Rotational dynamics in supercooled water from nuclear spin relaxation and molecular simulations

Structural dynamics in liquid water slow down dramatically in the supercooled regime. To shed further light on the origin of this super-Arrhenius temperature dependence, we report high-precision (17)O and (2)H NMR relaxation data for H(2)O and D(2)O, respectively, down to 37 K below the equilibrium freezing point. With the aid of molecular dynamics (MD) simulations, we provide a detailed analysis of the rotational motions probed by the NMR experiments. The NMR-derived rotational correlation time τ(R) is the integral of a time correlation function (TCF) that, after a subpicosecond librational decay, can be described as a sum of two exponentials. Using a coarse-graining algorithm to map the MD trajectory on a continuous-time random walk (CTRW) in angular space, we show that the slowest TCF component can be attributed to large-angle molecular jumps. The mean jump angle is ～48° at all temperatures and the waiting time distribution is non-exponential, implying dynamical heterogeneity. We have previously used an analogous CTRW model to analyze quasielastic neutron scattering data from supercooled water. Although the translational and rotational waiting times are of similar magnitude, most translational jumps are not synchronized with a rotational jump of the same molecule. The rotational waiting time has a stronger temperature dependence than the translation one, consistent with the strong increase of the experimentally derived product τ(R)?D(T) at low temperatures. The present CTRW jump model is related to, but differs in essential ways from the extended jump model proposed by Laage and co-workers. Our analysis traces the super-Arrhenius temperature dependence of τ(R) to the rotational waiting time. We present arguments against interpreting this temperature dependence in terms of mode-coupling theory or in terms of mixture models of water structure.     

Cationic polyfluorene: Conformation and aggregation in a “good” solvent

The conjugated polyelectrolyte (CPE) poly{9,9′-bis[6″-(N,N,N-trimethylammonium)-hexylfluorene-alt-co-phenylene] dibromide} (PFPN⁺Br⁻) demonstrates a high solubility in methanol in comparison to other more hydrophilic or hydrophobic solvents. We have employed a combination of pulsed-field-gradient-NMR, photoluminescence (PL), and Raman spectroscopy to establish the conformation and aggregation behavior of PFPN⁺Br⁻ in methanol, with the aim to attain information on how to design CPEs with a high solubility in a preferred solvent. We find that the diffusion coefficient and PL spectrum of PFPN⁺Br⁻, as well as the Raman-active methyl rocking mode of methanol, all exhibit a strong dependence on PFPN⁺Br⁻ concentration. We rationalize our findings with a model in which PFPN⁺Br⁻ forms aggregates via π–π interactions between main-chain segments, while the ionic side chains are surrounded and electrostatically screened by the methanol solvent. Accordingly, the notably high solubility of PFPN⁺Br⁻ in methanol is rationalized by favorable interactions between the ionic side chains and the methanol molecules. We propose that an appropriate design of a high-solubility CPE should consider a matching of the mixed hydrophobic/hydrophilic character of the ionic side chain with that of the preferred solvent.     

The Néron component series of an abelian variety

We introduce the Néron component series of an abelian variety A over a complete discretely valued field. This is a power series in ${\mathbb{Z}}\left[\left[T\right]\right]$ , which measures the behaviour of the number of components of the Néron model of A under tame ramification of the base field. If A is tamely ramified, then we prove that the Néron component series is rational. It has a pole at T = 1, whose order equals one plus the potential toric rank of A. This result is a crucial ingredient of our proof of the motivic monodromy conjecture for abelian varieties. We expect that it extends to the wildly ramified case; we prove this if A is an elliptic curve, and if A has potential purely multiplicative reduction.     

Imaging of Hypochlorous Acid by Fluorescence and Applications in Biological Systems

In recent decades, HOCl research has attracted a lot of scientists from around the world. This chemical species is well known as an important player in the biological systems of eukaryotic organisms including humans. In the human body, HOCl is produced by the myeloperoxidase enzyme from superoxide in very low concentrations (20 to 400 μm ); this species is secreted by neutrophils and monocytes to help fight pathogens. However, in the condition called “oxidative stress”, HOCl has the capability to attack many important biomolecules such as amino acids, proteins, nucleotides, nucleic acids, carbohydrates, and lipids; these reactions could ultimately contribute to a number of diseases such as neurodegenerative diseases (AD, PD, and ALS), cardiovascular diseases, and diabetes. In this review, we discuss recent efforts by scientists to synthesize various fluorophores which are attached to receptors to detect HOCl such as: chalcogen‐based oxidation, oxidation of 4‐methoxyphenol, oxime/imine, lactone ring opening, and hydrazine. These synthetic molecules, involving rational synthetic pathways, allow us to chemoselectively target HOCl and to study the level of HOCl selectivity through emission responses. Virtually all the reports here deal with well‐defined and small synthetic molecular systems. A large number of published compounds have been reported over the past years; this growing field has given scientists new insights regarding the design of the chemosensors. Reversibility, for example is considered important from the stand point of chemosensor reuse within the biological system; facile regenerability using secondary analytes to obtain the initial probe is a very promising avenue. Another aspect which is also important is the energy of the emission wavelength of the sensor; near‐infrared (NIR) emission is favorable to prevent autofluorescence and harmful irradiation of tissue; thus, extended applicability of such sensors can be made to the mouse model or animal model to help image internal organs. In this review, we describe several well‐known types of receptors that are covalently attached to the fluorophore to detect HOCl. We also discuss the common fluorophores which are used by chemist to detect HOCl, Apart from the chemical aspects, we also discuss the capabilities of the compounds to detect HOCl in living cells as measured through confocal imaging. The growing insight from HOCl probing suggests that there is still much room for improvement regarding the available molecular designs, knowledge of interplay between analytes, biological applicability, biological targeting, and chemical switching, which can also serve to further sensor and theurapeutic agent development alike.     

Synthesis and 270 MHz Nmr structural studies of the isomers of 2,3,5-trimethyl- and 2,3,6-trimethylmorpholine

The four isomers of 2,3,5-trimethylmorpholine and those of 2,3,6-trimethylmorpholine have been synthesized from appropriately substituted ethanolamines and separated by means of preparative gas-liquid chromatography. The configuration of each isomer was determined from 270 MHz FT-nmr studies of the magnitudes of the methine-methine and methine-methylene proton coupling constants. The evaluated chemical shifts of axial methyl groups are discussed.     

An explicit method to determine response coefficients in finite elasticity

Some classical solutions to problems involving controllable deformations of isotropic incompressible elastic solids are recapitulated. It is shown that, when only one deformation mechanism is inhomogeneous, a parametric differentiation of the load-deformation relations yields a possibility to determine explicitly the material response coefficients from data conveniently measurable at tests. The method is illustrated for two cases; extension, inflation and torsion of a tube and inflation of a spherical shell.

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Résumé Quelques solutions classiques de problèmes en déformation pour des solides élastiques isotropes incompressibles sont rappelies. On montre que, quand un seul mécanisme est nonhomogène, une dérivation parametrique des relations force-déformation rend possible la détermination explicite des coefficients characteristiques du solide à partir de données expérimentales facilement accessibles.Deux examples illustrent la méthode: cas d'un tube soumis à une extension, une expansion et une torsion et cas d'une coque sphérique en expansion.