Experimental capabilities for liquid jet samples at sub-MHz rates at the FXE Instrument at European XFEL.

The Femtosecond X-ray Experiments (FXE) instrument at the European X-ray Free-Electron Laser (EuXFEL) provides an optimized platform for investigations of ultrafast physical, chemical and biological processes. It operates in the energy range 4.7-20 keV accommodating flexible and versatile environments for a wide range of samples using diverse ultrafast X-ray spectroscopic, scattering and diffraction techniques. FXE is particularly suitable for experiments taking advantage of the sub-MHz repetition rates provided by the EuXFEL. In this paper a dedicated setup for studies on ultrafast biological and chemical dynamics in solution phase at sub-MHz rates at FXE is presented. Particular emphasis on the different liquid jet sample delivery options and their performance is given. Our portfolio of high-speed jets compatible with sub-MHz experiments includes cylindrical jets, gas dynamic virtual nozzles and flat jets. The capability to perform multi-color X-ray emission spectroscopy (XES) experiments is illustrated by a set of measurements using the dispersive X-ray spectrometer in von Hamos geometry. Static XES data collected using a multi-crystal scanning Johann-type spectrometer are also presented. A few examples of experimental results on ultrafast time-resolved X-ray emission spectroscopy and wide-angle X-ray scattering at sub-MHz pulse repetition rates are given.

Inducing ovulation with oestradiol cypionate allows flexibility in the timing of insemination and removes the need for gonadotrophin-releasing hormone in timed AI protocols for dairy cows.

The effects of addition of gonadotrophin-releasing hormone (GnRH) to a progesterone plus oestradiol-based protocol and timing of insemination in Holstein cows treated for timed AI (TAI) were evaluated. Cows (n=481) received a progesterone device and 2mg oestradiol benzoate. After 8 days, the device was removed and 25mg dinoprost was administered. Cows were allocated to one of three (Study 1; n=57) or four (Study 2; n=424) groups, accordingly to ovulation inducer alone (Study 1; oestradiol cypionate (EC), GnRH or both) or ovulation inducer (EC alone or combined with GnRH) and timing of insemination (48 or 54h after device removal; Study 2). In Study 1, the diameter of the ovulatory follicle was greater for GnRH than EC. Oestrus and ovulation rates were similar regardless of ovulatory stimuli. However, time to ovulation was delayed when GnRH only was used. In Study 2, cows treated with GnRH or not had similar pregnancy per AI (P/AI) 30 days (41.5% vs 37.3%; P=0.28) and 60 days (35.9% vs 33.0%; P=0.61) after TAI. TAI 48 and 54h after device removal resulted similar P/AI at 30 days (40.3% vs 38.5%; P=0.63) and 60 days (33.8% vs 35.1%; P=0.72). Thus, adding GnRH at TAI does not improve pregnancy rates in dairy cows receiving EC. The flexibility of time to insemination enables TAI of a large number of cows using the same protocol and splitting the time of AI.

XDS: a flexible beamline for X-ray diffraction and spectroscopy at the Brazilian synchrotron.

The majority of the beamlines at the Brazilian Synchrotron Light Source Laboratory (LNLS) use radiation produced in the storage-ring bending magnets and are therefore currently limited in the flux that can be used in the harder part of the X-ray spectrum (above ∼10 keV). A 4 T superconducting multipolar wiggler (SCW) was recently installed at LNLS in order to improve the photon flux above 10 keV and fulfill the demands set by the materials science community. A new multi-purpose beamline was then installed at the LNLS using the SCW as a photon source. The XDS is a flexible beamline operating in the energy range between 5 and 30 keV, designed to perform experiments using absorption, diffraction and scattering techniques. Most of the work performed at the XDS beamline concentrates on X-ray absorption spectroscopy at energies above 18 keV and high-resolution diffraction experiments. More recently, new setups and photon-hungry experiments such as total X-ray scattering, X-ray diffraction under high pressures, resonant X-ray emission spectroscopy, among others, have started to become routine at XDS. Here, the XDS beamline characteristics, performance and a few new experimental possibilities are described.

