A figure of merit for efficiency roll-off in TADF-based organic LEDs.

Organic light-emitting diodes (OLEDs) are a revolutionary light-emitting display technology that has been successfully commercialized in mobile phones and televisions1,2. The injected charges form both singlet and triplet excitons, and for high efficiency it is important to enable triplets as well as singlets to emit light. At present, materials that harvest triplets by thermally activated delayed fluorescence (TADF) are a very active field of research as an alternative to phosphorescent emitters that usually use heavy metal atoms3,4. Although excellent progress has been made, in most TADF OLEDs there is a severe decrease of efficiency as the drive current is increased, known as efficiency roll-off. So far, much of the literature suggests that efficiency roll-off should be reduced by minimizing the energy difference between singlet and triplet excited states (ΔEST) to maximize the rate of conversion of triplets to singlets by means of reverse intersystem crossing (kRISC)5-20. We analyse the efficiency roll-off in a wide range of TADF OLEDs and find that neither of these parameters fully accounts for the reported efficiency roll-off. By considering the dynamic equilibrium between singlets and triplets in TADF materials, we propose a figure of merit for materials design to reduce efficiency roll-off and discuss its correlation with reported data of TADF OLEDs. Our new figure of merit will guide the design and development of TADF materials that can reduce efficiency roll-off. It will help improve the efficiency of TADF OLEDs at realistic display operating conditions and expand the use of TADF materials to applications that require high brightness, such as lighting, augmented reality and lasing.

Distinguishing Electron Diffusion and Extraction in Methylammonium Lead Iodide.

Charge diffusion and extraction are crucial steps in the operation of solar cells. Here we show that time-resolved photoluminescence can be used to study electron diffusion in hybrid perovskite films and subsequent transfer to the adjacent electron extraction layer. As diffusion and transfer to the extraction layer are consecutive processes, they can be hard to distinguish, but by exciting from each side of the sample we can separate them and identify which process limits charge extraction. We find that the introduction of a fullerene monolayer between the methylammonium lead iodide (MAPbI3) and the electron-transporting SnO2 layers greatly increases the electron transfer velocity between them to the extent that electron diffusion limits the rate of electron extraction. Our results suggest that increasing the electron diffusion coefficient in MAPbI3 would further enhance the electron extraction rate, which could result in more efficient n-i-p type solar cells.

The synthesis of brominated-boron-doped PAHs by alkyne 1,1-bromoboration: mechanistic and functionalisation studies.

The synthesis of a range of brominated-B n -containing (n = 1, 2) polycyclic aromatic hydrocarbons (PAHs) is achieved simply by reacting BBr3 with appropriately substituted alkynes via a bromoboration/electrophilic C-H borylation sequence. The brominated-B n -PAHs were isolated as either the borinic acids or B-mesityl-protected derivatives, with the latter having extremely deep LUMOs for the B2-doped PAHs (with one example having a reduction potential of E 1/2 = -0.96 V versus Fc+/Fc, Fc = ferrocene). Mechanistic studies revealed the reaction sequence proceeds by initial alkyne 1,1-bromoboration. 1,1-Bromoboration also was applied to access a number of unprecedented 1-bromo-2,2-diaryl substituted vinylboronate esters directly from internal alkynes. Bromoboration/C-H borylation installs useful C-Br units onto the B n -PAHs, which were utilised in Negishi coupling reactions, including for the installation of two triarylamine donor (D) groups onto a B2-PAH. The resultant D-A-D molecule has a low optical gap with an absorption onset at 750 nm and emission centered at 810 nm in the solid state.

