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1.
Summary Both bottom-up sensory information and top-down influences contribute to the perception processes. We studied the perceptual
alternations of a multistable ambiguous pattern. We observed that it is possible to interfere on the process of the perception
alternance by means of subliminal visual stimuli, which either contrast or second the previous perception. We investigated
also the effect of the top-down volitional factor on the perceptual alternation. By using a combination of such top-down factor
and bottom-up stimulation, we ascertained that a non-linear type of interaction occurs between the two above factors.
Paper presented at the International Workshop ?Fluctuations in Physics and Biology: Stochastic Resonance, Signal Processing
and Related Phenomena?, Elba, 5–10 June 1994. 相似文献
2.
de Ceglie MC Musio B Affortunato F Moliterni A Altomare A Florio S Luisi R 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(1):286-296
A highly stereo‐ and regioselective functionalisation of chiral non‐racemic aziridines is reported. By starting from a parent enantioenriched aziridine and finely tuning the reaction conditions, it is possible to address the regio‐ and stereoselectivity of the lithiation/electrophile trapping sequence, thereby allowing the preparation of highly enantioenriched functionalised aziridines. From chiral N‐alkyl trans‐2,3‐diphenylaziridines (S,S)‐ 1 a , b , two differently configured chiral aziridinyllithiums could be generated (trans‐ 1 a , b‐Li in toluene and cis‐ 1 a , b‐Li in THF), thus disclosing a solvent‐dependent reactivity that is useful for the synthesis of chiral tri‐substituted aziridines with different stereochemistry. In contrast, chiral aziridine (S,S)‐ 1 c showed a temperature‐dependent reactivity to give chiral ortho‐lithiated aziridine 1 c‐ ortho ‐Li at ?78 °C and α‐lithiated aziridine 1 c‐α‐Li at 0 °C. Both lithiated intermediates react with electrophiles to give enantioenriched ortho‐ and α‐functionalised aziridines. The reaction of all the lithiated aziridines with carbonyl compounds furnished useful chiral hydroxyalkylated derivatives, the stereochemistry of which was ascertained by X‐ray and NMR spectroscopic analysis. The usefulness of chiral non‐racemic functionalised aziridines has been demonstrated by reductive ring‐opening reactions furnishing chiral amines that bear quaternary stereogenic centres and chiral 1,2‐, 1,3‐ and 1,5‐aminoalcohols. It is remarkable that the solvent‐dependent reactivity observed with (S,S)‐ 1 a , b permits the preparation of both the enantiomers of amines ( 11 and ent‐ 11 ) and 1,2‐aminoalcohols ( 13 and ent‐ 13 ) starting from the same parent aziridine. Interestingly, for the first time, a configurationally stable chiral α‐lithiated aziridine ( 1 c‐α‐Li ) has been generated at 0 °C. In addition, ortho‐hydroxyalkylated aziridines have been easily converted into chiral aminoalkyl phthalans, which are useful building blocks in medicinal chemistry. 相似文献
3.
Capriati V Florio S Luisi R Mazzanti A Musio B 《The Journal of organic chemistry》2008,73(8):3197-3204
The alpha-lithiation-trapping sequence of trans-N-alkyl-2,3-diphenylaziridines (s-BuLi or s-BuLi/TMEDA), taking place with a stereochemistry which dramatically depends on the solvent coordinating ability (inversion of configuration in THF and retention in toluene), has been carefully investigated. 1H,13C, and 7Li multinuclear NMR investigations at low temperature suggest that two differently configured lithiated aziridines (monomeric cis-1-Li in THF and dimeric trans-1-Li in toluene) are involved. 相似文献
4.
[structure: see text]. The lithiation reaction of cis- and trans-N-alkyl-2,3-diphenylaziridines has been investigated. While cis-diphenylaziridines do not undergo any lithiation upon treatment with organolithiums, the lithiation reaction of the trans counterparts is completely alpha-regioselective and the stereochemical course of the lithiation-trapping sequence is solvent dependent: inversion of configuration in coordinating solvents (THF or toluene/crown ether) and retention in hexane, ether, or toluene. The preparation of stereodefined functionalized N-alkyl-2,3-diphenylaziridines is described. 相似文献
5.
