Pressure-dependence Raman spectroscopy and the lattice dynamic calculations of Bi2(MoO4)3 crystal.

This work reports a pressure-dependent Raman spectroscopic study and the theoretical lattice dynamics calculations of a Bi2(MoO4)3 crystal. The lattice dynamics calculations were performed, based on a rigid ion model, to understand the vibrational properties of the Bi2(MoO4)3 system and to assign the experimental Raman modes under ambient conditions. The calculated vibrational properties were helpful to support pressure-dependent Raman results, including eventual structural changes induced by pressure changes. Raman spectra were measured in the spectral region between 20 and 1000 cm-1 and the evolution of the pressures values was recorded in the range of 0.1-14.7 GPa. Pressure-dependent Raman spectra showed changes observed at 2.6, 4.9 and 9.2 GPa, these changes being associated with structural phase transformations. Finally, principal component analysis (PCA) and hierarchical cluster analysis (HCA) were performed to infer the critical pressure of phase transformations undergone by the Bi2(MoO4)3 crystal.

A temperature-dependent Raman scattering and X-ray diffraction study of K2Mo2O7·H2O and ab initio calculations of K2Mo2O7.

This study reports a temperature-dependent Raman scattering and X-ray diffraction study of K2Mo2O7·H2O. The high-temperature Raman scattering analysis shows that the material remains structurally stable, with triclinic symmetry, in a temperature range from 300 to 413 K and undergoes a structural phase transition between 413 and 418 K. This phase transition is most likely connected with the dehydration process of K2Mo2O7·H2O. The temperature-dependent X-ray diffraction patterns are measured from 30 to 573 K. The results show that the discovered phase transition occurs between 419 and 433 K, in good agreement with the Raman scattering results. According to the Raman data, with increasing temperature, the dehydrated crystal of K2Mo2O7 undergoes a new phase transformation at 603 K and melts at ~843 K. Principal component and hierarchical cluster analyses are performed based on the treatment of the raw spectral data to infer the phase transformations occurring in the material. Assignments of the Raman modes for the K2Mo2O7 system at ambient conditions are studied through first-principles calculations based on density functional perturbation theory. These calculations are applied to understand the electronic properties, including the band structure and the associated projected density of states, of K2Mo2O7 under the local density approximation.

Evaluation of phytochemical composition, toxicity in Drosophila melanogaster and effects on antibiotics modulation of Plathymenia reticulata Benth extract.

Bacterial resistance is interfering with the action of antibiotics for clinical use in treating pathologies. The search for new substances capable of combating this resistance is necessary. An alternative to the search for these substances is in the extract of medicinal plants. Plathymenia reticulata, plant of the Fabaceae family, is a common tree species from the Brazilian cerrado, and is commonly used in areas of environmental degradation. This species is rich in phenolic compounds, such as flavonoids and tannins, compounds that are associated with various biological effects. A hydroethanolic extract from the bark of Plathymenia reticulata (HEPrB) was produced and then tests were carried out to verify the direct antibacterial activity, the modulatory effect of antibiotics for clinical use and their toxicity in Drosophila melanogaster flies. Through the analysis with UPLC, a wide variety of flavonoids contained in the HEPrB was observed. Direct antibacterial activity was observed for the standard strain of Staphylococcus aureus, however, the extract showed antagonistic activity or no significance in relation to the antibiotics tested in this study. As for toxicity, the HEPrB did not show significant damage in the proposed model. The results emphasize care when associating the consumption of teas with treatments with antibiotics for clinical use.

