Phase Separation by Entanglement of Active Polymerlike Worms

We investigate the aggregation and phase separation of thin, living T. tubifex worms that behave as active polymers. Randomly dispersed active worms spontaneously aggregate to form compact, highly entangled blobs, a process similar to polymer phase separation, and for which we observe power-law growth kinetics. We find that the phase separation of active polymerlike worms does not occur through Ostwald ripening, but through active motion and coalescence of the phase domains. Interestingly, the growth mechanism differs from conventional growth by droplet coalescence: the diffusion constant characterizing the random motion of a worm blob is independent of its size, a phenomenon that can be explained from the fact that the active random motion arises from the worms at the surface of the blob. This leads to a fundamentally different phase-separation mechanism that may be unique to active polymers.Comment: 4 pages, 4 figure

Polarization-modulation setup for ultrafast infrared anisotropy experiments to study liquid dynamics

An infrared pump-probe setup using rapid polarization modulation has been developed to perform time-resolved vibrational anisotropy measurements. A photo-elastic modulator is used as a rapidly switchable half-wave plate, enabling the measurement of transient absorptions for parallel and perpendicular polarizations of the pump and probe pulses on a shot-to-shot basis. In this way, infrared intensity fluctuations are nearly completely canceled, significantly enhancing the accuracy of the transient-anisotropy measurement. The method is tested on the OD-stretch vibration of HDO in H2O, for which the signal-to-noise ratio is found to be 4 times better than with conventional methods

Lifetime-Associated Two-Dimensional Infrared Spectroscopy Reveals the Hydrogen-Bond Structure of Supercooled Water in Soft Confinement

[Image: see text] We demonstrate a method to address the problem of spectral overlap in multidimensional vibrational spectroscopy and use it to investigate supercooled aqueous sorbitol solutions. The absence of crystallization in these solutions has been attributed to “soft” confinement of water in subnanometer voids in the sorbitol matrix, but the details of the hydrogen-bond structure are still largely unknown. 2D-IR spectroscopy of the OH-stretch mode is an excellent tool to investigate hydrogen bonding, but in this case it seems difficult because of the overlapping water and sorbitol contributions to the 2D-IR spectrum. Using the difference in OH-stretch lifetimes of water and sorbitol we can cleanly separate these contributions. Surprisingly, the separated 2D-IR spectra show that the hydrogen-bond disorder of soft-confined water is independent of temperature and decoupled from its orientational order. We believe the approach we use to separate overlapping 2D-IR spectra will enhance the applicability of 2D-IR spectroscopy to study multicomponent systems

D₂O as an Imperfect Replacement for H₂O:Problem or Opportunity for Protein Research?

D2O is commonly used as a solvent instead of H2O in spectroscopic studies of proteins, in particular, in infrared and nuclear-magnetic-resonance spectroscopy. D2O is chemically equivalent to H2O, and the differences, particularly in hydrogen-bond strength, are often ignored. However, replacing solvent water with D2O can affect not only the kinetics but also the structure and stability of biomolecules. Recent experiments have shown that even the mesoscopic structures and the elastic properties of biomolecular assemblies, such as amyloids and protein networks, can be very different in D2O and H2O. We discuss these findings, which probably are just the tip of the iceberg, and which seem to call for obtaining a better understanding of the H2O/D2O-isotope effect on water-water and water-protein interactions. Such improved understanding may change the differences between H2O and D2O as biomolecular solvents from an elephant in the room to an opportunity for protein research.</p

On the origin of the extremely different solubilities of polyethers in water

The solubilities of polyethers are surprisingly counter-intuitive. The best-known example is the difference between polyethylene glycol ([–CH2–CH2–O–]n) which is infinitely soluble, and polyoxymethylene ([–CH2–O–]n) which is completely insoluble in water, exactly the opposite of what one expects from the C/O ratios of these molecules. Similar anomalies exist for oligomeric and cyclic polyethers. To solve this apparent mystery, we use femtosecond vibrational and GHz dielectric spectroscopy with complementary ab initio calculations and molecular dynamics simulations. We find that the dynamics of water molecules solvating polyethers is fundamentally different depending on their C/O composition. The ab initio calculations and simulations show that this is not because of steric effects (as is commonly believed), but because the partial charge on the O atoms depends on the number of C atoms by which they are separated. Our results thus show that inductive effects can have a major impact on aqueous solubilities

Local orientational order in liquids revealed by resonant vibrational energy transfer

We demonstrate that local orientational ordering in a liquid can be observed in the decay of the vibrational anisotropy caused by resonant transfer of vibrational excitations between its constituent molecules. We show that the functional form of this decay is determined by the (distribution of) angles between the vibrating bonds of the molecules between which energy transfer occurs, and that the initial drop in the decay reflects the average angle between nearest neighbors. We use this effect to observe the difference in local orientational ordering in the two hydrogen-​bonded liquids ethanol and N-​methylacetamide