The (9)Be((8)Li, (9)Be)(8)Li elastic-transfer reaction

Angular distributions for the (9)Be((8)Li, (9)Be) (8)Li elastic-transfer reaction have been measured with a 27-MeV (8)Li radioactive nuclear beam. Spectroscopic factors for the <(9)Be vertical bar(8)Li + p > bound system were obtained from the comparison between the experimental differential cross sections and finite-range distorted-wave Born approximation calculations made with the code FRESCO. The spectroscopic factors so obtained are compared with shell-model calculations and other experimental values. Using the present value for the spectroscopic factors, cross sections and reaction rates for the (8)Li(p,gamma) (9)Be direct proton-capture reaction of astrophysical interest were calculated in the framework of the potential model.

Solvent Effects in Chemical Processes. Water-Assisted Proton Transfer Reaction of Pterin in Aqueous Environment

Pterins are members of a family of heterocyclic compounds present in a wide variety of biological systems and may exist in two forms, corresponding to an acid and a basic tautomer. In this work, the proton transfer reaction between these tautomeric forms was investigated in the gas phase and in aqueous solution. In gas phase, the intramolecular mechanism was carried out for die isolated pterin by quantum mechanical second-order Moller-Plesset Perturbation theory (MP2/aug-cc-pVDZ) calculations and it indicates that the acid form is more stable than the basic form by -1.4 kcal/mol with a barrier of 34.2 kcal/mol with respect to the basic form. In aqueous solution, the role of the water molecules in the proton transfer reaction was analyzed in two separated parts, the direct participation of one water molecule in the reaction path, called water-assisted mechanism, and the complementary participation of the aqueous solvation. The water-assisted mechanism was carried out for one pterin-water cluster by quantum mechanical calculations and it indicates that the acid form is still more stable by -3.3 kcal/mol with a drastic reduction of 70% of the barrier, The bulk solution effect on the intramolecular and water-assisted mechanisms was included by free energy perturbation implemented on Monte Carlo simulations. The bulk water effect is found to be substantial and decisive when the reaction path involves the water-assisted mechanism. In this case, the free energy barrier is only 6.7 kcal/mol and the calculated relative Gibbs free energy for the two tautomers is -11.2 kcal/mol. This value is used to calculate the pK(a) value of 8.2 +/- 0.6 that is in excellent agreement with the experimental result of 7.9.

Transfer reactions in the investigation of light-nuclei nucleosynthesis

Cross sections for the (6)Li(p,gamma)(7)Be, (7)Li(n,gamma)(8)Li (8)Li(n,gamma)(9)Li and (8)Li(p,gamma)(9)Be capture reactions have been investigated in the framework of the potential model. The main ingredients of the potential model are the potentials used to generate the continuum and bound-state wave functions and spectroscopic factors of the corresponding bound systems. The spectroscopic factors for the (7)Li circle times n=(8)Li(gs), (8)Li circle times n=(9)Li(gs) bound systems were obtained from a FR-DWBA analysis of neutron transfer reactions induced by (8)Li radioactive beam on a (9)Be target, while spetroscopic factor for the (8)Li circle times n=(9)Be(gs) bound system were obained from a proton transfer reaction. From the obtained capture reaction cross section, reaction rate for the (8)Li(n,gamma)(9)Li and (8)Li(p,gamma)(9)Be direct neutron and proton capture were determined and compared with other experimental and calculated values.

Picosecond Dynamics of Proton Transfer of a 7-Hydroxyflavylium Salt in Aqueous-Organic Solvent Mixtures

The intermediacy of the geminate base proton pair (A*center dot center dot center dot H(+)) in excited-state proton-transfer (ESPT) reactions (two-step mechanism) has been investigated employing the synthetic flavylium salt 7-hydroxy-4-methyl-flavylium chloride (HMF). In aqueous solution, the ESPT mechanism involves solely the excited acid AH* and base A* forms of HMF as indicated by the fluorescence spectra and double-exponential fluorescence decays (two species, two decay times). However, upon addition of either 1,4-dioxane or 1,2-propylene glycol, the decays become triple-exponential with a term consistent with the presence of the geminate base proton pair A*center dot center dot center dot H(+). The geminate pair becomes detectable because of the increase in the recombination rate constant, k(rec), of (A*center dot center dot center dot H(+)) with increasing the mole fraction of added organic cosolvent. Because the two-step ESPT mechanism splits the intrinsic prototropic reaction rates (deprotonation of AH(+)*, k(d), and recombination, k(rec) of A*center dot center dot center dot H(+)) from the diffusion controlled rates (dissociation, k(diss) and formation, k(diff)[H(+)], of A*center dot center dot center dot H+), the experimental detection of the geminate pair provides a wealth of information on the proton-transfer reaction (k(d) and k(rec)) as well as on proton diffusion/migration (k(diss) and k(diff)).

