Syntheses and Properties of Two Heterocyclically Substituted Hypericin Derivatives: 10,11-Dibenzothiazolyl-10,11-didemethylhypericin and 10,11-Dibenzoxazolyl-10,11-didemethylhypericin

Summary. The syntheses of the two heterocyclically substituted title hypericin derivatives were achieved starting either from 6-benzothiazolyl-tri-O-methyl-6-demethylemodin or 6-benzoxazolyl-tri-O-methyl-6-demethylemodin. The use of microwave assisted synthesis for the preparation of these anthraquinone synthons and the chemical as well as photochemical properties of the corresponding unique hypericin derivatives, which might constitute new photodynamic therapy agents, are reported. The tautomeric and stereochemical aspects of these hypericin derivatives were investigated by means of semiempirical calculations (AM1).     

Circulating Levels of Dephosphorylated-Uncarboxylated Matrix Gla Protein in Patients with Acute Coronary Syndrome

Vascular calcification contributes to the pathogenesis of coronary artery disease while matrix Gla protein (MGP) was recently identified as a potent inhibitor of vascular calcification. MGP fractions, such as dephosphorylated-uncarboxylated MGP (dp-ucMGP), lack post-translational modifications and are less efficient in vascular calcification inhibition. We sought to compare dp-ucMGP levels between patients with acute coronary syndrome (ACS), stratified by ST-elevation myocardial infarction (STEMI) and non-ST-elevation myocardial infarction (NSTEMI) status. Physical examination and clinical data, along with plasma dp-ucMGP levels, were obtained from 90 consecutive ACS patients. We observed that levels of dp-ucMGP were significantly higher in patients with NSTEMI compared to STEMI patients (1063.4 ± 518.6 vs. 742.7 ± 166.6 pmol/L, p < 0.001). NSTEMI status and positive family history of cardiovascular diseases were only independent predictors of the highest tertile of dp-ucMGP levels. Among those with NSTEMI, patients at a high risk of in-hospital mortality (adjudicated by GRACE score) had significantly higher levels of dp-ucMGP compared to non-high-risk patients (1417.8 ± 956.8 vs. 984.6 ± 335.0 pmol/L, p = 0.030). Altogether, our findings suggest that higher dp-ucMGP levels likely reflect higher calcification burden in ACS patients and might aid in the identification of NSTEMI patients at increased risk of in-hospital mortality. Furthermore, observed dp-ucMGP levels might reflect differences in atherosclerotic plaque pathobiology between patients with STEMI and NSTEMI.     

LC–MS Analysis of the Essential Oils of Achillea millefolium and Achillea crithmifolia

The chemical composition of the hydro-distilled essential oils of Achillea millefolium and Achillea crithmifolia was analyzed by GC, GC–MS, ¹³C NMR and high resolution LC–MS. For the first time, the use of the combination of different chromatographic and spectral methods, primarily the advantage of LC-Orbitrap over standard methods, enabled the detection of azulenes and their progenitors, in minute quantities, in previously believed proazulene free Achillea taxon (A. crithmifolia). Furthermore, the LC-Orbitrap hyphenated method provided the means for detection of these and related non-volatile (GC-injector compared to water steam distillation) metabolites up to know unreported as essential oil constituents.     

Γ-convergence for one-dimensional Ginzburg-Landau functional with generalized Lipschitz penalizing term

We use the approach developed in the paper G. Alberti, S. Muller: A new approach to variational problems with multiple scales, Comm. Pure Appl. Math. 54 , 761-825 (2001) to obtain Γ-convergence for a class of Ginzburg-Landau functionals I^ε(v), where v = v(s) is appropriate Sobolev function. We generalize results from the paper A. Raguž: Relaxation of Ginzburg-Landau functional with 1-Lipschitz penalizing term in one dimension by Young measures on micropatterns, Asymptotic Anal. 41 ( 3,4 ), 331-361 (2005), where original functional was penalized by 1-Lipschitz function g = g(s). In this note we prove Γ-convergence when g = g(s, v(s), v′(s)) under suitable growth conditions imposed on g. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Calorimetric study of phase transitions in a liquid-crystal-based microemulsion

A lyotropic inverse micelle phase composed of water, thermotropic liquid-crystal octylcyanobiphenyl (8CB), and surfactant (DDAB) was studied by using high-resolution calorimetry on several mixtures with 3%, 8%, and 15% micelle concentration. Calorimetric results show strong depression of the isotropic to nematic (I-N) phase-transition temperature. Broad heat-capacity anomalies show the existence of a wide coexistence range of isotropic, nematic, and smectic-A phases, which mimics the behavior of a new nearly stable thermodynamic phase. An observation of the rather sharp almost bulklike nematic to smectic-A (N-A) transition at low-temperatures indicates that our heat capacity results are consistent with the phase separation scenario in which significant number of micelles is expelled during I-N conversion leaving almost pure nematic phase at lower temperatures. It was found that micelles get almost completely remixed on heating the mixture back to the isotropic phase.     

Minimization of asymptotic energy of Müller's functional endowed with local nonlinear lower-order term

We solve a minimization problem associated to a generalization of the Müller functional studied in the paper G. Alberti, S. Müller: A new approach to variational problems with multiple scales, Comm. Pure Appl. Math. 54 , 761–825 (2001), whereby the lower order term ∫¹₀a(s)v²(s)ds (involving a primitive of the mass density function, v = v(s) , and the weight function a = a(s) ) is replaced by ∫¹₀a(s, v(s), v′(s))v²(s)ds (where a belongs to a suitable Carathéodory class). We calculate the rescaled asymptotic energy of the functional as small parameter epsilon tends to zero. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)