Interactions of flexible polymers and globular colloids : understanding protein partitioning in two-phase aqueous polymer systems

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 1992.Science hard copy is bound in 1 v.Includes bibliographical references (leaves 364-377).by Nicholas L. Abbott.Ph.D

Single-Step Synthesis of Shape-Controlled Polymeric Particles using Initiated Chemical Vapor Deposition in Liquid Crystals

The ability to synthesize shape-controlled polymer particles will benefit a wide range of applications including targeted drug delivery and metamaterials with reconfigurable structures, but existing synthesis approaches are commonly multistep and limited to a narrow size/shape range. Using a novel single-step synthesis technique, a variety of shapes including nanospheres, hemispherical micro-domes, orientation-controlled microgels, microspheres, spheroids, and micro-discs were obtained. The shape-controlled particles were synthesized by polymerizing divinylbenzene (DVB) via initiated chemical vapor deposition (iCVD) in nematic liquid crystals (LC). iCVD continuously and precisely delivered vapor-phase reactants, thus avoiding disruption of the LC structure, a critical limitation in past LC-templated polymerization. That shape controllability was further enabled by leveraging LC as a real-time display of the polymerization conditions and progression, using a custom in-situ long-focal range microscope. Detailed image analysis unraveled key mechanisms in polymer synthesis in LC. Poor solubilization by nematic LC led to the formation of pDVB nanospheres, distinct from microspheres obtained in isotropic solvents. The nanospheres precipitated to the LC-solid interface and further aggregated into microgel clusters with controlled orientation that was guided by the LC molecular alignment. On further polymerization, microgel clusters phase separated to form microspheres, spheroids, and unique disc-shaped particles.Comment: 35 pages, 5 figure

Immobilization of Polymer-Decorated Liquid Crystal Droplets on Chemically Tailored Surfaces

We demonstrate that the assembly of an amphiphilic polyamine on the interfaces of micrometer-sized droplets of a thermotropic liquid crystal (LC) dispersed in aqueous solutions can be used to facilitate the immobilization of LC droplets on chemically functionalized surfaces. Polymer 1 was designed to contain both hydrophobic (alkylfunctionalized) and hydrophilic (primary and tertiary amine-functionalized) side chain functionality. The assembly of this polymer at the interfaces of aqueous dispersions of LC droplets was achieved by the spontaneous adsorption of polymer from aqueous solution. Polymer adsorption triggered transitions in the orientational ordering of the LCs, as observed by polarized light and bright-field microscopy. We demonstrate that the presence of polymer 1 on the interfaces of these droplets can be exploited to immobilize LC droplets on planar solid surfaces through covalent bond formation (e.g., for surfaces coated with polymer multilayers containing reactive azlactone functionality) or through electrostatic interactions (e.g., for surfaces coated with multilayers containing hydrolyzed azlactone functionality). The characterization of immobilized LC droplets by polarized, fluorescence, and laser scanning confocal microscopy revealed the general spherical shape of the polymer-coated LC droplets to be maintained after immobilization, and that immobilization led to additional ordering transitions within the droplets that were dependent on the nature of the surfaces with which they were in contact. Polymer 1-functionalized LC droplets were not immobilized on polymer multilayers treated with poly(ethylene imine) (PEI). We demonstrate that the ability to design surfaces that promote or prevent the immobilization of polymer-functionalized LC droplets can be exploited to pattern the immobilization of LC droplets on surfaces. The results of this investigation provide the basis of an approach that could be used to tailor the properties of dispersed LC emulsions and to immobilize these droplets on functional surfaces of interest in a broad range of fundamental and applied contexts

Dynamic Ordering Transitions of Liquid Crystals Driven by Interfacial Complexes Formed Between Polyanions and Amphiphilic Polyamines

We report the design of an amphiphilic polyamine (polymer 1) based on poly(2-alkenyl azlactone) that strongly couples the formation of polyelectrolyte complexes at aqueous/liquid crystal (LC) interfaces to ordering transitions in the LC. We demonstrate that the addition of a strong anionic polyelectrolyte to aqueous solutions in contact with polymer 1-laden LC interfaces (prepared by Langmuir-Schaefer transfer of monolayers of polymer 1 onto micrometerthick films of nematic LC) triggers ordering transitions in the LCs. We further demonstrate that changes in the ordering of the LCs (i) are driven by electrostatic interactions between the polyelectrolytes, (ii) involve multivalent interactions between the polyelectrolytes, and (iii) are triggered by reorganization of the hydrophobic side chains of amphiphilic polymer 1 upon formation of the interfacial complexes. The results presented in this paper lead us to conclude that ordering transitions in LCs can be used to provide insights into the structure and dynamics of interfacial complexes formed between polyelectrolytes

