Microfluidic Diatomite Analytical Devices for Illicit Drug Sensing with ppb-Level Sensitivity.

The escalating research interests in porous media microfluidics, such as microfluidic paper-based analytical devices, have fostered a new spectrum of biomedical devices for point-of-care (POC) diagnosis and biosensing. In this paper, we report microfluidic diatomite analytical devices (µDADs), which consist of highly porous photonic crystal biosilica channels, as an innovative lab-on-a-chip platform to detect illicit drugs. The µDADs in this work are fabricated by spin-coating and tape-stripping diatomaceous earth on regular glass slides with cross section of 400×30µm2. As the most unique feature, our µDADs can simultaneously perform on-chip chromatography to separate small molecules from complex biofluidic samples and acquire the surface-enhanced Raman scattering spectra of the target chemicals with high specificity. Owing to the ultra-small dimension of the diatomite microfluidic channels and the photonic crystal effect from the fossilized diatom frustules, we demonstrate unprecedented sensitivity down to part-per-billion (ppb) level when detecting pyrene (1ppb) from mixed sample with Raman dye and cocaine (10 ppb) from human plasma. This pioneering work proves the exclusive advantage of µDADs as emerging microfluidic devices for chemical and biomedical sensing, especially for POC drug screening.

Surface-Enhanced Infrared Absorption: Pushing the Frontier for On-Chip Gas Sensing.

Surface-enhanced infrared absorption (SEIRA) is capable of identifying molecular fingerprints by resonant detection of infrared vibrational modes through the coupling with plasmonic modes of metallic nanostructures. However, SEIRA for on-chip gas sensing is still not very successful due to the intrinsically weak light-matter interaction between photons and gas molecules and the technical challenges in accumulating sufficient gas species in the vicinity of the spatially localized enhanced electric field, namely, the "hot-spots", generated through plasmonics. In this paper, we present a suspended silicon nitride (Si3N4) nanomembrane device by integrating plasmonic nanopatch gold antennas with metal-organic framework (MOF), which can largely adsorb carbon dioxide (CO2) through its nanoporous structure. Unlike conventional SEIRA sensing relying on highly localized hot-spots of plasmonic nanoantennas or nanoparticles, the device reported in this paper engineered the coupled surface plasmon polaritons in the metal-Si3N4 and metal-MOF interfaces to achieve strong optical field enhancement across the entire MOF film. We successfully demonstrated on-chip gas sensing of CO2 with more than 1800× enhancement factors by combining the concentration effect from the 2.7 µm MOF thin film and the optical field enhancement of the plasmonic nanopatch antennas.

Ultra-Sensitive Lab-on-a-Chip Detection of Sudan I in Food using Plasmonics-Enhanced Diatomaceous Thin Film.

Sudan I is a carcinogenic compound containing an azo group that has been illegally utilized as an adulterant in food products to impart a bright red color to foods. In this paper, we develop a facile lab-on-a-chip device for instant, ultra-sensitive detection of Sudan I from real food samples using plasmonics-enhanced diatomaceous thin film, which can simultaneously perform on-chip separation using thin layer chromatography (TLC) and highly specific sensing using surface-enhanced Raman scattering (SERS) spectroscopy. Diatomite is a kind of nature-created photonic crystal biosilica with periodic pores and was used both as the stationary phase of the TLC plate and photonic crystals to enhance the SERS sensitivity. The on-chip chromatography capability of the TLC plate was verified by isolating Sudan I in a mixture solution containing Rhodamine 6G, while SERS sensing was achieved by spraying gold colloidal nanoparticles into the sensing spot. Such plasmonics-enhanced diatomaceous film can effectively detect Sudan I with more than 10 times improvement of the Raman signal intensity than commercial silica gel TLC plates. We applied this lab-on-a-chip device for real food samples and successfully detected Sudan I in chili sauce and chili oil down to 1 ppm, or 0.5 ng/spot. This on-chip TLC-SERS biosensor based on diatomite biosilica can function as a cost-effective, ultra-sensitive, and reliable technology for screening Sudan I and many other illicit ingredients to enhance food safety.

Plasmonic nanopatch array with integrated metal-organic framework for enhanced infrared absorption gas sensing.

In this letter, we present a nanophotonic device consisting of plasmonic nanopatch array (NPA) with integrated metal-organic framework (MOF) for enhanced infrared absorption gas sensing. By designing a gold NPA on a sapphire substrate, we are able to achieve enhanced optical field that spatially overlaps with the MOF layer, which can adsorb carbon dioxide (CO2) with high capacity. Experimental results show that this hybrid plasmonic-MOF device can effectively increase the infrared absorption path of on-chip gas sensors by more than 1100-fold. The demonstration of infrared absorption spectroscopy of CO2 using the hybrid plasmonic-MOF device proves a promising strategy for future on-chip gas sensing with ultra-compact size.

