Organic super-reducing photocatalysts generate solvated electrons via two consecutive photon induced processes.

Photocatalysts with extremely strong reducing potential are often thought to operate through a consecutive photoinduced electron transfer (ConPeT) mechanism, where a first photon generates the radical anion of the photocatalyst via electron transfer and a second photon excites the radical anion into a super-reducing agent. Among them, 4CzIPN, (2,4,5,6-tetrakis(9H-carbazol-9-yl) isophthalonitrile) and the analogous 4DPAIPN (2,4,5,6-tetrakis(diphenylamino)isophthalonitrile) are supposed to operate following this principle, but the knowledge of the photophysical properties of the photogenerated radical anions is still very limited. An in-depth spectroscopic and computational study of their radical anions demonstrates that the excited states of 4CzIPN˙- and 4DPAIPN˙- are not behaving as super-reducing agents: they are very short lived (ca. 20 ps), not emissive and not quenched by common organic substrates. Most importantly, longer lived solvated electrons are generated upon excitation of these radical anions in acetonitrile and we propose that it is the solvated electron the species responsible for the exceptional reducing capability of this photocatalytic system.

Rhizophagus intraradices and Azospirillum brasilense improve growth of herbaceous plants and soil biological activity in revegetation of a recovering coal-mining area.

We assessed, in a field experiment, the effects of arbuscular mycorrhizal fungi (Rhizophagus intraradices) and plant growth-promoting bacteria (Azospirillum brasilense) on the soil biological activity and the growth of key pioneer species used in the revegetation of coal-mining areas undergoing recovery. We applied four inoculation treatments to the pioneer plant species (Lablab purpureus, Paspalum notatum, Crotalaria juncea, Neonotonia wightii, Stylosanthes guianensis, Andropogon gayanus and Trifolium repens) used in the recovery process: NI (Control - Non-inoculated), AZO (A. brasilense), AMF (R. intraradices), and co-inoculation of AZO and AMF. On the 75th and 180th days, we measured plant dry mass, mycorrhizal colonization, N and P concentration, and accumulation in plant tissue. We collected soil to quantify glomalin content and soil enzyme activity. After 180 days, we did a phytosociological characterization of the remaining spontaneous plants.The both microorganisms, singly or co-inoculated, promoted increases in different fractions of soil glomalin, acid phosphatase activity, and fluorescein diacetate activity at 75 and 180 days. The inoculation was linked to higher plant biomass production (62-89%) and increased plant P and N accumulation by 34-75% and 70-85% at 180 days, compared with the non-inoculated treatment. Among the pioneer species sown Crotalaria juncea produced the highest biomass at the 75th and 180th days (67% and 76% of all biomass), followed by Lablab purpureus (3% and 0.5%), while the other species failed to establish. At 180 days, we observed twenty spontaneous plant species growing in the area, primarily from the Poaceae family (74%). That suggests that the pioneer species present in the area do not hinder the ecological succession process. Inoculation of R. intraradices and A. brasilense, isolated or combined, increases soil biological activity, growth, and nutrient accumulation in key pioneer plant species, indicating the potential of that technique for the recovery of lands degraded by coal mining.

Int&in: A machine learning-based web server for active split site identification in inteins.

Inteins are proteins that excise themselves out of host proteins and ligate the flanking polypeptides in an auto-catalytic process called protein splicing. In nature, inteins are either contiguous or split. In the case of split inteins, the two fragments must first form a complex for the splicing to occur. Contiguous inteins have previously been artificially split in two fragments because split inteins allow for distinct applications than contiguous ones. Even naturally split inteins have been split at unnatural split sites to obtain fragments with reduced affinity for one another, which are useful to create conditional inteins or to study protein-protein interactions. So far, split sites in inteins have been heuristically identified. We developed Int&in, a web server freely available for academic research (https://intein.biologie.uni-freiburg.de) that runs a machine learning model using logistic regression to predict active and inactive split sites in inteins with high accuracy. The model was trained on a dataset of 126 split sites generated using the gp41-1, Npu DnaE and CL inteins and validated using 97 split sites extracted from the literature. Despite the limited data size, the model, which uses various protein structural features, as well as sequence conservation information, achieves an accuracy of 0.79 and 0.78 for the training and testing sets, respectively. We envision Int&in will facilitate the engineering of novel split inteins for applications in synthetic and cell biology.

