Effects of CO2 Concentration on Leaf Photosynthesis and Stomatal Conductance of Potatoes Grown Under Different Irradiance Levels and Photoperiods

NASA Technical Reports Server (NTRS)

Wheeler, R. M.; Fitzpatrick, A. H.; Tibbitts, T. W.

2012-01-01

Potato (Solanum tuberosum L.) cvs. Russet Burbank, Denali, and Norland, were grown in environmental rooms controlled at approx 350 micro mol/mol (ambient during years 1987/1988) and 1000 micro mol/mol (enriched) CO2 concentrations. Plants and electric lamps were arranged to provide two irradiance zones, 400 and 800 micro mol/mol/square m/S PPF and studies were repeated using two photoperiods (12-h light / 12-h dark and continuous light). Leaf photosynthetic rates and leaf stomatal conductance were measured using fully expanded, upper canopy leaves at weekly intervals throughout growth (21 through 84 days after transplanting). Increasing the CO2 from approx 350 to 1000 micro mol/mol under the 12-h photoperiod increased leaf photosynthetic rates by 39% at 400 micro mol/mol/square m/S PPF and 27% at 800 micro mol/mol/square m/S PPF. Increasing the CO2 from approx 350 to 1000 micro mol/mol under continuous light decreased leaf photosynthetic rates by 7% at 400 micro mol/mol/square m/S PPF and 13% at 800 micro mol/mol/square m/S PPF. Increasing the CO2 from approx 350 to 1000 micro mol/mol under the 12-h photoperiod plants decreased stomatal conductance by an average of 26% at 400 micro mol/mol/square m/S PPF and 42% at 800 micro mol/mol/square m/S PPF. Under continuous light, CO2 enrichment resulted in a small increase (2%) of stomatal conductance at 400 micro mol/mol/square m/S PPF, and a small decrease (3%) at 800 micro mol/mol/square m/S PPF. Results indicate that CO2 enrichment under the 12-h photoperiod showed the expected increase in photosynthesis and decrease in stomatal conductance for a C3 species like potato, but the decreases in leaf photosynthetic rates and minimal effect on conductance from CO2 enrichment under continuous light were not expected. The plant leaves under continuous light showed more chlorosis and some rusty flecking versus plants under the 12-h photoperiod, suggesting the continuous light was more stressful on the plants. The increased rates of leaf photosynthesis with increased CO2 concentration paralleled trends in biomass production (published previously) but were not proportional to the biomass yields.

Analysis of trace impurities in neon by a customized gas chromatography.

PubMed

Yin, Min Kyo; Lim, Jeong Sik; Moon, Dong Min; Lee, Gae Ho; Lee, Jeongsoon

2016-09-09

Excimer lasers, widely used in the semiconductor industry, are crucial for analyzing the purity of premix laser gases for the purpose of controlling stable laser output power. In this study, we designed a system for analyzing impurities in pure neon (Ne) base gas by customized GC. Impurities in pure neon (H2 and He), which cannot be analyzed at the sub-μmol/mol level using commercial GC detectors, were analyzed by a customized pulsed-discharge Ne ionization detector (PDNeD) and a pressurized injection thermal conductivity detector using Ne as the carrier gas (Pres. Inj. Ne-TCD). From the results, trace species in Ne were identified with the following detection limits: H2, 0.378μmol/mol; O2, 0.119μmol/mol; CH4, 0.880μmol/mol; CO, 0.263μmol/mol; CO2, 0.162μmol/mol (PDNeD); and He, 0.190μmol/mol (Pres. Inj. Ne-TCD). This PDNeD and pressurized injection Ne-TCD technique thus developed permit the quantification of trace impurities present in high-purity Ne. Copyright © 2016. Published by Elsevier B.V.

PVO / NGO initiatives, Latin America. Grupo pela VIDDA, Brazil.

PubMed

1996-01-01

"VIDDA" is a Portuguese acronym representing enhancement, integration, and dignity of people living with HIV/AIDS (PWAs). The groups are composed of people infected with HIV, their friends, relatives, lovers, and anyone who feels that his or her everyday life has been affected by the epidemic. They hope that through solidarity they can respond to the difficult situation facing people who are HIV positive in Brazil. Grupo pela VIDDA seeks to raise the consciousness of the government and the society and force them to take responsibility for the epidemic. Their fundamental objective is to fight for PWAs to have a full range of civil rights. "This is a fight that we have in common with all the Brazilian people who are searching for democracy, the right to work, and access to good health services," states a Grupo pela VIDDA brochure. Through their network they provide accurate and current information, counseling, legal assistance, and sponsor support groups. For more information, please contact Grupo pela VIDDA, Rua General Jardim, 556 CEP 01223-010, Cx Postal 54063, CEP 01296, Sao Paulo SP, tel/fax: +55 11 258 7729; or Rua 7 de Setembro, 48 12 andar CEP 20050-000, tel: +55 21 224 1654, fax: +55 21 294 5602. There are also offices in Curitiba, Goiania, Niteroi, Recife, and Vitoria. full text

Levels of 1-hydroxypyrene in urine of people living in an oil producing region of the Andean Amazon (Ecuador and Peru).

PubMed

Webb, Jena; Coomes, Oliver T; Mergler, Donna; Ross, Nancy A

2018-01-01

Polycyclic aromatic hydrocarbons (PAHs) are contaminants with carcinogenic effects but little is known about their presence in environments surrounding oil drilling operations and spills or exposure levels in nearby communities. The objective of this study was to characterize PAH levels in people living near oil drilling operations in relation to fish consumption, occupation, source of water and other socio-demographic characteristics. This pilot study examined PAH exposure by measuring 1-hydroxypyrene (1-OHP) in urine samples using high-performance liquid chromatography and fluorescence detection from 75 women and men in the Ecuadorian and Peruvian Amazon living near oil drilling operations and who answered a questionnaire collecting socio-demographic, occupational and dietary information. Data were analyzed using multiple linear regression models. The mean value of 1-OHP was 0.40 μmol/mol creatinine, 95% CI 0.32-0.46 μmol/mol creatinine. Women who used water from a surface source (for washing clothes or bathing) had almost twice the amount of 1-OHP in their urine (mean 1-OHP = 0.41 μmol/mol creatinine, 95% CI 0.28-0.54 μmol/mol creatinine, n = 23) as women who used water from either a well, a spring or rain (mean 1-OHP = 0.22 μmol/mol creatinine, 95% CI 0.11-0.34 μmol/mol creatinine, n = 6). Men who reported eating a bottom-dwelling species as their most commonly consumed fish (mean 1-OHP = 0.50 μmol/mol creatinine, 95% CI 0.36-0.64 μmol/mol creatinine, n = 31) had twice as much 1-OHP in their urine as men who reported a pelagic fish (mean 1-OHP = 0.25 μmol/mol creatinine, 95% CI 0.15-0.35 μmol/mol creatinine, n = 15), signaling either oral (fish consumption) or dermal (while standing in water fishing benthic species) exposure. More contact with surface water and benthic fish may result in higher levels of 1-OHP in human urine among the study population. Reducing the amount of oil and wastes entering the waterways in Andean Amazonia would be one way to reduce exposure.

Effects of CO2 on stomatal conductance: do stomata open at very high CO2 concentrations?

NASA Technical Reports Server (NTRS)

Wheeler, R. M.; Mackowiak, C. L.; Yorio, N. C.; Sager, J. C.

1999-01-01

Potato and wheat plants were grown for 50 d at 400, 1000 and 10000 micromoles mol-1 carbon dioxide (CO2). and sweetpotato and soybean were grown at 1000 micromoles mol-1 CO2 in controlled environment chambers to study stomatal conductance and plant water use. Lighting was provided with fluorescent lamps as a 12 h photoperiod with 300 micromoles m-2 s-1 PAR. Mid-day stomatal conductances for potato were greatest at 400 and 10000 micromoles mol-1 and least at 1000 micromoles mol-1 CO2. Mid-day conductances for wheat were greatest at 400 micromoles mol-1 and least at 1000 and 10000 micromoles mol-1 CO2. Mid-dark period conductances for potato were significantly greater at 10000 micromoles mol-1 than at 400 or 1000 micromoles mol-1, whereas dark conductance for wheat was similar in all CO2 treatments. Temporarily changing the CO2 concentration from the native 1000 micromoles mol-1 to 400 micromoles mol-1 increased mid-day conductance for all species, while temporarily changing from 1000 to 10000 micromoles mol-1 also increased conductance for potato and sweetpotato. Temporarily changing the dark period CO2 from 1000 to 10000 micromoles mol-1 increased conductance for potato, soybean and sweetpotato. In all cases, the stomatal responses were reversible, i.e. conductances returned to original rates following temporary changes in CO2 concentration. Canopy water use for potato was greatest at 10000, intermediate at 400, and least at 1000 micromoles mol-1 CO2, whereas canopy water use for wheat was greatest at 400 and similar at 1000 and 10000 micromoles mol-1 CO2. Elevated CO2 treatments (i.e. 1000 and 10000 micromoles mol-1) resulted in increased plant biomass for both wheat and potato relative to 400 micromoles mol-1, and no injurious effects were apparent from the 10000 micromoles mol-1 treatment. Results indicate that super-elevated CO2 (i.e. 10000 micromoles mol-1) can increase stomatal conductance in some species, particularly during the dark period, resulting in increased water use and decreased water use efficiency.

Pyrolysis kinetics and thermal behavior of waste sawdust biomass using thermogravimetric analysis.

PubMed

Mishra, Ranjeet Kumar; Mohanty, Kaustubha

2018-03-01

The present study reports pyrolysis behavior of three waste biomass using thermogravimetric analysis to determine kinetic parameters at five different heating rates. Physiochemical characterization confirmed that these biomass have the potential for fuel and energy production. Pyrolysis experiments were carried out at five different heating rates (5-25 °C min -1 ). Five model-free methods such as Kissinger-Akahira-Sunose (KAS), Ozawa-Flynn-Wall (OFW), Friedman, Coats-Redfern, and distributed activation energy (DAEM) were used to calculate the kinetic parameters. The activation energy was found to be 171.66 kJ mol -1 , 148.44 kJ mol -1 , and 171.24 kJ mol -1 from KAS model; 179.29 kJ mol -1 , 156.58 kJ mol -1 , and 179.47 kJ mol -1 from OFW model; 168.58 kJ mol -1 , 181.53 kJ mol -1 , and 184.61 kJ mol -1 from Friedman model; and 206.62 kJ mol -1 , 171.63 kJ mol -1 , and 160.45 kJ mol -1 from DAEM model for PW, SW, AN biomass respectively. The calculated kinetic parameters are in good agreement with other reported biomass. Copyright © 2017 Elsevier Ltd. All rights reserved.

The nutritional effect of Moringa oleifera fresh leaves as feed supplement on Rhode Island Red hen egg production and quality.

PubMed

Abou-Elezz Fouad Mohammed, Khaled; Sarmiento-Franco, Luis; Santos-Ricalde, Ronald; Solorio-Sanchez, Javier Francisco

2012-06-01

This study aimed to evaluate the potential of Moringa oleifera fresh leaves (MOL) as feed supplement on the performance and egg quality of Rhode Island Red (RIR) hens under the tropical conditions of Yucatan, Mexico. Forty-eight RIR hens were allocated in 12 floor pen replicates each with four birds. Thereafter, the replicates were divided into three groups which were corresponded to ad libitum feed (control), ad libitum feed supplemented with MOL T1 (AL + MOL) and restricted feed amount (20% lower than control) with MOL T2 (RCD + MOL), respectively. T1 (AL + MOL) had higher egg laying rate (71.4% versus 66.6%), higher daily egg mass production (45.4 versus 41.9 g/day), lower feed intake (121.3 versus 127.5 g/day) and better feed conversion ratio (2.8 versus 3.2 g feed:g egg) versus control. T2 / (RCD + MOL) had lower values of body weight, egg laying rate, egg weight and egg mass, and recorded better feed conversion ratio than the control group. The control group recorded a higher percentage of pecked eggs versus T1 and T2 (6.5% versus 1.2% and 2.0 %). Similar intake of MOL (3.1 and 3.4 g DM/day) was recorded in T1 (AL + MOL) and T2 (RCD + MOL). Yolk color was improved significantly in T1 (AL + MOL) than both control and T2 (RCD + MOL), while T2 (RCD + MOL) had eggs with lower yolk and higher albumen percentages than the other two ad libitum groups. The results suggest that MOL could be used successfully as sustainable tropical feed resource for RIR hens.

Effect of irradiance, sucrose, and CO2 concentration on the growth of potato (Solanum tuberosum L.) in vitro

NASA Technical Reports Server (NTRS)

Yorio, Neil C.; Wheeler, Raymond M.; Weigel, Russell C.

1995-01-01

Growth measurements were taken of potato plantlets (Solanum tuberosum L.) cvs. Norland (NL), Denali (DN), and Kennebec (KN), grown in vitro. Studies were conducted in a growth chamber, with nodal explants grown for 21 days on Murashige and Skoog salts with either 0, 1, 2, or 3% sucrose and capped with loose-fitted Magenta 2-way caps that allowed approximately 2.25 air exchanges/hour. Plantlets were exposed to either 100 or 300 micro mol/sq m/s photosynthetic photon flux (PPF), and the growth chamber was maintained at either 400 or 4000 micro mol/mol CO2. Regardless of PPF, all cvs. that were grown at 4000 micro mol/mol CO2 showed significant increases in total plantlet dry weight (TDW) and shoot length (SL) when sucrose was omitted from the media, indicating an autotrophic response. At 400 micro mol/mol CO2, all cvs. showed an increase in TDW and SL with increasing sucrose under both PPF levels. Within any sucrose treatment, the highest TDW for all cvs. resulted from 300 micro mol/sq m/s PPF and 4000 micro mol/mol CO2 At 4000 micro mol/mol CO2, TDW showed no further increase with sucrose levels above 1% for cvs. NL and DN at both PPF levels, suggesting that sucrose levels greater than 1% may hinder growth when CO2 enrichment is used.

Ureaplasma parvum causes hyperammonemia in a pharmacologically immunocompromised murine model.

PubMed

Wang, X; Greenwood-Quaintance, K E; Karau, M J; Block, D R; Mandrekar, J N; Cunningham, S A; Mallea, J M; Patel, R

2017-03-01

A relationship between hyperammonemia and Ureaplasma infection has been shown in lung transplant recipients. We have demonstrated that Ureaplasma urealyticum causes hyperammonemia in a novel immunocompromised murine model. Herein, we determined whether Ureaplasma parvum can do the same. Male C3H mice were given mycophenolate mofetil, tacrolimus, and prednisone for 7 days, and then challenged with U. parvum intratracheally (IT) and/or intraperitoneally (IP), while continuing immunosuppression over 6 days. Plasma ammonia concentrations were determined and compared using Wilcoxon rank-sum tests. Plasma ammonia concentrations of immunosuppressed mice challenged IT/IP with spent broth (median, 188 μmol/L; range, 102-340 μmol/L) were similar to those of normal (median, 226 μmol/L; range, 154-284 μmol/L, p > 0.05), uninfected immunosuppressed (median, 231 μmol/L; range, 122-340 μmol/L, p > 0.05), and U. parvum IT/IP challenged immunocompetent (median, 226 μmol/L; range, 130-330 μmol/L, p > 0.05) mice. Immunosuppressed mice challenged with U. parvum IT/IP (median 343 μmol/L; range 136-1,000 μmol/L) or IP (median 307 μmol/L; range 132-692 μmol/L) had higher plasma ammonia concentrations than those challenged IT/IP with spent broth (p < 0.001). U. parvum can cause hyperammonemia in pharmacologically immunocompromised mice.

Simultaneous application of ethylene and 1-MCP affects banana ripening features during storage.

PubMed

Botondi, Rinaldo; De Sanctis, Federica; Bartoloni, Serena; Mencarelli, Fabio

2014-08-01

In order to avoid the ripening blocking effect of 1-MCP (1-methylcyclopropene) on bananas when applied before ethylene commercial treatment, 1-MCP in combination with 'CD ethylene' (ethylene-cyclodextrin complex) was used in gas formulations: 300 nmol mol(-1) 1-MCP + 1200, 2400 or 4800 nmol mol(-1) ethylene (ETH). Control bananas received 1-MCP alone or 4800 nmol mol(-1) ethylene alone or no treatment. Treatments were done on overseas shipped bananas, at 14 °C, 90% relative humidity (RH), for 16 h; the bananas were stored under the same atmospheric conditions. After 4 or 12 days the bananas were commercially treated with 500 µmol mol(-1) ethylene. A 300 nmol mol(-1) 1-MCP treatment significantly blocked banana ripening in terms of physiological and technological parameters, inhibiting ethylene production and respiration, despite the commercial ethylene treatment. The application of 300 nmol mol(-1) 1-MCP + 1200 or 2400 nmol mol(-1) ethylene delayed ripening but with a regular pattern. A 300 nmol mol(-1) 1-MCP + 4800 nmol mol(-1) ethylene application did not delay ripening as did 4800 nmol mol(-1) ethylene treatment. The development of black spots was closely associated with advanced ripening/senescence of fruits. The combined 300 nmol mol(-1) 1-MCP + 1200 or 2400 nmol mol(-1) ethylene treatment appears to be a promising treatment to extend banana storage, following overseas shipping. © 2014 Society of Chemical Industry.

Mitochondrial pathway mediated by reactive oxygen species involvement in α-hederin-induced apoptosis in hepatocellular carcinoma cells.

PubMed

Li, Jiao; Wu, Dan-Dan; Zhang, Ji-Xiang; Wang, Jing; Ma, Jing-Jing; Hu, Xue; Dong, Wei-Guo

2018-05-07

To investigate the antitumor activity of α-hederin in hepatocellular carcinoma (HCC) cells and its underlying mechanisms in vitro and in vivo . SMMC-7721, HepG-2 and Huh-7 HCC cells were cultured in vitro and treated with α-hederin (0, 5 μmol/L, 10 μmol/L, 15 μmol/L, 20 μmol/L, 25 μmol/L, 30 μmol/L, 35 μmol/L, 40 μmol/L, 45 μmol/L, 50 μmol/L, 55 μmol/L, or 60 μmol/L) for 12 h, 24 h, or 36 h, and cell viability was then detected by the Cell Counting Kit-8. SMMC-7721 cells were treated with 0, 5 μmol/L, 10 μmol/L, or 20 μmol/L α-hederin for 24 h with or without DL-buthionine- S , R -sulfoximine (2 mmol/L) or N -acetylcysteine (5 mmol/L) pretreatment for 2 h, and additional assays were subsequently performed. Apoptosis was observed after Hoechst staining. Glutathione (GSH) and adenosine triphosphate (ATP) levels were measured using GSH and ATP Assay Kits. Intracellular reactive oxygen species (ROS) levels were determined by measuring the oxidative conversion of 2',7'-dichlorofluorescin diacetate. Disruption of the mitochondrial membrane potential was evaluated using JC-1 staining. The protein levels of Bax, Bcl-2, cleaved caspase-3, cleaved caspase-9, apoptosis-inducing factor and cytochrome C were detected by western blotting. The antitumor efficacy of α-hederin in vivo was evaluated in a xenograft tumor model. The α-hederin treatment induced apoptosis of HCC cells. The apoptosis rates in the control, low-dose α-hederin (5 μmol/L), mid-dose α-hederin (10 μmol/L) and high-dose α-hederin (20 μmol/L) groups were 0.90% ± 0.26%, 12% ± 2.0%, 21% ± 2.1% and 37% ± 3.8%, respectively ( P < 0.05). The α-hederin treatment reduced intracellular GSH and ATP levels, induced ROS, disrupted the mitochondrial membrane potential, increased the protein levels of Bax, cleaved caspase-3, cleaved caspase-9, apoptosis-inducing factor and cytochrome C, and decreased Bcl-2 expression. The α-hederin treatment also inhibited xenograft tumor growth in vivo . The α-hederin saponin induces apoptosis of HCC cells via the mitochondrial pathway mediated by increased intracellular ROS and may be an effective treatment for human HCC.

Paleoenvironmental implications of early diagenetic siderites of the Paraíba do Sul Deltaic Complex, eastern Brazil

NASA Astrophysics Data System (ADS)

Rodrigues, Amanda Goulart; De Ros, Luiz Fernando; Neumann, Reiner; Borghi, Leonardo

2015-06-01

Abundant early diagenetic siderites occur as spherulites and rhombohedral microcrystalline and macrocrystalline crystals in the cores of the 2-MU-1-RJ well, drilled in the Paraíba do Sul Deltaic Complex, Rio de Janeiro (Brazil). The host sediments of the siderites are siliciclastic, hybrid, and carbonate deposits. Intense pedogenetic processes affected the siliciclastic sediments immediately after deposition, comprising clay illuviation, plants bioturbation, feldspar dissolution, and iron oxide/hydroxide precipitation. Siderite and pyrite are the main diagenetic constituents. The other diagenetic products are kaolinite, smectite, argillaceous and carbonate pseudomatrix, quartz overgrowths, diagenetic titanium minerals, jarosite, and iron oxides/hydroxides. Early diagenetic siderites were separated into four groups based on their elemental and stable isotopic composition, as well as on their paragenetic relationships with the other constituents and with the host sediments. Spherulitic to macrocrystalline siderites from group 1 are almost pure (average: 94.7 mol% FeCO3; 1.2 mol% MgCO3; 2.3 mol% CaCO3; 1.8 mol% MnCO3) and precipitated from meteoric porewaters in continental siliciclastic rocks under suboxic conditions (δ18Ovpdb values range in - 10.28 to - 5.57‰ and the δ13Cvpdb values in - 12.68 to - 4.33‰). Microcrystalline rhombohedral siderites from group 2 have zonation due to substantial Ca and Mg substitution (core average: 78.5 mol% FeCO3; 4.2 mol% MgCO3; 15.7 mol% CaCO3; 1.6 mol% MnCO3; edge average: 74.0 mol% FeCO3; 9.2 mol% MgCO3; 15.6 mol% CaCO3; 1.1 mol% MnCO3), and δ13Cvpdb and δ18Ovpdb values of + 0.17‰ and - 1.96‰, precipitated from marine porewaters in packstones/wackestones under methanogenic conditions. The group 3 is represented by irregular spherulitic siderites with moderate Ca and Mg substitutions (average: 80.2 mol% FeCO3; 7.9 mol% MgCO3; 11.3 mol% CaCO3; 0.6 mol% MnCO3), with δ18Ovpdb values ranging from - 5.96 to - 7.61‰ and δ13Cvpdb values ranging from - 5.15 to - 10.41‰. The group 4 microcrystalline siderites are magnesium-rich (average: 57.3 mol% FeCO3; 31.4 mol% MgCO3; 9.6 mol% CaCO3; 1.7 mol% MnCO3; δ13Cvpdb + 1.43‰ and δ18Ovpdb - 14.09‰). The group 3 and 4 siderites were formed from brackish porewater under suboxic conditions in hybrid and siliciclastic rocks. These variations in siderites are probably related to the Paraíba do Sul River dynamics, to sea level changes and to climatic variations that took place during the Quaternary.

The thermochemistry of cubane 50 years after its synthesis: a high-level theoretical study of cubane and its derivatives.

PubMed

Agapito, Filipe; Santos, Rui C; Borges dos Santos, Rui M; Martinho Simões, José A

2015-03-26

The gas-phase enthalpy of formation of cubane (603.4 ± 4 kJ mol(-1)) was calculated using an explicitly correlated composite method (W1-F12). The result obtained for cubane, together with the experimental value for the enthalpy of sublimation, 54.8 ± 2.0 kJ mol(-1), led to 548.6 ± 4.5 kJ mol(-1) for the solid-phase enthalpy of formation. This value is only 6.8 kJ mol(-1) higher than the 50-year-old original calorimetric result. The carbon-hydrogen bond dissociation enthalpy (C-H BDE) of cubane (438.4 ± 4 kJ mol(-1)), together with properties relevant for its experimental determination using gas-phase ion thermochemistry, namely the cubane gas-phase acidity (1704.6 ± 4 kJ mol(-1)), cubyl radical electron affinity (45.8 ± 4 kJ mol(-1)), cubane ionization energy (1435.1 ± 4 kJ mol(-1)), cubyl radical cation proton affinity (918.8 ± 4 kJ mol(-1)), cubane cation appearance energy (1099.6 ± 4 kJ mol(-1)), and cubyl ionization energy (661.2 ± 4 kJ mol(-1)), were also determined. These values were compared with those calculated for unstrained hydrocarbons (viz., methane, ethane, and isobutane). The strain energy of cubane (667.2 kJ mol(-1)) and cubyl radical (689.4 kJ mol(-1)) were independently estimated via quasihomodesmotic reactions. These values were related via a simple model to the C-H BDE in cubane. Taking into account the accuracy of the computational method, the comparison with high-precision experimental results, and the data consistency afforded by the relevant thermodynamic cycles, we claim an uncertainty better than ±4 kJ mol(-1) for the new enthalpy of formation values presented.

Phenytoin intoxication during concurrent diazepam therapy

PubMed Central

Rogers, Howard J.; Haslam, Robert A.; Longstreth, James; Lietman, Paul S.

1977-01-01

Phenytoin elimination is a saturable process obeying Michaelis-Menten kinetics. Plasma phenytoin levels are not related linearly to dose, and small changes in enzyme activity produced by concurrent drug therapy could alter plasma levels. Two cases of phenytoin intoxication associated with simultaneous administration of diazepam are reported. Intravenous phenytoin infusions were given and the apparent Km and Vmax computed from the resulting plasma phenytoin levels. In one case `Km' and `Vmax' were 0.8 μmol/1 and 1.3 μmol/1/hour respectively during concurrent diazepam administration, and 50.3 μmol/1 and 4.4 μmol/1/hour after discontinuation of diazepam. In the second case phenytoin infusion with diazepam gave `Km' and `Vmax' values of 0.012 μmol/1 and 0.95 μmol/1/hour. Without diazepam these were 28.8 μmol/1 and 0.92 μmol/1/hour respectively. PMID:599366

40 CFR 1065.670 - NOX intake-air humidity and temperature corrections.

Code of Federal Regulations, 2010 CFR

2010-07-01

... concentrations for intake-air humidity. You may use a time-weighted mean combustion air humidity to calculate this correction if your combustion air humidity remains within a tolerance of ±0.0025 mol/mol of the... equation: ER30AP10.095 Example: x NOxuncor = 700.5 µmol/mol x H2O = 0.022 mol/mol x NOxcor = 700.5 · (9.953...

40 CFR 1065.670 - NOX intake-air humidity and temperature corrections.

Code of Federal Regulations, 2011 CFR

2011-07-01

... concentrations for intake-air humidity. You may use a time-weighted mean combustion air humidity to calculate this correction if your combustion air humidity remains within a tolerance of ±0.0025 mol/mol of the... equation: ER30AP10.095 Example: x NOxuncor = 700.5 µmol/mol x H2O = 0.022 mol/mol x NOxcor = 700.5 · (9.953...

Low-melting point heat transfer fluid

DOEpatents

Cordaro, Joseph Gabriel; Bradshaw, Robert W.

2010-11-09

A low-melting point, heat transfer fluid made of a mixture of five inorganic salts including about 29.1-33.5 mol % LiNO.sub.3, 0-3.9 mol % NaNO.sub.3, 2.4-8.2 mol % KNO.sub.3, 18.6-19.9 mol % NaNO.sub.2, and 40-45.6 mol % KNO.sub.2. These compositions can have liquidus temperatures below 80.degree. C. for some compositions.

Allocation of secondary metabolites, photosynthetic capacity, and antioxidant activity of Kacip Fatimah (Labisia pumila Benth) in response to CO2 and light intensity.

PubMed

Ibrahim, Mohd Hafiz; Jaafar, Hawa Z E; Karimi, Ehsan; Ghasemzadeh, Ali

2014-01-01

A split plot 3 by 4 experiment was designed to investigate and distinguish the relationships among production of secondary metabolites, soluble sugar, phenylalanine ammonia lyase (PAL; EC 4.3.1.5) activity, leaf gas exchange, chlorophyll content, antioxidant activity (DPPH), and lipid peroxidation under three levels of CO2 (400, 800, and 1200 μ mol/mol) and four levels of light intensity (225, 500, 625, and 900 μ mol/m(2)/s) over 15 weeks in Labisia pumila. The production of plant secondary metabolites, sugar, chlorophyll content, antioxidant activity, and malondialdehyde content was influenced by the interactions between CO2 and irradiance. The highest accumulation of secondary metabolites, sugar, maliondialdehyde, and DPPH activity was observed under CO2 at 1200 μ mol/mol + light intensity at 225 μ mol/m(2)/s. Meanwhile, at 400 μ mol/mol CO2 + 900 μ mol/m(2)/s light intensity the production of chlorophyll and maliondialdehyde content was the highest. As CO2 levels increased from 400 to 1200 μ mol/mol the photosynthesis, stomatal conductance, f v /f m (maximum efficiency of photosystem II), and PAL activity were enhanced. The production of secondary metabolites displayed a significant negative relationship with maliondialdehyde indicating lowered oxidative stress under high CO2 and low irradiance improved the production of plant secondary metabolites that simultaneously enhanced the antioxidant activity (DPPH), thus improving the medicinal value of Labisia pumila under this condition.

Growth, pod, and seed yield, and gas exchange of hydroponically grown peanut in response to CO2 enrichment

NASA Technical Reports Server (NTRS)

Stanciel, K.; Mortley, D. G.; Hileman, D. R.; Loretan, P. A.; Bonsi, C. K.; Hill, W. A.

2000-01-01

The effects of elevated CO2 on growth, pod, and seed yield, and gas exchange of 'Georgia Red' peanut (Arachis hypogaea L.) were evaluated under controlled environmental conditions. Plants were exposed to concentrations of 400 (ambient), 800, and 1200 micromoles mol-1 CO2 in reach-in growth chambers. Foliage fresh and dry weights increased with increased CO2 up to 800 micromoles mol-1, but declined at 1200 micromoles mol-1. The number and the fresh and dry weights of pods also increased with increasing CO2 concentration. However, the yield of immature pods was not significantly influenced by increased CO2. Total seed yield increased 33% from ambient to 800 micromoles mol-1 CO2, and 4% from 800 to 1200 micromoles mol-1 CO2. Harvest index increased with increasing CO2. Branch length increased while specific leaf area decreased linearly as CO2 increased from ambient to 1200 micromoles mol-1. Net photosynthetic rate was highest among plants grown at 800 micromoles mol-1. Stomatal conductance decreased with increased CO2. Carboxylation efficiency was similar among plants grown at 400 and 800 micromoles mol-1 and decreased at 1200 micromoles mol-1 CO2. These results suggest that CO2 enrichment from 400 to 800 micromoles mol-1 had positive effects on peanut growth and yield, but above 800 micromoles mol-1 enrichment seed yield increased only marginally.

Piezoresponse force microscopy of ferroelectric relaxors =

NASA Astrophysics Data System (ADS)

Kiselev, Dmitry

Nesta tese, ferroelectricos relaxor (I dont know uf the order is correct) de base Pb das familias (Pb,La)(Zr,Ti)O3 (PLZT), Pb(Mg1/3,Nb2/3)O3-PbTiO3 (PMN-PT), Pb(Zn1/3,Nb2/3)O3-PbTiO3 (PZN-PT) foram investigados e analisados. As propriedades ferroelectricas e dielectricas das amostras foram estudadas por metodos convencionais de macro e localmente por microscopia de forca piezoelectrica (PFM). Nos cerâmicos PLZT 9.75/65/35 o contraste da PFM a escala nanometrica foi investigado em funcao do tamanho e orientacao dos graos. Apurou-se que a intensidade do sinal piezoelectrico das nanoestruturas diminui com o aumento da temperatura e desaparece a 490 K (La mol. 8%) e 420 K (9,5%). Os ciclos de histerese locais foram obtidos em funcao da temperatura. A evolucao dos parâmetros macroscopicos e locais com a temperatura de superficie sugere um forte efeito de superficie nas transicoes de fase ferroelectricas do material investigado. A rugosidade da parede de dominio e determinada por PFM para a estrutura de dominio natural existente neste ferroelectrico policristalino. Alem disso, os dominios ferroelectricos artificiais foram criados pela aplicacao de pulsos electricos a ponta do condutor PFM e o tamanho de dominio in-plane foi medido em funcao da duracao do pulso. Todas estas experiencias levaram a conclusao de que a parede de dominio em relaxors do tipo PZT e quase uma interface unidimensional. O mecanismo de contraste na superficie de relaxors do tipo PLZT e medido por PFMAs estruturas de dominio versus evolucao da profundidade foram estudadas em cristais PZN-4,5%PT, com diferentes orientacoes atraves da PFM. Padroes de dominio irregulares com tamanhos tipicos de 20-100 nm foram observados nas superficies com orientacao das amostras unpoled?. Pelo contrario, os cortes de cristal exibem dominios regulares de tamanho micron normal, com os limites do dominio orientados ao longo dos planos cristalograficos permitidos. A existencia de nanodominios em cristais com orientacao esta provisoriamente (wrong Word) atribuida a natureza relaxor de PZN-PT, onde pequenos grupos polares podem formar-se em coindicoes de zero-field-cooling (ZFC). Estes nanodominios sao considerados como os nucleos do estado de polarizacao oposta e podem ser responsaveis pelo menor campo coercitivo para este corte de cristal em particular. No entanto, a histerese local piezoeletrica realizada pelo PFM a escala nanometrica indica uma mudanca de comportamento de PZN-PT semelhante para ambas as orientacoes cristalograficas investigadas. A evolucao das estruturas de dominio com polimento abaixo da superficie do cristal foi investigada. O dominio de ramificacoes e os efeitos de polarizacao de triagem apos o polimento e as medicoes de temperatura tem sido estudados pela PFM e pela analise SEM. Alem disso, verificou-se que a intensidade do sinal piezoelectrico a partir das estruturas de nanodominio diminui com o aumento da temperatura, acabando por desaparecer aos 430 K (orientacao ) e 470 K (orientacao ). Esta diferenca de temperatura nas transicoes de fase local em cristais de diferentes orientacoes e explicada pelo forte efeito de superficie na transicao da fase ferroeletrica em relaxors. A comutacao da polarizacao em relaxor ergodico e nas fases ferroelectricas do sistema PMN-PT foram realizadas pela combinacao de tres metodos, Microscopia de Forca Piezoelectrica, medicao de um unico ponto de relaxamento eletromecânico e por ultimo mapeamento de espectroscopia de tensao. A dependencia do comportamento do relaxamento na amplitude e tempo da tensao de pulso foi encontrada para seguir um comportamento logaritmico universal com uma inclinacao quase constante. Este comportamento e indicativo da progressiva populacao dos estados de relaxamento lento, ao contrario de uma relaxacao linear na presenca de uma ampla distribuicao do tempo de relaxamento. O papel do comportamento de relaxamento, da nao-linearidade ferroelectrica e da heterogeneidade espacial do campo na ponta da sonda de AFM sobre o comportamento do ciclo de histerese e analisada em detalhe. Os ciclos de histerese para ergodica PMN- 10%PT sao mostrados como cineticamente limitados, enquanto que no PMN, com maior teor de PT, sao observados verdadeiros ciclos de histerese ferroelectrica com vies de baixa nucleacao.

Transcriptional and Functional Analysis of the Effects of Magnolol: Inhibition of Autolysis and Biofilms in Staphylococcus aureus

PubMed Central

Liang, Junchao; Shen, Fengge; Xing, Mingxun; Deng, Xuming; Yu, Lu

2011-01-01

Background The targeting of Staphylococcus aureus biofilm structures are now gaining interest as an alternative strategy for developing new types of antimicrobial agents. Magnolol (MOL) shows inhibitory activity against S. aureus biofilms and Triton X-100-induced autolysis in vitro, although there are no data regarding the molecular mechanisms of MOL action in bacteria. Methodology/Principal Findings The molecular basis of the markedly reduced autolytic phenotype and biofilm inhibition triggered by MOL were explored using transcriptomic analysis, and the transcription of important genes were verified by real-time RT-PCR. The inhibition of autolysis by MOL was evaluated using quantitative bacteriolytic assays and zymographic analysis, and antibiofilm activity assays and confocal laser scanning microscopy were used to elucidate the inhibition of biofilm formation caused by MOL in 20 clinical isolates or standard strains. The reduction in cidA, atl, sle1, and lytN transcript levels following MOL treatment was consistent with the induced expression of their autolytic repressors lrgA, lrgB, arlR, and sarA. MOL generally inhibited or reversed the expression of most of the genes involved in biofilm production. The growth of S. aureus strain ATCC 25923 in the presence of MOL dose-dependently led to decreases in Triton X-100-induced autolysis, extracellular murein hydrolase activity, and the amount of extracellular DNA (eDNA). MOL may impede biofilm formation by reducing the expression of cidA, a murein hydrolase regulator, to inhibit autolysis and eDNA release, or MOL may directly repress biofilm formation. Conclusions/Significance MOL shows in vitro antimicrobial activity against clinical and standard S. aureus strains grown in planktonic and biofilm cultures, suggesting that the structure of MOL may potentially be used as a basis for the development of drugs targeting biofilms. PMID:22046374

In situ gas analysis for high pressure applications using property measurements

NASA Astrophysics Data System (ADS)

Moeller, J.; Span, R.; Fieback, T.

2013-10-01

As the production, distribution, and storage of renewable energy based fuels usually are performed under high pressures and as there is a lack of in situ high pressure gas analysis instruments on the market, the aim of this work was to develop a method for in situ high pressure gas analysis of biogas and hydrogen containing gas mixtures. The analysis is based on in situ measurements of optical, thermo physical, and electromagnetic properties in gas mixtures with newly developed high pressure sensors. This article depicts the calculation of compositions from the measured properties, which is carried out iteratively by using highly accurate equations of state for gas mixtures. The validation of the method consisted of the generation and measurement of several mixtures, of which three are presented herein: a first mixture of 64.9 mol. % methane, 17.1 mol. % carbon dioxide, 9 mol. % helium, and 9 mol. % ethane at 323 K and 423 K in a pressure range from 2.5 MPa to 17 MPa; a second mixture of 93.0 mol. % methane, 4.0 mol. % propane, 2.0 mol. % carbon dioxide, and 1.0 mol. % nitrogen at 303 K, 313 K, and 323 K in a pressure range from 1.2 MPa to 3 MPa; and a third mixture of 64.9 mol. % methane, 30.1 mol. % carbon dioxide, and 5.0 mol. % nitrogen at 303 K, 313 K, and 323 K in a pressure range from 2.5 MPa to 4 MPa. The analysis of the tested gas mixtures showed that with measured density, velocity of sound, and relative permittivity the composition can be determined with deviations below 1.9 mol. %, in most cases even below 1 mol. %. Comparing the calculated compositions with the generated gas mixture, the deviations were in the range of the combined uncertainty of measurement and property models.

Effects of Moringa oleifera leaves as a substitute for alfalfa meal on nutrient digestibility, growth performance, carcass trait, meat quality, antioxidant capacity and biochemical parameters of rabbits.

PubMed

Sun, B; Zhang, Y; Ding, M; Xi, Q; Liu, G; Li, Y; Liu, D; Chen, X

2018-02-01

This contribution reports the effects of Moringa oleifera leaves (MOLs) meal on the growth performances, nutrient digestibility, carcass trait, meat quality, antioxidant capacity and biochemical parameters of growing New Zealand white rabbits. The MOL was substituted for alfalfa meal at levels of 0, 10%, 20% and 30% to obtain respective diets MOL0, MOL10, MOL20 and MOL30. Each treatment was replicated five times with 10 rabbits per replicate. Results showed the average daily weight gain (ADWG) and feed conversion ratio (FCR) of rabbits fed MOL20 diet were significantly better (p < 0.05) than those of other three dietary groups. Liver and spleen index of rabbits fed MOL20 and MOL30 diets was significantly higher (p < 0.05) than that of the groups fed with lower M. oleifera leaves (MOL0, MOL10). The meat drip loss of rabbits fed with diet MOL10 was significantly lower (p < 0.05) than that of rabbits fed other diets. All rabbits fed MOL dietary groups had lower (p < 0.05) shear force of longissimus dorsi than the group without M. oleifera leaves. No significant differences were found in the digestibility of crude fibre (CF), crude fat (EE), ash, crude protein (CP) and nitrogen-free extract (NFE) among the dietary groups. Moringa oleifera leaves also have a significant impact on serum albumin (ALB), low-density lipoprotein cholesterol (LDLC), triiodothyroxine (T 3 ) and tetraiodothyroxine (T 4 ) values and the activity of superoxide dismutase (SOD) and catalase (CAT) in serum and liver. The results indicated that M. oleifera leaves could be developed as a good feed source, and it not only could substitute for alfalfa meal well but also has a significant effect on growth performance, meat quality, antioxidant and biochemical parameters of rabbits. © 2017 Blackwell Verlag GmbH.

Analysis of Advanced Glycation Endproducts in Rat Tail Collagen and Correlation to Tendon Stiffening.

PubMed

Jost, Tobias; Zipprich, Alexander; Glomb, Marcus A

2018-04-18

Methylglyoxal is a major 1,2-dicarbonyl compound in vivo and leads to nonenzymatic protein modifications, known as advanced glycation endproducts. Especially long-lived proteins like collagen are prone to changes of the mechanical or biological function, respectively, by accumulation of Maillard-derived modifications. Specifically, the resulting nonenzymatic cross-link structures in parallel to the natural maturation process of collagen fibrils lead to complications with age or during disease. A novel lysine-lysine amide cross-link derived from methylglyoxal, 2,15-diamino-8-methyl-9-oxo-7,10-diaza-1,16-hexadecanedioic acid, named MOLA, was synthesized and identified in vitro and in vivo. Tail tendons of young, adult, and old rats (3, 12, and 22 months) were enzymatically digested prior to analysis of acid-labile glycation products via liquid chromatography-tandem mass spectrometry (LC-MS/MS). As a result, nine monovalent amino acid modifications, mostly originating from methylglyoxal (36 μmol/mol leucine-equivalents in total), and four glycation cross-links (0.72 μmol/mol glucosepane, 0.24 μmol/mol DODIC (3-deoxyglucosone-derived imidazoline cross-link), 0.04 μmol/mol MODIC (methylglyoxal-derived imidazoline cross-link), 0.34 μmol/mol MOLA) were quantitated in senescent tendon collagen. The results correlated with increased tail tendon breaking time from 10 to 190 min and indicate that methylglyoxal is a major player in the aging process of connective tissue.

Coral Ba/Ca and Mn/Ca ratios as proxies of precipitation and terrestrial input at the eastern offshore area of Hainan Island

NASA Astrophysics Data System (ADS)

Jiang, Qiaowen; Cao, Zhimin; Wang, Daoru; Li, Yuanchao; Wu, Zhongjie; Ni, Jianyu

2017-12-01

Geochemical ratios in coral reef skeletons could be used as proxies to reconstruct past climatological and environmental records in data-poor regions. Using a 103-year data set (1902 to 2005), the annual variations in Ba/Ca and Mn/Ca ratios of Porites lutea skeletons at an eastern offshore area of Hainan Island (19°12´28.4´´N, 110°37´38.8´´E) were analyzed using inductively coupled plasma-optic emission spectrometry (ICP-OES). The analysis results showed that Ba/Ca ratios varied from a minimum of 3.120 μmol mol-1 in 1903 to a maximum of 10.064 μmol mol-1 in 1944, with an average of 5.256 μmol mol-1. Mn/Ca ratios varied from 0.206 to 5.708 μmol mol-1 with an annual average of 1.234 μmol mol-1, with peak values in 2001, 1964 and 1932, that correlated with strong rainfall events caused by typhoons. Variation in Ba/Ca and Mn/Ca ratios were compared with available river discharge and precipitation records, providing insight into past climatological events. Human activities and their indirect effects could impact the strength of the relationship between Ba/Ca and Mn/Ca ratios and observed precipitation and terrestrial input in the future.

Atmospheric air pollutants: CO in Nitrogen, 5 μmol/mol

NASA Astrophysics Data System (ADS)

Konopelko, L. A.; Pankratov, V. V.; Pankov, A. A.; Ivahnenko, B. V.; Efremova, O. V.; Bakovec, N. V.; Mironchik, A. M.; Aleksandrov, V. V.

2017-01-01

This article presents the report on the COOMET supplementary comparison "Atmospheric air pollutants: CO in Nitrogen, 5 μmol/mol". Carbon monoxide (CO) is present in atmosphere due to different natural and anthropogenic sources. CO is a toxic gas and in concentrations higher than (3-5) μmol/mol it is hazardous to human health. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Recombinant protein expression of Moringa oleifera lectin in methylotrophic yeast as active coagulant for sustainable high turbid water treatment.

PubMed

Abd Wahid, Muhamad Azhar; Megat Mohd Noor, Megat Johari; Goto, Masafumi; Sugiura, Norio; Othman, Nor'azizi; Zakaria, Zuriati; Ahmad Mohammed, Thamer; Jusoh, Ahmad; Hara, Hirofumi

2017-08-01

The natural coagulant Moringa oleifera lectin (MoL) as cationic protein is a promising candidate in coagulation process of water treatment plant. Introducing the gene encoding MoL into a host, Pichia pastoris, to secrete soluble recombinant protein is assessed in this study. Initial screening using PCR confirmed the insertion of MoL gene, and SDS-PAGE analysis detected the MoL protein at 8 kDa. Cultured optimization showed the highest MoL protein at 520 mg/L was observed at 28 °C for 144 h of culturing by induction in 1% methanol. Approximately, 0.40 mg/mL of recombinant MoL protein showed 95 ± 2% turbidity removal of 1% kaolin suspension. In 0.1% kaolin suspension, the concentration of MoL at 10 μg/mL exhibits the highest turbidity reduction at 68 ± 1%. Thus, recombinant MoL protein from P. pastoris is an effective coagulant for water treatment.

AC Conductivity and Dielectric Properties of Borotellurite Glass

NASA Astrophysics Data System (ADS)

Taha, T. A.; Azab, A. A.

2016-10-01

Borotellurite glasses with formula 60B2O3-10ZnO-(30 - x)NaF- xTeO2 ( x = 0 mol.%, 5 mol.%, 10 mol.%, and 15 mol.%) have been synthesized by thermal melting. X-ray diffraction (XRD) analysis confirmed that the glasses were amorphous. The glass density ( ρ) was determined by the Archimedes method at room temperature. The density ( ρ) and molar volume ( V m) were found to increase with increasing TeO2 content. The direct-current (DC) conductivity was measured in the temperature range from 473 K to 623 K, in which the electrical activation energy of ionic conduction increased from 0.27 eV to 0.48 eV with increasing TeO2 content from 0 mol.% to 15 mol.%. The dielectric parameters and alternating-current (AC) conductivity ( σ ac) were investigated in the frequency range from 1 kHz to 1 MHz and temperature range from 300 K to 633 K. The AC conductivity and dielectric constant decreased with increasing TeO2 content from 0 mol.% to 15 mol.%.

Iron oxide nanoparticles stabilized by lignocellulosic waste as green adsorbent for Cr(VI) removal from wastewater

NASA Astrophysics Data System (ADS)

Ouma, Immaculate L. A.; Naidoo, Eliazer B.; Ofomaja, Augustine E.

2017-08-01

Magnetite nanoparticles and magnetite-pine cone nanocomposite were prepared and applied in the adsorption of hexavalent chromium from water. Pine cone powder stabilized the nanoparticles and acted as a support while simultaneously introducing functional groups which improved metal adsorption. The nanocomposite retained the nanoparticles magnetic properties while improving chromium adsorption efficiency. Adsorption of hexavalent chromium on both materials was pH and concentration dependent with the most efficient adsorption occurring at pH 2 and 75 mg/L. On both materials, chromium adsorption was spontaneous with Gibbs free energy values of -19.2 kJ mol-1 to -23.7 kJ mol-1 and -18.0 kJ mol-1 to -24.2 kJ mol-1 for nanoparticles and nanocomposite respectively between 298 K and 319 K. The changes in enthalpy and entropy were determined to be 44.4 kJ mol-1, 212.7 J K-1 mol-1 and 78.3 kJ mol-1, 323.3 J K-1 mol-1 for the prepared nanoparticles and nanocomposite respectively.

Effect of somatostatin-14 on duodenal mucosal bicarbonate secretion in guinea pigs.

PubMed

Odes, H S; Muallem, R; Reimer, R; Ioffe, S; Beil, W; Schwenk, M; Sewing, K F

1995-03-01

The role of somatostatin-14 in duodenal mucosal HCO3- secretion was investigated in anesthetized, indomethacin-treated guinea pigs. Net HCO3- output from the isolated, perfused (24 mM NaHCO3 + 130 mM NaCl) proximal duodenum was measured during intravenous infusion (alone or in combination) of somatostatin-14, carbachol, vasoactive intestinal peptide (VIP), and prostaglandin E2 (PGE2). In homogenates of duodenal enterocytes, the effect of these agents on adenylate cyclase activity was studied. Basal duodenal HCO3- secretion (3.5 +/- 0.2 mumol/cm/10 min) was reduced dose dependently by somatostatin-14 (10(-11) mol/kg, 10(-9) mol/kg, and 10(-7) mol/kg). Carbachol, VIP, and PGE2 (all 10(-8) mol/kg) increased basal duodenal HCO3- secretion two- to threefold. Somatostatin-14 (10(-7) mol/kg) abolished the stimulatory effect of carbachol and VIP, but not that of PGE2. Basal adenylate cyclase activity in isolated duodenal enterocytes (9.4 +/- 1.0 pmol cAMP/mg protein/min) was unaltered by somatostatin (10(-6) mol/liter) or carbachol (10(-3) mol/liter). VIP (10(-8) mol/liter) and PGE2 (10(-7) mol/liter) increased adenylate cyclase activity two- to threefold, and these effects were unchanged by somatostatin-14 (10(-6) mol/liter). In conclusion, somatostatin-14 inhibits basal and carbachol- and VIP-stimulated duodenal HCO3- secretion, and its mechanism of action is not via inhibition of adenylate cyclase activity in duodenal enterocytes.

Gas-phase acidities of cysteine-polyalanine peptides I: A(3,4)CSH and HSCA(3,4).

PubMed

Ren, Jianhua; Tan, John P; Harper, Robert T

2009-10-15

The gas-phase acidities of four cysteine-polyalanine peptides, A(3,4)CSH and HSCA(3,4), were determined using the extended Cooks kinetic method with full entropy analysis. A triple-quadrupole mass spectrometer with an electrospray interface was employed for the experimental study. The ion activation was achieved via collision-induced dissociation (CID) experiments. The deprotonation enthalpies (Delta(acid)H) of the peptides were determined to be 332.2 +/- 2.0 kcal/mol (A(3)CSH), 325.9 +/- 2.0 kcal/mol (A(4)CSH), 319.3 +/- 3.0 kcal/mol (HSCA(3)), and 319.2 +/- 4.0 kcal/mol (HSCA(4)). The deprotonation entropies (Delta(acid)S) of the peptides were estimated based on the entropy term (Delta(DeltaS)) and the deprotonation entropies of the reference acids. By using the deprotonation enthalpies and entropies, the gas-phase acidities (Delta(acid)G) of the peptides were derived: 325.0 +/- 2.0 kcal/mol (A(3)CSH), 320.2 +/- 2.0 kcal/mol (A(4)CSH), 316.3 +/- 3.0 kcal/mol (HSCA(3)), and 315.4 +/- 4.0 kcal/mol (HSCA(4)). Conformations and energetic information of the peptides were calculated through simulated annealing (Tripos), geometry optimization (AM1), and single-point energy calculations (B3LYP/6-31+G(d)), respectively. The calculated theoretical deprotonation enthalpies (Delta(acid)H) of 334.2 kcal/mol (A(3)CSH), 327.7 kcal/mol (A(4)CSH), 320.6 kcal/mol (HSCA(3)), and 318.6 kcal/mol (HSCA(4)) are in good agreement with the experimentally determined values. Both the experimental and computational studies suggest that the two N-terminal cysteine peptides, HSCA(3,4), are significantly more acidic than the corresponding C-terminal ones, A(3,4)CSH. The high acidities of the former are likely due to the helical conformational effects for which the thiolate anion may be strongly stabilized by the interaction with the helix macrodipole.

Human thyrotropin receptor subunits characterized by thyrotropin affinity purification and western blotting.

PubMed

Leedman, P J; Newman, J D; Harrison, L C

1989-07-01

We studied the subunit structure of the human TSH receptor in thyroid tissue from patients with Graves' disease and multinodular goiter by TSH affinity chromatography, immunoprecipitation with Graves' immunoglobulins (Igs), and a modified technique of Western blotting. Human TSH receptor-binding activity was purified about 1,270-fold by sequential affinity chromatography on wheat germ lectin-agarose and TSH-agarose. Analysis by sodium dodecyl sulfate-polyacrylamide gel electrophoresis of nonreduced affinity-purified receptors eluted in sodium dodecyl sulfate sample buffer revealed three noncovalently linked subunits of 70,000, 50,000, and 35,000 mol wt. When reduced, a major subunit of 25,000 mol wt was identified. When 3 mol/L NaCl was used to elute affinity-purified receptors only the 50,000 mol wt nonreduced subunit was detected. This subunit bound [125I]bovine TSH and was precipitated by Graves' Igs. Modifications to the conventional Western blotting technique enabled thyroglobulin components (approximately 220,000 mol wt), thyroid microsomal antigen (a doublet of approximately 110,000 mol wt), and putative TSH receptor subunits of 70,000 and 50,000 mol wt to be identified in thyroid particulate membranes by Graves' Igs. Blotting of affinity-purified receptors eluted in sodium dodecyl sulfate sample buffer revealed subunits of either 70,000 or 50,000 mol wt, with a minority of Graves' serum samples. We conclude that the nonreduced human TSH receptor is an oligomeric complex comprising three different subunits of 70,000, 50,000, and 35,000 mol wt. The reduced receptor exists as a single subunit of 25,000 mol wt, which may be disulfide linked to form the higher mol wt forms. The 70,000 and 50,000 mol wt subunits contain epitopes that bind Graves' Igs in modified Western blots, thus directly confirming that the human TSH receptor is a target for Graves' Igs.

Determination of enhancement ratios of HCOOH relative to CO in biomass burning plumes by the Infrared Atmospheric Sounding Interferometer (IASI)

NASA Astrophysics Data System (ADS)

Pommier, Matthieu; Clerbaux, Cathy; Coheur, Pierre-Francois

2017-09-01

Formic acid (HCOOH) concentrations are often underestimated by models, and its chemistry is highly uncertain. HCOOH is, however, among the most abundant atmospheric volatile organic compounds, and it is potentially responsible for rain acidity in remote areas. HCOOH data from the Infrared Atmospheric Sounding Interferometer (IASI) are analyzed from 2008 to 2014 to estimate enhancement ratios from biomass burning emissions over seven regions. Fire-affected HCOOH and CO total columns are defined by combining total columns from IASI, geographic location of the fires from Moderate Resolution Imaging Spectroradiometer (MODIS), and the surface wind speed field from the European Centre for Medium-Range Weather Forecasts (ECMWF). Robust correlations are found between these fire-affected HCOOH and CO total columns over the selected biomass burning regions, allowing the calculation of enhancement ratios equal to 7.30 × 10-3 ± 0.08 × 10-3 mol mol-1 over Amazonia (AMA), 11.10 × 10-3 ± 1.37 × 10-3 mol mol-1 over Australia (AUS), 6.80 × 10-3 ± 0.44 × 10-3 mol mol-1 over India (IND), 5.80 × 10-3 ± 0.15 × 10-3 mol mol-1 over Southeast Asia (SEA), 4.00 × 10-3 ± 0.19 × 10-3 mol mol-1 over northern Africa (NAF), 5.00 × 10-3 ± 0.13 × 10-3 mol mol-1 over southern Africa (SAF), and 4.40 × 10-3 ± 0.09 × 10-3 mol mol-1 over Siberia (SIB), in a fair agreement with previous studies. In comparison with referenced emission ratios, it is also shown that the selected agricultural burning plumes captured by IASI over India and Southeast Asia correspond to recent plumes where the chemistry or the sink does not occur. An additional classification of the enhancement ratios by type of fuel burned is also provided, showing a diverse origin of the plumes sampled by IASI, especially over Amazonia and Siberia. The variability in the enhancement ratios by biome over the different regions show that the levels of HCOOH and CO do not only depend on the fuel types.

PA-1, a Versatile Anaerobe Obtained in Pure Culture, Catabolizes Benzenoids and Other Compounds in Syntrophy with Hydrogenotrophs, and P-2 plus Wolinella sp. Degrades Benzenoids

PubMed Central

Barik, Sudhakar; Brulla, W. J.; Bryant, M. P.

1985-01-01

Methanogenic enrichments catabolizing 13 mM phenylacetate or 4 mM phenol were established at 37°C, using a 10% inoculum from a municipal anaerobic digester. By using agar roll tubes of the basal medium plus 0.1% yeast extract-25 mM fumarate, a hydrogenotrophic lawn of Wolinella succinogenes and phenol or phenylacetate, strains P-2 and PA-1, respectively, were isolated in coculture with W. succinogenes. With the lawn deleted, PA-1 was isolated in pure culture. Strain P-2 is apparently a new species of anaerobic, motile, gram-negative, spindle-shaped, small rod that as yet has been grown only in coculture with W. succinogenes. It used phenol, hydrocinnamate, benzoate, and phenylacetate as energy sources. Product recovery by the coculture, per mole of phenol and 4.4 mol of fumarate used, included 2.03, 0.12, 0.08, and 3.23 mol, respectively, of acetate, propionate, butyrate, and succinate. Carbon recovery was 75% and H recovery was 80%, although CO2 and a few other possible products were not determined. That P-2 is an obligate proton-reducing acetogen and possible pathways for its degradation of phenol are discussed. Strain PA-1 is apparently a new species of anaerobic, motile, relatively small, gram-negative rod. It utilized compounds such as phenylacetate, hydrocinnamate, benzoate, phenol, resorcinol, gallate, 4-aminophenol, 2-aminobenzoate, pyruvate, Casamino Acids, and aspartate as energy sources in coculture with W. succinogenes. Per mole of phenylacetate and 1.44 mol of fumarate used, 1.04, 0.53, and 0.78 mol of acetate, propionate, and succinate, respectively, were recovered from the coculture. Only about 50% of the carbon and H were recovered. In coculture with Methanospirillum hungatei, 0.96 mol of acetate and 0.25 mol of methane were recovered per mol of pyruvate used; 0.90 mol of acetate and 0.33 mol of methane, per mol of fumarate used; 0.93 mol of acetate and 0.54 mol of methane, per mol of aspartate used; and 1.71 mol of acetate and 0.57 mol of methane, per mol of glucose used. Carbon and H recoveries, assuming CO2 and ammonia were produced in stoichiometric amounts, were 97 and 98% for pyruvate, 72.5 and 82% for fumarate, 96.5 and 98% for aspartate, and 61.8 and 76% for glucose. No explanation such as contamination could be found for the fact that the coculture PA-1 plus Wolinella sp. did not use glucose; after growth with M. hungatei on pyruvate, however, the latter coculture used glucose. The PA-1 pure culture produced 0.86 mol of propionate per mol of succinate used during growth. PA-1 produced a small amount of H2. Strain PA-1 is the most versatile anaerobic bacterium yet known that catabolizes monobenzenoids in the absence of electron acceptors such as sulfate or nitrate. PMID:16346852

Improving rice models for more reliable prediction of responses of rice yield to CO2 and temperature elevaton

USDA-ARS?s Scientific Manuscript database

Materials and Methods The simulation exercise and model improvement were implemented in phase-wise. In the first modelling activities, the model sensitivities were evaluated to given CO2 concentrations varying from 360 to 720 'mol mol-1 at an interval of 90 'mol mol-1 and air temperature increments...

Allocation of Secondary Metabolites, Photosynthetic Capacity, and Antioxidant Activity of Kacip Fatimah (Labisia pumila Benth) in Response to CO2 and Light Intensity

PubMed Central

Jaafar, Hawa Z. E.; Karimi, Ehsan; Ghasemzadeh, Ali

2014-01-01

A split plot 3 by 4 experiment was designed to investigate and distinguish the relationships among production of secondary metabolites, soluble sugar, phenylalanine ammonia lyase (PAL; EC 4.3.1.5) activity, leaf gas exchange, chlorophyll content, antioxidant activity (DPPH), and lipid peroxidation under three levels of CO2 (400, 800, and 1200 μmol/mol) and four levels of light intensity (225, 500, 625, and 900 μmol/m2/s) over 15 weeks in Labisia pumila. The production of plant secondary metabolites, sugar, chlorophyll content, antioxidant activity, and malondialdehyde content was influenced by the interactions between CO2 and irradiance. The highest accumulation of secondary metabolites, sugar, maliondialdehyde, and DPPH activity was observed under CO2 at 1200 μmol/mol + light intensity at 225 μmol/m2/s. Meanwhile, at 400 μmol/mol CO2 + 900 μmol/m2/s light intensity the production of chlorophyll and maliondialdehyde content was the highest. As CO2 levels increased from 400 to 1200 μmol/mol the photosynthesis, stomatal conductance, f v/f m (maximum efficiency of photosystem II), and PAL activity were enhanced. The production of secondary metabolites displayed a significant negative relationship with maliondialdehyde indicating lowered oxidative stress under high CO2 and low irradiance improved the production of plant secondary metabolites that simultaneously enhanced the antioxidant activity (DPPH), thus improving the medicinal value of Labisia pumila under this condition. PMID:24683336

Study on separation of minor actinides from HLLW with new extractant of TODGA-DHOA/Kerosene

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ye, Guo-an; Zhu, Wen-bin; Li, Feng-feng

2013-07-01

The extraction behavior of U, Np, Pu, Am, rare earth elements and Sr from nitric acid solutions by TODGA/dodecan, DHOA/dodecane and TODGA-DHOA/dodecane were investigated, respectively. Based on experimental results, a separation process was proposed for minor actinide isolation from high level liquid waste (HLLW): the TODGA-DHOA/kerosene system. The multi-stage counter-current cascade experiments were carried out for the purpose by 0.1 mol/l TODGA-1.0 mol/l DHOA/kerosene with miniature mixer- settler contactor rigs (8 stages for extraction, 6 stages for scrubbing, 8 stages for first stripping, 8 stages for second stripping). The results show that the recovery efficiencies of the actinides and lanthanidesmore » are more than 99.9%, whereas less than 1% Sr was extracted by 0.1 mol/l TODGA - 1.0 mol/l DHOA/kerosene. The stripping efficiencies of U, Np and Pu are more than 95% in the first stripping step by 0.5 mol/l HNO{sub 3} + 0.5 mol/l AHA(aceto-hydroxamic acid), all of the remained actinides and lanthanides can be stripped by 0.01 mol/l HNO{sub 3} in the second stripping step. 99% Sr was extracted by 0.1 mol/l TODGA/kerosene, so Sr can be recovered efficiently directly from the raffinate by 0.1 mol/l TODGA/kerosene. (authors)« less

Comparative evaluation of antiplatelet effect of lycopene with aspirin and the effect of their combination on platelet aggregation: An in vitro study.

PubMed

Sawardekar, Swapna B; Patel, Tejal C; Uchil, Dinesh

2016-01-01

The objective was to compare antiplatelet effect of lycopene with aspirin and to study effect of combination of the two on platelet aggregation in vitro, using platelets from healthy volunteers. Platelets were harvested; platelet count of platelet-rich plasma adjusted to 2.5 Χ 10(5)/μL. Aspirin (140 μmol/L) and lycopene (4, 6, 8, 10, and 12 μmol/L) were studied in vitro against adenosine-5'- diphosphate (ADP) (2.5 μM/L) and collagen. All the concentrations of lycopene (4-12 μmol/L) exhibited reduction in maximum platelet aggregation induced by aggregating agents ADP and collagen (P < 0.01 vs. vehicle) and were comparable with aspirin. Lycopene at concentration 10 μmol/L showed maximum platelet inhibition (47.05% ± 19.56%) against ADP, whereas lycopene at concentration 8 μmol/L showed maximum platelet inhibition (54.26% ± 30.71%) against collagen. Four μmol/L of lycopene combined with 140 μmol/L and 70 μmol/L aspirin showed greater inhibition of platelets as compared to aspirin 140 μmol/L alone, against both ADP and collagen. The study favorably compares lycopene and aspirin with respect to their antiplatelet activities against ADP and collagen. Lycopene can be considered as a potential target for modifying the thrombotic and pro-inflammatory events associated with platelet activation.

EFFECTS OF ELEVATED CO2 AND N-FERTILIZATION ON SURVIVAL OF PONDEROSA PINE FINE ROOTS

EPA Science Inventory

We used minihizaotrons to assess the effects of elevated CO2N and season on the life-span of ponderosa pine (Pinus ponderosa Dougl. Ex Laws.) fine roots. CO2 levels were ambient air (A), ambient air + 175 ?mol mol-1 (A+175) and ambient air + 350 ?mol mol-1 (A+350). N treatments ...

The Thermodynamic Conjugation Stabilization of 1,3-Butadiyne Is Zero

ERIC Educational Resources Information Center

Rogers, Donald W.; Zavitsas, Andreas A.; Matsunaga, Nikita

2010-01-01

Many textbooks point out that the thermodynamic stabilization enthalpy of 1 mol of 1,3-butadiene relative to 2 mol of 1-butene or to 1 mol of 1,4-pentadiene is slightly less than 4 kcal mol[superscript -1], owing to conjugation between the double bonds in the 1,3 configuration. It is reasonable to suppose that the analogous thermochemical…

3-(2,3-Dioxoindolin-1-yl)propane­nitrile

PubMed Central

Qachchachi, Fatima-Zahrae; Kandri Rodi, Youssef; Essassi, El Mokhtar; Bodensteiner, Michael; El Ammari, Lahcen

2014-01-01

The asymmetric unit of the title compound, C11H8N2O2, contains two independent mol­ecules (A and B). Each mol­ecule is build up from fused five- and six-membered rings with the former linked to a cyano­ethyl group. The indoline ring and two carbonyl O atoms of each mol­ecule are nearly coplanar, with the largest deviations from the mean planes being 0.0198 (9) (mol­ecule A) and 0.0902 (9) Å (mol­ecule B), each by a carbonyl O atom. The fused ring system is nearly perpendicular to the mean plane passing through the cyano­ethyl chains, as indicated by the dihedral angles between them of 69.72 (9) (mol­ecule A) and 69.15 (9)° (mol­ecule B). In the crystal, mol­ecules are linked by C—H⋯O and π–π [inter­centroid distance between inversion-related indoline (A) rings = 3.6804 (7) Å] inter­actions into a double layer that stacks along the a-axis direction. PMID:24765047

Strength, Fracture Toughness, and Slow Crack Growth of Zirconia/alumina Composites at Elevated Temperature

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Bansal, Narottam P.

2003-01-01

Various electrolyte materials for solid oxide fuel cells were fabricated by hot pressing 10 mol% yttria-stabilized zirconia (10-YSZ) reinforced with two different forms of alumina particulates and platelets each containing 0 to 30 mol% alumina. Flexure strength and fracture toughness of platelet composites were determined as a function of alumina content at 1000 C in air and compared with those of particulate composites determined previously. In general, elevated-temperature strength and fracture toughness of both composite systems increased with increasing alumina content. For a given alumina content, flexure strength of particulate composites was greater than that of platelet composites at higher alumina contents (greater than or equal to 20 mol%), whereas, fracture toughness was greater in platelet composites than in particulate composites, regardless of alumina content. The results of slow crack growth (SCG) testing, determined at 1000 C via dynamic fatigue testing for three different composites including 0 mol% (10-YSZ matrix), 30 mol % particulate and 30 mol% platelet composites, showed that susceptibility to SCG was greatest with SCG parameter n = 6 to 8 for both 0 and 30 mol% particulate composites and was least with n = 33 for the 30 mol% platelet composite.

Key role of temperature monitoring in interpretation of microwave effect on transesterification and esterification reactions for biodiesel production.

PubMed

Mazubert, Alex; Taylor, Cameron; Aubin, Joelle; Poux, Martine

2014-06-01

Microwave effects have been quantified, comparing activation energies and pre-exponential factors to those obtained in a conventionally-heated reactor for biodiesel production from waste cooking oils via transesterification and esterification reactions. Several publications report an enhancement of biodiesel production using microwaves, however recent reviews highlight poor temperature measurements in microwave reactors give misleading reaction performances. Operating conditions have therefore been carefully chosen to investigate non-thermal microwave effects alone. Temperature is monitored by an optical fiber sensor, which is more accurate than infrared sensors. For the transesterification reaction, the activation energy is 37.1kJ/mol (20.1-54.2kJ/mol) in the microwave-heated reactor compared with 31.6kJ/mol (14.6-48.7kJ/mol) in the conventionally-heated reactor. For the esterification reaction, the activation energy is 45.4kJ/mol (31.8-58.9kJ/mol) for the microwave-heated reactor compared with 56.1kJ/mol (55.7-56.4kJ/mol) for conventionally-heated reactor. The results confirm the absence of non-thermal microwave effects for homogenous-catalyzed reactions. Copyright © 2014 Elsevier Ltd. All rights reserved.

Production of hydrogen, ethanol and volatile fatty acids from the seaweed carbohydrate mannitol.

PubMed

Xia, Ao; Jacob, Amita; Herrmann, Christiane; Tabassum, Muhammad Rizwan; Murphy, Jerry D

2015-10-01

Fermentative hydrogen from seaweed is a potential biofuel of the future. Mannitol, which is a typical carbohydrate component of seaweed, was used as a substrate for hydrogen fermentation. The theoretical specific hydrogen yield (SHY) of mannitol was calculated as 5 mol H2/mol mannitol (615.4 mL H2/g mannitol) for acetic acid pathway, 3 mol H2/mol mannitol (369.2 mL H2/g mannitol) for butyric acid pathway and 1 mol H2/mol mannitol (123.1 mL H2/g mannitol) for lactic acid and ethanol pathways. An optimal SHY of 1.82 mol H2/mol mannitol (224.2 mL H2/g mannitol) was obtained by heat pre-treated anaerobic digestion sludge under an initial pH of 8.0, NH4Cl concentration of 25 mM, NaCl concentration of 50mM and mannitol concentration of 10 g/L. The overall energy conversion efficiency achieved was 96.1%. The energy was contained in the end products, hydrogen (17.2%), butyric acid (38.3%) and ethanol (34.2%). Copyright © 2015 Elsevier Ltd. All rights reserved.

A Novel Nanosecond Pulsed Power Unit for the Formation of ·OH in Water

NASA Astrophysics Data System (ADS)

Li, Shengli; Hu, Sheng; Zhang, Han

2012-04-01

A novel nanosecond pulsed power unit was developed for plasma treatment of wastewater, based on the theory of magnetic pulse compression and semiconductor opening switch (SOS). The peak value, rise time and pulse duration of the output voltage were observed to be -51 kV, 60 ns and 120 ns, respectively. The concentrations of ·OH generated by the novel nanosecond pulsed plasma power were determined using the method of high-performance liquid chromatography (HPLC). The results showed that the concentrations of ·OH increased with the increase in peak voltage, and the generation rates of ·OH were 4.1 × 10-10 mol/s, 5.7 × 10-10 mol/s, and 7.7 × 10-10 mol/s at 30 kV, 35 kV, and 40 kV, respectively. The efficiency of OH generation was found to be independent of the input parameters for applied power, with an average value of 3.23×10-12 mol/J obtained.

N-[2-(2,2-Di-methyl-propanamido)-pyrimidin-4-yl]-2,2-di-methyl-propanamide n-hexane 0.25-solvate hemihydrate.

PubMed

Ośmiałowski, Borys; Valkonen, Arto; Chęcińska, Lilianna

2013-10-05

The asymmetric unit of the title compound, C14H22N4O2·0.25C6H14·0.5H2O, contains two independent mol-ecules of 2,4-bis-(pivaloyl-amino)-pyrimidine (M) with similar conformations, one water mol-ecule and one-half n-hexane solvent mol-ecule situated on an inversion center. In one independent M mol-ecule, one of the two tert-butyl groups is rotationally disordered between two orientations in a 3:2 ratio. The n-hexane solvent mol-ecule is disordered between two conformations in the same ratio. The water mol-ecule bridges two independent M mol-ecules via O-H⋯O, N-H⋯O and O-H⋯N hydrogen bonds into a 2M·H2O unit, and these units are further linked by N-H⋯N hydrogen bonds into chains running in the [010] direction. Weak C-H⋯O inter-actions are observed between the adjacent chains.

2,11-Dibromo-5,8-dibut­yl[4]helicene

PubMed Central

Isobe, Hiroyuki; Matsuno, Taisuke; Hitosugi, Shunpei; Nakanishi, Waka

2012-01-01

A racemic mixture of the title compound, C26H26Br2, a brominated [4]helicene, crystallizes, forming columns of stacked mol­ecules. There are two crystallographically unique mol­ecules in the asymmetric unit, both with the same helical handedness. As is typical with helicene congeners, the unique mol­ecules show short inter­atomic contacts between H atoms at the fjord region, with H⋯H distances of 1.87 and 1.94 Å. Mol­ecules with the same helical handedness segregate in the crystal packing, forming homochiral columns. The stacked mol­ecules are piled in a column with alternate orientations. The shortest C⋯C distance in the stacked mol­ecules is 3.306 (4) Å. PMID:22606172

Photosynthetic response of Cannabis sativa L. to variations in photosynthetic photon flux densities, temperature and CO2 conditions.

PubMed

Chandra, Suman; Lata, Hemant; Khan, Ikhlas A; Elsohly, Mahmoud A

2008-10-01

Effect of different photosynthetic photon flux densities (0, 500, 1000, 1500 and 2000 μmol m(-2)s(-1)), temperatures (20, 25, 30, 35 and 40 °C) and CO2 concentrations (250, 350, 450, 550, 650 and 750 μmol mol(-1)) on gas and water vapour exchange characteristics of Cannabis sativa L. were studied to determine the suitable and efficient environmental conditions for its indoor mass cultivation for pharmaceutical uses. The rate of photosynthesis (PN) and water use efficiency (WUE) of Cannabis sativa increased with photosynthetic photon flux densities (PPFD) at the lower temperatures (20-25 °C). At 30 °C, PN and WUE increased only up to 1500 μmol m(-2)s(-1) PPFD and decreased at higher light levels. The maximum rate of photosynthesis (PN max) was observed at 30 °C and under 1500 μmol m(-2)s(-1) PPFD. The rate of transpiration (E) responded positively to increased PPFD and temperature up to the highest levels tested (2000 μmol m(-2)s(-1) and 40 °C). Similar to E, leaf stomatal conductance (gs) also increased with PPFD irrespective of temperature. However, gs increased with temperature up to 30 °C only. Temperature above 30 °C had an adverse effect on gs in this species. Overall, high temperature and high PPFD showed an adverse effect on PN and WUE. A continuous decrease in intercellular CO2 concentration (Ci) and therefore, in the ratio of intercellular CO2 to ambient CO2 concentration (Ci/Ca) was observed with the increase in temperature and PPFD. However, the decrease was less pronounced at light intensities above 1500 μmol m(-2)s(-1). In view of these results, temperature and light optima for photosynthesis was concluded to be at 25-30 °C and ∼1500 μmol m(-2)s(-1) respectively. Furthermore, plants were also exposed to different concentrations of CO2 (250, 350, 450, 550, 650 and 750 μmol mol(-1)) under optimum PPFD and temperature conditions to assess their photosynthetic response. Rate of photosynthesis, WUE and Ci decreased by 50 %, 53 % and 10 % respectively, and Ci/Ca, E and gs increased by 25 %, 7 % and 3 % respectively when measurements were made at 250 μmol mol-1 as compared to ambient CO2 (350 μmol mol(-1)) level. Elevated CO2 concentration (750 μmol mol(-1)) suppressed E and gs ∼ 29% and 42% respectively, and stimulated PN, WUE and Ci by 50 %, 111 % and 115 % respectively as compared to ambient CO2 concentration. The study reveals that this species can be efficiently cultivated in the range of 25 to 30 °C and ∼1500 μmol m(-2)s(-1) PPFD. Furthermore, higher PN, WUE and nearly constant Ci/Ca ratio under elevated CO2 concentrations in C. sativa, reflects its potential for better survival, growth and productivity in drier and CO2 rich environment.

Synthesis of SrAl2O4:Eu2+ phosphors co-doped with Dy3+, Tb3+, Si4+ and optimization of co-doping amount by response surface method

NASA Astrophysics Data System (ADS)

Wang, Huan; Liang, Xiaoping; Liu, Kai; Zhou, Qianqian; Chen, Peng; Wang, Jun; Li, Jianxin

2016-03-01

Dy3+ doped SrAl2O4:Eu2+ phosphors were synthesized by high temperature solid phase method in a weak reducing atmosphere (5% H2 + 95% N2). The relationship between the crushed granularity and the phosphors brightness was studied. The effect of co-doping amount of Dy3+, Tb3+ and Si4+ on the structure and properties of SrAl2O4:Eu2+ via response surface method was investigated. Photoluminescence measurement results showed that the initial afterglow brightness of 0.002 mol% Dy3+ doped SrAl2O4:Eu2+0.002 phosphors decreased after first increased within the sintering temperature range from 1150 to 1400 °C, which created the highest value of 12,101 mcd/m2 at 1300 °C. Numerous coarse particles in the powder ought to be crushed for the practical application, however, the brightness became lower accompanied by the decrease of the granularity. The luminescence property of SrAl2O4:Eu2+ sintered at 1200 °C improved by co-doping Dy3+-Tb3+-Si4+. The results of response surface method showed that the influence extent on the luminescence property was Dy3+ > Tb3+ > Si4+. When the co-doping amount in SrAl2O4:Eu2+0.002 phosphors of Dy3+, Tb3+ and Si4+ was 0.001 mol%, 0.0005 mol% and 0.002 mol%, respectively, the initial afterglow brightness of SrAl2O4 was up to the highest value of 12,231 mcd/m2, which was in good agreement on the predicted maximum value of 12,519 mcd/m2 with the optimum co-doping amount of 0.0015 mol% Dy3+, 0.0005 mol% Tb3+ and 0.0017 mol% Si4+. The brightness of co-doped phosphors not only increased by 56.79% than that of SrAl2O4:Eu2+0.002, Dy3+0.002 sintered at 1200 °C, but also was above that of 1300 °C. The emission spectra results showed that, compared with 0.001 mol% Dy3+ doped phosphor, the emission peak of 0.001 mol% Dy3+-0.001 mol% Tb3+ co-doped phosphor generated red shift and increased by 9.3% in emission intensity; 0.001 mol% Dy3+-0.004 mol% Si4+ and 0.001 mol% Dy3+-0.001 mol% Tb3+-0.004 mol% Si4+ co-doped SrAl2O4:Eu2+0.002 emission peak created blue shift and increased by 37.2% and 47.6% in emission intensity, respectively.

Methods for Using Ab Initio Potential Energy Surfaces in Studies of Gas-Phase Reactions of Energetic Molecules

DTIC Science & Technology

2014-08-20

including zero-point energy ( ZPE ) corrections, 43.21 kcal/mol and 50.46 kcal/mol, respectively. The decomposition initiated by trans-HONO elimination can...CCSD(T)/cc-pVTZ level with ZPE corrections) of 47.00 kcal/mol and 48.27 kcal/mol, respectively. Thus, at the CCSD(T)/cc-pVTZ level, the ordering of

CO2 AND N-FERTILIZATION EFFECTS ON FINE ROOT LENGTH, PRODUCTION, AND MORTALITY: A 4-YEAR PONDEROSA PINE STUDY

EPA Science Inventory

We conducted a 4-year study of Pinus ponderosa fine root (<2 mm) responses to atmospheric CO2 and N-fertilization. Seedlings were grown in open-top chambers at 3 CO2 levels (ambient, ambient+175 mol/mol, ambient+350 mol/mol) and 3 N-fertilization levels (0, 10, 20 g?m-2?yr-1). ...

A novel Ru/TiO2 hybrid nanocomposite catalyzed photoreduction of CO2 to methanol under visible light

NASA Astrophysics Data System (ADS)

Kumar, Pawan; Joshi, Chetan; Labhsetwar, Nitin; Boukherroub, Rabah; Jain, Suman L.

2015-09-01

A novel in situ synthesized Ru(bpy)3/TiO2 hybrid nanocomposite is developed for the photoreduction of CO2 into methanol under visible light irradiation. The prepared composite was characterized by means of SEM, TEM, XRD, DT-TGA, XPS, UV-Vis and FT-IR techniques. The photocatalytic activity of the synthesized hybrid catalyst was tested for the photoreduction of CO2 under visible light using triethylamine as a sacrificial donor. The methanol yield for the Ru(bpy)3/TiO2 hybrid nanocomposite was found to be 1876 μmol g-1 cat (φMeOH 0.024 mol Einstein-1) that was much higher in comparison with the in situ synthesized TiO2, 828 μmol g-1 cat (φMeOH 0.010 mol Einstein-1) and the homogeneous Ru(bpy)3Cl2 complex, 385 μmol g-1 cat (φMeOH 0.005 mol Einstein-1).A novel in situ synthesized Ru(bpy)3/TiO2 hybrid nanocomposite is developed for the photoreduction of CO2 into methanol under visible light irradiation. The prepared composite was characterized by means of SEM, TEM, XRD, DT-TGA, XPS, UV-Vis and FT-IR techniques. The photocatalytic activity of the synthesized hybrid catalyst was tested for the photoreduction of CO2 under visible light using triethylamine as a sacrificial donor. The methanol yield for the Ru(bpy)3/TiO2 hybrid nanocomposite was found to be 1876 μmol g-1 cat (φMeOH 0.024 mol Einstein-1) that was much higher in comparison with the in situ synthesized TiO2, 828 μmol g-1 cat (φMeOH 0.010 mol Einstein-1) and the homogeneous Ru(bpy)3Cl2 complex, 385 μmol g-1 cat (φMeOH 0.005 mol Einstein-1). Electronic supplementary information (ESI) available: GC chromatograms of reaction products and calibration curve for methanol analysis. See DOI: 10.1039/c5nr03712c

Benzoate fermentation by the anaerobic bacterium Syntrophus aciditrophicus in the absence of hydrogen-using microorganisms.

PubMed

Elshahed, M S; McInerney, M J

2001-12-01

The anaerobic bacterium Syntrophus aciditrophicus metabolized benzoate in pure culture in the absence of hydrogen-utilizing partners or terminal electron acceptors. The pure culture of S. aciditrophicus produced approximately 0.5 mol of cyclohexane carboxylate and 1.5 mol of acetate per mol of benzoate, while a coculture of S. aciditrophicus with the hydrogen-using methanogen Methanospirillum hungatei produced 3 mol of acetate and 0.75 mol of methane per mol of benzoate. The growth yield of the S. aciditrophicus pure culture was 6.9 g (dry weight) per mol of benzoate metabolized, whereas the growth yield of the S. aciditrophicus-M. hungatei coculture was 11.8 g (dry weight) per mol of benzoate. Cyclohexane carboxylate was metabolized by S. aciditrophicus only in a coculture with a hydrogen user and was not metabolized by S. aciditrophicus pure cultures. Cyclohex-1-ene carboxylate was incompletely degraded by S. aciditrophicus pure cultures until a free energy change (DeltaG') of -9.2 kJ/mol was reached (-4.7 kJ/mol for the hydrogen-producing reaction). Cyclohex-1-ene carboxylate, pimelate, and glutarate transiently accumulated at micromolar levels during growth of an S. aciditrophicus pure culture with benzoate. High hydrogen (10.1 kPa) and acetate (60 mM) levels inhibited benzoate metabolism by S. aciditrophicus pure cultures. These results suggest that benzoate fermentation by S. aciditrophicus in the absence of hydrogen users proceeds via a dismutation reaction in which the reducing equivalents produced during oxidation of one benzoate molecule to acetate and carbon dioxide are used to reduce another benzoate molecule to cyclohexane carboxylate, which is not metabolized further. Benzoate fermentation to acetate, CO(2), and cyclohexane carboxylate is thermodynamically favorable and can proceed at free energy values more positive than -20 kJ/mol, the postulated minimum free energy value for substrate metabolism.

Changes in growth, carbon and nitrogen enzyme activity and mRNA accumulation in the halophilic microalga Dunaliella viridis in response to NaCl stress

NASA Astrophysics Data System (ADS)

Wang, Dongmei; Wang, Weiwei; Xu, Nianjun; Sun, Xue

2016-12-01

Many species of microalga Dunaliella exhibit a remarkable tolerance to salinity and are therefore ideal for probing the effects of salinity. In this work, we assessed the effects of NaCl stress on the growth, activity and mRNA level of carbon and nitrogen metabolism enzymes of D. viridis. The alga could grow over a salinity range of 0.44 mol L-1 to 3.00 mol L-1 NaCl, but the most rapid growth was observed at 1.00 mol L-1 NaCl, followed by 2.00 mol L-1 NaCl. Paralleling these growth patterns, the highest initial and total Rubisco activities were detected in the presence of 1.00 mol L-1 NaCl, decreasing to 37.33% and 26.39% of those values, respectively, in the presence of 3.00 mol L-1 NaCl, respectively. However, the highest extracellular carbonic anhydrase (CA) activity was measured in the presence of 2.00 mol L-1 NaCl, followed by 1.00 mol L-1 NaCl. Different from the two carbon enzymes, nitrate reductase (NR) activity showed a slight change under different NaCl concentrations. At the transcriptional level, the mRNAs of Rubisco large subunit ( rbcL), and small subunit ( rbcS), attained their highest abundances in the presence of 1.00 and 2.00 mol L-1 NaCl, respectively. The CA mRNA accumulation was induced from 0.44 mol L-1 to 3.00 mol L-1 NaCl, but the NR mRNA showed the decreasing tendency with the increasing salinity. In conclusion, the growth and carbon fixation enzyme of Rubisco displayed similar tendency in response to NaCl stress, CA was proved be salt-inducible within a certain salinity range and NR showed the least effect by NaCl in D. viridis.

Benzoate Fermentation by the Anaerobic Bacterium Syntrophus aciditrophicus in the Absence of Hydrogen-Using Microorganisms

PubMed Central

Elshahed, Mostafa S.; McInerney, Michael J.

2001-01-01

The anaerobic bacterium Syntrophus aciditrophicus metabolized benzoate in pure culture in the absence of hydrogen-utilizing partners or terminal electron acceptors. The pure culture of S. aciditrophicus produced approximately 0.5 mol of cyclohexane carboxylate and 1.5 mol of acetate per mol of benzoate, while a coculture of S. aciditrophicus with the hydrogen-using methanogen Methanospirillum hungatei produced 3 mol of acetate and 0.75 mol of methane per mol of benzoate. The growth yield of the S. aciditrophicus pure culture was 6.9 g (dry weight) per mol of benzoate metabolized, whereas the growth yield of the S. aciditrophicus-M. hungatei coculture was 11.8 g (dry weight) per mol of benzoate. Cyclohexane carboxylate was metabolized by S. aciditrophicus only in a coculture with a hydrogen user and was not metabolized by S. aciditrophicus pure cultures. Cyclohex-1-ene carboxylate was incompletely degraded by S. aciditrophicus pure cultures until a free energy change (ΔG′) of −9.2 kJ/mol was reached (−4.7 kJ/mol for the hydrogen-producing reaction). Cyclohex-1-ene carboxylate, pimelate, and glutarate transiently accumulated at micromolar levels during growth of an S. aciditrophicus pure culture with benzoate. High hydrogen (10.1 kPa) and acetate (60 mM) levels inhibited benzoate metabolism by S. aciditrophicus pure cultures. These results suggest that benzoate fermentation by S. aciditrophicus in the absence of hydrogen users proceeds via a dismutation reaction in which the reducing equivalents produced during oxidation of one benzoate molecule to acetate and carbon dioxide are used to reduce another benzoate molecule to cyclohexane carboxylate, which is not metabolized further. Benzoate fermentation to acetate, CO2, and cyclohexane carboxylate is thermodynamically favorable and can proceed at free energy values more positive than −20 kJ/mol, the postulated minimum free energy value for substrate metabolism. PMID:11722901

NK2 tachykinin receptors mediate contraction of the pig intravesical ureter: tachykinin-induced enhancement of non-adrenergic non-cholinergic excitatory neurotransmission.

PubMed

Bustamante, S; Orensanz, L M; Barahona, M V; García-Sacristán, A; Hernández, M

2001-01-01

The current study was designed to characterize the functionally active tachykinin receptors involved in tachykinin-elicited contractions in the pig intravesical ureter, and to investigate the possible modulation exerted by the natural tachykinins substance P (SP) and neurokinin A (NKA) on the non-adrenergic non-cholinergic (NANC) excitatory ureteral neurotransmission. In pig intravesical ureteral strips pretreated with phosphoramidon (10(-5) mol/L) to block the endopeptidase activities, isometric force recordings showed that SP, NKA, and the NK2 receptor selective agonist [beta-Ala(8)]-NKA (4-10), all three induced contractions, with the following potency order: NKA > [beta-Ala(8) ]-NKA (4-10) > SP. [Sar(9), Met(O(2))(11)]-SP and senktide, selective agonists of the NK1 and NK3 receptors, respectively, failed to modify the ureteral tone. Urothelium removal and incubation with tetrodotoxin (10(-6) mol/L), phentolamine (10(-7) mol/L), propranolol (3 x 10(-6) mol/L), atropine (10(-7) mol/L) and indomethacin (3 x 10(-6) mol/L), did not alter the contraction induced by a submaximal (10(-7) mol/L) dose of [beta-Ala(8)]-NKA (4-10). MEN 10,376 (10(-8)-10(-7) mol/L), a NK2 receptor antagonist, reduced the contraction to 3 x 10(-8) mol/L NKA. GR 82334 (10(-6) -10(-5) mol/L) and SR 142801 (10(-8)-10(-7) mol/L), selective antagonists of the NK1 and NK3 receptors, respectively, did not modify that contraction. In pig intravesical ureteral strips in NANC conditions, SP and NKA induced a potentiation of the contractions to electrical field stimulation (EFS) and to exogenous ATP. The results suggest that the tachykinins evoke a direct contraction of pig intravesical ureteral strips through NK2 receptors located in the smooth muscle. SP and NKA exert an enhancement of the NANC excitatory neurotransmission of the pig intravesical ureter.

Decrease of serum carnitine levels in patients with or without gastrointestinal cancer cachexia

PubMed Central

Malaguarnera, Mariano; Risino, Corrado; Gargante, Maria Pia; Oreste, Giovanni; Barone, Gloria; Tomasello, Anna Veronica; Costanzo, Mario; Cannizzaro, Matteo Angelo

2006-01-01

AIM: To evaluate the levels of serum carnitine in patients with cancer in digestive organs and to compare them with other cancers in order to provide new insights into the mechanisms of cachexia. METHODS: Fifty-five cachectic patients with or without gastrointestinal cancer were enrolled in the present study. They underwent routine laboratory investigations, including examination of the levels of various forms of carnitine present in serum (i.e., long-chain acylcarnitine, short-chain acylcarnitine, free carnitine, and total carnitine). These values were compared with those found in 60 cancer patients in good nutritional status as well as with those of 30 healthy control subjects. RESULTS: When the cachectic patients with gastro-intestinal cancer were compared with the cachectic patients without gastrointestinal cancer, the difference was -6.8 μmol/L in free carnitine (P < 0.005), 0.04 μmol/L in long chain acylcarnitine (P < 0.05), 8.7 μmol/L in total carnitine (P < 0.001). In the cachectic patients with or without gastrointestinal cancer, the difference was 12.2 μmol/L in free carnitine (P < 0.001), 4.60 μmol/L in short chain acylcarnitine (P < 0.001), and 0.60 μmol /L in long-chain acylcarnitine (P < 0.005) and 17.4 μmol/L in total carnitine (P < 0.001). In the cachectic patients with gastrointestinal cancer and the healthy control subjects, the difference was 15.5 μmol/L in free carnitine (P < 0.001), 5.2 μmol /L in short-chain acylcarnitine (P < 0.001), 1.0 μmol/L in long chain acylcarnitine (P < 0.001), and 21.8 μmol/L in total carnitine (P < 0.001). CONCLUSION: Low serum levels of carnitine in terminal neoplastic patients are decreased greatly due to the decreased dietary intake and impaired endogenous synthesis of this substance. These low serum carnitine levels also contribute to the progression of cachexia in cancer patients. PMID:16874868

Myosin dephosphorylation during rapid relaxation of hog carotid artery smooth muscle.

PubMed

Driska, S P; Stein, P G; Porter, R

1989-02-01

Changes in myosin light chain phosphorylation were measured during histamine-induced rhythmic contractions of hog carotid artery smooth muscle strips. Histamine made the muscle strips contract spontaneously every 1-5 min, and this allowed measurement of the time course of phosphorylation in relation to force development under conditions where diffusion of the agonist through tissue would not complicate the interpretation of the data. In the absence of histamine, phosphorylation was low [0.12 +/- 0.04 mol P/mol of the 20,000-Da light chain (LC 20)]. Phosphorylation was slightly (but not significantly) higher in the presence of 10 microM histamine in the relaxed state between contractions (0.20 +/- 0.03 mol P/mol LC 20). In muscle strips frozen during force development, when force had reached half of its peak value, phosphorylation was 0.38 +/- 0.06 mol P/mol LC 20. The highest levels of phosphorylation (0.49 +/- 0.04 mol P/mol LC 20) were found in strips frozen at the peak of the rhythmic contractions. Strips frozen when force had declined to half of the peak force showed low levels of phosphorylation (0.17 +/- 0.07 mol P/mol LC 20), indicating that the myosin light chain phosphatase activity was quite high. Mathematical modeling of the kinase and phosphatase reactions suggested that the apparent first-order phosphatase rate constant was at least 0.08 s-1 under these conditions. To obtain a better estimate of this rate constant, a second series of phosphorylation measurements were made early in the relaxation phase of the rhythmic contractions. The highest phosphatase rate constant obtained from these measurements was 0.23 s-1.(ABSTRACT TRUNCATED AT 250 WORDS)

N-(4-Meth-oxy-phen-yl)-6-methyl-2-phenyl-5-{[4-(tri-fluoro-meth-yl)anilino]meth-yl}pyrimidin-4-amine.

