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.

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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.

     

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.     

Two combinatorial problems on posets

Bialostocki proposed the following problem: Let nk2 be integers such that k|n. Let p(n, k) denote the least positive integer having the property that for every poset P, |P|p(n, k) and every Z _k -coloring f: P Z _k there exists either a chain or an antichain A, |A|=n and _aA f(a) 0 (modk). Estimate p(n, k). We prove that there exists a constant c(k), depends only on k, such that (n+k–2)²–c(k) p(n, k) (n+k–2)²+1. Another problem considered here is a 2-dimensional form of the monotone sequence theorem of Erdös and Szekeres. We prove that there exists a least positive integer f(n) such that every integral square matrix A of order f(n) contains a square submatrix B of order n, with all rows monotone sequences in the same direction and all columns monotone sequences in the same direction (direction means increasing or decreasing).     

Quantitative analysis of six pesticides in fruits by capillary electrophoresis-electrospray-mass spectrometry

A method to identify and quantify six pesticide residues - dinoseb, pirimicarb, procymidone, pyrifenox, pyrimethanil, and thiabendazole - in peaches and nectarines using capillary electrophoresis-electrospray ionization-quadrupole ion trap-tandem mass spectrometry (CE-ESI-MS/MS) is described. Separation was carried out using a buffer of 0.3 M ammonium acetate at pH 4 with 10% methanol. Pesticide residues present in peach and nectarine samples were preconcentrated by solid-phase extraction using C(18), eluted with CH(2)Cl(2), concentrated to dryness, and redissolved in buffer to obtain lower detection limits. The recoveries of the analytes ranged from 58 to 99% and the relative standard deviations were 9 to 19%. Under optimized CE-MS/MS conditions the minimum detectable levels for the six pesticides in spiked peach samples were between 0.01 mg/kg for pirimicarb and 0.05 mg/kg for procymidone with pressure injection of 50 mbar for 5 s (5 nL) at a signal-to-noise ratio of 3, which constitutes a severalfold increase in sensitivity compared to CE-MS, using a single quadrupole, and to conventional CE-UV. The potential of the method was demonstrated by analyzing different samples taken from regional agricultural cooperatives. The pesticides most often detected were thiabendazole and procymidone.