Modulation of the Excited States of Ruthenium(II)-perylene Dyad to Access Near-IR Luminescence, Long-Lived Perylene Triplet State and Singlet Oxygen Photosensitization.

Herein, we present a novel ruthenium(II)-perylene dyad (RuPDI-Py) that combines the photophysical properties of pyrrolidine-substituted perylene diimide (PDI-Py) and the ruthenium(II) polypyridine complex [Ru(phen)3]2+. A comprehensive study of excited-state dynamics was carried out using time-resolved and steady-state methods in a dimethyl sulfoxide solution. The RuPDI-Py dyad demonstrated excitation wavelength-dependent photophysical behavior. Upon photoexcitation above 600 nm, the dyad exclusively exhibits the near-infrared (NIR) fluorescence of the 1PDI-Py state at 785 nm (τfl = 1.50 ns). In contrast, upon photoexcitation between 350 and 450 nm, the dyad also exhibits a photoinduced electron transfer from the {[Ru(phen)3]2+} moiety to PDI-Py, generating the charge-separated intermediate state {Ru(III)-(PDI-Py)•-} (4 µs). This state subsequently decays to the long-lived triplet excited state 3PDI-Py (36 µs), which is able to sensitize singlet oxygen (1O2). Overall, tuning 1O2 photoactivation or NIR fluorescence makes RuPDI-Py a promising candidate for using absorbed light energy to perform the desired functions in theranostic applications.

Soil phosphorus availability and uptake by mycorrhizal and non-mycorrhizal plants in an onion no-tillage system / Disponibilidade e absorção de fósforo no solo por plantas micorrízicas e não micorrízicas em sistema de plantio direto de cebola

ABSTRACT: Onion is an important vegetable crop, predominantly grown under conventional tillage system management. Alternatively, the vegetable no-tillage system uses cover crops to form a residue layer, which improves soil physical, chemical, and biological attributes. Aiming to understand the interaction of mycorrhizal and non-mycorrhizal cover crops, phosphatase activity, and soil phosphorus availability and uptake by plants, a no-tillage vegetable production system experiment with onion was carried out in Ituporanga, Southern Brazil. The treatments were black oats (Avena strigosa); rye (Secale cereale); oilseed radish (Raphanus sativus); rye + oilseed radish; black oats + oilseed radish, and a control with spontaneous plants. Additionally, two plots, a conventional tillage system area and a forest, both adjacent to the experiment, were evaluated. We measured cover crop biomass, onion yield, acid phosphatase activity, and resin-extracted phosphorus in the soil, shoot and root phosphorus content, and root colonization in cover crops, spontaneous plants, and onions. The treatments with cover crops had the highest plant biomass in winter and onion yield. Available soil phosphorus and acid phosphatase activity were higher in no-tillage plots than in the conventional tillage system area. The presence of non-mycorrhizal oilseed radish was associated with decreased colonization of rye and onion roots by arbuscular mycorrhizal fungi. No-tillage areas with cover crops or spontaneous plants in winter accumulated more phosphorus than conventional tillage system areas. The conventional tillage system showed adverse effects on most soil attributes, as shown by a Principal Component Analysis.