PubMed

Cieplik, Jerzy; Pluta, Janusz; Bryndal, Iwona; Lis, Tadeusz

2013-11-27

The title compound, C26H23F3N4O, crystallizes with two symmetry-independent mol-ecules in the asymmetric unit, denoted A and B, which differ mainly in the rotation of the meth-oxy-phenyl ring. The -CF3 group of mol-ecule B is disordered by rotation, with the F atoms split over two sets of sites; the occupancy factor for the major component is 0.853 (4). The dihedral angles between the pyrimidine ring and the attached phenyl, meth-oxy-phenyl and tri-fluoro-methyl-phenyl rings are 8.1 (2), 37.5 (2) and 70.7 (2)°, respectively, in mol-ecule A, and 9.3 (2), 5.3 (2) and 79.7 (2)° in mol-ecule B. An intra-molecular N-H⋯N hydrogen bond occurs in each mol-ecule. In the crystal, two crystallographically independent mol-ecules associate into a dimer via a pair of N-H⋯N hydrogen bonds, with a resulting R 2 (2)(12) ring motif and π-π stacking inter-actions [centroid-centroid distance = 3.517 (4) Å] between the pyrimidine rings. For the A mol-ecules, there are inter-molecular C-H⋯O hydrogen bonds between an aryl C atom of meth-oxy-phenyl ring and a meth-oxy O atom of an adjacent mol-ecule. A similar inter-action is lacking in the B mol-ecules.

Comparative evaluation of antiplatelet effect of lycopene with aspirin and the effect of their combination on platelet aggregation: An in vitro study

PubMed Central

Sawardekar, Swapna B.; Patel, Tejal C.; Uchil, Dinesh

2016-01-01

Introduction: The objective was to compare antiplatelet effect of lycopene with aspirin and to study effect of combination of the two on platelet aggregation in vitro, using platelets from healthy volunteers. Materials and Methods: Platelets were harvested; platelet count of platelet-rich plasma adjusted to 2.5 Χ 105/μL. Aspirin (140 μmol/L) and lycopene (4, 6, 8, 10, and 12 μmol/L) were studied in vitro against adenosine-5’- diphosphate (ADP) (2.5 μM/L) and collagen Results: All the concentrations of lycopene (4–12 μmol/L) exhibited reduction in maximum platelet aggregation induced by aggregating agents ADP and collagen (P < 0.01 vs. vehicle) and were comparable with aspirin. Lycopene at concentration 10 μmol/L showed maximum platelet inhibition (47.05% ± 19.56%) against ADP, whereas lycopene at concentration 8 μmol/L showed maximum platelet inhibition (54.26% ± 30.71%) against collagen. Four μmol/L of lycopene combined with 140 μmol/L and 70 μmol/L aspirin showed greater inhibition of platelets as compared to aspirin 140 μmol/L alone, against both ADP and collagen. Conclusion: The study favorably compares lycopene and aspirin with respect to their antiplatelet activities against ADP and collagen. Lycopene can be considered as a potential target for modifying the thrombotic and pro-inflammatory events associated with platelet activation. PMID:26997718

Basic studies on the pyrolysis of lignin compounds

Treesearch

Byung-ho Hwang

2003-01-01

By pyrolyzing lignin model compounds 1-lV at 315°C, an investigation was carried out with some results. In the pyrolysis of lignin model compound I and 11, 0.47 mol of guaiacol, 0.57 mol of dimethoxyphenol (DMP), and 0.12 and 0.23 mol of dimethoxyaceton ophenone (DMAP) were produced respectively. In the pyrolysis of lignin model compound lll and lV, 0.26 mol of...

Stabilized aqueous hydrogen peroxide solution

DOE Office of Scientific and Technical Information (OSTI.GOV)

Malin, M.J.; Sciafani, L.D.

1988-05-17

This patent describes a stabilized aqueous hydrogen peroxide solution having a pH below 7 and an amount of Ferric ion up to about 2 ppm comprising hydrogen peroxide, acetanilide having a concentration which ranges between 0.74 M Mol/L and 2.22 mMol/L, and o-benzene disulfonic acid or salt thereof at a concentration between about 0.86 mMol/L to about 1.62 mMol/L.

Crystal structure of bis-(N-methyl-N-phenyl-amino)-tris-ulfane.

PubMed

Barany, George; Henley, Matthew J; Polski, Lauren A; Schroll, Alayne L; Young, Victor G

2015-07-01

The title compound, C14H16N2S3, crystallized with two independent mol-ecules [(1 a ) and (1 b )] in the asymmetric unit. Both mol-ecules display a pseudo-trans conformation. The two consecutive S-S bond lengths of the tris-ulfane unit of mol-ecule (1 a ) are 2.06 (3) and 2.08 (3) Å, and 2.08 (3) and 2.07 (2) Å for mol-ecule (1 b ). Torsion angles about each of the two S-S bonds are 86.6 (2) and 87.0 (2)° for (1 a ), and -84.6 (2) and -85.9 (2)° for (1 b ). The core atoms, viz. the N-S-S-S-N moiety, of the two mol-ecules superimpose well if one is inverted on the other, but the phenyl groups do not. Thus, the two units are essentially conformational enanti-omers. In mol-ecule (1 a ), the two phenyl rings are inclined to one another by 86.7 (3)°, and in mol-ecule (1 b ), by 81.1 (3)°. In the crystal, mol-ecules are linked via C-H⋯π inter-actions, forming sheets lying parallel to (010).

Role of carbonic anhydrase in basal and stimulated bicarbonate secretion by the guinea pig duodenum.

PubMed

Muallem, R; Reimer, R; Odes, H S; Schwenk, M; Beil, W; Sewing, K F

1994-05-01

The role of carbonic anhydrase in the process of proximal duodenal mucosal bicarbonate secretion was investigated in the guinea pig. In a series of experiments in vivo, the duodenum was perfused with 24 mmol/liter NaHCO3 solution (+ NaCl for isotonicity) to ensure that active duodenal HCO3- secretion against a concentration gradient was measured. Acetazolamide (80 mg/kg) was infused intravenously to examine the role of carbonic anhydrase on basal and agonist-stimulated HCO3- secretion. Acetazolamide abolished basal HCO3- secretion and significantly decreased HCO3- secretion after stimulation with dibutyryl 5'-cyclic adenosine monophosphate (dBcAMP, 10(-5) mol/kg), dibutyryl 5'-cyclic guanosine monophosphate (dBcGMP, 10(-5) mol/kg), prostaglandin E2 (PGE2, 10(-6) mol/kg), PGF2 alpha (10(-6) mol/kg), tetradecanoyl-phorbol-acetate (TPA, 10(-7) mol/kg), glucagon (10(-7) mol/kg), vasoactive intestinal polypeptide (VIP, 10(-8) mol/kg), and carbachol (10(-8) mol/kg). Utilizing a fluorescence technique, we could detect the enzyme carbonic anhydrase in equal amounts in villous and crypt cells of the proximal duodenal epithelium; no activity was demonstrated in tissues pretreated with acetazolamide. In conclusion, carbonic anhydrase is required for both basal and stimulated duodenal HCO3- secretion.

Hydrogen-bonding patterns in 5-fluoro-cytosine-melamine co-crystal (4/1).

PubMed

Mohana, Marimuthu; Muthiah, Packianathan Thomas; Sanjeewa, Liurukara D; McMillen, Colin D

2016-04-01

The asymmetric unit of the title compound, 4C4H4FN3O·C3H6N6, comprises of two independent 5-fluoro-cytosine (5FC) mol-ecules (A and B) and one half-mol-ecule of melamine (M). The other half of the melamine mol-ecule is generated by a twofold axis. 5FC mol-ecules A and B are linked through two different homosynthons [R 2 (2)(8) ring motif]; one is formed via a pair of N-H⋯O hydrogen bonds and the second via a pair of N-H⋯N hydrogen bonds. In addition to this pairing, the O atoms of 5FC mol-ecules A and B inter-act with the N2 amino group on both sides of the melamine mol-ecule, forming a DDAA array of quadruple hydrogen bonds and generating a supra-molecular pattern. The 5FC (mol-ecules A and B) and two melamine mol-ecules inter-act via N-H⋯O, N-H⋯N and N-H⋯O, N-H⋯N, C-H⋯F hydrogen bonds forming R 6 (6)(24) and R 4 (4)(15) ring motifs. The crystal structure is further strengthened by C-H⋯F, C-F⋯π and π-π stacking inter-actions.

Microstructure and Properties of KSr2Nb5O15 Ceramics with Excess K+

NASA Astrophysics Data System (ADS)

Wang, Min; Gao, Feng; Xu, Jie; Zhang, Chaochao; Qin, Mengjie; Wang, Li; Guo, Yiting

2017-03-01

KSr2Nb5O15- xK (KSN- xK, x = 0 mol.%, 4 mol.%, 8 mol.%, 12 mol.%, 16 mol.%, and 20 mol.%) lead-free ferroelectric ceramics have been prepared by a buried sintering method using needle-like KSN particles synthesized by molten salt synthesis, and their microstructure, dielectric properties, and infrared transmittance investigated. The results suggest that the KSN- xK ceramics had simplex tungsten bronze structure for x ≤ 12 mol.%, but K2Nb8O21 secondary phase appeared at higher x. Excess K+ compensated the shortage of A-site ions in KSN crystallites, alleviated lattice distortion, and drove the KSN component closer to stoichiometric ratio, all of which increased the Curie temperature. The dielectric relaxor behavior of the ceramics was enhanced as the excess K+ content was increased. The dielectric constant, dielectric tunability, and infrared transmittance initially increased then decreased with increasing x. The specimen with 12 mol.% excess K+ showed optimum electrical properties, including maximum infrared transmittance of ˜60%. This work confirms that A-site vacancies in KSN can be compensated by excess K+, and that this effect can be used to adjust the local composition, alleviate structural distortion of the oxygen octahedron, enhance the Curie temperature, etc.

Carbonate dissolution rates in high salinity brines: Implications for post-Noachian chemical weathering on Mars

NASA Astrophysics Data System (ADS)

Phillips-Lander, Charity M.; Parnell, S. R.; McGraw, L. E.; Elwood Madden, M. E.

2018-06-01

A diverse suite of carbonate minerals including calcite (CaCO3) and magnesite (MgCO3) have been observed on the martian surface and in meteorites. Terrestrial carbonates usually form via aqueous processes and often record information about the environment in which they formed, including chemical and textural biosignatures. In addition, terrestrial carbonates are often found in association with evaporite deposits on Earth. Similar high salinity environments and processes were likely active on Mars and some areas may contain active high salinity brines today. In this study, we directly compare calcite and magnesite dissolution in ultrapure water, dilute sulfate and chloride solutions, as well as near-saturated sulfate and chloride brines with known activity of water (aH2O) to determine how dissolution rates vary with mineralogy and aH2O, as well as aqueous cation and anion chemistry to better understand how high salinity fluids may have altered carbonate deposits on Mars. We measured both calcite and magnesite initial dissolution rates at 298 K and near neutral pH (6-8) in unbuffered solutions containing ultrapure water (18 MΩ cm-1 UPW; aH2O = 1), dilute (0.1 mol kg-1; aH2O = 1) and near-saturated Na2SO4 (2.5 mol kg-1, aH2O = 0.92), dilute (0.1 mol kg-1, aH2O = 1) and near-saturated NaCl (5.7 mol kg-1, aH2O = 0.75). Calcite dissolution rates were also measured in dilute and near-saturated MgSO4 (0.1 mol kg-1, aH2O = 1 and 2.7 mol kg-1, aH2O = 0.92, respectively) and MgCl2 (0.1 mol kg-1, aH2O = 1 and 3 mol kg-1, aH2O = 0.73, respectively), while magnesite dissolution rates were measured in dilute and near-saturated CaCl2 (0.1 mol kg-1, aH2O = 1 and 9 mol kg-1, aH2O = 0.35). Initial calcite dissolution rates were fastest in near-saturated MgCl2 brine, while magnesite dissolution rates were fastest in dilute (0.1 mol kg-1) NaCl and CaCl2 solutions. Calcite dissolution rates in near-saturated Na2SO4 were similar to those observed in the dilute solutions (-8.00 ± 0.12 log mol m-2 s-1), while dissolution slowed in both NaCl solutions (0.1 mol kg-1; -8.23 ± 0.10 log mol m-2 s-1 and (5.7 mol kg-1; -8.44 ± 0.11 log mol m-2 s-1), as well as near-saturated MgSO4 brine (2.7 mol kg-1; -8.35 ± 0.05 log mol m-2 s-1). The slowest calcite dissolution rates observed in the near-saturated NaCl brine. Magnesite dissolution rates were ∼5 times faster in the dilute salt solutions relative to UPW, but similar to UPW (-8.47 ± 0.06 log mol m-2 s-1) in near-saturated Na2SO4 brines (-8.41 ± 0.18 log mol m-2 s-1). Magnesite dissolution slowed significantly in near-saturated CaCl2 brine (-9.78 ± 0.10 log mol m-2 s-1), likely due to the significantly lower water activity in these experiments. Overall, magnesite dissolution rates are slower than calcite dissolution rates and follow the trend: All dilute salt solutions >2.5 mol kg-1 Na2SO4 ≈ UPW > 5.7 mol kg-1 NaCl >> 9 mol kg-1 CaCl2. Calcite rates follow the trend 3 mol kg-1 MgCl2 > 2.5 mol kg-1 Na2SO4 ≈ UPW ≈ all dilute salt solutions >2.7 mol kg-1 MgSO4 ≈ 5.7 mol kg-1 NaCl. Magnesite dissolution rates in salt solutions generally decrease with decreasing aH2O in both chloride and sulfate brines, which indicates water molecules act as ligands and participate in the rate-limiting magnesite dissolution step. However, there is no general trend associated with water activity observed in the calcite dissolution rates. Calcite dissolution accelerates in near-saturated MgCl2, but slows in near-saturated NaCl brine despite both brines having similar water activities (aH2O = 0.73 and 0.75, respectively). High Mg calcite was observed as a reaction product in the near-saturated MgCl2, indicating Mg2+ from solution likely substituted for Ca2+ in the initial calcite, releasing additional Ca2+ into solution and increasing the observed calcite dissolution rate. Calcite dissolution rates also increase slightly as Na2SO4 concentration increases, while calcite dissolution rates slow slightly with increasing concentration of MgSO4 and NaCl. However, all of the carbonate rates vary by less than 0.5 log units and are within or near the standard deviation observed for each set of replicate experiments. Carbonate mineral lifetimes in high salinity brines indicate magnesite may be preferentially preserved compared to calcite on Mars. Therefore, Mg-carbonates that have experienced post-depositional aqueous alteration are more likely to preserve paleoenvironmental indicators and potential biosignatures. Rapid weathering of carbonates in circum-neutral pH sulfate brines may provide a potential source of cations for abundant sulfate minerals observed on Mars, Ceres, and other planetary bodies.

Low-melting point heat transfer fluid

DOEpatents

Cordaro, Joseph G [Oakland, CA; Bradshaw, Robert W [Livermore, CA

2011-04-12

A low-melting point, heat transfer fluid comprising a mixture of LiNO.sub.3, NaNO.sub.3, KNO.sub.3, NaNO.sub.2 and KNO.sub.2 salts where the Li, Na and K cations are present in amounts of about 20-33.5 mol % Li, about 18.6-40 mol % Na, and about 40-50.3 mol % K and where the nitrate and nitrite anions are present in amounts of about 36-50 mol % NO.sub.3, and about 50-62.5 mol % NO.sub.2. These compositions can have liquidus temperatures between 70.degree. C. and 80.degree. C. for some compositions.

Evolução química de galáxias HII anãs

NASA Astrophysics Data System (ADS)

Ferraresi, M., Jr.; Cuisinier, F.; Telles, E.

2003-08-01

Galáxias HII anãs são galáxias de baixa massa, com alto conteúdo de gás, e se encontram em uma fase intensa de formação estelar. A taxa de formação estelar está tão alta nestas galáxias que não pode ter se mantido durante sua vida inteira. O tempo máximo de duração do episódio atual de formação estelar deve ser no máximo de algumas dezenas de milhões de anos, bem inferior à idade destas galáxias. Isto leva naturalmente a idéia de que já aconteceram surtos anteriores. Abundâncias químicas oferecem uma ferramenta poderosa para investigar a história evolutiva destas galáxias, porque aumentam de geração em geração estelar. O hidrogênio, o oxigênio, o nitrogênio produzem algumas das linhas mais importantes em um gás foto-ionizado, permitindo a determinação das abundâncias destes elementos facilmente. A dispersão das abundâncias em oxigênio e nitrogênio é significativa, sendo maior que os erros observacionais. O oxigênio é produzido em estrelas massivas, que explodem quase instâneamente, enquanto o nitrogênio é produzido em estrelas de massa intermediária, que só o liberam depois de um atraso de @ 500 mihões de anos. Construímos um modelo de evolução química semi-analítico, utilizando rendimentos empíricos baseados nas abundâncias observadas destes dois elementos. Conseguimos através deste modelo rudimentar explicar nas galáxias de mais baixas metalicidades as abundâncias de oxigênio e de nitrogênio, assim como a dispersão dos dados observacionais devida a formação estelar descontínua, e isto com um número baixo de surtos (1 ou 2, no máximo 3).

The ozone acetylene reaction: concerted or non-concerted reaction mechanism? A quantum chemical investigation

NASA Astrophysics Data System (ADS)

Cremer, Dieter; Kraka, Elfi; Crehuet, Ramon; Anglada, Josep; Gräfenstein, Jürgen

2001-10-01

The ozone-acetylene reaction is found to proceed via an intermediate van der Waals complex (rather than a biradical), which is the precursor for a concerted symmetry-allowed [4+2] cycloaddition reaction leading to 1,2,3-trioxolene. CCSD(T)/6-311G+(2d, 2p) and CCSD(T)/CBS (complete basis set) calculations predict the ozone-acetylene van der Waals complex to be stable by 2.2 kcal mol -1, the calculated activation enthalpy for the cycloaddition reaction is 9.6 kcal mol -1 and the reaction enthalpy -55.5 kcal mol -1. Calculated kinetic data for the overall reaction ( k=0.8 l mol -1 s-1, A=1.71×10 6 l mol -1 s-1, E a=8.6 kcal mol -1) suggest that there is a need for refined kinetic measurements.

INTERACTION OF LASER RADIATION WITH MATTER: Influence of Ca and Pb impurities on the bulk optical strength of ultrapure NaCl and KCl crystals

NASA Astrophysics Data System (ADS)

Vinogradov, An V.; Voszka, R.; Kovalev, Valerii I.; Faĭzullov, F. S.; Janszky, J.

1987-06-01

A significant increase (by a factor of about 3) of the bulk damage threshold in the case of interaction of CO2 laser radiation pulses with ultrapure NaCl and KCl crystals grown in a reactive atmosphere was observed on introduction of divalent metal ions Ca and Pb in concentrations of 10-5-10-6 mol/mol. Impurities were introduced in concentrations of 10-8-10-3 and 2×10-7-10-4 mol/mol into the melts of KCl and NaCl, respectively. The concentration of other impurities (including OH) did not exceed ~10-6 mol/mol. A physical model was developed to account for the observed dependence on the basis of an analogy between a system of colloidal particles and F centers in a crystal and a liquid-vapor system.

HackaMol: An Object-Oriented Modern Perl Library for Molecular Hacking on Multiple Scales

DOE PAGES

Riccardi, Demian M.; Parks, Jerry M.; Johs, Alexander; ...

2015-03-20

HackaMol is an open source, object-oriented toolkit written in Modern Perl that organizes atoms within molecules and provides chemically intuitive attributes and methods. The library consists of two components: HackaMol, the core that contains classes for storing and manipulating molecular information, and HackaMol::X, the extensions that use the core. We tested the core; it is well-documented and easy to install across computational platforms. Our goal for the extensions is to provide a more flexible space for researchers to develop and share new methods. In this application note, we provide a description of the core classes and two extensions: HackaMol::X::Calculator, anmore » abstract calculator that uses code references to generalize interfaces with external programs, and HackaMol::X::Vina, a structured class that provides an interface with the AutoDock Vina docking program.« less

HackaMol: An Object-Oriented Modern Perl Library for Molecular Hacking on Multiple Scales.

PubMed

Riccardi, Demian; Parks, Jerry M; Johs, Alexander; Smith, Jeremy C

2015-04-27

HackaMol is an open source, object-oriented toolkit written in Modern Perl that organizes atoms within molecules and provides chemically intuitive attributes and methods. The library consists of two components: HackaMol, the core that contains classes for storing and manipulating molecular information, and HackaMol::X, the extensions that use the core. The core is well-tested, well-documented, and easy to install across computational platforms. The goal of the extensions is to provide a more flexible space for researchers to develop and share new methods. In this application note, we provide a description of the core classes and two extensions: HackaMol::X::Calculator, an abstract calculator that uses code references to generalize interfaces with external programs, and HackaMol::X::Vina, a structured class that provides an interface with the AutoDock Vina docking program.

HackaMol: An Object-Oriented Modern Perl Library for Molecular Hacking on Multiple Scales

DOE Office of Scientific and Technical Information (OSTI.GOV)

Riccardi, Demian M.; Parks, Jerry M.; Johs, Alexander

HackaMol is an open source, object-oriented toolkit written in Modern Perl that organizes atoms within molecules and provides chemically intuitive attributes and methods. The library consists of two components: HackaMol, the core that contains classes for storing and manipulating molecular information, and HackaMol::X, the extensions that use the core. We tested the core; it is well-documented and easy to install across computational platforms. Our goal for the extensions is to provide a more flexible space for researchers to develop and share new methods. In this application note, we provide a description of the core classes and two extensions: HackaMol::X::Calculator, anmore » abstract calculator that uses code references to generalize interfaces with external programs, and HackaMol::X::Vina, a structured class that provides an interface with the AutoDock Vina docking program.« less

Properties of the LiCl-KCl-Li2O system as operating medium for pyro-chemical reprocessing of spent nuclear fuel

NASA Astrophysics Data System (ADS)

Mullabaev, Albert; Tkacheva, Olga; Shishkin, Vladimir; Kovrov, Vadim; Zaikov, Yuriy; Sukhanov, Leonid; Mochalov, Yuriy

2018-03-01

Crystallization temperatures (liquidus and solidus) in the LiCl-Li2O and (LiCl-KCl)-Li2O systems with the KCl content of 10 and 20 mol.% were obtained with independent methods of thermal analysis using cooling curves, isothermal saturation, and differential scanning calorimetry. The linear sweep voltammetry was applied to control the time of the equilibrium establishment in the molten system after the Li2O addition, which depended on the composition of the base melt and the concentration of Li2O. The fragments of the binary LiCl-Li2O and quazi-binary [LiCl-KCl(10 mol.%)]-Li2O and [LiCl-KCl(20 mol.%)]-Li2O phase diagrams in the Li2O concentration range from 0 to 12 mol.% were obtained. The KCl presence in the LiCl-KCl-Li2O molten mixture in the amount of 10 and 20 mol.% reduces the liquidus temperature by 30 and 80°, respectively, but the region of the homogeneous molten state of the system is considerably narrowed, which complicates its practical application. The Li2O solubility in the molten LiCl, LiCl-KCl(10 mol.%) and LiCl-KCl(20 mol.%) decreases with increasing the KCl content and is equal to 11.5, 7.7 and 3.9 mol.% at 650°С, respectively. The LiCl-KCl melt with 10 mol.% KCl can be recommended for practical use as a medium for the SNF pyro-chemical reprocessing at temperature below 700 °C.

Bile Acids Increase Independently From Hypocaloric Restriction After Bariatric Surgery.

PubMed

Jahansouz, Cyrus; Xu, Hongliang; Hertzel, Ann V; Serrot, Federico J; Kvalheim, Nicholas; Cole, Abigail; Abraham, Anasooya; Luthra, Girish; Ewing, Kristin; Leslie, Daniel B; Bernlohr, David A; Ikramuddin, Sayeed

2016-12-01

To measure changes in the composition of serum bile acids (BA) and the expression of Takeda G-protein-coupled receptor 5 (TGR5) acutely after bariatric surgery or caloric restriction. Metabolic improvement after bariatric surgery occurs before substantial weight loss. BA are important metabolic regulators acting through the farnesoid X receptor and TGR5 receptor. The acute effects of surgery on BA and the TGR5 receptor in subcutaneous white adipose tissue (WAT) are unknown. A total of 27 obese patients with type 2 diabetes mellitus were randomized to Roux-en-Y gastric bypass (RYGB) or to hypocaloric diet (HC diet) restriction (NCT 1882036). A cohort of obese patients with and without type 2 diabetes mellitus undergoing vertical sleeve gastrectomy was also recruited (n = 12) as a comparison. After vertical sleeve gastrectomy, the level of BA increased [total: 1.17 ± 1.56 μmol/L to 4.42 ± 3.92 μmol/L (P = 0.005); conjugated BA levels increased from 0.99 ± 1.42 μmol/L to 3.59 ± 3.70 μmol/L (P = 0.01) and unconjugated BA levels increased from 0.18 ± 0.24 μmol/L to 0.83 ± 0.70 μmol/L (P = 0.009)]. With RYGB, there was a trend toward increased BA [total: 1.37 ± 0.97 μmol/L to 3.26 ± 3.01 μmol/L (P = 0.07); conjugated: 1.06 ± 0.81 μmol/L to 2.99 ± 3.02 μmol/L (P = 0.06)]. After HC diet, the level of unconjugated BA decreased [0.92 ± 0.55 μmol/L to 0.32 ± 0.43 μmol/L (P = 0.05)]. The level of WAT TGR5 gene expression decreased after surgery, but not in HC diet. Protein levels did not change. The levels of serum BA increase after bariatric surgery independently from caloric restriction, whereas the level of WAT TGR5 protein is unaffected.

Conformational stability, barriers to internal rotation, normal coordinate analyses, and vibrational assignments of bromoacetyl halides

NASA Astrophysics Data System (ADS)

Durig, J. R.; Phan, H. V.; Little, T. S.

1989-09-01

The Raman (3200-10 cm -1) and IR (3200-30 cm -1) spectra of bromoacetyl fluoride, bromoacetyl chloride and bromoacetyl bromide in the gaseous and annealed solid phases have been recorded. Additionally, the Raman spectra and the qualitative depolarization measurements for each molecule in the liquid phase have been obtained. All of these data indicate that these bromoacetyl halides exist in mixtures of two conformers, with the trans rotamer (halogen atoms oriented trans to one another) being the thermodynamically preferred, and the gauche conformation being the high energy form. From the studies of Raman spectra at different temperatures, the enthalpy differences have been determined for the gaseous and liquid phases, respectively, to be 185 ± 23 cm -1 (0.53 ± 0.06 kcal mol -1) and 249 ± 27 cm -1 (0.71 ± 0.08 kcal mol -1) for bromoacetyl fluoride, 391 ± 130 cm -1 (1.12 ± 0.37 kcal mol -1) and 317 ± 27 cm -1 (0.91 ± 0.08 kcal mol -1) for bromoacetyl chloride, and 341 ± 48 cm -1 (0.98 ± 0.14 kcal mol -1) and 286 ± 26 cm -1 (0.82 ± 0.07 kcal mol -1) for bromoacetyl bromide. Potential functions have been calculated for the fluoride and chloride from the observed asymmetric torsional frequencies and values of 580 ± 11 cm -1 (1.66 ± 0.03 kcal mol -1), 359 ± 8 cm -1 (1.03 ± 0.02 kcal mol -1), and 387 ± 16 cm -1 (1.11 ± 0.04 kcal mol -1) for the trans to gauche, gauche to gauche to gauche and gauche to trans barrier, respectively, were determined for bromoacetyl fluoride. The corresponding quantities were 967 ± 30 cm -1 (2.76 ± 0.08 kcal mol -1), 696 ± 67 cm -1 (1.99 ± 0.19 kcal mol -1), and 663 ± 30 cm -1 (1.61 ± 0.08 kcal mol -1) for bromoacetyl chloride. These potential functions are consistent with the dihedral angle of the gauche conformation being 120° and 117° for the fluoride and chloride, respectively. Complete vibrational assignments have been carried out based on the observed IR band contours, the depolarization ratios, and group frequencies. The results are compared to those for other haloacetyl halides.

eMolTox: prediction of molecular toxicity with confidence.

PubMed

Ji, Changge; Svensson, Fredrik; Zoufir, Azedine; Bender, Andreas

2018-03-07

In this work we present eMolTox, a web server for the prediction of potential toxicity associated with a given molecule. 174 toxicology-related in vitro/vivo experimental datasets were used for model construction and Mondrian conformal prediction was used to estimate the confidence of the resulting predictions. Toxic substructure analysis is also implemented in eMolTox. eMolTox predicts and displays a wealth of information of potential molecular toxicities for safety analysis in drug development. The eMolTox Server is freely available for use on the web at http://xundrug.cn/moltox. chicago.ji@gmail.com or ab454@cam.ac.uk. Supplementary data are available at Bioinformatics online.

Photoluminescence and doping mechanism of theranostic Eu3+/Fe3+ dual-doped hydroxyapatite nanoparticles.

PubMed

Chen, Min-Hua; Yoshioka, Tomohiko; Ikoma, Toshiyuki; Hanagata, Nobutaka; Lin, Feng-Huei; Tanaka, Junzo

2014-10-01

Theranostic nanoparticles currently have been regarded as an emerging concept of 'personalized medicine' with diagnostic and therapeutic dual-functions. Eu 3+ doped hydroxyapatite (HAp) has been regarded as a promising fluorescent probe for in vivo imaging applications. Additionally, substitution of Ca 2+ with Fe 3+ in HAp crystal may endow the capability of producing heat upon exposure to a magnetic field. Here we report a preliminary study of doping mechanism and photoluminescence of Eu 3+ and Fe 3+ doped HAp nanoparticles (Eu/Fe:HAp). HAp with varied concentration of Eu 3+ and Fe 3+ doping are presented as Eu(10 mol%):HAp, Eu(7 mol%)-Fe(3 mol%):HAp, Eu(5 mol%)-Fe(5 mol%):HAp, Eu(3 mol%)-Fe(7 mol%):HAp, and Fe(10 mol%):HAp in the study. The results showed that the HAp particles, in nano-size with rod-like morphology, were successfully doped with Eu 3+ and Fe 3+ , and the particles can be well suspended in cell culture medium. Photoluminescence analysis revealed that particles have prominent emissions at 536 nm, 590 nm, 615 nm, 650 nm and 695 nm upon excitation at a wavelength of 397 nm. Moreover, these Eu/Fe:HAp nanoparticles belonged to B-type carbonated HAp, which has been considered an effective biodegradable and biocompatible drug/gene carrier in biological applications.

Crystal structure of bis­(N-methyl-N-phenyl­amino)­tris­ulfane

PubMed Central

Barany, George; Henley, Matthew J.; Polski, Lauren A.; Schroll, Alayne L.; Young, Victor G.

2015-01-01

The title compound, C14H16N2S3, crystallized with two independent mol­ecules [(1 a) and (1 b)] in the asymmetric unit. Both mol­ecules display a pseudo-trans conformation. The two consecutive S—S bond lengths of the tris­ulfane unit of mol­ecule (1 a) are 2.06 (3) and 2.08 (3) Å, and 2.08 (3) and 2.07 (2) Å for mol­ecule (1 b). Torsion angles about each of the two S—S bonds are 86.6 (2) and 87.0 (2)° for (1 a), and −84.6 (2) and −85.9 (2)° for (1 b). The core atoms, viz. the N—S—S—S—N moiety, of the two mol­ecules superimpose well if one is inverted on the other, but the phenyl groups do not. Thus, the two units are essentially conformational enanti­omers. In mol­ecule (1 a), the two phenyl rings are inclined to one another by 86.7 (3)°, and in mol­ecule (1 b), by 81.1 (3)°. In the crystal, mol­ecules are linked via C—H⋯π inter­actions, forming sheets lying parallel to (010). PMID:26279880

PMMA microreactor for chemiluminescence detection of Cu (II) based on 1,10-Phenanthroline-hydrogen peroxide reaction.

PubMed

Chen, Xueye; Shen, Jienan; Li, Tiechuan

2016-01-01

A microreactor for the chemiluminescence detection of copper (II) in water samples, based on the measurement of light emitted from the copper (II) catalysed oxidation of 1,10-phenanthroline by hydrogen peroxide in basic aqueous solution, is presented. Polymethyl methacrylate (PMMA) was chose as material for fabricating the microreactor with mill and hot bonding method. Optimized reagents conditions were found to be 6.3 × 10(-5)mol/L 1,10-phenanthroline, 1.5 × 10(-3)mol/L hydrogen peroxide, 7.0 × 10(-2)mol/L sodium hydroxide and 2.4 × 10(-5)mol/L Hexadecyl trimethyl ammonium Bromide (CTMAB). In the continuous flow injection mode the system can perform fully automated detection with a reagent consumption of only 3.5 μL each time. The linear range of the Cu (II) ions concentration was 1.5 × 10(-8) mol/L to 1.0 × 10(-4) mol/L, and the detection limit was 9.4 × 10(-9)mol/L with the S/N ratio of 4. The relative standard deviation was 3.0 % for 2.0 × 10(-6) mol/L Cu (II) ions (n = 10). The most obvious features of the detection method are simplicity, rapidity and easy fabrication of the microreactor.

A novel membrane-less direct alcohol fuel cell

NASA Astrophysics Data System (ADS)

Yi, Qingfeng; Chen, Qinghua; Yang, Zheng

2015-12-01

Membrane-less fuel cell possesses such advantages as simplified design and lower cost. In this paper, a membrane-less direct alcohol fuel cell is constructed by using multi-walled carbon nanotubes (MWCNT) supported Pd and ternary PdSnNi composites as the anode catalysts and Fe/C-PANI composite, produced by direct pyrolysis of Fe-doped polyaniline precursor, as the oxygen reduction reaction (ORR) catalyst. The alcohols investigated in the present study are methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol and sec-butanol. The cathode catalyst Fe/C-PANI is electrochemically inactive to oxidation of the alcohols. The performance of the cell with various alcohols in 1 mol L-1 NaOH solution on either Pd/MWCNT or PdSnNi/MWCNT catalyst has been evaluated. In any case, the performance of the cell using the anode catalyst PdSnNi/MWCNT is considerably better than Pd/MWCNT. For the PdSnNi/MWCNT, the maximum power densities of the cell using methanol (0.5 mol L-1), ethanol (0.5 mol L-1), n-propanol (0.5 mol L-1), iso-propanol (0.5 mol L-1), n-butanol (0.2 mol L-1), iso-butanol (0.2 mol L-1) and sec-butanol (0.2 mol L-1) are 0.34, 1.03, 1.07, 0.44, 0.50, 0.31 and 0.15 mW cm-2, respectively.

Hydrogen-bonding patterns in 5-fluoro­cytosine–melamine co-crystal (4/1)

PubMed Central

Mohana, Marimuthu; Muthiah, Packianathan Thomas; Sanjeewa, Liurukara D.; McMillen, Colin D.

2016-01-01

The asymmetric unit of the title compound, 4C4H4FN3O·C3H6N6, comprises of two independent 5-fluoro­cytosine (5FC) mol­ecules (A and B) and one half-mol­ecule of melamine (M). The other half of the melamine mol­ecule is generated by a twofold axis. 5FC mol­ecules A and B are linked through two different homosynthons [R 2 2(8) ring motif]; one is formed via a pair of N—H⋯O hydrogen bonds and the second via a pair of N—H⋯N hydrogen bonds. In addition to this pairing, the O atoms of 5FC mol­ecules A and B inter­act with the N2 amino group on both sides of the melamine mol­ecule, forming a DDAA array of quadruple hydrogen bonds and generating a supra­molecular pattern. The 5FC (mol­ecules A and B) and two melamine mol­ecules inter­act via N—H⋯O, N—H⋯N and N—H⋯O, N—H⋯N, C—H⋯F hydrogen bonds forming R 6 6(24) and R 4 4(15) ring motifs. The crystal structure is further strengthened by C—H⋯F, C—F⋯π and π–π stacking inter­actions. PMID:27375887

Simultaneous square-wave voltammetric determination of aspartame and cyclamate using a boron-doped diamond electrode.

PubMed

Medeiros, Roberta Antigo; de Carvalho, Adriana Evaristo; Rocha-Filho, Romeu C; Fatibello-Filho, Orlando

2008-07-30

A simple and highly selective electrochemical method was developed for the simultaneous determination of aspartame and cyclamate in dietary products at a boron-doped diamond (BDD) electrode. In square-wave voltammetric (SWV) measurements, the BDD electrode was able to separate the oxidation peak potentials of aspartame and cyclamate present in binary mixtures by about 400 mV. The detection limit for aspartame in the presence of 3.0x10(-4) mol L(-1) cyclamate was 4.7x10(-7) mol L(-1), and the detection limit for cyclamate in the presence of 1.0x10(-4) mol L(-1) aspartame was 4.2x10(-6) mol L(-1). When simultaneously changing the concentration of both aspartame and cyclamate in a 0.5 mol L(-1) sulfuric acid solution, the corresponding detection limits were 3.5x10(-7) and 4.5x10(-6) mol L(-1), respectively. The relative standard deviation (R.S.D.) obtained was 1.3% for the 1.0x10(-4) mol L(-1) aspartame solution (n=5) and 1.1% for the 3.0x10(-3) mol L(-1) cyclamate solution. The proposed method was successfully applied in the determination of aspartame in several dietary products with results similar to those obtained using an HPLC method at 95% confidence level.

Photoluminescence and doping mechanism of theranostic Eu3+/Fe3+ dual-doped hydroxyapatite nanoparticles

NASA Astrophysics Data System (ADS)

Chen, Min-Hua; Yoshioka, Tomohiko; Ikoma, Toshiyuki; Hanagata, Nobutaka; Lin, Feng-Huei; Tanaka, Junzo

2014-10-01

Theranostic nanoparticles currently have been regarded as an emerging concept of ‘personalized medicine’ with diagnostic and therapeutic dual-functions. Eu3+ doped hydroxyapatite (HAp) has been regarded as a promising fluorescent probe for in vivo imaging applications. Additionally, substitution of Ca2+ with Fe3+ in HAp crystal may endow the capability of producing heat upon exposure to a magnetic field. Here we report a preliminary study of doping mechanism and photoluminescence of Eu3+ and Fe3+ doped HAp nanoparticles (Eu/Fe:HAp). HAp with varied concentration of Eu3+ and Fe3+ doping are presented as Eu(10 mol%):HAp, Eu(7 mol%)-Fe(3 mol%):HAp, Eu(5 mol%)-Fe(5 mol%):HAp, Eu(3 mol%)-Fe(7 mol%):HAp, and Fe(10 mol%):HAp in the study. The results showed that the HAp particles, in nano-size with rod-like morphology, were successfully doped with Eu3+ and Fe3+, and the particles can be well suspended in cell culture medium. Photoluminescence analysis revealed that particles have prominent emissions at 536 nm, 590 nm, 615 nm, 650 nm and 695 nm upon excitation at a wavelength of 397 nm. Moreover, these Eu/Fe:HAp nanoparticles belonged to B-type carbonated HAp, which has been considered an effective biodegradable and biocompatible drug/gene carrier in biological applications.

Mechanisms of vasodilation in the dorsal aorta of the elephant fish, Callorhinchus milii (Chimaeriformes: Holocephali).

PubMed

Jennings, Brett L; Bell, Justin D; Hyodo, Susumu; Toop, Tes; Donald, John A

2007-07-01

This study investigated vasodilator mechanisms in the dorsal aorta of the elephant fish, Callorhinchus milii, using anatomical and physiological approaches. Nitric oxide synthase could only be located in the perivascular nerve fibres and not the endothelium of the dorsal aorta, using NADPH histochemistry and immunohistochemistry. In vitro organ bath experiments demonstrated that a NO/soluble guanylyl cyclase (GC) system appeared to be absent in the vascular smooth muscle, since the NO donors SNP (10(-4) mol l(-1)) and SIN-1 (10(-5) mol l(-1)) were without effect. Nicotine (3 x 10(-4) mol l(-1)) mediated a vasodilation that was not affected by ODQ (10(-5) mol l(-1)), L-NNA (10(-4) mol l(-1)), indomethacin (10(-5) mol l(-1)), or removal of the endothelium. In contrast, the voltage-gated sodium channel inhibitor, tetrodotoxin (10(-5) mol l(-1)), significantly decreased the dilation induced by nicotine, suggesting that it contained a neural component. Pre-incubation of the dorsal aorta with the calcitonin gene-related peptide (CGRP) receptor antagonist, CGRP(8-37) (10(-6) mol l(-1)) also caused a significant decrease in the nicotine-induced dilation. We propose that nicotine is mediating a neurally-derived vasodilation in the dorsal aorta that is independent of NO, prostaglandins and the endothelium, and partly mediated by CGRP.

[Effects of elevated ozone concentrations on reactive oxygen metabolism and related gene expression in Ginkgo biloba leaves].

PubMed

Ruan, Ya Nan; Xu, Sheng; Guo, Long; Zhu, Ming Zhu; Wang, Cong; Li, Shu Yuan; Wang, Hong Yan

2017-11-01

By using the open top chambers (OTCs) fumigation method, this paper investigated the changes of foliar injury, level of reactive oxygen species (ROS), activities and gene expression of antioxidant enzymes in Ginkgo biloba leaves under different ozone (ambient ozone≈40, 80, 160, 200 nmol·mol -1 ) concentrations, in order to study the effects of elevated ozone (O 3 ) concentrations on reactive metabolism. The results showed that the obvious foliar injuries were observed in 160 and 200 nmol·mol -1 O 3 treatments, while no visible injury was observed in 80 nmol·mol -1 O 3 and ambient O 3 treatments. After 20 d, a significant increase in O 2 -· generation rate was observed in G. biloba leaves exposed to 160, 200 nmol·mol -1 O 3 , compared with ambient ozone and 80 nmol·mol -1 O 3 , and there were no significant differences between ambient O 3 and 80 nmol·mol -1 treatments. After 40 d, H 2 O 2 content of G. biloba leaves in 160 and 200 nmol·mol -1 O 3 was significantly higher than that in 80 nmol·mol -1 and ambient ozone, respectively. The activities of catalase (CAT) in 160 and 200 nmol·mol -1 treatments were also significantly higher than that in 80 nmol·mol -1 and ambient O 3 treatments. The ascorbate peroxidase (APX) activity of leaves for each elevated O 3 treatment was lower than that of ambient ozone. The level of CAT and APX expression increased progressively after 40 d O 3 treatment. The expression intensity of GbD was conspicuously strengthened along with the increase of ozone concentration and fumigation time. Le-vel of reactive oxygen increased, activities of antioxidant enzyme decreased, level of gene expression down-regulated, and foliar visible injury was observed in leaves of G. biloba in elevated ozone stress.

Crystal structure of (E)-1-[4-({4-[(4-meth­oxy­benzyl­idene)amino]­phen­yl}sulfan­yl)phen­yl]ethan-1-one

PubMed Central

Hebbachi, Rabihe; Djedouani, Amel; Kadri, Soumia; Mousser, Hénia; Mousser, Abdelhamid

2015-01-01

The title Schiff base compound, C22H19NO2S, crystallized with two independent mol­ecules (A and B) in the asymmetric unit. Both mol­ecules have an E conformation about the C=N bond. The two mol­ecules differ in the orientation of the aromatic rings with respect to each other. The outer 4-meth­oxy­benzene ring is inclined to the central benzene ring and the outer 4-acetyl­benzene ring by 1.80 (19) and 63.73 (19)°, respectively, in mol­ecule A, and by 6.72 (18) and 68.53 (19)°, respectively, in mol­ecule B. The two outer benzene rings are inclined to one another by 63.77 (18) and 63.19 (18)° in mol­ecules A and B, respectively. In the crystal, the individual mol­ecules stack in columns along [010], and are linked by a number of C—H⋯π inter­actions, forming slabs lying parallel to (001). PMID:25878856

Diabetes Complications at Presentation and One Year by Glycated Haemoglobin at Diagnosis in a Multiethnic and Diverse Socioeconomic Population: Results from the South London Diabetes Study.

PubMed

Azam, Mohsin; Marwood, Lindsey; Ismail, Khalida; Evans, Tyrrell; Sivaprasad, Sobha; Winkley, Kirsty; Amiel, Stephanie Anne

2015-01-01

Background. WHO's recommendation of HbA1c ≥ 48 mmol/mol (6.5%) as diagnostic for type 2 diabetes mellitus (T2DM) was adopted by three UK London boroughs in May 2012. The South London Diabetes (SOUL-D) study has recruited people with newly diagnosed T2DM since 2008. We compared participants diagnosed before May 2012 with HbA1c < 48 mmol/mol to those with diagnostic HbA1c ≥ 48 mmol/mol. Methods. A prospective cohort study of newly diagnosed T2DM participants from 96 primary care practices, comparing demographic and biomedical variables between those with diagnostic HbA1c < 48 mmol/mol or HbA1c ≥ 48 mmol/mol at recruitment and after one year. Results. Of 1488 participants, 22.8% had diagnostic HbA1c < 48 mmol/mol. They were older and more likely to be white (p < 0.05). At recruitment and one year, there were no between-group differences in the prevalence of diabetic complications, except that those diagnosed with HbA1c < 48 mmol/mol had more sensory neuropathy at recruitment (p = 0.039) and, at one year, had new myocardial infarction (p = 0.012) but less microalbuminuria (p = 0.012). Conclusions. Use of HbA1c ≥ 48 mmol/mol as the sole T2DM diagnostic criterion may miss almost a quarter of those previously diagnosed in South London yet HbA1c < 48 mmol/mol may not exclude clinically important diabetes.

HA-1077 inhibits cell migration/invasion of oral squamous cell carcinoma.

PubMed

Moreira Carboni, Simone de Sales Costa; Rodrigues Lima, Nathália Alves; Pinheiro, Nanci Mendes; Tavares-Murta, Beatriz Martins; Crema, Virgínia Oliveira

2015-10-01

Oral squamous cell carcinoma (OSCC) is the most malignant lesion occurring in the head and neck. The Rho-kinases (ROCKs), effectors of Rho proteins, are involved in actin cytoskeletal organization, cell migration, and maintenance cortex. The HA-1077 inhibits the ROCKs. This study aimed to evaluate the effect of treatment with HA-1077 on cell motility in SCC-4 cells, a cell line originating from human OSCC. F-actin of SCC-4 cells treated or not with HA-1077 (1, 50 and 100 μmol/l), and also HA-1077 50 μmol/l and/or inhibitors Y-27632 30 μmol/l was stained with rhodamine-conjugated phalloidin and analyzed by confocal microscopy. Approximately 1×10 cells/well, control and treated with HA-1077 (25, 50, and 100 μmol/l) were added to the migration plate assay. In addition, 1×10 cells/well, control and treated with HA-1077 50 μmol/l, were tested by invasion assays (plate coated with Matrigel). The inhibition of ROCKs with HA-1077 and/or Y-27632 leads to morphological changes, affecting the organization of the actin. The inhibitory effect of HA-1077 (P<0.0001) was dose dependent as the number of cells migrated at 100 μmol/l was statistically different: 25 μmol/l (P<0.0001) and 50 μmol/l (P<0.01). The number of cells treated with HA-1077 50 μmol/l decreased compared with control cells that invaded through Matrigel (P<0.0001). This study shows an inhibitory effect of HA-1077 on cell migration and invasion, suggesting that the use of HA-1077 can be a potential therapy for OSCC.

Diabetes Complications at Presentation and One Year by Glycated Haemoglobin at Diagnosis in a Multiethnic and Diverse Socioeconomic Population: Results from the South London Diabetes Study

PubMed Central

Azam, Mohsin; Marwood, Lindsey; Ismail, Khalida; Evans, Tyrrell; Sivaprasad, Sobha; Winkley, Kirsty; Amiel, Stephanie Anne

2015-01-01

Background. WHO's recommendation of HbA1c ≥ 48 mmol/mol (6.5%) as diagnostic for type 2 diabetes mellitus (T2DM) was adopted by three UK London boroughs in May 2012. The South London Diabetes (SOUL-D) study has recruited people with newly diagnosed T2DM since 2008. We compared participants diagnosed before May 2012 with HbA1c < 48 mmol/mol to those with diagnostic HbA1c ≥ 48 mmol/mol. Methods. A prospective cohort study of newly diagnosed T2DM participants from 96 primary care practices, comparing demographic and biomedical variables between those with diagnostic HbA1c < 48 mmol/mol or HbA1c ≥ 48 mmol/mol at recruitment and after one year. Results. Of 1488 participants, 22.8% had diagnostic HbA1c < 48 mmol/mol. They were older and more likely to be white (p < 0.05). At recruitment and one year, there were no between-group differences in the prevalence of diabetic complications, except that those diagnosed with HbA1c < 48 mmol/mol had more sensory neuropathy at recruitment (p = 0.039) and, at one year, had new myocardial infarction (p = 0.012) but less microalbuminuria (p = 0.012). Conclusions. Use of HbA1c ≥ 48 mmol/mol as the sole T2DM diagnostic criterion may miss almost a quarter of those previously diagnosed in South London yet HbA1c < 48 mmol/mol may not exclude clinically important diabetes. PMID:26090473

Crystal structure of (E)-4-hy-droxy-N'-(3-meth-oxy-benzyl-idene)benzohydrazide.

PubMed

Chantrapromma, Suchada; Prachumrat, Patcharawadee; Ruanwas, Pumsak; Boonnak, Nawong; Kassim, Mohammad B

2016-09-01

The title compound, C 15 H 14 N 2 O 3 , crystallizes with two independent mol-ecules ( A and B ) in the asymmetric unit that differ in the orientation of the 3-meth-oxy-phenyl group with respect to the methyl-idenebenzohydrazide unit. The dihedral angles between the two benzene rings are 24.02 (10) and 29.30 (9)° in mol-ecules A and B , respectively. In mol-ecule A , the meth-oxy group is twisted slightly relative to its bound benzene ring, with a C meth-yl -O-C-C torsion angle of 14.2 (3)°, whereas it is almost co-planar in mol-ecule B , where the corresponding angle is -2.4 (3)°. In the crystal, the mol-ecules are linked by N-H⋯O, O-H⋯N and O-H⋯O hydrogen bonds, as well as by weak C-H⋯O inter-actions, forming sheets parallel to the bc plane. The N-H⋯O hydrogen bond and weak C-H⋯O inter-action link different mol-ecules ( A ⋯ B ) whereas both O-H⋯N and O-H⋯O hydrogen bonds link like mol-ecules ( A ⋯ A ) and ( B ⋯ B ). Pairs of inversion-related B mol-ecules are stacked approximately along the a axis by π-π inter-actions in which the distance between the centroids of the 3-meth-oxy-phenyl rings is 3.5388 (12) Å. The B mol-ecules also participate in weak C-H⋯π inter-actions between the 4-hy-droxy-phenyl and the 3-meth-oxy-phenyl rings.

Enzyme architecture: deconstruction of the enzyme-activating phosphodianion interactions of orotidine 5'-monophosphate decarboxylase.

PubMed

Goldman, Lawrence M; Amyes, Tina L; Goryanova, Bogdana; Gerlt, John A; Richard, John P

2014-07-16

The mechanism for activation of orotidine 5'-monophosphate decarboxylase (OMPDC) by interactions of side chains from Gln215 and Try217 at a gripper loop and R235, adjacent to this loop, with the phosphodianion of OMP was probed by determining the kinetic parameters k(cat) and K(m) for all combinations of single, double, and triple Q215A, Y217F, and R235A mutations. The 12 kcal/mol intrinsic binding energy of the phosphodianion is shown to be equal to the sum of the binding energies of the side chains of R235 (6 kcal/mol), Q215 (2 kcal/mol), Y217 (2 kcal/mol), and hydrogen bonds to the G234 and R235 backbone amides (2 kcal/mol). Analysis of a triple mutant cube shows small (ca. 1 kcal/mol) interactions between phosphodianion gripper side chains, which are consistent with steric crowding of the side chains around the phosphodianion at wild-type OMPDC. These mutations result in the same change in the activation barrier to the OMPDC-catalyzed reactions of the whole substrate OMP and the substrate pieces (1-β-D-erythrofuranosyl)orotic acid (EO) and phosphite dianion. This shows that the transition states for these reactions are stabilized by similar interactions with the protein catalyst. The 12 kcal/mol intrinsic phosphodianion binding energy of OMP is divided between the 8 kcal/mol of binding energy, which is utilized to drive a thermodynamically unfavorable conformational change of the free enzyme, resulting in an increase in (k(cat))(obs) for OMPDC-catalyzed decarboxylation of OMP, and the 4 kcal/mol of binding energy, which is utilized to stabilize the Michaelis complex, resulting in a decrease in (K(m))(obs).

Classification of a Haemophilus influenzae ABC Transporter HI1470/71 through Its Cognate Molybdate Periplasmic Binding Protein, MolA

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tirado-Lee, Leidamarie; Lee, Allen; Rees, Douglas C.

2014-10-02

molA (HI1472) from H. influenzae encodes a periplasmic binding protein (PBP) that delivers substrate to the ABC transporter MolB{sub 2}C{sub 2} (formerly HI1470/71). The structures of MolA with molybdate and tungstate in the binding pocket were solved to 1.6 and 1.7 {angstrom} resolution, respectively. The MolA-binding protein binds molybdate and tungstate, but not other oxyanions such as sulfate and phosphate, making it the first class III molybdate-binding protein structurally solved. The {approx}100 {mu}M binding affinity for tungstate and molybdate is significantly lower than observed for the class II ModA molybdate-binding proteins that have nanomolar to low micromolar affinity for molybdate.more » The presence of two molybdate loci in H. influenzae suggests multiple transport systems for one substrate, with molABC constituting a low-affinity molybdate locus.« less

Solvent effects and potential of mean force study of the SN2 reaction of CH3+CN‑ in water

NASA Astrophysics Data System (ADS)

Li, Chen; Liu, Peng; Li, Yongfang; Wang, Dunyou

2018-03-01

We used a combined quantum mechanics and molecular mechanics (QM/MM) method to investigate the solvent effects and potential of mean force of the CH3F+CN‑ reaction in water. Comparing to gas phase, the water solution substantially affects the structures of the stationary points along the reaction path. We quantitatively obtained the solvent effects’ contributions to the reaction: 1.7 kcal/mol to the activation barrier and ‑26.0 kcal/mol to the reaction free energy. The potential mean of force calculated with the density functional theory/MM theory has a barrier height at 19.7 kcal/mol, consistent with the experimental result at 23.0 kcal/mol; the calculated reaction free energy at ‑43.5 kcal/mol is also consistent with the one estimated based on the gas-phase data at ‑39.7 kcal/mol. Project supported by the National Natural Science Foundation of China (Grant No. 11774206) and Taishan Scholarship Fund from Shandong Province, China.

N-(1-Allyl-1H-indazol-5-yl)-4-meth-oxy-benzene-sulfonamide hemihydrate.

PubMed

Chicha, Hakima; Rakib, El Mostapha; Geffken, Detlef; Saadi, Mohamed; El Ammari, Lahcen

2013-01-01

In the title compound, C17H17N3O3 (.)0.5H2O, the indazole system makes a dihedral angle of 46.19 (8)° with the plane through the benzene ring and is nearly perpendicular to the allyl group, as indicated by the dihedral angle of 81.2 (3)°. In the crystal, the water mol-ecule, disordered over two sites related by an inversion center, forms O-H⋯N bridges between indazole N atoms of two sulfonamide mol-ecules. It is also connected via N-H⋯O inter-action to the third sulfonamide mol-ecule; however, due to the water mol-ecule disorder, only every second mol-ecule of sulfonamide participates in this inter-action. This missing inter-action results in a slight disorder of the sulfonamide S,O and N atoms which are split over two sites with half occupancy. With the help of C-H⋯O hydrogen bonds, the mol-ecules are further connected into a three-dimensional network.

The effects of nitrogen, phosphorus, vitamins and trace metals on the growth of the red tide organism Prorocentrum Micans

NASA Astrophysics Data System (ADS)

Wang, Zheng-Fang; Zhang, Qing; Gong, Min

1995-12-01

Laboratory culture experiments showed that <100μ mol/L nitrate, amonium or mixture of amino acids promote the growth of the red tide organism Prorocentrum micans Ehrenb, but that >100μmol/L of ammonium, or mixture of glycine and glutamate was harmful to growth, and that orthophosphate was P. micans’ main phosphorous source in the ocean. Presence of 80μ mol/L EDTA, 0.5 to 1 μmol/L Fe3+, 1.0 to 20.0 μ mol/L Mn2+ 0.1 to 0.4 μmol/L Co2+ in the culture medium could improve the growth of P. micans. Vitamin B1 promoted growth, but vitamin B12 and biotin did not. The estimated minimum cell quotas ( q o) for nitrogen and phosphorus being 0.74 pmole/cell and 0.045 pmole/cell show that phosphorus (more than nitrogen) limits the growth of P. micans in the study area.

[Effects of CO2 fertilization on photosynthesis and growth of cut Anthurium andraeanum in solar greenhouse in winter].

PubMed

Yang, Ke Bin; Meng, Fan Zhi; Guo, Xian Feng

2017-06-18

Aiming at the problem of the acute shortage of CO 2 in winter production of cut Anthurium andraeanum in solar greenhouse, the effect of CO 2 fertilization on photosynthetic characteristics and growth performance of A. andraeanum 'Fire' was investigated. Three treatments with different concentrations of CO 2 were designed, i.e., 700, 1000 and 1300 Μmol·mol -1 , with receiving no extra CO 2 as the control. The results showed that for the CO 2 -fertilized plants, the photosynthetic rate, intercellular CO 2 concentration and water use efficiency were significantly greater than those in the control plants after CO 2 fertilization for 60 days, and the largest increase range was observed in the 1000 Μmol·mol -1 CO 2 treatment, whereas the stomata conductance was significantly reduced compared with the control. Meanwhile, the contents of soluble sugar, starch and soluble protein in CO 2 -fertilized plants were significantly higher than those in control plants. Moreover, the quality of cut flowers with CO 2 fertilization was remarkably superior to control flowers in term of the parameters including spathe size, spathe color, peduncle length, leaf growth performance and peduncle growth rate. The most superior improvement was observed in the 1000 Μmol·mol -1 CO 2 treatment. It was therefore concluded that CO 2 fertilization of 1000 Μmol·mol -1 could effectively improve the winter production of cut A. andraeanum in solar greenhouse.

(E)-1-(2-Amino­phen­yl)-3-(3,4,5-trimeth­oxy­phen­yl)prop-2-en-1-one

PubMed Central

Chantrapromma, Suchada; Ruanwas, Pumsak; Fun, Hoong-Kun

2011-01-01

In the asymmetric unit of the title chalcone derivative, C18H19NO4, there are three crystallographically independent mol­ecules (mol­ecules A, B and C). In mol­ecule A, the dihedral angle between two benzene rings is 12.22 (10)° and the plane of the central prop-2-en-1-one unit makes dihedral angles of 11.02 (13) and 2.64 (12)° with the two adjacent benzene rings. The corresponding angles in mol­ecule B are 12.35 (10), 18.78 (12) and 7.29 (12)°, respectively, and those in mol­ecule C are 15.40 (10), 15.62 (3) and 3.19 (13)°. In each mol­ecule, an intra­molecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal structure, the mol­ecules B are linked by inter­molecular N—H⋯O hydrogen bonds into a zigzag chain along the c axis, while the mol­ecules A and C are linked together via an N—H⋯O hydrogen bond into a dimer. Adjacent dimers are further connected by N—H⋯N hydrogen bonds into a three-dimensional network. Weak C—H⋯O and C—H⋯π inter­actions are also observed. PMID:22064816

Effects of dietary inclusion of Moringa oleifera leaves on growth and some systemic and mucosal immune parameters of seabream.

PubMed

Mansour, Abdallah Tageldein; Miao, Liang; Espinosa, Cristóbal; García-Beltrán, José María; Ceballos Francisco, Diana C; Esteban, M Ángeles

2018-08-01

The effect of the dietary incorporation of drumstick, Moringa oleifera, leaf meal (MOL; 0, 5, 10 and 15%) on the growth, feed utilization, some skin mucus and systemic immune parameters and intestinal immune-related gene expression in gilthead seabream (Sparus aurata) specimens. The experiment lasted 4 weeks. The results revealed that MOL can be incorporated in S. aurata diet up to 10% with no significant negative effect on growth and feed utilization. However, there was a significant decrease with MOL at a level of 15% after 2 weeks of feeding. The systemic immune status of fish fed with the different levels of MOL showed an improvement in head kidney leucocyte phagocytosis, respiratory burst and peroxidase activities. Also, serum humoral components, including protease, ACH 50 and lysozyme activities and IgM level, increased with MOL inclusion especially at the 5% level. MOL at 5% improved skin-mucosal immunity such as protease, antiprotease, peroxidase and lysozyme activities. Moreover, the feeding of MOL revealed an upregulation of the intestinal mucosal immunity genes (lyso and c3), tight junction proteins (occludin and zo-1) and anti-inflammatory cytokines (tgf-β) with a downregulation of pro-inflammatory cytokine (tnf-α). Therefore, it is recommended to incorporate MOL in S. aurata diets at a level of 5% for the best immune status or 10% for the high growth performance and acceptable immune surveillance. Graphical abstract ᅟ.

Binding Pattern Elucidation of NNK and NNAL Cigarette Smoke Carcinogens with NER Pathway Enzymes: an Onco- Informatics Study.

PubMed

Jamal, Qazi Mohammad Sajid; Dhasmana, Anupam; Lohani, Mohtashim; Firdaus, Sumbul; Ansari, Md Yousuf; Sahoo, Ganesh Chandra; Haque, Shafiul

2015-01-01

Cigarette smoke derivatives like NNK (4-(Methylnitrosamino)-1-(3-pyridyl)-1-butanone) and NNAL (4-(methylnitrosamino)-1-(3-pyridyl)-1-butan-1-ol) are well-known carcinogens. We analyzed the interaction of enzymes involved in the NER (nucleotide excision repair) pathway with ligands (NNK and NNAL). Binding was characterized for the enzymes sharing equivalent or better interaction as compared to +Ve control. The highest obtained docking energy between NNK and enzymes RAD23A, CCNH, CDK7, and CETN2 were -7.13 kcal/mol, -7.27 kcal/mol, -8.05 kcal/mol and -7.58 kcal/mol respectively. Similarly the highest obtained docking energy between NNAL and enzymes RAD23A, CCNH, CDK7, and CETN2 were -7.46 kcal/mol, -7.94 kcal/mol, -7.83 kcal/mol and -7.67 kcal/mol respectively. In order to find out the effect of NNK and NNAL on enzymes involved in the NER pathway applying protein-protein interaction and protein-complex (i.e. enzymes docked with NNK/NNAL) interaction analysis. It was found that carcinogens are well capable to reduce the normal functioning of genes like RAD23A (HR23A), CCNH, CDK7 and CETN2. In silico analysis indicated loss of functions of these genes and their corresponding enzymes, which possibly might be a cause for alteration of DNA repair pathways leading to damage buildup and finally contributing to cancer formation.

Activation of Cellular Immunity in Herpes Simplex Virus Type 1-Infected Mice by the Oral Administration of Aqueous Extract of Moringa oleifera Lam. Leaves.

PubMed

Kurokawa, Masahiko; Wadhwani, Ashish; Kai, Hisahiro; Hidaka, Muneaki; Yoshida, Hiroki; Sugita, Chihiro; Watanabe, Wataru; Matsuno, Koji; Hagiwara, Akinori

2016-05-01

Moringa oleifera Lam. is used as a nutritive vegetable and spice. Its ethanol extract has been previously shown to be significantly effective in alleviating herpetic skin lesions in mice. In this study, we evaluated the alleviation by the aqueous extract (AqMOL) and assessed the mode of its anti-herpetic action in a murine cutaneous herpes simplex virus type 1 (HSV-1) infection model. AqMOL (300 mg/kg) was administered orally to HSV-1-infected mice three times daily on days 0 to 5 after infection. AqMOL significantly limited the development of herpetic skin lesions and reduced virus titers in the brain on day 4 without toxicity. Delayed-type hypersensitivity (DTH) reaction to inactivated HSV-1 antigen was significantly stronger in infected mice administered AqMOL and AqMOL augmented interferon (IFN)-γ production by HSV-1 antigen from splenocytes of HSV-1-infected mice at 4 days post-infection. AqMOL administration was effective in elevating the ratio of CD11b(+) and CD49b(+) subpopulations of splenocytes in infected mice. As DTH is a major host defense mechanism for intradermal HSV infection, augmentation of the DTH response by AqMOL may contribute to their efficacies against HSV-1 infection. These results provided an important insights into the mechanism by which AqMOL activates cellular immunity. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Oxides of nitrogen at two sites in New Zealand

NASA Astrophysics Data System (ADS)

Stedman, D. H.; McEwan, M. J.

1983-02-01

Oxides of nitrogen, ozone and solar UV radiation were measured at two New Zealand sites, four months at Mt. John near Lake Tekapo, and one month at the New Zealand Department of scientific and Industrial Research, Physics and Engineering Laboratory Atmospheric Station (PELAS) near Lauder. The former site proved ideal for clean-air measurements. Ozone concentrations of ˜20-25 ppb, with little diurnal variation were accompanied by total nitrogen oxide (NOy) levels frequently less than 150 ppt (parts in 1012 by volume). The noon NO and NO2 data were well correlated with a slope comparable to model values. Gaseous HNO3 was observed to be significantly above the noise level (˜15 ppt) for only twenty-seven four-hour averages. For these a median of 43 ppt was obtained with a median ([NOy]-[HNO3])/[HNO3] ratio of 7.5, not comparable with model values of around 1.1. This low HNO3 may arise from the fact that the Mt. John site is downwind of a mountain range which experiences significant upwind precipitation. At the PELAS site, strong diurnal variation of ozone and much larger NOy concentrations were observed. The difference is apparently caused by local sources of nitrogen oxides and the local meteorology at the fertile valley PELAS site.

Impact of Air Pollution on Age and Gender Related Increase in Cough Reflex Sensitivity of Healthy Children in Slovakia

PubMed Central

Demoulin-Alexikova, Silvia; Plevkova, Jana; Mazurova, Lenka; Zatko, Tomas; Alexik, Mikulas; Hanacek, Jan; Tatar, Milos

2016-01-01

Background: Numerous studies show higher cough reflex sensitivity (CRS) and cough outcomes in children compared to adults and in females compared to males. Despite close link that exists between cough and environment the potential influence of environmental air pollution on age- and gender -related differences in cough has not been studied yet. Purpose: The purpose of our study was to analyse whether the effects of exposure to environmental tobacco smoke (ETS) from parental smoking and PM10 from living in urban area are implied in age- and gender-related differences in cough outcomes of healthy, non-asthmatic children. Assessment of CRS using capsaicin and incidence of dry and wet cough was performed in 290 children (mean age 13.3 ± 2.6 years (138 females/152 males). Results: CRS was significantly higher in girls exposed to ETS [22.3 μmol/l (9.8–50.2 μmol/l)] compared to not exposed girls [79.9 μmol/l (56.4–112.2 μmol/l), p = 0.02] as well as compared to exposed boys [121.4 μmol/l (58.2–253.1 μmol/l), p = 0.01]. Incidence of dry cough lasting more than 3 weeks was significantly higher in exposed compared to not exposed girls. CRS was significantly higher in school-aged girls living in urban area [22.0 μmol/l (10.6–45.6 μmol/l)] compared to school-aged girls living in rural area [215.9 μmol/l (87.3–533.4 μmol/l); p = 0.003], as well as compared to teenage girls living in urban area [108.8 μmol/l (68.7–172.9 μmol/l); p = 0.007]. No CRS differences were found between urban and rural boys when controlled for age group. No CRS differences were found between school-aged and teenage boys when controlled for living area. Conclusions: Our results have shown that the effect of ETS on CRS was gender specific, linked to female gender and the effect of PM10 on CRS was both gender and age specific, related to female gender and school-age. We suggest that age and gender related differences in incidence of cough and CRS might be, at least partially, ascribed to the effect of environmental pollutants. The role of age and gender in the effect of air pollution on cough strongly suggest some interplay of development with biological and behavioral factors. PMID:26941651

Hydride affinities of cumulated, isolated, and conjugated dienes in acetonitrile.

PubMed

Zhu, Xiao-Qing; Liang, Hao; Zhu, Yan; Cheng, Jin-Pei

2008-11-07

The hydride affinities (defined as the enthalpy changes in this work) of 15 polarized dienes [five phenyl sulfone substituted allenes (1a), the corresponding five isolated dienes (1b), and the corresponding five conjugated dienes (1c)] in acetonitrile solution were determined by titration calorimetry for the first time. The results display that the hydride affinity scales of the 15 dienes in acetonitrile range from -71.6 to -73.9 kcal/mol for 1a, from -46.2 to -49.7 kcal/mol for 1b, and from -45.0 to -46.5 kcal/mol for 1c, which indicates that the hydride-obtaining abilities of the cumulated dienes (1a) are not only much larger than those of the corresponding conjugated dienes (1c) but also much larger than those of the corresponding isolated dienes (1b). The hydrogen affinities of the 15 dienes as well as the hydrogen affinities and the proton affinities of the radical anions of the dienes (1(-*)) in acetonitrile were also evaluated by using relative thermodynamic cycles according to Hess's law. The results show that (i) the hydrogen affinities of the neutral dienes 1 cover a range from -44.5 to -45.6 kcal/mol for 1a, from -20.4 to -21.4 kcal/mol for 1b, and from -17.3 to -18.5 kcal/mol for 1c; (ii) the hydrogen affinities of the radical anions of the dienes (1(-*)) in acetonitrile cover a range from -40.6 to -47.2 kcal/mol for 1a(-*), from -21.6 to -29.6 kcal/mol for 1b(-*), and from -10.0 to -15.4 kcal/mol for 1c(-*); (iii) the proton affinities of the 15 1a(-*) in acetonitrile cover a range from -97.0 to -100.6 kcal/mol for 1a(-*), from -77.8 to -83.4 kcal/mol for 1b(-*), and from -66.2 to -68.9 kcal/mol for 1c(-*). The main reasons for the great difference between the cumulated dienes and the corresponding isolated and conjugated dienes in the hydride affinity, hydrogen affinity, and proton affinity have been examined. It is evident that these experimental results should be quite valuable to facilitate the elucidation of the origins of the especially high chemical potencies of the allenes, the choice of suitable hydride reducing agents to reduce the dienes, and the analyses on the reduction mechanisms.

Impact of Air Pollution on Age and Gender Related Increase in Cough Reflex Sensitivity of Healthy Children in Slovakia.

PubMed

Demoulin-Alexikova, Silvia; Plevkova, Jana; Mazurova, Lenka; Zatko, Tomas; Alexik, Mikulas; Hanacek, Jan; Tatar, Milos

2016-01-01

Numerous studies show higher cough reflex sensitivity (CRS) and cough outcomes in children compared to adults and in females compared to males. Despite close link that exists between cough and environment the potential influence of environmental air pollution on age- and gender -related differences in cough has not been studied yet. The purpose of our study was to analyse whether the effects of exposure to environmental tobacco smoke (ETS) from parental smoking and PM10 from living in urban area are implied in age- and gender-related differences in cough outcomes of healthy, non-asthmatic children. Assessment of CRS using capsaicin and incidence of dry and wet cough was performed in 290 children (mean age 13.3 ± 2.6 years (138 females/152 males). CRS was significantly higher in girls exposed to ETS [22.3 μmol/l (9.8-50.2 μmol/l)] compared to not exposed girls [79.9 μmol/l (56.4-112.2 μmol/l), p = 0.02] as well as compared to exposed boys [121.4 μmol/l (58.2-253.1 μmol/l), p = 0.01]. Incidence of dry cough lasting more than 3 weeks was significantly higher in exposed compared to not exposed girls. CRS was significantly higher in school-aged girls living in urban area [22.0 μmol/l (10.6-45.6 μmol/l)] compared to school-aged girls living in rural area [215.9 μmol/l (87.3-533.4 μmol/l); p = 0.003], as well as compared to teenage girls living in urban area [108.8 μmol/l (68.7-172.9 μmol/l); p = 0.007]. No CRS differences were found between urban and rural boys when controlled for age group. No CRS differences were found between school-aged and teenage boys when controlled for living area. Our results have shown that the effect of ETS on CRS was gender specific, linked to female gender and the effect of PM10 on CRS was both gender and age specific, related to female gender and school-age. We suggest that age and gender related differences in incidence of cough and CRS might be, at least partially, ascribed to the effect of environmental pollutants. The role of age and gender in the effect of air pollution on cough strongly suggest some interplay of development with biological and behavioral factors.

Nitroso-sulfide coupled signaling triggers specific vasoactive effects in the intrarenal arteries of patients with arterial hypertension.

PubMed

Cacanyiova, S; Berenyiova, A; Balis, P; Kristek, F; Grman, M; Ondrias, K; Breza, J; Breza, J

2017-08-01

In normotensive conditions, it has been confirmed that S-nitrosothiols (RSNO), can interact with hydrogen sulfide (H 2 S) and create new substances with specific vasoactive effects. This interaction could also represent a new regulator signaling pathway in conditions of hypertension. Until now, these effects were studied only in normotensive rats, and they have not been carried out in humans yet. We investigated the vasoactive effects of the products of the H 2 S/S-nitrosoglutathione (S/GSNO) interaction in lobar arteries (LA) isolated from the nephrectomized kidneys of patients suffering from arterial hypertension and in renal arteries (RA) of spontaneously hypertensive rats (SHR). The changes in the isometric tension of pre-contracted arteries were evaluated. Acetylcholine-induced vasorelaxation of LA was reduced compared to the effect induced by an NO donor, sodium nitroprusside suggesting an endothelium dysfunction. While 1 μmol/L Na2S had a minimal effect on the vascular tone, the concentration 20 μmol/L evoked a slight vasorelaxation. GSNO at 0.1 μmol/L induced vasorelaxation, which was less pronounced compared to the effect induced by 1 μmol/L. The S/GSNO products (final concentration 0.1 μmol/L) prepared as the mixture of GSNO (0.1 μmol/L) + Na2S (1 μmol/L) induced a higher vasorelaxation compared to GSNO (0.1 μmol/L) alone only in the 5 th minute and without the differences in the speed. On the other hand, the S/GSNO products (final concentration 1 μmol/L) prepared as the mixture of GSNO (1 μmol/L) + Na2S (10 μmol/L) induced a higher and faster vasorelaxation compared to the effect induced by GSNO (1 μmol/L) alone. In RA of SHR this S/GSNO products induced similar vasorelaxation (higher and faster than GSNO) with involvement of HNO (partially) and cGMP as mediators. However, the products of the H 2 S/NO donor (DEA NONOate) manifested differently than S/GSNO indicating the unique interaction between GSNO and H 2 S. In this study, we confirmed for the first time that specific vasoactive effects of coupled nitroso-sulfide signaling were also triggered in human arterial tissue. We suggest that in hypertension, H 2 S in interaction with GSNO regulated a vasoconstrictor-induced increase in arterial tone towards a stronger vasorelaxation compared to GSNO alone or H 2 S alone.

Inhibitory effects of patchouli alcohol on stress-induced diarrhea-predominant irritable bowel syndrome

PubMed Central

Zhou, Tian-Ran; Huang, Jing-Jing; Huang, Zi-Tong; Cao, Hong-Ying; Tan, Bo

2018-01-01

AIM To elucidate the mechanism of patchouli alcohol (PA) in treatment of rat models of diarrhea-predominant irritable bowel syndrome (IBS-D). METHODS We studied the effects of PA on colonic spontaneous motility using its cumulative log concentration (3 × 10−7 mol/L to 1 × 10−4 mol/L). We then determined the responses of the proximal and distal colon segments of rats to the following stimuli: (1) carbachol (1 × 10−9 mol/L to 1 × 10−5 mol/L); (2) neurotransmitter antagonists including Nω-nitro-L-arginine methyl ester hydrochloride (10 μmol/L) and (1R*, 2S*)-4-[2-Iodo-6-(methylamino)-9H-purin-9-yl]-2-(phosphonooxy)bicyclo[3.1.0]hexane-1-methanol dihydrogen phosphate ester tetraammonium salt (1 μmol/L); (3) agonist α,β-methyleneadenosine 5′-triphosphate trisodium salt (100 μmol/L); and (4) single KCl doses (120 mmol/L). The effects of blockers against antagonist responses were also assessed by pretreatment with PA (100 μmol/L) for 1 min. Electrical-field stimulation (40 V, 2-30 Hz, 0.5 ms pulse duration, and 10 s) was performed to observe nonadrenergic, noncholinergic neurotransmitter release in IBS-D rat colon. The ATP level of Kreb’s solution was also determined. RESULTS PA exerted a concentration-dependent inhibitory effect on the spontaneous contraction of the colonic longitudinal smooth muscle, and the half maximal effective concentration (EC50) was 41.9 μmol/L. In comparison with the KCl-treated IBS-D group, the contractile response (mg contractions) in the PA + KCl-treated IBS-D group (11.87 ± 3.34) was significantly decreased in the peak tension (P < 0.01). Compared with CCh-treated IBS-D rat colon, the cholinergic contractile response of IBS-D rat colonic smooth muscle (EC50 = 0.94 μmol/L) was significantly decreased by PA (EC50 = 37.43 μmol/L) (P < 0.05). Lack of nitrergic neurotransmitter release in stress-induced IBS-D rats showed contraction effects on colonic smooth muscle. Pretreatment with PA resulted in inhibitory effect on L-NAME-induced (10 μmol/L) contraction (P < 0.05). ATP might not be the main neurotransmitter involved in inhibitory effects of PA in the colonic relaxation of stress-induced IBS-D rats. CONCLUSION PA application may serve as a new therapeutic approach for IBS-D. PMID:29456408

Final report of APMP.QM-K46 ammonia in nitrogen at 30 μmol/mol level

NASA Astrophysics Data System (ADS)

Uehara, Shinji; Qiao, Han; Shimosaka, Takuya

2017-01-01

This report describes the results for a bilateral comparison of ammonia in nitrogen gas mixture. The nominal amount-of-substance fraction was 30 μmol/mol. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Fotoexcitación de Moléculas Pequeñas

NASA Astrophysics Data System (ADS)

González Díaz, P. F.

El modelo estocástico no puede justificar la excitación multi-fotónica de moléculas pequeñas o muy simétricas. Basándonos en un escenario de interacción radiación-molécula cooperativo para la absorción de N-1 fotones IR por un sistema de N niveles, se especula que un posible mecanismo para la excitación no estocástica de moléculas pudiera ser la generación de procesos caóticos intra-moleculares.

Li corrosion resistant glasses for headers in ambient temperature Li batteries

DOEpatents

Hellstrom, E.E.; Watkins, R.D.

1985-10-11

Glass compositions containing 10 to 50 mol% CaO, 10 to 50 mol% Al/sub 2/O/sub 3/, 30 to 60 mol% B/sub 2/O/sub 3/, and 0 to 30 mol% MgO are provided. These compositions are capable of forming a stable glass-to-metal seal possessing electrical insulating properties for use in a lithium battery. Also provided are lithium cells containing a stainless steel body and molybdenum center pin electrically insulated by means of a seal produced according to the invention.

Benzene-1,4-diol–5-(1H-imidazol-1-yl)pyrimidine (1/1)

PubMed Central

Jiang, Yan-Ke; Hou, Gui-Ge

2011-01-01

The asymmetric unit of title compound, C7H6N4·C6H6O2, contains one 5-(1H-imidazol-1-yl)pyrimidine mol­ecule and two half benzene-1,4-diol mol­ecules; the benzene-1,4-diol mol­ecules are located on individual inversion centers. In the pyrimidine mol­ecule, the imidazole ring is twisted with respect to the pyrimidine ring at a dihedral angle of 25.73 (7)°. In the crystal, O—H⋯N hydrogen bonds link the mol­ecules to form supra­molecular chains. π–π stacking is also observed in the crystal, the centroid–centroid distance between parallel imdazole rings being 3.5543 (16) Å. PMID:22220081

Optimized MOL-PCR for Characterization of Microbial Pathogens.

PubMed

Wuyts, Véronique; Roosens, Nancy H C; Bertrand, Sophie; Marchal, Kathleen; De Keersmaecker, Sigrid C J

2016-01-06

Characterization of microbial pathogens is necessary for surveillance, outbreak detection, and tracing of outbreak sources. This unit describes a multiplex oligonucleotide ligation-PCR (MOL-PCR) optimized for characterization of microbial pathogens. With MOL-PCR, different types of markers, like unique sequences, single-nucleotide polymorphisms (SNPs) and indels, can be simultaneously analyzed in one assay. This assay consists of a multiplex ligation for detection of the markers, a singleplex PCR for signal amplification, and hybridization to MagPlex-TAG beads for readout on a Luminex platform after fluorescent staining. The current protocol describes the MOL-PCR, as well as methods for DNA isolation, probe design, and data interpretation and it is based on an optimized MOL-PCR assay for subtyping of Salmonella Typhimurium. Copyright © 2016 John Wiley & Sons, Inc.

4-Amino-N-(3-meth­oxy­pyrazin-2-yl)benzene­sulfonamide

PubMed Central

Bruni, Bruno; Coran, Silvia A.; Bartolucci, Gianluca; Di Vaira, Massimo

2010-01-01

The overall mol­ecular geometry of the title compound, C11H12N4O3S, is bent, with a dihedral angle of 89.24 (5)° between the best planes through the two aromatic rings. Each mol­ecule behaves as a hydrogen-bond donor toward three different mol­ecules, through its amidic and the two aminic H atoms, and it behaves as a hydrogen-bond acceptor from two other mol­ecules via one of its sulfonamidic O atoms. In the crystal, mol­ecules linked by N—H⋯N and N—H⋯O hydrogen bonds form kinked layers parallel to (001), adjacent layers being connected by van der Waals inter­actions. PMID:21587634

Alumina-Reinforced Zirconia Composites

NASA Technical Reports Server (NTRS)

Choi, Sung R.; Bansal, Narottam P.

2003-01-01

Alumina-reinforced zirconia composites, used as electrolyte materials for solid oxide fuel cells, were fabricated by hot pressing 10 mol percent yttria-stabilized zirconia (10-YSZ) reinforced with two different forms of alumina particulates and platelets each containing 0 to 30 mol percent alumina. Major mechanical and physical properties of both particulate and platelet composites including flexure strength, fracture toughness, slow crack growth, elastic modulus, density, Vickers microhardness, thermal conductivity, and microstructures were determined as a function of alumina content either at 25 C or at both 25 and 1000 C. Flexure strength and fracture toughness at 1000 C were maximized with 30 particulate and 30 mol percent platelet composites, respectively, while resistance to slow crack growth at 1000 C in air was greater for 30 mol percent platelet composite than for 30 mol percent particulate composites.

1,2-Di-2-quinolylethene

PubMed Central

Fun, Hoong-Kun; Kia, Reza; Maity, Annada C.; Chakrabarty, Rinku; Goswami, Shyamaprosad

2009-01-01

The title compound, C20H14N2, comprises two crystallographically independent centrosymmetric mol­ecules (A and B) with different conformations due to the disorder of molecule B. The whole of mol­ecule B is disordered over two sets of positions, corresponding to a 180° rotation of the molecule, with a site-occupancy ratio of 0.780 (6):0.220 (6). The minor component of the disordered part in B has the same configuration as mol­ecule A, but the major component is different. The dihedral angle between the planes of mol­ecule A and mol­ecule B (major component) is 63.22 (3)°. The crystal structure is stabilized by inter­molecular C—H⋯π inter­actions. PMID:21581953

Solubility enhancement of simvastatin by arginine: thermodynamics, solute-solvent interactions, and spectral analysis.

PubMed

Meor Mohd Affandi, M M R; Tripathy, Minaketan; Shah, Syed Adnan Ali; Majeed, A B A

2016-01-01

We examined the solubility of simvastatin in water in 0.01 mol·dm(-3), 0.02 mol·dm(-3), 0.04 mol·dm(-3), 0.09 mol·dm(-3), 0.18 mol·dm(-3), 0.36 mol·dm(-3), and 0.73 mol·dm(-3) arginine (ARG) solutions. The investigated drug is termed the solute, whereas ARG the cosolute. Phase solubility studies illustrated a higher extent of solubility enhancement for simvastatin. The aforementioned system was subjected to conductometric and volumetric measurements at temperatures (T) of 298.15 K, 303.15 K, 308.15 K, and 313.15 K to illustrate the thermodynamics involved and related solute-solvent interactions. The conductance values were used to evaluate the limiting molar conductance and association constants. Thermodynamic parameters (ΔG (0), ΔH (0), ΔS (0), and E s) for the association process of the solute in the aqueous solutions of ARG were calculated. Limiting partial molar volumes and expansibilities were evaluated from the density values. These values are discussed in terms of the solute-solvent and solute-cosolute interactions. Further, these systems were analyzed using ultraviolet-visible analysis, Fourier-transform infrared spectroscopy, and (13)C, (1)H, and two-dimensional nuclear overhauser effect spectroscopy nuclear magnetic resonance to complement thermophysical explanation.

Hydration Resistance of Y2O3 Doped CaO and Its Application to Melting Titanium Alloys

NASA Astrophysics Data System (ADS)

Fanlong, Meng; Zhiwei, Cheng; Guangyao, Chen; Xionggang, Lu; Chonghe, Li

Various amount Y2O3(1-8 mol%) doped CaO powder was synthesized by the solid state reaction method, the pellete and crucible were fabricated by the cold isostatic pressing and were sintered at 1750°C for 4h. The microstructural characterization was revealed by X-ray diffraction(XRD) and scanning electron microscopy(SEM).The XRD results showed that when Y2O3 doped 2 mol%, metastable CaY2O4 phase existed in CaO grain boundary, when Y2O3 doped 3 mol%-8 mol%, in addition to the above structure, Y2O3 phase also be found in CaO grain boundary. Hydration experiment results showed when Y2O3 doped 0 mol%-4 mol%, CaO had excellent hydration resistance performance, Y2O3 doped 2 mol% had the best hydration resistance, its weight addition stored after 7 weeks (49 days) was only about 0.2 wt%. Melting experiment results showed that it was no reaction between crucible and alloy layer. Oxygen, calcium, titanium, nickle and yttrium element not diffusion between the CaO crucible and TiNi alloy, it was no oxygen content increase after melting.

(2E)-3-(6-Meth­oxy­naphthalen-2-yl)-1-[4-(methyl­sulfan­yl)phen­yl]prop-2-en-1-one

PubMed Central

Fun, Hoong-Kun; Chia, Tze Shyang; Padaki, Mahesh; Isloor, Arun M.; Ismail, A. F.

2012-01-01

The asymmetric unit of the title compound, C21H18O2S, consists of two crystallographically independent mol­ecules (A and B). The mol­ecules exist in a trans conformation with respect to the central C=C bond. The naphthalene ring system makes dihedral angles of 51.62 (12) (mol­ecule A) and 52.69 (12)° (mol­ecule B) with the benzene ring. In mol­ecule A, the prop-2-en-1-one group forms dihedral angles of 22.84 (15) and 29.02 (12)° with the adjacent naphthalene ring system and benzene ring, respectively, whereas the corresponding angles are 30.04 (12) and 23.33 (12)° in mol­ecule B. In the crystal, mol­ecules are linked by inter­molecular C—H⋯O hydrogen bonds into head-to-tail chains along the a axis. The crystal packing also features C—H⋯π inter­actions. The crystal studied was a pseudo-merohedral twin with twin law (100 0-10 00-1) and a refined component ratio of 0.6103 (16):0.3897 (16). PMID:22798922

4-Bromo-N-(di-n-propyl-carbamothioyl)-benzamide.

PubMed

Binzet, Gün; Flörke, Ulrich; Külcü, Nevzat; Arslan, Hakan

2009-02-04

The synthesis of the title compound, C(14)H(19)BrN(2)OS, involves the reaction of 4-bromo-benzoyl chloride with potassium thio-cyanate in acetone followed by condensation of the resulting 4-bromo-benzoyl isothio-cyanate with di-n-propyl-amine. Typical thio-urea carbonyl and thio-carbonyl double bonds, as well as shortened C-N bonds, are observed in the title compound. The short C-N bond lengths in the centre of the mol-ecule reveal the effects of resonance in this part of the mol-ecule. The asymmetric unit of the title compound contains two crystallographically independent mol-ecules, A and B. There is very little difference between the bond lengths and angles of these mol-ecules. In mol-ecule B, one di-n-propyl group is twisted in a -anti-periplanar conformation with C-C-C-H = -179.1 (3)° and the other adopts a -synclinal conformation with C-C-C-H = -56.7 (4)°; in mol-ecule A the two di-n-propyl groups are twisted in + and -anti-periplanar conformations, with C-C-C-H = -179.9 (3) and 178.2 (3)°, respectively. In the crystal, the mol-ecules are linked into dimeric pairs via pairs of N-H⋯S hydrogen bonds.

Rhizobacterial population density and nitrogen fixation in seagrass community of Gulf of Mannar, India.

PubMed

Raja, S; Thangaradjou, T; Sivakumar, K; Kannan, L

2012-11-01

Seagrass rhizosphere generally supports high bacterial population density which plays a major role in determining the nutrient cycles of the sea. Higher densities of total heterotrphic bacteria (26.3 x 10(6) CFU g(-1)), nitrogen fixing (27.3 x 10(3) CFUg(-1), ammonifying (44.66 x 10(6) MPN g(-1)) and nitrifying bacteria (42.33 X 10(6) MPN g(-1)) have been registered in the seagrass areas than the non seagrass area. In particular, all these rhizosphere microbial population was higher in Thalassia hemprichii. The rates of nitrogen fixation was recorded in the different species of seagrasses such as Enhalus acoroides (1.166 n mol g(-1) d(-1)), Halophila ovalis (0.166 n mol g(-1) d(-1)), Thalassia hemprichii(18.5 n mol g(-1) d(-1)), Cymodocea serrulata (10.5 n mol g(-1) d(-1)), Halodule uninervis (5.375 n mol g(-1) d(-1)) and Syringodium isoetifolium (0.666 n mol g(-1) d(-1)) using gas chromatography. The average nitrogen fixation by the seagrasses of Gulf of Mannar alone was estimated to be 7640.58 n mol m(-2) d(-1) and the contributions from the rhizosphere microbes will increase the quantity to many fold.

Nine Different Chemical Species and Action Mechanisms of Pancreatic Lipase Ligands Screened Out from Forsythia suspensa Leaves All at One Time.

PubMed

Chen, Tinggui; Li, Yayun; Zhang, Liwei

2017-05-12

It is difficult to screen out as many active components as possible from natural plants all at one time. In this study, subfractions of Forsythia suspensa leaves were firstly prepared; then, their inhibitive abilities on pancreatic lipase were tested; finally, the highest inhibiting subfraction was screened by self-made immobilized pancreatic lipase. Results showed that nine ligands, including eight inhibitors and one promotor, were screened out all at one time. They were three flavonoids (rutin, IC 50 : 149 ± 6.0 μmol/L; hesperidin, 52.4 μmol/L; kaempferol-3- O -rutinoside, isolated from F. suspensa leaves for the first time, IC 50 notably reached 2.9 ± 0.5 μmol/L), two polyphenols (chlorogenic acid, 3150 ± 120 μmol/L; caffeic acid, 1394 ± 52 μmol/L), two lignans (phillyrin, promoter; arctigenin, 2129 ± 10.5 μmol/L), and two phenethyl alcohol (forsythiaside A, 2155 ± 8.5 μmol/L; its isomer). Their action mechanisms included competitive inhibition, competitive promotion, noncompetitive inhibition, and uncompetitive inhibition. In sum, using the appropriate methods, more active ingredients can be simply and quickly screened out all at one time from a complex natural product system. In addition, F. suspensa leaves contain numerous inhibitors of pancreatic lipase.

Solubility enhancement of simvastatin by arginine: thermodynamics, solute–solvent interactions, and spectral analysis

PubMed Central

Meor Mohd Affandi, MMR; Tripathy, Minaketan; Shah, Syed Adnan Ali; Majeed, ABA

2016-01-01

We examined the solubility of simvastatin in water in 0.01 mol·dm−3, 0.02 mol·dm−3, 0.04 mol·dm−3, 0.09 mol·dm−3, 0.18 mol·dm−3, 0.36 mol·dm−3, and 0.73 mol·dm−3 arginine (ARG) solutions. The investigated drug is termed the solute, whereas ARG the cosolute. Phase solubility studies illustrated a higher extent of solubility enhancement for simvastatin. The aforementioned system was subjected to conductometric and volumetric measurements at temperatures (T) of 298.15 K, 303.15 K, 308.15 K, and 313.15 K to illustrate the thermodynamics involved and related solute–solvent interactions. The conductance values were used to evaluate the limiting molar conductance and association constants. Thermodynamic parameters (ΔG0, ΔH0, ΔS0, and Es) for the association process of the solute in the aqueous solutions of ARG were calculated. Limiting partial molar volumes and expansibilities were evaluated from the density values. These values are discussed in terms of the solute–solvent and solute–cosolute interactions. Further, these systems were analyzed using ultraviolet–visible analysis, Fourier-transform infrared spectroscopy, and 13C, 1H, and two-dimensional nuclear overhauser effect spectroscopy nuclear magnetic resonance to complement thermophysical explanation. PMID:27041998

Oxidation of 2,4-dichlorophenoxyacetic acid by ionizing radiation: degradation, detoxification and mineralization

NASA Astrophysics Data System (ADS)

Zona, Robert; Solar, Sonja

2003-02-01

The gamma-radiation-induced degradation of 2,4-dichlorophenoxyacetic acid (2,4-D) was studied in aerated (A) and in during irradiation air saturated (AS) solutions. Whereas the decomposition rates were not influenced by AS, chloride elimination, detoxification as well as mineralization were significantly enhanced. In the range 50-500 μmol dm -3 2,4-D, degradation showed proportionality to concentration, while chloride formation was successively retarded. The ratios of the pseudo first-order rate constants for degradation and chloride formation, kde/ kCl, increase in AS solutions from 1.4 (50 μmol dm -3) to 2.7 (500 μmol dm -3) and in A solutions from 1.4 to 3.3. In AS for total chloride release 0.7 kGy (50 μmol dm -3) to 10 kGy (500 μmol dm -3) were required, the reduction of organic carbon at 10 kGy was 95% (50 μmol dm -3) and 50% (500 μmol dm -3). Increase and decrease of toxicity during irradiation correlated well with formation and degradation of intermediate phenolic products. The doses for detoxification corresponded to those of total dehalogenation. The oxygen uptake was ˜1.1 ppm 100 Gy -1. The presence of the inorganic components of Vienna drinking water affect the degradation parameters insignificantly.

