Synthesis and Metal-ion Binding Properties of New N2S4O2- and N2S5O2-Donor Macrocycles

Synthetic procedures for new mixed-donor macrocycle compounds were reported. The macrocyclic compounds were used in solvent extraction metal picrates such as Ag+, Hg2+, Cd2+, Zn2+, Cu2+, Ni2+, Mn2+, Pb2+, and Co2+. The metal picrate extractions were investigated at 25±0.1°C with the aid of UV-visible spectrometry. It was found that 6,7,9,10,12,13,23,24-octahydro-19H,26Hdibenzo[h,t](1,4,7,13,16,22,10,19) dioxatetrathiadiazasiclotetracosine-20,27(21H,28H)-dione showed selectivity towards Ag+, Hg2+, and Cd2+ among the other metals. The extraction constants (Log Kex) and complex compositions were determined for the Ag+ and Hg2+ complexes for this compound and 9,10,12,13,23,24,26,27,29,30-decahydro-5H,15H-dibenzo-[h,w][1,4,7,13,16,19,25-,10,22] dioxapentathiadiazacycloheptacosine-6,16(7H,17H)-dione.

Biodegradable amphiphilic polymer-drug conjugate micelles

The coupling of drugs to macromolecular carriers received an important impetus from Ringsdorf's notion of polymer-drug conjugates. Several water-soluble polymers, poly(ethylene glycol), poly[N-(2-hydroxypropyl) methacrylamidel, poly(L-glutamic acid) and dextran, are studied intensively and have been utilized successfully in clinical research. The promising results arising from clinical trials with polymer-drug conjugates (e.g., paclitaxel, doxorubicin, camptothecins) have provided a firm foundation for other synthetic polymers, especially biodegradable polymers, used as drug delivery vehicles. This review discusses biodegradable polymeric micelles as an alternative drug-conjugate system. Particular focus is on A-B or B-A-B type biodegradable amphiphilic block copolymer such as polylactide, morpholine-2,5-dione derivatives and cyclic carbonates, which can form a core-shell micellar structure, with the hydrophobic drug-binding segment forming the hydrophobic core and the hydrophilic segment as a hydrated outer shell. Polymeric micelles can be designed to avoid uptake by cells of reticuloendothelial system and thus enhance their blood lifetime via the enhanced permeability and retention effect.

Efficient organic electroluminescent devices based on an organosamarium complex

Several organic electroluminescent devices with different device structures were fabricated based on an organosamarium complex Sm(HFNH)(3)phen[HFNH=4, 4, 5, 5, 6, 6, 6-heptafluoro-l-(2-naphthvl)hexane-1, 3-dione; phen=1, 10-phenanthroline] as emitter. Their electroluminescent properties were investigated in detail. Although the devices with the optimal structure ITO/TPD (50nm)/ Sm(HFNH)(3)phen (xwt%):CBP (50nm)/BCP (20nm)/AIQ (30nm)/LiF (1 nm),/Al (200nm) show high brightness (more than 400cd/m(2)) and high current efficiency (about 1 cd/A), there are emissions from CBP, BCP and even from AIQ existing in the electroluminescence (EL) spectra besides emission from Sm(HFNH)(3)Phen. The reason to this was discussed. The device with the structure ITO/TPD (50 nm)/ Sm(HFNH)(3)phen (50 nm)/AIQ (30 nm)/LiF (1 nm)/Al (200 nm) exhibits the maximum brightness of 118 cd/m(2) and current efficiency of 0.029 cd/A, and shows emissions from AIQ and Sm(HFNH)(3)phen at high voltages. However, with the BCP hole-block layer added, the device [ITO/TPD (50 nm)/Sm(HFNH)(3)phen (50 nm)/BCP (20 nm)/AIQ (30 nm)/LiF (1 nm)/Al (200 nm)] exhibits pure Sm3+ emission in 2 the EL spectra even at high voltages, with the maximum current efficiency of 0.29cd/A and brightness of 82cd/m(2)

Thia-michael addition reactions in water using 3-[Bis(alkylthio) methylene]pentane-2,4-diones as odorless and efficient thiol equivalents

3-[Bis(ethylthio)methylene]pentane-2,4-dione (1a) and 3-[bis(benzylthio)methylene]pentane-2,4-dione (1b) have been investigated as non-thiolic and odorless thiol equivalents in thia-Michael addition reactions. In the presence of aqueous p-dodecyl benzenesulfonic acid (DBSA), compound (1) was cleaved and the generated thiols underwent facile conjugate addition to alpha,beta-unsaturated ketones 2 in-situ, affording the corresponding beta-keto sulfides (3) in good yields.

