Solvent release upon ion association from entropy data

The translational entropy loss on the association of two ions to form an ion pair or 11 complex is overcompensated by a rotational entropy gain, an electrostatic entropy gain, and an entropy gain due to solvent release from translational immobilization. The first three effects can be calculated, leaving the fourth as a difference from the experimental entropy change on association. The ratio of the solvent release entropy gain to the entropy change on melting of the solvent indicates the number of solvent molecules released on the association. A similar value is obtained from data for the volume change on association.Presented as a poster at the 10th International Conference on Non-Aqueous Solvents (ICNAS) at Leuven, Belgium, August 1986, and at the 24th International Congress on Coordination Chemistry (ICCC) at Athens, Greece, August 1986.     

Organic synthesis on the microgram scale. V

Summary This paper describes a method for theg synthesis of flavone acetates in a sealed capillary tube. The reaction products are separated and purified on a thin-layer plate. The esters are then hydrolyzed on the plate and the parent flavones regenerated. A simple heating device is used which allows for observation of the reaction.

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Zusammenfassung Beschreibung der Mikrogrammsynthese von Flavonacetaten in einem verschmolzenen Kapillarröhrchen. Die Reaktionsprodukte werden auf einer Dünnschichtplatte getrennt und gereinigt. Dann verseift man die Ester auf der Platte und stellt die freien Flavone dar. Ein einfaches Heizgerät ermöglicht die Beobachtung der Reaktion.

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For part IV of this series see Mikrochim. Acta [Wien]1969, 352.     

Relation of the Gibbs free energy of transfer of ions from water to polar solvents to the properties of the solvents and the ions

A statistical treatment of data for the standard molar Gibbs free energies of transfer of monovalent ions from water to polar solvents has been made in terms of properties of the solvents and the ions. A common multiple regression equation with seven fitting constants, for almost 200 data points, has been found to describe the data in terms of four solvent properties: their electron donor and acceptor abilities, dielectric constant, and cohesive energy density, and three ionic properties: charge, size, and softness. For the ions Na⁺, K⁺, Rb⁺, Cs⁺, Tl⁺, (Ph)₄As⁺, Cl^?, Br^? and N ₃ ^? the predictions of the equation are within acceptable error limits of the data, and encourage its application to solvents beyond the thirteen used for the data base. For other ions, e.g. H⁺, Ag⁺, and the larger anions, further interactions must be taken into account.     

Thermodynamics of mixed electrolyte solutions. XI. An isopiestic study of the quaternary system NaCl−KCl−CaCl2−H2O at 25°C

Osmotic and activity coefficients in the aqueous quaternary system sodium chloride-potassium chloride-calcium chloride were derived from isopiestic measurements at 25°C. The isopiestic data were treated by the various procedures of Scatchard, Friedman, and Reilly, Wood, and Robinson. The results obtained showed good agreement with those obtained by pseudo-ternary transforms. Interaction parameters obtained indicated the preponderance of pairwise interactions. Excess Gibbs free energies of mixing were calculated.     

The effectiveness of solvents as hydrogen bond donors

Taft and Kamlet's -scale of solvent hydrogen bond donation ability is reexamined with regard to its correlations with three widely used polarity scales: Dimroth and Reichardt's E _T (30), Kosower's Z and Mayer's A _N , as well as with the _m values of the solvents when present as monomeric solutes. The correlation with E _T serves to extend the solvent -scale according to the expression:

Influence of camphorsulfonic acid in nitroxide‐mediated styrene miniemulsion polymerization

The rate‐accelerating effects of camphorsulfonic acid (CSA) on nitroxide‐mediated styrene miniemulsion polymerization were studied. Polymerizations were initiated with benzoyl peroxide (BPO) as an initiator and mediated with either 2,2,6,6‐tetramethylpiperidinyloxy (TEMPO) or 4‐hydroxy‐2,2,6,6‐tetramethylpiperidinyloxy (OH‐TEMPO). Although CSA has been used to accelerate the rate in bulk nitroxide‐mediated polymerizations, it has not been well studied in emulsion/miniemulsion. With dispersed systems, the effectiveness of CSA is likely to be affected by partitioning between the aqueous and organic phases. In styrene miniemulsion experiments performed over a range of conditions, the effect of adding CSA varied from negligible to significantly increasing the final conversion and molecular weight, depending on the nitroxide:BPO ratio. At a ratio of nitroxide:BPO = 1.7, the effect of CSA addition is small, whereas the final conversion and molecular weight are dramatically enhanced by CSA addition when the nitroxide:BPO ratio is 3.6. CSA is most effective in enhancing the rate and molecular weight when the initial free‐nitroxide concentration is higher. The magnitude of the rate and molecular weight enhancement was similar for TEMPO and OH‐TEMPO despite their differences in water solubility. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2828–2841, 2002     

