Fmoc-POAC: [(9-fluorenylmethyloxycarbonyl)-2,2,5,5-tetramethylpyrrolidine-N-oxyl-3-amino-4-carboxylic acid]: A novel protected spin labeled beta-amino acid for peptide and protein chemistry

The stable free radical 2,2,6,6-tetramethylpiperidine-N-oxyl-4-amino-4-carboxylic acid (TOAC) is the only spin labeled amino acid that has been used to date to successfully label peptide sequences for structural studies. However, severe difficulty in coupling the subsequent amino acid has been the most serious shortcoming of this paramagnetic marker. This problem stems from the low nucleophilicity of TOAC's amine group towards the acylation reaction during peptide chain elongation. The present report introduces the alternative beta -amino acid 2,2,5,5-tetramethylpyrrolidine-N-oxyl-3-amino-4-carboxylic acid (POAC), potentially useful in peptide and protein chemistry. Investigations aimed at addressing the stereochemistry of this cyclic molecule through X-ray diffraction measurements of crystalline and bulk samples revealed that it consists only of the trans conformer. The 9-fluorenylmethyloxyearbonyl group (Fmoc) was chosen for temporary protection of the POAC amine function, allowing insertion of the probe at any position in a peptide sequence. The vasoactive octapeptide angiotensin II (AII, DRVYIHPF) was synthesized by replacing Pro(7) with POAC. The reaction of Fmoc-POAC with the peptidyl-resin occurred smoothly, and the coupling of the subsequent amino acid showed a much faster reaction when compared with TOAC. POAC(7)-AII was obtained in good yield, demonstrating that, in addition to TOAC, POAC is a convenient amino acid for the synthesis of spin labeled peptide analogues. The present findings open the possibility of a wide range of chemical and biological applications for this novel beta -amino acid derivative, including structural investigations involving its differentiated bend-inducing characteristics.

Integrable anisotropic spin-ladder model

We present an integrable spin-ladder model, which possesses a free parameter besides the rung coupling J. Wang's system based on the SU(4) symmetry can be obtained as a special case. The model is exactly solvable by means of the Bethe ansatz method. We determine the dependence on the anisotropy parameter of the phase transition between gapped and gapless spin excitations and present the phase diagram. Finally, we show that the model is a special case of a more general Hamiltonian with three free parameters.

Deposition of controlled thickness ultrathin SnO2 : Sb films by spin-coating

The technological interest in transparent conductive oxide films (TCOs) has motivated several works in processing techniques, in order to obtain adequate routes to application. In this way, this work describes a new route to obtain antimony-doped tin oxide (ATO) films, based in colloidal dispersions of oxide nanocrystals. The nanoparticles were obtained by a hydrolisis method, using SnCl2 and SbCl3 in ethanolic solutions. The residual halides were removed by dyalisis, obtaining a limpid and transparent colloidal suspension. By this, the method offers the advantage of producing ultrathin films without organic contaminants. This route was employed to produce films with 5, 10, 14, and 18 mol% Sb doping, with thickness ranging from 40 to 70 nm. The physical characterization of the samples showed a uniform layer deposition, resulting in good packing density and high transmittance. A preliminar electrical study confirmed the low electrical resistivity even in the ultrathin films, in such level similar of reported data. The method described is similar in some aspects to layer-by-layer (LbL) techniques, allowing fine control of thickness and interesting properties for ultrathin films, however, with low cost when compared to similar routes.

Spin tunneling in magnetic molecules: Quantitative estimates for Fe8 clusters

Spin tunneling in the particular case of the magnetic molecular cluster octanuclear iron(III), Fe8, is treated by an effective Hamiltonian that allows for an angle-based description of the process. The presence of an external magnetic field along the easy axis is also taken into account in this description. Analytic expressions for the energy levels and barriers are obtained from a harmonic approximation of the potential function which give results in good agreement with the experimental results. The energy splittings due to spin tunneling is treated in an adapted WKB approach and it is shown that the present description can give results to a reliable degree of accuracy. (c) 2007 Elsevier B.V. All rights reserved.

INPLANE RESISTIVITY IN GRAPHITE-INTERCALATION COMPOUNDS OBTAINED FROM CONDUCTION-ELECTRON-SPIN-RESONANCE MEASUREMENTS

We developed a procedure to take advantage of the magnetic-field-modulation-frequency effect on the line shape of conduction-electron-spin resonance of graphite intercalation compounds (GIC's) to extract the absolute value of the in-plane resistivity. We calculated the power absorbed in each slice of the sample normal to the wave penetration, multiplied by a factor to account for the magnetic-field-modulation-frequency effect. Room-temperature spectra of stage-I AlCl3-intercalated GIC in both H-0 perpendicular-to c and H-0 parallel-to c configurations were fitted to the theoretical line shapes and the value of in-plane resistivity (and also the value of c-axis resistivity) obtained from the fitting parameters are in reasonable agreement with those from the literature.

INFLUENCE OF HIGH MICROWAVE DIELECTRIC-CONSTANTS ON THE LINESHAPE OF CONDUCTION-ELECTRON SPIN-RESONANCE

Some synthetic metals show in addition to good conductivity, high microwave dielectric constants. In this work, it is shown how conduction-electron spin resonance(CESR) lineshape can be affected by these high constants. The conditions for avoiding these effects in the CESR measurements are discussed as well as a method for extracting microwave dielectric constants from CESR lines. (C) 1995 Academic Press, Inc.

