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A short and efficient total synthesis of isoroquefortine C, the 3,12-(Z)-isomer of roquefortine C, from L-tryptophan methyl ester hydrochloride and 4(5)-(hydroxy)methylimidazole hydrochloride is described. 相似文献
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New LC-MS (full scan) and LC-MS-MS (selected ion reaction monitoring) methods for the simultaneous determination of mycophenolic acid, griseofulvin, roquefortine C, chaetoglobosin B, verruculogen and penitrem A, and other Penicillium derived mycotoxins in food and feed samples are described. The methodologies involve sample extraction with acetonitrile-water, defatting with hexane and quantification using LC-MS with atmospheric pressure chemical ionisation or LC-MS-MS. Detector responses, for each of the methods and mycotoxins, were found to be linear over the range 10-1000 ng of mycotoxin/g of extracted food mixture material. The mean recoveries (n = 3 to 6) of the mycotoxins from spiked food mixture samples determined using MS and MS-MS detection were 87-116 and 91-112%, respectively, for mycophenolic acid, 104-109 and 91-112%, respectively, for griseofulvin, 70-85 and 75-110%, respectively, for roquefortine C, 94-109 and 81-116%, respectively, for chaetoglobosin B, 110-115 and 90-106%, respectively, for verruculogen and 78-97 and 99-108%, respectively, for penitrem A. RSDs varied from 5.6% at the 1000 ng/g level to 23.1% at the 10 ng/g level. The limits of detection for the mycotoxins using MS and MS-MS were 70 and 10 ng/g, respectively, for mycophenolic acid, 10 and 5 ng/g, respectivley, for griseofulvin, 50 and 20 ng/g, respectively, for roquefortine C, 25 and 20 ng/g, respectively, for chaetoglobosin B, 25 and 20 ng/g, respectively, for verruculogen and 10 and 5 ng/g, respectively, for penitrem A. 相似文献
4.
Biosynthesis of Bromoroquefortines in a High Saline Medium by Penicillium chrysogenum,a Terrestrial Endophyte Collected from Coffea arabica
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José Vinicius da Silva Taicia Pacheco Fill Letícia Veras Lotufo Cláudia do Ó. Pessoa Edson Rodrigues‐Filho 《Helvetica chimica acta》2014,97(10):1345-1353
Roquefortine C ( 1 ) and 11‐bromoroquefortine C ( 4 ) were isolated from Penicillium chrysogenum, an endophyte obtained from green leaves of Coffea arabica, during induction experiments by adding halide salts to the culture media. In our studies, 11‐bromoroquefortine D and 11‐bromo‐17‐hydroxybromoroquefortine C were identified by LC/HR‐MS. It is the first time that bromoroquefortine C and D are described as halogenated natural products. These halo alkaloids were shown to be biosynthesized from brominated tryptophan as the biosynthetic precursor. Cytotoxic and antibiotic assays using roquefortine C and 11‐bromoroquefortine C showed that the presence of the 11‐Br substituent impairs some biological activities of this alkaloid. 相似文献
5.
Chad E. Hadden David J. Richard Madeleine M. Joulli Gary E. Martin 《Journal of heterocyclic chemistry》2003,40(2):359-362
Synthetic efforts towards the indole alkaloid natural product roquefortine C resulted in the formation of an unknown intermediate. Elucidation of the structure of this molecule relied on the use of long‐range 1H‐15N 2D‐NMR. Computational predictions were used to facilitate the location of weak responses in long‐range 1H‐13C HMBC spectra. These methods provided conclusive evidence that this compound possessed a novel tetracycle. The complete 12H, 13C, and 15N chemical shift assignments of this unique fused imidazolidinone tetrahydropyrroloindole derivative are reported. 相似文献
6.
N. G. Vinokurova N. F. Zelenkova B. P. Baskunov M. U. Arinbasarov 《Journal of Analytical Chemistry》2001,56(3):258-262
Electronic absorption spectra and the chromatographic retention of six alkaloids from the roquefortine group under conditions of thin-layer chromatography and high-performance liquid chromatography were examined. The applicability of these techniques to the identification of diketopiperazine alkaloids in culture liquid extracts was demonstrated using the fungusPenicillium chrysogenumVKM F-1987 as an example. 相似文献
7.
