C5b-9 Staining Correlates With Clinical and Tumor Stage in Gastric Adenocarcinoma.

PubMed

Chen, Jian; Yang, Wei-Jun; Sun, Hai-Jian; Yang, Xia; Wu, Yu-Zhang

2016-08-01

The complement system is a critical part of the immune response, acting in defense against viral infections, clearance of immune complexes, and maintenance of tissue homeostasis. Upregulated expression of the terminal complement complex, C5b-9, has been observed on various tumor cells, such as stomach carcinoma cells, and on cells in the necrotic regions of these tumors as well; however, whether and how C5b-9 is related to gastric cancer progression and severity remains unknown. In this study, human gastric adenocarcinoma (HGAC) tissues (n=47 cases) and patient-matched adjacent nontumoral parenchyma (n=20 cases) were evaluated by tissue microarray and immunohistochemistry. The HGAC tissues showed upregulated C5b-9 expression. Multinomial logistic regression and likelihood ratio testing showed that overexpression of C5b-9 in HGAC tissue was significantly correlated with clinical stage (P=0.007) and tumor stage (P=0.005), but not with tumor distant organ metastasis, lymphoid nodal status, sex, or age. Patients with late-stage gastric adenocarcinoma had a higher amount of tumor cells showing positive staining for C5b-9 than patients with early-stage disease. These results may help in diagnosis and assessment of disease severity of human gastric carcinoma.

Plasma Kallikrein-Kinin system mediates immune-mediated renal injury in trichloroethylene-sensitized mice.

PubMed

Wang, Hui; Zhang, Jia-Xiang; Ye, Liang-Ping; Li, Shu-Long; Wang, Feng; Zha, Wan-Sheng; Shen, Tong; Wu, Changhao; Zhu, Qi-Xing

2016-07-01

Trichloroethylene (TCE) is a major environmental pollutant. An immunological response is a newly-recognized mechanism for TCE-induced kidney damage. However, the role of the plasma kallikrein-kinin system (KKS) in immune-mediated kidney injury has never been examined. This study aimed to explore the role of the key components of the KKS, i.e. plasma kallikrein (PK), bradykinin (BK) and its receptors B1R and B2R, in TCE-induced kidney injury. A mouse model of skin sensitization was used to explore the mechanism of injury with or without a PK inhibitor PKSI. Kidney function was evaluated by measuring blood urea nitrogen (BUN) and creatinine (Cr) in conjunction with histopathologic characterization. Plasma BK was determined by ELISA; Renal C5b-9 membrane attack complex was evaluated by immunohistochemistry. Expression of BK and PK in the kidney was detected by immunofluorescence. mRNA and protein levels of B1R and B2R were assessed by real-time qPCR and Western blot. As expected, numerous inflammatory cell infiltration and tubular epithelial cell vacuolar degeneration were observed in TCE-sensitized mice. Moreover, serum BUN and Cr and plasma BK were increased. In addition, deposition of BK, PK and C5b-9 were observed and B1R and B2R mRNA and proteins levels were up-regulated. Pre-treatment with PKSI, a highly selective inhibitor of PK, alleviated TCE-induced renal damage. In addition, PKSI attenuated TCE-induced up-regulation of BK, PK and its receptors and C5b-9. These results provided the first evidence that activation of the KKS contributed to immune-mediated renal injury induced by TCE and also helped to identify the KKS as a potential therapeutic target for mitigating chemical sensitization-induced renal damage.

Molecular characterization of the alpha subunit of complement component C8 (GcC8α) in the nurse shark (Ginglymostoma cirratum)

PubMed Central

Aybar, Lydia; Shin, Dong-Ho; Smith, Sylvia L.

2009-01-01

Target cell lysis by complement is achieved by the assembly and insertion of the membrane attack complex (MAC) composed of glycoproteins C5b through C9. The lytic activity of shark complement involves functional analogues of mammalian C8 and C9. Mammalian C8 is composed of α, β, and γ subunits. The subunit structure of shark C8 is not known. This report describes a 2341 nucleotide sequence that translates into a polypeptide of 589 amino acid residues, orthologue to mammalian C8α and has the same modular architecture with conserved cysteines forming the peptide bond backbone. The C8γ-binding cysteine is conserved in the perforin-like domain. Hydrophobicity profile indicates the presence of hydrophobic residues essential for membrane insertion. It shares 41.1% and 47.4 % identity with human and Xenopus C8α respectively. Southern blot analysis showed GcC8α exists as a single copy gene expressed in most tissues except the spleen with the liver being the main site of synthesis. Phylogenetic analysis places it in a clade with C8α orthologs and as a sister taxa to the Xenopus. PMID:19524681

Ring Opening Polymerization and Copolymerization of Cyclic Esters Catalyzed by Group 2 Metal Complexes Supported by Functionalized P-N Ligands.

PubMed

Harinath, Adimulam; Bhattacharjee, Jayeeta; Sarkar, Alok; Nayek, Hari Pada; Panda, Tarun K

2018-03-05

We report the preparation of alkali and alkaline earth (Ae) metal complexes supported by 2-picolylamino-diphenylphosphane chalcogenide [(Ph 2 P(=E)NHCH 2 (C 5 H 4 N)] [E = S (1-H); Se (2-H)] ligands. The treatment of the protic ligand, 1-H or 2-H, with alkali metal hexamethyldisilazides at room temperature afforded the corresponding alkali metal salts [M(THF) 2 (Ph 2 P(=E)NCH 2 (C 5 H 4 N)] [M = Li, E = S (3a), Se (3b)] and [{M(THF) n (Ph 2 P(=E)NCH 2 (C 5 H 4 N)} 2 ] [M = Na, E = S (4a), Se (4b); M = K, E = Se (5b)] in good yield. The homoleptic Ae metal complexes [κ 2 -(Ph 2 P(=Se)NCH 2 (C 5 H 4 N)Mg(THF)] (6b) and [κ 3 -{(Ph 2 P(=Se)NCH 2 (C 5 H 4 N)} 2 M(THF) n ] (M = Ca (7b), Sr (8b), Ba (9b)] were synthesized by the one-pot reaction of 2-H with [KN(SiMe 3 ) 2 ] and MI 2 in a 2:2:1 molar ratio at room temperature. The molecular structures of the protic-ligands 1-H and 2-H, as well as complexes 3a,b-5a,b and 6b-9b were established using single-crystal X-ray analysis. The Ae metal complexes 6b-9b were tested for ring-opening polymerization (ROP) of racemic lactide ( rac-LA) and copolymerization of rac-LA and ε-caprolactone (ε-CL) at room temperature. In the ROP of rac-LA, the calcium complex 7b exhibited high isoselectivity, with P i = 0.89, whereas both the barium and strontium complexes showed lower isoselectivity with P i = 0.78-0.62. In the copolymerization of rac-LA and ε-CL, both barium and strontium complexes proved to be efficient precatalysts for the formation of the block copolymer rac-LA-CL, but the reactivity of 9b was found to be better than that of 8b. All the polymers were fully characterized using differential scanning calorimetry, thermogravimetric analysis, and gel permeation chromatography analyses. Kinetic studies on the ROP reaction of LA confirmed that the rate of polymerization followed the order Ba ≫ Sr ≈ Ca.

Blood SC5b-9 complement levels increase at parturition during term and preterm labor.

PubMed

Segura-Cervantes, Enrique; Mancilla-Ramirez, Javier; Zurita, Luis; Paredes, Yuriria; Arredondo, José Luis; Galindo-Sevilla, Norma

2015-06-01

We explored the hypothesis that complement, an innate and adaptive immune effector, is active in the plasma of parturient women and is deposited on fetal membranes collected after delivery. A cross-sectional study was designed to evaluate complement activity at parturition. Pregnant women (n = 97) between 15 and 41 years of age were enrolled in a hospital protocol during the perinatal period to assess both SC5b-9 complement activity in blood and complement deposition on fetal membranes during parturition. Soluble SC5b-9 complement activity in plasma fractions was measured using a standard enzyme-linked immunosorbent assay (ELISA) that included specific anti-complement antibodies. Complement deposition on membranes was analyzed using immuno-dot blots and immunohistochemistry. Soluble SC5b-9 complement complex levels were increased in the plasma of women during term labor (TL; median 3361; range 1726-5670 ng/mL), preterm labor (PL; median 2958; range 1552-7092 ng/mL), and preterm premature rupture of membranes (PPROM; median 2272; range 167-6540 ng/mL) compared with pregnant women who were not in labor (P; median 1384; range 174-4570 ng/mL; P < 0.001, Kruskal-Wallis test). Active complement, as assessed by the C9 neo-antigen in C5b-9 complexes, was deposited on fetal membranes, with no difference between term and preterm delivery. The deposition of active complement on fetal membranes was confirmed by immunohistochemistry. Women who underwent non-labor-indicated Cesarean sections did not exhibit complement deposition. Soluble SC5b-9 complement complex levels increased in the plasma of women during parturition, and complement C5b-9 complexes were deposited on fetal membranes. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Novel Mutations Causing C5 Deficiency in Three North-African Families.

PubMed

Colobran, Roger; Franco-Jarava, Clara; Martín-Nalda, Andrea; Baena, Neus; Gabau, Elisabeth; Padilla, Natàlia; de la Cruz, Xavier; Pujol-Borrell, Ricardo; Comas, David; Soler-Palacín, Pere; Hernández-González, Manuel

2016-05-01

The complement system plays a central role in defense to encapsulated bacteria through opsonization and membrane attack complex (MAC) dependent lysis. The three activation pathways (classical, lectin, and alternative) converge in the cleavage of C5, which initiates MAC formation and target lysis. C5 deficiency is associated to recurrent infections by Neisseria spp. In the present study, complement deficiency was suspected in three families of North-African origin after one episode of invasive meningitis due to a non-groupable and two uncommon Meningococcal serotypes (E29, Y). Activity of alternative and classical pathways of complement were markedly reduced and the measurement of terminal complement components revealed total C5 absence. C5 gene analysis revealed two novel mutations as causative of the deficiency: Family A propositus carried a homozygous deletion of two adenines in the exon 21 of C5 gene, resulting in a frameshift and a truncated protein (c.2607_2608del/p.Ser870ProfsX3 mutation). Families B and C probands carried the same homozygous deletion of three consecutive nucleotides (CAA) in exon 9 of the C5 gene, leading to the deletion of asparagine 320 (c.960_962del/p.Asn320del mutation). Family studies confirmed an autosomal recessive inheritance pattern. Although sharing the same geographical origin, families B and C were unrelated. This prompted us to investigate this mutation prevalence in a cohort of 768 North-African healthy individuals. We identified one heterozygous carrier of the p.Asn320del mutation (allelic frequency = 0.065 %), indicating that this mutation is present at low frequency in North-African population.

Cooperation between Hsp90 and mortalin/GRP75 in resistance to cell death induced by complement C5b-9.

PubMed

Rozenberg, Perri; Ziporen, Lea; Gancz, Dana; Saar-Ray, Moran; Fishelson, Zvi

2018-02-02

Cancer cells are commonly more resistant to cell death activated by the membranolytic protein complex C5b-9. Several surface-expressed and intracellular proteins that protect cells from complement-dependent cytotoxicity (CDC) have been identified. In this study, we investigated the function of heat shock protein 90 (Hsp90), an essential and ubiquitously expressed chaperone, overexpressed in cancer cells, in C5b-9-induced cell death. As shown, inhibition of Hsp90 with geldanamycin or radicicol is enhancing sensitivity of K562 erythroleukemia cells to CDC. Similarly, Hsp90 inhibition confers in Ramos B cell lymphoma cells elevated sensitivity to treatment with rituximab and complement. C5b-9 deposition is elevated on geldanamycin-treated cells. Purified Hsp90 binds directly to C9 and inhibits zinc-induced C9 polymerization, indicating that Hsp90 may act directly on the C5b-9 complex. Mortalin, also known as stress protein 70 or GRP75, is a mitochondrial chaperone that confers resistance to CDC. The postulated cooperation between Hsp90 and mortalin in protection from CDC was tested. Geldanamycin failed to sensitize toward CDC cells with knocked down mortalin. Direct binding of Hsp90 to mortalin was shown by co-immunoprecipitation in cell extracts after triggering with complement as well as by using purified recombinant proteins. These results provide an insight into the protective mechanisms utilized by cancer cells to evade CDC. They suggest that Hsp90 protects cells from CDC by inhibiting, together with mortalin, C5b-9 assembly and/or stability at the plasma membrane.

Crystal Structure of the MACPF Domain of Human Complement Protein C8[alpha] in Complex with the C8[gamma] Subunit

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

Slade, Daniel J.; Lovelace, Leslie L.; Chruszcz, Maksymilian

2010-03-04

Human C8 is one of five complement components (C5b, C6, C7, C8, and C9) that assemble on bacterial membranes to form a porelike structure referred to as the 'membrane attack complex' (MAC). C8 contains three genetically distinct subunits (C8{alpha}, C8{beta}, C8{gamma}) arranged as a disulfide-linked C8{alpha}-{gamma} dimer that is noncovalently associated with C8{beta}. C6, C7 C8{alpha}, C8{beta}, and C9 are homologous. All contain N- and C-terminal modules and an intervening 40-kDa segment referred to as the membrane attack complex/perforin (MACPF) domain. The C8{gamma} subunit is unrelated and belongs to the lipocalin family of proteins that display a {beta}-barrel fold andmore » generally bind small, hydrophobic ligands. Several hundred proteins with MACPF domains have been identified based on sequence similarity; however, the structure and function of most are unknown. Crystal structures of the secreted bacterial protein Plu-MACPF and the human C8{alpha} MACPF domain were recently reported and both display a fold similar to those of the bacterial pore-forming cholesterol-dependent cytolysins (CDCs). In the present study, we determined the crystal structure of the human C8{alpha} MACPF domain disulfide-linked to C8{gamma} ({alpha}MACPF-{gamma}) at 2.15 {angstrom} resolution. The {alpha}MACPF portion has the predicted CDC-like fold and shows two regions of interaction with C8{gamma}. One is in a previously characterized 19-residue insertion (indel) in C8{alpha} and fills the entrance to the putative C8{gamma} ligand-binding site. The second is a hydrophobic pocket that makes contact with residues on the side of the C8{gamma} {beta}-barrel. The latter interaction induces conformational changes in {alpha}MACPF that are likely important for C8 function. Also observed is structural conservation of the MACPF signature motif Y/W-G-T/S-H-F/Y-X{sub 6}-G-G in {alpha}MACPF and Plu-MACPF, and conservation of several key glycine residues known to be important for refolding and pore formation by CDCs.« less

Controlled oxidation of organic sulfides to sulfoxides under ambient conditions by a series of titanium isopropoxide complexes using environmentally benign H2O2 as an oxidant.

PubMed

Panda, Manas K; Shaikh, Mobin M; Ghosh, Prasenjit

2010-03-07

Controlled oxidation of organic sulfides to sulfoxides under ambient conditions has been achieved by a series of titanium isopropoxide complexes that use environmentally benign H(2)O(2) as a primary oxidant. Specifically, the [N,N'-bis(2-oxo-3-R(1)-5-R(2)-phenylmethyl)-N,N'-bis(methylene-R(3))-ethylenediamine]Ti(O(i)Pr)(2) [R(1) = t-Bu, R(2) = Me, R(3) = C(7)H(5)O(2) (1b); R(1) = R(2) = t-Bu, R(3) = C(7)H(5)O(2) (2b); R(1) = R(2) = Cl, R(3) = C(7)H(5)O(2) (3b) and R(1) = R(2) = Cl, R(3) = C(6)H(5) (4b)] complexes efficiently catalyzed the sulfoxidation reactions of organic sulfides to sulfoxides at room temperature within 30 min of the reaction time using aqueous H(2)O(2) as an oxidant. A mechanistic pathway, modeled using density functional theory for a representative thioanisole substrate catalyzed by 4b, suggested that the reaction proceeds via a titanium peroxo intermediate 4c', which displays an activation barrier of 22.5 kcal mol(-1) (DeltaG(++)) for the overall catalytic cycle in undergoing an attack by the S atom of the thioanisole substrate at its sigma*-orbital of the peroxo moiety. The formation of the titanium peroxo intermediate was experimentally corroborated by a mild ionization atmospheric pressure chemical ionization (APCI) mass spectrometric technique.

Molecular characterization of the alpha subunit of complement component C8 (GcC8alpha) in the nurse shark (Ginglymostoma cirratum).

PubMed

Aybar, Lydia; Shin, Dong-Ho; Smith, Sylvia L

2009-09-01

Target cell lysis by complement is achieved by the assembly and insertion of the membrane attack complex (MAC) composed of glycoproteins C5b through C9. The lytic activity of shark complement involves functional analogues of mammalian C8 and C9. Mammalian C8 is composed of alpha, beta, and gamma subunits. The subunit structure of shark C8 is not known. This report describes a 2341 nucleotide sequence that translates into a polypeptide of 589 amino acid residues, orthologue to mammalian C8alpha and has the same modular architecture with conserved cysteines forming the peptide bond backbone. The C8gamma-binding cysteine is conserved in the perforin-like domain. Hydrophobicity profile indicates the presence of hydrophobic residues essential for membrane insertion. It shares 41.1% and 47.4% identity with human and Xenopus C8alpha respectively. Southern blot analysis showed GcC8alpha exists as a single copy gene expressed in most tissues except the spleen with the liver being the main site of synthesis. Phylogenetic analysis places it in a clade with C8alpha orthologs and as a sister taxa to the Xenopus. 2009 Elsevier Ltd.

High Levels of Soluble C5b-9 Complex in Dialysis Fluid May Predict Poor Prognosis in Peritonitis in Peritoneal Dialysis Patients.

PubMed

Mizuno, Masashi; Suzuki, Yasuhiro; Higashide, Keiko; Sei, Yumi; Iguchi, Daiki; Sakata, Fumiko; Horie, Masanobu; Maruyama, Shoichi; Matsuo, Seiichi; Morgan, B Paul; Ito, Yasuhiko

2017-01-01

We searched for indicators to predict the prognosis of infectious peritonitis by measuring levels of complement proteins and activation products in peritoneal dialysis (PD) fluid (PDF) of patients at early stages of peritonitis. We retrospectively analyzed the relationship between the levels of sC5b-9, C3 and C4 in PDF and the subsequent clinical prognosis. We measured levels of sC5b-9, C3 and C4 in PDF on days 1, 2 and 5 post-onset of peritonitis in 104 episodes of infectious peritonitis in PD patients from 2008 and retrospectively compared levels with clinical outcomes. Further analysis for the presence of causative microorganisms or to demonstrate bacterial culture negative peritonitis was performed and correlated with change of levels of sC5b-9 in PDF. When PD patients with peritonitis were divided into groups that either failed to recover from peritonitis and were finally withdrawn from PD (group 1; n = 25) or recovered (group 2; n = 79), levels of sC5b-9, C3 and C4 in PDF were significantly higher in group 1 patients compared to those in group 2 on day5. Analysis of microorganisms showed significantly higher sC5b-9 levels in PDF of peritonitis cases caused by culture negative peritonitis in group 1 compared with group 2 when we analyzed for individual microorganisms. Of note, on day5, the sC5b-9 levels in PDF were similarly high in peritonitis caused by fungi or other organisms. Our results suggested that levels of complement markers in PDF, especially sC5b-9, have potential as surrogate markers to predict prognosis of PD-related peritonitis.

Complexing agents and pH influence on chemical durability of type I moulded glass containers.

PubMed

Biavati, Alberto; Poncini, Michele; Ferrarini, Arianna; Favaro, Nicola; Scarpa, Martina; Vallotto, Marta

2017-06-16

Among the factors that affect the glass surface chemical durability, pH and complexing agents presence in aqueous solution have the main role (1). Glass surface attack can be also related to the delamination issue with glass particles appearance in the pharmaceutical preparation. A few methods to check for glass containers delamination propensity and some control guidelines have been proposed (2,3). The present study emphasizes the possible synergy between a few complexing agents with pH on the borosilicate glass chemical durability. Hydrolytic attack was performed in small volume 23 ml type I glass containers autoclaved according to EP or USP for 1 hour at 121°C, in order to enhance the chemical attack due to time, temperature and the unfavourable surface/volume ratio. 0,048 M or 0.024 M (moles/liter) solutions of the acids citric, glutaric, acetic, EDTA (ethylenediaminetetraacetic acid) and sodium phosphate with water for comparison, were used for the trials. The pH was adjusted ± 0,05 units at fixed values 5,5-6,6-7-7,4-8-9 by LiOH diluted solution. Since silicon is the main glass network former, silicon release into the attack solutions was chosen as the main index of the glass surface attack and analysed by ICPAES. The work was completed by the analysis of the silicon release in the worst attack conditions, of moulded glass, soda lime type II and tubing borosilicate glass vials to compare different glass compositions and forming technologies. Surface analysis by SEM was finally performed to check for the surface status after the worst chemical attack condition by citric acid. Copyright © 2017, Parenteral Drug Association.

Persistent complement activation on tumor cells in breast cancer.

PubMed Central

Niculescu, F.; Rus, H. G.; Retegan, M.; Vlaicu, R.

1992-01-01

The neoantigens of the C5b-9 complement complex, IgG, C3, C4, S-protein/vitronectin, fibronectin, and macrophages were localized on 17 samples of breast cancer and on 6 samples of benign breast tumors using polyclonal or monoclonal antibodies and the streptavidin-biotin-peroxidase technique. All the tissue samples with carcinoma in each the TNM stages presented C5b-9 deposits on the membranes of tumor cells, thin granules on cell remnants, and diffuse deposits in the necrotic areas. When chemotherapy and radiation therapy preceded surgery, C5b-9 deposits were more intense and extended. The C5b-9 deposits were absent in all the samples with benign lesions. S-protein/vitronectin was present as fibrillar deposits in the connective tissue matrix and as diffuse deposits around the tumor cells, less intense and extended than fibronectin. IgG, C3, and C4 deposits were present only in carcinoma samples. The presence of C5b-9 deposits is indicative of complement activation and its subsequent pathogenetic effects in breast cancer. Images Figure 1 PMID:1374587

Activation of SO2 with [(η(5) -C5 Me5 )2 Ln(THF)2 ] (Ln=Eu, Yb) leading to dithionite and sulfinate complexes.

PubMed

Klementyeva, Svetlana V; Gamer, Michael T; Schmidt, Anna-Corina; Meyer, Karsten; Konchenko, Sergey N; Roesky, Peter W

2014-10-13

The reaction of decamethylytterbocene [(η(5) -C5 Me5 )2 Yb(THF)2 ] with SO2 at low temperature gave two new compounds, namely, the Yb(III) dithionite/sulfinate complex [{(η(5) -C5 Me5 )2 Yb(μ3 ,1κ(2) O(1,3) ,2κ(3) O(2,2',4) -S2 O4 )}2 {(η(5) -C5 Me5 )Yb(μ,1κO,2κO'-C5 Me5 SO2 )}2 ] (1) and the Yb(III) dithionite complex [{(η(5) -C5 Me5 )2 Yb}2 (μ,1κ(2) O(1,3) ,2κ(2) O(2,4) -S2 O4 )] (2). After extraction of 1, the mixture was heated to give the dinuclear tetrasulfinate complex [{(η(5) -C5 Me5 )Yb}2 (μ,κO,κO'-C5 Me5 SO2 )4 ] (3 a). In contrast, from the reaction of [(η(5) -C5 Me5 )2 Eu(THF)2 ] with SO2 only the tetrasulfinate complex [{(η(5) -C5 Me5 )Eu}2 (μ,κO,κO'-C5 Me5 SO2 )4 ] (3 b) was isolated. Two major reaction pathways were observed: 1) reductive coupling of two SO2 molecules to form the dithionite anion S2 O4 (2-) ; and 2) nucleophilic attack of one metallocene C5 Me5 ligand on the sulfur atom of SO2 . The compounds presented are the first dithionite and sulfinate complexes of the f-elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Crystallization of the C-terminal domain of the addiction antidote CcdA in complex with its toxin CcdB

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

Buts, Lieven; De Jonge, Natalie; Loris, Remy, E-mail: reloris@vub.ac.be

2005-10-01

The CcdA C-terminal domain was crystallized in complex with CcdB in two crystal forms that diffract to beyond 2.0 Å resolution. CcdA and CcdB are the antidote and toxin of the ccd addiction module of Escherichia coli plasmid F. The CcdA C-terminal domain (CcdA{sub C36}; 36 amino acids) was crystallized in complex with CcdB (dimer of 2 × 101 amino acids) in three different crystal forms, two of which diffract to high resolution. Form II belongs to space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 37.6, b = 60.5, c = 83.8 Å and diffracts to 1.8more » Å resolution. Form III belongs to space group P2{sub 1}, with unit-cell parameters a = 41.0, b = 37.9, c = 69.6 Å, β = 96.9°, and diffracts to 1.9 Å resolution.« less

Synthesis, structure and reactivity of rare-earth metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2.

PubMed

Yang, Jingying; Xie, Zuowei

2015-04-14

Rare-earth metallacarborane alkyls can be stabilized by the incorporation of a functional sidearm into both π and σ ligands. Reaction of [Me3NH][7,8-O(CH2)2-7,8-C2B9H10] with one equiv. of Ln(CH2C6H4-o-NMe2)3 gave metallacarborane alkyls [η(1):η(5)-O(CH2)2C2B9H9]Ln(σ:η(1)-CH2C6H4-o-NMe2)(THF)2 (Ln = Y (), Gd (), Er ()) via alkane elimination. They represent the first examples of rare-earth metallacarborane alkyls. Treatment of with RN[double bond, length as m-dash]C[double bond, length as m-dash]NR (R = Cy, (i)Pr) or 2-benzoylpyridine afforded the corresponding mono-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[η(2)-(RN)2C(CH2C6H4-o-NMe2)](DME) (R = Cy (), (i)Pr ()) or [η(1):η(5)-O(CH2)2C2B9H9]Y[C5H4NC(Ph)(CH2C6H4-o-NMe2)O](THF)2 (), respectively. Complex also reacted with ArNCO or ArNC (Ar = 2,6-diisopropylphenyl, 2,6-dimethylphenyl) to give di-insertion products [η(1):η(5)-O(CH2)2C2B9H9]Y[OC([double bond, length as m-dash]NC6H3Me2)N(C6H3Me2)C(CH2C6H4-o-NMe2)O](THF)2 () or [η(1):η(5)-O(CH2)2C2B9H9]Y[C([double bond, length as m-dash]NC6H3(i)Pr2)C([double bond, length as m-dash]NC6H3(i)Pr2)(CH2C6H4-o-NMe2)](DME) (). These results showed that the reactivity pattern of the Ln-C σ bond in rare-earth metallacarborane alkyls was dependent on the nature of the unsaturated organic molecules. New complexes were characterized by various spectroscopic techniques and elemental analysis. Some were further confirmed by single-crystal X-ray analysis.

Crystallization and preliminary crystallographic analysis of human Atg4B–LC3 complex

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

Satoo, Kenji; Suzuki, Nobuo N.; Fujioka, Yuko

2007-02-01

Human Atg4B and LC3 were expressed, purified and crystallized as a complex. Diffraction data were collected to a resolution of 1.9 Å. The reversible modification of Atg8 with phosphatidylethanolamine (PE) is crucial for autophagy, the bulk degradation process of cytoplasmic components by the vacuolar/lysosomal system. Atg4 is a cysteine protease that is responsible for the processing and deconjugation of Atg8. Human Atg4B (HsAtg4B; a mammalian orthologue of yeast Atg4) and LC3 (a mammalian orthologue of yeast Atg8) were expressed and purified and two complexes, one consisting of HsAtg4B(1–354) and LC3(1–120) (complex I; the product complex) and the other consisting ofmore » HsAtg4B(1–354) and LC3(1–124) (complex II; the substrate complex), were crystallized using polyethylene glycol 3350 as a precipitant. In both complexes His280 of HsAtg4B was mutated to alanine. The crystals belong to the same space group P2{sub 1}2{sub 1}2{sub 1}, with unit-cell parameters a = 47.5, b = 91.8, c = 102.6 Å for complex I and a = 46.9, b = 90.9, c = 102.5 Å for complex II. Diffraction data were collected to a resolution of 1.9 Å from both crystals.« less

Constructing a Catalytic Cycle for C-F to C-X (X = O, S, N) Bond Transformation Based on Gold-Mediated Ligand Nucleophilic Attack.

PubMed

Hu, Ji-Yun; Zhang, Jing; Wang, Gao-Xiang; Sun, Hao-Ling; Zhang, Jun-Long

2016-03-07

A tricoordinated gold(I) chloride complex, tBuXantphosAuCl, supported by a sterically bulky 9,9-dimethyl-4,5-bis(di-tert-butylphosphino)xanthene ligand (tBuXantphos) was synthesized. This complex features a remarkably longer Au-Cl bond length [2.632(1) Å] than bicoordinated linear gold complexes (2.27-2.30 Å) and tricoordinated XantphosAuCl [2.462(1) Å]. Single-crystal X-ray diffraction analysis of a cocrystal of tBuXantphosAuCl and pentafluoronitrobenzene (PFNB) and UV-vis spectroscopic titration experiments revealed the existence of an anion-π interaction between the Cl anion ligand and PFNB. Stoichiometric reaction between PFNB and tBuXantphosAuOtBu, after replacement of Cl by a more nucleophilic tBuO anion ligand, showed higher reactivity and para selectivity in the transformation of C-F to C-OtBu bond, distinctively different from that when only KOtBu was used (ortho selectivity) under the identical condition. Mechanistic studies including density functional theory calculations suggested a gold-mediated nucleophilic ligand attack of the C-F bond pathway via an SNAr process. On the basis of these results, using trimethylsilyl derivatives TMS-X (X = OMe, SEt, NEt2) as the nucleophilic ligand source and the fluorine acceptor, catalytic transformation of the C-F bond of aromatic substrates to the C-X (X = O, S, N) bond was achieved with tBuXantphosAuCl as the catalyst (up to 20 turnover numbers).

Role of a disulfide-bonded peptide loop within human complement C9 in the species-selectivity of complement inhibitor CD59.

PubMed

Husler, T; Lockert, D H; Sims, P J

1996-03-12

CD59 antigen is a membrane glycoprotein that inhibits the activity of the C9 component of the C5b-9 membrane attack complex (MAC), thereby protecting human cells from lysis by human complement. The complement-inhibitory activity of CD59 is species-selective, and is most effective toward C9 derived from human or other primate plasma. The species-selective activity of CD59 was recently used to map the segment of human C9 that is recognized by this MAC inhibitor, using recombinant rabbit/human C9 chimeras that retain lytic function within the MAC [Husler, T., Lockert, D. H., Kaufman, K. M., Sodetz, J. M., & Sims, P. J. (1995) J. Biol. Chem. 270,3483-3486]. These experiments suggested that the CD59 recognition domain was contained between residues 334 and 415 in human C9. By analyzing the species-selective lytic activity of recombinant C9 with chimeric substitutions internal to this segment, we now demonstrate that the site in human C9 uniquely recognized by CD59 is centered on those residues contained between C9 Cys359/Cys384, with an additional contribution by residues C-terminal to this segment. Consistent with its role as a CD59 recognition domain, CD59 specifically bound a human C9-derived peptide corresponding to residues 359-384, and antibody (Fab) raised against this C9-derived peptide inhibited the lytic activity of human MAC. Mutant human C9 in which Ala was substituted for Cys359/384 was found to express normal lytic activity and to be fully inhibited by CD59. This suggests that the intrachain Cys359/Cys384 disulfide bond within C9 is not required to maintain the conformation of this segment of C9 for interaction with CD59.

An Analysis of Two Layers of Encryption to Protect Network Traffic

DTIC Science & Technology

2010-06-01

Published: 06/18/2001 CVSS Severity: 7.5 (HIGH) CVE-2001-1141 Summary: The Pseudo-Random Number Generator (PRNG) in SSLeay and OpenSSL be- fore 0.9.6b allows...x509cert function in KAME Racoon successfully verifies certifi- cates even when OpenSSL validation fails, which could allow remote attackers to...montgomery function in crypto/bn/bn mont.c in OpenSSL 0.9.8e and earlier does not properly perform Montgomery multiplication, which might allow local users to

High Levels of Soluble C5b-9 Complex in Dialysis Fluid May Predict Poor Prognosis in Peritonitis in Peritoneal Dialysis Patients

PubMed Central

Mizuno, Masashi; Suzuki, Yasuhiro; Higashide, Keiko; Sei, Yumi; Iguchi, Daiki; Sakata, Fumiko; Horie, Masanobu; Maruyama, Shoichi; Matsuo, Seiichi; Morgan, B. Paul; Ito, Yasuhiko

2017-01-01

Background We searched for indicators to predict the prognosis of infectious peritonitis by measuring levels of complement proteins and activation products in peritoneal dialysis (PD) fluid (PDF) of patients at early stages of peritonitis. We retrospectively analyzed the relationship between the levels of sC5b-9, C3 and C4 in PDF and the subsequent clinical prognosis. Methods We measured levels of sC5b-9, C3 and C4 in PDF on days 1, 2 and 5 post-onset of peritonitis in 104 episodes of infectious peritonitis in PD patients from 2008 and retrospectively compared levels with clinical outcomes. Further analysis for the presence of causative microorganisms or to demonstrate bacterial culture negative peritonitis was performed and correlated with change of levels of sC5b-9 in PDF. Results When PD patients with peritonitis were divided into groups that either failed to recover from peritonitis and were finally withdrawn from PD (group 1; n = 25) or recovered (group 2; n = 79), levels of sC5b-9, C3 and C4 in PDF were significantly higher in group 1 patients compared to those in group 2 on day5. Analysis of microorganisms showed significantly higher sC5b-9 levels in PDF of peritonitis cases caused by culture negative peritonitis in group 1 compared with group 2 when we analyzed for individual microorganisms. Of note, on day5, the sC5b-9 levels in PDF were similarly high in peritonitis caused by fungi or other organisms. Conclusion Our results suggested that levels of complement markers in PDF, especially sC5b-9, have potential as surrogate markers to predict prognosis of PD-related peritonitis. PMID:28046064

CORESAFE: A Formal Approach against Code Replacement Attacks on Cyber Physical Systems

DTIC Science & Technology

2018-04-19

AFRL-AFOSR-JP-TR-2018-0035 CORESAFE:A Formal Approach against Code Replacement Attacks on Cyber Physical Systems Sandeep Shukla INDIAN INSTITUTE OF...Formal Approach against Code Replacement Attacks on Cyber Physical Systems 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA2386-16-1-4099 5c.  PROGRAM ELEMENT...Institute of Technology Kanpur India Final Report for AOARD Grant “CORESAFE: A Formal Approach against Code Replacement Attacks on Cyber Physical

Vortex Breakdown over Slender Delta Wings (Eclatement tourbillonnaire sur les ailes delta effil es)

DTIC Science & Technology

2009-11-01

flow patterns for a) experiments of Mitchell et. al ., b) grid G9A4 fully 15-12 turbulent, c) grid G9A4 laminar to turbulent transition at 30% root...tourbillonnaires et en particulier les tourbillons de bord d’attaque subissent une désorganisation soudaine connue sous le nom de rupture du vortex. Ce...attack in the range of –10° to 36°, an amplitude of 5° to 26° and an oscillation frequency of 0.2 to 1.5 Hz. 8) TPI Test Case De Luca et al . tested a

Identity of a peptide domain of human C9 that is bound by the cell-surface complement inhibitor, CD59.

PubMed

Chang, C P; Hüsler, T; Zhao, J; Wiedmer, T; Sims, P J

1994-10-21

The CD59 antigen is a plasma membrane glycoprotein that serves as an inhibitor of the C5b-9 complex of complement. This inhibitory activity appears related to the capacity of CD59 to bind with high affinity to sites that are nascently exposed in the alpha-chain subunit of human C8, as well as within the C9b domain (amino acid residues 245-538) of human C9, during assembly of the C5b-9 complex on the target membrane (Ninomiya, H., and Sims, P. J. (1992) J. Biol. Chem. 267, 13675-13680). The CD59 binding site in C9 was first investigated by N-terminal sequencing of CD59-binding peptides generated by limited digest of the isolated C9b domain. These experiments revealed a 17-kDa fragment (starting at C9 residue Thr-320) that retained affinity for CD59, suggesting the possibility for localizing the CD59 binding site by mapping with small C9-derived peptides. Peptides spanning the entire C9b sequence were expressed in Escherichia coli and then probed with CD59. CD59 bound specifically to all peptides starting N-terminal to C9 residue 359 with C termini extending beyond residue 411. Little to no CD59 binding was observed for various C9-derived peptides that started C-terminal to residue 359 or that were truncated N-terminal to residue 411. Affinity-purified antibody against C9 residues 320-411 inhibited CD59 binding to C9 by > 50% and completely inhibited its binding to the isolated C9b domain. Little to no specific binding of CD59 was detected for peptides restricted to the putative hinge domain within C9b (residues 245-271). These results indicate that a CD59 binding site is located between residues 320 and 411 of the C9 polypeptide and suggest that the affinity of this site is principally determined by residues 359-411.

High Angle of Attack Missile Aerodynamics at Mach Numbers 0.30 to 1.5

DTIC Science & Technology

1980-11-01

I AFWAL-TR-80-3070 I 45~//1° 4. N3B2 Cn 3d . 35 10 -2 36 30 37 50 2- S Cy ’ -1I __- 40 0 45 CAh ------ 50 -555 70- * 6C 50 504 40 ZS 8 9 LO R*N a 4. 5...Continued) 36. Drescher, H., "Messung Der Auf Querange-Sti"mte Zylinder Ausgeubten Zeitlich Verabderten Druck ," Z.F. Flugwss, Vol. 4, No. 1/2, 1956

Effectiveness of icatibant for treatment of hereditary angioedema attacks is not affected by body weight: findings from the Icatibant Outcome Survey, a cohort observational study.

PubMed

Caballero, Teresa; Zanichelli, Andrea; Aberer, Werner; Maurer, Marcus; Longhurst, Hilary J; Bouillet, Laurence; Andresen, Irmgard

2018-01-01

Icatibant is a bradykinin B2-receptor antagonist used for the treatment of hereditary angioedema attacks resulting from C1-inhibitor deficiency. Treatment is not adjusted by body weight however the impact of body mass index (BMI) on the effectiveness of icatibant is not documented in the literature. We examined disease characteristics and icatibant treatment effectiveness in patients stratified by BMI in the Icatibant Outcome Survey, an ongoing, international, observational study monitoring the real-world safety and effectiveness of icatibant. Attack and treatment characteristics as well as outcomes following treatment with icatibant were compared among patients with underweight, normal, overweight, and obese BMI. Data from 2697 icatibant-treated attacks in 342 patients (3.5, 44.7, 34.8, and 17.0% patients of underweight, normal, overweight, and obese BMI, respectively) were analyzed. There was no significant difference in the frequency and severity of attacks across BMI groups, although obese patients tended to have more attacks of high severity. There was no impact of BMI on the frequency of laryngeal attacks, but patients with normal BMI had fewer cutaneous attacks and more abdominal attacks. Most attacks (71.9-83.8%) were treated with a single icatibant injection without the need for rescue with plasma-derived C1-inhibitor (pdC1-INH), regardless of BMI. Patients with obese BMI used pdC1-INH as rescue treatment more often (P < 0.0001; P = 0.0232 excluding 2 outliers) and treated attacks earlier than patients with normal BMI (P = 0.007). Furthermore, time to resolution and duration of attack were shorter for patients with high BMI (P < 0.001 for overweight and P < 0.05 for obese versus normal). Overall, icatibant was comparatively effective in treating attacks in patients across all BMI groups. Trial registration NCT01034969.

Syntheses, characterization, superoxide dismutase, antimicrobial, crystal structure and molecular studies of copper (II) and nickel (II) complexes with 2-((E)-(2, 4-dibromophenylimino) methyl)-4-bromophenol as Schiff base ligand

NASA Astrophysics Data System (ADS)

Bharti, Sulakshna; Choudhary, Mukesh; Mohan, Bharti; Rawat, S. P.; Sharma, S. R.; Ahmad, Khursheed

2017-12-01

Three new copper (II) and nickel (II) complexes viz. [Cu(L)2](1a), [Cu(L)2](1b) and [Ni(L)2].DMF(2), where HL = 2-((E)-(2, 4-dibromophenylimino) methyl)-4-bromophenol, have been synthesized and characterized by using various physico-chemical and spectroscopic techniques. The crystal structures of Schiff base (HL) and their metal complexes (1a), (1b) and (2) were determined by single crystal X-ray diffraction. IR and UV-Vis spectra and magnetic susceptibility measurements agree with the observed crystal structures. The crystallographic and spectroscopic studies confirmed four coordinate environments around the metal (II) ions. The synthesized Schiff base ligand (HL) crystallizes in the orthorhombic system of the space group Pbca. Complex (1a) of HL was crystallized in the monoclinic system of the space group P21/c, a = 10.1712(9) Å, b = 10.9299(10) Å,c = 12.7684(11) Å,α = 90̊,β = 104.649(2)̊, γ = 90̊ and Z = 2 whereas complex (1b) and (2) crystallized in the triclinic system of the space group P-1, a = 11.499(5)Å, b = 11.598(5)Å, c = 12.211(5)Å, α = 98.860(5), β = 115.653(5),γ = 100.906(5) and Z = 2 for (1b), a = 9.080(6) Å, b = 9.545(8)Å, c = 9.545(8)Å, α = 101.43(4)º,β = 99.63(3)̊, γ = 117.71(2)º and Z = 1 for (2). The synthesized ligand (HL) was behaved as monobasic bidentate Schiff base ligand having N and O donor sites. The electron paramagnetic resonance spectra indicate a dx2-y2ground state (g|| > g⊥> 2.0023) for (1a) and (1b). Copper (II) complexes display X-band EPR spectra in 100% DMSO and 77 K, giving indicating dx2-y2ground state. Superoxide dismutase-like activities of HL and its complexes were investigated by nitrobluetetrazolium chloride-DMSO assay and IC50 values were evaluated. These complexes were also tested for their in vitro antimicrobial activities against two bacteria (E. coli and Salmonella typhi) and two fungi (Pencillium, Aspergillus sp.) comparing with the Schiff base. The antimicrobial results showed that the complexes were more biologically active compounds to the Schiff base (HL).

Aftermath of Terror: A Nationwide Longitudinal Study of Posttraumatic Stress and Worry Across the Decade Following the September 11, 2001 Terrorist Attacks.

PubMed

Garfin, Dana Rose; Poulin, Michael J; Blum, Scott; Silver, Roxane Cohen

2018-02-01

Research conducted in the early years after the September 11, 2001 (9/11) terrorist attacks in New York, Pennsylvania, and Washington, DC demonstrated adverse psychological outcomes among residents of the United States who were exposed to the attacks both directly and indirectly via the media. However, less is known about the impact of this collective trauma over time. Beginning at the end of December 2006, a longitudinal study of a nationally representative sample of U.S. residents (Cohort 2, N = 1,613) examined the long-term effects of 9/11, with annual assessments administered every year for 3 years. We assessed rates of 9/11-related posttraumatic stress (PTS) annually during the first 2 years of the study; during the second and third years of the study, we assessed fear and worry regarding future terrorism. Rates of PTS among participants were compared with those assessed annually in a nationally representative sample between 2002 and 2004 (Cohort 1); results indicated a relatively stable pattern of 9/11-related PTS symptoms for 6 years following the attacks. Five to six years after 9/11, we found an association between 9/11-related PTS and both direct, B = 8.45, 95% CI [4.32, 12.59] and media-based (live television), B = 1.78, 95% CI [0.90, 2.65] exposure to the attacks. Six to 7 years post-9/11, fear and worry regarding future terrorism were predicted by 9/11-related PTS symptoms that had been reported approximately 5 years after the attacks, B = 0.04, 95% CI [0.03, 0.05]. The psychological legacy of 9/11 was perceptible among many U.S. residents throughout the decade that followed. Copyright © 2018 International Society for Traumatic Stress Studies.

Theoretical study on the multi-channel reaction of OH radical with 5-methylcytosine

NASA Astrophysics Data System (ADS)

Wang, Wenliang; Jin, Lingxia; Wang, Weina; Lu, Jian; Yang, Jianming

2007-08-01

All the possible addition and hydrogen abstraction reactions of OH radical with 5-methylcytosine (5-MeC) have been investigated at B3LYP/6-31++G(d,p)//B3LYP/6-31G(d,p)+ZPE level. The results indicate that OH radical may form complexes with 5-MeC, and the reaction is assumed to occur from these complexes. The estimated activation energies corresponding to addition reactions at N3, C4, C5 and C6 sites of the 5-MeC are 80.96, 63.41, 0.00 and 0.30 kJ/mol, respectively. The order of stability of adducts is P4(C6) > P3(C5) > P2(C4) > P1(N3). The activation energies corresponding to the H9, H10, H11, and H14 abstraction reactions from the 5-MeC are all small, and the stabilization of the products is P8(H14) > P6(H10) > P5(H9) > P7(H11).

C-C bond formation and related reactions at the CNC backbone in (smif)FeX (smif = 1,3-di-(2-pyridyl)-2-azaallyl): dimerizations, 3 + 2 cyclization, and nucleophilic attack; transfer hydrogenations and alkyne trimerization (X = N(TMS)2, dpma = (di-(2-pyridyl-methyl)-amide)).

PubMed

Frazier, Brenda A; Williams, Valerie A; Wolczanski, Peter T; Bart, Suzanne C; Meyer, Karsten; Cundari, Thomas R; Lobkovsky, Emil B

2013-03-18

Molecular orbital analysis depicts the CNC(nb) backbone of the smif (1,3-di-(2-pyridyl)-2-azaallyl) ligand as having singlet diradical and/or ionic character where electrophilic or nucleophilic attack is plausible. Reversible dimerization of (smif)Fe{N(SiMe3)2} (1) to [{(Me3Si)2N}Fe]2(μ-κ(3),κ(3)-N,py2-smif,smif) (2) may be construed as diradical coupling. A proton transfer within the backbone-methylated, and o-pyridine-methylated smif of putative ((b)Me2(o)Me2smif)FeN(SiMe3)2 (8) provides a route to [{(Me3Si)2N}Fe]2(μ-κ(4),κ(4)-N,py2,C-((b)Me,(b)CH2,(o)Me2(smif)H))2 (9). A 3 + 2 cyclization of ditolyl-acetylene occurs with 1, leading to the dimer [{2,5-di(pyridin-2-yl)-3,4-di-(p-tolyl-2,5-dihydropyrrol-1-ide)}FeN(SiMe3)2]2 (11), and the collateral discovery of alkyne cyclotrimerization led to a brief study that identified Fe(N(SiMe3)2(THF) as an effective catalyst. Nucleophilic attack by (smif)2Fe (13) on (t)BuNCO and (2,6-(i)Pr2C6H3)NCO afforded (RNHCO-smif)2Fe (14a, R = (t)Bu; 14b, 2,6-(i)PrC6H3). Calculations suggested that (dpma)2Fe (15) would favorably lose dihydrogen to afford (smif)2Fe (13). H2-transfer to alkynes, olefins, imines, PhN═NPh, and ketones was explored, but only stoichiometric reactions were affected. Some physical properties of the compounds were examined, and X-ray structural studies on several dinuclear species were conducted.

Complexing Agents and pH Influence on Chemical Durability of Type I Molded Glass Containers.

PubMed

Biavati, Alberto; Poncini, Michele; Ferrarini, Arianna; Favaro, Nicola; Scarpa, Martina; Vallotto, Marta

2017-01-01

Among the factors that affect the glass surface chemical durability, pH and complexing agents present in aqueous solution have the main role. Glass surface attack can be also related to the delamination issue causing glass particles' appearance in the pharmaceutical preparation. A few methods to check for glass containers delamination propensity and some control guidelines have been proposed. The present study emphasizes the possible synergy between a few complexing agents with pH on borosilicate glass chemical durability.Hydrolytic attack was performed in small-volume 23 mL type I glass containers autoclaved according to the European Pharmacopoeia or United States Pharmacopeia for 1 h at 121 °C, in order to enhance the chemical attack due to time, temperature, and the unfavorable surface/volume ratio. Solutions of 0.048 M or 0.024 M (M/L) of the acids citric, glutaric, acetic, EDTA (ethylenediaminetetraacetic acid), together with sodium phosphate with water for comparison, were used for the trials. The pH was adjusted ±0.05 units at fixed values 5.5, 6.6, 7, 7.4, 8, and 9 by LiOH diluted solution.Because silicon is the main glass network former, silicon release into the attack solutions was chosen as the main index of the glass surface attack and analysed by inductively coupled plasma atomic emission spectrophotometry. The work was completed by the analysis of the silicon release in the worst attack conditions of molded glass, soda lime type II glass, and tubing borosilicate glass vials to compare different glass compositions and forming technologies. Surface analysis by scanning electron microscopy was finally performed to check for the surface status after the worst chemical attack condition by citric acid. LAY ABSTRACT: Glass, like every packaging material, can have some usage limits, mainly in basic pH solutions. The issue of glass surface degradation particles that appear in vials (delamination) has forced a number of drug product recalls in recent years. To prevent such situations, pharmaceutical and biopharmaceutical manufacturers need to understand the reasons for accelerate surface glass corrosion mainly in the case of injectables.Some drugs can contain active components with known ability to corrode glass silica networks. Sometimes these ingredients are dissolved in an alkaline medium that dramatically increases the glass corrosion and potentially causes the issue. As this action is strongly affected by time and temperature, flaking may become visible only after a long storage time. The purpose of this investigation is to verify the borosilicate glass chemical durability during controlled conditions of time and temperature when in contact with testing solutions containing different complexing agents by varying the pH. Si concentration in the extract solution is taken as an index of glass dissolution during constant autoclaving conditions for 1 h at 121 °C, which simulates approximately five years of contact at room temperature.Acetate, citrate, ethylenediaminetetraacetic acid (EDTA), phosphate, and glutarate 0.048 M or 0.024 M solutions were used at increasing pH from 5.5 to 9.0. The chemical durability of two borosilicate tubing glass vials of different glass compositions were compared with the molded one in the worst attack conditions by citric acid. Even if no delamination issue has been experienced by this study in type I molded and tubing containers, the conclusions developed can provide pharmaceutical manufacturers with useful information to prevent glass delamination risk in their processes. © PDA, Inc. 2017.

Sport skill level and gender with relation to age, physical development and special fitness of the participants of Olympic volleyball tournament Beijing 2008.

PubMed

Sterkowicz-Przybycien, Katarzyna; Sterkowicz, Stanislaw; Zak, Stanislaw

2014-06-01

The aim of this study was to provide an answer to the question whether and how age, body height, body mass, body mass index and results from fitness tests are related to sport skill level and gender of the participants of the Olympic volleyball tournament. Two-Way ANOVA was used to find the dependency of the variables on the factor of sport skill level (A--teams which took places 1 to 4, B--places from 5 to 8; C--places from 9 to 12) and gender (F--female; M--male). Statistical significance was set at p < 0.05. The Bonferroni's adjustment was carried out for three p = 0.017 and fifteen p = 0.003 pairs of comparisons). The M and F athletes included in A-C groups (N = 48 in each group) were than compared to the classification in the neural network of Probabilistic Neural Network (PNN). A combined effect of the factors of sports level and gender on the height of attack jump (F = 4.13; p = 0.02) and block jump (F = 9.22; p < 0.001) was identified. The level of achievement was modified by the differences between the men and women. A significant advantage over the groups B and C was found for attack height and block height. In the group A, the differences between the results obtained for women and men in the ranges of attack and block with respect to the net height were not significant. Mean range of block jump did not match up to attack jump, particularly in women. The application of PNN network showed that age, BMI, relative attack jump and block jump are good predictors of sport results. The percentage of properly classified players in the group of men was lower than in women (42.4 vs. 56.3%). In this regard, big differences were found at the lower level of sport results: A (77.1 vs. 79.2%), B (25.0 vs. 25.0%) and C (25.0 vs. 64.6%). In conclusion, selection for national teams should take into consideration the players with long competitive experience with adequate weight/height ratios, who exhibit good training adaptations to jumping exercise.

Complement System Part II: Role in Immunity

PubMed Central

Merle, Nicolas S.; Noe, Remi; Halbwachs-Mecarelli, Lise; Fremeaux-Bacchi, Veronique; Roumenina, Lubka T.

2015-01-01

The complement system has been considered for a long time as a simple lytic cascade, aimed to kill bacteria infecting the host organism. Nowadays, this vision has changed and it is well accepted that complement is a complex innate immune surveillance system, playing a key role in host homeostasis, inflammation, and in the defense against pathogens. This review discusses recent advances in the understanding of the role of complement in physiology and pathology. It starts with a description of complement contribution to the normal physiology (homeostasis) of a healthy organism, including the silent clearance of apoptotic cells and maintenance of cell survival. In pathology, complement can be a friend or a foe. It acts as a friend in the defense against pathogens, by inducing opsonization and a direct killing by C5b–9 membrane attack complex and by triggering inflammatory responses with the anaphylatoxins C3a and C5a. Opsonization plays also a major role in the mounting of an adaptive immune response, involving antigen presenting cells, T-, and B-lymphocytes. Nevertheless, it can be also an enemy, when pathogens hijack complement regulators to protect themselves from the immune system. Inadequate complement activation becomes a disease cause, as in atypical hemolytic uremic syndrome, C3 glomerulopathies, and systemic lupus erythematosus. Age-related macular degeneration and cancer will be described as examples showing that complement contributes to a large variety of conditions, far exceeding the classical examples of diseases associated with complement deficiencies. Finally, we discuss complement as a therapeutic target. PMID:26074922

Selective Optimization

DTIC Science & Technology

2015-07-06

NUMBER 5b. GRANT NUMBER AFOSR FA9550-12-1-0154 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Shabbir Ahmed and Santanu S. Dey 5d. PROJECT NUMBER 5e. TASK...standard mixed-integer programming (MIP) formulations of selective optimization problems. While such formulations can be attacked by commercial...F33615-86-C-5169. 5b. GRANT NUMBER. Enter all grant numbers as they appear in the report, e.g. AFOSR-82-1234. 5c. PROGRAM ELEMENT NUMBER. Enter

Rhenium in homogeneous catalysis: [ReBrH(NO)(labile ligand)(large-bite-angle diphosphine)] complexes as highly active catalysts in olefin hydrogenations.

PubMed

Dudle, Balz; Rajesh, Kunjanpillai; Blacque, Olivier; Berke, Heinz

2011-06-01

The reaction of [ReBr(2)(MeCN)(NO)(P∩P)] (P∩P = 1,1'-bisdiphenylphosphinoferrocene (dppfc) (1a), 1,1'-bisdiisopropylphosphinopherrocene (diprpfc) (1b), 2,2'-bis(diphenylphosphino)diphenyl ether (dpephos) (1c), 10,11-dihydro-4,5-bis(diphenylphosphino)dibenzo[b,f]oxepine (homoxantphos) (1d) and 4,6-bis(diphenylphosphino)-10,10-dimethylphenoxasilin (Sixantphos) (1e)) led in the presence of HSiEt(3) and ethylene to formation of the ethylene hydride complexes [ReBrH(η(2)-C(2)H(4))(NO)(P∩P)] (3a,b,d), the MeCN ethyl complex [ReBr(Et)(MeCN)(NO)(dpephos)] (5c) and two ortho-metalated stereoisomers of [ReBr(η(2)-C(2)H(4))(NO)(η(3)-o-C(6)H(4)-Sixantphos)] 8e(up) and 8e(down). The complexes 3a,b,d, and 5c and the isomers of 8e showed high catalytic activity (TOFs ranging from 22 to 4870 h(-1), TONs up to 24000) in the hydrogenation of monosubstituted olefins. For 8e(down) and 8e(up) a remarkable functional group tolerance and catalyst stability were noticed. Kinetic experiments revealed k(obs) to be first order in c(cat) and c(H(2)) and zeroth order in c(olefin). Mechanistic studies and DFT calculations suggest the catalysis to proceed along an Osborn-type catalytic cycle with olefin before H(2) addition. The unsaturated key intermediates [ReBrH(NO)(P∩P)] (2a-e) could be intercepted with MeCN as [ReBrH(MeCN)(NO)(P∩P)] (10a-d) complexes or isolated as dimeric μ(2)-(H)(2) complexes [{ReBr(μ(2)-H)(NO)(P∩P)}(2)] (9b and 9e). Variation of the bidentate ligand demonstrated a crucial influence of the (large)-bite-angle on the catalytic performance and reactivity of 3a,b,d, 5c, and 8e. © 2011 American Chemical Society

The Lectin Complement Pathway Is Involved in Protection Against Enteroaggregative Escherichia coli Infection.

PubMed

Adler Sørensen, Camilla; Rosbjerg, Anne; Hebbelstrup Jensen, Betina; Krogfelt, Karen Angeliki; Garred, Peter

2018-01-01

Enteroaggregative Escherichia coli (EAEC) causes acute and persistent diarrhea worldwide. Still, the involvement of host factors in EAEC infections is unresolved. Binding of recognition molecules from the lectin pathway of complement to EAEC strains have been observed, but the importance is not known. Our aim was to uncover the involvement of these molecules in innate complement dependent immune protection toward EAEC. Binding of mannose-binding lectin, ficolin-1, -2, and -3 to four prototypic EAEC strains, and ficolin-2 binding to 56 clinical EAEC isolates were screened by a consumption-based ELISA method. Flow cytometry was used to determine deposition of C4b, C3b, and the bactericidal C5b-9 membrane attack complex (MAC) on the bacteria in combination with different complement inhibitors. In addition, the direct serum bactericidal effect was assessed. Screening of the prototypic EAEC strains revealed that ficolin-2 was the major binder among the lectin pathway recognition molecules. However, among the clinical EAEC isolates only a restricted number ( n  = 5) of the isolates bound ficolin-2. Using the ficolin-2 binding isolate C322-17 as a model, we found that incubation with normal human serum led to deposition of C4b, C3b, and to MAC formation. No inhibition of complement deposition was observed when a C1q inhibitor was added, while partial inhibition was observed when ficolin-2 or factor D inhibitors were used separately. Combining the inhibitors against ficolin-2 and factor D led to virtually complete inhibition of complement deposition and protection against direct bacterial killing. These results demonstrate that ficolin-2 may play an important role in innate immune protection against EAEC when an appropriate ligand is exposed, but many EAEC strains evade lectin pathway recognition and may, therefore, circumvent this strategy of innate host immune protection.

Novel types of tetra-, hexa-, octa-, and dodecanuclear silver clusters containing (2,7-Di-tert-butylfluoren-9-ylidene)methanedithiolate.

PubMed

Vicente, José; González-Herrero, Pablo; García-Sánchez, Yolanda; Jones, Peter G

2009-03-02

The reaction of AgClO(4) with piperidinium 2,7-di-tert-butyl-9H-fluorene-9-carbodithioate (pipH)[S(2)C(t-Bu-Hfy)] (1) (t-Bu-Hfy = 2,7-di-tert-butylfluoren-9-yl) afforded [Ag(n){S(2)C(t-Bu-Hfy)}(n)] (2), which reacted with phosphines to give [Ag{S(2)C(t-Bu-Hfy)}L(2)] [L = PPh(3) (3a); L(2) = bis(diphenylphosphino)ethane (dppe, 3b), 1,1'-bis(diphenylphosphino)ferrocene (dppf, 3c). By reacting complex 2 with AgClO(4) and piperidine in a 1:1:1 molar ratio, the dodecanuclear cluster [Ag(12){S(2)C(t-Bu-fy)}(6)] (4) (t-Bu-fy = 2,7-di-tert-butylfluoren-9-ylidene) was obtained. Compound 4 can also be directly prepared from the reaction of 1 with AgClO(4) and piperidine in a 1:2:1 molar ratio. The reactions of 1 with AgClO(4), phosphines, and piperidine afforded the compounds [Ag(6){S(2)C(t-Bu-fy)}(3)L(5)] [1:2:2:1 molar ratio; L = PPh(3) (5a), P(p-To)(3) (5b)], [Ag(4){S(2)C(t-Bu-fy)}(2)(dppf)(2)] (6) (1:2:1:1 molar ratio), [Ag(n){S(2)C(t-Bu-fy)}(n/2){P(i-Pr)(3)}(n)] (7) (1:2:2:1 molar ratio), or [Ag(8){S(2)C(t-Bu-fy)}(4){P(i-Pr)(3)}(4)] (8) (1:2:1:1 molar ratio). Complexes 5a,b, 6, 7, and 8 can be also obtained by reacting 4 with the corresponding phosphine in the appropriate molar ratio. The crystal structures of 4, 5b, and 8 have been determined by X-ray diffraction studies. The nuclearity of complex 6 was established from its (31)P{(1)H} NMR data, which reveal a very fast dynamic process leading to an average coupling of each of the P atoms of the dppf ligands with four Ag atoms.

Eculizumab for dense deposit disease and C3 glomerulonephritis.

PubMed

Bomback, Andrew S; Smith, Richard J; Barile, Gaetano R; Zhang, Yuzhou; Heher, Eliot C; Herlitz, Leal; Stokes, M Barry; Markowitz, Glen S; D'Agati, Vivette D; Canetta, Pietro A; Radhakrishnan, Jai; Appel, Gerald B

2012-05-01

The principle defect in dense deposit disease and C3 glomerulonephritis is hyperactivity of the alternative complement pathway. Eculizumab, a monoclonal antibody that binds to C5 to prevent formation of the membrane attack complex, may prove beneficial. In this open-label, proof of concept efficacy and safety study, six subjects with dense deposit disease or C3 glomerulonephritis were treated with eculizumab every other week for 1 year. All had proteinuria >1 g/d and/or AKI at enrollment. Subjects underwent biopsy before enrollment and repeat biopsy at the 1-year mark. The subjects included three patients with dense deposit disease (including one patient with recurrent dense deposit disease in allograft) and three patients with C3 glomerulonephritis (including two patients with recurrent C3 glomerulonephritis in allograft). Genetic and complement function testing revealed a mutation in CFH and MCP in one subject each, C3 nephritic factor in three subjects, and elevated levels of serum membrane attack complex in three subjects. After 12 months, two subjects showed significantly reduced serum creatinine, one subject achieved marked reduction in proteinuria, and one subject had stable laboratory parameters but histopathologic improvements. Elevated serum membrane attack complex levels normalized on therapy and paralleled improvements in creatinine and proteinuria. Clinical and histopathologic data suggest a response to eculizumab in some but not all subjects with dense deposit disease and C3 glomerulonephritis. Elevation of serum membrane attack complex before treatment may predict response. Additional research is needed to define the subgroup of dense deposit disease/C3 glomerulonephritis patients in whom eculizumab therapy can be considered.

Results of investigations (OA20C) on an 0.015-scale configuration 140A/B space shuttle vehicle orbiter model (49-0) in the NASA/Langley Research Center Unitary Plan Wind Tunnel

NASA Technical Reports Server (NTRS)

Nichols, M. E.

1974-01-01

Data obtained from the wind tunnel tests of a scale model of the space shuttle orbiter configuration 140 A/B are presented. The test was conducted at Mach numbers of 2.5, 3.9, and 4.6 with Reynolds numbers from 1.25 million per foot to 5.0 million per foot. Various control surface settings were used ranging from an angle of attack range from minus 4 to plus 42 degrees at zero angle of yaw. Longitudinal stability and control characteristics of the space shuttle configuration were analyzed.

Relative Contribution of Cellular Complement Inhibitors CD59, CD46, and CD55 to Parainfluenza Virus 5 Inhibition of Complement-Mediated Neutralization

PubMed Central

Li, Yujia; Parks, Griffith D.

2018-01-01

The complement system is a part of the innate immune system that viruses need to face during infections. Many viruses incorporate cellular regulators of complement activation (RCA) to block complement pathways and our prior work has shown that Parainfluenza virus 5 (PIV5) incorporates CD55 and CD46 to delay complement-mediated neutralization. In this paper, we tested the role of a third individual RCA inhibitor CD59 in PIV5 interactions with complement pathways. Using a cell line engineered to express CD59, we show that small levels of functional CD59 are associated with progeny PIV5, which is capable of blocking assembly of the C5b-C9 membrane attack complex (MAC). PIV5 containing CD59 (PIV5-CD59) showed increased resistance to complement-mediated neutralization in vitro comparing to PIV5 lacking regulators. Infection of A549 cells with PIV5 and RSV upregulated CD59 expression. TGF-beta treatment of PIV5-infected cells also increased cell surface CD59 expression and progeny virions were more resistant to complement-mediated neutralization. A comparison of individual viruses containing only CD55, CD46, or CD59 showed a potency of inhibiting complement-mediated neutralization, which followed a pattern of CD55 > CD46 > CD59. PMID:29693588

Trichinella spiralis Paramyosin Binds to C8 and C9 and Protects the Tissue-Dwelling Nematode from Being Attacked by Host Complement

PubMed Central

Zhang, Zhifei; Yang, Jing; Wei, Junfei; Yang, Yaping; Chen, Xiaoqin; Zhao, Xi; Gu, Yuan; Cui, Shijuan; Zhu, Xinping

2011-01-01

Background Paramyosin is a thick myofibrillar protein found exclusively in invertebrates. Evidence suggested that paramyosin from helminths serves not only as a structural protein but also as an immunomodulatory agent. We previously reported that recombinant Trichinella spiralis paramyosin (Ts-Pmy) elicited a partial protective immunity in mice. In this study, the ability of Ts-Pmy to bind host complement components and protect against host complement attack was investigated. Methods and Findings In this study, the transcriptional and protein expression levels of Ts-Pmy were determined in T. spiralis newborn larva (NBL), muscle larva (ML) and adult worm developmental stages by RT-PCR and western blot analysis. Expression of Ts-Pmy at the outer membrane was observed in NBL and adult worms using immunogold electron microscopy and immunofluorescence staining. Functional analysis revealed that recombinant Ts-Pmy(rTs-Pmy) strongly bound to complement components C8 and C9 and inhibited the polymerization of C9 during the formation of the membrane attack complex (MAC). rTs-Pmy also inhibited the lysis of rabbit erythrocytes (ER) elicited by an alternative pathway-activated complement from guinea pig serum. Inhibition of native Ts-Pmy on the surface of NBL with a specific antiserum reduced larvae viability when under the attack of complement in vitro. In vivo passive transfer of anti-Ts-Pmy antiserum and complement-treated larvae into mice also significantly reduced the number of larvae that developed to ML. Conclusion These studies suggest that the outer membrane form of T. spiralis paramyosin plays an important role in the evasion of the host complement attack. PMID:21750743

C4B gene influences intestinal microbiota through complement activation in patients with paediatric-onset inflammatory bowel disease.

