Synthesis of novel hyperbranched polymers featuring oxazoline linear units and their application in fast-drying solvent-borne coating formulations

Novel acid-terminated hyperbranched polymers (HBPs) containing adipic acid and oxazoline monomers derived from oleic and linoleic acid have been synthesized via a bulk polymerization procedure. Branching was achieved as a consequence of an acid-catalyzed opening of the oxazoline ring to produce a trifunctional monomer in situ which delivered branching levels of >45% as determined by 1H and 13C NMR spectroscopy. The HBPs were soluble in common solvents, such as CHCl3, acetone, tetrahydrofuran, dimethylformamide, and dimethyl sulfoxide and were further functionalized by addition of citronellol to afford white-spirit soluble materials that could be used in coating formulations. During end group modification, a reduction in branching levels of the HBPs (down to 12–24%) was observed, predominantly on account of oxazoline ring reformation and trans-esterification processes under the reaction conditions used. In comparison to commercial alkyd resin paint coatings, formulations of the citronellol-functionalized hyperbranched materials blended with a commercial alkyd resin exhibited dramatic decreases of the blend viscosity when the HBP content was increased. The curing characteristics of the HBP/alkyd blend formulations were studied by dynamic mechanical analysis which revealed that the new coatings cured more quickly and produced tougher materials than otherwise identical coatings prepared from only the commercial alkyd resins.

Evidence of a universal scaling relationship for leaf CO2 drawdown along an aridity gradient

The leaf carbon isotope ratio (δ13C) of C3 plants is inversely related to the drawdown of CO2 concentration during photosynthesis, which increases towards drier environments. We aimed to discriminate between the hypothesis of universal scaling, which predicts between-species responses of δ13C to aridity similar to within-species responses, and biotic homoeostasis, which predicts offsets in the δ13C of species occupying adjacent ranges. The Northeast China Transect spans 130–900 mm annual precipitation within a narrow latitude and temperature range. Leaves of 171 species were sampled at 33 sites along the transect (18 at ≥ 5 sites) for dry matter, carbon (C) and nitrogen (N) content, specific leaf area (SLA) and δ13C. The δ13C of species generally followed a common relationship with the climatic moisture index (MI). Offsets between adjacent species were not observed. Trees and forbs diverged slightly at high MI. In C3 plants, δ13C predicted N per unit leaf area (Narea) better than MI. The δ13C of C4 plants was invariant with MI. SLA declined and Narea increased towards low MI in both C3 and C4 plants. The data are consistent with optimal stomatal regulation with respect to atmospheric dryness. They provide evidence for universal scaling of CO2 drawdown with aridity in C3 plants.

Impact of strong deep ocean stratification on the glacial carbon cycle

During the Last Glacial Maximum, the climate was substantially colder and the carbon cycle was clearly different from the late Holocene. According to proxy data deep oceanic δ13C was very low, and the atmospheric CO2 concentration also reduced. Several mechanisms have been proposed to explain these changes, but none can fully explain the data, especially the very low deep ocean δ13C values. Oceanic core data show that the deep ocean was very cold and salty, which would lead to enhanced deep ocean stratification. We show that such an enhanced stratification in the coupled climate model CLIMBER-2 helps get very low deep oceanic δ13C values. Indeed the simulated δ13C reaches values as low as −0.8‰ in line with proxy data evidences. Moreover it increases the oceanic carbon reservoir leading to a small, yet robust, atmospheric CO2 drop of approximately 10 ppm.

