Solvation thermodynamics: theory and applications

Potential distribution and coupling parameter theories are combined to interrelate previous solvation thermodynamic results and derive several new expressions for the solvent reorganization energy at both constant volume and constant pressure. We further demonstrate that the usual decomposition of the chemical potential into noncompensating energetic and entropic contributions may be extended to obtain a Gaussian fluctuation approximation for the chemical potential plus an exact cumulant expansion for the remainder. These exact expressions are further related to approximate first-order thermodynamic perturbation theory predictions and used to obtain a coupling-parameter integral expression for the sum of all higher-order terms in the perturbation series. The results are compared with the experimental global solvation thermodynamic functions for xenon dissolved in n-hexane and water (under ambient conditions). These comparisons imply that the constant-volume solvent reorganization energy has a magnitude of at most approximately kT in both experimental solutions. The results are used to extract numerical values of the solute-solvent mean interaction energy and associated fluctuation entropy directly from experimental solvation thermodynamic measurements.     

Tentoxin as a scaffold for drug discovery. Total solid-phase synthesis of tentoxin and a library of analogues

[reaction: see text] A solid-phase method for the synthesis of tentoxin has been developed. Two key steps-dehydration and N-alkylation-are carried out while the peptide is anchored to the resin. The method, which has been validated by the preparation of a library of tentoxin analogues, should be applicable to the generation of further libraries that have the tentoxin scaffold structure, as well as other structures containing N-alkylated didehydroamino acids.     

1-Alkyl-2,4-dihydro-1H-pyrazino[2,1-b]quinazoline-3,6-diones as glycine templates. Synthesis of Fiscalin B

An excess of base allows the regio- and diastereoselective alkylation at C(4) of the glycine templates 1-methyl(isopropyl)-2,4-dihydro-1H-pyrazino[2,1-b]quinazoline-3,6-diones 9a and 9b without the need for N(2)-protecting groups. While the alkylation of 9a gave exclusively the 1,4-anti-isomers, the isopropyl derivative 9b required much longer reaction times and occurred with lower diastereoselectivity. Fiscalin B 3 was obtained by alkylation of 9b with N-Boc-3-indolylmethyl bromide followed by indole deprotection.     

Diverse motifs of mannoside clustering on a beta-cyclodextrin core

[reaction: see text] A new method for the synthesis of beta-cyclodextrin-based cluster mannosides by application of the Sonogashira cross-coupling reaction is described. The method allows for the persubstitution of the beta-cyclodextrin at either 2- and 3-positions to give two types of heptavalent clusters, at both 2- and 6-positions to give clusters with 14 mannopyranoside units and at 2-, 3-, and 6-positions to obtain clusters with 21 mannopyranoside ligands.     

Synthesis of 6,19-sulfamidate bridged pregnanes

Conformationally restrained substituted pregnane-20-one derivatives were obtained by an intramolecular nitrene addition onto a C-5/C-6 double bond involving a tethered C-19 sulfamoyl moiety. The resulting aziridine underwent regioselective nucleophilic ring opening at C-5 at room temperature with cyanide, fluoride, and acetate. In the isolated case of acetate, a reversal of regioselectivity was observed at higher temperatures, a result attributed to a rearrangement process involving aziridine ring opening at the C-5 position and subsequent migration of the acetyl moiety to C-6.     

SFE of rosemary oil: Assessment of the influence of process variables and extract characterization

The effects of temperature and solvent density on the characteristics of the extracts obtained from supercritical fluid extraction (SFE) of the volatile compounds from Brazilian rosemary (Rosamarinus officianalis L., Labiatae) using carbon dioxide (CO₂) as solvent were investigated. The experiments were performed in a semi-batch laboratory scale home-made unit at two temperatures, viz. 310.15 and 320.15 K, over the pressure range of 100-160 bar. This study allowed to determine the crossover point and the maximum solubility of the oil. The products were analyzed by HRGC-MS, and compounds grouped in three different classes according to their molecular mass distribution in order to evaluate the influence of the variables studied on the characteristics of the extracts. The model proposed by Sovová was adopted in an attempt to interpret the mass transfer phenomena in the extraction process.     

Further studies on the rotational barriers of Carbamates. An NMR and DFT analysis of the solvent effect for Cyclohexyl N,N-dimethylcarbamate

The solvent effect on the Gibbs energy of activation for rotation around the (C=O)–N bond in cyclohexyl N,N-dimethylcarbamate was investigated by dynamic NMR spectroscopy and density-functional theory at the B3LYP/6-311+G^** level. The experimental barriers were about 15 kcal mol⁻¹ with no appreciable variation when the solvent polarity was changed. A reaction field model was applied to theoretically mediate the solvent effect and the results were comparable to the experimental data. An analysis, based on the Onsager solvation theory, showed that the solvent effect on rotational barriers can be understood employing the total molecular dipole moment, the difference between the dipole moments of the ground and the transition state structures, or both, as appropriate.     