Influence of the Nd:YAG laser pulse duration on the temperature of primary enamel.

The aim of this study is to evaluate the temperature change on specimens of primary enamel irradiated with different pulse duration of Nd:YAG laser. Fifteen sound primary molars were sectioned mesiodistally, resulting in 30 specimens (3.5 × 3.5 × 2.0 mm). Two small holes were made on the dentin surface in which K-type thermocouples were installed to evaluate thermal changes. Specimens were randomly assigned in 3 groups (n = 10): A = EL (extra long pulse, 10.000 µs), B = LP (long pulse, 700 µs), and C = SP (short pulse, 350 µs). Nd:YAG laser (λ = 1.064 µm) was applied at contact mode (10 Hz, 0.8 W, 80 mJ) and energy density of 0.637 mJ/mm(2). Analysis of variance (ANOVA) was performed for the statistical analysis (P = 0.46). Nd:YAG laser pulse duration provided no difference on the temperature changes on primary enamel, in which the following means were observed: A = EL (23.15°C ± 7.75), B = LP (27.33°C ± 11.32), and C = SP (26.91°C ± 12.85). It can be concluded that the duration of the laser pulse Nd:YAG increased the temperature of the primary enamel but was not influenced by different pulse durations used in the irradiation.

SLC24A5 and ASIP as phenotypic predictors in Brazilian population for forensic purposes.

Pigmentation is a variable and complex trait in humans and it is determined by the interaction of environmental factors, age, disease, hormones, exposure to ultraviolet radiation and genetic factors, including pigmentation genes. Many polymorphisms of these genes have been associated with phenotypic diversity of skin, eyes and hair color in homogeneous populations. Phenotype prediction from biological samples using genetic information has benefited forensic area in some countries, leading some criminal investigations. Herein, we evaluated the association between polymorphisms in the genes SLC24A5 (rs1426654) and ASIP (rs6058017) with skin, eyes and hair colors, in 483 healthy individuals from Brazilian population for attainable use in forensic practice. The volunteers answered a questionnaire where they self-reported their skin, eye and hair colors. The polymorphic homozygous genotype of rs1426654∗A and rs6058017∗A in SLC24A5 and ASIP respectively, showed strongest association with fairer skin (OR 47.8; CI 14.1-161.6 and OR 8.6; CI 2.5-29.8); SLC24A5 alone showed associations with blue eyes (OR 20.7; CI 1.2-346.3) and blond hair (OR 26.6; CI 1.5-460.9). Our data showed that polymorphic genotypes (AA), in both genes, are correlated with characteristics of light pigmentation, while the ancestral genotype (GG) is related to darker traits, corroborating with previous studies in European and African populations. These associations show that specific molecular information of an individual may be useful to access some phenotypic features in an attempt to help forensic investigations, not only on crime scene samples but also in cases of face reconstructions in unknown bodies.

Photooxidation and photoaquation of iron hexacyanide in aqueous solution: A picosecond X-ray absorption study.

We present a picosecond Fe K-edge absorption study of photoexcited ferrous and ferric hexacyanide in water under 355 and 266 nm excitation. Following 355 nm excitation, the transient spectra for the ferrous and ferric complexes exhibit a red shift of the edge reflecting an increased electron density at the Fe atom. For the former, an enhanced pre-edge transition is also observed. These observations are attributed to the aquated [Fe(CN)5OH2](3-) species, based on quantum chemical calculations which also provide structural parameters. Upon 266 nm excitation of the ferric complex, a transient reminiscent of the aquated species is observed (appearance of a pre-edge feature and red shift of the edge) but it is different from that obtained under 355 nm excitation. This points to a new reaction channel occurring through an intermediate state lying between these two excitation energies. Finally, 266 nm excitation of the ferrous species is dominated by the photooxidation channel with formation of the ferric complex as main photoproduct. However, we observe an additional minor photoproduct, which is identical to the 266 nm generated photoproduct of the ferric species, suggesting that under our experimental conditions, the pump pulse photooxidises the ferrous complex and re-excites the primary ferric photoproduct.

