Non-bilayer formation in the DPPE-DPPG vesicle system induced by deep rough mutant of Salmonella minnesota R595 lipopolysaccharide

The vesicle system consisting of 80 mol% dipalmitoylphosphatidylethanolamine (DPPE) and 20 mol% dipalmitoylphosphatidylglycerol (DPPG) undergoes to structural changes caused by various concentrations of Salmonella minnesota R595 lipopolysaccharide (LPS). The phenomenon was investigated by methods applying small- and wide-angle X-ray scattering (SAXS and WAXS), calorimetry (DSC) and freeze-fracture. In the low LPS concentration regime (investigated at 0.02 LPS/DPPE–DPPG molar ratio) a phase separation was observed. Two kind of domains are formed which are rich and poor in DPPE and in these domains cubic and lamellar structures are present, respectively. Increasing the LPS concentration up to 0.1 LPS/DPPE–DPPG molar ratio the phase separation is more expressed and the temperature domains of the phase transitions are more different. Increasing the temperature chain melting of the lamellar phase occurs first and destruction of the cubic phase is observed later. At high LPS concentration (equimolar ratio of LPS/DPPE–DPPG), where this amphiphilic molecule cannot be considered any more a guest molecule, the cubic structure dominates the phase behaviour of the LPS molecules.     

Every Large Point Set contains Many Collinear Points or an Empty Pentagon

We prove the following generalised empty pentagon theorem for every integer ℓ ≥ 2, every sufficiently large set of points in the plane contains ℓ collinear points or an empty pentagon. As an application, we settle the next open case of the “big line or big clique” conjecture of Kára, Pór, and Wood [Discrete Comput. Geom. 34(3):497–506, 2005].     

Stable isotope geochemistry of calcrete nodules and septarian concretions in a Quaternary 'red clay' paleovertisol from Hungary

Calcrete nodules and concretions in unusually large amounts are embedded in the Quaternary clay-rich (Vertisol-type) 'red clay' soil-sedimentary complex at the pediment of the Mátra Mountains (Hungary). Stable isotope signatures were studied in nodules and septarian concretions, uncommon due to their several millimeter sized calcite crystals filling voids and fractures, to reveal their origin. The isotope composition of calcrete covers a wide range: delta18O=-5.9 to-10.4 per thousand and delta13C=-8.9 to-12.3 per thousand (vs. V-PDB). Isotope compositions support pedogenic (sensu stricto) and/or shallow groundwater origin for the calcrete nodules and concretions, the role of 'evolved' (isotopically modified) groundwaters in the formation of secondary carbonate was possibly subordinate. Late-stage, large, Mn-rich euhedral calcite crystals in concretions have the lowest delta13C values, which are interpreted as a result of larger contribution of isotopically light organic carbon due to decomposition of organic matter under reducing conditions. Precipitation of late calcite crystals in concretions occurred in early diagenetic environment after shallow burial of the 'red clay' paleovertisol.     

Simple approach to one-laser, broadband coherent anti-Stokes Raman scattering microscopy

Coherent anti-Stokes Raman scattering (CARS) microscopy is emerging as a powerful method for imaging materials and biological systems, partly because of its noninvasiveness and selective chemical sensitivity. However, its full potential for species-selective imaging is limited by a restricted spectral bandwidth. Recent increases in bandwidth are promising but still are not sufficient for the level of robust component discrimination that would be needed in a chemically complex milieu found, for example, in intracellular and extracellular environments. We demonstrate a truly broadband CARS imaging instrument that we use to acquire hyperspectral images with vibrational spectra over a bandwidth of 2500 cm(-1) with a resolution of 13 cm(-1).     

Determination of the Absolute Configuration of Super-Carbon-Chain Compounds by a Combined Chemical,Spectroscopic, and Computational Approach: Gibbosols A and B

Marine dinoflagellates produce remarkable organic molecules, particularly those with polyoxygenated long-carbon-chain backbones, namely super-carbon-chain compounds (SCCCs), characterized by the presence of numerous stereogenic carbon centers on acyclic polyol carbon chains. Even today, it is a challenge to determine the absolute configurations of these compounds. In this work, the planar structures and absolute configurations of two highly flexible SCCCs, featuring either a C₆₉- or C₇₁-linear carbon backbone, gibbosols A and B, respectively, each containing thirty-seven stereogenic carbon centers, were unambiguously established by a combined chemical, spectroscopic, and computational approach. The discovery of gibbosols A and B with two hydrophilic acyclic polyol chains represents an unprecedented class of SCCCs. A reasonable convergent strategy for the biosynthesis of these SCCCs was proposed.     

Diophantine equations with products of consecutive members of binary recurrences

We prove a finiteness result for the number of solutions of a Diophantine equation of the form \(u_n u_{n+1}\cdots u_{n+k}\pm 1 =\pm u_m^2\), where \(\{ u_n\}_{n\ge 1}\) is a binary recurrent sequence whose characteristic equation has roots which are real quadratic units.     

Weakly separative weakly commutative semigroups

A semigroup S is called a weakly commutative semigroup if, for every a,b∈S, there is a positive integer n such that (ab) ⁿ ∈Sa∩bS. A semigroup S is called archimedean if, for every a,b∈S, there are positive integers m and n such that a ⁿ ∈SbS and b ^m ∈SaS. It is known that every weakly commutative semigroup is a semilattice of weakly commutative archimedean semigroups. A semigroup S is called a weakly separative semigroup if, for every a,b∈S, the assumption a ²=ab=b ² implies a=b. In this paper we show that a weakly commutative semigroup is weakly separative if and only if its archimedean components are weakly cancellative. This result is a generalization of Theorem 4.16 of Clifford and Preston (The Algebraic Theory of Semigroups, Am. Math. Soc., Providence, 1961).     

Demixing in polystyrene/methylcyclohexane solutions

Cloudpoint data for polystyrene/methylcyclohexane solutions extending over moderate ranges of pressure and molecular weight are available in the literature. Those data are supplemented with new results from this laboratory to fill in gaps and extend the MW range (to 761 ≤ MW/amu ≤ 2 × 10⁷). The resulting data net is discussed and reasons to extend studies to higher pressure are presented. © 1996 John Wiley & Sons, Inc.     

Kinetics and mechanism of the reaction between hypochlorous acid and tetrathionate ion

The reaction has been studied spectrophotometrically monitoring the absorbance in the 240–400 nm wavelength range. The spectra of the reactants, intermediates, and products in this system are overlapping; thus special programs [ 1 , 2 ] have been used (and tested) to unravel the kinetics and mechanism of the reaction. The stoichiometry of the reaction in excess hypochlorous acid is S₄O₆²⁻ + 7HOCl + 3H₂O → 4SO₄²⁻ + 7Cl⁻ + 13H⁺. Various experiments are presented to show that—in excess tetrathionate—the reaction produces a light‐absorbing intermediate identified as S₂O₃Cl⁻. The intermediate slowly hydrolyzes into sulfur and sulfate and it yields pentathionate in excess tetrathionate. The rate‐determining steps and their rate constants are The further oxidation of S₂O₄²⁻ and SO₃²⁻ by HOCl to sulfate are fast processes. © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 32: 395–402, 2000