Deciphering the activation sequence of ferrociphenol anticancer drug candidates

The complete oxidation sequence of a model for ferrociphenols, a new class of anticancer drug candidate, is reported. Cyclic voltammetry was used to monitor the formation of oxidation intermediates on different timescales, thereby allowing the electrochemical characterization of both the short-lived and stable species obtained from the successive electron-transfer and deprotonation steps. The electrochemical preparation of the ferrocenium intermediate enabled a stepwise voltammetric determination of the stable oxidation compounds obtained upon addition of a base as well as the electron stoichiometry observed for the overall oxidation process. A mechanism has been established from the electrochemical data, which involves a base-promoted intramolecular electron transfer between the phenol and the ferrocenium cation. The resulting species is further oxidized then deprotonated to yield a stable quinone methide. To further characterize the transient species successively formed during the two-electron oxidation of the ferrociphenol to its quinone methide, EPR was used to monitor the fate of the paramagnetic species generated upon addition of imidazole to the electrogenerated ferrocenium. The study revealed the passage from an iron-centered to a carbon-centered radical, which is then oxidized to yield the quinone methide, namely, the species that interacts with proteins and so forth under biological conditions.     

Green/red dual fluorescence detection of total protein and alkaline phosphate-conjugated probes on blotting membranes

A two-color fluorescence detection method is described based upon covalently coupling the succinimidyl ester of BODIPY FL-X to proteins immobilized on poly(vinylidene difluoride) (PVDF) membranes, followed by detection of target proteins using the fluorogenic substrate 9H-(1,3-dichloro-9,9-dimethylacridin-2-one-7-yl(DDAO)-phosphate in combination with alkaline-phosphatase-conjugated reporter molecules. This results in all proteins in the profile being visualized as green signal while those detected specifically with the alkaline-phosphatase conjugate appear as red signal. The dichromatic detection system is broadly compatible with a wide range of analytical imaging devices including UV epi- or transilluminators combined with photographic or charge-coupled device (CCD) cameras, xenon-arc sources equipped with appropriate excitation/emission filters, and dual laser gel scanners outfitted with a 473 nm second-harmonic generation or 488 nm argon-ion laser as well as a 633 nm helium-neon or 635 nm diode laser. The dichromatic detection method permits detection of low nanogram amounts of protein and allows for unambiguous identification of target proteins relative to the entire protein profile on a single electroblot, obviating the need to run replicate gels that would otherwise require visualization of total proteins by silver staining and subsequent alignment with chemiluminescent or colorimetric signals generated on electroblots.     

Quantum mechanical treatment of the collinear H+ + H2 system. The uncoupled system

A fully converged close coupling study is performed of the collinear (H⁺ + H₂) system on the lower potential energy surface. The surface is derived by the DIMZO (diatomic in molecules-zero overlap) method. Transition probabilities for the reactions: H⁺ + H₂ (ν = 0, 1) → H₂ (ν′) + H⁺; ν′ = 0,..., 7 are given for a number of total energies in the range from 1 eV to 3 eV. It is found that for this energy region the transition ν = 0 → ν′ = 0 is the most preferential. This fact leads us to believe that addition of the upper surface will have a minor effect on the calculated probabilities of transitions from ν = 0 in the above-mentioned energy range.     

Pseudoasymetrie dans la serie du benchrotrene I. Synthese des trois glycols ortho-substitues (OC)3CrC6H4(CHOHCH3)2

The three stereoisomeric glycols (CHOHCH₃)₂C₆H₄Cr(CO)₃ have been prepared via 1,2-diformyl- and 1,2-diacetyl-benchrotrenes. The racemic (pseudosymmetric) form and the two meso (pseudoasymmetric) forms of the glycols have been identified by chemical derivatization and analysis of the spectroscopic data. The photochemical decomplexation of these glycols is a specific route for the preparation of the two corresponding benzenic glycols. The stereoselectivity which has been observed in some reactions is discussed.     

Analysis of essential oil of Satureja thymbra by hydrodistillation, thermal desorber, and headspace GC/MS techniques and its antimicrobial activity

The essential oil composition of Satureja thymbra was analyzed by direct thermal desorber and Headspace GC/MS analysis methods. Its constituents were determined to be mainly carvacrol (40.15%), gamma-terpinene (26.56%), p-cymene (16.39%), and thymol (13.16%). The other techniques, thermal desorber and Headspace GC/MS, were used for the plant leaves at three different temperature, which showed similar results. The thermal desorber GC/MS gave better and more sensitive results than Headspace GC/MS. The essential oil was found to be active against the bacteria Escherichia coli, Pseudomonas aeruginosa, Salmonella typhimurium, Shigella sonnei, and Staphylococcus aureus and the yeast Candida albicans.     