Wanda Sikorska Piotr Dacko Michał Sobota Joanna Rydz Marta Musioł Marek Kowalczuk 《Macromolecular Symposia》2008,272(1):132-135
Summary: Polyesters produced from renewable resources and susceptible to hydrolysis under the industrial composting conditions offer ecological advantages as compared to thermoplastics polymers and elastomers produced from fossil carbon sources. In this paper the degradation behaviour of polymer compositions of BTA, PLA and a-PHB in natural environment of industrial composting pile, consisting of leaves - 40%, branches - 30% and grass - 30%, have been presented. The extend of degradation was monitored by macroscopic observations of sample surfaces, changes of molecular weight, polydispersity and composition of the tested materials and their weight loss. 相似文献
6.
Roberta Musio Oronzo Sciacovelli 《Journal of magnetic resonance (San Diego, Calif. : 1997)》2001,153(2):259
The potential of 33S NMR spectroscopy for biochemical investigations on taurine (2-aminoethanesulfonic acid) is explored. It is demonstrated that 33S NMR spectroscopy allows the selective and unequivocal identification of taurine in biological samples. 33S NMR spectra of homogenated and intact tissues are reported for the first time, together with the spectrum of a living mollusc. Emphasis is placed on the importance of choosing appropriate signal processing methods to improve the quality of the 33S NMR spectra of biological tissues. 相似文献
7.
33S NMR parameters (chemical shifts and linewidths) in 2-substituted sodium ethanesulfonates, XCH2CH2SO3Na (X = H, CH3, OH, SH, NH2, Cl, Br, NH3+) depend upon the electronic properties of substituents. To explain experimental results and obtain additional information on the origin of the observed substituent effect (SE), sulfur isotropic absolute shielding constants have been calculated at DFT level of theory (B3LYP/6-311++G(2d,p)) by gauge-including atomic orbitals (GIAO) method. Data have been interpreted with the aid of natural bond orbital (NBO) method and natural chemical shielding (NCS) analysis. It has been demonstrated that in the class of compounds considered the diamagnetic contribution to sulfur-shielding constant is constant and the observed upfield shift of 33S resonance induced by electron-withdrawing substituents (reverse chemical shift effect) can be related to variations of the paramagnetic contribution. Substituents with different electronic properties cause variations in the polarization of S-C and S-O bonds of the -C-SO3- moiety thus determining changes of the electron density at sulfur nucleus and consequently the expansion or contraction of 3p sulfur orbitals. Also oxygen lone-pairs and sulfur core 2p electrons can play an active role in determining the paramagnetic contribution to sulfur shielding. With regard to linewidth variations, they can be ascribed primarily to changes in the nuclear quadrupole coupling constant values. B3LYP/6-311++G(2d,p) method allows obtaining a good reproducibility of SE on the electric field gradient (EFG) at sulfur, although its values tend to be underestimated significantly. Moreover, 17O shielding constants have been calculated. 相似文献
8.
Summary Two procedures aimed at a synthetic, quantitative characterization of the integrative activity in a small system of nerve
cells are proposed, and applications to the buccal ganglion of the molluskAplysia are described. Both methods are based on cross-correlation evaluation. The first method processes intracellular signals simultaneously
recorded from pairs of neurones, and reveals and measures the occurrence of shared synaptic input. The second method processes
extracellular multiunit signals recorded by two cuff electrodes placed around one nerve, and evaluates the impulse traffic,
subdivided according to direction and speed of propagation. The outcome of both methods may be used to represent the state
of the system, and may provide a basis to further studies on its dynamics.
Paper presented at the International Workshop ?Fluctuations in Physics and Biology: Stochastic Resonance, Signal Processing
and Related Phenomena?, Elba, 5–10 June 1994. 相似文献
9.
We use a version of Non-standard Analysis with a double scale of order of magnitude to develop an alternative foundation for
Statistics. The corresponding theory is intermediate between Statistics and Probability Theory and we view it as a link between
Frequency Statistics and Probability. 相似文献
10.
Trinchera P Musio B Degennaro L Moliterni A Falcicchio A Luisi R 《Organic & biomolecular chemistry》2012,10(10):1962-1965
Herein we report a new straightforward synthesis of cis and trans 2,5-disubstituted N,N-dialkylpiperazines, even in enantioenriched form, by reacting non-activated N-alkyl arylaziridines in the presence of a catalytic amount of a Lewis acid. A stereochemical and NMR investigation revealed useful mechanistic insights for this process. 相似文献