Improved Approach for ab Initio Calculations of Rate Coefficients for Secondary Reactions in Acrylate Free-Radical Polymerization.

Secondary reactions in radical polymerization pose a challenge when creating kinetic models for predicting polymer structures. Despite the high impact of these reactions in the polymer structure, their effects are difficult to isolate and measure to produce kinetic data. To this end, we used solvation-corrected M06-2X/6-311+G(d,p) ab initio calculations to predict a complete and consistent data set of intrinsic rate coefficients of the secondary reactions in acrylate radical polymerization, including backbiting, ß-scission, radical migration, macromonomer propagation, mid-chain radical propagation, chain transfer to monomer and chain transfer to polymer. Two new approaches towards computationally predicting rate coefficients for secondary reactions are proposed: (i) explicit accounting for all possible enantiomers for reactions involving optically active centers; (ii) imposing reduced flexibility if the reaction center is in the middle of the polymer chain. The accuracy and reliability of the ab initio predictions were benchmarked against experimental data via kinetic Monte Carlo simulations under three sufficiently different experimental conditions: a high-frequency modulated polymerization process in the transient regime, a low-frequency modulated process in the sliding regime at both low and high temperatures and a degradation process in the absence of free monomers. The complete and consistent ab initio data set compiled in this work predicts a good agreement when benchmarked via kMC simulations against experimental data, which is a technique never used before for computational chemistry. The simulation results show that these two newly proposed approaches are promising for bridging the gap between experimental and computational chemistry methods in polymer reaction engineering.

Impact of diversified grazing systems on milk production, nutrient use and enteric methane emissions in dual-purpose cows.

This study evaluated three continuous grazing systems: Brachiaria Brizantha, Clitoria ternatea and naturalized pastures, complemented with commercial concentrate and C. ternatea silage on milk yield, nutrient use and enteric methane (CH4) emissions. Nine multiparous cows of local Zebu breeds, with an average weight of 448 ± 87 kg, were used. The chemical composition of the food was determined. Live weight, milk production, and quality were assessed. Furthermore, serum urea, urea nitrogen, creatinine and glucose in blood were monitored, and nitrogen use efficiency were calculated. Enteric methane (CH4) emissions were estimated using Tier-2 methodology. A 3 × 3 latin square experimental design was applied. The grazing systems of B. brizantha and C. ternatea had the greater live weights of 465.8 and 453.3 kg/cow, although the latter is similar to naturalized pasture. Milk production and quality were not affected by grazing system, with the exception of the non-fat solids, where the C. ternatea system was lower (102.2 g/kg) than the other grazing systems. The crude protein and N intake, and N excretion in feces and urine were lower in naturalized pasture systems (1139.0 g/day). N outputs in milk was high in the C. ternatea system (56.3 g/cow/day). The naturalized pastures systems showed the better feed use efficiency (25.7%) compared to others. Serum urea and blood urea nitrogen were greater in B. brizantha followed by C. ternatea. Enteric CH4 emissions were indifferent among grazing systems when expressed as a percentage of greenhouse gases (7.1%). In conclusion, the grazing C. ternatea supplemented with commercial concentrate and C. ternatea silage maintains milk production and quality, reduced cow/day emissions (by 2.5%) and lowered energy losses as methane.

Residual Feed Intake and Rumen Metabolism in Growing Pelibuey Sheep.

This study was carried out to evaluate the residual feed intake (RFI), volatile fatty acid (VFA) production and enteric methane (CH4) from growing Pelibuey sheep. In this case, 12 non-castrated Pelibuey with an initial average live weight (LW) of 21.17 ± 3.87 kg and an age of 3 months, were housed in individual pens and fed a basal diet with 16% of crude protein and 11 MJ ME for 45 days. Dry matter intake (DMI) was measured and the daily weight gain (DWG) was calculated using a linear regression between the LW and experimental period. Mean metabolic live weight (LW0.75) was calculated. RFI was determined by linear regression with DWG and LW0.75 as independent variables. Lambs were classified as low, medium, and high RFI. Feed efficiency was determined as DWG/DMI. For determining rumen pH, ammonia nitrogen concentration NH3-N), and VFA, ruminal fluid was obtained using an esophageal probe on day 40. Feed intake of low RFI lambs was approximately 16% lower (p < 0.05) while growth rate was not significantly different. Their average energy loss, expressed as CH4 production per kilogram of metabolic weight, was 17% lower (p < 0.05).