Characteristics of positive and negative secondary ions emitted from [Formula: see text] and [Formula: see text] impacts.

The current limitation for SIMS analyses is insufficient secondary ion yields, due in part to the inefficiency of traditional primary ions. Massive gold clusters are shown to be a route to significant gains in secondary ion yields relative to other commonly used projectiles. At an impact energy of 520 keV, [Formula: see text] is capable of generating an average of greater than ten secondary ions per projectile, with some impact events generating >100 secondary ions. The capability of this projectile for signal enhancement is further displayed through the observation of up to seven deprotonated molecular ions from a single impact on a neat target of the model pentapeptide leu-enkephalin. Positive and negative spectra of leu-enkephalin reveal two distinct emission regimes responsible for the emission of either intact molecular ions with low internal energies or small fragment species. The internal energy distribution for this projectile is measured using a series of benzylpyridinium salts and compared with the small polyatomic projectile [Formula: see text] at 110 keV as well as distributions previously reported for electrospray ionization and fast atom bombardment. These results show that [Formula: see text] offers high secondary ion yields not only for small fragment ions, e.g. CN-, typically observed in SIMS analyses, but also for characteristic molecular ions. For the leu-enkephalin example, the yields for each of these species are greater than unity.

Characterization of individual nano-objects with nanoprojectile-SIMS.

Secondary ion mass spectrometry (SIMS) applied in the event-by-event bombardment/detection mode is uniquely suited for the characterization of individual nano-objects. In this approach, nano-objects are examined one-by-one, allowing for the detection of variations in composition. The validity of the analysis depends upon the ability to physically isolate the nano-objects on a chemically inert support. This requirement can be realized by deposition of the nano-objects on a Nano-Assisted Laser Desorption/Ionization (NALDI™) plate. The featured nanostructured surface provides a support where nano-objects can be isolated if the deposition is performed at a proper concentration. We demonstrate the characterization of individual nano-objects on a NALDI™ plate for two different types of nanometric bacteriophages: Qß and M13. Scanning electron microscope (SEM) images verified that the integrity of the phages is preserved on the NALDI™ substrate. Mass spectrometric data show secondary ions from the phages are identified and resolved from those from the underlying substrate.

Simultaneous detection and localization of secondary ions and electrons from single large cluster impacts.

The use of large cluster primary ions (e.g. C60, Au400) in secondary ion mass spectrometry has become prevalent in recent years due to their enhanced emission of secondary ions, in particular, molecular ions (MW ≤ 1500 Da). The co-emission of electrons with SIs was investigated per projectile impact. It has been found that SI and electrons yields increased with increasing projectile energy and size. The use of the emitted electrons from impacts of C60 for localization has been demonstrated for cholesterol deposited on a copper grid. The instrumentation, methodologies, and results from these experiments are presented.

Surface characterization of biological nanodomains using NP-ToF-SIMS.

This paper describes the application of nanoparticle bombardment with time-of-flight secondary ion mass spectrometry (NP-ToF-SIMS) for the analysis of native biological surfaces for the case of sagittal sections of mammalian brain tissue. The use of high energy, single nanoparticle impacts (e.g. 520 keV Au400) permits desorption of intact lipid molecular ions, with enhanced molecular ion yield and reduced fragmentation. When coupled with complementary molecular ion fragmentation and exact mass measurement analysis, high energy nanoparticle probes (e.g. 520 keV Au400 NP) provide a powerful tool for the analysis of the lipid components from native brain sections without the need for surface preparation and with ultimate spatial resolution limited to the desorption volume per impact (~103 nm3).

