Multi-level study of C3H2: The first interstellar hydrocarbon ring

NASA Technical Reports Server (NTRS)

Madden, S. C.; Irvine, W. M.; Matthews, H. E.; Avery, L. W.

1986-01-01

Cyclic species in the interstellar medium have been searched for almost since the first detection of interstellar polyatomic molecules. Eleven different C3H2 rotational transitions were detected; 9 of which were studied in TMC-1, a nearby dark dust cloud, are shown. The 1 sub 10 yields 1 sub 01 and 2 sub 20 yields 2 sub 11 transitions were observed with the 43 m NRAO telescope, while the remaining transitions were detected with the 14 m antenna of the Five College Radio Observatory (FCRAO). The lines detected in TMC-1 have energies above the ground state ranging from 0.9 to 17.1 K and consist of both ortho and para species. Limited maps were made along the ridge for several of the transitions. The HC3N J = 2 yields 1 transition were mapped simultaneously with the C3H2 1 sub 10 yields 1 sub 01 line and therefore can compare the distribution of this ring with a carbon chain in TMC-1. C3H2 is distributed along a narrow ridge with a SE - NW extension which is slightly more extended than the HC2N J = 2 yields 1. Gaussian fits gives a FWHP extension of 8'5 for C3H2 while HC3N has a FWHP of 7'. The data show variations of the two velocity components along the ridge as a function of transition. Most of the transitions show a peak at the position of strongest HC3N emission while the 2 sub 21 yields 2 sub 10 transition shows a peak at the NH3 position.

Mechanism of cyanoacetylene photochemistry at 185 and 254 nm

NASA Technical Reports Server (NTRS)

Clarke, D. W.; Ferris, J. P.

1996-01-01

The role of cyanoacetylene (HC3N) in the atmospheric photochemistry of Titan and its relevance to polymer formation are discussed. Investigation of the relative light absorption of HC3N, acetylene (C2H2), and diacetylene (C4H2) revealed that HC3N is an important absorber of UV light in the 205- to 225-nanometer wavelength region in Titan's polar regions. Laboratory studies established that photolysis of C2H2 initiates the polymerization of HC3N even though the HC3N is not absorbing the UV light. Quantum yield measurements establish that HC3N is 2-5 times as reactive as C2H2 for polymer formation. Photolysis of HC3N with 185-nanometer light in the presence of N2, H2, Ar, or CF4 results in a decrease in the yield of 1,3,5-tricyanobenzene (1,3,5-tcb), while photolysis in the presence of CH4, C2H6, or n-C4H10 results in an increase in 1,3,5-tcb. The rate of loss of HC3N is increased by all gases except H2, where it is unchanged. It was not possible to detect 1,3,5-tcb as a photoproduct when the partial pressure of HC3N was decreased to 1 torr. Photolysis of HC3N with 254-nanometer light in the presence of H2 or N2 results in the formation of 1,2,4-tcb, while photolysis in the presence of CH4, C2H6, or n-C4H10 results in the formation of increasing amounts of 1,3,5-tcb. Mechanisms for the formation of polymers are presented.

Sialylation on O-glycans protects platelets from clearance by liver Kupffer cells.

PubMed

Li, Yun; Fu, Jianxin; Ling, Yun; Yago, Tadayuki; McDaniel, J Michael; Song, Jianhua; Bai, Xia; Kondo, Yuji; Qin, Yannan; Hoover, Christopher; McGee, Samuel; Shao, Bojing; Liu, Zhenghui; Sonon, Roberto; Azadi, Parastoo; Marth, Jamey D; McEver, Rodger P; Ruan, Changgeng; Xia, Lijun

2017-08-01

Most platelet membrane proteins are modified by mucin-type core 1-derived glycans (O-glycans). However, the biological importance of O-glycans in platelet clearance is unclear. Here, we generated mice with a hematopoietic cell-specific loss of O-glycans (HC C1galt1 -/- ). These mice lack O-glycans on platelets and exhibit reduced peripheral platelet numbers. Platelets from HC C1galt1 -/- mice show reduced levels of α-2,3-linked sialic acids and increased accumulation in the liver relative to wild-type platelets. The preferential accumulation of HC C1galt1 -/- platelets in the liver was reduced in mice lacking the hepatic asialoglycoprotein receptor [Ashwell-Morell receptor (AMR)]. However, we found that Kupffer cells are the primary cells phagocytosing HC C1galt1 -/- platelets in the liver. Our results demonstrate that hepatic AMR promotes preferential adherence to and phagocytosis of desialylated and/or HC C1galt1 -/- platelets by the Kupffer cell through its C-type lectin receptor CLEC4F. These findings provide insights into an essential role for core 1 O-glycosylation of platelets in their clearance in the liver.

Sialylation on O-glycans protects platelets from clearance by liver Kupffer cells

PubMed Central

Li, Yun; Fu, Jianxin; Ling, Yun; Yago, Tadayuki; McDaniel, J. Michael; Song, Jianhua; Bai, Xia; Kondo, Yuji; Qin, Yannan; Hoover, Christopher; McGee, Samuel; Shao, Bojing; Liu, Zhenghui; Sonon, Roberto; Azadi, Parastoo; Marth, Jamey D.; McEver, Rodger P.; Ruan, Changgeng; Xia, Lijun

2017-01-01

Most platelet membrane proteins are modified by mucin-type core 1-derived glycans (O-glycans). However, the biological importance of O-glycans in platelet clearance is unclear. Here, we generated mice with a hematopoietic cell-specific loss of O-glycans (HC C1galt1−/−). These mice lack O-glycans on platelets and exhibit reduced peripheral platelet numbers. Platelets from HC C1galt1−/− mice show reduced levels of α-2,3-linked sialic acids and increased accumulation in the liver relative to wild-type platelets. The preferential accumulation of HC C1galt1−/− platelets in the liver was reduced in mice lacking the hepatic asialoglycoprotein receptor [Ashwell–Morell receptor (AMR)]. However, we found that Kupffer cells are the primary cells phagocytosing HC C1galt1−/− platelets in the liver. Our results demonstrate that hepatic AMR promotes preferential adherence to and phagocytosis of desialylated and/or HC C1galt1−/− platelets by the Kupffer cell through its C-type lectin receptor CLEC4F. These findings provide insights into an essential role for core 1 O-glycosylation of platelets in their clearance in the liver. PMID:28716912

3-Hz postural tremor in multiple system atrophy cerebellar type (MSA-C)-a static posturography study.

PubMed

Li, Xiaodi; Wang, Yuzhou; Wang, Zhanhang; Xu, Yan; Zheng, Wenhua

2018-01-01

The objective of the study is to evaluate postural dysfunction of multiple system atrophy-parkinsonian type (MSA-P) and cerebellar type (MSA-C) by static posturography exam. A total of 29 MSA-P patients, 40 MSA-C patients, and 23 healthy controls (HC) were recruited and engaged in a sensory organization test (SOT). The amplitude of the postural sway was measured and transformed into energy value by Fourier analyzer. SOT scores, frequency of falls and typical 3-Hz postural tremors during the four stance tasks, and energy value in three different frequency bands were recorded and compared. Compared with HC, SOT scores were significantly lower in MSA groups (P < 0.01). Compared with MSA-P, the vestibular scores were further reduced in MSA-C patients (P < 0.05). Falls were more frequent in MSA groups, especially in SOT4 task (foam surface with eyes closed) or in MSA-C group (P < 0.05). Typical 3-Hz postural tremor was observed in 97.5% MSA-C patients, in 24.1% MSA-P patients but in none of the HC (P < 0.05). Compared with HC, much more energy was consumed in every task, every direction, and nearly every frequency band in MSA groups. Energy value of MSA-C group was significantly higher than that of MSA-P, especially in higher frequency band (2 ~ 20 Hz) or in more difficult stance tasks (SOT 3 ~ 4, foam surface with eyes open or closed) (P < 0.05). Both MSA-P and MSA-C were characterized by severe static postural dysfunction. However, typical 3-Hz postural tremor was predominant in MSA-C and was very useful in the differential diagnosis between MSA-P and MSA-C.

{Mo96La8} eggshell ring and self-assembly to {Mo132} Keplerate through Mo-blue intermediate, involved in UV-photolysis of [Mo7O24](6-)/carboxylic acid system at pH 4.

PubMed

Yamase, Toshihiro; Kumagai, Shun; Prokop, Petra V; Ishikawa, Eri; Tomsa, Adrian-Raul

2010-10-18

The prolonged UV-photolysis of aqueous solutions containing [Mo(7)O(24)](6-) and C(2)H(5)CO(2)H (as electron donor) at pH 3.9-4.1 generates the carboxylate-coordinated {Mo(132)} Keplerate (1a) isolated as a formamidinium/ammonium-mixed salt, [HC(NH(2))(2)](26)(NH(4))(28)[Mo(V)(60)Mo(VI)(72)O(372)(H(2)O)(48)(C(2)H(5)CO(2))(36)((i)C(3)H(7)CO(2))(6)]·16H(2)O (1), through the Mo-blue intermediate (2). The coordination of 2 to La(3+) gives rise to the formation of the chain structure of the C(2)-symmetric {Mo(96)La(8)} eggshell rings, formulated by H(22)[Mo(V)(20)Mo(VI)(76)O(301)(H(2)O)(29){La(H(2)O)(6)}(2)]{La(H(2)O)(5)}(6)]·54.5H(2)O (3). The eggshell-ring geometry results from the insertion of [Mo(VI)(2)O(7)(H(2)O)](2-) (spacer) into the equator outer ring of the wheel-shaped Mo-blue, and 10 {(Mo(VI))(Mo(VI)(5))} pentagonal subunits alternately above and below the equator outer ring are connected by eight La(3+) and two {Mo(VI)(2)} linkers within two inner rings. The neighboring eggshell rings are linked through two Mo-O-Mo bonds formed by dehydrative condensation between the {Mo(VI)(2)} linkers to result in the chain structure. Together with the results of the elemental analysis and IR, electronic absorption, (13)C NMR, and ESI-MS spectra for 2, the ring profile analysis of 3 let us identify 2 with a carbolylate-coordinated Mo-blue ring of high nuclearity. The Mo(VI)→Mo(V) photoreductive change of 2 to the 60-electron reduced Keplerate in the presence of C(2)H(5)CO(2)H involves both degradation of the outer ring and splitting of the binuclear linkers, which leads to the formation of [(Mo(VI))Mo(VI)(5)O(21)(H(2)O)(4)(carboxylate)](7-) pentagonal subunits and [Mo(V)(2)O(4)(carboxylate)](+)/[Mo(V)O(2)(carboxylate)(1/2)](0.5+)-mixed linkers for 1.

Photochemistry of furyl- and thienyldiazomethanes: spectroscopic characterization of triplet 3-thienylcarbene.

PubMed

Pharr, Caroline R; Kopff, Laura A; Bennett, Brian; Reid, Scott A; McMahon, Robert J

2012-04-11

Photolysis (λ > 543 nm) of 3-thienyldiazomethane (1), matrix isolated in Ar or N(2) at 10 K, yields triplet 3-thienylcarbene (13) and α-thial-methylenecyclopropene (9). Carbene 13 was characterized by IR, UV/vis, and EPR spectroscopy. The conformational isomers of 3-thienylcarbene (s-E and s-Z) exhibit an unusually large difference in zero-field splitting parameters in the triplet EPR spectrum (|D/hc| = 0.508 cm(-1), |E/hc| = 0.0554 cm(-1); |D/hc| = 0.579 cm(-1), |E/hc| = 0.0315 cm(-1)). Natural Bond Orbital (NBO) calculations reveal substantially differing spin densities in the 3-thienyl ring at the positions adjacent to the carbene center, which is one factor contributing to the large difference in D values. NBO calculations also reveal a stabilizing interaction between the sp orbital of the carbene carbon in the s-Z rotamer of 13 and the antibonding σ orbital between sulfur and the neighboring carbon-an interaction that is not observed in the s-E rotamer of 13. In contrast to the EPR spectra, the electronic absorption spectra of the rotamers of triplet 3-thienylcarbene (13) are indistinguishable under our experimental conditions. The carbene exhibits a weak electronic absorption in the visible spectrum (λ(max) = 467 nm) that is characteristic of triplet arylcarbenes. Although studies of 2-thienyldiazomethane (2), 3-furyldiazomethane (3), or 2-furyldiazomethane (4) provided further insight into the photochemical interconversions among C(5)H(4)S or C(5)H(4)O isomers, these studies did not lead to the spectroscopic detection of the corresponding triplet carbenes (2-thienylcarbene (11), 3-furylcarbene (23), or 2-furylcarbene (22), respectively). © 2012 American Chemical Society

Roseomonas aerofrigidensis sp. nov., isolated from an air conditioner.

PubMed

Hyeon, Jong Woo; Jeon, Che Ok

2017-10-01

A Gram-stain-negative, strictly aerobic bacterium, designated HC1 T , was isolated from an air conditioner in South Korea. Cells were orange, non-motile cocci with oxidase- and catalase-positive activities and did not contain bacteriochlorophyll a. Growth of strain HC1 T was observed at 10-45 °C (optimum, 30 °C), pH 4.5-9.5 (optimum, pH 7.0) and 0-3 % (w/v) NaCl (optimum, 0 %). Strain HC1 T contained summed feature 8 (comprising C18 : 1ω7c/C18 : 1ω6c), C16 : 0 and cyclo-C19 : 0ω8c as the major fatty acids and ubiquinone-10 as the sole isoprenoid quinone. Phosphatidylglycerol, phosphatidylethanolamine, phosphatidylcholine and an unknown aminolipid were detected as the major polar lipids. The major carotenoid was hydroxyspirilloxanthin. The G+C content of the genomic DNA was 70.1 mol%. Phylogenetic analysis, based on 16S rRNA gene sequences, showed that strain HC1 T formed a phylogenetic lineage within the genus Roseomonas. Strain HC1 T was most closely related to the type strains of Roseomonas oryzae, Roseomonas rubra, Roseomonas aestuarii and Roseomonas rhizosphaerae with 98.1, 97.9, 97.6 and 96.8 % 16S rRNA gene sequence similarities, respectively, but the DNA-DNA relatedness values between strain HC1 T and closely related type strains were less than 70 %. Based on phenotypic, chemotaxonomic and molecular properties, strain HC1 T represents a novel species of the genus Roseomonas, for which the name Roseomonas aerofrigidensis sp. nov. is proposed. The type strain is HC1 T (=KACC 19097 T =JCM 31878 T ).

Zinc complex chemistry of N,N,O ligands providing a hydrophobic cavity.

PubMed

Gross, Florian; Vahrenkamp, Heinrich

2005-05-02

Three new highly substituted bis(2-picolyl)(2-hydroxybenzyl)amine ligands were synthesized, and their biomimetic zinc complex chemistry was explored. They have tert-butyl substituents at the 3-and 5-positions of their phenyl rings, and they bear one phenyl group (HL2), two methyl groups (HL3), or two phenyl groups (HL4) at the 6-positions of their pyridyl rings. Their reactions with hydrated zinc perchlorate yield three distinctively different complex types. L2 forms a trigonal-bipyramidal aqua complex, and L3, a square-pyramidal aqua complex. The substituents on L4 leave no room for a water ligand, and the resulting zinc complex is trigonal-monopyramidal with a vacant coordination site. The water ligands on the L2Zn and L3Zn units can be replaced by anionic halide, thiocyanate, p-nitrophenolate, benzoate, and organophosphate as well as uncharged pyridine ligands. The L4Zn unit forms labile halide, p-nitrophenolate, and pyridine complexes. Triethylamine converts the aqua complexes to the labile hydroxides L2Zn-OH and L3Zn-OH, and in polar media [L3Zn-OH2]+ seems to be in equilibrium with L3Zn-OH. The hydroxides, but not the water complexes, effect the hydrolytic cleavage of tris(p-nitrophenyl) phosphate to bis(p-nitrophenyl) phosphate. The kinetic investigation of the cleavage reactions has shown them to be second-order reactions, thereby supporting the proposed four-center mechanism.

Insights into the role of the unusual disulfide bond in copper-zinc superoxide dismutase.

PubMed

Sea, Kevin; Sohn, Se Hui; Durazo, Armando; Sheng, Yuewei; Shaw, Bryan F; Cao, Xiaohang; Taylor, Alexander B; Whitson, Lisa J; Holloway, Stephen P; Hart, P John; Cabelli, Diane E; Gralla, Edith Butler; Valentine, Joan Selverstone

2015-01-23

The functional and structural significance of the intrasubunit disulfide bond in copper-zinc superoxide dismutase (SOD1) was studied by characterizing mutant forms of human SOD1 (hSOD) and yeast SOD1 lacking the disulfide bond. We determined x-ray crystal structures of metal-bound and metal-deficient hC57S SOD1. C57S hSOD1 isolated from yeast contained four zinc ions per protein dimer and was structurally very similar to wild type. The addition of copper to this four-zinc protein gave properly reconstituted 2Cu,2Zn C57S hSOD, and its spectroscopic properties indicated that the coordination geometry of the copper was remarkably similar to that of holo wild type hSOD1. In contrast, the addition of copper and zinc ions to apo C57S human SOD1 failed to give proper reconstitution. Using pulse radiolysis, we determined SOD activities of yeast and human SOD1s lacking disulfide bonds and found that they were enzymatically active at ∼10% of the wild type rate. These results are contrary to earlier reports that the intrasubunit disulfide bonds in SOD1 are essential for SOD activity. Kinetic studies revealed further that the yeast mutant SOD1 had less ionic attraction for superoxide, possibly explaining the lower rates. Saccharomyces cerevisiae cells lacking the sod1 gene do not grow aerobically in the absence of lysine, but expression of C57S SOD1 increased growth to 30-50% of the growth of cells expressing wild type SOD1, supporting that C57S SOD1 retained a significant amount of activity. © 2015 by The American Society for Biochemistry and Molecular Biology, Inc.

Insights into the Role of the Unusual Disulfide Bond in Copper-Zinc Superoxide Dismutase*

PubMed Central

Sea, Kevin; Sohn, Se Hui; Durazo, Armando; Sheng, Yuewei; Shaw, Bryan F.; Cao, Xiaohang; Taylor, Alexander B.; Whitson, Lisa J.; Holloway, Stephen P.; Hart, P. John; Cabelli, Diane E.; Gralla, Edith Butler; Valentine, Joan Selverstone

2015-01-01

The functional and structural significance of the intrasubunit disulfide bond in copper-zinc superoxide dismutase (SOD1) was studied by characterizing mutant forms of human SOD1 (hSOD) and yeast SOD1 lacking the disulfide bond. We determined x-ray crystal structures of metal-bound and metal-deficient hC57S SOD1. C57S hSOD1 isolated from yeast contained four zinc ions per protein dimer and was structurally very similar to wild type. The addition of copper to this four-zinc protein gave properly reconstituted 2Cu,2Zn C57S hSOD, and its spectroscopic properties indicated that the coordination geometry of the copper was remarkably similar to that of holo wild type hSOD1. In contrast, the addition of copper and zinc ions to apo C57S human SOD1 failed to give proper reconstitution. Using pulse radiolysis, we determined SOD activities of yeast and human SOD1s lacking disulfide bonds and found that they were enzymatically active at ∼10% of the wild type rate. These results are contrary to earlier reports that the intrasubunit disulfide bonds in SOD1 are essential for SOD activity. Kinetic studies revealed further that the yeast mutant SOD1 had less ionic attraction for superoxide, possibly explaining the lower rates. Saccharomyces cerevisiae cells lacking the sod1 gene do not grow aerobically in the absence of lysine, but expression of C57S SOD1 increased growth to 30–50% of the growth of cells expressing wild type SOD1, supporting that C57S SOD1 retained a significant amount of activity. PMID:25433341

Sol-gel zinc oxide humidity sensors integrated with a ring oscillator circuit on-a-chip.

PubMed

Yang, Ming-Zhi; Dai, Ching-Liang; Wu, Chyan-Chyi

2014-10-28

The study develops an integrated humidity microsensor fabricated using the commercial 0.18 μm complementary metal oxide semiconductor (CMOS) process. The integrated humidity sensor consists of a humidity sensor and a ring oscillator circuit on-a-chip. The humidity sensor is composed of a sensitive film and branch interdigitated electrodes. The sensitive film is zinc oxide prepared by sol-gel method. After completion of the CMOS process, the sensor requires a post-process to remove the sacrificial oxide layer and to coat the zinc oxide film on the interdigitated electrodes. The capacitance of the sensor changes when the sensitive film adsorbs water vapor. The circuit is used to convert the capacitance of the humidity sensor into the oscillation frequency output. Experimental results show that the output frequency of the sensor changes from 84.3 to 73.4 MHz at 30 °C as the humidity increases 40 to 90%RH.

Identification of a New Zinc Binding Chemotype by Fragment Screening.

PubMed

Chrysanthopoulos, Panagiotis K; Mujumdar, Prashant; Woods, Lucy A; Dolezal, Olan; Ren, Bin; Peat, Thomas S; Poulsen, Sally-Ann

2017-09-14

The discovery of a new zinc binding chemotype from screening a nonbiased fragment library is reported. Using the orthogonal fragment screening methods of native state mass spectrometry and surface plasmon resonance a 3-unsubstituted 2,4-oxazolidinedione fragment was found to have low micromolar binding affinity to the zinc metalloenzyme carbonic anhydrase II (CA II). This affinity approached that of fragment sized primary benzenesulfonamides, the classical zinc binding group found in most CA II inhibitors. Protein X-ray crystallography established that 3-unsubstituted 2,4-oxazolidinediones bound to CA II via an interaction of the acidic ring nitrogen with the CA II active site zinc, as well as two hydrogen bonds between the oxazolidinedione ring oxygen and the CA II protein backbone. Furthermore, 3-unsubstituted 2,4-oxazolidinediones appear to be a viable starting point for the development of an alternative class of CA inhibitor, wherein the medicinal chemistry pedigree of primary sulfonamides has dominated for several decades.

Parkin, A Top Level Manager in the Cell’s Sanitation Department

PubMed Central

Rankin, Carolyn A; Roy, Ambrish; Zhang, Yang; Richter, Mark

2011-01-01

Parkin belongs to a class of multiple RING domain proteins designated as RBR (RING, in between RING, RING) proteins. In this review we examine what is known regarding the structure/function relationship of the Parkin protein. Parkin contains three RING domains plus a ubiquitin-like domain and an in-between-RING (IBR) domain. RING domains are rich in cysteine amino acids that act as ligands to bind zinc ions. RING domains may interact with DNA or with other proteins and perform a wide range of functions. Some function as E3 ubiquitin ligases, participating in attachment of ubiquitin chains to signal proteasome degradation; however, ubiquitin may be attached for purposes other than proteasome degradation. It was determined that the C-terminal most RING, RING2, is essential for Parkin to function as an E3 ubiquitin ligase and a number of substrates have been identified. However, Parkin also participates in a number of other fiunctions, such as DNA repair, microtubule stabilization, and formation of aggresomes. Some functions, such as participation in a multi-protein complex implicated in NMDA activity at the post synaptic density, do not require ubiquitination of substrate molecules. Recent observations of RING proteins suggest their function may be regulated by zinc ion binding. We have modeled the three RING domains of Parkin and have identified a new set of RING2 ligands. This set allows for binding of two rather than just one zinc ion, opening the possibility that the number of zinc ions bound acts as a molecular switch to modulate Parkin function. PMID:21633666

Comparison of low- and high-carbohydrate diets for type 2 diabetes management: a randomized trial.

PubMed

Tay, Jeannie; Luscombe-Marsh, Natalie D; Thompson, Campbell H; Noakes, Manny; Buckley, Jonathan D; Wittert, Gary A; Yancy, William S; Brinkworth, Grant D

2015-10-01

Few well-controlled studies have comprehensively examined the effects of very-low-carbohydrate diets on type 2 diabetes (T2D). We compared the effects of a very-low-carbohydrate, high-unsaturated fat, low-saturated fat (LC) diet with a high-carbohydrate, low-fat (HC) diet on glycemic control and cardiovascular disease risk factors in T2D after 52 wk. In this randomized controlled trial that was conducted in an outpatient research clinic, 115 obese adults with T2D [mean ± SD age: 58 ± 7 y; body mass index (in kg/m(2)): 34.6 ± 4.3; glycated hemoglobin (HbA1c): 7.3 ± 1.1%; duration of diabetes: 8 ± 6 y] were randomly assigned to consume either a hypocaloric LC diet [14% of energy as carbohydrate (carbohydrate <50 g/d), 28% of energy as protein, and 58% of energy as fat (<10% saturated fat)] or an energy-matched HC diet [53% of energy as carbohydrate, 17% of energy as protein, and 30% of energy as fat (<10% saturated fat)] combined with supervised aerobic and resistance exercise (60 min; 3 d/wk). Outcomes were glycemic control assessed with use of measurements of HbA1c, fasting blood glucose, glycemic variability assessed with use of 48-h continuous glucose monitoring, diabetes medication, weight, blood pressure, and lipids assessed at baseline, 24, and 52 wk. Both groups achieved similar completion rates (LC diet: 71%; HC diet: 65%) and mean (95% CI) reductions in weight [LC diet: -9.8 kg (-11.7, -7.9 kg); HC diet: -10.1 kg (-12.0, -8.2 kg)], blood pressure [LC diet: -7.1 (-10.6, -3.7)/-6.2 (-8.2, -4.1) mm Hg; HC diet: -5.8 (-9.4, -2.2)/-6.4 (-8.4, -4.3) mm Hg], HbA1c [LC diet: -1.0% (-1.2%, -0.7%); HC diet: -1.0% (-1.3%, -0.8%)], fasting glucose [LC diet: -0.7 mmol/L (-1.3, -0.1 mmol/L); HC diet: -1.5 mmol/L (-2.1, -0.8 mmol/L)], and LDL cholesterol [LC diet: -0.1 mmol/L (-0.3, 0.1 mmol/L); HC diet: -0.2 mmol/L (-0.4, 0.03 mmol/L)] (P-diet effect ≥ 0.10). Compared with the HC-diet group, the LC-diet group achieved greater mean (95% CI) reductions in the diabetes medication score [LC diet: -0.5 arbitrary units (-0.7, -0.4 arbitrary units); HC diet: -0.2 arbitrary units (-0.4, -0.06 arbitrary units); P = 0.02], glycemic variability assessed by measuring the continuous overall net glycemic action-1 [LC diet: -0.5 mmol/L (-0.6, -0.3 mmol/L); HC diet: -0.05 mmol/L (-0.2, -0.1 mmol/L); P = 0.003], and triglycerides [LC diet: -0.4 mmol/L (-0.5, -0.2 mmol/L); HC diet: -0.01 mmol/L (-0.2, 0.2 mmol/L); P = 0.001] and greater mean (95% CI) increases in HDL cholesterol [LC diet: 0.1 mmol/L (0.1, 0.2 mmol/L); HC diet: 0.06 mmol/L (-0.01, 0.1 mmol/L); P = 0.002]. Both diets achieved substantial weight loss and reduced HbA1c and fasting glucose. The LC diet, which was high in unsaturated fat and low in saturated fat, achieved greater improvements in the lipid profile, blood glucose stability, and reductions in diabetes medication requirements, suggesting an effective strategy for the optimization of T2D management. This trial was registered at www.anzctr.org.au as ACTRN12612000369820. © 2015 American Society for Nutrition.

Synthesis and Crystal Structure of Dibromido{2-[(4-tert-butylmethylphenyl) iminomethyl]pyridine-κ2 N, N'}Zinc

NASA Astrophysics Data System (ADS)

Khalaj, M.; Ghazanfarpour-Darjani, M.; Seftejani, F. B.; Lalegani, A.

2017-12-01

The title compound [Zn( dip)Br2] was synthesized using the Schiff base bidentate ligand (E)-4- tert-butyl- N-(pyridine-2-ylmethylene)benzeneamine ( dip) and zinc(II) bromide salts. It has been characterized by elemental analysis, X-ray diffraction, and optical spectroscopy. The X-ray diffraction analysis demonstrates that in this structure, the zinc(II) ion is located on an inversion center and exhibits a ZnN2Br2 tetrahedral geometry. In this structure the dip ligand is coordinated with zinc(II) ion in a cyclic-bidentate fashion forming a five-membered metallocyclic ring. The compound crystallizes in the monoclinic sp. gr. P21/ m with a = 9.2700(13) Å, b = 7.6128(11) Å, c = 12.3880(17) Å, and β = 97.021(3)°.

Flowering-Related RING Protein 1 (FRRP1) Regulates Flowering Time and Yield Potential by Affecting Histone H2B Monoubiquitination in Rice (Oryza Sativa).

PubMed

Du, Yiwei; He, Wei; Deng, Changwang; Chen, Xi; Gou, Lanming; Zhu, Fugui; Guo, Wei; Zhang, Jianfu; Wang, Tao

2016-01-01

Flowering time is a critical trait for crops cultivated under various temperature/photoperiod conditions around the world. To understand better the flowering time of rice, we used the vector pTCK303 to produce several lines of RNAi knockdown transgenic rice and investigated their flowering times and other agronomic traits. Among them, the heading date of FRRP1-RNAi knockdown transgenic rice was 23-26 days earlier than that of wild-type plants. FRRP1 is a novel rice gene that encodes a C3HC4-type Really Interesting Novel Gene (RING) finger domain protein. In addition to the early flowering time, FRRP1-RNAi knockdown transgenic rice caused changes on an array of agronomic traits, including plant height, panicle length and grain length. We analyzed the expression of some key genes associated with the flowering time and other agronomic traits in the FRRP1-RNAi knockdown lines and compared with that in wild-type lines. The expression of Hd3a increased significantly, which was the key factor in the early flowering time. Further experiments showed that the level of histone H2B monoubiquitination (H2Bub1) was noticeably reduced in the FRRP1-RNAi knockdown transgenic rice lines compared with wild-type plants and MBP-FRRP1-F1 was capable of self-ubiquitination. The results indicate that Flowering Related RING Protein 1 (FRRP1) is involved in histone H2B monoubiquitination and suggest that FRRP1 functions as an E3 ligase in vivo and in vitro. In conclusion, FRRP1 probably regulates flowering time and yield potential in rice by affecting histone H2B monoubiquitination, which leads to changes in gene expression in multiple processes.

Flowering-Related RING Protein 1 (FRRP1) Regulates Flowering Time and Yield Potential by Affecting Histone H2B Monoubiquitination in Rice (Oryza Sativa)

PubMed Central

Deng, Changwang; Chen, Xi; Gou, Lanming; Zhu, Fugui; Guo, Wei; Zhang, Jianfu; Wang, Tao

2016-01-01

Flowering time is a critical trait for crops cultivated under various temperature/photoperiod conditions around the world. To understand better the flowering time of rice, we used the vector pTCK303 to produce several lines of RNAi knockdown transgenic rice and investigated their flowering times and other agronomic traits. Among them, the heading date of FRRP1-RNAi knockdown transgenic rice was 23–26 days earlier than that of wild-type plants. FRRP1 is a novel rice gene that encodes a C3HC4-type Really Interesting Novel Gene (RING) finger domain protein. In addition to the early flowering time, FRRP1-RNAi knockdown transgenic rice caused changes on an array of agronomic traits, including plant height, panicle length and grain length. We analyzed the expression of some key genes associated with the flowering time and other agronomic traits in the FRRP1-RNAi knockdown lines and compared with that in wild-type lines. The expression of Hd3a increased significantly, which was the key factor in the early flowering time. Further experiments showed that the level of histone H2B monoubiquitination (H2Bub1) was noticeably reduced in the FRRP1-RNAi knockdown transgenic rice lines compared with wild-type plants and MBP-FRRP1-F1 was capable of self-ubiquitination. The results indicate that Flowering Related RING Protein 1 (FRRP1) is involved in histone H2B monoubiquitination and suggest that FRRP1 functions as an E3 ligase in vivo and in vitro. In conclusion, FRRP1 probably regulates flowering time and yield potential in rice by affecting histone H2B monoubiquitination, which leads to changes in gene expression in multiple processes. PMID:26934377

Synthesis, spectral, and structural studies of porphyrins having sterically hindered [η(5)-CpCo(η(4)-C4Ph4)] cobalt sandwich units at the meso positions.

PubMed

Keshav, Karunesh; Kumar, Dheeraj; Elias, Anil J

2013-11-04

Synthesis, spectral, and structural studies of the first examples of porphyrins substituted at the meso positions with sterically hindered η(5)-CpCo(η(4)-C4Ph4) cobalt sandwich units are described. The novel dipyrromethane derived cobalt sandwich compound {η(5)-[(C4H4N)2CH]C5H4}Co(η(4)-C4Ph4) 1, as well as its parent aldehyde, η(5)-[C5H4(CHO)]Co(η(4)-C4Ph4), were used in the synthesis of porphyrins having one or two η(5)-CpCo(η(4)-C4Ph4) groups at their meso positions. 1,9-Diformyldipyrromethane derived η(5)-CpCo(η(4)-C4Ph4) 2 was synthesized using dipyrromethane 1 under Vilsmeier conditions. A reaction of 2 with unsubstituted dipyrromethane under basic conditions in the presence of Pd(C6H5CN)2Cl2 yielded an A-type palladium coordinated porphyrin 3 [where A = η(5)-CpCo(η(4)-C4Ph4)]. A similar reaction of 2 with meso aryl and ferrocenyl-substituted dipyrromethanes yielded trans-AB type palladium coordinated porphyrins 4-6 [where A = η(5)-CpCo(η(4)-C4Ph4) and B = 4-tert-butylphenyl 4, ferrocenyl 5, and pentafluorophenyl 6]. Reactions of 2 with 5-ferrocenyl dipyrromethane under the same reaction conditions in the presence of Ni(acac)2 and Zn(OAc)2 gave the trimetallic nickel(II) and zinc(II) complexed trans-AB type porphyrins 7 and 8 having both cobalt and iron sandwich units at the meso positions. Crystal structure of the Pd(II) porphyrin 5 and nickel(II) porphyrin 7 showed nonplanar structures having distinct ruffle type distortion of the porphyrin ring. Demetalation of the zinc(II) trans-AB type porphyrin 8 in the presence of trifluoroacetic acid gave the metal free base porphyrin 9. Reactions of the cobalt sandwich aldehyde [(η(5)-C5H4(CHO)]Co(η(4)-C4Ph4) with sterically hindered dipyrromethane derivatives under acid-catalyzed condensation reactions gave trans-A2B2 type porphyrins [where A = η(5)-CpCo(η(4)-C4Ph4) and B = pentafluorophenyl, 10 mesityl 11]. In contrast, reactions of [η(5)-C5H4(CHO)]Co(η(4)-C4Ph4) with sterically unhindered meso-4-tert-butylphenyl dipyrromethane resulted in both AB3 12 and cis-A2B2 13 type porphyrins [where A = η(5)-CpCo(η(4)-C4Ph4) and B = (4-tert-butylphenyl] as a result of scrambling. The new porphyrin derivatives have been structurally characterized, and their spectral and electrochemical features were determined.

Atomic-Resolution Structures of Horse Liver Alcohol Dehydrogenase with NAD[superscript +] and Fluoroalcohols Define Strained Michaelis Complexes

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

Plapp, Bryce V.; Ramaswamy, S.; Iowa)

2013-01-16

Structures of horse liver alcohol dehydrogenase complexed with NAD{sup +} and unreactive substrate analogues, 2,2,2-trifluoroethanol or 2,3,4,5,6-pentafluorobenzyl alcohol, were determined at 100 K at 1.12 or 1.14 {angstrom} resolution, providing estimates of atomic positions with overall errors of 0.02 {angstrom}, the geometry of ligand binding, descriptions of alternative conformations of amino acid residues and waters, and evidence of a strained nicotinamide ring. The four independent subunits from the two homodimeric structures differ only slightly in the peptide backbone conformation. Alternative conformations for amino acid side chains were identified for 50 of the 748 residues in each complex, and Leu-57 andmore » Leu-116 adopt different conformations to accommodate the different alcohols at the active site. Each fluoroalcohol occupies one position, and the fluorines of the alcohols are well-resolved. These structures closely resemble the expected Michaelis complexes with the pro-R hydrogens of the methylene carbons of the alcohols directed toward the re face of C4N of the nicotinamide rings with a C-C distance of 3.40 {angstrom}. The oxygens of the alcohols are ligated to the catalytic zinc at a distance expected for a zinc alkoxide (1.96 {angstrom}) and participate in a low-barrier hydrogen bond (2.52 {angstrom}) with the hydroxyl group of Ser-48 in a proton relay system. As determined by X-ray refinement with no restraints on bond distances and planarity, the nicotinamide rings in the two complexes are slightly puckered (quasi-boat conformation, with torsion angles of 5.9{sup o} for C4N and 4.8{sup o} for N1N relative to the plane of the other atoms) and have bond distances that are somewhat different compared to those found for NAD(P){sup +}. It appears that the nicotinamide ring is strained toward the transition state on the path to alcohol oxidation.« less

N(4)-Methyl-N(4)-(2-methylphenyl)-1H-pyrazolo[3,4-d]pyrimidine-4,6-diamine-ethanol-hydrazine (1/0.865/0.135): hydrogen-bonded ribbons containing four independent ring types.

PubMed

Trilleras, Jorge; Quiroga, Jairo; Cobo, Justo; Glidewell, Christopher

2009-06-01

N(4)-Methyl-N(4)-(2-methylphenyl)-1H-pyrazolo[3,4-d]pyrimidine-4,6-diamine crystallizes from ethanol as a mixed solvate, C(13)H(14)N(6).0.865C(2)H(6)O.0.135N(2)H(4), (I), where the hydrazine has been carried through from the initial preparation. Within the heterocyclic component, the 2-methylphenyl substituent is disordered over two sets of sites. There is an intramolecular C-H...pi(arene) hydrogen bond, which may control the molecular conformation of the heterocycle. The heterocyclic molecules are linked by two independent N-H...N hydrogen bonds in a chain containing two types of R(2)(2)(8) ring. The ethanol component is linked to this chain by a combination of O-H...N and N-H...O hydrogen bonds and the hydrazine component by two N-H...N hydrogen bonds, so generating two R(3)(3)(9) rings and thus forming a ribbon containing four distinct ring types.

Long-Term Effects of a Very Low Carbohydrate Compared With a High Carbohydrate Diet on Renal Function in Individuals With Type 2 Diabetes: A Randomized Trial.

PubMed

Tay, Jeannie; Thompson, Campbell H; Luscombe-Marsh, Natalie D; Noakes, Manny; Buckley, Jonathan D; Wittert, Gary A; Brinkworth, Grant D

2015-11-01

To compare the long-term effects of a very low carbohydrate, high-protein, low saturated fat (LC) diet with a traditional high unrefined carbohydrate, low-fat (HC) diet on markers of renal function in obese adults with type 2 diabetes (T2DM), but without overt kidney disease.One hundred fifteen adults (BMI 34.6 ± 4.3 kg/m, age 58 ± 7 years, HbA1c 7.3 ± 1.1%, 56 ± 12 mmol/mol, serum creatinine (SCr) 69 ± 15 μmol/L, glomerular filtration rate estimated by the Chronic Kidney Disease Epidemiology Collaboration formula (eGFR 94 ± 12 mL/min/1.73 m)) were randomized to consume either an LC (14% energy as carbohydrate [CHO < 50 g/day], 28% protein [PRO], 58% fat [<10% saturated fat]) or an HC (53% CHO, 17% PRO, 30% fat [<10% saturated fat]) energy-matched, weight-loss diet combined with supervised exercise training (60 min, 3 day/wk) for 12 months. Body weight, blood pressure, and renal function assessed by eGFR, estimated creatinine clearance (Cockcroft-Gault, Salazar-Corcoran) and albumin excretion rate (AER), were measured pre- and post-intervention.Both groups achieved similar completion rates (LC 71%, HC 65%) and reductions in weight (mean [95% CI]; -9.3 [-10.6, -8.0] kg) and blood pressure (-6 [-9, -4]/-6[-8, -5] mmHg), P ≥ 0.18. Protein intake calculated from 24 hours urinary urea was higher in the LC than HC group (LC 120.1 ± 38.2 g/day, 1.3 g/kg/day; HC 95.8 ± 27.8 g/day, 1 g/kg/day), P < 0.001 diet effect. Changes in SCr (LC 3 [1, 5], HC 1 [-1, 3] μmol/L) and eGFR (LC -4 [-6, -2], HC -2 [-3, 0] mL/min/1.73 m) did not differ between diets (P = 0.25). AER decreased independent of diet composition (LC --2.4 [-6, 1.2], HC -1.8 [-5.4, 1.8] mg/24 h, P = 0.24); 6 participants (LC 3, HC 3) had moderately elevated AER at baseline (30-300 mg/24 h), which normalized in 4 participants (LC 2, HC 2) after 52 weeks.Compared with a traditional HC weight loss diet, consumption of an LC high protein diet does not adversely affect clinical markers of renal function in obese adults with T2DM and no preexisting kidney disease.

Sol-Gel Zinc Oxide Humidity Sensors Integrated with a Ring Oscillator Circuit On-a-Chip

PubMed Central

Yang, Ming-Zhi; Dai, Ching-Liang; Wu, Chyan-Chyi

2014-01-01

The study develops an integrated humidity microsensor fabricated using the commercial 0.18 μm complementary metal oxide semiconductor (CMOS) process. The integrated humidity sensor consists of a humidity sensor and a ring oscillator circuit on-a-chip. The humidity sensor is composed of a sensitive film and branch interdigitated electrodes. The sensitive film is zinc oxide prepared by sol-gel method. After completion of the CMOS process, the sensor requires a post-process to remove the sacrificial oxide layer and to coat the zinc oxide film on the interdigitated electrodes. The capacitance of the sensor changes when the sensitive film adsorbs water vapor. The circuit is used to convert the capacitance of the humidity sensor into the oscillation frequency output. Experimental results show that the output frequency of the sensor changes from 84.3 to 73.4 MHz at 30 °C as the humidity increases 40 to 90 %RH. PMID:25353984

32 CFR 256.6 - Runway classification by aircraft type.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 32 National Defense 2 2010-07-01 2010-07-01 false Runway classification by aircraft type. 256.6... type. Class A runways S-2, VC-6, C-1, C-2, TC-4C, U-10, U-11, LU-16, TU-16, HU-16, C-7, C-8, C-12, C-47...-130, A-7, A-38, AV-8, P-2, P-3, T-29, T-33, T-37, T-39, T-1, HC-130B, C-131, C-140, C-5A, KC-97, F-9...

32 CFR 256.6 - Runway classification by aircraft type.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 32 National Defense 2 2011-07-01 2011-07-01 false Runway classification by aircraft type. 256.6... type. Class A runways S-2, VC-6, C-1, C-2, TC-4C, U-10, U-11, LU-16, TU-16, HU-16, C-7, C-8, C-12, C-47...-130, A-7, A-38, AV-8, P-2, P-3, T-29, T-33, T-37, T-39, T-1, HC-130B, C-131, C-140, C-5A, KC-97, F-9...

C4'/H4' selective, non-uniformly sampled 4D HC(P)CH experiment for sequential assignments of (13)C-labeled RNAs.

PubMed

Saxena, Saurabh; Stanek, Jan; Cevec, Mirko; Plavec, Janez; Koźmiński, Wiktor

2014-11-01

A through bond, C4'/H4' selective, "out and stay" type 4D HC(P)CH experiment is introduced which provides sequential connectivity via H4'(i)-C4'(i)-C4'(i-1)-H4'(i-1) correlations. The (31)P dimension (used in the conventional 3D HCP experiment) is replaced with evolution of better dispersed C4' dimension. The experiment fully utilizes (13)C-labeling of RNA by inclusion of two C4' evolution periods. An additional evolution of H4' is included to further enhance peak resolution. Band selective (13)C inversion pulses are used to achieve selectivity and prevent signal dephasing due to the of C4'-C3' and C4'-C5' homonuclear couplings. For reasonable resolution, non-uniform sampling is employed in all indirect dimensions. To reduce sensitivity losses, multiple quantum coherences are preserved during shared-time evolution and coherence transfer delays. In the experiment the intra-nucleotide peaks are suppressed whereas inter-nucleotide peaks are enhanced to reduce the ambiguities. The performance of the experiment is verified on a fully (13)C, (15)N-labeled 34-nt hairpin RNA comprising typical structure elements.

Observation of the hc(1P1) state of charmonium.

PubMed

Rosner, J L; Adam, N E; Alexander, J P; Berkelman, K; Cassel, D G; Crede, V; Duboscq, J E; Ecklund, K M; Ehrlich, R; Fields, L; Galik, R S; Gibbons, L; Gittelman, B; Gray, R; Gray, S W; Hartill, D L; Heltsley, B K; Hertz, D; Jones, C D; Kandaswamy, J; Kreinick, D L; Kuznetsov, V E; Mahlke-Krüger, H; Meyer, T O; Onyisi, P U E; Patterson, J R; Peterson, D; Phillips, E A; Pivarski, J; Riley, D; Ryd, A; Sadoff, A J; Schwarthoff, H; Shi, X; Shepherd, M R; Stroiney, S; Sun, W M; Urner, D; Wilksen, T; Weaver, K M; Weinberger, M; Athar, S B; Avery, P; Breva-Newell, L; Patel, R; Potlia, V; Stoeck, H; Yelton, J; Rubin, P; Cawlfield, C; Eisenstein, B I; Gollin, G D; Karliner, I; Kim, D; Lowrey, N; Naik, P; Sedlack, C; Selen, M; White, E J; Williams, J; Wiss, J; Edwards, K W; Besson, D; Pedlar, T K; Cronin-Hennessy, D; Gao, K Y; Gong, D T; Hietala, J; Kubota, Y; Klein, T; Lang, B W; Li, S Z; Poling, R; Scott, A W; Smith, A; Dobbs, S; Metreveli, Z; Seth, K K; Tomaradze, A; Zweber, P; Ernst, J; Mahmood, A H; Severini, H; Asner, D M; Dytman, S A; Love, W; Mehrabyan, S; Mueller, J A; Savinov, V; Li, Z; Lopez, A; Mendez, H; Ramirez, J; Huang, G S; Miller, D H; Pavlunin, V; Sanghi, B; Shipsey, I P J; Adams, G S; Cravey, M; Cummings, J P; Danko, I; Napolitano, J; He, Q; Muramatsu, H; Park, C S; Park, W; Thorndike, E H; Coan, T E; Gao, Y S; Liu, F; Artuso, M; Boulahouache, C; Blusk, S; Butt, J; Dorjkhaidav, O; Li, J; Menaa, N; Mountain, R; Nandakumar, R; Randrianarivony, K; Redjimi, R; Sia, R; Skwarnicki, T; Stone, S; Wang, J C; Zhang, K; Csorna, S E; Bonvicini, G; Cinabro, D; Dubrovin, M; Briere, R A; Chen, G P; Chen, J; Ferguson, T; Tatishvili, G; Vogel, H; Watkins, M E

2005-09-02

The h(c)((1)P(1)) state of charmonium has been observed in the reaction psi(2S) --> pi(0)h(c) --> (gammagamma)(gammaeta(c)) using 3.08 x10(6) psi(2S) decays recorded in the CLEO detector. Data have been analyzed both for the inclusive reaction, where the decay products of the eta(c) are not identified, and for exclusive reactions, in which eta(c) decays are reconstructed in seven hadronic decay channels. We find M(h(c)) = 3524.4 +/- 0.6 +/- 0.4 MeV which corresponds to a hyperfine splitting DeltaM(hf)(1P) triple-bond pi(0)h(c)) x B(h(c) --> gammaeta(c)) = (4.0 +/- 0.8 +/- 0.7) x 10(-4).

Submillimeter-Wave Observations of C_3N^- in AN Extended Negative Glow Discharge

NASA Astrophysics Data System (ADS)

Amano, T.

2009-06-01

Extended negative glow and hollow anode discharges are found to be good sources of negative ions, such as CN^-, C_2H^-, and C_4H^-, for observations of pure rotational lines in the submillimeter-wave region. Thaddeus et al. detected C_3N^- in a glow discharge in HC_3N diluted in Ar buffer gas, and its rotational lines up to 378 GHz (J=39-38) were measured. In the present investigation, this anion has been observed in an extended negative glow discharge in a gas mixture of C_2N_2 (˜ 2 mTorr) and C_2H_2 (˜ 3 mTorr) in Ar buffer gas of ˜ 15 mTorr at the cell wall temperature of 230 K. The optimum discharge current was 2-4 mA with 250 Gauss longitudinal magnetic field. The rotational lines of up to J=51-50 in the 495 GHz region have been measured, and the improved rotational and centrifugal distortion constants are obtained. In the discharge optimum for production of C_3N^-, neither CN nor C_3N was detected with a similar signal accumulation time used for observations of the anion. However, this reaction has been found to be an excellent source for HC_3N, and the dominant formation mechanism of C_3N^- is likely to be the dissociative electron attachment to HC_3N. The radiative association of C_3N with electrons seems to be unlikely at least for the extended negative glow discharge. Apparently HC_3N is synthesized by a fast neutral and neutral reaction (C_2{H}_2 + CN → HC_3{N} + {H} It is interesting to see that an isomer, HCCNC, is also detected in the discharge, although the number density of this species is found to be about two orders of magnitude smaller than that of HC_3N. Another isomer, HNCCC, has also been observed with much weaker signal intensity. This species might have been produced by the dissociative recombination reaction of HC_3NH^+ with electrons, although the detection of this cation has not been successful in this type of discharge. T. Amano, J. Chem. Phys., 129, 244305 (2008). P. Thaddeus et al.,Astrophys. J., 677,1132-1139 (2008) K. Graupner et al., New J. Phys., 8,117 (2006) I. R. Sims et al.,Chem. Phys. Lett., 211, 461-468(1992) D. E. Woon and E. Herbst,Astrophys. J., 477, 204-208(1997)

Development and applications of 3D-DIVIMP(HC) Monte Carlo impurity modeling code

NASA Astrophysics Data System (ADS)

Mu, Yarong

A self-contained gas injection system for the Divertor Material Evaluation System (DiMES) on DIII-D, the Porous Plug Injector (PPI), has been employed by A. McLean for in-situ study of chemical erosion in the tokamak divertor environment by injection of CH4. The principal contribution of the present thesis is a new interpretive code, 3D-DIVIMP(HC), which has been developed and successfully applied to the interpretation of the CH, C I, and C II emissions measured during the PPI experiments. The two principal types of experimental data which are compared here with 3D-DIVIMP(HC) code modeling are (a) absolute emissivities measured with a high resolution spectrometer, and (b) 2D filtered camera (TV) pictures taken from a view essentially straight down on the PPI. Incorporating the Janev-Reiter database for the breakup reactions of methane molecules in a plasma, 3D-DIVIMP(HC) is able to replicate these measurements to within the combined experimental and database uncertainties. It is therefore concluded that the basic elements of the physics and chemistry controlling the breakup of methane entering an attached divertor plasma have been identified and are incorporated in 3D-DIVIMP(HC).

Selectivity of arsenite interaction with zinc finger proteins.

PubMed

Zhao, Linhong; Chen, Siming; Jia, Liangyuan; Shu, Shi; Zhu, Pingping; Liu, Yangzhong

2012-08-01

Arsenic is a carcinogenic element also used for the treatment of acute promyelocytic leukemia. The reactivity of proteins to arsenic must be associated with the various biological functions of As. Here, we investigated the selectivity of arsenite to zinc finger proteins (ZFPs) with different zinc binding motifs (C2H2, C3H, and C4). Single ZFP domain proteins were used for the direct comparison of the reactivity of different ZFPs. The binding constants and the reaction rates have been studied quantitatively. Results show that both the binding affinity and reaction rates of single-domain ZFPs follow the trend of C4 > C3H ≫ C2H2. Compared with the C2H2 motif ZFPs, the binding affinities of C3H and C4 motif ZFPs are nearly two orders of magnitude higher and the reaction rates are approximately two-fold higher. The formation of multi-domain ZFPs significantly enhances the reactivity of C2H2 type ZFPs, but has negligible effects on C3H and C4 ZFPs. Consequently, the reactivities of the three types of multi-domain ZFPs are rather similar. The 2D NMR spectra indicate that the As(III)-bound ZFPs are also unfolded, suggesting that arsenic binding interferes with the function of ZFPs.

NIa-Pro of Papaya ringspot virus interacts with Carica papaya eukaryotic translation initiation factor 3 subunit G (CpeIF3G).

PubMed

Gao, Le; Tuo, Decai; Shen, Wentao; Yan, Pu; Li, Xiaoying; Zhou, Peng

2015-02-01

The interaction of papaya eukaryotic translation initiation factor 3 subunit G (CpeIF3G) with Papaya ringspot virus (PRSV) NIa-Pro was validated using a bimolecular fluorescence complementation assay in papaya protoplasts based on the previous yeast two-hybrid assay results. The C-terminal (residues 133-239) fragment of PRSV NIa-Pro and the central domain (residues 59-167) of CpeIF3G were required for effective interaction between NIa-Pro and CpeIF3G as shown by a Sos recruitment yeast two-hybrid system with several deletion mutants of NIa-Pro and CpeIF3G. The central domain of CpeIF3G, which contains a C2HC-type zinc finger motif, is required to bind to other eIFs of the translational machinery. In addition, quantitative real-time reverse transcription PCR assay confirmed that PRSV infection leads to a 2- to 4.5-fold up-regulation of CpeIF3G mRNA in papaya. Plant eIF3G is involved in various stress response by enhancing the translation of resistance-related proteins. It is proposed that the NIa-Pro-CpeIF3G interaction may impair translation preinitiation complex assembly of defense proteins and interfere with host defense.

Cyanopolyyne Chemistry in TMC-1

NASA Astrophysics Data System (ADS)

Winstanley, N.; Nejad, L. A. M.

1996-03-01

Using pseudo-time-dependent models and three different reaction networks, a detailed study of the dominant reaction pathways for the formation of cyanopolyynes and their abundances in TMC-1 is presented. The analysis of the chemical reactions show that for the formation of cyanopolyynes there are two major chemical regimes. First, early times of less than ˜104 yrs when ion-molecule reactions are dominant, the main chemical route for the formation of larger cyanopolyynes is C_n H^ + xrightarrow{N}C_n N^ + xrightarrow{{H_2 }}HC_n N^ + xrightarrow{{H_2 }}H_2 C_n N^ + xrightarrow{{e^ - }}HC_n N wheren=5, 7, and 9. Second, at times greater than 104 yrs, when neutral-neutral reactions become dominant, two major reaction routes for the formation of cyanopolyynes are (a), HCNxrightarrow{{C_2 H}}HC_3 Nxrightarrow{{C_2 H}}HC_5 Nxrightarrow{{C_2 H}}HC_7 Nxrightarrow{{C_2 H}}HC_9 N and (b) C_n H_2 + CN to HC_{n + 1} N + H,{text{ }}n = 4,6, and 8 depending on the reaction network used. The results indicate that for route (a) large abundances ofC 2 H (fractional abundances of ˜10-7), and for route (b) large abundances ofC 2 H 2 are required in order to reproduce the observed abundances of cyanopolyynes. The calculated abundances of cyanopolyynes show great sensitivity to the value of extinction particularly att≳5×105 yrs (i.e. photochemical timescale). The effect of other physical parameters, such as the cosmic-ray ionization abundances are also examined. In general, the model calculations show that the observed abundances of cyanopolyynes can be achieved by pseudo-time-dependent models at late times of several million years.

Direct measurement of the Bose-Einstein condensation universality class in NiCl2-4SC(NH2)2 at ultralow temperatures.

PubMed

Yin, L; Xia, J S; Zapf, V S; Sullivan, N S; Paduan-Filho, A

2008-10-31

In this work, we demonstrate field-induced Bose-Einstein condensation (BEC) in the organic compound NiCl2-4SC(NH2)_{2} using ac susceptibility measurements down to 1 mK. The Ni S=1 spins exhibit 3D XY antiferromagnetism between a lower critical field H_{c1} approximately 2 T and a upper critical field H_{c2} approximately 12 T. The results show a power-law temperature dependence of the phase transition line H_{c1}(T)-H_{c1}(0)=aT;{alpha} with alpha=1.47+/-0.10 and H_{c1}(0)=2.053 T, consistent with the 3D BEC universality class. Near H_{c2}, a kink was found in the phase boundary at approximately 150 mK.

Biosynthesis of pteridines. Reaction mechanism of GTP cyclohydrolase I.

PubMed

Rebelo, Jorge; Auerbach, Günter; Bader, Gerd; Bracher, Andreas; Nar, Herbert; Hösl, Cornelia; Schramek, Nicholas; Kaiser, Johannes; Bacher, Adelbert; Huber, Robert; Fischer, Markus

2003-02-14

GTP cyclohydrolase I catalyses the hydrolytic release of formate from GTP followed by cyclization to dihydroneopterin triphosphate. The enzymes from bacteria and animals are homodecamers containing one zinc ion per subunit. Replacement of Cys110, Cys181, His112 or His113 of the enzyme from Escherichia coli by serine affords catalytically inactive mutant proteins with reduced capacity to bind zinc. These mutant proteins are unable to convert GTP or the committed reaction intermediate, 2-amino-5-formylamino-6-(beta-ribosylamino)-4(3H)-pyrimidinone 5'-triphosphate, to dihydroneopterin triphosphate. The crystal structures of GTP complexes of the His113Ser, His112Ser and Cys181Ser mutant proteins determined at resolutions of 2.5A, 2.8A and 3.2A, respectively, revealed the conformation of substrate GTP in the active site cavity. The carboxylic group of the highly conserved residue Glu152 anchors the substrate GTP, by hydrogen bonding to N-3 and to the position 2 amino group. Several basic amino acid residues interact with the triphosphate moiety of the substrate. The structure of the His112Ser mutant in complex with an undefined mixture of nucleotides determined at a resolution of 2.1A afforded additional details of the peptide folding. Comparison between the wild-type and mutant enzyme structures indicates that the catalytically active zinc ion is directly coordinated to Cys110, Cys181 and His113. Moreover, the zinc ion is complexed to a water molecule, which is in close hydrogen bond contact to His112. In close analogy to zinc proteases, the zinc-coordinated water molecule is suggested to attack C-8 of the substrate affording a zinc-bound 8R hydrate of GTP. Opening of the hydrated imidazole ring affords a formamide derivative, which remains coordinated to zinc. The subsequent hydrolysis of the formamide motif has an absolute requirement for zinc ion catalysis. The hydrolysis of the formamide bond shows close mechanistic similarity with peptide hydrolysis by zinc proteases.

Development of a multipurpose hand controller for JEMRMS

NASA Technical Reports Server (NTRS)

Matsuhira, Nobuto; Iikura, Shoichi; Asakura, Makoto; Shinomiya, Yasuo

1990-01-01

A prototype multipurpose hand controller for the JEMRMS (Japanese Experiment Module Remote Manipulator System) was developed. The hand controller (H/C) is an orthogonal type, with 6 degrees of freedom (DOF) and small size. The orthogonal type H/C is very simple for coordinate transformations and can easily control any type of manipulators. In fact, the JEMRMS is planned to have two manipulators controlled by a common H/C at this stage. The H/C was able to be used as a rate control joystick and a force reflection master arm, using an experimental 6 DOF manipulator. Good maneuverability was confirmed in the verification test. The orthogonal type H/C is suitable for use as a common H/C for the two manipulators of the JEMRMS.

Effect of cobalt substitution on magnetic properties of Ba4Ni2-xCoxFe36O60 hexaferrite

NASA Astrophysics Data System (ADS)

Jiang, Xiaona; Li, Songze; Yu, Zhong; Harris, Vincent G.; Su, Zhijuan; Sun, Ke; Wu, Chuanjian; Guo, Rongdi; Lan, Zhongwen

2018-05-01

Co-substituted U-type hexagonal ferrite bulks, with composition of Ba4Ni2-xCoxFe36O60 (x=0.2, 0.4, 0.6, 0.8), were prepared by a conventional ceramic method. Saturation magnetization (4πMs), coercivity (Hc), and Curie temperature (Tc) were investigated. Anisotropy constant (K1) was calculated by fitting the magnetization curve (M-H) according to the law of approach to saturation, and anisotropy field (Ha) was calculated accordingly. The results reveal that all the samples possess the U-type hexagonal crystallographic structure. With increasing cobalt substitution content (x), the lattice parameters (a and c) almost remain the same owing to the similar radii of Ni2+ (0.72 Å) Co2+ (0.74 Å) ions. 4πMs goes up, while Hc Hc shows an opposite trend. K1 and Ha monotonously decrease resulting from that cobalt substitution weakens the c-axis orientation. Additionally, Tc increases from 467 °C to 484 °C.

The genes for the {alpha}-type HC3 (PMSA2) and {beta}-type HC5 (PMSB1) subunits of human proteasomes map to chromosomes 6q27 and 7p12-p13 by fluorescence in situ hybridization

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

Okumura, Katsuzumi; Nogami, Masahiro; Taguchi, Hiroshi

1995-05-20

The authors have determined the locations of the genes for the two subunits, HC3 and HC5, by fluorescence in situ hybridization (FISH). Chromosome spreads were obtained from phytohemagglutinin-stimulated blood lymphocytes of a healthy donor after thymidine synchronization and bromodeoxyuridine incorporation by the method of Takahashi et al. Genomic DNA fragments of HC3 (4.3 kb, including exons 3, 4, and 5) and HC5 (7.5 kb including exons 1 and 2) (11) were labeled with biotin-16-dUTP by nick-translation. In situ hybridization was performed according to Lichter et al. in the presence of COT-1 DNA as a competitor. Hybridized probe was detected withmore » FITC-conjugated avidin without further signal amplification. Comparison of the fluorescence signals and the banding patterns of the chromosomes indicated that the HC3 and HC5 genes were located on chromosome band 6q27 and 7p12-p13, respectively.« less

Searching for Bio-Precursors and Complex Organic Molecules in Space using the GBT

NASA Technical Reports Server (NTRS)

Cordiner, M.; Charnley, S.; Kisiel, Z.

2012-01-01

Using the latest microwave receiver technology, large organic molecules with abundances as low as approx. 10(exp -11) times that of molecular hydrogen are detectable in cold interstellar clouds via their rotational emission line spectra. We report new observations to search for complex molecules, including molecules of possible pre-biotic importance, using the newly-commissioned Kband focal plane array (KFPA) of the NRAO Robert C. Byrd Green Bank Telescope. Spectra are presented of the dense molecular cloud TMC-1, showing strict upper limits on the level of emission from nitrogen-bearing rings pyrimidine, quinoline and iso-quinoline, carbon-chain oxides C60, C70, HC60 and HC70, and the carbon-chain anion C4H-. The typical RMS brightness temperature noise levels we achieved are approx. 1 mK at around 20 GHz.

Comparison of antibody responses against Mycobacterium tuberculosis antigen Rv0679c in tuberculosis patients from the endemic and non-endemic regions of the Beijing genotype: a case control study.

PubMed

Zhao, Jingge; Matsuba, Takashi; Zhang, Xiaoyan; Leano, Susan; Nakajima, Chie; Chagan-Yasutan, Haorile; Telan, Elizabeth Freda; Suzuki, Yasuhiko; Hattori, Toshio

2017-05-15

Strains of the Beijing genotype of Mycobacterium tuberculosis (MTB) are reportedly associated with the virulence of tuberculosis (TB) infection, unfavorable outcomes of anti-TB treatment, and the global TB pandemic. Rv0679c, a hypothetical membrane protein related to host cell invasion, has a Beijing genotype-specific mutation at residue 142 (Asn142Lys). Antigenicity differences between Rv0679c-Asn142 (N-type) and Rv0679c-Lys142 (K-type) have been previously observed in mice antigen-antibody responses. However, the immune response to Rv0679c in humans remains unknown. Therefore, we aimed to investigate the anti-Rv0679c immune response in TB patients from the endemic and non-endemic regions of the Beijing MTB genotype. We analyzed the Rv0679c-specific antibody responses in 84 subjects from the endemic region of the Beijing genotype MTB in China, including 45 pulmonary TB patients (C-PTB) and 39 healthy controls (C-HC), and 81 subjects from the Philippines (the endemic region of the non-Beijing genotype), including 51 pulmonary TB patients (P-PTB) and 30 healthy controls (P-HC). Anti-tuberculous-glycolipid (TBGL) antigen was used as the control antibody. TBGL IgG titers were higher in both C-PTB and P-PTB than those in their corresponding HC (C-PTB median 4.2, P-PTB median 11.2; C-PTB vs. P-PTB, p > 0.05), suggesting immune response comparability in PTB from two different countries. C-PTB showed a higher response compared to C-HC for anti-K-type IgG (53.3%) than anti-N-type IgG (6.67%); this response was not observed in P-PTB (both N-type and K-type 9.80%). Dimorphic antigen Rv0679c was found to be associated with distinct immune response patterns, indicating the role of Beijing/non-Beijing genotype of MTB in stimulating specific responses in TB patients from the endemic region of Beijing MTB. Meanwhile, reactions to Rv0679c in patients and HC from non-endemic regions of the Beijing MTB may be caused by the response to the common epitope of Rv0679c N/K-type.

Effect of cyclical thermal to mechanical properties of Hybrid Laminate Composites (HLC) with skin recycle polypropylene/natural fiber/halloysite and core PP/KF composites

NASA Astrophysics Data System (ADS)

Sri Suharty, Neng; Ismail, Hanafi; Suci Handayani, Desi; Diharjo, Kuncoro; Rachman Wibowo, Fajar; Arnita Wuri, Margaretha

2016-02-01

This research has successfully synthesized six hybrid laminate composites (HLC). These HLC consist of two layers skin composites and one layer of core PP/KF composites. There are sticked with epoxy adhesive by using cold press method. In this research 6 types of skin are used, namely the rPP (recycled polypropylene, HC1); rPP/DVB/PP-g-AA/KF (HC2); rPP/DVB/PP-g-AA/Hall (HC3); rPP/DVB/PP-g-AA/Hall+ZB (HC4); rPP/DVB/PP-g-AA/KF/Hall (HC5) and rPP/DVB/PP-g-AA/KF/Hall+ZB (HC6) composites. The mechanical properties assessment tensile strength (TS) of various HLC before and after cyclical thermal (CT) was done by ASTM D638. While testing the flame retardant: such as time to ignition (TTI) and burning rate (BR) was done by ASTM D635. Heat stability of HLC can be recognized by conducting the CT treatment. It is to determine the effect of fluctuating heat loads on mechanical properties of HLC materials. The TS result of five HLCs (HC2, HC3, HC4, HC5 and HC6) before CT treatment were higher than HC1 (blank HLC). Those five HLC are also able to increase the TTI and reduce the BR compared to HC1. The CT treatment conditions performed at 45 oC as much as 125 times. After CT treatment, the TS values only slightly decline compared to before CT treatment.

Thermal stability of hydrocarbons in nature: Limits, evidence, characteristics, and possible controls

USGS Publications Warehouse

Price, L.C.

1993-01-01

Numerous petroleum-geochemical analyses of deeply buried, high-rank, fine-grained rocks from ultra-deep wellbores by different investigators demonstrate that C15+ hydrocarbons (HCs) persist in moderate to high concentrations at vitrinite reflectance (R0) values of 2.0-5.0% and persist in measurable concentrations up to R0 = 7.0-8.0%, at which point the thermal deadline for C15+ HC's is finally approached. Qualitative analyses have been carried out on 1. (1) high-rank gas condensates which have been exposed to the HC-thermal-destructive phase, 2. (2) bitumens from high-temperature aqueous-pyrolysis experiments in the HC-thermal-destructive phase, and 3. (3) bitumens from high-rank, fine-grained rocks near the HC-thermal-destructive phase. These analyses clearly demonstrate that well-defined compositional suites are established in the saturated, aromatic, and sulfur-bearing aromatic HCs in and near the HC-thermal-destructive phase. On the other hand, accepted petroleum-geochemical paradigms place rigid limits on HC thermal stability: C15+ HCs begin thermal cracking at R0 values of 0.9% and are completely thermally destroyed by R0 = 1.35%; C2-C4 HC gases are thermally destroyed by R0 = 2.0% and methane is thermally destroyed by R0 = 4.0%. Furthermore, published data and observations in many HC basins worldwide support these models; for example, 1. (1) sharp basinal zonations of gas and oil deposits vs. maturation rank in HC basins and 2. (2) decreasing C15+ HC concentrations in some fine-grained rocks at ranks of R0 ??? 0.9%. The fact that observed data (C15+ HCs thermally stable to R0 = 7.0-8.0%) is so far removed from predicted behavior (C15+) HCs expected to be thermally destroyed by R0 = 1.35%) may be due to 1. (1) a lack of recognition of some important possible controlling parameters of organic matter (OM) metamorphism and too much importance given to other assumed controlling parameters; and 2. (2) assigning HC distribution patterns in petroleum basins to HC thermal cracking when such patterns may be due to other causes. In the first case, laboratory experiments strongly suggest that the presence of water, increasing fluid pressures, and closed systems (product retention) all suppress OM metamorphic reactions. Conversely, the absence of water, low fluid pressures, and open systems (product escape) all promote OM metamorphic reactions. These experiments also demonstrate that OM metamorphic reactions proceed by reaction kinetics greater than first order. Thus, the effect of geologic time appears to have been over-estimated in OM metamorphism. In the second case, the strong decreases in C15+ HC concentrations in fine-grained rocks with Type III OM over R0 = 0.9-1.35% are most probably due to intense primary migration and loss of HCs to drilling muds during the trip uphole in drilling operations. Data from coals demonstrate that these decreases in HC concentrations cannot be due to C15+ HC thermal destruction. Oil deposits are generally found at shallow depths in basins, and "dry gas" (methane ??? 98% of all HC gases) deposits are found at the greatest depths. This HC distribution pattern would be caused by methane, generated during the late stages of C15+ HC generation, flushing oil (including C2-C4 HC gases condensed into the liquid phase) out of deep basinal traps by Gussow's (1954) principle of differential entrapment. Hence, only "dry gas" deposits are left in the basin deeps. Oil emplacement processes in traps during expulsion and secondary migration could also contribute to the HC distribution pattern observed in petroleum basins. ?? 1993.

Degradation of 4-chloro 2-aminophenol using a novel combined process based on hydrodynamic cavitation, UV photolysis and ozone.

PubMed

Barik, Arati J; Gogate, Parag R

2016-05-01

The degradation of 4-chloro 2-aminophenol (4C2AP), an acute toxic organic compound, has been studied using different approaches based on the hydrodynamic cavitation (HC) with orifice plate as cavitating device, photolysis (UV) and ozonation (O3). The dependency of extent of degradation on operating parameters like operating pressure (2-5 bar), initial pH (3-8) and temperature (30-38 °C) have been established initially to maximize the efficacy of hydrodynamic cavitation. Subsequently the degradation has been studied using combined treatment strategies as HC+UV, HC+O3, UV+O3 and HC+UV+O3 at the established optimum parameters of operating temperature as 30 °C, initial pH of 6 and inlet pressure of 4 bar. The maximum extent of degradation as 96.85% and 73.6% reduction in TOC has been obtained using hydrodynamic cavitation in combination with UV photolysis and ozonation under the optimized operating conditions. The degradation products of 4C2AP have been identified using GC-MS. The present work has clearly established the efficacy of combined treatment approach (HC+UV+O3) for the removal of organic pollutant for the first time. Copyright © 2015 Elsevier B.V. All rights reserved.

Ion-molecule reactions relevant to Titan's ionosphere.

NASA Astrophysics Data System (ADS)

McEwan, M. J.; Scott, G. B. I.; Anicich, V. G.

1998-02-01

Twenty four new ion-molecule reactions are presented for inclusion in the modeling of the ionosphere of Saturn's satellite Titan. Sixteen reactions were re-examined to reduce uncertainties in the previous literature results. In this study the authors have examined the reactions of N+ and N2+ with CH4, C2H2, C2H4, C2H6, HCN, CH2CHCN and HC3N; the reaction of N+ with CH3CN; the reactions of C3H5+ with CH4, C2H2 C2H4, C2H6, H2, HCN, HC3N and CH2CHCN; the reactions of C2N2+ with C2H2; C2H2+ and C2N2; C2H4 with C2H3+, C2H4+, CHCCNH+, and HC5N+; HCNH+ with C2H6; C3H6+ with C3H6; HCN with C2H6+, C3H6+, c-C3H6+, C2N2+ and NO+; N2 with C2H2+ and C2H5+; C2H4+ and HC3N. The ions selected for this study were derived either from nitrogen, appropriate hydrocarbons or nitriles. The reactant neutrals were selected on the basis of their known presence in Titan's atmosphere. The reaction products are consistent with the expected increase in ion size through ion-molecule reaction processing. Data are also presented for the reactions of 23 ions with molecular nitrogen. Almost all of these ions are unreactive with N2.

Different mechanisms at different temperatures for the ring-opening polymerization of lactide catalyzed by binuclear magnesium and zinc alkoxides.

PubMed

Sun, Yangyang; Cui, Yaqin; Xiong, Jiao; Dai, Zhongran; Tang, Ning; Wu, Jincai

2015-10-07

Two binuclear magnesium and zinc alkoxides supported by a bis-salalen type dinucleating heptadentate Schiff base ligand were synthesized and fully characterized. The two complexes are efficient initiators for the ring-opening polymerization (ROP) of L-lactide, affording polymers with narrow polydispersities and desirable molecular weights. Interestingly, the mechanisms for the ROP of lactide are different at different temperatures. At a high temperature of 130 °C, a coordination-insertion mechanism is reasonable for the bulk melt polymerization of lactide. At a low temperature, the alkoxide cannot initiate the ROP reaction; however, upon the addition of external benzyl alcohol into the system, the ROP of lactide can smoothly proceed via an "activated monomer" mechanism. In addition, these complexes display slight stereo-selectivity for the ring-opening polymerization of rac-lactide, affording partially isotactic polylactide in toluene with a Pm value of 0.59.

A quasi-hexagonal prism-shaped carbon nitride for photoreduction of carbon dioxide under visible light.

PubMed

He, Zhiqiao; Wang, Danfen; Tang, Juntao; Song, Shuang; Chen, Jianmeng; Tao, Xinyong

2017-03-01

A quasi-hexagonal prism-shaped carbon nitride (H-C 3 N 4 ) was synthesized from urea-derived C 3 N 4 (U-C 3 N 4 ) using an alkaline hydrothermal process. U-C 3 N 4 decomposition followed by hydrogen bond rearrangement of hydrolyzed products leads to the formation of a quasi-hexagonal prism-shaped structure. The H-C 3 N 4 catalysts displayed superior activity in the photoreduction of CO 2 with H 2 O compared to U-C 3 N 4 . The enhanced photocatalytic activities can be attributed to the promotion of incompletely coordinated nitrogen atom formation in the C 3 N 4 molecules. Graphical abstract ᅟ.

RING Type E3 Ligase CaAIR1 in Pepper Acts in the Regulation of ABA Signaling and Drought Stress Response.

PubMed

Park, Chanmi; Lim, Chae Woo; Baek, Woonhee; Lee, Sung Chul

2015-09-01

Several E3 ubiquitin ligases have been associated with the response to abiotic and biotic stresses in higher plants. Here, we report that the hot pepper (Capsicum annuum) ABA-Insensitive RING protein 1 gene (CaAIR1) is essential for a hypersensitive response to drought stress. CaAIR1 contains a C3HC4-type RING finger motif, which plays a role for attachment of ubiquitins to the target protein, and a putative transmembrane domain. The expression levels of CaAIR1 are up-regulated in pepper leaves by ABA treatments, drought and NaCl, suggesting its role in the response to abiotic stress. Our analysis showed that CaAIR1 displays self-ubiquitination and is localized in the nucleus. We generated CaAIR1-silenced peppers via virus-induced gene silencing (VIGS) and CaAIR1-overexpressing (OX) transgenic Arabidopsis plants to evaluate their responses to ABA and drought. VIGS of CaAIR1 in pepper plants conferred an enhanced tolerance to drought stress, which was accompanied by low levels of transpirational water loss in the drought-treated leaves. CaAIR1-OX plants displayed an impaired sensitivity to ABA during seed germination, seedling and adult stages. Moreover, these plants showed enhanced sensitivity to drought stress because of reduced stomatal closure and decreased expression of stress-responsive genes. Thus, our data indicate that CaAIR1 is a negative regulator of the ABA-mediated drought stress tolerance mechanism. © The Author 2015. Published by Oxford University Press on behalf of Japanese Society of Plant Physiologists. All rights reserved. For permissions, please email: journals.permissions@oup.com.

Molecular and functional characterization of pigeon (Columba livia) tumor necrosis factor receptor-associated factor 3.

PubMed

Zhou, Yingying; Kang, Xilong; Xiong, Dan; Zhu, Shanshan; Zheng, Huijuan; Xu, Ying; Guo, Yaxin; Pan, Zhiming; Jiao, Xinan

2017-04-01

Tumor necrosis factor receptor-associated factor 3 (TRAF3) plays a key antiviral role by promoting type I interferon production. We cloned the pigeon TRAF3 gene (PiTRAF3) according to its predicted mRNA sequence to investigate its function. The 1704-bp full-length open reading frame encodes a 567-amino acid protein. One Ring finger, two TRAF-type Zinc fingers, one Coiled coil, and one MATH domain were inferred. RT-PCR showed that PiTRAF3 was expressed in all tissues, with relatively weak expression in the heart and liver. In HEK293T cells, over-expression of wild-type, △Ring, △Zinc finger, and △Coiled coil PiTRAF3, but not a △MATH form, significantly increased IFN-β promoter activity. Zinc finger and Coiled coil domains were essential for NF-κB activation. In chicken HD11 cells, PiTRAF3 increased IFN-β promoter activity and four domains were all contributing. R848 stimulation of pigeon peripheral blood mononuclear cells and splenocytes significantly increased expression of PiTRAF3 and the inflammatory cytokine genes CCL5, IL-8, and IL-10. These data demonstrate TRAF3's innate immune function and improve understanding of its involvement in poultry antiviral defense. Copyright © 2016 Elsevier Ltd. All rights reserved.

Long-Term Effects of a Very Low Carbohydrate Compared With a High Carbohydrate Diet on Renal Function in Individuals With Type 2 Diabetes

PubMed Central

Tay, Jeannie; Thompson, Campbell H.; Luscombe-Marsh, Natalie D.; Noakes, Manny; Buckley, Jonathan D.; Wittert, Gary A.; Brinkworth, Grant D.

2015-01-01

Abstract To compare the long-term effects of a very low carbohydrate, high-protein, low saturated fat (LC) diet with a traditional high unrefined carbohydrate, low-fat (HC) diet on markers of renal function in obese adults with type 2 diabetes (T2DM), but without overt kidney disease. One hundred fifteen adults (BMI 34.6 ± 4.3 kg/m2, age 58 ± 7 years, HbA1c 7.3 ± 1.1%, 56 ± 12 mmol/mol, serum creatinine (SCr) 69 ± 15 μmol/L, glomerular filtration rate estimated by the Chronic Kidney Disease Epidemiology Collaboration formula (eGFR 94 ± 12 mL/min/1.73 m2)) were randomized to consume either an LC (14% energy as carbohydrate [CHO < 50 g/day], 28% protein [PRO], 58% fat [<10% saturated fat]) or an HC (53% CHO, 17% PRO, 30% fat [<10% saturated fat]) energy-matched, weight-loss diet combined with supervised exercise training (60 min, 3 day/wk) for 12 months. Body weight, blood pressure, and renal function assessed by eGFR, estimated creatinine clearance (Cockcroft–Gault, Salazar–Corcoran) and albumin excretion rate (AER), were measured pre- and post-intervention. Both groups achieved similar completion rates (LC 71%, HC 65%) and reductions in weight (mean [95% CI]; −9.3 [−10.6, −8.0] kg) and blood pressure (−6 [−9, −4]/−6[−8, −5] mmHg), P ≥ 0.18. Protein intake calculated from 24 hours urinary urea was higher in the LC than HC group (LC 120.1 ± 38.2 g/day, 1.3 g/kg/day; HC 95.8 ± 27.8 g/day, 1 g/kg/day), P < 0.001 diet effect. Changes in SCr (LC 3 [1, 5], HC 1 [−1, 3] μmol/L) and eGFR (LC −4 [−6, −2], HC −2 [−3, 0] mL/min/1.73 m2) did not differ between diets (P = 0.25). AER decreased independent of diet composition (LC −−2.4 [−6, 1.2], HC −1.8 [−5.4, 1.8] mg/24 h, P = 0.24); 6 participants (LC 3, HC 3) had moderately elevated AER at baseline (30–300 mg/24 h), which normalized in 4 participants (LC 2, HC 2) after 52 weeks. Compared with a traditional HC weight loss diet, consumption of an LC high protein diet does not adversely affect clinical markers of renal function in obese adults with T2DM and no preexisting kidney disease. PMID:26632754

Unimolecular Thermal Fragmentation of Ortho-Benzyne

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

Zhang, X.; Maccarone, A. T.; Nimlos, M. R.

2007-01-01

The ortho-benzyne diradical, o-C{sub 6}H{sub 4} has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments: o-C{sub 6}H{sub 4} + {Delta} {yields} products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C{sub 6}H{sub 4} + {Delta} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. The experimentalmore » {Delta}{sub rxn}H{sub 298}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) is found to be 57 {+-} 3 kcal mol{sup -1}. Further experiments with the substituted benzyne, 3,6-(CH{sub 3}){sub 2}-o-C{sub 6}H{sub 2}, are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)/H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connected quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C{sub 2v}-symmetric decomposition of o-benzyne, E{sub b}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) = 88.0 {+-} 0.5 kcal mol{sup -1}. A barrier of this magnitude is consistent with the experimental results. A careful assessment of the thermochemistry for the high temperature fragmentation of benzene is presented: C{sub 6}H{sub 6} {yields} H+[C{sub 6}H{sub 5}] {yields} H+[o-C{sub 6}H{sub 4}] {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. Benzyne may be an important intermediate in the thermal decomposition of many alkylbenzenes (arenes). High engine temperatures above 1500 K may crack these alkylbenzenes to a mixture of alkyl radicals and phenyl radicals. The phenyl radicals will then dissociate first to benzyne and then to acetylene and diacetylene.« less

Unimolecular thermal fragmentation of ortho-benzene.

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

Zhang, X.; Maccarone, A. T.; Nimlos, M. R.

2007-01-01

The ortho-benzyne diradical, o-C{sub 6}H{sub 4} has been produced with a supersonic nozzle and its subsequent thermal decomposition has been studied. As the temperature of the nozzle is increased, the benzyne molecule fragments o-C{sub 6}H{sub 4}{sup +} {Delta} {yields} products. The thermal dissociation products were identified by three experimental methods: (i) time-of-flight photoionization mass spectrometry, (ii) matrix-isolation Fourier transform infrared absorption spectroscopy, and (iii) chemical ionization mass spectrometry. At the threshold dissociation temperature, o-benzyne cleanly decomposes into acetylene and diacetylene via an apparent retro-Diels-Alder process: o-C{sub 6}H{sub 4}{sup +}{Delta}{yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH. The experimental {Delta}{sub rxn}H{submore » 298}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) is found to be 57 {+-} 3 kcal mol{sup -1}. Further experiments with the substituted benzyne, 3,6-(CH{sub 3}){sub 2}-o-C{sub 6}H{sub 2}, are consistent with a retro-Diels-Alder fragmentation. But at higher nozzle temperatures, the cracking pattern becomes more complicated. To interpret these experiments, the retro-Diels-Alder fragmentation of o-benzyne has been investigated by rigorous ab initio electronic structure computations. These calculations used basis sets as large as [C(7s6p5d4f3g2h1i)/H(6s5p4d3f2g1h)] (cc-pV6Z) and electron correlation treatments as extensive as full coupled cluster through triple excitations (CCSDT), in cases with a perturbative term for connected quadruples [CCSDT(Q)]. Focal point extrapolations of the computational data yield a 0 K barrier for the concerted, C{sub 2v}-symmetric decomposition of o-benzyne, E{sub b}(o-C{sub 6}H{sub 4} {yields} HC {triple_bond} CH+HC {triple_bond} C-C {triple_bond} CH) = 88.0 {+-} 0.5 kcal mol{sup -1}. A barrier of this magnitude is consistent with the experimental results. A careful assessment of the thermochemistry for the high temperature fragmentation of benzene is presented: C{sub 6}H{sub 6} {yields} H+[C{sub 6}H{sub 5}] {yields} H+[o-C{sub 6}H{sub 4}] {yields} HC {triple_bond} CH-HC {triple_bond} C-C {triple_bond} CH. Benzyne may be an important intermediate in the thermal decomposition of many alkylbenzenes (arenes). High engine temperatures above 1500 K may crack these alkylbenzenes to a mixture of alkyl radicals and phenyl radicals. The phenyl radicals will then dissociate first to benzyne and then to acetylene and diacetylene.« less

Effect prediction of identified SNPs linked to fruit quality and chilling injury in peach [Prunus persica (L.) Batsch].

PubMed

Martínez-García, Pedro J; Fresnedo-Ramírez, Jonathan; Parfitt, Dan E; Gradziel, Thomas M; Crisosto, Carlos H

2013-01-01

Single nucleotide polymorphisms (SNPs) are a fundamental source of genomic variation. Large SNP panels have been developed for Prunus species. Fruit quality traits are essential peach breeding program objectives since they determine consumer acceptance, fruit consumption, industry trends and cultivar adoption. For many cultivars, these traits are negatively impacted by cold storage, used to extend fruit market life. The major symptoms of chilling injury are lack of flavor, off flavor, mealiness, flesh browning, and flesh bleeding. A set of 1,109 SNPs was mapped previously and 67 were linked with these complex traits. The prediction of the effects associated with these SNPs on downstream products from the 'peach v1.0' genome sequence was carried out. A total of 2,163 effects were detected, 282 effects (non-synonymous, synonymous or stop codon gained) were located in exonic regions (13.04 %) and 294 placed in intronic regions (13.59 %). An extended list of genes and proteins that could be related to these traits was developed. Two SNP markers that explain a high percentage of the observed phenotypic variance, UCD_SNP_1084 and UCD_SNP_46, are associated with zinc finger (C3HC4-type RING finger) family protein and AOX1A (alternative oxidase 1a) protein groups, respectively. In addition, phenotypic variation suggests that the observed polymorphism for SNP UCD_SNP_1084 [A/G] mutation could be a candidate quantitative trait nucleotide affecting quantitative trait loci for mealiness. The interaction and expression of affected proteins could explain the variation observed in each individual and facilitate understanding of gene regulatory networks for fruit quality traits in peach.

Dimensionality Alteration and Intra- versus Inter-SBU Void Encapsulation in Zinc Phosphate Frameworks.

PubMed

Dar, Aijaz A; Bhat, Gulzar A; Murugavel, Ramaswamy

2016-06-06

4,4'-Bipyridine-N-oxide (BIPYMO, 1), a less commonly employed coordination polymer linker, has been used as a ditopic spacer to bridge double-four-ring (D4R) zinc phosphate clusters to form novel framework coordination polymers. Zinc phosphate framework compounds [Zn4(X-dipp)4(BIPYMO)2]n·2MeOH [X = H (2), Cl (3), Br (4), I (5); dipp = 2,6-diisopropylphenyl phosphate] have been obtained by treating a methanol solution of zinc acetate with X-dippH2 and BIPYMO (in a 1:1:1 molar ratio) at ambient conditions. Framework phosphates 2-5 can also be obtained by treating the preformed D4R cubanes [Zn(X-dipp)(DMSO)]4 with required quantities of BIPYMO in methanol. Single-crystal X-ray diffraction studies reveal that these framework solids are two-dimensional (2D) networks as opposed to the diamondoid networks obtained when the parent unoxidized 4,4'-bipyridine is used as the linker (Inorg. Chem. 2014, 53, 8959). The two types of voids (viz., smaller intra-D4R and larger inter-D4R) present in these framework solids can be utilized for different types of encapsulation processes. For example, the in situ generated 2D framework 2 encapsulates fluoride ions accompanied by a change in the dimensionality of the framework to yield {[(nC4H9)4N][F@(Zn4(dipp)4(BIPYMO)2)]}n (6). The three-dimensional framework 6 represents the first structurally characterized example of a fluoride-ion-encapsulated polymeric coordination compound or a metal-organic framework. The possibility of utilizing inter-D4R voids as hosts for small organic molecules has been explored by treating in situ generated 2 with a series of organic molecules of appropriate size. Framework 2 has been found to be a selective host for benzil and not for other structurally similar molecules such as benzoquinone, benzidine, anthracene, naphthalene, α-pyridoin, etc. The benzil-occluded isolated framework [benzil@{Zn4(dipp)4(BIPYMO)2}]n (7) has been isolated as single crystals, and its crystal structure determination revealed the binding of benzil molecules to the framework through strong π-π interactions.

Fractional quantization of the magnetic flux in cylindrical unconventional superconductors.

PubMed

Loder, F; Kampf, A P; Kopp, T

2013-07-26

The magnetic flux threading a conventional superconducting ring is typically quantized in units of Φ0=hc/2e. The factor of 2 in the denominator of Φ0 originates from the existence of two different types of pairing states with minima of the free energy at even and odd multiples of Φ0. Here we show that spatially modulated pairing states exist with energy minima at fractional flux values, in particular, at multiples of Φ0/2. In such states, condensates with different center-of-mass momenta of the Cooper pairs coexist. The proposed mechanism for fractional flux quantization is discussed in the context of cuprate superconductors, where hc/4e flux periodicities were observed.

Low programmed cell death-1 (PD-1) expression in peripheral CD4(+) T cells in Japanese patients with autoimmune type 1 diabetes.

PubMed

Fujisawa, R; Haseda, F; Tsutsumi, C; Hiromine, Y; Noso, S; Kawabata, Y; Mitsui, S; Terasaki, J; Ikegami, H; Imagawa, A; Hanafusa, T

2015-06-01

Programmed cell death-1 (PD-1) is a co-stimulatory molecule that inhibits T cell proliferation. We aimed to clarify PD-1 expression in CD4(+) T cells and the association between PD-1 expression and the 7785C/T polymorphism of PDCD1, with a focus on the two subtypes of type 1 diabetes, type 1A diabetes (T1AD) and fulminant type 1 diabetes (FT1D), in the Japanese population. We examined 22 patients with T1AD, 15 with FT1D, 19 with type 2 diabetes (T2D) and 29 healthy control (HC) subjects. Fluorescence-activated cell sorting (FACS) and real-time PCR were utilized to analyse PD-1 expression quantitatively. Genotyping of 7785C/T in PDCD1 was performed using the TaqMan method in a total of 63 subjects (21 with T1AD, 15 with FT1D and 27 HC). FACS revealed a significant reduction in PD-1 expression in CD4(+) T cells in patients with T1AD (mean: 4.2 vs. 6.0% in FT1D, P=0.0450; vs. 5.8% in T2D, P=0.0098; vs. 6.0% in HC, P=0.0018). PD-1 mRNA expression in CD4(+) T cells was also significantly lower in patients with T1AD than in the HC subjects. Of the 63 subjects, PD-1 expression was significantly lower in individuals with the 7785C/C genotype than in those with the C/T and T/T genotypes (mean: 4.1 vs. 5.9%, P=0.0016). Our results indicate that lower PD-1 expression in CD4(+) T-cells might contribute to the development of T1AD through T cell activation. © 2015 British Society for Immunology.

Degradation of 2,4-dinitrophenol using a combination of hydrodynamic cavitation, chemical and advanced oxidation processes.

PubMed

Bagal, Manisha V; Gogate, Parag R

2013-09-01

In the present work, degradation of 2,4-dinitrophenol (DNP), a persistent organic contaminant with high toxicity and very low biodegradability has been investigated using combination of hydrodynamic cavitation (HC) and chemical/advanced oxidation. The cavitating conditions have been generated using orifice plate as a cavitating device. Initially, the optimization of basic operating parameters have been done by performing experiments over varying inlet pressure (over the range of 3-6 bar), temperature (30 °C, 35 °C and 40 °C) and solution pH (over the range of 3-11). Subsequently, combined treatment strategies have been investigated for process intensification of the degradation process. The effect of HC combined with chemical oxidation processes such as hydrogen peroxide (HC/H2O2), ferrous activated persulfate (HC/Na2S2O8/FeSO4) and HC coupled with advanced oxidation processes such as conventional Fenton (HC/FeSO4/H2O2), advanced Fenton (HC/Fe/H2O2) and Fenton-like process (HC/CuO/H2O2) on the extent of degradation of DNP have also been investigated at optimized conditions of pH 4, temperature of 35 °C and inlet pressure of 4 bar. Kinetic study revealed that degradation of DNP fitted first order kinetics for all the approaches under investigation. Complete degradation with maximum rate of DNP degradation has been observed for the combined HC/Fenton process. The energy consumption analysis for hydrodynamic cavitation based process has been done on the basis of cavitational yield. Degradation intermediates have also been identified and quantified in the current work. The synergistic index calculated for all the combined processes indicates HC/Fenton process is more feasible than the combination of HC with other Fenton like processes. Copyright © 2013 Elsevier B.V. All rights reserved.

