Christoph Fenzl

Photonic Crystals for Chemical Sensing and Biosensing

This Review covers photonic crystals (PhCs) and their use for sensing mainly chemical and biochemical parameters, with a particular focus on the materials applied. Specific sections are devoted to a) a lead-in into natural and synthetic photonic nanoarchitectures, b) the various kinds of structures of PhCs, c) reflection and diffraction in PhCs, d) aspects of sensing based on mechanical, thermal, optical, electrical, magnetic, and purely chemical stimuli, e) aspects of biosensing based on biomolecules incorporated into PhCs, and f) current trends and limitations of such sensors.

Optical sensing of the ionic strength using photonic crystals in a hydrogel matrix.

Monodisperse, highly negatively charged, cross-linked polystyrene nanoparticles with diameters between 80 and 120 nm have been incorporated into a polyacrylamide hydrogel, where they display an iridescent color that conventionally is attributed to the so-called photonic crystal effect. The film is of red color if placed in plain water but turns to green in the presence of a 1 mM solution of an electrolyte such as sodium chloride and to purple in 100 mM solutions of electrolytes. Quantitative reflection spectroscopy was performed at various wavelengths and resulted in plots of reflected light wavelength versus ionic strength (IS) that are almost linear in the logarithmic concentration range from 5 × 10(-5) to 10(-2) mol·L(-1). We show that such films are capable of monitoring the IS of aqueous solutions in the pH range from 5 to 9. We also show that, in addition to visual and instrumental readout, the sensor films can be analyzed with a digital camera at fixed angle. The digital images were separated into their red, green, and blue channels and analyzed. The red channel was found to be best suited for determination of the IS and resulted in calibration plots that are comparable if not better than those obtained by reflectometry.

Photonic Crystal Based Sensor for Organic Solvents and for Solvent-Water Mixtures

Monodisperse polystyrene nanoparticles with a diameter of 173 nm were incorporated into a polydimethylsiloxane matrix where they display an iridescent color that can be attributed to the photonic crystal effect. The film is of violet color if placed in plain water, but turns to red in the presence of the non-polar solvent n-hexane. Several solvents were studied in some detail. We show that such films are capable of monitoring the water content of ethanol/water mixtures, where only 1% (v/v) of water leads to a shift of the peak wavelength of reflected light by 5 nm. The method also can be applied to determine, both visually and instrumentally, the fraction of methanol in ethanol/methanol mixtures. Here, a fraction of 1% of methanol (v/v) results in a wavelength shift of 2 nm. The reflected wavelength is not influenced by temperature changes nor impeded by photobleaching. The signal changes are fully reversible and response times are <1 s.

A photonic crystal based sensing scheme for acetylcholine and acetylcholinesterase inhibitors

We present a new scheme for sensing biomolecules by combining an enzyme hydrogel with a photonic crystal hydrogel layer that responds to ionic strength and pH changes. We demonstrate this unique combination by successfully detecting acetylcholine (ACh) and acetylcholinesterase (AChE) inhibitors. Specifically, the sandwich assembly is composed of layers of photonic crystals and a polyacrylamide hydrogel functionalized with AChE. The photonic crystal film has a red color and turns dark purple within 2-6 minutes of the enzymatic reaction upon analyte addition. This 3D photonic crystal sensor responds to acetylcholine in the 1 nM to 10 μM concentration range (which includes the relevant range of ACh concentrations in human body fluids). Michaelis-Menten kinetics of the enzyme were determined which correlated well with literature data demonstrating the uninhibited reactivity of the immobilized enzyme. Furthermore, the presence of the acetylcholinesterase inhibitor neostigmine at concentrations as low as 1 fM was demonstrated, which is even below the necessary detection limit for clinical diagnostics. We suggest that this novel concept will find its application in clinical diagnostics, for pesticide and nerve agent detection.

Surface plasmon resonance sensor for dissolved and gaseous carbon dioxide.

We describe a novel kind of sensor for carbon dioxide. It is based on surface plasmon resonance (SPR) and a polymer blend that is capable of fully reversibly binding carbon dioxide. The interaction results in a change in the polarity and refractive index that can be detected via SPR. The sensor responds with high specificity. The method is simple and, unlike previous ones, enables continuous sensing over extended periods of time. It can be applied to sense both dissolved and gaseous carbon dioxide. The limits if detection of gaseous CO(2) is as low as 10 ppm.

Laser-Scribed Graphene Electrodes for Aptamer-Based Biosensing

Graphene as a transducer material has produced some of the best-performing sensing approaches to date opening the door toward integrated miniaturized all-carbon point-of-care devices. Addressing this opportunity, laser-scribed graphene (LSG) electrodes are demonstrated here as highly sensitive and reliable biosensor transducers in blood serum analysis. These flexible electrodes with large electrochemical surface areas were fabricated using a direct-write laser process on polyimide foils. A universal immobilization approach is established by anchoring 1-pyrenebutyric acid to the graphene and subsequently covalently attaching an aptamer against the coagulation factor thrombin as an exemplary bioreceptor to the carboxyl groups. The resulting biosensor displays extremely low detection limits of 1 pM in buffer and 5 pM in the complex matrix of serum.