PubMed

Nissilä, E; Korpela, K; Lokki, A I; Paakkanen, R; Jokiranta, S; de Vos, W M; Lokki, M-L; Kolho, K-L; Meri, S

2017-12-01

Complement C4 genes are linked to paediatric inflammatory bowel disease (PIBD), but the mechanisms have remained unclear. We examined the influence of C4B gene number on intestinal microbiota and in-vitro serum complement activation by intestinal microbes in PIBD patients. Complement C4A and C4B gene numbers were determined by genomic reverse transcription-polymerase chain reaction (RT-PCR) from 64 patients with PIBD (Crohn's disease or ulcerative colitis). The severity of the disease course was determined from faecal calprotectin levels. Intestinal microbiota was assessed using the HITChip microarray. Complement reactivity in patients was analysed by incubating their sera with Yersinia pseudotuberculosis and Akkermansia muciniphila and determining the levels of C3a and soluble terminal complement complex (SC5b-9) using enzyme immunoassays. The microbiota diversity was wider in patients with no C4B genes than in those with one or two C4B genes, irrespective of intestinal inflammation. C4B and total C4 gene numbers correlated positively with soluble terminal complement complex (TCC, SC5b-9) levels when patient serum samples were stimulated with bacteria. Our results suggest that the C4B gene number associates positively with inflammation in patients with PIBD. Multiple copies of the C4B gene may thus aggravate the IBD-associated dysbiosis through escalated complement reactivity towards the microbiota. © 2017 British Society for Immunology.

Synthesis of backbone P-functionalized imidazol-2-ylidene complexes: en route to novel functional ionic liquids.

PubMed

Majhi, Paresh Kumar; Sauerbrey, Susanne; Schnakenburg, Gregor; Arduengo, Anthony J; Streubel, Rainer

2012-10-01

1-Alkyl-3-methyl-4-diphenylphosphoryl-imidazolium hydrogensulfate (4a,b) (a: R(1) = R(2) = Me; b: R(1) = (i)Pr, R(2) = Me) and 1-alkyl-3-methyl-4,5-bis(diphenylphosphoryl)imidazolium hydrogensulfate (6a,c) (c: R(1) = (n)Bu, R(2) = Me) were obtained selectively and in good yields by oxidative desulfurization of 1-alkyl-3-methyl-4-diphenylphosphino-imidazole-2-thiones (2a,b) and 1-n-butyl-3-methyl-4,5-bis(diphenylphosphoryl)imidazole-2-thione (3c) or 1,3-dimethyl-4-diphenylthiophosphoryl-5-diphenylphosphino-imidazole-2-thione (5a), respectively, with hydrogen peroxide. Synthesis of phosphoryl functionalized imidazol-2-ylidene complexes of group VI metal pentacarbonyls (7a-9a) and (10b-12b) and bis(phosphoryl) functionalized imidazol-2-ylidene complexes of group VI metal pentacarbonyls (13c-15c) and (16a) with low steric demand (methyl, isopropyl, n-butyl) at both N-centers was achieved through deprotonation of imidazolium salts (4a,b) and (6a,c), respectively,-having HSO(4)(-) as a counterion-with potassium tert-butoxide followed by rapid addition of metal pentacarbonyl acetonitrile complexes [M(CO)(5)(CH(3)CN)] (M = Cr, Mo, W). The products were unambiguously characterized by elemental analyses, spectroscopic and spectrometric methods, and in addition, by single-crystal X-ray structure studies in the cases of 4b, 8a, 15c, and 16a; the latter two reveal imidazole ring bond distance alternation in contrast to 8a.

Synthesis, characterization and cytotoxic properties of platinum(II) complexes containing the nucleosides adenosine and cytidine.

PubMed

Montagner, Diego; Gandin, Valentina; Marzano, Cristina; Longato, Bruno

2011-06-01

Cytidine (cyt) and adenosine (ado) react with cis-[L(2)Pt(μ-OH)](2)(NO(3))(2) (L=PMe(3), PPh(3)) in various solvents to give the nucleoside complexes cis-[L(2)Pt{cyt(-H),N(3)N(4)}](3)(NO(3))(3) (L=PMe(3), 1),cis-[L(2)Pt{cyt(-H),N(4)}(cyt,N(3))]NO(3) (L=PPh(3), 2), cis-[L(2)Pt{ado(-H),N(1)N(6)}](2)(NO(3))(2) (L=PMe(3), 3) and cis-[L(2)Pt{ado(-H),N(6)N(7)}]NO(3) (L=PPh(3), 4). When the condensation reaction is carried out in solution of nitriles (RCN, R=Me, Ph) the amidine derivatives cis-[(PPh(3))(2)PtNH=C(R){cyt(-2H)}]NO(3) (R=Me, 5a; R=Ph, 5b) and cis-[(PPh(3))(2)PtNH=C(R){ado(-2H)}]NO(3) (R=Me, 6a: R=Ph, 6b) are quantitatively formed. The coordination mode of these nucleosides, characterized in solution by multinuclear NMR spectroscopy and mass spectrometry, is similar to that previously observed for the nucleobases 1-methylcytosine (1-MeCy) and 9-methyladenine (9-MeAd). The cytotoxic properties of the new complexes, and those of the nucleobase analogs, cis-[(PPh(3))(2)PtNH=C(R){1-MeCy(-2H)}]NO(3) (R=Me, 7a: R=Ph, 7b), cis-[(PPh(3))(2)PtNH=C(R){9-MeAd(-2H)}]NO(3) (R=Me, 8a: R=Ph, 8b) have been investigated in a wide panel of human cancer cells. Interestingly, whereas the Pt(II) nucleoside complexes (1-4) did not show appreciable cytotoxicity, the corresponding amidine derivatives (7a, 7b, 8a, 8b, 5b, and 6b) exhibited a significant in vitro antitumor activity. Copyright © 2011 Elsevier Inc. All rights reserved.

Synthesis, structural, photophysical and thermal studies of benzoate bridged Sm(III) complexes

NASA Astrophysics Data System (ADS)

Singh, Udai P.; Kumar, Rajeev; Upreti, Shailesh

2007-04-01

One samarium coordination polymer (chain like) 1 with composition [{Sm(OBz) 3(MeO) 2} 2] n has been prepared from the reaction of SmCl 3 and sodium benzoate in 1:3 ratio whereas four binuclear samarium complexes with chemical composition [{(tp)Sm(μ- p-X-OBz) 2} 2] have been prepared by the reaction of SmCl 3, potassium hydrotris(pyrazol-1-yl)borate [K(tp)] and sodium p-X-benzoate (where X = H, Cl, F, NO 2) in 1:1:2 ratio. These complexes have been characterized by elemental analysis, IR spectroscopy, thermogravimetry, optical properties, X-ray and magnetic measurement studies. The X-ray structure shows that the complexes 2- 5 are isostructural whereas the structure of 1 is different. The coordination number around metal center in 1 is eight whereas in complexes 2- 5, each samarium is seven coordinate. The X-ray studies indicate that the complex 1 crystallizes in monoclinic space group P2(1)/ c with the cell dimensions a = 9.75(7), b = 21.83(15), c = 22.28(15) Å, whereas the complexes 2 and 3 crystallizes isostructurally in the triclinic space group P1¯ with the cell dimension a = 11.77(10), b = 12.60(10), c = 17.57(13) Å and a = 9.55(3), b = 12.80(4), c = 14.47(5) Å, respectively. The samarium ions in 2 and 3 are coordinated by three N atoms of pyrazolylborate ligand and four O atoms from benzoate groups. The photophysical properties of above complexes have been studied with ultraviolet absorption, excitation and emission spectral studies. The complexes 1- 5 excited at 240 nm wavelength produced characteristic luminescence features, arising mostly due to the f-f transitions.

Benchmark ab Initio Characterization of the Complex Potential Energy Surfaces of the X- + NH2Y [X, Y = F, Cl, Br, I] Reactions.

PubMed

Hajdu, Bálint; Czakó, Gábor

2018-02-22

We report a comprehensive high-level explicitly correlated ab initio study on the X - + NH 2 Y [X,Y = F, Cl, Br, I] reactions characterizing the stationary points of the S N 2 (Y - + NH 2 X) and proton-transfer (HX + NHY - ) pathways as well as the reaction enthalpies of various endothermic additional product channels such as H - + NHXY, XY - + NH 2 , XY + NH 2 - , and XHY - + NH. Benchmark structures and harmonic vibrational frequencies are obtained at the CCSD(T)-F12b/aug-cc-pVTZ(-PP) level of theory, followed by CCSD(T)-F12b/aug-cc-pVnZ(-PP) [n = Q and 5] and core correlation energy computations. In the entrance and exit channels we find two equivalent hydrogen-bonded C 1 minima, X - ···HH'NY and X - ···H'HNY connected by a C s first-order saddle point, X - ···H 2 NY, as well as a halogen-bonded front-side complex, X - ···YNH 2 . S N 2 reactions can proceed via back-side attack Walden inversion and front-side attack retention pathways characterized by first-order saddle points, submerged [X-NH 2 -Y] - and high-energy [H 2 NXY] - , respectively. Product-like stationary points below the HX + NHY - asymptotes are involved in the proton-transfer processes.

Eculizumab for Dense Deposit Disease and C3 Glomerulonephritis

PubMed Central

Smith, Richard J.; Barile, Gaetano R.; Zhang, Yuzhou; Heher, Eliot C.; Herlitz, Leal; Stokes, M. Barry; Markowitz, Glen S.; D’Agati, Vivette D.; Canetta, Pietro A.; Radhakrishnan, Jai; Appel, Gerald B.

2012-01-01

Summary Background and objectives The principle defect in dense deposit disease and C3 glomerulonephritis is hyperactivity of the alternative complement pathway. Eculizumab, a monoclonal antibody that binds to C5 to prevent formation of the membrane attack complex, may prove beneficial. Design, setting, participants, & measurements In this open-label, proof of concept efficacy and safety study, six subjects with dense deposit disease or C3 glomerulonephritis were treated with eculizumab every other week for 1 year. All had proteinuria >1 g/d and/or AKI at enrollment. Subjects underwent biopsy before enrollment and repeat biopsy at the 1-year mark. Results The subjects included three patients with dense deposit disease (including one patient with recurrent dense deposit disease in allograft) and three patients with C3 glomerulonephritis (including two patients with recurrent C3 glomerulonephritis in allograft). Genetic and complement function testing revealed a mutation in CFH and MCP in one subject each, C3 nephritic factor in three subjects, and elevated levels of serum membrane attack complex in three subjects. After 12 months, two subjects showed significantly reduced serum creatinine, one subject achieved marked reduction in proteinuria, and one subject had stable laboratory parameters but histopathologic improvements. Elevated serum membrane attack complex levels normalized on therapy and paralleled improvements in creatinine and proteinuria. Conclusions Clinical and histopathologic data suggest a response to eculizumab in some but not all subjects with dense deposit disease and C3 glomerulonephritis. Elevation of serum membrane attack complex before treatment may predict response. Additional research is needed to define the subgroup of dense deposit disease/C3 glomerulonephritis patients in whom eculizumab therapy can be considered. PMID:22403278

The Falklands War, 1982: How Technological Deployments Shaped Decisions and the Outcome of the War

DTIC Science & Technology

2010-04-01

attacks resulted in four Skyhawks shot down, thre~ e by Brilliant and one mistakenly by the Argentinean anti-air defense at Port Stanley.97 The second...P(ly/ortd: maximum external wcapun lond, 5,0001b/2,270kg Ran/( e : with one in-ilight rdudling, over :~,000 nnmicd miles/5,560km/3,455 scarmc miles...scril\\c radius, 250 namical miks /463km/2.HS smtntc miles I’VCAIIA Speed: rrmximlllll h;vcl spct:d ar J,OOOm.or 9,8 115 feet <~ltirudc, 27

Plasma Control of Separated Flows on Delta Wings at High Angles of Attack

DTIC Science & Technology

2009-03-18

of Attack 5a. CONTRACT NUMBER ISTC Registration No: 3646 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) Dr. Anatoly Alexandrovich...NUMBER(S) ISTC 06-7002 12. DISTRIBUTION/AVAILABILITY STATEMENT Approved for public release; distribution is unlimited. 13. SUPPLEMENTARY...This work is supported financially by EOARD and performed under the agreement with the International Science and Technology Center ( ISTC ), Moscow

Identity of the segment of human complement C8 recognized by complement regulatory protein CD59.

PubMed

Lockert, D H; Kaufman, K M; Chang, C P; Hüsler, T; Sodetz, J M; Sims, P J

1995-08-25

CD59 antigen is a membrane glycoprotein that inhibits the activity of the C5b-9 membrane attack complex (MAC), thereby protecting human cells from lysis by human complement. The inhibitory function of CD59 derives from its capacity to interact with both the C8 and C9 components of MAC, preventing assembly of membrane-inserted C9 polymer. MAC-inhibitory activity of CD59 is species-selective and is most effective when both C8 and C9 derive from human or other primate plasma. Rabbit C8 and C9, which can substitute for human C8 and C9 in MAC, mediate virtually unrestricted lysis of human cells expressing CD59. In order to identify the segment of human C8 that is recognized by CD59, recombinant peptides containing human or rabbit C8 sequence were expressed in Escherichia coli and purified. CD59 was found to specifically bind to a peptide corresponding to residues 334-385 of the human C8 alpha-subunit, and to require a disulfide bond between Cys345 and Cys369. No specific binding was observed to the corresponding sequence from rabbit C8 alpha (residues 334-386). To obtain functional evidence that this segment of human C8 alpha is selectively recognized by CD59, recombinant C8 proteins were prepared by co-transfecting COS-7 cells with human/rabbit chimeras of the C8 alpha cDNA, and cDNAs encoding the C8 beta and C8 gamma chains. Hemolytic activity of MAC formed with chimeric C8 was analyzed using target cells reconstituted with CD59. These experiments confirmed that CD59 recognizes a conformationally sensitive epitope that is within a segment of human C8 alpha internal to residues 320-415. Our data also suggest that optimal interaction of CD59 with this segment of human C8 alpha is influenced by N-terminal flanking sequence in C8 alpha and by human C8 beta, but is unaffected by C8 gamma.

Multiple bonds between transition metals and main-group elements. 73. Synthetic routes to rhenium(V) alkyl and rhenium(VII) alkylidyne complexes. X-ray crystal structures of (. eta. sup 5 -C sub 5 Me sub 5 )Re( double bond O)(CH sub 3 )(CH sub 2 C(CH sub 3 ) sub 3 ) and (. eta. sup 5 -C sub 5 Me sub 5 )(Br) sub 3 Re triple bond CC(CH sub 3 ) sub 3

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

Herrmann, W.A.; Felixberger, J.K.; Anwander, R.

1990-05-01

Dialkyloxo({eta}{sup 5}pentamethylcyclopentadienyl)rhenium(V) complexes ({eta}{sup 5}-C{sub 5}Me{sub 5})Re({double bond}O)(CH{sub 3})R{prime}(R{prime} = C{sub 2}H{sub 5}, CH{sub 2}Si(CH{sub 3}){sub 3}, CH{sub 2}C(CH{sub 3}){sub 3}), 1c-e, have become accessible through alkylation of ({eta}{sup 5}-C{sub 5}Me{sub 5})Re({double bond}O)(Cl)(CH{sub 3}) (7) with R{prime}MgCl. 1c-e are the first rhenium complexes containing different alkyl ligands. The neopentyl derivative 1e (R{prime} = CH{sub 2}C(CH{sub 3}){sub 3}) crystallizes in the orthorhombic space group Pbca with a = 960.7 (2), b = 2.844.5 (4), c = 1,260.7 (2) pm, and Z = 8. The X-ray crystal structure was refined to R{sub W} = 3.9%. The chiral molecule shows a distorted tetrahedralmore » geometry around the rhenium center. The tribromide 3b has been structurally characterized. Brown crystals of 3b belong to space group P2{sub 1}/c with unit cell dimensions a = 1,311.5 (2), b = 723.0 (1), c = 1,901.6 (2) pm, {beta} = 92.68 (1){degree}, and Z = 4. The structure exhibits a four-legged piano stool geometry with no trans influence of the neopentylidyne ligand to the bromine atom.« less

Predictive value of the complement system for sepsis-induced disseminated intravascular coagulation in septic patients in emergency department.

PubMed

Zhao, Xin; Chen, Yun-Xia; Li, Chun-Sheng

2015-04-01

To investigate changes in circulating complement component C3, membrane attack complex (MAC), and mannose-binding lectin (MBL) in patients with sepsis-induced disseminated intravascular coagulation (DIC). Adult septic patients admitted to the emergency department (ED) of Beijing Chao-Yang Hospital were enrolled. A DIC score of 5 or higher was considered sepsis-induced DIC. Circulating C3, MAC, and MBL levels were detected on ED arrival and compared between patients with and without DIC. The predictive value of C3, MAC, and MBL for sepsis-induced DIC at ED arrival and development of DIC after admission were assessed by receiver operating characteristic curve and logistic regression. We enrolled 267 septic patients between February and December 2013. Complement 3, MAC, and MBL were higher in the DIC group (P < .01). Membrane attack complex was the independent predictor of sepsis-induced DIC. The area under the curve of MAC in predicting sepsis-induced DIC was 0.793. During hospitalization, 25 patients without DIC at enrollment developed DIC. Membrane attack complex and Sequential Organ Failure Assessment independently predicted progress to DIC. The area under the curve of MAC was 0.741. Complement 3, MAC, and MBL were significantly increased in septic patients with DIC. Membrane attack complex independently predicted sepsis-induced DIC and development of DIC after ED admission. Copyright © 2014 Elsevier Inc. All rights reserved.

The alternative complement pathway control protein H binds to immune complexes and serves their detection

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

Nydegger, U.E.; Corvetta, A.; Spaeth, P.J.

1983-01-01

During solubilization of immune complexes C3b becomes fixed to the immunoglobulin part and serves as a receptor for the alternative complement pathway control protein H. The H-C3b immune complex interaction can be made detectable using 4% polyethyleneglycol to separate free from bound /sup 125/I-H. Tetanus toxoid (Te)/anti-Te complexes kept soluble with fresh serum and containing 125 IU of specific antibody bound 18% of /sup 125/I-H; when fresh serum was chelated with 10 mM EDTA, /sup 125/I-H binding was only 5%. On sucrose density gradients, the H-binding material sedimented in the range of 12 to 30 S. In 36 serum samplesmore » from rheumatoid arthritis (RA) patients and in 12 serum samples from patients with systemic lupus erythematosus (SLE), /sup 125/I-H binding was significantly elevated to 9.5 +/- 4.7% (mean +/- 1 SD) and 13.3 +/- 5.6%, respectively, while /sup 125/I-H binding by 36 normal human sera was 4 +/- 2%. RA samples (17/36, 47%) and SLE samples (9/12, 75%) had H-binding values increased by more than 2 SD above the normal mean. The serum samples were also assessed for conglutinin- and C1q-binding activities; a significant correlation between H and C1q binding was observed (P less than 0.001); there was no correlation between H and conglutinin binding. Although binding to immune complexes through its interaction with C3b, H clearly detects a population of complexes other than conglutinin, thus expanding the possibilities of further characterizing pathological complexes.« less

Molecular modeling of methyl-α-Neu5Ac analogues docked against cholera toxin--a molecular dynamics study.

PubMed

Blessy, J Jino; Sharmila, D Jeya Sundara

2015-02-01

Molecular modeling of synthetic methyl-α-Neu5Ac analogues modified in C-9 position was investigated by molecular docking and molecular dynamics (MD) simulation methods. Methyl-α-Neu5Ac analogues were docked against cholera toxin (CT) B subunit protein and MD simulations were carried out for three Methyl-α-Neu5Ac analogue-CT complexes (30, 10 and 10 ns) to estimate the binding activity of cholera toxin-Methyl-α-Neu5Ac analogues using OPLS_2005 force field. In this study, direct and water mediated hydrogen bonds play a vital role that exist between the methyl-α-9-N-benzoyl-amino-9-deoxy-Neu5Ac (BENZ)-cholera toxin active site residues. The Energy plot, RMSD and RMSF explain that the simulation was stable throughout the simulation run. Transition of phi, psi and omega angle for the complex was calculated. Molecular docking studies could be able to identify the binding mode of methyl-α-Neu5Ac analogues in the binding site of cholera toxin B subunit protein. MD simulation for Methyl-α-9-N-benzoyl-amino-9-deoxy-Neu5Ac (BENZ), Methyl-α-9-N-acetyl-9-deoxy-9-amino-Neu5Ac and Methyl-α-9-N-biphenyl-4-acetyl-deoxy-amino-Neu5Ac complex with CT B subunit protein was carried out, which explains the stable nature of interaction. These methyl-α-Neu5Ac analogues that have computationally acceptable pharmacological properties may be used as novel candidates for drug design for cholera disease.

Comparing acquired angioedema with hereditary angioedema (types I/II): findings from the Icatibant Outcome Survey.

PubMed

Longhurst, H J; Zanichelli, A; Caballero, T; Bouillet, L; Aberer, W; Maurer, M; Fain, O; Fabien, V; Andresen, I

2017-04-01

Icatibant is used to treat acute hereditary angioedema with C1 inhibitor deficiency types I/II (C1-INH-HAE types I/II) and has shown promise in angioedema due to acquired C1 inhibitor deficiency (C1-INH-AAE). Data from the Icatibant Outcome Survey (IOS) were analysed to evaluate the effectiveness of icatibant in the treatment of patients with C1-INH-AAE and compare disease characteristics with those with C1-INH-HAE types I/II. Key medical history (including prior occurrence of attacks) was recorded upon IOS enrolment. Thereafter, data were recorded retrospectively at approximately 6-month intervals during patient follow-up visits. In the icatibant-treated population, 16 patients with C1-INH-AAE had 287 attacks and 415 patients with C1-INH-HAE types I/II had 2245 attacks. Patients with C1-INH-AAE versus C1-INH-HAE types I/II were more often male (69 versus 42%; P = 0·035) and had a significantly later mean (95% confidence interval) age of symptom onset [57·9 (51·33-64·53) versus 14·0 (12·70-15·26) years]. Time from symptom onset to diagnosis was significantly shorter in patients with C1-INH-AAE versus C1-INH-HAE types I/II (mean 12·3 months versus 118·1 months; P = 0·006). Patients with C1-INH-AAE showed a trend for higher occurrence of attacks involving the face (35 versus 21% of attacks; P = 0·064). Overall, angioedema attacks were more severe in patients with C1-INH-HAE types I/II versus C1-INH-AAE (61 versus 40% of attacks were classified as severe to very severe; P < 0·001). Median total attack duration was 5·0 h and 9·0 h for patients with C1-INH-AAE versus C1-INH-HAE types I/II, respectively. © 2016 British Society for Immunology.

Comparing acquired angioedema with hereditary angioedema (types I/II): findings from the Icatibant Outcome Survey

PubMed Central

Zanichelli, A.; Caballero, T.; Bouillet, L.; Aberer, W.; Maurer, M.; Fain, O.; Fabien, V.; Andresen, I.

2017-01-01

Summary Icatibant is used to treat acute hereditary angioedema with C1 inhibitor deficiency types I/II (C1‐INH‐HAE types I/II) and has shown promise in angioedema due to acquired C1 inhibitor deficiency (C1‐INH‐AAE). Data from the Icatibant Outcome Survey (IOS) were analysed to evaluate the effectiveness of icatibant in the treatment of patients with C1‐INH‐AAE and compare disease characteristics with those with C1‐INH‐HAE types I/II. Key medical history (including prior occurrence of attacks) was recorded upon IOS enrolment. Thereafter, data were recorded retrospectively at approximately 6‐month intervals during patient follow‐up visits. In the icatibant‐treated population, 16 patients with C1‐INH‐AAE had 287 attacks and 415 patients with C1‐INH‐HAE types I/II had 2245 attacks. Patients with C1‐INH‐AAE versus C1‐INH‐HAE types I/II were more often male (69 versus 42%; P = 0·035) and had a significantly later mean (95% confidence interval) age of symptom onset [57·9 (51·33–64·53) versus 14·0 (12·70–15·26) years]. Time from symptom onset to diagnosis was significantly shorter in patients with C1‐INH‐AAE versus C1‐INH‐HAE types I/II (mean 12·3 months versus 118·1 months; P = 0·006). Patients with C1‐INH‐AAE showed a trend for higher occurrence of attacks involving the face (35 versus 21% of attacks; P = 0·064). Overall, angioedema attacks were more severe in patients with C1‐INH‐HAE types I/II versus C1‐INH‐AAE (61 versus 40% of attacks were classified as severe to very severe; P < 0·001). Median total attack duration was 5·0 h and 9·0 h for patients with C1‐INH‐AAE versus C1‐INH‐HAE types I/II, respectively. PMID:27936514

Complement C5a-C5aR interaction enhances MAPK signaling pathway activities to mediate renal injury in trichloroethylene sensitized BALB/c mice.

PubMed

Zhang, Jia-xiang; Zha, Wan-sheng; Ye, Liang-ping; Wang, Feng; Wang, Hui; Shen, Tong; Wu, Chang-hao; Zhu, Qi-xing

2016-02-01

We have previously shown complement activation as a possible mechanism for trichloroethylene (TCE) sensitization, leading to multi-organ damage including the kidneys. In particular, excessive deposition of C5 and C5b-9-the membrane attack complex, which can generate significant tissue damage, was observed in the kidney tissue after TCE sensitization. The present study tested the hypothesis that anaphylatoxin C5a binding to its receptor C5aR mediates renal injury in TCE-sensitized BALB/c mice. BALB/c mice were sensitized through skin challenge with TCE, with or without pretreatment by the C5aR antagonist W54011. Kidney histopathology and the renal functional test were performed to assess renal injury, and immunohistochemistry and fluorescent labeling were carried out to assess C5a and C5aR expressions. TCE sensitization up-regulated C5a and C5aR expressions in kidney tissue, generated inflammatory infiltration, renal tubule damage, glomerular hypercellularity and impaired renal function. Antagonist pretreatment blocked C5a binding to C5aR and attenuated TCE-induced tissue damage and renal dysfunction. TCE sensitization also caused the deposition of major pro-inflammatory cytokines IL-2, TNF-α and IFN-γ in the kidney tissue (P < 0.05); this was accompanied by increased expression of P-p38, P-ERK and P-JNK proteins (P < 0.05). Pretreatment with the C5aR antagonist attenuated the increase of expression of P-p38, P-ERK and P-JNK proteins (P < 0.05) and also consistently reduced the TCE sensitization-induced increase of IL-2, TNF-α and IFN-γ (P < 0.05). These data identify C5a binding to C5aR, MAP kinase activation, and inflammatory cytokine release as a novel mechanism for complement-mediated renal injury by sensitization with TCE or other environmental chemicals. Copyright © 2015 John Wiley & Sons, Ltd.

Study on the immunological safety of universal plasma in the Chinese population in vitro.

PubMed

Chen, Guanyi; Zhu, Liguo; Wang, Shufang; Zhuang, Yuan; Yu, Yang; Wang, Deqing

2017-04-01

The prepared procedure for universal plasma in the Chinese population has been developed. However, the immunological safety with the level of antibodies, soluble immune complexes and complements is necessary to investigate. The universal plasma was pooled at the optimal ratio of A:B:AB=6:2.5:1.5 at 22°C for 1 hour. The titer of IgM antibodies was detected by saline agglutination, and the titer of IgG antibodies was detected by a Polybrene test after IgM destroyed by 2-mereaptoethanol. The hemolysis extent of RBC was investigated by an extracorporal hemolysis test, and the concentration of free-hemoglobin was determined by the ortho-tolidine method. The levels of CIC-C1q, C3b and TCC (C5-9) were tested using an enzyme linked immunosorbent assay (ELISA). The titer of IgM and IgG in universal plasma was lower than 2 and 4, respectively. The hemolysis of the universal plasma with A, B and AB group RBCs was negative with values of 5.5, 6.8 and 5.7, respectively. The level of CIC-C1q and TCC (C5-9) in universal plasma was comparable to that in A or B type pooled plasma, but CIC-C1q was lower than that and TCC (C5-9) was higher than that in AB type pooled plasma. The level of complement C3b was comparable to that in A type pooled plasma, but lower than that in B type pooled plasma and higher than that in AB type pooled plasma. The results of this study demonstrated that the immunological levels were within an acceptable range and confirmed the safety in vitro. Copyright © 2016 Elsevier Ltd. All rights reserved.

C1q-targeted inhibition of the classical complement pathway prevents injury in a novel mouse model of acute motor axonal neuropathy.

PubMed

McGonigal, Rhona; Cunningham, Madeleine E; Yao, Denggao; Barrie, Jennifer A; Sankaranarayanan, Sethu; Fewou, Simon N; Furukawa, Koichi; Yednock, Ted A; Willison, Hugh J

2016-03-02

Guillain-Barré syndrome (GBS) is an autoimmune disease that results in acute paralysis through inflammatory attack on peripheral nerves, and currently has limited, non-specific treatment options. The pathogenesis of the acute motor axonal neuropathy (AMAN) variant is mediated by complement-fixing anti-ganglioside antibodies that directly bind and injure the axon at sites of vulnerability such as nodes of Ranvier and nerve terminals. Consequently, the complement cascade is an attractive target to reduce disease severity. Recently, C5 complement component inhibitors that block the formation of the membrane attack complex and subsequent downstream injury have been shown to be efficacious in an in vivo anti-GQ1b antibody-mediated mouse model of the GBS variant Miller Fisher syndrome (MFS). However, since gangliosides are widely expressed in neurons and glial cells, injury in this model was not targeted exclusively to the axon and there are currently no pure mouse models for AMAN. Additionally, C5 inhibition does not prevent the production of early complement fragments such as C3a and C3b that can be deleterious via their known role in immune cell and macrophage recruitment to sites of neuronal damage. In this study, we first developed a new in vivo transgenic mouse model of AMAN using mice that express complex gangliosides exclusively in neurons, thereby enabling specific targeting of axons with anti-ganglioside antibodies. Secondly, we have evaluated the efficacy of a novel anti-C1q antibody (M1) that blocks initiation of the classical complement cascade, in both the newly developed anti-GM1 antibody-mediated AMAN model and our established MFS model in vivo. Anti-C1q monoclonal antibody treatment attenuated complement cascade activation and deposition, reduced immune cell recruitment and axonal injury, in both mouse models of GBS, along with improvement in respiratory function. These results demonstrate that neutralising C1q function attenuates injury with a consequent neuroprotective effect in acute GBS models and promises to be a useful new target for human therapy.

Silylene extrusion from organosilanes via double geminal Si-H bond activation by a Cp*Ru(kappa2-P,N)+ complex: observation of a key stoichiometric step in the glaser-tilley alkene hydrosilylation mechanism.

PubMed

Rankin, Matthew A; MacLean, Darren F; Schatte, Gabriele; McDonald, Robert; Stradiotto, Mark

2007-12-26

Treatment of Cp*RuCl(kappa2-P,N-2b) (2b = 2-NMe2-3-PiPr2-indene) with TlSO3CF3 produced the cyclometalated complex [4]+SO3CF3- in 94% isolated yield. Exposure of [4]+X- (X = B(C6F5)4 or SO3CF3) to Ph2SiH2 (10 equiv) or PhSiH3 afforded the corresponding [Cp*(mu-P,N-2b)(H)2Ru=SiRPh]+X- complexes, [5]+X- (R = Ph; X = B(C6F5)4, 82%; X = SO3CF3, 39%) and [6]+X- (R = H; X = B(C6F5)4, 94%; X = SO3CF3, 95%). Notably, these transformations represent the first documented examples of Ru-mediated silylene extrusion via double geminal Si-H bond activation of an organosilane-a key step in the recently proposed Glaser-Tilley (G-T) alkene hydrosilylation mechanism. Treatment of [5]+B(C6F5)4- with KN(SiMe3)2 or [6]+SO3CF3- with NaN(SiMe3)2 afforded the corresponding zwitterionic Cp*(mu-2-NMe2-3-PiPr2-indenide)(H)2Ru=SiRPh complex in 69% (R = Ph, 7) or 86% (R = H, 8) isolated yield. Both [6]+X- and 8 proved unreactive toward 1-hexene and styrene and provided negligible catalytic turnover in the attempted metal-mediated hydrosilylation of these substrates with PhSiH3, thereby providing further empirical evidence for the required intermediacy of base-free Ru=Si species in the G-T mechanism. Isomerization of the P,N-indene ligand backbone in [6]+X-, giving rise to [Cp*(mu-1-PiPr2-2-NMe2-indene)(H)2Ru=SiHPh]+X- ([9]+X-), was observed. In the case of [9]+SO3CF3-, net intramolecular addition of the Ru=Si-H group across the styrene-like C=C unit within the ligand backbone to give 10 (96% isolated yield) was observed. Crystallographic characterization data are provided for [4]+X-, [5]+X-, [6]+X-, 8, and 10.

Ruthenium bidentate phosphine complexes for the coordination and catalytic dehydrogenation of amine- and phosphine-boranes.

PubMed

Ledger, Araminta E W; Ellul, Charles E; Mahon, Mary F; Williams, Jonathan M J; Whittlesey, Michael K

2011-07-25

Addition of the amine-boranes H(3)B⋅NH(2)tBu, H(3)B⋅NHMe(2) and H(3)B⋅NH(3) to the cationic ruthenium fragment [Ru(xantphos)(PPh(3))(OH(2))H][BAr(F)(4)] (2; xantphos=4,5-bis(diphenylphosphino)-9,9-dimethylxanthene; BAr(F)(4)=[B{3,5-(CF(3))(2)C(6)H(3)}(4)](-)) affords the η(1)-B-H bound amine-borane complexes [Ru(xantphos)(PPh(3))(H(3)B⋅NH(2)tBu)H][BAr(F)(4)] (5), [Ru(xantphos)(PPh(3))(H(3) B⋅NHMe(2))H][BAr(F)(4)] (6) and [Ru(xantphos)(PPh(3))(H(3)B⋅NH(3))H][BAr(F)(4)] (7). The X-ray crystal structures of 5 and 7 have been determined with [BAr(F)(4)] and [BPh(4)] anions, respectively. Treatment of 2 with H(3)B⋅PHPh(2) resulted in quite different behaviour, with cleavage of the B-P interaction taking place to generate the structurally characterised bis-secondary phosphine complex [Ru(xantphos)(PHPh(2))(2)H][BPh(4)] (9). The xantphos complexes 2, 5 and 9 proved to be poor precursors for the catalytic dehydrogenation of H(3)B⋅NHMe(2). While the dppf species (dppf=1,1'-bis(diphenylphosphino)ferrocene) [Ru(dppf)(PPh(3))HCl] (3) and [Ru(dppf)(η(6)-C(6)H(5)PPh(2))H][BAr(F)(4)] (4) showed better, but still moderate activity, the agostic-stabilised N-heterocyclic carbene derivative [Ru(dppf)(ICy)HCl] (12; ICy=1,3-dicyclohexylimidazol-2-ylidene) proved to be the most efficient catalyst with a turnover number of 76 h(-1) at room temperature. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis, X-ray structure and cytotoxic effect of nickel(II) complexes with pyrazole ligands.

PubMed

Sobiesiak, Marta; Lorenz, Ingo-Peter; Mayer, Peter; Woźniczka, Magdalena; Kufelnicki, Aleksander; Krajewska, Urszula; Rozalski, Marek; Budzisz, Elzbieta

2011-12-01

Here we present the synthesis of the new Ni(II) complexes with chelating ligands 1-benzothiazol-2-yl-3,5-dimethyl-1H-pyrazole (a), 5-(2-hydroxyphenyl)-3-methyl-1-(2-pyridylo)-1H-pyrazole-4-carboxylic acid methyl ester (b) and 1-benzothiazol-2-yl-5-(2-hydroxyphenyl)-3-methyl-1H-pyrazole-4-carboxylic acid methyl ester (c). These ligands a-c create solid complexes with Ni(II). The crystal and molecular structures of two complexes were determined by X-ray diffraction method. Thermal stability of two complexes with ligand c by TG/DTG and DSC methods were also shown. Cytotoxic activity of all the complexes against three tumour cell lines and to normal endothelial cells (HUVEC) was also estimated. Complexes with ligand c exhibited relatively high cytotoxic activity towards HL-60 and NALM-6 leukaemia cells and WM-115 melanoma cells. Cytotoxic effectiveness of one of these complexes against melanoma WM-115 cells was two times higher than that of cisplatin. The protonation constant log K=9.63 of ligand b corresponding to the phenol 2-hydroxy group has been determined in 10% (v/v) DMSO/water solution (25°C). The coordination modes (formation of two monomeric species: NiL and NiL(2)) in the complexes with Ni(II) are discussed for b on the basis of the potentiometric and UV/Vis data. Copyright © 2011 Elsevier Masson SAS. All rights reserved.

Syntheses, Structural Characterization and Thermoanalysis of Transition-Metal Compounds Derived from 3,5-Dinitropyridone

PubMed Central

Fan, Rong; Zhou, Qiu-Ping; Zhang, Guo-Fang; Cai, Mei-Yu; Li, Ping; Gan, Li-Hua; Zhao, Feng-Qi; Li, Ji-Zhen; Fan, Xue-Zhong; Ng, Seik Weng

2010-01-01

Nine metal compounds of Mn(II), Zn(II) and Cd(II) derived from dinitropyridone ligands (3,5-dinitro-pyrid-2-one, 2HDNP; 3,5-dinitropyrid-4-one, 4HDNP and 3,5-dinitropyrid-4-one-N- hydroxide, 4HDNPO) were characterized by elemental analysis, FT-IR and partly by TG-DSC. Three of which were further structurally characterized by X-ray single-crystal diffraction analysis. The structures of the three compounds, Mn(4DNP)2(H2O)4, 4, Zn(4DNPO)2(H2O)4, 8, and Cd(4DNPO)2(H2O)4, 9, crystallize in the monoclinic space group P2(1)/n and Z = 2, with a = 8.9281(9), b = 9.1053(9), c = 10.6881(11) Å, β = 97.9840(10)° for 4; a = 8.4154(7), b = 9.9806(8), c = 10.5695(8) Å, β = 97.3500(10)° for 8; a = 8.5072(7), b = 10.2254(8), c = 10.5075(8) Å, β 96.6500(10)° for 9. All three complexes are octahedral consisting of four equatorial water molecules, and two nitrogen or oxygen donor ligands (DNP or DNPO). The abundant hydrogen-bonding and π-π stacking interactions seem to contribute to stabilization of the crystal structures of the compounds. The TG-DTG results revealed that the complexes showed a weight loss sequence corresponding to all coordinated water molecules, nitro groups, the breaking of the pyridine rings and finally the formation of metal oxides. PMID:20526459

Syntheses, Structural Characterization and Thermoanalysis of Transition-Metal Compounds Derived from 3,5-Dinitropyridone.

PubMed

Fan, Rong; Zhou, Qiu-Ping; Zhang, Guo-Fang; Cai, Mei-Yu; Li, Ping; Gan, Li-Hua; Zhao, Feng-Qi; Li, Ji-Zhen; Fan, Xue-Zhong; Ng, Seik Weng

2009-09-28

Nine metal compounds of Mn(II), Zn(II) and Cd(II) derived from dinitropyridone ligands (3,5-dinitro-pyrid-2-one, 2HDNP; 3,5-dinitropyrid-4-one, 4HDNP and 3,5-dinitropyrid-4-one-N- hydroxide, 4HDNPO) were characterized by elemental analysis, FT-IR and partly by TG-DSC. Three of which were further structurally characterized by X-ray single-crystal diffraction analysis. The structures of the three compounds, Mn(4DNP)(2)(H(2)O)(4), 4, Zn(4DNPO)(2)(H(2)O)(4), 8, and Cd(4DNPO)(2)(H(2)O)(4), 9, crystallize in the monoclinic space group P2(1)/n and Z = 2, with a = 8.9281(9), b = 9.1053(9), c = 10.6881(11) A, beta = 97.9840(10) degrees for 4; a = 8.4154(7), b = 9.9806(8), c = 10.5695(8) A, beta = 97.3500(10) degrees for 8; a = 8.5072(7), b = 10.2254(8), c = 10.5075(8) A, beta 96.6500(10) degrees for 9. All three complexes are octahedral consisting of four equatorial water molecules, and two nitrogen or oxygen donor ligands (DNP or DNPO). The abundant hydrogen-bonding and pi-pi stacking interactions seem to contribute to stabilization of the crystal structures of the compounds. The TG-DTG results revealed that the complexes showed a weight loss sequence corresponding to all coordinated water molecules, nitro groups, the breaking of the pyridine rings and finally the formation of metal oxides.

Structural Analysis of Der p 1–Antibody Complexes and Comparison with Complexes of Proteins or Peptides with Monoclonal Antibodies

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

Osinski, Tomasz; Pomés, Anna; Majorek, Karolina A.

Der p 1 is a major allergen from the house dust mite, Dermatophagoides pteronyssinus, that belongs to the papain-like cysteine protease family. To investigate the antigenic determinants of Der p 1, we determined two crystal structures of Der p 1 in complex with the Fab fragments of mAbs 5H8 or 10B9. Epitopes for these two Der p 1–specific Abs are located in different, nonoverlapping parts of the Der p 1 molecule. Nevertheless, surface area and identity of the amino acid residues involved in hydrogen bonds between allergen and Ab are similar. The epitope for mAb 10B9 only showed a partialmore » overlap with the previously reported epitope for mAb 4C1, a cross-reactive mAb that binds Der p 1 and its homolog Der f 1 from Dermatophagoides farinae. Upon binding to Der p 1, the Fab fragment of mAb 10B9 was found to form a very rare α helix in its third CDR of the H chain. To provide an overview of the surface properties of the interfaces formed by the complexes of Der p 1–10B9 and Der p 1–5H8, along with the complexes of 4C1 with Der p 1 and Der f 1, a broad analysis of the surfaces and hydrogen bonds of all complexes of Fab–protein or Fab–peptide was performed. This work provides detailed insight into the cross-reactive and specific allergen–Ab interactions in group 1 mite allergens. The surface data of Fab–protein and Fab–peptide interfaces can be used in the design of conformational epitopes with reduced Ab binding for immunotherapy.« less

Viral replication. Structural basis for RNA replication by the hepatitis C virus polymerase.

PubMed

Appleby, Todd C; Perry, Jason K; Murakami, Eisuke; Barauskas, Ona; Feng, Joy; Cho, Aesop; Fox, David; Wetmore, Diana R; McGrath, Mary E; Ray, Adrian S; Sofia, Michael J; Swaminathan, S; Edwards, Thomas E

2015-02-13

Nucleotide analog inhibitors have shown clinical success in the treatment of hepatitis C virus (HCV) infection, despite an incomplete mechanistic understanding of NS5B, the viral RNA-dependent RNA polymerase. Here we study the details of HCV RNA replication by determining crystal structures of stalled polymerase ternary complexes with enzymes, RNA templates, RNA primers, incoming nucleotides, and catalytic metal ions during both primed initiation and elongation of RNA synthesis. Our analysis revealed that highly conserved active-site residues in NS5B position the primer for in-line attack on the incoming nucleotide. A β loop and a C-terminal membrane-anchoring linker occlude the active-site cavity in the apo state, retract in the primed initiation assembly to enforce replication of the HCV genome from the 3' terminus, and vacate the active-site cavity during elongation. We investigated the incorporation of nucleotide analog inhibitors, including the clinically active metabolite formed by sofosbuvir, to elucidate key molecular interactions in the active site. Copyright © 2015, American Association for the Advancement of Science.

New Methods for the Analysis of Water-Soluble Vitamins in Infant Formula and Adult/Pediatric Nutritionals.

PubMed

Martin, Frederic; Giménez, Ester Campos; Konings, Erik

2016-01-01

Water-soluble vitamins (WSVs) are a group of organic compounds which are essential micronutrients. WSVs could be divided between the B complex group and vitamin C (l-ascorbic acid). Within the B complex group, eight vitamins are recognized: vitamins B1 (thiamin), B2 (riboflavin), B3 (niacin or niacinamide), B5 (pantothenic acid), B6 (pyridoxine, pyridoxal, or pyridoxamine), B7 (biotin), B9 (folic acid), and B12 (various cobalamins). This paper reviews the new methods for the analysis of these vitamins, with a focus on infant formula and adult nutritionals.

Roles of Bridging Ligand Topology and Conformation in Controlling Exchange Interactions between Paramagnetic Molybdenum Fragments in Dinuclear and Trinuclear Complexes.

PubMed

Ung VÂ, V&acaron;n Ân; Cargill Thompson, Alexander M. W.; Bardwell, David A.; Gatteschi, Dante; Jeffery, John C.; McCleverty, Jon A.; Totti, Federico; Ward, Michael D.

1997-07-30

The magnetic properties of two series of dinuclear complexes, and one trinuclear complex, have been examined as a function of the bridging pathway between the metal centers. The first series of dinuclear complexes is [{Mo(V)(O)(Tp)Cl}(2)(&mgr;-OO)], where "OO" is [1,4-O(C(6)H(4))(n)O](2)(-) (n = 1, 1; n = 2, 3), [4,4'-O(C(6)H(3)-2-Me)(2)O](2)(-) (4), or [1,3-OC(6)H(4)O](2)(-) (2) [Tp = tris(3,5-dimethylpyrazolyl)hydroborate]. The second series of dinuclear complexes is [{Mo(I)(NO)(Tp)Cl}(2)(&mgr;-NN)], where "NN" is 4,4'-bipyridyl (5), 3,3'-dimethyl-4,4'-bipyridine (6), 3,8-phenanthroline (7), or 2,7-diazapyrene (8). The trinuclear complex is [{Mo(V)(O)(Tp)Cl}(3)(1,3,5-C(6)H(3)O(3))] (9), whose crystal structure was determined [9.5CH(2)Cl(2): C(56)H(81)B(3)Cl(13)Mo(3)N(18)O(6); monoclinic, P2(1)/n; a = 13.443, b = 41.46(2), c = 14.314(6) Å; beta = 93.21(3) degrees; V = 7995(5) Å(3); Z = 4; R(1) = 0.106]. In these complexes, the sign and magnitude of the exchange coupling constant J is clearly related to both the topology and the conformation of the bridging ligand [where J is derived from H = -JS(1)().S(2)() for 1-8 and H = -J(S(1)().S(2)() + S(2)().S(3)() + S(1)().S(3)()) for 9]. The values are as follows: 1, -80 cm(-)(1); 2, +9.8 cm(-)(1); 3, -13.2 cm(-)(1); 4, -2.8 cm(-)(1); 5, -33 cm(-)(1); 6, -3.5 cm(-)(1); 7, -35.6 cm(-)(1); 8, -35.0 cm(-)(1); 9, +14.4 cm(-)(1). In particular the following holds: (1) J is negative (antiferromagnetic exchange) across the para-substituted bridges ligands of 1 and 3-8 but positive (ferromagnetic exchange) across the meta-substituted bridging ligands of 2 and 9. (2) J decreases in magnitude dramatically as the bridging ligand conformation changes from planar to twisted (compare 3 and 4, or 6 and 8). These observations are consistent with a spin-polarization mechanism for the exchange interaction, propagated across the pi-system of the bridging ligand by via overlap of bridging ligand p(pi) orbitals with the d(pi) magnetic orbitals of the metals. The EPR spectrum of 9 is characteristic of a quartet species and shows weak Deltam(s) = 2 and Deltam(s) = 3 transitions at one-half and one-third, respectively, of the field strength of the principal Deltam(s) = 1 component.

Neutral Fe(IV) alkylidenes, including some that bind dinitrogen.

PubMed

Lindley, Brian M; Jacobs, Brian P; MacMillan, Samantha N; Wolczanski, Peter T

2016-03-11

Neutral, formally Fe(IV) alkylidene species are sought as plausible olefin metathesis catalysts, and the synthesis of several is described herein. The complexes are prepared via nucleophilic attack (Nu = MeLi, PhCH2K, 2-picolyllithium, Me2PCH2Li, MePhPCH2Li, Ph2PCH2Li) at the imine of cationic [mer-{κ-C,N,C-(C6H4-yl)-2-CH=N(2-C6H4-C(iPr)=)}Fe(PMe3)3][B(3,5-CF3-C6H3)4]. In contrast, MeMgCl and mesityllithium displaced and deprotonated bound PMe3, respectively. Structural details are provided for mer-{κ-C,N,C-(C6H4-yl)-2-CH(Bn)N(2-C6H4-C(iPr))}Fe{trans-(PMe3)2}N2 and {κ-C,N,C,P-(C6H4-yl)-2-CH(CH2PMe2)N(2-C6H4-C(iPr)=)}Fe(PMe3)2.

Pincer phosphine complexes of ruthenium: formation of Ru(P-O-P)(PPh3)HCl (P-O-P = xantphos, DPEphos, (Ph2PCH2CH2)2O) and Ru(dppf)(PPh3)HCl and characterization of cationic dioxygen, dihydrogen, dinitrogen, and arene coordinated phosphine products.

PubMed

Ledger, Araminta E W; Moreno, Aitor; Ellul, Charles E; Mahon, Mary F; Pregosin, Paul S; Whittlesey, Michael K; Williams, Jonathan M J

2010-08-16

Treatment of Ru(PPh(3))(3)HCl with the pincer phosphines 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene (xantphos), bis(2-diphenylphosphinophenyl)ether (DPEphos), or (Ph(2)PCH(2)CH(2))(2)O affords Ru(P-O-P)(PPh(3))HCl (xantphos, 1a; DPEphos, 1b; (Ph(2)PCH(2)CH(2))(2)O, 1c). The X-ray crystal structures of 1a-c show that all three P-O-P ligands coordinate in a tridentate manner through phosphorus and oxygen. Abstraction of the chloride ligand from 1a-c by NaBAr(4)(F) (BAr(4)(F) = B(3,5-C(6)H(3)(CF(3))(2))(4)) gives the cationic aqua complexes [Ru(P-O-P)(PPh(3))(H(2)O)H]BAr(4)(F) (3a-c). Removal of chloride from 1a by AgOTf yields Ru(xantphos)(PPh(3))H(OTf) (2a), which reacts with water to form [Ru(xantphos)(PPh(3))(H(2)O)H](OTf). The aqua complexes 3a-b react with O(2) to generate [Ru(xantphos)(PPh(3))(eta(2)-O(2))H]BAr(4)(F) (5a) and [Ru(DPEphos)(PPh(3))(eta(2)-O(2))H]BAr(4)(F) (5b). Addition of H(2) or N(2) to 3a-c yields the thermally unstable dihydrogen and dinitrogen species [Ru(P-O-P)(PPh(3))(eta(2)-H(2))H]BAr(4)(F) (6a-c) and [Ru(P-O-P)(PPh(3))(N(2))H]BAr(4)(F) (7a-c), which have been characterized by multinuclear NMR spectroscopy at low temperature. Ru(PPh(3))(3)HCl reacts with 1,1'-bis(diphenylphosphino)ferrocene (dppf) to give the 16-electron complex Ru(dppf)(PPh(3))HCl (1d), which upon treatment with NaBAr(4)(F), affords [Ru(dppf){(eta(6)-C(6)H(5))PPh(2)}H]BAr(4)(F) (8), in which the PPh(3) ligand binds eta(6) through one of the PPh(3) phenyl rings. Reaction of 8 with CO or PMe(3) at elevated temperatures yields the 18-electron products [Ru(dppf)(PPh(3))(CO)(2)H]BAr(F)(4) (9) and [Ru(PMe(3))(5)H]BAr(4)(F) (10).

Synthesis and structure of the first discrete dinuclear cationic aluminum complexes.

PubMed

Wang, Xingbao; Dorcet, Vincent; Luo, Yi; Carpentier, Jean-Francois; Kirillov, Evgueni

2016-08-02

The reactions of the charge neutral dinuclear aluminum tetraalkyl complexes of di-Schiff base ligands, i.e. [AlMe2{ON}-R-{ON}AlMe2] (1a, R = 1,3-propylene; 1b, R = 1,3-cyclohexylene) with B(C6F5)3 and [H(Et2O)2](+)[H2N{B(C6F5)3}2](-) were investigated. When B(C6F5)3 was used as the cationizing agent (1 or 2 equiv. vs. Al), only monocationic dinuclear complexes [2a,b]+[MeB(C6F5)3]- were obtained. In contrast, with [H(Et2O)2](+)[H2N{B(C6F5)3}2](-), both mixed-dicationic [3a,b·(OEt2)2]2+[MeB(C6F5)3]-[H2N{B(C6F5)3}2]- and homo-dicationic [3a,b·(OEt2)2]2+[H2N{B(C6F5)3}2]-2 ion-pairs were prepared. All cationic complexes were characterized by (1)H, (13)C, (19)F and (11)B NMR spectroscopy, and an X-ray diffraction study was performed for [3b·(OEt2)2]2+[H2N{B(C6F5)3}2]-2.

21 CFR 184.1212 - Calcium pantothenate.

Code of Federal Regulations, 2012 CFR

2012-04-01

... ((C9H16NO5)2Ca, CAS Reg. No. of the D-isomer, 137-08-6) is a salt of pantothenic acid, one of the vitamins of the B complex. Only the D-isomer of pantothenic acid has vitamin activity, although both the D-isomer..._regulations/ibr_locations.html. (c) In accordance with § 184.1(b)(1), the ingredient is used in food with no...

21 CFR 184.1212 - Calcium pantothenate.

Code of Federal Regulations, 2013 CFR

2013-04-01

... ((C9H16NO5)2Ca, CAS Reg. No. of the D-isomer, 137-08-6) is a salt of pantothenic acid, one of the vitamins of the B complex. Only the D-isomer of pantothenic acid has vitamin activity, although both the D-isomer..._regulations/ibr_locations.html. (c) In accordance with § 184.1(b)(1), the ingredient is used in food with no...

A contribution to the rational design of Ru(CO)3Cl2L complexes for in vivo delivery of CO.

PubMed

Seixas, João D; Santos, Marino F A; Mukhopadhyay, Abhik; Coelho, Ana C; Reis, Patrícia M; Veiros, Luís F; Marques, Ana R; Penacho, Nuno; Gonçalves, Ana M L; Romão, Maria J; Bernardes, Gonçalo J L; Santos-Silva, Teresa; Romão, Carlos C

2015-03-21

A few ruthenium based metal carbonyl complexes, e.g. CORM-2 and CORM-3, have therapeutic activity attributed to their ability to deliver CO to biological targets. In this work, a series of related complexes with the formula [Ru(CO)3Cl2L] (L = DMSO (3), L-H3CSO(CH2)2CH(NH2)CO2H) (6a); D,L-H3CSO(CH2)2CH(NH2)CO2H (6b); 3-NC5H4(CH2)2SO3Na (7); 4-NC5H4(CH2)2SO3Na (8); PTA (9); DAPTA (10); H3CS(CH2)2CH(OH)CO2H (11); CNCMe2CO2Me (12); CNCMeEtCO2Me (13); CN(c-C3H4)CO2Et) (14)) were designed, synthesized and studied. The effects of L on their stability, CO release profile, cytotoxicity and anti-inflammatory properties are described. The stability in aqueous solution depends on the nature of L as shown using HPLC and LC-MS studies. The isocyanide derivatives are the least stable complexes, and the S-bound methionine oxide derivative is the more stable one. The complexes do not release CO gas to the headspace, but release CO2 instead. X-ray diffraction of crystals of the model protein Hen Egg White Lysozyme soaked with 6b (4UWN) and 8 (4UWN) shows the addition of Ru(II)(CO)(H2O)4 at the His15 binding site. Soakings with 7(4UWN) produced the metallacarboxylate [Ru(COOH)(CO)(H2O)3](+) bound to the His15 site. The aqueous chemistry of these complexes is governed by the water-gas shift reaction initiated with the nucleophilic attack of HO(-) on coordinated CO. DFT calculations show this addition to be essentially barrierless. The complexes have low cytotoxicity and low hemolytic indices. Following i.v. administration of CORM-3, the in vivo bio-distribution of CO differs from that obtained with CO inhalation or with heme oxygenase stimulation. A mechanism for CO transport and delivery from these complexes is proposed.

Enchancement of Gamma-Aminobutyric Acid Production by Co-Localization of Neurospora crassa OR74A Glutamate Decarboxylase with Escherichia coli GABA Transporter Via Synthetic Scaffold Complex.

PubMed

Somasundaram, Sivachandiran; Maruthamuthu, Murali Kannan; Ganesh, Irisappan; Eom, Gyeong Tae; Hong, Soon Ho

2017-09-28

Gamma-aminobutyric acid is a precursor of nylon-4, which is a promising heat-resistant biopolymer. GABA can be produced from the decarboxylation of glutamate by glutamate decarboxylase. In this study, a synthetic scaffold complex strategy was employed involving the Neurospora crassa glutamate decarboxylase (GadB) and Escherichia coli GABA antiporter (GadC) to improve GABA production. To construct the complex, the SH3 domain was attached to the N. crassa GadB, and the SH3 ligand was attached to the N-terminus, middle, and C-terminus of E. coli GadC. In the C-terminus model, 5.8 g/l of GABA concentration was obtained from 10 g/l glutamate. When a competing pathway engineered strain was used, the final GABA concentration was further increased to 5.94 g/l, which corresponds to 97.5% of GABA yield. With the introduction of the scaffold complex, the GABA productivity increased by 2.9 folds during the initial culture period.

Space shuttle: Static stability and control investigation of the NR-GD/C delta wing booster (B-15B-1) and a Reusable Nuclear Stage (RNS) M = 0.6 - 4.96

NASA Technical Reports Server (NTRS)

Allen, E. C.

1971-01-01

Experimental aerodynamic investigations were made in the NASA/MSFC 14 x 14 inch trisonic wind tunnel on a NR-GD/C 0.0031 scale model delta wing booster (B-15B-1) and reusable nuclear stage (RNS). Three basic configurations were tested: (1) the B-15B-1 booster alone, (2) the RNS alone, and (3) the booster with the RNS mounted piggyback. Six component force and moment data were recorded for each of these configurations over an angle of attack range from -16 deg to 4 deg at zero degrees sideslip, and over an angle of sideslip range from -10 deg to 10 deg at zero and -6 degrees angle of attack. The configurations were tested over a Mach number range of 0.6 to 5.0 with a nominal Reynolds number of 6.5 million per foot except for Mach 1.2 and 3.0 where the Reynolds number were 12.4 million and 4.4 million per foot respectively.

Reactions of a Ruthenium Complex with Substituted N-Propargyl Pyrroles.

PubMed

Chia, Pi-Yeh; Huang, Shou-Ling; Liu, Yi-Hong; Lin, Ying-Chih

2016-04-05

In an investigation into the chemical reactions of N-propargyl pyrroles 1 a-c, containing aldehyde, keto, and ester groups on the pyrrole ring, with [Ru]-Cl ([Ru]=Cp(PPh3 )2 Ru; Cp=C5 H5 ), an aldehyde group in the pyrrole ring is found to play a crucial role in stimulating the cyclization reaction. The reaction of 1 a, containing an aldehyde group, with [Ru]-Cl in the presence of NH4 PF6 yields the vinylidene complex 2 a, which further reacts with allyl amine to give the carbene complex 6 a with a pyrrolizine group. However, if 1 a is first reacted with allyl amine to yield the iminenyne 8 a, then the reaction of 8 a with [Ru]-Cl in the presence of NH4 PF6 yields the ruthenium complex 9 a, containing a cationic pyrrolopyrazinium group, which has been fully characterized by XRD analysis. These results can be adequately explained by coordination of the triple bond of the propargyl group to the ruthenium metal center first, followed by two processes, that is, formation of a vinylidene intermediate or direct nucleophilic attack. Additionally, the deprotonation of 2 a by R4 NOH yields the neutral acetylide complex 3 a. In the presence of NH4 PF6 , the attempted alkylation of 3 a resulted in the formation the Fischer-type amino-carbene complex 5 a as a result of the presence of NH3, which served as a nucleophile. With KPF6, the alkylation of 3 a with ethyl and benzyl bromoacetates afforded the disubstituted vinylidene complexes 10 a and 11 a, containing ester groups, which underwent deprotonation reactions to give the furyl complexes 12 a and 13 a, respectively. For 13 a, containing an O-benzyl group, subsequent 1,3-migration of the benzyl group was observed to yield product 14 a with a lactone unit. Similar reactivity was not observed for the corresponding N-propargyl pyrroles 1 b and 1 c, which contained keto and ester groups, respectively, on the pyrrole ring. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Combined Radiation and Thermal Injury after Nuclear Attack

DTIC Science & Technology

1990-01-01

0T’Fit f-copy Combined Radiation and Thermal Injury 04 After Nuclear Attack , (M) William K. Becker, Teresa M. Buescher, William G. Cioffi, William F...Chicago, 1979, pp. 5-61. 4. Reiss, E., Stirman, J. A., Artz, C . P., et al. Fluid and electrolyte balance in burns. JAMA 152:1309- 1313, 1953. 5...et al. Septicemia in burn injury. J Trauma 1:22-31,1961. 7. Moncrief , J. A., Lindberg, R. B., Switzer, W. E., et al. Use of topical antibacterial

Rotary balance data for a typical single-engine general aviation design for an angle of attack range of 8 deg to 90 deg. 1: Low wing model C. [wind tunnel tests

NASA Technical Reports Server (NTRS)

Mulcay, W. J.; Rose, R. A.

1980-01-01

Aerodynamic characteristics obtained in a helical flow environment utilizing a rotary balance located in the Langley spin tunnel are presented in plotted form for a 1/6 scale, single engine, low wing, general aviation model (model C). The configurations tested included the basic airplane and control deflections, wing leading edge and fuselage modification devices, tail designs and airplane components. Data are presented without analysis for an angle of attack range of 8 deg to 90 deg and clockwise and counter clockwise rotations covering an omega b/2v range from 0 to .9.

Separation of Bombyxin from a neuropeptide of Bombyx mori showing Summer-morph-producing Hormone (SMPH) activity in the Asian Comma Butterfly, Polygonia c-aureum L.

PubMed

Endo, K; Yamanaka, A; Mitsumasu, K; Sakurama, T; Tanaka, D

1997-02-21

A neuropeptide from brain-suboesophageal ganglion (Br-SG) complexes of the silkmoth, Bombyx mori, shows summer-morph-producing hormone (SMPH) activity in the Asian comma butterfly, P. c-aureum. The SMPH-active peptide was extracted and demonstrated to be almost the same molecular size as bombyxin (4-5kD), a nueropeptide which shows prothoracicotropic hormone (PTTH) activity when assayed in vitro with prothoracic glands (PGs) of 4th-instar B. mori larvae in vitro. A Sephadex G-50 fraction of 3-8kD molecules prepared from Br-SG complexes of B. mori adults was applied to CM-, SP-, DEAE- or QAE- Toyoperal columns at pH 5.6 (or pH 6.9). The SMPH-activity could be separated from the PTTH-activity (or bombyxin) by subjecting a SMPH- and PTTH-active preparation of B. mori to anion-exchange chromatography at pH 6.9. By reversed-phase HPLC following an anion-exchange chromatography, SMPH-activity was recovered in two fractions of 40-45% acetonitril. Results demonstrate that the B. mori peptide showing the SMPH-activity in P. c-aureum is a different molecule than bombyxin.

Menière's disease: combined pharmacotherapy with betahistine and the MAO-B inhibitor selegiline-an observational study.

PubMed

Strupp, Michael; Kraus, Ludwig; Schautzer, Franz; Rujescu, Dan

2018-03-12

Since oral betahistine has a very high first-pass effect (ca. 99%), metabolized by monoamine oxidases (MAO), the benefits of a high-dosage betahistine monotherapy were compared with those of a lower dosage of betahistine in combination with the MAO-B inhibitor (MAO-B) selegiline on the frequency of acute attacks of vertigo in patients with Menière's disease (MD). Thirteen adults aged 40-75 years (mean 58.9 years; six females) had initially been treated with a high dosage of betahistine dihydrochloride for at least 1 year. Under this therapy, all of them had ≤ 1 attack for ≥ 3 months prior to the combination pharmacotherapy. Subsequently, they received 5 mg/day selegiline and the dosage of betahistine was reduced to about one tenth and then individually adjusted to the dosage needed to achieve the same treatment response (≤ 1 per 3 months, observational period of at least 6 months). The initial dosage for the long-term "titration" of the attacks of vertigo was 9-80 24-mg tablets/day (mean 37.3), i.e. 216-1920 mg/day (mean 895.4 mg/day). After the combination with selegiline, the dosage needed to achieve the same benefit for ≥ 3 months was 3-36 24-mg tablets (mean 8.5), i.e., 72-864 mg/day [mean 204.9 mg/day, p < 0.001 (paired t test)]. One patient transiently stopped the treatment with selegiline, another one reduced the dosage to 2.5 mg/day and the attacks re-occurred after 2-4 weeks. Six out of 13 patients reported transient fullness of the head during the combined treatment; in 2 of them this went away when they switched to 2.5 mg bid. In the longer term (> 9 months), one patient had to increase the selegiline dosage to 5 mg bd, one patient stopped the treatment with selegiline. The achievement of the same clinical effect with a significantly lower (about 1/5) dosage of betahistine can be explained by the inhibition of the MAO-B by selegiline leading to higher serum concentrations of betahistine. This approach is in line with recent developments to bypass the first-pass effect of betahistine by transbuccal or intranasal application. Despite the substantial methodological limitations of such an observational study, this combined pharmacotherapy could be an alternative to a high-dosage monotherapy with betahistine of MD.

The membrane attack complex of complement contributes to plasmin-induced synthesis of platelet-activating factor by endothelial cells and neutrophils

PubMed Central

Lupia, Enrico; Del Sorbo, Lorenzo; Bergerone, Serena; Emanuelli, Giorgio; Camussi, Giovanni; Montrucchio, Giuseppe

2003-01-01

Thrombolytic agents, used to restore blood flow to ischaemic tissues, activate several enzymatic systems with pro-inflammatory effects, thus potentially contributing to the pathogenesis of ischaemia–reperfusion injury. Platelet-activating factor (PAF), a phospholipid mediator of inflammation, has been implicated in the pathogenesis of this process. We previously showed that the infusion of streptokinase (SK) induces the intravascular release of PAF in patients with acute myocardial infarction (AMI), and that cultured human endothelial cells (EC) synthesized PAF in response to SK and plasmin (PLN). In the present study, we investigated the role of the membrane attack complex (MAC) of complement in the PLN-induced synthesis of PAF. In vivo, we showed a correlation between the levels of soluble terminal complement components (sC5b-9) and the concentrations of PAF detected in blood of patients with AMI infused with SK. In vitro both EC and polymorphonuclear neutrophils (PMN), incubated in the presence of PLN and normal human serum, showed an intense staining for the MAC neoepitope, while no staining was detected when they were incubated with PLN in the presence of heat-inactivated normal human serum. Moreover, the insertion of MAC on EC and PMN plasmamembrane elicited the synthesis of PAF. In conclusion, our results elucidate the mechanisms involved in PAF production during the activation of the fibrinolytic system, showing a role for complement products in this setting. The release of PAF may increase the inflammatory response, thus limiting the beneficial effects of thrombolytic therapy. Moreover, it may have a pathogenic role in other pathological conditions, such as transplant rejection, tumoral angiogenesis, and septic shock, where fibrinolysis is activated. PMID:12871223

The membrane attack complex of complement contributes to plasmin-induced synthesis of platelet-activating factor by endothelial cells and neutrophils.

