Antonio Barbon

Analysis of the Spatial Distribution of Free Radicals in Ammonium Tartrate by Pulse EPR Techniques

Abstract Marrale, M., Brai, M., Barbon, A. and Brustolon, M. Analysis of the Spatial Distribution of Free Radicals in Ammonium Tartrate by Pulse EPR Techniques. Radiat. Res. 171, 349–359 (2009). Using pulse electron paramagnetic resonance (EPR) on a series of l(+)-ammonium tartrate (AT) dosimeters exposed to radiations with different linear energy transfer (LET), we assessed the ability of pulse EPR spectroscopy to discriminate the quality of various radiation beams such as 60Co γ-ray photons, protons and thermal neutrons at various doses by analyzing the local radical distributions produced by the different beams. We performed two types of pulse EPR investigations: two-pulse electron spin echo decay obtained by varying the microwave power, and a double electron-electron resonance (DEER) study. Both methods provide information about the dipolar interactions among the free radicals and about their spatial distributions. The first method provided information on the instantaneous diffusion and hence the microscopic concentration of the radicals that is compared with the macroscopic one obtained by CW-EPR. The DEER spectra yielded the distributions of distances between pairs of radicals two to five crystal cells apart produced by the same radiation event, a result reported here for the first time. The inter-radical distributions given by the DEER results have been simulated by modeling the radical distributions according to the details of the matter-radiation interactions for the various beams. The results of both types of pulse experiments are strongly dependent on the radiation quality. This was also observed for samples giving indistinguishable CW-EPR spectral profiles. We conclude that the pulse EPR measurements can be valuable tools for distinguishing the LET of the radiation beams, an important parameter for radiobiological considerations.

The Selective Oxidation of n-Butane to Maleic Anhydride : Comparison of Bulk and Supported V-P-O Catalysts

V–P–O catalysts supported on the surface of silica and titania particles were studied and compared with bulk V–P–O. The catalytic performance was tested in the η‐butane oxidation reaction to maleic anhydride, and the structure of the equilibrated catalysts was characterised with X‐ray absorption spectroscopy (EXAFS) and (low‐temperature) ESR spectroscopy. Our results show considerable differences in catalytic performance between VPO/TiO2 on the one hand, and VPO/SiO2 and VPO/bulk on the other hand, the yield to maleic anhydride being comparable for VPO/bulk and VPO/SiO2. The differences in catalytic behaviour are attributed to differences in the local structure around vanadium (EXAFS). Furthermore, different spin exchange interactions between vanadium atoms in the three samples have been observed (ESR). The combination of characterisation methods suggests that the structure of the supported V–P–O phase is amorphous and differs considerably from that of bulk crystalline vanadylpyrophosphate. We therefore propose that the oxidation of η‐butane to maleic anhydride takes place over an amorphous surface V–P–O phase. This finding has high relevance for our understanding of the catalytic activity of bulk crystalline V–P–O catalysts as well.

Triplet states of the nonlinear optical chromophore DCM in single crystals of potassium hydrogen phthalate and their relationship to single-molecule dark states

Single-molecule dark states are often attributed to photoexcited triplets with scant evidence of the participation of paramagnetic molecules. The photodynamics of blinking single molecules of 4-dicyanomethylene-2-methyl-6-p-dimethylaminostyryl-4H-pyran (DCM) in crystals of potassium hydrogen phthalate (KAP) were compared with the lifetimes of DCM triplet states, likewise in KAP, whose zero-field splitting (ZFS) tensors were fully characterized by time-resolved electron paramagnetic resonance (TR-EPR) spectroscopy. Luminescent mixed crystals of KAP were grown from solutions containing 10(-4) -10(-9) M DCM, a model optically nonlinear chromophore. The luminescent dye was localized in the {111} crystalline growth sectors. The photoexcited triplets states of DCM in the heavily dyed (10(-4) M) crystals were analyzed by TR-EPR spectroscopy. The photoexcited singlet states of DCM in lightly dyed crystals (10(-9) M) were analyzed by single-molecule microscopy. Large blue shifts in the absorption and emission spectra of DCM in KAP were interpreted as a consequence of protonation at the dimethylamino nitrogen atom, an assignment supported by calculations of the zero-field splitting (ZFS) tensors of molecules in their triplet states. Experimental ZFS tensors with eigenvalues comparable to those of the computed tensors were determined from the angular dependence of the EPR spectra of DCMH(+) triplets within KAP single crystals with respect to the applied magnetic field. Data from individual growth sectors failed to show magnetically equivalent site occupancies, evidence of the kinetic ordering during growth. The intermittent fluorescence of individual chromophores was analyzed. The distributions of on(off) times were characterized by distributed rates fit to power laws. The lifetime of the triplet states was analyzed from the time decay of the EPR signals between 100 and 165 K. The data were well fit with a single time constant for the signal decay, a result wholly inconsistent with the blinking of single molecules with off times commonly of tens of seconds. Triplet decay was extrapolated to approximately 25 micros at room temperature. Therefore, the assumption that single-molecule dark states originate with triplet excited states is not sustainable for single DCM molecules in KAP.

