Porphyrin–nanodiamond hybrid materials—active, stable and reusable cyclohexene oxidation catalysts

funded by FCT-Foundation for Science and Technology, I.P., under projects UIDB/00313/2020; PTDC/QUI-OUT/27996/2017 (DUALPI); POCI-01-0145-FEDER-027996; POCI-01-0145-FEDER-016387; UIDB/50006/2020 (Associate Laboratory for Green Chemistry-LAQV); MATIS (CENTRO-010145-FEDER-00014); Base Funding-UIDB/50020/2020 of the Associate Laboratory LSRE-LCM-funded by national funds through FCT/MCTES (PIDDAC); and 5625-DRI-DAAD-2020/21. SACC also acknowledges FCT Investigador FCT program (IF/01381/2013/CP1160/CT0007) and Scientific Employment Stimulus -Institutional Call (CEECINST/00102/2018). The authors also thank Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP) for CEPOF 2013/07276-1, and INCT "Basic Optics and Applied to Life Sciences" (FAPESP 2014/50857-8, CNPq 465360/2014-9). A.R.L. Caires acknowledges CAPES-PrInt funding program (grant number 88887.353061/2019-00 and 88881.311921/2018-01). J.G.B. thanks the Dutch Research Council (NWO) for funding as a part of the Open Technology Programme (project number 16361). L.D. Dias thanks FAPESP for the Post-doc grant 2019/13569-8. F.M.S.R. thanks FCT for the PhD grant (PD/BD/114340/2016).The quest for active, yet “green” non-toxic catalysts is a continuous challenge. In this work, covalently linked hybrid porphyrin–nanodiamonds were prepared via ipso nitro substitution reaction and characterized by X-ray photoelectron spectroscopy (XPS), fluorescence spectroscopy, infrared spectroscopy (IR) and thermogravimetry-differential scanning calorimetry (TG-DSC). The amine-functionalized nanodiamonds (ND@NH2 ) and 2-nitro-5,10,15,20-tetra(4-trifluoromethylphenyl)porphyrin covalently linked to nanodiamonds (ND@βNH-TPPpCF3 ) were tested using Allium cepa as a plant model, and showed neither phytotoxicity nor cytotoxicity. The hybrid nanodiamond–copper(II)–porphyrin material ND@βNH-TPPpCF3-Cu(II) was also evaluated as a reusable catalyst in cyclohexene allylic oxidation, and displayed a remarkable turnover number (TON) value of ≈265,000, using O2 as green oxidant, in the total absence of sacrificial additives, which is the highest activity ever reported for said allylic oxidation. Additionally, ND@βNH-TPPpCF3-Cu(II) could be easily separated from the reaction mixture by centrifugation, and reused in three consecutive catalytic cycles without major loss of activity.publishersversionpublishe

Phytotoxicity of silver nanoparticles on Vicia faba: evaluation of particle size effects on photosynthetic performance and leaf gas exchange

Nanotechnology is an emerging field in science and engineering, which presents significant impacts on the economy, society and the environment. The nanomaterials’ (NMs) production, use, and disposal is inevitably leading to their release into the environment where there are uncertainties about its fate, behaviour, and toxicity. Recent works have demonstrated that NMs can penetrate, translocate, and accumulate in plants. However, studies about the effects of the NMs on plants are still limited because most investigations are carried out in the initial stage of plant development. The present study aimed to evaluate and characterize the photochemical efficiency of photosystem II (PSII) of broad bean (Vicia faba) leaves when subjected to silver nanoparticles (AgNPs) with diameters of 20, 51, and 73 nm as well as to micrometer-size Ag particles (AgBulk). The AgNPs were characterized by transmission electron microscopy and dynamic light scattering. The analyses were performed by injecting the leaves with 100 mg L-1 aqueous solution of Ag and measuring the chlorophyll fluorescence imaging, gas exchange, thermal imaging, and reactive oxygen species (ROS) production. In addition, silver ion (Ag+) release from Ag particles was determined by dialysis. The results revealed that AgNPs induce a decrease in the photochemical efficiency of photosystem II (PSII) and an increase in the non-photochemical quenching. The data also revealed that AgNPs affected the stomatal conductance (gs) and CO2 assimilation. Further, AgNPs induced an overproduction of ROS in Vicia faba leaves. Finally, all observed effects were particle diameter-dependent, increasing with the reduction of AgNPs diameter and revealing that AgBulk caused only a small or no changes on plants. In summary, the results point out that AgNPs may negatively affect the photosynthesis process when accumulated in the leaves, and that the NPs themselves were mainly responsible since negligible Ag+ release was detected

High-throughput phenotyping by applying digital morphometrics and fluorescence induction curves in seeds to identifying variations: A case study of Annona (Annonaceae) species