[The physiologic significance of 2,3-diphosphoglycerate and changes in its erythrocyte levels in an experiment].

PubMed

Béder, I; Orgonásová, M; Brozman, B; Horecký, J; Mataseje, A

1990-05-01

The regulatory effect of 2,3-DPG on oxygen transport and binding to hemoglobin was analyzed. Under conditions of substitution hemodilution by isooncotic 3.4% Rheodextran (Spofa), changes in the content of 2,3-DPG in arterial and venous blood were enzymatically determined over several days. Reference values of 2,3-DPG were obtained in the studied series of dogs (2.05 +/- 0.74 x 10(-6) mol.ml-1 in whole blood 4.69 +/- 1.52 x 10(-6) mol.g-1 of erythrocyte volume, and 13.39 +/- 2.82 x 10(-6) mol.ml-1 of hemoglobin). In anesthetized animals the content of 2,3-DPG in arterial blood was significantly higher (6.28 +/- 0.84 x 10(-6) mol.ml-1 of erythrocyte volume) than in venous blood (6.01 +/- 0.80 x 10(-6) mol.ml-1 of erythrocyte volume). At substitution hemodilution the 2,3-DPG content in erythrocytes of venous blood decreased from 5.46 +/- 0.67 to 4.97 +/- 1.31 x 10(-6) mol.ml-1 of erythrocyte volume. The subsequent increase to 6.04 +/- 0.71 x 10(-6) mol.ml-1 of erythrocyte volume was achieved by nonlinear increase over the following days, at persisting low hemoglobin content in blood.

2,2′-Bi(9,9-di­ethyl­fluorene)

PubMed Central

Park, Ki-Min; Oh, Hankook; Kang, Youngjin

2014-01-01

The title compound, C34H34, systematic name 9,9,9′,9′-tetra­ethyl-2,2′-bi(9H-fluorene), crystallized with two crystallographically independent mol­ecules (A and B) in the asymmetric unit. These differ mainly in the orientation of the lateral ethyl chains: in mol­ecule A, they are both on the same side of the mol­ecule whereas in mol­ecule B, one di­ethyl­fluorene moiety has undergone a 180° rotation such that the two pairs of ethyl residues appear on opposite sides of the mol­ecule. The fluorene ring systems subtend dihedral angles of 31.37 (4) and 43.18 (3)° in mol­ecules A and B, respectively. Hence the two fluorene moieties are tilted slightly toward one another. This may be due to the presence of inter­molecular C—H⋯π inter­actions between neighboring mol­ecules. The lateral ethyl chains (excluding H atoms) are also almost planar, with each pair almost perpendicular to the plane of the fluorene system to which they are attached with dihedral angles between the ethyl and fluorene planes in the range 86.04 (8)–89.5 (1)°. PMID:24764898

MP2, DFT-D, and PCM study of the HMB-TCNE complex: Thermodynamics, electric properties, and solvent effects

NASA Astrophysics Data System (ADS)

Kysel, Ondrej; Budzák, Scaronimon; Medveď, Miroslav; Mach, Pavel

Geometry, thermodynamic, and electric properties of the pi-EDA complex between hexamethylbenzene (HMB) and tetracyanoethylene (TCNE) are investigated at the MP2/6-31G* and, partly, DFT-D/6-31G* levels. Solvent effects on the properties are evaluated using the PCM model. Fully optimized HMB-TCNE geometry in gas phase is a stacking complex with an interplanar distance 2.87 × 10-10 m and the corresponding BSSE corrected interaction energy is -51.3 kJ mol-1. As expected, the interplanar distance is much shorter in comparison with HF and DFT results. However the crystal structures of both (HMB)2-TCNE and HMB-TCNE complexes have interplanar distances somewhat larger (3.18 and 3.28 × 10-10 m, respectively) than our MP2 gas phase value. Our estimate of the distance in CCl4 on the basis of PCM solvent effect study is also larger (3.06-3.16 × 10-10 m). The calculated enthalpy, entropy, Gibbs energy, and equilibrium constant of HMB-TCNE complex formation in gas phase are: DeltaH0 = -61.59 kJ mol-1, DeltaSc0 = -143 J mol-1 K-1, DeltaG0 = -18.97 kJ mol-1, and K = 2,100 dm3 mol-1. Experimental data, however, measured in CCl4 are significantly lower: DeltaH0 = -34 kJ mol-1, DeltaSc0 = -70.4 J mol-1 K-1, DeltaG0 = -13.01 kJ mol-1, and K = 190 dm3 mol-1. The differences are caused by solvation effects which stabilize more the isolated components than the complex. The total solvent destabilization of Gibbs energy of the complex relatively to that of components is equal to 5.9 kJ mol-1 which is very close to our PCM value 6.5 kJ mol-1. MP2/6-31G* dipole moment and polarizabilities are in reasonable agreement with experiment (3.56 D versus 2.8 D for dipole moment). The difference here is due to solvent effect which enlarges interplanar distance and thus decreases dipole moment value. The MP2/6-31G* study supplemented by DFT-D parameterization for enthalpy calculation, and by the PCM approach to include solvent effect seems to be proper tools to elucidate the properties of pi-EDA complexes.

DFT study of gases adsorption on sharp tip nano-catalysts surface for green fertilizer synthesis

NASA Astrophysics Data System (ADS)

Yahya, Noorhana; Irfan, Muhammad; Shafie, Afza; Soleimani, Hassan; Alqasem, Bilal; Rehman, Zia Ur; Qureshi, Saima

2016-11-01

The energy minimization and spin modifications of sorbates with sorbents in magnetic induction method (MIM) play a vital role in yield of fertilizer. Hence, in this article the focus of study is the interaction of sorbates/reactants (H2, N2 and CO2) in term of average total adsorption energies, average isosteric heats of adsorption energies, magnetic moments, band gaps energies and spin modifications over identical cone tips nanocatalyst (sorbents) of Fe2O3, Fe3O4 (magnetic), CuO and Al2O3 (non-magnetic) for green nano-fertilizer synthesis. Study of adsorption energy, band structures and density of states of reactants with sorbents are purely classical and quantum mechanical based concepts that are vividly illustrated and supported by ADSORPTION LOCATOR and Cambridge Seriel Total Energy Package (CASTEP) modules following classical and first principle DFT simulation study respectively. Maximum values of total average energies, total average adsorption energies and average adsorption energies of H2, N2 and CO2 molecules are reported as -14.688 kcal/mol, -13.444 kcal/mol, -3.130 kcal/mol, - kcal/mol and -6.348 kcal/mol over Al2O3 cone tips respectively and minimum over magnetic cone tips. Whereas, the maximum and average minimum values of average isosteric heats of adsorption energies of H2, N2 and CO2 molecules are figured out to be 3.081 kcal/mol, 4.842 kcal/mol and 6.848 kcal/mol, 0.988 kcal/mol, 1.554 kcal/mol and 2.236 kcal/mol over aluminum oxide and Fe3O4 cone tips respectively. In addition to the adsorption of reactants over identical cone sorbents the maximum and minimum values of net spin, electrons and number of bands for magnetite and aluminum oxide cone structures are attributed to 82 and zero, 260 and 196, 206 and 118 for Fe3O4 and Al2O3 cones respectively. Maximum and least observed values of band gap energies are figured out to be 0.188 eV and 0.018 eV with Al2O3 and Fe3O4 cone structures respectively. Ultimately, with the adsorption of reactants an identical increment of 14 electrons each in up and down spins is resulted.

[The role of transforming growth factor-β1/connective tissue growth factor signaling pathway in paraquat-induced pulmonary fibrosis].

PubMed

Li, H H; Cai, Q; Wang, Y P; Liu, H R; Huang, M

2016-07-20

Objective: To investigate the effects of Paraquat on human embryonic lung fibroblasts (MRC5) and explore the role of transforming growth factor-β 1 /connective tissue growth factor signaling pathway in paraquat-induced pulmonary fibrosis. Methods: MRC5 cells were cultured with different concentration of PQ (0, 12.5, 25, 50, 100, 200, 400 μmol/L) for 24 h. The viability of cells was measured by MTT. The protein level of TGF-β 1 were analyzed by ELISA after PQ treatment (0, 25, 50, 100 μmol/L) . To examine whether TGF-β 1 /CTGF signaling pathway was involved in paraquat-induced cytotoxicity, cells was divided into 6 groups: (1) control; (2) 25 μmol/L PQ group; (3) 50 μmol/L PQ group; (4) 100 μmol/L PQ group; (5) TGF-β 1 positive control group (50 μmol/L rhTGF-β 1 ) ; (6) stimulate group (100 μmol/L PQ+50 μmol/L TGF-β 1 ) . The protein levels of p-Smad2, p-Smad3 and CTGF were assayed by western blot. The mRNA level of CTGF was assayed by real time RT-PCR. Results: MTT showed that cell viability decreased with increasing PQ concentration ( P <0.05) . The protein expression of TGF-β 1 treated with PQ (25, 50, 100 μmol/L) significantly increased compared with control in a dose-independent manner ( P <0.05) . Exposure to PQ (25, 50, 100 μmol/L) induced increase of protein levels of p-Smad2 and p-Smad3. Noteworthy, the expression of p-Smad2 and p-Smad3 were dramatically increased following PQ plus TGF-β 1 stimulation ( P <0.05) . Exposure to PQ (50, 100μmol/L) induced increase of CTGF protein expression and similar greatly increase following PQ plus TGF-β 1 stimulation ( P <0.05) . Real time RT-PCR showed CTGF mRNA in all groups also significantly up-regulated compared with control ( P <0.05) . Conclusion: TGF-β 1 regulates the expression of target gene CTGF to exhibit its pro-fibrogenic effects by activating TGF-β 1 /Smad signaling pathway in PQ-induced pulmonary fibrosis.

Carbon monoxide contributes to the constipating effects of granisetron in rat colon.

PubMed

Nacci, Carmela; Fanelli, Margherita; Potenza, Maria Assunta; Leo, Valentina; Montagnani, Monica; De Salvia, Maria Antonietta

2016-11-14

To investigate the mechanisms underlying the potential contribution of the heme oxygenase/carbon monoxide (HO/CO) pathway in the constipating effects of granisetron. For in vivo studies, gastrointestinal motility was evaluated in male rats acutely treated with granisetron [25, 50, 75 μg/kg/subcutaneous (sc)], zinc protoporphyrin IX [ZnPPIX, 50 μg/kg/intraperitoneal (ip)] and hemin (50 μmol/L/kg/ip), alone or in combination. For in vitro studies, the contractile neurogenic response to electrical field stimulation (EFS, 3, 5, 10 Hz, 14 V, 1 ms, pulse trains lasting 10 s), as well as the contractile myogenic response to acetylcholine (ACh, 0.1-100 μmol/L) were evaluated on colon specimens incubated with granisetron (3 μmol/L, 15 min), ZnPPIX (10 μmol/L, 60 min) or CO-releasing molecule-3 (CORM-3, 100, 200, 400 μmol/L) alone or in combination. These experiments were performed under co-treatment with or without atropine (3 μmol/L, a muscarinic receptor antagonist) or N G -nitro-L-Arginine (L-NNA, 100 μmol/L, a nitric oxide synthase inhibitor). Administration of granisetron (50, 75 μg/kg) in vivo significantly increased the time to first defecation ( P = 0.045 vs vehicle-treated rats), clearly suggesting a constipating effect of this drug. Although administration of ZnPPIX or hemin alone had no effect on this gastrointestinal motility parameter, ZnPPIX co-administered with granisetron abolished the granisetron-induced constipation. On the other hand, co-administration of hemin and granisetron did not modify the increased constipation observed under granisetron alone. When administered in vitro , granisetron alone (3 μmol/L) did not significantly modify the colon's contractile response to either EFS or ACh. Incubation with ZnPPIX alone (10 μmol/L) significantly reduced the colon's contractile response to EFS ( P = 0.016) but had no effect on contractile response to ACh. Co-administration of ZnPPIX and atropine (3 μmol/L) abolished the ZnPPIX-mediated decrease in contractile response to EFS. Conversely, incubation with CORM-3 (400 μmol/L) alone increased both the contractile response to EFS at 10 Hz (10 Hz: 71.02 ± 19.16 vs 116.25 ± 53.70, P = 0.01) and the contractile response to ACh (100 μmol/L) ( P = 0.012). Co-administration of atropine abolished the CORM-3-mediated effects on the EFS-mediated response. When granisetron was co-incubated in vitro with ZnPPIX, the ZnPPIX-mediated decrease in colon contractile response to EFS was lost. On the other hand, co-incubation of granisetron and CORM-3 (400 μmol/L) further increased the colon's contractile response to EFS (at 5 Hz: P = 0.007; at 10 Hz: P = 0.001) and to ACh (ACh 10 μmol/L: P = 0.001; ACh 100 μmol/L: P = 0.001) elicited by CORM-3 alone. L-NNA co-administered with granisetron and CORM-3 abolished the potentiating effect of CORM-3 on granisetron on both the EFS-induced and ACh-induced contractile response. Taken together, findings from in vivo and in vitro studies suggest that the HO/CO pathway is involved in the constipating effects of granisetron.

Carbon monoxide contributes to the constipating effects of granisetron in rat colon

PubMed Central

Nacci, Carmela; Fanelli, Margherita; Potenza, Maria Assunta; Leo, Valentina; Montagnani, Monica; De Salvia, Maria Antonietta

2016-01-01

AIM To investigate the mechanisms underlying the potential contribution of the heme oxygenase/carbon monoxide (HO/CO) pathway in the constipating effects of granisetron. METHODS For in vivo studies, gastrointestinal motility was evaluated in male rats acutely treated with granisetron [25, 50, 75 μg/kg/subcutaneous (sc)], zinc protoporphyrin IX [ZnPPIX, 50 μg/kg/intraperitoneal (ip)] and hemin (50 μmol/L/kg/ip), alone or in combination. For in vitro studies, the contractile neurogenic response to electrical field stimulation (EFS, 3, 5, 10 Hz, 14 V, 1 ms, pulse trains lasting 10 s), as well as the contractile myogenic response to acetylcholine (ACh, 0.1-100 μmol/L) were evaluated on colon specimens incubated with granisetron (3 μmol/L, 15 min), ZnPPIX (10 μmol/L, 60 min) or CO-releasing molecule-3 (CORM-3, 100, 200, 400 μmol/L) alone or in combination. These experiments were performed under co-treatment with or without atropine (3 μmol/L, a muscarinic receptor antagonist) or NG-nitro-L-Arginine (L-NNA, 100 μmol/L, a nitric oxide synthase inhibitor). RESULTS Administration of granisetron (50, 75 μg/kg) in vivo significantly increased the time to first defecation (P = 0.045 vs vehicle-treated rats), clearly suggesting a constipating effect of this drug. Although administration of ZnPPIX or hemin alone had no effect on this gastrointestinal motility parameter, ZnPPIX co-administered with granisetron abolished the granisetron-induced constipation. On the other hand, co-administration of hemin and granisetron did not modify the increased constipation observed under granisetron alone. When administered in vitro, granisetron alone (3 μmol/L) did not significantly modify the colon’s contractile response to either EFS or ACh. Incubation with ZnPPIX alone (10 μmol/L) significantly reduced the colon’s contractile response to EFS (P = 0.016) but had no effect on contractile response to ACh. Co-administration of ZnPPIX and atropine (3 μmol/L) abolished the ZnPPIX-mediated decrease in contractile response to EFS. Conversely, incubation with CORM-3 (400 μmol/L) alone increased both the contractile response to EFS at 10 Hz (10 Hz: 71.02 ± 19.16 vs 116.25 ± 53.70, P = 0.01) and the contractile response to ACh (100 μmol/L) (P = 0.012). Co-administration of atropine abolished the CORM-3-mediated effects on the EFS-mediated response. When granisetron was co-incubated in vitro with ZnPPIX, the ZnPPIX-mediated decrease in colon contractile response to EFS was lost. On the other hand, co-incubation of granisetron and CORM-3 (400 μmol/L) further increased the colon’s contractile response to EFS (at 5 Hz: P = 0.007; at 10 Hz: P = 0.001) and to ACh (ACh 10 μmol/L: P = 0.001; ACh 100 μmol/L: P = 0.001) elicited by CORM-3 alone. L-NNA co-administered with granisetron and CORM-3 abolished the potentiating effect of CORM-3 on granisetron on both the EFS-induced and ACh-induced contractile response. CONCLUSION Taken together, findings from in vivo and in vitro studies suggest that the HO/CO pathway is involved in the constipating effects of granisetron. PMID:27895421

[UTP regulates spontaneous transient outward currents in porcine coronary artery smooth muscle cells through PLC-IP(3) signaling pathway].

PubMed

Li, Peng-Yun; Zeng, Xiao-Rong; Yang, Yan; Cai, Fang; Li, Miao-Ling; Liu, Zhi-Fei; Pei, Jie; Zhou, Wen

2008-02-25

The aim of the present study was to investigate the effects of inositol 1,4,5-trisphosphate (IP(3))-generating agonist UTP on spontaneous transient outward currents (STOCs), and explore the role of intracellular Ca(2+) release in the current response mediated by IP(3) in porcine coronary artery smooth muscle cells (CASMCs). The coronary artery was excised from the fresh porcine heart and cut into small segments (2 mm × 5 mm) and then transferred to enzymatic dissociation solution for incubation. Single CASMCs were obtained by two-step enzyme digestion at 37 °C. STOCs were recorded and characterized using the perforated whole-cell patch-clamp configuration in freshly isolated porcine CASMCs. The currents were amplified and filtered by patch-clamp amplifier (Axopatch 200B), and then the digitized data were recorded by pClamp 9.0 software and further analyzed by MiniAnalysis 6.0 program. The results were as follows: (1) UTP led to conspicuous increases in STOC amplitude by (57.54±5.34)% and in frequency by (77.46±8.42)% (P<0.01, n=38). (2) The specific blocker of phospholipase C (PLC) - U73122 (5 μmol/L) remarkably reduced STOC amplitude by (31.04±7.46)% and frequency by (41.65±16.59)%, respectively (P<0.05, n=10). In the presence of U73122, UTP failed to reactivate STOCs (n=7). (3) Verapamil (20 μmol/L) and CdCl2 (200 μmol/L), two blockers of L-type voltage-dependent Ca(2+) channels, had little effects on STOCs initiated by UTP (n=8). (4) 1 μmol/L bisindolylmaleimide I (BisI), a potent blocker of protein kinase C (PKC), significantly increased STOC amplitude by (65.44±24.66)% and frequency by (61.35±21.47)% (P<0.01, n=12); UTP (40 μmol/L), applied in the presence of 1 μmol/L BisI, could further increase STOC activity (P<0.05, P<0.01, n=12). Subsequent application of ryanodine (50 μmol/L) abolished STOC activity. (5) In the presence of UTP (40 μmol/L), inhibition of IP(3) receptors (IP(3)Rs) by 2-aminoethoxydiphenyl borate (2-APB, 40 μmol/L) reduced STOC amplitude by (24.08±3.97)% (P<0.05, n=8), but had little effect on STOC frequency (n=8). While application of 2-APB (80 μmol/L) significantly reduced STOC amplitude by (31.43±6.34)% and frequency by (40.59±19.01)%, respectively (P<0.05, P<0.01, n=6). Subsequent application of ryanodine (50 μmol/L) completely blocked STOC activity. Pretreatment of cells with 2-APB (40 μmol/L) or ryanodine (50 μmol/L), UTP (40 μmol/L) failed to reactivate STOCs. The results suggest that UTP activates STOCs mainly via PLC and IP(3)-dependent mechanisms. Complex Ca(2+)-mobilization pathways are involved in UTP-mediated STOC activation in porcine CASMCs.

Excel-Based Tool for Pharmacokinetically Guided Dose Adjustment of Paclitaxel.

PubMed

Kraff, Stefanie; Lindauer, Andreas; Joerger, Markus; Salamone, Salvatore J; Jaehde, Ulrich

2015-12-01

Neutropenia is a frequent and severe adverse event in patients receiving paclitaxel chemotherapy. The time above a paclitaxel threshold concentration of 0.05 μmol/L (Tc > 0.05 μmol/L) is a strong predictor for paclitaxel-associated neutropenia and has been proposed as a target pharmacokinetic (PK) parameter for paclitaxel therapeutic drug monitoring and dose adaptation. Up to now, individual Tc > 0.05 μmol/L values are estimated based on a published PK model of paclitaxel by using the software NONMEM. Because many clinicians are not familiar with the use of NONMEM, an Excel-based dosing tool was developed to allow calculation of paclitaxel Tc > 0.05 μmol/L and give clinicians an easy-to-use tool. Population PK parameters of paclitaxel were taken from a published PK model. An Alglib VBA code was implemented in Excel 2007 to compute differential equations for the paclitaxel PK model. Maximum a posteriori Bayesian estimates of the PK parameters were determined with the Excel Solver using individual drug concentrations. Concentrations from 250 patients were simulated receiving 1 cycle of paclitaxel chemotherapy. Predictions of paclitaxel Tc > 0.05 μmol/L as calculated by the Excel tool were compared with NONMEM, whereby maximum a posteriori Bayesian estimates were obtained using the POSTHOC function. There was a good concordance and comparable predictive performance between Excel and NONMEM regarding predicted paclitaxel plasma concentrations and Tc > 0.05 μmol/L values. Tc > 0.05 μmol/L had a maximum bias of 3% and an error on precision of <12%. The median relative deviation of the estimated Tc > 0.05 μmol/L values between both programs was 1%. The Excel-based tool can estimate the time above a paclitaxel threshold concentration of 0.05 μmol/L with acceptable accuracy and precision. The presented Excel tool allows reliable calculation of paclitaxel Tc > 0.05 μmol/L and thus allows target concentration intervention to improve the benefit-risk ratio of the drug. The easy use facilitates therapeutic drug monitoring in clinical routine.

Sustainable recovery of valuable metals from spent lithium-ion batteries using DL-malic acid: Leaching and kinetics aspect.

PubMed

Sun, Conghao; Xu, Liping; Chen, Xiangping; Qiu, Tianyun; Zhou, Tao

2018-02-01

An eco-friendly and benign process has been investigated for the dissolution of Li, Co, Ni, and Mn from the cathode materials of spent LiNi 1/3 Co 1/3 Mn 1/3 O 2 batteries, using DL-malic acid as the leaching agent in this study. The leaching efficiencies of Li, Co, Ni, and Mn can reach about 98.9%, 94.3%, 95.1%, and 96.4%, respectively, under the leaching conditions of DL-malic acid concentration of 1.2 M, hydrogen peroxide content of 1.5 vol.%, solid-to-liquid ratio of 40 g l -1 , leaching temperature of 80°C, and leaching time of 30 min. In addition, the leaching kinetic was investigated based on the shrinking model and the results reveal that the leaching reaction is controlled by chemical reactions within 10 min with activation energies (Ea) of 21.3 kJ·mol -1 , 30.4 kJ·mol -1 , 27.9 kJ·mol -1 , and 26.2 kJ·mol -1 for Li, Co, Ni, and Mn, respectively. Diffusion process becomes the controlled step with a prolonged leaching time from 15 to 30 min, and the activation energies (Ea) are 20.2 kJ·mol -1 , 28.9 kJ·mol -1 , 26.3 kJ·mol -1 , and 25.0 kJ·mol -1 for Li, Co, Ni, and Mn, respectively. This hydrometallurgical route was found to be effective and environmentally friendly for leaching metals from spent lithium batteries.

[Inhibitory effect of baicalein on the proliferation and invasion of osteosarcoma cells and mechanism].

PubMed

Tang, Zhibin; Li, Chun; Chen, Zhiwei

2015-03-01

To explore the effect of baicalein on the proliferation and invasion of osteosarcoma cells and its related mechanism. Osteosarcoma MG-63 cells that were cultured in vitro were respectively treated with 20 μL culture medium (control group), dehydrated alcohol (0 μmol/L baicalein group), 100 and 200 μmol/L baicalein solution for 48 hours. Cell proliferation was analyzed by MTT assay. The cell invasion ability was detected using Transwell(TM) invasion assay. The expression of ezrin mRNA was examined by real-time quantitative PCR. The expressions of ezrin protein and p-ezrin protein were measured using Western blotting. Apoptosis index (AI) was determined by terminal deoxynucleotidyl transferase-mediated dUTP nick end labeling (TUNEL). The inhibitory rates of cell proliferation significantly increased in 100 and 200 μmol/L baicalein groups as compared with 0 μmol/L baicalein group. Moreover, that was higher in 200 μmol/L baicalein group than in 100 μmol/L baicalein group. In comparison with control and 0 μmol/L baicalein groups, the mean cell numbers of permeated membrane and levels of ezrin mRNA, ezrin protein and p-ezrin protein gradually decreased, but AI was gradually elevated with the increase of baicalein concentrations, whereas there was no significant difference in these indicators between 0 μmol/L baicalein group and control group. Baicalein can inhibit the proliferation and invasion of osteosarcoma MG-63 cells. The mechanism may be associated with the inhibited expression and activity of ezrin protein and the promoted tumor cell apoptosis.

Simultaneous determination of albumin and low-molecular-mass thiols in plasma by HPLC with UV detection.

PubMed

Borowczyk, Kamila; Wyszczelska-Rokiel, Monika; Kubalczyk, Paweł; Głowacki, Rafał

2015-02-15

In this paper, we describe a simple and robust HPLC based method for determination of total low- and high-molecular-mass thiols, protein S-linked thiols and reduced albumin in plasma. The method is based on derivatization of analytes with 2-chloro-1-methylquinolinium tetrafluoroborate, separation and quantification by reversed-phase liquid chromatography followed by UV detection. Disulfides were converted to their thiol counterparts by reductive cleavage with tris(2-carboxyethyl)phosphine. Linearity in detector response for total thiols was observed over the range of 1-40 μmol L(-1) for Hcy and glutathione (GSH), 5-100 μmol L(-1) for Cys-Gly, 20-300 μmol L(-1) for Cys and 3.1-37.5 μmol L(-1) (0.2-2.4gL(-1)) for human serum albumin (HSA). For the protein S-bound forms these values were as follows: 0.5-30 μmol L(-1) for Hcy and GSH, 2.5-60 μmol L(-1) for Cys-Gly and 5-200 μmol L(-1) for Cys. The LOQs for total HSA, Cys, Hcy, Cys-Gly and GSH were 0.5, 0.2, 0.4, 0.3 and 0.4 μmol L(-1), respectively. The estimated validation parameters for all analytes are more than sufficient to allow the analytical method to be used for monitoring of the total and protein bound thiols as well as redox status of HSA in plasma. Copyright © 2015 Elsevier B.V. All rights reserved.

Assessment of sediment quality based on acid-volatile sulfide and simultaneously extracted metals in heavily industrialized area of Asaluyeh, Persian Gulf: concentrations, spatial distributions, and sediment bioavailability/toxicity.

PubMed

Arfaeinia, Hossein; Nabipour, Iraj; Ostovar, Afshin; Asadgol, Zahra; Abuee, Ehsan; Keshtkar, Mozhgan; Dobaradaran, Sina

2016-05-01

Sediment samples from the coastal area of Asaluyeh harbor were collected during autumn and spring 2015. The acid-volatile sulfide (AVS) and simultaneously extracted metals (SEMs) were measured to assess the sediment quality and potential ecological risks. The average concentrations (and relative standard deviation (RSD)) of AVS in the industrial sediments were 12.32 μmol/g (36.91) and 6.34 μmol/g (80.05) in autumn and spring, respectively, while in the urban area, these values were 0.44 μmol/g (123.50) and 0.31 μmol/g (160.0) in autumn and spring, respectively. The average concentrations of SEM (and RSD) in the industrial sediments were 15.02 μmol/g (14.38) and 12.34 μmol/g (20.65) in autumn and spring, respectively, while in the urban area, these values were 1.10 μmol/g (43.03) and 1.06 μmol/g (55.59) in autumn and spring, respectively. Zn was the predominant component (34.25-86.24 %) of SEM, while the corresponding value for Cd, much more toxic ingredient, was less than 1 %. Some of the coastal sediments in the harbor of Asaluyeh (20 and 47 % in autumn and spring, respectively) had expected adverse biological effects based on the suggested criterion by United States Environmental Protection Agency (USEPA), while most stations (80 and 53 % in autumn and spring, respectively) had uncertain adverse effects.

Bond Dissociation Energies for Diatomic Molecules Containing 3d Transition Metals: Benchmark Scalar-Relativistic Coupled-Cluster Calculations for 20 Molecules

DOE PAGES

Cheng, Lan; Gauss, Jürgen; Ruscic, Branko; ...

2017-01-12

Benchmark scalar-relativistic coupled-cluster calculations for dissociation energies of the 20 diatomic molecules containing 3d transition metals in the 3dMLBE20 database ( J. Chem. Theory Comput. 2015, 11, 2036) are reported in this paper. Electron correlation and basis set effects are systematically studied. The agreement between theory and experiment is in general satisfactory. For a subset of 16 molecules, the standard deviation between computational and experimental values is 9 kJ/mol with the maximum deviation being 15 kJ/mol. The discrepancies between theory and experiment remain substantial (more than 20 kJ/mol) for VH, CrH, CoH, and FeH. To explore the source of themore » latter discrepancies, the analysis used to determine the experimental dissociation energies for VH and CrH is revisited. It is shown that, if improved values are used for the heterolytic C–H dissociation energies of di- and trimethylamine involved in the experimental determination, the experimental values for the dissociation energies of VH and CrH are increased by 18 kJ/mol, such that D 0(VH) = 223 ± 7 kJ/mol and D 0(CrH) = 204 ± 7 kJ/mol (or D e(VH) = 233 ± 7 kJ/mol and D e(CrH) = 214 ± 7 kJ/mol). Finally, the new experimental values agree quite well with the calculated values, showing the consistency of the computation and the measured reaction thresholds.« less

Effect of gingerol on colonic motility via inhibition of calcium channel currents in rats.

PubMed

Cai, Zheng-Xu; Tang, Xu-Dong; Wang, Feng-Yun; Duan, Zhi-Jun; Li, Yu-Chun; Qiu, Juan-Juan; Guo, Hui-Shu

2015-12-28

To investigate the effect of gingerol on colonic motility and the action of L-type calcium channel currents in this process. The distal colon was cut along the mesenteric border and cleaned with Ca(2+)-free physiological saline solution. Muscle strips were removed and placed in Ca(2+)-free physiological saline solution, which was oxygenated continuously. Longitudinal smooth muscle samples were prepared by cutting along the muscle strips and were then placed in a chamber. Mechanical contractile activities of isolated colonic segments in rats were recorded by a 4-channel physiograph. Colon smooth muscle cells were dissociated by enzymatic digestion. L-type calcium currents were recorded using the conventional whole-cell patch-clamp technique. Gingerol inhibited the spontaneous contraction of colonic longitudinal smooth muscle in a dose-dependent manner with inhibition percentages of 13.3% ± 4.1%, 43.4% ± 3.9%, 78.2% ± 3.6% and 80.5% ± 4.5% at 25 μmol/L, 50 μmol/L, 75 μmol/L and 100 μmol/L, respectively (P < 0.01). Nifedipine, an L-type calcium channel blocker, diminished the inhibition of colonic motility by gingerol. Gingerol inhibited L-type calcium channel currents in colonic longitudinal myocytes of rats. At a 75 μmol/L concentration of gingerol, the percentage of gingerol-induced inhibition was diminished by nifedipine from 77.1% ± 4.2% to 42.6% ± 3.6% (P < 0.01). Gingerol suppressed IBa in a dose-dependent manner, and the inhibition rates were 22.7% ± 2.38%, 35.77% ± 3.14%, 49.78% ± 3.48% and 53.78% ± 4.16% of control at 0 mV, respectively, at concentrations of 25 μmol/L, 50 μmol/L, 75 μmol/L and 100 μmol/L (P < 0.01). The steady-state activation curve was shifted to the right by treatment with gingerol. The value of half activation was -14.23 ± 1.12 mV in the control group and -10.56 ± 1.04 mV in the 75 μmol/L group (P < 0.05) with slope factors, Ks, of 7.16 ± 0.84 and 7.02 ± 0.93 (P < 0.05) in the control and 75 μmol/L groups, respectively. However, the steady-state inactivation curve was not changed, with a half-inactivation voltage, 0.5 V, of -27.43 ± 1.26 mV in the control group and -26.56 ± 1.53 mV in the 75 μmol/L gingerol group (P > 0.05), and a slope factor, K, of 13.24 ± 1.62 in the control group and 13.45 ± 1.68 (P > 0.05) in the 75 μmol/L gingerol group. Gingerol inhibits colonic motility by preventing Ca(2+) influx through L-type calcium channels.

Effect of gingerol on colonic motility via inhibition of calcium channel currents in rats

PubMed Central

Cai, Zheng-Xu; Tang, Xu-Dong; Wang, Feng-Yun; Duan, Zhi-Jun; Li, Yu-Chun; Qiu, Juan-Juan; Guo, Hui-Shu

2015-01-01

AIM: To investigate the effect of gingerol on colonic motility and the action of L-type calcium channel currents in this process. METHODS: The distal colon was cut along the mesenteric border and cleaned with Ca2+-free physiological saline solution. Muscle strips were removed and placed in Ca2+-free physiological saline solution, which was oxygenated continuously. Longitudinal smooth muscle samples were prepared by cutting along the muscle strips and were then placed in a chamber. Mechanical contractile activities of isolated colonic segments in rats were recorded by a 4-channel physiograph. Colon smooth muscle cells were dissociated by enzymatic digestion. L-type calcium currents were recorded using the conventional whole-cell patch-clamp technique. RESULTS: Gingerol inhibited the spontaneous contraction of colonic longitudinal smooth muscle in a dose-dependent manner with inhibition percentages of 13.3% ± 4.1%, 43.4% ± 3.9%, 78.2% ± 3.6% and 80.5% ± 4.5% at 25 μmol/L, 50 μmol/L, 75 μmol/L and 100 μmol/L, respectively (P < 0.01). Nifedipine, an L-type calcium channel blocker, diminished the inhibition of colonic motility by gingerol. Gingerol inhibited L-type calcium channel currents in colonic longitudinal myocytes of rats. At a 75 μmol/L concentration of gingerol, the percentage of gingerol-induced inhibition was diminished by nifedipine from 77.1% ± 4.2% to 42.6% ± 3.6% (P < 0.01). Gingerol suppressed IBa in a dose-dependent manner, and the inhibition rates were 22.7% ± 2.38%, 35.77% ± 3.14%, 49.78% ± 3.48% and 53.78% ± 4.16% of control at 0 mV, respectively, at concentrations of 25 μmol/L, 50 μmol/L, 75 μmol/L and 100 μmol/L (P < 0.01). The steady-state activation curve was shifted to the right by treatment with gingerol. The value of half activation was -14.23 ± 1.12 mV in the control group and -10.56 ± 1.04 mV in the 75 μmol/L group (P < 0.05) with slope factors, Ks, of 7.16 ± 0.84 and 7.02 ± 0.93 (P < 0.05) in the control and 75 μmol/L groups, respectively. However, the steady-state inactivation curve was not changed, with a half-inactivation voltage, 0.5 V, of -27.43 ± 1.26 mV in the control group and -26.56 ± 1.53 mV in the 75 μmol/L gingerol group (P > 0.05), and a slope factor, K, of 13.24 ± 1.62 in the control group and 13.45 ± 1.68 (P > 0.05) in the 75 μmol/L gingerol group. CONCLUSION: Gingerol inhibits colonic motility by preventing Ca2+ influx through L-type calcium channels. PMID:26730157

40 CFR 1065.750 - Analytical gases.

Code of Federal Regulations, 2010 CFR

2010-07-01

... O2 concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen... concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen. (3) Use the....41) mol/mol, balance He, and a stated total hydrocarbon concentration of 0.05 µmol/mol or less. (ii...

40 CFR 1065.750 - Analytical gases.

Code of Federal Regulations, 2012 CFR

2012-07-01

... O2 concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen... concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen. (3) Use the....41) mol/mol, balance He, and a stated total hydrocarbon concentration of 0.05 µmol/mol or less. (ii...

40 CFR 1065.750 - Analytical gases.

Code of Federal Regulations, 2013 CFR

2013-07-01

... O2 concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen... concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen. (3) Use the....41) mol/mol, balance He, and a stated total hydrocarbon concentration of 0.05 µmol/mol or less. (ii...

40 CFR 1065.750 - Analytical gases.

Code of Federal Regulations, 2011 CFR

2011-07-01

... O2 concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen... concentration in the exhaust sample is zero, we recommend using a balance gas of purified nitrogen. (3) Use the....41) mol/mol, balance He, and a stated total hydrocarbon concentration of 0.05 µmol/mol or less. (ii...

Radical graft polymerization of an Allyl Monomer onto Hydrophilic Polymers and their antibacterial nanofibrous membranes

USDA-ARS?s Scientific Manuscript database

Hydrophilic poly (vinyl alcohol-co-ethylene) (PVA-co-PE) copolymers with 27 mol %, 32 mol % and 44 mol % ethylene were functionalized by melt radical graft copolymerization with 2,4-diamino-6-diallylamino-1,3,5-triazine (NDAM) using reactive extrusion. This functionalization imparts antibacterial pr...

Enhanced hydrogen production from glucose using ldh- and frd-inactivated Escherichia coli strains.

PubMed

Yoshida, Akihito; Nishimura, Taku; Kawaguchi, Hideo; Inui, Masayuki; Yukawa, Hideaki

2006-11-01

We improved the hydrogen yield from glucose using a genetically modified Escherichia coli. E. coli strain SR15 (DeltaldhA, DeltafrdBC), in which glucose metabolism was directed to pyruvate formate lyase (PFL), was constructed. The hydrogen yield of wild-type strain of 1.08 mol/mol glucose, was enhanced to 1.82 mol/mol glucose in strain SR15. This figure is greater than 90 % of the theoretical hydrogen yield of facultative anaerobes (2.0 mol/mol glucose). Moreover, the specific hydrogen production rate of strain SR15 (13.4 mmol h(-1) g(-1) dry cell) was 1.4-fold higher than that of wild-type strain. In addition, the volumetric hydrogen production rate increased using the process where cells behaved as an effective catalyst. At 94.3 g dry cell/l, a productivity of 793 mmol h(-1) l(-1) (20.2 l h(-1) l(-1) at 37 degrees C) was achieved using SR15. The reported productivity substantially surpasses that of conventional biological hydrogen production processes and can be a trigger for practical applications.

Thermodynamic and kinetic analyses of curcumin and bovine serum albumin binding.

PubMed

Hudson, Eliara Acipreste; de Paula, Hauster Maximiler Campos; Ferreira, Guilherme Max Dias; Ferreira, Gabriel Max Dias; Hespanhol, Maria do Carmo; da Silva, Luis Henrique Mendes; Pires, Ana Clarissa Dos S

2018-03-01

Bovine serum albumin (BSA)/curcumin binding and dye photodegradation stability were evaluated. BSA/curcumin complex showed 1:1 stoichiometry, but the thermodynamic binding parameters depended on the technique used and BSA conformation. The binding constant was of the order of 10 5 L·mol -1 by fluorescence and microcalorimetric, and 10 3 and 10 4 L·mol -1 by surface plasmon resonance (steady-state equilibrium and kinetic experiments, respectively). For native BSA/curcumin, fluorescence indicated an enthalpic and entropic driven process based on the standard enthalpy change (ΔH ○ F =-8.67kJ·mol -1 ), while microcalorimetry showed an entropic driven binding process (ΔH ○ cal =29.11kJ·mol -1 ). For the unfolded BSA/curcumin complex, it was found thatp ΔH ○ F =-16.12kJ·mol -1 and ΔH ○ cal =-42.63kJ·mol -1 . BSA (mainly native) increased the curcumin photodegradation stability. This work proved the importance of using different techniques to characterize the protein-ligand binding. Copyright © 2017 Elsevier Ltd. All rights reserved.

Methyl (2Z)-2-bromo­meth­yl-3-(3-chloro­phen­yl)prop-2-enoate

PubMed Central

Swaminathan, K.; Sethusankar, K.; Selvakumar, Raman; Bakthadoss, Manickam

2013-01-01

There are two independent mol­ecules (A and B) in the asymmetric unit of the title compound C11H10BrClO2, which represents the Z isomer. The methyl­acrylate moieties are essentially planar, within 0.084 (2) and 0.027 (5) Å in mol­ecules A and B, respectively. The benzene ring makes dihedral angles of 13.17 (7) and 27.89 (9)° with the methyl­acrylate moiety in mol­ecules A and B, respectively. The methyl­bromide moiety is almost orthogonal to the benzene ring, making dihedral angles of 81.46 (16)° in mol­ecule A and 79.61 (16)° in mol­ecule B. The methyl­acrylate moiety exhibits an extended trans conformation in both mol­ecules. In the crystal, pairs of C—H⋯O hydrogen bonds result in the formation of quasi-centrosymmetric R 2 2(14) AB dimers. PMID:23795037

Ab initio calculation of infrared intensities for hydrogen peroxide

NASA Technical Reports Server (NTRS)

Rogers, J. D.; Hillman, J. J.

1982-01-01

Results of an ab initio SCF quantum mechanical study are used to derive estimates for the infrared intensities of the fundamental vibrations of hydrogen peroxide. Atomic polar tensors (APTs) were calculated on the basis of a 4-31G basis set, and used to derive absolute intensities for the vibrational transitions. Comparison of the APTs calculated for H2O2 with those previously obtained for H2O and CH3OH, and of the absolute intensities derived from the H2O2 APTs with those derived from APTs transferred from H2O and CH3OH, reveals the sets of values to differ by no more than a factor of two, supporting the validity of the theoretical calculation. Values of the infrared intensities obtained correspond to A1 = 14.5 km/mol, A2 = 0.91 km/mol, A3 = 0.058 km/mol, A4 = 123 km/mol, A5 = 46.2 km/mol, and A6 = 101 km/mol. Charge, charge flux and overlap contributions to the dipole moment derivatives are also computed.

Ab initio calculation of infrared intensities for hydrogen peroxide

NASA Astrophysics Data System (ADS)

Rogers, J. D.; Hillman, J. J.

1982-04-01

Results of an ab initio SCF quantum mechanical study are used to derive estimates for the infrared intensities of the fundamental vibrations of hydrogen peroxide. Atomic polar tensors (APTs) were calculated on the basis of a 4-31G basis set, and used to derive absolute intensities for the vibrational transitions. Comparison of the APTs calculated for H2O2 with those previously obtained for H2O and CH3OH, and of the absolute intensities derived from the H2O2 APTs with those derived from APTs transferred from H2O and CH3OH, reveals the sets of values to differ by no more than a factor of two, supporting the validity of the theoretical calculation. Values of the infrared intensities obtained correspond to A1 = 14.5 km/mol, A2 = 0.91 km/mol, A3 = 0.058 km/mol, A4 = 123 km/mol, A5 = 46.2 km/mol, and A6 = 101 km/mol. Charge, charge flux and overlap contributions to the dipole moment derivatives are also computed.

N-(1-Allyl-1H-indazol-5-yl)-4-meth­oxy­benzene­sulfonamide hemihydrate

PubMed Central

Chicha, Hakima; Rakib, El Mostapha; Geffken, Detlef; Saadi, Mohamed; El Ammari, Lahcen

2013-01-01

In the title compound, C17H17N3O3 .0.5H2O, the indazole system makes a dihedral angle of 46.19 (8)° with the plane through the benzene ring and is nearly perpendicular to the allyl group, as indicated by the dihedral angle of 81.2 (3)°. In the crystal, the water mol­ecule, disordered over two sites related by an inversion center, forms O—H⋯N bridges between indazole N atoms of two sulfonamide mol­ecules. It is also connected via N—H⋯O inter­action to the third sulfonamide mol­ecule; however, due to the water mol­ecule disorder, only every second mol­ecule of sulfonamide participates in this inter­action. This missing inter­action results in a slight disorder of the sulfonamide S,O and N atoms which are split over two sites with half occupancy. With the help of C–H⋯O hydrogen bonds, the mol­ecules are further connected into a three-dimensional network. PMID:24098264

Positron annihilation study on ZnO-based scintillating glasses

NASA Astrophysics Data System (ADS)

Nie, Jiaxiang; Yu, Runsheng; Wang, Baoyi; Ou, Yuwen; Zhong, Yurong; Xia, Fang; Chen, Guorong

2009-04-01

Positron lifetime of ZnO-based scintillating glasses (55 - x)SiO 2-45ZnO- xBaF 2 ( x = 5, 10, 15 mol%) were measured with a conventional fast-fast spectrometer. Three positron lifetime components τ1, τ 2, and τ3 are ˜0.23 ns, ˜0.45 ns, and ˜1.6 ns, respectively. All the three positron lifetime components first increase with increasing BaF 2 concentration from 5 mol% to 10 mol%, then decreases as BaF 2 further increases to 15 mol%. The result suggests that the glass sample with 10 mol% BaF 2 contains the highest defect density, and is in excellent agreement with glass chemistry, glass density, thermal properties, and calculated crystallinity. Therefore, positron annihilation lifetime measurement is an effective tool for analyzing defects in ZnO-based scintillating glasses.

Enthalpies of melting of LnSF compounds (Ln = La, Ce, Pr, Nd, Sm)

NASA Astrophysics Data System (ADS)

Andreev, P. O.; Mikhalkina, O. G.; Andreev, O. V.; Elyshev, A. V.

2015-05-01

The melting temperatures and enthalpies of such congruently melting compounds as LaSF ( T m = 1713 ± 7 K, Δ H = 45.7 ± 4.6 kJ/mol), CeSF ( T m = 1683 ± 7 K, Δ H = 40.7 ± 4.1 kJ/mol), PrSF ( T m = 1661 ± 7 K, Δ H = 39.7 ± 4.0 kJ/mol), NdSF ( T m = 1654 ± 7 K, Δ H = 40.2 ± 4.0 kJ/mol), and SmSF ( T m = 1587 ± 7 K, Δ H = 36.1 ± 3.6 kJ/mol) are determined via synchronous thermal analysis. The tetrad effect is evident in the change of the melting temperatures and enthalpies of LnSF compounds (Ln = La, Ce, Pr, Nd, Sm) depending on r(Ln3+).

Effect of dietary supplementation with Moringa Oleifera leaf on performance, meat quality, and oxidative stability of meat in broilers.

PubMed

Cui, Yao-Ming; Wang, Jing; Lu, Wei; Zhang, Hai-Jun; Wu, Shu-Geng; Qi, Guang-Hai

2018-04-11

The objective of this study was to evaluate the effects of dietary supplementation with Moringa oleifera leaf (MOL) on performance, carcass characteristics, meat quality, and oxidative stability of breast muscle in broilers. A total of 720 1-d-old male Arbor Acres birds were randomly divided into 6 dietary groups, which were fed a basal diet supplemented with 0, 1, 2, 5, 10, and 15% MOL, respectively. Each group had 6 replicates of 20 birds each. The feeding trial lasted for 42 d. The results showed dietary MOL supplementation linearly and quadratically decreased body weight and average daily gain (P < 0.01), and increased feed conversion ratio (P < 0.001). Abdominal fat decreased linearly and quadratically in response to the supplementation of MOL in diets, both on d 21 and 42 (P < 0.001). In breast muscle, dietary supplementation with MOL quadratically increased the contents of C18:2, C18:3n-3, C20:4, polyunsaturated fatty acids (PUFA), n-3 PUFA, n-6 PUFA (P < 0.01), and decreased thrombogenic index (TI; P = 0.019). Dietary inclusion of MOL improved meat color, evidenced by quadratically reduced b* (yellowness) values (45 min postmortem, P = 0.001; 24 h postmortem, P = 0.018) and increased a* (redness) values (24 h postmortem, P < 0.001). Besides, diets supplemented with MOL quadratically decreased malondialdehyde (MDA) levels in breast muscle during storage (P < 0.001). Plasma total anti-oxidative capacity, total superoxide dismutase, glutathione peroxidase activities increased quadratically (P < 0.01), whereas MDA decreased quadratically (P < 0.001), in response to dietary MOL supplementation. In summary, MOL could be used as a feed ingredient for broilers to improve PUFA contents, oxidative stability, color of breast muscle, and abdominal fat without adverse effects on growth performance, with an inclusion of 1.56% in the diets.

Effects of vitamin C, vitamin E, and molecular hydrogen on the placental function in trophoblast cells.

PubMed

Guan, Zhong; Li, Huai-Fang; Guo, Li-Li; Yang, Xiang

2015-08-01

This study aimed to investigate the effects of three different antioxidants, namely vitamin C, vitamin E, and molecular hydrogen, on cytotrophoblasts in vitro. Two trophoblast cell lines, JAR and JEG-3, were exposed to different concentrations of vitamin C (0, 25, 50, 100, 500, 1,000, 5,000 μmol/L), vitamin E (0, 25, 50, 100, 500, 1,000, 5,000 μmol/L), and molecular hydrogen (0, 25, 50, 100, 500 μmol/L) for 48 h. The cell viability was detected using the MTS assay. The secretion of human chorionic gonadotropin (hCG) and the tumor necrosis factor-α (TNF-α) were assessed and the expression of TNF-α mRNA was observed by real-time RT-PCR. Cell viability was significantly suppressed by 500 μmol/L vitamins C and E (P < 0.05), but not by 500 μmol/L molecular hydrogen (P > 0.05). The expression of TNF-α was increased by 100 μmol/L vitamin C and 50 μmol/L vitamins E, separately or combined (P < 0.05), but not by molecular hydrogen (0-500 μmol/L), as validated by real-time RT-PCR. But the secretion of hCG was both inhibited by 50-500 μmol/L molecular hydrogen and high levels of vitamin C and E, separately or combined. High levels of antioxidant vitamins C and E may have significant detrimental effects on placental function, as reflected by decreased cell viability and secretion of hCG; and placental immunity, as reflected by increased production of TNF-a. Meanwhile hydrogen showed no such effects on cell proliferation and TNF-α expression, but it could affect the level of hCG, indicating hydrogen as a potential candidate of antioxidant in the management of preeclampsia (PE) should be further studied.

Pathways for the OH + Br2 → HOBr + Br and HOBr + Br → HBr + BrO Reactions.

PubMed

Wang, Hongyan; Qiu, Yudong; Schaefer, Henry F

2016-02-11

The OH radical reaction with Br2 and the subsequent reaction HOBr + Br are of exceptional importance to atmospheric chemistry and environmental chemistry. The entrance complex, transition state, and exit complex for both reactions have been determined using the coupled-cluster method with single, double, and perturbative triple excitations CCSD(T) with correlation consistent basis sets up to size cc-pV5Z and cc-pV5Z-PP. Coupled cluster effects with full triples (CCSDT) and full quadruples (CCSDTQ) are explicitly investigated. Scalar relativistic effects, spin-orbit coupling, and zero-point vibrational energy corrections are evaluated. The results from the all-electron basis sets are compared with those from the effective core potential (ECP) pseudopotential (PP) basis sets. The results are consistent. The OH + Br2 reaction is predicted to be exothermic 4.1 ± 0.5 kcal/mol, compared to experiment, 3.9 ± 0.2 kcal/mol. The entrance complex HO···BrBr is bound by 2.2 ± 0.2 kcal/mol. The transition state lies similarly well below the reactants OH + Br2. The exit complex HOBr···Br is bound by 2.7 ± 0.6 kcal/mol relative to separated HOBr + Br. The endothermicity of the reaction HOBr + Br → HBr + BrO is 9.6 ± 0.7 kcal/mol, compared with experiment 8.7 ± 0.3 kcal/mol. For the more important reverse (exothermic) HBr + BrO reaction, the entrance complex BrO···HBr is bound by 1.8 ± 0.6 kcal/mol. The barrier for the HBr + BrO reaction is 6.8 ± 0.9 kcal/mol. The exit complex (Br···HOBr) for the HBr + BrO reaction is bound by 1.9 ± 0.2 kcal/mol with respect to the products HOBr + Br.

Exploring inhibitory potential of Curcumin against various cancer targets by in silico virtual screening.

PubMed

Mahajanakatti, Arpitha Badarinath; Murthy, Geetha; Sharma, Narasimha; Skariyachan, Sinosh

2014-03-01

Various types of cancer accounts for 10% of total death worldwide which necessitates better therapeutic strategies. Curcumin, a curcuminoid present in Curcuma longa, shown to exhibit antioxidant, anti-inflammatory and anticarcinogenic properties. Present study, we aimed to analyze inhibitory properties of curcumin towards virulent proteins for various cancers by computer aided virtual screening. Based on literature studies, twenty two receptors were selected which have critical virulent functions in various cancer. The binding efficiencies of curcumin towards selected targets were studied by molecular docking. Out of all, curcumin showed best results towards epidermal growth factor (EGF), virulent protein of gastric cancer; glutathione-S-transferase Pi gene (GST-PI), virulent protein for prostate cancer; platelet-derived growth factor alpha (PDGFA), virulent protein for mesothelioma and glioma compared with their natural ligands. The calculated binding energies of their docked conformations with curcumin found to be -7.59 kcal/mol, -7.98 kcal/mol and -7.93 kcal/mol respectively. Further, a comparative study was performed to screen binding efficiency of curcumin with two conventional antitumor agents, litreol and triterpene. Docking studies revealed that calculated binding energies of docked complex of litreol and EGF, GST-PI and PDGFA were found to be -5.08 kcal/mol, -3.69 kcal/mol and -1.86 kcal/mol respectively. The calculated binding energies of triterpene with EGF and PDGFA were found to be -4.02 kcal/mol and -3.11 kcal/mol respectively, whereas GST-PI showed +6.07 kcal/mol, indicate poor binding. The predicted pharmacological features of curcumin found to be better than litreol and triterpene. Our study concluded that curcumin has better interacting properties towards these cancer targets than their normal ligands and conventional antitumor agents. Our data pave insight for designing of curcumin as novel inhibitors against various types of cancer.

Theoretical Study of Spin Crossover in 30 Iron Complexes.

PubMed

Kepp, Kasper P

2016-03-21

Iron complexes are important spin crossover (SCO) systems with vital roles in oxidative metabolism and promising technological potential. The SCO tendency depends on the free energy balance of high- and low-spin states, which again depends on physical effects such as dispersion, relativistic effects, and vibrational entropy. This work studied 30 different iron SCO systems with experimentally known thermochemical data, using 12 different density functionals. Remarkably general entropy-enthalpy compensation across SCO systems was identified (R = 0.82, p = 0.002) that should be considered in rational SCO design. Iron(II) complexes displayed higher ΔH and ΔS values than iron(III) complexes and also less steep compensation effects. First-coordination sphere ΔS values computed from numerical frequencies reproduce most of the experimental entropy and should thus be included when modeling spin-state changes in inorganic chemistry (R = 0.52, p = 3.4 × 10(-3); standard error in TΔS ≈ 4.4 kJ/mol at 298 K vs 16 kJ/mol of total TΔS on average). Zero-point energies favored high-spin states by 9 kJ/mol on average. Interestingly, dispersion effects are surprisingly large for the SCO process (average: 9 kJ/mol, but up to 33 kJ/mol) and favor the more compact low-spin state. Relativistic effects favor low-spin by ∼9 kJ/mol on average, but up to 24 kJ/mol. B3LYP*, TPSSh, B2PLYP, and PW6B95 performed best for the typical calculation scheme that includes ZPE. However, if relativistic and dispersion effects are included, only B3LYP* remained accurate. On average, high-spin was favored by LYP by 11-15 kJ/mol relative to other correlation functionals, and by 4.2 kJ/mol per 1% HF exchange in hybrids. 13% HF exchange was optimal without dispersion, and 15% was optimal with all effects included for these systems.

Feasibility study of using a "travelling" CO2 and CH4 instrument to validate continuous in situ measurement stations

NASA Astrophysics Data System (ADS)

Hammer, S.; Konrad, G.; Vermeulen, A. T.; Laurent, O.; Delmotte, M.; Jordan, A.; Hazan, L.; Conil, S.; Levin, I.

2013-05-01

In the course of the ICOS (Integrated Carbon Observation System) Demonstration Experiment a feasibility study on the usefulness of a travelling comparison instrument (TCI) was conducted in order to evaluate continuous atmospheric CO2 and CH4 measurements at two European stations. The aim of the TCI is to independently measure ambient air in parallel to the standard station instrumentation, thus providing a comprehensive comparison that includes the sample intake system, the instrument itself as well as its calibration and data evaluation. Observed differences between the TCI and a gas chromatographic system, which acted as a reference for the TCI, were -0.02 ± 0.08 μmol mol-1 for CO2 and -0.3 ± 2.3 nmol mol-1 for CH4. Over a period of two weeks each, the continuous CO2 and CH4 measurements at two ICOS field stations, Cabauw (CBW), the Netherlands and Houdelaincourt (Observatoire Pérenne de l'Environnement, OPE), France, were compared to co-located TCI measurements. At Cabauw mean differences of 0.21 ± 0.06 μmol mol-1 for CO2 and 0.41 ± 0.50 nmol mol-1 for CH4 were found. For OPE the mean differences were 0.13 ± 0.07 μmol mol-1 for CO2 and 0.44 ± 0.36 nmol mol-1 for CH4. Offsets arising from differences in the working standard calibrations or leakages/contaminations in the drying systems are too small to explain the observed differences. Hence the most likely causes of these observed differences are leakages or contaminations in the intake lines and/or their flushing pumps. For the Cabauw instrument an additional error contribution originates from insufficient flushing of standard gases. Although the TCI is an extensive quality control approach it cannot replace other quality control systems. Thus, a comprehensive quality management strategy for atmospheric monitoring networks is proposed as well.

THE MECHANISM OF ACTION OF COLCHICINE

PubMed Central

Wilson, Leslie; Meza, Isaura

1973-01-01

The thermal depolymerization procedure of Stephens (1970. J. Mol. Biol. 47:353) has been employed for solubilization of Strongylocentrotus purpuratus sperm tail outer doublet microtubules with the use of a buffer during solubilization which is of optimal pH and ionic strength for the preservation of colchicine binding activity of chick embryo brain tubulin. Colchicine binding values were corrected for first-order decay during heat solubilization at 50°C (t½ = 5.4 min) and incubation with colchicine at 37°C in the presence of vinblastine sulfate (t½ = 485 min). The colchicine binding properties of heat-solubilized outer doublet tubulin were qualitatively identical with those of other soluble forms of tubulin. The solubilized tubulin (mol wt, 115,000) bound 0.9 ± 0.2 mol of colchicine per mol of tubulin, with a binding constant of 6.3 x 105 liters/mol at 37°C. The colchicine binding reaction was both time and temperature dependent, and the binding of colchicine was prevented in a competitive manner by podophyllotoxin (Ki = 1.3 x 10-6 M). The first-order decay of colchicine binding activity was substantially decreased by the addition of the vinca alkaloids, vinblastine sulfate or vincristine sulfate, thus demonstrating the presence of a vinca alkaloid binding site(s) on the outer doublet tubulin. Tubulin contained within the assembled microtubules did not decay. Intact outer doublet microtubules bound less than 0.001 mol of colchicine per mol of tubulin contained in the microtubules, under conditions where soluble tubulin would have bound 1 mol of colchicine per mol of tubulin (saturating concentration of colchicine, no decay of colchicine binding activity). The presence of colchicine had no effect on the rate of solubilization of outer doublet microtubules during incubation at 37°C. Therefore, the colchicine binding site on tubulin is blocked (not available to bind colchicine) when the tubulin is in the assembled outer doublet microtubules. PMID:4747924

Monoamine Oxidase and Dopamine β-Hydroxylase Inhibitors from the Fruits of Gardenia jasminoides

PubMed Central

Kim, Ji Ho; Kim, Gun Hee; Hwang, Keum Hee

2012-01-01

This research was designed to determine what components of Gardenia jasminoides play a major role in inhibiting the enzymes related antidepressant activity of this plant. In our previous research, the ethyl acetate fraction of G. jasminosides fruits inhibited the activities of both monoamine oxidase-A (MAO-A) and monoamine oxidase-B (MAO-B), and oral administration of the ethanolic extract slightly increased serotonin concentrations in the brain tissues of rats and decreased MAO-B activity. In addition, we found through in vitro screening test that the ethyl acetate fraction showed modest inhibitory activity on dopamine-β hydroxylase (DBH). The bioassay-guided fractionation led to the isolation of five bio-active compounds, protocatechuic acid (1), geniposide (2), 6'-O-trans-p-coumaroylgeniposide (3), 3,5-d-ihydroxy-1,7-bis (4-hydroxyphenyl) heptanes (4), and ursolic acid (5), from the ethyl acetate fraction of G. jasminoides fruits. The isolated compounds showed different inhibitory potentials against MAO-A, -B, and DBH. Protocatechuic acid showed potent inhibition against MAO-B (IC50 300 μmol/L) and DBH (334 μmol/L), exhibiting weak MAO-A inhibition (2.41 mmol/L). Two iridoid glycosides, geniposide (223 μmol/L) and 6'-O-trans-p-coumaroylgeniposide (127μmol/L), were selective MAO-B inhibitor. Especially, 6'-O-trans-p-coumaroylgeniposide exhibited more selective MAO-B inhibition than deprenyl, well-known MAO-B inhibitor for the treatment of early-stage Parkinson’s disease. The inhibitory activity of 3,5-di-hydroxy-1,7-bis (4-hydroxyphenyl) heptane was strong for MAO-B (196 μmol/L), modest for MAO-A (400 μmol/L), and weak for DBH (941 μmol/L). Ursolic acid exhibited significant inhibition of DBH (214 μmol/L), weak inhibition of MAO-B (780 μmol/L), and no inhibition against MAO-A. Consequently, G. jasminoides fruits are considerable for development of biofunctional food materials for the combination treatment of depression and neurodegenerative disorders. PMID:24116298

Towards an understanding of the molecular mechanism of solvation of drug molecules: a thermodynamic approach by crystal lattice energy, sublimation, and solubility exemplified by paracetamol, acetanilide, and phenacetin.

PubMed

Perlovich, German L; Volkova, Tatyana V; Bauer-Brandl, Annette

2006-10-01

Temperature dependencies of saturated vapor pressure for the monoclinic modification of paracetamol (acetaminophen), acetanilide, and phenacetin (acetophenetidin) were measured and thermodynamic functions of sublimation calculated (paracetamol: DeltaGsub298=60.0 kJ/mol; DeltaHsub298=117.9+/-0.7 kJ/mol; DeltaSsub298=190+/-2 J/mol.K; acetanilide: DeltaGsub298=40.5 kJ/mol; DeltaHsub298=99.8+/-0.8 kJ/mol; DeltaSsub298=197+/-2 J/mol.K; phenacetin: DeltaGsub298=52.3 kJ/mol; DeltaHsub298=121.8+/-0.7 kJ/mol; DeltaSsub298=226+/-2 J/mol.K). Analysis of packing energies based on geometry optimization of molecules in the crystal lattices using diffraction data and the program Dmol3 was carried out. Parameters analyzed were: (a) energetic contribution of van der Waals forces and hydrogen bonding to the total packing energy; (b) contributions of fragments of the molecules to the packing energy. The fraction of hydrogen bond energy in the packing energy increases as: phenacetin (17.5%)

Effect of supplementing crossbred Xhosa lop-eared goat castrates with Moringa oleifera leaves on growth performance, carcass and non-carcass characteristics.

PubMed

Moyo, Busani; Masika, Patrick J; Muchenje, Voster

2012-04-01

The objective of the study was to determine the effect of supplementing Moringa oleifera leaves (MOL) on growth performance, carcass and non-carcass characteristics of crossbred Xhosa lop-eared goats. A total of 24 castrated goats aged 8 months, with a mean initial weight of 15.1 ± 2.3 kg, were randomly divided into three diet groups with eight goats in each. The duration of the trial was 60 days. All goats received a basal diet of grass hay (GH) ad libitum and wheat bran (200 g/day each). The MOL and sunflower cake (SC) groups were fed additional 200 g of dried M. oleifera leaves and 170 g of SC, respectively. The third group (GH) did not receive any additional ration. The crude protein of MOL (23.75%) and SC (23.27%) were higher (P < 0.05) than that of the GH diet (14.08%). The attained average daily weight gain for goats fed MOL, SC and GH were 103.3, 101.3 and 43.3 g, respectively (P < 0.05). Higher (P < 0.05) feed intakes observed were in SC (491.5 g) and MOL (490.75 g) compared with GH (404.5 g). The hot carcass weight was higher (P < 0.05) for SC (10.48 kg) and MOL (10.34 kg) than for the GH group (8.59 kg). The dressing percentage in SC (55.8%) and MOL (55.1%) were higher (P < 0.05) than that of the GH (52.9%). The growth performance and carcass characteristics of SC and MOL goats were not different. Feeding MOL or SC improved the growth performance and carcass characteristics of goats in an almost similar way, which indicates that M. oleifera could be used as an alternative protein supplement in goats.

Vasorelaxant and antihypertensive effects of formononetin through endothelium-dependent and -independent mechanisms.

PubMed

Sun, Tao; Liu, Rui; Cao, Yong-xiao

2011-08-01

To investigate the mechanisms underlying the vasorelaxant effect of formononetin, an O-methylated isoflavone, in isolated arteries, and its antihypertensive activity in vivo. Arterial rings of superior mesenteric arteries, renal arteries, cerebral basilar arteries, coronary arteries and abdominal aortas were prepared from SD rats. Isometric tension of the arterial rings was recorded using a myograph system. Arterial pressure was measured using tail-cuff method in spontaneously hypertensive rats. Formononetin (1-300 μmol/L) elicited relaxation in arteries of the five regions that were pre-contracted by KCl (60 mmol/L), U46619 (1 μmol/L) or phenylephrine (10 μmol/L). The formononetin-induced relaxation was reduced by removal of endothelium or by pretreatment with L-NAME (100 μmol/L). Under conditions of endothelium denudation, formononetin (10, 30, and 100 μmol/L) inhibited the contraction induced by KCl and that induced by CaCl(2) in Ca(2+)-free depolarized medium. In the absence of extracellular Ca(2+), formononetin (10, 30, and 100 μmol/L) depressed the constriction caused by phenylephrine (10 μmol/L), but did not inhibit the tonic contraction in response to the addition of CaCl(2) (2 mmol/L). The contraction caused by caffeine (30 mmol/L) was not inhibited by formononetin (100 μmol/L). Formononetin (10 and 100 μmol/L) reduced the change rate of Ca(2+)-fluorescence intensity in response to KCl (50 mmol/L). In spontaneously hypertensive rats, formononetin (5, 10, and 20 mg/kg) slowly lowered the systolic, diastolic and mean arterial pressure. Formononetin causes vasodilatation via two pathways: (1) endothelium-independent pathway, probably due to inhibition of voltage-dependent Ca(2+) channels and intracellular Ca(2+) release; and (2) endothelium-dependent pathway by releasing NO. Both the pathways may contribute to its antihypertensive effect.

Vasorelaxant and antihypertensive effects of formononetin through endothelium-dependent and -independent mechanisms

PubMed Central

SUN, Tao; LIU, Rui; CAO, Yong-xiao

2011-01-01

Aim: To investigate the mechanisms underlying the vasorelaxant effect of formononetin, an O-methylated isoflavone, in isolated arteries, and its antihypertensive activity in vivo. Methods: Arterial rings of superior mesenteric arteries, renal arteries, cerebral basilar arteries, coronary arteries and abdominal aortas were prepared from SD rats. Isometric tension of the arterial rings was recorded using a myograph system. Arterial pressure was measured using tail-cuff method in spontaneously hypertensive rats. Results: Formononetin (1–300 μmol/L) elicited relaxation in arteries of the five regions that were pre-contracted by KCl (60 mmol/L), U46619 (1 μmol/L) or phenylephrine (10 μmol/L). The formononetin-induced relaxation was reduced by removal of endothelium or by pretreatment with L-NAME (100 μmol/L). Under conditions of endothelium denudation, formononetin (10, 30, and 100 μmol/L) inhibited the contraction induced by KCl and that induced by CaCl2 in Ca2+-free depolarized medium. In the absence of extracellular Ca2+, formononetin (10, 30, and 100 μmol/L) depressed the constriction caused by phenylephrine (10 μmol/L), but did not inhibit the tonic contraction in response to the addition of CaCl2 (2 mmol/L). The contraction caused by caffeine (30 mmol/L) was not inhibited by formononetin (100 μmol/L). Formononetin (10 and 100 μmol/L) reduced the change rate of Ca2+-fluorescence intensity in response to KCl (50 mmol/L). In spontaneously hypertensive rats, formononetin (5, 10, and 20 mg/kg) slowly lowered the systolic, diastolic and mean arterial pressure. Conclusion: Formononetin causes vasodilatation via two pathways: (1) endothelium-independent pathway, probably due to inhibition of voltage-dependent Ca2+ channels and intracellular Ca2+ release; and (2) endothelium-dependent pathway by releasing NO. Both the pathways may contribute to its antihypertensive effect. PMID:21818108

Toxicity Profile and Pharmacokinetic Study of A Phase I Low-Dose Schedule-Dependent Radiosensitizing Paclitaxel Chemoradiation Regimen for Inoperable Non-Small-Cell Lung Cancer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Yuhchyau; Pandya, Kishan J.; Feins, Richard

Purpose: We report the toxicity profile and pharmacokinetic data of a schedule-dependent chemoradiation regimen using pulsed low-dose paclitaxel for radiosensitization in a Phase I study for inoperable non-small-cell lung cancer. Methods and Materials: Paclitaxel at escalating doses of 15 mg/m{sup 2}, 20 mg/m{sup 2}, and 25 mg/m{sup 2} were infused on Monday, Wednesday, and Friday with daily chest radiation in cohorts of 6 patients. Daily radiation was delayed for maximal G2/M arrest and apoptotic effect, an observation from preclinical investigations. Plasma paclitaxel concentration was determined by high-performance liquid chromatography. Results: Dose-limiting toxicities included 3 of 18 patients with Grade 3more » pneumonitis and 3 of 18 patients with Grade 3 esophagitis. There was no Grade 4 or 5 pneumonitis or esophagitis. There was also no Grade 3 or 4 neutropenia, thrombocytopenia, anemia or neuropathy. For Dose Levels I (15 mg/m{sup 2}), II (20 mg/m{sup 2}), and III (25 mg/m{sup 2}), the mean peak plasma level was 0.23 {+-} 0.06 {mu}mol/l, 0.32 {+-} 0.05 {mu}mol/l, and 0.52 {+-} 0.14 {mu}mol/l, respectively; AUC was 0.44 {+-} 0.09 {mu}mol/l, 0.61 {+-} 0.1 {mu}mol/l, and 0.96 {+-} 0.23 {mu}mol/l, respectively; and duration of drug concentration >0.05 {mu}mol/l (t > 0.05 {mu}mol/l) was 1.6 {+-} 0.3 h, 1.9 {+-} 0.2 h, and 3.0 {+-} 0.9 h, respectively. Conclusion: Pulsed low-dose paclitaxel chemoradiation is associated with low toxicity. Pharmacokinetic data showed that plasma paclitaxel concentration >0.05 {mu}mol/l for a minimum of 1.6 h was sufficient for effective radiosensitization.« less

Final report of international comparison APMP.QM-S2.2015 of oxygen in nitrogen at 0.2 mol/mol

NASA Astrophysics Data System (ADS)

Aoki, Nobuyuki; Shimosaka, Takuya; Lin, Tsai-Yin; Liu, Hsin-Wang; Huang, Chiung-Kun; Wongjuk, Arnuttachai; Rattanasombat, Soponrat; Sinweeruthai, Ratirat; Uehara, Shinji; Aleksandrov, Vladimir

2017-01-01

This document describes the results of the supplementary comparison for oxygen in nitrogen gas mixture. The nominal amount-of-substance fraction of oxygen is 0.20 mol/mol. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

Thermal Conductivity of Alumina-Toughened Zirconia Composites

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.; Zhu, Dong-Ming

2003-01-01

10-mol% yttria-stabilized zirconia (10YSZ)-alumina composites containing 0 to 30 mol% alumina were fabricated by hot pressing at 1500 C in vacuum. Thermal conductivity of the composites, determined at various temperatures using a steady-state laser heat flux technique, increased with increase in alumina content. Composites containing 0, 5, and 10-mol% alumina did not show any change in thermal conductivity with temperature. However, those containing 20 and 30-mol% alumina showed a decrease in thermal conductivity with increase in temperature. The measured values of thermal conductivity were in good agreement with those calculated from simple rule of mixtures.

MOLECULAR GAS AND STAR FORMATION IN NEARBY DISK GALAXIES

DOE Office of Scientific and Technical Information (OSTI.GOV)

Leroy, Adam K.; Munoz-Mateos, Juan-Carlos; Walter, Fabian

2013-08-01

We compare molecular gas traced by {sup 12}CO (2-1) maps from the HERACLES survey, with tracers of the recent star formation rate (SFR) across 30 nearby disk galaxies. We demonstrate a first-order linear correspondence between {Sigma}{sub mol} and {Sigma}{sub SFR} but also find important second-order systematic variations in the apparent molecular gas depletion time, {tau}{sub dep}{sup mol}={Sigma}{sub mol}/{Sigma}{sub SFR}. At the 1 kpc common resolution of HERACLES, CO emission correlates closely with many tracers of the recent SFR. Weighting each line of sight equally, using a fixed {alpha}{sub CO} equivalent to the Milky Way value, our data yield a molecularmore » gas depletion time, {tau}{sub dep}{sup mol}={Sigma}{sub mol}/{Sigma}{sub SFR}{approx}2.2 Gyr with 0.3 dex 1{sigma} scatter, in very good agreement with recent literature data. We apply a forward-modeling approach to constrain the power-law index, N, that relates the SFR surface density and the molecular gas surface density, {Sigma}{sub SFR}{proportional_to}{Sigma}{sub mol}{sup N}. We find N = 1 {+-} 0.15 for our full data set with some scatter from galaxy to galaxy. This also agrees with recent work, but we caution that a power-law treatment oversimplifies the topic given that we observe correlations between {tau}{sub dep}{sup mol} and other local and global quantities. The strongest of these are a decreased {tau}{sub dep}{sup mol} in low-mass, low-metallicity galaxies and a correlation of the kpc-scale {tau}{sub dep}{sup mol} with dust-to-gas ratio, D/G. These correlations can be explained by a CO-to-H{sub 2} conversion factor ({alpha}{sub CO}) that depends on dust shielding, and thus D/G, in the theoretically expected way. This is not a unique interpretation, but external evidence of conversion factor variations makes this the most conservative explanation of the strongest observed {tau}{sub dep}{sup mol} trends. After applying a D/G-dependent {alpha}{sub CO}, some weak correlations between {tau}{sub dep}{sup mol} and local conditions persist. In particular, we observe lower {tau}{sub dep}{sup mol} and enhanced CO excitation associated with nuclear gas concentrations in a subset of our targets. These appear to reflect real enhancements in the rate of star formation per unit gas, and although the distribution of {tau}{sub dep} does not appear bimodal in galaxy centers, {tau}{sub dep} does appear multivalued at fixed {Sigma}{sub H2}, supporting the idea of ''disk'' and ''starburst'' modes driven by other environmental parameters.« less

Improved Model for Predicting the Free Energy Contribution of Dinucleotide Bulges to RNA Duplex Stability.

PubMed

Tomcho, Jeremy C; Tillman, Magdalena R; Znosko, Brent M

2015-09-01

Predicting the secondary structure of RNA is an intermediate in predicting RNA three-dimensional structure. Commonly, determining RNA secondary structure from sequence uses free energy minimization and nearest neighbor parameters. Current algorithms utilize a sequence-independent model to predict free energy contributions of dinucleotide bulges. To determine if a sequence-dependent model would be more accurate, short RNA duplexes containing dinucleotide bulges with different sequences and nearest neighbor combinations were optically melted to derive thermodynamic parameters. These data suggested energy contributions of dinucleotide bulges were sequence-dependent, and a sequence-dependent model was derived. This model assigns free energy penalties based on the identity of nucleotides in the bulge (3.06 kcal/mol for two purines, 2.93 kcal/mol for two pyrimidines, 2.71 kcal/mol for 5'-purine-pyrimidine-3', and 2.41 kcal/mol for 5'-pyrimidine-purine-3'). The predictive model also includes a 0.45 kcal/mol penalty for an A-U pair adjacent to the bulge and a -0.28 kcal/mol bonus for a G-U pair adjacent to the bulge. The new sequence-dependent model results in predicted values within, on average, 0.17 kcal/mol of experimental values, a significant improvement over the sequence-independent model. This model and new experimental values can be incorporated into algorithms that predict RNA stability and secondary structure from sequence.

Structural, Thermodynamic, Elastic, and Electronic Properties of α-SnS at High Pressure from First-Principles Investigations

NASA Astrophysics Data System (ADS)

Liu, Chun Mei; Xu, Chao; Duan, Man Yi

2015-10-01

SnS has potential technical applications, but many of its properties are still not well studied. In this work, the structural, thermodynamic, elastic, and electronic properties of α-SnS have been investigated by the plane wave pseudo-potential density functional theory with the framework of generalised gradient approximation. The calculated pressure-dependent lattice parameters agree well with the available experimental data. Our thermodynamic properties of α-SnS, including heat capacity CP , entropy S, and Gibbs free energy relation of -(GT -H0) curves, show similar growth trends as the experimental data. At T=298.15 K, our CP =52.31 J/mol·K, S=78.93 J/mol·K, and -(GT -H0)=12.03 J/mol all agree very well with experimental data CP =48.77 J/mol·K and 49.25 J/mol·K, S=76.78 J/mol·K, and -(GT -H0)=12.38 J/mol. The elastic constants, together with other elastic properties, are also computed. The anisotropy analyses indicate obvious elastic anisotropy for α-SnS along different symmetry planes and axes. Moreover, calculations demonstrate that α-SnS is an indirect gap semiconductor, and it transforms to semimetal with pressure increasing up to 10.2 GPa. Combined with the density of states, the characters of the band structure have been analysed in detail.

Probing phenylalanine/adenine pi-stacking interactions in protein complexes with explicitly correlated and CCSD(T) computations.

PubMed

Copeland, Kari L; Anderson, Julie A; Farley, Adam R; Cox, James R; Tschumper, Gregory S

2008-11-13

To examine the effects of pi-stacking interactions between aromatic amino acid side chains and adenine bearing ligands in crystalline protein structures, 26 toluene/(N9-methyl)adenine model configurations have been constructed from protein/ligand crystal structures. Full geometry optimizations with the MP2 method cause the 26 crystal structures to collapse to six unique structures. The complete basis set (CBS) limit of the CCSD(T) interaction energies has been determined for all 32 structures by combining explicitly correlated MP2-R12 computations with a correction for higher-order correlation effects from CCSD(T) calculations. The CCSD(T) CBS limit interaction energies of the 26 crystal structures range from -3.19 to -6.77 kcal mol (-1) and average -5.01 kcal mol (-1). The CCSD(T) CBS limit interaction energies of the optimized complexes increase by roughly 1.5 kcal mol (-1) on average to -6.54 kcal mol (-1) (ranging from -5.93 to -7.05 kcal mol (-1)). Corrections for higher-order correlation effects are extremely important for both sets of structures and are responsible for the modest increase in the interaction energy after optimization. The MP2 method overbinds the crystal structures by 2.31 kcal mol (-1) on average compared to 4.50 kcal mol (-1) for the optimized structures.

Amorphous/crystalline (A/C) thermodynamic "rules of thumb": estimating standard thermodynamic data for amorphous materials using standard data for their crystalline counterparts.

PubMed

Holland, Diane; Jenkins, H Donald Brooke

2012-05-07

Standard thermochemical data (in the form of Δ(f)H° and Δ(f)G°) are available for crystalline (c) materials but rarely for their corresponding amorphous (a) counterparts. This paper establishes correlations between the sets of data for the two material forms (where known), which can then be used as a guideline for estimation of missing data. Accordingly, Δ(f)H°(a)/kJ mol(-1) ≈ 0.993Δ(f)H°(c)/kJ mol(-1) + 12.52 (R(2) = 0.9999; n = 50) and Δ(f)G°/kJ mol(-1) ≈ 0.988Δ(f)H°(c)/kJ mol(-1) + 0.70 (R(2) = 0.9999; n = 10). Much more tentatively, we propose that S°(298)(c)/J K(-1) mol(-1) ≈ 1.084S°(298)(c)/J K(-1) mol(-1) + 6.54 (R(2) = 0.9873; n = 11). An amorphous hydrate enthalpic version of the Difference Rule is also proposed (and tested) in the form [Δ(f)H°(M(p)X(q)·nH(2)O,a) - Δ(f)H°(M(p)X(q),a)]/kJ mol(-1) ≈ Θ(Hf)n ≈ -302.0n, where M(p)X(q)·nH(2)O represents an amorphous hydrate and M(p)X(q) the corresponding amorphous anhydrous parent salt.

Enzyme architecture: optimization of transition state stabilization from a cation-phosphodianion pair.

PubMed

Reyes, Archie C; Koudelka, Astrid P; Amyes, Tina L; Richard, John P

2015-04-29

The side chain cation of R269 lies at the surface of l-glycerol 3-phosphate dehydrogenase (GPDH) and forms an ion pair to the phosphodianion of substrate dihydroxyacetone phosphate (DHAP), which is buried at the nonpolar protein interior. The R269A mutation of GPDH results in a 110-fold increase in K(m) (2.8 kcal/mol effect) and a 41,000-fold decrease in k(cat) (6.3 kcal/mol effect), which corresponds to a 9.1 kcal/mol destabilization of the transition state for GPDH-catalyzed reduction of DHAP by NADH. There is a 6.7 kcal/mol stabilization of the transition state for the R269A mutant GPDH-catalyzed reaction by 1.0 M guanidinium ion, and the transition state for the reaction of the substrate pieces is stabilized by an additional 2.4 kcal/mol by their covalent attachment at wildtype GPDH. These results provide strong support for the proposal that GPDH invests the 11 kcal/mol intrinsic phosphodianion binding energy of DHAP in trapping the substrate at a nonpolar active site, where strong electrostatic interactions are favored, and obtains a 9 kcal/mol return from stabilizing interactions between the side chain cation and transition state trianion. We propose a wide propagation for the catalytic motif examined in this work, which enables strong transition state stabilization from enzyme-phosphodianion pairs.

Modeling Biogeochemical-Physical Interactions and Carbon Flux in the Sargasso Sea (Bermuda Atlantic Time-series Study site)

NASA Technical Reports Server (NTRS)

Signorini, Sergio R.; McClain, Charles R.; Christian, James R.

2001-01-01

An ecosystem-carbon cycle model is used to analyze the biogeochemical-physical interactions and carbon fluxes in the Bermuda Atlantic Time-series Study (BATS) site for the period of 1992-1998. The model results compare well with observations (most variables are within 8% of observed values). The sea-air flux ranges from -0.32 to -0.50 mol C/sq m/yr, depending upon the gas transfer algorithm used. This estimate is within the range (-0.22 to -0.83 mol C/sq m/yr) of previously reported values which indicates that the BATS region is a weak sink of atmospheric CO2. The overall carbon balance consists of atmospheric CO2 uptake of 0.3 Mol C/sq m/yr, upward dissolved inorganic carbon (DIC) bottom flux of 1.1 Mol C/sq m/yr, and carbon export of 1.4 mol C/sq m/yr via sedimentation. Upper ocean DIC levels increased between 1992 and 1996 at a rate of approximately 1.2 (micro)mol/kg/yr, consistent with observations. However, this trend was reversed during 1997-1998 to -2.7 (micro)mol/kg/yr in response to hydrographic changes imposed by the El Nino-La Nina transition, which were manifested in the Sargasso Sea by the warmest SST and lowest surface salinity of the period (1992-1998).

Crystal structure of bis-[(phenyl-methanamine-κN)(phthalocyaninato-κ(4) N)zinc] phenyl-methan-amine tris-olvate.

PubMed

Shamsudin, Norzianah; Tan, Ai Ling; Wimmer, Franz L; Young, David J; Tiekink, Edward R T

2015-09-01

The asymmetric unit of the title compound, 2[Zn(C32H16N8)(C7H9N)]·3C7H9N, comprises two independent complex mol-ecules and three benzyl-amine solvent mol-ecules. Each complex mol-ecule features a penta-coordinated Zn(2+) ion within a square-pyramidal geometry, whereby the N5 donor set is defined by four atoms of the phthalocyaninate dianion (PC) and an N-bound benzyl-amine mol-ecule; it is the relative orientations of the latter that differentiate between the independent complex mol-ecules. The uncoordinated benzyl-amine mol-ecules display different conformations in the structure, with syn-Car-Car-Cm-N (ar = aromatic, m = methyl-ene) torsion angles spanning the range -28.7 (10) to 35.1 (14)°. In the crystal, N-H⋯N and N-H⋯π inter-actions lead to supra-molecular layers in the ab plane. The layers have a zigzag topology, have the coordinating and non-coordinating benzyl-amine mol-ecules directed to the inside, and present the essentially flat PC resides to the outside. This arrangement enables adjacent layers to associate via π-π inter-actions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593 (2) Å] so that a three-dimensional architecture is formed.

[The influence of mitomycin C and paclitaxel on the proliferation and apoptosis of human pulmonary fibroblast].

PubMed

Chen, Nan; Zhang, Jie; Xu, Min; Wang, Ting; Wang, Yu-ling; Pei, Ying-hua

2013-09-01

To observe the inhibitory effect and potential mechanism of mitomycin C and paclitaxel on the proliferation of Human Pulmonary Fibroblast in vitro. So as to providing an experimental reference for the design of drug eluting airway stents. Cell viability was measured by MTT assay after different concentrations of mitomycin C or paclitaxel varying from 10(-1)1 mol/L to 10(-4) mol/L had been applied to the fibroblasts for 24, 48 or 72 h, respectively. Cell apoptosis was assessed by flow cytometry using dual staining with annexin V-FITC and propidium iodide 48 h after administering mitomycin C or paclitaxel at a concentration of 5×10(-6), 10(-5), 5×10(-5), 10(-4), 2×10(-4) mol/L, respectively. And the morphological character of cell apoptosis was observed by Hoechst 33342 fluorescent staining. The results of MTT revealed that cell proliferation were inhibited by mitomycin C and paclitaxel at all concentrations and exposure times. Among them, the inhibitory effect of mitomycin C were weak when the concentrations were between 10(-1)1 mol/L to 10(-8) mol/L. And within this context, the inhibitory ratio didn't correspond to the elevation of the concentration or the prolongation of the exposure times.However, when the concentration were between 10(-7) mol/L to 10(-4) mol/L, the inhibitory ratio rise progressively as the elevation of the concentration at all exposure times. The inhibitory ratio were 53.52%, 60.23%, 89.81% and 96.47% respectively when cells were treated by 10(-7), 10(-6), 10(-5) mol/L and 10(-4) mol/L mitomycin C for 72 h. An apparent "threshold dose effect" was observed in the paclitaxel treated groups.It's worth noting that the inhibitory ratio was only 48.22% when the cells had already been treated by 10(-5) mol/L paclitaxel for 72 h.However, when the concentration had reached 10(-4) mol/L, the inhibitory ratio sharply climbed to 93.38% even the cells had only been treated for 24 h. And the inhibitory ratio continued to rise as time prolonged. The results of cell apoptosis were consistent with MTT.When a significant inhibitory effect were detected by MTT, remarkable cell apoptosis could be observed by flow cytometry, and typical apoptotic cell could be identified by Hoechst 33342 fluorescent staining. A certain concentration of mitomycin C or paclitaxel can inhibit Human Pulmonary Fibroblast proliferation in vitro. Both of these two drugs have potential value for the preparation of drug eluting airway stents. In order to ensure the inhibitory effect, the eluting concentration of mitomycin C and paclitaxel should not be less than 10(-7) mol/L and 10(-5) mol/L. But the eluting concentration of these two drugs should not exceed 10(-4) mol/L when both of the inhibitory ratio of these two drugs were higher than 95%.On this basis, elevating the drug concentration has little significance for improving the inhibitory effect, but increase the risk of systemic toxicity. Inducing cell apoptosis is one of the potential mechanisms of mitomycin C and paclitaxel in inhibiting cell proliferation.

A 300,000-mol-wt intermediate filament-associated protein in baby hamster kidney (BHK-21) cells.

PubMed

Yang, H Y; Lieska, N; Goldman, A E; Goldman, R D

1985-02-01

Native intermediate filament (IF) preparations from the baby hamster kidney fibroblastic cell line (BHK-21) contain a number of minor polypeptides in addition to the IF structural subunit proteins desmin, a 54,000-mol-wt protein, and vimentin, a 55,000-mol-wt protein. A monoclonal antibody was produced that reached exclusively with a high molecular weight (300,000) protein representative of these minor proteins. Immunological methods and comparative peptide mapping techniques demonstrated that the 300,000-mol-wt species was biochemically distinct from the 54,000- and 55,000-mol-wt proteins. Double-label immunofluorescence observations on spread BHK cells using this monoclonal antibody and a rabbit polyclonal antibody directed against the 54,000- and 55,000-mol-wt proteins showed that the 300,000-mol-wt species co-distributed with IF in a fibrous pattern. In cells treated with colchicine or those in the early stages of spreading, double-labeling with these antibodies revealed the co-existence of the respective antigens in the juxtanuclear cap of IF that is characteristic of cells in these physiological states. After colchicine removal, or in the late stages of cell spreading, the 300,00-mol-wt species and the IF subunits redistributed to their normal, highly coincident cytoplasmic patterns. Ultrastructural localization by the immunogold technique using the monoclonal antibody supported the light microscopic findings in that the 300,000-mol-wt species was associated with IF in the several physiological and morphological cell states investigated. The gold particle pattern was less intimately associated with IF than that defined by anti-54/55 and was one of non-uniform distribution along IF, being clustered primarily at points of proximity between IF, where an amorphous, proteinaceous material was often the labeled element. Occasionally, "bridges" of label were seen extending outward from such clusters on IF. Gold particles were infrequently bound to microtubules, microfilaments, or other cellular organelles, and when so, IF were usually contiguous. During multiple cycles of in vitro disassembly/assembly of the IF from native preparations, the 300,000-mol-wt protein remained in the fraction containing the 54,000- and 55,000-mol-wt structural subunits, whether the latter were in the soluble state or pelleted as formed filaments. In keeping with the nomenclature developed for the microtubule-associated proteins (MAPs), the acronym IFAP-300K (intermediate filament associated protein) is proposed for this molecule.

The 1:1 co-crystal of 2-bromo-naphthalene-1,4-dione and 1,8-di-hydroxy-anthracene-9,10-dione: crystal structure and Hirshfeld surface analysis.

PubMed

Tonin, Marlon D L; Garden, Simon J; Jotani, Mukesh M; Wardell, Solange M S V; Wardell, James L; Tiekink, Edward R T

2017-05-01

The asymmetric unit of the title co-crystal, C 10 H 5 BrO 2 ·C 14 H 8 O 4 [systematic name: 2-bromo-1,4-di-hydro-naphthalene-1,4-dione-1,8-dihy-droxy-9,10-di-hydro-anthracene-9,10-dione (1/1)], features one mol-ecule of each coformer. The 2-bromo-naphtho-quinone mol-ecule is almost planar [r.m.s deviation of the 13 non-H atoms = 0.060 Å, with the maximum deviations of 0.093 (1) and 0.099 (1) Å being for the Br atom and a carbonyl-O atom, respectively]. The 1,8-di-hydroxy-anthra-quinone mol-ecule is planar (r.m.s. deviation for the 18 non-H atoms is 0.022 Å) and features two intra-molecular hy-droxy-O-H⋯O(carbon-yl) hydrogen bonds. Dimeric aggregates of 1,8-di-hydroxy-anthra-quinone mol-ecules assemble through weak inter-molecular hy-droxy-O-H⋯O(carbon-yl) hydrogen bonds. The mol-ecular packing comprises stacks of mol-ecules of 2-bromo-naphtho-quinone and dimeric assembles of 1,8-di-hydroxy-anthra-quinone with the shortest π-π contact within a stack of 3.5760 (9) Å occurring between the different rings of 2-bromo-naphtho-quinone mol-ecules. The analysis of the Hirshfeld surface reveals the importance of the inter-actions just indicated but, also the contribution of additional C-H⋯O contacts as well as C=O⋯π inter-actions to the mol-ecular packing.

Leaf water use efficiency of C{sub 4} plants grown at glacial to elevated CO{sub 2} concentrations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Polley, H.W.; Johnson, H.B.; Mayeux, H.S.

