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.

Surface and Quantum Confinement Effects in ZnO Nanocrystals

ZnO nanocrystals are studied using theoretical calculations based on the density functional theory. The two main effects related to the reduced size of the nanocrystals are investigated: quantum confinement and a large surface:volume ratio. The effects of quantum confinement are studied by saturating the surface dangling bonds of the nanocrystals with hypothetical H atoms. To understand the effects of the surfaces of the nanocrystals, all saturation is removed and the system is relaxed to its minimum energy position. Several different surface motifs are reported, which should be observed experimentally. Spin-polarized calculations are performed in the nonsaturated nanocrystals, leading to different magnetic moments. We propose that this magnetic moment can be responsible for the intrinsic magnetism observed in ZnO nanostructures.

Confinement and surface effects in B and P doping of silicon nanowires

Several experimental groups have achieved effective n- and p-type doping of silicon nanowires (SiNWs). However, theoretical analyses on ultrathin SiNWs suggest that dopants tend to segregate to their surfaces, where they would combine with defects such as dangling bonds (DB), becoming electronically inactive. Using fully ab initio calculations, we show that the differences in formation energies among surface and core substitutional sites decrease rapidly as the diameters of the wires increase, indicating that the dopants will be uniformly distributed. Moreover, occurrence of the electronically inactive impurity/DB complex rapidly becomes less frequent for NWs of larger diameters. We also show that the high confinement in the ultrathin SiNWs causes the impurity levels to be deeper than in the silicon bulk, but our results indicate that for NWs of diameters larger than approximately 3 nm the impurity levels recover bulk characteristics. Finally, we show that different surfaces will lead to different dopant properties in the gap.

Breakup effects in fusion and total reaction cross sections of weakly bound systems

We use a new technique to investigate the systematic behavior of near barrier complete fusion, total fusion and total reaction cross sections of weakly bound systems. A dimensionless fusion excitation function is used as a benchmark to which renormalized fusion data are compared and dynamic breakup effects can be disentangled from static effects. The same reduction procedure is used to study the effect of the direct reaction mechanisms on the total reaction cross section.

Proton-halo effects in the (8)B+(58)Ni reaction near the Coulomb barrier

Elastic scattering of (8)B and (7)Be on a (58)Ni target has been measured at energies near the Coulomb barrier. The total reaction cross sections were deduced from Optical-model fits to the experimental angular distributions. Comparison with other systems shows evidence for proton-halo effects on (8)B, as well as for neutron-halo on (6)He reactions. While the enhancement in the cross section observed for (8)B is explained in terms of projectile breakup, in the case of (6)He reactions, the particle transfer proces explains the observed enhancement.

Joint Experimental and Theoretical Analysis of Order Disorder Effects in Cubic BaZrO(3) Assembled Nanoparticles under Decaoctahedral Shape

Periodic first-principles calculations based on density functional theory at the B3LYP level has been carried out to investigate the photoluminescence (PL) emission of BaZrO(3) assembled nanoparticles at room temperature. The defect created in the nanocrystals and their resultant electronic features lead to a diversification of electronic recombination within the BaZrO(3) band gap. Its optical phenomena are discussed in the light of photoluminescence emission at the green-yellow region around 570 nm. The theoretical model for displaced atoms and/or angular changes leads to the breaking of the local symmetry, which is based on the refined structure provided by Rietveld methodology. For each situation a band structure, charge mapping, and density of states were built and analyzed. X-ray diffraction (XRD) patterns, UV-vis measurements, and field emission scanning electron microscopy (FE-SEM) images are essential for a full evaluation of the crystal structure and morphology.

Combined Crystallographic and Solution Molecular Dynamics Study of Allosteric Effects in Ester and Ketone p-tert-Butylcalix[4]arene Derivatives and Their Complexes with Acetonitrile, Cd(II), and Pb(II)

We describe here a procedure to bridge the gap in the field of calixarene physicochemistry between solid-state atomic-resolution structural information and the liquid-state low-resolution thermodynamics and spectroscopic data. We use MD simulations to study the kinetics and energetics involved in the complexation of lower rim calix[4]arene derivatives (L), containing bidentate ester (1) and ketone (2) pendant groups, with acetonitrile molecule (MeCN) and Cd2+ and Pb2+ ions (M2+) in acetonitrile solution. On one hand, we found that the prior inclusion of MeCN into the calix to form a L(MeCN) adduct has only a weak effect in preorganizing the hydrophilic cavity toward metal ion binding. On the other hand, the strong ion-hydrophilic cavity interaction produces a wide open calix which enhances the binding of one MeCN molecule (allosteric effect) to stabilize the whole (M2+)1(MeCN) bifunctional complex. We reach two major conclusions: (i) the MD results for the (M2+)1(MeCN) binding are in close agreement with the ""endo"", fully encapsulated, metal complex found by X-ray diffraction and in vacuo MD calculations, and (ii) the MD structure for the more flexible 2 ligand, however, differs from the also endo solid-state molecule. In fact, it shows strong solvation effects at the calixarene lower bore by competing MeCN molecules that share the metal coordination sphere with the four C=O oxygens of an ""exo"" (M2+)2(MeCN) complex.