Organic metamorphism in the California petroleum basins; Chapter B, Insights from extractable bitumen and saturated hydrocarbons

USGS Publications Warehouse

Price, Leigh C.

2000-01-01

Seventy-five shales from the Los Angeles, Ventura, and Southern San Joaquin Valley Basins were extracted and analyzed. Samples were chosen on the basis of ROCK-EVAL analyses of a much larger sample base. The samples ranged in burial temperatures from 40 ? to 220 ? C, and contained hydrogen-poor to hydrogen-rich organic matter (OM), based on OM visual typing and a correlation of elemental kerogen hydrogen to carbon ratios with ROCK-EVAL hydrogen indices. By extractable bitumen measurements, rocks with hydrogen- poor OM in the Los Angeles Basin began mainstage hydrocarbon (HC) generation by 90 ? C. The HC concentrations maximized by 165 ? C, and beyond 165 ? C, HC and bitumen concentrations and ROCK-EVAL hydrogen indices all began decreasing to low values reached by 220 ? C, where HC generation was largely complete. Rocks with hydrogen-poor OM in the Southern San Joaquin Valley Basin commenced mainstage HC generation at 135 ? C and HC concentrations maximized by 180 ? C. Above 180 ? C, HC and bitumen concentrations and ROCK-EVAL hydrogen indices all decreased to low values reached by 214 ? C, again the process of HC generation being largely complete. In both cases, bell-shaped HC-generation curves were present versus depth (burial temperature). Mainstage HC generation had not yet begun in Ventura Basin rocks with hydrogen-poor OM by 140 ? C. The apparent lower temperature for initiation of mainstage generation in the Los Angeles Basin is attributed to very recent cooling in that basin from meteoric-water flow. Thus, HC generation there most probably occurred at higher burial temperatures. In contrast, mainstage HC generation, and all aspects of organic metamorphism, were strongly suppressed in rocks with hydrogen-rich OM at temperatures as high as 198 ? C. For example, shales from the Wilmington field (Los Angeles Basin) from 180 ? to 198 ? C retained ROCK-EVAL hydrogen indices of 550- 700 and had saturated-HC coefficients of only 4-15 mg/g organic carbon. The rocks with hydrogen-rich OM were subjected to the same burial conditions as the rocks with hydrogenpoor OM. We attribute this suppression of organic metamorphism in this study primarily to much stronger bonds in the hydrogen-rich OM compared to the bonds in hydrogen-poor OM. Trends in bitumen compositions (qualitative characteristics) versus burial temperature were also very different for rocks with hydrogen-poor OM compared to that in rocks with hydrogen- rich OM. This observation demonstrated that the two OM types also had significantly different reaction pathways, in addition to different reaction kinetics. Strong exploration implications arise from these observations. Above 40?C, but before mainstage HC generation, a lowtemperature (pre-mainstage) HC generation occurred in all rocks, and all OM types, studied. This low-temperature generation resulted in significant qualitative changes in the bitumen and HCS (hydrocarbons) from rocks of all OM types, especially in rocks with hydrogen-rich OM, from 40 ? to 70 ? C. This, and previous studies, document that very high carbon-normalized concentrations of indigenous bitumen and HCS occur in late Neogene immature rocks of any OM type in all southern California basins. This characteristic is attributed to the low-temperature generation occurring in both sulfur-poor and sulfur-rich kerogens, which originally had unusually high concentrations of weak (15-40 Kcal/mole) bonds. These observations and considerations have marked relevance to exploration regarding the possible formation of commercial oil deposits at immature ranks in these basins. Other significant geochemical observations also result from this study.

TMRT OBSERVATIONS OF CARBON-CHAIN MOLECULES IN SERPENS SOUTH 1a

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

Li, Juan; Shen, Zhi-Qiang; Wang, Junzhi

2016-06-20

We report Shanghai Tian Ma Radio Telescope (TMRT) detections of several long carbon-chain molecules in the C and Ku bands, including HC{sub 3}N, HC{sub 5}N, HC{sub 7}N, HC{sub 9}N, C{sub 3}S, C{sub 6}H, and C{sub 8}H toward the starless cloud Serpens South 1a. We detected some transitions (HC{sub 9}N J = 13–12, F = 12–11, and F = 14–13; H{sup 13}CCCN J = 2–1, F = 1–0, and F = 1–1; HC{sup 13}CCN J = 2–1, F = 2–2, F = 1–0, and F = 1–1; HCC{sup 13}CN J = 2–1, F = 1–0, and F = 1–1) and resolvedmore » some hyperfine components (HC{sub 5}N J = 6–5, F = 5–4; H{sup 13}CCCN J = 2–1, F = 2–1) for the first time in the interstellar medium. The column densities of these carbon-chain molecules in the range 10{sup 12}–10{sup 13} cm{sup −2} are comparable to two carbon-chain molecule rich sources, TMC-1 and Lupus-1A. The abundance ratios are 1.00:(1.11 ± 0.15):(1.47 ± 0.18) for [H{sup 13}CCCN]:[HC{sup 13}CCN]:[HCC{sup 13}CN]. This result implies that the {sup 13}C isotope is also concentrated in the carbon atom adjacent to the nitrogen atom in HC{sub 3}N in Serpens South 1a, which is similar to TMC-1. The [HC{sub 3}N]/[H{sup 13}CCCN] ratio of 78 ± 9, the [HC{sub 3}N]/[HC{sup 13}CCN] ratio of 70 ± 8, and the [HC{sub 3}N]/[HCC{sup 13}CN] ratio of 53 ± 4 are also comparable to those in TMC-1. Serpens South 1a proves to be a suitable testing ground for understanding carbon-chain chemistry.« less

Dichloridobis(phenanthridine-κN)zinc(II).

PubMed

Khoshtarkib, Zeinab; Ebadi, Amin; Alizadeh, Robabeh; Ahmadi, Roya; Amani, Vahid

2009-06-06

In the mol-ecule of the title compound, [ZnCl(2)(C(13)H(9)N)(2)], the Zn(II) atom is four-coordinated in a distorted tetra-hedral configuration by two N atoms from two phenanthridine ligands and by two terminal Cl atoms. The dihedral angle between the planes of the phenanthridine ring systems is 69.92 (3)°. An intra-molecular C-H⋯Cl inter-action results in the formation of a planar five-membered ring, which is oriented at a dihedral angle of 8.32 (3)° with respect to the adjacent phenanthridine ring system. In the crystal structure, π-π contacts between the phenanthridine systems [centroid-centroid distances = 3.839 (2), 3.617 (1) and 3.682 (1) Å] may stabilize the structure. Two weak C-H⋯π inter-actions are also found.

Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13C NMR spectroscopy

USGS Publications Warehouse

Mao, J.; Fang, X.; Lan, Y.; Schimmelmann, A.; Mastalerz, Maria; Xu, L.; Schmidt-Rohr, K.

2010-01-01

We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R0 from 0.29% to 1.27%). Specific functional groups such as CH3, CH2, alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as "oil prone" and "gas prone" carbons, have been quantified by 13C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (???30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ???30 carbons, and of ???20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1H-13C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters. ?? 2010 Elsevier Ltd. All rights reserved.

Cross-bridge kinetics of fast and slow fibres of cat jaw and limb muscles: correlations with myosin subunit composition.

PubMed

Hoh, Joseph F Y; Li, Zhao-Bo; Qin, Han; Hsu, Michael K H; Rossmanith, Gunther H

2007-01-01

Mechanical properties of the jaw-closing muscles of the cat are poorly understood. These muscles are known to differ in myosin and fibre type compositions from limb muscles. This work aims to correlate mechanical properties of single fibres in cat jaw and limb muscles with their myosin subunit compositions. The stiffness minimum frequency, f(min), which reflects isometric cross-bridge kinetics, was measured in Ca(2+)-activated glycerinated fast and slow fibres from cat jaw and limb muscles for temperatures ranging between 15 and 30 degrees C by mechanical perturbation analysis. At 15 degrees C, f(min) was 0.5 Hz for limb-slow fibres, 4-6 Hz for jaw-slow fibres, and 10-13 Hz for limb-fast and jaw-fast fibres. The activation energy for f(min) obtained from the slope of the Arrhenius plot for limb-slow fibres was 30-40% higher than values for the other three types of fibres. SDS-PAGE and western blotting using highly specific antibodies verified that limb-fast fibres contained IIA or IIX myosin heavy chain (MyHC). Jaw-fast fibres expressed masticatory MyHC while both jaw-fast and jaw-slow fibres expressed masticatory myosin light chains (MLCs). The nucleotide sequences of the 3' ends of the slow MyHC cDNAs isolated from cat masseter and soleus cDNA libraries showed identical coding and 3'-untranslated regions, suggesting that jaw-slow and limb-slow fibres express the same slow MyHC gene. We conclude that the isometric cross-bridge cycling kinetics of jaw-fast and limb-fast fibres detected by f(min) are indistinguishable in spite of differences in MyHC and light chain compositions. However, jaw-slow fibres, in which the same slow MyHCs are found in combination with MLCs of the jaw type, show enhanced cross-bridge cycling kinetics and reduced activation energy for cross-bridge detachment.

Store Separations From a Supersonic Cone

DTIC Science & Technology

2006-03-01

L DK/9H|; 21W-0< ,.LMD >DK/@HX½1¢, H|3*]�&¢DK>4ɜH|C H�I21WDK, > L@C 14L95 :H|3 > 3 ;=,.L H|L9C H|; .H 1 HJ3K1 ,.L ? ODK /9H...4; @I)DKH¯C > .I9D ,.> L@C{143 >4I@L@5 -J> ; .H 5¢L21W; , - HJ> ;=HJDK36,.HJC|8QA236> ; 14LH -J,.HJL@-C6D01WL@5 :> ,.LMD? ODK /9H 3...H 93 H|C6C I@36H > ]�[)8 [ ` I@C6,.L $ �I21^DK,.>4L@CQ\\ D /@3 > I /a º` ` [ t8 P½C½>4L@HU-14LC HJH4? ODK /@H

Performance characteristics of zinc-rich coatings applied to carbon steel

NASA Technical Reports Server (NTRS)

Paton, W. J.

1973-01-01

A program was conducted to evaluate the performance of topcoated and untopcoated zinc-rich coatings. Sacrificial coatings of this type are required for protecting carbon steel structures from the aggressive KSC sea coast environment. A total of 59 commercially available zinc-rich coatings and 47 topcoated materials were exposed for an 18-month period. Test panels were placed in special racks placed approximately 30.5 m (100 feet) above the high tide line at the KSC Corrosion Test Site. Laboratory tests to determine the temperature resistance, abrasion resistance, and adhesion of the untopcoated zinc-rich coatings were also performed. It has been concluded that: (1) The inorganic types of zinc-rich coatings are far superior to the organic types in the KSC environment. (2) Organic zinc-rich coatings applied at 0.1 - 0.15 mm (4-6 mils) film thickness provide better corrosion protection than when applied at the manufacturers' recommended nominal film thickness of .08 mm (3 mils). (3) Topcoats are not necessary, or even desirable, when used in conjunction with zinc-rich coatings in the KSC environment. (4) Some types of inorganic zinc-rich coatings require an extended outdoor weathering period in order to obtain adequate mechanical properties. and (5) A properly formulated inorganic zinc-rich coating is not affected by a 24-hour thermal exposure to 400 C (752 F).

The photochemistry of some possible cometary CN parent species

NASA Technical Reports Server (NTRS)

Halpern, Joshua B.

1987-01-01

Laboratory work on the photochemistry of HC3N, C4N2, and CH3CN in relation to their possible role as CN parent molecules in comets is discussed. Photodissociation of HC3N, photolysis of C4N2, and quantum yields of excited CN(B) and CN(A) radicals from the VUV photolysis of CH3CN are considered.

40 CFR 1065.341 - CVS and batch sampler verification (propane check).

Code of Federal Regulations, 2010 CFR

2010-07-01

... contamination. Otherwise, zero, span, and verify contamination of the HC sampling system, as follows: (1) Select... flow rates. (2) Zero the HC analyzer using zero air introduced at the analyzer port. (3) Span the HC analyzer using C3H8 span gas introduced at the analyzer port. (4) Overflow zero air at the HC probe inlet...

40 CFR 1065.341 - CVS and batch sampler verification (propane check).

Code of Federal Regulations, 2011 CFR

2011-07-01

... contamination. Otherwise, zero, span, and verify contamination of the HC sampling system, as follows: (1) Select... flow rates. (2) Zero the HC analyzer using zero air introduced at the analyzer port. (3) Span the HC analyzer using C3H8 span gas introduced at the analyzer port. (4) Overflow zero air at the HC probe inlet...

Indicators of nutritional status in restricting-type anorexia nervosa patients: a 1-year follow-up study.

PubMed

Nova, Esther; Lopez-Vidriero, Irene; Varela, Pilar; Toro, Olga; Casas, J José; Marcos, A Ascensión

2004-12-01

Despite severely reduced intakes, anorexia nervosa (AN) patients seem to maintain serum biochemical parameters within the safe limit. The aim of this study was to assess the evolution of some traditional serum biochemical indicators of nutritional status in a 1-year follow-up of patients with restricting-type AN. 14 adolescent female patients were studied at four different time points: (1) on hospital admission (t0), (2) 1 month later (t1), (3) 6 months after admission (t6) and (4) 12 months after admission (t12). At each time point serum albumin, prealbumin, retinol-binding protein, transferrin, complement factors C3 and C4, zinc and iron status were analysed. 15 healthy adolescents formed the control group. Among the liver-synthesised proteins, a significant time effect was only demonstrated on transferrin and C3 and C4 (ANOVA, P<0.05). Transferrin level in patients on admission was lower than in controls, increased significantly during the first month and showed an opposite pattern in subjects gaining and non-gaining weight between t1 and t12, decreasing only in the group failing to gain further weight. C3 and C4 decreased significantly in t12. Changes in ferritin and zinc showed significant negative correlations with changes in anthropometrical parameters. The changes in transferrin, C3 and C4 levels during the out-patient treatment reveal an increased risk of relapses after 1 year since hospital admission. Ferritin and zinc levels seem to be affected by the nutrient requirements for anabolic processes during nutritional recovery.

Co3O4/MnO2/Hierarchically Porous Carbon as Superior Bifunctional Electrodes for Liquid and All-Solid-State Rechargeable Zinc-Air Batteries.

PubMed

Li, Xuemei; Dong, Fang; Xu, Nengneng; Zhang, Tao; Li, Kaixi; Qiao, Jinli

2018-05-09

The design of efficient, durable, and affordable catalysts for oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is very indispensable in liquid-type and flexible all-solid-state zinc-air batteries. Herein, we present a high-performance bifunctional catalyst with cobalt and manganese oxides supported on porous carbon (Co 3 O 4 /MnO 2 /PQ-7). The optimized Co 3 O 4 /MnO 2 /PQ-7 exhibited a comparable ORR performance with commercial Pt/C and a more superior OER performance than all of the other prepared catalysts, including commercial Pt/C. When applied to practical aqueous (6.0 M KOH) zinc-air batteries, the Co 3 O 4 /MnO 2 /porous carbon hybrid catalysts exhibited exceptional performance, such as a maximum discharge peak power density as high as 257 mW cm -2 and the most stable charge-discharge durability over 50 h with negligible deactivation to date. More importantly, a series of flexible all-solid-state zinc-air batteries can be fabricated by the Co 3 O 4 /MnO 2 /porous carbon with a layer-by-layer method. The optimal catalyst (Co 3 O 4 /MnO 2 /PQ-7) exhibited an excellent peak power density of 45 mW cm -2 . The discharge potentials almost remained unchanged for 6 h at 5 mA cm -2 and possessed a long cycle life (2.5 h@5 mA cm -2 ). These results make the optimized Co 3 O 4 /MnO 2 /PQ-7 a promising cathode candidate for both liquid-type and flexible all-solid-state zinc-air batteries.

Crystal Structures of Human Choline Kinase Isoforms in Complex with Hemicholinium-3 Single Amino Acid near the Active Site Influences Inhibitor Sensitivity

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

Hong, Bum Soo; Allali-Hassani, Abdellah; Tempel, Wolfram

2010-07-06

Human choline kinase (ChoK) catalyzes the first reaction in phosphatidylcholine biosynthesis and exists as ChoK{alpha} ({alpha}1 and {alpha}2) and ChoK{beta} isoforms. Recent studies suggest that ChoK is implicated in tumorigenesis and emerging as an attractive target for anticancer chemotherapy. To extend our understanding of the molecular mechanism of ChoK inhibition, we have determined the high resolution x-ray structures of the ChoK{alpha}1 and ChoK{beta} isoforms in complex with hemicholinium-3 (HC-3), a known inhibitor of ChoK. In both structures, HC-3 bound at the conserved hydrophobic groove on the C-terminal lobe. One of the HC-3 oxazinium rings complexed with ChoK{alpha}1 occupied the choline-bindingmore » pocket, providing a structural explanation for its inhibitory action. Interestingly, the HC-3 molecule co-crystallized with ChoK{beta} was phosphorylated in the choline binding site. This phosphorylation, albeit occurring at a very slow rate, was confirmed experimentally by mass spectroscopy and radioactive assays. Detailed kinetic studies revealed that HC-3 is a much more potent inhibitor for ChoK{alpha} isoforms ({alpha}1 and {alpha}2) compared with ChoK{beta}. Mutational studies based on the structures of both inhibitor-bound ChoK complexes demonstrated that Leu-401 of ChoK{alpha}2 (equivalent to Leu-419 of ChoK{alpha}1), or the corresponding residue Phe-352 of ChoK{beta}, which is one of the hydrophobic residues neighboring the active site, influences the plasticity of the HC-3-binding groove, thereby playing a key role in HC-3 sensitivity and phosphorylation.« less

Identification of copy number variation-driven genes for liver cancer via bioinformatics analysis.

PubMed

Lu, Xiaojie; Ye, Kun; Zou, Kailin; Chen, Jinlian

2014-11-01

To screen out copy number variation (CNV)-driven differentially expressed genes (DEGs) in liver cancer and advance our understanding of the pathogenesis, an integrated analysis of liver cancer-related CNV data from The Cancer Genome Atlas (TCGA) and gene expression data from EBI Array Express database were performed. The DEGs were identified by package limma based on the cut-off of |log2 (fold-change)|>0.585 and adjusted p-value<0.05. Using hg19 annotation information provided by UCSC, liver cancer-related CNVs were then screened out. TF-target gene interactions were also predicted with information from UCSC using DAVID online tools. As a result, 25 CNV-driven genes were obtained, including tripartite motif containing 28 (TRIM28) and RanBP-type and C3HC4-type zinc finger containing 1 (RBCK1). In the transcriptional regulatory network, 8 known cancer-related transcription factors (TFs) interacted with 21 CNV-driven genes, suggesting that the other 8 TFs may be involved in liver cancer. These genes may be potential biomarkers for early detection and prevention of liver cancer. These findings may improve our knowledge of the pathogenesis of liver cancer. Nevertheless, further experiments are still needed to confirm our findings.

Simulation of Titan's atmospheric photochemistry. Formation of non-volatile residue from polar nitrile ices

NASA Astrophysics Data System (ADS)

Couturier-Tamburelli, Isabelle; Piétri, Nathalie; Gudipati, Murthy S.

2015-06-01

We studied the photochemistry of frozen ice of a polar Titan's atmospheric molecule cyanodiacetylene (HC5N) to determine the possible contribution of this compound to the lower altitude photochemistry of haze layers found on Titan. We used infrared analysis to examine the residue produced by irradiation of solid HC5N at λ > 300 nm. The resulting polymer is orange-brown in color. Based on theoretical analysis and the general tendency of HC5N and C4N2 to undergo similar ice photochemistry at longer wavelengths accessible in Titan's lower atmosphere, we conclude that Titan's lower atmosphere is photochemically active in the regions of cloud, ice, and aerosol formation. C4N2is a symmetric molecule with no net dipole moment whereas, HC5N has a large dipole moment of ~4 D. Consequently, though both these molecules have very similar molecular weight and size, their sublimation temperatures are different, HC5N subliming around 170 K compared to 160 K for C4N2. Based on our studies we conclude that in Titan's atmosphere the cyanoacetylene class of molecules (HCN, HC3N, HC5N, etc.) would condense first followed by the dicyanoacetylenes (C2N2, C4N2, C6N2, etc.), leading to fractionation of different class of molecules. From the fluxes used in the laboratory and depletion of the original HC5N signals, we estimate Titan's haze ice photochemistry involving polar nitriles to be significant and very similar to their non-polar counterparts.

Peptide-based, two-fluorophore, ratiometric probe for quantifying mobile zinc in biological solutions.

PubMed

Zhang, Daniel Y; Azrad, Maria; Demark-Wahnefried, Wendy; Frederickson, Christopher J; Lippard, Stephen J; Radford, Robert J

2015-02-20

Small-molecule fluorescent sensors are versatile agents for detecting mobile zinc in biology. Capitalizing on the abundance of validated mobile zinc probes, we devised a strategy for repurposing existing intensity-based sensors for quantitative applications. Using solid-phase peptide synthesis, we conjugated a zinc-sensitive Zinpyr-1 derivative and a zinc-insensitive 7-hydroxycoumarin derivative onto opposite ends of a rigid P9K peptide scaffold to create HcZ9, a ratiometric fluorescent probe for mobile zinc. A plate reader-based assay using HcZ9 was developed, the accuracy of which is comparable to that of atomic absorption spectroscopy. We investigated zinc accumulation in prostatic cells and zinc levels in human seminal fluid. When normal and tumorigenic cells are bathed in zinc-enriched media, cellular mobile zinc is buffered and changes slightly, but total zinc levels increase significantly. Quantification of mobile and total zinc levels in human seminal plasma revealed that the two are positively correlated with a Pearson's coefficient of 0.73.

Associations of anthropometric markers with serum metabolites using a targeted metabolomics approach: results of the EPIC-potsdam study

PubMed Central

Bachlechner, U; Floegel, A; Steffen, A; Prehn, C; Adamski, J; Pischon, T; Boeing, H

2016-01-01

Background/Objectives: The metabolic consequences of type of body shape need further exploration. Whereas accumulation of body mass in the abdominal area is a well-established metabolic risk factor, accumulation in the gluteofemoral area is controversially debated. We evaluated the associations of anthropometric markers of overall body mass and body shape with 127 serum metabolites within a sub-sample of the European Prospective Investigation into Cancer and Nutrition (EPIC)-Potsdam cohort. Subjects/Methods: The cross-sectional analysis was conducted in 2270 participants, randomly drawn from the EPIC-Potsdam cohort. Metabolites were measured by targeted metabolomics. To select metabolites related with both waist circumference (WC) (abdominal subcutaneous and visceral fat) and hip circumference (HC) (gluteofemoral fat, muscles and bone structure) correlations (r) with body mass index (BMI) as aggregating marker of body mass (lean and fat mass) were calculated. Relations with body shape were assessed by median metabolite concentrations across tertiles of WC and HC, mutually adjusted to each other. Results: Correlations revealed 23 metabolites related to BMI (r⩾I0.20 I). Metabolites showing relations with BMI were showing similar relations with HC adjusted WC (WCHC). In contrast, relations with WC adjusted HC (HCWC) were less concordant with relations of BMI and WCHC. In both sexes, metabolites with concordant relations regarding WCHC and HCWC included tyrosine, diacyl-phosphatidylcholine C38:3, C38:4, lyso-phosphatidylcholine C18:1, C18:2 and sphingomyelin C18:1; metabolites with opposite relations included isoleucine, diacyl-phosphatidylcholine C42:0, acyl–alkyl-phosphatidylcholine C34:3, C42:4, C42:5, C44:4 and C44:6. Metabolites specifically related to HCWC included acyl–alkyl-phosphatidylcholine C34:2, C36:2, C38:2 and C40:4, and were solely observed in men. Other metabolites were related to WCHC only. Conclusions: The study revealed specific metabolic profiles for HCWC as marker of gluteofemoral body mass differing from those for BMI and WCHC as markers of overall body mass and abdominal fat, respectively. Thus, the study suggests that gluteofemoral mass may have less-adverse metabolic implications than abdominal fat. PMID:27348203

Synthesis, Structure and Thermal Behavior of Oxalato-Bridged Rb+ and H3O+ Extended Frameworks with Different Dimensionalities

PubMed Central

Kherfi, Hamza; Hamadène, Malika; Guehria-Laïdoudi, Achoura; Dahaoui, Slimane; Lecomte, Claude

2010-01-01

Correlative studies of three oxalato-bridged polymers, obtained under hydrothermal conditions for the two isostructural compounds {Rb(HC2O4)(H2C2O4)(H2O)2}∞1, 1, {H3O(HC2O4)(H2C2O4).2H2O}∞1, 2, and by conventional synthetic method for {Rb(HC2O4)}∞3, 3, allowed the identification of H-bond patterns and structural dimensionality. Ferroïc domain structures are confirmed by electric measurements performed on 3. Although 2 resembles one oxalic acid sesquihydrate, its structure determination doesn’t display any kind of disorder and leads to recognition of a supramolecular network identical to hybrid s-block series, where moreover, unusual H3O+ and NH4+ similarity is brought out. Thermal behaviors show that 1D frameworks with extended H-bonds, whether with or without a metal center, have the same stability. Inversely, despite the dimensionalities, the same metallic intermediate and final compounds are obtained for the two Rb+ ferroïc materials.

A very low-carbohydrate, low-saturated fat diet for type 2 diabetes management: a randomized trial.

PubMed

Tay, Jeannie; Luscombe-Marsh, Natalie D; Thompson, Campbell H; Noakes, Manny; Buckley, Jon D; Wittert, Gary A; Yancy, William S; Brinkworth, Grant D

2014-11-01

To comprehensively compare the effects of a very low-carbohydrate, high-unsaturated/low-saturated fat diet (LC) with those of a high-unrefined carbohydrate, low-fat diet (HC) on glycemic control and cardiovascular disease (CVD) risk factors in type 2 diabetes (T2DM). Obese adults (n = 115, BMI 34.4 ± 4.2 kg/m(2), age 58 ± 7 years) with T2DM were randomized to a hypocaloric LC diet (14% carbohydrate [<50 g/day], 28% protein, and 58% fat [<10% saturated fat]) or an energy-matched HC diet (53% carbohydrate, 17% protein, and 30% fat [<10% saturated fat]) combined with structured exercise for 24 weeks. The outcomes measured were as follows: glycosylated hemoglobin (HbA1c), glycemic variability (GV; assessed by 48-h continuous glucose monitoring), antiglycemic medication changes (antiglycemic medication effects score [MES]), and blood lipids and pressure. A total of 93 participants completed 24 weeks. Both groups achieved similar completion rates (LC 79%, HC 82%) and weight loss (LC -12.0 ± 6.3 kg, HC -11.5 ± 5.5 kg); P ≥ 0.50. Blood pressure (-9.8/-7.3 ± 11.6/6.8 mmHg), fasting blood glucose (-1.4 ± 2.3 mmol/L), and LDL cholesterol (-0.3 ± 0.6 mmol/L) decreased, with no diet effect (P ≥ 0.10). LC achieved greater reductions in triglycerides (-0.5 ± 0.5 vs. -0.1 ± 0.5 mmol/L), MES (-0.5 ± 0.5 vs. -0.2 ± 0.5), and GV indices; P ≤ 0.03. LC induced greater HbA1c reductions (-2.6 ± 1.0% [-28.4 ± 10.9 mmol/mol] vs. -1.9 ± 1.2% [-20.8 ± 13.1 mmol/mol]; P = 0.002) and HDL cholesterol (HDL-C) increases (0.2 ± 0.3 vs. 0.05 ± 0.2 mmol/L; P = 0.007) in participants with the respective baseline values HbA1c >7.8% (62 mmol/mol) and HDL-C <1.29 mmol/L. Both diets achieved substantial improvements for several clinical glycemic control and CVD risk markers. These improvements and reductions in GV and antiglycemic medication requirements were greatest with the LC compared with HC. This suggests an LC diet with low saturated fat may be an effective dietary approach for T2DM management if effects are sustained beyond 24 weeks. © 2014 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.

Comparative structural analysis of cytidine, ethenocytidine and their protonated salts III. 1H, 13C and 15N NMR studies at natural isotope abundance.

PubMed Central

Kozerski, L; Sierzputowska-Gracz, H; Krzyzosiak, W; Bratek-Wiewiórowska, M; Jaskólski, M; Wiewiórowski, M

1984-01-01

The 1H, 13C, 15N NMR spectra of cytidine /Cyd/, ethenocytidine /epsilon Cyd/ and their hydrochlorides /Cyd X HC1/ and /epsilon Cyd X HC1/ have been analysed to compare structural differences observed in solution with those existing in the crystalline state. The effects of ethenobridging and protonation of the hertero-aromatic base on the intramolecular stereochemistry, intermolecular interactions and electronic structure of the whole molecule are discussed on the basis of the NMR studies in DMSO solutions. Particular interest is devoted to the discussion of the conformation of the ribose ring, the presence of the intramolecular C-5'-0...H-6-C hydrogen bond, unambiguous assignment of the site of protonation, the mechanism of the 5C-H deuterium exchange in Cyd X HC1, and the intermolecular interactions in solution. PMID:6701098

Cloning of an SNF2/SWI2-related protein that binds specifically to the SPH motifs of the SV40 enhancer and to the HIV-1 promoter.

PubMed

Sheridan, P L; Schorpp, M; Voz, M L; Jones, K A

1995-03-03

We have isolated a human cDNA clone encoding HIP116, a protein that binds to the SPH repeats of the SV40 enhancer and to the TATA/inhibitor region of the human immunodeficiency virus (HIV)-1 promoter. The predicted HIP116 protein is related to the yeast SNF2/SWI2 transcription factor and to other members of this extended family and contains seven domains similar to those found in the vaccinia NTP1 ATPase. Interestingly, HIP116 also contains a C3HC4 zinc-binding motif (RING finger) interspersed between the ATPase motifs in an arrangement similar to that found in the yeast RAD5 and RAD16 proteins. The HIP116 amino terminus is unique among the members of this family, and houses a specific DNA-binding domain. Antiserum raised against HIP116 recognizes a 116-kDa nuclear protein in Western blots and specifically supershifts SV40 and HIV-1 protein-DNA complexes in gel shift experiments. The binding site for HIP116 on the SV40 enhancer directly overlaps the site for TEF-1, and like TEF-1, binding of HIP116 to the SV40 enhancer is destroyed by mutations that inhibit SPH enhancer activity in vivo. Purified fractions of HIP116 display strong ATPase activity that is preferentially stimulated by SPH DNA and can be inhibited specifically by antibodies to HIP116. These findings suggest that HIP116 might affect transcription, directly or indirectly, by acting as a DNA binding site-specific ATPase.

TT-C-490 -Implementing Alternatives Through Specifications (Briefing Charts)

DTIC Science & Technology

2014-11-18

currently valid OMB control number. 1. REPORT DATE 18 NOV 2014 2. REPORT TYPE 3. DATES COVERED 00-00-2014 to 00-00-2014 4. TITLE AND SUBTITLE TT-C...Existing Pretreatments for CARC Coating System TT-C-490E – Pretreatments specific for ferrous substrates – Specifies either zinc phosphate conversion...Only pretreatment allowed for multi- metal application – Zinc phosphate is either applied by immersion or spray in a contained area Prior to 2013

Hydrocarbon emission fingerprints from contemporary vehicle/engine technologies with conventional and new fuels

NASA Astrophysics Data System (ADS)

Montero, Larisse; Duane, Matthew; Manfredi, Urbano; Astorga, Covadonga; Martini, Giorgio; Carriero, Massimo; Krasenbrink, Alois; Larsen, B. R.

2010-06-01

The present paper presents results from the analysis of 29 individual C 2-C 9 hydrocarbons (HCs) specified in the European Commission Ozone Directive. The 29 HCs are measured in exhaust from common, contemporary vehicle/engine/fuel technologies for which very little or no data is available in the literature. The obtained HC emission fingerprints are compared with fingerprints deriving from technologies that are being phased out in Europe. Based on the total of 138 emission tests, thirteen type-specific fingerprints are extracted (Mean ± SD percentage contributions from individual HCs to the total mass of the 29 HCs), essential for receptor modelling source apportionment. The different types represent exhaust from Euro3 and Euro4 light-duty (LD) diesel and petrol-vehicles, Euro3 heavy-duty (HD) diesel exhaust, and exhaust from 2-stroke preEuro, Euro1 and Euro2 mopeds. The fuels comprise liquefied petroleum gas, petrol/ethanol blends (0-85% ethanol), and mineral diesel in various blends (0-100%) with fatty acid methyl esters, rapeseed methyl esters palm oil methyl esters, soybean oil methyl or sunflower oil methyl esters. Type-specific tracer compounds (markers) are identified for the various vehicle/engine/fuel technologies. An important finding is an insignificant effect on the HC fingerprints of varying the test driving cycle, indicating that combining HC fingerprints from different emission studies for receptor modelling purposes would be a robust approach. The obtained results are discussed in the context of atmospheric ozone formation and health implications from emissions (mg km -1 for LD and mopeds and mg kW h -1 for HD, all normalised to fuel consumption: mg dm -3 fuel) of the harmful HCs, benzene and 1,3-butadiene. Another important finding is a strong linear correlation of the regulated "total" hydrocarbon emissions (tot-HC) with the ozone formation potential of the 29 HCs (ΣPO 3 = (1.66 ± 0.04) × tot-RH; r2 = 0.93). Tot-HC is routinely monitored in emission control laboratories, whereas C 2-C 9 are not. The revealed strong correlations broadens the usability of data from vehicle emission control laboratories and facilitates the comparison of the ozone formation potential of HCs in exhaust from of old and new vehicle/engine/fuel technologies.

The growth of carbon chains in IRC +10216 mapped with ALMA⋆

PubMed Central

Agúndez, M.; Cernicharo, J.; Quintana-Lacaci, G.; Castro-Carrizo, A.; Velilla Prieto, L.; Marcelino, N.; Guélin, M.; Joblin, C.; Martín-Gago, J. A.; Gottlieb, C. A.; Patel, N. A.; McCarthy, M. C.

2017-01-01

Linear carbon chains are common in various types of astronomical molecular sources. Possible formation mechanisms involve both bottom-up and top-down routes. We have carried out a combined observational and modeling study of the formation of carbon chains in the C-star envelope IRC +10216, where the polymerization of acetylene and hydrogen cyanide induced by ultraviolet photons can drive the formation of linear carbon chains of increasing length. We have used ALMA to map the emission of λ 3 mm rotational lines of the hydrocarbon radicals C2H, C4H, and C6H, and the CN-containing species CN, C3N, HC3N, and HC5N with an angular resolution of ~1″. The spatial distribution of all these species is a hollow, 5-10″ wide, spherical shell located at a radius of 10-20″ from the star, with no appreciable emission close to the star. Our observations resolve the broad shell of carbon chains into thinner sub-shells which are 1-2″ wide and not fully concentric, indicating that the mass loss process has been discontinuous and not fully isotropic. The radial distributions of the species mapped reveal subtle differences: while the hydrocarbon radicals have very similar radial distributions, the CN-containing species show more diverse distributions, with HC3N appearing earlier in the expansion and the radical CN extending later than the rest of the species. The observed morphology can be rationalized by a chemical model in which the growth of polyynes is mainly produced by rapid gas-phase chemical reactions of C2H and C4H radicals with unsaturated hydrocarbons, while cyanopolyynes are mainly formed from polyynes in gas-phase reactions with CN and C3N radicals. PMID:28469283

Synthesis and crystal structures of (2E)-1,4-bis-(4-chloro-phen-yl)but-2-ene-1,4-dione and (2E)-1,4-bis-(4-bromo-phen-yl)but-2-ene-1,4-dione.

PubMed

Lastovickova, Dominika N; La Scala, John J; Sausa, Rosario C

2018-03-01

The mol-ecular structure of (2 E )-1,4-bis-(4-chloro-phen-yl)but-2-ene-1,4-dione [C 16 H 10 Cl 2 O 2 , ( 1 )] is composed of two p -chlorophenyl rings, each bonded on opposite ends to a near planar 1,4- trans enedione moiety [-C(=O)-CH=CH-(C=O)-] [r.m.s. deviation = 0.003 (1) Å]. (2 E )-1,4-Bis(4-bromo-phen-yl)but-2-ene-1,4-dione [C 16 H 10 Br 2 O 2 , ( 2 )] has a similar structure to ( 1 ), but with two p -bromophenyl rings and a less planar enedione group [r.m.s. deviation = 0.011 (1) Å]. Both mol-ecules sit on a center of inversion, thus Z ' = 0.5. The dihedral angles between the ring and the enedione group are 16.61 (8) and 15.58 (11)° for ( 1 ) and ( 2 ), respectively. In the crystal, mol-ecules of ( 1 ) exhibit C-Cl⋯Cl type I inter-actions, whereas mol-ecules of ( 2 ) present C-Br⋯Br type II inter-actions. van der Waals-type inter-actions contribute to the packing of both mol-ecules, and the packing reveals face-to-face ring stacking with similar inter-planar distances of approximately 3.53 Å.

The structure of human 4F2hc ectodomain provides a model for homodimerization and electrostatic interaction with plasma membrane.

PubMed

Fort, Joana; de la Ballina, Laura R; Burghardt, Hans E; Ferrer-Costa, Carles; Turnay, Javier; Ferrer-Orta, Cristina; Usón, Isabel; Zorzano, Antonio; Fernández-Recio, Juan; Orozco, Modesto; Lizarbe, María Antonia; Fita, Ignacio; Palacín, Manuel

2007-10-26

4F2hc (CD98hc) is a multifunctional type II membrane glycoprotein involved in amino acid transport and cell fusion, adhesion, and transformation. The structure of the ectodomain of human 4F2hc has been solved using monoclinic (Protein Data Bank code 2DH2) and orthorhombic (Protein Data Bank code 2DH3) crystal forms at 2.1 and 2.8 A, respectively. It is composed of a (betaalpha)(8) barrel and an antiparallel beta(8) sandwich related to bacterial alpha-glycosidases, although lacking key catalytic residues and consequently catalytic activity. 2DH3 is a dimer with Zn(2+) coordination at the interface. Human 4F2hc expressed in several cell types resulted in cell surface and Cys(109) disulfide bridge-linked homodimers with major architectural features of the crystal dimer, as demonstrated by cross-linking experiments. 4F2hc has no significant hydrophobic patches at the surface. Monomer and homodimer have a polarized charged surface. The N terminus of the solved structure, including the position of Cys(109) residue located four residues apart from the transmembrane domain, is adjacent to the positive face of the ectodomain. This location of the N terminus and the Cys(109)-intervening disulfide bridge imposes space restrictions sufficient to support a model for electrostatic interaction of the 4F2hc ectodomain with membrane phospholipids. These results provide the first crystal structure of heteromeric amino acid transporters and suggest a dynamic interaction of the 4F2hc ectodomain with the plasma membrane.

New Line Lists for planetological applications: HC3N and C4H2

NASA Astrophysics Data System (ADS)

Jolly, A.; Benilan, Y.; Fayt, A.

2009-04-01

The Composite Infrared Spectrometer (CIRS) on-board Cassini, after four years of operation in Saturnian orbit with over thirty close fly-bys of Titan, has obtained spectra in the far and mid-infrared with a spectral resolution of 0.5 cm-1. Mismatch between observed spectra and model spectra obtained from the available line lists has led us to study the bending bands of HC3N and C4H2, the longest carbon chains observed on Titan. Our experimental study for HC3N (Jolly et al. 2007, J.Mol.Spec) has shown that band intensities had to be revised and that including hot bands with lower level as high as 1300 cm-1 was necessary to model our experimental spectra at 0.5 cm-1 resolution. A new extended line list could be obtained by fitting high resolution data with the help of a global analysis. This line list was made available to the astronomers of the CIRS team and will be included in the next version of the GEISA data base. Thanks to the precision of the new spectroscopic data, 13C isotopologues of HC3N have been detected and quantified for the first time in the atmosphere of Titan (Jennings et al. 2008, ApJL). Search for the 15N isotopologues of HC3N will also be presented. The proportion of hot bands is even more important for C4H2 than for HC3N and a new extended line list was absolutely necessary to improve the CIRS spectral analysis. We will present a new line list and show comparison between synthetic spectra and experimental spectra of C4H2 obtained between 193 and 296 K at 0.1 and 0.5 cm-1 resolution. Comparison of model spectra to CIRS observations of C4H2 at 220 and 630 cm-1 will also be presented. Detections of hot bands and isotopes in cold environments such as Titan will be emphasized.

Structural basis for suppression of hypernegative DNA supercoiling by E. coli topoisomerase I

DOE PAGES

Tan, Kemin; Zhou, Qingxuan; Cheng, Bokun; ...

2015-10-20

Escherichia coli topoisomerase I has an essential function in preventing hypernegative supercoiling of DNA. A full length structure of E. coli topoisomerase I reported here shows how the C-terminal domains bind single-stranded DNA (ssDNA) to recognize the accumulation of negative supercoils in duplex DNA. These C-terminal domains of E. coli topoisomerase I are known to interact with RNA polymerase, and two flexible linkers within the C-terminal domains may assist in the movement of the ssDNA for the rapid removal of transcription driven negative supercoils. The structure has also unveiled for the first time how the 4-Cys zinc ribbon domain andmore » zinc ribbon-like domain bind ssDNA with primarily π -stacking interactions. Finally, this novel structure, in combination with new biochemical data, provides important insights into the mechanism of genome regulation by type IA topoisomerases that is essential for life, as well as the structures of homologous type IA TOP3α and TOP3β from higher eukaryotes that also have multiple 4-Cys zinc ribbon domains required for their physiological functions.« less

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

Tan, Kemin; Zhou, Qingxuan; Cheng, Bokun

Escherichia coli topoisomerase I has an essential function in preventing hypernegative supercoiling of DNA. A full length structure of E. coli topoisomerase I reported here shows how the C-terminal domains bind single-stranded DNA (ssDNA) to recognize the accumulation of negative supercoils in duplex DNA. These C-terminal domains of E. coli topoisomerase I are known to interact with RNA polymerase, and two flexible linkers within the C-terminal domains may assist in the movement of the ssDNA for the rapid removal of transcription driven negative supercoils. The structure has also unveiled for the first time how the 4-Cys zinc ribbon domain andmore » zinc ribbon-like domain bind ssDNA with primarily π -stacking interactions. Finally, this novel structure, in combination with new biochemical data, provides important insights into the mechanism of genome regulation by type IA topoisomerases that is essential for life, as well as the structures of homologous type IA TOP3α and TOP3β from higher eukaryotes that also have multiple 4-Cys zinc ribbon domains required for their physiological functions.« less

Anisotropic upper critical magnetic fields in Rb 2 Cr 3 As 3 superconductor

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

Tang, Zhang-Tu; Liu, Yi; Bao, Jin-Ke

Rb2Cr3As3 is a structurally one-dimensional superconductor containing Cr3As3 chains with a superconducting transition temperature of T-c = 4.8 K. Here we report the electrical resistance measurements for Rb2Cr3As3 single crystals, under magnetic fields up to 29.5 T and at temperatures down to 0.36 K, from which the upper critical fields, H-c2(T), can be obtained in a broad temperature range. For field parallel to the Cr3As3 chains, H-c2(parallel to)(T) is paramagnetically limited with an initial slope of mu(0)dH(c2)(parallel to)/dT|T-c = - 16 T K-1 and a zero-temperature upper critical field of mu H-0(c2)parallel to(0) = 17.5 T. For field perpendicular tomore » the Cr3As3 chains, however, H-c2(perpendicular to)(T) is only limited by orbital pair-breaking effect with mu(0)dH(c2)(perpendicular to)/dT|(Tc) = - 3 T K-1. As a consequence, the anisotropy gamma H = H-c2(parallel to)/H-c2(perpendicular to) decreases sharply near T-c and reverses below 2 K. Remarkably, the low- temperature H-c2(perpendicular to)(T) down to 0.075 T-c remains to increase linearly up to over three times the Pauli paramagnetic limit, which strongly suggests dominant spin-triplet superconductivity in Rb2Cr3As3.« less

The PTPN22 1858T allele but not variants in the proximal promoter region of IL-21 gene is associated with the susceptibility to type 1 diabetes and the presence of autoantibodies in a Brazilian cohort

PubMed Central

Mainardi-Novo, D T O; Santos, A S; Fukui, R T; Gamberini, M; Correia, M R S; Ruiz, M O; Mangueira, C L P; Matioli, S R; Vasconcelos, D M; Silva, M E R

2013-01-01

Interleukin (IL)-21 and protein tyrosine phosphatase non-receptor 22 (PTPN22) regulate lymphocyte function and have been implicated in the pathogenesis of autoimmune diabetes. We sequenced the proximal promoter of the IL-21 gene for the first time and analysed the PTPN22 1858T polymorphism in type 1A diabetes (T1AD) patients and healthy controls (HC). We correlated the frequencies of islet and extra-pancreatic autoantibodies with genotypes from both loci. The case series comprised 612 T1AD patients and 792 HC. Genotyping of PTPN22 C1858T was performed on 434 T1AD patients and 689 HC. The −448 to +83 base pairs (bp) region of the IL-21 gene was sequenced in 309 Brazilian T1AD and 189 HC subjects. We also evaluated human leucocyte antigen (HLA) DR3/DR4 alleles. The frequencies of glutamic acid decarboxylase (GAD65), tyrosine phosphatase-like protein (IA)-2, anti-nuclear antibody (ANA), thyroid peroxidase (TPO), thyroglobulin (TG), thyrotrophin receptor autoantibody (TRAb), anti-smooth muscle (ASM) and 21-hydroxylase (21-OH) autoantibodies were higher in T1AD patients than in HC. The PTPN22 1858T allele was associated with an increased risk for developing T1AD [odds ratio (OR) = 1·94; P < 0·001], particularly in patients of European ancestry, and with a higher frequency of GAD65 and TG autoantibodies. HLA-DR3/DR4 alleles predominated in T1AD patients. A heterozygous allelic IL-21 gene variant (g.-241 T > A) was found in only one patient. In conclusion, only PTPN22 C1858T polymorphism and HLA-DR3 and/or DR4 alleles, but not allelic variants in the 5′-proximal region of the IL-21 gene were associated with T1AD risk. Patients with T1AD had increased frequencies of anti-islet-cell, anti-thyroid, anti-nuclear, anti-smooth muscle and anti-21-OH autoantibodies. The C1858T PTPN22 polymorphism was also associated with a higher frequency of GAD65 and TG autoantibodies. PMID:23480181

The PTPN22 1858T allele but not variants in the proximal promoter region of IL-21 gene is associated with the susceptibility to type 1 diabetes and the presence of autoantibodies in a Brazilian cohort.

PubMed

Mainardi-Novo, D T O; Santos, A S; Fukui, R T; Gamberini, M; Correia, M R S; Ruiz, M O; Mangueira, C L P; Matioli, S R; Vasconcelos, D M; Silva, M E R

2013-04-01

Interleukin (IL)-21 and protein tyrosine phosphatase non-receptor 22 (PTPN22) regulate lymphocyte function and have been implicated in the pathogenesis of autoimmune diabetes. We sequenced the proximal promoter of the IL-21 gene for the first time and analysed the PTPN22 1858T polymorphism in type 1A diabetes (T1AD) patients and healthy controls (HC). We correlated the frequencies of islet and extra-pancreatic autoantibodies with genotypes from both loci. The case series comprised 612 T1AD patients and 792 HC. Genotyping of PTPN22 C1858T was performed on 434 T1AD patients and 689 HC. The -448 to +83 base pairs (bp) region of the IL-21 gene was sequenced in 309 Brazilian T1AD and 189 HC subjects. We also evaluated human leucocyte antigen (HLA) DR3/DR4 alleles. The frequencies of glutamic acid decarboxylase (GAD65), tyrosine phosphatase-like protein (IA)-2, anti-nuclear antibody (ANA), thyroid peroxidase (TPO), thyroglobulin (TG), thyrotrophin receptor autoantibody (TRAb), anti-smooth muscle (ASM) and 21-hydroxylase (21-OH) autoantibodies were higher in T1AD patients than in HC. The PTPN22 1858T allele was associated with an increased risk for developing T1AD [odds ratio (OR) = 1·94; P < 0·001], particularly in patients of European ancestry, and with a higher frequency of GAD65 and TG autoantibodies. HLA-DR3/DR4 alleles predominated in T1AD patients. A heterozygous allelic IL-21 gene variant (g.-241 T > A) was found in only one patient. In conclusion, only PTPN22 C1858T polymorphism and HLA-DR3 and/or DR4 alleles, but not allelic variants in the 5'-proximal region of the IL-21 gene were associated with T1AD risk. Patients with T1AD had increased frequencies of anti-islet-cell, anti-thyroid, anti-nuclear, anti-smooth muscle and anti-21-OH autoantibodies. The C1858T PTPN22 polymorphism was also associated with a higher frequency of GAD65 and TG autoantibodies. © 2012 British Society for Immunology.

Synthesis and crystal structure of a novel pentaborate, Na{sub 3}ZnB{sub 5}O{sub 10}

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

Chen Xuean; Li Ming; Chang Xinan

A novel ternary borate, trisodium zinc pentaborate, Na{sub 3}ZnB{sub 5}O{sub 10}, has been prepared by solid-state reaction at temperature below 750deg. C. The single-crystal X-ray structural analysis showed that Na{sub 3}ZnB{sub 5}O{sub 10} crystallizes in the monoclinic space group P2{sub 1}/n with a=6.6725(7)A, b=18.1730(10)A, c=7.8656(9)A, {beta}=114.604(6){sup o}, Z=4. It represents a new structure type in which double ring [B{sub 5}O{sub 10}]{sup 5-} building units are bridged by ZnO{sub 4} tetrahedra through common O atoms to form a two-dimensional {sub {approx}}{sup 2}[ZnB{sub 5}O{sub 10}]{sup 3-}-layer that affords one-dimensional channels running parallel to the [101] direction. Symmetry-center related {sub {approx}}{sup 2}[ZnB{sub 5}O{submore » 10}]{sup 3-} layers are stacked along the b-axis, with the interlayer void spaces and intralayer open channels filled by Na{sup +} cations to balance charge. The IR spectrum further confirms the presence of both BO{sub 3} and BO{sub 4} groups and UV-vis diffuse reflectance spectrum shows a band gap of about 3.2eV.« less

Annular dynamics after mitral valve repair with different prosthetic rings: A real-time three-dimensional transesophageal echocardiography study.

PubMed

Nishi, Hiroyuki; Toda, Koichi; Miyagawa, Shigeru; Yoshikawa, Yasushi; Fukushima, Satsuki; Kawamura, Masashi; Yoshioka, Daisuke; Saito, Tetsuya; Ueno, Takayoshi; Kuratani, Toru; Sawa, Yoshiki

2016-09-01

We assessed the effects of different types of prosthetic rings on mitral annular dynamics using real-time three-dimensional echocardiography (RT3DE). RT3DE was performed in 44 patients, including patients undergoing mitral annuloplasty using the Cosgrove-Edwards flexible band (Group A, n = 10), the semi-rigid Sorin Memo 3D ring (Group B, n = 17), the semi-rigid Edwards Physio II ring (Group C, n = 7) and ten control subjects. Various annular diameters were measured throughout the cardiac cycle. We observed flexible anterior annulus motion in all of the groups except Group C. A flexible posterior annulus was only observed in Group B and the Control group. The mitral annular area changed during the cardiac cycle by 8.4 ± 3.2, 6.3 ± 2.0, 3.2 ± 1.3, and 11.6 ± 5.0 % in Group A, Group B, Group C, and the Control group, respectively. The dynamic diastolic to systolic change in mitral annular diameters was lost in Group C, while it was maintained in Group A, and to a good degree in Group B. In comparison to the Control group, the mitral annulus shape was more ellipsoid in Group B and Group C, and more circular in Group A. Although mitral regurgitation was well controlled by all of the types of rings that were utilized in the present study, we demonstrated that the annulus motion and annulus shape differed according to the type of prosthetic ring that was used, which might provide important information for the selection of an appropriate prosthetic ring.

Upper critical fields in Ba2Ti2Fe2As4O single crystals: Evidence for dominant Pauli paramagnetic effect

NASA Astrophysics Data System (ADS)

Abdel-Hafiez, M.; Brisbois, J.; Zhu, Z.; Adamski, A.; Hassen, A.; Vasiliev, A. N.; Silhanek, A. V.; Krellner, C.

2018-03-01

We report on magneto-optical imaging and the temperature dependency of the upper critical fields Hc2 c(T ) parallel to the c axis and Hc2 a b(T ) parallel to the a b plane in Ba2Ti2Fe2As4O single crystals. These data were inferred from the measurements of the temperature-dependent resistance in static magnetic fields up to 14 T and magnetoresistance in pulsed fields up to 60 T. Hc 2 values are found to be 52 and 50 T for H ∥a b and H ∥c , respectively. These values are 1.2-1.35 times larger than the weak-coupling Pauli paramagnetic limit (Hp˜1.84 Tc ), indicating that enhanced paramagnetic limiting is essential and this superconductor is unconventional. Our observations of strong bending in the Hc2 a b(T ) curves and a nearly isotropic maximum upper critical field Hc2 a b(0 ) ≈Hc2 c(0 ) support the presence of a strong Pauli paramagnetic effect. We show that the Werthamer-Helfand-Hohenberg (WHH) formula that includes the spin-orbit scattering can effectively describe the Hc2 a b(T ) curve, whereas Hc 2 deviates from the conventional WHH theoretical model without considering the spin paramagnetic effect for the H ∥c and H ∥a b directions. For H ∥c , a two-band model is required to fully reproduce the behavior of Hc 2, while for H ∥a b the spin paramagnetic effect is responsible for the behavior of Hc 2. The anisotropy of Hc 2 is close to 3 near Tc and decreases rapidly at lower temperatures.

Characterization and Promoter Analysis of a Cotton Ring-Type Ubiquitin Ligase (E3) Gene

USDA-ARS?s Scientific Manuscript database

A cotton fiber cDNA, GhRING1, and its corresponding gene have been cloned and characterized. The GhRING1 gene encodes a RING-type ubiquitin ligase (E3) containing 337 amino acids (aa). The GhRING1 protein contains a RING finger motif with conserved cysteine and histine residues at the C-terminus a...

Organic Chemistry of Low-Mass Star-Forming Cores. I. 7 mm Spectroscopy of Chamaeleon MMSl

NASA Technical Reports Server (NTRS)

Cordiner, Martn A.; Charnley, Steven B.; Wirtstroem, Eva S.; Smith, Robert G.

2012-01-01

Observations are presented of emission lines from organic molecules at frequencies 32-50 GHz in the vicinity of Chamaeleon MMS1. This chemically rich dense cloud core harbors an extremely young, very low luminosity protostellar object and is a candidate first hydrostatic core. Column densities are derived and emission maps are presented for species including polyynes, cyanopolyynes, sulphuretted carbon chains, and methanol. The polyyne emission peak lies about 5000 AU from the protostar, whereas methanol peaks about 15,000 AU away. Averaged over the telescope beam, the molecular hydrogen number density is calculated to be 10(exp 6) / cubic cm and the gas kinetic temperature is in the range 5-7 K. The abundances of long carbon chains are very large and are indicative of a nonequilibrium carbon chemistry; C6H and HC7N column densities are 5.9(sup +2.9) (sub -1.3) x 10(exp 11) /cubic cm and 3.3 (sup +8.0)(sub -1.5) x 10(exp 12)/sq cm, respectively, which are similar to the values found in the most carbon-chain-rich protostars and prestellar cores known, and are unusually large for star-forming gas. Column density upper limits were obtained for the carbon chain anions C4H(-) and C6H(-), with anion-to-neutral ratios [C4H(-)]/[C4H] < 0.02% and [C6H(-l)]/[C6H] < 10%, consistent with previous observations in interstellar clouds and low-mass protostars. Deuterated HC,3 and c-C3H2 were detected. The [DC3N]/[HC,N] ratio of approximately 4% is consistent with the value typically found in cold interstellar gas.

β-Lactam Ring Opening: A Useful Entry to Amino Acids and Relevant Nitrogen-Containing Compounds

NASA Astrophysics Data System (ADS)

Palomo, C.; Oiarbide, M.

The main strategies for the ring opening of β-lactams by chemical means are described. The discovery of each approach is put into context, sometimes in connection to processes occurring in biological systems, and the synthetic opportunities each approach offers are shown. Thus, this β-lactam route affords a number of synthetically relevant building-blocks, including α-amino acids, β-amino acids, their derived peptides, and other nitrogen containing heterocycles and open chain molecules. The content, which encompases references to initial work, further major development, and the most relevant recent literature contributions, is categorized according to the ring bond cleavaged (N 1-C 2, C 2-C 3, C 3 -C 4 , N 1-C 4), to finish with ring opening strategies leading to large heterocyclic compounds. Within each category, distinction has been made according to the type of nucleophilic agent employed, principally O-, N-, and C-nucleophiles. Also, a variety of applications of the strategy to the synthesis of interesting target compounds are shown.

A new type of two-dimensional carbon crystal prepared from 1,3,5-trihydroxybenzene

NASA Astrophysics Data System (ADS)

Du, Qi-Shi; Tang, Pei-Duo; Huang, Hua-Lin; Du, Fang-Li; Huang, Kai; Xie, Neng-Zhong; Long, Si-Yu; Li, Yan-Ming; Qiu, Jie-Shan; Huang, Ri-Bo

2017-01-01

A new two-dimensional (2D) carbon crystal, different from graphene, has been prepared from 1,3,5-trihydroxybenzene, consisting of 4-carbon and 6-carbon rings in 1:1 ratio, named 4-6 carbophene by authors, in which all carbon atoms possess sp2 hybrid orbitals with some distortion, forming an extensive conjugated π-bonding planar structure. The angles between the three σ-bonds of the carbon sp2 orbitals are roughly 120°, 90°, and 150°. Each of the three non-adjacent sides of a 6C-ring is shared with a 4C-ring; and each of the two opposite sides of a 4C-ring is shared with a 6C-ring. Dodecagonal holes with a diameter of approximate 5.8 Å are regularly located throughout the 2D carbon crystal. Even though the bond energies in 4-6 carbophene are weaker than those in the graphene, the new planar crystal is quite stable in ambient conditions. The 4-6 carbophene can be synthetized from 1,3,5-trihydroxybenzene or other benzene derivatives through dehydration and polymerization reactions, and may possess several possible patterns that form a family of 2D carbon crystals. A possible side reaction involving 1,3,5-trihydroxybenzene is also discussed, which may produce a carbon-oxygen two dimensional crystal.

Carbon Dioxide Utilization by the Five-Membered Ring Products of Cyclometalation Reactions

PubMed Central

Omae, Iwao

2016-01-01

In carbon dioxide utilization by cyclometalated five-membered ring products, the following compounds are used in four types of applications: 1. 2-Phenylpyrazole iridium compounds, pincer phosphine iridium compounds and 2-phenylimidazoline iridium compounds are used as catalysts for both formic acid production from CO2 and H2, and hydrogen production from the formic acid. This formic acid can be a useful agent for H2 production and storage for fuel cell electric vehicles. 2. Other chemicals, e.g., dimethyl carbonate, methane, methanol and CO, are produced with dimethylaminomethylphenyltin compounds, pincer phosphine iridium compounds, pincer phosphine nickel compound and ruthenium carbene compound or 2-phenylpyridine iridium compounds, and phenylbenzothiazole iridium compounds as the catalysts for the reactions with CO2. 3. The five-membered ring intermediates of cyclometalation reactions with the conventional substrates react with carbon dioxide to afford their many types of carboxylic acid derivatives. 4. Carbon dioxide is easily immobilized at room temperature with immobilizing agents such as pincer phosphine nickel compounds, pincer phosphine palladium compounds, pincer N,N-dimethylaminomethyltin compounds and tris(2-pyridylthio)methane zinc compounds. PMID:28503084

Carbon Dioxide Utilization by the Five-Membered Ring Products of Cyclometalation Reactions.

PubMed

Omae, Iwao

2016-04-01

In carbon dioxide utilization by cyclometalated five-membered ring products, the following compounds are used in four types of applications: 1. 2-Phenylpyrazole iridium compounds, pincer phosphine iridium compounds and 2-phenylimidazoline iridium compounds are used as catalysts for both formic acid production from CO 2 and H 2 , and hydrogen production from the formic acid. This formic acid can be a useful agent for H 2 production and storage for fuel cell electric vehicles. 2. Other chemicals, e.g. , dimethyl carbonate, methane, methanol and CO, are produced with dimethylaminomethylphenyltin compounds, pincer phosphine iridium compounds, pincer phosphine nickel compound and ruthenium carbene compound or 2-phenylpyridine iridium compounds, and phenylbenzothiazole iridium compounds as the catalysts for the reactions with CO 2 . 3. The five-membered ring intermediates of cyclometalation reactions with the conventional substrates react with carbon dioxide to afford their many types of carboxylic acid derivatives. 4. Carbon dioxide is easily immobilized at room temperature with immobilizing agents such as pincer phosphine nickel compounds, pincer phosphine palladium compounds, pincer N , N -dimethylaminomethyltin compounds and tris(2-pyridylthio)methane zinc compounds.

Synthesis and crystal structures of (2 E )-1,4-bis(4-chlorophenyl)but-2-ene-1,4-dione and (2 E )-1,4-bis(4-bromophenyl)but-2-ene-1,4-dione

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

Lastovickova, Dominika N.; La Scala, John J.; Sausa, Rosario C.

The molecular structure of (2 E )-1,4-bis(4-chlorophenyl)but-2-ene-1,4-dione [C 16 H 10 Cl 2 O 2 , ( 1 )] is composed of two p -chlorophenyl rings, each bonded on opposite ends to a near planar 1,4- trans enedione moiety [–C(=O)—CH=CH—(C=O)–] [r.m.s. deviation = 0.003 (1) Å]. (2 E )-1,4-Bis(4-bromophenyl)but-2-ene-1,4-dione [C 16 H 10 Br 2 O 2 , ( 2 )] has a similar structure to ( 1 ), but with two p -bromophenyl rings and a less planar enedione group [r.m.s. deviation = 0.011 (1) Å]. Both molecules sit on a center of inversion, thus Z ′ = 0.5. The dihedral angles between themore » ring and the enedione group are 16.61 (8) and 15.58 (11)° for ( 1 ) and ( 2 ), respectively. In the crystal, molecules of ( 1 ) exhibit C—Cl...Cl type I interactions, whereas molecules of ( 2 ) present C—Br...Br type II interactions. van der Waals-type interactions contribute to the packing of both molecules, and the packing reveals face-to-face ring stacking with similar interplanar distances of approximately 3.53 Å.« less

Synthesis and crystal structures of (2 E )-1,4-bis(4-chlorophenyl)but-2-ene-1,4-dione and (2 E )-1,4-bis(4-bromophenyl)but-2-ene-1,4-dione

DOE PAGES

Lastovickova, Dominika N.; La Scala, John J.; Sausa, Rosario C.

2018-02-13

The molecular structure of (2 E )-1,4-bis(4-chlorophenyl)but-2-ene-1,4-dione [C 16 H 10 Cl 2 O 2 , ( 1 )] is composed of two p -chlorophenyl rings, each bonded on opposite ends to a near planar 1,4- trans enedione moiety [–C(=O)—CH=CH—(C=O)–] [r.m.s. deviation = 0.003 (1) Å]. (2 E )-1,4-Bis(4-bromophenyl)but-2-ene-1,4-dione [C 16 H 10 Br 2 O 2 , ( 2 )] has a similar structure to ( 1 ), but with two p -bromophenyl rings and a less planar enedione group [r.m.s. deviation = 0.011 (1) Å]. Both molecules sit on a center of inversion, thus Z ′ = 0.5. The dihedral angles between themore » ring and the enedione group are 16.61 (8) and 15.58 (11)° for ( 1 ) and ( 2 ), respectively. In the crystal, molecules of ( 1 ) exhibit C—Cl...Cl type I interactions, whereas molecules of ( 2 ) present C—Br...Br type II interactions. van der Waals-type interactions contribute to the packing of both molecules, and the packing reveals face-to-face ring stacking with similar interplanar distances of approximately 3.53 Å.« less

Synthesis of a new class of fused cyclotetraphosphazene ring systems.

PubMed

Beşli, Serap; Mutlu, Ceylan; İbişoğlu, Hanife; Yuksel, Fatma; Allen, Christopher W

2015-01-05

Octachlorocyclotetraphosphazene (1) was reacted with butylamines [n-butyl, i-butyl, sec-butyl, and t-butyl] in a 1:0.8 mol ratio in THF to obtain cyclotetraphosphazenes bearing a P-NH group, N4P4Cl7(NHR) [R = n-butyl (2a), i-butyl (2b), sec-butyl (2c), t-butyl (2d)](2a-d). The cyclotetraphosphazene derivatives 2a, 2b, and 2c were treated with sodium hydride giving rise to a new type of cyclophosphazene compounds (P8N8 ring) consisting of three fused tetramer rings (3a-c). Whereas reaction of sodium hydride with the t-butylaminocyclophosphazene derivative (2d) gave a P-O-P bridged compound (4) presumably as a result of hydrolysis reaction associated with moisture in the solvent. It is likely that the 16-membered cyclooctaphosphazene derivatives (3a-c) are formed by a proton abstraction/chloride ion elimination, intramolecular nucleophilic attack, ring opening and intermolecular condensation processes, respectively.

Crystal structure of di­methyl­ammonium hydrogen oxalate hemi(oxalic acid)

PubMed Central

Diallo, Waly; Gueye, Ndongo; Crochet, Aurélien; Plasseraud, Laurent; Cattey, Hélène

2015-01-01

Single crystals of the title salt, Me2NH2 +·HC2O4 −·0.5H2C2O4, were isolated as a side product from the reaction involving Me2NH, H2C2O4 and Sn(n-Bu)3Cl in a 1:2 ratio in methanol or by the reaction of the (Me2NH2)2C2O4 salt and Sn(CH3)3Cl in a 2:1 ratio in ethanol. The asymmetric unit comprises a di­methyl­ammonium cation (Me2NH2 +), an hydrogenoxalate anion (HC2O4 −), and half a mol­ecule of oxalic acid (H2C2O4) situated about an inversion center. From a supra­molecular point of view, the three components inter­act together via hydrogen bonding. The Me2NH2 + cations and the HC2O4 − anions are in close proximity through bifurcated N—H⋯(O,O) hydrogen bonds, while the HC2O4 − anions are organized into infinite chains via O—H⋯O hydrogen bonds, propagating along the a-axis direction. In addition, the oxalic acid (H2C2O4) mol­ecules play the role of connectors between these chains. Both the carbonyl and hydroxyl groups of each diacid are involved in four inter­molecular inter­actions with two Me2NH2 + and two HC2O4 − ions of four distinct polymeric chains, via two N—H⋯O and two O—H⋯O hydrogen bonds, respectively. The resulting mol­ecular assembly can be viewed as a two-dimensional bilayer-like arrangement lying parallel to (010), and reinforced by a C—H⋯O hydrogen bond. PMID:25995858

Reactive carbon-chain molecules: synthesis of 1-diazo-2,4-pentadiyne and spectroscopic characterization of triplet pentadiynylidene (H-C[triple bond]C-:C-C[triple bond]C-H).

PubMed

Bowling, Nathan P; Halter, Robert J; Hodges, Jonathan A; Seburg, Randal A; Thomas, Phillip S; Simmons, Christopher S; Stanton, John F; McMahon, Robert J

2006-03-15

1-Diazo-2,4-pentadiyne (6a), along with both monodeuterio isotopomers 6b and 6c, has been synthesized via a route that proceeds through diacetylene, 2,4-pentadiynal, and 2,4-pentadiynal tosylhydrazone. Photolysis of diazo compounds 6a-c (lambda > 444 nm; Ar or N2, 10 K) generates triplet carbenes HC5H (1) and HC5D (1-d), which have been characterized by IR, EPR, and UV/vis spectroscopy. Although many resonance structures contribute to the resonance hybrid for this highly unsaturated carbon-chain molecule, experiment and theory reveal that the structure is best depicted in terms of the dominant resonance contributor of penta-1,4-diyn-3-ylidene (diethynylcarbene, H-C[triple bond]C-:C-C[triple bond]C-H). Theory predicts an axially symmetric (D(infinity h)) structure and a triplet electronic ground state for 1 (CCSD(T)/ANO). Experimental IR frequencies and isotope shifts are in good agreement with computed values. The triplet EPR spectrum of 1 (absolute value(D/hc) = 0.6157 cm(-1), absolute value(E/hc) = 0.0006 cm(-1)) is consistent with an axially symmetric structure, and the Curie law behavior confirms that the triplet state is the ground state. The electronic absorption spectrum of 1 exhibits a weak transition near 400 nm with extensive vibronic coupling. Chemical trapping of triplet HC5H (1) in an O2-doped matrix affords the carbonyl oxide 16 derived exclusively from attack at the central carbon.

Hydrogen-bonded supramolecular structures of three related 4-(5-nitro-2-furyl)-1,4-dihydropyridines.

PubMed

Quesada, Antonio; Argüello, Jacqueline; Squella, Juan A; Wardell, James L; Low, John N; Glidewell, Christopher

2006-01-01

In ethyl 5-cyano-2,6-dimethyl-4-(5-nitro-2-furyl)-1,4-dihydropyridine-3-carboxylate, C15H15N3O5, the molecules are linked into chains by a single N-H...O hydrogen bond. The molecules in diethyl 2,6-dimethyl-4-(5-nitro-2-furyl)-1,4-dihydropyridine-3,5-dicarboxylate, C17H20N2O7, are linked by a combination of one N-H...O hydrogen bond and two C-H...O hydrogen bonds into sheets built from equal numbers of R(2)(2)(17) and R(4)(4)(18) rings. In 2,6-dimethyl-4-(5-nitro-2-furyl)-1,4-dihydropyridine-3,5-dicarbonitrile, C13H10N4O3, the molecules are linked by a combination of a three-centre N-H...(O)2 hydrogen bond and two independent two-centre C-H...O hydrogen bonds into complex sheets containing four types of ring.

Crystal structure and luminescence properties of silver in AgM(PO{sub 3}){sub 3} (M = Mg, Zn, Ba) polyphosphates

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

Belharouak, I.; Parent, C.; Tanguy, B.

1999-06-01

The relationships between the crystal structures and the luminescent properties of the AgM(PO{sub 3}){sub 3} (M = Mg, Zn, Ba) polyphosphates are reported in comparison with those of AgPO{sub 3}. The structure of the magnesium and zinc phosphates is characterized by long polyphosphates chains connected to infinite chains of [AgO{sub 6}] and [MO{sub 6}] polyhedra sharing faces. The basic structural phosphate unit in AgBa(PO{sub 3}){sub 3} is a P{sub 3}O{sub 9} ring. Silver atoms are located in distorted octahedral sites. Two types of luminescent centers have been observed. The UV emission observed in all these materials is typical of isolatedmore » Ag{sup +} ions. The visible emission observed only in the zinc phosphate is probably the result of a silver-zinc association. 16 refs., 8 figs., 3 tabs.« less

Head circumference in untreated and IGF-I treated patients with Laron syndrome: comparison with untreated and hGH-treated children with isolated growth hormone deficiency.

PubMed

Laron, Zvi; Iluz, Moshe; Kauli, Rivka

2012-04-01

Head circumference (HC) is a simple and practical measure of brain size, development and longitudinal measurements of the HC in childhood are an index of brain growth. To determine the effects of long IGF-I deficiency and treatment on HC in patients with Laron syndrome (LS). 20 untreated adult LS patients, aged 48.4±11.2 years and 13 LS patients treated between ages of 5.6±4 to 11.3±3 years were studied. 15 patients with congenital IGHD treated between age 6.1±4 and 13±4 by hGH served as controls. HC was expressed as standard deviation (SD) and Ht as SDS. HC was measured and plotted on Nellhaus charts. Linear height (Ht) was measured by a Harpenden Stadiometer. The mean HC deficit of the adult untreated LS males was -2.9±0.6 SD compared to a Ht deficit of -7.0±1.7 SDS. The HC of the LS adult females was -3.6±1 SD compared to a Ht SDS of -6.9±1.5 (p<0.001). IGF-I treatment (150-200 μg/kg once daily) increased the HC from -3.3±0.9 (m±SD) to normal values (0.87±1.8 SD) (p<0.001) in 11/13 children. The Ht SDS deficit decreased only by 1.5 SDS. hGH treatment of cIGHD children increased the HC from -2.0±1.8 to 0.3±1.2 SD and the Ht SDS from -4.8±1.6 to 1.6±1.0. Copyright © 2012 Elsevier Ltd. All rights reserved.

Highly Active N,O Zinc Guanidine Catalysts for the Ring-Opening Polymerization of Lactide.

PubMed

Schäfer, Pascal M; Fuchs, Martin; Ohligschläger, Andreas; Rittinghaus, Ruth; McKeown, Paul; Akin, Enver; Schmidt, Maximilian; Hoffmann, Alexander; Liauw, Marcel A; Jones, Matthew D; Herres-Pawlis, Sonja

2017-09-22

New zinc guanidine complexes with N,O donor functionalities were prepared, characterized by X-Ray crystallography, and examined for their catalytic activity in the solvent-free ring-opening polymerization (ROP) of technical-grade rac-lactide at 150 °C. All complexes showed a high activity. The fastest complex [ZnCl 2 (DMEGasme)] (C1) produced colorless poly(lactide) (PLA) after 90 min with a conversion of 52 % and high molar masses (M w =69 100, polydispersity=1.4). The complexes were tested with different monomer-to-initiator ratios to determine the rate constant k p . Furthermore, a polymerization with the most active complex C1 was monitored by in situ Raman spectroscopy. Overall, conversion of up to 90 % can be obtained. End-group analysis was performed to clarify the mechanism. All four complexes combine robustness against impurities in the lactide with high polymerization rates, and they represent the fastest robust lactide ROP catalysts to date, opening new avenues to a sustainable ROP catalyst family for industrial use. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

"Solid State" Chemistry in Titan Ice Particles

NASA Image and Video Library

2016-09-20

Scientists from NASA's Cassini mission suggested in a 2016 paper that the appearance of a cloud of dicyanoacetylene (C4N2) ice in Titan's stratosphere may be explained by "solid-state" chemistry taking place inside ice particles. The particles have an inner layer of cyanoacetylene (HC3N) ice coated with an outer layer of hydrogen cyanide (HCN) ice. Left: When a photon of light penetrates the outer shell, it can interact with the HC3N, producing C3N and H. Center: The C3N then reacts with HCN to yield C4N2 and H (shown at right). Another reaction that also yields C4N2 ice and H also is possible, but the researchers think it is less likely. http://photojournal.jpl.nasa.gov/catalog/PIA20715

Solubilization of rehydrated frozen highly concentrated micellar casein for use in liquid food applications.

PubMed

Lu, Y; McMahon, D J; Metzger, L E; Kommineni, A; Vollmer, A H

2015-09-01

Highly concentrated micellar casein concentrate (HC-MCC), a potential ingredient of protein-fortified food, is a gel at cold temperature. It contains ~17 to 21% casein, with most serum proteins and lactose removed by microfiltration and diafiltration, and it is then further concentrated using vacuum evaporation. The HC-MCC can be stored frozen, and our objective was to determine the conditions needed to obtain complete solubility of thawed HC-MCC in water and to understand its gelation upon cooling. Dispersibility (ability to pass through a 250-µm mesh sieve), suspendability (percentage of protein not sedimented at 80 × g within 5min), and solubility (percentage of protein not sedimented at 20,000 × g within 5min) were measured at 4, 12, or 20°C after various mixing conditions. Gelation upon cooling from 50 to 5°C was monitored based on storage (G') and loss (G'') moduli. The gelled HC-MCC was also examined by transmission electron microscopy. Thawed HC-MCC was added to water to reach a protein concentration of 3% and mixed using high shear (7,500rpm) for 1min or low shear (800rpm) for 30min at 4, 12, 20, or 50°C and at pH 6.4 to 7.2. The HC-MCC completely dispersed at 50°C, or at ≤20°C followed by overnight storage at 4°C. Suspendability at 50°C was ~90% whereas mixing at ≤20°C followed by overnight storage resulted in only ~57% suspendability. Solubility followed a similar trend with ~83% at 50°C and only ~29% at ≤20°C. Mixing HC-MCC with 60mM trisodium citrate increased dispersibility to 99% and suspendability and solubility to 81% at 20°C. Cold-gelling temperature, defined as the temperature at which G'=G'' when cooling from 50 to 5°C, was positively correlated with protein level in HC-MCC. Gelation occurred at 38, 28, and 7°C with 23, 20, and 17% of protein, respectively. Gelation was reversible upon heating, although after a second cooling cycle the HC-MCC gel had lower G'. In micrographs of gelled HC-MCC, the casein micelles were observed to be within the normal size range but packed very closely together, with only ~20 to 50 nm of space between them. We proposed that cold-gelation of HC-MCC occurs when the kinetic energy of the casein micelles is sufficiently reduced to inhibit their mobility in relation to adjacent casein micelles. Understanding solubilization of rehydrated frozen HC-MCC and its rheological properties can help in designing process systems for using HC-MCC as a potential ingredient in liquid food. Copyright © 2015 American Dairy Science Association. Published by Elsevier Inc. All rights reserved.

A spectral line survey of IRC +10216 between 13.3 and 18.5 GHz

NASA Astrophysics Data System (ADS)

Zhang, Xiao-Yan; Zhu, Qing-Feng; Li, Juan; Chen, Xi; Wang, Jun-Zhi; Zhang, Jiang-Shui

2017-10-01

A spectral line survey of IRC +10216 between 13.3 and 18.5 GHz was carried out using the Shanghai Tian Ma 65 m Radio Telescope (TMRT-65 m) with a sensitivity of <7 mK. Thirty-five spectral lines of 12 different molecules and radicals were detected in total. Except for SiS, the detected molecules are all carbon-chain molecules, including HC3N, HC5N, HC7N, HC9N, C6H, C6H-, C8H, SiC2, SiC4, c-C3H2, and l-C5H. The presence of rich carbon-bearing molecules is consistent with the identity of IRC +10216 as a carbon-rich asymptotic giant branch (AGB) star. The excitation temperatures and column densities of the observed species are derived by assuming a local thermodynamic equilibrium and homogeneous conditions. The reduced spectrum as a FITS file is only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/606/A74

In-depth study of the H - T phase diagram of Sr 4 Ru 3 O 10 by magnetization experiments

DOE PAGES

Weickert, F.; Civale, L.; Maiorov, B.; ...

2017-09-28

Here, we present magnetization measurements on Sr4Ru3O10 as a function of temperature and magnetic field applied perpendicular to the magnetic easy c-axis inside the ferromagnetic phase. Peculiar metamagnetism evolves in Sr4Ru3O10 below the ferromagnetic transition TC as a double step in the magnetization at two critical fields Hc1 and Hc2. We map the H-T phase diagram with special focus on the temperature range 50 K ≤T≤TC. We find that the critical field Hc1(T) connects the field and temperature axes of the phase diagram, whereas the Hc2 boundary starts at 2.8 T for the lowest temperatures and ends in a criticalmore » endpoint at (1 T; 80 K). We also conclude from the temperature dependence of the ratio Hc1Hc2(T) that the double metamagnetic transition is an intrinsic effect of the material and it is not caused by sample stacking faults such as twinning or partial in-plane rotation between layers.« less

In-depth study of the H - T phase diagram of Sr4Ru3O10 by magnetization experiments

NASA Astrophysics Data System (ADS)

Weickert, F.; Civale, L.; Maiorov, B.; Jaime, M.; Salamon, M. B.; Carleschi, E.; Strydom, A. M.; Fittipaldi, R.; Granata, V.; Vecchione, A.

2018-05-01

We present magnetization measurements on Sr4Ru3O10 as a function of temperature and magnetic field applied perpendicular to the magnetic easy c-axis inside the ferromagnetic phase. Peculiar metamagnetism evolves in Sr4Ru3O10 below the ferromagnetic transition TC as a double step in the magnetization at two critical fields Hc1 and Hc2. We map the H - T phase diagram with special focus on the temperature range 50 K ≤ T ≤TC . We find that the critical field Hc1 (T) connects the field and temperature axes of the phase diagram, whereas the Hc2 boundary starts at 2.8 T for the lowest temperatures and ends in a critical endpoint at (1 T; 80 K). We conclude from the temperature dependence of the ratio Hc 1/Hc 2 (T) that the double metamagnetic transition is an intrinsic effect of the material and it is not caused by sample stacking faults such as twinning or partial in-plane rotation between layers.

Chemical Complexity in Local Diffuse and Translucent Clouds: Ubiquitous Linear C3H and CH3CN, a Detection of HC3N and an Upper Limit on the Abundance of CH2CN

NASA Astrophysics Data System (ADS)

Liszt, Harvey; Gerin, Maryvonne; Beasley, Anthony; Pety, Jerome

2018-04-01

We present Jansky Very Large Array observations of 20–37 GHz absorption lines from nearby Galactic diffuse molecular gas seen against four cosmologically distant compact radio continuum sources. The main new observational results are that l-C3H and CH3CN are ubiqitous in the local diffuse molecular interstellar medium at {\\text{}}{A}{{V}} ≲ 1, while HC3N was seen only toward B0415 at {\\text{}}{A}{{V}} > 4 mag. The linear/cyclic ratio is much larger in C3H than in C3H2 and the ratio CH3CN/HCN is enhanced compared to TMC-1, although not as much as toward the Horsehead Nebula. More consequentially, this work completes a long-term program assessing the abundances of small hydrocarbons (CH, C2H, linear and cyclic C3H and C3 {{{H}}}2, and C4H and C4H‑) and the CN-bearing species (CN, HCN, HNC, HC3N, HC5N, and CH3CN): their systematics in diffuse molecular gas are presented in detail here. We also observed but did not strongly constrain the abundances of a few oxygen-bearing species, most prominently HNCO. We set limits on the column density of CH2CN, such that the anion CH2CN‑ is only viable as a carrier of diffuse interstellar bands if the N(CH2CN)/N(CH2CN‑) abundance ratio is much smaller in this species than in any others for which the anion has been observed. We argue that complex organic molecules (COMS) are not present in clouds meeting a reasonable definition of diffuse molecular gas, i.e., {\\text{}}{A}{{V}} ≲ 1 mag. Based on observations obtained with the NRAO Jansky Very Large Array (VLA).

Location of the synaptosome-binding regions on botulinum neurotoxin B.

PubMed

Dolimbek, Behzod Z; Steward, Lance E; Aoki, K Roger; Atassi, M Zouhair

2012-01-10

The regions of botulinum neurotoxin B (BoNT/B) involved in binding to mouse brain synaptosomes (snps) were localized. Sixty 19-residue overlapping peptides (peptide C31 consisted of 24 residues) encompassing BoNT/B H chain (residues 442-1291) were synthesized and used to inhibit binding of (125)I-labeled BoNT/B to snps. Synaptosome-binding regions were noncompeting and existed on both H(N) and H(C) domains of neurotoxin. At 37 °C, inhibitory activities on H(N) resided, in decreasing order, in peptides 638-656 (26.7%), 596-614 (18.2%), 512-530 (13.9%), 778-796 (13.8%), and 526-544 (11.6%). On H(C), activity resided in decreasing order in peptides 1170-1188 (44.6%), 1128-1146 (21.6%), 1184-1202 (18.6%), 1156-1174 (13.0%), 946-964 (11.8%), 1114-1132 (11.2%), 1100-1118 (6.2%), 876-894 (6.1%), 1268-1291 (4.6%), and 1226-1244 (4.3%). The 45 remaining H(N) and H(C) peptides had no activity. At 4 °C, peptide C24 (1170-1188) remained quite active (inhibiting, 31.2%), while activities of peptides N15, C21, and C25 were little under 10%. The snp-binding regions contained sites that bind synaptotagmin II and gangliosides. Despite the low degree of sequence homology, BoNT/B and BoNT/A display significant structural homology and appeared to bind in part to the same snp-binding regions. Binding of each labeled toxin to snps was inhibited ~50% by the other toxin, 70-72% by its correlate H(C), and by the H(C) of the other toxin [29% (BoNT/A by H(C) of B) or 32% (BoNT/B by H(C) of A)]. In the three-dimensional structure of BoNT/B, the greater part of H(C), one H(N) face, and part of the belt on the same side interact with snps. Thus, BoNT/B binds to snps through the H(C) head and employs regions on one H(N) face and the belt, reserving flexibility for the belt's unbound part to release the light chain. Most snp-binding regions coincide or overlap with blocking antibody (Ab)-binding regions explaining how such Abs prevent BoNT/B toxicity.

Hybrid treatment strategies for 2,4,6-trichlorophenol degradation based on combination of hydrodynamic cavitation and AOPs.

PubMed

Barik, Arati J; Gogate, Parag R

2018-01-01

Utilization of hybrid treatment schemes involving advanced oxidation processes and hydrodynamic cavitation in the wastewater treatment forms the prime focus of the present work. The initial phase of the work includes analysis of recent literature relating to the performance of combined approach based on hydrodynamic cavitation (HC) for degradation of different pollutants followed by a detailed investigation into degradation of 2,4,6-trichlorophenol (2,4,6-TCP). The degradation of the priority pollutant, 2,4,6-TCP, using combination of HC based on slit-venturi used as the cavitating device, ozone and H 2 O 2 has been investigated. The effect of operating pressure (2-5bar) and initial pH (3-11) have been investigated for the degradation using only HC. The degradation using only ozone (100-400mg/h) and only H 2 O 2 has also been studied. The efficacy of the combined operation of HC+O 3 at different ozone flow rates (100-400mg/h) and the combined operation of HC+H 2 O 2 at different loadings of H 2 O 2 (2,4,6-TCP:H 2 O 2 as 1:1-1:7) have been subsequently investigated. The degradation efficacy has also been established for the combined treatment strategies of O 3 +H 2 O 2 and HC+O 3 +H 2 O 2 at the optimum conditions of temperature as 30°C, inlet pressure of 4bar and initial pH of 7. Extent of 2,4,6-TCP degradation, TOC and COD removal obtained for HC+O 3 process were 97.1%, 94.4% and 78.5% respectively whereas for O 3 +H 2 O 2 process, the values were 95.5%, 94.8% and 76.2% and for HC+O 3 +H 2 O 2 process the extent of reduction were 100%, 95.6% and 80.9% in the same order. The combined treatment approach as HC+O 3 +H 2 O 2 was established as the most efficient approach for complete removal of 2,4,6-TCP with near complete TOC removal. Copyright © 2017 Elsevier B.V. All rights reserved.

Accumulation of kaempferitrin and expression of phenyl-propanoid biosynthetic genes in kenaf (Hibiscus cannabinus).

PubMed

Zhao, Shicheng; Li, Xiaohua; Cho, Dong Ha; Arasu, Mariadhas Valan; Al-Dhabi, Naif Abdullah; Park, Sang Un

2014-10-23

Kenaf (Hibiscus cannabinus) is cultivated worldwide for its fiber; however, the medicinal properties of this plant are currently attracting increasing attention. In this study, we investigated the expression levels of genes involved in the biosynthesis of kaempferitrin, a compound with many biological functions, in different kenaf organs. We found that phenylalanine ammonia lyase (HcPAL) was more highly expressed in stems than in other organs. Expression levels of cinnamate 4-hydroxylase (HcC4H) and 4-coumarate-CoA ligase (Hc4CL) were highest in mature leaves, followed by stems and young leaves, and lowest in roots and mature flowers. The expression of chalcone synthase (HcCHS), chalcone isomerase (HcCHI), and flavone 3-hydroxylase (HcF3H) was highest in young flowers, whereas that of flavone synthase (HcFLS) was highest in leaves. An analysis of kaempferitrin accumulation in the different organs of kenaf revealed that the accumulation of this compound was considerably higher (>10-fold) in leaves than in other organs. On the basis of a comparison of kaempferitrin contents with the expression levels of different genes in different organs, we speculate that HcFLS plays an important regulatory role in the kaempferitrin biosynthetic pathway in kenaf.

Transient Receptor Potential Channel Opening Releases Endogenous Acetylcholine, which Contributes to Endothelium-Dependent Relaxation Induced by Mild Hypothermia in Spontaneously Hypertensive Rat but Not Wistar-Kyoto Rat Arteries.

PubMed

Zou, Q; Leung, S W S; Vanhoutte, P M

2015-08-01

Mild hypothermia causes endothelium-dependent relaxations, which are reduced by the muscarinic receptor antagonist atropine. The present study investigated whether endothelial endogenous acetylcholine contributes to these relaxations. Aortic rings of spontaneously hypertensive rats (SHRs) and normotensive Wistar-Kyoto (WKY) rats were contracted with prostaglandin F2 α and exposed to progressive mild hypothermia (from 37 to 31°C). Hypothermia induced endothelium-dependent, Nω-nitro-l-arginine methyl ester-sensitive relaxations, which were reduced by atropine, but not by mecamylamine, in SHR but not in WKY rat aortae. The responses in SHR aortae were also reduced by acetylcholinesterase (the enzyme responsible for acetylcholine degradation), bromoacetylcholine (inhibitor of acetylcholine synthesis), hemicholinium-3 (inhibitor of choline uptake), and vesamicol (inhibitor of acetylcholine release). The mild hypothermia-induced relaxations in both SHR and WKY rat aortae were inhibited by AMTB [N-(3-aminopropyl)-2-[(3-methylphenyl)methoxy]-N-(2-thienylmethyl)-benzamide; the transient receptor potential (TRP) M8 inhibitor]; only those in SHR aortae were inhibited by HC-067047 [2-methyl-1-[3-(4-morpholinyl)propyl]-5-phenyl-N-[3-(trifluoromethyl)phenyl]-1H-pyrrole-3-carboxamide; TRPV4 antagonist] while those in WKY rat aortae were reduced by HC-030031 [2-(1,3-dimethyl-2,6-dioxo-1,2,3,6-tetrahydro-7H-purin-7-yl)-N-(4-isopropylphenyl)acetamide; TRPA1 antagonist]. The endothelial uptake of extracellular choline and release of cyclic guanosine monophosphate was enhanced by mild hypothermia and inhibited by HC-067047 in SHR but not in WKY rat aortae. Compared with WKY rats, the SHR preparations expressed similar levels of acetylcholinesterase and choline acetyltransferase, but a lesser amount of vesicular acetylcholine transporter, located mainly in the endothelium. Thus, mild hypothermia causes nitric oxide-dependent relaxations by opening TRPA1 channels in WKY rat aortae. By contrast, in SHR aortae, TRPV4 channels are opened, resulting in endothelial production of acetylcholine, which, in an autocrine manner, activates muscarinic receptors on neighboring cells to elicit endothelium-dependent relaxations in response to mild hypothermia. Copyright © 2015 by The American Society for Pharmacology and Experimental Therapeutics.

Detection of HC5N and HC7N Isotopologues in TMC-1 with the Green Bank Telescope

NASA Astrophysics Data System (ADS)

Burkhardt, A. M.; Herbst, E.; Kalenskii, S. V.; McCarthy, M. C.; Remijan, A. J.; McGuire, B. A.

2018-03-01

We report the first interstellar detection of DC7N and six 13C-bearing isotopologues of HC7N towards the dark cloud TMC-1 through observations with the Green Bank Telescope, and confirm the recent detection of HC515N. For the average of the 13C isotopomers, DC7N, and HC515N, we derive column densities of 1.9(2) × 1011, 2.5(9) × 1011, and 1.5(4) × 1011 cm-2, respectively. The resulting isotopic ratios are consistent with previous values derived from similar species in the source, and we discuss the implications for the formation chemistry of the observed cyanopolyynes. Within our uncertainties, no significant 13C isotopomer variation is found for HC7N, limiting the significance CN could have in its production. The results further show that, for all observed isotopes, HC5N may be isotopically depleted relative to HC3N and HC7N, suggesting that reactions starting from smaller cyanopolyynes may not be efficient to form HCnN. This leads to the conclusion that the dominant production route may be the reaction between hydrocarbon ions and nitrogen atoms.

