Reactive processing of polymers:effect of in situ compatibilisation on characteristics of blends of polyethylene terephthalate and ethylene-propylene rubber

Ethylene-propylene rubber (EPR) functionalised with glycidyl methacrylate (GMA) (f-EPR) during melt processing in the presence of a co-monomer, such as trimethylolpropane triacrylate (Tris), was used to promote compatibilisation in blends of polyethylene terephthalate (PET) and f-EPR, and their characteristics were compared with those of PET/f-EPR reactive blends in which the f-EPR was functionalised with GMA via a conventional free radical melt reaction (in the absence of a co-monomer). Binary blends of PETand f-EPR (with two types of f-EPR prepared either in presence or absence of the co-monomer) with various compositions (80/20, 60/40 and 50/50 w/w%) were prepared in an internal mixer. The blends were evaluated by their rheology (from changes in torque during melt processing and blending reflecting melt viscosity, and their melt flow rate), morphology scanning electron microscopy (SEM), dynamic mechanical properties (DMA), Fourier transform infrared (FTIR) analysis, and solubility (Molau) test. The reactive blends (PET/f-EPR) showed a marked increase in their melt viscosities in comparison with the corresponding physical (PET/EPR) blends (higher torque during melt blending), the extent of which depended on the amount of homopolymerised GMA (poly-GMA) present and the level of GMA grafting in the f-EPR. This increase was accounted for by, most probably, the occurrence of a reaction between the epoxy groups of GMA and the hydroxyl/carboxyl end groups of PET. Morphological examination by SEM showed a large improvement of phase dispersion, indicating reduced interfacial tension and compatibilisation, in both reactive blends, but with the Tris-GMA-based blends showing an even finer morphology (these blends are characterised by absence of poly-GMA and presence of higher level of grafted GMA in its f-EPR component by comparison to the conventional GMA-based blends). Examination of the DMA for the reactive blends at different compositions showed that in both cases there was a smaller separation between the glass transition temperatures compared to their position in the corresponding physical blends, which pointed to some interaction or chemical reaction between f-EPR and PET. The DMA results also showed that the shifts in the Tgs of the Tris-GMA-based blends were slightly higher than for the conventional GMA-blends. However, the overall tendency of the Tgs to approach each other in each case was found not to be significantly different (e.g. in a 60/40 ratio the former blend shifted by up to 4.5 °C in each direction whereas in the latter blend the shifts were about 3 °C). These results would suggest that in these blends the SEM and DMA analyses are probing uncorrelatable morphological details. The evidence for the formation of in situ graft copolymer between the f-EPR and PET during reactive blending was clearly illustrated from analysis by FTIR of the separated phases from the Tris-GMA-based reactive blends, and the positive Molau test pointed out to graft copolymerisation in the interface. A mechanism for the formation of the interfacial reaction during the reactive blending process is proposed.

Chemical specificity in REDOX-responsive materials:the diverse effects of different Reactive Oxygen Species (ROS) on polysulfide nanoparticles

REDOX responsive (nano)materials typically exhibit chemical changes in response to the presence and concentration of oxidants/reductants. Due to the complexity of biological environments, it is critical to ascertain whether the chemical response may depend on the chemical details of the stimulus, in addition to its REDOX potential, and whether chemically different responses can determine a different overall performance of the material. Here, we have used oxidation-sensitive materials, although these considerations can be extended also to reducible ones. In particular, we have used poly(propylene sulfide) (PPS) nanoparticles coated with a PEGylated emulsifier (Pluronic F127); inter alia, we here present also an improved preparative method. The nanoparticles were exposed to two Reactive Oxygen Species (ROS) typically encountered in inflammatory reactions, hydrogen peroxide (H2O2) and hypochlorite (ClO−); their response was evaluated with a variety of techniques, including diffusion NMR spectroscopy that allowed to separately characterize the chemically different colloidal species produced. The two oxidants triggered a different chemical response: H2O2 converted sulfides to sulfoxides, while ClO− partially oxidized them further to sulfones. The different chemistry correlated to a different material response: H2O2 increased the polarity of the nanoparticles, causing them to swell in water and to release the surface PEGylated emulsifier; the uncoated oxidized particles still exhibited very low toxicity. On the contrary, ClO− rapidly converted the nanoparticles into water-soluble, depolymerized fragments with a significantly higher toxicity. The take-home message is that it is more correct to discuss ‘smart’ materials in terms of an environmentally specific response to (REDOX) stimuli. Far from being a problem, this could open the way to more sophisticated and precisely targeted applications.

