Low energy secondary electron induced damage of condensed nucleotides.

Radiation damage and stimulated desorption of nucleotides 2'-deoxyadenosine 5'-monophosphate (dAMP), adenosine 5'-monophosphate (rAMP), 2'-deoxycytidine 5'-monophosphate (dCMP), and cytidine 5'-monophosphate (rCMP) deposited on Au have been measured using x-rays as both the probe and source of low energy secondary electrons. The fluence dependent behavior of the O-1s, C-1s, and N-1s photoelectron transitions was analyzed to obtain phosphate, sugar, and nucleobase damage cross sections. Although x-ray induced reactions in nucleotides involve both direct ionization and excitation, the observed bonding changes were likely dominated by the inelastic energy-loss channels associated with secondary electron capture and transient negative ion decay. Growth of the integrated peak area for the O-1s component at 531.3 eV, corresponding to cleavage of the C-O-P phosphodiester bond, yielded effective damage cross sections of about 23 Mb and 32 Mb (1 Mb = 10-18 cm2) for AMP and CMP molecules, respectively. The cross sections for sugar damage, as determined from the decay of the C-1s component at 286.4 eV and the glycosidic carbon at 289.0 eV, were slightly lower (about 20 Mb) and statistically similar for the r- and d- forms of the nucleotides. The C-1s component at 287.6 eV, corresponding to carbons in the nucleobase ring, showed a small initial increase and then decayed slowly, yielding a low damage cross section (∼5 Mb). Although there is no statistical difference between the sugar forms, changing the nucleobase from adenine to cytidine has a slight effect on the damage cross section, possibly due to differing electron capture and transfer probabilities.

Local spin dynamics of iron oxide magnetic nanoparticles dispersed in different solvents with variable size and shape: A 1H NMR study.

Colloidal magnetic nanoparticles (MNPs) based on a nearly monodisperse iron oxide core and capped by oleic acid have been used as model systems for investigating the superparamagnetic spin dynamics by means of magnetometry measurements and nuclear magnetic resonance (1H NMR) relaxometry. The key magnetic properties (saturation magnetization, coercive field, and frequency dependent "blocking" temperature) of MNPs with different core size (3.5 nm, 8.5 nm, and 17.5 nm), shape (spherical and cubic), and dispersant (hexane and water-based formulation) have been determined. 1H NMR dispersion profiles obtained by measuring the r1 (longitudinal) and r2 (transverse) nuclear relaxivities in the frequency range 0.01-60 MHz confirmed that in all samples the physical mechanisms that drive the nuclear relaxation are the Néel reversal at low temperature and the Curie relaxation at high frequency. The magnetization reversal time at room temperature extracted from the fitting of NMR data falls in the typical range of superparamagnetic systems (10-9-10-10 s). Furthermore, from the distance of minimum approach we could conclude that water molecules do not arrive in close vicinity of the magnetic core. Our findings contribute to elucidate the local spin dynamics mechanisms in colloidal superparamagnetic nanoparticles which are useful in biomedical application as, e.g., contrast agents for magnetic resonance imaging.

NMR relaxation induced by iron oxide particles: testing theoretical models.

Superparamagnetic iron oxide particles find their main application as contrast agents for cellular and molecular magnetic resonance imaging. The contrast they bring is due to the shortening of the transverse relaxation time T 2 of water protons. In order to understand their influence on proton relaxation, different theoretical relaxation models have been developed, each of them presenting a certain validity domain, which depends on the particle characteristics and proton dynamics. The validation of these models is crucial since they allow for predicting the ideal particle characteristics for obtaining the best contrast but also because the fitting of T 1 experimental data by the theory constitutes an interesting tool for the characterization of the nanoparticles. In this work, T 2 of suspensions of iron oxide particles in different solvents and at different temperatures, corresponding to different proton diffusion properties, were measured and were compared to the three main theoretical models (the motional averaging regime, the static dephasing regime, and the partial refocusing model) with good qualitative agreement. However, a real quantitative agreement was not observed, probably because of the complexity of these nanoparticulate systems. The Roch theory, developed in the motional averaging regime (MAR), was also successfully used to fit T 1 nuclear magnetic relaxation dispersion (NMRD) profiles, even outside the MAR validity range, and provided a good estimate of the particle size. On the other hand, the simultaneous fitting of T 1 and T 2 NMRD profiles by the theory was impossible, and this occurrence constitutes a clear limitation of the Roch model. Finally, the theory was shown to satisfactorily fit the deuterium T 1 NMRD profile of superparamagnetic particle suspensions in heavy water.