Valor nutricional do capim-elefante verde colhido em diferentes idades de rebrota / [Nutritional value of fresh elephantgrass harvested at different regrowth ages]

Avaliou-se o valor nutricional do capim-elefante verde colhido aos 56, 84 e 112 dias de idade, por meio do consumo e da digestibilidade em ovinos, da degradabilidade in situ e da cinética da fermentação ruminal. O capim-elefante colhido aos 56 dias proporcionou maiores valores de consumo da MS (1204,81g/dia), da EB (4910,41kcal/dia), da ED (3436,21kcal/dia) e da PB (130,90g/dia). Para o capim-elefante colhido aos 56 dias, ainda foram observados os maiores valores de digestibilidade da MS (70,64%), da EB (70,11%), da PB (68,96%), da FDN (71,4%) e do conteúdo ED (2,86Mcal/kg MS). Com o avanço da idade de corte, houve redução da degradabilidade potencial da MS (77,99% x 68,33%), da PB (84,80% x 56,52%) e da FDN (72,18% x 64,33%), para as idades de corte de 56 e 112 dias, respectivamente. O capim cortado aos 56 dias apresentou maior valor de produção cumulativa de gases (210,50mL/g de MS) e de degradabilidade da matéria seca (63,9%) após 96 horas de fermentação. O capim-elefante verde deve ser colhido aos 56 dias de rebrota em razão das características nutricionais apresentadas.(AU)

The nutritional value of fresh elephant grass harvested at 56, 84 and 112 days of age was evaluated by intake and digestibility in sheep, in situ degradability, and ruminal fermentation's kinetics. The elephant grass harvested at 56 days provided higher DM intake (1204.81g/day), GE (4910.41kcal/day), DE (3436.21kcal/day), and CP (130.90g/day) values. Furthermore, the highest DM (70.64%), GE (70.11%), DE (2.86%) and CP (68.96%) digestibility values were observed at 56 days. With the increase in the harvest age there was a reduction in the DM (77.99 x 68.33%), CP (84.80 x 56.52%) and NDF (72.18 x 64.33%) potential degradability in the treatments 56 and 112 days, respectively. Higher values of cumulative gas production (210,50mL/g DM) and DM degradability for elephant grass were observed at 56 days, after 96 hours of fermentation. The fresh elephant grass should be harvested at 56 days of regrowth due to the nutritional characteristics found in this study.(AU)

Raman spectroscopy of captopril crystals under low-temperature conditions.

The polymorphism is a characteristic of several active principles, and can affect the bioavailability of a drug. Among the drugs used in the treatment of heart diseases, captopril is one of the most widely used in the world. Despite the knowledge of vibrational properties of captopril under high temperature and under high pressure, a lack of information impedes the understanding of the substance in the crystal form at low temperatures. In this research, we investigated the vibrational properties of captopril crystals under cryogenic conditions in the 300-8 K interval using Raman spectroscopy. By observing the behavior of the inter- and intra-molecular vibrations it was possible to infer that the captopril molecules suffered a rearranging into the unit cell due slight orientational changes mainly involving CH⋯O hydrogen bonds. The phenomenon occurs in a large temperature range. However, the observed changes do not suggest the occurrence of a structural phase transition and the Raman spectra indicate that the trans conformation is recorded down to the lowest temperature available in the experiments.

Lattice dynamics calculations and high-pressure Raman spectra of the ZnMoO4.

We report here the analysis of vibrational properties of the ZnMoO4 by using theoretical and experimental approaches, well as results of high pressure experiments in this system. The analysis of the lattice dynamics calculations through the classical rigid ion model, was applied to determine the mode assignment in the triclinic phase of the ZnMoO4. Additionally, the experimental high-pressure Raman spectra of the ZnMoO4 were carried out from 0 GPa up to 6.83 GPa to shed light on the structural stability of this system. The pressure-dependent studies showed that this crystal undergoes a first order phase transition at around 1.05 GPa. The Raman spectrum analysis of the new phase shows a significant change in the number of modes for the spectral range of 20-1000 cm-1. The instability of this phase occurs due to the decrease of the MoO bond lengths in the high-pressure phase, connected with tilting and/or rotations of the MoO4 tetrahedra leading to a disorder at the MoO4 sites. The second and third phase transformations were observed, respectively, at about 2.9 GPa and 4.77 GPa, with strong evidences, in the Raman spectra, of crystal symmetry change. The principal component analysis (PCA) and the hierarchical cluster analysis (HCA) were used in order to infer the intervals of pressure where the different phases do exist. Discussion about the number of non equivalent sites for Mo ions and the kind of coordination for molybdenum atoms is also furnished.

Temperature dependence Raman spectroscopy and DFT calculations of Bi2(MoO4)3.

