| 1. |
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| 2. |
- Elsik, Christine G., et al.
(författare)
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The Genome Sequence of Taurine Cattle : A Window to Ruminant Biology and Evolution
- 2009
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Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 324:5926, s. 522-528
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Tidskriftsartikel (refereegranskat)abstract
- To understand the biology and evolution of ruminants, the cattle genome was sequenced to about sevenfold coverage. The cattle genome contains a minimum of 22,000 genes, with a core set of 14,345 orthologs shared among seven mammalian species of which 1217 are absent or undetected in noneutherian (marsupial or monotreme) genomes. Cattle-specific evolutionary breakpoint regions in chromosomes have a higher density of segmental duplications, enrichment of repetitive elements, and species-specific variations in genes associated with lactation and immune responsiveness. Genes involved in metabolism are generally highly conserved, although five metabolic genes are deleted or extensively diverged from their human orthologs. The cattle genome sequence thus provides a resource for understanding mammalian evolution and accelerating livestock genetic improvement for milk and meat production.
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| 3. |
- Householder, John Ethan, et al.
(författare)
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One sixth of Amazonian tree diversity is dependent on river floodplains
- 2024
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Ingår i: NATURE ECOLOGY & EVOLUTION. - 2397-334X.
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Tidskriftsartikel (refereegranskat)abstract
- Amazonia's floodplain system is the largest and most biodiverse on Earth. Although forests are crucial to the ecological integrity of floodplains, our understanding of their species composition and how this may differ from surrounding forest types is still far too limited, particularly as changing inundation regimes begin to reshape floodplain tree communities and the critical ecosystem functions they underpin. Here we address this gap by taking a spatially explicit look at Amazonia-wide patterns of tree-species turnover and ecological specialization of the region's floodplain forests. We show that the majority of Amazonian tree species can inhabit floodplains, and about a sixth of Amazonian tree diversity is ecologically specialized on floodplains. The degree of specialization in floodplain communities is driven by regional flood patterns, with the most compositionally differentiated floodplain forests located centrally within the fluvial network and contingent on the most extraordinary flood magnitudes regionally. Our results provide a spatially explicit view of ecological specialization of floodplain forest communities and expose the need for whole-basin hydrological integrity to protect the Amazon's tree diversity and its function.
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| 4. |
- Bentham, James, et al.
(författare)
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A century of trends in adult human height
- 2016
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Ingår i: eLIFE. - 2050-084X. ; 5
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Tidskriftsartikel (refereegranskat)abstract
- Being taller is associated with enhanced longevity, and higher education and earnings. We reanalysed 1472 population-based studies, with measurement of height on more than 18.6 million participants to estimate mean height for people born between 1896 and 1996 in 200 countries. The largest gain in adult height over the past century has occurred in South Korean women and Iranian men, who became 20.2 cm (95% credible interval 17.522.7) and 16.5 cm (13.319.7) taller, respectively. In contrast, there was little change in adult height in some sub-Saharan African countries and in South Asia over the century of analysis. The tallest people over these 100 years are men born in the Netherlands in the last quarter of 20th century, whose average heights surpassed 182.5 cm, and the shortest were women born in Guatemala in 1896 (140.3 cm; 135.8144.8). The height differential between the tallest and shortest populations was 19-20 cm a century ago, and has remained the same for women and increased for men a century later despite substantial changes in the ranking of countries.
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| 5. |
- Bentham, James, et al.
(författare)
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A century of trends in adult human height
- 2016
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Ingår i: eLIFE. - : eLife Sciences Publications Ltd. - 2050-084X. ; 5
-
Tidskriftsartikel (refereegranskat)abstract
- Being taller is associated with enhanced longevity, and higher education and earnings. We reanalysed 1472 population-based studies, with measurement of height on more than 18.6 million participants to estimate mean height for people born between 1896 and 1996 in 200 countries. The largest gain in adult height over the past century has occurred in South Korean women and Iranian men, who became 20.2 cm (95% credible interval 17.5–22.7) and 16.5 cm (13.3– 19.7) taller, respectively. In contrast, there was little change in adult height in some sub-Saharan African countries and in South Asia over the century of analysis. The tallest people over these 100 years are men born in the Netherlands in the last quarter of 20th century, whose average heights surpassed 182.5 cm, and the shortest were women born in Guatemala in 1896 (140.3 cm; 135.8– 144.8). The height differential between the tallest and shortest populations was 19-20 cm a century ago, and has remained the same for women and increased for men a century later despite substantial changes in the ranking of countries.
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| 6. |
- Kattge, Jens, et al.
(författare)
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TRY plant trait database - enhanced coverage and open access
- 2020
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Ingår i: Global Change Biology. - : Wiley-Blackwell. - 1354-1013 .- 1365-2486. ; 26:1, s. 119-188
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Tidskriftsartikel (refereegranskat)abstract
- Plant traits-the morphological, anatomical, physiological, biochemical and phenological characteristics of plants-determine how plants respond to environmental factors, affect other trophic levels, and influence ecosystem properties and their benefits and detriments to people. Plant trait data thus represent the basis for a vast area of research spanning from evolutionary biology, community and functional ecology, to biodiversity conservation, ecosystem and landscape management, restoration, biogeography and earth system modelling. Since its foundation in 2007, the TRY database of plant traits has grown continuously. It now provides unprecedented data coverage under an open access data policy and is the main plant trait database used by the research community worldwide. Increasingly, the TRY database also supports new frontiers of trait-based plant research, including the identification of data gaps and the subsequent mobilization or measurement of new data. To support this development, in this article we evaluate the extent of the trait data compiled in TRY and analyse emerging patterns of data coverage and representativeness. Best species coverage is achieved for categorical traits-almost complete coverage for 'plant growth form'. However, most traits relevant for ecology and vegetation modelling are characterized by continuous intraspecific variation and trait-environmental relationships. These traits have to be measured on individual plants in their respective environment. Despite unprecedented data coverage, we observe a humbling lack of completeness and representativeness of these continuous traits in many aspects. We, therefore, conclude that reducing data gaps and biases in the TRY database remains a key challenge and requires a coordinated approach to data mobilization and trait measurements. This can only be achieved in collaboration with other initiatives.
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| 7. |
- Luize, Bruno Garcia, et al.
