Single-ion solvation free energies and the normal hydrogen electrode potential in methanol, acetonitrile, and dimethyl sulfoxide

The division of thermodynamic solvation free energies of electrolytes into contributions from individual ionic constituents is conventionally accomplished by using the single-ion solvation free energy of one reference ion, conventionally the proton, to set the single-ion scales. Thus, the determination of the free energy of solvation of the proton in various solvents is a fundamental issue of central importance in solution chemistry. In the present article, relative solvation free energies of ions and ion-solvent clusters in methanol, acetonitrile, and dimethyl sulfoxide (DMSO) have been determined using a combination of experimental and theoretical gas-phase free energies of formation, solution-phase reduction potentials and acid dissociation constants, and gas-phase clustering free energies. Applying the cluster pair approximation to differences between these relative solvation free energies leads to values of -263.5, -260.2, and -273.3 kcal/mol for the absolute solvation free energy of the proton in methanol, acetonitrile, and DMSO, respectively. The final absolute proton solvation free energies are used to assign absolute values for the normal hydrogen electrode potential and the solvation free energies of other single ions in the solvents mentioned above.     

Rates of ligand exchange between >FeIII-OH2 functional groups on a nanometer-sized aqueous cluster and bulk solution

Variable-temperature 17O NMR experiments were conducted on the nanometer-sized Keplerate Mo72Fe30 cluster, with the stoichiometry [Mo72Fe30O252(CH3COO)12[Mo2O7(H2O)]2[H2Mo2O8(H2O)](H2O)91]. approximately 150H2O. This molecule contains on its surface 30 Fe(H2O) groups forming a well-defined icosidodecahedron, and we estimated the rates of exchange of the isolated >FeIII-OH2 waters with bulk aqueous solution. Both longitudinal and transverse 17O-relaxation times were measured, as well as chemical shifts, and these parameters were then fit to the Swift-Connick equations in order to obtain the rate parameters. Correspondingly, we estimate: k(ex)298 = 6.7(+/-0.8) x 106 s-1, which is about a factor of approximately 4 x 104 times larger than the corresponding rate coefficient for the Fe(OH2)63+ ion of k(ex)298 = 1.6 x 102 s-1 (Grant and Jordan, 1981; Inorg. Chem. 20, 55-60) and DeltaH and DeltaS are 26.3 +/- 0.6 kJ mol-1 and -26 +/- 0.9 J mol-1 K-1, respectively. High-pressure 17O NMR experiments were also conducted, but the cluster decomposed slightly under pressure, which precluded confident quantitative estimation of the DeltaV. However, the increase in the reduced transverse-relaxation time with pressure suggests a dissociative character, such as a D or Id mechanism. The enhanced reactivity of waters on the Mo72Fe30 cluster is associated with an increase in the FeIII-OH2 bond length in the solid state of approximately 0.1 A relative to the Fe(OH2)63+ ion, suggesting that a correlation exists between the FeIII-OH2 bond length and k(ex)298. Although there are only few high-spin Fe(III) complexes where both exchange rates and structural data are available, these few seem to support a general correlation.     

The keto-enol tautomerization of ethyl butylryl acetate studied by LC-NMR

The keto-enol tautomerism of ethyl butylryl acetate was studied in mixed solvents under a variety of experimental conditions. The direct measurement of ketonization of the enol tautomer was performed by using the hyphenated technique LC-NMR. The keto and enol tautomers can be separated by using HPLC and their interconversion is a slow process on the NMR timescale. The ketonization reaction was found to be acid catalyzed and the solvent isotope effect, kH2O/kD2O, in an acetonitrile/water mixture, is 5.4. The ketonization rate constants were also measured at different compositions of binary solvents, such as CH3CN/D2O, CD3OD/D2O, and CH3CN/CD3OD. The rate constant and water percentage were found to have an exponential relationship. The reaction rate as a function of solvent polarity will be discussed in this paper.     

Thin stationary sets and disjoint club sequences

We describe two opposing combinatorial properties related to adding clubs to : the existence of a thin stationary subset of and the existence of a disjoint club sequence on . A special Aronszajn tree on implies there exists a thin stationary set. If there exists a disjoint club sequence, then there is no thin stationary set, and moreover there is a fat stationary subset of which cannot acquire a club subset by any forcing poset which preserves and . We prove that the existence of a disjoint club sequence follows from Martin's Maximum and is equiconsistent with a Mahlo cardinal.

