Ion‐Specific Assembly of Strong,Tough, and Stiff Biofibers

Designing engineering materials with high stiffness and high toughness is challenging as stiff materials tend to be brittle. Many biological materials realize this objective through multiscale (i.e., atomic‐ to macroscale) mechanisms that are extremely difficult to replicate in synthetic materials. Inspired from the architecture of such biological structures, we here present flow‐assisted organization and assembly of renewable native cellulose nanofibrils (CNFs), which yields highly anisotropic biofibers characterized by a unique combination of high strength (1010 MPa), high toughness (62 MJ m^?3) and high stiffness (57 GPa). We observed that properties of the fibers are primarily governed by specific ion characteristics such as hydration enthalpy and polarizability. A fundamental facet of this study is thus to elucidate the role of specific anion binding following the Hofmeister series on the mechanical properties of wet fibrillar networks, and link this to the differences in properties of dry nanostructured fibers. This knowledge is useful for rational design of nanomaterials and is critical for validation of specific ion effect theories. The bioinspired assembly demonstrated here is relevant example for designing high‐performance materials with absolute structural control.     

Ion‐Specific Assembly of Strong,Tough, and Stiff Biofibers

Designing engineering materials with high stiffness and high toughness is challenging as stiff materials tend to be brittle. Many biological materials realize this objective through multiscale (i.e., atomic‐ to macroscale) mechanisms that are extremely difficult to replicate in synthetic materials. Inspired from the architecture of such biological structures, we here present flow‐assisted organization and assembly of renewable native cellulose nanofibrils (CNFs), which yields highly anisotropic biofibers characterized by a unique combination of high strength (1010 MPa), high toughness (62 MJ m^?3) and high stiffness (57 GPa). We observed that properties of the fibers are primarily governed by specific ion characteristics such as hydration enthalpy and polarizability. A fundamental facet of this study is thus to elucidate the role of specific anion binding following the Hofmeister series on the mechanical properties of wet fibrillar networks, and link this to the differences in properties of dry nanostructured fibers. This knowledge is useful for rational design of nanomaterials and is critical for validation of specific ion effect theories. The bioinspired assembly demonstrated here is relevant example for designing high‐performance materials with absolute structural control.     

Layering and position-dependent diffusive dynamics of confined fluids

We study the diffusive dynamics of a hard-sphere fluid confined between parallel smooth hard walls. The position-dependent diffusion coefficient normal to the walls is larger in regions of high local packing density. High density regions also have the largest available volume, consistent with the fast local diffusivity. Indeed, local and global diffusivities as a function of the Widom insertion probability approximately collapse onto a master curve. Parallel and average normal diffusivities are strongly coupled at high densities and deviate from bulk fluid behavior.     

Catalytic Three‐Component Machinery: Control of Catalytic Activity by Machine Speed

Three supramolecular slider‐on‐deck systems DS1 – DS3 were obtained as two‐component aggregates from the sliders S1 – S3 and deck D with its three zinc porphyrin (ZnPor) binding sites. The binding of the two‐footed slider to the deck varies with the donor qualities of and the steric hindrance at the pyridine/pyrimidine (pyr) feet, and was effected by two N_pyr→ZnPor interactions. Accordingly, the sliders move over the three zinc porphyrins in the deck at different speeds, namely with 32.2, 220, and 440 kHz at room temperature. The addition of N‐methylpyrrolidine as an organocatalyst to DS1 – DS3 generates catalytic three‐component machineries. By using a conjugate addition as a probe reaction, we observed a correlation between the operating speed of the slider‐on‐deck systems and the yields of the catalytic reaction. As the thermodynamic binding of the slider decreases, both the frequency of the sliding motion and the yield of the catalytic reaction increase.     

PNIPAAM Grafted Polymeric Monoliths Synthesized by the Reactive Gelation Process and their Swelling/Deswelling Characteristics

The production of macroporous monoliths functionalized with a thermo‐responsive polymer (PNIPAAM) is described. The surface functionalization was achieved by copolymerization of acrylic end capped atom transfer radical polymerization initiator (BPOEA) with divinylbenzene with or without styrene. Monoliths were generated by swelling them with styrene, BPOEA and divinylbenzene followed by gelation with salt and post polymerization. Subsequent grafting of these monoliths with PNIPAAM was achieved by atom transfer radical polymerization and their swelling deswelling characteristics quantified. The grafted monoliths provide a unique chromatographic stationary phase where adsorption/desorption can be driven by the use of temperature only.