Triboluminescence of a new europate complex

A new europium (III) complex Eu(HFNH)(3)Phen (HFNH: 4, 4, 5, 5, 6, 6, 6-heptafluoro-1-(2-naphthyl) hexane-1,3-dione; phen: 1, 10-phenanthroline) was synthesized and its triboltuninescent phenomenon was observed. Photoluminescence and triboluminescence spectra were successfully determined. The most intense triboluminescent emission originates front the transition of the, central Eu3+ ion from D-5(0) level to F-7(2) level. The triboluminescent spectrum is basically similar to that of photoluminescence, which correlates with the disorders of F atoms.

Biodegradable amphiphilic triblock copolymer bearing pendant glucose residues: Preparation and specific interaction with Concanavalin A molecules

A novel biodegradable amphiphilic block copolymer PLGG-PEG-PLGG bearing pendant glucose residues is successfully prepared by the coupling reaction of 3-(2-aminoethylthio) propyl-R-D-glucopyranoside with the pendant carboxyl groups of PLGG-PEG-PLGG in the presence of N,N'-carbonyldiimidazole. The polymer PLGG-PEG-PLGG, i.e., poly {(lactic acid)-co-[(glycolic acid)-alt-(L-glutamic acid)]}-block-poly(ethylene glycol)-block-poly{( lactic acid)-co-[( glycolic acid)-alt-(L-glutamic acid)]}, is prepared by ring-opening copolymerization of L-lactide (LLA) with (3s)-benzoxylcarbonylethylmorpholine-2,5-dione (BEMD) in the presence of dihydroxyl PEG with molecular weight of 2000 as macroinitiator and Sn(Oct)(2) as catalyst, and then by catalytic hydrogenation. The glucose-grafted copolymer shows a lower degree of cytotoxicity to ECV-304 cells and improved specific recognition and binding with Concanavalin A (Con A). Therefore, this kind of glucose-grafted copolymer may find biomedical applications.

Syntheses, structures and near-IR luminescent studies on ternary lanthanide (Er-III, Ho-III, Yb-III, Nd-III) complexes containing 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate

The ligand Hhfth [4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dione], which contains a heptafluoropropyl group, has been used to synthesize several new ternary lanthanide complexes (Ln = Er, Ho, Yb, Nd) in which the synergistic ligand is 1,10-phenanthroline (phen) or 2,2'-bipyridine (bipy). The two series of complexes are [Ln(hfth)(3)phen] [abbreviated as (Ln)1, where Ln = Er, Ho, Yb] and [Ln(hfth)(3)bipy] [abbreviated as (Ln)2, where Ln = Er, Ho, Yb, Nd]. Members of the two series have been structurally characterized. The growth morphology, diffuse reflectance (DR) spectra, thermogravimetric analyses, and photophysical studies of these complexes are described in detail. After ligand-mediated excitation of the complexes, they all show the characteristic near-infrared (NIR) luminescence of the corresponding Ln(3+) ions (Ln = Er, Ho, Yb, Nd). This is attributed to efficient energy transfer from the ligands to the central Ln(3+) ions, i.e. an antenna effect. The heptafluorinated substituent in the main hfth sensitizer serves to reduce the degree of vibrational quenching. With these NIR-luminescent lanthanide complexes, the luminescent spectral region from 1300 to 1600 nm, which is of particular interest for telecommunication applications, can be covered completely.

