Microfluidic devices fabricated using soft lithography for the study of protein structures using synchrotron radiation circular dichroism

The combination of microfluidic with Synchrotron Radiation Circular Dichroism (SRCD) is highly promising for the study of protein interactions and misfolding in real time. However, due to the strong absorption of many materials in the far-UV region, the fabrication of microfluidic devices has been limited to fused silica devices. Here we present two device architectures, fabricated using conventional PDMS-based soft-lithography, compatible with SRCD

Photo-induced optical activity in phase-change memory materials

We demonstrate that optical activity in amorphous isotropic thin films of pure Ge2Sb2Te5 and N-doped Ge2Sb2Te5N phase-change memory materials can be induced using rapid photo crystallisation with circularly polarised laser light. The new anisotropic phase transition has been confirmed by circular dichroism measurements. This opens up the possibility of controlled induction of optical activity at the nanosecond time scale for exploitation in a new generation of high-density optical memory, fast chiroptical switches and chiral metamaterials

Resolving protein mixtures using microfluidic diffusional sizing combined with synchrotron radiation circular dichroism.

Circular dichroism spectroscopy has become a powerful tool to characterise proteins and other biomolecules. For heterogeneous samples such as those present for interacting proteins, typically only average spectroscopic features can be resolved. Here we overcome this limitation by using free-flow microfluidic size separation in-line with synchrotron radiation circular dichroism to resolve the secondary structure of each component of a model protein mixture containing monomers and fibrils. To enable this objective, we have integrated far-UV compatible measurement chambers into PDMS-based microfluidic devices. Two architectures are proposed so as to accommodate for a wide range of concentrations. The approach, which can be used in combination with other bulk measurement techniques, paves the way to the study of complex mixtures such as the ones associated with protein misfolding and aggregation diseases including Alzheimer's and Parkinson's diseases

Giant photoinduced chirality in thin film Ge2Sb2Te5

Induction, tuning, or amplification of chirality in various classes of materials and probing their chiral response are subjects of growing research. Herein, a large chiral signal that is rapidly imprinted in achiral amorphous Ge2Sb2Te5 (GST) thin films measured using synchrotron circular dichroism spectroscopy is reported. The chirality is induced by illuminating the films with pulsed circularly polarized (chiral) laser light for less than 2 μs in total. The effects of laser fluence and film thickness on the chiral response are described. The correlation of the optical results with structural studies by electron diffraction and model simulations suggests that alignment of reamorphized fragments in the crystallized film along the electric field vector of the light forms the centers that are responsible for the observed chirality. These results suggest opportunities for practical applications of this phenomenon and provide avenues for further studies of chirality induction in materials with impact in a wide range of disciplines

Natural optical activity as the origin of the large chiroptical properties in π-conjugated polymer thin films

Polymer thin films that emit and absorb circularly polarised light have been demonstrated with the promise of achieving important technological advances; from efficient, high-performance displays, to 3D imaging and all-organic spintronic devices. However, the origin of the large chiroptical effects in such films has, until now, remained elusive. We investigate the emergence of such phenomena in achiral polymers blended with a chiral small-molecule additive (1-aza[6]helicene) and intrinsically chiral-sidechain polymers using a combination of spectroscopic methods and structural probes. We show that – under conditions relevant for device fabrication – the large chiroptical effects are caused by magneto-electric coupling (natural optical activity), not structural chirality as previously assumed, and may occur because of local order in a cylinder blue phase-type organisation. This disruptive mechanistic insight into chiral polymer thin films will offer new approaches towards chiroptical materials development after almost three decades of research in this area

Anisotropic organization and microscopic manipulation of self-assembling synthetic porphyrin microrods that mimic chlorosomes: Bacterial light-harvesting systems

Being able to control in time and space the positioning, orientation, movement, and sense of rotation of nano- to microscale objects is currently an active research area in nanoscience, having diverse nanotechnological applications. In this paper, we demonstrate unprecedented control and maneuvering of rod-shaped or tubular nanostructures with high aspect ratios which are formed by self-assembling synthetic porphyrins. The self-assembly algorithm, encoded by appended chemical-recognition groups on the periphery of these porphyrins, is the same as the one operating for chlorosomal bacteriochlorophylls (BChl's). Chlorosomes, rod-shaped organelles with relatively long-range molecular order, are the most efficient naturally occurring light-harvesting systems.(1, 2) They are used by green photosynthetic bacteria to trap visible and infrared light of minute intensities even at great depths, e.g., 100 m below water surface or in volcanic vents in the absence of solar radiation. In contrast to most other natural light-harvesting systems, the chlorosomal antennae are devoid of a protein scaffold to orient the BChl's; thus, they are an attractive goal for mimicry by synthetic chemists, who are able to engineer more robust chromophores to self-assemble. Functional devices with environmentally friendly chromophores-which should be able to act as photosensitizers within hybrid solar cells, leading to high photon-to-current conversion efficiencies even under low illumination conditions-have yet to be fabricated. The orderly manner in which the BChl's and their synthetic counterparts self-assemble imparts strong diamagnetic and optical anisotropies and flow/shear characteristics to their nanostructured assemblies, allowing them to be manipulated by electrical, magnetic, or tribomechanical forces. © 2011 American Chemical Society