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The organic matter (OM) in biopore walls and aggregate coatings may be important for sorption of reactive solutes and water as well as for solute mass exchange between the soil matrix and the preferential flow (PF) domains in structured soil. Structural surfaces are coated by illuvial clay-organic material and by OM of different origin, e.g., earthworm casts and root residues. The objectives were to verify the effect of OM on wettability and infiltration of intact structural surfaces in clay-illuvial horizons (Bt) of Luvisols and to investigate the relevance of the mm-scale distribution of OM composition on the water and solute transfer. Intact aggregate surfaces and biopore walls were prepared from Bt horizons of Luvisols developed from Loess and glacial till. The mm-scale spatial distribution of OM composition was scanned using diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The ratio between alkyl and carboxyl functional groups in OM was used as potential wettability index (PWI) of the OM. The infiltration dynamics of water and ethanol droplets were determined measuring contact angles (CA) and water drop penetration times (WDPT). At intact surfaces of earthworm burrows and coated cracks of the Loess-Bt, the potential wettability of the OM was significantly reduced compared to the uncoated matrix. These data corresponded to increased WDPT, indicating a mm-scaled sub-critical water repellency. The relation was highly linear for earthworm burrows and crack coatings from the Loess-Bt with WDPT >2.5 s. Other surfaces of the Loess-Bt and most surfaces of the till-derived Bt were not found to be repellent. At these surfaces, no relations between the potential wettability of the OM and the actual wettability of the surface were found. The results suggest that water absorption at intact surface structures, i.e., mass exchange between PF paths and soil matrix, can be locally affected by a mm-scale OM distribution if OM is of increased content and is enriched in alkyl functional groups. For such surfaces, the relation between potential and actual wettability provides the possibility to evaluate the mm-scale spatial distribution of wettability and sorption and mass exchange from DRIFT spectroscopic scanning.
BACKGROUND: There is an increased need to replace materials derived from fossil sources by renewables. Sugar-cane derived carbohydrates are very abundant in Brazil and are the cheapest sugars available in the market, with more than 400 million tons of sugarcane processed in the year 2007. The objective of this work was to study the preparation of sugar acrylates from free sugars and free acrylic acid, thus avoiding the previous preparation of protected sugar derivatives, such as glycosides, or activated acrylates, such as vinyl acrylate. RESULTS: Lipase catalyzed esterification of three mono- and two disaccharides with acrylic acid, in the presence or absence of molecular sieves was investigated. The reactions were monitored by high-performance liquid chromatography (HPLC) and the products were analyzed by matrix-assisted laser desorption ionization–time of flight (MALDI-TOF) mass spectrometry. The main products are mono- and diacrylates, while higher esters are formed as minor products. The highest conversion to sugar acrylates was observed for the D-glucose and D-fructose, followed by D-xylose and D-maltose. Molecular sieves had no pronounced effect on the conversion CONCLUSIONS: A feasible method is described to produce and to characterize sugar acrylates, including those containing more than two acrylate groups. The process for production of these higher esters could potentially be optimized further to produce molecules for cross-linking in acrylate polymerization and other applications. The direct enzymatic esterification of free carbohydrates with acrylic acid is unprecedented.
Background: There is an increased need to replace materials derived from fossil sources by renewables. Sugar- cane derived carbohydrates are very abundant in Brazil and are the cheapest sugars available in the market, with more than 400 million tons of sugarcane processed in the year 2007. The objective of this work was to study the prepn. of sugar acrylates from free sugars and free acrylic acid, thus avoiding the previous prepn. of protected sugar derivs., such as glycosides, or activated acrylates, such as vinyl acrylate. Results: Lipase catalyzed esterification of three mono- and two disaccharides with acrylic acid, in the presence or absence of mol. sieves was investigated. The reactions were monitored by high-performance liq. chromatog. (HPLC) and the products were analyzed by matrix-assisted laser desorption ionization-time of flight (MALDI-TOF) mass spectrometry. The main products are mono- and diacrylates, while higher esters are formed as minor products. The highest conversion to sugar acrylates was obsd. for the D-glucose and D- fructose, followed by D-xylose and D-maltose. Mol. sieves had no pronounced effect on the conversion. Conclusions: A feasible method is described to produce and to characterize sugar acrylates, including those contg. more than two acrylate groups. The process for prodn. of these higher esters could potentially be optimized further to produce mols. for crosslinking in acrylate polymn. and other applications. The direct enzymic esterification of free carbohydrates with acrylic acid is unprecedented. [on SciFinder (R)].