Impact of brine-induced stratification on the glacial carbon cycle

During the cold period of the Last Glacial Maximum (LGM, about 21 000 years ago) atmospheric CO2 was around 190 ppm, much lower than the pre-industrial concentration of 280 ppm. The causes of this substantial drop remain partially unresolved, despite intense research. Understanding the origin of reduced atmospheric CO2 during glacial times is crucial to comprehend the evolution of the different carbon reservoirs within the Earth system (atmosphere, terrestrial biosphere and ocean). In this context, the ocean is believed to play a major role as it can store large amounts of carbon, especially in the abyss, which is a carbon reservoir that is thought to have expanded during glacial times. To create this larger reservoir, one possible mechanism is to produce very dense glacial waters, thereby stratifying the deep ocean and reducing the carbon exchange between the deep and upper ocean. The existence of such very dense waters has been inferred in the LGM deep Atlantic from sediment pore water salinity and δ18O inferred temperature. Based on these observations, we study the impact of a brine mechanism on the glacial carbon cycle. This mechanism relies on the formation and rapid sinking of brines, very salty water released during sea ice formation, which brings salty dense water down to the bottom of the ocean. It provides two major features: a direct link from the surface to the deep ocean along with an efficient way of setting a strong stratification. We show with the CLIMBER-2 carbon-climate model that such a brine mechanism can account for a significant decrease in atmospheric CO2 and contribute to the glacial-interglacial change. This mechanism can be amplified by low vertical diffusion resulting from the brine-induced stratification. The modeled glacial distribution of oceanic δ13C as well as the deep ocean salinity are substantially improved and better agree with reconstructions from sediment cores, suggesting that such a mechanism could have played an important role during glacial times.

Impact of oceanic processes on the carbon cycle during the last termination

During the last termination (from ~18 000 years ago to ~9000 years ago), the climate significantly warmed and the ice sheets melted. Simultaneously, atmospheric CO2 increased from ~190 ppm to ~260 ppm. Although this CO2 rise plays an important role in the deglacial warming, the reasons for its evolution are difficult to explain. Only box models have been used to run transient simulations of this carbon cycle transition, but by forcing the model with data constrained scenarios of the evolution of temperature, sea level, sea ice, NADW formation, Southern Ocean vertical mixing and biological carbon pump. More complex models (including GCMs) have investigated some of these mechanisms but they have only been used to try and explain LGM versus present day steady-state climates. In this study we use a coupled climate-carbon model of intermediate complexity to explore the role of three oceanic processes in transient simulations: the sinking of brines, stratification-dependent diffusion and iron fertilization. Carbonate compensation is accounted for in these simulations. We show that neither iron fertilization nor the sinking of brines alone can account for the evolution of CO2, and that only the combination of the sinking of brines and interactive diffusion can simultaneously simulate the increase in deep Southern Ocean δ13C. The scenario that agrees best with the data takes into account all mechanisms and favours a rapid cessation of the sinking of brines around 18 000 years ago, when the Antarctic ice sheet extent was at its maximum. In this scenario, we make the hypothesis that sea ice formation was then shifted to the open ocean where the salty water is quickly mixed with fresher water, which prevents deep sinking of salty water and therefore breaks down the deep stratification and releases carbon from the abyss. Based on this scenario, it is possible to simulate both the amplitude and timing of the long-term CO2 increase during the last termination in agreement with ice core data. The atmospheric δ13C appears to be highly sensitive to changes in the terrestrial biosphere, underlining the need to better constrain the vegetation evolution during the termination.

A metabolic system-wide characterisation of the pig: a model for human physiology

The pig is a single-stomached omnivorous mammal and is an important model of human disease and nutrition. As such, it is necessary to establish a metabolic framework from which pathology-based variation can be compared. Here, a combination of one and two-dimensional 1H and 13C nuclear magnetic resonance spectroscopy (NMR) and high-resolution magic angle spinning (HR-MAS) NMR was used to provide a systems overview of porcine metabolism via characterisation of the urine, serum, liver and kidney metabolomes. The metabolites observed in each of these biological compartments were found to be qualitatively comparable to the metabolic signature of the same biological matrices in humans and rodents. The data were modelled using a combination of principal components analysis and Venn diagram mapping. Urine represented the most metabolically distinct biological compartment studied, with a relatively greater number of NMR detectable metabolites present, many of which are implicated in gut-microbial co-metabolic processes. The major interspecies differences observed were in the phase II conjugation of extra-genomic metabolites; the pig was observed to conjugate p-cresol, a gut microbial metabolite of tyrosine, with glucuronide rather than sulfate as seen in man. These observations are important to note when considering the translatability of experimental data derived from porcine models.

