Anion-directed synthesis of metal-organic frameworks based on 2-picolinate Cu(II) complexes: a ferromagnetic alternating chain and two unprecedented ferromagnetic fish backbone chains

Three new polynuclear copper(II) complexes of 2-picolinic acid (Hpic), {[Cu-2(pic)(3)(H2O)]ClO4}(n) (1), {[Cu-2(pic)(3)(H2O)]BF4}(n) (2), and [Cu-2(pic)3(H2O)(2)(NO3)](n) (3), have been synthesized by reaction of the "metalloligand" [Cu-(pic)(2)] with the corresponding copper(II) salts. The compounds are characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. Compounds 1 and 2 are isomorphous and crystallize in the triclinic system with space group P (1) over bar, while 3 crystallizes in the monoclinic system with space group P2(1)/n. The structural analyses reveal that complexes 1 and 2 are constructed by "fish backbone" chains through syn-anti (equatorial-equatorial) carboxylate bridges, which are linked to one another by syn-anti (equatorial-axial) carboxylate bridges, giving rise to a rectangular grid-like two-dimensional net. Complex 3 is formed by alternating chains of syn-anti carboxylate-bridged copper(II) atoms, which are linked together by strong H bonds involving coordinated nitrate ions and water molecules and uncoordinated oxygen atoms from carboxylate groups. The different coordination ability of the anions along with their involvement in the H-bonding network seems to be responsible for the difference in the final polymeric structures. Variable-temperature (2-300 K) magnetic susceptibility measurement shows the presence of weak ferromagnetic coupling for all three complexes that have been fitted with a fish backbone model developed for 1 and 2 (J = 1.74 and 0.99 cm(-1); J' = 0.19 and 0.25 cm(-1), respectively) and an alternating chain model for 3 (J = 1.19 cm(-1) and J' = 1.19 cm(-1)).

In vivo transformations of dihydroartemisinic acid in Artemisia annua plants

[15-(CH3)-C-13-H-2]-dihydroartemisinic acid (2a) and [15-(CH3)-H-2]-dihydroartemisinic acid (2b) have been fed via the root to intact Artemisia annua plants and their transformations studied in vivo by one-dimensional H-2 NMR spectroscopy and two-dimensional, C-13-H-2 correlation NMR spectroscopy (C-13-(2) H COSY). Labelled dihydroartemisinic acid was transformed into 16 12-carboxy-amorphane and cadinane sesquiterpenes within a few days in the aerial parts of A. annua, although transformations in the root were much slower and more limited. Fifteen of these 16 metabolites have been reported previously as natural products from A. annua. Evidence is presented that the first step in the transformation of dihydroartemisinic acid in vivo is the formation of allylic hydroperoxides by the reaction of molecular oxygen with the Delta(4,5)-double bond in this compound. The origin of all 16 secondary metabolites might then be explained by the known further reactions of such hydroperoxides. The qualitative pattern for the transformations of dihydroartemisinic acid in vivo was essentially unaltered when a comparison was made between plants, which had been kept alive and plants which were allowed to die after feeding of the labelled precursor. This, coupled with the observation that the pattern of transformations of 2 in vivo demonstrated very close parallels with the spontaneous autoxidation chemistry for 2, which we have recently demonstrated in vitro, has lead us to conclude that the main 'metabolic route' for dihydroartemisinic acid in A. annua involves its spontaneous autoxidation and the subsequent spontaneous reactions of allylic hydroperoxides which are derived from 2. There may be no need to invoke the participation of enzymes in any of the later biogenetic steps leading to all 16 of the labelled 11,13-dihydro-amorphane sesquiterpenes which are found in A. annua as natural products. (C) 2003 Elsevier Ltd. All rights reserved.

Synthesis of labelled dihydroartemisinic acid

[15-(CH3)-C-13-H-2]-Dihydroartemisinic acid (2a), [15-(CH3)-H-2]-dihydroartemisinic acid (2b) and [15-(CH3)-C-13]-dihydroartemisinic acid (2c) have been obtained in good yield and high isotopic enrichment by a reconstructive synthesis from artemisinin. These labelled compounds were designed to be used in biosynthetic experiments to determine the origins of artemisinin and other sesquiterpene natural products from Artemisia annua. (C) 2003 Elsevier Ltd. All rights reserved.

