Synthesis,Characterization, Structural Description,Micellization Behavior,DNA Binding Study and Antioxidant Activity of 4, 5 and 6-Coordinated Copper(II) and Zinc(II) Complexes

Four mononuclear copper(II) and zinc(II) complexes were synthesized by the reaction of copper and zinc salts with 3,4-dichlorophenylactic acid, 2-bromophenylactic acid, biphenylacetic acid (O-donor ligand) and bipyridine (N-donor ligands) having the general formulae [(L)₂Cu(bp)(H₂O)] ( 1 ), [(BpA)₂Cu(bp)] ( 2 ), [(L)₂Zn(bp)(H₂O)] ( 3 ) and [(L*)₂Zn(bp)] ( 4 ) (L = 3,4-dichlorophenylacetate, L* = 2-bromophenylacetate bp = bipyridine, and BpA = biphenylacetate). Structures of all compounds were characterized through FT-IR spectroscopy and X-ray diffraction analysis. FT-IR spectra of all complexes confirmed the binding mode of Cu-O and Zn-O. XRD data revealed that complexes 1 – 3 exhibited distorted octahedral arrangement, whereas complex 4 has a distorted tetrahedral environment. Micellization behavior was examined with anionic surfactant (SDS) by conductance measurement as well as absorption spectral analysis. DNA binding study was assessed through viscosity measurement and UV/Vis spectrophotometry. DPPH free radical scavenging assay was measured by UV/Vis spectrophotometry. The results showed nice biological potential of all the complexes.     

Use of quasi-isoelectric buffers to limit protein adsorption in capillary zone electrophoresis

The use of quasi-isoelectric buffers consisting of narrow pH cuts of carrier ampholytes (NC) has been investigated to limit protein adsorption on capillary walls during capillary zone electrophoresis experiments. To quantify protein adsorption on the silica surface, a method derived from that of Towns and Regnier has been developed. alpha-Lactalbumin (14 kDa, pI 4.8) and alpha-chymotrypsinogen A (25 kDa, pI 9.2) have been used as model proteins. Acidic narrow pH cuts of carrier ampholytes (NC, pH 3.0) obtained from fractionation of Serva 4-9 carrier ampholytes were used as BGE in bare-silica capillaries, and allowed to decrease significantly protein adsorption, as compared to experiments performed with classical formate buffer. The use of NC as BGE appeared to be as efficient as the use of polydimethylacrylamide coating to prevent protein adsorption. This increase of protein recovery when using NC was attributed to the interaction of carrier ampholytes with the silica surface, leading to a shielding of the capillary wall.     

Isolation of Indonesian cananga oil using multi-cycle pressure drop process

New process, instantaneous controlled pressure drop (DIC) was applied on Cananga odorata dry flowers with the aim to isolate essential oil. DIC is based on high temperature, short time heating followed by an abrupt pressure drop into a vacuum. A part of volatile compounds is carried away from flowers in the form of vapor (DIC direct oil) that evolves adiabatically during the pressure drop (proper isolation process) and the other part remains in the DIC-treated flowers (DIC residual oil). In the present paper, the effect of DIC cycle number (1-9) and heating time (4.3-15.7 min) on the availability of oil compounds was investigated at three levels of steam pressure (0.28, 0.4 and 0.6 MPa). The availability was defined as the amount of a compound in direct or residual oil divided by the amount of this compound in the reference oil extracted from non-treated flowers by chloroform during 2h. The total availability and yield of volatiles in the direct oil increased with pressure and cycle number. At a higher pressure, the effect of heating time was insignificant. The amount of oxygenated monoterpenes and other light oxygenated compounds (i.e. predominantly exogenous compounds) in the residual flowers was lower than in the direct oil and this amount decreased with cycle number. On the other hand, the availability of oxygenated sesquiterpenes and other heavy oxygenated compounds (i.e. predominantly endogenous compounds) in residual flowers exhibited a maximum for about five cycles and their quantity at this point was three times as much as in the direct oil. The total availability of each compound at 0.6 MPa was higher than one. The rapid DIC process (0.6 MPa, 8 cycles, 6 min) gave better results than steam distillation (16 h) concerning direct oil yield (2.8%dm versus 2.5%dm) and content of oxygenated compounds (72.5% versus 61.7%).     

