Dihydrocinnamic acid derivatives from Hortia species and their chemotaxonomic value in the Rutaceae

Phytochemical studies of Hortia brasiliana and Hortia oreadica (Rutaceae) have led to the identification of three novel dihydrocinnamic acids: 5-methoxy-2,2-dimethyl-2H-1-benzopyran-8-propanoic acid, 5,6-dimethoxy-2,2-dimethyl-2H-1-benzopyran-8-propanoic acid and erythro-2-hydroxy-4-methoxy-3-(1,2,3-trihydroxy-3-methylbutyl) benzenepropanoic acid from H. brasiliana and the second compound and six known dihydrocinnamic acids from H. oreadica. Engler included Hortia as the single Neotropical genus in the Toddalioideae subtribe Toddaliinae. However, the range of dihydrocinnamic acid derivatives found in H. brasiliana and H. oreadica show that they contain similar compounds to other species of Hortia and clearly point to their phytochemical affinities with other Rutoideae species. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis of Chromanes and 4H-Chromenes: Exploring the Oxidation of 2H-Chromenes and Dihydro-1-benzoxepines by Hypervalent Iodine(III)

The reaction of various oxygen-containing benzo-fused cycloalkenes were studied with the hypervalent iodine reagent hydroxy(tosyloxy) iodo]benzene [PhI(OH)OTs, HTIB]. 2H-Chromene and 4-methyl-2H-chromene resulted in substituted 4H-chromene and cis-3,4-dialkoxy-4-methyl-3,4-dihydro-2H-chromenes, respectively. Ring contraction to chromanes and benzofurans was observed for dihydrobenzoxepines and 2,2-dimethyl-2H-chromenes, respectively.

Practical synthesis of a functionalized 1-oxo-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid

The synthesis of a functionalized 1-oxo-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid has been performed in 10 steps from the readily available dimedone. Only three purifications by flash chromatography are required through the whole sequence. The key step is the reaction between a dimedone derivative and a chlorotetrolic ester, that gives a tetrasubstituted benzene ring (through a Diels-Alder/retro- Diels-Alder process) bearing the substituents in the suitable positions for further functionalization. (C) 2012 Elsevier Ltd. All rights reserved.

Toll-like receptor 2 knockdown modulates Interleukin (IL)-6 and IL-8 but not Stromal Derived Factor-1 (SDF-1/CXCL12) in human periodontal ligament and gingival fibroblasts

Background: Fibroblasts are now seen as active components of the immune response because these cells express Toll-like receptors (TLRs), recognize pathogen-associated molecular patterns, and mediate the production of cytokines and chemokines during inflammation. The innate host response to lipopolysaccharide (LPS) from Porphyromonas gingivalis is unusual inasmuch as different studies have reported that it can be an agonist for Toll-like receptor 2 (TLR2) and an antagonist or agonist for Toll-like receptor 4 (TLR4). This study investigates and compares whether signaling through TLR2 or TLR4 could affect the secretion of interleukin (IL)-6, IL-8, and stromal derived factor-1 (SDF-1/CXCL12) in both human gingival fibroblasts (HGF) and human periodontal ligament fibroblasts (HPDLF). Methods: After small interfering RNA-mediated silencing of TLR2 and TLR4, HGF and HPDLF from the same donors were stimulated with P. gingivalis LPS or with two synthetic ligands of TLR2, Pam2CSK4 and Pam3CSK4, for 6 hours. IL-6, IL-8, and CXCL12 mRNA expression and protein secretion were evaluated by quantitative polymerase chain reaction and enzyme-linked immunosorbent assay, respectively. Results: TLR2 mRNA expression was upregulated in HGF but not in HPDLF by all the stimuli applied. Knockdown of TLR2 decreased IL-6 and IL-8 in response to P. gingivalis LPS, or Pam2CSK4 and Pam3CSK4, in a similar manner in both fibroblasts subpopulations. Conversely, CXCL12 remained unchanged by TLR2 or TLR4 silencing. Conclusion: These results suggest that signaling through TLR2 by gingival and periodontal ligament fibroblasts can control the secretion of IL-6 and IL-8, which contribute to periodontal pathogenesis, but do not interfere with CXCL12 levels, an important chemokine in the repair process.

