Experimental protection of quantum coherence by using a phase-tunable image drive.

The protection of quantum coherence is essential for building a practical quantum computer able to manipulate, store and read quantum information with a high degree of fidelity. Recently, it has been proposed to increase the operation time of a qubit by means of strong pulses to achieve a dynamical decoupling of the qubit from its environment. We propose and demonstrate a simple and highly efficient alternative route based on Floquet modes, which increases the Rabi decay time ([Formula: see text]) in a number of materials with different spin Hamiltonians and environments. We demonstrate the regime [Formula: see text] with [Formula: see text] the relaxation time, thus providing a route for spin qubits and spin ensembles to be used in quantum information processing and storage.

Formation of copper nanoparticles in LTL nanosized zeolite: spectroscopic characterization.

The state of copper species stabilized in nanosized LTL zeolite subjected to various post-synthesis treatments was unveiled by a range of spectroscopic techniques. FTIR and UV-Vis studies demonstrated that the reduction process of copper in the LTL nanosized zeolite leads to the formation of different species including Cu2+, Cu+ and Cu nanoparticles (Cu NPs). The adsorption of probe molecules (NO and CO) was used to selectively monitor the copper species in the LTL nanosized zeolite upon oxidation and reduction post-synthesis treatments. Both the Cu2+ and Cu+ species were probed by NO and CO, respectively. The amount of Cu+ in the LTL zeolite nanocrystals was about 43% as determined by FTIR, while the amount of Cu NPs was about 55% determined by the UV-Vis spectroscopic characterization. These results were complemented by EPR, 29Si and 63Cu MAS NMR spectroscopic data. The EPR spectroscopy was further applied to monitor the effective reduction of the Cu2+ species and their re-oxidation, while the 63Cu MAS NMR verified the presence of Cu NPs in the LTL nanosized zeolite crystals.

Anisotropic longitudinal electronic relaxation affects DNP at cryogenic temperatures.

We report the observation of anisotropic longitudinal electronic relaxation in nitroxide radicals under typical dynamic nuclear polarization conditions. This anisotropy affects the efficiency of dynamic nuclear polarization at cryogenic temperatures of 4 K and high magnetic fields of 6.7 T. Under our experimental conditions, the electron paramagnetic resonance spectrum of nitroxides such as TEMPOL (4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl) is only partly averaged by electronic spectral diffusion, so that the relaxation times T1e(ω) vary across the spectrum. We demonstrate how the anisotropy of T1e(ω) can be taken into account in simple DNP models.

Non-homogeneous distribution of Al3+ in doped phosphate glasses revealed by 27Al/31P solid state NMR.

Solid state NMR is applied in this contribution on the xAl2O3-(50-x/2)Na2O-(50-x/2)P2O5 composition line (with 0

Electron paramagnetic resonance imaging for real-time monitoring of Li-ion batteries.

Batteries for electrical storage are central to any future alternative energy paradigm. The ability to probe the redox mechanisms occurring at electrodes during their operation is essential to improve battery performances. Here we present the first report on Electron Paramagnetic Resonance operando spectroscopy and in situ imaging of a Li-ion battery using Li2Ru0.75Sn0.25O3, a high-capacity (>270 mAh g(-1)) Li-rich layered oxide, as positive electrode. By monitoring operando the electron paramagnetic resonance signals of Ru(5+) and paramagnetic oxygen species, we unambiguously prove the formation of reversible (O2)(n-) species that contribute to their high capacity. In addition, we visualize by imaging with micrometric resolution the plating/stripping of Li at the negative electrode and highlight the zones of nucleation and growth of Ru(5+)/oxygen species at the positive electrode. This efficient way to locate 'electron'-related phenomena opens a new area in the field of battery characterization that should enable future breakthroughs in battery research.

Origin of voltage decay in high-capacity layered oxide electrodes.

Although Li-rich layered oxides (Li1+xNiyCozMn1-x-y-zO2 > 250 mAh g(-1)) are attractive electrode materials providing energy densities more than 15% higher than today's commercial Li-ion cells, they suffer from voltage decay on cycling. To elucidate the origin of this phenomenon, we employ chemical substitution in structurally related Li2RuO3 compounds. Li-rich layered Li2Ru1-yTiyO3 phases with capacities of ~240 mAh g(-1) exhibit the characteristic voltage decay on cycling. A combination of transmission electron microscopy and X-ray photoelectron spectroscopy studies reveals that the migration of cations between metal layers and Li layers is an intrinsic feature of the charge-discharge process that increases the trapping of metal ions in interstitial tetrahedral sites. A correlation between these trapped ions and the voltage decay is established by expanding the study to both Li2Ru1-ySnyO3 and Li2RuO3; the slowest decay occurs for the cations with the largest ionic radii. This effect is robust, and the finding provides insights into new chemistry to be explored for developing high-capacity layered electrodes that evade voltage decay.