Nitrogen use efficiency and soil chemical composition in small-scale dairy systems.

In dairy production systems, the efficient use of resources is required to guarantee its sustainability. Worldwide, the efficiency of feed utilization and its effects have been widely studied. However, few studies have quantified animal nitrogen use and its corresponding soil contribution in small-scale production systems. Therefore, this study aimed to determine the efficiency of feed utilization and quantify the soil chemical composition in small-scale production systems using two different feeding strategies. Twelve dairy farms were evaluated from May 2016 to April 2017. Data analysis was performed using an ANOVA following a completely randomized model and using feeding strategies as treatment. Regarding the feeding systems' characteristics, significant differences (P < 0.05) were only observed in land surface and land used to produce mixed-grass and corn. Nitrogen (N) input and output in dairy cattle were significantly different (P < 0.05) for crude protein intake. The highest results were observed in grazing feeding systems. The cut and carry strategies excreted 71% of the consumed N in the manure; grazing strategies excreted 72%. The efficiency of feed utilization (EFU) is low; only 19% of the consumed N is recovered during milk production. As for the soil chemical composition, significant differences (P < 0.05) were observed in the percentage of total N and the carbon to nitrogen (C:N) ratio. The remaining components behaved similarly in both feeding systems. Systems that include crops and livestock can positively change the biophysical and socioeconomic dynamics of agricultural systems.

Heightened Virulence of Yersinia Is Associated with Decreased Function of the YopJ Protein.

Despite the maintenance of YopP/J alleles throughout the human-pathogenic Yersinia lineage, the benefit of YopP/J-induced phagocyte death for Yersinia pathogenesis in animals is not obvious. To determine how the sequence divergence of YopP/J has impacted Yersinia virulence, we examined protein polymorphisms in this type III secreted effector protein across 17 Yersinia species and tested the consequences of polymorphism in a murine model of subacute systemic yersiniosis. Our evolutionary analysis revealed that codon 177 has been subjected to positive selection; the Yersinia enterocolitica residue had been altered from a leucine to a phenylalanine in nearly all Yersinia pseudotuberculosis and Yersinia pestis strains examined. Despite this change being minor, as both leucine and phenylalanine have hydrophobic side chains, reversion of YopJF177 to the ancestral YopJL177 variant yielded a Y. pseudotuberculosis strain with enhanced cytotoxicity toward macrophages, consistent with previous findings. Surprisingly, expression of YopJF177L in the mildly attenuated ksgA- background rendered the strain completely avirulent in mice. Consistent with this hypothesis that YopJ activity relates indirectly to Yersinia pathogenesis in vivo, ksgA- strains lacking functional YopJ failed to kill macrophages but actually regained virulence in animals. Also, treatment with the antiapoptosis drug suramin prevented YopJ-mediated macrophage cytotoxicity and enhanced Y. pseudotuberculosis virulence in vivo. Our results demonstrate that Yersinia-induced cell death is detrimental for bacterial pathogenesis in this animal model of illness and indicate that positive selection has driven YopJ/P and Yersinia evolution toward diminished cytotoxicity and increased virulence, respectively.

Mitigation of Rumen Methane Emissions with Foliage and Pods of Tropical Trees.

Methane produced by enteric fermentation contributes to the emission of greenhouse gases (GHG) into the atmosphere. Methane is one of the GHG resulting from anthropogenic activities with the greater global warming contribution. Ruminant production systems contribute between 18% and 33% of methane emissions. Due to this, there has been growing interest in finding feed alternatives which may help to mitigate methane production in the rumen. The presence of a vast range of secondary metabolites in tropical trees (coumarins, phenols, tannins, and saponins, among others) may be a valuable alternative to manipulate rumen fermentation and partially defaunate the rumen, and thus reduce enteric methane production. Recent reports suggest that it is possible to decrease methane emissions in sheep by up to 27% by feeding them saponins from the tea leaves of Camellia sinensis; partial defaunation (54%) of the rumen has been achieved using saponins from Sapindus saponaria. The aim of this review was to collect, analyze, and interpret scientific information on the potential of tropical trees and their secondary metabolites to mitigate methane emissions from ruminants.

