Gemini-induced columnar jointing in vitreous ice. Cryo-HRSEM as a tool for discovering new colloidal morphologies

A gemini surfactant is able to promote columnar jointing in vitreous ice where long pillars, often of hexagonal cross section, are formed. This jointing is visible by cryo-high-resolution scanning electron microscopy (cryo-HRSEM), in which colloidal suspensions in bulk water are cooled rapidly in liquid ethane, thereby avoiding the potential artifacts with other types of EM. The jointing is proposed to arise from a new type of colloidal morphology where the surfactant self-assembles into hexagonal columns. Evidence for this mechanism comes from a cryo-HRSEM photo of an ice-free hexagonal "skeleton" composed of surfactant. Cryo-HRSEM, a method that is just beginning to realize its potential, would seem to have a promising future in the discovery of additional and as yet unimagined colloidal structures.     

Morphological characterization of elastin-mimetic block copolymers utilizing cryo- and cryoetch-HRSEM.

Elastin-mimetic block copolymers were produced by genetic engineering. Genetically driven synthesis permitted control of the final physiochemical characteristics of the block copolymers. We designed BB and BAB block copolymers in which the A-block was hydrophilic and the B-block was hydrophobic. By designing the copolymers in this manner, it was proposed that they would self-assemble into micellar aggregates that, at high concentration, would form thermoreversible hydrogels. To analyze the three-dimensional fine surface morphology of the copolymers, to the resolution level of a few nanometers, we employed cryo-HRSEM. This method provided vast expanses of the specimen in its frozen hydrated state for survey. In our initial cryo-HRSEM studies, we observed the protein filaments and micelles surrounded by lakes of vitreous ice. Upon examination at low and intermediate magnifications, there was an extensive honeycomb-like filamentous network. To delineate the fine morphology of the hydrogel network at high magnification and to greater depths, we cryoetched away unbound water from the sample surface, in high vacuum, prior to chromium deposition. By using this technique, we were able to visualize for characterization purposes the fine fibril networks formed from the micellar aggregates over the surface of the hydrogel.     

In-lens cryo-high resolution scanning electron microscopy: methodologies for molecular imaging of self-assembled organic hydrogels.

The micro- and nanoarchitectures of water-swollen hydrogels were routinely analyzed in three dimensions at very high resolution by two cryopreparation methods that provide stable low-temperature specimens for in-lens high magnification recordings. Gemini surfactants (gS), poly-N-isopropylacrylamides (p-NIP Am), and elastin-mimetic di- (db-E) and triblock (tb-E) copolymer proteins that form hydrogels have been routinely analyzed to the sub-10-nm level in a single day. After they were quench or high pressure frozen, samples in bulk planchets were subsequently chromium coated and observed at low temperature in an in-lens field emission SEM. Pre-equilibrated planchets (4-40 degrees C) that hold 5-10 microl of hydrogel facilitate dynamic morphological studies above and below their transition temperatures. Rapidly frozen samples were fractured under liquid nitrogen, low-temperature metal coated, and observed in-lens to assess the dispersion characteristics of micelles and fragile colloidal assemblies within bulk frozen water. Utilizing the same planchet freezing system, the cryoetch-HRSEM technique removed bulk frozen water from the hydrogel matrix by low-temperature, high-vacuum sublimation. The remaining frozen solid-state sample faithfully represented the hydrogel matrix. Cryo- and cryoetch-HRSEM provided vast vistas of hydrogels at low and intermediate magnifications whereas high magnification recordings and anaglyphs (stereo images) provided a three-dimensional prospective and measurements on a molecular level.     

Non-Smooth Optimization for Robust Control of Infinite-Dimensional Systems

We use a non-smooth trust-region method for H _∞-control of infinite-dimensional systems. Our method applies in particular to distributed and boundary control of partial differential equations. It is computationally attractive as it avoids the use of system reduction or identification. For illustration the method is applied to control a reaction-convection-diffusion system, a Van de Vusse reactor, and to a cavity flow control problem.     

Nonsmooth Bundle Trust-region Algorithm with Applications to Robust Stability

We propose a bundle trust-region algorithm to minimize locally Lipschitz functions which are potentially nonsmooth and nonconvex. We prove global convergence of our method and show by way of an example that the classical convergence argument in trust-region methods based on the Cauchy point fails in the nonsmooth setting. Our method is tested experimentally on three problems in automatic control.     

Vibronic dynamics of I(2) trapped in amorphous ice: coherent following of cage relaxation

Four-wave mixing measurements are carried out on I(2)-doped ice, prepared by quench condensing the premixed vapor at 128 K. Coherent vibrational dynamics is observed in two distinct ensembles. The first is ascribed to trapping in asymmetric polar cages in which, as in water, the valence absorption of the molecule is blueshifted by 3500 cm(-1), predissociation of the B state is complete upon the first extension of the molecular bond, and the vibrational frequency in the ground state (observed through coherent anti-Stokes Raman scattering) is reduced by 6.5%. The effect is ascribed to polarization of the molecule. The implied local field and the ionicity of the molecule are extracted, to conclude that the molecule is oxygen bonded to one water molecule on one side and hydrogen bonded on the other side. The second ensemble is characterized by the transient grating signal, which shows coherent vibrational dynamics on the B state. The small predissociation rate in this site suggests a symmetric cage in which the local electric field undergoes effective cancellation; and consistent with this, the extracted blueshift of the valence transition in this site (approximately 1500 cm(-1)) coincides with that observed in clathrate hydrates of iodine. Remarkably, in this site, the vibrational period of the B state packet coherently stretches from an initial value of 245 fs to 325 fs in the course of five oscillations (1.3 ps), indicative of vibrationally adiabatic following of the cage expansion. The dynamics is characteristic of a molecule trapped in a tight symmetric cage, with a soft cage coordinate that relaxes without eliciting elastic response. Enclathration in low-density amorphous ice is concluded.     

Shamrock surfactants with terminal carboxylate headgroups and a central phosphorodithioate or quaternary ammonium headgroup

Surfactants 3 (tripotassium O,O'-di-[11-(carboxylato)undecyl]phosphorodithioate) and 4 (sodium 12-[dimethyl-(11-carboxylatoundecyl)ammonio]dodecanoate), which are new shamrock surfactants, were prepared and characterized. Shamrock surfactants represent a novel class of surfactants that contain a central headgroup connected to two flanking headgroups by hydrocarbon chains; they do not contain long-chain alkyl groups. Surfactants 3 and 4 were characterized in water by measurement of their Krafft temperatures and critical aggregation concentrations, and their aggregates were studied by 1H and 31P NMR spectroscopy, dynamic laser light scattering, and phase-contrast optical microscopy. Aqueous 3 and 4 were also studied by cryoetch high-resolution scanning electron microscopy, which revealed fences with interposed lacelike patterns for the former and compartments formed by irregular fences for the latter. Coacervates were likely formed upon the undisturbed hydration of 3 and 4, as determined by phase-contrast optical microscopy.     

Rational design of a reversible pH-responsive switch for peptide self-assembly

Peptide TZ1H, based on the heptad sequence of a coiled-coil trimer, undergoes fully reversible, pH-dependent self-assembly into long-aspect-ratio helical fibers. Substitution of isoleucine residues with histidine at the core d-positions of alternate heptads introduces a mechanism by which self-assembly is coupled to the protonation state of the imidazole side chain. Circular dichroism spectroscopy, transmission electron microscopy, and microrheology techniques revealed that the self-assembly of TZ1H coincides with a distinct coil-helix conformational transition that occurs within a narrow pH range near the pKa of the imidazole side chains of the core histidine residues.