Electroluminescence based on a beta-diketonate ternary samarium complex

The triplet energy state of the HTH [HTH: 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl) hexane-1,3-dione] ligand was measured to be 20 400 cm(-1), which indicated that Sm(HTH)(3) phen (phen: 1,10-phenanthroline) is a good complex to produce strong PL intensity and high fluorescence yield. Electroluminescent (EL) devices using the Sm( HTH) 3 phen complex as the emissive center were fabricated by vapor deposition and spin-coating methods. The relative intensity of the EL spectra changed compared to the photoluminescence (PL) spectrum, which suggested that the luminescence mechanisms of PL and EL have differences. A luminance of 9 cd m(-2) and a higher brightness of 21 cd m(-2) were obtained from the devices ITO/TPD (40 nm)/ Sm( HTH)(3) phen (50 nm)/ PBD (30 nm)/ Al (200 nm) and ITO/PVK (40 nm)/ PVK : Sm( HTH)(3) phen (2.5 wt%, 50 nm)/ PBD (30 nm)/ Al (200 nm), respectively.

Benzodiazepine Alkaloids from Marine-Derived Endophytic Fungus Aspergillus ochraceus

A new fungus-derived benzodiazepine analogue, 2-hydroxycircumdatin C (1), and a compound which has been isolated from a natural resource for the first time, but has been previously synthesized, namely (11aS)-2,3-dihydro-7-methoxy-1H-pyrrolo[2,1-c][1,4]benzodiazepine-5,11(10H,11aH)-dione (2), along with five structurally related known alkaloids (3-7), were isolated from Aspergillus ochraceus, an endophytic fungus derived from the marine brown alga Sargassum kjellmanianum. Their structures were established on the basis of spectroscopic methods. The absolute configuration of I was determined through CD evidence. Compound 1 displayed significant DPPH radical-scavenging activity with an IC50 value of 9.9 mu M, which is 8.9-fold more potent than that of butylated hydroxytoluene (BHT), a well-known synthetic positive control.

Hymeniacidon perleve associated bioactive bacterium Pseudomonas sp NJ6-3-1

Among marine bacteria isolated from the cytotoxic sponge Hymeniacidon perleve, one strain NJ6-3-1 classified as Pseudomonas sp. showed both cytotoxic and antimicrobial activities. Fatty acid analysis indicated that the bacterial strain consists mainly of C16:1, C16:0, C18:1, C18:0, C15:0, C14:0. One unusual 9,10-cyclopropane-C17:0 fatty acid and C26:0 also constitute major components, as well as the existence of squalene, the precursor of triterpenoids. The major metabolites in the culture broth were identified as alkaloids, including diketopiperazines and indole compounds, namely 3,6-diisopropylpiperazine-2,5-dione, 3-benzyl-3-isopropylpiperazine-2,5-dione, 3,6-bis-(2-methylpropyl)-piperazine-2,5-dione, indole-3-carboxaldehyde, indole-3-carboxylic acid methyl ester, indole-3-ethanol, and quinazoline-2,4-dione.

Bromophenols coupled with nucleoside bases and brominated tetrahydroisoquinolines from the red alga Rhodomela confervoides

Three new bromophenols C-N coupled with nucleoside base derivatives (1-3) and three new brominated 1,2,3,4-tetrahydroisoquinolines (5-7, together with a new brominated tyrosine derivative (4, have been isolated from polar fractions of an ethanolic extract of the red alga Rhodomela confervoides. By spectroscopic and chemical methods including HRMS and 2D NMR data, their structures were determined as 7-[3-bromo-2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyl]-3,7-dihydro-1H-purine-2,6-dione (1), 7-(2,3-dibromo-4,5-dihydroxybenzyl)-3,7-dihydro-1H-purine-2,6-dione (2, 9-[3-bromo-2-(2,3-dibromo-4,5-dihydroxybenzyl)-4,5-dihydroxybenzyl]adenine (3), (-)-8S-(3-bromo-5-hydroxy-4-methoxy)phenylalanine (4), (-)-3S-8-bromo-6-hydroxy-7-methoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylic acid (5), methyl (-)-3S-8-bromo-6-hydroxy-7-methoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylate (6), and methyl (-)-3S-6-bromo-8-hydroxy-7-methoxy-1,2,3,4-tetrahydroisoquinoline-3-carboxylate (7). Compounds 5-7 were semisynthesized by using 4 as the starting material.

