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71.
Poschalko A Lancelot N Marin J Larras V Limal D Elbayed K Raya J Piotto M Briand JP Guichard G Bianco A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(18):4532-4537
A novel resin called DEUSS (perdeuterated poly(oxyethylene)-based solid support) has been prepared by anionic polymerization of deuterated [D4]ethylene oxide, followed by cross-linking with deuterated epichlorohydrin. DEUSS can be suspended in a wide range of solvents including organic and aqueous solutions, in which it displays a high swelling capacity. As measured by proton HRMAS of the swollen polymer, the signal intensity of the oxyethylene protons is reduced by a factor of 110 relative to the corresponding nondeuterated poly(oxyethylene)poly(oxypropylene) (POEPOP) resin, thus facilitating detailed HRMAS NMR studies of covalently linked molecules. This 1H NMR invisible matrix was used for the solid-phase synthesis of peptides, oligoureas, and a series of amides as well as their characterization by HRMAS NMR spectroscopy. On-bead NMR spectra of high quality and with resolution comparable to that of liquid samples were obtained and readily interpreted. The complete absence of the parasite resin signals will be of great advantage, for example, for the optimization of multistep solid-phase stereoselective reactions, and for the conformational study of resin-bound molecules in a large variety of solvents. 相似文献
72.
73.
The method of differences is used to establish that every 2-regular multigraph onv– 10,2 (mod 3) points occurs as the neighbourhood graph of an element in a twofold triple system of orderv, with two exceptions: C2C3and C3C3.Dedicated to Professor Hanfried Lenz on the occasion of his seventieth birthday 相似文献
74.
Shoenfield's unramified version of Cohen's forcing is defined in two stages: one which does not preserve double negation and the other which modifies the former so as to preserve double negation. Here we express the unramified forcing, which preserves double negation, in a single stage. Surprisingly enough, the corresponding definition of forcing for equality acquires a rather simple form. In [2] forcing ∥- is expressed in terms of strong forcing \( \Vdash * \) viap∥-Q iffp \( \Vdash * \) ¬ ¬Q for every formulaQ ofZF set theory and every elementp of a partially ordered set (P, ≦). In its turn,p \( \Vdash * \) Q is defined by the following five clauses: (1) $$p \Vdash * a \in biff(\exists c)(\exists q \geqq p)((c,q) \in b \wedge p \Vdash * a = c)$$ (2) $$\begin{gathered} p \Vdash * a \ne biff(\exists c)(\exists q \geqq p)(((c,q) \in a \wedge p \Vdash * c \notin b) \hfill \\ ((c,q) \in b \wedge p \Vdash * c \notin a)) \hfill \\ \end{gathered} $$ (3) $$p \Vdash * \neg Qiff(\forall q)(q \leqq p \to \neg (q \Vdash * Q))$$ (4) $$p \Vdash * (Q \vee S)iff(p \Vdash * Q) \vee (p \Vdash * S)$$ (5) $$p \Vdash * (\exists x)Q(x)iff(\exists b)(p \Vdash * Q(b))$$ . 相似文献
75.
S. Banerjee S. N. Ganguli A. Gurtu R. Raghavan A. Subramanian Y. Goldschmidt-Clermont R. T. Ross S. Squarcia K. Dziunikowska T. Haupt P. Girtler D. Kuhn K. W. J. Barnham J. Wells P. R. S. Wright J. Macnaughton F. Mandl F. Shabaan M. Bardadin-Otwinowska M. Szczekowski 《Zeitschrift fur Physik C Particles and Fields》1986,31(3):401-408
Results on inclusive ? production inK ? p interactions at 110 GeV/c are presented. The production cross section is found to be larger than in πp andpp interactions at similar energies, suggesting OZI allowed \(s\bar s\) fusion to be the dominant mechanism in ? production. Thex distributions of ? and \(\bar K^{*0} \) are found to be similar to each other over the entirex range suggesting an overall strangeness suppression factor of 0.20±0.04 in the sea to be the dominant source of the difference in the cross section for ? and \(\bar K^{*0} \) . There is no evidence of a narrowφπ ? state around 2.1 GeV/c2 as suggested byK + experiments, but there is some excess of events in the region 1.94?1.98 GeV/c2 consistent with theF-meson mass as observed ine + e ? experiments. 相似文献
76.
77.
Silva L Coutinho A Fedorov A Prieto M 《Journal of photochemistry and photobiology. B, Biology》2003,72(1-3):17-26
Nystatin is a polyene antibiotic frequently applied in the treatment of topical fungal infections. In this work, a 7-nitrobenz-2-oxa-1,3-diazole (NBD) hexanoyl amide derivative of nystatin was synthesized and its detailed photophysical characterization is presented. The average conformation of the labelled antibiotic in tetrahydrofuran, ethanol and methanol was determined by intramolecular (tetraene to NBD) fluorescence resonance energy transfer measurements. At variance with the literature [Can. J. Chem. 63 (1985) 77-85], it was concluded that there is no need to invoke a solvent-dependent conformational equilibrium between extended and closed conformers of the antibiotic, because the mean tetraene-to-NBD separating distance was found to remain constant (approximately 18 A) in all the solvents studied. In addition, the large solvent dependence of the fluorescence anisotropy observed for the non-derivatized nystatin, was rationalized on the basis of the prolate ellipsoidal geometry of the molecule. It was concluded that the rod shaped and amphipathic antibiotic remains monomeric in different solvents within the concentration range studied (2-20 microM). 相似文献
78.
