Temperature and enantioseparation by macrocyclic glycopeptide chiral stationary phases

Seventy-one chiral compounds were separated on four macrocyclic glycopeptide chiral selectors: teicoplanin, its aglycone, ristocetin A and vancomycin, using three possible separation modes: reversed phase with methanol/buffer mobile phases, normal phase with hexane/ethanol mobile phases and polar ionic mode (PIM) with 100% methanol mobile phase with trace amounts of acid and/or base. These 148 separations were studied in a 5-45 degrees C temperature range. Peak efficiencies always increased with temperature, but in only 17% of the separations studied a small increase of the enantioresolution factor was observed. In the majority (83%) of the cases, the enantioresolution decreased or even vanished when temperature increased. All 148 Van't Hoff plots were linear showing that the selector did not change in the temperature range studied. The calculated enthalpy and entropy variations showed that the interaction of the solute with the stationary phase was always enthalpy driven with normal and reversed mobile phases. It could be enthalpy as well as entropy driven with PIM mobile phases strongly dependent on the solute. The plots of delta(deltaH) versus delta(deltaS) were linear in most cases (enthalpy entropy compensation). This observation cannot be used to give clear information on chiral recognition mechanisms, but it allowed identifying specific stationary phase-solute interactions because the points corresponding to the respective thermodynamic parameters were clearly delineated from the general compensation lines.     

Transcendence order over Qp in Cp

Let (K, ∥ · ∥) be a valued transcendence degree 1 extension of $\text{Q}$_p. An element x ∈ K transcendental over $\text{Q}$_p is said to have order ≤a (a > 0) if there exists C_x > 0 such that every polynomial P(X) ∈ $\text{Q}$_p [X] satisfies

$\text{?}\text{log;}\text{(P(x))? ?}\text{log}\text{∥P∥+c}{}_{\mathrm{x}}\text{(}\text{deg}\text{P)}{}^{\mathrm{a}}$

when ∥ · ∥ is the Gauss norm on $\text{Q}$_p[X]. No x ∈ $\text{C}$_p can have order ≤α if α < 1 but we construct some x ∈ $\text{C}$_p with order ≤ 1. Furthermore, we prove order ≤α is stable by algebraic extension.     

Does charge carrier dimensionality increase in mixed-valence salts of tetrathiafulvalene-terminated dendrimers?

[structure: see text] In four new dendrimers terminated by 12 electroactive tetrathiafulvalenyl substituents, the tridimensional character of the inter- and intradendrimeric charge and electron transfer, and hence of the electroconductivity, is evidenced by examination of the electronic spectra of their corresponding neutral state and cation radical, dication, and mixed-valence salts, including a closed-shell anion.     

Application of comprehensive multidimensional gas chromatography combined with time-of-flight mass spectrometry (GC x GC-TOFMS) for high resolution analysis of hop essential oil

The selection and quality of hops is a major determinant in beer flavour. Brewers acknowledge that distinctive characteristics of different hop varieties can be traced to the composition of their essential oils. The difficulty in characterising complex mixtures such as hop oil using 1-D chromatography is that many compounds co-elute. With the introduction of comprehensive multidimensional capillary gas chromatography (GC x GC), there is a tremendous improvement in the separation power or peak capacity. Recent work using GC x GC with flame ionisation detection has suggested that there may be over 1,000 compounds in hop oil. This work describes the use of GC x GC combined with TOFMS detection (Leco Pegasus 4D instrument) to analyse Target hop oil. The TOFMS spectral acquisition rate of 60 Hz provided sufficient spectra per peak (2-D peak base width of 0.1-0.2 s) for identification (119 components were identified with 45 previously unreported compounds). When analysing results, an advantage of GC x GC coupled to TOFMS is that 2-D chromatograms can be viewed for individual masses that are characteristic of particular functional groups. This allows the analyst to view the various homologous series of compounds although in certain cases coelution may still be present as shown by the esters with mass 75.     

Aromastoffe der roten Passionsfrucht. Zwei neue Edulanderivate

Aroma Constituents of the Purple Passion Fruit. Two New Edulan Derivatives The isolation of (2R*, 4S*, 4aS*, 8aS*)-4,4a-epoxy-4,4a-dihydroedulan ( 1 ), and (2R*, 3S*, 8aS*)-3-hydroxyedulan ( 2 ), two new constituents of the purple passion-fruit (Passiflora edulis SIMS ), is reported. Racemic epoxide 1 was synthesized by oxidation of edulan 6 with peracidic acid, and racemate of alcohol 2 was obtained by reduction of ketone 7 , one of the chromic acid oxidation-products of edulan 6 .     

