Quantification of taxanes in a leaf and twig extract from Taxus baccata L. using 13C NMR spectroscopy

In the course of our ongoing work on the chemical characterization of Taxus baccata L. growing wild in Corsica, we have developed and validated a method for direct quantification of taxane derivatives by ¹³C NMR using 10‐deacetylbaccatin III as reference compound and 1,6‐hexanediol as internal standard. We have observed good accuracy (relative errors between 0.3% and 3.5%), linearity (R² = 0.999) and precision (reproducibility 8.5 mg ± 1.1%) of the measurements. The experimental procedure was applied to the quantification of six identified taxanes in a fraction of chromatography of a methanol extract of T. baccata leaves. This method can be applied to other compounds bearing the taxane skeleton. Copyright © 2013 John Wiley & Sons, Ltd.     

Anti-inflammatory and antioxidant activities of Rungia congoensis,a traditional vegetable consumed by Yombe people from Kongo Central area (DR. Congo)

Rungia congoensis, a traditional vegetable from Kongo Central area (DR. Congo) was studied for establishing microscopic characters and characterised by chromatographic techniques and their in vitro biochemical activities against ROS production were evaluated in cellular models and on an enzyme, myeloperoxidase (MPO), involved in inflammation. Microscopically leaf can be characterised by non-glandular and glandular trichomes, sinuous anticlinal epidermal cells, diacytic stomata and helical vessels. Methanolic extract displayed high cellular antioxidant activity at the concentrations range of 0.1–10 μg mL^?1 and 1–20 μg mL^?1 using lucigenin on neutrophils and DCFH-DA on HL 60, respectively. This extract also showed, more efficient effects on extracellular and intracellular ROS production and MPO activity. Antioxidant and anti-inflammatory activities of R. congoensis were significantly higher, positively correlated with their phytochemical constituents such as flavonoids, iridoids and phenolic acids; and could justify their use as traditional vegetable and potent local nutraceutical resource.     

Eudesm-5-en-11-ol from Helichrysum italicum essential oil

Eudesm-5-en-11-ol was isolated from the oil of Helichrysum italicum and its structure was elucidated by 1D and 2D NMR spectroscopy.     

New Natural Oxygenated Sesquiterpenes and Chemical Composition of Leaf Essential Oil from Ivoirian Isolona dewevrei (De Wild. & T. Durand) Engl. & Diels

This study aimed to investigate the chemical composition of the leaf essential oil from Ivoirian Isolona dewevrei. A combination of chromatographic and spectroscopic techniques (GC(RI), GC-MS and ¹³C-NMR) was used to analyze two oil samples (S1 and S2). Detailed analysis by repetitive column chromatography (CC) of essential oil sample S2 was performed, leading to the isolation of four compounds. Their structures were elucidated by QTOF-MS, 1D and 2D-NMR as (10βH)-1β,8β-oxido-cadin-4-ene (38), 4-methylene-(7αH)-germacra-1(10),5-dien-8β-ol (cis-germacrene D-8-ol) (52), 4-methylene-(7αH)-germacra-1(10),5-dien-8α-ol (trans-germacrene D-8-ol) (53) and cadina-1(10),4-dien-8β-ol (56). Compounds 38, 52 and 53 are new, whereas NMR data of 56 are reported for the first time. Lastly, 57 constituents accounting for 95.5% (S1) and 97.1% (S2) of the whole compositions were identified. Samples S1 and S2 were dominated by germacrene D (23.6 and 20.5%, respectively), followed by germacrene D-8-one (8.9 and 8.7%), (10βH)-1β,8β-oxido-cadin-4-ene (7.3 and 8.7), 4-methylene-(7αH)-germacra-1(10),5-dien-8β-ol (7.8 and 7.4%) and cadina-1(10),4-dien-8β-ol (7.6 and 7.2%). Leaves from I. dewevrei produced sesquiterpene-rich essential oil with an original chemical composition, involving various compounds reported for the first time among the main components. Integrated analysis by GC(RI), GC-MS and ¹³C-NMR appeared fruitful for the knowledge of such a complex essential oil.     

Composition and chemical variability of the leaf oil from Corsican Juniperus thurifera. Integrated analysis by GC(RI), GC-MS and 13C NMR

The composition of 16 samples of leaf oil from Corsican Juniperus thurifera was investigated by integrated techniques, GC, GC-MS and 13C NMR. K-means partitioning and PCA analysis of the data allowed the definition of a main group (14 samples) dominated by limonene (mean = 52.2%, SD = 6.4) and alpha-pinene (mean = 7.2%, SD = 3.8). Limonene and beta-elemol (up to 19.7%) were identified as the major components of two atypic samples.     

