Beyond PDMS: off-stoichiometry thiol-ene (OSTE) based soft lithography for rapid prototyping of microfluidic devices

In this article we introduce a novel polymer platform based on off-stoichiometry thiol-enes (OSTEs), aiming to bridge the gap between research prototyping and commercial production of microfluidic devices. The polymers are based on the versatile UV-curable thiol-ene chemistry but takes advantage of off-stoichiometry ratios to enable important features for a prototyping system, such as one-step surface modifications, tuneable mechanical properties and leakage free sealing through direct UV-bonding. The platform exhibits many similarities with PDMS, such as rapid prototyping and uncomplicated processing but can at the same time mirror the mechanical and chemical properties of both PDMS as well as commercial grade thermoplastics. The OSTE-prepolymer can be cast using standard SU-8 on silicon masters and a table-top UV-lamp, the surface modifications are precisely grafted using a stencil mask and the bonding requires only a single UV-exposure. To illustrate the potential of the material we demonstrate key concepts important in microfluidic chip fabrication such as patterned surface modifications for hydrophobic stops, pneumatic valves using UV-lamination of stiff and rubbery materials as well as micromachining of chip-to-world connectors in the OSTE-materials.     

An electrospun degradable scaffold based on a novel hydrophilic polyester for tissue-engineering applications

Scaffolds based on a novel functionalized polyester, pHMGCL, are electrospun and characterized morphologically and physically. In vitro degradation studies of pHMGCL films show considerable mass loss and molecular weight reduction within 70 weeks. Scaffolds composed of fibers with uniform diameter (≈ 900 nm) and with melting temperatures higher than body temperature are prepared. As an indication for the feasibility of this material for regenerative medicine approaches, articular chondrocytes are seeded onto electrospun pHMGCL scaffolds. Chondrocytes attach to the fibers and re-differentiate as demonstrated by the production of GAG and collagen type II within four weeks of in vitro culture. Hydrophilic pHMGCL scaffolds may thus be useful for tissue engineering applications.     

Recent applications of chemometrics in one‐ and two‐dimensional chromatography

The proliferation of increasingly more sophisticated analytical separation systems, often incorporating increasingly more powerful detection techniques, such as high‐resolution mass spectrometry, causes an urgent need for highly efficient data‐analysis and optimization strategies. This is especially true for comprehensive two‐dimensional chromatography applied to the separation of very complex samples. In this contribution, the requirement for chemometric tools is explained and the latest developments in approaches for (pre‐)processing and analyzing data arising from one‐ and two‐dimensional chromatography systems are reviewed. The final part of this review focuses on the application of chemometrics for method development and optimization.     

Synthesis of the Natural Product Building Block 5‐(3‐Bromophenyl)‐4‐hydroxy‐5‐methylhexan‐2‐one and its Chiral Characterization by Using Chiroptical Spectroscopy

The absolute configuration of 5‐(3‐bromophenyl)‐4‐hydroxy‐5‐methylhexan‐2‐one, an intermediate in the synthesis of various natural products, is assigned by using vibrational circular dichroism (VCD), electronic circular dichroism (ECD), and optical rotatory dispersion (ORD). Experimental spectra were compared to density functional theory (DFT) calculations of the molecule with known configuration. These three techniques independently confirm that the absolute configuration is (S)‐5‐(3‐bromophenyl)‐4‐hydroxy‐5‐methylhexan‐2‐one, thus enabling us to assign the absolute configuration with high reliability. The reliability of the VCD analysis was assessed quantitatively by using the CompareVOA program. We found that, in cases in which the agreement between theory and experiment was very good, a value of 10 cm^?1 for the triangular weighting function gave a more‐realistic discriminative power between enantiomers than the default value of 20 cm^?1.     

Measurement of correlations between low-frequency vibrational modes and particle rearrangements in quasi-two-dimensional colloidal glasses

We investigate correlations between low-frequency vibrational modes and rearrangements in two-dimensional colloidal glasses composed of thermosensitive microgel particles, which readily permit variation of the sample packing fraction. At each packing fraction, the particle displacement covariance matrix is measured and used to extract the vibrational spectrum of the "shadow" colloidal glass (i.e., the particle network with the same geometry and interactions as the sample colloid but absent damping). Rearrangements are induced by successive, small reductions in the packing fraction. The experimental results suggest that low-frequency quasilocalized phonon modes in colloidal glasses, i.e., modes that present low energy barriers for system rearrangements, are spatially correlated with rearrangements in this thermal system.     

Reflected Brownian motion in generic triangles and wedges

Consider a generic triangle in the upper half of the complex plane with one side on the real line. This paper presents a tailored construction of a discrete random walk whose continuum limit is a Brownian motion in the triangle, reflected instantaneously on the left and right sides with constant reflection angles. Starting from the top of the triangle, it is evident from the construction that the reflected Brownian motion lands with the uniform distribution on the base. This raises some questions on the possible distributions of hulls generated by local processes.     

