Heck reaction catalyzed by Pd/C, in a triphasic-organic/Aliquat 336/aqueous-solvent system

The rate of the Pd/C catalyzed Heck coupling of Ar-I with CH(2)=CH-R is accelerated tenfold by the presence of Aliquat 336 (A336), a well known phase transfer catalyst, and an ionic liquid. Both when conducted in A336 as solvent, and in an isooctane/A336/aqueous triphasic mixture, the Heck reaction of aryl iodides with electron deficient olefins, catalyzed by Pd/C, proceeds with high yields and selectivity. When KOH is used instead of Et(3)N, selective formation of the biphenyl rather than the Heck product, is observed. Aryl bromides react more sluggishly, and only the more activated ones undergo the Heck reaction. In the absence of the olefin, aryl halides possessing an electron withdrawing group are reduced to the corresponding Ar-H.     

Degradation and stabilization of high molecular weight polyethylene in solution

The changes in the molar mass of high molecular weight polyethylene, in o-dichlorobenzene, with time are examined using viscometry. The results show that the molar mass decreases with time and that the observed decay can be satisfactorily explained by a simple degradation model. Commercial antioxidants can inhibit the degradation process if the appropriate concentration is chosen. Thus, at very low concentrations a polynuclear phenol shows good antioxidant behavior but this decreases with an increase in concentration due to direct oxidation of the inhibitor. Conversely, zinc dimethyldithiocarbamate shows the best stabilizing activity which increases with concentration. The results are explained on the basis of the established mechanistic action of these compounds and show that viscometry is not an accurate method for measuring the molar mass of high molecular weight polyethylene samples unless the appropriate conditions are chosen. Even with the best inhibitor, some degradation is still observed.     

Stripping polarography and the reduction of copper(II) in sea water at the hanging mercury drop electrode

An approximate but general theoretical treatment for reversible and irreversible stripping polarographic systems is presented. The treatment is based on the development of an average current (i), which at plating times exceeding 15 s. is analogous to the instantaneous current in d.c. polarography. Plots of i vs. (E – E°) are generated for reversible and irreversible waves and are discussed for the reduction of copper(II) in sea water as an example. From stripping polarography and anodic stripping voltammetry, this work indicates that the overall reduction of copper(II) at the natural pH is kinetically hindered and thus is “irreversible”. The reversibility and the determination of copper in sea water by a.s.v. can be improved by acidification and/or by the addition of ethylenediamine.     

Exploring the potential energy surfaces of association of NO with aminoacids and related organic functional groups: the role of entropy of association

Association between NO and each of the 20 amino acids and their related organic functional groups was studied by exploring the configuration space of the potential energy of association surface by using the multiple minima hypersurface procedure. AM1 semiempirical Hamiltonian was used in order to explore such complex hypersurfaces of biological molecular interactions at finite computational times. An appropriate test with a set of NO and small molecule complexes obtained at the MP2/6-311++g(2d,2p) level of theory was also carried out. Stabilization energies of larger models were also evaluated at the conventional PBE1PBE/6-31g(d,p) DFT level. NO–aminoacid hypersurface explorations yielded that interactions of NO with NH group together with the C=O belonging to the backbone appeared predominant in all cases. Models of polar aminoacids and NO also show stable interactions with the lateral chains. Interactions with charged amino acids were found as the most stable and Lys was, undoubtedly, the preferred association. The study of these kinds of interactions must take into account the deepest and other minima because the entropy of association plays an important role. Contribution to the Serafin Fraja Memorial Issue. Dedicated to Prof. Serafín Fraga, an unforgettable friend.     

Antiprotozoal 6-substituted-5,6-dihydro-alpha-pyrones from Raimondia cf. monoica

Dichloromethane extracts of both the roots and the leaves of Raimondia cf. monoica showed in vitro antiplasmodial and leishmanicidal activities against Plasmodium falciparum and Leishmania panamensis, respectively. Three 6-substituted 5,6-dihydro-2H-pyran-2-ones were isolated. (1) and (2) were identified as (6S)-(5'-oxohepten-1'E,3'E-dienyl)-5,6-dihydro-2H-pyran-2-one (1) and (6R)-(5'-oxohepten-1'Z,3'E-dienyl)-5,6-dihydro-2H-pyran-2-one (2), respectively. (-)-Arentilactone (3) was also isolated. The structure of the new compound (1) was determined by spectroscopic methods; additional spectroscopic data for (2) are reported for the first time.     

