Versatile coordination chemistry towards multifunctional carbon nanotube nanohybrids

Dispersible single-walled carbon nanotubes grafted with poly(4-vinylpyridine), SWNT-PVP, were tested in coordination assays with zinc tetraphenylporphyrin (ZnP). Kinetic and spectroscopic evidence corroborates the successful formation of a SWNT-PVPZnP nanohybrid. Within this SWNT-PVPZnP nanohybrid, static electron-transfer quenching (2.0+/-0.1) x 10(9) s(-1) converts the photoexcited-ZnP chromophore into a radical-ion-pair state with a microsecond lifetime, namely one-electron oxidized-ZnP and reduced-SWNT.     

Role and effective treatment of dispersive forces in materials: Polyethylene and graphite crystals as test cases

A semiempirical addition of dispersive forces to conventional density functionals (DFT-D) has been implemented into a pseudopotential plane-wave code. Test calculations on the benzene dimer reproduced the results obtained by using localized basis set, provided that the latter are corrected for the basis set superposition error. By applying the DFT-D/plane-wave approach a substantial agreement with experiments is found for the structure and energetics of polyethylene and graphite, two typical solids that are badly described by standard local and semilocal density functionals.     

A Reevaluation of the Ambident Reactivity of the Guanine Moiety Towards Hydroxyl Radicals

Radically different : Contrary to previous proposals, the main reaction of the HO^. radical with guanosine or 2′‐deoxyguanosine is the hydrogen abstraction from the NH₂ moiety to give a guanyl radical. This radical, characterized by a broad band in the visible region (around 610 nm), undergoes tautomerization to the most stable isomer.

     

A full multiple scattering model for the analysis of time-resolved X-ray difference absorption spectra

A full multiple theoretical model (MXAN) is applied to fit picosecond difference X-ray absorption spectra at the ruthenium L(3) edge upon photoexcitation of aqueous [RuII(bpy)3]2+. We show that fitting difference spectra allows an increase in sensitivity, such that slight structural changes can be retrieved, which are not detected in fitting full spectra. The Ru-N bond distances of the excited complex in the (3)MLCT state are in good agreement with recently published values. The implementation of the present approach to L-edge spectra and its high sensitivity opens opportunities for its extension to a large class of experiments where difference X-ray absorption spectra are recorded.     

Rare earth elements,thorium and uranium in ores of the North-Latium (Italy)

In geochemistry, the distribution of the Rare Earth Elements (REEs) in earth crust and mantle allows to understand geochemical cycles and origin and age of igneous rocks. In this article REEs (Ce, Dy, Eu, La, Nd, Sm, Tb, and Yb), Th and U in ores of the North-Latium (Bracciano area, Ceriti Mt., Fate Mt., Sabatini Mt., Vulsini Mt., Acqua Rossa basin), have been investigated for evaluating the extraction feasibility for industrial applications. 107 samples were irradiated in the rotating rack of the TRIGA Mark II reactor of the R.C. Casaccia (ENEA) at neutron flux of 2.6 × 10¹² n × cm⁻² × s⁻¹ for 12 h together with primary and secondary standards. The gamma spectrometry measurements were performed after 8 h, 3 and 30 days of decay by means of HPGe detector (FWHM 1.75 keV at 1332.5 keV, peak/Compton ratio 55.1, relative efficiency of 22%) connected to a multi-channel analyzer. The total REE mean content is 105 μg g⁻¹, ranging widely between 2.23 and 410.5 μg g⁻¹ (average coefficient of variation 112%). A similar behavior is found for Th and U: their average levels are 13.5 and 6.0 μg g⁻¹, respectively. A quite good correlation between REEs and Th (and U) is found for Ceriti Mt. (r ² > 0.8) whereas for the other areas the correlation is <0.7. The results obtained evidence the low U content in the investigated locations.     

Dimerization mechanism of bis(triphenylphosphine)copper(I) tetrahydroborate: proton transfer via a dihydrogen bond

The mechanism of transition-metal tetrahydroborate dimerization was established for the first time on the example of (Ph(3)P)(2)Cu(η(2)-BH(4)) interaction with different proton donors [MeOH, CH(2)FCH(2)OH, CF(3)CH(2)OH, (CF(3))(2)CHOH, (CF(3))(3)CHOH, p-NO(2)C(6)H(4)OH, p-NO(2)C(6)H(4)N═NC(6)H(4)OH, p-NO(2)C(6)H(4)NH(2)] using the combination of experimental (IR, 190-300 K) and quantum-chemical (DFT/M06) methods. The formation of dihydrogen-bonded complexes as the first reaction step was established experimentally. Their structural, electronic, energetic, and spectroscopic features were thoroughly analyzed by means of quantum-chemical calculations. Bifurcate complexes involving both bridging and terminal hydride hydrogen atoms become thermodynamically preferred for strong proton donors. Their formation was found to be a prerequisite for the subsequent proton transfer and dimerization to occur. Reaction kinetics was studied at variable temperature, showing that proton transfer is the rate-determining step. This result is in agreement with the computed potential energy profile of (Ph(3)P)(2)Cu(η(2)-BH(4)) dimerization, yielding [{(Ph(3)P)(2)Cu}(2)(μ,η(4)-BH(4))](+).     