(författare)
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Geography and ecology shape the phylogenetic composition of Amazonian tree communities
- 2024
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Ingår i: JOURNAL OF BIOGEOGRAPHY. - 0305-0270 .- 1365-2699.
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Tidskriftsartikel (refereegranskat)abstract
- Aim: Amazonia hosts more tree species from numerous evolutionary lineages, both young and ancient, than any other biogeographic region. Previous studies have shown that tree lineages colonized multiple edaphic environments and dispersed widely across Amazonia, leading to a hypothesis, which we test, that lineages should not be strongly associated with either geographic regions or edaphic forest types. Location: Amazonia. Taxon: Angiosperms (Magnoliids; Monocots; Eudicots). Methods: Data for the abundance of 5082 tree species in 1989 plots were combined with a mega-phylogeny. We applied evolutionary ordination to assess how phylogenetic composition varies across Amazonia. We used variation partitioning and Moran's eigenvector maps (MEM) to test and quantify the separate and joint contributions of spatial and environmental variables to explain the phylogenetic composition of plots. We tested the indicator value of lineages for geographic regions and edaphic forest types and mapped associations onto the phylogeny. Results: In the terra firme and v & aacute;rzea forest types, the phylogenetic composition varies by geographic region, but the igap & oacute; and white-sand forest types retain a unique evolutionary signature regardless of region. Overall, we find that soil chemistry, climate and topography explain 24% of the variation in phylogenetic composition, with 79% of that variation being spatially structured (R-2 = 19% overall for combined spatial/environmental effects). The phylogenetic composition also shows substantial spatial patterns not related to the environmental variables we quantified (R-2 = 28%). A greater number of lineages were significant indicators of geographic regions than forest types. Main Conclusion: Numerous tree lineages, including some ancient ones (>66 Ma), show strong associations with geographic regions and edaphic forest types of Amazonia. This shows that specialization in specific edaphic environments has played a long-standing role in the evolutionary assembly of Amazonian forests. Furthermore, many lineages, even those that have dispersed across Amazonia, dominate within a specific region, likely because of phylogenetically conserved niches for environmental conditions that are prevalent within regions.
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| 8. |
- ter Steege, Hans, et al.
(författare)
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Mapping density, diversity and species-richness of the Amazon tree flora
- 2023
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Ingår i: COMMUNICATIONS BIOLOGY. - 2399-3642. ; 6:1
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Tidskriftsartikel (refereegranskat)abstract
- Using 2.046 botanically-inventoried tree plots across the largest tropical forest on Earth, we mapped tree species-diversity and tree species-richness at 0.1-degree resolution, and investigated drivers for diversity and richness. Using only location, stratified by forest type, as predictor, our spatial model, to the best of our knowledge, provides the most accurate map of tree diversity in Amazonia to date, explaining approximately 70% of the tree diversity and species-richness. Large soil-forest combinations determine a significant percentage of the variation in tree species-richness and tree alpha-diversity in Amazonian forest-plots. We suggest that the size and fragmentation of these systems drive their large-scale diversity patterns and hence local diversity. A model not using location but cumulative water deficit, tree density, and temperature seasonality explains 47% of the tree species-richness in the terra-firme forest in Amazonia. Over large areas across Amazonia, residuals of this relationship are small and poorly spatially structured, suggesting that much of the residual variation may be local. The Guyana Shield area has consistently negative residuals, showing that this area has lower tree species-richness than expected by our models. We provide extensive plot meta-data, including tree density, tree alpha-diversity and tree species-richness results and gridded maps at 0.1-degree resolution. A study mapping the tree species richness in Amazonian forests shows that soil type exerts a strong effect on species richness, probably caused by the areas of these forest types. Cumulative water deficit, tree density and temperature seasonality affect species richness at a regional scale.
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| 9. |
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| 10. |
- Abolfathi, Bela, et al.
(författare)
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The Fourteenth Data Release of the Sloan Digital Sky Survey : First Spectroscopic Data from the Extended Baryon Oscillation Spectroscopic Survey and from the Second Phase of the Apache Point Observatory Galactic Evolution Experiment
- 2018
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Ingår i: Astrophysical Journal Supplement Series. - : IOP Publishing Ltd. - 0067-0049 .- 1538-4365. ; 235:2
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Tidskriftsartikel (refereegranskat)abstract
- The fourth generation of the Sloan Digital Sky Survey (SDSS-IV) has been in operation since 2014 July. This paper describes the second data release from this phase, and the 14th from SDSS overall (making this Data Release Fourteen or DR14). This release makes the data taken by SDSS-IV in its first two years of operation (2014-2016 July) public. Like all previous SDSS releases, DR14 is cumulative, including the most recent reductions and calibrations of all data taken by SDSS since the first phase began operations in 2000. New in DR14 is the first public release of data from the extended Baryon Oscillation Spectroscopic Survey; the first data from the second phase of the Apache Point Observatory (APO) Galactic Evolution Experiment (APOGEE-2), including stellar parameter estimates from an innovative data-driven machine-learning algorithm known as "The Cannon"; and almost twice as many data cubes from the Mapping Nearby Galaxies at APO (MaNGA) survey as were in the previous release (N = 2812 in total). This paper describes the location and format of the publicly available data from the SDSS-IV surveys. We provide references to the important technical papers describing how these data have been taken (both targeting and observation details) and processed for scientific use. The SDSS web site (www.sdss.org) has been updated for this release and provides links to data downloads, as well as tutorials and examples of data use. SDSS-IV is planning to continue to collect astronomical data until 2020 and will be followed by SDSS-V.
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| 11. |
- Aguado, D. S., et al.