Differences in physical and structural characteristics of seeds may indicate variability within and between plant populations. In the present study, we performed a close characterization of dimension, shape, and tegument delayed chlorophyll fluorescence in seeds obtained from three species of the genus Annona (Annonaceae), i.e., Annona coriacea, A. montana, A. squamosa. Results showed that studied seeds may be sorted as scalene ellipsoids expressing low values for the seed sphericity. The morphological estimates suggested differences in seed shape for all species. A high correlation was observed between surface area and volume (r2 > 99%) for all the three species suggesting that in addition to structural shape. In addition, we also observed very high positive correlations (Rho = 1.000, p < 0.001) between surface area and arithmetic mean diameterof the seeds for all species. The first principal component (PCA1) of elliptical Fourier descriptors explained most of the variations in morphological structure of the seeds in the three species. Additionally, a less intense tegument delayed chlorophyll fluorescence was observed for A. montana while the highest intensity was recorded for A. squamosa, revealing the potential use of fluorescence spectroscopy in discrimination at the species level by analyzing the frequency domain by means of Fourier Transform spectra as well as the relationship time-frequency of chlorophyll fluorescence. Keywords: Dynamics of fluorescence, Fourier descriptors, Structural traits, Phenomic

Alterações em atributos do solo decorrentes da aplicação de nitrogênio e palha em sistema semeadura direta na cultura do milho Changes in soil properties due to application of nitrogen and straw in maize grown under no-till system

Nos últimos anos, tem-se procurado elevar os teores de C orgânico do solo e, ao mesmo tempo, aumentar a produtividade das culturas. Neste contexto, o sistema semeadura direta (SSD) tem importante participação, principalmente na região dos Cerrados. Entretanto, para se alcançar altas produtividades, as gramíneas requerem a adição de doses elevadas de adubos nitrogenados. Este trabalho teve por objetivo avaliar as alterações no solo decorrentes da aplicação de palha e de N em solo cultivado com milho por 10 anos (1991-2001) em SSD. O experimento foi desenvolvido na Embrapa-Milho e Sorgo, em Sete Lagoas-MG, em um Latossolo Vermelho distrófico típico sob cerrado. Os tratamentos constaram da combinação de palha sobre o solo (0, 3, 6, 9 e 12Mg ha-1 de matéria seca) dispostas nas parcelas, e de cinco níveis de N aplicados em cobertura (0, 40, 80, 120 e 160kg ha-1), na forma de uréia, dispostos nas subparcelas. Foram realizadas duas coletas de solo (antes e após uma calagem), nas profundidades de 0-0,025; 0,025-0,05; 0,05-0,10; 0,10-0,20; 0,20-0,40m. Análises químicas e físicas de rotina foram efetuadas usando-se métodos padrões. Os teores de C orgânico e de K foram influenciados pelas doses de palha e aumentaram à medida que se aumentou a aplicação de palha sobre o solo. A variação nas doses de N promoveu alterações no pH, nos teores de Ca, Mg e nas saturações por bases e por Al até a profundidade de 0,20m. A calagem superficial promoveu o aumento do pH do solo em profundidade e dos teores de Ca, até 0,20m, provavelmente devido à alta pluviosidade no período pós-calagem (1600mm em oito meses).<br>Agricultural practices have been trying to increase the content of organic C in soils and at the same time to increase yields. In this context, the no-till system (NTS) has an important role to play, particularly in the Cerrado region of Brazil. However, to reach high yields, the crops demand high inputs of N fertilizers. The objective of this work was to evaluate the modifications induced in the soil after ten years (1991-2001) of NTS, influenced by different straw and N doses. The experiment was set at the Embrapa farm in Sete Lagoas-MG, on a typic Dystrofic Red Latosol under Cerrado vegetation. The treatments consisted of five straw doses (0, 3, 6, 9 e 12Mg ha-1 of dry matter) in the plot and five doses of N (0, 40, 80, 120 e 160kg ha-1) as urea in the subplot. Two samplings were accomplished, before and after liming. The soil layers sampled were 0-0.025; 0.025-0.05; 0.05-0.10; 0.10-0.20; and 0.20-0.40m. Routine soil physical and chemical variables were measured according to standard procedures. The contents of organic C and K were influenced by the different straw doses and increased as the application of straw increased. The different doses of N influenced pH, Ca, Mg, Al, base and Al saturation, up to 0.20m. The surface liming was capable of increasing pH, in some cases up to 0.20m, and the same happened for Ca. The vertical movement of the lime in the profile was probably due to the good physical properties of the soil and to the heavy rainfall (1600mm in eight months)

Electrochemical attributes and availability of nutrients, toxic elements, and heavy metals in tropical soils Atributos eletroquímicos e disponibilidade de nutrientes, elementos tóxicos e metais pesados em solos tropicais