Udder Measurements and Their Relationship with Milk Yield in Pelibuey Ewes.

The study aimed to evaluate the relationship between udder measurements and milk yield (MY) in dairy Pelibuey ewes. Udder measurements were taken twice a week for eight weeks before (initial) and after (final) milking, including udder depth (UD), udder circumference (UC), udder width (UW), teat length (TL) and teat diameter (TD) in 38 multiparous ewes. Additionally, udder volume (UV) and the difference (VDF) between initial UV (UVi) and final (UVf) was calculated as VDF = UVi - UVf. The MY varied from 0.10 kg/d to 1.04 kg/d, with a mean of 0.39 kg/d, ± 0.18 kg/d. Initial UC (UCi) ranged from 25.80 cm to 53.30 cm, and VDF varied from 1 cm3 to 2418 cm3. The TL and TD were not correlated with MY (p > 0.05), while UCi, UVi and VDF were positively correlated with MY (p < 0.0001; r = from 0.66 to 0.74). For the prediction of MY, the obtained equations had an r2 ranging from 0.54 to 0.63. The UCi, UDf, UWi and UWf were included in these models (p < 0.05). It is concluded that there was an acceptable correlation (r = 0.60) between the measurements of the udder, the volume of the udder and the daily milk yield in Pelibuey sheep. When direct measurements of milk production cannot be performed in practice, the measurement of udders and their volume could be a viable alternative to estimate milk yield production as an indirect method.

Estimation of body weight in hair ewes using an indirect measurement method.

The aim of the present study was to develop and evaluate an equation to predict body weight (BW) using hip width (HW) in Pelibuey ewe lambs and ewes. Five hundred seventy-seven 2-month-old to 3-year-old, non-pregnant, non-lactating, clinically healthy ewe lambs and adult ewes with a mean BW of 34.7 ± 12.4 kg and HW of 15.6 ± 3.4 cm were considered. Three equations were evaluated: BW (kg): - 19.17 + 3.46 × HW (Eq. 1), BW (kg): - 17.79 + 3.25 × HW + 0.007 × HW2 (Eq. 2) and BW (kg): 0.39 × HW1.63 (Eq. 3). Independent data from 80 animals with similar characteristics (BW of 23.4 ± 10.9 kg and HW of 12 ± 3.1 cm) were also considered to evaluate the developed equations. The evaluation was based on the relationship between the observed and predicted values of BW analysed using a linear regression, the mean squared error of prediction (MSEP), the root MSEP (RMSEP) and the concordance correlation coefficients (CCCs). Additionally, cross-validation analyses were performed using the k-folds validation (k = 10) procedure. The correlation coefficient (r) between BW and HW was 0.94 (P < 0.001). The parameters for precision and accuracy showed that the proposed equations had high precision (R2 > 0.95%), accuracy (Cb > 0.98) and reproducibility (CCC > 0.96) in predicting the BW of ewe lambs and adult ewes. Equation (1) accurately predicted observed BW, with a bias (observed - predicted) of 4.3 kg and RMSEP of 9.68% with respect to the observed BW (random error of 84.23%); it also generated the best prediction according to the residual mean squared prediction error, coefficient of determination and mean absolute error. In conclusion, the highly correlated relationship between BW and HW in Pelibuey ewe lambs and adult ewes under humid tropic conditions enabled the development of mathematical models herein to estimate BW with an adequate goodness of fit. The linear model showed the best performance according to the goodness-of-fit evaluation and internal and external validation; hence, this model is proposed for use in both the experimental and commercial farms.