A New Triterpenoid from Amoora dasyclada

Five compounds were isolated from the EtOH extraction of the stem of Amoora dasyclada (How et T. Chen) C. Y. Wu (Meliaceae). On the basis of spectroscopic methods, their structures were elucidated as 24, 25-epoxy-tirucall-7-ene-3, 23-dione (1), 24, 25, 26, 27-tetranortirucall-7-ene-3-oxo-23(21)-lactone (2), taraxerone (3), taraxerol (4) and b-sitosterol (5). Among them, compound 1 was a new triterpenoid, compounds 3-5 were firstly obtained from this plant; compound 2, an tetranortriterpenoid, was firstly isolated from natural sources, and its NMR data were assigned for the first time. Moreover, the D7-bond and the Me-14 in compound 2 were never changed, which has never been found in other tetranortriterpenoids. And the biosynthetic pathway of tetranortriterpenoid was further discussed.

Diterpenoids from Euphorbia wallichii

Object To study the chemical constituents of Euphorbia wallichii.Methods The constituents were repeatedly separated and purified on silica gel column.They were identified on the basis of spectral methods.Results Nine diterpenoids were obtained from the roots of E. wallichii.Among them jolkinol B(I) is lathyrane type;caudicifolin (Ⅱ),helioscopinolides A(Ⅲ),C(Ⅳ),and E(Ⅴ) belong to abietane type;while ent-atisane-3β,16α,17-triol(Ⅵ),ent-16α,17-dihydroxyatisan-3-one(Ⅶ),ent-3β,(13S)-dihydroxyatis-16-en-14-one(Ⅷ),and ent-2-hydroxy-atis-1,16(17)-dien-3,14-dione(Ⅸ) possess an ent-atisane skeleon.Conclusion All of them are isolated from E. wallichii for the first time.

Recomendações técnicas para o cultivo de hortaliças em agricultura familiar.

2007

Minhocário campeiro de baixo custo para a agricultura familiar.

MINHOCÁRIO CAMPEIRO: RESUMO:A minhocultura é uma atividade muito interessante para a produção de adubo orgânico de qualidade nas propriedades familiares. O húmus de minhoca, além de ser rico em nutrientes para as plantas, ajuda a melhorar as características físicas do solo, como a aeração e a retenção de água. Ao contrário do que grande parte dos agricultores pensa, a principal causa do insucesso de um minhocário está em seu no manejo inadequado e não na falta de uma maior infraestrutura, feita com tijolos, telhas e cimento. O minhocário campeiro de baixo custo é construído com materiais disponíveis na própria propriedade e pode ser adaptado a diversas condições. Sugere-se contruir o minhocário com bambus e adotar a largura máxima de 1 metro; o comprimento pode ser variável. Os bambus devem ser colocados intercalados um sobre o outro de forma que suas pontas se cruzem cerca de 5 cm. Para guarnecer as pontas, deve ser fixada uma estaca de cada lado da cruz formada na junção. Os bambus devem ser empilhados até atingirem a altura de 30 cm, embora esse limite possa ser maior conforme a necessidade. O fato de não requerer o uso de arame na sua estrutura e de poder ter sua altura aumentada a qualquer momento, é o que diferencia esse minhocário de outros modelos também construídos com bambu. O interior do minhocário deve ser forrado com sombrite ou filme plástico perfurado, para, ao mesmo tempo, conter o alimento e as minhocas e permitir a drenagem da água da chuva que por ventura venha a cair em seu interior. Para reduzir ao máximo o efeito do impacto da gota da chuva sobre o minhocário, deve ser colocada uma cobertura de folhas secas ou construir uma tampa com ripas de bambus cortadas ao meio e revestí-la com lona plástica. O minhocário deve ser montado em um local onde faça sombra durante a maior parte do dia. A área deve ter uma leve declividade, para que a água da chuva ou de escorrimento não acumule em seu interior. SCHIEDECK, G.; SCHWENGBER, J.E.; GONÇALVES, M. de M.; SCHIAVON, G. de A.; CARDOSO, J.H. Minhocário campeiro de baixo custo para a agricultura familiar. Pelotas: Embrapa Clima Temperado, 2007. (Comunicado Técnico, 171).