Oral atorvastatin therapy increases nitric oxide-dependent cutaneous vasodilation in humans by decreasing ascorbate-sensitive oxidants

PubMed Central

Kenney, W. Larry

2011-01-01

Elevated low-density lipoproteins (LDL) are associated with cutaneous microvascular dysfunction partially mediated by increased arginase activity, which is decreased following a systemic atorvastatin therapy. We hypothesized that increased ascorbate-sensitive oxidant stress, partially mediated through uncoupled nitric oxide synthase (NOS) induced by upregulated arginase, contributes to cutaneous microvascular dysfunction in hypercholesterolemic (HC) humans. Four microdialysis fibers were placed in the skin of nine HC (LDL = 177 ± 6 mg/dl) men and women before and after 3 mo of a systemic atorvastatin intervention and at baseline in nine normocholesterolemic (NC) (LDL = 95 ± 4 mg/dl) subjects. Sites served as control, NOS inhibited, L-ascorbate, and arginase-inhibited+L-ascorbate. Skin blood flow was measured while local skin heating (42°C) induced NO-dependent vasodilation. After the established plateau in all sites, 20 mM ≪ngname≫ was infused to quantify NO-dependent vasodilation. Data were normalized to maximum cutaneous vascular conductance (CVC) (sodium nitroprusside + 43°C). The plateau in vasodilation during local heating (HC: 78 ± 4 vs. NC: 96 ± 2% CVCmax, P < 0.01) and NO-dependent vasodilation (HC: 40 ± 4 vs. NC: 54 ± 4% CVCmax, P < 0.01) was reduced in the HC group. Acute L-ascorbate alone (91 ± 5% CVCmax, P < 0.001) or combined with arginase inhibition (96 ± 3% CVCmax, P < 0.001) augmented the plateau in vasodilation in the HC group but not the NC group (ascorbate: 96 ± 2; combo: 93 ± 4% CVCmax, both P > 0.05). After the atorvastatin intervention NO-dependent vasodilation was augmented in the HC group (HC postatorvastatin: 64 ± 4% CVCmax, P < 0.01), and there was no further effect of ascorbate alone (58 ± 4% CVCmax, P > 0.05) or combined with arginase inhibition (67 ± 4% CVCmax, P > 0.05). Increased ascorbate-sensitive oxidants contribute to hypercholesteromic associated cutaneous microvascular dysfunction which is partially reversed with atorvastatin therapy. PMID:21715698

Extraordinary cluster formation and intramolecular ligand-ligand interactions in cyanoacetylene [corrected] mediated by Mg+*: implications for the atmospheric chemistry of titan and for circumstellar chemistry.

PubMed

Milburn, Rebecca K; Hopkinson, Alan C; Bohme, Diethard K

2005-09-21

Experimental results are reported that track the kinetics of gas-phase reactions initiated by Mg+*, (c-C5H5)Mg+ and (c-C5H5)2Mg+* in hydrogen cyanide and cyanoacetylene. The experiments were performed with a selected-ion flow tube (SIFT) tandem mass spectrometer at a helium buffer-gas pressure of 0.35 +/- 0.01 Torr and at 294 +/- 3 K. The observed chemistries of Mg+* and (c-C5H5)Mg+ are dominated by sequential ligation, while that of (c-C5H5)2Mg+* is by ligand switching. The rate-coefficient measurements for sequential addition of cyanoacetylene to Mg+* indicate an extraordinary pattern in alternating chemical reactivity while multiple-collision induced dissociation experiments revealed an extraordinary stability for the Mg(HC3N)4+* cluster ion. Molecular orbital calculations with density functional theory (DFT) at the B3LYP level, Hartree-Fock (HF) and second-order Mphiller-Plesset (MP2) levels, all performed with a 6-31+G(d) basis set, have been used to calculate structures and energies for the observed Mg(HC3N)1-4(+)* cations. These calculations indicate that the path of formation of Mg(HC3N)4+* involves ligand-ligand interactions leading to two cyclic (HC3N)2 ligands which then interact to form 2,4,6,8-tetracyanosemibullvalene-Mg+ or 1,2,5,6-tetracyano-1,3,5,7-cyclooctatetraene-Mg+ cations. A case is made for the formation of similar complex organomagnesium ions in the upper atmosphere of Titan where subsequent electron-ion recombination may produce cyano derivatives of large unsaturated hydrocarbons. In contrast, circumstellar environments with their much higher relative content of free electrons are less likely to give rise to such chemistry.

Insight into Oxide-Bridged Heterobimetallic Al/Zr Olefin Polymerization Catalysts.

PubMed

Boulho, Cédric; Zijlstra, Harmen S; Hofmann, Alexander; Budzelaar, Peter H M; Harder, Sjoerd

2016-11-21

Reaction of (TBBP)AlMe⋅THF with [Cp* 2 Zr(Me)OH] gave [(TBBP)Al(THF)-O-Zr(Me)Cp* 2 ] (TBBP=3,3',5,5'-tetra-tBu-2,2'-biphenolato). Reaction of [DIPPnacnacAl(Me)-O-Zr(Me)Cp 2 ] with [PhMe 2 NH] + [B(C 6 F 5 ) 4 ] - gave a cationic Al/Zr complex that could be structurally characterized as its THF adduct [(DIPPnacnac)Al(Me)-O-Zr(THF)Cp 2 ] + [B(C 6 F 5 ) 4 ] - (DIPPnacnac=HC[(Me)C=N(2,6-iPr 2 -C 6 H 3 )] 2 ). The first complex polymerizes ethene in the presence of an alkylaluminum scavenger but in the absence of methylalumoxane (MAO). The adduct cation is inactive under these conditions. Theoretical calculations show very high energy barriers (ΔG=40-47 kcal mol -1 ) for ethene insertion with a bridged AlOZr catalyst. This is due to an unfavorable six-membered-ring transition state, in which the methyl group bridges the metal and ethene with an obtuse metal-Me-C angle that prevents synchronized bond-breaking and making. A more-likely pathway is dissociation of the Al-O-Zr complex into an aluminate and the active polymerization catalyst [Cp* 2 ZrMe] + . © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Benzo[a]carbazoles and an Indolo[2,3-a]carbazole from 3-Aryltetramic Acids.

PubMed

Truax, Nathanyal J; Banales Mejia, Fernando; Kwansare, Deborah O; Lafferty, Megan M; Kean, Maeve H; Pelkey, Erin T

2016-08-05

A simple and flexible approach to 3-pyrrolin-2-one fused carbazoles is disclosed. The key step involves the BF3-mediated electrophilic substitution of indoles with N-alkyl-substituted 3-aryltetramic acids, which provides access to indole-substituted 3-pyrrolin-2-ones. Scholl-type oxidative cyclizations of these materials led to the formation of the corresponding 3-pyrrolin-2-one-fused benzo[a]carbazoles and indolo[2,3-a]carbazoles. This work represents the first synthesis of the benzo[a]pyrrolo[3,4-c]carbazol-3(8H)-one ring system, while the indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-one ring system is found in a number of biologically active compounds including the protein kinase C (PKC) inhibitor, staurosporine.

Preparation of dibenzo[e,g]isoindol-1-ones via Scholl-type oxidative cyclization reactions.

PubMed

van Loon, Amy A; Holton, Maeve K; Downey, Catherine R; White, Taryn M; Rolph, Carly E; Bruening, Stephen R; Li, Guanqun; Delaney, Katherine M; Pelkey, Sarah J; Pelkey, Erin T

2014-09-05

A flexible synthesis of dibenzo[e,g]isoindol-1-ones has been developed. Dibenzo[e,g]isoindol-1-ones represent simplified benzenoid analogues of biological indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-ones (indolocarbazoles), compounds that have demonstrated a wide range of biological activity. The synthesis of the title compounds involved tetramic acid sulfonates. Different aryl groups were introduced at C4 of the heterocyclic ring via Suzuki-Miyaura cross-coupling reactions. Finally, mild Scholl-type oxidative cyclizations mediated by phenyliodine(III) bis(trifluoroacetate) (PIFA) converted some of the latter compounds into the corresponding dibenzo[e,g]isoindol-1-ones. A systematic study of the oxidative cyclization revealed the following reactivity trend: 3,4-dimethoxyphenyl ≫ 3-methoxyphenyl > 3,4,5-trimethoxyphenyl > 4-methoxyphenyl ≈ phenyl. Overall, the oxidative cyclization required at least two methoxy groups distributed in the aromatic rings, at least one of which had to be located para to the site of the cyclization.

Preparation of Dibenzo[e,g]isoindol-1-ones via Scholl-Type Oxidative Cyclization Reactions

PubMed Central

2015-01-01

A flexible synthesis of dibenzo[e,g]isoindol-1-ones has been developed. Dibenzo[e,g]isoindol-1-ones represent simplified benzenoid analogues of biological indolo[2,3-a]pyrrolo[3,4-c]carbazol-5-ones (indolocarbazoles), compounds that have demonstrated a wide range of biological activity. The synthesis of the title compounds involved tetramic acid sulfonates. Different aryl groups were introduced at C4 of the heterocyclic ring via Suzuki–Miyaura cross-coupling reactions. Finally, mild Scholl-type oxidative cyclizations mediated by phenyliodine(III) bis(trifluoroacetate) (PIFA) converted some of the latter compounds into the corresponding dibenzo[e,g]isoindol-1-ones. A systematic study of the oxidative cyclization revealed the following reactivity trend: 3,4-dimethoxyphenyl ≫ 3-methoxyphenyl > 3,4,5-trimethoxyphenyl > 4-methoxyphenyl ≈ phenyl. Overall, the oxidative cyclization required at least two methoxy groups distributed in the aromatic rings, at least one of which had to be located para to the site of the cyclization. PMID:25138638

New fluorescent azo-Schiff base Cu(II) and Zn(II) metal chelates; spectral, structural, electrochemical, photoluminescence and computational studies

NASA Astrophysics Data System (ADS)

Purtas, Fatih; Sayin, Koray; Ceyhan, Gokhan; Kose, Muhammet; Kurtoglu, Mukerrem

2017-06-01

A new Schiff base containing azo chromophore group obtained by condensation of 2-hydroxy-4-[(E)-phenyldiazenyl]benzaldehyde with 3,4-dimethylaniline (HL) are used for the syntheses of new copper(II) and zinc(II) chelates, [Cu(L)2], and [Zn(L)2], and characterized by physico-chemical and spectroscopic methods such as 1H and 13C NMR, IR, UV.-Vis. and elemental analyses. The solid state structure of the ligand was characterized by single crystal X-ray diffraction study. X-ray diffraction data was then used to calculate the harmonic oscillator model of aromaticity (HOMA) indexes for the rings so as to investigate of enol-imine and keto-amine tautomeric forms in the solid state. The phenol ring C10-C15 shows a considerable deviation from the aromaticity with HOMA value of 0.837 suggesting the shift towards the keto-amine tautomeric form in the solid state. The analytical data show that the metal to ligand ratio in the chelates was found to be 1:2. Theoretical calculations of the possible isomers of the ligand and two metal complexes are performed by using B3LYP method. Electrochemical and photoluminescence properties of the synthesized azo-Schiff bases were also investigated.

40 CFR 1065.341 - CVS, PFD, and batch sampler verification (propane check).

Code of Federal Regulations, 2014 CFR

2014-07-01

... may use the HC contamination procedure in § 1065.520(f) to verify HC contamination. Otherwise, zero... range that can measure the C3H8 concentration expected for the CVS and C3H8 flow rates. (2) Zero the HC analyzer using zero air introduced at the analyzer port. (3) Span the HC analyzer using C3H8 span gas...

40 CFR 1065.341 - CVS and batch sampler verification (propane check).

Code of Federal Regulations, 2012 CFR

2012-07-01

... may use the HC contamination procedure in § 1065.520(g) to verify HC contamination. Otherwise, zero... range that can measure the C3H8 concentration expected for the CVS and C3H8 flow rates. (2) Zero the HC analyzer using zero air introduced at the analyzer port. (3) Span the HC analyzer using C3H8 span gas...

40 CFR 1065.341 - CVS and batch sampler verification (propane check).

Code of Federal Regulations, 2013 CFR

2013-07-01

... may use the HC contamination procedure in § 1065.520(g) to verify HC contamination. Otherwise, zero... range that can measure the C3H8 concentration expected for the CVS and C3H8 flow rates. (2) Zero the HC analyzer using zero air introduced at the analyzer port. (3) Span the HC analyzer using C3H8 span gas...

Exceptional sensitivity of metal-aryl bond energies to ortho-fluorine substituents: influence of the metal, the coordination sphere, and the spectator ligands on M-C/H-C bond energy correlations.

PubMed

Clot, Eric; Mégret, Claire; Eisenstein, Odile; Perutz, Robin N

2009-06-10

DFT calculations are reported of the energetics of C-H oxidative addition of benzene and fluorinated benzenes, Ar(F)H (Ar(F) = C(6)F(n)H(5-n), n = 0-5) at ZrCp(2) (Cp = eta(5)-C(5)H(5)), TaCp(2)H, TaCp(2)Cl, WCp(2), ReCp(CO)(2), ReCp(CO)(PH(3)), ReCp(PH(3))(2), RhCp(PH(3)), RhCp(CO), IrCp(PH(3)), IrCp(CO), Ni(H(2)PCH(2)CH(2)PH(2)), Pt(H(2)PCH(2)CH(2)PH(2)). The change in M-C bond energy of the products fits a linear function of the number of fluorine substituents, with different coefficients corresponding to ortho-, meta-, and para-fluorine. The values of the ortho-coefficient range from 20 to 32 kJ mol(-1), greatly exceeding the values for the meta- and para-coefficients (2.0-4.5 kJ mol(-1)). Similarly, the H-C bond energies of Ar(F)H yield ortho- and para-coefficients of 10.4 and 3.4 kJ mol(-1), respectively, and a negligible meta-coefficient. These results indicate a large increase in the M-C bond energy with ortho-fluorine substitution on the aryl ring. Plots of D(M-C) vs D(H-C) yield slopes R(M-C/H-C) that vary from 1.93 to 3.05 with metal fragment, all in excess of values of 1.1-1.3 reported with other hydrocarbyl groups. Replacement of PH(3) by CO decreases R(M-C/H-C) significantly. For a given ligand set and metals in the same group of the periodic table, the value of R(M-C/H-C) does not increase with the strength of the M-C bond. Calculations of the charge on the aryl ring show that variations in ionicity of the M-C bonds correlate with variations in M-C bond energy. This strengthening of metal-aryl bonds accounts for numerous experimental results that indicate a preference for ortho-fluorine substituents.

Synthesis, anisotropy, and superconducting properties of LiFeAs single crystal

NASA Astrophysics Data System (ADS)

Song, Yoo Jang; Ghim, Jin Soo; Min, Byeong Hun; Kwon, Yong Seung; Jung, Myung Hwa; Rhyee, Jong-Soo

2010-05-01

A LiFeAs single crystal with Tconset˜19.7 K was grown in a sealed tungsten crucible using the Bridgeman method. The electrical resistivity experiments revealed a ratio of room temperature to residual resistivity of approximately 46 and 18 for the in-plane and out-of plane directions, respectively. The estimated anisotropic resistivity, γρ=ρc/ρab, was approximately 3.3 at Tconset. The upper critical fields had large Hc2∥ab and Hc2∥c values of 83.4 T and 72.5 T, respectively, and an anisotropy ratio is γH=Hc2∥ab/Hc2∥c˜1.15. The high upper critical field value and small anisotropy highlight the potential use of LiFeAs in a variety of applications. The calculated critical current density (Jc) from the M-H loop is approximately 103 A/cm2

Long Life Elastomeric Aircraft Hydraulic Seals. Part 3

DTIC Science & Technology

1976-03-01

J.O 1.0 Dibutoxyethyl Sebacate 5.0 - - - Diethylhexyl Azelate 5.0 - - - Varox 3.0 3.0 3.0 3.0 Original Physical Properties: (2-214 0 -rings... Acid 1.0 HiSil EP 30.0 N650 GPF-HS 40.0 Zinc Oxide 5.0 Polydispersion A(ZCNj D85 - Di(Butoxy-Ethoxy- Ethyl) Formal 10.0 Dicup 40C 5.0 Original...Polysar XPRD 435 llycar 4043 Sulfur Aminox Agerite White Stearic Acid Acrawax C N550 FEF N326 HAF-LS Sodium Stearate Potassium Stearate

C-shaped diastereomers containing cofacial thiophene-substituted quinoxaline rings: synthesis, photophysical properties, and X-ray crystallography.

PubMed

DeBlase, Catherine R; Finke, Ryan T; Porras, Jonathan A; Tanski, Joseph M; Nadeau, Jocelyn M

2014-05-16

Synthesis and characterization of two diastereomeric C-shaped molecules containing cofacial thiophene-substituted quinoxaline rings are described. A previously known bis-α-diketone was condensed with an excess of 4-bromo-1,2-diaminobenzene in the presence of zinc acetate to give a mixture of two C-shaped diastereomers with cofacial bromine-substituted quinoxaline rings. After chromatographic separation, thiophene rings were installed by a microwave-assisted Suzuki coupling reaction, resulting in highly emissive diastereomeric compounds that were studied by UV-vis, fluorescence, and NMR spectroscopy, as well as X-ray crystallography. The unique symmetry of each diastereomer was confirmed by NMR spectroscopy. NMR data indicated that the syn isomer has restricted rotation about the bond connecting the thiophene and quinoxaline rings, which was also observed in the solid state. The spectroscopic properties of the C-shaped diastereomers were compared to a model compound containing only a single thiophene-substituted quinoxaline ring. Ground state intramolecular π-π interactions in solution were detected by NMR and UV-vis spectroscopy. Red-shifted emission bands, band broadening, and large Stokes shifts were observed, which collectively suggest excited state π-π interactions that produce excimer-like emissions, as well as a remarkable positive emission solvatochromism, indicating charge-transfer character in the excited state.

Nutritional adequacy of energy restricted diets for young obese women.

PubMed

O'Connor, Helen; Munas, Zahra; Griffin, Hayley; Rooney, Kieron; Cheng, Hoi Lun; Steinbeck, Katharine

2011-01-01

Energy restricted meal plans may compromise nutrient intake. This study used diet modelling to assess the nutritional adequacy of energy restricted meal plans designed for weight management in young obese women. Diet modelling of 6000 kJ/d animal protein based meal plans was performed using Australian nutrient databases with adequacy compared to the Australian Nutrient Reference Values (NRVs) for women (19-30 years). One diet plan was based on the higher carbohydrate (HC) version of the Australian Guide to Healthy Eating for women 19-60 years. An alternative higher protein (HP) plan was adapted from the CSIRO Total Wellbeing Diet. Vegan and lacto-ovo versions of these plans were also modelled and compared to the appropriate vegetarian NRVs. Both animal protein diets met the estimated average requirement (EAR) or adequate intake (AI) for all nutrients analysed. The recommended dietary intake (RDI) was also satisfied, except for iron. HC met 75±30% and HP 81±31% of the iron RDI when red meat and iron fortified cereal were both included three days a week, and remained below the RDI even when red meat was increased to seven days. Iron for the modified vegan (57±5% HC; 66±4% HP) and lacto-ovo (48±6% HC; 59±7% HP) plans was below the RDI and zinc below the EAR for the vegan (76±8% HC; 84±9% HP) plans. The 6000 kJ/d animal protein meal plans met the RDI for all nutrients except iron. Iron and zinc failed to meet the vegetarian RDI and EAR respectively for the vegan plans.

Magnesium, zinc, and chromium levels in children, adolescents, and young adults with type 1 diabetes.

PubMed

Lin, Ching-Chiang; Tsweng, Guey-Ju; Lee, Cheng-Fa; Chen, Bai-Hsiun; Huang, Yeou-Lih

2016-08-01

Several trace elements are involved in insulin signal transduction and glucose metabolism. Our aim for this present study was to determine the levels of three important elements-magnesium, chromium, and zinc-as well as one oxidative stress marker-malondialdehyde (MDA)-in young type 1 diabetic patients at different periods of their growth, and to realize the relationships between trace elements, oxidative stress, and growth stages. A total of 88 patients with type 1 diabetes mellitus in different growth stages and 76 gender- and age-matched healthy subjects were included in this study. The levels of MDA were measured through HPLC using a C-18 column. Zinc, magnesium, and chromium concentrations in serum were assessed using atomic absorption spectrophotometry. We found higher levels of blood malondialdehyde (MDA; p < 0.001), significantly lower levels of magnesium (p < 0.001), and no differences in zinc and chromium levels (p = 0.153 and 0.515, respectively) in younger type 1 diabetic subjects relative to those of control subjects. Only 3.4% (3/88) of younger diabetic subjects exhibited hypomagnesemia; similar results were obtained when comparing different subgroups: children, adolescents, and adults. We also observed no differences in the levels of the three elements between the genders and among the growth stages (p > 0.05) of the diabetic subjects. There were no correlations between the three trace elements and HbA1C, diabetes duration, and insulin dose/BMI (all p > 0.05), but there was a significant difference between zinc levels and insulin dose/BMI (p = 0.043) in the diabetic patients. We found elevated blood MDA, decreased magnesium, and no changes in zinc and chromium levels in younger type 1 diabetic subjects relative to those of control subjects. Only 3.4% of younger diabetic subjects exhibited hypomagnesemia. Whether magnesium supplementation is suitable for improving insulin sensitivity and decreasing oxidative stress and inflammation will require confirmation through additional studies. Copyright © 2015 Elsevier Ltd and European Society for Clinical Nutrition and Metabolism. All rights reserved.

Coexistence of ferromagnetism and unconventional spin-glass freezing in the site-disordered kagome ferrite SrS n2F e4O11

NASA Astrophysics Data System (ADS)

Shlyk, L.; Strobel, S.; Farmer, B.; De Long, L. E.; Niewa, R.

2018-02-01

Single-crystal x-ray diffraction refinements indicate SrS n2F e4O11 crystallizes in the hexagonal R -type ferrite structure with noncentrosymmetric space group P 63m c and lattice parameters a =5.9541 (2 )Å , c =13.5761 (5 )Å , Z =2 (R (F )=0.034 ). Octahedrally coordinated 2 a [M (1) and M (1a)] and 6 c sites [M (2 )] have random, mixed occupation by Sn and Fe; whereas the tetrahedrally coordinated 2 b sites [Fe(3) and Fe(3a)] are exclusively occupied by Fe, whose displacement from the ideal position with trigonal-bipyramidal coordination causes the loss of inversion symmetry. Our dc and ac magnetization data indicate SrS n2F e4O11 single crystals undergo a ferro- or ferri-magnetic transition below a temperature TC=630 K with very low coercive fields μoHc ⊥=0.27 Oe and μoHc ∥=1.5 Oe at 300 K, for applied field perpendicular and parallel to the c axis, respectively. The value for TC is exceptionally high, and the coercive fields exceptionally low, among the known R-type ferrites. Time-dependent dc magnetization and frequency-dependent ac magnetization data indicate the onset of short-range, spin-glass freezing below Tf=35.8 K , which results from crystallographic disorder of magnetic F e3 + and nonmagnetic S n4 + ions on a frustrated Kagome sublattice. Anomalous ac susceptibility and thermomagnetic relaxation behavior in the short-range-ordered state differs from that of conventional spin glasses. Optical measurements in the ultraviolet to visible frequency range in a diffuse reflectance geometry indicate an overall optical band gap of 0.8 eV, consistent with observed semiconducting properties.

Performance evaluation of Samsung LABGEO(HC10) Hematology Analyzer.

PubMed

Park, Il Joong; Ahn, Sunhyun; Kim, Young In; Kang, Seon Joo; Cho, Sung Ran

2014-08-01

The Samsung LABGEO(HC10) Hematology Analyzer (LABGEO(HC10)) is a recently developed automated hematology analyzer that uses impedance technologies. The analyzer provides 18 parameters including 3-part differential at a maximum rate of 80 samples per hour. To evaluate the performance of the LABGEO(HC10). We evaluated precision, linearity, carryover, and relationship for complete blood cell count parameters between the LABGEO(HC10) and the LH780 (Beckman Coulter Inc) in a university hospital in Korea according to the Clinical and Laboratory Standards Institute guidelines. Sample stability and differences due to the anticoagulant used (K₂EDTA versus K₃EDTA) were also evaluated. The LABGEO(HC10) showed linearity over a wide range and minimal carryover (<1%) for white blood cell, hemoglobin, red blood cell, and platelet parameters. Correlation between the LABGEO(HC10) and the LH780 was good for all complete blood cell count parameters (R > 0.92) except for mean corpuscular hemoglobin concentration. The bias estimated was acceptable for all parameters investigated except for monocyte count. Most parameters were stable until 24 hours both at room temperature and at 4°C. The difference by anticoagulant type was statistically insignificant for all parameters except for a few red cell parameters. The accurate results achievable and simplicity of operation make the unit recommendable for small to medium-sized laboratories.

Molecules in Laboratory and in Interstellar Space?

NASA Astrophysics Data System (ADS)

Thimmakondu, Venkatesan S.

2016-06-01

In this talk, the quantum chemistry of astronomically relevant molecules will be outlined with an emphasis on the structures and energetics of C_7H_2 isomers, which are yet to be identified in space. Although more than 100's of isomers are possible for C_7H_2, to date only 6 isomers had been identified in the laboratory. The equilibrium geometries of heptatriynylidene (1), cyclohepta-1,2,3,4-tetraen-6-yne (2), and heptahexaenylidene (3), which we had investigated theoretically will be discussed briefly. While 1 and 3 are observed in the laboratory, 2 is a hypothetical molecule. The theoretical data may be useful for the laboratory detection of 2 and astronomical detection of 2 and 3. THIS WORK IS SUPPORTED BY A RESEARCH GRANT (YSS/2015/00099) FROM SERB, DST, GOVERNMENT OF INDIA. Apponi, A. P.; McCarthy, M. C.; Gottlieb, C. A.; Thaddeus, P. Laboratory Detection of Four New Cumulene Carbenes: H_2C_7, H_2C_8, H_2C_9, and D_2C10, Astrophys. J. 2000, 530, 357-361 Ball, C. D; McCarthy, M. C.; Thaddeus, P. Cavity Ringdown Spectroscopy of the Linear Carbon Chains HC_7H, HC_9H, HC11H, and HC13H. J. Chem. Phys. 2000, 112, 10149-10155 Dua, S.; Blanksby, S. J.; Bowie, J. H. Formation of Neutral C_7H_2 Isomers from Four Isomeric C_7H_2 Radical Anion Precursors in the Gas Phase. J. Phys. Chem. A, 2000, 104, 77-85. Thimmakondu, V. S. The equilibrium geometries of heptatriynylidene, cyclohepta-1,2,3,4-tetraen-6-yne, and heptahexaenylidene, Comput. Theoret. Chem. 2016, 1079, 1-10

Fragment C Domain of Tetanus Toxin Mitigates Methamphetamine Neurotoxicity and Its Motor Consequences in Mice

PubMed Central

Mendieta, Liliana; Granado, Noelia; Aguilera, José; Tizabi, Yousef

2016-01-01

Background: The C-terminal domain of the heavy chain of tetanus toxin (Hc-TeTx) is a nontoxic peptide with demonstrated in vitro and in vivo neuroprotective effects against striatal dopaminergic damage induced by 1-methyl-4-phenylpyridinium and 6-hydoxydopamine, suggesting its possible therapeutic potential in Parkinson’s disease. Methamphetamine, a widely abused psychostimulant, has selective dopaminergic neurotoxicity in rodents, monkeys, and humans. This study was undertaken to determine whether Hc-TeTx might also protect against methamphetamine-induced dopaminergic neurotoxicity and the consequent motor impairment. Methods: For this purpose, we treated mice with a toxic regimen of methamphetamine (4mg/kg, 3 consecutive i.p. injections, 3 hours apart) followed by 3 injections of 40 ug/kg of Hc-TeTx into grastrocnemius muscle at 1, 24, and 48 hours post methamphetamine treatment. Results: We found that Hc-TeTx significantly reduced the loss of dopaminergic markers tyrosine hydroxylase and dopamine transporter and the increases in silver staining (a well stablished degeneration marker) induced by methamphetamine in the striatum. Moreover, Hc-TeTx prevented the increase of neuronal nitric oxide synthase but did not affect microglia activation induced by methamphetamine. Stereological neuronal count in the substantia nigra indicated loss of tyrosine hydroxylase-positive neurons after methamphetamine that was partially prevented by Hc-TeTx. Importantly, impairment in motor behaviors post methamphetamine treatment were significantly reduced by Hc-TeTx. Conclusions: Here we demonstrate that Hc-TeTx can provide significant protection against acute methamphetamine-induced neurotoxicity and motor impairment, suggesting its therapeutic potential in methamphetamine abusers. PMID:26945022

Hydrogen sulfide-induced itch requires activation of Cav3.2 T-type calcium channel in mice

PubMed Central

Wang, Xue-Long; Tian, Bin; Huang, Ya; Peng, Xiao-Yan; Chen, Li-Hua; Li, Jun-Cheng; Liu, Tong

2015-01-01

The contributions of gasotransmitters to itch sensation are largely unknown. In this study, we aimed to investigate the roles of hydrogen sulfide (H2S), a ubiquitous gasotransmitter, in itch signaling. We found that intradermal injection of H2S donors NaHS or Na2S, but not GYY4137 (a slow-releasing H2S donor), dose-dependently induced scratching behavior in a μ-opioid receptor-dependent and histamine-independent manner in mice. Interestingly, NaHS induced itch via unique mechanisms that involved capsaicin-insensitive A-fibers, but not TRPV1-expressing C-fibers that are traditionally considered for mediating itch, revealed by depletion of TRPV1-expressing C-fibers by systemic resiniferatoxin treatment. Moreover, local application of capsaizapine (TRPV1 blocker) or HC-030031 (TRPA1 blocker) had no effects on NaHS-evoked scratching. Strikingly, pharmacological blockade and silencing of Cav3.2 T-type calcium channel by mibefradil, ascorbic acid, zinc chloride or Cav3.2 siRNA dramatically decreased NaHS-evoked scratching. NaHS induced robust alloknesis (touch-evoked itch), which was inhibited by T-type calcium channels blocker mibefradil. Compound 48/80-induced itch was enhanced by an endogenous precursor of H2S (L-cysteine) but attenuated by inhibitors of H2S-producing enzymes cystathionine γ-lyase and cystathionine β-synthase. These results indicated that H2S, as a novel nonhistaminergic itch mediator, may activates Cav3.2 T-type calcium channel, probably located at A-fibers, to induce scratching and alloknesis in mice. PMID:26602811

BK virus (BKV) quantification in urine samples of bone marrow transplanted patients is helpful for diagnosis of hemorrhagic cystitis, although wide individual variations exist.

PubMed

Priftakis, Peter; Bogdanovic, Gordana; Kokhaei, Parviz; Mellstedt, Håkan; Dalianis, Tina

2003-01-01

Hemorrhagic cystitis (HC) in allogeneic bone marrow transplanted (BMT) patients is associated with BK virus (BKV) reactivation manifested as BK viruria. However, since 77-90% of all adult BMT patients excrete BKV, viral reactivation alone cannot be responsible for HC. Recently, a significant overrepresentation of C-->G mutations in the Sp1 binding site in the non-coding control region (NCCR) of BKV was shown to be present in HC patients and absent in non-HC patients. We aimed to investigate if this mutation resulted in excessive BKV excretion in HC patients. A Real-Time PCR was developed and used to quantify BKV in urine samples from 21 patients with HC, with and without the mutations, as well as from patients without HC. Quantification of BKV was successful in 18 of 21 urine patients (six with and six without C-->G mutations) and six patients without HC. A mean of 3.0 x 10(6) BKV copies/microl was detected in urine samples of HC patients with C-->G mutations, compared to a mean of 1.5 x 10(6) BKV copies/microl in HC patients without C-->G mutations and a mean of 1.0 x 10(6) BKV copies/microl in patients without HC. The obtained differences were however not statistically significant, due to one individual non-HC patient with an extremely high BKV copy number. Nevertheless, while 50% of the samples in the HC groups expressed 1 x 10(6) copies/microl or more, only one of the samples in the non-HC group contained a virus quantity higher than 5 x 10(5) copies. Although we could not confirm that the C-->G mutations in the Sp1 site of BKV were responsible for an increased viral load in patients with HC, our data suggest that levels of BKV above 10(4) copies/microl may indicate a risk for HC.

Molecular analysis of transmission of hepatitis C virus in a nurse who acquired acute hepatitis C after caring for a viremic patient with epistaxis.

PubMed

Toda, Takayuki; Mitsui, Takehiro; Tsukamoto, Yukie; Ebara, Takeshi; Hirose, Akinori; Masuko, Kazuo; Nagashima, Shigeo; Takahashi, Masaharu; Okamoto, Hiroaki

2009-08-01

A 23-year-old nurse (HC-IP) developed acute hepatitis C. Intrafamilial transmission of hepatitis C virus (HCV) was suspected initially because her parents were carriers of HCV of the same genotype (1b) as that of Patient HC-IP. However, the HCV isolate from Patient HC-IP and those from her parents shared identities of only 92.4-92.7% in the 1,087-nucleotide (nt) sequence within the NS5B region. It was then suspected that she contracted HCV infection during medical practice. Sixteen patients with antibodies to HCV (anti-HCV) were hospitalized 1-3 months before she became positive for anti-HCV. Upon analysis of stored serum samples, 14 of the 16 patients were found to be positive for HCV RNA, and 9 of the 14 viremic patients had genotype 1b HCV. Although the shared identities between the HCV isolate from Patient HC-IP and those from eight of the nine patients were merely 90.6-93.9% within the 1,087-nt NS5B sequence, the HCV isolate from the remaining one patient (HC-P12) was 99.7% identical to that from Patient HC-IP. Upon analysis of the E1 and E2 junctional region including hypervariable region 1 (283 nt), there was a close relationship (99.3-100%) between clones obtained from Patients HC-IP and HC-P12. Although the nurse HC-IP had a finger injury, she took care of Patient HC-P12, a 70-year-old man with HCV-related cirrhosis and recurrent epistaxis, occasionally without wearing protective gloves. This study indicates the occurrence of HCV transmission by exposure of nonintact skin to blood in health care settings. 2009 Wiley-Liss, Inc.

A cosmid and cDNA fine physical map of a human chromosome 13q14 region frequently lost in B-cell chronic lymphocytic leukemia and identification of a new putative tumor suppressor gene, Leu5.

PubMed

Kapanadze, B; Kashuba, V; Baranova, A; Rasool, O; van Everdink, W; Liu, Y; Syomov, A; Corcoran, M; Poltaraus, A; Brodyansky, V; Syomova, N; Kazakov, A; Ibbotson, R; van den Berg, A; Gizatullin, R; Fedorova, L; Sulimova, G; Zelenin, A; Deaven, L; Lehrach, H; Grander, D; Buys, C; Oscier, D; Zabarovsky, E R; Einhorn, S; Yankovsky, N

1998-04-17

B-cell chronic lymphocytic leukemia (B-CLL) is a human hematological neoplastic disease often associated with the loss of a chromosome 13 region between RB1 gene and locus D13S25. A new tumor suppressor gene (TSG) may be located in the region. A cosmid contig has been constructed between the loci D13S1168 (WI9598) and D13S25 (H2-42), which corresponds to the minimal region shared by B-CLL associated deletions. The contig includes more than 200 LANL and ICRF cosmid clones covering 620 kb. Three cDNAs likely corresponding to three different genes have been found in the minimally deleted region, sequenced and mapped against the contigged cosmids. cDNA clone 10k4 as well as a chimeric clone 13g3, codes for a zinc-finger domain of the RING type and shares homology to some known genes involved in tumorigenesis (RET finger protein, BRCA1) and embryogenesis (MID1). We have termed the gene corresponding to 10k4/13g3 clones LEU5. This is the first gene with homology to known TSGs which has been found in the region of B-CLL rearrangements.

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

Weickert, F.; Civale, L.; Maiorov, B.

Here, we present magnetization measurements on Sr4Ru3O10 as a function of temperature and magnetic field applied perpendicular to the magnetic easy c-axis inside the ferromagnetic phase. Peculiar metamagnetism evolves in Sr4Ru3O10 below the ferromagnetic transition TC as a double step in the magnetization at two critical fields Hc1 and Hc2. We map the H-T phase diagram with special focus on the temperature range 50 K ≤T≤TC. We find that the critical field Hc1(T) connects the field and temperature axes of the phase diagram, whereas the Hc2 boundary starts at 2.8 T for the lowest temperatures and ends in a criticalmore » endpoint at (1 T; 80 K). We also conclude from the temperature dependence of the ratio Hc1Hc2(T) that the double metamagnetic transition is an intrinsic effect of the material and it is not caused by sample stacking faults such as twinning or partial in-plane rotation between layers.« less

[A comparative study of three types of IUD].

PubMed

Lai, K R; Chen, Q B

1991-11-01

In Zhejiang Province, China, there are 2.7 million IUD users. 90% of them use stainless steel single ring. In order to evaluate the effectiveness of the IUDs, the Provincial Family Planning Commission organized a prospective comparative study on 3 kinds of IUDs: the single ring made in Wuxi, the metal ring with plastic core made in Beijing, and the copper TCU 220c made in Tianjin. Between October 1985 and March 1986 1199 healthy women aged 20-39 who had 2 or fewer normal deliveries and without previous history of ectopic pregnancy were screened and recruited to the study. They were randomly assigned to be inserted with the IUDs. 400 women had single ring, 402 women had metal with plastic core, and 397 had TCu 220c. 8 postinsertion follow-up visits were conducted up to 3 years, and menstruations were recorded every month. During the study, 4 cases were lost to follow-up. In the single-ring group, the cumulative continuation rates at 12, 24, and 36 months were 73.4, 66.7, and 65.7% respectively. For the metal-plastic ring group, it was 80.9, 72.3, and 69.3% and for the TCu 220c group, it was 94.5, 88.4, and 83.1%, respectively. The expulsion rates among the 3 kinds of IUDs were statistically significant at 12, 24, and 36 months. The highest expulsion rates were the single ring and TCu 220c were the lowest. The pregnancy rates were highest among metal-plastic ring users and lowest among TCu 220c users. The differences were not statistically significant between single ring and metal-plastic ring users. Discontinuation due to excessive menstrual bleeding were similar among the 3 methods probably due to treatment of the users who experienced excessive bleeding. Younger women and women who experienced fewer pregnancies were found to have higher expulsion and pregnancy rates. But the occurrence of side effects such as prolonged menstrual periods, spotting, and back pain were highest among TCu 220c users. It was recommended that the more effective TCu 220c should be promoted to replace the single ring. Since different sizes of TCu IUDs have been developed, it would be possible to reduce excessive menstrual bleeding and its side effects.

Selective Complexation and Reactivity of Metallic Nitride and OxoMetallic Fullerenes with Lewis Acids and Use as an Effective Purification Method

PubMed Central

Stevenson, Steven; Mackey, Mary A.; Pickens, Jane E.; Stuart, Melissa A.; Confait, Bridget S.; Phillips, J. Paige

2009-01-01

Metallic nitride fullerenes (MNFs) and oxometallic fullerenes (OMFs) react quickly with an array of Lewis acids. Empty-cage fullerenes are largely unreactive under conditions used in this study. The reactivity order is Sc4O2@Ih-C80 > Sc3N@C78 > Sc3N@C68 > Sc3N@D5h-C80 > Sc3N@Ih-C80. Manipulations of Lewis acids, molar ratios and kinetic differences within the family of OMF and MNF metallofullerenes are demonstrated in a selective precipitation scheme, which can be used either alone for purifying Sc3N@Ih-C80 or combined with a final HPLC pass for Sc4O2@Ih-C80, Sc3N@D5h-C80, Sc3N@C68, or Sc3N@C78. The purification process is scalable. Analysis of experimental rate constants versus electrochemical band gap explains the order of reactivity among the OMF and MNFs. PMID:19911812

The molecular core in G34.3 + 0.2 - Millimeter interferometric observations of HCO(+), H(C-13)N, H(C-15)N, and SO

NASA Technical Reports Server (NTRS)

Carral, Patricia; Welch, William J.

1992-01-01

This study presents high-resolution observations of the molecular core in the star-forming region G34.3 + 0.2. Maps at 6-arcsec resolution of emission and absorption of the J = 1 - 0 transitions of HCO(+), H (C-13)N, H(C-15)N, and of the 2(2) - 1(1) transition of SO were obtained in addition to a map of the 3.4-mm continuum emission from the compact H II component. The HCL(+) emission toward G34.3 + 0.2 traces a warm molecular core about 0.9 pc in size. Emission from H (C-13)N is detected over about 0.3 pc. The cometary H II region lies near the edge of the molecular core. The blueshift of the radio recombination lines with respect to the molecular emission suggests that gas from the H II region is accelerated in a champagne flow caused by a steep gradient in the ambient gas density.

Changes in fatty acid metabolism induced by varied micro-supplementation with zinc in snails Helix pomatia (Gastropoda Pulmonata).

PubMed

Kowalczyk-Pecka, Danuta; Pecka, Stanisław; Kowalczuk-Vasilev, Edyta

2017-04-01

We analyzed the changes in the profile of fatty acids (FA) in the foot tissues and hepatopancreas (HP) of snails Helix pomatia exposed to five microdoses of zinc (0.1, 0.25, 0.5, 0.75, or 1mg/l) administered in the form of a pure salt solution and in the form of EDTA and lysine chelates. Selection from a pool of 56 fatty acids analyzed in snail tissues yielded a set of 12 biomarker acids undergoing significant changes in contact with toxic substances. The selection criteria included the greatest percentage among the FA profile and their significant role in physiological processes. The proposed palette of acids of the biomarker FAs comprised C16:0; C18:0; C23:0; C18:1 n-9; C20:1 n-9; C18:2 n-6; C18:3 n-3; C20:2; C20:4 n-6; C20:5 n-3; C22:4 n-6; and C22:5 n-3, and saturated fatty acids (SFAs), monounsaturated fatty acids (MUFAs), and polyunsaturated fatty acids (PUFAs), determined separately in the foot tissues and hepatopancreas. The significant (p=0.01) influence of the dose as well as the source of the zinc on its' concentration in the tissues and on changes in the fatty acid profiles. Among the three zinc forms administered to the snails, the highest bioaccumulation of zinc in both tissues was noted in the group receiving the Zn-EDTA chelate. The content of PUFAs increased as the supplementation with zinc increased up to 0.75mg/l, but at 1mg/l, the share of these FAs began to decrease. This trend was observed in both analyzed tissue types - foot and hepatopancreas. The dose of 1mg Zn/l might be considered as a threshold dose above which the saturation of FAs increases. The results proved that determination of FA profile in snails can be used in ecotoxicological research as a reliable test of the effect of trace doses of stressors. The micro-supplementation of the mollusks diet with zinc is an example of a non-routine approach to issues connected with both diet and toxicology. Copyright © 2017 Elsevier Inc. All rights reserved.

Large-scale complementary macroelectronics using hybrid integration of carbon nanotubes and IGZO thin-film transistors.

PubMed

Chen, Haitian; Cao, Yu; Zhang, Jialu; Zhou, Chongwu

2014-06-13

Carbon nanotubes and metal oxide semiconductors have emerged as important materials for p-type and n-type thin-film transistors, respectively; however, realizing sophisticated macroelectronics operating in complementary mode has been challenging due to the difficulty in making n-type carbon nanotube transistors and p-type metal oxide transistors. Here we report a hybrid integration of p-type carbon nanotube and n-type indium-gallium-zinc-oxide thin-film transistors to achieve large-scale (>1,000 transistors for 501-stage ring oscillators) complementary macroelectronic circuits on both rigid and flexible substrates. This approach of hybrid integration allows us to combine the strength of p-type carbon nanotube and n-type indium-gallium-zinc-oxide thin-film transistors, and offers high device yield and low device variation. Based on this approach, we report the successful demonstration of various logic gates (inverter, NAND and NOR gates), ring oscillators (from 51 stages to 501 stages) and dynamic logic circuits (dynamic inverter, NAND and NOR gates).

Comparison of several satellite-derived databases of surface solar radiation against ground measurement in Morocco

NASA Astrophysics Data System (ADS)

Marchand, Mathilde; Ghennioui, Abdellatif; Wey, Etienne; Wald, Lucien

2018-04-01

HelioClim-3v4 (HC3v4), HelioClim-3v5 (HC3v5) and the radiation service version 2 of the Copernicus Atmosphere Monitoring Service (CAMS-Rad) are databases that contain hourly values of solar radiation at ground level. These estimated hourly irradiations are compared to coincident measurements made at five stations in Morocco. The correlation coefficients between measurements and estimates are similar for the three databases and around 0.97-0.98 for global irradiation. For the direct irradiation, the correlation coefficients are around 0.70-0.79 for HC3v4, 0.79-0.84 for HC3v5 and 0.78-0.87 for CAMS-Rad. For global irradiation, the bias relative to the average of the measurements is small and ranges between -6 and -1 % for HC3v4, -4 and 0 % for HC3v5, and -4 and 7 % for CAMS-Rad; HC3v4 and HC3v5 exhibit a tendency to slightly underestimate the global irradiation. The root mean square error (RMSE) ranges between 53 (12 %) and 72 Wh m-2 (13 %) for HC3v4, 55 (12 %) and 71 Wh m-2 (13 %) for HC3v5, and 59 (11 %) and 97 Wh m-2 (21 %) for CAMS-Rad. For the direct irradiation, the relative bias ranges between -16 and 21 % for HC3v4, -7 and 22 % for HC3v5, and -18 and 7 % for CAMS-Rad. The RMSE ranges between 170 (28 %) and 210 Wh m-2 (33 %) for HC3v4, 153 (25 %) and 209 Wh m-2 (40 %) for HC3v5, and 159 (26 %) and 244 Wh m-2 (39 %) for CAMS-Rad. HC3v5 captures the temporal and spatial variability of the irradiation field well. The performance is poorer for HC3v4 and CAMS-Rad which exhibit more variability from site to site. As a whole, the three databases are reliable sources on solar radiation in Morocco.

Potential ecological risk assessment and predicting zinc accumulation in soils.

PubMed

Baran, Agnieszka; Wieczorek, Jerzy; Mazurek, Ryszard; Urbański, Krzysztof; Klimkowicz-Pawlas, Agnieszka

2018-02-01

The aims of this study were to investigate zinc content in the studied soils; evaluate the efficiency of geostatistics in presenting spatial variability of zinc in the soils; assess bioavailable forms of zinc in the soils and to assess soil-zinc binding ability; and to estimate the potential ecological risk of zinc in soils. The study was conducted in southern Poland, in the Malopolska Province. This area is characterized by a great diversity of geological structures and types of land use and intensity of industrial development. The zinc content was affected by soil factors, and the type of land use (arable lands, grasslands, forests, wastelands). A total of 320 soil samples were characterized in terms of physicochemical properties (texture, pH, organic C content, total and available Zn content). Based on the obtained data, assessment of the ecological risk of zinc was conducted using two methods: potential ecological risk index and hazard quotient. Total Zn content in the soils ranged from 8.27 to 7221 mg kg -1 d.m. Based on the surface semivariograms, the highest variability of zinc in the soils was observed from northwest to southeast. The point sources of Zn contamination were located in the northwestern part of the area, near the mining-metallurgical activity involving processing of zinc and lead ores. These findings were confirmed by the arrangement of semivariogram surfaces and bivariate Moran's correlation coefficients. The content of bioavailable forms of zinc was between 0.05 and 46.19 mg kg -1 d.m. (0.01 mol dm -3 CaCl 2 ), and between 0.03 and 71.54 mg kg -1 d.m. (1 mol dm -3 NH 4 NO 3 ). Forest soils had the highest zinc solubility, followed by arable land, grassland and wasteland. PCA showed that organic C was the key factor to control bioavailability of zinc in the soils. The extreme, very high and medium zinc accumulation was found in 69% of studied soils. There is no ecological risk of zinc to living organisms in the study area, and in 90% of the soils there were no potentially negative effects of zinc to ecological receptors.

Identification of the acclimation genes in transcriptomic responses to heat stress of White Pekin duck.

PubMed

Kim, Jun-Mo; Lim, Kyu-Sang; Byun, Mijeong; Lee, Kyung-Tai; Yang, Young-Rok; Park, Mina; Lim, Dajeong; Chai, Han-Ha; Bang, Han-Tae; Hwangbo, Jong; Choi, Yang-Ho; Cho, Yong-Min; Park, Jong-Eun

2017-11-01

White Pekin duck is an important meat resource in the livestock industries. However, the temperature increase due to global warming has become a serious environmental factor in duck production, because of hyperthermia. Therefore, identifying the gene regulations and understanding the molecular mechanism for adaptation to the warmer environment will provide insightful information on the acclimation system of ducks. This study examined transcriptomic responses to heat stress treatments (3 and 6 h at 35 °C) and control (C, 25 °C) using RNA-sequencing analysis of genes from the breast muscle tissue. Based on three distinct differentially expressed gene (DEG) sets (3H/C, 6H/C, and 6H/3H), the expression patterns of significant DEGs (absolute log2 > 1.0 and false discovery rate < 0.05) were clustered into three responsive gene groups divided into upregulated and downregulated genes. Next, we analyzed the clusters that showed relatively higher expression levels in 3H/C and lower levels in 6H/C with much lower or opposite levels in 6H/3H; we referred to these clusters as the adaptable responsive gene group. These genes were significantly enriched in the ErbB signaling pathway, neuroactive ligand-receptor interaction and type II diabetes mellitus in the KEGG pathways (P < 0.01). From the functional enrichment analysis and significantly regulated genes observed in the enriched pathways, we think that the adaptable responsive genes are responsible for the acclimation mechanism of ducks and suggest that the regulation of phosphoinositide 3-kinase genes including PIK3R6, PIK3R5, and PIK3C2B has an important relationship with the mechanisms of adaptation to heat stress in ducks.

Microbial protein synthesis, ruminal digestion, microbial populations, and nitrogen balance in sheep fed diets varying in forage-to-concentrate ratio and type of forage.

PubMed

Ramos, S; Tejido, M L; Martínez, M E; Ranilla, M J; Carro, M D

2009-09-01

Six ruminally and duodenally cannulated sheep were used in a partially replicated 4 x 4 Latin square to evaluate the effects of 4 diets on microbial synthesis, microbial populations, and ruminal digestion. The experimental diets had forage to concentrate ratios (F:C; DM basis) of 70:30 (HF) or 30:70 (HC) with alfalfa hay (A) or grass hay (G) as forage and were designated as HFA, HCA, HFG, and HCG. The concentrate was based on barley, gluten feed, wheat middlings, soybean meal, palmkern meal, wheat, corn, and mineral-vitamin premix in the proportions of 22, 20, 20, 13, 12, 5, 5, and 3%, respectively (as-is basis). Sheep were fed the diets at a daily rate of 56 g/kg of BW(0.75) to minimize feed selection. High-concentrate diets resulted in greater (P < 0.001) total tract apparent OM digestibility compared with HF diets, but no differences were detected in NDF digestibility. Ruminal digestibility of OM, NDF, and ADF was decreased by increasing the proportion of concentrate, but no differences between forages were detected. Compared with sheep fed HF diets, sheep receiving HC diets had less ruminal pH values and acetate proportions, but greater butyrate proportions. No differences among diets were detected in numbers of cellulolytic bacteria, but protozoa numbers were less (P = 0.004) and total bacteria numbers tended (P = 0.08) to be less for HC diets. Carboxymethylcellulase, xylanase, and amylase activities were greater for HC compared with HF diets, with A diets showing greater (P = 0.008) carboxymethylcellulase activities than G diets. Retained N ranged from 28.7 to 37.9% of N intake and was not affected by F:C (P = 0.62) or the type of forage (P = 0.31). Microbial N synthesis and its efficiency was greater (P < 0.001) for HC diets compared with HF diets. The results indicate that concentrates with low cereal content can be included in the diet of sheep up to 70% of the diet without detrimental effects on ruminal activity, microbial synthesis efficiency, and N losses.

Constructing Highly Uniform Onion-Ring-like Graphitic Carbon Nitride for Efficient Visible-Light-Driven Photocatalytic Hydrogen Evolution.

PubMed

Cui, Lifeng; Song, Jialing; McGuire, Allister F; Kang, Shifei; Fang, Xueyou; Wang, Junjie; Yin, Chaochuang; Li, Xi; Wang, Yangang; Cui, Bianxiao

2018-06-13

The introduction of microstructure to the metal-free graphitic carbon nitride (g-C 3 N 4 ) photocatalyst holds promise in enhancing its catalytic performance. However, producing such microstructured g-C 3 N 4 remains technically challenging due to a complicated synthetic process and high cost. In this study, we develop a facile and in-air chemical vapor deposition (CVD) method that produces onion-ring-like g-C 3 N 4 microstructures in a simple, reliable, and economical manner. This method involves the use of randomly packed 350 nm SiO 2 microspheres as a hard template and melamine as a CVD precursor for the deposition of a thin layer of g-C 3 N 4 in the narrow space between the SiO 2 microspheres. After dissolution of the microsphere template, the resultant g-C 3 N 4 exhibits uniquely uniform onion-ring-like microstructures. Unlike previously reported g-C 3 N 4 powder morphologies that show various degrees of agglomeration and irregularity, the onion-ring-like g-C 3 N 4 is highly dispersed and uniform. The calculated band gap for onion-ring-like g-C 3 N 4 is 2.58 eV, which is significantly narrower than that of bulk g-C 3 N 4 at 2.70 eV. Experimental characterization and testing suggest that, in comparison with bulk g-C 3 N 4 , onion-ring-like g-C 3 N 4 facilitates charge separation, extends the lifetime of photoinduced carriers, exhibits 5-fold higher photocatalytic hydrogen evolution, and shows great potential for photocatalytic applications.

A Study of Underwater Sound Ray Tracing Methodology

DTIC Science & Technology

1990-09-01

SRER ,LB,SV,SVU2,SVU,SU2,SU4,GI,G PIE = 3.14159265359D0 77 lEST = 0 MI = M C DISTRIBUTE THE K SOURCES EQUALLY AROUND THE CIRCLE COUNTER C CLOCKWISE...C(I) - TI-R(I TIMER(I = TIMCO) - T(5) HER(IW HC(I - Hl ZER(IW ZC(I - ZI SR = DSQRT(HI**2 + WA - Zl)**2) SRER = DSQRT(HC(I)**2 + (A2 - Zl)**2) - SR 50

A search for cyanopolyynes in L1157-B1

NASA Astrophysics Data System (ADS)

Mendoza, Edgar; Lefloch, B.; Ceccarelli, C.; Kahane, C.; Jaber, A. A.; Podio, L.; Benedettini, M.; Codella, C.; Viti, S.; Jimenez-Serra, I.; Lepine, J. R. D.; Boechat-Roberty, H. M.; Bachiller, R.

2018-04-01

We present here a systematic search for cyanopolyynes in the shock region L1157-B1 and its associated protostar L1157-mm in the framework of the Large Program`Astrochemical Surveys At IRAM' (ASAI), dedicated to chemical surveys of solar-type star-forming regions with the IRAM 30-m telescope. Observations of the millimeter windows between 72 and 272 GHz permitted the detection of HC3N and its 13C isotopologues, and HC5N (for the first time in a protostellar shock region). In the shock, the analysis of the line profiles shows that the emission arises from the outflow cavities associated with L1157-B1 and L1157-B2. Molecular abundances and excitation conditions were obtained from the analysis of the Spectral Line Energy Distributions under the assumption of Local Thermodynamical Equilibrium or using a radiative transfer code in the Large Velocity Gradient approximation. Towards L1157 mm, the HC3N emission arises from the cold envelope (T_rot=10K) and a higher-excitation region (Trot = 31K) of smaller extent around the protostar. We did not find any evidence of 13C or D fractionation enrichment towards L1157-B1. We obtain a relative abundance ratio HC3N/HC5N of 3.3 in the shocked gas. We find an increase by a factor of 30 of the HC3N abundance between the envelope of L1157-mm and the shock region itself. Altogether, these results are consistent with a scenario in which the bulk of HC3N was produced by means of gas phase reactions in the passage of the shock. This scenario is supported by the predictions of a parametric shock code coupled with the chemical model UCL_CHEM.

Molecular and functional characterization of two drought-induced zinc finger proteins, ZmZnF1 and ZmZnF2 from maize kernels

USDA-ARS?s Scientific Manuscript database

We have isolated two cDNA clones encoding Zinc Finger proteins, designated as ZmZnF1 and ZmZnF2, from water-stressed maize kernels. Sequence analyses indicates that ZmZnF1 is homologous to the A20/AN1-type zinc finger protein and contains the zinc finger motif of Cx2–Cx10–CxCx4Cx2Hx5HxC. Whereas ZmZ...

[Concordance between a head circumference growth function and intellectual disability in relation with the cause of microcephaly].

PubMed

Coronado, R; Macaya Ruíz, A; Giraldo Arjonilla, J; Roig-Quilis, M

2015-08-01

Our aim was to investigate the correlations between patterns of head growth and intellectual disability among distinct aetiological presentations of microcephaly. 3,269 head circumference (HC) charts of patients from a tertiary neuropediatric unit were reviewed and 136 microcephalic participants selected. Using the Z-scores of registered HC measurements we defined the variables: HC Minimum, HC Drop and HC Catch-up. We classified patients according to the presence or absence of intellectual disability (IQ below 71) and according to the cause of microcephaly (idiopathic, familial, syndromic, symptomatic and mixed). Using Discriminant Analysis a C-function was defined as C=HC Minimum + HC Drop with a cut-off level of C=-4.32 Z-score. In our sample 95% of patients scoring below this level, severe microcephaly, were classified in the disabled group while the overall concordance was 66%. In the symptomatic-mixed group the concordance between HC function and outcome reached 82% in contrast to only 54% in the idiopathic-syndromic group (P-value=0.0002). We defined a HC growth function which discriminates intellectual disability of microcephalic patients better than isolated HC measurements, especially for those with secondary and mixed aetiologies. Copyright © 2014 Asociación Española de Pediatría. Published by Elsevier España, S.L.U. All rights reserved.

The 1:1 inclusion compounds zolmitriptan-benzene and zolmitriptan-phenol.

PubMed

Swamy, G Y S K; Sridhar, B; Ravikumar, K; Krishnan, Harihara

2007-07-01

In the benzene and phenol solvates of (S)-4-{3-[2-(dimethylamino)ethyl]-1H-indol-5-ylmethyl}oxazolidin-2-one, viz. C(16)H(21)N(3)O(2) x C(6)H(6), (I), and C(16)H(21)N(3)O(2) x C(6)H(5)OH, (II), the host molecule has three linked residues, namely a planar indole ring system, an ethylamine side chain and an oxazolidinone system. It has comparable features to that of sumatriptan, although the side-chain orientations of (I) and (II) differ from those of sumatriptan. Both (I) and (II) have host-guest-type structures. The host molecule in (I) and (II) has an L-shaped form, with the oxazolidinone ring occupying the base and the remainder of the molecule forming the upright section. In (I), each benzene guest molecule is surrounded by four host molecules, and these molecules are linked by a combination of N-H...N, N-H...O and C-H...O hydrogen bonds into chains of edge-fused R(4)(4)(33) rings. In (II), two independent molecules are present in the asymmetric unit, with similar conformations. The heterocyclic components are connected through N-H...N, N-H...O and C-H...O interactions to form chains of edge-fused R(6)(4)(38) rings, from which the phenol guest molecules are pendent, linked by O-H...O hydrogen bonds. The structures are further stabilized by extensive C-H...pi interactions.

Weak hydrogen bonding and fluorous interactions in the chloride and bromide salts of 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium.

PubMed

Lu, Norman; Wei, Rong Jyun; Lin, Kwan Yu; Alagesan, Mani; Wen, Yuh Sheng; Liu, Ling Kang

2017-04-01

Neutralization of 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridine with hydrohalo acids HX (X = Cl and Br) yielded the pyridinium salts 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium chloride, C 9 H 10 F 4 NO + ·Cl - , (1), and 4-[(2,2,3,3-tetrafluoropropoxy)methyl]pyridinium bromide, C 9 H 10 F 4 NO + ·Br - , (2), both carrying a fluorous side chain at the para position of the pyridinium ring. Single-crystal X-ray diffraction techniques revealed that (1) and (2) are isomorphous. The halide anions accept four hydrogen bonds from N-H, ortho-C-H and CF 2 -H groups. Two cations and two anions form a centrosymmetric dimeric building block, utilizing complimentary N-H...X...H-Csp 3 connections. These dimers are further crosslinked, utilizing another complimentary Csp 2 -H...X...H-Csp 2 connection. The pyridinium rings are π-stacked, forming columns running parallel to the a axis that make angles of ca 44-45° with the normal to the pyridinium plane. There are also supramolecular C-H...F-C interactions, namely bifurcated C-H...F and bifurcated C-F...H interactions; additionally, one type II C-F...F-C halogen bond has been observed.

Ethyl 2-(4-meth-oxy-phen-yl)-6-oxa-3-aza-bicyclo[3.1.0]hexane-3-carboxyl-ate: crystal structure and Hirshfeld analysis.

PubMed

Zukerman-Schpector, Julio; Sugiyama, Fabricia H; Garcia, Ariel L L; Correia, Carlos Roque D; Jotani, Mukesh M; Tiekink, Edward R T

2017-07-01

The title compound, C 14 H 17 NO 4 , features an epoxide-O atom fused to a pyrrolidyl ring, the latter having an envelope conformation with the N atom being the flap. The 4-meth-oxy-phenyl group is orthogonal to [dihedral angle = 85.02 (6)°] and lies to the opposite side of the five-membered ring to the epoxide O atom, while the N-bound ethyl ester group (r.m.s. deviation of the five fitted atoms = 0.0187 Å) is twisted with respect to the ring [dihedral angle = 17.23 (9)°]. The most prominent inter-actions in the crystal are of the type methine-C-H⋯O(carbon-yl) and these lead to the formation of linear supra-molecular chains along the c axis; weak benzene-C-H⋯O(epoxide) and methine-C-H⋯O(meth-oxy) inter-actions connect these into a three-dimensional architecture. The analysis of the Hirshfeld surface confirms the presence of C-H⋯O inter-actions in the crystal, but also the dominance of H⋯H dispersion contacts.

Dichloridobis(phenanthridine-κN)zinc(II)

PubMed Central

Khoshtarkib, Zeinab; Ebadi, Amin; Alizadeh, Robabeh; Ahmadi, Roya; Amani, Vahid

2009-01-01

In the mol­ecule of the title compound, [ZnCl2(C13H9N)2], the ZnII atom is four-coordinated in a distorted tetra­hedral configuration by two N atoms from two phenanthridine ligands and by two terminal Cl atoms. The dihedral angle between the planes of the phenanthridine ring systems is 69.92 (3)°. An intra­molecular C—H⋯Cl inter­action results in the formation of a planar five-membered ring, which is oriented at a dihedral angle of 8.32 (3)° with respect to the adjacent phenanthridine ring system. In the crystal structure, π–π contacts between the phenanthridine systems [centroid–centroid distances = 3.839 (2), 3.617 (1) and 3.682 (1) Å] may stabilize the structure. Two weak C—H⋯π inter­actions are also found. PMID:21582680

Fragment C Domain of Tetanus Toxin Mitigates Methamphetamine Neurotoxicity and Its Motor Consequences in Mice.

PubMed

Mendieta, Liliana; Granado, Noelia; Aguilera, José; Tizabi, Yousef; Moratalla, Rosario

2016-08-01

The C-terminal domain of the heavy chain of tetanus toxin (Hc-TeTx) is a nontoxic peptide with demonstrated in vitro and in vivo neuroprotective effects against striatal dopaminergic damage induced by 1-methyl-4-phenylpyridinium and 6-hydoxydopamine, suggesting its possible therapeutic potential in Parkinson's disease. Methamphetamine, a widely abused psychostimulant, has selective dopaminergic neurotoxicity in rodents, monkeys, and humans. This study was undertaken to determine whether Hc-TeTx might also protect against methamphetamine-induced dopaminergic neurotoxicity and the consequent motor impairment. For this purpose, we treated mice with a toxic regimen of methamphetamine (4mg/kg, 3 consecutive i.p. injections, 3 hours apart) followed by 3 injections of 40 ug/kg of Hc-TeTx into grastrocnemius muscle at 1, 24, and 48 hours post methamphetamine treatment. We found that Hc-TeTx significantly reduced the loss of dopaminergic markers tyrosine hydroxylase and dopamine transporter and the increases in silver staining (a well stablished degeneration marker) induced by methamphetamine in the striatum. Moreover, Hc-TeTx prevented the increase of neuronal nitric oxide synthase but did not affect microglia activation induced by methamphetamine. Stereological neuronal count in the substantia nigra indicated loss of tyrosine hydroxylase-positive neurons after methamphetamine that was partially prevented by Hc-TeTx. Importantly, impairment in motor behaviors post methamphetamine treatment were significantly reduced by Hc-TeTx. Here we demonstrate that Hc-TeTx can provide significant protection against acute methamphetamine-induced neurotoxicity and motor impairment, suggesting its therapeutic potential in methamphetamine abusers. © The Author 2016. Published by Oxford University Press on behalf of CINP.

Organic metamorphism in the California petroleum basins; Chapter A, Rock-Eval and vitrinite reflectance

USGS Publications Warehouse

Price, Leigh C.; Pawlewicz, Mark J.; Daws, Ted A.

1999-01-01

The results of ROCK-EVAL and vitrinite reflectance analyses of a large sample base from more than 70 wells located in three oil-rich California petroleum basins are reported. The cores from these wells have a wide range of present-day burial temperatures (40 ? to 220 ? C). The rocks in these basins were deposited under highly variable conditions, sometimes resulting in substantially different organic matter (OM) types in rocks tens of meters vertically apart from each other in one well. The kinetic response of these different OM types to equivalent wellknown burial histories is a pivotal point of this study. In the Los Angeles and Ventura Basins, rock organic-richness significantly increased with depth, as did kerogen hydrogen content, and the percentage of fine-grained versus coarsegrained rocks. The shales in these basins are perceived as containing primarily hydrogen-rich amorphous OM. In actuality, the shallowest 2,000 to 3,000 m of rocks in the basins, and at least the upper 6,000 m of rocks in parts of the Los Angeles Basin central syncline, are dominated by type III/IV OM. In the Los Angeles Basin, mainstage hydrocarbon (HC) generation commences in the type III/IV OM at present-day burial temperatures of 85 ? to 110 ? C, most likely around 100 ? C, and is largely complete by 220 ? C. In the Southern San Joaquin Valley Basin, mainstage HC generation commences in type III/IV OM at 150 ? C and is also largely complete by 220 ? C. In the Ventura Basin, mainstage HC generation commences above 140 ? C in type III/IV OM. The apparent lower temperatures for commencement of HC generation in the Los Angeles Basin are attributed to the fact that parts of the basin were cooled from maximal burial temperatures by increased meteoric water flows during the last glaciations. All aspects of organic metamorphism, including mainstage HC generation, are strongly suppressed in rocks with hydrogenrich OM in these basins. For example, ROCK-EVAL data suggest that mainstage HC generation has not commenced in rocks with hydrogen-rich OM at present-day temperatures of 198?C. This observation is attributed to much stronger bonds in hydrogen- rich OM compared to types III and IV OM and, therefore, significantly higher burial temperatures are required to break these bonds. This difference in OM kinetics has profound ramifications for petroleum-geochemical exploration models. Organic-matter characteristics inherited from original depositional conditions were overlaid on, and at times confused interpretation of, characteristics from organic metamorphism in all study areas. In all the basins examined in this study, immature fine-grained rocks occasionally had high to very high carbon-normalized concentrations of pre-generation indigenous bitumen. This unusual characteristic may be due to unique depositional conditions in these basins.

Characteristic Study of Some Different Kinds of Coal Particles Combustion with Online TG-MS-FTIR

NASA Astrophysics Data System (ADS)

Pan, Guanfu

2018-01-01

Four kinds of pulverized coal samples from China and Indonesia were studied by thermogravimetry coupled with mass spectrometry and fourier transform infrared spectroscopy (TG-MS-FTIR). The thermal behaviors and gaseous emissions of these coals were analyzed in this work. The results indicate that the relative lower values of H/C ratios, which normally represent the degree of aromatization and ring condensation in coal samples, could lead to the relative more intense thermal reaction. The time-evolved profiles of some typical gas products (i.e., CO, SO2, CH4, NO, NO2, NH3 and etc.) were provided by TG-MS-FTIR, and their variations are different. For all the samples, the releases of SO2 and COS can be found at lower temperature than those of NO and CO. As the temperature increases, the possible conversion of NO2 and NH3 to NO is deduced in this work.

Oral atorvastatin therapy increases nitric oxide-dependent cutaneous vasodilation in humans by decreasing ascorbate-sensitive oxidants.

PubMed

Holowatz, Lacy A; Kenney, W Larry

2011-09-01

Elevated low-density lipoproteins (LDL) are associated with cutaneous microvascular dysfunction partially mediated by increased arginase activity, which is decreased following a systemic atorvastatin therapy. We hypothesized that increased ascorbate-sensitive oxidant stress, partially mediated through uncoupled nitric oxide synthase (NOS) induced by upregulated arginase, contributes to cutaneous microvascular dysfunction in hypercholesterolemic (HC) humans. Four microdialysis fibers were placed in the skin of nine HC (LDL = 177 ± 6 mg/dl) men and women before and after 3 mo of a systemic atorvastatin intervention and at baseline in nine normocholesterolemic (NC) (LDL = 95 ± 4 mg/dl) subjects. Sites served as control, NOS inhibited, L-ascorbate, and arginase-inhibited+L-ascorbate. Skin blood flow was measured while local skin heating (42°C) induced NO-dependent vasodilation. After the established plateau in all sites, 20 mM ≪ngname≫ was infused to quantify NO-dependent vasodilation. Data were normalized to maximum cutaneous vascular conductance (CVC) (sodium nitroprusside + 43°C). The plateau in vasodilation during local heating (HC: 78 ± 4 vs. NC: 96 ± 2% CVC(max), P < 0.01) and NO-dependent vasodilation (HC: 40 ± 4 vs. NC: 54 ± 4% CVC(max), P < 0.01) was reduced in the HC group. Acute L-ascorbate alone (91 ± 5% CVC(max), P < 0.001) or combined with arginase inhibition (96 ± 3% CVC(max), P < 0.001) augmented the plateau in vasodilation in the HC group but not the NC group (ascorbate: 96 ± 2; combo: 93 ± 4% CVC(max), both P > 0.05). After the atorvastatin intervention NO-dependent vasodilation was augmented in the HC group (HC postatorvastatin: 64 ± 4% CVC(max), P < 0.01), and there was no further effect of ascorbate alone (58 ± 4% CVC(max,) P > 0.05) or combined with arginase inhibition (67 ± 4% CVC(max,) P > 0.05). Increased ascorbate-sensitive oxidants contribute to hypercholesteromic associated cutaneous microvascular dysfunction which is partially reversed with atorvastatin therapy.

Physiological and Perceived Effects of Forearm or Head Cooling During Simulated Firefighting Activity and Rehabilitation

PubMed Central

Yeargin, Susan; McKenzie, Amy L.; Eberman, Lindsey E.; Kingsley, J. Derek; Dziedzicki, David J.; Yoder, Patrick

2016-01-01

Context: Cooling devices aim to protect firefighters by attenuating a rise in body temperature. Devices for head cooling (HC) while firefighting and forearm cooling (FC) during rehabilitation (RHB) intervals are commonly marketed, but research regarding their efficacy is limited. Objective: To investigate the physiological and perceived effects of HC and FC during firefighting drills and RHB. Design: Randomized controlled clinical trial. Setting: Firefighter training center. Patients or Other Participants: Twenty-seven male career firefighters (age = 39 ± 7 years; height = 169 ± 7 cm; weight = 95.4 ± 16.8 kg). Intervention(s): Firefighters were randomly assigned to 1 condition: HC (n = 9), in which participants completed drills wearing a cold gel pack inside their helmet; FC (n = 8), in which participants sat on a collapsible chair with water-immersion arm troughs during RHB; or control (n = 10), in which participants used no cooling devices. Firefighters completed four 15-minute drills (D1−D4) wearing full bunker gear and breathing apparatus. Participants had a 15-min RHB after D2 (RHB1) and D4 (RHB2). Main Outcome Measure(s): Change (Δ) in gastrointestinal temperature (TGI), heart rate (HR), physiological strain index, and perceived thermal sensation. Results: The TGI increased similarly in the HC and control groups, respectively (D1: 0.57°C ± 0.41°C, 0.73°C ± 0.30°C; D2: 0.92°C ± 0.28°C, 0.85°C ± 0.27°C; D3: −0.37°C ± 0.34°C, −0.01°C ± 0.72°C; D4: 0.25°C ± 0.42°C, 0.57°C ± 0.26°C; P > .05). The ΔHR, Δ physiological strain index, and Δ thermal sensation were similar between the HC and control groups during drills (P > .05). The FC group demonstrated a decreased TGI compared with the control group after RHB1 (−1.61°C ± 0.35°C versus −0.23°C ± 0.34°C; P < .001) and RHB2 (−1.40°C ± 0.38°C versus −0.38°C ± 0.24°C; P < .001). The physiological strain index score decreased in the FC group compared with the control group after RHB1 (−7.9 ± 1.3 versus −2.6 ± 1.7; P < .001) and RHB2 (−7.9 ± 1.6 versus −3.6 ± 1.1; P < .001), but no differences between groups were demonstrated for ΔHR or Δ thermal sensation (P > .05). Conclusions: The HC did not attenuate rises in physiological or perceptual variables during firefighting drills. The FC effectively reduced TGI and the physiological strain index score but not HR or thermal sensation during RHB. Clinicians and firefighters should not recommend the use of HC during firefighting but can consider using FC during RHB intervals in the field. PMID:28068165

Reduction of the ganglioside binding activity of the tetanus toxin HC fragment destroys immunogenicity: implications for development of novel tetanus vaccines.

PubMed

Qazi, Omar; Sesardic, Dorothea; Tierney, Robert; Söderbäck, Zahra; Crane, Dennis; Bolgiano, Barbara; Fairweather, Neil

2006-08-01

In this study, the immunogenicities of the nontoxic H(C) fragment of tetanus toxin and derivatives lacking ganglioside binding activity were compared with that of tetanus toxoid after subcutaneous immunization of mice. Wild-type H(C) (H(C)WT) protein and tetanus toxoid both elicited strong antibody responses against toxoid and H(C) antigens and provided complete protection against toxin challenge. Mutants of H(C) containing deletions essential for ganglioside binding elicited lower responses than H(C)WT. H(C)M115, containing two amino acid substitutions within the ganglioside binding site, provided reduced protection against tetanus toxin challenge compared with H(C)WT, consistent with lower anti-H(C) and anti-toxoid antibody titers. Circular-dichroism spectroscopy and intrinsic fluorescence spectroscopy showed minimal structural perturbation in H(C)M115. We conclude that the presence of the ganglioside binding site within H(C) may be essential for induction of a fully protective anti-tetanus response comparable to that induced by tetanus toxoid by subcutaneous injection.

Oxidative metabolism of phenanthrene and anthracene by soil pseudomonads. The ring-fission mechanism

PubMed Central

Evans, W. C.; Fernley, H. N.; Griffiths, E.

1965-01-01

1. Phenanthrene is oxidatively metabolized by soil pseudomonads through trans-3,4-dihydro-3,4-dihydroxyphenanthrene to 3,4-dihydroxyphenanthrene, which then undergoes cleavage. 2. Some properties of the ring-fission product, cis-4-(1-hydroxynaphth-2-yl)-2-oxobut-3-enoic acid, are described. The Fe2+-dependent oxygenase therefore disrupts the bond between C-4 and the angular C of the phenanthrene nucleus. 3. An enzyme of the aldolase type converts the fission product into 1-hydroxy-2-naphthaldehyde (2-formyl-1-hydroxynaphthalene). An NAD-specific dehydrogenase is also present in the cell-free extract, which oxidizes the aldehyde to 1-hydroxy-2-naphthoic acid. This is then oxidatively decarboxylated to 1,2-dihydroxynaphthalene, thus allowing continuation of metabolism via the naphthalene pathway. 4. Anthracene is similarly metabolized, through 1,2-dihydro-1,2-dihydroxyanthracene to 1,2-dihydroxyanthracene, in which ring-fission occurs to give cis-4-(2-hydroxynaphth-3-yl)-2-oxobut-3-enoic acid. The position of cleavage is again at the bond between the angular C and C-1 of the anthracene nucleus. 5. Enzymes that convert the fission product through 2-hydroxy-3-naphthaldehyde into 2-hydroxy-3-naphthoic acid were demonstrated. The further metabolism of this acid is discussed. 6. The Fe2+-dependent oxygenase responsible for cleavage of all the o-dihydroxyphenol derivatives appears to be catechol 2,3-oxygenase, and is a constitutive enzyme in the Pseudomonas strains used. PMID:14342521

Hydrothermal synthesis and structural characterization of a novel three-dimensional supramolecular framework constructed by zinc salt and pyridine-2,5-dicarboxylate

NASA Astrophysics Data System (ADS)

Wang, Xinlong; Qin, Chao; Wang, Enbo; Hu, Changwen; Xu, Lin

2004-07-01

A novel metal-organic coordination polymer, [Zn(PDB)(H 2O) 2] 4 n (H 2PDB=pyridine-2,5-dicarboxylic acid), has been hydrothermally synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. Colorless crystals crystallized in the triclinic system, space group P-1, a=7.0562(14) Å, b=7.38526(15) Å, c=18.4611(4) Å, α=90.01(3)°, β=96.98(3)°, γ=115.67(3)°, V=859.1(3) Å 3, Z=1 and R=0.0334. The structure of the compound exhibits a novel three-dimensional supramolecular network, mainly based on multipoint hydrogen bonds originated from within and outside of a large 24-membered ring. Interestingly, the three-dimensional network consists of one-dimensional parallelogrammic channels in which coordinated water molecules point into the channel wall.

Crystal structure of 5''-(4-chloro-benzyl-idene)-4'-(4-chloro-phen-yl)-1'-methyltri-spiro[acenapthylene-1,2'-pyrrolidine-3',1''-cyclo-hexane-3'',2'''-[1,3]dioxane]-2(1H),6''-dione.

PubMed

Chandralekha, Kuppan; Gavaskar, Deivasigamani; Sureshbabu, Adukamparai Rajukrishnan; Lakshmi, Srinivasakannan

2015-11-01

In the title compound, C36H29Cl2NO4, two spiro links connect the methyl-substituted pyrrolidine ring to the ace-naphthyl-ene and cyclo-hexa-none rings. The cyclo-hexa-none ring is further connected to the dioxalane ring by a third spiro junction. The five-membered ring of the ace-naphthylen-1-one ring system adopts a flattened envelope conformation, with the ketonic C atom as the flap, whereas the dioxalane and pyrrolidine rings each have a twist conformation. The cyclo-hexenone ring assumes a boat conformation. An intra-molecular C-H⋯O hydrogen-bond inter-action is present. In the crystal, mol-ecules are linked by non-classical C-H⋯O hydrogen bonds, forming chains extending parallel to the a axis.

Bacterial synthesis of N-hydroxycinnamoyl phenethylamines and tyramines.

PubMed

Sim, Geun Young; Yang, So-Mi; Kim, Bong Gyu; Ahn, Joong-Hoon

2015-10-13

Hydroxycinnamic acids (HCAs) including cinnamic acid, p-coumaric acid, caffeic acid, and ferulic acid, are C6-C3 phenolic compounds that are synthesized via the phenylpropanoid pathway. HCAs serve as precursors for the synthesis of lignins, flavonoids, anthocyanins, stilbenes and other phenolic compounds. HCAs can also be conjugated with diverse compounds including quinic acid, hydroxyl acids, and amines. Hydroxycinnamoyl (HC) amine conjugates such as N-HC tyramines and N-HC phenethylamines have been considered as potential starting materials to develop antiviral and anticancer drugs. We synthesized N-HC tyramines and N-HC phenethylamines using three different approaches in Escherichia coli. Five N-HC phenethylamines and eight N-HC tyramines were synthesized by feeding HCAs and phenethylamine or tyramine to E. coli harboring 4CL (encoding 4-coumarate CoA:ligase) and either SHT (encoding phenethylamine N-HC transferase) or THT (encoding tyramine N-HC transferase). Also, N-(p-coumaroyl) phenethylamine and N-(p-coumaroyl) tyramine were synthesized from p-coumaric acid using E. coli harboring an additional gene, PDC (encoding phenylalanine decarboxylase) or TDC (encoding tyrosine decarboxylase). Finally, we synthesized N-(p-coumaroyl) phenethylamine and N-(p-coumaroyl) tyramine from glucose by reconstructing the metabolic pathways for their synthesis in E. coli. Productivity was maximized by optimizing the cell concentration and incubation temperature. We reconstructed the metabolic pathways for synthesis of N-HC tyramines and N-HC phenethylamines by expressing several genes including 4CL, TST or SHT, PDC or TDC, and TAL (encoding tyrosine ammonia lyase) and engineering the shikimate metabolic pathway to increase endogenous tyrosine concentration in E. coli. Approximately 101.9 mg/L N-(p-coumaroyl) phenethylamine and 495.4 mg/L N-(p-coumaroyl) tyramine were synthesized from p-coumaric acid. Furthermore, 152.5 mg/L N-(p-coumaroyl) phenethylamine and 94.7 mg/L N-(p-coumaroyl) tyramine were synthesized from glucose.

Identification and preliminary characterization of a protein motif related to the zinc finger.

PubMed Central

Lovering, R; Hanson, I M; Borden, K L; Martin, S; O'Reilly, N J; Evan, G I; Rahman, D; Pappin, D J; Trowsdale, J; Freemont, P S

1993-01-01

We have identified a protein motif, related to the zinc finger, which defines a newly discovered family of proteins. The motif was found in the sequence of the human RING1 gene, which is proximal to the major histocompatibility complex region on chromosome six. We propose naming this motif the "RING finger" and it is found in 27 proteins, all of which have putative DNA binding functions. We have synthesized a peptide corresponding to the RING1 motif and examined a number of properties, including metal and DNA binding. We provide evidence to support the suggestion that the RING finger motif is the DNA binding domain of this newly defined family of proteins. Images Fig. 1 Fig. 4 PMID:7681583

The site of antiviral action of 3-nitrosobenzamide on the infectivity process of human immunodeficiency virus in human lymphocytes.

PubMed Central

Rice, W G; Schaeffer, C A; Graham, L; Bu, M; McDougal, J S; Orloff, S L; Villinger, F; Young, M; Oroszlan, S; Fesen, M R

1993-01-01

The C-nitroso compound 3-nitrosobenzamide, which has been shown to remove zinc from the retroviral-type zinc finger of p7NC nucleocapsid proteins, inhibits acute infection of human immunodeficiency virus type 1 in cultured human lymphocytes. The attachment of the virus to lymphocytes and the activities of critical viral enzymes, such as reverse transcriptase, protease, and integrase, are not affected by 3-nitrosobenzamide. However, the process of reverse transcription to form proviral DNA is effectively abolished by the drug, identifying the mode of action of 3-nitrosobenzamide as interrupting the role of p7NC in accurate proviral DNA synthesis during the infectious phase of the virus life cycle. Images Fig. 3 Fig. 4 PMID:7692451

Fulde-Ferrell-Larkin-Ovchinnikov superconductivity in the layered organic superconductor β "-(BEDT-TTF ) 4[(H3O ) Ga (C2O4)3] C6H5NO2

NASA Astrophysics Data System (ADS)

Uji, S.; Iida, Y.; Sugiura, S.; Isono, T.; Sugii, K.; Kikugawa, N.; Terashima, T.; Yasuzuka, S.; Akutsu, H.; Nakazawa, Y.; Graf, D.; Day, P.

2018-04-01

Resistance and magnetic torque measurements are reported in a layered organic superconductor, β "-(BEDT-TTF ) 4[(H3O ) Ga (C2O4)3] C6H5NO2 with Tc=4.8 K, where BEDT-TTF stands for bis(ethylenedithio)tetrathiafulvalene. Because of the large anion between the BEDT-TTF conducting layers, the superconductivity of this salt is highly anisotropic. In magnetic fields parallel to the conducting layers for T =0.4 K, the magnetic torque shows a large diamagnetic signal associated with hysteresis up to ˜21 T, suggesting the upper critical field Hc 2≳21 T at 0.4 K. The large reduction of the diamagnetic signal is observed above 16 T, which shows a Fulde and Ferrell and Larkin and Ovchinnikov (FFLO) phase transition. For T =0.5 K, the interlayer resistance has nonzero value in a wide field region up to Hc 2, arising from the Josephson vortex dynamics. Successive dips in the second derivative curves of the resistance are observed between 16 T and Hc 2, which are ascribed to the commensurability effect between the Josephson vortex lattice and the order parameter oscillation of the FFLO phase. The commensurability effect is observed only in nearly parallel fields, showing that the FFLO phase is stable in a very limited field angle region. The temperature-field phase diagram is determined.

Type- and age-specific distribution of human papillomavirus in women attending cervical cancer screening in Finland

PubMed Central

Leinonen, M K; Anttila, A; Malila, N; Dillner, J; Forslund, O; Nieminen, P

2013-01-01

Background: Large-scale data on type-specific HPV prevalences and disease burden are needed to monitor the impact of HPV vaccination and to plan for HPV-based cervical screening. Methods: 33 043 women (aged 25–65) were screened for HPV by a Hybrid Capture 2 (HC2) in a population-based programme. HPV-positive women (n=2574) were triaged by cytology and HPV genotyped using PCR-Luminex. Type-specific prevalence of HPV infection and its correlation to findings in cytology triage and histology as well as Population Attributable Fractions for a referral to colposcopy and findings in histology were calculated. Results: Among HC2-positive women, 61.5% had normal, 23.1% had ASC-US and 15.5% had LSIL or more severe (LSIL+) results in cytology. Out of HC2-positive samples, 57% contained the 13 Group 1/2A HPV types, which were targeted by the HC2, 15% contained Group 2B types, 8.5% Group 3 types and 30% were found to be negative in HPV genotyping. The proportion of samples positive for HPV by the HC2, but negative in HPV genotyping increased with age and decreased with increasing cytological abnormality. The most frequent types were HPV 16 (0.9% of screened women and 12.1% of the HC2-positive women), HPV 31 (0.7% and 8.9%, respectively) and HPV 52 (0.5% and 6.3%, respectively). The prevalence of Group 1/2A HPV types increased with increasing CIN grade and attributed 78.3% (95% CI 53.4–89.9) of the CIN 3+ lesions, while HPV 16 attributed 55.8% (40.0–67.5) of them. Conclusion: The type-specific prevalence of HPV were slightly lower than the average in international meta-analyses. Genotyping for HPV 16 better identified women with CIN 3+ than cytology triage at the threshold of LSIL+. The high proportion of women that were HC2-positive but HPV-negative in genotyping suggests that HPV genotyping may be useful also for validation of results in HPV screening. The large-scale HPV genotyping data were found to be directly useful for planning further preventive efforts for cervical cancer. PMID:24136148

Obese type 2 diabetics have a blunted hypotensive response to acute hyperthermia therapy that does not affect the perception of thermal stress or physiological strain compared to healthy adults.

PubMed

Rivas, Eric; Newmire, Dan E; Ben-Ezra, Vic

2016-10-15

The objective of this study was to test the hypothesis that a hyperthermia-hypotensive challenge via whole body hot water immersion would alter the perception of hyperthermia and physiological strain in obese type 2 diabetics (T2DM) compared to healthy non-obese (HC) individuals. Additionally, we hypothesize that the mechanisms would be attributed to impaired blood pressure adjustments and afferent signals (via changes in internal and mean skin temperatures). In random order, eleven obese T2DM (50±12y, 45±7% fat mass, 7.5±1.8% HbA1c) and nine similar aged (41±14y, P>0.05) HC non-obese (33±8% fat mass, P<0.01) non-diabetic (5.3±0.4% HbA1c, P<0.01) underwent a 60min bout of whole body passive hyperthermia followed by 60min of recovery or a 2h resting control condition. The perception of thermal sensation (TS, scale range: 1-13), calculated physiological strain (PSI), internal (Tre, rectal) and mean skin (Tsk) temperatures, heart rate (HR) and blood pressures (BP) were the primary dependent variables. Hyperthermia similarly increased Tre by 1.4±0.4°C, Tsk by 6.5±0.8°C and HR by 34±8bpm in both groups (P>0.5). Hyperthermia reduced diastolic BP (27% in T2DM and 33% in HC, P<0.05) and mean arterial BP (reduced by 15% in T2DM and by 19% in HC) relative to control conditions (P<0.05). The reduction of mean arterial BP area under the curve was attenuated in T2DM (12%) compared to HC (30%) (group×condition, P<0.01). TS and PSI during hyperthermia were not different between groups. Pearson product correlation reported strong correlations (r=0.69-0.89) with Tre and Tsk with TS in both populations. The linear stepwise regression analysis revealed similar relative contributions for Tre (~60%) and Tsk (~40%) on TS for both groups. These data indicate that obese T2DM with moderate metabolic control have an attenuated hyperthermia-hypotensive response that does not affect TS and PSI. This also may suggest behavioral thermoregulation is intact in this study group. Copyright © 2016 Elsevier Inc. All rights reserved.

Density functional theory study of the mechanism and origins of stereoselectivity in the asymmetric Simmons-Smith cyclopropanation with Charette chiral dioxaborolane ligand.

PubMed

Wang, Tao; Liang, Yong; Yu, Zhi-Xiang

2011-06-22

Asymmetric Simmons-Smith reaction using Charette chiral dioxaborolane ligand is a widely applied method for the construction of enantiomerically enriched cyclopropanes. The detailed mechanism and the origins of stereoselectivity of this important reaction were investigated using density functional theory (DFT) calculations. Our computational studies suggest that, in the traditional Simmons-Smith reaction conditions, the monomeric iodomethylzinc allyloxide generated in situ from the allylic alcohol and the zinc reagent has a strong tendency to form a dimer or a tetramer. The tetramer can easily undergo an intramolecular cyclopropanation to give the racemic cyclopropane product. However, when a stoichiometric amount of Charette chiral dioxaborolane ligand is employed, monomeric iodomethylzinc allyloxide is converted into an energetically more stable four-coordinated chiral zinc/ligand complex. The chiral complex has the zinc bonded to the CH(2)I group and coordinated by three oxygen atoms (one from the allylic alcohol and the other two oxygen atoms from the carbonyl oxygen and the ether oxygen in the dioxaborolane ligand), and it can undergo the cyclopropanation reaction easily. Three key factors influencing the enantioselectivity have been identified through examining the cyclopropanation transition states: (1) the torsional strain along the forming C-C bond, (2) the 1,3-allylic strain caused by the chain conformation, and (3) the ring strain generated in the transition states. In addition, the origin of the high anti diastereoselectivity for the substituent on the zinc reagent and the hydroxymethyl group of the allylic alcohol has been rationalized through analyzing the steric repulsion and the ring strain in the cyclopropanation transition states.

Cadmium Alternatives High Strength Steel JTP

DTIC Science & Technology

2005-03-01

Cadmium Alternatives HSS JTP Alternative Coatings Selected by JCAT: Primary Repair LHE Cadmium (control) IVD Aluminum (control) Zinc-Nickel, acid...Tin-Zinc Cadmium Alternatives HSS JTP Demonstration Tests Selected by JCAT: Phase I Phase II Hydrogen Embrittlement Hydrogen Re-Embrittlement (NRB...immersion, exposed C-ring (Army)) Bend Adhesion (Q/A) Appearance Throwing Power Composition Uniformity Strippability Galvanic Potential Bend Adhesion

Ethnic studies of dietary intakes of zinc, copper, iron, and calcium

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

Matthews, C.; Figueroa, M.; Tam, C.F.

