Studies on comblike polymers. X. Characterization of comblike polyesters by 13C NMR spectroscopy

The ¹³C NMR spectra of aromatic comblike polyesters obtained from 1,2-icosanediol and isomeric phthalic acids are reported and discussed. The analysis shows that the most informative spectral regions are those of the carbonyl and quaternary carbon resonances, whose peak multiplicities have been interpreted in terms of dyad and triad sequences. The results indicate that the extent of structural characterization possible for the polymers examined is dependent on the type of isomerism of the aromatic acid involved.     

Thermodynamics of alcohols and monosaccharides in aqueous solutions of biuret at 25°C

The excess enthalpies of ternary aqueous solutions of biuret with four aliphatic alcohols or four isomeric pentoses have been determined by flow microcalorimetry at 25°C. The coefficients of the virial expansion of the excess enthalpies have been evaluated and compared with those already reported for urea and thiourea with the same alcohols and pentoses used here. For biuret-alcohol systems, the cross coefficients are positive and depend on the length and branching of the alkyl chain of the alcohols. On the contrary, they are negative for biuret-pentose systems. Hence, biuret, as urea and thioura, is able to differentiate the behavior of families of solutes characterized by the same functional groups. The results are interpreted in terms of the relative stabilities of the hydration cospheres of predominantly hydrophobic or predominantly hydrophilic cosolutes. However, hypotheses about the hydration cospheres of the saccharides, which are more complex than those used previously, seem to be necessary to rationalize their complete behavior in water.     

Metal-metabolomics of microalga Chlorella sorokiniana growing in selenium- and iodine-enriched media

The microalga Chlorella sorokiniana has been used to accumulate selenium and iodine from culture media enriched with these elements as a first stage in the production of supplemented foods. The microalgal colony was grown in a conventional culture medium containing iodine (KI) at concentrations in the range of 150?C4000 ??g mL^?1. Similar experiments were performed with selenium (SeO ₄ ^2? ) at concentrations in the range of 20?C500 ??g mL^?1. The concentration of iodine and selenium in the culture medium was analytically monitored daily and the viability of the colony was checked by biomass concentration measurement and by evaluation of the total content of chlorophyll and carotenoids. In addition, photosynthetic activity and the number of cells were also monitored. Iodine accumulation in the algal biomass increased rapidly with time and reached a steady state after 4 h of exposure. With Se exposure the colony viability decreased, although the culture grew well with concentrations of the element of 50 ??g mL^?1 in the culture medium; this experiment produced Se-enrichment in the alga (3 ??g g^?1) within 100 h. Sequential extraction of an algal pellet was performed in order to separate Se compounds according to their affinity with the following solvents: hot water to recover low molecular mass Se species, enzymatic extraction with driselase for species associated with the cell wall, sodium dodecyl sulphate (SDS) for water insoluble selenoproteins and, finally, enzymolysis with lipase and pronase that release and fragment residual selenoproteinsproducing compounds with low molecular mass. Size-exclusion chromatography (SEC) coupled with an ICP-MS detector showed the preponderance of Se-containing molecules with low molecular mass, possibly seleno-amino acids. Only a peak of low intensity located at 10 min was observed in the SDS extract that could be associated with a protein with molecular mass of 67 kDa. Finally, analysis of the aqueous extract of alga by reverse-phase chromatography with inductively-coupled plasma mass-spectrometry (RPC-ICP-MS) detection revealed the presence of selenocysteine (SeCys₂), selenomethylselenocysteine (SeMetSeCys), selenomethionine (SeMet), and Se(VI), particularly the last two species.     

Implementation and validation of the Lacks-Gordon exchange functional in conventional density functional and adiabatic connection methods

We present an analysis of the numerical performances of the exchange functional proposed by Lacks and Gordon, which we have implemented in the Gaussian series of programs. This functional has been built with the double aim of respecting most of the known scaling and asymptotic properties and of giving good numerical performances, especially as concerns noncovalent interactions. We have found that the coupling of the Lacks-Gordon exchange and Lee-Yang-Parr correlation functionals provides a reliable conventional density functional approach. The corresponding parameter-free adiabatic connection model, in which the ratio between Hartree-Fock and Lacks-Gordon exchange is determined a priori from purely theoretical considerations, allows us to obtain remarkable results for both covalent and noncovalent interactions in a satisfactory theoretical scheme, encompassing the free electron gas limit and most of the known scaling conditions. © 1998 John Wiley & Sons, Inc. J Comput Chem 19: 418–429, 1998     