Flow injection AAS determination of Cd, Cu, and Pb at trace levels in wine using solid phase extraction

A comparative study is reported between C-18 bonded silica gel and powdered polyethylene (PE) as sorbent for Cd, Cu, and Pb determination using ammonium diethyldithiophosphate (ADTP) as the complexing agent in a flow injection system. The complexes were formed in 0.14 mol L-1 HNO3 and processed in a simple flow system comprising a peristaltic pump, a manual injector-commutator, and a sorbent-packed minicolumn. Ethanol was selected as the eluent and analytes in the eluate were determined by flame atomic absorption spectrometry. The optimum concentration of the complexing agent was 0.1% (m/v) ADTP for Cu and Pb determination using either C-18 or PE, and 0.25% (m/v) ADTP for Cd determination using PE. The sample loading flow rates were 5.0, 3.6, and 3.0 mL min(-1) for Cu, Pb, and Cd, respectively. The best elution flow rate was 6.5 mL min(-1). For a 60-sec preconcentration time, the sampling rate was 40 h(-1) and the enrichment factors of 33, 36, and 11 times (C-18) or 18, 22, and 23 times (PE) were obtained for Cu, Pb, and Cd, respectively. The limits of detection (LOD) were 1.6 mug L-1 Cu, 11 mug L-1 Pb, and 2.0 mug L-1 Cd using C-18 or 2.9 mug L-1 Cu, 19 mug L-1 Pb, and 1.0 mug L-1 Cd using PE, respectively. The relative standard deviations (n = 12) were typically <2%, <2%, and <6% for Cd, Cu, and Pb, respectively. The recoveries of Cd, Cu, and Pb added to wine samples varied from 96-99%, 97-102%, and 90-99%, respectively, using C-18 or PE. Accuracy was checked for Cd, Cu, and Pb determination in six wine samples digested by block digestor and open-vessel microwave-assisted digestion systems. The results revealed that C-18 was more efficient for Cu and Pb determination, while PE was the best sorbent for Cd.

Effect of spin-polarized subbands in the inhomogeneous hole gas providing the indirect exchange in GaMnAs bilayers

The magnetic order resulting from the indirect exchange in the metallic phase of a (Ga,Mn)As/GaAs double layer structure is studied via Monte Carlo simulation. The polarization of the hole gas is taken into account, establishing a self-consistency between the magnetic order and the electronic structure. The Curie-Weiss temperatures calculated for these low-dimensional systems are in the range of 50-80 K, and the dependence of the transition temperature with the GaAs separation layer is established. (C) 2003 Published by Elsevier B.V.

Evaluation of sample treatment for the simultaneous flow injection hydride generation and determination of As, Bi, Sb and Se by GRAS

A new method was developed for the simultaneous determination of As, Bi, Sb, and Se by flow injection hydride generation graphite furnace atomic absorption spectrometry. An alternative two-step sample treatment procedure was used. The sample was heated (80degreesC) for 10 min in 6 M HCl to reduce Se(VI) to Se(IV), followed by the addition of 1% (m/v) thiourea solution to reduce arsenic and antimony from the pentavalent to the trivalent states.With this procedure, all analytes were converted to their most favorable and sensitive oxidation states to generate the corresponding hydrides. The pre-treated sample solution was then processed in the flow system for in situ trapping and atomization in a graphite tube coated with iridium. The impermanent modifier remained stable up to 300 firings and new coating out significant were possible wit changes in the analytical performance.The accuracy was checked for As, Bi, Sb, and Se determination in water standard reference materials NIST 1640 and 1643d and the results were in agreement with the certified values at a 95% confidence level. Good recoveries (94-104%.) of spiked mineral waters and synthetic As(V), Sb(Ill), mixtures of As(Ill), Sb(V), Se(VI), and Se(IV) were also found. Calculated characteristic masses were 32 mug As, 79 mug Bi, 35 mug Sb, and 130 pg Se, and the corresponding limits of detection were 0.06, 0.16, 0.19, and 0.59 mug L-1, respectively. The repeatability for a typical solution containing 5 mug L-1 As, Bi, Sb, and Se was in the 1-3% range.

Spectrophotometric detection of arsenic using flow-injection hydride generation following sorbent extraction preconcentration

An automated system with a C-18 bonded silica gel packed minicolumn is proposed for spectrophotometric detection of arsenic using flow-injection hydride generation following sorbent extraction preconcentration. Complexes formed between arsenic(III) and ammonium diethyl dithiophosphate (ADDP) are retained on a C-18 sorbent. The eluted As-DDP complexes are merged with a 1.5% (w/v) NaBH4 and the resulting solution is thereafter injected into the hydride generator/gas-liquid separator. The arsine generated is carried out by a stream of N-2 and trapped in an alkaline iodine solution in which the analyte is determined by the arsenomolybdenum blue method. With preconcentration time of 120 s, calibration in the 5.00-50.0 mu g As l(-1) range and sampling rate of about 20 samples h(-1) are achieved, corresponding to 36 mg ADDP plus 36 mg ammonium heptamolybdate plus 7 mg hydrazine sulfate plus 0.7 mg stannous chloride and about 7 mi sample consumed per determination. The detection limit is 0.06 mu g l(-1) and the relative standard deviation (n = 12) for a typical 17.0 mu g As l(-1) sample is ca. 6%. The accuracy was checked for arsenic determination in plant materials from the NIST (1572 citrus leaves; 1573 tomato leaves) and the results were in agreement with the certified values at 95% confidence level. Good recoveries (94-104%) of spiked tap waters, sugars and synthetic mixtures of trivalent and pentavalent arsenic were also found. (C) 1999 Elsevier B.V. B.V. All rights reserved.

Characterization of gallotannins from Astronium species by flow injection analysis-electrospray ionization-ion trap-tandem mass spectrometry and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)