Novel evaluation procedure for internal and extraction efficiency of high-power blue LEDs

Internal quantum efficiency (IQE) of a high-brightness blue LED has been evaluated from the external quantum efficiency measured as a function of current at room temperature. Processing the data with a novel evaluation procedure based on the ABC-model, we have determined separately IQE of the LED structure and light extraction efficiency (LEE) of UX:3 chip. Full text Nowadays, understanding of LED efficiency behavior at high currents is quite critical to find ways for further improve­ment of III-nitride LED performance [1]. External quantum ef­ficiency ηe (EQE) provides integral information on the recom­bination and photon emission processes in LEDs. Meanwhile EQE is the product of IQE ηi and LEE ηext at negligible car­rier leakage from the active region. Separate determination of IQE and LEE would be much more helpful, providing correla­tion between these parameters and specific epi-structure and chip design. In this paper, we extend the approach of [2,3] to the whole range of the current/optical power variation, provid­ing an express tool for separate evaluation of IQE and LEE. We studied an InGaN-based LED fabricated by Osram OS. LED structure grown by MOCVD on sapphire substrate was processed as UX:3 chip and mounted into the Golden Dragon package without molding. EQE was measured with Labsphere CDS-600 spectrometer. Plotting EQE versus output power P and finding the power Pm corresponding to EQE maximum ηm enables comparing the measurements with the analytical rela­tionships ηi = Q/(Q+p1/2+p-1/2) ,p = P/Pm , and Q = B/(AC) 1/2 where A, Band C are recombination constants [4]. As a result, maximum IQE value equal to QI(Q+2) can be found from the ratio ηm/ηe plotted as a function of p1/2 +p1-1/2 (see Fig.la) and then LEE calculated as ηext = ηm (Q+2)/Q . Experimental EQE as a function of normalized optical power p is shown in Fig. 1 b along with the analytical approximation based on the ABC­model. The approximation fits perfectly the measurements in the range of the optical power (or operating current) variation by eight orders of magnitude. In conclusion, new express method for separate evaluation of IQE and LEE of III-nitride LEDs is suggested and applied to characterization of a high-brightness blue LED. With this method, we obtained LEE from the free chip surface to the air as 69.8% and IQE as 85.7% at the maximum and 65.2% at the operation current 350 rnA. [I] G. Verzellesi, D. Saguatti, M. Meneghini, F. Bertazzi, M. Goano, G. Meneghesso, and E. Zanoni, "Efficiency droop in InGaN/GaN blue light-emitting diodes: Physical mechanisms and remedies," 1. AppL Phys., vol. 114, no. 7, pp. 071101, Aug., 2013. [2] C. van Opdorp and G. W. 't Hooft, "Method for determining effective non radiative lifetime and leakage losses in double-heterostructure las­ers," 1. AppL Phys., vol. 52, no. 6, pp. 3827-3839, Feb., 1981. [3] M. Meneghini, N. Trivellin, G. Meneghesso, E. Zanoni, U. Zehnder, and B. Hahn, "A combined electro-optical method for the determination of the recombination parameters in InGaN-based light-emitting diodes," 1. AppL Phys., vol. 106, no. II, pp. 114508, Dec., 2009. [4] Qi Dai, Qifeng Shan, ling Wang, S. Chhajed, laehee Cho, E. F. Schubert, M. H. Crawford, D. D. Koleske, Min-Ho Kim, and Yongjo Park, "Carrier recombination mechanisms and efficiency droop in GalnN/GaN light-emitting diodes," App/. Phys. Leu., vol. 97, no. 13, pp. 133507, Sept., 2010. © 2014 IEEE.

