SU-8 as a structural material for labs-on-chips and microelectromechanical systems

Since its introduction in the nineties, the negative resist SU-8 has been increasingly used in micro- and nanotechnologies. SU-8 has made the fabrication of high-aspect ratio structures accessible to labs with no high-end facilities such as X-ray lithography systems or deep reactive ion etching systems. These low-cost techniques have been applied not only in the fabrication of metallic parts or molds, but also in numerous other micromachining processes. Its ease of use has made SU-8 to be used in many applications, even when high-aspect ratios are not required. Beyond these pattern transfer applications, SU-8 has been used directly as a structural material for microelectromechanical systems and microfluidics due to its properties such as its excellent chemical resistance or the low Young modulus. In contrast to conventional resists, which are used temporally, SU-8 has been used as a permanent building material to fabricate microcomponents such as cantilevers, membranes, and microchannels. SU-8-based techniques have led to new low-temperature processes suitable for the fabrication of a wide range of objects, from the single component to the complete lab-on-chip. First, this article aims to review the different techniques and provides guidelines to the use of SU-8 as a structural material. Second, practical examples from our respective labs are presented.     

On weakly eutactic forms

We make precise some properties of the Hermite function in relationwith the Morse theory introduced by Avner Ash in his papers‘On eutactic forms’,Canad. J. Math. 29 (1977) 1040–1054and ‘On the existence of eutactic forms’,Bull. LondonMath. Soc. 12 (1980) 192–196, and with the cellular decompositionof the space of positive definite quadratic forms. We also establisha link between Ash's and Bavard's mass formulae.     

Parallel synthesis of a lipopeptide library by hydrazone-based chemical ligation

alpha-Melanocyte-stimulating hormone (alpha-MSH) is an endogeneous linear tridecapeptide with potential application for the modulation of skin tanning. To evaluate the interest of introducing a lipid moiety onto this peptide, we developed an efficient chemoselective parallel method to prepare a large series of analogues of alpha-melanocortin with high purity, varying the nature or the relative position of the lipid moiety. Two sets of building blocks containing lipidic alpha-oxo-aldehydes or alpha-hydrazinoacetyl peptides were combined to obtain a 102-membered library of amphiphilic alpha-MSH analogues. This library was pharmacologically tested at 1 x 10(-7) M for the ability to induce AMPc production in M4Be melanoma cell line after stimulation of the human melanocortin MC1 receptor. Among theses lipopeptides, 84 compounds exhibited an AMPc induction higher than Melitane, a patented alpha-MSH agonist. These results provide strong evidence of the interest of introduction of a lipid tail for the pharmacomodulation of bioactive peptides.     

2-(Glucosylthio)ethyl Groups as Potential Biolabile Phosphate- Protecting Groups of Mononucleotides

The in vitro anti-HIV effects and the stability studies of mononucleoside phosphotriester derivatives 1 – 3 of 3′-azido-3′-deoxythymidine (AZT) containing 2-(glucosylthio)ethyl moieties as potential biolabile phosphate-protecting groups are reported. The results of the anti-HIV evaluation demonstrate that the described compounds act via the release of the free nucleoside analogue and cannot be considered as mononucleotide prodrugs (pronucleotides). These data can be related to the lack of substrate affinity of these derivatives towards target-enzymes as corroborated by decomposition studies in various media and experiments with a purified β-D glucosidase.     

Electrochemical assessment of water|ionic liquid biphasic systems towards cesium extraction from nuclear waste