1995-09-01

Leaf gas exchange and stable carbon isotope compositions were measured on C{sub 4} species grown from near glacial to current CO{sub 2} concentrations (200 to 350 {mu}mol/mol) and from the current concentration to levels possible in the future (700 and 1000 {mu}mol/mol) to determine effects of rising CO{sub 2} on intrinsic water use efficiency (CO{sub 2} assimilation, A/stomatal conductance to water, g) of C{sub 4} plants. The increase in A/g was proportionally greater than that in CO{sub 2} from near glacial to present concentrations in the perennial grass Schizachyrium scoparium and, in one of two years, in the annual grassmore » Zea mays, because of a corresponding decrease in the ratio of leaf intercellular (c{sub i}) to external CO{sub 2} concentration (c{sub a}). Leaf A/g increased 66% in S. scoparium and 80% in the perennial shrub Atriplex canescens from 350 to 700 {mu}mol/mol CO{sub 2}, but averaged across species declined 15% from 700 to 1000 {mu}mol/mol because of an accompanying increase in c{sub i}/c{sub a}. At each CO{sub 2} level, A/g was higher in the grass than shrub. There were substantial differences in A/g at a given CO{sub 2} concentration and in the response of A/g to CO{sub 2} among the species examined. Because much of the positive response of C{sub 4} plants to CO{sub 2} derives from higher water use efficiency, these differences could influence the relative productivities of C{sub 4} species.« less

Comparison of two pre-exposure treatment regimens in acute organophosphate (paraoxon) poisoning in rats: Tiapride vs. pyridostigmine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Petroianu, G.A.; Hasan, M.Y.; Nurulain, S.M.

Recently, the FDA approved the medical use of oral pyridostigmine as prophylactic treatment of possible nerve agent exposure: the concept is to block the cholinesterase transitorily using the carbamate (pyridostigmine) in order to deny access to the active site of the enzyme to the irreversible inhibitor (nerve agent) on subsequent exposure. We have shown previously that tiapride is in vitro a weak inhibitor of acetylcholinesterase and that in rats administration of tiapride before the organophosphate paraoxon significantly decreases mortality. The purpose of the present study was to compare tiapride- and pyridostigmine-based pretreatment strategies, either alone or in combination with pralidoximemore » reactivation, by using a prospective, non-blinded study in a rat model of acute high-dose paraoxon exposure. Groups 1-6 received 1 {mu}Mol paraoxon ({approx} LD{sub 75}) groups 2-6 received in addition: G{sub 2} 50 {mu}Mol tiapride 30 min before paraoxon; G{sub 3} 50 {mu}Mol tiapride 30 min before paraoxon and 50 {mu}Mol pralidoxime 1 min after paraoxon; G{sub 4} 1 {mu}Mol pyridostigmine 30 min before paraoxon; G{sub 5} 1 {mu}Mol pyridostigmine 30 min before paraoxon and 50 {mu}Mol pralidoxime 1 min after paraoxon; G{sub 6} 50 {mu}Mol pralidoxime 1 min after paraoxon; Mortality data were compared using Kaplan-Meier plots and logrank tests. Mortality is statistically significantly influenced by all treatment strategies. Tiapride pretreatment followed by pralidoxime treatment (G{sub 3}) is aux par with pyridostigmine pretreatment followed by pralidoxime treatment (G{sub 5}). Tiapride pretreatment only (G{sub 2}) is inferior to pyridostigmine pretreatment only (G{sub 4}). The best results are achieved with pyridostigmine pretreatment only or pralidoxime treatment only (G{sub 4} and G{sub 6})« less

Crystal structure of 3-[(4-benzyl-piperazin-1-yl)meth-yl]-5-(thio-phen-2-yl)-2,3-di-hydro-1,3,4-oxa-diazole-2-thione.

PubMed

Al-Omary, Fatmah A M; El-Emam, Ali A; Ghabbour, Hazem A; Chidan Kumar, C S; Quah, Ching Kheng; Fun, Hoong-Kun

2015-03-01

The title 1,3,4-oxa-diazole-2-thione derivative, C18H20N4OS2, crystallized with two independent mol-ecules (A and B) in the asymmetric unit. The 2-thienyl rings in both mol-ecules are rotationally disordered over two orientations by approximately 180° about the single C-C bond that connects it to the oxa-diazole thione ring; the ratios of site occupancies for the major and minor components were fixed in the structure refinement at 0.8:0.2 and 0.9:0.1 in mol-ecules A and B, respectively. The 1,3,4-oxa-diazole-2-thione ring forms dihedral angles of 7.71 (16), 10.0 (11) and 77.50 (12)° (mol-ecule A), and 6.5 (3), 6.0 (9) and 55.30 (12)° (mol-ecule B) with the major and minor parts of the disordered thio-phene ring and the mean plane of the adjacent piperazine ring, respectively, resulting in approximately V-shaped conformations for the mol-ecules. The piperazine ring in both mol-ecules adopts a chair conformation. The terminal benzene ring is inclined towards the mean plane of the piperazine ring with N-C-C-C torsion angles of -58.2 (3) and -66.2 (3)° in mol-ecules A and B, respectively. In the crystal, no inter-molecular hydrogen bonds are observed. The crystal packing features short S⋯S contacts [3.4792 (9) Å] and π-π inter-actions [3.661 (3), 3.664 (11) and 3.5727 (10) Å], producing a three-dimensional network.

Amine binding and oxidation at the catalytic site for photosynthetic water oxidation

PubMed Central

Ouellette, Anthony J. A.; Anderson, Lorraine B.; Barry, Bridgette A.

1998-01-01

Photosynthetic water oxidation occurs at the Mn-containing catalytic site of photosystem II (PSII). By the use of 14C-labeled amines and SDS-denaturing PAGE, covalent adducts derived from primary amines and the PSII subunits, CP47, D2/D1, and the Mn-stabilizing protein, can be observed. When PSII contains the 18- and 24-kDa extrinsic proteins, which restrict access to the active site, no 14C labeling is obtained. NaCl, but not Na2SO4, competes with 14C labeling in Mn-containing PSII preparations, and the concentration dependence of this competition parallels the activation of oxygen evolution. Formation of 14C-labeled adducts is observed in the presence or in the absence of a functional manganese cluster. However, no significant Cl− effect on 14C labeling is observed in the absence of the Mn cluster. Isolation and quantitation of the 14C-labeled aldehyde product, produced from [14C]benzylamine, gives yields of 1.8 ± 0.3 mol/mol PSII and 2.9 ± 0.2 mol/mol in Mn-containing and Mn-depleted PSII, respectively. The corresponding specific activities are 0.40 ± 0.07 μmol(μmol PSII-hr)−1 and 0.64 ± 0.04 μmol(μmol PSII-hr)−1. Cl− suppresses the production of [14C]benzaldehyde in Mn-containing PSII, but does not suppress the production in Mn-depleted preparations. Control experiments show that these oxidation reactions do not involve the redox-active tyrosines, D and Z. Our results suggest the presence of one or more activated carbonyl groups in protein subunits that form the active site of PSII. PMID:9482863

Apparent bioavailability of isoflavones after intake of liquid and solid soya foods

PubMed Central

Franke, Adrian A.; Ashburn, Leslie A.; Kakazu, Kerry; Suzuki, Shana; Wilkens, Lynne R.; Halm, Brunhild M.

2015-01-01

Isoflavone (IFL) intake may provide numerous health benefits, but IFL bioavailability differences among soya foods remains uncertain. Urinary IFL excretion (UIE) was shown to provide a reliable surrogate for systemic IFL exposure and therefore can be used as a measure of ‘apparent bioavailability’ (AB). We investigated the AB of IFL in fourteen healthy adults, consuming two liquid and two solid soya foods in a crossover designed study. Volunteers consumed the foods with a self-selected breakfast, which was kept identical for all four soya items (soya nuts, soya milk, soya protein bar and soya protein powder drink in water; average 23·7 mg IFL, 88–96 % glycosides, by HPLC analysis) and collected all urine up to 26 h. Liquid foods showed initially higher UIE values than solid foods, but this difference was considerably reduced or disappeared entirely after 24–26 h. Conclusive AB results were obtained only after 24–26 h; earlier collections were not reliable. At 26 h, adjusted UIE values for daidzein (DE) were 20 μmol in the milk and bar and 17 μmol for the nut and powder; urinary genistein excretion was the highest in the milk group (10 μmol) followed by the nut, bar (both 6 μmol) and powder groups (5 μmol); the UIE for glycitein was the highest for bars (4 μmol), followed by powder and nuts (3 μmol), and milk (2 μmol). DE makes the largest contribution to urinary total IFL. The AB of IFL was found to be variable depending on the analyte and soya food consumed. PMID:19450369

Archaeal Production of Polyhydroxyalkanoate (PHA) Co- and Terpolyesters from Biodiesel Industry-Derived By-Products

PubMed Central

Hermann-Krauss, Carmen; Koller, Martin; Stelzer, Franz; Braunegg, Gerhart

2013-01-01

The archaeon Haloferax mediterranei was selected for production of PHA co- and terpolyesters using inexpensive crude glycerol phase (CGP) from biodiesel production as carbon source. CGP was assessed by comparison with the application of pure glycerol. Applying pure glycerol, a copolyester with a molar fraction of 3-hydroxybutyrate (3HB) of 0.90 mol/mol and 3-hydroxyvalerate (3HV) of 0.10 mol/mol, was produced at a volumetric productivity of 0.12 g/Lh and an intracellular PHA content of 75.4 wt.-% in the sum of biomass protein plus PHA. Application of CGP resulted in the same polyester composition and volumetric productivity, indicating the feasibility of applying CGP as feedstock. Analysis of molar mass distribution revealed a weight average molar mass M w of 150 kDa and polydispersity P i of 2.1 for pure glycerol and 253 kDa and 2.7 for CGP, respectively; melting temperatures ranged between 130 and 140°C in both setups. Supplying γ-butyrolactone as 4-hydroxybutyrate (4HB) precursor resulted in a poly[(R)-3-hydroxybutyrate-co-(R)-3-hydroxyvalerate-co-4-hydroxybutyrate] (PHBHV4HB) terpolyester containing 3HV (0.12 mol/mol) and 4HB (0.05 mol/mol) in the poly[(R)-3-hydroxybutyrate] (PHB) matrix; in addition, this process runs without sterilization of the bioreactor. The terpolyester displayed reduced melting (melting endotherms at 122 and 137°C) and glass transition temperature (2.5°C), increased molar mass (391 kDa), and a polydispersity similar to the copolyesters. PMID:24453697

Comparative evaluation of neonatal bilirubin using Radiometer whole blood co-oximetry and plasma bilirubin methods from Roche Diagnostics and Ortho Clinical Diagnostics.

PubMed

Lano, Ian Marie; Lyon, Andrew W; Wang, Li; Ruskin, Rob; Lyon, Martha E

2018-03-01

Clinically significant variation has been reported within and between plasma and whole blood total bilirubin methods used to identify neonates for whom clinical intervention for hyperbilirubinemia may be required. To evaluate total bilirubin measurements between the Radiometer whole blood co-oximeter and plasma bilirubin methods from Roche Diagnostics and Ortho Clinical Diagnostics using neonatal specimens. Total bilirubin levels were analyzed by whole blood co-oximetry (Radiometer® ABL90). Specimens were centrifuged and plasma analyzed for total bilirubin with a diazo method (Roche Cobas® C-601) and a reflectance spectrophotometric BuBc dry film method (Ortho Clinical Diagnostics VITROS® 350). Results were evaluated by regression, Bland-Altman comparisons and t-tests. The patient correlation study yielded the following regression equations in μmol/L: a) Radiometer=1.03 Roche - 3.5μmol/L b) Radiometer=0.98 Ortho - 5.7μmol/L c) Roche=0.97 Ortho - 2.4μmol/L. The mean bias over the range of total bilirubin levels examined was -1.0μmol/L for the Radiometer versus the Roche (p≤0.305); -4.4μmol/L for the Radiometer versus Ortho (p≤0.005) and -4.4μmol/L for the Roche versus Ortho (p≤0.002). Whole blood total bilirubin measurement using the Radiometer ABL90 blood gas analyzer provides accurate and precise results compared to the Roche plasma diazo method. Compared to the reflectance spectrophotometric method, results are precise and had a small but statistically significant bias of -4.4μmol/L. Copyright © 2017 The Canadian Society of Clinical Chemists. Published by Elsevier Inc. All rights reserved.

Adjusting irradiance to enhance growth and lipid production of Chlorella vulgaris cultivated with monosodium glutamate wastewater.

PubMed

Jiang, Liqun; Ji, Yan; Hu, Wenrong; Pei, Haiyan; Nie, Changliang; Ma, Guixia; Song, Mingming

2016-09-01

Light is one of the most important factors affecting microalgae growth and biochemical composition. The influence of illumination on Chlorella vulgaris cultivated with diluted monosodium glutamate wastewater (MSGW) was investigated. Six progressive illumination intensities (0, 30, 90, 150, 200 and 300μmol·m(-2)s(-1)), were used for C. vulgaris cultivation at 25°C. Under 150μmol·m(-2)s(-1), the corresponding specific light intensity of 750×10(-6)μmol·m(-2)s(-1) per cell, algae obtained the maximum biomass concentration (1.46g·L(-1)) on the 7th day, which was 3.5 times of that under 0μmol·m(-2)s(-1), and the greatest average specific growth rate (0.79 d(-1)) in the first 7days. The results showed the importance role of light in mixotrophic growth of C. vulgaris. High light intensities of 200 and 300μmol·m(-2)s(-1) would inhibit microalgae growth to a certain degree. The algal lipid content was the greatest (30.5%) at 150μmol·m(-2)s(-1) light intensity, which was 2.42 times as high as that cultured in dark. The protein content of C. vulgaris decreased at high light intensities of 200 and 300μmol·m(-2)s(-1). The effect of irradiance on carbohydrate content was inversely correlated with that on protein. The available light at an appropriate intensity, not higher than 200μmol·m(-2)s(-1), was feasible for economical cultivation of C. vulgaris in MSGW. Copyright © 2016 Elsevier B.V. All rights reserved.

Drug targeted virtual screening and molecular dynamics of LipU protein of Mycobacterium tuberculosis and Mycobacterium leprae.

PubMed

Kaur, Gurkamaljit; Pandey, Bharati; Grover, Arbind; Garewal, Naina; Grover, Abhinav; Kaur, Jagdeep

2018-03-30

The lipolytic protein LipU was conserved in mycobacterium sp. including M. tuberculosis (MTB LipU) and M. leprae (MLP LipU). The MTB LipU was identified in extracellular fraction and was reported to be essential for the survival of mycobacterium. Therefore to address the problem of drug resistance in pathogen, LipU was selected as a drug target and the viability of finding out some FDA approved drugs as LipU inhibitors in both the cases was explored. Three-dimensional (3D) model structures of MTB LipU and MLP LipU were generated and stabilized through molecular dynamics (MD). FDA approved drugs were screened against these proteins. The result showed that the top-scoring compounds for MTB LipU were Diosmin, Acarbose and Ouabain with the Glide XP score of -12.8, -11.9 and -11.7 kcal/mol, respectively, whereas for MLP LipU protein, Digoxin (-9.2 kcal/mol), Indinavir (-8.2 kcal/mol) and Travoprost (-8.2 kcal/mol) showed highest affinity. These drugs remained bound in the active site pocket of MTB LipU and MLP LipU structure and interaction grew stronger after dynamics. RMSD, RMSF and Rg were found to be persistent throughout the simulation period. Hydrogen bonds along with large number of hydrophobic interactions stabilized the complex structures. Binding free energies obtained through Prime/MM-GBSA were found in the significant range from -63.85 kcal/mol to -34.57 kcal/mol for MTB LipU and -71.33 kcal/mol to -23.91 kcal/mol for MLP LipU. The report suggested high probability of these drugs to demolish the LipU activity and could be probable drug candidates to combat TB and leprosy disease.

The temperature-dependence of adenylate cyclase from baker's yeast.

PubMed Central

Londesborough, J; Varimo, K

1979-01-01

The Michaelis constant of membrane-bound adenylate cyclase increased from 1.1 to 1.8 mM between 7 and 38 degrees C (delta H = 13 kJ/mol). Over this temperature range, the maximum velocity increased 10-fold, and the Arrhenius plot was nearly linear, with an average delta H* of 51 kJ/mol. The temperature-dependence of the reaction rate at 2 mM-ATP was examined in more detail: for Lubrol-dispersed enzyme, Arrhenius plots were nearly linear with average delta H* values of 45 and 68 kJ/mol, respectively, for untreated and gel-filtered enzymes; for membrane-bound enzyme, delta H changed from 40 kJ/mol above about 21 degrees C to 62 kJ/mol below 21 degrees C, but this behaviour does not necessarily indicate an abrupt, lipid-induced, transition in the reaction mechanism. PMID:391221

Crystal structure of 3-hy-droxy-methyl-1,2,3,4-tetra-hydro-isoquinolin-1-one.

PubMed

Caracelli, Ignez; Hino, Camila Lury; Zukerman-Schpector, Julio; Biaggio, Francisco Carlos; Tiekink, Edward R T

2015-08-01

In the title compound, C10H11NO2, two independent but virtually superimposable mol-ecules, A and B, comprise the asymmetric unit. The heterocyclic ring in each mol-ecule has a screw-boat conformation, and the methyl-hydroxyl group occupies a position to one side of this ring with N-C-C-O torsion angles of -55.30 (15) (mol-ecule A) and -55.94 (16)° (mol-ecule B). In the crystal, O-H⋯O and N-H⋯O hydrogen bonding leads to 11-membered {⋯HNCO⋯HO⋯HNC2O} heterosynthons, involving three different mol-ecules, which are edge-shared to generate a supra-molecular chain along the a axis. Inter-actions of the type C-H⋯O provide additional stability to the chains, and link these into a three-dimensional architecture.

Purification and characterization of NADPH--cytochrome c reductase from the midgut of the southern armyworm (Spodoptera eridania).

PubMed

Crankshaw, D L; Hetnarski, K; Wilkinson, C F

1979-09-01

1. NADPH-cytochrome c reductase was solubilized with bromelain and purified about 400-fold from sucrose/pyrophosphate-washed microsomal fractions from southern armyworm (Spodoptera eridania) larval midguts. 2. The enzyme has a mol.wt. of 70 035 +/- 1300 and contained 2 mol of flavin/mol of enzyme consisting of almost equimolar amounts of FMN and FAD. 3. Aerobic titration of the enzyme with NADPH caused the formation of a stable half-reduced state at 0.5 mol of NADPH/mol of flavin. 4. Kinetic analysis showed that the reduction of cytochrome c proceeded by a Bi Bi Ping Pong mechanism. 5. Apparent Km values for NADPH and cytochrome c and Ki values for NADP+ and 2'-AMP were considerably higher for the insect reductase than for the mammalian liver enzyme. 6. These are discussed in relation to possible differences in the active sites of the enzymes.

N-(1-Allyl-1H-indazol-5-yl)-4-methyl-benzene-sulfonamide.

PubMed

Chicha, Hakima; Rakib, El Mostapha; Abderrafia, Hafid; Saadi, Mohamed; El Ammari, Lahcen

2013-11-30

The asymmetric unit of the title compound, C17H17N3O2S, contains two independent mol-ecules linked by an N-H⋯O hydrogen bond. The mol-ecules show different conformations. In the first mol-ecule, the fused five- and six-membered ring system is almost perpendicular to the plane through the atoms forming the allyl group, as indicated by the dihedral angle of 85.1 (4)°. The dihedral angle with the methyl-benzene-sulfonamide group is 78.8 (1)°. On the other hand, in the second mol-ecule, the dihedral angles between the indazole plane and the allyl and methyl-benzene-sulfonamide groups are 80.3 (3) and 41.5 (1)°, respectively. In the crystal, mol-ecules are further linked by N-H⋯N and C-H⋯O hydrogen bonds, forming a three-dimensional network.

The Effects of Spark-Plasma Sintering (SPS) on the Microstructure and Mechanical Properties of BaTiO3/3Y-TZP Composites

PubMed Central

Li, Jing; Cui, Bencang; Wang, Huining; Lin, Yuanhua; Deng, Xuliang; Li, Ming; Nan, Cewen

2016-01-01

Composite ceramics BaTiO3/3Y-TZP containing 0 mol %, 3 mol %, 5 mol %, 7 mol %, and 10 mol % BaTiO3 have been prepared by conventional sintering and spark-plasma sintering (SPS), respectively. Analysis of the XRD patterns and Raman spectra reveal that the phase composition of t-ZrO2, m-ZrO2, and BaTiO3 has been obtained. Our results indicate that SPS can be effective for the decrease in grain size and porosity compared with conventional sintering, which results in a lower concentration of m-ZrO2 and residual stress. Therefore, the fracture toughness is enhanced by the BaTiO3 phase through the SPS technique, while the behavior was impaired by the piezoelectric second phase through conventional sintering. PMID:28773445

[Influence of wall polymer and preparation process on the particle size and encapsulation of hemoglobin microcapsules].

PubMed

Qiu, Wei; Ma, Guang-Hui; Meng, Fan-Tao; Su, Zhi-Guo

2004-03-01

Methoxypoly (ethylene glycol)- block-poly (DL-lactide) (PELA) microcapsules containing bovine hemoglobin (BHb) were prepared by a W/O/W double emulsion-solvent diffusion process. The P50 and Hill coeffcient were 3466 Pa and 2.4 respectively, which were near to the natural bioactivity of bovine hemoglobin. The results suggested that polymer composition had significant influence on encapsulation efficiency and particle size of microcapsules. The encapsulation efficiency could reach 90% and the particle size 3 - 5 microm when the PELA copolymer containing MPEG 2000 block was used. The encapsulation efficiency and particle size increased with the concentration of PELA. Increasing the concentrations of NaCl in outer aqueous solution resulted in the increase of encapsulation efficiency and the decrease of particle size. As the concentration of stabilizer in outer aqueous solution increased in the range of 10 g/L to 20 g/L, the particle size reduced while encapsulation efficiency was increased, further increase of the stabilizer concentration would decrease encapsulation efficiency. Increasing of primary emulsion stirring rate was advantageous to the improvement of encapsulation efficiency though it had little influence on the particle size. The influence of re-emulsion stirring rate was complicated, which was not apparent in the case of large volume of re-emulsion solution. When the wall polymer and primary emulsion stirring rate were fixed, the encapsulation efficiency decreased as the particle size reduced.

40 CFR 1065.750 - Analytical gases.

Code of Federal Regulations, 2014 CFR

2014-07-01

... recommend using a balance gas of purified nitrogen. (v) FID CH 4 span gas. If you always span and calibrate....41) mol/mol, balance He or N2, and a stated total hydrocarbon concentration of 0.05 µmol/mol or less. For GC-FIDs that measure methane (CH4) using a FID fuel that is balance N2, perform the CH4...

N-(3-Chloro-1-methyl-1H-indazol-5-yl)-4-methylbenzene-sulfonamide.

PubMed

Chicha, Hakima; Rakib, El Mostapha; Amiri, Ouafa; Saadi, Mohamed; El Ammari, Lahcen

2014-02-01

The asymmetric unit of the title compound, C15H14ClN3O2S, contains two independent mol-ecules showing different conformations: in one mol-ecule, the indazole ring system makes a dihedral angle of 51.5 (1)° with the benzene ring whereas in the other, the indazole unit is almost perpendicular to the benzene ring [dihedral angle 77.7 (1)°]. In the crystal, the mol-ecules are linked by N-H⋯N and N-H⋯O hydrogen bonds, forming a set of four mol-ecules linked in pairs about an inversion centre.

3-Amino­benzoic acid–1,2-bis­(4-pyrid­yl)ethane (1/1)

PubMed Central

Shen, Fwu Ming; Lush, Shie Fu

2010-01-01

The asymmetric unit of the title compound, C12H12N2·C7H7NO2, contains two 3-amino­benzoic acid mol­ecules and two 1,2-bis­(4-pyrid­yl)ethane mol­ecules. In the two 1,2-bis­(4-pyrid­yl)ethane mol­ecules, the dihedral angles between the pyridyl rings are 2.99 (9) and 46.78 (8)°. In the crystal, the mol­ecules associate through amine and carboxyl group N—H⋯O=C inter­actions between one of the 3-amino­benzoic acid mol­ecules and one of the 1,2-bis­(4-pyrid­yl)ethane mol­ecules, generating R 2 2(14) dimers, which are extended head-to-tail via amine and pyridine N—H⋯N hydrogen bonds. Inter­molecular O—H⋯N, N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonding are observed in the crystal structure. C—H⋯π and π–π stacking inter­actions [centroid–centroid distance = 3.9985 (10) Å] are also present. PMID:21579186

Virtual screening using MTiOpenScreen and PyRx 0,8 revealed ZINC95486216 as a human acetylcholinesterase inhibitor candidate

NASA Astrophysics Data System (ADS)

Sulistyo Dwi K., P.; Arindra Trisna, W.; Vindri Catur P., W.; Wijayanti, Erna; Ichsan, Mochammad

2016-03-01

One of the efforts to prevent Alzheimer's disease becomes more severe is by inhibiting the activity of Human acetylcholinesterase enzyme (PDB ID: 4BDT). In this study, virtual screening againts 885 natural compounds from AfroDB has been done using MTIOpenScreen and this step has been successful in identifying ZINC15121024 (-12,9) and ZINC95486216 (-12,7) as the top rank compounds. This data then strengthened by the results of second docking step using Autodock software that has been integrated in PyRx 0.8 software. From this stage, ZINC95486216 (-11,3 kcal/mol) is a compound with the most negative binding affinity compared with four Alzheimer's drugs that have been officially used to date including Rivastigmine (-6,3 Kcal/mol), Donepenzil (-7.9 kcal/mol), Galantamine (-8.4 kcal/mol), and Huprine W (-7.3 kcal/mol). In addition, based on the results of the 2D and 3D visualization using LigPlus and PyMol softwares, respectively, known that the five compounds above are equally capable of binding to several amino acids (Trp 286, Phe295, and Tyr341) located in the active site of Human Acetylcholinesterase enzyme.

Modification of mature non-reducible collagen cross-link concentrations in bovine m. gluteus medius and semitendinosus with steer age at slaughter, breed cross and growth promotants.

PubMed

Roy, B C; Sedgewick, G; Aalhus, J L; Basarab, J A; Bruce, H L

2015-12-01

Increased meat toughness with animal age has been attributed to mature trivalent collagen cross-link formation. Intramuscular trivalent collagen cross-link content may be decreased by reducing animal age at slaughter and/or inducing muscle re-modeling with growth promotants. This hypothesis was tested in m. gluteus medius (GM) and m. semitendinosus (ST) from 112 beef steers finished at either 12 to 13 (rapid growth) or 18 to 20 (slow growth) months of age. Hereford-Aberdeen Angus (HAA) or Charolais-Red Angus (CRA) steers were randomly assigned to receive implants (IMP), ractopamine (RAC), both IMP and RAC, or none (control). RAC decreased pyridinoline (mol/mol collagen) and IMP increased Ehrlich chromogen (EC) (mol/mol collagen) in the GM. In the ST, RAC increased EC (mol/mol collagen) but decreased EC (nmol/g raw muscle) in slow growing CRA steers. Also, IMP increased ST pyridinoline (nmol/g raw muscle) of slow-growing HAA steers. Results indicated alteration of perimysium collagen cross-links content in muscle in response to growth promotants. Copyright © 2015 Elsevier Ltd. All rights reserved.

Crystal structure of fac-tri-carbonyl-chlorido-bis-(4-hy-droxy-pyridine)-rhenium(I)-pyridin-4(1H)-one (1/1).

PubMed

Argibay-Otero, Saray; Carballo, Rosa; Vázquez-López, Ezequiel M

2017-10-01

The asymmetric unit of the title compound, [ReCl(C 5 H 5 NO) 2 (CO) 3 ]·C 5 H 5 NO, contains one mol-ecule of the complex fac -[ReCl(4-pyOH) 2 (CO) 3 ] (where 4-pyOH represents 4-hy-droxy-pyridine) and one mol-ecule of pyridin-4(1 H )-one (4-HpyO). In the mol-ecule of the complex, the Re atom is coordinated to two N atoms of the two 4-pyOH ligands, three carbonyl C atoms, in a facial configuration, and the Cl atom. The resulting geometry is slightly distorted octa-hedral. In the crystal structure, both fragments are associated by hydrogen bonds; two 4-HpyO mol-ecules bridge between two mol-ecules of the complex using the O=C group as acceptor for two different HO- groups of coordinated 4-pyOH from two neighbouring metal complexes. The resulting square arrangements are extented into infinite chains by hydrogen bonds involving the N-H groups of the 4-HpyO mol-ecule and the chloride ligands. The chains are further stabilized by π-stacking inter-actions.

Non-covalent binding analysis of sulfamethoxazole to human serum albumin: Fluorescence spectroscopy, UV-vis, FT-IR, voltammetric and molecular modeling.

PubMed

Naik, Praveen N; Nandibewoor, Sharanappa T; Chimatadar, Shivamurthi A

2015-06-01

This study was designed to examine the interaction of sulfamethoxazole (SMZ) with human serum albumin(HSA). Spectroscopic analysis of the emission quenching at different temperatures revealed that the quenching mechanism of human serum albumin by SMZ was static mechanism. The binding constant values for the SMZ-HSA system were obtained to be 22,500 L/mol at 288 K, 15,600 L/mol at 298 K, and 8500 L/mol at 308 K. The distance r between donor and acceptor was evaluated according to the theory of Föster energy transfer. The results of spectroscopic analysis and molecular modeling techniques showed that the conformation of human serum albumin had been changed in the presence of SMZ. The thermodynamic parameters, namely enthalpy change (∆ H 0 ) -36.0 kJ/mol, entropy change (∆ S 0 ) -41.3 J/mol K and free energy change (∆ G 0 ) -23.7 kJ/mol, were calculated by using van׳t Hoff equation. The effect of common ions on the binding of SMZ to HSA was tested.

MolTalk – a programming library for protein structures and structure analysis

PubMed Central

Diemand, Alexander V; Scheib, Holger

2004-01-01

Background Two of the mostly unsolved but increasingly urgent problems for modern biologists are a) to quickly and easily analyse protein structures and b) to comprehensively mine the wealth of information, which is distributed along with the 3D co-ordinates by the Protein Data Bank (PDB). Tools which address this issue need to be highly flexible and powerful but at the same time must be freely available and easy to learn. Results We present MolTalk, an elaborate programming language, which consists of the programming library libmoltalk implemented in Objective-C and the Smalltalk-based interpreter MolTalk. MolTalk combines the advantages of an easy to learn and programmable procedural scripting with the flexibility and power of a full programming language. An overview of currently available applications of MolTalk is given and with PDBChainSaw one such application is described in more detail. PDBChainSaw is a MolTalk-based parser and information extraction utility of PDB files. Weekly updates of the PDB are synchronised with PDBChainSaw and are available for free download from the MolTalk project page following the link to PDBChainSaw. For each chain in a protein structure, PDBChainSaw extracts the sequence from its co-ordinates and provides additional information from the PDB-file header section, such as scientific organism, compound name, and EC code. Conclusion MolTalk provides a rich set of methods to analyse and even modify experimentally determined or modelled protein structures. These methods vary in complexity and are thus suitable for beginners and advanced programmers alike. We envision MolTalk to be most valuable in the following applications: 1) To analyse protein structures repetitively in large-scale, i.e. to benchmark protein structure prediction methods or to evaluate structural models. The quality of the resulting 3D-models can be assessed by e.g. calculating a Ramachandran-Sasisekharan plot. 2) To quickly retrieve information for (a limited number of) macro-molecular structures, i.e. H-bonds, salt bridges, contacts between amino acids and ligands or at the interface between two chains. 3) To programme more complex structural bioinformatics software and to implement demanding algorithms through its portability to Objective-C, e.g. iMolTalk. 4) To be used as a front end to databases, e.g. PDBChainSaw. PMID:15096277

An accurate and efficient computational protocol for obtaining the complete basis set limits of the binding energies of water clusters at the MP2 and CCSD(T) levels of theory: Application to (H₂O) m, m=2-6, 8, 11, 16 and 17

DOE Office of Scientific and Technical Information (OSTI.GOV)

Miliordos, Evangelos; Xantheas, Sotiris S.

2015-06-21

We report MP2 and CCSD(T) binding energies with basis sets up to pentuple zeta quality for the m = 2-6, 8 clusters. Or best CCSD(T)/CBS estimates are -4.99 kcal/mol (dimer), -15.77 kcal/mol (trimer), -27.39 kcal/mol (tetramer), -35.9 ± 0.3 kcal/mol (pentamer), -46.2 ± 0.3 kcal/mol (prism hexamer), -45.9 ± 0.3 kcal/mol (cage hexamer), -45.4 ± 0.3 kcal/mol (book hexamer), -44.3 ± 0.3 kcal/mol (ring hexamer), -73.0 ± 0.5 kcal/mol (D 2d octamer) and -72.9 ± 0.5 kcal/mol (S4 octamer). We have found that the percentage of both the uncorrected (dimer) and BSSE-corrected (dimer CP e) binding energies recovered with respectmore » to the CBS limit falls into a narrow range for each basis set for all clusters and in addition this range was found to decrease upon increasing the basis set. Relatively accurate estimates (within < 0.5%) of the CBS limits can be obtained when using the “ 2/3, 1/3” (for the AVDZ set) or the “½ , ½” (for the AVTZ, AVQZ and AV5Z sets) mixing ratio between dimer e and dimer CPe. Based on those findings we propose an accurate and efficient computational protocol that can be used to estimate accurate binding energies of clusters at the MP2 (for up to 100 molecules) and CCSD(T) (for up to 30 molecules) levels of theory. This work was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences. Pacific Northwest National Laboratory (PNNL) is a multi program national laboratory operated for DOE by Battelle. This research also used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. AC02-05CH11231.« less

MolTalk--a programming library for protein structures and structure analysis.

PubMed

Diemand, Alexander V; Scheib, Holger

2004-04-19

Two of the mostly unsolved but increasingly urgent problems for modern biologists are a) to quickly and easily analyse protein structures and b) to comprehensively mine the wealth of information, which is distributed along with the 3D co-ordinates by the Protein Data Bank (PDB). Tools which address this issue need to be highly flexible and powerful but at the same time must be freely available and easy to learn. We present MolTalk, an elaborate programming language, which consists of the programming library libmoltalk implemented in Objective-C and the Smalltalk-based interpreter MolTalk. MolTalk combines the advantages of an easy to learn and programmable procedural scripting with the flexibility and power of a full programming language. An overview of currently available applications of MolTalk is given and with PDBChainSaw one such application is described in more detail. PDBChainSaw is a MolTalk-based parser and information extraction utility of PDB files. Weekly updates of the PDB are synchronised with PDBChainSaw and are available for free download from the MolTalk project page http://www.moltalk.org following the link to PDBChainSaw. For each chain in a protein structure, PDBChainSaw extracts the sequence from its co-ordinates and provides additional information from the PDB-file header section, such as scientific organism, compound name, and EC code. MolTalk provides a rich set of methods to analyse and even modify experimentally determined or modelled protein structures. These methods vary in complexity and are thus suitable for beginners and advanced programmers alike. We envision MolTalk to be most valuable in the following applications:1) To analyse protein structures repetitively in large-scale, i.e. to benchmark protein structure prediction methods or to evaluate structural models. The quality of the resulting 3D-models can be assessed by e.g. calculating a Ramachandran-Sasisekharan plot.2) To quickly retrieve information for (a limited number of) macro-molecular structures, i.e. H-bonds, salt bridges, contacts between amino acids and ligands or at the interface between two chains.3) To programme more complex structural bioinformatics software and to implement demanding algorithms through its portability to Objective-C, e.g. iMolTalk.4) To be used as a front end to databases, e.g. PDBChainSaw.

Crystal structures of five (2-chloro­quinolin-3-yl)methyl ethers: supra­molecular assembly in one and two dimensions mediated by hydrogen bonding and π–π stacking

PubMed Central

Sowmya, Haliwana B. V.; Suresha Kumara, Tholappanavara H.; Gopalpur, Nagendrappa; Jasinski, Jerry P.; Millikan, Sean P.; Yathirajan, Hemmige S.; Glidewell, Christopher

2015-01-01

In the mol­ecules of the title compounds, methyl 5-bromo-2-[(2-chloro­quinolin-3-yl)meth­oxy]benzoate, C18H13BrClNO3, (I), methyl 5-bromo-2-[(2-chloro-6-methyl­quinolin-3-yl)meth­oxy]benzoate, C19H15BrClNO3, (II), methyl 2-[(2-chloro-6-methyl­quinolin-3-yl)meth­oxy]benzoate, C19H16ClNO3, (III), which crystallizes with Z′ = 4 in space group P212121, and 2-chloro-3-[(naphthalen-1-yl­oxy)meth­yl]quinoline, C20H14ClNO, (IV), the non-H atoms are nearly coplanar, but in {5-[(2-chloro­quinolin-3-yl)meth­oxy]-4-(hy­droxy­meth­yl)-6-methyl­pyridin-3-yl}methanol, C18H17ClN2O3, (V), the planes of the quinoline unit and of the unfused pyridine ring are almost parallel, although not coplanar. The mol­ecules of (I) are linked by two independent π–π stacking inter­actions to form chains, but there are no hydrogen bonds present in the structure. In (II), the mol­ecules are weakly linked into chains by a single type of π–π stacking inter­action. In (III), three of the four independent mol­ecules are linked by π–π stacking inter­actions but the other mol­ecule does not participate in such inter­actions. Weak C—H⋯O hydrogen bonds link the mol­ecules into three types of chains, two of which contain just one type of independent mol­ecule while the third type of chain contains two types of mol­ecule. The mol­ecules of (IV) are linked into chains by a C—H⋯π(arene) hydrogen bond, but π–π stacking inter­actions are absent. In (V), there is an intra­molecular O—H⋯O hydrogen bond, and mol­ecules are linked into sheets by a combination of O—H⋯N hydrogen bonds and π–π stacking inter­actions. PMID:26090133

[Inhibition of osthole for resorption of rats femur tissue in vitro].

PubMed

Zhou, Jian; Ren, Xue-mei; Ma, Xiao-ni; Gao, Yu-hai; Yan, Li-juan; Shi, Wen-gui; Chen, Ke-ming

2015-09-01

To investigate osthole effect on femoral tissue resorption activity of rat in vitro. Six SD rats weighted (80 ± 5) g were used to isolate and culture femoral tissue (diaphyses and metaphysis) in vitro. The cultured tissue were devided into control group, estradiol group and osthole group. The femoral tissue was treated with final concentration of 1 x 10(-5) mol/L osthole and 1 x 10(-8) mol/L estradiol culture in vitro at 48 hours after cultured. Tartrate-resistant acid phosphatase (StrACP) activity, glucose and Lactic acid content, StrACP, MCSF (Macrophage colony stimulating factor) and CTSK (Cathepsin K) mRNA was detected by Real-Time RT-PCR were detected. Concetration of Alkaline phosphatase activity were 2226 and 2498 in 1 x 10(-5) mol/L osthole and 1 x 10(-8) mol/L estradiol respectively. As compared with control group, the activity of StrACP of 1 x 10(-5) mol/L osthole and 1 x 10(-8) mol/L estradiol were inhibited at 6, 9, 12 days (P < 0.05); under treatment of in l x 10(-5) mol/L osthole, the content of Lactic acid were increased and the content of glucose were decreased at 3, 6, 9 days (P < 0.05); StrACP, MCSF and CTSK mRNA expression level were inhibited at 6, 9 days (P < 0.05). Osthole can inhibit bone resorption and raise the level of nutrition metabolism of femurs tissue.

Routine internal- and external-quality control data in clinical laboratories for estimating measurement and diagnostic uncertainty using GUM principles.

PubMed

Magnusson, Bertil; Ossowicki, Haakan; Rienitz, Olaf; Theodorsson, Elvar

2012-05-01

Healthcare laboratories are increasingly joining into larger laboratory organizations encompassing several physical laboratories. This caters for important new opportunities for re-defining the concept of a 'laboratory' to encompass all laboratories and measurement methods measuring the same measurand for a population of patients. In order to make measurement results, comparable bias should be minimized or eliminated and measurement uncertainty properly evaluated for all methods used for a particular patient population. The measurement as well as diagnostic uncertainty can be evaluated from internal and external quality control results using GUM principles. In this paper the uncertainty evaluations are described in detail using only two main components, within-laboratory reproducibility and uncertainty of the bias component according to a Nordtest guideline. The evaluation is exemplified for the determination of creatinine in serum for a conglomerate of laboratories both expressed in absolute units (μmol/L) and relative (%). An expanded measurement uncertainty of 12 μmol/L associated with concentrations of creatinine below 120 μmol/L and of 10% associated with concentrations above 120 μmol/L was estimated. The diagnostic uncertainty encompasses both measurement uncertainty and biological variation, and can be estimated for a single value and for a difference. This diagnostic uncertainty for the difference for two samples from the same patient was determined to be 14 μmol/L associated with concentrations of creatinine below 100 μmol/L and 14 % associated with concentrations above 100 μmol/L.

Vildagliptin vs sulfonylurea in Indian Muslim diabetes patients fasting during Ramadan

PubMed Central

Shete, Abhijit; Shaikh, Aheson; Nayeem, K Javeed; Rodrigues, Lily; Ali, Mohamed Sheikamunadeen Sadiq; Shah, Parag; Khanna, Rajiv; Majid, Sarfaraj; Rasheed, Sabeer A; Shaikh, Shehla; Rahman, Tawfiqur

2013-01-01

AIM: To compare the use of vildagliptin and sulfonylurea with or without metformin in Indian Muslim patients with type 2 diabetes mellitus, fasting during Ramadan. METHODS: This was a 4-wk, multicenter, non-interventional, open-label, observational study. Incidence of hypoglycemic events (HEs), adverse events, and changes in glycosylated hemoglobin A1c (HbA1c), fasting plasma glucose, postprandial plasma glucose and body weight were measured pre- and post-Ramadan. RESULTS: Totally, 97 patients were recruited and all completed the study (vildagliptin group, n = 55; sulfonylurea group, n = 42). HEs were reported in low frequencies in both the vildagliptin and the sulfonylurea groups [0 vs 2 (4.8%) patients, respectively]. Interestingly, HbA1c reduced by -0.43% (-4.71 mmol/mol) in the vildagliptin group [8.75% (72.10 mmol/mol) to 8.32% (67.38 mmol/mol), P = 0.009] while in the sulfonylurea group there was a small increase by 0.01% [0.08 mmol/mol; 8.64% (70.92 mmol/mol) to 8.65% (71.00 mmol/mol), P = 0.958]. Higher percentage of vildagliptin-treated patients achieved HbA1c < 7.0% (< 53 mmol/mol) compared with sulfonylurea (16.4% vs 4.8%). Mean decrease in the body weight was 1.2 kg and 0.03 kg, respectively (P < 0.001). Both treatment groups were well tolerated during Ramadan. CONCLUSION: Vildagliptin is an attractive treatment option for Indian patients with type 2 diabetes mellitus who are fasting during Ramadan. PMID:24379927

Vildagliptin vs sulfonylurea in Indian Muslim diabetes patients fasting during Ramadan.

PubMed

Shete, Abhijit; Shaikh, Aheson; Nayeem, K Javeed; Rodrigues, Lily; Ali, Mohamed Sheikamunadeen Sadiq; Shah, Parag; Khanna, Rajiv; Majid, Sarfaraj; Rasheed, Sabeer A; Shaikh, Shehla; Rahman, Tawfiqur

2013-12-15

To compare the use of vildagliptin and sulfonylurea with or without metformin in Indian Muslim patients with type 2 diabetes mellitus, fasting during Ramadan. This was a 4-wk, multicenter, non-interventional, open-label, observational study. Incidence of hypoglycemic events (HEs), adverse events, and changes in glycosylated hemoglobin A1c (HbA1c), fasting plasma glucose, postprandial plasma glucose and body weight were measured pre- and post-Ramadan. Totally, 97 patients were recruited and all completed the study (vildagliptin group, n = 55; sulfonylurea group, n = 42). HEs were reported in low frequencies in both the vildagliptin and the sulfonylurea groups [0 vs 2 (4.8%) patients, respectively]. Interestingly, HbA1c reduced by -0.43% (-4.71 mmol/mol) in the vildagliptin group [8.75% (72.10 mmol/mol) to 8.32% (67.38 mmol/mol), P = 0.009] while in the sulfonylurea group there was a small increase by 0.01% [0.08 mmol/mol; 8.64% (70.92 mmol/mol) to 8.65% (71.00 mmol/mol), P = 0.958]. Higher percentage of vildagliptin-treated patients achieved HbA1c < 7.0% (< 53 mmol/mol) compared with sulfonylurea (16.4% vs 4.8%). Mean decrease in the body weight was 1.2 kg and 0.03 kg, respectively (P < 0.001). Both treatment groups were well tolerated during Ramadan. Vildagliptin is an attractive treatment option for Indian patients with type 2 diabetes mellitus who are fasting during Ramadan.

Effect of specific activity on neuroblastoma uptake of I-123-meta-iodobenzylguanidine in nude mice xenografted with SK-N-SH cells.

PubMed

Farahati, J; Coenen, H; Dutschka, K; Stuben, G; Knuhmann, K; Budach, W; Kremens, B; Reiners, C

1997-01-01

The effect of specific activity of meta[I-123]iodobenzylguanidine ([I-123]MIBG) on neuroblastoma uptake was studied in a nude mouse model (NMRI nu/nu) xenografted subcutaneously with SK-N-SH cells. Groups of eight animals received [I-123]MIBG intravenously with a specific activity of greater than or equal to 260 GBq/mu mol (no-carrier-added), 3.7 GBq/mu mol, 37 MBq/mu mol, and 0.37 MBq/mu mol, respectively. All animals in the group injected with 0.37 MBq/mu mol died immediately after the injection. Al 4 and 24 h, there was no significant effect of specific activity on tumor uptake of [I-123]MIBG in the different groups. The uptake of non-tumor tissue was in general lower with 37 MBq/mu mol compared to higher specific activities. The differences in blood, heart, liver, spleen and lungs were statistically significant at 24 h, whereas at 4 h significant differences were only present in the heart, liver and lungs. The results suggest that for the treatment of children with neuroblastoma a lower specific activity of radioiodinated MIBG may minimize the radiation exposure to non-tumor tissue but not to the tumor. Higher mass of MIBG >0.5 mu mol/g, however, is considered as lethal dose in our nude mice model and corresponding doses may cause toxic side effects in human.

Sodium doping effect on physicochemical properties of K{sub 1−x}Na{sub x}CaPb{sub 3}(PO{sub 4}){sub 3} (0 ≤ x ≤ 1) for the determination of mercury(II): Application in seawater samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lahrich, Sara; University Hassan 1, Laboratoire Sciences des Matériaux, des Milieux et de la Modélisation, 25000 Khouribga; Manoun, Bouchaib

Highlights: • The apatite, K{sub 1−x}Na{sub x}CaPb{sub 3}(PO{sub 4}){sub 3} (0 ≤ x ≤ 1), was synthesized using reaction solid. • The obtained apatite was used to determine mercury in seawater samples from Morocco. • The effect of doping sodium into apatite on physic-chemical parameters was studied. • The influence of the electrochemical variables was investigated to determine mercury. - Abstract: A new chemically modified electrode was synthesized for the determination of mercury(II) using differential pulse anodic stripping voltammetry (DPASV). The electrode was modified by lacunar apatite K{sub 1−x}Na{sub x}CaPb{sub 3}(PO{sub 4}){sub 3} (0 ≤ x ≤ 1) synthesized usingmore » solid reaction. These powders were crystallized in the hexagonal system, space group P6{sub 3}/m. The effect of sodium content on structural, thermodynamic and electrochemical properties of prepared apatite has been studied. Therefore, the best results was obtained using NaCaPb{sub 3}(PO{sub 4}){sub 3} (x = 1) as modifier of carbon paste electrode for the electrochemical detection of mercury(II). The later ions were preconcentrated on the surface of the modified electrode and oxidized at 0.06 V vs. Ag/AgCl. The electroanalytical procedure comprises of two steps: the chemical accumulation of the analyte under open-circuit conditions followed by the electrochemical detection of the preconcentrated species using differential pulse voltammetry. The different parameters that govern the two steps were optimized. A linear response was obtained in the concentration range from 1.0 mol L{sup −1} × 10{sup −4} mol L{sup −1} to 2.0 mol L{sup −1} × 10{sup −7} mol L{sup −1} Hg(II) after activation of the electrode surface under the optimized conditions. The standard deviation was evaluated in a high and low concentration of mercury(II). The values ​​obtained for seven consecutive measurements were 1.24% and 5.07% of 1.0 mol L{sup −1} × 10{sup −4} mol L{sup −1} and 5.0 mol L{sup −1} × 10{sup −6} mol L{sup −1} mercury(II) solutions respectively. The detection limit and quantification limit for mercury(II), calculated from nine times standard deviation of blank/slope of the calibration graph, were 1.086 mol L{sup −1} × 10{sup −8} mol L{sup −1} and 3.62 mol L{sup −1} × 10{sup −8} mol L{sup −1}, respectively. The proposed chemically modified electrode was applied to determine mercury(II) in seawater samples.« less

Improved Kinetic Models for High-Speed Combustion Simulation

DTIC Science & Technology

2008-06-01

142 Appendix F1: USC_Skeletal_Ethylene_chem.inp ....................................................................... 143 ...to form a strong carbonyl double bond ( keto -Q) gaining 80 kcal mol-1, which is sufficient to immediately cleave the weak RO—OH bond (45 kcal mol-1...in the hydroperoxide. Relative to the stabilized adduct this reaction to ( keto -Q+OH), product set is 65.9 kcal mol-1 below the entrance channel

1-[1-(4-Chloro-phen-yl)ethyl-idene]carbono-hydrazide.

PubMed

Du, Lingyun; Du, Lei; Wang, Shuhao

2009-08-12

The mol-ecular skeleton of the title mol-ecule, C(9)H(11)ClN(4)O, is essentially planar, the dihedral angle between the ring and the and N/N/C plane being 6.7 (3)°. In the crystal, inter-molecular N-H⋯O and N-H⋯N hydrogen bonds link the mol-ecules into ribbons propagated along [010].

Thin films for gas sensors

NASA Astrophysics Data System (ADS)

Pires, Jose Miguel Alves Correia

Nos ultimos anos tem-se assistido a um aumento dos investimentos na investigacao de novos materiais para aplicacao em sensores. Apesar de ja existir um bom numero de dispositivos explorados comercialmente, muitas vezes, quer devido aos elevados custos de producao, quer devido a uma crescente exigencia do ponto de vista das caracteristicas de funcionamento, continua a ser necessario procurar novos materiais ou novas formas de producao que permitam baixar os custos e melhorar o desempenho dos dispositivos. No campo dos sensores de gases tem-se verificado continuos avancos nos ultimos anos. Continua todavia a ser necessario conhecer melhor, tanto os processos de producao dos materiais, como os mecanismos que regulam a sensibilidade dos dispositivos aos gases, de modo a orientar adequadamente a investigacao dos novos materiais, nomeadamente no que se refere a optimizacao dos parâmetros que nao satisfazem ainda os requisitos do mercado. Um dos materiais que tem mostrado melhores qualidades para aplicacao em sensores de gases de tipo resistivo e o dioxido de estanho. Este material tem sido produzido sob diversas formas e usando diferentes tecnicas, como sejam: sol-gel [1], pulverizacao catodica (sputtering) por magnetrao [2-4], sinterizacao de pos [5, 6], ablacao laser [7] ou RGTO [8]. Os resultados obtidos revelam que as caracteristicas dos dispositivos sao muito dependentes das tecnicas usadas na sua producao. A deposicao usando sputtering reactivo por magnetrao e uma tecnica que permite obter filmes finos de oxido de estanho com diferentes caracteristicas, quer do ponto de vista da estrutura, quer da composicao, e por isso, tambem, com diferentes sensibilidades aos gases. No âmbito deste trabalho, foram produzidos filmes de SnO2 usando sputtering DC reactivo com diferentes condicoes de deposicao. Os substratos usados foram lâminas de vidro e o alvo foi estanho com 99.9% de pureza. Foi estudada a influencia da atmosfera de deposicao, da pressao parcial do O2, da temperatura do substrato e da potencia da descarga na estrutura do material depositado. Durante a deposicao, alem dos parâmetros ja referidos, foram tambem registados a pressao de base antes da entrada dos gases de sputtering, os fluxos de oxigenio e argon durante a deposicao, a distância alvo-substrato, o tempo de deposicao, a corrente e a tensao aplicadas ao magnetrao. Foram feitas algumas experiencias usando uma fonte RF, para comparacao. (Abstract shortened by ProQuest.).

P2Y receptor-mediated transient relaxation of rat longitudinal ileum preparations involves phospholipase C activation, intracellular Ca(2+) release and SK channel activation.

PubMed

Mader, Felix; Krause, Ludwig; Tokay, Tursonjan; Hakenberg, Oliver W; Köhling, Rüdiger; Kirschstein, Timo

2016-05-01

Purinergic signaling plays a major role in the enteric nervous system, where it governs gut motility through a number of P2X and P2Y receptors. The aim of this study was to investigate the P2Y receptor-mediated motility in rat longitudinal ileum preparations. Ileum smooth muscle strips were prepared from rats, and fixed in an organ bath. Isometric contraction and relaxation responses of the muscle strips were measured with force transducers. Drugs were applied by adding of stock solutions to the organ bath to yield the individual final concentrations. Application of the non-hydrolyzable P2 receptor agonists α,β-Me-ATP or 2-Me-S-ADP (10, 100 μmol/L) dose-dependently elicited a transient relaxation response followed by a sustained contraction. The relaxation response was largely blocked by SK channel blockers apamin (500 nmol/L) and UCL1684 (10 μmol/L), PLC inhibitor U73122 (100 μmol/L), IP3 receptor blocker 2-APB (100 μmol/L) or sarcoendoplasmic Ca(2+) ATPase inhibitor thapsigargin (1 μmol/L), but not affected by atropine, NO synthase blocker L-NAME or tetrodotoxin. Furthermore, α,β-Me-ATP-induced relaxation was suppressed by P2Y1 receptor antagonist MRS2179 (50 μmol/L) or P2Y13 receptor antagonist MRS2211 (100 μmol/L), and was abolished by co-application of the two antagonists, whereas 2-Me-S-ADP-induced relaxation was abolished by P2Y6 receptor antagonist MRS2578 (50 μmol/L). In addition, P2Y1 receptor antagonist MRS2500 (1 μmol/L) not only abolished α,β-Me-ATP-induced relaxation, but also suppressed 2-Me-S-ADP-induced relaxation. P2Y receptor agonist-induced transient relaxation of rat ileum smooth muscle strips is mediated predominantly by P2Y1 receptor, but also by P2Y6 and P2Y13 receptors, and involves PLC, IP3, Ca(2+) release and SK channel activation, but is independent of acetylcholine and NO release.

Comparing the sensitivity of chlorophytes, cyanobacteria, and diatoms to major-use antibiotics.

PubMed

Guo, Jiahua; Selby, Katherine; Boxall, Alistair B A

2016-10-01

The occurrence of antibiotic residues in the aquatic environment is an emerging concern. In contrast to daphnia and fish, algae are known to be particularly sensitive to antibiotic exposure. However, to date, a systematic evaluation of the sensitivity of different algal species to antibiotics has not been performed. The aim of the present study was therefore to explore the sensitivity of a battery of algal species toward antibiotic exposures. The present study investigated the growth inhibition effects of 3 major-use antibiotics, tylosin, lincomycin, and trimethoprim, on 7 algal species from the chlorophyte, cyanobacteria, and diatom groups. Based on median effective concentration (EC50) values, cyanobacteria (EC50 = 0.095-0.13 μmol/L) were found to be the most sensitive group to lincomycin followed by chlorophytes (EC50 = 7.36-225.73 μmol/L) and diatoms (EC50 > 225.73 μmol/L). Cyanobacteria were also the most sensitive group to tylosin (EC50 = 0.09-0.092 μmol/L), but, for this compound, diatoms (EC50 = 1.33-5.7 μmol/L) were more sensitive than chlorophytes (EC50 = 4.14-81.2 μmol/L). Diatoms were most sensitive to trimethoprim (EC50 = 7.36-74.61 μmol/L), followed by cyanobacteria (EC50 = 315.78-344.45 μmol/L), and chlorophytes (EC50 > 344.45 μmol/L) for trimethoprim. Although these results partly support the current approach to regulatory environmental risk assessment (whereby cyanobacterial species are recommended for use with antibiotic compounds), they indicate that for some antibiotics this group might not be the most appropriate test organism. It is therefore suggested that environmental risk assessments consider data on 3 algal groups (chlorophytes, cyanobacteria, and diatoms) and use test species from these groups, which are consistently found to be the most sensitive (Pseudokirchneriella subcapitata, Anabaena flos-aquae, and Navicula pelliculosa). Environ Toxicol Chem 2016;35:2587-2596. © 2016 SETAC. © 2016 SETAC.

Energy transfer and 2.0 μm emission in Tm{sup 3+}/Ho{sup 3+} co-doped α-NaYF{sub 4} single crystals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feng, Zhigang; Yang, Shuo; Xia, Haiping, E-mail: hpxcm@nbu.edu.cn

2016-04-15

Highlights: • Cubic NaYF{sub 4} single crystals co-doped with ∼1.90 mol% Tm{sup 3+} and various Ho{sup 3+} concentrations were grown by Bridgman method. • The maximum fluorescence lifetime was 23.23 ms for Tm{sup 3+} (1.90 mol%)/Ho{sup 3+} (3.89 mol%) co-doped α-NaYF{sub 4}. • The obtained energy transfer rate (W{sub ET}) and energy transfer efficiency (η) of Tm{sup 3+}:{sup 3}F{sub 4} are 1077 s{sup −1} and 95.0%, respectively. • The maximum emission cross section reached 1.06 × 10{sup −20} cm{sup 2}. - Abstract: Cubic NaYF{sub 4} single crystals co-doped with ∼1.90 mol% Tm{sup 3+} and various Ho{sup 3+} concentrations were grownmore » by Bridgman method. The energy transfer from Tm{sup 3+} to Ho{sup 3+} and the optimum fluorescence emission around 2.04 μm of Ho{sup 3+} ion were investigated based on the measured absorption spectra, emission spectra, emission cross section and decay curves under excitation of 800 nm LD. The emission intensity at 2.04 μm increased with the increase of Ho{sup 3+} concentration from 0.96 mol% to 3.89 mol% when the concentration of Tm{sup 3+} was held constantly at ∼1.90 mol%. Moreover, the maximum emission cross section reached 1.06 × 10{sup −20} cm{sup 2} and the maximum fluorescence lifetime was 23.23 ms for Tm{sup 3+}(1.90 mol%)/Ho{sup 3+}(3.89 mol%) co-doped one. According to the measured lifetime of Tm{sup 3+} single-doped and Tm{sup 3+}/Ho{sup 3+} co-doped samples, the maximum energy transfer efficiency of Tm{sup 3+}:{sup 3}F{sub 4} level was 95.0%. Analysis on the fluorescence dynamics indicated that electric dipole–dipole is dominant for the energy transfer from Tm{sup 3+} to Ho{sup 3+}.« less

Study of the interaction of flavonoids with 3-mercaptopropionic acid modified CdTe quantum dots mediated by cetyltrimethyl ammonium bromide in aqueous medium

NASA Astrophysics Data System (ADS)

Aucelio, Ricardo Q.; Carvalho, Juliana M.; Real, Juliana T.; Maqueira-Espinosa, Luis; Pérez-Gramatges, Aurora; da Silva, Andrea R.

2017-02-01

Flavonoids are polyphenols that help the maintenance of health, aiding the prevention of diseases. In this work, CdTe QDs coated with 3-mercaptopropionic acid (3MPA), with an average size of 2.7 nm, were used as photoluminescence probe for flavonoids in different conditions. The interaction between 14 flavonoids and QDs was evaluated in aqueous dispersions in the absence and in the presence of cetyltrimethylammonium bromide (CTAB). To establish a relationship between photoluminescence quenching and the concentration of flavonoids, the Stern-Volmer model was used. In the absence of CTAB, the linear ranges for quercetin, morin and rutin were from 5.0 × 10- 6 mol L- 1 to 6.0 × 10- 5 mol L- 1 and from 1.0 × 10- 5 mol L- 1 to 6.0 × 10- 4 mol L- 1 for kaempferol. The sensibility of the Stern-Volmer curves (Ks) indicated that quercetin interacts more strongly with the probe: Ks quercetin > Ks kaempferol > Ks rutin > Ks morin. The conjugation extension in the 3 rings, and the acidic hydroxyl groups (positions 3ʹand 4ʹ) in the B-ring enhanced the interaction with 3MPA-CdTe QDs. The other flavonoids do not interact with the probe at 10- 5 mol L- 1 level. In CTAB organized dispersions, Ks 3-hydroxyflavone > Ks 7-hydroxyflavone > Ks flavona > Ks rutin in the range from 1.0 × 10- 6 mol L- 1 to 1.2 × 10- 5 mol L- 1 for flavones and of 1.0 × 10- 6 mol L- 1 to 1.0 × 10- 5 mol L- 1 for rutin. Dynamic light scattering, conductometric measurements and microenvironment polarity studies were employed to elucidate the QDs-flavonoids interaction in systems containing CTAB. The quenching can be attributed to the preferential solubility of hydrophobic flavonoid in the palisade layer of the CTAB aggregates adsorbed on the surface of the 3MPA CdTe QDs.

Differential half-maximal effects of human insulin and its analogs for in situ glucose transport and protein synthesis in rat soleus muscle

NASA Technical Reports Server (NTRS)

Weinstein, Randi B.; Eleid, Noura; LeCesne, Catherine; Durando, Bianca; Crawford, Julie T.; Heffner, Michelle; Layton, Christle; O'Keefe, Matthew; Robinson, Jennifer; Rudinsky, Suzy;

Mapping the Mariana Seismogenic Zone Through the Measurement of Geochemical Tracers in Serpentinite Seamounts

NASA Astrophysics Data System (ADS)

Hulme, S. M.; Wheat, C. G.; Mottl, M. J.; Fryer, P.

2003-12-01

The Mariana forearc contains tens of seamounts up to 2 km high and 20-50 km in diameter. These seamounts were formed by serpentinite mud volcanism, sometimes in combination with uplift of serpentinized forearc mantle blocks, in which fluids driven off of the subducting slab infiltrated the overlying mantle and serpentinized the harzburgite and dunite rocks creating a density imbalance within the mantle. The resulting fluid-rock matrix flows along faults and exposes mantle-sourced serpentinite muds, blueschist facies metamorphosed mafic clasts, and slab-sourced fluids at the seafloor. The protrusion of these materials allows direct observation of active subduction zone components that are elsewhere buried beneath kilometers of rock and sediment. A multi-disciplinary survey of the Mariana Forearc was conducted in the spring of 2003 to study the biogeochemical properties of this mud volcanism. Seven different seamounts were sampled using shipboard and subsea coring techniques employing RV Thomas G. Thompson and ROV Jason II, respectively. Pore waters were extracted from these sediment cores and analyzed for several chemical constituents at sea. The measured values were consistent with preliminary work from 1997. Systematic trends in chemical composition of these high pH fluids (up to 12.3) are observed with distance from the trench (proxy for the depth to slab). These trends include low alkalinity and high Ca near the trench (e.g., Blue Moon Seamount; 0.26 mmol alkalinity/kg and 55 mmol Ca/kg), and high alkalinity and low Ca further from the trench (e.g., Big Blue Seamount; 69 mmol alkalinity/kg and 0.14 mmol Ca/kg) consistent with carbonate dissolution at the top of the plate between depths of 17 km and 22 km. Here we report results from trace element analyses that similarly show trends across the forearc region. For example, fluids upwelling at Baby Blue Seamount have; 58 μ mol Sr/kg, 31 μ mol Li/kg, 1.4 μ mol Rb/kg, 10 nmol Cs/kg, 0.2 μ mol Ba/kg, 0.1 μ mol Mo/kg, 0.6 nmol U/kg, and 5 nmol Y/kg. In contrast, fluids from Big Blue Seamount, only 23 km away, have; 10 μ mol Sr/kg, 0.7 μ mol Li/kg, 6 μ mol Rb/kg, 0.2 μ mol Cs/kg, 60 nmol Ba/kg, 0.1 μ mol Mo/kg, 0.2 μ mol U/kg, and 0.1 nmol Y/kg.Trace element analyses for a host of chemical species and for each of the sampled seamounts offer insight into the conditions and interactions currently occurring within the Mariana seismogenic zone.

Fifty years of Jaynes-Cummings physics

NASA Astrophysics Data System (ADS)

Greentree, Andrew D.; Koch, Jens; Larson, Jonas

2013-11-01

This special issue commemorates the 50th anniversary of the seminal paper published by E T Jaynes and F W Cummings [1], the fundamental model which they introduced and now carries their names, and celebrates the remarkable host of exciting research on Jaynes-Cummings physics throughout the last five decades. The Jaynes-Cummings model has been taking the prominent stance as the 'hydrogen atom of quantum optics' [2]. Generally speaking, it provides a fundamental quantum description of the simplest form of coherent radiation-matter interaction. The Jaynes-Cummings model describes the interaction between a single electromagnetic mode confined to a cavity, and a two-level atom. Energy is exchanged between the field and the atom, which leads directly to coherent population oscillations (Rabi oscillations) and superposition states (dressed states). Being exactly solvable, the Jaynes-Cummings model serves as a most useful toy model, and as such it is a textbook example of the physicists' popular strategy of simplifying a complex problem to its most elementary constituents. Thanks to the simplicity of the Jaynes-Cummings model, this caricature of coherent light-matter interactions has never lost its appeal. The Jaynes-Cummings model is essential when discussing experiments in quantum electrodynamics (indeed the experimental motivation of the Jaynes-Cummings model was evident already in the original paper, dealing as it does with the development of the maser), and it has formed the starting point for much fruitful research ranging from ultra-cold atoms to cavity quantum electrodynamics. In fact, Jaynes-Cummings physics is at the very heart of the beautiful experiments by S Haroche and D Wineland, which recently earned them the 2012 Nobel Prize in physics. Indeed, as with most significant models in physics, the model is invoked in settings that go far beyond its initial framework. For example, recent investigations involving multi-level atoms, multiple atoms [3, 4], multiple electromagnetic modes, arrays of coupled cavities [5-7], and optomechanical systems [8] have further enriched the physics of the Jaynes-Cummings model. From the early interests in masers and the consistent quantum description of radiation and atom-photon interaction, the Jaynes-Cummings model has evolved into a cornerstone of quantum state engineering [9]. The authors of this editorial had not been born when Jaynes and Cummings wrote their remarkable paper. It is, therefore, a special honour for us to be able to draw the reader's attention to the accompanying reminiscence contributed by Frederick Cummings where he gives us a glimpse of the early history of the Jaynes-Cummings model from his perspective [11]. By now, the original 1963 paper by Jaynes and Cummings has gathered numerous citations and, at the time of writing, the number of articles involving Jaynes-Cummings physics is approaching 15 000.1 This special issue does not attempt to review this impressive wealth of research. The interested reader, however, is urged to consult the definitive article by Shore and Knight [10] for a comprehensive review of the first 30 years of Jaynes-Cummings physics. The collection of 26 papers presented in this issue, showcases a snapshot of some of the most recent and continuing research devoted to Jaynes-Cummings physics. We begin our special issue with Professor Cumming's recollections [11]. We then have six papers on quantum information aspects of the Jaynes-Cummings model [12-17]. The next topic includes seven papers on the Dicke and generalized Jaynes-Cummings models [18-24], followed by six papers on circuit QED, which is one of the most important experimental frameworks for Jaynes-Cummings systems [25-30]. Finally, we have six papers on the extension to many cavities, the Jaynes-Cummings-Hubbard model [31-36]. The snapshot of research captured in this special issue illustrates the unifying language provided by the Jaynes-Cummings model, tying together research in a number of subfields in physics. Jaynes-Cummings physics started with the diagonalization of a 2 × 2 matrix, as Frederick Cummings points out. There is no doubt that this elegance of simplicity will continue to guide exciting new research in the decades to come. References [1] Jaynes E T and Cummings F W 1963 Comparison of quantum and semiclassical radiation theories with application to the beam maser Proc. IEEE 51 89 [2] Shore B W and Knight P L 2004 Physics and Probability: Essays in Honor of Edwin T Jaynes (Cambridge: Cambridge University Press) [3] Tavis M and Cummings F W 1968 Exact solution for an N -molecule-radiation-field Hamiltonian Phys. Rev. 170 379-84 [4] Tavis M and Cummings F W 1969 Approximate solutions for an N -molecule-radiation-field Hamiltonian Phys. Rev. 188 692-5 [5] Hartmann M J, Brandão F G S L and Plenio M B 2006 Strongly interacting polaritons in coupled arrays of cavities Nature Phys. 2 849-55 [6] Greentree A D, Tahan C, Cole J H and Hollenberg L C L 2006 Quantum phase transitions of light Nature Phys. 2 856-61 [7] Angelakis D G, Santos M F and Bose S 2007 Photon-blockade-induced Mott transitions and XY spin models in coupled cavity arrays Phys. Rev. A 76 031805(R) [8] Schwab K C and Roukes M L 2005 Putting mechanics into quantum mechanics Phys. Today 58 36-42 [9] Blatt R, Milburn G J and Lvovksy A 2013 The 20th anniversary of quantum state engineering J. Phys. B: At. Mol. Opt. Phys. 46 100201 [10] Shore B and Knight P L 1993 The Jaynes-Cummings model J. Mod. Opt. 40 1195-238 [11] Cummings F W 2013 J. Phys. B: At. Mol. Opt. Phys. 46 220202 [12] Arenz C 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224001 [13] Quesada N 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224002 [14] Everitt M 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224003 [15] Kitajima S 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224004 [16] Groves E 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224005 [17] Bougouffa S 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224006 [18] Braak D 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224007 [19] Emary C 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224008 [20] Miroshnychenko Y 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224009 [21] Dombi A 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224010 [22] Tavis M 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224011 [23] Grimsmo A 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224012 [24] Stenholm S I 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224013 [25] Kockum A F 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224014 [26] Larson J 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224015 [27] Larson J 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224016 [28] Agarwal S 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224017 [29] Deng W-W 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224018 [30] Leppaekangas J 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224019 [31] Schmidt S 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224020 [32] Schiro M 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224021 [33] Susa C 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224022 [34] del Valle E 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224023 [35] Correa B V 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224024 [36] Schetakis N 2013 J. Phys. B: At. Mol. Opt. Phys. 46 224025 1Number estimate based on a Google Scholar search.

Propane in nitrogen, 1000 μmol/mol

NASA Astrophysics Data System (ADS)

Konopelko, L. A.; Kustikov, Y. A.; Kolobova, A. V.; Pankratov, V. V.; Pankov, A. A.; Efremova, O. V.; Rozhnov, M. S.; Melnyk, D. M.; Petryshyn, P. V.; Levbarg, O. S.; Kisel, S. P.; Shpilnyi, S. A.; Yakubov, S. Ye; Bakovec, N. V.; Mironchik, A. M.; Aleksandrov, V. V.

2017-01-01

This article presents the report on the COOMET key comparison COOMET.QM-K111, which is linking to the appropriate CCQM comparison—CCQM-K111 'Propane in nitrogen 1000 μmol/mol'. CCQM-K111 was carried out in 2014-2016 and it was one of a series of key comparisons in the gas analysis area assessing core competences. Main text To reach the main text of this paper, click on Final Report. Note that this text is that which appears in Appendix B of the BIPM key comparison database kcdb.bipm.org/. The final report has been peer-reviewed and approved for publication by the CCQM, according to the provisions of the CIPM Mutual Recognition Arrangement (CIPM MRA).

1,5-Bis[1-(2,4-dihy­droxy­phen­yl)ethyl­idene]carbonohydrazide dimethyl­formamide disolvate

PubMed Central

He, Qing-Peng; Tan, Bo; Lu, Ze-Hua

2010-01-01

In the title compound, C17H18N4O5·2C3H7NO, two solvent mol­ecules are linked to the main mol­ecule via N—H⋯O and O—H⋯O hydrogen bonds, forming a hydrogen-bonded trimer. Intra­molecular O—H⋯N hydrogen bonds influence the mol­ecular conformation of the main mol­ecule, and the two benzene rings form a dihedral angle of 10.55 (18)°. In the crystal, inter­molecular O—H⋯O hydrogen bonds link hydrogen-bonded trimers into ribbons extending along the b axis. PMID:21589135

Molybdenum cofactor (chlorate-resistant) mutants of Klebsiella pneumoniae M5al can use hypoxanthine as the sole nitrogen source.

PubMed Central

Garzón, A; Li, J; Flores, A; Casadesus, J; Stewart, V

1992-01-01

Selection for chlorate resistance yields mol (formerly chl) mutants with defects in molybdenum cofactor synthesis. Complementation and genetic mapping analyses indicated that the Klebsiella pneumoniae mol genes are functionally homologous to those of Escherichia coli and occupy analogous genetic map positions. Hypoxanthine utilization in other organisms requires molybdenum cofactor as a component of xanthine dehydrogenase, and thus most chlorate-resistant mutants cannot use hypoxanthine as a sole source of nitrogen. Surprisingly, the K. pneumoniae mol mutants and the mol+ parent grew equally well with hypoxanthine as the sole nitrogen source, suggesting that K. pneumoniae has a molybdenum cofactor-independent pathway for hypoxanthine utilization. PMID:1400180

pH-Sensitive Liposomes: Acid-Induced Liposome Fusion

NASA Astrophysics Data System (ADS)

Connor, Jerome; Yatvin, Milton B.; Huang, Leaf

1984-03-01

Sonicated unilamellar liposomes containing phosphatidylethanolamine and palmitoylhomocysteine fuse rapidly when the medium pH is lowered from 7 to 5. Liposome fusion was demonstrated by (i) mixing of the liposomal lipids as shown by resonance energy transfer, (ii) gel filtration, and (iii) electron microscopy. The pH-sensitive fusion of liposomes was observed only when palmitoylhomocysteine (>= 20 mol%) was present in the liposomes. The presence of phosphatidyl-ethanolamine in the liposomes greatly enhanced fusion whereas the presence of phosphatidylcholine inhibited fusion. During fusion of liposomes containing phosphatidylethanolamine and palmitoylhomocysteine (8:2, mol/mol), almost all of the encapsulated calcein was released. Inclusion of cholesterol (40 mol%) in the liposomes substantially decreased leakage without impairing fusion.

6-Chloro-3-phenethyl-2-thioxo-2,3-di­hydro­quinazolin-4(1H)-one

PubMed Central

Hashim, Norhafizah Mohd; Osman, Hasnah; Rahim, Afidah Abdul; Yeap, Chin Sing; Fun, Hoong-Kun

2010-01-01

The asymmetric unit of the title quinazolinone compound, C16H13ClN2OS, consists of two crystallographically independent mol­ecules, A and B. The dihedral angles between the quinazoline and benzene rings are 16.88 (6) and 32.34 (6)° for mol­ecules A and B, respectively. In the crystal structure, mol­ecules A and B are linked by two bifurcated inter­molecular N—H⋯S and C—H⋯S hydrogen bonds. Pairs of mol­ecules are further linked by C—H⋯O and C—H⋯Cl hydrogen bonds into a chain aligned approximately along [110]. PMID:21580754

The Dissociation Energies of CH4 and C2H2 Revisited

NASA Technical Reports Server (NTRS)

Partridge, Harry; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

The bond dissociation energies of CH4 and C2H2 and their fragments are investigated using basis set extrapolations and high levels of correlation. The computed bond dissociation energies (D(sub e)) are accurate to within 0.2 kcal/mol. The agreement with the experimental (D(sub 0)) values is excellent if we assume that the zero-point energy of C2H is 9.18 kcal/mol. The effect of core (1s) correlation on the bond dissociation energies of C-H bonds is shown to vary from 0.2 to 0.7 kcal/mol and that for C-C bonds varies from 0.4 to 2.2 kcal/mol.

Thermal Conductivity of Alumina-reinforced Zirconia Composites

NASA Technical Reports Server (NTRS)

Bansal, Narottam P.

2005-01-01

10-mol% yttria-stabilized zirconia (10SZ) - alumina composites containing 0-30 mol% alumina were fabricated by hot pressing at 1500 C in vacuum. Thermal conductivity was determined at various temperatures using a steady-state laser heat flux technique. Thermal conductivity of the composites increased with increase in alumina content. Composites containing 0, 5, and 10-mol% alumina did not show any change in thermal conductivity with temperature. However, those containing 20 and 30-mol% alumina showed a decrease in thermal conductivity with increase in temperature. The measured values of thermal conductivity were in good agreement with those calculated from the Maxwell-Eucken model where one phase is uniformly dispersed within a second major continuous phase.

A MRCC study of the isomerisation of cyclopropane

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lang, Jakub; Švaňa, Matej; Demel, Ondřej

2017-01-19

Mukherjee’s and Brillouin-Wigner multi-reference coupled cluster methods were used to study the isomerization of cyclopropane to propene through a trimethylene/propylidene diradicals. Main aim was to obtain high quality ab-initio data using advanced methods that treat both static and dynamic correlation in the involved species. The MkCCSD(T)/cc-pVQZ activation energy of cyclopropane isomerization via trimethylene is 65.6 kcal/mol, in a good agreement with experimental values in the range 60-65 kcal/mol. The MkCCSD(T)/cc-pV5Z adiabatic singlet-triplet gap in trimethylene is 0.6 kcal/mol, slightly higher than previous CASPT2 result -0.7 kcal/mol by Skancke et al.

N-(3-Chloro-1-methyl-1H-indazol-5-yl)-4-methylbenzene­sulfonamide

PubMed Central

Chicha, Hakima; Rakib, El Mostapha; Amiri, Ouafa; Saadi, Mohamed; El Ammari, Lahcen

2014-01-01

The asymmetric unit of the title compound, C15H14ClN3O2S, contains two independent mol­ecules showing different conformations: in one mol­ecule, the indazole ring system makes a dihedral angle of 51.5 (1)° with the benzene ring whereas in the other, the indazole unit is almost perpendicular to the benzene ring [dihedral angle 77.7 (1)°]. In the crystal, the mol­ecules are linked by N—H⋯N and N—H⋯O hydrogen bonds, forming a set of four mol­ecules linked in pairs about an inversion centre. PMID:24764895

Mechanical behaviour of AlSiC nano composites produced by ball milling and spark plasma sintering =

NASA Astrophysics Data System (ADS)

Buchheim, Claudia Sofia de Andrade Redondo Murilhas

Neste trabalho foram produzidos nanocompositos de AlSiC misturando aluminio puro com nano particulas de SiC com diâmetro de 45 - 55 nm, usando, de forma sequencial, a tecnica da metalurgia do po e a compactacao por "Spark Plasma Sintering". O composito obtido apresentava graos com 100 nm de diâmetro, encontrandose as particulas de SiC localizadas, principalmente, nas fronteiras de grao. O nanocomposito sob a forma de provetes cilindricos foi submetido a testes de compressao uniaxial e a testes de nanoindentacao para analisar a influencia das nanoparticulas de SiC, da fracao volumica de acido estearico e do tempo de moagem, nas propriedades mecânicas do material. Para efeitos de comparacao, utilizouse o comportamento mecânico do Al puro processado em condicoes similares e da liga de aluminio AA1050O. A tensao limite de elasticidade do nanocomposito com 1% Vol./Vol. de SiC e dez vezes superior a do AA1050. O refinamento de grao a escala nano constitui o principal mecanismo de aumento de resistencia mecânica. Na realidade, o Al nanocristalino sem reforco de particulas de SiC, apresenta uma tensao limite de elasticidade sete vezes superior a da liga AA1050O. A adicao de 0,5 % Vol./Vol. e de 1 % Vol./Vol. de SiC conduzem, respetivamente, ao aumento da tensao limite de elasticidade em 47 % e 50%. O aumento do tempo de moagem e a adicao de acido estearico ao po durante a moagem conduzem apenas a um pequeno aumento da tensao de escoamento. A dureza do material medida atraves de testes de nanoindentacao confirmaram os dados anteriores. A estabilidade das microestruturas do aluminio puro e do nanocomposito AlSiC, foi testada atraves de recozimento de restauracao realizado as temperaturas de 150 °C e 250 °C durante 2 horas. Aparentemente, o tratamento termico nao influenciou as propriedades mecânicas dos materiais, excepto do nanocomposito com 1 % Vol./Vol. de SiC restaurado a temperatura de 250 °C, para o qual se observou uma reducao da tensao limite de elasticidade na ordem dos 13 %. No aluminio nanocristalino, a tensao de escoamento e controlada pelo efeito de HallPetch. As particulas de SiC, sao segregadas pelas fronteiras do grao e nao contribuem para o aumento de resistencia mecânica segundo o mecanismo de Orowan. Alternativamente, as nanoparticulas de SiC constituem um reforco das fronteiras do grao, impedindo o seu escorregamento e estabilizando a nanoestrutura. Deste modo, as propriedades mecânicas do aluminio nanocristalino e do nanocomposito de AlSiC poderao estar relacionadas com a facilidade ou dificuldade do escorregamento das fronteiras de grao, embora nao seja apresentada prova explicita deste mecanismo a temperatura ambiente.

Purification and characterization of NADPH--cytochrome c reductase from the midgut of the southern armyworm (Spodoptera eridania).

PubMed Central

Crankshaw, D L; Hetnarski, K; Wilkinson, C F

1979-01-01

1. NADPH-cytochrome c reductase was solubilized with bromelain and purified about 400-fold from sucrose/pyrophosphate-washed microsomal fractions from southern armyworm (Spodoptera eridania) larval midguts. 2. The enzyme has a mol.wt. of 70 035 +/- 1300 and contained 2 mol of flavin/mol of enzyme consisting of almost equimolar amounts of FMN and FAD. 3. Aerobic titration of the enzyme with NADPH caused the formation of a stable half-reduced state at 0.5 mol of NADPH/mol of flavin. 4. Kinetic analysis showed that the reduction of cytochrome c proceeded by a Bi Bi Ping Pong mechanism. 5. Apparent Km values for NADPH and cytochrome c and Ki values for NADP+ and 2'-AMP were considerably higher for the insect reductase than for the mammalian liver enzyme. 6. These are discussed in relation to possible differences in the active sites of the enzymes. Images Fig. 3. PMID:117798

Proton dependence of tobacco mosaic virus dissociation by pressure.

PubMed

Santos, Jose L R; Bispo, Jose A C; Landini, Gustavo F; Bonafe, Carlos F S

2004-09-01

Tobacco mosaic virus (TMV) is an intensely studied model of viruses. This paper reports an investigation into the dissociation of TMV by pH and pressure up to 220 MPa. The viral solution (0.25 mg/ml) incubated at 277 K showed a significant decrease in light scattering with increasing pH, suggesting dissociation. This observation was confirmed by HPLC gel filtration and electron microscopy. The calculated volume change of dissociation (DeltaV) decreased (absolute value) from -49.7 ml/mol of subunit at pH 3.8 to -21.7 ml/mol of subunit at pH 9.0. The decrease from pH 9.0 to 3.8 caused a stabilization of 14.1 kJ/mol of TMV subunit. The estimated proton release calculated from pressure-induced dissociation curves was 0.584 mol H(+)/mol of TMV subunit. These results suggest that the degree of virus inactivation by pressure and the immunogenicity of the inactivated structures can be optimized by modulating the surrounding pH.

Strong CH/O interactions between polycyclic aromatic hydrocarbons and water: Influence of aromatic system size.

PubMed

Veljković, Dušan Ž

2018-03-01

Energies of CH/O interactions between water molecule and polycyclic aromatic hydrocarbons with a different number of aromatic rings were calculated using ab initio calculations at MP2/cc-PVTZ level. Results show that an additional aromatic ring in structure of polycyclic aromatic hydrocarbons significantly strengthens CH/O interactions. Calculated interaction energies in optimized structures of the most stable tetracene/water complex is -2.27 kcal/mol, anthracene/water is -2.13 kcal/mol and naphthalene/water is -1.97 kcal/mol. These interactions are stronger than CH/O contacts in benzene/water complex (-1.44 kcal/mol) while CH/O contacts in tetracene/water complex are even stronger than CH/O contacts in pyridine/water complexes (-2.21 kcal/mol). Electrostatic potential maps for different polycyclic aromatic hydrocarbons were calculated and used to explain trends in the energies of interactions. Copyright © 2017 Elsevier Inc. All rights reserved.

(1E,4E)-1,5-Bis[4-(di­ethyl­amino)­phen­yl]penta-1,4-dien-3-one

PubMed Central

Ruanwas, Pumsak; Chantrapromma, Suchada; Ghabbour, Hazem A.; Fun, Hoong-Kun

2014-01-01

There are two crystallograpically independent mol­ecules in the asymmetric unit of the title bis­chalcone derivative, C25H32N2O. Both mol­ecules are twisted with a dihedral angle between the two substituted benzene rings of 11.19 (16)° in one mol­ecule and 14.40 (15)° in the other. The central penta-1,4-dien-3-one fragments make dihedral angles of 8.49 (17) and 4.26 (17)° with the two adjacent benzene rings in one mol­ecule, whereas the corresponding values are 8.42 (16) and 6.18 (16)° in the other. In the crystal, mol­ecules are arranged into chains along the c-axis direction. Adjacent chains are inter-linked by weak inter­molecular C—H⋯O inter­actions. The crystal is further stabilized by C—H⋯π inter­actions. PMID:24860388

Effects of chemical cues on larval survival, settlement and metamorphosis of abalone Haliotis asinina

NASA Astrophysics Data System (ADS)

Wang, Xiaobing; Bai, Yang; Huang, Bo

2010-11-01

Low larval survival, poor settlement, and abnormal metamorphosis are major problems in seed production of donkey-ear abalone Haliotis asinina. We examined the effects of chemical cues including epinephrine, nor-epinephrine, and serotonin on larval survival, settlement, and metamorphosis in order to determine the possibility of using these chemicals to induce the problems. The results show that epinephrine could enhance metamorphosis rate at 10-6 mol/L only but higher concentrations (10-3-10-4 mol/L); and nor-epinephrine could inhibit the performance significantly, and serotonin could increase significantly the performance at a wide-range concentration (10-3-10-6 mol/L). Treatment with serotonin at 10-5 mol/L for 72 hours resulted in the highest settlement rate (42.2%) and survival rate (49.3%), while at 10-4 mol/L for 72 hours resulted in the highest metamorphosis rate (38.8%). Therefore, serotonin may be used as a fast metamorphosis inducer in abalone culture.

Devitrification properties of lead borate glasses

NASA Astrophysics Data System (ADS)

Bajaj, Anu; Khanna, Atul; Krishnan, K.; Aggarwal, Suresh K.

2013-06-01

Lead borate glasses containing 30 to 60 mol% PbO were prepared by melt quenching technique and devitrified by long duration heat treament in the supercooled region. Glasses crystallized on heating above their glass transition temperature, and the crystalline phases produced on devitrification were characterized by XRD and DSC analyses. Glass with 30 mol% PbO slowly formed a solid solution of Pb6B10O21 and Pb5B8O17 crystalline phases, while glasses with 40 and 50 mol% PbO formed a mixture of Pb6B10O21, Pb5B8O17 and the remanent glassy phase. Glasses with higher PbO concentration of 56 to 60 mol% devitrified completely and produced only Pb5B8O17 crystalline phase. Lead borate glasses with PbO concentration of 40 to 50 mol% showed maximum thermal stability against devitrification, the ease of crystallization of glasses was correlated with the fraction of tetrahedral borons in them.

Crystal structure of benzyl (E)-2-(3,4-di-meth-oxy-benzyl-idene)hydrazine-1-carbodi-thio-ate.

PubMed

Tan, Yew-Fung; Break, Mohammed Khaled Bin; Tahir, M Ibrahim M; Khoo, Teng-Jin

2015-02-01

The title compound, C17H18N2O2S2, synthesized via a condensation reaction between S-benzyl di-thio-carbazate and 3,4-di-meth-oxy-benzaldehyde, crystallized with two independent mol-ecules (A and B) in the asymmetric unit. Both mol-ecules have an L-shape but differ in the orientation of the benzyl ring with respect to the 3,4-di-meth-oxy-benzyl-idine ring, this dihedral angle is 65.59 (8)° in mol-ecule A and 73.10 (8)° in mol-ecule B. In the crystal, the A and B mol-ecules are linked via pairs of N-H⋯S hydrogen bonds, forming dimers with an R 2 (2)(8) ring motif. The dimers are linked via pairs of C-H⋯O hydrogen bonds, giving inversion dimers of dimers. These units are linked by C-H⋯π inter-actions, forming ribbons propagating in the [100] direction.

Crystal structure of 3-hy­droxy­methyl-1,2,3,4-tetra­hydro­isoquinolin-1-one

PubMed Central

Caracelli, Ignez; Hino, Camila Lury; Zukerman-Schpector, Julio; Biaggio, Francisco Carlos; Tiekink, Edward R. T.

2015-01-01

In the title compound, C10H11NO2, two independent but virtually superimposable mol­ecules, A and B, comprise the asymmetric unit. The heterocyclic ring in each mol­ecule has a screw-boat conformation, and the methyl­hydroxyl group occupies a position to one side of this ring with N—C—C—O torsion angles of −55.30 (15) (mol­ecule A) and −55.94 (16)° (mol­ecule B). In the crystal, O—H⋯O and N—H⋯O hydrogen bonding leads to 11-membered {⋯HNCO⋯HO⋯HNC2O} heterosynthons, involving three different mol­ecules, which are edge-shared to generate a supra­molecular chain along the a axis. Inter­actions of the type C—H⋯O provide additional stability to the chains, and link these into a three-dimensional architecture. PMID:26396795

Effects of metal ions on biomass and 5-aminolevulinic acid production in Rhodopseudomonas palustris wastewater treatment.

PubMed

Liu, Shuli; Zhang, Guangming; Li, Jianzheng; Li, Xiangkun; Zhang, Jie

2016-01-01

This work investigated the effects of eight metal ions on Rhodopseudomonas palustris growth and 5-aminolevulinic acid (ALA) yield in wastewater treatment. Results show that metal ions (Mg(2+) of 15 mmol/L, Fe(2+) of 400 μmol/L, Co(2+) of 4 μmol/L, Ni(2+) of 8 μmol/L and Zn(2+) of 4 μmol/L) could effectively improve the chemical oxygen demand (COD) removal, Rp. palustris biomass and ALA yield. The highest ALA yield of 13.1 mg/g-biomass was achieved with Fe(2+) of 400 μmol/L. ALA yields were differentially increased under different metal ions in the following order: Fe(2+) group > Mg(2+) group > Co(2+) group = Ni(2+) group > Zn(2+) group = Mo(2+) group > control. Cu(2+) and Mn(2+) inhibited Rp. palustris growth and ALA production. Mechanism analysis revealed that metal ions changed ALA yields by influencing the activities of ALA synthetase and ALA dehydratase.

Metabolic stability of new anticonvulsants in body fluids and organ homogenates.

PubMed

Marszałek, Dorota; Goldnik, Anna; Pluciński, Franciszek; Mazurek, Aleksander P; Jakubiak, Anna; Lis, Ewa; Tazbir, Piotr; Koziorowska, Agnieszka

2012-01-01

The stability as a function of time of compounds with established anticonvulsant activity: picolinic acid benzylamide (Pic-BZA), picolinic acid 2-fluorobenzylamide (Pic-2-F-BZA), picolinic acid 3-fluorobenzylamide (Pic-3-F-BZA), picolinic acid 4-fluorobenzylamide (Pic-4-F-BZA) and picolinic acid 2-methylbenzylamide (Pic-2-Me-BZA) in body fluids and homogenates of body organs were determined after incubation. It was found that they decompose relatively rapidly in liver and kidney and are stable against enzymes present in body fluids and some organs. These results are consistent with the bond strength expressed as total energy of amide bonds (calculated by quantum chemical methods) in the studied anticonvulsants. The calculated values of the amide bond energy are: 199.4 kcal/mol, 200.2 kcal/mol, 207.5 kcal/mol, 208.4 kcal/mol and 198.2 kcal/mol, respectively. The strength of the amide bonds in the studied anticonvulsants correctly reflects their stability in liver or kidney.

Understanding the new HbA1c units for the diagnosis of Type 2 diabetes.

PubMed

Braatvedt, Geoff D; Cundy, Tim; Crooke, Michael; Florkowski, Chris; Mann, Jim I; Lunt, Helen; Jackson, Rod; Orr-Walker, Brandon; Kenealy, Timothy; Drury, Paul L

2012-09-21

In New Zealand laboratories the measurement of glycated haemoglobin (HbA1c) for diagnosis of diabetes is now only reported in SI units of mmol/mol. HbA1c is now recommended as the preferred test to diagnose diabetes in most circumstances. The requirement for a second positive test in asymptomatic individuals is retained. An HbA1c greater than and equal to 50 mmol/mol (repeated on a second occasion in asymptomatic patients) is diagnostic of diabetes and a value less than and equal to 40 mmol/mol represents normal glucose tolerance. For patients with an initial HbA1c result of 41-49 mmol/mol, cardiovascular risk assessment and lifestyle interventions are recommended with repeat HbA1c screening in 6-12 months. For patients whose HbA1c is less than and equal to 40 mmol/mol, repeat screening (including for CVD risk) at intermittent intervals is recommended as per published guidelines.