     

Search for a bound trineutron with the 3He(π−pgr;+)nnn reaction

A search for the production of a bound trineutron state has been performed using the reaction ³He(π⁻,π⁺)nnn at incident pion energies of 65, 75, and 120 MeV. No evidence for the existence of the ³n was found, and an upper limit for the production cross section of approximately 30 nb/sr (2σ confidence level) was obtained. Received: 22 October 1998     

Changes in vocal intensity in Parkinson's disease following pallidotomy surgery

The present study was designed to examine changes in vocal intensity following unilateral posteroventral pallidotomy (PVP) in a large sample of speakers with Parkinson's disease (PD) that exhibited a range of hypokinetic dysarthria. Twenty-five persons with PD were recorded using a variety of speech tasks, once prior to and once following PVP. The pre-PVP vocal SPL was subtracted from the post-PVP vocal SPL to derive a relative change in vocal SPL. Mildly dysarthric participants had significantly greater relative increases in vocal SPL following PVP than either moderately or severely dysarthric participants who had reduced vocal SPL following PVP. If future results follow those observed in the present data, mildly dysarthric Parkinson's patients may benefit most from unilateral PVP perhaps due to less overall destruction of the basal ganglia sensorimotor control circuits involved in oral facial functions, thus increasing the chances to observe improvements postsurgery.     

Scaling units via the canonical correlation analysis in the DEA context

This paper deals with the evaluation of decision making units which have multiple inputs and outputs. A new method (CCA/DEA) is developed where the Canonical Correlation Analysis (CCA) is utilized to provide a full rank scaling for all the units rather than a categorical classification (for efficient and inefficient units) as done by the Data Envelopment Analysis (DEA). The CCA/DEA approach is an attempt to bridge the gap between the frontier approach of DEA and the average tendencies of statistics (econometrics). Nonparametric statistical tests are employed to validate the consistency between the classification from the DEA and the postclassification that was generated by the CCA/DEA.     

T3P-Promoted Synthesis of a Series of 2-Aryl-3-phenyl-2,3-dihydro-4H-pyrido[3,2-e][1,3]thiazin-4-ones and Their Activity against the Kinetoplastid Parasite Trypanosoma brucei

A series of fourteen 2-aryl-3-phenyl-2,3-dihydro-4H-pyrido[3,2-e][1,3]thiazin-4-ones was prepared at room temperature by T3P-mediated cyclization of N-phenyl-C-aryl imines with thionicotinic acid, two difficult substrates. The reactions were operationally simple, did not require specialized equipment or anhydrous solvents, could be performed as either two or three component reactions, and gave moderate–good yields as high as 63%. This provides ready access to N-phenyl compounds in this family, which have been generally difficult to prepare. As part of the study, the first crystal structure of neutral thionicotinic acid is also reported, and showed the molecule to be in the form of the thione tautomer. Additionally, the synthesized compounds were tested against T. brucei, the causative agent of Human African Sleeping Sickness. Screening at 50 µM concentration showed that five of the compounds strongly inhibited growth and killed parasites.     

An Improved Method to Determine Particle Dispersion Width for Efficient Modeling of Turbulent Two‐Phase Flows

An improved approach is presented for the hybrid Eulerian‐Lagrangian modeling of turbulent two‐phase flows. The hybrid model consists of a nonlinear k–ε model for the fluid flow and an efficient Lagrangian trajectory model for the particulate flow. The improved approach avoids an empirical correlation required to determine the dispersion width for the existing Stochastic‐Probabilistic Efficiency Enhanced Dispersion (SPEED) model. The improved SPEED model is validated using experimental data for a poly‐dispersed water spray interacting with a turbulent annular air jet behind a bluff‐body. Numerical results for the number‐mean and Sauter‐mean droplet diameters, as well as mean and fluctuating droplet velocities are compared with the experimental data and with the predictions of other dispersion models. It is demonstrated that higher computational efficiency and smoother profiles of Sauter‐mean diameter can be obtained with the improved stochastic‐probabilistic model than with the eddy‐interaction model.