Ações de vigilância para influenza aviária desenvolvida no Brasil, no período de 2004 e 2007 / Avian influenza surveillance activities, developed in Brazil from 2004 to 2007

No início dos anos 2000, o Brasil se consolidou como maior exportador mundial de carne de frango, mesmo período em que se observou a emergência global de focos de HPAI. Para assegurar a qualidade sanitária do produto avícola nacional, o Mapa organizou um programa oficial de vigilância para o vírus de IA. Na primeira fase, foram coletados 106.226 soros e 7.017 pools de suabes traqueais e cloacais, provenientes de granjas avícolas de produção comercial intensiva de frangos de corte, no período entre janeiro de 2004 e março de 2005. Não se obteve isolamento viral para IA, porém foi identificado um conglomerado epidemiológico de 24 municípios, delineado pela interpolação de dados relacionados às localizações geográficas, e os resultados sorológicos das amostras dessas origens, ELISA reagente para IA, no estado de Rondônia. Na segunda fase da vigilância, três distintas ações para pesquisa do vírus de IA foram executadas entre 2006 e 2007, em: 1) aves comerciais de corte de criação intensiva; 2) aves de reprodução; e 3) aves migratórias e de subsistência. Não houve identificação de resposta sorológica ou isolamento de vírus de IA em aves dos grupos 1 e 2. Foram isolados vírus de IA do subtipo H3 em aves migratórias, capturadas nos estados de Pará e Pernambuco. Também foram identificados vírus de IA dos subtipos H2, H3 e H4 em aves de subsistência, de propriedades localizadas no Amazonas, Pará, Pernambuco, Rio Grande do Sul e Santa Catarina. Observou-se risco sanitário para LPAI associado às populações de aves silvestres e de subsistência localizadas em áreas próximas ao sistema comercial. Estudos adicionais serão necessários para se avaliar o risco associado à introdução de IA no sistema comercial avícola brasileiro.

In the early 2000s Brazil had established itself as the world's largest exporter of poultry meat, the same period in which the emergence of HPAI global outbreaks was observed. To ensure the national health quality of Brazilian poultry product, MAPA organized an official AI surveillance program. In the first stage, during the period between January 2004 and March 2005, 106.226 sera were collected and 7.017 tracheal and cloacae pools of swabs were obtained from intensive commercial broiler farms. No AI virus isolation was obtained, however, an epidemiological cluster was identified in the state of Rondonia, outlined by the interpolation of data related to municipalities' geographic location and serological response to AI in ELISA tests. Between 2006 and 2007, during the second stage, three AI surveillance actions were executed in: 1) intensive commercial broiler farms, 2) breeding farms and 3) migratory and backyard birds. There was neither serological response identification nor IA virus isolation in birds belonging to groups 1 and 2. H3 LPAI subtype viruses were isolated from migratory birds captured in the states of Pará and Pernambuco. H2, H3 and H4 LPAI subtypes were also identified in backyard birds from samples collected in the states of Amazonas, Pará, Pernambuco, Rio Grande do Sul and Santa Catarina. There are health risks to LPAI associated to wild and backyard bird populations located in areas close to commercial farms. Additional studies are needed for risk assessment regarding the possibility of AI introduction in the Brazilian commercial poultry system.

Catechin attenuates behavioral neurotoxicity induced by 6-OHDA in rats.

This study was designed to investigate the beneficial effect of catechin in a model of Parkinson's disease. Unilateral, intrastriatal 6-hydroxydopamine (6-OHDA)-lesioned rats were pretreated with catechin (10 and 30 mg/kg) by intraperitoneal (i.p.) injection 2h before surgery and for 14 days afterwards. After treatments, apomorphine-induced rotations, locomotor activity, working memory and early and late aversive memories were evaluated. The mesencephalon was used to determine the levels of monoamines and measurement of glutathione (GSH). Immunohistochemical staining was also used to evaluate the expression of tyrosine hydroxylase (TH) in mesencephalic and striatal tissues. Catechin administration attenuated the increase in rotational behavior and the decrease in locomotor activity observed in lesioned rats. Although catechin did not rescue the impairment of late aversive memory, it protected the animals against 6-OHDA-induced working memory deficits. Furthermore, catechin treatment restored GSH levels, and significantly increased dopamine and DOPAC content, and TH-immunoreactivity in 6-OHDA-lesioned rats. Catechin protected 6-OHDA-lesioned rats due to its antioxidant action, indicating that it could be useful as an adjunctive therapy for the treatment of Parkinson's disease.