An Electron-Deficient Triosmium Cluster Containing the Thianthrene Ligand: Synthesis, Structure and Reactivity of [Os3(CO)9(μ3-η2-C12H7S2)(μ-H)]

Reaction of [Os₃(CO)₁₀(CH₃CN)₂] with thianthrene at 80 °C leads to the nonacarbonyl dihydride compound [Os₃(CO)₉(μ-3,4-η²-C₁₂H₆S₂)(μ-H)₂] (1) and the 46-electron monohydride compound [Os₃(CO)₉(μ₃-η²-C₁₂H₇S₂)(μ-H)] (2). Compound 2 reacts reversibly with CO to give the CO adduct [Os₃(CO)₁₀(μ-η²-C₁₂H₇S₂)(μ-H)] (3) whereas with PPh₃ it gives the addition product [Os₃(CO)₉)(PPh₃)(μ-η²-C₁₂H₇S₂)(μ-H)] (4) as well as the substitution product 1,2-[Os₃(CO)₁₀((PPh₃)₂] (5) Compound 2 represents a unique example of an electron-deficient triosmium cluster in which the thianthrene ring is bound to cluster by coordination of the sulfur lone pair and a three-center-two-electron bond with the C(2) carbon which bridges the same edge of the triangle as the hydride. Electrochemical and DFT studies which elucidate the electronic properties of 2 are reported. Dedicated to the memory of a great scientist, F. Albert Cotton.     

Small generators of the ideal class group

Assuming the Generalized Riemann Hypothesis, Bach has shown that the ideal class group of a number field can be generated by the prime ideals of having norm smaller than . This result is essential for the computation of the class group and units of by Buchmann's algorithm, currently the fastest known. However, once has been computed, one notices that this bound could have been replaced by a much smaller value, and so much work could have been saved. We introduce here a short algorithm which allows us to reduce Bach's bound substantially, usually by a factor 20 or so. The bound produced by the algorithm is asymptotically worse than Bach's, but favorable constants make it useful in practice.

     

Steady-state diffusion regime in solid-phase microextraction kinetics

The temporal evolution of diffusion-controlled analyte accumulation in solid-phase microextraction (SPME) is critically discussed in terms of the various aspects of steady-state diffusion in the two phases under conditions of fast exchange of the analyte at the solid phase film/water interface. For partition coefficients (K_sw) much larger than unity and a sufficiently thin polymer film, the concentration gradient of the analyte in the polymer phase is largely insignificant. The growth of the accumulated amount of analyte is then adequately described by the well-known exponential expression for steady-state diffusion under non-depletive conditions, provided the initial transient stage is properly taken into account. In case of fiber-type solid phases, the cylindrical nature of the diffusion complicates the nature of the transient stage as well as the magnitude of the steady-state flux.     

Sol‐Gel‐Derived Biosensor Based on Plant Tissue: The Inhibitory Effect of Atrazine on Polyphenol Oxidase Activity for Determination of Atrazine

This work presents a sol‐gel based biosensor for atrazine determination which has been obtained by introducing the enzyme polyphenol oxidase from apple tissue in a sol‐gel matrix. Apple tissue acts as a molecular recognition element. Atrazine is an inactive compound electrochemically; redox coupling of dopamine was used for studying atrazine behavior. Atrazine was determined by monitoring the inhibition power of polyphenol oxidase activity. The measurements were performed in 0.1 M KH₂PO₄‐NaOH buffer (pH 7.5). The effect of various experimental parameters such as pH, concentration of buffer, concentration of dopamine, incubation time and matrix composition has been investigated for optimum analytical performance. The biosensor consisted of 10.3% (w/w) of apple tissue. The bioelectrode exhibits a linear response for dopamine and atrazine concentrations in the range of 5.66 × 10^?6?2.27 × 10^?3M and 1 × 10^?5 ?1 × 10^?4 M with a detection limit of 4.2 × 10^?6 and 5.5 × 10^?6 M, respectively. A correlation coefficient of 0.9945 and a relative standard deviation (R.S.D.) of 3.29% for dopamine, 0.9944 and 3.69% for a trazine were achieved.