RESUMO: A cebola é uma importante cultura vegetal, cultivada predominantemente sob sistema de preparo convencional. Como alternativa, o sistema de plantio direto de hortaliças utiliza culturas de cobertura para formar uma camada de biomassa, o que melhora os atributos físicos, químicos e biológicos do solo. Com o objetivo de entender a interação de culturas de cobertura micorrízicas e não-micorrízicas, atividade da fosfatase ácida e disponibilidade e absorção de fósforo do solo pelas plantas, foi realizado um experimento em sistema de plantio direto de hortaliças com a cultura da cebola em Ituporanga, sul do Brasil. Os tratamentos foram: aveia preta (Avena strigosa); centeio (Secale cereale); nabo forrageiro (Raphanus sativus); centeio + nabo forrageiro; aveia preta + nabo forrageiro e um controle com vegetação espontânea. Além disso, duas outras parcelas, uma área em sistema de preparo convencional e uma floresta, ambas adjacentes ao experimento, foram avaliadas. Medimos a biomassa da cultura de cobertura, o rendimento de cebola, a atividade de fosfatase ácida e o fósforo extraído por resina no solo, bem como o conteúdo de fósforo da parte aérea e da raiz e a colonização das raízes em plantas de cobertura, plantas espontâneas e cebolas. Os tratamentos com plantas de cobertura apresentaram a maior biomassa de culturas de cobertura e rendimento de cebola. A atividade de fosfatase ácida e fósforo disponível no solo foram maiores nas parcelas de plantio direto do que na área convencional. A presença de nabo forrageiro, uma planta não micorrízica, foi associada a reduções na colonização de raízes de centeio e cebola por fungos micorrízicos arbusculares. As áreas de plantio direto com plantas de cobertura ou plantas espontâneas no inverno acumularam mais fósforo do que as áreas com preparo convencional. O sistema convencional de lavoura mostrou efeitos adversos para a maioria dos atributos do solo, como mostra a Análise de Componentes Principais.

Matéria seca de plantas de cobertura, produção de cebola e atributos químicos do solo em sistema plantio direto agroecológico / Dry matter of cover crops, onion yield and soil chemical attributes in agroecological no-tillage system

O cultivo e a deposição de resíduos de plantas de cobertura em sistema plantio direto podem afetar os atributos químicos do solo e a produção de cebola. O trabalho objetivou avaliar a interferência do cultivo de plantas de cobertura sobre a produção de cebola e sobre os atributos químicos do solo em sistema plantio direto (SPD) agroecológico. O experimento foi conduzido na EPAGRI, em Ituporanga (SC), em um Cambissolo Húmico, nas safras de 2010 e 2011. Em abril, foram implantados os tratamentos: testemunha com vegetação espontânea (T1); cevada (2010)/aveia-preta (2011) (T2); centeio (T3); nabo-forrageiro (T4); centeio + nabo-forrageiro (T5); e cevada (2010)/aveia-preta (2011) + nabo-forrageiro (T6). Aos 60, 80 e 95 dias após a semeadura (DAS) das espécies de inverno, coletou-se a parte aérea das plantas e determinou-se a produção de matéria seca por hectare. Em julho, foram transplantadas mudas de cebola e, em novembro, avaliou-se a produção. Após o acamamento das plantas de cobertura de inverno e a colheita da cebola, foi coletado solo na camada de 0-10 cm e submetido à análise de atributos químicos. O cultivo e a deposição dos resíduos de matéria seca das espécies de plantas de cobertura em SPD contribuíram para o aumento e a manutenção da produção total de cebola ao longo dos anos. Os atributos químicos do solo, com exceção do K trocável, P disponível e valores de saturação da CTCpH7,0 por bases não foram afetados pelo cultivo de plantas de cobertura.

