On the Molecular Origin of the Cooperative Coil-to-globule Transition of Poly(N-isopropylacrylamide) in Water

By means of atomistic molecular dynamics simulations we investigate the behaviour of poly(N-isopropylacrylamide), PNIPAM, in water at temperatures below and above the lower critical solution temperature (LCST), including the undercooled regime. The transition between water soluble and insoluble states at the LCST is described as a cooperative process involving an intramolecular coil-to-globule transition preceding the aggregation of chains and the polymer precipitation. In this work we investigate the molecular origin of such cooperativity and the evolution of the hydration pattern in the undercooled polymer solution. The solution behaviour of an atactic 30-mer at high dilution is studied in the temperature interval from 243 to 323 K with a favourable comparison to available experimental data. In the PNIPAM water soluble states we detect a correlation between polymer segmental dynamics and diffusion motion of bound water, occurring with the same activation energy. Simulation results show that below the coil-to-globule transition temperature PNIPAM is surrounded by a network of hydrogen bonded water molecules and that the cooperativity arises from the structuring of water clusters in proximity to hydrophobic groups. Differently, the perturbation of the hydrogen bond pattern involving water and amide groups occurs above the transition temperature. Altogether these findings reveal that even above the LCST PNIPAM remains largely hydrated and that the coil-to-globule transition is related with a significant rearrangement of the solvent in proximity of the surface of the polymer. The comparison between the hydrogen bonding of water in the surrounding of PNIPAM isopropyl groups and in bulk displays a decreased structuring of solvent at the hydrophobic polymer-water interface across the transition temperature, as expected because of the topological extension along the chain of such interface

Molecular insights on poly(N-isopropylacrylamide) coil-to-globule transition induced by pressure

By using extensive all-atom molecular dynamics simulations of an atactic linear polymer chain, we provide microscopic insights into poly(N-isopropylacrylamide) (PNIPAM) coil-to-globule transition addressing the roles played by both temperature and pressure. We detect a coil-to-globule transition up to large pressures, showing a reentrant behavior of the critical temperature with increasing pressure in agreement with experimental observations. Furthermore, again confirming the experimental findings, we report the existence at high pressures of a new kind of globular state. It is characterized by a more structured hydration shell that is closer to PNIPAM hydrophobic domains, as compared to the globular state observed at atmospheric pressure. Our results highlight that temperature and pressure induce a PNIPAM coil-to-globule transition through different molecular mechanisms, opening the way for a systematic use of both thermodynamic variables to tune the location of the transition and the properties of the associated swollen/collapsed states

Microgel particles with distinct morphologies and common chemical compositions: a unified descrip-tion of the responsivity to temperature and osmotic stress

Poly(N-isopropylacrylamide) (PNIPAM) hydrogel microparticles with different core-shell morphologies have been designed, while maintaining an unvaried chemical composition: a morphology with (i) an un-crosslinked core with a crosslinked shell of PNIPAM chains and (ii) PNIPAM chains crosslinked to form the core with a shell consisting of tethered un-crosslinked PNIPAM chains to the core. Both morphologies with two different degrees of crosslinking have been assessed by confocal microscopy and tested with respect to their temperature responsivity and deformation by applying an osmotic stress. The thermal and mechanical behavior of these architectures have been framed within a Flory-Rehner modified model in order to describe the microgel volume shrinking occurring as response to a temperature increase or an osmotic perturbation. This study provides a background for assessing to what extent the mechanical features of the microgel particle surface affect the interactions occurring at the interface of a microgel particle with a cell, in addition to the already know ligand/receptor interaction. These results have direct implications in triggering a limited phagocytosis of microdevices designed as injectable drug delivery systems

Assembling patchy plasmonic nanoparticles with aggregation-dependent antibacterial activity

