Micromechanical Properties of Microstructured Elastomeric Hydrogels

Local, micromechanical environment is known to influence cellular function in heterogeneous hydrogels, and knowledge gained in micromechanics will facilitate the improved design of biomaterials for tissue regeneration. In this study, a system comprising microstructured resilin‐like polypeptide (RLP)–poly(ethylene glycol) (PEG) hydrogels is utilized. The micromechanical properties of RLP‐PEG hydrogels are evaluated with oscillatory shear rheometry, compression dynamic mechanic analysis, small‐strain microindentation, and large‐strain indentation and puncture over a range of different deformation length scales. The measured elastic moduli are consistent with volume averaging models, indicating that volume fraction, not domain size, plays a dominant role in determining the low strain mechanical response. Large‐strain indentation under a confocal microscope enables the visualization of the microstructured hydrogel micromechanical deformation, emphasizing the translation, rotation, and deformation of RLP‐rich domains. The fracture initiation energy results demonstrate that failure of the composite hydrogels is controlled by the RLP‐rich phase, and their independence with domain size suggested that failure initiation is controlled by multiple domains within the strained volume. This approach and findings provide new quantitative insight into the micromechanical response of soft hydrogel composites and highlight the opportunities in employing these methods to understand the physical origins of mechanical properties of soft synthetic and biological materials.     

Chiral symmetry breaking during crystallization: complete chiral purity induced by nonlinear autocatalysis and recycling

We report experimental results that show a large and symmetric population of D and L crystals moving into complete chiral purity, with one of the enantiomers completely disappearing. The results indicate (i) a new symmetry breaking process incompatible with the hypothesis of an initial single chiral phase or "mother crystal," (ii) that total symmetry breaking and complete chiral purity can be achieved from a system that initially includes both enantiomers, and (iii) that this is achieved through a nonlinear autocatalytic-recycling process.     

The effect of cocurrent and countercurrent gas shear on entrance region mass transfer in turbulent falling liquid films

Predictions of average film thickness and mass transfer coefficients in the entrance region of gas absorption with high cocurrent and countercurrent gas flow in a turbulent falling film are presented. The model used is a modified van Driest eddy diffusivity in the inner wall region and an interface damping eddy diffusivity in the outher region of the film modified to include the effect of interfacial shear. The calculations show that the entrance length for mass transfer decreases with increasing film Reynolds number and interfacial shear for cocurrent flow. Also the model predicts a decrease in mass transfer coefficient with an increase in Schmidt number in accordance with experimental data. On the other hand, for counterflow and at a fixedRe, an increase in upward gas shear increases the film thickness and eventually leads to rising film flow. The entrance length for mass transfer decreases with increasing Reynolds number but slightly increases with countercurrent interfacial shear. The calculations show that, in practice, the entrance region for mass transfer for gas absorption with shear-thinned film can be neglected for cocurrent shear but often cannot be neglected for countercurrent shear with a shear-thickened film.Es werden Berechnungen für die mittlere Film-dicke und die Stoffübertragungs-Koeffizienten in der Eintrittsregion der Gasabsorption mit starkem Gleich- und Gegenstrom von Gas in einem turbulent fließenden Film aufgestellt. Das benutzte Modell ist ein modifizierter van Driest-Wirbel-Diffuser für die Innenwand und ein gedämpfter Grenzflächen-Wirbel-Diffuser in der Außenregion des Filmes, der so modifiziert ist, daß die Effekte der Grenzschichtschubspannungen berücksichtigt werden. Die Berechnungen zeigen, daß die Eintrittslänge für die Stoffübertragung mit zunehmender Grenzflächenschubspannung für Gleichstrom abnimmt. Das Modell sagt ebenso ein Sinken des Stoffübertragungs-Koeffizienten mit einer Zunahme der Schmidt-Zahl in Übereinstimmung mit den experimentellen Daten voraus. Auf der anderen Seite führt im Falle von Gegenstrom und einer konstanten Reynolds-Zahl ein Ansteigen der Gasschubspannung zu einem Anwachsen der Filmdicke und eventuell zu wachsender Filmströmung. Die Eintrittslänge für die Stoffübertragung sinkt mit zunehmender Reynolds-Zahl, steigt aber langsam bei Grenzflächenschubspannungen in Gegenstromrichtung. Die Berechnungen zeigen, daß in der Praxis die Eintrittsregion für die Stoffübertragung bei der Gasabsorption mit verdünntem Film für Gleichstromschubspannung vernachlässigt werden kann, bei Gegenstromschubspannung mit verdicktem Film diese jedoch meist berücksichtigt werden muß.     

Real Quadratic Julia Sets Can Have Arbitrarily High Complexity

Foundations of Computational Mathematics - We show that there exist real parameters $$c\in (-2,0)$$ for which the Julia set $$J_{c}$$ of the quadratic map $$z^{2} + c$$ has arbitrarily high...     

