Assembling of dimeric entities of Cd(II) with 6-mercaptopurine to afford one-dimensional coordination polymers: synthesis and scanning probe microscopy characterization

The direct reaction between 6-mercaptopurine (6-MP) and Cd(II) under different conditions yields either [Cd2(6-MP)4(NO3)2](NO3)2 (1) or [Cd(6-MP-)2.2H2O]n (4). Compound 1 behaves as the building block of the polymer [Cd(6-MP2-)2]n[Ca(H2O)6]n (3), by deprotonation of 6-MP ligand. In the reaction of 1 to give 3, the dinuclear compound [Cd2(6-MP)4(H2O)2](NO3)4.2H2O (2) can be isolated as an intermediate. Polymers 3 and 4 convert into each other in water via deprotonation-protonation reactions. The structures of compounds 1-3 have been determined by X-ray diffraction. Given the small differences in the arrangement shown in the crystal structures of the polymer 4 and the polyanion of 3, the stabilities and energetics of the two arrangements have been examined by DFT calculations to determine the possibility of identifying new conformations of both polymers. In addition, the two polymers have been characterized on surfaces by means of AFM. The direct reaction between 6-MP and Cd(II) and the deprotonation of the polymer 4 have proven to be useful routes for the isolation of one-dimensional systems on surfaces. The development of new strategies to characterize these types of polymers on surfaces opens the possibility to perform nanoscale studies on their properties and their potential use as nanomaterials.     

Solid-phase reactors as high stability reagent sources in flow analysis: selective flow injection spectrophotometric determination of cysteine in pharmaceutical formulations

The flow injection spectrophotometric determination of cysteine was carried out by reaction with cobalt(II) ions entrapped in a polymeric material and filling a packed-bed reactor; the released cobalt(II) complexed with the amino acid was monitored at 360 nm. The method worked with a high repeatability, even with independent reactors, days and solutions. Selectivity of the procedure was tested with twenty different foreign compounds found in pharmaceutical formulations containing cysteine, parent amino acids included; no serious interferences were observed. The calibration graph for cysteine was linear over the range 1-90 micrograms ml-1 with a relative standard deviation of 0.8% at 60 micrograms ml-1 (n = 158). The calculated sample throughput was 90 h-1. The method was applied to determine the content of cysteine in pharmaceutical formulations.     

A tandem-flow assembly for the chemiluminometric determination of hydroquinone

A direct chemiluminescent procedure for determination of hydroquinone based on the emergent flow methodology known as multicommutation or tandem-flow is presented for first time. The manifold was based on a set of three channels and three solenoid valves; and, the determination was performed at 60 °C and at flow-rate of 7.5 ml min⁻¹. The complete cycle lasted 35 s, which resulted in a sample flow trough of 103 h⁻¹. The chemical process was the hydroquinone oxidation with the system sulphuric acid-potassium permanganate; and the light emission was clearly enhanced by the presence of quinine sulphate and benzalkonium chloride reaching a detection limit of 30 μg l⁻¹. The dynamic interval was over the range 0.1-15.0 mg l⁻¹ and a large list of interferents were assayed; the chemical robustness was also tested. The method was applied to different type of samples: namely, pharmaceutical formulations, a photographic solution and irrigation and residual superficial waters.     

Application of GRAM and TLD to the resolution and quantitation of real complex multicomponent mixtures by fluorescence spectroscopy

The application of the generalised rank annihilation method (GRAM) and the trilinear decomposition (TLD) method to the resolution and quantitation of fluorescence excitation-emission matrices of a ternary mixture of pesticides, carbendazim, fuberidazole, and thiabendazole, with overlapped spectra is described. The results obtained with both methods are compared and evaluated using measures of similarity (correlation coefficients) between the real and estimated spectra. Both approaches have been tested using augmented data matrices containing only two samples, but none of these methods succeeded completely in resolution of the system. When TLD was applied to augmented data matrices containing more than two samples better performance was achieved. To illustrate the application of both algorithms to real samples, they were used in the analysis of water samples containing the target pesticides. Again, TLD had an advantage over GRAM because the ability to analyse data from multiple (more than two) samples simultaneously allowed the resolution of the mixtures.     

Magnetic and structural properties of the Nd2(Fe100−x Nb x )14B system prepared by arc melting

In this work the magnetic and structural properties are investigated by Mössbauer spectrometry, Vibrating Sample Magnetometry and X-ray diffraction of Nd₂(Fe_100?x Nb _x )₁₄B powdered alloys with x?=?0, 2 and 4 prepared by arc melting. The Mössbauer spectra of the samples were fitted with several contributions from: Nd₂Fe₁₄B, α-Fe and a paramagnetic phase associated with Nd_1.1Fe₄B₄ for x?=?0 and additionally from NbFeB and Nd₂Fe₁₇ for x?=?2 and x?=?4. The relative fractions of α-Fe and Nd₂Fe₁₄B are smaller for x?=?4 than for x?=?0, indicating that the amount of these two phases is reduced with increasing Nb content, while the relative fraction of Nd₂Fe₁₇ increases. The α-Fe grain size slightly decreases while that of the Nd₂Fe₁₄B phase is increasing, when the Nb content increases. The hysteresis loops indicate that these samples behave as hard ferromagnets, with a coercive field which decreases when the Nb content increases, but with rather low remanent magnetization.     

A new family of expansive graphs

An affine graph is a pair (G,σ) where G is a graph and σ is an automorphism assigning to each vertex of G one of its neighbors. On one hand, we obtain a structural decomposition of any affine graph (G,σ) in terms of the orbits of σ. On the other hand, we establish a relation between certain colorings of a graph G and the intersection graph of its cliques K(G). By using the results we construct new examples of expansive graphs. The expansive graphs were introduced by Neumann-Lara in 1981 as a stronger notion of the K-divergent graphs. A graph G is K-divergent if the sequence |V(Kⁿ(G))| tends to infinity with n, where Kⁿ⁺¹(G) is defined by Kⁿ⁺¹(G)=K(Kⁿ(G)) for n?1. In particular, our constructions show that for any k?2, the complement of the Cartesian product C^k, where C is the cycle of length 2k+1, is K-divergent.     

Scanning probe microscopy characterization of single chains based on a one-dimensional oxalato-bridged manganese(II) complex with 4-aminotriazole

The compound [Mn(mu-ox)(4atr)2]n (1) (ox = oxalato and 4atr = 4-amine-1,2,4-triazole) has been synthesized and characterized by FT-IR spectroscopy, thermal analysis, variable-temperature magnetic measurements, and X-ray single-crystal diffraction methods. The crystal structure of compound 1 consists of one-dimensional linear chains in which trans-[Mn(4atr)2]2+ units are sequentially bridged by centrosymmetric bis-bidentate oxalato ligands. Cryomagnetic measurements show an overall antiferromagnetic behavior of the compound. Isolated chains of this polymer have been obtained by sonication of 1 in ethanol or treatment of the polymer with NaOH and morphologically characterized on highly oriented pyrolitic graphite and mica surfaces by atomic force microscopy and scanning tunneling microscopy. The procedures employed to obtain single chains of this coordination polymer open a route for future nanotechnological applications of these types of materials.     

On the 0-dimensional irreducible components of the singular locus of \mathcal{A}_g

In this short note we give a characterization of extremal principally polarized abelian varieties determining an isolated point in Sing The case g = 5 is treated in depth.Received: 14 June 2004