Two New Phenylpropanoid Glycosides from the Leaves and Flowers of Erica arborea

Two new phenylpropanoid glucosides, 1,2‐erythro‐1‐(3,4,5‐trimethoxyphenyl)‐2‐(β‐D ‐glucopyranosyloxy)propan‐1,3‐diol ( 1 ) and 7,8‐threo‐2′,8‐epoxysyringylglycerol‐7‐O‐α‐D ‐glucopyranoside (ericarboside; 2 ) have been isolated together with four known compounds 2′,7‐epoxysyringylglycerol‐8‐O‐β‐D ‐glucopyranoside (ficuscarpanoside B; 3 ), benzylrutinoside (hydrangeifolin; 4 ), phenethylrutinoside ( 5 ), and caffeic acid from the BuOH soluble part of the MeOH extract of the leaves and flowers of E. arborea L. Final purification of the compounds was achieved on a reversed‐phase HPLC. Their structures have been elucidated by extensive 1D‐ and 2D‐NMR, and mass spectroscopic techniques.     

Study of the atom-phonon coupling model for (SC) partition function: first order phase transition for an infinite linear chain

In spin-conversion (SC) compounds containing molecules organized around an iron (II) ion the fundamental level of the ion is low spin (LS), S = 0, and its first excited one is high spin (HS), S = 2. This energy diagram is due to the ligands field interaction on 3d electrons and to the spin pairing energy. Heating the compound increases the magnetic susceptibility which corresponds to a change of populations of both levels and consequently a change of spin value of the molecules. This mechanism, called spin conversion (SC), can be accompagnied by thermal hysteresis observed by studying magnetic susceptibility or high spin fraction. In that case one considers that the (SC) takes place through a first-order phase transition due to intermolecular interactions. In the atom-phonon coupling model the molecules are considered as two-level systems, or two-level atoms, and it is assumed that the elastic force constant value of the spring which links two atoms first neighbours is depending on the electronic states of both atoms. In this study we calculate the partition function of a linear chain of N atoms (N ≤ 16) and we describe the role of phonons and that of the parameter Δ which corresponds to the distance in energy between both levels. The chain free-energy function is F _atph . We introduce for the chain a free-energy function defined by the set (F _HS , F _LS , F _barr ) and we show that F _atph tends towards the previous set when N → ∞. The previous set allows to describe a first order phase transition between a (LS) phase and a (HS) one. At the crossing point between the function F _LS and F _HS , and around this point, there is an intermediate free-energy barrier which prevents the chain to change phase which can lead to thermal hysteresis. The energy gap between the free-energy function F _atph and that defined by the set (F _HS , F _LS , F _barr ) is small. So we can expect that a nanoparticule takes for free-energy function that defined by the set and then displays a thermal hysteresis.     

A novel isopimarane diterpenoid with acetylcholinesterase inhibitory activity from Nepeta sorgerae, an endemic species to the Nemrut Mountain

From the dichloromethane extract of Nepeta sorgerae, the isolation and structure elucidation are now reported of a new isopimarane diterpenoid, named sorgerolone, and two known triterpenoids, oleanolic acid and ursolic acid. Antioxidant activity of the extracts and the isolated terpenoids was determined by the DPPH free radical scavenging and lipid peroxidation inhibition (beta-carotene bleaching) methods. Anticholinesterase activity of the extracts and isolates was investigated by Ellman's method against AChE and BChE enzymes. Although the antioxidant activity results were low, the AChE enzyme inhibition of the extracts and terpenoids was very promising.     

Two-dimensional atom-phonon coupling model for spin conversion: role of metastable states

Spin conversion, (SC), compounds are composed of molecules organized around a transition metal ion. The ion spin value is smaller for the ion fundamental level than for its first excited one. So, increasing the temperature changes the spin mean value. This spin conversion can be continuous or can display a first order phase transition called spin transition. The atom phonon coupling model, introduced recently, allows to describe at least qualitatively different experimental results. Up to now, this model has been applied on a linear chain of atoms. In this paper we apply it on a square lattice. We study the thermal variations of different thermodynamic parameters and the metastable states which are present around the transition. In this study, it is expected that the critical point of some (SC) compounds can be reached by applying on them a small hydrostatic pressure; it is also expected that ultrasound pulses can induce, at a very low temperature, a conversion between the stable low spin state and the metastable high spin state and it is also predicted that the crystal sound velocity can display a discontinuity at the first order phase transition.