Electrochemically prepared polypyrrole-2-carboxylic acid films: synthesis protocols and studies on biosensors

The process for obtaining polypyrrole-2-carboxylic acid (PPY-2-COOH) films in acetonitrile was investigated using cyclic voltammetry, electrochemical quartz crystal microgravimetry (EQCM), and infrared spectroscopy (FTIR). Different potential ranges were applied during cyclic voltammetry experiments with the aim of obtaining films without and with the presence of controlled amounts of water added in acetonitrile. The FTIR spectra of the films have evidenced that cations and anions from the electrolyte solution were incorporated into the PPY-2-COOH structure, with a preferential adsorption of cations. After chemically immobilizing polyphenoloxidase (tyrosinase, PPO), PPY-2-COOH/PPO films were build for amperometric detection of catechol, establishing a linear limit of concentrations ranging from 5.0 x 10-4 to 2.5 x 10-2 mol L-1.

Theoretical and experimental studies on the electronic, optical, and structural properties of poly-pyrrole-2-carboxylic acid films

A theoretical approach is used here to explain experimental results obtained from the electrosynthesis of polypyrrole-2-carboxylic acid (PPY-2-COOH) films in nonaqueous medium. An analysis of the Fukui function (reactivity index) indicates that the monomer (pyrrole-2-carboxylic acid, PY-2-COOH), and dimers and trimers are oxidized in the C4 or C5 positions of the heterocyclic ring of the PY-2-COOH structure. After calculating the heat of formation using semiempirical Austin Model 1 post-Hartree-Fock parameterization for dimer species, both C4 and C5 positions adjacent to the aromatic rings of PPY-2-COOH were considered the most susceptible ones to oxidative coupling reactions. The ZINDO-S/CI semiempirical method was used to simulate the electronic transitions typically seen in the UV-VIS-NIR range in monomer and oligomers with different conjugation lengths. The use of an electrochemical quartz crystal microbalance provides sufficient information to propose a polymerization mechanism of PY-2-COOH based on molecular modeling and experimental results.

Further monoterpene chromane esters from Peperomia obtusifolia: VCD determination of the absolute configuration of a new diastereomeric mixture

A reinvestigation of the monoterpene chromane ester enriched fraction from Peperomia obtusifolia using chiral chromatography led to the identification of a minor peak, which was elucidated by NMR and HRMS as fenchyl-3,4-dihydro-5-hydroxy-2,7-dimethyl-8-(3 ''-methyl-2 ''-butenyl)-2-(4'-methyl-1',3'-pentadienyl)-2H-1-benzopyran-6-carboxylate, the same structure assigned to two other fenchyl esters described previously, pointing out a stereoisomeric relationship among them. Further NMR analysis revealed that it was actually a mixture of two compounds, whose absolute configurations were determined by VCD measurements. Although, almost no vibrational transitions could be assigned to the chiral chromane, the experimental VCD spectrum was largely opposite to that obtained for the average experimental VCD [(2S,1'''R,2'''R,4'''S + 2R,1'''R,2'''R,4'''S)/2] for fenchol derivatives. These results allowed us to assign the putative compounds as a racemic mixture of the chiral chromane esterified with the monoterpene (1S,2S,4R)fenchol, which had not been identified in our early work. (C) 2012 Elsevier Ltd. All rights reserved.

First report on the kinetics of the uncatalyzed esterification of cellulose under homogeneous reaction conditions: a rationale for the effect of carboxylic acid anhydride chain-length on the degree of biopolymer substitution

The kinetics of the homogeneous acylation of microcrystalline cellulose, MCC, with carboxylic acid anhydrides with different acyl chain-length (Nc; ethanoic to hexanoic) in LiCl/N,N-dimethylacetamide have been studied by conductivity measurements from 65 to 85 A degrees C. We have employed cyclohexylmethanol, CHM, and trans-1,2-cyclohexanediol, CHD, as model compounds for the hydroxyl groups of the anhydroglucose unit of cellulose. The ratios of rate constants of acylation of primary (CHM; Prim-OH) and secondary (CHD; Sec-OH) groups have been employed, after correction, in order to split the overall rate constants of the reaction of MCC into contributions from the discrete OH groups. For the model compounds, we have found that k((Prim-OH))/k((Sec-OH)) > 1, akin to reactions of cellulose under heterogeneous conditions; this ratio increases as a function of increasing Nc. The overall, and partial rate constants of the acylation of MCC decrease from ethanoic- to butanoic-anhydride and then increase for pentanoic- and hexanoic anhydride, due to subtle changes in- and compensations of the enthalpy and entropy of activation.

