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61.
Ripalda JM Diaz N Roman E Galan L Montero I Goldoni A Baraldi A Lizzit S Comelli G Paolucci G 《Physical review letters》2000,84(10):2132-2135
We present a method to derive an upper bound for the entropy density of coupled map lattices with local interactions from local observations. To do this, we use an embedding technique that is a combination of time delay and spatial embedding. This embedding allows us to identify the local character of the equations of motion. Based on this method we present an approximate estimate of the entropy density by the correlation integral. 相似文献
62.
Santucci SC Goldoni A Larciprete R Lizzit S Bertolo M Baraldi A Masciovecchio C 《Physical review letters》2004,93(10):106105
We have developed a method to measure simultaneously the internal energy of bulk and the first layer atoms of a crystal. The internal energy of bulk and the surface atoms of lithium (110) have been evaluated from 22 K up to above the melting transition, applying the Debye model to the thermal broadening of the respective 1s photoemission lines. Our measurements clearly reveal two phase changes: the known liquid to solid transition and the surface melting, occurring 50 K below the bulk melting point. 相似文献
63.
Rational design, synthesis, and evaluation of key analogues of CC-1065 and the duocarmycins 总被引:2,自引:0,他引:2
Tichenor MS MacMillan KS Stover JS Wolkenberg SE Pavani MG Zanella L Zaid AN Spalluto G Rayl TJ Hwang I Baraldi PG Boger DL 《Journal of the American Chemical Society》2007,129(45):14092-14099
The design, synthesis, and evaluation of a predictably more potent analogue of CC-1065 entailing the substitution replacement of a single skeleton atom in the alkylation subunit are disclosed and were conducted on the basis of design principles that emerged from a fundamental parabolic relationship between chemical reactivity and cytotoxic potency. Consistent with projections, the 7-methyl-1,2,8,8a-tetrahydrocyclopropa[c]thieno[3,2-e]indol-4-one (MeCTI) alkylation subunit and its isomer 6-methyl-1,2,8,8a-tetrahydrocyclopropa[c]thieno[2,3-e]indol-4-one (iso-MeCTI) were found to be 5-6 times more stable than the MeCPI alkylation subunit found in CC-1065 and slightly more stable than even the DSA alkylation subunit found in duocarmycin SA, placing it at the point of optimally balanced stability and reactivity for this class of antitumor agents. Their incorporation into the key analogues of the natural products provided derivatives that surpassed the potency of MeCPI derivatives (3-10-fold), matching or slightly exceeding the potency of the corresponding DSA derivatives, consistent with projections made on the basis of the parabolic relationship. Notable of these, MeCTI-TMI proved to be as potent as or slightly more potent than the natural product duocarmycin SA (DSA-TMI, IC50 = 5 vs 8 pM), and MeCTI-PDE2 proved to be 3-fold more potent than the natural product CC-1065 (MeCPI-PDE2, IC50 = 7 vs 20 pM). Both exhibited efficiencies of DNA alkylation that correlate with this enhanced potency without impacting the intrinsic selectivity characteristic of this class of antitumor agents. 相似文献
64.
Pier Giovanni Baraldi Gian Piero Pollini Daniele Simoni Achille Barco Simonetta Benetti 《Tetrahedron》1984,40(4):761-764
A convenient entry to both title compounds 1 and 2, as well as to cis- and trans-4-iodomethyl-bicyclo [3.1.0]-hexan-2-ones 3and 4 and to 4-methyl-bicyclo [3.1.0]-hex-3-en-2-one 5 involving base-promoted reactions of cis- and -trans-3,4-diiodomethylcyclopentanones 6 and 7 is reported, and the behaviour of 6 and 7 towards different bases. bfv40bp4761b 相似文献
65.
66.
NMR spectra of partially oriented allene in 14 different liquid crystal solvents have been analyzed. The resulting direct couplings corrected for harmonic vibrations were used to determine the rα-structures. Considerable solvent effects were detected which disappeared, if the data were corrected also for the correlated molecule deformation. A solvent independent rα-structure which agreed well with IR results, and the interaction parameters of the CH and CC bonds of allene for all the solvents were determined. 相似文献
67.
R. Francini S. Pinelli A. Baraldi R. Capelletti E. Sani A. Toncelli 《辐射效应与固体损伤》2013,168(6-12):1009-1013
In the present work we report on the spectroscopic properties of the Ce 3+ ion in BaY 2 F 8 single crystals. The absorption and excitation spectra of the emission centered at 340 v nm have been measured in the temperature range 15-300 v K. The 340 v nm emission consists of two broad partially overlapping bands, peaking at 324 and 347 v nm (at 15 v K), respectively. The full width at half maximum is about 0.5 v eV at room temperature. The absorption spectrum of the lowest in energy component of the f M d transition of Ce 3+ reveals at low temperature a marked vibronic structure. High resolution (0.02 v cm m 1 ) Fourier transform infrared spectroscopy in the wave number range 500-5000 v cm m 1 and in the temperature range 9-300 v K has been exploited to monitor the f level splitting. The absorption transitions from the three Stark components of the 2 F 5/2 manifold to the four of the 2 F 7/2 one, have been monitored in the wave number range 2000-3400 v cm m 1 . The wave number separation at 9 v K between the lowest level of the ground 2 F 5/2 manifold and lowest one of the 2 F 7/2 manifold is found to be 2197.47 v cm m 1 in good agreement with the splitting detected between the two components of the d M f emission. 相似文献
68.