Diversidad de macro-invertebrados en sistemas silvopastoriles del sur de Quintana Roo, México

La diversidad de macro-invertebrados está relacionada con el estado de conservación del suelo, no obstante, la remoción de la cubierta vegetal natural para el establecimiento de sistemas ganaderos extensivos afecta su integridad. Una estrategia para la conservación de estos organismos es la implementación de sistemas silvopastoriles; no obstante, en el sureste de México la información aún es limitada. El propósito del presente estudio fue evaluar y comparar la riqueza y la abundancia de macro-invertebrados en cuatro agro-ecosistemas contrastantes: dos sistemas silvopastoriles conformados por Leucaena leucocephala y pastos asociados (i.e. Panicum máximum cv mombaza y Cynodon plectostachyus), un pastizal convencional de Brachiaria brizantha con árboles dispersos en baja densidad y una selva mediana subperennifolia. En cada sistema se delimitó una superficie de una hectárea y se estableció un transecto de 50 m de longitud en los que se colocaron cinco trampas de caída tipo pit-fall cada 10 m. El muestreo se realizó en febrero y mayo 2018 y en cada mes se realizaron cinco recolectas con intervalos de cinco días. Se recolectaron un total de 1 737 organismos pertenecientes a 10 órdenes de la clase Insecta y uno a la clase Gastropoda. Los sistemas con mayor abundancia de macro-invertebrados fueron el sistema de selva media subperennifolia (923 individuos) y el sistema silvopastoril de L. leucocephala con C. plectostachyus (354 individuos). Los órdenes más abundantes fueron: Hymenoptera, Coleoptera, Araneae y Orthoptera. La mayor diversidad de macro-invertebrados se presentó en los sistemas silvopastoriles de L. leucocephala con P. maximum (H'=1.58) y L. leucocephala con C. plectostachyus (H´=1.44). Los resultados encontrados muestran que los sistemas pecuarios manejados con componentes leñosos (árboles/arbustos) albergan una riqueza y abundancia importante de órdenes de macro-invertebrados en comparación con sistemas como selva mediana subperennifolia. Esta diversidad de macro-invertebrates podría contribuir a la integridad y funcionalidad de los agro-ecosistemas.

The diversity of macro-invertebrates is related to the state of disturbance of the soil, caused mainly by the land-use change for agricultural activities. A strategy for the conservation of these organisms is the implementation of diversified production systems such as silvopastoral systems. However, in the Southeast of Mexico, information is still limited. The aim of the present study was to evaluate and compare the richness, abundance and composition of macro-invertebrates in four contrasting agro-ecosystems: two silvopastoral systems made of Leucaena leucocephala and associated pastures (i.e. Panicum maximum cv mombaza and Cynodon plectostachyus), a pasture of Brachiaria brizantha with scattered trees in low density and, a medium-statured tropical dry forest. In each system, an area of one hectare was delimited and a transect of 50 m in length was established in which five pit-fall traps were placed every 10 m. The sampling was carried out in February and May of 2018 and in each month five collections were made with five-day intervals. A total of 1 737 organisms belonging to 10 orders of the class Insecta and one of the class Gastropoda were collected. The medium-statured tropical dry forest (923 individuals) and the silvopastoral systems of L. leucocephala with C. Plectostachyus (354 individuals) show the highest abundance of macro-invertebrates. The most abundant genera were: Hymenoptera, Coleoptera, Aracninae and Orthoptera. The higher macro-invertebrate diversity was found in the silvopastoral systems of L. leucocephala with P. maximum (H '= 1.58) and L. leucocephala with C. plectostachyus (H' = 1.44). The results show that livestock systems managed with woody components (trees or shrubs) are home of an important abundance and richness of macro-invertebrates, compared to tropical forests. This diversity of macro-invertebrates may contribute to the integrity and functionality of the agro-ecosystems.

Adrenomedullin2 (ADM2)/Intermedin (IMD): A Potential Role in the Pathophysiology of Preeclampsia.