Lipid Transfer to HDL is Higher in Marathon Runners than in Sedentary Subjects, but is Acutely Inhibited During the Run

Although exercise increases HDL-cholesterol, exercise-induced changes in HDL metabolism have been little explored. Lipid transfer to HDL is essential for HDL's role in reverse cholesterol transport. We investigated the effects of acute exhaustive exercise on lipid transfer to HDL. We compared plasma lipid, apolipoprotein and cytokine levels and in vitro transfer of four lipids from a radioactively labeled lipid donor nanoemulsion to HDL in sedentary individuals (n = 28) and in marathon runners (n = 14) at baseline, immediately after and 72 h after a marathon. While HDL-cholesterol concentrations and apo A1 levels were higher in marathon runners, LDL-cholesterol, apo B and triacylglycerol levels were similar in both groups. Transfers of non-esterified cholesterol [6.8 (5.7-7.2) vs. 5.2 (4.5-6), p = 0.001], phospholipids [21.7 (20.4-22.2) vs. 8.2 (7.7-8.9), p = 0.0001] and triacylglycerol [3.7 (3.1-4) vs. 1.3 (0.8-1.7), p = 0.0001] were higher in marathon runners, but esterified-cholesterol transfer was similar. Immediately after the marathon, LDL- and HDL-cholesterol concentrations and apo A1 levels were unchanged, but apo B and triacylglycerol levels increased. Lipid transfer of non-esterified cholesterol [6.8 (5.7-7.2) vs. 5.8 (4.9-6.6), p = 0.0001], phospholipids [21.7 (20.4-22.2) vs. 19.1 (18.6-19.3), p = 0.0001], esterified-cholesterol [3.2 (2.2-3.8) vs. 2.3 (2-2.9), p = 0.02] and triacylglycerol [3.7 (3.1-4) vs. 2.6 (2.1-2.8), p = 0.0001] to HDL were all reduced immediately after the marathon but returned to baseline 72 h later. Running a marathon increased IL-6 and TNF-alpha levels, but after 72 h these values returned to baseline. Lipid transfer, except esterified-cholesterol transfer, was higher in marathon runners than in sedentary individuals, but the marathon itself acutely inhibited lipid transfer. In light of these novel observations, further study is required to clarify how these metabolic changes can influence HDL composition and anti-atherogenic function.

Comparison of multisensory and strength training for postural control in the elderly

Objective: The objective of this study was to analyze the efficacy of multisensory versus muscle strengthening to improve postural control in healthy community-dwelling elderly. Participants: We performed a single-blinded study with 46 community-dwelling elderly allocated to strength (GS, n = 23; 70.18 +/- 4.8 years 22 women and 1 man) and multisensory exercises groups (GM, n = 23; 68.8 +/- 5.9 years; 22 women and 1 man) for 12 weeks. Methods: We performed isokinetic evaluations of muscle groups in the ankle and foot including dorsiflexors, plantar flexors, inversion, and eversion. The oscillation of the center of pressure was assessed with a force platform. Results: The GM group presented a reduction in the oscillation (66.8 +/- 273.4 cm(2) to 11.1 +/- 11.6 cm(2); P = 0.02), which was not observed in the GS group. The GM group showed better results for the peak torque and work than the GS group, but without statistical significance. Conclusion: Although the GM group presented better results, it is not possible to state that one exercise regimen proved more efficacious than the other in improving balance control.

Doenças respiratórias e fatores associados: estudo de base populacional em São Paulo, 2008-2009

OBJETIVO: Estimar a prevalência de bronquite aguda, rinite e sinusite em crianças e adolescentes e identificar fatores associados. MÉTODOS: Estudo transversal, de base populacional. Foi realizado inquérito domiciliar com 1.185 crianças e adolescentes de São Paulo, SP, de 2008 a 2009. Os participantes foram selecionados a partir de amostragem probabilística, estratificada por sexo e idade e por conglomerados em dois estágios. Para análise ajustada foi realizada regressão múltipla de Poisson. RESULTADOS: Dos entrevistados, 7,3% referiram bronquite aguda, 22,6% rinite e 15,3% sinusite. Após análise ajustada, associaram-se à bronquite aguda auto-referida: idade de zero a quatro anos (RP = 17,86; IC95%: 3,65;90,91), cinco a nove anos (RP = 37,04; IC95%: 8,13;166,67), dez a 14 anos (RP = 20,83; IC95%: 4,93;90,91), referir ter alergia (RP = 3,12; IC95%: 1,70;5,73), cor da pele preta/parda (RP = 2,29; IC95%: 1,21;4,35) e morar em domicílio com um a três cômodos (RP = 1,85; IC95%: 1,17;2,94); à rinite auto-referida: idade dez a 14 anos (RP = 2,77; IC95%: 1,60;4,78), 15 a 19 anos (RP = 2,58; IC95%: 1,52;4,39), referir ter alergia (RP = 4,32; IC95%: 2,79;6,70), referir ter asma (RP = 2,30; IC95%: 1,30;4,10) e morar em apartamento (RP = 1,70; IC95%: 1,06;2,73); à sinusite auto-referida: idade cinco a nove anos (RP = 2,44; IC95%: 1,09;5,43), dez a 14 anos (RP = 2,99; IC95%: 1,36;6,58), 15 a 19 anos (RP = 3,62; IC95%: 1,68;7,81), referir ter alergia (RP = 2,23; IC95%: 1,41;3,52) e apresentar obesidade (RP = 4,42; IC95%: 1,56;12,50). CONCLUSÕES: As doenças respiratórias foram mais prevalentes em grupos populacionais com características definidas, como grupo etário, doenças auto-referidas, tipo de moradia e obesidade.

