SALDI-MS and SERS Multimodal Imaging: One Nanostructured Substrate to Rule Them Both.

Imaging techniques based on mass spectrometry or spectroscopy methods inform in situ about the chemical composition of biological tissues or organisms, but they are sometimes limited by their specificity, sensitivity, or spatial resolution. Multimodal imaging addresses these limitations by combining several imaging modalities; however, measuring the same sample with the same preparation using multiple imaging techniques is still uncommon due to the incompatibility between substrates, sample preparation protocols, and data formats. We present a multimodal imaging approach that employs a gold-coated nanostructured silicon substrate to couple surface-assisted laser desorption/ionization mass spectrometry (SALDI-MS) and surface-enhanced Raman spectroscopy (SERS). Our approach integrates both imaging modalities by using the same substrate, sample preparation, and data analysis software on the same sample, allowing the coregistration of both images. We transferred molecules from clean fingertips and fingertips covered with plasticine modeling clay onto our nanostructure and analyzed their chemical composition and distribution by SALDI-MS and SERS. Multimodal analysis located the traces of plasticine on fingermarks and provided chemical information on the composition of the clay. Our multimodal approach effectively combines the advantages of mass spectrometry and vibrational spectroscopy with the signal enhancing abilities of our nanostructured substrate.

Lamellar nanoporous gold thin films with tunable porosity for ultrasensitive SERS detection in liquid and gas phase.

Lamellar nanoporous gold thin films, constituted of a stack of very thin layers of porous gold, are synthesized by chemical etching from a stack of successively deposited nanolayers of copper and gold. The gold ligament size, the pore size and the distance between lamellas are tunable in the few tens nanometer range by controlling the initial thickness of the layers and the etching time. The SERS activity of these lamellar porous gold films is characterized by their SERS responses after adsorption of probe bipyridine and naphtalenethiol molecules. The SERS signal is investigated as a function of the bipyridine concentration from 10-14 mol L-1 to 10-3 mol L-1. The higher SERS response corresponds to an experimental detection limit down to 10-12 mol L-1. These performance is mainly attributed to the specific nanoporous gold architecture and the larger accessible surface to volume ratio. The lamellar nanoporous gold substrate is explored for sensitive SERS detection of dimethyl methylphosphonate (DMMP), a surrogate molecule of the highly toxic G-series nerve agents. The resultant nanostructure facilitates the diffusion of target molecules through the nanopores and their localization at the enhancing metallic surface leading to the unequivocal Raman signature of DMMP at a concentration of 5 parts per million.

A Multiparameter Gas-Monitoring System Combining Functionalized and Non-Functionalized Microcantilevers.

The aim of the study is to develop a compact, robust and maintenance free gas concentration and humidity monitoring system for industrial use in the field of inert process gases. Our multiparameter gas-monitoring system prototype allows the simultaneous measurement of the fluid physical properties (density, viscosity) and water vapor content (at ppm level) under varying process conditions. This approach is enabled by the combination of functionalized and non-functionalized resonating microcantilevers in a single sensing platform. Density and viscosity measuring performance is evaluated over a wide range of gases, temperatures and pressures with non-functionalized microcantilevers. For the humidity measurement, microporous Y-type zeolite and mesoporous silica MCM48 are evaluated as sensing materials. An easily scalable functionalization method to high-throughput production is herein adopted. Experimental results with functionalized microcantilevers exposed to water vapor (at ppm level) indicate that frequency changes cannot be attributed to a mass effect alone, but also stiffness effects dependent on adsorption of water and working temperature must be considered. To support this hypothesis, the mechanical response of such microcantilevers has been modelled considering both effects and the simulated results validated by comparison against experimental data.

Gas phase detection of chemical warfare agents CWAs with portable Raman.

The development of SERS substrates for chemical detection of specific analytes requires appropriate selection of plasmonic metal and the surface where it is deposited. Here we deposited Ag nanoplates on three substrates: i) conventional SiO2/Si wafer, ii) stainless steel mesh and iii) graphite foils. The SERS enhancement of the signal was studied for Rhodamine 6 G (R6 G) as common liquid phase probe molecule. We conducted a comprehensive study with λ = 532, 633 and 785 nm on all the substrates. The best substrate was investigated, at the optimum laser 785 nm, for gas phase detection of dimethyl methyl phosphonate (DMMP), simulant of the G-series nerve agents, at a concentration of 2.5 ppmV (14 mg/m3). The spectral fingerprint was clearly observed; with variations on the relative intensities of SERS Raman bands compared to bulk DMMP in liquid phase reflects the DMMP-Ag interactions. These interactions were simulated by Density Functional Theory (DFT) calculations and the simulated spectra matched with the experimental one. Finally, we were detected the characteristics DMMP fingerprint with hand-held portable equipment. These results open the way for the application of SERS technique on real scenarios where robust, light-weight, miniaturized and simple to use and cost-effective tools are required by first responders.

Three-Dimensional Fractal Geometry for Gas Permeation in Microchannels.