Cysteine-grafted nonwoven geotextile: a new and efficient material for heavy metals sorption--Part B.

The development of a new material designed to trap heavy metals from sediments or wastewater, based on a polypropylene non-woven covalently grafted with cysteine, has been reported in a previous paper (Part A). The non-woven was first functionalized with acrylic acid (AA) which is used as spacer, and then cysteine was immobilized on the substrate through covalent coupling in order to obtain the so-called PP-g-AA-cysteine. Some preliminary heavy metals adsorption tests gave interesting results: at 20 °C for 24 h and in a 1000 mg/L heavy metals solution, PP-g-AA-cysteine adsorbs 95 mg Cu/g PP (CuSO4 solution), 104 mg Cu/g PP (Cu(NO3)2 solution), 135 mg Pb/g PP (Pb(NO3)2 solution) and 21 mg Cr/g PP (Cr(NO3)3 solution). In this second part of the work, heavy metals sorption tests were carried out with Cu (II), Pb (II), and Cr (III) separately, in order to determine the sorption capacity of this new sorbent as a function of (i) the heavy metals concentration in the solution, (ii) the contact time with the solution, (iii) the pH and (iv) the ionic strength of the solution containing heavy metals. Moreover, the sorption capacity of PP-g-AA-Cysteine was studied using a polluted solution consisting of a mixture of these different heavy metals. An Electron Paramagnetic Resonance study was finally carried out in order to determine the coordination geometry in the environment of the copper trapped by the PP-g-AA-cysteine.

Electron transfers in a TiO2-containing MOR zeolite: synthesis of the nanoassemblies and application using a probe chromophore molecule.

New assemblies constituted by a microporous matrix of mordenite (MOR) zeolite on which TiO2 nanoclusters are deposited were synthesized using ionic oxalate complexes and TiCl3 titanium precursors. The samples were used to investigate the transfer of electrons produced by spontaneous or photo-induced ionization of a guest molecule (t-stilbene, t-St) occluded in the porous volume towards the conduction band of a conductive material placed nearby, in the pores or at least close to their entrance. The reaction mechanisms were compared in these Ti-rich solids and in a Ti-free mordenite sample. The characterization by XRD, N2 physisorption, TEM, XPS and DRIFT spectroscopy of the supramolecular TiO2/MOR systems before t-St adsorption showed the preservation of the crystalline structure after Ti addition and thermal activation treatments. They also revealed that titanium is mainly located at the external surface of the zeolite grains, in the form of highly dispersed and/or aggregated anatase. After incorporation of the guest molecule in the new assemblies, diffuse reflectance UV-visible and EPR spectroscopies indicate that the electron transfer processes are similar with and without TiO2 but strongly stabilized t-St˙(+) radicals are detected in the TiO2-MOR samples whereas such species were never detected earlier in TiO2-free mordenite using these techniques. The stabilization process is found to be more efficient in the sample prepared with TiCl3 as the precursor than with titanium oxalates. It is proposed that the proximity of TiO2 with the formed t-St˙(+) radicals provokes the stabilization of the radical through capture of the ejected electron by the semi-conductor and that confinement effects can also play a role.

State of the art in nail dosimetry: free radicals identification and reaction mechanisms.