This work reports a theoretical and experimental study on the electronic and vibrational properties of Bi2(MoO4)3. First-principle calculations were applied to increase the understanding on the properties of the chemical composition through the energy bands. The conduction band minimum (CBM) is found at the high symmetric Γ-point, while the valence-band maximum (VBM) is located between the Z and the Γ-points. Therefore, these facts confirm that the Bi2(MoO4)3 crystal is a semiconductor compound with an indirect band-gap of about 2.1 eV. Moreover, lattice dynamic properties were calculated using density functional perturbation theory (DFPT) in order to assign the experimental Raman bands. In addition, we performed temperature-dependent Raman spectroscopic studies in the Bi2(MoO4)3 crystals to obtain information on structural changes induced by effects of the temperature change. From the changes observed in the Raman spectra phase transitions at ∼ 668 and 833 K were inferred, with the last one possibly related to the disorder due to the heating process.

High-pressure studies on l,l-dileucine crystals by Raman spectroscopy and synchrotron X-ray diffraction combined with DFT calculations.

The vibrational properties of the dipeptide l-leucyl-l-leucine hydrate were investigated through Raman and infrared spectroscopy. With the aid of first principle calculations using the density functional theory, the assignment of the vibrational modes from the material was furnished. In addition, the behavior of the crystal under high pressure was investigated using Raman spectroscopy (~8 GPa) and synchrotron X-ray diffraction (~26 GPa). The results show significant changes in both the X-ray diffractogram and the Raman spectra, suggesting that l-leucyl-l-leucine hydrate undergoes a phase transition between 2.3 and 2.9 GPa. Finally, for pressures above 16 GPa the broadening of X-ray peaks suggests a disorder in the crystal lattice induced by high-pressure effects.

The Role of Physical Frailty Independent Components on Increased Disabilities in Institutionalized Older Women.

The purpose of this study was to identify the independent components of physical frailty that most influence disability indicators in institutionalized older women. A cross-sectional study with 319 participants (81.96±7.89 years old) was performed. Disability was assessed through dynamic and static balance tests, activities of daily life and falls risk screen. Fried physical frailty protocol was used to access physical frailty. The frail subgroup displayed the weakest results for all disability indicators (p < 0.05). Regression analysis showed that in the two models tested, low physical activity levels and slowness were the physical frailty independent components that better associated with the disability indicators. More studies with larger samples will help to better understand the independent relationship of each physical frailty component with disability outcomes and assist to design a co-adjuvant treatment to reverse physical frailty.

Landsat phenological metrics and their relation to aboveground carbon in the Brazilian Savanna.

BACKGROUND: The quantification and spatially explicit mapping of carbon stocks in terrestrial ecosystems is important to better understand the global carbon cycle and to monitor and report change processes, especially in the context of international policy mechanisms such as REDD+ or the implementation of Nationally Determined Contributions (NDCs) and the UN Sustainable Development Goals (SDGs). Especially in heterogeneous ecosystems, such as Savannas, accurate carbon quantifications are still lacking, where highly variable vegetation densities occur and a strong seasonality hinders consistent data acquisition. In order to account for these challenges we analyzed the potential of land surface phenological metrics derived from gap-filled 8-day Landsat time series for carbon mapping. We selected three areas located in different subregions in the central Brazil region, which is a prominent example of a Savanna with significant carbon stocks that has been undergoing extensive land cover conversions. Here phenological metrics from the season 2014/2015 were combined with aboveground carbon field samples of cerrado sensu stricto vegetation using Random Forest regression models to map the regional carbon distribution and to analyze the relation between phenological metrics and aboveground carbon. RESULTS: The gap filling approach enabled to accurately approximate the original Landsat ETM+ and OLI EVI values and the subsequent derivation of annual phenological metrics. Random Forest model performances varied between the three study areas with RMSE values of 1.64 t/ha (mean relative RMSE 30%), 2.35 t/ha (46%) and 2.18 t/ha (45%). Comparable relationships between remote sensing based land surface phenological metrics and aboveground carbon were observed in all study areas. Aboveground carbon distributions could be mapped and revealed comprehensible spatial patterns. CONCLUSION: Phenological metrics were derived from 8-day Landsat time series with a spatial resolution that is sufficient to capture gradual changes in carbon stocks of heterogeneous Savanna ecosystems. These metrics revealed the relationship between aboveground carbon and the phenology of the observed vegetation. Our results suggest that metrics relating to the seasonal minimum and maximum values were the most influential variables and bear potential to improve spatially explicit mapping approaches in heterogeneous ecosystems, where both spatial and temporal resolutions are critical.

