RESUMO
Through phase-space analysis of Dumond diagrams for a flat Bragg crystal, a single bent Laue crystal and a monochromator consisting of double-bent Laue crystals, this work shows that it is possible to match the flat Bragg crystal to both the single-crystal and double-crystal Laue monochromators. The matched system has the advantage that the phase space of the bent crystal's output beam is much larger than that of the flat crystal, making the combined system stable. Here it is suggested that such a matched system can be used at synchrotron facilities to realize X-ray dark-field imaging, analyzer-based imaging and diffraction-enhanced imaging at beamlines using double-Laue monochromators.
RESUMO
A systematic process is introduced to compare (13)C NMR spectra of two (or more) candidate samples of known structure to a natural product sample of unknown structure. The process is designed for the case where the spectra involved can reasonably be expected to be very similar, perhaps even identical. It is first validated by using published (13)C NMR data sets for the natural product 4,6,8,10,16,18-hexamethyldocosane. Then the stereoselective total syntheses of two candidate isomers of the related 4,6,8,10,16-pentamethyldocosane natural product are described, and the process is applied to confidently assign the configuration of the natural product as (4S,6R,8R,10S,16S). This is accomplished even though the chemical shift differences between this isomer and its (16R)-epimer are only ±5-10 ppb (±0.005-0.01 ppm).
Assuntos
Alcanos/síntese química , Produtos Biológicos/química , Besouros/química , Hidrocarbonetos/síntese química , Alcanos/química , Animais , Hidrocarbonetos/química , Espectroscopia de Ressonância Magnética , Estrutura Molecular , EstereoisomerismoRESUMO
Reactions of 5-benzyloxy-4-methylpent-2-enyl(tributyl)stannane with aldehydes promoted by bismuth(III) iodide were usefully stereoselective in favour of the (E)-1,5-anti-6-benzyloxy-5-methylalk-3-en-1-ols. Similar stereoselectivity was observed for reactions of analogous 5-benzyloxy-4-methylpent-2-enyl bromides with aldehydes when promoted by a low valency bismuth species prepared by reduction of bismuth(III) triiodide with powdered zinc so providing a "tin-free" procedure. The analogous reactions of 4-benzyloxypent-2-enyl(tributyl)stannane with aldehydes promoted by bismuth(III) iodide were also stereoselective but gave lower yields. Attempted 1,6-stereocontrol using these reactions resulted in only modest stereoselectivities. Aspects of the chemistry of the products were studied in particular their stereoselective conversion into aliphatic compounds with methyl bearing stereogenic centres at 1,5,9,13- and 1,3,5-positions along the aliphatic chain. Mechanistically, allylic organobismuth species may be involved in both sets of reactions but this was not confirmed although the similar stereoselectivities observed for both the bismuth(III) iodide mediated reactions of the pent-2-enylstannanes and the low-valency bismuth promoted reactions of the pent-2-enyl bromides are consistent with participation of similar intermediates.
RESUMO
The stereoselective reaction of an allyl bromide with an aldehyde mediated by a low valency bismuth species was the key reaction in stereoselective syntheses of (4S,6R,8R,10S,16S)- and (4S,6R,8R,10S,16R)-4,6,8,10,16-pentamethyldocosanes. (13)C NMR data for these compounds confirmed that the cuticular hydrocarbon isolated from the cane beetle Antitrogus parvulus was the (4S,6R,8R,10S,16S)-stereoisomer.
Assuntos
Besouros/química , Hidrocarbonetos/síntese química , Animais , Besouros/anatomia & histologia , Estrutura Molecular , EstereoisomerismoRESUMO
INTRODUCTION: Breastfeeding is the first step to forming children who are not only healthier but smarter, with a better emotional quotient (EQ) and spiritual quotient (SQ). Babies need physical closeness and warmth from their mother as much as optimal nourishment. Poor knowledge and attitudes towards exclusive breastfeeding can result from information that is not intensive and maximal, due to limited breastfeeding counseling staff. Other reasons include cultural factors, especially in coastal areas, such as the belief in prelacteal feeding before the first breastfeeding; the baby has then automatically not exclusively breastfed. METHODS: This study used an intervention with a one-group pretest-posttest design. It aimed to analyze the role of breastfeeding counseling in increasing mothers' knowledge and attitudes regarding exclusive breastfeeding. The participants were pregnant women from the end of the second trimester to the third trimester, selected using stratified systematic random sampling. RESULTS: Counseling had a significant effect on mothers' knowledge (p = 0.004) and attitude (p = 0.000) in changing the behavior of coastal communities towards giving exclusive breastfeeding (p = 0.03). Intensified counseling is recommended for pregnant women in the third trimester to realize exclusive breastfeeding. CONCLUSIONS: A positive and significant effect of breastfeeding counseling was found on the level of knowledge, attitudes, and changes in the behavior of coastal communities in exclusive breastfeeding.