N-(1-Allyl-1H-indazol-5-yl)-4-methyl­benzene­sulfonamide

PubMed Central

Chicha, Hakima; Rakib, El Mostapha; Abderrafia, Hafid; Saadi, Mohamed; El Ammari, Lahcen

2013-01-01

The asymmetric unit of the title compound, C17H17N3O2S, contains two independent mol­ecules linked by an N—H⋯O hydrogen bond. The mol­ecules show different conformations. In the first mol­ecule, the fused five- and six-membered ring system is almost perpendicular to the plane through the atoms forming the allyl group, as indicated by the dihedral angle of 85.1 (4)°. The dihedral angle with the methyl­benzene­sulfonamide group is 78.8 (1)°. On the other hand, in the second mol­ecule, the dihedral angles between the indazole plane and the allyl and methyl­benzene­sulfonamide groups are 80.3 (3) and 41.5 (1)°, respectively. In the crystal, mol­ecules are further linked by N—H⋯N and C—H⋯O hydrogen bonds, forming a three-dimensional network. PMID:24454264

Spectroscopic analysis on the resveratrol-DNA binding interactions at physiological pH

NASA Astrophysics Data System (ADS)

Zhang, Shufang; Sun, Xuejun; Jing, Zhihong; Qu, Fengli

2011-11-01

The interaction of resveratrol with calf thymus deoxyribonucleic acid (ctDNA) under physiological conditions (Tris-HCl buffer solutions, pH 7.4) was studied by spectroscopy, fluorescence spectroscopy and viscosity measurement method, respectively. Results indicated that a complex of resveratrol with ctDNA was formed with a binding constant of K17 °C = 5.49 × 10 3 L mol -1 and K37 °C = 1.90 × 10 4 L mol -1. The fluorescence quenching mechanism of acridine orange (AO)-ctDNA by resveratrol was shown to be a static quenching type. The thermodynamic parameters of the complex were calculated by a double reciprocal method: ΔHms=4.64×10 J mol, ΔSms=231.8 J K mol and ΔGms=-2.54×10 J mol (37 °C). Spectroscopic techniques together with viscosity determination provided evidences of intercalation mode of binding for the interaction between resveratrol and ctDNA.

Epoxidation of cottonseed oil by aqueous hydrogen peroxide catalysed by liquid inorganic acids.

PubMed

Dinda, Srikanta; Patwardhan, Anand V; Goud, Vaibhav V; Pradhan, Narayan C

2008-06-01

The kinetics of epoxidation of cottonseed oil by peroxyacetic acid generated in situ from hydrogen peroxide and glacial acetic acid in the presence of liquid inorganic acid catalysts were studied. It was possible to obtain up to 78% relative conversion to oxirane with very less oxirane cleavage by in situ technique. The rate constants for sulphuric acid catalysed epoxidation of cottonseed oil were in the range 0.39-5.4 x 10(-6)L mol(-1)s(-1) and the activation energy was found to be 11.7 kcal mol(-1). Some thermodynamic parameters such as enthalpy, entropy, and free energy of activation were determined to be of 11.0 kcal mol(-1), -51.4 cal mol(-1)K(-1) and 28.1 kcal mol(-1), respectively. The order of effectiveness of catalysts was found to be sulphuric acid>phosphoric acid>nitric acid>hydrochloric acid. Acetic acid was found to be superior to formic acid for the in situ cottonseed oil epoxidation.

Building Cultural Capability for Full-Spectrum Operations

DTIC Science & Technology

2008-01-01

Mol, Born, Willemsen, & Van der Molen , 2005; Caligiuri & Day, 2000). In addition to these broad traits, antecedents to cross-cultural competence...510-517. 18 Mol, S. T., Born, M. P., Willemsen, M. E., & Van Der Molen , H. T. (2005). Predicting expatriate job performance for selection purposes: A...et al., 2003). In addition, self-regulation has been shown to be critical for adjustment (Matsumoto et al., 2003; van Oudenhoven, Mol, & Van der Zee

Sensitive determination of norepinephrine, synephrine, and isoproterenol by capillary electrophoresis with indirect electrochemiluminescence detection.

PubMed

Liu, Yan-Ming; Cao, Jun-Tao; Zheng, Yan-Li; Chen, Yong-Hong

2008-07-01

A new and sensitive method for the determination of norepinephrine (NE), synephrine, and isoproterenol was developed by CE separation and indirect electrochemiluminescence detection (ECL) based on their quenching effects on the tris(2,2'-bipyridyl)-ruthenium(II)/tripropylamine (TPA) system. The conditions for CE separation and ECL detection were investigated in detail. Under the optimum conditions, the three analytes were well separated within 9 min. The LODs (S/N = 3) in standard solution are 2.6 x 10(-8) mol/L for NE, 6.6 x 10(-9) mol/L for synephrine and 8.4 x 10(-8) mol/L for isoproterenol, respectively. The precisions of intraday and interday are less than 4.4 and 6.1%, respectively. The LOQs (S/N = 10) in real human urine samples are 2.6 x 10(-7) mol/L for NE, 8.8 x 10(-8 ) mol/L for synephrine, and 8.8 x 10(-7) mol/L for isoproterenol, respectively. The applicability of the proposed method was illustrated in the determination of 20 human urine samples from diabetic patients and healthy persons. The results obtained indicated that the level of NE in patients (mean value 0.41 micromol/L) was higher than that in healthy persons (mean value 0.24 micromol/L).

Extraction of Proanthocyanidins and Anthocyanins from Grape Skin by Using Ionic Liquids

PubMed Central

2017-01-01

Summary In this study, eight different types of imidazolium-based ionic liquids (ILs) were applied as new solvents in the extraction of flavonoids from grape skin, and compared to the conventional organic solvent extraction that was not reported earlier. The structure of anions, cations and concentration of ILs significantly affected extraction yields. The highest mass fractions of proanthocyanidins and anthocyanins were obtained with 2.5 mol/L of 1-butyl-3-methylimidazolium bromide [C4mim][Br] and 2.5 mol/L of 1-ethyl-3-methylimidazolium bromide [C2mim][Br], respectively. The studied ILs provided an excellent preliminary result in the extraction of anthocyanins. Significantly higher mass fractions of total and all free anthocyanins were extracted with 2.5 mol/L of [C2mim][Br] and 2.5 mol/L of 1-methylimidazolium hydrogen sulfate [mim][HSO4] than with conventional solvent with the exception of anthocyanin-3-O-acetylmonoglucosides in the latter. On the other hand, 2.5 mol/L of [C4mim][Br] and 2.5 mol/L of 1-(4-sulfobutyl)-3-methylimidazolium hydrogen sulfate [sC4mim][HSO4] showed significantly higher selectivity towards anthocyanin-3-O-acetylmonoglucosides and anthocyanin-3-(6-O-p-coumaroyl)monoglucosides. PMID:29089857

DDT, DDE, and 1-hydroxypyrene levels in children (in blood and urine samples) from Chiapas and Oaxaca, Mexico.

PubMed

Pérez-Maldonado, Iván N; Trejo-Acevedo, Antonio; Pruneda-Alvarez, Lucia Guadalupe; Gaspar-Ramirez, Octavio; Ruvalcaba-Aranda, Selene; Perez-Vazquez, Francisco Javier

2013-11-01

The aim of this study was to evaluate the DDT, DDE, and 1-hydroxypyrene exposure levels of children living in communities located in southeastern Mexico. The study communities were Lacanja and Victoria in Chiapas state and Ventanilla in Oaxaca state. Children living in Lacanja had total blood DDT levels (mean ± SD, 29,039.6 ± 11,261.4 ng/g lipid) that were significantly higher than those of children in Victoria (10,220.5 ± 7,893.1 ng/g lipid) and Ventanilla (11,659.7 ± 6,683.7 ng/g lipid). With respect to the 1-hydroxypyrene levels in urine samples, the levels in Lacanja (4.8 ± 4.1 μg/L or 4.5 ± 3.9 μmol/mol creatinine) and Victoria (4.6 ± 3.8 μg/L or 3.9 ± 3.0 μmol/mol Cr) were significantly higher than levels found in Ventanilla (3.6 ± 1.4 μg/L or 2.5 ± 0.5 μmol/mol Cr). In conclusion, our data indicate high levels of exposure in children living in the communities studied in this work. The evidence found in this study could be further used as a trigger to revisit local policies on environmental exposures.

Improving CO2 permeation and separation performance of CO2-philic polymer membrane by blending CO2 absorbents

NASA Astrophysics Data System (ADS)

Cheng, Jun; Hu, Leiqing; Li, Yannan; Liu, Jianzhong; Zhou, Junhu; Cen, Kefa

2017-07-01

To research effects of CO2 absorption capacity and type of CO2 absorbent on the CO2 separation and free-volume properties of facilitated transport membranes, two types of CO2 absorbents, namely monoethanolamine (MEA) and ionic liquids (ILs:[P66614][Triz] and [P66614][2-Op]), were adopted. The CO2 absorption capacities of MEA, [P66614][Triz] and [P66614][2-Op] were about 0.561 mol CO2 per mol, 0.95 mol CO2 per mol and 1.60 mol CO2 per mol, respectively. All mean free-volume hole radiuses of membranes decreased after blending CO2 absorbents. After polymer membrane blended with two ILs, number of free-volume hole increased, resulting in modest increase of the fractional free volume. Both CO2 permeability and selectivity increased after blending MEA and ILs. The increasing range of CO2 permeability corresponded with CO2 absorption capacity of CO2 absorbents, and membrane blending with [P66614][2-Op] showed the highest CO2 permeability of 672.1 Barrers at 25 °C. Pebax/PEGDME membrane blending with MEA obtained the highest CO2/H2 and CO2/CH4 selectivity at 17.8 and 20.5, respectively.

Reaction mechanism of guanidinoacetate methyltransferase, concerted or step-wise.

PubMed

Zhang, Xiaodong; Bruice, Thomas C

2006-10-31

We describe a quantum mechanics/molecular mechanics investigation of the guanidinoacetate methyltransferase catalyzed reaction, which shows that proton transfer from guanidinoacetate (GAA) to Asp-134 and methyl transfer from S-adenosyl-L-methionine (AdoMet) to GAA are concerted. By self-consistent-charge density functional tight binding/molecular mechanics, the bond lengths in the concerted mechanism's transition state are 1.26 A for both the OD1 (Asp-134)-H(E) (GAA) and H(E) (GAA)-N(E) (GAA) bonds, and 2.47 and 2.03 A for the S8 (AdoMet)-C9 (AdoMet) and C9 (AdoMet)-N(E) (GAA) bonds, respectively. The potential-energy barrier (DeltaE++) determined by single-point B3LYP/6-31+G*//MM is 18.9 kcal/mol. The contributions of the entropy (-TDeltaS++) and zero-point energy corrections Delta(ZPE)++ by normal mode analysis are 2.3 kcal/mol and -1.7 kcal/mol, respectively. Thus, the activation enthalpy of this concerted mechanism is predicted to be DeltaH++ = DeltaE++ plus Delta(ZPE)++ = 17.2 kcal/mol. The calculated free-energy barrier for the concerted mechanism is DeltaG++ = 19.5 kcal/mol, which is in excellent agreement with the value of 19.0 kcal/mol calculated from the experimental rate constant (3.8 +/- 0.2.min(-1)).

The compressibility of cubic white and orthorhombic, rhombohedral, and simple cubic black phosphorus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Clark, Simon M; Zaug, Joseph

2010-03-10

The effect of pressure on the crystal structure of white phosphorus has been studied up to 22.4 GPa. The ?alpha phase was found to transform into the alpha' phase at 0.87 +- 0.04 GPa with a volume change of 0.1 +- 0.3 cc/mol. A fit of a second order Birch- Murnaghan equation to the data gave Vo = 16.94 ? 0.08 cc/mol and Ko = 6.7 +- 0.5 GPa for the alpha phase and Vo = 16.4 +- 0.1 cc/mol and Ko = 9.1 +- 0.3 GPa for the alpha' phase. The alpha' phase was found to transform to themore » A17 phase of black phosphorus at 2.68 +- 0.34 GPa and then with increasing pressure to the A7 and then simple cubic phase of black phosphorus. A fit of a second order Birch-Murnaghan equation to our data combined with previous measurements gave Vo = 11.43 +- 0.05 cc/mol and Ko = 34.7 +- 0.5 GPa for the A17 phase, Vo = 9.62 +- 0.01 cc/mol and Ko = 65.0 +- 0.6 GPa for the A7 phase and , Vo = 9.23 +- 0.01 cc/mol and Ko = 72.5 +- 0.3 GPa for the simple cubic phase.« less

MAGNETIC BEHAVIOR OF IRON IONS IN THE P2O5·CaO GLASS MATRIX

NASA Astrophysics Data System (ADS)

ARDELEAN, I.; ANDRONACHE, C.; PǍŞCUŢǍ, P.

The temperature dependence of the magnetic susceptibility of xFe2O3·(100-x)-[P2O5·CaO] glasses with 035 mol%, the evaluated values of the μeff indicate either the presence of Fe+ ions or the coordination influence on the magnetic moment of iron ions, but the presence of small quantities of the antiferromagnetic or ferrimagnetic interactions between iron ions in studied temperature range cannot be excluded. The high temperature susceptibility results indicate that the iron ions are isolated or participate in dipole-dipole interactions for glasses with x≤35 mol% and are antiferromagnetically coupled for higher contents of Fe2O3.

Discrimination of magnoliae officinalis cortex based on the quantitative profiles of magnolosides by two-channel liquid chromatography with electrochemical detection.

PubMed

Xue, Zhenzhen; Kotani, Akira; Yang, Bin; Hakamata, Hideki

2018-05-31

A two-channel liquid chromatography with electrochemical detection system (2LC-ECD) was newly designed for the simultaneous determination of magnolosides A, B, F, H, and L in the first channel and other magnolosides D and M in the second channel, respectively. Peak heights had linear relationships to the magnoloside concentrations in a range of 0.02-16 μmol/L for H, 0.01-12 μmol/L for A, 0.02-12 μmol/L for F and L, 0.01-8 μmol/L for B, 0.002-6 μmol/L for D, and 0.002-4 μmol/L for M, respectively. Seven magnolosides in magnoliae officinalis cortex (MOC) were determined by the 2LC-ECD, and the obtained quantitative profiles of magnolosides were applied to the discrimination between the MOC samples harvested from Hubei and Sichuan (called Chuan po) and from Zhejiang and Fujian (called Wen po). By principal component analysis (PCA) and supervised partial least squares discriminant analysis (PLS-DA) based on the quantitative profiles of the magnolosides, Chuan po were clearly discriminated from Wen po on the plots obtained from our multivariable analyses. Copyright © 2018 Elsevier B.V. All rights reserved.

Kinetic study of hydrolysis of xylan and agricultural wastes with hot liquid water.

PubMed

Zhuang, Xinshu; Yuan, Zhenhong; Ma, Longlong; Wu, Chuangzhi; Xu, Mingzhong; Xu, Jingliang; Zhu, Shunni; Qi, Wei

2009-01-01

We investigated the kinetics of hot liquid water (HLW) hydrolysis over a 60-min period using a self-designed setup. The reaction was performed within the range 160-220 degrees C, under reaction conditions of 4.0 MPa, a 1:20 solid:liquid ratio (g/mL), at 500 rpm stirring speed. Xylan was chosen as a model compound for hemicelluloses, and two kinds of agricultural wastes-rice straw and palm shell-were used as typical feedstocks representative of herbaceous and woody biomasses, respectively. The hydrolysis reactions for the three kinds of materials followed a first-order sequential kinetic model, and the hydrolysis activation energies were 65.58 kJ/mol for xylan, 68.76 kJ/mol for rice straw, and 95.19 kJ/mol for palm shell. The activation energies of sugar degradation were 147.21 kJ/mol for xylan, 47.08 kJ/mol for rice straw and 79.74 kJ/mol for palm shell. These differences may be due to differences in the composition and construction of the three kinds of materials. In order to reduce the decomposition of sugars, the hydrolysis time of biomasses such as rice straw and palm shell should be strictly controlled.

Why Do Enolate Anions Favor O-Alkylation over C-Alkylation in the Gas Phase? The Roles of Resonance and Inductive Effects in the Gas-Phase SN2 Reaction between the Acetaldehyde Enolate Anion and Methyl Fluoride.

PubMed

Seitz, Christian G; Zhang, Huaiyu; Mo, Yirong; Karty, Joel M

2016-05-06

Contributions by resonance and inductive effects toward the net activation barrier were determined computationally for the gas-phase SN2 reaction between the acetaldehyde enolate anion and methyl fluoride, for both O-methylation and C-methylation, in order to understand why this reaction favors O-methylation. With the use of the vinylogue extrapolation methodology, resonance effects were determined to contribute toward increasing the size of the barrier by about 9.5 kcal/mol for O-methylation and by about 21.2 kcal/mol for C-methylation. Inductive effects were determined to contribute toward increasing the size of the barrier by about 1.7 kcal/mol for O-methylation and 4.2 kcal/mol for C-methylation. Employing our block-localized wave function methodology, we determined the contributions by resonance to be 12.8 kcal/mol for O-methylation and 22.3 kcal/mol for C-methylation. Thus, whereas inductive effects have significant contributions, resonance is the dominant factor that leads to O-methylation being favored. More specifically, resonance serves to increase the size the barrier for C-methylation significantly more than it does for O-methylation.

Effect of the temperature, pH and irradiance on the photosynthetic activity by Scenedesmus obtusiusculus under nitrogen replete and deplete conditions.

PubMed

Cabello, Juan; Toledo-Cervantes, Alma; Sánchez, León; Revah, Sergio; Morales, Marcia

2015-04-01

This paper evaluates the effect of the irradiance, pH and temperature on the photosynthetic activity (PA) of Scenedesmus obtusiusculus under N-replete and N-deplete conditions through oxygen measurements. The highest PA values were 160 mgO2 gb(-1) h(-1) at 620 μmol m(-2) s(-1), 35 °C and pH of 8 under N-replete conditions and 3.3 mgO2 gb(-1) h(-1) at 100 μmol m(-2) s(-1), 28.5 °C and pH of 5.5 for N-deplete conditions. Those operation conditions were tested in a flat-panel photobioreactor. The biomass productivity was 0.97 gb L(-1) d(-1) under N-replete conditions with a photosynthetic efficiency (PE) of 4.4% yielding 0.85 gb mol photon(-1). Similar biomass productivity was obtained under N-deplete condition; and the lipid productivity was 0.34 gL L(-1) d(-1) with a PE of 7.8% yielding 0.39 gL mol photon(-1). The apparent activation and deactivation energies were 16.1 and 30 kcal mol(-1), and 11.9 and 15.3 kcal mol(-1), for N-replete and N-deplete conditions, respectively. Copyright © 2015 Elsevier Ltd. All rights reserved.

Thin Layer Drying Kinetics of By-Products from Olive Oil Processing

PubMed Central

Montero, Irene; Miranda, Teresa; Arranz, Jose Ignacio; Rojas, Carmen Victoria

2011-01-01

The thin-layer behavior of by-products from olive oil production was determined in a solar dryer in passive and active operation modes for a temperature range of 20–50 °C. The increase in the air temperature reduced the drying time of olive pomace, sludge and olive mill wastewater. Moisture ratio was analyzed to obtain effective diffusivity values, varying in the oil mill by-products from 9.136 × 10−11 to 1.406 × 10−9 m2/s in forced convection (ma = 0.22 kg/s), and from 9.296 × 10−11 to 6.277 × 10−10 m2/s in natural convection (ma = 0.042 kg/s). Diffusivity values at each temperature were obtained using the Fick’s diffusion model and, regardless of the convection, they increased with the air temperature. The temperature dependence on the effective diffusivity was determined by an Arrhenius type relationship. The activation energies were found to be 38.64 kJ/mol, 30.44 kJ/mol and 47.64 kJ/mol for the olive pomace, the sludge and the olive mill wastewater in active mode, respectively, and 91.35 kJ/mol, 14.04 kJ/mol and 77.15 kJ/mol in natural mode, in that order. PMID:22174639

Calorimetric determination of the enthalpy of 1-butyl-3-methylimidazolium bromide synthesis: a key quantity in thermodynamics of ionic liquids.

PubMed

Paulechka, Yauheni U; Kabo, Andrey G; Blokhin, Andrey V

2009-11-05

The enthalpy of the 1-butyl-3-methylimidazolium bromide [C(4)mim]Br ionic liquid synthesis reaction 1-methylimidazole (liq) + 1-bromobutane (liq) --> [C(4)mim]Br (liq) was determined in a homemade small-volume isoperibol calorimeter to be Delta(r)H degrees (298) = -87.7 +/- 1.6 kJ x mol(-1). The activation energy for this reaction in a homogeneous system E(A) = 73 +/- 4 kJ x mol(-1) was found from the results of calorimetric measurements. The formation enthalpies for the crystalline and liquid [C(4)mim]Br were determined from the calorimetric data: Delta(f)H degrees (298)(cr) = -178 +/- 5 kJ x mol(-1) and Delta(f)H degrees (298)(liq) = -158 +/- 5 kJ x mol(-1). The ideal-gas formation enthalpy of this compound Delta(f)H degrees (298)(g) = 16 +/- 7 kJ x mol(-1) was calculated using the methods of quantum chemistry and statistical thermodynamics. The vaporization enthalpy of [C(4)mim]Br, Delta(vap)H degrees (298) = 174 +/- 9 kJ x mol(-1), was estimated from the experimental and calculated formation enthalpies. It was demonstrated that vapor pressure of this ionic liquid cannot be experimentally determined.

The functional significance of C3-C4 intermediate traits in Heliotropium L. (Boraginaceae): gas exchange perspectives.

PubMed

Vogan, Patrick J; Frohlich, Michael W; Sage, Rowan F

2007-10-01

We demonstrate for the first time the presence of species exhibiting C3-C4 intermediacy in Heliotropium (sensu lato), a genus with over 100 C3 and 150 C4 species. CO2 compensation points (Gamma) and photosynthetic water-use efficiencies (WUEs) were intermediate between C3 and C4 values in three species of Heliotropium: Heliotropium convolvulaceum (Gamma = 20 micromol CO2 mol(-1) air), Heliotropium racemosum (Gamma = 22 micromol mol(-1)) and Heliotropium greggii (Gamma = 17 micromol mol(-1)). Heliotropium procumbens may also be a weak C3-C4 intermediate based on a slight reduction in Gamma (48.5 micromol CO2 mol(-1)) compared to C3Heliotropium species (52-60 micromol mol(-1)). The intermediate species H. convolvulaceum, H. greggii and H. racemosum exhibited over 50% enhancement of net CO2 assimilation rates at low CO2 levels (200-300 micromol mol(-1)); however, no significant differences in stomatal conductance were observed between the C3 and C3-C4 species. We also assessed the response of Gamma to variation in O2 concentration for these species. Heliotropium convolvulaceum, H. greggii and H. racemosum exhibited similar responses of Gamma to O2 with response slopes that were intermediate between the responses of C3 and C4 species below 210 mmol O2 mol(-1) air. The presence of multiple species displaying C3-C4 intermediate traits indicates that Heliotropium could be a valuable new model for studying the evolutionary transition from C3 to C4 photosynthesis.

Desorption Kinetics of H2O from Cab-O-Sil-M-7D and Hi-Sil-233 Silica Particles

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dinh, L.; Balooch, M.; LeMay, J.D.

2000-01-26

Temperature programmed desorption (TPD) was performed at temperatures up to 850K on Cab-O-Sil-M-7D and Hi-Sil-233 silica particles. Physisorbed water molecules on both types of silica had activation energies in the range of 9-14.5 kcal/mol. However, the activation energies of desorption for chemisorbed water varied from {approx} 19 kcal/mol to > 59 kcal/mol for Cab-O-Sil-M-7D, and {approx} 23-37 kcal/mol for Hi-Sil-233. Our results suggest that physisorbed water can be effectively pumped away at room temperature (or preferably at 320 K) in a matter of hours. Chemisorbed water with high activation energies of desorption (>30 kcal/mol) will not escape the silica surfacesmore » in 100 years even at 320 K, while a significant amount of the chemisorbed water with medium activation energies (19-26 kcal/mol) will leave the silica surfaces in that time span. Most of the chemisorbed water with activation energies < 30 kcal/mol can be pumped away in a matter of days in a good vacuum environment at 500 K. We had previously measured about 0.1-0.4 wt. % of water in M9787 polysiloxane formulations containing {approx} 21% Cab-O-Sil-M-7D and {approx} 4% Hi-Sil-233. Comparing present results with these formulations, we conclude that absorbed H{sub 2}O and Si-OH bonds on the silica surfaces are the major contributors to water outgassing from M97 series silicones.« less

Actin filaments in the acrosomal reaction of Limulus sperm. Motion generated by alterations in the packing of the filaments.

PubMed

Tilney, L G

1975-02-01

When Limulus sperm are induced to undergo the acrosomal reaction, a process, 50 mum in length, is generated in a few seconds. This process rotates as it elongates; thus the acrosomal process literally screws through the jelly of the egg. Within the process is a bundle of filaments which before induction are coiled up inside the sperm. The filament bundle exists in three stable states in the sperm. One of the states can be isolated in pure form. It is composed of only three proteins whose molecular weights (mol wt) are 43,000, 55,000, and 95,000. The 43,000 mol wt protein is actin, based on its molecular weight, net charge, morphology, G-F transformation, and heavy meromyosin (HMM) binding. The 55,000 mol wt protein is in equimolar ratio to actin and is not tubulin, binds tenaciously to actin, and inhibits HMM binding. Evidence is presented that both the 55,000 mol wt protein and the 95,000 mol wt protein (possibly alpha-actinin) are also present in Limulus muscle. Presumably these proteins function in the sperm in holding the actin filaments together. Before the acrosomal reaction, the actin filaments are twisted over one another in a supercoil; when the reaction is completed, the filaments lie parallel to each other and form an actin paracrystal. This change in their packing appears to give rise to the motion of the acrosomal process and is under the control of the 55,000 mol wt protein and the 95,000 mol wt protein.

Retinol induces morphological alterations and proliferative focus formation through free radical-mediated activation of multiple signaling pathways.

PubMed

Gelain, Daniel Pens; Pasquali, Matheus Augusto de Bittencourt; Caregnato, Fernanda Freitas; Castro, Mauro Antonio Alves; Moreira, José Claudio Fonseca

2012-04-01

Toxicity of retinol (vitamin A) has been previously associated with apoptosis and/or cell malignant transformation. Thus, we investigated the pathways involved in the induction of proliferation, deformation and proliferative focus formation by retinol in cultured Sertoli cells of rats. Sertoli cells were isolated from immature rats and cultured. The cells were subjected to a 24-h treatment with different concentrations of retinol. Parameters of oxidative stress and cytotoxicity were analyzed. The effects of the p38 inhibitor SB203580 (10 μmol/L), the JNK inhibitor SP600125 (10 μmol/L), the Akt inhibitor LY294002 (10 μmol/L), the ERK inhibitor U0126 (10 μmol/L) the pan-PKC inhibitor Gö6983 (10 μmol/L) and the PKA inhibitor H89 (1 μmol/L) on morphological and proliferative/transformation-associated modifications were studied. Retinol (7 and 14 μmol/L) significantly increases the reactive species production in Sertoli cells. Inhibition of p38, JNK, ERK1/2, Akt, and PKA suppressed retinol-induced [(3)H]dT incorporation into the cells, while PKC inhibition had no effect. ERK1/2 and p38 inhibition also blocked retinol-induced proliferative focus formation in the cells, while Akt and JNK inhibition partially decreased focus formation. ERK1/2 and p38 inhibition hindered transformation-associated deformation in retinol-treated cells, while other treatments had no effect. Our results suggest that activation of multiple kinases is responsible for morphological and proliferative changes associated to malignancy development in Sertoli cells by retinol at the concentrations higher than physiological level.

A density functional for core-valence correlation energy

NASA Astrophysics Data System (ADS)

Ranasinghe, Duminda S.; Frisch, Michael J.; Petersson, George A.

2015-12-01

A density functional, ɛCV-DFT(ρc, ρv), describing the core-valence correlation energy has been constructed as a linear combination of ɛLY Pcorr(ρc), ɛV WN5corr(ρc, ρv), ɛPBEcorr(ρc, ρv), ɛSlaterex(ρc, ρv), ɛHCTHex(ρc, ρv), ɛHFex(ρc, ρv), and F CV -DFT (" separators=" N i , Z i ) , a function of the nuclear charges. This functional, with 6 adjustable parameters, reproduces (±0.27 kcal/mol rms error) a benchmark set of 194 chemical energy changes including 9 electron affinities, 18 ionization potentials, and 167 total atomization energies covering the first- and second-rows of the periodic table. This is almost twice the rms error (±0.16 kcal/mol) obtained with CCSD(T)/MTsmall calculations, but less than half the rms error (±0.65 kcal/mol) obtained with MP2/GTlargeXP calculations, and somewhat smaller than the rms error (±0.39 kcal/mol) obtained with CCSD/MTsmall calculations. The largest positive and negative errors from ɛCV-DFT(ρc, ρv) were 0.88 and -0.75 kcal/mol with the set of 194 core-valence energy changes ranging from +3.76 kcal/mol for the total atomization energy of propyne to -9.05 kcal/mol for the double ionization of Mg. Evaluation of the ɛCV-DFT(ρc, ρv) functional requires less time than a single SCF iteration, and the accuracy is adequate for any model chemistry based on the CCSD(T) level of theory.

Magnetic, Electric and Optical Properties of Mg-Substituted Ni-Cu-Zn Ferrites

NASA Astrophysics Data System (ADS)

Kabbur, S. M.; Ghodake, U. R.; Kambale, Rahul C.; Sartale, S. D.; Chikhale, L. P.; Suryavanshi, S. S.

2017-10-01

The Ni0.25- x Mg x Cu0.30Zn0.45Fe2O4 ( x = 0.00 mol, 0.05 mol, 0.10 mol, 0.15 mol, 0.20 mol and 0.25 mol) magnetic oxide system was prepared by a sol-gel auto-combustion method using glycine as a fuel. X-ray diffraction study reveals the formation of pure spinel lattice symmetry along with the presence of a small fraction of unreacted Fe2O3 phase as a secondary phase due to incomplete combustion reaction between fuel and oxidizer. The lattice constant ( a) was found to decrease with the increase of Mg2+ content; the average crystallite size ( D) is observed in the range of 26.78-33.14 nm. At room temperature, all the samples show typical magnetic hysteresis loops with the decrease of magnetic moment ( n B) of Ni-Cu-Zn ferrites with the increase of Mg2+ content. The intrinsic vibrational absorption bands for the tetrahedral and octahedral sites of the spinel structure were confirmed by infrared (IR) spectroscopy. The optical parameters such as refractive index ( η), velocity of IR waves ( v) and jump rates ( J 1, J 2, J) were studied and found to be dependent on the variation of the lattice constant. The Curie temperature ( T c) of Ni-Cu-Zn mixed ferrite was found to decrease with Mg2+ addition. The composition x = 0.15 mol.% with a low dielectric loss tangent of 2% seems to have potential for multilayer chip inductor applications at a wide range of frequencies.

Photosynthesis and antioxidant defense system of Gynura Bicolor DC grown at different elevated CO2 levels

NASA Astrophysics Data System (ADS)

Wang, Minjuan; Liu, Hong; Fu, Yuming

Atmospheric carbon dioxide concentration [CO _{2}] will increase in the future and will affect global climate and ecosystem productivity. However, this is not clearly an area that requires further study on the most appropriate [CO _{2}] selection for plant growth and quality in a closed, controlled environment. The aim of this study was to determine the variation of photosynthetic characteristics and antioxidant status under five CO _{2} concentration (400, 800, 1200, 2000 and 3000 umol mol (-1) ) on the leaf of Gynura bicolor DC. Here the results show that net photosynthetic rate(Pn), Chl content, edible biomass(EB), leaf blade width(LBW), root weight(RW), fructose(Fru) and sucrose(Suc) of Gynura bicolor DC increased under elevated [CO _{2}] of 800 umol mol (-1) , 1200 umol mol (-1) and 2000 umol mol (-1) . On the contrary, photosynthesis and biomass production declined significantly at 3000 umol mol (-1) CO _{2}, While Lipid peroxidation (LPO), malondialdehyde (MDA) and hydrogen peroxide (H _{2}O _{2}) achieved the highest levels. Furthermore, the contents of glutathione (GSH), vitamin C (VC), and vitamin E (VE), and total antioxidant capacity (T-AOC), the activity of superoxide dismutase (SOD), catalase (CAT) and peroxidase (POD) reached the highest level at 2000 umol mol ({-1) }CO _{2}. Results imply that a significant increase in growth and antioxidant defense system of Gynura bicolor DC occurred under 800-2000 umol mol (-1) of CO _{2} concentration provided a theoretical basis for the application for plants selection in Bioregeneration Life Support System (BLSS) and a closed controlled environment.

Distillation Separation of Hydrofluoric Acid and Nitric Acid from Acid Waste Using the Salt Effect on Vapor-Liquid Equilibrium

NASA Astrophysics Data System (ADS)

Yamamoto, Hideki; Sumoge, Iwao

2011-03-01

This study presents the distillation separation of hydrofluoric acid with use of the salt effect on the vapor-liquid equilibrium for acid aqueous solutions and acid mixtures. The vapor-liquid equilibrium of hydrofluoric acid + salt systems (fluorite, potassium nitrate, cesium nitrate) was measured using an apparatus made of perfluoro alkylvinylether. Cesium nitrate showed a salting-out effect on the vapor-liquid equilibrium of the hydrofluoric acid-water system. Fluorite and potassium nitrate showed a salting-in effect on the hydrofluoric acid-water system. Separation of hydrofluoric acid from an acid mixture containing nitric acid and hydrofluoric acid was tested by the simple distillation treatment using the salt effect of cesium nitrate (45 mass%). An acid mixture of nitric acid (5.0 mol · dm-3) and hydrofluoric acid (5.0 mol · dm-3) was prepared as a sample solution for distillation tests. The concentration of nitric acid in the first distillate decreased from 5.0 mol · dm-3 to 1.13 mol · dm-3, and the concentration of hydrofluoric acid increased to 5.41 mol · dm-3. This first distillate was further distilled without the addition of salt. The concentrations of hydrofluoric acid and nitric acid in the second distillate were 7.21 mol · dm-3 and 0.46 mol · dm-3, respectively. It was thus found that the salt effect on vapor-liquid equilibrium of acid mixtures was effective for the recycling of acids from acid mixture wastes.

Molecular energetics of cytosine revisited: a joint computational and experimental study.

PubMed

Gomes, José R B; Ribeiro da Silva, Maria D M C; Freitas, Vera L S; Ribeiro da Silva, Manuel A V

2007-08-02

A static bomb calorimeter has been used to measure the standard molar energy of combustion, in oxygen, at T = 298.15 K, of a commercial sample of cytosine. From this energy, the standard (p degrees = 0.1 MPa) molar enthalpy of formation in the crystalline state was derived as -(221.9 +/- 1.7) kJ.mol(-1). This value confirms one experimental value already published in the literature but differs from another literature value by 13.5 kJ.mol(-1). Using the present standard molar enthalpy of formation in the condensed phase and the enthalpy of sublimation due to Burkinshaw and Mortimer [J. Chem. Soc., Dalton Trans. 1984, 75], (155.0 +/- 3.0) kJ.mol(-1), results in a value for the gas-phase standard molar enthalpy of formation for cytosine of -66.9 kJ.mol(-1). A similar value, -65.1 kJ.mol(-1), has been estimated after G3MP2B3 calculations combined with the reaction of atomization on three different tautomers of cytosine. In agreement with experimental evidence, the hydroxy-amino tautomer is the most stable form of cytosine in the gas phase. The enthalpies of formation of the other two tautomers were also estimated as -60.7 kJ.mol(-1) and -57.2 kJ.mol(-1) for the oxo-amino and oxo-imino tautomers, respectively. The same composite approach was also used to compute other thermochemical data, which is difficult to be measured experimentally, such as C-H, N-H, and O-H bond dissociation enthalpies, gas-phase acidities, and ionization enthalpies.

Structure and stability of the N-hydroxyurea dimer: Post-Hartree-Fock quantum mechanical study

NASA Astrophysics Data System (ADS)

Jabalameli, Ali; Venkatraman, Ramaiyer; Nowek, Andrzej; Sullivan, Richard H.

2000-10-01

The potential energy surface (PES) search of the N-hydroxyurea dimer was searched with second-order Møller-Plesset perturbation theory (MP2) and the 6-31G(d,p) basis set. Eight local minimum energy structures have been found. Four of them have relatively strong (ΔE˜-10 to -13 kcal/mol) intermolecular interactions and the others are moderately strongly interacting species (ΔE˜-3 to -7 kcal/mol). Final estimation of interaction energies was performed using the larger 6-311G(df,pd) and 6-311G(2df,2pd) basis sets. The predicted interaction energies are ΔE=-14.26 kcal/mol and -3.43 kcal/mol for the strongest and the weakest interacting forms of the studied complex, respectively, at the MP2/6-311G(2df,2pd)//MP2/6-31G(d,p) level of theory. The self-consistent field (SCF) interaction energy decomposition indicates the important influence of the deformation term magnitude on ΔE(SCF). The calculated electron correlation contribution to ΔE(MP2) depends on the geometry of the system and varies from -0.5 to -5 kcal/mol. The estimated influence of water on the stability (free energy of hydration) of N-hydroxyurea dimers using the self-consistent isodensity polarized continuum (SCI-PCM) model of solvation varies from ˜-11 kcal/mol to ˜-21 kcal/mol. The forms predicted to be more strongly interacting species in gas phase are less influenced by hydration than the more weakly interacting ones.

Poly (3-hydroxybutyrate-co-15 mol% 3hydroxyhexanoate)/ZnO nanocomposites by solvent casting method: a study of optical, surface, and thermal properties

NASA Astrophysics Data System (ADS)

Vishnu Chandar, J.; Shanmugan, S.; Mutharasu, D.; Azlan, A. A.

2017-01-01

Biopolymer nanocomposites are gaining interest due to their biodegradable and biocompatible nature, with exceptional properties which are superior to those of pure polymer and that can be used as a replacement for petroleum-based plastics. Pure poly (3-hydroxybutyrate-co-15 mol% 3hydroxyhexanoate) [P(3HB-co-15 mol% 3HHx)] and ZnO nanoparticles (NPs) reinforced P(3HB-co-15 mol% 3HHx) composite films were prepared and their morphological, optical, and thermal analyses were carried out to study the effect of ZnO NPs on P(3HB-co-15 mol% 3HHx) copolymer. From optical analysis, a strong absorbance peak at ˜358 nm with high intensity for 5%ZnO NPs reinforced P(3HB-co-15 mol% 3HHx) composite sample was observed. Nano-sized particles and their increased trend with increased ZnO NPs concentration were confirmed by UV-Vis spectral analysis. In addition to that, ZnO NPs reduced the reflectance behaviour of P(3HB-co-15 mol% 3HHx) copolymer in the UV region. Field emission scanning electron microscopy analysis evidenced that the pore numbers and their size in the composite matrix was decreased with increased ZnO NPs concentration. Improved thermal stability and melting temperature of the copolymer matrix was confirmed by thermogravimetric analysis and differential scanning calorimetry analysis, respectively. ZnO NPs acted as a retarding agent and showed a low degree of crystallinity (X c ) and enthalpy of melting (ΔH M ). From these observations, ZnO NPs reinforced P(3HB-co-15 mol% 3HHx) composites can be integrated with suitable resin and can be used as an LED encapsulant to block UV rays. They can also be used as a UV blocking coating material in the glass, plastic, and textile industries, for NIR shielding and food packaging applications.

Solubility of pyromorphite Pb 5(PO 4) 3Cl at 5–65°C and its experimentally determined thermodynamic parameters

DOE PAGES

Topolska, Justyna; Manecki, Maciej; Bajda, Tomasz; ...

2016-03-19

Here, the solubility of synthetic pyromorphite Pb 5(PO 4) 3Cl was determined in a series of dissolution experiments conducted at 5–65 °C and at pH = 2.0. The equilibrium was established within 4 months. The dissolution of pyromorphite was congruent at all the temperatures, and the measured solubility product log K sp,298 for the dissolution reaction: Pb 5(PO 4) 3Cl ⇌ 5Pb 2+ + 3PO 4 3- + Cl - was determined to be –79.6 ± 0.15. The equilibrium ion activity product of pyromorphite increased with temperature, indicating a positive enthalpy of the dissolution reaction in the temperature range frommore » 5 to 65 °C. The temperature dependence of the log K sp was nonlinear: log K sp = A – B/T + D log(T), where A = 478.77 ± 136.62, B = 29,378 ± 6215, and D = –185.81 ± 46.77. This allowed for calculation of ΔG° r = 454.0 ± 1.7 kJ·mol –1, ΔH° r = 101.8 ± 6.0 J·mol –1·K –1, ΔC° p,r = –1545 ± 388.9 J·mol –1·K –1, and ΔS° r = –1181 ± 382 J·mol –1·K –1 of the dissolution reaction. Using these values and the published standard state quantities for constituent ions, the values of ΔG° f = –3764.3 ± 3.5 kJ·mol –1, ΔH° f = –4108.4 ± 7.9 J·mol –1·K –1, S° f = 622 ± 382 J·mol –1·K –1, and C° pf = 402 ± 398 J·mol –1·K –1 were calculated for synthetic pyromorphite Pb 5(PO 4) 3Cl.« less

Elevated Levels of Urinary 8-Hydroxy-2′-deoxyguanosine, Lymphocytic Micronuclei, and Serum Glutathione S-Transferase in Workers Exposed to Coke Oven Emissions

PubMed Central

Liu, Ai-Lin; Lu, Wen-Qing; Wang, Zeng-Zhen; Chen, Wei-Hong; Lu, Wen-Hong; Yuan, Jing; Nan, Pei-Hong; Sun, Jian-Ya; Zou, Ya-Lin; Zhou, Li-Hong; Zhang, Chi; Wu, Tang-Chun

2006-01-01

To investigate associations among occupational exposure to coke oven emissions (COEs), oxidative stress, cytogenotoxic effects, change in the metabolizing enzyme glutathione S-transferase (GST), and internal levels of polycyclic aromatic hydrocarbons (PAHs) in coke oven workers, we recruited 47 male coke oven workers and 31 male control subjects from a coke oven plant in northern China. We measured the levels of 1-hydroxypyrene (1-OHP) and 8-hydroxy-2′-deoxyguanosine (8-OHdG) in urine, micronucleated binucleated cells (BNMNs) in peripheral blood lymphocyte, and GST in serum. Our results showed that the group exposed to COEs had significantly increased levels of 1-OHP [median 5.7; interquartile range (IQR), 1.4–12.0 μmol/mol creatinine] compared with the control group (3; 0.5–6.4 μmol/mol creatinine). In addition, the median levels (IQR) of 8-OHdG, BNMNs, and GST were markedly increased in the exposed [1.9 (1.4–15.4) μmol/mol creatinine; 6 (2–8) per thousand; 22.1 (14.9–31.2) U/L, respectively] compared with controls [1.3 (1.0–4.0) μmol/mol creatinine, 2 (0–4) per thousand; and 13.1 (9.5–16.7) U/L, respectively]. These results appeared to be modified by smoking. However, multivariate logistic regression analysis revealed that exposure to COEs had the highest odds ratio among variables analyzed and that smoking was not a significant confounder of the levels of studied biomarkers. Overall, the present findings suggest that COE exposure led to increased internal PAH burden, genetic damage, oxidative stress, and GST activity. The consequences of the changes in these biomarkers, such as risk of cancer, warrant further investigations. PMID:16675419

Studies of the kinetics and thermochemistry of the forward and reverse reaction Cl + C6H6 = HCl + C6H5.

PubMed

Alecu, I M; Gao, Yide; Hsieh, P-C; Sand, Jordan P; Ors, Ahmet; McLeod, A; Marshall, Paul

2007-05-17

The laser flash photolysis resonance fluorescence technique was used to monitor atomic Cl kinetics. Loss of Cl following photolysis of CCl4 and NaCl was used to determine k(Cl + C6H6) = 6.4 x 10(-12) exp(-18.1 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 578-922 K and k(Cl + C6D6) = 6.2 x 10(-12) exp(-22.8 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 635-922 K. Inclusion of literature data at room temperature leads to a recommendation of k(Cl + C6H6) = 6.1 x 10(-11) exp(-31.6 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) for 296-922 K. Monitoring growth of Cl during the reaction of phenyl with HCl led to k(C6H5 + HCl) = 1.14 x 10(-12) exp(+5.2 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 294-748 K, k(C6H5 + DCl) = 7.7 x 10(-13) exp(+4.9 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 292-546 K, an approximate k(C6H5 + C6H5I) = 2 x 10(-11) cm(3) molecule(-1) s(-1) over 300-750 K, and an upper limit k(Cl + C6H5I) < or = 5.3 x 10(-12) exp(+2.8 kJ mol(-1)/RT) cm(3) molecule(-1) s(-1) over 300-750 K. Confidence limits are discussed in the text. Third-law analysis of the equilibrium constant yields the bond dissociation enthalpy D(298)(C6H5-H) = 472.1 +/- 2.5 kJ mol(-1) and thus the enthalpy of formation Delta(f)H(298)(C6H5) = 337.0 +/- 2.5 kJ mol(-1).

Predictors of adverse neonatal outcomes in intrahepatic cholestasis of pregnancy.

PubMed

Kawakita, Tetsuya; Parikh, Laura I; Ramsey, Patrick S; Huang, Chun-Chih; Zeymo, Alexander; Fernandez, Miguel; Smith, Samuel; Iqbal, Sara N

2015-10-01

We sought to determine predictors of adverse neonatal outcomes in women with intrahepatic cholestasis of pregnancy (ICP). This study was a multicenter retrospective cohort study of all women diagnosed with ICP across 5 hospital facilities from January 2009 through December 2014. Obstetric and neonatal complications were evaluated according to total bile acid (TBA) level. Multivariable logistic regression models were developed to evaluate predictors of composite neonatal outcome (neonatal intensive care unit admission, hypoglycemia, hyperbilirubinemia, respiratory distress syndrome, transient tachypnea of the newborn, mechanical ventilation use, oxygen by nasal cannula, pneumonia, and stillbirth). Predictors including TBA level, hepatic transaminase level, gestational age at diagnosis, underlying liver disease, and use of ursodeoxycholic acid were evaluated. Of 233 women with ICP, 152 women had TBA levels 10-39.9 μmol/L, 55 had TBA 40-99.9 μmol/L, and 26 had TBA ≥100 μmol/L. There was no difference in maternal age, ethnicity, or prepregnancy body mass index according to TBA level. Increasing TBA level was associated with higher hepatic transaminase and total bilirubin level (P < .05). TBA levels ≥100 μmol/L were associated with increased risk of stillbirth (P < .01). Increasing TBA level was also associated with earlier gestational age at diagnosis (P < .01) and ursodeoxycholic acid use (P = .02). After adjusting for confounders, no predictors were associated with composite neonatal morbidity. TBA 40-99.9 μmol/L and TBA ≥100 μmol/L were associated with increased risk of meconium-stained amniotic fluid (adjusted odds ratio, 3.55; 95% confidence interval, 1.45-8.68 and adjusted odds ratio, 4.55; 95% confidence interval, 1.47-14.08, respectively). In women with ICP, TBA level ≥100 μmol/L was associated with increased risk of stillbirth. TBA ≥40 μmol/L was associated with increased risk of meconium-stained amniotic fluid. Copyright © 2015 Elsevier Inc. All rights reserved.

Elevated phenylalanine on newborn screening: follow-up testing may reveal undiagnosed galactosaemia.

PubMed

Shakespeare, Lynette; Downing, Melanie; Allen, Joyce; Casbolt, Ann-Marie; Ellin, Sheila; Maloney, Martin; Race, Gillian; Bonham, Jim

2010-11-01

Introduction Newborn screening for phenylketonuria (PKU) can reveal other conditions which lead to an increased blood spot phenylalanine (Phe) concentration. We have investigated the proportion of blood spot samples that gave a positive screen due to clinically significant conditions other than PKU, compared the positive predictive value (PPV) of our referral Phe cut-off with that recommended by the UK Newborn Screening Programme Centre (UKNSPC) (>210 and >240 μmol/L, respectively) and evaluated the effectiveness of reflex testing for galactosaemia using a lower blood spot Phe cut-off concentration of 130 μmol/L. All blood spot samples that screened positive, for an increased Phe concentration, between April 2001 and March 2008, were identified from the records of the Sheffield Newborn Screening Laboratory and the diagnoses noted. In addition, all cases of galactosaemia detected in or notified to our screening laboratory within this time were also examined and the screened Phe concentrations compared. Out of 438,674 babies who were screened, 67 had Phe concentration >210 μmol/L (15 per 100,000). Of these, 40 had PKU or persistent hyperphenylalaninaemia with a Phe concentration identified by screening between 270 and 2350 μmol/L. A further 11 were diagnosed with another clinically significant disorder: galactosaemia (n = 8), biopterin defects (n = 2), tyrosinaemia Type 1 (n = 1). In addition, 16 had transient elevations in Phe. In total, nine cases of galactosaemia were identified, of whom, three had Phe concentrations <240 μmol/L with one asymptomatic individual having a concentration <210 μmol/L. Adoption of the UKNSPC recommended cut-off (>240 μmol/L) will not affect the detection rate of classical PKU, but will improve the PPV from 76% to 80%. The use of a lower cut-off (130 μmol/L) for reflex galactosaemia testing enables the timely identification of asymptomatic cases that benefit particularly from early treatment, without prompting any unnecessary clinical referrals or delaying any referrals. This intervention may reduce mortality in this vulnerable group.

Thermodynamic characterization of three polymorphic forms of piracetam.

PubMed

Picciochi, Ricardo; Diogo, Hermínio P; da Piedade, Manuel E Minas

2011-02-01

Combustion calorimetry, solution calorimetry, and differential scanning calorimetry (DSC) were used to determine the standard (p° = 0.1 MPa) molar enthalpies of formation of Forms I, II, and III piracetam at 298.15 K, namely, Δ(f) H(m)° (C(6)H(10)O(2)N(2), cr I) = -520.6 ± 1.6 kJ·mol(-1), Δ(f) H(m)° (C(6)H(10)O(2)N(2), cr II) = -523.8 ± 1.6 kJ·mol(-1), and Δ(f) H(m)° (C(6)H(10)O(2)N(2), cr III) = -524.1 ± 1.6 kJ·mol(-1). The enthalpy of formation of gaseous piracetam at 298.15 K was also derived as Δ(f) H(m)° (C(6)H(10)O(2)N(2), g) = -401.3 ± 2.1 kJ·mol(-1), by combining the standard molar enthalpy of formation of Form II piracetam with the corresponding enthalpy of sublimation, Δ(sub) H(m)° (C(6) H(10) O(2) N(2), cr II) = 122.5 ± 1.4 kJ·mol(-1), obtained by drop-sublimation Calvet microcalorimetry and the Knudsen effusion method. The Δ(f) H(m)° (C(6)H(10)O(2)N(2), g) value was used to assess the corresponding predictions by the B3LYP/cc-pVTZ (-335.3 kJ·mol(-1)), G3MP2 (-388.7 kJ·mol(-1)), and CBS-QB3 (-402.8 kJ·mol(-1)) methods, based on the calculation of the atomization enthalpy of piracetam. Finally, the results of the solution and DSC experiments indicate that the stability hierarchy of Forms I, II, and III piracetam at 298.15 K, for which there was conflicting evidence in the literature, is III > II > I. Copyright © 2010 Wiley-Liss, Inc.

Anthropogenic CO2 emissions from a megacity in the Yangtze River Delta of China.

PubMed

Hu, Cheng; Liu, Shoudong; Wang, Yongwei; Zhang, Mi; Xiao, Wei; Wang, Wei; Xu, Jiaping

2018-06-03

Anthropogenic CO 2 emissions from cities represent a major source contributing to the global atmospheric CO 2 burden. Here, we examined the enhancement of atmospheric CO 2 mixing ratios by anthropogenic emissions within the Yangtze River Delta (YRD), China, one of the world's most densely populated regions (population greater than 150 million). Tower measurements of CO 2 mixing ratios were conducted from March 2013 to August 2015 and were combined with numerical source footprint modeling to help constrain the anthropogenic CO 2 emissions. We simulated the CO 2 enhancements (i.e., fluctuations superimposed on background values) for winter season (December, January, and February). Overall, we observed mean diurnal variation of CO 2 enhancement of 23.5~49.7 μmol mol -1 , 21.4~52.4 μmol mol -1 , 28.1~55.4 μmol mol -1 , and 29.5~42.4 μmol mol -1 in spring, summer, autumn, and winter, respectively. These enhancements were much larger than previously reported values for other countries. The diurnal CO 2 enhancements reported here showed strong similarity for all 3 years of the study. Results from source footprint modeling indicated that our tower observations adequately represent emissions from the broader YRD area. Here, the east of Anhui and the west of Jiangsu province contributed significantly more to the anthropogenic CO 2 enhancement compared to the other sectors of YRD. The average anthropogenic CO 2 emission in 2014 was 0.162 (± 0.005) mg m -2  s -1 and was 7 ± 3% higher than 2010 for the YRD. Overall, our emission estimates were significantly smaller (9.5%) than those estimated (0.179 mg m -2  s -1 ) from the EDGAR emission database.

Pharmacological characterization of mechanisms involved in the vasorelaxation produced by rosuvastatin in aortic rings from rats with a cafeteria-style diet

PubMed Central

López-Canales, Jorge Skiold; Lozano-Cuenca, Jair; López-Canales, Oscar Alberto; Aguilar-Carrasco, José Carlos; Aranda-Zepeda, Lidia; López-Sánchez, Pedro; Castillo-Henkel, Enrique Fernando; López-Mayorga, Ruth Mery; Valencia-Hernández, Ignacio

2015-01-01

The present study aimed to investigate the possible influence of several inhibitors and blockers on the vascular effect produced by the acute in vitro application of rosuvastatin to phenylephrine-precontracted aortic rings from rats with a semi-solid, cafeteria-style (CAF) diet. It also aimed to examine the effects of rosuvastatin on the expression of endothelial nitric oxide synthase (eNOS), inducible nitric oxide synthase, constitutive cyclooxygenase, and inducible cyclooxygenase in aortic rings from rats with a CAF diet. From comparisons of the effect on phenylephrine-precontracted aortic rings extracted from rats with two different diets (a standard and a CAF diet), it was found that 10−9–10−5-mol/L rosuvastatin produced lower concentration-dependent vasorelaxation on rings from the CAF diet group. The vasorelaxant effect was unaffected by the vehicle, but it was significantly attenuated by 10−5-mol/L NG-nitro-l-arginine methyl ester, 10−2-mol/L tetraethylammonium, 10−3-mol/L 4-aminopyridine, 10−7-mol/L apamin plus 10−7-mol/L charybdotoxin, 10−5-mol/L indomethacin, or 10−5-mol/L cycloheximide. Moreover, in aortic rings from rats with a CAF diet, rosuvastatin enhanced the expression of eNOS, inducible nitric oxide synthase, constitutive cyclooxygenase, and inducible cyclooxygenase. The acute in vitro application of rosuvastatin to phenylephrine-precontracted aortic rings from rats with a CAF diet had a vasorelaxant effect. Overall, the present results suggest that the stimulation of eNOS, the opening of Ca2+-activated and voltage-activated K+ channels, the stimulation of prostaglandin synthesis and enhanced protein levels of eNOS, inducible nitric oxide synthase, constitutive cyclooxygenase, and inducible cyclooxygenase are involved in this relaxant effect. PMID:25881486

In-vitro study of methylglyoxal and aspirin effects on fibrinolysis parameters.

PubMed

Pouya, Fahima D; Zavar-Reza, Javad; Jalali, Beman A

2013-10-01

Methylglyoxal is a reactive α, β dicarbonyl aldehyde compound that originates from various biochemical pathways. Some studies suggest that increased methylglyoxal in blood leads to changes in fibrinolysis; however, the precise mechanism is not clear. The aim of this study was to compare different concentrations of methylglyoxal and aspirin on fibrinolysis in the plasma of healthy individuals in vitro. Different concentrations of methylglyoxal (5, 50, 100, and 500 μmol/l) and aspirin (1, 10, and 100 mg/l) were added to the plasma citrate. They were incubated at 37°C for 24 h. Then, fibrinolysis parameters were analyzed by the turbidimetric procedure at 405 nm. The Independent Samples t-test was utilized to compare them (P < 0.05). Findings revealed that methylglyoxal at 500 μmol/l with aspirin 100 mg/l had significant changes in the maximum lysis velocity (0.163 ± 0.003), half-time lysis (240 ± 10.00), the total lysis time (485 ± 5.00), lag time in lysis (126 ± 5.77), compared with methylglyoxal at 500 μmol/l (0.104 ± 0.005), (276 ± 5.77), (570 ± 10.00), and (186 ± 5.77), respectively (P < 0.05). Methylglyoxal at 500 μmol/l with aspirin 1 mg/l did not significantly change in either parameter (P > 0.05). Methylglyoxal at 100 μmol/l with aspirin 1 mg/l did not significantly change in either fibrinolysis parameter (P > 0.05), compared with methylglyoxal at 100 μmol/l. Methylglyoxal at 5 μmol/l with aspirin (1, 10, 100  mg/l) changed in all fibrinolysis parameters (P < 0.05), compared with methylglyoxal at 5 μmol/l. The other concentrations were compared in the same way. Aspirin (more than 1 mg/l) had more effect on higher concentrations of methylglyoxal. It increased the velocity of lysis of the clot and shortened clot lysis.

Thermochemical properties for isooctane and carbon radicals: computational study.

PubMed

Snitsiriwat, Suarwee; Bozzelli, Joseph W

2013-01-17

Thermochemical properties for isooctane, its internal rotation conformers, and radicals with corresponding bond energies are determined by use of computational chemistry. Enthalpies of formation are determined using isodesmic reactions with B3LYP density function theory and composite CBS-QB3 methods. Application of group additivity with comparison to calculated values is illustrated. Entropy and heat capacities are determined using geometric parameters, internal rotor potentials, and frequencies from B3LYP/6-31G(d,p) calculations for the lowest energy conformer. Internal rotor potentials are determined for the isooctane parent and for the primary, secondary, and tertiary radicals in order to identify isomer energies. Intramolecular interactions are shown to have a significant effect on the enthalpy of formation of the isooctane parent and its radicals. The computed standard enthalpy of formation for the lowest energy conformers of isooctane from this study is -54.40 ± 1.60 kcal mol(-1), which is 0.8 kcal mol(-1) lower than the evaluated experimental value -53.54 ± 0.36 kcal mol(-1). The standard enthalpy of formation for the primary radical for a methyl on the quaternary carbon is -5.00 ± 1.69 kcal mol(-1), for the primary radical on the tertiary carbon is -5.18 ± 1.69 kcal mol(-1), for the secondary isooctane radical is -9.03 ± 1.84 kcal mol(-1), and for the tertiary isooctane radical is -12.30 ± 2.02 kcal mol(-1). Bond energy values for the isooctane radicals are 100.64 ± 1.73, 100.46 ± 1.73, 96.41 ± 1.88 and 93.14 ± 2.05 kcal mol(-1) for C3•CCCC2, C3CCCC2•, C3CC•CC2, and C3CCC•C2, respectively. Entropy and heat capacity values are reported for the lowest energy homologues.

[Effect of aspirin on cell biological activities in murine bone marrow stromal cells].

PubMed

Du, Mi; Pan, Wan; Yang, Pishan; Ge, Shaohua

2016-03-01

To determine the effect of aspirin on cell proliferation, alkaline phosphatase (ALP) activity, cell cycle and apoptosis in murine bone marrow stromal cells, so as to explore an appropriate dose range to improve bone regeneration in periodontal treatment. ST2 cells were stimulated with aspirin (concentrations of 1, 10, 100 and 1 000 μmol/L) for 1, 2, 3, 5 and 7 d. Cell proliferation was measured by methyl thiazolyl tetrazolium (MTT) assay. After ST2 cells were treated for 1, 3 and 7 d, ALP activity was measured by ALP kit, cell cycle and apoptosis were measured by flow cytometry (FCM) after treated for 48 h. MTT assays showed that various doses of aspirin have different effects on the cell growth. Briefly, lower concentrations (1, 10 μmol/L) of aspirin promoted the cell growth, the A value of 0, 1 and 10 μmol/L aspirin 7-day-treated cells were 0.313±0.012, 0.413±0.010 and 0.387±0.017 respectively (P <0.01 vs control), and so did the ALP level ([4.3±0.9], [6.0±0.3] and [7.7±0.4] μmol·min(-1)·g(-1), P <0.05 vs control), while higher concentrations, especially 1000 μmol/L of aspirin might inhibit the cell growth with time going, A value and ALP level were 0.267±0.016, (4.3±1.3) μmol·min(-1)·g(-1) respectively (P <0.05 vs control). Cell cycle analysis revealed no changes in comparison to control cells after treatment with 1 or 10 μmol/L aspirin, but it was observed that cell mitosis from S phase to G2/M phase proceeded at higher concentrations of 100 μmol/L aspirin, and the cell cycle in phase G0/G1 arrested at 1000 μmol/L. Parallel apoptosis/necrosis studies showed that the percentage of cells in apoptosis decreased dramatically at all doses of aspirin, the apoptosis rates of ST2 cells responded to 0, 1, 10, 100 and 1000 μmol/L aspirin were (11.50±0.90)%, (5.30±0.10)%, (5.50±0.10)%, (4.90±0.90)% and (7.95±0.25)% respectively (P<0.05 vs control). This study demonstrated that lower dosage of aspirin can promote ST2 cells growth, osteogenic activity and inhibit its apoptosis. Aspirin maybe used for the bone reconstruction with a proper concentration.

19-nor vitamin-D analogs: a new class of potent inhibitors of proliferation and inducers of differentiation of human myeloid leukemia cell lines.

PubMed

Asou, H; Koike, M; Elstner, E; Cambell, M; Le, J; Uskokovic, M R; Kamada, N; Koeffler, H P

1998-10-01

We have studied the in vitro biological activities and mechanisms of action of 1,25-dihydroxyvitamin D3 (1,25D3) and nine potent 1,25D3 analogs on proliferation and differentiation of myeloid leukemia cell lines (HL-60, retinoic acid-resistant HL-60 [RA-res HL-60], NB4 and Kasumi-1). The common novel structural motiff for almost all the analogs included removal of C-19 (19-nor); each also had unsaturation of the side chain. All the compounds were potent; for example, the concentration of analogs producing a 50% clonal inhibition (ED50) ranged between 1 x 10(-9) to 4 x 10(-11) mol/L when using the HL-60 cell line. The most active compound [1, 25(OH)2-16,23E-diene-26-trifluoro-19-nor-cholecalciferol (Ro 25-9716)] had an ED50 of 4 x 10(-11) mol/L; in contrast, the 1,25D3 produced an ED50 of 10(-9) mol/L with the HL-60 target cells. Ro 25-9716 (10(-9) mol/L, 3 days) was a strong inducer of myeloid differentiation because it caused 92% of the HL-60 cells to express CD11b and 75% of these cells to reduce nitroblue tetrazolium (NBT). This compound (10(-8) mol/L, 4 days) also caused HL-60 cells to arrest in the G1 phase of the cell cycle (88% cells in G1 v 48% of the untreated control cells). The p27(kip-1), a cyclin-dependent kinase inhibitor which is important in blocking the cell cycle, was induced more quickly and potently by Ro 25-9716 (10(-7) mol/L, 0 to 5 days) than by 1,25D3, suggesting a possible mechanism by which these analogs inhibit proliferation of leukemic growth. The NB4 promyelocytic leukemia cells cultured with the Ro 25-9716 were also inhibited in their clonal proliferation (ED50, 5 x 10(-11) mol/L) and their expression of CD11b was enhanced (80% positive [10(-9) mol/L, 4 days] v 27% untreated NB4 cells). Moreover, the combination of Ro 25-9716 (10(-9) mol/L) and all-trans retinoic acid (ATRA, 10(-7) mol/L) induced 92% of the NB4 cells to reduce NBT, whereas only 26% of the cells became NBT positive after a similar exposure to the combination of 1,25D3 and ATRA. Surprisingly, Ro 25-9716 also inhibited the clonal growth of poorly differentiated leukemia cell lines (RA-res HL-60 [ED50, 4 x 10(-9) mol/L] and Kasumi-1 [ED50, 5 x 10(-10) mol/L]). For HL-60 cells, Ro 25-9716 markedly decreased the percent of the cells in S phase of the cell cycle and increased the expression of the cyclin-dependent kinase inhibitor, p27(kip-1). In summary, 19-nor vitamin D3 compounds strongly induced differentiation and inhibited clonal proliferation of various myeloid leukemia cell lines, suggesting a therapeutic niche for their use in myeloid leukemia.

Multilocus analysis using putative fungal effectors to describe a population of Fusarium oxysporum from sugar beet.

PubMed

Covey, Paul A; Kuwitzky, Brett; Hanson, Mia; Webb, Kimberly M

2014-08-01

Sugar beet (Beta vulgaris) Fusarium yellows is caused by Fusarium oxysporum f. sp. betae and can lead to significant reductions in root yield, sucrose percentage, juice purity, and storability. F. oxysporum f. sp. betae can be highly variable and many F. oxysporum strains isolated from symptomatic sugar beet are nonpathogenic. Identifying pathogenicity factors and their diversity in the F. oxysporum f. sp. betae population could further understanding of how this pathogen causes disease and potentially provide molecular markers to rapidly identify pathogenic isolates. This study used several previously described fungal effector genes (Fmk1, Fow1, Pda1, PelA, PelD, Pep1, Prt1, Rho1, Sge1, Six1, Six6, Snf1, and Ste12) as genetic markers, in a population of 26 pathogenic and nonpathogenic isolates of F. oxysporum originally isolated from symptomatic sugar beet. Of the genes investigated, six were present in all F. oxysporum isolates from sugar beet (Fmk1, Fow1, PelA, Rho1, Snf1, and Ste12), and seven were found to be dispersed within the population (Pda1, PelD, Pep1, Prt1, Sge1, Six1, and Six6). Of these, Fmk1, Fow1, PelA, Rho1, Sge1, Snf1, and Ste12 were significant in relating clade designations and PelD, and Prt1 were significant for correlating with pathogenicity in F. oxysporum f. sp. betae.

Cardiovascular Risk Stratification and Statin Eligibility Based on the Brazilian vs. North American Guidelines on Blood Cholesterol Management.

PubMed

Cesena, Fernando Henpin Yue; Laurinavicius, Antonio Gabriele; Valente, Viviane A; Conceição, Raquel D; Santos, Raul D; Bittencourt, Marcio S

2017-06-01

The best way to select individuals for lipid-lowering treatment in the population is controversial. In healthy individuals in primary prevention: to assess the relationship between cardiovascular risk categorized according to the V Brazilian Guideline on Dyslipidemia and the risk calculated by the pooled cohort equations (PCE); to compare the proportion of individuals eligible for statins, according to different criteria. In individuals aged 40-75 years consecutively submitted to routine health assessment at one single center, four criteria of eligibility for statin were defined: BR-1, BR-2 (LDL-c above or at least 30 mg/dL above the goal recommended by the Brazilian Guideline, respectively), USA-1 and USA-2 (10-year risk estimated by the PCE ≥ 5.0% or ≥ 7.5%, respectively). The final sample consisted of 13,947 individuals (48 ± 6 years, 71% men). Most individuals at intermediate or high risk based on the V Brazilian Guideline had a low risk calculated by the PCE, and more than 70% of those who were considered at high risk had this categorization because of the presence of aggravating factors. Among women, 24%, 17%, 4% and 2% were eligible for statin use according to the BR-1, BR-2, USA-1 and USA-2 criteria, respectively (p < 0.01). The respective figures for men were 75%, 58%, 31% and 17% (p < 0.01). Eighty-five percent of women and 60% of men who were eligible for statin based on the BR-1 criterion would not be candidates for statin based on the USA-1 criterion. As compared to the North American Guideline, the V Brazilian Guideline considers a substantially higher proportion of the population as eligible for statin use in primary prevention. This results from discrepancies between the risk stratified by the Brazilian Guideline and that calculated by the PCE, particularly because of the risk reclassification based on aggravating factors. Existe controvérsia sobre a melhor forma de selecionar indivíduos para tratamento hipolipemiante na população. Em indivíduos saudáveis em prevenção primária: avaliar a relação entre o risco cardiovascular segundo a V Diretriz Brasileira de Dislipidemias e o risco calculado pelas pooled cohort equations (PCE); comparar a proporção de indivíduos elegíveis para estatinas, de acordo com diferentes critérios. Em indivíduos de 40 a 75 anos submetidos consecutivamente a avaliação rotineira de saúde em um único centro, quatro critérios de elegibilidade para estatina foram definidos: BR-1, BR-2 (LDL-c acima ou pelo menos 30 mg/dL acima da meta preconizada pela diretriz brasileira, respectivamente), EUA-1 e EUA-2 (risco estimado pelas PCE em 10 anos ≥ 5,0% ou ≥ 7,5%, respectivamente). Foram estudados 13.947 indivíduos (48 ± 6 anos, 71% homens). A maioria dos indivíduos de risco intermediário ou alto pela V Diretriz apresentou risco calculado pelas PCE baixo e mais de 70% daqueles considerados de alto risco o foram devido à presença de fator agravante. Foram elegíveis para estatina 24%, 17%, 4% e 2% das mulheres pelos critérios BR-1, BR-2, EUA-1 e EUA-2, respectivamente (p < 0,01). Os respectivos valores para os homens foram 75%, 58%, 31% e 17% (p < 0,01). Oitenta e cinco por cento das mulheres e 60% dos homens elegíveis para estatina pelo critério BR-1 não seriam candidatos pelo critério EUA-1. Comparada à diretriz norte-americana, a V Diretriz Brasileira considera uma proporção substancialmente maior da população como elegível para estatina em prevenção primária. Isso se relaciona com discrepâncias entre o risco estratificado pela diretriz brasileira e o calculado pelas PCE, particularmente devido à reclassificação de risco baseada em fatores agravantes.

Geomicrobiology of the Ocean Crust: The Phylogenetic Diversity, Abundance, and Distribution of Microbial Communities Inhabiting Basalt and Implications for Rock Alteration Processes

DTIC Science & Technology

2007-06-01

AF317741) 93 EPR3970- MOlA -Bc32 gamma-Proteobacteria Uncultured gamma proteobacterium clone AT-s80 (AY225635) 99 FPR3970-MO IA-Bc33 Actinobacteria...bacterium partial I AJ966584) 99 1iPR3970- MOlA -Bc65 Unidentified Uncultured bacterium clone CV90 (DQ499320) 89 1iPR3970- MOlA -Bc66 Unidentified Uncultured

1-[1-(4-Chloro­phen­yl)ethyl­idene]carbono­hydrazide

PubMed Central

Du, Lingyun; Du, Lei; Wang, Shuhao

2009-01-01

The mol­ecular skeleton of the title mol­ecule, C9H11ClN4O, is essentially planar, the dihedral angle between the ring and the and N/N/C plane being 6.7 (3)°. In the crystal, inter­molecular N—H⋯O and N—H⋯N hydrogen bonds link the mol­ecules into ribbons propagated along [010]. PMID:21577542

Solvent-Free Benzoin and Stetter Reactions with a Small Amount of NHC Catalyst in the Liquid or Semisolid State.

PubMed

Ema, Tadashi; Nanjo, Yoshiko; Shiratori, Sho; Terao, Yuta; Kimura, Ryo

2016-11-04

The intermolecular or intramolecular asymmetric benzoin reaction was catalyzed by a small amount of N-heterocyclic carbene (NHC) (0.2-1 mol %) under solvent-free conditions. The solvent-free intramolecular asymmetric Stetter reaction also proceeded efficiently with NHC (0.2-1 mol %). In some cases, even solid-to-solid or solid-to-liquid conversions took place with low catalyst loading (0.2-1 mol %).

Theoretical Studies of Oxygen Reduction and Proton Transfer in SOFCs and Nerve Agents on Selected Surfaces

DTIC Science & Technology

2015-11-19

hand, the energy change for CO3 2- +O2→CO5 2- is calculated to be - 105.5 kJ/mol and -87.3 kJ/mol by B3LYP and CCSD(T), respectively. Similarly, the...formation energy of CO4 2- ( CO3 2- +1/2O2→CO4 2- ) is -9.8 kJ/mol and -5.4 kJ/mol by B3LYP and CCSD(T), respectively. All testing results have...This configuration is same as those in their crystal structures of bulk Li2CO3, Na2CO3, and K2CO3. In addition, the average bond length between alkali

Oxidation of 1,3,7-trimethylxanthine by hypochlorite ion

NASA Astrophysics Data System (ADS)

Kheidorov, V. P.; Ershov, Yu. A.; Chalyi, G. Yu.; Titorovich, O. V.

2011-08-01

The kinetics of the oxidative conversion of 1,3,7-trimethylxanthine upon treatment with hypochlorite ions (OCl-) in aqueous medium at 283-298 K and pH 8.2 was studied. The reaction order with respect to each component was determined and proved to be 1. It was established that the temperature dependence of the reaction rate follows the Arrhenius equation. The activation parameters of the reaction were measured: E a = 33.58 kJ/mol, Δ H ≠ = 31.12 kJ/mol, Δ S ≠ = -170.02 J/(K mol), Δ G ≠ = 81.45 kJ/mol. The stoichiometry of the reaction was studied, and the chemistry of the oxidative conversion of caffeine treated with OCl- is discussed.

1,1′:4′,1′′-Terphenyl-2′,5′-dicarb­oxy­lic acid dimethyl sulfoxide-d 6 disolvate

PubMed Central

Pop, Lucian C.; Preite, Marcelo; Manriquez, Juan Manuel; Vega, Andrés; Chavez, Ivonne

2012-01-01

The asymmetric unit of the title solvate, C20H14O4·2C2D6OS, contains half of the substituted terephthalic acid mol­ecule and one solvent mol­ecule. The centroid of the central benzene ring in the acid mol­ecule is coincident with a crystallographic inversion center. Neither the carboxyl nor the phenyl substituents are coplanar with the central aromatic ring, showing dihedral angles of 53.18 (11) and 47.83 (11)°, respectively. The dimethyl sulfoxide solvent mol­ecules are hydrogen bonded to the carb­oxy­lic acid groups. PMID:22606132

Gas standards development in support of NASA's sensor calibration program around the space shuttle.

PubMed

Rhoderick, George C; Thorn, William J; Miller, Walter R; Guenther, Franklin R; Gore, Eric J; Fish, Timothy O

2009-05-15

The National Aeronautics and Space Administration (NASA) Kennedy Space Center (KSC) requires accurate gas mixtures containing argon (Ar), helium (He), hydrogen (H(2)), and oxygen (O(2)) in a balance of nitrogen (N(2)) to calibrate mass spectrometer-based sensors used around their manned and unmanned space vehicles. This also includes space shuttle monitoring around the launch area and inside the shuttle cabin. NASA was in need of these gas mixtures to ensure the safety of the shuttle cabin and the launch system. In 1993, the National Institute of Standards and Technology (NIST) was contracted by NASA to develop a suite of primary standard mixtures (PSMs) containing helium, hydrogen, argon, and oxygen in a balance gas of nitrogen. NIST proceeded to develop a suite of 20 new gravimetric primary PSMs. At the same time NIST contracted Scott Specialty Gases (Plumsteadville, PA) to prepare 18 cylinder gas mixtures which were then sent to NIST. NIST used their newly prepared PSMs to assign concentration values ranging from 100 to 10,000 micromol/mol with relative expanded uncertainties (95% confidence interval) of 0.8-10% to the 18 Scott Specialty Gases prepared mixtures. A total of 12 of the mixtures were sent to NASA as NIST traceable standards for calibration of their mass spectrometers. The remaining 6 AIRGAS mixtures were retained at NIST. In 2006, these original 12 gas standards at NASA had become low in pressure and additionally NASA needed a lower concentration level; therefore, NIST was contracted to certify three new sets of gas standards. NIST prepared a new suite of 22 PSMs with weighing uncertainties of <0.1%. These 22 PSMs were compared to some of the original 20 PSMs developed in 1993 and with the NIST valued assigned Scott Specialty Gas mixtures that NIST had retained. Results between the two suites of primary standards and the 1993 NASA mixtures agreed, verifying their stability. At the same time, NASA contracted AIRGAS (Chicago, Illinois) to prepare 45 cylinder gas mixtures which were then sent to NIST. Each of the 3 sets of standards contained 15 cylinder gas mixtures: set no. 1, He at 12,000 micromol/mol, H(2) at 600 micromol/mol, Ar at 100 micromol/mol, and O(2) at 600 micromol/mol; set no. 2, He at 15 000 micromol/mol, H(2) at 5000 micromol/mol, Ar at 1000 micromol/mol, O(2) at 5000 micromol/mol; and set no. 3, He at 50 micromol/mol, H(2), Ar, and O(2) each at 25 micromol/mol with a balance gas of N(2). NIST used their newly prepared primary standards to assign concentration values to each component in these three new mixture sets to relative expanded uncertainties of 0.5-2.2%. The NIST certified AIRGAS prepared mixtures were then sent to NASA to use as "working standards" to calibrate their mass spectrometers (MSs).

Statin therapy and plasma coenzyme Q10 concentrations--A systematic review and meta-analysis of placebo-controlled trials.

PubMed

Banach, Maciej; Serban, Corina; Ursoniu, Sorin; Rysz, Jacek; Muntner, Paul; Toth, Peter P; Jones, Steven R; Rizzo, Manfredi; Glasser, Stephen P; Watts, Gerald F; Blumenthal, Roger S; Lip, Gregory Y H; Mikhailidis, Dimitri P; Sahebkar, Amirhossein

2015-09-01

Statin therapy may lower plasma coenzyme Q10 (CoQ10) concentrations, but the evidence as to the significance of this effect is unclear. We assessed the impact of statin therapy on plasma CoQ10 concentrations through the meta-analysis of available RCTs. The literature search included selected databases up to April 30, 2015. The meta-analysis was performed using either a fixed-effects or random-effect model according to I(2) statistic. Effect sizes were expressed as weighted mean difference (WMD) and 95% confidence interval (CI). The data from 8 placebo-controlled treatment arms suggested a significant reduction in plasma CoQ10 concentrations following treatment with statins (WMD: -0.44 μmol/L, 95%CI: -0.52, -0.37, p<0.001). The pooled effect size was robust and remained significant in the leave-one-out sensitivity analysis. Subgroup analysis suggested that the impact of statins on plasma CoQ10 concentrations is significant for all 4 types of statins studied i.e. atorvastatin (WMD: -0.41 μmol/L, 95%CI: -0.53, -0.29, p<0.001), simvastatin (WMD: -0.47 μmol/L, 95% CI: -0.61, -0.33, p<0.001), rosuvastatin (WMD: -0.49 μmol/L, 95%CI: -0.67, -0.31, p<0.001) and pravastatin (WMD: -0.43 μmol/L, 95%CI: -0.69, -0.16, p=0.001). Likewise, there was no differential effect of lipophilic (WMD: -0.43 μmol/L, 95%CI: -0.53, -0.34, p<0.001) and hydrophilic statins (WMD: -0.47 μmol/L, 95%CI: -0.62, -0.32, p<0.001). With respect to treatment duration, a significant effect was observed in both subsets of trials lasting <12 weeks (WMD: -0.51 μmol/L, 95%CI: -0.64, -0.39, p<0.001) and ≥12 weeks (WMD: -0.40 μmol/L, 95%CI: -0.50, -0.30, p<0.001). The meta-analysis showed a significant reduction in plasma CoQ10 concentrations following treatment with statins. Further well-designed trials are required to confirm our findings and elucidate their clinical relevance. Copyright © 2015 Elsevier Ltd. All rights reserved.

Mechanism and kinetics for ammonium dinitramide (ADN) sublimation: a first-principles study.

PubMed

Zhu, R S; Chen, Hui-Lung; Lin, M C

2012-11-08

The mechanism for sublimation of NH(4)N(NO(2))(2) (ADN) has been investigated quantum-mechanically with generalized gradient approximation plane-wave density functional theory calculations; the solid surface is represented by a slab model and the periodic boundary conditions are applied. The calculated lattice constants for the bulk ADN, which were found to consist of NH(4)(+)[ON(O)NNO(2)](-) units, instead of NH(4)(+)[N(NO(2))(2)](-), agree quite well with experimental values. Results show that three steps are involved in the sublimation/decomposition of ADN. The first step is the relaxation of the surface layer with 1.6 kcal/mol energy per NH(4)ON(O)NNO(2) unit; the second step is the sublimation of the surface layer to form a molecular [NH(3)]-[HON(O)NNO(2)] complex with a 29.4 kcal/mol sublimation energy, consistent with the experimental observation of Korobeinichev et al. (10) The last step is the dissociation of the [H(3)N]-[HON(O)NNO(2)] complex to give NH(3) and HON(O)NNO(2) with the dissociation energy of 13.9 kcal/mol. Direct formation of NO(2) (g) from solid ADN costs a much higher energy, 58.3 kcal/mol. Our calculated total sublimation enthalpy for ADN(s) → NH(3)(g) + HON(O)NNO(2)) (g), 44.9 kcal/mol via three steps, is in good agreement with the value, 42.1 kcal/mol predicted for the one-step sublimation process in this work and the value 44.0 kcal/mol computed by Politzer et al. (11) using experimental thermochemical data. The sublimation rate constant for the rate-controlling step 2 can be represented as k(sub) = 2.18 × 10(12) exp (-30.5 kcal/mol/RT) s(-1), which agrees well with available experimental data within the temperature range studied. The high pressure limit decomposition rate constant for the molecular complex H(3)N···HON(O)NNO(2) can be expressed by k(dec) = 3.18 × 10(13) exp (-15.09 kcal/mol/RT) s(-1). In addition, water molecules were found to increase the sublimation enthalpy of ADN, contrary to that found in the ammonium perchlorate system, in which water molecules were shown to reduce pronouncedly the enthalpy of sublimation.

Atorvastatin enhances neurite outgrowth in cortical neurons in vitro via up-regulating the Akt/mTOR and Akt/GSK-3β signaling pathways

PubMed Central

Jin, Ying; Sui, Hai-juan; Dong, Yan; Ding, Qi; Qu, Wen-hui; Yu, Sheng-xue; Jin, Ying-xin

2012-01-01

Aim: To investigate whether atorvastatin can promote formation of neurites in cultured cortical neurons and the signaling mechanisms responsible for this effect. Methods: Cultured rat cerebral cortical neurons were incubated with atorvastatin (0.05–10 μmol/L) for various lengths of time. For pharmacological experiments, inhibitors were added 30 min prior to addition of atorvastatin. Control cultures received a similar amount of DMSO. Following the treatment period, phase-contrast digital images were taken. Digital images of neurons were analyzed for total neurite branch length (TNBL), neurite number, terminal branch number, and soma area by SPOT Advanced Imaging software. After incubation with atorvastatin for 48 h, the levels of phosphorylated 3-phosphoinoside-dependent protein kinase-1 (PDK1), phospho-Akt, phosphorylated mammalian target of rapamycin (mTOR), phosphorylated 4E-binding protein 1 (4E-BP1), p70S6 kinase (p70S6K), and glycogen synthase kinase-3β (GSK-3β) in the cortical neurons were evaluated using Western blotting analyses. Results: Atorvastatin (0.05–10 μmol/L) resulted in dose-dependent increase in neurite number and length in these neurons. Pretreatment of the cortical neurons with phosphatidylinositol 3-kinase (PI3K) inhibitors LY294002 (30 μmol/L) and wortmannin (5 μmol/L), Akt inhibitor tricribine (1 μmol/L) or mTOR inhibitor rapamycin (100 nmol/L) blocked the atorvastatin-induced increase in neurite outgrowth, suggesting that atorvastatin promoted neurite outgrowth via activating the PI3K/Akt/mTOR signaling pathway. Atorvastatin (10 μmol/L) significantly increased the levels of phosphorylated PDK1, Akt and mTOR in the cortical neurons, which were prevented by LY294002 (30 μmol/L). Moreover, atorvastatin (10 μmol/L) stimulated the phosphorylation of 4E-BP1 and p70S6K, the substrates of mTOR, in the cortical neurons. In addition, atorvastatin (10 μmol/L) significantly increased the phosphorylated GSK-3β level in the cortical neurons, which was prevented by both LY294002 and tricribine. Conclusion: These results suggest that activation of both the PI3K/Akt/mTOR and Akt/GSK-3β signaling pathways is responsible for the atorvastatin-induced neurite outgrowth in cultured cortical neurons. PMID:22705730

Trapping-mediated dissociative chemisorption of C3H8 and C3D8 on Ir(110)

NASA Astrophysics Data System (ADS)

Kelly, D.; Weinberg, W. H.

1996-07-01

We have employed molecular beam techniques to investigate the molecular trapping and trapping-mediated dissociative chemisorption of C3H8 and C3D8 on Ir(110) at low beam translational energies, Ei≤5 kcal/mol, and surface temperatures, Ts, from 85 to 1200 K. For Ts=85 K, C3H8 is molecularly adsorbed on Ir(110) with a trapping probability, ξ, equal to 0.94 at Ei=1.6 kcal/mol and ξ=0.86 at Ei=5 kcal/mol. At Ei=1.9 kcal/mol and Ts=85 K, ξ of C3D8 is equal to 0.93. From 150 K to approximately 700 K, the initial probabilities of dissociative chemisorption of propane decrease with increasing Ts. For Ts from 700 to 1200 K, however, the initial probability of dissociative chemisorption maintains the essentially constant value of 0.16. These observations are explained within the context of a kinetic model which includes both C-H (C-D) and C-C bond cleavage. Below 450 K propane chemisorption on Ir(110) arises essentially solely from C-H (C-D) bond cleavage, an unactivated mechanism (with respect to a gas-phase energy zero) for this system, which accounts for the decrease in initial probabilities of chemisorption with increasing Ts. With increasing Ts, however, C-C bond cleavage, the activation energy of which is greater than the desorption energy of physically adsorbed propane, increasingly contributes to the measured probability of dissociative chemisorption. The activation energies, referenced to the bottom of the physically adsorbed molecular well, for C-H and C-C bond cleavage for C3H8 on Ir(110) are found to be Er,CH=5.3±0.3 kcal/mol and Er,CC=9.9±0.6 kcal/mol, respectively. The activation energies for C-D and C-C bond cleavage for C3D8 on Ir(110) are 6.3±0.3 kcal/mol and 10.5±0.6 kcal/mol, respectively. The desorption activation energy of propane from Ir(110) is approximately 9.5 kcal/mol. These activation energies are compared to activation energies determined recently for ethane and propane adsorption on Ir(111), Ru(001), and Pt(110)-(1×2), and ethane activation on Ir(110).

Recommendations for newborn screening for galactokinase deficiency: A systematic review and evaluation of Dutch newborn screening data.

PubMed

Stroek, Kevin; Bouva, Marelle J; Schielen, Peter C J I; Vaz, Frédéric M; Heijboer, Annemieke C; de Jonge, Robert; Boelen, Anita; Bosch, Annet M

2018-03-21

Galactokinase (GALK) deficiency causes cataract leading to severe developmental consequences unless treated early. Because of the easy prevention and rapid reversibility of cataract with treatment, the Dutch Health Council advised to include GALK deficiency in the Dutch newborn screening program. The aim of this study is to establish the optimal screening method and cut-off value (COV) for GALK deficiency screening by performing a systematic review of the literature of screening strategies and total galactose (TGAL) values and by evaluating TGAL values in the first week of life in a cohort of screened newborns in the Netherlands. Systematic literature search strategies in OVID MEDLINE and OVID EMBASE were developed and study selection, data collection and analyses were performed by two independent investigators. A range of TGAL values measured by the Quantase Neonatal Total Galactose screening assay in a cohort of Dutch newborns in 2007 was evaluated. Eight publications were included in the systematic review. All four studies describing screening strategies used TGAL as the primary screening marker combined with galactose-1-phosphate uridyltransferase (GALT) measurement that is used for classical galactosemia screening. TGAL COVs of 2200 μmol/L, 1665 μmol/L and 1110 μmol/L blood resulted in positive predictive values (PPV) of 100%, 82% and 10% respectively. TGAL values measured in the newborn period were reported for 39 GALK deficiency patients with individual values ranging from 3963 to 8159 μmol/L blood and 2 group values with mean 8892 μmol/L blood (SD ± 5243) and 4856 μmol/L blood (SD ± 461). Dutch newborn screening data of 72,786 newborns from 2007 provided a median TGAL value of 110 μmol/L blood with a range of 30-2431 μmol/L blood. Based on TGAL values measured in GALK deficiency patients reported in the literature and TGAL measurements in the Dutch cohort by newborn screening we suggest to perform the GALK screening with TGAL as a primary marker with a COV of 2500 μmol/L blood, combined with GALT enzyme activity measurement as used in the classical galactosemia screening, to ensure detection of GALK deficiency patients and minimize false positive referrals. Copyright © 2018. Published by Elsevier Inc.

Assessment of dopamine receptor blockade by neuroleptic drugs in the living human brain

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wong, D.F.; Wagner, H.N. Jr.; Coyle, J.

1985-05-01

Positron emission tomography (PET) makes it possible to attempt to relate directly the antipsychotic effect of neuroleptic drugs and their blocking effect on dopamine receptors (D2) in vivo. The authors have examined the ability of haloperidol (HAL) and molindone (MOL) to block the binding of C-11 n-methylspiperone (NMSP) in 6 normal subjects. A dose of 0.05 mg/kg of HAL resulted in a 68% drop in the slope of the caudate/cerebellum (Ca/Cb) vs. time. This slope is related to the rate of specific binding of NMSP to the receptor. A dose response was seen with both drugs. With increasing doses ofmore » HAL from .05 to 0.082 mg/kg, CA/Cb vs. time slope fell from .235 to .156/min. (N=4), progressively. Similarly with increasing doses of MOL of .16-.44 mg/kg slopes decreased from .0335 to .0155/min. (N=4). Similar degrees of post injection Ca/Cb ratio were produced with quantities of MOL and HAL administered in the oral dose ratio of doses 3-5:1 times greater than HAL. This is also the dose ratio at which we found similar dopamine receptor blockade by PET in vivo. A question that arises is why the in vitro affinity of HAL for D2 is 30 times greater than that of MOL in the human brain. The results raise the possibility that MOL metabolites are not only active in blocking D2 but indeed may possibly be more potent than MOL itself. It also helps confirm the site of action of MOL and its in vivo metabolites.« less

Blood plasma response and urinary excretion of nitrite and nitrate in milk-fed calves after oral nitrite and nitrate administration.

PubMed

Hüsler, B R.; Blum, J W.

2001-05-01

There is marked endogenous production of nitrate in young calves. Here we have studied the contribution of exogenous nitrate and nitrite to plasma concentrations and urinary excretion of nitrite and nitrate in milk-fed calves. In experiment 1, calves were fed 0 or 200 &mgr;mol nitrate or nitrite/kg(0.75) or 100 &mgr;mol nitrite plus 100 &mgr;mol nitrate/kg(0.75) with milk for 3 d. In experiment 2, calves were fed 400 &mgr;mol nitrate or nitrite/kg(0.75) with milk for 1 d. Plasma nitrate rapidly and comparably increased after feeding nitrite, nitrate or nitrite plus nitrate. The rise of plasma nitrate was greater if 400 than 200 &mgr;mol nitrate or nitrite/kg(0.75) were fed. Plasma nitrate decreased slowly after the 3-d administration of 200 &mgr;mol nitrate or nitrite/kg(0.75) and reached pre-experimental concentrations 4 d later. Urinary nitrate excretions nearly identically increased if nitrate, nitrite or nitrite plus nitrate were administered and excreted amounts were greater if 400 than 200 &mgr;mol nitrate or nitrite/kg(0.75) were fed. After nitrite ingestion plasma nitrite only transiently increased after 2 and 4 h and urinary excretion rates remained unchanged. Plasma nitrate concentration remained unchanged if milk was not supplemented with nitrite or nitrate. Nitrate concentrations were stable for 24 h after addition of nitrite to full blood in vitro, whereas nitrite concentrations decreased within 2 h. In conclusion, plasma nitrate concentrations and urinary nitrate excretions are enhanced dose-dependently by feeding low amounts of nitrate and nitrite, whereas after ingested nitrite only a transient and small rise of plasma nitrite is observed because of rapid conversion to nitrate.

Haemoglobin A1c as a screening tool for type 2 diabetes and prediabetes in populations of Swedish and Middle-East ancestry.

PubMed

Hellgren, Margareta; Hjörleifsdottir Steiner, Kristin; Bennet, Louise

2017-08-01

To explore and compare sensitivity and specificity for HbA1c ≥48mmol/mol as a predictor for type 2 diabetes mellitus (T2DM) in two populations with different ethnicity and to examine the predictive value of two levels of HbA1c (≥42mmol/mol, ≥39mmol/mol) for prediabetes in these populations. Four cohorts were examined with an oral glucose tolerance test. (1) The MEDIM Study (n=1991 individuals of Swedish and Iraqi ancestry); (2) The Skaraborg Project (n=1327 individuals of Swedish ancestry); (3) The 4-D study (n=424 individuals of Swedish, Iraqi and Turkish ancestry); (4) The Flemingsberg study (n=212 participants of Turkish ancestry). HbA1c ≥48mmol/mol had a sensitivity for T2DM of 31% and 25% respectively in individuals of Middle-East and Swedish ancestry. The positive and negative predictive value was high in both populations (70.3, 96.4 and 96.2, 97.6 respectively). Using HbA1c ≥42mmol/mol and ≥39mmol/mol as a predictor for prediabetes gave a sensitivity of 17% and 36% in individuals of Middle-East and 15% and 34% in individuals of Swedish ancestry. Even if HbA1c ≥48mmol/mol is a valuable diagnostic tool, it is a blunt and insensitive tool for screening and would exclude most people with T2DM, independent of ancestry and age. HbA1c is an inefficient way to detect individuals with prediabetes. Copyright © 2017 Primary Care Diabetes Europe. Published by Elsevier Ltd. All rights reserved.

