A rapid and sensitive extractive spectrophotometric determination of copper(II) in pharmaceutical and environmental samples using benzildithiosemicarbazone.

Benzildithiosemicarbazone (BDTSC) is proposed as a sensitive and selective analytical reagent for the extractive spectrophotometric determination of copper(II). BDTSC reacts with copper(II) in the pH range 1.0-7.0 to form a yellowish complex. Beer's law is obeyed in the concentration range 0.5-0.4 microg cm(-3). The yellowish Cu(II)-BDTSC complex in chloroform shows a maximum absorbance at 380 nm, with molar absorptivity and Sandell's sensitivity values of 1.63 x 10(4) dm3 mol(-1) cm(-1) and 0.00389 microg cm(-2), respectively. A repetition of the method is checked by finding the relative standard deviation (RSD) (n = 10), which is 0.6%. The composition of the Cu(II)-BDTSC complex is established as 1:1 by slope analysis, molar ratio and Asmus' methods. An excellent linearity with a correlation coefficient value of 0.98 is obtained for the Cu(II)-BDTSC complex. The instability constant of the complex calculated from Edmond and Birnbaum's method is 7.70 x 10(-4) and that of Asmus' method is 7.66 x 10(-4), at room temperature. The method is successfully employed for the determination copper(II) in pharmaceutical and environmental samples. The reliability of the method is assured by analyzing the standard alloys (BCS 5g, 10g, 19e, 78, 32a, 207 and 179) and by inter-comparison of experimental values, using an atomic absorption spectrometer.     

Pt(IV)-catalyzed cyclization of arene-alkyne substrates via C-H bond functionalization

We herein report that PtCl₄ has proven to be a hydroarylation catalyst with an efficiency and substrate scope superior to previously known methods. This catalyst demonstrated consistent performance with arene-yne substrates of diverse structural features, including propargyl ethers, propargylamines, and alkynoate esters, providing good to excellent yields of the 6-endo products (chromenes, dihydroquinolines, and coumarins). In contrast, Pt(II), Pd(II), and Ga(III) salts were shown to be sensitive to the substitution on the alkyne moiety. PtCl₄ is compatible with both terminal and disubstituted alkynes, as well as with various functionalities on the arene ring, including methyl, methoxyl, hydroxyl, protected amine, and halide.     

Reaction of Chloroacetone with Cytisine and d-Pseudoephedrine Alkaloids

Alkylation of cytisine and d-pseudoephedrine alkaloids with chloroacetone was performed. The target product of the reaction with cytisine is aminoacetone and of the reaction with d-pseudoephedrine, a morpholine derivative.     

Grothendieck Spaces of Compact Operators

In this paper we study the Grothendieck spaces among the operator spaces L_e(E'_c, F). Conditions under which L_e(E'_c, F) contains complemented copy of c₀ are given. We apply these results to spaces of the type C_b(X; F) endowed with strict topologies.     

Nonnegative curvature and cobordism type

We show that in each dimension n = 4k, k≥ 2, there exist infinite sequences of closed simply connected Riemannian n-manifolds with nonnegative sectional curvature and mutually distinct oriented cobordism type. W. Tuschmann’s research was supported in part by a DFG Heisenberg Fellowship.     

Ab-initio simulation of elastic constants for some ceramic materials

Athermal elasticity for some ceramic materials (α-Al₂O₃, SiC (α and β phases), TiO₂ (rutile and anatase), hexagonal AlN and TiB₂, cubic BN and CaF₂, and monoclinic ZrO₂) have been investigated via density functional theory. Energy-volume equation-of-state computations to obtain the zero pressure equilibrium volume and bulk modulus as well as computations of the full elastic constant tensor of these ceramics at the experimental zero pressure volume have been performed. The present results for the single crystal elasticity are in good agreement with experiments both for the aggregate properties (bulk and shear modulus) and the elastic anisotropy. In contrast, a considerable discrepancy for the zero pressure bulk modulus of some ceramics evaluated from the energy-volume fit to the computational zero pressure volume has been observed.     

Ultrafast creation and annihilation of space-charge domains in a semiconductor superlattice observed by use of Terahertz fields

We report an experimental study indicating ultrafast creation and annihilation of space-charge domains in a semiconductor superlattice under the action of a THz field. Our experiment was performed for an InGaAs/InAlAs superlattice with the conduction electrons undergoing miniband transport. We applied to a superlattice a dc bias that was slightly smaller than a critical bias necessary for the formation of space-charge domains caused by a static negative differential conductivity. Additionally subjecting the superlattice to a strong THz field, resulted in a dc transport governed by the formation of domains if the frequency of the field was smaller than an upper frequency limit (~3 THz). From this frequency limit for the creation and annihilation of domains we determined the characteristic time of the domain buildup. Our analysis shows that the buildup time of domains in a wide miniband and heavily doped superlattice is limited by the relaxation time due to scattering of the miniband electrons at polar optic phonons. Our results are of importance for both an understanding of ultrafast dynamics of pattern formation in nanostructures and the development of THz electronic devices.Received: 25 March 2004, Published online: 23 July 2004PACS: 72.20.Ht High-field and nonlinear effects - 72.30. + q High-frequency effects; plasma effects - 73.21.Cd SuperlatticesK.N. Alekseev: Permanent address: Department of Physical Sciences, P.O. Box 3000, University of Oulu FIN-90014, Finland.     

Relations for extrema of the work of aggregation in micellar solutions

Exact relations for the dependence of the positions of extrema of the aggregation work on the aggregation number axis on the surfactant monomer concentration are found for a dilute micellar solution. Relations for the half-widths of the vicinities of the extrema of the aggregation work are determined also. These half-widths are determined by the condition that, within the boundaries of their values, the aggregation work deviates from its extreme values by a thermal unit. The relations derived are illustrated by calculations based on the droplet and quasi-droplet models of spherical aggregates of nonionic surfactant. Some important applications of the obtained results to the theory of relaxation in micellar solutions are considered.