Langmuir Films of Flexible Polymers Transferred to Aqueous/Liquid Crystal Interfaces Induce Uniform Azimuthal Alignment of the Liquid Crystal

We reported recently that amphiphilic polymers can be assembled at interfaces created between aqueous phases and thermotropic liquid crystals (LCs) in ways that: (i) couple the organization of the polymer to the order of the LC and (ii) respond to changes in the properties of aqueous phases that can be characterized as changes in the optical appearance of the LC. This investigation sought to characterize the behavior of aqueous-LC interfaces decorated with uniaxially compressed thin films of polymers transferred by Langmuir-Schaefer (LS) transfer. Here, we report physicochemical characterization of interfaces created between aqueous phases and the thermotropic LC 4-cyano-4′-pentylbiphenyl (5CB) decorated with Langmuir films of a novel amphiphilic polymer (polymer 1), synthesized by the addition of hydrophobic and hydrophilic side chains to poly(2-vinyl-4,4′-dimethylazlactone). Initial characterization of this system resulted in the unexpected observation of uniform azimuthal alignment of 5CB after LS transfer of the polymer films to aqueous-5CB interfaces. This paper describes characterization of Langmuir films of polymer 1 hosted at aqueous-5CB interfaces as well as the results of our investigations into the origins of the uniform ordering of the LC observed upon LS transfer. Our results, when combined, support the conclusion that uniform azimuthal alignment of 5CB is the result of long-range ordering of polymer chains in the Langmuir films (in a preferred direction orthogonal to the direction of compression) that is generated during uniaxial compression of the films prior to LS transfer. Although past studies of Langmuir films of polymers at aqueous-air interfaces have demonstrated that in-plane alignment of polymer backbones can be induced by uniaxial compression, these past reports have generally made use of polymers with rigid backbones. One important outcome of this current study is thus the observation of anisotropy and long-range order in Langmuir films of a novel flexible polymer. A second important outcome is the observation that the existence, extent, and dynamics of this order can be identified and characterized optically by transfer of the Langmuir film to a thin film of LC. Additional characterization of Langmuir films of two other flexible polymers [poly(methyl methacrylate) and poly(vinyl stearate)] using this method also resulted in uniform azimuthal alignment of 5CB, suggesting that the generation of long-range order in uniaxially compressed Langmuir films of polymers may also occur more generally over a broader range of polymers with flexible backbones

Generation and propagation of solitary waves in nematic liquid crystals

Solitons in nematic liquid crystals offer intriguing opportunities for transport and sensing in microfluidic systems. Little is known about the elementary conditions that are needed to create solitons in nematic materials. In this work, theory, simulations and experiments are used to study the generation and propagation of solitary waves (or "solitons") in nematic liquid crystals upon the application of an alternating current (AC) electric field. We find that these solitary waves exhibit "butterfly"-like or "bullet"-like structures that travel in the direction perpendicular to the applied electric field. Such structures propagate over long distances without losing their initial shape. The theoretical model adopted here serves to identify some of the key requirements that are needed to generate solitons in the absence of electrostatic interactions. These include surface imperfections that introduce a twist in the director, unequal elastic constants, and negative anisotropic dielectric permittivity. The results of simulations are shown to be in good agreement with our own experimental observations, serving to establish the validity of the theoretical concepts advanced in this work

Colloid-in-Liquid Crystal Gels that Respond to Biomolecular Interactions

This paper advances the design of stimuli-responsive materials based on colloidal particles dispersed in liquid crystals (LCs). Specifically, thin films of colloid-in-liquid crystal (CLC) gels undergo easily visualized ordering transitions in response to reversible and irreversible (enzymatic) biomolecular interactions occurring at the aqueous interfaces of the gels. In particular, LC ordering transitions can propagate across the entire thickness of the gels. However, confinement of the LC to small domains with lateral sizes of approximate to 10 m does change the nature of the anchoring transitions, as compared to films of pure LC, due to the effects of confinement on the elastic energy stored in the LC. The effects of confinement are also observed to cause the response of individual domains of the LC within the CLC gel to vary significantly from one to another, indicating that manipulation of LC domain size and shape can provide the basis of a general and facile method to tune the response of these LC-based physical gels to interfacial phenomena. Overall, the results presented in this paper establish that CLC gels offer a promising approach to the preparation of self-supporting, LC-based stimuli-responsive materials