The short-chain fatty acid acetate reduces appetite via a central homeostatic mechanism

Increased intake of dietary carbohydrate that is fermented in the colon by the microbiota has been reported to decrease body weight, although the mechanism remains unclear. Here we use in vivo11C-acetate and PET-CT scanning to show that colonic acetate crosses the blood–brain barrier and is taken up by the brain. Intraperitoneal acetate results in appetite suppression and hypothalamic neuronal activation patterning. We also show that acetate administration is associated with activation of acetyl-CoA carboxylase and changes in the expression profiles of regulatory neuropeptides that favour appetite suppression. Furthermore, we demonstrate through 13C high-resolution magic-angle-spinning that 13C acetate from fermentation of 13C-labelled carbohydrate in the colon increases hypothalamic 13C acetate above baseline levels. Hypothalamic 13C acetate regionally increases the 13C labelling of the glutamate–glutamine and GABA neuroglial cycles, with hypothalamic 13C lactate reaching higher levels than the ‘remaining brain’. These observations suggest that acetate has a direct role in central appetite regulation.

Serum carbon and nitrogen stable isotopes as potential biomarkers of dietary intake and their relation with incident type 2 diabetes: the EPIC-Norfolk study

Background: Stable-isotope ratios of carbon (13C/12C, expressed as δ13C) and nitrogen (15N/14N, or δ15N) have been proposed as potential nutritional biomarkers to distinguish between meat, fish, and plant-based foods. Objective: The objective was to investigate dietary correlates of δ13C and δ15N and examine the association of these biomarkers with incident type 2 diabetes in a prospective study. Design: Serum δ13C and δ15N (‰) were measured by using isotope ratio mass spectrometry in a case-cohort study (n = 476 diabetes cases; n = 718 subcohort) nested within the European Prospective Investigation into Cancer and Nutrition (EPIC)–Norfolk population-based cohort. We examined dietary (food-frequency questionnaire) correlates of δ13C and δ15N in the subcohort. HRs and 95% CIs were estimated by using Prentice-weighted Cox regression. Results: Mean (±SD) δ13C and δ15N were −22.8 ± 0.4‰ and 10.2 ± 0.4‰, respectively, and δ13C (r = 0.22) and δ15N (r = 0.20) were positively correlated (P < 0.001) with fish protein intake. Animal protein was not correlated with δ13C but was significantly correlated with δ15N (dairy protein: r = 0.11; meat protein: r = 0.09; terrestrial animal protein: r = 0.12, P ≤ 0.013). δ13C was inversely associated with diabetes in adjusted analyses (HR per tertile: 0.74; 95% CI: 0.65, 0.83; P-trend < 0.001], whereas δ15N was positively associated (HR: 1.23; 95% CI: 1.09, 1.38; P-trend = 0.001). Conclusions: The isotope ratios δ13C and δ15N may both serve as potential biomarkers of fish protein intake, whereas only δ15N may reflect broader animal-source protein intake in a European population. The inverse association of δ13C but a positive association of δ15N with incident diabetes should be interpreted in the light of knowledge of dietary intake and may assist in identifying dietary components that are associated with health risks and benefits.

Simulated last glacial maximum D14Catm and the deep glacial ocean carbon reservoir