PubMed

Lupia, Enrico; Del Sorbo, Lorenzo; Bergerone, Serena; Emanuelli, Giorgio; Camussi, Giovanni; Montrucchio, Giuseppe

2003-08-01

Thrombolytic agents, used to restore blood flow to ischaemic tissues, activate several enzymatic systems with pro-inflammatory effects, thus potentially contributing to the pathogenesis of ischaemia-reperfusion injury. Platelet-activating factor (PAF), a phospholipid mediator of inflammation, has been implicated in the pathogenesis of this process. We previously showed that the infusion of streptokinase (SK) induces the intravascular release of PAF in patients with acute myocardial infarction (AMI), and that cultured human endothelial cells (EC) synthesized PAF in response to SK and plasmin (PLN). In the present study, we investigated the role of the membrane attack complex (MAC) of complement in the PLN-induced synthesis of PAF. In vivo, we showed a correlation between the levels of soluble terminal complement components (sC5b-9) and the concentrations of PAF detected in blood of patients with AMI infused with SK. In vitro both EC and polymorphonuclear neutrophils (PMN), incubated in the presence of PLN and normal human serum, showed an intense staining for the MAC neoepitope, while no staining was detected when they were incubated with PLN in the presence of heat-inactivated normal human serum. Moreover, the insertion of MAC on EC and PMN plasmamembrane elicited the synthesis of PAF. In conclusion, our results elucidate the mechanisms involved in PAF production during the activation of the fibrinolytic system, showing a role for complement products in this setting. The release of PAF may increase the inflammatory response, thus limiting the beneficial effects of thrombolytic therapy. Moreover, it may have a pathogenic role in other pathological conditions, such as transplant rejection, tumoral angiogenesis, and septic shock, where fibrinolysis is activated.

Cryopreservation of Schistosome Larvae.

DTIC Science & Technology

1980-10-02

anacardic acid, obtained by fractionation of an extract from the cashew nut shell, were tested for toxicity to B. glabrata. The triene form was most toxic...attacked and destroyed muscle cells of the atrium, a reaction against self; 6# 5) Molluscicidal effect of cashew nut shell extract for D. abgata was...Passive unsuliibll !Nd& bl. gjabn phawed amebocytes attacking and destroying mul" ea- Y ad~t effct f cshe nut shell extract for 9, a~ was shown to be due

Computational Investigation of a Pitch Oscillating Canard on Lift Enhancement and Tip Vortex Mitigation

DTIC Science & Technology

2017-04-01

dimensional canard and computational domain ..........................4 Fig. 3 Prescribed dynamic ramp motion for the 2-D airfoil at k2 = 0.5 (a) and...airfoil as a function of equivalent mean angle of attack, unfiltered (a, c) and filtered (b, d), for reduced frequency of oscillation of k2 = 0.5 (a–b...filtered (b, d), for reduced frequency of oscillation of k2 = 0.5 (a–b) and 1.0 (c–d), M∞ = 0.5 .....10 Fig. 6 Lift coefficient of dynamic canard

Results of investigations (OA77 and OA78) on an 0.015-scale 140A/B configuration space shuttle vehicle orbiter model 49-0 in the AEDC VKF B and C wind tunnels, revision A

NASA Technical Reports Server (NTRS)

Gillins, R. L.

1975-01-01

Aerodynamic data obtained from wind tunnel tests of an 0.015-scale 140A/B configuration SSV Orbiter model in the AEDC VKF B and C wind tunnels are presented. Tests were conducted at Mach numbers of 6 and 8 in the B tunnel and at a Mach number of 10 to in the C tunnel to verify hypersonic stability and control characteristics, determine control surface effectiveness, and investigate Reynolds number effects of the 140A/B configuration. Force data were obtained for various control surface settings and Reynolds numbers in the angle-of-attack range of 15 deg to 45 deg and at angles of sideslip of -5 deg to +10 deg. Data were obtained for a few configurations at angles of attack from -27 deg to 45 deg. Control surface variables included elevon, rudder, speedbrake and bodyflap deflections. The effects of an alternate wing leading edge shape were investigated to determine its hypersonic stability and control characteristics.

Expression, purification, crystallization and preliminary X-ray analysis of a C-terminal fragment of the Epstein–Barr virus ZEBRA protein

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

Morand, Patrice; Laboratoire de Virologie Moléculaire et Structurale, EA 2939, Université Joseph Fourier, Grenoble; Budayova-Spano, Monika

A C-terminal fragment of the Epstein–Barr virus lytic switch protein ZEBRA has been crystallized in complex with DNA. A C-terminal fragment of the Epstein–Barr virus immediate-early transcription factor ZEBRA has been expressed as a recombinant protein in Escherichia coli and purified to homogeneity. The fragment behaves as a dimer in solution, consistent with the presence of a basic region leucine-zipper (bZIP) domain. Crystals of the fragment in complex with a DNA duplex were grown by the hanging-drop vapour-diffusion technique using polyethylene glycol 4000 and magnesium acetate as crystallization agents. Crystals diffract to better than 2.5 Å resolution using synchrotron radiationmore » (λ = 0.976 Å). Crystals belong to space group C2, with unit-cell parameters a = 94.2, b = 26.5, c = 98.1 Å, β = 103.9°.« less

C-F activation of fluorinated arenes using NHC-stabilized nickel(0) complexes: selectivity and mechanistic investigations.

PubMed

Schaub, Thomas; Fischer, Peter; Steffen, Andreas; Braun, Thomas; Radius, Udo; Mix, Andreas

2008-07-23

The reaction of [Ni2((i)Pr2Im)4(COD)] 1a or [Ni((i)Pr2Im)2(eta(2)-C2H4)] 1b with different fluorinated arenes is reported. These reactions occur with a high chemo- and regioselectivity. In the case of polyfluorinated aromatics of the type C6F5X such as hexafluorobenzene (X = F) octafluorotoluene (X = CF3), trimethyl(pentafluorophenyl)silane (X = SiMe3), or decafluorobiphenyl (X = C6F5) the C-F activation regioselectively takes place at the C-F bond in the para position to the X group to afford the complexes trans-[Ni((i)Pr2Im)2(F)(C6F5)]2, trans-[Ni((i)Pr2Im)2(F)(4-(CF3)C6F4)] 3, trans-[Ni((i)Pr2Im)2(F)(4-(C6F5)C6F4)] 4, and trans-[Ni((i)Pr2Im)2(F)(4-(SiMe3)C6F4)] 5. Complex 5 was structurally characterized by X-ray diffraction. The reaction of 1a with partially fluorinated aromatic substrates C6H(x)F(y) leads to the products of a C-F activation trans-[Ni((i)Pr2Im)2(F)(2-C6FH4)] 7, trans-[Ni((i)Pr2Im)2(F)(3,5-C6F2H3)] 8, trans-[Ni((i)Pr2Im)2(F)(2,3-C6F2H3)] 9a and trans-[Ni((i)Pr2Im)2(F)(2,6-C6F2H3)] 9b, trans-[Ni((i)Pr2Im)2(F)(2,5-C6F2H3)] 10, and trans-[Ni((i)Pr2Im)2(F)(2,3,5,6-C6F4H)] 11. The reaction of 1a with octafluoronaphthalene yields exclusively trans-[Ni((i)Pr2Im)2(F)(1,3,4,5,6,7,8-C10F7)] 6a, the product of an insertion into the C-F bond in the 2-position, whereas for the reaction of 1b with octafluoronaphthalene the two isomers trans-[Ni((i)Pr2Im)2(F)(1,3,4,5,6,7,8-C10F7)] 6a and trans-[Ni((i)Pr2Im)2(F)(2,3,4,5,6,7,8-C10F7)] 6b are formed in a ratio of 11:1. The reaction of 1a or of 1b with pentafluoropyridine at low temperatures affords trans-[Ni((i)Pr2Im)2(F)(4-C5NF4)] 12a as the sole product, whereas the reaction of 1b performed at room temperature leads to the generation of trans-[Ni((i)Pr2Im)2(F)(4-C5NF4)] 12a and trans-[Ni((i)Pr2Im)2(F)(2-C5NF4)] 12b in a ratio of approximately 1:2. The detection of intermediates as well as kinetic studies gives some insight into the mechanistic details for the activation of an aromatic carbon-fluorine bond at the {Ni((i)Pr2Im)2} complex fragment. The intermediates of the reaction of 1b with hexafluorobenzene and octafluoronaphthalene, [Ni((i)Pr2Im)2(eta(2)-C6F6)] 13 and [Ni((i)Pr2Im)2(eta(2)-C10F8)] 14, have been detected in solution. They convert into the C-F activation products. Complex 14 was structurally characterized by X-ray diffraction. The rates for the loss of 14 at different temperatures for the C-F activation of the coordinated naphthalene are first order and the estimated activation enthalpy Delta H(double dagger) for this process was determined to be Delta H(double dagger) = 116 +/- 8 kJ mol(-1) (Delta S(double dagger) = 37 +/- 25 J K(-1) mol(-1)). Furthermore, density functional theory calculations on the reaction of 1a with hexafluorobenzene, octafluoronaphthalene, octafluorotoluene, 1,2,4-trifluorobenzene, and 1,2,3-trifluorobenzene are presented.

Gyroscope-Like Complexes Based on Dibridgehead Diphosphine Cages That Are Accessed by Three-Fold Intramolecular Ring Closing Metatheses and Encase Fe(CO)3, Fe(CO)2(NO)(+), and Fe(CO)3(H)(+) Rotators.

PubMed

Lang, Georgette M; Shima, Takanori; Wang, Leyong; Cluff, Kyle J; Skopek, Katrin; Hampel, Frank; Blümel, Janet; Gladysz, John A

2016-06-22

Reactions of trans-Fe(CO)3(P((CH2)mCH═CH2)3)2 (m = a/4; b/5, c/6, e/8) and Grubbs' catalyst (12-24 mol %, CH2Cl2, reflux) give the cage-like trienes trans- Fe(CO)3(P((CH2)mCH═CH(CH2)m)3 P) (3a-c,e, 60-81%). Hydrogenations (ClRh(PPh3)3, 60-80 °C) yield the title compounds trans- Fe(CO)3(P((CH2)n)3 P) (4a-c,e, 74-86%; n = 2m + 2), which have idealized D3h symmetry. A crystal structure of 4c suggests enough van der Waals clearance for the Fe(CO)3 moiety to rotate within the three P(CH2)14P linkages; structures of E,E,E-3a show rotation to be blocked by the shorter P(CH2)4CH═CH(CH2)4P linkages. Additions of NO(+)BF4(-) give the isoelectronic and isosteric cations [ Fe(CO)2(NO)(P((CH2)n)3 P)](+)BF4(-) (5a-c(+)BF4(-); 81-98%). Additions of [H(OEt2)2](+)BArf(-) (BArf = B(3,5-C6H3(CF3)2)4) afford the metal hydride complexes mer,trans-[ Fe(CO)3(H)(P((CH2)n)3 P)](+)BArf(-) (6a-c,e(+)BArf(-); 98-99%). The behavior of the rotators in the preceding complexes is probed by VT NMR. At ambient temperature in solution, 5a,b(+)BF4(-) and 6a(+)BArf(-) show two sets of P(CH2)n/2 (13)C NMR signals (2:1), whereas 5c(+)BF4(-) and 6b,c(+)BArf(-) show only one. At higher temperatures, the signals of 5b(+)BF4(-) coalesce; at lower temperatures, those of 5c(+)BF4(-) and 6b(+)BArf(-) decoalesce. These data give ΔH(⧧)/ΔS(⧧) values (kcal/mol and eu) of 8.3/-28.4 and 9.5/-6.5 for Fe(CO)2(NO)(+) rotation (5b,c(+)) and 6.1/-23.5 for Fe(CO)3(H)(+) rotation (6b(+)). (13)C CP/MAS NMR spectra show that the Fe(CO)3 moiety in polycrystalline 4c (but not 4a) undergoes rapid rotation between -60 and 95 °C. Approaches to minimizing these barriers and developing molecular gyroscopes are discussed.

Intramolecular Pauson-Khand reactions of methylenecyclopropane and bicyclopropylidene derivatives as an approach to spiro(cyclopropanebicyclo[n.3.0]alkenones).

PubMed

de Meijere, Armin; Becker, Heike; Stolle, Andreas; Kozhushkov, Sergei I; Bes, M Teresa; Salaün, Jacques; Noltemeyer, Mathias

2005-04-08

The trimethylsilyl-protected enynes 9a-c and 14a,b with alkynyl substituents on the three-membered ring or on the double bond of a methylenecyclopropane or a bicyclopropylidene moiety were prepared in two steps from the alcohols 6a-c and 12a,b, respectively, by conversion to the iodides and their coupling with lithium (trimethylsilyl)acetylide (8) in 38-73% overall yields. The bicyclopropylidene derivative 9d was synthesized in 49% yield directly from bicyclopropylidene (3) by lithiation followed by coupling with (5-iodopent-1-ynyl)trimethylsilane (11). Enynes 9b-d were protiodesilylated by treatment with K2CO3 in methanol to give the corresponding unprotected enynes 10b-d in 53, 74 and 94% yield, respectively. Enynes 17a-c with a carbonyl group adjacent to the acetylenic moiety were synthesized from oxo derivatives 15a-c by Wittig olefination followed by coupling with 8 in 47, 18 and 12% overall yield, respectively. Pauson-Khand reactions of the methylenecyclopropane derivatives with a substituent on the ring (9a,b and 10a) as well as on the double bond (14a,b and their in situ prepared protiodesilylated analogues) proceeded smoothly by stirring of the corresponding enyne with [Co2(CO)8] in dichloromethane at ambient temperature followed by treatment of the formed complexes with trimethylamine N-oxide under an oxygen atmosphere at -78 degrees C to give tricyclic or spirocyclopropanated bicyclic enones 18a,b, 19a, 20a,b, 21a,b in good yields. Alkynylbicyclopropylidene derivatives 9c,d and 10c,d formed the corresponding cobalt complexes at -78 to -20 degrees C. Treatment of the latter with N-methylmorpholine N-oxide under an argon atmosphere at -20 degrees C gave the spirocyclopropanated tricyclic enones 18c, 19c and 18d in 31-45% yields. The structure of 19c was proved by X-ray crystal structure analysis. The cyclization of enynones 17a-c in MeCN at 80 degrees C gave the spirocyclopropanated bicyclic diketones 22a-c in 38-65% yields. Intramolecular PKRs of the enynes 25a,d with a chiral auxiliary adjacent to the triple bond gave the corresponding products 26a,d in 70 and 79% yield, respectively, as 5:1 and 8:1 mixtures of diastereomers, respectively. Addition of lithium dimethylcuprate or higher order cuprates to the double bond of the former furnished bridgehead-substituted bicyclo[3.3.0]octanones 27a-c in 57-86% yields. Protiodesilylation of 27a followed by acetal cleavage gave the enantiomerically pure spirocyclopropanated bicyclo[3.3.0]octanedione (1R,5R)- 29a with [alpha]D(20)=-148 (c=1.0 in CHCl3) in 55% overall yield.

Regioselectivity in the gas-phase reactions of the O- radical anion with ([eta]5-cyclopentadienyl)tricarbonylmanganese(I) and ([eta]5-methylcyclopentadienyl)tricarbonylmanganese(I): formation and structure of C5H5MnO-n and C6H7MnO-n (n = 1, 2) ions

NASA Astrophysics Data System (ADS)

van den Berg, Klaas Jan; Ingemann, Steen; Nibbering, Nico M. M.

1994-06-01

The gas-phase reactions of the O- ion with ([eta]5-cyclopentadienyl)tricarbonylmanganese(I), CpMn(CO)3, and ([eta]5-methylcyclopentadienyl)tricarbonylmanganese(I), CH3CpMn(CO)3, have been studied with Fourier transform ion cyclotron resonance. The main reactions are (i) proton abstraction, (ii) loss of CO2, and (iii) expulsion of two or three CO molecules from the collision complex. Initial attack on a CO ligand is the main process as indicated by experiments with 18O- and the ion/molecule reactions of the product ions resulting from the loss of three CO molecules with water, aliphatic alcohols, methanethiol and SO2. The attack on a CO ligand followed by loss of three CO molecules is suggested to yield C5H5MnO- ions with a (cyclopentadienone)MnH- structure in the reaction with CpMn(CO)3 and (methylcyclopentadienone)MnH- ions if CH3CpMn(CO)3 is the substrate. A possible mechanism for the process leading to the indicated transformation of the Cp and CH3Cp ligands into C5H4O and CH3C5H3O ligands, respectively, is discussed together with the formation of (fulvene)Mn(OH)- ions following attack of O- on CH3CpMn(CO)3. The (cyclopentadienone)MnH- and (methylcyclopentadienone)MnH- ions react with N2O by oxygen atom abstraction to form C5H5MnO-2 and C6H7MnO-2 ions, respectively.

A Comparison of Ulnar Shortening Osteotomy Alone Versus Combined Arthroscopic Triangular Fibrocartilage Complex Debridement and Ulnar Shortening Osteotomy for Ulnar Impaction Syndrome

PubMed Central

Song, Hyun Seok

2011-01-01

Background This study compared the results of patients treated for ulnar impaction syndrome using an ulnar shortening osteotomy (USO) alone with those treated with combined arthroscopic debridement and USO. Methods The results of 27 wrists were reviewed retrospectively. They were divided into three groups: group A (USO alone, 10 cases), group B (combined arthroscopic debridement and USO, 9 cases), and group C (arthroscopic triangular fibrocartilage complex [TFCC] debridement alone, 8 cases). The wrist function was evaluated using the modified Mayo wrist score, disabilities of the arm, shoulder and hand (DASH) score and Chun and Palmer grading system. Results The modified Mayo wrist score in groups A, B, and C was 74.5 ± 8.9, 73.9 ± 11.6, and 61.3 ± 10.2, respectively (p < 0.05). The DASH score in groups A, B, and C was 15.6 ± 11.8, 19.3 ± 11.9, and 33.2 ± 8.5, respectively (p < 0.05). The average Chun and Palmer grading score in groups A and B was 85.7 ± 8.9 and 84.7 ± 6.7, respectively. The difference in the Mayo wrist score, DASH score and Chun and Palmer grading score between group A and B was not significant (p > 0.05). Conclusions Both USO alone and combined arthroscopic TFCC debridement with USO improved the wrist function and reduced the level of pain in the patients treated for ulnar impaction syndrome. USO alone may be the preferred method of treatment in patients if the torn flap of TFCC is not unstable. PMID:21909465

Steric and electronic ligand perturbations in catalysis: asymmetric allylic substitution reactions using C2-symmetrical phosphorus-chiral (bi)ferrocenyl donors.

PubMed

Nettekoven, U; Widhalm, M; Kalchhauser, H; Kamer, P C; van Leeuwen, P W; Lutz, M; Spek, A L

2001-02-09

Three series of P-chiral diphosphines based on ferrocene (1a-f, 2a-c) and biferrocenyl skeletons (3a-c), including novel ligands 1f and 3c, were employed in palladium-catalyzed allylic substitution reactions. Steric effects imposed by the phosphine residues were studied using C2-symmetrical donors 1 (1 = 1,1'-bis(arylphenylphosphino)ferrocene with aryl groups a = 1-naphthyl, b = 2-naphthyl, c = 2-anisyl, d = 2-biphenylyl, e = 9-phenanthryl, and f = ferrocenyl), whereas para-methoxy- and/or para-trifluoromethyl substitution of the phenyl moieties in 1a enabled investigation of ligand electronic effects applying ferrocenyl diphosphines 2a-c. Ligands 3 (3 = 2,2'-bis- (arylphenylphosphino)-1,1'-biferrocenyls with aryl substituents a,c = 1-naphthyl (diastereomers) and b = 2-biphenylyl) allowed for comparison of backbone structure effects (bite angle variation) in catalysis. Linear and cyclic allylic acetates served as substrates in typical test reactions; upon attack of soft carbon and nitrogen nucleophiles on (E)-1,3-diphenylprop-2-ene-1-yl acetate the respective malonate, amine, or imide products were obtained in enantioselectivities of up to 99% ee. A crystal structure analysis of a palladium 1,3-diphenyl-eta 3-allyl complex incorporating ligand (S,S)-1a revealed a marked distortion of the allyl fragment, herewith defining the regioselectivity of nucleophile addition.

An X-ray study of the effect of the bite angle of chelating ligands on the geometry of palladium(allyl) complexes: implications for the regioselectivity in the allylic alkylation.

PubMed

van Haaren, R J; Goubitz, K; Fraanje, J; van Strijdonck, G P; Oevering, H; Coussens, B; Reek, J N; Kamer, P C; van Leeuwen, P W

2001-07-02

X-ray crystal structures of a series of cationic (P-P)palladium(1,1-(CH(3))(2)C(3)H(3)) complexes (P-P = dppe (1,2-bis(diphenylphosphino)ethane), dppf (1,1'-bis(diphenylphosphino)ferrocene), and DPEphos (2,2'-bis(diphenylphosphino)diphenyl ether)) and the (Xantphos)Pd(C(3)H(5))BF(4) (Xantphos = 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene) complex have been determined. In the solid state structure, the phenyl rings of the ligand are oriented in the direction of the nonsymmetrically bound [1,1-(CH(3))(2)C(3)H(3)] moiety. An increase of the bite angle of the chelating ligand results in an increase of the cone angle. In complexes containing ligands having a large cone angle, the distances between the phenyl rings and the allyl moiety become small, resulting in a distortion of the symmetry of the palladium-allyl bond. In solution, two types of dynamic exchange have been observed, the pi-sigma rearrangement and the apparent rotation of the allyl moiety. At the same time, the folded structure of the ligand changes from an endo to an exo orientation or vice versa. The regioselectivity in the palladium-catalyzed allylic alkylation of 3-methyl-but-2-enyl acetate is determined by the cone angle of the bidentate phosphine ligand. Nucleophilic attack by a malonate anion takes place preferentially at the allylic carbon atom having the largest distance to palladium. Ligands with a larger cone angle direct the regioselectivity to the formation of the branched product, from 8% for dppe (1) to 61% found for Xantphos (6). The influence of the cone angle on the regioselectivity has been assigned to a sterically induced electronic effect.

On the IDAGAM I Combat Model.

DTIC Science & Technology

1977-06-01

defense missions in locations between the FEBA and the attackers’ targets; b) AAA can attack only aircraft attacking the guns them- selves or the targets...the guns are defending; c) SAM weapon systems can attack not only aircraft attack- ing them and the targets they defend but also, although possibly...Corporation), P.E. Louer (Department of the Army) and B.R. McEnany (Joint Chiefs of Staff/Studies, Analysis and Gaming Agency) for their help- ful

Complement System in Dermatological Diseases – Fire Under the Skin

PubMed Central

Panelius, Jaana; Meri, Seppo

2015-01-01

The complement system plays a key role in several dermatological diseases. Overactivation, deficiency, or abnormality of the control proteins are often related to a skin disease. Autoimmune mechanisms with autoantibodies and a cytotoxic effect of the complement membrane attack complex on epidermal or vascular cells can cause direct tissue damage and inflammation, e.g., in systemic lupus erythematosus (SLE), phospholipid antibody syndrome, and bullous skin diseases like pemphigoid. By evading complement attack, some microbes like Borrelia spirochetes and staphylococci can persist in the skin and cause prolonged symptoms. In this review, we present the most important skin diseases connected to abnormalities in the function of the complement system. Drugs having an effect on the complement system are also briefly described. On one hand, drugs with free hydroxyl on amino groups (e.g., hydralazine, procainamide) could interact with C4A, C4B, or C3 and cause an SLE-like disease. On the other hand, progress in studies on complement has led to novel anti-complement drugs (recombinant C1-inhibitor and anti-C5 antibody, eculizumab) that could alleviate symptoms in diseases associated with excessive complement activation. The main theme of the manuscript is to show how relevant the complement system is as an immune effector system in contributing to tissue injury and inflammation in a broad range of skin disorders. PMID:25688346

Effect of single doses of pindolol and d-fenfluramine on flumazenil-induced anxiety in panic disorder patients.

PubMed

Bernik, M; Ramos, R T; Hetem, L A B; Graeff, F

2017-11-04

The effects of the 5-HT 1A receptor blocker pindolol and the 5-HT releasing and uptake blocking agent d-fenfluramine, both used as indirect serotonin agonists, on flumazenil-induced acute anxiety reactions were studied in panic disorder patients to test the hypothesis that serotonin (5-HT) inhibits neural systems mediating panic attacks. Thirty never treated or drug free PD patients (16 females) aged 22-49 y (mean±SD, 32.9±8) received single doses of d-fenfluramine (n=10; 30mg, p.o.), pindolol (n=10; 5mg, p.o.), or placebo (n=10) 90 and 45min before a challenge test with flumazenil (1.5mg, i.v., in 10min), under double-blind conditions. Panic attacks occurred in 5 control subjects (placebo-flumazenil group), 5 subjects in the pindolol group and in 7 in the d-fenluramine pre-treated patients. Patients experiencing anxiety attacks following flumazenil reported higher increases in anxiety scores. Respiratory rate increases were not different between patients experiencing or not a panic attack. Despite sample size limitation, this study suggests that flumazenil induced anxiety reaction is not a good pharmacological model of panic attacks, considering the absence of serotonergic modulation of its effects. Copyright © 2017. Published by Elsevier B.V.

Risk Due to Radiological Terror Attacks With Natural Radionuclides

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

Friedrich, Steinhaeusler; Lyudmila, Zaitseva; Stan, Rydell

The naturally occurring radionuclides radium (Ra-226) and polonium (Po-210) have the potential to be used for criminal acts. Analysis of international incident data contained in the Database on Nuclear Smuggling, Theft and Orphan Radiation Sources (CSTO), operated at the University of Salzburg, shows that several acts of murder and terrorism with natural radionuclides have already been carried out in Europe and Russia. Five different modes of attack (T) are possible: (1) Covert irradiation of an individual in order to deliver a high individual dose; (2) Covert irradiation of a group of persons delivering a large collective dose; (3) Contamination ofmore » food or drink; (4) Generation of radioactive aerosols or solutions; (5) Combination of Ra-226 with conventional explosives (Dirty Bomb).This paper assesses the risk (R) of such criminal acts in terms of: (a) Probability of terrorist motivation deploying a certain attack mode T; (b) Probability of success by the terrorists for the selected attack mode T; (c) Primary damage consequence (C) to the attacked target (activity, dose); (d) Secondary damage consequence (C') to the attacked target (psychological and socio-economic effects); (e) Probability that the consequences (C, C') cannot be brought under control, resulting in a failure to manage successfully the emergency situation due to logistical and/or technical deficits in implementing adequate countermeasures. Extensive computer modelling is used to determine the potential impact of such a criminal attack on directly affected victims and on the environment.« less

Risk Due to Radiological Terror Attacks With Natural Radionuclides

NASA Astrophysics Data System (ADS)

Friedrich, Steinhäusler; Stan, Rydell; Lyudmila, Zaitseva

2008-08-01

The naturally occurring radionuclides radium (Ra-226) and polonium (Po-210) have the potential to be used for criminal acts. Analysis of international incident data contained in the Database on Nuclear Smuggling, Theft and Orphan Radiation Sources (CSTO), operated at the University of Salzburg, shows that several acts of murder and terrorism with natural radionuclides have already been carried out in Europe and Russia. Five different modes of attack (T) are possible: (1) Covert irradiation of an individual in order to deliver a high individual dose; (2) Covert irradiation of a group of persons delivering a large collective dose; (3) Contamination of food or drink; (4) Generation of radioactive aerosols or solutions; (5) Combination of Ra-226 with conventional explosives (Dirty Bomb). This paper assesses the risk (R) of such criminal acts in terms of: (a) Probability of terrorist motivation deploying a certain attack mode T; (b) Probability of success by the terrorists for the selected attack mode T; (c) Primary damage consequence (C) to the attacked target (activity, dose); (d) Secondary damage consequence (C') to the attacked target (psychological and socio-economic effects); (e) Probability that the consequences (C, C') cannot be brought under control, resulting in a failure to manage successfully the emergency situation due to logistical and/or technical deficits in implementing adequate countermeasures. Extensive computer modelling is used to determine the potential impact of such a criminal attack on directly affected victims and on the environment.

Controlled synthesis of racemic indenyl rare-earth metal complexes via the cooperation between the intramolecular coordination of donor atoms and a bridge.

PubMed

Zhou, Shuangliu; Wu, Zhangshuan; Zhou, Lingmin; Wang, Shaowu; Zhang, Lijun; Zhu, Xiancui; Wei, Yun; Zhai, Jinhua; Wu, Jie

2013-06-03

The reactions of Me2Si(C9H6CH2CH2-DG)2 (DG = NMe2 (1), CH2NMe2 (2), OMe (3), and N(CH2CH2)2O (4)) with [(Me3Si)2N]3RE(μ-Cl)Li(THF)3 in toluene afforded a series of racemic divalent rare-earth metal complexes: {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2-DG)2}RE (DG = NMe2, RE = Yb (6) and Eu (7); DG = CH2NMe2, RE = Yb (8), Eu (9), and Sm (10); DG = OMe, RE = Yb (11) and Eu (12); DG = N(CH2CH2)2O, RE = Yb (13) and Eu (14)). Similarly, the racemic divalent rare-earth metal complexes {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2CH2NMe2)(C9H5CH2CH2OMe)}RE (RE = Yb (15) and Eu (16)) were also obtained. The reaction of Me2Si(C9H5CH2CH2OMe)2Li2 with NdCl3 gave a racemic dimeric neodymium chloride {η(5):η(1):η(5)-Me2Si(C9H5CH2CH2OMe)2NdCl}2 (17), whereas the reaction of Me2Si(C9H5CH2CH2NMe2)2Li2 with SmCl3 afforded a racemic dinuclear samarium chloride bridged by lithium chloride {η(5):η(1):η(5):η(1)-Me2Si(C9H5CH2CH2NMe2)2SmCl}2(μ-LiCl) (18). Further reaction of complex 18 with LiCH2SiMe3 provided an unexpected rare-earth metal alkyl complex {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Sm (19) through the activation of an sp(3) C-H bond α-adjacent to the nitrogen atom. Complexes 19 and {η(5):η(1):η(5):η(1):σ-Me2Si(C9H5CH2CH2NMe2)[(C9H5CH2CH2N(CH2)Me]}Y (20) were also obtained by one-pot reactions of Me2Si(C9H5CH2CH2NMe2)2Li2 with RECl3 followed by treatment with LiCH2SiMe3. All compounds were fully characterized by spectroscopic methods and elemental analysis. Complexes 6-10 and 14-20 were further characterized by single-crystal X-ray diffraction analysis. All of the prepared rare-earth metal complexes were racemic, suggesting that racemic organo rare-earth metal complexes could be controllably synthesized by the cooperation between a bridge and the intramolecular coordination of donor atoms.

Mercury-Bridged Cobaltacarborane Complexes Containing B-Hg-B Three-Center Bonds. Synthesis and Structure of mu, mu’-((n5-C5R5)Co(CH3)2C2B3H4)Hg, mu-(n(5)-C5R5)Co(CH3)2C2B3H4)HgCl, (R=H, CH3) and Related Compounds.

DTIC Science & Technology

1980-11-01

MERCURY-BRIDGED COBALTACARBORANE COMPLEXES CONTAINING B-HG-B TH--ETC(U) NOV 80 D C FINSTER . R N GRIMES N0 0 0 1 4-75-0305 UNCLASSXFIED TR󈧨 NL ILn...C5R5) Co 3)2C2B3 4 2 5 .- -C5R5 )Co(CH3)2C2B3H4 ]HgCl, (R=H, CH3 ) and Related Compounds, David C./ Finster -- Russell N./Grimes ( Department of Chemistry...Compounds 1 \\David C. Finster And Russell N. Grimes* Abstract. Reactions of the nid~p-cobaltacarborane anions 01CR )(C 3 )C BH and [n (H 1oC ihH~5n 5

DIBALH mediated reduction of the acetal moiety on perhydrofuro[2,3-b]pyran derivatives.

PubMed

Marco-Contelles, J; Ruiz-Caro, J

2001-09-21

The reaction of DIBALH with bis(heteroannulated)-pyranosides containing the perhydrofuro[2,3-b]pyran moiety is described. The hydride attack at the anomeric carbon (C-9a) resulted in the exclusive tetrahydrofuran ring opening. The selectivity of this reaction has been evaluated as other benzylidene acetals built on these substrates remain practically or partially unaltered in these conditions depending on the steric volume of the O-protecting group located at C-4 (TBDMS vs. Me). This protocol can be considered as a new entry for the synthesis of chiral and highly functionalized cyclopentanes.

Characterization of monoclonal antibodies that specifically recognize the palm subdomain of hepatitis C virus nonstructural protein 5B polymerase.

PubMed

Ingravallo, P; Lahser, F; Xia, E; Sodowich, B; Lai, V C; Hong, Z; Zhong, W

2001-06-01

The nonstructural protein 5B (NS5B) of hepatitis C virus (HCV) is an RNA-dependent RNA polymerase (RdRp) which plays an essential role in viral RNA replication. Antibodies that specifically recognize NS5B will have utilities in monitoring NS5B production and subcellular localization, as well as in structure-function studies. In this report, three mouse monoclonal antibodies (mAbs), 16A9C9, 16D9A4 and 20A12C7, against a recombinant NS5B protein (genotype 1a, H-77 strain) were produced. These mAbs specifically recognize HCV NS5B, but not RdRps of polivirus (PV), bovine viral diarrhea virus (BVDV) or GB virus B (GBV-B). The mAbs can readily detect NS5B in cellular lysates of human osteosarcoma Saos2 cells constitutively expressing the nonstructural region of HCV (NS3-NS4A-NS4B-NS5A-NS5B). NS5B proteins of different HCV genotypes/subtypes (1a, 1b, 2a, 2c, 5a) showed varied affinity for these mAbs. Interestingly, the epitopes for the mAbs were mapped to the palm subdomain (amino acid 188-370) of the HCV RdRp as determined by immunoblotting analysis of a panel of HCV/GBV-B chimeric NS5B proteins. The binding site was mapped between amino acid 231 and 267 of NS5B for 16A9C9, and between 282 and 372 for 16D9A4 and 20A12C7. Furthermore, these mAbs showed no inhibitory effect on the NS5B polymerase activity in vitro.

Super Hydrides.

DTIC Science & Technology

1982-03-18

31/81 C. P . Mathew 2/1/79 - 10/31/79 S. Narasimhan 4/1/79 - present K. Ruralidhar 8/15/79 - 8/15/81 B. Nazer 9/1/80 - present V. Somayaji 8/15/81...readily / - 5. hydrolyzed to the corresponding amines. CH2RI+ R-C- N + H3B*SMe2 0.25 h ,H HCIH 2 >II NaOH RHNH RCH 2N\\ NCH2R 70-90% AB 70-90+ H On...derivatives, which are sufficiently weakly basic as not to complex with BMS. / 0 B R-C---NH 2 + 4/3 BH3’SMe 2 -> RCH2- N + 2 H2 (6) \\B - I - \\ 6. Treatment of

Quantification and Analysis of Offensive Situations in Different Formats of Sided Games In Soccer

PubMed Central

Garcia, Jorge Diaz-Cidoncha; Román, Ignacio Refoyo; Calleja-González, Julio; Dellal, Alexandre

2014-01-01

There has been a lot of research that enabled soccer to improve: its technique, tactics and strategy through analysis and training. Nevertheless, players’ need to interact with each other turns any defending or attacking situation into complex solutions with a wide range of variables to be considered, in which the player is never isolated and must make the move that has the most positive impact on play. Fifty-four sided games played in three different formats (5v5, 7v7 and 9v9) and with two age groups (U9 and U14) were filmed at three soccer clubs in Spain in order to identify the most relevant attacking moves, from a technical and tactical perspective. This study used the observational method; it is descriptive and is applied through well-prepared systematic quantitative observation in a natural environment. A key part of the method involved viewing the match recordings and logging moves that had been categorised beforehand. Cohen’s Kappa analysis showed that the results for the most representative variables presented a substantial degree of concordance (0.61–0.80). The results show that there were significant variations depending on the game format, and the following study will present a description and analysis of the aspects that had considerable influence on attacking moves in different formats of sided games (5v5, 7v7 and 9v9). The study also presents various practical applications for the area of training and analysing both youth and professional soccer. PMID:25713680

Complement Activation in Arterial and Venous Thrombosis is Mediated by Plasmin

PubMed Central

Foley, Jonathan H.; Walton, Bethany L.; Aleman, Maria M.; O'Byrne, Alice M.; Lei, Victor; Harrasser, Micaela; Foley, Kimberley A.; Wolberg, Alisa S.; Conway, Edward M.

2016-01-01

Thrombus formation leading to vaso-occlusive events is a major cause of death, and involves complex interactions between coagulation, fibrinolytic and innate immune systems. Leukocyte recruitment is a key step, mediated partly by chemotactic complement activation factors C3a and C5a. However, mechanisms mediating C3a/C5a generation during thrombosis have not been studied. In a murine venous thrombosis model, levels of thrombin–antithrombin complexes poorly correlated with C3a and C5a, excluding a central role for thrombin in C3a/C5a production. However, clot weight strongly correlated with C5a, suggesting processes triggered during thrombosis promote C5a generation. Since thrombosis elicits fibrinolysis, we hypothesized that plasmin activates C5 during thrombosis. In vitro, the catalytic efficiency of plasmin-mediated C5a generation greatly exceeded that of thrombin or factor Xa, but was similar to the recognized complement C5 convertases. Plasmin-activated C5 yielded a functional membrane attack complex (MAC). In an arterial thrombosis model, plasminogen activator administration increased C5a levels. Overall, these findings suggest plasmin bridges thrombosis and the immune response by liberating C5a and inducing MAC assembly. These new insights may lead to the development of strategies to limit thrombus formation and/or enhance resolution. PMID:27077125

Detoxification of VX by Chloramine-B. Final report, August 1989-April 1992

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

Yang, Y.C.; Szafraniec, L.L.; Beaudry, W.T.

1993-07-01

At ambient temperature, the nerve agent O-ethyl S-2(diisopropylamino)ethyl methylphosphonothiolate (VX), can be detoxified in an aqueous solution of Chloramine-B CAB, C6H5SQ2N(Cl)Na only in the presence of sufficient acid (pH 3). The thiolo sulfur is first attacked by the reactive species, benzene chlorosulfonamide, to form a chlorosulfonium ion intermediate followed by hydrolysis and substitution reactions with the sulfonamide anion at the P-S bond. These reactions produce strongly acidic products, which further accelerate the initial reaction. Consequently, one of the acidic hydrolysis products of VX, the toxic S-2-(diisopropylamino)ethyl methylphosphonothioic acid (EA 2192) reacts with CAB instantaneously. This acid-catalyzed mechanism is similar tomore » that reported for bivalent sulfides; direct attack by active chlorine is considered insignificant. A neutral VX analog, O,S-diethyl methylphoshonothiolate, reacts with CAB rapidly in H20 with an initial pH of 8.9 but requires the addition of 0.006 N (H+) for the reaction to occur in D20. By comparison, bivalent sulfides are more reactive than the phosphonothiolates, in general, and can be rapidly oxidized in both H20 and D20, even at high pH values. Chloramine-B, VX, Bivalent sulfide, Benzenechlorosulfonamide, Thiolo sulfur, Phosphonothiolate.« less

Discovery of Selective Phosphodiesterase 1 Inhibitors with Memory Enhancing Properties.

PubMed

Dyck, Brian; Branstetter, Bryan; Gharbaoui, Tawfik; Hudson, Andrew R; Breitenbucher, J Guy; Gomez, Laurent; Botrous, Iriny; Marrone, Tami; Barido, Richard; Allerston, Charles K; Cedervall, E Peder; Xu, Rui; Sridhar, Vandana; Barker, Ryan; Aertgeerts, Kathleen; Schmelzer, Kara; Neul, David; Lee, Dong; Massari, Mark Eben; Andersen, Carsten B; Sebring, Kristen; Zhou, Xianbo; Petroski, Robert; Limberis, James; Augustin, Martin; Chun, Lawrence E; Edwards, Thomas E; Peters, Marco; Tabatabaei, Ali

2017-04-27

A series of potent thienotriazolopyrimidinone-based PDE1 inhibitors was discovered. X-ray crystal structures of example compounds from this series in complex with the catalytic domain of PDE1B and PDE10A were determined, allowing optimization of PDE1B potency and PDE selectivity. Reduction of hERG affinity led to greater than a 3000-fold selectivity for PDE1B over hERG. 6-(4-Methoxybenzyl)-9-((tetrahydro-2H-pyran-4-yl)methyl)-8,9,10,11-tetrahydropyrido[4',3':4,5]thieno[3,2-e][1,2,4]triazolo[1,5-c]pyrimidin-5(6H)-one was identified as an orally bioavailable and brain penetrating PDE1B enzyme inhibitor with potent memory-enhancing effects in a rat model of object recognition memory.

Inhibition of the Membrane Attack Complex by Dengue Virus NS1 through Interaction with Vitronectin and Terminal Complement Proteins

PubMed Central

Conde, Jonas Nascimento; da Silva, Emiliana Mandarano; Allonso, Diego; Coelho, Diego Rodrigues; Andrade, Iamara da Silva; de Medeiros, Luciano Neves; Menezes, Joice Lima; Barbosa, Angela Silva

2016-01-01

ABSTRACT Dengue virus (DENV) infects millions of people worldwide and is a major public health problem. DENV nonstructural protein 1 (NS1) is a conserved glycoprotein that associates with membranes and is also secreted into the plasma in DENV-infected patients. The present study describes a novel mechanism by which NS1 inhibits the terminal complement pathway. We first identified the terminal complement regulator vitronectin (VN) as a novel DENV2 NS1 binding partner by using a yeast two-hybrid system. This interaction was further assessed by enzyme-linked immunosorbent assay (ELISA) and surface plasmon resonance (SPR) assay. The NS1-VN complex was also detected in plasmas from DENV-infected patients, suggesting that this interaction occurs during DENV infection. We also demonstrated that the DENV2 NS1 protein, either by itself or by interacting with VN, hinders the formation of the membrane attack complex (MAC) and C9 polymerization. Finally, we showed that DENV2, West Nile virus (WNV), and Zika virus (ZIKV) NS1 proteins produced in mammalian cells inhibited C9 polymerization. Taken together, our results points to a role for NS1 as a terminal pathway inhibitor of the complement system. IMPORTANCE Dengue is the most important arthropod-borne viral disease nowadays and is caused by dengue virus (DENV). The flavivirus NS1 glycoprotein has been characterized functionally as a complement evasion protein that can attenuate the activation of the classical, lectin, and alternative pathways. The present study describes a novel mechanism by which DENV NS1 inhibits the terminal complement pathway. We identified the terminal complement regulator vitronectin (VN) as a novel DENV NS1 binding partner, and the NS1-VN complex was detected in plasmas from DENV-infected patients, suggesting that this interaction occurs during DENV infection. We also demonstrated that the NS1-VN complex inhibited membrane attack complex (MAC) formation, thus interfering with the complement terminal pathway. Interestingly, NS1 itself also inhibited MAC activity, suggesting a direct role of this protein in the inhibition process. Our findings imply a role for NS1 as a terminal pathway inhibitor of the complement system. PMID:27512066

Serotonin₂A/C receptors mediate the aggressive phenotype of TLX gene knockout mice.

PubMed

Juárez, Pablo; Valdovinos, Maria G; May, Michael E; Lloyd, Blair P; Couppis, Maria H; Kennedy, Craig H

2013-11-01

Deleting the tailless (TLX) gene in mice produces a highly aggressive phenotype yet to be characterized in terms of heterozygous animals or neurotransmitter mechanisms. We sought to establish pharmacological control over aggression and study the role of serotonin (5-HT)(2A/C) receptors in mediating changes in aggression. We analyzed aggression in mice heterozygous (+/-) or homozygous (-/-) for the TLX gene and wild-types (+/+) using a resident-intruder paradigm. No +/+ mice were aggressive, 36% of +/- TLX and 100% of -/- TLX mice showed aggression. Dose-effect functions were established for clozapine (0.1-1.5mg/kg, ip), ketanserin (0.3-1.25 mg/kg, ip), and (±)-1-(2,5-dimethoxy-4-iodophenyl)-2-aminopropane [(±)DOI] (0.5-2.0 mg/kg, ip). Injecting clozapine decreased the frequency and duration of attacks for +/- TLX and -/- TLX mice. Clozapine did not decrease grooming in either +/- TLX or -/- TLX mice but may have increased locomotion for -/- TLX mice. Injecting ketanserin, a 5-HT(2A/C) receptor antagonist, produced differential decreases in frequency and latency to aggression between genotypes and corresponding increases in locomotor behavior. Injecting (±)DOI, a 5-HT(2A/C) receptor agonist, increased the frequency and duration of attacks, decreased the latency to attacks, and decreased locomotion in +/- and -/- TLX mice. Results of the current study suggest aggression displayed by TLX null and heterozygous mice involves 5-HT(2A/C) receptors. Copyright © 2013 Elsevier B.V. All rights reserved.

Military Aircraft Modernization: A Better Solution to Manage the Fighter Shortfall - the Sole Answer is NOT the F-35 Program

DTIC Science & Technology

2017-04-21

oclc. org /eds/ detai I/ detai l?vid=5 &sid=5b9e08 b 7-0abf- 4502-a8 l d-42c5 l Od59863%40sessionmgr I 07 &hid= I 04&bdata=JnNpdGU9ZWRzLWxpdm...eds.b.ebscohost.com.nduezproxy.idm.oclc. org /eds/detail/detail?vid=9&sid=5b9e08b7-0abf-4502-a8 l d-42c5 l Od59863%40sessionmgr I 07 &hid= I 04&bdata...nduezproxy. i dm. ocl c. org / eds/pdfviewer/pdfvi ewer?vid = l 3&sid=5b9e08b7-0abf-4502-a8 l d-42c5 l Od59863%40sessionmgr l 07&hid= l 04 (accessed December

Low-intensity laser irradiation at 660 nm stimulates transcription of genes involved in the electron transport chain.

PubMed

Masha, Roland T; Houreld, Nicolette N; Abrahamse, Heidi

2013-02-01

Low-intensity laser irradiation (LILI) has been shown to stimulate cellular functions leading to increased adenosine triphosphate (ATP) synthesis. This study was undertaken to evaluate the effect of LILI on genes involved in the mitochondrial electron transport chain (ETC, complexes I-IV) and oxidative phosphorylation (ATP synthase). Four human skin fibroblast cell models were used in this study: normal non-irradiated cells were used as controls while wounded, diabetic wounded, and ischemic cells were irradiated. Cells were irradiated with a 660 nm diode laser with a fluence of 5 J/cm(2) and gene expression determined by quantitative real-time reverse transcription (RT) polymerase chain reaction (PCR). LILI upregulated cytochrome c oxidase subunit VIb polypeptide 2 (COX6B2), cytochrome c oxidase subunit VIc (COX6C), and pyrophosphatase (inorganic) 1 (PPA1) in diabetic wounded cells; COX6C, ATP synthase, H+transporting, mitochondrial Fo complex, subunit B1 (ATP5F1), nicotinamide adenine dinucleotide (NADH) dehydrogenase (ubiquinone) 1 alpha subcomplex, 11 (NDUFA11), and NADH dehydrogenase (ubiquinone) Fe-S protein 7 (NDUFS7) in wounded cells; and ATPase, H+/K+ exchanging, beta polypeptide (ATP4B), and ATP synthase, H+ transporting, mitochondrial Fo complex, subunit C2 (subunit 9) (ATP5G2) in ischemic cells. LILI at 660 nm stimulates the upregulation of genes coding for subunits of enzymes involved in complexes I and IV and ATP synthase.

German General Officer Casualties in World War II -- Harbinger for U.S. Army General Officer Casualties in Airland Battle

DTIC Science & Technology

1988-12-07

grenades, air attacks, tank fire, snipers, and partisans. Many of these causes, such as air attacks and tank fire, were relatively infrequent occurrences...Tank Fire 5 9 Small Arms Fire 7 13 Grenade 3 5 Air Attack 18 32 Tank Fire 2 4 Partisans 5 9 Sniper 3 5 In World War I personal danger for officers had...accounts of individual demises reflect this increased lethality, and better describe the significant dangers to these senior commanders. 18 AIR ATTACK

Thermally induced defluorination during a mer to fac transformation of a blue-green phosphorescent cyclometalated iridium(III) complex.

PubMed

Zheng, Yonghao; Batsanov, Andrei S; Edkins, Robert M; Beeby, Andrew; Bryce, Martin R

2012-01-02

The new homoleptic tris-cyclometalated [Ir(C^N)(3)] complexes mer-8, fac-8, and fac-9 incorporating γ-carboline ligands are reported. Reaction of 3-(2,4-difluorophenyl)-5-(2-ethylhexyl)-pyrido[4,3-b]indole 6 with iridium(III) chloride under standard cyclometalating conditions gave the homoleptic complex mer-8 in 63% yield. The X-ray crystal structure of mer-8 is described. The Ir-C and Ir-N bonds show the expected bond length alternations for the differing trans influence of phenyl and pyridyl ligands. mer-8 quantitatively isomerized to fac-8 upon irradiation with UV light. However, heating mer-8 at 290 °C in glycerol led to an unusual regioselective loss of one fluorine atom from each of the ligands, yielding fac-9 in 58% yield. fac-8 is thermally very stable: no decomposition was observed when fac-8 was heated in glycerol at 290 °C for 48 h. The γ-carboline system of fac-8 enhances thermal stability compared to the pyridyl analogue fac-Ir(46dfppy)(3)10, which decomposes extensively upon being heated in glycerol at 290 °C for 2 h. Complexes mer-8, fac-8, and fac-9 are emitters of blue-green light (λ(max)(em) = 477, 476, and 494 nm, respectively). The triplet lifetimes for fac-8 and fac-9 are ~4.5 μs at room temperature; solution Φ(PL) values are 0.31 and 0.22, respectively.

Prime Contract Awards Alphabetically by Contractor, by State or Country, and Place, FY83, Part 10 (Universal Aircraft Parts Inc-Zytron Corp).

DTIC Science & Technology

1983-01-01

FIELDS & ALI 33-88 B C B 5 2 2 J070 000 A7 MAINT-REPAIR OF EQ/ADP EQUIP 3 6 4 1 1 K OCAO 0029 DAC , 33-88 B C A 5 3 2 W070 000 $1 LEASE-RENTAL OF EQ...D OCW63 0071 DAC 83-C0414 B C Z 5 3 2 S206 000 SI GUARD SERVICES 7 9 3 5 L 06 1 B J 2 D 83-C0450 B C Z 5 3 2 S206 000 Si GUARD SERVICES 7 9 7 5 L 06...C2470 J085 N62’ CONTRACTOR TOTAL 9 1,541 WALLER TODD & SADLI LA JUNTA COLORADO 040309 1520 06 1 C OCA65 0055 DAC 0-82-D4446 E C B 5 3 2 9140 000 A8A

Anti-GM2 gangliosides IgM paraprotein induces neuromuscular block without neuromuscular damage.

PubMed

Santafé, Manel M; Sabaté, M Mar; Garcia, Neus; Ortiz, Nico; Lanuza, M Angel; Tomàs, Josep

2008-11-15

We analyzed the effect on the mouse neuromuscular synapses of a human monoclonal IgM, which binds specifically to gangliosides with the common epitope [GalNAc beta 1-4Gal(3-2 alpha NeuAc)beta 1-]. We focused on the role of the complement. Evoked neurotransmission was partially blocked by IgM both acutely (1 h) and chronically (10 days). Transmission electron microscopy shows important nerve terminal growth and retraction remodelling though axonal injury can be ruled out. Synapses did not show mouse C5b-9 immunofluorescence and were only immunolabelled when human complement was added. Therefore, the IgM-induced synaptic changes occur without complement-mediated membrane attack.

Fundamental studies of hydrogen attack in carbon-0.5molybdenum steel and weldments applied in petroelum and petrochemical industries

NASA Astrophysics Data System (ADS)

Liu, Peng

High temperature hydrogen attack (HTHA) is a form of surface decarburization, internal decarburization, and/or intergranular cracking in steels exposed to high temperature (>400°F) and high hydrogen pressure. Hydrogen attack is an irreversible process which can cause permanent damage resulting in degradation of mechanical properties and failures such as leakage, bursting, fire, and/or explosion. The continuous progression of hydrogen attack in C-0.5Mo steel and weldments below the C-0.5Mo Nelson Curve has caused a significant concern for the integrity and serviceability of C-0.5Mo steel utilized for pressure vessels and piping in the petroleum refinery and petrochemical industries. A state-of-the-art literature review was implemented to provide a comprehensive overview of the published research efforts on hydrogen attack studies. The evolution of "Nelson Curves" for carbon steel, C-0.5Mo, and Cr-Mo steels was historically reviewed in regard to design applications and limitations. Testing techniques for hydrogen attack assessment were summarized under the categories of hydrogen exposure testing, mechanical evaluation, and dilatometric swelling testing. In accord with the demands of these industries, fundamental studies of hydrogen attack in C-0.5Mo steel and weldments were accomplished in terms of quantitative methodologies for hydrogen damage evaluation; hydrogen damage assessment of service exposed weldments and autoclave exposed materials; effects of carbon and alloying elements, heat treatments, hot and cold working, welding processes and postweld heat treatment (PWHT) on hydrogen attack susceptibility; development of continuous cooling transformation (CCT) diagrams for C-0.5Mo base metals and the coarse grained heat-affected zone (CGHAZ); carbide evaluation for the C-0.5Mo steel after service exposure and heat treatment; methane evolution by the reaction of hydrogen and carbides; hydrogen diffusion and methane pressure through the wall thickness of one-sided hydrogen exposure assembly; hydrogen attack mechanism and hydrogen attack limit modeling.

Inflammatory Response in Preterm and Very Preterm Newborns with Sepsis

PubMed Central

Segura-Cervantes, Enrique; Mancilla-Ramírez, Javier; González-Canudas, Jorge; Alba, Erika; Santillán-Ballesteros, René; Morales-Barquet, Deneb; Sandoval-Plata, Gabriela

2016-01-01

The response of the adaptive immune system is usually less intense in premature neonates than term neonates. The primary objective of this study was to determine whether immunological parameters vary between preterm (PT) neonates (≥32 weeks of gestational age) and very preterm (VPT) neonates (<32 weeks of gestational age). A cross-sectional study was designed to prospectively follow PT and VPT neonates at risk of developing sepsis. Plasma concentrations of IFN-γ, TNF-α, IL-6, IL-4, and IL-10 were detected using flow cytometry. C-reactive protein (C-RP) and the complex SC5b-9 were detected in the plasma using commercial kits. A total of 83 patients were included. The laboratory results and clinical histories showed that 26 patients had sepsis; 14 were VPT, and 12 were PT. The levels of C-RP, SC5b-9 (innate immune response mediators), and IL-10 or IL-4 (anti-inflammatory cytokines) were elevated during sepsis in both groups. IFN-γ, TNF-α, and IL-6 (proinflammatory cytokines) were differentially elevated only in PT neonates. The VPT neonates with sepsis presented increases in C-RP, SC5b-9, and anti-inflammatory cytokines but not in proinflammatory cytokines, whereas PT neonates showed increases in all studied mediators of inflammation. PMID:27293317

'Pincer' dicarbene complexes of some early transition metals and uranium.

PubMed

Pugh, David; Wright, Joseph A; Freeman, Sandra; Danopoulos, Andreas A

2006-02-14

The complexes [(C-N-C)MX(n)(thf)(m)] with the 'pincer' 2,6-bis(imidazolylidene)pyridine, (C-N-C) = 2,6-bis(arylimidazol-2-ylidene)pyridine, aryl = 2,6-Pr(i)2C6H3, M = V, X = Cl, n = 2, m = 1 1a; M = Cr, X = Cl, n = 2, m = 0, 2a, X = Br, 2b; M = Mn, X = Br, n = 2, m = 0, 3; M = Nb, X = Cl, n = 3, m = 0, 4; and M = U, X = Cl, n = 4, m = 0, 5, were synthesised by (a) substitution of labile tmed (1a), thf (2a, 3, 5) or dme (4) by free (C-N-C) or by (b) reaction of the bisimidazolium salt (CH-N-CH)Br2 with {Cr[N(SiMe3)2]2(thf)2} followed by amine elimination (2b). Attempted alkylation of 1a, 2, 3a and 4 with Grignard or alkyl lithiums gave intractable mixtures, and in one case [reaction of 1a with (mesityl)MgBr] resulted in exchange of Cl by Br (1b). Oxidation of 1a or [(C-N-C)VCl3] with 4-methylmorpholine N-oxide afforded the trans-V(C-N-C)(=O)Cl2, 6, which by reaction with AgBF4 in MeCN gave trans-[V(C-N-C)(=O)(MeCN)2][BF4]2, 7. Reaction of 1a with p-tolyl azide gave trans-V(C-N-C)(=N-p-tolyl)Cl2 8. The complex trans-Ti(C-N-C)(=NBu(t))Cl2, 9, was prepared by substitution of the pyridine ligands in Ti(NBu(t))Cl2(py)3 by C-N-C.

Navy Force Structure and Shipbuilding Plans: Background and Issues for Congress

DTIC Science & Technology

2014-08-01

submarines (SSBNs) 12b 12-14b 12b 12b 14 14 14 14 14 Cruise missile submarines (SSGNs) 0c 0-4c 4c 0c 4 4 4 4 2 or 4d Attack submarines ( SSNs ...aircraft carrier 1 1 Virginia ( SSN -774) class attack submarine 2 2 2 2 2 10 Arleigh Burke (DDG-51) class destroyer 2 2 2 2 2 10 Littoral Combat Ship...shows the Navy’s FY2015 30-year (FY2015-FY2044) shipbuilding plan. Table 3. Navy FY2015 30-Year (FY2015-FY2044) Shipbuilding Plan FY CVN LSC SSC SSN

Comparing shame in clinical and nonclinical populations: Preliminary findings.

PubMed

Dyer, Kevin F W; Dorahy, Martin J; Corry, Mary; Black, Rebecca; Matheson, Laura; Coles, Holly; Curran, David; Seager, Lenaire; Middleton, Warwick

2017-03-01

To conduct a preliminary study comparing different trauma and clinical populations on types of shame coping style and levels of state shame and guilt. A mixed independent groups/correlational design was employed. Participants were recruited by convenience sampling of 3 clinical populations-complex trauma (n = 65), dissociative identity disorder (DID; n = 20), and general mental health (n = 41)-and a control group of healthy volunteers (n = 125). All participants were given (a) the Compass of Shame Scale, which measures the four common shame coping behaviors/styles of "withdrawal," "attack self," "attack other," and "avoidance," and (b) the State Shame and Guilt Scale, which assesses state shame, guilt, and pride. The DID group exhibited significantly higher levels of "attack self," "withdrawal," and "avoidance" relative to the other groups. The complex trauma and general mental health groups did not differ on any shame variable. All three clinical groups had significantly greater levels of the "withdrawal" coping style and significantly impaired shame/guilt/pride relative to the healthy volunteers. "Attack self" emerged as a significant predictor of increased state shame in the complex trauma, general mental health, and healthy volunteer groups, whereas "withdrawal" was the sole predictor of state shame in the DID group. DID emerged as having a different profile of shame processes compared to the other clinical groups, whereas the complex trauma and general mental health groups had comparable shame levels and variable relationships. These differential profiles of shame coping and state shame are discussed with reference to assessment and treatment. (PsycINFO Database Record (c) 2017 APA, all rights reserved).

Strains Responsible for Invasive Meningococcal Disease in Patients With Terminal Complement Pathway Deficiencies.

PubMed

Rosain, Jérémie; Hong, Eva; Fieschi, Claire; Martins, Paula Vieira; El Sissy, Carine; Deghmane, Ala-Eddine; Ouachée, Marie; Thomas, Caroline; Launay, David; de Pontual, Loïc; Suarez, Felipe; Moshous, Despina; Picard, Capucine; Taha, Muhamed-Kheir; Frémeaux-Bacchi, Véronique

2017-04-15

Patients with terminal complement pathway deficiency (TPD) are susceptible to recurrent invasive meningococcal disease (IMD). Neisseria meningitidis (Nm) strains infecting these patients are poorly documented in the literature. We identified patients with TPD and available Nm strains isolated during IMD. We investigated the genetic basis of the different TPDs and the characteristics of the Nm strains. We included 56 patients with C5 (n = 8), C6 (n = 20), C7 (n = 18), C8 (n = 9), or C9 (n = 1) deficiency. Genetic study was performed in 47 patients and 30 pathogenic variants were identified in the genes coding for C5 (n = 4), C6 (n = 5), C7 (n = 12), C8 (n = 7), and C9 (n = 2). We characterized 61 Nm strains responsible for IMD in the 56 patients with TPD. The most frequent strains belonged to groups Y (n = 27 [44%]), B (n = 18 [30%]), and W (n = 8 [13%]). Hyperinvasive clonal complexes (CC11, CC32, CC41/44, and CC269) were responsible for 21% of IMD cases. The CC23 predominates and represented 26% of all invasive isolates. Eleven of the 15 clonal complexes identified fit to 12 different clonal complexes belonging to carriage strains. Unusual meningococcal strains with low level of virulence similar to carriage strains are most frequently responsible for IMD in patients with TPD. © The Author 217. Published by Oxford University Press for the Infectious Diseases Society of America. All rights reserved. For permissions, e-mail: journals.permissions@oup.com.

Fas Ligand-Mediated Lysis of Self Bystander Targets by Human Papillomavirus-Specific CD8+ Cytotoxic T Lymphocytes

PubMed Central

Smyth, Mark J.; Krasovskis, Erika; Johnstone, Ricky W.

1998-01-01

Mouse cytotoxic T lymphocytes (CTL) reactive with a H-2Db-presented 9-mer peptide of the human papillomavirus type 16 protein E749-57 (RAHYNIVTF) were generated from the spleen cells of wild-type C57BL/6 (B6) or B6 perforin-deficient (B6.P0) mice. CD8+ B6 CTL displayed peptide-specific perforin- and Fas-mediated lysis of E7-transfected mouse RMA lymphoma cells (RMA-E7), while CD8+ CTL from B6.P0 mice lysed RMA-E7 cells via Fas ligand (FasL) exclusively. Rapid and efficient lysis of syngeneic bystander B6 blasts or RMA cells by either B6 or B6.P0 Ag-activated CTL was mediated by a FasL-Fas mechanism. Fas-resistant bystanders were not lysed, nor were allogeneic Fas-sensitive C3H/HeJ (H-2k) or BALB/c (H-2d) bystander blasts. Interestingly, however, phorbol myristate acetate-ionomycin preactivation of B6.P0 effectors enabled lysis of allogeneic H-2k and H-2d bystanders even in the absence of antigenic stimulation. Lysis of syngeneic bystander cells was always FasL-Fas dependent and required effector-bystander contact and, in particular, an interaction between CTL LFA-1 and bystander ICAM-1. Thus, in the context of major histocompatibility complex class I molecule-peptide ligation of the T-cell receptors of CD8+ CTL, neighboring bystander cells that are syngeneic and Fas sensitive and express the adhesion molecule ICAM-1 are potential targets of CTL attack. PMID:9621057

Synthesis, characterization, crystal structure, superoxide dismutase and biological activities of nickel (II) complexes with bidentate ligands possessing N and O donor atoms

NASA Astrophysics Data System (ADS)

Sangeeta, S.; Ahmad, K.; Noorussabah, N.; Bharti, S.; Mishra, M. K.; Sharma, S. R.; Choudhary, M.

2017-12-01

Two new Schiff bases 2-((E)-(4-bromo-2-chlorophenylimino)methyl)-4-bromophenol(HL1) and1-((E)-(4-bromo-2-chlorophenylimino)methyl)naphthalene-2-ol (HL2) and their new nickel (II) complexes [Ni(L1)2]·DMF(1) and [Ni(L2)2] (2) have been synthesized and characterized by various physico- chemical and spectroscopic methods. The solid-state structures of synthesized compounds were determined by single crystal X-ray crystallography, which revealed square planar geometry around Ni (II) ion. Infrared spectra, UV-Vis, thermal analysis and magnetic susceptibility measurements agreed with the observed crystal structures. The ligand (HL1) crystallized in the Orthorhombic system of the space group Pbca,a = 7.5485(4)Å, b = 11.5514(5) Å, c = 30.1370(14)Å, α = 90°, β = 90°, γ = 90°and Z = 8. Complex[Ni(L1)2]·DMF(1) crystallized in the Triclinic system of the space group P-1, a = 8.9954(3) Å, b = 9.4593(4) Å, c = 13.2657(5) Å, α = 101.478°, β = 99.595°, γ = 117.651°and Z = 2, whereas complex [Ni(L2)2]·(2) crystallized in the Monoclinic system of the space group P21/c, a = 9.301(9)Å, b = 12.149(8)Å, c = 13.792(10)Å, α = 90°, β = 106.35(4).°, γ = 90°and Z = 2. The Schiff bases (HL1and HL2) behaved as monobasic bidentate ligands possessing N and O donor atoms. The SOD activities of HL1 and its Ni (II) complex[Ni(L1)2]·DMF(1) have been measured using xanthine-xanthine oxidase as a source of superoxide radical and NBT assay as O2- scavenger. In vitro antimicrobial activities of the Ni(II) complexes (1) and (2)against Bacillus cereus and Staphylococcus aureus as Gram + ve and Salmonella typhi, Klebsiella pneumonia and Escherichia coli as Gram-ve species have been investigated comparing with the Schiff base ligands (HL1and HL2).

Crystal structures of the ternary complex of APH(4)-Ia/Hph with hygromycin B and an ATP analog using a thermostable mutant.