1986-01-01

Immigrants, such as S.E. Asians who live in the L.A. area, often suffer high incidences of diseases. It is of interest to examine ethnic eating patterns whether they influence dietary Zn, Cu, Fe, Ca, protein and Kcal, which are essential for proper immune functions. Three-day dietary intake of adult ethnic groups, Asian(A)(N=18), Caucasian(C)(26), Black(B)(7), Latino(L)(12), Middle Easterner(ME)(9) and Filipino(F)(6) were analyzed for Zn, Cu, Fe, Ca, protein and Kcal by Ohio Data Base Foods II(ODBF) then statistically compared by PROPHET. Zn and Cu were also analyzed by hand calculation(HC). No statistical differences were observed for mean Zn between groups analyzedmore » by ODBF whereas HC of mean Zn between A vs C (A=11.3 +/- S.D.2.9 mg vs C=8.8 +/- 2.8, P<0.01) and A vs L (11.3+/-2.9 vs L=8.9+/-2.2, P<0.05) were statistically different. No differences were found for Cu between the groups. By ODBF, none of mean Cu or Zn met 2/3 RDA for any of the groups. For Fe, no differences were found between groups and only 50% of the subjects met 2/3 RDA. Significant differences were observed for Ca only between A vs C and B vs C. Both A and B had lower mean Ca than C. All groups had adequate protein. Mean Kcal of all groups were found to be at or about 2/3 RDA. Both insufficient Kcal and eating patterns contribute to inadequate Cu, Zn, and Fe intakes and hence may affect immune competency.« less

Rings of Molecular Line Emission in the Disk Orbiting the Young, Close Binary V4046 Sgr

NASA Astrophysics Data System (ADS)

Dickson-Vandervelde, Dorothy; Kastner, Joel H.; Qi, C.; Forveille, Thierry; Hily-Blant, Pierre; Oberg, Karin; Wilner, David; Andrews, Sean; Gorti, Uma; Rapson, Valerie; Sacco, Germano; Principe, David

2018-01-01

We present analysis of a suite of subarcsecond ALMA Band 6 (1.1 - 1.4 mm) molecular line images of the circumbinary, protoplanetary disk orbiting V4046 Sgr. The ~20 Myr-old V4046 Sgr system, which lies a mere ~73 pc from Earth, consists of a close (separation ~10 Rsun) pair of roughly solar-mass stars that are orbited by a gas-rich crcumbinary disk extending to ~350 AU in radius. The ALMA images reveal that the molecules CO and HCN and their isotopologues display centrally peaked surface brightness morphologies, whereas the cyanide group molecules (HC3N, CH3CN), deuterated molecules (DCN, DCO+), hydrocarbons (as traced by C2H), and potential CO ice line tracers (N2H+, and H2CO) appear as a sequence of sharp and diffuse rings of increasing radii. The characteristic sizes of these molecular emission rings, which range from ~25 to >100 AU in radius, are evident in radial emission-line surface brightness profiles extracted from the deprojected disk images. We find that emission from 13CO emission transitions from optically thin to thick within ~50 AU, whereas C18O emission remains optically thin within this radius. We summarize the insight into the physical and chemical processes within this evolved protoplanetary disk that can be obtained from comparisons of the various emission-line morphologies with each other and with that of the continuum (large-grain) emission on size scales of tens of AU.This research is supported by NASA Exoplanets program grant NNX16AB43G to RIT

275 C Downhole Microcomputer System

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

Chris Hutchens; Hooi Miin Soo

2008-08-31

An HC11 controller IC and along with serial SRAM and ROM support ICs chip set were developed to support a data acquisition and control for extreme temperature/harsh environment conditions greater than 275 C. The 68HC11 microprocessor is widely used in well logging tools for control, data acquisition, and signal processing applications and was the logical choice for a downhole controller. This extreme temperature version of the 68HC11 enables new high temperature designs and additionally allows 68HC11-based well logging tools and MWD tools to be upgraded for high temperature operation in deep gas reservoirs, The microcomputer chip consists of the microprocessormore » ALU, a small boot ROM, 4 kbyte data RAM, counter/timer unit, serial peripheral interface (SPI), asynchronous serial interface (SCI), and the A, B, C, and D parallel ports. The chip is code compatible with the single chip mode commercial 68HC11 except for the absence of the analog to digital converter system. To avoid mask programmed internal ROM, a boot program is used to load the microcomputer program from an external mask SPI ROM. A SPI RAM IC completes the chip set and allows data RAM to be added in 4 kbyte increments. The HC11 controller IC chip set is implemented in the Peregrine Semiconductor 0.5 micron Silicon-on-Sapphire (SOS) process using a custom high temperature cell library developed at Oklahoma State University. Yield data is presented for all, the HC11, SPI-RAM and ROM. The lessons learned in this project were extended to the successful development of two high temperature versions of the LEON3 and a companion 8 Kbyte SRAM, a 200 C version for the Navy and a 275 C version for the gas industry.« less

Proteomics and immunohistochemistry identify the expression of α-cardiac myosin heavy chain in the jaw-closing muscles of sooty mangabeys (order Primates).

PubMed

Wall, Christine E; Holmes, Megan; Soderblom, Erik J; Taylor, Andrea B

2018-07-01

The jaw-closing muscles of humans and nonprimate mammals express alpha-cardiac fibers but MyHC α-cardiac has not been identified in the jaw adductors of nonhuman primates. We determined whether MyHC α-cardiac is expressed in the superficial masseter and temporalis muscles of the sooty mangabey (Cercocebus atys), an African Old World monkey that specializes on hard seeds. LC-MS/MS based proteomics was used to identify the presence of MyHC Iα. Immunohistochemistry was used to analyze the composition and distribution of fiber types in the superficial masseter and temporalis muscles of eight C. atys. Serial sections were stained against MyHC α-cardiac (MYH6), as well as MyHC-1 (NOQ7.5.4D), MyHC-2 (MY-32), and MyHC-M (2F4). Proteomics analysis identified the presence of Myosin-6 (MyHC α-cardiac) in both heart atrium and superficial masseter. MyHC α-cardiac was expressed in abundance in the superficial masseter and temporalis muscles of all eight individuals and hybrid fibers were common. The identification of MyHC α-cardiac in the jaw adductors of sooty mangabeys is a novel finding for nonhuman primates. The abundance of MyHC α-cardiac indicates a fatigue-resistant fiber population characterized by intermediate speed of contraction between pure MyHC-1 and MyHC-2 isoforms. We suggest that α-cardiac fibers may be advantageous to sooty mangabeys, whose feeding behavior includes frequent crushing of relatively large, hard seeds during the power stroke of ingestion. Additional studies comparing jaw-adductor fiber phenotype of hard-object feeding primates and other mammals are needed to explore this relationship further. Copyright © 2018 Elsevier Ltd. All rights reserved.

{[Ga(en){sub 3}]{sub 2}(Ge{sub 2}Te{sub 15})}n : a polymeric semiconducting polytelluride with boat-shaped Te{sub 8}{sup 4-} rings and cross-shaped Te{sub 5}{sup 6-} units.

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

Zhang, Q.; Malliakas, C. D.; Kanatzidis, M. G.

2009-11-11

The reaction of the Zintl compound K{sub 4}Ge{sub 9} with Te and Ga{sub 2}Te{sub 3} in ethylenediamine (en) at 190 C gave the germanium polytelluride {l_brace}[Ga(en){sub 3}]{sub 2}[(GeTe){sub 2}(Te{sub 5}){sup 6-}(Te{sub 8}){sup 4-}]{r_brace}n (1). The single-crystal structure analysis revealed that 1 has two different polytelluride fragments: cross-shaped 36-e- TeTe{sub 4}{sup 6-} anions and boat-shaped 52-e- Te{sup 8}{sup 4-} rings. The new material is a p-type semiconductor at room temperature and switches to n-type at 380 K.

504 Participation of Invariant NKT Cells (Vα24Jα18) during Asthma Exacerbation in Children

PubMed Central

Carpio-Pedroza, Juan Carlos; del Rio-Navarro, Blanca Estela; del Río-Chivardí, Jaime Mariano; Morales-Flores, Amelia; Jiménez-Zamudio, Luis Antonio; Moreno-Lafont, Martha; Pedraza-Sánchez, Sigifredo; Vaughan-Figueroa, Juan Gilberto; Escobar-Gutiérrez, Alejandro

2012-01-01

Background Invariant NKT cells (or type 1 NKT cells) co-express CD3 marker and NK receptors (CD56, CD161) and use a single type of TCRα chain (Vα24Jα18 for humans), comprising CD4-CD8-, CD4+ and CD8+ subsets. Participation of these cells and their cytokines in asthmatic children, in stable conditions and under exacerbation, was studied. Methods Three groups on children (6–12 years old) were selected: 1) asthmatics under exacerbation attack (AE) within the first 24 hours after the attack and before starting any treatment; 2) asthmatics with stable asthma (SA), without symptoms for at least a month before bleeding; and 3) healthy controls (HC) without history of asthma, atopy and with normal lung function were selected in the Allergy and Clinical Immunology Service, Hospital Infantil de Mexico. Invariant NKT cells and subset levels as well as intracellular cytokines were evaluated in whole blood by 4-color flow cytometry (antibodies against CD3, CD4, CD8, CD161, Va24, IL-4 and IFN-g). Results Proportion of iNKT cells among total CD3+ cells in HC group was 0.9%, while in SA patients they were increased up to 2.6%; interestingly, during exacerbation such cells were dimished (1.8%). Concerning iNKT CD4+ cells were 0.6% in HC, 1.8% in SA, and 0.7% in AE, while iNKT CD8+ cells were 0.1% in HC, 0.7% in SA, and 0.4% in AE. Both iNKT cell subsets expressed intracellular IFN-g and IL-4 cytokines in AE, SA and HC but predominantly IFN-g in iNKT CD8+ cells from AE patients. Conclusions iNKT cells participation in asthma pathogenesis was confirmed. Increase of IFN-g production in patients with exacerbations, may provide a regulatory environment to stabilize the condition.

A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

NASA Astrophysics Data System (ADS)

Nguyen, Trong-Nghia; Putikam, Raghunath; Lin, M. C.

2015-03-01

We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH2OO and anti/syn-CH3C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH2OO and anti-CH3C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH3C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C-H bonds. For syn-CH3C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH3 group by the terminal O atom producing CH2C(H)O-OH. At 298 K, the intramolecular insertion process in CH2OO was found to be 600 times faster than the commonly assumed ring-closing reaction.

The Evolution of REM Sleep Behavior Disorder in Early Parkinson Disease

PubMed Central

Sixel-Döring, Friederike; Zimmermann, Johannes; Wegener, Andrea; Mollenhauer, Brit; Trenkwalder, Claudia

2016-01-01

Study Objectives: To investigate the development of REM sleep behavior disorder (RBD) and REM sleep behavioral events (RBE) not yet fulfilling diagnostic criteria for RBD as markers for neurodegeneration in a cohort of Parkinson disease (PD) patients between their de novo baseline assessment and two-year follow-up in comparison to healthy controls (HC). Methods: Clinically confirmed PD patients and HC with video-supported polysomnography (vPSG) data at baseline were re-investigated after two years. Diagnostic scoring for RBE and RBD was performed in both groups and related to baseline findings. Results: One hundred thirteen PD patients and 102 healthy controls (HC) were included in the study. Within two years, the overall occurrence of behaviors during REM sleep in PD patients increased from 50% to 63% (P = 0.02). RBD increased from 25% to 43% (P < 0.001). Eleven of 29 (38%) RBE positive PD patients and 10/56 (18%) patients with normal REM sleep at baseline converted to RBD. In HC, the occurrence of any REM behavior increased from 17% to 20% (n.s.). RBD increased from 2% to 4% (n.s.). One of 15 (7%) RBE positive HC and 1/85 (1%) HC with normal REM at baseline converted to RBD. Conclusions: RBD increased significantly in PD patients from the de novo state to two-year follow-up. We propose RBE being named “prodromal RBD” as it may follow a continuous evolution in PD possibly similar to the spreading of Lewy bodies in PD patients. RBD itself was shown as a robust and stable marker of early PD. Citation: Sixel-Döring F, Zimmermann J, Wegener A, Mollenhauer B, Trenkwalder C. The evolution of REM sleep behavior disorder in early Parkinson disease. SLEEP 2016;39(9):1737–1742. PMID:27306265

Analysis of failed and nickel-coated 3093 beam clamp components at the East Tennessee Technology Park (ETTP).

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

Singh, D.; Pappacena, K.; Gaviria, J.

2010-10-11

The U.S. Department of Energy and its contractor, Bechtel Jacobs Company (BJC), are undertaking a major effort to clean up the former gaseous diffusion facility (K-25) located in Oak Ridge, TN. The decontamination and decommissioning activities require systematic removal of contaminated equipment and machinery followed by demolition of the buildings. As part of the cleanup activities, a beam clamp, used for horizontal life lines (HLLs) for fall protection, was discovered to be fractured during routine inspection. The beam clamp (yoke and D-ring) was a component in the HLL system purchased from Reliance Industries LLC. Specifically, the U-shaped stainless steel yokemore » of the beam clamp failed in a brittle mode at under less than 10% of the rated design capacity of 14,500 lb. The beam clamp had been in service for approximately 16 months. Bechtel Jacobs approached Argonne National Laboratory to assist in identifying the root cause of the failure of the beam clamp. The objectives of this study were to (1) review the prior reports and documents on the subject, (2) understand the possible failure mechanism(s) that resulted in the failed beam clamp components, (3) recommend approaches to mitigate the failure mechanism(s), and (4) evaluate the modified beam clamp assemblies. Energy dispersive x-ray analysis and chemical analysis of the corrosion products on the failed yoke and white residue on an in-service yoke indicated the presence of zinc, sulfur, and calcium. Analysis of rainwater in the complex, as conducted by BJC, indicated the presence of sulfur and calcium. It was concluded that, as a result of galvanic corrosion, zinc from the galvanized components of the beam clamp assembly (D-ring) migrated to the corroded region in the presence of the rainwater. Under mechanical stress, the corrosion process would have accelerated, resulting in the catastrophic failure of the yoke. As suggested by Bechtel Jacobs personnel, hydrogen embrittlement as a consequence of corrosion was also explored as a failure mechanism. Corroded and failed yoke samples had hydrogen concentrations of 20-60 ppm. However, the hydrogen content reduced to 4-11 ppm (similar to baseline as-received yoke samples) when the corrosion products were polished off. The hydrogen content in the scraped off corrosion product powders was >7000 ppm. These results indicate that hydrogen is primarily present in the corrosion products and not in the underlying steel. Rockwell hardness values on the corroded yoke and D-rings were R{sub c} {approx} 41-46. It was recommended to the beam clamp manufacturer that the beam clamp components be annealed to reduce the hardness values so that they are less susceptible to brittle failure. Upon annealing, hardness values of the beam clamp components reduced to R{sub c} {approx} 25. Several strategies were recommended and put in place to mitigate failure of the beam clamp components: (a) maintain hardness levels of both yokes and D-rings at R{sub c} < 35, (b) coat the yoke and D-rings with a dual coating of nickel (with 10% phosphorus) to delay corrosion and aluminum to prevent galvanic corrosion since it is more anodic to zinc, and (c) optimize coating thicknesses for nickel and aluminum while maintaining the physical integrity of the coatings. Evaluation of the Al- and Ni-coated yoke and D-ring specimens indicated they appear to have met the recommendations. Average hardness values of the dual-coated yokes were R{sub c} {approx} 25-35. Hardness values of dual-coated D-ring were R{sub c} {approx} 32. Measured average coating thicknesses for the aluminum and nickel coatings for yoke samples were 22 {micro}m (0.9 mils) and 80 {micro}m (3 mils), respectively. The D-rings also showed similar coating thicknesses. Microscopic examination showed that the aluminum coating was well bonded to the underlying nickel coating. Some observed damage was believed to be an artifact of the cutting-and-polishing steps during sample preparation for microscopy.« less

Polymorphic one-dimensional (N2H4)2ZnTe: soluble precursors for the formation of hexagonal or cubic zinc telluride.

PubMed

Mitzi, David B

2005-10-03

Two hydrazine zinc(II) telluride polymorphs, (N2H4)2ZnTe, have been isolated, using ambient-temperature solution-based techniques, and the crystal structures determined: alpha-(N2H4)2ZnTe (1) [P21, a = 7.2157(4) Angstroms, b = 11.5439(6) Angstroms, c = 7.3909(4) Angstroms, beta = 101.296(1) degrees, Z = 4] and beta-(N2H4)2ZnTe (2) [Pn, a = 8.1301(5) Angstroms, b = 6.9580(5) Angstroms, c = 10.7380(7) Angstroms, beta = 91.703(1) degrees, Z = 4]. The zinc atoms in 1 and 2 are tetrahedrally bonded to two terminal hydrazine molecules and two bridging tellurium atoms, leading to the formation of extended one-dimensional (1-D) zinc telluride chains, with different chain conformations and packings distinguishing the two polymorphs. Thermal decomposition of (N2H4)2ZnTe first yields crystalline wurtzite (hexagonal) ZnTe at temperatures as low as 200 degrees C, followed by the more stable zinc blende (cubic) form at temperatures above 350 degrees C. The 1-D polymorphs are soluble in hydrazine and can be used as convenient precursors for the low-temperature solution processing of p-type ZnTe semiconducting films.

Methyl 6-eth-oxy-3-phenyl-3a,4-dihydro-3H-chromeno[4,3-c]isoxazole-3a-car-boxylate.

PubMed

Suresh, G; Srinivasan, J; Bakthadoss, M; Aravindhan, S

2013-02-01

In the title compound, C(20)H(19)NO(5), the dihedral angle between the mean plane of the pyran ring (which has a half-chair conformation) and the benzene ring of the chromeno ring system is 7.21 (7)°. The dihedral angle between the mean plane of the chromeno ring system and the isoxazole ring is 21.78 (6)°, while the isoxazole ring forms a dihedral angle of 72.60 (8)° with the attached phenyl ring. In the crystal, mol-ecules are linked via pairs of C-H⋯O hydrogen bonds, forming inversion dimers with an R(2) (2)(10) ring motif. These dimers are linked via C-H⋯N hydrogen bonds, forming chains along [001].

Laboratory Study of Aliphatic Organic Spectral Signatures and Applications to Ceres and Primitive Asteroids

NASA Astrophysics Data System (ADS)

Kaplan, H. H.; Milliken, R.

2017-12-01

Aliphatic organics were recently discovered on the surface of Ceres with Dawn's Visible and InfraRed (VIR) mapping spectrometer, which has implications for prebiotic chemistry of Ceres and other asteroids. An absorption in the spectrum at 3.4 µm was used to identify and provide initial estimates of the amount of organic material. We have studied the 3.4 µm absorption in reflectance spectra of bulk rock and meteorite powders and isolated organic materials in the NASA RELAB facility at Brown University to determine how organic composition and abundance affects absorption strength. Reflectance spectra of insoluble organic matter (IOM) extracted from carbonaceous chondrites were measured from 0.35 - 25 µm. These IOM have known elemental (H, C, N, O) and isotopic compositions that were compared with spectral properties. Bulk meteorites were measured as chips and particulates over the same wavelength range. Despite overall low reflectance values (albedo <0.01), the 3.4 µm absorption is observed for some IOM samples, specifically those with a H/C ratio greater than 0.4. The absorption strength (band depth) increases with increasing H/C ratio, which corroborates similar findings in our previous study of sedimentary rocks and isolated kerogens. The absorption strength in the bulk meteorites reflects both H/C of the IOM and the concentration of IOM in the inorganic (mineral) matrix. Overlapping absorptions from carbonates and phyllosilicates (OH/H2O) can also influence the aliphatic organic bands in bulk rocks and meteorites. This laboratory work provides a foundation that can be used to constrain the composition of Ceres' aliphatic organic matter using band depth as a proxy for H/C. Reflectance spectra collected for this work will also be used to model the Dawn VIR data and obtain abundance and H/C estimates assuming that the organic material on Ceres' surface is similar to carbonaceous chondrite IOM. These spectra and findings can aid interpretation of reflectance data from Ceres and other asteroid missions, such as OSIRIS-REx and Hayabusa2.

Full exploration of the Diels-Alder cycloaddition on metallofullerenes M3N@C80 (M = Sc, Lu, Gd): the D(5h) versus I(h) isomer and the influence of the metal cluster.

PubMed

Osuna, Sílvia; Valencia, Ramón; Rodríguez-Fortea, Antonio; Swart, Marcel; Solà, Miquel; Poblet, Josep M

2012-07-16

In this work a detailed investigation of the exohedral reactivity of the most important and abundant endohedral metallofullerene (EMF) is provided, that is, Sc(3)N@I(h)-C(80) and its D(5h) counterpart Sc(3)N@D(5h)-C(80) , and the (bio)chemically relevant lutetium- and gadolinium-based M(3)N@I(h)/D(5h)-C(80) EMFs (M = Sc, Lu, Gd). In particular, we analyze the thermodynamics and kinetics of the Diels-Alder cycloaddition of s-cis-1,3-butadiene on all the different bonds of the I(h)-C(80) and D(5h)-C(80) cages and their endohedral derivatives. First, we discuss the thermodynamic and kinetic aspects of the cycloaddition reaction on the hollow fullerenes and the two isomers of Sc(3)N@C(80). Afterwards, the effect of the nature of the metal nitride is analyzed in detail. In general, our BP86/TZP//BP86/DZP calculations indicate that [5,6] bonds are more reactive than [6,6] bonds for the two isomers. The [5,6] bond D(5h)-b, which is the most similar to the unique [5,6] bond type in the icosahedral cage, I(h)-a, is the most reactive bond in M(3)N@D(5h)-C(80) regardless of M. Sc(3)N@C(80) and Lu(3)N@C(80) give similar results; the regioselectivity is, however, significantly reduced for the larger and more electropositive M = Gd, as previously found in similar metallofullerenes. Calculations also show that the D(5h) isomer is more reactive from the kinetic point of view than the I(h) one in all cases which is in good agreement with experiments. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

C2H2 type of zinc finger transcription factors in foxtail millet define response to abiotic stresses.

PubMed

Muthamilarasan, Mehanathan; Bonthala, Venkata Suresh; Mishra, Awdhesh Kumar; Khandelwal, Rohit; Khan, Yusuf; Roy, Riti; Prasad, Manoj

2014-09-01

C2H2 type of zinc finger transcription factors (TFs) play crucial roles in plant stress response and hormone signal transduction. Hence considering its importance, genome-wide investigation and characterization of C2H2 zinc finger proteins were performed in Arabidopsis, rice and poplar but no such study was conducted in foxtail millet which is a C4 Panicoid model crop well known for its abiotic stress tolerance. The present study identified 124 C2H2-type zinc finger TFs in foxtail millet (SiC2H2) and physically mapped them onto the genome. The gene duplication analysis revealed that SiC2H2s primarily expanded in the genome through tandem duplication. The phylogenetic tree classified these TFs into five groups (I-V). Further, miRNAs targeting SiC2H2 transcripts in foxtail millet were identified. Heat map demonstrated differential and tissue-specific expression patterns of these SiC2H2 genes. Comparative physical mapping between foxtail millet SiC2H2 genes and its orthologs of sorghum, maize and rice revealed the evolutionary relationships of C2H2 type of zinc finger TFs. The duplication and divergence data provided novel insight into the evolutionary aspects of these TFs in foxtail millet and related grass species. Expression profiling of candidate SiC2H2 genes in response to salinity, dehydration and cold stress showed differential expression pattern of these genes at different time points of stresses.

White Light Emission from Planar Remote Phosphor Based on NHC Cycloplatinated Complexes.

PubMed

Fuertes, Sara; Chueca, Andrés J; Perálvarez, Mariano; Borja, Pilar; Torrell, Marc; Carreras, Josep; Sicilia, Violeta

2016-06-29

We report on the generation of bright white luminescence through solid-state illumination of remote phosphors based on novel cycloplatinated N-heterocyclic carbene (NHC) compounds. Following a stepwise protocol we got the new NHC compound [{Pt(μ-Cl)(C(∧)C*)}2] (4) (HC(∧)C*-κC* = 1-(4-(ethoxycarbonyl)phenyl)-3-methyl-1H-imidazol-2-ylidene), which was used together with the related ones 4a (HC(∧)C*-κC*= 1-(4-cyanophenyl)-3-methyl-1H-imidazol-2-ylidene) and 4b (HC(∧)C*-κC*= 3-methyl-1-(naphthalen-2-yl)-1H-imidazol-2-ylidene) as starting materials for the synthesis of the new ionic derivatives [Pt(R-C(∧)C*) (CNR')2]PF6 (R = -COOEt, R' = t-Bu (5), Xyl (6); R = -CN, R' = t-Bu (7), Xyl (8); R(∧)C = Naph, R' = t-Bu (9), Xyl (10)). The X-ray structures of 6 and 8-10 have been determined. The photophysical properties of these cationic compounds have been studied and supported by the time-dependent-density functional theory (TD-DFT) calculations. The compounds 5, 8, and 9 have been revealed as the most efficient emitters in the solid state with quantum yields of 41%, 21%, and 40%, respectively. White-light remote-phosphors have been prepared just by stacking different combinations of these compounds and [Pt(bzq) (CN) (CN(t)Bu)] (R1) as blue (5, 8), yellow (9), and red (R1) components onto the same substrate. The CCT (correlated color temperature) and the CRI (color rendering index) of the emitted white-light have been tuned by accurately controlling the individual contributions.

Health promotion for patients with diabetes: health coaching or formal health education?

PubMed

Basak Cinar, Ayse; Schou, Lone

2014-02-01

The purpose of this study was to determine if a Health Coaching (HC) approach compared with formal health education (HE) resulted in better health outcomes among type II diabetes (T2DM) patients in improving glycaemic control and oral health, by use of clinical and subjective outcome measures. The study is part of a prospective intervention among randomly selected T2DM patients (n = 186) in Istanbul, Turkey. The data analysed were clinical [glycated haemoglobin (HbA(1C)), clinical attachment loss (CAL)] and psychological measures [tooth-brushing self efficacy (TBSES)]. Data were collected initially and at the end of intervention. Participants were allocated randomly to HC (intervention) (n = 77) and HE (control) (n = 111) groups. At baseline, there was no statistical difference between HC and HE regarding clinical and psychological measures, (P > 0.05). At post-intervention the HC group had significantly lower HBA(1C) and CAL (reduction: 7%, 56%) than the HE group (reduction: HbA(1C) 0%; CAL 26%), (P ≤ 0.01). Similarly, HC group, compared with HE group, had better TBSES (increase: 61% vs. 25%) and stress (reduction: 16% vs. 1%), (P ≤ 0.01). Among high-risk group patients, the HC patients had significant improvements compared with the HE group (reduction: HbA(1C) 16% vs. 5%; CAL 63% vs. 18%; stress 39% vs. 2%; fold increase: TBSES 6.6 vs. 3.6) (P ≤ 0.01). The present findings may imply that HC has a significantly greater impact on better management of oral health and glycaemic control than HE. It is notable that the impact was more significant among high-risk group patients, thus HC may be recommended especially for high-risk group patients. © 2013 FDI World Dental Federation.

Derivation of freshwater quality criteria for zinc using interspecies correlation estimation models to protect aquatic life in China.

PubMed

Feng, C L; Wu, F C; Dyer, S D; Chang, H; Zhao, X L

2013-01-01

Species sensitivity distributions (SSDs) are usually used in the development of water quality criteria and require a large number of toxicity values to define a hazard level to protect the majority of species. However, some toxicity data for certain chemicals are limited, especially for endangered and threatened species. Thus, it is important to predict the unknown species toxicity data using available toxicity data. To address this need, interspecies correlation estimation (ICE) models were developed by US EPA to predict acute toxicity of chemicals to diverse species based on a more limited data set of surrogate species toxicity data. Use of SSDs generated from ICE models allows for the prediction of protective water quality criteria, such as the HC5 (hazard concentration, 5th percentile). In the present study, we tested this concept using toxicity data collected for zinc. ICE-based-SSDs were generated using three surrogate species (common carp (Cyprinus carpio), rainbow trout (Oncorhynchus mykiss), and Daphnia magna) and compared with the measured-based SSD and corresponding HC5. The results showed that no significant differences were observed between the ICE- and the measured-based SSDs and HC5s. Furthermore, the examination of species placements within the SSDs indicated that the most sensitive species to zinc were invertebrates, especially crustaceans. Given the similarity of SSD and HC5s for zinc, the use of ICE to derive potential water quality criteria for diverse chemicals in China is proposed. Further, a combination of measured and ICE-derived data will prove useful for assessing water quality and chemical risks in the near future. Copyright © 2012 Elsevier Ltd. All rights reserved.

Experimental Investigation of Performance and emission characteristics of Various Nano Particles with Bio-Diesel blend on Di Diesel Engine

NASA Astrophysics Data System (ADS)

Karthik, N.; Goldwin Xavier, X.; Rajasekar, R.; Ganesh Bairavan, P.; Dhanseelan, S.

2017-05-01

Present study provides the effect of Zinc Oxide (ZnO) and Cerium Oxide (CeO2) nanoparticles additives on the Performance and emission uniqueness of Jatropha. Jatropha blended fuel is prepared by the emulsification technique with assist of mechanical agitator. Nano particles (Zinc Oxide (ZnO)) and Cerium Oxide (CeO2)) mixed with Jatropha blended fuel in mass fraction (100 ppm) with assist of an ultrasonicator. Experiments were conducted in single cylinder constant speed direct injection diesel engine for various test fuels. Performance results revealed that Brake Thermal Efficiency (BTE) of Jatropha blended Cerium Oxide (B20CE) is 3% and 11% higher than Jatropha blended zinc oxide (B20ZO) and Jatropha blended fuel (B20) and 4% lower than diesel fuel (D100) at full load conditions. Emission result shows that HC and CO emissions of Jatropha blended Cerium Oxide (B20CE) are (6%, 22%, 11% and 6%, 15%, 12%) less compared with Jatropha blended Zinc Oxide (B20ZO), diesel (D100) and Jatropha blended fuel (B20) at full load conditions. NOx emissions of Jatropha blended Cerium Oxide is 1 % higher than diesel fuel (D100) and 2% and 5% lower than Jatropha blended Zinc Oxide, and jatropha blended fuel.

Crystal structure of 3-{[4-(2-meth-oxy-phen-yl)piperazin-1-yl]meth-yl}-5-(thio-phen-2-yl)-1,3,4-oxa-diazole-2(3H)-thione.

PubMed

Al-Alshaikh, Monirah A; Abuelizz, Hatem A; El-Emam, Ali A; Abdelbaky, Mohammed S M; Garcia-Granda, Santiago

2016-02-01

The title compound, C18H20N4O2S2, is a new 1,3,4-oxa-diazole and a key pharmacophore of several biologically active agents. It is composed of a meth-yl(thio-phen-2-yl)-1,3,4-oxa-diazole-2(3H)-thione moiety linked to a 2-meth-oxy-phenyl unit via a piperazine ring that has a chair conformation. The thio-phene ring mean plane lies almost in the plane of the oxa-diazole ring, with a dihedral angle of 4.35 (9)°. The 2-meth-oxy-phenyl ring is almost normal to the oxa-diazole ring, with a dihedral angle of 84.17 (10)°. In the crystal, mol-ecules are linked by weak C-H⋯S hydrogen bonds and C-H⋯π inter-actions, forming layers parallel to the bc plane. The layers are linked via weak C-H⋯O hydrogen bonds and slipped parallel π-π inter-actions [inter-centroid distance = 3.6729 (10) Å], forming a three-dimensional structure. The thio-phene ring has an approximate 180° rotational disorder about the bridging C-C bond.

A comprehensive computational study on pathogenic mis-sense mutations spanning the RING2 and REP domains of Parkin protein.

PubMed

Biswas, Ria; Bagchi, Angshuman

2017-04-30

Various mutations in PARK2 gene, which encodes the protein parkin, are significantly associated with the onset of autosomal recessive juvenile Parkinson (ARJP) in neuronal cells. Parkin is a multi domain protein, the N-terminal part contains the Ubl and the C-terminal part consists of four zinc coordinating domains, viz., RING0, RING1, in between ring (IBR) and RING2. Disease mutations are spread over all the domains of Parkin, although mutations in some regions may affect the functionality of Parkin more adversely. The mutations in the RING2 domain are seen to abolish the neuroprotective E3 ligase activity of Parkin. In this current work, we carried out detailed in silico analysis to study the extent of pathogenicity of mutations spanning the Parkin RING2 domain and the adjoining REP region by SIFT, Mutation Accessor, PolyPhen2, SNPs and GO, GV/GD and I-mutant. To study the structural and functional implications of these mutations on RING2-REP domain of Parkin, we studied the solvent accessibility (SASA/RSA), hydrophobicity, intra-molecular hydrogen bonding profile and domain analysis by various computational tools. Finally, we analysed the interaction energy profiles of the mutants and compared them to the wild type protein using Discovery studio 2.5. By comparing the various analyses it could be safely concluded that except P437L and A379V mutations, all other mutations were potentially deleterious affecting various structural aspects of RING2 domain architecture. This study is based purely on computational approach which has the potential to identify disease mutations and the information could further be used in treatment of diseases and prognosis. Copyright © 2017 Elsevier B.V. All rights reserved.

Multifunctional Involvement of a C2H2 Zinc Finger Protein (PbZfp) in Malaria Transmission, Histone Modification, and Susceptibility to DNA Damage Response

PubMed Central

Gopalakrishnan, Anusha M.; Aly, Ahmed S. I.; Aravind, L.

2017-01-01

ABSTRACT In sexually reproducing organisms, meiosis is an essential step responsible for generation of haploid gametes from diploid somatic cells. The quest for understanding regulatory mechanisms of meiotic recombination in Plasmodium led to identification of a gene encoding a protein that contains 11 copies of C2H2 zinc fingers (ZnF). Reverse genetic approaches were used to create Plasmodium berghei parasites either lacking expression of full-length Plasmodium berghei zinc finger protein (PbZfp) (knockout [KO]) or expressing PbZfp lacking C-terminal zinc finger region (truncated [Trunc]). Mice infected with KO parasites survived two times longer (P < 0.0001) than mice infected with wild-type (WT) parasites. In mosquito transmission experiments, the infectivity of KO and Trunc parasites was severely compromised (>95% oocyst reduction). KO parasites revealed a total lack of trimethylation of histone 3 at several lysine residues (K4, K27, and K36) without any effect on acetylation patterns (H3K9, H3K14, and H4K16). Reduced DNA damage and reduced expression of topoisomerase-like Spo11 in the KO parasites with normal Rad51 expression further suggest a functional role for PbZfp during genetic recombination that involves DNA double-strand break (DSB) formation followed by DNA repair. These finding raise the possibility of some convergent similarities of PbZfp functions to functions of mammalian PRDM9, also a C2H2 ZnF protein with histone 3 lysine 4 (H3K4) methyltransferase activity. These functions include the major role played by the latter in binding recombination hotspots in the genome during meiosis and trimethylation of the associated histones and subsequent chromatin recruitment of topoisomerase-like Spo11 to catalyze DNA DSB formation and DMC1/Rad51-mediated DNA repair and homologous recombination. PMID:28851851

Intrapartum fetal head circumference and estimated fetal weight as predictors of operative delivery.

PubMed

Rabei, Noha H; El-Helaly, Amr M; Farag, Amr H; El-Naggar, Ahmed K; Etman, Mohamed K; El-Moteily, Moataz M

2017-04-01

To assess intrapartum sonographic measurements of fetal head circumference (HC) and estimated fetal weight (EFW) to predict operative delivery. In a prospective study, 200 spontaneously parturient primiparous women aged 20-30 years were enrolled at a teaching hospital in Cairo, Egypt, between October 2, 2015, and January 28, 2016. HC and EFW were measured by transabdominal ultrasonography. After delivery, the association between type of delivery and ultrasonography findings was assessed. Intrapartum HC and EFW were significantly higher among women with operative delivery (n=76) than among those with normal vaginal delivery (n=124; P<0.001 for both). Intrapartum HC of 36.8 cm or more was associated with an increased risk of operative delivery (relative risk [RR] 2.87, 95% CI 1.87-4.41), as was EFW of 3920 g or more (RR 3.69, 95% CI 2.13-6.40). The area under the receiver operating characteristic curve was 0.807 and 0.748 for HC and EFW, respectively (P<0.001 for both). At 36.8-cm cutoff, HC had 44.7% sensitivity, 91.9% specificity, 77.3% positive predictive value (PPV), and 73.1% negative predictive value (NPV). At 3920-g cutoff, EFW had 68.4% sensitivity, 82.3% specificity, 70.3% PPV, and 81.0% NPV. Intrapartum HC and EFW were directly correlated with second-stage duration (P=0.005 and 0.002, respectively). Intrapartum HC and EFW seem to be good predictors of operative delivery. © 2017 International Federation of Gynecology and Obstetrics.

Ethyl 2-{4-[(1,5-dibenzyl-2,4-dioxo-2,3,4,5-tetra-hydro-1H-1,5-benzo-diazepin-3-yl)meth-yl]-1H-1,2,3-triazol-1-yl}acetate.

PubMed

Jabli, Hind; Kandri Rodi, Y; Ladeira, Sonia; Essassi, El Mokhtar; Ng, Seik Weng

2009-12-12

The reaction of 1,5-dibenzyl-3-propargyl-1,5-benzodiazepine-2,4-dione with ethyl azido-acetate in the presence of copper sulfate pentahydrate and sodium ascorbate leads to the formation of the title regioisomer, C(30)H(29)N(5)O(4), which features a phenyl-ene ring fused with a seven-membered diazepinyl ring. The latter ring adopts a boat conformation (with the methyl-triazolylacetate-bearing C atom as the prow and the fused-ring C atoms as the stern). The benzyl groups connected to the diazepinyl ring jprotrude from the sides; the methyl-triazolylacetate substituent occupies an axial position.

Crystal structure of methyl 3'-benzamido-4'-(4-meth-oxy-phen-yl)-1'-methyl-spiro-[indeno-[1,2-b]quinoxaline-11,2'-pyrrolidine]-3'-carboxyl-ate.

PubMed

Chandralekha, Kuppan; Sureshbabu, Adukamparai Rajukrishnan; Gavaskar, Deivasigamani; Lakshmi, Srinivasakannan

2016-09-01

In the title compound, C 35 H 30 N 4 O 3 , the spiro C atom connects the five-membered pyrrolidine ring and the indeno-quinoxaline ring system. The pyrrolidine ring adopts a twist conformation. An intra-molecular N-H⋯N inter-action between the amino group and the pyrazine ring is observed. In the crystal, mol-ecules are linked by a pairs of C-H⋯O hydrogen bonds, forming inversion dimers.

RING-type ubiquitin ligase McCPN1 catalyzes UBC8-dependent protein ubiquitination and interacts with Argonaute 4 in halophyte ice plant.

PubMed

Li, Chang-Hua; Chiang, Chih-Pin; Yang, Jun-Yi; Ma, Chia-Jou; Chen, Yu-Chan; Yen, Hungchen Emilie

2014-07-01

RING-type copines are a small family of plant-specific RING-type ubiquitin ligases. They contain an N-terminal myristoylation site for membrane anchoring, a central copine domain for substrate recognition, and a C-terminal RING domain for E2 docking. RING-type copine McCPN1 (copine1) from halophyte ice plant (Mesembryanthemum crystallinum L.) was previously identified from a salt-induced cDNA library. In this work, we characterize the activity, expression, and localization of McCPN1 in ice plant. An in vitro ubiquitination assay of McCPN1 was performed using two ice plant UBCs, McUBC1 and McUBC2, characterized from the same salt-induced cDNA library. The results showed that McUBC2, a member of the UBC8 family, stimulated the autoubiquitination activity of McCPN1, while McUBC1, a homolog of the UBC35 family, did not. The results indicate that McCPN1 has selective E2-dependent E3 ligase activity. We found that McCPN1 localizes primarily on the plasma membrane and in the nucleus of plant cells. Under salt stress, the accumulation of McCPN1 in the roots increases. A yeast two-hybrid screen was used to search for potential McCPN1-interacting partners using a library constructed from salt-stressed ice plants. Screening with full-length McCPN1 identified several independent clones containing partial Argonaute 4 (AGO4) sequence. Subsequent agro-infiltration, protoplast two-hybrid analysis, and bimolecular fluorescence complementation assay confirmed that McCPN1 and AGO4 interacted in vivo in the nucleus of plant cells. The possible involvement of a catalyzed degradation of AGO4 by McCPN1 in response to salt stress is discussed. Copyright © 2014 Elsevier Masson SAS. All rights reserved.

State-Dependent Cross-Brain Information Flow in Borderline Personality Disorder.

PubMed

Bilek, Edda; Stößel, Gabriela; Schäfer, Axel; Clement, Laura; Ruf, Matthias; Robnik, Lydia; Neukel, Corinne; Tost, Heike; Kirsch, Peter; Meyer-Lindenberg, Andreas

2017-09-01

Although borderline personality disorder (BPD)-one of the most common, burdensome, and costly psychiatric conditions-is characterized by repeated interpersonal conflict and instable relationships, the neurobiological mechanism of social interactive deficits remains poorly understood. To apply recent advancements in the investigation of 2-person human social interaction to investigate interaction difficulties among people with BPD. Cross-brain information flow in BPD was examined from May 25, 2012, to December 4, 2015, in pairs of participants studied in 2 linked functional magnetic resonance imaging scanners in a university setting. Participants performed a joint attention task. Each pair included a healthy control individual (HC) and either a patient currently fulfilling DSM-IV criteria for BPD (cBPD) (n = 23), a patient in remission for 2 years or more (rBPD) (n = 17), or a second HC (n = 20). Groups were matched for age and educational level. A measure of cross-brain neural coupling was computed following previously published work to indicate synchronized flow between right temporoparietal junction networks (previously shown to host neural coupling abilities in health). This measure is derived from an independent component analysis contrasting the time courses of components between pairs of truly interacting participants compared with bootstrapped control pairs. In the sample including 23 women with cBPD (mean [SD] age, 26.8 [5.7] years), 17 women with rBPD (mean [SD] age, 28.5 [4.3] years), and 80 HCs (mean [SD] age, 24.0 [3.4] years]) investigated as dyads, neural coupling was found to be associated with disorder state (η2 = 0.17; P = .007): while HC-HC pairs showed synchronized neural responses, cBPD-HC pairs exhibited significantly lower neural coupling just above permutation-based data levels (η2 = 0.16; P = .009). No difference was found between neural coupling in rBPD-HC and HC-HC pairs. The neural coupling in patients was significantly associated with childhood adversity (T = 2.3; P = .03). This study provides a neural correlate for a core diagnostic and clinical feature of BPD. Results indicate that hyperscanning may deliver state-associated biomarkers for clinical social neuroscience. In addition, at least some neural deficits of BPD may be more reversible than is currently assumed for personality disorders.

Beneficial postprandial effect of a small amount of alcohol on diabetes and cardiovascular risk factors: modification by insulin resistance.

PubMed

Greenfield, Jerry R; Samaras, Katherine; Hayward, Chris S; Chisholm, Donald J; Campbell, Lesley V

2005-02-01

Moderate alcohol consumption protects against type 2 diabetes and cardiovascular disease. Because humans spend most of their time in the postprandial state, we examined the effect of 15 g alcohol on postprandial metabolic factors in 20 postmenopausal women over 6 h. We measured 1) glucose, insulin, lipids, C-reactive protein, and adiponectin levels; 2) augmentation index by applanation tonometry; and 3) energy expenditure and substrate oxidation by indirect calorimetry. Subjects received low carbohydrate (LC; visits 1 and 2) and high carbohydrate (HC; visits 3 and 4) high fat meals with and without alcohol. Alcohol augmented the postprandial increment in insulin (P = 0.07) and reduced the postprandial increment in glucose (P = 0.04) after the LC meal only. Triglycerides were increased by alcohol after the LC (P = 0.002) and HC (P = 0.008) meals. Total and high-density lipoprotein cholesterol, fatty acids, and total adiponectin responses were unaffected. C-reactive protein levels decreased postprandially; reductions were enhanced by alcohol after the HC meal, but were attenuated after the LC meal. Postprandial reductions in the augmentation index were increased by alcohol after the LC meal only (P = 0.007). Alcohol enhanced the postprandial increase in energy expenditure 30-60 min after the LC meal (increase, 373 +/- 49 vs. 236 +/- 32 kcal/d; P = 0.02) and HC meal (increase, 362 +/- 36 vs. 205 +/- 34 kcal/d; P = 0.0009), but suppressed fat and carbohydrate oxidation. Some of our findings may be mechanisms for lower diabetes and cardiovascular risks in moderate drinkers.

Supramolecular complex of a fused zinc phthalocyanine-zinc porphyrin dyad assembled by two imidazole-C60 units: ultrafast photoevents.

PubMed

Follana-Berná, Jorge; Seetharaman, Sairaman; Martín-Gomis, Luis; Charalambidis, Georgios; Trapali, Adelais; Karr, Paul A; Coutsolelos, Athanassios G; Fernández-Lázaro, Fernando; D'Souza, Francis; Sastre-Santos, Ángela

2018-03-14

A new zinc phthalocyanine-zinc porphyrin dyad (ZnPc-ZnP) fused through a pyrazine ring has been synthesized as a receptor for imidazole-substituted C 60 (C 60 Im) electron acceptor. Self-assembly via metal-ligand axial coordination and the pertinent association constants in solution were determined by 1 H-NMR, UV-Vis and fluorescence titration experiments at room temperature. The designed host was able to bind up to two C 60 Im electron acceptor guest molecules to yield C 60 Im:ZnPc-ZnP:ImC 60 donor-acceptor supramolecular complex. The spectral data showed that the two binding sites behave independently with binding constants similar in magnitude. Steady-state fluorescence studies were indicative of an efficient singlet-singlet energy transfer from zinc porphyrin to zinc phthalocyanine within the fused dyad. Accordingly, the transient absorption studies covering a wide timescale of femto-to-milli seconds revealed ultrafast energy transfer from 1 ZnP* to ZnPc (k EnT ∼ 10 12 s -1 ) in the fused dyad. Further, a photo induced electron transfer was observed in the supramolecularly assembled C 60 Im:ZnPc-ZnP:ImC 60 donor-acceptor complex leading to charge separated states, which persisted for about 200 ns.

Unprotected primary sulfonamide group facilitates ring-forming cascade en route to polycyclic [1,4]oxazepine-based carbonic anhydrase inhibitors.

PubMed

Sapegin, Alexander; Kalinin, Stanislav; Angeli, Andrea; Supuran, Claudiu T; Krasavin, Mikhail

2018-02-01

4-Chloro-3-nitrobenzenesulfonamide reacted cleanly at room-temperature with a range of bis-electrophilic phenols bearing an NH-acidic functionality (secondary carboxamide or pyrazole) in the ortho-position. This produced a novel class of [1,4]oxazepine-based primary sulfonamides which exhibited strong inhibition of therapeutically relevant human carbonic anhydrases. 2-Chloronitrobenzene did not enter a similar cyclocondensation process, even under prolonged heating. Thus, the primary sulfonamide functionality plays a dual role by enabling the [1,4]oxazepine ring construction and acting as a enzyme prosthetic zinc-binding group when the resulting [1,4]oxazepine sulfonamides are employed as carbonic anhydrase inhibitors. Copyright © 2017 Elsevier Inc. All rights reserved.

Experimental clean combustor program, phase 2

NASA Technical Reports Server (NTRS)

Gleason, C. C.; Rogers, D. W.; Bahr, D. W.

1976-01-01

The primary objectives of this three-phase program are to develop technology for the design of advanced combustors with significantly lower pollutant emission levels than those of current combustors, and to demonstrate these pollutant emission reductions in CF6-50C engine tests. The purpose of the Phase 2 Program was to further develop the two most promising concepts identified in the Phase 1 Program, the double annular combustor and the radial/axial staged combustor, and to design a combustor and breadboard fuel splitter control for CF6-50 engine demonstration testing in the Phase 3 Program. Noise measurement and alternate fuels addendums to the basic program were conducted to obtain additional experimental data. Twenty-one full annular and fifty-two sector combustor configurations were evaluated. Both combustor types demonstrated the capability for significantly reducing pollutant emission levels. The most promising results were obtained with the double annular combustor. Rig test results corrected to CF-50C engine conditions produced EPA emission parameters for CO, HC, and NOX of 3.4, 0.4, and 4.5 respectively. These levels represent CO, HC, and NOX reductions of 69, 90, and 42 percent respectively from current combustor emission levels. The combustor also met smoke emission level requirements and development engine performance and installation requirements.

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.

[Short-term effectiveness of minimally invasive percutaneous plate osteosynthesis in treatment of anterior pelvic ring fracture].

PubMed

Chen, Ming; Han, Zhimin; Li, Zhiyun; Cai, Qiangqiang; Tu, Junling

2014-09-01

To investigate the short-term effectiveness of minimally invasive percutaneous plate osteosynthesis (MIPPO) in treatment of anterior pelvic ring fractures. Between January 2012 and October 2013, 16 patients with anterior pelvic ring fractures were treated with MIPPO. There were 10 males and 6 females at the age of 20-63 years (mean, 41 years). The causes of injury were traffic accident in 9 cases and falling from height in 7 cases. The duration of injury to admission was 2 hours to 5 days (mean, 1 day). According to Tile classification, 8 cases were rated as type B2, 4 cases as type B3, 2 cases as type C1, and 2 cases as type C2. Of them, 2 cases had iliac wing fracture, and 4 cases had pelvic posterior ring fracture. The time from admission to operation was 3-12 days (mean, 6 days). The bleeding volume was 60-120 mL (mean, 70 mL). All wounds healed by first intention. No postoperative complication of deep venous thrombosis or long-term continuous pain occurred. All cases were followed up 5-27 months (mean, 11.5 months). No clinical manifestation of lateral femoral cutaneous nerve injury or spermatic cord injury was found, and cremasteric reflex existed in males. All cases obtained bony union, and the healing time was 12-16 weeks (mean, 13 weeks). During the follow-up period, no loss of fracture reduction and no internal fixation loosening or broken were observed. According to Matta radiological evaluation criterion, 16 cases had anatomical reduction, and 3 cases had satisfactory reduction; according to Majeed scoring system of pelvic fracture, the results were excellent in 12 cases and good in 4 cases. MIPPO for treatment of anterior pelvic ring fractures has the advantages of less intraoperative blood loss, few soft tissue complications, and low infection rate, and can get satisfactory short- term effectiveness.

Steric modulation of coordination number and reactivity in the synthesis of lanthanoid(III) formamidinates.

PubMed

Cole, Marcus L; Deacon, Glen B; Forsyth, Craig M; Junk, Peter C; Konstas, Kristina; Wang, Jun

2007-01-01

Reactions of a range of the readily prepared and sterically tunable N,N'-bis(aryl)formamidines with lanthanoid metals and bis(pentafluorophenyl)mercury (Hg(C6F5)2) in THF have given an extensive series of tris(formamidinato)lanthanoid(III) complexes, [Ln(Form)3(thf)n], namely [La(o-TolForm)3(thf)2], [Er(o-TolForm)3(thf)], [La(XylForm)3(thf)], [Sm(XylForm)3], [Ln(MesForm)3] (Ln=La, Nd, Sm and Yb), [Ln(EtForm)3] (Ln=La, Nd, Sm, Ho and Yb), and [Ln(o-PhPhForm)3] (Ln=La, Nd, Sm and Er). [For an explanation of the N,N'-bis(aryl)formamidinate abbreviations used see Scheme 1.] Analogous attempts to prepare [Yb(o-TolForm)3] by this method invariably yielded [{Yb(o-TolForm)2(mu-OH)(thf)}2], but [Yb(o-TolForm)3] was isolated from a metathesis synthesis. X-ray crystal structures show exclusively N,N'-chelation of the Form ligands and a gradation in coordination number with Ln3+ size and with Form ligand bulk. The largest ligands, MesForm, EtForm and o-PhPhForm give solely homoleptic complexes, the first two being six-coordinate, the last having an eta1-pi-Ar--Ln interaction. Reaction of lanthanoid elements and Hg(C6F5)2 with the still bulkier DippFormH in THF resulted in C--F activation and formation of [Ln(DippForm)2F(thf)] (Ln=La, Ce, Nd, Sm and Tm) complexes, and o-HC6F4O(CH2)4DippForm in which the formamidine is functionalised by a ring-opened THF that has trapped tetrafluorobenzyne. Analogous reactions between Ln metals, Hg(o-HC6F4)2 and DippFormH yielded [Ln(DippForm)2F(thf)] (Ln=La, Sm and Nd) and 3,4,5-F3C6H2O(CH2)4DippForm. X-ray crystal structures of the heteroleptic fluorides show six-coordinate monomers with two chelating DippForm ligands and cisoid fluoride and THF ligands in a trigonal prismatic array. The organometallic species [Ln(DippForm)2(C[triple chemical bond]CPh)(thf)] (Ln=Nd or Sm) are obtained from reaction of Nd metal, bis(phenylethynyl)mercury (Hg(C[triple chemical bond]CPh)2) and DippFormH, and the oxidation of [Sm(DippForm)2(thf)2] with Hg(C[triple chemical bond]CPh)2, respectively. The monomeric, six-coordinate, cisoid [Ln(DippForm)2(C[triple chemical bond]CPh)(thf)] complexes have trigonal prismatic geometries and rare (for Ln) terminal C[triple chemical bond]CPh groups with contrasting Ln--C[triple chemical bond]C angles (Ln=Nd, 170.9(4) degrees; Ln=Sm, 142.9(7) degrees). Their formation lends support to the view that [Ln(DippForm)2F(thf)] complexes arise from oxidative formation and C--F activation of [Ln(DippForm)2(C6F5)] intermediates.

Electron attachment and positive ion chemistry of monohydrogenated fluorocarbon radicals

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

Wiens, Justin P.; Shuman, Nicholas S.; Miller, Thomas M.

Rate coefficients and product branching fractions for electron attachment and for reaction with Ar{sup +} are measured over the temperature range 300–585 K for three monohydrogenated fluorocarbon (HFC) radicals (CF{sub 3}CHF, CHF{sub 2}CF{sub 2}, and CF{sub 3}CHFCF{sub 2}), as well as their five closed-shell precursors (1-HC{sub 2}F{sub 4}I, 2-HC{sub 2}F{sub 4}I, 2-HC{sub 2}F{sub 4}Br, 1-HC{sub 3}F{sub 6}I, 2-HC{sub 3}F{sub 6}Br). Attachment to the HFC radicals is always fairly inefficient (between 0.1% and 10% of the Vogt–Wannier capture rate), but generally faster than attachment to analogous perfluorinated carbon radicals. The primary products in all cases are HF-loss to yield C{sub n}F{submore » m−1}{sup −} anions, with only a minor branching to F{sup −} product. In all cases the temperature dependences are weak. Attachment to the precursor halocarbons is near the capture rate with a slight negative temperature dependence in all cases except for 2-HC{sub 2}F{sub 4}Br, which is ∼10% efficient at 300 K and becomes more efficient, approaching the capture rate at higher temperatures. All attachment kinetics are successfully reproduced using a kinetic modeling approach. Reaction of the HFC radicals with Ar{sup +} proceeds at or near the calculated collisional rate coefficient in all cases, yielding a wide variety of product ions.« less

Impact of a high-cholesterol diet on expression levels of Niemann-Pick C1-like 1 and intestinal transporters in rats and mice.

PubMed

Kawase, Atsushi; Araki, Yasuha; Ueda, Yukiko; Nakazaki, Sayaka; Iwaki, Masahiro

2016-08-01

Niemann-Pick C1-like 1 (NPC1L1), ATP-binding cassette (ABC)G5, and ABCG8 are all involved in intestinal cholesterol absorption. It is unclear whether a high-cholesterol (HC) diet affects the expression of these transporters in rats and mice as well as humans. We examined the effects of an HC diet on their expression in small intestine and the differences between rats and mice in the responsive of this expression to an HC diet. In addition to these transporters, alterations in six representative drug and nutrient transporters (multidrug resistance-associated protein, breast cancer resistance protein, peptide transporter, sodium-glucose linked transporter, glucose transporter, and L-type amino acid transporter) and transcriptional factors such as hepatocyte nuclear factor (HNF)4α, sterol regulatory element-binding protein (SREBP)2, and liver X receptor (LXR)α were determined. In rats and mice fed an HC diet for 7 days, the mRNA and protein levels of NPC1L1 in the small intestine were determined by real-time reverse transcription polymerase chain reaction and western blotting, respectively. The mRNA levels of ABCG5 and ABCG8, six representative transporters, and transcriptional factors such as HNF4α, SREBP2, and LXR were examined. Significant decreases in the expression levels of NPC1L1 were observed in mice, but not rats, fed the HC diet. The mRNA levels of ABCG5 and ABCG8 were significantly increased in HC rats but not in mice. Only minor changes in the mRNA levels of the other transporters were seen in HC rats and mice. Decreased mRNA levels of HNF4α and SREBP2 in mice could be involved in the reduction in NPC1L1 expression observed upon the introduction of an HC diet. These results indicate that the effects of an HC diet on the expression levels of NPC1L1, ABCG5, and ABCG8 differ between mice and rats.

Isotopic Ratios in Titan's Atmosphere from Cassini CIRS Limb Sounding: HC3N in the North

NASA Astrophysics Data System (ADS)

Jennings, D. E.; Nixon, C. A.; Jolly, A.; Bézard, B.; Coustenis, A.; Vinatier, S.; Irwin, P. G. J.; Teanby, N. A.; Romani, P. N.; Achterberg, R. K.; Flasar, F. M.

2008-07-01

This Letter reports the first detection of the three 13C isotopologues of HC3N on Titan, from Cassini Composite Infrared Spectrometer (CIRS) infrared spectra. The data are limb spectra taken at latitudes N54°-N69° in 2006 and 2007 when HC3N was enhanced in the north. Using a new line list for the ν5 bands of all isotopologues, we have modeled the isolated emission of H13CCCN at 658.7 cm-1 and both HC13CCN and HCC13CN at 663.0 cm-1, which are blended with the Q-branch of HC3N at 663.3 cm-1 at the resolution of CIRS (0.5 cm-1) and detectable as an increase in the intensity of the low-frequency wing. Using the resolved pair H13CCCN/HC3N we find 12C/13C = 79 +/- 17, in line with other measurements on Titan from Cassini and Huygens.

Closer insight into the reactivity of TMP-dialkyl zincates in directed ortho-zincation of anisole: experimental evidence of amido basicity and structural elucidation of key reaction intermediates.

PubMed

Clegg, William; Conway, Ben; Hevia, Eva; McCall, Matthew D; Russo, Luca; Mulvey, Robert E

2009-02-18

The new dialkyl(aryl) lithium zincates [(THF)(2)Li(C(6)H(4)-OMe)MeZnMe] (4), [(TMEDA)Li(C(6)H(4)-OMe)MeZnMe] (6), [(THF)(3)Li(C(6)H(4)-OMe)(t)BuZn(t)Bu] (7), and [(PMDETA)Li(C(6)H(4)-OMe)(t)BuZn(t)Bu] (8) have been prepared by co-complexation reactions of lithiated anisole with the relevant dialkylzinc compound and the relevant Lewis base. These new heterobimetallic compounds have been characterized in solution using (1)H, (13)C{H}, and (7)Li NMR spectroscopy, and the molecular structures of 6 and 8 have been elucidated by X-ray crystallography. In 6 the distinct metals are connected through the anisole ligand which binds in an ambidentate fashion (through carbon-zinc and oxygen-lithium contacts) and also through one of the methyl groups, to close a [LiOCCZnC] six-membered ring; whereas 8 displays an open structure where anisole connects the two metals (in the same mode as in 6) but with the tert-butyl groups exclusively bonded terminally to zinc. Reactivity studies of zincates 4 and 7 with the amine TMP(H) supply experimental evidence that these heterobimetallic compounds are intermediates in the two-step deprotonation reaction of anisole by TMP-dialkyl zincates and show the relevance of the alkyl groups in the efficiency of TMP-dialkyl zincate bases. In addition, important solvent effects have also been evaluated. When hexane is added to THF solutions of compounds 4 or 7, the homoleptic tetraorganozincate [(THF)(2)Li(2)Zn(C(6)H(4)-OMe)(4)] (5) is obtained as the result of a disproportionation process. This lithium-rich zincate has also been spectroscopically and crystallographically characterized.

Habenular commissure formation in zebrafish is regulated by the pineal gland-specific gene unc119c.

PubMed

Toyama, Reiko; Kim, Mi Ha; Rebbert, Martha L; Gonzales, John; Burgess, Harold; Dawid, Igor B

2013-09-01

The zebrafish pineal gland (epiphysis) is a site of melatonin production, contains photoreceptor cells, and functions as a circadian clock pacemaker. Since it is located on the surface of the forebrain, it is accessible for manipulation and, therefore, is a useful model system to analyze pineal gland function and development. We previously analyzed the pineal transcriptome during development and showed that many genes exhibit a highly dynamic expression pattern in the pineal gland. Among genes preferentially expressed in the zebrafish pineal gland, we identified a tissue-specific form of the unc119 gene family, unc119c, which is highly preferentially expressed in the pineal gland during day and night at all stages examined from embryo to adult. When expression of unc119c was inhibited, the formation of the habenular commissure (HC) was specifically compromised. The Unc119c interacting factors Arl3l1 and Arl3l2 as well as Wnt4a also proved indispensible for HC formation. We suggest that Unc119c, together with Arl3l1/2, plays an important role in modulating Wnt4a production and secretion during HC formation in the forebrain of the zebrafish embryo. Copyright © 2013 Wiley Periodicals, Inc.

Habenular commissure formation in zebrafish is regulated by the pineal gland specific gene unc119c

PubMed Central

Toyama, Reiko; Kim, Mi Ha; Rebbert, Martha L.; Gonzales, John; Burgess, Harold; Dawid, Igor B.

2013-01-01

Background The zebrafish pineal gland (epiphysis) is a site of melatonin production, contains photoreceptor cells, and functions as a circadian clock pacemaker. Since it is located on the surface of the forebrain, it is accessible for manipulation and therefore is a useful model system to analyze pineal gland function and development. We previously analyzed the pineal transcriptome during development and showed that many genes exhibit a highly dynamic expression pattern in the pineal gland. Results Among genes preferentially expressed in the zebrafish pineal gland, we identified a tissue-specific form of the unc119 gene family, unc119c, which is highly preferentially expressed in the pineal gland during day and night at all stages examined from embryo to adult. When expression of unc119c was inhibited, the formation of the habenular commissure (HC) was specifically compromised. The Unc119c interacting factors Arl3l1 and Arl3l2 as well as Wnt4a also proved indispensible for HC formation. Conclusions We suggest that Unc119c, together with Arl3l1/2, plays an important role in modulating Wnt4a production and secretion during HC formation in the forebrain of the zebrafish embryo. PMID:23749482

Improved synthesis of fine zinc borate particles using seed crystals

NASA Astrophysics Data System (ADS)

Gürhan, Deniz; Çakal, Gaye Ö.; Eroğlu, İnci; Özkar, Saim

2009-03-01

Zinc borate is a flame retardant additive used in polymers, wood applications and textile products. There are different types of zinc borate having different chemical compositions and structures. In this study, the production of zinc borate having the molecular formula of 2ZnO·3B 2O 3·3.5H 2O was reexamined by studying the effects of reaction parameters on the properties of product as well as the reaction kinetics. Production of zinc borate from the reaction of boric acid and zinc oxide in the presence of seed crystals was performed in a continuously stirred, temperature-controlled batch reactor having a volume of 1.5 L. Samples taken in regular time intervals during the experiments were analyzed for the concentration of zinc oxide and boron oxide in the solid as well as for the conversion of zinc oxide to zinc borate versus time. The zinc borate production reaction was fit to the logistic model. The reaction rate, reaction completion time, composition and particle size distribution of zinc borate product were determined by varying the following parameters: the boric acid to zinc oxide ratio (H 3BO 3:ZnO=3:1, 3.5:1, 5:1 and 7:1), the particle size of zinc oxide (10 and 25 μm), stirring rate (275, 400, 800 and 1600 rpm), temperature (75, 85 and 95 °C) and the size of seed crystals (10 and 2 μm). The products were also analyzed for particle size distribution. The experimental results showed that the reaction rate increases with the increase in H 3BO 3:ZnO ratio, particle size of zinc oxide, stirring rate and temperature. Concomitantly, the reaction completion time is decreased by increasing the H 3BO 3:ZnO ratio, stirring rate and temperature. The average particle sizes of the zinc borate products are in the range 4.3-16.6 μm (wet dispersion analysis).

Alterations in protein kinase C activity and processing during zinc-deficiency-induced cell death.

PubMed

Chou, Susan S; Clegg, Michael S; Momma, Tony Y; Niles, Brad J; Duffy, Jodie Y; Daston, George P; Keen, Carl L

2004-10-01

Protein kinases C (PKCs) are a family of serine/threonine kinases that are critical for signal transduction pathways involved in growth, differentiation and cell death. All PKC isoforms have four conserved domains, C1-C4. The C1 domain contains cysteine-rich finger-like motifs, which bind two zinc atoms. The zinc-finger motifs modulate diacylglycerol binding; thus, intracellular zinc concentrations could influence the activity and localization of PKC family members. 3T3 cells were cultured in zinc-deficient or zinc-supplemented medium for up to 32 h. Cells cultured in zinc-deficient medium had decreased zinc content, lowered cytosolic classical PKC activity, increased caspase-3 processing and activity, and reduced cell number. Zinc-deficient cytosols had decreased activity and expression levels of PKC-alpha, whereas PKC-alpha phosphorylation was not altered. Inhibition of PKC-alpha with Gö6976 had no effect on cell number in the zinc-deficient group. Proteolysis of the novel PKC family member, PKC-delta, to its 40-kDa catalytic fragment occurred in cells cultured in the zinc-deficient medium. Occurrence of the PKC-delta fragment in mitochondria was co-incident with caspase-3 activation. Addition of the PKC-delta inhibitor, rottlerin, or zinc to deficient medium reduced or eliminated proteolysis of PKC-delta, activated caspase-3 and restored cell number. Inhibition of caspase-3 processing by Z-DQMD-FMK (Z-Asp-Gln-Met-Asp-fluoromethylketone) did not restore cell number in the zinc-deficient group, but resulted in processing of full-length PKC-delta to a 56-kDa fragment. These results support the concept that intracellular zinc concentrations influence PKC activity and processing, and that zinc-deficiency-induced apoptosis occurs in part through PKC-dependent pathways.

Exploring the Transphobia Effect on Heteroleptic NHC Cycloplatinated Complexes.

PubMed

Fuertes, Sara; Chueca, Andrés J; Sicilia, Violeta

2015-10-19

The synthesis of 1-(4-cyanophenyl)-1H-imidazol (1) has been carried out by an improved method. Then its corresponding imidazolium iodide salt, 2, has been used to prepare the N-heterocyclic carbene (NHC) cycloplatinated compound [{Pt(μ-Cl)(C^C*)}2] (4) (HC^C*-κC* = 1-(4-cyanophenyl)-3-methyl-1H-imidazol-2-ylidene) following a step-by-step protocol. The intermediate complex [PtCl(η(3)-2-Me-C3H4) (HC^C*-κC*)] (3) has also been isolated and characterized. Using 4 as precursor, several heteroleptic complexes of stoicheometry [PtCl(C^C*)L] (L = PPh3 (5), pyridine (py, 6), 2,6-dimethylphenyl isocyanide (CNXyl, 7), and 2-mercapto-1-methylimidazole (MMI, 8)) and [Pt(C^C*)LL']PF6 (L = PPh3, L' = py (9), CNXyl (10), and MMI (11)) have been synthesized. Complexes 6-8 were obtained as a mixture of cis- and trans-(C*,L) isomers, while trans-(C*,L) isomer was the only one observed for complexes 5 and 9-11. Their geometries have been discussed in terms of the degree of transphobia (T) of pairs of trans ligands and supported by theoretical calculations. The trans influence of the two σ Pt-C bonds present in these molecules, Pt-C(Ar) and Pt-C*(NHC), has been compared from the J(Pt-P) values observed in the new complex [Pt(C^C*)(dppe)]PF6 (dppe = 1, 2-bis(diphenylphosphino)ethane, 12).

Photolysis and oxidation of azidophenyl-substituted radicals: delocalization in heteroatom-based radicals.

PubMed

Serwinski, Paul R; Esat, Burak; Lahti, Paul M; Liao, Yi; Walton, Richard; Lan, Jiang

2004-08-06

2-(4-Azidophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (14), 2-(4-azidophenyl)benzimidazole-1-oxide-3-oxyl (16), 2-(4-azidophenyl)-1,2,6-triphenylverdazyl (19), 2-(3-azidophenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazole-3-oxide-1-oxyl (21), and (3-azidophenyl)-N-tert-butyl-N-aminoxyl (25) were photolyzed in frozen solution to give S = 3/2 state ESR spectra of the corresponding nitrenophenyl radicals with the following zero-field splitting parameters: |D/hc| = 0.277 cm(-1), |E/hc| < or = 0.002 cm(-1) (7 from 14); |D/hc| = 0.256 cm(-1), |E/hc| < or = 0.002 cm(-1) (8 from 16); |D/hc| = 0.288 cm(-1), |E/hc| < or = 0.002 cm(-1) (9 from 19); |D/hc| = 0.352 cm(-1), |E/hc| = 0.006 cm(-1) (10 from 21); |D/hc| = 0.336 cm(-1), |E/hc| = 0.004 cm(-1) (11 from 25). UB3LYP/6-31G computations and ESR spectroscopic analyses suggest that these are nitreno radicals, even para-linked systems with possible quinonoidal resonance forms. Neat samples of azidophenyl radicals 14 and 21 showed bulk paramagnetic behavior, consistent with the lack of close contacts in their crystal structures. Efforts to make photolabile coordination complexes of 14 and 21 with paramagnetic transition metal ions were unsuccessful: Cu(ClO4)2 x 6H2O instead oxidized them to the corresponding diamagnetic nitrosonium perchlorate salts. Copyright 2004 American Chemical Society

Microbial biotransformation of bioactive flavonoids.

PubMed

Cao, Hui; Chen, Xiaoqing; Jassbi, Amir Reza; Xiao, Jianbo

2015-01-01

The bioactive flavonoids are considered as the most important phytochemicals in food, which exert a wide range of biological benefits for human being. Microbial biotransformation strategies for production of flavonoids have attracted considerable interest because they allow yielding novel flavonoids, which do not exist in nature. In this review, we summarize the existing knowledge on the production and biotransformation of flavonoids by various microbes. The main reactions during microbial biotransformation are hydroxylation, dehydroxylation, O-methylation, O-demethylation, glycosylation, deglycosylation, dehydrogenation, hydrogenation, C ring cleavage of the benzo-γ-pyrone system, cyclization, and carbonyl reduction. Cunninghamella, Penicillium, and Aspergillus strains are very popular to biotransform flavonoids and they can perform almost all the reactions with excellent yields. Aspergillus niger is one of the most applied microorganisms in the flavonoids' biotransformation; for example, A. niger can transfer flavanone to flavan-4-ol, 2'-hydroxydihydrochalcone, flavone, 3-hydroxyflavone, 6-hydroxyflavanone, and 4'-hydroxyflavanone. The hydroxylation of flavones by microbes usually happens on the ortho position of hydroxyl group on the A ring and C-4' position of the B ring and microbes commonly hydroxylate flavonols at the C-8 position. The microorganisms tend to hydroxylate flavanones at the C-5, 6, and 4' positions; however, for prenylated flavanones, dihydroxylation often takes place on the C4α=C5α double bond on the prenyl group (the side chain of A ring). Isoflavones are usually hydroxylated at the C-3' position of the B ring by microorganisms. The microbes convert flavonoids to their 7-O-glycosides and 3-O-glycosides (when flavonoids have a hydroxyl moiety at the C-3 position). The demethylation of multimethoxyl flavonoids by microbes tends to happen at the C-3' and C-4' positions of the B ring. Multimethoxyl flavanones and isoflavone are demethylated at the C-7 and C-4' positions. The O-methylation of flavonols happens at the C-3' and C-4' and microorganisms O-methylate flavones at the C-6 position and the O-methylation of flavanones, usually took place on the hydroxyl groups of the A ring. The prenyl flavanones were cyclized at the prenyl side chain to form a new five-member ring attached to the A ring. Chalcones were regioselectively cyclized to flavanones. Hydrogenation of flavonoids was only reported on transformation of chalcones to dihydrochalcones. The dehydrogenation of flavanoids to flavonoids was not comprehensively studied. Copyright © 2014 Elsevier Inc. All rights reserved.

Structure of the Siz/PIAS SUMO E3 ligase Siz1 and determinants required for SUMO modification of PCNA

PubMed Central

Yunus, Ali A.; Lima, Christopher D.

2009-01-01

Summary Siz1 is a founding member of the Siz/PIAS RING family of SUMO E3 ligases. The x-ray structure of an active Siz1 ligase revealed an elongated tripartite architecture comprised of an N-terminal PINIT domain, a central zinc-containing RING-like SP-RING domain, and a C-terminal domain we term the SP-CTD. Structure-based mutational analysis and biochemical studies show that the SP-RING and SP-CTD are required for activation of the E2~SUMO thioester while the PINIT domain is essential for redirecting SUMO conjugation to the proliferating cell nuclear antigen (PCNA) at lysine 164, a non-consensus lysine residue that is not modified by the SUMO E2 in the absence of Siz1. Mutational analysis of Siz1 and PCNA revealed surfaces on both proteins that are required for efficient SUMO modification of PCNA in vitro and in vivo. PMID:19748360

Characterisation of zinc-binding domains of peroxisomal RING finger proteins using size exclusion chromatography/inductively coupled plasma-mass spectrometry.

PubMed

Koellensperger, Gunda; Daubert, Simon; Erdmann, Ralf; Hann, Stephan; Rottensteiner, Hanspeter

2007-11-01

We determined the zinc binding stoichiometry of peroxisomal RING finger proteins by measuring sulfur/metal ratios using inductively coupled plasma-mass spectrometry coupled to size exclusion chromatography, a strategy that provides a fast and quantitative overview on the binding of metals in proteins. As a quality control, liquid chromatography-electrospray ionisation-time of flight-mass spectrometry was used to measure the molar masses of the intact proteins. The RING fingers of Pex2p, Pex10p, and Pex12p showed a stoichiometry of 2.0, 2.1, and 1.2 mol zinc/mol protein, respectively. Thus, Pex2p and Pex10p possess a typical RING domain with two coordinated zinc atoms, whereas that of Pex12p coordinates only a single zinc atom.

Comparative metabolism and genotoxicity of the structurally similar nitrophenylenediamine dyes, HC Blue 1 and HC Blue 2, in mouse hepatocytes.

PubMed

Kari, F W; Driscoll, S M; Abu-Shakra, A; Strom, S C; Jenkins, W L; Volosin, J S; Rudo, K M; Langenbach, R

1990-04-01

Previous studies indicated that HC Blue 1 induced heptocellular carcinomas in B6C3F1 mice whereas the structurally similar nitroaromatic amine HC Blue 2 did not. In an attempt to elucidate the biochemical mechanisms responsible for their different carcinogenic potencies, comparative metabolism and genetic toxicity studies were undertaken. Eighteen-hour urinary recovery of administered radioactivity was equivalent for both compounds following oral gavage (100 mg/kg) in female B6C3F1 mice. By HPLC analysis, HC Blue 1 yielded 3 major polar metabolite peaks, one of which was susceptible to glucuronidase. In vivo metabolism of HC Blue 2 yielded a single major metabolite peak which was not hydrolyzed by glucuronidase. Metabolism by B6C3F1 mouse hepatocytes yielded metabolite profiles which were qualitatively similar to the profiles observed after in vivo metabolism. HC Blue 1 was metabolized by hepatocytes at approximately twice the rate of HC Blue 2. Cytogenetic evaluations of mouse hepatocytes after in vitro treatment indicated HC Blue 1 was more potent than HC Blue 2 in inducing chromosomal aberrations while both chemicals showed weak activity for inducing sister-chromatid exchanges. Furthermore, in the V79 cell metabolic cooperation assay, HC Blue 1, but not HC Blue 2, inhibited cell-to-cell communication suggesting a non-genotoxic activity may be present for HC Blue 1. It is concluded that qualitative and quantitative differences exist in the metabolism of these compounds and that genotoxic as well as nongenotoxic effects may contribute to their different carcinogenic potencies.

4-(4-Bromo-phen-yl)-1-(2,6-difluoro-benz-yl)-3-(3,4,5-trimeth-oxy-phen-yl)-1H-1,2,4-triazole-5(4H)-thione.

PubMed

Fun, Hoong-Kun; Ooi, Chin Wei; Chandrakantha, B; Isloor, Arun M; Shetty, Prakash

2012-01-01

In the title compound, C(24)H(20)BrF(2)N(3)O(3)S, the triazole ring (r.m.s. deviation = 0.0107 Å) makes dihedral angles of 28.18 (14), 63.76 (14) and 77.01 (18)°, respectively, with the trimeth-oxy-, bromo-, and difluoro-substituted benzene rings. The C atoms of the meta meth-oxy groups are roughly coplanar with their ring [displacements = -0.289 (4) and 0.083 (7) Å], whereas the C atom of the para group is displaced [1.117 (3) Å]. In the crystal, inversion dimers linked by two pairs of C-H⋯O hydrogen bonds occur. The ring motif of the two hydrogen bonds to their symmetry-generated O-atom acceptors is R(2) (2)(8).

Low carbohydrate, high fat diet increases C-reactive protein during weight loss.

PubMed

Rankin, Janet W; Turpyn, Abigail D

2007-04-01

Chronic inflammation is associated with elevated risk of heart disease and may be linked to oxidative stress in obesity. Our objective was to evaluate the effect of weight loss diet composition (low carbohydrate, high fat, LC or high carbohydrate, low fat, HC) on inflammation and to determine whether this was related to oxidative stress. Twenty nine overweight women, BMI 32.1 +/- 5.4 kg/m(2), were randomly assigned to a self-selected LC or HC diet for 4 wks. Weekly group sessions and diet record collections helped enhance compliance. Body weight, markers of inflammation (serum interleukin-6, IL-6; C-reactive protein, CRP) oxidative stress (urinary 8-epi-prostaglandin F2alpha, 8-epi) and fasting blood glucose and free fatty acids were measured weekly. The diets were similar in caloric intake (1357 kcal/d LC vs. 1361 HC, p=0.94), but differed in macronutrients (58, 12, 30 and 24, 59, 18 for percent of energy as fat, carbohydrate, and protein for LC and HC, respectively). Although LC lost more weight (3.8 +/- 1.2 kg LC vs. 2.6 +/- 1.7 HC, p=0.04), CRP increased 25%; this factor was reduced 43% in HC (p=0.02). For both groups, glucose decreased with weight loss (85.4 vs. 82.1 mg/dl for baseline and wk 4, p<0.01), while IL-6 increased (1.39 to 1.62 pg/mL, p=0.04). Urinary 8-epi varied differently over time between groups (p<0.05) with no consistent pattern. Diet composition of the weight loss diet influenced a key marker of inflammation in that LC increased while HC reduced serum CRP but evidence did not support that this was related to oxidative stress.

Titan haze: structure and properties of cyanoacetylene and cyanoacetylene-acetylene photopolymers

NASA Technical Reports Server (NTRS)

Clarke, D. W.; Ferris, J. P.

1997-01-01

The structure and morphological properties of polymers produced photochemically from the UV irradiation of cyanoacetylene and cyanoacetylene mixtures have been examined to evaluate their possible contribution to the haze layers found on Titan. A structural analysis of these polymers may contribute to our understanding of the data returned from the Huygens probe of the Cassini mission that will pass through the atmosphere of Titan in the year 2004. Infrared analysis, elemental analysis, and thermal methods (thermogravimetric analysis, thermolysis, pyrolysis) were used to examine structures of polycyanoacetylenes produced by irradiation of the gas phase HC3N at 185 and 254 nm. The resulting brown to black polymer, which exists as small particles, is believed to be a branched chain of conjugated carbon-carbon double bonds, which, on exposure to heat, cyclizes to form a graphitic structure. Similar methods of analysis were used to show that when HC3N is photolyzed in the presence of Titan's other atmospheric constituents (CH4, C2H6, C2H2, and CO), a copolymer is formed in which the added gases are incorporated as substituents on the polymer chain. Of special significance is the copolymer of HC3N and acetylene (C2H2). Even in experiments where C2H2 was absorbing nearly all of the incident photons, the ratio of C2H2 to HC3N found in the resulting polymer was only 2:1. Scanning electron microscopy was used to visually examine the polymer particles. While pure polyacetylene particles are amorphous spheres roughly 1 micrometer in diameter, polycyanoacetylenes appear to be strands of rough, solid particles slightly smaller in size. The copolymer of HC3N and C2H2 exhibits characteristics of both pure polymers. This is particularly important as pure polyacetylenes do not match the optical constants measured for Titan's atmospheric hazes. The copolymers produced by the incorporation of other minor atmospheric constituents, like HC3N, into the polyacetylenes are expected to have optical constants more comparable to those of the Titan haze.

5-phosphonato-3,4-dihydropyrimidin-2(1H)-ones: Zinc triflate-catalyzed one-pot multi-component synthesis, X-ray crystal structure and anti-inflammatory activity

NASA Astrophysics Data System (ADS)

Essid, Idris; Lahbib, Karima; Kaminsky, Werner; Ben Nasr, Cherif; Touil, Soufiane

2017-08-01

Herein we report a simple and efficient one-pot three-component synthesis of 5-phosphonato-3,4-dihydropyrimidin-2(1H)-ones, through the zinc triflate-catalyzed Biginelli-type reaction of β-ketophosphonates, aldehydes and urea. The compounds obtained were characterized by various spectroscopic tools including IR, NMR (1H, 31P, 13C) spectroscopy, mass spectrometry and single crystal X-ray diffraction. All the synthesized compounds were screened, for the first time, for anti-inflammatory activity by carrageenan-induced hind paw edema method, using female Wister rats and they showed significant anti-inflammatory activity in some cases higher than the standard indomethacin.

Felix Spectroscopy of Likely Astronomical Molecular Ions: HC_3O^+, C_2H_3CNH^+, and C_2H_5CNH^+

NASA Astrophysics Data System (ADS)

Thorwirth, Sven; Asvany, Oskar; Brünken, Sandra; Jusko, Pavol; Schlemmer, Stephan; Martin-Drumel, Marie-Aline; McCarthy, Michael C.

2017-06-01

Infrared signatures of three molecular ions of relevance to the interstellar medium and planetary atmospheres have been detected at the Free Electron Laser for Infrared eXperiments, FELIX, at Radboud University (Nijmegen, The Netherlands) in combination with the 4K FELion 22-pole ion trap facility. Mid-infrared vibrational modes of protonated tricarbon monoxide, HC_3O^+, protonated vinyl cyanide, C_2H_3CNH^+, and protonated ethyl cyanide, C_2H_5CNH^+, were detected using resonant photodissociation of the respective Ne-complexes by monitoring the depletion of their cluster mass signal as a function of wavenumber. The infrared fingerprints compare very favorably with results from high-level quantum-chemical calculations performed at the CCSD(T) level of theory.

Growth of antimony doped P-type zinc oxide nanowires for optoelectronics

DOEpatents

Wang, Zhong Lin; Pradel, Ken

2016-09-27

In a method of growing p-type nanowires, a nanowire growth solution of zinc nitrate (Zn(NO.sub.3).sub.2), hexamethylenetetramine (HMTA) and polyethylenemine (800 M.sub.w PEI) is prepared. A dopant solution to the growth solution, the dopant solution including an equal molar ration of sodium hydroxide (NaOH), glycolic acid (C.sub.2H.sub.4O.sub.3) and antimony acetate (Sb(CH.sub.3COO).sub.3) in water is prepared. The dopant solution and the growth solution combine to generate a resulting solution that includes antimony to zinc in a ratio of between 0.2% molar to 2.0% molar, the resulting solution having a top surface. An ammonia solution is added to the resulting solution. A ZnO seed layer is applied to a substrate and the substrate is placed into the top surface of the resulting solution with the ZnO seed layer facing downwardly for a predetermined time until Sb-doped ZnO nanowires having a length of at least 5 .mu.m have grown from the ZnO seed layer.

Four faces of the interaction between ions and aromatic rings.

PubMed

Papp, Dóra; Rovó, Petra; Jákli, Imre; Császár, Attila G; Perczel, András

2017-07-15

Non-covalent interactions between ions and aromatic rings play an important role in the stabilization of macromolecular complexes; of particular interest are peptides and proteins containing aromatic side chains (Phe, Trp, and Tyr) interacting with negatively (Asp and Glu) and positively (Arg and Lys) charged amino acid residues. The structures of the ion-aromatic-ring complexes are the result of an interaction between the large quadrupole moment of the ring and the charge of the ion. Four attractive interaction types are proposed to be distinguished based on the position of the ion with respect to the plane of the ring: perpendicular cation-π (CP ⊥ ), co-planar cation-π (CP ∥ ), perpendicular anion-π (AP ⊥ ), and co-planar anion-π (AP ∥ ). To understand more than the basic features of these four interaction types, a systematic, high-level quantum chemical study is performed, using the X -  + C 6 H 6 , M +  + C 6 H 6 , X -  + C 6 F 6 , and M +  + C 6 F 6 model systems with X -  = H - , F - , Cl - , HCOO - , CH 3 COO - and M +  = H + , Li + , Na + , NH4+, CH 3 NH3+, whereby C 6 H 6 and C 6 F 6 represent an electron-rich and an electron-deficient π system, respectively. Benchmark-quality interaction energies with small uncertainties, obtained via the so-called focal-point analysis (FPA) technique, are reported for the four interaction types. The computations reveal that the interactions lead to significant stabilization, and that the interaction energy order, given in kcal mol -1 in parentheses, is CP ⊥ (23-37) > AP ⊥ (14-21) > CP ∥ (9-22) > AP ∥ (6-16). A natural bond orbital analysis performed leads to a deeper qualitative understanding of the four interaction types. To facilitate the future quantum chemical characterization of ion-aromatic-ring interactions in large biomolecules, the performance of three density functional theory methods, B3LYP, BHandHLYP, and M06-2X, is tested against the FPA benchmarks, with the result that the M06-2X functional performs best. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

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.

Uranium and organic matters: use of pyrolysis-gas chromatography, carbon, hydrogen, and uranium contents to characterize the organic matter from sandstone-type deposits

USGS Publications Warehouse

Leventhal, Joel S.

1979-01-01

Organic matter seems to play an important role in the genesis of uranium deposits in sandstones in the western United States. Organic materials associated with ore from the Texas coastal plain, Tertiary basins of Wyoming, Grants mineral belt of New Mexico, and the Uravan mineral belt of Utah and Colorado vary widely in physical appearance and chemical composition. Partial characterization of organic materials is achieved by chemical analyses to determine atomic hydrogen-to-carbon (H/C) ratios and by gas chromatographic analyses to determine the molecular fragments evolved during stepwise pyrolysis. From the pyrolysis experiments the organic materials can be classified and grouped: (a) lignites from Texas and Wyoming and (b) hydrogen poor materials, from Grants and Uravan mineral belts and Wyoming; (c) naphthalene-containing materials from Grants mineral belt and Wyoming; and (d) complex and aromatic materials from Uravan, Grants and Wyoming. The organic materials analyzed have atomic H/C ratios that range from approximately 0.3 to at least 1.5. The samples with higher H/C ratios yield pyrolysis products that contain as many as 30 carbon atoms per molecule. Samples with low H/C ratios are commonly more uraniferous and yield mostly methane and low-molecular-weight gases during pyrolysis.

Structural characterization by both positive and negative electrospray ion trap mass spectrometry of oligogalacturonates purified by high-performance anion-exchange chromatography.

PubMed

Quéméner, Bernard; Désiré, Cédric; Debrauwer, Laurent; Rathahao, Estelle

2003-01-17

The off-line coupling of high-performance anion-exchange chromatography to electrospray ion trap mass spectrometry (ESI-IT-MS) is described. Two sets of isocratic conditions were optimised for the semi-preparative purification of oligogalacturonates of degree of polymerisation from 4 to 6 by monitoring eluates with either pulsed amperometric detection or evaporative light scattering detection in the presence of an online Dionex Carbohydrate Membrane Desalter (CMD). In these conditions, purified oligogalacturonate solutions were suitable, without further desalting steps, for infusion ESI-IT-MS experiments. This paper provides some interesting features of positive and negative ESI-IT-multiple MS (MSn) of these acidic oligosaccharides. The spectra acquired in both ion modes show characteristic fragments resulting from glycosidic bond and cross-ring cleavages. Under negative ionization conditions, the fragmentation of the singly-charged [M-H]- ions, as well as the Ci-, and Zi-, fragment ions through sequential MSn experiments, was always dominated by product ions from C- and Z-type glycosidic cleavages. All spectra also displayed 0.2 A-type cross-ring cleavage ions which carry linkage information. Collision-induced dissociation (CID) spectra of sodium-cationized species obtained under positive ionization conditions were more complex. Successive MSn experiments also led to the 0.2 A-type cross-ring cleavage ions observed together with B- and Y-type ions. The presence of the 0.2 A ion series was related to Mr 60 (C2H4O2) losses. Combined with the absence of the Mr 30 (CH2O) and the Mr 90 (C3H6O3) ions, these ions were indicative of 1-4 type glycosidic linkage.

Two-dimensional Zn(II) and one-dimensional Co(II) coordination polymers based on benzene-1,4-dicarboxylate and pyridine ligands.

PubMed

Zhou, Li-Juan; Han, Chang-Bao; Wang, Yu-Ling

2016-02-01

Coordination polymers constructed from metal ions and organic ligands have attracted considerable attention owing to their diverse structural topologies and potential applications. Ligands containing carboxylate groups are among the most extensively studied because of their versatile coordination modes. Reactions of benzene-1,4-dicarboxylic acid (H2BDC) and pyridine (py) with Zn(II) or Co(II) yielded two new coordination polymers, namely, poly[(μ4-benzene-1,4-dicarboxylato-κ(4)O:O':O'':O''')(pyridine-κN)zinc(II)], [Zn(C8H4O2)(C5H5N)]n, (I), and catena-poly[aqua(μ3-benzene-1,4-dicarboxylato-κ(3)O:O':O'')bis(pyridine-κN)cobalt(II)], [Co(C8H4O2)(C5H5N)2(H2O)]n, (II). In compound (I), the Zn(II) cation is five-coordinated by four carboxylate O atoms from four BDC(2-) ligands and one pyridine N atom in a distorted square-pyramidal coordination geometry. Four carboxylate groups bridge two Zn(II) ions to form centrosymmetric paddle-wheel-like Zn2(μ2-COO)4 units, which are linked by the benzene rings of the BDC(2-) ligands to generate a two-dimensional layered structure. The two-dimensional layer is extended into a three-dimensional supramolecular structure with the help of π-π stacking interactions between the aromatic rings. Compound (II) has a one-dimensional double-chain structure based on Co2(μ2-COO)2 units. The Co(II) cations are bridged by BDC(2-) ligands and are octahedrally coordinated by three carboxylate O atoms from three BDC(2-) ligands, one water O atom and two pyridine N atoms. Interchain O-H...O hydrogen-bonding interactions link these chains to form a three-dimensional supramolecular architecture.

(3+1)-Dimensional topologically massive 2-form gauge theory: geometrical superfield approach

NASA Astrophysics Data System (ADS)

Kumar, R.; Mukhopadhyay, Debmalya

2018-06-01

We derive the complete set of off-shell nilpotent and absolutely anticommuting Becchi-Rouet-Stora-Tyutin (BRST) and anti-BRST symmetry transformations corresponding to the combined "scalar" and "vector" gauge symmetry transformations for the (3+1)-dimensional (4D) topologically massive non-Abelian (B \\wedge F) theory with the help of geometrical superfield formalism. For this purpose, we use three horizontality conditions (HCs). The first HC produces the (anti-)BRST transformations for the 1-form gauge field and corresponding (anti-)ghost fields whereas the second HC yields the (anti-)BRST transformations for 2-form field and associated (anti-)ghost fields. The integrability of second HC produces third HC. The latter HC produces the (anti-)BRST symmetry transformations for the compensating auxiliary vector field and corresponding ghosts. We obtain five (anti-)BRST invariant Curci-Ferrari (CF)-type conditions which emerge very naturally as the off-shoots of superfield formalism. Out of five CF-type conditions, two are fermionic in nature. These CF-type conditions play a decisive role in providing the absolute anticommutativity of the (anti-)BRST transformations and also responsible for the derivation of coupled but equivalent (anti-)BRST invariant Lagrangian densities. Furthermore, we capture the (anti-)BRST invariance of the coupled Lagrangian densities in terms of the superfields and translation generators along the Grassmannian directions θ and \\bar{θ }.

A priori predictions of the rotational constants for HC13N, HC15N, C5O

NASA Technical Reports Server (NTRS)

DeFrees, D. J.; McLean, A. D.

1989-01-01

Ab initio molecular orbital theory is used to estimate the rotational constant for several carbon-chain molecules that are candidates for discovery in interstellar space. These estimated rotational constants can be used in laboratory or astronomical searches for the molecules. The rotational constant for HC13N is estimated to be 0.1073 +/- 0.0002 GHz and its dipole moment 5.4 D. The rotational constant for HC15N is estimated to be 0.0724 GHz, with a somewhat larger uncertainty. The rotational constant of C5O is estimated to be 1.360 +/- 2% GHz and its dipole moment 4.4. D.

