Interfacial assembly of star-shaped polymers for organized ultrathin films

Surface-assisted directed assembly allows ultrasoft and replusive functional polymeric “colloids” to assemble into the organized supramolecular ultrathin films on a monomolecular level. This study aims at achieving a fundamental understanding of molecular morphology and responsive behavior of major classes of branched star-shaped polymers (star amphiphilic block copolymers and star polyelectrolytes) and their aggregation into precisely engineered functional ultrathin nanofilms. Thus, we focus on elucidating the role of molecular architecture, chemical composition, and intra/intermolecular interactions on the assembly behavior of highly-branched entities under variable environmental and confined interfacial conditions. The inherent molecular complexity of branched architectures facilitates rich molecular conformations and phase states from the combination of responsive dynamics of flexible polymer chains (amphiphilic, ionizable arms, multiple segments, and free chain ends) and extened molecular design parameters (number of arms, arm length, and segment composition/sequence). These marcromolecular building components can be affected by external conditions (pH, salinity, solvent polarity, concentration, surface pressure, and substrate nature) and transformed into a variety of complex nanostructures, such as two-dimensional circular micelles, core/shell unimicelles, nanogel particles, pancake & brush micelles, Janus-like nanoparticles, and highly nanoporous fractal networks. The fine balance between repulsive mulitarm interactions and surface energetic effects in the various confined surfaces and interfaces enables the ability to fabricate and tailor well-organized ultrathin nanofilms. The most critical findings in this study include: (1) densely packed circular unimicelle monolayers from amphiphilic and amphoteric multiblock stars controlled by arm number, end blocks, and pH/pressure induced aggregation, (2) monolayer polymer-metal nanocomposites by in-situ nanoparticle growth at confined interfaces, (3) on-demand control of exponentially or linearly grown heterogeneous stratified multilayers from self-diffusive pH-sensitive star polyelectrolyte nanogels, (4) core/shell umimicelle based microcapsules with a fractal nanoporous multidomain shell morphology, and (5) preferential binding and ordering of Janus-like unimicelles on chemically heterogeneous graphene oxide surfaces for biphasic hybrid assembly. The advanced branched molecular design coupled with stimuli responsive conformational and compositional behavior presents an opportunity to control the lateral diffusion and phase segregation of branched compact supermolecules on the surface resulting in the generation of well-controllable monolayers with tunable ordering and complex morphology, as well as to tailor their stratified layered nanostructures with switchable morphological heterogeneity and multicompartmental architectures. These surface-driven star polymer supramolecular assemblies and interfaces will enable the design of multifunctional nanofilms as hierarchical responsive polymer materials.Ph.D

Geomechanical stability of the caprock during CO2 sequestration in deep saline aquifers

8 páginas, 5 figuras.Sequestration of carbon dioxide (CO2) in deep saline aquifers has emerged as a mitigation strategy for reducing greenhouse gas emissions to the atmosphere. The large amounts of supercritical CO2 that need to be injected into deep saline aquifers may cause large fluid pressure buildup. The resulting overpressure will produce changes in the effective stress field. This will deform the rock and may promote reactivation of sealed fractures or the creation of new ones in the caprock seal, which could lead to escape paths for CO2. To understand these coupled hydromechanical phenomena, we model an axisymmetric horizontal aquifer-caprock system. We study plastic strain propagation patterns using a viscoplastic approach. Simulations illustrate that plastic strain may propagate through the whole thickness of the caprock if horizontal stress is lower than vertical stress. In contrast, plastic strain concentrates in the contact between the aquifer and the caprock if horizontal stress is larger than vertical stress. Aquifers that present a low-permeability boundary experience an additional fluid pressure increase once the pressure buildup cone reaches the outer boundary. However, fluid pressure does not evolve uniformly in the aquifer. While it increases in the low-permeability boundary, it drops in the vicinity of the injection well because of the lower viscosity of CO2. Thus, caprock stability does not get worse in semi-closed aquifers compared to open aquifers. Overall, the caprock acts as a plate that bends because of pressure buildup, producing a horizontal extension of the upper part of the caprock. This implies a vertical compression of this zone, which may produce settlements instead of uplift in low-permeability (k≤10-18 m2) caprocks at early times of injection.V.V. would like to acknowledge the Spanish Ministry of Science and Innovation (MIC) for financial support through the “Formación de Profesorado Universitario” program. V.V. also wishes to acknowledge the “Colegio de Ingenieros de Caminos, Canales y Puertos – Catalunya” for their financial support. This project has been funded by the Spanish Ministry of Science and Innovation through the project CIUDEN (Ref.: 030102080014), and through the MUSTANG project, from the European Community’s Seventh Framework Programme FP7/2007-2013 under grant agreement nº 227286.Peer reviewe

Inkjet-Assisted Layer-by-Layer Printing of Encapsulated Arrays

We present the facile fabrication of hydrogen-bonded layer-by-layer (LbL) microscopic dot arrays with encapsulated dye compounds. We demonstrate patterned encapsulation of Rhodamine dye as a model compound within poly­(vinylpyrrolidone)/poly­(methacrylic acid) (PVPON/PMAA) LbL dots constructed without an intermediate washing step. The inkjet printing technique improves encapsulation efficiency, reduces processing time, facilitates complex patterning, and controls lateral and vertical dimensions with diameters ranging from 130 to 35 μm (mostly controlled by the droplet size and the substrate hydrophobicity) and thickness of several hundred nanometers. The microscopic dots composed of hydrogen-bonded PVPON/PMAA components are also found to be stable in acidic solution after fabrication. This facile, fast, and sophisticated inkjet encapsulation method can be applied to other systems for fast fabrication of large-scale, high-resolution complex arrays of dye-encapsulated LbL dots

pH-Controlled Exponential and Linear Growing Modes of Layer-by-Layer Assemblies of Star Polyelectrolytes