∆14Catm has been estimated as 420 ± 80‰ (IntCal09) during the Last Glacial Maximum (LGM) compared to preindustrial times (0‰), but mechanisms explaining this difference are not yet resolved. ∆14Catm is a function of both cosmogenic production in the high atmosphere and of carbon cycling and partitioning in the Earth system. 10Be-based reconstructions show a contribution of the cosmogenic production term of only 200 ± 200‰ in the LGM. The remaining 220‰ have thus to be explained by changes in the carbon cycle. Recently, Bouttes et al. (2010, 2011) proposed to explain most of the difference in pCO2atm and δ13C between glacial and interglacial times as a result of brine-induced ocean stratification in the Southern Ocean. This mechanism involves the formation of very saline water masses that contribute to high carbon storage in the deep ocean. During glacial times, the sinking of brines is enhanced and more carbon is stored in the deep ocean, lowering pCO2atm. Moreover, the sinking of brines induces increased stratification in the Southern Ocean, which keeps the deep ocean well isolated from the surface. Such an isolated ocean reservoir would be characterized by a low ∆14C signature. Evidence of such 14C-depleted deep waters during the LGM has recently been found in the Southern Ocean (Skinner et al. 2010). The degassing of this carbon with low ∆14C would then reduce ∆14Catm throughout the deglaciation. We have further developed the CLIMBER-2 model to include a cosmogenic production of 14C as well as an interactive atmospheric 14C reservoir. We investigate the role of both the sinking of brine and cosmogenic production, alongside iron fertilization mechanisms, to explain changes in ∆14Catm during the last deglaciation. In our simulations, not only is the sinking of brine mechanism consistent with past ∆14C data, but it also explains most of the differences in pCO2atm and ∆14Catm between the LGM and preindustrial times. Finally, this study represents the first time to our knowledge that a model experiment explains glacial-interglacial differences in pCO2atm, δ13C, and ∆14C together with a coherent LGM climate.

Effect of cinnamon on gastric emptying, arterial stiffness, postprandial lipemia, glycemia, and appetite responses to high-fat breakfast

Abstract BACKGROUND: Cinnamon has been shown to delay gastric emptying of a high-carbohydrate meal and reduce postprandial glycemia in healthy adults. However, it is dietary fat which is implicated in the etiology and is associated with obesity, type 2 diabetes and cardiovascular disease. We aimed to determine the effect of 3 g cinnamon (Cinnamomum zeylanicum) on GE, postprandial lipemic and glycemic responses, oxidative stress, arterial stiffness, as well as appetite sensations and subsequent food intake following a high-fat meal. METHODS: A single-blind randomized crossover study assessed nine healthy, young subjects. GE rate of a high-fat meal supplemented with 3 g cinnamon or placebo was determined using the 13C octanoic acid breath test. Breath, blood samples and subjective appetite ratings were collected in the fasted and during the 360 min postprandial period, followed by an ad libitum buffet meal. Gastric emptying and 1-day fatty acid intake relationships were also examined. RESULTS: Cinnamon did not change gastric emptying parameters, postprandial triacylglycerol or glucose concentrations, oxidative stress, arterial function or appetite (p < 0.05). Strong relationships were evident (p < 0.05) between GE Thalf and 1-day palmitoleic acid (r = -0.78), eiconsenoic acid (r = -0.84) and total omega-3 intake (r = -0.72). The ingestion of 3 g cinnamon had no effect on GE, arterial stiffness and oxidative stress following a HF meal. CONCLUSIONS: 3 g cinnamon did not alter the postprandial response to a high-fat test meal. We find no evidence to support the use of 3 g cinnamon supplementation for the prevention or treatment of metabolic disease. Dietary fatty acid intake requires consideration in future gastrointestinal studies.

Addition of different fats to a carbohydrate food: impact on gastric emptying, glycaemic and satiety responses and comparison with in vitro digestion

In vitro, the addition of lipids to a carbohydrate food has been found to increase the digestibility of starch. In contrast, in vivo studies have shown that the addition of fat to a food can reduce the glycaemic response (GR). The aim of this study was to assess if delayed gastric emptying (GE) causes reduced GR with the addition of lipids to a carbohydrate food and if a relationship between GR and in vitro digestion of starch exists for high fat foods. Ten healthy volunteers were tested on five occasions after consuming pancakes containing 50 g of available carbohydrate and 202 kcal of sunflower oil, olive oil, butter, medium chain triglyceride (MCT) oil or a control containing no oil. GR was measured using fingerpick blood samples, satiety using visual analogue scales and GE using the 13C octanoic acid breath test. There was a significant difference in GR between the different pancake breakfasts (p = 0.05). The highest GR was observed following the control pancakes and the lowest following the olive oil pancakes. There were significant differences in GE half time, lag phase and ascension time (p < 0.05) between the different pancakes with the control pancakes having the shortest GE time and the MCT pancakes the longest. There was a significant difference in satiety parameters fullness (p = 0.003) and prospective consumption (p = 0.050), with satiety being lowest following the control pancakes. There was a significant inverse correlation between the GR and all satiety parameters. A significant inverse correlation (p = 0.009) was also observed between the digestibility of starch in vitro and GR in vivo. The paper indicates that the digestibility of starch in vitro does not predict the GR for high fat containing foods

