Experimental and computational characterisation of an artificial light harvesting complex.

Photosynthesis has been shown to be a highly efficient process for energy transfer in plants and bacteria. Like natural photosynthetic systems, the artificial light harvesting complex (LHC) BODIPY pillar[5]arene exhibits Förster resonance energy transfer (FRET). However, extensive characterisation of the BODIPY pillar[5]arene LHC to determine its suitability as an artificial LHC has yet to occur. In this paper we experimentally and computationally investigate the photophysical properties of the LHC by comparing the light absorption of the BODIPY LHC to individual BODIPY chromophores. Our results show evidence for quantum coherence, with oscillation frequencies of 100 cm-1 and 600 cm-1, which are attributable to vibronic, or exciton-phonon type coupling. Computational analysis suggests strong couplings of the molecular orbitals of the LHC resulting from the stacking of neighbouring BODIPY chromophore units. Interestingly, we find a 40% reduction in the absorbance of light for the BODIPY LHC compared to the individual chromophores which we attribute to electronic interactions between the conjugated π-systems of the BODIPY chromophores and the pillar[5]arene backbone.

A Multiplexed Microfluidic Platform toward Interrogating Endocrine Function: Simultaneous Sensing of Extracellular Ca2+ and Hormone.

Extracellular Ca2+ ([Ca2+]ex) is an important regulator of various physiological and pathological functions, including intercellular communication for synchronized cellular activities (e.g., coordinated hormone secretion from endocrine tissues). Yet it is rarely possible to concurrently quantify the dynamic changes of [Ca2+]ex and related bioactive molecules with high accuracy and temporal resolution. This work aims to develop a multiplexed microfluidic platform to enable monitoring oscillatory [Ca2+]ex and hormone(s) in a biomimetic environment. To this end, a low-affinity fluorescent indicator, Rhod-5N, is identified as a suitable sensor for a range of [Ca2+]ex based on its demonstrated high sensitivity and selectivity to Ca2+ in biomedical samples, including human serum and cell culture medium. A microfluidic chip is devised to allow for the immobilization of microscale subjects (analogous to biological tissues), precise control of the perfusion gradient at sites of interest, and integration of modalities for fluorescence measurement and enzyme-linked immunosorbent assay. As this analytical system is demonstrated to be viable to quantify the dynamic changes of Ca2+ (0.2-2 mM) and insulin (15-150 mU L-1) concurrently, with high temporal resolution, it has the potential to provide key insights into the essential roles of [Ca2+]ex in the secretory function of endocrine tissues and to identify novel therapeutic targets for human diseases.

Surface Functionalization of Exposed Core Glass Optical Fiber for Metal Ion Sensing.

One of the biggest challenges associated with exposed core glass optical fiber-based sensing is the availability of techniques that can be used to generate reproducible, homogeneous and stable surface coating. We report a one step, solvent free method for surface functionalization of exposed core glass optical fiber that allows achieving binding of fluorophore of choice for metal ion sensing. The plasma polymerization-based method yielded a homogeneous, reproducible and stable coating, enabling high sensitivity aluminium ion sensing. The sensing platform reported in this manuscript is versatile and can be used to bind different sensing molecules opening new avenues for optical fiber-based sensing.

Control of Molecular Recognition via Modulation of the Nanoenvironment.

Many biological processes are driven by the interaction of a host with a guest molecule. We show such interactions can be modulated by carefully defining the local molecular environment to give a specific chemical outcome. Particularly, the selectivity of a host toward two different ions (Ca2+ and Al3+) is defined by it being in solution or the physisorbed state. In solution, the host displays greater selectivity toward Ca2+. When physisorbed, the selectivity profile of the host is reversed with enhanced binding of Al3+. This demonstrates a single host molecule can be tailored to selectively bind multiple guests by altering its nanoenvironment.

Nanofilm-induced spectral tuning of third harmonic generation.

Intermodal third-harmonic generation using waveguides is an effective frequency conversion process due to the combination of long interaction lengths and strong modal confinement. Here we introduce the concept of tuning the third harmonic phase-matching condition via the use of dielectric nanofilms located on an open waveguide core. We experimentally demonstrate that tantalum oxide nanofilms coated onto the core of an exposed core fiber allow tuning the third harmonic wavelength over 30 nm, as confirmed by qualitative simulations. Due to its generic character, the presented tuning scheme can be applied to any form of exposed core waveguide and will find applications in fields including microscopy, biosensing, and quantum optics.

Third harmonic generation in exposed-core microstructured optical fibers.

Inter-modal phase-matched third harmonic generation has been demonstrated in an exposed-core microstructured optical fiber. Our fiber, with a partially open core having a diameter of just 1.85 µm, shows efficient multi-peak third-harmonic generation between 500 nm and 530 nm, with a maximum visible-wavelength output of 0.96 µW. Mode images and simulations show strong agreement, confirming the phase-matching process and polarization dependence. We anticipate this work will lead to tailorable and tunable visible light sources by exploiting the open access to the optical fiber core, such as depositing thin-film coatings in order to shift the phase matching conditions.

Microstructured Optical Fiber-based Biosensors: Reversible and Nanoliter-Scale Measurement of Zinc Ions.

Sensing platforms that allow rapid and efficient detection of metal ions would have applications in disease diagnosis and study, as well as environmental sensing. Here, we report the first microstructured optical fiber-based biosensor for the reversible and nanoliter-scale measurement of metal ions. Specifically, a photoswitchable spiropyran Zn(2+) sensor is incorporated within the microenvironment of a liposome attached to microstructured optical fibers (exposed-core and suspended-core microstructured optical fibers). Both fiber-based platforms retains high selectivity of ion binding associated with a small molecule sensor, while also allowing nanoliter volume sampling and on/off switching. We have demonstrated that multiple measurements can be made on a single sample without the need to change the sensor. The ability of the new sensing platform to sense Zn(2+) in pleural lavage and nasopharynx of mice was compared to that of established ion sensing methodologies such as inductively coupled plasma mass spectrometry (ICP-MS) and a commercially available fluorophore (Fluozin-3), where the optical-fiber-based sensor provides a significant advantage in that it allows the use of nanoliter (nL) sampling when compared to ICP-MS (mL) and FluoZin-3 (µL). This work paves the way to a generic approach for developing surface-based ion sensors using a range of sensor molecules, which can be attached to a surface without the need for its chemical modification and presents an opportunity for the development of new and highly specific ion sensors for real time sensing applications.

Fabrication, splicing, Bragg grating writing, and polyelectrolyte functionalization of exposed-core microstructured optical fibers.

Femtosecond laser written Bragg gratings have been written in exposed-core microstructured optical fibers with core diameters ranging from 2.7 µm to 12.5 µm and can be spliced to conventional single mode fiber. Writing a Bragg grating on an open core fiber allows for real-time refractive index based sensing, with a view to multiplexed biosensing. Smaller core fibers are shown both experimentally and theoretically to provide a higher sensitivity. A 7.5 µm core diameter fiber is shown to provide a good compromise between sensitivity and practicality and was used for monitoring the deposition of polyelectrolyte layers, an important first step in developing a biosensor.