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1.
A new high-performance liquid chromatographic method with diode array detection was developed for the separation and simultaneous determination of the carrot polyacetylenes falcarindiol (FaDOH), falcarindiol 3-acetate (FaDOAc) and falcarinol (FaOH) in carrot root extracts. The optimal chromatographic conditions were achieved on a C18 column with a linear gradient elution of water and acetonitrile as mobile phases, at the flow rate of 1.0 mL/min. All calibration curves of the three carrot polyacetylenes showed good linear regression (R2 > 0.998) within the test ranges. The developed method showed good precision for quantification of all polyacetylenes with overall intraday and interday variation of less than 3.3% and with average recovery rates of 99.2, 96.8 and 99.7% for FaDOH, FaDOAc and FaOH, respectively. The LOD (S/N = 3) and LOQ (S/N = 10) were less than 0.19 and 0.42 microg/mL, respectively, for all analytes. The established method was successfully used to determine the spatial distribution of FaDOH, FaDOAc and FaOH in six carrot genotypes (Bolero, Independent, Line 1, Mello Yello, Purple Haze and Tornado) by analysing peeled carrots and the corresponding peels for these polyacetylenes. 相似文献
2.
An extract of the roots of Levisticum officinale L. (Apiaceae) exhibited significant antimycobacterial activity against Mycobacterium fortuitum, where diacetylene compounds were identified as the active components in this extract. In contrast, polyacetylenes isolated
from different sources surprisingly exhibited no anti-mycobacterial activity. Additionally, a whole series of furanocoumarin
ethers of the polyacetylene falcarindiol exhibited anti-proliferative properties. We have studied the relationship between
the electronic properties and biological activity of these structurally related compounds and a good qualitative correlation
between predicted lipophilic parameters and activity has been established. 相似文献
3.
Cryo In-SEM Raman has been used for the first time to localise carotene compounds in a food matrix. Raman spectra of lycopene and β-carotene have been obtained from sampling oil droplets and plant cell structures visualised with cryo-SEM in tomato and carrot based emulsions containing 5% oil. It was possible to identify the carotenoids in both the oil droplets and the cell walls. Furthermore our results gave some indication that the carotenoids were in the non-crystalline state. It has been suggested that a higher amount of carotenes solubilised into the oil phase of the food matrix would lead to a higher bioaccessibility, thus understanding the effect of processing conditions on micronutrients distribution in a food matrix might help the design of plant based food products with a better nutritional quality. This shows improved structural characterisation of the cryo-SEM with the molecular sensitivity of Raman spectroscopy as a promising approach for complex biological problems. 相似文献
4.
5.
This paper describes the use of principal component analysis (PCA) to de-noise Raman spectra and considerably shorten data acquisition time in Raman mapping experiments. A solid dosage pharmaceutical material (bead) is mapped by a Raman line-mapping system. The mapping acquisition time was varied from 30 s (usually employed in practice) to only 3 s. Apparently excessive noise in the maps measured for 3 s is removed by PCA and the maps of all three components of the bead are then binarized and compared. It is found that spatial difference is negligible despite the remarkably different acquisition times employed. The spectra acquired for 3 s and reconstructed via PCA are found to largely overlap with the spectra acquired for 30 s. The signal to noise ratio of the Raman mapping spectra does not obey the expected root t dependence, thereby preventing straightforward estimation of the shortest usable acquisition time (which is to a lesser extent also a function of the binarization threshold). The results reveal that Raman microscopy can be considered a fast method for mapping some materials, in contrast to the established opinion that it is an inherently slow technique. 相似文献
6.