Thermal and Residual Excited-State Population in a 3D Transmon Qubit.

Remarkable advancements in coherence and control fidelity have been achieved in recent years with cryogenic solid-state qubits. Nonetheless, thermalizing such devices to their milliKelvin environments has remained a long-standing fundamental and technical challenge. In this context, we present a systematic study of the first-excited-state population in a 3D transmon superconducting qubit mounted in a dilution refrigerator with a variable temperature. Using a modified version of the protocol developed by Geerlings et al., we observe the excited-state population to be consistent with a Maxwell-Boltzmann distribution, i.e., a qubit in thermal equilibrium with the refrigerator, over the temperature range 35-150 mK. Below 35 mK, the excited-state population saturates at approximately 0.1%. We verified this result using a flux qubit with ten times stronger coupling to its readout resonator. We conclude that these qubits have effective temperature T(eff)=35 mK. Assuming T(eff) is due solely to hot quasiparticles, the inferred qubit lifetime is 108 µs and in plausible agreement with the measured 80 µs.

The relationship between interfacial bonding and radiation damage in adsorbed DNA.

We have performed a comparison of the radiation damage occurring in DNA adsorbed on gold in two different configurations, when the DNA is thiolated and bound covalently to the substrate and when it is unthiolated and interacts with the substrate through the bases. Both molecules were found to organize so as to protrude from the surface at ~45 degrees. Changes in the time-dependent C 1s and O 1s X-ray photoelectron (XP) spectra resulting from irradiation were interpreted to arise from cleavage of the phosphodiester bond and possibly COH desorption. By fitting the time-dependent XP spectra to a simple kinetic model, time constants were extracted, which were converted to cross sections and quantum yields for the damage reaction. The radiation induced damage is significantly higher for the thiolated DNA. N 1s X-ray absorption spectrum revealed the N-C=N LUMO is more populated in the unthiolated molecule, which is due to a higher degree of charge transfer from the substrate to this LUMO in the unthiolated case. Since the N-C=N LUMO of the thiolated molecule is comparatively less populated, it is more effective in capturing low energy electrons resulting in a higher degree of damage.

Taxonomic notes on the group of Mischocyttarus heliconius Richards 1941, with description of four new species (Hymenoptera: Vespidae, Polistinae).

Mischocyttarus heliconius was described by Richards (1941), being initially assigned to subgenus Kappa, and later to Clypeopolybia. That author subsequently described other similar species, and Silveira (2008) conceived the group as also including M. iperuae Richards, M. sericeus Richards, M. chanchamayoensis Richards, and M. piger Richards. However, the latter species is not a member of this group, which otherwise can be easily recognized by morphological characters. Three of these species were retrieved as forming a monophyletic group by Silveira (2008), but relations with other groups in Mischocyttarus are uncertain. Types and new material of the M. heliconius group are here revised, with addition of four new species (M. gorotire sp. nov., M. ipixuna sp. nov., M. luciliae sp. nov., M. ticuna sp. nov.), and a new identification key is presented. Mischocyttarus piger Richards is reassigned to the group of M. iheringi Zikn in the subgenus Haplometrobius Richards.

Divergence time analysis of the Neotropical wasp genus Protopolybia Ducke, 1905 (Vespidae, Polistinae, Epiponini) using a Multilocus Phylogenetic Approach.

The genus Protopolybia Ducke was analyzed using a multilocus phylogenetic approach, which confirmed its monophyly. In contrast with the arrangements derived solely from morphological data, however, this analysis divides the genus into only two major clades. The study also presents divergence times for the origin and diversification of Protopolybia, which are related to possible vicariant events occurring in the Amazon biome.

Driven dynamics and rotary echo of a qubit tunably coupled to a harmonic oscillator.

We have investigated the driven dynamics of a superconducting flux qubit that is tunably coupled to a microwave resonator. We find that the qubit experiences an oscillating field mediated by off-resonant driving of the resonator, leading to strong modifications of the qubit Rabi frequency. This opens an additional noise channel, and we find that low-frequency noise in the coupling parameter causes a reduction of the coherence time during driven evolution. The noise can be mitigated with the rotary-echo pulse sequence, which, for driven systems, is analogous to the Hahn-echo sequence.

Rediscovery of the social wasp Mischocyttarus (Kappa) tapuya Schulz, with description of the female, larva and nest (Vespidae, Polistinae).