Pressure induced transformations in sorbic acid.

This research reports a pressure dependent Raman study of the sorbic acid between 0.0 and 10.0GPa. The unpolarized Raman spectra were measured in the spectral range of 20-3000cm-1. The high-pressure Raman scattering study of the sorbic acid showed that it underwent a gradual, disordering process. At the room temperature and at the ambient pressure conditions, the crystal structure of the sorbic acid belongs to the monoclinic system with a C2/c (C2h6) space group. The pressure increase induced a higher disorder in the monoclinic unit cell, since a single bending mode, and only very broad stretching Raman modes are present at pressure of ~10GPa. Upon pressure release the high-pressure phase transforms directly into the ambient-pressure phase. The presence of the internal vibrational modes is a guarantee that the molecular structure is maintained. Beyond this, the presence of external modes shows that the crystal has a memory to reverse the process and suggest that the crystal, which was in high disorder (broad Raman bands), does not suffer decomposition in the crystalline structure. The DFT calculations for the sorbic acid were performed in order to understand the vibrational properties. The theoretical study showed that the volume of the unit cell and beta angle decrease significatively when passing from the 0.0GPa to 8.0GPa. The decreases in the volume and beta angle of this particular unit cell were supposed to induce the larger increase in the bandwidths of the observed bands, pointing to some disorder in the monoclinic phase.

Effects of a chair-yoga exercises on stress hormone levels, daily life activities, falls and physical fitness in institutionalized older adults.

UNLABELLED: The aim of this study was to assess the changes mediated by exercise on activities of daily life and falls, physical fitness, salivary cortisol and alpha amylase in older adults living in social and health care givers centers. METHODS: Sample consisted in 35 women (83.81 ± 6.6 years old) were divided into two groups: chair-yoga exercises group (CY, n = 20) and control group (CG, n = 15). All subjects were evaluated before and after 14-weeks. CY was involved in exercise classes two times per week, while the GC did not participate in any exercise. RESULTS: Fear of falling decreased in both groups, cortisol increased and alpha-amylase decreased in the CG. No significant changes occurred in physical fitness outcomes. CONCLUSION: CY practice was able to maintain the physical fitness scores and stress hormone levels, but was not able to improve the subject's perception on the ability to perform the instrumental activities of daily life.

Conformational change in the C form of palmitic acid investigated by Raman spectroscopy and X-ray diffraction.

Fatty acids are substances found in most living beings in nature. Here we report the effect of the low temperature in the vibrational and structural properties of the C form of palmitic acid, a fatty acid with 16 carbon atoms. The Raman spectra were obtained in the temperature interval from 300 to 18K in the spectral range between 30 and 3100 cm(-1). The assignment of the duly observed bands was done based on the density functional theory. On cooling, the main changes observed in the lattice mode region of the Raman spectra were interpreted as a conformational modification undergone by the palmitic acid molecules in the unit cell. The X-ray diffraction measurements were obtained from 290 to 80K showing a slight modification in the lattice parameters at about 210K. Differential scanning calorimetry (DSC) measurements were recorded between 150 and 300K and no enthalpic anomaly in the DSC thermogram was observed. These techniques provided strong evidence of the conformational change in the molecules of palmitic acid at low temperatures.

Changes of Hematological Markers during a Multi-stage Ultra-marathon Competition in the Heat.

