On-Chip Photonic Detection Techniques for Non-Invasive In Situ Characterizations at the Microfluidic Scale.

Microfluidics has emerged as a robust technology for diverse applications, ranging from bio-medical diagnostics to chemical analysis. Among the different characterization techniques that can be used to analyze samples at the microfluidic scale, the coupling of photonic detection techniques and on-chip configurations is particularly advantageous due to its non-invasive nature, which permits sensitive, real-time, high throughput, and rapid analyses, taking advantage of the microfluidic special environments and reduced sample volumes. Putting a special emphasis on integrated detection schemes, this review article explores the most relevant advances in the on-chip implementation of UV-vis, near-infrared, terahertz, and X-ray-based techniques for different characterizations, ranging from punctual spectroscopic or scattering-based measurements to different types of mapping/imaging.

Microfluidic lab-on-a-chip characterization of nano- to microparticles suspensions by light extinction spectrometry.

The analysis of nano- and microparticle suspensions with micro systems affords improved space-time yields, selectivity, reaction residence times and conversions capabilities. These capabilities are of primary importance in various fields of research and industry. The few microfluidic lab-on-a-chip approaches that have been developed are essentially designed to analyse fluid phases or involve the use of benchtop particle sizing instruments.

Microfluidic In-Situ Spectrophotometric Approaches to Tackle Actinides Analysis in Multiple Oxidation States.

The study and development of present and future processes for the treatment/recycling of spent nuclear fuels require many steps, from design in the laboratory to setting up on an industrial scale. In all of these steps, analysis and instrumentation are key points. For scientific reasons (small-scale studies, control of phenomena, etc.

Microfluidics: A Novel Approach for Dehydration Protein Droplets.

The equation of state of colloids plays an important role in the modelling and comprehension of industrial processes, defining the working conditions of processes such as drying, filtration, and mixing. The determination of the equation is based on the solvent equilibration, by dialysis, between the colloidal suspension and a reservoir with a known osmotic pressure. In this paper, we propose a novel microfluidic approach to determine the equation of state of a lysozyme solution.

Attaining atomic resolution from in situ data collection at room temperature using counter-diffusion-based low-cost microchips.

Sample handling and manipulation for cryoprotection currently remain critical factors in X-ray structural determination. While several microchips for macromolecular crystallization have been proposed during the last two decades to partially overcome crystal-manipulation issues, increased background noise originating from the scattering of chip-fabrication materials has so far limited the attainable resolution of diffraction data. Here, the conception and use of low-cost, X-ray-transparent microchips for in situ crystallization and direct data collection, and structure determination at atomic resolution close to 1.

Uranium(VI) On-Chip Microliter Concentration Measurements in a Highly Extended UV-Visible Absorbance Linearity Range.

The reduction of effluents deriving from analytical control is a serious concern in the nuclear industry, for both production and R&D units. In this work we report an alternative methodology for the standard UV-vis absorbance analyses for actinides concentration monitoring along the plutonium uranium refining extraction (PUREX) process. This methodology, based on photonic lab-on-a-chip (PhLoC) technology, enables drastic sampling reduction down to a few microliters and simultaneously allows to track concentrations over several orders of magnitude while maintaining a detection linearity range.

Innovative High-Throughput SAXS Methodologies Based on Photonic Lab-on-a-Chip Sensors: Application to Macromolecular Studies.

The relevance of coupling droplet-based Photonic Lab-on-a-Chip (PhLoC) platforms and Small-Angle X-Ray Scattering (SAXS) technique is here highlighted for the performance of high throughput investigations, related to the study of protein macromolecular interactions. With this configuration, minute amounts of sample are required to obtain reliable statistical data. The PhLoC platforms presented in this work are designed to allow and control an effective mixing of precise amounts of proteins, crystallization reagents and buffer in nanoliter volumes, and the subsequent generation of nanodroplets by means of a two-phase flow.

Broadcasting photonic lab on a chip concept through a low cost manufacturing approach.

A low cost fabrication process for photonic lab on a chip systems is here proposed. For the implementation of the masters suitable for cast molding fabrication, an inexpensive dry film photoresist, patternable using standard laboratory equipment, is benchmarked against standardized SU-8 masters obtained using UV lithography and systems manufacture in clean room facilities. Results show adequate system fabrication and a comparable performance of the photonic structures for absorbance/extinction measurements.

Continuous Sensing Photonic Lab-on-a-Chip Platform Based on Cross-Linked Enzyme Crystals.

