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51.
Erik L. RegaladoGregory Genta-Jouve Deniz TasdemirPhilippe Amade Clara NogueirasOlivier P. Thomas 《Tetrahedron》2011,67(5):1011-1018
Seven novel steroid glycosides, acanthifoliosides A-F (1-6), and the methyl ester of 6 (7), were isolated from the marine sponge Pandaros acanthifolium as minor components. Acanthifoliosides are characterized by a rare C-15 and C-16 oxidized D ring, which was previously found in saponins produced by starfishes. Very uncommon is the presence of additional sugar residues at C-15 or C-16. Their structures were determined on the basis of extensive spectroscopic analyses, including two-dimensional NMR and HRESIMS data. The absolute configurations of the aglycones were assigned by comparison between experimental and TDDFT calculated CD spectra of 1, whereas the absolute configurations of the monosaccharide units were determined by chiral GC analyses of the acid methanolysates. Some of the acanthifoliosides exhibit moderate antiprotozoal activity but to a lesser extent than the most potent pandarosides. 相似文献
52.
Deniz E Tomasulo M Cusido J Sortino S Raymo FM 《Langmuir : the ACS journal of surfaces and colloids》2011,27(19):11773-11783
The stringent limitations imposed by diffraction on the spatial resolution of fluorescence microscopes demand the identification of viable strategies to switch fluorescence under optical control. In this context, the photoinduced and reversible transformations of photochromic compounds are particularly valuable. In fact, these molecules can be engineered to regulate the emission intensities of complementary fluorophores in response to optical stimulations. On the basis of this general design logic, we assembled a functional molecular construct consisting of a borondipyrromethene fluorophore and a nitrospiropyran photochrome and demonstrated that the emission of the former can be modulated with the interconversion of the latter. This fluorophore-photochrome dyad, however, has a slow switching speed and poor fatigue resistance. To improve both parameters, we developed a new family of photochromic switches based on the photoinduced opening and thermal closing of an oxazine ring. These compounds switch back and forth between ring-closed and -open isomers on nanosecond-microsecond timescales and tolerate thousands of switching cycles with no sign of degradation. In addition, the attachment of appropriate chromophoric fragments to their switchable oxazine ring can be exploited to either deactivate or activate fluorescence reversibly in response to illumination with a pair of exciting beams. Specifically, we assembled three dyads, each based on either a borondipyrromethene or a coumarin fluorophore and an oxazine photochrome, and modulated their fluorescence in a few microseconds with outstanding fatigue resistance. The unique photochemical and photophysical properties of our fluorophore-photochrome dyads can facilitate the development of switchable fluorophores for superresolution imaging and, ultimately, provide valuable molecular probes for the visualization of biological samples on the nanometer level. 相似文献
53.
A strongly fluorescent bistable rotaxane is described in which the relative position of the macrocyclic ring with respect to a solvatochromic fluorophore gives a strong response in the spectral domain. 相似文献
54.
Kushima A Parfitt D Chroneos A Yildiz B Kilner JA Grimes RW 《Physical chemistry chemical physics : PCCP》2011,13(6):2242-2249
We report on the mechanism and energy barrier for oxygen diffusion in tetragonal La(2)CoO(4+δ). The first principles-based calculations in the Density Functional Theory (DFT) formalism were performed to precisely describe the dominant migration paths for the interstitial oxygen atom in La(2)CoO(4+δ). Atomistic simulations using molecular dynamics (MD) were performed to quantify the temperature dependent collective diffusivity, and to enable a comparison of the diffusion barriers found from the force field-based simulations to those obtained from the first principles-based calculations. Both techniques consistently predict that oxygen migrates dominantly via an interstitialcy mechanism. The single interstitialcy migration path involves the removal of an apical lattice oxygen atom out from the LaO-plane and placing it into the nearest available interstitial site, whilst the original interstitial replaces the displaced apical oxygen on the LaO-plane. The facile migration of the interstitial oxygen in this path is enabled by the cooperative titling-untilting of the CoO(6) octahedron. DFT calculations indicate that this process has an activation energy significantly lower than that of the direct interstitial site exchange mechanism. For 800-1000 K, the MD diffusivities are consistent with the available experimental data within one order of magnitude. The DFT- and the MD-predictions suggest that the diffusion barrier for the interstitialcy mechanism is within 0.31-0.80 eV. The identified migration path, activation energies and diffusivities, and the associated uncertainties are discussed in the context of the previous experimental and theoretical results from the related Ruddlesden-Popper structures. 相似文献
55.