Revealing 4-hydroxynonenal-histidine adducts as qualitative and quantitative biomarker of oxidative stress, lipid peroxidation and oxidative homeostasis

Findings on growth regulating activities of the end-product of lipid peroxidation 4-hydroxy-2-nonenal (HNE), which acts as a “second messenger of free radicals”, overlapped with the development of antibodies specific for the aldehyde-protein adducts. These led to qualitative immunochemical determinations of the HNE presence in various pathophysiological processes and to the change of consideration of the aldehyde’s bioactivities from toxicity into cell signalling. Moreover, findings of the HNE-protein adduct in various organs under physiological circumstances support the concept of “oxidative homeostasis”, which implies that oxidative stress and lipid peroxidation are not only pathological but also physiological processes. Reactive aldehydes, at least HNE, could play important role in oxidative homeostasis, while complementary research approaches might reveal the relevance of the aldehydic-protein adducts as major biomarkers of oxidative stress, lipid peroxidation and oxidative homeostasis. Aiming to join efforts in such research activities researchers interacting through the International 4-Hydroxynonenal Club acting within the SFRR-International and through networking projects of the system of the European Cooperation in Science and Technology (COST) carried validation of the methods for lipid peroxidation and further developed the genuine 4-HNE-His ELISA founding quantitative and qualitative methods for detection of 4-HNE-His adducts as valuable tool to study oxidative stress and lipid peroxidation in cell cultures, various organs and tissues and eventually for human plasma and serum analyses [1]. Reference: 1. Weber, Daniela. Lidija, Milkovic. Measurement of HNE-protein adducts in human plasma and serum by ELISA—Comparison of two primary antibodies. Redox Biol. 2013. 226-233.

Mechanistic studies on the degradation of gasoline oxygenates by advanced oxidation technologies and the reaction of 4-methyl-1,2,4-triazoline-3,5-dione with tetracyclopropylethylene

Gasoline oxygenates (MTBE, methyl tert-butyl ether; DIPE, di-isopropyl ether; ETBE, ethyl tert-butyl ether; TAME, tert-amyl ether) are added to gasoline to boost octane and enhance combustion. The combination of large scale use, high water solubility and only minor biodegradability has now resulted in a significant gasoline oxygenate contamination occurring in surface, ground, and drinking water systems. Combination of hydroxyl radical formation and the pyrolytic environment generated by ultrasonic irradiation (665 kHz) leads to the rapid degradation of MTBE and other gasoline oxygenates in aqueous media. ^ The presence of oxygen promotes the degradation processes by rapid reaction with carbon centered radicals indicating radical processes involving O 2 are significant pathways. A number of the oxidation products were identified. The formation of products (alcohols, ketones, aldehydes, esters, peroxides, etc) could be rationalized by mechanisms which involve hydrogen abstraction by OH radical and/or pyrolysis to form carboncentered radicals which react with oxygen and follow standard oxidation chain processes. ^ The reactions of N-substituted R-triazolinediones (RTAD; R = CH 3 or phenyl) have attracted considerable interest because they exhibit a number of unusual mechanistic characteristics that are analogous to the reactions of singlet oxygen (1O2) and offer an easy way to provide C-N bond(s) formation. The reactions of triazolinedione with olefins have been widely studied and aziridinium imides are generally accepted to be the reactive intermediates. ^ We observed the rapid formation of an unusual intermediate upon mixing tetracyclopropylethylene with 4-methyl-1,2,4-triazoline-3,5-dione in CDCl 3. Detailed characterization by NMR (proton, 13C, 2-D NMRs) indicates the intermediate is 5,5,6,6-tetracyclopropyl-3-methyl-5,6-dihydro-oxazolo[3,2- b][1,2,4]-triazolium-2-olate. Such products are extremely rare and have not been studied. Upon warming the intermediate is converted to 2 + 2 diazetidine (major) and ene product (minor). ^ To further explore the kinetics and dynamics of the reaction activation energies were obtained using Arrhenius plots. Activation energies for the formation of the intermediate from reactants, and 2+2 adduct from the intermediate were determined as 7.48 kcal moll and 19.8 kcal mol−1 with their pre-exponential values of 2.24 × 105 dm 3 mol−1 sec−1 and 2.75 × 108 sec−1, respectively, meaning net slow reactions because of low pre-exponential values caused by steric hindrance. ^

4-hydroxy estradiol-induced oxidant-mediated signaling is involved in the development of breast cancer

