Anisotropic Ionic Mobility of Lithium Salts in Lamellar Liquid Crystalline Polymer Networks

New mesogens presenting smectic A (SmA) phases and capable of hosting lithium salts are designed. The mesogens comprise a vinyl‐functionalized spacer to allow further reaction to the polymer backbone, an aromatic core and ethylene oxide chains, able to coordinate lithium ions. Copolymerizing these monomers with a suitable crosslinker yields the first lithium containing liquid crystalline elastomers (LCEs). The SmA structure where the ethylene oxide chains are microphase separated in layers is fixed by the crosslinking and permanent macroscopic orientation is obtained. Diffusion and conductivity measurements of the monomer sample show a large anisotropy of the ion mobility (100 for the cation and 400 for the anion). In the elastomer the anisotropy of the lithium mobility is comparable to that in the monomers.     

Identification of isomeric 5‐hydroxytryptophan‐ and oxindolylalanine‐containing peptides by mass spectrometry

Cells continuously produce reactive oxidative species that can modify all cellular components. In proteins, for example, cysteine, methionine, tryptophan (Trp), and tyrosine residues are particularly prone to oxidation. Here, we report two new approaches to distinguish two isomeric oxidation products of Trp residues, i.e. 5‐hydroxytryptophan (5‐HTP) and oxindolylalanine (Oia) residues, in peptides. First, 2‐nitrobenzenesulfenyl chloride, known to derivatize Trp residues in position 2 of the indole ring, was used to label 5‐HTP residues. The mass shift of 152.98 m/z units allowed identifying 5‐HTP‐ besides Trp‐containing peptides by mass spectrometry, whereas Oia residues were not labeled. Second, fragmentation of the Oia‐ and 5‐HTP‐derived immonium ions at m/z 175.08 produced ions characteristic for each residue that allowed their identification even in the presence of y₁ ions at m/z 175.12 derived from peptides with C‐terminal arginine residues. The pseudo MS³ spectra acquired on a quadrupole time‐of‐flight hybrid mass spectrometer displayed two signals at m/z 130.05 and m/z 132.05 characteristic for Oia‐containing peptides and a group of six signals (m/z 103.04, 120.04, 130.04, 133.03, 146.04, and 148.04) for 5‐HTP‐cointaining peptides. In both cases, the relative signal intensities appeared to be independent of the sequence providing a specific fingerprint of each oxidative modification. Copyright © 2012 John Wiley & Sons, Ltd.     

An Almost Accurate Location of the Maximum Stirling Number(s) of the Second Kind

The Stirling number of the second kind S(n, k) is the number of ways of partitioning a set of n elements into k nonempty subsets. It is well known that the numbers S(n, k) are unimodal in k, and there are at most two consecutive values K _n such that (for fixed n) S(n, K _n ) is maximal. We determine asymptotic bounds for K _n , which are unexpectedly good and improve earlier results. The method used here shows a possible strategy for obtaining numerical bounds such that in almost all cases K _n can be uniquely determined.     

Monotonicity Properties of the Riemann Zeta Function

Let $$F_{a}(s) = \left(1 - 1\frac{1}{\zeta(s)}\right)^{1/(s-a)}(a \leq 1; s > 1),$$ where ?? denotes the Riemann zeta function. We prove: F _a is strictly decreasing on (1, ??) if and only if a ?? 0, whereas F _a is strictly increasing on (1, ??) if and only if a =?1. In particular, this settles a conjecture of Batir, who claimed that F ₀ is strictly monotonic for s >?1. Moreover, we apply the monotonicity theorem to obtain some inequalities involving F _a .     

The transition from direct to delayed ionisation of C 60

The timescale for the coupling of electronic and vibrational excitation in isolated fullerenes is determined by recording positive ion time-of-flight mass spectra on excitation with ultrashort laser pulses at 790 nm of the same fluence but different pulse durations. The coupling leads to the onset of a delayed ionisation “tail” on the parent fullerene ion peak. This occurs for a pulse duration of 500-1000 fs, depending on laser fluence. Received 20 October 2000     

Partonic scattering cross sections in the QCD medium

A medium modified gluon propagator is used to evaluate the scattering cross section for the process gg→gg in the QCD medium by performing an explicit sum over the polarizations of the gluons. We incorporate a magnetic screening mass from a non-perturbative study. It is shown that the medium modified cross section is finite, divergence free, and is independent of any ad-hoc momentum transfer cut-off parameters. The medium modified finite cross sections are necessary for a realistic investigation of the production and equilibration of the minijet plasma expected at RHIC and LHC.     

Free Factorizations

Given any morphism, we construct extensions of the original category in which this morphism admits certain factorizations, in particular a (retraction, section)-factorization. To this end, we solve the word problem for a certain type of systems of generators and relations for categories. This also enables us to prove preservation properties for the said extensions, e.g. preservation of a pair of diagonalizing classes of epimorphisms and monomorphisms.Iterating such extension processes, we obtain factorizable extensions of categories; in particular, we construct a free proper factorization structure on a given category, which leads to a characterization of preimages of proper factorization structures under full embeddings. As a further application, we characterize an absoluteness property regarding factorizations of functorial images of a morphism.     

Dephasing relaxation of the electron spin echo of the vibronic Cu(H(2)O)(6) complexes in Tutton salt crystals at low temperatures.

Two-pulse electron spin echo (ESE) measurements of the phase relaxation (phase memory time T(M)) were performed in a series of Tutton salt crystals M(I)(2)M(II)(SO(4))(2).6X(2)O (M(I)=NH(4), K, Cs; M(II)=Zn, Mg; X=H, D) weakly doped with Cu(2+) ions (c approximately equal to 10(18) ions/cm(3)) in temperature range 4-60 K where ESE signals were detectable. The ESE decay was strongly modulated with proton (or deuteron) frequencies and described by the decay function V(2tau)=V(0)exp(-btau-mtau(2)) with the mtau(2) term being temperature independent and negligible above 20 K. Various mechanisms leading to the tau- or tau(2)-type ESE decay are reviewed. The m and b coefficients for nuclear spectral diffusion (NSD), electron spectral diffusion (SD), and instantaneous diffusion (ID) were calculated in terms of existing theories and the resulting rigid lattice T(0)(M) times were found to be close one to another within the crystal family with average values: 17.5 micros (NSD protons), 200 micros (NSD deuterons), 8 micros (SD), and 5 micros (ID). The ID dominates but the calculated effective T(M)(0) is longer than the experimental T(M)(0)=2 micros. This is due to a nonuniform distribution of the Cu(2+) ions with a various degree of the disorder in the studied crystals. The acceleration of the dephasing rate 1/T(M) with temperature is due to the mechanisms producing exp(-btau) decay. They are reviewed and two of them were found to be operative in Tutton salt crystals: (a) Excitations to the vibronic levels of energy Delta leading to the temperature dependence 1/T(M)=B exp(-Delta/kT), with the vibronic levels produced by strong Jahn-Teller effect, and (b) spin-lattice relaxation processes being effective above 50 K. Based on the Delta values being on the order of 100 cm(-1), the scheme of vibronic levels in the Tutton salts is presented, and the independence of the Delta on temperature proves that the adiabatic potential surface shape of Jahn-Teller active Cu(H(2)O)(6) complexes is not affected by temperature below 65 K.     

On the intersection of two-parameter mean value families

We determine all means which are in the intersection of two multivariable two-parameter mean value families. These families were introduced by C. Gini (1938) and K.B. Stolarsky (1975).