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81.
Angelo Mugnoli Giampaolo Barone Silvestre Buscemi Camilla Zaira Lanza Andrea Pace Marcella Pani Domenico Spinelli 《Journal of Physical Organic Chemistry》2009,22(11):1086-1093
An accurate crystal structure determination has provided evidence for a planar conformation for 3‐acetylamino‐5‐methyl‐1,2,4‐oxadiazole ( 5 ), in agreement with quantum‐mechanical calculations in the gas phase. In the crystal, a series of strong intermolecular N7H7….O9 hydrogen bonds link the amido groups of different molecules, causing the formation of infinite parallel ordered chains. The effect of the DMSO solvent on the energy and charge distribution of compound 5 and on its relevant 5 ? anion, involved in a fully degenerate rearrangement (FDR), has been deepened by quantum‐mechanical DFT calculations. The calculated energy barrier for the FDR increases in going from in vacuo to DMSO, in agreement with previsions based on the Hughes and Ingold rules concerning the nucleophilic substitution of an anionic reagent (the deprotonated amido group in the side chain) on a neutral substrate (the 1,2,4‐oxadiazole ring). Copyright © 2009 John Wiley & Sons, Ltd. 相似文献
82.
Giovanna Gomez dAyala Emilia Di Pace Paola Laurienzo Diletta Pantalena Elvira Somma Maria Rossella Nobile 《European Polymer Journal》2009,45(11):3217-3229
Functionalization of polymers is a particular relevant approach in the field of biodegradable polymers, where modifications are often required to allow these materials to replace more conventional, not biodegradable polymers in a wider range of applications. This article will report on functionalization of poly(ε-caprolactone) with unsaturated monomers bearing either anhydride groups (PCL-g-(MA-GMA)) or tertiary amines (PCL-g-DMAEA), obtained through radical grafting in a Brabender mixer. Crystallization kinetics parameters have been determined with several techniques (rheology, optical microscopy and differential scanning calorimetry) and the results obtained are in good agreement. It was observed that the crystallization rate significantly increases in the case of the modified polymers. 相似文献
83.
Debbie J. Beard Chandler R. Pace Charles U. Pittman Jr. Svein Saebø 《Structural chemistry》2009,20(6):961-967
Cyclic ketene acetals are a class of organic molecules characterized by a nucleophilic exo-methylene carbon attached to a
carbon with two adjacent O, N, or S atoms. We have carried out a systematic computational study of a series of five-membered
cyclic acetals like 2-methylene-1,3-dioxolane and its OS, SS, NO, NS, and NN analogs as well as all the protonated species. The calculations were performed at the MP2 level using a triple zeta plus
polarization basis set. The nucleophilicity was discussed in terms of geometrical factors, calculated atomic charges, calculated
chemical shifts, and proton affinities. All the six neutral species were strong nucleophiles. The NN analog was predicted to be the strongest and the SS analog the weakest nucleophile. 相似文献
84.
A. Renee Siler Michael R. Brindza Robert A. Walker 《Analytical and bioanalytical chemistry》2009,395(4):1063-1073
Resonance-enhanced, second harmonic generation (SHG) is used to measure the electronic structure of solutes sensitive to specific
solvation adsorbed to liquid/liquid and liquid/solid interfaces. Here, specific solvation refers to solvent–solute interactions
that are directional and localized. N-methyl-p-methoxyaniline (NMMA) is a solute whose first allowed electronic transition wavelength remains almost constant (∼315 nm)
in non-hydrogen-bonding solvents regardless of solvent polarity. However, in hydrogen-bond-accepting solvents such as dimethylsulfoxide,
NMMA’s absorbance shifts to longer wavelengths (320 nm), whereas in hydrogen-bond-donating solvents (e.g., water), the absorbance
shifts to shorter wavelengths (∼300 nm). SHG experiments show that at alkane/silica interfaces, surface silanol groups serve
as moderately strong hydrogen-bond donors as evidenced by NMMA’s absorbance of 307 nm. At the carbon tetrachloride/water interface,
NMMA absorbance also shifts to slightly shorter wavelengths (298 nm) implying that water molecules at this liquid/liquid interface
are donating strong hydrogen bonds to the adsorbed NMMA solutes. In contrast, experiments using newly developed molecular
ruler surfactants with NMMA as a model hydrophobic solute and a hydrophilic, cationic headgroup imply that, as NMMA migrates
across an aqueous/alkane interface, it carries with it water that functions as a hydrogen-bond-accepting partner. 相似文献
85.