Until very recently, analysis of bone biopsies by means of the method of electron paramagnetic resonance (EPR) collected after surgery or amputation has been considered as the sole reliable method for radiation dose assessment in hands and feet. EPR measurements in finger- and toenail have been considered for accident dosimetry for a long time. Human nails are very attractive biophysical materials because they are easy to collect and pertinent to whole body irradiation. Information on the existence of a radiation-induced signal in human nails has been reported almost 25 years ago. However, no practical application of EPR dosimetry on nails is known to date because, from an EPR perspective, nails represent a very complex material. In addition to the radiation-induced signal (RIS), parasitic and intense signals are induced by the mechanical stress caused when collecting nail samples (mechanically induced signals-MIS). Moreover, it has been demonstrated that the RIS stability is strongly influenced not only by temperature but also by humidity. Most studies of human nails were carried out using conventional X-band microwave band (9 GHz). Higher frequency Q-band (37 GHz) provides higher spectral resolution which allows obtaining more detailed information on the nature of different radicals in human nails. Here, we present for the first time a complete description of the different EPR signals identified in nails including parasitic, intrinsic and RIS. EPR in both X- and Q-bands was used. Four different MIS signals and five different signals specific to irradiation with ionizing radiation have been identified. The most important outcome of this work is the identification of a stable RIS component. In contrast with other identified (unstable) RIS components, this component is thermally and time stable and not affected by the physical contact of fingernails with water. A detailed description of this signal is provided here. The discovery of stable radiation-induced radical(s) associated with the RIS component mentioned opens a way for broad application of EPR dosimetry in human nails. Consequently, several recent dosimetry assessments of real accident cases have been performed based on the described measurements and analyses of this component.

Origin of the decoherence of the extended electron spin state in Ti-doped ß-Ga2O3.

The mechanism of decoherence of the electron spin of Ti(3+) in ß-Ga2O3 was investigated by pulsed electron paramagnetic resonance. At 4.2 K, both instantaneous and spectral diffusion contribute to the decoherence. For electron spin concentrations ≈10(25) m(-3) in the studied samples, calculations indicate that electron-electron couplings and electron couplings with (69)Ga and (71)Ga nuclei yield similar contributions to the spectral diffusion, but that electron-nuclei interactions could become the dominant cause of spectral diffusion for only slightly lower spin concentrations. Above 20 K, an additional contribution to the decoherence as well as to the spin-lattice relaxation arises from a two-optical-phonon Raman process, which becomes the leading decoherence mechanism for T > 39 K. Rabi oscillations with a damping time of about 79 ns at 4.2 K could also be observed. The damping of the Rabi oscillations, independent of the oscillation frequency, is suspected to arise from electron-nuclei interactions.

Reversible anionic redox chemistry in high-capacity layered-oxide electrodes.

Li-ion batteries have contributed to the commercial success of portable electronics and may soon dominate the electric transportation market provided that major scientific advances including new materials and concepts are developed. Classical positive electrodes for Li-ion technology operate mainly through an insertion-deinsertion redox process involving cationic species. However, this mechanism is insufficient to account for the high capacities exhibited by the new generation of Li-rich (Li(1+x)Ni(y)Co(z)Mn(1-x-y-z)O2) layered oxides that present unusual Li reactivity. In an attempt to overcome both the inherent composition and the structural complexity of this class of oxides, we have designed structurally related Li2Ru(1-y)Sn(y)O3 materials that have a single redox cation and exhibit sustainable reversible capacities as high as 230 mA h g(-1). Moreover, they present good cycling behaviour with no signs of voltage decay and a small irreversible capacity. We also unambiguously show, on the basis of an arsenal of characterization techniques, that the reactivity of these high-capacity materials towards Li entails cumulative cationic (M(n+)→M((n+1)+)) and anionic (O(2-)→O2(2-)) reversible redox processes, owing to the d-sp hybridization associated with a reductive coupling mechanism. Because Li2MO3 is a large family of compounds, this study opens the door to the exploration of a vast number of high-capacity materials.

Clusters dissolution of Yb3+ in codoped SiO2-Al2O3-P2O5 glass fiber and its relevance to photodarkening.

Using a combination of pulse electron paramagnetic resonance and photoluminescence spectroscopy, we demonstrate the major role of phosphorous rather than aluminium in the rare-earth dissolution process, an essential advance in telecommunication and solid laser fields. Our results also provide new insight into the micro-structural origin of the photodarkening process occurring in Yb doped fiber.

Spontaneous charge separation induced by phenothiazine sorption within acidic H(n)ZSM-5.