Rai DK Brunton NP Koidis A Rawson A McLoughlin P Griffiths WJ 《Rapid communications in mass spectrometry : RCM》2011,25(15):2231-2239
The potential use of negative electrospray ionisation mass spectrometry (ESI-MS) in the characterisation of the three polyacetylenes common in carrots (Daucus carota) has been assessed. The MS scans have demonstrated that the polyacetylenes undergo a modest degree of in-source decomposition in the negative ionisation mode while the positive ionisation mode has shown predominantly sodiated ions and no [M+H](+) ions. Tandem mass spectrometric (MS/MS) studies have shown that the polyacetylenes follow two distinct fragmentation pathways: one that involves cleavage of the C3-C4 bond and the other with cleavage of the C7-C8 bond. The cleavage of the C7-C8 bond generated product ions m/z 105.0 for falcarinol, m/z 105/107.0 for falcarindiol, m/z 147.0/149.1 for falcarindiol-3-acetate. In addition to these product ions, the transitions m/z 243.2 → 187.1 (falcarinol), m/z 259.2 → 203.1 (falcarindiol), m/z 301.2 → 255.2/203.1 (falcarindiol-3-acetate), mostly from the C3-C4 bond cleavage, can form the basis of multiple reaction monitoring (MRM)-quantitative methods which are poorly represented in the literature. The 'MS(3) ' experimental data confirmed a less pronounced homolytic cleavage site between the C11-C12 bond in the falcarinol-type polacetylenes. The optimised liquid chromatography (LC)/MS conditions have achieved a baseline chromatographic separation of the three polyacetylenes investigated within 40 min total run-time. 相似文献
7.
《Polymer Degradation and Stability》1987,17(1):5-12
High resolution 13C-NMR spectra of solid polyacetylenes were observed by the CP-MAS technique after oxidation in air. On the basis of the analysis of the observed spectra one can conclude that networks were formed during the oxidation by cross-linking between saturated carbon atoms in the polyacetylene molecules. Formation of carbonyl groups in the polyacetylene started in the early stages of the oxidation but was not the predominant reaction throughout the oxidation process. These conclusions were supported by the results of elemental analysis, infra-red and optical spectroscopies. 相似文献
8.
Withnall R Chowdhry BZ Silver J Edwards HG de Oliveira LF 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(10):2207-2212
Resonance Raman spectra of naturally occurring carotenoids have been obtained from nautilus, periwinkle (Littorina littorea) and clam shells under 514.5 nm excitation and these spectra are compared with the resonance Raman spectra obtained in situ from tomatoes, carrots, red peppers and saffron. The tomatoes, carrots and red peppers gave rise to resonance Raman spectra exhibiting a nu1 band at ca. 1520 cm(-1), in keeping with its assignment to carotenoids with ca. nine conjugated carbon-carbon double bonds in their main chains, whereas the resonance Raman spectrum of saffron showed a nu1 band at 1537 cm(-1) which can be assigned to crocetin, having seven conjugated carbon-carbon double bonds. A correlation between nu1 wavenumber location and effective conjugated chain length has been used to interpret the data obtained from the shells, and the wavenumber position (1522 cm(-1)) of the nu1 band of the carotenoid in the orange clam shell suggests that it contains nine conjugated double bonds in the main chain. However, the black periwinkle and nautilus shells exhibit nu1 bands at 1504 and 1496 cm(-1), respectively. On the basis of the correlation between nu1 wavenumber location and effective conjugated chain length, this indicates that they contain carotenoids with longer conjugated chains, the former having ca. 11 double bonds and the latter ca. 13 or even more. Raman spectra of the nautilus, periwinkle and clam shells also exhibited a strong band at 1085 cm(-1) and a doublet with components at 701 and 705 cm(-1), which can be assigned to biogenic calcium carbonate in the aragonite crystallographic form. 相似文献
9.
Jacky W. Y. Lam Ben Zhong Tang 《Journal of polymer science. Part A, Polymer chemistry》2003,41(17):2607-2629
Rigid polymer backbones have often been considered to be detrimental to the packing of mesogenic pendants, and polyacetylenes have generally been regarded as unpromising materials for light‐emitting applications. Our group, however, has succeeded in creating a series of liquid‐crystalline polyacetylenes with rigid backbones and a variety of light‐emitting polyacetylenes with luminescent chromophores. Here we demonstrate that the rigid polyacetylene skeleton can play a constructive role in guiding the alignments of mesogenic pendants and prove that polyacetylenes can be highly emissive with photoluminescence quantum yields of up to 98% and electroluminescence performances comparable or superior to those of the best blue‐light‐emitting polymers. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2607–2629, 2003 相似文献
10.