Although quantitative isotope data from speleothems has been used to evaluate isotope-enabled model simulations, currently no consensus exists regarding the most appropriate methodology through which to achieve this. A number of modelling groups will be running isotope-enabled palaeoclimate simulations in the framework of the Coupled Model Intercomparison Project Phase 6, so it is timely to evaluate different approaches to using the speleothem data for data–model comparisons. Here, we illustrate this using 456 globally distributed speleothem δ18O records from an updated version of the Speleothem Isotopes Synthesis and Analysis (SISAL) database and palaeoclimate simulations generated using the ECHAM5-wiso isotope-enabled atmospheric circulation model. We show that the SISAL records reproduce the first-order spatial patterns of isotopic variability in the modern day, strongly supporting the application of this dataset for evaluating model-derived isotope variability into the past. However, the discontinuous nature of many speleothem records complicates the process of procuring large numbers of records if data–model comparisons are made using the traditional approach of comparing anomalies between a control period and a given palaeoclimate experiment. To circumvent this issue, we illustrate techniques through which the absolute isotope values during any time period could be used for model evaluation. Specifically, we show that speleothem isotope records allow an assessment of a model's ability to simulate spatial isotopic trends. Our analyses provide a protocol for using speleothem isotope data for model evaluation, including screening the observations to take into account the impact of speleothem mineralogy on δ18O values, the optimum period for the modern observational baseline and the selection of an appropriate time window for creating means of the isotope data for palaeo-time-slices.
Ten ice-sheet models are used to study sensitivity of the Greenland and Antarctic ice sheets to prescribed changes of surface mass balance, sub-ice-shelf melting and basal sliding. Results exhibit a large range in projected contributions to sea-level change. In most cases, the ice volume above flotation lost is linearly dependent on the strength of the forcing. Combinations of forcings can be closely approximated by linearly summing the contributions from single forcing experiments, suggesting that nonlinear feedbacks are modest. Our models indicate that Greenland is more sensitive than Antarctica to likely atmospheric changes in temperature and precipitation, while Antarctica is more sensitive to increased ice-shelf basal melting. An experiment approximating the Intergovernmental Panel on Climate Change's RCP8.5 scenario produces additional first-century contributions to sea level of 22.3 and 8.1 cm from Greenland and Antarctica, respectively, with a range among models of 62 and 14 cm, respectively. By 200 years, projections increase to 53.2 and 26.7 cm, respectively, with ranges of 79 and 43 cm. Linear interpolation of the sensitivity results closely approximates these projections, revealing the relative contributions of the individual forcings on the combined volume change and suggesting that total ice-sheet response to complicated forcings over 200 years can be linearized.
Impact of multivalence and self-assembly in the design of polymeric antimicrobial peptide mimics
(2020)
Antimicrobial resistance is an increasingly serious challenge for public health and could result in dramatic negative consequences for the health care sector during the next decades. To solve this problem, antibacterial materials that are unsusceptible toward the development of bacterial resistance are a promising branch of research. In this work, a new type of polymeric antimicrobial peptide mimic featuring a bottlebrush architecture is developed, using a combination of reversible addition-fragmentation chain transfer (RAFT) polymerization and ring-opening metathesis polymerization (ROMP). This approach enables multivalent presentation of antimicrobial subunits resulting in improved bioactivity and an increased hemocompatibility, boosting the selectivity of these materials for bacterial cells. Direct probing of membrane integrity of treated bacteria revealed highly potent membrane disruption caused by bottlebrush copolymers. Multivalent bottlebrush copolymers clearly outperformed their linear equivalents regarding bioactivity and selectivity. The effect of segmentation of cationic and hydrophobic subunits within bottle brushes was probed using heterograft copolymers. These materials were found to self-assemble under physiological conditions, which reduced their antibacterial activity, highlighting the importance of precise structural control for such applications. To the best of our knowledge, this is the first example to demonstrate the positive impact of multivalence, generated by a bottlebrush topology in polymeric antimicrobial peptide mimics, making these polymers a highly promising material platform for the design of new bactericidal systems.