Quantitative and sensitive detection of rare mutations using droplet-based microfluidics 总被引:2,自引:0,他引:2
Pekin D Skhiri Y Baret JC Le Corre D Mazutis L Salem CB Millot F El Harrak A Hutchison JB Larson JW Link DR Laurent-Puig P Griffiths AD Taly V 《Lab on a chip》2011,11(13):2156-2166
Somatic mutations within tumoral DNA can be used as highly specific biomarkers to distinguish cancer cells from their normal counterparts. These DNA biomarkers are potentially useful for the diagnosis, prognosis, treatment and follow-up of patients. In order to have the required sensitivity and specificity to detect rare tumoral DNA in stool, blood, lymph and other patient samples, a simple, sensitive and quantitative procedure to measure the ratio of mutant to wild-type genes is required. However, techniques such as dual probe TaqMan(?) assays and pyrosequencing, while quantitative, cannot detect less than ~1% mutant genes in a background of non-mutated DNA from normal cells. Here we describe a procedure allowing the highly sensitive detection of mutated DNA in a quantitative manner within complex mixtures of DNA. The method is based on using a droplet-based microfluidic system to perform digital PCR in millions of picolitre droplets. Genomic DNA (gDNA) is compartmentalized in droplets at a concentration of less than one genome equivalent per droplet together with two TaqMan(?) probes, one specific for the mutant and the other for the wild-type DNA, which generate green and red fluorescent signals, respectively. After thermocycling, the ratio of mutant to wild-type genes is determined by counting the ratio of green to red droplets. We demonstrate the accurate and sensitive quantification of mutated KRAS oncogene in gDNA. The technique enabled the determination of mutant allelic specific imbalance (MASI) in several cancer cell-lines and the precise quantification of a mutated KRAS gene in the presence of a 200,000-fold excess of unmutated KRAS genes. The sensitivity is only limited by the number of droplets analyzed. Furthermore, by one-to-one fusion of drops containing gDNA with any one of seven different types of droplets, each containing a TaqMan(?) probe specific for a different KRAS mutation, or wild-type KRAS, and an optical code, it was possible to screen the six common mutations in KRAS codon 12 in parallel in a single experiment. 相似文献
56.
Kirmizibekmez H Atay I Kaiser M Yesilada E Tasdemir D 《Natural product communications》2011,6(11):1697-1700
The in vitro antiprotozoal activities of crude methanolic extracts from the aerial parts of five Lamiaceae plants (Salvia tomentosa, S. sclarea, S. dichroantha, Nepeta nuda subsp. nuda and Marrubium astracanicum subsp. macrodon) were evaluated against four parasitic protozoa, i.e. Trypanosoma brucei rhodesiense, T. cruzi, Leishmania donovani and Plasmodium falciparum. The cytotoxic potentials of the extracts on L6 cells were also evaluated. Melarsoprol, benznidazole, miltefosine, chloroquine and podophyllotoxin were used as reference drugs. All crude MeOH extracts showed antiprotozoal potential against at least three parasites, so they were dispersed in water and partitioned against n-hexane and chloroform to yield three subextracts that were screened in the same test systems. The n-hexane extract of N. nuda was the most active against T. brucei rhodesiense while the CHCl3 extracts of S. tomentosa and S. dichroantha showed significant activity against L. donovani. All organic extracts displayed in vitro antimalarial and moderate trypanocidal activities against T. cruzi with the n-hexane extract of S. sclarea being the most active against the latter. The extracts displayed low or no cytotoxicity towards mammalian L6 cells. 相似文献
57.
Abdullin S. Banerjee S. Bellucci L. Charlot C. Denegri D. Dittmar M. Drollinger V. Dubinin M.N. Dzelalija M. Green D. Iasvili I. Ilyin V.A. Kinnunen R. Kunori S. Lassila-Perini K. Lehti S. Mazumdar K. Moortgat F. Muller Th. Nikitenko A. Puljak I. Salmi P. Seez C. Slabospitsky S. Stepanov N. Vidal R. Wu W. Yildiz H.D. Zeyrek M. 《The European Physical Journal C - Particles and Fields》2005,39(2):41-61
The European Physical Journal C - This work summarizes the studies for the Higgs boson searches in CMS at the LHC collider. The main discovery channels are presented and the potential is given for... 相似文献
58.
This paper concerns the optimum thickness distribution of unconstrained viscoelastic damping layer treatments for plates. The system loss factor is expressed in terms of the mechanical properties of the plate and damping layer and the layer/plate thickness ratio. Optimum distributions of the thickness ratio that maximize the system loss factor are obtained through sequential unconstrained minimization techniques. Results are presented for both simply-supported and edge-fixed rectangular plates with aspect ratios of 1·0 to 4·0. These results indicate that the system loss factor can be increased by as much as 100%, or more, by optimizing the thickness distribution of the damping treatment. Also revealed are the regions of the plate where added damping treatments are most effective. 相似文献
59.
A detailed DSC study has been done for the substance HxBPA in the temperature range 170 to 380 K and the scheme of transitions in this compound has been deduced. From X-ray work, values for the smectic layer thickness and inplane intermolecular distance have been found in two of the liquid crystalline phases, P2 and SH. 相似文献
60.