The cultivation and deposition of waste from cover crops in no-tillage can affect soil chemical attributes and onion yield. The aim of this study was to evaluate the dry matter yield of plant species from winter cover crops, onion yield and chemical attributes of soil in agroecological no-tillage system. The experiment was carried out at EPAGRI Experimental Station in Ituporanga (SC) under Humic Haplumbrept in the agricultural years of 2010 and 2011. The following treatments was implanted in April: weed vegetation (T1), Hordeum vulgare L. (2010)/Avena strigosa L. (2011) (T2), Secale cereale L. (T3), Raphanus sativus L. (T4), Secale cereale L + Raphanus sativus L. (T5) e Hordeum vulgare L. (2010)/Avena strigosa L. (2011) + Raphanus sativus L. (T6). At 60, 80 and 95 days after sowing (DAS) of winter species, the cover crops were collected to determine the dry matter yield. In July the onion seedlings were transplanted and in November the yield was evaluated. After the rolling of winter cover crops and after onion harvest, soil was collected at 0-10cm for the evaluation of chemical attributes. The cultivation and deposition of waste from cover crops in no-tillage contributed to the growth and maintenance of the total production of onion over the years. The soil chemical attributes in 0-10cm layer, with the exception of exchangeable K, available P and CTCpH7,0 saturation values for bases, were not affected by cover crops cultivation and deposition of waste.

Prevalencia de hiperreactividad cardiovascular en personas con presión arterial normal del área urbana del municipio de Cienfuegos / Prevalence of cardiovascular hyperreactivity in individuals with normal blood pressure in the urban area of Cienfuegos

Fundamento: la hiperreactividad cardiovascular constituye un marcador de riesgo cardiovascular, sin embargo, su prevalencia no es bien conocida por la población. Objetivo: describir la prevalencia de la hiperreactividad cardiovascular en la población de personas normotensas del área urbana del municipio de Cienfuegos.Método: se realizó un estudio descriptivo de corte transversal. La muestra estuvo constituida por 859 normotensos a los cuales se les aplicó la prueba del peso sostenido. Las variables estudiadas fueron: edad, sexo, color de la piel, nivel de escolaridad, estado conyugal y las relacionadas con la hiperreactividad cardiovascular: presión sistólica, presión diastólica, presión arterial media, presión diferencial, índice de reactividad cardiovascular. Se determinó la razón de prevalencia en el intervalo con su intervalo de confianza del 95 por ciento. En algunos casos se realizó la prueba chi cuadrado de Pearson con un nivel de significación del 95 por cientoResultados: la prevalencia de hiperreactividad cardiovascular fue de 45,1 por ciento IC 95 por ciento (41,8; 48,5). Se observó una razón de prevalencia de 1,44 IC 95 por ciento (1,2;1,6) veces mayor en los hombres en relación a las mujeres. El 44,5 por ciento de los blancos y el 46,8 por ciento de los negros tuvieron hiperreactividad cardiovascular, así como el 52,8 por ciento de las personas con más de 40 años por solo el 38,1 por ciento cuando la edad era menor a este nivel. Conclusiones: la prevalencia de hiperreactividad cardiovascular es alta, y mayor en los hombres, en los obesos y en los que tienen una edad superior a los 40 años(AU)

Background: cardiovascular hyperactivity is a marker of cardiovascular risk. Nevertheless, its prevalence in the population is not well known. Objective: to describe the prevalence of cardiovascular hyperreactivity in individuals with normal blood pressure in the population of the urban area in the municipality of Cienfuegos. Methods: a cross-sectional and descriptive study was performed. The sample consisted of 859 normotensive individuals who were applied the sustained weight test. The variables studied were age, sex, skin color, educational level, marital status and related cardiovascular hyperreactivity: systolic pressure, diastolic pressure, average arterial pressure, differential pressure and cardiovascular reactivity index. Their relative frequencies trusts intervals. We determined the prevalence ratio interval with a confidence interval of 95 percent. In some cases Pearsons Chi square test was performed with a significance level of 95 percent. Results: the prevalence of cardiovascular hyperreactivity was 45,1 percent (9 5 percent CI 1,8-48,5). There was a prevalence ratio of 1,44 (95 percent CI 1,2-1,6) times higher in men in relation to women. 44,5 percent of white skinned individuals and 46,8 percent of black skinned individuals presented cardiovascular hyperreactivity as well as 52,8 percent of those with more than 40 years and only 38,1 percent in ages under this level. Conclusions: the prevalence of cardiovascular hyperreactivity is high and even higher in men, obese individuals and in those older than 40 years(AU)