Antioxidant activity of o-bisphenols: the role of intramolecular hydrogen bonding

A kinetic and thermodynamic investigation on the antioxidant activity of 2,2'-methylenebis(6-tert-butyl-4-methylphenol) (2), 2,2'-ethylidenebis(4,6-di-tert-butylphenol) (3), and 4,4'-methylenebis(2,6-di-tert-butylphenol) (4) are reported. EPR studies of the equilibration between 3 or 4 and a reference phenol, and the corresponding phenoxyl radicals, allowed us to determine the O-H bond dissociation enthalpy (BDE) of the O-H bond as 81.2 and 81.1 kcal/mol in 3 and 4, respectively. Despite this similarity, the absolute rate constants for the reaction with peroxyl radicals, determined by autoxidation studies under controlled conditions, indicate that the o-bisphenols 2 and 3 behave as excellent antioxidants while the p-bisphenol 4 is less effective by a factor of 64 and 22, respectively. FT-IR spectroscopy and product studies suggest that the very good antioxidant activity of the o-bisphenols largely arises from both the reduced steric crowding about the hydroxyl group and the stabilization of the aroxyl radical due to the formation of an intramolecular hydrogen bond between the residual OH and the oxygen radical center.     

Quantum mechanical study of the conformational behavior of proline and 4R-hydroxyproline dipeptide analogues in vacuum and in aqueous solution

The conformational behavior of the title compounds has been investigated by Hartree-Fock, MP2, and DFT computations on the most significant structures related to variations of the backbone dihedral angles, cis/trans isomerism around the peptide bond, and diastereoisomeric puckering of the pyrrolidine ring. In vacuum the reversed gamma turn (gammal), characterized by an intramolecular hydrogen bridge, corresponds to the absolute energy minimum for both puckerings (up and down) of the pyrrolidine ring. An additional energy minimum is found in the helix region, but only for an up puckering of the pyrrolidine ring. When solvent effects are included by means of the polarizable continuum model the conformer observed experimentally in condensed phases becomes the absolute minimum. The down puckering is always favored over its up counterpart, albeit by different amounts (0.4-0.5 kcal/mol for helical structures and about 2 kcal/mol for gammal structures). In helical structures cis arrangements of the peptide bond are only slightly less stable than their trans counterparts. This is no longer true for gammal structures, because the formation of an intramolecular hydrogen bond is possible only for trans peptide bonds. In most cases, proline and hydroxyproline show the same general trends; however, the electronegative 4(R) substituent of hydroxyproline leads to a strong preference for up puckerings irrespective of the backbone conformation.     

Reliable molecular simulations of solute-solvent systems with a minimum number of solvent shells

In this work, the mean field (MF) method, a continuum-based model designed for treating complex molecular systems, such as liquids and solutions, recently presented by Brancato et al. [J. Chem. Phys. 122, 154109 (2005)], has been further developed and improved especially in the treatment of the electrostatics. The revised model has been used to investigate the size effects on several physical properties of various solute-solvent systems by increasing the number of explicitly included solvent molecules from few tens up to thousands. Results on simple ions, such as sodium and chloride ions, and on a small peptide, such as alanine dipeptide analog (AcAlaNHMe), have shown that solvation structures and dynamics, as well as solvent-induced changes in the solute conformation, can be correctly reproduced by the MF model, providing that only two or three solvent layers are treated explicitly.     

JOC Recent Reviews, Number 81

Reviews are listed in order of appearance in the sources indicated. In multidisciplinary review journals, only those reviews which fall within the scope of this Journal are included. Sources are listed alphabetically in three categories: regularly issued review journals and series volumes, contributed volumes, and other monographs. Titles are numbered serially, and these numbers are used for reference in the index. Major English-language sources of critical reviews are covered. Encyclopedic treatises, annual surveys such as Specialist Periodical Reports, and compilations of symposia proceedings are omitted. This installment of Recent Reviews covers principally the early part of the 2006 literature. Previous installment: J. Org. Chem. 2006, 71(7), 2926-34.