(författare)
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The Fifteenth Data Release of the Sloan Digital Sky Surveys : First Release of MaNGA-derived Quantities, Data Visualization Tools, and Stellar Library
- 2019
-
Ingår i: Astrophysical Journal Supplement Series. - : Institute of Physics Publishing (IOPP). - 0067-0049 .- 1538-4365. ; 240:2
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Tidskriftsartikel (refereegranskat)abstract
- Twenty years have passed since first light for the Sloan Digital Sky Survey (SDSS). Here, we release data taken by the fourth phase of SDSS (SDSS-IV) across its first three years of operation (2014 July-2017 July). This is the third data release for SDSS-IV, and the 15th from SDSS (Data Release Fifteen; DR15). New data come from MaNGA-we release 4824 data cubes, as well as the first stellar spectra in the MaNGA Stellar Library (MaStar), the first set of survey-supported analysis products (e.g., stellar and gas kinematics, emission-line and other maps) from the MaNGA Data Analysis Pipeline, and a new data visualization and access tool we call "Marvin." The next data release, DR16, will include new data from both APOGEE-2 and eBOSS; those surveys release no new data here, but we document updates and corrections to their data processing pipelines. The release is cumulative; it also includes the most recent reductions and calibrations of all data taken by SDSS since first light. In this paper, we describe the location and format of the data and tools and cite technical references describing how it was obtained and processed. The SDSS website (www.sdss.org) has also been updated, providing links to data downloads, tutorials, and examples of data use. Although SDSS-IV will continue to collect astronomical data until 2020, and will be followed by SDSS-V (2020-2025), we end this paper by describing plans to ensure the sustainability of the SDSS data archive for many years beyond the collection of data.
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| 12. |
- Gao, Hong, et al.
(författare)
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The landscape of tolerated genetic variation in humans and primates
- 2023
-
Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 380:6648
-
Tidskriftsartikel (refereegranskat)abstract
- Personalized genome sequencing has revealed millions of genetic differences between individuals, but our understanding of their clinical relevance remains largely incomplete. To systematically decipher the effects of human genetic variants, we obtained whole-genome sequencing data for 809 individuals from 233 primate species and identified 4.3 million common protein-altering variants with orthologs in humans. We show that these variants can be inferred to have nondeleterious effects in humans based on their presence at high allele frequencies in other primate populations. We use this resource to classify 6% of all possible human protein-altering variants as likely benign and impute the pathogenicity of the remaining 94% of variants with deep learning, achieving state-of-the-art accuracy for diagnosing pathogenic variants in patients with genetic diseases.
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| 13. |
- Kuderna, Lukas F. K., et al.
(författare)
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A global catalog of whole-genome diversity from 233 primate species
- 2023
-
Ingår i: Science. - : American Association for the Advancement of Science (AAAS). - 0036-8075 .- 1095-9203. ; 380:6648, s. 906-913
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Tidskriftsartikel (refereegranskat)abstract
- The rich diversity of morphology and behavior displayed across primate species provides an informative context in which to study the impact of genomic diversity on fundamental biological processes. Analysis of that diversity provides insight into long-standing questions in evolutionary and conservation biology and is urgent given severe threats these species are facing. Here, we present high-coverage wholegenome data from 233 primate species representing 86% of genera and all 16 families. This dataset was used, together with fossil calibration, to create a nuclear DNA phylogeny and to reassess evolutionary divergence times among primate clades. We found within-species genetic diversity across families and geographic regions to be associated with climate and sociality, but not with extinction risk. Furthermore, mutation rates differ across species, potentially influenced by effective population sizes. Lastly, we identified extensive recurrence of missense mutations previously thought to be human specific. This study will open a wide range of research avenues for future primate genomic research.
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| 14. |
- Kuderna, Lukas F. K., et al.
(författare)
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Identification of constrained sequence elements across 239 primate genomes
- 2024
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Ingår i: Nature. - : Springer Nature. - 0028-0836 .- 1476-4687. ; 625:7996, s. 735-742
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Tidskriftsartikel (refereegranskat)abstract
- Noncoding DNA is central to our understanding of human gene regulation and complex diseases1,2, and measuring the evolutionary sequence constraint can establish the functional relevance of putative regulatory elements in the human genome3,4,5,6,7,8,9. Identifying the genomic elements that have become constrained specifically in primates has been hampered by the faster evolution of noncoding DNA compared to protein-coding DNA10, the relatively short timescales separating primate species11, and the previously limited availability of whole-genome sequences12. Here we construct a whole-genome alignment of 239 species, representing nearly half of all extant species in the primate order. Using this resource, we identified human regulatory elements that are under selective constraint across primates and other mammals at a 5% false discovery rate. We detected 111,318 DNase I hypersensitivity sites and 267,410 transcription factor binding sites that are constrained specifically in primates but not across other placental mammals and validate their cis-regulatory effects on gene expression. These regulatory elements are enriched for human genetic variants that affect gene expression and complex traits and diseases. Our results highlight the important role of recent evolution in regulatory sequence elements differentiating primates, including humans, from other placental mammals.
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| 15. |
- Silva, Bruno F. B., et al.
(författare)
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Aqueous phase behavior of salt-free catanionic surfactants: the influence of solubility mismatch on spontaneous curvature and balance of forces
- 2011
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Ingår i: Soft Matter. - : Royal Society of Chemistry (RSC). - 1744-6848 .- 1744-683X. ; 7:1, s. 225-236
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Tidskriftsartikel (refereegranskat)abstract
- In this paper, we investigate the phase behavior and microstructure for a series of salt-free catanionic surfactants of the type Cm+Cn- with varied chain length mismatch (m not equal n), using light microscopy, DSC, turbidity, surface tension, SAXS and SANS. The compounds consist of alkyltrimethylammonium alkylsulfonates, denoted by TA(m)So(n). Depending on the asymmetry between both ions, three regimes can be identified: (i) weakly asymmetric; (ii) approximately symmetric; and (iii) highly asymmetric. For the TA(16)So(n) compounds, with n = 8 and 9 (weakly asymmetric), the surfactant forms a lamellar phase in water, however, with a striking miscibility gap. This miscibility gap is a consequence of the concentration dependent bilayer charge density. For n = 8, also a temperature-dependent vesicle-to-micelle transition at low surfactant concentration is observed. When the mismatch is low (n = 10) only a non-swelling lamellar phase is formed (approximately symmetric regime). For high mismatch, (n = 6 and 7) an extensive micellar phase is obtained - highly asymmetric regime. Conversely, for the TA(m)So(8) compounds, where m = 12 and 14, the unconventional lamellar miscibility gap and vesicle-micelle transition are again present. These findings are rationalized by considering the effect of film charge density-arising from the chain solubility difference-on the spontaneous curvature and balance of colloidal forces. The type of phase behavior reported here should be extensive to other families of salt-free catanionic amphiphiles, where an appropriate tuning of the solubility mismatch can allow the control of self-assembly.