Discrimination of Radiation Quality Through Second Harmonic Out-of- Phase cw-ESR Detection

The ability to discriminate the quality of ionizing radiation is important because the biological effects produced in tissue strongly depends on both absorbed dose and linear energy transfer (LET) of ionizing particles. Here we present an experimental electron spin resonance (ESR) analysis aimed at discriminating the effective LETs of various radiation beams (e.g., 19.3 MeV protons, 60Co photons and thermal neutrons). The measurement of the intensities of the continuous wave spectrometer signal channel first harmonic in-phase and the second harmonic out-of-phase components are used to distinguish the radiation quality. A computational analysis, was carried out to evaluate the dependence of the first harmonic in-phase and second harmonic out-of-phase components on microwave power, modulation amplitude and relaxation times, and highlights that these components could be used to point out differences in the relaxation times. On the basis of this numerical analysis the experimental results are discussed. The methodology described in this study has the potential to provide information on radiation quality.

Radical-Enhanced Intersystem Crossing in New Bodipy Derivatives and Application for Efficient Triplet–Triplet Annihilation Upconversion

A long-lived triplet excited state of the well-known fluorophore boron dipyrromethene (Bodipy) was observed for the first time via efficient radical-enhanced intersystem crossing (EISC). The triplet state has been obtained in two dyads in which the Bodipy unit is linked to a nitroxide radical, 2,2,6,6-tetramethyl-1-piperidinyloxyl (TEMPO), with two different length spacers. The photophysical properties were studied with steady-state and time-resolved transient optical spectroscopies and electron spin resonance (cw-ESR and TR-ESR). The fluorescence of Bodipy units is significantly quenched in the dyads, and the spin-polarized TEMPO signals were observed with TR-ESR, generated by a radical triplet pair mechanism. Efficient EISC (ΦT = 80%) was observed for the dyad with a shorter linker, and the triplet state lifetime of the Bodipy chromophore is exceptionally long (62 μs). The EISC takes 250 ps. Poor ISC was observed for the dyad with a longer linker. The efficient ISC and long-lived triplet excited state in this flexible system are in stark contrast to the previously studied rigid EISC systems. The EISC effect was employed for the first time to perform triplet-triplet annihilation (TTA) upconversion (quantum yield ΦUC = 6.7%).

A comparative electron paramagnetic resonance study of expanded graphites and graphene

Graphene, a novel electronic system with unprecedented characteristics, can be obtained using different methods, each producing materials with specific characteristics from the electronic point of view. Among these procedures, methods based on the expansion of graphite allow to obtain graphene material in rather high quantities. We have, then, conducted a comparative study of graphene materials produced by these methods by using electron paramagnetic resonance (EPR) techniques; single-layer commercial graphene produced using the Hummers method has been used as the reference. EPR techniques enable the study of some magnetic properties of different types of electrons exhibiting paramagnetic nature. We have analysed the EPR spectra to identify the different types of paramagnetic centres contributing to the spectrum. The analysis of the temperature-dependent EPR spectra and the use of pulse techniques allowed us to separate and characterize the contribution of free conduction electrons from the contributions of localized edge states and molecular-type paramagnetic states.

