Protein Crystallization in a Microfluidic Contactor with Nafion®117 Membranes.

Protein crystallization still remains mostly an empirical science, as the production of crystals with the required quality for X-ray analysis is dependent on the intensive screening of the best protein crystallization and crystal's derivatization conditions. Herein, this demanding step was addressed by the development of a high-throughput and low-budget microfluidic platform consisting of an ion exchange membrane (117 Nafion® membrane) sandwiched between a channel layer (stripping phase compartment) and a wells layer (feed phase compartment) forming 75 independent micro-contactors. This microfluidic device allows for a simultaneous and independent screening of multiple protein crystallization and crystal derivatization conditions, using Hen Egg White Lysozyme (HEWL) as the model protein and Hg2+ as the derivatizing agent. This microdevice offers well-regulated crystallization and subsequent crystal derivatization processes based on the controlled transport of water and ions provided by the 117 Nafion® membrane. Diffusion coefficients of water and the derivatizing agent (Hg2+) were evaluated, showing the positive influence of the protein drop volume on the number of crystals and crystal size. This microfluidic system allowed for crystals with good structural stability and high X-ray diffraction quality and, thus, it is regarded as an efficient tool that may contribute to the enhancement of the proteins' crystals structural resolution.

Escaping undesired gas-phase chemistry: Microwave-driven selectivity enhancement in heterogeneous catalytic reactors.

Research in solid-gas heterogeneous catalytic processes is typically aimed toward optimization of catalyst composition to achieve a higher conversion and, especially, a higher selectivity. However, even with the most selective catalysts, an upper limit is found: Above a certain temperature, gas-phase reactions become important and their effects cannot be neglected. Here, we apply a microwave field to a catalyst-support ensemble capable of direct microwave heating (MWH). We have taken extra precautions to ensure that (i) the solid phase is free from significant hot spots and (ii) an accurate estimation of both solid and gas temperatures is obtained. MWH allows operating with a catalyst that is significantly hotter than the surrounding gas, achieving a high conversion on the catalyst while reducing undesired homogeneous reactions. We demonstrate the concept with the CO2-mediated oxidative dehydrogenation of isobutane, but it can be applied to any system with significant undesired homogeneous contributions.

Development of fluorescent thermoresponsive nanoparticles for temperature monitoring on membrane surfaces.

In this work, tris(phenantroline)ruthenium(II) chloride (Ru(phen)3) was immobilized in silica nanoparticles prepared according to the Stöber method. Efforts were devoted on the optimization of the nano-thermometer in terms of size, polydispersity, intensity of the emission and temperature sensitivity. In particular, the immobilization of the luminophore in an external thin shell made of silica grown in a second step on bare silica nanoparticles allowed producing fluorescent monodisperse silica nanoparticles (420±20nm). A systematic study was addressed to maximize the intensity of the emission of the fluorescent nanoparticles by adjusting the concentration of Ru(phen)32+ in the shell from 0.2 to 24wt.%, whereas the thickness of the shell is affected by the amount of silica precursor employed. The luminescent activity of the doped nanoparticles was found to be sensitive to the temperature. In fact, the intensity of the emission linearly decreased by increasing the temperature from 20°C to 65°C. The thermoresponsive nanoparticles were functionalized with long aliphatic chains in order to obtain hydrophobic nanoparticles. The developed nanoparticles were immobilized via dip-coating procedure on the surface of hydrophobic porous membranes, such as Polyvinylidene fluoride (PVDF) prepared via Non-Solvent Induced Phase Separation (NIPS), providing local information about the membrane surface temperature.

Brugada Phenocopy as a Dynamic Electrocardiographic Pattern during Acute Anterior Myocardial Infarction.

Brugada phenocopies represent some unusual clinical cases with identical characteristics to Brugada syndrome (BrS) elicited by various clinical circumstances. We report the case of a woman exhibiting "Brugada Phenocopy" during an acute anterior myocardial infarction, highlighting differential diagnosis with true BrS and discussing possible mechanisms underlying its dynamic ECG pattern.