Liposomes with High Refractive Index Encapsulants as Tunable Signal Amplification Tools in Surface Plasmon Resonance Spectroscopy.

One major goal in the surface plasmon resonance (SPR) technique is the reliable detection of small molecules as well as low analyte concentrations. This can be achieved by a viable signal amplification strategy. We therefore investigated optimal liposome characteristics for use as a signal enhancement system for SPR sensors, as liposomes excel not only at versatility but also at colloidal stability and ease of functionalization. These characteristics include the encapsulation of high refractive index markers, lipid composition, liposome size, and surface modifications to best match the requirements of the SPR system. Our studies of the binding of biotinylated liposomes to surface-immobilized streptavidin show that the refractive index of the encapsulant has a major influence on the SPR signal and outweighs the influence of the thin lipid bilayer. Thus, the signal amplification properties of liposomes can be adjusted to the respective needs of any analytical task by simply exchanging the encapsulant solution. In this work, a maximum enhancement factor of 23 was achieved by encapsulating a 500 mM sucrose solution. Dose-response studies with and without liposome enhancement revealed an improvement of the limit of detection from 10 nmol L(-1) to 320 pmol L(-1) streptavidin concentration with a much higher sensitivity of 3 mRIU per logarithmic unit of the concentration between 500 pmol L(-1) and 10 nmol L(-1).

Passive Mixing Capabilities of Micro- and Nanofibres When Used in Microfluidic Systems

Nanofibres are increasingly being used in the field of bioanalytics due to their large surface-area-to-volume ratios and easy-to-functionalize surfaces. To date, nanofibres have been studied as effective filters, concentrators, and immobilization matrices within microfluidic devices. In addition, they are frequently used as optical and electrochemical transduction materials. In this work, we demonstrate that electrospun nanofibre mats cause appreciable passive mixing and therefore provide dual functionality when incorporated within microfluidic systems. Specifically, electrospun nanofibre mats were integrated into Y-shaped poly(methyl methacrylate) microchannels and the degree of mixing was quantified using fluorescence microscopy and ImageJ analysis. The degree of mixing afforded in relationship to fibre diameter, mat height, and mat length was studied. We observed that the most mixing was caused by small diameter PVA nanofibres (450–550 nm in diameter), producing up to 71% mixing at the microchannel outlet, compared to up to 51% with polystyrene microfibres (0.8–2.7 μm in diameter) and 29% mixing in control channels containing no fibres. The mixing afforded by the PVA nanofibres is caused by significant inhomogeneity in pore size and distribution leading to percolation. As expected, within all the studies, fluid mixing increased with fibre mat height, which corresponds to the vertical space of the microchannel occupied by the fibre mats. Doubling the height of the fibre mat led to an average increase in mixing of 14% for the PVA nanofibres and 8% for the PS microfibres. Overall, mixing was independent of the length of the fibre mat used (3–10 mm), suggesting that most mixing occurs as fluid enters and exits the fibre mat. The mixing effects observed within the fibre mats were comparable to or better than many passive mixers reported in literature. Since the nanofibre mats can be further functionalized to couple analyte concentration, immobilization, and detection with enhanced fluid mixing, they are a promising nanomaterial providing dual-functionality within lab-on-a-chip devices.

Embedded nanolamps in electrospun nanofibers enabling online monitoring and ratiometric measurements

A multifunctional composite nanomaterial based on nanofiber embedding upconversion nanoparticles (UCNPs) is designed to address the common limitations of bioanalysis including the colloidal stability of nanoparticles, high background signals and small sample volumes. We fabricate thin and uniform electrospun polyvinylpyrrolidone (PVP) nanofibers with a diameter of 170 ± 80 nm, containing up to 254 ± 9 mg mL−1 of non-agglomerated UCNPs. On distributing these nanofibers in a microfluidic channel a 50-fold increase in luminescence over dispersed particles can be obtained. A versatile miniaturized platform is created to work with small sample volumes by transferring the upconversion nanofibers into microfluidic channels. Fast and reproducible analytical signal response to their environment is demonstrated by taking advantage of the isotope effect between H2O and D2O upon 980 nm excitation. Furthermore, relevance to analytical applications employing energy transfer was confirmed using the spectral overlap of the green UCNP emission with the absorption spectra of a dye. At minute optical path lengths (e.g. 50 μm) the luminescence properties of the UCNPs help in avoiding the most disturbing light scattering effects of the excitation source and channel geometries. This new nanomaterial platform enables rapid, simple and reliable online monitoring in microfluidic systems, medical applications (e.g. in-tissue, in vivo) and anti-counterfeiting in contrast to solution-based UCNP applications.