PubMed

Iino, Daisuke; Takakura, Yasuaki; Fukano, Kazuhiro; Sasaki, Yasuyuki; Hoshino, Takayuki; Ohsawa, Kanju; Nakamura, Akira; Yajima, Shunsuke

2013-07-01

Aminoglycoside 4-phosphotransferase-Ia (APH(4)-Ia)/Hygromycin B phosphotransferase (Hph) inactivates the aminoglycoside antibiotic hygromycin B (hygB) via phosphorylation. The crystal structure of the binary complex of APH(4)-Ia with hygB was recently reported. To characterize substrate recognition by the enzyme, we determined the crystal structure of the ternary complex of non-hydrolyzable ATP analog AMP-PNP and hygB with wild-type, thermostable Hph mutant Hph5, and apo-mutant enzyme forms. The comparison between the ternary complex and apo structures revealed that Hph undergoes domain movement upon binding of AMP-PNP and hygB. This was about half amount of the case of APH(9)-Ia. We also determined the crystal structures of mutants in which the conserved, catalytically important residues Asp198 and Asn203, and the non-conserved Asn202, were converted to Ala, revealing the importance of Asn202 for catalysis. Hph5 contains five amino acid substitutions that alter its thermostability by 16°C; its structure revealed that 4/5 mutations in Hph5 are located in the hydrophobic core and appear to increase thermostability by strengthening hydrophobic interactions. Copyright © 2013 Elsevier Inc. All rights reserved.

Displacement of ethene from the decamethyltitanocene-ethene complex with internal alkynes, substituent-dependent alkyne-to-allene rearrangement, and the electronic transition relevant to the back-bonding interaction.

PubMed

Pinkas, Jiří; Gyepes, Róbert; Císařová, Ivana; Kubišta, Jiří; Horáček, Michal; Mach, Karel

2015-04-28

The titanocene-ethene complex [Ti(II)(η(2)-C2H4)(η(5)-C5Me5)2] (1) with simple internal alkynes R(1)C≡CR(2) gives complexes [Ti(II)(η(2)-R(1)C≡CR(2))(η(5)-C5Me5)2] {R(1), R(2): Ph, Ph (3), Ph, Me (4), Me, SiMe3 (5), Ph, SiMe3 (6), t-Bu, SiMe3 (7), and SiMe3, SiMe3 (8). In contrast, alkynes with R(1) = Me and R(2) = t-Bu or i-Pr afford allene complexes [Ti(II)(η(2)-CH2=C=CHR(2))(η(5)-C5Me5)2] (11) and (12), whereas for R(2) = Et a mixture of alkyne complex (13A) and minor allene (13) is obtained. Crystal structures of 4, 6, 7 and 11 have been determined; the latter structure proved the back-bonding interaction of the allene terminal double bond. Only the synthesis of 8 from 1 was inefficient because the equilibrium constant for the reaction [1] + [Me3SiC≡CSiMe3] ⇌ [8] + [C2H4] approached 1. Compound 9 (R(1), R(2): Me), not obtainable from 1, together with compounds 3–6 and 10 (R(1), R(2): Et) were also prepared by alkyne exchange with 8, however this reaction did not take place in attempts to obtain 7. Compounds 1 and 3–9 display the longest-wavelength electronic absorption band in the range 670-940 nm due to the HOMO → LUMO transition. The assignment of the first excitation to be of predominantly a b2 → a1 transition was confirmed by DFT calculations. The calculated first excitation energies for 3–9 followed the order of hypsochromic shifts of the absorption band relative to 8 that were induced by acetylene substituents: Me > Ph ≫ SiMe3. Computational results have also affirmed the back-bonding nature in the alkyne-to-metal coordination.

Targeting the Human Complement Membrane Attack Complex to Selectively Kill Prostate Cancer Cells

DTIC Science & Technology

2013-10-01

prostate cancer cells in vitro . Evaluate CD59 expression in human prostate cancer microarrays. Aim 4: Evaluate toxicity and efficacy of the lead PAC5...fragment in vitro . Since PSA is the major chymotrypsin-like serine protease in the seminal plasma and prostatic fluid, we hypothesized that PSA was...that the evolution -related complement protein C5, but not C4, is a substrate of PSA as well. *Department of Pharmacology and Molecular Sciences, The

[Role of C5b-9 expression in skeletal muscle blood vessels in necrotizing myopathy].

PubMed

Cong, Lu; Pu, Chuanqiang; Mao, Yanling; Liu, Jiexiao; Lu, Xianghui; Wang, Qian

2012-05-01

To investigate the expression of C5b-9 in the skeletal muscle blood vessels in patients with necrotizing myopathy and explore its role in the pathogenesis of this disease. The expression of C5b-9 and MHC-I in the skeletal muscular fibers and blood vessels in 4 patients with necrotizing myopathy was detected using enzymohistochemistry and immunohistochemistry. Focal or dispersive necrotic muscle fibers with obvious phagocytosis were observed in all the 4 patients. No inflammatory cell infiltration was found in the perimysium or perivascular regions. HE staining showed a decreased number of local small blood vessels, and the some small blood vessels showed thickened vascular walls. Immunohistochemistry detected prominent C5b-9 expression in the necrotic muscle fibers and the blood vessels, and diffuse strong C5b-9 expression was found in the vascular walls, vascular endothelial cells and the smooth muscle layer. No MHC-I deposition was detected in the muscular fibers and blood vessels. C5b-9 contributes to the pathogenesis of necrotizing myopathy mediated by pathologies in the blood vessels.

Asymmetrical A-Frame Triplatinum Clusters Bridged by Small Organic Molecules and Bis((diphenylphosphino)methyl)phenylphosphine.

PubMed

Tanase, Tomoaki; Ukaji, Hirokazu; Igoshi, Toshiaki; Yamamoto, Yasuhiro

1996-07-03

Reactions of the linear triplatinum complex [Pt(3)(&mgr;-dpmp)(2)(XylNC)(2)](2+) (3) with small organic molecules led to formation of asymmetrical A-frame triplatinum complexes with an additional bridge across one of the metal-metal bonds, where dpmp is bis((diphenylphosphino)methyl)phenylphosphine. Reaction of complex 3 with electron deficient alkynes (R(1)C&tbd1;CR(2): R(1) = R(2) = CO(2)Me; R(1) = H, R(2) = CO(2)Me; R(1) = R(2) = CO(2)Et) afforded a new series of triplatinum clusters formulated as [Pt(3)(&mgr;-dpmp)(2)(&mgr;-R(1)CCR(2))(XylNC)(2)](PF(6))(2) (5a, R(1) = R(2) = CO(2)Me; 5b, R(1) = H, R(2) = CO(2)Me; 5c, R(1) = R(2) = CO(2)Et) in good yields. The complex cation of 5b was characterized by X-ray crystallography to have an asymmetrical A-frame structure comprising three Pt atoms bridged by two dpmp ligands, in which an acetylene molecule was inserted into one of the Pt-Pt bonds (triclinic, P&onemacr;, a = 19.507(3) Å, b = 20.327(4) Å, c = 14.499(4) Å, alpha = 107.69(2) degrees, beta = 102.08(2) degrees, gamma = 71.30(1) degrees, V = 5148 Å(3), Z = 2, R = 0.070, and R(w) = 0.084). The Pt-Pt bond length is 2.718(1) Å and the Pt.Pt nonbonded distance is 3.582(1) Å. Treatment of 3 with an excess of HBF(4).Et(2)O gave the asymmetrical cluster [Pt(3)(&mgr;-dpmp)(2)(&mgr;-H)(XylNC)(2)](BF(4))(3).CH(2)Cl(2) (6.CH(2)Cl(2)), in 61% yield, and a similar reaction with p-NO(2)C(6)H(4)NC led to the formation of [Pt(3)(&mgr;-dpmp)(2)(&mgr;-R(3)NC)(XylNC)(2)](PF(6))(2).CH(2)Cl(2) (7.CH(2)Cl(2)) in 94% yield (R(3) = p-NO(2)C(6)H(4)). Complexes 6 and 7 are assumed to have a single atom-bridged, asymmetrical A-frame structures. Reaction of the complex syn-[Pt(2)(&mgr;-dpmp)(2)(XylNC)(2)](2+) (1) with [MCl(2)(cod)] (M = Pt, Pd) gave the dimer-monomer combined trinuclear cluster [Pt(2)MCl(2)(&mgr;-dpmp)(2)(XylNC)(2)](PF(6))(2) (8a, M = Pt, 89%; 8b, M = Pd, 55%). The structure of 8a was determined by X-ray crystallography to be comprised of a metal-metal-bonded diplatinum core and a monomeric platinum center bridged by two dpmp ligands with a face-to-face arrangement (triclinic, P&onemacr;, a = 18.082(7) Å, b = 19.765(6) Å, c = 15.662(4) Å, alpha = 98.51(2) degrees, beta = 94.24(3) degrees, gamma = 109.82(2) degrees, V = 5161 Å(3), Z = 2, R = 0.069, and R(w) = 0.080). The Pt-Pt bond length is 2.681(2) Å and the Pt.Pt nonbonded distance is 3.219(2) Å. The heteronuclear complex 8b was transformed to an A-frame trinuclear cluster, [Pt(2)PdCl(&mgr;-Cl)(&mgr;-dpmp)(2)(XylNC)](PF(6))(2) (9), which was characterized by X-ray crystallography (monoclinic, C2/c, a = 33.750(9) Å, b = 28.289(9) Å, c = 23.845(8) Å, beta = 118.19(4) degrees, V = 20066 Å(3), Z = 8, R = 0.082, and R(w) = 0.077). The diplatinum unit (Pt-Pt = 2.606(2) Å) is connected to the mononuclear Pd center by a chloride bridge (Pt.Pd = 3.103(3) Å, Pt-Cl-Pd = 79.6(3) degrees ).

Results of an experimental investigation to determine separation characteristics for the Orbiter/747 using a 0.0125-scale model (48-0 AX1318I-1 747) in the Ames Research center 14-foot wind tunnel (CA23B), volume 1

NASA Technical Reports Server (NTRS)

Esparza, V.

1976-01-01

Separation data were obtained at a Mach number of 0.6 and three incidence angles of 4 deg, 6 deg, and 9 deg. The orbiter angle of attack was varied from 0 to 14 degrees. Longitudinal, lateral and normal separation increments were obtained for fixed 747 angles of attack of 0 deg, 2 deg, and 4 deg while varying orbiter angle of attack. Control surface settings on the 747 carrier included rudder deflections of 0 deg and 10 deg and horizontal stabilizer deflections of -1 deg and +5 deg. Photographs of tested configurations are shown.

Initial experience with a magnetic navigation system for invasive treatment in patients with non-ST-segment elevation acute coronary syndromes.

PubMed

Wang, Hui; Li, Chunjian; Wang, Liansheng; Yang, Zhijian; Cao, Kejiang

2011-12-01

Magnetic navigation system (MNS) assisted percutaneous coronary intervention (MPCI) has been demonstrated an advantage over conventional PCI (CPCI) in complex lesions and tortuous vessels. However, the benefits of MNS in clinical unstable and vulnerable lesions were little studied. The aim of this study is to evaluate the feasibility and benefits of MPCI versus CPCI in patients with non-ST-segment elevation acute coronary syndromes (NSTE-ACS). Thirty-seven consecutive patients with NSTE-ACS undergoing MPCI were compared with 37 matched CPCI patients selected from the same concurrent database. Time to cross lesion, fluoroscopy time, and contrast usage to cross lesion were used as primary end-points. Of the 37 culprit lesions in MPCI, 36 were crossed successfully giving a success rate of 97.3%. The procedure and the fluoroscopy time to cross the lesion were similar between the magnetic and conventional PCI groups (82.0 ± 67.9 seconds vs. 85.8 ± 59.2 seconds, P = 0.692, and 62.6 ± 57.6 seconds vs. 65.4 ± 49.5 seconds, P = 0.738, respectively). In Type A/B1 lesions, there seemed no difference in contrast use (2.7 ± 0.7 mL vs. 3.3 ± 0.9 mL, P = 0.284). But as lesion complexity increased from type B2 to C, significantly less contrast was needed in type B2 (5.1 ± 2.6 mL vs. 7.9 ± 4.0 mL, P = 0.019) and type C (9.8 ± 5.7 mL vs. 14.7 ± 7.4 mL, P = 0.030). No major adverse cardiac events were observed in either the MPCI or CPCI group. MNS assisted technique appears to be feasible and effective in NSTE-ACS patients with more complex lesions; however, it probably offers little benefit in simple lesions like ACC/AHA type A/B1.  ©2011, Wiley Periodicals, Inc.

Palladium complexes of a phosphorus ylide with two stabilizing groups: synthesis, structure, and DFT study of the bonding modes.

PubMed

Falvello, Larry R; Ginés, Juan Carlos; Carbó, Jorge J; Lledós, Agustí; Navarro, Rafael; Soler, Tatiana; Urriolabeitia, Esteban P

2006-08-21

The phosphorus ylide ligand [Ph3P=C(CO2Me)C(=NPh)CO2Me] (L1) has been prepared and fully characterized by spectroscopic, crystallographic, and density functional theory (DFT) methods (B3LYP level). The reactivity of L1 toward several cationic Pd(II) and Pt(II) precursors, with two vacant coordination sites, has been studied. The reaction of [M(C/\\X)(THF)2]ClO4 with L1 (1:1 molar ratio) gives [M(C/\\X)(L1)]ClO4 [M = Pd, C/\\X = C6H4CH2NMe2 (1), S-C6H4C(H)MeNMe2 (2), CH2-8-C9H6N (3), C6H4-2-NC5H4 (4), o-CH2C6H4P(o-tol)2 (6), eta3-C3H5 (7); M = Pt, C/\\X = o-CH2C6H4P(o-tol)2 (5); M(C/\\X) = Pd(C6F5)(SC4H8) (8), PdCl2 (9)]. In complexes 1-9, the ligand L1 bonds systematically to the metal center through the iminic N and the carbonyl O of the stabilizing CO2Me group, as is evident from the NMR data and from the X-ray structure of 3. Ligand L1 can also be orthopalladated by reaction with Pd(OAc)2 and LiCl, giving the dinuclear derivative [Pd(mu-Cl)(C6H4-2-PPh2=C(CO2Me)C(CO2Me)=NPh)]2 (10). The X-ray crystal structure of 10 is also reported. In none of the prepared complexes 1-10 was the C(alpha) atom found to be bonded to the metal center. DFT calculations and Bader analysis were performed on ylide L1 and complex 9 and its congeners in order to assess the preference of the six-membered N,O metallacycle over the four-membered C,N and five-membered C,O rings. The presence of two stabilizing groups at the ylidic C causes a reduction of its bonding capabilities. The increasing strength of the Pd-C, Pd-O, and Pd-N bonds along with other subtle effects are responsible for the relative stabilities of the different bonding modes.

Synthesis, characterization, and electrochemistry of cis-oxothio- and cis-bis(thio)tungsten(VI) complexes of hydrotris(3,5-dimethylpyrazol-1-yl)borate.

PubMed

Eagle, A A; Tiekink, E R; George, G N; Young, C G

2001-08-27

The complexes TpWO2X react with sulfiding agents such as B2S3 or P4S10 to give the oxothio- and bis(thio)tungsten(VI) complexes TpWOSX (X = Cl(-)) and TpWS2X [X = Cl(-), S2PPh2(-); Tp = hydrotris(3,5-dimethylpyrazol-1-yl)borate]. The reaction of TpWS2Cl with (i) PPh3 in pyridine and (ii) dimethyl sulfoxide affords TpWOSCl in good overall yield. The chloro complexes undergo metathesis with alkali metal salts to yield species of the type TpWOSX and TpWS2X [X = OPh(-), SPh(-), SePh(-), (-)-mentholate]. The diamagnetic complexes exhibit NMR spectra indicative of C(1) (TpWOSX) or C(s) (TpWS2X) symmetry and IR spectra consistent with terminal oxo and thio ligation (nu(W=O), 940-925 cm(-1); nu(W=S) or nu(WS2), 495-475 cm(-1)). Crystals of (R,S)-TpWOS[(-)-mentholate] are monoclinic, space group P2(1), with a = 11.983(2) A, b = 18.100(3) A, c = 13.859(3) A, beta = 91.60(2) degrees, V = 3004.6(8) A(3), and Z = 4. Crystals of TpWS2(OPh)-CH2Cl2 are orthorhombic, space group Pbca, with a = 16.961(4) A, b = 33.098(7) A, c = 9.555(2) A, V = 5364(2) A(3), and Z = 8. The mononuclear, distorted-octahedral tungsten centers are coordinated by a tridentate Tp ligand, an alkoxy or aryloxy ligand, and two terminal chalcogenide ligands. The average W=O and W=S distances are 1.726(7) and 2.125(2) A, respectively, and the O=W=S and S=W=S angles 102.9(3) and 102.9(1) degrees, respectively. The tungsten and sulfur X-ray absorption spectra of TpWOSCl and TpWS2Cl are consistent with the presence of terminal pi-bonded thio ligands in both complexes. The thio complexes generally undergo a reversible one-electron reduction at potentials significantly more positive than their oxo analogues. The chemical, spectroscopic, and electrochemical properties of the complexes are heavily influenced by the presence of W=S pi frontier orbitals.

Identification With Terrorist Victims of the Washington, DC Sniper Attacks: Posttraumatic Stress and Depression.

PubMed

Herberman Mash, Holly B; Ursano, Robert J; Benevides, K Nikki; Fullerton, Carol S

2016-02-01

In October 2002, a series of sniper attacks in the Washington, DC area left 10 people dead and 3 wounded. We examined the association between identification with terrorist victims and psychological and behavioral outcomes. Participants were 1,238 residents of the Washington, DC area (ages 18-90 years; M = 41.73, SD = 12.56) who completed the Impact of Event Scale-Revised, Patient Health Questionnaire-9, and items pertaining to identification with attack victims approximately 3 weeks following the first sniper shooting. We examined 3 types of identification with the victims: (a) as like oneself, (b) as like a friend, and (c) as like a family member. The relationships of identification to posttraumatic stress and depressive symptoms were examined using linear regression analyses. Greater total identification was associated with more posttraumatic stress and depressive symptoms (B = 0.27, p < .001, and B = 0.44, p < .001, respectively), after adjusting for demographics. Those who specifically identified with the victims as either self (B = 0.24, p < .001), friend (B = 0.30, p < .001), or family member (B = 0.27, p < .001) reported more PTSD symptoms (n = 1,101). Identifying with victims as like a friend or family member, but not as like oneself, was associated with increased depressive symptoms (B = 0.61, p < .001, and B = 0.45, p = .01, respectively; n = 1,222). Presence and type of identification play a differential role in psychological and behavioral responses during traumatic events. Copyright © 2016 International Society for Traumatic Stress Studies.

Halo-substituted thiosemicarbazones and their copper(II), nickel(II) complexes: Detailed spectroscopic characterization and study of antitumour activity against HepG2 human hepatoblastoma cells

NASA Astrophysics Data System (ADS)

Jagadeesh, M.; Kalangi, Suresh K.; Sivarama Krishna, L.; Reddy, A. Varada

2014-01-01

Copper(II) and nickel(II) complexes of two different halogen substituted thiosemicarbazone ligands were synthesized. The ligands 3,4-difluoroacetophenone thiosemicarbazone (1) and 2-bromo-4'-chloroacetophenone thiosemicarbazone (2) were characterized and confirmed spectroscopically by FT-IR, FT-Raman, UV-vis and fluorescence spectral analysis, while the respective copper(II) complexes [Cu(C9H9N3F2S)2Cl2] (1a), [Cu(C9H9N3ClBrS)2Cl2] (2a) and nickel(II) complexes [Ni(C9H9N3F2S)2] (1b), [Ni(C9H9N3ClBrS)2] (2b) were characterized by FT-IR, UV-vis and electron paramagnetic spectroscopy (EPR). The EPR spectra of the Cu(II) complexes provided the rhombic octahedral and axial symmetry of the complexes 1a and 2a respectively. For the complex 1a, the g values calculated as g1 = 2.1228, g2 = 2.0706 and g3 = 2.001 between 2900 and 3300 G. While for the complex 2a, a set of two resonance absorptions were observed. The synthesized compounds were tested for antitumor activity and showed that the ability to kill liver cancer cells significantly. Out of all the synthesized compounds, copper(II) complexes 1a and 2a showed high cytotoxic effect on liver cancer cells with 67.51% and 42.77% of cytotoxicity respectively at 100 μM.

Synthesis, molecular structure investigations and antimicrobial activity of 2-thioxothiazolidin-4-one derivatives

NASA Astrophysics Data System (ADS)

Barakat, Assem; Al-Najjar, Hany J.; Al-Majid, Abdullah Mohammed; Soliman, Saied M.; Mabkhot, Yahia Nasser; Al-Agamy, Mohamed H. M.; Ghabbour, Hazem A.; Fun, Hoong-Kun

2015-02-01

A variety of 2-thioxothiazolidin-4-one derivatives were prepared and their in vitro antimicrobial activities were studied. Most of these compounds showed significant antibacterial activity specifically against Gram-positive bacteria, among which compounds 4a,e,g, 5b,e,g,h and 6f exhibit high levels of antimicrobial activity against Bacillus subtilis ATCC 10400 with Minimum Inhibitory Concentration (MIC) value of 16 μg/mL. All compounds have antifungal activity against Candida albicans. Unfortunately, however, none of the compounds were active against Gram-negative bacteria. The chemical structure of 3 was confirmed by X-ray single crystal diffraction technique. DFT calculations of 3 have been performed on the free C10H7Cl2NO2S2, 3a and the H-bonded complex, C10H7Cl2NO2S2·H2O, 3b to explore the effect of the H-bonding interactions on the geometric and electronic properties of the studied systems. A small increase in bond length was observed in the C12-O6 due to the H-bonding interactions between 3a and water molecule. MEP study has been used to recognize the most reactive sites towards electrophilic and nucleophilic attacks as well as the possible sites for the H-bonding interactions. The TD-DFT calculations have been used to predict theoretically the electronic spectra of the studied compound. The most intense transition band is predicted at 283.9 nm due to the HOMO-2/HOMO-1 to LUMO transitions. NBO analyses were carried out to investigate the stabilization energy of the various intramolecular charge transfer interactions within the studied molecules.

Voltammetric study of the boric acid-salicylaldehyde-H-acid ternary system and its application to the voltammetric determination of boron.

PubMed

Kajiwara, Mari; Ito, Yoshio N; Miyazaki, Yoshinobu; Fujimori, Takao; Takehara, Kô; Yoshimura, Kazuhisa

2015-02-14

The ternary system of boric acid, salicylaldehyde (SA) and H-acid (HA) was voltammetrically studied from kinetic and equilibrium points of view. The effect of the SA substituents was also studied by using two analogs, 5-fluorosalicylaldehyde (F-SA) and 5-methylsalicylaldehyde (Me-SA). The three cathodic peaks of Azomethine H (AzH), Azomethine H-boric acid complex (AzB), and free SA were observed in the solution containing boric acid, SA and HA. The peak potentials of AzH and SA were shifted to negative potentials with increasing pH, while the peak potential of AzB was pH-independent. This difference indicates that a proton participates in the charge-transfer steps of the AzH and SA reductions, but not in that of the AzB reduction. The formation constants for the AzB complexation were similar among all the examined analogs. In the kinetic study, the reaction rate was higher in an acidic condition for the AzH formation, but in a neutral condition for the AzB formation. The rate constants for the AzB complexes were in the order of F-SA > SA ≈ Me-SA, indicating that the fluoro group accelerates the F-AzB complexation. The AzB complexation mechanism is considered to consist of more than three steps, i.e., the pre-equilibrium of the salicylaldehyde-boric acid complex (SA-B) formation, the nucleophilic attack of HA on SA-B, and the remaining some steps to form AzB. Based on these results, the voltammetric determination method of boron using F-SA was optimized, which allowed the boron concentration to be determined within only 5 min with a 0.03 mg B dm(-3) detection limit.

Magnetic properties of diruthenium(II,III) carboxylate compounds. Crystal structures of Ru2Cl(mu-O2CCH=CHCH=CHMe)4 and Ru2Cl(mu-O2CCH2OMe)4.

PubMed

Barral, M C; Jiménez-Aparicio, R; Pérez-Quintanilla, D; Priego, J L; Royer, E C; Torres, M R; Urbanos, F A

2000-01-10

The reaction of Ru2Cl(mu-O2CMe)4 with 2,4-hexadienoic and 2-methoxyacetic acids affords the compounds Ru2Cl(mu-O2CR)4 [R = CH=CHCH=CHCH3 (1), CH2OMe (2)]. The structures of both complexes have been determined by X-ray crystallography. 1 crystallizes in the triclinic space group P-1 with a = 9.264(1) A, b = 12.661(8) A, c = 12.839(5) A, alpha = 106.09(3) degrees, beta = 77.89(2) degrees, gamma = 97.73(3) degrees, and Z = 2. 2 crystallizes in the nonstandard monoclinic space group P2(1)/c with a = 12.132(4) A, b = 11.570(2) A, c = 13.674(2) A, beta = 91.18(2) degrees, and Z = 4. Complexes 1 and 2 show [Ru2(mu-O2CR)4]+ units linked by chloride ions, giving zigzag chains with Ru-Cl-Ru angles of 119.43(4) degrees and 110.11(7) degrees, respectively. The Ru-Ru bond distances are 2.2857(9) A (1) and 2.290(1) A (2). A magnetic study, in the 2-300 K temperature range, of the new compounds and the previously described Ru2Cl(mu-O2CR)4 [R = CHMe2 (3), CMe3 (4), C4H4N (5)] is described. The polymeric complexes 1 and 2 and the nonpolymeric 3-5 show a large zero-field splitting which varies from 53.9 to 68.1 cm-1. These complexes also show a weak, but not negligible, through-space intermolecular antiferromagnetic coupling not observed in the previous magnetic studies carried out on these types of compounds.

Low speed aerodynamic characteristics of the GD/C B-18E3 booster

NASA Technical Reports Server (NTRS)

Carter, W. V.; Gallaher, W. H.

1972-01-01

A 0.02 scale model of the B-18E3 space shuttle booster was tested in a low speed wind tunnel to evaluate the low speed aerodynamic charactersitics. The basic configuration, including build-up, was tested at a Mach number of 0.201 and Reynolds number per foot of 1.39 million. The normal angle-of-attack range was -4 to +24 degrees in 2 degree increments, at sideslip angles of 0 and 5 degrees. Some lateral data were obtained at the sideslip angle range of -6 to 10 degrees at angles-of attack of 0, 10, and 15 degrees. Data were obtained for canard, split elevon, and split rudder deflections.

Educating Special Forces Junior Leaders for a Complex Security Environment

DTIC Science & Technology

2009-07-01

Security Environment 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR( S ) 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK...UNIT NUMBER 7. PERFORMING ORGANIZATION NAME( S ) AND ADDRESS(ES) Joint Special Operations University,357 Tully Street Alison Building,Hurlburt Field,FL...32544 8. PERFORMING ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING AGENCY NAME( S ) AND ADDRESS(ES) 10. SPONSOR/MONITOR’S ACRONYM( S ) 11. SPONSOR

Molecular and expression analysis of complement component C5 in the nurse shark (Ginglymostoma cirratum) and its predicted functional role.

PubMed

Graham, Matthew; Shin, Dong-Ho; Smith, Sylvia L

2009-07-01

We present the complete cDNA sequence of shark (Ginglymostoma cirratum) pro-C5 and its molecular characterization with a descriptive analysis of the structural elements necessary for its potential functional role as a potent mediator of inflammation (fragment C5a) and initiator molecule (fragment C5b) for the assembly of the membrane attack complex (MAC) upon activation by C5 convertase. In mammals the three complement activation cascades, the classical, alternative and lectin pathways, converge at the activation of C3, a pivotal complement protein. It is, however, the subsequent activation of the next complement component, C5, which is the focal point at which the initiation of the terminal lytic pathway takes place and involves the stepwise assembly of the MAC. The effector cytolytic function of complement occurs with the insertion of MAC into target membranes causing dough-nut like holes and cell leakage. The lytic activity of shark complement results in structurally similar holes in target membranes suggesting the assembly of a shark MAC that likely involves a functional analogue of C5. The composition of shark MAC remains unresolved and to date conclusive evidence has been lacking for shark C5. The gene has not been cloned nor has the serum protein been characterized for any elasmobranch species. This report is the first to confirm the presence of C5 homologue in the shark. GcC5 is remarkably similar to human C5 in overall structure and domain arrangement. The GcC5 cDNA measured 5160-bp with 5' and 3' UTRs of 35 bp and 79 bp, respectively. Structural analysis of the derived protein sequence predicts a molecule that is a two-chain structure which lacks a thiolester bond and contains a C5 convertase cleavage site indicating that activation will generate two peptides, akin to C5b and C5a. The putative GcC5 molecule also contains the C-terminal C345C/Netrin module that characterizes C3, C4 and C5. Multiple alignment of deduced amino acid sequences shows that GcC5 shares more amino acid identities/similarities with mammals than that with bony fish. We conclude that at the time of emergence of sharks the elaborate mosaic structure of C5 had already evolved.

Molecular and expression analysis of complement component C5 in the nurse shark (Ginglymostoma cirratum) and its predicted functional role

PubMed Central

Graham, Matthew; Shin, Dong-Ho; Smith, Sylvia L.

2009-01-01

We present the complete cDNA sequence of shark (Ginglymostoma cirratum) pro-C5 and its molecular characterization with a descriptive analysis of the structural elements necessary for its potential functional role as a potent mediator of inflammation (fragment C5a) and initiator molecule (fragment C5b) for the assembly of the membrane attack complex (MAC) upon activation by C5 convertase. In mammals the three complement activation cascades, the classical, alternative and lectin pathways, converge at the activation of C3, a pivotal complement protein. It is, however, the subsequent activation of the next complement component, C5, which is the focal point at which the initiation of the terminal lytic pathway takes place and involves the stepwise assembly of the MAC. The effector cytolytic function of complement occurs with the insertion of MAC into target membranes causing dough-nut like holes and cell leakage. The lytic activity of shark complement results in structurally similar holes in target membranes suggesting the assembly of a shark MAC that likely involves a functional analogue of C5. The composition of shark MAC remains unresolved and to date conclusive evidence has been lacking for shark C5. The gene has not been cloned nor has the serum protein been characterized for any elasmobranch species. This report is the first to confirm the presence of C5 homologue in the shark. GcC5 is remarkably similar to human C5 in overall structure and domain arrangement. The GcC5 cDNA measured 5160-bp with 5′ and 3′ UTRs of 35bp and 79bp, respectively. Structural analysis of the derived protein sequence predicts a molecule that is a two-chain structure which lacks a thiolester bond and contains a C5 convertase cleavage site indicating that activation will generate two peptides, akin to C5b and C5a. The putative GcC5 molecule also contains the C-terminal C345C/Netrin module that characterizes C3, C4 and C5. Multiple alignment of deduced amino acid sequences show that GcC5 shares more amino acid identities/similarities with mammals than that with bony fish. We conclude that at the time of emergence of sharks the elaborate mosaic structure of C5 had already evolved. PMID:19410004

New Spectrophotometric Assay of Pyrantel Pamoate in Pharmaceuticals and Spiked Human Urine Using Three Complexing Agents

NASA Astrophysics Data System (ADS)

Swamy, N.; Prashanth, K. N.; Basavaiah, K.

2015-07-01

Three simple, rapid, inexpensive, and highly sensitive spectrophotometric methods are described for the quantifi cation of pyrantel pamoate (PYP) in pure drug and formulations. The methods are based on the molecular charge-transfer (CT) complexation reaction involving pyrantel base (PYL) as n-donor and iodine as σ-acceptor (I 2 , method A), and 2,4-dinitrophenol (DNP, method B) or picric acid (PA, method C) as π-acceptors. Spectrophotometrically, the CT complexes showed absorption maxima at 380, 420, and 430 nm, for methods A, B, and C, respectively. Under optimum conditions, Beer's law was obeyed over the concentration ranges 0.12-2.9, 0.12-3.75, and 0.12-2.9 μg/ml for methods A, B, and C, respectively. The apparent molar absorptivity of the CT complexes at the respective λmax are calculated to be 2.63 × 10 5 , 6.91 × 10 4 , and 1.73 × 10 5 l/mol· cm respectively and the corresponding Sandell sensitivity values are 0.0009, 0.003, and 0.0012. The limits of detection (LOD) and quantification (LOQ) are calculated to be (0.02 and 0.07), (0.05 and 0.15), and (0.02 and 0.07) μg/ml with methods A, B, and C, respectively. The intra-day and inter-day accuracy expressed as %RE and precision expressed as %RSD are less than 3%. The methods have been applied to the determination of PYP in tablets, suspensions, and spiked human urine. Parallel assay by a reference method and statistical analysis of the results obtained show no significant difference between the proposed methods and the reference method with respect to accuracy and precision, as evident from the Student's t and variation ratio tests. The accuracy of the methods has been further ascertained by recovery tests via the standard addition technique.

Synthesis and Characterization of the First Cyclic Monothioether Derivative of 1,2-o-Carborane and Its Reactivity toward Phosphine Transition Metal Complexes.

PubMed

Viñas, Clara; Cirera, M. Rosa; Teixidor, Francesc; Kivekäs, Raikko; Sillanpää, Reijo; Llibre, Joan

1998-12-28

The first cyclic monothioether derivative of [C(2)B(9)H(12)](-) has been synthesized from 1-(SH)-1,2-C(2)B(10)H(11). Reaction of the latter with (n)BuLi and 1,3-dibromopropane leads to 1,2-&mgr;-(S(CH(2))(3))-1,2-C(2)B(10)H(10). Partial degradation leads to [7,8-&mgr;-(S(CH(2))(3))-7,8-C(2)B(9)H(10)](-). Reaction of [7,8-&mgr;-(S(CH(2))(3))-7,8-C(2)B(9)H(10)](-) with [PdCl(2)(PRR'(2))(2)] leads to different sets of compounds depending on the nature of R and R'. If R = R' = (t)Bu, a closo compound with one vertex occupied by "[Pd(P(t)Bu(3))(2)]" is obtained. When aryl groups are present in the starting phosphine complex, the zwitterionic non-metal-containing compounds are obtained. The crystal structure of one of them has been determined, and the compound has been proven to be 7,8-&mgr;-(S(CH(2))(3))-11-PPh(3)-7,8-C(2)B(9)H(9). The reaction of [7,8-&mgr;-(S(CH(2))(3))-7,8-C(2)B(9)H(10)](-) with [RhCl(PPh(3))(3)] leads to [Rh(7,8-&mgr;-(S(CH(2))(3))-7,8-C(2)B(9)H(10))(PPh(3))(2)]. An agostic B-Hright harpoon-up Rh interaction has been produced, identified by a (1)H{(11)B} NMR resonance at -4.78 ppm. In this instance the cluster is connected to "Rh" via the thioether and B(11)-H. The reaction of [7,8-&mgr;-(S(CH(2))(3))-7,8-C(2)B(9)H(10)](-) with [RuCl(2)(PPh(3))(3)] leads to a compound with two B-Hright harpoon-up Ru interactions. Contrarily to its noncyclic analogues, it seems that only one isomer has been obtained.

Two-Phase (TiAl+TiCrAl) Coating Alloys for Titanium Aluminides

NASA Technical Reports Server (NTRS)

Brady, Michael P. (Inventor); Smialek, James L. (Inventor); Brindley, William J. (Inventor)

1998-01-01

A coating for protecting titanium aluminide alloys, including the TiAl gamma + Ti3Al (alpha(sub 2)) class, from oxidative attack and interstitial embrittlement at temperatures up to at least 1000 C. is disclosed. This protective coating consists essentially of titanium, aluminum. and chromium in the following approximate atomic ratio: Ti(41.5-34.5)Al(49-53)Cr(9.5-12.5)

Aqueous V(V)-peroxo-amino acid chemistry. Synthesis, structural and spectroscopic characterization of unusual ternary dinuclear tetraperoxo vanadium(V)-glycine complexes.

PubMed

Gabriel, C; Kaliva, M; Venetis, J; Baran, P; Rodriguez-Escudero, I; Voyiatzis, G; Zervou, M; Salifoglou, A

2009-01-19

Vanadium participation in cellular events entails in-depth comprehension of its soluble and bioavailable forms bearing physiological ligands in aqueous distributions of binary and ternary systems. Poised to understand the ternary V(V)-H(2)O(2)-amino acid interactions relevant to that metal ion's biological role, we have launched synthetic efforts involving the physiological ligands glycine and H(2)O(2). In a pH-specific fashion, V(2)O(5), glycine, and H(2)O(2) reacted and afforded the unusual complexes (H(3)O)(2)[V(2)(O)(2)(mu(2):eta(2):eta(1)-O(2))(2)(eta(2)-O(2))(2)(C(2)H(5)NO(2))] x 5/4 H(2)O (1) and K(2)[V(2)(O)(2)(mu(2):eta(2):eta(1)-O(2))(2)(eta(2)-O(2))(2)(C(2)H(5)NO(2))] x H(2)O (2). 1 crystallizes in the triclinic space group P1, with a = 7.805(4) A, b = 8.134(5) A, c = 12.010(7) A, alpha = 72.298(9) degrees, beta = 72.991(9) degrees, gamma = 64.111(9) degrees, V = 641.9(6) A(3), and Z = 2. 2 crystallizes in the triclinic space group P1, with a = 7.6766(9) A, b = 7.9534(9) A, c = 11.7494(13) A, alpha = 71.768(2) degrees, beta = 73.233(2) degrees, gamma = 65.660(2) degrees, V = 610.15(12) A(3), and Z = 2. Both complexes 1 and 2 were characterized by UV/visible, LC-MS, FT-IR, Raman, NMR spectroscopy, cyclic voltammetry, and X-ray crystallography. The structures of 1 and 2 reveal the presence of unusual ternary dinuclear vanadium-tetraperoxo-glycine complexes containing [(V(V)=O)(O(2))(2)](-) units interacting through long V-O bonds and an effective glycinate bridge. The latter ligand is present in the dianionic assembly as a bidentate moiety spanning both V(V) centers in a zwitterionic form. The collective physicochemical properties of the two ternary species 1 and 2 project the chemical role of the low molecular mass biosubstrate glycine in binding V(V)-diperoxo units, thereby stabilizing a dinuclear V(V)-tetraperoxo dianion. Structural comparisons of the anions in 1 and 2 with other known dinuclear V(V)-tetraperoxo binary anionic species provide insight into the chemical reactivity of V(V)-diperoxo species in key cellular events such as insulin mimesis and antitumorigenicity, potentially modulated by the presence of glycinate and hydrogen peroxide.

A pharmacological evidence of positive association between mouse intermale aggression and brain serotonin metabolism.

PubMed

Kulikov, A V; Osipova, D V; Naumenko, V S; Terenina, E; Mormède, P; Popova, N K

2012-07-15

The neurotransmitter serotonin (5-HT) is involved in the regulation of mouse intermale aggression. Previously, it was shown that intensity of mouse intermale aggression was positively associated with activity of the key enzyme of 5-HT synthesis - tryptophan hydroxylase 2 (TPH2) in mouse brain. The aim of the present study was to investigate the effect of pharmacological activation or inhibition of 5-HT synthesis in the brain on intermale aggression in two mouse strains differing in the TPH2 activity: C57BL/6J (B6, high TPH2 activity, high aggressiveness) and CC57BR/Mv (BR, low TPH2 activity, low aggressiveness). Administration of 5-HT precursor L-tryptophan (300 mg/kg, i.p.) to BR mice significantly increased the 5-HT and 5-hydroxyindoleacetic acid (5-HIAA) levels in the midbrain as well as the number of attacks and their duration in the resident-intruder test. And vice versa, administration of TPH2 inhibitor p-chlorophenylalanine (pCPA) (300 mg/kg, i.p., for 3 consecutive days) to B6 mice dramatically reduced the 5-HT and 5-HIAA contents in brain structures and attenuated the frequency and the duration of aggressive attacks. At the same time, L-tryptophan or pCPA did not influence the percentage of aggressive mice and the attack latency reflecting the threshold of aggressive reaction. This result indicated that the intensity of intermale aggression, but not the threshold of aggressive reaction is positively dependent on 5-HT metabolism in mouse brain. Copyright © 2012 Elsevier B.V. All rights reserved.

Cocaine-associated retiform purpura: a C5b-9-mediated microangiopathy syndrome associated with enhanced apoptosis and high levels of intercellular adhesion molecule-1 expression.

PubMed

Magro, Cynthia M; Wang, Xuan

2013-10-01

Cocaine-associated retiform purpura is a recently described entity characterized by striking hemorrhagic necrosis involving areas of skin associated with administration of cocaine. Levamisole, an adulterant in cocaine, has been suggested as the main culprit pathogenetically. Four cases of cocaine-associated retiform purpura were encountered in the dermatopathology practice of C. M. Magro. The light microscopic findings were correlated with immunohistochemical and immunofluorescence studies. All 4 cases showed a very striking thrombotic diathesis associated with intravascular macrophage accumulation. Necrotizing vasculitis was noted in 1 case. Striking intercellular adhesion molecule-1 (ICAM-1)/CD54 expression in vessel wall along with endothelial expression of caspase 3 and extensive vascular C5b-9 deposition was observed in all biopsies examined. Cocaine-induced retiform purpura is a C5b-9-mediated microvascular injury associated with enhanced apoptosis and prominent vascular expression of ICAM-1, all of which have been shown in prior in vitro and in vivo murine models to be a direct effect of cocaine metabolic products. Antineutrophilic cytoplasmic antibody and antiphospholipid antibodies are likely the direct sequelae of the proapoptotic microenvironment. The inflammatory vasculitic lesion could reflect the downstream end point reflective of enhanced ICAM-1 expression and the development of antineutrophilic cytoplasmic antibody. Levamisole likely works synergistically with cocaine in the propagation of this syndromic complex.

Biodiesel fuel production from waste cooking oil by the inclusion complex of heteropoly acid with bridged bis-cyclodextrin.

PubMed

Zou, Changjun; Zhao, Pinwen; Shi, Lihong; Huang, Shaobing; Luo, Pingya

2013-10-01

The inclusion complex of Cs2.5H0.5PW12O40 with bridged bis-cyclodextrin (CsPW/B) is prepared as a highly efficient catalyst for the direct production of biodiesel via the transesterification of waste cooking oil. CsPW/B is characterized by X-ray diffraction, and the biodiesel is analyzed by Gas Chromatography-Mass Spectrometer. The conversion rate of waste cooking oil is up to 94.2% under the optimum experimental conditions that are methanol/oil molar ratio of 9:1, catalyst dosage of 3 wt%, temperature of 65 °C and reaction time of 180 min. The physical properties of biodiesel sample satisfy the requirement of ASTM D6751 standards. The novel CsPW/B catalyst used for the transesterification can lead to 96.9% fatty acid methyl esters and 86.5% of the biodiesel product can serve as the ideal substitute for diesel fuel, indicating its excellent potential application in biodiesel production. Copyright © 2013 Elsevier Ltd. All rights reserved.

X-ray mapping in heterocyclic design: 18. X-ray diffraction study of a series of derivatives of 3-cyanopyridine-2-one with annelated heptane and octane cycles

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

Rybakov, V. B., E-mail: Rybakov20021@yandex.ru; Babaev, E. V.; Paronikyan, E. G., E-mail: Ervand.paronikyan@mail.ru

Seven new, previously unknown, bicyclic and tricyclic heterocycles based on derivatives of 3-cyanopyrid-2-ones are obtained: 2-oxo-2,5,6,7,8,9-hexahydro-1H-cyclohepta[b]pyridine-3-carbonitrile, C{sub 11}H{sub 12}N{sub 2}O (1a); 2-[2-(4-chlorophenyl)-2-oxoethoxy]-6,7,8,9-tetrahydro-5H-cyclohepta[b] pyridine-3-carbonitrile, C{sub 19}H{sub 17}ClN{sub 2}O{sub 2} (2a); (3-amino-6,7,8,9-tetrahydro-5H-cyclohepta[b]furo[3,2-e]pyridin-2-yl)(4- chlorophenyl)methanone, C{sub 19}H{sub 17}ClN{sub 2}O{sub 2} (3); 2-oxo-1,2,5,6,7,8,9,10-octahydrocycloocta[b]pyridine-3-carboxamide, C{sub 12}H{sub 16}N{sub 2}O{sub 2} (4); 2-[2-(4-chorophenyl)-2-oxoethoxy]-5,6,7,8,9,10 -hexahydrocycloocta[b]pyridine-3-carboxamide, C{sub 20}H{sub 21}ClN{sub 2}O{sub 3} (5a); 1-[2-(4-chlorophenyl)-2-oxoethyl]-2-oxo-1,2,5,6,7,8,9,10 -octahydrocycloocta[b]pyridine-3-carboxamide, C{sub 20}H{sub 21}ClN{sub 2}O{sub 3} (5b); and 2-[2-(4-chlorophenyl)-2-oxoethoxy]-5,6,7,8,9,10-hexahydrocycloocta[b] pyridine-3-carbonitrile, C{sub 20}H{sub 19}ClN{sub 2}O{sub 2}, (6). All compounds are characterized by {sup 1}H NMR spectroscopy, and their crystal structures are determined by X-ray diffraction.

Subcontract Competition.

DTIC Science & Technology

1982-11-01

McAreavy Advanced Attack Helicopter, ATTN;. DRCPM-AAH Target Acquisition Designation System/Pilot Night Vision System, ATTN; nRCPM-AAH-TP USA Aviation...Arabian National Guard Modernization Program, ATTN: DRCPM-NG USA Communications-Electronics Command, ATTN: DRCPM-GARS SMOKE/OBSCURANTS, ATTN; DRCPM...LI~ C.’ t4 oo C) ON )~ al C a;- n en𔃾D 9- C% L In C) c! o c5 4o Lo’ w - 0) ’. co L t~0 0l C)O~L 1,.- ool *.- # 0 t; -, j CC -J tmj Li -00 0 0 C 0*J

Synthesis and X-ray crystal structures of heavy-metal complexes of 1,5,9,13-tetrathiacyclohexadecane

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

Setzer, W.N.; Tang, Yaping; Grant, G.J.

1991-09-18

Heavy-metal complexes of the macrocyclic tetrathioether 1,5,9,13-tetrathiacyclohexadecane (16S4) have been prepared by reaction of the ligand with the appropriate heavy-metal salts. The complexes [Hg(16S4)](ClO[sub 4])[sub 2], [Cd(16S4)](ClO[sub 4])[sub 2], and (16S4)(HgCl[sub 2])[sub 2] have been synthesized and characterized. Single-crystal X-ray structural studies have been carried out on [Hg(16S4)](ClO[sub 4])[sub 2] and [Cd(16S4)](ClO[sub 4])[sub 2]. Crystal data for [Hg(16S4)](ClO[sub 4])[sub 2]: C[sub 12]H[sub 24]S[sub 4]HgCl[sub 2]O[sub 8]; monoclinic space group C2/c; a = 10.033 (3), b = 13.421 (4), c = 15.960 (4) [angstrom]; [beta] = 96.48 (2)[degree]; Z = 4; R = 0.051. Crystal data for [Cd(16S4)](ClO[sub 4])[sub 2]: C[submore » 12]H[sub 24]S[sub 4]CdCl[sub 2]O[sub 8]; triclinic space group P[bar I]; a = 8.346 (2), b = 8.349 (3), c = 8.688 (2) [angstrom]; [alpha] = 69.87 (2), [beta] = 68.97 (2), [gamma] = 82.33 (2)[degree]; Z = 1; R = 0.043. Molecular mechanics calculations have been carried out on the 16S4 ligand, and the lowest energy conformation is a quadrangular [4444] conformation with the sulfur atoms occupying the corners (exodentate) of the quadrangle.« less

Inhibition of the Membrane Attack Complex by Dengue Virus NS1 through Interaction with Vitronectin and Terminal Complement Proteins.

PubMed

Conde, Jonas Nascimento; da Silva, Emiliana Mandarano; Allonso, Diego; Coelho, Diego Rodrigues; Andrade, Iamara da Silva; de Medeiros, Luciano Neves; Menezes, Joice Lima; Barbosa, Angela Silva; Mohana-Borges, Ronaldo

2016-11-01

Dengue virus (DENV) infects millions of people worldwide and is a major public health problem. DENV nonstructural protein 1 (NS1) is a conserved glycoprotein that associates with membranes and is also secreted into the plasma in DENV-infected patients. The present study describes a novel mechanism by which NS1 inhibits the terminal complement pathway. We first identified the terminal complement regulator vitronectin (VN) as a novel DENV2 NS1 binding partner by using a yeast two-hybrid system. This interaction was further assessed by enzyme-linked immunosorbent assay (ELISA) and surface plasmon resonance (SPR) assay. The NS1-VN complex was also detected in plasmas from DENV-infected patients, suggesting that this interaction occurs during DENV infection. We also demonstrated that the DENV2 NS1 protein, either by itself or by interacting with VN, hinders the formation of the membrane attack complex (MAC) and C9 polymerization. Finally, we showed that DENV2, West Nile virus (WNV), and Zika virus (ZIKV) NS1 proteins produced in mammalian cells inhibited C9 polymerization. Taken together, our results points to a role for NS1 as a terminal pathway inhibitor of the complement system. Dengue is the most important arthropod-borne viral disease nowadays and is caused by dengue virus (DENV). The flavivirus NS1 glycoprotein has been characterized functionally as a complement evasion protein that can attenuate the activation of the classical, lectin, and alternative pathways. The present study describes a novel mechanism by which DENV NS1 inhibits the terminal complement pathway. We identified the terminal complement regulator vitronectin (VN) as a novel DENV NS1 binding partner, and the NS1-VN complex was detected in plasmas from DENV-infected patients, suggesting that this interaction occurs during DENV infection. We also demonstrated that the NS1-VN complex inhibited membrane attack complex (MAC) formation, thus interfering with the complement terminal pathway. Interestingly, NS1 itself also inhibited MAC activity, suggesting a direct role of this protein in the inhibition process. Our findings imply a role for NS1 as a terminal pathway inhibitor of the complement system. Copyright © 2016, American Society for Microbiology. All Rights Reserved.

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

Sanjeewa, Liurukara. D.; McGuire, Michael A.; McMillen, Colin D.

We synthesized new complex manganese vanadate materials as high-quality single crystals in multi-millimeter lengths using a high-temperature, high-pressure hydrothermal method. We grew one compound, Mn 5(VO 4) 2(OH) 4, from Mn 2O 3 and V 2O 5 in 3 M CsOH at 580 °C and 1.5 kbar. Changing the mineralizer to 1 M CsOH/3MCsCl leads to the formation of another product, Mn 6O(VO 4) 2(OH). Both compounds were structurally characterized by single-crystal X-ray diffraction (Mn 5(VO 4) 2(OH) 4: C2/m, Z = 2, a = 9.6568(9) Å, b = 9.5627(9) Å, c = 5.4139(6) Å, β = 98.529(8)°; Mn 6O(VOmore » 4) 2(OH): P21/m, Z = 2, a = 8.9363(12) Å, b = 6.4678(8) Å, c = 10.4478(13) Å, β = 99.798(3)°), revealing interesting low-dimensional transition-metal features. Mn 5(VO 4) 2(OH) 4 possesses complex honeycomb-type Mn–O layers, built from edge-sharing [MnO 6] octahedra in the bc plane, with bridging vanadate groups connecting these layers along the a-axis. Mn 6O(VO 4) 2(OH) presents a more complicated structure with both octahedral [MnO 6] and trigonal bipyramidal [MnO 5] units. A different pattern of planar honeycomb sheets are formed by edge-shared [MnO6] octahedra, and these sublattices are connected through edge-shared dimers of [MnO 5] trigonal bipyramids to form corrugated sheets. Vanadate groups again condense the sheets into a three-dimensional framework. Infrared and Raman spectroscopies indicated the presence of OH groups and displayed characteristic Raman scattering due to vanadate groups. Furthermore, temperature-dependent magnetic studies indicated Curie–Weiss behavior above 100 K with significant anti-ferromagnetic coupling for both compounds, with further complex magnetic behavior at lower temperatures. The data indicate canted anti-ferromagnetic order below 57 K in Mn 5(VO 4) 2(OH) 4 and below 45 K in Mn 6O(VO 4) 2(OH). Members of another class of compounds, K 2M 3(VO 4) 2(OH) 2 (M = Mn, Co), also containing a honeycomb-type sublattice, were also synthesized to allow a comparison of the structural features across all three structure types and to demonstrate extension to other transition metals.« less

Synthesis and Structure of Vanadium Halide Complexes Containing Diphosphine Ligands with Pendant Amines

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

Egbert, Jonathan D.; Labios, Liezel A.; Darmon, Jonathan M.

2016-02-18

A series of vanadium(III) diiodide complexes of the formula CpV(P RN R'P R)I 2 (Cp = 5-C 5H 5; P RN R'P R = (R 2PCH 2) 2N(R)), where R = Et, R = Me (1a), R = Ph (1b); R = Ph, R = Me (1c)) is reported. The corresponding vanadium(II) monoiodide complexes of the formula CpV(P RN R' PR)I, where R = Et, R = Me (2a), R = Ph (2b); R = Ph, R = Me (2c)) were prepared in THF by reduction of 1a-c with Zn powder. The paramagnetic complexes 1a-c and 2a-c are characterized bymore » elemental analysis, 1H NMR spectroscopy, and by cyclic voltammetry for complexes 2b and 4b. Complexes 1c and 2a-c were also characterized in the single crystal by X-ray crystallography. We report the preparation of the vanadium(II) complexes CpV(P Ph 2N Ph 2)I (3) (P Ph 2N Ph 2 = 1,5-diphenyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) and trans-[VCl 2(PEtNMePEt)2] (4a) and trans-[VCl 2(PEtNPhPEt) 2] (4b). These complexes represent initial coordination chemistry of vanadium complexes with P RN R'P R and P Ph 2N Ph 2 diphosphine ligands, which contain a pendant amine in the second coordination sphere. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for the U.S. Department of Energy.« less

Dual fluorescence from an isonido ReIII rhenacarborane phosphine complex, [7,10-mu-H-7-CO-7,7-(PPh3)2-isonido-7,8,9-ReC2B7H9].

PubMed

Buckner, Steven W; Fischer, Matthew J; Jelliss, Paul A; Luo, Rensheng; Minteer, Shelley D; Rath, Nigam P; Siemiarczuk, Aleksander

2006-09-04

The complex [7,10-mu-H-7-CO-7,7-(PPh3)2-isonido-7,8,9-ReC2B7H9] has been synthesized by treatment of the complex salt [NHMe3][3,3-Cl2-3,3-(CO)2-closo-3,1,2-ReC2B9H11] with PPh3 in refluxing THF (tetrahydrofuran) and isolated as intensely colored orange-red microcrystals. Spectroscopic NMR and IR data have suggested that the product has a highly asymmetric structure with two inequivalent PPh3 ligands and a single CO ligand. Measurement of 11B NMR spectra in particular have indicated seven distinct boron vertexes, although the resulting cage degradation by removal of two BH vertexes was confirmed only following X-ray crystallographic analysis, which revealed the pentadecahedral isonido-7,8,9-ReC2B7 architecture. The 11B NMR resonances span an enormous chemical shift range (Deltadelta = 113), and this appears to be a direct consequence of the deshielding of the boron vertex directly opposite the quadrilateral |ReCCB| aperture. The new complex has been shown by electrochemical measurements to undergo a reversible one-electron oxidation. Digitally simulated cyclic voltammograms support a proposed square scheme (E(1/2) = 0.58, 0.69 V vs ferrocene) involving a reversible isonido-closo transition of the metallacarborane cage. Most unusually for a metallacarborane complex, ambient temperature solutions in CH2Cl2 and DMF have been shown to be intensely turquoise-blue fluorescent (lambda(em) = 442 nm, Phi = 0.012). Fluorescence spectroscopy measurements in MeTHF (2-methyltetrahydrofuran) glass at 77 K have indicated that the likely cause of such a broad emission is dual fluorescence (lambda(em) = 404, 505 nm), with both emissions displaying vibronic structure. Following excited-state lifetime decay analysis, the emissive behavior has been accredited to metal-perturbed 1IL states, with the lower energy emission arising from a slight geometric distortion of the initially excited complex.

Utility of the ACC/AHA lesion classification as a predictor of procedural, 30-day and 12-month outcomes in the contemporary percutaneous coronary intervention era.

PubMed

Theuerle, James; Yudi, Matias B; Farouque, Omar; Andrianopoulos, Nick; Scott, Peter; Ajani, Andrew E; Brennan, Angela; Duffy, Stephen J; Reid, Christopher M; Clark, David J

2017-11-15

Correlations between the ACC/AHA coronary lesion classification and clinical outcomes in the contemporary percutaneous coronary intervention (PCI) era are not well established. We analyzed clinical characteristics and outcomes according to ACC/AHA lesion classification (A, B1, B2, C) in 13,701 consecutive patients from the Melbourne Interventional Group (MIG) registry. Patients presenting with STEMI, cardiogenic shock and out-of-hospital cardiac arrest were excluded. The primary endpoints were 30-day and 12-month mortality. Secondary endpoints were procedural success as well as 30-day and 12-month major adverse cardiac events. Of the 13,701 patients treated, 1,246 (9.1%) had type A lesions, 5,519 (40.3%) had type B1 lesions, 4,449 (32.5%) had Type B2 lesions and 2,487 (18.2%) had Type C lesions. Patients with type C lesions were more likely to be older and have impaired renal function, diabetes, previous myocardial infarction, peripheral vascular disease and prior bypass graft surgery (all P < 0.01). They were also more likely to require rotational atherectomy, drug-eluting stents and longer stent lengths (all P < 0.01). Increasing lesion complexity was associated with lower procedural success (99.6% vs. 99.1% vs. 96.6% vs. 82.7%, P < 0.001) and worse 30-day (0.2% vs. 0.3% vs. 0.7% vs. 0.6%, P < 0.001) and 12-month mortality (2.2% vs. 2.0% vs. 3.2% vs. 2.9%, P <0.01). Kaplan Meier analysis showed complex lesions (type B2 and C) had lower survival at 12-months (P = 0.003). PCI to more complex lesions continues to be associated with lower procedural success rates as well as inferior medium-term clinical outcomes. Thus the ACC/AHA lesion classification should still be calculated preprocedure to predict acute PCI success and clinical outcomes. © 2017 Wiley Periodicals, Inc.

Electroluminescent TCC, C3dg and fB/Bb epitope assays for profiling complement cascade activation in vitro using an activated complement serum calibration standard.

PubMed

van Vuuren, B Jansen; Bergseth, G; Mollnes, T E; Shaw, A M

2014-01-15

Electroluminescent assays for epitopes on the complement components C3dg, terminal complement complex (TCC) and factor B/Bb (fB/Bb) have been developed with capture and detection antibodies to produce detection limits C3dg=91±9ng/mL, TCC=3±0.1ng/mL and fB=55.7±0.1ng/mL. The assay performance was assessed against a series of zymosan and heat aggregated IgG (HAIgG) in vitro activations of complement using a calibrated activated complement serum (ACS) as calibration standard. The ACS standard was stable within 20% accuracy over a 6-month period with freeze-thaw cycles as required. Differential activation of the complement cascade was observed for TCC showing a pseudo-first order formation half-life of 3.5h after activation with zymosan. The C3dg activation fragment indicates a 10% total activation for both activation agents. The kinetic-epitope analysis for fB indicates that the capture epitope is on the fB/Bb protein fragment which can then become covered by the formation of C3bBb or C3bBbP complexes during the time course of the cascade. Copyright © 2013 Elsevier B.V. All rights reserved.

Prevalence of DSM-IV Major Depression Among U.S. Military Personnel: Meta-Analysis and Simulation

DTIC Science & Technology

2012-08-01

Enduring Freedom, 3b from Operation Iraqi Freedom, and 3c from other locations. kStudies 3 and 7 to 9 are based on the mandatory Postdeployment Health (Re...physical disorders, including cardiovascular disorders (heart attack, stroke, hypertension , heart disease), respiratory disorders (COPD, asthma), diabetes...ulcer, HIV-AIDS, epilepsy or seizure disor- der, Crohn’s disease, cancer (except skin cancer), severe migraines, and extreme obesity ; and (4) severe

Observation of inductive effects that cause a change in the rate-determining step for the conversion of rhenium azides to imido complexes.

PubMed

Travia, Nicholas E; Xu, Zhenggang; Keith, Jason M; Ison, Elon A; Fanwick, Phillip E; Hall, Michael B; Abu-Omar, Mahdi M

2011-10-17

The cationic oxorhenium(V) complex [Re(O)(hoz)(2)(CH(3)CN)][B(C(6)F(5))(4)] [1; Hhoz = 2-(2'-hydroxyphenyl)-2-oxazoline] reacts with aryl azides (N(3)Ar) to give cationic cis-rhenium(VII) oxoimido complexes of the general formula [Re(O)(NAr)(hoz)(2)][B(C(6)F(5))(4)] [2a-2f; Ar = 4-methoxyphenyl, 4-methylphenyl, phenyl, 3-methoxyphenyl, 4-chlorophenyl, and 4-(trifluoromethyl)phenyl]. The kinetics of formation of 2 in CH(3)CN are first-order in both azide (N(3)Ar) and oxorhenium(V) complex 1, with second-order rate constants ranging from 3.5 × 10(-2) to 1.7 × 10(-1) M(-1) s(-1). A strong inductive effect is observed for electron-withdrawing substituents, leading to a negative Hammett reaction constant ρ = -1.3. However, electron-donating substituents on phenyl azide deviate significantly from this trend. Enthalpic barriers (ΔH(‡)) determined by the Eyring-Polanyi equation are in the range 14-19 kcal mol(-1) for all aryl azides studied. However, electron-donating 4-methoxyphenyl azide exhibits a large negative entropy of activation, ΔS(‡) = -21 cal mol(-1) K(-1), which is in sharp contrast to the near zero ΔS(‡) observed for phenyl azide and 4-(trifluoromethyl)phenyl azide. The Hammett linear free-energy relationship and the activation parameters support a change in the mechanism between electron-withdrawing and electron-donating aryl azides. Density functional theory predicts that the aryl azides coordinate via N(α) and extrude N(2) directly. For the electron-withdrawing substituents, N(2) extrusion is rate-determining, while for the electron-donating substituents, the rate-determining step becomes the initial attack of the azide. The barriers for these two steps are inverted in their order with respect to the Hammett σ values; thus, the Hammett plot appears with a break in its slope.

The complete mitochondrial genome of the cryptic "lineage B" big-fin reef squid, Sepioteuthis lessoniana (Cephalopoda: Loliginidae) in Indo-West Pacific.

PubMed

Shen, Kang-Ning; Yen, Ta-Chi; Chen, Ching-Hung; Ye, Jeng-Jia; Hsiao, Chung-Der

2016-05-01

In this study, the complete mitogenome sequence of the cryptic "lineage B" big-fin reef squid, Sepioteuthis lessoniana (Cephalopoda: Loliginidae) has been sequenced by next-generation sequencing method. The assembled mitogenome consisting of 16,694 bp, includes 13 protein coding genes, 25 transfer RNAs, 2 ribosomal RNAs genes. The overall base composition of "lineage B" S. lessoniana is 36.7% for A, 18.9 % for C, 34.5 % for T and 9.8 % for G and show 90% identities to "lineage C" S. lessoniana. It is also exhibits high T + A content (71.2%), two non-coding regions with TA tandem repeats. The complete mitogenome of the cryptic "lineage B" S. lessoniana provides essential and important DNA molecular data for further phylogeography and evolutionary analysis for big-fin reef squid species complex.

Efficacy and safety of an intravenous C1-inhibitor concentrate for long-term prophylaxis in hereditary angioedema

PubMed Central

Craig, Timothy; Shapiro, Ralph; Vegh, Arthur; Baker, James W.; Bernstein, Jonathan A.; Busse, Paula; Magerl, Markus; Martinez-Saguer, Inmaculada; Riedl, Marc A.; Lumry, William; Williams-Herman, Debora; Edelman, Jonathan; Feuersenger, Henrike; Machnig, Thomas

2017-01-01

Background: The plasma-derived, pasteurized, nanofiltered C1-inhibitor concentrate (pnfC1-INH) is approved in the United States as an intravenous (IV) on-demand treatment for hereditary angioedema (HAE) attacks, and, in Europe, as on demand and short-term prophylaxis. Objective: This analysis evaluated Berinert Patient Registry data regarding IV pnfC1-INH used as long-term prophylaxis (LTP). Methods: The international registry (2010–2014) collected prospective and retrospective usage, dosing, and safety data on individuals who used pnfC1-INH for any reason. Results: The registry included data on 47 subjects (80.9% female subjects; mean age, 44.8 years), which reflected 4082 infusions categorized as LTP and a total of 430.2 months of LTP administration. The median absolute dose of pnfC1-INH given for LTP was 1000 IU (range, 500–3000 IU), with a median time interval between infusion and a subsequent pnfC1-INH–treated attack of 72.0 hours (range, 0.0–166.4 hours). Fifteen subjects (31.9%) had no pnfC1-INH–treated HAE attacks within 7 days after pnfC1-INH infusion for LTP; 32 subjects (68.1%) experienced 246 attacks, with rates of 0.06 attacks per infusion and 0.57 attacks per month. A total of 81 adverse events were reported in 16 subjects (34.0%) (0.02 events per infusion; 0.19 events per month); only 3 adverse events were considered related to pnfC1-INH (noncardiac chest pain, postinfusion headache, deep vein thrombosis in a subject with an IV port). Conclusion: In this international registry, IV pnf-C1-INH given as LTP for HAE was safe and efficacious, with a low rate of attacks that required pnfC1-INH treatment, particularly within the first several days after LTP administration. PMID:28381322

Host-pathogen interaction in Fusarium oxysporum infections: where do we stand?

PubMed

Husaini, Amjad M; Sakina, Aafreen; Cambay, Souliha R

2018-03-16

Fusarium oxysporum, a ubiquitous soil-borne pathogen causes devastating vascular wilt in more than 100 plant species and ranks fifth among top ten fungal plant pathogens. It has emerged as a human pathogen too, causing infections in immune-compromised patients. It is, therefore, important to gain insight into the molecular processes involved in the pathogenesis of this trans-kingdom pathogen. A complex network comprising of interconnected and over lapping signal pathways; mitogen-activated protein kinase (MAPK) signaling pathways, Ras proteins, G-protein signaling components and their downstream pathways, components of the velvet (LaeA/VeA/VelB) complex and cAMP pathways, is involved in perceiving the host. This network regulates the expression of various pathogenicity genes. Plants have however evolved an elaborate protection system to combat this attack. They too possess intricate mechanisms at molecular level, which once triggered by pathogen attack transduce signals to activate defense response. This review focuses on understanding and presenting a wholistic picture of the molecular mechanisms of F. oxysporum-host interactions in plant immunity.