Zinc deficiency mediates alcohol-induced apoptotic cell death in the liver of rats through activating ER and mitochondrial cell death pathways

PubMed Central

Sun, Qian; Zhong, Wei; Zhang, Wenliang; Li, Qiong; Sun, Xiuhua; Tan, Xiaobing; Sun, Xinguo; Dong, Daoyin

2015-01-01

Hepatic zinc deficiency has been well documented in alcoholic patients, but the mechanisms by which zinc deficiency mediates cell death have not been well defined. The objectives of this study were to determine whether alcohol perturbs subcellular zinc homeostasis and how organelle zinc depletion may link with cell death pathways. Wistar rats were pair-fed with the Lieber-DeCarli control or ethanol diet for 5 mo. Chronic alcohol exposure significantly reduced zinc level in isolated hepatic endoplasmic reticulum (ER) and mitochondria. Among the detected zinc transporters, ER Zrt/Irt-like protein (ZIP)13 and mitochondrial ZIP8, which transport zinc from ER and mitochondria to cytosol, were significantly increased. Mitochondrial zinc transporter (ZnT) 4, which transports zinc from cytosol to mitochondria, was also increased. ER phosphorylated eukaryotic initiation factor 2α, activating transcription factor 4, and C/EBP homologous protein were significantly upregulated, and mitochondrial cytochrome c release and Bax insertion were detected in association with caspase-3 activation and apoptotic cell death. To define the role of zinc deficiency in ER and mitochondrial stress, H4IIEC3 cells were treated with 3 μM N,N,N′,N′-tetrakis (2-pyridylmethyl) ethylenediamine for 6 h with or without supplementation with zinc or N-acetylcysteine (NAC). The results demonstrated that zinc deprivation induced caspase-3 activation and apoptosis in association with ER and mitochondria dysfunction, which were inhibited by zinc as low as 10 μM but not by 2 mM NAC. These results suggest that chronic ethanol exposure induced in ER and mitochondrial zinc deficiency might activate intrinsic cell death signaling pathway, which could not be effectively rescued by antioxidant treatment. PMID:25767260

Synthesis and structures of bis-ligated zinc complexes supported by tridentate ketoimines that initiate L-lactide polymerization.

PubMed

Gerling, Kimberly A; Rezayee, Nomaan M; Rheingold, Arnold L; Green, David B; Fritsch, Joseph M

2014-11-21

Eight bis-ligated, homoleptic, zinc complexes were synthesized through the reaction of NNO Schiff base ketoimines bearing varying substituents with diethyl zinc in an inert atmosphere glovebox at room temperature and isolated in 62-95% yield. The complexes were characterized with (1)H, (13)C, and (19)F nuclear magnetic resonance spectroscopy, absorbance spectroscopy, high resolution mass spectrometry, elemental analysis, and single crystal X-ray crystallography. The complexes were shown to adopt distorted octahedral coordination geometry around zinc. The (1)H and (19)F NMR spectra of complexes 1-7 showed stable zinc coordination at 300 K while the effect of steric encumbrance and two trifluoromethyl groups in complex 8 was investigated with variable temperature NMR. The bis-ligated zinc complexes were effective initiators for the ring opening polymerization of L-lactide into poly-L-lactic acid (PLLA). With [L-lac]/[Zn complex] = 50, the bis-ligated zinc complexes yielded percentage conversion of 14-98% with polymerization times varying from 15-1440 min, where the longest reaction times were required when two trifluoromethyl groups were present. The addition of 4-fluorophenol co-catalyst resulted in up to a 5-fold increase in the percentage conversion in toluene solution and up to a 14-fold increase in bulk melt polymerization with reductions in the poly-dispersity index values for the isolated PLLA. Addition of 4-fluorophenol to complex 1 was studied with (1)H and (19)F NMR and appeared to yield an in situ generated zinc alkoxide complex.

AT1 Receptor Modulator Attenuates the Hypercholesterolemia-Induced Impairment of the Myocardial Ischemic Post-Conditioning Benefits.

PubMed

Li, Yun-Wei; Li, Yan-Ming; Hon, Yan; Wan, Qi-Lin; He, Rui-Li; Wang, Zhi-Zhong; Zhao, Cui-Hua

2017-03-01

Ischemic post-conditioning (PostC) has been demonstrated as a novel strategy to harness nature's protection against myocardial ischemia-reperfusion (I/R). Hypercholesterolemia (HC) has been reported to block the effect of PostC on the heart. Angiotensin II type-1 (AT1) modulators have shown benefits in myocardial ischemia. The present study investigates the effect of a novel inhibitor of AT1, azilsartan in PostC of the heart of normocholesterolemic (NC) and HC rats. HC was induced by the administration of high-fat diet to the animals for eight weeks. Isolated Langendorff's perfused NC and HC rat hearts were exposed to global ischemia for 30 min and reperfusion for 120 min. I/R-injury had been assessed by cardiac hemodynamic parameters, myocardial infarct size, release of tumor necrosis factor-alpha troponin I, lactate dehydrogenase, creatine kinase, nitrite in coronary effluent, thiobarbituric acid reactive species, a reduced form of glutathione, superoxide anion, and left ventricle collagen content in normal and HC rat hearts. Azilsartan post-treatment and six episodes of PostC (10 sec each) afforded cardioprotection against I/R-injury in normal rat hearts. PostC protection against I/R-injury was abolished in HC rat hearts. Azilsartan prevented the HC-mediated impairment of the beneficial effects of PostC in I/R-induced myocardial injury, which was inhibited by L-N 5 -(1-Iminoethyl)ornithinehydrochloride, a potent inhibitor of endothelial nitric oxide synthase (eNOS). Azilsartan treatment has attenuated the HC-induced impairment of beneficial effects of PostC in I/R-injury of rat hearts, by specifically modulating eNOS. Azilsartan may be explored further in I/R-myocardial injury, both in NC and HC conditions, with or without PostC.

AT1 Receptor Modulator Attenuates the Hypercholesterolemia-Induced Impairment of the Myocardial Ischemic Post-Conditioning Benefits

PubMed Central

Li, Yun-Wei; Hon, Yan; Wan, Qi-Lin; He, Rui-Li; Wang, Zhi-Zhong; Zhao, Cui-Hua

2017-01-01

Background and Objectives Ischemic post-conditioning (PostC) has been demonstrated as a novel strategy to harness nature's protection against myocardial ischemia-reperfusion (I/R). Hypercholesterolemia (HC) has been reported to block the effect of PostC on the heart. Angiotensin II type-1 (AT1) modulators have shown benefits in myocardial ischemia. The present study investigates the effect of a novel inhibitor of AT1, azilsartan in PostC of the heart of normocholesterolemic (NC) and HC rats. Materials and Methods HC was induced by the administration of high-fat diet to the animals for eight weeks. Isolated Langendorff's perfused NC and HC rat hearts were exposed to global ischemia for 30 min and reperfusion for 120 min. I/R-injury had been assessed by cardiac hemodynamic parameters, myocardial infarct size, release of tumor necrosis factor-alpha troponin I, lactate dehydrogenase, creatine kinase, nitrite in coronary effluent, thiobarbituric acid reactive species, a reduced form of glutathione, superoxide anion, and left ventricle collagen content in normal and HC rat hearts. Results Azilsartan post-treatment and six episodes of PostC (10 sec each) afforded cardioprotection against I/R-injury in normal rat hearts. PostC protection against I/R-injury was abolished in HC rat hearts. Azilsartan prevented the HC-mediated impairment of the beneficial effects of PostC in I/R-induced myocardial injury, which was inhibited by L-N5-(1-Iminoethyl)ornithinehydrochloride, a potent inhibitor of endothelial nitric oxide synthase (eNOS). Conclusion Azilsartan treatment has attenuated the HC-induced impairment of beneficial effects of PostC in I/R-injury of rat hearts, by specifically modulating eNOS. Azilsartan may be explored further in I/R-myocardial injury, both in NC and HC conditions, with or without PostC. PMID:28382073

Crystal structure of catena-poly[[[tetra-aqua-zinc(II)]-μ-1,4-bis-[4-(1H-imidazol-1-yl)benzo-yl]piperazine] dinitrate monohydrate].

PubMed

Hou, Chen; Gan, Hong-Mei; Liu, Jia-Cheng

2015-05-01

In the title polymeric complex, {[Zn(C24H22N6O2)(H2O)4](NO3)2·2H2O} n , the Zn(II) cation, located about a twofold rotation axis, is coordinated by two imidazole groups and four water mol-ecules in a distorted N2O4 octa-hedral geometry; among the four coordinate water mol-ecules, two are located on the same twofold rotation axis. The 1,4-bis-[4-(1H-imidazol-1-yl)benzo-yl]piperazine] ligand is centro-symmetric, with the centroid of the piperazine ring located on an inversion center, and bridges the Zn(II) cations, forming polymeric chains propagating along [201]. In the crystal, O-H⋯O and weak C-H⋯O hydrogen bonds link the polymeric chains, nitrate anions and solvent water mol-ecules into a three-dimensional supra-molecular architecture. A short O⋯O contact of 2.823 (13) Å is observed between neighboring nitrate anions.

CaB2 S4 O16 : A Borosulfate Exhibiting a New Structure Type with Phyllosilicate Analogue Topology.

PubMed

Bruns, Jörn; Podewitz, Maren; Schauperl, Michael; Joachim, Bastian; Liedl, Klaus R; Huppertz, Hubert

2017-11-27

The reaction of Ca(CO 3 ) with H 3 BO 3 in oleum (20 % SO 3 ) yielded colorless single-crystals of CaB 2 S 4 O 16 (monoclinic, P2 1 /c, a=5.5188(2), b=15.1288(6), c=13.2660(6) Å, β=92.88(1)°, V=1106.22(8) Å 3 ). X-ray single-crystal structure analysis revealed a phyllosilicate-analogue anionic sub-structure, forming 2D infinite anionic layers, which exhibit an unprecedented arrangement of condensed twelve-membered (zwölfer) and four-membered (vierer) rings of corner-shared (SO 4 ) and (BO 4 ) tetrahedra. Charge compensation is achieved by Ca 2+ cations, residing exclusively above the centers of the twelve-membered rings. DFT investigations on the solid-state structure corroborate the experimental findings and allow for a detailed valuation of charge distribution within the anionic network and an assignment of vibrational frequencies. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The Association of Combined GSTM1 and CYP2C9 Genotype Status with the Occurrence of Hemorrhagic Cystitis in Pediatric Patients Receiving Myeloablative Conditioning Regimen Prior to Allogeneic Hematopoietic Stem Cell Transplantation

PubMed Central

Uppugunduri, Chakradhara Rao S.; Storelli, Flavia; Mlakar, Vid; Huezo-Diaz Curtis, Patricia; Rezgui, Aziz; Théorêt, Yves; Marino, Denis; Doffey-Lazeyras, Fabienne; Chalandon, Yves; Bader, Peter; Daali, Youssef; Bittencourt, Henrique; Krajinovic, Maja; Ansari, Marc

2017-01-01

Hemorrhagic cystitis (HC) is one of the complications of busulfan-cyclophosphamide (BU-CY) conditioning regimen during allogeneic hematopoietic stem cell transplantation (HSCT) in children. Identifying children at high risk of developing HC in a HSCT setting could facilitate the evaluation and implementation of effective prophylactic measures. In this retrospective analysis genotyping of selected candidate gene variants was performed in 72 children and plasma Sulfolane (Su, water soluble metabolite of BU) levels were measured in 39 children following treatment with BU-CY regimen. The cytotoxic effects of Su and acrolein (Ac, water soluble metabolite of CY) were tested on human urothelial cells (HUCs). The effect of Su was also tested on cytochrome P 450 (CYP) function in HepaRG hepatic cells. Cumulative incidences of HC before day 30 post HSCT were estimated using Kaplan–Meier curves and log-rank test was used to compare the difference between groups in a univariate analysis. Multivariate Cox regression was used to estimate hazard ratios with 95% confidence intervals (CIs). Multivariate analysis included co-variables that were significantly associated with HC in a univariate analysis. Cumulative incidence of HC was 15.3%. In the univariate analysis, HC incidence was significantly (p < 0.05) higher in children older than 10 years (28.6 vs. 6.8%) or in children with higher Su levels (>40 vs. <11%) or in carriers of both functional GSTM1 and CYP2C9 (33.3 vs. 6.3%) compared to the other group. In a multivariate analysis, combined GSTM1 and CYP2C9 genotype status was associated with HC occurrence with a hazards ratio of 4.8 (95% CI: 1.3–18.4; p = 0.02). Ac was found to be toxic to HUC cells at lower concentrations (33 μM), Su was not toxic to HUC cells at concentrations below 1 mM and did not affect CYP function in HepaRG cells. Our observations suggest that pre-emptive genotyping of CYP2C9 and GSTM1 may aid in selection of more effective prophylaxis to reduce HC development in pediatric patients undergoing allogeneic HSCT. Article summary: (1) Children carrying functional alleles in GSTM1 and CYP2C9 are at high risk for developing hemorrhagic cystitis following treatment with busulfan and cyclophosphamide based conditioning regimen. (2) Identification of children at high risk for developing hemorrhagic cystitis in an allogeneic HSCT setting will enable us to evaluate and implement optimal strategies for its prevention. Trial registration: This study is a part of the trail “clinicaltrials.gov identifier: NCT01257854.” PMID:28744217

The Association of Combined GSTM1 and CYP2C9 Genotype Status with the Occurrence of Hemorrhagic Cystitis in Pediatric Patients Receiving Myeloablative Conditioning Regimen Prior to Allogeneic Hematopoietic Stem Cell Transplantation.

PubMed

Uppugunduri, Chakradhara Rao S; Storelli, Flavia; Mlakar, Vid; Huezo-Diaz Curtis, Patricia; Rezgui, Aziz; Théorêt, Yves; Marino, Denis; Doffey-Lazeyras, Fabienne; Chalandon, Yves; Bader, Peter; Daali, Youssef; Bittencourt, Henrique; Krajinovic, Maja; Ansari, Marc

2017-01-01

Hemorrhagic cystitis (HC) is one of the complications of busulfan-cyclophosphamide (BU-CY) conditioning regimen during allogeneic hematopoietic stem cell transplantation (HSCT) in children. Identifying children at high risk of developing HC in a HSCT setting could facilitate the evaluation and implementation of effective prophylactic measures. In this retrospective analysis genotyping of selected candidate gene variants was performed in 72 children and plasma Sulfolane (Su, water soluble metabolite of BU) levels were measured in 39 children following treatment with BU-CY regimen. The cytotoxic effects of Su and acrolein (Ac, water soluble metabolite of CY) were tested on human urothelial cells (HUCs). The effect of Su was also tested on cytochrome P 450 (CYP) function in HepaRG hepatic cells. Cumulative incidences of HC before day 30 post HSCT were estimated using Kaplan-Meier curves and log-rank test was used to compare the difference between groups in a univariate analysis. Multivariate Cox regression was used to estimate hazard ratios with 95% confidence intervals (CIs). Multivariate analysis included co-variables that were significantly associated with HC in a univariate analysis. Cumulative incidence of HC was 15.3%. In the univariate analysis, HC incidence was significantly ( p < 0.05) higher in children older than 10 years (28.6 vs. 6.8%) or in children with higher Su levels (>40 vs. <11%) or in carriers of both functional GSTM1 and CYP2C9 (33.3 vs. 6.3%) compared to the other group. In a multivariate analysis, combined GSTM1 and CYP2C9 genotype status was associated with HC occurrence with a hazards ratio of 4.8 (95% CI: 1.3-18.4; p = 0.02). Ac was found to be toxic to HUC cells at lower concentrations (33 μM), Su was not toxic to HUC cells at concentrations below 1 mM and did not affect CYP function in HepaRG cells. Our observations suggest that pre-emptive genotyping of CYP2C9 and GSTM1 may aid in selection of more effective prophylaxis to reduce HC development in pediatric patients undergoing allogeneic HSCT. Article summary : (1) Children carrying functional alleles in GSTM1 and CYP2C9 are at high risk for developing hemorrhagic cystitis following treatment with busulfan and cyclophosphamide based conditioning regimen. (2) Identification of children at high risk for developing hemorrhagic cystitis in an allogeneic HSCT setting will enable us to evaluate and implement optimal strategies for its prevention. Trial registration : This study is a part of the trail "clinicaltrials.gov identifier: NCT01257854."

Comparison of clinical and analytical performance of the Abbott Realtime High Risk HPV test to the performance of hybrid capture 2 in population-based cervical cancer screening.

PubMed

Poljak, Mario; Ostrbenk, Anja; Seme, Katja; Ucakar, Veronika; Hillemanns, Peter; Bokal, Eda Vrtacnik; Jancar, Nina; Klavs, Irena

2011-05-01

The clinical performance of the Abbott RealTime High Risk HPV (human papillomavirus) test (RealTime) and that of the Hybrid Capture 2 HPV DNA test (hc2) were prospectively compared in the population-based cervical cancer screening setting. In women >30 years old (n = 3,129), the clinical sensitivity of RealTime for detection of cervical intraepithelial neoplasia of grade 2 (CIN2) or worse (38 cases) and its clinical specificity for lesions of less than CIN2 (3,091 controls) were 100% and 93.3%, respectively, and those of hc2 were 97.4% and 91.8%, respectively. A noninferiority score test showed that the clinical specificity (P < 0.0001) and clinical sensitivity (P = 0.011) of RealTime were noninferior to those of hc2 at the recommended thresholds of 98% and 90%. In the total study population (women 20 to 64 years old; n = 4,432; 57 cases, 4,375 controls), the clinical sensitivity and specificity of RealTime were 98.2% and 89.5%, and those of hc2 were 94.7% and 87.7%, respectively. The analytical sensitivity and analytical specificity of RealTime in detecting targeted HPV types evaluated with the largest sample collection to date (4,479 samples) were 94.8% and 99.8%, and those of hc2 were 93.4% and 97.8%, respectively. Excellent analytical agreement between the two assays was obtained (kappa value, 0.84), while the analytical accuracy of RealTime was significantly higher than that of hc2. RealTime demonstrated high intralaboratory reproducibility and interlaboratory agreement with 500 samples retested 61 to 226 days after initial testing in two different laboratories. RealTime can be considered to be a reliable and robust HPV assay clinically comparable to hc2 for the detection of CIN2+ lesions in a population-based cervical cancer screening setting.

Mapping the interactome of HPV E6 and E7 oncoproteins with the ubiquitin-proteasome system.

PubMed

Poirson, Juline; Biquand, Elise; Straub, Marie-Laure; Cassonnet, Patricia; Nominé, Yves; Jones, Louis; van der Werf, Sylvie; Travé, Gilles; Zanier, Katia; Jacob, Yves; Demeret, Caroline; Masson, Murielle

2017-10-01

Protein ubiquitination and its reverse reaction, deubiquitination, regulate protein stability, protein binding activity, and their subcellular localization. These reactions are catalyzed by the enzymes E1, E2, and E3 ubiquitin (Ub) ligases and deubiquitinases (DUBs). The Ub-proteasome system (UPS) is targeted by viruses for the sake of their replication and to escape host immune response. To identify novel partners of human papillomavirus 16 (HPV16) E6 and E7 proteins, we assembled and screened a library of 590 cDNAs related to the UPS by using the Gaussia princeps luciferase protein complementation assay. HPV16 E6 was found to bind to the homology to E6AP C terminus-type Ub ligase (E6AP), three really interesting new gene (RING)-type Ub ligases (MGRN1, LNX3, LNX4), and the DUB Ub-specific protease 15 (USP15). Except for E6AP, the binding of UPS factors did not require the LxxLL-binding pocket of HPV16 E6. LNX3 bound preferentially to all high-risk mucosal HPV E6 tested, whereas LNX4 bound specifically to HPV16 E6. HPV16 E7 was found to bind to several broad-complex tramtrack and bric-a-brac domain-containing proteins (such as TNFAIP1/KCTD13) that are potential substrate adaptors of Cullin 3-RING Ub ligases, to RING-type Ub ligases implicated in innate immunity (RNF135, TRIM32, TRAF2, TRAF5), to the substrate adaptor DCAF15 of Cullin 4-RING Ub ligase and to some DUBs (USP29, USP33). The binding to UPS factors did not require the LxCxE motif but rather the C-terminal region of HPV16 E7 protein. The identified UPS factors interacted with most of E7 proteins across different HPV types. This study establishes a strategy for the rapid identification of interactions between host or pathogen proteins and the human ubiquitination system. © 2017 Federation of European Biochemical Societies.

The surface of 1-euro coins studied by X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Gou, F.; Gleeson, M. A.; Villette, J.; Kleyn, S. E. F.; Kleyn, A. W.

2004-03-01

The two alloy surfaces (pill and ring) that are present on 1-euro coins have been studied by X-ray photoelectron spectroscopy (XPS). Comparison is made between coins from general circulation and coin surfaces that have been subjected to a variety of cleaning and oxidation treatments. The concentrations and possible oxidation states of the metals (nickel, copper and zinc) at the surface were derived from analysis of the 2p 3/2 core levels. The surface atomic ratios measured for the pill and the ring parts of the euro coins were compared to the official bulk ratios. This study shows a clear nickel enrichment of both pill and ring surfaces. Nickel at surface seems to be present mainly in hydroxide form although the chloride form cannot be excluded. A small concentration of zinc was present on the surface of the pill, even though it is not present in the bulk alloy. Evidence of both nickel and zinc surface enrichment is observed for the ring. No surface enrichment is observed for the atomically clean or oxidized alloy surfaces over a 60-h time scale.

Crystal structure of 5''-benzyl-idene-1'-methyl-4'-phenyl-tri-spiro-[ace-naphthyl-ene-1,2'-pyrrolidine-3',1''-cyclo-hexane-3'',2'''-[1,3]dioxane]-2,6''-dione.

PubMed

Chandralekha, Kuppan; Gavaskar, Deivasigamani; Sureshbabu, Adukamparai Rajukrishnan; Lakshmi, Srinivasakannan

2016-03-01

In the title compound, C36H31NO4, two spiro links connect the methyl-substituted pyrrolidine ring to the ace-naphthyl-ene and cyclo-hexa-none rings. The cyclo-hexa-none ring is further connected to the dioxalane ring by a third spiro junction. The five-membered ring of the ace-naphthylen-1-one ring system adopts a flattened envelope conformation with the ketonic C atom as flap, whereas the dioxalane and pyrrolidine rings each have a twist conformation. The cyclo-hexa-none ring assumes a boat conformation. Three intra-molecular C-H⋯O hydrogen bonds involving both ketonic O atoms as acceptors are present. In the crystal, C-H⋯O hydrogen bonds connect centrosymmetrically related mol-ecule into chains parallel to the b axis, forming rings of R 2 (2)(10)and R 2 (2)(8) graph-set motifs.

Migraine headaches in chronic fatigue syndrome (CFS): comparison of two prospective cross-sectional studies.

PubMed

Ravindran, Murugan K; Zheng, Yin; Timbol, Christian; Merck, Samantha J; Baraniuk, James N

2011-03-05

Headaches are more frequent in Chronic Fatigue Syndrome (CFS) than healthy control (HC) subjects. The 2004 International Headache Society (IHS) criteria were used to define CFS headache phenotypes. Subjects in Cohort 1 (HC = 368; CFS = 203) completed questionnaires about many diverse symptoms by giving nominal (yes/no) answers. Cohort 2 (HC = 21; CFS = 67) had more focused evaluations. They scored symptom severities on 0 to 4 anchored ordinal scales, and had structured headache evaluations. All subjects had history and physical examinations; assessments for exclusion criteria; questionnaires about CFS related symptoms (0 to 4 scale), Multidimensional Fatigue Inventory (MFI) and Medical Outcome Survey Short Form 36 (MOS SF-36). Demographics, trends for the number of diffuse "functional" symptoms present, and severity of CFS case designation criteria symptoms were equivalent between CFS subjects in Cohorts 1 and 2. HC had significantly fewer symptoms, lower MFI and higher SF-36 domain scores than CFS in both cohorts. Migraine headaches were found in 84%, and tension-type headaches in 81% of Cohort 2 CFS. This compared to 5% and 45%, respectively, in HC. The CFS group had migraine without aura (60%; MO; CFS+MO), with aura (24%; CFS+MA), tension headaches only (12%), or no headaches (4%). Co-morbid tension and migraine headaches were found in 67% of CFS. CFS+MA had higher severity scores than CFS+MO for the sum of scores for poor memory, dizziness, balance, and numbness ("Neuro-construct", p = 0.002) and perceived heart rhythm disturbances, palpitations and noncardiac chest pain ("Cardio-construct"; p = 0.045, t-tests after Bonferroni corrections). CFS+MO subjects had lower pressure-induced pain thresholds (2.36 kg [1.95-2.78; 95% C.I.] n = 40) and a higher prevalence of fibromyalgia (47%; 1990 criteria) compared to HC (5.23 kg [3.95-6.52] n = 20; and 0%, respectively). Sumatriptan was beneficial for 13 out of 14 newly diagnosed CFS migraine subjects. CFS subjects had higher prevalences of MO and MA than HC, suggesting that mechanisms of migraine pathogenesis such as central sensitization may contribute to CFS pathophysiology. Georgetown University IRB # 2006-481

Damage-free back channel wet-etch process in amorphous indium-zinc-oxide thin-film transistors using a carbon-nanofilm barrier layer.

PubMed

Luo, Dongxiang; Zhao, Mingjie; Xu, Miao; Li, Min; Chen, Zikai; Wang, Lang; Zou, Jianhua; Tao, Hong; Wang, Lei; Peng, Junbiao

2014-07-23

Amorphous indium-zinc-oxide thin film transistors (IZO-TFTs) with damage-free back channel wet-etch (BCE) process were investigated. A carbon (C) nanofilm was inserted into the interface between IZO layer and source/drain (S/D) electrodes as a barrier layer. Transmittance electron microscope images revealed that the 3 nm-thick C nanofilm exhibited a good corrosion resistance to a commonly used H3PO4-based etchant and could be easily eliminated. The TFT device with a 3 nm-thick C barrier layer showed a saturated field effect mobility of 14.4 cm(2) V(-1) s(-1), a subthreshold swing of 0.21 V/decade, an on-to-off current ratio of 8.3 × 10(10), and a threshold voltage of 2.0 V. The favorable electrical performance of this kind of IZO-TFTs was due to the protection of the inserted C to IZO layer in the back-channel-etch process. Moreover, the low contact resistance of the devices was proved to be due to the graphitization of the C nanofilms after annealing. In addition, the hysteresis and thermal stress testing confirmed that the usage of C barrier nanofilms is an effective method to fabricate the damage-free BCE-type devices with high reliability.

Growth of carbon chains in IRC +10216 mapped with ALMA

NASA Astrophysics Data System (ADS)

Agúndez, M.; Cernicharo, J.; Quintana-Lacaci, G.; Castro-Carrizo, A.; Velilla Prieto, L.; Marcelino, N.; Guélin, M.; Joblin, C.; Martín-Gago, J. A.; Gottlieb, C. A.; Patel, N. A.; McCarthy, M. C.

2017-05-01

Linear carbon chains are common in various types of astronomical molecular sources. Possible formation mechanisms involve both bottom-up and top-down routes. We have carried out a combined observational and modeling study of the formation of carbon chains in the C-star envelope IRC +10216, where the polymerization of acetylene and hydrogen cyanide induced by ultraviolet photons can drive the formation of linear carbon chains of increasing length. We have used ALMA to map the emission of λ 3 mm rotational lines of the hydrocarbon radicals C2H, C4H, and C6H, and the CN-containing species CN, C3N, HC3N, and HC5N with an angular resolution of 1''. The spatial distribution of all these species is a hollow 5-10'' wide spherical shell located at a radius of 10-20'' from the star, with no appreciable emission close to the star. Our observations resolve the broad shell of carbon chains into thinner subshells that are 1-2'' wide and not fully concentric, indicating that the mass-loss process has been discontinuous and not fully isotropic. The radial distributions of the species mapped reveal subtle differences: while the hydrocarbon radicals have very similar radial distributions, the CN-containing species show more diverse distributions, with HC3N appearing earlier in the expansion and the radical CN extending later than the rest of the species. The observed morphology can be rationalized by a chemical model in which the growth of polyynes is mainly produced by rapid gas-phase chemical reactions of C2H and C4H radicals with unsaturated hydrocarbons, while cyanopolyynes are mainly formed from polyynes in gas-phase reactions with CN and C3N radicals. Based on observations carried out with ALMA and the IRAM 30 m Telescope. ALMA is a partnership of ESO (representing its member states), NSF (USA) and NINS (Japan), together with NRC (Canada) and NSC and ASIAA (Taiwan), in cooperation with the Republic of Chile. The Joint ALMA Observatory is operated by ESO, AUI/NRAO and NAOJ. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain). This paper makes use of the following ALMA data: ADS/JAO.ALMA#2013.1.00432.S.Data cube (FITS file) is available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/601/A4

Using intra annual density fluctuations and d13C to assess the impact of summer drought on Mediterranean ecosystem

NASA Astrophysics Data System (ADS)

Battipaglia, G.; Brand, W. A.; Linke, P.; Schaefer, I.; Noetzli, M.; Cherubini, P.

2009-04-01

Tree- ring growth and wood density have been used extensively as indicators of climate change, and tree-ring has been commonly applied as a proxy estimate for seasonal integration of temperatures and precipitation with annual resolution (Hughes 2002). While these relationships have been well established in temperate ecosystems (Fritts, 1976; Schweingruber, 1988, Briffa et al., 1998, 2004), in Mediterranean region dendrochronological studies are still scarce (Cherubini et al, 2003). In Mediterranean environment, trees may form intra-annual density fluctuations, also called "false rings" or "double rings" (Tingley 1937; Schulman 1938). They are usually induced by sudden drought events, occurring during the vegetative period, and, allowing intra-annual resolution, they may provide detailed information at a seasonal level, as well as species-specific sensitivity to drought. We investigated the variability of tree- ring width and carbon stable isotopes of a Mediterranean species, Arbutus unedo L., sampled on Elba island, (Tuscany, Italy). The samples were taken at two different sites, one characterized by wet and one by dry conditions. d13C was measured using Laser- Ablation- Combustion -GC-IRMS. Here, we present first results showing the impact of drought on tree growth and on false ring formation at the different sites and we underline the importance of using Laser Ablation to infer drought impact at the intra -annual level. Briffa KR, Schweingruber FH, Jones PD, Osborn TJ, Harris IC, Shiyatov SG, Vaganov EA, Grudd H (1998) Trees tell of past climates: but are they speaking less clearly today? Phil Transact Royal Soc London 353:65-73 Briffa KR, Osborn TJ, Schweingruber FH (2004) Large-scale temperature inferences from tree rings: a review. Glob Panet Change 40:11-26 Cherubini, P., B.L. Gartner, R. Tognetti, O.U. Bräker, W. Schoch & J.L. Innes. 2003. Identification, measurement and interpretation of tree rings in woody species from Mediterranean climates. Biol. Rev. 78: 119-14 Fritts, H.C. 1976. Tree rings and climate. Academic Press, London, UK. Hughes, M.K. 2002. Dendrochronology in climatology - the state of the art. Dendrochronologia 20: 95-116. Schulman, E. 1938. Classification of false annual rings in Monterey pine. Tree-Ring Bull. 4:4-7 Schweingruber FH (1988) Tree-ring: Basics and applications of dendrochronology. Reidel. Publ., Dordrecht, 276 p Tingley, M.A. 1937. Double growth rings in Red Astrachan. Proc. Am. Soc. Hort. Sci. 34: 61.

Crystallographic study of three coronary vasodilators of the nitrate ester type: 1,4- trans-cyclohexanedimethanol dinitrate, 1,4:3,6-dianhydro- D-glucitol-2,5-dinitrate and 1,4:3,6-dianhydro- D-glucitol-2-mononitrate

NASA Astrophysics Data System (ADS)

Kanters, J. A.; Schouten, A.; Sterk, G. J.; de Jong, M. H.

1993-10-01

The crystal structures of three vasodilators of the nitrate ester type have been determined by X-ray diffraction. Compound I, 1,4- trans-cyclohexanedimethanol dinitrate (CDDN), C 8H 14N 2O 6, is a recently developed nitrate ester with a promising haemodynamic profile in the treatment of ischaemic heart diseases. CDDN crystallizes in space group P2 1/a with a = 5.9443(4), b = 16.7052(9), c = 6.2022(2) Å, β = 116.669(4)°, Z = 2 and T = 295 K. The molecule lies on a centre of inversion and the structure refined to R = 0.042 for 991 reflections with I > 2.5σ( I). The cyclohexane ring approaches an ideal chair conformation and the C-O-NO 2 fragment is strictly planar. Compound II is the widely applied vasodilator in angina pectoris, isosorbide dinitrate or 1,4:3,6-dianhydro- D-glucitol-2,5-dinitrate (ISDN), C 6H 8N 2O 8. ISDN crystallizes in space group P22 12 1 with a = 5.7535(2), b = 10.9393(5), c = 14.6599(5)Å, Z = 4 and T = 295 K. The structure refined to R = 0.033 for 1104 reflections with I > 2.5σ( I). The molecular skeleton consists of two cis-fused five-membered rings, which each adopt an envelope conformation such that the torsion angels about the central CC bond are 0.3(2) and -7.8(2)°. The angle between the rings is 60.8(1)° and the two nitrate groups are planar. Compound III, isosorbide-2-mononitrate or 1,4:3,6-dianhydro- D-glucitol-2-mononitrate (IS-2MN), C 6H 9NO 6, is an active metabolite of II and crystallizes in space group P2 12 12 1 with a = 6.4318(4), b = 7.5273(4), c = 15.866(1)Å Z = 4 and T = 100 K. The structure refined to R = 0.031 for 1488 reflections with I > 2.5σ( I). The skeleton of III is very similar to that of II. The torsion angles about the central CC bond are 2.4(2) and -3.1(2)°, the interplanar angle is 61.5(1)° and the nitrate group is strictly planar.

The conserved RNA recognition motif and C3H1 domain of the Not4 ubiquitin ligase regulate in vivo ligase function.

PubMed

Chen, Hongfeng; Sirupangi, Tirupataiah; Wu, Zhao-Hui; Johnson, Daniel L; Laribee, R Nicholas

2018-05-25

The Ccr4-Not complex controls RNA polymerase II (Pol II) dependent gene expression and proteasome function. The Not4 ubiquitin ligase is a Ccr4-Not subunit that has both a RING domain and a conserved RNA recognition motif and C3H1 domain (referred to as the RRM-C domain) with unknown function. We demonstrate that while individual Not4 RING or RRM-C mutants fail to replicate the proteasomal defects found in Not4 deficient cells, mutation of both exhibits a Not4 loss of function phenotype. Transcriptome analysis revealed that the Not4 RRM-C affects a specific subset of Pol II-regulated genes, including those involved in transcription elongation, cyclin-dependent kinase regulated nutrient responses, and ribosomal biogenesis. The Not4 RING, RRM-C, or RING/RRM-C mutations cause a generalized increase in Pol II binding at a subset of these genes, yet their impact on gene expression does not always correlate with Pol II recruitment which suggests Not4 regulates their expression through additional mechanisms. Intriguingly, we find that while the Not4 RRM-C is dispensable for Ccr4-Not association with RNA Pol II, the Not4 RING domain is required for these interactions. Collectively, these data elucidate previously unknown roles for the conserved Not4 RRM-C and RING domains in regulating Ccr4-Not dependent functions in vivo.

Comparative studies on acid leaching of zinc waste materials

NASA Astrophysics Data System (ADS)

Rudnik, Ewa; Włoch, Grzegorz; Szatan, Leszek

2017-11-01

Three industrial waste materials were characterized in terms of their elemental and phase compositions, leaching behaviour in 10% sulfuric acid solution as well as leaching thermal effects. Slag from melting of mixed metallic scrap contained about 50% Zn and 10% Pb. It consisted mainly of various oxides and oxy-chlorides of metals. Zinc spray metallizing dust contained about 77% Zn in form of zinc and/or zinc-iron oxides, zinc metal and Zn-Fe intermetallic. Zinc ash from hot dip galvanizing was a mixture of zinc oxide, metallic zinc and zinc hydroxide chloride and contained about 80% Zn. Dissolution efficiency of zinc from the first material was 80% (independently on the solid to liquid ratio, 50-150 kg/m3), while decrease of the efficacy from 80% to 60% with increased solid to liquid ratio for the two remaining materials was observed. Both increase in the temperature (20 °C to 35 °C) and agitation rate (300 rpm to 900 rpm) did not improve seriously the leaching results. In all cases, transfer of zinc ions to the leachate was accompanied by different levels of solution contamination, depending on the type of the waste. Leaching of the materials was exothermic with the similar reaction heats for two high oxide-type products (slag, zinc ash) and higher values for the spray metallizing dust.

{sup 13}C ISOTOPIC FRACTIONATION OF HC{sub 3}N IN STAR-FORMING REGIONS: LOW-MASS STAR-FORMING REGION L1527 AND HIGH-MASS STAR-FORMING REGION G28.28-0.36

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

Taniguchi, Kotomi; Saito, Masao; Ozeki, Hiroyuki, E-mail: kotomi.taniguchi@nao.ac.jp

2016-10-20

We observed the J = 9–8 and 10–9 rotational lines of three {sup 13}C isotopologues of HC{sub 3}N in L1527 and G28.28-0.36, with the 45 m radio telescope of the Nobeyama Radio Observatory, in order to constrain the main formation mechanisms of HC{sub 3}N in each source. The abundance ratios of the three {sup 13}C isotopologues of HC{sub 3}N are found to be 0.9 (±0.2) : 1.00 : 1.29 (±0.19) (1 σ ), and 1.0 (±0.2) : 1.00 : 1.47 (±0.17) (1 σ ), for [H{sup 13}CCCN : HC{sup 13}CCN : HCC{sup 13}CN] in L1527 and G28.28-0.36, respectively. We recognize,more » from a similar {sup 13}C isotopic fractionation pattern, that the abundances of H{sup 13}CCCN and HC{sup 13}CCN are comparable, and HCC{sup 13}CN is more abundant than the others. Based on the results, we discuss the main formation pathway of HC{sub 3}N. The {sup 13}C isotopic fractionation pattern derived from our observations can be explained by the neutral-neutral reaction between C{sub 2}H{sub 2} and CN in both the low-mass (L1527) and high-mass (G28.28-0.36) star-forming regions.« less

Thyroid Hormone Indices in Computer Workers with Emphasis on the Role of Zinc Supplementation.

PubMed

Amin, Ahmed Ibrahim; Hegazy, Noha Mohamed; Ibrahim, Khadiga Salah; Mahdy-Abdallah, Heba; Hammouda, Hamdy A A; Shaban, Eman Essam

2016-06-15

This study aimed to investigate the effects of computer monitor-emitted radiation on thyroid hormones and the possible protective role of zinc supplementation. The study included three groups. The first group (group B) consisted of 42 computer workers. This group was given Zinc supplementation in the form of one tablet daily for eight weeks. The second group (group A) comprised the same 42 computer workers after zinc supplementation. A group of 63 subjects whose job does not entail computer use was recruited as a control Group (Group C). All participants filled a questionnaire including detailed medical and occupational histories. They were subjected to full clinical examination. Thyroid stimulating hormone (TSH), free triiodothyronine (FT3), free thyroxine (FT4) and zinc levels were measured in all participants. TSH, FT3, FT4 and zinc concentrations were decreased significantly in group B relative to group C. In group A, all tested parameters were improved when compared with group B. The obtained results revealed that radiation emitted from computers led to changes in TSH and thyroid hormones (FT3 and FT4) in the workers. Improvement after supplementation suggests that zinc can ameliorate hazards of such radiation on thyroid hormone indices.

Iron and Vitamin C Co-Supplementation Increased Serum Vitamin C Without Adverse Effect on Zinc Level in Iron Deficient Female Youth

PubMed Central

Khoshfetrat, Mohammad Reza; Mortazavi, Sima; Neyestani, Tirang; Mahmoodi, Mohammad Reza; Zerafati-Shoae, Nahid; Mohammadi-Nasrabadi, Fatemeh

2014-01-01

Background: Iron supplementation can decrease the absorption of zinc and influence other antioxidants levels such as vitamin C. This study aimed to investigate the effect of iron supplements alone and in combination with vitamin C on zinc and vitamin C status in iron deficient female students. Methods: In a double-blind randomized clinical trail, 60 iron deficient students were selected from 289 volunteers residing in dormitory. After matching, subjects were randomly assigned into two groups: Group I (50 mg elemental iron supplements) and Group II (50 mg elemental iron + 500 mg ascorbic acid). Serum ferritin, iron, serum zinc, and plasma vitamin C concentrations were measured by using enzyme-linked immunosorbent assay, spectrophotometer, atomic absorption spectrometer, and colorimeter, respectively after 6 and 12 weeks supplementation. Student's t-test and repeated measures analysis of variance were applied to analyze the data using SPSS software. Results: Serum zinc levels had no significant differences between 2 groups at the baseline; however, its concentration decreased from 80.9 ± 4.2-68.9 ± 2.7 μg/dl to 81.2 ± 4.5-66.1 ± 2.9 μg/dl (P < 0.001) in Groups I and II, respectively after 6 weeks of supplementation. Continuous supplementation increased serum zinc concentration to baseline levels (79.0 ± 2.9 μg/dl; P < 0.01) in Group I and 70.5 ± 3.1 μg/dl in Group II following 12 weeks of supplementation. Plasma vitamin C increased from 3 ± 0/1-3.3 ± 0.2 mg/dl to 2.7 ± 0. 1-4.2 ± 0.2 mg/dl (P < 0.01) in Groups I and II, respectively. At the end of study, plasma vitamin C significantly increased from 3.3 ± 0.3-4.7 ± 0.3 (P < 0.01) to 4.2 ± 0.2-7.1 ± 0.2 (P < 0.001) in Groups I and II, respectively. Conclusions: Iron supplementation with and without vitamin C led to reduction in serum Zn in iron-deficient female students after 6 weeks. However, the decreasing trend stops after repletion of iron stores and Zn levels returned to the approximately baseline values after 12 weeks. PMID:25489453

Spectroscopic and structural investigation of oxocarbon salts with tetraalkylammonium ions

NASA Astrophysics Data System (ADS)

Georgopoulos, Stéfanos L.; Garcia, Humberto C.; Edwards, Howell G. M.; Cappa de Oliveira, Luiz Fernando

2016-03-01

In this study the synthesis, vibrational spectra (infrared and Raman) and crystal structures of three oxocarbon compounds with tetra-alkyl ammonium counter cations, namely [N(C3H7)4](HC4O4) (1), [N(C4H9)4]2[(C4O4) (H2C4O4)2] (2) and [N(C2H5)4]2(C5O5)·5H2O (3), have been reported. The supramolecular arrangement for all compounds as shown by x-ray diffraction indicate that strong donor (D)-acceptor (A) hydrogen bonds D-H…A are present in the dimer formation with monohydrogen squarate anion HC4O4- (2.503 Å) and for the trimer with two squaric acid moieties (H2C4O4) and the squarate dianion C4O42- (2.500 Å), for compounds 1 and 2, respectively. In contrast, compound 3 was stabilized through only averagely strong hydrogen bonds (2.735 Å) between all five oxygen atoms of the croconate dianion with different water molecules of crystallization of the supramolecular system. The presence of bands in the Raman spectrum at 1793 and 1670 cm-1 for compounds 1 and 2 have been assigned to the ν(Cdbnd O), ν(Cdbnd C) + ν(Cdbnd O) modes, thus confirming the oxocarbon presence in the solid structure, as well as the bands at 1716 and 1601 cm-1 for compound 3, assigned to the ν(Cdbnd O) and ν(CO) + ν(CC) + δ(CCC) + δ(CO) coupled modes of the associated croconate dianion (C5O52-). An important Raman signal observed for all structures can be seen at ca. 2950 cm-1 which is associated with the ν(CH2) and ν(CH3) stretching modes from the tetraalkylammonium cations.

Zinc-induced Self-association of Complement C3b and Factor H

PubMed Central

Nan, Ruodan; Tetchner, Stuart; Rodriguez, Elizabeth; Pao, Po-Jung; Gor, Jayesh; Lengyel, Imre; Perkins, Stephen J.

2013-01-01

The sub-retinal pigment epithelial deposits that are a hallmark of age-related macular degeneration contain both C3b and millimolar levels of zinc. C3 is the central protein of complement, whereas C3u is formed by the spontaneous hydrolysis of the thioester bridge in C3. During activation, C3 is cleaved to form active C3b, then C3b is inactivated by Factor I and Factor H to form the C3c and C3d fragments. The interaction of zinc with C3 was quantified using analytical ultracentrifugation and x-ray scattering. C3, C3u, and C3b associated strongly in >100 μm zinc, whereas C3c and C3d showed weak association. With zinc, C3 forms soluble oligomers, whereas C3u and C3b precipitate. We conclude that the C3, C3u, and C3b association with zinc depended on the relative positions of C3d and C3c in each protein. Computational predictions showed that putative weak zinc binding sites with different capacities exist in all five proteins, in agreement with experiments. Factor H forms large oligomers in >10 μm zinc. In contrast to C3b or Factor H alone, the solubility of the central C3b-Factor H complex was much reduced at 60 μm zinc and even more so at >100 μm zinc. The removal of the C3b-Factor H complex by zinc explains the reduced C3u/C3b inactivation rates by zinc. Zinc-induced precipitation may contribute to the initial development of sub-retinal pigment epithelial deposits in the retina as well as reducing the progression to advanced age-related macular degeneration in higher risk patients. PMID:23661701

1-(2-Chloro­acet­yl)-3-methyl-2,6-bis­(3,4,5-trimethoxy­phen­yl)piperidine-4-one

PubMed Central

Lakshminarayana, B. N.; Shashidhara Prasad, J.; Gnanendra, C. R.; Sridhar, M. A.; Chenne Gowda, D.

2009-01-01

In the crystal structure of the title compound, C26H32ClNO8, the piperidine ring is in a twist-chair conformation, with puckering parameters Q = 0.655 (4) Å, θ = 93.1 (1) and ϕ = 254.4 (3)°. The ortho C atoms of the piperidine ring deviate from the plane defined by the remaining ring atoms by 0.380 (3) and −0.250 (3) Å. PMID:21583104

A novel and facile decay path of Criegee intermediates by intramolecular insertion reactions via roaming transition states

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

Nguyen, Trong-Nghia; Department of Physical Chemistry, Hanoi University of Science and Technology, Hanoi; Putikam, Raghunath

2015-03-28

We have discovered a new and highly competitive product channel in the unimolecular decay process for small Criegee intermediates, CH{sub 2}OO and anti/syn-CH{sub 3}C(H)OO, occurring by intramolecular insertion reactions via a roaming-like transition state (TS) based on quantum-chemical calculations. Our results show that in the decomposition of CH{sub 2}OO and anti-CH{sub 3}C(H)OO, the predominant paths directly produce cis-HC(O)OH and syn-CH{sub 3}C(O)OH acids with >110 kcal/mol exothermicities via loose roaming-like insertion TSs involving the terminal O atom and the neighboring C–H bonds. For syn-CH{sub 3}C(H)OO, the major decomposition channel occurs by abstraction of a H atom from the CH{sub 3} groupmore » by the terminal O atom producing CH{sub 2}C(H)O–OH. At 298 K, the intramolecular insertion process in CH{sub 2}OO was found to be 600 times faster than the commonly assumed ring-closing reaction.« less

Supramolecular interactions in carboxylate and sulfonate salts of 2,6-diamino-4-chloropyrimidinium.

PubMed

Mohana, Marimuthu; Thomas Muthiah, Packianathan; Butcher, Ray J

2017-07-01

Two new salts, namely 2,6-diamino-4-chloropyrimidinium 2-carboxy-3-nitrobenzoate, C 4 H 6 ClN 4 + ·C 8 H 4 NO 6 - , (I), and 2,6-diamino-4-chloropyrimidinium p-toluenesulfonate monohydrate, C 4 H 6 ClN 4 + ·C 7 H 7 O 3 S - ·H 2 O, (II), have been synthesized and characterized by single-crystal X-ray diffraction. In both crystal structures, the N atom in the 1-position of the pyrimidine ring is protonated. In salt (I), the protonated N atom and the amino group of the pyrimidinium cation interact with the carboxylate group of the anion through N-H...O hydrogen bonds to form a heterosynthon with an R 2 2 (8) ring motif. In hydrated salt (II), the presence of the water molecule prevents the formation of the familiar R 2 2 (8) ring motif. Instead, an expanded ring [i.e. R 3 2 (8)] is formed involving the sulfonate group, the pyrimidinium cation and the water molecule. Both salts form a supramolecular homosynthon [R 2 2 (8) ring motif] through N-H...N hydrogen bonds. The molecular structures are further stabilized by π-π stacking, and C=O...π, C-H...O and C-H...Cl interactions.

Bulk superconductivity in bismuth oxysulfide Bi4O4S3.

PubMed

Singh, Shiva Kumar; Kumar, Anuj; Gahtori, Bhasker; Shruti; Sharma, Gyaneshwar; Patnaik, Satyabrata; Awana, Veer P S

2012-10-10

A very recent report on the observation of superconductivity in Bi(4)O(4)S(3) [Mizuguchi, Y.; http://arxiv.org/abs/1207.3145] could potentially reignite the search for superconductivity in a broad range of layered sulfides. We report here the synthesis of Bi(4)O(4)S(3) at 500 °C by a vacuum encapsulation technique and its basic characterizations. The as-synthesized Bi(4)O(4)S(3) was contaminated with small amounts of Bi(2)S(3) and Bi impurities. The majority phase was found to be tetragonal (space group I4/mmm) with lattice parameters a = 3.9697(2) Å and c = 41.3520(1) Å. Both AC and DC magnetization measurements confirmed that Bi(4)O(4)S(3) is a bulk superconductor with a superconducting transition temperature (T(c)) of 4.4 K. Isothermal magnetization (M-H) measurements indicated closed loops with clear signatures of flux pinning and irreversible behavior. The lower critical field (H(c1)) at 2 K for the new superconductor was found to be ~15 Oe. Magnetotransport measurements showed a broadening of the resistivity (ρ) and a decrease in T(c) (ρ = 0) with increasing magnetic field. The extrapolated upper critical field H(c2)(0) was ~31 kOe with a corresponding Ginzburg-Landau coherence length of ~100 Å . In the normal state, the ρ ~ T(2) dependence was not indicated. Hall resistivity data showed a nonlinear magnetic field dependence. Our magnetization and electrical transport measurements substantiate the appearance of bulk superconductivity in as-synthesized Bi(4)O(4)S(3). On the other hand, Bi heat-treated at the same temperature is not superconducting, thus excluding the possibility of impurity-driven superconductivity in the newly discovered superconductor Bi(4)O(4)S(3).

A Survey of Large Molecules toward the Protoplanetary Nebula CRL 61 8

NASA Technical Reports Server (NTRS)

Remijan, Anthony J.; Wyrowski, Friedrich; Friedel, Douglas N.; Meier, David S.; Snyder, Lewis E.

2005-01-01

We present the results of our survey toward the protoplanetary nebula CRL 618 for several large, highly saturated, oxygen bearing organic molecules of biological importance including acetaldehyde (CH3CHO), acetic acid (CH3OOH), dimethyl ether (CH3OCH3), ethanol (CH3CH2OH), formic acid (HCOOH) and methyl formate (HCOOCH3); large carbon chain molecules including methyl cyanide (CH3CN) , methylcyanoacetylene (CH3C3N), cyanoacetylene (HC3N), cyanodiacetylene (HC5N), and C6H; and finally smaller molecules including SO-34, SO2, O(C-34)S and MgNC. No biologically important organic molecules were detected. However, we report the first interferometric detections of CH3CN and vibrationally excited HC3N and HC5N toward this source. The temperature and distribution of CH3CN toward CRL 618 indicates it is formed in the outer envelope surrounding the UC HII region. Furthermore, the P-Cygni line profile and corresponding channel maps of vibrationally excited HC5N supports its distribution in the extended envelope expanding radially from the central star. The detection of vibrationally excited HC3N confirmed the temperature structure and column density of HC3N in the inner envelope found by Wyrowski and colleagues (2003). Finally, our observations clearly indicate that CRL 618 is a good source of large carbon chain species but is a very poor source to detect or produce organic species of biological importance.

Synthesis and biological evaluation of 2-thioxopyrimidin-4(1H)-one derivatives as potential non-nucleoside HIV-1 reverse transcriptase inhibitors.

PubMed

Khalifa, Nagy M; Al-Omar, Mohamed A

2014-11-12

A series of new 5-allyl-6-benzylpyrimidin-4(3H)-ones bearing different substituents at the C-2 position of the pyrimidine core have been synthesized and evaluated for their in vitro activities against human immunodeficiency virus type 1 (HIV-1) in the human T-lymphotropic type (MT-4 cell cultures). The majority of the title compounds showed moderate to good activities against HIV-1. Amongst them, 5-allyl-6-benzyl-2-(3-hydroxypropylthio)pyrimidin-4(3H)-one analogue 11c exhibited the most potent anti-HIV-1 activity (IC50 0.32 µM). The biological testing results clearly indicated that the substitution at C-2 position of the pyrimidine ring could increase the anti-HIV-1 reverse transcriptase (RT) activity.

Synthesis and Biological Evaluation of 2-Thioxopyrimidin-4(1H)-one Derivatives as Potential Non-Nucleoside HIV-1 Reverse Transcriptase Inhibitors

PubMed Central

Khalifa, Nagy M.; Al-Omar, Mohamed A.

2014-01-01

A series of new 5-allyl-6-benzylpyrimidin-4(3H)-ones bearing different substituents at the C-2 position of the pyrimidine core have been synthesized and evaluated for their in vitro activities against human immunodeficiency virus type 1 (HIV-1) in the human T-lymphotropic type (MT-4 cell cultures). The majority of the title compounds showed moderate to good activities against HIV-1. Amongst them, 5-allyl-6-benzyl-2-(3-hydroxypropylthio)pyrimidin-4(3H)-one analogue 11c exhibited the most potent anti-HIV-1 activity (IC50 0.32 µM). The biological testing results clearly indicated that the substitution at C-2 position of the pyrimidine ring could increase the anti-HIV-1 reverse transcriptase (RT) activity. PMID:25397597

Enhancement of Hc2 and Jc by carbon-based chemical doping

NASA Astrophysics Data System (ADS)

Yeoh, W. K.; Dou, S. X.

2007-06-01

In the past 5 years, various kinds of doping of MgB 2, including single elements (metal and non-metal), silicates, various carbon sources, and other compounds have been investigated and reported. Most nanoparticle doping leads to improvement of critical current density, Jc( H), and performance, but some types show a negative effect. In this paper, the effect of carbon doping on Jc and the upper critical field, Hc2, of MgB 2 is reviewed. Carbon substitution effects make two distinguishable contributions to the enhancement of Jc field performance: increase of Hc2 and improvement of flux pinning, both because carbon substitutes for boron in the MgB 2 lattice. Among all the carbon sources so far, nano-SiC has been confirmed to be the most effective dopant to enhance the Jc in magnetic fields and Hc2. An irreversibility field, Hirr, of 10 T has been achieved with nano-SiC doping at 20 K, exceeding Hirr of NbTi at 4.2 K. Besides that, Hc2 of carbon alloyed MgB 2 film has reached the value of 71 T. The significant enhancement in Jc( H) and Hc2 via carbon substitution has provided great potential for practical applications of MgB 2. The dual reaction model proposed by the authors’ group provides a comprehensive understanding of the mechanism of enhancement in Jc and Hc2 by chemical doping. Further improvement in self-field Jc performance while maintaining the already achieved in-field performance remains as a major challenge in the development of MgB 2.

Effect of oral zinc supplementation upon Taenia crassiceps murine cysticercosis.

PubMed

Fragoso, G; Lastra, M D; Aguilar, A E; Pastelin, R; Rosas, G; Meneses, G; Sciutto, E; Lamoyi, E

2001-10-01

The effect of zinc supplementation on Taenia crassiceps murine cysticercosis was studied in susceptible BALB/cAnN mice. Female offspring of mice supplemented with high zinc throughout gestation and lactation were intraperitoneally infected with T. crassiceps cysticerci. Offspring from nonsupplemented mothers were used as controls. Significantly fewer parasites were recovered from zinc-supplemented mice (Zsm) 30 days after infection. Increased resistance was not related to the IgG antibody response. At early stages of infection, T cells from Zsm proliferated to T. crassiceps antigens, whereas cells from control mice did not respond. Infection caused in both groups a decrease in CD3+ cell percentages, which was more pronounced in the controls, and paralleled by a decrease in CD8+ cells; CD3+ and CD8+ percentages returned to normal levels at later stages of infection. In contrast, the CD4+ subpopulation only decreased in control mice. Intracellular cytokine determinations indicate that zinc supplementation favored a stronger and persistent type-1 T cell response in cysticerci-infected mice, which probably participates in the observed increased resistance.

Exploring the structure determinants of pyrazinone derivatives as PDE5 3HC8 inhibitors: an in silico analysis.

PubMed

Li, Yan; Wu, Wenzhao; Ren, Hong; Wang, Jinghui; Zhang, Shuwei; Li, Guohui; Yang, Ling

2012-09-01

Phosphodiesterase type 5 (PDE5) inhibitors are clinically indicated for the treatment of erectile dysfunction, pulmonary hypertension and various other diseases. In this work, both ligand- and receptor-based three-dimensional quantitative structure-activity relationship (3D-QSAR) studies were carried out using comparative molecular field analysis (CoMFA) and comparative molecular similarity indices analysis (CoMSIA) techniques on 122 pyrazinone derivatives as PDE inhibitors. The resultant optimum 3D-QSAR model exhibits a proper predictive ability as indicated by the statistical results of Q² of 0.584, R(ncv)² of 0.884 and R(pre)² of 0.817, respectively. In addition, docking analysis and molecular dynamics (MD) simulation were also applied to elucidate the probable binding modes of these inhibitors. Our main findings are: (1) Introduction of bulky, electropositive and hydrophobic substituents at 12- and 19-positions can increase the biological activities. (2) N atom at 8-position is detrimental to the inhibitor activity, and the effect of N atoms at 5- and 6-positions on compound activity is co-determined by both the hydrophobic force and the π-π stacking interaction. (3) Bulky and hydrophilic substitutions are favored at the 27-position of ring D. (4) Electronegative and hydrophilic substitutions around 5- and 6-positions increase the inhibitory activity. (5) Hydrophobic forces and π-π stacking interaction with Phe786 and Phe820 are crucial in determining the binding of pyrazinone derivatives to PDE5. (6) Bulky substitutions around ring C favors selectivity against PDE11, while bulky groups near the 21-position disfavor the selectivity. The information obtained from this work can be utilized to accurately predict the binding affinity of related analogues and also facilitate future rational designs of novel PDE5 inhibitors with improved activity and selectivity. Copyright © 2012 Elsevier Inc. All rights reserved.

Effect of Fluorocarbon and Hydrocarbon Chain Lengths in Hybrid Surfactants for Supercritical CO2.

PubMed

Sagisaka, Masanobu; Ono, Shinji; James, Craig; Yoshizawa, Atsushi; Mohamed, Azmi; Guittard, Frédéric; Rogers, Sarah E; Heenan, Richard K; Yan, Ci; Eastoe, Julian

2015-07-14

Hybrid surfactants containing both fluorocarbon (FC) and hydrocarbon (HC) chains have recently been shown to solubilize water and form elongated reversed micelles in supercritical CO2. To clarify the most effective FC and HC chain lengths, the aggregation behavior and interfacial properties of hybrid surfactants FCm-HCn (FC length m/HC length n = 4/2, 4/4, 6/2, 6/4, 6/5, 6/6, and 6/8) were examined in W/CO2 mixtures as functions of pressure, temperature, and water-to-surfactant molar ratio (W0). The solubilizing power of hybrid surfactants for W/CO2 microemulsions was strongly affected by not only the FC length but also by that of the HC. Although the surfactants having short FC and/or HC tails (namely, m/n = 4/2, 4/4, and 6/2) did not dissolve in supercritical CO2 (even at ∼17 mM, ≤400 bar, temperature ≤ 75 °C, and W0 = 0-40), the other hybrid surfactants were able to yield transparent single-phase W/CO2 mixtures identified as microemulsions. The solubilizing power of FC6-HCm surfactants reached a maximum (W0 ∼ 80 at 45 °C and 350 bar) with a hydrocarbon length, m, of 4. The W0 value of 80 is the highest for a HC-FC hybrid surfactant, matching the highest value reported for a FC surfactant which contained more FC groups. High-pressure small-angle neutron scattering measurements from FCm-HCn/D2O/CO2 microemulsions were consistent with growth of the microemulsion droplets with increasing W0. In addition, not only spherical reversed micelles but also nonspherical assemblies (rodlike or ellipsoidal) were found for the systems with FC6-HCn (n = 4-6). At fixed surfactant concentration and W0 (17 mM and W0 = 20), the longest reversed micelles were obtained for FC6-HC6 where a mean aspect ratio of 6.3 was calculated for the aqueous cores.

miR-192 suppresses T follicular helper cell differentiation by targeting CXCR5 in childhood asthma.

PubMed

Zhang, Defeng; Wu, Yuanbo; Sun, Gengyun

2018-05-01

The aim of this study was to investigate the role of miR-192 in differentiation of T follicular helper cells in childhood asthma. Blood samples were taken from eighteen children with acute asthma attacks and fifteen healthy children (HC). Quantitative real-time PCR and Western blotting were used to detect the expression levels of miR-192, C-X-C chemokine receptor type 5 (CXCR5), B-cell lymphoma 6 (BCL-6) and inducible T-cell costimulator (ICOS). The flow cytometry was performed to detect the proportion of CD4 + CXCR5+ Tfh cells on CD4 + T lymphocytes. The enzyme-linked immunosorbent assay (ELISA) was carried out to determine the plasma concentrations of total IgE and IL-21. The effect of miR-192 on the T follicular helper cells differentiation by targeting CXCR5 was determined by dual-luciferase reporter assay. Children with asthma had lower levels of miR-192 than HC. The proportion of CD4 + CXCR + Tfh cells was significantly higher in the acute asthma group than HC. Similarly, the plasma concentration of total IgE and IL-21 in the acute group markedly increased compared with the HC, and IgE concentration was positively correlated with the proportion of CD4 + CXCR5 + Tfh cells. Furthermore, the expression levels of CXCR5, Bcl-6 and ICOS were significantly higher in the acute group than in the HC. While the proportion of CD4 + CXCR5 + Tfh cells, IL-21, CXCR5, Bcl-6 and ICOS were obviously lower in the CD4 + T cells transfected with miR-192 plasmid than that in miR-192 + CXCR5 group and control group. In conclusion, miR-192 blocks the activation pathway of Tfh cells by targeting CXCR5, which is a reasonable cellular target for therapeutic intervention.

Transcriptome-wide identification of Camellia sinensis WRKY transcription factors in response to temperature stress.

PubMed

Wu, Zhi-Jun; Li, Xing-Hui; Liu, Zhi-Wei; Li, Hui; Wang, Yong-Xin; Zhuang, Jing

2016-02-01

Tea plant [Camellia sinensis (L.) O. Kuntze] is a leaf-type healthy non-alcoholic beverage crop, which has been widely introduced worldwide. Tea is rich in various secondary metabolites, which are important for human health. However, varied climate and complex geography have posed challenges for tea plant survival. The WRKY gene family in plants is a large transcription factor family that is involved in biological processes related to stress defenses, development, and metabolite synthesis. Therefore, identification and analysis of WRKY family transcription factors in tea plant have a profound significance. In the present study, 50 putative C. sinensis WRKY proteins (CsWRKYs) with complete WRKY domain were identified and divided into three Groups (Group I-III) on the basis of phylogenetic analysis results. The distribution of WRKY family transcription factors among plantae, fungi, and protozoa showed that the number of WRKY genes increased in higher plant, whereas the number of these genes did not correspond to the evolutionary relationships of different species. Structural feature and annotation analysis results showed that CsWRKY proteins contained WRKYGQK/WRKYGKK domains and C2H2/C2HC-type zinc-finger structure: D-X18-R-X1-Y-X2-C-X4-7-C-X23-H motif; CsWRKY proteins may be associated with the biological processes of abiotic and biotic stresses, tissue development, and hormone and secondary metabolite biosynthesis. Temperature stresses suggested that the candidate CsWRKY genes were involved in responses to extreme temperatures. The current study established an extensive overview of the WRKY family transcription factors in tea plant. This study also provided a global survey of CsWRKY transcription factors and a foundation of future functional identification and molecular breeding.

1-(2,4-Di-nitro-phen-yl)-2-[(E)-(3,4,5-tri-meth-oxy-benzyl-idene)]hydrazine.

PubMed

Chantrapromma, Suchada; Ruanwas, Pumsak; Boonnak, Nawong; Chidan Kumar, C S; Fun, Hoong-Kun

2014-02-01

Mol-ecules of the title compound, C16H16N4O7, are not planar with a dihedral angle of 5.50 (11)° between the substituted benzene rings. The two meta-meth-oxy groups of the 3,4,5-tri-meth-oxy-benzene moiety lie in the plane of the attached ring [Cmeth-yl-O-C-C torsion angles -0.1 (4)° and -3.7 (3)°] while the para-meth-oxy substituent lies out of the plane [Cmeth-yl-O-C-C, -86.0 (3)°]. An intra-molecular N-H⋯O hydrogen bond involving the 2-nitro substituent generates an S(6) ring motif. In the crystal structure, mol-ecules are linked by weak C-H⋯O inter-actions into screw chains, that are arranged into a sheet parallel to the bc plane. These sheets are connected by π-π stacking inter-actions between the nitro and meth-oxy substituted aromatic rings with a centroid-centroid separation of 3.9420 (13) Å. C-H⋯π contacts further stabilize the two-dimensional network.

A novel dihydropyridine with 3-aryl meta-hydroxyl substitution blocks L-type calcium channels in rat cardiomyocytes.

PubMed

Galvis-Pareja, David; Zapata-Torres, Gerald; Hidalgo, Jorge; Ayala, Pedro; Pedrozo, Zully; Ibarra, Cristián; Diaz-Araya, Guillermo; Hall, Andrew R; Vicencio, Jose Miguel; Nuñez-Vergara, Luis; Lavandero, Sergio

2014-08-15

Dihydropyridines are widely used for the treatment of several cardiac diseases due to their blocking activity on L-type Ca(2+) channels and their renowned antioxidant properties. We synthesized six novel dihydropyridine molecules and performed docking studies on the binding site of the L-type Ca(2+) channel. We used biochemical techniques on isolated adult rat cardiomyocytes to assess the efficacy of these molecules on their Ca(2+) channel-blocking activity and antioxidant properties. The Ca(2+) channel-blocking activity was evaluated by confocal microscopy on fluo-3AM loaded cardiomyocytes, as well as using patch clamp experiments. Antioxidant properties were evaluated by flow cytometry using the ROS sensitive dye 1,2,3 DHR. Our docking studies show that a novel compound with 3-OH substitution inserts into the active binding site of the L-type Ca(2+) channel previously described for nitrendipine. In biochemical assays, the novel meta-OH group in the aryl in C4 showed a high blocking effect on L-type Ca(2+) channel as opposed to para-substituted compounds. In the tests we performed, none of the molecules showed antioxidant properties. Only substitutions in C2, C3 and C5 of the aryl ring render dihydropyridine compounds with the capacity of blocking LTCC. Based on our docking studies, we postulate that the antioxidant activity requires a larger group than the meta-OH substitution in C2, C3 or C5 of the dihydropyridine ring. Copyright © 2014 Elsevier Inc. All rights reserved.

Electrochemical and Density Functional Theory Study on the Reactivity of Fisetin and Its Radicals: Implications on in Vitro Antioxidant Activity

NASA Astrophysics Data System (ADS)

Marković, Zoran S.; Mentus, Slavko V.; Dimitrić Marković, Jasmina M.

2009-12-01

Antioxidative properties of naturally occurring flavon-3-ol, fisetin, were examined by both cyclic voltammetry and quantum-chemical based calculations. The three voltametrically detectable consecutive steps, reflected the fisetin molecular structure, catecholic structural unit in the ring B, C3-OH, and C7-OH groups in the rings C and A. Oxidation potential values, used as quantitative parameter in determining its oxidation capability, indicated good antioxidative properties found with this molecule. Oxidation of the C3'C4' dixydroxy moiety at the B ring occurred first at the lowest positive potentials. The first oxidation step induced fast intramolecular transformations in which the C3 hydroxy group disappeared and the product of this transformation participated in the second oxidation step. The highest potential of oxidation was attributed to the oxidation of C7 hydroxy group. The structural and electronic features of fisetin were investigated at the B3LYP/6-311++G** level of theory. Particularly, the interest was focused on the C3' and C4'-OH sites in the B ring and on C3-OH site in the C ring. The calculated bond dissociation enthalpy values for all OH sites of fisetin clearly indicated the importance of the B ring and C3' and C4'-OH group. The importance of keto-enol tautomerism has also been considered. The analysis also included the Mulliken spin density distribution for the radicals formed after H removal on each OH site. The results showed the higher values of the BDE on the C7-OH and C3-OH sites.

Impact of High-Carbohydrate Diet on Metabolic Parameters in Patients with Type 2 Diabetes

PubMed Central

Jung, Chan-Hee; Choi, Kyung Mook

2017-01-01

In patients with type 2 diabetes mellitus (T2DM), whether dietary carbohydrates have beneficial or detrimental effects on cardiometabolic risk factors has drawn attention. Although a high-carbohydrate (HC) diet and a low-carbohydrate (LC) diet have gained popularity for several decades, there is scarce review focusing on the effects of HC diet on glucose, lipids and body weight in patients with T2DM. In this review, we examined recently-published literature on the effects of HC diets on metabolic parameters in T2DM. HC diets are at least as effective as LC diets, leading to significant weight loss and a reduction in plasma glucose, HbA1c and low density lipoprotein-cholesterol (LDL-C) levels. The major concern is that HC diets may raise serum triglyceride levels and reduce high density lipoprotein-cholesterol (HDL-C) levels, increasing the risk of cardiovascular disease. However, these untoward effects were not a persistent consequence and may be ameliorated with the consumption of a low glycemic index (GI)/low glycemic load (GL) and high fiber. Carbohydrate intake should be individualized, and low caloric intake remains a crucial factor to improve insulin sensitivity and reduce body weight; however, an HC diet, rich in fiber and with a low GI/GL, may be recommendable in patients with T2DM. PMID:28338608

Impact of High-Carbohydrate Diet on Metabolic Parameters in Patients with Type 2 Diabetes.

PubMed

Jung, Chan-Hee; Choi, Kyung Mook

2017-03-24

In patients with type 2 diabetes mellitus (T2DM), whether dietary carbohydrates have beneficial or detrimental effects on cardiometabolic risk factors has drawn attention. Although a high-carbohydrate (HC) diet and a low-carbohydrate (LC) diet have gained popularity for several decades, there is scarce review focusing on the effects of HC diet on glucose, lipids and body weight in patients with T2DM. In this review, we examined recently-published literature on the effects of HC diets on metabolic parameters in T2DM. HC diets are at least as effective as LC diets, leading to significant weight loss and a reduction in plasma glucose, HbA1c and low density lipoprotein-cholesterol (LDL-C) levels. The major concern is that HC diets may raise serum triglyceride levels and reduce high density lipoprotein-cholesterol (HDL-C) levels, increasing the risk of cardiovascular disease. However, these untoward effects were not a persistent consequence and may be ameliorated with the consumption of a low glycemic index (GI)/low glycemic load (GL) and high fiber. Carbohydrate intake should be individualized, and low caloric intake remains a crucial factor to improve insulin sensitivity and reduce body weight; however, an HC diet, rich in fiber and with a low GI/GL, may be recommendable in patients with T2DM.

Hypophyllins A-D, Labdane-Type Diterpenoids with Vasorelaxant Activity from Hypoestes phyllostachya "Rosea".

PubMed

Wu, Xing-De; Luo, Dan; Tu, Wen-Chao; Deng, Zhen-Tao; Chen, Xue-Jiao; Su, Jia; Ji, Xu; Zhao, Qin-Shi

2016-12-16

Three rearranged labdane-type diterpenoids, hypophyllins A-C (1-3), and a caged labdane diterpenoid possessing a 8,9-dioxatricyclic[4.2.1.1 3,7 ]decane moiety, hypophyllin D (4), as well as two new biogenetically related diterpernoids, hypophyllins E (5) and F (6), were isolated from the aerial parts of Hypoestes phyllostachya "Rosea". The absolute configurations of 1-4 were determined by X-ray diffraction analysis. The plausible biogenetic pathway for 1-4 was also proposed. Compounds 4 and 5 showed potent vasorelaxant activity on endothelium-intact thoracic aorta rings precontracted with KCl.

Effect of quorum sensing signals produced by seaweed-associated bacteria on carpospore liberation from Gracilaria dura

PubMed Central

Singh, Ravindra Pal; Baghel, Ravi S.; Reddy, C. R. K.; Jha, Bhavanath

2015-01-01

Epiphytic and endophytic bacteria associated with green macroalgae Ulva (U. fasciata and U. lactuca) and red macroalgae Gracilaria (G. corticata and G. dura) have been identified from three different seasons to evaluate the effect of quorum sensing (QS) molecules on carpospores liberation from Gracilaria dura. The bacterial isolates belonging to the orders Bacillales, Pseudomonadales, Alteromonadales, and Vibrionales were present in all seasons, whereas Actinomycetales and Enterobacteriales were confined to pre-monsoon and post-monsoon seasons, respectively. Among all the Gram-negative bacteria, seven isolates were found to produce different types of N-acyl homoserine lactones (AHLs). Interestingly, Shewanella algae produced five types of AHL: C4-HSL, HC4-HSL, C6-HSL, 3-oxo-C6-HSL, and 3-oxo-C12-HSL. Subsequently, the AHLs producing bacterial isolates were screened for carpospore liberation from G. dura and these isolates were found to positively induce carpospore liberation over the control. Also, observed that carpospore liberation increased significantly in C4- and C6-HSL treated cystocarps. Sodium dodecyl sulfate and native polyacrylamide gel electrophoresis of the total protein of the C4- and C6-HSL treated cystocarps showed two specific peptide bands of different molecular weights (50 kDa and 60 kDa) as compared to the control, confirming their indirect effect on carpospore liberation. PMID:25788899

Thermodynamic and transport properties of YbNi 4Cd

NASA Astrophysics Data System (ADS)

Lee, J.; Park, H.; Lee-Hone, N. R.; Broun, D. M.; Mun, E.

2018-05-01

The single crystal growth and the physical properties of the intermetallic compounds R Ni4Cd (R =Y and Yb) which crystallize in the face-centered cubic (fcc) MgCu4Sn -type structure (space group F 4 ¯3 m ) are discussed. Thermodynamic and transport properties of YbNi4Cd are studied by measuring the magnetization, electrical resistivity, and specific heat. The magnetic susceptibility measurement shows that the 4 f electrons of Yb3 + ions are well localized. The electrical resistivity and specific heat exhibits an antiferromagnetic ordering below TN=0.97 K. Applying the field along the [111] direction results in the suppression of TN below 0.4 K at the critical field Hc˜4.5 kOe. No non-Fermi liquid behavior has been observed in the vicinity of Hc. Above Hc, the magnetoresistivity shows an unconventional temperature dependence ρ (T ) =ρ0+A Tn with n >2 , suggesting that an additional scattering mechanism in the resistivity needs to be considered. Based on the analysis of experimental results, we conclude that the Yb3 + moments and conduction electrons are weakly coupled. Despite the antiferromagnetic ordering below TN, YbNi4Cd exhibits a large frustration parameter | θp/TN|˜16 , where the magnetic Yb3 + ions occupy the tetrahedra on the fcc lattice.

Dense-gas properties in Arp 220 revealed by isotopologue lines

NASA Astrophysics Data System (ADS)

Wang, Junzhi; Zhang, Zhi-Yu; Zhang, Jiangshui; Shi, Yong; Fang, Min

2016-02-01

We present observations of isotopologue lines of dense-gas tracers at 3 mm and 1 mm towards the nearest ultra-luminous infrared galaxy Arp 220. The 3-mm and 1-mm observations were performed with the Institut de Radioastronomie Millimétrique 30-m telescope and the Atacama Pathfinder Experiment 12-m telescope, respectively. We detected H13CN and HN13C in 1-0 and 3-2, and HC15N 1-0, among which HC15N 1-0 and HN13C 1-0 are detected in Arp 220 for the first time. The H13CO+ 1-0 and 3-2 lines are unlikely to be detected because of the confusion of SiO lines. We find that the ratio of the line brightness temperatures of HN13C 3-2/1-0 is 2.4, which is significantly higher than that of H13CN 3-2/1-0 (0.73). This indicates that HN13C and HNC molecules are in denser regions than H13CN and HCN molecules. With the line ratio of H13CN 1-0 and HC15N 1-0, the 14N/15N ratio was estimated to be 440^{+140}_{-82}, which is larger than that of the local interstellar medium.

Tenotomy of m.soleus antagonists prevents the changes in fiber type characteristics and sarcomeric cytoskeletal proteins in unloaded rats

NASA Astrophysics Data System (ADS)

Moukhina, Alexandra; Ardabievskaya, Anna; Vikhlyantsev, Ivan; Podlubnaya, Zoya; Nemirovskaya, Tatiana; Shenkman, Boris

2005-08-01

It is known that activity of postural extensors (m. soleus) decreases and activity of flexors (m. tibialis anterior) increases under unloading conditions. We have tested the hypothesis supposing that increased flexor activities during unloading exert suppressive influence on postural extensor activities and thus lead to dramatic changes in fiber size, MHC expression, sarcomeric proteins content in m.soleus. We have inactivated hindlimb flexor muscles (m.soleus antagonists) by bilateral tenotomy. 20 male Wistar rats were divided on 3 groups: cage control (C), hindlimb suspension for 14 days (HS), tenotomy of hindlimb flexor muscles with 14 days hindlimb suspension afterwards (HST). Several soleus muscle fiber characteristics decreased significantly in HS group (p<0.05) as compared with C group: cross sectional area (CSA) of type I muscle fibers, titin/MyHC ratio and nebulin/MyHC ratio. MyHC isoform pattern shifted slow-to-fast significantly. NFATc1 content increased in nuclear protein extract of m. soleus in HS group. None of these parameters was significantly different in HST group from those of C group. It has been concluded that the tenotomy of flexors under hindlimb suspension prevents atrophy of type I muscle fibers, decrease the degradation of titin and nebulin and prevent slow-to-fast shift of fiber MyHC isoform pattern, possibly through prevention of increase NFATc1 content in muscle fiber nuclear protein extract. Therefore, suppressive influence of increased flexor activity could be one of mechanisms that lead to the changes in m. soleus under unloading conditions. The work was supported by RFBR grants: 02-04-50025, 03- 04-48487 and the special program of RAS "Integration mechanisms of functional control in the living system".

Changes in carbon sources fueling benthic secondary production over depth and time: coupling Chironomidae stable carbon isotopes to larval abundance.

PubMed

Frossard, Victor; Verneaux, Valérie; Millet, Laurent; Magny, Michel; Perga, Marie-Elodie

2015-06-01

Stable C isotope ratio (δ(13)C) values of chironomid remains (head capsules; HC) were used to infer changes in benthic C sources over the last 150 years for two French sub-Alpine lakes. The HCs were retrieved from a series of sediment cores from different depths. The HC δ(13)C values started to decrease with the onset of eutrophication. The HC δ(13)C temporal patterns varied among depths, which revealed spatial differences in the contribution of methanotrophic bacteria to the benthic secondary production. The estimates of the methane (CH4)-derived C contribution to chironomid biomass ranged from a few percent prior to the 1930s to up to 30 % in recent times. The chironomid fluxes increased concomitantly with changes in HC δ(13)C values before a drastic decrease due to the development of hypoxic conditions. The hypoxia reinforced the implication for CH4-derived C transfer to chironomid production. In Lake Annecy, the HC δ(13)C values were negatively correlated to total organic C (TOC) content in the sediment (Corg), whereas no relationship was found in Lake Bourget. In Lake Bourget, chironomid abundances reached their maximum with TOC contents between 1 and 1.5 % Corg, which could constitute a threshold for change in chironomid abundance and consequently for the integration of CH4-derived C into the lake food webs. Our results indicated that the CH4-derived C contribution to the benthic food webs occurred at different depths in these two large, deep lakes (deep waters and sublittoral zone), and that the trophic transfer of this C was promoted in sublittoral zones where O2 gradients were dynamic.

Bis(N'-{(E)-[(2E)-1,3-di-phenyl-prop-2-en-1-yl-idene]amino}-N-ethyl-carbamimido-thio-ato-κ2N',S)zinc(II): 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

2017-07-01

The title Zn II complex, [Zn(C 18 H 18 N 3 S) 2 ], (I), features two independent but chemically equivalent mol-ecules in the asymmetric unit. In each, the thio-semicarbazonate monoanion coordinates the Zn II atom via the thiol-ate-S and imine-N atoms, with the resulting N 2 S 2 donor set defining a distorted tetra-hedral geometry. The five-membered ZnSCN 2 chelate rings adopt distinct conformations in each independent mol-ecule, i.e. one ring is almost planar while the other is twisted about the Zn-S bond. In the crystal, the two mol-ecules comprising the asymmetric unit are linked by amine-N-H⋯N(imine) and amine-N-H⋯S(thiol-ate) hydrogen bonds via an eight-membered heterosynthon, {⋯HNCN⋯HNCS}. The dimeric aggregates are further consolidated by benzene-C-H⋯S(thiol-ate) inter-actions and are linked into a zigzag supra-molecular chain along the c axis via amine-N-H⋯S(thiol-ate) hydrogen bonds. The chains are connected into a three-dimensional architecture via phenyl-C-H⋯π(phen-yl) and π-π inter-actions, the latter occurring between chelate and phenyl rings [inter-centroid separation = 3.6873 (11) Å]. The analysis of the Hirshfeld surfaces calculated for (I) emphasizes the different inter-actions formed by the independent mol-ecules in the crystal and the impact of the π-π inter-actions between chelate and phenyl rings.

Rb3In(H2O)Si5O13: a novel indium silicate with a CdSO4-topological-type structure.

PubMed

Hung, Ling-I; Wang, Sue-Lein; Chen, Chia-Yi; Chang, Bor-Chen; Lii, Kwang-Hwa

2005-05-02

A novel indium silicate, Rb3In(H2O)Si5O13, has been synthesized using a high-temperature, high-pressure hydrothermal method and characterized by single-crystal X-ray diffraction. The structure consists of five-membered rings of corner-sharing SiO4 tetrahedra connected via corner sharing to four adjacent five-membered rings to form a 3D silicate framework that belongs to the CdSO4 topological type. The InO6 octahedron shares five of its corners with five different SiO4 tetrahedra to form a 3D frame-work that delimits two types of channels to accommodate the rubidium cations. The sixth corner of InO6 is coordinated H2O. The structure is related to that of the titanium silicate ETS-10, and these are the only two metal silicates that have the CdSO4-topological-type structure. In addition, the crystal of Rb3In(H2O)Si5O13 shows an intense second harmonic generation signal. Crystal data: H2Rb3InSi5O14, monoclinic, space group Cc (No. 9), a = 9.0697(5) A, b = 11.5456(6) A, c = 13.9266(8) A, beta = 102.300(1) degrees, V = 1424.8(1) A3, and Z = 4.

Educational career and predictors of type of education in young adults with spina bifida.

PubMed

Barf, H A; Verhoef, M; Post, M W M; Jennekens-Schinkel, A; Gooskens, R H J M; Mullaart, R A; Prevo, A J H

2004-03-01

Children with spina bifida (SB) often require special education. To date, little information is available about the educational career of these children. This study focuses on educational career and predictors of attending special education of young adults with SB, using a cross-sectional study including 178 young Dutch adults with SB aged from 16-25. The main outcome was attending regular versus special education. For searching predictive power we selected age, gender, type of SB, level of lesion, hydrocephalus (HC), number of surgical interventions, ambulation, continence and cognitive functioning. Chi-square tests and binary logistic regression were used in the data analysis. Participants with HC attended special primary education more often (59%) than participants without HC (17%). For those participants with HC, the necessity of special primary education was associated with below average intelligence (75% versus 35%), wheelchair dependence (82% versus 39%) and surgical interventions (74% versus 44%). Only half of the participants with HC followed regular secondary education, whereas for participants with SB without HC, the outcome in secondary education was similar to that of the general population (92%). Intelligence was the main predictor of attending special secondary education (odds 5.1:1), but HC (odds 4.3:1) and wheelchair dependence (odds 2.6:1) were also a significant. Other variables were not significant predictors of special secondary education.

Structural, morphological and magnetic properties of Sr0.3La0.48Ca0.25n[Fe(2-0.4/n)O3]Co0.4 (n = 5.5, 5.6,5.7,5.8, 5.9, 6.0) hexaferrites prepared by facile ceramic route methodology

NASA Astrophysics Data System (ADS)

Rehman, Khalid Mehmood Ur; Liu, Xiansong; Yang, Yujie; Feng, Shuangjiu; Tang, Jin; Ali, Zulfiqar; Wazir, Z.; Khan, Muhammad Wasim; Shezad, Mudssir; Iqbal, Muhammad Shahid; Zhang, Cong; Liu, Chaocheng

2018-03-01

In present work, M-type strontium hexaferrite with chemical composition of Sr0.3La0.48Ca0.25n[Fe(2-0.4/n)O3]Co0.4 (n = 5.5, 5.6, 5.7, 5.8, 5.9, 6.0) magnetic powder were synthesized by using facile ceramic route methodology. The structural, morphological and magnetic properties of the products were investigated by using X-rays diffraction (XRD), Scanning Electron Microscopy (SEM) and Vibrating Sample Magnetometer (VSM) techniques, respectively. There is a single magnetoplumbite phase in the magnetic powders containing (5.5 ≤ n ≤5.8) and (n ≥ 5.9) magnetic some impurities begin to seem in the structure. The magnets have shaped hexagonal structures. Magnetic properties of the samples were metric by permanent magnetic measuring equipment Vibrating Sample Magnetometer, respectively. We report our investigation of n-aggregation iron content on crystalline size characterization and magnetic properties of the specimen. It is originate that the desirable quantity of n-aggregation iron content substitution may curiously increase saturation magnetization (Ms) and intrinsic coercivity (Hc). With the iron addition for the same sintering temperature at 1260 °C, (Ms) and (Hc) first increase and then decrease gradually.

Optimization of a polymer top electrode for inverted semitransparent organic solar cells

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

Zhou, Yinhua; Cheun, Hyeunseok; Choi, Seungkeun

We report on semitransparent organic solar cells using a single-layer blend based on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the top electrode. The PEDOT:PSS blend was prepared by mixing a high-conductivity formulation of PEDOT:PSS (H.C. Starck CLEVIOS PH-1000) and another formulation of PEDOT:PSS (H.C. Starck CLEVIOS CPP 105D). The PEDOT:PSS blend yields good wetting properties on the hydrophobic surface of a blend of poly(3-hexylthiophene) (P3HT) with phenyl-C 61-butyric acid methyl ester (PC 60 BM), and shows a conductivity over 400 S cm -1. Semitransparent organic solar cells using the PEDOT:PSS blend as the top electrode with a structure of glass/ITO/ZnO/P3HT:PC 60BM/PEDOT:PSS-blend exhibited anmore » average power conversion efficiency of 2.4% estimated for 100 mW cm -2 AM 1.5G illumination.« less

The bacterial degradation of flavonoids. Oxidative fission of the A-ring of dihydrogossypetin by a Pseudomonas sp

PubMed Central

Jeffrey, A. M.; Jerina, D. M.; Self, R.; Evans, W. C.

1972-01-01

Cell-free extracts prepared from a Pseudomonas sp., grown on (+)-catechin, oxidized dihydrogossypetin (3′,4′,5,7,8-pentahydroxyflavanonol) by cleaving the A-ring to form oxaloacetic acid from C-5, C-6, C-7 and C-8 together with 5-(3,4-dihydroxyphenyl)-4-hydroxy-3-oxovalero-δ-lactone. The structure of this lactone was confirmed by synthesis of related phenylvalerolactones. PMID:4198081

Synthesis, structural characterization and DNA interaction of zinc complex from 2,6-diacetylpyridine dihydrazone and {4-[(2E)-2-(hydroxyimino)acetyl]phenoxy} acetic acid.

PubMed

Gup, Ramazan; Gökçe, Cansu; Dilek, Nefise

2015-03-01

A new water soluble zinc complex has been prepared and structurally characterized. The Zn(II) complex was synthesized by the reaction of 2,6-diacetylpyridine dihydrazone (dph) with {4-[(2E)-2-(hydroxyimino)acetyl]phenoxy} acetic acid (H₂L) in the presence of zinc(II) acetate. Single crystal X-ray diffraction study revealed that the zinc ion is situated in distorted trigonal-bipyramidal environment where the equatorial position is occupied by the nitrogen atom of pyridine ring and the oxygen atoms of acetate groups of two oxime ligands (H₂L) whereas the axial positions of the zinc complex are occupied by the imine nitrogen atoms of dph ligand. Characterization of the complex with FTIR, (1)H and (13)C NMR, UV-vis and elemental analysis also confirmed the proposed structure. Interaction of the Zn(II) complex with calf-thymus DNA (CT-DNA) was investigated through UV-vis spectroscopy and viscosity measurements. The results suggest that the complex preferably bind to DNA through the groove binding mode. The zinc complex cleaves plasmid pBR 322 DNA in the presence and absence of an oxidative agent (H₂O₂), possibly through a hydrolytic pathway which is also supported by DNA cleave experiments in the presence of different radical scavengers. The nuclease activity of the zinc complex significantly depends on concentration of the complex and incubation time both in the presence and absence of H₂O₂. DNA cleave activity is inhibited in the presence of methyl green indicating that the zinc complex seems to bind the major groove of DNA. Copyright © 2015 Elsevier B.V. All rights reserved.

Coexistence of ferromagnetism and spin glass freezing in the site-disordered kagome ferrite SrSn2Fe4O11

NASA Astrophysics Data System (ADS)

Shlyk, Larysa; Strobel, S.; Farmer, B.; De Long, L. E.; Niewa, R.

2018-05-01

Single-crystal x-ray diffraction refinements indicate SrSn2Fe4O11 crystallizes in the hexagonal R-type ferrite structure with non-centrosymmetric space group P63mc and lattice parameters a = 5.9541(2) Å, c = 13.5761(5) Å, Z = 2 (R(F) = 0.034). Octahedrally coordinated sites are randomly occupied by Sn and Fe; whereas tetrahedrally coordinated sites are exclusively occupied by Fe, whose displacement from ideal trigonal-bipyramidal coordination causes the loss of inversion symmetry. DC magnetization data indicate SrSn2Fe4O11 single crystals undergo ferro- or ferri-magnetic order below a transition temperature TC = 630 K with very low coercive fields Hc ⊥ = 0.27 Oe and Hc// = 1.5 Oe at 300 K, for applied fields perpendicular and parallel to the c-axis, respectively. The value for TC is exceptionally high, and the coercive fields exceptionally low, among the known R-type ferrites. Enhanced coercivity and thermomagnetic hysteresis suggest the onset of short-range, spin glass order occurs below Tf = 35 K. Optical measurements indicate a band gap of 0.8 eV, consistent with wide-gap semiconducting behavior and a previously established empirical correlation between the semiconducting gap and TC for R-type ferrites based upon Ru.

Characterization of the recognition specificity of BH2, a monoclonal antibody prepared against the HLA-B27 heavy chain.

PubMed

Yu, Hui-Chun; Huang, Kuang-Yung; Lu, Ming-Chi; Huang, Hsien-Lu; Liu, Wei-Ting; Lee, Wen-Chien; Liu, Su-Qin; Huang, Hsien-Bin; Lai, Ning-Sheng

2015-04-13

BH2, a monoclonal antibody prepared against the denatured human leukocytic antigen-B27 heavy chain (HLA-B27 HC), can immunoprecipitate the misfolded HLA-B27 HC complexed with Bip in the endoplasmic reticulum and recognize the homodimerized HLA-B27 HC that is often observed on the cell membrane of patients suffered from ankylosing spondylitis (AS). However, the recognition specificity of BH2 toward the other molecules of HLA-B type and toward the different types of HLA molecules remained uncharacterized. In this study, we carried out the HLA-typing by using the Luminex Technology to characterize the recognition specificity of BH2 and analyzed the binding domain of HLA-B27 HC by BH2. Our results indicated that BH2 preferably binds to molecules of HLA-B and -C rather than HLA-A and the binding site is located within the α2 domain of HLA-B27 HC.