Spin-polarization effects in homogeneous and non-homogeneous diluted magnetic semiconductor heterostructures

Spin polarization is a key characteristic in developing spintronic devices. Diluted magnetic heterostructures (DMH), where subsequent layers of conventional and diluted magnetic semiconductors (DMS) are alternate, are one of the possible ways to obtain it. Si being the basis of modern electronics, Si or other group-IV DMH can be used to build spintronic devices directly integrated with conventional ones. In this work we study the physical properties and the spin-polarization effects of p-type DMH based in group-IV semiconductors (Si, Ge, SiGe, and SiC), by performing self-consistent (k) over right arrow . (p) over right arrow calculations in the local spin density approximation. We show that high spin polarization can be maintained in these structures below certain values of the carrier concentrations. Full spin polarization is attained in the low carrier concentration regime for carrier concentrations in the DMS layer up to similar to 2.0 x 10(19) cm(-3) for Si and up to similar to 6.0 x 10(19) cm(-3) for SiC. Partial, but still important spin polarization can be achieved for all studied group-IV DMH, with the exception of Ge for carrier concentrations up to 6.0 x 10(19) cm(-3). The role played by the effective masses and the energy splitting of the spin-orbit split-off hole bands is also discussed throughout the paper.

Nuclear magnetic resonance water relaxation time changes in bananas during ripening: a new mechanism

BACKGROUND: Nuclear magnetic resonance studies of banana fragments during ripening show an increase on the water transverse relaxation time (T(2)) and a decrease in water self-diffusion coefficient (D). As T(2) and D are normally directly correlated, we studied these two properties in intact bananas during ripening, in an attempt to rule out the effect of injury on the apparent discrepancies in the behavior of T(2) and D. RESULTS: The results show that injury in bananas causes a decrease in T(2) of the water in vacuoles (T(2vac)). They also show that T(2vac) increased and D decreased during ripening, ruling out the injury effect. To explain the apparent discrepancies, we propose a new hypothesis for the increase in T(2) values, based on the reduction of Fe(3+) ions to Fe(2+) by galacturonic acid, produced by the hydrolysis of pectin and a decrease in internal oxygen concentration during ripening. CONCLUSION: As injury alters T(2) values it is necessary to use intact bananas to study relaxation times during ripening. The novel interpretation for the increase in T(2vac) based on reduction of Fe(+3) and O(2) concentration is an alternative mechanism to that based on the hydrolysis of starch in amyloplasts. (C) 2010 Society of Chemical Industry

A Cost Model for the Effect of Setup Time Reduction in Stainless Steel Strip Production

Setup time reduction facilitate the flexibility needed for just-in-time production. An integrated steel mill with meltshop, continuous caster and hot rolling mill is often operated as decoupled processes. Setup time reduction provides the flexibility needed to reduce buffering, shorten lead times and create an integrated process flow. The interdependency of setup times, process flexibility and integration were analysed through system dynamics simulation. The results showed significant reductions of energy consumption and tied capital. It was concluded that setup time reduction in the hot strip mill can aid process integration and hence improve production economy while reducing environmental impact.

Influences of infrastructure and attitudes to health on value of travel time savings in bicycle journeys

In this paper we investigate how attitudes to health and exercise in connection with cycling influence the estimation of values of travel time savings in different kinds of bicycle environments (mixed traffic, bicycle lane in the road way, bicycle path next to the road, and bicycle path not in connection with the road). The results, based on two Swedish stated choice studies, suggest that the values of travel time savings are lower when cycling in better conditions. Surprisingly, the respondents do not consider cycling on a path next to the road worse than cycling on a path not in connection to the road, indicating that they do not take traffic noise and air pollution into account in their decision to cycle. No difference can be found between cycling on a road way (mixed traffic) and cycling in a bicycle lane in the road way. The results also indicate that respondents that include health aspects in their choice to cycle have lower value of travel time savings for cycling than respondents that state that health aspects are of less importance, at least when cycling on a bicycle path. The appraisals of travel time savings regarding cycling also differ a lot depending on the respondents’ alternative travel mode. The individuals who stated that they will take the car if they do not cycle have a much higher valuation of travel time savings than the persons stating public transport as the main alternative to cycling.