Photochemically catalyzed reaction of ochratoxin A with D- and L-cysteine

The photolysis (>300 nm) of ochratoxin A (OTA, N-[[(3R)-5-chloro-8-hydroxy-3-methyl-1-oxo-7-isochromanyl]carbonyl]-3-phenyl-L-alanine, 1) in the presence of excess (2 and 12 molar equiv) cysteine (CySH) has been investigated and found to yield sulfur adducts 5 and 6 that are characterized by liquid chromatography-mass spectrometry and 1H-NMR spectroscopy. The adduct 5 was ascribed to the Michael addition conjugate resulting from covalent attachment of CySH to the ochratoxin quinone (4) generated by photooxidation of OTA. This species was also formed by photolysis of a synthetic sample of the hydroquinone of OTA (ochratoxin hydroquinone, 3) in the presence of 12 equiv L-CySH. The conjugate 5 derived from photolysis of 3 with L-CySH was used for 1H-NMR analysis. The sulfur adduct 6 was the major species detected from covalent attachment of CySH to photoactivated OTA, and it resulted from direct displacement of the OTA Cl atom by CySH. The implications of the cysteinyl adducts to the in vivo toxicity of OTA are discussed, with particular emphasis given to conjugate 5, as products from the photooxidative pathway may be of relevance to the nephrotoxic properties of OTA.     

Single particle versus ensemble average: from power-law intermittency of a single quantum dot to quasistretched exponential fluorescence decay of an ensemble

Light-induced diffusion-controlled electron transfer is proposed as an underlying mechanism for the intermittency (power law and breakdown) of a single quantum dot and ensemble-averaged fluorescence decay. The intensity decay can be approximated to a stretched exponential expression. The physical links to the free energy gap, reorganization energy, electronic coupling, and diffusion correlation times are discussed. A procedure is described for extracting these molecular-based parameters from experiments and is demonstrated with examples using existing data.     

Neutral and ionic aluminum,gallium, and indium compounds carrying two or three terminal ethynyl groups

The syntheses of the ionic compounds [Li(+).2 dioxane (2,6-iPr(2)C(6)H(3)N(SiMe(3))Al(C triplebond CSiMe(3))(3))(-)].0.75 dioxane (1), [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))Ga(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (2), and [(Li(+))(2).(dioxane)(7)](0.5) [2,6-iPr(2)C(6)H(3)N(SiMe(3))In(C triplebond CSiMe(3))(3)(-)].1.5 dioxane (3) by the reaction of the corresponding organo metal chloride with LiC triplebond CSiMe(3) are reported. The neutral ethynyl compounds Br-Al(C triplebond CtBu)(2).2 THF (4), Cl-Ga(C triplebond CtBu)(2).THF (5), Cl-In(C triplebond CtBu)(2).2 THF (6), Al(C triplebond CtBu)(3).C[N(Me)CMe](2) (7), Ga(C triplebond CtBu)(3).dioxane (8), and In(C triplebond CtBu)(3).NEt(3) (9) have been obtained in good yields from the reaction of AlBr(3), GaCl(3), and InCl(3) with LiC triplebond CtBu in the presence of a Lewis base. Compound 7 is the first heterocyclic carbene substituted ethynyl derivative. Aluminum and gallium compounds with three terminal ethynyl groups Al(C triplebond CPh)(3).NMe(3) (10) and Ga(C triplebond CPh)(3).NMe(3) (11) have been prepared by the reaction of AlH(3).NMe(3) or GaH(3).NMe(3) with three equivalents of phenylethyne. All the above-mentioned compounds have been structurally studied. In compound 1 the lithium ion is coordinated to the three terminal ethynyl groups, whereas in compounds 2 and 3 the lithium is coordinated to the solvent (dioxane). Compound 8 crystallizes as a coordination polymer with dioxane molecules bridging the individual gallium units.