625 research outputs found

    Material valorisation of amorphous polylactide. Influence of thermo-mechanical degradation on the morphology, segmental dynamics, thermal and mechanical performance

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    This paper reports the effects of multiple mechanical recycling on the structure and properties of amorphous polylactide (PLA). The influence of the thermo-mechanical degradation induced by means of five successive injection cycles was initially addressed in terms of macroscopic mechanical properties and surface modification. A deeper inspection on the structure and morphology of PLA was associated to the thermal properties and viscoelastic behaviour. Although FT-IR analysis did not show significant changes in functional groups, a remarkable reduction in molar mass was found by viscometry. PLA remained amorphous throughout the reprocessing cycles, but the occurrence of a cold-crystallization during DSC and DMTA measurements, which enthalpy increased with each reprocessing step, suggested chain scission due to thermo-mechanical degradation. The effect of chain shortening on the glass-rubber relaxation studied by DMTA showed an increase in free volume affecting the segmental dynamics of PLA, particularly after the application of the second reprocessing step, in connection to the overall loss of performance showed by the remaining properties

    Synthesis of Oligodeoxyribo‐ and Oligoribonucleotides According to the H‐Phosphonate Method

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    Oligonucleotides can be synthesized by condensing a protected nucleoside H‐phosphonate monoester with a second nucleoside in the presence of a coupling agent to produce a dinucleoside H‐phosphonate diester. This can then be converted to a dinucleoside phosphate or to a backbone‐modified analog such as a phosphorothioate or phosphoramidite. This unit discusses four alternative methods for synthesizing nucleoside H‐phosphonate monoesters. The methods are efficient and experimentally simple, and use readily available reagents. The unit describes the activation of the monoesters, as well as competing acylation and other potential side reactions.Peer Reviewedhttps://deepblue.lib.umich.edu/bitstream/2027.42/143594/1/cpnc0304.pd

    Decoupling the Spread of Grasslands from the Evolution of Grazer-type Herbivores in South America

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    The evolution of high-crowned cheek teeth (hypsodonty) in herbivorous mammals during the late Cenozoic is classically regarded as an adaptive response to the near-global spread of grass-dominated habitats. Precocious hypsodonty in middle Eocene (~38 million years (Myr) ago) faunas from Patagonia, South America, is therefore thought to signal Earth’s first grasslands, 20 million years earlier than elsewhere. Here, using a high-resolution, 43–18 million-year record of plant silica (phytoliths) from Patagonia, we show that although open-habitat grasses existed in southern South America since the middle Eocene (~40 Myr ago), they were minor floral components in overall forested habitats between 40 and 18 Myr ago. Thus, distinctly different, continent-specific environmental conditions (arid grasslands versus ash-laden forests) triggered convergent cheek–tooth evolution in Cenozoic herbivores. Hypsodonty evolution is an important example where the present is an insufficient key to the past, and contextual information from fossils is vital for understanding processes of adaptation

    Decoupling the spread of grasslands from the evolution of grazer-type herbivores in South America

    Get PDF
    The evolution of high-crowned cheek teeth (hypsodonty) in herbivorous mammals during the late Cenozoic is classically regarded as an adaptive response to the near-global spread of grass-dominated habitats. Precocious hypsodonty in middle Eocene (∼38 million years (Myr) ago) faunas from Patagonia, South America, is therefore thought to signal Earth's first grasslands, 20 million years earlier than elsewhere. Here, using a high-resolution, 43-18 million-year record of plant silica (phytoliths) from Patagonia, we show that although open-habitat grasses existed in southern South America since the middle Eocene (∼40 Myr ago), they were minor floral components in overall forested habitats between 40 and 18 Myr ago. Thus, distinctly different, continent-specific environmental conditions (arid grasslands versus ash-laden forests) triggered convergent cheek-tooth evolution in Cenozoic herbivores. Hypsodonty evolution is an important example where the present is an insufficient key to the past, and contextual information from fossils is vital for understanding processes of adaptation.Facultad de Ciencias Naturales y Muse

    Decoupling the spread of grasslands from the evolution of grazer-type herbivores in South America

    Get PDF
    The evolution of high-crowned cheek teeth (hypsodonty) in herbivorous mammals during the late Cenozoic is classically regarded as an adaptive response to the near-global spread of grass-dominated habitats. Precocious hypsodonty in middle Eocene (∼38 million years (Myr) ago) faunas from Patagonia, South America, is therefore thought to signal Earth's first grasslands, 20 million years earlier than elsewhere. Here, using a high-resolution, 43-18 million-year record of plant silica (phytoliths) from Patagonia, we show that although open-habitat grasses existed in southern South America since the middle Eocene (∼40 Myr ago), they were minor floral components in overall forested habitats between 40 and 18 Myr ago. Thus, distinctly different, continent-specific environmental conditions (arid grasslands versus ash-laden forests) triggered convergent cheek-tooth evolution in Cenozoic herbivores. Hypsodonty evolution is an important example where the present is an insufficient key to the past, and contextual information from fossils is vital for understanding processes of adaptation.Facultad de Ciencias Naturales y Muse

    Effect of the dissolution time into an acid hydrolytic solvent to taylor electrospun nanofibrous polycaprolactone scaffolds

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    The hydrolysis of the polycaprolactone (PCL) as a function of the dissolution time in a formic/ acetic acid mixture was considered as a method for tailoring the morphology of nanofibrous PCL scaffolds. Hence, the aim of this research was to establish a correlation between the dissolution time of the polymer in the acid solvent with the physicochemical properties of the electrospun nanofibrous scaffolds and their further service life behaviour. The physico-chemical properties of the scaffolds were assessed in terms of fibre morphology, molar mass and thermal behaviour. A reduction of the molar mass and the lamellar thickness as well as an increase of the crystallinity degree were observed as a function of dissolution time. Bead-free fibres were found after 24 and 48 h of dissolution time, with similar diameter distributions. The decrease of the fibre diameter distributions along with the apparition of beads was especially significant for scaffolds prepared after 72 h and 120 h of dissolution time in the acid mixture. The service life of the obtained devices was evaluated by means of in vitro validation under abiotic physiological conditions. All the scaffolds maintained the nanofibrous structure after 100 days of immersion in water and PBS. The molar mass was barely affected and the crystallinity degree and the lamellar thickness increased along immersion, preventing scaffolds from degradation. Scaffolds prepared after 24 h and 48 h kept their fibre diameters, whereas those prepared after 72 h and 120 h showed a significant reduction. This PCL tailoring procedure to obtain scaffolds that maintain the nanoscaled structure after such long in vitro evaluation will bring new opportunities in the design of longterm biomedical patches
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