Synthesis of 3-amino-4-fluoropyrazoles

Fluorinated pyrazoles bearing additional functional groups that allow further functionalization are of considerable interest as building blocks in medicinal chemistry. The developed synthetic strategy for new 3-amino-4-fluoropyrazoles consists of a monofluorination of β-methylthio-β-enaminoketones using 1-(chloromethyl)-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane bis(tetrafluoroborate) (Selectfluor) toward the corresponding monofluorinated enaminoketones, followed by condensation with different hydrazines.     

60]Fullerene-based monolayers as neuroprotective biocompatible hybrid materials

Here we report on the surface immobilization of redox-active [60]fullerene derivatives and the consequent neuroprotective effects toward l-glutamate induced excitotoxicity in human derived undifferentiated neuroblastoma cells.     

Environmental effects on vibrational properties of carotenoids: experiments and calculations on peridinin

Carotenoids are employed in light-harvesting complexes of dinoflagellates with the two-fold aim to extend the spectral range of the antenna and to protect it from radiation damage. We have studied the effect of the environment on the vibrational properties of the carotenoid peridinin in different solvents by means of vibrational spectroscopies and QM/MM molecular dynamics simulations. Three prototypical solvents were considered: cyclohexane (an apolar/aprotic solvent), deuterated acetonitrile (a polar/aprotic solvent) and methanol (a polar/protic solvent). Thanks to effective normal mode analysis, we were able to assign the experimental Raman and IR bands and to clarify the effect of the solvent on band shifts. In the 1500-1650 cm(-1) region, seven vibrational modes of the polyene chain were identified and assigned to specific molecular vibrations. In the 1700-1800 cm(-1) region a strong progressive down-shift of the lactonic carbonyl frequency is observed passing from cyclohexane to methanol solutions. This has been rationalized here in terms of solvent polarity and solute-solvent hydrogen bond interactions. On the basis of our data we propose a classification of non-equivalent peridinins in the Peridinin-Chlorophyll-Proteins, light-harvesting complexes of dinoflagellates.     

Excitonic effects in two-dimensional vibrational spectra of liquid formamide

The linear and two-dimensional infrared (2DIR) responses of the amide I vibrational mode in liquid formamide are investigated experimentally and theoretically using molecular dynamics simulations. The recent method based on the numerical integration of the Schr?dinger equation is employed to calculate the 2DIR spectra. Special attention is devoted to the interplay of the structural dynamics and the excitonic nature of the amide I modes in determining the optical response of the studied system. In particular, combining experimental data, simulated spectra and analysis of the simulated atomic trajectory in terms of a transition dipole coupling model, we provide a convincing explanation of the peculiar features of the 2DIR spectra, which show a substantial increase of the antidiagonal bandwidth with increasing frequency. We point out that, at variance with liquid water, the 2DIR spectral profile of formamide is determined more by the excitonic nature of the vibrational states than by the fast structural dynamics responsible for the frequency fluctuations.     

Nonlinear Correction to the Euler Buckling Formula for Compressed Cylinders with Guided-Guided End Conditions

Euler’s celebrated buckling formula gives the critical load N for the buckling of a slender cylindrical column with radius B and length L as

Magic angle carbon-13 NMR study of solid poly(ethylene naphthalene-2,6-dicarboxylate)

Amorphous (1) and semicrystalline (2) samples of poly(ethylene naphthalene-2,6-dicarboxylate) (PEN) have been investigated by cross-polarization/magic angle spinning (CP/MAS) ¹³C NMR at 26°C (1 and 2), 100°C (1) and 120°C (2) in order to study the phase structure and the local motion of polymer chain segments at temperatures below and close to T_g (120°C). The lineshape of the ethylene unit ¹³C signal in sample 2 is consistent with the presence of two components which were assigned to trans and gauche conformations. The first component arises mainly from the crystalline regions and the second one from the amorphous part. Cross-polarization curves were traced by changing the contact time between carbon and proton reservoirs. T_CH (cross relaxation time) and proton T_1p (spin-lattice relaxation time in the rotating frame) values were obtained as best fit parameters by fitting calculated curves to the experimental data. All ¹³C NMR data are consistent with the presence of highly rigid ethylene units in both semicrystalline and amorphous samples within the temperature range (T) investigated. This result is in disagreement with the ¹H NMR wide line spectra which showed a noticeable narrowing of the linewidth with increasing temperature in the same range, hence indicating a great mobility of the chain segments. To account for this discrepancy a qualitative model based on the existence of two distinct dynamic regions, one where motion is highly restricted and the other one where large reorientations of ethylene group torsional angles take place, is suggested. The NMR results led to the conclusion that three structural phases are present in PEN: crystalline, very rigid amorphous, and very mobile amorphous. © 1995 John Wiley & Sons, Inc.     

On the varieties defined by Riemann-Mumford's relations

In this paper we consider varieties defined by Riemann-Mumford's relations. An irreducible component of these varieties is related to Siegel modular varieties. We prove that in most cases Riemann-Mumford varieties are not irreducible.

     

Selective grafting of amine groups on polyethylene by means of NH3−H2 RF glow discharges

Plasma treatments in Radio Frequency Glow Discharges fed with NH₃−H₂ mixtures have been performed for modifying polyethylene surfaces. Treatment kinetics and the role of species present in the glow have been investigated. Actinometric Optical Emission Spectroscopy has been utilized as a plasma diagnostic technique. Electron Spectroscopy for Chemical Analysis has been utilized for studying surface composition of treated substrates, which have been examined both astreated and after derivatization of amine-functionalities with 4-trifluoromethylbenzaldehyde vapors. It has been found that experimental plasma parameters and plasma density of active species can be controlled to achieve selective grafting of-NH₂ among all other nitrogen-containing groups.