Environmentally Resistant Mo-Si-B-Based Coatings

NASA Astrophysics Data System (ADS)

Perepezko, J. H.; Sossaman, T. A.; Taylor, M.

2017-06-01

High-temperature applications have demonstrated aluminide-coated nickel-base superalloys to be remarkably effective, but are reaching their service limit. Alternate materials such as refractory (e.g., W, Mo) silicide alloys and SiC composites are being considered to extend high temperature capability, but the silica surfaces on these materials require coatings for enhanced environmental resistance. This can be accomplished with a Mo-Si-B-based coating that is deposited by a spray deposition of Mo followed by a chemical vapor deposition of Si and B by pack cementation to develop an aluminoborosilica surface. Oxidation of the as-deposited (Si + B)-pack coatings proceeds with partial consumption of the initial MoSi2 forming amorphous silica. This Si depletion leads to formation of a B-saturated Mo5Si3 (T1) phase. Reactions between the Mo and the B rich phases develop an underlying Mo5SiB2 (T2) layer. The T1 phase saturated with B has robust oxidation resistance, and the Si depletion is prevented by the underlying diffusion barrier (T2). Further, due to the natural phase transformation characteristics of the Mo-Si-B system, cracks or scratches to the outer silica and T1 layers can be repaired from the Si and B reservoirs of T2 + MoB layer to yield a self-healing characteristic. Mo-Si-B-based coatings demonstrate robust performance up to at least 1700 °C not only to the rigors of elevated temperature oxidation, but also to CMAS attack, hot corrosion attack, water vapor and thermal cycling.

A False Foundation? AQAP, Tribes and Ungoverned Spaces in Yemen

DTIC Science & Technology

2011-09-01

to have learned from the mistakes of its predecessors. Operationally, AQAP’s targets, tactics, personnel and objectives are vastly different from...AQAP’s targets.135 The complexity of the strikes varied dramatically, ranging from small arms attacks against tourists to blended VBIED and active...4131-8140-8b76c7795e49. 349 “ Tam fiha Taqlid Tanzim al-`Iraq: bi-Tariqa Mubtakarah Tanzim al-Qa`ida Y`arid Maqt`a Fidyu Yuzhir I’adam Dabit Mabahith bi

A halogenophilic pathway in the reactions of transition metal carbonyl anions with [(η⁶-iodobenzene)Cr(CO)₃].

PubMed

Sazonov, Petr K; Ivushkin, Vasiliy A; Khrustalev, Victor N; Kolotyrkina, Natal'ya G; Beletskaya, Irina P

2014-09-21

The paper provides the first example of formal nucleophilic substitution by the halogenophilic pathway in Cr(CO)3 complexes of haloarenes with metal carbonyl anions. All metal carbonyl anions examined attack [(η(6)-iodobenzene)Cr(CO)3] at halogen, which is shown by aryl carbanion scavenging with t-BuOH. The reaction with K[CpFe(CO)2] gives only the dehalogenated arene, but the reaction with K[Cp*Fe(CO)2] (Cp* = η(5)-C5Me5) results in nucleophilic substitution to give [(η(6)-C6H5FeCp*(CO)2)Cr(CO)3]. Reaction with Na[Re(CO)5] quantitatively gives the iodo(acyl)rhenate anion Na[(η(6)-C6H5C(O)ReI(CO)4)Cr(CO)3] and in the case of K[Mn(CO)5] a mixture of σ-aryl complexes [(η(6)-C6H5Mn(CO)5)Cr(CO)3] and K[(η(6)-C6H5Mn(CO)4I)Cr(CO)3]. An analogous rhenium complex Na[(η(6)-C6H5Re(CO)4I)Cr(CO)3] is formed from the initial iodo(acyl)rhenate upon prolonged standing at 20 °C, and its structure (in the form of [NEt4](+) salt) is established by X-ray diffraction analysis. The reaction of [(η(6)-chlorobenzene)Cr(CO)3] with K[CpFe(CO)2], in contrast, proceeds by the common S(N)2Ar mechanism.

Results of a pressure loads investigation on a 0.030-scale model (47-OTS) of the integrated space shuttle vehicle configuration 5 in the NASA Ames Research Center 9 by 7 foot leg of the unitary plan wind tunnel (IA81B), volume 1

NASA Technical Reports Server (NTRS)

Chee, E.

1975-01-01

The investigations of pressure distributions are presented for aeroloads analysis at Mach numbers from 1.55 through 2.5. Angles of attack and sideslip varied from -6 to +6 degrees. Photographs of wind tunnel models are shown.

A Theoretical Study of 8-Chloro-9-Hydroxy-Aflatoxin B1, the Conversion Product of Aflatoxin B1 by Neutral Electrolyzed Water

PubMed Central

Escobedo-González, René; Méndez-Albores, Abraham; Villarreal-Barajas, Tania; Aceves-Hernández, Juan Manuel; Miranda-Ruvalcaba, René; Nicolás-Vázquez, Inés

2016-01-01

Theoretical studies of 8-chloro-9-hydroxy-aflatoxin B1 (2) were carried out by Density Functional Theory (DFT). This molecule is the reaction product of the treatment of aflatoxin B1 (1) with hypochlorous acid, from neutral electrolyzed water. Determination of the structural, electronic and spectroscopic properties of the reaction product allowed its theoretical characterization. In order to elucidate the formation process of 2, two reaction pathways were evaluated—the first one considering only ionic species (Cl+ and OH−) and the second one taking into account the entire hypochlorous acid molecule (HOCl). Both pathways were studied theoretically in gas and solution phases. In the first suggested pathway, the reaction involves the addition of chlorenium ion to 1 forming a non-classic carbocation assisted by anchimeric effect of the nearest aromatic system, and then a nucleophilic attack to the intermediate by the hydroxide ion. In the second studied pathway, as a first step, the attack of the double bond from the furanic moiety of 1 to the hypochlorous acid is considered, accomplishing the same non-classical carbocation, and again in the second step, a nucleophilic attack by the hydroxide ion. In order to validate both reaction pathways, the atomic charges, the highest occupied molecular orbital and the lowest unoccupied molecular orbital were obtained for both substrate and product. The corresponding data imply that the C9 atom is the more suitable site of the substrate to interact with the hydroxide ion. It was demonstrated by theoretical calculations that a vicinal and anti chlorohydrin is produced in the terminal furan ring. Data of the studied compound indicate an important reduction in the cytotoxic and genotoxic potential of the target molecule, as demonstrated previously by our research group using different in vitro assays. PMID:27455324

Density functional theory mechanistic study of the reduction of CO2 to CH4 catalyzed by an ammonium hydridoborate ion pair: CO2 activation via formation of a formic acid entity.

PubMed

Wen, Mingwei; Huang, Fang; Lu, Gang; Wang, Zhi-Xiang

2013-10-21

Density functional theory computations have been applied to gain insight into the CO2 reduction to CH4 with Et3SiH, catalyzed by ammonium hydridoborate 1 ([TMPH](+)[HB(C6F5)3](-), where TMP = 2,2,6,6-tetramethylpiperidine) and B(C6F5)3. The study shows that CO2 is activated through the concerted transfer of H(δ+) and H(δ-) of 1 to CO2, giving a complex (IM2) with a well-formed HCOOH entity, followed by breaking of the O-H bond of the HCOOH entity to return H(δ+) to TMP, resulting in an intermediate 2 ([TMPH](+)[HC(═O)OB(C6F5)3)](-)), with CO2 being inserted into the B-H bond of 1. However, unlike CO2 insertion into transition-metal hydrides, the direct insertion of CO2 into the B-H bond of 1 is inoperative. The computed CO2 activation mechanism agrees with the experimental synthesis of 2 via reacting HCOOH with TMP/B(C6F5)3. Subsequent to the CO2 activation and B(C6F5)3-mediated hydrosilylation of 2 to regenerate the catalyst (1), giving HC(═O)OSiEt3 (5), three hydride-transfer steps take place, sequentially transferring H(δ-) of Et3SiH to 5 to (Et3SiO)2CH2 (6, the product of the first hydride-transfer step) to Et3SiOCH3 (7, the product of the second hydride-transfer step) and finally resulting in CH4. These hydride transfers are mediated by B(C6F5)3 via two SN2 processes without involving 1. B(C6F5)3 acts as a hydride carrier that, with the assistance of a nucleophilic attack of 5-7, first grabs H(δ-) from Et3SiH (the first SN2 process), giving HB(C6F5)3(-), and then leave H(δ-) of HB(C6F5)3(-) to the electrophilic C center of 5-7 (the second SN2 process). The SN2 processes utilize the electrophilic and nucleophilic characteristics possessed by the hydride acceptors (5-7). The hydride-transfer mechanism is different from that in the CO2 reduction to methanol catalyzed by N-heterocyclic carbene (NHC) and PCP-pincer nickel hydride ([Ni]H), where the characteristic of possessing a C═O double bond of the hydride acceptors is utilized for hydride transfer. The mechanistic differences elucidate why the present system can completely reduce CO2 to CH4, whereas NHC and [Ni]H catalysts can only mediate the reduction of CO2 to [Si]OCH3 and catBOCH3, respectively. Understanding this could help in the development of catalysts for selective CO2 reduction to CH4 or methanol.

The Role of Education in an Historically Challenging and Politically Complex Environment: The Response of Public Universities to the September 11 Attacks

ERIC Educational Resources Information Center

Khan, Nigar J.

2012-01-01

The dissertation critically analyzes the response of a major research public university to the attacks of 9/11 in order to gain a deeper understanding of public universities' stance on the relevance of Middle East studies, particularly in the context of the serious and far-reaching impact of 9/11. The absence of an articulated position of the…

Synthesis and crystal structure of bis(di- n-butyldithiocarbamato)(1,10-phenanthroline)cadmium(II)

NASA Astrophysics Data System (ADS)

Ivanchenko, A. V.; Gromilov, S. A.; Zemskova, S. M.; Baidina, I. A.; Glinskaya, L. A.

2002-02-01

A new mixed-ligand complex, Cd(S2CN(C4H9)2)2Phen, is synthesized and investigated by thermal, element, and IR analyses and by diffractometry of polycrystals (DRON-3M, CuKα radiation, Ni filter). The crystal structure was determined on a CAD-4 Enraf-Nonius automatic diffractometer (MoKα radiation, θ from 1.5 to 25‡, 2325 nonzero independent reflections, 190 refined parameters, R = 0.036 for I > 2Σ(I)). Crystal data for C30H44CdN4S4 : a = 15.592(3), b = 22.724(5), c = 9.922(2) å, space group Pbcn, V = 3515.5(12) å3, Z = 4, M = 701.33, dcalc = 1.325 g/cm3. The structure involves monomeric molecules in which the cadmium atom has a distorted octahedral environment.

Magnetic Properties of Mononuclear Co(II) Complexes with Carborane Ligands.

PubMed

Alcoba, Diego R; Oña, Ofelia B; Massaccesi, Gustavo E; Torre, Alicia; Lain, Luis; Melo, Juan I; Peralta, Juan E; Oliva-Enrich, Josep M

2018-06-12

We analyze the magnetic properties of three mononuclear Co(II) coordination complexes using quantum chemical complete active space self-consistent field and N-electron valence perturbation theory approaches. The complexes are characterized by a distorted tetrahedral geometry in which the central ion is doubly chelated by the icosahedral ligands derived from 1,2-(HS) 2 -1,2-C 2 B 10 H 10 (complex I), from 1,2-(HS) 2 -1,2-C 2 B 10 H 10 and 9,12-(HS) 2 -1,2-C 2 B 10 H 10 (complex II), and from 9,12-(HS) 2 -1,2-C 2 B 10 H 10 (complex III), which are two positional isomers of dithiolated 1,2-dicarba- closo-dodecaborane (complex I). Complex I was realized experimentally recently (Tu, D.; Shao, D.; Yan, H.; Lu, C. Chem. Commun. 2016, 52, 14326) and served to validate the computational protocol employed in this work, while the remaining two proposed complexes can be considered positional isomers of I. Our calculations show that these complexes present different axial and rhombic zero-field splitting anisotropy parameters and different values of the most significant components of the g tensor. The predicted axial anisotropy D = -147.2 cm -1 for complex II is twice that observed experimentally for complex I, D = -72.8 cm -1 , suggesting that this complex may be of interest for practical applications. We also analyze the temperature dependence of the magnetic susceptibility and molar magnetization for these complexes when subject to an external magnetic field. Overall, our results suggest that o-carborane-incorporated Co(II) complexes are worthwhile candidates for experimental exploration as single-ion molecular magnets.

Preparation and Single-Crystal X-Ray Structures of Four Related Mixed-Ligand 4-Methylpyridine Indium Halide Complexes

NASA Technical Reports Server (NTRS)

Hepp, Aloysius F.; Clark, Eric B.; Schupp, John D.; Williams, Jennifer N.; Duraj, Stan A.; Fanwick, Philip E.

2013-01-01

We describe the structures of four related indium complexes obtained during synthesis of solid-state materials precursors. Indium adducts of halides and 4-methylpyridine, InX3(pic)3 (X = Cl, Br; pic = 4-methylpyridine) consist of octahedral molecules with meridional (mer) geometry. Crystals of mer-InCl3(pic)3 (1) are triclinic, space group P1(bar) (No. 2), with a = 9.3240(3), b = 13.9580(6), c = 16.7268 (7) A, alpha = 84.323(2), beta = 80.938(2), gamma = 78.274(3)Z = 4, R = 0.035 for 8820 unique reflections. Crystals of mer-InBr3(pic)3 (2) are monoclinic, space group P21/n (No. 14), with a = 15.010(2), b = 19.938(2), c = 16.593(3), beta = 116.44(1)Z = 8, R = 0.053 for 4174 unique reflections. The synthesis and structures of related compounds with phenylsulfide (chloride) (3) and a dimeric complex with bridging hydroxide (bromide) (4) coordination is also described. Crystals of trans-In(SC6H5)Cl2(pic)3 (3) are monoclinic, space group P21/n (No. 14), with a = 9.5265(2), b = 17.8729(6), c = 13.8296(4), beta = 99.7640(15)Z = 4, R = 0.048 for 5511 unique reflections. Crystals of [In(mu-OH)Br2(pic)22 (4) are tetragonal, space group = I41cd (No. 110) with a = 19.8560(4), b = 19.8560(4), c = 25.9528(6), Z = 8, R = 0.039 for 5982 unique reflections.

Thermodynamic consideration and ground-state search of icosahedral boron subselenide B12(B1-xSex) 2 from a first-principles cluster expansion

NASA Astrophysics Data System (ADS)

Ektarawong, A.

2018-05-01

The phase stability of icosahedral boron subselenide B12(B1-xSex) 2 , where 0.5 ≤x ≤1 , is explored using a first-principles cluster expansion. The results shows that, instead of a continuous solid solution, B12(B1-xSex) 2 is thermodynamically stable as an individual line compound at the composition of B9.5Se . The ground-state configuration of B9.5Se is represented by a mixture of B12(Se-Se), B12(B-Se), and B12(Se-B) with a ratio of 1:1:1, where they form a periodic A B C A B C ⋯ stacking sequence of B12(Se-Se), B12(B-Se), and B12(Se-B) layers along the c axis of the hexagonal conventional unit cell. The structural and electronic properties of the ground-state B9.5Se are also derived and discussed. By comparing the derived ground-state properties of B9.5Se to the existing experimental data of boron subselenide B˜13Se , I proposed that the as-synthesized boron subselenide B˜13Se , as reported in the literature, has the actual composition of B9.5Se .

Sleep duration versus sleep insufficiency as predictors of cardiometabolic health outcomes.

PubMed

Altman, Nicole G; Izci-Balserak, Bilgay; Schopfer, Elizabeth; Jackson, Nicholas; Rattanaumpawan, Pinyo; Gehrman, Philip R; Patel, Nirav P; Grandner, Michael A

2012-12-01

The objective of the present study was to investigate the relationship between sleep insufficiency and sleep duration, particularly regarding negative cardiometabolic health outcomes already considered to be affected by reduced sleep time. A total of N=30,934 participants from the 2009 Behavioural Risk Factor Surveillance System (BRFSS) answered questions about their sleep duration as well as subjective feelings of sleep insufficiency. Outcomes included body mass index (BMI), obesity (BMI ≥ 30kgm(-2)) and history of hypertension, diabetes, hypercholesterolaemia, heart attack and stroke. Linear and logistic regression models examined whether cardiometabolic outcomes were associated with (1) sleep duration alone, (2) sleep insufficiency alone and (3) the combined effect of sleep duration and sleep insufficiency. Results indicated that, when examined alone, sleep duration <5h (versus 7h) was related to BMI (B=2.716, p<0.01), obesity (B=2.080, p<0.000001), diabetes (B=3.162, p<0.000001), hypertension (B=2.703, p<0.000001), hypercholesterolaemia (B=1.922, p<0.00001), heart attack (B=4.704, p<0.000001) and stroke (B=4.558, p<0.000001), and sleep insufficiency (days per week, continuous) was related to BMI (B=0.181, p<0.01), obesity (B=1.061, p<0.000001) and hypercholesterolaemia (B=1.025, p<0.01). All of these relationships remained significant after adjustment for covariates, except for diabetes and sleep duration. Also, after adjustment, a significant relationship between insufficient sleep and hypertension emerged (B=1.039, p<0.001). When evaluated together, after adjustment for covariates, significant relationships remained between sleep duration <5h (versus 7h) and BMI (B=1.266, p<0.05), obesity (B=1.389, p<0.05), hypertension (B=1.555, p<0.01), heart attack (B=2.513, p<0.01) and stroke (B=1.807, p<0.05). It should be noted that relationships between sleep duration >9h (versus 7h) were seen for heart attack (B=1.863, p<0.001) and stroke (B=1.816, p<0.01). In these models, sleep insufficiency was associated with hypercholesterolaemia (B=1.031, p<0.01) and hypertension (B=1.027, p<0.05). These analyses show that both sleep duration and insufficiency are related to cardiometabolic health outcomes, and that when evaluated together, both variables demonstrate unique effects. Copyright © 2012 Elsevier B.V. All rights reserved.

Dioxo-Fluoroalkoxide Tungsten(VI) Complexes for Growth of WOx Thin Films by Aerosol-Assisted Chemical Vapor Deposition.

PubMed

Bonsu, Richard O; Kim, Hankook; O'Donohue, Christopher; Korotkov, Roman Y; Abboud, Khalil A; Anderson, Timothy J; McElwee-White, Lisa

2015-08-03

The soluble bis(fluoroalkoxide) dioxo tungsten(VI) complexes WO2(OR)2(DME) [1, R = C(CF3)2CH3; 2, R = C(CF3)3] have been synthesized by alkoxide-chloride metathesis and evaluated as precursors for aerosol-assisted chemical vapor deposition (AACVD) of WOx. The (1)H NMR and (19)F NMR spectra of 1 and 2 are consistent with an equilibrium between the dimethoxyethane (DME) complexes 1 and 2 and the solvato complexes WO2(OR)2(CD3CN)2 [1b, R = C(CF3)2CH3; 2b, R = C(CF3)3] in acetonitrile-d3 solution. Studies of the fragmentation of 1 and 2 by mass spectrometry and thermolysis resulted in observation of DME and the corresponding alcohols, with hexafluoroisobutylene also generated from 1. DFT calculations on possible decomposition mechanisms for 1 located pathways for hydrogen abstraction by a terminal oxo to form hexafluoroisobutylene, followed by dimerization of the resulting terminal hydroxide complex and dissociation of the alcohol. AACVD using 1 occurred between 100 and 550 °C and produced both substoichiometric amorphous WOx and a polycrystalline W18O49 monoclinic phase, which exhibits 1-D preferred growth in the [010] direction. The work function (4.9-5.6 eV), mean optical transmittance (39.1-91.1%), conductivity (0.4-2.3 S/cm), and surface roughness (3.4-7.9 nm) of the WOx films are suitable for charge injection layers in organic electronics.

Sleep Duration versus Sleep Insufficiency as Predictors of Cardiometabolic Health Outcomes

PubMed Central

Altman, Nicole G.; Schopfer, Elizabeth; Jackson, Nicholas; Izci-Balserak, Bilgay; Rattanaumpawan, Pinyo; Gehrman, Philip R.; Patel, Nirav P.; Grandner, Michael A.

2012-01-01

Objective The objective of the present study was to investigate the relationship between sleep insufficiency and sleep duration, particularly regarding negative cardiometabolic health outcomes already considered to be affected by reduced sleep time. Methods A total of N=30,934 participants from the 2009 Behavioral Risk Factor Surveillance System (BRFSS) answered questions about their sleep duration as well as subjective feelings of sleep insufficiency. Outcomes included body mass index (BMI), obesity (BMI≥30), and history of hypertension, diabetes, hypercholesterolemia, heart attack, and stroke. Linear and logistic regression models examined whether cardiometabolic outcomes were associated with (1) sleep duration alone, (2) sleep insufficiency alone, and (3) the combined effect of sleep duration and sleep insufficiency. Results Results indicated that, when examined alone, sleep duration <5 hours (vs 7 hours) was related to BMI (B=2.716, p<0.01), obesity (B=2.080, p<0.000001), diabetes (B=3.162, p<0.000001), hypertension (B=2.703, p<0.000001), hypercholesterolemia (B=1.922, p<0.00001), heart attack (B=4.704, p<0.000001), and stroke (B=4.558, p<0.000001), and sleep insufficiency (days per week, continuous) was related to BMI (B=0.181, p<.01), obesity (B=1.061, p<0.000001), and hypercholesterolemia (B=1.025, p<.01). All of these relationships remained significant after adjustment for covariates, except for diabetes and sleep duration. Also, after adjustment, a significant relationship between insufficient sleep and hypertension emerged (B=1.039, p<.001). When evaluated together, after adjustment for covariates, significant relationships remained between sleep duration <5 hours (vs 7 hours) and BMI (B=1.266, p<0.05), obesity (B=1.389, p<.05), hypertension (B=1.555, p<0.01), heart attack (B=2.513, p<0.01)and stroke (B=1.807, p<0.05). It should be noted that relationships between sleep duration >9 hours (vs 7 hours) were seen for heart attack (B=1.863, p<0.001) and stroke (B=1.816, p<0.01). In these models, sleep insufficiency was associated with hypercholesterolemia (B=1.031, p<0.01)and hypertension (B=1.027, p<0.05). Conclusions These analyses show that both sleep duration and insufficiency are related to cardiometabolic health outcomes, and that when evaluated together, both variables demonstrate unique effects. PMID:23141932

Synthesis, crystal structure and biological activity of the Schiff base organotin(IV) complexes based on salicylaldehyde-o-aminophenol

NASA Astrophysics Data System (ADS)

Tan, Yu-Xing; Zhang, Zhi-Jian; Liu, Yang; Yu, Jiang-Xi; Zhu, Xiao-Ming; Kuang, Dai-Zhi; Jiang, Wu-Jiu

2017-12-01

Schiff base organotin(IV) complexes C1 ∼ C5b have been synthesized via the reaction of the substituted salicylaldehyde-o-aminophenol Schiff base ligands (L1 ∼ L3) with the dibenzyltin dichloride, n-butyltin trichloride or dibutyltin oxide, respectively. The complexes have been characterized by IR, UV-Vis, 1H NMR, 13C NMR spectra, elemental analysis and the crystal structures have been determined by X-ray diffraction. The anticancer activity of the Schiff base ligand and complexes C1 ∼ C5b against five species of cancer cell which are Hela, MCF7, HepG2, Colo205, NCIsbnd H460 were tested respectively, the tests showed that C1 ∼ C5b exhibited significant anticancer activity for the cancer cells in comparison with the ligand, and the activity was greater than carboplatin.

Conclusive evidence on the mechanism of the rhodium-mediated decyanative borylation.

PubMed

Esteruelas, Miguel A; Oliván, Montserrat; Vélez, Andrea

2015-09-30

The stoichiometric reactions proposed in the mechanism of the rhodium-mediated decyanative borylation have been performed and all relevant intermediates isolated and characterized including their X-ray structures. Complex RhCl{xant(P(i)Pr2)2} (1, xant(P(i)Pr2)2 = 9,9-dimethyl-4,5-bis(diisopropylphosphino)xanthene) reacts with bis(pinacolato)diboron (B2pin2), in benzene, to give the rhodium(III) derivative RhHCl(Bpin){xant(P(i)Pr2)2} (4) and PhBpin. The reaction involves the oxidative addition of B2pin2 to 1 to give RhCl(Bpin)2{xant(P(i)Pr2)2}, which eliminates ClBpin generating Rh(Bpin){xant(P(i)Pr2)2} (2). The reaction of the latter with the solvent yields PhBpin and the monohydride RhH{xant(P(i)Pr2)2} (6), which adds the eliminated ClBpin. Complex 4 and its catecholboryl counterpart RhHCl(Bcat){xant(P(i)Pr2)2} (7) have also been obtained by oxidative addition of HBR2 to 1. Complex 2 is the promoter of the decyanative borylation. Thus, benzonitrile and 4-(trifluoromethyl)benzonitrile insert into the Rh-B bond of 2 to form Rh{C(R-C6H4)═NBpin}{xant(P(i)Pr2)2} (R = H (8), p-CF3 (9)), which evolve into the aryl derivatives RhPh{xant(P(i)Pr2)2} (3) and Rh(p-CF3-C6H4){xant(P(i)Pr2)2} (10), as a result of the extrusion of CNBpin. The reactions of 3 and 10 with B2pin2 yield the arylBpin products and regenerate 2.

Membrane attack complex of complement is not essential for immune mediated demyelination in experimental autoimmune neuritis.

PubMed

Tran, Giang T; Hodgkinson, Suzanne J; Carter, Nicole M; Killingsworth, Murray; Nomura, Masaru; Verma, Nirupama D; Plain, Karren M; Boyd, Rochelle; Hall, Bruce M

2010-12-15

Antibody deposition and complement activation, especially membrane attack complex (MAC) formation are considered central for immune mediated demyelination. To examine the role of MAC in immune mediated demyelination, we studied experimental allergic neuritis (EAN) in Lewis rats deficient in complement component 6 (C6) that cannot form MAC. A C6 deficient Lewis (Lewis/C6-) strain of rats was bred by backcrossing the defective C6 gene, from PVG/C6- rats, onto the Lewis background. Lewis/C6- rats had the same C6 gene deletion as PVG/C6- rats and their sera did not support immune mediated haemolysis unless C6 was added. Active EAN was induced in Lewis and Lewis/C6- rats by immunization with bovine peripheral nerve myelin in complete Freund's adjuvant (CFA), and Lewis/C6- rats had delayed clinical EAN compared to the Lewis rats. Peripheral nerve demyelination in Lewis/C6- was also delayed but was similar in extent at the peak of disease. Compared to Lewis, Lewis/C6- nerves had no MAC deposition, reduced macrophage infiltrate and IL-17A, but similar T cell infiltrate and Th1 cytokine mRNA expression. ICAM-1 and P-selectin mRNA expression and immunostaining on vascular endothelium were delayed in Lewis C6- compared to Lewis rats' nerves. This study found that MAC was not required for immune mediated demyelination; but that MAC enhanced early symptoms and early demyelination in EAN, either by direct lysis or by sub-lytic induction of vascular endothelial expression of ICAM-1 and P-selectin. Copyright © 2010 Elsevier B.V. All rights reserved.

A comparison of complexation of Li+ ion with macrocyclic ligands 15-crown-5 and 12-crown-4 in binary nitromethane-acetonitrile mixtures by using lithium-7 NMR technique and ab initio calculation.

PubMed

Alizadeh, Nina

2011-01-01

Lithium-7 NMR measurements were used to investigate the stoichiometry and stability of Li+ complexes with 15-crown-5 (15C5), benzo-15-crown-5 (B15C5), dibenzo-15-crown-5 (DB15C5) and 12-crown-4 (12C4) in a number of nitromethane (NM)-acetonitrile (AN) binary mixtures. In all cases, the exchange between the free and complexed lithium ion was fast on the NMR time scale and a single population average resonance was observed. While all crown ethers form 1:1 complexes with Li+ ion in the binary mixtures used, both 1:1 and 2:1 (sandwich) complexes were observed between lithium ion and 12C4 in pure nitromethane solution. Stepwise formation constants of the 1:1 and 2:1 (ligand/metal) complexes were evaluated from computer fitting of the NMR-mole ratio data to equations which relate the observed metal ion chemical shifts to formation constants. There is an inverse linear relationship between the logarithms of the stability constants and the mole fraction of acetonitrile in the solvent mixtures. The stability order of the 1:1 complexes was found to be 15C5·Li+>B15C5·Li+>DB15C5·Li+>12C4·Li+. The optimized structures of the free ligands and their 1:1 and 2:1 complexes with Li+ ion were predicted by ab initio theoretical calculations using the Gaussian 98 software, and the results are discussed. Copyright © 2010 Elsevier B.V. All rights reserved.

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

Lin, Wei; Pringle, Wallace C.; Novick, Stewart E.

The rotational spectrum of the argon-tropolone van der Waals complex in the ground vibrational state has been measured in the frequency range of 6 to 17 GHz using a pulsed-jet, Balle-Flygare-type Fourier transform microwave spectrometer. Eighty-six transitions for the complex (Ar- 12C 7H 6 16O 2) were observed, assigned, and fit using a Watson A-reduction Hamiltonian giving the rotational and centrifugal distortion constants A = 1080.4365(3) MHz, B = 883.4943(3) MHz, C = 749.0571(2) MHz, Δ J = 2.591(2) kHz, Δ JK = -3.32(1) kHz, Δ K = 5.232(9) kHz, δ J = 0.944(1) kHz, and δ K = -0.028(8)more » kHz. The tunneling motion of the hydroxyl proton in the tropolone moiety is quenched in the ground electronic state by complexation with argon. The coordinates of the argon atom in the monomer’s principal axis system are a = 0.43 Å, b = 0.23 Å, c = 3.48 Å.« less

Wind tunnel test of the 0.019 (2A configuration) jet plume space shuttle integrated vehicle in the ARC 9- by 7-foot unitary wind tunnel (IA12B)

NASA Technical Reports Server (NTRS)

Hardin, R. B.; Burrows, R. R.

1974-01-01

The wind tunnel test of the 0.019 jet plume space shuttle integrated vehicle in the Ames 9 ft by 7 ft unitary wind tunnel was conducted at Mach numbers of 1.55 and 2.0 over a Reynolds number range from 3.5 million to 4.1 million/ft. Data were obtained at angles of attack from minus 8 deg to plus 8 deg at 0 deg sideslip and at angles of sideslip from minus 9 deg to plus 8 deg at 0 deg angle of attack. The basic configuration tested was the 2A vehicle with the orbiter at 0 deg angle of incidence with respect to the external tank. The other deviations to the 2A configuration were the solid rocket motor shrouds, which were designed to vehicle '3' lines, and the tank nose, which consisted of the retro-package being removed and replaced by a 16.5 inch full scale radius nose.

Rhodium mediated bond activation: from synthesis to catalysis

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

Ho, Hung-An

Recently, our lab has developed monoanionic tridentate ligand, To R, showing the corresponding coordination chemistry and catalyst reactivity of magnesium, zirconium, zinc and iridium complexes. This thesis details synthetic chemistry, structural study and catalytic reactivity of the To R-supported rhodium compounds. Tl[To R] has been proved to be a superior ligand transfer agent for synthesizing rhodium complexes. The salt metathesis route of Tl[To M] with [Rh(μ-Cl)(CO)] 2 and [Rh(μ- Cl)(COE)] 2 gives To MRh(CO) 2 (2.2) and To MRhH(β 3-C 8H 13) (3.1) respectively while Tl[To M] with [Rh(μ-Cl)(CO)] 2 affords To PRh(CO) 2 (2.3). 2.2 reacts with both strongmore » and weak electrophiles, resulting in the oxazoline N-attacked and the metal center-attacked compounds correspondingly. Using one of the metal center-attacked electrophiles, 2.3 was demonstrated to give high diastereoselectivity. Parallel to COE allylic C-H activation complex 3.1, the propene and allylbenzene allylic C-H activation products have also been synthesized. The subsequent functionalization attempts have been examined by treating with Brønsted acids, Lewis acids, electrophiles, nucleophiles, 1,3-dipolar reagents and reagents containing multiple bonds able to be inserted. Various related complexes have been obtained under these conditions, in which one of the azide insertion compounds reductively eliminates to give an allylic functionalization product stoichiometrically. 3.1 reacts with various primary alcohols to give the decarbonylation dihydride complex To MRh(H) 2CO (4.1). 4.1 shows catalytic reactivity for primary alcohol decarbonylation under a photolytic condition. Meanwhile, 2.2 has been found to be more reactive than 4.1 for catalytic alcohol decarbonylation under the same condition. Various complexes and primary alcohols have been investigated as well. The proposed mechanism is based on the stochiometric reactions of the possible metal and organic intermediates. Primary amines, hypothesized to undergo a similar reaction pathway, have been verified to give dehydrogenative coupling product, imines. In the end, the well-developed neutral tridentate Tpm coordinates to the rhodium bis(ethylene) dimer in the presence of TlPF 6 to give the cationic complex, [TpmRh(C 2H 4) 2][PF 6] (5.1). 5.1 serves as the first example of explicit determination of the solid state hapticity, evidenced by X-ray structure, among all the cationic Tpm RM(C 2H 4) 2 + (Tpm R = Tpm, Tpm*, M = Rh, Ir) derivatives. The substitution chemistry of this compound has been studied by treating with soft and hard donors. The trimethylphosphine-sbustituted complex activates molecular hydrogen to give the dihydride compound.« less

Prothrombotic mechanisms in patients with congenital p.Cys89Tyr mutation in CD59.

PubMed

Tabib, Adi; Hindi, Issam; Karbian, Netanel; Zelig, Orly; Falach, Batla; Mevorach, Dror

2018-06-11

Thrombosis is the prognostic factor with the greatest effect on survival in patients with paroxysmal nocturnal hemoglobinuria (PNH), who lack dozens of membrane surface proteins. We recently described a primary homozygous Cys89Tyr congenital nonfunctioning CD59 in humans with clinical manifestation in infancy, associated with chronic hemolysis, recurrent strokes, and relapsing peripheral demyelinating neuropathy. Here we investigated hypercoagulability mechanisms characterizing the syndrome. Membrane attack complex (MAC) deposition (anti-SC5b-9) and free hemoglobin (colorimetric assay) were assessed. Platelet activation was identified (anti-CD61, anti-CD62P), and microparticles (MPs) of 0.5-0.9 μm, were characterized (Annexin V, anti-human GlyA, anti-CD15, anti-CD14, anti-CD61). Platelet-monocyte aggregation was assessed with FlowSight. 2/7 patients (29%) with homozygosity for Cys89Tyr and 6/12 (50%) with any of four described CD59 mutations had recurrent strokes. In plasma samples from four patients carrying identical mutations, MAC deposition was increased on RBCs (p < 0.0003), neutrophils (p < 0.009), and platelets (p < 0.0003). Free-plasma hemoglobin levels were abnormally high, up to 100 mg/dl. Patients with CD59 mutation had RBC-derived MP levels 9-fold higher than those in healthy controls (p < 0.01), and 2-2.5 fold higher than PNH patients (p < 0.09). Leukocyte-activated platelet aggregation was increased (p < 0.0062). Loss of CD59 was shown in the endothelium of these patients. Nonfunctioning CD59 is a major risk factor for stroke and hypercoagulability. Uncontrolled hemolysis causes massive MP release and endothelial heme damage. MAC attack on unprotected endothelium and platelet activation and aggregation with leukocytes mediate additional mechanisms leading to vascular occlusion. It is suggested that CD59 loss represents a major arterial prothrombotic factor in PNH and additional diseases. Copyright © 2018. Published by Elsevier Ltd.

Studies of molecular species of the human androgen receptor (AR): comparison of the physicochemical properties of the (/sup 3/H)methyltrienolone-AR complex formed in cytosol to the complex produced in intact genital skin fibroblasts

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

Keenan, B.S.; Greger, N.C.; Hedge, A.M.

1986-07-01

Two forms of the human genital skin fibroblast (GSF) androgen receptor (AR) complexed with (/sup 3/H)17 alpha-methyltrienolone were compared: 1) the intact complex formed in cytosol at 4 C (broken cell or B/C complex); and 2) the complex formed in the whole cell at 37 C (W/C complex). The intact form of the B/C complex was distinguished from partly degraded forms by the gel filtration profile in 0.5 M KCl. The W/C complex was considered to represent the transformed state of the receptor. The W/C complex had a smaller molecular radius than the B/C complex by gel filtration (Kav =more » 0.26-0.28 vs. 0.11-0.18). By low salt density gradient centrifugation, the B/C complex sedimented at 8.8S and the W/C complex at 6.6S. However, in 0.5 M KCl, each sedimented at 5.1S, and they were homogeneous, indicating that the monomeric forms differed markedly in molecular radius, but by only about 20,000 daltons in calculated mol wt (134,500 vs. 114,300 daltons). The complexes were separated from DNA, desalted, and compared by chromatography on DEAE-Sephacel and hydroxylapatite (HAP). The B/C complex bound readily to both column matrices and eluted from each as a sharp homogeneous peak: from DEAE at 172-190 mM KCl and from HAP at 123 mM phosphate. The W/C complex, however, was heterogeneous. One component did not bind to DEAE, and one eluted at 22-40 mM KCl. The W/C complex eluted from HAP as a peak at 42 mM, with a shoulder at 102 mM phosphate. Thus, transformation of the human genital skin fibroblast androgen receptor involves a major decrease in molecular radius and loss of negative charge with a possible loss of a 20,000-dalton macromolecular component.« less

EnviroAtlas Estimated Percent Tree Cover Along Walkable Roads Web Service

EPA Pesticide Factsheets

This EnviroAtlas dataset estimates tree cover along walkable roads. The road width is estimated for each road and percent tree cover is calculated in a 8.5 meter strip beginning at the estimated road edge. Percent tree cover is calculated for each block between road intersections. Tree cover provides valuable benefits to neighborhood residents and walkers by providing shade, improved aesthetics, and outdoor gathering spaces. For specific information about each community's Estimated Percent Tree Cover Along Walkable Roads layer, consult their individual metadata records: Austin, TX (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7B4876FD99-C14A-464A-9E31-5CB5F2225687%7D); Cleveland, OH (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7B28e3f937-6f22-45c5-98cf-1707b0fc92df%7D); Des Moines, IA (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7B09FE7D60-B636-405C-BB07-68147DFE8CAF%7D); Durham, NC (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7BF341A26B-4972-4C6B-B675-9B5E02F4F25F%7D); Fresno, CA (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7BB71334B9-C53A-4674-A739-1031969E5163%7D); Green Bay, WI (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7BB9AFEBED-9C29-4DB0-8B54-0CAF58BE5A2D%7D); Memphis, TN (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7BBE552E7A-A789-4AA9-ADF9-234109C6517E%7D); Mi

Study of new mononuclear platinum group metal complexes containing η 5 and η 6 - Carbocyclic ligands and nitrogen based derivatives and formation of helices due to N sbnd H⋯Cl interactions

NASA Astrophysics Data System (ADS)

Gupta, Gajendra; Gloria, Sairem; Das, Babulal; Rao, Kollipara Mohan

2010-08-01

A quite general approach for the preparation of η 5- and η 6-cyclichydrocarbon platinum group metal complexes is reported. The dinuclear arene ruthenium complexes [(η 6-arene)Ru(μ-Cl)Cl] 2 (arene = C 6H 6, C 10H 14 and C 6Me 6) and η 5-pentamethylcyclopentadienyl rhodium and iridium complexes [(η 5-C 5Me 5)M(μ-Cl)Cl] 2 (M = Rh and Ir) reacts with two equivalents of the ligands 2-chloro-3-(pyrazolyl)quinoxaline ( L 1) and di-(2-pyridyl)amine ( L 2) in presence of NH 4PF 6 to afford the corresponding mononuclear complexes of the type [(η 6-arene)Ru(L 1)Cl]PF 6 {arene = C 6H 6 ( 1), C 10H 14 ( 2) and C 6Me 6 ( 3)}, [(η 6-arene)Ru(L 2)Cl]PF 6 {arene = C 6H 6 ( 4), C 10H 14 ( 5) and C 6Me 6 ( 6)}, and [(η 5-C 5Me 5)M(L 1)Cl]PF 6 {M = Rh ( 7), Ir ( 8)} and [(η 5-C 5Me 5)M(L 2)Cl]PF 6 {M = Rh ( 9), Ir ( 10)}. However the mononuclear η 5-cyclopentadienyl analogues such as [(η 5-C 5H 5)Ru(PPh 3) 2Cl], [(η 5-C 5H 5)Os(PPh 3) 2Br], [(η 5-C 5Me 5)Ru(PPh 3) 2Cl] and [(η 5-C 9H 7)Ru(PPh 3) 2Cl] complexes react in presence of one equivalent of ligands 2-chloro-3-(pyrazolyl)quinoxaline ( L 1) and di-(2-pyridyl)amine ( L 2) and one equivalent of NH 4PF 6 in methanol yielded mononuclear complexes [(η 5-C 5H 5)Ru(PPh 3)(L 1)]PF 6 ( 11), [(η 5-C 5H 5)Os(PPh 3)(L 1)]PF 6 ( 12), [(η 5-C 5Me 5)Ru(PPh 3)(L 1)]PF 6 ( 13) and [(η 5-C 9H 7)Ru(PPh 3)(L 1)]PF 6 ( 14) and [(η 5-C 5H 5)Ru(PPh 3)(L 2)]PF 6 ( 15), [(η 5-C 5H 5)Os(PPh 3)(L 2)]PF 6 ( 16), [(η 5-C 5Me 5)Ru(PPh 3)(L 2)]PF 6 ( 17) and [(η 5-C 9H 7)Ru(PPh 3)(L 2)]PF 6 ( 18) respectively. These compounds have been systematically characterized by IR, NMR and mass spectrometry. The molecular structures of 2, 4 and 15 have been established by single crystal X-ray diffraction study and some of the representative complexes have also been studied by UV-visible spectroscopy. The crystal packing diagram of complex 4 reveals that the cation [(η 6-C 6H 6)Ru(L 2)Cl] + is engaged in non-covalent interaction. This compound gives rise to a 1D helical architecture along the ' a' axis via intermolecular N sbnd H⋯Cl hydrogen bonds.

Cognitive-Behavior Therapy for Vietnamese Refugees with PTSD and Comorbid Panic Attacks

ERIC Educational Resources Information Center

Hinton, Devon E.; Safren, Steven A.; Pollack, Mark H.; Tran, Minh

2006-01-01

For Vietnamese refugees, we describe (a) how headache- and orthostasis-focused panic attacks are generated, (b) a culturally sensitive treatment for PTSD with comorbid headache- and orthostasis-focused panic attacks, and (c) the outcome of a treatment series. In a multiple-baseline, across-subjects design (N = 3), all patients demonstrated…

Air Land Sea Bulletin, Issue No. 2013-2, Joint Close Air Support

DTIC Science & Technology

2013-05-01

game plan between his aircraft or element and the coor- dinated attack aircraft or element (s) for a specific JTAC/FAC(A) designated target. However...5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e. TASK NUMBER 5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME...Service Department of Defense field agency sponsored by the US Army Train - ing and Doctrine Command (TRADOC), Marine Corps Combat Development Command

η(4) -HBCC-σ,π-Borataallyl Complexes of Ruthenium Comprising an Agostic Interaction.

PubMed

Saha, Koushik; Joseph, Benson; Ramalakshmi, Rongala; Anju, R S; Varghese, Babu; Ghosh, Sundargopal

2016-06-01

Thermolysis of [Cp*Ru(PPh2 (CH2 )PPh2 )BH2 (L2 )] 1 (Cp*=η(5) -C5 Me5 ; L=C7 H4 NS2 ), with terminal alkynes led to the formation of η(4) -σ,π-borataallyl complexes [Cp*Ru(μ-H)B{R-C=CH2 }(L)2 ] (2 a-c) and η(2) -vinylborane complexes [Cp*Ru(R-C=CH2 )BH(L)2 ] (3 a-c) (2 a, 3 a: R=Ph; 2 b, 3 b: R=COOCH3 ; 2 c, 3 c: R=p-CH3 -C6 H4 ; L=C7 H4 NS2 ) through hydroboration reaction. Ruthenium and the HBCC unit of the vinylborane moiety in 2 a-c are linked by a unique η(4) -interaction. Conversions of 1 into 3 a-c proceed through the formation of intermediates 2 a-c. Furthermore, in an attempt to expand the library of these novel complexes, chemistry of σ-borane complex [Cp*RuCO(μ-H)BH2 L] 4 (L=C7 H4 NS2 ) was investigated with both internal and terminal alkynes. Interestingly, under photolytic conditions, 4 reacts with methyl propiolate to generate the η(4) -σ,π-borataallyl complexes [Cp*Ru(μ-H)BH{R-C=CH2 }(L)] 5 and [Cp*Ru(μ-H)BH{HC=CH-R}(L)] 6 (R=COOCH3 ; L=C7 H4 NS2 ) by Markovnikov and anti-Markovnikov hydroboration. In an extension, photolysis of 4 in the presence of dimethyl acetylenedicarboxylate yielded η(4) -σ,π-borataallyl complex [Cp*Ru(μ-H)BH{R-C=CH-R}(L)] 7 (R=COOCH3 ; L=C7 H4 NS2 ). An agostic interaction was also found to be present in 2 a-c and 5-7, which is rare among the borataallyl complexes. All the new compounds have been characterized in solution by IR, (1) H, (11) B, (13) C NMR spectroscopy, mass spectrometry and the structural types were unequivocally established by crystallographic analysis of 2 b, 3 a-c and 5-7. DFT calculations were performed to evaluate possible bonding and electronic structures of the new compounds. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dinuclear Nickel(II) Complexes as Models for the Active Site of Urease.

PubMed

Volkmer, Dirk; Hommerich, Birgit; Griesar, Klaus; Haase, Wolfgang; Krebs, Bernt

1996-06-19

Dinuclear nickel(II) complexes of the ligands 2,6-bis[bis((2-benzimidazolylmethyl)amino)methyl]-p-cresol (bbapOH), N,N,N',N'-tetrakis(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane (tbpOH), N-methyl-N,N',N'-tris(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane (m-tbpOH) and 1-[N,N-bis(2-benzimidazolylmethyl)amino]-3-[2-(3,5-dimethyl-1H-pyrazol-1-yl)ethoxy]-2-hydroxypropane (bpepOH) were prepared in order to model the active site of urease. The novel asymmetric structures of the dinuclear complexes were characterized by X-ray structure analysis. The complex [Ni(2)(bbapO)(ClO(4))(H(2)O)(MeOH)](ClO(4))(2).Et(2)O, 1, crystallizes in the monoclinic space group P2(1)/c, with a = 10.258(2) Å, b = 19.876(3) Å, c = 25.592(4) Å, and beta = 97.12(2) degrees. The nickel ions in 1 are bridged by the phenoxy donor of the ligand and a perchlorate anion. The complexes [Ni(2)(tbpO)(MeCOO)(H(2)O)](ClO(4))(2).H(2)O.Et(2)O, 2, [Ni(2)(m-tbpO)(PhCOO)(EtOH)(2)](ClO(4))(2).EtOH, 3, and [Ni(2)(bpepO)(MeCOO)(H(2)O)(2)](ClO(4))(2).H(2)O.Et(2)O.2EtOH, 4, also crystallize in the monoclinic crystal system with the following unit cell parameters: 2, C2/c, a = 35.360(13) Å, b = 10.958(3) Å, c = 24.821(10) Å, beta = 103.55(3) degrees; 3, Cc, a = 14.663(5) Å, b = 32.630(13) Å, c = 9.839(3) Å, beta = 92.49(2) degrees; 4, C2/c, a = 27.689(13) Å, b = 12.187(5) Å, c = 31.513(14) Å, beta = 115.01(3) degrees. The dinuclear centers of all these complexes are bridged by the alkoxy donor of the ligand and a carboxylate function. Compounds 2 and 3 have one of the nickel ions in a five-coordinated, trigonal bipyramidal coordination environment and thus show a high structural similarity to the dinuclear active site of urease from Klebsiella aerogenes. Furthermore, their magnetic and spectroscopic properties were determined and related to those of the urease enzymes. Activity toward hydrolysis of test substrates (4-nitrophenyl)urea, 4-nitroacetanilide, 4-nitrophenyl phosphate or bis(4-nitrophenyl) phosphate by the dinuclear complexes were examined by UV spectroscopic measurements.

D-beta-hydroxybutyrate protects dopaminergic SH-SY5Y cells in a rotenone model of Parkinson's disease.

PubMed

Imamura, Keiko; Takeshima, Takao; Kashiwaya, Yoshihiro; Nakaso, Kazuhiro; Nakashima, Kenji

2006-11-01

It has been postulated that the pathogenesis of Parkinson's disease (PD) is associated with mitochondrial dysfunction. Rotenone, an inhibitor of mitochondrial complex I, provides models of PD both in vivo and in vitro. We investigated the neuroprotective effect of D-beta-hydroxybutyrate (bHB), a ketone body, against rotenone toxicity by using SH-SY5Y dopaminergic neuroblastoma cells. SH-SY5Y cells, differentiated by all-trans-retinoic acid, were exposed to rotenone at concentrations ranging from 0 to 1,000 nM. We evaluated cellular oxidation reduction by the alamarBlue assay, viability by lactate dehydrogenase (LDH) assay, and survival/death ratio by live/dead assays. Exposure to rotenone for 48 hr oxidized cells and decreased their viability and survival rate in a concentration-dependent manner. Pretreatment of cells with 8 mM bHB provided significant protection to SH-SY5Y cells. Whereas rotenone caused the loss of mitochondrial membrane potential, released cytochrome c into the cytosol, and reduced cytochrome c content in mitochondria, addition of bHB blocked this toxic effect. bHB also attenuated the rotenone-induced activation of caspase-9 and caspase-3. Administration of 0-10 mM 3-nitropropionic acid, a complex II inhibitor, also decreased the reducing power of SH-SY5Y cells measured by alamarBlue assay. Pretreatment with 8 mM bHB attenuated the decrease of alamarBlue fluorescence. These data demonstrated that bHB had a neuroprotective effect that supported the mitochondrial respiration system by reversing the inhibition of complex I or II. Ketone bodies, the alternative energy source in the mammalian brain, appear to have therapeutic potential in PD. Copyright 2006 Wiley-Liss, Inc.

Tetranuclear copper(II) complexes bridged by alpha-D-glucose-1-phosphate and incorporation of sugar acids through the Cu4 core structural changes.

PubMed

Kato, Merii; Sah, Ajay Kumar; Tanase, Tomoaki; Mikuriya, Masahiro

2006-08-21

Tetranuclear copper(II) complexes containing alpha-D-glucose-1-phosphate (alpha-D-Glc-1P), [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(bpy)4(H2O)2]X3 [X = NO3 (1a), Cl (1b), Br (1c)], and [Cu4(mu-OH){mu-(alpha-D-Glc-1P)}2(phen)4(H2O)2](NO3)3 (2) were prepared by reacting the copper(II) salt with Na2[alpha-D-Glc-1P] in the presence of diimine ancillary ligands, and the structure of 2 was characterized by X-ray crystallography to comprise four {Cu(phen)}2+ fragments connected by the two sugar phosphate dianions in 1,3-O,O' and 1,1-O mu4-bridging fashion as well as a mu-hydroxo anion. The crystal structure of 2 involves two chemically independent complex cations in which the C2 enantiomeric structure for the trapezoidal tetracopper(II) framework is switched according to the orientation of the alpha-D-glucopyranosyl moieties. Temperature-dependent magnetic susceptibility data of 1a indicated that antiferromagnetic spin coupling is operative between the two metal ions joined by the hydroxo bridge (J = -52 cm(-1)) while antiferromagnetic interaction through the Cu-O-Cu sugar phosphate bridges is weak (J = -13 cm(-1)). Complex 1a readily reacted with carboxylic acids to afford the tetranuclear copper(II) complexes, [Cu4{mu-(alpha-D-Glc-1P)}2(mu-CA)2(bpy)4](NO3)2 [CA = CH3COO (3), o-C6H4(COO)(COOH) (4)]. Reactions with m-phenylenediacetic acid [m-C6H4(CH2COOH)2] also gave the discrete tetracopper(II) cationic complex [Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)(CH2COOH))2(bpy)4](NO3)2 (5a) as well as the cluster polymer formulated as {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-m-C6H4(CH2COO)2)(bpy)4](NO3)2}n (5b). The tetracopper structure of 1a is converted into a symmetrical rectangular core in complexes 3, 4, and 5b, where the hydroxo bridge is dissociated and, instead, two carboxylate anions bridge another pair of Cu(II) ions in a 1,1-O monodentate fashion. The similar reactions were applied to incorporate sugar acids onto the tetranuclear copper(II) centers. Reactions of 1a with delta-D-gluconolactone, D-glucuronic acid, or D-glucaric acid in dimethylformamide resulted in the formation of discrete tetracopper complexes with sugar acids, [Cu4{mu-(alpha-D-Glc-1P)}2(mu-SA)2(bpy)4](NO3)2 [SA = D-gluconate (6), D-glucuronate (7), D-glucarateH (8a)]. The structures of 6 and 7 were determined by X-ray crystallography to be almost identical with that of 3 with additional chelating coordination of the C-2 hydroxyl group of D-gluconate moieties (6) or the C-5 cyclic O atom of D-glucuronate units (7). Those with D-glucaric acid and D-lactobionic acid afforded chiral one-dimensional polymers, {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-D-glucarate)(bpy)4](NO3)2}n (8b) and {[Cu4{mu-(alpha-D-Glc-1P)}2(mu-D-lactobionate)(bpy)4(H2O)2](NO3)3}n (9), respectively, in which the D-Glc-1P-bridged tetracopper(II) units are connected by sugar acid moieties through the C-1 and C-6 carboxylate O atoms in 8b and the C-1 carboxylate and C-6 alkoxy O atoms of the gluconate chain in 9. When complex 7 containing d-glucuronate moieties was heated in water, the mononuclear copper(II) complex with 2-dihydroxy malonate, [Cu(mu-O2CC(OH)2CO2)(bpy)] (10), and the dicopper(II) complex with oxalate, [Cu2(mu-C2O4)(bpy)2(H2O)2](NO3)2 (11), were obtained as a result of oxidative degradation of the carbohydrates through C-C bond cleavage reactions.

Topological and Geometric Tools for the Analysis fo Complex Networks

DTIC Science & Technology

2013-10-01

CONTRACT NUMBER FA 9550-09-1-0090 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR( S ) Ali Jadbabaie (Penn) Shing-Tung Yau (Harvard) Fan Chung...NUMBER 7. PERFORMING ORGANIZATION NAME( S ) AND ADDRESS(ES) University of Pennsylvania 34th and Spruce Street, Philadelphia 19104-6303 8. PERFORMING...ORGANIZATION REPORT NUMBER 9. SPONSORING/MONITORING AGENCY NAME( S ) AND ADDRESS(ES) Air Force Office of Scientific Research 875 North Randolph Street

[Aggression faced by doctors during social service in Mexico].

PubMed

Arredondo Trujillo, Francisco; Gascón Santos, Santiago; Espino Álvarez, Luis Arturo; Torres Morquecho, Maricela

2014-12-01

Physicians during their work activities have been exposed to suffering physical and non-physical aggression (insults, threats, sexual assaults and even murder) by patients. The frequency of such attacks has increased in recent years. The aim of this study is to identify the risk of attacks on physicians associated with the type of work place that health institutions have assigned them for their year of social service in Mexico. A cross-sectional questionnaire survey was conducted during 2012 of 371 physicians who were assigned to work in various community health centers called type "A", "B" or "C". Having worked in a work place type "C" was associated with physical aggression (OR: 2.32; 95% CI: 1.03-5.37), threats (OR: 2.64; 95% CI: 1.43-4.93), and insults (OR: 2.28; 95% CI: 1.35-3.88). The results should be interpreted with caution, but they suggest that physicians who are assigned to work in the places type "C" (where they must care for patients in a solitary manner and at night) during the year of social service in Mexico have a significant risk of being attacked.

Crystallization and X-ray diffraction analysis of the HMG domain of the chondrogenesis master regulator Sox9 in complex with a ChIP-Seq-identified DNA element

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

Vivekanandan, Saravanan; Moovarkumudalvan, Balasubramanian; Lescar, Julien

Sox9 is a fundamental sex-determining gene and the master regulator of chondrogenesis, and is involved in the development of various vital organs such as testes, kidney, heart and brain, and in skeletal development. Similar to other known Sox transcription factors, Sox9 recognizes and binds DNA with the consensus sequence C(T/A)TTG(T/A)(T/A) through the highly conserved HMG domain. Nonetheless, the molecular basis of the functional specificity of Sox9 in key developmental processes is still unclear. As an initial step towards a mechanistic understanding of Sox9 transcriptional regulation, the current work describes the details of the purification of the mouse Sox9 HMG domainmore » (mSox9HMG), its crystallization in complex with a ChIP-Seq-identified FOXP2 promoter DNA element and the X-ray diffraction data analysis of this complex. The mSox9HMG–FOXP2 promoter DNA complex was crystallized by the hanging-drop vapour-diffusion method using 20% PEG 3350 in 200 mMsodium/potassium phosphate with 100 mMbis-tris propane at pH 8.5. The crystals diffracted to 2.7 Å resolution and the complex crystallized in the tetragonal space groupP4 12 12, with unit-cell parametersa=b= 99.49,c= 45.89 Å. Crystal-packing parameters revealed that asymmetric unit contained one mSox9HMG–FOXP2 promoter DNA complex with an estimated solvent content of 64%.« less

Structural comparative studies on new Mn(II), Cr(III) and Ru(III) complexes derived from 2,4,6-tri-(2-pyridyl)-1,3,5-triazine (TPTZ).

PubMed

Al-Assy, Waleed H; El-Askalany, Abdel Moneum H; Mostafa, Mohsen M

2013-12-01

The structure of a new Mn(II) complex, [Mn(TPTZ)Cl2(H2O)]⋅H2O, was established by a single crystal X-ray diffraction. Crystal data are as follow: monoclinic, P21/c,a = 8.7202 (3)Å, b = 11.5712 (4)Å, c = 20.8675 (9)Å, β=11 (18) × 1010, V = 2029.27 (13)Å(3), Z = 4. The HOMO, LUMO and other DFT parameters on the atoms have been calculated to confirm the geometry of the ligand and its complexes using material studio program. The complexes were characterized by elemental analyses, spectral, magnetic, thermal and cyclic voltammetry measurements. Electronic spectra and magnetic moments of the complexes suggest distorted-octahedral structures around the metal ions (Mn(II), Cr(III) and Ru(III)). The redox properties were investigated by cyclic voltammetry. Kinetic parameters were determined using Coats-Redfern and Horowitz-Metzger methods. The results of DNA studies of the metal complexes promised to be effective in tumour treatment. Copyright © 2013 Elsevier B.V. All rights reserved.

Solar Ultraviolet-B Radiation Affects Seedling Emergence, DNA Integrity, Plant Morphology, Growth Rate, and Attractiveness to Herbivore Insects in Datura ferox.

PubMed Central

Ballare, C. L.; Scopel, A. L.; Stapleton, A. E.; Yanovsky, M. J.

1996-01-01

To study functional relationships between the effects of solar ultraviolet-B radiation (UV-B) on different aspects of the physiology of a wild plant, we carried out exclusion experiments in the field with the summer annual Datura ferox L. Solar UV-B incident over Buenos Aires reduced daytime seedling emergence, inhibited stem elongation and leaf expansion, and tended to reduce biomass accumulation during early growth. However, UV-B had no effect on calculated net assimilation rate. Using a monoclonal antibody specific to the cyclobutane-pyrimidine dimer (CPD), we found that plants receiving full sunlight had more CPDs per unit of DNA than plants shielded from solar UV-B, but the positive correlation between UV-B and CPD burden tended to level off at high (near solar) UV-B levels. At our field site, Datura plants were consumed by leaf beetles (Coleoptera), and the proportion of plants attacked by insects declined with the amount of UV-B received during growth. Field experiments showed that plant exposure to solar UV-B reduced the likelihood of leaf beetle attack by one-half. Our results highlight the complexities associated with scaling plant responses to solar UV-B, because they show: (a) a lack of correspondence between UV-B effects on net assimilation rate and whole-plant growth rate, (b) nonlinear UV-B dose-response curves, and (c) UV-B effects of plant attractiveness to natural herbivores. PMID:12226382

Hereditary Angioedema Attacks Resolve Faster and Are Shorter after Early Icatibant Treatment

PubMed Central

Maurer, Marcus; Kaplan, Allen; Investigators, on behalf of I. O. S.

2013-01-01

Background Attacks of hereditary angioedema (HAE) are unpredictable and, if affecting the upper airway, can be lethal. Icatibant is used for physician- or patient self-administered symptomatic treatment of HAE attacks in adults. Its mode of action includes disruption of the bradykinin pathway via blockade of the bradykinin B2 receptor. Early treatment is believed to shorten attack duration and prevent severe outcomes; however, evidence to support these benefits is lacking. Objective To examine the impact of timing of icatibant administration on the duration and resolution of HAE type I and II attacks. Methods The Icatibant Outcome Survey is an international, prospective, observational study for patients treated with icatibant. Data on timings and outcomes of icatibant treatment for HAE attacks were collected between July 2009–February 2012. A mixed-model of repeated measures was performed for 426 attacks in 136 HAE type I and II patients. Results Attack duration was significantly shorter in patients treated <1 hour of attack onset compared with those treated ≥1 hour (6.1 hours versus 16.8 hours [p<0.001]). Similar significant effects were observed for <2 hours versus ≥2 hours (7.2 hours versus 20.2 hours [p<0.001]) and <5 hours versus ≥5 hours (8.0 hours versus 23.5 hours [p<0.001]). Treatment within 1 hour of attack onset also significantly reduced time to attack resolution (5.8 hours versus 8.8 hours [p<0.05]). Self-administrators were more likely to treat early and experience shorter attacks than those treated by a healthcare professional. Conclusion Early blockade of the bradykinin B2 receptor with icatibant, particularly within the first hour of attack onset, significantly reduced attack duration and time to attack resolution. PMID:23390491

21 CFR 184.1212 - Calcium pantothenate.

Code of Federal Regulations, 2010 CFR

2010-04-01

... ((C9H16NO5)2Ca, CAS Reg. No. of the D-isomer, 137-08-6) is a salt of pantothenic acid, one of the vitamins of the B complex. Only the D-isomer of pantothenic acid has vitamin activity, although both the D-isomer...)(2) of the Act. (d) Prior sanctions for this ingredient different from the uses established in this...

Honeycomb-like S = 5/2 Spin–Lattices in Manganese(II) Vanadates

DOE PAGES

Sanjeewa, Liurukara. D.; McGuire, Michael A.; McMillen, Colin D.; ...

2016-08-26

We synthesized new complex manganese vanadate materials as high-quality single crystals in multi-millimeter lengths using a high-temperature, high-pressure hydrothermal method. We grew one compound, Mn 5(VO 4) 2(OH) 4, from Mn 2O 3 and V 2O 5 in 3 M CsOH at 580 °C and 1.5 kbar. Changing the mineralizer to 1 M CsOH/3MCsCl leads to the formation of another product, Mn 6O(VO 4) 2(OH). Both compounds were structurally characterized by single-crystal X-ray diffraction (Mn 5(VO 4) 2(OH) 4: C2/m, Z = 2, a = 9.6568(9) Å, b = 9.5627(9) Å, c = 5.4139(6) Å, β = 98.529(8)°; Mn 6O(VOmore » 4) 2(OH): P21/m, Z = 2, a = 8.9363(12) Å, b = 6.4678(8) Å, c = 10.4478(13) Å, β = 99.798(3)°), revealing interesting low-dimensional transition-metal features. Mn 5(VO 4) 2(OH) 4 possesses complex honeycomb-type Mn–O layers, built from edge-sharing [MnO 6] octahedra in the bc plane, with bridging vanadate groups connecting these layers along the a-axis. Mn 6O(VO 4) 2(OH) presents a more complicated structure with both octahedral [MnO 6] and trigonal bipyramidal [MnO 5] units. A different pattern of planar honeycomb sheets are formed by edge-shared [MnO6] octahedra, and these sublattices are connected through edge-shared dimers of [MnO 5] trigonal bipyramids to form corrugated sheets. Vanadate groups again condense the sheets into a three-dimensional framework. Infrared and Raman spectroscopies indicated the presence of OH groups and displayed characteristic Raman scattering due to vanadate groups. Furthermore, temperature-dependent magnetic studies indicated Curie–Weiss behavior above 100 K with significant anti-ferromagnetic coupling for both compounds, with further complex magnetic behavior at lower temperatures. The data indicate canted anti-ferromagnetic order below 57 K in Mn 5(VO 4) 2(OH) 4 and below 45 K in Mn 6O(VO 4) 2(OH). Members of another class of compounds, K 2M 3(VO 4) 2(OH) 2 (M = Mn, Co), also containing a honeycomb-type sublattice, were also synthesized to allow a comparison of the structural features across all three structure types and to demonstrate extension to other transition metals.« less

Pathogenic Leptospira Species Acquire Factor H and Vitronectin via the Surface Protein LcpA

PubMed Central

da Silva, Ludmila Bezerra; Miragaia, Lidia dos Santos; Breda, Leandro Carvalho Dantas; Abe, Cecilia Mari; Schmidt, Mariana Costa Braga; Moro, Ana Maria; Monaris, Denize; Conde, Jonas Nascimento; Józsi, Mihály; Isaac, Lourdes; Abreu, Patrícia Antônia Estima

2014-01-01

Upon infection, pathogenic Leptospira species bind several complement regulators in order to overcome host innate immunity. We previously characterized a 20-kDa leptospiral surface protein which interacts with C4b binding protein (C4BP): leptospiral complement regulator-acquiring protein A (LcpA). Here we show that LcpA also interacts with human factor H (FH), which remains functionally active once bound to the protein. Antibodies directed against short consensus repeat 20 (SCR20) inhibited binding of FH to LcpA by approximately 90%, thus confirming that this particular domain is involved in the interaction. We have also shown for the first time that leptospires bind human vitronectin and that the interaction is mediated by LcpA. Coincubation with heparin blocked LcpA-vitronectin interaction in a dose-dependent manner, strongly suggesting that binding may occur through the heparin binding domains of vitronectin. LcpA also bound to the terminal pathway component C9 and inhibited Zn2+-induced polymerization and membrane attack complex (MAC) formation. Competitive binding assays indicated that LcpA interacts with C4BP, FH, and vitronectin through distinct sites. Taken together, our findings indicate that LcpA may play a role in leptospiral immune evasion. PMID:25534939

Pathogenic Leptospira species acquire factor H and vitronectin via the surface protein LcpA.

