First Experimental Evidence of Anti-Stokes Laser-Induced Fluorescence Emission in Microdroplets and Microfluidic Systems Driven by Low Thermal Conductivity of Fluorocarbon Carrier Oil.

With the advent of many optofluidic and droplet microfluidic applications using laser-induced fluorescence (LIF), the need for a better understanding of the heating effect induced by pump laser excitation sources and good monitoring of temperature inside such confined microsystems started to emerge. We developed a broadband highly sensitive optofluidic detection system, which enabled us to show for the first time that Rhodamine-B dye molecules can exhibit standard photoluminescence as well as blue-shifted photoluminescence. We demonstrate that this phenomenon originates from the interaction between the pump laser beam and dye molecules when surrounded by the low thermal conductive fluorocarbon oil, generally used as a carrier medium in droplet microfluidics. We also show that when the temperature is increased, both Stokes and anti-Stokes fluorescence intensities remain practically constant until a temperature transition is reached, above which the fluorescence intensity starts to decrease linearly with a thermal sensitivity of about -0.4%/°C for Stokes emission or -0.2%/°C for anti-Stokes emission. For an excitation power of 3.5 mW, the temperature transition was found to be about 25 °C, whereas for a smaller excitation power (0.5 mW), the transition temperature was found to be about 36 °C.

Ion chromatograph with three-dimensional printed absorbance detector for indirect ultraviolet absorbance detection of phosphate in effluent and natural waters.

An ion chromatography system employing a low-cost three-dimensional printed absorbance detector for indirect ultraviolet detection towards portable phosphate analysis of environmental and industrial waters has been developed. The optical detection cell was fabricated using stereolithography three-dimensional printing of nanocomposite material. Chromatographic analysis and detection of phosphate were carried out using a CS5A 4 × 250 mm analytical column with indirect ultraviolet detection using a 255 nm light-emitting diode. Isocratic elution using a 0.6 mM potassium phthalate eluent combined with 1.44 mM sodium bicarbonate was employed at a flow rate of 0.75 mL/min. A linear calibration range of 0.5 to 30 mg/L PO4 3- applicable to environmental and wastewater analysis was achieved. For retention time and peak area repeatability, relative standard deviation values were 0.68 and 4.09%, respectively. Environmental and wastewater samples were analyzed with the optimized ion chromatography platform and the results were compared to values obtained by an accredited ion chromatograph. For the analysis of environmental samples, relative errors of <14 % were achieved. Recovery analysis was also carried out on both freshwater and wastewater samples and recovery results were within the acceptable range for water analysis using standard ion chromatography methods.

Dye-Doped ZnO Microcapsules for High Throughput and Sensitive Optofluidic Micro-Thermometry.

The main objective of this work is to show the proof of concept of a new optofluidic method for high throughput fluorescence-based thermometry, which enables the measure of temperature inside optofluidic microsystems at the millisecond (ms) time scale (high throughput). We used droplet microfluidics to produce highly monodisperse microspheres from dispersed zinc oxide (ZnO) nanocrystals and doped them with rhodamine B (RhB) or/and rhodamine 6G (Rh6G). The fluorescence intensities of these two dyes are known to depend linearly on temperature but in two opposite manner. Their mixture enables for the construction of reference probe whose fluorescence does not depend practically on temperature. The use of zinc oxide microparticles as temperature probes in microfluidic channels has two main advantages: (i) avoid the diffusion and the adsorption of the dyes inside the walls of the microfluidic channels and (ii) enhance dissipation of the heat generated by the focused incident laser beam thanks to the high thermal conductivity of this material. Our results show that the fluorescence intensity of RhB decreases linearly with increasing temperature at a rate of about -2.2%/°C, in a very good agreement with the literature. In contrast, we observed for the first time a nonlinear change of the fluorescence intensity of Rh6G in ZnO microparticles with a minimum intensity at a temperature equal to 40 °C. This behaviour is reproducible and was observed only with ZnO microparticles doped with Rh6G.

Fast Active Merging of Microdroplets in Microfluidic Chambers Driven by Photo-Isomerisation of Azobenzene Based Surfactants.

In this work, we report on the development of a newly synthesized photoactive reversible azobenzene derived surfactant polymer, which enables active and fast control of the merging of microdroplets in microfluidic chambers, driven by a pulsed UV laser optical stimulus and the well known cis-trans photo-isomerisation of azobenzene groups. We show for the first time that merging of microdroplets can be achieved optically based on a photo-isomerization process with a high spatio-temporal resolution. Our results show that the physical process lying behind the merging of microdroplets is not driven by a change in surface activity of the droplet stabilizing surfactant under UV illumination (as originally expected), and they suggest an original mechanism for the merging of droplets based on the well-known opto-mechanical motion of azobenzene molecules triggered by light irradiation.

High-Throughput Optofluidic Acquisition of Microdroplets in Microfluidic Systems.

Droplet optofluidics technology aims at manipulating the tiny volume of fluids confined in micro-droplets with light, while exploiting their interaction to create "digital" micro-systems with highly significant scientific and technological interests. Manipulating droplets with light is particularly attractive since the latter provides wavelength and intensity tunability, as well as high temporal and spatial resolution. In this review study, we focus mainly on recent methods developed in order to monitor real-time analysis of droplet size and size distribution, active merging of microdroplets using light, or to use microdroplets as optical probes.

Microfluidic-assisted Formation of Highly Monodisperse and Mesoporous Silica Soft Microcapsules.

The fabrication of mesoporous silica microcapsules with a highly controlled particle size ranging in the micrometer size presents a major challenge in many academic and industrial research areas, such as for the developement of smart drug delivery systems with a well controlled loading and release of (bio)active molecules. Many studies based on the solvent evaporation or solvent diffusion methods have been developed during the last two decades in order to control the particle size, which is often found to range at a sub-micrometer scale. Droplet-based microfluidics proved during the last decade a powerful tool to produce highly monodisperse and mesoporous silica solid microspheres with a controllable size in the micrometer range. We show in the present study, in contrast with previous microfluidic-assisted approaches, that a better control of the diffusion of the silica precursor sol in a surrounding perfluorinated oil phase during the silica formation process allows for the formation of highly monodisperse mesoporous silica microcapsules with a diameter ranging in the 10 micrometer range. We show also, using optical, scanning and transmission electron microscopies, small angle x-ray diffraction and BET measurements, that the synthesized mesoporous silica microcapsules exhibit a soft-like thin shell with a thickness of about 1 µm, across which 5.9 nm sized mesopores form a well-ordered hexagonal 2D network. We suggest and validate experimentally a model where the formation of such microcapsules is controlled by the solvent evaporation process at the droplet-air interface.

Photolysis-driven merging of microdroplets in microfluidic chambers.

Photolysis of microdroplets, stabilized by aminoquinoline-derived photosensitive surfactants composed of polyethyleneglycol/perfluorinated polyether (PEG/PFPE) diblock amphiphiles by using 355 nm ps pulsed laser light, resulted in rapid controlled coalescence of targeted microdroplets offering the prospect of a novel type of droplet merging with high stereospatial integrity for microfluidic systems.