Numerical Homogenization of the Absolute Permeability Using the Conformal-Nodal and Mixed-Hybrid Finite Element Method

The modeling of hydrocarbon reservoirs and of aquifer-aquitard systems can be separated into two activities: geological modeling and fluid flow modeling. The geological model focuses on the geometry and the dimensions of the subsurface layers and faults, and on its rock types. The fluid flow model focuses on quantities like pressure, flux and dissipation, which are related to each other by rock parameters like permeability, storage coefficient, porosity and capillary pressure. The absolute permeability, which is the relevant parameter for steady single-phase flow of a fluid with constant viscosity and density, is studied here. When trying to match the geological model with the fluid flow model, it generally turns out that the spatial scale of the fluid flow model is built from units that are at least a hundred times larger in volume than the units of the geological model. To counter this mismatch in scales, the fine-scale permeabilities of the geological data model have to be upscaled' to coarse-scale permeabilities that relate the spatially averaged pressure, flux and dissipation to each other. The upscaled permeabilities may be considered as complicated averages, which are derived from the spatially averaged flow quantities in such a way that the continuity equation, Darcy's law and the dissipation equation remain valid on the coarse scale. In this paper the theory of upscaling will be presented from a physical point of view aiming at understanding, rather than mathematical rigorousness. Under the simplifying assumption of spatial periodicity of the fine-scale permeability distributions, homogenization theory can be applied. However, even then the spatial distribution of the permeability is generally so intricate that exact solutions of the homogenized permeability cannot be found. Therefore, numerical approximation methods have to be applied. To be able to estimate the approximation error, two numerical methods have been developed: one based on the conventional nodal finite element method (CN-FEM) and the other based on the mixed-hybrid finite element method (MH-FEM). CN-FEM gives an upper bound for the sum of the diagonal components of the homogenized mobility matrix, while MH-FEM gives a lower bound. Three numerical examples are presented.     

The Edge-Based Face Element Method for 3D-Stream Function and Flux Calculations in Porous Media Flow

We present a velocity-oriented discrete analog of the partial differential equations governing porous media flow: the edge-based face element method. Conventional finite element techniques calculate pressures in the nodes of the grid. However, such methods do not satisfy the requirement of flux continuity at the faces. In contrast, the edge-based method calculates vector potentials along the edges, leading to continuity of fluxes. The method is algebraically equivalent with the popular block-centered finite difference method and with the mixed-hybrid finite element method, but is algorithmically different and has the same robustness as the more conventional node-based velocity-oriented method. The numerical examples are computed analytically and may, therefore, be considered as an 'heuristic proof' of the theory and its practical applicability for reservoir engineering and geohydrology.     

The symmetry approximation for nonsymmetric permeability tensors and its consequences for mass transport

It is well known that the permeability has a tensor character. In practical applications, this is accounted for by the introduction of three principal permeabilities — three scalars — and three mutually orthogonal principal axes. In this paper, it is investigated whether this is always the exact way of describing anisotropy and, if not, what the consequences of the principal axes approximation are for flow and transport. First, it is shown that spatial upscaling may result in nonsymmetric large-scale permeability tensors, for which principal axes do not exist. However, it is possible to define generalized principal axes: three principal axes for the flux and three for the pressure gradient, with only three principal permeabilities. Since nonsymmetric permeability tensors are undesirable in practical applications, an approximation method making the nonsymmetric permeability symmetric is introduced. The important conclusion is then that the exact large-scale flux and large-scale pressure gradient do not have the same directions as the approximate flux and approximate pressure gradient. A practical consequence is that the principal axes approximation results in a difference between flux and transport direction. When considering miscible displacement or transport of mass dissolved in groundwater, the velocity component normal to the flux direction may be considered as a contribution to the transverse macro dispersion.     

Tuning the Halogen/Hydrogen Bond Competition: A Spectroscopic and Conceptual DFT Study of Some Model Complexes Involving CHF2I

Insight into the key factors driving the competition of halogen and hydrogen bonds is obtained by studying the affinity of the Lewis bases trimethylamine (TMA), dimethyl ether (DME), and methyl fluoride (MF) towards difluoroiodomethane (CHF₂I). Analysis of the infrared and Raman spectra of solutions in liquid krypton containing mixtures of TMA and CHF₂I and of DME and CHF₂I reveals that for these Lewis bases hydrogen and halogen‐bonded complexes appear simultaneously. In contrast, only a hydrogen‐bonded complex is formed for the mixtures of CHF₂I and MF. The complexation enthalpies for the C?H ??? Y hydrogen‐bonded complexes with TMA, DME, and MF are determined to be ?14.7(2), ?10.5(5) and ?5.1(6) kJ mol^?1, respectively. The values for the C?I ??? Y halogen‐bonded isomers are ?19.0(3) kJ mol^?1 for TMA and ?9.9(8) kJ mol^?1 for DME. Generalization of the observed trends suggests that, at least for the bases studied here, softer Lewis bases such as TMA favor halogen bonding, whereas harder bases such as MF show a substantial preference for hydrogen bonding.