Lipase-catalyzed diacylglycerol production under sonochemical irradiation.

The present paper describes a protocol for production of diacylglycerol by the partial hydrolysis of soybean oil catalyzed by lipase under ultrasound irradiation. Better yields and shorter reaction times were obtained under sonication as compared to the thermal process.

Pseudo-peptides derived from isomannide: inhibitors of serine proteases.

In this paper, we describe the synthesis of a novel class of pseudo-peptides derived from isomannide and several oxazolones as potential inhibitors of serine proteases as well as preliminary pharmacological assays for hepatitis C. Hepatitis C, dengue and West Nile fever are among the most important flaviviruses that share one important serine protease enzyme. Serine proteases belong to the most studied class of proteolytic enzymes and are a primary target in the drug development field. Several pseudo-peptides were obtained in good yields from the reaction of isomannide and oxazolones, and their anti-HCV potential using the HCV replicon-based assay was shown.

Catalase vs peroxidase activity of a manganese(II) compound: identification of a Mn(III)-(mu-O)(2)-Mn(IV) reaction intermediate by electrospray ionization mass spectrometry and electron paramagnetic resonance spectroscopy.

Herein, we report reactivity studies of the mononuclear water-soluble complex [Mn(II)(HPClNOL)(eta(1)-NO(3))(eta(2)-NO(3))] 1, where HPClNOL = 1-(bis-pyridin-2-ylmethyl-amino)-3-chloropropan-2-ol, toward peroxides (H(2)O(2) and tert-butylhydroperoxide). Both the catalase (in aqueous solution) and peroxidase (in CH(3)CN) activities of 1 were evaluated using a range of techniques including electronic absorption spectroscopy, volumetry (kinetic studies), pH monitoring during H(2)O(2) disproportionation, electron paramagnetic resonance (EPR), electrospray ionization mass spectrometry in the positive ion mode [ESI(+)-MS], and gas chromatography (GC). Electrochemical studies showed that 1 can be oxidized to Mn(III) and Mn(IV). The catalase-like activity of 1 was evaluated with and without pH control. The results show that the pH decreases when the reaction is performed in unbuffered media. Furthermore, the activity of 1 is greater in buffered than in unbuffered media, demonstrating that pH influences the activity of 1 toward H(2)O(2). For the reaction of 1 with H(2)O(2), EPR and ESI(+)-MS have led to the identification of the intermediate [Mn(III)Mn(IV)(mu-O)(2)(PClNOL)(2)](+). The peroxidase activity of 1 was also evaluated by monitoring cyclohexane oxidation, using H(2)O(2) or tert-butylhydroperoxide as the terminal oxidants. Low yields (<7%) were obtained for H(2)O(2), probably because it competes with 1 for the catalase-like activity. In contrast, using tert-butylhydroperoxide, up to 29% of cyclohexane conversion was obtained. A mechanistic model for the catalase activity of 1 that incorporates the observed lag phase in O(2) production, the pH variation, and the formation of a Mn(III)-(mu-O)(2)-Mn(IV) intermediate is proposed.

A new oxo-vanadium complex employing an imidazole-rich tripodal ligand: a bioinspired bromide and hydrocarbon oxidation catalyst.

A vanadyl complex with the ligand (bis(1-methylimidazol-2-yl)methyl)(2-(pyridyl-2-yl)ethyl)amine was synthesized and fully characterized by X-ray crystallography, elemental analyses, cyclic voltammetry and infrared, electronic and electron paramagnetic resonance spectroscopies. This compound was designed under the so called hybrid concept. It shows to be able to promiscuously use hydrogen peroxide to oxidize bromide and to catalyze the oxidation of benzene and cyclohexane with very good selectivities.

Electronic nature of carbonium ions and their silicon analogues.

Nonclassical ions or carbonium ions have multi-center bonding from delocalized sigma or pi electrons. The 2-norbornyl cation, its derivative 6,6-difluoro-2-norbornyl cation, tris-homocyclopropenyl cation, 7-norbornenyl cation, and 4-cyclopentenyl cation and their corresponding silicon analogues were studied in this work. All carbocations have topologically different 3c-2e systems. The magnitude of all delocalization indexes between each atomic pair of the 3c-2e bond can be used to predict homoaromaticity. The silicon analogues have a topologically different 3c-2e bond from their corresponding carbocation.

