Easy Access to Phosphido-Selenido Clusters. Reaction of [Ru3(CO)12] with Ph2(pyth)PSe {pyth=5-(2-Pyridyl)-2-Thienyl} and Crystal Structure of [Ru3(μ3-Se)(μ-PPh2)(μ-pyth)(CO)6{P(pyth)Ph2}]

The reaction of [Ru₃(CO)₁₂] with Ph₂(pyth)PSe (pyth=5-(2-pyridyl)-2-thienyl) allows to obtain two novel clusters [Ru₃(₃-Se)₂(CO)₇{P(pyth)Ph₂}₂] 1 and [Ru₃(₃-Se)(-PPh₂)(-pyth)(CO)₆{P(pyth)Ph₂}] 2 in satisfactory yields. The first one exhibits the well-known bicapped, open triangular, 50-electron nido-core, whereas 2, whose crystal structure has been determined, shows the rather rare Ru₃Se tetrahedron with the Ph₂P and pyth fragments as side-bridging ligands. Morever cluster 2 belongs to the exiguous family of selenido-phosphido clusters not easily achievable by other routes.     

Bismuth Oxyiodide Nanoflakes Showed Toxicity Against the Malaria Vector <Emphasis Type="Italic">Anopheles stephensi</Emphasis> and In Vivo Antiplasmodial Activity

Anopheles stephensi is a mosquito vector of malaria, which is still considered a relevant public health problem due to increasing outdoor transmission, growing resistance to insecticides used to target vectors, and antiplasmodial drugs as well. Thus, there is a vital need to explore novel sources of effective compounds. In this study, the hydrothermal method was used for the synthesis of bismuth oxyiodide (BiOI) nanoflakes. Furthermore, the toxicity of BiOI nanoflakes was evaluated for the first time on A. stephensi, as well as in vivo against the malaria parasite Plasmodium berghei. The synthesis of BiOI nanoflakes was confirmed by various characterization techniques, including X-ray diffraction, Fourier transform-infrared spectroscopy, field emission scanning electron microscopy and transmission electron microscopy (HR-TEM). LC₅₀ of BiOI nanoflakes on A. stephensi were 2.263 ppm (larva I), 3.414 ppm (II), 4.956 ppm (III), 6.983 ppm (IV) and 8.605 ppm (pupae). In vivo antiplasmodial experiments conducted on P. berghei infecting albino mice showed 27.2% of chemosuppression after 4 days of treatment with 300 mg/kg/day of BiOI, a lower performance if compared to chloroquine. Overall, our results suggested that hydrothermal synthesis of BiOI nanoflakes may be considered to develop newer and safer tools for malaria vector control.     

Structural studies on Ba(II) adducts of the cytosine nucleobase and its derivative 1-Methylcytosine*

Abstract

The use of the cytosine nucleobase or its 1-Methylcytosine derivative as ligands toward barium(II) cations led to the formation of three compounds, {[Ba(1-Mecyt)(H₂O)X₂]}_n [X=Cl (1), Br (2)], and {[Ba(cyt)₂(H₂O)(ClO₄)₂]}_n (3). Depending on the ligand and the counterion employed, 1–3 exhibit different architectures, which serve as a playground to study how the methyl substitution, together with the nature of the counterion are both significant in the self-assembling process of such species. The effect of the nature and size of the alkaline-earth metal ion on the final structural motif is also evident when comparing these structures with parent complexes of the Ca(II) ion.     

Synthesis of lupeol derivatives and their antileishmanial and antitrypanosomal activities

The natural product lupeol 1 was isolated from aerial parts of Vernonia scorpioides with satisfactory yield, which made it viable to be used as starting material in semisynthetic approach. Ten lupeol derivatives 2–11 were prepared by classical procedures. Including, five new esters derivatives 7–11, which were obtained by structural modifications in the isopropylidene fragment. All semisynthetic compounds and lupeol 1–11 were confirmed by ¹H NMR, ¹³C NMR and HRMS. Their antiprotozoal activity was evaluated in vitro against L. amazonensis and T. cruzi. Derivative 6 showed the best antitrypanosomal activity (IC₅₀ = 12.48 μg/mL) and the lowest cytotoxic derivative (CC₅₀ = 161.50 μg/mL). The mechanism of action of the most active derivatives (4, 6 and 11) is not dependent from the enzyme trypanothione reductase.     