Mischocyttarus tapuya was originally described from a single male specimen collected in a forest near Belm, state of Par, Brazil, in the year of 1893, and had never been found again. We recently collected a colony of this species in an urban forest locality near Belm, and here describe the previously unknown female, mature larva, and nest of this social wasp.

Nitroxide Derivatives for Dynamic Nuclear Polarization in Liquids: The Role of Rotational Diffusion.

Polarization transfer efficiency in liquid-state dynamic nuclear polarization (DNP) depends on the interaction between polarizing agents (PAs) and target nuclei modulated by molecular motions. We show how translational and rotational diffusion differently affect the DNP efficiency. These contributions were disentangled by measuring 1H-DNP enhancements of toluene and chloroform doped with nitroxide derivatives at 0.34 T as a function of either the temperature or the size of the PA. The results were employed to analyze 13C-DNP data at higher fields, where the polarization transfer is also driven by the Fermi contact interaction. In this case, bulky nitroxide PAs perform better than the small TEMPONE radical due to structural fluctuations of the ring conformation. These findings will help in designing PAs with features specifically optimized for liquid-state DNP at various magnetic fields.

Electron Spin-Polarization Dependent Damage to Chiral Amino Acid l-Histidine.

The damage of approximately monolayer films of l-histidine by low-energy spin-polarized electrons (SPE) ejected from a magnetized cobalt substrate has been probed using X-ray photoelectron spectroscopy (XPS). Average damage cross sections for N-containing motifs of l-histidine are 25-30 and 2-5 Mb for zwitterions and neutral molecules, respectively. The magnetization direction of the substrate, which controls the ejected SPE helicity, was reversed in situ, and statistically significant differences in the damage cross sections of 10-30% were measured between positive and negative electron helicities. This is the first measurement of spin dichroism (SD) in an amino acid. The differential cross sections suggest that inelastic scattering of SPE with chiral molecules could contribute to the persistence of one enantiomer vs the other under certain irradiation conditions, particularly for the zwitterionic species.

Taxonomic revision of the Protopolybia picteti-emortualis species-group (Richards, 1978), with descriptions of two new species (Hymenoptera: Vespidae, Polistinae).

A taxonomic revision of the Protopolybia picteti-emortualis species-group now demonstrates that this group is possibly the largest in Protopolybia, comprising 15 species: P. eldinaris sp. nov.; P. djaneteae sp. nov.; P. cameranii (Zavattari 1906) = P. bella (Von Ihering 1903) syn. nov.; P. fulvotincta stat. rev.; P. biguttata, P. nitida, P. alvarengai, P. iheringi, P. perfulvula, P. steinbachi, P. wheeleri, P. rotundata, P. picteti, P. emortualis and P. duckei. Male and female genitalia are illustrated for P. biguttata Bequaert, P. bella, P. nitida, P. fulvotincta and P. picteti. New collection records and a new identification key are presented for this species-group.

Taxonomic revision of the P. chartergoides species-group of the genus Protopolybia Ducke, 1905 (Hymenoptera: Vespidae, Polistinae).

A taxonomic revision of the Protopolybia chartergoides species-group was undertaken. Protopolybia isthmensis (Richards) stat. nov. is elevated to the level of species. The male genitalia of P. chartergoides (Gribodo), P. fuscata (Fox), and P. pallidibalteatus (Cameron) are illustrated and described. New collection records and new identification keys are presented for the species groups of Protopolybia, and the species within the P. chartergoides species-group.

Generating spatially entangled itinerant photons with waveguide quantum electrodynamics.

Realizing a fully connected network of quantum processors requires the ability to distribute quantum entanglement. For distant processing nodes, this can be achieved by generating, routing, and capturing spatially entangled itinerant photons. In this work, we demonstrate the deterministic generation of such photons using superconducting transmon qubits that are directly coupled to a waveguide. In particular, we generate two-photon N00N states and show that the state and spatial entanglement of the emitted photons are tunable via the qubit frequencies. Using quadrature amplitude detection, we reconstruct the moments and correlations of the photonic modes and demonstrate state preparation fidelities of 84%. Our results provide a path toward realizing quantum communication and teleportation protocols using itinerant photons generated by quantum interference within a waveguide quantum electrodynamics architecture.

Quantum superposition of macroscopic persistent-current states.

