Hilic MS/MS determination of amino acids in herbs of Fumaria schleicheri L., Ocimum basilicum L., and leaves of Corylus avellana L.

The aim of research was to study the content of amino acids using in extracts of Fumaria schleicheri L., Ocimum basilicum L., and Corylus avellana L. by HILIC MS/MS method. Separation of amino acids in the samples was carried out with Acquity H-class UPLC system (Waters, Milford, USA) equipped with SeQuant ZIC-Hilic collumn (2.1 × 150 mm, 3.5 μm) (Merck Millipore, Darmstadt, Germany). The MS/MS fragment ion chromatograms of the test solutions established the presence of 19 amino acids. The obtained results have shown that O. basilicum L. characterized the highest concentrations of different neurogenic amino acids (128.1 mg/kg), comparing with F. schleicheri L. and C. avellana L. (57.72 and 52.91 mg/kg, respectively).     

Synthesis of the proposed structure of queenslandon

The proposed structure of the benzolactone queenslandon (6) was synthesized utilizing a triol containing building block prepared from d-ribose. While a ring-closing metathesis approach did not lead to the macrocycle, alkylation of a benzyl(phenyl)selane, elimination to generate the styrene double bond, followed by Mitsunobu macrolactonization proved to be successful. Spectral data suggest that the structure of queenslandon should be revised, probably to the C11 epimer.     

Total synthesis and biological evaluation of (-)-9-deoxy-englerin A

An effective total synthesis of (-)-9-deoxy-englerin (4), an analogue of the natural guaiane sesquiterpene englerin A (1), has been achieved. The synthesis features a transannular epoxide opening to construct the 5,7-fused ring system followed by transannular ether formation with mercury(II) trifluoroacetate.     

An approach to the core structure of leiodermatolide

The synthesis of the 16-membered core structure of leiodermatolide 40 has been achieved in 26 linear steps starting from (R)-Roche ester. The key steps in the synthesis of 40 are a Stille cross-coupling between two main fragments 11 and 33 having roughly equal size. For the trisubstituted C4/C5 double bond a carbometalation reaction followed by a Suzuki coupling was used. A Yamaguchi macrolactonization furnished macrolactone 39.     

Development and Validation of the UPLC-DAD Methodology for the Detection of Triterpenoids and Phytosterols in Fruit Samples of Vaccinium macrocarpon Aiton and Vaccinium oxycoccos L.

Cranberries are used in the production of medicinal preparations and food supplements, which highlights the importance of triterpene compounds determination in cranberry fruit raw material. The aim of our study was to develop and validate for routine testing suitable UPLC-DAD methodology for the evaluation of triterpene acids, neutral triterpenoids, phytosterols, and squalene content in cranberry samples. The developed and optimized UPLC-DAD methodology was validated according to the guidelines of the International Council for Harmonization (ICH), evaluating the following parameters: range, specificity, linearity (R² > 0.999), precision, LOD (0.27–1.86 µg/mL), LOQ (0.90–6.18 µg/mL), and recovery (80–110%). The developed and validated technique was used for the evaluation of triterpenic compounds in samples of Vaccinium macrocarpon and Vaccinium oxycoccos fruits, and their peels, pulp and seeds. The studied chromatogram profiles of Vaccinium macrocarpon and Vaccinium oxycoccos were identical but differed in the areas of the analytical peaks. Ursolic acid was the dominant compound in fruit samples of Vaccinium macrocarpon and Vaccinium oxycoccos. The highest amounts of triterpenic compounds were detected in the cranberry peels samples. The developed method for the detection of triterpene compounds can be applied in further studies for routine testing on the qualitative and quantitative composition of fruit samples of Vaccinium macrocarpon and Vaccinium oxycoccos species and cultivars.     

The central limit theorem for a sequence of random processes with space-varying long memory*

In this paper, we investigate a sequence of square-integrable random processes with space-varying memory. We establish sufficient conditions for the central limit theorem in the space L ²(μ) for the partial sums of the sequence of random processes with space-varying long memory. Of particular interest is a nonstandard normalization of the partial sums in the central limit theorem.     

mTHPC-mediated photodynamic treatment up-regulates the cytokines VEGF and IL-1alpha

Photodynamic therapy (PDT) of cancer induces oxidative stress, which intervenes in the expression of cytokines by tumor cells. The cytokines might have either a positive or a negative impact on tumor eradication. Here, we studied the expression of cytokines vascular endothelial growth factor (VEGF) and interleukin-1alpha (IL-1alpha) in the human epidermoid carcinoma A-431 cells following m-tetra(3-hydroxyphenyl)-chlorin (mTHPC)-mediated PDT in vitro and assessed the IL-1alpha effect on VEGF expression. Quantitative polymerase chain reaction and enzyme-linked immunosorbent assay revealed the enhanced production of VEGF and IL-1alpha both on mRNA and protein levels by mTHPC-loaded cells after light exposure. The silencing of IL1A by small interfering RNA resulted in decreased production of IL-1alpha and a reduced amount of VEGF. Furthermore, exogenous recombinant IL-1alpha stimulated the VEGF expression after PDT. Thus, in addition to the cytotoxic action on the A-431 cells, mTHPC-mediated PDT stimulated the production of VEGF and IL-1alpha, and IL-1alpha contributed to the VEGF overexpression. These data establish IL-1alpha as a possible target of combined cancer treatment.