CONTEXT: It is not known whether decreases in trophoblast invasion promoting the peptide, adrenomedullin2 (ADM2) system is associated with preeclampsia (PreE). OBJECTIVE: The objective of the study was to assess the changes in ADM2 levels in plasma, placenta, and amniotic fluid (AF) and its receptor components in placenta from PreE pregnancy compared with the age-matched normal and study the effect of ADM2 on the synthesis of nitric oxide (NO), endothelial nitric oxide synthase (eNOS), and matrix-metalloproteinase (MMP)-2 and MMP-9 in trophoblast cells. RESULTS: PreE is associated with a decreased expression of ADM2 in plasma and placenta (P < .05); ADM2 interacts with a seven-transmembrane G protein-coupled receptor, calcitonin receptor-like receptor (CRLR) in HTR-8/SVneo cells; placental expression of ADM2/CRLR complex is lower in PreE; mRNA for CRLR and receptor activity-modifying protein-3 are lower, whereas receptor activity-modifying protein-2 is higher in the PreE placenta (P < .05); ADM2 levels in the second trimester are lower in the AF from pregnant women who develop PreE later in gestation (P < .05); ADM2 is localized to the epithelium of the amnion and the ectoderm and mesoderm of the chorion in term fetal membranes; ADM2 increases NO production, eNOS, and MMP2/9-immunoreactivity, whereas ADM2 knockdown inhibits the expression of eNOS and MMP2/9 mRNA and S-nitrosylation in HTR-8/SVneo cells; and ADM2-induced increases in MMP2/9 activity is inhibited by L-nitro-arginine methyl ester in HTR-8SV/neo cells. CONCLUSION: Decreases in the ADM2 system in PreE at term, in AF from pregnant women during the second trimester who develop PreE later in gestation, and ADM2-induced increases in the NO and MMP-2/9 levels in trophoblast cells suggest a potential role for ADM2 via the NO-MMP system in the pathophysiology of PreE.

Pregnancy Increases Relaxation in Human Omental Arteries to the CGRP Family of Peptides.

Calcitonin gene-related peptide (CALCB) and its family members adrenomedullin (ADM) and intermedin (ADM2) play important roles in maintaining vascular adaptations during pregnancy in animal models. The present study was designed to evaluate the responses of omental arteries to CALCB, ADM, and ADM2 in pregnant and nonpregnant women, and to determine the mechanisms involved. By using resistance omental arteries collected from nonpregnant women (n = 15) during laparotomy and from term pregnant women (n = 15) at cesarean delivery, this study shows that the receptor components--calcitonin receptor-like receptor (CALCRL) and receptor activity-modifying proteins (RAMPs) 1, 2 and 3--are localized to endothelial and smooth muscle cells in omental arteries, with increased expressions of both mRNA and protein in pregnant compared with nonpregnant women. The myography study demonstrated that CALCB, ADM, and ADM2 (0.1-100 nM) dose dependently relax U46619 (1 muM) precontracted omental artery segments, and the maximum possible effects to CALCB and ADM2, but not to ADM, are significantly enhanced in pregnant compared with nonpregnant women. Further, the vasodilatory responses to CALCB, ADM, and ADM2 are reduced by inhibitors of nitric oxide (NO) synthase (L-NAME), adenylyl cyclase (SQ22536), voltage-activated potassium channels (4-aminopyrodin and tetrabutylammonium), Ca(2+)-activated potassium channel (charybdotoxin), and cyclooxygenase (indomethacin). In conclusion, the CALCB family of peptides, CALCB and ADM2, increase human omental artery relaxation during pregnancy through diverse mechanisms, including NO, endothelium-derived hyperpolarizing factors (EDHFs) and prostaglandins, and thus could contribute to the vascular adaptations during pregnancy in the human.

Ensayos biologicos aplicables para el control de inocuidad de cosmeticos / Biology trials applicable for the control of inocular cosmetics

Esta monografía dedicada al ensayo biológico aplicables alos productos cosméticos así a la materia prima utilizada en la elaboración de ellos, fué realizada a fin de: difundir parte de la actividad docente, presentar consideraciones relativas a la necesidad de incluir los ensayos biológicos como parte del proceso de control de calidad de productos cosméticos, nombrar los tipos de ensayos bilogicos a ser aplicados a las diferentes formas cosméticas. Se espera que monogarfía contribuya a la formación de recursos humanos, y al uso permanente dequienes se desempeñan en el campo del control de la calidad de estos productos