Thin-layer chromatography of mycotoxins 总被引:2,自引:0,他引:2
V Betina 《Journal of chromatography. A》1985,334(3):211-276
TLC has become an extremely powerful, rapid and in most instances inexpensive separation technique in mycotoxicology. This review presents achievements of its applications in this field. General technical aspects of the TLC of mycotoxins that are discussed include extraction and clean-up procedures, adsorbents and solvent systems, detection methods, two-dimensional TLC, high-performance TLC (HPTLC), quantitation and preparative TLC (PLC). Special applications of TLC deal with multi-mycotoxin analyses and with structurally related or individual mycotoxins (aflatoxins, sterigmatocystins, versicolorins, ochratoxins, rubratoxins, patulin, penicillic acid, mycophenolic acid, butenolide, citreoviridin, trichothecenes, cytochalasans, tremorgenic toxins, epipolythiopiperazine-3,6-diones, hydroxyanthraquinones, zearalenone, citrinin, secalonic acids, cyclopiazonic acid, PR toxin, roquefortine, xanthomegnin, viomellein and naphtho-gamma-pyrones). 相似文献
8.
We have performed density functional calculations for the structures and stabilities of various isomers of the defect fullerene clusters of C(60): C(59), C(58), and C(57). The C(59_)5-8, C(58_)5-5-7, and C(57_)4-5-9 clusters were calculated to be the most stable isomers of the C(59), C(58), and C(57) clusters, respectively. There are obvious relationships between structure and stability of the defect fullerene clusters. First, an unsaturated carbon atom favors being located at a 6-membered ring rather than a 5-membered ring. Second, the most stable isomers prefer to have newly formed 5-membered rings, rather than newly formed 4-membered rings. 相似文献
9.
A numerical simulation was done to check the possibility of using planar C/C/C multilayers with density contrast 0.2 and 0.7 g/cm3 as an X-ray waveguide. After an optimization procedure, suitable waveguide layer thicknesses were found which provide a high degree of resonant standing wave field intensity enhancement in the core layer at incident beam energy of 13 keV. The obtained results were compared with those of the Mo/Be/Mo waveguide, whose high waveguiding capability at the same energy value was reported in the 1990s. The comparison shows that standing wave field intensity resonant enhancement provided by C/C/C planar multilayers is very high and, consequently, a guided beam can be well detected. 相似文献
10.
Different from C60 dianion which readily reacts with electrophiles, supramolecular C60 dianion (2) generated from gamma-cyclodextrin-bicapped C60 (1) and NaBH4 (or diborate) in DMSO-H2O (9:1, v/v) is able to reduce N-N+, C=C-EWG and C=O bonds to provide the respective dihydro derivatives; 1-mediated reduction of acetophenone with NaBH4 in the presence of (Me2N)2CH2 and EtONa gives turn over frequency (TOF)/h of 400. 相似文献
11.
The material formed by depositing C(2)(-) anions onto/into thin C(60) films (on graphite) at room temperature has been studied by means of thermal desorption mass spectroscopy, ultraviolet photoionization spectroscopy, atomic force microscopy (AFM), and surface enhanced Raman spectroscopy. As-prepared, C(2)/C(60) films manifest thermal desorption behaviour which differs significantly from pure C(60) films. Whereas the latter can be fully sublimed, we observe decomposition of C(2)/C(60) films to a high-temperature-stable material while predominantly C(60), C(62), and C(64) are desorbed in parallel. Deposition of C(2)(-) also leads to significantly modified electronic and vibrational properties. Based on DFT model calculations of the Raman spectra, we suggest that as-prepared C(2)/C(60) films contain appreciable amounts of polymeric networks comprising -C(2)-C(60)-C(2)-C(60)- chains. Detection of sublimed C(62) and C(64) upon heating implies that thermal decomposition of C(2)/C(60) films involves addition/uptake of C(2) units into individual fullerene cages. Correspondingly, annealing films up to various intermediate temperatures results in significant modifications to valence-band UP spectra as well as to surface topographies as imaged by AFM. The novel carbonaceous material obtained by heating to T > 950 K has a finite density of states at the Fermi level in contrast to as-prepared C(2)/C(60). It comprises fused fullerene cages. 相似文献
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Three electronic absorption systems for C5 at 511, 445, and 232 nm and one for C6, C8, and C9 centered at 228, 259, and 288 nm have been observed in the gas phase. The C5 chain was produced in both discharge and ablation sources and detected using resonant two-color two-photon ionization spectroscopy involving 10.5 eV photons. The decay of the excited singlet electronic states indicates fast intramolecular processes on a subpicosecond time scale. The internal energy is assumed to be trapped in a triplet state for at least 15 micros. Hole-burning experiments on the 2 (3)Sigma(u)- <-- X (3)Sigma(g)- transition of C6, C8, and (1)Sigma(u)+ <-- X (1)Sigma(g)+ of C9 confirm the predissociative nature of the excited electronic states. 相似文献
13.