Abstract High resolution FTIR spectroscopy is applied at 9—300 K to KTiOPO4 single crystals doped with Er or W. The vibrational transitions due to the impurity-OH defect interaction have been detected and studied. By means of polarized absorption measurements in KTP:W the orientation of the OH dipole along the Ti-O-Ti chains has been established with the presence of tetravalent tungsten at the Ti2 site. Thermally induced line-broadening and shifts are also reported and analyzed according to the single phonon coupling model. 相似文献
69.
Iole Maria Di Gangi Paola Pirillo Silvia Carraro Antonina Gucciardi Mauro Naturale Eugenio Baraldi Giuseppe Giordano 《Analytica chimica acta》2012
Background
Exhaled breath condensate (EBC) is a biofluid collected non invasively that, enabling the measurement of several biomarkers, has proven useful in the study of airway inflammatory diseases, including asthma, COPD and cystic fibrosis. To the best of our knowledge, there is no previous report of any analytical method to detect ADMA in EBC.Objectives
Aim of this work was to develop an online sample trapping and enrichment system, coupled with an UPLC–MS/MS method, for simultaneous quantification of seven metabolites related to “Arginine-ADMA cycle”, using the isotopic dilution.Methods
Butylated EBC samples were trapped in an online cartridge, washed before and after each injection with cleanup solution to remove matrix components and switched inline into the high pressure analytical column. Multiple reaction monitoring in positive mode was used for analyte quantification by tandem mass spectrometry.Results
Validation studies were performed in EBC to examine accuracy, precision and robustness of the method. For each compound, the calibration curves showed a coefficient of correlation (r2) greater than 0.992. Accuracy (%Bias) was <3% except for NMMA and H-Arg (<20%), intra- and inter-assay precision (expressed as CV%) were within ±20% and recovery ranged from 97.1 to 102.8% for all analytes.Inter-day variability analysis on 20 EBC of adult subjects did not demonstrate any significant variation of quantitative data for each metabolite. ADMA and SDMA mean concentrations (μmol L−1), measured in EBC samples of asthmatic adolescents are significantly increased (p < 0.0001) than in normal controls (0.0040 ± 0.0021 vs. 0.0012 ± 0.0005 and 0.0020 ± 0.0015 vs. 0.0002 ± 0.0001, respectively), as well the ADMA/Tyr (0.34 ± 0.09 vs. 0.12 ± 0.02, p < 0.0001) and the SDMA/Tyr ratio (0.10 ± 0.04 vs. 0.015 ± 0.004, p < 0.0001).Conclusions
The proposed method features simple specimen preparation, maintenance of an excellent peak shape of all metabolites and reduced matrix effects as well mass spectrometer noise. Moreover, the possibility to perform different cycles of enrichment, using large injection volumes, compensated for the low concentration of analytes contained in EBC, leading to a good analytical sensitivity. Preliminary data obtained from asthmatic and healthy adolescents, demonstrated that the analytical method applied to EBC seems suitable not only for research purposes, but also for clinical routinely analysis. 相似文献70.
Mazzera M Capelletti R Baraldi A Buffagni E Magnani N Bettinelli M 《J Phys Condens Matter》2012,24(20):205501
High resolution spectroscopy (the finest being 0.01 cm(-1)) was applied in the 75-25,000 cm(-1) and 9-300 K ranges to a 1 mol% holmium doped Y PO(4) single crystal with two purposes: (1) to study the hyperfine splitting of Ho(3+) energy levels of interest for possible quantum manipulation media and (2) to analyze the electron-phonon interaction. The hyperfine structure was clearly revealed for a high number of lines in a wide wavenumber range (up to ~21,500 cm(-1)) and for a large number of multiplets. Several hyperfine patterns were monitored, differing in the number of components (a maximum of 16 could be easily distinguished in a single beautiful pattern), in their separation, and in their relative statistical weight. These features were all understood in terms of a crystal-field model, whose results are in good agreement with experiments and account for the involved level symmetry, the type of transitions (electric and magnetic dipole allowed), and the contribution of a second-order (pseudoquadrupolar) hyperfine coupling between close levels. The electron-phonon interaction, investigated through the thermally induced line shift, was critically discussed in the framework of single phonon coupling and of two phonon Raman scattering models. 相似文献