We measured the viscosity of poly(ethylene glycol) (PEG 6000, 12 000, 20 000) in water using capillary electrophoresis and fluorescence correlation spectroscopy with nanoscopic probes of different diameters (from 1.7 to 114 nm). For a probe of diameter smaller than the radius of gyration of PEG (e.g.rhodamine B or lyzozyme) the measured nanoviscosity was orders of magnitude smaller than the macroviscosity. For sizes equal to (or larger than) the polymer radius of gyration, macroscopic value of viscosity was measured. A mathematical relation for macro and nanoviscosity was found as a function of PEG radius of gyration, Rg, correlation length in semi-dilute solution, ξ, and probe size, R. For R < Rg, the nanoviscosity (normalized by water viscosity) is given by exp(b(R/ξ)a), and for R > Rg, both nano and macroviscosity follow the same curve, exp(b(R/ξ)a), where a and b are two constants close to unity. This mathematical relation was shown to equally well describe rhodamine (of size 1.7 nm) in PEG 20 000 and the macroviscosity of PEG 8 000 000, whose radius of gyration exceeds 200 nm. Additionally, for the smallest probes (rhodamine B and lysozyme) we have verified, using capillary electrophoresis and fluorescence correlation spectroscopy, that the Stokes–Einstein (SE) relation holds, providing that we use a size-dependent viscosity in the formula. The SE relation is correct even in PEG solutions of very high viscosity (three orders of magnitude larger than that of water).
1 December 2004 in The European Physical Journal B
Transverse Brillouin spectra of orthoterphenyl are measured in the (250–305 K; 0.1–100 MPa) temperature-pressure range, which corresponds to the supercooled phase of this organic glass former. We show that the analysis of these spectra combined with an extrapolation of the reorientation times under pressure leads to an estimate of the static shear viscosity in a pressure range whose validity extends beyond the range of the Brillouin measurements. The relative contributions of temperature and of density to the change of this reorientation time measured along an isobar are extracted from our results in a large temperature range extending from the liquid to the low temperature supercooled state. They appear to be always of the same order of magnitude. It is also shown that in the range of the experiment, the orientational time is depending on a unique parameter built on temperature and density.
Bacterial DNA gyrase introduces negative supercoils into chromosomal DNA and relaxes positive supercoils introduced by replication and transiently by transcription. Removal of these positive supercoils is essential for replication fork progression and for the overall unlinking of the two duplex DNA strands, as well as for ongoing transcription. To address how gyrase copes with these topological challenges, we used high-speed single-molecule fluorescence imaging in live Escherichia coli cells. We demonstrate that at least 300 gyrase molecules are stably bound to the chromosome at any time, with ∼12 enzymes enriched near each replication fork. Trapping of reaction intermediates with ciprofloxacin revealed complexes undergoing catalysis. Dwell times of ∼2 s were observed for the dispersed gyrase molecules, which we propose maintain steady-state levels of negative supercoiling of the chromosome. In contrast, the dwell time of replisome-proximal molecules was ∼8 s, consistent with these catalyzing processive positive supercoil relaxation in front of the progressing replisome.
Relaxation times of the α-process in the fragile glass-forming liquid diglycidyl ether of bisphenol-A (EPON 828) were measured in a broad pressure (1–1500 bar) and temperature (264–293 K) ranges by means of the depolarized dynamic light scattering—photon correlation spectroscopy. Based on this experimental data the fragility of the supercooled liquid was calculated in two ways: as a steepness index m of the “Angell plot” and as the -parameter from the Vogel–Fulcher–Tammann Law, and was studied as a function of pressure. It was found, that while the steepness index depends on pressure, the parameter is pressure independent. The pressure dependence of the glass transition temperature in EPON 828 was found to be nonlinear. Additionally, we established a relationship between the steepness index the activation volume and the coefficient In this pressure dependent study we found that also for EPON 828 the nonexponentiality of the correlation function of the α-process correlates well with the non-Arrhenius behavior (steepness index) of the relaxation times. An equation of state describing the temperature and pressure dependence of the structural relaxation time was proposed and verified using experimental data.