Gas-Phase Acylium Ion Transfer Reactions Mediated by a Proton Shuttle Mechanism

The mechanism and the energy profile of the gas-phase reaction that mimics esterification under acidic conditions have been investigated at different levels of theory. These reactions are known to proceed with rate constants close to the collision limit in the gas-phase and questions have been raised as to whether the typical addition-elimination mechanism via a tetrahedral intermediate can explain the ease of these processes. Because these reactions are common to many organic and biochemical processes it is important to understand the intrinsic reactivity of these systems. Our calculations at different levels of theory reveal that a stepwise mechanism via a tetrahedral species is characterized by energy barriers that are inconsistent with the experimental results. For the thermoneutral exchange between protonated acetic acid and water and the exothermic reaction of protonated acetic acid and methanol our calculations show that these reactions proceed initially by a proton shuttle between the carbonyl oxygen and the hydroxy oxygen of acetic acid mediated by water, or methanol, followed by displacement at the acylium ion center. These findings suggest that the reactions in the gas-phase should be viewed as an acylium ion transfer reaction. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 111: 1596-1606, 2011

Electrochemical and spectroscopic characterization of screen-printed gold-based electrodes modified with self-assembled monolayers and Tc85 protein

This work investigates the formation of self-assembled monolayers (SAMs) of cystamine and cystamine-glutaraldehyde on a screen-printed electrode, and the immobilization of the Tc85 protein (from Trypanosoma cruzi) on these monolayers. The methods used included infrared techniques, cyclic voltammetry, and electrochemical impedance spectroscopy. The electrochemical studies were performed at pH 6.9 in 0.1 mol L(-1) phosphate buffer solution containing Fe(CN)(6)(-3/-4) redox species. The surface coverage (0) of the electrode was 0.10 (cystamine), 0.35 (cystamine-glutaraldehyde) and 0.84 (Tc85). Interpretation of electrochemical impedance spectroscopy results was based on a charge-transfer reaction involving Fe(CN)(6)(-3/-4) species at high frequencies, followed by a diffusion through the monolayers at lower frequencies. Estimates of the electrode surface coverage, active site radius, and distance between two adjacent sites assumed that charge transfer occurred at the active sites, and that there was a planar diffusion of redox species to these sites. (C) 2009 Elsevier B.V. All rights reserved.

Syntheses, electrochemistry and photophysical properties of a series of meso-pyridylpentafluorophenylporphyrins

This work presents the synthesis and characterization of a series of substituted pyridylpentafluroporphyrins, including the separation of the cis- and trans-isomers, the latter being characterized by X-ray crystallography. The spectroscopic and electrochemical properties of the series are dependent on the number of electron withdrawing pentafluorophenyl substituent, but they do not depend on the symmetry of the molecule. Ongoing from the monosubstituted to the more substituted pentafluorophenyl porphyrin H(2)(MPyTFPP) derivative, the Soret bands are slightly red-shifted and their quantum fluorescence yields range from 0.035 to 0.046, consistent with the value of 0.045 for the fully substituted 5,10,15,20-tetrapentafluorophenylporphyrin (dichloromethane solutions). The redox potentials of the reductive processes of monoanion and dianion formation are also sensitive to the number of pentafluoro substituents, shifting 180 mV to more positive values for the P(0)/P(-1) process ongoing from the monopentafluoro to the tris-pentafluorophenyl substituted derivative.