Breast cancer is a disease associated with excess exposures to estrogens. While the mode of cancer causation is unknown, others have shown that oxidative stress induced by prolonged exposure to estrogens mediates renal, liver, endometrial and mammary tumorigenesis though the mechanism(s) underling this process is unknown. In this study, we show that 4-hydroxyl 17β-estradiol (4-OHE2), a catechol metabolite of estrogen, induces mammary tumorigenesis in a redox dependent manner. We found that the mechanism of tumorigenesis involves redox activations of nuclear respiratory factor-1 (NRF1); a transcriptions factor associated with regulation of mitochondria biogenesis and oxidative phosphorylation (OXPHOS), as well as mediation of cell survival and growth of cells during periods of oxidative stress. Key findings from our study are as follows: (i) Prolonged treatments of normal mammary epithelial cells with 4-OHE2, increased the formation of intracellular reactive oxygen species (ROS). (ii) Estrogen-induced ROS activates redox sensitive transcription factors NRF1. (iii) 4-OHE2 through activation of serine-threonine kinase and histone acetyl transferase, phosphorylates and acetylate NRF1 respectively. (iv) Redox mediated epigenetic modifications of NRF1 facilitates mammary tumorigenesis and invasive phenotypes of breast cancer cells via modulations of genes involved in proliferation, growth and metastasis of exposed cells. (v) Animal engraftment of transformed clones formed invasive tumors. (vi) Treatment of cells or tumors with biological or chemical antioxidants, as well as silencing of NRF1 expressions, prevented 4-OHE2 induced mammary tumorigenesis and invasive phenotypes of MCF-10A cells. Based on these observations, we hypothesize that 4-OHE2 induced ROS epigenetically activate NRF1 through its phosphorylation and acylation. This, in turn, through NRF1-mediated transcriptional activation of the cell cycle genes, controls 4-OHE2 induced cell transformation and tumorigenesis.^

Relationship of Omega-3 Fatty Acids on C-Reactive Protein and Homocysteine in Haitian and African Americans with and without Type 2 Diabetes

Background: Omega-3 fatty acids (n-3) may be protective of cardiovascular risk factors for vulnerable populations. The purpose of this study was to assess the association between n-3 with, C-reactive protein (CRP), and homocysteine (HCY) in Black minorities with and without type 2 diabetes. Methods: A cross-sectional study was conducted with 406 participants: Haitian Americans (HA): n=238. African Americans (AA): n=172. Participants were recruited from a randomly generated mailing lists, local diabetes educators, community health practitioners and advertisements from 2008-2010. Sociodemographics and anthropometrics were collected and used to adjust analyses. All dietary variables were collected using the semi-quantitative food frequency questionnaire (FFQ) and used to quantify vitamin components. Blood was collected to measure CVD risk factors (blood lipids, HCY, and CRP). Results: African Americans had higher waist circumferences and C-reactive protein and consumed more calories as compared to Haitian Americans. Omega 3 fatty acid intake per calorie did not differ between these ethnicities, yet African Americans with low n-3 intake were three times more likely to have high C-reactive protein as compared to their counterparts [OR=3. 32 (1. 11, 9. 26) p=0.031]. Although homocysteine did not differ by ethnicity, African Americans with low omega 3 intake (<1 g/day) were four times as likely to have high homocysteine (>12 mg/L) as compared to their counterparts, adjusting for confounders [OR=4.63 (1.59, 12.0) p=0.004]. Consumption of n-3 by diabetes status was not associated with C-reactive protein or homocysteine levels. Conclusions: Consumption of n-3 may be protective of cardiovascular risk factors such as C-r

Obesity and Serum High Sensitivity C-Reactive Protein Levels Among Elderly Turkish Immigrants in the Netherlands with Type 2 Diabetes

