidazole in aqueous solutions.

4(5)-methylimidazole (4-MeI) is a potential carcinogen widely used in food colours. EU regulations specify a maximum allowable concentration of 200 ppm for 4-MeI in caramel colours. This study reports an electrochemical determination technique for 4-MeI in caramel colours for the first time. The effect of pH and interference from air were studied to optimize the detection conditions on a glassy carbon electrode in aqueous alkaline solutions using square wave voltammetry (SWV) technique. The concentration of 4-MeI was quantitatively measured down to 10 µM (∼0.8 ppm). Traditional methods such as HPLC, GC, spectrometry and immunoassays involve either expensive instrumentation and reagents or time consuming preparation and detection processes. This study demonstrates the possibility of rapid and simple electrochemical determination of (4-MeI) in food colours with minimum workup using a portable potentiostat.

Nanoscale molecular rectifiers.

The use of molecules bridged between two electrodes as a stable rectifier is an important goal in molecular electronics. Until recently, however, and despite extensive experimental and theoretical work, many aspects of our fundamental understanding and practical challenges have remained unresolved and prevented the realization of such devices. Recent advances in custom-designed molecular systems with rectification ratios exceeding 105 have now made these systems potentially competitive with existing silicon-based devices. Here, we provide an overview and critical analysis of recent progress in molecular rectification within single molecules, self-assembled monolayers, molecular multilayers, heterostructures, and metal-organic frameworks and coordination polymers. Examples of conceptually important and best-performing systems are discussed, alongside their rectification mechanisms. We present an outlook for the field, as well as prospects for the commercialization of molecular rectifiers.

Electrochemical Potential-Driven High-Throughput Molecular Electronic and Spintronic Devices: From Molecules to Applications.

Molecules are fascinating candidates for constructing tunable and electrically conducting devices by the assembly of either a single molecule or an ensemble of molecules between two electrical contacts followed by current-voltage (I-V) analysis, which is often termed "molecular electronics". Recently, there has been also an upsurge of interest in spin-based electronics or spintronics across the molecules, which offer additional scope to create ultrafast responsive devices with less power consumption and lower heat generation using the intrinsic spin property rather than electronic charge. Researchers have been exploring this idea of utilizing organic molecules, organometallics, coordination complexes, polymers, and biomolecules (proteins, enzymes, oligopeptides, DNA) in integrating molecular electronics and spintronics devices. Although several methods exist to prepare molecular thin-films on suitable electrodes, the electrochemical potential-driven technique has emerged as highly efficient. In this Review we describe recent advances in the electrochemical potential driven growth of nanometric various molecular films on technologically relevant substrates, including non-magnetic and magnetic electrodes to investigate the stimuli-responsive charge and spin transport phenomena.

Orbital Control of Photocurrents in Large Area All-Carbon Molecular Junctions.

Photocurrents generated by illumination of carbon-based molecular junctions were investigated as diagnostics of how molecular structure and orbital energies control electronic behavior. Oligomers of eight aromatic molecules covalently bonded to an electron-beam deposited carbon surface were formed by electrochemical reduction of diazonium reagents, with layer thicknesses in the range of 5-12 nm. Illumination through either the top or bottom partially transparent electrodes produced both an open circuit potential (OCP) and a photocurrent (PC), and the polarity and spectrum of the photocurrent depended directly on the relative positions of the frontier orbitals and the electrode Fermi level (EF). Electron donors with relatively high HOMO energies yielded positive OCP and PC, and electron acceptors with LUMO energies closer to EF than the HOMO energy produced negative OCP and PC. In all cases, the PC spectrum and the absorption spectrum of the oligomer in the molecular junction had very similar shapes and wavelength maxima. Asymmetry of electronic coupling at the top and bottom electrodes due to differences in bonding and contact area cause an internal potential gradient which controls PC and OCP polarities. The results provide a direct indication of which orbital energies are closest to EF and also indicate that transport in molecular junctions thicker than 5 nm is controlled by the difference in energy of the HOMO and LUMO orbitals.

Nanometric building blocks for robust multifunctional molecular junctions.

Much of the motivation for developing molecular electronic devices is the prospect of achieving novel electronic functions by varying molecular structure. We describe a "building block" approach for molecular junctions resulting in one, two or three nanometer-thick molecular layers in a commercially proven junction design. A single layer of anthraquinone between carbon electrodes provides a tunnel device with applications in electronic music, and a second layer of a thiophene derivative yields a molecular rectifier with quite different audio characteristics. A third layer of lithium benzoate produces a redox-active device with possible applications in non-volatile memory devices or on-chip energy storage. The building block approach forms a basis for "rational design" of electronic functions, in which layers of varying structure produce distinct and desirable electronic behaviours.

Control of Electronic Symmetry and Rectification through Energy Level Variations in Bilayer Molecular Junctions.

Two layers of molecular oligomers were deposited on flat carbon electrode surfaces by electrochemical reduction of diazonium reagents, then a top contact applied to complete a solid-state molecular junction containing a molecular bilayer. The structures and energy levels of the molecular layers included donor molecules with relatively high energy occupied orbitals and acceptors with low energy unoccupied orbitals. When the energy levels of the two molecular layers were similar, the device had electronic characteristics similar to a thick layer of a single molecule, but if the energy levels differed, the current voltage behavior exhibited pronounced rectification. Higher current was observed when the acceptor molecule was biased negatively in eight different bilayer combinations, and the direction of rectification was reversed if the molecular layers were also reversed. Rectification persisted at very low temperature (7 K), and was activationless between 7 and 100 K. The results are a clear example of a "molecular signature" in which electronic behavior is directly affected by molecular structure and orbital energies. The rectification mechanism is discussed, and may provide a basis for rational design of electronic properties by variation of molecular structure.

Bilayer molecular electronics: all-carbon electronic junctions containing molecular bilayers made with "click" chemistry.

Bilayer molecular junctions were fabricated by using the alkyne/azide "click" reaction on a carbon substrate, followed by deposition of a carbon top contact in a crossbar configuration. The click reaction on an alkyne layer formed by diazonium reduction permitted incorporation of a range of molecules into the resulting bilayer, including alkane, aromatic, and redox-active molecules, with high yield (>90%) and good reproducibility. Detailed characterization of the current-voltage behavior of bilayer molecular junctions indicated that charge transport is consistent with tunneling, but that the effective barrier does not strongly vary with molecular structure for the series of molecules studied.