Aerosol properties, in-canopy gradients, turbulent fluxes and VOC concentrations at a pristine forest site in Amazonia

Aerosol physical and chemical properties were measured in a forest site in central Amazonia (Cuieiras reservation, 2.61S; 60.21W) during the dry season of 2004 (Aug-Oct). Aerosol light scattering and absorption, mass concentration, elemental composition and size distributions were measured at three tower levels (Ground: 2 m; Canopy: 28 m, and Top: 40 m). For the first time, simultaneous eddy covariance fluxes of fine mode particles and volatile organic compounds (VOC) were measured above the Amazonian forest canopy. Aerosol fluxes were measured by eddy covariance using a Condensation Particle Counter (CPC) and a sonic anemometer. VOC fluxes were measured by disjunct eddy covariance using a Proton Transfer Reaction Mass Spectrometer (PTR-MS). At nighttime, a strong vertical gradient of phosphorus and potassium in the aerosol coarse mode was observed, with higher concentrations at Ground level. This suggests a source of primary biogenic particles below the canopy. Equivalent black carbon measurements indicate the presence of light-absorbing aerosols from biogenic origin. Aerosol number size distributions typically consisted of superimposed Aitken (76 nm) and accumulation modes (144 nm), without clear events of new particle formation. Isoprene and monoterpene fluxes reached respectively 7.4 and 0.82 mg m(-2) s(-1) around noon. An average fine particle flux of 0.05 +/- 0.10 10(6) m(-2) s(-1) was calculated, denoting an equilibrium between emission and deposition fluxes of fine mode particles at daytime. No significant correlations were found between VOC and fine mode aerosol concentrations or fluxes. (C) 2009 Elsevier Ltd. All rights reserved.

Scientific program of the Radioactive Ion Beams Facility in Brasil (RIBRAS)

The RIBRAS facility (Radioactive Ion Beams in Brasil) is installed in connection with the 8MV Pelletron tandem of the University of Sao Paulo Physics Institute. It consists of two superconducting solenoids which focalize light radioactive secondary beams of low energy, produced by transfer reactions. Recent experimental results include the elastic scattering and transfer reactions of (6)He halo nucleus on (9)Be, (27)Al, (51)V and (120)Sn targets. The elastic scattering and transfer of (8)Li and (7)Be on several targets is also being studied. The transfer reaction (8)Li(p,alpha)(5)He of astrophysical interest was also Studied in the E(cm)=0.2-2.5 MeV energy range.

Optimization of incubation time of protein Tc85 in the construction of biosensor: Is the EIS a good tool?

Electrochemical impedance spectroscopy (EIS) in pH 6.9 phosphate buffer solution was used to investigate each step of the procedure employed to modify a screen-printed electrode (SPE). The SPE was modified with self-assembled monolayers (SAMs) of cystamine (CYS, deposited from 20 mM solution), followed by glutaraldehyde (GA, 0.3 M solution). The Trypanosoma cruzi antigen was immobilized using different deposition times. The influence of incubation time (2-18 h) of protein was also investigated. The topography of modified electrode with this protein was investigated by atomic force microscopy (AFM). Interpretation of impedance data was based on physical and chemical adsorption, and degradation of the layer at high and meddle frequencies, and charge transfer reaction involving mainly the reduction of oxygen at low frequencies. EIS studies on modified electrodes with Tc85 protein immobilized for different incubation times indicated that the optimum incubation time was 6-8 h. It was demonstrated that EIS is a good technique to evaluate the different steps and the integrity of the surface modifications, and to optimize the incubation time of protein in the development of biosensors. (C) 2010 Elsevier B.V. All rights reserved.

Thionicotinamide SAM on Gold: Adsorption Studies and Electroactivity

STM and impedance results of the self-assembled monolayer (SAM) formed with thionicotinamide (TNA) on gold indicate the presence of defects that increase with the immersion time of the electrode in the TNA solution affecting the SAM electroactivity toward the electron transfer reaction of the cytochrome e metalloprotein and [Fe(CN)(6)](4-) and [Ru(NH(3))(6)](3+) complexes. It was observed that this electroactivity was also affected by the pH of the electrolyte solution. SERS and STM data indicate sulfur coordination to the surface with contribution of the NH(2) group. From the dependence of the TNA surface coverage on the temperature and concentration in solution, thermodynamic parameters of adsorption were determined.