Contribución de la dieta a la exposición al plomo en niños de 1 a 7 años / Contribution of diet to lead exposure in children from 1 to 7 years

INTRODUCCIÓN El plomo es un metal tóxico, que aun a bajas concentraciones sanguíneas es capaz de alterar el normal desarrollo neurológico de los niños. Se sabe que la absorción de plomo de los alimentos es la mayor contribución a los niveles de plombemia en la población no expuesta laboralmente. OBJETIVOS Determinar la contribución dietaria a la exposición al plomo en niños de 1 a 7 años de edad que concurren por controles de salud al Hospital de Niños de La Plata. MÉTODOS En una primera etapa se realizó una encuesta alimentaria sobre cuya base, en una segunda etapa, se seleccionaron los alimentos a analizar. En una tercera fase los alimentos se muestrearon en distintos comercios. El cuarto paso fue la determinación de plomo en los grupos de alimentos y, finalmente, se estimó la ingesta diaria de plomo (Ipb) de la población estudiada. RESULTADOS La Ipb fue de 138 µg/día. Los grupos de alimentos que tuvieron mayor contribución fueron los productos cárnicos (15,4%), los panificados (14,8%), la leche (12,5%) y la carne (11,7%). DISCUSIÓN Se combina la carga excesiva de plomo en la dieta a la que está expuesta la población estudiada con las deficiencias en micronutrientes en una importante proporción. De este modo, el componente dietario es un factor de riesgo con un rol preponderante en la exposición al plomo de los niños.

A Comparative Toxidrome Analysis of Human Organophosphate and Nerve Agent Poisonings Using Social Media.

Here we utilized social media to compare the toxidrome of three lethal chemical exposures worldwide. YouTube videos were the main source from which the data were collected, but published reports and news were also utilized to fill in some gaps. All videos were organized in a database detailing symptoms and severity of each victim, along with demographics such as approximate age and gender. Each symptom was rated as mild, moderate, or severe and corresponding pie graphs for each incident were compared. The videos displayed symptoms ranging from mild to severe cholinergic toxicity and life-threatening convulsions. Social media may represent an important resource in developing a viable approach to the early detection and identification of chemical exposure, reinforce our preparedness for better antidotes, long-term follow up, and training about deadly chemical nerve agent attacks.

Grain-based versus alfalfa-based subacute ruminal acidosis induction experiments: Similarities and differences between changes in milk fatty acids.

Subacute ruminal acidosis (SARA) is one of the most important metabolic disorders, traditionally characterized by low rumen pH, which might be induced by an increase in the dietary proportion of grains as well as by a reduction of structural fiber. Both approaches were used in earlier published experiments in which SARA was induced by replacing part of the ration by a grain mixture or alfalfa hay by alfalfa pellets. The main differences between both experiments were the presence of blood lipopolysaccharide and Escherichia coli and associated effects on the rumen microbial population in the rumen of grain-based induced SARA animals as well as a great amount of quickly fermentable carbohydrates in the grain-based SARA induction experiment. Both induction approaches changed rumen pH although the pH decrease was more substantial in the alfalfa-based SARA induction protocol. The goal of the current analysis was to assess whether both acidosis induction approaches provoked similar shifts in the milk fatty acid (FA) profile. Similar changes of the odd- and branched-chain FA and the C18 biohydrogenation intermediates were observed in the alfalfa-based SARA induction experiment and the grain-based SARA induction experiment, although they were more pronounced in the former. The proportion of trans-10 C18:1 in the last week of the alfalfa-based induction experiment was 6 times higher than the proportion measured during the control week. The main difference between both induction experiments under similar rumen pH changes was the decreasing sum of iso FA during the grain-based SARA induction experiment whereas the sum of iso FA remained stable during the alfalfa-based SARA induction experiment. The cellulolytic bacterial community seemed to be negatively affected by either the presence of E. coli and the associated lipopolysaccharide accumulation in the rumen or by the amount of starch and quickly fermentable carbohydrates in the diet. In general, changes in the milk FA profile were related to changes in rumen pH. Nevertheless, feed characteristics (low in structural fiber vs. high in starch) also affected the milk FA profile and, as such, both effects should be taken into account when subacute acidosis occurs.

The logistic curve as a tool to describe the daily ruminal pH pattern and its link with milk fatty acids.