In situ diffuse reflectance UV-visible, Raman scattering and EPR experiments, carried out as a function of time after phenothiazine (PTZ) direct exposure to thermally activated acid H(n)ZSM-5 zeolite without any solvent, provide evidence of phenothiazine sorption and simultaneous spontaneous ionization. For comparison, phenothiazine behavior was investigated within non acidic zeolite and showed that most of the phenothiazine molecules were occluded as intact molecules and that ionization was very weak. The multivariate curve resolution analysis of the diffuse reflectance UV-visible spectra set recorded during the sorption process resolve the absorption spectra and respective concentrations of individual species involved in the sorption course. When PTZ entered through the acidic zeolite channels, PTZ (+)@H(n)ZSM-5 (-) radical pair is generated by the polarization energy. Subsequent PTZ(2+) formation was fast but only partial. After months, equilibrium including PTZ (+), PTZ(2+) and occluded PTZ was reached within acid H(n)ZSM-5 but depends on the Si/Al ratio: the higher the Al content, the easier the spontaneous ionization. The close match between PTZ and the pore size of zeolites combined with efficient polarizing effect of proton and aluminium electron trapping sites appear to be the most important factors responsible for the stabilization of PTZ (+) and PTZ(2+) and hinder efficiently the charge recombination. No evidence of Brønsted acid sites of H(n)ZSM-5 was found during the sorption of phenothiazine through generation of protonated species.

Conjugated dicarboxylate anodes for Li-ion batteries.

Present Li-ion batteries for portable electronics are based on inorganic electrodes. For upcoming large-scale applications the notion of materials sustainability produced by materials made through eco-efficient processes, such as renewable organic electrodes, is crucial. We here report on two organic salts, Li(2)C(8)H(4)O(4) (Li terephthalate) and Li(2)C(6)H(4)O(4)(Li trans-trans-muconate), with carboxylate groups conjugated within the molecular core, which are respectively capable of reacting with two and one extra Li per formula unit at potentials of 0.8 and 1.4 V, giving reversible capacities of 300 and 150 mA h g(-1). The activity is maintained at 80 degrees C with polyethyleneoxide-based electrolytes. A noteworthy advantage of the Li(2)C(8)H(4)O(4) and Li(2)C(6)H(4)O(4) negative electrodes is their enhanced thermal stability over carbon electrodes in 1 M LiPF(6) ethylene carbonate-dimethyl carbonate electrolytes, which should result in safer Li-ion cells. Moreover, as bio-inspired materials, both compounds are the metabolites of aromatic hydrocarbon oxidation, and terephthalic acid is available in abundance from the recycling of polyethylene terephthalate.

New bis-catechols 5-lipoxygenase inhibitors.

Three polyhydroxy-2-phenylnaphthalenes (1-3) and the oxy analogue of tetrahydroxypavinan (4) were prepared and evaluated for their antioxidant properties (inhibition of diphenylpycrylhydrazyl radical (DPPH), reduction of iron (III) ion) and inhibition of 5-lipoxygenase (5-LO) activity. Their three-dimensional structures were established on the basis of spectroscopic data and semiempirical calculations. Compounds 1 and 2 were found as potent 5-LO inhibitors as nordihydroguaiaretic acid (NDGA), whereas 4 is 2.5 times less potent than NDGA. The reliability of the 3-D structures with the 5-LO inhibition properties is discussed. Their antioxidant properties show that tested compounds are expected to act as redox inhibitors.

DNA topoisomerase II inhibition by peroxisomicine A(1) and its radical metabolite induces apoptotic cell death of HL-60 and HL-60/MX2 human leukemia cells.

Peroxisomicine A(1) (T-514) is a dimeric anthracenone first isolated from the plant Karwinskia humboldtiana. The compound presents a high and selective toxicity toward liver and skin cell cultures and is currently the subject of preclinical studies as an antitumor drug. To date, the molecular basis for its diverse biological effects remains poorly understood. To elucidate its mechanism of action, we studied its interaction with DNA and its effects on human DNA topoisomerases. Practically no interaction with DNA was detected. Peroxisomicine was found to inhibit topoisomerase II but not topoisomerase I. DNA relaxation and decatenation assays indicated that the drug interferes with the catalytic activity of topoisomerase II but does not stimulate DNA cleavage, in contrast to conventional topoisomerase poisons such as etoposide. Two human leukemia cell lines sensitive or resistant to mitoxantrone were used to assess the cytotoxicity of the toxin and its effect on the cell cycle. In both cases, peroxisomicine treatment was associated with a loss of cells from every phase of the cell cycle and was accompanied by a large increase in the sub-G1 region which is characteristic of apoptotic cells. The cell cycle changes were more pronounced with the sensitive HL-60 cells than with the resistant HL-60/MX2 cells (with reduced topoisomerase II activity), in agreement with the cytotoxicity measurements. Treatment of HL-60 cells with T-514 stimulated the cleavage of the poly(ADP-ribose) polymerase by intracellular proteases such as caspase-3. The cytometry and Western blot analyses reveal that peroxisomicine induces apoptosis in leukemia cells. In addition, we characterized a catabolite of peroxisomicine, named T-510R, in the form of a highly stable radical metabolite. The electron spin resonance and mass spectrometry data are consistent with the formation of an anionic semiquinonic radical. The oxidized product T-510R inhibits topoisomerase II with a reduced efficiency compared to the parent toxin and was found to be about 3-4 times less toxic to both the sensitive and resistant leukemia cell lines than T-514. Collectively, the results suggest that topoisomerase II inhibition plays a role in the cytotoxicity of the plant toxin peroxisomicine. Inhibition of topoisomerase II may serve as an inducing signal triggering the apoptotic cell death of leukemia cells exposed to the toxin. The dihydroxyanthracenone unit may represent a useful chemotype for the preparation of topoisomerase II-targeted anticancer agents.