A room temperature ionic liquid (IL) composed of a quaternary alkylphosphonium (trihexyltetradecylphosphonium, P₆₆₆₁₄⁺) and tetrakis(pentafluorophenyl)borate anion (TB⁻) was employed within a water|P₆₆₆₁₄TB (w|P₆₆₆₁₄TB or w|IL) biphasic system to evaluate cesium ion extraction in comparison to that with a traditional water|organic solvent (w|o) combination. ¹³⁷Cs is a major contributor to the radioactivity of spent nuclear fuel as it leaves the reactor, and its extraction efficiency is therefore of considerable importance. The extraction was facilitated by the ligand octyl(phenyl)-N,N′-diisobutylcarbamoylphosphine oxide (CMPO) used in TRans-Uranium EXtraction processes and investigated through well established liquid|liquid electrochemistry. This study gave access to the metal ion to ligand (1:n) stoichiometry and overall complexation constant, β, of the interfacial complexation reaction which were determined to be 1:3 and 1.6 × 10¹¹ at the w|P₆₆₆₁₄TB interface while the study at w|o elicited an n equal to 1 with β equal to 86.5. Through a straightforward relationship, these complexation constant values were converted to distribution coefficients, δ_α, with the ligand concentrations studied for comparison to other studies present in the literature; the w|o and w|IL systems gave δ_α of 2 and 8.2 × 10⁷, respectively, indicating a higher overall extraction efficiency for the latter. For the w|o system, the metal ion-ligand stoichiometries were confirmed through isotopic distribution analysis of mass spectra obtained by the direct injection of an emulsified water–organic solvent mixture into an electron spray ionization mass spectrometer.     

Controlled plasmon resonance properties of hollow gold nanosphere aggregates

Hollow gold nanospheres (HGNs) ranging from 29.9 nm/8.5 nm (outer diameter/shell thickness) to 51.5 nm/4.5 nm and having aspect ratios spanning 3.5-11.7 were employed to investigate the ability to tailor charge oscillations of HGN aggregates by systematic variation of particle aspect ratio, interparticle gap, and nanosphere inner surface spatial separation. Altering these properties in aggregated HGNs led to control over the interparticle plasmon resonance. Thiol-mediated aggregation was accomplished using either ethanedithiol or cysteine, resulting in dimeric structures in which monomer subunits were spatially separated by <3 ? and 1.2 ± 0.7 nm, respectively. Particle dimensions and separation distances were confirmed by transmission electron microscopy. Experimental absorption spectra obtained for high-aspect ratio nanospheres dimerized using ethanedithiol exhibited an obvious blue shift of the surface plasmon resonance (SPR) relative to that observed for the native, monomeric HGN. This spectral difference likely results from a charge-transfer plasmon resonance at the dimer interface. The extent of the blue shift was dependent upon shell thickness. Dimers comprised of thin-shelled HGNs exhibited the largest shift; aggregates containing HGNs with thick shells (≥7 nm) did not display a significant SPR shift when the individual particles were in contact. By comparison, all cysteine-induced aggregates examined in this study displayed large interparticle gaps (>1 nm) and a red-shifted SPR, regardless of particle dimensions. This effect can be described fully by a surface mode coupling model. All experimental measurements were verified by finite difference time domain calculations. In addition, simulated electric field maps highlighted the importance of the inner HGN surface in the interparticle coupling mechanism. These findings, which describe structure-dependent SPR properties, may be significant for applications derived from the plasmonic nanostructure platform.     

Ab initio calculations on Pro-Ala and Pro-Gly dipeptides

The geometries of the dipeptides -Pro- -Ala, -Pro- -Ala and -Pro-Gly were investigated by a grid scan ab initio calculation. The 6-31G basis set was used to estimate the effect of the alanyl side-chain on the conformation of the peptide backbone and to provide a computational basis for the interpretation of known physical-chemical properties of larger peptides that contain these dipeptides. These calculations furnish a direct quantum mechanical assessment of the energetic consequences of a methyl side-chain in the i + 2 position of a turn. The results of the calculation support the current view that the presence of a -Ala residue in the i + 2 position favors a type II β-turn over a type I β-turn conformation, while -Ala has the opposite effect. Total and relative energies for all the optimized conformations identified by the grid search are given and geometric parameters (bond lengths, bond angles and dihedral angles) and net atomic charges have been calculated.     

Thioacylation reactions for the surface functionalization of phosphorus-containing dendrimers

The functionalization of phosphorus-containing dendrimers was easily achieved through thioacylation reactions involving new dendrimers capped with dithioester end groups and various functionalized amines. These reactions were successfully applied to the first generation (12 end groups) and the third generation of the dendrimer (48 end groups) and allowed their functionalization by various primary or secondary amines, alcohols, glycols, and azides. [reaction: see text]