Matkovich KM Thorne LM Wolf MO Pace TC Bohne C Patrick BO 《Inorganic chemistry》2006,45(12):4610-4618
A series of Ru(II) complexes, tcc-RuX2(POC4Pyr-P,O)2 (X = Cl (3), Br (4), I (5)), containing the hemilabile phosphine pyrenyl ether ligand 4-{2-(diphenylphosphino)phenoxy}butylpyrene (POC4Pyr (1)) are reported. The synthesis and spectroscopic properties of both the ligand, POC4pyr (1), and ligand oxide, P(=O)OC4pyr 2, and the solid-state structure of 1 are reported. Complexes 3-5 react rapidly with CO to give complexes ttt-RuX2(CO)2(POC4pyr-P)2 (X = Cl (6), Br (7), I (8)). No pyrene excimer emission is detected from 3-5; however, different intensities of excimer emission are observed for 6-8. The intensity of excimer emission decreases through the series, with 6 showing the most intense response. The emission is solely due to intramolecular pyrene excimers at low concentrations (< or =10(-4) M). Comparison of the UV-vis and steady-state fluorescence spectra shows overlap between the low energy d-d absorption of 7 and 8 with excimer emission (480 nm), suggesting nonradiative energy transfer may be occurring. Once excess CO is removed, complexes 6-8 isomerize to cis-dicarbonyl complexes cct-RuX2(CO)2(POC4Pyr-P)2 (X = Cl (9), Br (10), I (11)). The intensity of excimer emission from 9-11 increases with respect to the excimer emission observed for 6-8, with 9 showing a significant increase in excimer intensity. 相似文献
86.
Buscemi S Pace A Piccionello AP Pibiri I Vivona N Giorgi G Mazzanti A Spinelli D 《The Journal of organic chemistry》2006,71(21):8106-8113
The hydrazinolysis reaction of 5-perfluoroalkyl-1,2,4-oxadiazoles with hydrazine or methylhydrazine as bidentate nucleophiles has been investigated. The reaction occurred through the addition of the bidentate nucleophile to the C(5)-N(4) double bond of the 1,2,4-oxadiazole followed by ring-opening and ring-closure (ANRORC) involving the second nucleophilic site of the reagent. This ring-closure step could involve either the original C(3) of the 1,2,4-oxadiazole (giving a five-to-five membered ring rearrangement) or an additional electrophilic center linked to it (exploiting a five-to-six membered ring rearrangement). An alternative initial nucleophilic attack may involve the additional electrophilic center linked at C(3), that is the carbonyl group, leading to the formation of the hydrazones which undergo the Boulton-Katritzky rearrangement (BKR). The chosen reaction path is a function of the used nucleophile and of the nature of the substituent at C(3). At variance with previous hypotheses, when methylhydrazine was used, the observed regiochemistry always showed the preferred initial attack by the less hindered NH(2) end of the nucleophile on C(5). Moreover, new spectroscopic evidence allowed the assignment of correct structures to the products formed by reaction of 5-perfluoroalkyl-3-phenyl-1,2,4-oxadiazoles with methylhydrazine. 相似文献
87.
Maria Valeria De Bonis Maria Cefola Bernardo Pace Gianpaolo Ruocco 《Heat and Mass Transfer》2013,49(6):799-808
Perishable bio-substrate behavior can be modeled during packaged storage. Local mass and heattransfer have been coupled to respiration rate and microbial growth. Validating measurements have also been performed, and a multi-objective optimization was employed to tune the model. The model is able to simulate gas composition history and local bacteria spoilage in storage modes commonly adopted by the food industry, depending on product features and temperature. Exploitation of this mathematical tool would allow for informed technical and management decisions. 相似文献
88.
Dongmei Zhang Jinming Song Jason Pace Deborah A. Roess B. George Barisas 《Journal of fluorescence》2018,28(2):533-542
Protein rotation in viscous environments can be measured by fluorescence depletion anisotropy (FDA) which combines long lifetimes of chromophore triplet states with the sensitivity of fluorescence excitation and detection. FDA achieves sensitivity well beyond that attainable by the more common technique of time-resolved phosphorescence anisotropy (TPA). We have now combined benefits of both time-domain and frequency-domain FDA into a single continuous technique (CFDA). Intensity and polarization of a single laser beam are modulated continuously according to a complex, repeating waveform. Fluorescence signals excited from triplet-forming fluorescent probes are digitized over recurring waveform periods by a high-speed signal averager. CFDA experiments typically involve substantial ground state depletion. Thus signals, unlike those of TPA, are not linear in the exciting light intensity and simple data analysis based on such linearity is not appropriate. An exact solution of the coupled diffusion and triplet production/decay equation describing CFDA within individual data points has been combined with simulated annealing optimization to extract triplet and anisotropy decay kinetics from experimental data. Related calculations compare possible excitation waveforms with respect to rotational information provided per fluorescence photon. We present CFDA results for the model system of eosin conjugates of carbonic anhydrase, BSA and immunoglobulin G in 90% glycerol at various temperatures and initial cellular results on eosin-IgE bound to 2H3 cell Type I Fcε receptors. We explore how CFDA reflects rotational parameters of heterogeneous systems and discuss challenges of extending this method to single cell microscopic measurements. 相似文献
89.
CH-π stacks up! Using the protein α(2) D as a model system, we estimate that a CH-π contact between cyclohexylalanine (Cha) and phenylalanine (F) contributes approximately -0.7?kcal mol(-1) to the protein stability. The stacking F-Cha pairs are sequestered in the core of the protein, where water interference does not exist (see figure). Therefore, the observed energetic gain should represent the inherent magnitude and upper limit of the CH-π interactions. 相似文献
90.