We realise an antibacterial nanomaterial based on the self-limited assembly of patchy plasmonic colloids, obtained by adsorption of lysozyme to gold nanoparticles. The possibility of selecting the size of the assemblies within several hundred nanometres allows for tuning their optical response in a wide range of frequencies from visible to near infrared. We also demonstrate an aggregation-dependent modulation of the catalytic activity, which results in an enhancement of the antibacterial performances for assemblies of the proper size. The gained overall control on structure, optical properties and biological activity of such nanomaterial paves the way for the development of novel antibacterial nanozymes with promising applications in treating multi drug resistant bacteria

Protein-like dynamical transition of hydrated polymer chains

Combining elastic incoherent neutron scattering experiments at different resolutions and molecular dynamics simulations, we report the observation of a protein-like dynamical transition in Poly(N-isopropylacrylamide) chains. We identify the onset of the transition at a temperature Td of about 225~K. Thanks to a novel global fit procedure, we find quantitative agreement between measured and calculated polymer mean-squared displacements at all temperatures and time resolutions. Our results confirm the generality of the dynamical transition in macromolecular systems in aqueous environments, independently of the internal polymer topology

The Fate of Carbon in Sediments of the Xingu and Tapajós Clearwater Rivers, Eastern Amazon

The Xingu and Tapajós rivers in the eastern Amazon are the largest clearwater systems of the Amazon basin. Both rivers have “fluvial rias” (i.e., lake-like channels) in their downstream reaches as they are naturally impounded by the Amazon mainstem. Fluvial rias are widespread in the Amazon landscape and most of the sedimentary load from the major clearwater and blackwater rivers is deposited in these channels. So far, little is known about the role of Amazon rias as a trap and reactor for organic sediments. In this study, we used organic and inorganic geochemistry, magnetic susceptibility, diatom, and pollen analyses in sediments (suspended, riverbed, and downcore) of the Xingu and Tapajós rias to investigate the effects of hydrologic variations on the carbon budget in these clearwater rivers over the Holocene. Ages of sediment deposition (~100 to 5,500 years) were constrained by optically stimulated luminescence and radiocarbon. Major elements geochemistry and concentration of total organic carbon (TOC) indicate that seasonal hydrologic variations exert a strong influence on riverine productivity and on the input and preservation of organic matter in sediments. Stable carbon isotope data (δ13C from −31.04 to −27.49‰) and pollen analysis indicate that most of the carbon buried in rias is derived from forests. In the Xingu River, diatom analysis in bottom sediments revealed 65 infrageneric taxa that are mostly well-adapted to slack oligotrophic and acidic waters. TOC values in sediment cores are similar to values measured in riverbed sediments and indicate suitable conditions for organic matter preservation in sediments of the Xingu and Tapajós rias at least since the mid-Holocene, with carbon burial rates varying from about 84 g m−2 yr−1 to 169 g m−2 yr−1. However, redox-sensitive elements in sediment core indicate alternation between anoxic/dysoxic and oxic conditions in the water-sediment interface that may be linked to abrupt changes in precipitation. The variation between anoxic/dysoxic and oxic conditions in the water-sediment interface controls organic matter mineralization and methanogenesis. Thus, such changes promoted by hydrological variations significantly affect the capacity of Amazon rias to act either as sources or sinks of carbon

Trans-Amazon Drilling Project (TADP): origins and evolution of the forests, climate, and hydrology of the South American tropics

This article presents the scientific rationale for an ambitious ICDP drilling project to continuously sample Late Cretaceous to modern sediment in four different sedimentary basins that transect the equatorial Amazon of Brazil, from the Andean foreland to the Atlantic Ocean. The goals of this project are to document the evolution of plant biodiversity in the Amazon forests and to relate biotic diversification to changes in the physical environment, including climate, tectonism, and the surface landscape. These goals require long sedimentary records from each of the major sedimentary basins across the heart of the Brazilian Amazon, which can only be obtained by drilling because of the scarcity of Cenozoic outcrops. The proposed drilling will provide the first long, nearly continuous regional records of the Cenozoic history of the forests, their plant diversity, and the associated changes in climate and environment. It also will address fundamental questions about landscape evolution, including the history of Andean uplift and erosion as recorded in Andean foreland basins and the development of west-to-east hydrologic continuity between the Andes, the Amazon lowlands, and the equatorial Atlantic. Because many modern rivers of the Amazon basin flow along the major axes of the old sedimentary basins, we plan to locate drill sites on the margin of large rivers and to access the targeted drill sites by navigation along these rivers