Sequential Proton Loss Electron Transfer in Deactivation of Iron(IV) Binding Protein by Tyrosine Based Food Components.

PubMed

Tang, Ning; Skibsted, Leif H

2017-08-02

The iron(IV) binding protein ferrylmyoglobin, MbFe(IV)═O, was found to be reduced by tyrosine based food components in aqueous solution through a sequential proton loss electron transfer reaction mechanism without binding to the protein as confirmed by isothermal titration calorimetry. Dopamine and epinephrine are the most efficient food components reducing ferrylmyoglobin to oxymyoglobin, MbFe(II)O 2 , and metmyoglobin, MbFe(III), as revealed by multivariate curve resolution alternating least-squares with second order rate constants of 33.6 ± 2.3 L/mol/s (ΔH ⧧ of 19 ± 5 kJ/mol, ΔS ⧧ of -136 ± 18 J/mol K) and 228.9 ± 13.3 L/mol/s (ΔH ⧧ of 110 ± 7 kJ/mol, ΔS ⧧ of 131 ± 25 J/mol K), respectively, at pH 7.4 and 25 °C. The other tyrosine based food components were found to reduce ferrylmyoglobin to metmyoglobin with similar reduction rates at pH 7.4 and 25 °C. These reduction reactions were enhanced by protonation of ferrylmyoglobin and facilitated proton transfer at acidic conditions. Enthalpy-entropy compensation effects were observed for the activation parameters (ΔH ⧧ and ΔS ⧧ ), indicating the common reaction mechanism. Moreover, principal component analysis combined with heat map were performed to understand the relationship between density functional theory calculated molecular descriptors and kinetic data, which was further modeled by partial least squares for quantitative structure-activity relationship analysis. In addition, a three tyrosine residue containing protein, lysozyme, was also found to be able to reduce ferrylmyoglobin with a second order rate constant of 66 ± 28 L/mol/s as determined by a competitive kinetic method.

Spectrofluorimetric determination of cefixime using terbium-danofloxacin probe

PubMed Central

Manzoori, Jamshid L.; Amjadi, Mohammad; Soltani, Naser; Jouyban, Abolghasem

2014-01-01

Objective(s): Cefixime (Cfx), is a semi-synthetic third-generation oral cephalosporin antibiotic that is prescribed for the treatment of susceptible infections. There are some procedures for the determination of Cfx in pharmaceutical formulations and biological samples. Herein a spectrofluorimetric method was proposed for Cfx determination based on the fluorescence quenching of terbium-danofloxacin (Tb3+-Dano) in the presence of Cfx. Materials and Methods: Cfx was detected based on fluorescence quenching of terbium-danofloxacin (Tb3+-Dano) in the presence of Cfx with maximum excitation and emission wavelengths at 347 nm and 545 nm, respectively. The quenched fluorescence intensity of Tb3+- Dano system is proportional to the concentration of Cfx. The optimum conditions for the determination of Cfx were studied. Results: The maximum response was achieved under optimum conditions of [Tris buffer]= 0.008 mol/l (pH 6.5), [Tb3+]=1×10-4 mol/l and [Dano]=1×10-4 mol/l. The developed method was evaluated in terms of accuracy, precision and limit of detection. The linear concentration ranges for quantification of Cfx were 8.8×10-8-8.8×10-7 mol/l and 1.1×10-7-8.8×10-7 mol/l in standard and human serum samples with the detection limits (S/N=3) of 2.8×10-8 mol/l and 3.9×10-8 mol/l, respectively. The Cfx was determined in pharmaceutical tablets and spiked serum samples and the results were satisfactory. Conclusion: This method is simple, practical and relatively interference-free for determination of Cfx in pharmaceutical tablets and serum samples. PMID:24904718

Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Wei; Bajdich, Michal; Carey, Spencer

The energetics of the reactions of water with metal oxide surfaces are of tremendous interest for catalysis, electrocatalysis, and geochemistry, yet the energy for the dissociative adsorption of water was only previously measured on one well-defined oxide surface, iron oxide. In the present paper, the enthalpy of the dissociative adsorption of water is measured on NiO(111)-2 × 2 at 300 K using single-crystal adsorption calorimetry. The differential heat of dissociative adsorption decreases with coverage from 170 to 117 kJ/mol in the first 0.25 ML of coverage. Water adsorbs molecularly on top of that, with a heat of ~92 kJ/mol. Densitymore » functional theory (DFT) calculations reproduce the measured energies well (all within 17 kJ/mol) and provide insight into the atomic-level structure of the surfaces studied experimentally. They show that the oxygen-terminated O-octo(2 × 2) structure is the most stable NiO(111)-2 × 2 termination and gives reaction energies with water that are more consistent with the calorimetry results than the metal-terminated surface. They show that water adsorbs dissociatively on this (2 × 2)-O-octo surface to produce a hydroxyl-covered surface with a heat of adsorption of 171 ± 5 kJ/mol in the low-coverage limit (very close to 170 kJ/mol experimentally) and an integral heat that decreases by 14 kJ/mol up to saturation (compared to ~30 kJ/mol experimentally). As a result, sensitivity of this reaction’s energy to choice of DFT method is tested using a variety of different exchange correlation functionals, including HSE06, and found to be quite weak.« less

Water dissociative adsorption on NiO(111): Energetics and structure of the hydroxylated surface

DOE PAGES

Zhao, Wei; Bajdich, Michal; Carey, Spencer; ...

2016-09-19

The energetics of the reactions of water with metal oxide surfaces are of tremendous interest for catalysis, electrocatalysis, and geochemistry, yet the energy for the dissociative adsorption of water was only previously measured on one well-defined oxide surface, iron oxide. In the present paper, the enthalpy of the dissociative adsorption of water is measured on NiO(111)-2 × 2 at 300 K using single-crystal adsorption calorimetry. The differential heat of dissociative adsorption decreases with coverage from 170 to 117 kJ/mol in the first 0.25 ML of coverage. Water adsorbs molecularly on top of that, with a heat of ~92 kJ/mol. Densitymore » functional theory (DFT) calculations reproduce the measured energies well (all within 17 kJ/mol) and provide insight into the atomic-level structure of the surfaces studied experimentally. They show that the oxygen-terminated O-octo(2 × 2) structure is the most stable NiO(111)-2 × 2 termination and gives reaction energies with water that are more consistent with the calorimetry results than the metal-terminated surface. They show that water adsorbs dissociatively on this (2 × 2)-O-octo surface to produce a hydroxyl-covered surface with a heat of adsorption of 171 ± 5 kJ/mol in the low-coverage limit (very close to 170 kJ/mol experimentally) and an integral heat that decreases by 14 kJ/mol up to saturation (compared to ~30 kJ/mol experimentally). As a result, sensitivity of this reaction’s energy to choice of DFT method is tested using a variety of different exchange correlation functionals, including HSE06, and found to be quite weak.« less

A computational study on the energetics and mechanisms for the dissociative adsorption of SiHx(x = 1-4) on W(1 1 1) surface

NASA Astrophysics Data System (ADS)

Lin, Y. H.; Raghunath, P.; Lin, M. C.

2016-01-01

The adsorption and dissociation mechanisms of SiHx(x = 1-4) species on W(1 1 1) surface have been investigated by using the periodic density functional theory with the projector-augmented wave approach. The adsorption of all the species on four surface sites: top (T), bridge (B), shallow (S), and deep (D) sites have been analyzed. For SiH4 on a top site, T-SiH4(a), it is more stable with an adsorption energy of 2.6 kcal/mol. For SiH3, the 3-fold shallow site is most favorable with adsorption energy of 46.0 kcal/mol. For SiH2, its adsorption on a bridge site is most stable with 73.0 kcal/mol binding energy, whereas for SiH and Si the most stable adsorption configurations are on 3-fold deep sites with very high adsorption energies, 111.8 and 134.7 kcal/mol, respectively. The potential energy surfaces for the dissociative adsorption of all SiHx species on the W(1 1 1) surface have been constructed using the CINEB method. The barriers for H-atom migration from SiHx(a) to its neighboring W atoms, preferentially on B-sites, were predicted to be 0.4, 1.0, 4.5 and, 8.0 kcal/mol, respectively, for x = 4, 3, 2, and 1, respectively. The adsorption energy of the H atom on a bridge site on the clean W(1 1 1) surface was predicted to be 65.9 kcal/mol, which was found to be slightly affected by the co-adsorption of SiHx-1 within ± 1 kcal/mol.

Effect of increasing concentration of Na2O on structural, elastic and optical properties of (90  -  x)GeO2-xNa2O-10PbO glass system in the germanate anomaly region

NASA Astrophysics Data System (ADS)

Zainudin, C. N.; Hisam, R.; Yusof, M. I. M.; Yahya, A. K.; Halimah, M. K.

2017-10-01

Ternary germanate glasses (90  -  x)GeO2-xNa2O-10PbO (x  =  10-30 mol%) have been prepared by the melt-quenching method. Density, ρ increased with Na2O content up to maxima at 20 mol% while molar volume, V a showed an opposite trend to the density, with a minima at 20 mol% of Na2O content indicating the presence of the germanate anomaly. Ultrasonic velocity measurements showed both longitudinal, v l and shear, v s velocities increased up to 20 mol% before decreasing with further addition of Na2O. Independent longitudinal, L and shear, G moduli along with Young’s modulus, Y, mean sound velocity, v m, Debye temperature, θ D, and hardness, H recorded maximum values at 20 mol% of Na2O content which were suggested to be related to the germanate anomaly. Structural modification occurring due to conversion of six-membered GeO4 rings to three-membered rings of GeO4 changed bond density and compactness of the glass systems and caused the increase in rigidity and stiffness of the glasses. Beyond 20 mol% of Na2O, the decrease in the elastic moduli was due to depolymerization of the glass network. Meanwhile, optical energy gap, E opt exhibited a minima at 20 mol% whereas Urbach energy, E U and refractive index, n showed a maxima at the same concentration, thereby indicating variation in polarizability due to changes in concentration of bridging and non-bridging oxygen.

Energetics of formic acid conversion to adsorbed formates on Pt(111) by transient calorimetry.

PubMed

Silbaugh, Trent L; Karp, Eric M; Campbell, Charles T

2014-03-12

Carboxylates adsorbed on solid surfaces are important in many technological applications, ranging from heterogeneous catalysis and surface organo-functionalization to medical implants. We report here the first experimentally determined enthalpy of formation of any surface bound carboxylate on any surface, formate on Pt(111). This was accomplished by studying the dissociative adsorption of formic acid on oxygen-presaturated (O-sat) Pt(111) to make adsorbed monodentate and bidentate formates using single-crystal adsorption calorimetry. The integral heat of molecular adsorption of formic acid on clean Pt(111) at 100 K is 62.5 kJ/mol at 0.25 monolayer (ML). On O-sat Pt(111), the integral heat of the dissociative adsorption of formic acid to make monodentate formate (HCOOmon,ad) plus the water-hydroxyl complex ((H2O-OH)ad) was found to be 76 kJ/mol at 3/8 ML and 100-150 K. Similarly, its integral heat of dissociative adsorption to make bidentate formate (HCOObi,ad) plus (H2O-OH)ad was 106 kJ/mol at 3/8 ML and 150 K. These heats give the standard enthalpies of formation of adsorbed monodentate and bidentate formate on Pt(111) to be -354 ± 5 and -384 ± 5 kJ/mol, respectively, and their net bond enthalpies to the Pt(111) surface to be 224 ± 13 and 254 ± 13 kJ/mol, respectively. Coverage-dependent enthalpies of formation were used to estimate the enthalpy of the elementary reaction HCOOHad → HCOObi,ad + Had to be -4 kJ/mol at zero coverage and +24 kJ/mol at 3/8 ML.

Associations of HbA1c and fasting plasma glucose with incident diabetes: Implications for pre-diabetes thresholds in a Japanese population.

PubMed

Nakagami, Tomoko; Tanaka, Yuki; Oya, Junko; Kurita, Moritoshi; Isago, Chisato; Hasegawa, Yukiko; Ito, Arata; Hirota, Naoki; Tsuzura, Reika; Uchigata, Yasuko

2016-12-01

This study assessed pre-diabetes (pre-DM) cutoffs for HbA1c and fasting plasma glucose (FPG) that were associated with an increased risk of incident DM. We evaluated 2267 non-diabetic Japanese health-check examinees (HbA1c: <6.5% [<48mmol/mol] and FPG: <7.0mmol/L) who were 30-79 years old and were followed-up for 5 years. Incident DM was defined as HbA1c of ≥6.5% (≥48mmol/mol), FPG of ≥7.0mmol/L, or physician-diagnosed DM. During 11047 person-years, we identified 99 incident DM cases (4.3%). The incidence of DM increased with increasing baseline HbA1c or FPG levels, and the change points (95% confidence intervals) were 5.7% (5.6-5.7%; 39mmol/mol [38-39mmol/mol]) for HbA1c and 5.5mmol/L (5.5-5.6mmol/L) for FPG. The adjusted hazard ratios (HRs) for incident DM per one standard deviation-increase in HbA1c and FPG were 5.5 (4.4-6.8) and 4.0 (3.2-4.8), respectively. The adjusted HRs for incident DM were significantly higher at HbA1c of 5.7-6.4% (39-46mmol/mol) or FPG of 5.5-6.9mmol/L, compared to HbA1c of <5.7% (<39mmol/mol) or FPG of <5.5mmol/L. The lower cut-offs for pre-DM may be 5.7% (39mmol/mol) for HbA1c and 5.5mmol/L for FPG in this Japanese population. Copyright © 2016 Primary Care Diabetes Europe. Published by Elsevier Ltd. All rights reserved.

Small substrate transport and mechanism of a molybdate ATP binding cassette transporter in a lipid environment.

PubMed

Rice, Austin J; Harrison, Alistair; Alvarez, Frances J D; Davidson, Amy L; Pinkett, Heather W

2014-05-23

Embedded in the plasma membrane of all bacteria, ATP binding cassette (ABC) importers facilitate the uptake of several vital nutrients and cofactors. The ABC transporter, MolBC-A, imports molybdate by passing substrate from the binding protein MolA to a membrane-spanning translocation pathway of MolB. To understand the mechanism of transport in the biological membrane as a whole, the effects of the lipid bilayer on transport needed to be addressed. Continuous wave-electron paramagnetic resonance and in vivo molybdate uptake studies were used to test the impact of the lipid environment on the mechanism and function of MolBC-A. Working with the bacterium Haemophilus influenzae, we found that MolBC-A functions as a low affinity molybdate transporter in its native environment. In periods of high extracellular molybdate concentration, H. influenzae makes use of parallel molybdate transport systems (MolBC-A and ModBC-A) to take up a greater amount of molybdate than a strain with ModBC-A alone. In addition, the movement of the translocation pathway in response to nucleotide binding and hydrolysis in a lipid environment is conserved when compared with in-detergent analysis. However, electron paramagnetic resonance spectroscopy indicates that a lipid environment restricts the flexibility of the MolBC translocation pathway. By combining continuous wave-electron paramagnetic resonance spectroscopy and substrate uptake studies, we reveal details of molybdate transport and the logistics of uptake systems that employ multiple transporters for the same substrate, offering insight into the mechanisms of nutrient uptake in bacteria. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Studies on comonomer compositional distribution of bacterial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate)s and thermal characteristics of their factions.

PubMed

Feng, Lidan; Watanabe, Takumi; Wang, Yi; Kichise, Tomoyasu; Fukuchi, Takeshi; Chen, Guo-Qiang; Doi, Yoshiharu; Inoue, Yoshio

2002-01-01

The comonomer-unit compositional distributions have been investigated for bacterial poly(3-hydroxybutyrate-co-3-hydroxyhexanoate) [P(3HB-co-3HH)] samples with 3HH unit content of 13.8, 18.0, 22.0, and 54.0 mol %. They were comonomer compositionally fractionated using chloroform/n-heptane mixed solvent at ambient temperature. The fractionation of P(3HB-co-18.0 mol %3HH) and P(3HB-co-22.0 mol % 3HH), which could not be carried out effectively at room temperature, were refractionated at 70 degrees C in the mixed solvent. Fractions with different 3HH unit content in a wide range (from 4.4 to 80.7 mol %) were obtained. By use of these fractions with narrow compositional distribution, the comonomer composition dependence of thermal properties was investigated by differential scanning calorimetry. The melting point (T(m)) and heat of fusion (DeltaH) decreased as the 3HH unit content increased in the range of low 3HH content (<40 mol %), while they increased as the 3HH unit content increased in the high 3HH content range (>70 mol %). The minimum T(m) and DeltaH values were found to exist at 3HH unit content of about 60 mol %. The glass transition temperature (T(g)) decreased linearly with the increase of 3HH unit content. The values of T(m), DeltaH, and T(g) of P(3HB-co-3HH)s were compared with those of poly(3-hydroxybutyrate-co-3-hydroxyvalerate), poly(3-hydroxybutyrate-co-3-hydroxypropionate), and poly(3-hydroxybutyrate-co-4-hydroxybutyrate), and the effects of comonomer types on the thermal properties were revealed.

Soluble Extract from Moringa oleifera Leaves with a New Anticancer Activity

PubMed Central

Jung, Il Lae

2014-01-01

Moringa oleifera has been regarded as a food substance since ancient times and has also been used as a treatment for many diseases. Recently, various therapeutic effects of M. oleifera such as antimicrobial, anticancer, anti-inflammatory, antidiabetic, and antioxidant effects have been investigated; however, most of these studies described only simple biological phenomena and their chemical compositions. Due to the increasing attention on natural products, such as those from plants, and the advantages of oral administration of anticancer drugs, soluble extracts from M. oleifera leaves (MOL) have been prepared and their potential as new anticancer drug candidates has been assessed in this study. Here, the soluble cold Distilled Water extract (4°C; concentration, 300 µg/mL) from MOL greatly induced apoptosis, inhibited tumor cell growth, and lowered the level of internal reactive oxygen species (ROS) in human lung cancer cells as well as other several types of cancer cells, suggesting that the treatment of cancer cells with MOL significantly reduced cancer cell proliferation and invasion. Moreover, over 90% of the genes tested were unexpectedly downregulated more than 2-fold, while just below 1% of the genes were upregulated more than 2-fold in MOL extract-treated cells, when compared with nontreated cells. Since severe dose-dependent rRNA degradation was observed, the abnormal downregulation of numerous genes was considered to be attributable to abnormal RNA formation caused by treatment with MOL extracts. Additionally, the MOL extract showed greater cytotoxicity for tumor cells than for normal cells, strongly suggesting that it could potentially be an ideal anticancer therapeutic candidate specific to cancer cells. These results suggest the potential therapeutic implications of the soluble extract from MOL in the treatment of various types of cancers. PMID:24748376

Search for β2 Adrenergic Receptor Ligands by Virtual Screening via Grid Computing and Investigation of Binding Modes by Docking and Molecular Dynamics Simulations

PubMed Central

Bai, Qifeng; Shao, Yonghua; Pan, Dabo; Zhang, Yang; Liu, Huanxiang; Yao, Xiaojun

2014-01-01

We designed a program called MolGridCal that can be used to screen small molecule database in grid computing on basis of JPPF grid environment. Based on MolGridCal program, we proposed an integrated strategy for virtual screening and binding mode investigation by combining molecular docking, molecular dynamics (MD) simulations and free energy calculations. To test the effectiveness of MolGridCal, we screened potential ligands for β2 adrenergic receptor (β2AR) from a database containing 50,000 small molecules. MolGridCal can not only send tasks to the grid server automatically, but also can distribute tasks using the screensaver function. As for the results of virtual screening, the known agonist BI-167107 of β2AR is ranked among the top 2% of the screened candidates, indicating MolGridCal program can give reasonable results. To further study the binding mode and refine the results of MolGridCal, more accurate docking and scoring methods are used to estimate the binding affinity for the top three molecules (agonist BI-167107, neutral antagonist alprenolol and inverse agonist ICI 118,551). The results indicate agonist BI-167107 has the best binding affinity. MD simulation and free energy calculation are employed to investigate the dynamic interaction mechanism between the ligands and β2AR. The results show that the agonist BI-167107 also has the lowest binding free energy. This study can provide a new way to perform virtual screening effectively through integrating molecular docking based on grid computing, MD simulations and free energy calculations. The source codes of MolGridCal are freely available at http://molgridcal.codeplex.com. PMID:25229694

Biosynthesis of 2-deoxysugars using whole-cell catalyst expressing 2-deoxy-D-ribose 5-phosphate aldolase.

PubMed

Li, Jitao; Yang, Jiangang; Men, Yan; Zeng, Yan; Zhu, Yueming; Dong, Caixia; Sun, Yuanxia; Ma, Yanhe

2015-10-01

2-Deoxy-D-ribose 5-phosphate aldolase (DERA) accepts a wide variety of aldehydes and is used in de novo synthesis of 2-deoxysugars, which have important applications in drug manufacturing. However, DERA has low preference for non-phosphorylated substrates. In this study, DERA from Klebsiella pneumoniae (KDERA) was mutated to increase its enzyme activity and substrate tolerance towards non-phosphorylated polyhydroxy aldehyde. Mutant KDERA(K12) (S238D/F200I/ΔY259) showed a 3.15-fold improvement in enzyme activity and a 1.54-fold increase in substrate tolerance towards D-glyceraldehyde compared with the wild type. Furthermore, a whole-cell transformation strategy using resting cells of the BL21(pKDERA12) strain, containing the expressed plasmid pKDERA12, resulted in increase in 2-deoxy-D-ribose yield from 0.41 mol/mol D-glyceraldehyde to 0.81 mol/mol D-glyceraldehyde and higher substrate tolerance from 0.5 to 3 M compared to in vitro assays. With further optimization of the transformation process, the BL21(pKDERA12) strain produced 2.14 M (287.06 g/L) 2-deoxy-D-robose (DR), with a yield of 0.71 mol/mol D-glyceraldehyde and average productivity of 0.13 mol/L·h (17.94 g/L·h). These results demonstrate the potential for large-scale production of 2-deoxy-D-ribose using the BL21(pKDERA12) strain. Furthermore, the BL21(pKDERA12) strain also exhibited the ability to efficiently produce 2-deoxy-D-altrose from D-erythrose, as well as 2-deoxy-L-xylose and 2-deoxy-L-ribose from L-glyceraldehyde.

A remarkable solvent effect on the nuclearity of neutral titanium(IV)-based helicate assemblies.

PubMed

Weekes, David Michael; Diebold, Carine; Mobian, Pierre; Huguenard, Clarisse; Allouche, Lionel; Henry, Marc

2014-04-22

The spontaneous self-assembly of a neutral circular trinuclear Ti(IV) -based helicate is described through the reaction of titanium(IV) isopropoxide with a rationally designed tetraphenolic ligand. The trimeric ring helicate was obtained after diffusion of n-pentane into a solution with dichloromethane. The circular helicate has been characterized by using single-crystal X-ray diffraction study, (13) C CP-MAS NMR and (1) H NMR DOSY solution spectroscopic, and positive electrospray ionization mass-spectrometric analysis. These analytical data were compared with those obtained from a previously reported double-stranded helicate that crystallizes in toluene. The trimeric ring was unstable in a pure solution with dichloromethane and transformed into the double-stranded helicate. Thermodynamic analysis by means of the PACHA software revealed that formation of the double-stranded helicates was characterized by ΔH(toluene)=-30 kJ mol(-1) and ΔS(toluene)=+357 J K(-1)  mol(-1) , whereas these values were ΔH(CH2 Cl2 )=-75 kJ mol(-1) and ΔS(CH2 Cl2 )=-37 J K(-1)  mol(-1) for the ring helicate. The transformation of the ring helicate into the double-stranded helicate was a strongly endothermic process characterized by ΔH(CH2 Cl2 )=+127 kJ mol(-1) and ΔH(n-pentane)=+644 kJ mol(-1) associated with a large positive entropy change ΔS=+1115 J K(-1) ⋅mol(-1) . Consequently, the instability of the ring helicate in pure dichloromethane was attributed to the rather high dielectric constant and dipole moment of dichloromethane relative to n-pentane. Suggestions for increasing the stability of the ring helicate are given. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Do older adults use the Method of Loci? Results from the ACTIVE Study

PubMed Central

Gross, Alden L.; Brandt, Jason; Bandeen-Roche, Karen; Carlson, Michelle C.; Stuart, Elizabeth A.; Marsiske, Michael; Rebok, George W.

2013-01-01

Background The method of loci (MoL) is a complex visuospatial mnemonic strategy. Previous research suggests older adults could potentially benefit from using the MoL, but that it is too attentionally demanding for them to use in practice. We evaluated the hypotheses that training can increase the use of MoL, and that MoL use is associated with better memory. Methods We analyzed skip patterns on response forms for the Auditory Verbal Learning Test (AVLT) in the Advanced Cognitive Training for Independent and Vital Elderly (ACTIVE, n=1,401) trial using 5 years of longitudinal follow-up. Results At baseline, 2% of participants skipped spaces. Fewer than 2% of control participants skipped spaces at any visit across 5 years, but 25% of memory-trained participants, taught the MoL, did so. Participants who skipped spaces used more serial clustering, a hallmark of the MoL (p<0.001). Trained participants who skipped spaces showed greater memory improvement after training than memory-trained participants who did not skip spaces (Cohen's d=0.84, P=0.007), and did not differ in the subsequent rate of long-term memory decline through up to 5 years of follow-up. Conclusion Despite being attentionally demanding, this study suggests that after training, the MoL is used by up to 25% of older adults, and that its use is associated with immediate memory improvement that was sustained through the course of follow-up. Findings are consistent with the notion that older adults balance complexity with novelty in strategy selection, and that changes in strategies used following memory training result in observable qualitative and quantitative differences in memory performance. PMID:24625044

Transients and cooperative action of β-carotene, vitamin E and C in biological systems in vitro under irradiation

NASA Astrophysics Data System (ADS)

Getoff, Nikola; Platzer, Isabel; Winkelbauer, Cornelia

1999-08-01

Using N •3 species as specific electron acceptor a defined ascorbate radical: AH •↔A •-+H + (λ max=360 nm, ɛ=3400 dm 3 mol -1 cm -1) is observed. The attack of DMSO •+ on vit.E results in a vit.E • radical ( k=1×10 9 dm 3 mol -1 s -1; λ max=425 nm, ɛ=2400 dm 3 mol -1 cm -1; 2 k=4.7×10 8 dm 3 mol -1 s -1). Vit.E-acetate leads to the formation of a radical cation (vit.E-ac •+). β-carotene reacts also with DMSO •+ forming a radical cation, β-car •+ ( k=1.75×10 8 dm 3 mol -1 s -1; λ max=942 nm, ɛ=14 600 dm 3 mol -1 cm -1), which probably leads to the formation of a dimer radical cation, (β-car) •+2 ( k=2.5×10 7 dm 3 mol -1 s -1). Using E.coli bacteria (AB1157) as a model system in vitro it was found that all three vitamins are rather efficient radiation protecting agents. They can also increase the activity of cytostatica, e.g., mitomycin C (MMC), by electron transfer process. The mixture of vit.E-ac and β-car acts contradictory, but adding vit.C to it a strong cooperative enhancement of the MMC activity is observed once again. A relationship between the pulse radiolysis and the radiation biological data is found and discussed. A possible explanation of the previously reported trials concerning the role of vit.E and β-car on the increased occurence of lung and other types of cancer in smokers and drinkers is presented.

A follow up study of occupational exposure to 4,4'-methylene-bis(2-chloroaniline) (MbOCA) and isocyanates in polyurethane manufacture in the UK.

PubMed

Keen, C; Coldwell, M; McNally, K; Baldwin, P; McAlinden, J; Cocker, J

2012-08-13

This is a follow up survey of exposure to 4,4'-methylene-bis(2-chloroaniline) (MbOCA) and isocyanates in the UK polyurethane industry. Urine samples (n=446) were collected from 90 different workers. MbOCA levels were below the limit of detection in 170 samples and 26 were above the UK Biological Monitoring Guidance Value (BMGV) of 15 μmol MbOCA/mol creatinine. Detailed advice and guidance was given to each workplace at the end of the survey in 2008 and the 90% value reduced from 10 to 3 μmol MbOCA/mol creatinine in samples collected since. There was a positive correlation between glove contamination and urinary MbOCA and levels were dependent upon individual working practices especially how gloves were used. Of the 446 samples analysed for urinary metabolites of toluene diisocyanate 280 were below the detection limit and 126 were above the BMGV (1 μmol/mol creatinine). Of the 326 urine samples that were analysed for metabolites of methylenediphenyl diisocyanate, 270 were below the detection limit and 13 were above the BMGV for isocyanates. There was no correlation between urinary levels of isocyanates and MbOCA suggesting different routes of absorption, most likely inhalation and dermal respectively. Crown Copyright © 2011. Published by Elsevier Ireland Ltd. All rights reserved.

Effect of carbon sources on the aggregation of photo fermentative bacteria induced by L-cysteine for enhancing hydrogen production.

PubMed

Xie, Guo-Jun; Liu, Bing-Feng; Ding, Jie; Wang, Qilin; Ma, Chao; Zhou, Xu; Ren, Nan-Qi

2016-12-01

Poor flocculation of photo fermentative bacteria resulting in continuous biomass washout from photobioreactor is a critical challenge to achieve rapid and stable hydrogen production. In this work, the aggregation of Rhodopseudomonas faecalis RLD-53 was successfully developed in a photobioreactor and the effects of different carbon sources on hydrogen production and aggregation ability were investigated. Extracellular polymeric substances (EPS) production by R. faecalis RLD-53 cultivated using different carbon sources were stimulated by addition of L-cysteine. The absolute ζ potentials of R. faecalis RLD-53 were considerably decreased with addition of L-cysteine, and aggregation barriers based on DLVO dropped to 15-43 % of that in control groups. Thus, R. faecalis RLD-53 flocculated effectively, and aggregation abilities of strain RLD-53 cultivated with acetate, propionate, lactate and malate reached 29.35, 32.34, 26.07 and 24.86 %, respectively. In the continuous test, hydrogen-producing activity was also promoted and reached 2.45 mol H 2 /mol lactate, 3.87 mol H 2 /mol propionate and 5.10 mol H 2 /mol malate, respectively. Therefore, the aggregation of R. faecalis RLD-53 induced by L-cysteine is independent on the substrate types, which ensures the wide application of this technology to enhance hydrogen recovery from wastewater dominated by different organic substrates.

Thermochemistry and gas-phase ion energetics of 2-hydroxy-4-methoxy-benzophenone (oxybenzone).

PubMed

Lago, A F; Jimenez, P; Herrero, R; Dávalos, J Z; Abboud, J-L M

2008-04-10

We have investigated the thermochemistry and ion energetics of the oxybenzone (2-hydroxy-4-methoxy-benzophenone, C14H12O3, 1H) molecule. The following parameters have been determined for this species: gas-phase enthalpy for the of neutral molecule at 298.15K, (Delta(f)H0(m)(g) = -303.5 +/- 5.1 kJ x mol-1), the intrinsic (gas-phase) acidity (GA(1H) = 1402.1 +/- 8.4 kJ x mol-1), enthalpy of formation for the oxybenzone anion (Delta(f)H0(m)(1-,g) = -402.3 +/- 9.8 kJ x mol-1). We also have obtained the enthalpy of formation of, 4-hydroxy-4'-methoxybenzophenone (Delta(f)H0(m)(g) = -275.4 +/- 10 kJ x mol-1) and 3-methoxyphenol anion (Delta(f)H0(m)(C7H7O2-,g) = -317.7 +/- 8.7 kJ x mol-1). A reliable experimental estimation of enthalpy related to intramolecular hydrogen bonding in oxybenzone has also been obtained (30.1 +/- 6.3 kJ x mol-1) and compared with our theoretical calculations at the B3LYP/6-311++G** level of theory, by means of an isodesmic reaction scheme. In addition, heat capacities, temperature, and enthalpy of fusion have been determined for this molecule by differential scanning calorimetry.

H2O and CO2 fluxes at the floor of a boreal pine forest

NASA Astrophysics Data System (ADS)

Kulmala, Liisa; Launiainen, Samuli; Pumpanen, Jukka; Lankreijer, Harry; Lindroth, Anders; Hari, Pertti; Vesala, Timo

2008-04-01

We measured H2O and CO2 fluxes at a boreal forest floor using eddy covariance (EC) and chamber methods. Maximum evapotranspiration measured with EC ranged from 1.5 to 2.0mmol m-2 s-1 while chamber estimates depended substantially on the location and the vegetation inside the chamber. The daytime net CO2 exchange measured with EC (0-2μmol m-2 s-1) was of the same order as measured with the chambers. The nocturnal net CO2 exchange measured with the chambers ranged from 4 to 7μmol m-2 s-1 and with EC from ~4 to ~5μmol m-2 s-1 when turbulent mixing below the canopy was sufficient and the measurements were reliable. We studied gross photosynthesis by measuring the light response curves of the most common forest floor species and found the saturated rates of photosynthesis (Pmax) to range from 0.008 (mosses) to 0.184μmol g-1 s-1 (blueberry). The estimated gross photosynthesis at the study site based on average leaf masses and the light response curves of individual plant species was 2-3μmol m-2 s-1. At the same time, we measured a whole community with another chamber and found maximum gross photosynthesis rates from 4 to 7μmol m-2 s-1.

N-(2-{[5-Bromo-2-(piperidin-1-yl)pyrimidin-4-yl]sulfan­yl}-4-meth­oxy­phen­yl)benzene­sulfonamide

PubMed Central

Kumar, Mohan; Mallesha, L.; Sridhar, M. A.; Kapoor, Kamini; Gupta, Vivek K.; Kant, Rajni

2012-01-01

The title compound, C22H23BrN4O3S2, crystallizes with two mol­ecules, A and B, in the asymmetric unit. In one of these, the meth­oxy group is disordered over two sets of sites in a 0.565 (9):0.435 (9) ratio. The benzene rings bridged by the sulfonamide group are tilted relative to each other by 37.4 (1) and 56.1 (1)° in mol­ecules A and B, respectively, while the dihedral angles between the sulfur-bridged pyrimidine and benzene rings are 72.4 (1) and 70.2 (1)° for A and B, respectively. The piperidine ring adopts a chair conformation in both mol­ecules. In the crystal, inversion dimers linked by pairs of N—H⋯N hydrogen bonds occur for both A and B; the dimers are linked into [010] chains by C—H⋯O hydrogen bonds. The crystal structure also features inversion-generated aromatic π–π stacking inter­actions between the pyrimidine rings for both mol­ecules [centroid–centroid distances = 3.412 (2) (mol­ecule A) and 3.396 (2) Å (mol­ecule B)]. PMID:23284517

Phase stability and photocatalytic activity of Zr-doped anatase synthesized in miniemulsion

NASA Astrophysics Data System (ADS)

Schiller, Renate; Weiss, Clemens K.; Landfester, Katharina

2010-10-01

A series of mesoporous anatase-type TiO2 doped with zirconium (0-50 mol% Zr) was synthesized by combining the sol-gel process with the inverse miniemulsion technique. Nanoparticles between 100 and 300 nm were directly prepared from acidic precursor solutions of titanium glycolate (EGMT) and zirconium isopropoxide. The miniemulsion technique is a simple and convenient method to synthesize nanoparticles of homogeneous size because the reactions (here hydrolysis and condensation) take place in the confined space of nanodroplets (several hundreds of nanometres) and therefore in a highly controlled manner. For low doping levels (0-7.1 mol% Zr), ZrxTi1 - xO2 solid solutions were formed where Zr was uniformly dispersed into the anatase framework. For higher amounts of zirconium (Zr >= 7.1 mol%), the crystallization of zirconium titanate (ZrTiO4) occurred at a low temperature of 650 °C and it was obtained as a pure material for 47.4 mol% <= Zr <= 50 mol%. The influence of the amount of zirconium on the crystallinity, crystallite size, phase composition and stability, morphology and specific surface area was investigated. For the characterization transmission electron microscopy (TEM), x-ray diffraction (XRD), nitrogen sorption (BET) and inductively coupled plasma-optical emission spectrometry (ICP-OES) were used. The photocatalytic activity of the crystalline mixed oxides (0-9.4 mol% Zr) was examined for the degradation of methylene blue under UV irradiation.

Reaction mechanism of guanidinoacetate methyltransferase, concerted or step-wise

PubMed Central

Zhang, Xiaodong; Bruice, Thomas C.

2006-01-01

We describe a quantum mechanics/molecular mechanics investigation of the guanidinoacetate methyltransferase catalyzed reaction, which shows that proton transfer from guanidinoacetate (GAA) to Asp-134 and methyl transfer from S-adenosyl-l-methionine (AdoMet) to GAA are concerted. By self-consistent-charge density functional tight binding/molecular mechanics, the bond lengths in the concerted mechanism's transition state are 1.26 Å for both the OD1 (Asp-134)–HE (GAA) and HE (GAA)–NE (GAA) bonds, and 2.47 and 2.03 Å for the S8 (AdoMet)–C9 (AdoMet) and C9 (AdoMet)–NE (GAA) bonds, respectively. The potential-energy barrier (ΔE‡) determined by single-point B3LYP/6–31+G*//MM is 18.9 kcal/mol. The contributions of the entropy (−TΔS‡) and zero-point energy corrections Δ(ZPE)‡ by normal mode analysis are 2.3 kcal/mol and −1.7 kcal/mol, respectively. Thus, the activation enthalpy of this concerted mechanism is predicted to be ΔH‡ = ΔE‡ + Δ(ZPE)‡ = 17.2 kcal/mol. The calculated free-energy barrier for the concerted mechanism is ΔG‡ = 19.5 kcal/mol, which is in excellent agreement with the value of 19.0 kcal/mol calculated from the experimental rate constant (3.8 ± 0.2·min−1). PMID:17053070

Removal of toxic Congo red dye from water employing low-cost coconut residual fiber.

PubMed

Rani, K C; Naik, Aduja; Chaurasiya, Ram Saran; Raghavarao, K S M S

2017-05-01

The coconut residual fiber (CRF) is the major byproduct obtained during production of virgin coconut oil. Its application as a biosorbent for adsorption of Congo red was investigated. The CRF was subjected to different pretreatments, namely, pressure cooking, hexane treatment, acid treatment and their combinations. The pretreatment of CRF with the combination of hexane, acid, and pressure cooking resulted in the highest degree of adsorption. The equilibrium data were analyzed and found to fit best to both Langmuir and Freundlich isotherms. Thermodynamic parameters such as standard free energy (ΔG 0 kJ mol -1 ), standard enthalpy (ΔH 0 , kJ mol -1 ) and standard entropy (ΔS 0 , kJ mol -1 K -1 ) of the systems were calculated by using the Langmuir constant. The ΔG 0 , ΔH 0 and ΔS 0 were found to be 16.51 kJ mol -1 , -19.39 kJ mol -1 and -0.12 kJ mol -1 K -1 , respectively, at 300 K. These thermodynamic parameters suggest the present adsorption process to be non-spontaneous and exothermic. The adsorption process was observed to follow pseudo-second-order kinetics. The results suggest that CRF has potential to be a biosorbent for the removal of hazardous material (Congo red dye) with a maximum adsorption capacity of 128.94 mg g -1 at 300 K.

Occupational tellurium exposure and garlic odour.

PubMed

Berriault, C J; Lightfoot, N E

2011-03-01

Few studies have considered garlic odour as a socially important outcome of occupational tellurium (Te) exposure or concurrent exposures, and most known guidelines focus on other signs and symptoms (e.g. weight loss and somnolence). This study considers workers exposed to tellurium and selenium (Se) at an Ontario, Canada silver refinery. To establish the relation of urinary tellurium concentrations to reporting garlic odour, while considering other work-related factors such as concurrent urinary selenium concentrations. Historical surveillance records of urinary analyses for tellurium and selenium concentrations (μmol Te or Se/mol creatinine in urine) and symptom self-reports were used. Records were available from December 1986 to June 2002. Logistic regression models were fitted using age at sampling, tellurium and selenium urine concentration and duration of employment. Individual main effects were age adjusted and the final model was fitted for tellurium and selenium urine concentration and duration of employment. Urinary tellurium concentration was significantly associated with garlic odour reporting (odds ratio = 1.74, 95% confidence interval 1.01-2.97, P < 0.05). Furthermore, the likelihood of reporting garlic odour rose as workers reached urinary tellurium concentrations >1 μmol/mol creatinine. Tellurium urinary concentrations of <1 μmol/mol creatinine appear to limit, but not eliminate, the likelihood of reporting garlic odour. Future studies should consider the effect of concurrent selenium exposure as well as other workplace factors and hygiene.

Development of a standard reference material containing 22 chlorinated hydrocarbon gases at 1 μmol/mol in nitrogen.

PubMed

Li, Ning; Du, Jian; Yang, Jing; Fan, Qiang; Tian, Wen

2017-11-01

A gas standard mixture containing 22 chlorinated hydrocarbons in high purity nitrogen was prepared using a two-step weighing method and a gasifying apparatus developed in-house. The concentration of each component was determined using a gas chromatograph with flame ionization detection (GC/FID). Linear regression analysis of every component was performed using the gas standard mixture with concentrations ranging from 1 to 10 μmol/mol, showing the complete gasification of volatile organic compound (VOCs) species in a selected cylinder. Repeatability was also examined to ensure the reliability of the preparation method. In addition, no significant difference was observed between domestic treated and imported treated cylinders, which were conducive to reduction of the cost of raw materials. Moreover, the results of stability testing at different pressures and long-term stability tests indicated that the gas standard at 1 μmol/mol level with relative expanded uncertainties of 5% was stable above 2 MPa for a minimum of 12 months. Finally, a quantity comparison was conducted between the gas standard and a commercial gas standard from Scott Specialty Gases (now Air Liquide America Specialty Gases). The excellent agreement of every species suggested the favorable accuracy of our gas standard. Therefore, this reference material can be applied to routine observation of VOCs and for other purposes.

[Synthesis of strontium-containing porous hydroxyaptite ceramics and study of its biological properties].

PubMed

Zou, Wen; Ran, Xu; Liang, Jie; Chen, Hezhong; Luo, Jiaoming

2012-12-01

Strontium added into porous hydroxyaptite ceramics has the functions of improving its osseointegration, decreasing its dissolution rate and improving the bone density. Strontium-containing hydroxyaptite (Sr-HA) ceramics has been used as bone replacement and scaffold to treat the osteoporosis and bone default in clinic, but the mechanism of interfacial tissue response caused by the trace element Sr in Sr-HA ceramics still remains to be further studied. Four types of Sr-HA ceramic samples with different contents of Sr were prepared by microwave plasma sintering for testing the response of the soft tissue implanted in dog muscles in our laboratory. The contents of Sr element in the samples are 0 mol%, 1 mol%, 5 mol%, and 7 mol%, respectively. The samples were implanted in the muscle of the dogs for 4 weeks, 8 weeks and 12 weeks, respectively. The histological observations at the end of each period showed that the irritant ranking increased with the content of Sr in Sr-HA ceramics at the end of 12 weeks, and there were rich bone tissue in Sr-HA ceramic samples with 5 mol% Sr element. The overdose of element Sr is harmful to soft tissues. When the content of Sr in Sr-HA ceramic was below 5 mol%, the soft tissue response was very slight and the new bones were induced to grow well.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cao, Lingyun; Lin, Zekai; Shi, Wenjie

The dimensionality dependency of resonance energy transfer is of great interest due to its importance in understanding energy transfer on cell membranes and in low-dimension nanostructures. Light harvesting two-dimensional metal–organic layers (2D-MOLs) and three-dimensional metal–organic frameworks (3D-MOFs) provide comparative models to study such dimensionality dependence with molecular accuracy. Here we report the construction of 2D-MOLs and 3D-MOFs from a donor ligand 4,4',4''-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tribenzoate (BTE) and a doped acceptor ligand 3,3',3''-nitro-4,4',4''-(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tribenzoate (BTE-NO2). These 2D-MOLs and 3D-MOFs are connected by similar hafnium clusters, with key differences in the topology and dimensionality of the metal–ligand connection. Energy transfer from donors to acceptors through themore » 2D-MOL or 3D-MOF skeletons is revealed by measuring and modeling the fluorescence quenching of the donors. We found that energy transfer in 3D-MOFs is more efficient than that in 2D-MOLs, but excitons on 2D-MOLs are more accessible to external quenchers as compared with those in 3D-MOFs. These results not only provide support to theoretical analysis of energy transfer in low dimensions, but also present opportunities to use efficient exciton migration in 2D materials for light-harvesting and fluorescence sensing.« less

Metabolic evolution of two reducing equivalent-conserving pathways for high-yield succinate production in Escherichia coli.

PubMed

Zhu, Xinna; Tan, Zaigao; Xu, Hongtao; Chen, Jing; Tang, Jinlei; Zhang, Xueli

2014-07-01

Reducing equivalents are an important cofactor for efficient synthesis of target products. During metabolic evolution to improve succinate production in Escherichia coli strains, two reducing equivalent-conserving pathways were activated to increase succinate yield. The sensitivity of pyruvate dehydrogenase to NADH inhibition was eliminated by three nucleotide mutations in the lpdA gene. Pyruvate dehydrogenase activity increased under anaerobic conditions, which provided additional NADH. The pentose phosphate pathway and transhydrogenase were activated by increased activities of transketolase and soluble transhydrogenase SthA. These data suggest that more carbon flux went through the pentose phosphate pathway, thus leading to production of more reducing equivalent in the form of NADPH, which was then converted to NADH through soluble transhydrogenase for succinate production. Reverse metabolic engineering was further performed in a parent strain, which was not metabolically evolved, to verify the effects of activating these two reducing equivalent-conserving pathways for improving succinate yield. Activating pyruvate dehydrogenase increased succinate yield from 1.12 to 1.31mol/mol, whereas activating the pentose phosphate pathway and transhydrogenase increased succinate yield from 1.12 to 1.33mol/mol. Activating these two pathways in combination led to a succinate yield of 1.5mol/mol (88% of theoretical maximum), suggesting that they exhibited a synergistic effect for improving succinate yield. Copyright © 2014 International Metabolic Engineering Society. Published by Elsevier Inc. All rights reserved.

The influence of elevated CO2 on non-structural carbohydrate distribution and fructan accumulation in wheat canopies

NASA Technical Reports Server (NTRS)

Smart, D. R.; Chatterton, N. J.; Bugbee, B.

1994-01-01

We grew 2.4 m2 wheat canopies in a large growth chamber under high photosynthetic photon flux (1000 micromoles m-2 s-1) and using two CO2 concentrations, 360 and 1200 micromoles mol-1. Photosynthetically active radiation (400-700 nm) was attenuated slightly faster through canopies grown in 360 micromoles mol-1 than through canopies grown in 1200 micromoles mol-1, even though high-CO2 canopies attained larger leaf area indices. Tissue fractions were sampled from each 5-cm layer of the canopies. Leaf tissue sampled from the tops of canopies grown in 1200 micromoles mol-1 accumulated significantly more total non-structural carbohydrate, starch, fructan, sucrose, and glucose (p < 0.05) than for canopies grown in 360 micromoles mol-1. Non-structural carbohydrate did not significantly increase in the lower canopy layers of the elevated CO2 treatment. Elevated CO2 induced fructan synthesis in all leaf tissue fractions, but fructan formation was greatest in the uppermost leaf area. A moderate temperature reduction of 10 degrees C over 5 d increased starch, fructan and glucose levels in canopies grown in 1200 micromoles mol-1, but concentrations of sucrose and fructose decreased slightly or remained unchanged. Those results may correspond with the use of fructosyl-residues and release of glucose when sucrose is consumed in fructan synthesis.

Two-Dimensional Metal-Organic Layers as a Bright and Processable Phosphor for Fast White-Light Communication.

PubMed

Hu, Xuefu; Wang, Zi; Lin, Bangjiang; Zhang, Cankun; Cao, Lingyun; Wang, Tingting; Zhang, Jingzheng; Wang, Cheng; Lin, Wenbin

2017-06-22

A metal-organic layer (MOL) is a new type of 2D material that is derived from metal-organic frameworks (MOFs) by reducing one dimension to a single layer or a few layers. Tetraphenylethylene-based tetracarboxylate ligands (TCBPE), with aggregation-induced emission properties, were assembled into the first luminescent MOL by linking with Zr 6 O 4 (OH) 6 (H 2 O) 2 (HCO 2 ) 6 clusters. The emissive MOL can replace the lanthanide phosphors in white light emitting diodes (WLEDs) with remarkable processability, color rendering, and brightness. Importantly, the MOL-WLED exhibited a physical switching speed three times that of commercial WLEDs, which is crucial for visible-light communication (VLC), an alternative wireless communication technology to Wi-Fi and Bluetooth, by using room lighting to carry transmitted signals. The short fluorescence lifetime (2.6 ns) together with high quantum yield (50 %) of the MOL affords fast switching of the assembled WLEDs for efficient information encoding and transmission. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Melaminium nitrate–melamine–water (1/1/1)

PubMed Central

Adam, Farook; Lin, Sek Kei; Hello, Kasim Mohammed; Hemamalini, Madhukar; Fun, Hoong-Kun

2010-01-01

In the crystal structure of the title salt, C3H7N6 +·NO3 −·C3H6N6·H2O, the asymmetric unit consists of two neutral melamine (1,3,5-triazine-2,4,6-triamine) mol­ecules, two melaminium cations, two nitrate anions and two solvent water mol­ecules. One of the nitrate anions is disordered over two sets of positions, with a refined occupancy ratio of 0.909 (3):0.091 (3). The cations and neutral mol­ecules are approximately planar, with maximum deviations of 0.018 (2), 0.024 (2), 0.019 (2) and 0.007 (2) Å for each, respectively. In the crystal structure, melaminium cations and netural melamine mol­ecules self-assemble via N—H⋯N hydrogen bonds to form a supra­molecular hexa­gonal-shaped motif. In addition, the nitrate anions and water mol­ecules are connected by N—H⋯O hydrogen bonds to form a three-dimensional network. PMID:21589188

pH dependence of the dissociation of multimeric hemoglobin probed by high hydrostatic pressure.

PubMed

Bispo, Jose A C; Santos, Jose L R; Landini, Gustavo F; Goncalves, Juliana M; Bonafe, Carlos F S

2007-02-01

We investigated the thermodynamic features of the classic alkaline dissociation of multimeric hemoglobin (3.1 MDa) from Glossoscolex paulistus (Annelidea) using high hydrostatic pressure. Light scattering measurements up to microscopic thermodynamic equilibrium indicated a high pH dependency of dissociation and association. Electron microscopy and gel filtration corroborated these findings. The volume change of dissociation decreased in absolute values from -48.0 mL/mol of subunit at pH 6.0 to -19.2 mL/mol at pH 9.0, suggesting a lack of protein interactions under alkaline conditions. Concomitantly, an increase in pH reduced the Gibbs free energy of dissociation from 37.7 to 27.5 kJ/mol of subunit. The stoichiometry of proton release calculated from the pressure-induced dissociation curves was +0.602 mol of H(+)/mol of subunit. These results provide a direct quantification of proton participation in stabilizing the aggregated state of the hemoglobin, and contribute to our understanding of protein-protein interactions and of the surrounding conditions that modulate the process of aggregation.

Electrophoresis-chemiluminescence detection of phenols catalyzed by hemin.

PubMed

Shu, Lu; Zhu, Jinkun; Wang, Qingjiang; He, Pingang; Fang, Yuzhi

2014-09-01

Based on the catalytic activity of hemin, an efficient biocatalyst, an indirect capillary electrophoresis-chemiluminescence (CE-CL) detection method for phenols using a hemin-luminol-hydrogen peroxide system was developed. Through a series of static injection experiments, hemin was found to perform best in a neutral solution rather than an acidic or alkaline medium. Although halide ions such as Br(-) and F(-) could further enhance the CL signal catalyzed by hemin, it is difficult to apply these conditions to this CE-CL detection system because of the self-polymerization of hemin, as it hinders the CE process. The addition of concentrated ammonium hydroxide to an aqueous/dimethyl sulfoxide solution of hemin-luminol afforded a stable CE-CL baseline. The indirect CE-CL detection of five phenols using this method gave the following limits of detections: 4.8 × 10(-8) mol/L (o-sec-butylphenol), 4.9 × 10(-8) mol/L (o-cresol), 5.4 × 10(-8) mol/L (m-cresol), 5.3 × 10(-8) mol/L (2,4-dichlorophenol) and 7.1 × 10(-8) mol/L (phenol). Copyright © 2013 John Wiley & Sons, Ltd.

Inosine-5'-monophosphate is a candidate agent to resolve rigor mortis of skeletal muscle.

PubMed

Matsuishi, Masanori; Tsuji, Mariko; Yamaguchi, Megumi; Kitamura, Natsumi; Tanaka, Sachi; Nakamura, Yukinobu; Okitani, Akihiro

2016-11-01

The object of the present study was to reveal the action of inosine-5'-monophosphate (IMP) toward myofibrils in postmortem muscles. IMP solubilized isolated actomyosin within a narrow range of KCl concentration, 0.19-0.20 mol/L, because of the dissociation of actomyosin into actin and myosin, but it did not solubilize the proteins in myofibrils with 0.2 mol/L KCl. However, IMP could solubilize both proteins in myofibrils with 0.2 mol/L KCl in the presence of 1 m mol/L pyrophosphate or 1.0-3.3 m mol/L adenosine-5'-diphosphate (ADP). Thus, we presumed that pyrophosphate and ADP released thin filaments composed of actin, and thick filaments composed of myosin from restraints of myofibrils, and then both filaments were solubilized through the IMP-induced dissociation of actomyosin. Thus, we concluded that IMP is a candidate agent to resolve rigor mortis because of its ability to break the association between thick and thin filaments. © 2016 Japanese Society of Animal Science.

Bis(μ-ferrocene­carboxyl­ato)bis­[aqua­­bis(ferrocene­carboxyl­ato)methano­l­erbium(III)] methanol disolvate

PubMed Central

Liu, Jianmin; Li, Yuanyuan; Li, Dacheng

2012-01-01

In the centrosymmetric title coordination compound, [Er2{Fe(C5H5)(C6H4O2)}6(CH3OH)2(H2O)2]·2CH3OH, the two ErIII ions are bridged by two ferrocene­carboxyl­ate anions as asymmetrically bridging ligands, leading to dimeric cores. The ErIII ion has a distorted dodeca­hedral coordination with six coordinating O atoms derived from the ferrocene­carboxyl­ate ligands and two coordinated O atoms from one water mol­ecule and one methanol mol­ecule. The asymmetric unit comprises a half of the complex mol­ecule and a methanol solvent mol­ecule. Intra­molecular O—H⋯O and C—H⋯O inter­actions occur. In the crystal, mol­ecules are linked by inter­molecular O—H⋯O hydrogen bonds and C—H⋯O as well as C—H⋯π inter­actions. PMID:22259358

Methanogenic degradation of acetone by an enrichment culture.

PubMed

Platen, H; Schink, B

1987-01-01

An anaerobic enrichment culture degraded 1 mol of acetone to 2 mol of methane and 1 mol of carbon dioxide. Two microorganisms were involved in this process, a filament-forming rod similar to Methanothrix sp. and an unknown rod with round to slightly pointed ends. Both organisms formed aggregates up to 300 micron in diameter. No fluorescing bacteria were observed indicating that hydrogen or formate-utilizing methanogens are not involved in this process. Acetate was utilized in this culture by the Methanothrix sp. Inhibition of methanogenesis by bromoethanesulfonic acid or acetylene decreased the acetone degradation rate drastically and led to the formation of 2 mol acetate per mol of acetone. Streptomycin completely inhibited acetone degradation, and neither acetate nor methane was formed. 14CO2 was incorporated exclusively into the C-1 atom of acetate indicating that acetone is degraded via carboxylation to an acetoacetate residue. It is concluded that acetone is degraded by a coculture of an eubacterium and an acetate-utilizing methanogen and that acetate is the only intermediate transferred between both. The energetical problems of the eubacterium converting acetone to acetate are discussed.

Evaluation of the effectiveness of non-irradiated and chlorine-free packaging for fresh beef preservation.

PubMed

Rodrigues, José B M; Sarantópoulos, Claire I G L; Bromberg, Renata; Andrade, Juliana C; Brunelli, Kleber; Miyagusku, Luciana; Marquezini, Miriam G; Yamada, Eunice A

2017-03-01

This study evaluates the potential of using non-irradiated barrier-shrink bags containing ethylene-vinyl alcohol copolymer (EVOH), polyamide (PA) and ethylene ionomer in their structures to preserve vacuum-packaged fresh beef as an alternative to traditional gamma-ray cross-linked bags containing polyvinylidene chloride (PVDC). Boneless beef rib eye roll cuts were vacuum-packed in an industrial processing plant using EVOH 44% mol, EVOH 32% mol and a control PVDC barrier shrink bags. The cuts were evaluated during storage at 0.5°C. The EVOH films presented similar performance compared to control PVDC barrier shrink bags related to bacteria growth and purge loss. Packages with EVOH 32% mol film presented better performance than control bag with respect to the meat sensorial attributes, including fewer bubbles and better adhesion. EVOH 44% mol bags presented the highest rate of colour loss. The EVOH 32% mol non-irradiated and chlorine-free film is as effective for the preservation of fresh beef as traditional PVDC-irradiated shrink bags. Copyright © 2016 Elsevier Ltd. All rights reserved.

Human oocyte cryopreservation as an adjunct to IVF-embryo transfer cycles.

PubMed

Boldt, Jeffrey; Cline, Donald; McLaughlin, David

2003-06-01

The purpose of this work was to develop methods for successful cryopreservation of human oocytes. Two cryopreservation procedures were used. Method 1 involved use of 1.5 mol/l propanediol (PrOH)-0.1 mol/l sucrose with medium containing sodium (Na) as cryoprotectant medium, seeding at -7 degrees C, and stepwise dilution of cryoprotectant post-thaw. Method 2 used Na-depleted media with 1.5 mol/l PrOH-0.2 mol/l sucrose for freezing, seeding at -6 degrees C, and use of high sucrose (0.5 and 0.2 mol/l) for cryoprotectant removal. The first method was used in seven patients, and gave poor (12.3%) survival results and no pregnancies. The second method was used in 15 patients (16 cycles), and yielded good survival and fertilization rates (74.4 and 59% respectively), with four pregnancies and five healthy infants born to 11 women receiving an embryo transfer. Using Na-depleted media along with other alterations in freezing and thawing procedures, human oocyte cryopreservation can provide excellent survival and pregnancy rates.

Macro-hydrogels versus nanoparticles by the controlled assembly of polysaccharides.

PubMed

Costalat, M; Alcouffe, P; David, L; Delair, T

2015-12-10

The controlled assembly of oppositely charged chitosan (CS, Mw ∼ 33 × 10(3) to 600 × 10(3)g mol(-1)) and dextran sulfate (DS, Mw = 1.3 × 10(6)g mol(-1)) or heparin (HP, Mw = 1.8 × 10(4)g mol(-1)) led either to nanoparticles or macro-hydrogels, at room temperature. The control over the electrostatic attractive interactions was achieved using 2 mol L(-1) NaCl in the polyion solutions and subsequent dialysis to let the assembly occur. Macrohydrogels formed with an excess of polyanion. In the presence of an excess of polycation, colloidal gels were exclusively obtained. At salt concentrations lower than 1 mol L(-1), the spontaneous gelation provided macro-hydrogels, whatever the polyion in excess. Rheology measurements showed a similar elastic behaviour for CS-DS and CS-HP hydrogels, though CS-HP hydrogels appeared less cohesive. SAXS experiments revealed an aggregate morphology with internal and surface structure depending on the degree of acetylation (DA) of chitosan. Copyright © 2015 Elsevier Ltd. All rights reserved.

Calibrations between the variables of microbial TTI response and ground pork qualities.

PubMed

Kim, Eunji; Choi, Dong Yeol; Kim, Hyun Chul; Kim, Keehyuk; Lee, Seung Ju

2013-10-01

A time-temperature indicator (TTI) based on a lactic acid bacterium, Weissella cibaria CIFP009, was applied to ground pork packaging. Calibration curves between TTI response and pork qualities were obtained from storage tests at 2°C, 10°C, and 13°C. The curves of the TTI vs. total cell number at different temperatures coincided to the greatest extent, indicating the highest representativeness of calibration, by showing the least coefficient of variance (CV=11%) of the quality variables at a given TTI response (titratable acidity) on the curves, followed by pH (23%), volatile basic nitrogen (VBN) (25%), and thiobarbituric acid-reactive substances (TBARS) (47%). Similarity of Arrhenius activation energy (Ea) could also reflect the representativeness of calibration. The total cell number (104.9 kJ/mol) was found to be the most similar to that of the TTI response (106.2 kJ/mol), followed by pH (113.6 kJ/mol), VBN (77.4 kJ/mol), and TBARS (55.0 kJ/mol). Copyright © 2013 Elsevier Ltd. All rights reserved.

Crystal structures of 1-hy­droxy-4-prop­yloxy-9,10-anthra­quinone and its acetyl derivative

PubMed Central

Nakagawa, Hidemi; Kitamura, Chitoshi

2017-01-01

1-Hy­droxy-4-prop­yloxy-9,10-anthra­quinone, C17H14O4, (I), and its acetyl derivative, 4-acet­yloxy-4-prop­yloxy-9,10-anthra­quinone, C19H16O5, (II), were synthesized from the commercially available dye quinizarin. In both compounds, the anthra­quinone frameworks are close to planarity. There is a large difference in the conformation of the prop­yloxy group; the mol­ecule of (I) adopts a gauche conformation [O—C—C—C = −64.4 (2)°], although the mol­ecule of (II) takes a trans-planar conformation (zigzag) [O—C—C—C = 176.1 (3)°]. In the mol­ecule of (I), there is an intra­molecular O—H⋯O hydrogen bond. In both crystals, the mol­ecules are linked by C—H ⋯O hydrogen bonds. A difference in the mol­ecular arrangements of (I) and (II) is found along the stacking directions. PMID:29250400

Chemical composition, fatty acid content and antioxidant potential of meat from goats supplemented with Moringa (Moringa oleifera) leaves, sunflower cake and grass hay.

PubMed

Qwele, K; Hugo, A; Oyedemi, S O; Moyo, B; Masika, P J; Muchenje, V

2013-03-01

The present study determined the chemical composition, fatty acid (FA) content and antioxidant capacity of meat from goats supplemented with Moringa oleifera leaves (MOL) or sunflower cake (SC) or grass hay (GH). The meat from goat supplemented with MOL had higher concentrations of total phenolic content (10.62±0.27 mg tannic acid equivalent E/g). The MOL significantly scavenged 2,2'-azino-bis-3-ethylbenzothiazoline-6-sulfonic-acid (ABTS) radical to 93.51±0.19% (93.51±0.19%) and 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical to 58.95±0.3% than other supplements. The antioxidative effect of MOL supplemented meat on catalase (CAT), reduced glutathione (GSH), superoxide dismutase (SOD) and lipid oxidation (LO) was significantly (P<0.05) higher than other meat from goat feed on grass hay or those supplemented with sunflower seed cake. The present study indicated that the anti-oxidative potential of MOL may play a role in improving meat quality (chemical composition, colour and lipid stability). Copyright © 2012 Elsevier Ltd. All rights reserved.

Coastal surface sediment quality assessment in Leizhou Peninsula (South China Sea) based on SEM-AVS analysis.

PubMed

Li, Feng; Lin, Jin-qin; Liang, Yan-yan; Gan, Hua-yang; Zeng, Xiang-yun; Duan, Zhi-peng; Liang, Kai; Liu, Xing; Huo, Zhen-hai; Wu, Chang-hua

2014-07-15

Surface sediments from the coastal area of the Leizhou Peninsula in the South China Sea were collected and analyzed and the potential ecological risks in the area were assessed based on acid-volatile sulfide (AVS) model. The AVS levels are between 0.109 and 55.6 μmol g(-1), with the average at 4.45 μmol g(-1). The high AVS-concentration zones include the aquaculture areas of Liusha Bay and the densely populated areas of Zhanjiang Bay. The simultaneously extracted metals (SEM) range from 0.026 μmol g(-1) to 8.61 μmol g(-1), with the average at 0.843 μmol g(-1). Most of high SEM-concentration stations were located in ports or aquaculture zones. Most of the coastal surface sediments of the Leizhou Peninsula (90%) had no adverse biological effects according to the criterion proposed by USEPA (2005); while adverse effects were uncertain in some stations (8%); even in 2 stations (2%) adverse biological effects may be expected. Copyright © 2014 Elsevier Ltd. All rights reserved.

A comparison of the coupled cluster and internally contracted averaged coupled-pair functional levels of theory for the calculation of the MCH2(+) binding energies for M = Sc to Cu

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.; Partridge, Harry; Scuseria, Gustavo E.

1992-01-01

The correlation contribution to the M-C binding energy for the MCH2(+) systems can exceed 100 kcal/mol. At the self-consistent field (SCF) level, these systems can be more than 50 kcal/mol above the fragment energies. In spite of the poor zeroth-order reference, the coupled cluster single and double excitation method with a perturbational estimate of triple excitations, CCSD(T), method is shown to provide an accurate description of these systems. The maximum difference between the CCSD(T) and internally contracted averaged coupled-pair functional binding energies is 1.5 kcal/mol for CrCH2(+), with the remaining systems agreeing to within 1.0 kcal/mol.

9-(3,4-Dimeth-oxy-phen-yl)-3,3,6,6-tetra-methyl-4,5,6,9-tetra-hydro-3H-xanthene-1,8(2H,7H)-dione.

PubMed

Mehdi, Sayed Hasan; Sulaiman, Othman; Ghalib, Raza Murad; Yeap, Chin Sing; Fun, Hoong-Kun

2011-07-01

The asymmetric unit of the title xanthene compound, C(25)H(30)O(5), contains two mol-ecules in which the pyran ring and the dimeth-oxy-phenyl ring are nearly perpendicular to one another [dihedral angles = 86.81 (8) and 84.45 (9)°]. One of the meth-oxy groups in one mol-ecule is twisted away from the phenyl ring [C-O-C-C torsion angle = -103.40 (16)°]. The pyran ring adopts a boat conformation whereas the two fused cyclo-hexane rings adopt envelope conformations in both mol-ecules. In the crystal, mol-ecules are linked into a three-dimensional network by C-H⋯O hydrogen bonds.

Isolation of copper-binding proteins from activated sludge culture.

PubMed

Fukushi, K; Kato, S; Antsuki, T; Omura, T

2001-01-01

Six copper-binding microbial proteins were isolated from activated sludge cultures grown on media containing copper at various concentrations. Molecular weights among isolated proteins were ranged from 1.3k to 1 74k dalton. Isolated proteins were compared for their copper binding capabilities. Proteins isolated from cultures grown in the presence of copper in the growth media exhibited higher copper binding capabilities than those isolated from the culture grown in the absence of copper. The highest metal uptake of 61.23 (mol copper/mol protein) was observed by a protein isolated from a culture grown with copper at a concentration of 0.25 mM. This isolated protein (CBP2) had a molecular weight of 24k dalton. Other protein exhibited copper binding capability of 4.8-32.5 (mol copper/mol protein).

Dopant occupancy and UV-VIS-NIR spectroscopy of Mg (0, 4, 5 and 6 mol.%):Dy:LiNbO3 crystal

NASA Astrophysics Data System (ADS)

Dai, Li; Liu, Chunrui; Han, Xianbo; Wang, Luping; Tan, Chao; Yan, Zhehua; Xu, Yuheng

2017-09-01

A series of Dy:LiNbO3 crystals with x mol.% Mg2+ ions (x =0, 4, 5 and 6 mol.%) were grown by the Czochralski method. The effective segregation coefficient of Mg2+ and Dy3+ ions was studied by the inductively coupled plasma-atomic emission spectrometry (ICP-AES). UV-VIS-NIR absorption spectra and Judd-Ofelt theory were used to investigate their spectroscopic properties. J-O intensity parameters (Ω2 = 7.53 × 10-20cm2, Ω4 = 6.98 × 10-20cm2, and Ω6 = 3.09 × 10-20cm2) and larger spectroscopic quality factor (X = 2.26) for Mg:(6 mol.%)Dy:LiNbO3 crystals were obtained.

G3X-K theory: A composite theoretical method for thermochemical kinetics

NASA Astrophysics Data System (ADS)

da Silva, Gabriel

2013-02-01

A composite theoretical method for accurate thermochemical kinetics, G3X-K, is described. This method is accurate to around 0.5 kcal mol-1 for barrier heights and 0.8 kcal mol-1 for enthalpies of formation. G3X-K is a modification of G3SX theory using the M06-2X density functional for structures and zero-point energies and parameterized for a test set of 223 heats of formation and 23 barrier heights. A reduced perturbation-order variant, G3X(MP3)-K, is also developed, providing around 0.7 kcal mol-1 accuracy for barrier heights and 0.9 kcal mol-1 accuracy for enthalpies, at reduced computational cost. Some opportunities to further improve Gn composite methods are identified and briefly discussed.

Chlorobium limicola forma thiosulfatophilum: Biocatalyst in the Production of Sulfur and Organic Carbon from a Gas Stream Containing H2S and CO2

PubMed Central

Cork, Douglas J.; Garunas, Ruta; Sajjad, Ashfaq

1983-01-01

Chlorobium limicola forma thiosulfatophilum (ATCC 17092) was grown in a 1-liter continuously stirred tank reactor (800-ml liquid volume) at pH 6.8, 30°C, saturated light intensity, and a gas flow rate of 23.6 ml/min from a gas cylinder blend consisting of 3.9 mol% H2S, 9.2 mol% CO2, 86.4 mol% N2, and 0.5 mol% H2. This is the first demonstration of photoautotrophic growth of a Chlorobium sp. on a continuous inorganic gas feed. A significant potential exists for applying this photoautotrophic process to desulfurization and CO2 fixation of gases containing acidic components (H2S and CO2). PMID:16346255

1,2-Diiodo-4,5-dimethyl­benzene

PubMed Central

Hathaway, Bruce A.; Kilgore, Uriah J.; Bond, Marcus R.

2009-01-01

The structure of the title compound, C8H8I2, conforms closely to the mm2 symmetry expected for the free mol­ecule and is the first reported structure of a diiodo­dimethyl­benzene. Repulsion by neighboring I atoms and the neighboring methyl groups opposite to them results in a slight elongation of the mol­ecule along the approximate twofold rotation axis that bis­ects the ring between the two I atoms. In the extended structure, the mol­ecules form inversion-related pairs which are organized in approximately hexa­gonal close-packed layers and the layers then stacked so that mol­ecules in neighboring layers abut head-to-tail in a manner that optimizes dipole–dipole inter­actions. PMID:21583089

An Ab Initio Study of CuCO

NASA Technical Reports Server (NTRS)

Bauschlicher, Charles W., Jr.

1994-01-01

Modified coupled-pair functional (MCPF) calculations and coupled cluster singles and doubles calculations, which include a perturbational estimate of the connected triples [CCSD(T)], yield a bent structure for CuCO, thus, supporting the prediction of a nonlinear structure based on density functional (DF) calculations. Our best estimate for the binding energy is 4.9 +/- 1.4 kcal/mol; this is in better agreement with experiment (6.0 +/- 1.2 kcal/mol) than the DF approach which yields a value (19.6 kcal/mol) significantly larger than experiment.

Phytoplankton Productivity in an Arctic Fjord (West Greenland): Estimating Electron Requirements for Carbon Fixation and Oxygen Production

PubMed Central

Hancke, Kasper; Dalsgaard, Tage; Sejr, Mikael Kristian; Markager, Stiig; Glud, Ronnie Nøhr

2015-01-01

Accurate quantification of pelagic primary production is essential for quantifying the marine carbon turnover and the energy supply to the food web. Knowing the electron requirement (Κ) for carbon (C) fixation (Κ C) and oxygen (O2) production (Κ O2), variable fluorescence has the potential to quantify primary production in microalgae, and hereby increasing spatial and temporal resolution of measurements compared to traditional methods. Here we quantify Κ C and Κ O2 through measures of Pulse Amplitude Modulated (PAM) fluorometry, C fixation and O2 production in an Arctic fjord (Godthåbsfjorden, W Greenland). Through short- (2h) and long-term (24h) experiments, rates of electron transfer (ETRPSII), C fixation and/or O2 production were quantified and compared. Absolute rates of ETR were derived by accounting for Photosystem II light absorption and spectral light composition. Two-hour incubations revealed a linear relationship between ETRPSII and gross 14C fixation (R2 = 0.81) during light-limited photosynthesis, giving a Κ C of 7.6 ± 0.6 (mean ± S.E.) mol é (mol C)−1. Diel net rates also demonstrated a linear relationship between ETRPSII and C fixation giving a Κ C of 11.2 ± 1.3 mol é (mol C)−1 (R2 = 0.86). For net O2 production the electron requirement was lower than for net C fixation giving 6.5 ± 0.9 mol é (mol O2)−1 (R2 = 0.94). This, however, still is an electron requirement 1.6 times higher than the theoretical minimum for O2 production [i.e. 4 mol é (mol O2)−1]. The discrepancy is explained by respiratory activity and non-photochemical electron requirements and the variability is discussed. In conclusion, the bio-optical method and derived electron requirement support conversion of ETR to units of C or O2, paving the road for improved spatial and temporal resolution of primary production estimates. PMID:26218096

Crystal structure of 2,2′′-bis­(2,7-di­chloro-9-hy­droxy-9H-fluoren-9-yl)-1,1′:4′,1′′-terphenyl tri­ethyl­amine trisolvate

PubMed Central

Klien, Henrik; Seichter, Wilhelm; Weber, Edwin

2015-01-01

In the title solvate, C44H26Cl4O2·3C6H15N, the asymmetric part of the unit cell comprises two halves of the diol mol­ecules, 2,2′′-bis­(2,7-di­chloro-9-hy­droxy-9H-fluoren-9-yl)-1,1′:4′,1′′-terphenyl, and three mol­ecules of tri­ethyl­amine, i. e. the diol mol­ecules are located on crystallographic symmetry centres. Two of the solvent mol­ecules are disordered over two positions [occupancy ratios of 0.567 (3):0.433 (3) and 0.503 (3):0.497 (3)]. In the diol mol­ecules, the outer rings of the 1,1′:4′,1′′-terphenyl elements are twisted with reference to their central arene ring and the mean planes of the fluorenyl moieties are inclined with respect to the terphenyl ring to which they are connected, the latter making dihedral angles of 82.05 (8) and 82.28 (8)°. The presence of two 9-fluoren-9-ol units attached at positions 2 and 2′′ of the terphenyl moiety induces a ‘folded’ geometry which is stabilized by intra­molecular C—H⋯O hydrogen bonds and π–π stacking inter­actions, the latter formed between the fluorenyl units and the central ring of the terphenyl unit [centroid–centroid distances = 3.559 (1) and 3.562 (1) Å]. The crystal is composed of 1:2 complex units, in which the solvent mol­ecules are associated with the diol mol­ecules via O—H⋯N hydrogen bonds, while the remaining solvent mol­ecule is linked to the host by a C—H⋯N hydrogen bond. The given pattern of inter­molecular inter­actions results in formation of chain structures extending along [010]. PMID:26870400

γ-Aminobutyric acid (GABA) oral rinse reduces capsaicin-induced burning mouth pain sensation: An experimental quantitative sensory testing study in healthy subjects.

PubMed

Zhang, Y; Wang, K; Arendt-Nielsen, L; Cairns, B E

2018-02-01

In burning mouth patients, analgesia after oral administration of clonazepam may result from modulation of peripheral γ-aminobutyric acid (GABA) receptors. The effect of oral administration of test solutions (water, 0.5 mol/L or 0.05 mol/L GABA, 1% lidocaine) was investigated for the amelioration of pain and sensitivity induced by application of capsaicin (1%, 2 min) to the tongue of thirty healthy male and female subjects in this four-session, randomized, placebo-controlled, double-blinded, cross-over study. Intra-oral quantitative sensory testing was used to assess cold (CDT), warm (WDT) and mechanical (MDT) detection thresholds as well as mechanical (MPT) and heat (HPT) pain thresholds. Capsaicin-induced pain intensity was continuously rated on a 0-10 electronic visual analogue scale (VAS). The area under the VAS curve (VASAUC) after rinsing was calculated for each solution. Capsaicin application on the tongue evoked burning pain with a peak of 4.8/10, and significantly increased CDT and MDT while significantly decreasing WDT, HPT, and MPT. The VASAUC was significantly smaller after oral rinse with 0.05 mol/L GABA, 0.5 mol/L GABA, and 1% lidocaine than after oral rinse with water. Rinse with 0.5 mol/L or 0.05 mol/L GABA were similarly effective in decreasing VASAUC. Rinsing with either 1% lidocaine, 0.5 mol/L or 0.05 mol/L GABA also significantly attenuated the effects of capsaicin on WDT and HPT in a treatment independent manner. There were no sex-related differences in these effects of GABA. Capsaicin-induced burning tongue pain and decreases in WDT and HPT can be ameliorated by rinsing the mouth with lidocaine and GABA solutions. Rinsing the mouth with an oral GABA containing solution ameliorated burning pain and increased heat sensitivity produced by application of capsaicin to the tongue. This finding suggests that GABA can act as a local analgesic agent in the oral cavity. © 2017 European Pain Federation - EFIC®.

Comparison of different cryopreservation methods for horse and donkey embryos.

PubMed

Pérez-Marín, C C; Vizuete, G; Vazquez-Martinez, R; Galisteo, J J

2018-05-01

Few studies have been published about cryopreservation and embryo assessment in horses and donkeys. To evaluate the viability of embryos collected from mares and jennies that were cryopreserved by slow freezing or by vitrification. Randomised controlled experiment. Horse (n=19) and donkey (n=16) embryos (≤300 μm) were recovered on days 6.5-7.5 post-ovulation and assigned to control or cryopreservation protocols of slow freezing or vitrification. For slow freezing, 1.5 mol/L ethylene glycol (EG) was used. For vitrification, horse embryos were exposed to 1.4 mol/L glycerol, 1.4 mol/L glycerol + 3.6 mol/L EG and 3.4 mol/L glycerol + 4.6 mol/L EG, using Fibreplug or a 0.25 mL straw; donkey embryos were vitrified using Fibreplug with similar EG-glycerol solutions to above or 7.0 mol/L EG. Dead cells, apoptotic and fragmented nuclei, and cytoskeleton quality were assessed on thawed/warmed embryos. A significant decrease in embryo quality was observed after cryopreservation (P<0.05). Although the percentage of dead cells was lower (P<0.05) in control than in cryopreserved embryos, no differences were observed between freezing protocols used for horse or donkey embryos. While no differences were detected in the number of apoptotic cells in warmed horse embryos, in donkey embryos a higher incidence of apoptosis was measured after vitrification with EG-glycerol in Fibreplug (P<0.05). Vitrified horse embryos had a significantly (P<0.05) higher percentage of nonviable cells than donkey embryo. Actin cytoskeleton quality did not differ between treatments. Difficulties in obtaining a large number of embryos meant that the number of embryos per group was low. Vitrified horse and donkey embryos did not show higher susceptibility to cell damage than those preserved by slow freezing, whether using straws or Fibreplug. However, Fibreplug with EG 7 mol/L resulted in fewer nonviable and apoptotic cells in donkey embryos. Donkey embryos showed lower susceptibility to vitrification than horse embryos. THE SUMMARY IS AVAILABLE IN SPANISH - SEE SUPPORTING INFORMATION. © 2017 EVJ Ltd.

Nutritional intervention and impact of polyphenol on glycohemoglobin (HbA1c) in non-diabetic and type 2 diabetic subjects: Systematic review and nmeta-analysis.

PubMed

Palma-Duran, Susana A; Vlassopoulos, Antonis; Lean, Mike; Govan, Lindsay; Combet, Emilie

2017-03-24

Polyphenols have been extensively studied for their antioxidant and anti-inflammatory properties. Recently, their antiglycative actions by oxidative stress modulation have been linked to the prevention of diabetes and associated complications. This article assesses the evidence for polyphenol interventions on glycohemoglobin (HbA1c) in non-diabetic, pre-diabetic, and type 2 diabetes mellitus (T2DM) subjects. A systematic review of polyphenols' clinical trials on HbA1c in humans was performed according to the Preferred Reporting Items for Systematic Review and Meta-Analysis. Thirty-six controlled randomized trials with HbA1c values were included. Polyphenols (extracts, supplements, and foods) were supplemented (28 mg to 1.5 g) for 0.7 to 12 months. Combining all subjects (n = 1954, mean baseline HbA1c = 7.03%, 53 mmol/mol), polyphenol supplementation significantly (P < 0.001) lowered HbA1c% by -0.53 ± 0.12 units (-5.79 ± 0.13 mmol/mol). This reduction was significant (P < 0.001) in T2DM subjects, specifically (n = 1426, mean baseline HbA1c = 7.44%, 58 mmol/mol), with HbA1c% lowered by -0.21 ± 0.04 units (-2.29 ± 0.4 mmol/mol). Polyphenol supplementation had no significant effect (P > 0.21) in the non-diabetic (n = 258, mean baseline HbA1c = 5.47%, 36 mmol/mol) and the pre-diabetic subjects (n = 270, mean baseline HbA1c = 6.06%, 43 mmol/mol) strata: -0.39 ± 0.27 HbA1c% units (-4.3 ± 0.3 mmol/mol), and -0.38 ± 0.31 units (-4.2 ± 0.31 mmol/mol), respectively. In conclusion, polyphenols can successfully reduce HbA1c in T2DM without any intervention at glycemia, and could contribute to the prevention of diabetes complications.

Alcohol Dehydrogenase-1B (rs1229984) and Aldehyde Dehydrogenase-2 (rs671) Genotypes and Alcoholic Ketosis Are Associated with the Serum Uric Acid Level in Japanese Alcoholic Men.

PubMed

Yokoyama, Akira; Yokoyama, Tetsuji; Mizukami, Takeshi; Matsui, Toshifumi; Kimura, Mitsuru; Matsushita, Sachio; Higuchi, Susumu; Maruyama, Katsuya

2016-05-01

To identify determinants of hyperuricemia in alcoholics. The serum uric acid (UA) levels of 1759 Japanese alcoholic men (≥40 years) were measured on their first visit or within 3 days after admission; ADH1B and ALDH2 genotyping on blood DNA samples were performed. Dipstick urinalyses for ketonuria and serum UA measurements were simultaneously performed for 621 men on their first visit. Serum UA levels of >416 μmol/l (7.0 mg/dl) and ≥535 μmol/l (9.0 mg/dl) were observed in 30.4 and 7.8% of the subjects, respectively. Ketonuria was positive in 35.9% of the subjects, and a multivariate analysis revealed that the ketosis level was positively associated with the UA level. The presence of the ADH1B*2 allele and the ALDH2*1/*1 genotype increased the odds ratio (OR; 95% confidence interval) among subjects with a high UA level of >416 μmol/l (vs. ≤416 μmol/l; 2.04 [1.58-2.65] and 1.48 [1.09-2.01], respectively) and those with a high UA level of ≥535 μmol/l (vs. ≤416 μmol/l; 2.29 [1.42-3.71] and 3.03 [1.51-6.08], respectively). The ADH1B*2 plus ALDH2*1/*1 combination yielded the highest ORs (2.86 [1.61-5.10] and 6.21 [1.49-25.88] for a UA level of >416 μmol/l and ≥535 μmol/l, respectively), compared with the ADH1B*1/*1 plus ALDH2*1/*2 combination. The presence of diabetes and the consumption of Japanese sake rather than beer were negatively associated with the UA levels. The faster metabolism of ethanol and acetaldehyde by the ADH1B*2 allele and ALDH2*1/*1 genotype and higher ketosis levels were associated with higher UA levels in alcoholics, while diabetes and the consumption of sake were negative determinants. © The Author 2015. Medical Council on Alcohol and Oxford University Press. All rights reserved.

Urinary hydroxy-metabolites of naphthalene, phenanthrene and pyrene as markers of exposure to diesel exhaust.

PubMed

Kuusimäki, Leea; Peltonen, Yrjö; Mutanen, Pertti; Peltonen, Kimmo; Savela, Kirsti

2004-01-01

The objective of this study was to assess the exposure of bus-garage and waste-collection workers to polycyclic aromatic hydrocarbons (PAHs) derived from diesel exhaust by the measurement of levels of seven urinary PAH metabolites: 2-naphthol, 1-hydroxyphenanthrene, 2-hydroxyphenanthrene, 3-hydroxyphenanthrene, 1+9-hydroxyphenanthrene, 4-hydroxyphenanthrene and 1-hydroxypyrene. One urine sample from each of 46 control persons, and one pre-shift and two post-shift spot urine samples from 32 exposed workers were obtained in winter and in summer. The metabolites were analysed after enzymatic hydrolysis by high performance liquid chromatography (HPLC) with fluorescence detection. The sum of seven PAH metabolites (mean 3.94 +/- 3.40 and 5.60 +/- 6.37 micromol/mol creatinine in winter and summer, respectively) was higher [P=0.01, degrees of freedom (df) =61.2 and P=0.01, df=67.6 in winter and summer, respectively] in the exposed group than in the control group (mean 3.18 +/- 3.99 and 3.03 +/- 2.01 micromol/mol creatinine in winter and summer, respectively). The mean concentrations of 2-naphthol among exposed and controls ranged between 3.34 and 4.85 micromol/mol creatinine and 2.51 and 2.58 micromol/mol creatinine, respectively (P<0.01 in winter, P<0.03 in summer). The mean level of the hydroxyphenanthrenes in the samples of exposed workers was between 0.40 and 0.70 micromol/mol creatinine and in the control samples 0.40-0.60 micromol/mol creatinine. The concentration of 1-hydroxypyrene was higher among exposed workers in both pre-shift and post-shift samples (mean 0.10-0.15 micromol/mol creatinine) than in control group (mean 0.05-0.06 micromol/mol creatinine) in winter (P=0.002, df=78) and in summer (P<0.001, df=68). The urinary hydroxy-metabolites of naphthalene, phenanthrene and pyrene showed low exposure to diesel-derived PAHs; however, it was higher in exposed workers than in control group. Urinary PAH monohydroxy-metabolites measured in this study did not correlate with the PAHs in the air samples, reported earlier, in 2002 and 2003.

Identification of Potential Biomarkers for Urine Metabolomics of Polycystic Ovary Syndrome Based on Gas Chromatography-Mass Spectrometry.

PubMed

Zou, Ying; Zhu, Fu-Fan; Fang, Chao-Ying; Xiong, Xi-Yue; Li, Hong-Yun

2018-04-20

Polycystic ovary syndrome (PCOS) is a complex endocrine and metabolic disorder, and it's diagnosis is difficult. The aim of this study was to investigate the metabolic profiles of PCOS patients by analyzing urine samples and identify useful biomarkers for diagnosis of PCOS. This study was carried out in the Department of Obstetrics and Gynecology of the Maternal and Child Health Hospital of Hunan Province from December 2014 to July 2016. In this study, the urine samples of 21 women with PCOS and 16 healthy controls were assessed through gas chromatography-mass spectrometry to investigate the urine metabolite characteristics of PCOS and identify useful biomarkers for the diagnosis of this disorder. The Student's t-test and rank sum test were applied to validate the statistical significance of the between the two groups. In total, 35 urine metabolites were found to be significantly different between the PCOS patients and the controls. In particular, a significant increase in the levels of lactose (10.01 [0,13.99] mmol/mol creatinine vs. 2.35 [0.16, 3.26] mmol/mol creatinine, P = 0.042), stearic acid (2.35 [1.47, 3.14] mmol/mol creatinine vs. 0.05 [0, 0.14] mmol/mol creatinine, P < 0.001), and palmitic acid (2.13 [1.07, 2.79] mmol/mol creatinine vs. 0 [0, 0] mmol/mol creatinine, P < 0.001) and a decrease in the levels of succinic acid (0 [0, 0] mmol/mol creatinine vs. 38.94 [4.16, 51.30] mmol/mol creatinine, P < 0.001) were found in the PCOS patients compared with the controls. It was possible to cluster the PCOS patients and the healthy controls into two distinct regions based on a principal component analysis model. Of the differentially expressed metabolites, four compounds, including stearic acid, palmitic acid, benzoylglycine, and threonine, were selected as potential biomarkers. This study offers new insight into the pathogenesis of PCOS, and the discriminating urine metabolites may provide a prospect for the diagnosis of PCOS.

The [C{sub 6}H{sub 10}]{sup {sm{underscore}bullet}+} hypersurface: The parent radical cation Diels-Alder reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hoffmann, M.; Schaefer, H.F. III

1999-07-21

Various possible reaction pathways between ethene and butadiene radical cation (cis- and trans-), have been investigated at different levels of theory up to UCCSD(T)/DZP/UMP2(fc)/DZP and with density functional theory at B3LYP/DZP. A stepwise addition involving open chain intermediates and leading to the Diels-Alder product, the cyclohexene radical cation, was found to have a total activation barrier {Delta}G{sup 298{ne}} = 6.3 kcal mol{sup {minus}1} and a change in free Gibbs energy, {Delta}G{sup 298}, of {minus}33.5 kcal mol{sup {minus}1}. On the E{degree} potential energy surface, all transition states are lower in energy than separated ethene and butadiene, the exothermicity {Delta}E = -45.6more » kcal mol{sup {minus}1}. A more direct path could be characterized as stepwise with one intermediate only at the SCF level but not at electron-correlated levels and hence might actually be a concerted strongly asynchronous addition with a very small or no activation barrier (UCCSD(T)/DZP/UHF/6-31G* gives a {Delta}G{sup 298{ne}} of 0.8 kcal mol{sup {minus}1}). The critical step for another alternative, the cyclobutanation-vinylcyclobutane/cyclohexene rearrangement, is a 1,3-alkyl shift which involves a barrier ({Delta}G{sup 298{ne}}) only 1.7 kcal mol{sup {minus}1} higher than that of stop use addition for both cis-, and trans-butadiene radical cation. However, from the (ethene and trans-butadiene) reactions, ring expansion of the vinylcyclobutane radical cation intermediate, to a methylene cyclopentane radical cation, requires an activation only 1.3 kcal mol{sup {minus}1} larger than for (trans-butadiene radical). While cis/trans isomerization of free butadiene radical cation requires a high activation (24.9 kcal mol{sup {minus}1}), a reaction sequence involving addition of ethene (to stepwise give an open chain intermediate and vinyl cyclobutane radical cation) has a barrier of only 3.5 kcal mol{sup {minus}1} ({Delta}G{sup 298{ne}}). This sequence also makes ethene and butadiene radical cations to exchange terminal methylene groups.« less

DFT benchmark study for the oxidative addition of CH 4 to Pd. Performance of various density functionals

NASA Astrophysics Data System (ADS)

de Jong, G. Theodoor; Geerke, Daan P.; Diefenbach, Axel; Matthias Bickelhaupt, F.

2005-06-01

We have evaluated the performance of 24 popular density functionals for describing the potential energy surface (PES) of the archetypal oxidative addition reaction of the methane C-H bond to the palladium atom by comparing the results with our recent ab initio [CCSD(T)] benchmark study of this reaction. The density functionals examined cover the local density approximation (LDA), the generalized gradient approximation (GGA), meta-GGAs as well as hybrid density functional theory. Relativistic effects are accounted for through the zeroth-order regular approximation (ZORA). The basis-set dependence of the density-functional-theory (DFT) results is assessed for the Becke-Lee-Yang-Parr (BLYP) functional using a hierarchical series of Slater-type orbital (STO) basis sets ranging from unpolarized double-ζ (DZ) to quadruply polarized quadruple-ζ quality (QZ4P). Stationary points on the reaction surface have been optimized using various GGA functionals, all of which yield geometries that differ only marginally. Counterpoise-corrected relative energies of stationary points are converged to within a few tenths of a kcal/mol if one uses the doubly polarized triple-ζ (TZ2P) basis set and the basis-set superposition error (BSSE) drops to 0.0 kcal/mol for our largest basis set (QZ4P). Best overall agreement with the ab initio benchmark PES is achieved by functionals of the GGA, meta-GGA, and hybrid-DFT type, with mean absolute errors of 1.3-1.4 kcal/mol and errors in activation energies ranging from +0.8 to -1.4 kcal/mol. Interestingly, the well-known BLYP functional compares very reasonably with an only slightly larger mean absolute error of 2.5 kcal/mol and an underestimation by -1.9 kcal/mol of the overall barrier (i.e., the difference in energy between the TS and the separate reactants). For comparison, with B3LYP we arrive at a mean absolute error of 3.8 kcal/mol and an overestimation of the overall barrier by 4.5 kcal/mol.

Reactivity of OHrad and e-aq from electron beam irradiation of aqueous solutions of EDTA and aminopolycarboxylic acids

NASA Astrophysics Data System (ADS)

Vel Leitner, N. Karpel; Guilbault, I.; Legube, B.

2003-05-01

Electron beam irradiation of aqueous solutions of EDTA, EDDA NN‧, NTA, IDA and Cu-EDTA was performed in the presence of scavengers for the hydroxyl radicals (methanol) or for the solvated electrons (hydrogen peroxide). Experiments showed that for each molecule, the G-value decreases as the radiation dose increases from 1 to 25 kGy, and for EDTA, when the initial concentration decreases from 10 to 0.1 mmol l-1. At pH 8 and for 5 kGy, the G-values of NTA, IDA, EDTA and EDDA NN‧ removal ascribed to OHrad radicals are, respectively, 0.06, 0.06, 0.15 and 0.20 μmol J-1, whereas for the solvated electrons the G-values were, respectively, 0.01, 0.01, 0.06 and 0.04 μmol J-1. The rate constants of hydroxyl radicals and solvated electrons were determined by comparison with one competitor. For each active species (hydroxyl radical or solvated electron), the reactivity is connected to the number of nitrogen atoms and acetate groups. The rate constants of OHrad radicals are above 1010 and 8.6×109 l mol-1 s-1 for EDDA NN‧ and EDTA, respectively, 2.1×109 l mol-1 s-1 for IDA and 6.1×108 l mol-1 s-1 for NTA. The reactivity of solvated electrons is smaller and the rate constants are in the range 1.9×106-3.7×106 l mol-1 s-1 for NTA, IDA and EDDA NN‧ and equal 1.4×107 l mol-1 s-1 for EDTA. The reactivity of the complex Cu-EDTA towards OHrad does not differ to a large extent from EDTA whereas with e-aq the reactivity of Cu-EDTA is better than EDTA since ke-/Cu-EDTA reaches 2.2×109 l mol-1 s-1. It follows that when both active entities (OHrad and e-aq) are involved in the electron beam irradiation process, the removal of free aminopolycarboxylic acids is mainly due to OHrad radicals. However, the complex Cu-EDTA is concerned by both e-aq and OHrad radicals.

