Behavior of the heterogeneous electron-transfer rate constants of arenes and substituted anthracenes in room-temperature ionic liquids

We report the anodic oxidation of several arenes and anthracenes within room-temperature ionic liquids (RTILs). In particular, the heterogeneous electron-transfer rates (k(0)) for substituted anthracenes and arenes are also investigated in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([C(2)mim][NTf2]) and found not to obey the outer-sphere Marcus-type behavior of these compounds in contrast to the behavior in traditional organic solvents,in particular the predictions for k(0) with molecular size and solvent static dielectric constant. To obtain the electron-transfer rate for 9-phenylanthracene, the dimerization and heterogeneous electron-transfer kinetics of its electrogenerated radical cations is studied in [C(2)mim][NTf2] and eight other RTILs and are both found to be largely independent of the solution viscosity.

The Madrilenian Chapel of San Isidro and its Previous Proyects

Desde antiguo ha examinado la historiografía la documentación relativa a la capilla de San Isidro en Madrid, deteniéndose en algunos proyectos que quedaron sin realizar hasta el definitivo de 1657. Sin embargo, esos intentos anteriores no han sido reseñados en su totalidad ni de manera correcta y exhaustiva. En este trabajo damos a conocer nuevos proyectos y precisamos muchos aspectos de los conocidos.

Ankle disease in juvenile idiopathic arthritis: ultrasound findings in clinically swollen ankles

The ankle joint is frequently involved in juvenile idiopathic arthritis (JIA), but it is unclear whether this is predominantly due to synovitis, tenosynovitis, or both. We performed clinic-based ultrasound examination to assess the prevalence of synovitis and tenosynovitis in children with JIA felt clinically to have active inflammatory disease of the ankle.

Human aflatoxin albumin adducts quantitatively compared by ELISA, HPLC with fluorescence detection, and HPLC with isotope dilution mass spectrometry

Essential to the conduct of epidemiologic studies examining aflatoxin exposure and the risk of heptocellular carcinoma, impaired growth, and acute toxicity has been the development of quantitative biomarkers of exposure to aflatoxins, particularly aflatoxin B-1. In this study, identical serum sample sets were analyzed for aflatoxin-albumin adducts by ELISA, high-performance liquid chromatography (HPLC) with fluorescence detection (HPLC-f), and HPLC with isotope dilution mass spectrometry (IDMS). The human samples analyzed were from an acute aflatoxicosis outbreak in Kenya in 2004 (n = 102) and the measured values ranged from 0.018 to 67.0, nondetectable to 13.6, and 0.002 to 17.7 ng/mg albumin for the respective methods. The Deming regression slopes for the HPLC-f and ELISA concentrations as a function of the IDMS concentrations were 0.71 (r(2) = 0.95) and 3.3 (r(2) = 0.96), respectively. When the samples were classified as cases or controls, based on clinical diagnosis, all methods were predictive of outcome (P < 0.01). Further, to evaluate assay precision, duplicate samples were prepared at three levels by dilution of an exposed human sample and were analyzed on three separate days. Excluding one assay value by ELISA and one assay by HPLC-f, the overall relative SD were 8.7%, 10.5%, and 9.4% for IDMS, HPLC-f, and ELISA, respectively. IDMS was the most sensitive technique and HPLC-f was the least sensitive method. Overall, this study shows an excellent correlation between three independent methodologies conducted in different laboratories and supports the validation of these technologies for assessment of human exposure to this environmental toxin and carcinogen.

Ex Vivo Expansion of Human Outgrowth Endothelial Cells Leads to IL-8-Mediated Replicative Senescence and Impaired Vasoreparative Function

Harnessing outgrowth endothelial cells (OECs) for vasoreparative therapy and tissue-engineering requires efficient ex-vivo expansion. How such expansion impacts on OEC function is largely unknown. In this study, we show that OECs become permanently cell-cycle arrested after ex-vivo expansion, which is associated with enlarged cell size, ß-galactosidase activity, DNA damage, tumour suppressor pathway activation and significant transcriptome changes. These senescence hallmarks were coupled with low telomerase activity and telomere shortening, indicating replicative senescence. OEC senescence limited their regenerative potential by impairing vasoreparative properties in-vitro and in-vivo. Integrated transcriptome-proteome analysis identified inflammatory signalling pathways as major mechanistic components of the OEC senescence programme. In particular, IL8 was an important facilitator of this senescence; depletion of IL8 in OECs significantly extended ex-vivo lifespan, delayed replicative senescence and enhanced function. While the ability to expand OEC numbers prior to autologous or allogeneic therapy remains a useful property, their replicative senescence and associated impairment of vasorepair needs to be considered. The current study also suggests that modulation of the senescence-associated secretory phenotype (SASP) could be used to optimise OEC therapy.