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| 16. |
- Silva, Bruno F. B., et al.
(författare)
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Headgroup Effects on the Unusual Lamellar-Lamellar Coexistence and Vesicle-to-Micelle Transition of Salt-Free Catanionic Amphiphiles
- 2010
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Ingår i: Langmuir. - 0743-7463. ; 26:5, s. 3058-3066
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Tidskriftsartikel (refereegranskat)abstract
- Salt-free ion-paired catanionic amphiphiles of the C-m(+) C-n(-) type, with a high solubility mismatch (n >> m or m >> n) display a remarkable phase behavior in water. A temperature-driven vesicle-to-micelle transition in the dilute side together with a coexistence of two lamellar phases oil the concentrated side is one of the peculiar effects that have been reported for the hexadecyltrimethylammonium octylsulfonate surfactant, C16C8 or TA(16)So(8) (extensive to C14C8 and C12C8). In this work, with TA(16)So(8) as a reference, the cationic trimethylammonium (TA(+)) and pyridinium (P+) headgroups are combined with the anionic sulfate (S-) and sulfonate (So(-)) headgroups to yield other C16C8 compounds: hexadecyltrimethylammonium octylsulfate (TA(16)S(8)) 1-hexadecylpyridinium octylsulfonate (P(16)So(8)), and 1-hexadecylpyridinium octylsulfate (P(16)So(8)). We show that, if the asymmetry of the chain lengths is kept constant at C16C8 and the headgroup chemistry is changed, most of the unusual self-assembly properties are still observed, indicating that they are not system-specific but extensive to other combinations of headgroups and mainly dictated by the ion-pair solubility mismatch. Thus, all the compounds in water quite remarkably show a lamellar-lamellar phase coexistence and spontaneously form vesicles upon solubilization. Moreover, P(16)So(8) undergoes at temperature-driven vesicle-to-micelle transition that involves an intermediate planar lamellar state, similar to TA(16)So(8). Some interesting effects on the global phase behavior, however, do arise when the headgroups are changed, Geometric packing effects are shown to be important, but the differences in phase behavior seem to be mainly dictated by (i) the charge density of the headgroups, which tunes the solubility mismatch of the ion-pair, and (ii) specific interactions between headgroups, which affect the short-range repulsive force that controls the swelling of the concentrated lamellar phase,
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| 17. |
- Silva, Bruno F. B., et al.
(författare)
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Lamellar miscibility gap in a binary catanionic surfactant-water system
- 2007
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Ingår i: The Journal of Physical Chemistry Part B. - : American Chemical Society (ACS). - 1520-5207 .- 1520-6106. ; 111:48, s. 13520-13526
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Tidskriftsartikel (refereegranskat)abstract
- The coexistence of two lamellar liquid-crystalline phases in equilibrium for binary surfactant-water systems is a rare and still puzzling phenomenon. In the few binary systems where it has been demonstrated experimentally, the surfactant is invariably ionic and the miscibility gap is thought to stem from a subtle balance between attractive and repulsive interbilayer forces. In this paper, we report for the first time a miscibility gap for a catanionic lamellar phase formed by the surfactant hexadecyltrimethylammonium octylsulfonate (TASo) in water. Synchrotron small-angle X-ray scattering, polarizing light microscopy, and H-2 NMR unequivocally show the coexistence of a dilute (or swollen) lamellar phase, L-alpha', and a concentrated (or collapsed) lamellar phase, L alpha ''. Furthermore, linear swelling is observed for each of the phases, with the immiscibility region occurring for 15-54 wt % surfactant. In the dilute region, the swollen lamellar phase is in equilibrium with an isotropic micellar region. Vesicles can be observed in this two-phase region as a dispersion of L alpha' in the solution phase. A theoretical cell model based on combined DLVO and short-range repulsive potentials is presented in order to provide physical insight into the miscibility gap. The surfactant TASo is net uncharged, but it undergoes partial dissociation owing to the higher aqueous solubility of the short octylsulfonate chain. Thus, a residual positive charge in the bilayer is originated and, consequently, an electrostatic repulsive force, whose magnitude is dependent on surfactant concentration. For physically reasonable values of the solubility of the octyl chain, assumed to be constant with surfactant volume fraction, a fairly good agreement is observed between the experimental miscibility gap and the theoretical one.
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| 18. |
- Silva, Bruno F B, et al.
(författare)
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Size, Shape, and Charge of Salt-Free Catanionic Microemulsion Droplets: A Small-Angle Neutron Scattering and Modeling Study.
- 2009
-
Ingår i: The Journal of Physical Chemistry Part B. - : American Chemical Society (ACS). - 1520-5207 .- 1520-6106. ; 113:30, s. 10230-10239
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Tidskriftsartikel (refereegranskat)abstract
- The formation and microstructure of a novel microemulsion based on a salt-free catanionic surfactant have been examined by considering the hexadecyltrimethylammonium octylsulfonate (TASo)-decane-D(2)O system and using small-angle neutron scattering and self-diffusion NMR. With focus on the emulsification failure boundary, o/w discrete droplets have been observed and characterized for all of the studied microemulsion range. The evaluation of the experimental data was facilitated by using structure factors of a model system composed of charged particles interacting with a screened Coulomb potential. Furthermore, a more simplified model involving a charge regulation mechanism has been employed. Both approaches support the view that the droplets are mainly spherical, fairly monodisperse, and charged. The net charge of the surfactant film is a consequence of the partial dissociation of the short-chain counterpart, owing to its higher solubility. We have further quantified how the droplet charge varies with volume fraction and, from that dependence, explained the unusual phase behavior of the TASo-water system, a seldom found coexistence of two lamellar liquid-crystalline phases in a binary system. This coexistence is quantitatively modeled in terms of a fine balance between the attractive and repulsive colloidal forces acting within the system.
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| 19. |
- Abreu, Barbara, et al.