Controlled deformation of vesicles by flexible structured media

Liquid crystalline (LC) materials, such as actin or tubulin networks, are known to be capable of deforming the shape of cells. Here, elements of that behavior are reproduced in a synthetic system, namely, a giant vesicle suspended in a LC, which we view as a first step toward the preparation of active, anisotropic hybrid systems that mimic some of the functionality encountered in biological systems. To that end, we rely on a coupled particle-continuum representation of deformable networks in a nematic LC represented at the level of a Landau–de Gennes free energy functional. Our results indicate that, depending on its elastic properties, the LC is indeed able to deform the vesicle until it reaches an equilibrium, anisotropic shape. The magnitude of the deformation is determined by a balance of elastic and surface forces. For perpendicular anchoring at the vesicle, a Saturn ring defect forms along the equatorial plane, and the vesicle adopts a pancake-like, oblate shape. For degenerate planar anchoring at the vesicle, two boojum defects are formed at the poles of the vesicle, which adopts an elongated, spheroidal shape. During the deformation, the volume of the topological defects in the LC shrinks considerably as the curvature of the vesicle increases. These predictions are confirmed by our experimental observations of spindle-like shapes in experiments with giant unilamellar vesicles with planar anchoring. We find that the tension of the vesicle suppresses vesicle deformation, whereas anchoring strength and large elastic constants promote shape anisotropy

A North Atlantic tephrostratigraphical framework for 130-60 ka b2k:new tephra discoveries, marine-based correlations, and future challenges

Building chronological frameworks for proxy sequences spanning 130–60 ka b2k is plagued by difficulties and uncertainties. Recent developments in the North Atlantic region, however, affirm the potential offered by tephrochronology and specifically the search for cryptotephra. Here we review the potential offered by tephrostratigraphy for sequences spanning 130–60 ka b2k. We combine newly identified cryptotephra deposits from the NGRIP ice-core and a marine core from the Iceland Basin with previously published data from the ice and marine realms to construct the first tephrostratigraphical framework for this time-interval. Forty-three tephra or cryptotephra deposits are incorporated into this framework; twenty three tephra deposits are found in the Greenland ice-cores, including nine new NGRIP tephras, and twenty separate deposits are preserved in various North Atlantic marine sequences. Major, minor and trace element results are presented for the new NGRIP horizons together with age estimates based on their position within the ice-core record. Basaltic tephras of Icelandic origin dominate the framework with only eight tephras of rhyolitic composition found. New results from marine core MD99-2253 also illustrate some of the complexities and challenges of assessing the depositional integrity of marine cryptotephra deposits. Tephra-based correlations in the marine environment provide independent tie-points for this time-interval and highlight the potential of widening the application of tephrochronology. Further investigations, however, are required, that combine robust geochemical fingerprinting and a rigorous assessment of tephra depositional processes, in order to trace coeval events between the two depositional realms

Andean drought and glacial retreat tied to Greenland warming during the last glacial period

Abrupt warming events recorded in Greenland ice cores known as Dansgaard-Oeschger (DO) interstadials are linked to changes in tropical circulation during the last glacial cycle. Corresponding variations in South American summer monsoon (SASM) strength are documented, most commonly, in isotopic records from speleothems, but less is known about how these changes affected precipitation and Andean glacier mass balance. Here we present a sediment record spanning the last ~50 ka from Lake Junín (Peru) in the tropical Andes that has sufficient chronologic precision to document abrupt climatic events on a centennial-millennial time scale. DO events involved the near-complete disappearance of glaciers below 4700 masl in the eastern Andean cordillera and major reductions in the level of Peru’s second largest lake. Our results reveal the magnitude of the hydroclimatic disruptions in the highest reaches of the Amazon Basin that were caused by a weakening of the SASM during abrupt arctic warming. Accentuated warming in the Arctic could lead to significant reductions in the precipitation-evaporation balance of the southern tropical Andes with deleterious effects on this densely populated region of South America