Comprehensive model of electromigrative transport in microfluidic paper based analytical devices

A complete mathematical model for electromigration in paper-based analytical devices is derived, based on differential equations describing the motion of fluids by pressure sources and EOF, the transport of charged chemical species, and the electric potential distribution. The porous medium created by the cellulose fibers is considered like a network of tortuous capillaries and represented by macroscopic parameters following an effective medium approach. The equations are obtained starting from their open-channel counterparts, applying scaling laws and, where necessary, including additional terms. With this approach, effective parameters are derived, describing diffusion, mobility, and conductivity for porous media. While the foundations of these phenomena can be found in previous reports, here, all the contributions are analyzed systematically and provided in a comprehensive way. Moreover, a novel electrophoretically driven dispersive transport mechanism in porous materials is proposed. Results of the numerical implementation of the mathematical model are compared with experimental data, showing good agreement and supporting the validity of the proposed model. Finally, the model succeeds in simulating a challenging case of free-flow electrophoresis in paper, involving capillary flow and electrophoretic transport developed in a 2D geometry.     

Experimental and theoretical N.M.R. studies of the coupling constants in seven isotopic ethyl fluorides

The N.M.R. spin-spin coupling constants and chemical shifts are reported for seven isotopically substituted ethyl fluorides. ¹H, ²H and ¹⁹F spectra have been observed and a consistent set of data obtained. Isotope effects are reported in ¹H and ¹⁹F spectra due to replacement of ¹H by ²H and ¹²C by ¹³C.

Using an accurate microwave structure of ethyl fluoride, CNDO and INDO calculations have been carried out, including dipolar and orbital terms. As independent options, configuration interaction between all single-excited states, variable radial electron distribution <r ^-3> and variable electron density at the site of nuclei, <s(0)²>, are included. Calculated values for all combinations of the options are given and a discussion of the results presented.     

Measurement of the impedance of very thin superconducting YBaCuO films at 10 GHz with a cavity perturbation method between 4 and 300 K

We have measured the complex film impedance 1/σd (σ conductivity, d film thickness) of three YBaCuO thin films with d = 44, 115, and 168 nm on MgO substrates at 10.2 GHz in the temperature range between 300 and 4 K. Below T_c, the experimental results are discussed in terms of the two-fluid model and the BCS theory. The residual resistance decreases with the film thickness. The thinnest film has a residual surface resistance of 3 · 10^?4 Ω. For this film, the complex microwave conductivity is calculated and compared with the models. Apart from the residual resistance, the measured conductivity is in agreement with the peak caused by the energy gap of the BCS theory. All measurements were performed with a cavity perturbation method which we have to our knowledge applied for the first time to superconducting thin films. The method allows to determine the complex impedance of films with arbitrary thickness. In particular, films with thicknesses small compared to the skin depth δ or the London penetration depth λ can be measured. Therefore, we are able to measure the impedance both in the normal and superconducting state.     

The conformation of poly(3-dodecyl thiophene) within methacrylic polymer matrix

Blends of poly(3-dodecyl thiophene) (PDDT) with poly(methyl methacrylate), poly(butyl methacrylate) (PBMA), and poly(methyl methacrylate-co-butyl methacrylate) (PMMA/PBMA) were studied by polarization optical microscopy, atomic-force microscopy, and absorption spectroscopy and were modeled using molecular dynamics (MD) simulations. The observed thermochromic transitions are shown to be host-matrix dependent, with PDDT/PBMA absorption spectra differing substantially from pristine PDDT. The dispersion of PDDT within PBMA matrix is observed to be greater than in the other host polymers. MD calculations of both individual PDDT molecules and molecular aggregates suggest that the distribution of dihedral angles present in the PDDT backbone is the narrowest for aggregates of PDDT embedded within a polymer matrix. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2909–2917, 1999     

Thioalkylated tetraethylene glycol: a new ligand for water soluble monolayer protected gold clusters

Ligand-stabilised, water-soluble gold nanoparticles of two different size ranges (2-4 and 5-8 nm) are readily prepared using monohydroxy (1-mercaptoundec-11-yl) tetraethylene glycol as a novel capping agent. These nanoparticles are as stable as alkylthiol-capped monolayer protected clusters (MPCs) and do not aggregate from aqueous solution under a wide range of stringent conditions. It is expected that this new material will be useful for a number of bio-analytical applications.     