Screening and identification of major phytochemical compounds in seeds,sprouts and leaves of Tuscan black kale Brassica oleracea (L.) ssp acephala (DC) var. sabellica L.

We report the spectrophotometric determination of total polyphenols, flavonoids, glucosinolates and antioxidant activity in seeds, seedlings and leaves of Tuscan black kale. The highest content of phytochemicals was observed in 10 days sprouts and antioxidant activity was maximum in 2, 4 days seedlings. Identification and characterisation of phytochemicals were performed by mass spectrometry (MS), high resolution and tandem MS with electrospray ionisation mode. Low-molecular-weight metabolites were evidenced in seeds while metabolites at high m/z range were detected in cotyledons and leaves. MS spectra evidenced different phenolic compounds (flavonoid caffeoyl glucose, hydroxycinnamic acid sinapine) and glucosinolates (glucoerucin, glucobrassicin and glucoraphanin) in function of developmental stage; galactolipids ω3 and ω6 were observed in leaves. Identification of stages with the highest phytochemicals content encourages the consumption of black kale sprouts and young leaves. Our research can support food and pharmaceutical industries for production of health promoting products from black kale.     

An ESI‐MS and NMR Study of the Self‐Assembly of Guanosine Derivatives

The self‐assembly of guanosine (G) derivatives in the presence of alkali‐metal ions gives octameric or polymeric aggregates composed of stacked G quartets. This process is studied for some lipophilic G derivatives by means of ESI‐MS. The ESI‐MS results are discussed in the light of complementary information obtained from NMR and SANS (small‐angle neutron scattering) studies. ESI‐MS gives an excellent picture of the self‐assembly process and gives new information on the effect of different cations and anions on the dimensions of the assembled species, information that could not have been obtained with SANS and NMR alone.     

Asymmetric Induction at C(β) and C(α) of N-Enoylsultams by Organomagnesium 1,4-Addition/Enolate Trapping

The 1,4-addition of alkylmagnesium chlorides to conjugated N-enoylsultams and subsequent ‘enolate trapping’ with aq. NH₄Cl or MeI/hexamethylphosphoric triamide generated centers of asymmetry at C(β) and/or at C(α) with good to excellent π-face defferentiation as demonstrated by the conversions 1 → 2 , 1 → 4 , and 8 → 9 . This holds also for the regioselective 1,4-addition of EtMgC1 to a dienoylsultam ( 15 → 16 ). Reactive conformations 1 ^≠, 8 ^≠, 13 , and 14 are postulated in agreement with X-ray evidence which also served for the structure determination of the product 9j .     

Analysis of phenolic compounds in extra virgin olive oil by using reversed-phase capillary electrochromatography

In this work, the simultaneous separation of ten phenolic compounds (protocatechuic, p-coumaric, o-coumaric, vanillic, ferulic, caffeic, syringic acids, hydroxytyrosol, tyrosol and oleuropein) in extra virgin olive oils (EVOOs) by isocratic RP CEC is proposed. A CEC method was optimized in order to completely resolve all the analyzed compounds by studying several experimental parameters. The influence of the stationary phase type (C(18) and C(8) modified silica gel), buffer concentration and pH as well as the organic modifier content of the mobile phase on retention factors, selectivity and efficiency were evaluated in details. A capillary column packed with Cogent bidentate C(18) particles for 23 cm and a mobile phase composed by 100 mM ammonium formate buffer pH 3/H(2)O/ACN (5:65:30 v/v/v) allowed the baseline resolution of the compounds under study in less than 35 min setting the applied voltage and temperature at 22 kV and 20 degrees C, respectively. A study, evaluating the intra- and interday precision as well as LOD and LOQ and method linearity was developed in accordance with the analytical procedures for method validation. LODs were in the range of 0.015-2.5 microg/mL, while calibration curves showed a good linearity (r(2) >0.997). The CEC method was applied to the separation and determination of these compounds in EVOO samples after a suitable liquid-liquid extraction procedure. The mean recovery values of the studied compounds ranged between 87 and 99%.