A Conformational Change of C Fragment of Tetanus Neurotoxin Reduces Its Ganglioside-Binding Activity but Does Not Destroy Its Immunogenicity ▿

PubMed Central

Yu, Rui; Yi, Shaoqiong; Yu, Changming; Fang, Ting; Liu, Shuling; Yu, Ting; Song, Xiaohong; Fu, Ling; Hou, Lihua; Chen, Wei

2011-01-01

The C fragment of tetanus neurotoxin (TeNT-Hc) with different conformations was observed due to the four cysteine residues within it which could form different intramolecular disulfide bonds. In this study, we prepared and compared three types of monomeric TeNT-Hc with different conformational components: free sulfhydryls (50 kDa), bound sulfhydryls (44 kDa), and a mixture of the two conformational proteins (half 50 kDa and half 44 kDa). TeNT-Hc with bound sulfhydryls reduced its binding activity to ganglioside GT1b and neuronal PC-12 cells compared to what was seen for TeNT-Hc with free sulfhydryls. However, there was no significant difference among their immunogenicities in mice, including induction of antitetanus toxoid IgG titers, antibody types, and protective capacities against tetanus neurotoxin challenge. Our results showed that the conformational changes of TeNT-Hc resulting from disulfide bond formation reduced its ganglioside-binding activity but did not destroy its immunogenicity, and the protein still retained continuous B cell and T cell epitopes; that is, the presence of the ganglioside-binding site within TeNT-Hc may be not essential for the induction of a fully protective antitetanus response. TeNT-Hc with bound sulfhydryls may be developed into an ideal human vaccine with a lower potential for side effects. PMID:21813664

Thieno[3,2-c]pyran-4-one based novel small molecules: their synthesis, crystal structure analysis and in vitro evaluation as potential anticancer agents.

PubMed

Nakhi, Ali; Adepu, Raju; Rambabu, D; Kishore, Ravada; Vanaja, G R; Kalle, Arunasree M; Pal, Manojit

2012-07-01

Novel thieno[3,2-c]pyran-4-one based small molecules were designed as potential anticancer agents. Expeditious synthesis of these compounds was carried out via a multi-step sequence consisting of few steps such as Gewald reaction, Sandmeyer type iodination, Sonogashira type coupling followed by iodocyclization and then Pd-mediated various C-C bond forming reactions. The overall strategy involved the construction of thiophene ring followed by the fused pyranone moiety and then functionalization at C-7 position of the resultant thieno[3,2-c]pyran-4-one framework. Some of the compounds synthesized showed selective growth inhibition of cancer cells in vitro among which two compounds for example, 5d and 6c showed IC(50) values in the range of 2.0-2.5 μM. The crystal structure analysis of an active compound along with hydrogen bonding patterns and molecular arrangement present within the molecule is described. Copyright © 2012 Elsevier Ltd. All rights reserved.

Virtual Exploration of the Ring Systems Chemical Universe.

PubMed

Visini, Ricardo; Arús-Pous, Josep; Awale, Mahendra; Reymond, Jean-Louis

2017-11-27

Here, we explore the chemical space of all virtually possible organic molecules focusing on ring systems, which represent the cyclic cores of organic molecules obtained by removing all acyclic bonds and converting all remaining atoms to carbon. This approach circumvents the combinatorial explosion encountered when enumerating the molecules themselves. We report the chemical universe database GDB4c containing 916 130 ring systems up to four saturated or aromatic rings and maximum ring size of 14 atoms and GDB4c3D containing the corresponding 6 555 929 stereoisomers. Almost all (98.6%) of these ring systems are unknown and represent chiral 3D-shaped macrocycles containing small rings and quaternary centers reminiscent of polycyclic natural products. We envision that GDB4c can serve to select new ring systems from which to design analogs of such natural products. The database is available for download at www.gdb.unibe.ch together with interactive visualization and search tools as a resource for molecular design.

Leptin, NPY, Melatonin and Zinc Levels in Experimental Hypothyroidism and Hyperthyroidism: The Relation to Zinc.

PubMed

Baltaci, Abdulkerim Kasım; Mogulkoc, Rasim

2017-06-01

Since zinc mediates the effects of many hormones or is found in the structure of numerous hormone receptors, zinc deficiency leads to various functional impairments in the hormone balance. And also thyroid hormones have important activity on metabolism and feeding. NPY and leptin are affective on food intake and regulation of appetite. The present study is conducted to determine how zinc supplementation and deficiency affect thyroid hormones (free and total T3 and T4), melatonin, leptin, and NPY levels in thyroid dysfunction in rats. The experiment groups in the study were formed as follows: Control (C); Hypothyroidism (PTU); Hypothyroidism+Zinc (PTU+Zn); Hypothyroidism+Zinc deficient; Hyperthyroidism (H); Hyperthyroidism+Zinc (H+Zn); and Hyperthyroidism+Zinc deficient. Thyroid hormone parameters (FT 3 , FT 4 , TT 3 , and TT 4 ) were found to be reduced in hypothyroidism groups and elevated in the hyperthyroidism groups. Melatonin values increased in hyperthyroidism and decreased in hypothyroidism. Leptin and NPY levels both increased in hypo- and hyperthyroidism. Zinc levels, on the other hand, decreased in hypothyroidism and increased in hyperthyroidism. Zinc supplementation, particularly when thyroid function is impaired, has been demonstrated to markedly prevent these changes.

A FORTRAN IV Computer Program for the Time Domain Analysis of the Two- Dimensional Dynamic Motions of General Buoy-Cable-Body Systems

DTIC Science & Technology

1977-06-01

SPHEROIDAL BUOYS As mentioned previously, for the limiting case of zero ; educed frequency where tile free surface behaves as a rigid plane, the...4P ) -4 -4 ft O D - % Cdd :# P) fy ou Cd 1d Cd’. . 6 - C3 ’o .. eg S w Cd *g.4C~dI~**II~.a Ký 0 4 : 10 In H-C IV ..4 _ C) bu 0 40 la W C2C W cc lp lqa

The nitrogen isotopic ratio of HC3N towards the L1544 prestellar core

NASA Astrophysics Data System (ADS)

Hily-Blant, P.; Faure, A.; Vastel, C.; Magalhaes, V.; Lefloch, B.; Bachiller, R.

2018-06-01

The origin of the heavily fractionated reservoir of nitrogen in comets remains an issue in the theory of their formation and hence of the solar system. Whether the fractionated reservoir traced by comets is inherited from the interstellar cloud or is the product of processes taking place in the protostar, or in the protoplanetary disk, remains unclear. So far, observations of nitrogen isotopic ratios in protostars or prestellar cores have not securely identified such a fractionated reservoir owing to the intrinsic difficulty of direct isotopic ratios measurements. In this article, we report the detection of 5 rotational lines of HC3N, including the weaker components of the hyperfine multiplets, and two rotational lines of its 15N isotopologue, towards the L1544 prestellar core. Based on a MCMC/non-LTE multi-line analysis at the hyperfine level, we derive the column densities of HC3N (8.0 ± 0.4 × 1013cm-2) and HC_3^{15}N (2.0 ± 0.4 × 1011cm-2) and derive an isotopic ratio of 400±20(1σ). This value suggests that HC3N is slightly depleted in 15N in L1544 with respect to the elemental 14N/15N ratio of ≈330 in the present-day local interstellar medium. Our study also stresses the need for radiative calculations at the hyperfine level. Finally, the comparison of the derived ratio with those obtained in CN and HCN in the same core seems to favor CN+C2H2 as the dominant formation route to HC3N. However, uncertainties in the isotopic ratios preclude definitive conclusions.

The photochemical fractionation of nitrogen isotopologues in Titan's atmosphere

NASA Astrophysics Data System (ADS)

Dobrijevic, M.; Loison, J. C.

2018-06-01

Nitrogen isotopologues could give in principle valuable constraints on the formation and evolution of Titan's atmosphere and its interior over geological time. For this purpose, we developed the first photochemical model dedicated to the study of the fractionation of several nitrogen isotopologues. Emphasis has been placed on several nitriles: HCN, CH3CN, HC3N, C2H3CN, C2H5CN. We show that the HCN/HC15N and HC3N/HC315N ratios are very sensitive to the production of magnetospheric electrons. So, these compounds can serve as probes to study the putative evolution with time of the production of magnetospheric electrons throughout the atmosphere. We also show that the CH3CN/CH3C15N and C2H5CN/C2H5C15N ratios are highly sensitive to cosmic rays. So, they can serve as probes to estimate their effect in the lower atmosphere of Titan (100-300 km). Detection of new isotopologues (particularly CH3C15N) could give strong constraints to photochemical models and could improve our understanding of the main physical and chemical processes at work in Titan's atmosphere.

Crystal structure of 3-({[(morpholin-4-yl)carbono-thio-yl]sulfan-yl}acet-yl)phenyl benzoate.

PubMed

Ambekar, Sachin P; Mahesh Kumar, K; Shirahatti, Arun Kumar M; Kotresh, O; Anil Kumar, G N

2014-11-01

In the title compound, C20H19NO4S2, the morpholine ring adopts the expected chair conformation. The central phenyl ring makes dihedral angles of 67.97 (4) and 7.74 (3)°, respectively, with the benzoate phenyl ring and the morpholine mean plane. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds, forming zigzag chains along the b-axis direction. C-H⋯π inter-actions link centrosymmetrically related mol-ecules, reinforcing the three-dimensional structure.

Protease signaling through protease activated receptor 1 mediate nerve activation by mucosal supernatants from irritable bowel syndrome but not from ulcerative colitis patients

PubMed Central

Buhner, Sabine; Hahne, Hannes; Hartwig, Kerstin; Li, Qin; Vignali, Sheila; Ostertag, Daniela; Meng, Chen; Hörmannsperger, Gabriele; Braak, Breg; Pehl, Christian; Frieling, Thomas; Barbara, Giovanni; De Giorgio, Roberto; Demir, Ihsan Ekin; Ceyhan, Güralp Onur; Zeller, Florian; Boeckxstaens, Guy; Haller, Dirk; Kuster, Bernhard

2018-01-01

Background & aims The causes of gastrointestinal complaints in irritable bowel syndrome (IBS) remain poorly understood. Altered nerve function has emerged as an important pathogenic factor as IBS mucosal biopsy supernatants consistently activate enteric and sensory neurons. We investigated the neurally active molecular components of such supernatants from patients with IBS and quiescent ulcerative colitis (UC). Method Effects of supernatants from 7 healthy controls (HC), 20 IBS and 12 UC patients on human and guinea pig submucous neurons were studied with neuroimaging techniques. We identify differentially expressed proteins with proteome analysis. Results Nerve activation by IBS supernatants was prevented by the protease activated receptor 1 (PAR1) antagonist SCHE79797. UC supernatants also activated enteric neurons through protease dependent mechanisms but without PAR1 involvement. Proteome analysis of the supernatants identified 204 proteins, among them 17 proteases as differentially expressed between IBS, UC and HC. Of those the four proteases elastase 3a, chymotrypsin C, proteasome subunit type beta-2 and an unspecified isoform of complement C3 were significantly more abundant in IBS compared to HC and UC supernatants. Of eight proteases, which were upregulated in IBS, the combination of elastase 3a, cathepsin L and proteasome alpha subunit-4 showed the highest prediction accuracy of 98% to discriminate between IBS and HC groups. Elastase synergistically potentiated the effects of histamine and serotonin–the two other main neuroactive substances in the IBS supernatants. A serine protease inhibitor isolated from the probiotic Bifidobacterium longum NCC2705 (SERPINBL), known to inhibit elastase-like proteases, prevented nerve activation by IBS supernatants. Conclusion Proteases in IBS and UC supernatants were responsible for nerve activation. Our data demonstrate that proteases, particularly those signalling through neuronal PAR1, are biomarker candidates for IBS, and protease profiling may be used to characterise IBS. PMID:29529042

Multiagent vaccines vectored by Venezuelan equine encephalitis virus replicon elicits immune responses to Marburg virus and protection against anthrax and botulinum neurotoxin in mice.

PubMed

Lee, John S; Groebner, Jennifer L; Hadjipanayis, Angela G; Negley, Diane L; Schmaljohn, Alan L; Welkos, Susan L; Smith, Leonard A; Smith, Jonathan F

2006-11-17

The development of multiagent vaccines offers the advantage of eliciting protection against multiple diseases with minimal inoculations over a shorter time span. We report here the results of using formulations of individual Venezuelan equine encephalitis (VEE) virus replicon-vectored vaccines against a bacterial disease, anthrax; a viral disease, Marburg fever; and against a toxin-mediated disease, botulism. The individual VEE replicon particles (VRP) expressed mature 83-kDa protective antigen (MAT-PA) from Bacillus anthracis, the glycoprotein (GP) from Marburg virus (MBGV), or the H(C) fragment from botulinum neurotoxin (BoNT H(C)). CBA/J mice inoculated with a mixture of VRP expressing BoNT H(C) serotype C (BoNT/C H(C)) and MAT-PA were 80% protected from a B. anthracis (Sterne strain) challenge and then 100% protected from a sequential BoNT/C challenge. Swiss mice inoculated with individual VRP or with mixtures of VRP vaccines expressing BoNT H(C) serotype A (BoNT/A H(C)), MAT-PA, and MBGV-GP produced antibody responses specific to the corresponding replicon-expressed protein. Combination of the different VRP vaccines did not diminish the antibody responses measured for Swiss mice inoculated with formulations of two or three VRP vaccines as compared to mice that received only one VRP vaccine. Swiss mice inoculated with VRP expressing BoNT/A H(C) alone or in combination with VRP expressing MAT-PA and MBGV GP, were completely protected from a BoNT/A challenge. These studies demonstrate the utility of combining individual VRP vaccines into multiagent formulations for eliciting protective immune responses to various types of diseases.

Thermal collapse and hierarchy of polymorphs in a faujasite-type zeolite and its analogous melt-quenched glass

NASA Astrophysics Data System (ADS)

Palenta, Theresia; Fuhrmann, Sindy; Greaves, G. Neville; Schwieger, Wilhelm; Wondraczek, Lothar

2015-02-01

We examine the route of structural collapse and re-crystallization of faujasite-type (Na,K)-LSX zeolite. As the first step, a rather stable amorphous high density phase HDAcollapse is generated through an order-disorder transition from the original zeolite via a low density phase LDAcollapse, at around 790 °C. We find that the overall amorphization is driven by an increase in the bond angle distribution within T-O-T and a change in ring statistics to 6-membered TO4 (T = Si4+, Al3+) rings at the expense of 4-membered rings. The HDAamorph transforms into crystalline nepheline, though, through an intermediate metastable carnegieite phase. In comparison, the melt-derived glass of similar composition, HDAMQ, crystallizes directly into the nepheline phase without the occurrence of intermediate carnegieite. This is attributed to the higher structural order of the faujasite-derived HDAcollapse which prefers the re-crystallization into the highly symmetric carnegieite phase before transformation into nepheline with lower symmetry.

Near-resonant vibration. -->. vibration energy transfer under single-collision conditions. [Propynal

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

Breener, D M

1981-01-01

Energy transfer in single collisions of propynal (HC triple bond C-CHO) subsequent to ir multiphonon absorption (CO/sub 2/ laser) was studied. SiF/sub 4/, CH/sub 3/F, CCl/sub 4/, and CH/sub 4/ were added. (DLC)

Conformational heterogeneity in the C-terminal zinc fingers of human MTF-1: an NMR and zinc-binding study.

PubMed

Giedroc, D P; Chen, X; Pennella, M A; LiWang, A C

2001-11-09

The human metalloregulatory transcription factor, metal-response element (MRE)-binding transcription factor-1 (MTF-1), contains six TFIIIA-type Cys(2)-His(2) motifs, each of which was projected to form well-structured betabetaalpha domains upon Zn(II) binding. In this report, the structure and backbone dynamics of a fragment containing the unusual C-terminal fingers F4-F6 has been investigated. (15)N heteronuclear single quantum coherence (HSQC) spectra of uniformly (15)N-labeled hMTF-zf46 show that Zn(II) induces the folding of hMTF-zf46. Analysis of the secondary structure of Zn(3) hMTF-zf46 determined by (13)Calpha chemical shift indexing and the magnitude of (3)J(Halpha-HN) clearly reveal that zinc fingers F4 and F6 adopt typical betabetaalpha structures. An analysis of the heteronuclear backbone (15)N relaxation dynamics behavior is consistent with this picture and further reveals independent tumbling of the finger domains in solution. Titration of apo-MTF-zf46 with Zn(II) reveals that the F4 domain binds Zn(II) significantly more tightly than do the other two finger domains. In contrast to fingers F4 and F6, the betabetaalpha fold of finger F5 is unstable and only partially populated at substoichiometric Zn(II); a slight molar excess of zinc results in severe conformational exchange broadening of all F5 NH cross-peaks. Finally, although Cd(II) binds to apo-hMTF-zf46 as revealed by intense S(-)-->Cd(II) absorption, a non-native structure results; addition of stoichiometric Zn(II) to the Cd(II) complex results in quantitative refolding of the betabetaalpha structure in F4 and F6. The functional implications of these results are discussed.

Distinctive Klf4 mutants determine preference for DNA methylation status

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

Hashimoto, Hideharu; Wang, Dongxue; Steves, Alyse N.

Reprogramming of mammalian genome methylation is critically important but poorly understood. Klf4, a transcription factor directing reprogramming, contains a DNA binding domain with three consecutive C2H2 zinc fingers. Klf4 recognizes CpG or TpG within a specific sequence. Mouse Klf4 DNA binding domain has roughly equal affinity for methylated CpG or TpG, and slightly lower affinity for unmodified CpG. The structural basis for this key preference is unclear, though the side chain of Glu446 is known to contact the methyl group of 5-methylcytosine (5mC) or thymine (5-methyluracil). We examined the role of Glu446 by mutagenesis. Substituting Glu446 with aspartate (E446D) resultedmore » in preference for unmodified cytosine, due to decreased affinity for 5mC. In contrast, substituting Glu446 with proline (E446P) increased affinity for 5mC by two orders of magnitude. Structural analysis revealed hydrophobic interaction between the proline's aliphatic cyclic structure and the 5-methyl group of the pyrimidine (5mC or T). As in wild-type Klf4 (E446), the proline at position 446 does not interact directly with either the 5mC N4 nitrogen or the thymine O4 oxygen. In contrast, the unmethylated cytosine's exocyclic N4 amino group (NH2) and its ring carbon C5 atom hydrogen bond directly with the aspartate carboxylate of the E446D variant. Both of these interactions would provide a preference for cytosine over thymine, and the latter one could explain the E446D preference for unmethylated cytosine. Finally, we evaluated the ability of these Klf4 mutants to regulate transcription of methylated and unmethylated promoters in a luciferase reporter assay.« less

Detergent-Induced Stabilization and Improved 3D Map of the Human Heteromeric Amino Acid Transporter 4F2hc-LAT2

PubMed Central

Harder, Daniel; Stauffer, Mirko; Jeckelmann, Jean-Marc; Brühlmann, Béla; Rosell, Albert; Ilgü, Hüseyin; Kovar, Karin; Palacín, Manuel; Fotiadis, Dimitrios

2014-01-01

Human heteromeric amino acid transporters (HATs) are membrane protein complexes that facilitate the transport of specific amino acids across cell membranes. Loss of function or overexpression of these transporters is implicated in several human diseases such as renal aminoacidurias and cancer. HATs are composed of two subunits, a heavy and a light subunit, that are covalently connected by a disulphide bridge. Light subunits catalyse amino acid transport and consist of twelve transmembrane α-helix domains. Heavy subunits are type II membrane N-glycoproteins with a large extracellular domain and are involved in the trafficking of the complex to the plasma membrane. Structural information on HATs is scarce because of the difficulty in heterologous overexpression. Recently, we had a major breakthrough with the overexpression of a recombinant HAT, 4F2hc-LAT2, in the methylotrophic yeast Pichia pastoris. Microgram amounts of purified protein made possible the reconstruction of the first 3D map of a human HAT by negative-stain transmission electron microscopy. Here we report the important stabilization of purified human 4F2hc-LAT2 using a combination of two detergents, i.e., n-dodecyl-β-D-maltopyranoside and lauryl maltose neopentyl glycol, and cholesteryl hemisuccinate. The superior quality and stability of purified 4F2hc-LAT2 allowed the measurement of substrate binding by scintillation proximity assay. In addition, an improved 3D map of this HAT could be obtained. The detergent-induced stabilization of the purified human 4F2hc-LAT2 complex presented here paves the way towards its crystallization and structure determination at high-resolution, and thus the elucidation of the working mechanism of this important protein complex at the molecular level. PMID:25299125

Detergent-induced stabilization and improved 3D map of the human heteromeric amino acid transporter 4F2hc-LAT2.

PubMed

Meury, Marcel; Costa, Meritxell; Harder, Daniel; Stauffer, Mirko; Jeckelmann, Jean-Marc; Brühlmann, Béla; Rosell, Albert; Ilgü, Hüseyin; Kovar, Karin; Palacín, Manuel; Fotiadis, Dimitrios

2014-01-01

Human heteromeric amino acid transporters (HATs) are membrane protein complexes that facilitate the transport of specific amino acids across cell membranes. Loss of function or overexpression of these transporters is implicated in several human diseases such as renal aminoacidurias and cancer. HATs are composed of two subunits, a heavy and a light subunit, that are covalently connected by a disulphide bridge. Light subunits catalyse amino acid transport and consist of twelve transmembrane α-helix domains. Heavy subunits are type II membrane N-glycoproteins with a large extracellular domain and are involved in the trafficking of the complex to the plasma membrane. Structural information on HATs is scarce because of the difficulty in heterologous overexpression. Recently, we had a major breakthrough with the overexpression of a recombinant HAT, 4F2hc-LAT2, in the methylotrophic yeast Pichia pastoris. Microgram amounts of purified protein made possible the reconstruction of the first 3D map of a human HAT by negative-stain transmission electron microscopy. Here we report the important stabilization of purified human 4F2hc-LAT2 using a combination of two detergents, i.e., n-dodecyl-β-D-maltopyranoside and lauryl maltose neopentyl glycol, and cholesteryl hemisuccinate. The superior quality and stability of purified 4F2hc-LAT2 allowed the measurement of substrate binding by scintillation proximity assay. In addition, an improved 3D map of this HAT could be obtained. The detergent-induced stabilization of the purified human 4F2hc-LAT2 complex presented here paves the way towards its crystallization and structure determination at high-resolution, and thus the elucidation of the working mechanism of this important protein complex at the molecular level.

2-Hy-droxy-16-[(E)-4-methyl-benzyl-idene]-13-(4-methyl-phen-yl)-12-phenyl-1,11-diaza-penta-cyclo-[12.3.1.0.0.0]octa-deca-3(8),4,6-triene-9,15-dione.

PubMed

Kumar, Raju Suresh; Osman, Hasnah; Abdul Rahim, Aisyah Saad; Goh, Jia Hao; Fun, Hoong-Kun

2010-07-24

In the title compound, C(37)H(32)N(2)O(3), an intra-molecular O-H⋯N hydrogen bond generates a five-membered ring, producing an S(5) motif. The piperidone ring adopts a half-chair conformation. The two fused pyrrolidine rings have similar envelope conformations. The interplanar angles between the benzene rings A/B and C/D are 75.68 (7) and 30.22 (6)°, respectively. In the crystal structure, adjacent mol-ecules are inter-connected into chains propagating along the [010] direction via inter-molecular C-H⋯O hydrogen bonds. Further stabilization is provided by weak C-H⋯π inter-actions.

Group 4 transition metal CH2=MF2, CHF=MF2, and HC/MF3 complexes formed by C-F activation and alpha-fluorine transfer.

PubMed

Lyon, Jonathan T; Andrews, Lester

2007-06-11

Group 4 transition metal methylidene difluoride complexes (CH2=MF2) are formed by the reaction of methylene fluoride with laser-ablated metal atoms and are isolated in an argon matrix. Isotopic substitution of the CH2F2 precursor and theoretical computations (B3LYP and CCSD) confirm product identifications and assignments. Our calculations indicate that the CH2=MF2 complexes have near C2v symmetry and are considerably more stable than other possible products (CH2(mu-F)MF and CHF=MHF). The primary reaction exothermicity provides more than enough energy to activate the initial bridge-bonded CH2(mu-F)MF products on the triplet potential energy surface to complete an alpha-F transfer to form the very stable CH2=MF2 products. Analogous experiments with CHF3 produce CHF=TiF2, which is not distorted at the C-H bond, whereas the heavier group 4 metals form lower-energy triplet HC/MF3 complexes, which contain weak degenerate C(p)-M(d) pi-bonding interactions. Comparisons are made with the CH2=MHF methylidene species, which showed considerable agostic distortions.

Bioavailability of trace elements in beans and zinc-biofortified wheat in pigs.

PubMed

Carlson, Dorthe; Nørgaard, Jan Værum; Torun, Bulent; Cakmak, Ismail; Poulsen, Hanne Damgaard

2012-12-01

The objectives of this experiment were to study bioavailability of trace elements in beans and wheat containing different levels of zinc and to study how the water solubility of trace elements was related to the bioavailability in pigs. Three wheat and two bean types were used: wheat of Danish origin as a control (CtrlW), two Turkish wheat types low (LZnW) and high (HZnW) in zinc, a common bean (Com), and a faba bean (Faba). Two diets were composed by combining 81 % CtrlW and 19 % Com or Faba beans. Solubility was measured as the trace element concentration in the supernatant of feedstuffs, and diets incubated in distilled water at pH 4 and 38°C for 3 h. The bioavailability of zinc and copper of the three wheat types and the two bean-containing diets were evaluated in the pigs by collection of urine and feces for 7 days. The solubility of zinc was 34-63 %, copper 18-42 %, and iron 3-11 %. The zinc apparent digestibility in pigs was similar in the three wheat groups (11-14 %), but was significantly higher in the CtrlW+Faba group (23 %) and negative in the CtrlW+Com group (-30 %). The apparent digestibility of copper was higher in the HZnW (27 %) and CtrlW+Faba (33 %) groups than in the CtrlW (17 %) and LZnW (18 %) groups. The apparent copper digestibility of the CtrlW+Com diet was negative (-7 %). The solubility and digestibility results did not reflect the concentration in feedstuffs. The in vitro results of water solubility showed no relationship to the results of trace mineral bioavailability in pigs.

Photochemistry of Pluto's atmosphere and ionosphere near perihelion

NASA Astrophysics Data System (ADS)

Krasnopolsky, Vladimir A.; Cruikshank, Dale P.

1999-09-01

We consider Pluto's photochemistry using a background model for a hydrodynamically escaping atmosphere by Krasnopolsky [1999]. Some adjustments are made in the basic continuity equation and in the boundary conditions to account for hydrodynamic flow in the atmosphere. We model the photochemistry for 44 neutral and 23 ion species. Because of the high methane mixing ratio, Pluto's photochemistry is more similar to that of Titan than that of Triton. Charge exchange between N2+ and CH4 significantly reduces the production of atomic nitrogen. The most abundant photochemical products are C2H2(3×1017), C4H2(1017), HCN(6×1016), H2(4×1016), C2H4(4×1016), HC3N(3.4×1016), C2H6(2×1016), C3H2(9×1015), and C3H4 (8×1015, all in cm-2). In addition to the parent N2, CH4, and CO molecules which absorb photons with λ<145nm, these products absorb almost completely photons with λ<185nm, therefore significantly increasing the number of dissociation events. Photochemical losses of the parent species are much smaller than their escape. Precipitation rates are the highest for C2H2, C4H2, HC3N, HCN, C2H6, and C2H4 (65, 58, 23, 14, 9, and 6 g cm-2 Byr-1, respectively, reduced by a factor of 3 to account for seasonal variations). Escape of photochemical products is highest for H2, H, C2H2, C2H4, HCN, and N(2×1026, 1.4×1026, 6×1024, 3.6×1024, 2.3×1024, and 1.8×1024s-1, respectively). The electron density reaches a maximum of 800 cm-3 at 2250 km. The most abundant ions are HCNH+, C3H3+, and C3H5+. Some of the photochemical products might be detected using the technique of UV solar occultation spectroscopy from a spacecraft flyby.

46 CFR 164.019-3 - Definitions.

Code of Federal Regulations, 2012 CFR

2012-10-01

... Guard-approved PFDs. Commandant means the Chief of the Lifesaving and Fire Safety Division, Office of... code PFD type acceptable for use 1 I, II, and III. 2 II and III. 3 III. 4B IV (all Ring Buoys). 4BC IV (Buoyant Cushions). 4RB IV (Recreational Ring Buoys only). 5 Wearable Type V (intended use must be...

High-level SUMO-mediated fusion expression of ABP-dHC-cecropin A from multiple joined genes in Escherichia coli.

PubMed

Zhang, Jiaxin; Movahedi, Ali; Wei, Zhiheng; Sang, Ming; Wu, Xiaolong; Wang, Mengyang; Wei, Hui; Pan, Huixin; Yin, Tongming; Zhuge, Qiang

2016-09-15

The antimicrobial peptide ABP-dHC-cecropin A is a small cationic peptide with potent activity against a wide range of bacterial species. Evidence of antifungal activity has also been suggested; however, evaluation of this peptide has been limited due to the low expression of cecropin proteins in Escherichia coli. To improve the expression level of ABP-dHC-cecropin A in E. coli, tandem repeats of the ABP-dHC-cecropin A gene were constructed and expressed as fusion proteins (SUMO-nABP-dHC-cecropin, n = 1, 2, 3, 4) via pSUMO-nABP-dHC-cecropin A vectors (n = 1, 2, 3, 4). Comparison of the expression levels of soluble SUMO-nABP-dHC-cecropin A fusion proteins (n = 1, 2, 3, 4) suggested that BL21 (DE3)/pSUMO-3ABP-dHC-cecropin A is an ideal recombinant strain for ABP-dHC-cecropin A production. Under the selected conditions of cultivation and isopropylthiogalactoside (IPTG) induction, the expression level of ABP-dHC-cecropin A was as high as 65 mg/L, with ∼21.3% of the fusion protein in soluble form. By large-scale fermentation, protein production reached nearly 300 mg/L, which is the highest yield of ABP-dHC-cecropin A reported to date. In antibacterial experiments, the efficacy was approximately the same as that of synthetic ABP-dHC-cecropin A. This method provides a novel and effective means of producing large amounts of ABP-dHC-cecropin A. Copyright © 2016 Elsevier Inc. All rights reserved.

Superconductivity in the Nb-Ru-Ge σ phase

DOE PAGES

Carnicom, Elizabeth M.; Xie, Weiwei; Sobczak, Zuzanna; ...

2017-12-07

Here, we show that the previously unreported ternary σ-phase material Nb 20.4Ru 5.7Ge 3.9 (Nb 0.68Ru 0.19Ge 0.13) is a superconductor with a critical temperature of 2.2 K. Temperature-dependent magnetic susceptibility, resistance, and specific heat measurements were used to characterize the superconducting transition. The Sommerfeld constant γ for Nb 20.4Ru 5.7Ge 3.9 is 91 mJ mol-f.u. -1K -2 (~3 mJ mol-atom -1K -2) and the specific heat anomaly at the superconducting transition, ΔC/γT c, is approximately 1.38. The zero-temperature upper critical field (µ 0Hc 2(0)) was estimated to be 2 T by resistance data. Field-dependent magnetization data analysis estimated µmore » 0Hc 1(0) to be 5.5 mT. Thus, the characterization shows Nb 20.4Ru 5.7Ge 3.9 to be a type II BCS superconductor. This material appears to be the first reported ternary phase in the Nb-Ru-Ge system, and the fact that there are no previously reported binary Nb-Ru, Nb-Ge, or Ru-Ge σ-phases shows that all three elements are necessary to stabilize the material. An analogous σ-phase in the Ta-Ru-Ge system did not display superconductivity above 1.7 K, which suggests that electron count cannot govern the superconductivity observed. Preliminary characterization of a possible superconducting σ-phase in the Nb-Ru-Ga system is also reported.« less

1-(4,4''-Difluoro-5'-meth-oxy-1,1':3',1''-terphenyl-4'-yl)ethanone.

PubMed

Fun, Hoong-Kun; Hemamalini, Madhukar; Samshuddin, S; Narayana, B; Sarojini, B K

2012-01-01

In the title compound, C(21)H(16)F(2)O(2), the central benzene ring is inclined at dihedral angles of 30.91 (8) and 46.88 (7)° to the two terminal fluoro-substituted rings. The dihedral angle between the two terminal fluoro-subsituted rings is 68.34 (8)°. An intra-molecular C-H⋯O hydrogen bond generates an S(6) ring motif. The crystal structure is stabilized by weak C-H⋯π inter-actions.

Interactions between 2,4-bis-pteridine-1,5-benzodiazepine and group 12 dihalides: synthesis, spectral and XRD structural studies and theoretical calculations.

PubMed

Illán-Cabeza, Nuria A; Jiménez-Pulido, Sonia B; Hueso-Ureña, Francisco; Peña-Ruiz, Tomás; Quirós-Olozábal, Miguel; Moreno-Carretero, Miguel N

2016-11-28

2,4-Bis(1,3,7-trimethyl-pteridine-2,4(1H,3H)-dione-6-yl)-2,3-dihydro-2-methyl-1H-1,5-benzodiazepine (DLMBZD) has been prepared and its molecular and crystal structures have been determined from spectral and XRD data. The benzodiazepine ligand was reacted with zinc(ii), cadmium(ii) and mercury(ii) chloride, bromide and iodide to give complexes with general formula [M(DLMBZD)X 2 ]. The complexes have been synthesized and characterized by IR, NMR and elemental analysis. The structure of seven complexes has been obtained by single crystal X-ray diffraction. In all the cases, the metal is (2 + 2 + 1)-five-coordinated by two halide ligands, two nitrogen atoms from pyrazine and diazepine rings and a carbonyl oxygen from a pteridine ring. The coordinated-metal environment is a square-based pyramid, with increasing trigonality from Hg(ii) to Zn(ii) complexes. To coordinate the metals, the ligand folds itself, establishing four intramolecular σ-π interactions with the pyrimidine and pyrazine rings. A topological analysis of the electron density using the Quantum Theory of Atoms in Molecules and the complexes stability has been performed.

3-(Adamantan-1-yl)-4-ethyl-1-{[4-(2-meth-oxy-phen-yl)piperazin-1-yl]meth-yl}-1H-1,2,4-triazole-5(4H)-thione.

PubMed

El-Emam, Ali A; Al-Tuwaijri, Hanaa M; Al-Abdullah, Ebtehal S; Chidan Kumar, C S; Fun, Hoong-Kun

2014-01-01

In the title compound, C26H37N5OS, the piperazine ring adopts a chair conformation. The triazole ring forms dihedral angles of 67.85 (9) and 59.41 (9)° with the piperazine and benzene rings, respectively, resulting in an approximate V-shaped conformation for the mol-ecule. An intra-molecular C-H⋯O hydrogen bond generates an S(6) ring motif. The crystal structure features C-H⋯π inter-actions, producing a two-dimensional supramolecular architecture.

Variations in CCR5, but not HFE, ELMO1, or SLC12A3, are associated with susceptibility to kidney disease in north Indian individuals with type 2 diabetes.

PubMed

Yadav, Ashok K; Kumar, Vinod; Dutta, Pinaki; Bhansali, Anil; Jha, Vivekanand

2014-11-01

Diabetic nephropathy (DN), the leading cause of end-stage renal disease worldwide, may have a genetic component. In the present study, we investigated variations in a set of genes with susceptibility to DN in a north Indian population. Four genes (HFE, ELMO1, SLC12A3, and CCR5) were selected on the basis of reported association with type 2 diabetes and nephropathy. In all, 417 diabetic subjects (215 without kidney disease [DM] and 202 with DN) and 197 healthy controls (HC) were evaluated for variations in HFE (845 G>A and 187G>C), SLC12A3 (g.34372G>A), CCR5 (59029A>G), and ELMO1 (+9170 G>A). Polymorphism analysis was performed by polymerase chain reaction-restriction fragment length polymorphism and Taqman allele discrimination assays. Significant differences were found in genotype and allelic frequency in SLC12A3 (g.34372G>A) between diabetic subjects and HC (P < 0.03). There were no differences in the SLC12A3 g.34372G>A (AA+GA) genotype between diabetic subjects with and without nephropathy. However, the CCR5 59029AA genotype and A allele were significantly more frequent in diabetics compared with the HC (P = 0.01 and 0.03, respectively) and subjects with DN versus DM (P = 0.002 and 0.01, respectively). For ELMO1 (+9170 G>A), the GG genotype frequency was higher in the diabetic versus HC group. There were no differences in the frequency of HFE-845 G>A and HFE-187G>C among the groups. This study shows that the CCR5 AA genotype is over-represented in subjects with kidney disease due to type 2 diabetes. The CCR5 59029G>A and ELMO1 (+9170 G>A) loci are more frequent, and the SLC12A3 34372 AA genotype is associated with a reduced risk of diabetes. © 2014 Ruijin Hospital, Shanghai Jiaotong University School of Medicine and Wiley Publishing Asia Pty Ltd.

The plant homeodomain fingers of fission yeast Msc1 exhibit E3 ubiquitin ligase activity.

PubMed

Dul, Barbara E; Walworth, Nancy C

2007-06-22

The DNA damage checkpoint pathway governs how cells regulate cell cycle progression in response to DNA damage. A screen for suppressors of a fission yeast chk1 mutant defective in the checkpoint pathway identified a novel Schizosaccharomyces pombe protein, Msc1. Msc1 contains 3 plant homeodomain (PHD) finger motifs, characteristically defined by a C4HC3 consensus similar to RING finger domains. PHD finger domains in viral proteins and in the cellular protein kinase MEKK1 (mitogen-activated protein kinase/extracellular signal-regulated kinase kinase kinase 1) have been implicated as ubiquitin E3 protein ligases that affect protein stability. The close structural relationship of PHD fingers to RING fingers suggests that other PHD domain-containing proteins might share this activity. We show that each of the three PHD fingers of Msc1 can act as ubiquitin E3 ligases, reporting for the first time that PHD fingers from a nuclear protein exhibit E3 ubiquitin ligase activity. The function of the PHD fingers of Msc1 is needed to rescue the DNA damage sensitivity of a chk1Delta strain. Msc1 co-precipitates Rhp6, the S. pombe homologue of the human ubiquitin-conjugating enzyme Ubc2. Strikingly, deletion of msc1 confers complete suppression of the slow growth phenotype, UV and hydroxyurea sensitivities of an rhp6 deletion strain and restores deficient histone H3 methylation observed in the rhp6Delta mutant. We speculate that the target of the E3 ubiquitin ligase activity of Msc1 is likely to be a chromatin-associated protein.

Crystal packing analysis of 1-(3,4-dimethoxyphenyl)-3-(4-bromophenyl)prop-2-en-1-one exhibiting a putative halogen bond Csbnd Br⋯O

NASA Astrophysics Data System (ADS)

Madan Kumar, Shankar; Fares Hezam, Al-Ostoot; Manjunath, B. C.; Shamprasad, Varija Raghu; Eissa Mohammed, Yasser Hussein; Mahesh, N.; Zabiulla; Shaukath, A. K.; Lokanath, N. K.; Byrappa, K.

2018-03-01

The title compound, 1-(3,4-dimethoxyphenyl)-3-(4-bromophenyl) prop-2-en-1-one (1DBr) was synthesized and characterized based on spectroscopic analysis (MS, FT-IR, Elemental analysis, UV-visible, 1H NMR and 13C NMR) and finally the three-dimensional structure is confirmed using single crystal X-ray diffraction studies. The molecule is almost planar and the C--H⋯O intramolecular hydrogen bond closes the ring S(5). In the crystal structure, the molecules are connected through intermolecular hydrogen bond C--H⋯O (R22(14) ring motif) and intermolecular interactions (C--H⋯π and C--O⋯π). Hirshfeld surfaces computational method was employed to quantify the inter-contacts (2D Fingerprint plots) and calculate enrichment ratio (E). The highest value of E is calculated for the contact Br⋯O (1.65) followed by C⋯C (1.02) and have high propensity for forming contacts in the crystal. This provides the basis for the existence of putative halogen bond of the type C-Br⋯O. In addition, the Energy-framework analysis was used to analyze and visualize the 3D-topology of the crystal packing. The dispersion energy framework is dominated over the electrostatic energy-frameworks. The thermogravimetric analysis (TGA) provided the thermal degradation of the 1DBr to be from 230 to 320 °C.

Formation of Cyclopenta[c]pyridine Derivatives from 2,5-Disubstituted Pyrroles and 1,4-Dibromo-1,3-butadienes via Pyrrole-Ring One-Carbon Expansion.

PubMed

Yin, Jianhao; Ye, Qingyu; Hao, Wei; Du, Shuaijing; Gu, Yucheng; Zhang, Wen-Xiong; Xi, Zhenfeng

2017-01-06

Reactions between 1,4-dibromo-1,3-butadienes and 2,5-disubstituted pyrroles afforded cyclopenta[c]pyridine derivatives in high yield, catalyzed by palladium and a cyclopentadiene-phosphine ligand (L1). Insertion of one terminal carbon of the butadienyl skeleton into one C═C double bond in the pyrrole ring resulted in ring expansion, along with a 1,2-shift of an alkyl or an aryl substituent on the butadienes.

1-(4-Chloro-2-fluoro-phen-yl)-4-difluoro-methyl-3-methyl-1H-1,2,4-triazol-5(4H)-one.

PubMed

Ren, Dong-Mei; Wang, Yong-Yi

2012-04-01

In the crystal structure of the title compound, C(10)H(7)ClF(3)N(3)O, pairs of mol-ecules are connected into dimers via pairs of C-H⋯O hydrogen bonds. The dihedral angle between the benzene ring and attached triazolone ring is 53.2 (1)°.

Dipeptidyl peptidase III is a zinc metallo-exopeptidase. Molecular cloning and expression.

PubMed Central

Fukasawa, K; Fukasawa, K M; Kanai, M; Fujii, S; Hirose, J; Harada, M

1998-01-01

We have purified dipeptidyl peptidase III (EC 3.4.14.4) from human placenta. It had a pH optimum of 8.8 and readily hydrolysed Arg-Arg-beta-naphthylamide. Monoamino acid-, Gly-Phe-, Gly-Pro- and Bz-Arg-beta-naphthylamides were not hydrolysed at all. The enzyme was inhibited by p-chloromercuriphenylsulphonic acid, metal chelators and 3,4-dichloroisocoumarin and contained 1 mol of zinc per mol of enzyme. The zinc dissociation constant was 250 fM at pH 7. 4 as determined by the zinc binding study. We isolated, by immunological screening of a Uni-ZAP XR cDNA library constructed from rat liver mRNA species, a cDNA clone with 2633 bp encoding the rat enzyme. The longest open reading frame encodes a 827-residue protein with a theoretical molecular mass of 92790 Da. Escherichia coli SOLR cells were infected with the pBluescript phagemid containing the cloned cDNA and established the overexpression of a protein that hydrolysed Arg-Arg-beta-naphthylamide. The recombinant protein was purified and the amino acid sequence of the protein was confirmed. We presumed that the putative zinc-binding domain involved in catalysis was present in the recombinant enzyme. It was a novel zinc-binding motif in that one amino acid residue was inserted into the conserved HEXXH motif characteristic of the metalloproteinases. PMID:9425109

Data Validation Package May 2015, Groundwater Sampling at the Shoal, Nevada, Site

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

Findlay, Rick; Kautsky, Mark

The U.S. Department of Energy Office of Legacy Management conducted annual sampling at the Shoal, Nevada, Site (Shoal) in May 2015. Groundwater samples were collected from wells MV-1, MV-2, MV-3, MV-4, MV-5, H-3, HC-1, HC-2d, HC-3, HC-4, HC-5, HC-6, HC-7, HC-8, and HS-1. Sampling was conducted as specified in the Sampling and Analysis Plan for US. Department of Energy Office of Legacy Management Sites (LMS/PRO/S04351, continually updated, http://energy.gov/lm/downloads/sampling-and-analysis-plan-us-department-energy­ office-legacy-management-sites). Monitoring wells MV-1, MV-2, MV-3, MV-4, MV-5, HC-2d, HC-4, HC-5, HC-7, HC-8, and HS-1 were purged prior to sampling using dedicated submersible pumps. At least one well casing volume was removed,more » and field parameters (temperature, pH, and specific conductance) were allowed to stabilize before samples were collected. Samples were collected from wells H-3, HC-1, HC-3, and HC-6 using a depth-specific bailer because these wells are not completed with dedicated submersible pumps. Samples were submitted under Requisition Index Number (RIN) 15057042 to ALS Laboratory Group in Fort Collins, Colorado, for the determination of bromide, gross alpha, gross beta, tritium, uranium isotopes, and total uranium (by mass); and under RIN 15057043 to the University of Arizona for the determination of carbon-14 and iodine-129. A duplicate sample from location MV-2 was included with RIN 15057042. The laboratory results from the 2015 sampling event are consistent with those of previous years with the exception of sample results from well HC-4. This well continues to be the only well with tritium concentrations above the laboratory’s minimum detectable concentration which is attributed to the wells proximity to the nuclear detonation. The tritium concentration (731 picocuries per liter [pCi/L]) is consistent with past results and is below the U.S. Environmental Protection Agency's (EPA) maximum contaminant level (MCL) of 20,000 pCi/L. However, concentrations of gross alpha, uranium, and carbon-14 all increased in the sample from well HC-4 during this sampling event. Concentrations of gross alpha and uranium have been above the EPA MCLs in this well since 2012 and the highest concentrations of gross alpha (60.6 pCi/L) and uranium (110 micrograms per liter) were detected during this sampling event. Refer to the time-concentration plots included with this report. Also see the 2015 Groundwater Monitoring Report Project Shoal Area: Subsurface Corrective Action Unit 447 for additional information on the 2015 sampling results.« less

Detection of the HC3NH+ and HCNH+ ions in the L1544 pre-stellar core

NASA Astrophysics Data System (ADS)

Quénard, D.; Vastel, C.; Ceccarelli, C.; Hily-Blant, P.; Lefloch, B.; Bachiller, R.

2017-09-01

The L1544 pre-stellar core was observed as part of the ASAI (Astrochemical Surveys At IRAM) Large Program. We report the first detection in a pre-stellar core of the HCNH+ and HC3NH+ ions. The high spectral resolution of the observations allows us to resolve the hyperfine structure of HCNH+. Local thermodynamic equilibrium (LTE) analysis leads to derive a column density equal to (2.0 ± 0.2) × 1013 cm-2 for HCNH+ and (1.5 ± 0.5) × 1011 cm-2 for HC3NH+. We also present non-LTE analysis of five transitions of HC3N, three transitions of H13CN and one transition of HN13C, all of them linked to the chemistry of HCNH+ and HC3NH+. We computed for HC3N, HCN and HNC a column density of (2.0 ± 0.4) × 1013 cm-2, (3.6 ± 0.9) × 1014 cm-2 and (3.0 ± 1.0) × 1014 cm-2, respectively. We used the gas-grain chemical code nautilus to predict the abundances of all these species across the pre-stellar core. Comparison of the observations with the model predictions suggests that the emission from HCNH+ and HC3NH+ originates in the external layer where non-thermal desorption of other species was previously observed. The observed abundance of both ionic species ([HCNH+] ≃ 3 × 10-10 and [HC3NH+] ≃ [1.5 - 3.0] × 10-12, with respect to H2) cannot be reproduced at the same time by the chemical modelling within the error bars of the observations only. We discuss the possible reasons for the discrepancy and suggest that the current chemical models are not fully accurate or complete. However, the modelled abundances are within a factor of 3, consistent with the observations, considering a late stage of the evolution of the pre-stellar core, compatible with previous observations.

Fusion-nonfusion hybrid construct versus anterior cervical hybrid decompression and fusion: a comparative study for 3-level cervical degenerative disc diseases.

PubMed

Ding, Fan; Jia, Zhiwei; Wu, Yaohong; Li, Chao; He, Qing; Ruan, Dike

2014-11-01

A retrospective analysis. This study aimed to compare the safety and efficacy between the fusion-nonfusion hybrid construct (HC: anterior cervical corpectomy and fusion plus artificial disc replacement, ACCF plus cADR) and anterior cervical hybrid decompression and fusion (ACHDF: anterior cervical corpectomy and fusion plus discectomy and fusion, ACCF plus ACDF) for 3-level cervical degenerative disc diseases (cDDD). The optimal anterior technique for 3-level cDDD remains uncertain. Long-segment fusion substantially induced biomechanical changes at adjacent levels, which may lead to symptomatic adjacent segment degeneration. Hybrid surgery consisting of ACDF and cADR has been reported with good results for 2-level cDDD. In this context, ACCF combining with cADR may be an alternative to ACHDF for 3-level cDDD. Between 2009 and 2012, 28 patients with 3-level cDDD who underwent HC (n=13) and ACHDF (15) were retrospectively reviewed. Clinical assessments were based on Neck Disability Index, Japanese Orthopedic Association disability scale, visual analogue scale, Japanese Orthopedic Association recovery rate, and Odom criteria. Radiological analysis included range of motion of C2-C7 and adjacent segments and cervical lordosis. Perioperative parameters, radiological adjacent-level changes, and the complications were also assessed. HC showed better Neck Disability Index improvement at 12 and 24 months, as well as Japanese Orthopedic Association and visual analogue scale improvement at 24 months postoperatively (P<0.05). HC had better outcome according to Odom criteria but not significantly (P>0.05). The range of motion of C2-C7 and adjacent segments was less compromised in HC (P<0.05). Both 2 groups showed significant lordosis recovery postoperatively (P<0.05), but no difference was found between groups (P>0.05). The incidence of adjacent-level degenerative changes and complications was higher in ACHDF but not significantly (P>0.05). HC may be an alternative to ACHDF for 3-level cDDD due to the equivalent or superior early clinical outcomes, less compromised C2-C7 range of motion, and less impact at adjacent levels. 3.

Degradation of carbamazepine using hydrodynamic cavitation combined with advanced oxidation processes.

PubMed

Thanekar, Pooja; Panda, Mihir; Gogate, Parag R

2018-01-01

Degradation of carbamazepine (CBZ), a widely detected recalcitrant pharmaceutical in sewage treatment plant (STP) effluent, has been studied in the present work using combination of hydrodynamic cavitation (HC) and advanced oxidation processes (AOPs). Due to its recalcitrant nature, it cannot be removed effectively by the conventional wastewater treatment plants (WWTPs) which make CBZ a pharmaceutical of very high environmental relevance and impact as well as stressing the need for developing new treatment schemes. In the present study, the effect of inlet pressure (3-5bar) and operating pH (3-11) on the extent of degradation have been initially studied with an objective of maximizing the degradation using HC alone. The established optimum conditions as pressure of 4bar and pH of 4 resulted in maximum degradation of CBZ as 38.7%. The combined approaches of HC with ultraviolet irradiation (HC+UV), hydrogen peroxide (HC+H 2 O 2 ), ozone (HC+O 3 ) as well as combination of HC, H 2 O 2 and O 3 (HC+H 2 O 2 +O 3 ) have been investigated under optimized pressure and operating pH. It was observed that a significant increase in the extent of degradation is obtained for the combined operations of HC+H 2 O 2 +O 3 , HC+O 3 , HC+H 2 O 2 , and HC+UV with the actual extent of degradation being 100%, 91.4%, 58.3% and 52.9% respectively. Kinetic analysis revealed that degradation of CBZ fitted into first order kinetics model for all the approaches. The processes were also compared on the basis of cavitational yield and also in terms of total treatment cost. Overall, it has been demonstrated that combined process of HC, H 2 O 2 and O 3 can be effectively used for treatment of wastewater containing CBZ. Copyright © 2017 Elsevier B.V. All rights reserved.

Synthesis, liquid crystallinity, and chiroptical properties of sterol-containing polyacetylenes

NASA Astrophysics Data System (ADS)

Lam, Jacky Wing Yip; Lai, Lo Ming; Tang, Ben Zhong

2006-08-01

Poly(phenylacetylene)s and poly(1-alkyne)s containing chiral sterol pendant groups with molecular structures of -[HC=C-C 6H 4-CO II-R] n-, -[HC=C-C 6H 4-O(CH II) 10-CO II-R] n- and -[HC=C(CH II) mCO II-R] n-, (where R = cholesterol, stigmasterol, ergosterol and m = 2, 3, 8} are designed and synthesized. The monomers are prepared by esterifications of acetylenic acids with cholesterol, stigmasterol, and ergosterol and exhibit cholestericity at high temperatures. Polymerizations of the monomers are effected by WCl 6-Ph 4Sn, MoCl 5-Ph 4Sn, and organorhodium catalysts, giving high molecular weight (M w up to 8.0 × 10 5) polymers in high yields (up to 99%). The structures and properties of the polymers are characterized and evaluated by IR, NMR, TGA, DSC, POM, X-ray, UV, and CD analyses. All the polymers are thermally stable (greater than or equal to 300 °C). Polymers with long flexible alkyl chains form smectic and cholesteric phases at elevated temperatures. With an increase in the spacer length in poly(1-alkyne)s, the packing arrangements of the mesogenic pendants in the mesophases change from bilayer or mixed mono- and bilayer into homogeneous monolayer structures. Few poly(phenylacetylene)s show CD bands in the absorption region of the polyacetylene backbones, revealing that the main chains are helically rotating with a preferred screw sense.

INDIUM AND ZINC MEDIATED ONE-ATOM CARBOCYCLE ENLARGEMENT IN WATER. (R822668)

EPA Science Inventory

Abstract

Six-, seven-, eight-membered rings are enlarged by one carbon-atom into seven-, eight- and nine-membered ring derivatives respectively, via indium or zinc mediated reactions in aqueous medium.

Preparation and sonodynamic activities of water-soluble tetra-α-(3-carboxyphenoxyl) zinc(II) phthalocyanine and its bovine serum albumin conjugate.

PubMed

Xu, He-Nan; Chen, Hai-Jun; Zheng, Bi-Yuan; Zheng, Yun-Quan; Ke, Mei-Rong; Huang, Jian-Dong

2015-01-01

Sonodynamic therapy (SDT) is a new approach for cancer treatment, involving the synergistic effect of ultrasound and certain chemical compounds termed as sonosensitizers. A water-soluble phthalocyanine, namely tetra-α-(3-carboxyphenoxyl) zinc(II) phthalocyanine (ZnPcC4), has been prepared and characterized. The interactions between ZnPcC4 and bovine serum albumin (BSA) were also investigated by absorption and fluorescence spectroscopy. It was found that there were strong interactions between ZnPcC4 and BSA with a binding constant of 6.83×10(7)M(-1). A non-covalent BSA conjugate of ZnPcC4 (ZnPcC4-BSA) was prepared. Both ZnPcC4 and ZnPcC4-BSA exhibited efficient sonodynamic activities against HepG2 human hepatocarcinoma cells. Compared with ZnPcC4, conjugate ZnPcC4-BSA showed a higher sonodynamic activity with an IC50 value of 7.5μM. Upon illumination with ultrasound, ZnPcC4-BSA can induce an increase of intracellular reactive oxygen species (ROS) level, resulting in cellular apoptosis. The results suggest that the albumin conjugates of zinc(II) phthalocyanines functionalized with carboxyls can serve as promising sonosensitizers for sonodynamic therapy. Copyright © 2014 Elsevier B.V. All rights reserved.

Crystal structure of N-(1-allyl-3-chloro-4-eth-oxy-1H-indazol-5-yl)-4-meth-oxybenzene-sulfonamide.

PubMed

Chicha, Hakima; Rakib, El Mostapha; Bouissane, Latifa; Saadi, Mohamed; El Ammari, Lahcen

2014-09-01

In the title compound, C19H20ClN3O4S, the benzene ring is inclined to the indazole ring system (r.m.s. deviation = 0.014 Å) by 65.07 (8)°. The allyl and eth-oxy groups are almost normal to the indazole ring, as indicated by the respective torsion angles [N-N-C-C = 111.6 (2) and C-C-O-C = -88.1 (2)°]. In the crystal, mol-ecules are connected by N-H⋯N hydrogen bonds, forming helical chains propagating along [010]. The chains are linked by C-H⋯O hydrogen bonds, forming a three-dimensional network.

Recovery of zinc and manganese, and other metals (Fe, Cu, Ni, Co, Cd, Cr, Na, K) from Zn-MnO2 and Zn-C waste batteries: Hydroxyl and carbonate co-precipitation from solution after reducing acidic leaching with use of oxalic acid

NASA Astrophysics Data System (ADS)

Sobianowska-Turek, A.; Szczepaniak, W.; Maciejewski, P.; Gawlik-Kobylińska, M.

2016-09-01

The article discusses the current situation of the spent batteries and portable accumulators management. It reviews recycling technologies of the spent batteries and portable accumulators which are used in the manufacturing installations in the world. Also, it presents the authors' research results on the reductive acidic leaching of waste material of the zinc-carbon batteries (Zn-C) and zinc-manganese batteries (alkaline Zn-MnO2) delivered by a company dealing with mechanical treatment of this type of waste stream. The research data proved that the reductive acidic leaching (H2SO4 + C2H2O4) of the battery's black mass allows to recover 85.0% of zinc and 100% of manganese. Moreover, it was found that after the reductive acidic leaching it is possible to recover nearly 100% of manganese, iron, cadmium, and chromium, 98.0% of cobalt, 95.5% of zinc, and 85.0% of copper and nickel from the solution with carbonate method. On the basis of the results, it is possible to assume that the carbonate method can be used for the preparation of manganese-zinc ferrite.

Structural characterization and identification of biflavones in Selaginella tamariscina by liquid chromatography-diode-array detection/electrospray ionization tandem mass spectrometry.

PubMed

Zhang, Yi-Xuan; Li, Qiu-Yue; Yan, Li-Li; Shi, Yue

2011-08-15

Biflavonoids, a special class of flavonoids, are widely distributed in gymnosperm plants and have various biological activities. They are also major bioactive ingredients in Selaginella tamariscina. In this work, we report the use of high-performance liquid chromatography with a diode-array detector (HPLC-DAD) and electrospray ionization multi-stage tandem mass spectrometry (ESI-MS(n)) to study the fragmentation behavior of three main types of biflavonoids using seven biflavonoid reference compounds and analyze the biflavonoids in Selaginella tamariscina. The most useful fragmentations in terms of structural identification are those involving the C-ring cleavage of biflavonoids. For amentoflavone-type biflavonoids (containing flavonoid parts I and II), fragmentation on the flavonoid part II at positions 1/3 and 0/4 are the primary pathways, whereas the chances are greater for C-ring cleavage fragmentation occurring on flavonoid part I at positions 1/3 and 1/4 for robustaflavone-type biflavonoids. However, the predominant diagnostic ions of the specific C-O-C-connected hinokiflavone-type biflavonoids are a series of ions resulting from the rupture of the connective C-O bond. Based on the fragmentation patterns of these reference compounds, 17 biflavonoids were identified in an extract of Selaginella tamariscina, three of which have not been previously reported as constituents of this plant. This study provides a powerful approach for the online structural elucidation and identification of different types of biflavonoids and positional isomers from Selaginella tamariscina and other biflavonoids distributed in related plants and prescriptions. Copyright © 2011 John Wiley & Sons, Ltd.

The TFIIH subunit Tfb3 regulates cullin neddylation

PubMed Central

Rabut, Gwenaël; Le Dez, Gaëlle; Verma, Rati; Makhnevych, Taras; Knebel, Axel; Kurz, Thimo; Boone, Charles; Deshaies, Raymond J.; Peter, Matthias

2011-01-01

Summary Cullin proteins are scaffolds for the assembly of multi-subunit ubiquitin ligases, which ubiquitylate a large number of proteins involved in widely-varying cellular functions. Multiple mechanisms cooperate to regulate cullin activity, including neddylation of their C-terminal domain. Interestingly, we found that the yeast Cul4-type cullin Rtt101 is not only neddylated but also ubiquitylated, and both modifications promote Rtt101 function in vivo. Surprisingly, proper modification of Rtt101 neither correlated with catalytic activity of the RING-domain of Hrt1 nor did it require the Nedd8 ligase Dcn1. Instead, ubiquitylation of Rtt101 was dependent on the ubiquitin-conjugating enzyme Ubc4, while efficient neddylation involves the RING-domain protein Tfb3, a subunit of the transcription factor TFIIH. Tfb3 also controls Cul3 neddylation and activity in vivo, and physically interacts with Ubc4 and the Nedd8-conjugating enzyme Ubc12 as well as the Hrt1/Rtt101 complex. Together, these results suggest that the conserved RING-domain protein Tfb3 controls activation of a subset of cullins. PMID:21816351

Superposed Redox Chemistry of Fused Carbon Rings in Cyclooctatetraene-Based Organic Molecules for High-Voltage and High-Capacity Cathodes.

PubMed

Zhao, Xiaolin; Qiu, Wujie; Ma, Chao; Zhao, Yingqin; Wang, Kaixue; Zhang, Wenqing; Kang, Litao; Liu, Jianjun

2018-01-24

Even though many organic cathodes have been developed and have made a significant improvement in energy density and reversibility, some organic materials always generate relatively low voltage and limited discharge capacity because their energy storage mechanism is solely based on redox reactions of limited functional groups [N-O, C═X (X = O, N, S)] linking to aromatic rings. Here, a series of cyclooctatetraene-based (C 8 H 8 ) organic molecules were demonstrated to have electrochemical activity of high-capacity and high-voltage from carbon rings by means of first-principles calculations and electronic structure analysis. Fused molecules of C 8 -C 4 -C 8 (C 16 H 12 ) and C 8 -C 4 -C 8 -C 4 -C 8 (C 24 H 16 ) contain, respectively, four and eight electron-deficient carbons, generating high-capacity by their multiple redox reactions. Our sodiation calculations predict that C 16 H 12 and C 24 H 16 exhibit discharge capacities of 525.3 and 357.2 mA h g -1 at the voltage change from 3.5 to 1.0 V and 3.7 to 1.3 V versus Na + /Na, respectively. Electronic structure analysis reveals that the high voltages are attributed to superposed electron stabilization mechanisms, including double-bond reformation and aromatization from carbon rings. High thermodynamic stability of these C 24 H 16 -based systems strongly suggests feasibility of experimental realization. The present work provides evidence that cyclooctatetraene-based organic molecules fused with the C 4 ring are promising in designing high-capacity and high-voltage organic rechargeable cathodes.

A novel 3D framework indium phosphite-oxalate based on a pcu-type topology

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

Zuo, Mengmeng; Zhou, Mingdong; Hu, Dianwen

2016-05-15

A new inorganic–organic hybrid indium phosphite-oxalate, formulated as H[In{sub 5}(HPO{sub 3}){sub 6}(H{sub 2}PO{sub 3}){sub 2}(C{sub 2}O{sub 4}){sub 2}]·(C{sub 4}N{sub 2}H{sub 11}){sub 2}·H{sub 2}O 1 has been hydrothermally synthesized in the presence of piperazine acting as a structure directing agent (SDA). The single crystal X-ray diffraction reveals that compound 1 shows three-dimensional open-framework with intersecting 12-ring channels along the [010] and [001] directions, which is constructed from strictly alternating double 6-ring units (D6Rs), [C{sub 2}O{sub 4}]{sup 2−} groups and [H{sub 2}PO{sub 3}]{sup −} pseudo-pyramids. It is noted that the classical D6R SBU is firstly reported in main metal phosphite/phosphite-oxalate. By regardingmore » D6R as the 6-connected nodes, the inorganic–organic hybrid framework is based on a pcu-type topology. The as-synthesized product was characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectroscopy, thermogravimetric analysis (TGA), ICP-AES and elemental analyses. - Graphical abstract: A 3D open-framework indium phosphite-oxalate has been synthesized under hydrothermal conditions. A classical SBU, D6R, is present in the structure. By regarding D6R as the 6-connected nodes, the inorganic–organic hybrid framework is based on a pcu-type topology. - Highlights: • A new indium phosphite-oxalate based on a pcu-type topology has been synthesized. • A classical SBU, D6R, is present in the structure. • The classical SBU is firstly reported in main metal phosphite/phosphite-oxalate.« less

Elevated levels of triglyceride and triglyceride-rich lipoprotein triglyceride induced by a high-carbohydrate diet is associated with polymorphisms of APOA5-1131T>C and APOC3-482C>T in Chinese healthy young adults.

PubMed

Lin, Jia; Fang, Ding Zhi; Du, Juan; Shigdar, Sarah; Xiao, Li Ying; Zhou, Xue Dong; Duan, Wei

2011-01-01

Changes in lipid profiles have been shown to be associated with diet and apolipoprotein (APO) polymorphisms. Therefore, 2 polymorphisms, i.e. APOA5-1131T>C and APOC3-482C>T, and serum lipids were examined in a Chinese healthy young population with high-carbohydrate/low-fat (HC/LF) diet intervention. After a wash-out diet for 7 days, 56 young adults (22.89 ± 1.80 years) received the HC/LF diet for 6 days. Body mass index (BMI) and fasting serum lipid profiles at baseline, after the wash-out diet, and after the HC/LF diet were measured. APOA5-1131C carriers had higher triglyceride (TG) and TG-rich lipoprotein TG (TRL-TG) levels at baseline and after the HC/LF diet, though this mainly corresponded to the female cohort. APOC3-482T carriers had higher TRL-TG levels following the wash-out and HC/LF diets, but these were not directly attributable to a single gender. Both polymorphisms may play an important role in the elevated TG and TRL-TG levels induced by the HC/LF diet, especially in females, thus indicating a potential dietary prevention of coronary heart disease in this Chinese cohort. Copyright © 2011 S. Karger AG, Basel.

Magnetic properties of epitaxial β-Nb2N thin film on SiC substrate

NASA Astrophysics Data System (ADS)

Yang, Zihao; Myers, Roberto; Katzer, D. Scott; Nepal, Neeraj; Meyer, David J.

Previously superconductivity in Nb2N was studied in thin films synthesized by reactive magnetron sputtering or pulsed laser deposition. Recently, Nb2N was synthesized by molecular beam epitaxy (MBE). Here, we report on the magnetic properties of MBE grown Nb2N measured by SQUID magnetometry. The single hexagonal β phase Nb2N is grown on a semi-insulating Si-face 4H SiC (0001) substrate in nitrogen rich conditions at a substrate temperature of 850 °C. In-plane magnetization as a function of magnetic field measured at 5 K shows type-II superconductivity with critical fields Hc1 and Hc2 of 300 Oe and 10 kOe, respectively. In-plane field-cooled and zero-field-cooled a critical temperature (Tc) of 11.5 K, higher than in sputtered Nb2N films. This work was supported by Army Research Office and the Office of Naval Research.

A new anthraquinone and eight constituents from Hedyotis caudatifolia Merr. et Metcalf: isolation, purification and structural identification.

PubMed

Luo, Peng; Su, Jiale; Zhu, Yilin; Wei, Jianhua; Wei, Wanxing; Pan, Weigao

2016-10-01

Hedyotis caudatifolia Merr. et Metcalf. (HC), a folk medicine in Yao nationalities areas in China, was used to investigate the chemical constituents. Through silica gel and Sephadex LH-20 column chromatography, nine compounds were isolated and purified. By physical and chemical properties, IR, MS (EI-MS, high resolution EI-MS), 1D NMR ((1)H NMR, (13)C NMR) and 2D NMR (HSQC, (1)H-(1)H COSY, HMBC), their structures were identified as β-sitosterol (1), stigmasterol (2), scopolin (3), 2-hydroxy-1,7,8-trimethoxyanthracene-9,10-dione (4), oleanolic acid (5), ursolic acid (6), methyl barbinervate (7), β-daucosterol (8) and p-Hydroxybenzoic acid (9). These compounds were isolated from HC for the first time, and 4 a new anthraquinone whose biological activities are worth to be investigated in future. These compounds may contribute to the HC's pharmacological effects on treating diseases, and may be used as candidates for control index in establishing the quality control standard of HC.

A medium range order structural connection to the configurational heat capacity of borate-silicate mixed glasses.

PubMed

Liu, Hao; Smedskjaer, Morten M; Tao, Haizheng; Jensen, Lars R; Zhao, Xiujian; Yue, Yuanzheng

2016-04-28

It has been reported that the configurational heat capacity (C(p,conf)) first increases and then becomes saturated with increasing B2O3/SiO2 ratio in borate-silicate mixed glasses. Through Raman spectroscopy measurements, we have, in this work, found an implication for the intermediate range order (IRO) structural connection to the composition dependence of the C(p,conf) of borate-silicate mixed glasses. In the silica-rich compositions, the C(p,conf) rapidly increases with increasing B2O3 content. This is attributed to the increase of the content of the B-O-Si network units ([B2Si2O8](2-)) and 6-membered borate rings with 1 or 2 B(4). In the boron-rich compositions, the C(p,conf) is almost constant, independent of the increase in the B2O3/SiO2 ratio. This is likely attributed to the counteraction between the decrease of the fraction of two types of metaborate groups and the increase of the fraction of other borate superstructural units (particularly 6-membered borate rings). The overall results suggest that the glasses containing more types of superstructural units have a larger C(p,conf).

Nitrogen enrichment potential of biochar in relation to pyrolysis temperature and feedstock quality.

PubMed

Jassal, Rachhpal S; Johnson, Mark S; Molodovskaya, Marina; Black, T Andrew; Jollymore, Ashlee; Sveinson, Kelly

2015-04-01

Nitrogen (N) enrichment of biochar from both inorganic and organic waste N sources has the potential to add economic and environmental value through its use as a slow release N fertilizer. We investigated the sorption of N by, and its release from, biochar made at pyrolysis temperatures of 400, 500 and 600 °C from three feedstocks: poultry litter (PL with a carbon (C) to N ratio (C:N) of 14), softwood chips of spruce-pine-fir (SPF with a C:N of 470), and a 50:50 mixture of PL and SPF (PL/SPF). The prepared biochars were enriched with ammonium nitrate (AN) and urea ammonium nitrate (UAN). PL biochars had the lowest C content (50-56% C), but the highest pH (9.3-9.9), electrical conductivity (EC, 780-960 dS m(-1)), cation exchange capacity (CEC, 40-46 cmol kg(-1)), and N content (3.3-4.5%). While N content and hydrogen (H) to C atomic ratio (H:C) decreased with increasing pyrolysis temperature irrespective of the feedstock used, both pH and EC slightly increased with pyrolysis temperature for all feedstocks. The PL and SPF biochars showed similar H:C and also similar N sorption and N release at all pyrolysis temperatures. These biochars sorbed up to 5% N by mass, irrespective of the source of N. However, PL/SPF biochar performed poorly in sorbing N from either AN or UAN. Biochar H:C was found to be unrelated to N sorption rates, suggesting that physical adsorption on active surfaces was the main mechanism of N sorption in these biochars. There were minor differences between N sorbed from NO3-N and NH4-N among different biochars. Very small amounts of sorbed N (0.2-0.4 mg N g(-1) biochar) was released when extracted with 1 M KCl solution, indicating that the retained N was strongly held in complex bonds, more so for NH4-N because the release of NO3-N was 3-4 times greater than that of NH4-N. NH4-N sorption far exceeded the effective CEC of the biochars, thereby suggesting that most of the sorption may be due to physical entrapment of NH4(+) in biochar pores. The results of this study suggest that biochar can be used to remove excess N from poultry and dairy manure and be a good mitigation option for reducing N leaching and gaseous losses. Copyright © 2015 Elsevier Ltd. All rights reserved.

Imidazolium 3-nitro­benzoate

PubMed Central

Hou, Guang-Yang; Zhou, Li-Na; Yin, Qiu-Xiang; Su, Wei-Yi; Mao, Hui-Lin

2009-01-01

In the title compound, C3H5N2 +·C7H4NO4 −, the benzene ring forms a dihedral angle of 40.60 (5)° with the imidizolium ring. The nitro­benzoate anion is approximately planar: the benzene ring makes dihedral angles of 3.8 (3) and 3.2 (1)° with the nitro and carboxyl­ate groups, respectively. In the crystal structure, the cations and anions are linked by inter­molecular N—H⋯O hydrogen bonds, forming a zigzag chain along the b axis. PMID:21583857

Zinc complexes supported by methyl salicylato ligands: synthesis, structure, and application in ring-opening polymerization of L-lactide.

PubMed

Petrus, Rafał; Sobota, Piotr

2013-10-14

Two novel zinc alkoxides supported by chelating methyl salicylato (MesalO; MesalOH = methyl salicylate) ligands were successfully synthesized and characterized. Reaction of MesalOH with ZnEt2 (2:1) gives a tetranuclear cluster [Zn(MesalO)2]4 (1), which by addition of pyridine is transformed to the mononuclear compound [Zn(MesalO)2(py)2] (2). Compounds 1 and 2 were characterized by elemental analysis, NMR, IR, and single crystal X-ray diffraction. The catalytic activity of both compounds was tested for the ring-opening polymerization (ROP) of L-lactide (L-LA). It was found that compounds 1 and 2 are efficient initiators of the ROP of L-LA, yielding cyclic PLLA with weight average molecular weights up to 100 kDa for 2. The treatment of 2 with 1 equiv. of BnOH in toluene afforded a dimeric compound [Zn(OBn)(MesalO)(py)]2 (3). The addition of L-LA to a combination of 1 and 4 equiv. of BnOH in THF or 2 and 1 equiv. of BnOH in toluene led to the rapid and efficient generation of PLLA with end-capped BnO groups.

Supramolecular architectures in the salt trimethoprimium ferrocene-1-carboxylate and the cocrystal 4-amino-5-chloro-2,6-dimethylpyrimidine-ferrocene-1-carboxylic acid (1/1).

PubMed

Swinton Darious, Robert; Thomas Muthiah, Packianathan; Perdih, Franc

2017-09-01

In the salt trimethoprimium ferrocenecarboxylate [systematic name: 2,4-diamino-5-(3,4,5-trimethoxybenzyl)pyrimidin-1-ium ferrocene-1-carboxylate], (C 14 H 19 N 4 O 3 )[Fe(C 5 H 5 )(C 6 H 4 O 2 )], (I), of the antibacterial compound trimethoprim, the carboxylate group interacts with the protonated aminopyrimidine group of trimethoprim via two N-H...O hydrogen bonds, generating a robust R 2 2 (8) ring motif (heterosynthon). However, in the cocrystal 4-amino-5-chloro-2,6-dimethylpyrimidine-ferrocene-1-carboxylic acid (1/1), [Fe(C 5 H 5 )(C 6 H 5 O 2 )]·C 6 H 8 ClN 3 , (II), the carboxyl-aminopyrimidine interaction [R 2 2 (8) motif] is absent. The carboxyl group interacts with the pyrimidine ring via a single O-H...N hydrogen bond. The pyrimidine rings, however, form base pairs via a pair of N-H...N hydrogen bonds, generating an R 2 2 (8) supramolecular homosynthon. In salt (I), the unsubstituted cyclopentadienyl ring is disordered over two positions, with a refined site-occupation ratio of 0.573 (10):0.427 (10). In this study, the two five-membered cyclopentadienyl (Cp) rings of ferrocene are in a staggered conformation, as is evident from the C...Cg...Cg...C pseudo-torsion angles, which are in the range 36.13-37.53° for (I) and 22.58-23.46° for (II). Regarding the Cp ring of the minor component in salt (I), the geometry of the ferrocene ring is in an eclipsed conformation, as is evident from the C...Cg...Cg...C pseudo-torsion angles, which are in the range 79.26-80.94°. Both crystal structures are further stabilized by weak π-π interactions.

Advance in dietary polyphenols as aldose reductases inhibitors: structure-activity relationship aspect.

PubMed

Xiao, Jianbo; Ni, Xiaoling; Kai, Guoyin; Chen, Xiaoqing

2015-01-01

The dietary polyphenols as aldose reductases inhibitors (ARIs) have attracted great interest among researchers. The aim of this review is to give an overview of the research reports on the structure-activity relationship of dietary polyphenols inhibiting aldose reductases (AR). The molecular structures influence the inhibition of the following: (1) The methylation and methoxylation of the hydroxyl group at C3, C3', and C4' of flavonoids decreased or little affected the inhibitory potency. However, the methylation and methoxylation of the hydroxyl group at C5, C6, and C8 significantly enhanced the inhibition. Moreover, the methylation and methoxylation of C7-OH influence the inhibitory activity depending on the substitutes on rings A and B of flavonoids. (2) The glycosylation on 3-OH of flavonoids significantly increased or little affected the inhibition. However, the glycosylation on 7-OH and 4'-OH of flavonoids significantly decreased the inhibition. (3) The hydroxylation on A-ring of flavones and isoflavones, especially at positions 5 and 7, significantly improved the inhibition and the hydroxylation on C3' and C4' of B-ring of flavonoids remarkably enhanced the inhibition; however, the hydroxylation on the ring C of flavones significantly weakened the inhibition. (4) The hydrogenation of the C2=C3 double bond of flavones reduced the inhibition. (5) The hydrogenation of α=β double bond of stilbenes hardly affected the inhibition and the hydroxylation on C3' of stilbenes decreased the inhibition. Moreover, the methylation of the hydroxyl group of stilbenes obviously reduced the activity. (6) The hydroxylation on C4 of chalcone significantly increased the inhibition and the methylation on C4 of chalcone remarkably weakened the inhibition.

Resveratrol and para-coumarate serve as ring precursors for coenzyme Q biosynthesis[S

PubMed Central

Xie, Letian X.; Williams, Kevin J.; He, Cuiwen H.; Weng, Emily; Khong, San; Rose, Tristan E.; Kwon, Ohyun; Bensinger, Steven J.; Marbois, Beth N.; Clarke, Catherine F.

2015-01-01

Coenzyme Q (Q or ubiquinone) is a redox-active polyisoprenylated benzoquinone lipid essential for electron and proton transport in the mitochondrial respiratory chain. The aromatic ring 4-hydroxybenzoic acid (4HB) is commonly depicted as the sole aromatic ring precursor in Q biosynthesis despite the recent finding that para-aminobenzoic acid (pABA) also serves as a ring precursor in Saccharomyces cerevisiae Q biosynthesis. In this study, we employed aromatic 13C6-ring-labeled compounds including 13C6-4HB, 13C6-pABA, 13C6-resveratrol, and 13C6-coumarate to investigate the role of these small molecules as aromatic ring precursors in Q biosynthesis in Escherichia coli, S. cerevisiae, and human and mouse cells. In contrast to S. cerevisiae, neither E. coli nor the mammalian cells tested were able to form 13C6-Q when cultured in the presence of 13C6-pABA. However, E. coli cells treated with 13C6-pABA generated 13C6-ring-labeled forms of 3-octaprenyl-4-aminobenzoic acid, 2-octaprenyl-aniline, and 3-octaprenyl-2-aminophenol, suggesting UbiA, UbiD, UbiX, and UbiI are capable of using pABA or pABA-derived intermediates as substrates. E. coli, S. cerevisiae, and human and mouse cells cultured in the presence of 13C6-resveratrol or 13C6-coumarate were able to synthesize 13C6-Q. Future evaluation of the physiological and pharmacological responses to dietary polyphenols should consider their metabolism to Q. PMID:25681964

Metformin improves circulating endothelial cells and endothelial progenitor cells in type 1 diabetes: MERIT study.

PubMed

Ahmed, Fahad W; Rider, Rachel; Glanville, Michael; Narayanan, Kilimangalam; Razvi, Salman; Weaver, Jolanta U

2016-08-26

Type 1 diabetes is associated with increased cardiovascular disease (CVD). Decreased endothelial progenitor cells (EPCs) number plays a pivotal role in reduced endothelial repair and development of CVD. We aimed to determine if cardioprotective effect of metformin is mediated by increasing circulating endothelial progenitor cells (cEPCs), pro-angiogenic cells (PACs) and decreasing circulating endothelial cells (cECs) count whilst maintaining unchanged glycemic control. This study was an open label and parallel standard treatment study. Twenty-three type 1 diabetes patients without overt CVD were treated with metformin for 8 weeks (treatment group-TG). They were matched with nine type 1 diabetes patients on standard treatment (SG) and 23 age- and sex-matched healthy volunteers (HC). Insulin dose was adjusted to keep unchanged glycaemic control. cEPCs and cECs counts were determined by flow cytometry using surface markers CD45(dim)CD34(+)VEGFR-2(+) and CD45(dim)CD133(-)CD34(+)CD144(+) respectively. Peripheral blood mononuclear cells were cultured to assess changes in PACs number, function and colony forming units (CFU-Hill's colonies). At baseline TG had lower cEPCs, PACs, CFU-Hills' colonies and PACs adhesion versus HC (p < 0.001-all variables) and higher cECs versus HC (p = 0.03). Metformin improved cEPCs, PACs, CFU-Hill's colonies number, cECs and PACs adhesion (p < 0.05-all variables) to levels seen in HC whilst HbA1c (one-way ANOVA p = 0.78) and glucose variability (average glucose, blood glucose standard deviation, mean amplitude of glycaemic excursion, continuous overall net glycaemic action and area under curve) remained unchanged. No changes were seen in any variables in SG. There was an inverse correlation between CFU-Hill's colonies with cECs. Metformin has potential cardio-protective effect through improving cEPCs, CFU-Hill's colonies, cECs, PACs count and function independently of hypoglycaemic effect. This finding needs to be confirmed by long term cardiovascular outcome studies in type 1 diabetes. Trial registration ISRCTN26092132.

VGF function in depression and antidepressant efficacy.

PubMed

Jiang, C; Lin, W-J; Sadahiro, M; Labonté, B; Menard, C; Pfau, M L; Tamminga, C A; Turecki, G; Nestler, E J; Russo, S J; Salton, S R

2017-11-21

Brain-derived neurotrophic factor (BDNF) is a critical effector of depression-like behaviors and antidepressant responses. Here, we show that VGF (non-acronymic), which is robustly regulated by BDNF/TrkB signaling, is downregulated in hippocampus (male/female) and upregulated in nucleus accumbens (NAc) (male) in depressed human subjects and in mice subjected to chronic social defeat stress (CSDS). Adeno-associated virus (AAV)-Cre-mediated Vgf ablation in floxed VGF mice, in dorsal hippocampus (dHc) or NAc, led to pro-depressant or antidepressant behaviors, respectively, while dHc- or NAc-AAV-VGF overexpression induced opposite outcomes. Mice with reduced VGF levels in the germ line (Vgf+/-) or in dHc (AAV-Cre-injected floxed mice) showed increased susceptibility to CSDS and impaired responses to ketamine treatment in the forced swim test. Floxed mice with conditional pan-neuronal (Synapsin-Cre) but not those with forebrain (αCaMKII-Cre) Vgf ablation displayed increased susceptibility to subthreshold social defeat stress, suggesting that neuronal VGF, expressed in part in inhibitory interneurons, regulates depression-like behavior. Acute antibody-mediated sequestration of VGF-derived C-terminal peptides AQEE-30 and TLQP-62 in dHc induced pro-depressant effects. Conversely, dHc TLQP-62 infusion had rapid antidepressant efficacy, which was reduced in BDNF floxed mice injected in dHc with AAV-Cre, and in NBQX- and rapamycin-pretreated wild-type mice, these compounds blocking α-amino-3-hydroxy-5-methyl-4-isoxazolepropionic acid (AMPA) receptor and mammalian target of rapamycin (mTOR) signaling, respectively. VGF is therefore a critical modulator of depression-like behaviors in dHc and NAc. In hippocampus, the antidepressant response to ketamine is associated with rapid VGF translation, is impaired by reduced VGF expression, and as previously reported, requires coincident, rapid BDNF translation and release.Molecular Psychiatry advance online publication, 21 November 2017; doi:10.1038/mp.2017.233.

Pilot scale intensification of rubber seed (Hevea brasiliensis) oil via chemical interesterification using hydrodynamic cavitation technology.

PubMed

Bokhari, Awais; Yusup, Suzana; Chuah, Lai Fatt; Klemeš, Jiří Jaromír; Asif, Saira; Ali, Basit; Akbar, Majid Majeed; Kamil, Ruzaimah Nik M

2017-10-01

Chemical interesterification of rubber seed oil has been investigated for four different designed orifice devices in a pilot scale hydrodynamic cavitation (HC) system. Upstream pressure within 1-3.5bar induced cavities to intensify the process. An optimal orifice plate geometry was considered as plate with 1mm dia hole having 21 holes at 3bar inlet pressure. The optimisation results of interesterification were revealed by response surface methodology; methyl acetate to oil molar ratio of 14:1, catalyst amount of 0.75wt.% and reaction time of 20min at 50°C. HC is compared to mechanical stirring (MS) at optimised values. The reaction rate constant and the frequency factor of HC were 3.4-fold shorter and 3.2-fold higher than MS. The interesterified product was characterised by following EN 14214 and ASTM D 6751 international standards. Copyright © 2017 Elsevier Ltd. All rights reserved.

Comparison of the BackJoy SitSmart Relief and Spine Buddy LT1 H/C Ergonomic Chair Supports on Short-Term Neck and Back Pain.

PubMed

Ward, John; Coats, Jesse

2017-01-01

The purpose of this study was to perform a needs assessment to determine whether short-term use of BackJoy SitSmart Relief and Spine Buddy LT1 H/C chair supports influences neck, upper back, and lower back pain. Forty-eight college students (age, 27.5 ± 6.3 years; height, 1.72 ± 0.08 m; body mass, 78.7 ± 19.8 kg; time seated that day, 4.3 ± 2.8 hours; means ± SD) were recruited for this study. The Nordic Musculoskeletal Questionnaire was used to measure pain for the neck, upper back, and lower back regions. Subjects were randomized to sit in a stationary office chair for a single 12-minute period under 1 of 4 conditions: office chair only (control group), BackJoy SitSmart Relief and chair, freezer-cooled Spine Buddy LT1 H/C and chair, or microwave-heated Spine Buddy LT1 H/C and chair. Participants then completed a posttest Nordic Musculoskeletal Questionnaire. A between-within repeated-measures analysis of variance using the between-subject factor intervention (group) and within-subject factor time (baseline and posttest) was used to analyze study data. The main effect of time across the whole sample was statistically significant for neck (P = .000), upper back (P = .032), and lower back (P = .000) pain; however, there was no statistically significant interaction effect between intervention and time. Thus, as long as participants sat down and rested, symptoms improved similarly across the different groups. In this preliminary study, short-term and single use of a support product for an office chair had no additive effect on reducing neck and back pain. Copyright © 2016. Published by Elsevier Inc.

S-Nitrosation and regulation of inducible nitric oxide synthase.

PubMed

Mitchell, Douglas A; Erwin, Phillip A; Michel, Thomas; Marletta, Michael A

2005-03-29

The inducible isoform of nitric oxide synthase (iNOS) and three zinc tetrathiolate mutants (C104A, C109A, and C104A/C109A) were expressed in Escherichia coli and purified. The mutants were found by ICP-AES and the zinc-specific PAR colorimetric assay to be zinc free, whereas the wild-type iNOS zinc content was 0.38 +/- 0.01 mol of Zn/mol of iNOS dimer. The cysteine mutants (C104A and C109A) had an activity within error of wild-type iNOS (2.24 +/- 0.12 micromol of NO min(-1) mg(-1)), but the double cysteine mutant had a modestly decreased activity (1.75 +/- 0.14 micromol of NO min(-1) mg(-1)). To determine if NO could stimulate release of zinc and dimer dissociation, wild-type protein was allowed to react with an NO donor, DEA/NO, followed by buffer exchange. ICP-AES of samples treated with 10 microM DEA/NO showed a decrease in zinc content (0.23 +/- 0.01 to 0.09 +/- 0.01 mol of Zn/mol of iNOS dimer) with no loss of heme iron. Gel filtration of wild-type iNOS treated similarly resulted in approximately 20% more monomeric iNOS compared to a DEA-treated sample. Only wild-type iNOS had decreased activity (42 +/- 2%) after reaction with 50 microM DEA/NO compared to a control sample. Using the biotin switch method under the same conditions, only wild-type iNOS had increased levels of S-biotinylation. S-Biotinylation was mapped to C104 and C109 on wild-type iNOS using LysC digestion and MALDI-TOF/TOF MS. Immunoprecipitation of iNOS from the mouse macrophage cell line, RAW-264.7, and the biotin switch method were used to confirm endogenous S-nitrosation of iNOS. The data show that S-nitrosation of the zinc tetrathiolate cysteine results in zinc release from the dimer interface and formation of inactive monomers, suggesting that this mode of inhibition might occur in vivo.

(E)-3-[3,4-Bis(meth-oxy-methoxy)phen-yl]-1-(7-hy-droxy-5-meth-oxy-2,2-dimethyl-chroman-8-yl)prop-2-en-1-one.

PubMed

Hashim, Nur Athirah; Ahmad, Farediah; Basar, Norazah; Awang, Khalijah; Ng, Seik Weng

2011-09-01

The reaction of 5,6-(2,2-dimethyl-chroman-yl)-2-hy-droxy-4-meth-oxy-acetophenone and 3,4-bis-(meth-oxy-meth-yloxy)benzaldehyde affords the intense orange title chalcone derivative, C(25)H(30)O(8). The two benzene rings are connected through a -C(=O)-CH=CH- (propenone) unit, which is in an E conformation; the ring with the hy-droxy substitutent is aligned at 19.5 (2)° with respect to this unit, whereas the ring with the meth-oxy-meth-yloxy substituent is aligned at 9.3 (3)°. The dihedral angle between the rings is 19.38 (10)°. The hy-droxy group engages in an intra-molecular O-H⋯O hydrogen bond with the carbonyl O atom of the propenone unit, generating an S(5) ring.

Proper coding of the Abbreviated Injury Scale: can clinical parameters help as surrogates in estimating blood loss?

PubMed

Burkhardt, M; Holstein, J H; Moersdorf, P; Kristen, A; Lefering, R; Pohlemann, T; Pizanis, A

2014-08-01

The Abbreviated Injury Scale (AIS) requires the estimation of the lost blood volume for some severity assignments. This study aimed to develop a rule of thumb for facilitating AIS coding by using objective clinical parameters as surrogate markers of blood loss. Using the example of pelvic ring fractures, a retrospective analysis of TraumaRegister DGU(®) data from 2002 to 2011 was performed. As potential surrogate markers of blood loss, we recorded the hemoglobin (Hb) level, systolic blood pressure (SBP), base excess (BE), Quick's value, units of packed red blood cells (PRBCs) transfused before intensive care unit (ICU) admission, and mortality within 24 h. We identified 11,574 patients with pelvic ring fractures (Tile/OTA classification: 39 % type A, 40 % type B, 21 % type C). Type C fractures were 73.1 % AISpelvis 4 and 26.9 % AISpelvis 5. Type B fractures were 47 % AISpelvis 3, 47 % AISpelvis 4, and 6 % AISpelvis 5. In type C fractures, cut-off values of <7 g/dL Hb, <90 mmHg SBP, <-9 mmol/L BE, <35 % Quick's value, >15 units PRBCs, and death within 24 h had a positive predictive value of 47 % and a sensitivity of 62 % for AISpelvis 5. In type B fractures, these cut-off values had poor sensitivity (48 %) and positive predictive value (11 %) for AISpelvis 5. We failed to develop a rule of thumb for facilitating a proper future AIS coding using the example of pelvic ring fractures. The estimation of blood loss for severity assignment still remains a noteworthy weakness in the AIS coding of traumatic injuries.

EELV Secondary Payload Adapter (ESPA) Ring: Overcoming Challenges to Enable Responsive Space

DTIC Science & Technology

2011-09-01

must also comply with the Air Force Space Command Manual ( AFSPCMAN ) 91 – 710 , Volumes 1, 3 , and 6 and will rely upon a sponsoring agency to...ONLY (Leave blank) 2. REPORT DATE September 2011 3 . REPORT TYPE AND DATES COVERED Master’s Thesis 4. TITLE AND SUBTITLE Robert M. Atkins 5...Strategy ...................................14 3 . EELV—Application and Intent ........................................................16 C. SPACE

Performance of ProEx C and PreTect HPV-Proofer E6/E7 mRNA tests in comparison with the hybrid capture 2 HPV DNA test for triaging ASCUS and LSIL cytology.