Daily ruminal pH variation can be summarized by a cumulative logistic curve based on the amount of time below multiple pH points and characterized by 2 parameters (ß(0) and ß(1)). Moreover, rumen pH variation affects the rumen microbiome as well as the biohydrogenation pathways resulting in a modified secretion of milk fatty acids (FA). The aims of this study were to assess the shifts in milk FA due to rumen pH changes and to estimate the relationship between milk FA and the 2 parameters of the logistic curve. The data consisted of milk samples of 2 experiments. In experiment 1, 3 cows were subjected to 5 treatments in which the type and amount of concentrate were changed during 33 d: (1) control diet 1, (2) stepwise replacement of a standard concentrate (CONC) by a CONC rich in rapidly fermentable carbohydrates, (3) increase in the total amount of CONC, (4) treatment with a buffer solution, and (5) control diet 2. A 3×3 Latin square design with 3 cows was used in the second experiment. During the first 14 d of each period, the cows received a control diet with a standard CONC, whereas in the last 7 d the standard CONC was replaced step-by-step by a CONC rich in rapidly fermentable carbohydrates and the amount of CONC was increased. During each period, a different buffer treatment was added to the diet. Milk FA and pH reacted similarly in both experiments: decreasing proportions of iso FA and increasing proportions of odd-chain FA were observed. However, an abrupt change to a 76% CONC diet as for one cow of experiment 1 led to almost a 10-fold increase in C18:1 trans-10 (0.79 vs. 6.75 g/100g of FA). In experiment 2, the stepwise approach of adding CONC and the continuous supplementation of buffer led to minimal increases in C18:1 trans-10 and decreases in rumen pH compared with the diet with standard CONC only. Fatty acid proportions were influenced by the level of rumen pH (ß(1)) or the rumen pH variation (ß(0)), or both. High proportions of C18:1 trans-10 (above 4 g/100g of FA) occurred with low and largely fluctuating pH (low ß(1), low ß(0)), whereas situations with low, stable pH (low ß(1), great ß(0)) did not induce a shift toward the secondary biohydrogenation pathway. C18:1 trans-11 and C18:2 cis-9, trans-11 were only influenced by the pH variation and not by the average pH, whereas iso C14:0 and iso C16:0 FA were only dependent on the average pH and not influenced by diurnal pH variation. Overall, milk FA changes were related to pH changes; however, this relationship is not straightforward and needs further research.

Analysis of milk odd- and branched-chain fatty acids using Fourier transform (FT)-Raman spectroscopy.

Fourier transform (FT)-Raman spectra of pure C13:0, C15:0, C17:0, iso C14:0, iso C15:0, and ante C15:0 fatty acid methyl ester standards (FAMESs) and 75 milk fat samples from 6 different dietary experiments were acquired at room temperature (RT) and immediately after freezing at -80 °C (FT). The latter generally included much more well-defined and sharper scattering bands than those obtained at RT. Further, the spectra at FT revealed additional acuate bands in the vicinity of peculiar wavenumber regions, as well as an increase of Raman scattering intensity, which was sometimes associated with a shift of the peak. Partial least-squares (PLS) regression models based on either selected regions or the full spectra and using two pretreatment methods [multiplicative scatter correction (MSC, using raw spectra of milk fat only) and modified MSC (MMSC, a combination of pure FAMESs and milk fat spectra)] with cross-validation were used to evaluate the different types of milk fat FT-Raman spectra for the predictions of individual odd- and branched-chain fatty acids (OBCFAs) and their sums. In general, most individual (C15:0, ante C15:0, iso C17:0, and ante C17:0) and grouped (ODD, ANTE, and total OBCFAs) fatty acids were favorably (coefficient of determination, R(2) > 0.65) predicted using models with FT spectra only or a combination of RT and FT spectra (RFT), when compared to models with spectra analyzed at RT only. The results indicate the interest to use FT-Raman spectra collected at different temperatures for the prediction of narrow concentrations of saturated OBCFAs in milk fat.