Microfluidics or lab-on-a-chip technology offer clear advantages over conventional systems such as a dramatic reduction of reagent consumption or a shorter analysis time, which are translated into cost-effective systems. In this work, we present a photonic enzymatic lab-on-a-chip reactor based on cross-linked enzyme crystals (CLECs), able to work in continuous flow, as a highly sensitive, robust, reusable, and stable platform for continuous sensing with superior performance as compared to the state of the art. The microreactor is designed to facilitate the in situ crystallization and crystal cross-linking generating enzymatically active material that can be stored for months/years.

Photonic Lab-on-a-Chip: Integration of Optical Spectroscopy in Microfluidic Systems.

The integration of micro-optical elements with microfluidics leads to the highly promising photonic lab-on-a-chip analytical systems (PhLoCs). In this work, we re-examine the main principles which are underneath the on-chip spectrophotometric detection, approaching the PhLoC concept to a nonexpert audience.

McCLEC, a robust and stable enzymatic based microreactor platform.

A microfluidic chip for cross-linked enzyme crystals (McCLEC) is presented and demonstrated to be a stable, reusable and robust biocatalyst-based device with very promising biotechnological applications. The cost-effective microfluidic platform allows in situ crystallization, cross-linking and enzymatic reaction assays on a single device. A large number of enzymatic reuses of the McCLEC platform were achieved and a comparative analysis is shown illustrating the efficiency of the process and its storage stability for more than one year.

A multiple path photonic lab on a chip for parallel protein concentration measurements.

We propose a PDMS-based photonic system for the accurate measurement of protein concentration with minute amounts of the sample. As opposed to the state of the art approach, in the multiple path photonic lab on a chip (MPHIL), analyte concentration or molar absorptivity is obtained with a single injection step, by performing simultaneous parallel optical measurements varying the optical path length. Also, as opposed to the standard calibration protocol, the MPHIL approach does not require a series of measurements at different concentrations.

Monitoring picoliter sessile microdroplet dynamics shows that size does not matter.

We monitor the dissolution of arrayed picoliter-size sessile microdroplets of the aqueous phase in oil, generated using a recently developed fluidic device. Initial pinning of the microdroplet perimeter leads to a nearly constant contact diameter, thus contraction proceeds via microdroplet (micrometer-diameter) height and contact angle reductions. This confirms that picoliter microdroplets contraction or dissolution due to the selective diffusion of water in oil has comparable dynamics with microliter droplet evaporation in air.

Analysis of the structural integrity of SU-8-based optofluidic systems for small-molecule crystallization studies.

The use of SU-8-based optofluidic systems (OFS) is validated as an affordable and easy alternative to expensive glass device manufacturing for small-molecule crystallization studies and, in comparison with other polymers, able to withstand most organic solvents. A comparison between two identical OFS (using SU-8 and poly(dimethylsiloxane), PDMS) against the 36 most commonly used organic solvents for small-molecule crystallization studies have confirmed both the structural and optical stability of the SU-8, whereas PDMS suffered from unsealing or tearing in most cases. In order to test its compatibility, measurements before and after 24 h of continued exposure against solvents have been pursued.

pH-responsive delivery of doxorubicin from citrate-apatite nanocrystals with tailored carbonate content.

In this work, the efficiency of bioinspired citrate-functionalized nanocrystalline apatites as nanocarriers for delivery of doxorubicin (DOXO) has been assessed. The nanoparticles were synthesized by thermal decomplexing of metastable calcium/citrate/phosphate solutions both in the absence (Ap) and in the presence (cAp) of carbonate ions. The presence of citrate and carbonate ions in the solution allowed us to tailor the size, shape, carbonate content, and surface chemistry of the nanoparticles.

Bio-inspired citrate-functionalized apatite thin films crystallized on Ti-6Al-4V implants pre-coated with corrosion resistant layers.

In this paper the crystallization of a bioinspired citrate-functionalized apatite (cit-Ap) thin film (thickness about 2μm) on Ti-6Al-4V supports pre-coated with bioactive and corrosion resistant buffer layer of silicon nitride (Si3N4), silicon carbide (SiC) or titanium nitride (TiN) is reported. The apatitic coatings were produced by a new coating technique based on the induction heating of the implants immersed in a flowing calcium-citrate-phosphate solution at pH11. The influence of the buffer layers and the surface roughness of the substrate on the chemical-physical features and adhesion of the cit-Ap films were investigated.