(författare)
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Gemini surfactants as efficient dispersants of multiwalled carbon nanotubes : Interplay of molecular parameters on nanotube dispersibility and debundling
- 2019
-
Ingår i: Journal of Colloid and Interface Science. - : ACADEMIC PRESS INC ELSEVIER SCIENCE. - 0021-9797 .- 1095-7103. ; 547, s. 69-77
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Tidskriftsartikel (refereegranskat)abstract
- Surfactants have been widely employed to debundle, disperse and stabilize carbon nanotubes in aqueous solvents. Yet, a thorough understanding of the dispersing mechanisms at molecular level is still warranted. Herein, we investigated the influence of the molecular structure of gemini surfactants on the dispersibility of multiwalled carbon nanotubes (MWNTs). We used dicationic n-s-n gemini surfactants, varying n and s, the number of alkyl tail and alkyl spacer carbons, respectively; for comparisons, single-tailed surfactant homologues were also studied. Detailed curves of dispersed MWNT concentration vs. surfactant concentration were obtained through a stringently controlled experimental procedure, allowing for molecular insight. The gemini are found to be much more efficient dispersants than their single-tailed homologues, i.e. lower surfactant concentration is needed to attain the maximum dispersed MWNT concentration. In general, the spacer length has a comparatively higher influence on the dispersing efficiency than the tail length. Further, scanning electron microscopy imaging shows a sizeable degree of MWNT debundling by the gemini surfactants in the obtained dispersions. Our observations also point to an adsorption process that does not entail the formation of micelle-like aggregates on the nanotube surface, but rather coverage by individual molecules, among which the ones that seem to be able to adapt best to the nanotube surface provide the highest efficiency. These studies are relevant for the rational design and choice of optimal dispersants for carbon nanomaterials and other similarly water-insoluble materials.
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| 20. |
- Antunes, Filipe E., et al.
(författare)
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Polymer-vesicle association
- 2009
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Ingår i: Advances in Colloid and Interface Science. - : Elsevier BV. - 1873-3727 .- 0001-8686. ; 147-48, s. 18-35
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Forskningsöversikt (refereegranskat)abstract
- Mixed polymer-surfactant systems have been intensively investigated in the last two decades, with the main focus on surfactant micelles as the surfactant aggregate in interaction. The main types of phase behavior, driving forces and structural/rheological effects at stake are now fairly well understood. Polymer-vesicle systems, on the other hand, have received comparatively less attention from a physico-chemical perspective. In this review, our main goal has been to bridge this gap, taking a broad approach to cover a field that is in clear expansion, in view of its multiple implications for colloid and biological sciences and in applied areas. We start by a general background on amphiphile self-assembly and phase separation phenomena in mixed polymer-surfactant solutions. We then address vesicle formation, properties and stability not only in classic lipids, but also in various other surfactant systems, among which catanionic vesicles are highlighted. Traditionally. lipid and surfactant vesicles have been studied separately, with little cross-information and comparison, giving duplication of physico-chemical interpretations. This situation has changed in more recent times. We then proceed to cover more in-depth the work done on different aspects of the associative behavior between vesicles (of different composition and type of stability) and different types of polymers, including polysaccharides. proteins and DNA. Thus. phase behavior features. effects of vesicle structure and stability, and the forces/mechanisms of vesicle-macromolecule interaction are addressed. Such association may generate gels with interesting theological properties and high potential for applications. Finally, special focus is also given to DNA, a high charge polymer. and its interactions with surfactants, and vesicles. in particular, in the context of gene transfection studies. (C) 2008 Elsevier B.V. All rights reserved
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| 21. |
- Brito, Rodrigo O., et al.
(författare)
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Self-assembly in a catanionic mixture with an aminoacid-derived surfactant: From mixed micelles to spontaneous vesicles
- 2006
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Ingår i: The Journal of Physical Chemistry Part B. - : American Chemical Society (ACS). - 1520-5207 .- 1520-6106. ; 110:37, s. 18158-18165
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Tidskriftsartikel (refereegranskat)abstract
- The aqueous self-assembly of a novel lysine-derived surfactant with a gemini-like architecture, designated here as 12-Lys-12, has been experimentally investigated for the amphiphile alone in water and in a mixture with dodecyltrimethylammonium bromide (DTAB). The neat surfactant forms interesting micrometer-sized rigid tubules in the dilute region, resulting in very viscous solutions. For the catanionic mixture with DTAB, various single and multiphase regions were identified (up to a total surfactant concentration of 1.5 wt %) by means of combined polarizing light microscopy, cryo-TEM, and NMR. In the DTAB-rich side, for a mixing molar ratio in the range 2 < DTAB/12-Lys-12 < 4, a region of stable, unilamellar vesicles can be found. Furthermore, it was found that upon addition of 12-Lys-12 to pure DTAB solutions, the mixed micelles grow and beyond a given mixing ratio, vesicles assemble and coexist with small micelles. The transition is not continuous, since there is a narrow mixing range where phase separation occurs. Self-diffusion measurements and cryo-TEM imaging show that the average vesicle radius is on the order of 30-40 nm.
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| 22. |
- Dai, Jing, et al.
(författare)
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Dispersing Carbon Nanotubes in Water with Amphiphiles : Dispersant Adsorption, Kinetics, and Bundle Size Distribution as Defining Factors
- 2018
-
Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 122:42, s. 24386-24393
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Tidskriftsartikel (refereegranskat)abstract
- Debundling and dispersing single-walled carbon nanotubes (SWNTs) is essential for applications, but the process is not well understood. In this work, aqueous SWNT dispersions were produced by sonicating pristine SWNT powder in the presence of an amphiphilic triblock copolymer (Pluronic F127) as dispersant. Upon centrifugation, one obtains a supernatant with suspended individual tubes and thin bundles and a precipitate with large bundles (and impurities). In the supernatant, that constitutes the final dispersion, we determined the dispersed SWNT concentration by thermogravi-metric analysis (TGA) and UV-vis spectroscopy, and the dispersant concentration by NMR The fraction of dispersant adsorbed at the SWNT surface was obtained by H-1 diffusion NMR Sigmoidal dispersion curves recording the concentration of dispersed SWNTs as a function of supernatant dispersant concentration were obtained at different SWNT loadings and sonication times. As SWNT bundles are debundled into smaller and smaller ones, the essential role of the dispersant is to sufficiently quickly cover the freshly exposed surfaces created by shear forces induced during sonication. Primarily kinetic reasons are behind the need for dispersant concentrations required to reach a substantial SWNT concentration. Centrifugation sets the size threshold below which SWNT particles are retained in the dispersion and consequently determines the SWNT concentration as a function of sonication time.