A slow relaxing species for molecular spin devices: EPR characterization of static and dynamic magnetic properties of a nitronyl nitroxide radical

Nitronyl nitroxides (NitR) are a family of persistent radicals widely used in molecular magnetism and recently suggested as potential candidates for spintronic applications. In this paper we characterize by X- and W- band Electron Paramagnetic Resonance (EPR) spectroscopy the new radical S-4-(nitronyl nitroxide) benzyl ethanethioate (NitSAc) designed for assembling on Au surfaces. We determined the radical magnetic tensors and studied by X-band pulse EPR its spin relaxation behaviour in fluid and glassy solutions of toluene. A comparison with the well known nitroxide 3-carbamoyl-2,2,5,5-tetramethyl-3-pyrrolin-1-oxyl (CTPO) is afforded. The advantages of using NitSAc in technological applications are discussed on the basis of the slow spin relaxation demonstrated by this study.

Limited influence of grain boundary defects in hot-wire CVD polysilicon films on solar cell performance

Abstract Grain boundary defects in poly-Si:H films have been analysed by infrared spectroscopy, photothermal deflection spectroscopy, dual beam photoconductivity and electron spin resonance techniques. Complete absence of 2100 cm−1 mode in infrared spectrum is observed in a material with a low defect concentration. The dangling bond resonance line at g=2.0055 showed narrowing (temperature-independent) with increasing defect density in the material. The narrowing is attributed to Heisenberg exchange at clustered defects. The transport path in a cell is through the grains and the carrier transport bypasses these grain boundary defects. This bypass explains why our n–i–p cell incorporating a 1.5-μm poly-Si:H i-layer generates a current of 18.2 mA cm−2 even though the defect density is 7.8×1016 cm−3.

Online Quantification of Criegee Intermediates of α-Pinene Ozonolysis by Stabilization with Spin Traps and Proton-Transfer Reaction Mass Spectrometry Detection

Biogenic alkenes, which are among the most abundant volatile organic compounds in the atmosphere, are readily oxidized by ozone. Characterizing the reactivity and kinetics of the first-generation products of these reactions, carbonyl oxides (often named Criegee intermediates), is essential in defining the oxidation pathways of organic compounds in the atmosphere but is highly challenging due to the short lifetime of these zwitterions. Here, we report the development of a novel online method to quantify atmospherically relevant Criegee intermediates (CIs) in the gas phase by stabilization with spin traps and analysis with proton-transfer reaction mass spectrometry. Ozonolysis of α-pinene has been chosen as a proof-of-principle model system. To determine unambiguously the structure of the spin trap adducts with α-pinene CIs, the reaction was tested in solution, and reaction products were characterized with high-resolution mass spectrometry, electron paramagnetic resonance, and nuclear magnetic resonance spectroscopy. DFT calculations show that addition of the Criegee intermediate to the DMPO spin trap, leading to the formation of a six-membered ring adduct, occurs through a very favorable pathway and that the product is significantly more stable than the reactants, supporting the experimental characterization. A flow tube set up has been used to generate spin trap adducts with α-pinene CIs in the gas phase. We demonstrate that spin trap adducts with α-pinene CIs also form in the gas phase and that they are stable enough to be detected with online mass spectrometry. This new technique offers for the first time a method to characterize highly reactive and atmospherically relevant radical intermediates in situ.

Photoexcited triplets of nitrodiphenylpolyenes hosted in channel cavities. A time resolved EPR study

The photoexcited triplet states of the three nitro substituted diphenylpolyenes 4-nitrostilbene, 4-nitrodiphenylbutadiene and 4,4′-dinitrodiphenylbutadiene included in nanostructured channel-like cavities of a PHTP-based inclusion compound have been investigated by time-resolved electron paramagnetic resonance. The inclusion compounds were synthesized by using as host dihydrotriphenylene partially hydrogenated. The same dyes have been studied also in disordered solid matrices. The triplet states produced in the inclusion compounds originate only from the ground state trans conformer, since the constraint of the host channel prevents the trans–cis photoisomerization. The simulation of all spectra in disordered matrices shows the presence of the same triplet from the trans isomer as in inclusion compounds, but also of another state with the same ZFS parameters and different spin polarization. This derives from the cis isomer through a photophysical path to the cis triplet relaxing therefore conformationally to the trans triplet. For the diphenylpolyene derivatives the effect of irradiation at two wavelengths has been studied, giving further support to this interpretation of the spectra. Comparison of the experimental ZFS parameters with the calculated ones and with those of the corresponding unsubstituted compounds shows that the nitro groups are tilted out of the π-system plane. The tilting angle is different in the inclusion compounds with respect to the disordered matrices as a consequence of the head-to-tail interactions between nitro groups in neighbour molecules packed in the channels.