Water-oil core-shell droplets for electrowetting-based digital microfluidic devices

Digital microfluidics based on electrowetting-on-dielectric (EWOD) has recently emerged as one of the most promising technologies to realize integrated and highly flexible lab-on-a-chip systems. In such EWOD-based digital microfluidic devices, the aqueous droplets have traditionally been manipulated either directly in air or in an immiscible fluid such as silicone oil. However, both transporting mediums have important limitations and neither offers the flexibility required to fulfil the needs of several applications. In this paper, we report on an alternative mode of operation for EWOD-based devices in which droplets enclosed in a thin layer of oil are manipulated in air. We demonstrate the possibility to perform on-chip the fundamental fluidic operations by using such water-oil core-shell droplets and compare systematically the results with the traditional approach where the aqueous droplets are manipulated directly in air or oil. We show that the core-shell configuration combines several advantages of both the air and oil mediums. In particular, this configuration not only reduces the operation voltage of EWOD-based devices but also leads to higher transport velocities when compared with the manipulation of droplets directly in air or oil.     

Programmed metalloporphyrins for self-assembly within light-harvesting stacks: (5,15-dicyano-10,20-bis(3,5-di-tert-butylphenyl)porphyrinato)zinc(II) and its push-pull 15-N,N-dialkylamino-5-cyano congeners obtained by a facile direct amination

The title dicyano compound was synthesized via cyanation and it self-assembles in nonpolar solvents giving red-shifted and broad absorption maxima just as the bacteriochlorophylls which are encountered in the light-harvesting organelles of early photosynthetic bacteria. In the crystal, stacks are formed through a hierarchic combination of pi-stacking and a CN-Zn electrostatic interaction. Push-pull 15-N,N-dialkylamino-5-cyano congeners could be obtained in high yields using a solvent- and catalyst-free direct amination of meso-bromoporphyrins. Importantly, the fluorescence of the self-assembled species due to the very orderly manner in which the chromophores are arranged is not entirely quenched and has a surprisingly long lifetime of over 1 ns. This lends hope of using the trapped energy in biomimetic hybrid solar cells.     

New ruthenium(II) complexes with enantiomerically pure bis- and tris(pinene)-fused tridentate ligands. Synthesis, characterization and stereoisomeric analysis

A new set of Ru-Cl complexes containing either the pinene[5,6]bpea ligand (L1) or the C3 symmetric pinene[4,5]tpmOMe (L2) tridentate ligand in combination with the bidentate (B) 2,2'-bipyridine (bpy) or 1,2-diphenylphosphinoethane (dppe) with general formula [RuCl(L1 or L2)(B)](+) have been prepared and thoroughly characterized. In the solid state, X-ray diffraction analysis techniques have been used. In solution, cyclic voltammetry (CV) and 1D and 2D NMR spectroscopy have been employed. DFT calculations have been also performed on these complexes and their achiral analogues previously reported in our group, to interpret and complement experimental results. Whereas isomerically pure complexes ([Ru(II)Cl(L2)(bpy)](BF4), 5 and [Ru(II)Cl(L2)(dppe)](BF4), 6) are obtained when starting from the highly symmetric [Ru(III)Cl3(L2)], 2, isomeric mixtures of cis, fac-[Ru(II)Cl(L1)(bpy)](BF4) (3b/3b'), trans,fac- (3a) and up/down,mer- (3c, 3d) isomers are formed when bpy is added to the less symmetric [Ru(III)Cl3(L1)], 1, in contrast to the case of the bulky dppe ligand that, upon coordination to 1, leads to the trans,fac-[Ru(II)Cl(L1)(dppe)](BF4) (4a) complex as a sole isomer due to steric factors.     

Surface modification of thermoplastics--towards the plastic biochip for high throughput screening devices

Microarrays have become one of the most convenient tools for high throughput screening, supporting major advances in genomics and proteomics. Other important applications can be found in medical diagnostics, detection of biothreats, drug discovery, etc. Integration of microarrays with microfluidic devices can be highly advantageous in terms of portability, shorter analysis time and lower consumption of expensive biological analytes. Since fabrication of microfluidic devices using traditional materials such as glass is rather expensive, there is great interest in employing polymeric materials as a low cost alternative that is suitable for mass production. A number of commercially available plastic materials were reviewed for this purpose and poly(methylmethacrylate) Zeonor 1060R and Zeonex E48R were identified as promising candidates, for which methods for surface modification and covalent immobilization of DNA oligonucleotides were developed. In addition, we present proof-of-concept plastic-based microarrays with and without integration with microfluidics.     