Isotopic examination of links between diet, social differentiation and DISH at the post-medieval Carmelite Friary of Aalst, Belgium

Stable isotope ratios (δ13C and δ15N) were measured in human burials from the post-medieval (16th–18th c. AD) Carmelite friary burial grounds at Aalst, a town in Flanders, Belgium. Dietary patterns of 39 adult individuals were analyzed, from a mixed monastic and lay population buried in three different locations, reflecting groups with differing social status. The data show significant variation in the consumption of perhaps meat, but certainly also marine protein between females and males. This result represents a remarkable continuity with medieval dietary patterns, suggesting that the social and economic changes of the early modern period had a limited effect on everyday life. When both sexes were examined together, individuals buried in the cloister garth consumed significantly less marine protein compared to people buried in the church, likely reflecting social stratification. No statistical differences were observed between isotopic values from the church and the cloister alley, suggesting a similarly diverse diet of the monastic part of the buried population and that of the richer lay population. Finally, the hypothesis that diffuse idiopathic skeletal hyperostosis (DISH) is linked to a diet rich in animal protein was tested. No systematic or statistically significant differences between pathological and non-pathological bones from the same individuals affected with DISH were observed, and no statistical differences were found between individuals with DISH and individuals without DISH

Mid- to late Holocene Indian Ocean monsoon variability recorded in four speleothems from Socotra Island, Yemen

Four stalagmites covering the last 7.0 ka were sampled on Socotra, an island in the northern Indian Ocean to investigate the evolution of the northeast Indian Ocean Monsoon (IOM) since the mid Holocene. On Socotra, rain is delivered at the start of the southwest IOM in May–June and at the start of the northeast IOM from September to December. The Haggeher Mountains act as a barrier forcing precipitation brought by the northeast winds to fall preferentially on the eastern side of the island, where the studied caves are located. δ18O and δ13C and Mg/Ca and Sr/Ca signals in the stalagmites reflect precipitation amounts brought by the northeast winds. For stalagmite STM6, this amount effect is amplified by kinetic effects during calcite deposition. Combined interpretation of the stalagmites' signals suggest a weakening of the northeast precipitation between 6.0 and 3.8 ka. After 3.8 ka precipitation intensities remain constant with two superimposed drier periods, between 0 and 0.6 ka and from 2.2 to 3.8 ka. No link can be established with Greenland ice cores and with the summer IOM variability. In contrast to the stable northeast rainy season suggested by the records in this study, speleothem records from western Socotra indicate a wettening of the southwest rainy season on Socotra after 4.4 ka. The local wettening of western Socotra could relate to a more southerly path (more over the Indian Ocean) taken by the southwest winds. Stalagmite STM5, sampled at the fringe between both rain areas displays intermediate δ18O values. After 6.2 ka, similar precipitation changes are seen between eastern Socotra and northern Oman indicating that both regions are affected similarly by the monsoon. Different palaeoclimatologic records from the Arabian Peninsula currently located outside the ITCZ migration pathway display an abrupt drying around 6 ka due to their disconnection from the southwest rain influence. Records that are nowadays still receiving rain by the southwest winds, suggest a more gradual drying reflecting the weakening of the southwest monsoon.