Pressure-supported packed capillary electrochromatography (CEC) and packed capillary high-performance liquid chromatography (pHPLC) have been coupled on-line to electrospray ionization-mass spectrometry (ESI-MS) and coordination ion spray-mass spectrometry (CIS-MS). Separation of enantiomers of barbiturates and chlorinated alkyl phenoxypropanoates were performed on a permethylated beta-cyclodextrin stationary phase by pressure-supported CEC. For on-line detection with ESI- and CIS-MS, a modified sheath-liquid interface was used. CIS-MS is a universal, novel ionization technique which improves the selectivity as well as the sensitivity. Charged complexes were formed through the addition of central complexing ions such as silver(I), cobalt(II), copper(II), and lithium(I) to the sheath flow. Advantages of CIS-MS detection compared to the ESI-MS mode are discussed. In the CIS-MS mode, increased sensitivity and high selectivity was attained through different possibilities of complexation. The superiority of pressure-supported CEC compared to pHPLC in the hyphenation with CIS-MS is demonstrated. 相似文献
79.
A Study of the Uptake of Toluidine Blue O by Porphyromonas gingivalis and the Mechanism of Lethal Photosensitization 总被引:2,自引:1,他引:2
Manpreet Bhatti Alexander MacRobert Sajeda Meghji Brian Henderson Michael Wilson 《Photochemistry and photobiology》1998,68(3):370-376
The purpose of the study was to determine the distribution of the photosensitizer toluidine blue O (TBO) within Porphyromonas gingivalis and the possible mechanism(s) involved in the lethal photosensitization of this organism. The distribution of TBO was determined by incubating P. gingivalis with tritiated TBO (3H-TBO) and fractionating the cells into outer membrane (OM), plasma membrane (PM), cytoplasmic proteins, other cytoplasmic constituents and DNA. The percentage of TBO in each of the fractions was found to be, 86.7, 5.4, 1.9, 5.7 and 0.3%, respectively. The involvement of cytotoxic species in the lethal photosensitization induced by light from a helium-neon (HeNe) laser and TBO was investigated by using deuterium oxide (D2O), which prolongs the lifetime of singlet oxygen, and the free radical and singlet oxygen scavenger L-tryptophan. There were 9.0 log10 and 2 log10 reductions in the presence of D2O and H2O (saline solutions), respectively, at a light dose of 0.44 J (energy density = 0.22 J/cm2), suggesting the involvement of singlet oxygen. Decreased kills were attained in the presence of increasing concentrations of L-tryptophan. The effect of lethal photosensitization on whole cell proteins was determined by measuring tryptophan fluorescence, which decreased by 30% using 4.3 J (energy density = 4.3 J/ cm2) of light. Effects on the OM and PM proteins were determined by sodium dodecyl sulfate polyacrylamide gel electrophoresis. There was evidence of change in the molecular masses of several PM proteins and OM proteins compared to controls. There was evidence of damage to the DNA obtained from irradiated cells. Scanning electron microscopic studies showed that there was coaggre-gation of P. gingivalis cells when sensitized and then exposed to laser light. These results suggest that lethal photosensitization of P. gingivalis may involve changes in OM and/or PM proteins and DNA damage mediated by singlet oxygen. 相似文献
80.
Alexander Aster Christopher Rumble Anna-Bea Bornhof Hsin-Hua Huang Naomi Sakai Tom olomek Stefan Matile Eric Vauthey 《Chemical science》2021,12(13):4908
1,4,5,8-Naphthalenediimides (NDIs) are widely used motifs to design multichromophoric architectures due to their ease of functionalisation, their high oxidative power and the stability of their radical anion. The NDI building block can be incorporated in supramolecular systems by either core or imide functionalization. We report on the charge-transfer dynamics of a series of electron donor–acceptor dyads consisting of a NDI chromophore with one or two donors linked at the axial, imide position. Photo-population of the core-centred π–π* state is followed by ultrafast electron transfer from the electron donor to the NDI. Due to a solvent dependent singlet–triplet equilibrium inherent to the NDI core, both singlet and triplet charge-separated states are populated. We demonstrate that long-lived charge separation in the triplet state can be achieved by controlling the mutual orientation of the donor–acceptor sub-units. By extending this study to a supramolecular NDI-based cage, we also show that the triplet charge-separation yield can be increased by tuning the environment.Ultrafast electron transfer from singlet and triplet excited states in equilibrium results in the population of both singlet and triplet charge-separated states. 相似文献