The Potential of a New Type of Carburettor to Assist SORE in Meeting EPA / CARB Phase 3 Legislation

Small off-road engines (SORE) have been recognised as a major source of air pollution. It is estimated that non handheld SORE annually produce over 1 million tonnes of HC+NOx and over 50 million tonnes of CO2. The fuel system design and its operating AFR are of key importance with regard to engine operation and engine out emissions. The conventional low-cost float carburettors used in these engines are relatively ineffective at atomising and preparing the fuel for combustion requiring a rich setting for acceptable functional performance. EPA and CARB have confirmed that Phase 3 limits are achievable for a “durable” engine fitted with a conventional well calibrated and manufactured “stock rich setting” float carburettor together with catalytic oxidation after-treatment and passive secondary air injection. The EPA and CARB strategy for meeting Phase 3 only considers the use of conventional float carburettors that operate at rich AFR’s over their entire engine operating range as no other cost effective alternative fuel system is yet available on the market. A cost effective alternative to the conventional carburettor that enabled leaner or optimised AFR operation with load and improved combustion performance would open the door to alternative strategies to meeting the phase 3 limits. This paper presents a completely new form of mechanical carburettor that gives AFR control with load, improved mixture preparation for improved combustion performance and has a lower production cost than conventional carburettors. The conventional and new fuel system designs and operation are discussed in detail and their technical merits demonstrated in the form of engine test data. The performance of different after-treatment systems is also simulated for different AFR profiles with load for a conventional or unmodified SORE engine. With optimised leaner operation and improved combustion characteristics, this new carburettor technology can provide significant engine out CO and HC+NOx reductions on the J1088 test cycle without loss of functional performance. Depending on the chosen emissions control strategy, minimum engine out emissions or optimum engine AFR for oxidation or three-way after-treatment or another, this new carburettor technology can be easily calibrated to provide the desired engine operating AFR profile on the J1088 cycle.

An Update on Sedimentary Pigments in Victoria Land Lakes (East Antarctica)

Antarctic ice-free areas contain lakes and ponds that have interesting limnological features and are of wide global significance as early warning indicators of climatic and environmental change. However, most linmological and paleolimnological studies in continental Antarctica are limited to certain regions. There are several ice-free areas in Victoria Land that have not yet been studied well. There is therefore a need to extend limnological studies in space and time to understand how different geological and climatic features affect the composition and biological activity of freshwater communities. With the aim of contributing to a better limnological characterization of Victoria Land, this paper reports data on sedimentary pigments (used to identify the main algal taxa) obtained through a methodology that is more sensitive and selective than that of previous studies. Analyses were extended to 48 water bodies in ice-free areas with differing lithology, latitude, and altitude, and with different morphometry and physical, chemical, and biological characteristics in order to identify environmental factors affecting the distribution and composition of freshwater autotrophic communities. A wider knowledge of lakes in a limnologically important region of Antarctica was obtained. Cyanophyta was found to be the most important algal group, followed by Chlorophyta and Bacillariophyta, whereas latitude and altitude are the main factors affecting pigment distribution.

Elevated Circulation Levels of an Antiangiogenic SERPIN in Patients with Diabetic Microvascular Complications Impair Wound Healing through Suppression of Wnt Signaling

Wound healing, angiogenesis and hair follicle maintenance are often impaired in the skin of diabetic patients, but the pathogenesis has not been well understood. Here, we report that circulation levels of kallistatin, a member of the serine proteinase inhibitor (SERPIN) superfamily with anti-angiogenic activities, were elevated in Type 2 diabetic patients with diabetic vascular complications. To test the hypothesis that elevated kallistatin levels could contribute to a wound healing deficiency via inhibition of Wnt/β-catenin signaling, we generated kallistatin-transgenic (KS-TG) mice. KS-TG mice had reduced cutaneous hair follicle density, microvascular density, and panniculus adiposus layer thickness as well as altered skin microvascular hemodynamics and delayed cutaneous wound healing. Using Wnt reporter mice, our results showed that Wnt/β-catenin signaling is suppressed in dermal endothelium and hair follicles in KS-TG mice. Lithium, a known activator of β-catenin via inhibition of glycogen synthase kinase-3β, reversed the inhibition of Wnt/β-catenin signaling by kallistatin and rescued the wound healing deficiency in KS-TG mice. These observations suggest that elevated circulating anti-angiogenic serpins in diabetic patients may contribute to impaired wound healing through inhibition of Wnt/β-catenin signaling. Activation of Wnt/β-catenin signaling, at a level downstream of Wnt receptors, may ameliorate the wound healing deficiency in diabetic patients.Journal of Investigative Dermatology accepted article preview online, 24 January 2014. doi:10.1038/jid.2014.40.

Enhancement of the properties of EPDM/NBR elastomers using nanoclay for seal applications

In this research, we have investigated the effects of addition of different percentages of nanoclay to the ethylene propylene diene monomer (EPDM) and nitrile butadiene rubber (NBR) on the characteristics of these rubbers as seal material. Properties such as tensile strength, modulus at different extensions, elongation at break, compressive set, hardness, and permeability and abrasion resistance are tested to assess the effect of addition of the nanoclay. Results indicate that addition of nanoclay at certain compositions could slightly reduce the strength of the rubber. However more stable modulus at different strains are provided, the hardness of the rubber is preserved and slightly enhanced, the permeability is reduced in both rubbers especially considerable decrease in EPDM is observed which is desirable in diminishing the effect of explosive decompression. At the same time the compression test shows that the nanoclay improves the performance of the rubbers under compression which is essential in seal application. The X-ray diffraction tests clarify that the dispersion of the nanoclay in the NBR samples is of high quality. In the EPDM samples, the dispersion is in need of improvement. POLYM. COMPOS., 30:1657-1667, 2009. © 2008 Society of Plastics Engineers.

Copper(I)/ketoABNO Catalysed Aerobic Alcohol Oxidation

A Cu(I)/9-azabicyclo[3.3.1]nonan-3-one N-oxyl (ketoABNO) aerobic catalyst system is highly effective for the oxidation of secondary alcohols, including unactivated aliphatic substrates. The effects of pressure and gas composition on catalyst performance are examined. The radical can be employed at low loadings and is also amenable to immobilisation on to solid supports.