Synthesis and catalytic epoxidation potentiality of oxodiperoxo molybdenum(VI) complexes with pyridine-2-carboxaldoxime and pyridine-2-carboxylate: the crystal structure of PMePh3[MoO(O-2)(2)(PyCO)]

[MoO(O-2)(2)(PyCOXH)(H2O)] and PMePh3[MoO(O-2)(2)(PyCO)] (PyCOXH = Pyridine-2-carboxaldoxime and PyCOH = Pyridine-2-carboxylic acid) have been synthesized. Both complexes have been characterized by physico-chemical and spectroscopic methods; in addition, the carboxylate complex has been structurally characterized by X-ray crystallography. The carboxylate complex is a more efficient catalyst than the oxime complex for epoxidation of olefins and shows excellent catalytic activity for the substrates: cyclooctene, cinnamyl alcohol, allyl alcohol and 1-hexene.

Lipid, fatty acid, protein, amino acid and ash contents in four Brazilian red algae species

Four species of marine benthic algae (Laurencia filiformis, L. intricata, Gracilaria domingensis and G. birdiae) that belong to the phylum Rhodophyta were collected in Espirito Santo State, Brazil and investigated concerning their biochemical composition (fatty acid, total lipid, soluble proteins, amino acid and ash). The total content of lipid (% dry weight) ranged from 1.1% to 6.2%: fatty acid from 0.7% to 1.0%: soluble protein from 4.6% to 18.3%, amino acid from 6.7% to 11.3% and ash from 22.5% to 38.4%. judging from their composition, the four species of algae appear to be potential sources of dietary proteins, amino acids, lipids and essential fatty acids for humans and animals. (C) 2009 Elsevier Ltd. All rights reserved.

Harpalycin 2 inhibits the enzymatic and platelet aggregation activities of PrTX-III, a D49 phospholipase A(2) from Bothrops pirajai venom

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Evaluation of the kinetics of xylose formation from dilute sulfuric acid hydrolysis of forest residues of Eucalyptus grandis

Dilute acid hydrolysis studies were performed on forest residues of Eucalyptus grandis, in a cylindrical reactor of stainless steel. The kinetics of this hydrolysis reaction was investigated employing 0.65% sulfuric acid, a residue/acid solution ratio of 1/9 (w/w), temperatures of 130, 140, 150, and 160 degrees C, and reaction times in the range 20-100 min. The results showed that, under the optimized conditions of acid hydrolysis employed in this study, the variables temperature and reaction time had a strong influence on hemicellulose removal and a small influence on the degree of lignin and cellulose removal. The highest xylose extraction yield was 87.6% attained at 160 degrees C, after 70 min reaction time, simultaneously with the formation of decomposition products, namely 2.8% acetic acid, 0.6% furfural, and 0.06% 5-hydroxymethylfurfural. A similar xylose extraction yield (82.8%) was observed at 150 degrees C after 100 min, with the formation of 3.2% acetic acid, 1.0% furfural, and 0.07% 5-hydroxymethylfurfural. The kinetic parameters determined at 130, 140, 150, and 160 degrees C for degradation of xylan present in the hemicellulose of the eucalyptus forest residue during the formation of xylose were the first-order reaction rate constants (k) for each temperature, 1.22 x 10(-4), 2.12 x 10(-4), 5.43 x 10(-4), and 9.05 x 10(-4) s(-1), respectively, and an activation energy (E-a) of 101.3 kJ mol(-1).