Algorithms for sampling a quantum microcanonical ensemble of harmonic oscillators at potential minima and conical intersections

Algorithms are presented for sampling quantum microcanonical ensembles for a potential energy minimum and for the conical intersection at the minimum energy crossing point of two coupled electronic states. These ensembles may be used to initialize trajectories for chemical dynamics simulations. The unimolecular dynamics of a microcanonical ensemble about a potential energy minimum may be compared with the dynamics predicted by quantum Rice-Ramsperger-Kassel-Marcus (RRKM) theory. If the dynamics is non-RRKM, it will be of particular interest to determine which states have particularly long lifetimes. Initializing a microcanonical ensemble for the electronically excited state at a conical intersection is a model for electronic nonadiabatic dynamics. The trajectory surface-hopping approach may be used to study the ensuing chemical dynamics. A strength of the model is that zero-point energy conditions are included for the initial nonadiabatic dynamics at the conical intersection.     

Radical-based grafting of GMA on sutures of different nature

Irradiation of a number of different sutures largely employed in the clinical practice with either high energy electrons or with γ-rays followed by quenching with glycidyl methacrylate (GMA) conveniently led to derivatization through a radical-based process. The radicals involved were detected by means of ESR spectroscopy and were characterized on the basis of their ESR spectral parameters which were also found to be consistent with the hfs constants predicted by DFT calculations. Evidence of the GMA derivatization of the sutures was obtained via(13)C CP-MAS NMR spectroscopy, while its extent was evaluated gravimetrically.     

Influence of hydrogenated oligo(cyclopentadiene) on the structure and the thermal degradation of polypropylene-based nanocomposites

Polypropylene has been compounded with a commercial organoclay both in the absence and in the presence of hydrogenated oligo(cyclopentadiene) (HOCP) as a compatibiliser. The characteristics and the properties of the nanocomposites were evaluated and compared. HOCP favours the intercalation of the polypropylene in the organoclay galleries and enables a more homogeneous dispersion of the nanoclay throughout the polymer matrix. In the compatibilised nanocomposite, the diluent effect ascribed to the HOCP component is associated with the nucleating action of the nanoclay, resulting in the development of the β-crystalline form of the polypropylene. The presence of HOCP preserves the molecular weight of the polymer during the processing and gives good overall mechanical properties to the compatibilised nanocomposite. The thermo-oxidative degradation of the polypropylene is strongly delayed in the compatibilised nanocomposite.     

Peptide anchored Langmuir–Blodgett films of a fullerene amphiphile

A new amphiphilic derivative of fullerene C₆₀ bearing an oligoglycyl tail (C₆₀CHCOgly₂OEt, 2) formed stable Langmuir floating films at the air–water interface. This occurred when the molecular assembly was stabilized by anchoring the amphiphilic C₆₀'s to the aqueous subphase, via hydrogen bonding interactions between a dipeptide (Gly–L–Leu) dissolved in the water subphase, and the oligoglycyl chain. The compression (π−A) isotherm of the Langmuir floating film constructed in such a way showed no hysteresis, was steep, and evidenced that the monolayer collapsed at a surface pressure π65 mN m⁻¹, thus confirming that the film was tightly packed, extremely stable, and rigid. A limiting area per molecule of 89.1 Ų was extrapolated, in agreement with the calculated cross-section area of the C₆₀ fullerene. On the contrary, when the dipeptide was absent and pure water was used as the subphase, the π−A isotherm yielded a limiting area <55 Ų which indicated the formation of multiple layers; moreover it showed significant hysteresis, the film was fragile, and it collapsed at π≈50 mN m⁻¹. Once anchored by the dipeptide, the floating monolayer of 2 could be transferred onto hydrophobic quartz, glass and silicon substrates, by successive vertical dipping cycles, each cycle made up of two down-strokes and two up-strokes, to yield the Langmuir–Blodgett film. Up to 200 down- and up-strokes could be repeated reproducibly, a noteworthy result for non-covalently assembled LB films of fullerenes. The transfer ratio was 1.0, except for the second down-stroke of each cycle that gave a transfer ratio of zero, making the sequence of successful transfers: D, U, U, (cleaning and spreading), D, U, U, (cleaning and spreading), and so on (D=down-stroke, U=up-stroke). The total number of deposited layers was therefore 150. X-ray diffraction spectra were registered and exhibited a peak, which was fitted by a Montecarlo method of simulation to obtain the distribution of the repeat unit responsible for scattering; such distribution, with thickness between 20 and 60 Å, was consistent with the size of the amphiphile and the transfer sequence. The UV–Vis spectra of the LB film exhibited the characteristic C₆₀ bands, and the absorption peaks in the 200–400 nm range were proportional to the number of layers, indicating that the deposition was reproducible and that the molecular environment of C₆₀ in each layer remained constant.