Macromolecular transport through nanostructured and porous hydrogels synthesized using the amphiphilic copolymer, PCL-b-PEO-b-PCL

We have studied macromolecular transport through nanostructured and porous hydrogels. These hydrogels were produced by (1) synthesizing poly(ε-caprolactone-b-ethylene oxide-b-ε-caprolactone) (PCL-PEO-PCL) block copolymers, (2) crosslinking the block copolymer in aqueous solutions at high concentrations, and (3) degrading the PCL blocks by hydrolysis. Lamellar morphologies of the PCL-b-PEO-b-PCL were observed using Small Angle X-ray Scattering (SAXS) and Atomic Force Microscopy (AFM). The regions formerly occupied by PCL domains have no spanning PEO chains and thus should allow fast transport of macromolecules without significant entanglement. This work presents Fluorescence Recovery After Photobleaching (FRAP) data showing that macromolecular diffusivities are higher in these nanostructured materials than in comparable homogeneous PEO hydrogels prepared under the same crosslinking conditions to yield similar crosslink density. These materials offer a route to high macromolecular mobility, and so may be useful in bioengineering areas such as drug delivery and protein separation.     

The free energy of a reaction coordinate at multiple constraints: a concise formulation

The free energy as a function of the reaction coordinate (rc) is the key quantity for the computation of equilibrium and kinetic quantities. When it is considered as the potential of mean force, the problem is the calculation of the mean force for given values of the rc. We reinvestigate the PMCF (potential of mean constraint force) method which applies a constraint to the rc to compute the mean force as the mean negative constraint force and a metric tensor correction. The latter allows for the constraint imposed to the rc and possible artefacts due to multiple constraints of other variables which for practical reasons are often used in numerical simulations. Two main results are obtained that are of theoretical and practical interest. First, the correction term is given a very concise and simple shape which facilitates its interpretation and evaluation. Secondly, a theorem describes various rcs and possible combinations with constraints that can be used without introducing any correction to the constraint force. The results facilitate the computation of free energy by molecular dynamics simulations.     

Proton conduction in materials comprising conducting domains with widths less than 6 nm

We review the literature on proton conductivity and water uptake of composite polymer electrolyte membranes comprising bicontinuous hydrophilic and hydrophobic domains with well-controlled geometries. Both quantities appear to be enhanced when the width of the hydrophilic channels is smaller than 6 nm.     

Grain boundary interface mechanics in strain gradient crystal plasticity

Interactions between dislocations and grain boundaries play an important role in the plastic deformation of polycrystalline metals. Capturing accurately the behaviour of these internal interfaces is particularly important for applications where the relative grain boundary fraction is significant, such as ultra fine-grained metals, thin films and micro-devices. Incorporating these micro-scale interactions (which are sensitive to a number of dislocation, interface and crystallographic parameters) within a macro-scale crystal plasticity model poses a challenge. The innovative features in the present paper include (i) the formulation of a thermodynamically consistent grain boundary interface model within a microstructurally motivated strain gradient crystal plasticity framework, (ii) the presence of intra-grain slip system coupling through a microstructurally derived internal stress, (iii) the incorporation of inter-grain slip system coupling via an interface energy accounting for both the magnitude and direction of contributions to the residual defect from all slip systems in the two neighbouring grains, and (iv) the numerical implementation of the grain boundary model to directly investigate the influence of the interface constitutive parameters on plastic deformation. The model problem of a bicrystal deforming in plane strain is analysed. The influence of dissipative and energetic interface hardening, grain misorientation, asymmetry in the grain orientations and the grain size are systematically investigated. In each case, the crystal response is compared with reference calculations with grain boundaries that are either ‘microhard’ (impenetrable to dislocations) or ‘microfree’ (an infinite dislocation sink).     

Constrained optimization in expensive simulation: Novel approach

This article presents a novel heuristic for constrained optimization of computationally expensive random simulation models. One output is selected as objective to be minimized, while other outputs must satisfy given threshold values. Moreover, the simulation inputs must be integer and satisfy linear or nonlinear constraints. The heuristic combines (i) sequentialized experimental designs to specify the simulation input combinations, (ii) Kriging (or Gaussian process or spatial correlation modeling) to analyze the global simulation input/output data resulting from these designs, and (iii) integer nonlinear programming to estimate the optimal solution from the Kriging metamodels. The heuristic is applied to an (s,S)$(s\text{,}S)$ inventory system and a call-center simulation, and compared with the popular commercial heuristic OptQuest embedded in the Arena versions 11 and 12. In these two applications the novel heuristic outperforms OptQuest in terms of number of simulated input combinations and quality of the estimated optimum.     

Biological effects of weak electromagnetic fields from 0 Hz to 200 MHz: a survey of the literature with special emphasis on possible magnetic resonance effects

The literature on biological effects of weak electromagnetic fields of a frequency of 200 MHz or less is surveyed. The topic has been extraordinarily controversial, in part because of disputed assertions about a role for electromagnetic fields in carcinogenesis or production of abnormalities in growth and development. There is fairly widespread acceptance of certain beneficial effects, particularly the stimulation of healing. An increasing number of reports point to interactions between static magnetic fields and time-varying fields in the production of some effects. Safety implications are noted along with the hypothetical possibility of production of experimental artifacts by electromagnetic fields in MRS research.     