Fatores de risco para trauma vascular durante a quimioterapia antineoplásica: contribuições do emprego do risco relativo

OBJETIVO: identificar a relação entre os fatores de risco para trauma vascular e o surgimento de eventos adversos de infiltração ou flebite por quimioterapia antineoplásica. MÉTODOS: Estudo de abordagem quantitativa observacional com 30 mulheres com câncer de mama. RESULTADOS: O tipo de material do cateter apresentou associação que sugere risco (RR=2,76; IC=1,199; 6,369); o fator velocidade de infusão apresentou RR=2,22; entretanto, IC= 0,7672; 6,436; os fatores trajetória, número de punção e mobilidade da veia apresentaram RR<1 mas não podem ser considerados como fatores de proteção. Local de inserção e a visibilidade da veia apresentaram risco próximo a 1. CONCLUSÃO: O uso de cateter com metal para punção venosa foi considerado neste estudo como fator para Risco de Trauma Vascular. A análise da associação pelo RR mostrou-se concordante com os dados da literatura pesquisada.

Carlosbarbosaite, ideally (UO2)(2)Nb2O6(OH)(2)center dot 2H(2)O, a new hydrated uranyl niobate mineral with tunnels from Jaguaracu, Minas Gerais, Brazil: description and crystal structure

Carlosbarbosaite, ideally (UO2)(2)Nb2O6(OH)(2)center dot 2H(2)O, is a new mineral which occurs as a late cavity filling in albite in the Jaguaracu pegmatite, Jaguaracu municipality, Minas Gerais, Brazil. The name honours Carlos do Prado Barbosa (1917-2003). Carlosbarbosaite forms long flattened lath-like crystals with a very simple orthorhombic morphology. The crystals are elongated along [001] and flattened on (100); they are up to 120 mu m long and 2-5 mu m thick. The colour is cream to pale yellow, the streak yellowish white and the lustre vitreous. The mineral is transparent (as individual crystals) to translucent (massive). It is not fluorescent under either long-wave or short-wave ultraviolet radiation. Carlosbarbosaite is biaxial(+) with alpha = 1.760(5), beta = 1.775(5), gamma = 1.795(5), 2V(meas) = 70(1)degrees, 2V(calc) = 83 degrees. The orientation is X parallel to a, Y parallel to b, Z parallel to c. Pleochroism is weak, in yellowish green shades, which are most intense in the Z direction. Two samples were analysed. For sample I, the composition is: UO3 54.52, CaO 2.07, Ce2O3 0.33, Nd2O3 0.49, Nb2O5 14.11, Ta2O5 15.25, TiO2 2.20, SiO2 2.14, Fe2O3 1.08, Al2O3 0.73, H2O (calc.) 11.49, total 104.41 wt.%; the empirical formula is (square 0.68Ca0.28Nd0.02Ce0.02)(Sigma=1.00)[U-1.44 square O-0.56(2.88)(H2O)(1.12)](Nb0.80Ta0.52Si0.27Ti0.21Al0.11Fe0.10)(Sigma=2.01) O-4.72(OH)(3.20)(H2O)(2.08). For sample 2, the composition is: UO3 41.83, CaO 2.10, Ce2O3 0.31, Nd2O3 1.12, Nb2O5 14.64, Ta2O5 16.34, TiO2 0.95, SiO2 3.55, Fe2O3 0.89, Al2O3 0.71, H2O (calc.) 14.99, total 97.43 wt.%; the empirical formula is (square 0.67Ca0.27Nd0.05Ce0.01)(Sigma=1.00)[U-1.04 square O-0.96(2.08)(H2O)(1.92)] (Nb0.79Ta0.53Si0.42Ti0.08Al0.10Fe0.08)(Sigma=2.00)O-4.00(OH)(3.96)(H2O)(2.04). The ideal endmember formula is (UO2)(2)Nb2O6(OH)(2)center dot 2H(2)O. Calculated densities are 4.713 g cm(-3) (sample 1) and 4.172 g cm(-3) (sample 2). Infrared spectra show that both (OH) and H2O are present. The strongest eight X-ray powder-diffraction lines [listed as d in angstrom(I)(hkl)] are: 8.405(8)(110), 7.081(10)(200), 4.201(9)(220), 3.333(6)(202), 3.053(8)(022), 2.931(7)(420), 2.803(6)(222) and 2.589(5)(040,402). The crystal structure was solved using single-crystal X-ray diffraction (R = 0.037) which gave the following data: orthorhombic, Cmem, a = 14.150(6), b = 10.395(4), c = 7.529(3) angstrom, V = 1107(1) angstrom(3), Z = 4. The crystal structure contains a single U site with an appreciable deficiency in electron scattering, which is populated by U atoms and vacancies. The U site is surrounded by seven 0 atoms in a pentagonal bipyramidal arrangemet. The Nb site is coordinated by four 0 atoms and two OH groups in an octahedral arrangement. The half-occupied tunnel Ca site is coordinated by four 0 atoms and four H2O groups. Octahedrally coordinated Nb polyhedra share edges and comers to form Nb2O6(OH)(2) double chains, and edge-sharing pentagonal bipyramidal U polyhedra form UO5 chains. The Nb2O6(OH)(2) and UO5 chains share edges to form an open U-Nb-phi framework with tunnels along [001] that contain Ca(H2O)(4) clusters. Carlosbarbosaite is closely related to a family of synthetic U-Nb-O framework tunnel structures, it differs in that is has an (OH)-bearing framework and Ca(H2O)(4) tunnel occupant. The structure of carlosbarbosaite resembles that of holfertite.