Fine-tuning ligand-receptor design for selective molecular recognition of dicarboxylic acids

The host-guest interaction between the hexaaza macrocyclic ligand 3,7,11,18,22,26-hexaazatricyclo[26.2.2.2]tetratriaconta-1(31),13(34),14,16(33),28(32),29-hexaene (P3) and three rigid dicarboxylic acids (isophthalic acid, H2is; phthtalic acid, H2ph; and terephthalic acid, H2te) has been investigated using potentiometric equilibrium methods and NMR spectroscopy including the measurement of intermolecular nuclear Overhauser effects (NOEs) and self-diffusion coefficients (D). Ternary complexes are formed in aqueous solution as a result of hydrogen bond formation and Coulombic interactions between the host and the guest. In the [(H6P3)(is)]4+ complex, those bonding interactions reach a maximum yielding a log K6R of 4.74. Competitive distribution diagrams and total species distribution diagrams are used to illustrate the main features of these systems. In particular, a selectivity of over 89% at p[H] = 5.0 is obtained for the complexation of the is versus the te substrates. The recognition capacity of P3 over dicarboxylic acids (da) is compared to the related hexaaza macrocycle Me2P3 (7,22-dimethyl-3,7,11,18,22,26-hexaazatricyclo[26.2.2.2]tetratriaconta-1(30),13,15,28,31,33-hexaene) that binds da with a lesser strength, and it is not selective. Theoretical calculations performed at molecular dynamics level have also been carried out and point out that the origin of selectivity is mainly due to the capacity of the P3 ligand receptor to adapt to the geometry of the dicarboxylic acid to form relatively strong hydrogen bonds.     

A simple method for measuring long-range 1H-13C coupling constants in organic molecules

This study presents a simple method for measuring long-range heteronuclear coupling constants between protons and proton-bearing carbons. The approach involves recording two conventional 1D-TOCSY experiments in which the offset of the selective proton pulse is set on the low- and high-frequency 13C satellites of an isolated proton signal, Hi. Long-range heteronuclear coupling values between the 13Ci bonded to Hi and the protons Hj,k...n that belong to the same spin system were easily determined from the relative displacement of the relayed Hj,k...n signals in the satellite-selective TOCSY spectra. The sense of the displacement indicated the sign of the coupling constants.     

Dihydroxyacetone Phosphate Aldolase Catalyzed Synthesis of Structurally Diverse Polyhydroxylated Pyrrolidine Derivatives and Evaluation of their Glycosidase Inhibitory Properties

The chemoenzymatic synthesis of a collection of pyrrolidine‐type iminosugars generated by the aldol addition of dihydroxyacetone phosphate (DHAP) to C‐α‐substituted N‐Cbz‐2‐aminoaldehydes derivatives, catalyzed by DHAP aldolases is reported. L ‐Fuculose‐1‐phosphate aldolase (FucA) and L ‐rhamnulose‐1‐phosphate aldolase (RhuA) from E. coli were used as biocatalysts to generate configurational diversity on the iminosugars. Alkyl linear substitutions at C‐α were well tolerated by FucA catalyst (i.e., 40–70 % conversions to aldol adduct), whereas no product was observed with C‐α‐alkyl branched substitutions, except for dimethyl and benzyl substitutions (20 %). RhuA was the most versatile biocatalyst: C‐α‐alkyl linear groups gave the highest conversions to aldol adducts (60–99 %), while the C‐α‐alkyl branched ones gave moderate to good conversions (50–80 %), with the exception of dimethyl and benzyl substituents (20 %). FucA was the most stereoselective biocatalyst (90–100 % anti (3R,4R) adduct). RhuA was highly stereoselective with (S)‐N‐Cbz‐2‐aminoaldehydes (90–100 % syn (i.e., 3R,4S) adduct), whereas those with R configuration gave mixtures of anti/syn adducts. For iPr and iBu substituents, RhuA furnished the anti adduct (i.e., FucA stereochemistry) with high stereoselectivity. Molecular models of aldol products with iPr and iBu substituents and as complexes with the RhuA active site suggest that the anti adducts could be kinetically preferred, while the syn adducts would be the equilibrium products. The polyhydroxylated pyrrolidines generated were tested as inhibitors against seven glycosidases. Among them, good inhibitors of α‐L ‐fucosidase (IC₅₀=1–20 μM ), moderate of α‐L ‐rhamnosidase (IC₅₀=7–150 μM ), and weak of α‐D ‐mannosidase (IC₅₀=80–400 μM ) were identified. The apparent inhibition constant values (K_i) were calculated for the most relevant inhibitors and computational docking studies were performed to understand both their binding capacity and the mode of interaction with the glycosidases.