Assuntos
Aleitamento Materno , Neoplasias da Mama , Lactente , Criança , Feminino , Humanos , Gravidez , Mães/psicologia , AconselhamentoRESUMO
BACKGROUND: It has been suggested that combined effect of natural products may improve the treatment effectiveness in combating proliferation of cancer cells. The present study was undertaken to evaluate the possibility that the combination of xanthorrhizol and curcumin might show synergistic growth inhibitory effect towards MDA-MB-231 human breast cancer cells via apoptosis induction. The effective dose that produced 50% growth inhibition (GI50) was calculated from the log dose-response curve of fixed-combinations of xanthorrhizol and curcumin generated from the sulforhodamine B (SRB) assay. The experimental GI50 value was used to determine the synergistic activity of the combination treatment by isobolographic analysis and combination-index method. Further investigation of mode of cell death induced by the combination treatment was conducted in the present study. RESULTS: Isobole analysis revealed that substances interaction was synergistic when xanthorrhizol and curcumin were added concurrently to the cultures but merely additive when they were added sequentially. The synergistic combination treatment was then applied to the cultures to investigate the mode of cell death induced by the treatment. Immunofluorescence staining using antibody MitoCapturetrade mark revealed the possibility of altered mitochondrial transmembrane potential, which is one of the hallmark of apoptosis. Hoechst 33258 nuclear staining assay showed the rate of apoptosis of MDA-MB-231 cells to increase in response to the treatment. Apoptotic cell death was further confirmed by DNA fragmentation assay, where internucleosomal excision of DNA was induced upon treatment with xanthorrhizol-curcumin. CONCLUSION: This is the first time the combined cytotoxic effect of xanthorrhizol and curcumin on MDA-MB-231 cells has been documented and our findings provide experimental support to the hypothesis that combined xanthorrhizol-curcumin showed synergistic growth inhibitory activity on MDA-MB-231 cells via apoptosis induction.
RESUMO
Current lithographic resists depend on large polymeric materials, which are starting to limit further improvements in line-width roughness and feature size. Fullerene molecular resists use much smaller molecules to avoid this problem. However, such resists have poor radiation sensitivity. Chemical amplification of a fullerene derivative using an epoxy crosslinker and a photoacid generator is demonstrated. The sensitivity of the material is increased by two orders of magnitude, and 20-nm line widths are patterned.
Assuntos
Elétrons , Fulerenos/química , Reagentes de Ligações Cruzadas/químicaRESUMO
Conventional x-ray radiography measures the projected x-ray attenuation of an object. It requires attenuation differences to obtain contrast of embedded features. In general, the best absorption contrast is obtained at x-ray energies where the absorption is high, meaning a high absorbed dose. Diffraction-enhanced imaging (DEI) derives contrast from absorption, refraction, and extinction. The refraction angle image of DEI visualizes the spatial gradient of the projected electron density of the object. The projected electron density often correlates well with the projected mass density and projected absorption in soft-tissue imaging, yet the mass density is not an "energy"-dependent property of the object, as is the case of absorption. This simple difference can lead to imaging with less x-ray exposure or dose. In addition, the mass density image can be directly compared (i.e., a signal-to-noise comparison) with conventional radiography. We present the method of obtaining the mass density image, the results of experiments in which comparisons are made with radiography, and an application of the method to breast cancer imaging.
