Conductive block copolymer elastomers and psychophysical thresholding for accurate haptic effects.

Electrotactile stimulus is a form of sensory substitution in which an electrical signal is perceived as a mechanical sensation. The electrotactile effect could, in principle, recapitulate a range of tactile experience by selective activation of nerve endings. However, the method has been plagued by inconsistency, galvanic reactions, pain and desensitization, and unwanted stimulation of nontactile nerves. Here, we describe how a soft conductive block copolymer, a stretchable layout, and concentric electrodes, along with psychophysical thresholding, can circumvent these shortcomings. These purpose-designed materials, device layouts, and calibration techniques make it possible to generate accurate and reproducible sensations across a cohort of 10 human participants and to do so at ultralow currents (≥6 microamperes) without pain or desensitization. This material, form factor, and psychophysical approach could be useful for haptic devices and as a tool for activation of the peripheral nervous system.

Decoupling Planarizing and Steric Energetics to Accurately Model the Rigidity of π-Conjugated Polymers.

The π-conjugated backbone of semiconducting polymers gives rise to both their electronic properties and structural rigidity. However, current computational methods for understanding the rigidity of polymer chains fail in one crucial way. Namely, standard torsional scan (TS) methods do not satisfactorily capture the behavior of polymers exhibiting a high degree of steric hindrance. This deficiency in part stems from the method by which torsional scans decouple energy related to electron delocalization from that related to nonbonded interactions. These methods do so by applying classical corrections of the nonbonded energy to the quantum mechanical (QM) torsional profile for polymers that are highly sterically hindered. These large corrections to the energy from nonbonded interactions can substantially skew the calculated QM energies related to torsion, resulting in an inaccurate or imprecise estimation of the rigidity of a polymer. As a consequence, simulations of the morphology of a highly sterically hindered polymer using the TS method can be highly inaccurate. Here, we describe an alternative, generalizable method by which the delocalization energy can be decoupled from the energy associated with nonbonded interactions─the "isolation of delocalization energy" (DE) method. From torsional energy calculations, we find that the relative accuracy of the DE method is similar to the TS method (within 1 kJ/mol) for two model polymers (P3HT, PTB7) when compared to quantum mechanical calculations. However, the DE method significantly increased the relative accuracy for simulations of PNDI-T, a highly sterically hindered polymer (8.16 kJ/mol). Likewise, we show that comparison of the planarization energy (i.e., backbone rigidity) from torsional parameters is significantly more precise for both PTB7 and PNDI-T when using the DE method as opposed to the TS method. These differences affect the simulated morphology, with the DE method predicting a significantly more planar configuration of PNDI-T.

Complete inhibition of a polyol nucleation by a micromolar biopolymer additive.

Preventing spontaneous crystallization of supersaturated solutions by additives is of critical interest to successful process design and implementation, with numerous applications in chemical, pharmaceutical, medical, pigment, and food industries, but challenges remain in laboratory and industry settings and fundamental understanding is lacking. When copresented with antifreeze proteins (AFPs), otherwise spontaneously crystallizing osmolytes are maintained at high supersaturations for months in over-wintering organisms. Thus, we here explore the inhibition phenomenon by AFPs, using persistent crystallization of a common sugar alcohol, D-mannitol, as a case study. We report experimentally that DAFP1, an insect AFP, completely inhibits D-mannitol nucleation. Computer simulations reveal a new mechanism for crystallization inhibition where the population of the crystal-forming conformers are selectively bound and randomized in solution by hydrogen bonding to the protein surface. These results highlight the advantages of using natural polymers to address crystallization inhibition challenges and suggest new strategies in controlling the nucleation processes.