Complexation of 2-acetylpyridine- and 2-benzoylpyridine-derived hydrazones to copper(II) as an effective strategy for antimicrobial activity improvement

Complexes [Cu(2AcPh)Cl]center dot 2H(2)O (1), [Cu(2AcpClPh)Cl]center dot 2H(2)O (2), [Cu(2AcpNO(2)Ph)Cl] (3), [Cu(2BzPh)Cl] (4). [Cu(2BzpClPh)Cl] (5) and [Cu(2BzpNO(2)Ph)Cl] (6) were obtained with 2-acetylpyridine-phenylhydrazone (H2AcPh), 2-acetylpyridine-para-chloro-phenylhydrazone (H2AcpClPh), 2-acetylpyridine-para-nitro-phenylhydrazone (H2AcpNO(2)Ph), 2-benzoylpyridine-phenylhydrazone (H2BzPh), 2-benzoylpyridine-para-chloro-phenylhydrazone (H2BzpClPh) and 2-benzoylpyridine-para-nitro-phenylhydrazone (H2BzpNO(2)Ph). The hydrazones showed poor antibacterial effect against Staphylococcus aureus, Enterococcus faecalis and Pseudomonas aeruginosa but demonstrated significant antifungal activity against Candida albicans. Upon coordination to copper(II) the antibacterial and antifungal activities appreciably increased. H2AcpClPh, H2BzpClPh and their copper(II) complexes (2) and (5), respectively, were as active as fluconazole against C. albicans. (C) 2012 Elsevier Ltd. All rights reserved.

On the search for potential anti-Trypanosoma cruzi drugs: Synthesis and biological evaluation of 2-hydroxy-3-methylamino and 1,2,3-triazolic naphthoquinoidal compounds obtained by click chemistry reactions

Five 2-hydroxy-3-substituted-aminomethyl naphthoquinones, nine 1,2,3-triazolic para-naphthoquinones, five nor-beta-lapachone-based 1,2,3-triazoles, and several other naphthoquinonoid compounds were synthesized and evaluated against the infective bloodstream form of Trypanosoma cruzi, the etiological agent of Chagas disease, continuing our screening program for new trypanocidal compounds. Among all the substances, 16-18, 23, 25-29 and 30-33 were herein described for the first time and fifteen substances were identified as more potent than the standard drug benznidazole, with IC50/24 h values in the range of 10.9-101.5 mu M. Compounds 14 and 19 with Selectivity Index of 18.9 and 6.1 are important structures for further studies. (C) 2012 Elsevier Masson SAS. All rights reserved.