Assuntos
Absorciometria de Fóton/métodos , Algoritmos , Neoplasias da Mama/diagnóstico por imagem , Mamografia/métodos , Intensificação de Imagem Radiográfica/métodos , Interpretação de Imagem Radiográfica Assistida por Computador/métodos , Difração de Raios X/métodos , Absorciometria de Fóton/instrumentação , Humanos , Técnicas In Vitro , Mamografia/instrumentação , Imagens de Fantasmas , Reprodutibilidade dos Testes , Sensibilidade e Especificidade , Difração de Raios X/instrumentaçãoRESUMO
We have investigated the contrast mechanisms of the refraction angle, and the apparent absorption images obtained from the diffraction enhanced imaging technique (DEI) and have correlated them with the absorption contrast of conventional radiography. The contrast of both the DEI refraction angle image and the radiograph have the same dependence on density differences of the tissues in the visualization of cancer; in radiography these differences directly relate to the contrast while in the DEI refraction angle image it is the density difference and thickness gradient that gives the refraction angle. We show that the density difference of fibrils in breast cancer as measured by absorption images correlate well with the density difference derived from refraction angle images of DEI. In addition we find that the DEI apparent absorption image and the image obtained with the DEI system at the top of the reflectivity curve have much greater contrast than that of the normal radiograph (x8 to 33-fold higher). This is due to the rejection of small angle scattering (extinction) from the fibrils enhancing the contrast.
Assuntos
Neoplasias da Mama/diagnóstico por imagem , Neoplasias da Mama/patologia , Absorção , Algoritmos , Fenômenos Biofísicos , Biofísica , Carcinoma Lobular/diagnóstico por imagem , Carcinoma Lobular/patologia , Meios de Contraste/farmacologia , Feminino , Humanos , Modelos Estatísticos , Radiografia/métodos , Espalhamento de Radiação , SíncrotronsRESUMO
Five flavonoids, 5-hydroxy-(6:7,3':4')-di(2,2-dimethylpyrano)flavone 1, carpachromene 2, cycloartocarpesin 3, norartocarpetin 4 and 2'-hydroxy-4,4',6'-trimethoxychalcone 5, along with three triterpenes, friedelin 6, lupeol 7 and 13-sitosterol 8 were isolated for the first time from the leaves of Artocarpus fulvicortex F.M. Jarrett. The structures of these compounds were established by analysis of their spectroscopic (1D and 2D NMR) and spectrometric (MS) data, as well as by comparison of these with those reported in the literature.
Assuntos
Artocarpus/química , Flavonoides/química , Triterpenos/química , Sequência de Carboidratos , Flavonoides/isolamento & purificação , Espectroscopia de Ressonância Magnética , Espectrometria de Massas , Dados de Sequência Molecular , Folhas de Planta/química , Triterpenos/isolamento & purificaçãoRESUMO
The essential oils obtained by hydrodistillation of the rhizomes of Alpinia aquatica Rosc. syn. Alpinia melanocarpa and Alpinia malaccensis Roscoe were analysed by capillary gas chromatography and gas chromatography-mass spectrometry. Eighteen compounds, representing 98.4% of the essential oil were identified in A. aquatica rhizome oil, with ß-sesquiphellandrene in 36.5% being the major constituent, while 20 compounds representing 99.7% of the rhizome oil of A. malaccensis were identified, among which methyl (E)-cinnamate (78.2%) was the major constituent.
Assuntos
Alpinia/química , Óleos de Plantas/química , Rizoma/química , Cromatografia Gasosa , MalásiaRESUMO
Phytochemical and bioactivity studies of the leaves and stem barks of Tibouchina semidecandra L. have been carried out. The ethyl acetate extract of the leaves yielded four flavonoid compounds, identified as quercetin, quercetin 3-O-α-l-(2''-O-acetyl) arabinofuranoside, avicularin, and quercitrin, while the stem barks gave one ellagitannin, identified as 3,3'-O-dimethyl ellagic acid 4-O-α-l-rhamnopyranoside. Evaluation of the antioxidative activity on the crude extracts and pure compounds by electron spin resonance (ESR) and ultraviolet-visible (UV-vis) spectrophotometric assays showed that the pure isolated polyphenols and the EtOAc extract possessed strong antioxidative capabilities. Quercetin was found to be the most active radical scavenger in DPPH-UV and ESR methods with SC(50) values of 0.7 µM ± 1.4 and 0.7 µM ± 0.6 µM, respectively, in the antioxidant assay. A combination of quercetin and quercitrin was tested for synergistic antioxidative capacity;, however, there was no significant improvement observed. Quercetin also exhibited strong antityrosinase activity with a percent inhibition of 95.0% equivalent to the positive control, kojic acid, in the tyrosinase inhibition assay.