Jorge Juan Cabrera-Trujillo Prof. Dr. Israel Fernández 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(51):11806-11813
The factors controlling the oxidative addition of C−C and C−H bonds in arenes mediated by AlI have been computationally explored by means of Density Functional Theory calculations. To this end, we compared the processes involving benzene, naphthalene and anthracene which are promoted by a recently prepared anionic AlI-carbenoid. It is found that this species exhibits a strong tendency to oxidatively activate C−H bonds over C−C bonds, with the notable exception of benzene, where the C−C bond activation is feasible but only under kinetic control reaction conditions. State-of-the-art computational methods based on the combination of the Activation Strain Model of reactivity and the Energy Decomposition Analysis have been used to rationalize the competition between both bond activation reactions as well as to quantitatively analyze in detail the ultimate factors controlling these transformations. 相似文献
14.
Reaction of red phosphorus with RfI in a 1:2 molar ratio at 230 degrees C led to the formation of a mixture of (Rf)2PI and (Rf)PI2 (Rf = C6F13, C7F15, C8F17) in about a 70:30 ratio, respectively. These mixtures were separated by vacuum distillation. (Rf)2PI (Rf = C6F13, C7F15) are yellow liquids whereas (C8F17)2PI is a yellow solid. Oxidation of (Rf)2PI with excess NO2 led to (Rf)2P(O)OH (Rf = C6F13, C7F15, C8F17) in > 90% isolated yields after aqueous hydrolysis of the anhydride intermediates. These highly fluorinated phosphinic acids are white solids with sharp melting points and are highly soluble in methyl sulfoxide (DMSO) and 1,1,2-trichlorotrifluoroethane. However, solubility in chloroform and methylene dichloride is low. These perfluoroalkylphosphinic acids were characterized by IR, NMR (1H, 19F, and 31P), and mass spectra and elemental analysis. 相似文献
15.
Bhattacharya S Nayak SK Chattopadhyay S Ghosh K Banerjee M 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2007,67(5):1257-1262
To improve the selectivity ratio of C70 over C60, a new designer molecule, viz., 3-fluoromesotetraphenylporphyrin (1) has been reported in the present investigations. Fluorescence studies reveal that the Q-absorption band of 1 gets sufficient quenching effect upon addition of both C60 and C70. Binding constants (K) of the C60/1 and C70/1 complexes are estimated to be 580 and 10,800 dm3 mol(-1), respectively. Thus, K(C70)/K(C60) is approximately 19 which is very large and even comparable with other macrocyclic host molecules like calix[5]arene, azacalix[m]arene[n]pyridine, cyclotriveratrylenophane and calixarene bisporphyrin. 1H NMR chemical shift measurements show that the -NH- proton of 1 suffers more shifts in presence of C70 compared to C60. This finding also offers a good support in favor of high K value for C70/1 complex as well as large selectivity ratio of C70 over C60. 相似文献
16.
Klupp G Borondics F Kováts E Pekker A Bényei G Jalsovszky I Hackl R Pekker S Kamarás K 《The journal of physical chemistry. B》2007,111(43):12375-12382
C(60).C(8)H(8) and C(70).C(8)H(8) are prototypes of rotor-stator cocrystals. We present infrared and Raman spectra of these materials and show how the rotor-stator nature is reflected in their vibrational properties. We measured the vibrational spectra of the polymer phases poly(C(60)C(8)H(8)) and poly(C(70)C(8)H(8)) resulting from a solid-state reaction occurring on heating. On the basis of the spectra, we propose a connection pattern for the fullerene in poly(C(60)C(8)H(8)), where the symmetry of the C(60) molecule is D(2h). On illuminating the C(60).C(8)H(8) cocrystal with green or blue light, a photochemical reaction was observed leading to a product similar to that of the thermal polymerization. 相似文献
17.