Bringing Japanese manufacturing systems to America: the feasibility of implementing just-in-time production in the United States

This paper addresses the feasibility of implementing Japanese manufacturing systems in the United States. The recent success of Japanese transplant companies suggests that Just-In-Time (JIT) production is possible within America's industrial environment. Once American workers receive proper training, they have little difficulty participating in rapid setup procedures and utilizing the kanban system. Japanese transplants are gradually developing Japanese-style relationships with their American supplier companies by initiating long-term, mutually beneficial agreements. They are also finding ways to cope with America's problem of distance, which is steadily decreasing as an obstacle to JIT delivery. American companies, however, encounter Significant problems in trying to convert traditionally organized, factories to the JIT system. This paper demonstrates that it is both feasible and beneficial for American manufacturers to implement JIT production techniques. Many of the difficulties manufacturers experience center around a general lack of information about JIT. Once a company realizes its potential for setup-time reduction, a prerequisite for the JIT system, workers and managers can work together to create a new process for handling equipment changeover. Significant results are possible with minimal investment. Also, supervisors often do not realize that the JIT method of ordering goods from suppliers is compatible with current systems. This "kanban system" not only enhances current systems but also reduces the amount of paperwork and scheduling involved. When arranging JlT delivery of supplier goods, American manufacturers tend to overlook important aspects of JIT supplier management. However, by making long-tenn commitments, initiating the open exchange of information, assisting suppliers in reaching new standards of performance, increasing the level of conununication, and relying more on suppliers' engineering capabilities, even American manufacturers can develop Japanese-style supplier relationships that enhance the effectiveness of the system.

Debt composition and exchange rate balance sheet effects in Brazil: A firm level analysis

In this paper we study the interaction between macroeconomic environment and firms’ balance sheet effects in Brazil during the 1990’s. We start by assessing the influence of macroeconomic conditions on firms’ debt composition in Brazil. We found that larger firms tend to change debt currency composition more in response to a change in the exchange rate risk than small firms. We then proceed to investigate if and how exchange rate balance sheet effects affected the firms’ investment decisions. We test directly the exchange rate balance sheet effect on investment. Contrary to earlier findings (Bleakley and Cowan, 2002), we found that firms more indebted in foreign currency tend to invest less when there is an exchange rate devaluation. We tried different controls for the competitiveness effect. First, we control directly for the effect of the exchange rate on exports and imported inputs. We then pursue an alternative investigation strategy, inspired by the credit channel literature. According to this perspective, Tobin’s q can provide an adequate control for the competitiveness effect on investment. Our results provide supporting evidence for imperfect capital markets, and for a negative exchange rate balance sheet effect in Brazil. The results concerning the exchange rate balance sheet effect on investment are statistically significant and robust across the different specifications. We tested the results across different periods, classified according to the macroeconomic environment. Our findings suggest that the negative exchange rate balance sheet effect we found in the whole sample is due to the floating exchange rate period. We also found that exchange rate devaluations have important negative impact on both cash flows and sales of indebted firms. Furthermore, the impact of exchange rate variations is asymmetric, and the significant effect detected when no asymmetry is imposed is engendered by exchange rate devaluations.

Demand aggregation and credit risk effects in pooled procurement: evidence from the Brazilian public purchases of pharmaceuticals and medical supplies

Pooled procurement has an important role in reducing acquisition prices of goods. A pool of buyers, which aggregates demand for its members, increases bargaining power and allows suppliers to achieve economies of scale and scope in the production. Such aggregation demand e ect lowers prices paid for buyers. However, when a buyer with a good reputation for paying suppliers in a timely manner is joined in the pool by a buyer with bad reputation may have its price paid increased due to the credit risk e ect on prices. This will happen because prices paid in a pooled procurement should refect the (higher) average buyers' credit risk. Using a data set on Brazilian public purchases of pharmaceuticals and medical supplies, we nd evidence supporting both e ects. We show that the prices paid by public bodies in Brazil are lower when they buy through pooled procurement than individually. On the other hand, federal agencies (i.e. good buyers) pay higher prices for products when they are joined by state agencies (i.e. bad buyers) in a pool. Such evidence suggests that pooled procurement should be carefully designed to avoid that prices paid increase for its members.

Anticipatory effects in the FTSE 100 index revisions

This paper examines the price impact of trading due to expected changes in the FTSE 100 index composition. We focus on the latter index because it employs publicly-known objective criteria to determine membership and hence it provides a natural context to investigate anticipatory trading e ects. We propose a panel-regression event study that backs out these anticipatory e ects by looking at the price impact of the ex-ante proba-bility of changing index membership status. Our ndings reveal that anticipative trading explains about 40% and 23% of the cumulative abnormal returns of additions and deletions, respectively. We con rm these in-sample results out of sample by tracking the performance of a trading strategy that relies on the addition/deletion probability estimates. The perfor-mance is indeed very promising in that it entails an average daily excess return of 11 basis points over the FTSE 100 index.