The structure of α-(1,2-dithiole-3-ylidene) ketones and α-(1,2-dithiole-3-ylidene) aldehydes studied by means of n.m.r. spectroscopy

1H and ¹³C n.m.r. studies of a series of twelve 1,2-dithiole-3-ylidene ketones and aldehydes have shown that the geometry of the carbon backbone is the same as found in 1,6,6aλ⁴-trithiapentalenes. No evidence has been found which favours a bicyclic structure for the system. A linear correlation of observed ¹³C chemical shifts with calculated charge densities is found to be valid. The observations are in agreement with a structure which is a hybrid between a true ketonic structure and a true mesoionic structure. By using the difference in the ¹³C chemical shifts of ortho and meta carbon atoms in substituent phenyl groups it is possible to qualify the degree of coplanarity of the phenyl groups with the backbone of the molecule.     

Numerical simulations of paper-based electrophoretic separations with open-source tools

A new tool for the solution of electromigrative separations in paper-based microfluidics devices is presented. The implementation is based on a recently published complete mathematical model for describing these types of separations, and was developed on top of the open-source toolbox electroMicroTransport , based on OpenFOAM^®, inheriting all its features as native 3D problem handling, support for parallel computation, and a GNU GPL license. The presented tool includes full support for paper-based electromigrative separations (including EOF and the novel mechanical and electrical dispersion effects), compatibility with a well-recognized electrolyte database, and a novel algorithm for computing and controlling the electric current in arbitrary geometries. Additionally, the installation on any operating system is available due to its novel installation option in the form of a Docker image. A validation example with data from literature is included, and two extra application examples are provided, including a 2D free-flow IEF problem, which demonstrates the capabilities of the toolbox for dealing with computational and physicochemical modeling challenges simultaneously. This tool will enable efficient and reliable numerical prototypes of paper-based electrophoretic devices to accompany the contemporary fast growth in paper-based microfluidics.     

Precise electroosmotic flow measurements on paper substrates

A novel method for electroosmotic flow (EOF) measurement on paper substrates is presented; it is based on dynamic mass measurements by simply using an analytical balance. This technique provides a more reliable alternative to other EOF measurement methods on porous media. The proposed method is used to increase the amount and quality of the available information about physical parameters that characterize fluid flow on microfluidic paper–based analytical devices (μPADs). Measurements were performed on some of the most frequently used materials for μPADs, i.e., Whatman #1 , S&S, and Muntktell 00A filter paper. Obtained experimental results are consistent with the few previously reported data, either experimental or numerical, characterizing EOF in paper substrates. Moreover, a thorough analysis is presented for the quantification of the different effects that affect the measurements such as Joule effect and evaporation. Experimental results enabled, for the first time, to establish well-defined electroosmotic characteristics for the three substrates in terms of the magnitude of EOF as funtion of pH, enabling researchers to make a rational choice of the substrate depending on the electrophoretic technique to be implemented. The measurement method can be described as robust, reliable, and affordable enough for being adopted by researchers and companies devoted to electrophoretic μPADs and related technologies.     

Sizes and Conformation of the Molecules of DNA–Surfactant Complexes in Dilute Solutions and on the Atomic Smooth Substrates

The conformations of the molecules of DNA–surfactant complexes in dilute solutions and on the atomic smooth surfaces of mica and highly oriented pyrolytic graphite were comparatively studied by the methods of isothermal diffusion, electric birefringence, and atomic force microscopy. The DNA–surfactant complexes were deposited onto the substrates from a chloroform solution. The number of particles of the DNA–surfactant complex on the substrate was changed by varying the concentration of the initial solution within three orders of magnitude. The particles of a shape close to ellipsoidal, 25–70 nm in diameter and 2–4 nm high, were observed at the lowest concentration of DNA–surfactant solution on the mica substrate. The shape and size of these particles correspond to those of a single DNA–surfactant complex, calculated from its translational diffusion coefficient and the time of orientational relaxation in dilute solutions. An increase in the number of molecules deposited onto the substrate leads to an increase in the characteristic sizes of DNA–surfactant complex particles observed by the atomic force microscopy. This may be associated with the aggregation of DNA–surfactant complexes.