Ishiwari F Fukasawa K Sato T Nakazono K Koyama Y Takata T 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(43):12067-12075
Directed helicity control of a polyacetylene dynamic helix was achieved by hybridization with a rotaxane skeleton placed on the side chain. Rotaxane-tethering phenylacetylene monomers were synthesized in good yields by the ester end-capping of pseudorotaxanes that consisted of optically active crown ethers and sec-ammonium salts with an ethynyl benzoic acid. The monomers were polymerized with [{RhCl(nbd)}(2)] (nbd=norbornadiene) to give the corresponding polyacetylenes in high yields. Polymers with optically active wheel components that are far from the main chain show no Cotton effect, thereby indicating the formation of racemic helices. Our proposal that N-acylative neutralization of the sec-ammonium moieties of the side-chain rotaxane moieties enables asymmetric induction of a one-handed helix as the wheel components approach the main chain is strongly supported by observation of the Cotton effect around the main-chain absorption region. A polyacetylene with a side-chain rotaxane that has a shorter axle component shows a Cotton effect despite the ammonium structure of the side-chain rotaxane moiety, thereby suggesting the importance of proximity between the wheel and the main chain for the formation of a one-handed helix. Through-space chirality induction in the present systems proved to be as powerful as through-bond chirality induction for formation of a one-handed helix, as demonstrated in an experiment using non-rotaxane-based polyacetylene that had an optically active binaphthyl group. The present protocol for controlling the helical structure of polyacetylene therefore provides the basis for the rational design of one-handed helical polyacetylenes. 相似文献
11.
R Manoharan J J Baraga M S Feld R P Rava 《Journal of photochemistry and photobiology. B, Biology》1992,16(2):211-233
We have developed a method for using near infrared Raman spectroscopy to quantitatively analyze the histochemical composition of human artery. The main contributors to bands observed in the Raman spectra of normal and atherosclerotic aorta are the proteins collagen and elastin, cholesterol lipids, and calcium hydroxyapatite. The Raman scattering cross-sections of different bands for these components have been determined in order to understand their relative contributions to the Raman spectra of biological tissue. The Raman signal is observed to behave linearly with the concentration of the components, even in a highly scattering medium such as a powder. Using these data, we have developed a linear model that can be used to extract the quantitative contribution of an individual component to the spectrum of a mixture. The model has been applied to several mixtures of known composition of tissue constituents in order to evaluate its precision and accuracy. The calculated fit coefficients from the spectra are in agreement with the measured values within experimental uncertainties. The spectra of different types of atherosclerotic aorta have also been modeled, and we have extracted quantitative information regarding the relative concentration of biological constituents in atherosclerotic aorta. 相似文献
12.
Malgorzata Baranska Rafal Baranski Ewa GrzebelusMaciej Roman 《Vibrational Spectroscopy》2011,56(2):166-169
It is the first report of direct, in situ detection of carotenoids at the subcellular level by using Raman microspectroscopy. Single crystals sequestered in a carrot cell were measured using FT-Raman spectrometer equipped with a microscope and 40× objective. The observed characteristic bands centered at 1518 cm−1 and 1156 cm−1 proved the crystals were composed of carotenoids with β-carotene being predominant. The obtained results show the potential of Raman microspectroscopy for identification and analysis of compounds localized in cytoplasm by taking measurements directly from a single plant cell. 相似文献
13.