Effect of induction of subacute ruminal acidosis on milk fat profile and rumen parameters.

High-concentrate diets can lead to subacute ruminal acidosis and are known to result in changes of the ruminal fermentation pattern and mammary secretion of fatty acids. The objective of this paper is to describe modifications in milk fatty acid proportions, particularly odd- and branched-chain fatty acids and rumen biohydrogenation intermediates, associated with rumen parameters during a 6-wk subacute ruminal acidosis induction protocol with 12 ruminally fistulated multiparous cows. The protocol involved a weekly gradual replacement of a standard dairy concentrate with a wheat-based concentrate (610 g of wheat/kg of concentrate) during the first 5 wk and an increase in the total amount of concentrate in wk 6. Before the end of induction wk 6, cows were switched to a control diet because 7 cows showed signs of sickness. The pH was measured continuously by an indwelling pH probe. Milk and rumen samples were taken on d 2 and 7 of each week. Data were analyzed using a linear mixed model and by principal component analysis. A pH decrease occurred after the first concentrate switch but rumen parameters returned to the original values and remained stable until wk 5. In wk 5 and 6, rumen pH values were indicative of increasing acidotic conditions. After switching to the control diet in wk 6, rumen pH values rapidly achieved normal values. Odd- and branched-chain fatty acids and C18:1 trans-10 increased with increasing amount of concentrate in the diet, whereas C18:1 trans-11 decreased. Four fatty acids [C18:1 trans-10, C15:0 and C17:0+C17:1 cis-9 (negative loadings), and iso C14:0 (positive loading)] largely correlated with the first principal component (PC1), with cows spread along the PC1 axis. The first 4 wk of the induction experiment showed variation across the second principal component (PC2) only, with high loadings of anteiso C13:0 (negative loading) and C18:2 cis-9,trans-11 and C18:1 trans-11 (positive loadings). Weeks 5 and 6 deviated from PC2 and tended toward the negative PC1 axis. A discriminant analysis using a stepwise approach indicated the main fatty acids discriminating between the control and acidotic samples as iso C13:0, iso C16:0, and C18:2 cis-9,trans-11 rather than milk fat content or C18:1 trans-10, which have been used before as indicators of acidosis. This shows that specific milk fatty acids have potential in discriminating acidotic cases.

Genetic parameters for intramuscular fatty acid composition and metabolism in pigs.

The aim of this study was to estimate genetic parameters for pork intramuscular fatty acid (FA) composition and indices for desaturase and elongase activities involved in n-3 and n-6 PUFA metabolism. The LM of 437 slaughter pigs was analyzed for FA composition (expressed as g/100 g of FA). Indices for enzyme activities were calculated from product to precursor FA ratios. Genetic parameters were estimated with single- and multi-trait animal models. The total FA content, reflecting the intramuscular fat content, was either included or not in the model. Results from the models without total FA content showed relatively high heritability estimates, generally above 0.50, for the proportion of the most important MUFA and PUFA, compared with much smaller values for the SFA. When total FA content was included in the models, heritability values decreased (P < 0.001) for most individual FA and for all sums of FA groups, except for C18:0, C18:3n-6, and C18:3n-3. Heritability estimates for the ratios C20:4n-6/C18:2n-6 and C22:6n-3/C18:3n-3, reflecting the overall conversion in the n-6 and n-3 PUFA pathway, respectively, were 0.29 and 0.35, respectively, with total FA content in the model and increased to 0.38 and 0.49, respectively, if total FA content was not in the model. Heritabilities for other more specific indices were of the same order. Genetic correlations between PUFA proportions and indices for enzyme activities with ADG were mostly negative, whereas the correlations with carcass lean meat percentage were mostly positive. It was concluded that there is meaningful genetic variation for long-chain PUFA metabolism that is only partly dependent on the carcass and muscle fat content. This may allow selection for improved FA composition of pork.

Visceral adiposity, increased adipocyte lipolysis, and metabolic dysfunction in obese postmenopausal women.

