‘Sacrificial’ supramolecular assembly and pressure-induced polymerization: toward sequence-defined functionalized nanothreads

Limited supramolecular strategies have been utilized to synthesize sequence-defined polymers, despite the prominence of noncovalent interactions in materials design. Herein, we illustrate the utility of ‘sacrificial’ aryl-perfluoroaryl supramolecular synthons to synthesize sp³-hybridized nanothreads from sp²-enriched reactants. Our strategy features A–B reactant pairs in the form of a phenol:pentafluorophenol co-crystal that is preorganized for an electronically-biased and sequence-defined polymerization. The polymerization, initiated at 12 GPa, affords an alternating copolymer featuring exogenous –OH functionalities. The external substitution is confirmed through IR spectroscopy. Importantly, the inclusion of the functional unit provides the first experimental glimpse at reaction mechanism: keto–enol tautomerization that can only occur during cycloaddition is observed through IR spectroscopy. Our approach realizes the first example of a functionalized nanothread and attains sequence definition through sacrificial supramolecular preorganization and presents a further approach for de novo design of complex nanothreads.

Supramolecular synthons are exploited to synthesize –OH functionalized sp³-rich sequence-defined nanothreads using pressure-induced polymerization of a phenol:pentafluorophenol co-crystal.      

Numerical simulation of Rhonegletscher from 1874 to 2100

Due to climatic change, many Alpine glaciers have significantly retreated during the last century. In this study we perform the numerical simulation of the temporal and spatial change of Rhonegletscher, Swiss Alps, from 1874 to 2007, and from 2007 to 2100.     

Dead regions and pitch perception

The perception of pitch for pure tones with frequencies falling inside low- or high-frequency dead regions (DRs) was examined. Subjects adjusted a variable-frequency tone to match the pitch of a fixed tone. Matches within one ear were often erratic for tones falling in a DR, indicating unclear pitch percepts. Matches across ears of subjects with asymmetric hearing loss, and octave matches within ears, indicated that tones falling within a DR were perceived with an unclear pitch and/or a pitch different from "normal" whenever the tones fell more than 0.5 octave within a low- or high-frequency DR. One unilaterally impaired subject, with only a small surviving region between 3 and 4 kHz, matched a fixed 0.5-kHz tone in his impaired ear with, on average, a 3.75-kHz tone in his better ear. When asked to match the 0.5-kHz tone with an amplitude-modulated tone, he adjusted the carrier and modulation frequencies to about 3.8 and 0.5 kHz, respectively, suggesting that some temporal information was still available. Overall, the results indicate that the pitch of low-frequency tones is not conveyed solely by a temporal code. Possibly, there needs to be a correspondence between place and temporal information for a normal pitch to be perceived.