Inverted critical adsorption of polyelectrolytes in confinement

What are the fundamental laws for the adsorption of charged polymers onto oppositely charged surfaces, for convex, planar, and concave geometries? This question is at the heart of surface coating applications, various complex formation phenomena, as well as in the context of cellular and viral biophysics. It has been a long-standing challenge in theoretical polymer physics; for realistic systems the quantitative understanding is however often achievable only by computer simulations. In this study, we present the findings of such extensive Monte-Carlo in silico experiments for polymer-surface adsorption in confined domains. We study the inverted critical adsorption of finite-length polyelectrolytes in three fundamental geometries: planar slit, cylindrical pore, and spherical cavity. The scaling relations extracted from simulations for the critical surface charge density $\sigma_c$-defining the adsorption-desorption transition-are in excellent agreement with our analytical calculations based on the ground-state analysis of the Edwards equation. In particular, we confirm the magnitude and scaling of $\sigma_c$ for the concave interfaces versus the Debye screening length $1/\kappa$ and the extent of confinement $a$ for these three interfaces for small $\kappa a$ values. For large $\kappa a$ the critical adsorption condition approaches the planar limit. The transition between the two regimes takes place when the radius of surface curvature or half of the slit thickness $a$ is of the order of $1/\kappa$. We also rationalize how $\sigma_c(\kappa)$ gets modified for semi-flexible versus flexible chains under external confinement. We examine the implications of the chain length onto critical adsorption-the effect often hard to tackle theoretically-putting an emphasis on polymers inside attractive spherical cavities.Comment: 12 pages, 10 figures, RevTe

Critical adsorption of polyelectrolytes onto charged Janus nanospheres

Based on extensive Monte Carlo simulations and analytical considerations we study the electrostatically driven adsorption of flexible polyelectrolyte chains onto charged Janus nanospheres. These net-neutral colloids are composed of two equally but oppositely charged hemispheres. The critical binding conditions for polyelectrolyte chains are analysed as function of the radius of the Janus particle and its surface charge density, as well as the salt concentration in the ambient solution. Specifically for the adsorption of finite-length polyelectrolyte chains onto Janus nanoparticles, we demonstrate that the critical adsorption conditions drastically differ when the size of the Janus particle or the screening length of the electrolyte are varied. We compare the scaling laws obtained for the adsorption-desorption threshold to the known results for uniformly charged spherical particles, observing significant disparities. We also contrast the changes to the polyelectrolyte chain conformations and the binding energy distributions close to the adsorption-desorption transition for Janus nanoparticles to those for simple spherical particles. Finally, we discuss experimentally relevant physico-chemical systems for which our simulations results may become important. In particular, we observe similar trends with polyelectrolyte complexation with oppositely but heterogeneously charged proteins.Comment: 13 pages, 11 figures, RevTeX

Retention of total carotenoid and β-carotene in yellow sweet cassava (Manihot esculenta Crantz) after domestic cooking

Background: Over the last decade, considerable efforts have been made to identify cassava cultivars to improve the vitamin A nutritional status of undernourished populations, especially in northeast Brazil, where cassava is one of the principal and essentially only nutritional source. Objectives: The aim of this study was to evaluate the total carotenoid, β-carotene, and its all-E-, 9-, and 13-Z-β-carotene isomers content in seven yellow sweet cassava roots and their retention after three boiling cooking methods. Design: The total carotenoid, β-carotene, and its all-E-, 9-, and 13-Z-β-carotene isomers in yellow sweet cassava samples were determined by ultraviolet/visible spectrometry and high-performance liquid chromatography, respectively, before and after applying the cooking methods. All analyses were performed in triplicate. Results: The total carotenoid in raw roots varied from 2.64 to 14.15 µg/g and total β-carotene from 1.99 to 10.32 µg/g. The β-carotene predominated in all the roots. The Híbrido 2003 14 08 cultivar presented the highest β-carotene content after cooking methods 1 and 3. The 1153 – Klainasik cultivar presented the highest 9-Z-β-carotene content after cooking by method 3. The highest total carotenoid retention was observed in cultivar 1456 – Vermelhinha and that of β-carotene for the Híbrido 2003 14 11 cultivar, both after cooking method 1. Evaluating the real retention percentage (RR%) in sweet yellow cassava after home cooking methods showed differences that can be attributed to the total initial carotenoid contents. However, no cooking method uniformly provided a higher total carotenoid or β-carotene retention in all the cultivars. Conclusion: Differences were found in the cooking methods among the samples regarding total carotenoid or β-carotene retention, suggesting that the different behaviors of the cultivars need to be further analyzed. However, high percentages of total carotenoid or β-carotene retention were observed and can minimize vitamin A deficiency in low-income populations

Selective oxidation of lupeol by iodosylbenzene catalyzed by manganese porphyrins.

