Using polymer brushes to tune the structure-plasmonic relationship in polymer nanocomposites containing nanorods

The thermodynamic factors that affect the dispersion of polymer-brush grafted gold nanorods (NRs) added to polymer matrix films have been studied by experiment and theory. When the brush (degree of polymerization N) and matrix (degree of polymerization P) have a favorable interaction (enthalpy driven), NRs uniformly disperse in the matrix, independent of P/N. When the brush and matrix are chemically similar, NRs randomly disperse for P/N \u3c 2 (i.e., wet brush), but align side-by-side for P/N \u3e 2. UV-visible spectroscopy is used to investigate the structure-optical property relationship as function of P/N. For P/N \u3e 2, self-consistent field theory (SCFT) and density functional theory (DFT) indicate that NR aggregation correlates with rod-rod interactions greater than -5kT. As NR aspect ratio (AR) increases, dry and wet brush behavior is observed for ARs from 2.5 to 6.3. For P/N \u3c 2, long NRs exhibit much longer range local order than short NRs and corresponding strong blue shift in the longitudinal surface plasmon resonance (LSPR). Chemically mixed brushes on NR surfaces provide another means to tune NR dispersion. To induce end-to-end linking, Au NRs are selectively functionalized with dithols and peptides to create permanent and revisable linking as well as a red shift in the LSPR

Experimental Validation Of An Integrated Guidance And Control System For Marine Surface Vessels

Autonomous operation of marine surface vessels is vital for minimizing human errors and providing efficient operations of ships under varying sea states and environmental conditions which is complicated by the highly nonlinear dynamics of marine surface vessels. To deal with modelling imprecision and unpredictable disturbances, the sliding mode methodology has been employed to devise a heading and a surge displacement controller. The implementation of such a controller necessitates the availability of all state variables of the vessel. However, the measured signals in the current study are limited to the global X and Y positioning coordinates of the boat that are generated by a GPS system. Thus, a nonlinear observer, based on the sliding mode methodology, has been implemented to yield accurate estimates of the state variables in the presence of both structured and unstructured uncertainties. Successful autonomous operation of a marine surface vessel requires a holistic approach encompassing a navigation system, robust nonlinear controllers and observers. Since the overwhelming majority of the experimental work on autonomous marine surface vessels was not conducted in truly uncontrolled real-world environments. The first goal of this work was to experimentally validate a fully-integrated LOS guidance system with a sliding mode controller and observer using a 16’ Tracker Pro Guide V-16 aluminium boat with a 60 hp. Mercury outboard motor operating in the uncontrolled open-water environment of Lake St. Clair, Michigan. The fully integrated guidance and controller-observer system was tested in a model-less configuration, whereby all information provided from the vessel’s nominal model have been ignored. The experimental data serves to demonstrate the robustness and good tracking characteristics of the fully-integrated guidance and controller/observer system by overcoming the large errors induced at the beginning of each segment and converging the boat to the desired trajectory in spite of the presence of environmental disturbances. The second focus of this work was to combine a collision avoidance method with the guidance system that accounted for “International Regulations for Prevention of Collisions at Sea” abbreviated as COLREGS. This new system then needed to be added into the existing architecture. The velocity obstacles method was selected as the base to build upon and additional restrictions were incorporated to account for these additional rules. This completed system was then validated with a software in the loop simulation

Breakdown of Dynamic Scaling in Thin Film Binary Liquids Undergoing Phase Separation

The kinetics of phase separation in thin polymer blend films displaying discrete and bicontinuous domain morphologies are examined. For discrete domains, the correlation length ξ grows as t1/3, in agreement with a coalescence model. By plotting ξ/d vs t/ti (initiation time), universal growth behavior is obtained for thickness values (d) from 1000 to 190 nm. In contrast, bicontinuous domains grow with a decreasing exponent, 0.62 to 0.28, as d decreases from 900 to 90 nm (i.e., no universal growth). This slowing down with reduced dimensionality suggests suppression of lateral hydrodynamic pumping

Polymer conformations in polymer nanocomposites containing spherical nanoparticles

We investigate the effect of various spherical nanoparticles on chain dimensions in polymer melts for high nanoparticle loading which is larger than the percolation threshold, using molecular dynamics simulations. We show that polymer chains are unperturbed by the presence of repulsive nanoparticles. In contrast polymer chains can be perturbed by the presence of attractive nanoparticles when the polymer radius of gyration is larger than the nanoparticle radius. At high nanoparticle loading, chains can be stretched and flattened by the nanoparticles, even oligomers can expand under the presence of attractive nanoparticles of very small size

Biomimetic dextran coatings on silicon wafers : thin film properties and wetting

There has been much recent interest in polysaccharide coatings for biotechnology applications. We obtained highly wettable dextran coatings applied to flat silicon wafer surfaces through a two-step process: in the first step, the silicon is aminated by the deposition of a selfassembled monolayer of 3-aminopropyltriethoxysilane (APTES); in the second step, polydisperse and low dispersity dextrans with molecular weights ranging from 1 kDa to 100 kDa are covalently grafted along the backbone to the surface amino groups to achieve strong interfacial anchoring. The effect of dextran concentration on film thickness and contact angle is investigated. Atomic force microscopy (AFM) has been employed to characterize surface roughness and coverage of the dextrans as well as the APTES monolayers. The synthetic surfaces were also tested for gas bubble adhesion properties

Entanglements in polymer nanocomposites containing spherical nanoparticles

We investigate the polymer packing around nanoparticles and polymer/nanoparticle topological constraints (entanglements) in nanocomposites containing spherical nanoparticles in comparison to pure polymer melts using molecular dynamics (MD) simulations. The polymer–nanoparticle attraction leads to good dispersion of nanoparticles. We observe an increase in the number of topological constraints (decrease of total entanglement length Ne with nanoparticle loading in the polymer matrix) in nanocomposites due to nanoparticles, as evidenced by larger contour lengths of the primitive paths. An increase of the nanoparticle radius reduces the polymer–particle entanglements. These studies demonstrate that the interaction between polymers and nanoparticles does not affect the total entanglement length because in nanocomposites with small nanoparticles, the polymer–nanoparticles topological constraints dominat

Dextran grafted silicon substrates : preparation, characterization and biomedical applications

Biodevices used in the cardiovascular system suffer from well-known problems associated with surface-induced gas embolism and thrombosis. In order to improve the biocompatibility of these devices, biomimetic coatings show good promise. We recently synthesized a coating layer of dextran, a relatively simple and well characterized neutral polysaccharide, with the purpose of mimicking the cells\u27 glycocalyx layer, that prevents non-specific cells-protein interactions. Systematic physical chemical characterization was performed on coatings obtained both from commonly used polydisperse dextrans and low-dispersity dextrans in the 1-100 kDalton molecular weight range. We have combined standard surface analysis techniques, such as ellipsometry, contact angle measurements and AFM, with less traditional vibrational spectroscopy techniques in the characterization of our biomimetic coatings. FTIR, micro-FTIR and micro-Raman spectroscopies were utilized to correlate the conformational and molecular aspects of the grafted poly- and monodisperse dextran chains to their attractive biological properties