Microwave spectroscopy experiments have been performed on two quantum levels of a macroscopic superconducting loop with three Josephson junctions. Level repulsion of the ground state and first excited state is found where two classical persistent-current states with opposite polarity are degenerate, indicating symmetric and antisymmetric quantum superpositions of macroscopic states. The two classical states have persistent currents of 0.5 microampere and correspond to the center-of-mass motion of millions of Cooper pairs.

Prebiotic Phosphorylation of Uridine using Diamidophosphate in Aerosols.

One of the most challenging fundamental problems in establishing prebiotically plausible routes for phosphorylation reactions using phosphate is that they are thermodynamically unfavorable in aqueous conditions. Diamidophosphate (DAP), a potentially prebiotically relevant compound, was shown to phosphorylate nucleosides in aqueous medium, albeit at a very slow rate (days/weeks). Here, we demonstrate that performing these reactions within an aerosol environment, a suitable model for the early Earth ocean-air interface, yields higher reaction rates when compared to bulk solution, thus overcoming these rate limitations. As a proof-of-concept, we demonstrate the effective conversion (~6.5-10%) of uridine to uridine-2',3'-cyclophosphate in less than 1 h. These results suggest that aerosol environments are a possible scenario in which prebiotic phosphorylation could have occurred despite unfavorable rates in bulk solution.

Taxonomic revision of the Protopolybia sedula species-group (Hymenoptera, Vespidae, Polistinae), with an new identification key to species.

A taxonomic review of the P. sedula species-group is presented. New diagnostic characters are described and all species redescribed. The male genitalia of P. sedula (de Saussure) and P. weyrauchi Bequaert are described and drawn. New collection records and a new identification key for the species-group are given.

Toxicity of clove essential oil and its ester eugenyl acetate against Artemia salina.

The production of compounds via enzymatic esterification has great scientific and technological interest due to the several inconveniences related to acid catalysis, mainly by these systems do not fit to the concept of "green chemistry". Besides, natural products as clove oil present compounds with excellent biological potential. Bioactives compounds are often toxic at high doses. The evaluation of lethality in a less complex animal organism can be used to a monitoring simple and rapid, helping the identification of compounds with potential insecticide activity against larvae of insect vector of diseases. In this sense, the toxicity against Artemia salina of clove essential oil and its derivative eugenyl acetate obtained by enzymatic esterification using Novozym 435 as biocatalyst was evaluated. The conversion of eugenyl acetate synthesis was 95.6%. The results about the evaluation of toxicity against the microcrustacean Artemia salina demonstrated that both oil (LC50= 0.5993 µg.mL-1) and ester (LC50= 0.1178 µg.mL-1) presented high toxic potential, being the eugenyl acetate almost 5 times more toxic than clove essential oil. The results reported here shows the potential of employing clove oil and eugenyl acetate in insecticide formulations.

Persistence of slow dynamics in Tb(OETAP)2 single molecule magnets embedded in conducting polymers.

UNLABELLED: The spin dynamics of Tb(OETAP)2 single ion magnets was investigated by means of muon spin relaxation (µSR) both in the bulk material as well as when the molecule is embedded into PEDOT: PSS polymer conductor. The spin fluctuation time is characterized by a high temperature activated trend, with an energy barrier around 320 K, and by a low temperature tunneling regime. When the single ion magnet is embedded into the polymer the energy barrier only slightly decreases and the fluctuation time remains of the same order of magnitude, even at low temperature. This finding shows that these single molecule magnets preserve their characteristics which, if combined with those of the conducting polymer, result in a hybrid material of potential interest for organic spintronics.

Characterization of magnetic nanoparticles from Magnetospirillum Gryphiswaldense as potential theranostics tools.

We investigated the theranostic properties of magnetosomes (MNs) extracted from magnetotactic bacteria, promising for nanomedicine applications. Besides a physico-chemical characterization, their potentiality as mediators for magnetic fluid hyperthermia and contrast agents for magnetic resonance imaging, both in vitro and in vivo, are here singled out. The MNs, constituted by magnetite nanocrystals arranged in chains, show a superparamagnetic behaviour and a clear evidence of Verwey transition, as signature of magnetite presence. The phospholipid membrane provides a good protection against oxidation and the MNs oxidation state is stable over months. Using an alternate magnetic field, the specific absorption rate was measured, resulting among the highest reported in literature. The MRI contrast efficiency was evaluated by means of the acquisition of complete NMRD profiles. The transverse relaxivity resulted as high as the one of a former commercial contrast agent. The MNs were inoculated into an animal model of tumour and their presence was detected by magnetic resonance images two weeks after the injection in the tumour mass.