The study examined the associations of anthropometric measures of obesity with high sensitivity C-reactive protein (hs-CRP) levels in Turkish immigrants with type 2 diabetes (T2D) living in the Netherlands. A total of 110 participants, physician-diagnosed with T2D, aged 30 years and older were recruited from multiple sources from The Hague, Netherlands. Serum hs-CRP levels were measured with immunoturbidimetric assay. Glycated hemoglobin (A1C) was determined by high-pressure liquid chromatography. Measures of obesity: body weight, body mass index (BMI), waist circumference (WC), hip circumference (HC), waist-to-hip ratio (WHR), and waist-to-height ratio (WHtR) were determined. Statistical analysis included descriptive statistics, Pearson’s correlations and multiple linear regressions (MLR) stratified by gender. Hs-CRP was log transformed to achieve normality. Subjects with hs-CRP levels >10 mg/L (n = 17) were excluded from the analysis. Females had a higher BMI (p = 0.007), HC (p < 0.001), and WHtR (p = 0.011) as compared to males. Conversely, males had a higher weight (p = 0.007), and WHR (p < 0.001) than females. MLR showed that after controlling for covariates, log hs-CRP was positively associated with BMI (B = 0.039, SE = 0.019, β = 0.287, p < 0.05), WC (B = 0.025, SE = 0.011, β = 0.332, p < 0.05) and WHtR (B = 4.015, SE = 1.464, β = 0.376, p < 0.01) in females only. Gender-specific associations between obesity measures and hs-CRP level need to be further investigated in the Turkish immigrant population. Hs-CRP assessment may be added as a standard of care for T2D treatment within this population.

China's Building of a Blue-Water Fleet

In recent years the People’s Republic of China has begun to exhibit a more aggressive naval policy as a result of its decision to switch its naval force from a primarily green-water fleet (coastal) to a blue-water fleet (expeditionary) (“China’s New,” n.d.). This decision has brought China to loggerheads not only with other local East and South Asian powers such as India and Japan, but also with the predominant blue-water power of the world, the United States, that sees its supremacy threatened (“When Grand,” n.d.). Why would China embark on a route that would pit it against the world naval superpower, the United States, which has a huge lead on China in terms of naval blue-water power? Why would China try to challenge and match the U.S. Navy’s eleven aircraft carriers (“The World’s,” n.d.)? What could compel China to embark on a plan that would so disrupt the balance of power in the waters around Asia? To fully understand the Chinese government’s decision, one must first look at Chinese import figures and Chinese trade routes.

Improving performance of a permeable reactive barrier in the degradation of trichloroethylene using ultrasound

The impact of ultrasound on improving the performance of a granular iron Permeable Reactive Barrier (PRB) in the degradation of Trichloroethylene (TCE) was evaluated. Two treatment columns made of clear Plexiglas with a height of 1ft and a diameter of 2 inches and filled with granular iron were used. One was fitted with 25Khz ultrasound probes. A solution of TCE was run through at constant flow rate. Samples obtained from the column at different residence times before and after sonication were analyzed for concentrations of TCE and used to generate concentration profiles to obtain rate constants, which were compared. An improvement of 23.4% in the reaction rate of TCE degradation was observed after sonication of the iron media suggesting that ultrasound may contribute to improving the performance of PRBs in the degradation of TCE in contaminated groundwater.

Seawater carbonate chemistry and biological processes during experiments with early life stages of the blue mussel Mytilus edulis, 2010

Several experiments have shown a decrease of growth and calcification of organisms at decreased pH levels. There is a growing interest to focus on early life stages that are believed to be more sensitive to environmental disturbances such as hypercapnia. Here, we present experimental data, acquired in a commercial hatchery, demonstrating that the growth of planktonic mussel (Mytilus edulis) larvae is significantly affected by a decrease of pH to a level expected for the end of the century. Even though there was no significant effect of a 0.25-0.34 pH unit decrease on hatching and mortality rates during the first 2 days of development nor during the following 13-day period prior to settlement, final shells were respectively 4.5±1.3 and 6.0±2.3% smaller at pHNBS~7.8 (pCO2~1100-1200 µatm) than at a control pHNBS of ~8.1 (pCO2~460-640 µatm). Moreover, a decrease of 12.0±5.4% of shell thickness was observed after 15d of development. More severe impacts were found with a decrease of ~0.5 pHNBS unit during the first 2 days of development which could be attributed to a decrease of calcification due to a slight undersaturation of seawater with respect to aragonite. Indeed, important effects on both hatching and D-veliger shell growth were found. Hatching rates were 24±4% lower while D-veliger shells were 12.7±0.9% smaller at pHNBS~7.6 (pCO2~1900 µatm) than at a control pHNBS of ~8.1 (pCO2~540 µatm). Although these results show that blue mussel larvae are still able to develop a shell in seawater undersaturated with respect to aragonite, the observed decreases of hatching rates and shell growth could lead to a significant decrease of the settlement success. As the environmental conditions considered in this study do not necessarily reflect the natural conditions experienced by this species at the time of spawning, future studies will need to consider the whole larval cycle (from fertilization to settlement) under environmentally relevant conditions in order to investigate the potential ecological and economical losses of a decrease of this species fitness in the field.