PubMed

da Silva, Ludmila Bezerra; Miragaia, Lidia Dos Santos; Breda, Leandro Carvalho Dantas; Abe, Cecilia Mari; Schmidt, Mariana Costa Braga; Moro, Ana Maria; Monaris, Denize; Conde, Jonas Nascimento; Józsi, Mihály; Isaac, Lourdes; Abreu, Patrícia Antônia Estima; Barbosa, Angela Silva

2015-03-01

Upon infection, pathogenic Leptospira species bind several complement regulators in order to overcome host innate immunity. We previously characterized a 20-kDa leptospiral surface protein which interacts with C4b binding protein (C4BP): leptospiral complement regulator-acquiring protein A (LcpA). Here we show that LcpA also interacts with human factor H (FH), which remains functionally active once bound to the protein. Antibodies directed against short consensus repeat 20 (SCR20) inhibited binding of FH to LcpA by approximately 90%, thus confirming that this particular domain is involved in the interaction. We have also shown for the first time that leptospires bind human vitronectin and that the interaction is mediated by LcpA. Coincubation with heparin blocked LcpA-vitronectin interaction in a dose-dependent manner, strongly suggesting that binding may occur through the heparin binding domains of vitronectin. LcpA also bound to the terminal pathway component C9 and inhibited Zn(2+)-induced polymerization and membrane attack complex (MAC) formation. Competitive binding assays indicated that LcpA interacts with C4BP, FH, and vitronectin through distinct sites. Taken together, our findings indicate that LcpA may play a role in leptospiral immune evasion. Copyright © 2015, American Society for Microbiology. All Rights Reserved.

Innate defensive behaviour and panic-like reactions evoked by rodents during aggressive encounters with Brazilian constrictor snakes in a complex labyrinth: behavioural validation of a new model to study affective and agonistic reactions in a prey versus predator paradigm.

PubMed

Guimarães-Costa, Raquel; Guimarães-Costa, Maria Beatriz; Pippa-Gadioli, Leonardo; Weltson, Alfredo; Ubiali, Walter Adriano; Paschoalin-Maurin, Tatiana; Felippotti, Tatiana Tocchini; Elias-Filho, Daoud Hibrahim; Laure, Carlos Júlio; Coimbra, Norberto Cysne

2007-09-15

Defensive behaviour has been extensively studied, and non-invasive methodologies may be interesting approaches to analyzing the limbic system function as a whole. Using experimental models of animals in the state of anxiety has been fundamental in the search for new anxiolytic and antipanic compounds. The aim of this present work is to examine a new model for the study of affective behaviour, using a complex labyrinth consisting of an arena and galleries forming a maze. Furthermore, it aims to compare the defensive behaviour of Wistar rats, Mongolian gerbils and golden hamsters in a complex labyrinth, as well as the defensive behaviour of Meriones unguiculatus in aggressive encounters with either Epicrates cenchria assisi or Boa constrictor amarali in this same model. Among species presently studied, the Mongolian gerbils showed better performance in the exploration of both arena and galleries of the labyrinth, also demonstrating less latency in finding exits of the galleries. This increases the possibility of survival, as well as optimizes the events of encounter with the predator. The duration of alertness and freezing increased during confrontation with living Epicrates, as well as the duration of exploratory behaviour in the labyrinth. There was an increase in the number of freezing and alertness behaviours, as well as in duration of alertness during confrontations involving E.c. assisi, compared with behavioural reactions elicited by jirds in presence of B.c. amarali. Interestingly, the aggressive behaviour of Mongolian gerbils was more prominent against B.c. amarali compared with the other Boidae snake. E.c. assisi elicited more offensive attacks and exhibited a greater time period of body movement than B.c. amarali, which spent more time in the arena and in defensive immobility than the E.c. assisi. Considering that jirds evoked more fear-like reaction in contact with E.c. assisi, a fixed E.c. assisi kept in a hermetically closed acrylic box was used as control. In these prey/predator encounter-based experiments, there was an increase in the number of alertness and freezing behaviours exhibited by gerbils, and a decrease in the number of crossing elicited by them, when comparing confrontations between the living E.c. assisi and the control. The experiments were performed at 7.0 p.m. In the labyrinth, the snakes showed in confrontation similar performance to that observed in nature (organizing hunting behaviour, offensive/defensive attack, constriction, prey inspection and feeding behaviour), which were essential to the validity of the experiments and gave behavioural validation within the complex labyrinth.

The Icatibant Outcome Survey: experience of hereditary angioedema management from six European countries.

PubMed

Caballero, T; Aberer, W; Longhurst, H J; Maurer, M; Zanichelli, A; Perrin, A; Bouillet, L; Andresen, I

2017-07-01

Hereditary angioedema (HAE) due to C1-inhibitor deficiency (C1-INH-HAE) is a rare, potentially fatal, bradykinin-mediated disease. Icatibant is a bradykinin B2 receptor antagonist originally approved in 2008 in the European Union and 2011 in the United States as an acute therapy option for HAE attacks in adults. To compare demographics, disease characteristics and treatment outcomes of icatibant-treated HAE attacks in patients with C1-INH-HAE enrolled in the Icatibant Outcome Survey across six European countries: Austria, France, Germany, Italy, Spain and the UK. The Icatibant Outcome Survey [IOS; Shire, Zug, Switzerland (NCT01034969)] is an international observational study monitoring the safety and effectiveness of icatibant. Descriptive, retrospective analyses compared IOS country data derived during July 2009-April 2015. Overall, 481 patients with C1-INH-HAE provided demographic data. A significant difference across countries in age at onset (P = 0.003) and baseline attack frequency (P < 0.001) was found although no significant differences were found with respect to gender (majority female; P = 0.109), age at diagnosis (P = 0.182) or delay in diagnosis (P = 0.059). Icatibant was used to treat 1893 attacks in 325 patients with majority self-administration in all countries. Overall, significant differences (all P < 0.001) were found across countries in time to treatment [median 1.8 h; median range: 0.0 (Germany-Austria) to 4.4 (France) h], time to resolution [median 6.5 h; median range: 3 (Germany-Austria) to 12 (France) h] and attack duration [median 10.5 h; median range: 3.1 (Germany-Austria) to 18.5 (France) h]. These data form the first European cross-country comparison of disease characteristics and icatibant use in patients with C1-INH-HAE who are enrolled in IOS. International variation in icatibant practice and treatment outcomes across the six European countries assessed highlight the need to further investigate the range of country-specific parameters driving regional variations in icatibant use. © 2017 The Authors. Journal of the European Academy of Dermatology and Venereology published by John Wiley & Sons Ltd on behalf of European Academy of Dermatology and Venereology.

Reaction of a (Salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (Salen)ruthenium(IV) sulfilamido species.

PubMed

Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu

2010-01-04

The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.

Pulse Shaping and Energy Storage Capabilities of Angularly-Multiplexed KrF Laser Fusion Drivers

DTIC Science & Technology

2009-01-01

6&-7 9)%:5?𔄃%1706-?1 6%5&1-J.% 5?./2 (% %x9%)-’%160//C -𔄃/%’%16%2 -1 )%0/ 6-’% ?1 0 )%9:)06%2 /07%) 7C76%’" 8&% 7-’./06-? 17 7&?K 6&06 6&-7 ’./6-(%0...8217 7C76%’ 501 05&-%=% 0 &-*& L2%/-6C 9./7% 7&09-1* 5090(-/-6CG %=%1 >?) 0 &-*& *0-1 7&?5B -*1-6-?1 9./7% K&?7% L10/ 79-B% )%J.-)%7 ?.69.6 -16% 17 -6-%7...K-26&7  " 17 " <?) 6&% 5&?7%1 9./7%G K&-5& *-=%7 0 9)%2-56%2 >.7-?1 %1%)*C *0-1  "#$G 6&% 7-’./06-? 17 9)%2-56 6&% ɠ< 501 2%/-=%) 0 6?60/ ?1:60)*%6

Dithiolato- and halogenido-bridged nickel-iron complexes related to the active site of [NiFe]-H2ases: preparation, structures, and electrocatalytic H2 production.

PubMed

Song, Li-Cheng; Han, Xiao-Feng; Chen, Wei; Li, Jia-Peng; Wang, Xu-Yong

2017-08-14

A new series of the structural and functional models for the active site of [NiFe]-H 2 ases has been prepared by a simple and convenient synthetic route. Thus, treatment of diphosphines RN(PPh 2 ) 2 (1a, R = p-MeC 6 H 4 CH 2 ; 1b, R = EtO 2 CCH 2 ) with an equimolar NiCl 2 ·6H 2 O, NiBr 2 ·3H 2 O, and NiI 2 in refluxing CH 2 Cl 2 /MeOH or EtOH gave the mononuclear Ni complexes RN(PPh 2 ) 2 NiX 2 (2a, R = p-MeC 6 H 4 CH 2 , X = Cl; 2b, R = EtO 2 CCH 2 , X = Cl; 3a, R = p-MeC 6 H 4 CH 2 , X = Br; 3b, R = EtO 2 CCH 2 , X = Br; 4a, R = p-MeC 6 H 4 CH 2 , X = I; 4b, R = EtO 2 CCH 2 , X = I) in 67-97% yields. Further treatment of complexes 2a,b-4a,b with an equimolar mononuclear Fe complex (dppv)(CO) 2 Fe(pdt) and NaBF 4 resulted in formation of the targeted model complexes [RN(PPh 2 ) 2 Ni(μ-pdt)(μ-X)Fe(CO)(dppv)](BF 4 ) (5a, R = p-MeC 6 H 4 CH 2 , X = Cl; 5b, R = EtO 2 CCH 2 , X = Cl; 6a, R = p-MeC 6 H 4 CH 2 , X = Br; 6b, R = EtO 2 CCH 2 , X = Br; 7a, R = p-MeC 6 H 4 CH 2 , X = I; 7b, R = EtO 2 CCH 2 , X = I) in 60-96% yields. All the new complexes 3a,b-4a,b and 5a,b-7a,b have been characterized by elemental analysis and spectroscopy, and particularly for some of them (3a,b/4a,b and 5b/6b) by X-ray crystallography. More interestingly, the electrochemical and electrocatalytic properties of such halogenido-bridged model complexes are first studied systematically and particularly they have been found to be pre-catalysts for proton reduction to H 2 under CV conditions.

Nickel(II) Complex of Polyhydroxybenzaldehyde N4-Thiosemicarbazone Exhibits Anti-Inflammatory Activity by Inhibiting NF-κB Transactivation

PubMed Central

Loh, Sheng Wei; Looi, Chung Yeng; Hassandarvish, Pouya; Phan, Alicia Yi Ling; Wong, Won Fen; Wang, Hao; Paterson, Ian C.; Ea, Chee Kwee; Mustafa, Mohd Rais; Maah, Mohd Jamil

2014-01-01

Background The biological properties of thiosemicarbazone have been widely reported. The incorporation of some transition metals such as Fe, Ni and Cu to thiosemicarbazone complexes is known to enhance its biological effects. In this study, we incorporated nickel(II) ions into thiosemicarbazone with N4-substitution groups H3L (H; H3L1, CH3; H3L2, C6H5; H3L3 and C2H5; H3L4) and examined its potential anti-inflammatory activity. Methodology/Principal Findings Four ligands (1–4) and their respective nickel-containing complexes (5–8) were synthesized and characterized. The compounds synthesized were tested for their effects on NF-κB nuclear translocation, pro-inflammatory cytokines secretion and NF-κB transactivation activity. The active compound was further evaluated on its ability to suppress carrageenan-induced acute inflammation in vivo. A potential binding target of the active compound was also predicted by molecular docking analysis. Conclusions/Significance Among all synthesized compounds tested, we found that complex [Ni(H2L1)(PPh3)]Cl (5) (complex 5), potently inhibited IκBα degradation and NF-κB p65 nuclear translocation in LPS-stimulated RAW264.7 cells as well as TNFα-stimulated HeLa S3 cells. In addition, complex 5 significantly down-regulated LPS- or TNFα-induced transcription of NF-κB target genes, including genes that encode the pro-inflammatory cytokines TNFα, IFNβ and IL6. Luciferase reporter assays confirmed that complex 5 inhibited the transactivation activity of NF-κB. Furthermore, the anti-inflammatory effect of complex 5 was also supported by its suppressive effect on carrageenan-induced paw edema formation in wild type C57BL/6 mice. Interestingly, molecular docking study showed that complex 5 potentially interact with the active site of IKKβ. Taken together, we suggest complex 5 as a novel NF-κB inhibitor with potent anti-inflammatory effects. PMID:24977407

Synthesis, characterisation and catalytic activity of 4, 5-imidazoledicarboxylate ligated Co(II) and Cd(II) metal-organic coordination complexes

NASA Astrophysics Data System (ADS)

Gangu, Kranthi Kumar; Maddila, Suresh; Mukkamala, Saratchandra Babu; Jonnalagadda, Sreekantha B.

2017-09-01

Two mono nuclear coordination complexes, namely, [Co(4,5-Imdc)2 (H2O)2] (1) and [Cd(4,5-Imdc)2(H2O)3]·H2O (2) were constructed using Co(II) and Cd(II) metal salts with 4,5-Imidazoledicarboxylic acid (4,5-Imdc) as organic ligand. Both 1, 2 were structurally characterized by single crystal XRD and the results reveal that 1 belongs to P21/n space group with unit cell parameters [a = 5.0514(3) Å, b = 22.5786(9) Å, c = 6.5377(3) Å, β = 111.5°] whereas, 2 belongs to P21/c space group with unit cell parameters [a = 6.9116(1) Å, b = 17.4579(2) Å, c = 13.8941(2) Å, β = 97.7°]. While Co(II) in 1 exhibited a six coordination geometry with 4,5-Imdc and water molecules, Cd(II) ion in 2 showed a seven coordination with the same ligand and solvent. In both 1 and 2, the hydrogen bond interactions with mononuclear unit generated 3D-supramolecular structures. Both complexes exhibit solid state fluorescent emission at room temperature. The efficacy of both the complexes as heterogeneous catalysts was examined in the green synthesis of six pyrano[2,3,c]pyrazole derivatives with ethanol as solvent via one-pot reaction between four components, a mixture of aromatic aldehyde, malononitrile, hydrazine hydrate and dimethyl acetylenedicarboxylate. Both 1 and 2 have produced pyrano [2,3,c]pyrazoles in impressive yields (92-98%) at room temperature in short interval of times (<20 min), with no need for any chromatographic separations. With good stability, ease of preparation and recovery plus reusability up to six cycles, both 1 and 2 prove to be excellent environmental friendly catalysts for the value-added organic transformations using green principles.

Observation of Ξ c(2930)^0 and updated measurement of B- → K- Λ c+ \\bar{Λ }c- at Belle

NASA Astrophysics Data System (ADS)

Li, Y. B.; Shen, C. P.; Adachi, I.; Ahn, J. K.; Aihara, H.; Al Said, S.; Asner, D. M.; Aushev, T.; Ayad, R.; Babu, V.; Badhrees, I.; Bakich, A. M.; Ban, Y.; Bansal, V.; Behera, P.; Berger, M.; Bhardwaj, V.; Bhuyan, B.; Biswal, J.; Bonvicini, G.; Bozek, A.; Bračko, M.; Browder, T. E.; Červenkov, D.; Chekelian, V.; Chen, A.; Cheon, B. G.; Chilikin, K.; Cho, K.; Choi, S.-K.; Choi, Y.; Cinabro, D.; Cunliffe, S.; Dash, N.; Di Carlo, S.; Doležal, Z.; Drásal, Z.; Eidelman, S.; Epifanov, D.; Fast, J. E.; Ferber, T.; Fulsom, B. G.; Garg, R.; Gaur, V.; Gabyshev, N.; Garmash, A.; Gelb, M.; Giri, A.; Goldenzweig, P.; Guido, E.; Haba, J.; Hara, T.; Hayasaka, K.; Hayashii, H.; Hedges, M. T.; Hou, W.-S.; Iijima, T.; Inami, K.; Inguglia, G.; Ishikawa, A.; Itoh, R.; Iwasaki, M.; Iwasaki, Y.; Jacobs, W. W.; Jia, S.; Jin, Y.; Joo, K. K.; Julius, T.; Karyan, G.; Kato, Y.; Kawasaki, T.; Kichimi, H.; Kiesling, C.; Kim, D. Y.; Kim, J. B.; Kim, K. T.; Kim, S. H.; Kinoshita, K.; Kodyš, P.; Korpar, S.; Kotchetkov, D.; Križan, P.; Kroeger, R.; Krokovny, P.; Kulasiri, R.; Kumita, T.; Kuzmin, A.; Kwon, Y.-J.; Lee, I. S.; Lee, S. C.; Li, L. K.; Li Gioi, L.; Libby, J.; Liventsev, D.; Lubej, M.; Luo, T.; MacNaughton, J.; Masuda, M.; Matsuda, T.; Merola, M.; Miyabayashi, K.; Miyata, H.; Mizuk, R.; Mohanty, G. B.; Moon, H. K.; Mori, T.; Mrvar, M.; Mussa, R.; Nakano, E.; Nakao, M.; Nanut, T.; Nath, K. J.; Natkaniec, Z.; Nayak, M.; Niiyama, M.; Nishida, S.; Ogawa, S.; Pakhlov, P.; Pakhlova, G.; Pal, B.; Pardi, S.; Park, C. W.; Park, H.; Paul, S.; Pedlar, T. K.; Pestotnik, R.; Piilonen, L. E.; Popov, V.; Rostomyan, A.; Russo, G.; Sakai, Y.; Salehi, M.; Sandilya, S.; Santelj, L.; Sanuki, T.; Schneider, O.; Schnell, G.; Schwanda, C.; Seino, Y.; Shebalin, V.; Shibata, T.-A.; Shiu, J.-G.; Shwartz, B.; Sokolov, A.; Solovieva, E.; Starič, M.; Strube, J. F.; Sumihama, M.; Sumiyoshi, T.; Takizawa, M.; Tamponi, U.; Tanida, K.; Tenchini, F.; Uchida, M.; Uglov, T.; Unno, Y.; Uno, S.; Van Hulse, C.; Varner, G.; Vorobyev, V.; Vossen, A.; Waheed, E.; Wang, B.; Wang, C. H.; Wang, M.-Z.; Wang, P.; Wang, X. L.; Watanabe, M.; Watanabe, Y.; Widmann, E.; Won, E.; Ye, H.; Yelton, J.; Yuan, C. Z.; Yusa, Y.; Zakharov, S.; Zhang, Z. P.; Zhilich, V.; Zhukova, V.; Zhulanov, V.

2018-03-01

We report the first observation of the Ξ c(2930)^0 charmed-strange baryon with a significance greater than 5σ . The Ξ c(2930)^0 is found in its decay to K^- Λ c^+ in B- → K- Λ c+ \\bar{Λ }c- decays. The measured mass and width are [2928.9 ± 3.0(stat.)^{+0.9}_{-12.0}(syst.)] MeV/c2 and [19.5 ± 8.4(stat.) ^{+5.9}_{-7.9}(syst.)] MeV, respectively, and the product branching fraction is B(B- → Ξ c(2930)^0 \\bar{Λ }c-) B(Ξ c(2930)^0 → K^- Λ c+)=[1.73 ± 0.45(stat.) ± 0.21(syst.)]× 10^{-4}. We also measure B(B- → K- Λ c+ \\bar{Λ }c-) = [4.80 ± 0.43(stat.) ± 0.60(syst.)] × 10^{-4} with improved precision, and search for the charmonium-like state Y(4660) and its spin partner, Y_{η }, in the Λ c+\\bar{Λ }c- invariant mass spectrum. No clear signals of the Y(4660) nor its spin partner are observed and the 90% credibility level (C.L.) upper limits on their production rates are determined. These measurements are obtained from a sample of (772± 11)× 106 B\\bar{B} pairs collected at the Υ (4S) resonance by the Belle detector at the KEKB asymmetric energy electron-positron collider.

First-Strike Advantage: The United States’ Counter to China’s Preemptive Integrated Network Electronic Warfare Strategy

DTIC Science & Technology

2013-06-01

Ground: Chinese Capabilities for Computer Network Operations and Cyber Espionage,” 9. 57 Lolita C. Baldor, “Chinese Cyber Attacks On U.S. Continue...the Secretary of Defense, 2009. Baldor, Lolita C. “Chinese Cyber Attacks on U.S. Continue Totally Unabated, Leon Panetta.” Huffington Post (2012

[Rhodobaculum claviforme gen. nov., sp. nov., a New Alkaliphilic Nonsulfur Purple Bacterium].

PubMed

Bryantseva, I A; Gaisin, V A; Gorlenko, V M

2015-01-01

Two alkaliphilic strains of nonsulfur purple bacteria (NPB), B7-4 and B8-2, were isolated from southeast Siberia moderately saline alkaline steppe lakes with pH values above 9.0. The isolates were motile, polymorphous cells (from short rods to long spindly cells) 2.0-3.2 x 9.6-20.0 μm. Intracellular membranes of vesicular type were mostly located at the cell periphery. The microorganisms contained bacteriochlorophyll a and carotenoids of the spheroidene and spirilloxanthin series. The photosynthetic apparatus was represented by LH2 and LH1 light-harvesting complexes. In the presence of organic compounds, the strains grew aerobically in the dark or anaerobically in the light. Capacity for photo- and chemoautotrophic growth was not detected. The cbbl gene encoding RuBisCO was not revealed. Optimal growth of both strains occurred at 2% NaCl (range from 0.5 to 4%), pH 8.0-8.8 (range from 7.5 to 9.7), and 25-35 degrees C. The DNA G+C content was 67.6-69.8 mol %. Pairwise comparison of the nucleotides of the 16S rRNA genes revealed that strains B7-4 and B8-2 belonged to the same species (99.9% homology) and were most closely related to the aerobic alkaliphilic bacteriochlorophyll a-containing anoxygenic phototrophic bacterium (APB) Roseibacula alcaliphilum De (95.2%) and to NPB strains Rhodobaca barguzinensis VKM B-2406(T) (94.2%) and Rbc. bogoriensis LBB1(T) (93.9%). The isolates were closely related to the NPB Rhodobacter veldkampii DSM 11550(T) (94.8%) and to aerobic bacteriochlorophyll a-containing bacteria Roseinatronobacter monicus ROS 35(T) and Roseicitreum antarcticul ZS2-28(T) (93.5 and 93.9%, respectively). New strains were described as a new NPB genus and species of the family Rhodobacteriaceae, Rhodobaculum claviforme gen. nov., sp. nov., with B7-4(T) (VKM B-2708, LMG 28126) as the type strain.

Enzymatic hydrolysis of p-nitroacetanilide: mechanistic studies of the aryl acylamidase from Pseudomonas fluorescens.

PubMed

Stein, Ross L

2002-01-22

Aryl acylamidase (EC 3.1.5.13; AAA) catalyzes the hydrolysis of p-nitroacetanilide (PNAA) via the standard three-step mechanism of serine hydrolases: binding of substrate (K(s)), acylation of active-site serine (k(acyl)), and hydrolytic deacylation (k(deacyl)). Key mechanistic findings that emerged from this study include that (1) AAA requires a deprotonated base with a pK(a) of 8.3 for expression of full activity toward PNAA. Limiting values of kinetic parameters at high pH are k(c) = 7 s(-1), K(m) = 20 microM, and k(c)/K(m) = 340 000 M(-1) s(-1). (2) At pH 10, where all the isotope effects were conducted, k(c) is equally rate-limited by k(acyl) and k(deacyl). (3) The following isotope effects were determined: (D)()2(O)(k(c)/K(m)) = 1.7 +/- 0.2, (D)()2(O)k(c) = 3.5 +/- 0.3, and (beta)(D)(k(c)/K(m)) = 0.83 +/- 0.04, (beta)(D)k(c) = 0.96 +/- 0.01. These values, together with proton inventories for k(c)/K(m) and k(c), suggest the following mechanism: (i) The initial binding of substrate to enzyme to form the Michaelis complex is accompanied by solvation changes that generate solvent deuterium isotope effects originating from hydrogen ion fractionation at multiple sites on the enzyme surface. (ii) From within the Michaelis complex, the active site serine attacks the carbonyl carbon of PNAA with general-base catalysis to form a substantially tetrahedral transition state enroute to the acyl-enzyme. (iii) Finally, deacylation occurs through a process involving a rate-limiting solvent isotope effect, generating conformational change of the acyl-enzyme that positions the carbonyl bond in a polarizing environment that is optimal for attack by water.

Molecular modeling studies of substrate binding by penicillin acylase.

PubMed

Chilov, G G; Stroganov, O V; Svedas, V K

2008-01-01

Molecular modeling has revealed intimate details of the mechanism of binding of natural substrate, penicillin G (PG), in the penicillin acylase active center and solved questions raised by analysis of available X-ray structures, mimicking Michaelis complex, which substantially differ in the binding pattern of the PG leaving group. Three MD trajectories were launched, starting from PDB complexes of the inactive mutant enzyme with PG (1FXV) and native penicillin acylase with sluggishly hydrolyzed substrate analog penicillin G sulfoxide (1GM9), or from the complex obtained by PG docking. All trajectories converged to a similar PG binding mode, which represented the near-to-attack conformation, consistent with chemical criteria of how reactive Michaelis complex should look. Simulated dynamic structure of the enzyme-substrate complex differed significantly from 1FXV, resembling rather 1GM9; however, additional contacts with residues bG385, bS386, and bN388 have been found, which were missing in X-ray structures. Combination of molecular docking and molecular dynamics also clarified the nature of extremely effective phenol binding in the hydrophobic pocket of penicillin acylase, which lacked proper explanation from crystallographic experiments. Alternative binding modes of phenol were probed, and corresponding trajectories converged to a single binding pattern characterized by a hydrogen bond between the phenol hydroxyl and the main chain oxygen of bS67, which was not evident from the crystal structure. Observation of the trajectory, in which phenol moved from its steady bound to pre-dissociation state, mapped the consequence of molecular events governing the conformational transitions in a coil region a143-a146 coupled to substrate binding and release of the reaction products. The current investigation provided information on dynamics of the conformational transitions accompanying substrate binding and significance of poorly structured and flexible regions in maintaining catalytic framework.

Alternative complement pathway activation during invasive coronary procedures in acute myocardial infarction and stable angina pectoris.

PubMed

Horváth, Zsófia; Csuka, Dorottya; Vargova, Katarina; Kovács, Andrea; Leé, Sarolta; Varga, Lilian; Préda, István; Tóth Zsámboki, Emese; Prohászka, Zoltán; Kiss, Róbert Gábor

2016-12-01

The effect of invasive percutaneous coronary procedures on complement activation has not been elucidated. We enrolled stable angina patients with elective percutaneous coronary intervention (SA-PCI, n=24), diagnostic coronary angiography (CA, n=52) and 23 patients with ST segment elevation myocardial infarction and primary PCI (STEMI-PCI). Complement activation products (C1rC1sC1inh, C3bBbP and SC5b-9) were measured on admission, 6 and 24h after coronary procedures. The alternative pathway product, C3bBbP significantly and reversibly increased 6h after elective PCI (baseline: 7.81AU/ml, 6h: 16.09AU/ml, 24h: 4.27AU/ml, p<0.01, n=23) and diagnostic angiography (baseline: 6.13AU/ml, 6h: 12.08AU/ml, 24h: 5.4AU/ml, p<0.01, n=52). Six hour C3bBbP values correlated with post-procedural CK, creatinine level and the applied contrast material volume (r=0.41, r=0.4, r=0.3, p<0.05, respectively). In STEMI-PCI, baseline C3bBbP level was higher, compared to SA-PCI or CA patients (11.33AU/ml vs. 7.81AU/ml or 6.13AU/ml, p<0.001). Similarly, the terminal complex (SC5b-9) level was already elevated at baseline compared to SA-PCI group (3.49AU/ml vs. 1.87AU/ml, p=0.011). Complement pathway products did not increase further after primary PCI. Elective coronary procedures induced transient alternative complement pathway activation, influenced by the applied contrast volume. In STEMI, the alternative complement pathway is promptly activated during the atherothrombotic event and PCI itself had no further detectable effect. Copyright © 2016 Elsevier B.V. All rights reserved.

Oxidative addition of allylic halides to ruthenium(II) compounds. Preparation, reactions, and X-ray crystallographic structure of ruthenium(IV)-allyl complexes

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

Nagashima, Hideo; Mukai, Katsunori; Shiota, Yusuke

1990-03-01

The oxidative addition of allylic halides to (C{sub 5}R{sub 5})RuL{sub 2}X (R = H, Me; L = CO, PPh{sub 3}) gave new Ru(IV)-{eta}{sup 3}-allyl complexes, (C{sub 5}R{sub 5})RuX{sub 2}({eta}{sup 3}-allyl). An X-ray structure determination was carried out on (C{sub 5}Me{sub 5})RuBr{sub 2}({eta}{sup 3}-C{sub 3}H{sub 5}), indicating a pseudo-piano-stool structure having two Br atoms and two terminal carbons of the endo-{eta}{sup 3}-allyl ligand located at the basal positions. There is a crystal mirror plane bisecting the pentamethylcyclopentadienyl and the {pi}-allyl ligands. Crystal data: orthorhombic, space group P2{sub 1}2{sub 1}2{sub 1}, a = 22.738 (1) {angstrom}, b = 13.367 (7) {angstrom}, cmore » = 9.383 (1) {angstrom}, Z = 4., data refined to R = 0.0695. Its {sup 1}H and {sup 13}C NMR spectra showed symmetric allyl signals, supporting that the above-described piano-stool structure is maintained even in solution.« less

Cytochrome b5 reductase is the component from neuronal synaptic plasma membrane vesicles that generates superoxide anion upon stimulation by cytochrome c.

PubMed

Samhan-Arias, Alejandro K; Fortalezas, Sofia; Cordas, Cristina M; Moura, Isabel; Moura, José J G; Gutierrez-Merino, Carlos

2018-05-01

In this work, we measured the effect of cytochrome c on the NADH-dependent superoxide anion production by synaptic plasma membrane vesicles from rat brain. In these membranes, the cytochrome c stimulated NADH-dependent superoxide anion production was inhibited by antibodies against cytochrome b 5 reductase linking the production to this enzyme. Measurement of the superoxide anion radical generated by purified recombinant soluble and membrane cytochrome b 5 reductase corroborates the production of the radical by different enzyme isoforms. In the presence of cytochrome c, a burst of superoxide anion as well as the reduction of cytochrome c by cytochrome b 5 reductase was measured. Complex formation between both proteins suggests that cytochrome b 5 reductase is one of the major partners of cytochrome c upon its release from mitochondria to the cytosol during apoptosis. Superoxide anion production and cytochrome c reduction are the consequences of the stimulated NADH consumption by cytochrome b 5 reductase upon complex formation with cytochrome c and suggest a major role of this enzyme as an anti-apoptotic protein during cell death. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.

Prevalence and psychological correlates of complicated grief among bereaved adults 2.5-3.5 years after September 11th attacks.

PubMed

Neria, Yuval; Gross, Raz; Litz, Brett; Maguen, Shira; Insel, Beverly; Seirmarco, Gretchen; Rosenfeld, Helena; Suh, Eun Jung; Kishon, Ronit; Cook, Joan; Marshall, Randall D

2007-06-01

A Web-based survey of adults who experienced loss during the September 11, 2001, terrorist attacks was conducted to examine the prevalence and correlates of complicated grief (CG) 2.5-3.5 years after the attacks. Forty-three percent of a study group of 704 bereaved adults across the United States screened positive for CG. In multivariate analyses, CG was associated with female gender, loss of a child, death of deceased at the World Trade Center, and live exposure to coverage of the attacks on television. Posttraumatic stress disorder, major depression, anxiety, suicidal ideation, and increase in post-9/11 smoking were common among participants with CG. A majority of the participants with CG reported receiving grief counseling and psychiatric medication after 9/11. Clinical and policy implications are discussed.

Ventilatory control of heart rate during inhalation of 5% CO2 and types of panic attacks.

PubMed

Ley, R

1991-09-01

Differences in the magnitude of increases in heart rate during prolonged inhalation of 5% CO2 range from a mean of 25 b/min for a group of eight panic-disorder patients who panicked (Woods, Charney, Goodman, & Heninger, 1988. Archives of General Psychiatry, 45, 43-52) to zero b/min for 16 patients, eight of whom panicked (Craske & Barlow, 1990. Journal of Abnormal Psychology, 99, 302-307). What accounts for this disparity? The present paper describes how heart rate can be increased by means of voluntary overbreathing during prolonged inhalation of 5% CO2 in air. This suggests that differences in the degree of overbreathing may explain differences in the magnitude of increases in heart rate during inhalation of 5% CO2. An explanation is also offered for the curious finding that some patients experience "panic attacks" with zero increase in heart rate. Evidence suggests that this is likely to happen in cognitively based panic attacks, in contrast to hyperventilatory attacks or anticipatory attacks.

Accurate diagnosis of acute abdomen in FMF and acute appendicitis patients: how can we use procalcitonin?

PubMed

Kisacik, Bunyamin; Kalyoncu, Umut; Erol, M Fatih; Karadag, Omer; Yildiz, Mustafa; Akdogan, Ali; Kaptanoglu, Bugra; Hayran, Mutlu; Ureten, Kemal; Ertenli, Ihsan; Kiraz, Sedat; Calguneri, Meral

2007-12-01

This study was conducted to define the value of procalcitonin (PCT) levels in the differential diagnosis of abdominal familial Mediterranean fever (FMF) attacks from acute appendicitis. From October 2006 to January 2007, 28 FMF (12 males, 16 females) patients with acute abdominal attacks and 34 patients (18 males) with acute abdomen who underwent operation with the clinical diagnosis of acute appendicitis were consecutively enrolled in this study. FMF patients with concurrent infectious diseases were excluded. PCT values were measured by an immunofluorescent method using the B.R.A.H.M.S. PCT kit (B.R.A.H.M.S. Diagnostica, Berlin, Germany). Erythrocyte sedimentation rate (ESR), C-reactive proteins (CRP) and leucocyte levels were also noted. Mean disease duration in FMF patients was 9.6 +/- 8.1 years (range 2-33 years) and all were on colchicine therapy with a mean colchicine dosage of 1.2 +/- 0.4 mg/day. Among the operated patients, 5 were excluded: 3 patients had normal findings and 2 had intestinal perforation (PCT levels were 2.69 and 4.93 ng/ml, respectively) at operative and pathologic evaluation. There were no significant differences between the two groups with respect to gender and age (p was not significant (NS) for all). Acute phase reactants and PCT levels were increased in patients with FMF compared to patients with acute appendicitis (0.529[0.12 +/- 0.96] vs 0.095 [0.01-0.80] p < 0.001, respectively). PCT levels higher than 0.5 ng/ml were found in 11% (3/28) of FMF patients compared to 62% (18/29) of acute appendicitis patients (p < 0.001). Our results suggest that PCT could be a useful test in the differentiation of abdominal FMF attacks from acute appendicitis, though it should not supplant more conventional investigations.

Tables of Asymptotic Directions and Vertical Cutoff Rigidities for a Five Degree by Fifteen Degree World Grid as Calculated Using the International Geomagnetic Reference Field for Epoch 1975.0

DTIC Science & Technology

1975-04-03

b-sos 01 I 𔃺 06 I 99.6991, S N - .b- NS.=O-O.sb- .rN4C..aCNSbM.cC-r 74 NCSCC NClb0.C lb ..-. %flJ I b9 O ncaaOtflbOOtCfCObbSCC. seSro 0 - acca ...ob.1 6.1.? 2 00 1 1 2ACRID~~i9 .1 10.2 750 L29:.0 56 D __r RIe•O -I IPO, 1 5 0¢ *j I b5 • f5 ,$ q,3 15, W O R L D G O O D 𔃻 . 2 0 9 2.0 2 1. 9 1 6

Federal and State Quarantine and Isolation Authority

DTIC Science & Technology

2006-08-16

agents that are naturally occurring or released during a terrorist attack, the isolation of infected persons, and the quarantine of certain cities or...http://www.cdc.gov/ncidod/dq/sars_facts/isolationquarantine.pdf]. 9 42 U.S.C. § 264(e) and 42 C.F.R. § 70.2. agent from infecting others.5 The... agents ,” which include “anthrax, ebola, plague, smallpox, tularemia, or other bacterial, fungal, rickettsial, or viral agent , biological toxin, or other

Electroregulated Metal-Binding with a Crown Ether Tetrathiafulvalene Derivative: Toward Electrochemically Addressed Metal Cation Sponges.

PubMed

Le Derf, Franck; Mazari, Miloud; Mercier, Nicolas; Levillain, Eric; Richomme, Pascal; Becher, Jan; Garín, Javier; Orduna, Jesus; Gorgues, Alain; Sallé, Marc

1999-12-27

A redox responsive ligand incorporating the tetrathiafulvalene unit has been synthesized. The crystal structure of the free ligand (Z)-1 (C(20)H(30)O(5)S(8), triclinic P&onemacr;, Z = 2, a = 9.087(6) Å, b = 11.637(7) Å, c = 14.370(8) Å, alpha = 65.54(3) degrees, beta = 82.32(5) degrees, gamma = 84.18(6) degrees, V = 1368 Å(3)) shows the redox-active tetrathiafulvalene core to be essentially planar, which allows observation of two reversible one-electron processes upon electrochemical oxidation. The efficiency of this system in the control of the reversible complexation/expulsion sequence of a metallic cation (i.e., Ba(2+)) has been made possible thanks to a combination of (a) an unprecedented high coordination ability among tetrathiafulvalene-based macrocycles as determined by LSI mass spectrometry (log K degrees = 3.5, NBA-matrix) as well as by solution investigations ((1)H NMR and cyclic voltammetry titration studies), which remarkably converge to similar binding constant values (i.e., log K degrees = 4.2-4.3), and (b) reversible metal cation expulsion upon electrochemical oxidation to the dicationic state. A channel-like solid-state structure is observed for the Ba(2+) complex (C(20)H(30)O(5)S(8), Ba(2+)(CF(3)SO(3))(2)(2-), (H(2)O)(2), CD(3)CN, monoclinic C2/c, Z = 8, a = 45.66(1) Å, b = 8.897(5) Å, c = 23.124(8) Å, beta = 105.54(4) degrees, V = 9050 Å(3)), which results from the segregated stacking mode of the crown ether and the redox-active tetrathiafulvalene subunits, respectively.

Synthesis, crystal structure and optical properties of a novel sodium lead pentaborate, NaPbB{sub 5}O{sub 9}

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

Zhang, Min; Graduate University of Chinese Academy of Sciences, Beijing 100049; Pan, Shilie, E-mail: slpan@ms.xjb.ac.c

A novel sodium lead pentaborate, NaPbB{sub 5}O{sub 9}, has been successfully synthesized by standard solid-state reaction. The single-crystal X-ray structural analysis showed that NaPbB{sub 5}O{sub 9} crystallizes in the monoclinic space group P2{sub 1}/c with a=6.5324(10) A, b=13.0234(2) A, c=8.5838(10) A, {beta}=104.971(10){sup o}, and Z=4. The crystal structure is composed of double ring [B{sub 5}O{sub 9}]{sup 3-} units, [PbO{sub 7}] and [NaO{sub 7}] polyhedra. [B{sub 5}O{sub 9}]{sup 3-} groups connect with each other forming two-dimensional infinite {sub {infinity}}[B{sub 5}O{sub 9}]{sup 3-} layers, while [PbO{sub 7}] and [NaO{sub 7}] polyhedra are located between the layers. [PbO{sub 7}] polyhedra linked together viamore » corner-sharing O atom forming novel infinite {sub {infinity}}[PbO{sub 6}] chains along the c axis. The thermal behavior, IR spectrum and the optical diffuse reflectance spectrum of NaPbB{sub 5}O{sub 9} were reported. -- Graphical abstract: A new phase, NaPbB{sub 5}O{sub 9}, has been discovered in the ternary M{sub 2}O-PbO-B{sub 2}O{sub 3} (M=alkali-metal) system. The crystal structure consists of a novel infinite {sub {infinity}}[PbO{sub 6}] chains. Display Omitted Research highlights: NaPbB{sub 5}O{sub 9} is the first borate discovered in the ternary M{sub 2}O-PbO-B{sub 2}O{sub 3} (M=alkali-metal) system. NaPbB{sub 5}O{sub 9} crystal structure includes a two-dimensional infinite {sub {infinity}}[B{sub 5}O{sub 9}]{sup 3-} layers and a novel one-dimensional infinite {sub {infinity}}[PbO{sub 6}] chains. [PbO{sub 7}] polyhedron has a highly asymmetric bonding configuration.« less

Dynamic Force Measurements and Boundary-Layer Transition Mapping on a Spinning 9-Deg Cone with and without Mass Addition at Mach Numbers 5 and 8

DTIC Science & Technology

1978-08-01

91 40. Aerodynamic Coefficients for Sharp Cone at Angle of Attack 93 41. Posttest Photograph of Ablated Camphor Nose Tip, rn/rb = 0.042...94 AEDC-TR-78-40 Figure Page 42. Aerodynamic Coefficients on Spinning Model with Camphor Nose Tip with Imbedded Metal Shaving 95 43. 3...shell could be replaced with camphor (in the case of the larger spin model only, Fig. 5a), asymmetric aluminum (Fig. 5b), or carbon phenolic frustums

The Control of Human Arm Movement: Models and Mechanical Constraints

DTIC Science & Technology

1990-06-01

joints o linear joint angle sensors These assumptions may be refined as needed (e.g., muscle geometry may be included), but such additional complexity... C +y (2.4) 26 where W_ = (a, a2 Y = (1 0 1 O )T, = , 9 and cos( o ’) cos(o4) cos(q1) sin( o ) sin(44) sin(01) C 1= (2.5) coS(qS) coS(02) coS(0b) The least...squares solution is o = (CTC)-1CT(-y). A unique solution is guaranteed provided that the columns of C are independent. Observe that the columns of C

Results of investigations on a 0.010-scale 140A/B configuration space shuttle vehicle orbiter model 72-0 in the NASA/Langley Research Center continuous flow hypersonic tunnel (OA90)

NASA Technical Reports Server (NTRS)

Hawthorne, P. J.

1975-01-01

Data are documented which were obtained during wind tunnel tests. The test was conducted beginning 4 March and ending 6 March 1974 for a total of 24 occupancy hours. all test runs were conducted at a Mach number of 10.3 and at Reynolds numbers of 0.65, 1.0 and 1.33 million per foot. Only the complete 140A/B was tested with various elevon, speedbrake, and bodyflap settings at angles of attack from 12 to 37 degrees at 0 and -5 degrees of beta, and from 0 to -9 degrees of beta at 20 and 30 degrees angle of attack. The purpose was to obtain hypersonic longitudinal and lateral-directional stability and control characteristics of the updated space shuttle vehicle configuration.

Crystallization and preliminary crystallographic analysis of calcium-binding protein-2 from Entamoeba histolytica and its complexes with strontium and the IQ1 motif of myosin V

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

Gourinath, S., E-mail: sgourinath@mail.jnu.ac.in; Padhan, Narendra; Alam, Neelima

2005-04-01

Calcium-binding protein-2 (EhCaBP2) crystals were grown using MPD as a precipitant. EhCaBP2 also crystallized in complex with strontium (replacing calcium) at similar conditions. Preliminary data for EhCaBP2 crystals in complex with an IQ motif are also reported. Calcium plays a pivotal role in the pathogenesis of amoebiasis, a major disease caused by Entamoeba histolytica. Two domains with four canonical EF-hand-containing calcium-binding proteins (CaBPs) have been identified from E. histolytica. Even though they have very high sequence similarity, these bind to different target proteins in a Ca{sup 2+}-dependent manner, leading to different functional pathways. Calcium-binding protein-2 (EhCaBP2) crystals were grown usingmore » MPD as a precipitant. The crystals belong to space group P2{sub 1}, with unit-cell parameters a = 111.74, b = 68.83, c = 113.25 Å, β = 116.7°. EhCaBP2 also crystallized in complex with strontium (replacing calcium) at similar conditions. The crystals belong to space group P2{sub 1}, with unit-cell parameters a = 69.18, b = 112.03, c = 93.42 Å, β = 92.8°. Preliminary data for EhCaBP2 crystals in complex with an IQ motif are also reported. This complex was crystallized with MPD and ethanol as precipitating agents. These crystals belong to space group P2{sub 1}, with unit-cell parameters a = 60.5, b = 69.86, c = 86.5 Å, β = 97.9°.« less

Zirconocene mediated acetylboron chemistry.

PubMed

Jian, Zhongbao; Daniliuc, Constantin G; Kehr, Gerald; Erker, Gerhard

2018-05-31

The methyl zirconocene complex Cp*2Zr(Me)OMes reacts with H3C-B(C6F5)2 and CO to give the respective acetyl(methyl)borate Zr complex. Cp*2Zr(H)OMes reacts with H3C-B(C6F5)2 and CO to give the respective acetyl(hydrido)borate Zr product, admixed with a minor amount of the formyl(methyl)borate Zr complex isomer. Prolonged exposure to CO under close to ambient conditions results in the uptake of another CO equivalent to yield the corresponding borata-β-lactone zirconocene product.

Investigation of diffusional interaction between P91 grade ferritic steel and Fe-15 wt.%B alloy and study of kinetics of boride formation at high temperature

NASA Astrophysics Data System (ADS)

Rai, Arun Kumar; Vijayashanthi, N.; Tripathy, H.; Hajra, R. N.; Raju, S.; Murugesan, S.; Saroja, S.

2017-11-01

In the present study, the feasibility of employing the indigenously developed ferroboron alloy (Fe-15 wt.%B) as an alternate neutron shield material in combination with 9Cr-based ferritic steel (P91) clad in future Indian fast breeder reactors (FBR), has been investigated from a metallurgical perspective. Towards this goal, a series of diffusion couple experiments have been conducted at three different temperatures namely, 600, 700 and 800 °C for time durations up to 5000 h. The thickness of interaction layer has been monitored using standard metallographic procedures. The experiments revealed that ferroboron/P91 combination exhibited a tendency to form complex intermetallic borides at the interface. The structural and microstructural characterization of the interface confirmed that the reaction layer consists predominantly of borides of Fe and Cr of type FeB, Fe2B, (Fe,Cr)2B and (Fe,Cr)B. The measured variation of interaction layer thickness as a function of time and temperature have been modelled in terms of diffusion mediated interaction. The growth kinetics of borided layer has followed the parabolic law at each temperature, and the apparent activation energy for boride layer formation is found to be of the order of 115 kJ mol-1. This indicates that the kinetics of boriding could be governed by diffusion of B into the P91 matrix. Based on the findings of present study, an extrapolative estimate of the clad attack thickness at 550 °C for 60 years of operating time has been made and it turns out to be 210 ± 15 μm, which is less than the clad thickness of FBR shielding subassembly (4 mm) [1]. Thus, this study confirms that at testing temperatures from 550 to 600 °C, the ferroboron/P91 steel combination can be safely employed for shielding subassembly applications in fast reactors.

A Zonal Approach for the Solution of Coupled Euler and Potential Solutions of Flows with Complex Geometries.

DTIC Science & Technology

1987-06-01

obtained from: A simple numerical intergration scheme is employed to perform the integral in Equations (B2) and (86) along the dividing streamline. A 11 4...angle of attack was small, the dividing streamline remained almost horizontal in this case. Results of a higher angle of attack case, in which the mesh

Multimeric complexes among ankyrin-repeat and SOCS-box protein 9 (ASB9), ElonginBC, and Cullin 5: insights into the structure and assembly of ECS-type Cullin-RING E3 ubiquitin ligases.

PubMed

Thomas, Jemima C; Matak-Vinkovic, Dijana; Van Molle, Inge; Ciulli, Alessio

2013-08-06

Proteins of the ankyrin-repeat and SOCS-box (ASB) family act as the substrate-recognition subunits of ECS-type (ElonginBC-Cullin-SOCS-box) Cullin RING E3 ubiquitin ligase (CRL) complexes that catalyze the specific polyubiquitination of cellular proteins to target them for degradation by the proteasome. Therefore, ASB multimeric complexes are involved in numerous cell processes and pathways; however, their interactions, assembly, and biological roles remain poorly understood. To enhance our understanding of ASB CRL systems, we investigated the structure, affinity, and assembly of the quaternary multisubunit complex formed by ASB9, Elongin B, Elongin C (EloBC), and Cullin 5. Here, we describe the application of several biophysical techniques including differential scanning fluorimetry, isothermal titration calorimetry (ITC), nanoelectrospray ionization, and ion-mobility mass spectrometry (IM-MS) to provide structural and thermodynamic information for a quaternary ASB CRL complex. We find that ASB9 is unstable alone but forms a stable ternary complex with EloBC that binds with high affinity to the Cullin 5 N-terminal domain (Cul5NTD) but not to Cul2NTD. The structure of the monomeric ASB9-EloBC-Cul5NTD quaternary complex is revealed by molecular modeling and is consistent with IM-MS and temperature-dependent ITC data. This is the first experimental study to validate structural information for the assembly of the quaternary N-terminal region of an ASB CRL complex. The results suggest that ASB E3 ligase complexes function and assemble in an analogous manner to that of other CRL systems and provide a platform for further molecular investigation of this important protein family. The data reported here will also be of use for the future development of chemical probes to examine the biological function and modulation of other ECS-type CRL systems.

Multimeric Complexes among Ankyrin-Repeat and SOCS-box Protein 9 (ASB9), ElonginBC, and Cullin 5: Insights into the Structure and Assembly of ECS-type Cullin-RING E3 Ubiquitin Ligases

PubMed Central

2013-01-01

Proteins of the ankyrin-repeat and SOCS-box (ASB) family act as the substrate-recognition subunits of ECS-type (ElonginBC–Cullin–SOCS-box) Cullin RING E3 ubiquitin ligase (CRL) complexes that catalyze the specific polyubiquitination of cellular proteins to target them for degradation by the proteasome. Therefore, ASB multimeric complexes are involved in numerous cell processes and pathways; however, their interactions, assembly, and biological roles remain poorly understood. To enhance our understanding of ASB CRL systems, we investigated the structure, affinity, and assembly of the quaternary multisubunit complex formed by ASB9, Elongin B, Elongin C (EloBC), and Cullin 5. Here, we describe the application of several biophysical techniques including differential scanning fluorimetry, isothermal titration calorimetry (ITC), nanoelectrospray ionization, and ion-mobility mass spectrometry (IM–MS) to provide structural and thermodynamic information for a quaternary ASB CRL complex. We find that ASB9 is unstable alone but forms a stable ternary complex with EloBC that binds with high affinity to the Cullin 5 N-terminal domain (Cul5NTD) but not to Cul2NTD. The structure of the monomeric ASB9–EloBC–Cul5NTD quaternary complex is revealed by molecular modeling and is consistent with IM–MS and temperature-dependent ITC data. This is the first experimental study to validate structural information for the assembly of the quaternary N-terminal region of an ASB CRL complex. The results suggest that ASB E3 ligase complexes function and assemble in an analogous manner to that of other CRL systems and provide a platform for further molecular investigation of this important protein family. The data reported here will also be of use for the future development of chemical probes to examine the biological function and modulation of other ECS-type CRL systems. PMID:23837592

Functionalization of metallabenzenes through nucleophilic aromatic substitution of hydrogen.

PubMed

Clark, George R; Ferguson, Lauren A; McIntosh, Amy E; Söhnel, Tilo; Wright, L James

2010-09-29

The cationic metallabenzenes [Ir(C(5)H(4){SMe-1})(κ(2)-S(2)CNEt(2))(PPh(3))(2)]PF(6) (1) and [Os(C(5)H(4){SMe-1})(CO)(2)(PPh(3))(2)][CF(3)SO(3)] (2) undergo regioselective nucleophilic aromatic substitution of hydrogen at the metallabenzene ring position γ to the metal in a two-step process that first involves treatment with appropriate nucleophiles and then oxidation. Thus, reaction between compound 1 and NaBH(4), MeLi, or NaOEt gives the corresponding neutral iridacyclohexa-1,4-diene complexes Ir(C(5)H(3){SMe-1}{H-3}{Nu-3})(κ(2)-S(2)CNEt(2))(PPh(3))(2) (Nu = H (3), Me (4), OEt (5)). Similarly, reaction between 2 and NaBH(4) or MeLi gives the corresponding osmacyclohexa-1,4-diene complexes Os(C(5)H(3){SMe-1}{H-3}{Nu-3})(CO)(2)(PPh(3))(2) (Nu = H (8), Me (9)). The metallacyclohexa-1,4-diene rings in all these compounds are rearomatized on treatment with the oxidizing agent O(2), CuCl(2), or 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ). Accordingly, the cationic metallabenzene 1 or 2 is returned after reaction between 3 and DDQ/NEt(4)PF(6) or between 8 and DDQ/NaO(3)SCF(3), respectively. The substituted cationic iridabenzene [Ir(C(5)H(3){SMe-1}{Me-3})(κ(2)-S(2)CNEt(2))(PPh(3))(2)]PF(6) (6) or [Ir(C(5)H(4){SMe-1}{OEt-3})(κ(2)-S(2)CNEt(2))(PPh(3))(2)]PF(6) (7) is produced in a similar manner through reaction between 4 or 5, respectively, and DDQ/NEt(4)PF(6), and the substituted cationic osmabenzene [Os(C(5)H(3){SMe-1}{Me-3})(CO)(2)(PPh(3))(2)]Cl (10) is formed in good yield on treatment of 9 with CuCl(2). The starting cationic iridabenzene 1 is conveniently prepared by treatment of the neutral iridabenzene Ir(C(5)H(4){SMe-1})Cl(2)(PPh(3))(2) with NaS(2)CNEt(2) and NEt(4)PF(6), and the related starting cationic osmabenzene 2 is obtained by treatment of Os(C(5)H(4){S-1})(CO)(PPh(3))(2) with CF(3)SO(3)CH(3) and CO. The stepwise transformations of 1 into 6 or 7 as well as 2 into 10 provide the first examples in metallabenzene chemistry of regioselective nucleophilic aromatic substitutions of hydrogen by external nucleophiles. DFT calculations have been used to rationalize the preferred sites for nucleophilic attack at the metallabenzene rings of 1 and 2. The crystal structures of 1, 3, 6, and 7 have been obtained.

Measured noise of a scale model high speed propeller at simulated takeoff/approach conditions

NASA Technical Reports Server (NTRS)

Woodward, Richard P.

1987-01-01

A model high-speed advanced propeller, SR-7A, was tested in the NASA Lewis 9x15 foot anechoic wind tunnel at simulated takeoff/approach conditions of 0.2 Mach number. These tests were in support of the full-scale Propfan Text Assessment (PTA) flight program. Acoustic measurements were taken with fixed microphone arrays and with an axially translating microphone probe. Limited aerodynamic measurements were also taken to establish the propeller operating conditions. Tests were conducted with the propeller alone and with three down-stream wing configurations. The propeller was run over a range of blade setting angles from 32.0 deg. to 43.6 deg., tip speeds from 183 to 290 m/sec (600 to 950 ft/sec), and angles of attack from -10 deg. to +15 deg. The propeller alone BPF tone noise was found to increase 10 dB in the flyover plane at 15 deg. propeller axis angle of attack. The installation of the straight wing at minimum spacing of 0.54 wing chord increased the tone noise 5 dB under the wing of 10 deg. propeller axis angle of attack, while a similarly spaced inboard upswept wing only increased the tone noise 2 dB.

75 FR 71781 - Self-Regulatory Organizations; EDGX Exchange, Inc.; Notice of Filing of Proposed Rule Change To...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-24

... 11.9(b)(1)(C) and 11.5(c)(7) Regarding Step-Up Orders November 18, 2010 Pursuant to Section 19(b)(1... Change The Exchange proposes to amend EDGX Rule 11.9(b)(1)(C) regarding the description of the Step-up... in response to Step-up orders to be processed pursuant to Rule 11.9(b)(1)(C). The text of the...

75 FR 71783 - Self-Regulatory Organizations; EDGA Exchange, Inc.; Notice of Filing of Proposed Rule Change To...

Federal Register 2010, 2011, 2012, 2013, 2014

2010-11-24

... 11.9(b)(1)(C) and 11.5(c)(7) Regarding Step-Up Orders November 18, 2010. Pursuant to Section 19(b)(1... Change The Exchange proposes to amend EDGA Rule 11.9(b)(1)(C) regarding the description of the Step-up... entered in response to Step-up orders to be processed pursuant to Rule 11.9(b)(1)(C).). The text of the...

The effects of an enrichment training program for youth football attackers

PubMed Central

Santos, Sara; Gonçalves, Bruno; Travassos, Bruno; Wong, Del P.; Schöllhorn, Wolfgang; Sampaio, Jaime

2018-01-01

The aim of this study was to identify the effects of a complementary training program based on differential learning approach in the physical, technical, creative and positioning performance of youth football attackers. Fifteen players were allocated into the control (U15C = 9, age: 13.9±0.5 years; U17C = 6, age: 16.1±0.7 years) and the experimental (U15E = 9, age: 14.2±0.8 years; U17E = 6, age: 15.8±0.5 years) groups. The experimental groups participated in 10-weeks of a complementary training program based on differential learning approach to improve physical literacy and players’ tactical behavior. Variables studied encompassed: motor (vertical jump, speed and repeated change-of direction), technical (pass, dribble and shot), creative (fluency, attempts, versatility) and positioning-related variables (stretch index, spatial exploration index and regularity of the lateral and longitudinal movements). Results revealed that U15E improved both the jump and repeated change-of-direction performance, while the U17E have only improved the jump performance. The U15E showed improvements in all technical variables (small to large effects), and in the fluency and versatility (moderate effects), while the U17 have only improved the successful shots (large effects). From a positional perspective, there was a moderate increase in the stretch index, and decreased longitudinal and lateral regularity (small to moderate effects) in the U15E compared to the U15C. In turn, the U17E revealed a moderate increase of the spatial exploration index and a small decrease in the stretch index. Overall, the results suggest that the complementary training program was effective for the development of the overall performance of the U15E attackers, while more time and/or variability may be needed for older age groups. Nevertheless, the overall higher values found in experimental groups, may suggest that this type of complementary training program improves performance. PMID:29897985

Supercondutivity at 9K in Mo 5PB 2 with evidence for multiple gaps

DOE PAGES

McGuire, Michael A.; Parker, David S.

2016-02-09

Superconductivity is observed with critical temperatures near 9 K in the tetragonal compound Mo 5PB 2. This material adopts the Cr 5B 3 structure type common to superconducting Nb 5Si 3–xBx, Mo 5SiB 2, and W 5SiB 2, which have critical temperatures of 5.8–7.8 K. We have synthesized polycrystalline samples of the compound, made measurements of electrical resistivity, magnetic susceptibility, and heat capacity, and performed first-principles electronic structure calculations. The highest T c value (9.2 K) occurs in slightly phosphorus rich samples, with composition near Mo 5P 1.1B 1.9, and the upper critical field H c2 at T = 0more » is estimated to be ≈17 kOe. Together, the measurements and band-structure calculations indicate intermediate coupling (λ=1.0), phonon mediated superconductivity. Here, the temperature dependence of the heat capacity and upper critical field H c2 below T c suggest multiple superconducting gaps may be present.« less

Wide diversity of PAX5 alterations in B-ALL: a Groupe Francophone de Cytogenetique Hematologique study.

PubMed

Coyaud, Etienne; Struski, Stephanie; Prade, Nais; Familiades, Julien; Eichner, Ruth; Quelen, Cathy; Bousquet, Marina; Mugneret, Francine; Talmant, Pascaline; Pages, Marie-Pierre; Lefebvre, Christine; Penther, Dominique; Lippert, Eric; Nadal, Nathalie; Taviaux, Sylvie; Poppe, Bruce; Luquet, Isabelle; Baranger, Laurence; Eclache, Virginie; Radford, Isabelle; Barin, Carole; Mozziconacci, Marie-Joëlle; Lafage-Pochitaloff, Marina; Antoine-Poirel, Hélène; Charrin, Christiane; Perot, Christine; Terre, Christine; Brousset, Pierre; Dastugue, Nicole; Broccardo, Cyril

2010-04-15

PAX5 is the main target of somatic mutations in acute B lymphoblastic leukemia (B-ALL). We analyzed 153 adult and child B-ALL harboring karyotypic abnormalities at chromosome 9p, to determine the frequency and the nature of PAX5 alterations. We found PAX5 internal rearrangements in 21% of the cases. To isolate fusion partners, we used classic and innovative techniques (rolling circle amplification-rapid amplification of cDNA ends) and single nucleotide polymorphism-comparative genomic hybridization arrays. Recurrent and novel fusion partners were identified, including NCoR1, DACH2, GOLGA6, and TAOK1 genes showing the high variability of the partners. We noted that half the fusion genes can give rise to truncated PAX5 proteins. Furthermore, malignant cells carrying PAX5 fusion genes displayed a simple karyotype. These data strongly suggest that PAX5 fusion genes are early players in leukemogenesis. In addition, PAX5 deletion was observed in 60% of B-ALL with 9p alterations. Contrary to cases with PAX5 fusions, deletions were associated with complex karyotypes and common recurrent translocations. This supports the hypothesis of the secondary nature of the deletion. Our data shed more light on the high variability of PAX5 alterations in B-ALL. Therefore, it is probable that gene fusions occur early, whereas deletions should be regarded as a late/secondary event.

Separated and Nonseparated Turbulent Flows about Axisymmetric Nozzle Afterbodies. Part II. Detailed Flow Measurements

DTIC Science & Technology

1979-10-01

total pressures and the model static pressures were converted to a d-c electrical signal by one of two Scanivalve ®, Druck Model PDCR22, 0- to l0...31 3d 33 3+ 3’:, 3~ 3~ ~d ~ 4 4 b 4 h ,.,.9 50 0 , 0 0 + 0 . 0 9 9 n . 0 1 4 0.019 0 , 0 ~ 4 0 . 0 2 9 C . 0 3 ~ ~ . 0 3...1 ° 5 8 5 £ 02 0 .322 - 1 ° 2 5 b £ O~ 0,3~2 - 9 . f i ~ 3 £ t)l 0 ,36~ - 7 , b P ~ £ 01 0 . 3d ~ - 5 , ~ 3 9 £ Ol 0 , ~ 0 ~ - ~ ° 5 1

Phytotoxicity, structural and computational analysis of 2-methyl-1,5-diarylpentadienones

NASA Astrophysics Data System (ADS)

Din, Zia Ud; Rodrigues-Filho, Edson; de Cassia Pereira, Viviane; Gualtieri, Sonia Cristina Juliano; Deflon, Victor Marcelo; da Silva Maia, Pedro Ivo; Kuznetsov, Aleksey E.

2017-08-01

In our studies aimed to produce new chemicals used in weed control, 2-methyl-1,5-diarylpentadienones were synthesized by the reaction of p-methoxybenzaldehyde, p-nitrobenzaldehyde and p-N,N-dimethylbenzaldehyde, respectively, with 2-butanone, resulting in four model compounds. The phytotoxicity of these compounds against wheat coleoptiles and Sesame seedling was observed at μM concentrations, indicating good potential for their usage in weed management in the field. Spectroscopic and computational studies were performed in order to gain understanding on their mechanisms of action and to clarify some structural complexities due existence of conformers and substituent effects. These compounds probably act as hydroxyphenylpyruvate dioxygenase inhibitors. The tested compounds were characterized by spectroscopic and single crystal X-ray diffraction analyses. Solid crystalline state of the compound A (2-Methyl-1-(p-methophyphenyl)-5-(phenyl)-diarylpentadienone) is observed in the monoclinic space group P21/c with unit cell dimensions a = 14.3366(4) Å, b = 11.3788(4) Å, c = 9.6319(3) Å, β = 96.596, V = 1560.88(9) Å3 and Z = 4. Compound C (2-Methyl-1-(p-methophyphenyl)-5-(p-nitrophenyl)-diarylpentadienone) crystallizes in the monoclinic space group P21/c with unit cell dimensions a = 17.8276(9) Å, b = 7.3627(4) Å, c = 12.9740(6) Å, β = 107.6230(10), V = 1623.04(14) Å3 and Z = 4. LC-UV-MS analysis furnished important data helpful for their characterization. The spectroscopic data and computational (DFT) analysis revealed the fact that each of the compounds A-D occurs in solution as four conformers.

Pyrrole multimers and pyrrole-acetylene hydrogen bonded complexes studied in N2 and para-H2 matrixes using matrix isolation infrared spectroscopy and ab initio computations

NASA Astrophysics Data System (ADS)

Sarkar, Shubhra; Ramanathan, N.; Gopi, R.; Sundararajan, K.

2017-12-01

Hydrogen bonded interaction of pyrrole multimer and acetylene-pyrrole complexes were studied in N2 and p-H2 matrixes. DFT computations showed T-shaped geometry for the pyrrole dimer and cyclic complex for the trimer and tetramer were the most stable structures, stabilized by Nsbnd H⋯π interactions. The experimental vibrational wavenumbers observed in N2 and p-H2 matrixes for the pyrrole multimers were correlated with the computed wavenumbers. Computations performed at MP2/aug-cc-pVDZ level of theory showed that C2H2 and C4H5N forms 1:1 hydrogen-bonded complexes stabilized by Csbnd H⋯π interaction (Complex A), Nsbnd H⋯π interaction (Complex B) and π⋯π interaction (Complex C), where the former complex is the global minimum and latter two complexes were the first and second local minima, respectively. Experimentally, 1:1 C2H2sbnd C4H5N complexes A (global minimum) and B (first local minimum) were identified from the shifts in the Nsbnd H stretching, Nsbnd H bending, Csbnd H bending region of pyrrole and Csbnd H asymmetric stretching and bending region of C2H2 in N2 and p-H2 matrixes. Computations were also performed for the higher complexes and found two minima corresponding to the 1:2 C2H2sbnd C4H5N and three minima for the 2:1 C2H2sbnd C4H5N complexes. Experimentally the global minimum 1:2 and 2:1 C2H2sbnd C4H5N complexes were identified in N2 and p-H2 matrixes.

Markers of immune-mediated inflammation in the brains of young adults and adolescents with type 1 diabetes and fatal diabetic ketoacidosis. Is there a difference?