Microwave-Assisted Derivatization of Cellulose in an Ionic Liquid: An Efficient, Expedient Synthesis of Simple and Mixed Carboxylic Esters

Microwave (MW)-assisted cellulose dissolution in ionic liquids (ILs) has routinely led either to incomplete biopolymer solubilization, or its degradation. We show that these problems can be avoided by use of low-energy MW heating, coupled with efficient stirring. Dissolution of microcrystalline cellulose in the IL 1-allyl-3-methylimidazolium chloride has been achieved without changing its degree of polymerization; regenerated cellulose showed pronounced changes in its index of crystallinity, surface area, and morphology. MW-assisted functionalization of MCC by ethanoic, propanoic, butanoic, pentanoic, and hexanoic anhydrides has been studied. Compared with conventional heating, MW irradiation has resulted in considerable decrease in dissolution and reaction times. The value of the degree of substitution (DS) was found to be DS(ethanoate) > DS(propanoate) > DS(butanoate). The values of DS(pentanoate) and DS(hexanoate) were found to be slightly higher than DS(ethanoate). This surprising dependence on the chain length of the acylating agent has been reported before, but not rationalized. On the basis of the rate constants and activation parameters of the hydrolysis of ethanoic, butanoic, and hexanoic anhydrides in aqueous acetonitrile (a model acyl transfer reaction), we suggest that this result may be attributed to the balance between two opposing effects, namely, steric crowding and (cooperative) hydrophobic interactions between the anhydride and the cellulosic surface, whose lipophilicity has increased, due to its partial acylation. Four ethanoate-based mixed esters were synthesized by the reaction with a mixture of the two anhydrides; the ethanoate moiety predominated in all products. The DS is reproducible and the IL is easily recycled. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 134-143, 2010

Asymmetric phase-transfer catalytic sulfanylation of some 2-methylsulfinyl cyclanones. Modeling of the stereochemical course of the aldol reaction of (SS,2S)-2-methylsulfinyl-2-methylsulfanylcyclohexanone

Increased diastereoisomeric excesses are obtained for the sulfanylation reactions of some 2-methylsulfinyl cyclanones under phase-transfer catalysis using the chiral catalyst QUIBEC instead of TEBA. The optically pure (SS,2S)-2-methylsulfinyl-2-methylsulfanylcyclohexanone thus prepared reacts with ethyl acetate lithium enolate affording, after hydrolysis, (R)-2-[(ethoxycarbonyl)methyl]-2-hydroxycyclohexanone in 60% ee. Density functional theory calculations (at the B3LYP/6-311++G(d,p) level) can successfully explain the origin of this result as the kinetically favored axial attack of the nucleophile to the carbonyl group of the most stable conformer of the cyclanone, in which the CH(3)SO and CH(3)S groups are at the equatorial and axial positions, respectively. (C) 2010 Elsevier Ltd. All rights reserved.

Elastic scattering and total reaction cross sections for the (8)Li+(12)C system

The elastic-scattering angular distribution for (8)Li on (12)C has been measured at E(LAB) = 23.9 MeV with (8)Li radioactive nuclear beam produced by the Radioactive Ion Beams in Brazil facility. This angular distribution was analyzed in terms of optical-model with Woods-Saxon and double-folding Sao Paulo potential. The roles of the breakup and inelastic channels were also investigated with cluster folding and deformed potentials, respectively, through coupled-channels calculations. The angular distribution for the proton-transfer (12)C((8)Li, (9)Be)(11)B reaction was also measured at the same energy. The spectroscopic factor for the <(9)Be|(8)Li + p > bound system was obtained and compared with shell-model calculations and with other experimental values. Total reaction cross sections for the present system were also extracted from the elastic-scattering analysis. A systematic of the reduced reaction cross sections obtained from the present and published data on (6,7,8)Li isotopes on (12)C was performed as a function of energy.

Reaction cross sections for (8)B, (7)Be, and (6)Li+(58)Ni near the Coulomb barrier: Proton-halo effects

Elastic scattering of (8)B, (7)Be, and (6)Li on a (58)Ni target has been measured at energies near the Coulomb barrier. Optical-model fits were made to the experimental angular distributions, and total reaction cross sections were deduced. A comparison with other systems provides striking evidence for proton-halo effects on (8)B reactions. As opposed to the situation for the neutron-halo nucleus (6)He, for which particle transfer dominates, the ""extra"" cross section observed for (8)B appears to result entirely from projectile breakup.