This study determines whether there are regional differences in lipolysis and whether adipocyte lipolysis is associated with the degree of visceral adiposity and its metabolic complications in 32 obese (28-37 kg/m2), nondiabetic, postmenopausal women. In vitro lipolysis was measured in the basal state and after addition of epinephrine (Epi), Epi plus yohimbine, Epi plus propranolol, and N6,2'-O-dibutyryl adenosine 3',5'-cyclic monophosphate (DBcAMP) in abdominal (ABD) and gluteal (GLT) adipocytes. Upper body obese [UBO, waist-to-hip ratio (WHR) > or = 0.80, n = 19] women had a greater intra-abdominal fat area (IA, 199 +/- 50 vs. 142 +/- 28 cm2) and Epi-stimulated lipolysis (ABD: 1.60 +/- 1.10 vs. 0.95 +/- 0.54 mumol glycerol.10(6) cells-1.2h; GLT: 1.14 +/- 0.70 vs. 0.66 +/- 0.42 mumol glycerol.10(6) cells-1.2 h) than lower body obese (LBO, WHR < 0.80, n = 13) women. The UBO women also had lower high-density lipoprotein cholesterol (1.39 +/- 0.40 vs. 1.64 +/- 0.39 mmol/l, P < 0.05), higher plasma triglycerides (1.89 +/- 0.48 vs. 1.44 +/- 0.56 mmol/l, P < 0.05), and higher fasting insulin levels (154 +/- 57 vs. 118 +/- 33 pmol/l, P < 0.05) than LBO women. Basal, adrenergic receptor-mediated, and DBcAMP-stimulated lipolytic rates in ABD and GLT adipocytes were positively correlated with IA (r = 0.44-0.76, P < 0.05, n = 28). In both UBO and LBO women, Epi-stimulated lipolysis was higher (+30%, P < 0.05) in ABD than GLT adipocytes. These results show that, in postmenopausal women, visceral obesity is associated with increased rates of lipolysis in both ABD and GLT subcutaneous adipocytes. The findings also indicate that Epi-stimulated lipolysis is greater in ABD than GLT adipocytes regardless of fat distribution.

Physiological predictors of increasing total and central adiposity in aging men and women.

BACKGROUND: Increasing levels of total and central body fat with advancing age contribute to the development of cardiovascular and metabolic disease. We examined gender-related differences and physiological predictors of the rate of increase in total and central body fat in men and women. METHODS: We studied 427 healthy men (age range, 17 to 90 years) and 293 women (age range, 18 to 88 years). We measured body fatness by hydrostatic weighing, central adiposity from the waist circumference, peak volume of oxygen utilization (VO2) from a treadmill test, leisure time physical activity (LTA) from a questionnaire, resting metabolic rate and respiratory quotient from indirect calorimetry, and energy intake from 3-day food diaries. RESULTS: Fat mass increased with age, and the rate was greater in women (r = .61; slope = 0.25 kg/y; P < .01) than in men (r = .43; slope = 0.16 kg/y; P < .01). Increasing fat mass in men and women was most strongly associated with declines in peak VO2 and LTA. Controlling for these variables reduced the increase in fat mass from 17% to 3% per decade in men and from 26% to 5% per decade in women. The increase in waist circumference with age was also greater in women (r = .53; slope = 0.28 cm/y) than in men (r = .39; slope = 0.18 cm/y; P < .01). Increasing waist circumference with age in men and women was most strongly associated with declines in LTA and peak VO2, respectively. Control for these variables reduced the age-related increase in waist circumference from 2% to 1% per decade in men and from 4% to 1% per decade in women. We observed no independent contribution of resting metabolic rate, respiratory quotient, menopause status, energy, or macronutrient intake to the age-related increase in fat mass and waist circumference. CONCLUSIONS: Our findings suggest that (1) the age-related increase in fat mass and waist circumference is greater in women than in men and (2) the physiological characteristics that reflect a decline in physical activity-related energy expenditure, rather than resting energy expenditure, are important predictors of the increases in total and central fatness. Lifestyle changes that increase the level of physical activity may be advantageous in blunting age-related increases in total and central body fatness.

