Synthesis and surface properties of environmentally responsive segmented polyurethanes

Polyurethanes, containing well-defined assemblies of perfluoro-polyether (PFPE or hexafluoropropene oxide oligomer), polydimethylsiloxane (PDMS), and polyethylene glycol (PEG) segments, exhibit oleophobic, hydrophobic, and hydrophilic properties in response to the polarity of the contacting medium. These polymers were prepared by reacting hydroxy(polyethyleneoxy)-propylether-terminated PDMS block copolymer (HO-PEG-PDMS-PEG-OH) with 4,4'-methylene-bis(phenylene isocyanate) (MDI) in the presence of dibutyltin dilaurate catalyst, followed by reaction with 1,2-diol functional PFPE and chain extension with 2,2,3,3-tetrafluoro-1,4-butanediol (FB). The oleophobic and hydrophobic properties of the segmented polyurethanes (SPU) are due to the segregation of PFPE segments at the polymer-air interface. Wettability studies revealed that the same surface becomes hydrophilic, presumably due to the segregation of the PEG segments at the polymer-water interface. This hydrophobic-to-hydrophilic transformation of the surface prevails not only when the polymer is in contact with liquid water but with water vapor as well. The understanding of the reconstruction mechanism of this novel family of SPU surfaces would furnish valuable information for various applications where dynamic transformation of surface activity is desired.     

Studying friction and shear fracture in thin confined films using a rotational shear apparatus

This paper describes the effects of the elastic modulus and sliding velocity on the friction and shear fracture of smooth silanized rigid disks rotating against thin confined films of poly(dimethylsiloxane) (PDMS) elastomers. A rigid glass disk is rotated against thin PDMS films of different thicknesses and moduli bonded to a glass plate at various speeds. While the disk rotates on the PDMS coated glass plate, a load cell measures the resulting force with a cantilever beam. One end of the cantilever beam is glued to the glass plate, while its other end presses against a load cell. From the balance of forces and torques, the friction force at a given slip velocity is determined. The friction force increases with the slip velocity sublinearly, which is consistent with the results reported previously by Vorvolakos and Chaudhury (Langmuir 2003, 19, 6778). During rotation, however, the glass disk comes off the PDMS film when the shear stress reaches a critical value. This critical shear stress increases with the modulus of the film, but it decreases with its thickness, following a square root relationship, which is similar to the adhesive fracture behavior in thin films under pull-off conditions. A simple model is presented that captures the essential physics of the fracture behavior under shear mode.     

Stochastic rolling of a rigid sphere in weak adhesive contact with a soft substrate

We study the rolling motion of a small solid sphere on a fibrillated rubber substrate in an external field in the presence of a Gaussian noise. From the nature of the drift and the evolution of the displacement fluctuation of the ball, it is evident that the rolling is controlled by a complex non-linear friction at a low velocity and a low noise strength (K), but by a linear kinematic friction at a high velocity and a high noise strength. This transition from a non-linear to a linear friction control of motion can be discerned from another experiment in which the ball is subjected to a periodic asymmetric vibration in conjunction with a random noise. Here, as opposed to that of a fixed external force, the rolling velocity decreases with the strength of the noise suggesting a progressive fluidization of the interface. A state (K) and rate (V) dependent friction model is able to explain both the evolution of the displacement fluctuation as well as the sigmoidal variation of the drift velocity with K. This research sets the stage for studying friction in a new way, in which it is submitted to a noise and then its dynamic response is studied using the tools of statistical mechanics. Although more works would be needed for a fuller realization of the above-stated goal, this approach has the potential to complement direct measurements of friction over several decades of velocities and other state variables. It is striking that the non-Gaussian displacement statistics as observed with the stochastic rolling is similar to that of a colloidal particle undergoing Brownian motion in contact with a soft microtubule.     

An improved pollen collection and cryopreservation method for highly recalcitrant tropical fruit species of mango (Mangifera indica L.) and litchi (Litchi chinensis Sonn.)

An improved method for pollen collection from freshly dehiscing anthers of mango (Mangifera indica L.) and litchi (Litchi chinensis Sonn.) using the organic solvent cyclohexane has been devised. Using this method pollen quantity sufficient for large scale pollinations could be collected and stored for future use. Transport of pollen in viable conditions over long distances, from site of collection (field genebank) to cryolab was successfully devised for both these fruit species. Cryopreservation was successfully applied to achieve long-term pollen storage over periods of up to four years. Pollen viability was tested using in vitro germination, the fluorochromatic reaction (FCR) method and by fruit set following field pollination. On retesting, four year cryostored pollen of different mango and litchi varieties showed high percentage viability as good as fresh control pollens. Pollens of more than 180 cultivars of mango and 19 cultivars of litchi have been stored in the cryogenebank using the technology developed, thus facilitating breeding programmes over the long-term.     

Oxoanionic or sulfur lone pair attack? The difference in reactivity of hydrogensulfite anion and neutral dimethylsulfite towards [Bu4N]2[MoO2(S2C2)CN)2)2] in the model reductive half reaction of sulfite oxidase

pH dependent reactivity differences of dimethylsulfite towards the title complex 1 demonstrate the crucial need of oxo-anionic coordination of sulfite to the molybdenum centre of 1 in the model reductive half reaction of sulfite oxidase.     

Full energy peak efficiency calibration of HPGe detector for point and extended sources using Monte Carlo code

Monte Carlo simulation is important to get efficiencies for cases where the experimental efficiencies are difficult to get such as for samples with nonstandard geometries and for large samples. In this paper, efficiency of the HPGe detector, routinely used in our lab for a variety of samples, has been computed for point source geometry and its parameters has been optimized to match MCNP and experimental efficiencies within 5% at different sample to detector distances. This optimized geometry was then validated by efficiency transfer to other geometries.     

Evolution of defect states in doped polythiophene: A study based on the method of simulated annealing

A modified Su–Schrieffer–Heeger Hamiltonian‐based model is used to compute the electronic and geometric structures of fairly long polythiophene (PT) chains, neutral as well as doped. The geometry optimization is carried out by the simulated annealing method. Both Metropolis and Glauber functions are used for sampling. It is shown that a bipolaron can be structurally represented by a fragment of the PT chain containing 14 thiophene units. As a series of bipolaronic defects are introduced in a long PT chain (50–100 rings), the highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gap energy (Δ) becomes vanishingly small, a feature not present in the PT chains of similar sizes containing polaronic defects. The Fermi energy level (E_F) also moves into the valency band and nonzero density of states at ? = E_F are created. Once again, this feature is shown to be missing in PT chains containing polaronic defects. Implications of these findings are analyzed. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003