DNA binding properties of the indolocarbazole antitumor drug NB-506.

Indolocarbazoles derived from the antibiotic rebeccamycin represent an important group of antitumor agents. Several indolocarbazoles are currently undergoing clinical trials. These compounds inhibit topoisomerase 1 to produce DNA breaks that are responsible for cell death. Unlike classical topoisomerase I poisons like camptothecin, glycosyl indolocarbazoles can form stable complexes with DNA even in the absence of topoisomerase I. At least in part, their mode of action is reminiscent of that of the anthracyclines, which also bind to nucleic acids and interfere with topoisomerase II. The lead synthetic compound in the series is the uncharged drug NB-506, which bears a glucose residue attached to the indolocarbazole chromophore substituted with two hydroxyl groups at positions 1 and 11. Here we report a detailed biophysical study aimed at characterizing the DNA binding properties of NB-506. Molecular modeling was used to compare the conformation and electronic properties of NB-506 and its analogue ED-571 bearing the two hydroxyl groups at positions 2 and 10. Surface plasmon resonance experiments, performed with DNA hairpin oligomers, indicate that NB-506 binds almost equally well to both AT and GC base pairs, and the binding affinity (K = 10(5) M(-1)) is similar to that of certain classical intercalators such as amsacrine and bisantrene. Isothermal titration calorimetry experiments show that the binding of NB-506 is enthalpy-driven (deltaH = -7.2 kcal/mol). The binding enthalpy measured for NB-506 is similar to that obtained with doxorubicin but the DNA interaction processes for the two drugs differ markedly in terms of entropy and deltaG. The free energy of NB-506 binding to DNA is considerably less favorable than that of doxorubicin. These biophysical data help us to understand further how rebeccamycin-type anticancer drugs interact with DNA.

4-Mercaptoimidazoles derived from the naturally occurring antioxidant ovothiols 1. Antioxidant properties.

4-Mercaptoimidazoles derived from the naturally occurring family of antioxidants, the ovothiols, were assayed for their antioxidant properties. These compounds are powerful HOCl scavengers, more potent than the aliphatic thiol N-acetylcysteine. They react slowly with hydrogen peroxide with second order rate constants of 0.13-0.89 M(-1)s(-1). Scavenging of hydroxyl radical occurs at a diffusion-controlled rate (k=2.0-5.0 x 10(10)M(-1)s(-1)) for the most active compounds, which are also able to inhibit copper-induced LDL peroxidation. The combination of radical scavenging and copper chelating properties may explain the inhibitory effects on LDL peroxidation. Two molecules of mercaptoimidazole can chelate a copper ion and form a square planar complex detected by EPR. Compounds bearing an electron-withdrawing group on position 2 of the imidazole ring are the most potent antioxidant molecules in this series.

4-Mercaptoimidazoles derived from the naturally occurring antioxidant ovothiols 2. Computational and experimental approach of the radical scavenging mechanism.

The radical-scavenging mechanism of fourteen 4-mercaptoimidazoles, derived from the natural family of ovothiols, was studied via a QSAR approach, cyclic voltammetry, ESR and NMR spectroscopy. A significant correlation was found between the DPPH scavenging abilities of test compounds and thermodynamic parameters like overall ease of disulphide formation. The production of a disulphide compound via thiyl radical formation is proposed. Upon DPPH scavenging, hydrogen abstraction from thiols yields transient short-lived thiyl radicals, which were characterised by ESR and rapidly dimerise to form a disulphide compound. Cyclic voltammetry showed that the best DPPH scavengers exhibit low oxidation potentials for their oxidation to disulphides.