This study examined the changes in resting hematological variables in ultra-endurance runners throughout a multi-stage ultra-marathon competition, and compared athletes that completed all stages with those that failed to complete at least one stage within the cut-off time of competition. 19 ultra-endurance runners competing in a 230 km multi-stage ultra-marathon, conducted over 5 consecutive days in hot ambient conditions (32-40°C T(max)), volunteered to participate in the study. Each day, whole blood samples were collected prior to stage commencement and analyzed for full cell counts by Coulter counter. Linear increases were observed for leukocytes, monocytes and lymphocytes; with increases until Stage 3 and a decrease thereafter. Granulocytes showed a cubic growth exponent, indicating decrements to baseline after the significant increments until Stage 3. Hemoglobin and hematocrit showed linear decrements throughout the multi-stage ultra-marathon. No changes in erythrocytes and platelets were observed throughout the multi-stage ultra-marathon. Granulocytes, erythrocytes, hemoglobin and hematocrit changes along the multi-stage ultra-marathon differed in runners that completed all stages compared to those who failed to complete at least one stage within the cut-off time. Multi-stage ultra-marathon in the heat has a large impact on hematological responses of ultra-endurance runners associated with altered performance.

Vibrational spectroscopy, ab initio calculations and Frontier Orbital analysis of 4,5,6,8,9-pentachloropyrimido-[1,2-a][1,8]naphthyridin-10-one.

In this work we present a study of the vibrational spectra of 4,5,6,8,9-pentachloropyrimido-[1,2-a][1,8]naphthyridin-10-one, C11H2Cl5N3O, a substance belonging to the important pharmacological class of 1,8-naphthyridine derivatives. The Fourier transform infrared and the Fourier transform Raman spectra of the crystal were recorded at room temperature in the regions 400-4000 and 50-4000 cm(-1), respectively. Vibrational wavenumbers were predicted using Density Functional Theory calculations with the B3LYP functional on 6-31G(d,p) and 6-311++G(d,p) basis sets. The descriptions of the normal modes were made after calculating the potential energy distribution. Additionally, potential reaction sites were evaluated through Mulliken population and Frontier Orbital analysis.

Temperature-dependent vibrational spectroscopic study and DFT calculations of the sorbic acid.

This work reports a temperature-dependent vibrational spectroscopic study of the sorbic acid (C6H8O2), as well as the mode assignment at ambient conditions, based on the density functional theory. Temperature-dependent vibrational properties have been performed in polycrystalline sorbic acid through both Raman and infrared spectroscopy in the 20-300 K and 80-300 K temperature ranges, respectively. These studies present the occurrence of some modifications in the Raman spectra that could be interpreted as a low temperature phase transition undergone by sorbic acid from the monoclinic phase to an unknown phase with conformational change of the molecules in the unit cell.

Cinética de degradação in situ das silagens de capim Andropogon gayanus produzidas em três idades de corte / In situ degradation kinetic of Andropogon gayanus grass silages harvested at three stages of maturity

A idade ao corte é considerada o principal fator a afetar o valor nutritivo das forragens. Objetivou-se avaliar e comparar a cinética de degradação ruminal da matéria seca (MS), proteína bruta (PB) e fibra insolúvel em detergente neutro (FDN) das silagens de capim Andropogon gayanus obtidas em três diferentes idades de corte (56, 84 e 112 dias). As amostras das silagens secas e trituradas (5 mm) foram incubadas em sacos de nylon no rúmen por 0, 6, 12, 24, 48 e 72 h. Os parâmetros da cinética de degradação das silagens de cada tratamento (3 silagens) em cada animal (5 vacas) foram determinados pelo modelo: y = a + b(1 − e −c(t−L)). Os parâmetros gerados pela equação foram analisados como blocos inteiramente ao acaso, sendo que as idades de corte foram inseridas como efeito fixo e os animais como efeito aleatório (blocos). A silagem da planta aos 56 dias de rebrote apresentou maiores (P<0,05) valores de degradabilidade efetiva da MS e da FDN calculada para a taxa de passagem de 2,0%/h. Todas as silagens apresentaram baixa fração solúvel (<25,4%) e degradabilidade efetiva (<40,1%) da proteína bruta com taxa de passagem de 2%. Foi observado maior (P<0,05) tempo de colonização da FDN para as silagens realizadas com as plantas aos 84 e 112 dias de crescimento em comparação com a silagem produzida aos 56 dias. Os resultados da cinética de degradação ruminal das silagens de capim Andropogon gayanus indicam que a planta ensilada aos 56 dias de rebrote apresentou melhor valor nutricional...