Electrochemical properties of soils are very important for the understanding of the physico-chemical phenomena which affect soil fertility and the availability of nutrients for plants. This review highlights the electrochemical properties of tropical soils, the behavior and the availability of nutrients, toxic elements and heavy metals in the soil, especially for soils with predominant variable charge minerals. Availability of the elements is related to ionic exchange, solution speciation, and electrostatic and specific adsorptive soil properties. Empirical and surface complexation models are briefly described, and some results of their application in tropical soils are presented. A better understanding of the role of the double diffuse layer of charges and CEC on nutrient cation availability for highly weathered soils is required, as well as a solid comprehension of surface complexation models, in order to improve the knowledge regarding the behavior of anions in soils. More studies have to be conducted to generate results that enable the use of chemical speciation concepts and calculation of several constants used in surface complexation models, especially for highly weathered soils from the humid tropics. There has to be a continuing development and use of computer softwares that have already incorporated the concepts of chemical speciation and adsorption models in the study of nutrients, toxic elements and heavy metal availability in the soil-plant system.<br>As propriedades eletroquímicas dos solos tropicais são muito importantes para entendimento dos fenômenos físico-químicos que afetam a fertilidade do solo e a disponibilidade dos nutrientes das plantas. Essa revisão destaca os atributos eletroquímicos de solos e o comportamento e a disponibilidade de nutrientes, elementos tóxicos e metais pesados no solo, especialmente aqueles com predominância de minerais com cargas variáveis. A disponibilidade dos elementos é relacionada com a troca iônica, especiação da solução e propriedades adsortivas eletrostáticas e específicas do solo. Modelos empíricos e de complexação de superfície são brevemente descritos, e são apresentados resultados de sua aplicação em solos tropicais. É necessário um melhor entendimento do papel da dupla camada difusa de cargas e da CTC na disponibildade de nutrientes em solos altamente intemperizados, assim como uma melhor compreensão dos modelos de complexação de superfície, a fim de melhorar o entendimento do comportamento dos ânions no solo. Mais estudos devem ser conduzidos para gerar resultados que tornem possível o uso de conceitos de especiação química e o cálculo de diversas constantes usadas em modelos de complexação, especialmente para solos altamente intemperizados do trópico úmido. Deve haver um contínuo desenvolvimento de programas computacionais que já tenham incorporado os conceitos de especiação e modelos de adsorção no estudo da disponibilidade de nutrientes, elementos tóxicos e metais pesados no sistema solo-planta

Brazilian Flora 2020: Leveraging the power of a collaborative scientific network

International audienceThe shortage of reliable primary taxonomic data limits the description of biological taxa and the understanding of biodiversity patterns and processes, complicating biogeographical, ecological, and evolutionary studies. This deficit creates a significant taxonomic impediment to biodiversity research and conservation planning. The taxonomic impediment and the biodiversity crisis are widely recognized, highlighting the urgent need for reliable taxonomic data. Over the past decade, numerous countries worldwide have devoted considerable effort to Target 1 of the Global Strategy for Plant Conservation (GSPC), which called for the preparation of a working list of all known plant species by 2010 and an online world Flora by 2020. Brazil is a megadiverse country, home to more of the world's known plant species than any other country. Despite that, Flora Brasiliensis, concluded in 1906, was the last comprehensive treatment of the Brazilian flora. The lack of accurate estimates of the number of species of algae, fungi, and plants occurring in Brazil contributes to the prevailing taxonomic impediment and delays progress towards the GSPC targets. Over the past 12 years, a legion of taxonomists motivated to meet Target 1 of the GSPC, worked together to gather and integrate knowledge on the algal, plant, and fungal diversity of Brazil. Overall, a team of about 980 taxonomists joined efforts in a highly collaborative project that used cybertaxonomy to prepare an updated Flora of Brazil, showing the power of scientific collaboration to reach ambitious goals. This paper presents an overview of the Brazilian Flora 2020 and provides taxonomic and spatial updates on the algae, fungi, and plants found in one of the world's most biodiverse countries. We further identify collection gaps and summarize future goals that extend beyond 2020. Our results show that Brazil is home to 46,975 native species of algae, fungi, and plants, of which 19,669 are endemic to the country. The data compiled to date suggests that the Atlantic Rainforest might be the most diverse Brazilian domain for all plant groups except gymnosperms, which are most diverse in the Amazon. However, scientific knowledge of Brazilian diversity is still unequally distributed, with the Atlantic Rainforest and the Cerrado being the most intensively sampled and studied biomes in the country. In times of “scientific reductionism”, with botanical and mycological sciences suffering pervasive depreciation in recent decades, the first online Flora of Brazil 2020 significantly enhanced the quality and quantity of taxonomic data available for algae, fungi, and plants from Brazil. This project also made all the information freely available online, providing a firm foundation for future research and for the management, conservation, and sustainable use of the Brazilian funga and flora