High‐resolution spectroscopy on an X‐ray absorption beamline

A bent‐crystal spectrometer based on the Rowland circle geometry has been installed and tested on the BM30b/FAME beamline at the European Synchrotron Radiation Facility to improve its performances. The energy resolution of the spectrometer allows different kinds of measurements to be performed, including X‐ray absorption spectroscopy, resonant inelastic X‐ray scattering and X‐ray Raman scattering experiments. The simplicity of the experimental device makes it easily implemented on a classical X‐ray absorption beamline. This improvement in the fluorescence detection is of particular importance when the probed element is embedded in a complex and/or heavy matrix, for example in environmental sciences.     

平行于异材界面的三维椭圆平片裂纹分析

讨论了拉伸载荷作用下平行于两相材料界面的椭圆平片裂纹问题．首先,使用有限部积分概念和两相材料界面完全接合时的点力基本解导出了一组以裂纹表面位移差为未知函数的超奇异积分方程组．该组方程表明,此时三种裂纹模型同时存在;其次,在数值求解该组方程的过程中,未知函数裂纹表面位移差被近似为位移差的基本密度函数与多项式之积．基本密度函数反映了裂纹前沿应力奇性性态;最后,以拉伸载荷为例,讨论了椭圆平片裂纹与界面的距离、裂纹形状比和不同材料组合对应力强度因子的影响,并以图表形式给出。     

How does organic matter constrain the nature, size and availability of Fe nanoparticles for biological reduction?

Few studies have so far examined the kinetics and extent of the formation of Fe-colloids in the presence of natural organic ligands. The present study used an experimental approach to investigate the rate and amount of colloidal Fe formed in presence of humic substances, by gradually oxidizing Fe(II) at pH 6.5 with or without humic substances (HS) (in this case, humic acid--HA and fulvic acid--FA). Without HS, micronic aggregates (0.1-1 μm diameter) of nano-lepidocrocite is obtained, whereas, in a humic-rich medium (HA and FA suspensions at 60 and 55 ppm of DOC respectively), nanometer-sized Fe particles are formed trapped in an organic matrix. A proportion of iron is not found to contribute to the formation of nanoparticles since iron is complexed to HS as Fe(II) or Fe(III). Humic substances tend to (i) decrease the Fe oxidation and hydrolysis, and (ii) promote nanometer-sized Fe oxide formation by both inhibiting the development of hydroxide nuclei and reducing the aggregation of Fe nanoparticles. Bioreduction experiments demonstrate that bacteria (Shewanella putrefaciens CIP 80.40 T) are able to use Fe nanoparticles associated with organic matter about eight times faster than in the case of nano-lepidocrocite. This increase in bioreduction rate appears to be related to the presence of humic acids that (i) indirectly control the size, shape and density of oxyhydroxides and (ii) directly enhance biological reduction of nanoparticles by electron shuttling and Fe complexation. These results suggest that, in wetlands but also elsewhere where mixed organic matter-Fe colloids occur, Fe nanoparticles closely associated with organic matter represent a bioavailable Fe source much more accessible for microfauna than do crystallized Fe oxyhydroxides.     

Total synthesis of discodermolide: optimization of the effective synthetic route

An efficient and modulable total synthesis of discodermolide (DDM), a unique marine anticancer polyketide is described including related alternative synthetic approaches. Particularly notable is the repeated application of a crotyltitanation reaction to yield homoallylic (Z)-O-ene-carbamate alcohols with excellent selectivity. Advantage was taken of this reaction not only for the stereocontrolled building of the syn-anti methyl-hydroxy-methyl triads of DDM, but also for the direct construction of the terminal (Z)-diene. Of particular interest is also the installation of the C13=C14 (Z)-double bond through a highly selective dyotropic rearrangement. The preparation of the middle C8-C14 fragment in two sequential stages and its coupling to the C1-C7 moiety was a real challenge and required careful optimization. Several synthetic routes were explored to allow high and reliable yields. Due to the flexibility and robust character of this approach, it might enable a systematic structural variation of DDM and, therefore, the elaboration and exploration of novel discodermolide structural analogues.