Síntese, caracterização e estudo fotofísico de complexos de 4,4- diaminoestilbeno-2,2-dissulfonato com íons lantanídeos

This is a work involving fundamental studies of chemistry where the synthesis and structural characterization, as well as a possible future application of these new compounds as luminescent sensors or sunscreen agents, complexes with 4,4 diaminostilbene-2,2-disulfonic (DSD) and trivalent lanthanide ions La3+, Nd3+, Eu3+, Gd3+ and Yb3+, were synthesized in the ratio of 3 mmol: 1 mmol (DSD: lanthanides). The complexes obtained with these ions were present in powder form and were characterized by complexometric titration with EDTA CHN Elemental analysis, molecular absorption spectroscopy in the ultraviolet region, the absorption spectroscopy in the infrared, thermal analysis (TG / DTG), Nuclear Magnetic Resonance - NMR 1H and Luminescence Spectroscopy. The complexometric titration and CHN analysis, confirmed the TG / DTG which suggest that these complexes have the following general chemical formulas: [La2(C14H12S2O6N2)2(H2O)2Cl2].7H2O,[Nd2(C14H12S2O6N2)2(H2O)2Cl2].6H2O,[Eu2(C14 H12S2O6N2)2(H2O)2Cl2].7H2O,[Gd2(C14H12S2O6N2)2(H2O)2Cl2].4H2O e [Yb2(C14H12S2O6N2)2(H2O)2].6H2O. The disappearance of the bands in the infrared spectrum at 2921 cm-1 and 2623 cm-1 and the displacement of the bands in the spectra of the amine complex indicate that the lanthanide ion is coordinated to the oxygen atoms and the sulfonate groups of the nitrogens amines, suggesting the formation of the dimer. The disappearance of the signal and the displacement signal SO3H amines in the 1H NMR spectrum of this complex are also indicative coordination and dimer formation. The Thermogravimetry indicates that the DSD is thermally stable in the range of 40º to 385°C and their complexes with lanthanide ions exhibit weight loss between 4 and 5 stages. The Uv-visible spectra indicated that the DSD and complexes exhibit cis isomers. The analysis of luminescence indicates that the complexes do not exhibit emission in the region of the lanthanides but an intense emission part of the binder. This is related to the triplet states of the ligand, which are in the lowest energy state emitting lanthanide ions, and also the formation of the dimer that suppress the luminescence of ion Eu3+. The formation of dimer was also confirmed by calculating the europium complex structure using the model Hamiltonian PM6 and Sparkle

(-)-Kolavenic acid

In the two, almost identical, molecules in the asymmetric unit of the title compound [ systematic name: (E)-3-methyl-5-(1,2,4a, 5-tetramethyl-1,2,3,4,4a,7,8,8a-octahydronaphthalen-1yl) pent-2-enoic acid], C20H32O2, the rings are trans fused. The cyclohexane ring has a chair conformation and the cyclohexene ring a distorted half-boat conformation. The two independent molecules are connected into a dimer via O-H center dot center dot center dot O hydrogen bonds. The dimers are associated into supramolecular chains along c via C-H center dot center dot center dot O contacts.

Determination of rice herbicides, their transformation products and clofibric acid using on-line solid-phase extraction followed by liquid chromatography with diode array and atmospheric pressure chemical ionization mass spectrometric detection

A simultaneous method for the trace determination of acidic, neutral herbicides and their transformation products in estuarine waters has been developed through an on-line solid-phase extraction method followed by liquid chromatography with diode array and mass spectrometric detection. An atmospheric pressure chemical ionization (APCI) interface was used in the negative ionization mode after optimization of the main APCI parameters. Limits of detection ranged from 0.1 to 0.02 ng/ml for 50 mi of acidified estuarine waters preconcentrated into polymeric precolumns and using time-scheduled selected ion monitoring mode. Two degradation products of the acidic herbicides (4-chloro-2-methylphenol and 2,4-dichlorophenol) did not show good signal response using APCI-MS at the concentration studied due to the higher fragmentor voltage needed for their determination For molinate and the major degradation product of propanil, 3,4-dichloroaniline, positive ion mode was needed for APCI-MS detection. The proposed method was applied to the determination of herbicides in drainage waters from rice fields of the Delta del Ebro (Spain). During the S-month monitoring of the herbicides, 8-hydroxybentazone and 4-chloro-2-methylphenoxyacetic acid were successively found in those samples. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Acid and fermented silage characterization and determination of apparent digestibility coefficient of crude protein for pacu Piaractus mesopotamicus