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| 23. |
- Fernandes, Ricardo M.F. 1983-, et al.
(författare)
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Assessing Surfactant Binding to Carbon Nanotubes via Competitive Adsorption : Binding strength and critical coverage
- 2015
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The displacement of a nonionic polymeric dispersant, Pluronic F127, adsorbed at the surface of single-walled carbon nanotubes, by low molecular-weight ionic dispersants (surfactants) is studied in aqueous dispersion. The method applied is diffusion NMR spectroscopy that can accurately measure the fraction of F127 molecules adsorbed at the tube surface because of the slow exchange (over the experimental time scale) of F127 between bulk and surface. In a series of surfactants with varying chain length and headgroups, we find that anionic surfactants replace in general more nonionic F127 than do cationic surfactants. The data collected show a strong correlation with the critical dispersibility concentration of the different surfactants, a parameter that signifies the concentration at which one obtains significant dispersed nanotube concentration by ultrasonication. We posit that this finding indicates the existence of a threshold surface coverage for dispersants that constitutes a necessary condition for de-bundling by ultrasonication. The results are discussed in relation to previous findings in the literature.
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| 24. |
- Fernandes, Ricardo M.F. 1983-, et al.
(författare)
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Dispersing Carbon Nanotubes with Ionic Surfactants under Controlled Conditions : Comparisons and Insight
- 2015
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 31:40, s. 10955-10965
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Tidskriftsartikel (refereegranskat)abstract
- A fundamental understanding of the mechanisms involved in the surfactant-assisted exfoliation and dispersion of carbon nanotubes (CNTs) in water calls for well-controlled experimental methodologies and reliable comparative metrics. We have assessed the ability of several ionic surfactants to disperse single and multiwalled carbon nanotubes, resorting to a stringently controlled sonication-centrifugation method for the preparation of the dispersions. The CNT concentration was accurately measured for a wide range of surfactant concentration, using combined thermogravimetric analysis and UV–vis spectroscopy. The obtained dispersibility curves yield several quantitative parameters, which in turn allow for the effects of nanotube morphology and surfactant properties (aromatic rings, chain length, headgroup charge, andcmc) to be assessed and rationalized, both in terms of dispersed nanotube mass and surface area. The data also indicate that the CNT-surfactant association follows patterns that are markedly different from other equilibrium processes governed by hydrophobicity (such as micellization); in particular, the surfactant concentration needed for maximum dispersibility,cs,max, and the number of surfactant molecules per unit CNT area at cs,max are shown to depend linearly on chain length. The results further suggest that the presence of micelles in the exfoliation process is not a key factor either for starting CNT dispersibility or attaining its saturation value.
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| 25. |
- Fernandes, Ricardo M.F. 1983-, et al.
(författare)
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Mechanical Agitation Induces Aggregation of Pre-Dispersed Carbon Nanotubes
- 2015
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Mechanical agitation is typically used to fragment and disperse insoluble materials in a solvent. We report here an aggregation process that, contrary to expectation, is induced by mechanical agitation: when aqueous dispersions of single-walled carbon nanotubes (SWNTs) are subject to vortex-shaking, weakly bound micron-sized aggregates are formed. The SWNT dispersions are prepared by adding various dispersants employing a sonication followed by centrifugation approach. While surfactant adsorption to the SWNTs during sonication results in stabilized exfoliated tubes and thin bundles, we find that vortex-shaking the fresh dispersions for short periods (10-60 s) results in re-aggregation into flocs in the 1-102 µm range. The aggregation is reversible: if the vortexed dispersions are mildly sonicated, the flocs break down and re-dispersal occurs. Imaging at different resolutions shows that the aggregates consist of loose networks of intertwined tubes and bundles. The data further indicate that the average aggregate size increases logarithmically with vortex time and is critically influenced by dispersant type (ionic or nonionic), centrifugation time (prior to vortexing) and initial concentration of dispersed SWNTs. These results are relevant if stabilization or destabilization of dispersions is sought for, i.e., in drug delivery or sensing applications, and could also be of interest for chiral sorting of SWNTs and percolation conductivity.
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| 26. |
- Fernandes, Ricardo M.F. 1983-, et al.
(författare)
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Strong Spacer Length Effects on The Thermal Behavior and Mesophase Formation By Gemini Surfactants
- 2015
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- The self-aggregation properties in aqueous solution of gemini surfactants of the type alkanediyl-α,ω-bis(dodecyldimethylammonium bromides), 12-s-12, have been extensively reported and are known to be significantly influenced by the number of methylene groups, s, of the covalent spacer. In contrast, the thermal behavior of the anhydrous compounds as a function of varying s has not been investigated in a similarly systematic way. Herein, we present the thermal phase behavior of eight compounds of the 12-s-12 family (with s = 2-6, 8, 10 and 12), resorting to differential scanning calorimetry (DSC), polarized light microscopy (PLM) and X-ray diffraction (XRD). We find that compounds with either the shortest spacer, s = 2, or the longest ones—8, 10 and 12—form several smectic liquid-crystalline phases prior to isotropization to the liquid phase, with appearance of oily streaks, focal conics, mosaic and fan-shaped birefringent textures. In sharp contrast, gemini compounds with intermediate spacers, s = 3-6, decompose and do not form any disordered, fluid mesophases. Both the DSC thermodynamic parameters for the phase transitions and d00l spacings obtained from XRD show non-monotonic trends with spacer variation, indicating that there are significant differences in solid-state packing and melting process. Plausible molecular packing arrangements in the solid-state are presented, consistent with the XRD information and geometric considerations, and their influence on the phase behavior trends critically discussed.
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| 27. |
- Fernandes, Ricardo M.F. 1983-, et al.