Detecting explosive molecules from nanoliter solution: A new paradigm of SERS sensing on hydrophilic photonic crystal biosilica.

We demonstrate a photonic crystal biosilica surface-enhanced Raman scattering (SERS) substrate based on a diatom frustule with in-situ synthesized silver nanoparticles (Ag NPs) to detect explosive molecules from nanoliter (nL) solution. By integrating high density Ag NPs inside the nanopores of diatom biosilica, which is not achievable by traditional self-assembly techniques, we obtained ultra-high SERS sensitivity due to dual enhancement mechanisms. First, the hybrid plasmonic-photonic crystal biosilica with three dimensional morphologies was obtained by electroless-deposited Ag seeds at nanometer sized diatom frustule surface, which provides high density hot spots as well as strongly coupled optical resonances with the photonic crystal structure of diatom frustules. Second, we discovered that the evaporation-driven microscopic flow combined with the strong hydrophilic surface of diatom frustules is capable of concentrating the analyte molecules, which offers a simple yet effective mechanism to accelerate the mass transport into the SERS substrate. Using the inkjet printing technology, we are able to deliver multiple 100pico-liter (pL) volume droplets with pinpoint accuracy into a single diatom frustule with dimension around 30µm×7µm×5µm, which allows for label-free detection of explosive molecules such as trinitrotoluene (TNT) down to 10-10M in concentration and 2.7×10-15g in mass from 120nL solution. Our research illustrates a new paradigm of SERS sensing to detect trace level of chemical compounds from minimum volume of analyte using nature created photonic crystal biosilica materials.

Broadband on-chip near-infrared spectroscopy based on a plasmonic grating filter array.

We demonstrate an ultra-compact, broadband on-chip near-infrared (NIR) spectroscopy system based on a narrow-band plasmonic filter array. The entire filter array, consisting of 28 individual subwavelength metallic gratings, was monolithically integrated in a thin gold film on a quartz substrate, covering a 270 nm spectra from 1510 nm to 1780 nm. In order to achieve a high spectral resolution, extremely narrow slits are created for the gratings with a polymer waveguide layer on top, generating narrow-band guided-mode resonances through coupling with the surface-plasmon resonances of the metallic gratings. Experimental results show that the transmission bands of the filter array have full width at half-maximum of only 7 nm-13 nm, which is sufficient for NIR spectroscopy. The NIR absorption spectroscopy of xylene using the on-chip plasmonic filter array matches very well with the results from conventional Fourier transform infrared spectroscopy, which proves the great potential for NIR sensing applications.

Slow-light effect via Rayleigh anomaly and the effect of finite gratings.

In this Letter, we investigate the slow-light effect of subwavelength diffraction gratings via the Rayleigh anomaly using a fully analytical approach without needing to consider specific grating structures. Our results show that the local group velocity of the transmitted light can be significantly reduced due to the optical vortex, which can inspire a new mechanism to enhance light-matter interactions for optical sensing and photodetection. However, the slow-light effect will diminish as the transmitted light propagates farther from the grating surface, and the slowdown factor decreases as the grating size shrinks.

Effect of finite metallic grating size on Rayleigh anomaly-surface plasmon polariton resonances.

Rayleigh anomalies (RAs) and surface plasmon polaritons (SPPs) on subwavelength metallic gratings play pivotal roles in many interesting phenomena such as extraordinary optical transmission. In this work, we present a theoretical analysis of the effect of finite metallic grating size on RA-SPP resonances based on the combination of rigorous coupled wave analysis and finite aperture diffraction. One-dimensional arrays of gold subwavelength gratings with different device sizes were fabricated and the optical transmission spectra were measured. As the grating size shrinks, the broadening of the RA-SPP resonances is predicted by the theoretical model. For the first order RA-SPP resonances, the results from this model are in good agreement with the spectra measured from the fabricated plasmonic gratings.

Plasmonics Resonance Enhanced Active Photothermal Effects of Aluminum and Iron Nanoparticles.

Localized Surface Plasmonics Resonance (LSPR) enhanced active photothermal effects of both aluminum nanoparticles (Al NPs) and iron nanoparticles (Fe NPs) are experimentally observed. Photothermally activated motion and ignition by low-energy xenon flash are quantitatively measured. For nanoparticles of comparable sizes, photothermally activated motion height of Fe NPs is about 60% lower than that of Al NPs, while photothermal Minimum Ignition Energy (MIE) of Fe NPs is about 50% lower than that of Al NPs. Joule heating by LSPR enhanced photothermal effects among nanoparticles and subsequently triggered oxidation reactions are found responsible for the motion and ignition of the nanoparticles.

Guided-Mode Resonance Grating with Self-Assembled Silver Nanoparticles for Surface-Enhanced Raman Scattering Spectroscopy.