Andreeva A Apostolova I Velitchkova M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2011,78(4):1261-1265
To understand the mechanism of the photoprotective and antioxidative functions of carotenoids, it is essential to have a profound knowledge of their excited electronic and vibronic states. In the present study we investigate the most powerful antioxidants: β-carotene and lutein by means of resonance Raman spectroscopy. The aim was to study in detail their Raman spectra in solution at room temperature and their changes as a function of temperature. To measure the spectra in their natural environment pyridine has been used as a solvent. It has been chosen because of its polarizability (n=1.5092) which is close to that of membrane lipids and proteins. The temperature dependence of the most intensive ν(1) band in the range from 77 K to 295 K at 514.5 nm excitation has been obtained. It was found that in pyridine the CC stretching frequency, its intensity, line shape, and line width are very sensitive to the temperature (the sensitivity being different for the two studied carotenoids). The observed linear temperature dependence of the CC stretching frequency is explained by a mechanism involving changes of the vibronic coupling and the extent of π-electron delocalization. The different behavior of the temperature-induced broadening of the ν(1) band and its intensity for the two studied carotenoids can be associated with the different nature of their solid matrices: glassy for β-carotene and crystalline-like for lutein, owing to their different chemical structures. 相似文献
14.
Time-resolved, low-temperature resonance Raman spectra of triplet states of the carotenoids specifically present in bacterial reaction centers in a strained cis conformation have been obtained, thus demonstrating the possibility of studying intermediate transient states of these structures using resonance Raman spectroscopy. Resonance Raman spectra of triplet cis spheroidene and cis methoxyneurosporene present in reaction centers of Rhodopseudomonas spheroides, (strains 2.4.1. and Ga, respectively) exhibit marked differences with those of triplet, all- trans carotenoids previously studied in vitro. These differences, together with the frequency shifts measured for the v 1 modes, indicate that triplet carotenoids bound to reaction centers retain a cis conformation, and that probably no isomerization occurs to all- trans carotenoids upon T ← S0 excitation. Pi electron distributions along the polyene backbone are probably less regular in the triplet state than in the singlet ground state, although probably not to the extent suggested by previous theoretical calculations. The apparently anomalous behaviour of the v 2 bands of all- trans carotenoids upon T ← S0 excitation is shown to result largely from the actual complexity of this region of the Raman spectra, together with a weak participation of the v c—–c internal coordinate in the corresponding modes. Finally, the Raman scattering efficiency of triplet spheroidene bound to reaction centers is lower than that of the singlet, ground state form, under equivalent excitation conditions. 相似文献
15.
The structural features of polyacetylenes carrying two substituents at double bonds with the general formula [-C(CH3)=CR-]
n
, where R = Si(CH3)3, -Ge(CH3)3, or CH(CH3)2, are studied. It is shown that the experimental IR and Raman spectra of the polymers and the theoretically calculated vibrational
spectra for the model polymers consisting of three units coincide well with experimental data. All bands in the IR spectra
are interpreted. The potential curves of internal rotation are calculated and constructed; high values of rotation barriers
indicate a high rigidity of chains for all polymers of interest. The orthogonal arrangement of neighboring monomer units and,
as a result, the absence of electron-density conjugation over the polymer chain are revealed. Charges on atoms and electron
density on bonds of the monomer unit obtained from theoretical calculations indicate the presence of strong polarization of
all bonds, including the -C=C- bond. This effect causes a shift in the frequencies of stretching vibrations due to double
bonds in the IR spectra of polyacetylenes with Si- and Ge-containing side substituents toward the longwave region. For polyacetylene
with hydrocarbon side substituents -CH(CH3)2, such polarization is absent. 相似文献
16.