Stomach content records for pelagic fish (herring, mackerel, blue whiting, albacore and bluefin tuna) in the northeast Atlantic

Fish stomach content records extracted from the DAPSTOM 4.5 database (held at the UK Centre for Environment, Fisheries and Aquaculture Science - CEFAS). Data collated as part of the EU Euro-Basin project and specifically concerning herring (Clupea harengus), mackerel (Scomber scombrus), blue whiting (Micromesistius poutassou), albacore (Thunnus alalunga) and bluefin tuna (Thunnus thynnus). The data set consist of 20720 records - collected throughout the northeast Atlantic, between 1906 and 2011 - mostly during routine fisheries monitoring research cruises.

MID-IR luminosities and UV/optical star formation rates at z < 1.4

Ultraviolet (UV) nonionizing continuum and mid-infrared (IR) emission constitute the basis of two widely used star formation (SF) indicators at intermediate and high redshifts. We study 2430 galaxies with z < 1.4 in the Extended Groth Strip with deep MIPS 24 μm observations from FIDEL, spectroscopy from DEEP2, and UV, optical, and near-IR photometry from the AEGIS. The data are coupled with dust-reddened stellar population models and Bayesian spectral energy distribution (SED) fitting to estimate dust-corrected star formation rates (SFRs). In order to probe the dust heating from stellar populations of various ages, the derived SFRs were averaged over various timescales—from 100 Myr for "current" SFR (corresponding to young stars) to 1-3 Gyr for long-timescale SFRs (corresponding to the light-weighted age of the dominant stellar populations). These SED-based UV/optical SFRs are compared to total IR luminosities extrapolated from 24 μm observations, corresponding to 10-18 μm rest frame. The total IR luminosities are in the range of normal star-forming galaxies and luminous IR galaxies (10^10-10^12 L_☉). We show that the IR luminosity can be estimated from the UV and optical photometry to within a factor of 2, implying that most z < 1.4 galaxies are not optically thick. We find that for the blue, actively star-forming galaxies the correlation between the IR luminosity and the UV/optical SFR shows a decrease in scatter when going from shorter to longer SFR-averaging timescales. We interpret this as the greater role of intermediate age stellar populations in heating the dust than what is typically assumed. Equivalently, we observe that the IR luminosity is better correlated with dust-corrected optical luminosity than with dust-corrected UV light. We find that this holds over the entire redshift range. Many so-called green valley galaxies are simply dust-obscured actively star-forming galaxies. However, there exist 24 μm detected galaxies, some with L_IR>10^11 L_☉, yet with little current SF. For them a reasonable amount of dust absorption of stellar light (but presumably higher than in nearby early-type galaxies) is sufficient to produce the observed levels of IR, which includes a large contribution from intermediate and old stellar populations. In our sample, which contains very few ultraluminous IR galaxies, optical and X-ray active galactic nuclei do not contribute on average more than ~50% to the mid-IR luminosity, and we see no evidence for a large population of "IR excess" galaxies.

Interactions between Paramoeba perurans, the causative agent of amoebic gill disease, and the blue mussel, Mytilus edulis

Acknowledgements The authors would like to thank staff at Marine Scotland Science Patricia White, Rebecca McIntosh, Julia Black and Mark Fordyce for their technical assistance and invaluable feedback on the project. Thanks also go to Alex Douglas at the University of Aberdeen for his advice on data analysis and statistics. For feedback on the manuscript thanks to Lesley McEvoy and Rhiannon Inkster at the NAFC Marine Centre. The study was supported by the Marine Collaborations Forum (MarCRF) which aims to develop cross-disciplinary research between the University of Aberdeen and Marine Scotland Science. Finally, thanks are also due to Scottish Fishermen's Trust for a student support bursary.

An Exploration of Fairness in International Law through the Blue Nile and GERD

Peer reviewed