Progesterone-mediated angiogenic activity of endothelial progenitor cell and angiogenesis in traumatic brain injury rats were antagonized by progesterone receptor antagonist.

PubMed

Yu, Peng; Li, Shengjie; Zhang, Zhifei; Wen, Xiaolong; Quan, Wei; Tian, Qilong; Gao, Chuang; Su, Wanqiang; Zhang, Jianning; Jiang, Rongcai

2017-10-01

Progesterone (P4) has the potential therapeutic effects for traumatic brain injury (TBI) whose recovery depended on the enhanced angiogenesis. Endothelial progenitor cell (EPC) plays an essential role in vascular biology. We previously demonstrated that P4 administration improved circulating EPC level and neurological recovery of rat with TBI. Here, we hypothesized that P4 augmented angiogenic potential of EPC and the angiogenesis-related neurorestoration after TBI through classical progesterone receptor (PR). EPC derived from rats were stimulated with graded concentrations (0, 10 -10 , 10 -9 , 5 × 10 -9 , 10 -8 , 10 -7  mol/L) of P4 or 10 -6  mol/L ulipristal acetate (UPA, a PR antagonist). Male rats were subjected to cortical impact injury and treated with (i) DMSO (dimethyl sulfoxide), (ii) P4 and (iii) P4 and UPA. It showed that P4 improved the angiogenic potential of EPC, including tube formation, adhesion, migration and vascular endothelial growth factor secretion, in a dose-dependent fashion with the maximal effect achieved at 10 -9  mol/L P4. High concentration (10 -7  mol/L) of P4 impaired the angiogenic potential of EPC. Notably, 10 -6  mol/L UPA antagonized the stimulatory effects of 10 -9  mol/L P4. After administrating P4, a significant improvement of neurological function and the restoration of the leaked blood-brain barrier were observed as well as a reduction of the brain water content. Both vessel density and expression of occludin of vessels were increased. When UPA was administered with P4, the neural restoration and angiogenesis were all reversed. Western blot showed that 10 -9  mol/L P4 increased the content of PRA and PRB of EPC, while 10 -7  mol/L P4 reduced the content of both PR isoforms, but there was no change found in the TBI rats. It may suggest that P4-mediated angiogenic activity of EPC and angiogenesis in TBI rats were antagonized by PR antagonist. © 2017 John Wiley & Sons Ltd.

Influence of capillary barrier effect on biogas distribution at the base of passive methane oxidation biosystems: Parametric study.

PubMed

Ahoughalandari, Bahar; Cabral, Alexandre R

2017-05-01

The efficiency of methane oxidation in passive methane oxidation biosystems (PMOBs) is influenced by, among other things, the intensity and distribution of the CH 4 loading at the base of the methane oxidation layer (MOL). Both the intensity and distribution are affected by the capillary barrier that results from the superposition of the two materials constituting the PMOB, namely the MOL and the gas distribution layer (GDL). The effect of capillary barriers on the unsaturated flow of water has been well documented in the literature. However, its effect on gas flow through PMOBs is still poorly documented. In this study, sets of numerical simulations were performed to evaluate the effect of unsaturated hydraulic characteristics of the MOL material on the value and distribution of moisture and hence, the ease and uniformity in the distribution of the upward flow of biogas along the GDL-MOL interface. The unsaturated hydraulic parameters of the materials used to construct the experimental field plot at the St-Nicephore landfill (Quebec, Canada) were adopted to build the reference simulation of the parametric study. The behavior of the upward flow of biogas for this particular material was analyzed based on its gas intrinsic permeability function, which was obtained in the laboratory. The parameters that most influenced the distribution and the ease of biogas flow at the base of the MOL were the saturated hydraulic conductivity and pore size distribution of the MOL material, whose effects were intensified as the slope of the interface increased. The effect of initial dry density was also assessed herein. Selection of the MOL material must be made bearing in mind that these three parameters are key in the effort to prevent unwanted restriction in the upward flow of biogas, which may result in the redirection of biogas towards the top of the slope, leading to high CH 4 fluxes (hotspots). In a well-designed PMOB, upward flow of biogas across the GDL-MOL interface is unrestricted and moisture distribution is uniform. This paper tries to show how to obtain this. Copyright © 2016 Elsevier Ltd. All rights reserved.

NIST gravimetrically prepared atmospheric level methane in dry air standards suite.

PubMed

Rhoderick, George C; Carney, Jennifer; Guenther, Franklin R

2012-04-17

The Gas Metrology Group at the National Institute of Standards and Technology was tasked, by a congressional climate change act, to support the atmospheric measurement community through standards development of key greenhouse gases. This paper discusses the development of a methane (CH(4)) primary standard gas mixture (PSM) suite to support CH(4) measurement needs over a large amount-of-substance fraction range 0.3-20,000 μmol mol(-1), but with emphasis at the atmospheric level 300-4000 nmol mol(-1). Thirty-six CH(4) in dry air PSMs were prepared in 5.9 L high-pressure aluminum cylinders with use of a time-tested gravimetric technique. Ultimately 14 of these 36 PSMs define a CH(4) standard suite covering the nominal ambient atmospheric range of 300-4000 nmol mol(-1). Starting materials of pure CH(4) and cylinders of dry air were exhaustively analyzed to determine the purity and air composition. Gas chromatography with flame-ionization detection (GC-FID) was used to determine a CH(4) response for each of the 14 PSMs where the reproducibility of average measurement ratios as a standard error was typically (0.04-0.26) %. An ISO 6134-compliant generalized least-squares regression (GenLine) program was used to analyze the consistency of the CH(4) suite. All 14 PSMs passed the u-test with residuals between the gravimetric and the GenLine solution values being between -0.74 and 1.31 nmol mol(-1); (0.00-0.16)% relative absolute. One of the 14 PSMs, FF4288 at 1836.16 ± 0.75 nmol mol(-1) (k = 1) amount-of-substance fraction, was sent to the Korea Research Institute of Standards and Science (KRISS), the Republic of Korea's National Metrology Institute, for comparison. The same PSM was subsequently sent to the National Oceanic and Atmospheric Administration (NOAA) for analysis to their standards. Results show agreement between KRISS-NIST of +0.13% relative (+2.3 nmol mol(-1)) and NOAA-NIST of -0.14% relative (-2.54 nmol mol(-1)).

Nitric oxide inhibition of NaCl secretion in the opercular epithelium of seawater-acclimated killifish, Fundulus heteroclitus.

PubMed

Gerber, Lucie; Jensen, Frank B; Madsen, Steffen S; Marshall, William S

2016-11-01

Nitric oxide (NO) modulates epithelial ion transport pathways in mammals, but this remains largely unexamined in fish. We explored the involvement of NO in controlling NaCl secretion by the opercular epithelium of seawater killifish using an Ussing chamber approach. Pharmacological agents were used to explore the mechanism(s) triggering NO action. A modified Biotin-switch technique was used to investigate S-nitrosation of proteins. Stimulation of endogenous NO production via the nitric oxide synthase (NOS) substrate l-arginine (2.0 mmol l -1 ), and addition of exogenous NO via the NO donor SNAP (10 -6 to 10 -4  mol l -1 ), decreased the epithelial short-circuit current (I sc ). Inhibition of endogenous NO production by the NOS inhibitor l-NAME (10 -4  mol l -1 ) increased I sc and revealed a tonic control of ion transport by NO in unstimulated opercular epithelia. The NO scavenger PTIO (10 -5  mol l -1 ) supressed the NO-mediated decrease in I sc , and confirmed that the effect observed was elicited by release of NO. The effect of SNAP on I sc was abolished by inhibitors of the soluble guanylyl cyclase (sGC), ODQ (10 -6  mol l -1 ) and Methylene Blue (10 -4  mol l -1 ), revealing NO signalling via the sGC/cGMP pathway. Incubation of opercular epithelium and gill tissues with SNAP (10 -4  mol l -1 ) led to S-nitrosation of proteins, including Na + /K + -ATPase. Blocking of NOS with l-NAME (10 -6  mol l -1 ) or scavenging of NO with PTIO during hypotonic shock suggested an involvement of NO in the hypotonic-mediated decrease in I sc Yohimbine (10 -4  mol l -1 ), an inhibitor of α 2 -adrenoceptors, did not block NO effects, suggesting that NO is not involved in the α-adrenergic control of NaCl secretion. © 2016. Published by The Company of Biologists Ltd.

[Baicalein promotes the apoptosis of HeLa cells by inhibiting ERK1/2 expression].

PubMed

Wang, Yongzhou; Xia, Jiyi; Tang, Xiaoping; Tang, Li; Mao, Xiguang; Zhang, Yujiao; Yu, Xiaolan

2016-11-01

Objective To investigate the effects of baicalein and U0126 treatment on the apoptosis of human cervical carcinoma HeLa cells and the potential mechanism. Methods HeLa cells were subjected to (1, 2, 5, 10, 20, 50, 100, 200, 300) μmol/L baicalein or (1, 2, 5, 10, 20, 30) μmol/L U0126 treatment for 24 hours. The optimal concentrations of baicalein and U0126 for HeLa inhibition was determined by a cell counting Kit-8 assay. HeLa cells were then treated with these inhibitory concentrations for 24 hours separately or in combination. The cell cycle and the degree of apoptosis were analyzed by flow cytometry. The cell apoptosis index was evaluated by the TUNEL assay. The expressions of extracellular signal-regulated kinase 1/2 (ERK1/2), Bax, and Bcl-2 at the mRNA and protein levels were examined by real-time PCR and Western blotting, respectively. Results Optimal inhibitory concentrations of baicalein and U0126 for HeLa cells were 200 μmol/L and 10 μmol/L, respectively. Compared with the control group, baicalein treatment increased the growth rate of cells in the G0/G1 phase but decreased the S phase. Combination treatment of 200 μmol/L baicalein and 10 μmol/L U0126 for 24 hours further reduced the S phase growth rate. Treatment with 10 μmol/L U0126 or 200 μmol/L baicalein for 24 hours induced cell apoptosis, and the combination treatment induced more apoptosis. Treatment by baicalein alone or in combination with U0126 for 24 hours significantly decreased ERK1/2 and Bcl-2 mRNA expressions, and upregulated Bax mRNA expression. It also downregulated ERK1/2 phosphorylation and Bcl-2 protein expression, while increasing Bax protein expression. Conclusion Both baicalein and U012 appear to inhibit proliferation, induce apoptosis, and increase the growth rate in the G0/G1 phase but reduce the S phase of HeLa cells. This effect is enhanced when they are used synergistically.

Stibiconite (Sb3O6OH), senarmontite (Sb2O3) and valentinite (Sb2O3): Dissolution rates at pH 2-11 and isoelectric points

NASA Astrophysics Data System (ADS)

Biver, M.; Shotyk, W.

2013-05-01

Batch reactor experiments were carried out in order to derive rate laws for the proton promoted dissolution of the main natural antimony oxide phases, namely stibiconite (idealized composition SbSb2O6OH), senarmontite (cubic Sb2O3) and (metastable) valentinite (orthorhombic Sb2O3) over the range 2 ⩽ pH ⩽ 11, under standard conditions and ionic strength I = 0.01 mol l-1. The rates of antimony release by stibiconite were r = (2.2 ± 0.2) × 10-9 a(H+)0.11±0.01 mol m-2 s-1 for 2.00 ⩽ pH ⩽ 4.74 and r = (4.3 ± 0.2) × 10-10 a(H+)-0.030±0.003 mol m-2 s-1 for 4.74 ⩽ pH ⩽ 10.54. The rates of dissolution of senarmontite were r = (5.3 ± 2.2) × 10-7 a(H+)0.54±0.05 mol m-2 s-1 for 2.00 ⩽ pH ⩽ 6.93 and r = (1.4 ± 0.3) × 10-14 a(H+)-0.53±0.07 mol m-2 s-1 for 6.93 ⩽ pH ⩽ 10.83. The rates of dissolution of valentinite were r = (6.3 ± 0.2) × 10-8 a(H+)0.052±0.003 mol m-2 s-1 for 1.97 ⩽ pH ⩽ 6.85. Above pH = 6.85, valentinite was found to dissolve at a constant rate of r = (2.79 ± 0.05) × 10-8 mol m-2 s-1. Activation energies were determined at selected pH values in the acidic and basic domain, over the temperature range 25-50 °C. The values for stibiconite are -10.6 ± 1.9 kJ mol-1 (pH = 2.00) and 53 ± 14 kJ mol-1 (pH = 8.7). For senarmontite, we found 46.6 ± 4.7 kJ mol-1 (pH = 3.0) and 68.1 ± 6.1 kJ mol-1 (pH = 9.9) and for valentinite 41.9 ± 1.1 kJ mol-1 (pH = 3.0) and 39.0 ± 4.6 kJ mol-1 (pH = 9.9). These activation energies are interpreted in the text. The solubility of stibiconite at 25 °C in the pH domain from 2 to 10 was determined; solubilities decrease from 452.0 μg l-1 (as Sb) at pH = 2.00 to 153.2 μg l-1 at pH = 7.55 and increase again in the basic region, up to 176.6 μg l-1 at pH = 9.92. A graphical synopsis of all the kinetic results, including those of stibnite (Sb2S3) from earlier work, is presented. This allows an easy comparison between the dissolution rates of stibnite and the minerals examined in the present work. The isoelectric point (i.e.p.) of the minerals was determined electrokinetically, as a proxy for the zero point of charge (pHzpc), which was experimentally inaccessible; the measured i.e.p. do not correspond to the dissolution rate minima. I.e.p. of antimony oxides have not yet been documented in the literature. The geochemical implications for the weathering of antimony oxide minerals and stibnite, with particular reference to the mobilization of antimony in the context of an abandoned antimony mine (Goesdorf, Luxembourg), are discussed.

[The CK2 inhibitor quninalizarin enhances the anti-proliferative effect of icotinib on EGFR-TKIs-resistant cell lines and its underlying mechanisms].

PubMed

Zhou, Y; Zhang, S; Li, K; Li, Q W; Zhou, F Z; Li, Z Y; Ma, H; Dong, X R; Liu, L; Wu, G; Meng, R

2016-02-01

To explore whether quninalizarin, an specific inhibitor of protein kinase CK2, could sensitize icotinib in EGFR-TKIs (epithelial growth factor receptor-tyrosine kinase inhibitor)-resistant cell lines and uncover the underlying mechanisms. MTT assay was performed to evaluate the inhibitory effect of quninalizarin, icotinib or the combination of both on cell proliferation in several lung adenocarcinoma cell lines. Western blot assay was used to assess if combined inhibition of EGFR and protein kinase CK2 by icotinib and quninalizarin, exerts effect on the expression and phosphorylation of major proteins of EGFR signaling pathways. The IC50 of HCC827, H1650, H1975 and A549 cells for icotinib were (8.07±2.00)μmol/L, (66.01±6.64)μmol/L, (265.60±9.47)μmol/L and (87.88±6.8)μmol/L, respectively, indicating that HCC827 cells are sensitive to icotinib, and the H1650, H1975 and A549 cells are relatively resistant to icotinib. When treated with both quninalizarin and icotinib in the concentration of 50 μmol/L, the viability of H1650, H1975 and A549 cells was (40.64±3.73)%, (65.74±3.27)% and (44.96±0.48)%, respectively, significantly lower than that of H1650, H1975 and A549 cells treated with 50 μmol/L icotinib alone (55.05±1.22)%, (71.98±1.60)% and (61.74±6.18)%, respectively (P<0.01 for all). When treated with both 100 μmol/L quninalizarin and 100 μmol/L icotinib, the viability of H1650, H1975 and A549 ells were (23.35±0.81)%, (55.70±1.03)%, (33.42±1.33)%, respectively, significantly lower than the viability of H1650, H1975 and A549 cells treated with 100 μmol/L icotinib alone (40.57±2.65)%, (62.40±2.05)% and (44.97±8.20)%, respectively, (P<0.01 for all). The two-way ANOVA analysis showed that compared with the viability of EGFR-TKIs-resistant cells (H1650, H1975, A549) treated with 50 μmol/L and 100 μmol/L icotinib alone, the viability of cells treated with icotinib and quinalizarin were significantly suppressed, and the differences were statistically significant (P<0.01). In addition, the phosphorylation form of Akt and ERK (namely p-Akt and p-ERK) were significantly down-regulated by treating with quninalizarin and icotinib together in the H1650 cells while the expression of Akt and ERK changed little. Quinalizarin, as a specific CK2 inhibitor, may overcome icotinib resistance by inhibiting proliferation mediated by Akt and ERK in human lung adenocarcinoma cell lines, and enhances the suppressive effect of icotinib on the proliferation of EGFR-TKIs-resistant human lung adenocarcinoma cells.

5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetra­methoxy­calix[4]arene dichloro­methane hemisolvate

PubMed Central

Fischer, Conrad; Gruber, Tobias; Seichter, Wilhelm; Schindler, Diana; Weber, Edwin

2008-01-01

In the title compound, C48H64O4·0.5CH2Cl2, both crystallographically independent calixarene mol­ecules display a partial cone conformation. Their crystal packing is stabilized by C—H⋯π contacts involving the meth­oxy groups. The solvent mol­ecule is located inter­stitially between two calixarene units with C—H⋯Cl contacts to meth­oxy and tert-butyl groups. One tert-butyl residue of each calixarene mol­ecule is disordered over two positions (occupancies 0.60/0.40 and 0.63/0.37), resulting in bond distances that deviate from ideal values. The tetra­mer calixarene mol­ecules present models with approximate non-crystallographic Cs symmetry. PMID:21202066

Crystal structure of 9-butyl-6-[2-(pyridin-4-yl)ethen­yl]carbazol-3-amine

PubMed Central

Zhang, Ping; Bai, Xiang-Yang; Zhang, Ting

2015-01-01

The asymmetric unit of the title compound, C23H23N3, consists of two mol­ecules, A and B, with different conformations. In mol­ecule A, the dihedral angle between the carbazole ring system (r.m.s. deviation = 0.028 Å) and the pyridine ring is 20.28 (9)° and the N—C—C—C torsion angle of the butyl side chain is −63.4 (3)°. The equivalent data for mol­ecule B are 0.065 Å, 48.28 (11)° and 61.0 (3)°, respectively. In the crystal, the components are connected by weak N—H⋯N hydrogen bonds, generating [030] C(14) chains of alternating A and B mol­ecules. PMID:25995940

4-(3-Methyl­anilino)-N-[N-(1-methyl­ethyl)carbamo­yl]pyridinium-3-sulfon­amidate (torasemide) methanol 0.25-solvate 0.25-hydrate

PubMed Central

Bartolucci, Gianluca; Bruni, Bruno; Coran, Silvia A.; Di Vaira, Massimo

2009-01-01

The title compound, C16H20N4O3S·0.25CH4O·0.25H2O, is a hydrate/methanol solvate of torasemide, a diuretic drug used in the treatment of hypertension. The asymmetric unit contains two torasemide mol­ecules and half-occupied methanol and water mol­ecules. It is isomorphous with the previously reported nonsolvated T–II form of torasemide. The water mol­ecules contribute to the stability of the structure by participating in an extensive system of O—H⋯O hydrogen bonds; N—H⋯N and N—H⋯O hydrogen bonds are also present. Both asymmetric mol­ecules of torasemide form inversion dimers in the crystal. PMID:21584012

[Mixture Leaching Remediation Technology of Arsenic Contaminated Soil].

PubMed

Chen, Xun-feng; Li, Xiao-ming; Chen, Can; Yang, Qi; Deng, Lin-jing; Xie, Wei-qiang; Zhong, Yui; Huang, Bin; Yang, Wei-qiang; Zhang, Zhi-bei

2016-03-15

Soil contamination of arsenic pollution has become a severely environmental issue, while soil leaching is an efficient method for remediation of arsenic-contaminated soil. In this study, batch tests were primarily conducted to select optimal mixture leaching combination. Firstly, five conventional reagents were selected and combined with each other. Secondly, the fractions were analyzed before and after the tests. Finally, to explore the feasibility of mixed leaching, three soils with different arsenic pollution levels were used to compare the leaching effect. Comparing with one-step washing, the two-step sequential washing with different reagents increased the arsenic removal efficiency. These results showed that the mixture of 4 h 0.5 mol · L⁻¹ NaOH + 4 h 0.1 mol · L⁻¹ EDTA was found to be practicable, which could enhance the removal rate of arsenic from 66.67% to 91.83%, and the concentration of arsenic in soil was decreased from 186 mg · kg⁻¹ to 15.2 mg · kg⁻¹. Furthermore, the results indicated that the distribution of fractions of arsenic in soil changed apparently after mixture leaching. Leaching process could significantly reduce the available contents of arsenic in soil. Moreover, the mixture of 0.5 mol · L⁻¹ NaOH + 0.1 mol L⁻¹ EDTA could well decrease the arsenic concentration in aluminum-type soils, while the mixture of 0.5 mol · L⁻¹ OX + 0.5 mol · L⁻¹ NaOH could well decrease the arsenic concentration in iron-type soils.

Effects of gaseous ammonia on intracellular pH values in leaves of C 3- and C 4-plants

NASA Astrophysics Data System (ADS)

Yin, Zu-Hua; Kaiser, Werner; Heber, Ulrich; Raven, John A.

Responses of cytosolic and vacuolar pH to different concentrations (1.3-5.4 μmol NH 3 mol -1 gas or 0.940-3.825 mg NH 3 m -3 gas) of gaseous NH 3 were studied in experiments of 3 h duration by recording changes in fluorescence of pyranine and esculin in leaves of C 3 and C 4 plants. After a lag phase of 0.5-4 min, the uptake of NH 3 at 50-200 nmol m -2 leaf area s -1 increased pyranine fluorescence, indicating cytosolic alkalinization in leaves of Pelargonium zonale L. (C 3) and Amaranthus caudatus L. (C 4). A smaller increase in esculin fluorescence induced by NH 3 indicated some vacuolar alkalization in a Spinacia oleracea L. leaf. Photosynthesis and transpiration remained unchanged during exposure of illuminated leaves to NH 3 for up to 30 min (the maximum tested). CO 2 concentrations influenced the extent of cytosolic alkalinization. 500 μmol CO 2 mol -1 gas suppressed the NH 3-induced cytosolic alkalinization relative to that found in 16 μmol CO 2 mol -1 gas. The suppressing effect of CO 2 on NH 3-induced alkalization was larger in illuminated leaves of the C 4Amaranthus than the C 3Pelargonium. These results indicate that the alkaline pH shift caused by solution and protonation of NH 3 in aqueous leaf compartments is affected by assimilation of NH 3.

Thermodynamic changes in mechanochemically synthesized magnesium hydride nanoparticles.

PubMed

Paskevicius, Mark; Sheppard, Drew A; Buckley, Craig E

2010-04-14

The thermodynamic properties of magnesium hydride nanoparticles have been investigated by hydrogen decomposition pressure measurements using the Sieverts technique. A mechanochemical method was used to synthesize MgH(2) nanoparticles (down to approximately 7 nm in size) embedded in a LiCl salt matrix. In comparison to bulk MgH(2), the mechanochemically produced MgH(2) with the smallest particle size showed a small but measurable decrease in the decomposition reaction enthalpy (DeltaH decrease of 2.84 kJ/mol H(2) from DeltaH(bulk) = 74.06 +/- 0.42 kJ/mol H(2) to DeltaH(nano) = 71.22 +/- 0.49 kJ/mol H(2)). The reduction in DeltaH matches theoretical predictions and was also coupled with a similar reduction in reaction entropy (DeltaS decrease of 3.8 J/mol H(2)/K from DeltaS(bulk) = 133.4 +/- 0.7 J/mol H(2)/K to DeltaS(nano) = 129.6 +/- 0.8 J/mol H(2)/K). The thermodynamic changes in the MgH(2) nanoparticle system correspond to a drop in the 1 bar hydrogen equilibrium temperature (T(1 bar)) by approximately 6 degrees C to 276.2 +/- 2.4 degrees C in contrast to the bulk MgH(2) system at 281.8 +/- 2.2 degrees C. The reduction in the desorption temperature is less than that expected from theoretical studies due to the decrease in DeltaS that acts to partially counteract the effect from the change in DeltaH.

Estimation of activation energy for electroporation and pore growth rate in liquid crystalline and gel phases of lipid bilayers using molecular dynamics simulations.

PubMed

Majhi, Amit Kumar; Kanchi, Subbarao; Venkataraman, V; Ayappa, K G; Maiti, Prabal K

2015-11-28

Molecular dynamics simulations of electroporation in POPC and DPPC lipid bilayers have been carried out at different temperatures ranging from 230 K to 350 K for varying electric fields. The dynamics of pore formation, including threshold field, pore initiation time, pore growth rate, and pore closure rate after the field is switched off, was studied in both the gel and liquid crystalline (Lα) phases of the bilayers. Using an Arrhenius model of pore initiation kinetics, the activation energy for pore opening was estimated to be 25.6 kJ mol(-1) and 32.6 kJ mol(-1) in the Lα phase of POPC and DPPC lipids respectively at a field strength of 0.32 V nm(-1). The activation energy decreases to 24.2 kJ mol(-1) and 23.7 kJ mol(-1) respectively at a higher field strength of 1.1 V nm(-1). At temperatures below the melting point, the activation energy in the gel phase of POPC and DPPC increases to 28.8 kJ mol(-1) and 34.4 kJ mol(-1) respectively at the same field of 1.1 V nm(-1). The pore closing time was found to be higher in the gel than in the Lα phase. The pore growth rate increases linearly with temperature and quadratically with field, consistent with viscosity limited growth models.

Efficient enzymatic production of hydroxy fatty acids by linoleic acid Δ9 hydratase from Lactobacillus plantarum AKU 1009a.

PubMed

Takeuchi, M; Kishino, S; Park, S-B; Hirata, A; Kitamura, N; Saika, A; Ogawa, J

2016-05-01

This study aims to produce hydroxy fatty acids efficiently. Escherichia coli overexpressing linoleic acid Δ9 hydratase from Lactobacillus plantarum AKU 1009a was employed to produce hydroxy fatty acids with industrial potential. We found that 280 g l(-1) of linoleic acid (1 mol l(-1)) was converted into (S)-10-hydoxy-cis-12-octadecenoic acid (HYA) with a high conversion rate of 98% (mol/mol) and more than 99·9% enantiomeric excess (e.e.) by recombinant E. coli cells in the presence of FAD and NADH. In the same way, many kinds of C18 unsaturated fatty acids with Δ9 carbon double bond (280 g l(-1)) were converted into corresponding 10-hydroxy fatty acids with the conversion rates over 95% (mol/mol). We also produced HYA at a high rate of accumulation (289 g l(-1) ) with a high yield (97 mol%) in a reaction mixture that contained glucose instead of NADH. We developed a process for producing several types of hydroxy fatty acids with high accumulation rates and high yields. Hydroxy fatty acids are important materials for the chemical, food, cosmetic and pharmaceutical industries, and thus they have recently attracted much interest in a variety of research fields. However, the mass production of hydroxy fatty acids has been limited. This method of hydroxy fatty acids production will facilitate the widespread application of hydroxy fatty acids in various industries. © 2016 The Society for Applied Microbiology.

Correlating steric hydration forces with water dynamics through surface force and diffusion NMR measurements in a lipid–DMSO–H2O system

PubMed Central

Schrader, Alex M.; Donaldson, Stephen H.; Song, Jinsuk; Cheng, Chi-Yuan; Lee, Dong Woog; Han, Songi; Israelachvili, Jacob N.

2015-01-01

Dimethyl sulfoxide (DMSO) is a common solvent and biological additive possessing well-known utility in cellular cryoprotection and lipid membrane permeabilization, but the governing mechanisms at membrane interfaces remain poorly understood. Many studies have focused on DMSO–lipid interactions and the subsequent effects on membrane-phase behavior, but explanations often rely on qualitative notions of DMSO-induced dehydration of lipid head groups. In this work, surface forces measurements between gel-phase dipalmitoylphosphatidylcholine membranes in DMSO–water mixtures quantify the hydration- and solvation-length scales with angstrom resolution as a function of DMSO concentration from 0 mol% to 20 mol%. DMSO causes a drastic decrease in the range of the steric hydration repulsion, leading to an increase in adhesion at a much-reduced intermembrane distance. Pulsed field gradient NMR of the phosphatidylcholine (PC) head group analogs, dimethyl phosphate and tetramethylammonium ions, shows that the ion hydrodynamic radius decreases with increasing DMSO concentration up to 10 mol% DMSO. The complementary measurements indicate that, at concentrations below 10 mol%, the primary effect of DMSO is to decrease the solvated volume of the PC head group and that, from 10 mol% to 20 mol%, DMSO acts to gradually collapse head groups down onto the surface and suppress their thermal motion. This work shows a connection between surface forces, head group conformation and dynamics, and surface water diffusion, with important implications for soft matter and colloidal systems. PMID:26261313

Inhibitors of peptidases: how they influence the biological activities of substance P, neurokinins, kinins and angiotensins in isolated vessels.

PubMed

Rouissi, N; Nantel, F; Drapeau, G; Rhaleb, N E; Dion, S; Regoli, D

1990-01-01

Myotropic effects of various peptides were measured in three isolated vessels, the dog carotid artery, the rabbit pulmonary artery and the rat portal vein in the absence and in presence of several peptidase inhibitors, in order to evaluate the interference by metabolism with the peptides' biological activities. After adequate controls, captopril (4.6 x 10(-6) mol/l), thiorphan (1.0 x 10(-6) mol/l), phosphoramidon (4.6 x 10(-6) mol/l), chymostatin (1 mg/l), bestatin (8.1 x 10(-6) mol/l) or bacitracin (1.4 x 10(-5) mol/l) were left in contact with the tissues for 20-40 min to inhibit tissue peptidases before measuring again the biological effects of the various peptides. In some experiments, mergetpa (5.4 x 10(-6) mol/l) was used. All peptidase inhibitors were inactive on their own and only captopril potentiated the effects of substance P, neurokinins, bradykinin and inhibited angiotensin I in two preparations, the dog carotid artery, the rat portal vein, and, excluding bradykinin, also in the rabbit pulmonary artery. Captopril and thiorphan significantly potentiated the maximal response of the rat portal vein to substance P and mergetpa inhibited completely the effect of bradykinin on the rabbit pulmonary artery. The present findings suggest that the most active proteolytic enzyme interfering with the biological effects of vasoactive peptides on three isolated vessels is the angiotensin-converting enzyme (kininase II).

Equilibrium unfolding studies of the rat liver methionine adenosyltransferase III, a dimeric enzyme with intersubunit active sites.

PubMed Central

Gasset, María; Alfonso, Carlos; Neira, José L; Rivas, Germán; Pajares, María A

2002-01-01

The reversible unfolding of rat liver methionine adenosyltransferase dimer by urea under equilibrium conditions has been monitored by fluorescence spectroscopy, CD, size-exclusion chromatography, analytical ultracentrifugation and enzyme activity measurements. The results obtained indicate that unfolding takes place through a three-state mechanism, involving an inactive monomeric intermediate. This intermediate has a 70% native secondary structure, binds less 8-anilinonaphthalene-1-sulphonic acid than the native dimer and has a sedimentation coefficient of 4.24+/-0.15. The variations of free energy in the absence of denaturant [DeltaG(H(2)O)] and its coefficients of urea dependence (m), calculated by the linear extrapolation model, were 36.15+/-2.3 kJ.mol(-1) and 19.87+/-0.71 kJ.mol(-1).M(-1) for the dissociation of the native dimer and 14.77+/-1.63 kJ.mol(-1) and 5.23+/-0.21 kJ.mol(-1).M(-1) for the unfolding of the monomeric intermediate respectively. Thus the global free energy change in the absence of denaturant and the m coefficient were calculated to be 65.69 kJ.mol(-1) and 30.33 kJ.mol(-1).M(-1) respectively. Analysis of the calculated thermodynamical parameters indicate the instability of the dimer in the presence of denaturant, and that the major exposure to the solvent is due to dimer dissociation. Finally, a minimum-folding mechanism for methionine adenosyltransferase III is established. PMID:11772402

Kinetic analysis of manure pyrolysis and combustion processes.

PubMed

Fernandez-Lopez, M; Pedrosa-Castro, G J; Valverde, J L; Sanchez-Silva, L

2016-12-01

Due to the depletion of fossil fuel reserves and the environmental issues derived from their use, biomass seems to be an excellent source of renewable energy. In this work, the kinetics of the pyrolysis and combustion of three different biomass waste samples (two dairy manure samples before (Pre) and after (Dig R) anaerobic digestion and one swine manure sample (SW)) was studied by means of thermogravimetric analysis. In this work, three iso-conversional methods (Friedman, Flynn-Wall-Ozawa (FWO) and Kissinger-Akahira-Sunose (KAS)) were compared with the Coats-Redfern method. The E a values of devolatilization stages were in the range of 152-170kJ/mol, 148-178kJ/mol and 156-209kJ/mol for samples Pre, Dig R and SW, respectively. Concerning combustion process, char oxidation stages showed lower E a values than that obtained for the combustion devolatilization stage, being in the range of 140-175kJ/mol, 178-199kJ/mol and 122-144kJ/mol for samples Pre, Dig R and SW, respectively. These results were practically the same for samples Pre and Dig R, which means that the kinetics of the thermochemical processes were not affected by anaerobic digestion. Finally, the distributed activation energy model (DAEM) and the pseudo-multi component stage model (PMSM) were applied to predict the weight loss curves of pyrolysis and combustion. DAEM was the best model that fitted the experimental data. Copyright © 2016 Elsevier Ltd. All rights reserved.

Reactivity of organic micropollutants with ozone: A kinetic study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brambilla, A.; Bolzacchini, E.; Meinardi, S.

1995-12-01

Studies about the chemical reactivity of compounds widely used in the environment are needed. The chemical reactivity of triazines (simazine, atrazine, terbutylazine) and phenylureas (linuron and diuron) was studied. The kinetics of the oxidation of the triazines and phenylureas with ozone at pH 3 and the kinetics of the saturation of the solution with ozone were evaluated. These data may be useful for the prediction of the persistency of these compuonds in the environment and for the treatment of wastewaters contaminated with these compounds. The solution was presaturated with ozone before the addition of the substrate, and the reaction constantsmore » for the pseudo first order kinetics -d[substrate]/dt = k{sub app} [substrate] at 298{degree}K were obtained, assuming a steady state concentration of ozone of 1.91 10{sup -4} mol L{sup -1} for the phenylureas and of 3.03 10{sup -4} and L{sup -1} for the triazines. The data obtained were: atrazine k = 6.86 (L mol{sup -1}s{sup -1}); simazine: 9.26; t-butylazine 7.26; linuron 11.00; diuron 43.90. The activation parameters for the reaction of simazine were {Delta}H{sup =} = 9.35 kcal mol{sup -1} and {Delta}S{sup =} = -22.3 cal mol{sup -1} {degree}K{sup -1} and for the reaction of diuron were {Delta}H{sup =} = 16.83 Kcal mol{sup -1}, {Delta}S{sup =} = 5.696 cal mol{sup -1} {degree}K{sup -1}.« less

Solid-State Gas Adsorption Studies with Discrete Palladium(II) [Pd2 (L)4 ]4+ Cages.

PubMed

Preston, Dan; White, Keith F; Lewis, James E M; Vasdev, Roan A S; Abrahams, Brendan F; Crowley, James D

2017-08-04

The need for effective CO 2 capture systems remains high, and due to their tunability, metallosupramolecular architectures are an attractive option for gas sorption. While the use of extended metal organic frameworks for gas adsorption has been extensively explored, the exploitation of discrete metallocage architectures to bind gases remains in its infancy. Herein the solid state gas adsorption properties of a series of [Pd 2 (L) 4 ] 4+ lantern shaped coordination cages (L = variants of 2,6-bis(pyridin-3-ylethynyl)pyridine), which had solvent accessible internal cavities suitable for gas binding, have been investigated. The cages showed little interaction with dinitrogen gas but were able to take up CO 2 . The best performing cage reversibly sorbed 1.4 mol CO 2 per mol cage at 298 K, and 2.3 mol CO 2 per mol cage at 258 K (1 bar). The enthalpy of binding was calculated to be 25-35 kJ mol -1 , across the number of equivalents bound, while DFT calculations on the CO 2 binding in the cage gave ΔE for the cage-CO 2 interaction of 23-28 kJ mol -1 , across the same range. DFT modelling suggested that the binding mode is a hydrogen bond between the carbonyl oxygen of CO 2 and the internally directed hydrogen atoms of the cage. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dark respiration and carbohydrate status of two forest species grown in elevated carbon dioxide. [Liriodendron tulipifera L. ; Quercus alba L

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wullschleger, S.D.; Norby, R.J.; Hendrix, D.L.

1991-05-01

Carbon assimilation is often increased by CO{sub 2} enrichment, but the response of dark respiration and carbohydrate metabolism to elevated CO{sub 2} is less well documented. The authors examined the diurnal response of these two processes in yellow-poplar (Liriodendron tulipifera L.) and white oak (Quercus alba L.) seedling exposed to CO{sub 2} enrichment under field conditions. One-year-old seedlings of yellow-poplar and white oak were grown in open-top chambers and exposed to ambient, +150 {mu}mol mol{sup {minus}1}, or +300 {mu}mol mol{sup {minus}1} CO{sub 2} concentrations. After 24 weeks, mature leaves of yellow-poplar and white oak seedlings grown at high CO{sub 2}more » showed a 37% and 52% reduction in nighttime respiration, respectively. Morning starch levels for yellow-poplar and white oak grown at +300 {mu}mol mol{sup {minus}1} increased 72% and 40%, respectively, compared to ambient-grown plants. Yellow-poplar and white oak seedlings grown at high CO{sub 2} contained 17% and 27% less morning sucrose, respectively than did plants grown at ambient CO{sub 2} concentration. Starch accumulation and the subsequent depletion of sucrose for plants grown under CO{sub 2} enrichment, resulted in a pronounced rise in the starch/sucrose ratio with increasing CO{sub 2} concentration. The diurnal pattern of dark respiration suggested that a relationship with carbohydrate status might exist.« less

Conditioning of renewable silver amalgam film electrode for the characterization of clothianidin and its determination in selected samples by adsorptive square-wave voltammetry.

PubMed

Brycht, Mariola; Skrzypek, Sławomira; Guzsvány, Valéria; Berenji, Janoš

2013-12-15

A new square-wave adsorptive stripping voltammetric (SWAdSV) method was developed for the determination of the neonicotinoid insecticide clothianidin (Clo), based on its reduction at a renewable silver amalgam film electrode (Hg(Ag)FE). The key point of the procedure is the pretreatment of the Hg(Ag)FE by applying the appropriate conditioning potential (-1.70 V vs. Ag/AgCl reference electrode). Under the optimized voltammetric conditions, such pretreatment resulted in the peak for the Clo reduction in Britton-Robinson buffer pH 9.0 at about -0.60 V, which was used for the analytical purpose. The developed SWAdSV procedure made it possible to determine Clo in the concentration range of 6.0×10(-7)-7.0×10(-6) mol L(-1) (LOD=1.8×10(-7) mol L(-1), LOQ=6.0×10(-7) mol L(-1)) and 7.0×10(-6)-4.0×10(-5) mol L(-1) (LOD=1.3×10(-6) mol L(-1), LOQ=4.2×10(-6) mol L(-1)). The repeatability, precision, and the recovery of the method were determined. The effect of common interfering pesticides was also investigated. Standard addition method was successfully applied and validated for the determination of Clo in spiked Warta River water, corn seeds samples, and in corn seeds samples treated with the commercial formulation PONCHO 600 FS. © 2013 Elsevier B.V. All rights reserved.

Kinetic and thermodynamic studies of a novel acid protease from Aspergillus foetidus.

PubMed

Souza, Paula Monteiro; Aliakbarian, Bahar; Filho, Edivaldo Ximenes Ferreira; Magalhães, Pérola Oliveira; Junior, Adalberto Pessoa; Converti, Attilio; Perego, Patrizia

2015-11-01

The kinetics of a thermostable extracellular acid protease produced by an Aspergillus foetidus strain was investigated at different pH, temperatures and substrate concentrations. The enzyme exhibited maximal activity at pH 5.0 and 55°C, and its irreversible deactivation was well described by first-order kinetics. When temperature was raised from 55 to 70°C, the deactivation rate constant increased from 0.018 to 5.06h(-1), while the half-life decreased from 37.6 to 0.13h. The results of activity collected at different temperatures were then used to estimate, the activation energy of the hydrolysis reaction (E*=19.03kJ/mol) and the standard enthalpy variation of reversible enzyme unfolding (ΔH°U=19.03kJ/mol). The results of residual activity tests carried out in the temperature range 55-70°C allowed estimating the activation energy (E(*)d=314.12kJ/mol), enthalpy (311.27≤(ΔH°d≤311.39kJ/mol), entropy (599.59≤ΔS(*)d≤610.49kJ/mol K) and Gibbs free energy (103.18≤ΔG(*)d≤113.87kJ/mol) of the enzyme irreversible denaturation. These thermodynamic parameters suggest that this new protease is highly thermostable and could be important for industrial applications. To the best of our knowledge, this is the first report on thermodynamic parameters of an acid protease produced by A. foetidus. Copyright © 2015 Elsevier B.V. All rights reserved.

Enthalpy of formation of anisole: implications for the controversy on the O-H bond dissociation enthalpy in phenol.

PubMed

Simões, Ricardo G; Agapito, Filipe; Diogo, Hermínio P; da Piedade, Manuel E Minas

2014-11-20

Significant discrepancies in the literature data for the enthalpy of formation of gaseous anisole, ΔfHmo(PhOCH3, g), have fueled an ongoing controversy regarding the most reliable enthalpy of formation of the phenoxy radical and of the gas phase O-H bond dissociation enthalpy, DHo(PhO-H), in phenol. In the present work ΔfHmo(PhOCH3, g) was reassessed using a combination of calorimetric determinations and high-level (W2-F12) ab initio calculations. Static-bomb combustion calorimetry led to the standard molar enthalpy of formation of liquid anisole at 298.15 K, ΔfHmo(PhOCH3, l) = −(117.1 ± 1.4) kJ·mol(-1). The corresponding enthalpy of vaporization was obtained as, ΔvapHmo(PhOCH3) = 46.41 ± 0.26 kJ·mol(-1), by Calvet-drop microcalorimetry. These results give ΔfHmo(PhOCH3, g) = −(70.7 ± 1.4) kJ·mol(-1), in excellent agreement with ΔfHmo(PhOCH3, g) = −(70.8 ± 3.2) kJ·mol(-1), obtained from the W2-F12 calculations. The ΔfHmo(PhOCH3, g) here recommended leads to ΔfHmo(PhO•, g) = 55.5 ± 2.4 kJ·mol(-)1 and DH°(PhO-H) = 368.1 ± 2.6 kJ·mol(-1).

Hexamethonium-induced augmentation of the electrical twitch response in the guinea-pig ileum longitudinal muscle-myenteric plexus strip.

PubMed

Donnerer, Josef; Liebmann, Ingrid; Holzer-Petsche, Ulrike

2014-08-08

Longitudinal muscle-myenteric plexus strips of the guinea-pig ileum were used to investigate the nature of the hexamethonium-induced augmentation of the twitch response. All preparations were set up in Tyrode solution and intermittent longitudinal twitch contractions were evoked by single pulse electrical field stimulation. Hexamethonium, a blocker of nicotinic ganglionic transmission, at 300 μmol/l and 1 mmol/l augmented the twitch contractions by 21% and 35%, respectively. First we tested for a possible nicotinic drive onto an inhibitory neuronal component to the longitudinal smooth muscle cells. However, guanethidine (5 μmol/l), naloxone (1 μmol/l), or l-NAME (300 μmol/l) were without effect on the hexamethonium-induced augmentation. The P2 purinoceptor antagonist pyridoxalphosphate-6-azophenyl-2'-4'-disulphonic acid (PPADS), 25-100 μmol/l, without altering the control twitch responses, dose-dependently reduced the hexamethonium-induced augmentation; at 100 μmol/l a statistically significantly inhibition was observed. Based on these functional experiments we found no evidence that blocking nicotinic transmission removed a tonic adrenergic, opioidergic or nitrergic inhibitory input to the longitudinal muscle. However, we provide evidence for a hexamethonium-induced augmentation of the P2 purinergic input to cholinergic motoneurons of the guinea-pig ileum longitudinal muscle. The P2-nicotinic receptor interaction presents a novel modulatory mechanism to cholinergic myenteric motor neurons. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Environmental conditions affect transcription of the pectinase genes of Erwinia chrysanthemi 3937.

PubMed Central

Hugouvieux-Cotte-Pattat, N; Dominguez, H; Robert-Baudouy, J

1992-01-01

To depolymerize plant pectin, the phytopathogenic enterobacterium Erwinia chrysanthemi produces a series of enzymes which include a pectin-methyl-esterase encoded by the pem gene and five isoenzymes of pectate lyases encoded by the five genes pelA, pelB, pelC, pelD, and pelE. We have constructed transcriptional fusions between the pectinase gene promoters and the uidA gene, encoding beta-glucuronidase, to study the regulation of these E. chrysanthemi pectinase genes individually. The transcription of the pectinase genes is dependent on many environmental conditions. All the fusions were induced by pectic catabolic products and responded, to different degrees, to growth phase, catabolite repression, temperature, and nitrogen starvation. Transcription of pelA, pelD, and pelE was also increased in anaerobic growth conditions. High osmolarity of the culture medium increased expression of pelE but decreased that of pelD; the other pectinase genes were not affected. The level of expression of each gene was different. Transcription of pelA was very low under all growth conditions. The expression of the pelB, pelC, and pem genes was intermediate. The pelE gene had a high basal level of expression. Expression of pelD was generally the most affected by changes in culture conditions and showed a low basal level but very high induced levels. These differences in the expression of the pectinase genes of E. chrysanthemi 3937 presumably reflect their role during infection of plants, because the degradation of pectic polymers of the plant cell walls is the main determinant of tissue maceration caused by soft rot erwiniae. PMID:1447147

Disintegration and cancer immunotherapy efficacy of a squalane-in-water delivery system emulsified by bioresorbable poly(ethylene glycol)-block-polylactide.

PubMed

Chen, Wei-Lin; Liu, Shih-Jen; Leng, Chih-Hsiang; Chen, Hsin-Wei; Chong, Pele; Huang, Ming-Hsi

2014-02-01

Vaccine adjuvant is conferred on the substance that helps to enhance antigen-specific immune response. Here we investigated the disintegration characteristics and immunotherapy potency of an emulsified delivery system comprising bioresorbable polymer poly(ethylene glycol)-polylactide (PEG-PLA), phosphate buffer saline (PBS), and metabolizable oil squalane. PEG-PLA-stabilized oil-in-water emulsions show good stability at 4 °C and at room temperature. At 37 °C, squalane/PEG-PLA/PBS emulsion with oil/aqueous weight ratio of 7/3 (denominated PELA73) was stable for 6 weeks without phase separation. As PEG-PLA being degraded, 30% of free oil at the surface layer and 10% of water at the bottom disassociated from the PELA73 emulsion were found after 3 months. A MALDI-TOF MS study directly on the DIOS plate enables us to identify low molecular weight components released during degradation. Our results confirm the loss of PLA moiety of the emulsifier PEG-PLA directly affected the stability of PEG-PLA-stabilized emulsion, leading to emulsion disintegration and squalane/water phase separation. As adjuvant for cancer immunotherapeutic use, an HPV16 E7 peptide antigen formulated with PELA73 plus immunostimulatory CpG molecules could strongly enhance antigen-specific T-cell responses as well as anti-tumor ability with respected to non-formulated or Alum-formulated peptide. Accordingly, these advances may be a potential immunoregulatory strategy in manipulating the immune responses induced by tumor-associated antigens. Copyright © 2013 The Authors. Published by Elsevier Ltd.. All rights reserved.

Subunit composition and structure of subcomponent C1q of the first component of human complement.

PubMed

Reid, K B; Porter, R R

1976-04-01

1. Unreduced human subcomponent C1q was shown by electrophoresis on polyacrylamide gels run in the presence of sodium dodecyl sulphate to be composed of two types of non-covalently linked subunits of apparent mol.wts. 69 000 and 54 000. The ratio of the two subunits was markedly affected by the ionic strength of the applied sample. At a low ionic strength of applied sample, which gave the optimum value for the 54 000-apparent mol.wt. subunit, a ratio of 1.99:1.00 was obtained for the ratio of the 69 000-apparent mol.wt. subunit to the 5400-apparent-mol.wt. subunit. The amount of the 54 000-apparent-mol.wt. subunit detected in the expected position on the gel was found to be inversely proportional to increases in the ionic strength of the applled sample. 2. Human subcomponent C1q on reduction and alkylation, or oxidation, yields equimolar amounts of three chains designated A, B and C [Reid et al. (1972) Biochem. J. 130, 749-763]. The results obtained by Yonemasu & Stroud [(1972) Immunochemistry 9, 545-554], which showed that the 69 000-apparent-mol.wt. subunit was a disulphide-linked dimer of the A and B chains and that the 54 000-apparent-mol.wt. subunit was a disulphide-linked dimer of the C chain, were confirmed. 3. Gel filtration on Sephadex G-200 in 6.0M-guanidinium chloride showed that both types of unreduced subunit were eluted together as a single symmetrical peak of apparent mol.wt. 49 000-50 000 when globular proteins were used as markers. The molecular weights of the oxidized or reduced A, B and C chains have been shown previously to be very similar all being in the range 23 000-24 000 [Reid et al. (1972) Biochem. J. 130, 749-763; Reid (1974) Biochem. J. 141, 189-203]. 4. It is proposed that subcomponent C1q (mol.wt. 410000) is composed of nine non-covalently linked subunits, i.e. six A-B dimers and three C-C dimers. 5. A structure for subcomponent C1q is proposed and is based on the assumption that the collagen-like regions of 78 residues in each of the A, B and C chains are combined to form a triple-helical structure of the same type as is found in collagens.

Kinetic Studies of Imidazoles in Tropospheric Aqueous-Phase Chemistry: Photochemistry of Imidazole-2-carboxaldehyde and Oxidation Reaction with Hydroxyl Radicals

NASA Astrophysics Data System (ADS)

Felber, T.; Otto, T.; Herrmann, H.

2017-12-01

The formation of imidazoles via the reaction of dicarbonyls with nitrogen containing compounds in the atmosphere and their potential to act as photosensitizers possibly initiating secondary organic aerosol (SOA) growth is a field of increasing activity. A recent field study quantified and qualified imidazoles in ambient aerosol samples from Europe and China. However, kinetic data and mechanisms of particle-phase reactions involving imidazoles are still scarce. In this study, kinetic measurements were investigated using laser flash photolysis-laser long path absorption (LFP-LLPA). Quenching rate constants for the reactions of the excited triplet state of imidazole-2-carboxaldehyde (IC) with bromide anion (kq = (1.6 ± 0.3) × 107 L mol-1 s-1), oxygen (kq = (2.5 ± 0.07) × 109 L mol-1 s-1), and formic acid (kq = (8.8 ± 0.5) × 109 L mol-1 s-1) are determined. IC is efficiently quenched by oxygen and formic acid. Furthermore, the quenching reaction of IC with isopropanol is investigated and compared to the reaction with formic acid to propose a preliminary mechanism of photosensitized reactions of IC with organic compounds. It is suggested that an electron transfer occurs, as it is the case for inorganics. Furthermore, rate constants of hydroxyl (OH) radical oxidation reactions with different imidazoles were determined. Following rate constants are obtained at a temperature of 298 K: k(imidazole-2-carboxaldehyde) = (3.3 ± 1.3) × 109 L mol-1 s-1, k(1-methylimidazolium hydrogen sulfate) = (2.7 ± 0.2) × 109 L mol-1 s-1, k(2-methylimidazole) = (5.4 ± 0.2) × 109 L mol-1 s-1, k(4(5)-methylimidazole) = (5.1 ± 0.3) × 109 L mol-1 s-1, k(1-ethylimidazole) = (3.0 ± 0.3) × 109 L mol-1 s-1, k(2-ethylimidazole) = (5.0 ± 0.2) × 109 L mol-1 s-1. The OH radical reaction rate constants of imidazoles are in the same range as for non-heteroaromatic compounds. Therefore, imidazoles can be expected to exist just for a limited time in the atmosphere (τ = 16 - 29 hours) after their formation. The received kinetic data will be added into model studies to evaluate the importance of aqueous-phase chemistry of imidazoles for atmospheric processes as well as the impact of photosensitized reactions on atmospheric particles possibly contributing to SOA formation.

2-Pyridinethiol/2-pyridinethione tautomeric equilibrium. A comparative experimental and computational study.

PubMed

Moran, Damian; Sukcharoenphon, Kengkaj; Puchta, Ralph; Schaefer, Henry F; Schleyer, Paul V R; Hoff, Carl D

2002-12-13

The gas phase and solvent dependent preference of the tautomerization between 2-pyridinethiol (2SH) and 2-pyridinethione (2S) has been assessed using variable temperature Fourier transform infrared (FTIR) experiments, as well as ab initio and density functional theory computations. No spectroscopic evidence (nu(S)(-)(H) stretch) for 2SH was observed in toluene, C(6)D(6), heptane, or methylene chloride solutions. Although, C(s)() 2SH is 2.61 kcal/mol more stable than C(s)() 2S (CCSD(T)/cc-pVTZ//B3LYP/6-311+G(3df,2p)+ZPE), cyclohexane solvent-field relative energies (IPCM-MP2/6-311+G(3df,2p)) favor 2S by 1.96 kcal/mol. This is in accord with the FTIR observations and in quantitative agreement with the -2.6 kcal/mol solution (toluene or C(6)D(6)) calorimetric enthalpy for the 2S/2SH tautomerization favoring the thione. As the intramolecular transition state for the 2S, 2SH tautomerization (2TS) lies 25 (CBS-Q) to 30 kcal/mol (CCSD/cc-pVTZ) higher in energy than either tautomer, tautomerization probably occurs in the hydrogen bonded dimer. The B3LYP/6-311+G(3df,2p) optimized C(2) 2SH dimer is 10.23 kcal/mol + ZPE higher in energy than the C(2)(h)() 2S dimer and is only 2.95 kcal/mol + ZPE lower in energy than the C(2) 2TS dimer transition state. Dimerization equilibrium measurements (FTIR, C(6)D(6)) over the temperature range 22-63 degrees C agree: K(eq)(298) = 165 +/- 40 M(-)(1), DeltaH = -7.0 +/- 0.7 kcal/mol, and DeltaS = -13.4 +/- 3.0 cal/(mol deg). The difference between experimental and B3LYP/6-311+G(3df,2p) [-34.62 cal/(mol deg)] entropy changes is due to solvent effects. The B3LYP/6-311+G(3df,2p) nucleus independent chemical shifts (NICS) are -8.8 and -3.5 ppm 1 A above the 2SH and 2S ring centers, respectively, and the thiol is aromatic. Although the thione is not aromatic, it is stabilized by the thioamide resonance. In solvent, the large 2S dipole, 2-3 times greater than 2SH, favors the thione tautomer and, in conclusion, 2S is thermodynamically more stable than 2SH in solution.

New Standard State Entropy for Sphene (Titanite)

NASA Astrophysics Data System (ADS)

Manon, M. R.; Dachs, E.; Essene, E. J.

2004-12-01

Several recent papers have questioned the accepted standard state (STP) entropy of sphene (CaTiSiO5), which had been considered to be in the range 129-132 J/mol.K (Berman, 1988: 129.3 Robie and Hemingway, 1995: 129.2 J/mol.K; Holland and Powell, 1995: 131.2 J/mol.K.). However, Xirouchakis and Lindsley (1998) recommended a much lower value of 106 J/mol.K for the STP entropy of sphene. Tangeman and Xirouchakis (2001) inferred a value less than 124 or 120 J/mol.K, based on based on enthalpy constraints combined with the tightly reversed reaction sphene+kyanite=rutile+anorthite by Bohlen and Manning (1991). Their recommendations are in conflict with the accepted values for STP entropy for sphene, including values calculated by direct measurement of Cp from 50 to 300 K by King (1954). In order to resolve this discrepancy, we have collected new data on the Cp of sphene between 5 and 300 K. Our measurements were made in the PPMS at Salzburg on a 21.4 g sample of sphene generously furnished by Tangeman and Xirouchakis (2001), the same sample as used in their experiments. The Cp data are slightly lower than those of King (1954) but merge smoothly with data of Tangeman and Xirouchakis (2001) from 330 to 483 K (or whatever) where a transition is recorded in the Cp data as a lambda anomaly. Tangeman and Xirouchakis also obtained data above the transition up to 950K. Integration of the new Cp data yields a STP entropy of 127.3 J/mol.K, lower than the generally accepted value by ca. 2 J/mol.K. A change in the STP entropy of sphene will have an effect on many Ti-bearing reactions which occur within the earth, although the magnitude of this change is not nearly as large as that suggested by Xirouchakis and Lindsley (1998). Above 700 K, the entropy calculated using the new STP entropy with the heat capacity equation of Tangeman and Xirouchakis (2001) is within 1 J/mol.K of the value tabulated in Robie and Hemingway (1995) and of that calculated from Berman (1988). The effect on most phase equilibrium calculations will not be large except for reactions with small Δ S. The use of 127.2 J/mol.K as the standard entropy of sphene is recommended especially in calculations of geobarometers involving that phase.

Preparation of Cu₂O-Reduced Graphene Nanocomposite Modified Electrodes towards Ultrasensitive Dopamine Detection.

PubMed

He, Quanguo; Liu, Jun; Liu, Xiaopeng; Li, Guangli; Deng, Peihong; Liang, Jing

2018-01-12

Cu₂O-reduced graphene oxide nanocomposite (Cu₂O-RGO) was used to modify glassy carbon electrodes (GCE), and applied for the determination of dopamine (DA). The microstructure of Cu₂O-RGO nanocomposite material was characterized by scanning electron microscope. Then the electrochemical reduction condition for preparing Cu₂O-RGO/GCE and experimental conditions for determining DA were further optimized. The electrochemical behaviors of DA on the bare electrode, RGO- and Cu₂O-RGO-modified electrodes were also investigated using cyclic voltammetry in phosphate-buffered saline solution (PBS, pH 3.5). The results show that the oxidation peaks of ascorbic acid (AA), dopamine (DA), and uric acid (UA) could be well separated and the peak-to-peak separations are 204 mV (AA-DA) and 144 mV (DA-UA), respectively. Moreover, the linear response ranges for the determination of 1 × 10 -8 mol/L~1 × 10 -6 mol/L and 1 × 10 -6 mol/L~8 × 10 -5 mol/L with the detection limit 6.0 × 10 -9 mol/L (S/N = 3). The proposed Cu₂O-RGO/GCE was further applied to the determination of DA in dopamine hydrochloride injections with satisfactory results.

Bis(acetato-κ2 O,O′)(4,4′-dimethyl-2,2′-bipyridine-κ2 N,N′)­zinc

PubMed Central

Harvey, Miguel A.; Suarez, Sebastian A.; Ibañez, Andres; Doctorovich, Fabio; Baggio, Ricardo

2012-01-01

The mol­ecular structure of the title compound, [Zn(CH3COO)2(C12H12N2)], consists of isolated mol­ecules bis­ected by a twofold rotation axis which goes through the ZnII cation and halves the organic base through the central C—C bond. The ZnII ion is coordinated by two N atoms from one mol­ecule of the aromatic base and four O atoms from two bidentate, symmetry-related acetate anions, which coordinate asym­metrically [Zn—O distances of 2.058 (2) and 2.362 (3) Å], while the two Zn—N bond distances are equal as imposed by symmetry [2.079 (2) Å]. The crystal structure is supported by a number of weak C—H⋯O inter­actions and C—H⋯π contacts, with no π–π inter­actions present, mainly hindered by the substituent methyl groups and the relative mol­ecular orientation. The result is a three-dimensional structure in which each mol­ecule is linked to eight different neighbors. PMID:23284355

Étude par la méthode de Monte Carlo de la phase plastique de la quinuclidine à différentes températures

NASA Astrophysics Data System (ADS)

Jumeau, Daniel; André, Daniel

La phase plastique (c.f.c.) de la quinuclidine est étudiée à différentes températures par la méthode de Monte Carlo utilisant la technique des matrices de compatibilité. Afin de ne pas modifier la symétrie moyenne du réseau, les centres de masse de molécules sont supposés fixes. Les orientations moléculaires sont choisies de façon aléatoire parmi les 48 orientations équivalentes et discernables du groupe c.f.c. Cela permet une mémorisation préalable des énergies d'interaction entre molécules voisines et un gain de temps de calcul considérable. Nous observons alors un blocage des réorientations moléculaires à basse température, tandis que la symétrie cristalline devient monoclinique. Ceci est interprété en termes de transition de phase dont la température (215 K) et la variation d'énergie (5 kJ mol-1) sont très proches des valeurs expérimentales.

Interaction Mode between Inclusion Complex of Vitamin K3 with γ- Cyclodextrin and Herring-Sperm DNA.

PubMed

Tang, Yan; Cai, Li; Xue, Kang; Wang, Chunling; Xiong, Xiaoli

2016-05-03

Methods including spectroscopy, electronic chemistry and thermodynamics were used to study the inclusion effect between γ-cyclodextrin (CD) and vitamin K3(K3), as well as the interaction mode between herring-sperm DNA (hsDNA) and γ-CD-K3 inclusion complex. The results from ultraviolet spectroscopic method indicated that VK3 and γ-CD formed 1:1 inclusion complex, with the inclusion constant Kf = 1.02 × 10(4) L/mol, which is based on Benesi-Hildebrand's viewpoint. The outcomes from the probe method and Scatchard methods suggested that the interaction mode between γ-CD-K3 and DNA was a mixture mode, which included intercalation and electrostatic binding effects. The binding constants were K (θ)25°C = 2.16 × 10(4) L/mol, and K(θ)37°C = 1.06 × 10(4) L/mol. The thermodynamic functions of the interaction between γ-CD-K3 and DNA were ΔrHm(θ) = -2.74 × 10(4) J/mol, ΔrSm(θ) = 174.74 J·mol(-1)K(-1), therefore, both ΔrHm(θ) (enthalpy) and ΔrSm(θ) (entropy) worked as driven forces in this action.

Effect of salts on the water sorption kinetics of dried pasta.

PubMed

Ogawa, Takenobu; Adachi, Shuji

2013-01-01

The water sorption kinetics of dried pasta were measured in the 20-90 °C range in 1.83 mol/L of NaCl and at 80 °C in 1.83 mol/L of LiCl, KCl, NaBr and NaI solutions in order to elucidate the role of salt in the kinetics. At the temperatures higher than 70.8 °C, the change in the enthalpy of sorption, ΔH, in the 1.83 mol/L NaCl solution was 33.1 kJ/mol, which was greater than the ΔH value in water, and the activation energy for the sorption, E, in the salt solution was 25.6 kJ/mol, which was slightly lower than the E value in water. The Hofmeister series of ions was an index for their effect on the equilibrium amount of the sorbed solution of pasta. The apparent diffusion coefficient of water into pasta was not correlated with the crystal radius of the salts, but was with the Stokes radius of the hydrated ions. Equations were formulated to predict the amount of sorbed solution under any condition of temperature and NaCl concentration.

Extensible Ontological Modeling Framefork for Subject Mediation

NASA Astrophysics Data System (ADS)

Kalinichenko, L. A.; Skvortsov, N. A.

An approach for extensible ontological model construction in a mediation environment intended for heterogeneous information sources integration in various subject domains is presented. A mediator ontological language (MOL) may depend on a subject domain and is to be defined at the mediator consolidation phase. On the other hand, for different information sources different ontological models (languages) can be used to define their own ontologies. Reversible mapping of the source ontological models into MOL is needed for information sources registration at the mediator. An approach for such reversible mapping is demonstrated for a class of the Web information sources. It is assumed that such sources apply the DAML+OIL ontological model. A subset of the hybrid object-oriented and semi-structured canonical mediator data model is used for the core of MOL. Construction of a reversible mapping of DAML+OIL into an extension of the core of MOL is presented in the paper. Such mapping is a necessary pre-requisite for contextualizing and registration of information sources at the mediator. The mapping shows how extensible MOL can be constructed. The approach proposed is oriented on digital libraries where retrieval is focused on information content, rather than on information entities.

Structure and properties of Li 2S-P 2S 5-P 2S 3 glass and glass-ceramic electrolytes

NASA Astrophysics Data System (ADS)

Minami, Keiichi; Hayashi, Akitoshi; Ujiie, Satoshi; Tatsumisago, Masahiro

High lithium ion conducting 70Li 2S·(30 - x)P 2S 5· xP 2S 3 (mol%) glasses and glass-ceramics were prepared by the mechanical milling method. Glasses were obtained in the composition range of 0 ≦ x ≦ 10. The substitution of P 2S 3 for P 2S 5 promoted the formation of the P 2S 6 4- units in the glasses. The conductivity of the glass increased with an increase in P 2S 3 contents up to 5 mol% and the glass with 5 mol% of P 2S 3 showed the conductivity of 1 × 10 -4 S cm -1 at room temperature. In the case of glass-ceramics, the conductivity increased with an increase in P 2S 3 contents up to 1 mol%, and the superionic conducting Li 7P 3S 11 crystal was precipitated in the glass-ceramic. The glass-ceramic with 1 mol% of P 2S 3 showed the highest conductivity of 3.9 × 10 -3 S cm -1 at room temperature.

[6]-Shogaol inhibits melanogenesis in B16 mouse melanoma cells through activation of the ERK pathway

PubMed Central

Yao, Cheng; Oh, Jang-hee; Oh, Inn Gyung; Park, Chi-hyun; Chung, Jin Ho

2013-01-01

Aim: To investigate the effect of [6]-shogaol, an active ingredient in ginger, on melanogenesis and the underlying mechanisms. Methods: B16F10 mouse melanoma cells were tested. Cell viability was determined with the MTT assay. Melanin content and tyrosinase activity were analyzed with a spectrophotometer. The protein expression of tyrosinase and microphthalmia associated transcription factor (MITF), as well as phosphorylated or total ERK1/2 and Akt were measured using Western blot. Results: Treatment of the cells with [6]-shogaol (1, 5, 10 μmol/L) reduced the melanin content in a concentration-dependent manner. [6]-Shogaol (5 and 10 μmol/L) significantly decreased the intracellular tyrosinase activity, and markedly suppressed the expression levels of tyrosinase and MITF proteins in the cells. Furthermore, [6]-shogaol (10 μmol/L) activated ERK, which was known to negatively regulate melanin synthesis in these cells. Pretreatment with the specific ERK pathway inhibitor PD98059 (20 μmol/L) greatly attenuated the inhibition of melanin synthesis by [6]-shogaol (10 μmol/L). Conclusion: The results demonstrate that [6]-shogaol inhibits melanogenesis in B16F10 mouse melanoma cells via activating the ERK pathway. PMID:23123645

[6]-Shogaol inhibits melanogenesis in B16 mouse melanoma cells through activation of the ERK pathway.

PubMed

Yao, Cheng; Oh, Jang-hee; Oh, Inn Gyung; Park, Chi-hyun; Chung, Jin Ho

2013-02-01

To investigate the effect of [6]-shogaol, an active ingredient in ginger, on melanogenesis and the underlying mechanisms. B16F10 mouse melanoma cells were tested. Cell viability was determined with the MTT assay. Melanin content and tyrosinase activity were analyzed with a spectrophotometer. The protein expression of tyrosinase and microphthalmia associated transcription factor (MITF), as well as phosphorylated or total ERK1/2 and Akt were measured using Western blot. Treatment of the cells with [6]-shogaol (1, 5, 10 μmol/L) reduced the melanin content in a concentration-dependent manner. [6]-Shogaol (5 and 10 μmol/L) significantly decreased the intracellular tyrosinase activity, and markedly suppressed the expression levels of tyrosinase and MITF proteins in the cells. Furthermore, [6]-shogaol (10 μmol/L) activated ERK, which was known to negatively regulate melanin synthesis in these cells. Pretreatment with the specific ERK pathway inhibitor PD98059 (20 μmol/L) greatly attenuated the inhibition of melanin synthesis by [6]-shogaol (10 μmol/L). The results demonstrate that [6]-shogaol inhibits melanogenesis in B16F10 mouse melanoma cells via activating the ERK pathway.

Fabrication strategy for amphiphilic microcapsules with narrow size distribution by premix membrane emulsification.

PubMed

Wei, Yi; Wang, Yuxia; Wang, Lianyan; Hao, Dongxia; Ma, Guanghui

2011-10-15

Amphiphilic co-polymer, which can maintain the stability of proteins and increase the protein loading efficiency, is considered as an exploring-worthy biodegrade polymer for drug delivery. However, amphiphilic microcapsules prepared by conventional methods, such like mechanical stirring and spray-drying methods, exhibit broad size distributions due to its hydrophilic sequences, leading to poor reproducibility. In this study, we employed poly(monomethoxypoly ethylene glycol-co-D,L-lactide) (mPEG-PLA, PELA), one of common amphiphilic polymers, as model to focus on investigating the process parameters and mechanisms to prepare PELA microcapsules with narrow size distribution and regular sphericity by combining premix membrane emulsification and double emulsion technique. The coarse double emulsion with broad size distribution was repeatedly pressed through Shirasu Porous Glass (SPG) membrane with relatively high pressure to form the fine emulsion with narrow size distribution. Then, the microcapsules with narrow size distribution can be obtained by solvent extraction method. It was found that it was more difficult to obtain PELA microcapsules with narrow size distribution and smooth surface due to its amphiphilic property, compared with the cases of PLA and PLGA. The smooth surface morphology was found to be related to several factors including internal water phase with less volume, slower stirring rate during solidification and using ethyl acetate as oil phase. It was also found that mass ratio of hydrophilic mPEG, stabilizer PVA concentration in external water phase and transmembrane pressure played important role on the distribution of microcapsules size. The suitable preparation conditions were determined as follows: for the membrane with pore size of 2.8 μm, the mass ratio of PLA/mPEG was 19:1, volume ratio of W(1)/O was 1:10 and O/W(2) was 1:5, PVA concentration (w/v) was 1.0%, magnetic stirring rate during solidification was 60 rpm and 300 kPa was chosen as transmembrane pressure. There was a linear relationship between the diameter of microcapsules and the pore size of the membranes. Finally, by manipulating the process parameters, PELA microcapsules with narrow size distributions (coefficient of variation was less than 15%), smooth morphology and various sizes, were obtained. Most importantly, the key factors affecting fabrication have been revealed and mechanisms were illustrated in detail, which would shed light on the research of amphiphilic polymer formulation. Copyright © 2011 Elsevier B.V. All rights reserved.

Molar heat capacity and entropy of calcium metal

USGS Publications Warehouse

Hemingway, B.S.; Robie, R.A.; Chase, M.W.

1997-01-01

The heat capacity of calcium has been measured at 85 mean temperatures between T ??? 8 K and T ??? 369 K using an adiabatically-shielded calorimeter in an intermittent heating mode. At T = 298.15 K, the recommended values for the molar heat capacity, molar entropy, and molar enthalpy increment referred to T = 0 are (25.77 ?? 0.08) J??K-1??mol-1, (42.90 ?? 0.11) J??K-1??mol-1, and (5811 ?? 12) J??mol-1, respectively. The uncertainties are twice the standard deviation of the mean. ?? 1997 Academic Press Limited.

Stress-State Effects on Strength and Fracture of Partially-Stabilized Zirconia

DTIC Science & Technology

1994-03-01

Ceramics and Test Procedures (1) Ce-TZP/AI 2 0 3 Ceramics A Ce-TZP/A120 3 powder of the nominal composition, 88 wt % of Ce-TZP (12 mol % CeO2 and 88...mol % ZrO2) and 10 wt % A120 3 and 2 wt % of proprietary dopants was obtained from a commercial source#. Billets of the Ce-TZP/A120 3 were prepared by...34Metastability of the Martensitic Transformation in a 12 mol % Ceria-Zirconia Alloy : 1, Deformation and Fracture Observations," J. Am. Ceram. Soc

Computational Prediction of Kinetic Rate Constants

DTIC Science & Technology

2006-06-09

24 Reactant: P(CH3)F2O (Difluor) Energetics: RHF DZP Frozen Core CCSD: -655.069925 Hartree CCSD(T): -655.090871 Hartree ZPE : 30.59 kcal...655.069925 Hartree CCSD(T): -655.090871 Hartree ZPE : 30.59 kcal/mol Geometry: RHF CCSD(T) Geom. Opt. PC Bond (Å): 1.79575 OP Bond (Å): 1.47117 FP Bond (Å... ZPE : 18.67 kcal/mol Intensity (km/mol)Frequency (cm -1)Symmetry 11.03833324.0968A1 11.03833324.0968A1 0.00003133.6602A1 2.38681429.9058A1

Possibilities and Limitations of Multioxides Crystals Growth

DTIC Science & Technology

2001-01-01

between 1 26 neodymium and lanthanum along growth direction of c,=33 mol % NdGaO3 Laj-,Nd.GaO3 single crystals 7. Concentration of 2 24- k= 0.77 (A-0.008...50, 60 and 66.6 mol.% of lanthanum aluminate concentration. The crystals adopt cubic structure at x up to 0.50 with the half of lattice constant...from the melt containing 22 mol.% and 30 Proc. SPIE Vol. 4412 more lanthanum aluminate were light yellow if the 3.90 processes were carried out in pure

(R,S)-3-Carb-oxy-2-(isoquinolinium-2-yl)propanoate monohydrate.

PubMed

Stilinović, Vladimir; Frkanec, Leo; Kaitner, Branko

2010-05-22

The title compound, C(13)H(11)NO(4)·H(2)O, is a monohydrate of a betaine exhibiting a positively charged N-substituted isoquino-line group and a deprotonated carboxyl group. In the crystal, mol-ecules are connected via short O-H⋯O hydrogen bonds between protonated and deprotonated carboxyl groups into chains of either R or S enanti-omers along [001]. These chains are additionally connected by hydrogen bonding between water mol-ecules and the deprotonated carb-oxy groups of neighbouring mol-ecules.

Intensive remote monitoring versus conventional care in type 1 diabetes: A randomized controlled trial.

PubMed

Gandrud, Laura; Altan, Aylin; Buzinec, Paul; Hemphill, Jesse; Chatterton, Jayne; Kelley, Tina; Vojta, Deneen

2018-02-21

While frequent contact with diabetes care providers may improve glycemic control among patients with type 1 diabetes (T1D), in-person visits are labor-intensive and costly. This study was conducted to assess the impact of an intensive remote therapy (IRT) intervention for pediatric patients with T1D. Pediatric patients with T1D were randomized to IRT or conventional care (CC) for 6 months. Both cohorts continued routine quarterly clinic visits and uploaded device data; for the IRT cohort, data were reviewed and patients were contacted if regimen adjustments were indicated. Glycated hemoglobin (HbA1c) change from baseline was assessed at 6 and 9 months. Diabetes-related quality of life (QoL), healthcare services utilization, and hypoglycemic events were also tracked. Among 117 enrollees (60 IRT, 57 CC), mean (SD) 6-month %HbA1c change for IRT vs CC was -0.34 (0.85) (-3.7 mmol/mol) vs -0.05 (0.74) (-0.5 mmol/mol) overall (P = .071); -0.15 (0.67) (1.6 mmol/mol) vs -0.02 (0.66) (0.2 mmol/mol) for ages 8 to 12 (P = .541); and -0.50 (0.95) (-5.5 mmol/mol) vs -0.06 (0.80) (-0.7 mmol/mol) for ages 13 to 17 (P = .056). Diabetes-related QoL increased by 6.5 and 1.3 points for IRT and CC, respectively (P = .062). Three months after intervention cessation, %HbA1c changed minimally among treated children aged 8 to 12 but increased by 0.22 (0.89) (2.4 mmol/mol) among those aged 13 to 17. IRT substantially affected diabetes metrics and improved QoL among pediatric patients with T1D. Adolescents experienced a stronger treatment effect, but had difficulty in sustaining improved control after intervention cessation. © 2018 John Wiley & Sons A/S. Published by John Wiley & Sons Ltd.

Synthesis of Phenolics and Flavonoids in Ginger (Zingiber officinale Roscoe) and Their Effects on Photosynthesis Rate

PubMed Central

Ghasemzadeh, Ali; Jaafar, Hawa Z. E.; Rahmat, Asmah

2010-01-01

The relationship between phenolics and flavonoids synthesis/accumulation and photosynthesis rate was investigated for two Malaysian ginger (Zingiber officinale) varieties grown under four levels of glasshouse light intensity, namely 310, 460, 630 and 790 μmol m−2s−1. High performance liquid chromatography (HPLC) was employed to identify and quantify the polyphenolic components. The results of HPLC analysis indicated that synthesis and partitioning of quercetin, rutin, catechin, epicatechin and naringenin were high in plants grown under 310 μmol m−2s−1. The average value of flavonoids synthesis in leaves for both varieties increased (Halia Bentong 26.1%; Halia Bara 19.5%) when light intensity decreased. Photosynthetic rate and plant biomass increased in both varieties with increasing light intensity. More specifically, a high photosynthesis rate (12.25 μmol CO2 m−2s−1 in Halia Bara) and plant biomass (79.47 g in Halia Bentong) were observed at 790 μmol m−2s−1. Furthermore, plants with the lowest rate of photosynthesis had highest flavonoids content. Previous studies have shown that quercetin inhibits and salicylic acid induces the electron transport rate in photosynthesis photosystems. In the current study, quercetin was an abundant flavonoid in both ginger varieties. Moreover, higher concentration of quercetin (1.12 mg/g dry weight) was found in Halia Bara leaves grown under 310 μmol m−2s−1 with a low photosynthesis rate. Furthermore, a high content of salicylic acid (0.673 mg/g dry weight) was detected in Halia Bara leaves exposed under 790 μmol m−2s−1 with a high photosynthesis rate. No salicylic acid was detected in gingers grown under 310 μmol m−2s−1. Ginger is a semi-shade loving plant that does not require high light intensity for photosynthesis. Different photosynthesis rates at different light intensities may be related to the absence or presence of some flavonoid and phenolic compounds. PMID:21151455

Dirac-Fock-Breit-Gaunt calculations for tungsten hexacarbonyl W(CO)6.

PubMed

Malli, Gulzari L

2016-05-21

The first all-electron fully relativistic Dirac-Fock-Breit-Gaunt (DFBG), Dirac-Fock (DF), and nonrelativistic (NR) Hartree-Fock (HF) calculations are reported for octahedral (Oh) tungsten hexacarbonyl W(CO)6. Our DF and NR HF calculations predict atomization energy of 73.76 and 70.33 eV, respectively. The relativistic contribution of ∼3.4 eV to the atomization energy of W(CO)6 is fairly significant. The DF and NR energy for the reaction W + 6CO → W(CO)6 is calculated as -7.90 and -8.86 eV, respectively. The mean bond energy predicted by our NR and DF calculations is 142.5 kJ/mol and 177.5 kJ/mol, respectively, and our predicted DF mean bond energy is in excellent agreement with the experimental value of 179 kJ/mol quoted in the literature. The relativistic effects contribute ∼35 kJ/mol to the mean bond energy and the calculated BSSE is 1.6 kcal/mol, which indicates that the triple zeta basis set used here is fairly good. The mean bond energy and the atomization energy calculated in our DFBG SCF calculations, which include variationally both the relativistic and magnetic Breit effects, is 157.4 kJ/mol and 68.84 eV, respectively. The magnetic Breit effects lead to a decrease of ∼20 kJ/mol and ∼4.9 eV for the mean bond energy and atomization energy, respectively, for W(CO)6. Our calculated magnetic Breit interaction energy of -9.79 eV for the energy of reaction (ΔE) for W + 6CO → W(CO)6 is lower by ∼1.90 eV as compared to the corresponding DF value (ΔE) and contributes significantly to the ΔE. A detailed discussion is presented of electronic structure, bonding, and molecular energy levels at various levels of theory for W(CO)6.

Effect of 5-hydroxytryptamine on duodenal mucosal bicarbonate secretion in mice.

PubMed

Tuo, Bi-Guang; Isenberg, Jon I

2003-09-01

5-hydroxytryptamine (5-HT) is an important neurotransmitter and intercellular messenger that modulates many gastrointestinal functions. Because little is known about the role of 5-HT in the regulation of duodenal bicarbonate secretion, we examined the role of 5-HT on duodenal bicarbonate secretion and define neural pathways involved in the actions of 5-HT. Duodenal mucosa from National Institutes of Health Swiss mice was stripped of seromuscular layers and mounted in Ussing chambers. The effect of 5-HT on duodenal bicarbonate secretion was determined by the pH stat technique. Acetylcholine (ACh) release from duodenal mucosa was assessed by preincubating the tissue with [(3)H] choline and measuring 5-HT-evoked release of tritium. 5-HT added to the serosal bath markedly stimulated duodenal bicarbonate secretion and short circuit current (Isc) in a dose-dependent manner (10(-7) mol/L to 10(-3) mol/L; P < 0.0001), whereas mucosally added 5-HT was without effect. 5-HT-stimulated bicarbonate secretion was independent of luminal Cl(-). Pretreatment with tetrodotoxin (TTX) (10(-6) mol/L) or atropine (10(-5) mol/L) markedly reduced 5-HT-stimulated duodenal bicarbonate secretion (by 60% and 65%, respectively; P < 0.001) and Isc (by 45% and 27%, respectively; P < 0.001 and P < 0.05). Pretreatment with N(omega)-nitro-l-arginine methyl ester (l-NAME) (10(-3) mol/L), propranolol (10(-5) mol/L), or phentolamine (10(-5) mol/L) did not significantly alter 5-HT-stimulated duodenal mucosal bicarbonate secretion or Isc. 5-HT concentration-dependently evoked ACh release from duodenal mucosal preparations (P < 0.0001). TTX markedly inhibited 5-HT-evoked ACh release (P < 0.001). 5-HT is a potent activator of duodenal mucosal bicarbonate secretion in mice. Duodenal bicarbonate secretion induced by 5-HT in vitro occurs principally via a cholinergic neural pathway.

Thermodynamics of the binding of L-arabinose and of D-galactose to the L-arabinose-binding protein of Escherichia coli.

PubMed

Fukada, H; Sturtevant, J M; Quiocho, F A

1983-11-10

The thermodynamics of the binding of L-arabinose and of D-galactose to the L-arabinose-binding protein of Escherichia coli have been studied by isothermal and scanning calorimetry. The binding reaction with arabinose is characterized by an enthalpy change of -15.3 +/- 0.5 kcal mol-1 at 25 degrees C, and a large decrease in apparent heat capacity, amounting to -0.44 +/- 0.05 kcal K-1 mol-1, which is constant over the temperature range 8 to 30 degrees C. Very similar results were obtained with D-galactose. These calorimetric results have been combined with binding constants determined by equilibrium dialysis (Clark, A. F., Gerken, T. A., and Hogg, R. W. (1982) Biochemistry 21, 2227-2233) to obtain free energy and entropy changes over the range 5 to 30 degrees C, and by extrapolation to 60 degrees C. The protein undergoes reversible unfolding on being heated with an increase in enthalpy at 53.5 degrees C of 151.8 +/- 1.1 kcal mol-1 (169.2 +/- 1.2 kcal mol-1 at 59.0 degrees C) and in apparent heat capacity of 3.16 +/- 0.07 kcal K-1 mol-1. In the presence of arabinose, the unfolding enthalpy is increased to 200.7 +/- 1.8 kcal mol-1 at 59.0 degrees C, the increase being due to the enthalpy of dissociation of the ligand which amounts to 31 kcal mol-1 at the unfolding temperature. The unfolding temperature is increased by the presence of excess arabinose or galactose, an effect which is due solely to displacement by the added ligand of the unfolding-dissociation equilibrium. The thermodynamic data are discussed in connection with the detailed structural information available for this system from x-ray crystallography (Newcomer, M. E., Gilliland, G. L. and Quiocho, F. A. (1981) J. Biol. Chem. 256, 13213-13217, and references cited therein).

Super-optimal CO2 reduces seed yield but not vegetative growth in wheat

NASA Technical Reports Server (NTRS)

Grotenhuis, T. P.; Bugbee, B.

1997-01-01

Although terrestrial atmospheric CO2 levels will not reach 1000 micromoles mol-1 (0.1%) for decades, CO2 levels in growth chambers and greenhouses routinely exceed that concentration. CO2 levels in life support systems in space can exceed 10000 micromoles mol-1(1%). Numerous studies have examined CO2 effects up to 1000 micromoles mol-1, but biochemical measurements indicate that the beneficial effects of CO2 can continue beyond this concentration. We studied the effects of near-optimal (approximately 1200 micromoles mol-1) and super-optimal CO2 levels (2400 micromoles mol-1) on yield of two cultivars of hydroponically grown wheat (Triticum aestivum L.) in 12 trials in growth chambers. Increasing CO2 from sub-optimal to near-optimal (350-1200 micromoles mol-1) increased vegetative growth by 25% and seed yield by 15% in both cultivars. Yield increases were primarily the result of an increased number of heads per square meter. Further elevation of CO2 to 2500 micromoles mol-1 reduced seed yield by 22% (P < 0.001) in cv. Veery-10 and by 15% (P < 0.001) in cv. USU-Apogee. Super-optimal CO2 did not decrease the number of heads per square meter, but reduced seeds per head by 10% and mass per seed by 11%. The toxic effect of CO2 was similar over a range of light levels from half to full sunlight. Subsequent trials revealed that super-optimal CO2 during the interval between 2 wk before and after anthesis mimicked the effect of constant super-optimal CO2. Furthermore, near-optimal CO2 during the same interval mimicked the effect of constant near-optimal CO2. Nutrient concentration of leaves and heads was not affected by CO2. These results suggest that super-optimal CO2 inhibits some process that occurs near the time of seed set resulting in decreased seed set, seed mass, and yield.

Measuring CO 2 and N 2 O Mass Transfer into GAP-1 CO 2 –Capture Solvents at Varied Water Loadings

DOE Office of Scientific and Technical Information (OSTI.GOV)

Whyatt, Greg A.; Zwoster, Andy; Zheng, Feng

This paper investigates the CO 2 and N 2 O absorption behavior in the water-lean gamma amino propyl (GAP)-1/TEG solvent system using a wetted-wall contactor. Testing was performed on a blend of GAP-1 aminosilicone in triethylene glycol at varied water loadings in the solvent. Measurements were made with CO 2 and N 2 O at representative lean (0.04 mol CO 2/mol alkalinity), middle (0.13 mol CO 2 /mol alkalinity) and rich (0.46 mol CO 2 /mol alkalinity) solvent loadings at 0, 5, 10 and 15 wt% water loadings at 40, 60 and 80C° and N 2 O at (0.08-0.09 molmore » CO 2 /mol alkalinity) at 5 wt% water at 40, 60 and 80C°. CO 2 flux was found to be non-linear with respect to log mean pressure driving force (LMPD). Liquid-film mass transfer coefficients (k'g) were calculated by subtracting the gas film resistance (determined from a correlation from literature) from the overall mass transfer measurement. The resulting k'g values for CO 2 and N 2 O in GAP-1/TEG mixtures were found to be higher than that of 5M aqueous monoethanolamine under comparable driving force albeit at higher solvent viscosities. The k'g values for CO 2 were also found to decrease with increasing solvent water content and increase with a decrease in temperature. These observations indicate that mass transfer of CO 2 in GAP-1/TEG is linked to the physical solubility of CO 2 , which is higher in organic solvents compared to water. This paper expands on the understanding of the unique mass transfer behavior and kinetics of CO 2 capture in water-lean solvents.« less

Crystal structures of Sr(ClO4)2·3H2O, Sr(ClO4)2·4H2O and Sr(ClO4)2·9H2O

PubMed Central

Hennings, Erik; Schmidt, Horst; Voigt, Wolfgang

2014-01-01

The title compounds, strontium perchlorate trihydrate {di-μ-aqua-aquadi-μ-perchlorato-strontium, [Sr(ClO4)2(H2O)3]n}, strontium perchlorate tetra­hydrate {di-μ-aqua-bis­(tri­aqua­diperchloratostrontium), [Sr2(ClO4)4(H2O)8]} and strontium perchlorate nona­hydrate {hepta­aqua­diperchloratostrontium dihydrate, [Sr(ClO4)2(H2O)7]·2H2O}, were crystallized at low temperatures according to the solid–liquid phase diagram. The structures of the tri- and tetra­hydrate consist of Sr2+ cations coordinated by five water mol­ecules and four O atoms of four perchlorate tetra­hedra in a distorted tricapped trigonal–prismatic coordination mode. The asymmetric unit of the trihydrate contains two formula units. Two [SrO9] polyhedra in the trihydrate are connected by sharing water mol­ecules and thus forming chains parallel to [100]. In the tetra­hydrate, dimers of two [SrO9] polyhedra connected by two sharing water mol­ecules are formed. The structure of the nona­hydrate contains one Sr2+ cation coordinated by seven water mol­ecules and by two O atoms of two perchlorate tetra­hedra (point group symmetry ..m), forming a tricapped trigonal prism (point group symmetry m2m). The structure contains additional non-coordinating water mol­ecules, which are located on twofold rotation axes. O—H⋯O hydrogen bonds between the water mol­ecules as donor and ClO4 tetra­hedra and water mol­ecules as acceptor groups lead to the formation of a three-dimensional network in each of the three structures. PMID:25552979

[Influence of carbodiimide-ethanol solution surface treatment on dentin microtensile bond strength].

PubMed

Zhang, Yi; Liu, Yu-hua; Zhou, Yong-sheng; Chung, Kwok-hung

2015-10-18

To evaluate the microtensile bond strength changes and patterns of fractures of the bonding interface after dentine surface treatment with carbodiimide-ethanol solution. 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) dissolved in ethanol was diluted into different concentrations of 2, 1, 0.3, 0.1 and 0.01 mol/L EDC-ethanol solutions. Twenty-eight caries-free extracted human third molars were ground metallurgically to prepare flat occlusal mid-coronal dentin surfaces and etched with 35% (mass fraction) phosphoric acid gel. Then they were treated with EDC-ethanol solution for 60 s before the bonding procedure and randomly divided into five experimental groups corresponding to the tested EDC-ethanol concentrations. The ethanol treated and no pre-treated surfaces were used as controls. Single Bond 2 adhesive was applied and resin composite disk was stacked on the treated dentine surface. The teeth with resin composite disks were stored in water at room temperature for 24 h and then sectioned longitudinally to produce stick specimens for microtensile bond strength test. Fracture patterns were observed with a stereomicroscope. The dentin surfaces pre-treated with 2 mol/L [(22.17±13.31) MPa] and 1 mol/L [(45.31±17.80) MPa] EDC-ethanol solutions resulted in statistically significant lower bond strength value (P<0.05). Increasing numbers of fracture pattern at the resin-dentin interface were also found in this two groups with percentages of 81.2% and 41.3% respectively. No significant difference was observed in the groups with 0.3, 0.1, 0.01 mol/L EDC surface treatment (P>0.05). No significant difference of immediate bond strengths was found in the 0.3, 0.1, 0.01 mol/L groups compared with the control group. EDC-ethanol solution surface treatment with concentrations of 2 mol/L and 1 mol/L resulted in decreasing of the bonding strength.

Curcumin and Natural Derivatives Inhibit Ebola Viral Proteins: An In silico Approach

PubMed Central

Baikerikar, Shruti

2017-01-01

Background: Ebola viral disease is a severe and mostly fatal disease in humans caused by Ebola virus. This virus belongs to family Filoviridae and is a single-stranded negative-sense virus. There is no single treatment for this disease which puts forth the need to identify new therapy to control and treat this fatal condition. Curcumin, one of the bioactives of turmeric, has proven antiviral property. Objective: The current study evaluates the inhibitory activity of curcumin, bisdemethoxycurcumin, demethoxycurcumin, and tetrahydrocurcumin against Zaire Ebola viral proteins (VPs). Materials and Methods: Molecular simulation of the Ebola VPs followed by docking studies with ligands comprising curcumin and related compounds was performed. Results: The highest binding activity for VP40 is −6.3 kcal/mol, VP35 is −8.3 kcal/mol, VP30 is −8.0 kcal/mol, VP24 is −7.7 kcal/mol, glycoprotein is −7.1 kcal/mol, and nucleoprotein is 6.8 kcal/mol. Conclusion: Bisdemethoxycurcumin shows better binding affinity than curcumin for most VPs. Metabolite tetrahydrocurcumin also shows binding affinity comparable to curcumin. These results indicate that curcumin, curcuminoids, and metabolite tetrahydrocurcumin can be potential lead compounds for developing a new therapy for Ebola viral disease. SUMMARY Curcumin, bisdemethoxycurcumin, and demethoxycurcumin are active constituents of turmeric. Tetrahydrocurcumin is the major metabolite of curcumin formed in the body after consumption and absorption of curcuminoidsCurcuminoids have proven antiviral activityBisdemethoxycurcumin showed maximum inhibition of Ebola viral proteins (VPs) among the curcuminoids in the docking procedure with a docking score as high as −8.3 kcal/molTetrahydrocurcumin showed inhibitory activity against Ebola VPs close to that of curcumin’s inhibitory action. Abbreviations Used: EBOV: Ebola virus, GP: Glycoprotein, NP: Nucleoprotein, NPT: Isothermal-isobaric Ensemble, amount of substance (N), pressure (P) and temperature (T) conserved, NVE: Canonical ensemble, amount of substance (N), volume (V) and temperature (T) conserved, VP: Viral protein. PMID:29333037

Structures, internal rotor potentials, and thermochemical properties for a series of nitrocarbonyls, nitroolefins, corresponding nitrites, and their carbon centered radicals.