LUMINESCENCE AND PHOTOCHEMISTRY OF 4-THIOURIDINE IN AQUEOUS SOLUTION

Abstract— In bidistilled water, 4-thiouridine (4TU) exhibits a weak unusual luminescence, the quantum yield of which is 3 × 10^-4 at 25°C. The excitation spectrum corresponds well to the 4TU absorption spectrum. The emission lies at longer wavelengths (Λ_max 550 nm) than the 4TU phosphorescence observed at 77 K (Λ_max, 470–480 nm). From the emission signal obtained after an excitation flash of 3 ns half-width, an "apparent" rate constant for the radiative deactivation process, shorter than 5 × 10⁶ s, can be inferred. The 300 K emission is efficiently quenched by halides and by oxygen: quenching involves a long-lived intermediate (⋍ 200 ns).
Clearly the emissive state X is populated through the S₀-S₁ electronic transition π→π* of 4TU. The nature of X cannot be unambiguously determined: it cannot be an excimer but can be either the 4TU triplet state or another chemical state distinct from the 4TU excited singlet or triplet states.
An interesting finding is that the 300 K emission and the ability of 4TU to photoreact are related: they are quenched with the same efficiency by halide anions. This indicates that quenching occurs at the same long-lived intermediate species , which is either a precursor of the emitter or the emitter itself.     

Evaluation of molecule-microbe interactions with capillary electrophoresis: procedures, utility and restrictions

Understanding the interactions between molecules and living organisms is of paramount importance for the evaluation of pharmaceutical activity, chemical toxicity and all manner of microbiological studies. The capability of capillary electrophoresis (CE) in the evaluation of molecule-microbe interactions is examined in the present paper. The fundamental chemical concept of the binding or association constant for molecular systems measured in free solution is discussed for biological systems where microorganisms uptake or associate with molecules from their environment. The heterogeneity of the living organisms must be understood and accounted for including differences related to semantics such as concentration units and the nature of the associations between two entities and large differences in the size and number of microorganisms as compared to molecules. Finally, the added complexity and even inhomogeneity of a cell compared to most molecular systems must be considered and possibly controlled. The binding of specific molecules to viruses is discussed. CE can be utilized to quickly determine if a molecule binds very strongly or not at all to a cell (i.e., a binary yes/no answer). This could be useful for initial high-throughput screening purposes when using capillary arrays, for example. CE can be useful for determining unusual (large) molecule/microbe stoichiometries. Finally, CE can sometimes be used to determine the size of binding constants (K(RL)) within certain limits provided experimental conditions can be formulated that minimize problems of biological heterogeneity.     

Electrospray ionization mass spectrometry studies of noncovalent myosin VI complexes reveal a new specific calmodulin binding site

Among the myosin superfamily, myosin VI differs from all others by a reverse directionality and a particular motility. Little structural information is available for myosin VI. It is known that it binds one calmodulin (CaM) by means of a single "IQ motif" and that myosin VI contains a specific insert located at the junction between the motor domain (MD) and the lever arm, likely to play a critical role for the unusual motility previously observed. Electrospray ionization mass spectrometry (MS) was used to determine the CaM and Ca2+ stoichiometries in several myosin VI constructs. In particular, the experimental conditions required for the observation of multiprotein/Ca2+ noncovalent assemblies are detailed for two truncated MD constructs (less than 20 kDa) and for three full MD constructs (more than 90 KDa). The specificity of the detected stoichiometries is discussed for each construct and the resolving power of Time of Flight mass spectrometry is stressed, in particular for the detection of metal ions binding to high molecular weight complexes. MS reveals a new CaM binding site for myosin VI and highlights a different behavior for the five myosin VI constructs versus Ca2+ binding. In addition to these stoichiometry based experiments, gas-phase dissociation analyses on intact complexes are described. They reveal that Ca2+ transfer between protein partners occurs during the dissociation process for one construct with a full MD. Charge-transfer and dissociation behavior has allowed to draw structural assumptions for the interaction of the MD with the CaM N-terminal lobe.     

Solid-State and solution studies of [Ln(n)(SiW11O39)] polyoxoanions: an example of building block condensation dependent on the nature of the rare earth

The reactivity of the [alpha-SiW(11)O(39)](8-) monovacant polyoxometalate with lanthanide has been investigated for four different trivalent rare-earth cations (Ln = Nd(III), Eu(III), Gd(III), Yb(III)). The crystal structures of KCs(4)[Yb(alpha-SiW(11)O(39))(H(2)O)(2)] x 24H(2)O (1), K(0.5)Nd(0.5)[Nd(2)(alpha-SiW(11)O(39))(H(2)O)(11)] x 17H(2)O (2a), and Na(0.5)Cs(4.5)[Eu(alpha-SiW(11)O(39))(H(2)O)(2)] x 23H(2)O (3a) are reported. The solid-state structure of compound 1 consists of linear wires built up of [alpha-SiW(11)O(39)](8-) anions connected by Yb(3+) cations, while the linkage of the building blocks by Eu(3+) centers in 3a leads to the formation of zigzag chains. In 2a, dimeric [Nd(2)(alpha-SiW(11)O(39))(2)(H(2)O)(8)](10-) entities are linked by four Nd(3+) cations. The resulting chains are connected by lanthanide ions, leading to a bidimensional arrangement. Thus, the dimensionality, the organization of the polyoxometalate building units, and the Ln/[alpha-SiW(11)O(39)](8-) ratio in the solid state can be tuned by choosing the appropriate lanthanide. The luminescent properties of compound 3a have been studied, showing that, in solution, the polymer decomposes to give the monomeric complex [Eu(alpha-SiW(11)O(39))(H(2)O)(4)](5-). The lability of the four exogenous ligands connected to the rare earth must allow the functionalization of this lanthanide polyanion.