Electronic nature of planar cyclobutenyl dication derivatives.

The cyclobutadiene dication was not experimentally characterized to the date. However, some of its derivatives were. Most of them have planar geometry, but tetramethylcyclobutadiene dication has a nonplanar geometry according to ab initio calculations. From the atoms in molecules (AIM) theoretical analysis, common electronic features for the planar and puckered cyclobutenyl dication derivatives were observed. The planar cyclobutenyl dication derivatives have bond order of chemical bonds in the ring close to unity and relatively small electronic density in the ring. The puckered cyclobutadiene dication and its puckered derivatives have relatively high electronic density in the ring.

Electrochemical behaviour of mononuclear Fe(III) complexes as models for oxygenases: reactivity of Fe(II) species electrochemically formed in situ toward dioxygen.

In this paper, we report the electrochemical study of a family of mononuclear Fe(III) complexes [Fe(BMPA)Cl(3)] 1, [Fe(MPBMPA)Cl(3)] 2, [Fe(PBMPA)Cl(2)]3 and [Fe(PABMPA)Cl(2)](ClO(4)) 4, where the ligand BMPA is bis-(2-pyridylmethyl)amine, and MPBMPA, PBMPA and PABMPA are the N-methylpropanoate, N-propanoate and N-propanamide BMPA-derivatives, respectively. It was possible to verify the influence of the different ligands on the redox properties of the complexes and from this to classify the complexes according to their Lewis acidity through the Fe(III)/Fe(II) redox process, resulting in the following decreasing order in CH(3)CN solution: 4> 2> 1> 3. The effect of the solvents CH(3)CN and DMSO on their electrochemical properties was also determined. Furthermore, we investigated the reactivity of the electrochemically-generated Fe(II) complexes toward dioxygen and of the Fe(III) complexes toward superoxide through cyclic voltammetry. All the complexes reacted with dioxygen and superoxide in DMSO solution. Redox processes attributed to oxygenated species were observed in a more cathodic potential than those of the original compounds. According to the data, the new species Fe(II)-O(2) converts itself to Fe(III)-O(2)(-), which presents a new redox wave attributed to the process Fe(III)-O(2)(-) + e(-) --> Fe(II)-O(2)(-). The same species Fe(III)-O(2)(-) is formed from the reaction of the Fe(III) form of the complexes and KO(2).

Catalytic oxidation of cyclohexane by a binuclear Fe(III) complex biomimetic to methane monooxygenase.

A novel binuclear Fe(III) complex [Fe(III)(BPMP)Cl(mu-O)Fe(III)Cl3] (1) was prepared from the reaction between (bis(2-pyridylmethyl)-1,4-piperazine) and [Fe(OH2)6]Cl3, in acetonitrile. The title compound was characterized by spectroscopic, electrochemical and X-ray crystallography analysis. The catalytic activity of the complex was evaluated through cyclohexane oxidation, using hydrogen peroxide as the terminal oxidant. Reaction products were identified by gas chromatography. Conversions up to 19.2% were observed (12.6% and 6.6% yields for cyclohexanol and cyclohexanone, respectively). The catalytic activity exhibited by 1 suggests that it can be considered as a functional biomimetic analog to methane monooxygenase.

Biochemical and molecular modeling analysis of the ability of two p-aminobenzamidine-based sorbents to selectively purify serine proteases (fibrinogenases) from snake venoms.

Snake venoms contain several trypsin-like enzymes with equivalent physicochemical characteristics and similar inhibition profiles. These are rather difficult to separate by classical purification procedures and therefore constitute a good model for affinity chromatography analysis. Some of these trypsin homologues present fibrinogenase activity, mimicking one or more features of the central mammalian coagulation enzyme, thrombin. It was previously demonstrated that a number of amidine derivatives are able to interact specifically with some of these serine proteases. To understand the enzyme-sorbent interactions we have investigated the ability of two commercially available benzamidine affinity matrices to purify thrombin-like serine proteases (TLSP) with similar biological properties from two snake venoms (Bothrops jararacussu and Lachesis muta rhombeata). Curiously, each sorbent retained a single but distinct TLSP from each venom with high yield. Molecular modeling analysis suggested that hydrophobic interactions within a specific region on the surface of these enzymes could be generated to explain this exquisite specificity. In addition, it was demonstrated that a specific tandem alignment of the two benzamidine sorbents enables the purification of three other enzymes from B. jararacussu venom.