Solvent-induced luminescence quenching: static and time-resolved X-ray absorption spectroscopy of a copper(I) phenanthroline complex.

We present a static and picosecond X-ray absorption study at the Cu K-edge of bis(2,9-dimethyl-1,10-phenanthroline)copper(I) ([Cu(dmp)2](+); dmp = 2,9-dimethyl-1,10-phenanthroline) dissolved in acetonitrile and dichloromethane. The steady-state photoluminescence spectra in dichloromethane and acetonitrile are also presented and show a shift to longer wavelengths for the latter, which points to a stronger stabilization of the excited complex. The fine structure features of the static and transient X-ray spectra allow an unambiguous assignment of the electronic and geometric structure of the molecule in both its ground and excited (3)MLCT states. Importantly, the transient spectra are remarkably similar for both solvents, and the spectral changes can be rationalized using the optimized ground- and excited-state structures of the complex. The proposed assignment of the lifetime shortening of the excited state in donor solvents (acetonitrile) to a metal-centered exciplex is not corroborated here. Molecular dynamics simulations confirm the lack of complexation; however, in both solvents the molecules come close to the metal but undergo rapid exchange with the bulk. The shortening of the lifetime of the title complex and nine additional related complexes can be rationalized by the decrease in the (3)MLCT energy. Deviations from this trend may be explained by means of the effects of the dihedral angle between the ligand planes, the solvent, and the (3)MLCT-(1)MLCT energy gap.

X-ray absorption spectroscopy of ground and excited rhenium-carbonyl-diimine complexes: evidence for a two-center electron transfer.

Steady-state and picosecond time-resolved X-ray absorption spectroscopy is used to study the ground and lowest triplet states of [ReX(CO)(3)(bpy)](n+), X = Etpy (n = 1), Cl, or Br (n = 0). We demonstrate that the transient spectra at both the Re L(3)- and Br K-edges show the emergence of a pre-edge feature, absent in the ground-state spectrum, which is associated with the electron hole created in the highest occupied molecular orbital following photoexcitation. Importantly, these features have the same dynamics, confirming previous predictions that the low-lying excited states of these complexes involve a two-center charge transfer from both the Re and the ligand, X. We also demonstrate that the DFT optimized ground and excited structures allow us to reproduce the experimental XANES and EXAFS spectra. The ground-state structural refinement shows that the Br atom contributes very little to the latter, whereas the Re-C-O scattering paths are dominant due to the so-called focusing effect. For the excited-state spectrum, the Re-X bond undergoes one of the largest changes but still remains a weak contribution to the photoinduced changes of the EXAFS spectrum.

On the Surface Mapping using Individual Cluster Impacts.

This paper describes the advantages of using single impacts of large cluster projectiles (e.g. C(60) and Au(400)) for surface mapping and characterization. The analysis of co-emitted time-resolved photon spectra, electron distributions and characteristic secondary ions shows that they can be used as surface fingerprints for target composition, morphology and structure. Photon, electron and secondary ion emission increases with the projectile cluster size and energy. The observed, high abundant secondary ion emission makes cluster projectiles good candidates for surface mapping of atomic and fragment ions (e.g., yield >1 per nominal mass) and molecular ions (e.g., few tens of percent in the 500 < m/z < 1500 range).