Manganese porphyrin-catalyzed oxidation of lupeol by iodosylbenzenewas achieved undermild conditionswith low isolated yields but with remarkable selectivity, depending on the catalyst of choice. Mn(III) mesotetraphenylporphyrin and Mn(III) meso-tetrakis(4-carbomethoxyphenyl)porphyrin provided an entry for the preparation of 3?,30-dihydroxylup-20(29)-ene (6?14% yields), whereas Mn(III) ?-octabromo-meso-tetrakis(4- carbomethoxyphenyl)porphyrin led to 20-oxo-3?-hydroxy-29-norlupeol (6% yield), as single products. Unreacted lupeol was recovered in quantitative yield. The oxidative transformations at lupeol C20 or C30 take place with no need for protection of C3 hydroxyl moiety

An Efficient Strategy for Evaluating New Non-invasive Screening Tests for Colorectal Cancer: The Guiding Principles

OBJECTIVE: New screening tests for colorectal cancer (CRC) are rapidly emerging. Conducting trials with mortality reduction as the end point supporting their adoption is challenging. We re-examined the principles underlying evaluation of new non-invasive tests in view of technological developments and identification of new biomarkers. DESIGN: A formal consensus approach involving a multidisciplinary expert panel revised eight previously established principles. RESULTS: Twelve newly stated principles emerged. Effectiveness of a new test can be evaluated by comparison with a proven comparator non-invasive test. The faecal immunochemical test is now considered the appropriate comparator, while colonoscopy remains the diagnostic standard. For a new test to be able to meet differing screening goals and regulatory requirements, flexibility to adjust its positivity threshold is desirable. A rigorous and efficient four-phased approach is proposed, commencing with small studies assessing the test\u27s ability to discriminate between CRC and non-cancer states ( CONCLUSION: New non-invasive tests can be efficiently evaluated by a rigorous phased comparative approach, generating data from unbiased populations that inform predictions of their health impact

COMPLEXIDADE RACIAL: mitos e realidades em duas freguesias de Salvador em 1775

A partir da análise minuciosa dos dados do Censo de 1775 sobre duas freguesias de Salvador (São Pedro e Penha), são colocados em questão cinco mitos dominantes sobre a escravidão no imaginário nacional: (1) o domínio total do trabalho escravo na sociedade; (2) uma sociedade formada apenas por senhores e escravos; (3) uma sociedade constituída, por um lado, por um segmento de dominantes e exploradores e, por outro, por dominados e explorados; (4) uma sociedade urbana segregada; (5) uma sociedade patriarcal, em que as mulheres eram submissas e economicamente subordinadas. Os resultados do censo, portanto, levantam novas questões para o entendimento da complexidade do nosso passado, o que ajuda a entender a manutenção das extremas desigualdades atuais, além de evidenciar a existência de diferenciações espaciais na cidade. PALAVRAS-CHAVE: escravos, libertos, agregados, freguesias, Salvador.RACIAL COMPLEXITY: myth and reality in two Salvador freguesias in 1775 Pedro de Almeida Vasconcelos The meticulous analysis of data from the Census of 1775 on two freguesias of Salvador (São Pedro and Penha), bring doubt to five dominant myths on slavery in the national imaginary: (1) the exclusivity of slave work in the society; (2) a society just formed by slave owners and slaves; (3) a society where, on one side, live a segment of dominant exploiters and, on the other, dominated explored people; (4) a segregated urban society; (5) a patriarchal society, in which women were submissive and economically subordinates. The results of the census, therefore, bring new subjects to understanding the complexity of our past, what helps to understand the maintenance of the extreme current inequalities, besides showing the existence of space differentiations in the city. KEYWORDS: slaves, freed men, agregados, freguesias, Salvador.COMPLEXITÉ RACIALE: mythes et réalités dans deux paroisses de Salvador en 1775 Pedro de Almeida Vasconcelos A partir de l’analyse minutieuse des données du recensement de 1775 concernant deux paroisses de Salvador (São Pedro et Penha) sont remis en question cinq mythes dominants à propos de l’esclavage dans l’imaginaire national: (1) l’exclusivité du travail esclave dans la société; (2) une société formée uniquement de seigneurs et d’esclaves; (3) une société constituée d’une part par un segment de dominants et d’exploiteurs et d’autre part de dominés et d’exploités; (4) une société urbaine ségréguée; (5) une société patriarcale où les femmes étaient soumises et subordonnées économiquement. Les résultats de ce recensement soulèvent donc de nouvelles questions pour la compréhension de la complexité de notre passé, ceci permet de comprendre le maintien d’extrêmes inégalités actuelles et de mettre aussi en évidence l’existence de différenciations spatiales dans la ville. MOTS-CLÉS: esclaves, personnes libres, domestiques, paroisses, Salvador. Publicação Online do Caderno CRH: http://www.cadernocrh.ufba.b

Pervasive gaps in Amazonian ecological research

Biodiversity loss is one of the main challenges of our time,1,2 and attempts to address it require a clear un derstanding of how ecological communities respond to environmental change across time and space.3,4 While the increasing availability of global databases on ecological communities has advanced our knowledge of biodiversity sensitivity to environmental changes,5–7 vast areas of the tropics remain understudied.8–11 In the American tropics, Amazonia stands out as the world’s most diverse rainforest and the primary source of Neotropical biodiversity,12 but it remains among the least known forests in America and is often underrepre sented in biodiversity databases.13–15 To worsen this situation, human-induced modifications16,17 may elim inate pieces of the Amazon’s biodiversity puzzle before we can use them to understand how ecological com munities are responding. To increase generalization and applicability of biodiversity knowledge,18,19 it is thus crucial to reduce biases in ecological research, particularly in regions projected to face the most pronounced environmental changes. We integrate ecological community metadata of 7,694 sampling sites for multiple or ganism groups in a machine learning model framework to map the research probability across the Brazilian Amazonia, while identifying the region’s vulnerability to environmental change. 15%–18% of the most ne glected areas in ecological research are expected to experience severe climate or land use changes by 2050. This means that unless we take immediate action, we will not be able to establish their current status, much less monitor how it is changing and what is being lostinfo:eu-repo/semantics/publishedVersio