Effects of weight loss vs aerobic exercise training on risk factors for coronary disease in healthy, obese, middle-aged and older men. A randomized controlled trial.

OBJECTIVE: To compare the effects of weight loss vs aerobic exercise training on coronary artery disease risk factors in healthy sedentary, obese, middle-aged and older men. DESIGN: Randomized controlled trial. SUBJECTS: A total of 170 obese (body mass index, 30 +/- 1 kg/m2 [mean +/- SEM]), middle-aged and older (61 +/- 1 years) men. INTERVENTIONS: A 9-month diet-induced weight loss interventions, 9-month aerobic exercise training program, and a weight-maintenance control group. MAIN OUTCOME MEASURES: Change in body composition, maximal aerobic capacity (V02 max), blood pressure, lipoprotein concentrations, and glucose tolerance. RESULTS: Forty-four of 73 men randomized to weight loss completed the intervention and had a 10% mean reduction in weight (- 9.5 +/- 0.7 kg; P < .001), with no 22 change in VO2 max. Forty-nine of 71 men randomized to aerobic exercise completed the intervention, increased their VO2 max by a mean of 17% (P < .001), and did not change their weight, whereas the 18 men who completed in the control group had no significant changes in body composition or VO2 max. Weight loss decreased fasting glucose concentrations by 2%, insulin by 18%, and glucose and insulin areas during the oral glucose tolerance test (OGTT) by 8% and 26%, respectively (P < .01). By contrast, aerobic exercise did not improve fasting glucose or insulin concentrations or glucose responses during the OGTT but decreased insulin areas by 17% (P < .001). In analysis of variance, the decrement in fasting glucose and insulin levels and glucose areas with intervention differed between weight loss and aerobic exercise when compared with the control group (P < .05). Similarly, weight loss but not aerobic exercise increased high-density lipoprotein cholesterol levels (+ 13%) and decreased blood pressure compared with the control group. In multiple regression analyses, the improvement in lipoprotein and glucose metabolism was related primarily to the reduction in obesity. CONCLUSIONS: These results suggest that weight loss is the preferred treatment to improve coronary artery disease risk factors in overweight, middle-aged and older men.

Weight loss reduces abdominal fat and improves insulin action in middle-aged and older men with impaired glucose tolerance.

Aging is associated with an increased accumulation of abdominal fat, glucose intolerance, and insulin resistance. We tested the hypothesis that diet-induced weight loss would reduce the abdominal distribution of fat and improve glucose tolerance and insulin action in a group of obese middle-aged and older men with normal or impaired glucose tolerance (IGT). Oral glucose tolerance tests (OGTTs) were performed at baseline and after 9 months of diet-induced weight loss in 35 men (mean age, 60 +/- 8 years). Fifteen men of comparable age and degree of obesity who did not participate in the weight loss intervention served as controls. Subjects lost 9.0 +/- 2.0 kg (mean +/- SD) body weight (P < .001), resulting in a 19% reduction in percent body fat (30.0 +/- 4.0% to 24.0% +/- 4.0%, P < .001), an 8% reduction in waist circumference (104.0 +/- 7.0 to 96.0 +/- 7.0 cm, P < .001), and a 2% reduction in waist to hip ratio [WHR] (0.97 +/- 0.06 to 0.95 +/- 0.06, P < .01). Weight loss improved glucose tolerance: nine men with IGT at baseline reverted to normal glucose tolerance following the intervention. Glucose area during the OGTT was significantly reduced after weight loss (-22.0%, P < .001), while it increased in control subjects (+32%, P < .004). In multiple regression analysis, the improvement in glucose area following weight loss in these 35 men was attributed to the reduction in waist circumference (P < .01) and baseline glucose area (P < .05).(ABSTRACT TRUNCATED AT 250 WORDS)