Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials.

Cytotoxicity Evaluation of Si-Diatom Frustules in a Mouse Model

Silica additives in bone substitute materials are topical, clinically interesting and have significant support in the Orthopaedic field. Biosilica, e.g isolated from diatoms, has many advantages over its synthetic counterparts, e.g. it is amorphous, thus will be absorbed by the body, however, issues such as purity, presence of endotoxins and cytotoxicity need to be addressed before it can be further exploited. Biosilica isolated from Cyclotella Meneghiniana was then tested in a mouse model, to test the immunological response, organ toxicity (kidney, spleen, liver) and route of metabolism/excretion of silica. Five-week-old Balb-c mice were injected subcutaneously with a single high dose (50mg/ml) of Si-frustules, Si-frustules + organic linker and vehicle only control. Animals were sacrificed at 1d and 28d. The animal studies were conducted under an ethically approved protocol at Queen’s University, Belfast. The animals showed no adverse stress during the experiment and remained healthy until sacrifice. Blood results using ICP-OES analysis suggest the frustules were metabolized between comparator groups at different rates, and clearly showed elevated levels of silicon in groups injected with frustules relative to control. The histology of organs showed no variation in morphology of mice injected frustules relative compared to the control group.
Acknowledgements: The authors would like to thank Marie Curie International Outgoing Fellowships from the EU and Beaufort Marine Biodiscovery Award as part of the Marine Biotechnology Ireland Programme for providing financial support to this project.

Epitaxial growth of molecular crystals on van der Waals substrates for high-performance organic electronics

Epitaxial van der Waals (vdW) heterostructures of organic and layered materials are demonstrated to create high-performance organic electronic devices. High-quality rubrene films with large single-crystalline domains are grown on h-BN dielectric layers via vdW epitaxy. In addition, high carrier mobility comparable to free-standing single-crystal counterparts is achieved by forming interfacial electrical contacts with graphene electrodes.

Electric Field Effects on Graphene Materials

Understanding the effect of electric fields on the physical and chemical properties of two-dimensional (2D) nanostructures is instrumental in the design of novel electronic and optoelectronic devices. Several of those properties are characterized in terms of the dielectric constant which play an important role on capacitance, conductivity, screening, dielectric losses and refractive index. Here we review our recent theoretical studies using density functional calculations including van der Waals interactions on two types of layered materials of similar two-dimensional molecular geometry but remarkably different electronic structures, that is, graphene and molybdenum disulphide (MoS2). We focus on such two-dimensional crystals because of they complementary physical and chemical properties, and the appealing interest to incorporate them in the next generation of electronic and optoelectronic devices. We predict that the effective dielectric constant (ε) of few-layer graphene and MoS2 is tunable by external electric fields (E ext). We show that at low fields (E ext < 0.01 V/Å) ε assumes a nearly constant value ∼4 for both materials, but increases at higher fields to values that depend on the layer thickness. The thicker the structure the stronger is the modulation of ε with the electric field. Increasing of the external field perpendicular to the layer surface above a critical value can drive the systems to an unstable state where the layers are weakly coupled and can be easily separated. The observed dependence of ε on the external field is due to charge polarization driven by the bias, which show several similar characteristics despite of the layer considered. All these results provide key information about control and understanding of the screening properties in two-dimensional crystals beyond graphene and MoS2