Pseudo-peptides derived from isomannide as potential inhibitors of serine proteases.

Hepatitis C, Dengue and West Nile virus are among of the most important flaviviruses that share one important serine protease enzyme. Serine proteases belong to the most studied class of proteolytic enzymes, and are a primary target in the drug development field. In this paper, we describe the synthesis and preliminary molecular modeling studies of a novel class of N-t-Boc amino acid amides derived of isomannide as potential serine proteases inhibitors.

N- t-Boc-amino acid esters of isomannide. Potential inhibitors of serine proteases.

Hepatitis C, Dengue and West Nile virus are some of the most important flaviviruses, that share one important serine protease enzyme. Serine proteases are the most studied class of proteolytic enzyme and, in these cases, a primary target for drug discovery. In this paper, we describe the synthesis and preliminary molecular modeling studies of a novel class of N- t-Boc amino acid esters derived of isomannide as potential serine proteases inhibitors.

Stability of immobilized D-hydantoinase from Vigna angularis and repeated cycles of highly enantioenriched production of N-carbamoyl-D-phenylglycines.

D-hydantoinase from Vigna angularis was immobilized by covalent linkage to aminopropyl glass beads. Thermal stability, resistance to storage at different pH values and temperatures of this biocatalyst were studied. This enzyme preparation was used as a catalyst to prepare enantioenriched N-carbamoyl-D-phenylglycine, N-carbamyl-D-p-fluorophenylglycine and N-carbamoyl-D-p-trifluoromethylphenylglycine, using a stirred batch reactor. Reactions were conducted during eight repeated reaction cycles, without loss of enzymatic activity or variation of the enantiomeric excess of the respective product (>98%).

Analysis of volatile compounds of taperebá (Spondias mombin L.) and cajá (Spondias mombin L.) by simultaneous distillation and extraction (SDE) and solid phase microextraction (SPME).

Volatile compounds of cajá and taperebá fruits, both classified as Spondias mombin, but from different geographic origins, were extracted (and analyzed) using solid phase microextraction (SPME) and simultaneous distillation and extraction (SDE). Forty-eight compounds were identified in taperebá and 47 in cajá by SPME using a DVB/CAR/PMDS fiber. (E)-Caryophyllene (18.7%), ethyl butyrate (10.0%), and ethyl hexanoate (7.0%) were the most abundant components in taperebá volatiles extracted by SPME, whereas myrcene (41.1%) and beta-phellandrene (8.5%) were the major compounds in cajá. In the taperebá SDE extract, 46 substances were identified, and (Z)-caryophyllene (13.2%) and limonene (9.5%) were predominant. From the 42 substances found in the SDE extract of cajá, the major components were myrcene (38.0%) and p-cymene (6.2%). The two fruits showed similar chromatograms upon the use of SDE and SPME. These methods made it possible to determine 30 identical components in both fruits by using SDE and 32 by using SPME.

Synthesis and anti-HIV activity of new C2 symmetric derivatives designed as HIV-1 protease inhibitors.

The synthesis of several new anti-HIV-1 compounds is described. The new compounds contain a C(2) symmetry axis and a dihidroxyethylene moiety based on the D-tartaric acid back bone. The synthesis of these compounds was achieved in 36-69% overall yields from D-tartaric acid. The protocol included: acetylation of hydroxyl groups, followed by diamide formation and deacetylation or reduction with LiAlH(4). The anti-HIV 1 activities of these substances were evaluated in PM-1 cells, using Indinavir as standard (IC(50) = 0.2 microM). Two amino alcohol derivatives showed good inhibitory activity against the virus, with IC(50) = 2.0 and 4 microM.