     

Adsorption of basic fuchsin using waste materials--bottom ash and deoiled soya--as adsorbents

Basic fuchsin, a triaminotriphenylmethane dye, was removed by adsorption utilizing two waste materials--"bottom ash," a power plant waste material, and "deoiled soya," an agriculture waste product. The adsorbents were characterized through IR spectroscopy and differential thermal analysis (DTA). Batch adsorption experiments were carried out by measuring effects of pH, adsorbate concentration, sieve size, amount of adsorbent, contact time, temperature, etc. The results have been verified on the basis of Langmuir and Freundlich adsorption isotherm models and data obtained have been applied to calculate thermodynamic parameters. Specific rate constants for the processes were calculated by kinetic measurements and a pseudo-second-order adsorption kinetics was observed in each case. To identify whether the ongoing process is particle diffusion or film diffusion, the treatment given by Boyd and Reichenberg was employed. To assess the practical utility of the adsorbent, the aqueous adsorbate samples were eluted through fixed-bed columns of respective adsorbents. Attempts were also made to recover the adsorbed dyes by passing suitable solvent through the columns.     

Physical adsorption of organic molecules on the surface of layered silicate clay platelets: a thermogravimetric study

Physical adsorption of various adsorbents on the surface of premodified montmorillonite platelets was performed to fully organophilize the inorganic platelets for the purpose of their easy nanoscale dispersion in the polymer matrices during compounding. Different extents of adsorption could be achieved owing to the nature and the functionality of the adsorbents. High molecular weight adsorbents not only enhanced the organic coverage of the platelets but also were observed to contribute toward the thermal stability improvement of the organic modification, thus further fitting the use of such clays for high temperature compounding. The amount of adsorption could also be quantified with respect to the initial amount of adsorbent used in the process. The importance of a clean surface free from any excess surface modification or adsorbent molecules was emphasized. The adsorption process is an effective means to generate such high potential montmorillonites and is much simpler in technique than the common methods of grafting of polymer chains from the clay surface.     

Anomalous particle rotation and resulting microstructure of colloids in AC electric fields

We study the transition of ordered structures to disordered bands and vortices in colloidal suspensions subjected to AC electric fields. We map the critical frequencies and field biases at which particles form disordered bands and vortices. These results are interpreted based on the trajectory dynamics of particle pairs using blinking optical tweezers. Under conditions that vortices are observed, individual particle pairs rotate out of alignment with the field. The direction and magnitude of these interactions determine the orientation and average angular velocity of the band revolution. Increasing the frequency of the electric field reduces the anomalous rotation of the particles pairs, consistent with the frequency dependence of the suspension order-to-disorder transition. This anomalous rotation is consistent with a torque on doublets generated by the mutual polarization of particles and phase lag of the induced dipoles.     

Electrons, phonons and superconductivity in C16 structured Zr2Fe

Inelastic neutron scattering and low-temperature specific heat measurements are reported for a polycrystalline sample of Zr₂Fe. Lattice dynamical calculation of the phonon spectrum, along with first-principles LMTO electronic structure calculations have been used for deriving the specific heat parameters, the electron–phonon coupling constant and the superconducting transition temperature. The results are in fair agreement with the experimental data.     

Computation of two‐dimensional flows past ram‐air parachutes

Computational results for flow past a two‐dimensional model of a ram‐air parachute with leading edge cut are presented. Both laminar (Re=10⁴) and turbulent (Re=10⁶) flows are computed. A well‐proven stabilized finite element method (FEM), which has been applied to various flow problems earlier, is utilized to solve the incompressible Navier–Stokes equations in the primitive variables formulation. The Baldwin–Lomax model is employed for turbulence closure. Turbulent flow computations past a Clarck‐Y airfoil without a leading edge cut, for α=7.5°, result in an attached flow. The leading edge cut causes the flow to become unsteady and leads to a significant loss in lift and an increase in drag. The flow inside the parafoil cell remains almost stagnant, resulting in a high value of pressure, which is responsible for giving the parafoil its shape. The value of the lift‐to‐drag ratio obtained with the present computations is in good agreement with those reported in the literature. The effect of the size and location of the leading edge cut is studied. It is found that the flow on the upper surface of the parafoil is fairly insensitive to the configuration of the cut. However, the flow quality on the lower surface improves as the leading edge cut becomes smaller. The lift‐to‐drag ratio for various configurations of the leading edge cut varies between 3.4 and 5.8. It is observed that even though the time histories of the aerodynamic coefficients from the laminar and turbulent flow computations are quite different, their time‐averaged values are quite similar. Copyright © 2001 John Wiley & Sons, Ltd.