Pronounced alterations in T-wave morphology during dipyridamole-induced ischaemia.

The case describes a 77-year-old woman with multivessel coronary disease exhibiting marked changes of T-wave morphology induced by dipyridamole, an unusual finding in which the diagnostic accuracy in this clinical context is uncertain. Gated-SPECT imaging demonstrated severe ischaemia extending through inferior and posterolateral regions of the left ventricle with normal motility and contractile function in response to vasodilator stress. Possible underlying mechanisms and clinical implications of observed electrocardiographic changes are discussed. T-loop modifications during vasodilator stress SPECT and correlation of these changes with the amount of ischaemic injury need further evaluation.

Facile production of stable silicon nanoparticles: laser chemistry coupled to in situ stabilization via room temperature hydrosilylation.

Stable, alkyl-terminated, light-emitting silicon nanoparticles have been synthesized in a continuous process by laser pyrolysis of a liquid trialkyl-silane precursor selected as a safer alternative to gas silane (SiH4). Stabilization was achieved by in situ reaction using a liquid collection system instead of the usual solid state filtration. The alkene contained in the collection liquid (1-dodecene) reacted with the newly formed silicon nanoparticles in an unusual room-temperature hydrosilylation process. It was achieved by the presence of fluoride species, also produced during laser pyrolysis from the decomposition of sulfur hexafluoride (SF6) selected as a laser sensitizer. This process directly rendered alkyl-passivated silicon nanoparticles with consistent morphology and size (<3 nm), avoiding the use of costly post-synthetic treatments.

Continuous production of iron-based nanocrystals by laser pyrolysis. Effect of operating variables on size, composition and magnetic response.

Well dispersed iron-based magnetic nanoparticles have been prepared by gas phase laser-driven decomposition of iron pentacarbonyl. Agglomeration of the newly synthesized nanoparticles could be avoided by using a liquid collection system in which the exit stream from the laser reactor was bubbled through triethylene glycol (TREG). The effect of different experimental parameters (precursor concentration, laser power, working pressure, residence time) was studied and, by selecting the appropriate conditions, the size of the resulting magnetic nanocrystals could be tuned from ultrasmall (ca. 2.5 nm) to around 12 nm. For nanoparticle sizes around 10 nm and larger a metallic iron core could be preserved. These iron/iron oxide core-shell compositions exhibit very high values of magnetization, 127 emu g(-1).

Use of a polyol liquid collection medium to obtain ultrasmall magnetic nanoparticles by laser pyrolysis.

The present work addresses the main bottleneck in the synthesis of magnetic nanoparticles by laser pyrolysis. Since the introduction of laser pyrolysis for the production of nanoparticles nearly three decades ago, this method has been repeatedly presented as a highly promising alternative, on account of two main characteristics: (i) its flexibility, since nanoparticles can be formed from a wide variety of precursors in both gas and liquid phase, and (ii) its continuous nature, avoiding the intrinsic variability of batch processing. However, the results reported to date invariably show considerable aggregation of the obtained nanoparticles, which strongly limits their application in most fields. In this work, we have been able to circumvent this problem by collecting the particles in a polyol liquid medium. This method prevents the formation of aggregates and renders a uniform distribution of well dispersed ultrasmall nanoparticles (<4 nm) in a water-compatible solvent. We consider that the effectiveness of this novel collection method for the production of well-dispersed magnetic nanoparticles will be of high interest to a wide range of scientists working in the nanoparticle synthesis field and may enable new applications wherever there is a strict requirement for non-agglomerated nanoparticles.

Preparation of highly accessible mordenite coatings on ceramic monoliths at loadings exceeding 50% by weight.

A mordenite layer with a high accessibility has been synthesised on cordierite monolith supports; substantial loadings of mordenite were achieved (above 50 wt%) under the synthesis conditions used.