The hexaanion of fullerene, C(60)(6-), was obtained in 1:5 (v/v) acetonitrile-toluene mixture with a mercury hemispherical ultramicroelectrode as a working electrode at a temperature of up to 30 degrees C. The C(70)(6-) ion also can be observed under the same conditions. The differences between the redox potentials of C(60) relative to C(70) indicate that it is easier to add electrons to C(70) and its anions compared to the counterparts of C(60). The results show that the mercury electrode is very suitable for investigation of the properties of the electrochemical reduction for the fullerenes, particularly C(60), at room temperature. 相似文献
18.
The isomers of the nitrogen-substituted fullerenes (azafullerenes) C19N, C59N, C69N, and C75N are examined using all-electron Gaussian atomic orbital basis density functional theory, to determine the doublet radical geometries and hyperfine coupling constants. We find that the inaccuracy of previously calculated hyperfine coupling constants of C59N resulted from a poor treatment of the geometry optimization. We find that UB3LYP minimization of the radical geometry in the 6-31G basis, followed by single-point evaluation of the hyperfine constants in which an expanded basis is used on the atomic sites of interest, forms an efficient compromise between computational cost and accuracy with respect to experimental hyperfine constants. Using this approach, we assign the hyperfine signals observed in experiments on the C69N radical by calculating the hyperfine coupling constants for all five of the isomers and examine the electron spin density distribution. Finally, we present predicted hyperfine coupling constants for the isomers of C19N and C75N for use in the interpretation of future experiments. 相似文献
19.
Cavallotti C Mancarella S Rota R Carrà S 《The journal of physical chemistry. A》2007,111(19):3959-3969
We have recently proposed that the addition of C2H2 to the cyclopentadienyl radical can lead to the rapid formation of the cycloheptatrienyl radical and, in succession, of the indenyl radical. These reactions represent an interesting and unexplored route for the enlargement of gas-phase cyclic species. In this work we report ab initio calculations we performed with the aim of investigating in detail the gas-phase reactivity of cycloheptatrienyl and indenyl radicals. We found that the reaction of the cycloheptatrienyl radical with atomic hydrogen can lead to its fast conversion into the more stable benzyl radical. This reaction pathway involves the intermediate formation of heptatriene, norcaradiene, and toluene. Successively we investigated whether this reaction mechanism can be extended to polycyclic aromatic hydrocarbons (PAHs). For this purpose we studied the reaction of C2H2 with the indenyl radical, which can be considered as a superior homologue of the cyclopentadienyl radical. This reaction proceeds through a pathway similar to that proposed for C5H5 but with a reaction rate about an order of magnitude smaller. The present calculations extend thus the previously proposed C5-C7-C9 mechanism to bicyclic PAH and suggest a fast route for the conversion of C5 into C6 cyclic radicals, mediated by the formation of C7 cyclic species. 相似文献
20.
A monodispersed fullerene material comprising exclusively C(58) cages was doped with Cs to generate Cs(x)C(58) films of various compositions. The resulting modified properties have been studied using a variety of surface analysis methods with emphasis on thermal desorption and ultraviolet photoelectron spectroscopies. Cs doping raises the thermal stability of C(58) films which are characterized by quasi-covalent cage-cage bonds between annelated pentagon sites. Desorption mass spectra show emission of significant amounts of C(60) at elevated temperatures implying that Cs doping can activate C(58)→C(60) conversion in the condensed phase. In the case of saturated Cs(x)C(58) films, up to 4.5% of the initially deposited C(58) can be desorbed as C(60). From the spectroscopic data, we infer that Cs insertion and transport into the interstitial sites of the C(58) solid is accompanied by spontaneous electron transfer to the electronegative fullerene framework-leading to a weakening of intercage carbon-carbon bonds. At the same time, the overall cohesion of the solid film is enhanced by the formation of multiple ionic Cs(+) (β)C(58) (-) (δ) interactions. Near 800 K, Cs(+) activates∕catalyzes concerted disproportionation reactions resulting in the transfer of C(2) from C(58) (-) (δ) to neighbouring cages to yield C(60) (and C(56)). Heating Cs(x)C(58) films to beyond this temperature range yields a (high temperature) stable reaction product with a significantly modified UP spectrum and a finite density of states at the Fermi level. 相似文献