Coherent control of phonon-polaritons in a terahertz resonator fabricated with femtosecond laser machining

Using femtosecond laser machining, we fabricated a terahertz resonant cavity in LiNbO3. Optical pulse sequences with variable repetition rates, generated through a novel pulse-shaping method, are used for characterization of the cavity resonances and for amplification of terahertz phonon-polaritons in the cavity.     

Quantifying the hydrophobic effect. 2. A computer simulation-molecular-thermodynamic model for the micellization of nonionic surfactants in aqueous solution

In this article, the validity and accuracy of the CS-MT model is evaluated by using it to model the micellization behavior of seven nonionic surfactants in aqueous solution. Detailed information about the changes in hydration that occur upon the self-assembly of the surfactants into micelles was obtained through molecular dynamics simulation and subsequently used to compute the hydrophobic driving force for micelle formation. This information has also been used to test, for the first time, approximations made in traditional molecular-thermodynamic modeling. In the CS-MT model, two separate free-energy contributions to the hydrophobic driving force are computed. The first contribution, gdehydr, is the free-energy change associated with the dehydration of each surfactant group upon micelle formation. The second contribution, ghydr, is the change in the hydration free energy of each surfactant group upon micelle formation. To enable the straightforward estimation of gdehydr and ghydr in the case of nonionic surfactants, a number of simplifying approximations were made. Although the CS-MT model can be used to predict a variety of micellar solution properties including the micelle shape, size, and composition, the critical micelle concentration (CMC) was selected for prediction and comparison with experimental CMC data because it depends exponentially on the free energy of micelle formation, and as such, it provides a stringent quantitative test with which to evaluate the predictive accuracy of the CS-MT model. Reasonable agreement between the CMCs predicted by the CS-MT model and the experimental CMCs was obtained for octyl glucoside (OG), dodecyl maltoside (DM), octyl sulfinyl ethanol (OSE), decyl methyl sulfoxide (C10SO), decyl dimethyl phosphine oxide (C10PO), and decanoyl-n-methylglucamide (MEGA-10). For five of these surfactants, the CMCs predicted using the CS-MT model were closer to the experimental CMCs than the CMCs predicted using the traditional molecular-thermodynamic (MT) model. In addition, CMCs predicted for mixtures of C10PO and C10SO using the CS-MT model were significantly closer to the experimental CMCs than those predicted using the traditional MT model. For dodecyl octa(ethylene oxide) (C12E8), the CMC predicted by the CS-MT model was not in good agreement with the experimental CMC and with the CMC predicted by the traditional MT model, because the simplifying approximations made to estimate gdehydr and ghydr in this case were not sufficiently accurate. Consequently, we recommend that these simplifying approximations only be used for nonionic surfactants possessing relatively small, non-polymeric heads. For MEGA-10, which is the most structurally complex of the seven nonionic surfactants modeled, the CMC predicted by the CS-MT model (6.55 mM) was found to be in much closer agreement with the experimental CMC (5 mM) than the CMC predicted by the traditional MT model (43.3 mM). Our results suggest that, for complex, small-head nonionic surfactants where it is difficult to accurately quantify the hydrophobic driving force for micelle formation using the traditional MT modeling approach, the CS-MT model is capable of making reasonable predictions of aqueous micellization behavior.     

Computational optimization of the configuration of a spatially resolved spectroscopy sensor for milk analysis

A global optimizer has been developed, capable of computing the optimal configuration in a probe for spatially resolved reflectance spectroscopy (SRS). The main objective is to minimize the number of detection fibers, while maintaining an accurate estimation of both absorption and scattering profiles. Multiple fibers are necessary to robustify the estimation of optical properties against noise, which is typically present in the measured signals and influences the accuracy of the inverse estimation. The optimizer is based on a robust metamodel-based inverse estimation of the absorption coefficient and a reduced scattering coefficient from the acquired SRS signals. A genetic algorithm is used to evaluate the effect of the fiber placement on the performance of the inverse estimator to find the bulk optical properties of raw milk. The algorithm to find the optimal fiber placement was repeatedly executed for cases with a different number of detection fibers, ranging from 3 to 30. Afterwards, the optimal designs for each considered number of fibers were compared based on their performance in separating the absorption and scattering properties, and the significance of the differences was tested. A sensor configuration with 13 detection fibers was found to be the combination with the lowest number of fibers which provided an estimation performance which was not significantly worse than the one obtained with the best design (30 detection fibers). This design resulted in the root mean squared error of prediction (RMSEP) of 1.411 cm⁻¹ (R² = 0.965) for the estimation of the bulk absorption coefficient values, and 0.382 cm⁻¹ (R² = 0.996) for the reduced scattering coefficient values.