Assuntos
Inibidores Enzimáticos/farmacologia , Flavonoides/isolamento & purificação , Flavonoides/farmacologia , Sequestradores de Radicais Livres/farmacologia , Melastomataceae/química , Monofenol Mono-Oxigenase/antagonistas & inibidores , Fenóis/isolamento & purificação , Fenóis/farmacologia , Antioxidantes/farmacologia , Espectroscopia de Ressonância de Spin Eletrônica , Casca de Planta/química , Folhas de Planta/química , Polifenóis , Quercetina/isolamento & purificação , Quercetina/farmacologiaRESUMO
Successive extraction of the dried leaves of Melastoma malabathricum, followed by purification using repeated chromatographic techniques, yielded six compounds, including two amides, auranamide and patriscabratine, a triterpene, alpha-amyrin, and three flavonoids, quercitrin, quercetin and kaempferol-3-O-(2'',6''-di-O-p-trans-coumaroyl)-beta-glucoside. Their structures were elucidated by spectroscopic means and also by direct comparison of their spectroscopic data with respective published data. These three phenolic constituents were found to be active as free radical scavengers, with quercetin being the strongest radical scavenger, having an IC(50) value of 0.69 microM in the UV method. Quercitrin and kaempferol-3-O-(2'',6''-di-O-p-trans-coumaroyl)-beta-glucoside showed moderate radical scavenging, with IC(50) values of 74.1 and 108.8 microM, respectively.
Assuntos
Flavonoides/isolamento & purificação , Melastomataceae , Folhas de Planta , Triterpenos/isolamento & purificação , Amidas/química , Amidas/isolamento & purificação , Antioxidantes/química , Antioxidantes/isolamento & purificação , Flavonoides/química , Extratos Vegetais/química , Extratos Vegetais/isolamento & purificação , Triterpenos/químicaRESUMO
Seven flavonoid compounds have been isolated from the aerial parts of tiger's betel (Piper porphyrophyllum), which were identified as 5,7-dimethoxyflavone, 4',5,7-trimethoxy-flavone, 3',4',5,7-tetramethoxyflavone, 4'-hydroxy-3',5,7-trimethoxyflavone, 5-hydroxy-3',4',7-trimethoxyflavone, 4',5-dihydroxy-3',7-dimethoxyflavone and 5-hydroxy-7-methoxyflavanone. The identification of all compounds was achieved by physical properties and spectroscopically. These data were also confirmed by comparison with previously reported spectral data. Flavonoid compounds with high content in P. porphyrophyllum can probably be used as a chemical marker for this Piper species.
Assuntos
Flavonoides/isolamento & purificação , Piperaceae/química , Cromatografia em Camada Fina , Flavonoides/química , Análise Espectral/métodosRESUMO
From the rhizomes of Curcuma ochrorhiza, four sesquiterpenes, isofuranodiene, germacrene, furanogermenone and zederone, have been isolated, the structures of which have been elucidated by spectroscopic methods.
Assuntos
Curcuma/química , Sesquiterpenos de Germacrano/isolamento & purificação , Cromatografia em Gel , Rizoma/química , Sesquiterpenos de Germacrano/químicaRESUMO
OBJECTIVE: To introduce a novel X-ray technology, diffraction-enhanced X-ray imaging (DEI), in its early stages of development, for the imaging of articular cartilage. DESIGN: Disarticulated and/or intact human knee and talocrural joints displaying both undegenerated and degenerated articular cartilage were imaged with DEI. A series of three silicon crystals were used to produce a highly collimated monochromatic X-ray beam to achieve scatter-rejection at the microradian level. The third crystal (analyser) was set at different angles resulting in images displaying different characteristics. Once the diffraction enhanced (DE) images were obtained, they were compared to gross and histological examination. RESULTS: Articular cartilage in both disarticulated and intact joints could be visualized through DEI. For each specimen, DE images were reflective of their gross and histological appearance. For each different angle of the analyser crystal, there was a slight difference in appearance in the specimen image, with certain characteristics changing in their contrast intensity as the analyser angle changed. CONCLUSIONS: DEI is capable of imaging articular cartilage in disarticulated, as well as in intact joints. Gross cartilage defects, even at early stages of development, can be visualized due to a combination of high spatial resolution and detection of X-ray refraction, extinction and absorption patterns. Furthermore, DE images displaying contrast heterogeneities indicative of cartilage degeneration correspond to the degeneration detected by gross and histological examination.