PubMed

Alaghehbandan, Reza; Fontaine, Daniel; Bentley, James; Escott, Nicholas; Ghatage, Prafull; Lear, Adrian; Coutlee, Francois; Ratnam, Samuel

2013-09-01

The clinical usefulness of the ProEx C (Becton Dickinson) and PreTect HPV-Proofer E6/E7 mRNA tests (Proofer; Norchip) for the triage of ASCUS and LSIL cytology was determined in comparison with the Hybrid Capture 2 HPV DNA test (HC2; Qiagen). The study population consisted of women with a history of abnormal cytology referred to colposcopy. Histology-confirmed CIN 2+ served as the disease endpoint. The study was based on 1,360 women (mean age 30.7 years), of whom 380 had CIN 2+. Among 315 with ASCUS (CIN 2+, n = 67), the sensitivities of ProEx C, Proofer, and HC2 to detect CIN 2+ were, 71.6, 71.6, and 95.5%, respectively, with a corresponding specificity of 74.6, 74.2, and 35.1%. Among 363 with LSIL (CIN 2+, n = 108), the sensitivities of ProEx C, Proofer, and HC2 were, 67.6, 74.1, and 96.3%, respectively, with a corresponding specificity of 60, 68.2, and 18.4%. Among 225 HC2-positive ASCUS (CIN 2+, n = 64), 105 tested positive by ProEx C, reducing colposcopy referral by 53.3% and detecting 71.9% of CIN 2+; Proofer was positive in 112/225, reducing colposcopy referral by 50.2% and detecting 75.0% of CIN 2+. Among 312 HC2-positive LSIL (CIN 2+, n = 104), 160 tested positive by ProEx C, reducing coloposcopy referral by 48.7% and detecting 66.3% of CIN 2+; Proofer was positive in 159/312, reducing colposcopy referral by 49.0% and detecting 75.0% of CIN 2+. In conclusion, both ProEx C and Proofer have a similar performance profile with a significantly higher specificity but lower sensitivity than HC2 for the detection of CIN 2+. Consequently, although they can reduce colposcopy referral, they will miss a proportion of CIN 2+ cases. This is a major limitation and should be taken into account if these tests are considered for ASCUS or LSIL triage. Copyright © 2012 Wiley Periodicals, Inc., a Wiley company.

Aquabis[1-hydroxy-2-(imidazol-3-ium-1-yl)-1,1′-ethylidenediphophonato-κ2 O,O′]zinc(II) dihydrate

PubMed Central

Freire, Eleonora; Vega, Daniel R.

2009-01-01

In the title complex, [Zn(C5H9NO7P2)2(H2O)]·2H2O, the zinc atom is coordinated by two zoledronate anions [zoledronate = (2-(1-imidazole)-1-hydr­oxy-1,1′-ethyl­idenediphophonate)] and one water mol­ecule. The coordination number is 5. There is one half-mol­ecule in the asymmetric unit, the zinc atom being located on a twofold rotation axis passing through the metal centre and the coordinating water O atom. The anion exists as a zwitterion with an overall charge of −1; the protonated nitro­gen in the ring has a positive charge and the two phospho­nates groups each have a single negative charge. Inter­molecular O—H⋯O hydrogen bonds link the mol­ecules. An N—H⋯O inter­action is also present. PMID:21578165

Crystal structure of 1-(8-meth-oxy-2H-chromen-3-yl)ethanone.

PubMed

Koh, Dongsoo

2014-09-01

In the structure of the title compound, C12H12O3, the di-hydro-pyran ring is fused with the benzene ring. The di-hydro-pyran ring is in a half-chair conformation, with the ring O and methyl-ene C atoms positioned 1.367 (3) and 1.504 (4) Å, respectively, on either side of the mean plane formed by the other four atoms. The meth-oxy group is coplanar with the benzene ring to which it is connected [Cb-Cb-Om-Cm torsion angle = -0.2 (4)°; b = benzene and m = meth-oxy], and similarly the aldehyde is coplanar with respect to the double bond of the di-hydro-pyran ring [Cdh-Cdh-Ca-Oa = -178.1 (3)°; dh = di-hydro-pyran and a = aldehyde]. In the crystal, mol-ecules are linked by weak meth-yl-meth-oxy C-H⋯O hydrogen bonds into supra-molecular chains along the a-axis direction.

Strategic Defense Initiative (SDI) System Architecture and Key Tradeoff Studies, Phase IIC, IDEF0 Functional Decomposition Flows; Appendix D

DTIC Science & Technology

1988-03-15

Number: MDA903-85-C-0065 Document Type: HC Number of Copies In Library : 000001 Record ID: 21248 o o I CO CO I Q CO CO r ^ CO 5 Q o CO...8217 • eg 2 CO <D 2? il n S.2 I a 0) c? *- CD a C3i.t fit mooc I- Q_ 8 £ CO « 3 Sa CO o F* c JS a. »| s-s CD U CO •o 2

Comparison crystal structure conformations of two structurally related biphenyl analogues: 4,4′-bis­[3-(pyrrolidin-1-yl)prop-1-yn-1-yl]-1,1′-biphenyl and 4,4′-bis­{3-[(S)-2-methyl­pyrrolidin-1-yl]prop-1-yn-1-yl}-1,1′-biphen­yl

PubMed Central

Wan, Anqi; Penthala, Narsimha Reddy; Fifer, E. Kim; Parkin, Sean; Crooks, Peter A.

2015-01-01

The title compounds, C26H28N2, (I), and C28H32N2, (II), were designed based on the structure of the potent α9α10 nicotinic acetyl­choline receptor antagonist ZZ161C {1,1′-[[1,1′-biphen­yl]-4,4′-diylbis(prop-2-yne-3,1-di­yl)]bis­(3,4-di­methyl­pyridin-1-ium) bromide}. In order to improve the druglikeness properties of ZZ161C for potential oral administration, the title compounds (I) and (II) were prepared by coupling 4,4′-bis­(3-bromo­prop-1-yn-1-yl)-1,1′-biphenyl with pyrrol­idine, (I), and (S)-2-methyl­pyrrolidine, (II), respectively, in aceto­nitrile at room temperature. The asymmetric unit of (I) contains two half mol­ecules that each sit on sites of crystallographic inversion. As a result, the biphenyl ring systems in compound (I) are coplanar. The biphenyl ring system in compound (II), however, has a dihedral angle of 28.76 (11)°. In (I), the two independent mol­ecules differ in the orientation of the pyrrolidine ring (the nitro­gen lone pair points towards the biphenyl rings in one mol­ecule, but away from the rings in the other). The torsion angles about the ethynyl groups between the planes of the phenyl rings and the pyrrolidine ring N atoms are 84.15 (10) and −152.89 (10)°. In compound (II), the corresponding torsion angles are 122.0 (3) and 167.0 (3)°, with the nitro­gen lone pairs at both ends of the mol­ecule directed away from the central biphenyl rings. PMID:26594393

Single crystal X-ray structure of the artists' pigment zinc yellow

NASA Astrophysics Data System (ADS)

Simonsen, Kim Pilkjær; Christiansen, Marie Bitsch; Vinum, Morten Gotthold; Sanyova, Jana; Bendix, Jesper

2017-08-01

The artists' pigment zinc yellow is in general described as a complex potassium zinc chromate with the empirical formula 4ZnCrO4·K2O·3H2O. Even though the pigment has been in use since the second half of the 19th century also in large-scale industrial applications, the exact structure had hitherto been unknown. In this work, zinc yellow was synthesised by precipitation from an aqueous solution of zinc nitrate and potassium chromate under both neutral and basic conditions, and the products were compared with the pigment used in industrial paints. Analyses by Raman microscopy (MRS), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), and powder X-ray diffraction (PXRD), showed that the synthesised products and the industrial pigment were identical. Single-crystal X-ray crystallography determined the structure of zinc yellow as KZn2(CrO4)2(H2O)(OH) or as KZn2(CrO4)2(H3O2) emphasizing the μ-H3O2- moiety. Notably, the zinc yellow is isostructural to the recently structurally characterized cadmium analog and both belong to the natrochalcite structure type.

Modulation of Muscle Fiber Compositions in Response to Hypoxia via Pyruvate Dehydrogenase Kinase-1

PubMed Central

Nguyen, Daniel D.; Kim, Gyuyoup; Pae, Eung-Kwon

2016-01-01

Muscle fiber-type changes in hypoxic conditions in accordance with pyruvate dehydrogenase kinase (Pdk)-1 and hypoxia inducible factor (Hif)-1α were investigated in rats. Hif-1α and its down-stream molecule Pdk-1 are well known for readily response to hypoxia. We questioned their roles in relation to changes in myosin heavy chain (MyHC) composition in skeletal muscles. We hypothesize that the level of Pdk-1 with respect to the level of Hif-1α determines MyHC composition of the muscle in rats in hypoxia. Young male rats were housed in a chamber maintained at 11.5% (for sustained hypoxia) or fluctuating between 11.5 and 20.8% (for intermittent hypoxia or IH) oxygen levels. Then, muscle tissues from the geniohyoid (GH), soleus, and anterior tibialis (TA) were obtained at the end of hypoxic conditionings. After both hypoxic conditionings, protein levels of Pdk-1 and Hif-1 increased in GH muscles. GH muscles in acute sustained hypoxia favor an anaerobic glycolytic pathway, resulting in an increase in glycolytic MyHC IIb protein-rich fibers while maintain original fatigue-resistant MyHC IIa protein in the fibers; thus, the numbers of IIa- and IIb MyHC co-expressing fibers increased. Exogenous Pdk-1 over-expression using plasmid vectors elevated not only the glycolytic MyHC IIb, but also IIx as well as IIa expressions in C2C12 myotubes in ambient air significantly. The increase of dual expression of IIa- and IIb MyHC proteins in fibers harvested from the geniohyoid muscle has a potential to improve endurance as shown in our fatigability tests. By increasing the Pdk-1/Hif-1 ratio, a mixed-type muscle could alter endurance within the innate characteristics of the muscle toward more fatigue resistant. We conclude that an increased Pdk-1 level in skeletal muscle helps maintain MyHC compositions to be a fatigue resistant mixed-type muscle. PMID:28018235

Short of War: Major USAF Contingency Operations, 1947-1997

DTIC Science & Technology

2000-01-01

4 , F-111, AC-130, C-130, HC-130, KC-135, OV-10, C-141, RF- 4 , U-2, C- 9 , C- 5 Operations On May 12, 1975, as the American civilian...130, MC-130, C-130, C-141, Q- 9 , C- 5 , KC-10, KC-135, E-3, F-15, A-10, SR-71, U-2, RF- 4 , RC-135 Operations In October 1983, a military coup on the tiny...many were needed . During the first phases of the operation, twelve- hour workdays and seven-day workweeks were common. Resultant fatigue threat-

Crystal structure of N-de­acetyl­lappa­coni­tine

PubMed Central

Shi, Xin-Wei; Lu, Qiang-Qiang; Zhou, Jun-Hui; Cui, Xin-Ai

2015-01-01

The title compound, C30H42N2O7 [systematic name: (1S,4S,5S,7S,8S,9S,10S,11S,13R,14S,16S,17R)-20-ethyl-4,8,9-trihy­droxy-1,14,16-tri­meth­oxy­aconitan-4-yl 2-amino­benzoate], isolated from roots of Aconitum sinomontanum Nakai, is a typical aconitane-type C19-diterpenoid alkaloid, which crystallizes with two independent mol­ecules in the asymmetric unit. The conformations of the two independent mol­ecules are closely similar. Each mol­ecule comprises four six-membered rings (A, B, D and E) including one six-membered N-containing heterocyclic ring (E), and two five-membered rings (C and F). Rings A, B and E adopt chair conformations, while ring D displays a boat conformation. Five-membered rings C and F exhibit envelope conformations. IntramolecularN—H⋯O hydrogen bonds between the amino group and carbonyl O atom help to stabilize molecular structure. In the crystal, O—H⋯O hydrogen bonds link the mol­ecules into zigzag chains propagating in [010]. PMID:26396805

Oligomeric flavanoids. Part 15a. Base-catalyzed pyran rearrangements of procyanidin B-2, and evidence for the oxidative transformation of B- to A-type procyanidins

Treesearch

Johann F.W. Burger; Herbert Kolodziej; Richard W. Hemingway; Jan P. Steynberg; Desmond A. Young; Daneel Ferreira

1990-01-01

Procyanidin B-2 3 is subject to facile C-ring isomerizations in 0.1M NaHCO3 solution to form a novel series of 3,4,9,1o-tetrahydro-2H,8H-pyrano[2,3-h]chromenes 7, 9, and 10. The low percentage conversion of B- to A-...

Crystal structure of 3-(adamantan-1-yl)-4-(4-chloro-phen-yl)-1H-1,2,4-triazole-5(4H)-thione.

PubMed

Al-Wabli, Reem I; El-Emam, Ali A; Alroqi, Obaid S; Chidan Kumar, C S; Fun, Hoong-Kun

2015-02-01

The title compound, C18H20ClN3S, is a functionalized triazoline-3-thione derivative. The benzene ring is almost perpendic-ular to the planar 1,2,4-triazole ring [maximum deviation = 0.007 (1) Å] with a dihedral angle of 89.61 (5)° between them and there is an adamantane substituent at the 3-position of the triazole-thione ring. In the crystal, N-H⋯S hydrogen-bonding inter-actions link the mol-ecules into chains extending along the c-axis direction. The crystal packing is further stabilized by weak C-H⋯π inter-actions that link adjacent chains into a two-dimensional structure in the bc plane. The crystal studied was an inversion twin with a 0.50 (3):0.50 (3) domain ratio.

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.

Bovicin HC5 inhibits wasteful amino acid degradation by mixed ruminal bacteria in vitro.

PubMed

Lima, Janaína R; Ribon, Andréa de O Barros; Russell, James B; Mantovani, Hilário C

2009-03-01

Streptococcus bovis HC5 produces a broad spectrum lantibiotic (bovicin HC5) that inhibits pure cultures of hyper ammonia-producing bacteria (HAB). Experiments were preformed to see if: (1) S. bovis HC5 cells could inhibit the deamination of amino acids by mixed ruminal bacteria taken directly from a cow, (2) semi-purified bovicin was as effective as S. bovis HC5 cells, and 3) semi-purified and the feed additive monensin were affecting the same types of ammonia-producing ruminal bacteria. Because purified and semi-purified bovicin HC5 was as effective as S. bovis HC5 cells, it appeared that bovicin HC5 was penetrating the cell membranes of HAB before it could be degraded by peptidases and proteinases. Mixed ruminal bacteria that were successively transferred and enriched nine times with trypticase did not become significantly more resistant to either bovicin HC5 (50 AU mL(-1)) or monensin (5 microM), and amplified rDNA restriction analysis indicated that bovicin HC5 and monensin appeared to be selecting against the same types of bacteria.

Thermodynamics of superconducting Nb3Al, Nb3Ge, Nb3Sn, and V3Ga

NASA Astrophysics Data System (ADS)

Mitrović, B.; Schachinger, E.; Carbotte, J. P.

1984-06-01

We have calculated the superconducting thermodynamic properties for several high-transition-temperature A15 compounds: Nb-Al, Nb-Ge, Nb-Sn, and V-Ga. In our calculations we have used the tunneling electron-phonon-coupling spectra α2F for all four systems considered, and in the case of Nb-Al and Nb-Ge we have also used α2F=CG, where G is the measured generalized phonon density of states and C is a constant. We find that all Nb-based A15 compounds display similar thermodynamic properties, which do not depend explicitly on the band density of states: 2Δ0κBTc≅4.6, ΔCγTc≅2.5-2.6,-Tc[dHc(T)dT]TcHc(0)≅2.1, γ[TcHc(0)]2≅0.134, and positive D(t)'s with the maximum value around 0.02. For Nb3Sn we find good agreement between the calculated properties and the old specific-heat experimental results (γ≅52 mJ/mol K2). The same applies to V3Ga, where the theoretical results have been compared with the experiments of Junod et al. However, we do not find good agreement between calculated ΔCγTc, - Tc[dHc(T)dT]TcHc(0), γ[TcHc(0)]2, and experimental values for Nb3Al and Nb3Ge, presumably due to broadened transitions. It is argued that the tunneling experiments underestimate the value of the gap which should be associated with the inverted α2F.

Selective Sensitization of Zinc Finger Protein Oxidation by Reactive Oxygen Species through Arsenic Binding*

PubMed Central

Zhou, Xixi; Cooper, Karen L.; Sun, Xi; Liu, Ke J.; Hudson, Laurie G.

2015-01-01

Cysteine oxidation induced by reactive oxygen species (ROS) on redox-sensitive targets such as zinc finger proteins plays a critical role in redox signaling and subsequent biological outcomes. We found that arsenic exposure led to oxidation of certain zinc finger proteins based on arsenic interaction with zinc finger motifs. Analysis of zinc finger proteins isolated from arsenic-exposed cells and zinc finger peptides by mass spectrometry demonstrated preferential oxidation of C3H1 and C4 zinc finger configurations. C2H2 zinc finger proteins that do not bind arsenic were not oxidized by arsenic-generated ROS in the cellular environment. The findings suggest that selectivity in arsenic binding to zinc fingers with three or more cysteines defines the target proteins for oxidation by ROS. This represents a novel mechanism of selective protein oxidation and demonstrates how an environmental factor may sensitize certain target proteins for oxidation, thus altering the oxidation profile and redox regulation. PMID:26063799

Photochemical electron transfer in chlorophyll-porphyrin-quinone triads. The role of the porphyrin-bridging molecule

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

Johnson, D.G.; Niemczyk, M.P.; Minsek, D.W.

1993-06-30

The photochemistry of four chlorophyll-porphyrin-naphthoquinone molecules possessing both fixed distances and orientations between the three components is described. These molecules consist of a methyl pyropheophorbide a or pyrochlorophyllide a that is directly bonded at its 3-position to the 5-position of a 2,8,12,18-tetraethyl-3,7,13,-17-tetramethylporphyrin, which is in turn bonded at its 15-position to a 2-triptycenenaphthoquinone. In addition, porphyrin-quinone compounds in which the chlorins are replaced by a p-tolyl group were also prepared as reference compounds. Selective metalation of the macrocycles with zinc gives the series ZCHPNQ, ZCZPNQ, HCZPNQ, HCHPNQ, HPNQ, and ZPNQ, where H, Z, C, P, and NQ denote free base,more » Zn derivative, chlorophyll, porphyrin, and naphthoquinone, respectively. Selective excitation of ZC in ZCZPNQ and ZCHPNQ, and HC in HCHPNQ dissolved in butyronitrile yields ZC[sup +]ZPNQ[sup [minus

Controlling the directionality of charge transfer in phthalocyaninato zinc sensitizer for a dye-sensitized solar cell: density functional theory studies.

PubMed

Wan, Liang; Qi, Dongdong; Zhang, Yuexing; Jiang, Jianzhuang

2011-01-28

Density functional theory (DFT) calculation on the molecular structures, charge distribution, molecular orbitals, electronic absorption spectra of a series of eight unsymmetrical phthalocyaninato zinc complexes with one peripheral (E)-2-cyano-3-(5-vinylthiophen-2-yl) acrylic acid substituent at 2 or 3 position as an electron-withdrawing group and a different number of electron-donating amino groups at the remaining peripheral positions (9, 10, 16, 17, 23, 24) of the phthalocyanine ring, namely ZnPc-β-A, ZnPc-β-A-I-NH(2), ZnPc-β-A-II-NH(2), ZnPc-β-A-III-NH(2), ZnPc-β-A-I,II-NH(2), ZnPc-β-A-I,III-NH(2), ZnPc-β-A-II,III-NH(2), and ZnPc-β-A-I,II,III-NH(2), reveals the effects of amino groups on the charge transfer properties of these phthalocyanine derivatives with a typical D-π-A electronic structure. The introduction of amino groups was revealed altering of the atomic charge distribution, lifting the frontier molecular orbital level, red-shift of the near-IR bands in the electronic absorption spectra, and finally resulting in enhanced charge transfer directionality for the phthalocyanine compounds. Along with the increase of the peripheral amino groups at the phthalocyanine ring from 0, 2, 4, to 6, the dihedral angle between the phthalocyanine ring and the average plane of the (E)-2-cyano-3-(5-vinylthiophen-2-yl) acrylic acid substituent increases from 0 to 3.3° in an irregular manner. This is in good contrast to the regular and significant change in the charge distribution, destabilization of frontier orbital energies, and red shift of near-IR bands of phthalocyanine compounds along the same order. In addition, comparative studies indicate the smaller effect of incorporating two amino groups onto the 16 and 17 than on 9 and 10 or 23 and 24 peripheral positions of the phthalocyanine ring onto the aforementioned electronic properties, suggesting the least effect on tuning the charge transfer property of the phthalocyanine compound via introducing two electron-donating amino groups onto the 16 and 17 peripheral positions. As expected, compound ZnPc-β-A-I,III-NH(2) with four amino groups at 9, 10, 23, and 24 positions of the phthalocyanine ring shows the best charge transfer directionality among the three phthalocyaninato zinc complexes with four peripheral amino groups.

Dipropyl 3,6-diphenyl-1,2-dihydro-1,2,4,5-tetrazine-1,2-dicarboxylate.

PubMed

Rao, Guo-Wu; Hu, Wei-Xiao

2003-05-01

The title compound, C(22)H(24)N(4)O(4), was prepared from propyl chloroformate and 3,6-diphenyl-1,2-dihydro-s-tetrazine. This reaction yields the title compound rather than dipropyl 3,6-diphenyl-1,4-dihydro-s-tetrazine-1,4-dicarboxylate. The 2,3-diazabutadiene group in the central six-membered ring is not planar; the C=N double-bond length is 1.285 (2) A, and the average N-N single-bond length is 1.401 (3) A, indicating a lack of conjugation. The ring has a twist conformation, in which adjacent N atoms lie +/- 0.3268 (17) A from the plane of the ring. The molecule has twofold crystallographic symmetry.

A polymorphic form of 4,4-dimethyl-8-methylene-3-azabicyclo[3.3.1]non-2-en-2-yl 3-indolyl ketone, an indole alkaloid extracted from Aristotelia chilensis (maqui).

PubMed

Paz, Cristian; Becerra, José; Silva, Mario; Freire, Eleonora; Baggio, Ricardo

2013-12-15

The title compound [systematic name: (4,4-dimethyl-8-methylene-3-azabicyclo[3.3.1]non-2-en-2-yl)(1H-indol-3-yl)methanone], C20H22N2O, (II), was obtained from mother liquors extracted from Aristotelia chilensis (commonly known as maqui), a native Chilean tree. The compound is a polymorphic form of that obtained from the same source and reported by Watson, Nagl, Silva, Cespedes & Jakupovic [Acta Cryst. (1989), C45, 1322-1324], (Ia). The molecule consists of an indolyl ketone fragment and a nested three-ring system, with both groups linked by a C-C bridge. Comparison of both forms shows that they do not differ in their gross features but in the relative orientation of the two ring systems, due to different rotations around the bridge, as measured by the O=C-C=N torsion angle [130.0 (7)° in (Ia) and 161.6 (2)° in (II)]. The resulting slight conformational differences are reflected in a number of intramolecular contacts being observed in (II) but not in (Ia). Regarding intermolecular interactions, both forms share a similar N-H···O synthon but with differing hydrogen-bonding strength, leading in both cases to C(6) catemers with different chain motifs. There are marked differences between the two forms regarding colour and the (de)localization of a double bond, which allows speculation about the possible existence of different variants of this type of molecule.

VpRFP1, a novel C4C4-type RING finger protein gene from Chinese wild Vitis pseudoreticulata, functions as a transcriptional activator in defence response of grapevine

PubMed Central

Yu, Yihe; Xu, Weirong; Wang, Shengyi; Xu, Yan; Li, Hui'e; Wang, Yuejin; Li, Shuxiu

2011-01-01

RING finger proteins comprise a large family and play important roles in regulation of growth and development, hormone signalling, and responses to biotic and abiotic stresses in plants. In this study, the identification and functional characterization of a C4C4-type RING finger protein gene from the Chinese wild grapevine Vitis pseudoreticulata (designated VpRFP1) are reported. VpRFP1 was initially identified as an expressed sequence tag (EST) from a cDNA library constructed from leaves of V. pseudoreticulata inoculated with the grapevine powdery mildew Uncinula necator. Sequence analysis of the deduced VpRFP1 protein based on the full-length cDNA revealed an N-terminal nuclear localization signal (NLS) and a C-terminal C4C4-type RING finger motif with the consensus sequence Cys-X2-Cys-X13-Cys-X1-Cys-X4-Cys-X2-Cys-X10-Cys-X2-Cys. Upon inoculation with U. necator, expression of VpRFP1 was rapidly induced to higher levels in mildew-resistant V. pseudoreticulata plants. In contrast, expression of VpRFP1 was down-regulated in mildew-susceptible V. vinifera plants. Western blotting using an antibody raised against VpRFP1 showed that VpRFP1 was also induced to higher levels in V. pseudoreticulata plants at 12–48 hours post-inoculation (hpi). However, there was only slight increase in VpRFP in V. vinifera plants in the same time frame, even though a more significant increase was observed at 96–144 hpi in these plants. Results from transactivation assays in yeast showed that the RING finger motif of VpRFP1 exhibited some activity of transcriptional activation; however, no activity was seen with the full-length VpRFP1. Overexpression of VpRFP1 in Arabidopsis plants was found to enhance resistance to Arabidopsis powdery mildew Golovinomyces cichoracearum, which seemed to be correlated with increased transcript levels of AtPR1 and AtPR2 in the pathogen-infected tissues. In addition, the Arabidopsis transgenic lines showed enhanced resistance to a virulent bacterial pathogen Pseudomonas syringae pv. tomato DC3000. Taken together, the results suggested that VpRFP1 may be a transcriptional activator of defence-related genes in grapevines. PMID:21862480

Characterization of the Minimum Energy Paths for the Ring Closure Reactions of C4H3 with Acetylene

NASA Technical Reports Server (NTRS)

Walch, Stephen P.

1995-01-01

The ring closure reaction of C4H3 with acetylene to give phenyl radical is one proposed mechanism for the formation of the first aromatic ring in hydrocarbon combustion. There are two low-lying isomers of C4H3; 1-dehydro-buta-l-ene-3-yne (n-C4H3) and 2-dehydro-buta-l-ene-3-yne (iso-C4H3). It has been proposed that only n-C4H3 reacts with acetylene to give phenyl radical, and since iso-C4H3 is more stable than n-C4H3, formation of phenyl radical by this mechanism is unlikely. We report restricted Hartree-Fock (RHF) plus singles and doubles configuration interaction calculations with a Davidson's correction (RHF+1+2+Q) using the Dunning correlation consistent polarized valence double zeta basis set (cc-pVDZ) for stationary point structures along the reaction pathway for the reactions of n-C4H3 and iso-C4H3 with acetylene. n-C4H3 plus acetylene (9.4) has a small entrance channel barrier (17.7) (all energetics in parentheses are in kcal/mol with respect to iso-C4H3 plus acetylene) and the subsequent closure steps leading to phenyl radical (-91.9) are downhill with respect to the entrance channel barrier. Iso-C4H3 Plus acetylene also has an entrance channel barrier (14.9) and there is a downhill pathway to 1-dehydro-fulvene (-55.0). 1-dehydro-fulvene can rearrange to 6-dehydro-fulvene (-60.3) by a 1,3-hydrogen shift over a barrier (4.0), which is still below the entrance channel barrier, from which rearrangement to phenyl radical can occur by a downhill pathway. Thus, both n-C4H3 and iso-C4H3 can react with acetylene to give phenyl radical with small barriers.

Four plant defensins from an indigenous South African Brassicaceae species display divergent activities against two test pathogens despite high sequence similarity in the encoding genes

PubMed Central

2011-01-01

Background Plant defensins are an important component of the innate defence system of plants where they form protective antimicrobial barriers between tissue types of plant organs as well as around seeds. These peptides also have other activities that are important for agricultural applications as well as the medical sector. Amongst the numerous plant peptides isolated from a variety of plant species, a significant number of promising defensins have been isolated from Brassicaceae species. Here we report on the isolation and characterization of four defensins from Heliophila coronopifolia, a native South African Brassicaceae species. Results Four defensin genes (Hc-AFP1-4) were isolated with a homology based PCR strategy. Analysis of the deduced amino acid sequences showed that the peptides were 72% similar and grouped closest to defensins isolated from other Brassicaceae species. The Hc-AFP1 and 3 peptides shared high homology (94%) and formed a unique grouping in the Brassicaceae defensins, whereas Hc-AFP2 and 4 formed a second homology grouping with defensins from Arabidopsis and Raphanus. Homology modelling showed that the few amino acids that differed between the four peptides had an effect on the surface properties of the defensins, specifically in the alpha-helix and the loop connecting the second and third beta-strands. These areas are implicated in determining differential activities of defensins. Comparing the activities after recombinant production of the peptides, Hc-AFP2 and 4 had IC50 values of 5-20 μg ml-1 against two test pathogens, whereas Hc-AFP1 and 3 were less active. The activity against Botrytis cinerea was associated with membrane permeabilization, hyper-branching, biomass reduction and even lytic activity. In contrast, only Hc-AFP2 and 4 caused membrane permeabilization and severe hyper-branching against the wilting pathogen Fusarium solani, while Hc-AFP1 and 3 had a mild morphogenetic effect on the fungus, without any indication of membrane activity. The peptides have a tissue-specific expression pattern since differential gene expression was observed in the native host. Hc-AFP1 and 3 expressed in mature leaves, stems and flowers, whereas Hc-AFP2 and 4 exclusively expressed in seedpods and seeds. Conclusions Two novel Brassicaceae defensin sequences were isolated amongst a group of four defensin encoding genes from the indigenous South African plant H. coronopifolia. All four peptides were active against two test pathogens, but displayed differential activities and modes of action. The expression patterns of the peptide encoding genes suggest a role in protecting either vegetative or reproductive structures in the native host against pathogen attack, or roles in unknown developmental and physiological processes in these tissues, as was shown with other defensins. PMID:22032337

Reduced 3,4'-bipyrazoles from a simple pyrazole precursor: synthetic sequence, molecular structures and supramolecular assembly.

PubMed

Cuartas, Viviana; Insuasty, Braulio; Cobo, Justo; Glidewell, Christopher

2017-10-01

The reaction of 5-chloro-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde and N-benzylmethylamine under microwave irradiation gives 5-[benzyl(methyl)amino]-3-methyl-1-phenyl-1H-pyrazole-4-carbaldehyde, C 19 H 19 N 3 O, (I). Subsequent reactions under basic conditions, between (I) and a range of acetophenones, yield the corresponding chalcones. These undergo cyclocondensation reactions with hydrazine to produce reduced bipyrazoles which can be N-formylated with formic acid or N-acetylated with acetic anhydride. The structures of (I) and of representative examples from this reaction sequence are reported, namely the chalcone (E)-3-{5-[benzyl(methyl)amino]-3-methyl-1-phenyl-1H-pyrazol-4-yl}-1-(4-bromophenyl)prop-2-en-1-one, C 27 H 24 BrN 3 O, (II), the N-formyl derivative (3RS)-5'-[benzyl(methyl)amino]-3'-methyl-1',5-diphenyl-3,4-dihydro-1'H,2H-[3,4'-bipyrazole]-2-carbaldehyde, C 28 H 27 N 5 O, (III), and the N-acetyl derivative (3RS)-2-acetyl-5'-[benzyl(methyl)amino]-5-(4-methoxyphenyl)-3'-methyl-1'-phenyl-3,4-dihydro-1'H,2H-[3,4'-bipyrazole], which crystallizes as the ethanol 0.945-solvate, C 30 H 31 N 5 O 2 ·0.945C 2 H 6 O, (IV). There is significant delocalization of charge from the benzyl(methyl)amino substituent onto the carbonyl group in (I), but not in (II). In each of (III) and (IV), the reduced pyrazole ring is modestly puckered into an envelope conformation. The molecules of (I) are linked by a combination of C-H...N and C-H...π(arene) hydrogen bonds to form a simple chain of rings; those of (III) are linked by a combination of C-H...O and C-H...N hydrogen bonds to form sheets of R 2 2 (8) and R 6 6 (42) rings, and those of (IV) are linked by a combination of O-H...N and C-H...O hydrogen bonds to form a ribbon of edge-fused R 2 4 (16) and R 4 4 (24) rings.

TRPV3 expression and vasodilator function in isolated uterine radial arteries from non-pregnant and pregnant rats.

PubMed

Murphy, Timothy V; Kanagarajah, Arjna; Toemoe, Sianne; Bertrand, Paul P; Grayson, T Hilton; Britton, Fiona C; Leader, Leo; Senadheera, Sevvandi; Sandow, Shaun L

2016-08-01

This study investigated the expression and function of transient receptor potential vanilloid type-3 ion channels (TRPV3) in uterine radial arteries isolated from non-pregnant and twenty-day pregnant rats. Immunohistochemistry (IHC) suggested TRPV3 is primarily localized to the smooth muscle in arteries from both non-pregnant and pregnant rats. IHC using C' targeted antibody, and qPCR of TRPV3 mRNA, suggested pregnancy increased arterial TRPV3 expression. The TRPV3 activator carvacrol caused endothelium-independent dilation of phenylephrine-constricted radial arteries, with no difference between vessels from non-pregnant and pregnant animals. Carvacrol-induced dilation was reduced by the TRPV3-blockers isopentenyl pyrophosphate and ruthenium red, but not by the TRPA1 or TRPV4 inhibitors HC-030031 or HC-067047, respectively. In radial arteries from non-pregnant rats only, inhibition of NOS and sGC, or PKG, enhanced carvacrol-mediated vasodilation. Carvacrol-induced dilation of arteries from both non-pregnant and pregnant rats was prevented by the IKCa blocker TRAM-34. TRPV3 caused an endothelium-independent, IKCa-mediated dilation of the uterine radial artery. NO-PKG-mediated modulation of TRPV3 activity is lost in pregnancy, but this did not alter the response to carvacrol. Copyright © 2016 Elsevier Inc. All rights reserved.

Structural characterization of analgesic isothiazolopyridines of Mannich base type; X-ray analysis of 2-[(4-phenylpiperazin-1-yl)ethyl]- and 2-[(4-methylpiperazin-1-yl)methyl]-4,6-dimethylisothiazolo[5,4- b]pyridin-3(2 H)-ones

NASA Astrophysics Data System (ADS)

Karczmarzyk, Zbigniew; Malinka, Wiesław

2008-10-01

The crystal and molecular structures of the title 2-[(4-phenylpiperazin-1-yl)ethyl], 6, and 2-[(4-methylpiperazin-1-yl)methyl], 7, derivatives of isothiazolo[5,4- b]pyridine were determined. The molecular packing in 6 is influenced by C-H…X (X = N, O) hydrogen bonds and π… π interactions of the pairs of isothiazolopyridine rings belonging to inversion related molecules. The crystal structure of 7 contains the net of O-H…N and C-H…O intermolecular hydrogen bonds. Moreover, isothiazole and pyridine rings show significant stacking with the shortest π… π distances of 3.453 Å. The conformations of the molecules 6 and 7 were compared with those observed in the crystals of related analgesic 4-arylpiperazine ( 2, 3) and 4-arylpiperidine ( 4, 5) derivatives of isothiazolopyridine of Mannich base type. Additionally, the computational investigations using semi-empirical AM1 and RHF/6-31G∗∗ ab initio methods are performed within series 2- 7 in order to find correlation between geometrical and electronic parameters of the molecules and their analgesic action. Results of the theoretical calculations show that the charge distribution on the piperazine N atoms is correlated with conformation of the (4-arylpiperazin-1-yl)methyl side chain and analgesic action of isothiazolopyridines analyzed.

Myosin isoforms and contractile properties of single fibers of human Latissimus Dorsi muscle.

PubMed

Paoli, Antonio; Pacelli, Quirico F; Cancellara, Pasqua; Toniolo, Luana; Moro, Tatiana; Canato, Marta; Miotti, Danilo; Reggiani, Carlo

2013-01-01

The aim of our study was to investigate fiber type distribution and contractile characteristics of Latissimus Dorsi muscle (LDM). Samples were collected from 18 young healthy subjects (9 males and 9 females) through percutaneous fine needle muscle biopsy. The results showed a predominance of fast myosin heavy chain isoforms (MyHC) with 42% of MyHC 2A and 25% of MyHC 2X, while MyHC 1 represented only 33%. The unbalance toward fast isoforms was even greater in males (71%) than in females (64%). Fiber type distribution partially reflected MyHC isoform distribution with 28% type 1/slow fibers and 5% hybrid 1/2A fibers, while fast fibers were divided into 30% type 2A, 31% type A/X, 4% type X, and 2% type 1/2X. Type 1/slow fibers were not only less abundant but also smaller in cross-sectional area than fast fibers. During maximal isometric contraction, type 1/slow fibers developed force and tension significantly lower than the two major groups of fast fibers. In conclusion, the predominance of fast fibers and their greater size and strength compared to slow fibers reveal that LDM is a muscle specialized mainly in phasic and powerful activity. Importantly, such specialization is more pronounced in males than in females.

Silica-Based, Hyper-Crosslinked Acid Stable Stationary Phases for High Performance Liquid Chromatography

PubMed Central

Zhang, Yu; Luo, Hao; Carr, Peter W.

2011-01-01

A new family of Hyper-Crosslinked (HC) phases has been recently introduced for use under very aggressive acid conditions including those encountered in ultra-fast, high temperature Two-Dimensional Liquid Chromatography (2DLC). This type of stationary phase showed significantly enhanced acid and thermal stability compared to the most acid stable, commercial RPLC phases. In addition, the use of “orthogonal” chemistry to make surface-confined polymer networks ensures good reproducibility and high efficiency. One of the most interesting features of the HC phases is the ability to derivatize the surface aromatic groups with various functional groups. This led to the development of a family of hyper-crosslinked phases possessing a wide variety of chromatographic selectivities by attaching hydrophobic (e.g. –C8), ionizable (e.g. -COOH, -SO3H), aromatic (e.g. –toluene) or polar (e.g. -OH) species to the aromatic polymer network. HC reversed phases with various degrees of hydrophobicity and mixed-mode HC phases with added strong and weak cation exchange sites have been synthesized, characterized and applied. These silica-based acid-stable HC phases, with their attractive chromatographic properties, should be very useful in the separations of bases or biological analytes in acidic media, especially at elevated temperatures. This work reviews the prior research on HC phases and introduces a novel HC phase made by alternative chemistry. PMID:21906745

Crystal structure of (3S*,4R*)-4-fluoro-3-(4-meth-oxy-phen-yl)-1-oxo-2-phenyl-1,2,3,4-tetra-hydro-iso-quinoline-4-carb-oxy-lic acid.

PubMed

Lehmann, Anna; Lechner, Lisa; Radacki, Krzysztof; Braunschweig, Holger; Holzgrabe, Ulrike

2017-06-01

The title compound, C 23 H 18 FNO 4 , crystallized as a racemate. It exhibits a cis conformation with respect to the F atom and the methine H atom. The piperidine ring has a screw-boat conformation. The meth-oxy-phenyl ring and the phenyl ring are inclined to the mean plane of the iso-quinoline ring system by 89.85 (4) and 46.62 (5)°, respectively, and by 78.15 (5)° to one another. In the crystal, mol-ecules are linked by an O-H⋯O hydrogen bond forming chains propagating along the a -axis direction. The chains are linked by C-H⋯F hydrogen bonds, forming layers lying parallel to the ab plane.

Crystal structure of azilsartan methyl ester ethyl acetate hemisolvate.

PubMed

Li, Zhengyi; Liu, Rong; Zhu, Meilan; Chen, Liang; Sun, Xiaoqiang

2015-02-01

The title compound, C26H22N4O5 (systematic name: methyl 2-eth-oxy-1-{4-[2-(5-oxo-4,5-di-hydro-1,2,4-oxa-diazol-3-yl)phenyl]benz-yl}-1H-1,3-benzo-diazole-7-carboxyl-ate ethyl acetate hemisolvate), was obtained via cyclization of methyl (Z)-2-eth-oxy-1-{(2'-(N'-hy-droxy-carbamimido-yl)-[1,1'-biphen-yl]-4-yl)meth-yl}-1H-benzo[d]imidazole-7-carboxyl-ate with diphen-yl carbonate. There are two independent mol-ecules (A and B) with different conformations and an ethyl acetate solvent mol-ecule in the asymmetric unit. In mol-ecule A, the dihedral angle between the benzene ring and its attached oxa-diazole ring is 59.36 (17); the dihedral angle between the benzene rings is 43.89 (15) and that between the benzene ring and its attached imidazole ring system is 80.06 (11)°. The corres-ponding dihedral angles in mol-ecule B are 58.45 (18), 50.73 (16) and 85.37 (10)°, respectively. The C-O-C-Cm (m = meth-yl) torsion angles for the eth-oxy side chains attached to the imidazole rings in mol-ecules A and B are 93.9 (3) and -174.6 (3)°, respectively. In the crystal, the components are linked by N-H⋯N and C-H⋯O hydrogen bonds, generating a three-dimensional network. Aromatic π-π stacking inter-actions [shortest centroid-centroid separation = 3.536 (3)Å] are also observed.

X-Ray study of hetero ring flexibility in norbornane, norbornene-fused 1,3-oxazin-2-thiones Structure of 5,8-methano- r-4-phenyl-c-4a, c-5,6,7, c-8, c- 8a-hexahydro-4H- 1 ,3-benzoxazin-2 (3H)-thione

NASA Astrophysics Data System (ADS)

Kálmán, A.; Argay, Gy.; Stájer, G.; Bernáth, G.

1991-08-01

The structure of S,8-methano- r-4-phenyl c4a, c5,6,7 c8 c8ahexahydro4 H 1,3 -benzoxazin- 2 (3 H)-thione (C 15H 17N0S, M r=259.37) has been established by X-ray crystallography from diffractometer data: it crystallizes in the monoclinic space group P2 1/n with a=6.150(2) Å, b=9.655(1) Å, c=22.093(4) Å,β=96.75(2)† V=1302.7(8) Å 3,4,D c=1.32gcm -3and p( Cu K) =20.4cm -. The structure has been solved by direct methods, refined to R=0.050 for 2193 observed reflections. The X-ray analysis substantiated the structure: the NMR spectra in- dicated that the 4-phenyl group assumes an exo-equatorial position. The puckering parameters of D. Cremer, J.A. Pople, J. Am. Chem. Soc., 97 (1975), 1354 (ref.1), of the distorted hetero ring (a transitional form between E 4-envelope, ( 5S 4-screw-boat) show that, depending on the positions of the hetero atoms, both the norbornane, norbornene skeletons markedly alter the characteristic transitional ( 5E/ 5H 6) shape of the 1,3-oxazine ring observed in other saturated, partly saturated l,3-benzoxazin-2-ones, analogous thiones.

Synthesis and spectral characterization of Zn(II) microsphere series for antimicrobial application

NASA Astrophysics Data System (ADS)

Singh, Ajay K.; Pandey, Sarvesh K.; Pandey, O. P.; Sengupta, S. K.

2014-09-01

Microsphere series have been synthesized by reacting zinc(II) acetate dihydrate with Schiff bases derived from 2-hydrazino-5-[substituted phenyl]-1,3,4-thiadiazole/oxadiazole/triazole with salicylaldehyde. Elemental analysis suggests that the complexes have 1:2 and 1:1 stoichiometry of the type [Zn(L)2(H2O)2] and [Zn(L‧)(H2O)2]; LH = Schiff bases derived from 2-hydrazino-5-[substituted phenyl]-1,3,4-thia/oxadiazole with salicylaldehyde; L‧H2 = Schiff bases derived from 3-(substituted phenyl)-4-amino-5-hydrazino-1,2,4-triazole and salicylaldehyde and were characterized by elemental analyses, IR, 1H NMR and 13C NMR spectral data. Scanning electron microscopy (SEM) showed that synthesized materials have microsphere like structure and there EDX analysis comparably matches with elemental analysis. For the antimicrobial application Schiff bases and their zinc(II) complexes were screened for four bacteria e.g. Bacillus subtilis, Pseudomonas aeruginosa, Salmonella typhi, Streptococcus pyogenes and four fungi e.g. Cyrtomium falcatum, Aspergillus niger, Fusarium oxysporium and Curvularia pallescence by the reported method. Schiff base and Zn(II) compounds showed significant antimicrobial activities. However, activities increase upon chelation. Thermal analysis (TGA) data of compound (10) showed its stability up to 300 °C.

Nanogel antigenic protein-delivery system for adjuvant-free intranasal vaccines

NASA Astrophysics Data System (ADS)

Nochi, Tomonori; Yuki, Yoshikazu; Takahashi, Haruko; Sawada, Shin-Ichi; Mejima, Mio; Kohda, Tomoko; Harada, Norihiro; Kong, Il Gyu; Sato, Ayuko; Kataoka, Nobuhiro; Tokuhara, Daisuke; Kurokawa, Shiho; Takahashi, Yuko; Tsukada, Hideo; Kozaki, Shunji; Akiyoshi, Kazunari; Kiyono, Hiroshi

2010-07-01

Nanotechnology is an innovative method of freely controlling nanometre-sized materials. Recent outbreaks of mucosal infectious diseases have increased the demands for development of mucosal vaccines because they induce both systemic and mucosal antigen-specific immune responses. Here we developed an intranasal vaccine-delivery system with a nanometre-sized hydrogel (`nanogel') consisting of a cationic type of cholesteryl-group-bearing pullulan (cCHP). A non-toxic subunit fragment of Clostridium botulinum type-A neurotoxin BoHc/A administered intranasally with cCHP nanogel (cCHP-BoHc/A) continuously adhered to the nasal epithelium and was effectively taken up by mucosal dendritic cells after its release from the cCHP nanogel. Vigorous botulinum-neurotoxin-A-neutralizing serum IgG and secretory IgA antibody responses were induced without co-administration of mucosal adjuvant. Importantly, intranasally administered cCHP-BoHc/A did not accumulate in the olfactory bulbs or brain. Moreover, intranasally immunized tetanus toxoid with cCHP nanogel induced strong tetanus-toxoid-specific systemic and mucosal immune responses. These results indicate that cCHP nanogel can be used as a universal protein-based antigen-delivery vehicle for adjuvant-free intranasal vaccination.

Deep K-band Observations of TMC-1 with the Green Bank Telescope: Detection of HC7O, Nondetection of HC11N, and a Search for New Organic Molecules

NASA Astrophysics Data System (ADS)

Cordiner, M. A.; Charnley, S. B.; Kisiel, Z.; McGuire, B. A.; Kuan, Y.-J.

2017-12-01

The 100 m Robert C. Byrd Green Bank Telescope K-band (KFPA) receiver was used to perform a high-sensitivity search for rotational emission lines from complex organic molecules in the cold interstellar medium toward TMC-1 (cyanopolyyne peak), focussing on the identification of new carbon-chain-bearing species as well as molecules of possible prebiotic relevance. We report a detection of the carbon-chain oxide species HC7O and derive a column density of (7.8+/- 0.9)× {10}11 cm-2. This species is theorized to form as a result of associative electron detachment reactions between oxygen atoms and C7H-, and/or reaction of C6H2 + with CO (followed by dissociative electron recombination). Upper limits are given for the related HC6O, C6O, and C7O molecules. In addition, we obtained the first detections of emission from individual 13C isotopologues of HC7N, and derive abundance ratios HC7N/HCCC13CCCCN = 110 ± 16 and HC7N/HCCCC13CCCN = 96 ± 11, indicative of significant 13C depletion in this species relative to the local interstellar elemental 12C/13C ratio of 60-70. The observed spectral region covered two transitions of HC11N, but emission from this species was not detected, and the corresponding column density upper limit is 7.4× {10}10 {{cm}}-2 (at 95% confidence). This is significantly lower than the value of 2.8× {10}11 {{cm}}-2 previously claimed by Bell et al. and confirms the recent nondetection of HC11N in TMC-1 by Loomis et al. Upper limits were also obtained for the column densities of malononitrile and the nitrogen heterocycles quinoline, isoquinoline, and pyrimidine.

N,N′-Dicyclo­hexyl­naphthalene-1,8;4:5-dicarboximide

PubMed Central

Shukla, Deepak; Rajeswaran, Manju

2008-01-01

The title compound, C26H26N2O4, synthesized by the reaction of naphthalene-1,4,5,8-tetra­carboxylic acid anhydride and cyclo­hexyl­amine, exhibits good n-type semiconducting properties. Accordingly, thin-film transistor devices comprising this compound show n-type behavior with high field-effect electron moblity ca 6 cm2/Vs [Shukla, Nelson, Freeman, Rajeswaran, Ahearn, Meyer & Carey(2008 ▶). Chem. Mater. Submitted]. The asymmetric unit comprises one-quarter of the centrosymmetric mol­ecule in which all but two methyl­ene C atoms of the cyclo­hexane ring lie on a mirror plane; the point-group symmetry is 2/m. The naphthalene­diimide unit is strictly planar, and the cyclo­hexane rings adopt chair conformations with the diimide unit in an equatorial position on each ring. PMID:21201718

Magnetostatic Surface Field Measurement Facility.

DTIC Science & Technology

1986-12-01

Sphere 106 4 Page C .2 Acoustically Hard Prolate 10 8 HC.3 Perfectly Conducting Sphere 110 C .4 Some Implications 113 C .5 References 115 APPENDIX D 117 0.1...I/a2+ r2+z2 - 2ar cos a d -3, C 2 var 1 -K2 )K - / - E Jo 3ɚ- (2.37) and since J cos a da 0 0 we have . ... 1 2)K A = - -~i)Ej + 0 (k 3) . (2.38...assumed exp(jwt) time convention. C - We begin by analyzing one of our eight secondary distribution sub- systems, as shown in Fig. D .2. V -j- Z 0j B e Vx

Synthesis and reaction of [[HC(CMeNAr)2]Mn]2 (Ar = 2,6-iPr2C6H3): the complex containing three-coordinate manganese(I) with a Mn-Mn bond exhibiting unusual magnetic properties and electronic structure.

PubMed

Chai, Jianfang; Zhu, Hongping; Stückl, A Claudia; Roesky, Herbert W; Magull, Jörg; Bencini, Alessandro; Caneschi, Andrea; Gatteschi, Dante

2005-06-29

This paper reports on the synthesis, X-ray structure, magnetic properties, and DFT calculations of [[HC(CMeNAr)2]Mn]2 (Ar = 2,6-iPr2C6H3) (2), the first complex with three-coordinate manganese(I). Reduction of the iodide [[HC(CMeNAr)2]Mn(mu-I)]2 (1) with Na/K in toluene afforded 2 as dark-red crystals. The molecule of 2 contains a Mn2(2+) core with a Mn-Mn bond. The magnetic investigations show a rare example of a high-spin manganese(I) complex with an antiferromagnetic interaction between the two Mn(I) centers. The DFT calculations indicate a strong s-s interaction of the two Mn(I) ions with the open shell configuration (3d54s1). This suggests that the magnetic behavior of 2 could be correctly described as the coupling between two S1 = S2 = 5/2 spin centers. The Mn-Mn bond energy is estimated at 44 kcal mol(-1) by first principle calculations with the B3LYP functional. The further oxidative reaction of 2 with KMnO4 or O2 resulted in the formation of manganese(III) oxide [[HC(CMeNAr)2]Mn(mu-O)]2 (3). Compound 3 shows an antiferromagnetic coupling between the two oxo-bridged manganese(III) centers by magnetic measurements.

Self-Consistent Kinetic Theory of Stochasticity.

DTIC Science & Technology

1979-08-01

induced contractions. The results indicated that there is a minor contaminant in yel l ow HC— 3 other than deanol which was a potent inhibitor of...pectively (Fi g. 2). Also , the wh i te HC-3 was a competitive inhibitor of AChE (Fig. 3), whereas the yellow HC-3 was a mixed—type inhibitor. Deanol ...by yellow HC-3 recrystallized one time from boiling methanol fell in between the white and yellow commercial samples (Fig. 1). Deanol has been

Evaluation of the Performance of O-rings Made with Different Elastomeric Polymers in Simulated Geothermal Environments at 300°C

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

Sugama, Toshifumi; Pyatina, Tatiana; Redline, Erica Marie

2014-12-01

This paper aims to evaluate the survival of O-rings made with six different elastomeric polymers, EPDM, type I- and II-FKM, FEPM, FFKM, and FSR, in five different simulated geothermal environments at 300°C. It further defines the relative strengths and weaknesses of the materials in each environment. The environments tested were: 1) non-aerated steam-cooling cycles, 2) aerated steam-cooling cycles, 3) water-based drilling fluid, 4) CO2-rich geo-brine fluid, and, 5) heat-cool water quenching cycles. Following exposure, the extent of oxidation, oxidationinduced degradation, thermal behaviors, micro-defects, permeation depths of ionic species present in environments throughout the O-ring, silicate-related scale-deposition, and changes in mechanicalmore » properties were assessed.« less

Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 2. Experimental and kinetic modeling studies.

PubMed

McIntosh, Grant J; Russell, Douglas K

2013-05-23

The mechanism of formation of benzene rings during the pyrolysis of dichloro- and trichloroethylenes has been investigated by the method of laser powered homogeneous pyrolysis coupled with product analysis by gas chromatography. Additionally, selected (co)pyrolyses between the chlorinated ethylenes, CH2Cl2, C4Cl4, C4Cl6, and C2H2 have been performed to explicitly probe the roles of 2C3 and C4/C2 reaction pairs in aromatic growth. The presence of odd-carbon products in neat C4Cl6 pyrolyses indicates that 2C3 processes are operative in these systems; however, comparison with product yields from C2HCl3 suggests that C4/C2 processes dominate most other systems. This is further evidenced by an absence of C3 and other odd-carbon species in (co)pyrolyses with dichloromethane which should seed C3-based growth. The reactions of perchlorinated C4 species C4Cl5, C4Cl3, and C4Cl4 with C2Cl2 were subsequently explored through extensive kinetic simulations of the possible reaction pathways based on previous kinetic models and the exhaustive quantum chemical investigations of our preceding work. The experimental and theoretical results strongly suggest that, at moderate temperatures, aromatic ring formation from chlorinated ethylenes normally follows a Diels-Alder coupling of C4 and C2 molecular units followed by internal shifts; the one exception is the C4Cl4 + C2Cl2 system, where steric factors lead to the formation of nonaromatic products. There is little evidence for radical-based routes in these systems.

Modeling the chemistry of the dense interstellar clouds. I - Observational constraints for the chemistry

NASA Technical Reports Server (NTRS)

Federman, S. R.; Huntress, W. T., Jr.; Prasad, S. S.

1990-01-01

A search for correlations arising from molecular line data is made in order to place constraints on the chemical models of interstellar clouds. At 10 to the 21st H2/sq cm, N(CO) for dark clouds is a factor of six greater than the value for diffuse clouds. This implies that the strength of the UV radiation field where CO shields itself from dissociation is about one-half the strength of the average Galactic field. The dark cloud data indicate that the abundance of CO continues to increase with A(V) for directions with A(V) of 4 mag or less, although less steeply with N(H2) than for diffuse clouds. For H2CO, a quadratic relationship is obtained in plots versus H2 column density. The data suggest a possible turnover at the highest values for A(V). NH3 shows no correlation with H2, C(O-18), HC3N, or HC5N; a strong correlation is found between HC5N and HC3N, indicating a chemical link between the cyanopolyynes.

Comparison of QEEG Findings between Adolescents with Attention Deficit Hyperactivity Disorder (ADHD) without Comorbidity and ADHD Comorbid with Internet Gaming Disorder

PubMed Central

2017-01-01

Internet gaming disorder (IGD) is often comorbid with attention deficit hyperactivity disorder (ADHD). In this study, we compared the neurobiological differences between ADHD comorbid with IGD (ADHD+IGD group) and ADHD without comorbidity (ADHD-only group) by analyzing quantitative electroencephalogram (QEEG) findings. We recruited 16 male ADHD+IGD, 15 male ADHD-only adolescent patients, and 15 male healthy controls (HC group). Participants were assessed using Young's Internet Addiction Scale and ADHD Rating Scale. Relative power and inter- and intra-hemispheric coherences of brain waves were measured using a digital electroencephalography (EEG) system. Compared to the ADHD-only group, the ADHD+IGD group showed lower relative delta power and greater relative beta power in temporal regions. The relative theta power in frontal regions were higher in ADHD-only group compared to HC group. Inter-hemispheric coherence values for the theta band between F3–F4 and C3–C4 electrodes were higher in ADHD-only group compared to HC group. Intra-hemispheric coherence values for the delta, theta, alpha, and beta bands between P4–O2 electrodes and intra-hemispheric coherence values for the theta band between Fz–Cz and T4–T6 electrodes were higher in ADHD+IGD group compared to ADHD-only group. Adolescents who show greater vulnerability to ADHD seem to continuously play Internet games to unconsciously enhance attentional ability. In turn, relative beta power in attention deficit in ADHD+IGD group may become similar to that in HC group. Repetitive activation of brain reward and working memory systems during continuous gaming may result in an increase in neuronal connectivity within the parieto-occipital and temporal regions for the ADHD+IGD group. PMID:28145657

Comparison of QEEG Findings between Adolescents with Attention Deficit Hyperactivity Disorder (ADHD) without Comorbidity and ADHD Comorbid with Internet Gaming Disorder.

PubMed

Park, Jeong Ha; Hong, Ji Sun; Han, Doug Hyun; Min, Kyoung Joon; Lee, Young Sik; Kee, Baik Seok; Kim, Sun Mi

2017-03-01

Internet gaming disorder (IGD) is often comorbid with attention deficit hyperactivity disorder (ADHD). In this study, we compared the neurobiological differences between ADHD comorbid with IGD (ADHD+IGD group) and ADHD without comorbidity (ADHD-only group) by analyzing quantitative electroencephalogram (QEEG) findings. We recruited 16 male ADHD+IGD, 15 male ADHD-only adolescent patients, and 15 male healthy controls (HC group). Participants were assessed using Young's Internet Addiction Scale and ADHD Rating Scale. Relative power and inter- and intra-hemispheric coherences of brain waves were measured using a digital electroencephalography (EEG) system. Compared to the ADHD-only group, the ADHD+IGD group showed lower relative delta power and greater relative beta power in temporal regions. The relative theta power in frontal regions were higher in ADHD-only group compared to HC group. Inter-hemispheric coherence values for the theta band between F3-F4 and C3-C4 electrodes were higher in ADHD-only group compared to HC group. Intra-hemispheric coherence values for the delta, theta, alpha, and beta bands between P4-O2 electrodes and intra-hemispheric coherence values for the theta band between Fz-Cz and T4-T6 electrodes were higher in ADHD+IGD group compared to ADHD-only group. Adolescents who show greater vulnerability to ADHD seem to continuously play Internet games to unconsciously enhance attentional ability. In turn, relative beta power in attention deficit in ADHD+IGD group may become similar to that in HC group. Repetitive activation of brain reward and working memory systems during continuous gaming may result in an increase in neuronal connectivity within the parieto-occipital and temporal regions for the ADHD+IGD group.

Effects of Low-Fat Diets Differing in Protein and Carbohydrate Content on Cardiometabolic Risk Factors during Weight Loss and Weight Maintenance in Obese Adults with Type 2 Diabetes.

PubMed

Watson, Nerylee; Dyer, Kathryn; Buckley, Jonathan; Brinkworth, Grant; Coates, Alison; Parfitt, Gaynor; Howe, Peter; Noakes, Manny; Murphy, Karen

2016-05-12

Despite evidence for the benefits of higher-protein (HP) diets in weight loss, their role in type 2 diabetes mellitus (T2DM) management and weight maintenance is not clear. This randomised study compared the effects of a HP diet (38% carbohydrate, 30% protein, 29% fat) to a isocaloric higher-carbohydrate diet (HC: 53%:21%:23%) on cardiometabolic risk factors for 12 weeks in energy restriction (~30% reduction) followed by 12 weeks of energy balance whilst performing regular exercise. Outcomes were measured at baseline and the end of each phase. Sixty-one overweight/obese adults (BMI (body mass index) 34.3 ± 5.1 kg/m², aged 55 ± 8 years) with T2DM who commenced the study were included in the intention-to-treat analysis including the 17 participants (HP n = 9, HC n = 8) who withdrew. Following weight loss (M ± SEM: -7.8 ± 0.6 kg), there were significant reductions in HbA1c (-1.4% ± 0.1%, p < 0.001) and several cardiometabolic health risk factors. Improvements were sustained for 12 weeks when weight was stabilised and weight loss maintained. Both the HP and HC dietary patterns with concurrent exercise may be effective strategies for weight loss and weight maintenance in T2DM although further studies are needed to determine the longer term effects of weight maintenance.

Effects of Low-Fat Diets Differing in Protein and Carbohydrate Content on Cardiometabolic Risk Factors during Weight Loss and Weight Maintenance in Obese Adults with Type 2 Diabetes

PubMed Central

Watson, Nerylee; Dyer, Kathryn; Buckley, Jonathan; Brinkworth, Grant; Coates, Alison; Parfitt, Gaynor; Howe, Peter; Noakes, Manny; Murphy, Karen

2016-01-01

Despite evidence for the benefits of higher-protein (HP) diets in weight loss, their role in type 2 diabetes mellitus (T2DM) management and weight maintenance is not clear. This randomised study compared the effects of a HP diet (38% carbohydrate, 30% protein, 29% fat) to a isocaloric higher-carbohydrate diet (HC: 53%:21%:23%) on cardiometabolic risk factors for 12 weeks in energy restriction (~30% reduction) followed by 12 weeks of energy balance whilst performing regular exercise. Outcomes were measured at baseline and the end of each phase. Sixty-one overweight/obese adults (BMI (body mass index) 34.3 ± 5.1 kg/m2, aged 55 ± 8 years) with T2DM who commenced the study were included in the intention-to-treat analysis including the 17 participants (HP n = 9, HC n = 8) who withdrew. Following weight loss (M ± SEM: −7.8 ± 0.6 kg), there were significant reductions in HbA1c (−1.4% ± 0.1%, p < 0.001) and several cardiometabolic health risk factors. Improvements were sustained for 12 weeks when weight was stabilised and weight loss maintained. Both the HP and HC dietary patterns with concurrent exercise may be effective strategies for weight loss and weight maintenance in T2DM although further studies are needed to determine the longer term effects of weight maintenance. PMID:27187457

Crystal structure of 2-(1,3-dioxoindan-2-yl)iso-quinoline-1,3,4-trione.

PubMed

Ghalib, Raza Murad; Chidan Kumar, C S; Hashim, Rokiah; Sulaiman, Othman; Fun, Hoong-Kun

2015-01-01

In the title iso-quinoline-1,3,4-trione derivative, C18H9NO5, the five-membered ring of the indane fragment adopts an envelope conformation with the nitro-gen-substituted C atom being the flap. The planes of the indane benzene ring and the iso-quinoline-1,3,4-trione ring make a dihedral angle of 82.06 (6)°. In the crystal, mol-ecules are linked into chains extending along the bc plane via C-H⋯O hydrogen-bonding inter-actions, enclosing R 2 (2)(8) and R 2 (2)(10) loops. The chains are further connected by π-π stacking inter-ations, with centroid-to-centroid distances of 3.9050 (7) Å, forming layers parallel to the b axis.

The Arabidopsis RING-Type E3 Ligase TEAR1 Controls Leaf Development by Targeting the TIE1 Transcriptional Repressor for Degradation[OPEN

PubMed Central

Zhang, Jinzhe; Wei, Baoye; Yuan, Rongrong; Yu, Hao

2017-01-01

The developmental plasticity of leaf size and shape is important for leaf function and plant survival. However, the mechanisms by which plants form diverse leaves in response to environmental conditions are not well understood. Here, we identified TIE1-ASSOCIATED RING-TYPE E3 LIGASE1 (TEAR1) and found that it regulates leaf development by promoting the degradation of TCP INTERACTOR-CONTAINING EAR MOTIF PROTEIN1 (TIE1), an important repressor of CINCINNATA (CIN)-like TEOSINTE BRANCHED1/CYCLOIDEA/PCF (TCP) transcription factors, which are key for leaf development. TEAR1 contains a typical C3H2C3-type RING domain and has E3 ligase activity. We show that TEAR1 interacts with the TCP repressor TIE1, which is ubiquitinated in vivo and degraded by the 26S proteasome system. We demonstrate that TEAR1 is colocalized with TIE1 in nuclei and negatively regulates TIE1 protein levels. Overexpression of TEAR1 rescued leaf defects caused by TIE1 overexpression, whereas disruption of TEAR1 resulted in leaf phenotypes resembling those caused by TIE1 overexpression or TCP dysfunction. Deficiency in TEAR partially rescued the leaf defects of TCP4 overexpression line and enhanced the wavy leaf phenotypes of jaw-5D. We propose that TEAR1 positively regulates CIN-like TCP activity to promote leaf development by mediating the degradation of the TCP repressor TIE1. PMID:28100709

A new approach to construct a fused 2-ylidene chromene ring: highly regioselective synthesis of novel chromeno quinoxalines.

PubMed

Kumar, K Shiva; Rambabu, D; Prasad, Bagineni; Mujahid, Mohammad; Krishna, G Rama; Rao, M V Basaveswara; Reddy, C Malla; Vanaja, G R; Kalle, Arunasree M; Pal, Manojit

2012-06-28

Regioselective construction of a fused 2-ylidene chromene ring was achieved for the first time by using AlCl(3)-induced C-C bond formation followed by Pd/C-Cu mediate coupling-cyclization strategy. A number of chromeno[4,3-b]quinoxaline derivatives were prepared by using this strategy. Single crystal X-ray diffraction study of a representative compound e.g. 6-(2,2-dimethylpropylidene)-4-methyl-6H-chromeno[4,3-b]quinoxalin-3-ol confirmed the presence of an exocyclic C-C double bond with Z-geometry. The crystal structure analysis and hydrogen bonding patterns of the same compound along with its structure elaboration via propargylation followed by Sonogashira coupling of the resulting terminal alkyne is presented. A probable mechanism for the formation of 2-ylidene chromene ring is discussed. Some of the compounds synthesized showed anticancer properties when tested in vitro.

Tree-ring variation in western larch (Larix occidentalis Nutt. ) exposed to sulfur dioxide emissions

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

Fox, C.A.; Kincaid, W.B.; Nash, T.H. III

1984-12-01

Tree-ring analysis of western larch (Larix occidentialis Nutt) demonstrated both direct and indirect affects of sulfur dioxide emissions from the lead/zinc smelter at Trail, B.C. Tree cores were collected from 5 stands known to have been polluted and from 3 control stands. Age effects were removed by fitting theoretical growth curves, and macrocliate was modeled using the average of the controls and two laged values thereof. Separate analyses were performed for years before and after installation of two tall stacks, for drought and nondrought years, and for years prior to initiation of smelting. Regression analyses revealed a negative effect onmore » annual growth that diminished with increasing distance from the smelter and during drought years. Furthermore, chronology statistics suggested an increase in sensitivity to climate that persisted decades beyond implementation of pollution controls, which reduced emissions 10-fold. 38 references, 6 figures, 3 tables.« less

Coordination Polymers Containing 1,3-Phenylenebis-((1H-1,2,4-triazol-1-yl)methanone) Ligand: Synthesis and ε-Caprolactone Polymerization Behavior.

PubMed

Bello-Vieda, Nestor J; Murcia, Ricardo A; Muñoz-Castro, Alvaro; Macías, Mario A; Hurtado, John J

2017-11-10

The reaction of isophthaloyl dichloride with 1 H -1,2,4-triazole afforded the new ligand 1,3-phenylenebis(1,2,4-triazole-1-yl)methanone ( 1 ). A series of Co(II), Cu(II), Zn(II) and Ni(II) complexes were synthesized using 1 and then characterized by melting point analysis, elemental analysis, theoretical calculations, thermogravimetric analysis, X-ray powder diffraction, nuclear magnetic resonance, infrared and Raman spectroscopy. Experimental and computational studies predict the formation of coordination polymers (CPs). The cobalt and copper CPs and zinc(II) complex were found to be good initiators for the ring-opening polymerization of ε-caprolactone (CL) under solvent-free conditions. ¹H-NMR analysis showed that the obtained polymers of CL were mainly linear and had terminal hydroxymethylene groups. Differential scanning calorimetry showed that the obtained polycaprolactones had high crystallinity, and TGA showed that they had decomposition temperatures above 400 °C. These results provide insight and guidance for the design of metal complexes with potential applications in the polymerization of CL.

5-(4-Bromo­phen­oxy)-1-methyl-3-methyl-1H-pyrazole-4-carbaldehyde-O-[(5-meth­oxy-1,3,4-thia­diazol-2-yl)-meth­yl]oxime

PubMed Central

Fan, Chong-Guang; Chen, Jian-Cun; Dai, Hong; Wei, Yun-Hua; Shi, Yu-Jun

2012-01-01

In the title mol­ecule, C16H16BrN5O3S, the 1,3,4-thia­diazole ring is situated under the benzene ring, forming a dihedral angle of 86.6 (2)°, and with an S⋯Cg (where Cg is the centroid of the benzene ring) distance of 3.312 (3) Å. The benzene and 1,3,4-thia­diazole rings form dihedral angles of 83.8 (3) and 57.7 (2)°, respectively, with the central pyrazole ring. In the absence of classical hydrogen bonds, the crystal packing is stabilized by a C—H⋯π inter­action.. PMID:23284447

Light-induced yellowing of selectively 13C-enriched dehydrogenation polymers (DHPs). Part 2, NMR assignments and photoyellowing of aromatic ring 1-, 3-, 4-, and 5-13C DHPs

Treesearch

Jim Parkas; Magnus Paulsson; Terashima Noritsugu; Ulla Westermark; Sally Ralph

2004-01-01

Light-induced yellowing of lignocellulosicmaterials has been studied using 13C-enriched DHP (dehydrogenation polymer), selectively 13C-enriched at positions 1, 3, 4, and 5 in the aromatic ring, and quantitative solution state 13C NMR spectroscopy. The NMR study confirmed the results of previous studies using side-chain labeled DHP, mainly that coniferyl alcohol end...

Biphasic zinc compartmentalisation in a human fungal pathogen.

PubMed

Crawford, Aaron C; Lehtovirta-Morley, Laura E; Alamir, Omran; Niemiec, Maria J; Alawfi, Bader; Alsarraf, Mohammad; Skrahina, Volha; Costa, Anna C B P; Anderson, Andrew; Yellagunda, Sujan; Ballou, Elizabeth R; Hube, Bernhard; Urban, Constantin F; Wilson, Duncan

2018-05-01

Nutritional immunity describes the host-driven manipulation of essential micronutrients, including iron, zinc and manganese. To withstand nutritional immunity and proliferate within their hosts, pathogenic microbes must express efficient micronutrient uptake and homeostatic systems. Here we have elucidated the pathway of cellular zinc assimilation in the major human fungal pathogen Candida albicans. Bioinformatics analysis identified nine putative zinc transporters: four cytoplasmic-import Zip proteins (Zrt1, Zrt2, Zrt3 and orf19.5428) and five cytoplasmic-export ZnT proteins (orf19.1536/Zrc1, orf19.3874, orf19.3769, orf19.3132 and orf19.52). Only Zrt1 and Zrt2 are predicted to localise to the plasma membrane and here we demonstrate that Zrt2 is essential for C. albicans zinc uptake and growth at acidic pH. In contrast, ZRT1 expression was found to be highly pH-dependent and could support growth of the ZRT2-null strain at pH 7 and above. This regulatory paradigm is analogous to the distantly related pathogenic mould, Aspergillus fumigatus, suggesting that pH-adaptation of zinc transport may be conserved in fungi and we propose that environmental pH has shaped the evolution of zinc import systems in fungi. Deletion of C. albicans ZRT2 reduced kidney fungal burden in wild type, but not in mice lacking the zinc-chelating antimicrobial protein calprotectin. Inhibition of zrt2Δ growth by neutrophil extracellular traps was calprotectin-dependent. This suggests that, within the kidney, C. albicans growth is determined by pathogen-Zrt2 and host-calprotectin. As well as serving as an essential micronutrient, zinc can also be highly toxic and we show that C. albicans deals with this potential threat by rapidly compartmentalising zinc within vesicular stores called zincosomes. In order to understand mechanistically how this process occurs, we created deletion mutants of all five ZnT-type transporters in C. albicans. Here we show that, unlike in Saccharomyces cerevisiae, C. albicans Zrc1 mediates zinc tolerance via zincosomal zinc compartmentalisation. This novel transporter was also essential for virulence and liver colonisation in vivo. In summary, we show that zinc homeostasis in a major human fungal pathogen is a multi-stage process initiated by Zrt1/Zrt2-cellular import, followed by Zrc1-dependent intracellular compartmentalisation.

4-{2-[2-(4-Chloro­benzyl­idene)hydrazinyl­idene]-3,6-dihydro-2H-1,3,4-thia­diazin-5-yl}-3-phenyl­sydnone

PubMed Central

Fun, Hoong-Kun; Loh, Wan-Sin; Nithinchandra; Kalluraya, Balakrishna

2011-01-01

The title compound, C18H13ClN6O2S, exists in trans and cis configurations with respect to the acyclic C=N bonds [C=N = 1.2837 (15) and 1.3000 (14) Å, respectively]. The 3,6-dihydro-2H-1,3,4-thia­diazine ring adopts a half-boat conformation. The sydnone ring is approximately planar [maximum deviation = 0.002 (1) Å] and forms dihedral angles of 50.45 (7) and 61.21 (6)° with the aromatic rings. In the crystal, inter­molecular N—H⋯N, C—H⋯Cl and C—H⋯S hydrogen bonds link the mol­ecules into layers parallel to ab plane. The crystal packing is stabilized by C—H⋯π inter­actions and further consolidated by π–π inter­actions involving the phenyl rings [centroid–centroid distance = 3.6306 (7) Å]. PMID:21754481

The coordination behaviour of ferrocene-based pyridylphosphine ligands towards Zn(II), Cd(II) and Hg(II).

PubMed

Siemeling, Ulrich; Klemann, Thorsten; Bruhn, Clemens; Schulz, Jiří; Štěpnička, Petr

2011-05-07

The reaction of Group 12 metal dihalides MX(2) with the P,N-ligands [Fe(C(5)H(4)-PPh(2))(C(5)H(4)-2-py)] (1) (2-py = pyrid-2-yl), [Fe(C(5)H(4)-PPh(2))(C(5)H(4)-CH(2)-2-py)] (2) and [Fe(C(5)H(4)-PPh(2))(C(5)H(4)-3-py)] (3) (3-py = pyrid-3-yl) was investigated. For a 1 : 1 molar ratio of MX(2) and the respective ligand, three structure types were found in the solid state, viz. chelate, cyclic dimer and chain-like coordination polymer. The M(II) coordination environment is distorted pseudo-tetrahedral in each case. The P-M-N angle is much larger in the chelates (≥119°) than in the ligand-bridged structures (≤109°). 1 prefers the formation of chelates [MX(2)(1-κ(2)N,P)]. 3 forms coordination polymers [MX(2)(μ-3)](n). With the more flexible 2 all three structure types can occur. Dynamic coordination equilibria were observed in solution for the molecular complexes obtained with 1 and 2. NMR data indicate that the N- and P-donor sites interact most strongly with Zn(II) and Hg(II), respectively. While the formation of bis(phosphine)mercury complexes (soft-soft) was easily achieved, no bis(pyridine)zinc complex (borderline-borderline) could be obtained, which is surprising in view of the HSAB principle.

[Assessment of efficiency of dietotherapy with addition of a vitamin-mineral complex in patients with diabetes mellitus type 2].

PubMed

Lapik, I A; Sokol'nikov, A A; Sharafetdinov, Kh Kh; Sentsova, T B; Plotnikova, O A

2014-01-01

The influence of diet inclusion of vitamin and mineral complex (VMC), potassium and magnesium in the form of asparaginate on micronutrient status, body composition and biochemical parameters in patients with diabetes mellitus type 2 (DM2) has been investigated. 120 female patients with DM2 and obesity of I-III degree (mean age - 58 +/- 6 years) have been included in the study. The patients were divided into two groups: main group (n = 60) and control group (n = 60). For 3 weeks patients of both groups received a low-calorie diet (1600 kcal/day). Patients of the main group received VMC, providing an additional intake of vitamins C and E (100-120% RDA), beta-carotene (40% RDA), nicotinamide (38% RDA), pantothenic acid and biotin (60% RDA), vitamins B12, B2 and folic acid (75-83% RDA), vitamins B1 and B6 (160-300% RDA), zinc (100% RDA) and chromium (400% RDA), and also received magnesium (17.7% RDA) and potassium (9.4% RDA) in the form of asparaginate. Body composition, biochemical parameters and micronutrient status (blood serum level of vitamins C, D, B6, B12, folate, potassium, calcium, magnesium, zinc, phosphorus) were evaluated in all patients before and after the 3-week course of diet therapy. After the low-calorie diet therapy average body weight reduction was 4.2 +/- 0.2 kg in the main group, and 4.4 +/- 0.1 kg in the control group, without statistically significant differences between groups. Statistically significant decrease of total cholesterol, triglycerides, and glucose concentration in blood serum was registered in both groups. It should be noted that in the control group glycemia decreased on 1.2 +/- 0.1 mmol/l, while the main group showed a decrease on 1.8 +/- 0.1 (p < 0.05) to normal values (5.4 +/- 0.1 mmol/l). Initial assessment of vitamin and mineral status revealed that most patients were optimal supplied with vitamins and minerals. After the dietotherapy significant increase of vitamin C, 25-hydroxyvitamin D, vitamin B6, folate, vitamin B12, potassium, magnesium, calcium, zinc and phosphorus concentration in blood serum was observed in patients receiving VMC. While in the control group statistically significant decrease of vitamin C, magnesium, zinc and phosphorus concentration in blood serum after the treatment was revealed. The obtained data shows the necessity of addition of the vitamin-mineral complex to the diet of patients with DM2 and obesity.

Superconducting Properties of CeIr3 Single Crystal

NASA Astrophysics Data System (ADS)

Sato, Yoshiki J.; Nakamura, Ai; Shimizu, Yusei; Maurya, Arvind; Homma, Yoshiya; Li, Dexin; Honda, Fuminori; Aoki, Dai

2018-05-01

Superconducting properties of CeIr3 single crystal with rhombohedral structure were examined for the first time using DC magnetization, specific heat, and electrical resistivity measurements. A bulk type-II superconductivity was clearly detected at Tc = 3.4 K, which is the second highest Tc among Ce-based intermetallic compounds. The thermodynamic properties as well as an upper critical field Hc2(0) ˜ 46.5 kOe for the H || c-axis are fully consistent with the weak-coupling BCS regime. The observed √{H} variation of C(H)/T becomes less pronounced upon cooling, possibly suggesting a suppression of low-energy quasiparticle excitations in an anisotropic s-wave gap in CeIr3, as observed in CeRu2. The origin of superconductivity is discussed from the viewpoints of the valence of Ce atom and Ir 5d-electron with a strong spin-orbit coupling.

Structural phase transition of as-synthesized Sr-Mn nanoferrites by annealing temperature

NASA Astrophysics Data System (ADS)

Amer, M. A.; Meaz, T. M.; Attalah, S. S.; Ghoneim, A. I.

2015-11-01

The Sr0.2Mn0.8Fe2O4 nanoparticle ferrites were synthesized by the co-precipitation method and annealed at different temperatures T. XRD, TEM, FT-IR, VSM and Mössbauer techniques were used to characterize the samples. This study proved that the structural phase of nanoferrites was transformed from cubic spinel for T≤500 °C to Z-type hexagonal for T≥700 °C. The structural transformation was attributed to Jahn-Teller effect of the Mn3+ ions and/or atomic disorder existed in the crystal lattice. The obtained spectra and parameters for the samples were affected by the transformation process. The lattice constant a showed a splitting to a and c for T>500 °C. The lattice constant c, grain and crystallite size R, strain, octahedral B-site band position and force constant, Debye temperature, coercivity Hc, remnant magnetization, squareness and magnetic moment, spontaneous magnetization and hyperfine magnetic fields showed increase against T. The lattice constant a, distortion and dislocation parameters, specific surface area, tetrahedral A-site band position and force constant, threshold frequency, Young's and bulk moduli, saturation magnetization Ms, area ratio of B-/A-sites, A-site line width were decreased with T. Experimental and theoretical densities, porosity, Poison ratio, stiffness constants, rigidity modulus, B-site line width and spontaneous magnetization showed dependence on T, whereas Ms and Hc proved dependence on R.

Zinc(II) complexes with potent cyclin-dependent kinase inhibitors derived from 6-benzylaminopurine: synthesis, characterization, X-ray structures and biological activity.

PubMed

Trávnícek, Zdenek; Krystof, Vladimír; Sipl, Michal

2006-02-01

The synthesis, characterization and biological activity of the first zinc(II) complexes with potent inhibitors of cyclin-dependent kinases (CDKs) derived from 6-benzylaminopurine are described. Based on the results following from elemental analyses, infrared, NMR and ES+MS (electrospray mass spectra in the positive ion mode) spectroscopies, conductivity data, thermal analysis and X-ray structures, the tetrahedral Zn(II) complexes of the compositions [Zn(Olo)Cl(2)](n) (1), [Zn(iprOlo)Cl(2)](n) (2), [Zn(BohH(+))Cl(3)] x H(2)O (3) and [Zn(iprOloH(+))Cl(3)] x H(2)O (4) have been prepared, where Olo=2-(2-hydroxyethylamino)-6-benzylamino-9-methylpurine (Olomoucine), iprOlo=2-(2-hydroxyethylamino)-6-benzylamino-9-isopropylpurine (i-propyl-Olomoucine), Boh=2-(3-hydroxypropylamino)-6-benzylamino-9-isopropylpurine (Bohemine). The 1D-polymeric chain structure for [Zn(Olo)Cl(2)](n) (1) as well as the monomeric one for [Zn(BohH(+))Cl(3)] x H(2)O (3) and [Zn(iprOloH(+))Cl(3)] x H(2)O (4) have been revealed unambiguously by single crystal X-ray analyses. The 1D-polymeric chain of 1 consists of Zn(Olo)Cl(2) monomeric units in which the Zn(II) ion is coordinated by two chlorine atoms and one oxygen atom of the 2-hydroxyethylamino group of Olomoucine. The next monomeric unit is bonded to Zn(II) through the N7 atom of a purine ring. Thus, each of Zn(II) ions is tetrahedrally coordinated and a ZnCl(2)NO chromophore occurs in the complex 1. The complexes 3 and 4 are mononuclear species with a distorted tetrahedral arrangement of donor atoms around the Zn(II) ion with a ZnCl(3)N chromophore. The corresponding CDK inhibitor, i.e., both Boh and iprOlo, is coordinated to Zn(II) via the N7 atom of the purine ring in 3 and 4. The cytotoxicity of the zinc(II) complexes against human melanoma, sarcoma, leukaemia and carcinoma cell lines has been determined as well as the inhibition of the CDK2/cyclin E kinase. A relationship between the structure and biological activity of the complexes is also discussed.

Evaluation of kinetic uncertainty in numerical models of petroleum generation

USGS Publications Warehouse

Peters, K.E.; Walters, C.C.; Mankiewicz, P.J.

2006-01-01

Oil-prone marine petroleum source rocks contain type I or type II kerogen having Rock-Eval pyrolysis hydrogen indices greater than 600 or 300-600 mg hydrocarbon/g total organic carbon (HI, mg HC/g TOC), respectively. Samples from 29 marine source rocks worldwide that contain mainly type II kerogen (HI = 230-786 mg HC/g TOC) were subjected to open-system programmed pyrolysis to determine the activation energy distributions for petroleum generation. Assuming a burial heating rate of 1??C/m.y. for each measured activation energy distribution, the calculated average temperature for 50% fractional conversion of the kerogen in the samples to petroleum is approximately 136 ?? 7??C, but the range spans about 30??C (???121-151??C). Fifty-two outcrop samples of thermally immature Jurassic Oxford Clay Formation were collected from five locations in the United Kingdom to determine the variations of kinetic response for one source rock unit. The samples contain mainly type I or type II kerogens (HI = 230-774 mg HC/g TOC). At a heating rate of 1??C/m.y., the calculated temperatures for 50% fractional conversion of the Oxford Clay kerogens to petroleum differ by as much as 23??C (127-150??C). The data indicate that kerogen type, as defined by hydrogen index, is not systematically linked to kinetic response, and that default kinetics for the thermal decomposition of type I or type II kerogen can introduce unacceptable errors into numerical simulations. Furthermore, custom kinetics based on one or a few samples may be inadequate to account for variations in organofacies within a source rock. We propose three methods to evaluate the uncertainty contributed by kerogen kinetics to numerical simulations: (1) use the average kinetic distribution for multiple samples of source rock and the standard deviation for each activation energy in that distribution; (2) use source rock kinetics determined at several locations to describe different parts of the study area; and (3) use a weighted-average method that combines kinetics for samples from different locations in the source rock unit by giving the activation energy distribution for each sample a weight proportional to its Rock-Eval pyrolysis S2 yield (hydrocarbons generated by pyrolytic degradation of organic matter). Copyright ?? 2006. The American Association of Petroleum Geologists. All rights reserved.

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.

Assessment of isolated electronic effects on conformation. NMR analysis of nicotine and related compounds and ab initio studies of model compounds

NASA Astrophysics Data System (ADS)

Cox, Richard H.; Kao, James; Secor, Henry V.; Seeman, Jeffrey I.

1986-01-01

The influence of electronegative substituents on the N'-methyl group of nicotine upon the conformation of the pyrrolidine ring has been evaluated by the exact analysis of the high field 1H NMR spectra of nicotine ( 1), N'-ethylnornicotine ( 2), N'-(2,2-difluoroethyl)-nornicotine ( 3) and N'-(2,2,2-trifluoroethyl) nornicotine ( 4). The vicinal coupling constants for the pyrrolidine ring of 1-4 remain nearly constant, suggesting that as the electronegativity of the N'-methyl substituent increases, only very small changes are seen for the C 3'—C 4'—C 5'—N' and the C 2'—C 3'—C 4'—C 5' dihedral angles. Substitution on the N'-methyl group appears to have little effect on the orientation of the pyridyl ring with respect to the pyrrolidine ring. Ab initio calculations have been performed on the analogous 2-substituted diethylamines (diethylamine, N-ethyl-2-fluoroethylamine, N-ethyl-2,2-difluoroamine, and N-ehtyl-2,2,2-trifluoroethylamine) which constitute substructure models of 1-4. These calculations confirm the NMR results in that they both indicate little, if any, effects on the rotational barriers and conformational energy profiles as a function of number of fluorine atoms.

Porphyrin amino acids-amide coupling, redox and photophysical properties of bis(porphyrin) amides.

PubMed

Melomedov, Jascha; Wünsche von Leupoldt, Anica; Meister, Michael; Laquai, Frédéric; Heinze, Katja

2013-07-14

New trans-AB2C meso-substituted porphyrin amino acid esters with meso-substituents of tunable electron withdrawing power (B = mesityl, 4-C6H4F, 4-C6H4CF3, C6F5) were prepared as free amines 3a-3d, as N-acetylated derivatives Ac-3a-Ac-3d and corresponding zinc(II) complexes Zn-Ac-3a-Zn-Ac-3d. Several amide-linked bis(porphyrins) with a tunable electron density at each porphyrin site were obtained from the amino porphyrin precursors by condensation reactions (4a-4d) and mono- and bis(zinc(II)) complexes Zn(2)-4d and Zn(1)Zn(2)-4d were prepared. The electronic interaction between individual porphyrin units in bis(porphyrins) 4 is probed by electrochemical experiments (CV, EPR), electronic absorption spectroscopy, steady-state and time-resolved fluorescence spectroscopy in combination with DFT/PCM calculations on diamagnetic neutral bis(porphyrins) 4 and on respective charged mixed-valent radicals 4(+/-). The interaction via the -C6H4-NHCO-C6H4- bridge, the site of oxidation and reduction and the lowest excited singlet state S1, is tuned by the substituents on the individual porphyrins and the metalation state.

Generation of photocurrent by visible-light irradiation of conjugated dawson polyoxophosphovanadotungstate-porphyrin copolymers.

PubMed

Azcarate, Iban; Huo, Zhaohui; Farha, Rana; Goldmann, Michel; Xu, Hualong; Hasenknopf, Bernold; Lacôte, Emmanuel; Ruhlmann, Laurent

2015-05-26

Four hybrid polyoxometalate-porphyrin copolymer films were obtained by the electrooxidation of zinc octaethylporphyrin in the presence of four different Dawson-type polyoxometalates bearing two pyridyl groups (POM(py)2) with various spacers. The POM monomers were designed around 1,3,5-trisubstituted benzene rings. Two of the substituents of the benzene ring are linked to the pyridyl groups, and the third is connected to the POM subunit. The four monomers vary in the relative positions of the nitrogen atoms of the pyridine rings or in the distance from the carbonyl group. The monomers were fully characterized by (1)H, (31)P, and (13)C NMR spectroscopy, electrospray mass spectrometry, IR and UV/Vis spectroscopy, and electrochemistry. The copolymers were characterized by UV/Vis spectroscopy, X-ray photoelectron spectroscopy, electrochemistry, and AFM. Their photovoltaic performance under visible light irradiation was investigated by photocurrent transient measurements under visible illumination. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vestibular function in patients with Niemann-Pick type C disease.

PubMed

Bremova, Tatiana; Krafczyk, Siegbert; Bardins, Stanislavs; Reinke, Jörg; Strupp, Michael

2016-11-01

We investigated whether vestibular dysfunction may cause or contribute to postural imbalance and falls in patients with Niemann-Pick type C disease (NP-C). Eight patients with NP-C disease and 20 healthy controls were examined using the video-based head impulse test (vHIT) and caloric irrigation to investigate horizontal canal function as well as ocular- and cervical vestibular evoked myogenic potentials (o- and cVEMP), and binocular subjective visual vertical estimation (SVV) for otolith function, and static posturography. There were no significant differences in vestibulo-ocular gain, caloric excitability, o-/cVEMP measures or SVV between the two groups. Posturographic total sway path (tSP) and root mean square (RMS) were significantly higher in NP-C than in controls in 3 out of 4 conditions. The Romberg quotient (RQ) to assess the amount of visual stabilization was significantly lower in the NP-C than in the HC group. In contrast to other inherited metabolic disorders, such as Morbus Gaucher type 3, we did not find any evidence for an impairment of canal or otolith function in patients with NP-C as their cause of postural imbalance. Since RQ was low in NP-C patients, indicating proper sensory input, the observed increased postural sway is most likely due to a cerebellar dysfunction in NP-C, which may therefore, explain postural imbalance.

Upregulation of Zinc Absorption Matches Increases in Physiologic Requirements for Zinc in Women Consuming High- or Moderate-Phytate Diets during Late Pregnancy and Early Lactation.

PubMed

Hambidge, K Michael; Miller, Leland V; Mazariegos, Manolo; Westcott, Jamie; Solomons, Noel W; Raboy, Victor; Kemp, Jennifer F; Das, Abhik; Goco, Norman; Hartwell, Ty; Wright, Linda; Krebs, Nancy F

2017-06-01

Background: Estimated physiologic requirements (PRs) for zinc increase in late pregnancy and early lactation, but the effect on dietary zinc requirements is uncertain. Objective: The aim of this study was to determine changes in daily fractional absorbed zinc and total absorbed zinc (TAZ) from ad libitum diets of differing phytate contents in relation to physiologic zinc requirements during pregnancy and lactation. Methods: This was a prospective observational study of zinc absorption at 8 (phase 1) and 34 (phase 2) wk of gestation and 2 (phase 3) and 6 (phase 4) mo of lactation. Participants were indigenous Guatemalan women of childbearing age whose major food staple was maize and who had been randomly assigned in a larger study to either of 2 ad libitum feeding groups: low-phytate maize (LP; 1.6 mg/g; n = 14) or control maize (C; 7.1 mg/g; n = 8). Total dietary zinc (milligrams per day, TDZ) and phytate (milligrams per day) were determined from duplicate diets and fractional absorption (FAZ) by dual isotope ratio technique (TAZ = TDZ × FAZ). All variables were examined longitudinally and by group and compared with PRs. TAZ values at later phases were compared with phase 1. Measured TAZ was compared with predicted TAZ for nonpregnant, nonlactating (NPNL) women. Results: TAZ was greater in the LP group than in the C group at all phases. All variables increased from phase 1 to phases 2 and 3 and declined at phase 4. TAZ increased by 1.25 mg/d ( P = 0.045) in the C group and by 0.81 mg/d ( P = 0.058) in the LP group at phase 2. At phase 3, the increases were 2.66 mg/d ( P = 0.002) in the C group and 2.28 mg/d ( P = 0.0004) in the LP group, compared with a 1.37-mg/d increase in PR. Measured TAZ was greater than predicted values in phases 2-4. Conclusions: Upregulation of zinc absorption in late pregnancy and early lactation matches increases in PRs of pregnant and lactating women, regardless of dietary phytate, which has implications for dietary zinc requirements of pregnant and lactating women. © 2017 American Society for Nutrition.

Crystal structures of five 1-alkyl-4-aryl-1,2,4-triazol-1-ium halide salts.