(författare)
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Surface Coverage and Competitive Adsorption on Carbon Nanotubes
- 2015
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 119:38, s. 22190-22197
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Tidskriftsartikel (refereegranskat)abstract
- The binding strength of dispersants to the surface of carbon nanotubes is of crucial importance for the efficiency of the dispersion process and for potential applications, yet data are scarce on this subject. Here we present the results of diffusion NMR experiments in dispersions of single-walled carbon nanotubes (SWNTs) prepared by either the polymer Pluronics F127 or the protein bovine serum albumin (BSA). The experiments detect the amount of F127 molecules adsorbed onto the SWNT surface. This quantity is recorded (i) in F127-SWNT dispersions to which BSA molecules are added and (ii) in BSA-SWNT dispersions to which F127 molecules are added. The data clearly show that F127 replaces BSA adsorbed at the SWNT surface, while BSA leaves the adsorbed F127 coverage intact. Consequently, F127 binds to the nanotube surface more strongly than BSA. Hence, we provide a way to categorize dispersants by adsorption strength. We also provide evidence showing that the nanotubes dispersed by BSA form loose aggregates where a large part of the surface is not in direct contact with the surrounding liquid. The results are discussed in relation to previous findings in the literature.
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| 28. |
- Ferreira da Silva, Eduardo, et al.
(författare)
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Heavy metal pollution downstream the abandoned Coval da Mó mine (Portugal) and associated effects on epilithic diatom communities
- 2009
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Ingår i: Science of the Total Environment. - : Elsevier BV. - 0048-9697 .- 1879-1026. ; 407:21, s. 5620-5636
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Tidskriftsartikel (refereegranskat)abstract
- This study examined trace-element concentrations in 39 sediment samples collected in the vicinity of the abandoned Coval da Mó mine, and evaluated the anthropogenic contaminant effects and other environmental variables in the taxonomic composition, structure and morphological changes of benthic diatom communities.The results show the existence of extremely high contamination in Pb, Zn and Cd (the mean values exceed the background values 376, 96 and 19 times, respectively) on the first 2.5 km in the water flow direction. Also Co, Cu, Mn and Ni are present in high concentrations. Dilution by relatively uncontaminated sediment reduces metal concentrations downstream, but Zn concentrations increase downstream Fílvida stream, as a result of several factors such as sewage and agriculture.To evaluate the biological effects caused by Pb, Cd and Zn, three sites were selected. In the stressed environment, near the mining area (C232), diatoms were extremely rare, however there was a slight recovery at site C79 located 2 km downstream. Fragilaria capucina var. rumpens, Fragilaria cf. crotonensis and Achnanthidium minutissimum showed abnormal valves which may be related to high levels of metals.Six km downstream, in Fílvida stream (C85), an increase in species richness and diversity was registered while the relative percentage of valve teratologies was lower. In the absence of OM, nutrients and low pH the diatom community patterns must be attributed to the metal concentration at some sites. Considering that community diversity can be affected by abiotic and biotic variables and valve deformations are caused by a small number of variables, basically metals, and acid conditions, we consider the presence of teratologies as an indication of the presence of metals.
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| 29. |
- Ferreira Fernandes, Ricardo Manuel, 1983-, et al.
(författare)
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Block Copolymers as Dispersants for Single-Walled Carbon Nanotubes : Modes of Surface Attachment and Role of Block Polydispersity
- 2018
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Ingår i: Langmuir. - : AMER CHEMICAL SOC. - 0743-7463 .- 1520-5827. ; 34:45, s. 13672-13679
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Tidskriftsartikel (refereegranskat)abstract
- When using amphiphilic polymers to exfoliate and disperse carbon nanotubes in water, the balance between the hydrophobic and hydrophilic moieties is critical and nontrivial. Here, we investigate the mode of surface attachment of a triblock copolymer, Pluronics F127, composed of a central hydrophobic polypropylene oxide block flanked by hydrophilic polyethylene oxide blocks, onto single-walled carbon nanotubes (SWNTs). Crucially, we analyze the composition in dispersant of both the as-obtained dispersion (the supernatant) and the precipitate-containing undispersed materials. For this, we combine the carefully obtained data from H-1 NMR peak intensities and self-diffusion and thermogravimetric analysis. The molecular motions behind the observed NMR features are clarified. We find that the hydrophobic blocks attach to the dispersed SWNT surface and remain significantly immobilized leading to H-1 NMR signal loss. On the other hand, the hydrophilic blocks remain highly mobile and thus readily detectable by NMR. The dispersant is shown to possess significant block polydispersity that has a large effect on dispersibility. Polymers with large hydrophobic blocks adsorb on the surface of the carbonaceous particles that precipitate, indicating that although a larger hydrophobic block is good for enhancing adsorption, it may be less effective in dispersing the tubes. A model is also proposed that consistently explains our observations in SWNT dispersions and some contradicting findings obtained previously in carbon nanohorn dispersions. Overall, our findings help elucidating the molecular picture of the dispersion process for SWNTs and are of interest when looking for more effective (i.e., well-balanced) polymeric dispersants.
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| 30. |
- Ferreira Fernandes, Ricardo Manuel, et al.
(författare)
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Lateral Diffusion of Dispersing Molecules On Nanotubes As Probed by NMR
- 2014
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Ingår i: The Journal of Physical Chemistry C. - : American Chemical Society (ACS). - 1932-7447 .- 1932-7455. ; 118:1, s. 582-589
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Tidskriftsartikel (refereegranskat)abstract
- Noncovalent dispersion of carbon nanotubes is essential to most applications but still poorly understood at the molecular level. The interaction of the dispersing molecule with the nanotube, wrapping or nonwrapping, still awaits consensus. Herein, we have studied by H-1 NMR diffusometry some features of molecular dynamics in the system of carbon nanotubes dispersed by triblock copolymer Pluronics F127 in water. The diffusional decays obtained at different diffusion times, Delta, are not single-exponential and have a complex Delta-dependent profile, ultimately implying that the polymer is observed in two states: free (in unimeric form) and nanotube-bound. Fitting a two-site exchange model to the data indicates that at any instant, only a small fraction of polymers are adsorbed on the nanotubes, with polydisperse residence times in the range of 100-400 ms. Most significantly, we further provide an estimate of D = (3-8) x 10(-12) m(2) s(-1) the coefficient of lateral diffusion of the polymer along the nanotube surface, which is an order of magnitude slower than the corresponding self-diffusion coefficient in water. The emerging picture is that of a nonwrapping mode for the polymer-nanotube interaction.
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| 31. |
- Margulis-Goshen, Katrin, et al.
