On the elucidation of the mechanism of Vinca alkaloid fluorination in superacidic medium

Detailed investigations on one of the key steps of the superacidic fluorination of Vinca alkaloids that is the origin of C20' activation are reported. While two different pathways can be envisioned for the emergence of the transient secondary carbocationic intermediate, isotopic labeling experiments unambiguously revealed the involvement of a 1,2-hydride shift mechanism.     

Preliminary Communications Thermotropic liquid crystal behaviour of 5,5'-[(4-hexadecyloxyphenyl)ethynyl]-2,2'-bipyridine

5,5'-[(4-Hexadecyloxyphenyl)ethynyl]-2,2'-bipyridine was synthesized by a palladium(O) cross-coupling reaction. Its thermotropic liquid crystalline behaviour was analysed using differential scanning calorimetry, polarizing microscopy, and X-ray diffraction. Three enantiotropic tilted smectic phases were identified upon heating: S_F, S_I, and S_C.     

Orientation de la réaction d'alkylation des pyrazoles dans des conditions neutres et en catalyse par transfert de phase

The n-butylation and N-benzylation of nine pyrazoles bearing different substituents in positions 3 and 5 have been studied in neutral and basic medium (phase transfert catalysis). The orientation of the reaction depends strongly on the method used when the position 3 (or 5) of the starting pyrazole bears a substituent with a lone pair in ortho position (pyrazolyl or pyridyl). The different products have been identified by proton nmr.     

Determination of REE by INAA in conodont apatite of Triassicage

Instrumental neutron activation analysis is applied to determine REE in very small, toothlike elements of an extinct animal, the conodont. The results are useful to obtain records of local oceanic events and processes connected to plate tectonics in the Tethys ocean from about 250 to 200 million years ago.     

Evaluation of process parameters of ultrasonic treatment of bacterial suspensions in a pilot scale water disinfection system

In this study, several process parameters that may contribute to the efficiency of ultrasound disinfection are examined on a pilot scale water disinfection system that mimics realistic circumstances as encountered in an industrial environment. The main parameters of sonication are: (i) power; (ii) duration of treatment; (iii) volume of the treated sample. The specific energy (E_s) is an indicator of the intensity of the ultrasound treatment because it incorporates the transferred power, the duration of sonication and the treated volume. In this study, the importance of this parameter for the disinfection efficiency was assessed through changes in volume of treated water, water flow rate and electrical power of the ultrasonic reactor. In addition, the influences of the initial bacterial concentration on the disinfection efficiency were examined. The disinfection efficiency of the ultrasonic technique was scored on a homogenous and on a mixed bacterial culture suspended in water with two different types of ultrasonic reactors (Telsonic and Bandelin). This study demonstrates that specific energy, treatment time of water with ultrasound and number of passages through the ultrasonic reactor are crucial influential parameters of ultrasonic disinfection of contaminated water in a pilot scale water disinfection system. The promising results obtained in this study on a pilot scale water disinfection system indicate the possible application of ultrasound technology to reduce bacterial contamination in recirculating process water to an acceptable low level. However, the energy demand of the ultrasound equipment is rather high and therefore it may be advantageous to apply ultrasound in combination with another treatment.     

Friedel–Crafts Reaction of Benzyl Fluorides: Selective Activation of C?F Bonds as Enabled by Hydrogen Bonding

A Friedel–Crafts benzylation of arenes with benzyl fluorides has been developed. The reaction produces 1,1‐diaryl alkanes in good yield under mild conditions without the need for a transition metal or a strong Lewis acid. A mechanism involving activation of the C F bond through hydrogen bonding is proposed. This mode of activation enables the selective reaction of benzylic C F bonds in the presence of other benzylic leaving groups.     

The 8 : 1 : 1 ternary hybrid framework in the system [EDT-TTF +][1,4-bis(iodoethynyl)benzene][Re6Se8(CN)6]4-: dual noncovalent expression of the octahedral halogen-bond hexa-acceptor nanonode

Complementary shapes of the neutral symmetrical halogen-bond bis-donor core and octahedral inorganic cluster core prevent halogen-bonded polymers developing in more than one direction, favouring further templating by conducting radical cation slabs and yielding an 8 : 1 : 1 phase formulation instead of n : 2 : 1, with a 2D net, or m : 3 : 1, with a pseudo-cubic architecture, which may in principle also be targeted.     