The novel concept of a microfluidic chip with an integrated three-dimensional fractal geometry with nanopores, acting as a gas transport membrane, is presented. The method of engineering the 3D fractal structure is based on a combination of anisotropic etching of silicon and corner lithography. The permeation of oxygen and carbon dioxide through the fractal membrane is measured and validated theoretically. The results show high permeation flux due to low resistance to mass transfer because of the hierarchical branched structure of the fractals, and the high number of the apertures. This approach offers an advantage of high surface to volume ratio and pores in the range of nanometers. The obtained results show that the gas permeation through the nanonozzles in the form of fractal geometry is remarkably enhanced in comparison to the commonly-used polydimethylsiloxane (PDMS) dense membrane. The developed chip is envisioned as an interesting alternative for gas-liquid contactors that require harsh conditions, such as microreactors or microdevices, for energy applications.

Exploring the Gas-Permeation Properties of Proton-Conducting Membranes Based on Protic Imidazolium Ionic Liquids: Application in Natural Gas Processing.

This experimental study explores the potential of supported ionic liquid membranes (SILMs) based on protic imidazolium ionic liquids (ILs) and randomly nanoporous polybenzimidazole (PBI) supports for CH4/N2 separation. In particular, three classes of SILMs have been prepared by the infiltration of porous PBI membranes with different protic moieties: 1-H-3-methylimidazolium bis (trifluoromethane sulfonyl)imide; 1-H-3-vinylimidazolium bis(trifluoromethane sulfonyl)imide followed by in situ ultraviolet (UV) polymerization to poly[1-(3H-imidazolium)ethylene] bis(trifluoromethanesulfonyl)imide. The polymerization process has been monitored by Fourier transform infrared (FTIR) spectroscopy and the concentration of the protic entities in the SILMs has been evaluated by thermogravimetric analysis (TGA). Single gas permeability values of N2 and CH4 at 313 K, 333 K and 363 K were obtained from a series of experiments conducted in a batch gas permeance system. The results obtained were assessed in terms of the preferential cavity formation and favorable solvation of methane in the apolar domains of the protic ionic network. The most attractive behavior exhibited poly[1-(3H-imidazolium)ethylene]bis(trifluoromethanesulfonyl)imide polymeric ionic liquid (PIL) cross-linked with 1% divinylbenzene supported membranes, showing stable performance when increasing the upstream pressure. The CH4/N2 permselectivity value of 2.1 with CH4 permeability of 156 Barrer at 363 K suggests that the transport mechanism of the as-prepared SILMs is solubility-dominated.

Hierarchical Porous Polybenzimidazole Microsieves: An Efficient Architecture for Anhydrous Proton Transport via Polyionic Liquids.

Liquid-induced phase-separation micromolding (LIPSµM) has been successfully used for manufacturing hierarchical porous polybenzimidazole (HPBI) microsieves (42-46% porosity, 30-40 µm thick) with a specific pore architecture (pattern of macropores: ∼9 µm in size, perforated, dispersed in a porous matrix with a 50-100 nm pore size). Using these microsieves, proton-exchange membranes were fabricated by the infiltration of a 1H-3-vinylimidazolium bis(trifluoromethanesulfonyl)imide liquid and divinylbenzene (as a cross-linker), followed by in situ UV polymerization. Our approach relies on the separation of the ion conducting function from the structural support function. Thus, the polymeric ionic liquid (PIL) moiety plays the role of a proton conductor, whereas the HPBI microsieve ensures the mechanical resistance of the system. The influence of the porous support architecture on both proton transport performance and mechanical strength has been specifically investigated by means of comparison with straight macroporous (36% porosity) and randomly nanoporous (68% porosity) PBI counterparts. The most attractive results were obtained with the poly[1-(3H-imidazolium)ethylene]bis(trifluoromethanesulfonyl)imide PIL cross-linked with 1% divinylbenzene supported on HPBI membranes with a 21-µm-thick skin layer, achieving conductivity values up to 85 mS cm-1 at 200 °C under anhydrous conditions and in the absence of mineral acids.

Constructing Straight Polyionic Liquid Microchannels for Fast Anhydrous Proton Transport.

Polymeric ionic liquids (PILs) have triggered great interest as all solid-state flexible electrolytes because of safety and superior thermal, chemical, and electrochemical stability. It is of great importance to fabricate highly conductive electrolyte membranes capable to operate above 120 °C under anhydrous conditions and in the absence of mineral acids, without sacrificing the mechanical behavior. Herein, the diminished dimensional and mechanical stability of poly[1-(3H-imidazolium)ethylene]bis(trifluoromethanesulfonyl)imide has been improved thanks to its infiltration on a polybenzimidale (PBI) support with specific pore architecture. Our innovative solution is based on the synergic combination of an emerging class of materials and sustainable large-scale manufacturing techniques (UV polymerization and replication by microtransfer-molding). Following this approach, the PIL plays the proton conduction role, and the PBI microsieve (SPBI) mainly provides the mechanical reinforcement. Among the resulting electrolyte membranes, conductivity values above 50 mS·cm-1 at 200 °C and 10.0 MPa as tensile stress are shown by straight microchannels of poly[1-(3H-imidazolium)ethylene]bis(trifluoromethanesulfonyl)imide cross-linked with 1% of dyvinylbenzene embedded in a PBI microsieve with well-defined porosity (36%) and pore diameter (17 µm).