PubMed

Snitsiriwat, Suarwee; Asatryan, Rubik; Bozzelli, Joseph W

2011-12-01

Structures, enthalpy (Δ(f)H°(298)), entropy (S°(T)), and heat capacity (C(p)(T)) are determined for a series of nitrocarbonyls, nitroolefins, corresponding nitrites, and their carbon centered radicals using the density functional B3LYP and composite CBS-QB3 calculations. Enthalpies of formation (Δ(f)H°(298)) are determined at the B3LYP/6-31G(d,p), B3LYP/6-31+G(2d,2p), and composite CBS-QB3 levels using several work reactions for each species. Entropy (S) and heat capacity (C(p)(T)) values from vibration, translational, and external rotational contributions are calculated using the rigid-rotor-harmonic-oscillator approximation based on the vibration frequencies and structures obtained from the density functional studies. Contribution to Δ(f)H(T), S, and C(p)(T) from the analysis on the internal rotors is included. Recommended values for enthalpies of formation of the most stable conformers of nitroacetone cc(═o)cno2, acetonitrite cc(═o)ono, nitroacetate cc(═o)no2, and acetyl nitrite cc(═o)ono are -51.6 kcal mol(-1), -51.3 kcal mol(-1), -45.4 kcal mol(-1), and -58.2 kcal mol(-1), respectively. The calculated Δ(f)H°(298) for nitroethylene c═cno2 is 7.6 kcal mol(-1) and for vinyl nitrite c═cono is 7.2 kcal mol(-1). We also found an unusual phenomena: an intramolecular transfer reaction (isomerization) with a low barrier (3.6 kcal mol(-1)) in the acetyl nitrite. The NO of the nitrite (R-ONO) in CH(3)C(═O')ONO moves to the C═O' oxygen in a motion of a stretching frequency and then a shift to the carbonyl oxygen (marked as O' for illustration purposes). © 2011 American Chemical Society

Assessing thermochemical data

NASA Astrophysics Data System (ADS)

Holmes, John L.; Aubry, Christiane; Wang, Xian

2007-11-01

This paper describes, with examples, a critical assessment of thermochemical data for some small molecules and free radicals. The available heats of formation, [Delta]fH° (all 298 K values). for simple alkyl hydroperoxides and di-alkyl peroxides were compared and new data are provided. The [Delta]fH° values, all ±5 kJ/mol, are: CH3OOH, -135; CH3CH2OOH, -168; n-C3H7OOH, -189; s-C3H7OOH, -205; t-C4H9OOH, -240; CH3OOCH3, -132; CH3CH2OOCH3, -165; C2H5OOC2H5, -198; n-C3H7OOn-C3H7, -240; s-C3H7OOs-C3H7, -272; t-C4H9OOt-C4H9, -342. These are consistent with established O-O bond dissociation energies and with additivity considerations. [Delta]fH° values for the corresponding alkoxy radicals are also addressed. A similar survey was applied to the homologous n-alkyl aldehydes, C2 to C8, for which recommended [Delta]fH° values, all ±1.5 kJ/mol, are: -166.5, -189, -207.5, -227, -248, -268 and -289, respectively. Particular attention was given to [Delta]fH°(CH3CO) = -10.3 ± 1.8 kJ/mol. The current NIST WebBook datum, [Delta]fH°(CS) = 280.3 kJ/mol, is arguably the best value, being consistent with related thermochemical data. Finally the [Delta]fH° values for the allylic free radicals CH2CHCH2, 174 ± 3 kJ/mol, CH2CHCH(OH), 4.5 ± 4 kJ/mol, and (CH2CH)2C(OH), 37 ± 4 kJ/mol, derived from experimental data and results of computational chemistry are described, together with some related homolytic bond strengths.

Gingerol Inhibits Serum-Induced Vascular Smooth Muscle Cell Proliferation and Injury-Induced Neointimal Hyperplasia by Suppressing p38 MAPK Activation.

PubMed

Jain, Manish; Singh, Ankita; Singh, Vishal; Maurya, Preeti; Barthwal, Manoj Kumar

2016-03-01

Gingerol inhibits growth of cancerous cells; however, its role in vascular smooth muscle cell (VSMC) proliferation is not known. The present study investigated the effect of gingerol on VSMC proliferation in cell culture and during neointima formation after balloon injury. Rat VSMCs or carotid arteries were harvested at 15 minutes, 30 minutes, 1, 6, 12, and 24 hours of fetal bovine serum (FBS; 10%) stimulation or balloon injury, respectively. Gingerol prevented FBS (10%)-induced proliferation of VSMCs in a dose-dependent manner (50 μmol/L-400 μmol/L). The FBS-induced proliferating cell nuclear antigen (PCNA) upregulation and p27(Kip1) downregulation were also attenuated in gingerol (200 μmol/L) pretreated cells. Fetal bovine serum-induced p38 mitogen-activated protein kinase (MAPK) activation, PCNA upregulation, and p27(Kip1) downregulation were abrogated in gingerol (200 μmol/L) and p38 MAPK inhibitor (SB203580, 10 μmol/L) pretreated cells. Balloon injury induced time-dependent p38 MAPK activation in the carotid artery. Pretreatment with gingerol (200 μmol/L) significantly attenuated injury-induced p38 MAPK activation, PCNA upregulation, and p27(Kip1) downregulation. After 14 days of balloon injury, intimal thickening, neointimal proliferation, and endothelial dysfunction were significantly prevented in gingerol pretreated arteries. In isolated organ bath studies, gingerol (30 nmol/L-300 μmol/L) inhibited phenylephrine-induced contractions and induced dose-dependent relaxation of rat thoracic aortic rings in a partially endothelium-dependent manner. Gingerol prevented FBS-induced VSMC proliferation and balloon injury-induced neointima formation by regulating p38 MAPK. Vasodilator effect of gingerol observed in the thoracic aorta was partially endothelium dependent. Gingerol is thus proposed as an attractive agent for modulating VSMC proliferation, vascular reactivity, and progression of vascular proliferative diseases. © The Author(s) 2015.

Thermal decomposition mechanism of 1-ethyl-3-methylimidazolium bromide ionic liquid.

PubMed

Chambreau, Steven D; Boatz, Jerry A; Vaghjiani, Ghanshyam L; Koh, Christine; Kostko, Oleg; Golan, Amir; Leone, Stephen R

2012-06-21

In order to better understand the volatilization process for ionic liquids, the vapor evolved from heating the ionic liquid 1-ethyl-3-methylimidazolium bromide (EMIM(+)Br(-)) was analyzed via tunable vacuum ultraviolet photoionization time-of-flight mass spectrometry (VUV-PI-TOFMS) and thermogravimetric analysis mass spectrometry (TGA-MS). For this ionic liquid, the experimental results indicate that vaporization takes place via the evolution of alkyl bromides and alkylimidazoles, presumably through alkyl abstraction via an S(N)2 type mechanism, and that vaporization of intact ion pairs or the formation of carbenes is negligible. Activation enthalpies for the formation of the methyl and ethyl bromides were evaluated experimentally, ΔH(‡)(CH(3)Br) = 116.1 ± 6.6 kJ/mol and ΔH(‡)(CH(3)CH(2)Br) = 122.9 ± 7.2 kJ/mol, and the results are found to be in agreement with calculated values for the S(N)2 reactions. Comparisons of product photoionization efficiency (PIE) curves with literature data are in good agreement, and ab initio thermodynamics calculations are presented as further evidence for the proposed thermal decomposition mechanism. Estimates for the enthalpy of vaporization of EMIM(+)Br(-) and, by comparison, 1-butyl-3-methylimidazolium bromide (BMIM(+)Br(-)) from molecular dynamics calculations and their gas phase enthalpies of formation obtained by G4 calculations yield estimates for the ionic liquids' enthalpies of formation in the liquid phase: ΔH(vap)(298 K) (EMIM(+)Br(-)) = 168 ± 20 kJ/mol, ΔH(f, gas)(298 K) (EMIM(+)Br(-)) = 38.4 ± 10 kJ/mol, ΔH(f, liq)(298 K) (EMIM(+)Br(-)) = -130 ± 22 kJ/mol, ΔH(f, gas)(298 K) (BMIM(+)Br(-)) = -5.6 ± 10 kJ/mol, and ΔH(f, liq)(298 K) (BMIM(+)Br(-)) = -180 ± 20 kJ/mol.

Thermodynamic and kinetic studies on pectinase extracted from Aspergillus aculeatus: Free and immobilized enzyme entrapped in alginate beads.

PubMed

de Oliveira, Rodrigo Lira; da Silva, Osmar Soares; Converti, Attilio; Porto, Tatiana Souza

2018-05-01

The kinetics and thermodynamics of Aspergillus aculeatus pectinase, either free or immobilized in alginate beads, were investigated. Pectinase immobilization ensured an enzyme immobilization yield of 59.71%. The irreversible denaturation of pectinase in both preparations was evaluated at temperatures ranging from 30 to 60 °C. When temperature was raised, the first-order thermal denaturation constant increased from 0.0011 to 0.0231 min -1 for the free enzyme and from 0.0017 to 0.0700 min -1 for the immobilized one, respectively. The results of residual activity tests enabled us to estimate, for denaturation of both free and immobilized pectinase, the activation energy (E ⁎ d  = 85.1 and 101.6 kJ·mol -1 ), enthalpy (82.59 ≤ ΔH ⁎ d  ≤ 82.34 kJ·mol -1 and 99.11 ≤ ΔH ⁎ d  ≤ 98.86 kJ·mol -1 ), entropy (-63.26 ≤ ΔS ⁎ d  ≤ -63.85 J·mol -1 ·K -1 and -5.50 ≤ ΔS ⁎ d  ≤ -5.23 J·mol -1 ·K -1 ) and Gibbs free energy (101.8 ≤ ΔG ⁎ d  ≤ 104.7 kJ·mol -1 and 100.6 ≤ ΔG ⁎ d  ≤ 102.0 kJ·mol -1 ). The integral activity of a continuous system using the free and immobilized enzyme was also predicted, whose results indicated a satisfactory enzyme long-term thermostability in both preparations at temperatures commonly used to clarify juice. These results suggest that both free and immobilized pectinase from A. aculeatus may be profitably exploited in future food industrial applications, with special concern to the immobilized enzyme because of its reusability. Copyright © 2018 Elsevier B.V. All rights reserved.

Getting to goal in newly diagnosed type 2 diabetes using combination drug "subtraction therapy".

PubMed

Jennings, Anthony S; Lovett, Alexandra J; George, Tina M; Jennings, Jonathan S

2015-09-01

The treatment of newly diagnosed type 2 diabetes mellitus is diverse, with no clear consensus regarding the initial drug regimen or dosing to achieve optimal glycemic control. We treated 44 consecutive patients with newly diagnosed type 2 diabetes with maximally tolerated doses of pioglitazone 45 mg/day, metformin 1000-2000 mg/day, and repaglinide 1-4 mg before meals. The doses and drugs were subsequently decreased ("subtraction therapy") to achieve optimal glycemic control and minimize side effects. Three primary outcomes were measured: the short term HbA1c response, the long term HbA1c response, and the incidence of hypoglycemia. All 44 patients responded with a rapid, progressive decline in their HbA1c levels from 11.43±2.3% to 6.17±0.72% (101±25.1 mmol/mol to 44±7.9 mmol/mol) by three months, and remained stable thereafter. An HbA1c ≤7.0% (≤53 mmol/mol) was reached within 1-4 months in 42 of 44 patients, and in every patient by 12 months. Each patient's lowest HbA1c level, 5.65±0.6% (38±6.6 mmol/mol), was reached over 6.3±2.9 months. Patients with initial HbA1c levels >10% (>86 mmol/mol) (n=33) responded similarly as those with HbA1c levels <10% (<86 mmol/mol) (n=11). Combination drug therapy maintained HbA1c levels between 5.0 and 7.0% (31 and 53 mmol/mol) for up to 14.83 years. Only one clinically significant hypoglycemic event occurred during 261.08 person-years of follow-up. In our experience, combination drug "subtraction therapy" was safe and effective for treating all newly diagnosed type 2 diabetic patients. Copyright © 2015 Elsevier Inc. All rights reserved.

Coupled cluster investigation on the thermochemistry of dimethyl sulphide, dimethyl disulphide and their dissociation products: the problem of the enthalpy of formation of atomic sulphur

NASA Astrophysics Data System (ADS)

Denis, Pablo A.

2014-04-01

By means of coupled cluster theory and correlation consistent basis sets we investigated the thermochemistry of dimethyl sulphide (DMS), dimethyl disulphide (DMDS) and four closely related sulphur-containing molecules: CH3SS, CH3S, CH3SH and CH3CH2SH. For the four closed-shell molecules studied, their enthalpies of formation (EOFs) were derived using bomb calorimetry. We found that the deviation of the EOF with respect to experiment was 0.96, 0.65, 1.24 and 1.29 kcal/mol, for CH3SH, CH3CH2SH, DMS and DMDS, respectively, when ΔHf,0 = 65.6 kcal/mol was utilised (JANAF value). However, if the recently proposed ΔHf,0 = 66.2 kcal/mol was used to estimate EOF, the errors dropped to 0.36, 0.05, 0.64 and 0.09 kcal/mol, respectively. In contrast, for the CH3SS radical, a better agreement with experiment was obtained if the 65.6 kcal/mol value was used. To compare with experiment avoiding the problem of the ΔHf,0 (S), we determined the CH3-S and CH3-SS bond dissociation energies (BDEs) in CH3S and CH3SS. At the coupled cluster with singles doubles and perturbative triples correction level of theory, these values are 48.0 and 71.4 kcal/mol, respectively. The latter BDEs are 1.5 and 1.2 kcal/mol larger than the experimental values. The agreement can be considered to be acceptable if we take into consideration that these two radicals present important challenges when determining their EOFs. It is our hope that this work stimulates new studies which help elucidate the problem of the EOF of atomic sulphur.

First evidence for the production of OH radicals by carbonyl oxides in solution phase A DFT investigation

NASA Astrophysics Data System (ADS)

Cremer, Dieter; Kraka, Elfi; Sosa, Carlos

2001-03-01

Dimesitylketone O-oxide ( 1) rearranges in solution to yield the alcohol 2-methylhydroxy-pentamethylbenzophenone ( 5) and dimesitylketone ( 6). DFT-B3LYP/cc-pVTZ calculations reveal that H migration from an o-methyl group to the terminal O atom of the COO unit of 1 rather than the isomerization of 1 is energetically the most favorable process. Calculated activation enthalpies (gas phase: 12.8 kcal/mol; CH 3CN solution: 12.4 kcal/mol) are in excellent agreement with measured activation enthalpies (CFCl 3 solution: 13.2±0.2 kcal/mol; CH 3CN solution: 12.5±0.3 kcal/mol). The hydroperoxide formed by H migration decomposes to a OH and a benzyl radical. Recombination in the solvent cage leads to alcohol 5 while diffusion of OH out of the solvent cage yields 6.

A theoretical study of the cyclization processes of energized CCCSi and CCCP.

PubMed

Maclean, Micheal J; Eichinger, Peter C H; Wang, Tianfang; Fitzgerald, Mark; Bowie, John H

2008-12-11

Calculations at the CCSD(T)/aug-cc-pVDZ//B3LYP/6-31+G(d) level of theory have shown that cyclization of both the ground state triplet and the corresponding singlet state of CCCSi may rearrange to give cyclic isomers which upon ring opening may reform linear C(3)Si isomers in which the carbon atoms are scrambled. The cyclization processes are energetically favorable with barriers to the transition states from 13 to 16 kcal mol(-1). This should be contrasted with the analogous process of triplet CCCC to triplet rhombic C(4), which requires an excess energy of 25.8 kcal mol(-1). A similar cyclization of doublet CCCP requires 50.4 kcal mol(-1) of excess energy; this should be contrasted with the same process for CCCN, which requires 54.7 kcal mol(-1) to effect cyclization.

Testing an Algae-Based Air-Regeneration System

NASA Technical Reports Server (NTRS)

Nienow, James

1998-01-01

The potential of an air-regeneration system based on the growth of unicellular algae on the surface of porous ceramic tubes was evaluated. The system is fairly robust with respect to environmental conditions and is capable of maintaining algal cultures for up to 365 days. Under standard conditions (50-66 micro mol/sq mm s (PPF), 450 micro mol mol of CO2), mature tubes can remove CO2 at a rate of up to 90 micro mol/sq m min. Under these conditions, approximately 200 square meters of area would be required for each member of the crew. However, the rate of uptake increases with both photon flux and CO2 concentration in accordance with Michaelis-Menton dynamics. An extrapolation to conditions of saturating light and carbon dioxide indicates that the area required can be reduced by a factor of at least 2.5.

Determination of Inorganic Ion Profiles of Illicit Drugs by Capillary Electrophoresis.

PubMed

Evans, Elizabeth; Costrino, Carolina; do Lago, Claudimir L; Garcia, Carlos D; Roux, Claude; Blanes, Lucas

2016-11-01

A portable capillary electrophoresis instrument with dual capacitively coupled contactless conductivity detection (C 4 D) was used to determine the inorganic ionic profiles of three pharmaceutical samples and precursors of two illicit drugs (contemporary samples of methylone and para-methoxymethamphetamine). The LODs ranged from 0.10 μmol/L to 1.25 μmol/L for the 10 selected cations, and from 0.13 μmol/L to 1.03 μmol/L for the eight selected anions. All separations were performed in less than 6 min with migration times and peak area RSD values ranging from 2 to 7%. The results demonstrate the potential of the analysis of inorganic ionic species to aid in the identification and/or differentiation of unknown tablets, and real samples found in illicit drug manufacture scenarios. From the resulting ionic fingerprint, the unknown tablets and samples can be further classified. © 2016 American Academy of Forensic Sciences.

Kinetics of Ni3S2 sulfide dissolution in solutions of sulfuric and hydrochloric acids

NASA Astrophysics Data System (ADS)

Palant, A. A.; Bryukvin, V. A.; Vinetskaya, T. N.; Makarenkova, T. A.

2008-02-01

The kinetics of Ni3S2 sulfide (heazlewoodite) dissolution in solutions of hydrochloric and sulfuric acids is studied. The process under study in the temperature range of 30 90°C is found to occur in a kinetic regime and is controlled by the corresponding chemical reactions of the Ni3S2 decomposition by solutions of inorganic acids ( E a = 67 92 kJ/mol, or 16 22 kcal/mol). The only exception is the Ni3S2-HCl system at elevated temperatures (60 90°C). In this case, the apparent activation energy decreases sharply to 8.8 kJ/mol (2.1 kcal/mol), which is explained by the catalytic effect of gaseous chlorine formed under these conditions. The studies performed are related to the physicochemical substantiation of the hydrometallurgical processing of the copper-nickel converter mattes produced in the industrial cycle of the Norilsk Mining Company.

Improved modification for the density-functional theory calculation of thermodynamic properties for C-H-O composite compounds.

PubMed

Liu, Min Hsien; Chen, Cheng; Hong, Yaw Shun

2005-02-08

A three-parametric modification equation and the least-squares approach are adopted to calibrating hybrid density-functional theory energies of C(1)-C(10) straight-chain aldehydes, alcohols, and alkoxides to accurate enthalpies of formation DeltaH(f) and Gibbs free energies of formation DeltaG(f), respectively. All calculated energies of the C-H-O composite compounds were obtained based on B3LYP6-311++G(3df,2pd) single-point energies and the related thermal corrections of B3LYP6-31G(d,p) optimized geometries. This investigation revealed that all compounds had 0.05% average absolute relative error (ARE) for the atomization energies, with mean value of absolute error (MAE) of just 2.1 kJ/mol (0.5 kcal/mol) for the DeltaH(f) and 2.4 kJ/mol (0.6 kcal/mol) for the DeltaG(f) of formation.

9-(3,4-Dimeth­oxy­phen­yl)-3,3,6,6-tetra­methyl-4,5,6,9-tetra­hydro-3H-xanthene-1,8(2H,7H)-dione

PubMed Central

Mehdi, Sayed Hasan; Sulaiman, Othman; Ghalib, Raza Murad; Yeap, Chin Sing; Fun, Hoong-Kun

2011-01-01

The asymmetric unit of the title xanthene compound, C25H30O5, contains two mol­ecules in which the pyran ring and the dimeth­oxy­phenyl ring are nearly perpendicular to one another [dihedral angles = 86.81 (8) and 84.45 (9)°]. One of the meth­oxy groups in one mol­ecule is twisted away from the phenyl ring [C—O—C—C torsion angle = −103.40 (16)°]. The pyran ring adopts a boat conformation whereas the two fused cyclo­hexane rings adopt envelope conformations in both mol­ecules. In the crystal, mol­ecules are linked into a three-dimensional network by C—H⋯O hydrogen bonds. PMID:21837111

2,3-Diamino-pyridinium sorbate-sorbic acid (1/1).

PubMed

Hemamalini, Madhukar; Goh, Jia Hao; Fun, Hoong-Kun

2012-01-01

In the title mol-ecular salt-adduct, C(5)H(8)N(3) (+)·C(6)H(7)O(2) (-)·C(6)H(8)O(2), the 2,3-diamino-pyridinium cation is essentially planar, with a maximum deviation of 0.013 (2) Å, and is protanated at its pyridine N atom. The sorbate anion and sorbic acid mol-ecules exist in extended conformations. In the crystal, the protonated N atom and one of the two amino-group H atoms are hydrogen bonded to the sorbate anion through a pair of N-H⋯O hydrogen bonds, forming an R(1) (2)(6) ring motif. The carboxyl groups of the sorbic acid mol-ecules and the carboxyl-ate groups of the sorbate anions are connected via O-H⋯O hydrogen bonds. Furthermore, the ion pairs and neutral mol-ecules are connected via inter-molecular N-H⋯O hydrogen bonds, forming sheets lying parallel to (100).

Kinetics of carotenoids degradation and furosine formation in dried apricots (Prunus armeniaca L.).

PubMed

Fratianni, A; Niro, S; Messia, M C; Cinquanta, L; Panfili, G; Albanese, D; Di Matteo, M

2017-09-01

The kinetics of carotenoid and color degradation, as well as furosine formation, were investigated in apricot fruits during convective heating at 50, 60 and 70°C. Degradation of carotenoids and color, expressed as total color difference (TCD), followed a first and zero order kinetic, respectively. The activation energy (Ea) for carotenoids degradation ranged from 73.7kJ/mol for 13-cis-β-carotene to 120.7kJ/mol for lutein, being about 91kJ/mol for all-trans-β-carotene. Violaxanthin and anteraxanthin were the most susceptible to thermal treatment. The furosine evolution was fitted at zero order kinetic model. The Ea for furosine formation was found to be 83.3kJ/mol and the Q 10 (temperature coefficient) varied from 1.59 to 4.14 at the temperature ranges 50-60°C and 60-70°C, respectively. Copyright © 2016 Elsevier Ltd. All rights reserved.

On the nature of hydrogen bonding between the phosphatidylcholine head group and water and dimethylsulfoxide

NASA Astrophysics Data System (ADS)

Dabkowska, Aleksandra P.; Lawrence, M. Jayne; McLain, Sylvia E.; Lorenz, Christian D.

2013-01-01

Molecular dynamics simulations are used to provide a detailed investigation of the hydrogen bond networks around the phosphatidylcholine (PC) head group in 1,2-dipropionyl-sn-glycero-3-phosphocholine in pure water, 10 mol.% and 30 mol.% dimethylsulfoxide (DMSO)-water solutions. Specifically, it is observed that DMSO replaces those water molecules that are within the first solvation shell of the choline, phosphate and ester groups of the PC head group, but are not hydrogen-bonded to the group. The effect of the presence of DMSO on the hydrogen bond network around the PC head groups of the lipid changes with the concentration of DMSO. In comparison to the hydrogen bond network observed in the pure water system, the number of hydrogen-bonded chains of solvent molecules increases slightly for the 10 mol.% DMSO system, while, in the 30 mol.% DMSO system, the number of hydrogen-bonded chains of solvent molecules decreases.

Dissociation energies of the hydrogen-bonded dimers RCN-HF (R = CH3, HCC) determined by rotational spectroscopy

NASA Astrophysics Data System (ADS)

Legon, A. C.; Millen, D. J.; North, Hazel M.

1987-03-01

The zero-point and equilibrium dissociation energies (D0 and De) of the hydrogen-bonded dimers CH3CN-HF and HCCCN-HF are determined experimentally on the basis of absolute intensity measurements of selected rotational transitions. A Stark-modulated microwave spectrometer is employed with the cooled absorption cell described by Legon et al. (1980). The results are presented in tables and analyzed. Energies determined are D0 = 26.1(0.6) kJ/mol and De = 29.0(0.9) kJ/mol for CH3CN-HF and D0 = 20.4(0.7) kJ/mol and De = 23.4(0.9) kJ/mol for HCCCN-HF. Theoretical De values calculated using the Morse potential function are found to be in much better agreement with the experimental results than those calculated with the Lennard-Jones potential function.

An engineered non-oxidative glycolysis pathway for acetone production in Escherichia coli.

PubMed

Yang, Xiaoyan; Yuan, Qianqian; Zheng, Yangyang; Ma, Hongwu; Chen, Tao; Zhao, Xueming

2016-08-01

To find new metabolic engineering strategies to improve the yield of acetone in Escherichia coli. Results of flux balance analysis from a modified Escherichia coli genome-scale metabolic network suggested that the introduction of a non-oxidative glycolysis (NOG) pathway would improve the theoretical acetone yield from 1 to 1.5 mol acetone/mol glucose. By inserting the fxpk gene encoding phosphoketolase from Bifidobacterium adolescentis into the genome, we constructed a NOG pathway in E.coli. The resulting strain produced 47 mM acetone from glucose under aerobic conditions in shake-flasks. The yield of acetone was improved from 0.38 to 0.47 mol acetone/mol glucose which is a significant over the parent strain. Guided by computational analysis of metabolic networks, we introduced a NOG pathway into E. coli and increased the yield of acetone, which demonstrates the importance of modeling analysis for the novel metabolic engineering strategies.

Low-temperature heat capacity and entropy of chalcopyrite (CuFeS2): estimates of the standard molar enthalpy and Gibbs free energy of formation of chalcopyrite and bornite (Cu5FeS4)

USGS Publications Warehouse

Robie, R.A.; Wiggins, L.B.; Barton, P.B.; Hemingway, B.S.

1985-01-01

The heat capacity of CuFeS2 (chalcopyrite) was measured between 6.3 and 303.5 K. At 298.15 K, Cp,mo and Smo(T) are (95.67??0.14) J??K-1??mol-1 and (124.9??0.2) J??K-1??mol-1, respectively. From a consideration of the results of two sets of equilibrium measurements we conclude that ??fHmo(CuFeS2, cr, 298.15 K) = -(193.6??1.6) kJ??mol-1 and that the recent bomb-calorimetric determination by Johnson and Steele (J. Chem. Thermodynamics 1981, 13, 991) is in error. The standard molar Gibbs free energy of formation of bornite (Cu5FeS4) is -(444.9??2.1) kJ??mol-1 at 748 K. ?? 1985.

Kinetics of non-isothermal decomposition of cinnamic acid

NASA Astrophysics Data System (ADS)

Zhao, Ming-rui; Qi, Zhen-li; Chen, Fei-xiong; Yue, Xia-xin

2014-07-01

The thermal stability and kinetics of decomposition of cinnamic acid were investigated by thermogravimetry and differential scanning calorimetry at four heating rates. The activation energies of this process were calculated from analysis of TG curves by methods of Flynn-Wall-Ozawa, Doyle, Distributed Activation Energy Model, Šatava-Šesták and Kissinger, respectively. There are only one stage of thermal decomposition process in TG and two endothermic peaks in DSC. For this decomposition process of cinnamic acid, E and log A[s-1] were determined to be 81.74 kJ mol-1 and 8.67, respectively. The mechanism was Mampel Power law (the reaction order, n = 1), with integral form G(α) = α (α = 0.1-0.9). Moreover, thermodynamic properties of Δ H ≠, Δ S ≠, Δ G ≠ were 77.96 kJ mol-1, -90.71 J mol-1 K-1, 119.41 kJ mol-1.

Octahydriodo diborane (B2H8) and its protonated cations containing five-, six-, and seven-coordinate boron atoms

PubMed Central

Olah, George A.; Surya Prakash, G. K.; Rasul, Golam

2012-01-01

Structures of octahydriodo diborane (B2H8) 1 and its protonated 3, diprotonated 5, triprotonated 6, and tetraprotonated 7 ions were found to be calculationally viable minima at the MP2/cc-pVTZ level of theory. Each structure contains two-electron three-center (2e-3c) bonds. The protonation of 1 to form 3 was found to be strongly exothermic by 176.0 kcal/mol. Subsequent protonation of 3 to form 5 was also found to be exothermic by 28.4 kcal/mol. Further protonation of 5 to form 6 was, however, computed to be endothermic by 122.0 kcal/mol whereas protonation of 6 to form 7 was again highly endothermic by 238.8 kcal/mol. Deprotonation barriers of the ions were also computed. PMID:22511715

Reaction rates and prediction of thermal instability during aluminum alloy 6061 dissolution

DOE Office of Scientific and Technical Information (OSTI.GOV)

McFarlane, J.; DePaoli, D. W.; Mattus, C. H.

Here, chemical kinetics of dissolution of aluminum alloy 6061 was investigated for the processing of Pu-238 for deep space missions. The rate of dissolution was measured by the heat release and appeared to be controlled by the rate of release of Al(OH) 4 – from the metal surface. Rates of reaction were measured from 273 to 365 K, giving an activation energy of 72 ± 13 kJ•(mol Al) –1 and a pre-exponential factor of 5 ± 3 × 10 9 dm 3mol –1min –1. Minor alloying elements did not appear to affect the reaction kinetics. The average heat of dissolutionmore » was –360 ± 70 kJ•(mol NaAlO 2) –1. When extrapolated to an infinitely dilute solution of aluminum, kJ•(mol NaAlO 2) –1.« less

Astaxanthin diferulate as a bifunctional antioxidant.

PubMed

Papa, T B R; Pinho, V D; do Nascimento, E S P; Santos, W G; Burtoloso, A C B; Skibsted, L H; Cardoso, D R

2015-01-01

Astaxanthin when esterified with ferulic acid is better singlet oxygen quencher with k2 = (1.58 ± 0.1) 10(10) L mol(-1)s(-1) in ethanol at 25°C compared with astaxanthin with k2 = (1.12 ± 0.01) 10(9) L mol(-1)s(-1). The ferulate moiety in the astaxanthin diester is a better radical scavenger than free ferulic acid as seen from the rate constant of scavenging of 1-hydroxyethyl radicals in ethanol at 25°C with a second-order rate constant of (1.68 ± 0.1) 10(8) L mol(-1)s(-1) compared with (1.60 ± 0.03) 10(7) L mol(-1)s(-1) for the astaxanthin:ferulic acid mixture, 1:2 equivalents. The mutual enhancement of antioxidant activity for the newly synthetized astaxanthin diferulate becoming a bifunctional antioxidant is rationalized according to a two-dimensional classification plot for electron donation and electron acceptance capability.

Comet Sugano-Saigusa-Fujikawa (1983V) - A small, puzzling comet

NASA Astrophysics Data System (ADS)

Hanner, M. S.; Newburn, R. L.; Spinrad, H.; Veeder, G. J.

1987-10-01

Spectroscopic and infrared observations of comet Sugano-Saigusa-Fujikawa (1983 V) were obtained during its close approach to the Earth on 11 - 14 June 1983. The [O I] production rates of 1.8±0.9×1026atoms/s observed on 12.3 June and 7±3.5×1026atoms/s on 13.4 June lead to derived water-production rates of 3×1027mol/s on 12 June and 1.1×1028mol/s on 13 June. The abundances of the minor species NH2, CN, C2, and C3 are unusually low relative to [O I]. The upper limit to the average nuclear radius from the infrared and visual photometry on 12 - 13 June (assuming that the entire signal came from the nucleus) is ≡370 m. The dust/gas mass ratio was <0.01 on June 12 and <0.005 on June 13.

Poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles-catalyzed hydrolysis of ammonia borane for hydrogen generation

NASA Astrophysics Data System (ADS)

Rakap, Murat

2015-02-01

The catalytic use of highly efficient poly(N-vinyl-2-pyrrolidone)-stabilized palladium-platinum nanoparticles (4.2 ± 1.9 nm) in the hydrolysis of ammonia-borane is reported. The catalyst is prepared by co-reduction of two metal ions in ethanol/water mixture by an alcohol reduction method and characterized by transmission electron microscopy, X-ray photoelectron spectroscopy and UV-Vis spectroscopy. They are recyclable and highly active for hydrogen generation from the hydrolysis of ammonia-borane even at very low concentrations and temperature, providing a record numbers of average turnover frequency value (125 mol H2/mol cat.min-1) and maximum hydrogen generation rate (3468 L H2 min-1 (mol cat)-1). They also provide activation energy of 51.7 ± 2 kJ/mol for the hydrolysis of ammonia borane.

Research on modified the estimates of NOx emissions combined the OMI and ground-based DOAS technique

NASA Astrophysics Data System (ADS)

Zhang, Qiong; Li*, Ang; Xie, Pinhua; Hu, Zhaokun; Wu, Fengcheng; Xu, Jin

2017-04-01

A new method to calibrate nitrogen dioxide (NO2) lifetimes and emissions from point sources using satellite measurements base on the mobile passive differential optical absorption spectroscopy (DOAS) and multi axis differential optical absorption spectroscopy (MAX-DOAS) is described. It is based on using the Exponentially-Modified Gaussian (EMG) fitting method to correct the line densities along the wind direction by fitting the mobile passive DOAS NO2 vertical column density (VCD). An effective lifetime and emission rate are then determined from the parameters of the fit. The obtained results were then compared with the results acquired by fitting OMI (Ozone Monitoring Instrument) NO2 using the above fitting method, the NOx emission rate was about 195.8mol/s, 160.6mol/s, respectively. The reason why the latter less than the former may be because the low spatial resolution of the satellite.

Development and characterization of a FIA system for selective assay of L-ascorbic acid in food samples.

PubMed

Vig, Attila; Igloi, Attila; Adanyi, Nora; Gyemant, Gyongyi; Csutoras, Csaba; Kiss, Attila

2010-10-01

An amperometric detector and an enzymatic reaction were combined for the measurement of L-ascorbic acid. The enzyme cell (containing immobilized ascorbate oxidase) was connected to a flow injection analyzer (FIA) system with a glassy carbon electrode as an amperometric detector. During optimization and measurements two sample injectors were used, one before and one after the enzyme cell, thus eliminating the background interferences. Subtraction of the signal area given in the presence of enzyme from the one given in the absence of enzyme was applied for measuring analyte concentrations and calibration at 400 mV. Analysis capacity of system is 25 samples/hour. The relative standard deviation (RSD) was below 5% (5 times repeated, 400 μmol/L conc.), linearity up to 400 μmol/L, limit of detection (LOD) 5 μmol/L, fitting of calibration curve in 25-400 μmol/L range was R (2) = 0.99.

Diosgenin hemihydrate

PubMed Central

Hernández Linares, María-Guadalupe; Bernès, Sylvain; Flores-Alamo, Marcos; Guerrero-Luna, Gabriel; Martínez-Gallegos, Anselmo A.

2012-01-01

Diosgenin [or (22R,25R)-spirost-5-en-3β-ol] is the starting material of the Marker degradation, a cheap semi-synthesis of progesterone, which has been designated as an Inter­national Historic Chemical Landmark. Thus far, a single X-ray structure for diosgenin is known, namely its dimethyl sulfoxide solvate [Zhang et al. (2005 ▶). Acta Cryst. E61, o2324–o2325]. We have now determined the structure of the hemihydrate, C27H42O3·0.5H2O. The asymmetric unit contains two diosgenin mol­ecules, with quite similar conformations, and one water mol­ecule. Hy­droxy groups in steroids and water mol­ecules form O—H⋯O hydrogen-bonded R 5 4(10) ring motifs. Fused edge-sharing R(10) rings form a backbone oriented along [100], which aggregates the diosgenin mol­ecules in the crystal structure. PMID:22904823

The Simultaneous Electrochemical Detection of Catechol and Hydroquinone with [Cu(Sal-β-Ala)(3,5-DMPz)2]/SWCNTs/GCE

PubMed Central

Alshahrani, Lina Abdullah; Li, Xi; Luo, Hui; Yang, Linlin; Wang, Mengmeng; Yan, Songling; Liu, Peng; Yang, Yuqin; Li, Quanhua

2014-01-01

A glassy carbon electrode was modified with a copper(II) complex [Cu(Sal-β-Ala) (3,5-DMPz)2] (Sal = salicylaldehyde, β-Ala = β-alanine, 3,5-DMPz = 3,5-dimethylpyrazole) and single-walled carbon nanotubes (SWCNTs). The modified electrode was used to detect catechol (CT) and hydroquinone (HQ) and exhibited good electrocatalytic activities toward the oxidation of CT and HQ. The peak currents were linear with the CT and HQ concentrations over the range of 5–215 μmol·L−1 and 5–370 μmol·L−1 with corresponding detection limits of 3.5 μmol·L−1 and 1.46 μmol·L−1 (S/N = 3) respectively. Moreover, the modified electrode exhibited good sensitivity, stability and reproducibility for the determination of CT and HQ, indicating the promising applications of the modified electrode in real sample analysis. PMID:25429411

(E)-N′-(5-Bromo-2-hy­droxy­benzyl­idene)-2-(4-isobutyl­phen­yl)propano­hydrazide

PubMed Central

Mohamed, Shaaban K.; Horton, Peter N.; Akkurt, Mehmet; Albayati, Mustafa R.; Abdelhamid, Antar A.

2012-01-01

The title compound, C20H23BrN2O2, containing an ibuprofen core, crystallizes with three independent mol­ecules of similar conformation in the asymmetric unit. In these three mol­ecules, the two benzene rings make dihedral angles of 82.7 (2), 71.2 (2) and 78.0 (3)° with respect to each other. The atoms of the isobutyl groups in two of the mol­ecules are disordered over two positions, with site-occupancy ratios of 0.516 (8):0.484 (8) and 0.580 (8):0.420 (8). In the crystal, mol­ecules are linked by N—H⋯O, C—H⋯O and O—H⋯N hydrogen bonds. Furthermore, C—H⋯π inter­actions are also observed. PMID:22904830

Design of magnetic system to produce intense beam of polarized molecules of H2 and D2

NASA Astrophysics Data System (ADS)

Yurchenko, A. V.; Nikolenko, D. M.; Rachek, I. A.; Shestakov, Yu V.; Toporkov, D. K.; Zorin, A. V.

2017-12-01

A magnetic-separating system is designed to produce polarized molecular high-density beams of H2/D2. The distribution of the magnetic field inside the aperture of the multipole magnet was calculated using the Mermaid software package. The calculation showed that the characteristic value of the magnetic field is 40 kGs, the field gradient is about 60 kGs/cm. A numerical calculation of the trajectories of the motion of molecules with different spin projections in this magnetic system is performed. The article discusses the possibility of using the magnetic system designed for the creation of a high-intensity source of polarized molecules. The expected intensity of this source is calculated. The expected flux of molecules focused in the receiver tube is 3.5·1016 mol/s for the hydrogen molecule and 2.0·1015 mol/s for the deuterium molecule.

Determination of the molecular weight of human gamma-3 chains by polyacrylamide gel electrophoresis in the presence of sodium dodecyl sulphate

PubMed Central

Virella, G.; Parkhouse, R. M. E.

1972-01-01

The molecular weights (mol. wt) for heavy chains of human IgG were estimated by polyacrylamide gel electrophoresis in the presence of sodium dodecyl sulphate. Polyclonal IgG and monoclonal IgG proteins of different subclasses were extensively reduced with 50 mM dithioerythritol, in the presence of 2 per cent sodium dodecyl sulphate, at 100°. Four control proteins of known mol. wt (cytochrome C, chymotrypsinogen A, egg albumin, and serum albumin) were used to construct a linear plot of electrophoretic mobility versus log mol. wt. From this plot, the following mol. wts were calculated: 53,650±700 for polyclonal IgG; 54,200±1065 for γ1, γ2, and γ4 chains, and 60,950±585 for γ3 chains. Those results confirm the larger size of γ3 chains reported by Saluk and Clem (1971). PMID:4346255

The crystal structure of a new ferrocenyl P,N ligand: 1-[(2,2-di-methyl-hydrazin-1-yl-idene)meth-yl]-1'-(di-phenyl-phospho-rothio-yl)ferrocene.

PubMed

Mouas, Toma Nardjes; Daran, Jean-Claude; Merazig, Hocine; Manoury, Eric

2018-02-01

The asymmetric unit of the title compound, [Fe(C 8 H 11 N 2 )(C 17 H 14 PS)], contains two independent mol-ecules ( A and B ) with very similar conformations. Each mol-ecule is built up from a ferrocene unit substituted in the 1 and 1' positions by a protected sulfur di-phenyl-phosphine and by a di-methyl-hydrazine, -C(H)=N-N(CH 3 ) 2 , fragment. The two independent mol-ecules are linked by a C-H⋯N hydrogen bond. In the crystal, the A - B dimer is linked by a pair of C-H⋯S hydrogen bonds, forming a centrosymmetric four-mol-ecule arrangement. These units are linked by C-H⋯π inter-actions, forming a supra-molecular three-dimensional structure.

Reaction rates and prediction of thermal instability during aluminum alloy 6061 dissolution

DOE PAGES

McFarlane, J.; DePaoli, D. W.; Mattus, C. H.

2017-11-10

Here, chemical kinetics of dissolution of aluminum alloy 6061 was investigated for the processing of Pu-238 for deep space missions. The rate of dissolution was measured by the heat release and appeared to be controlled by the rate of release of Al(OH) 4 – from the metal surface. Rates of reaction were measured from 273 to 365 K, giving an activation energy of 72 ± 13 kJ•(mol Al) –1 and a pre-exponential factor of 5 ± 3 × 10 9 dm 3mol –1min –1. Minor alloying elements did not appear to affect the reaction kinetics. The average heat of dissolutionmore » was –360 ± 70 kJ•(mol NaAlO 2) –1. When extrapolated to an infinitely dilute solution of aluminum, kJ•(mol NaAlO 2) –1.« less

Quantifying Marine Emissions of Biogenic Volatile Organic Compounds Using Laboratory Measurements of Plankton Monocultures and Field Samples

NASA Astrophysics Data System (ADS)

Sabolis, A. W.; Meskhidze, N.; Kamykowski, D.; Reed, R. E.

2010-12-01

Marine biogenic volatile organic compounds (BVOCs) have been suggested to contribute significant portion of the organic carbon present in ocean atmosphere. In this study emission rates of 40 different hydrocarbons are quantified for lab-grown non-axenic phytoplankton monocultures and ambient samples from the Pamlico-Neuse Estuary, NC. The outcome of environmental conditions on production of BVOCs was examined for different light and temperature conditions. These different regimes are considered proxies for physiological stress-induced effects observed in natural ecosystems. The samples were incubated in a climate controlled room; they were then transferred to smaller volumes (200 ml) for analysis. BVOCs accumulated in the water and headspace above the water were measured by bubbling hydrocarbon-free gas mixture through the sample and passing the gas stream through a gas chromatography/mass spectrometry system equipped with a sample pre-concentrator. Inside the pre-concentrator, the compounds were trapped on a sorbent material, heated, and flushed into the GC-MS column. The pre-concentrator/GC-MS system gave at least 1000 times magnification of the sample concentrations, allowing detection of low ppt levels of hydrocarbons. Here we report results for lab-grown diatoms Thalassiosira weissflogii and Thalassiosira pseudonana, prymnesiophyte Pleurochrysis carterae, and dinoflagellates Karina brevis and Procentrum minimum, as well as field samples. To make results widely usable, all the emissions are normalized to Chlorophyll-a (Chl-a) concentration and cell counts. Our results show that diatoms had the highest isoprene production rate of 2.8 μmol (g Chl-a)-1 h-1 with ranges between 1.4 and 3.6 μmol (g Chl-a)-1 h-1 at light levels between 90 and 900 μE m-2 s-1, respectively. The prymnesiophyte and dinoflagellate species had isoprene production rates of 1.3±0.4 μmol (g Chl-a)-1 h-1 with a similar light dependency as diatoms. Field samples had comparable isoprene production rate of 3.5 μmol (g Chl-a)-1 h-1 with ranges between 0.6 and 4.1 μmol (g Chl-a)-1 h-1 for similar light levels and temperatures between 18 to 30°C. Three monoterpenes detected were α-pinene, camphene, and d-limonene. Diatoms had the highest α-pinene and d-limonene production rates of 0.045 μmol (g Chl-a)-1 h-1 and 0.015 μmol (g Chl-a)-1 h-1, respectively. The prymnesiophyte species had the highest camphene production of 0.021 μmol (g Chl-a)-1 h-1. Production rates of d-limonene and camphene did not show a well-defined light dependency, but both isoprene and α-pinene showed an increase in terpene production with increasing light intensities. Field samples show α-pinene, d-limonene, and camphene production rates of 0.05 μmol (g Chl-a)-1 h-1, 0.02 μmol (g Chl-a)-1 h-1 and 0.018 μmol (g Chl-a)-1 h-1, respectively. Field samples acclimated at 26°C had the highest terpene production rates. This study tabulates a large number of BVOC emission rates for various phytoplankton species under diverse environmental conditions.

Solution structure, mutagenesis, and NH exchange studies of the MutT enzyme-Mg 2+-8-oxo-dGMP complex

NASA Astrophysics Data System (ADS)

Massiah, M. A.; Saraswat, V.; Azurmendi, H. F.; Mildvan, A. S.

2004-08-01

The MutT pyrophosphohydrolase from E. coli (129 residues) catalyzes the hydrolysis of nucleoside triphosphates (NTP), including 8-oxo-dGTP, by substitution at Pβ, to yield NMP and pyrophosphate. The product, 8-oxo-dGMP is an unusually tight binding, slowly exchanging inhibitor with a KD=52 nM, (Δ G°=-9.8 kcal/mol) which is 6.1 kcal/mol tighter than the binding of dGMP (Δ G°=-3.7 kcal/mol). The higher affinity for 8-oxo-dGMP results from a more favorable Δ Hbinding (-32 kcal/mol) despite an unfavorable - TΔ S° binding (+22 kcal/mol). The solution structure of the MutT-Mg 2+-8-oxo-dGMP complex shows a narrowed, hydrophobic nucleotide-binding cleft with Asn-119 and Arg-78 among the few polar residues. The N119A, N119D, R78K and R78A single mutations, and the R78K+N119A double mutant all showed largely intact active sites, on the basis of small changes in the kinetic parameters of dGTP hydrolysis and in 1H- 15N HSQC spectra. However, the N119A mutation profoundly weakened the active site binding of 8-oxo-dGMP by 4.3 kcal/mol (1650-fold). The N119D mutation also weakened 8-oxo-dGMP binding but only by 2.1 kcal/mol (37-fold), suggesting that Asn-119 functioned both as a hydrogen bond donor to C8O, and a hydrogen bond acceptor from N7H of 8-oxo-dGMP, while aspartate at position -119 functioned as an acceptor of a single hydrogen bond. Much smaller weakening effects (0.3-0.4 kcal/mol) on the binding of dGMP and dAMP were found, indicating specific hydrogen bonding of Asn-119 to 8-oxo-dGMP. While formation of the wild type MutT-Mg 2+-8-oxo-dGMP complex slowed the backbone NH exchange rates of 45 residues distributed throughout the protein, the same complex of the N119A mutant slowed the exchange rates of only 11 residues at or near the active site, indicating an increase in conformational flexibility of the N119A mutant. The R78K and R78A mutations weakened the binding of 8-oxo-dGMP by 1.7 and 1.1 kcal/mol, respectively, indicating a lesser role of Arg-78 than of Asn-119 in the selective binding of 8-oxo-dGMP, likely donating a single hydrogen bond to its C6O. The R78K+N119A double mutant weakened the binding of 8-oxo-dGMP ( KIslope=3.1 mM) by 6.5±0.2 kcal/mol which overlaps, within error with the sum of the effects of the two single mutants (6.0±0.3 kcal/mol). Such additive effects of the two single mutants in the double mutant are most simply explained by the independent functioning of Asn-119 and Arg-78 in the binding of 8-oxo-dGMP. Independent functioning of these two residues in nucleotide binding is consistent with their locations in the MutT-Mg 2+-8-oxo-dGMP complex, on opposite sides of the active site cleft, with a distance of 8.4±0.5 Å between their side chain nitrogens.

Structural Dynamics in Metal Tris-hydroxyquinolines: Interconversion of Meridianal and Facial Alq3 Isomers

NASA Astrophysics Data System (ADS)

Ferris, Kim; Sapochak, Linda; Burrows, Paul; Rodovsky, Deanna; Marmolejo, Theresa

2004-03-01

While previous work investigating the charge transport properties of Alq3 has indicated that the meridianal (mer) conformation of Alq3 is predominant species, recent work suggesting identification of a facial (fac) form raises again the question of heterogeneity. Electronic structure computations from our group have noted that the energy difference(in parenthesis) between the mer and fac conformations is highly sensitive to basis set description (8.6 kcal/mol//3-21g*/SCF; 6.9 kcal/mol//6-31g*/SCF), electron correlation (6.0 kcal/mol//3-21g*/MP2; 4.7 kcal/mol//6-31g*/MP2), and solvent effects (4.4 kcal/mol/3-21g*/SCF/DMSO). Given these small energy differences, we have conducted a series of Hartree-Fock and first principles electronic structure computations on the interconversion of these structural forms, and will report on the structural and energetic aspects of the transformation. The likely reaction path involves lengthening of the Al-N bond to the point where a pentacoordinate intermediate or transition state would be formed, followed by flipping of the ligand through rotation around the Al-O bond. Following Schmidbauer's earlier work, we note that transformation involving only one ligand will actually lead to a facial isomer. Preliminary characterization of this transition state suggests that the activation energy is approximately 20-25 kcal/mol above the mer conformation. The authors gratefully acknowledge financial support from PNNL Laboratory Directed Research and Development Project and the U.S. Department of Energy, Office of Science, Materials Sciences Division.

Preliminary evaluation of monolithic column high-performance liquid chromatography with tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence detection for the determination of quetiapine in human body fluids.

PubMed

Bellomarino, Sara A; Brown, Allyson J; Conlan, Xavier A; Barnett, Neil W

2009-03-15

High-performance liquid chromatography (HPLC) with tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence detection methodology is reported for the determination of the atypical antipsychotic drug quetiapine and the observation of its major active and inactive metabolites in human urine and serum. The method uses a monolithic chromatographic column allowing high flow rates of 3 mLmin(-1) enabling rapid quantification. Flow injection analysis (FIA) with tris(2,2'-bipyridyl)ruthenium(II) chemiluminescence detection and HPLC time of flight mass spectrometry (TOF-MS) were used for the determination of quetiapine in a pharmaceutical preparation to establish its suitability as a calibration standard. The limit of detection achieved with FIA was 2 x 10(-11) molL(-1) in simple aqueous solution. The limits of detection achieved with HPLC were 7 x 10(-8) and 2 x 10(-10) molL(-1) in urine and serum, respectively. The calibration range for FIA was between 5 x 10(-9) and 1 x 10(-6) molL(-1). The calibration ranges for HPLC were between 1 x 10(-7)-1 x 10(-4) and 1 x 10(-8)-1 x 10(-4) molL(-1) in urine and serum, respectively. The quetiapine concentrations in patient samples were found to be 3 x 10(-6) molL(-1) in urine and 7 x 10(-7) molL(-1) in serum. Without the need for preconcentration, the HPLC detection limits compared favourably with those in previously published methodologies. The metabolites were identified using HPLC-TOF-MS.

Mechanism of atomic layer deposition of SiO2 on the silicon (100)-2×1 surface using SiCl4 and H2O as precursors

NASA Astrophysics Data System (ADS)

Kang, Jeung Ku; Musgrave, Charles B.

2002-03-01

We use density functional theory to investigate atomic layer deposition (ALD) mechanism of silicon dioxide on the Si(100)-2×1 surface from the precursors SiCl4 and H2O. First, we explore the reaction mechanism of water with the bare Si(100)-2×1 surface to produce surface hydroxyl groups. We find that this reaction proceeds through a two-step pathway with an overall barrier of 33.3 kcal/mol. Next, we investigate the ALD mechanism for the binary reaction sequence: the SiCl4 half reaction and the H2O half reaction. For the SiCl4 half reaction, SiCl4 first forms a σ-bond with the oxygen of the surface OH group and then releases an HCl molecule. The predicted barrier for this process is 15.8 kcal/mol. Next, adsorbed SiCl3 reacts with a neighboring OH group to form bridged SiCl2 with a barrier of 22.6 kcal/mol. The H2O half reaction also proceeds through two sequential steps with an overall barrier of 19.1 kcal/mol for the reaction of H2O with bridged SiCl2 to form bridged Si(OH)2. The predicted barrier of 22.6 kcal/mol for the rate-limiting step of the ALD binary reaction mechanism is consistent with the experimental value of 22.0 kcal/mol. In addition, we find that the calculated frequencies are in good agreement with the experimentally measured IR spectra.

Highly Efficient Catalytic Hydrogen Evolution from Ammonia Borane Using the Synergistic Effect of Crystallinity and Size of Noble-Metal-Free Nanoparticles Supported by Porous Metal-Organic Frameworks.

PubMed

Liu, Penglong; Gu, Xiaojun; Kang, Kai; Zhang, Hao; Cheng, Jia; Su, Haiquan

2017-03-29

A series of nonprecious metal nanoparticles (NPs) supported by metal-organic framework MIL-101 were synthesized using four methods and their catalytic performance on hydrogen evolution from ammonia borane (NH 3 BH 3 ) was studied. The results showed that the crystalline Co NPs with size of 4.5-8.5 and 14.5-24.5 nm had low activities featuring the total turnover frequency (TOF) values of 9.9 and 4.5 mol H2 mol cat -1 min -1 , respectively. In contrast, the amorphous Co NPs with size of 1.6-2.6 and 13.5-24.5 nm exhibited high activities featuring the total TOF values of 51.4 and 22.3 mol H2 mol cat -1 min -1 , respectively. The remarkably different activities could be ascribed to the different crystallinity and size of Co NPs in the catalysts. Moreover, the ultrasound-assisted in situ method was also successfully applied to bimetallic systems, and MIL-101-supported amorphous CuCo, FeCo and NiCo NPs had the catalytic activities with total TOF values of 51.7, 50.8, and 44.3 mol H2 mol cat -1 min -1 , respectively, which were the highest in the values of the reported non-noble metal Co-based catalysts. The present approach, namely, using the synergistic effect of crystallinity and size of metal NPs, may offer a new prospect for high-performance and low-cost nanocatalysts.

3-{(E)-[4-(4-Hy-droxy-3-meth-oxy-phen-yl)butan-2-yl-idene]amino}-1-phenyl-urea: crystal structure and Hirshfeld surface analysis.

PubMed

Tan, Ming Yueh; Crouse, Karen A; Ravoof, Thahira B S A; Jotani, Mukesh M; Tiekink, Edward R T

2018-01-01

Two independent mol-ecules ( A and B ) comprise the asymmetric unit of the title compound, C 18 H 21 N 3 O 3 . The urea moiety is disubstituted with one amine being linked to a phenyl ring, which is twisted out of the plane of the CN 2 O urea core [dihedral angles = 25.57 (11) ( A ) and 29.13 (10)° ( B )]. The second amine is connected to an imine ( E conformation), which is linked in turn to an ethane bridge that links a disubstituted benzene ring. Intra-molecular amine-N-H⋯N(imine) and hydroxyl-O-H⋯O(meth-oxy) hydrogen bonds close S (5) loops in each case. The mol-ecules have twisted conformations with the dihedral angles between the outer rings being 38.64 (81) ( A ) and 48.55 (7)° ( B ). In the crystal, amide-N-H⋯O(amide) hydrogen bonds link the mol-ecules A and B via an eight-membered {⋯HNCO} 2 synthon. Further associations between mol-ecules, leading to supra-molecular layers in the ac plane, are hydrogen bonds of the type hydroxyl-O-H⋯N(imine) and phenyl-amine-N-H⋯O(meth-oxy). Connections between layers, leading to a three-dimensional architecture, comprise benzene-C-H⋯O(hy-droxy) inter-actions. A detailed analysis of the calculated Hirshfeld surfaces shows mol-ecules A and B participate in very similar inter-molecular inter-actions and that any variations relate to conformational differences between the mol-ecules.

Possible role of organic peroxides in the detection of irradiated food

NASA Astrophysics Data System (ADS)

Shengchu, Qi; Jilan, Wu; Yan, Zhu

1993-07-01

In order to determine the level of organic peroxides induced by autooxidation, random sampling of pork has been performed with ˜ 300 analytical data. The organic peroxide content in unirradiated pork has been estimated as (5.4±3.0)X10 -5mol.kg -1. The dependence of yield of peroxide in pork, minced meat and braised chicken on absorbed dose has been investigated. For killing trichinae 0.5˜1 kGy is used, the quantity of peroxide in pork will be 2X10 -4mol.kg -1 (or 4X10 -4 mol.kg -1 for 1 kGy), which is 3.7˜7.4 times greater than the background. If 3 kGy is used to eliminate Samonella, the quantity of peroxides in pork will be 1.3X10 -3mol.kg -1., which approaches 24 times greater than the average value of background. When minced meat was irradiated in the presence of air, a chain reaction takes place with G (organic peroxides) value 30.2. Radiation processing dose of braised chicken for shelf-life extension is ˜ 9kGy, organic peroxide content in braised chicken fat is 32.5X10 -4mol.kg -1, which is about 14.7 times greater than average value (2.2X10 -4mol.kg -1) in unirradiated one. Applying peroxide method to qualitatively detect the irradiated food containing fat is satisfactory. Recombining with measuring ESR signal of irradiated bone will cause the method of detection more accurate and perfect.

Nitrogenase from the photosynthetic bacterium Rhodopseudomonas capsulata: purification and molecular properties.

PubMed Central

Hallenbeck, P C; Meyer, C M; Vignais, P M

1982-01-01

Nitrogenase proteins were isolated from cultures of the photosynthetic bacterium Rhodopseudomonas capsulata grown on a limiting amount of ammonia. Under these conditions, the nitrogenase N2ase A was active in vivo, and nitrogenase activity in vitro was not dependent upon manganese and the activating factor. The nitrogenase proteins were also isolated from nitrogen-limited cultures in which the in vivo nitrogenase activity had been stopped by an ammonia shock. This nitrogenase activity, N2ase R, showed an in vitro requirement for manganese and the activating factor for maximal activity. The Mo-Fe protein (dinitrogenase) was composed of two dissimilar subunits with molecular weights of 55,000 and 59,500; the Fe protein (dinitrogenase reductase), from either type of culture, was composed of a single subunit (molecular weight), 33,500). The metal and acid labile sulfur contents of both nitrogenase proteins were similar to those found for previously isolated nitrogenases. The Fe proteins from both N2ase A and N2ase R contained phosphate and ribose, 2 mol of each per mol of N2ase R Fe protein and about 1 mol of each per mol of N2ase A Fe protein. The greatest difference between the two types of Fe protein was that the N2ase R Fe protein contained about 1 mol per mol of an adenine-like molecule, whereas the N2ase A Fe protein content of this compound was insignificant. These results are compared with various models previously presented for the short-term regulation of nitrogenase activity in the photosynthetic bacteria. PMID:6799495

Observation and estimation of photosynthetically active radiation in Lhasa (Tibetan Plateau)

NASA Astrophysics Data System (ADS)

Peng, Simao; Du, Qingyun; Lin, Aiwen; Hu, Bo; Xiao, Ke; Xi, Yuliang

2015-03-01

In this study, we measured photosynthetically active radiation (PAR) and global solar radiation (G) in Lhasa, located on the Tibetan Plateau, from 2006 to 2012 to examine the PAR and PAR/G (PAR fraction) seasonal characteristics. The maximum and minimum values of both PAR and the PAR fraction occurred in summer and winter, respectively. Moreover, the PAR and PAR fraction annual averages were 38.64 mol m-2 d-1 and 1.84 mol M J-1, respectively. An efficient all-weather model used for estimating PAR under various sky conditions was developed based on the relationships among PAR, the cosine of the solar zenith angle and the clearness index in Lhasa. The model also produced acceptable estimations of PAR with high accuracy at the Donghu and Sanjiang weather stations. A PAR dataset was reconstructed from G using the newly developed model for the period 1961-2012. The modelled annual mean daily PAR was approximately 37.62 mol m-2 d-1. A significant decreasing trend (-0.61 mol m-2 per decade) over the last 50 years was observed on the Tibetan Plateau; this decrease was largest in autumn (-1.024 mol m-2 per decade), and relatively small decreases were observed in summer. The results also revealed that PAR began increasing at 0.164 mol m-2 per year from 1991 to 2012, which was inconsistent with the variations of G. The proposed all-weather PAR model could be useful for ecological modelling and agricultural processes in the Tibetan Plateau region of China.

Marginal Ascorbate Status (Hypovitaminosis C) Results in an Attenuated Response to Vitamin C Supplementation.

PubMed

Carr, Anitra C; Pullar, Juliet M; Bozonet, Stephanie M; Vissers, Margreet C M

2016-06-03

Inadequate dietary intake of vitamin C results in hypovitaminosis C, defined as a plasma ascorbate concentration ≤23 μmol/L. Our objective was to carry out a retrospective analysis of two vitamin C supplementation studies to determine whether supplementation with 50 mg/day vitamin C is sufficient to restore adequate ascorbate status (≥50 μmol/L) in individuals with hypovitaminosis C. Plasma ascorbate data from 70 young adult males, supplemented with 50 or 200 mg/day vitamin C for up to six weeks, was analyzed. Hypovitaminosis C status was identified based on plasma ascorbate being ≤23 μmol/L and the response of these individuals to vitamin C supplementation was examined. Of the participants consuming 50 mg/day vitamin C for up to six weeks, those with hypovitaminosis C at baseline achieved plasma concentrations of only ~30 μmol/L, whereas the remainder reached ~50 μmol/L. Participants who consumed 200 mg/day vitamin C typically reached saturating concentrations (>65 μmol/L) within one week, while those with hypovitaminosis C required two weeks to reach saturation. Regression modelling indicated that the participants' initial ascorbate status and body weight explained ~30% of the variability in the final ascorbate concentration. Overall, our analysis revealed that supplementation with 50 mg/day vitamin C, which resulted in a total dietary vitamin C intake of 75 mg/day, was insufficient to achieve adequate plasma ascorbate concentrations in individuals with hypovitaminosis C. Furthermore, increased body weight had a negative impact on ascorbate status.

Quantum chemical ab initio prediction of proton exchange barriers between CH{sub 4} and different H-zeolites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tuma, Christian; Sauer, Joachim, E-mail: js@chemie.hu-berlin.de

2015-09-14

A hybrid MP2:DFT (second-order Møller–Plesset perturbation theory–density functional theory) method that combines MP2 calculations for cluster models with DFT calculations for the full periodic structure is used to localize minima and transition structures for proton jumps at different Brønsted sites in different frameworks (chabazite, faujasite, ferrierite, and ZSM-5) and at different crystallographic positions of a given framework. The MP2 limit for the periodic structures is obtained by extrapolating the results of a series of cluster models of increasing size. A coupled-cluster (CCSD(T)) correction to MP2 energies is calculated for cluster models consisting of three tetrahedra. For the adsorption energies, thismore » difference is small, between 0.1 and 0.9 kJ/mol, but for the intrinsic proton exchange barriers, this difference makes a significant (10.85 ± 0.25 kJ/mol) and almost constant contribution across different systems. The total values of the adsorption energies vary between 22 and 34 kJ/mol, whereas the total proton exchange energy barriers fall in the narrow range of 152–156 kJ/mol. After adding nuclear motion contributions (harmonic approximation, 298 K), intrinsic enthalpy barriers between 134 and 141 kJ/mol and apparent energy barriers between 105 and 118 kJ/mol are predicted for the different sites examined for the different frameworks. These predictions are consistent with experimental results available for faujasite, ferrierite, and ZSM-5.« less

Response of Photosynthesis and Yield of Sweetpotato and Peanut to Super-optimal CO2 levels

NASA Astrophysics Data System (ADS)

Bonsi, C.; Bullard, J.; Hileman, D.; Mortley, D.; Hill, J.; Hill, W.; Morrris, C.

The fate of persons involved in long-term space travel and habitation will depend greatly on the ability to provide food and a livable environment for them In the National Aeronautics and Space Administration NASA Advanced Life Support ALS program photosynthesis of higher plants will be utilized to provide food and oxygen while removing carbon dioxide produced by humans and other heterotrophs as well as transpiring water that can be recycled for drinking This plant-mediated process is collectively referred to as Bioregenerative Life Support Carbon dioxide concentrations on board a space shuttle cabin atmosphere range between 4000 and 6000 mu mol mol -1 CO 2 but with large crews may exceed 10 000- mu mol mol -1 CO 2 Thus it is critical to evaluate the responses of candidate crops to super optimal levels of CO 2 Soybean and potato have been exposed to CO 2 concentrations up to 5000 and 10 000- mu mol mol -1 Very little research has been published about the effects of super-optimal CO 2 levels on sweetpotato and peanut growth and physiology thus indicating a need for extensive research on these plants The aim of this study was to evaluate the effects of super-optimal CO 2 enrichment on growth of TU-82-155 sweetpotato and Georgia Red peanut in a Microporous Tube Membrane MPT using Turface Media and Nutrient Film Technique NFT nutrient delivery systems Sweetpotato Ipomoea batatas L Lam and peanut Arachis hypogaea L were exposed to three CO 2 levels of 400

Bleeding tendency in dual antiplatelet therapy with aspirin/clopidogrel: rescue of the template bleeding time in a single-center prospective study

PubMed Central

2012-01-01

Background Patients with heightened platelet reactivity in response to antiplatelet agents are at an increased risk of recurrent ischemic events. However, there is a lack of diagnostic criteria for increased response to combined aspirin/clopidogrel therapy. The challenge is to identify patients at risk of bleeding. This study sought to characterize bleeding tendency in patients treated with aspirin and clopidogrel. Patients/methods In a single-center prospective study, 100 patients under long-term aspirin/clopidogrel treatment, the effect of therapy was assayed by template bleeding time (BT) and the inhibition of platelet aggregation (IPA) by light transmission aggregometry (LTA). Arachidonic acid (0.625 mmol/L) and adenosine diphosphate (ADP; 2, 4, and 8 μmol/L) were used as platelet agonists. Results Bleeding episodes (28 nuisance, 2 hematuria [1 severe], 1 severe proctorrhagia, 1 severe epistaxis) were significantly more frequent in patients with longer BT. Template BT ≥ 24 min was associated with bleeding episodes (28 of 32). Risk of bleeding increased 17.4% for each 1 min increase in BT. Correlation was found between BT and IPAmax in response to ADP 2 μmol/L but not to ADP 4 or 8 μmol/L. Conclusion In patients treated with dual aspirin/clopidogrel therapy, nuisance and internal bleeding were significantly associated with template BT and with IPAmax in response to ADP 2 μmol/L but not in response to ADP 4 μmol/L or 8 μmol/L. PMID:22236361

Photosynthetic Response of Soybean to Microclimate in 26-Year-Old Tree-Based Intercropping Systems in Southern Ontario, Canada.

PubMed

Peng, Xiaobang; Thevathasan, Naresh V; Gordon, Andrew M; Mohammed, Idris; Gao, Pengxiang

2015-01-01

In order to study the effect of light competition and microclimatic modifications on the net assimilation (NA), growth and yield of soybean (Glycine max L.) as an understory crop, three 26-year-old soybean-tree (Acer saccharinum Marsh., Populus deltoides X nigra, Juglans nigra L.) intercropping systems were examined. Tree competition reduced photosynthetically active radiation (PAR) incident on soybeans and reduced net assimilation, growth and yield of soybean. Soil moisture of 20 cm depth close (< 3 m) to the tree rows was also reduced. Correlation analysis showed that NA and soil water content were highly correlated with growth and yield of soybean. When compared with the monoculture soybean system, the relative humidity (RH) of the poplar-soybean, silver maple-soybean, and black walnut-soybean intercropped systems was increased by 7.1%, 8.0% and 5.9%, soil water content was reduced by 37.8%, 26.3% and 30.9%, ambient temperature was reduced by 1.3°C, 1.4°C and 1.0°C, PAR was reduced by 53.6%, 57.9% and 39.9%, and air CO2 concentration was reduced by 3.7μmol·mol(-1), 4.2μmol·mol(-1) and 2.8μmol·mol(-1), respectively. Compared to the monoculture, the average NA of soybean in poplar, maple and walnut treatments was also reduced by 53.1%, 67.5% and 46.5%, respectively. Multivariate stepwise regression analysis showed that PAR, ambient temperature and CO2 concentration were the dominant factors influencing net photosynthetic rate.

Photosynthetic Response of Soybean to Microclimate in 26-Year-Old Tree-Based Intercropping Systems in Southern Ontario, Canada

PubMed Central

Peng, Xiaobang; Thevathasan, Naresh V.; Gordon, Andrew M.; Mohammed, Idris; Gao, Pengxiang

2015-01-01

In order to study the effect of light competition and microclimatic modifications on the net assimilation (NA), growth and yield of soybean (Glycine max L.) as an understory crop, three 26-year-old soybean-tree (Acer saccharinum Marsh., Populus deltoides X nigra, Juglans nigra L.) intercropping systems were examined. Tree competition reduced photosynthetically active radiation (PAR) incident on soybeans and reduced net assimilation, growth and yield of soybean. Soil moisture of 20 cm depth close (< 3 m) to the tree rows was also reduced. Correlation analysis showed that NA and soil water content were highly correlated with growth and yield of soybean. When compared with the monoculture soybean system, the relative humidity (RH) of the poplar-soybean, silver maple-soybean, and black walnut-soybean intercropped systems was increased by 7.1%, 8.0% and 5.9%, soil water content was reduced by 37.8%, 26.3% and 30.9%, ambient temperature was reduced by 1.3°C, 1.4°C and 1.0°C, PAR was reduced by 53.6%, 57.9% and 39.9%, and air CO2 concentration was reduced by 3.7μmol·mol-1, 4.2μmol·mol-1 and 2.8μmol·mol-1, respectively. Compared to the monoculture, the average NA of soybean in poplar, maple and walnut treatments was also reduced by 53.1%, 67.5% and 46.5%, respectively. Multivariate stepwise regression analysis showed that PAR, ambient temperature and CO2 concentration were the dominant factors influencing net photosynthetic rate. PMID:26053375

Dual add-on therapy in type 2 diabetes poorly controlled with metformin monotherapy: a randomized double-blind trial of saxagliptin plus dapagliflozin addition versus single addition of saxagliptin or dapagliflozin to metformin.

PubMed

Rosenstock, Julio; Hansen, Lars; Zee, Pamela; Li, Yan; Cook, William; Hirshberg, Boaz; Iqbal, Nayyar

2015-03-01

This study compared the efficacy and safety of dual add-on of saxagliptin plus dapagliflozin versus saxagliptin and dapagliflozin added on alone in patients with type 2 diabetes poorly controlled with metformin. This was a double-blind trial in adults with HbA1c ≥8.0% and ≤12.0% (64-108 mmol/mol), randomized to saxagliptin (SAXA) (5 mg/day) plus dapagliflozin (DAPA) (10 mg/day; n = 179), or SAXA (5 mg/day) and placebo (n = 176), or DAPA (10 mg/day) and placebo (n = 179) on background metformin extended release (MET) ≥1,500 mg/day. Primary objective compared changes from baseline in HbA1c with SAXA+DAPA+MET versus SAXA+MET and DAPA+MET. Patients had a mean baseline HbA1c of 8.9% (74 mmol/mol), diabetes duration of 7.6 years, and a BMI of 32 kg/m(2). At week 24, the adjusted mean change from the baseline HbA1c was -1.5% (-16.1 mmol/mol) with SAXA+DAPA+MET versus -0.9% (-9.6 mmol/mol) with SAXA+MET (difference -0.59% [-6.4 mmol/mol], P < 0.0001) and -1.2% (-13.1 mmol/mol) with DAPA+MET (difference -0.27% [3.0 mmol/mol], P < 0.02). The proportion of patients achieving HbA1c <7% (53 mmol/mol) was 41% with SAXA+DAPA+MET versus 18% with SAXA+MET and 22% with DAPA+MET. Urinary and genital infections occurred in ≤1% of patients receiving SAXA+DAPA+MET. Hypoglycemia was infrequent, with no episodes of major hypoglycemia. In this first report of adding a well-tolerated combination of saxagliptin plus dapagliflozin to background metformin therapy in patients poorly controlled with metformin, greater improvements in glycemic control were obtained with triple therapy by the dual addition of saxagliptin and dapagliflozin than dual therapy with the addition of saxagliptin or dapagliflozin alone. © 2015 by the American Diabetes Association. Readers may use this article as long as the work is properly cited, the use is educational and not for profit, and the work is not altered.

Eliminating a global regulator of carbon catabolite repression enhances the conversion of aromatic lignin monomers to muconate in Pseudomonas putida KT2440

DOE PAGES

Johnson, Christopher W.; Abraham, Paul E.; Linger, Jeffrey G.; ...

2017-05-31

Carbon catabolite repression refers to the preference of microbes to metabolize certain growth substrates over others in response to a variety of regulatory mechanisms. Such preferences are important for the fitness of organisms in their natural environments, but may hinder their performance as domesticated microbial cell factories. In a Pseudomonas putida KT2440 strain engineered to convert lignin-derived aromatic monomers such as p-coumarate and ferulate to muconate, a precursor to bio-based nylon and other chemicals, metabolic intermediates including 4-hydroxybenzoate and vanillate accumulate and subsequently reduce productivity. We hypothesized that these metabolic bottlenecks may be, at least in part, the effect ofmore » carbon catabolite repression caused by glucose or acetate, more preferred substrates that must be provided to the strain for supplementary energy and cell growth. Using mass spectrometry-based proteomics, we have identified the 4-hydroxybenzoate hydroxylase, PobA, and the vanillate demethylase, VanAB, as targets of the Catabolite Repression Control (Crc) protein, a global regulator of carbon catabolite repression. By deleting the gene encoding Crc from this strain, the accumulation of 4-hydroxybenzoate and vanillate are reduced and, as a result, muconate production is enhanced. In cultures grown on glucose, the yield of muconate produced from p-coumarate after 36 h was increased nearly 70% with deletion of the gene encoding Crc (94.6 ± 0.6% vs. 56.0 ± 3.0% (mol/mol)) while the yield from ferulate after 72 h was more than doubled (28.3 ± 3.3% vs. 12.0 ± 2.3% (mol/mol)). The effect of eliminating Crc was similar in cultures grown on acetate, with the yield from p-coumarate just slightly higher in the Crc deletion strain after 24 h (47.7 ± 0.6% vs. 40.7 ± 3.6% (mol/mol)) and the yield from ferulate increased more than 60% after 72 h (16.9 ± 1.4% vs. 10.3 ± 0.1% (mol/mol)). In conclusion, these results are an example of the benefit that reducing carbon catabolite repression can have on conversion of complex feedstocks by microbial cell factories, a concept we posit could be broadly considered as a strategy in metabolic engineering for conversion of renewable feedstocks to value-added chemicals.« less

Dissolution of Nickel Ferrite in Aqueous Solutions Containing Oxalic Acid and Ferrous Salts.

PubMed

Figueroa, Carlos A.; Sileo, Elsa E.; Morando, Pedro J.; Blesa, Miguel A.

2000-05-15

The dissolution of nickel ferrite in oxalic acid and in ferrous oxalate-oxalic acid aqueous solution was studied. Nickel ferrite was synthesized by thermal decomposition of a mixed tartrate; the particles were shown to be coated with a thin ferric oxide layer. Dissolution takes place in two stages, the first one corresponding to the dissolution of the ferric oxide outer layer and the second one being the dissolution of Ni(1.06)Fe(1.96)O(4). The kinetics of dissolution during this first stage is typical of ferric oxides: in oxalic acid, both a ligand-assisted and a redox mechanism operates, whereas in the presence of ferrous ions, redox catalysis leads to a faster dissolution. The rate dependence on both oxalic acid and on ferrous ion is described by the Langmuir-Hinshelwood equation; the best fitting corresponds to K(1)(ads)=25.6 mol(-1) dm(-3) and k(1)(max)=9.17x10(-7) mol m(-2) s(-1) and K(2)(ads)=37.1x10(3) mol(-1) dm(-3) and k(2)(max)=62.3x10(-7) mol m(-2) s(-1), respectively. In the second stage, Langmuir-Hinshelwood kinetics also describes the dissolution of iron and nickel from nickel ferrite, with K(1)(ads)=20.8 mol(-1) dm(3) and K(2)(ads)=1.16x10(5) mol(-1) dm(3). For iron, k(1)(max)=1.02x10(-7) mol of Fe m(-2) s(-1) and k(2)(max)=2.38x10(-7) mol of Fe m(-2) s(-1); for nickel, the rate constants k(1)(max) and k(2)(max) are 2.4 and 1.79 times smaller, respectively. The factor 1.79 agrees nicely with the stoichiometric ratio, whereas the factor 2.4 implies the accumulation of some nickel in the residual particles. The rate of nickel dissolution in oxalic acid is higher than that in bunsenite by a factor of 8, whereas hematite is more reactive by a factor of 9 (in the absence of Fe(II)) and 27 (in the presence of Fe (II)). It may be concluded that oxalic acid operates to dissolve iron, and the ensuing disruption of the solid framework accelerates the release of nickel. Copyright 2000 Academic Press.

Success Rates in a Diabetes Specialist Nurse-Led Education Programme: Re-setting the Glucostat.

PubMed

Heald, A H; Anderson, S G; Khan, A; Stocker, J; Davies, S; Bliss, K; Livingston, M; Donnelly, P

2017-05-01

Analysis of National Diabetes Audit data from 2011-2012 of newly diagnosed people with type 1 diabetes mellitus (DM) found low initial success rates in much of the UK at 20% on initial training, while an unusually high success rate of 75% achieving target HbA1C<58 mmol/mol (< 7.5%) was found in Cheshire (England average=40.8%). We present a review of the approach taken by the Cheshire Diabetes team in the 12 months following diagnosis. Between 2012 and 2013, 15 consecutive newly diagnosed people with type 1 DM were followed up for 18 months. All received support and advice by community Diabetes Specialist Nurses (DSNs) and Dieticians covering Central and Eastern Cheshire, UK. Mean±SD age at diagnosis was 23±3 years. The period of contact with the DSN service varied from 7-12 weeks. Baseline HbA1C of 99 mmol/mol [11.2%] (95% CI: 86-111 mmol/mol [10.0-12.3%]) declined by ~50% to 49 mmol/mol [6.6%] (41-57 mmol/mol [5.9-7.4%]; F=16.9, p<0.001) at 6 months and did not change between 6-12 months. Of those newly diagnosed with type 1 DM, 84.6% achieved a target HbA1C<58 mmol/mol (<7.5%) and 61.5% met a target<48 mmol/mol (<6.5%). There was no significant weight change during the study. The key elements of this bio-psycho-social approach by the DSN team included providing psychological support, patient engagement, demonstrating positive regard, gaining trust, identifying health-seeking behaviour, providing key decision-making skills and developing a self-management plan. This resulted in improvements in overall glycaemic control well above the national average without untoward weight gain. The UK National Diabetes Audit (2011-2012) in newly diagnosed type 1 diabetics in Cheshire, UK, showed a success rate at 6 months post-diagnosis of 75% achieving a target HbA1C<58 mmol/mol (<7.5%) compared with the national average of 40.8%. Initially thought to be erroneous, these excellent results were confirmed. The approach taken to achieve them is herein described. © Georg Thieme Verlag KG Stuttgart · New York.

Quantum theory of atoms in molecules/charge-charge flux-dipole flux models for fundamental vibrational intensity changes on H-bond formation of water and hydrogen fluoride

DOE Office of Scientific and Technical Information (OSTI.GOV)

Silva, Arnaldo F.; Richter, Wagner E.; Bruns, Roy E., E-mail: bruns@iqm.unicamp.br

The Quantum Theory of Atoms In Molecules/Charge-Charge Flux-Dipole Flux (QTAIM/CCFDF) model has been used to investigate the electronic structure variations associated with intensity changes on dimerization for the vibrations of the water and hydrogen fluoride dimers as well as in the water-hydrogen fluoride complex. QCISD/cc-pVTZ wave functions applied in the QTAIM/CCFDF model accurately provide the fundamental band intensities of water and its dimer predicting symmetric and antisymmetric stretching intensity increases for the donor unit of 159 and 47 km mol{sup −1} on H-bond formation compared with the experimental values of 141 and 53 km mol{sup −1}. The symmetric stretching ofmore » the proton donor water in the dimer has intensity contributions parallel and perpendicular to its C{sub 2v} axis. The largest calculated increase of 107 km mol{sup −1} is perpendicular to this axis and owes to equilibrium atomic charge displacements on vibration. Charge flux decreases occurring parallel and perpendicular to this axis result in 42 and 40 km mol{sup −1} total intensity increases for the symmetric and antisymmetric stretches, respectively. These decreases in charge flux result in intensity enhancements because of the interaction contributions to the intensities between charge flux and the other quantities. Even though dipole flux contributions are much smaller than the charge and charge flux ones in both monomer and dimer water they are important for calculating the total intensity values for their stretching vibrations since the charge-charge flux interaction term cancels the charge and charge flux contributions. The QTAIM/CCFDF hydrogen-bonded stretching intensity strengthening of 321 km mol{sup −1} on HF dimerization and 592 km mol{sup −1} on HF:H{sub 2}O complexation can essentially be explained by charge, charge flux and their interaction cross term. Atomic contributions to the intensities are also calculated. The bridge hydrogen atomic contributions alone explain 145, 237, and 574 km mol{sup −1} of the H-bond stretching intensity enhancements for the water and HF dimers and their heterodimer compared with total increments of 149, 321, and 592 km mol{sup −1}, respectively.« less

[Proapoptotic effect of angiotensin II on renal tubular epithelial cells and protective effect of Cordyceps sinensis].

PubMed

Tu, Shan; Zhou, Qiaoling; Tang, Rong; Tang, Tianfeng; Hu, Sai; Ao, Xiang

2012-01-01

To investigate the mechanism of the protective effect of Cordyceps sinensis (C. sinensis) on the apoptosis of cultured NRK-52E induced by angiotension II (AngII). NRK-52E cells were incubated with C. sinensis (0, 5, 10, 20, and 40 mg/L) and 10(-8) mol/ L AngII for 24, 48, 72 h. The optimal concentration of C. sinensis was selected. Either NRK-52E cells were incubated with different doses of AngII (0, 10(-12), 10(-10), 10(-8), and 10(-6) mol/L) for 24 h, or with 10(-8) mol/L AngII for 24, 48, and 72 h, to observe the effect of AngII on the apoptosis of NRK- 52E cells. The optimal concentration and time of AngII were selected. In another experiment cells were divided into 5 groups: a control, AngII (10(-8) mol/L), AngII (10(-8) mol/L)+ C. sinensis (40 mg/ L), Ang II (10(-8) mol/L)+ fosinopril (10(-5) mmol/L), and Ang II (10(-8) mol/L)+ fosinopril (10(-5) mol/ L)+C. sinensis (40 mg/L). MTT assay was used to test the changes in the proliferation of NRK-52E cultured with different concentration of C. sinensis for 24, 48, 72 h. The Annecxin V-FITC and PI stainings were applied to detect the apoptosis rate induced by AngII by flow cytometer (FCM) and to determine the eddects of C. sinensis. The activity of caspase-3 was assayed by spectrophotometry. Certain concentrations of C. sinensis (10-40 mg/L) promoted the proliferation of NRK- 52E cells inhibited by AngII(P<0.05). AngII induced the apoptosis of NRK-52E in a dose and timedependent manner, accompanied with increased activity of caspase-3 (P<0.05). C. sinensis partially suppressed the apoptosis of NRK-52E induced by AngII, and declined the activity of caspase-3 (P<0.05). No significant difference was shown as between the fosinopril group and the fosinopril+C. sinensis group (P>0.05). C. sinensis can suppress the apoptosis of NRK-52E by AngII, and the protective effect of C. sinensis may be inhibiting the activation of caspase-3 during the AngII-induced apoptosis of NRK-52E.

Biological Conversion of Glycerol to Ethanol by Enterobacter aerogenes

NASA Astrophysics Data System (ADS)

Nwachukwu, Raymond E. S.

In a search to turn the economically and environmentally non-valuable "waste" streams of biodiesel production into a profitable byproduct, a mutant strain of Enterobacter aerogenes ATCC 13048 was developed by six-tube subculturing technique. This technique is based on the principle of adaptive evolution, and involved subculturing the bacterium in a tryptic soy broth without dextrose (TSB) containing specific glycerol and ethanol concentration for six consecutive times. Then, the six consecutive subculturing was repeated in a fresh TSB of higher glycerol and ethanol concentrations. A new mutant strain, E. aerogenes S012, which could withstand a combination of 200 g/l glycerol and 30 g/l ethanol concentrations, was developed. The wild and mutant strains were used for the fermentation of pure (P-) and recovered (R-) glycerol. Taguchi and full factorial methods of design of experiments were used to screen and optimize the important process factors that influence the microbial production of ethanol. A statistically sound regression model was used to establish the mathematical relationship between the process variables and ethanol production. Temperature of 38°C, agitation speed of 200 rpm, pH of 6.3-6.6, and microaerobic condition were the optimum process conditions. Different pretreatment methods to recover glycerol from the crude glycerol and the subsequent fermentation method showed that direct acidification using 85% H3PO4 was the best. The R-glycerol contained 51% pure glycerol and 21% methanol. The wild strain, E. aerogenes ATCC 13048, produced only 12 g/l and 12.8 g/l ethanol from 20 g/l P- and R-glycerol respectively, and could not utilize higher glycerol concentrations. The mutant, E. aerogenes S012, produced ethanol amount and yield of 43 g/l and 1.12 mol/mol-glycerol from P-glycerol, respectively within 96 h. It also produced ethanol amount and yield of 26.8 g/l and 1.07 mol/mol-glycerol, respectively, from R-glycerol within the same duration. In a fermentation to estimate hydrogen production using a respirometer, the hydrogen yield and volumetric rate of 1.06 mol/mol-glycerol and 217 ml/l/h, respectively were obtained from 6% P-glycerol in 72 h by E. aerogenes S012. The result was higher from R-glycerol, which produced hydrogen yield and productivity of 1.83 mol/mol-glycerol and 326 ml/l/h, respectively.

Very high CO2 reduces photosynthesis, dark respiration and yield in wheat

NASA Technical Reports Server (NTRS)

Reuveni, J.; Bugbee, B.

1997-01-01

Although terrestrial CO2 concentrations, [CO2] are not expected to reach 1000 micromoles mol-1 for many decades, CO2 levels in closed systems such as growth chambers and glasshouses, can easily exceed this concentration. CO2 levels in life support systems in space can exceed 10000 micromoles mol-1 (1%). Here we studied the effect of six CO2 concentrations, from ambient up to 10000 micromoles mol-1, on seed yield, growth and gas exchange of two wheat cultivars (USU-Apogee and Veery-l0). Elevating [CO2] from 350 to 1000 micromoles mol-1 increased seed yield (by 33%), vegetative biomass (by 25%) and number of heads m-2 (by 34%) of wheat plants. Elevation of [CO2] from 1000 to 10000 micromoles mol-1 decreased seed yield (by 37%), harvest index (by 14%), mass per seed (by 9%) and number of seeds per head (by 29%). This very high [CO2] had a negligible, non-significant effect on vegetative biomass, number of heads m-2 and seed mass per head. A sharp decrease in seed yield, harvest index and seeds per head occurred by elevating [CO2] from 1000 to 2600 micromoles mol-1. Further elevation of [CO2] from 2600 to 10000 micromoles mol-1 caused a further but smaller decrease. The effect of CO2 on both wheat cultivars was similar for all growth parameters. Similarly there were no differences in the response to high [CO2] between wheat grown hydroponically in growth chambers under fluorescent lights and those grown in soilless media in a glasshouse under sunlight and high pressure sodium lamps. There was no correlation between high [CO2] and ethylene production by flag leaves or by wheat heads. Therefore, the reduction in seed set in wheat plants is not mediated by ethylene. The photosynthetic rate of whole wheat plants was 8% lower and dark respiration of the wheat heads 25% lower when exposed to 2600 micromoles mol-1 CO2 compared to ambient [CO2]. It is concluded that the reduction in the seed set can be mainly explained by the reduction in the dark respiration in wheat heads, when most of the respiration is functional and is needed for seed development.

T2DM Self-Management via Smartphone Applications: A Systematic Review and Meta-Analysis.

PubMed

Cui, Mingxuan; Wu, Xueyan; Mao, Jiangfeng; Wang, Xi; Nie, Min

2016-01-01

Mobile health interventions (mHealth) based on smartphone applications (apps) are promising tools to help improve diabetes care and self-management; however, more evidence on the efficacy of mHealth in diabetes care is needed. The objective of this study was to conduct a systematic review and meta-analysis of randomized controlled trials (RCTs) assessing the effect of mHealth apps on changes in hemoglobin A1c (HbA1c), blood glucose, blood pressure, serum lipids, and body weight in type 2 diabetes mellitus (T2DM) patients. Two independent reviewers searched three online databases (PubMed, the Cochrane Library, and EMBASE) to identify relevant studies published between January 2005 and June 2016. Of the 2,596 articles retrieved, 13 RCTs were included. We used random effects model to estimate the pooled results. Thirteen studies were selected for the systematic review, six of which with data available containing 1,022 patients were included for the meta-analysis. There was a moderate effect on glycemic control after the mHealth app-based interventions. The overall effect on HbA1c shown as mean difference (MD) was -0.40% (-4.37 mmol/mol) (95% confidence interval [CI] -0.69 to -0.11% [-7.54 to -1.20 mmol/mol]; p = 0.007) and standardized mean differences (SMD) was -0.40% (-4.37 mmol/mol) (95% confidence interval [CI] -0.69 to -0.10% [-7.54 to -1.09 mmol/mol]; p = 0.008). A subgroup analysis showed a similar effect with -0.33% (-3.61 mmol/mol) (95% CI -0.59 to -0.06% [-6.45 to -0.66 mmol/mol]; p = 0.02) in MD and -0.38% (-4.15 mmol/mol) (95% CI -0.71 to -0.05% [-7.76 to -0.55 mmol/mol]; p = 0.02) in SMD in studies where patients' baseline HbA1c levels were less than 8.0%. No effects of mHealth app interventions were found on blood pressure, serum lipids, or weight. Assessment of overall study quality and publication bias demonstrated a low risk of bias among the six studies. Smartphone apps offered moderate benefits for T2DM self-management. However, more research with valid study designs and longer follow-up is needed to evaluate the impact of mHealth apps for diabetes care and self-management.

Mechanism of epoxide hydrolysis in microsolvated nucleotide bases adenine, guanine and cytosine: a DFT study.

PubMed

Vijayalakshmi, Kunduchi P; Mohan, Neetha; Ajitha, Manjaly J; Suresh, Cherumuttathu H

2011-07-21

Six water molecules have been used for microsolvation to outline a hydrogen bonded network around complexes of ethylene epoxide with nucleotide bases adenine (EAw), guanine (EGw) and cytosine (ECw). These models have been developed with the MPWB1K-PCM/6-311++G(3df,2p)//MPWB1K/6-31+G(d,p) level of DFT method and calculated S(N)2 type ring opening of the epoxide due to amino group of the nucleotide bases, viz. the N6 position of adenine, N2 position of guanine and N4 position of cytosine. Activation energy (E(act)) for the ring opening was found to be 28.06, 28.64, and 28.37 kcal mol(-1) respectively for EAw, EGw and ECw. If water molecules were not used, the reactions occurred at considerably high value of E(act), viz. 53.51 kcal mol(-1) for EA, 55.76 kcal mol(-1) for EG and 56.93 kcal mol(-1) for EC. The ring opening led to accumulation of negative charge on the developing alkoxide moiety and the water molecules around the charge localized regions showed strong hydrogen bond interactions to provide stability to the intermediate systems EAw-1, EGw-1 and ECw-1. This led to an easy migration of a proton from an activated water molecule to the alkoxide moiety to generate a hydroxide. Almost simultaneously, a proton transfer chain reaction occurred through the hydrogen bonded network of water molecules and resulted in the rupture of one of the N-H bonds of the quaternized amino group. The highest value of E(act) for the proton transfer step of the reaction was 2.17 kcal mol(-1) for EAw, 2.93 kcal mol(-1) for EGw and 0.02 kcal mol(-1) for ECw. Further, the overall reaction was exothermic by 17.99, 22.49 and 13.18 kcal mol(-1) for EAw, EGw and ECw, respectively, suggesting that the reaction is irreversible. Based on geometric features of the epoxide-nucleotide base complexes and the energetics, the highest reactivity is assigned for adenine followed by cytosine and guanine. Epoxide-mediated damage of DNA is reported in the literature and the present results suggest that hydrated DNA bases become highly S(N)2 active on epoxide systems and the occurrence of such reactions can inflict permanent damage to the DNA.