Metal complexes of porphycene,corrphycene, and hemiporphycene: stability and coordination chemistry

Porphyrin (P), porphycene (Pc), corrphycene (Cn), and hemiporphycene (Hpc) represent a series of well defined "4-N in" constitutional porphyrin isomers. These isomers, in the form of their octaethyl derivatives, represent a congruent set of porphyrinoids whose properties can be compared. In this study we report how variations in electronic structure and nitrogen-core size in the free-base forms of these four systems are reflected in the properties of their corresponding metal complexes. Specifically, the effects that these differences have on the axial ligation properties of the Zn(II), Mg(II), Ni(II), and Co(II) complexes of P, Pc, Cn, and Hpc in toluene using pyridine as the axial ligand are detailed. Also reported are the relative stabilities of these complexes under acidic conditions. It is shown that for the zinc, magnesium, and cobalt complexes, there are distinct differences in the ability to maintain four-, five-, or six-coordinate geometries in the presence of similar concentrations of pyridine. By contrast, no apparent differences in axial ligand binding affinity are seen for the four nickel complexes. Little difference in stability was likewise seen when these same complexes were subject to acid-mediated demetallation, with all four falling into stability class II, according to the accepted porphyrin stability ranking system. High stabilities were also seen in the case of the cobalt complexes, with the Pc and Cn complexes being of stability class III and the P and Hpc derivatives falling into stability class II. The Zn(II) and Mg(II) complexes were all far less stable than the corresponding Ni(II) and Co(II) complexes. In this case, semiquantitative analyses of the rate of acid-induced decomposition revealed the following stability sequence P>Cn>Hpc>Pc for both the Zn(II) and Mg(II) complexes. Single-crystal X-ray diffraction structures were solved for the Zn(II), Mg(II), and Ni(II) complexes of the octaethyl derivatives of Hpc, Cn, and Pc as well as a Co(II) octamethylcorrphycene and are reported as part of this study. These solid-state structures confirm four-coordinate species for the Ni(II) complexes, four- and five-coordinate species for the Mg(II) and Zn(II) complexes, and a six-coordinate species for the lone Co(II) complex.     

Impact of solar ultraviolet radiation on marine phytoplankton of Patagonia, Argentina

Patagonia area is located in close proximity to the Antarctic ozone "hole" and thus receives enhanced ultraviolet B (UV-B) radiation (280-315 nm) in addition to the normal levels of ultraviolet A (UV-A; 315-400 nm) and photosynthetically available radiation (PAR; 400-700 nm). In marine ecosystems of Patagonia, normal ultraviolet radiation (UVR) levels affect phytoplankton assemblages during the three phases of the annual succession: (1) prebloom season (late summer-fall), (2) bloom season (winter-early spring) and (3) postbloom season (late spring-summer). Small-size cells characterize the pre- and postbloom communities, which have a relatively high photosynthetic inhibition because of high UVR levels during those seasons. During the bloom, characterized by microplankton diatoms, photosynthetic inhibition is low because of the low UVR levels reaching the earth's surface during winter; this community, however, is more sensitive to UV-B when inhibition is normalized by irradiance (i.e. biological weighting functions). In situ studies have shown that UVR significantly affects not only photosynthesis but also the DNA molecule, but these negative effects are rapidly reduced in the water column because of the differential attenuation of solar radiation. UVR also affects photosynthesis versus irradiance (P vs E) parameters of some natural phytoplankton assemblages (i.e. during the pre- but not during the postbloom season). However, there is a significant temporal variability of P vs E parameters, which are influenced by the nutrient status of cells and taxonomic composition; taxonomic composition is in turn associated with the stratification conditions (e.g. wind speed and duration). In Patagonia, wind speed is one of the most important variables that conditions the development of the winter bloom by regulating the depth of the upper mixed layer (UML) and hence the mean irradiance received by cells. Studies on the interactive effects of UVR and mixing show that responses of phytoplankton vary according to the taxonomic composition and cell structure of assemblages; therefore cells use UVR if >90% of the euphotic zone is being mixed. In fact, cell size plays a very important role when estimating the impact of UVR on phytoplankton, with large cells being more sensitive when determining photosynthesis inhibition, whereas small cells are more sensitive to DNA damage. Finally, in long-term experiments, it was determined that UVR can shape the diatom community structure in some assemblages of coastal waters, but it is virtually unknown how these changes affect the trophodynamics of marine systems. Future studies should consider the combined effects of UVR on both phytoplankton and grazers to establish potential changes in biodiversity of the area.     

Photooxygenation of 9-methyl-1,2,3,4-tetrahydrocarbazole: A kinetic study

The reaction of the singlet oxygen with 9-methyl-1,2,3,4-tetrahydrocarbazole has been undertaken to give a benzazonine derivative in good yield. Rose-bengal supported on an anionic resin was used as heterogeneous photosensitizing agent. Kinetic evaluation has been made for the additon of singlet oxygen to the indole ring at room temperature.

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