We designed and fabricated guided-mode resonance (GMR) gratings on indium-tin-oxide (ITO) thin film to generate a significantly enhanced local electric field for surface-enhanced Raman scattering (SERS) spectroscopy. Ag nanoparticles (NPs) were self-assembled onto the surface of the grating, which can provide a large amount of "hot-spots" for SERS sensing. The ITO gratings also exhibit excellent tolerance to fabrication deviations due to the large refractive index contrast of the ITO grating. Quantitative experimental results of 5,5'-dithiobis(2-nitrobenzoic acid) (DTNB) demonstrate the best enhancement factor of ~14× on ITO gratings when compared with Ag NPs on a flat ITO film, and the limit of detection (LOD) of DTNB is as low as 10 pM.

Polarization-interferometry-based wavelength-interrogation surface plasmon resonance imager for analysis of microarrays.

Polarization interferometry (PI) techniques, which are able to improve surface plasmon resonance (SPR) sensing performance and reduce restrictions on allowable parameters of SPR-supporting metal films, have been experimentally realized only in SPR sensors using monochromatic light as a source. Wavelength-interrogation SPR sensors modulated by PI techniques have not been reported due to the wavelength-sensitive characterization of PI phase compensators. In this work we develop a specially designed rhombic prism for phase compensating which is totally insensitive to wavelength. For the first time we successfully apply PI technique to a wavelength-interrogation SPR imager. This imager is able to offer two-dimensional imaging of the whole array plane. As a result of PI modulation, resolutions of 1.3×10(-6) refractive index unit (RIU) under the normal condition and 3.9×10(-7) RIU under a more time-consuming condition are acquired. The application of this imager was demonstrated by reading microarrays for identification of bacteria, and SPR results were confirmed by means of fluorescence imaging.

Parallel-scan based microarray imager capable of simultaneous surface plasmon resonance and hyperspectral fluorescence imaging.

With the development of the microarray technology, demands for array detection techniques become higher and higher. For many microarrays, several biomolecular interactions occur simultaneously and the interplay of various factors that affect these interactions remains poorly understood. Detecting such interactions with a single technique can often be a difficult and complicated process. In this work we propose a combined technique which enables simultaneous angle-interrogation surface plasmon resonance (SPR) sensing and hyperspectral fluorescence imaging. This tandem technique offers two-dimensional imaging of the whole array plane. The refractive index information obtained from SPR sensing and the physicochemical properties obtained from fluorescence imaging provide a comprehensive analysis of biological events on the array-chip. In addition, SPR and fluorescence detection techniques confirm each other in experimental results to exclude false-positive or false-negative cases. In terms of SPR sensing performance, the refractive index resolution is 3.86×10(-6) refractive index units (RIU), and the detection limit is 10(4) cfu/ml of Escherichia coli bacteria. The resolving power and detection sensitivity of fluorescence imaging are approximately 20 µm and 0.61 fluors/µm(2), respectively. Finally, two model experiments, detecting the DNA hybridization and biotin-avidin interactions respectively, demonstrate the biomedical application of this system.

A two-dimensional polarization interferometry based parallel scan angular surface plasmon resonance biosensor.

We describe a two-dimensional polarization interferometry based parallel scan angular surface plasmon resonance (SPR) biosensing technique. The method of line-shaped light illumination and parallel scan offers a high throughput. The simultaneous record of SPR angular spectrum enables the system to be unaffected by the time-dependent variation of the light source. The polarization interferometry technique lowers the minimum of the SPR dip and thereby reduces the noise related to the light intensity. Refractive index resolutions of 1.4 × 10(-6) refractive index unit (RIU) under normal condition and 4.6 × 10(-7) RIU under a more time-consuming condition are achieved in our angle interrogation based sensor. Meanwhile, a manually prepared DNA microarray has been detected, showing the potential applications of this technique in microarray analysis.

MiRNA-26b regulates the expression of cyclooxygenase-2 in desferrioxamine-treated CNE cells.

Here we report that miR-26b is involved in COX-2 overexpression in desferrioxamine (DFOM)-treated carcinoma of nasopharyngeal epithelial (CNE) cells. The level of miR-26b in DFOM-treated CNE cells is inversely proportional to the expression level of the COX-2 protein. Overexpression of miR-26b in DFOM-treated CNE cells inhibits cell proliferation. A luciferase reporter gene experiment suggests that the 3' untranslated region of COX-2 carries a binding site for miR-26b. Overexpression of miR-26b marginally reduces the levels of COX-2 protein in DFOM-treated CNE cells. Moreover, knockdown of COX-2 expression had a similar effect to overexpression of miR-26b. Taken together, these results suggest that miR-26b regulates COX-2 expression in DFOM-treated cells.