In vivo PHYTOCHROME-MEDIATED PERCEPTION OF REFLECTED LIGHT SIGNALS

The spectrophotometric assay of phytochrome in vivo in etiolated plant material was used to determine the effects of changes in reflected light on the state of the photoreceptor in etiolated seedlings exposed simultaneously to direct and reflected light. Changes in reflected light that were small in terms of the total (direct + reflected) radiation incident on the seedlings produced detectable changes in the state of phytochrome in vivo. The contribution of reflected light to the state of phytochrome in vertical organs was greater than expected from its low contribution to total incident light. These data from laboratory studies complement and are consistent with results of field studies on the effects of light reflected from neighboring vegetation on plant growth under natural radiation conditions.     

Solid-phase synthesis of fullerene-peptides

The solid-phase synthesis of peptides (SPPS) containing [60]fullerene-functionalized amino acids is reported. A new amino acid, fulleropyrrolidino-glutamic acid (Fgu), is used for the SPPS of a series of analogues of different length based on the natural Leu(5)-Enkephalin and on cationic antimicrobial peptides. These fullero-peptides were prepared on different solid supports to analyze the influence of the resin on the synthesis. Optimized protocols for the coupling and deprotection procedures were determined allowing the synthesis of highly pure peptides in sufficient quantities for evaluation of biological activities. In particular, to avoid side reactions of the fullerene moiety with bases and nucleophiles, the removal of the protecting groups was performed under inert conditions (nitrogen or argon in the dark). We have encountered serious problems with the recovery of the crude compounds, especially when Fgu was inserted in the proximity of the resin core as fullero-peptides tend to remain embedded inside the resin. Eventually, all of the fullero-peptides were easily purified, and the cationic peptides were tested for their antimicrobial activities. They displayed a specific activity against the Gram-positive bacterium S. aureus and also lysed erythrocytes. The availability of a fullero-amino acid easily useable in the SPPS of fullero-peptides may thus open the way to the synthesis of new types of biologically active oligomers.     

Selective fluorescence sensing of Li+ in an aqueous environment by a ferrocene-anthracene-linked dyad

A new 1-(9-anthryl)-4-ferrocenyl-2-aza-1,3-butadiene showing selective fluorescence enhancement upon binding to lithium cations over other alkaline cations in aqueous environment has been conveniently synthesized and characterized. [structure: see text]     

Synthesis and Structural Characterization of the Trimeric Furoxan (= Furazan 2-Oxide) System,a New Potent Vasodilating Moiety

The synthesis, structural characterization, and NO donor properties of a series of terfuroxan (= terfurazan trioxide) derivatives 1a–h and 2a–j are reported (Schemes 1 and 2). Structural assignments were confirmed principally by mass and ¹³C- and ¹H-NMR spectroscopy. The extent and the initial rate of NO release in the presence of thiol cofactor was evaluated for each derivative. Vasodilator effects of all the terfuroxan derivatives were evaluated on endothelium-denuded strips of rat aorta precontracted with noradrenaline. Concentration-response curves were also evaluated in the presence of 10 m?M oxyhemoglobin (HbO₂), a well known NO scavenger. The whole series displays high vasodilating potency; the most active terfuroxans ( 1a, b, g and 2i ) are 5–10 times as potent as glyceryl trinitrate taken as reference (see Table 3). The potency decrease observed in the presence of HbO₂ agrees with the involvement of NO in the vasorelaxing action. The 4,3′:4′,4″ connection (series 1 ; furoxan numbering) gives rise to the most potent compounds. The conformational factors seem to play important roles in the activity. No clear relationship between physico-chemical properties of the substituents and potencies of derivative emerges.