PubMed

Hoffman, William H; Artlett, Carol M; Boodhoo, Dallas; Gilliland, Mary G F; Ortiz, Luis; Mulder, Dries; Tjan, David H T; Martin, Alvaro; Tatomir, Alexandru; Rus, Horea

2017-06-01

Due to the limited data on diabetic ketoacidosis and brain edema (DKA/BE) in children/adolescents and the lack of recent data on adults with type 1 diabetes (T1D), we addressed the question of whether neuroinflammation was present in the fatal DKA of adults. We performed immunohistochemistry (IHC) studies on the brains of two young adults with T1D and fatal DKA and compared them with two teenagers with poorly controlled diabetes and fatal DKA. C5b-9, the membrane attack complex (MAC) had significantly greater deposits in the grey and white matter of the teenagers than the young adults (p=0.03). CD59, a MAC assembly inhibitory protein was absent, possibly suppressed by the hyperglycemia in the teenagers but was expressed in the young adults despite comparable average levels of hyperglycemia. The receptor for advanced glycation end products (RAGE) had an average expression in the young adults significantly greater than in the teenagers (p=0.02). The autophagy marker Light Chain 3 (LC3) A/B was the predominant form of programmed cell death (PCD) in the teenage brains. The young adults had high expressions of both LC3A/B and TUNEL, an apoptotic cell marker for DNA fragmentation. BE was present in the newly diagnosed young adult with hyperglycemic hyperosmolar DKA and also in the two teenagers. Our data indicate that significant differences in neuroinflammatory components, initiated by the dysregulation of DKA and interrelated metabolic and immunologic milieu, are likely present in the brains of fatal DKA of teenagers when compared with young adults. Copyright © 2017 Elsevier Inc. All rights reserved.

The Crystal Structure of Cobra Venom Factor, a Cofactor for C3- and C5-Convertase CVFBb

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

Krishnan, Vengadesan; Ponnuraj, Karthe; Xu, Yuanyuan

2009-05-26

Cobra venom factor (CVF) is a functional analog of human complement component C3b, the active fragment of C3. Similar to C3b, in human and mammalian serum, CVF binds factor B, which is then cleaved by factor D, giving rise to the CVFBb complex that targets the same scissile bond in C3 as the authentic complement convertases C4bC2a and C3bBb. Unlike the latter, CVFBb is a stable complex and an efficient C5 convertase. We solved the crystal structure of CVF, isolated from Naja naja kouthia venom, at 2.6 {angstrom} resolution. The CVF crystal structure, an intermediate between C3b and C3c, lacksmore » the TED domain and has the CUB domain in an identical position to that seen in C3b. The similarly positioned CUB and slightly displaced C345c domains of CVF could play a vital role in the formation of C3 convertases by providing important primary binding sites for factor B.« less

The crystal structure of cobra venom factor, a cofactor for C3- and C5-convertase CVFBb.

PubMed

Krishnan, Vengadesan; Ponnuraj, Karthe; Xu, Yuanyuan; Macon, Kevin; Volanakis, John E; Narayana, Sthanam V L

2009-04-15

Cobra venom factor (CVF) is a functional analog of human complement component C3b, the active fragment of C3. Similar to C3b, in human and mammalian serum, CVF binds factor B, which is then cleaved by factor D, giving rise to the CVFBb complex that targets the same scissile bond in C3 as the authentic complement convertases C4bC2a and C3bBb. Unlike the latter, CVFBb is a stable complex and an efficient C5 convertase. We solved the crystal structure of CVF, isolated from Naja naja kouthia venom, at 2.6 A resolution. The CVF crystal structure, an intermediate between C3b and C3c, lacks the TED domain and has the CUB domain in an identical position to that seen in C3b. The similarly positioned CUB and slightly displaced C345c domains of CVF could play a vital role in the formation of C3 convertases by providing important primary binding sites for factor B.

Association Between CYP2C19 Loss-of-Function Allele Status and Efficacy of Clopidogrel for Risk Reduction Among Patients With Minor Stroke or Transient Ischemic Attack.

PubMed

Wang, Yilong; Zhao, Xingquan; Lin, Jinxi; Li, Hao; Johnston, S Claiborne; Lin, Yi; Pan, Yuesong; Liu, Liping; Wang, David; Wang, Chunxue; Meng, Xia; Xu, Jianfeng; Wang, Yongjun

2016-07-05

Data are limited regarding the association between CYP2C19 genetic variants and clinical outcomes of patients with minor stroke or transient ischemic attack treated with clopidogrel. To estimate the association between CYP2C19 genetic variants and clinical outcomes of clopidogrel-treated patients with minor stroke or transient ischemic attack. Three CYP2C19 major alleles (*2, *3, *17) were genotyped among 2933 Chinese patients from 73 sites who were enrolled in the Clopidogrel in High-Risk Patients with Acute Nondisabling Cerebrovascular Events (CHANCE) randomized trial conducted from January 2, 2010, to March 20, 2012. Patients with acute minor ischemic stroke or transient ischemic attack in the trial were randomized to treatment with clopidogrel combined with aspirin or to aspirin alone. The primary efficacy outcome was new stroke. The secondary efficacy outcome was a composite of new composite vascular events (ischemic stroke, hemorrhagic stroke, myocardial infarction, or vascular death). Bleeding was the safety outcome. Among 2933 patients, 1948 (66.4%) were men, with a mean age of 62.4 years. Overall, 1207 patients (41.2%) were noncarriers and 1726 patients (58.8%) were carriers of loss-of-function alleles (*2, *3). After day 90 follow-up, clopidogrel-aspirin reduced the rate of new stroke in the noncarriers but not in the carriers of the loss-of-function alleles (P = .02 for interaction; events among noncarriers, 41 [6.7%] with clopidogrel-aspirin vs 74 [12.4%] with aspirin; hazard ratio [HR], 0.51 [95% CI, 0.35-0.75]; events among carriers, 80 [9.4%] with clopidogrel-aspirin vs 94 [10.8%] with aspirin; HR, 0.93 [95% CI, 0.69 to 1.26]). Similar results were observed for the secondary composite efficacy outcome (noncarriers: 41 [6.7%] with clopidogrel-aspirin vs 75 [12.5%] with aspirin; HR, 0.50 [95% CI, 0.34-0.74]; carriers: 80 [9.4%] with clopidogrel-aspirin vs 95 [10.9%] with aspirin; HR, 0.92 [95% CI, 0.68-1.24]; P = .02 for interaction). The effect of treatment assignment on bleeding did not vary significantly between the carriers and the noncarriers of the loss-of-function alleles (2.3% for carriers and 2.5% for noncarriers in the clopidogrel-aspirin group vs 1.4% for carriers and 1.7% for noncarriers in the aspirin only group; P = .78 for interaction). Among patients with minor ischemic stroke or transient ischemic attack, the use of clopidogrel plus aspirin compared with aspirin alone reduced the risk of a new stroke only in the subgroup of patients who were not carriers of the CYP2C19 loss-of-function alleles. These findings support a role of CYP2C19 genotype in the efficacy of this treatment. clinicaltrials.gov Identifier: NCT00979589.

Analysis of Special Operations Forces in Decision Aids: Recommendations,

DTIC Science & Technology

1994-01-01

Soviet-made armored scout cars operated by Malaysian troops. By that time, the United States had lost 102 men-18 killed and 84 wounded. Somali leaders...designation of targets; attack by F-15E and F-16C using CBU-87, -89 Execution and GBU; attack by A-10 using Maverick and 30-mm cannon; attack by B-52 using...patrolling designated areas of the battlefield and attacking individual armored vehicles with precision-guided weapons such as Maverick . Discontinuity

Breakthrough attacks in patients with hereditary angioedema receiving long-term prophylaxis are responsive to icatibant: findings from the Icatibant Outcome Survey.

PubMed

Aberer, Werner; Maurer, Marcus; Bouillet, Laurence; Zanichelli, Andrea; Caballero, Teresa; Longhurst, Hilary J; Perrin, Amandine; Andresen, Irmgard

2017-01-01

Patients with hereditary angioedema (HAE) due to C1-inhibitor deficiency (C1-INH-HAE) experience recurrent attacks of cutaneous or submucosal edema that may be frequent and severe; prophylactic treatments can be prescribed to prevent attacks. However, despite the use of long-term prophylaxis (LTP), breakthrough attacks are known to occur. We used data from the Icatibant Outcome Survey (IOS) to evaluate the characteristics of breakthrough attacks and the effectiveness of icatibant as a treatment option. Data on LTP use, attacks, and treatments were recorded. Attack characteristics, treatment characteristics, and outcomes (time to treatment, time to resolution, and duration of attack) were compared for attacks that occurred with versus without LTP. Data on 3228 icatibant-treated attacks from 448 patients with C1-INH-HAE were analyzed; 30.1% of attacks occurred while patients were using LTP. Attack rate, attack severity, and the distribution of attack sites were similar across all types of LTP used, and were comparable to the results found in patients who did not receive LTP. Attacks were successfully treated with icatibant; 82.5% of all breakthrough attacks were treated with a single icatibant injection without C1-INH rescue medication. Treatment outcomes were comparable for breakthrough attacks across all LTP types, and for attacks without LTP. Patients who use LTP should be aware that breakthrough attacks can occur, and such attacks can be severe. Thus, patients with C1-INH-HAE using LTP should have emergency treatment readily available. Data from IOS show that icatibant is effective for the treatment of breakthrough attacks. Trial Registration NCT01034969.

Low-speed cascade investigation of loaded leading-edge compressor blades

NASA Technical Reports Server (NTRS)

Emery, James C

1956-01-01

Six percent thick NACA 63-series compressor-blade sections having a loaded leading-edge A4K6 mean line have been investigated systematically in a two-dimensional porous-wall cascade over a range of Reynolds numbers from 160,000 to 385,000. Blades cambered to have isolated-airfoil lift coefficients of 0.6, 1.2, 1.8, and 2.4 were tested over the usable angle-of-attack range at inlet-air angles of 30 degrees, 45 degrees, and 60 degrees and solidities of 1.0 and 1.5. A comparison with data of NACA RM L51G31, shows that the angle-of-attack operating range is 2 degrees to 4 degrees less than the range for the uniformly loaded section; however, the wake losses near design angle of attack are slightly lower than those for the uniformly loaded section. Except for highly cambered blades at high inlet angles, the 63-(C s oA4K6)06 compressor-blade sections are capable of more efficient operation for moderate-speed subsonic compressors at design angle of attack than are the 65-(C s oa10)10 or the 65-(c s oA2I8b)10 compressor-blade sections. In contrast to the other sections, the loaded leading-edge sections are capable of operating efficiently at the lower Reynolds numbers.

Crystal chemistry of thorium nitrates and chromates

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

Sigmon, Ginger E.; Burns, Peter C., E-mail: pburns@nd.ed

2010-07-15

The structures and infrared spectra of six novel thorium compounds are reported. Th(NO{sub 3}){sub 2}(OH){sub 2}(H{sub 2}O){sub 2} (1) crystallizes in space group C2/c, a=14.050(1), b=8.992(7), c=5.954(5) A, {beta}=101.014(2){sup o}. K{sub 2}Th(NO{sub 3}){sub 6} (2), P-3, a=13.606(1), c=6.641(6) A. (C{sub 12}H{sub 28}N){sub 2}Th(NO{sub 3}){sub 6} (3), P2{sub 1}/c, a=14.643(4), b=15.772(5), c=22.316(5) A, {beta}=131.01(1){sup o}. KTh(NO{sub 3}){sub 5}(H{sub 2}O){sub 2} (4), P2{sub 1}/c, a=10.070(8), b=12.731(9), c=13.231(8) A, {beta}=128.647(4){sup o}. Th(CrO{sub 4}){sub 2}(H{sub 2}O){sub 2} (5), P2{sub 1}/n, a=12.731(1), b=9.469(8), c=12.972(1) A, {beta}=91.793(2){sup o}. K{sub 2}Th{sub 3}(CrO{sub 4}){sub 7}(H{sub 2}O){sub 10} (6), Ama2, a=19.302(8), b=15.580(6), c=11.318(6) A. The coordination polyhedra about Thmore » in these structures are diverse. Th is coordinated by 9 O atoms in 5 and 6, seven of which are from monodentate (CrO{sub 4}) tetrahedra and two are (H{sub 2}O). The Th in compound 1 is coordinated by ten O atoms, four of which are O atoms of two bidentate (NO{sub 3}) triangles and six of which are (OH) and (H{sub 2}O). In compounds 2, 3 and 4 the Th is coordinate by 12 O atoms. In 2 and 3 there are six bidentate (NO{sub 3}) triangles, and in 4 ten of the O atoms are part of five bidentate (NO{sub 3}) triangles and the others are (H{sub 2}O) groups. The structural units of these compounds consist of a chain of thorium and nitrate polyhedra (1), isolated thorium hexanitrate clusters (2, 3), an isolated thorium pentanitrate dihydrate cluster (4), and a sheet (6) and framework (5) of thorium and chromate polyhedra. These structures illustrate the complexity inherent in the crystal chemistry of Th. - Graphical Abstract: The structures and infrared spectra of four new Th nitrates and two Th chromates are reported. The coordination numbers of the Th cations range from nine to 12 in these compounds. Structural units consist of isolated clusters, chains, sheets and frameworks.« less

45 CFR Appendix A to Part 13 - Appendix A to Part 13

Code of Federal Regulations, 2011 CFR

2011-10-01

...-3(h)(2)(B)(ii); 1395l(q)(2)(B)(i); 1395m(a)(11)(A), (c)(4)(C); 1395w-2(b)(2)(A); 1395w-4(g)(1), (g)(3)(B), (g)(4)(B)(ii); 1395nn(g)(5); 1395ss(a)(2), (p)(8), (p)(9)(C), (q)(5)(C), (r)(6)(A), (s)(3...-7a(c)(2); 1320b-10(c); 1395i-3(b)(3)(B)(ii), (g)(2)(A)(i); 1395l (h)(5)(D), (i)(6); 1395m(a)(11)(A...

Acoustic Surveys of a Scaled-Model CESTOL Transport Aircraft in Static and Forward Speed Conditions

NASA Technical Reports Server (NTRS)

Burnside, Nathan; Horne, Clifton

2012-01-01

An 11% scale-model of a Cruise-Efficient Short Take-off and Landing (CESTOL) scalemodel test was recently completed. The test was conducted in the AEDC National Full-Scale Aerodynamic Complex (NFAC) 40- by 80-Foot Wind Tunnel at NASA Ames Research Center. The model included two over-wing pod-mounted turbine propulsion simulators (TPS). The hybrid blended wing-body used a circulation control wing (CCW) with leadingand trailing-edge blowing. The bulk of the test matrix included three forward velocities (40 kts, 60 kts, and 100kts), angle-of-attack variation between -5 and 25 , and CCW mass flow variation. Seven strut-mounted microphones outboard of the left wing provided source directivity. A phased microphone array was mounted outboard of the right wing for source location. The goal of this paper is to provide a preliminary look at the acoustic data acquired during the Advanced Model for Extreme Lift and Improved Aeroacoustics (AMELIA) test for 0 angle-of-attack and 0 sideslip conditions. Data presented provides a good overview of the test conditions and the signal-to-noise quality of the data. TPS height variation showed a difference of 2 dB to 3 dB due to wing shielding. Variation of slot mass flow showed increases of 12 dB to 26 dB above the airframe noise and the TPS increased the overall levels an additional 5 dB to 10 dB.

B4C as a stable non-carbon-based oxygen electrode material for lithium-oxygen batteries

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

Song, Shidong; Xu, Wu; Cao, Ruiguo

Lithium-oxygen (Li-O 2) batteries have extremely high theoretical specific capacities and energy densities when compared with Li-ion batteries. However, the instability of both electrolyte and carbon-based oxygen electrode related to the nucleophilic attack of reduced oxygen species during oxygen reduction reaction and the electrochemical oxidation during oxygen evolution reaction are recognized as the major challenges in this field. Here we report the application of boron carbide (B 4C) as the non-carbon based oxygen electrode material for aprotic Li-O 2 batteries. B 4C has high resistance to chemical attack, good conductivity, excellent catalytic activity and low density that are suitable formore » battery applications. The electrochemical activity and chemical stability of B4C are systematically investigated in aprotic electrolyte. Li-O 2 cells using B4C based air electrodes exhibit better cycling stability than those used TiC based air electrode in 1 M LiTf-Tetraglyme electrolyte. The degradation of B 4C based electrode is mainly due to be the loss of active sites on B 4C electrode during cycles as identified by the structure and composition characterizations. These results clearly demonstrate that B 4C is a very promising alternative oxygen electrode material for aprotic Li-O 2 batteries. It can also be used as a standard electrode to investigate the stability of electrolytes.« less

Platinum(0)-mediated C-O bond activation of ethers via an SN2 mechanism.

PubMed

Ortuño, Manuel A; Jasim, Nasarella A; Whitwood, Adrian C; Lledós, Agustí; Perutz, Robin N

2016-11-29

A computational study of the C(methyl)-O bond activation of fluorinated aryl methyl ethers by a platinum(0) complex Pt(PCyp 3 ) 2 (Cyp = cyclopentyl) (N. A. Jasim, R. N. Perutz, B. Procacci and A. C. Whitwood, Chem. Commun., 2014, 50, 3914) demonstrates that the reaction proceeds via an S N 2 mechanism. Nucleophilic attack of Pt(0) generates an ion pair consisting of a T-shaped platinum cation with an agostic interaction with a cyclopentyl group and a fluoroaryloxy anion. This ion-pair is converted to a 4-coordinate Pt(ii) product trans-[PtMe(OAr F )(PCyp 3 ) 2 ]. Structure-reactivity correlations are fully consistent with this mechanism. The Gibbs energy of activation is calculated to be substantially higher for aryl methyl ethers without fluorine substituents and higher still for alkyl methyl ethers. These conclusions are in accord with the experimental results. Further support was obtained in an experimental study of the reaction of Pt(PCy 3 ) 2 with 2,3,5,6-tetrafluoro-4-allyloxypyridine yielding the salt of the Pt(η 3 -allyl) cation and the tetrafluoropyridinolate anion [Pt(PCy 3 ) 2 (η 3 -allyl)][OC 5 NF 4 ]. The calculated activation energy for this reaction is significantly lower than that for fluorinated aryl methyl ethers.

Strengthening Hospital Surge Capacity in the Event of Explosive or Chemical Terrorist Attacks

DTIC Science & Technology

2009-03-01

the hospital and have 202 S . Einav, Z. Feigenberg, C. Weissman, D. Zolchik, G. Caspi, D. Kotler... S . Fertel, B. Lackey, M. Marr, and B. P. Dreyer. “Overcoming Legal Obstacles involving the Voluntary Care of Children Who are Separated from their... HOSPITAL SURGE CAPACITY IN THE EVENT OF EXPLOSIVE OR CHEMICAL TERRORIST ATTACKS by Joan McInerney March 2009 Thesis Advisor: Anke Richter

Trust and Decision Making: An Empirical Platform

DTIC Science & Technology

2008-06-01

13th ICCRTS “C2 for Complex Endeavors” Trust and Decision Making : An Empirical Platform Topic(s): Cognitive and Social Issues...and Decision Making : An Empirical Platform 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM ELEMENT NUMBER 6. AUTHOR(S) 5d. PROJECT NUMBER 5e...PERSON a. REPORT unclassified b. ABSTRACT unclassified c. THIS PAGE unclassified Trust and Decision Making : An Empirical Platform Dr. Joseph B

Benchmarks for Evaluation of Distributed Denial of Service (DDOS)

DTIC Science & Technology

2008-01-01

publications: [1] E. Arikan , Attack Profiling for DDoS Benchmarks, MS Thesis, University of Delaware, August 2006. [2] J. Mirkovic, A. Hussain, B. Wilson...Sigmetrics 2007, June 2007 [5] J. Mirkovic, E. Arikan , S. Wei, S. Fahmy, R. Thomas, and P. Reiher Benchmarks for DDoS Defense Evaluation, Proceedings of the...Security Experimentation, June 2006. [9] J. Mirkovic, E. Arikan , S. Wei, S. Fahmy, R. Thomas, P. Reiher, Benchmarks for DDoS Defense Evaluation

Knowledge of heart attack symptoms and risk factors among native Thais: a street-intercept survey method.

PubMed

Poomsrikaew, Ornwanya; Ryan, Catherine J; Zerwic, Julie J

2010-10-01

This study aimed to determine Thais' knowledge of heart attack symptoms and risk factors and whether that knowledge was related to age, gender or education. Via a street-intercept survey method, a convenience sample of people aged ≥ 35 years (n = 192) was recruited. Mean age was 47 ± 9.6 years (range 35-81), and 55.2% were female. Participants identified on average 5.6 of 9 heart attack symptoms (SD 1.8) and 5.3 of 8 heart attack risk factors (SD 2.1). However, 66.7% mistakenly thought the chest discomfort would be severe, sharp and stabbing, and many subjects erroneously selected symptoms that are actually stroke symptoms. There were no gender or educational differences in knowledge of heart attack symptoms and risk factors. Older adults recognized fewer total symptoms than did younger adults. These findings could direct health-care providers to help the Thai population differentiate symptoms of heart attack from stroke. © 2010 Blackwell Publishing Asia Pty Ltd.

Kinetics of the Decomposition of Hydrogen Peroxide Catalyzed by Ferric Ethylenediaminetetraacetate Complex

PubMed Central

Walling, Cheves; Partch, Richard E.; Weil, Tomas

1975-01-01

Added substrates, acetone and t-butyl alcohol, strongly retard the decomposition of H2O2 brought about by ferric ethylenediaminetetraacetate (EDTA) at pH 8-9.5. Their relative effectiveness and the kinetic form of the retardation are consistent with their interruption of a hydroxyl radical chain that is propagated by HO· attack both upon H2O2 and on complexed and uncomplexed EDTA. Similar retardation is observed with decompositions catalyzed by ferric nitrilotriacetate and hemin, and it is proposed that such redox chains may be quite a general path for transition metal ion catalysis of H2O2 decomposition. PMID:16592209

Synthesis of carbon-11-labeled bivalent β-carbolines as new PET agents for imaging of cholinesterase in Alzheimer's disease.

PubMed

Wang, Min; Zheng, David X; Gao, Mingzhang; Hutchins, Gary D; Zheng, Qi-Huang

2011-04-01

Carbon-11-labeled bivalent β-carbolines, 9,9'-(pentane-1,5-diyl)bis(2-[(11)C]methyl-9H-pyrido[3,4-b]indol-2-ium)iodide ([(11)C]2a), 9,9'-(nonane-1,9-diyl)bis(2-[(11)C]methyl-9H-pyrido[3,4-b]indol-2-ium)iodide ([(11)C]2b), 9,9'-(dodecane-1,12-diyl)bis(2-[(11)C]methyl-9H-pyrido[3,4-b]indol-2-ium)iodide ([(11)C]2c) and 1,9-bis(2-[(11)C]methyl-3,4-dihydro-1H-pyrido[3,4-b]indol-9(2H)-yl)nonane ([(11)C]3), were prepared by N-[(11)C]methylation of their corresponding amine precursors using [(11)C]CH(3)I and isolated by either a simplified solid-phase extraction (SPE) method or HPLC in 40-60% radiochemical yields based on [(11)C]CO(2) and decay corrected to end of bombardment (EOB). The overall synthesis time from EOB was 20-30min, the radiochemical purity was >99%, and the specific activity at end of synthesis (EOS) was 185-370 GBq/μmol. Copyright © 2011 Elsevier Ltd. All rights reserved.

Three-Fold Intramolecular Ring Closing Alkene Metatheses of Square Planar Complexes with cis Phosphorus Donor Ligands P(X(CH2) mCH═CH2)3 (X = -, m = 5-10; X = O, m = 3-5): Syntheses, Structures, and Thermal Properties of Macrocyclic Dibridgehead Diphosphorus Complexes.

PubMed

Joshi, Hemant; Kharel, Sugam; Ehnbom, Andreas; Skopek, Katrin; Hess, Gisela D; Fiedler, Tobias; Hampel, Frank; Bhuvanesh, Nattamai; Gladysz, John A

2018-05-17

Reactions of cis-PtCl 2 (P((CH 2 ) m CH═CH 2 ) 3 ) 2 and Grubbs' first generation catalyst and then hydrogenations afford cis- PtCl 2 (P((CH 2 ) n ) 3 P) ( cis-2; n = 2 m + 2 = 12 (b), 14 (c), 16 (d), 18 (e), 20 (f), 22 (g); 6-40%), derived from 3-fold interligand metatheses. The phosphite complexes cis-PtCl 2 (P(O(CH 2 ) m* CH═CH 2 ) 3 ) 2 are similarly converted to cis- PtCl 2 (P(O(CH 2 ) n* O) 3 P) ( cis-5; n* = 8 (a), 10 (b), 12 (c), 10-20%). The substitution products cis- PtPh 2 (P((CH 2 ) n ) 3 P) ( cis-6c,d) and cis- PtI 2 (P(O(CH 2 ) 10 O) 3 P) are prepared using Ph 2 Zn and NaI, respectively. Crystal structures of cis-2c,d,f, cis-5a,b, and cis-6c show one methylene bridge that roughly lies in the platinum coordination plane and two that are perpendicular. The thermal behavior of the complexes is examined. When the bridges are sufficiently long, they rapidly exchange via an unusual "triple jump rope" motion over the PtX 2 moieties. NMR data establish Δ H ⧧ , Δ S ⧧ , and Δ G 298K ⧧ /Δ G 393K ⧧ values of 7.8 kcal/mol, -27.9 eu, and 16.1/18.8 kcal/mol for cis-2d, and a Δ G 393K ⧧ of ≥19.6 kcal/mol for the shorter bridged cis-2c. While cis-2c,g gradually convert to trans-2c,g at 150-185 °C in haloarenes, trans-2c,g give little reaction under analogous conditions, establishing the stability order trans > cis. Similar metathesis/hydrogenation sequences with octahedral complexes containing two cis phosphine ligands, fac-ReX(CO) 3 (P((CH 2 ) 6 CH═CH 2 ) 3 ) 2 (X = Cl, Br), give fac- ReX(CO) 3 ( P(CH 2 ) 13 CH 2 )((CH 2 ) 14 )( P(CH 2 ) 13 CH 2 ) (19-50%), which are derived from a combination of interligand and intraligand metathesis. The relative stabilities of cis/ trans and other types of isomers are probed by combinations of molecular dynamics and DFT calculations.

Herontwerp Ballistisch vest voor Vrouwen: Fase 1 (Redesign Ballistic Vest for Women: Phase 1)

DTIC Science & Technology

2008-09-01

Cupmaten van de verschillende respondenten. Proefpersoon Cupmaat 1 85b 2 3 80C 4 85g 5 řb 6 80b 7 75b 8 75c 9 75b 10 75alb 11 75ald 12 85c 13 75C 14 80c...Klantmianagement KPU-bedrijf / Vertegenwoordiger KBG vrouwen S. Eckhardt 9 /10 TNO Defensie en Veiligheid. vestiging Soesterberg, (Archief) 11 /12 TNO Defensie...Kampweg 5 PostbUs 23 3769 ZG Soesterberg TNO-rapport www.tno.ni T1+31 346 3562 11 TNO-DV 2008 A323 F +31 346 35 39 77 Info-DenV@tno. n1 Herontwerp

Reactions between atomic chlorine and pyridine in solid para-hydrogen: infrared spectrum of the 1-chloropyridinyl (C5H5N-Cl) radical.

PubMed

Das, Prasanta; Bahou, Mohammed; Lee, Yuan-Pern

2013-02-07

With infrared absorption spectra we investigated the reaction between Cl atom and pyridine (C(5)H(5)N) in a para-hydrogen (p-H(2)) matrix. Pyridine and Cl(2) were co-deposited with p-H(2) at 3.2 K; a planar C(5)H(5)N-Cl(2) complex was identified from the observed infrared spectrum of the Cl(2)/C(5)H(5)N/p-H(2) matrix. Upon irradiation at 365 nm to generate Cl atom in situ and annealing at 5.1 K for 3 min to induce secondary reaction, the 1-chloropyridinyl radical (C(5)H(5)N-Cl) was identified as the major product of the reaction Cl + C(5)H(5)N in solid p-H(2); absorption lines at 3075.9, 1449.7, 1200.6, 1148.8, 1069.3, 1017.4, 742.9, and 688.7 cm(-1) were observed. The assignments are based on comparison of observed vibrational wavenumbers and relative IR intensities with those predicted using the B3PW91/6-311++G(2d, 2p) method. The observation of the preferential addition of Cl to the N-site of pyridine to form C(5)H(5)N-Cl radical but not 2-, 3-, or 4-chloropyridine (ClC(5)H(5)N) radicals is consistent with the reported theoretical prediction that formation of the former proceeds via a barrierless path.

Crystallization and X-ray diffraction analysis of a putative bacterial class I labdane-related diterpene synthase.

PubMed

Serrano-Posada, Hugo; Centeno-Leija, Sara; Rojas-Trejo, Sonia; Stojanoff, Vivian; Rodríguez-Sanoja, Romina; Rudiño-Piñera, Enrique; Sánchez, Sergio

2015-09-01

Labdane-related diterpenoids are natural products with potential pharmaceutical applications that are rarely found in bacteria. Here, a putative class I labdane-related diterpene synthase (LrdC) identified by genome mining in a streptomycete was successfully crystallized using the microbatch method. Crystals of the LrdC enzyme were obtained in a holo form with its natural cofactor Mg(2+) (LrdC-Mg(2+)) and in complex with inorganic pyrophosphate (PPi) (LrdC-Mg(2+)-PPi). Crystals of native LrdC-Mg(2+) diffracted to 2.50 Å resolution and belonged to the trigonal space group P3221, with unit-cell parameters a = b = 107.1, c = 89.2 Å. Crystals of the LrdC-Mg(2+)-PPi complex grown in the same conditions as the native enzyme with PEG 8000 diffracted to 2.36 Å resolution and also belonged to the trigonal space group P3221. Crystals of the LrdC-Mg(2+)-PPi complex grown in a second crystallization condition with PEG 3350 diffracted to 2.57 Å resolution and belonged to the monoclinic space group P21, with unit-cell parameters a = 49.9, b = 104.1, c = 66.5 Å, β = 111.4°. The structure was determined by the single-wavelength anomalous dispersion (SAD) technique using the osmium signal from a potassium hexachloroosmate (IV) derivative.

In vivo immunologic selection of class I major histocompatibility complex gene deletion variants from the B16-BL6 melanoma.

PubMed

Talmadge, J E; Talmadge, C B; Zbar, B; McEwen, R; Meeker, A K; Tribble, H

1987-06-01

The mechanism by which tumor allografts escape host immunologic attack was investigated. B16-BL6 cells (the bladder 6 subline of the B16 melanoma) (H-2b) were transfected with a gene (Dd) encoding an allogeneic class I major histocompatibility complex antigen. Clones that expressed Dd antigen were injected into the footpads of nonimmune syngeneic mice, syngeneic immune mice, and nude mice. Under conditions of immunologic selection a clone that contained multiple copies of the transfected gene formed variants that lacked the transfected gene. Primary tumors and pulmonary metastases of immunized mice and pulmonary metastases of nonimmunized mice had lost the Dd gene and, in most cases, all of the associated plasmid. In contrast, in immunodeficient nude mice, primary tumors and pulmonary metastases retained the Dd gene and the associated plasmid. Deletion of genes encoding cell surface antigens may be one of the mechanisms by which allogeneic tumors escape immunologic attack.

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.

C1473G polymorphism in mouse tryptophan hydroxylase-2 gene in the regulation of the reaction to emotional stress.

PubMed

Bazhenova, Ekaterina Y; Bazovkina, Daria V; Kulikova, Elizabeth A; Fursenko, Dariya V; Khotskin, Nikita V; Lichman, Daria V; Kulikov, Alexander V

2017-02-15

Neurotransmitter serotonin (5-HT) is involved in the regulation of stress response. Tryptophan hydroxylase-2 (TPH2) is the key enzyme of serotonin (5-HT) synthesis in the brain. C1473G polymorphism in Tph2 gene is the main factor defining the enzyme activity in the brain of laboratory mice. The effect of interaction between C1473G polymorphism and 30min restriction stress on the behavior in the open field test, c-Fos gene expression and 5-HT metabolism in the brain in adult male of B6-1473C and B6-1473G congenic mouse lines with high and low TPH2 activity was investigated. A significant effect of genotype x stress interaction on c-Fos mRNA in the hypothalamus (F 1,21 =10.66, p<0.001) and midbrain (F 1,21 =9.18, p<0.01) was observed. The stress-induced rise of c-Fos mRNA in these structures is more intensive in B6-1473G than in B6-1473C mice. A marked effect of genotype x stress interaction on 5-HT level in the cortex (F 1,18 =9.38, p<0.01) and 5-HIAA/5-HT turnover rate in the hypothalamus (F 1,18 =9.01, p<0.01) was revealed. The restriction significantly decreased 5-HT level in the cortex (p<0.01) and increased 5-HIAA/5-HT rate (p<0.001) in the hypothalamus in B6-1473C mice, but not in B6-1473G mice. The present result is the first experimental evidence that C1473G polymorphism is involved in the regulation of the reaction to emotional stress in mice. Copyright © 2017 Elsevier B.V. All rights reserved.

Concurrent synergism and inhibition in bimetallic catalysis: catalytic binuclear elimination, solute-solute interactions and a hetero-bimetallic hydrogen-bonded complex in rh-mo hydroformylations.

PubMed

Li, Chuanzhao; Cheng, Shuying; Tjahjono, Martin; Schreyer, Martin; Garland, Marc

2010-04-07

Hydroformylations of cyclopentene and 3,3-dimethylbut-1-ene were performed using both Rh(4)(CO)(12) and (eta(5)-C(5)H(5))Mo(CO)(3)H as precursors in n-hexane at 298 K. Both stoichiometric and catalytic hydroformylations were conducted as well as isotopic labeling experiments. Six organometallic pure component spectra were recovered from the high-pressure FTIR experiments, namely the known species Rh(4)(CO)(12), (eta(5)-C(5)H(5))Mo(CO)(3)H, RCORh(CO)(4), and the new heterobimetallic complexes RhMo(CO)(7)(eta(5)-C(5)H(5)), a weak hydrogen bonded species (eta(5)-C(5)H(5))Mo(CO)(3)H-C(5)H(9)CORh(CO)(4), and a substituted RhMo(CO)(7-y)(eta(5)-C(5)H(5))L(y), where y = 1 or 2 and L = (pi-C(5)H(8)). The main findings were (1) catalytic binuclear elimination (CBER) occurs between (eta(5)-C(5)H(5))Mo(CO)(3)H and RCORh(CO)(4) resulting in aldehyde and RhMo(CO)(7)(eta(5)-C(5)H(5)), and this mechanism is responsible for ca. 10% of the product formation; (2) molecular hydrogen is readily activated by the new heterobimetallic complex(es); (3) FTIR and DFT spectroscopic evidence suggests that the weak hydrogen bonded species (eta(5)-C(5)H(5))Mo(CO)(3)H-C(5)H(9)CORh(CO)(4) has an interaction of the type eta(5)-C(5)H(4)-H...O=C; and (4) independent physicochemical experiments for volumes of interaction confirm that significant solute-solute interactions are present. With respect to the efficiency of the catalytic cycle, the formation of a weak (eta(5)-C(5)H(5))Mo(CO)(3)H-C(5)H(9)CORh(CO)(4) complex results in a significant decrease in the measured turnover frequency (TOF) and is the primary reason for the inhibition observed in the bimetallic catalytic hydroformylation. Such hydrogen bonding through the eta(5)-C(5)H(5) ring might have relevance to inhibition observed in other catalytic metallocene systems. The present catalytic system is an example of concurrent synergism and inhibition in bimetallic homogeneous catalysis.

Effects of Siderophores on Metal Adsorption to Kaolinite

NASA Astrophysics Data System (ADS)

Hepinstall, S. E.; Maurice, P. A.; Miller, M. J.

2003-12-01

Siderophores are metal-complexing ligands with high affinities for Fe(III), produced by many microorganisms in Fe-deficient environments. Siderophores can also form strong complexes with other metals such as Pb and Cd; hence, siderophores may play an important role in controlling metal mobility in porous media. This study compared the effects of siderophores desferrioxamine-B (DFO-B), desferrioxamine-D (DFO-D1), desferrioxamine-E (DFO-E), as well as siderophore-like ligand acetohydroxamic acid (aHA) on Pb and Cd adsorption to kaolinite (KGa-1b) at pH 4.5 to 9, in 0.1 M NaClO4, at 22 \\deg C, in the dark. At pH > 6.5 all of the siderophores plus aHA, inhibited Pb adsorption, with inhibition increasing in the order aHA < DFO-D1 < DFO-B < DFO-E. At lower pH, all four ligands slightly enhanced Pb adsorption. These ligands also inhibited Cd adsorption at high pH, but had little or no effect at low pH. These results suggest that siderophore effects on metal mobility through porous media are likely to be complex and variable with pH.

Temporo-spatial dynamics and behavioural patterns of 2012 cholera epidemic in the African mega-city of Conakry, Guinea.

PubMed

Blake, Alexandre; Keita, Veronique Sarr; Sauvageot, Delphine; Saliou, Mamadou; Njanpop, Berthe Marie; Sory, Fode; Sudre, Bertrand; Lamine, Koivogui; Mengel, Martin; Gessner, Bradford D; Sakoba, Keita

2018-02-15

Cholera is endemic in Guinea, having suffered consecutive outbreaks from 2004 to 2008 followed by a lull until the 2012 epidemic. Here we describe the temporal-spatial and behavioural characteristics of cholera cases in Conakry during a three-year period, including the large-scale 2012 epidemic. We used the national and African Cholera Surveillance Network (Africhol) surveillance data collected from every cholera treatment centre in Conakry city from August 2011 to December 2013. The prevalence of suspect and confirmed cholera cases, the case fatality ratio (CFR), and the factors associated with suspected cholera were described according to three periods: pre-epidemic (A), epidemic 2012 (B) and post epidemic (C). Weekly attack rates and temporal-spatial clustering were calculated at municipality level for period B. Cholera was confirmed by culture at the cholera national reference laboratory. A total of 4559 suspect cases were reported: 66, 4437, and 66 suspect cases in periods A, B and C, respectively. Among the 204 suspect cases with culture results available, 6%, 60%, and 70% were confirmed in periods A, B, and C, respectively. With 0.3%, the CFR was significantly lower in period B than in periods A (7.6%) and C (7.1%). The overall attack rate was 0.28% in period B, ranging from 0.17% to 0.31% across municipalities. Concomitantly, a cluster of cases was identified in two districts in the northern part of Conakry. At 14%, rice water stools were less frequent in period A than in period B and C (78% and 84%). Dehydration (31% vs 94% and 89%) and coma (0.4% vs 3.1% and 2.9%) were lower during period B than in periods A and C. The treatment of drinking water was less frequent in period A, while there were more reports of recent travel in period C. The epidemic dynamic and the sociological description of suspect cases before, during, and after the large-scale epidemic revealed that the Vibrio cholerae was already present before the epidemic. However, it appeared that infected individuals reacted differently in terms of disease severity as well as their access to treated water and travel habits. Such an in-depth description of cholera epidemics should be systematically carried out in cholera endemic settings in order to prioritize higher risk areas, identify transmission factors, and optimize preventive interventions.

Bioavailability of vitamin B-6 from rat diets containing wheat bran or cellulose

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

Hudson, C.A.; Betschart, A.A.; Oace, S.M.

1988-01-01

Bioavailability of vitamin B-6 (B-6) in the total diet was studied in male, weanling Sprague-Dawley rats fed fiber-free (FF) diets with 0.2 or 6.9 mg pyridoxine/kg diet (0-, 2- or 6.9-PYR), 20% wheat bran (WB) diets with 3.9- or 5.5-PYR or 7% cellulose (C) diets with 0- or 2-PYR for 28 d. Body weight gain (mean +/- SEM) with 0-PYR was 70 +/- 9.0 and 81.2 +/- 4.2 g for FF and C, respectively. All other groups gained 170-180 g. Urinary excretion of 4-pyridoxic acid (4-PA), a major B-6 metabolite, for FF groups was 1.31 +/- 0.22, 2.26 +/- 0.28more » and 6.39 +/- 1.73 micrograms/24 h, at 0-, 2- and 6.9-PYR, respectively. Rats fed WB diets excreted 4.99 +/- 0.58 and 9.81 +/- 0.76 micrograms/24 h (3.9- and 5.5-PYR, respectively) and those fed C diets excreted 1.46 +/- 0.34 and 2.69 +/- 0.72 micrograms/24 h (0- and 2-PYR). There was increasing turnover and shorter biological half-life of (/sup 14/C)pyridoxine (1 mu Ci injected on d 1) with increasing dietary B-6. Growth, 4-PA and /sup 14/C turnover data indicated that WB contributed to B-6 intake of these rats. Cellulose acted as a simple dietary diluent and had no effect on indices of B-6 status. These data suggest that dietary fiber, as cellulose or the indigestible component of wheat bran, does not adversely affect the bioavailability of vitamin B-6.« less

Logarithmic phase Escherichia coli K1 efficiently avoids serum killing by promoting C4bp-mediated C3b and C4b degradation

PubMed Central

Wooster, David G; Maruvada, Ravi; Blom, Anna M; Prasadarao, Nemani V

2006-01-01

Meningitis caused by Escherichia coli K1 is a serious illness in neonates with neurological sequelae in up to 50% of survivors. A high degree of bacteremia is required for E. coli K1 to cross the blood–brain barrier, which suggests that the bacterium must evade the host defence mechanisms and survive in the bloodstream. We previously showed that outer membrane protein A (OmpA) of E. coli binds C4b-binding protein (C4bp), an inhibitor of complement activation via the classical pathway. Nevertheless, the exact mechanism by which E. coli K1 survives in serum remains elusive. Here, we demonstrate that log phase (LP) OmpA+E. coli K1 avoids serum bactericidal activity more effectively than postexponential phase bacteria. OmpA–E. coli cannot survive in serum grown to either phase. The increased serum resistance of LP OmpA+E. coli is the result of increased binding of C4bp, with a concomitant decrease in the deposition of C3b and the downstream complement proteins responsible for the formation of the membrane attack complex. C4bp bound to E. coli K1 acts as a cofactor to factor I in the cleavage of both C3b and C4b, which shuts down the ensuing complement cascade. Accordingly, a peptide corresponding to the complement control protein domain 3 of C4bp sequence, was able to compete with C4bp binding to OmpA and cause increased deposition of C3b. Thus, binding of C4bp appears to be responsible for survival of E. coli K1 in human serum. PMID:16556262

A series of silver(I) coordination polymers with saccarinate and flexible aliphatic diamines

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

Yeşilel, Okan Zafer, E-mail: yesilel@ogu.edu.tr; Karamahmut, Bingül; Semerci, Fatih

A series of Ag(I) complexes with aliphatic diamines having a different chain length (NH{sub 2}-(CH{sub 2}){sub n}-NH{sub 2}, n=4–9), with the formulas, [Ag(μ-sac)(μ-db){sub 0.5}]{sub n} (1), ([Ag{sub 4}(sac){sub 4}(μ-dp){sub 2}]·4H{sub 2}O){sub n} (2){sub ,} ([Ag{sub 2}(sac){sub 2}(μ-dz)]·2H{sub 2}O){sub n} (3), ([Ag{sub 2}(sac){sub 2}(μ-dh)]·H{sub 2}O){sub n} (4), ([Ag{sub 2}(sac){sub 2}(μ-do)]·H{sub 2}O){sub n} (5a), [Ag{sub 2}(sac){sub 2}(μ-do){sub 2}] (5b) and [Ag{sub 4}(sac){sub 4}(μ-dn){sub 2}]·2H{sub 2}O (6), where sac=saccharinate, db=1,4-diaminobutane, dp=1,5-diaminopentane, dz=1,6-diaminohexane, dh=1,7-diaminoheptane, do=1,8-diaminooctane and dn=1,9-diaminononane, were synthesized and characterized by elemental analysis, infrared spectra and single-crystal X-ray diffraction analysis. In 1, the sac ligand bridges adjacent Ag(I) ions through the nitrogen andmore » carbonyl oxygen atoms to form eight-membered bimetallic rings with the Ag···Ag distance being 3.897 Å, which are linked by db ligands to give a 1D zigzag chain. The complexes 2–5a consist of a one-dimensional (1D) linear cationic chains and discrete mononuclear anions. The discreet complex units are further connected by ligand unsupported argentophilic interactions. In 6, the dn ligands bridge adjacent silver centers to form 24-membered macrometallacyclic rings, which are further connected to the anionic [Ag(sac){sub 2}]{sup -} units by argentophilic Ag1···Ag2 interactions to form a tetranuclear structure. The adjacent dinuclear units are further linked together through ligand-unsupported argentophilic Ag···Ag (3.207(1) Å) interactions, generating a one-dimensional linear chain. The most striking feature of complexes is the presence of the rare intermolecular C-H···Ag interactions. In 5b, the do ligand bridges two Ag(I) ions to form a dinuclear with a 22-membered macrometallacyclic ring. Furthermore, biological activities, luminescence properties and thermal analysis (TG/DTA) of the complexes were investigated. - Graphical abstract: In this study, six new silver coordination compounds were synthesized by using saccharinate and flexible aliphatic diamine derivatives. All the compounds were characterized by elemental analysis, IR and single-crystal X-ray analysis. TG/DTA. Furthermore, biological activities, luminescence properties and thermal analysis (TG/DTA) of the complexes have been investigated. Complexes 1–5a and 6 were synthesized with the same reactant ratio and room temperature by using a mixture of AgNO{sub 3}, sac and different length diamine derivatives. The complex 5b is also synthesized was similar to that of 1 at 80 °C. In the complexes, the diamine derivatives ligands show bis(bridging) coordination mode. The sac ligand exhibits a µ-bridging coordination mode in 1 and N-donor monodentate coordination mode in 2–6. Complexes 1–5 exhibit 1D chain structure while complex 6 are tetranuclear structure. In the crystal packing of complexes, 3D supramolecular frameworks are formed via C-H···Ag, Ag···π and Ag···Ag interactions.« less

Geologic and well-construction data for the H-9 borehole complex near the proposed Waste Isolation Pilot Plant site, southeastern New Mexico

USGS Publications Warehouse

Drellack, S.L.; Wells, J.G.

1982-01-01

The H-9 complex, a group of three closely spaced boreholes, is located 5.5 miles south of the proposed Waste Isolation Pilot Plant (WIPP) site in east-central Eddy County, New Mexico. The holes were drilled during July, August, and September 1979 to obtain geologic and hydrologic data to better define the regional ground-water-flow system. The geologic data presented in this report are part of a site-characterization study for the possible storage of defense-associated radioactive wastes within salt beds of the Salado Formation of Permian age. The geologic data include detailed descriptions of cores, cuttings, and geophysical logs. Each borehole was designed to penetrate a distinct water-bearing zone: H-9a (total depth 559 feet) was completed just below the Magenta Dolomite Member of the Rustler Formation; H-9b (total depth 708 feet) was completed just below the Culebra Dolomite Member of the Rustler Formation; H-9c (total depth 816 feet) was completed below the Rustler Formation-Salado Formation contact. The geologic units penetrated in borehole H-9c are eolian sand of Holocene age (0-5 feet); the Gatuna Formation of Pleistocene age; (5-25 feet); and the Dewey Lake Red Beds (25-455 feet), the Rustler Formation (455.791 feet), and part of the Salado Formation (791-816 feet), all of Permian age. Three sections (494-501 feet, 615-625 feet, 692-712 feet) in the Rustler Formation penetrated by borehole H-9c are composed of remnant anhydrite (locally altered to gypsum) and clay and silt residue from the dissolution of much thicker seams of argillaceous and silty halite. This indicates that the eastward-moving dissolution within the Rustler Formation, found just to the west of the WIPP site, is present at the H-9 site. (USGS)

The course of posttraumatic stress disorder in a follow-up study of survivors of the Oklahoma City bombing.

PubMed

North, Carol S; Pfefferbaum, Betty; Tivis, Laura; Kawasaki, Aya; Reddy, Chandrashekar; Spitznagel, Edward L

2004-01-01

The course of posttraumatic stress disorder (PTSD) in populations directly exposed to terrorist attacks is of major importance in the post-9/11 era. Because no systematic diagnostic studies of the most highly exposed individuals of the 9/11 terrorist attacks have yet been done, the Oklahoma City bombing remains a unique opportunity to examine PTSD over time in high-exposure terrorist victims. This study assessed 137 survivors in the direct path of the explosion at approximately 6 and 17 months postdisaster, using the Diagnostic Interview Schedule. Combined index and follow-up data yielded a higher (41%) incidence of PTSD than detected at index (32%) or follow-up (31%). All PTSD was chronic (89% unremitted at 17 months) with no delayed-onset cases. The avoidance and numbing symptom group C, unlike groups B and D alone, was pivotal to current PTSD status and was associated with indicators of functioning at index and follow-up. The findings at index were sustainable. This follow-up study confirmed the immediacy of onset of PTSD and its persistence over time, pointing to the need for early interventions that continue over the long term. Group C avoidance and numbing symptoms may aid in early recognition of PTSD and in predicting long-term functioning.

Antifungal susceptibilities of Candida glabrata species complex, Candida krusei, Candida parapsilosis species complex and Candida tropicalis causing invasive candidiasis in China: 3 year national surveillance.

PubMed

Xiao, Meng; Fan, Xin; Chen, Sharon C-A; Wang, He; Sun, Zi-Yong; Liao, Kang; Chen, Shu-Lan; Yan, Yan; Kang, Mei; Hu, Zhi-Dong; Chu, Yun-Zhuo; Hu, Tie-Shi; Ni, Yu-Xing; Zou, Gui-Ling; Kong, Fanrong; Xu, Ying-Chun

2015-03-01

To define the antifungal susceptibility patterns of the most common non-albicans Candida spp. in China. We evaluated the susceptibilities to nine antifungal drugs of Candida parapsilosis species complex, Candida tropicalis, Candida glabrata species complex and Candida krusei isolates from patients with invasive candidiasis at 11 hospitals over 3 years. Isolates were identified by MALDI-TOF MS supplemented by DNA sequencing. MICs were determined by Sensititre YeastOne(TM) using current clinical breakpoints/epidemiological cut-off values to assign susceptibility (or WT), and by CLSI M44-A2 disc diffusion for fluconazole and voriconazole. Of 1072 isolates, 392 (36.6%) were C. parapsilosis species complex. C. tropicalis, C. glabrata species complex and C. krusei comprised 35.4%, 24.3% and 3.7% of the isolates, respectively. Over 99.3% of the isolates were of WT phenotype to amphotericin B and 5-flucytosine. Susceptibility/WT rates to azoles among C. parapsilosis species complex were ≥97.5%. However, 11.6% and 9.5% of C. tropicalis isolates were non-susceptible to fluconazole and voriconazole, respectively (7.1% were resistant to both). Approximately 14.3% of C. glabrata sensu stricto isolates (n = 258) were fluconazole resistant, and 11.6% of C. glabrata sensu stricto isolates were cross-resistant to fluconazole and voriconazole. All C. krusei isolates were susceptible/WT to voriconazole, posaconazole and itraconazole. Overall, 97.7%-100% of isolates were susceptible to caspofungin, micafungin and anidulafungin, but 2.3% of C. glabrata were non-susceptible to anidulafungin. There was no azole/echinocandin co-resistance. Disc diffusion and Sensititre YeastOne(TM) methods showed >95% categorical agreement for fluconazole and voriconazole. In summary, reduced azole susceptibility was seen among C. tropicalis. Resistance to echinocandins was uncommon. © The Author 2014. Published by Oxford University Press on behalf of the British Society for Antimicrobial Chemotherapy. All rights reserved. For Permissions, please e-mail: journals.permissions@oup.com.

Survival at Sea for Mariners, Aviators and Search and Rescue Personnel (Survie en mer pour les marins, les aviateurs et le personnel de recherche et de sauvetage)

DTIC Science & Technology

2008-02-01

think that death from sinking in cold water is a thing of the past – the Titanic, the Empress of Ireland, the Lusitania , etc. Nothing could be further...Luftwaffe, 9B-3 Lusitania , 9C-5 M Macintosh, R.R., 9B-3 Mae West, 9B-3 Mallison’s Seamen’s Friend and Bather’s Companion, 9B-2 Manikin, 9C-10

CTC Sentinel. Volume 2, Issue 3, March 2009. Somalia’s New Government and the Challenge of Al-Shabab

DTIC Science & Technology

2009-03-01

Somalia’s New Government and the Challenge of Al-Shabab By David H. Shinn Contents FEATURE ARTICLE 1 Somalia’s New Government and the Challenge...2009 to 00-00-2009 4. TITLE AND SUBTITLE Somalia?s New Government and the Challenge of Al-Shabab 5a. CONTRACT NUMBER 5b. GRANT NUMBER 5c. PROGRAM...forces and African Union peacekeepers.22 In a mid- February 2009 video, Abu Yahya called on Somalis to oppose the new Somali government and attack

The nido-osmaboranes [2,2,2-(CO)(PPh(3))(2)-nido-2-OsB(5)H(9)] and [6,6,6-(CO)(PPh(3))(2)-nido-6-OsB(9)H(13)].

PubMed

Bould, J; Kennedy, J D; Thomas, R L; Rath, N P; Barton, L

2001-11-01

The structural characterization of the osmahexaborane 2-carbonyl-2,2-bis(triphenylphosphine)-nido-2-osmahexaborane(9), [Os(B(5)H(9))(C(18)H(15)P)(2)(CO)], (I), a metallaborane analogue of B(6)H(10), confirms the structure proposed from NMR spectroscopy. The structure of the osmadecaborane 6-carbonyl-6,6-bis(triphenylphosphine)-nido-6-osmadecaborane(13), [Os(B(9)H(13))(C(18)H(15)P)(2)(CO)], (IV), is similarly confirmed. The short basal B-B distance of 1.652 (8) A in (I), not bridged by an H atom, mirrors that in the parent hexaborane(10) [1.626 (4) A].

[Hospital care for stroke patients in the Valencian Region using the basic minimum data set from the International Classification of Diseases, 9th revision, clinical modification].

PubMed

Geffner-Sclarsky, D

To determine the load and characteristics of cerebrovascular diseases (CVD) admitted in the hospital network throughout the Valencian Region. The paper reports on an analysis of the information included in the basic minimum data set (BMDS) from the 26 hospitals run by the Valencian Regional Ministry of Health in the year 2001. Patients that were selected were those whose main diagnosis was codes C.430 to C.437, according to the International Classification of Diseases, 9th revision, clinical modification (ICD-9-CM). A total of 10,558 patients with CVD were discharged, which accounts for 2.6% of admissions and 3% of hospital stays. The mean age of the series was 71.03 years -standard deviation (SD): 9- and 94.8% were admitted as emergencies. By diagnoses, 3% (319) were subarachnoid haemorrhages (SAH; C.430); 13.4% (1,412) were cerebral haemorrhages (ICH; C.431); 18.5% (1,956) were transient ischemic attacks (TIA; C.435); 49.5% (5,225) were cases of cerebral infarction (CI; C.434 and C.436); and 15.6% involved other vascular processes (C.433 and C.437). Mortality rates were 30.1% in SAH; 33.9% in ICH; 11.7% in CI; and 2.7% in TIA. Mean number of days in hospital: SAH 17.4 (SD: 15); ICH 13.1 (SD: 11.8); CI 9.9 (SD: 6.4) and in cases of TIA 7.2 (SD: 4). The percentages of survivors who were discharged home were 78.9 % in SAH, 83.2% in ICH and 91.9% in the case of CI. In all, 51.3% (5,413 patients) were discharged by neurological units. In spite of possible insufficiencies analysed in this work, the use of the BMDS provides valuable epidemiological information that is very useful for health care management.

All Prime Contract Awards by State or Country, Place, and Contractor, FY83, Part 1 (Argentina-Goodyear, Arizona).

DTIC Science & Technology

1983-01-01

C Z 5 2 2 5110 000 69 HAND TOOLS EDGED NONPOWERED 7 9 3 5 L 06 1 B 4 1 0 100 WAESCHEREI KRAUSE GERMANY 088616 0000 GY I L OJA37 2913 DAJA37-82-00210 B...0 27 WOLFGANG PRAYON GERMANY 090010 0000 GY I D OJA37 0369 DAJA37-82-DO261 B C 2 5 3 2 V212 000 S MOTOR PASSENGER SERVICE 7 9 4 5 L 06 1 B J 1 J 34

Large scale mitochondrial sequencing in Mexican Americans suggests a reappraisal of Native American origins.

PubMed

Kumar, Satish; Bellis, Claire; Zlojutro, Mark; Melton, Phillip E; Blangero, John; Curran, Joanne E

2011-10-07

The Asian origin of Native Americans is largely accepted. However uncertainties persist regarding the source population(s) within Asia, the divergence and arrival time(s) of the founder groups, the number of expansion events, and migration routes into the New World. mtDNA data, presented over the past two decades, have been used to suggest a single-migration model for which the Beringian land mass plays an important role. In our analysis of 568 mitochondrial genomes, the coalescent age estimates of shared roots between Native American and Siberian-Asian lineages, calculated using two different mutation rates, are A4 (27.5 ± 6.8 kya/22.7 ± 7.4 kya), C1 (21.4 ± 2.7 kya/16.4 ± 1.5 kya), C4 (21.0 ± 4.6 kya/20.0 ± 6.4 kya), and D4e1 (24.1 ± 9.0 kya/17.9 ± 10.0 kya). The coalescent age estimates of pan-American haplogroups calculated using the same two mutation rates (A2:19.5 ± 1.3 kya/16.1 ± 1.5 kya, B2:20.8 ± 2.0 kya/18.1 ± 2.4 kya, C1:21.4 ± 2.7 kya/16.4 ± 1.5 kya and D1:17.2 ± 2.0 kya/14.9 ± 2.2 kya) and estimates of population expansions within America (~21-16 kya), support the pre-Clovis occupation of the New World. The phylogeography of sublineages within American haplogroups A2, B2, D1 and the C1b, C1c and C1d subhaplogroups of C1 are complex and largely specific to geographical North, Central and South America. However some sub-branches (B2b, C1b, C1c, C1d and D1f) already existed in American founder haplogroups before expansion into the America. Our results suggest that Native American founders diverged from their Siberian-Asian progenitors sometime during the last glacial maximum (LGM) and expanded into America soon after the LGM peak (~20-16 kya). The phylogeography of haplogroup C1 suggest that this American founder haplogroup differentiated in Siberia-Asia. The situation is less clear for haplogroup B2, however haplogroups A2 and D1 may have differentiated soon after the Native American founders divergence. A moderate population bottle neck in American founder populations just before the expansion most plausibly resulted in few founder types in America. The similar estimates of the diversity indices and Bayesian skyline analysis in North America, Central America and South America suggest almost simultaneous (~ 2.0 ky from South to North America) colonization of these geographical regions with rapid population expansion differentiating into more or less regional branches across the pan-American haplogroups.

Large scale mitochondrial sequencing in Mexican Americans suggests a reappraisal of Native American origins

PubMed Central

2011-01-01

Background The Asian origin of Native Americans is largely accepted. However uncertainties persist regarding the source population(s) within Asia, the divergence and arrival time(s) of the founder groups, the number of expansion events, and migration routes into the New World. mtDNA data, presented over the past two decades, have been used to suggest a single-migration model for which the Beringian land mass plays an important role. Results In our analysis of 568 mitochondrial genomes, the coalescent age estimates of shared roots between Native American and Siberian-Asian lineages, calculated using two different mutation rates, are A4 (27.5 ± 6.8 kya/22.7 ± 7.4 kya), C1 (21.4 ± 2.7 kya/16.4 ± 1.5 kya), C4 (21.0 ± 4.6 kya/20.0 ± 6.4 kya), and D4e1 (24.1 ± 9.0 kya/17.9 ± 10.0 kya). The coalescent age estimates of pan-American haplogroups calculated using the same two mutation rates (A2:19.5 ± 1.3 kya/16.1 ± 1.5 kya, B2:20.8 ± 2.0 kya/18.1 ± 2.4 kya, C1:21.4 ± 2.7 kya/16.4 ± 1.5 kya and D1:17.2 ± 2.0 kya/14.9 ± 2.2 kya) and estimates of population expansions within America (~21-16 kya), support the pre-Clovis occupation of the New World. The phylogeography of sublineages within American haplogroups A2, B2, D1 and the C1b, C1c andC1d subhaplogroups of C1 are complex and largely specific to geographical North, Central and South America. However some sub-branches (B2b, C1b, C1c, C1d and D1f) already existed in American founder haplogroups before expansion into the America. Conclusions Our results suggest that Native American founders diverged from their Siberian-Asian progenitors sometime during the last glacial maximum (LGM) and expanded into America soon after the LGM peak (~20-16 kya). The phylogeography of haplogroup C1 suggest that this American founder haplogroup differentiated in Siberia-Asia. The situation is less clear for haplogroup B2, however haplogroups A2 and D1 may have differentiated soon after the Native American founders divergence. A moderate population bottle neck in American founder populations just before the expansion most plausibly resulted in few founder types in America. The similar estimates of the diversity indices and Bayesian skyline analysis in North America, Central America and South America suggest almost simultaneous (~ 2.0 ky from South to North America) colonization of these geographical regions with rapid population expansion differentiating into more or less regional branches across the pan-American haplogroups. PMID:21978175

[Macrovascular diseases-based on the data of Japanese cohort study (JCDM) including 1,016 very elderly diabetic individuals older than 75 years old].

PubMed

Hayashi, Toshio

2013-11-01

LDL-cholesterol and glucose are risk for ischemic heart disease (IHD) in middle-aged diabetic individuals; however, the risk among elderly, especially very elderly, is not well-known. We performed a prospective cohort study (JCDM) with 5.5 years of follow-up. Four thousand fourteen type 2 diabetic patients without previous IHD or cerebrovascular attack (CVA) (1,936 women: 67.4 +/- 9.5 years, > or = 75 years, n = 1,016) were recruited. One hundred fifty-three IHDs and 104 CVAs occurred over 5.5 years. Lower HDL-cholesterol (HDL-C) was correlated with IHD in patients > or = 75 years old. In contrast, systolic BP, HbA1c, LDL-C and non-HDL-C were correlated in subjects < 65 years old, and LDL-C/HDL-C ratio was correlated in all subjects. HDL-C was correlated with CVA in patients > or = 75 years old. These age-dependent differences in risk are important for developing individualized strategies to prevent atherosclerotic disease.

Homeland Security Within State Departments of Agriculture: Success Factors and Barriers to an Effective Security Program

DTIC Science & Technology

2010-09-01

13. ABSTRACT (maximum 200 words ) The food and agriculture sector in the United States is vulnerable to attack. One solution is to ensure that...Bureau of Investigation FEMA Federal Emergency Management Agency FMD Foot and Mouth Disease GAO General Accounting Office (changed name to...will need to respond to an FMD [foot and mouth disease] outbreak” (GAO, 2002b, p. 5). In many cases, veterinarians serve as 9 first-line

Leading-Edge Votex-System Details Obtained on F-106B Aircraft Using a Rotating Vapor Screen and Surface Techniques

NASA Technical Reports Server (NTRS)

Lamar, John E.; Brandon, Jay; Stacy, Kathryn; Johnson, Thomas D., Jr.; Severance, Kurt; Childers, Brooks A.

1993-01-01

A flight research program to study the flow structure and separated-flow origins over an F-106B aircraft wing is described. The flight parameters presented include Mach numbers from 0.26 to 0.81, angles of attack from 8.5 deg to 22.5 deg, Reynolds numbers from 22.6 x 10(exp 6) to 57.3 x 10(exp 6) and load factors from 0.9 to 3.9 times the acceleration due to gravity. Techniques for vapor screens, image enhancement, photogrammetry, and computer graphics are integrated to analyze vortex-flow systems. Emphasis is placed on the development and application of the techniques. The spatial location of vortex cores and their tracks over the wing are derived from the analysis. Multiple vortices are observed and are likely attributed to small surface distortions in the wing leading-edge region. A major thrust is to correlate locations of reattachment lines obtained from the off-surface (vapor-screen) observations with those obtained from on-surface oil-flow patterns and pressure-port data. Applying vapor-screen image data to approximate reattachment lines is experimental, but depending on the angle of attack, the agreement with oil-flow results is generally good. Although surface pressure-port data are limited, the vapor-screen data indicate reattachment point occurrences consistent with the available data.

Rhenium(V)-oxo complexes of neutral and monoanionic tetraazamacrocycles. X-ray structures of trans-oxohydroxo(1,4,8,11-tetraazacyclotetradecane)rhenium(V) bis(perchlorate)

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

Tsang, B.W.; Reibenspies, J.; Martell, A.E.

1993-03-17

The complexes of ReO[sub 2][sup +] and ReO(OH)[sup 2+] with 1,4,8,11-tetraazacyclotetradecane (cyclam) and 1,4,8,11-tetraazacyclotetradecan-2-one (O[sub 1]cyclam) have been synthesized and characterized. The complexes were prepared by ligand exchange reactions of the macrocycles with a variety of starting compounds including ReOCl[sub 3](PPh[sub 3])[sub 2] and ReO[sub 2](en)[sub 2]Cl. The ReO(OH)[sup 2+] complexes have been structurally characterized. ReO(OH)(H[sub [minus]1]O[sub 1]cyclam)ReO[sub 4] crystallizes in the monoclinic P2[sub 1]/n space group with a = 10.308(3) [Angstrom], b = 9.527(2) [Angstrom], c = 17.808(3) [Angstrom], and [beta] = 106.57(2)[degrees]. ReO(OH)(cyclam)(ClO[sub 4])[sub 2] crystallizes in the monoclinic C2/c space group with a = 9.734(4) [Angstrom], bmore » = 16.999(5) [Angstrom], c = 12.187(5) [Angstrom], and [beta] = 106.36[degrees]. The complex ReO(OH)(H[sub [minus]1]O[sub 1]cyclam)ReO[sub 4] has a distorted octahedral structure with one short ReO(oxo) bond and one long ReO(hydroxo) bond (1.685(8) vs 1.970(8) [Angstrom]). The deprotonated amide ReN(sp[sup 2]) bond is shorter than the other three ReN(sp[sup 3]) bond lengths (1.98(1) vs 2.13(3) [Angstrom] (average)). The structure of the ReO(OH)(cyclam)(ClO[sub 4])[sub 2] complex shows no distinction between the lengths of the two ReO(oxo and hydroxo) bonds (1.766(5) [Angstrom]) due to disorder of the oxo and hydroxo groups. Spectroscopic evidence is reported to confirm the presence of both oxo and hydroxo groups coordinated to rhenium. 38 refs., 7 figs., 6 tabs.« less

Synthesis of a Neutral Mixed-Valence Diferrocenyl Carborane for Molecular Quantum-Dot Cellular Automata Applications.