Zhiquan Shen 《Macromolecular Symposia》1994,84(1):5-13
The polymerization of acetylene and its derivatives by rare earth coordination catalysts and the characterization of the polymers so obtained in our laboratory are reviewed. Because of the metallic conductivity possessed by doped polyacetylene and the unique properties such as conductivity (semiconductivity), paramagnetism, migration and transfer of energy and chemical reactivity and complex formation ability often shown by acetylenic polymers, which seem promising as specialty polymers, there has been considerable interest in the polymers of acetylene and its derivatives. A wide variety of catalyst systems have been developed for the polymerization of acetylenes. But there has been no information concerning the use of rare earth compounds as catalysts in the polymerization of acetylene and its derivatives. We for the first time in 1981 have succeeded in the polymerization of acetylene with rare earth coordination catalysts, which in turn is a development based upon earlier work on the diene polymerization using rare earth coordination catalysts(Ref. 1). Using rare earth catalysts, acetylene can be polymerized conveniently into high cis polyacetylene films with metallic sheen at room temperature and phenylacetylene can also be polymerized into high molecular weight, high cis polyphenylacetylene films at ambient temperature. Thus new varieties of polyacetylenes have been developed and a novel family of coordination catalysts consisting of a rare earth compound plus trialkyl aluminum for the polymerization of acetylenes has been exploited. This article reviews our studies on the polymerization of acetylene and its derivatives with rare earth coordination catalysts and on the characterization of the polyacetylenes prepared. 相似文献
17.
THE ROLE OF OXYGEN IN PHOTOSENSITIZATIONS WITH POLYACETYLENES AND THIOPHENE DERIVATIVES 总被引:1,自引:0,他引:1
Abstract— The mechanism of photosensitization by polyacetylenes and biosynthetically derived thiophenes from species of the plant family Asteraceae was examined. With thiophenes photosensitization of yeast and E. coli occurred under aerobic but not anaerobic conditions. For similar experiments with polyacetylenes, both photodynamic and non-photodynamic mechanisms were observed. While the relative toxicities of thiophenes and polyacetylenes under near UV radiation was in general similar, the in vitro generation of singlet oxygen was considerably less for polyacetylenes than thiophenes, which is additional evidence for the existence of an alternate mechanism of action in polyacetylene photosensitization. Rates of photodegradation of polyacetylenes are higher than for thiophenes suggesting that bond breaking/formation processes are more favored relative to energy transfer to oxygen for polyacetylenes than thiophenes. 相似文献
18.
SOLUBLE POLYACETYLENE OBTAINED WITH RARE-EARTH CATALYST AND SOME ASPECTS OF POLYMERIZATION MECHANISM
Soluble polyacetylene (PA) with well--defined nature has been synthesized with catalyst system Nd(i-OPr)_3/AIR_3 (R=C_2H_5-, i-C_4H_9-) and characterized by IR, Raman and ESR Spectra etc. Number average molecular weight of the soluble specimen were determined by VPO to be about 500g/mol. or lower. The IR and NMR spectra and end group analysis of" the soluble polyacetylene fully demonstrate that polymerization of acetylene with rare-earth catalyst is realized through monomer insertion between the transition metal-carbon bond. 相似文献
19.
20.
Anti‐Inflammatory Activity of a Novel Acetylene Isolated from the Roots of Angelica tenuissima Nakai
Hyun Gyu Choi Hyukjae Choi Jeong‐Hyung Lee Byung Sun Min Jeong Ah Kim 《Helvetica chimica acta》2016,99(6):447-451
Three polyacetylenes, one novel and two known, were isolated from the root of Angelica tenuissima. Using 1H‐ and 13C‐NMR, COSY, HMBC, and HMQC, their structures were found to be (3R,8S)‐heptadeca‐1‐en‐4,6‐diyne‐3,8‐diol ( 1 ), falcarindiol ( 2 ), and oplopandiol ( 3 ). Absolute configurations of compound 1 were established using Mosher's esterification. In addition, the polyacetylenes ( 1 – 3 ) were evaluated for their anti‐inflammatory activity. Compounds 1 and 3 showed potent inhibitory activity against lipopolysaccharide‐induced nitric oxide (NO) production in RAW267.7 macrophage cells with IC50 values of 4.31 and 5.06 μm, respectively. Compound 1 strongly inhibited inducible nitric oxide synthase (iNOS) and cyclooxygenase (COX)‐2 in a concentration‐dependent manner. 相似文献