The expression of the Cenomanian-Turonian oceanic anoxic event in Tibet

The Gongzha section of Tibet, China is located at the northern margin of the Indian Plate (SE Tethys) and is characterized by hemipelagic grey marls and marly limestones, light grey limestones and silty limestones, but no organic-rich sediments. High-resolution biostratigraphy reveals an expanded Cenomanian–Turonian (CT) boundary interval and the δ13C record includes the main features of the classical positive carbon-isotope excursion that characterizes the CT oceanic anoxic event. The biotic response inferred from the foraminifera suggests that oxic to dysoxic conditions prevailed, except for a short interval marked by peak abundance of Heterohelix that indicates a significantly dysoxic environment during the δ13C “b” peak excursion. The overall decreasing trend in redox-sensitive trace elements (RSTE) during the maximum δ13C excursion confirms the absence of significant longer-lasting anoxia in the Gongzha section. Enrichments in RSTE are linked to phases of increased detrital input. Chemical weathering indices suggest that the upper Cenomanian sediments accumulated under an increasingly hot and humid climate that culminated near the CT boundary. In the early Turonian lower weathering indices suggest a warm, drier climatic regime with reduced continental runoff. Phosphorus mass-accumulation rates show a significant peak at the onset of the positive δ13C excursion, followed by a decrease up to the basal Turonian. This pattern is positively correlated with the long-term decrease in detrital index as also observed in numerous other CT boundary sections (e.g., Eastbourne, Pueblo, and Whadi El Ghaib, Sinaï). Long-term phosphorus accumulation in the Gongzha section is therefore associated with changes in detrital input. The overall decreased detrital input can be explained by the increasingly remote continental sources due to the major transgression at the end of Cenomanian, coupled with changes in continental weathering intensity linked to increasingly more arid climate conditions.

Late Barremian-Early Aptian palaeoenvironmental change: the Cassis-La Bedoule section (SE France)

The well-dated section of Cassis-La Bédoule in the South Provencal Basin (southern France) allows for a detailed reconstruction of palaeoenvironmental change during the latest Barremian and Early Aptian. For this study, phosphorus (P) and clay-mineral contents, stable-isotope ratios on carbonate (δ13Ccarb) and organic matter (δ13Corg), and redox-sensitive trace elements (RSTE: V, U, As, Co, and Mo) have been measured in this historical stratotype. The base of the section consists of rudist limestone, which is attributed to the Urgonian platform. The presence of low P and RSTE content, and content of up to 30% kaolinite indicate deposition under oligotrophic and oxic conditions, and the presence of warm, humid climatic conditions on the adjacent continent. The top of the Urgonian succession is marked by a hardground with encrusted brachiopods and bivalves, which is interpreted as a drowning surface. The section continues with a succession of limestone and marl containing the first occurrence of planktonic foraminifera. This interval includes several laminated, organic-rich layers recording RSTE enrichments and high Corg:Ptot ratios. The deposition of these organic-rich layers was associated with oxygen-depleted conditions and a large positive excursion in δ13Corg. During this interval, a negative peak in the δ13Ccarb record is observed, which dates as latest Barremian. This excursion is coeval with negative excursions elsewhere in Tethyan platform and basin settings and is explained by the increased input of light dissolved inorganic carbon by rivers and/or volcanic activity. In this interval, an increase in P content, owing to reworking of nearshore sediments during the transgression, is coupled with a decrease in kaolinite content, which tends to be deposited in more proximal areas. The overlying hemipelagic sediments of the Early Aptian Deshayesites oglanlensis and D. weissi zones indicate rather stable palaeoenvironmental conditions with low P content and stable δ13C records. A change towards marl-dominated beds occurs close to the end of the D. weissi zone. These beds display a long decrease in their δ13Ccarb and δ13Corg records, which lasted until the end of the Deshayesites deshayesi subzone (corresponding to C3 in Menegatti et al., 1998). This is followed by a positive shift during the Roloboceras hambrovi and Deshayesites grandis subzones, which corresponds in time to oceanic anoxic event (OAE) 1a interval. This positive shift is coeval with two increases in the P content. The marly interval equivalent to OAE 1a lacks organic-rich deposits and RSTE enrichments indicating that oxic conditions prevailed in this particular part of the Tethys ocean. The clay mineralogy is dominated by smectite, which is interpreted to reflect trapping of kaolinite on the surrounding platforms rather than indicating a drier climate.