Highly Sensitive Enzyme-free Sensor Based on a Carbon Paste Electrode Modified with Binary Zinc Oxide/Polyaniline Nanocomposites for Dopamine,Ascorbic Acid and Uric Acid Sensing

Hybrid composites ZnO/PANI were facily synthesized by a sonication process at room temperature. This procedure is non-expensive, time/energy saving and environmentally safe. The as-prepared ZnO/PANI were characterized by FTIR, UV-vis spectroscopies and SEM in order to investigate the structure and morphology of the studied composites. The samples were used to modify carbon paste electrode (CPE) in order to develop electrochemical biosensors (ZnO/PANI/CPE). The sensing properties of the nanoparticles were evaluated for dopamine, ascorbic acid and uric acid non-enzymatic detection. The effect of percentage of polyaniline in the composites and the effect of calcination on the biosensor's response were also examined in the present study. It was revealed that the existence of PANI in ZnO/PANI/CPE largely enhanced the electroactive surface area and therefore the sensitivity for electrochemical sensing. A good electrochemical behavior was noted for ZnO/40 wt% PANI-cal/CPE modified electrode toward DA, AA and UA oxidation. The electroactive surface area of the previously mentioned modified electrode (0.235 cm²) was two times higher than that of the bare electrode (0.117 cm²). The liner relationships between current intensities and concentrations were found to be 0.01–1.4 mM, 0.1–1.3 mM and 0.01–0.12 mM, with detection limit of 0.029 mM, 0.063 mM and 0.007 mM, for DA, AA and UA respectively. In the mixtures of ascorbic acid (AA), dopamine (DA) uric acid (UA) and glucose (Glu) the sensor showed high selectivity of DA with low interference of ascorbic acid by a current change of 14 %. The as-prepared ZnO/PANI/CPE biosensor displayed a good reproducibility and stability.     

Molecular-programmed self-assembly of homo- and heterometallic penta- and hexanuclear coordination compounds: synthesis, crystal structures, and magnetic properties of ladder-type CuII2MIIx (M=Cu, Ni; x=3, 4) oxamato complexes with CuII2 metallacyclophane cores

New homo- and heterometallic, hexa- and pentanuclear complexes of formula {[Cu2(mpba)2(H2O)F][Cu(Me5dien)]4}(PF6)(3).5H2O (1), {[Cu2(Me3mpba)2(H2O)2][Cu(Me5dien)]4}(ClO4)(4).12H2O (2), {[Cu2(ppba)2][Cu(Me5dien)]4}(ClO4)4 (3), and [Ni(cyclam)]{[Cu2(mpba)2][Ni(cyclam)]3}(ClO4)(4).6H2O (4) [mpba=1,3-phenylenebis(oxamate), Me3mpba=2,4,6-trimethyl-1,3-phenylenebis(oxamate), ppba=1,4-phenylenebis(oxamate), Me5dien=N,N,N'N' ',N' '-pentamethyldiethylenetriamine, and cyclam=1,4,8,11-tetraazacyclotetradecane] have been synthesized through the use of the "complex-as-ligand/complex-as-metal" strategy. The structures of 1-3 consist of cationic CuII6 entities with an overall [2x2] ladder-type architecture which is made up of two oxamato-bridged CuII3 linear units connected through two m- or p-phenylenediamidate bridges between the two central copper atoms to give a binuclear metallacyclic core of the cyclophane-type. Complex 4 consists of cationic CuII2NiII3 entities with an incomplete [2x2] ladder-type architecture which is made up of oxamato-bridged CuIINiII and CuIINiII2 linear units connected through two m-phenylenediamidate bridges between the two copper atoms to give a binuclear metallacyclophane core. The magnetic properties of 1-3 and 4 have been interpreted according to their distinct "dimer-of-trimers" and "dimer-plus-trimer" structures, respectively, (H=-J(S1A.S3A+S1A.S4A+S2B.S5B+S2B.S6B)-J'S1A.S2B). Complexes 1-4 exhibit moderate to strong antiferromagnetic coupling through the oxamate bridges (-JCu-Cu=81.3-105.9 cm-1; -JCu-Ni=111.6 cm-1) in the trinuclear and/or binuclear units. Within the binuclear metallacyclophane core, a weak to moderate ferromagnetic coupling (J'Cu-Cu=1.7-9.0 cm-1) operates through the double m-phenylenediamidate bridge, while a strong antiferromagnetic coupling (J'Cu-Cu=-120.6 cm-1) is mediated by the double p-phenylenediamidate bridge.     

Dual-cure processes: towards deformable crosslinked coatings

Two dual-cure processes consisting of a UV-initiated radical polymerization followed by either a UV-induced cationic polymerisation, or a thermal addition reaction, were investigated. The feasibility of the processes was studied using an acrylate-oxetane monomer for the UV/UV combination, and an acrylated oligoester for the UV/Heat combination. It was shown by FTIR and Tg measurements, that both steps of each process could be performed efficiently and separately. This allowed the production of a deformable partially cured coating, whose cure can then be completed, leading to the required final properties. Furthermore, it was demonstrated that the increase of the functionality of the reactive diluent led to a decrease of the thermal crosslinking extent. This is probably due to the reduced mobility of the reactive species that is caused by an enhanced UV crosslinking taking place during the first step.