Efeitos da suplementação com fósforo em caprinos no semiárido do nordeste brasileiro / Effect of phosphorus supplementation for goats in the Brazilian semiarid region

To evaluate the effect of phosphorus supplementation for goats grazing for the semiarid region, one group of 16 recently weaned Moxotó goats was supplemented with a mineral supplement containing Na, Cl, Zn, Cu, Se, Co, and P during 240 days. Another similar group was supplemented with a similar mineral supplement without P. The mean daily consumption of supplement by animal was of 7.09±2.77g and 7.67±3.14g for the groups with and without P, respectively. The mean weight gain of the P supplemented group (45.20±5.56g) was significantly higher (P<0.05) than the non-supplemented group (40.03±2.80g). The average total P in soil was 30.8mg/kg and in the pasture 0.13 percent in dry matter. These results demonstrate the occurrence of P deficiency in some areas of the Brazilian semiarid region.

Photon emission from massive projectile impacts on solids.

First evidence of photon emission from individual impacts of massive gold projectiles on solids for a number of projectile-target combinations is reported. Photon emission from individual impacts of massive Au(n) (+q) (1 ≤ n ≤ 400; q = 1-4) projectiles with impact energies in the range of 28-136 keV occurs in less than 10 ns after the projectile impact. Experimental observations show an increase in the photon yield from individual impacts with the projectile size and velocity. Concurrently with the photon emission, electron emission from the impact area has been observed below the kinetic emission threshold and under unlikely conditions for potential electron emission. We interpret the puzzling electron emission and correlated luminescence observation as evidence of the electronic excitation resulting from the high-energy density deposited by massive cluster projectiles during the impact.

Note: Integration of trapped ion mobility spectrometry with mass spectrometry.

The integration of a trapped ion mobility spectrometer (TIMS) with a mass spectrometer (MS) for complementary fast, gas-phase mobility separation prior to mass analysis (TIMS-MS) is described. The ion transmission and mobility separation are discussed as a function of the ion source condition, bath gas velocity, analysis scan speed, RF ion confinement, and downstream ion optical conditions. TIMS mobility resolution depends on the analysis scan speed and the bath gas velocity, with the unique advantage that the IMS separation can be easily tuned from high speed (~25 ms) for rapid analysis to slower scans for higher mobility resolution (R > 80).

Head hair reduces sweat rate during exercise under the sun.

The purpose of this study was to evaluate the effects of human head hair on thermoregulation during exercise carried out under solar radiation. 10 healthy male subjects (mean±SD: 25.1±2.5 yr; height: 176.2±4.0 cm; weight: 73.7±6.7 kg; VO(2max) 56.2±5.3 mLO(2)·kg (-1)·min (-1)) took part in 2 1 h-long trials of continuous exercise on a treadmill at 50% VO2(max) under solar radiation that were separated by at least 2 days. Whereas for the first trial they retained their natural head hair (HAIR), in the second trial their hair was totally shaved (NOHAIR). Several properties were measured, including environmental heat stress (Wet Bulb Globe Temperature index - WBGT, °C), heart rate, rectal temperature, skin temperature, head temperature, and global sweat rate. The main findings were that whereas there was a lower sweat rate in the HAIR condition (HAIR: 7.08±0.79 vs. NOHAIR: 7.67±0.79 g·m (-2)·min (-1); p=0.03), there were no significant differences in any of the other variables between the HAIR and NOHAIR trials. In conclusion, the presence of head hair resulted in a lower sweat rate.

Photon, Electron and Secondary Ion Emission from Single C(60) keV Impacts.

This paper presents the first observation of coincidental emission of photons, electrons and secondary ions from individual C(60) keV impacts. An increase in photon, electron and secondary ion yields is observed as a function of C(60) projectile energy. The effect of target structure/composition on photon and electron emissions at the nanometer level is shown for a CsI target. The time-resolved photon emission may be characterized by a fast component emission in the UV-Vis range with a short decay time, while the electron and secondary ion emission follow a Poisson distribution.