A novel solventless sample preparation, stir-bar sorptive extraction (SBSE), for extraction, and sample enrichment of organic compounds from biological fluids, is described in this manuscript from principle to applications. The SBSE is based on sorptive extraction, whereby the compounds are extracted into a polymer coating, polydimethylsiloxane (PDMS), on a magnetic stirring rod. The extraction is controlled by the partitioning coefficient of drugs between the PDMS and sample matrix, and upon the sample-extraction medium phase ratio. The SBSE technique has been applied successfully, with high sensitivities, to biomedical analysis of volatiles and for semi-volatiles drugs from biological sample, including urine, plasma, and saliva. SBSE combined with in situ derivatization, drugs quite more polar (e.g. metabolites) also can be analyzed

ENDE: An End-to-End Network Delay Emulator

ENDE: An End-to-end Network Delay Emulator. (August 1998) Ikjun Yeom, B.S.,Yonsei University Chair of Advisory Committee: Reddy, Dr. Narasimha The Internet provides a common interface between different types of computers and networks, and various applications and protocols are constantly being developed. A new protocol or application after being developed has to be tested on the real Internet or simulated on a testbed for debugging and performance evaluation. A protocol developer typically requires access to multiple machines across the Internet for this reason. In this thesis we present a new tool that can emulate end-to-end delays between two hosts without requiring access to the second host. The tool enables the user to test new protocols realistically on a single machine. The tool observes network status on a particular path using ICMP packets and uses it as a real-time traffic source. Experimented results are presented to show that this approach is effective and quite accurate. ..

Технічний проект будинкового газопостачання житлового району м. Харків з удосконаленням конструкції регулятора тиску газу

Практичні результати: – виконано аналіз об’єкту газифікації; – розроблено проект газопостачання району населеного пункту; – удосконалено конструкцію регулятора тиску газу; – проведено аналіз з охорони праці та навколишнього середовища.Мета роботи – розробка проекту газопостачання району населеного пункту м. Харків з удосконаленням конструкції регулятора тиску газу

SIRT1 Activation Attenuates the Cardiac Dysfunction Induced by Endothelial Cell-Specific Deletion of CRIF1

The CR6-interacting factor1 (CRIF1) mitochondrial protein is indispensable for peptide synthesis and oxidative phosphorylation. Cardiomyocyte-specific deletion of CRIF1 showed impaired mitochondrial function and cardiomyopathy. We developed an endothelial cell-specific CRIF1 deletion mouse to ascertain whether dysfunctional endothelial CRIF1 influences cardiac function and is mediated by the antioxidant protein sirtuin 1 (SIRT1). We also examined the effect of the potent SIRT1 activator SRT1720 on cardiac dysfunction. Mice with endothelial cell-specific CRIF1 deletion showed an increased heart-to-body weight ratio, increased lethality, and markedly reduced fractional shortening of the left ventricle, resulting in severe cardiac dysfunction. Moreover, endothelial cell-specific CRIF1 deletion resulted in mitochondrial dysfunction, reduced ATP levels, inflammation, and excessive oxidative stress in heart tissues, associated with decreased SIRT1 expression. Intraperitoneal injection of SRT1720 ameliorated cardiac dysfunction by activating endothelial nitric oxide synthase, reducing oxidative stress, and inhibiting inflammation. Furthermore, the decreased endothelial junction-associated protein zonula occludens-1 in CRIF1-deleted mice was significantly recovered after SRT1720 treatment. Our results suggest that endothelial CRIF1 plays an important role in maintaining cardiac function, and that SIRT1 induction could be a therapeutic strategy for endothelial dysfunction-induced cardiac dysfunction

Star Polymer Unimicelles on Graphene Oxide Flakes

We report the interfacial assembly of amphiphilic heteroarm star copolymers (PS_<i>n</i>P2VP_<i>n</i> and PS_<i>n</i>(P2VP-<i>b</i>-P<i>t</i>BA)_<i>n</i> (<i>n</i> = 28 arms)) on graphene oxide flakes at the air–water interface. Adsorption, spreading, and ordering of star polymer micelles on the surface of the basal plane and edge of monolayer graphene oxide sheets were investigated on a Langmuir trough. This interface-mediated assembly resulted in micelle-decorated graphene oxide sheets with uniform spacing and organized morphology. We found that the surface activity of solvated graphene oxide sheets enables star polymer surfactants to subsequently adsorb on the presuspended graphene oxide sheets, thereby producing a bilayer complex. The positively charged heterocyclic pyridine-containing star polymers exhibited strong affinity onto the basal plane and edge of graphene oxide, leading to a well-organized and long-range ordered discrete micelle assembly. The preferred binding can be related to the increased conformational entropy due to the reduction of interarm repulsion. The extent of coverage was tuned by controlling assembly parameters such as concentration and solvent polarity. The polymer micelles on the basal plane remained incompressible under lateral compression in contrast to ones on the water surface due to strongly repulsive confined arms on the polar surface of graphene oxide and a preventive barrier in the form of the sheet edges. The densely packed biphasic tile-like morphology was evident, suggesting the high interfacial stability and mechanically stiff nature of graphene oxide sheets decorated with star polymer micelles. This noncovalent assembly represents a facile route for the control and fabrication of graphene oxide-inclusive ultrathin hybrid films applicable for layered nanocomposites