(författare)
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Formation of solid organic nanoparticles from a volatile catanionic microemulsion
- 2011
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Ingår i: Soft Matter. - : Royal Society of Chemistry (RSC). - 1744-6848 .- 1744-683X. ; 7:19, s. 9359-9365
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Tidskriftsartikel (refereegranskat)abstract
- A novel volatile microemulsion formed by the catanionic surfactant hexadecyltrimethylammonium octylsulfonate (TA(16)So(8)), heptane and water has been explored as a template for producing nanoparticles of hydrophobic organic materials. Butylated hydroxytoluene (BHT) was employed as the model hydrophobic substance. First, the oil-in-water microemulsion was formed, containing TA16So8 as the single emulsifier and BHT dispersed in the volatile microphase. Microstructure characterization by self-diffusion NMR revealed that BHT was indeed incorporated into the oil droplets and that the mean diameter of the main droplet population was 30 nm, larger than in the BHT-free microemulsion. Next, a rapid solvent and water removal by freeze drying allowed converting the microemulsion droplets into nanoparticles in the form of a dry, fine powder. This powder was freely dispersible in water to yield a stable suspension of amorphous BHT particles with a mean size of 19 nm and zeta-potential of +37 mV. The solid nanoparticles in the aqueous dispersion were thus smaller than the initial microemulsion droplets. For comparison, a conventional o/w microemulsion composed of CTAB and sec-butanol was also tested as a template for BHT particle formation by the same process, and it was found that it yielded crystalline particles of micrometre size. On the basis of our results, we anticipate the catanionic microemulsion method to be an efficient one for producing size-controlled, water-dispersible nanoparticles of other hydrophobic organic materials.
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| 32. |
- Marques, Eduardo F., et al.
(författare)
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Liquid Crystals and Phase Equilibria Binary Bile Salt-Water Systems
- 2000
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Ingår i: Langmuir. - : American Chemical Society (ACS). - 0743-7463 .- 1520-5827. ; 16:11, s. 5178-5186
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Tidskriftsartikel (refereegranskat)abstract
- The phase behavior of several binary sodium bile salt-water systems is investigated over the entire concentration range, with emphasis on concentrated regions beyond the isotropic solution phase. The studied bile acid salts comprise the free salt sodium deoxycholate (SDC), the taurine conjugates sodium taurocholate (STC), sodium taurodeoxycholate (STDC), and sodium taurochenodeoxycholate (STCDC) and the glycine conjugate sodium glycodeoxycholate (SGDC). A combination of classical techniques is used, including phase diagram determination, polarizing microscopy, 2H NMR, and small-angle X-ray scattering (SAXS). The aggregation behavior in the isotropic micellar solutions of STC and STDC is also investigated by pulsed-field gradient NMR self-diffusion. The optical textures and the data from SAXS and 2H NMR clearly point to the formation of hexagonal liquid crystals, possibly of the reverse type, beyond the micellar solution for all the bile salts. Several unusual kinetic effects, such as very slow equilibration times and the formation of transient spherulitic crystals in biphasic regions, are observed. The phase diagrams and structural data are qualitatively discussed in terms of the molecular structure and solubility of the different salts. The formation of lyotropic liquid crystals by bile salts, which has remained unknown for decades, is clearly demonstrated in this work.
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| 33. |
- Rocha, Jessica, et al.
(författare)
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Gemini Surfactants as Dispersants of Multiwalled Carbon Nanotubes : a Systematic Study on the Role of Molecular Structure
- 2015
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Annan publikation (övrigt vetenskapligt/konstnärligt)abstract
- Surfactants have been widely used as non-covalent dispersants of carbon nanotubes and yet a deeper and systematic understanding of the role of their molecular properties on dispersibility still awaits consensus. Herein, we report on the dispersibility of multiwalled carbon nanotubes (MWNTs) using a set of dicationic gemini surfactants of the n-s-n type, where both the length of the covalent spacer (s) that bridges the two cationic headgroups and the length of the tails (n) are systematically varied. Thus, 12-s-12 gemini with s = 2, 6, and 12 are studied together with 16-s-16 (s = 2 and 12). In addition, the single-tailed homologues dodecyltrimethylammonium bromide, DTAB (n = 12), and cetyltrimethylammonium bromide, CTAB (n = 16), are employed for comparisons. High precision dispersion curves (dispersed NT vs. surfactant concentration) are presented, obtained through a well-controlled sonication/centrifugation procedure combined with an accurate determination of MWNT concentration. The gemini amphiphiles, despite being double-tailed and double-charged, are found to be less effective dispersants than CTAB and roughly as effective as DTAB. Among the gemini, the following pattern emerges as concerning dispersion behavior. (i) The tail length, n, is less influential than spacer length, s, in dispersing ability, implying that the spacer hydrophobicity rather than that of the tail may govern the affinity for the nanotube surface. (ii) In the 12-s-12 series, the surfactant concentration needed for maximum MWNT dispersibility depends linearly on s, while it is known that the neat cmc depends non-monotonically on s. (iii) Similarly to single-tailed ionic surfactants, the presence of micelles has no direct effect on the dispersion behavior. In combination, these observations also point to an adsorption mechanism that does not involve the formation of micelle-like aggregates on the nanotube surface but rather coverage by individual dispersant molecules.
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| 34. |
- Silva, Bruno F. B., et al.
(författare)
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Fusion and fission of catanionic bilayers
- 2011
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Ingår i: Soft Matter. - : Royal Society of Chemistry (RSC). - 1744-6848 .- 1744-683X. ; 7:5, s. 1686-1689
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Tidskriftsartikel (refereegranskat)abstract
- We herein report the reversible formation of a planar lamellar phase as an intermediate structure in a vesicle-micelle transition induced by temperature, for a salt-free catanionic surfactant-water system. Turbidity, small-angle neutron scattering, dynamic light scattering and microscopy data altogether demonstrate that the vesicles formed by hexadecyltrimethylammonium octylsulfonate (TA(16)So(8)) in water fuse at high temperature into planar lamellae before transforming into elongated micelles. On cooling the micelles first nucleate into lamellae, and only then vesicles appear through lamellae fission. This behavior is both intriguing and counter-intuitive, since a monotonous dependence of the spontaneous curvature of the surfactant film on temperature should be expected.
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