Maturity is considered the primary factor affecting the nutritive value of forages. The aim of this study was to evaluate and compare dry matter (DM), crude protein (CP) and neutral detergent fiber (NDF) ruminal degradation kinetics of Andropogon gayanus grass silages harvested at three stages of maturity (56, 84 and 112 d). Dried and ground silage samples (5 mm) were incubated in nylon bags inside the rumen for 0, 6, 12, 24, 48, 72 and 96 h to estimate the kinetics of ruminal DM, CP and NDF degradation. The ruminal kinetic parameters of the silages from each treatment (56, 84 and 112 d of regrowth) in each animal (5 cows) were determined by the model: y = a + b(1 − e−c(t−L)). The parameters generated by the model were analyzed as randomized block design, with grass regrowth age as the fixed effect and animal the as random effect (blocks). The grass silage ensiled with 56 days of regrowth had the highest (P<0.05) effective degradability of DM and NDF calculated for fractional rate of particulate passage of 2%/h. All silages had low CP soluble fraction (<25.4%) and effective degradability calculated for fractional rate of particulate passage of 2%/h (<40.1%). A greater (P<0.05) NDF lag time was observed for the silages ensiled with 84 and 112d compared to the silage produced with 56d of regrowth. The ruminal degradation kinetics of Andropogon gayanus grass silages showed that the grass ensiled with 56 days of regrowth had higher nutritional value...

Production, Nutritional Quality and In vitro Methane Production from Andropogon gayanus Grass Harvested at Different Maturities and Preserved as Hay or Silage.

Andropogon gayanus is an important grass due to its high biomass production, drought tolerance and favorable growth on low fertility acidic soils. Currently, there is little research on the impact of growth stage on the nutritional quality or the degree of CH4 production that may arise from this forage during ruminal fermentation. The objectives of this study were to determine the effects of regrowth stage of A. gayanus on its chemical composition, in vitro production of gas and CH4, as well as in vitro dry matter (DM) digestibility when grown under tropical Brazilian conditions and conserved as hay or as silage. The nutritional value of A. gayanus grass declined with increasing maturity; however digestible DM yield linearly increased. After 112 d of regrowth, A. gayanus produced higher quality silage (higher lactate and lower pH and butyrate content) and higher DM yield. However, the low levels of crude protein at this time would make protein supplementation a necessity for proper rumen fermentation. No differences in CH4 kinetic parameters were found with advancing maturity or preservation method (hay or silage).

The impact of a 24-h ultra-marathon on salivary antimicrobial protein responses.

Depressed oral respiratory mucosal immunity and increased incidence of upper respiratory symptoms are commonly reported after bouts of prolonged exercise. The current study observed the impact of a 24-h continuous overnight ultra-marathon competition (distance range: 122-208 km; ambient temperature range: 0-20 °C) on salivary antimicrobial protein responses and incidence of upper respiratory symptoms. Body mass, unstimulated saliva and venous blood samples were taken from ultra-endurance runners (n=25) and controls (n=17), before and immediately after competition. Upper respiratory symptoms were assessed during and until 4-weeks after event completion. Samples were analyzed for salivary IgA, lysozyme, α-amylase and cortisol in addition to plasma osmolality. Decreased saliva flow rate (p<0.001), salivary IgA (p<0.001) and lysozyme (p=0.015) secretion rates, and increased salivary α-amylase secretion rate (p<0.001) and cortisol responses (p<0.001) were observed post-competition in runners, with no changes being observed in controls. No incidences of upper respiratory symptoms were reported by participants. A 24-h continuous overnight ultra-marathon resulted in the depression of some salivary antimicrobial protein responses, but no incidences of upper respiratory symptoms were evident during or following competition. Salivary antimicrobial protein synergism, effective management of non-infectious episodes, maintaining euhydration, and (or) favourable environmental influences could have accounted for the low prevalence of upper respiratory symptoms.