Transition metal complexes with thiosemicarbazide-based ligands,IV: Synthesis and molecular structure of 5-nitrosalicylaldehyde S-methylisothiosemicarbazonato-piperidine-copper(II)

Summary The reaction of warmDMF solutions of Cu(II) perchlorate, 5-nitrosalicylaldehyde S-methylisothiosemicarbazone (H₂ L) and piperidine (Pip) yielded the paramagnetic (_eff=2.19 B.M.) Cu(L)Pip complex, whereL is the dianionic form of H₂ L, formed as a result of deprotonation of the phenolic hydroxyl and NH₂ group. Crystal data of the complex are: monoclinic P2₁,a=11.902(4),b=6.765(3),c=11.343(4)Å; =112.92°,V=841.20(8)ų,M=400.9,Z=2,d ₀=1.60 gcm^–3,d _c =1.58 gcm^–3,F(000)=424. The structure was refined to a residualR=0.047. The copper(II) ion is coordinated in a square-planar arrangement by the piperidine nitrogen and the NNO set of donor atoms ofL.

---

Komplexe der Übergangsmetalle mit Thiosemicarbazid-Liganden, IV. Synthese und molekulare Struktur von 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazonato-piperidin-kupfer(II)

Zusammenfassung Durch die Reaktion in warmenDMF-Lösungen von Cu(II) Perchlorat, 5-Nitrosalicylaldehyd-S-methylisothiosemicarbazon (H₂ L) und Piperidin (Pip) wurde ein paramagnetischer Komplex (_eff=2.19 B.M.) Cu(L)Pip erhalten, wobeiL nach doppelter Deprotonierung (NH₂- und Phenolhydroxyl-Gruppe) als dianionische Form von H₂ L vorliegt. Die kristallographischen Daten des Komplexes sind: monokline Raumgruppe P2₁,a=11.902(4),b=6.765(3),c=11.343(4)Å, =112.92°;V=841.20ų,M=400.9,Z=2,d ₀=1.60 gcm^–3,d _c =1.58 gcm^–3,F(000)=424. Die struktur wurde bis zu einemR-Wert von 0.047 verfeinert. Die Koordination des Kupfers wird quadratisch-planar über den Piperidin-Stickstoff und die NNO-Donorhülle der Chelatliganden gebildet.

     

Determination of oxidized and reduced glutathione, by capillary zone electrophoresis, in Brassica juncea plants treated with copper and cadmium

A rapid method of capillary zone electrophoresis is described to determine the oxidized (GSSG) and reduced (GSH) form of glutathione in plant tissue. In order to separate both analytes in a fused-silica capillary, the pH and composition of the electrolyte solution were optimized. The electrolyte composition was 100 mmol/L, borate 25 mmol/L Tris, and 0.2% w/v metaphosphoric acid (MPA), pH 8.2. Some instrumental conditions used to run the samples were hydrostatic injection for 30 s, 30 kV applied voltage, and UV detection (185 nm) at 25 degrees C. Linearity and useful range obtained for the calibration curves were optimum, with correlation coefficients about 0.999 in the 0-120 micromol/L range. The migration time was highly reproducible, less than 5 min being afforded to run a sample. Electrolyte buffer and samples required a careful pH control for optimal separation of both analytes. This aspect constitutes a critical analytical step when acids are used in the procedure for sample preparation. Simultaneous analysis of GSH and GSSG may provide a useful tool for comparative studies of plants in order to select those species with a potential capacity for detoxification from toxic elements or those appearing promising from phytoremediation for these elements.     

Molybdenum-phosphorus triple bond stabilization by ancillary alkoxide ligation: synthesis and structure of a terminal phosphide tris-1-methylcyclohexanoxide complex

Using alcoholysis, we converted terminal phosphide PMo(N[i-Pr]Ar)3 into a new, monomeric terminal phosphide PMo(OR)3, where R = 1-methylcyclohexyl or 1-adamantyl. Dimerization of the PMo unit was observed upon alcoholysis with 2,6-dimethylphenol, and the dimer [PMo(N[i-Pr]Ar)(O-2,6-C6H3Me2)2]2 was isolated and characterized by X-ray crystallography.     