Surface hydrophobicity modulates the operation of actomyosin-based dynamic nanodevices

We studied the impact of surface hydrophobicity on the motility of actin filaments moving on heavy-meromyosin (HMM)-coated surfaces. Apart from nitrocellulose (NC), which is the current standard for motility assays, all materials tested are good candidates for microfabrication: hydrophilic and hydrophobic glass, poly(methyl methacrylate) (PMMA), poly(tert-butyl methacrylate) (PtBuMA), and a copolymer of O-acryloyl acetophenone oxime with a 4-acryloyloxybenzophenone (AAPO). The most hydrophilic (hydrophilic glass, contact angle 35 degrees) and the most hydrophobic (PtBuMA, contact angle 78 degrees) surfaces do not maintain the motility of actin filaments, presumably because of the low density of adsorbed HMM protein or its high levels of denaturation, respectively. The velocity of actin filaments presents higher values in the middle of this "surface hydrophobicity motility window" (NC, PMMA), and a bimodal distribution, which is more apparent at the edges of this motility window (hydrophobic glass and AAPO). A molecular surface analysis of HMM and its S1 units suggests that the two very different, temporally separated conformations of the HMM heads could exacerbate the surface-modulated protein behavior, which is common to all microdevices using surface-immobilized proteins. An explanation for the above behavior proposes that the motility of actin filaments on HMM-functionalized surfaces is the result of the action of three populations of motors, each in a different surface-protein conformation, that is, HMM with both heads working (high velocities), working with one head (low velocities), and fully denatured HMM (no motility). It is also proposed that the molecularly dynamic nature of polymer surfaces amplifies the impact of surface hydrophobicity on protein behavior. The study demonstrates that PMMA is a good candidate for the fabrication of future actomyosin-driven dynamic nanodevices because it induces the smoothest motility of individual nano-objects with velocities comparable with those obtained on NC.     

Hydrogen‐bonding interactions in the active site of a low molecular weight protein‐tyrosine phosphatase

Molecular dynamics simulation of the Michaelis complex, phospho‐enzyme intermediate, and the wild‐type and C12S mutant have been carried out to examine hydrogen‐bonding interactions in the active site of the bovine low molecular weight protein‐tyrosine phosphatase (BPTP). It was found that the S_γ atom of the nucleophilic residue Cys‐12 is ideally located at a position opposite from the phenylphosphate dianion for an inline nucleophilic substitution reaction. In addition, electrostatic and hydrogen‐bonding interactions from the backbone amide groups of the phosphate‐binding loop strongly stabilize the thiolate anion, making Cys‐12 ionized in the active site. In the phospho‐enzyme intermediate, three water molecules are found to form strong hydrogen bonds with the phosphate group. In addition, another water molecule can be identified to form bridging hydrogen bonds between the phosphate group and Asp‐129, which may act as the nucleophile in the subsequent phosphate hydrolysis reaction, with Asp‐129 serving as a general base. The structural difference at the active site between the wild‐type and C12S mutant has been examined. It was found that the alkoxide anion is significantly shifted toward one side of the phosphate binding loop, away from the optimal position enjoyed by the thiolate anion of the wild‐type enzyme in an S_N2 process. This, coupled with the high pK_a value of an alcoholic residue, makes the C12S mutant catalytically inactive. These molecular dynamics simulations provided details of hydrogen bonding interactions in the active site of BPTP, and a structural basis for further studies using combined quantum mechanical and molecular mechanical potential to model the entire dephosphorylation reaction by BPTP. © 2000 John Wiley & Sons, Inc. J Comput Chem 21: 1192–1203, 2000     

Theoretical representation of solvation in biochemical systems: From discrete solute-solvent interactions to bulk solvation

The interaction between solutes and simple solvents in dilute solutions is analyzed in a systematic way. Different theoretical methods to describe specific solute-solvent interactions and general solvation effects are presented. Finally, the importance of solvent-induced changes in solute properties is discussed through the use of mixed quantum mechanics/classical mechanics strategies. © 1996 John Wiley & Sons, Inc.     

Generation of polymerosomes from double-emulsions

Diblock copolymers are known to spontaneously organize into polymer vesicles. Typically, this is achieved through the techniques of film rehydration or electroformation. We present a new method for generating polymer vesicles from double emulsions. We generate precision water-in-oil-in-water double emulsions from the breakup of concentric fluid streams; the hydrophobic fluid is a volatile mixture of organic solvent that contains dissolved diblock copolymers. We collect the double emulsions and slowly evaporate the organic solvent, which ultimately directs the self-assembly of the dissolved diblock copolymers into vesicular structures. Independent control over all three fluid streams enables precision assembly of polymer vesicles and provides for highly efficient encapsulation of active ingredients within the polymerosomes. We also use double emulsions with several internal drops to form new polymerosome structures.     

Comparison of NDDO and quasi-ab initio approaches to compute semiempirical molecular electrostatic potentials

The suitability of the two most widely used strategies to compute semiempirical MEPs is examined. For this purpose, MEP minima, electrostatic charges, and dipoles for a large number of molecules were computed at the AM1, MNDO, and PM3 levels using both the NDDO strategy developed by Ferenczy, Reynolds, and Richards and our own quasi-ab initio method. Results demonstrate that the quasi-ab initio is preferred over the NDDO method for the computation of MEP minima. It is also found that the best set of semiempirical charges and dipoles are obtained using either the AM1 NDDO or the MNDO quasi-ab initio methods. In these two cases, the quality of the results is fully comparable with 6-31G* values. © 1994 by John Wiley & Sons, Inc.