PubMed

Guino-O, Marites A; Talbot, Meghan O; Slitts, Michael M; Pham, Theresa N; Audi, Maya C; Janzen, Daron E

2015-06-01

The asymmetric units for the salts 4-(4-fluoro-phen-yl)-1-isopropyl-1,2,4-triazol-1-ium iodide, C11H13FN3 (+)·I(-), (1), 1-isopropyl-4-(4-methyl-phen-yl)-1,2,4-triazol-1-ium iodide, C12H16N3 (+)·I(-), (2), 1-isopropyl-4-phenyl-1,2,4-triazol-1-ium iodide, C11H14N3 (+)·I(-), (3), and 1-methyl-4-phenyl-1,2,4-triazol-1-ium iodide, C9H10N3 (+)·I(-), (4), contain one cation and one iodide ion, whereas in 1-benzyl-4-phenyl-1,2,4-triazol-1-ium bromide monohydrate, C15H14N3 (+)·Br(-)·H2O, (5), there is an additional single water mol-ecule. There is a predominant C-H⋯X(halide) inter-action for all salts, resulting in a two-dimensional extended sheet network between the triazolium cation and the halide ions. For salts with para-substitution on the aryl ring, there is an additional π-anion inter-action between a triazolium carbon and iodide displayed by the layers. For salts without the para-substitution on the aryl ring, the π-π inter-actions are between the triazolium and aryl rings. The melting points of these salts agree with the predicted substituent inductive effects.

A novel dihydropyridine with 3-aryl meta-hydroxyl substitution blocks L-type calcium channels in rat cardiomyocytes

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

Galvis-Pareja, David; Centro Estudios Moleculares de la Célula; Zapata-Torres, Gerald

2014-08-15

Rationale: Dihydropyridines are widely used for the treatment of several cardiac diseases due to their blocking activity on L-type Ca{sup 2+} channels and their renowned antioxidant properties. Methods: We synthesized six novel dihydropyridine molecules and performed docking studies on the binding site of the L-type Ca{sup 2+} channel. We used biochemical techniques on isolated adult rat cardiomyocytes to assess the efficacy of these molecules on their Ca{sup 2+} channel-blocking activity and antioxidant properties. The Ca{sup 2+} channel-blocking activity was evaluated by confocal microscopy on fluo-3AM loaded cardiomyocytes, as well as using patch clamp experiments. Antioxidant properties were evaluated by flowmore » cytometry using the ROS sensitive dye 1,2,3 DHR. Results: Our docking studies show that a novel compound with 3-OH substitution inserts into the active binding site of the L-type Ca{sup 2+} channel previously described for nitrendipine. In biochemical assays, the novel meta-OH group in the aryl in C4 showed a high blocking effect on L-type Ca{sup 2+} channel as opposed to para-substituted compounds. In the tests we performed, none of the molecules showed antioxidant properties. Conclusions: Only substitutions in C2, C3 and C5 of the aryl ring render dihydropyridine compounds with the capacity of blocking LTCC. Based on our docking studies, we postulate that the antioxidant activity requires a larger group than the meta-OH substitution in C2, C3 or C5 of the dihydropyridine ring. - Highlights: • Dihydropyridine (DHP) molecules are widely used in cardiovascular disease. • DHPs block Ca{sup 2+} entry through LTCC—some DHPs have antioxidant activity as well. • We synthesized 6 new DHPs and tested their Ca{sup 2+} blocking and antioxidant activities. • 3-Aryl meta-hydroxyl substitution strongly increases their Ca{sup 2+} blocking activity. • 3-Aryl meta-hydroxyl substitution did not affect the antioxidant properties.« less

Influence of substrate type on transport properties of superconducting FeSe0.5Te0.5 thin films

NASA Astrophysics Data System (ADS)

Yuan, Feifei; Iida, Kazumasa; Langer, Marco; Hänisch, Jens; Ichinose, Ataru; Tsukada, Ichiro; Sala, Alberto; Putti, Marina; Hühne, Ruben; Schultz, Ludwig; Shi, Zhixiang

2015-06-01

FeSe0.5Te0.5 thin films were grown by pulsed laser deposition on CaF2, LaAlO3 and MgO substrates and structurally and electro-magnetically characterized in order to study the influence of the substrate on their transport properties. The in-plane lattice mismatch between FeSe0.5Te0.5 bulk and the substrate shows no influence on the lattice parameters of the films, whereas the type of substrate affects the crystalline quality of the films and, therefore, the superconducting properties. The film on MgO showed an extra peak in the angular dependence of critical current density Jc(θ) at θ = 180° (H||c), which arises from c-axis defects as confirmed by transmission electron microscopy. In contrast, no Jc(θ) peaks for H||c were observed in films on CaF2 and LaAlO3. Jc(θ) can be scaled successfully for both films without c-axis correlated defects by the anisotropic Ginzburg-Landau approach with appropriate anisotropy ratio γJ. The scaling parameter γJ is decreasing with decreasing temperature, which is different from what we observed in FeSe0.5Te0.5 films on Fe-buffered MgO substrates.

Search for a spin-nematic phase in the quasi-one-dimensional frustrated magnet LiCuVO4

NASA Astrophysics Data System (ADS)

Büttgen, N.; Nawa, K.; Fujita, T.; Hagiwara, M.; Kuhns, P.; Prokofiev, A.; Reyes, A. P.; Svistov, L. E.; Yoshimura, K.; Takigawa, M.

2014-10-01

We have performed nuclear magnetic resonance (NMR) experiments on the quasi-one-dimensional frustrated spin-1/2 system LiCuVO4 in magnetic fields H applied along the c axis up to field values near the saturation field Hsat. For the field range Hc241.4 T, indicating that the majority of magnetic moments in LiCuVO4 are already saturated in this field range. This result is inconsistent with the previously observed linear field dependence of the magnetization M (H) for Hc3

Occupancy of a C2-C2 type 'zinc-finger' protein domain by copper. Direct observation by electrospray ionization mass spectrometry.

PubMed

Hutchens, T W; Allen, M H; Li, C M; Yip, T T

1992-09-07

The metal ion specificity of most 'zinc-finger' metal binding domains is unknown. The human estrogen receptor protein contains two different C2-C2 type 'zinc-finger' sequences within its DNA-binding domain (ERDBD). Copper inhibits the function of this protein by mechanisms which remain unclear. We have used electrospray ionization mass spectrometry to evaluate directly the 71-residue ERDBD (K180-M250) in the absence and presence of Cu(II) ions. The ERDBD showed a high affinity for Cu and was completely occupied with 4 Cu bound; each Cu ion was evidently bound to only two ligand residues (net loss of only 2 Da per bound Cu). The Cu binding stoichiometry was confirmed by atomic absorption. These results (i) provide the first direct physical evidence for the ability of the estrogen receptor DNA-binding domain to bind Cu and (ii) document a twofold difference in the Zn- and Cu-binding capacity. Differences in the ERDBD domain structure with bound Zn and Cu are predicted. Given the relative intracellular contents of Zn and Cu, our findings demonstrate the need to investigate further the Cu occupancy of this and other zinc-finger domains both in vitro and in vivo.

The zinc-binding region (ZBR) fragment of Emi2 can inhibit APC/C by targeting its association with the coactivator Cdc20 and UBE2C-mediated ubiquitylation

PubMed Central

Shoji, Shisako; Muto, Yutaka; Ikeda, Mariko; He, Fahu; Tsuda, Kengo; Ohsawa, Noboru; Akasaka, Ryogo; Terada, Takaho; Wakiyama, Motoaki; Shirouzu, Mikako; Yokoyama, Shigeyuki

2014-01-01

Anaphase-promoting complex or cyclosome (APC/C) is a multisubunit ubiquitin ligase E3 that targets cell-cycle regulators. Cdc20 is required for full activation of APC/C in M phase, and mediates substrate recognition. In vertebrates, Emi2/Erp1/FBXO43 inhibits APC/C-Cdc20, and functions as a cytostatic factor that causes long-term M phase arrest of mature oocytes. In this study, we found that a fragment corresponding to the zinc-binding region (ZBR) domain of Emi2 inhibits cell-cycle progression, and impairs the association of Cdc20 with the APC/C core complex in HEK293T cells. Furthermore, we revealed that the ZBR fragment of Emi2 inhibits in vitro ubiquitin chain elongation catalyzed by the APC/C cullin-RING ligase module, the ANAPC2–ANAPC11 subcomplex, in combination with the ubiquitin chain-initiating E2, E2C/UBE2C/UbcH10. Structural analyses revealed that the Emi2 ZBR domain uses different faces for the two mechanisms. Thus, the double-faced ZBR domain of Emi2 antagonizes the APC/C function by inhibiting both the binding with the coactivator Cdc20 and ubiquitylation mediated by the cullin-RING ligase module and E2C. In addition, the tail region between the ZBR domain and the C-terminal RL residues [the post-ZBR (PZ) region] interacts with the cullin subunit, ANAPC2. In the case of the ZBR fragment of the somatic paralogue of Emi2, Emi1/FBXO5, these inhibitory activities against cell division and ubiquitylation were not observed. Finally, we identified two sets of key residues in the Emi2 ZBR domain that selectively exert each of the dual Emi2-specific modes of APC/C inhibition, by their mutation in the Emi2 ZBR domain and their transplantation into the Emi1 ZBR domain. PMID:25161877

Readressing the role of Toll-like receptor-4 alleles in inflammatory bowel disease: colitis, smoking, and seroreactivity.

PubMed

Manolakis, Anastassios C; Kapsoritakis, Andreas N; Kapsoritaki, Anastasia; Tiaka, Elisavet K; Oikonomou, Konstantinos A; Lotis, Vassilis; Vamvakopoulou, Dimitra; Davidi, Ioanna; Vamvakopoulos, Nikolaos; Potamianos, Spyros P

2013-02-01

Toll-like receptor (TLR) polymorphisms, and especially TLR-4 Asp299Gly and TLR-4 Thr399Ile, have been linked with Crohn's disease (CD) and to a lesser extent with ulcerative colitis (UC), CD behavior, and compromised seroreactivity to microbial antigens. Available data, however, are conflicting. To address these issues, the distribution of TLR-4 polymorphic alleles was assessed in patients with UC, CD, and healthy controls (HC), considering patient and disease characteristics as well as related serological markers. TLR-4 Asp299Gly and TLR-4 Thr399Ile polymorphisms were determined in 187 UC and 163 CD patients and 274 randomly selected HC. C reactive protein, anti-Saccharomyces cerevisiae mannan antibodies, anti-mannobioside carbohydrate antibodies, anti-laminariobioside carbohydrate antibodies IgG, and anti-chitobioside carbohydrate antibodies (ACCA) IgA levels were also assessed. UC and especially pancolitis patients carried the mutant alleles more frequently compared to CD patients and HC or UC patients with different disease extents (P = 0.002 and P < 0.0001, respectively). Involvement of the colon was more frequent in CD patients with mutant TLR-4 compared to those with wild-type alleles (P = 0.004). Levels and positivity rates of ACCA IgA were lower in inflammatory bowel disease (IBD) patients carrying the mutant compared to those with wild-type alleles (0.075 < P < 0.05). Despite the mutant TLR-4 predisposition for UC pancolitis, smoking was associated with more limited disease (P < 0.001). The presence of TLR-4 Asp299Gly and TLR-4 Thr399Ile polymorphisms is related to UC pancolitis, involvement of the colon in CD, and lower ACCA IgA levels. Smoking reduces the extent of UC, even in the presence of mutant alleles.

Molecular mechanism and genetic determinants of buprofezin degradation.

PubMed

Chen, Xueting; Ji, Junbin; Zhao, Leizhen; Qiu, Jiguo; Dai, Chen; Wang, Weiwu; He, Jian; Jiang, Jiandong; Hong, Qing; Yan, Xin

2017-07-14

Buprofezin is a widely used insect growth regulator whose residue has been frequently detected in the environment, posing a threat to aquatic organisms and non-target insects. Microorganisms play an important role in the degradation of buprofezin in the natural environment. However, the relevant catabolic pathway has not been fully characterized, and the molecular mechanism of catabolism is still completely unknown. Rhodococcus qingshengii YL-1 can utilize buprofezin as a sole source of carbon and energy for growth. In this study, the upstream catabolic pathway in strain YL-1 was identified using tandem mass spectrometry. Buprofezin is composed of a benzene ring and a heterocyclic ring. The degradation is initiated by the dihydroxylation of the benzene ring and continues via dehydrogenation, aromatic ring cleavage, breaking of an amide bond and the release of the heterocyclic ring 2- tert -butylimino-3-isopropyl-1,3,5-thiadiazinan-4-one (2-BI). A buprofezin degradation-deficient mutant strain YL-0 was isolated. Comparative genomic analysis combined with gene deletion and complementation experiments revealed that the gene cluster bfzBA3A4A1A2C is responsible for the upstream catabolic pathway of buprofezin. bfzA3A4A1A2 encodes a novel Rieske non-heme iron oxygenase (RHO) system that is responsible for the dihydroxylation of buprofezin at the benzene ring; bfzB is involved in dehydrogenation, and bfzC is in charge of benzene ring cleavage. Furthermore, the products of bfzBA3A4A1A2C can also catalyze dihydroxylation, dehydrogenation and aromatic ring cleavage of biphenyl, flavanone, flavone and bifenthrin. In addition, a transcriptional study revealed that bfzBA3A4A1A2C is organized in one transcriptional unit that is constitutively expressed in strain YL-1. Importance There is an increasing concern about the residue and environmental fate of buprofezin. Microbial metabolism is an important mechanism responsible for the buprofezin degradation in natural environment. However, the molecular mechanism and genetic determinants of microbial degradation of buprofezin has not been well identified. This work revealed that gene cluster bfzBA3A4A1A2C is responsible for the upstream catabolic pathway of buprofezin in R. qingshengii YL-1. The products of bfzBA3A4A1A2C could also degrade bifenthrin, a widely used pyrethroid insecticide. These findings enhance our understanding of the microbial degradation mechanism of buprofezin and benefit the application of strain YL-1 and bfzBA3A4A1A2C in the bioremediation of buprofezin contamination. Copyright © 2017 American Society for Microbiology.

Molecular Mechanism and Genetic Determinants of Buprofezin Degradation

PubMed Central

Chen, Xueting; Ji, Junbin; Zhao, Leizhen; Qiu, Jiguo; Dai, Chen; Wang, Weiwu; He, Jian; Jiang, Jiandong; Hong, Qing

2017-01-01

ABSTRACT Buprofezin is a widely used insect growth regulator whose residue has been frequently detected in the environment, posing a threat to aquatic organisms and nontarget insects. Microorganisms play an important role in the degradation of buprofezin in the natural environment. However, the relevant catabolic pathway has not been fully characterized, and the molecular mechanism of catabolism is still completely unknown. Rhodococcus qingshengii YL-1 can utilize buprofezin as a sole source of carbon and energy for growth. In this study, the upstream catabolic pathway in strain YL-1 was identified using tandem mass spectrometry. Buprofezin is composed of a benzene ring and a heterocyclic ring. The degradation is initiated by the dihydroxylation of the benzene ring and continues via dehydrogenation, aromatic ring cleavage, breaking of an amide bond, and the release of the heterocyclic ring 2-tert-butylimino-3-isopropyl-1,3,5-thiadiazinan-4-one (2-BI). A buprofezin degradation-deficient mutant strain YL-0 was isolated. A comparative genomic analysis combined with gene deletion and complementation experiments revealed that the gene cluster bfzBA3A4A1A2C is responsible for the upstream catabolic pathway of buprofezin. The bfzA3A4A1A2 cluster encodes a novel Rieske nonheme iron oxygenase (RHO) system that is responsible for the dihydroxylation of buprofezin at the benzene ring; bfzB is involved in dehydrogenation, and bfzC is in charge of benzene ring cleavage. Furthermore, the products of bfzBA3A4A1A2C can also catalyze dihydroxylation, dehydrogenation, and aromatic ring cleavage of biphenyl, flavanone, flavone, and bifenthrin. In addition, a transcriptional study revealed that bfzBA3A4A1A2C is organized in one transcriptional unit that is constitutively expressed in strain YL-1. IMPORTANCE There is an increasing concern about the residue and environmental fate of buprofezin. Microbial metabolism is an important mechanism responsible for the buprofezin degradation in the natural environment. However, the molecular mechanism and genetic determinants of microbial degradation of buprofezin have not been well identified. This work revealed that gene cluster bfzBA3A4A1A2C is responsible for the upstream catabolic pathway of buprofezin in Rhodococcus qingshengii YL-1. The products of bfzBA3A4A1A2C could also degrade bifenthrin, a widely used pyrethroid insecticide. These findings enhance our understanding of the microbial degradation mechanism of buprofezin and benefit the application of strain YL-1 and bfzBA3A4A1A2C in the bioremediation of buprofezin contamination. PMID:28710269

R102Q mutation shifts the salt-bridge network and reduces the structural flexibility of human neuronal calcium sensor-1 protein.

PubMed

Zhu, Yuzhen; Wu, Ying; Luo, Yin; Zou, Yu; Ma, Buyong; Zhang, Qingwen

2014-11-20

Neuronal calcium sensor-1 (NCS-1) protein has a variety of different neuronal functions and interacts with multiple binding partners mostly through a large solvent-exposed hydrophobic crevice (HC). A single R102Q mutation in human NCS-1 protein was demonstrated to be associated with autism disease. Solution NMR study reported that this R102Q mutant had long-range chemical shift effects on the HC and the C-terminal tail (L3). To understand the influence of the R102Q mutation on the HC and L3 of NCS-1, we have investigated the conformational dynamics and the structural flexibility of wild type (WT) NCS-1 and its R102Q mutant by conducting extensive all-atom molecular dynamics (MD) simulations. On the basis of six independent 450 ns MD simulations, we have found that the R102Q mutation in NCS-1 protein (1) dramatically reduces the flexibility of loops L2 and L3, (2) facilitates L3 in a more extended state to occupy the hydrophobic crevice to a larger extent, (3) significantly affects the intersegment salt bridges, and (4) changes the subspace of the free energy landscape of NCS-1 protein. Analysis of the salt bridge network in both WT and the R102Q variant demonstrates that the R102Q-mutation-induced salt bridge alternations play a critical role on the reduced flexibility of L2 and L3. These results reveal the important role of salt bridges on the structural properties of NCS-1 protein and that R102Q mutation disables the dynamic relocation of C-terminus, which may block the binding of NCS-1 protein to its receptors. This study may provide structural insights into the autistic spectrum disorder associated with R102Q mutation.

Anisotropy of the upper critical field and its thickness dependence in superconducting FeSe electric-double-layer transistors

NASA Astrophysics Data System (ADS)

Shiogai, Junichi; Kimura, Shojiro; Awaji, Satoshi; Nojima, Tsutomu; Tsukazaki, Atsushi

2018-05-01

Anisotropy of superconductivity is one of the fundamental physical parameters for understanding layered iron-based superconductors (IBSs). Here we investigated the anisotropic response of resistive transition as a function of thickness (d ) in iron selenide (FeSe) based electric-double-layer transistors (EDLTs) on SrTi O3 , which exhibit superconducting transition temperatures Tc as high as 40 K below d =10 nm . According to the analyses of the in-plane (Hc2 //) and out-of-plane (Hc2 ⊥) upper critical fields (Hc 2) and the magnetic field angle dependence of the resistance (Rs-θ ) in ultrathin condition, we found that the anisotropy factor ɛ0=Hc2 ///Hc2 ⊥ is 7.4 in the thin limit of d ˜1 nm , which is larger than that of bulk IBSs. In addition, we observed the shorter out-of-plane coherence length ξc of 0.19 nm compared to the c -axis lattice constant, which implies the confinement of the order parameter in the one unit cell FeSe. These findings suggest that high-Tc superconductivity in the ultrathin FeSe-EDLT exhibits an anisotropic three-dimensional (3D) or quasi-two-dimensional (2D) nature rather than the pure 2D one, leading to the robust superconductivity. Moreover, we carried out the systematic evaluation of the anisotropic Hc 2 against thickness reduction in the FeSe channel. The in-plane Hc 2 as a function of normalized temperature T /Tc is almost independent of d until the thin limit condition. On the other hand, the out-of-plane Hc 2 near T /Tc˜1 decreases with increasing d , resulting in the increase of ɛ0 at around Tc to 32.0 at the thick condition of d =9.3 nm , which is also confirmed by Rs-θ measurements. The counterintuitive behavior can be attributed to the degree of coupling strength between two electron-rich layers possessing a high superconducting order parameter induced by electrostatic gating at the top interface and charge transfer from SrTi O3 substrates at the bottom interface. Besides a large Hc2 ⊥ for d =9.3 nm exceeding 20 T even at T =0.8 Tc , we observe the decoupling crossover of the two superconducting layers at low temperature, which is a unique feature for the high-Tc FeSe-EDLT on SrTi O3 .

Comparison of Onclarity Human Papillomavirus (HPV) Assay with Hybrid Capture II HPV DNA Assay for Detection of Cervical Intraepithelial Neoplasia Grade 2 and 3 Lesions

PubMed Central

Sideri, M.; Gulmini, C.; Igidbashian, S.; Tricca, A.; Casadio, C.; Carinelli, S.; Boveri, S.; Ejegod, D.; Bonde, J.; Sandri, M. T.

2015-01-01

Analytical and clinical performance validation is essential before introduction of a new human papillomavirus (HPV) assay into clinical practice. This study compares the new BD Onclarity HPV assay, which detects E6/E7 DNA from 14 high-risk HPV types, to the Hybrid Capture II (HC2) HPV DNA test, to concurrent cytology and histology results, in order to evaluate its performance in detecting high-grade cervical lesions. A population of 567 women, including 325 with ≥ASCUS (where ASCUS stands for atypical cells of undetermined significance) and any HC2 result and 242 with both negative cytology and negative HC2 results, were prospectively enrolled for the study. The overall agreement between Onclarity and HC2 was 94.6% (95% confidence intervals [CI], 92.3% to 96.2%). In this population with a high prevalence of disease, the relative sensitivities (versus adjudicated cervical intraepithelial neoplasia grades 2 and 3 [CIN2+] histology endpoints) of the Onclarity and HC2 tests were 95.2% (95% CI, 90.7% to 97.5%) and 96.9% (95% CI, 92.9% to 98.7%), respectively, and the relative specificities were 50.3% (95% CI, 43.2% to 57.4%) for BD and 40.8% (95% CI, 33.9%, 48.1%) for HC2. These results indicate that the BD Onclarity HPV assay has sensitivity comparable to that of the HC2 assay, with a trend to an increased specificity. Moreover, as Onclarity gives the chance to discriminate between the different genotypes, we calculated the genotype prevalence and the absolute risk of CIN2+: HPV 16 was the most prevalent genotype (19.8%) with an absolute risk of CIN2+ of 77.1%. PMID:25903574

Detection of Interstellar HC5O in TMC-1 with the Green Bank Telescope

NASA Astrophysics Data System (ADS)

McGuire, Brett A.; Burkhardt, Andrew M.; Shingledecker, Christopher N.; Kalenskii, Sergei V.; Herbst, Eric; Remijan, Anthony J.; McCarthy, Michael C.

2017-07-01

We report the detection of the carbon-chain radical HC5O for the first time in the interstellar medium toward the cold core TMC-1 using the 100 m Green Bank Telescope. We observe four hyperfine components of this radical in the J=17/2\\to 15/2 rotational transition that originates from the {}2{{{\\Pi }}}1/2 fine structure level of its ground state and calculate an abundance of n/{n}{H2}=1.7× {10}-10, assuming an excitation temperature of {T}{ex}=7 K. No indication of HC3O, HC4O, or HC6O, is found in these or archival observations of the source, while we report tentative evidence for HC7O. We compare calculated upper limits and the abundance of HC5O to predictions based on (1) the abundance trend of the analogous HC n N family in TMC-1 and (2) a gas-grain chemical model. We find that the gas-grain chemical model well reproduces the observed abundance of HC5O, as well as the upper limits of HC3O, HC6O, and HC7O, but HC4O is overproduced. The prospects for astronomical detection of both shorter and longer HC n O chains are discussed.

A new superhard carbon allotrope: Orthorhombic C20

NASA Astrophysics Data System (ADS)

Wei, Qun; Zhao, Chenyang; Zhang, Meiguang; Yan, Haiyan; Zhou, Yingjiao; Yao, Ronghui

2018-06-01

A new superhard carbon orthorhombic allotrope oC20 is proposed, which exhibits distinct topologies including C4, C3 and two types of C6 carbon rings. The calculated elastic constants and phonon spectra reveal that oC20 is mechanically and dynamically stable at ambient pressure. The calculated electronic band structure of oC20 shows that it is an indirect band gap semiconductor with a band gap of 4.46 eV. The Vickers hardness of oC20 is 75 GPa. The calculated tensile and shear strength indicate that the weakest tensile strength is 64 GPa and the weakest shear strength is 48 GPa, which means oC20 is a potential superhard material.

3-Methyl-1,4-dioxo-1,4-dihydro­naphthalen-2-yl 4-amino­benzoate

PubMed Central

Bambagiotti-Alberti, Massimo; Bartolucci, Gianluca; Bruni, Bruno; Coran, Silvia; Di Vaira, Massimo

2008-01-01

The crystal structure of the title compound, C18H13NO4, the oxidized form of the drug aminaftone used in venous disease therapy, is characterized by the presence of ribbons of hydrogen-bonded mol­ecules parallel to the [111] crystallographic direction and by stacking inter­actions between rings [centroid–centroid distance between quinone rings = 3.684 (3) Å and between amino­benzoate rings = 4.157 (3) Å] along the ribbons. PMID:21202108

SOLIS IV. Hydrocarbons in the OMC-2 FIR4 Region, a Probe of Energetic Particle Irradiation of the Region

NASA Astrophysics Data System (ADS)

Favre, C.; Ceccarelli, C.; López-Sepulcre, A.; Fontani, F.; Neri, R.; Manigand, S.; Kama, M.; Caselli, P.; Jaber Al-Edhari, A.; Kahane, C.; Alves, F.; Balucani, N.; Bianchi, E.; Caux, E.; Codella, C.; Dulieu, F.; Pineda, J. E.; Sims, I. R.; Theulé, P.

2018-06-01

We report new interferometric images of cyclopropenylidene, c-C3H2, toward the young protocluster OMC-2 FIR 4. The observations were performed at 82 and 85 GHz with the NOrthern Extended Millimeter Array (NOEMA) as part of the project Seeds Of Life In Space (SOLIS). In addition, IRAM-30 m data observations were used to investigate the physical structure of OMC-2 FIR 4. We find that the c-C3H2 gas emits from the same region where previous SOLIS observations showed bright HC5N emission. From a non-LTE analysis of the IRAM-30 m data, the c-C3H2 gas has an average temperature of ∼40 K, a H2 density of ∼3 × 105 cm‑3, and a c-C3H2 abundance relative to H2 of (7 ± 1) × 10‑12. In addition, the NOEMA observations provide no sign of significant c-C3H2 excitation temperature gradients across the region (about 3–4 beams), with T ex in the range 8 ± 3 up to 16 ± 7 K. We thus infer that our observations are inconsistent with a physical interaction of the OMC-2 FIR 4 envelope with the outflow arising from OMC-2 FIR 3, as claimed by previous studies. The comparison of the measured c-C3H2 abundance with the predictions from an astrochemical PDR model indicates that OMC-2 FIR 4 is irradiated by an FUV field ∼1000 times larger than the interstellar one, and by a flux of ionizing particles ∼4000 times larger than the canonical value of 1 × 10‑17 s‑1 from the Galaxy cosmic rays, which is consistent with our previous HC5N observations. This provides an important and independent confirmation of other studies that one, or more, source inside the OMC-2 FIR 4 region emits energetic (≥10 MeV) particles. Based on observations carried out under project number L15AA with the IRAM NOEMA Interferometer. IRAM is supported by INSU/CNRS (France), MPG (Germany) and IGN (Spain).

Role of methyl group number on SOA formation from aromatic hydrocarbons photooxidation under low NOx conditions

NASA Astrophysics Data System (ADS)

Li, L.; Tang, P.; Nakao, S.; Chen, C.-L.; Cocker, D. R., III

2015-11-01

Substitution of methyl groups onto the aromatic ring determines the SOA formation from the aromatic hydrocarbon precursor. This study links the number of methyl groups on the aromatic ring to SOA formation from aromatic hydrocarbons photooxidation under low NOx conditions (HC / NO > 10 ppb C : ppb). Aromatic hydrocarbons with increasing numbers of methyl groups are systematically studied. SOA formation from pentamethylbenzene and hexamethylbenzene are reported for the first time. A decreasing SOA yield with increasing number of methyl groups is observed. Linear trends are found in both f44 vs. f43 and O / C vs. H / C for SOA from aromatic hydrocarbons with zero to six methyl groups. An SOA oxidation state predictive method based on benzene is used to examine the effect of added methyl groups on aromatic oxidation under low NOx conditions. Further, the impact of methyl group number on density and volatility of SOA from aromatic hydrocarbons is explored. Finally, a mechanism for methyl group impact on SOA formation is suggested. Overall, this work suggests as more methyl groups are attached on the aromatic ring, SOA products from these aromatic hydrocarbons become less oxidized per mass/carbon.

Separation and characterization of polycyclic aromatic hydrocarbons and alkylphenols in coal derived solvents

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

Hurtubise, R.J.; Allen, T.W.; Hussain, A.

1981-03-29

Dry-column chromatography with an aluminum oxide stationary phase and a n-hexane-ether (19:1) mobile phase was used to separate polycyclic aromatic hydrocarbons (PAH) by ring size. Prior to the dry-column chromatography step, the coal derived solvents were added to an acid treated silica gel column and eluted with chloroform. This step removed pyridine-type nitrogen heterocycles. After separation of the individual ring fractions, the fractions were further separated by either thin layer chromatography (TLC) or high performance liquid chromatography (HPLC). If TLC was used, then after separation fluorescence profiles of each PAH ring fraction distributed on 30%-acetylated cellulose chromatoplates were obtained withmore » a spectrodensitometer. Measurement of fluorescence peak heights gave an approximate measure of the amount of the 3-, 4-, 5-, and 6- ring PAH. For HPLC separation, the 3- and 4- ring PAH fractions obtained from the dry-column chromatography step were separated with a ..mu..-Bondapak C/sub 18/ column and methanol:water (65:35) mobile phase. The HPLC separated PAH were characterized by chromatographic correlation factors and corrected fluorescence excitation spectra. Alkylphenols were identified in coal recycle solvent sample following separation by HPLC.« less

Post-exercise protein synthesis rates are only marginally higher in type I compared with type II muscle fibres following resistance-type exercise.

PubMed

Koopman, René; Gleeson, Benjamin G; Gijsen, Annemie P; Groen, Bart; Senden, Joan M G; Rennie, Michael J; van Loon, Luc J C

2011-08-01

We examined the effect of an acute bout of resistance exercise on fractional muscle protein synthesis rates in human type I and type II muscle fibres. After a standardised breakfast (31 ± 1 kJ kg(-1) body weight, consisting of 52 Energy% (En%) carbohydrate, 34 En% protein and 14 En% fat), 9 untrained men completed a lower-limb resistance exercise bout (8 sets of 10 repetitions leg press and leg extension at 70% 1RM). A primed, continuous infusion of L: -[ring-(13)C(6)]phenylalanine was combined with muscle biopsies collected from both legs immediately after exercise and after 6 h of post-exercise recovery. Single muscle fibres were dissected from freeze-dried biopsies and stained for ATPase activity with pre-incubation at a pH of 4.3. Type I and II fibres were separated under a light microscope and analysed for protein-bound L: -[ring-(13)C(6)]phenylalanine labelling. Baseline (post-exercise) L: -[ring-(13)C(6)]phenylalanine muscle tissue labelling, expressed as (∂(13)C/(12)C), averaged -32.09 ± 0.28, -32.53 ± 0.10 and -32.02 ± 0.16 in the type I and II muscle fibres and mixed muscle, respectively (P = 0.14). During post-exercise recovery, muscle protein synthesis rates were marginally (8 ± 2%) higher in the type I than type II muscle fibres, at 0.100 ± 0.005 versus 0.094 ± 0.005%/h, respectively (P < 0.05), whereby rates of mixed muscle protein were 0.091 ± 0.005%/h. Muscle protein synthesis rates following resistance-type exercise are only marginally higher in type I compared with type II muscle fibres.

Reduction Behavior of Assmang and Comilog ore in the SiMn Process

NASA Astrophysics Data System (ADS)

Kim, Pyunghwa Peace; Holtan, Joakim; Tangstad, Merete

The reduction behavior of raw materials from Assmang and Comilog based charges were experimentally investigated with CO gas up to 1600 °C. Quartz, HC FeMn slag or limestone were added to Assmang or Comilog according to the SiMn production charge, and mass loss results were obtained by using a TGA furnace. The results showed that particle size, type of manganese ore and mixture have close relationship to the reduction behavior of raw materials during MnO and SiO2 reduction. The influence of particle size to mass loss was apparent when Assmang or Comilog was mixed with only coke (FeMn) while it became insignificant when quartz and HC FeMn slag (SiMn) were added. This implied that quartz and HC FeMn slag had favored the incipient slag formation regardless of particle size. This explained the similar mass loss tendencies of SiMn charge samples between 1200-1500 °C, contrary to FeMn charge samples where different particle sizes showed significant difference in mass loss. Also, while FeMn charge samples showed progressive mass loss, SiMn charge samples showed diminutive mass loss until 1500 °C. However, rapid mass losses were observed with SiMn charge samples in this study above 1500 °C, and they have occurred at different temperatures. This implied rapid reduction of MnO and SiO2 and the type of ore and addition of HC FeMn slag have significant influence determining these temperatures. The temperatures observed for the rapid mass loss were approximately 1503 °C (Quartz and HC FeMn slag addition in Assmang), 1543 °C (Quartz addition in Assmang) and 1580-1587 °C (Quartz and limestone addition in Comilog), respectively. These temperatures also showed indications of possible SiMn production at process temperatures lower than 1550 °C.

The Feasibility of Detecting Neuropsychologic and Neuroanatomic Effects of Type 1 Diabetes in Young Children

PubMed Central

Aye, Tandy; Reiss, Allan L.; Kesler, Shelli; Hoang, Sherry; Drobny, Jessica; Park, Yaena; Schleifer, Kristin; Baumgartner, Heidi; Wilson, Darrell M.; Buckingham, Bruce A.

2011-01-01

OBJECTIVE To determine if frequent exposures to hypoglycemia and hyperglycemia during early childhood lead to neurocognitive deficits and changes in brain anatomy. RESEARCH DESIGN AND METHODS In this feasibility, cross-sectional study, young children, aged 3 to 10 years, with type 1 diabetes and age- and sex-matched healthy control (HC) subjects completed neuropsychologic (NP) testing and magnetic resonance imaging (MRI) scans of the brain. RESULTS NP testing and MRI scanning was successfully completed in 98% of the type 1 diabetic and 93% of the HC children. A significant negative relationship between HbA1c and Wechsler Intelligence Scale for Children (WISC) verbal comprehension was observed. WISC index scores were significantly reduced in type 1 diabetic subjects who had experienced seizures. White matter volume did not show the expected increase with age in children with type 1 diabetes compared with HC children (diagnosis by age interaction, P = 0.005). A similar trend was detected for hippocampal volume. Children with type 1 diabetes who had experienced seizures showed significantly reduced gray matter and white matter volumes relative to children with type 1 diabetes who had not experienced seizures. CONCLUSIONS It is feasible to perform MRI and NP testing in young children with type 1 diabetes. Further, early signs of neuroanatomic variation may be present in this population. Larger cross-sectional and longitudinal studies of neurocognitive function and neuroanatomy are needed to define the effect of type 1 diabetes on the developing brain. PMID:21562318

Titan's Gas Behavior During the South Pole Fall

NASA Astrophysics Data System (ADS)

Cottini, Valeria; Nixon, Conor A.; Achterberg, Richard K.; Jennings, Donald E.; Gorius, Nicolas; Irwin, Patrick G. J.

2015-11-01

Titan’s southern middle atmosphere has been showing several changes since the start of fall season in 2009. In 2012 a large cloud appeared [1], [2], [3], temperatures became very low and condensation and gas concentration at the South Pole increased [3], [4].In this work we will show the results of gas abundances retrievals in the South Pole and their latitudinal variation changes as the cold season evolved with time.We analyzed several Cassini Composite InfraRed Spectrometer (CIRS [5]) mid-infrared observations of the South Pole acquired during 2013-2014. The data coordinates were converted in order to be centered on the atmospheric pole and refer to the 1 mbar level and not to the surface. We first determine stratospheric temperatures from the same data and latitudes from the n4 band of methane centered around 1300 cm-1. We retrieve the temperature profiles applying a radiative transfer forward model combined with a non-linear optimal estimation inversion method [6]. We then retrieve the main gases abundances and track their variation with latitude using the same method.Latitudinal changes of the main Titan’s gases - HC3N, C4H2, C6H6, C2H2, C2H4, C3H8 and HCN - show different trends in the Southern polar regions over 2014, when winter was getting closer. We observe a ring-shape in some of the gas abundance distributions, with a local maximum peak around -75 deg of latitude. We also observe an increase of abundance of most of the gases toward the south pole, as seen previously in the North during the winter. The observed increase of benzene over the South Pole is definitely evident and strong. References: [1] West, R. A. et al. (2013) BAAS, 45, 305.03. [2] Jennings, D. E. et al. (2012) ApJ, 754, L3. [3] de Kok, R. et al. (2014), Nature, 514, 7520, 65-67. [4] Vinatier S. et al. (2015) Icarus, Volume 250, p. 95-115. [5] Flasar et al. (2004) Space Sci. Rev., 115, 169-297. [6] Irwin, P.G.J. et al. (2008) J. Quant. Spectrosc. Radiat. Trans., 109, 1136-1150.

Superconductivity in single crystalline YPd2Ge2

NASA Astrophysics Data System (ADS)

Chajewski, G.; Wiśniewski, P.; Hackemer, A.; Pikul, A. P.; Kaczorowski, D.

2018-05-01

Single crystals of the YPd2Ge2 compound, crystallizing in the body-centered tetragonal ThCr2Si2-type structure, were studied by means of low-temperature magnetization, specific heat and electrical resistivity measurements. The zero-field data confirmed bulk and intrinsic superconductivity of the compound with the critical temperature 1.14 K, while the experiments performed in magnetic fields revealed a non-trivial character of the superconducting state. In particular, low and close to each other critical fields μ0Hc1 and μ0Hc2 (of about 20-30 mT) and field-induced first-order phase transition occurring only in the field parallel to the ab plane suggest possible cross-over from the type-I to type-II/1 superconductivity. Moreover, YPd2Ge2 exhibits robust surface superconductivity with the critical field μ0Hc3 about 20 times larger than μ0Hc1 and μ0Hc2.

4,5-Dibromo-2,7-di-tert-butyl-9,9-dimethyl-9H-thioxanthene

PubMed Central

Rubio, Omayra H.; Fuentes de Arriba, Angel L.; Sanz, Francisca; Muniz, Francisco M.; Morán, Joaquín R.

2012-01-01

In the title compound, C23H28Br2S, the thioxanthene unit is twisted, showing a dihedral angle of 29.3 (5)° between the benzene rings. When projected along [001], the packing shows two types of channels. The crystal studied was a racemic twin. PMID:22719586

Nonequilibrium Effects in Ion and Electron Transport

DTIC Science & Technology

1990-11-01

GaAs, Si oxide, Si nitride , metals) CF4, CxFy, SF6, SF 4, NF3, CClxFy, Cl2, CC14, BC13, HC1, PC 3, SiCl4, H2, 02, CF3H, Br2, CBrxFy, Rare gases, plus...numerous stable and intermediate product species Deposition Gases (For Si, Si oxides, Ti oxides, Si,B nitride , metals) SiH4, 5i2H6, TEOS, 02, N20, C02...I. C. Walker, and K. J. Mathieson, 1988, J. Phys. D 21, 1271. Davies, D. K., August 1982, "Measurements of swarm parameters in chlorine -bearing

Condensed tannins: A novel rearrangement of procyanidins and prodelphinidins in thiolytic cleavage

Treesearch

G. Wayne McGraw; Jan P. Steynberg; Richard W. Hemingway

1993-01-01

Conditions commonly used for the thiolytic cleavage of interflavanoid bonds of condensed tannins also result in cleavage of the C4 to C10 bond of flavan units. Subsequenet lectrophilic attack of the C4 carbocation on the C2' or C6' of the B-ring, and loss of phloroglucinol (the A-ring), result in the formation of a mixture of 1,3-dithiobenzyl-2,4,s,6-...

Expression and characterization of the antimicrobial peptide ABP-dHC-cecropin A in the methylotrophic yeast Pichia pastoris.

PubMed

Sang, Ming; Wei, Hui; Zhang, Jiaxin; Wei, Zhiheng; Wu, Xiaolong; Chen, Yan; Zhuge, Qiang

2017-12-01

ABP-dHC-cecropin A is a linear cationic peptide that exhibits antimicrobial properties. To explore a new approach for expression of ABP-dHC-cecropin A using the methylotrophic yeast Pichia pastoris, we cloned the ABP-dHC-cecropin A gene into the vector pPICZαA. The SacI-linearized plasmid pPICZαA-ABP-dHC-cecropin A was then transformed into P. pastoris GS115 by electroporation. Expression was induced after a 96-h incubation with 0.5% methanol at 20 °C in a culture supplied with 2% casamino acids to avoid proteolysis. Under these conditions, approximately 48 mg of ABP-dHC-cecropin A was secreted into 1L (4 × 250-mL)of medium. Recombinant ABP-dHC-cecropin A was purified using size-exclusion chromatography, and 21 mg of pure active ABP-dHC-cecropin A was obtained from 1L (4 × 250-mL)of culture. Electrophoresis on 4-20% gradient gels indicated that recombinant ABP-dHC-cecropin A was secreted as a protein approximately 4 kDa in size. Recombinant ABP-dHC-cecropin A was successfully expressed, as the product displayed antibacterial and antifungal activities (based on an antibacterial assay, scanning electron microscopy, and antifungal assay) indistinguishable from those of the synthesized protein. Copyright © 2017 Elsevier Inc. All rights reserved.

Retention of metal-ceramic crowns with contemporary dental cements.

PubMed

Johnson, Glen H; Lepe, Xavier; Zhang, Hai; Wataha, John C

2009-09-01

New types of crown and bridge cement are in use by practitioners, and independent studies are needed to assess their effectiveness. The authors conducted a study in three parts (study A, study B, and study C) and to determine how well these new cements retain metal-ceramic crowns. The authors prepared teeth with a 20-degree taper and a 4-millimeter length. They cast high-noble metal-ceramic copings, then fitted and cemented them with a force of 196 newtons. The types of cements they used were zinc phosphate, resin-modified glass ionomer, conventional resin and self-adhesive modified resin. They thermally cycled the cemented copings, then removed them. They recorded the removal force and calculated the stress of dislodgment by using the surface area of each preparation. They used a single-factor analysis of variance to analyze the data (alpha = .05). The mean stresses necessary to remove crowns, in megapascals, were 8.0 for RelyX Luting (3M ESPE, St. Paul, Minn.), 7.3 for RelyX Unicem (3M ESPE), 5.7 for Panavia F (Kuraray America, New York) and 4.0 for Fuji Plus (GC America, Alsip, Ill.) in study A; 8.1 for RelyX Luting, 2.6 for RelyX Luting Plus (3M ESPE) and 2.8 for Fuji CEM (GC America) in study B; and 4.9 for Maxcem (Kerr, Orange, Calif.), 4.0 for BisCem (Bisco, Schaumburg, Ill.), 3.7 for RelyX Unicem Clicker (3M ESPE), 2.9 for iCEM (Heraeus Kulzer, Armonk, N.Y.) and 2.3 for Fleck's Zinc Cement (Keystone Industries, Cherry Hill, N.J.) in study C. Powder-liquid versions of new cements were significantly more retentive than were paste-paste versions of the same cements. The mean value of crown removal stress for the new self-adhesive modified-resin cements varied appreciably among the four cements tested. All cements retained castings as well as or better than did zinc phosphate cement. Powder-liquid versions of cements, although less convenient to mix, may be a better clinical choice when crown retention is an issue. All cements tested will retain castings adequately on ideal preparations because the corresponding removal stresses are comparable with or higher than those associated with zinc phosphate. Powder-liquid resin-modified glass ionomer cement, selected self-adhesive modified-resin cements and conventional resin cements provide additional retention when desired.

Anti-malarial activities of Andrographis paniculata and Hedyotis corymbosa extracts and their combination with curcumin

PubMed Central

Mishra, Kirti; Dash, Aditya P; Swain, Bijay K; Dey, Nrisingha

2009-01-01

Background Herbal extracts of Andrographis paniculata (AP) and Hedyotis corymbosa (HC) are known as hepato-protective and fever-reducing drugs since ancient time and they have been used regularly by the people in the south Asian sub-continent. Methanolic extracts of these two plants were tested in vitro on choloroquine sensitive (MRC-pf-20) and resistant (MRC-pf-303) strains of Plasmodium falciparum for their anti-malarial activity. Methods Growth inhibition was determined using different concentrations of these plant extracts on synchronized P. falciparum cultures at the ring stage. The interactions between these two plant extracts and individually with curcumin were studied in vitro. The performance of these two herbal extracts in isolation and combination were further evaluated in vivo on Balb/c mice infected with Plasmodium berghei ANKA and their efficacy was compared with that of curcumin. The in vivo toxicity of the plant derived compounds as well as their parasite stage-specificity was studied. Results The 50% inhibitory concentration (IC50) of AP (7.2 μg/ml) was found better than HC (10.8 μg/ml). Combination of these two herbal drugs showed substantial enhancement in their anti-malarial activity. Combinatorial effect of each of these with curcumin also revealed anti-malarial effect. Additive interaction between the plant extracts (AP + HC) and their individual synergism with curcumin (AP+CUR, HC+CUR) were evident from this study. Increased in vivo potency was also observed with the combination of plant extracts over the individual extracts and curcumin. Both the plant extracts were found to inhibit the ring stage of the parasite and did not show any in vivo toxicity, whether used in isolation or in combination. Conclusion Both these two plant extracts in combination with curcumin could be an effective, alternative source of herbal anti-malarial drugs. PMID:19216765

Crystal structure of bis-(μ-3-nitro-benzoato)-κ3O,O':O;κ3O:O,O'-bis-[bis-(3-cyano-pyridine-κN1)(3-nitro-benzoato-κ2O,O')cadmium].

PubMed

Hökelek, Tuncer; Akduran, Nurcan; Özen, Azer; Uğurlu, Güventürk; Necefoğlu, Hacali

2017-03-01

The asymmetric unit of the title compound, [Cd 2 (C 7 H 4 NO 4 ) 4 (C 6 H 4 N 2 ) 4 ], contains one Cd II atom, two 3-nitro-benzoate (NB) anions and two 3-cyano-pyridine (CPy) ligands. The two CPy ligands act as monodentate N(pyridine)-bonding ligands, while the two NB anions act as bidentate ligands through the carboxyl-ate O atoms. The centrosymmetric dinuclear complex is generated by application of inversion symmetry, whereby the Cd II atoms are bridged by the carboxyl-ate O atoms of two symmetry-related NB anions, thus completing the distorted N 2 O 5 penta-gonal-bipyramidal coordination sphere of each Cd II atom. The benzene and pyridine rings are oriented at dihedral angles of 10.02 (7) and 5.76 (9)°, respectively. In the crystal, C-H⋯N hydrogen bonds link the mol-ecules, enclosing R 2 2 (26) ring motifs, in which they are further linked via C-H⋯O hydrogen bonds, resulting in a three-dimensional network. In addition, π-π stacking inter-actions between parallel benzene rings and between parallel pyridine rings of adjacent mol-ecules [shortest centroid-to-centroid distances = 3.885 (1) and 3.712 (1) Å, respectively], as well as a weak C-H⋯π inter-action, may further stabilize the crystal structure.

Low-cost synthesis and physical characterization of thieno[3,4-c]pyrrole-4,6-dione-based polymers.

PubMed

Berrouard, Philippe; Dufresne, Stéphane; Pron, Agnieszka; Veilleux, Justine; Leclerc, Mario

2012-09-21

The improved synthesis of thieno[3,4-c]pyrrole-4,6-dione (TPD) monomers, including Gewald thiophene ring formation, a Sandmeyer-type reaction, and neat condensation with an amine, is presented. This protocol enables faster, cheaper, and more efficient preparation of TPD units in comparison to traditional methods. Furthermore, a series of TPD homo- and pseudohomopolymers bearing various alkyl chains was synthesized via a direct heteroarylation polymerization (DHAP) procedure. UV-visible absorption and powder X-ray diffraction measurements revealed the relationship between the ratio of branched to linear alkyl chains and the optoelectronic properties of the polymers as well as their packing in the solid state.

Conformational Preference and Donor Atom Interaction Leading to Hexacoordination vs Pentacoordination in Bicyclic Tetraoxyphosphoranes(1).

PubMed

Sherlock, David J.; Chandrasekaran, A.; Prakasha, T. K.; Day, Roberta O.; Holmes, Robert R.

1998-01-12

New bicyclic tetraoxyphosphoranes all containing a six-membered oxaphosphorinane ring, C(6)H(8)(CH(2)O)(2)P(OC(12)H(8))(OXyl) (1), (C(6)H(4)O)(2)P(OC(12)H(8))(OXyl) (2), CH(2)[(t-Bu)(2)C(6)H(2)O](2)P(OC(12)H(8))(OXyl) (3), O(2)S[(t-Bu)MeC(6)H(2)O](2)P(OC(12)H(8))(OXyl) (4), and S[(t-Bu)MeC(6)H(2)O](2)P(OC(12)H(8))(OXyl) (5), were synthesized by the oxidative addition reaction of the cyclic phosphine P(OC(12)H(8))(OXyl) (6) with an appropriate diol in the presence of N-chlorodiisopropylamine. X-ray analysis revealed trigonal bipyramidal (TBP) geometries for 1-4 where the dioxa ring varied in size from six- to eight-membered. With a sulfur donor atom as part of an eight-membered ring in place of a potential oxygen donor atom of a sulfone group as in 4, the X-ray study of 5 showed the formation of a hexacoordinated structure via a P-S interaction. Ring constraints are evaluated to give an order of conformational flexibility associated with the (TBP) tetraoxyphosphoranes 4 > 3 approximately 1 > 2 which parallels the degree of shielding from (31)P NMR chemical shifts: 4 > 3 > 1 > 2. The six- and seven-membered dioxa rings in 1 and 2, respectively, are positioned at axial-equatorial sites, whereas the eight-membered dioxa ring in 3 and 4 occupies diequatorial sites of a TBP. V-T (1)H NMR data give barriers to xylyl group rotation about the C-OXyl bond. The geometry of 5 is located along a coordinate from square pyramidal toward octahedral to the extent of 60.7%. Achieving hexacoordination in bicyclic tetraoxyphosphoranes of reduced electrophilicity relative to bicyclic pentaoxyphosphoranes appears to be dependent on the presence of a sufficiently strong donor atom.

Crystal structure of 1-ferrocenyl-2-(4-methyl-benzo-yl)spiro-[11H-pyrrolidizine-3,11'-indeno[1,2-b]quinoxaline].

PubMed

Chandralekha, Kuppan; Gavaskar, Deivasigamani; Sureshbabu, Adukamparai Rajukrishnan; Lakshmi, Srinivasakannan

2014-09-01

In the title compound, [Fe(C5H5)(C34H28N3O)], the four-fused-rings system of the 11H-indeno-[1,2-b]quinoxaline unit is approximately planar [maximum deviation = 0.167 (4) Å] and forms a dihedral angle of 37.25 (6)° with the plane of the benzene ring of the methyl-benzoyl group. Both pyrrolidine rings adopt a twist conformation. An intra-molecular C-H⋯O hydrogen bond is observed. In the crystal, mol-ecules are linked by C-H⋯O hydrogen bonds and weak C-H⋯π inter-actions, forming double chains extending parallel to the c axis.

Relationships between Endogenous Plasma Biomarkers of Constitutive Cytochrome P450 3A Activity and Single-Time-Point Oral Midazolam Microdose Phenotype in Healthy Subjects.

PubMed

Woolsey, Sarah J; Beaton, Melanie D; Choi, Yun-Hee; Dresser, George K; Gryn, Steven E; Kim, Richard B; Tirona, Rommel G

2016-04-01

Due to high basal interindividual variation in cytochrome P450 3A (CYP3A) activity and susceptibility to drug interactions, there has been interest in the application of efficient probe drug phenotyping strategies, as well as endogenous biomarkers for assessment of in vivo CYP3A activity. The biomarkers 4β-hydroxycholesterol (4βHC) and 6β-hydroxycortisol (6βHCL) are sensitive to CYP3A induction and inhibition. However, their utility for the assessment of constitutive CYP3A activity remains uncertain. We investigated whether endogenous plasma biomarkers (4βHC and 6βHCL) are associated with basal CYP3A metabolic activity in healthy subjects assessed by a convenient single-time-point oral midazolam (MDZ) phenotyping strategy. Plasma 4βHC and 6βHCL metabolic ratios (MRs) were analysed in 51 healthy adult participants. CYP3A activity was determined after administration of an oral MDZ microdose (100 μg). Simple linear and multiple linear regression analyses were performed to assess relationships between MDZ oral clearance, biomarkers and subject covariates. Among study subjects, basal MDZ oral clearance, 4βHC and 6βHCL MRs ranged 6.5-, 10- and 13-fold, respectively. Participant age and alcohol consumption were negatively associated with MDZ oral clearance (p = 0.03 and p = 0.045, respectively), while weight and female sex were associated with lower plasma 4βHC MR (p = 0.0003 and p = 0.032, respectively). Neither 4βHC nor 6βHCL MRs were associated with MDZ oral clearance. Plasma 4βHC and 6βHCL MRs do not relate to MDZ single-time-point metabolic phenotype in the assessment of constitutive CYP3A activity among healthy individuals. © 2015 Nordic Association for the Publication of BCPT (former Nordic Pharmacological Society).

Central catalytic domain of BRAP (RNF52) recognizes the types of ubiquitin chains and utilizes oligo-ubiquitin for ubiquitylation.

PubMed

Shoji, Shisako; Hanada, Kazuharu; Ohsawa, Noboru; Shirouzu, Mikako

2017-09-07

Really interesting new gene (RING)-finger protein 52 (RNF52), an E3 ubiquitin ligase, is found in eukaryotes from yeast to humans. Human RNF52 is known as breast cancer type 1 susceptibility protein (BRCA1)-associated protein 2 (BRAP or BRAP2). The central catalytic domain of BRAP comprises four subdomains: nucleotide-binding α/β plait (NBP), really interesting new gene (RING) zinc finger, ubiquitin-specific protease (UBP)-like zinc finger (ZfUBP), and coiled-coil (CC). This domain architecture is conserved in RNF52 orthologs; however, the domain's function in the ubiquitin system has not been delineated. In the present study, we discovered that the RNF52 domain, comprising NBP-RING-ZfUBP-CC, binds to ubiquitin chains (oligo-ubiquitin) but not to the ubiquitin monomers, and can utilize various ubiquitin chains for ubiquitylation and auto-ubiquitylation. The RNF52 domain preferentially bound to M1- and K63-linked di-ubiquitin chains, weakly to K27-linked chains, but not to K6-, K11-, or K48-linked chains. The binding preferences of the RNF52 domain for ubiquitin-linkage types corresponded to ubiquitin usage in the ubiquitylation reaction, except for K11-, K29-, and K33-linked chains. Additionally, the RNF52 domain directly ligated the intact M1-linked, tri-, and tetra-ubiquitin chains and recognized the structural alterations caused by the phosphomimetic mutation of these ubiquitin chains. Full-length BRAP had nearly the same specificity for the ubiquitin-chain types as the RNF52 domain alone. Mass spectrometry analysis of oligomeric ubiquitylation products, mediated by the RNF52 domain, revealed that the ubiquitin-linkage types and auto-ubiquitylation sites depend on the length of ubiquitin chains. Here, we propose a model for the oligomeric ubiquitylation process, controlled by the RNF52 domain, which is not a sequential assembly process involving monomers. © 2017 The Author(s). Published by Portland Press Limited on behalf of the Biochemical Society.

A large head circumference is more strongly associated with unplanned cesarean or instrumental delivery and neonatal complications than high birthweight.

PubMed

Lipschuetz, Michal; Cohen, Sarah M; Ein-Mor, Eliana; Sapir, Hanna; Hochner-Celnikier, Drorith; Porat, Shay; Amsalem, Hagai; Valsky, Dan V; Ezra, Yossef; Elami-Suzin, Matan; Paltiel, Ora; Yagel, Simcha

2015-12-01

Fetal size impacts on perinatal outcomes. We queried whether the fetal head, as the fetal part interfacing with the birth canal, might impact on obstetric outcomes more than birthweight (BW). We examined associations between neonatal head circumference (HC) and delivery mode and risk of perinatal complications as compared to high BW. This was an electronic medical records-based study of term singleton births (37-42 weeks' gestation) from January 2010 through December 2012 (N = 24,780, 6343 primiparae). We assessed risks of unplanned cesarean or instrumental delivery and maternal and fetal complications in cases with HC or BW ≥95th centile (large HC, high BW) vs those with parameters <95th centile (normal). Newborns were stratified into 4 subgroups: normal HC/normal BW (reference, n = 22,548, primiparae 5862); normal HC/high BW (n = 817, P = 213); large HC/normal BW (n = 878, P = 265); and large HC/high BW (n = 537, P = 103). Multinomial multivariable regression provided adjusted odds ratio (aOR) while controlling for potential confounders. Infants with HC ≥95th centile (n = 1415) were delivered vaginally in 62% of cases, unplanned cesarean delivery 16%, and instrumental delivery 11.2%; 78.4% of infants with HC <95th centile were delivered vaginally, 7.8% unplanned cesarean, and 6.7% instrumental delivery. Odds ratio (OR) for unplanned cesarean was 2.58 (95% confidence interval [CI], 2.22-3.01) and for instrumental delivery OR was 2.13 (95% CI, 1.78-2.54). In contrast, in those with BW ≥95th centile (n = 1354) 80.3% delivered vaginally, 10.2% by unplanned cesarean (OR, 1.2; 95% CI, 1.01-1.44), and 3.4% instrumental delivery (OR, 0.46; 95% CI, 0.34-0.62) compared to infants with BW <95th centile: spontaneous vaginal delivery, 77.3%, unplanned cesarean 8.2%, instrumental 7.1%. Multinomial regression with normal HC/normal BW as reference group showed large HC/normal BW infants were more likely to be delivered by unplanned cesarean (aOR, 3.08; 95% CI, 2.52-3.75) and instrumental delivery (aOR, 3.03; 95% CI, 2.46-3.75). Associations were strengthened in primiparae. Normal HC/high BW was not associated with unplanned cesarean (aOR, 1.18; 95% CI, 0.91-1.54), while large HC/high BW was (aOR, 1.93; 95% CI, 1.47-2.52). Analysis of unplanned cesarean indications showed large HC infants had more failure to progress (27.7% vs 14.1%, P < .001), while smaller HC infants had more fetal distress (23.4% vs 16.9%, P < .05). A large HC is more strongly associated with unplanned cesarean and instrumental delivery than high BW. Prospective studies are needed to test fetal HC as a predictive parameter for prelabor counseling of women with "big babies." Copyright © 2015 Elsevier Inc. All rights reserved.

Peripheral Administration of Tetanus Toxin Hc Fragment Prevents MPP+ Toxicity In Vivo.

PubMed

Moreno-Galarza, Natalia; Mendieta, Liliana; Palafox-Sánchez, Victoria; Herrando-Grabulosa, Mireia; Gil, Carles; Limón, Daniel I; Aguilera, José

2018-02-19

Several studies have shown that intrastriatal application of 1-methyl-4-phenylpyridinium (MPP + ) produces similar biochemical changes in rat to those seen in Parkinson's disease (PD), such as dopaminergic terminal degeneration and consequent appearance of motor deficits, making the MPP + lesion a widely used model of parkinsonism in rodents. Previous results from our group have shown a neuroprotective effect of the carboxyl-terminal domain of the heavy chain of tetanus toxin (Hc-TeTx) under different types of stress. In the present study, pretreatment with the intraperitoneal injection of Hc-TeTx in rats prevents the decrease of tyrosine hydroxylase immunoreactivity in the striatum due to injury with MPP + , when applied stereotaxically in the striatum. Similarly, striatal catecholamine contents are restored, as well as the levels of two other dopaminergic markers, the dopamine transporter (DAT) and the vesicular monoamine transporter-2 (VMAT-2). Additionally, uptake studies of [ 3 H]-dopamine and [ 3 H]-MPP + reveal that DAT action is not affected by Hc-TeTx, discarding a protective effect due to a reduced entry of MPP + into nerve terminals. Behavioral assessments show that Hc-TeTx pretreatment improves the motor skills (amphetamine-induced rotation, forelimb use, and adjusting steps) of MPP + -treated rats. Our results lead us to consider Hc-TeTx as a potential therapeutic tool in pathologies caused by impairment of dopaminergic innervation in the striatum, as is the case of PD.

Identification of mildly oxidized low-density lipoprotein (electronegative LDL) and its auto-antibodies IgG in children and adolescents hypercholesterolemic offsprings.

PubMed

Barros, Marcos Roberto Andrade Costa; Bertolami, Marcelo Chiara; Abdalla, Dulcinéia Saes Parra; Ferreira, Waldinai Pereira

2006-01-01

Oxidative modification of low-density lipoproteins (LDL) is an essential step in atherogenesis, generating minimally oxidized LDL, also called electronegative LDL [LDL(-)], which has chemotactic, cytotoxic and immunogenic properties. Serum LDL(-) and anti-LDL(-) auto-antibodies (IgG) were evaluated in 28 children and adolescents with familial hypercholesterolemia (FH) antecedents, with or without early coronary artery disease in first-degree relatives (eCAD), hypercholesterolemic (hc) or normocholesterolemic (nc) versus a control group of normocholesterolemic children without pathologic antecedents (C). ELISA method was used for detection of LDL(-) and anti-LDL(-) IgG. LDL(-) serum levels did not differ among the four groups (FH-eCAD-hc 41.4 +/- 24.9 microg/dl; FH-hc 38.3 +/- 11.2 microg/dl; FH-nc 47.3 +/- 17.0 microg/dl and C 44.2 +/- 28.8 microg/dl, p = 0.659). However, IgG anti-LDL(-) auto-antibodies were significantly higher in the control group in comparison to the FH groups with or without eCAD, independent of hypercholesterolemia or normocholesterolemia (FH-eCAD-hc 0.825 +/- 0.289 microg/dl; FH-hc 0.667 +/- 0.307 microg/dl; FH-nc 0.763 +/- 0.204 microg/dl and C 1.105 +/- 0.233 microg/dl, p = 0.006). When the auto-antibodies of groups with FH, with or without eCAD and with or without hypercholesterolemia were compared, no differences were found (p = 0.509). These results showed that FH and/or eCAD children and adolescents have lower titers of auto-antibodies anti-LDL(-) than children from normal families, independent of serum LDL-cholesterol or serum LDL(-).

2-(Naphthalen-1-yl)-4-(naphthalen-1-yl­methyl­idene)-1,3-oxazol-5(4H)-one

PubMed Central

Gündoğdu, Cevher; Alp, Serap; Ergün, Yavuz; Tercan, Barış; Hökelek, Tuncer

2011-01-01

In the title compound, C24H15NO2, the oxazole ring is oriented at dihedral angles of 10.09 (4) and 6.04 (4)° with respect to the mean planes of the naphthalene ring systems, while the two naphthalene ring systems make a dihedral angle of 4.32 (3)°. Intra­molecular C—H⋯N hydrogen bonds link the oxazole N atom to the naphthalene ring systems. In the crystal, inter­molecular weak C—H⋯O hydrogen bonds link the mol­ecules into centrosymmetric dimers. π–π contacts between the oxazole and naphthalene rings and between the naphthalene ring systems [centroid–centroid distances = 3.5947 (9) and 3.7981 (9) Å] may further stabilize the crystal structure. Three weak C—H⋯π inter­actions also occur. PMID:21754548

Molecular dynamics simulation reveals insights into the mechanism of unfolding by the A130T/V mutations within the MID1 zinc-binding Bbox1 domain.

PubMed

Zhao, Yunjie; Zeng, Chen; Massiah, Michael A

2015-01-01

The zinc-binding Bbox1 domain in protein MID1, a member of the TRIM family of proteins, facilitates the ubiquitination of the catalytic subunit of protein phosphatase 2A and alpha4, a protein regulator of PP2A. The natural mutation of residue A130 to a valine or threonine disrupts substrate recognition and catalysis. While NMR data revealed the A130T mutant Bbox1 domain failed to coordinate both structurally essential zinc ions and resulted in an unfolded structure, the unfolding mechanism is unknown. Principle component analysis revealed that residue A130 served as a hinge point between the structured β-strand-turn-β-strand (β-turn-β) and the lasso-like loop sub-structures that constitute loop1 of the ββα-RING fold that the Bbox1 domain adopts. Backbone RMSD data indicate significant flexibility and departure from the native structure within the first 5 ns of the molecular dynamics (MD) simulation for the A130V mutant (>6 Å) and after 30 ns for A130T mutant (>6 Å). Overall RMSF values were higher for the mutant structures and showed increased flexibility around residues 125 and 155, regions with zinc-coordinating residues. Simulated pKa values of the sulfhydryl group of C142 located near A130 suggested an increased in value to ~9.0, paralleling the increase in the apparent dielectric constants for the small cavity near residue A130. Protonation of the sulfhydryl group would disrupt zinc-coordination, directly contributing to unfolding of the Bbox1. Together, the increased motion of residues of loop 1, which contains four of the six zinc-binding cysteine residues, and the increased pKa of C142 could destabilize the structure of the zinc-coordinating residues and contribute to the unfolding.

Regulation of vascular endothelial genes by dietary flavonoids: structure-expression relationship studies and the role of the transcription factor KLF-2.

PubMed

Martínez-Fernández, Leyre; Pons, Zara; Margalef, Maria; Arola-Arnal, Anna; Muguerza, Begoña

2015-03-01

Physiological concentrations (1 μM) of 15 flavonoids were evaluated in human umbilical vein endothelial cells in the presence of hydrogen peroxide (H₂O₂) for their ability to affect endothelial nitric oxide synthase (eNOS) and endothelin-1 (ET-1) expression in order to establish the structural basis of their bioactivity. Flavonoid effects on eNOS transcription factor Krüpple like factor-2 (KLF-2) expression were also evaluated. All studied flavonoids appeared to be effective compounds for counteracting the oxidative stress-induced effects on vascular gene expression, indicating that flavonoids are an excellent source of functional endothelial regulator products. Notably, the more effective flavonoids for KLF-2 up-regulation resulted in the highest values for eNOS expression, showing that the increment of eNOS expression would take place through KLF-2 induction. Structure-activity relationship studies showed that the combinations of substructures on flavonoid skeleton that regulate eNOS expression are made up of the following elements: glycosylation and hydroxylation of C-ring, double bond C2=C3 at C-ring, methoxylation and hydroxylation of B-ring, ketone group in C4 at C-ring and glycosylation in C7 of A-ring, while flavonoid features involved in the reduction of vasoconstrictor ET-1 expression are as follows: double bond C2=C3 at C-ring glycosylation in C7 of A-ring and ketone group in C4 of C-ring. Copyright © 2015 Elsevier Inc. All rights reserved.

The effect of hypercholesterolemia on carbachol-induced contractions of the detrusor smooth muscle in rats: increased role of L-type Ca2+ channels.

PubMed

Balkanci, Zeynep Dicle; Pehlivanoğlu, Bilge; Bayrak, Sibel; Karabulut, Ismail; Karaismailoğlu, Serkan; Erdem, Ayşen

2012-11-01

To investigate a possible relation between hypercholesterolemia and detrusor smooth muscle function, we studied the contractile response to potassium challenge, carbachol (CCh), and the components of CCh-induced contractile mechanism in high-cholesterol diet-fed rats. Adult male Sprague-Dawley rats were fed with standard (control group, N = 17) or 4 % cholesterol diet (hypercholesterolemia group (HC), N = 16) for 4 weeks. Spontaneous contractions of detrusor muscle strips and their responses to potassium chloride (KCl) or cumulative dose-contraction curves to CCh were recorded. The effects of muscarinic receptor antagonists (methoctramin and/or 4-diphenylacetoxy-N-methylpiperidine), L-type Ca(+2) channel blocker (nifedipine), and/or rho-kinase inhibitor Y-27632 were investigated. Blood cholesterol level was increased in the HC group with no sign of atherosclerosis. The KCl-induced detrusor smooth muscle contractions were higher in HC, whereas spontaneous and CCh-induced responses were similar in both groups. Preincubation with receptor antagonist for M(3) but not for M(2) attenuated contraction significantly, shifting the dose-response curve to the right. This response was similar in both groups. Among two effector mechanisms of M(3)-mediated detrusor smooth muscle contraction, rho-kinase pathway was not affected by hypercholesterolemia, whereas blockade of L-type Ca(+2) channels potently reduced contractions. The results of this study point out a relation between hypercholesterolemia and contractile mechanism of detrusor smooth muscle likely to change urinary bladder function, via altering L-type Ca(+2) channels. Taken together with escalating incidence of hypercholesterolemia and lower urinary tract symptoms, it is a field which deserves to be investigated further.

Capillarization in skeletal muscle of rats with cardiac hypertrophy.

PubMed

Degens, Hans; Anderson, Rebecca K; Alway, Stephen E

2002-02-01

Exercise intolerance during chronic heart failure (CHF) is localized mainly in skeletal muscle. A decreased capillarization may impair exchange of oxygen between capillaries and muscle tissue and in this way contribute to exercise intolerance. We assessed changes in capillary supply in plantaris and diaphragm muscles of a rat aorta-caval fistula (ACF) preparation, a volume overload model for CHF. An ACF was created under equithesin anesthesia. Plantaris and diaphragm muscles were removed 6 wk postsurgery and examined for myosin heavy chain (MyHC) content and capillary supply. Cardiac hypertrophy was 96% (P < 0.002) after ACF. The Type IIb MyHC content of the plantaris muscles increased (33.9 +/- 3.3 vs 49.8 +/- 3.8%; mean +/- SEM) at the expense of Type IIa MyHC (17.6 +/- 1.8 vs 11.2 +/- 1.7%) in ACF rats (P < 0.05). In the diaphragm, the number of Type I (32.1 +/- 2.3 vs 40.6 +/- 2.7%) and IIb fibers (40.6 +/- 1.9 vs 49.6 +/- 3.6%) increased at the expense of Type IIa fibers (26.8 +/- 2.5 vs 9.4 +/- 0.9%) (P < 0.05). The capillary number per fiber did not change, and this indicated that no capillary loss occurred with ACF. Also, the capillary density was maintained in the diaphragm and plantaris muscles of ACF rats. Furthermore, the coupling between fiber type, size, and metabolic type of surrounding fibers, with the capillary supply to a fiber, was maintained in rats with an ACF. The cardiac hypertrophy induced by volume overload seems adequate to prevent atrophy and changes in the microcirculation of limb and diaphragm muscles.

Treatment of contaminated greywater using pelletised mine water sludge.

PubMed

Abed, Suhail N; Almuktar, Suhad A; Scholz, Miklas

2017-07-15

Precipitated sludge (ochre) obtained from a mine water treatment plant was considered as an adsorbent substance for pollutants, since ochre is relatively free from problematic levels of toxic elements, which could impair on the quality of water to be treated. Artificially created ochre pellets from mixing Portland cement with raw ochre sludge were utilised to remediate either high (HC) or low (LC) contaminated synthetic greywater (SGW) in mesocosm-scale stabilisation ponds at 2-day and 7-day contact times under real weather conditions in Salford. After a specific retention time, treated SGW was agitated before sampling to evaluate pollutant removal mechanisms (other than sedimentation) such as adsorption by ochre pellets, before replacing the treated water with new inflow SGW. The results showed that cement-ochre pellets have a high ability to adsorb ortho-phosphate-phosphorous (PO 4 -P) significantly (p < 0.05) by 70.7% and 56.0% at 7-day contact time for HC-SGW and LC-SGW, respectively. After the experiment, an analysis revealed that elements such as boron (B), cadmium (Cd), magnesium (Mg), manganese (Mn), nickel (Ni) and zinc (Zn) accumulated significantly (p < 0.05) within the ochre pellets. The notable accumulation of Cd within ochre pellets reflects the significant (p < 0.05) remediation of greywater during the first 35 and 20 successive times of treatment for HC-SGW at 2- and 7-day contact times, respectively. Cadmium was still adsorbed significantly (p < 0.05) during the treatment of LC-SGW. However, the calcium (Ca) content decreased significantly (p < 0.05) within ochre pellets treating both types of greywaters due to mobilisation. The corresponding increases of Ca in greywater were significant (p < 0.05). Copyright © 2017 Elsevier Ltd. All rights reserved.

Concise synthesis of the bryostatin A-ring via consecutive C-C bond forming transfer hydrogenations.

PubMed

Lu, Yu; Krische, Michael J

2009-07-16

Under the conditions of C-C bond forming transfer hydrogenation, 1,3-propanediol 1 engages in double asymmetric carbonyl allylation to furnish the C(2)-symmetric diol 2. Double ozonolysis of 2 followed by TBS protection delivers aldehyde 3, which is subject to catalyst directed carbonyl reverse prenylation via transfer hydrogenation to deliver neopentyl alcohol 4 and, ultimately, the bryostatin A-ring 7. Through use of two consecutive C-C bond forming transfer hydrogenations, the Evans' bryostatin A-ring 7 is prepared in less than half the manipulations previously reported.

40 CFR 86.348-79 - Alternative to fuel H/C analysis.

Code of Federal Regulations, 2010 CFR

2010-07-01

... PROGRAMS (CONTINUED) CONTROL OF EMISSIONS FROM NEW AND IN-USE HIGHWAY VEHICLES AND ENGINES Emission... average H/C ratios are used for all calculations. (1) #1B1 Diesel: 1:93 (2) #1B2 Diesel: 1:80 (3) Gasoline...

Kinetics and thermochemistry of polyatomic free radicals: New results and new understandings

NASA Technical Reports Server (NTRS)

Gutman, David; Slagle, Irene R.

1990-01-01

An experimental facility for the study of the chemical kinetics of polyatomic free radicals is described which consists of a heatable tubular reactor coupled to a photoionization mass spectrometer. Its use in different kinds of chemical kinetic studies is also discussed. Examples presented include studies of the C2H3 + O2, C2H3 + HC1, CH3 + O, and CH3 + CH3 reactions. The heat of formation of C2H3 was obtained from the results of the study of the C2H3 + HC1 reaction.

A Mobile Health Intervention for Self-Management and Lifestyle Change for Persons With Type 2 Diabetes, Part 2: One-Year Results From the Norwegian Randomized Controlled Trial RENEWING HEALTH

PubMed Central

Torbjørnsen, Astrid; Wahl, Astrid Klopstad; Jenum, Anne Karen; Småstuen, Milada Cvancarova; Årsand, Eirik; Ribu, Lis

2014-01-01

Background Self-management is crucial in the daily management of type 2 diabetes. It has been suggested that mHealth may be an important method for enhancing self-management when delivered in combination with health counseling. Objective The objective of this study was to test whether the use of a mobile phone–based self-management system used for 1 year, with or without telephone health counseling by a diabetes specialist nurse for the first 4 months, could improve glycated hemoglobin A1c (HbA1c) level, self-management, and health-related quality of life compared with usual care. Methods We conducted a 3-arm prospective randomized controlled trial involving 2 intervention groups and 1 control group. Eligible participants were persons with type 2 diabetes with an HbA1c level ≥7.1% (≥54.1 mmol/mol) and aged ≥18 years. Both intervention groups received the mobile phone–based self-management system Few Touch Application (FTA). The FTA consisted of a blood glucose–measuring system with automatic wireless data transfer, diet manual, physical activity registration, and management of personal goals, all recorded and operated using a diabetes diary app on the mobile phone. In addition, one intervention group received health counseling based on behavior change theory and delivered by a diabetes specialist nurse for the first 4 months after randomization. All groups received usual care by their general practitioner. The primary outcome was HbA1c level. Secondary outcomes were self-management (heiQ), health-related quality of life (SF-36), depressive symptoms (CES-D), and lifestyle changes (dietary habits and physical activity). Data were analyzed using univariate methods (t test, ANOVA) and multivariate linear and logistic regression. Results A total of 151 participants were randomized: 51 to the FTA group, 50 to the FTA-health counseling (FTA-HC) group, and 50 to the control group. Follow-up data after 1 year were available for 120 participants (79%). HbA1c level decreased in all groups, but did not differ between groups after 1 year. The mean change in the heiQ domain skills and technique acquisition was significantly greater in the FTA-HC group after adjusting for age, gender, and education (P=.04). Other secondary outcomes did not differ between groups after 1 year. In the FTA group, 39% were substantial users of the app; 34% of the FTA-HC group were substantial users. Those aged ≥63 years used the app more than their younger counterparts did (OR 2.7; 95% CI 1.02-7.12; P=.045). Conclusions The change in HbA1c level did not differ between groups after the 1-year intervention. Secondary outcomes did not differ between groups except for an increase in the self-management domain of skill and technique acquisition in the FTA-HC group. Older participants used the app more than the younger participants did. PMID:25499872

Crystal structures of three 3-chloro-3-methyl-2,6-di­aryl­piperidin-4-ones

PubMed Central

Arulraj, R.; Sivakumar, S.; Kaur, Manpreet; Jasinski, Jerry P.

2017-01-01

The syntheses and crystal structure of 3-chloro-3-methyl-r-2,c-6-di­phenyl­piperidin-4-one, C18H18ClNO, (I), 3-chloro-3-methyl-r-2,c-6-di-p-tolyl­piperidin-4-one, C20H22ClNO, (II), and 3-chloro-3-methyl-r-2,c-6-bis­(4-chloro­phen­yl)piperidin-4-one, C18H16Cl3NO, (III), are described. In each structure, the piperidine ring adopts a chair conformation and dihedral angles between the mean planes of the phenyl rings are 58.4 (2), 73.5 (5) and 78.6 (2)° in (I), (II) and (III), respectively. In the crystals, mol­ecules are linked into C(6) chains by weak N—H⋯O hydrogen bonds and C—H⋯π inter­actions are also observed. PMID:28217321

Plasma zinc in institutionalized elderly individuals: Relation with immune and cardiometabolic biomarkers.

PubMed

Sales, Márcia Cristina; de Oliveira, Larissa Praça; de Araújo Cabral, Natalia Louise; de Sousa, Sara Estéfani Soares; das Graças Almeida, Maria; Lemos, Telma Maria Araújo Moura; de Oliveira Lyra, Clélia; de Lima, Kenio Costa; Sena-Evangelista, Karine Cavalcanti Mauricio; de Fatima Campos Pedrosa, Lucia

2018-04-24

Changes in zinc metabolism caused by aging and the institutionalization process may contribute to zinc deficiency in elderly individuals. Hypozincemia results in changes in glycemic, lipid, and inflammatory profiles. The aim of this study was to evaluate plasma zinc concentrations and their relationships with sociodemographic, dietary, inflammatory, and cardiometabolic biomarkers in institutionalized elderly individuals. A cross-sectional study was carried out including 255 elderly adults living in nursing homes. The associations between plasma zinc and dietary zinc intake, sociodemographic indicators, and glycemic, lipid, and inflammatory biomarkers were evaluated. Independent variables were analyzed according to quartiles of plasma zinc concentrations (Q1: <71.1 μg/dL; Q2: 71.1-83.3 μg/dL; Q3: <83.3-93.7 μg/dL; Q4: >93.7 μg/dL). The relationship between plasma zinc concentrations and predictor variables was also tested. In Q1, higher concentrations of the following variables were observed, compared with those in other quartiles: total cholesterol and low-density lipoprotein cholesterol (LDL-c; Q1 > Q2, Q3, Q4; all p <0.001); triglycerides (Q1 > Q3, Q4; all p < 0.001); interleukin (IL)-6 (Q1 > Q3, Q4; p = 0.024 and p = 0.010, respectively); tumor necrosis factor (TNF)-α (Q1 > Q3, p = 0.003). A significant reduction in plasma zinc concentrations was observed with increasing age-adjusted institutionalization time (Δ = - 0.10; 95% confidence interval [CI]: -0.18 to -0.01). The concentrations of total cholesterol (Δ = - 0.19; 95% CI: -0.23 to -0.15), LDL-c (Δ = - 0.19; 95% CI: -0.23 to -0.15), triglycerides (Δ = - 0.11; 95% CI: -0.16 to -0.06), IL-6 (Δ = - 1.41; 95% CI: -2.64 to -0.18), and TNF-α (Δ = - 1.04; 95% CI: -1.71 to -0.36) were also significantly increased. In conclusion, decreased plasma zinc concentrations were associated with longer institutionalization time and worse lipid and inflammatory profiles in elderly institutionalized individuals. Published by Elsevier GmbH.

Synthesis, structural characterization and density functional studies of ethyl 4-(biphenyl-4-yl)-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexahydroquinoline-3-carboxylate A non-merohedral twinned structure

NASA Astrophysics Data System (ADS)

Yıdırım, Sema Öztürk; Büyükmumcu, Zeki; Butcher, Ray J.; Çetin, Gökalp; Şimşek, Rahime; Şafak, Cihat

2018-07-01

1,4-Dihydropyridine (1,4-DHP) derivatives have the reducing effect of extracellular Ca2+ ions influx on the L-type calcium channel. Because of this effect many 1,4-DHP derivatives are potent calcium channel blockers and antihypertensive agents. The biphenyl group is present in the structures of the most biologically active compounds and thus is an important group. By introducing this moiety into the structure of various compounds, active compounds are obtained. Thus, pharmacologically active structures can be condensed with the biphenyl structure to achieve novel biologically active compounds or compounds with increased activity. In this study, to achieve an active calcium channel blocker compound, the biphenyl group was introduced into the 1,4-DHP structure. The structure of the compound is proved by IR, 1H NMR, Mass spectroscopy, X-ray crystallography and elemental analysis. The cytotoxic activity assays have continued and positive results have been obtained. The phenyl rings [C16-C21 and C22-C27] make dihedral angles of 84.4 (1) and 87.5 (1)°, respectively, with the 1,4-dihydropyridine ring [N1/C1/C4-C9]. In the crystal, adjacent molecules are linked by Nsbnd H … O and Csbnd H … O hydrogen bonds into chains parallel to [010].

Implication of the ryanodine receptor in TRPV4-induced calcium response in pulmonary arterial smooth muscle cells from normoxic and chronically hypoxic rats.

PubMed

Dahan, Diana; Ducret, Thomas; Quignard, Jean-François; Marthan, Roger; Savineau, Jean-Pierre; Estève, Eric

2012-11-01

There is a growing body of evidence indicating that transient receptor potential (TRP) channels are implicated in calcium signaling and various cellular functions in the pulmonary vasculature. The aim of this study was to investigate the expression, functional role, and coupling to reticulum calcium channels of the type 4 vanilloid TRP subfamily (TRPV4) in the pulmonary artery from both normoxic (Nx) and chronically hypoxic (CH) rats. Activation of TRPV4 with the specific agonist 4α-phorbol-12,13-didecanoate (4α-PDD, 5 μM) increased the intracellular calcium concentration ([Ca(2+)](i)). This effect was significantly reduced by a high concentration of ryanodine (100 μM) or chronic caffeine (5 mM) that blocked ryanodine receptor (RyR) but was insensitive to xestospongin C (10 μM), an inositol trisphosphate receptor antagonist. Inhibition of RyR1 and RyR3 only with 10 μM of dantrolene did not attenuate the 4α-PDD-induced [Ca(2+)](i) increase. Western blotting experiments revealed the expression of TRPV4 and RyR2 with an increase in both receptors in pulmonary arteries from CH rats vs. Nx rats. Accordingly, the 4α-PDD-activated current, measured with patch-clamp technique, was increased in pulmonary artery smooth muscle cells (PASMC) from CH rats vs. Nx rats. 4α-PDD increased isometric tension in artery rings, and this response was also potentiated under chronic hypoxia conditions. 4α-PDD-induced calcium response, current, and contraction were all inhibited by the selective TRPV4 blocker HC-067047. Collectively, our findings provide evidence of the interplay between TRPV4 and RyR2 in the Ca(2+) release mechanism and contraction in PASMC. This study provides new insights onto the complex calcium signaling in PASMC and point out the importance of the TRPV4-RyR2 signaling pathway under hypoxic conditions that may lead to pulmonary hypertension.

Investigation of the hydrochlorination of SiCl4

NASA Technical Reports Server (NTRS)

Mui, J. Y. P.

1982-01-01

The hyrochlorination of SiC14 and m.g. silicon metal to produce SiHC13, was investigated. Reaction kinetic measurements were carried out to collect additional rate data at 525 C and 550 C. A theoretical study was carried out to provide a kinetic model and a rate equation for the hydrochlorination reaction. Results of this preliminary study show that the rate of formation of SiHC13 follows a pseudo first order kinetics. The rate constants were measured at three temperatures, 550 C, 500 C and 450 C, respectively. The activation energy was determined from the Arrhenius plot to give a value of 13.2 Kcal/mole. The design of a quartz reactor to measure reaction rates and equilibrium conversion of SiHC13 at reaction temperature up to 650 C was completed.

dl-Asparaginium nitrate

PubMed Central

Moussa Slimane, Nabila; Cherouana, Aouatef; Bendjeddou, Lamia; Dahaoui, Slimane; Lecomte, Claude

2009-01-01

In the title compound, C4H9N2O3 +·NO3 −, alternatively called (1RS)-2-carbamoyl-1-carboxy­ethanaminium nitrate, the asymmetric unit comprises one asparaginium cation and one nitrate anion. The strongest cation–cation O—H⋯O hydrogen bond in the structure, together with other strong cation–cation N—H⋯O hydrogen bonds, generates a succession of infinite chains of R 2 2(8) rings along the b axis. Additional cation–cation C—H⋯O hydrogen bonds link these chains into two-dimensional layers formed by alternating R 4 4(24) and R 4 2(12) rings. Connections between these layers are provided by the strong cation–anion N—H⋯O hydrogen bonds, as well as by one weak C—H⋯O inter­action, thus forming a three-dimensional network. Some of the cation–anion N—H⋯O hydrogen bonds are bifurcated of the type D—H⋯(A 1,A 2). PMID:21577586

The chemistry of (ring)Ru sup 2+ (ring = tetramethylthiophene, p-cymene)

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

Ganja, E.A.; Rauchfuss, T.B.; Stern, C.L.

1991-01-01

Described are the compounds ((ring)Ru(OTf){sub 2}){sub x}, where ring = 2,3,4,5-tetramethylthiophene (TMT, 1), and p-cymene (2). These electrophilic reagents serve as precursors to ((ring)RuL{sub 3}){sup 2+}, where L{sub 3} = (H{sub 2}O){sub 3}, (NH{sub 3}){sub 3}, and (PH{sub 3}){sub 3}. Solutions of 1 and 2 react with carbon monoxide to give (ring)Ru(CO)(OTf){sub 2}. The addition of thiophenes to CH{sub 2}Cl{sub 2} solutions of 1 or 2 leads to the precipitation of the sandwich compounds ((ring)(SC{sub 4}R{sub 4})Ru)(OTf){sub 2}, where SC{sub 4}R{sub 4} = thiophene, 2,5-dimethylthiophene, and TMT. ((TMT)Ru(H{sub 2}O){sub 3})(OTf){sub 2} was characterized by single-crystal X-ray crystallography, which established amore » piano-stool geometry with a planar TMT ligand. ((TMT)Ru(D{sub 2}O){sub 3})(OTf){sub 2} decomposes in D{sub 2}O solution at 150C to give ((TMT){sub 2}Ru){sup 2+}, which undergoes selective deuteration at the 2,5-methyl groups. D{sub 2}O solutions of ((TMT){sub 2}Ru){sup 2+} undergo photochemical loss of one TMT ligand in water to give ((TMT)Ru(H{sub 2}O){sub 3}){sup 2+}. A procedure is described for the reversible loading of 1 onto {gamma}-alumina, which in turn was characterized by {sup 13}C CP-MAS NMR spectroscopy.« less

3,3,6,6-Tetra-methyl-9-(2-nitro-phen-yl)-3,4,6,7-tetra-hydro-2H-xanthene-1,8(5H,9H)-dione.

PubMed

Mo, Yingming; Zang, Hong-Jun; Cheng, Bo-Wen

2010-07-31

In the title compound, C(23)H(25)NO(5), the pyran ring adopts a flattened boat conformation, while the two cyclo-hexenone rings are in envelope conformations. The 3-nitro-phenyl ring is almost perpendicular to the pyran ring, making a dihedral angle of 87.1 (3)°.

Experimental investigation on thermochemical sulfate reduction by H2S initiation

USGS Publications Warehouse

Zhang, T.; Amrani, A.; Ellis, G.S.; Ma, Q.; Tang, Y.

2008-01-01

Hydrogen sulfide (H2S) is known to catalyze thermochemical sulfate reduction (TSR) by hydrocarbons (HC), but the reaction mechanism remains unclear. To understand the mechanism of this catalytic reaction, a series of isothermal gold-tube hydrous pyrolysis experiments were conducted at 330 ??C for 24 h under a constant confining pressure of 24.1 MPa. The reactants used were saturated HC (sulfur-free) and CaSO4 in the presence of variable H2S partial pressures at three different pH conditions. The experimental results showed that the in-situ pH of the aqueous solution (herein, in-situ pH refers to the calculated pH of aqueous solution under the experimental conditions) can significantly affect the rate of the TSR reaction. A substantial increase in the TSR reaction rate was recorded with a decrease in the in-situ pH value of the aqueous solution involved. A positive correlation between the rate of TSR and the initial partial pressure of H2S occurred under acidic conditions (at pH ???3-3.5). However, sulfate reduction at pH ???5.0 was undetectable even at high initial H2S concentrations. To investigate whether the reaction of H2S(aq) and HSO4- occurs at pH ???3, an additional series of isothermal hydrous pyrolysis experiments was conducted with CaSO4 and variable H2S partial pressures in the absence of HC at the same experimental temperature and pressure conditions. CaSO4 reduction was not measurable in the absence of paraffin even with high H2S pressure and acidic conditions. These experimental observations indicate that the formation of organosulfur intermediates from H2S reacting with hydrocarbons may play a significant role in sulfate reduction under our experimental conditions rather than the formation of elemental sulfur from H2S reacting with sulfate as has been suggested previously (Toland W. G. (1960) Oxidation of organic compounds with aqueous sulphate. J. Am. Chem. Soc. 82, 1911-1916). Quantification of labile organosulfur compounds (LSC), such as thiols and sulfides, was performed on the products of the reaction of H2S and HC from a series of gold-tube non-isothermal hydrous pyrolysis experiments conducted at about pH 3 from 300 to 370 ??C and a 0.1-??C/h heating rate. Incorporation of sulfur into HC resulted in an appreciable amount of thiol and sulfide formation. The rate of LSC formation positively correlated with the initial H2S pressure. Thus, we propose that the LSC produced from H2S reaction with HC are most likely the reactive intermediates for H2S initiation of sulfate reduction. We further propose a three-step reaction scheme of sulfate reduction by HC under reservoir conditions, and discuss the geological implications of our experimental findings with regard to the effect of formation water and oil chemistry, in particular LSC content. ?? 2008 Elsevier Ltd. All rights reserved.

Thermodynamic properties of pressurized PH3 superconductor

NASA Astrophysics Data System (ADS)

Koka, S.; Rao, G. Venugopal

2018-05-01

The paper presents the superconducting thermodynamic functions determined for pressurized phosphorus trihydride (PH3). In particular, free energy difference ΔF, thermodynamic critical field Hc, specific heat etc. have been calculated using analytical expressions. The calculations were performed in the frame work of the strong-coupling formalism. The obtained dimensionless parameters: RΔ ≡ 2Δ(0)/kBTc, RC ≡ ΔC(Tc)/CN(Tc) and RH≡TcCN(Tc)/Hc2(0) are 4.05, 1.96 and 0.156 respectively, which significantly differ from the values arising from the BCS theory of superconductivity. The thermodynamic properties strongly depend on the depairing electron correlations and retardation effects.

4-Meth-oxy-3-(meth-oxy-meth-yl)benzalde-hyde.

PubMed

Zhang, Jing-Chao; Sun, Jun; Zhang, Juan; Liu, Guang-Lin; Guo, Cheng

2013-01-01

In the title compound, C10H12O3, the dihedral angle between the benzene ring and the meth-oxy-methyl side chain is 9.7 (2)°. The O atom of the aldehyde group and the C atom of the meth-oxy group deviate from the plane of the ring by 0.039 (3) and 0.338 (4) Å, respectively. The only inter-molecular inter-actions are very weak C-H⋯π inter-actions.