Three types of raw materials including commercial waste from saltwater (SW), freshwater fish (FW) and tilapia fillet residue (FR) were used to produce fish silage by either acid digestion (2% formic acid and 2% sulfuric acid) or anaerobic fermentation (5% of Lactobacillus plantarum and 15% sugar cane molasses). Six test diets were used in digestibility trials prepared with 70% reference diet and 30% of each experimental silage. These diets were fed to juvenile pacu Piaractus mesopotamicus (146 g average weight) in triplicate. Fish were kept in 500-L tanks and feces collected by manual extrusion. It was observed for both processes that SW waste always had the highest moisture content and lowest fat and ash. Highest crude protein levels were found in silages from commercial fish waste (SW and FW) made from whole fish unfit for human consumption. However, apparent digestibility coefficients did not vary among diets (P > 0.05). Although values did not differ statistically, fermented silage consistently displayed higher digestibility coefficients compared to acid silage. The silages exhibited relatively high protein digestibility (72.5-80.0%), thus suggesting the feasibility of using fish industry by-products in aquaculture feeds.

Light emission from tryptophan oxidation by hypobromous acid

The emission of ultraweak light from cells is a phenomenon associated with the oxidation of biomolecules by reactive oxygen species. The indole moiety present in tryptophan, serotonin and melatonin is frequently associated with the emission of light during the oxidation of these metabolites. This study presents results for hypobromous acid (HOBr) oxidation of tryptophan as a putative endogenous source of ultraweak light emission. We found that chemiluminescence elicited by the oxidation of tryptophan by HOBr was significantly higher than by hypochlorous acid (HOCl). This difference was related to secondary oxidation reactions, which were more intense using HOBr. The products identified during oxidation by HOCl, but depleted by using HOBr, were N-formylkynurenine, kynurenine, 1,2,3,3a,8,8a-hexahydro-3a-hydroxypyrrolo[2,3-b]-indole-2-carboxylic acid, oxindolylalanine and dioxindolylalanine. The emission of light is dependent on the free α-amino group of tryptophan, and hence, the indole of serotonin and melatonin, although efficiently oxidized, did not produce chemiluminescence. The emission of light was even greater using taurine monobromamine and dibromamine as the oxidant compared to HOBr. A mechanism based on bromine radical intermediates is suggested for the higher efficiency in light emission. Altogether, the experimental evidence described in the present study indicates that the oxidation of free tryptophan or tryptophan residues in proteins is an important source of ultraweak cellular emission of light. This light emission is increased in the presence of taurine, an amino acid present in large amounts in leukocytes, where this putative source of ultraweak light emission is even more relevant.

Advances in drug design based on the amino acid approach: Taurine analogues for the treatment of CNS diseases

Amino acids are well known to be an important class of compounds for the maintenance of body homeostasis and their deficit, even for the polar neuroactive aminoacids, can be controlled by supplementation. However, for the amino acid taurine (2-aminoethanesulfonic acid) this is not true. Due its special physicochemical properties, taurine is unable to cross the blood-brain barrier. In addition of injured taurine transport systems under pathological conditions, CNS supplementation of taurine is almost null. Taurine is a potent antioxidant and anti-inflammatory semi-essential amino acid extensively involved in neurological activities, acting as neurotrophic factor, binding to GABA A/glycine receptors and blocking the excitotoxicity glutamate-induced pathway leading to be a neuroprotective effect and neuromodulation. Taurine deficits have been implicated in several CNS diseases, such as Alzheimer's, Parkinson's, epilepsy and in the damage of retinal neurons. This review describes the CNS physiological functions of taurine and the development of new derivatives based on its structure useful in CNS disease treatment.&; 2012 by the authors; licensee MDPI, Basel, Switzerland.

Síntese, caracterização e estudo do comportamento térmico dos 2-metoxibenzoatos de Mn(II), Co(II), Ni(II), Cu(II) e Zn(II) no estado sólido

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Complexos de zinco(II), de európio(III) e heterobimetálico com os ácidos tiofeno 2 e 3-carboxílico. Síntese, caracterização e propriedades luminescentes

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