NADH Electrooxidation Using Bis(1,10-phenanthroline-5,6-dione) (2,2'-bipyridine)ruthenium(II)-Exchanged Zirconium Phosphate Modified Carbon Paste Electrodes

We present a carbon paste electrode (CPE) modified using the electron mediator bis(1,10‐phenanthroline‐5,6‐dione)(2,2′‐bipyridine)ruthenium(II) ([Ru(phend)₂bpy]²⁺) exchanged into the inorganic layered material zirconium phosphate (ZrP). X‐Ray powder diffraction showed that the interlayer distance of ZrP increases upon [Ru(phend)₂bpy]²⁺ intercalation from 10.3 Å to 14.2 Å. The UV‐vis and IR spectroscopies results showed the characteristic peaks expected for [Ru(phend)₂bpy]²⁺. The UV‐vis spectrophotometric results indicate that the [Ru(phend)₂bpy]²⁺ concentration inside the ZrP layers increased as a function of the loading level. The exchanged [Ru(phend)₂bpy]²⁺ exhibited luminescence even at low concentration. Modified CPEs were constructed and analyzed using cyclic voltammetry. The intercalated mediator remained electroactive within the layers (E°′=–38.5 mV vs. Ag/AgCl, 3.5 M NaCl) and electrocatalysis of NADH oxidation was observed. The kinetics of the modified CPE shows a Michaelis–Menten behavior. This CPE was used for the oxidation of NADH in the presence of Bakers' yeast alcohol dehydrogenase. A calibration plot for ethanol is presented.     

Hair color changes and protein damage caused by ultraviolet radiation

Ultraviolet and visible radiations are known to damage hair. However, quantitative data relating damage to hair type, proteins and color to the radiation wavelength are missing. We studied the effect of UV plus visible, UVA plus visible, visible mercury-vapor lamp radiation and sunlight on (blended) virgin dark-brown, blond and red hair and (one head) virgin black and curly dark-brown hair. All hair types showed a substantial increase in protein loss in water after lamp and sun irradiation. The damaging effect of UVB was about 2-5 times higher than that of UVA plus visible radiation, depending on the hair type. Significant color changes were also observed in every hair type, after lamp and sun irradiation, being more pronounced for the light colored hairs. The luminosity difference parameter was the major contributor to the hair color changes, but significant changes in the red-green and yellow-blue parameters of every hair were observed. In this case, the damaging effect is ascribable mainly to UVA radiation. No significant changes in the mechanical properties or topography were observed in any case. We discuss these results in terms of hair type and composition and melanin types.     

Optimization model to support sustainable crop planning for reducing unfairness among farmers

Central European Journal of Operations Research - Agri-food production must increase while food waste needs to be reduced for improving the position of farmers. To do so it is necessary to...     

A remark on a maximal function over a Cantor set of directions

LetM _e ⁰ be the maximal operator over segments of length 1 with directions belonging to a Cantor set. It has been conjectured that this operator is bounded onL ². We consider a sequence of operators over finite sets of directions converging toM _e ⁰ . We improve the previous estimate for the (L ²,L ²)-norm of these particular operators. We also prove thatM _e ⁰ is bounded from some subsets ofL ² toL ². These subsets are composed of positive functions whose Fourier transforms have a very weak decay or are supported in a vertical strip. Partially supported by Spanish DGICYT grant no. PB90-0187.     

Directional operators and radial functions on the plane

LetEçS ¹ be a set with Minkowski dimensiond(E)1. We consider the Hardy-Littlewood maximal function, the Hilbert transform and the maximal Hilbert transform along the directions ofE. The main result of this paper shows that these operators are bounded onL _rad ^p (R²) forp>1+d(E) and unbounded whenp<1+d(E). We also give some end-point results.     

Lines of curvature near umbilical points on surfaces immersed in R4

LetM be a compact orientable surface,I:M R⁴ an immersion of classC ^r and a normal unitary smooth vector field. We prove that in the space of pairs (I, ) the family of pairs all whose umbilical points are Darbouxian is generic.