Assessing young people's political engagement: a critical and systematic literature review of the instruments used to measure political engagement

Over the past few decades, there has been an increasing interest in understanding youth political engagement. However, it has been argued that the instruments used to assess the concept often lack adequate validation, and this is important as this practice may result in biased statistical conclusions. Consequently, the main aim of the present study was to systematically review, summarize, and critique the extant research evidence on the development of psychometric instruments that assess young people’s political engagement. Following a systematic review of the literature, seven instruments were identified that were both valid and reliable, but none explicitly assessed young people’s political engagement. Instead, they considered broad concepts and/or dimensions related to political engagement. Emphasising the lack of statistically robust standardised measurement tools that empirically assess young people’s political engagement, the available evidence confirms the pressing need to adopt a robust psychometric approach to assess political engagement in youth

Solution behaviour of poly(N-isopropylacrylamide) stereoisomers in water: a molecular dynamics simulation study

The water affinity of poly(N-isopropylacrylamide), PNIPAM, is tuned by tacticity, since the hydrophobicity raises with the increase of the degree of isotacticity. On the basis of this experimental evidence, atomistic molecular dynamics simulations of pairs of PNIPAM stereoisomers in 1.6 % w/w polymer aqueous solution, a condition intermediate between the dilute and semidilute regimes, were carried out to comparatively investigate the solution behaviour and hydration of atactic and isotactic rich PNIPAMs, both below and above the lower critical solution temperature, LCST. 30-mers with content of meso dyads, m, of 45 % and 59 %, built assuming a Bernoullian dyad distribution, are used as models since their stereochemical composition corresponds to that of experimentally characterized PNIPAM stereoisomers. Simulation results at 283 K, below the LCST, show a scarce influence of the tacticity on the chain size, but a higher propensity for inter-chain association of the meso-dyad-rich system, in agreement with experimental results. Junctions between chains are formed because of hydrophobic interactions and are stabilized by a layer of hydrogen bonded water molecules, whose mobility is reduced as compared to that observed for the same meso-dyad-rich stereoisomer at infinite dilution. At 323 K, above the LCST, simulations detect both the coil-globule transition and the aggregation of chains. In this condition the influence of tacticity on the characteristics of PNIPAM aggregate is negligible

Influence of Tacticity on Hydrophobicity of Poly(N-isopropylacrylamide): A Single Chain Molecular Dynamics Simulation Study

Several pieces of experimental evidence show that the water affinity of poly(N-isopropylacrylamide), PNIPAM, decreases with the increase of the degree of isotacticity. To give a rationale to such effect we carried out atomistic molecular dynamics simulations of PNIPAM 30-mers with content of meso dyads, m, of 45% and 59%, assuming a Bernoullian dyad distribution. The single chain behavior of these stereoisomers in water was modeled at 283 and 323 K, i.e., below and above the lower critical solution temperature, LCST. Simulation results show that the dyad composition has influence on size and conformation of the oligomer below the LCST, the isotactic-rich stereoisomer preferring conformations with lower radius of gyration. With reference to the cooperative hydration model of PNIPAM, we analyzed the organization and the dynamics of water in the surroundings of the polymer. Below the LCST the number of hydrogen bonds per water molecule in the first hydration shell and the water surface concentration around PNIPAM are affected by the meso/racemo dyad ratio, showing the higher hydrophobicity of the isotactic-rich system. Above the LCST the subtle effects leading to the modulation of conformation and hydration by means of tacticity are overtaken, and the chain collapse is observed for both systems up to a similar globular state. The comparison of simulation findings of the m 45% stereoisomer with available experimental results of atactic PNIPAM highlights additional molecular details of this macromolecule in aqueous environment. The characteristic time for motion of water molecules in the PNIPAM first hydration shell at 283 K is about 34 ps, in agreement with the experimental value