PubMed

Christie, John A; Forrest, Ryan P; Corcelli, Steven A; Wasio, Natalie A; Quardokus, Rebecca C; Brown, Ryan; Kandel, S Alex; Lu, Yuhui; Lent, Craig S; Henderson, Kenneth W

2015-12-14

The preparation of 7-Fc(+) -8-Fc-7,8-nido-[C2 B9 H10 ](-) (Fc(+) FcC2 B9 (-) ) demonstrates the successful incorporation of a carborane cage as an internal counteranion bridging between ferrocene and ferrocenium units. This neutral mixed-valence Fe(II) /Fe(III) complex overcomes the proximal electronic bias imposed by external counterions, a practical limitation in the use of molecular switches. A combination of UV/Vis-NIR spectroscopic and TD-DFT computational studies indicate that electron transfer within Fc(+) FcC2 B9 (-) is achieved through a bridge-mediated mechanism. This electronic framework therefore provides the possibility of an all-neutral null state, a key requirement for the implementation of quantum-dot cellular automata (QCA) molecular computing. The adhesion, ordering, and characterization of Fc(+) FcC2 B9 (-) on Au(111) has been observed by scanning tunneling microscopy. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Incidence of Hepatocellular Carcinoma According to Hepatitis B Virus Genotype in Alaska Native People

PubMed Central

Ching, Lance K.; Gounder, Prabhu P.; Bulkow, Lisa; Spradling, Philip R.; Bruce, Michael; Negus, Susan; Snowball, Mary; McMahon, Brian J.

2016-01-01

Background & Aims Most regions of the world have <3 co-circulating hepatitis B virus (HBV) genotypes, which limits direct comparisons of hepatocellular carcinoma (HCC) risk among HBV-infected persons by genotype. We evaluated HCC incidence by HBV genotype in a cohort of Alaska Native (AN) persons where 5 HBV genotypes (A, B, C, D, F) have been identified. Methods Our cohort comprised AN persons with chronic HBV infection identified during 1983–2012 who consented to participate in the study. Cohort persons were offered annual hepatitis B e antigen (HBeAg) testing and semiannual HCC screening. We developed a logistic regression model to compare HCC risk by genotype, adjusting for age, sex, region, and HBeAg status. Results Among the 1,235 consenting study participants, 711 (57.6%) were male, 510 (41.3%) were HBeAg positive at cohort entry, and 43 (3.5%) developed HCC. The HBV genotype was known for 1,142 (92.5%) persons (13.5% A, 3.9% B, 6.7% C, 56.9% D, 19.0% F). The HCC incidence/1,000 person-years of follow-up for genotypes A, B, C, D, and F was 1.3, 0, 5.5, 0.4, and 4.2, respectively. Compared with persons with HBV genotype B/D infection, the HCC risk was higher for persons with genotypes A (adjusted odds ratio [aOR]: 3.9, 95% CI: 1.14–13.74), C (aOR: 16.3, 95% CI: 5.20–51.11), and F (aOR: 13.9, 95% CI: 5.30–36.69). Conclusion HBV genotype is independently associated with HCC risk. AN persons with genotypes A, C, and F are at higher risk compared with genotypes B or D. PMID:27009849

Studies of the conformational stability of invasion plasmid antigen B from Shigella

PubMed Central

Choudhari, Shyamal P; Kramer, Ryan; Barta, Michael L; Greenwood, Jamie C; Geisbrecht, Brian V; Joshi, Sangeeta B; Picking, William D; Middaugh, C Russell; Picking, Wendy L

2013-01-01

Shigella spp. are the causative agent of shigellosis, the second leading cause of diarrhea in children of ages 2–5. Despite many years of research, a protective vaccine has been elusive. We recently demonstrated that invasion plasmid antigens B and D (IpaB and IpaD) provide protection against S. flexneri and S. sonnei. These proteins, however, have very different properties which must be recognized and then managed during vaccine formulation. Herein, we employ spectroscopy to assess the stability of IpaB as well as IpgC (invasion protein gene), IpaB's cognate chaperone, and the IpaB/IpgC complex. The resulting data are mathematically summarized into a visual map illustrating the stability of the proteins and their complex as a function of pH and temperature. The IpaB/IpgC complex exhibits thermal stability at higher pH values but, though initially stable, quickly unfolds with increasing temperature when maintained at lower pH. In contrast, IpaB is a much more complex protein exhibiting increased stability at higher pH, but shows initial instability at lower pH values with pH 5 showing a distinct transition. IpgC precipitates at and below pH 5 and is stable above pH 7. Most strikingly, it is clear that complex formation results in stabilization of the two components. This work serves as a basis for the further development of IpaB as a vaccine candidate as well as extends our understanding of the structural stability of the Shigella type III secretion system. PMID:23494968

Granulocyte and monocyte CD11b expression during plasma separation is dependent on complement factor 5 (C5) - an ex vivo study with blood from a C5-deficient individual.

PubMed

Hardersen, Randolf; Enebakk, Terje; Christiansen, Dorte; Bergseth, Grethe; Brekke, Ole-Lars; Mollnes, Tom Eirik; Lappegård, Knut Tore; Hovland, Anders

2018-04-01

The aim of the study was to investigate the role of complement factor 5 (C5) in reactions elicited by plasma separation using blood from a C5-deficient (C5D) individual, comparing it to C5-deficient blood reconstituted with C5 (C5DR) and blood from healthy donors. Blood was circulated through an ex vivo plasma separation model. Leukocyte CD11b expression and leukocyte-platelet conjugates were measured by flow cytometry during a 30-min period. Other markers were assessed during a 240-min period. Granulocyte and monocyte CD11b expression did not increase in C5D blood during plasma separation. In C5DR samples granulocytes CD11b expression, measured by mean fluorescence intensity (MFI), increased from 10481 ± 6022 (SD) to 62703 ± 4936, and monocytes CD11b expression changed from 13837 ± 7047 to 40063 ± 713. Granulocyte-platelet conjugates showed a 2.5-fold increase in the C5DR sample compared to the C5D sample. Monocyte-platelet conjugates increased independently of C5. In the C5D samples, platelet count decreased from 210 × 10 9 /L (201-219) (median and range) to 51 × 10 9 /L (50-51), and C3bc increased from 14 CAU/mL (21-7) to 198 CAU/mL (127-269), whereas TCC formation was blocked during plasma separation. In conclusion, up-regulation of granulocyte and monocyte CD11b during plasma separation was C5-dependent. The results also indicate C5 dependency in granulocyte-platelet conjugates formation. © 2018 APMIS. Published by John Wiley & Sons Ltd.

Fast WEP-Key Recovery Attack Using Only Encrypted IP Packets

NASA Astrophysics Data System (ADS)

Teramura, Ryoichi; Asakura, Yasuo; Ohigashi, Toshihiro; Kuwakado, Hidenori; Morii, Masakatu

Conventional efficient key recovery attacks against Wired Equivalent Privacy (WEP) require specific initialization vectors or specific packets. Since it takes much time to collect the packets sufficiently, any active attack should be performed. An Intrusion Detection System (IDS), however, will be able to prevent the attack. Since the attack logs are stored at the servers, it is possible to prevent such an attack. This paper proposes an algorithm for recovering a 104-bit WEP key from any IP packets in a realistic environment. This attack needs about 36, 500 packets with a success probability 0.5, and the complexity of our attack is equivalent to about 220 computations of the RC4 key setups. Since our attack is passive, it is difficult for both WEP users and administrators to detect our attack.

Oxidation of a guanine derivative coordinated to a Pt(IV) complex initiated by intermolecular nucleophilic attacks.

PubMed

Choi, Sunhee; Personick, Michelle L; Bogart, Justin A; Ryu, DaWeon; Redman, Romany M; Laryea-Walker, Edith

2011-03-28

In this study we report that fac-[Pt(IV)(dach)(9-EtG)Cl(3)](+) (dach = d,l-1,2-diaminocyclohexane, 9-EtG = 9-ethylguanine) in high pH (pH 12) or phosphate solution (pH 7.4) produces 8-oxo-9-EtG and Pt(II) species. The reaction in H(2)(18)O revealed that the oxygen atom in hydroxide or phosphate ends up at the C8 position of 8-oxo-G. The kinetics of the redox reaction was first order with respect to both Pt(IV)-G and free nucleophiles (OH(-) and phosphate). The oxidation of G initiated by hydroxide was approximately 30∼50 times faster than by phosphate in 100 mM NaCl solutions. The large entropy of activation of OH(-1) (ΔS(‡) = 26.6 ± 4.3 J mol(-1) K(-1)) due to the smaller size of OH(-) is interpreted to be responsible for the faster kinetics compared to phosphate (ΔS(‡) = -195.5 ± 11.1 J mol(-1) K(-1)). The enthalpy of activation for phosphate reaction is more favorable relative to the OH(-) reaction (ΔH(‡) = 35.4 ± 3.5 kJ mol(-1) for phosphate vs. 96.6 ± 11.4 kJ mol(-1) for OH(-1)). The kinetic isotope effect of H8 was determined to be 7.2 ± 0.2. The rate law, kinetic isotope effect, and isotopic labeling are consistent with a mechanism involving proton ionization at the C8 position as the rate determining step followed by two-electron transfer from G to Pt(IV).

Results of an experimental aerodynamic investigation to obtain static stability and control characteristics of the SSV configurations: The 2A(VL70-000089B) model 1 and 3(VL70-000139B) model 2 orbiter at Mach numbers of 2.5, 3.9 and 4.6 in the NASA LaRC 4 X 4-foot UPWT (OA44)

NASA Technical Reports Server (NTRS)

Esparza, V.; Milam, M. D.

1974-01-01

Investigation of space shuttle orbiter configurations 2A(VL70-000089B) and 3(VL70-000139B) was performed at the Langley Research Center Unitary Plan Wind Tunnel (UPWT) from June 1, 1973, to June 15, 1973, for 60 test hours. The primary test objectives were to obtain stability and control characteristics for Configurations 2A and 3 and an alternate forebody used with Configuration 3. In addition, hinge moments were measured on the elevons and rudder for Configuration 2A only. The configurations were tested at Mach numbers 2.5, 3.9 and 4.6. Pitch runs were made at angles of attack from -4 to 44 deg and sideslip angles from -4 to +6. Static pressures were measured at the fuselage base for use in force data correction.

Analysis of the Causes of Inflight Refueling Mishaps with the KC-135

DTIC Science & Technology

1989-09-01

Air Service. During the spring of 1923 in San Diego , California, a Do Havilland DH -4 biplane was modified S with a 50 foot home. This ’banker...The remaining 15 were considered to be fighter/attack aircraft. Overall, the F-4, B-52, C-141, and F- 106 were involved in over fifty percent of the...AIRCRAFT 1 2 3 4 5 6 7 TYPE AIRCRAFT F-4 34 0 8 6 0 8 3 59 21.15 B-52 18 0 10 4 1 6 0 39 13.98 C-141 14 0 1 1 3 4 2 25 8.96 F- 106 13 0 2 0 0 1 2 18

Magnetic properties of 1 : 4 complexes of CoCl2 and pyridines carrying carbenes (S(0) = 4/2, 6/2, and 8/2) in diluted frozen solution; influence of carbene multiplicity on heterospin single-molecule magnets.

PubMed

Karasawa, Satoru; Nakano, Kimihiro; Tanokashira, Jun-ichi; Yamamoto, Noriko; Yoshizaki, Takahito; Koga, Noboru

2012-11-28

The microcrystalline sample of a parent complex, [CoCl(2)(py)(4)], showed a single-molecule magnet (SMM) behavior with an effective activation barrier, U(eff)/k(B), of 16 K for reversal of the magnetism in the presence of a dc field of 3 kOe. Pyridine ligands having 2-4 diazo moieties, DYpy; Y = 2, 3l, 3b, and 4, were prepared and confirmed to be quintet, septet, septet, and nonet in the ground state, respectively, after irradiation. The 1 : 4 complexes, CoCl(2)(DYpy)(4); Y = 2, 3l, 3b, and 4 in frozen solutions after irradiation showed the magnetic behaviors of SMMs with total spin multiplicity, S(total) = 17/2, 25/2, 25/2, and 33/2, respectively. Hysteresis loops depending on the temperature were observed and the values of coercive force, H(c), at 1.9 K were 12, 8.4, 11, and 8.1 kOe for CoCl(2)(CYpy)(4); Y = 2, 3l, 3b, and 4, respectively. In dynamic magnetic susceptibility experiments, ac magnetic susceptibility data obeyed the Arrhenius law to give U(eff)/k(B) values of 94, 92, 93, and 87 K for CoCl(2)(CYpy)(4); Y = 2, 3l, 3b, and 4, respectively, while the relaxation times for CoCl(2)(CYpy)(4); Y = 2 and 3l, obtained by dc magnetization decay in the range of 3.5-1.9 K slightly deviated downward from Arrhenius plots on cooling. The dynamic magnetic behaviors for CoCl(2)(CYpy)(4) including [CoCl(2)(py)(4)] and CoCl(2)(C1py)(4) suggested that the generated carbenes interacted with the cobalt ion to increase the relaxation time, τ(q), due to the spin quantum tunneling magnetization, which became larger with increasing S(total) of the complex.

Inhibition of C5a-induced inflammation with preserved C5b-9-mediated bactericidal activity in a human whole blood model of meningococcal sepsis.

PubMed

Sprong, Tom; Brandtzaeg, Petter; Fung, Michael; Pharo, Anne M; Høiby, E Arne; Michaelsen, Terje E; Aase, Audun; van der Meer, Jos W M; van Deuren, Marcel; Mollnes, Tom E

2003-11-15

The complement system plays an important role in the initial defense against Neisseria meningitidis. In contrast, uncontrolled activation in meningococcal sepsis contributes to the development of tissue damage and shock. In a novel human whole blood model of meningococcal sepsis, we studied the effect of complement inhibition on inflammation and bacterial killing. Monoclonal antibodies (mAbs) blocking lectin and alternative pathways inhibited complement activation by N meningitidis and oxidative burst induced in granulocytes and monocytes. Oxidative burst was critically dependent on CD11b/CD18 (CR3) expression but not on Fc gamma-receptors. Specific inhibition of C5a using mAb 137-26 binding the C5a moiety of C5 before cleavage prohibited CR3 up-regulation, phagocytosis, and oxidative burst but had no effect on C5b-9 (TCC) formation, lysis, and bacterial killing. An mAb-blocking cleavage of C5, preventing C5a and TCC formation, showed the same effect on CR3, phagocytosis, and oxidative burst as the anti-C5a mAb but additionally inhibited TCC formation, lysis, and bacterial killing, consistent with a C5b-9-dependent killing mechanism. In conclusion, the anti-C5a mAb 137-26 inhibits the potentially harmful effects of N meningitidis-induced C5a formation while preserving complement-mediated bacterial killing. We suggest that this may be an attractive approach for the treatment of meningococcal sepsis.

Synthesis and characterization of aluminum- and gallium-bridged [1.1]chromarenophanes and [1.1]molybdarenophanes.

PubMed

Lund, Clinton L; Schachner, Jörg A; Burgess, Ian J; Quail, J Wilson; Schatte, Gabriele; Müller, Jens

2008-07-07

The synthesis and structural characterization of the first [1.1]chromarenophanes and the first [1.1]molybdarenophanes are described. A salt-metathesis reaction of [2-(Me 2NCH 2)C 6H 4]AlCl 2 with freshly prepared [Cr(LiC 6H 5) 2].TMEDA (TMEDA = N, N, N', N'-tetramethylethylenediamine) resulted in the dialumina[1.1]chromarenophane [{2-(Me 2NCH 2)C 6H 4}Al(eta (6)-C 6H 5) 2Cr] 2 ( 2a). The poor solubility of 2a in organic solvents prompted us to synthesize the new intramolecularly coordinated aluminum- and gallium dichlorides [5- tBu-2-(Me 2NCH 2)C 6H 3]ECl 2 [E = Al ( 3a), Ga ( 3b)] in which the phenyl group was equipped with a tert-butyl group. Salt-metathesis reactions of 3a and 3b, respectively, with freshly prepared [M(LiC 6H 5) 2].TMEDA (M = Cr, Mo) resulted in four new [1.1]metallarenophanes of the general type [{5- tBu-2-(Me 2NCH 2)C 6H 3}E(eta (6)-C 6H 5) 2M] 2 [E = Al, M = Cr ( 4a); E = Ga, M = Cr ( 4b); E = Al, M = Mo ( 5a); E = Ga, M = Mo ( 5b)]. 2a, 4a, b, and 5a, b have been structurally characterized by single-crystal analysis [ 2a.1/2C 6H 12: C 48H 56Al 2Cr 2N 2, monoclinic, P2 1/ c, a = 9.9117(9) A, b = 19.9361(16) A, c = 10.638(2) A, alpha = 90 degrees , beta = 112.322(5) degrees , gamma = 90 degrees , Z = 2; 4a.2C 6H 6: C 62H 72Al 2Cr 2N 2, monoclinic, P2 1/ c, a = 10.9626(9) A, b = 19.3350(18) A, c = 12.4626(9) A, alpha = 90 degrees , beta = 100.756(5) degrees , gamma = 90 degrees , Z = 2; 4b.2C 6H 6: C 62H 72Cr 2Ga 2N 2, monoclinic, P2 1/ c, a = 10.8428(2) A, b = 19.4844(4) A, c = 12.4958(2) A, alpha = 90 degrees , beta = 100.6187 degrees , gamma = 90 degrees , Z = 2; 5a.2C 6H 6: C 62H 72Al 2Mo 2N 2, triclinic, P1, a = 10.4377(4) A, b = 11.6510(4) A, c = 11.6514(4) A, alpha = 73.545(3) degrees , beta = 89.318(2) degrees , gamma = 76.120(2) degrees , Z = 1; 5b.2C 6H 6: C 62H 72Ga 2Mo 2N 2, triclinic, P1, a = 10.3451(5) A, b = 11.6752(6) A, c = 11.6900(5) A, alpha = 73.917(3) degrees , beta = 89.550(3) degrees , gamma = 76.774(2) degrees , Z = 1]. All five [1.1]metallarenophanes 2a, 4a, b, and 5a, b crystallize as anti isomers with both Me 2N donor groups in exo positions ( C i point group symmetry). The new [1.1]metallarenophanes show NMR spectra that can be interpreted as being caused by time-averaged C 2 h symmetrical species, which is consistent with the findings of their molecular structures in the solid state. Variable-temperature (1)H NMR measurements for 4a, b and 5a, b (500 MHz; -90 to 90 degrees C) revealed only peak broadening in the lower temperature range of -70 to -90 degrees C. (1)H NMR saturation transfer difference experiments did not show an expected anti-to-anti isomerization, rendering the new [1.1]metallacyclophanes rigid on the NMR time scale. Electrochemical measurements were performed for 4a, b and 5a, b. However, reproducible cyclic voltammograms could only be obtained for the two gallium species 4b and 5b, revealing the expected weak communication between the two transition-metal atoms in both compounds (class II).

Functional Status after Blast-Plus-Impact Complex Concussive Traumatic Brain Injury in Evacuated United States Military Personnel

DTIC Science & Technology

2014-01-01

r o ps y c h o l o g ic a l T e st P e r fo r m...n = 4 1 ) p va lu e (n = 1 8 ) (n = 2 9 ) p va lu e 2 5 -f o o t w al k (s ec ) (m o to r st re n g th , b al an ce , co o rd in at io n ) 5 .2 – 2 .1...f A d u lt R ea d in g (e st im at e o f p re -i n ju ry v er b al in te ll ig en

Gold(III) chloride catalyzed synthesis of chiral substituted 3-formyl furans from carbohydrates: application in the synthesis of 1,5-dicarbonyl derivatives and furo[3,2-c]pyridine.

PubMed

Mal, Kanchan; Sharma, Abhinandan; Das, Indrajit

2014-09-08

This report describes a gold(III)-catalyzed efficient general route to densely substituted chiral 3-formyl furans under extremely mild conditions from suitably protected 5-(1-alkynyl)-2,3-dihydropyran-4-one using H2 O as a nucleophile. The reaction proceeds through the initial formation of an activated alkyne-gold(III) complex intermediate, followed by either a domino nucleophilic attack/anti-endo-dig cyclization, or the formation of a cyclic oxonium ion with subsequent attack by H2 O. To confirm the proposed mechanistic pathway, we employed MeOH as a nucleophile instead of H2 O to result in a substituted furo[3,2-c]pyran derivative, as anticipated. The similar furo[3,2-c]pyran skeleton with a hybrid carbohydrate-furan derivative has also been achieved through pyridinium dichromate (PDC) oxidation of a substituted chiral 3-formyl furan. The corresponding protected 5-(1-alkynyl)-2,3-dihydropyran-4-one can be synthesized from the monosaccharides (both hexoses and pentose) following oxidation, iodination, and Sonogashira coupling sequences. Furthermore, to demonstrate the potentiality of chiral 3-formyl furan derivatives, a TiBr4 -catalyzed reaction of these derivatives has been shown to offer efficient access to 1,5-dicarbonyl compounds, which on treatment with NH4 OAc in slightly acidic conditions afforded substituted furo[3,2-c]pyridine. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hereditary angioedema: management of laryngeal attacks.

PubMed

Christiansen, Sandra C; Zuraw, Bruce L

2011-01-01

Hereditary angioedema (HAE) patients suffering from laryngeal attacks in the United States faced severely limited treatment options until 2008. These potentially life-threatening episodes occur in over one-half of the patients affected by HAE during their lifetimes. Acute therapy had been relegated to supportive care, intubation, and consideration of fresh frozen plasma (FFP)--the latter with the potential for actually accelerating the speed and severity of the swelling. In this article we will review the recently approved and emerging HAE treatments that have evolved from the recognition that bradykinin generation is the fundamental abnormality leading to attacks of angioedema. Acute therapy for laryngeal attacks will be discussed including purified plasma-derived C1 inhibitor (C1INH), recombinant C1INH, an inhibitor of plasma kallikrein (ecallantide), and a B2 receptor antagonist (icatibant). Prophylactic care has also been transformed from a reliance on attenuated androgens with their attendant side effects to C1INH replacement. The arrival of these novel therapies promises to transform the future management of HAE.

[Optimization of acupoint application scheme in the treatment of bronchial asthma based on the orthogonal design method].

PubMed

Shi, Kuan; Wu, Wenzhong; Liu, Lanying; Wang, Hesheng; Chen, Dong; Liu, Chengyong; Zhang, Cong

2017-06-12

To study the primary and secondary factors of the allergic history, the frequency of acupoint application and the time of acupoint application in the treatment of bronchial asthma and optimize its scheme. Eighty patients of bronchial asthma were selected as the subjects in the orthogonal trial. The herbal medicines were the empirical formula of acupoint application (prepared at the ratio as 2:2:1:1:1:1:1:1:1 of semen brassicae , rhizome corydalis , unprocessed radix kansui , asarum sieboldii , ephedra , semen lepidii , syzygium aromaticum , cortex cinnamomi and fructus gleditsiae ) and used on bilateral Feishu (BL 13), Xinshu (BL 15), Geshu (BL 17) and Shenshu (BL 23). Firstly, two groups were divided according to allergic history (40 cases with allergic history and 40 cases without allergic history), and then four subgroups were divided on the basis of the two main groups, 10 cases in each one. Through studying three factors and two levels, i.e. allergic history (Factor A:A Ⅰ :with allergic history; A Ⅱ :without allergic history), the frequency of acupoint application (Factor B:B Ⅰ :4 times; B Ⅱ :10 times, in which, in the group of 4-time applications, the application was given once every 10 days; in the group of 10-time applications, the application was given once every 4 days); and the time of application (Factor C:C Ⅰ :4 h; C Ⅱ :8 h), the optimal scheme was screened on the basis of the attack frequency before and after treatment and the score of the asthma quality life questionnaire (AQLQ) before treatment and 6 months after treatment in the patients of each group. ① The orthogonal trial indicated that the best optimal scheme was A Ⅰ B Ⅱ C Ⅰ , meaning the patients with allergic history were treated with acupoint application for 10 times, remained for 4 h. ②Factor B (frequency of acupoint application) and C (time of acpoint application) were the significant influential factors of AQLQ scores (both P <0.05). ③The comparison of the attack frequency and AQLQ score before and after treatment in all of the patients showed that the different combinations of factor levels induced the different impacts on the asthma attack frequency and AQLQ scores. Except in the group No.1 and the group No.5, the improvements were all significant in the rest groups, indicating the significant differences ( P <0.05, P <0.01). Acupoint application reduces apparently the attack frequency of asthma in the patients and improves the living quality. The primary and secondary relationship among the allergic history, the frequency of acupoint application and the time of acupoint application for the impacts on the therapeutic effects are:the frequency of acupoint application > the time of acupoint application > the allergic history. The best optimal scheme is A Ⅰ B Ⅱ C Ⅰ , meaning the patients with allergic history are treated with acupoint application for 10 times, remained for 4h.

Trinuclear Lanthanoid Complexes of 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol with a Unique, Sandwich-Type Cage Structure(1).

PubMed

Hedinger, Roman; Ghisletta, Michele; Hegetschweiler, Kaspar; Tóth, Eva; Merbach, André E.; Sessoli, Roberta; Gatteschi, Dante; Gramlich, Volker

1998-12-28

A variety of trinuclear complexes [M(3)(H(-)(3)L)(2)](3+) [M = Y, La, Eu, Gd, Dy; L = 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci)] was prepared as solid materials of the composition M(3)(H(-)(3)L)(2)X(3).pH(2)O.qEtOH (X = Cl, NO(3); 2.5

Glass-to-metal seals comprising relatively high expansion metals

NASA Technical Reports Server (NTRS)

Hirayama, C. (Inventor)

1974-01-01

A glass suitable for glass-to-metal seals that has a resistance to attack by moisture and a high coefficient of linear thermal expansion is introduced. Linear expansion covers the range from 12 to 14 x 10 to the minus 6 C between room temperature and 500 C. The glass is essentially composed of, by molar percent, about 9% of K2O, about 10% of Na2O, about 70% of SiO2, about 6% Al2O3, and about 5% of MgO.

Synthesis of platinum(II) and palladium(II) complexes with 9,9-dihexyl-4,5-diazafluorene and their in vivo antitumour activity against Hep3B xenografted mice.

PubMed

Wang, Q-W; Lam, P-L; Wong, R S-M; Cheng, G Y-M; Lam, K-H; Bian, Z-X; Ho, C-L; Feng, Y-H; Gambari, R; Lo, Y-H; Wong, W-Y; Chui, C-H

2016-11-29

Two complexes dichloro(9,9-dihexyl-4,5-diazafluorene)platinum(II) (Pt-DHF) and dichloro(9,9-dihexyl-4,5-diazafluorene)palladium(II) (Pd-DHF) were synthesized and their in vivo antitumour activity was investigated using an athymic nude mice model xenografted with human Hep3B carcinoma cells. Pt-DHF- and Pd-DHF-treated groups showed significant tumour growth inhibition (with about 9-fold and 3-fold tumour growth retardation) when compared with the vehicle control group. The liver toxicology effects on the animals of the two compounds were investigated. Pt-DHF and Pd-DHF-treated groups had a lower alanine transaminase and aspartate transaminase values than those of the vehicle treated group as the animals from the vehicle control group had very heavy hepatoma burden. We assume that both complexes could be further investigated as effective antitumour agents and it is worthwhile to study their underlying working mechanism. Copyright © 2016 Elsevier Masson SAS. All rights reserved.

Vaccine effectiveness of tetanus toxoid, reduced diphtheria toxoid, and acellular pertussis vaccine during a pertussis outbreak in Maine.

PubMed

Terranella, Andrew; Rea, Vicki; Griffith, Matthew; Manning, Susan; Sears, Steven; Farmer, Ann; Martin, Stacey; Patel, Manisha

2016-05-11

Multiple school-associated pertussis outbreaks were reported in Maine from 2010 to 2011. These outbreaks were associated with an overall increase in pertussis cases statewide. Waning of protection in students recently vaccinated with tetanus, diphtheria, and acellular pertussis (Tdap) has been implicated in the increase in reported rates of pertussis nationally. We conducted a retrospective cohort study to evaluate Tdap vaccine effectiveness (VE) among students aged 11-19 years in two schools reporting outbreaks in 2011. All pertussis cases reported from August through November, 2011 at the two schools were included. Vaccination history was verified using provider information, state vaccine registry data, and parental verification. Attack rates (AR) were calculated. VE and duration of protection was calculated as VE=1-(ARvaccinated/ARunvaccinated)×100% using a log binomial regression model. Of 416 students enrolled, 314 were included in the analyses. Twenty-nine cases collectively in Schools A and B. Tdap coverage was 65% at School A and 42% at School B before the start of the outbreak. Among students enrolled in the study, attack rates were 11.9% and 7.7% at Schools A and B, respectively. Overall VE was 68.5% (95% confidence interval (CI) 37.7-86.2). VE was 70.4% (95% CI 17.5-89.4) for School A and 65.2% (95% CI -19.2 to 89.9) for School B. VE <2 years versus ≥2 years from outbreak onset was not significantly different. Tdap was moderately effective in preventing disease among vaccinated students. Vaccine coverage of 65% or less was suboptimal and might contribute to outbreaks. Waning VE was not demonstrated. Increased vaccination coverage rates as well as further evaluation of the role of acellular vaccine on VE is needed. Published by Elsevier Ltd.

Three novel lanthanide metal-organic frameworks (Ln-MOFs) constructed by unsymmetrical aromatic dicarboxylatic tectonics: synthesis, crystal structures and luminescent properties.

PubMed

Wu, Ya-Pan; Li, Dong-Sheng; Xia, Wei; Guo, Sha-Sha; Dong, Wen-Wen

2014-09-11

Three novel Ln(III)-based coordination polymers, {[Ln2 (2,4-bpda)3 (H2O)x]·yH2O}n (Ln = La (III) (1), x = 2, y = 0, Ce (III) (2), Pr (III) (3), x = 4, y = 1) (2,4-H2bpda = benzophenone-2,4-dicarboxylic acid) have been prepared via a solvothermal method and characterized by elemental analysis, IR, and single-crystal X-ray diffraction techniques. Complex 1 exhibits a 3D complicated framework with a new 2-nodal (3,7)-connected (42·5) (44·51·66·8) topology. Complexes 2 and 3 are isomorphous, and feature a 3D 4-connected (65·8)-CdSO4 network. Moreover, solid-state properties such as thermal stabilities and luminescent properties of 1 and 2 were also investigated. Complex 1 crystallized in a monoclinic space group P21/c with a = 14.800 (3), b = 14.500 (3), c = 18.800 (4) Å, β = 91.00 (3), V = 4033.9 (14) Å3 and Z = 4. Complex 2 crystallized in a monoclinic space group Cc with a = 13.5432 (4), b = 12.9981 (4), c = 25.7567 (11) Å, β = 104.028 (4), V = 1374.16 (7) Å3 and Z = 4.

Reversible CO exchange at platinum(0). An example of similar complex properties produced by ligands with very different stereoelectronic characteristics.

PubMed

Forrest, Sebastian J K; Pringle, Paul G; Sparkes, Hazel A; Wass, Duncan F

2014-11-21

The ligands 1,2-C6H4(CH2P(t)Bu2)2 (La) and 1,2-C6H4(P(t)Bu2)(CH2P(t)Bu2) (Lb) displace norbornene (nbe) from [Pt(η(2)-nbe)3] to give [PtL(η(2)-nbe)] where L = La (1a) or Lb (1b); 1a is fluxional on the NMR timescale. Reaction of 1a,b with CO gives the corresponding monocarbonyls [PtL(CO)] where L = La (2a) or Lb (2b) which then react further, and reversibly, to give the dicarbonyls [PtL(CO)2] where L = La (3a) or Lb (3b). The CO interchange between 2a,b and 3a,b is compared with the only other such system (2f and 3f), which are complexes of (C2F5)2PCH2CH2P(C2F5)2 (Lf). Ethene reacts smoothly with 2a to give (4a) and H2 with 2a generates some [PtH2(La)]. Protonation of 2a gives [Pt(La)(H)(CO)][B(C6F5)4] (5a) whose crystal structure has been determined. Similarly protonation of 2b gives [Pt(Lb)(H)(CO)][B(C6F5)4] as a mixture of geometric isomers 5b–6b.

Ministry of Defence Main Estimates 2009-10

DTIC Science & Technology

2009-07-02

fR 2 M O G C ha ng es " 13 .7 " 13 .7 " 13 .7 0. 0 F le x C ap it al to R es ou rc e. 60 0. 0 60 0. 0...as h R el ea se 48 .9 48 .9 " 48 .9 0 0. 0 N D P B C os ts 13 2. 1 9. 5 14 1. 6 14 1. 6 0. 9 0. 9 R fR 1 T ot al 23 ,8 87 .1 11 ,6 32 .5 35 ,5 19 .6 17...rs O ut " 28 .0 " 28 .0 " 28 .0 R es er ve B id 2, 38 4. 3 42 2.

The 8th and 9th tandem spectrin-like repeats of utrophin cooperatively form a functional unit to interact with polarity-regulating kinase PAR-1b.

PubMed

Yamashita, Kazunari; Suzuki, Atsushi; Satoh, Yoshinori; Ide, Mariko; Amano, Yoshiko; Masuda-Hirata, Maki; Hayashi, Yukiko K; Hamada, Keisuke; Ogata, Kazuhiro; Ohno, Shigeo

2010-01-01

Utrophin is a widely expressed paralogue of dystrophin, the protein responsible for Duchenne muscular dystrophy. Utrophin is a large spectrin-like protein whose C-terminal domain mediates anchorage to a laminin receptor, dystroglycan (DG). The rod domain, composed of 22 spectrin-like repeats, connects the N-terminal actin-binding domain and the C-terminal DG binding domain, and thus mediates molecular linkage between intracellular F-actin and extracellular basement membrane. Previously, we demonstrated that a cell polarity-regulating kinase, PAR-1b, interacts with the utrophin-DG complex, and positively regulates the interaction between utrophin and DG. In this study, we demonstrate that the 8th and 9th spectrin-like repeats (R8 and R9) of utrophin cooperatively form a PAR-1b-interacting domain, and that Ser1258 within R9 is specifically phosphorylated by PAR-1b. Substitution of Ser1258 to alanine reduces the interaction between utrophin and DG, suggesting that the Ser1258 phosphorylation contributes to the stabilization of the utrophin-DG complex. Interestingly, PAR-1b also binds and phosphorylates R8-9 of dystrophin, and colocalizes with dystrophin at the skeletal muscle membrane. These results reveal a novel function of the rod domain of utrophin beyond that of a passive structural linker connecting the N- and C-terminal domain. Copyright 2009 Elsevier Inc. All rights reserved.

Teaching Patriotism--with Conviction

ERIC Educational Resources Information Center

Finn, Chester E., Jr.

2006-01-01

Americans will debate for many years to come the causes and implications of the September 11 attacks on New York City and Washington, D.C., as well as the foiled attack that led to the crash of United Airlines Flight 93 in a Pennsylvania field. Between the first and second "anniversaries" of 9/11, another development deepened their…

Target discovery of cytotoxic withanolides from Physalis angulata var. villosa via reactivity-based screening.

PubMed

Zhang, Yi; Chen, Chen; Zhang, Ya-Long; Kong, Ling-Yi; Luo, Jian-Guang

2018-03-20

The reactivity-based screening (RBS) was developed for directed discovery of cytotoxic withanolides. In this study, a thiol probe, 4-chlorobenzenethiol, was used to selectively attack cytotoxic withanolides containing potential pharmacophore, 2(3)-en-1-one in ring A (AEO) and 5β,6β-epoxy in ring B (BE), from the plant extract of Physalis angulata var. villosa. The screening was performed based on the potential mechanism of 4-chlorobenzenethiol nucleophilic addition to AEO, followed by detection of adducts using liquid chromatography quadrupole-time-of-flight mass spectrometry (LC-Q-TOF-MS). Guided by RBS, eleven target withanolides, including five new compounds, physagulides R-V (10-14) and six known ones (2, 7-9, 15, 16) were discovered. All of them exhibited cytotoxicity against the both tested cell lines, especially, compounds 2, 7, 8 and 14 showed potent activities with IC 50 values of 1.57-6.29 μM. The results suggested that RBS was efficient and accurate for rapid identification of cytotoxic withanolides and could guide isolation of target components from the complex medicinal plant extract. Copyright © 2018 Elsevier B.V. All rights reserved.

FY 1980 Report on Dye Laser Materials

DTIC Science & Technology

1981-02-01

C02H H Rh 19 H C2H 5 CH3 CO9H H i Rh6G H C2H 5 CH3 Co2 C2H5 H RhB C2H5 C2H!5 H CO,H H Rh3B C2A5 C2H5 H CO2CH 5 H Rh 101 RING- RING RING...Dye designations Ring SRh 101 Rh 101 - Diethyl SRh B Rh B Rhb 3B Mono ethyl (methyl) -- Rh 19 (116) Rh 6G Unsubstituted -- Rh 110 Rh 123 Nominal Single...Broadband Lasing Wave-lengths of the Rhodamine Dyes. Lasing Wavelength, n Approximate Dye Conc. x 104 Range Midpoint Rh 110 1.0 567-577 572 2.0 Rh 123

Diverse reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) towards alkali metal, group 9 metal, and coinage metal precursors† †Electronic supplementary information (ESI) available: Experimental and calculation details, and crystallographic information for 2, 3, 4, 6, 8. CCDC 1038665, 1038666, 1038667, 1011534, and 1011533. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc00404g Click here for additional data file. Click here for additional data file.

PubMed Central

Kong, Lingbing; Ganguly, Rakesh; Li, Yongxin

2015-01-01

The reactivity of a tricoordinate organoboron L2PhB: (L = oxazol-2-ylidene) 1 towards metal precursors and its coordination chemistry were comprehensively studied. While the boron center in 1 is reluctant to coordinate to the alkali metals in their trifluoromethanesulfonate salts (MOTf) (M = Li, Na, K), the unprecedented compound 2 containing two L2PhB: units linked by a cyclic Li(OTf)2Li spacer was obtained from the reaction of 1 with LiOTf. Treatment of 1 with group 9 metal complexes [MCl(COD)]2 (M = Rh, Ir) afforded the first zwitterionic rhodium(i)–boronium complex 3 and the iridium(iii)–borane complex 4, respectively. The reaction pathway may involve C–H activation followed by proton migration from the metals to the boron center, demonstrating the first example of the deprotonation of metal hydrides by a basic boron. In the reactions with coinage metals, 1 could act as a two-electron reducing agent towards the metal chlorides MCl (M = Cu, Ag, Au). Meanwhile, the reaction of 1 with gold chloride supported by a N-heterocyclic carbene (NHC) produced a heteroleptic cationic gold complex [(L2PhB)Au(NHC)]Cl (6) featuring both carbene and L2PhB: ligands on the gold atom. In contrast, an isolable gold chloride complex (L2PhB)AuCl (8) was obtained by direct complexation between 1 and triphenylphosphine-gold chloride via ligand exchange. X-ray diffraction analysis and computational studies revealed the nature of the B:→Au bonding interaction in complexes 6 and 8. Natural Population Analysis (NPA) and Natural Bond Orbital (NBO) analysis support the strong σ-donating property of the L2PhB: ligand. Moreover, preliminary studies showed that complex 8 can serve as an efficient precatalyst for the addition of X–H (X = N, O, C) to alkynes under ambient conditions, demonstrating the first application of a metal complex featuring a neutral boron-based ligand in catalysis. PMID:29308167

Cellulosic-Derived Biofuels Program in Kentucky - Part 2

DTIC Science & Technology

2014-04-30

and lignin, are complex raw materials. Selection of robust strains of algae that are able to convert C6 (glucose) and C5 carbohydrates from...13 Task B2.03 Development of Metalloporphyrin-Ionic Liquid Complexes for Degradation of Biomass . 14 Task B2.04 –Biomass Conversion Process Scale...Up ............................................................................. 15 Task B3: Carbohydrate to Oil Conversion Process Development

Biophysical Characterization of Copolymer-Protected Gene Vectors (COPROGs)

PubMed Central

Hönig, Daniel; DeRouchey, Jason; Jungmann, Ralf; Koch, Christian; Plank, Christian; Rädler, Joachim O.

2010-01-01

A copolymer-protected gene vector (COPROG) is a three component gene delivery system consisting of a preformed DNA and branched polyethylenimine (bPEI) complex subsequently modified by the addition of a copolymer (P6YE5C) incorporating both poly(ethylene glycol) (PEG) and anionic peptides. Using fluorescence correlation spectroscopy (FCS) and atomic force microscopy (AFM), we characterized and compared the self-assembly of bPEI/DNA particles and COPROG complexes. In low salt buffer, both bPEI/DNA and COPROG formulations form stable nanoparticles with hydrodynamic radii between 60–120 nm. COPROG particles, as compared to bPEI/DNA, show greatly improved particle stability to both physiological salt as well as low pH conditions. Binding stoichiometry of the three-component COPROG system was investigated by dual-color fluorescence cross-correlation spectroscopy (FCCS). It was found that a significant fraction of P6YE5C copolymer aggregates with excess bPEI forming bPEI/P6YE5C “ghost complexes” with no DNA inside. The ratio of ghost particles to COPROG complexes is about 4:1. In addition we find a large fraction of excess P6YE5C copolymer, which remains unbound in solution. We observe a 2–4 fold enhanced reporter gene expression with COPROG formulations at various equivalents as compared to bPEI-DNA alone. We believe that both complex stabilization as well as the capture of excess bPEI into ghost particles induced by the copolymer is responsible for the improvement in gene expression. PMID:20672861

Novel Processing of Boron Carbide (B4C): Plasma Synthesized Nano Powders and Pressureless Sintering Forming of Complex Shapes

DTIC Science & Technology

2008-12-01

Figure 4. B4C plates formed via hot pressing with a curved shape. Commercial B4C shows a large number of lenticular graphitic inclusions, Figure 5...materials and they act as crack initiation points in flexure testing. Figure 5. SEM micrograph showing large lenticular graphitic inclusions in commercial

Clinical roundtable monograph: Paroxysmal nocturnal hemoglobinuria: a case-based discussion.

PubMed

Szer, Jeff; Hill, Anita; Weitz, Ilene Ceil

2012-11-01

Paroxysmal nocturnal hemoglobinuria (PNH) is a rare, acquired disorder characterized by chronic intravascular hemolysis as the primary clinical manifestation and morbidities that include anemia, thrombosis, renal impairment, pulmonary hypertension, and bone marrow failure. The prevalence of the PNH clone (from <1-100% PNH granulocytes) is approximately 16 per million, and careful monitoring is required. The average age of onset of the clinical disease is the early 30s, although it can present at all ages. PNH is caused by the acquisition of a somatic mutation of the gene phosphatidylinositol glycan anchor (PIG-A) in a multipotent hematopoietic stem cell (HSC), with clonal expansion of the mutated HSC. The mutation causes a deficiency in the synthesis of glycosylphosphatidylinositol (GPI). In cells derived from normal HSCs, the complement regulatory proteins CD55 and CD59 are anchored to the hematopoietic cell membrane surface via GPI, protecting the cells from complement-mediated lysis. However, in patients with PNH, these 2 proteins, along with numerous other GPI-linked proteins, are absent from the cell surface of red cells, granulocytes, monocytes, and platelets, resulting in complement-mediated intravascular hemolysis and other complications. Lysis of red blood cells is the most obvious manifestation, but as other cell lineages are also affected, this complement-mediated attack contributes to additional complications, such as thrombosis. Eculizumab, a humanized monoclonal antibody against the C5 complement protein, is the only effective drug therapy for PNH patients. The antibody prevents cleavage of the C5 protein by C5 convertase, in turn preventing generation of C5b-9 and release of C5a, thereby protecting from hemolysis of cells lacking the CD59 surface protein and other complications associated with complement activation. Drs. Ilene C. Weitz, Anita Hill, and Jeff Szer discuss 3 recent cases of patients with PNH.

Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

PubMed

Heshmat, Mojgan; Privalov, Timofei

2017-07-06

By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H 2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C 6 F 5 ) 3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H 2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H 2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H 2 splitting at the carbonyl carbon atom of (C 6 F 5 ) 3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C 6 F 5 ) 3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C 6 F 5 ) 3 B, as a catalyst, namely, 1) the step of H 2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C 6 F 5 ) 3 B-ketone adducts in which (C 6 F 5 ) 3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C 6 F 5 ) 3 B-alkoxide intermediate giving the (C 6 F 5 ) 3 B-alcohol adduct, and 3) the S N 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogenation of Carbon Dioxide Catalyzed by Ruthenium Trimethylphosphine Complexes: A Mechanistic Investigation using High-Pressure NMR Spectroscopy

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

Getty, April D.; Tai, Chih-Cheng; Linehan, John C.

2009-08-26

The previously reported complex, cis-(PMe3)4RuCl(OAc) (1) acts as a catalyst for CO2 hydrogenation into formic acid in the presence of a base and an alcohol co-catalyst. NMR spectroscopy has revealed that 1 exists in solution in equilibrium with fac-(PMe3)3RuCl(h2-OAc) (2), [(PMe3)4Ru(h2-OAc)]Cl (3a), and free PMe3. Complex 2 has been isolated and characterized by elemental analysis, NMR spectroscopy, and X-ray crystallography. 2 has been tested as a CO2 hydrogenation catalyst, however, it performed poorly under the conditions of catalysis used for 1. Complex 3a can be prepared by adding certain alcohols, such as MeOH, EtOH, or o-C6H5OH, to a solution ofmore » 1 in CDCl3. The chloride ion of 3a has been exchanged for the non-coordinating anions BPh4 or B(ArF )4 (B(ArF)4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate) to produce [(PMe3)4Ru(h2-OAc)]BPh4 (3b) and [(PMe3)4Ru(h2-OAc)]B(ArF)4 (3c). Both of these complexes have been isolated and characterized by elemental analysis, NMR spectroscopy, and in the case of 3b, X-ray crystallography. Complexes 3b and 3c perform just as well as 1 for CO2 hydrogenation to formic acid in the presence of an alcohol co-catalyst; however, 3b,c perform equally well without the added alcohol. High-pressure NMR has been used to investigate the mechanism of CO2 hydrogenation via 3a,b in the presence of base. Two of the intermediates involved have been identified as cis-(PMe3)4RuH2 (5) and cis-(PMe3)4Ru(H)O2CH (6), and the role of the base includes not only trapping of the formic acid product, but also initiation of the catalysis by aiding the conversion of 3b,c to 5.« less

Space shuttle: Longitudinal and lateral aerodynamic characteristics of the 0.0035-scale GD/C aerospace booster (B-15B-1)

NASA Technical Reports Server (NTRS)

Debevoise, J. M.; Mcginnis, R. F.

1972-01-01

Force tests on a 0.0035-scale model of the General Dynamics/Convair space shuttle B-15B-1 booster were conducted in the MSFC trisonic wind tunnel during February and March 1971. Longitudinal and lateral characteristics were obtained at Mach numbers from 0.6 to 4.96. The configuration tested had a low delta wing, all-movable canard controls of delta planform, and a single vertical tail. Most of the test was devoted to obtaining data relevant to the transition from atmospheric reentry to subsonic cruise. In that portion of the test the angles of attack ranged from 6 degrees to 60 degrees, and yaw runs were made at angles of attack of 15 and 35 degrees. The rest of the test was devoted to obtaining booster-alone buildup data relevant to the launch phase. For the launch phase, the Mach number range was from 0.6 to 2.0, the angles of attack were from -10 to +10 degrees, and yaw runs were made at zero angle of attack.

Officer Career Development: Cross-Sectional Sample -- Fiscal Years 1986 - 1987

DTIC Science & Technology

1991-09-01

E9B7 - - - - - - 1 0545 4. Recruiting E9El1 E9Bl1 - - - - - - 1 0546 5. PG School E9E13 E9B13 - - - - - - 1 0547 NOTES: Respose sale iffes in SOResponse...been made to me. 7. I had accepted a job offer. 8. Net applicable-I knew that I would be self - employed. 9. Nct applicanle-I had not looked for a job...1 1635 8. Self -employ - - - - C9H C9H - - 1 16363 9. Not applicabl- - - - C91 C91 - - 1 1637 NOTES:3 F-118 PERSONNEL DISTRIBUTION AND CAREER

Synthesis of New Inorganic and Organometallic Materials.

DTIC Science & Technology

1981-04-23

15. 16. & 17 . Distribution Statement Approved for public release; distribution unlimited. 18. Supplementary, Note’s’ 19. Key Words .. t rganometallic...CarbametallIaboranes 12 2. Activation of Acetylenes and Olefins by Metal Complexes 16 (a) Nickel 16 (b) Molybdenum 17 (c) Platinum 24 3. Fluorocarbon...Figure 9).3 - CO / Pt -. . . Pt 4Ph ’ / C-Fe C C C0 0 oc-( I C- Co FIGURE 9. Possible mode for conversion C’,p - h 3 of the anion into the metal

Comparative Heavy Metal Uptake by Soil-Dwelling Invertebrates and the Bioassay Earthworm Eisenia Foetida

DTIC Science & Technology

1988-03-31

NUMBER IN POOLED SAMPLE AT EACH PLOT Al Tettigoniidao 5-- -- -- - -- -- - -- -- - -- -- - - -- - -- - Al Tettigoniidae 5 A3 Tettigoniidas 7 A4... Tettigoniidae 28 B) Tettigoniidae 10 82 Tettigoniidae 34 B3 Tettigoniidae 8 B4 Tettlioniidae 9 B5 Tettigoniidae 14 Cl Tottigoniida. 81 Acridiidae I C2...Ttttigoniidat 58 C3Tettigoniidae 28 C4 Tettigoniida . 17 15 TABLE 2 contd... TABLE 2(c) Composition of soil dwelling invertebrate fauna sampled by pitfall traps

Photovoltaic Array Space Power Plus Diagnostics Experiment

DTIC Science & Technology

1990-11-01

28.97144 71 01000111 47 01100100 64 -28.4806 72 01001000 48 01101100 6C -27.98926 73 01001001 In 01101101 6D -27.49739 74 01001010 4A 01101111 6F...107 01101011 6B 01011110 5E -10.46867 108 01101100 6C 01011010 5A -9.960138 109 01101101 6D 01011011 5B -9.451286 110 01101110 6E 01011001 59

Molecular structure, vibrational spectra and quantum chemical MP2/DFT studies toward the rational design of hydroxyurea imprinted polymer

NASA Astrophysics Data System (ADS)

Prasad, Bhim Bali; Rai, Garima

2013-03-01

In this study, both experimental and theoretical vibrational spectra of template (hydroxyurea, HU), monomer (N-(4,6-bisacryloyl amino-[1,3,5] triazine-2-yl-)-acryl amide, TAT), and HU-TAT complexes were compared and these were respectively found to be in good agreement. Binding energies of HU, when complexed with different monomers, were computed using second order Moller Plesset theory (MP2) at 6-311++G(d,p) level both in the gas as well as solution phases. HU is an antineoplastic agent extensively being used in the treatment of polycythaemia Vera and thrombocythemia. It is also used to reduce the frequency of painful attacks in sickle cell anemia. It has antiretroviral property in disease like AIDS. All spectral characterizations were made using Density Functional Theory (DFT) at B3LYP employing 6-31+g(2d, 2p) basis set. The theoretical values for 13C and 1H NMR chemical shifts were found to be in accordance with the corresponding experimental values. Of all different monomers studied for the synthesis of molecularly imprinted polymer (MIP) systems, the monomer TAT (2 mol) was typically found to have a best binding score requisite for complexation with HU (1 mol) at the ground state.

A Next Generation Repository for Sharing Sensitive Network and Security Data

DTIC Science & Technology

2018-01-01

submission, and 5 yearly IRB reviews d. Provided legal support for MOA data provider and host agreements and amendments e. Feedback and bug reporting...intrusion detection methods and systems , b) event- reconstruction and evidence-based insights into global trends (e.g., DDoS attacks and malware...propagation), and c) situational awareness (e.g., outage detection). We have leveraged IMPACT’s policy and legal framework to minimize any risks associated

Bytes: Weapons of Mass Disruption

DTIC Science & Technology

2002-04-01

advances compound the problems of protecting complex global infrastructures from attacks. How should the U.S. integrate the many disparate...deploy and sustain military forces.".16 According to the direst of information warfare theories , all computer systems are vulnerable to attack. The...Crisis Show of Force Punitive Strikes Armed Intervention Regional Conflict Regional War Global Conventional War Strategic Nuclear War IW & C2W area of

Winning Teams: Mobilization -- Related Correlates of Success in American World War II Infantry Divisions.

DTIC Science & Technology

1985-05-10

piecemeal to form an overall impression of a division first battle. 4 5 The 92nd Infantry Division, consisting of black 4 enlisted men and black and white...The conventional wisdom was that the 92nd’s failure reflected a complex of problems at the time 47associated with black divisions. There were, as we...attacked after Ii. having been hurriedly rushed forward to plug holes in the line.9 8 None of the divisions unsuccessful in their first major battles

Crystal structure of a photolysis product of vitamin B6: A pyridodihydrofuran-condensed skeleton compound of pyridoxal 5‧-phosphate

NASA Astrophysics Data System (ADS)

Aoki, Katsuyuki; Nakamura, Hideyuki; Hattori, Toshiaki; Hu, Ning-Hai; Onishi, Masayoshi

2017-11-01

An aqueous solution dissolving pyridoxal 5‧-phosphate (PLP) was exposed to sun-light at room temperature to yield a photolysis product, 4b,9b-dihydro-4b,9b-dihydroxy-1,6-dimethyl-4,9-bis(phosphonooxymethyl){pyrido[3‧,4‧:2,3]furo[4,5-b]}pyrido[4,3-d]furan (1), whose structure was crystallographically determined. The product 1 was found to be a novel C(sp3)-C(sp3) side-sharing pyridodihydrofuran-condensed skeleton compound with the two pyridodihydrofuran planes taking a 'V-shape'-like molecular configuration. Hydrogen bonding patterns of molecules of 1 in the crystal lattice are analyzed by the graph set approach. The most probable mechanism for the formation of 1 is described.

Unexpected Reactivity of [(η(5) -1,2,4-tBu3 C5 H2 )Ni(η(3) -P3 )] towards Main Group Nucleophiles and by Reduction.

PubMed

Mädl, Eric; Balázs, Gábor; Peresypkina, Eugenia V; Scheer, Manfred

2016-06-27

The reduction of [Cp'''Ni(η(3) -P3 )] (1; Cp'''=η(5) -1,2,4-tBu3 C5 H2 ) with potassium produces the complex anion [(Cp'''Ni)2 (μ,η(2:2) -P8 )](2-) (2), which contains a realgar-like P8 unit. The anionic triple-decker sandwich complex [(Cp'''Ni)2 (μ,η(3:3) -P3 )](-) (3) with a cyclo-P3 middle deck is obtained when 1 is treated with NaNH2 as a nucleophile. Na[3] can subsequently be oxidized with AgOTf to the neutral triple-decker complex [(Cp'''Ni)2 (μ,η(3:3) -P3 )] (4). In contrast, 1 reacts with LiPPh2 to give the anionic compound [(Cp'''Ni)2 (μ,η(2:2) -P6 PPh2 )](-) (5), a complex containing a bicyclic P7 fragment capped by two Cp'''Ni units. Protonation of Li[5] with HBF4 leads to the neutral complex [(Cp'''Ni)2 (μ,η(2:2) -(HP6 PPh2 )] (6). Adding LiNMe2 to 1 results in [Cp'''Ni(η(2) -P3 NMe2 )](-) (7) becoming accessible, a complex which forms as a result of nucleophilic attack at the cyclo-P3 ring of 1. The complexes K2 [2], Na[3], 4, 6, and Li[7] were fully characterized and their structures determined by single-crystal X-ray diffraction. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bis(1,3-di-tert-butylimidazolin-2-iminato) titanium complexes as effective catalysts for the monodisperse polymerization of propylene.

PubMed

Sharma, Manab; Yameen, Haneen Simaan; Tumanskii, Boris; Filimon, Sabina-Alexandra; Tamm, Matthias; Eisen, Moris S

2012-10-17

The use of bis(1,3-di-tert-butylimidazolin-2-iminato) titanium dichloride (1) and dimethyl (2) complexes in the polymerization of propylene is presented. The complexes were activated using different amounts of methylalumoxane (MAO), giving in each case a very active catalytic mixture and producing polymers with a narrow molecular weight distribution (polydispersity = 1.10). The use of the cocatalyst triphenylcarbenium (trityl) tetra(pentafluorophenyl)borate totally inhibits the reaction, producing the corresponding bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(III) methyl complex, the trityl radical ((•)CPh(3)), the anionic MeB(C(6)F(5))(4)(-), B(C(6)F(5))(3), and the bis(1,3-di-tert-butylimidazolin-2-iminato) titanium(IV) dimethyl·B(C(6)F(5))(3) complex. The use of a combination of physical methods such as NMR, ESR-C(60), and MALDI-TOF analyses enabled us to propose a plausible mechanism for the polymerization of propylene, presenting that the polymerization is mainly carried out in a living fashion. In addition, we present a slow equilibrium toward a small amount of a dormant species responsible for 2,1-misinsertions and chain transfer processes.

Determination of the Complex Elastic Moduli of Materials Using A Free- Free Bar Technique

DTIC Science & Technology

1994-03-01

LCDR, Dr. D. L alner 1 Dept. of Physics (Code PH) Naval Postgrdumt School Monterey, CA 93943 10 . Cgimd Ofric. Naval Reserh Labrary ATI’N: Dr. N...Postgraduate School ( fAp~hicbl) Naval Postgraduate School 6c. ADDRESS MclY- $Mae, 02t c7;w 3 7b. ADDRESS (city, MUk and ii? code) Mogntere CA 93943-5=0...Monery CA 93943-5000 Sa. NAME OF FUNDDOISIONS0R]NG G. OFMiCE SYMBOL 9. FUU1ENIICMN IDTFCTONNUMBER ORGANUAT1ON j (If Appkiabie) NSWC. CRANE. NPS

Better Ceramics Through Chemistry IV. Materials Research Society Sumposium Proceedings. Volume 180

DTIC Science & Technology

1991-03-31

GELS 117 L.F. Nazar, D.G. Napier, D. Lapham, and E. Epperson SMALL ANGLE X - RAY SCATTERING STUDIES Or POLYMERIC ZIRCONIUM SPECIES IN AQUEOUS SOLUTION...recently obtained the first X - ray crystallographic data on bismuth alkoxides, Bi(OR) 3 (R = C(CH3) 3 and C6 H4 (CH 3 )2 -2,6) [8]. These data showed that...d8, ppm): 12.5 (O2CMe), 9.6 (OCMe3). The complex was identified by X - ray crystallography. 1 crystallizes in space group P21/n with a = 13.149(2) A, b

Synthesis of novel Eu(III) luminescent probe based on 9- acridinecarboxylic acid skelton for sensing of ds-DNA.

PubMed

Azab, Hassan A; Hussein, Belal H M; El-Falouji, Abdullah I

2012-03-01

Eu(III)-9-acridinecarboxylate (9-ACA) complex was synthesized and characterized by elemental analysis, conductivity measurement, IR spectroscopy, thermal analysis, mass spectroscopy, (1)H-NMR, fluorescence and ultraviolet spectra. The results indicated that the composition of this complex is [Eu(III)-(9-ACA)(2)(NCS)(C(2)H(5)OH)(2)] 2.5 H(2)O and the oxygen of the carbonyl group coordinated to Eu(III). The interaction between the complex with nucleotides guanosine 5'- monophosphate (5'-GMP), adenosine 5'-diphosphates (5'-ADP), inosine (5'-IMP) and CT-DNA was studied by fluorescence spectroscopy. The fluorescence intensity of Eu(III)-9-acridinecarboxylate complex was enhanced with the addition of CT-DNA. The effect of pH values on the fluorescence intensity of Eu(III) complex was investigated. Under experimental conditions, the linear range was 9-50 ng mL(-1) for calf thymus DNA (CT- DNA) and the corresponding detection limit was 5 ng mL(-1). The results showed that Eu(III)-(9-ACA)(2) complex binds to CT-DNA with stability constant of 2.41 × 10(4) M.

Analysis and Evaluation of Project EVERGREEN Data

DTIC Science & Technology

1991-09-01

1 9 9c9" 9 9 9 91?t- VI vi rl i v AH AR AA R a- 6 4 h 1" t - 10 i h t -: .4 .a: : t : 3 t : ta at ~ ~’~ M ~4C ~ C0.~b ~ ~ qO ~ Cm @ el 0. z ~M C q f... Anton , Howard and Rorres , Chris, Elementary Linear Algebra with AyDlications, John Wiley and Sons, New York, 1987. 2. Binnall, Eugene P., EVERGREEN... C . ANALYSIS OF INDIVIDUAL WAVEFORMS.........52 1. Directory 5-1-90 . . . . . .. .. .. .. ... 58 a. Waveform NTSO4BO1.WFM............58 b. Waveform

C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex.

PubMed

Man, Wai-Lun; Xie, Jianhui; Pan, Yi; Lam, William W Y; Kwong, Hoi-Ki; Ip, Kwok-Wa; Yiu, Shek-Man; Lau, Kai-Chung; Lau, Tai-Chu

2013-04-17

We report experimental and computational studies of the facile oxidative C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex. We provide evidence that the initial step involves nucleophilic attack of aniline at the nitrido ligand of the ruthenium complex, which is followed by proton and electron transfer to afford a (salen)ruthenium(II) diazonium intermediate. This intermediate then undergoes unimolecular decomposition to generate benzene and N2.

Scandium complexes with the tetraphenylethylene and anthracene dianions.

PubMed

Ellis, John E; Minyaev, Mikhail E; Nifant'ev, Ilya E; Churakov, Andrei V

2018-06-01

The structural study of Sc complexes containing dianions of anthracene and tetraphenylethylene should shed some light on the nature of rare-earth metal-carbon bonding. The crystal structures of (18-crown-6)bis(tetrahydrofuran-κO)sodium bis(η 6 -1,1,2,2-tetraphenylethenediyl)scandium(III) tetrahydrofuran disolvate, [Na(C 4 H 8 O) 2 (C 12 H 24 O 6 )][Sc(C 26 H 20 ) 2 ]·2C 4 H 8 O or [Na(18-crown-6)(THF) 2 ][Sc(η 6 -C 2 Ph 4 ) 2 ]·2(THF), (1b), (η 5 -1,3-diphenylcyclopentadienyl)(tetrahydrofuran-κO)(η 6 -1,1,2,2-tetraphenylethenediyl)scandium(III) toluene hemisolvate, [Sc(C 17 H 13 )(C 26 H 20 )(C 4 H 8 O)]·0.5C 7 H 8 or [(η 5 -1,3-Ph 2 C 5 H 3 )Sc(η 6 -C 2 Ph 4 )(THF)]·0.5(toluene), (5b), poly[[(μ 2 -η 3 :η 3 -anthracenediyl)bis(η 6 -anthracenediyl)bis(η 5 -1,3-diphenylcyclopentadienyl)tetrakis(tetrahydrofuran)dipotassiumdiscandium(III)] tetrahydrofuran monosolvate], {[K 2 Sc 2 (C 14 H 10 ) 3 (C 17 H 13 ) 2 (C 4 H 8 O) 4 ]·C 4 H 8 O} n or [K(THF) 2 ] 2 [(1,3-Ph 2 C 5 H 3 ) 2 Sc 2 (C 14 H 10 ) 3 ]·THF, (6), and 1,4-diphenylcyclopenta-1,3-diene, C 17 H 14 , (3a), have been established. The [Sc(η 6 -C 2 Ph 4 ) 2 ] - complex anion in (1b) contains the tetraphenylethylene dianion in a symmetrical bis-η 3 -allyl coordination mode. The complex homoleptic [Sc(η 6 -C 2 Ph 4 ) 2 ] - anion retains its structure in THF solution, displaying hindered rotation of the coordinated phenyl rings. The 1D 1 H and 13 C{ 1 H}, and 2D COSY 1 H- 1 H and 13 C- 1 H NMR data are presented for M[Sc(Ph 4 C 2 ) 2 ]·xTHF [M = Na and x = 4 for (1a); M = K and x = 3.5 for (2a)] in THF-d 8 media. Complex (5b) exhibits an unsymmetrical bis-η 3 -allyl coordination mode of the dianion, but this changes to a η 4 coordination mode for (1,3-Ph 2 C 5 H 3 )Sc(Ph 4 C 2 )(THF) 2 , (5a), in THF-d 8 solution. A 45 Sc NMR study of (2a) and UV-Vis studies of (1a), (2a) and (5a) indicate a significant covalent contribution to the Sc-Ph 4 C 2 bond character. The unique Sc ate complex, (6), contains three anthracenide dianions demonstrating both a η 6 -coordination mode for two bent ligands and a μ 2 -η 3 :η 3 -bridging mode of a flat ligand. Each [(1,3-Ph 2 C 5 H 3 ) 2 Sc 2 (C 14 H 10 ) 3 ] 2- dianionic unit is connected to four neighbouring units via short contacts with [K(THF) 2 ] + cations, forming a two-dimensional coordination polymer framework parallel to (001).

Free-radical reactions induced by OH-radical attack on cytosine-related compounds: a study by a method combining ESR, spin trapping and HPLC.

PubMed Central

Hiraoka, W; Kuwabara, M; Sato, F; Matsuda, A; Ueda, T

1990-01-01

Free-radical reactions induced by OH-radical attack on cytosine-related compounds were investigated by a method combining ESR, spin trapping with 2-methyl-2-nitrosopropane and high-performance liquid chromatography (HPLC). Cytidine, 2'-deoxycytidine, cytidine 3'-monophosphate, cytidine 5'-monophosphate, 2'-deoxycytidine 5'-monophosphate and their derivatives, of which 5,6-protons at the base moiety were replaced by deuterons, and polycytidylic acid (poly(C] were employed as samples. OH radicals were generated by X-irradiating an N2O-saturated aqueous solution. Five spin adducts were separated by HPLC. Examination of them by ESR spectroscopy and UV photospectrometry showed that spin adducts assigned to C5 and C6 radicals due to OH addition to the 5,6 double-bond, a deaminated form of the spin adduct derived from a C5 radical due to the cyclization reaction between C5' of the sugar and C6 of the base, and a spin adduct assigned to the C4' radical due to H abstraction by OH radicals were produced. From these results the sites of OH-radical attack and the subsequent radical reactions in cytosine-related compounds were clarified. PMID:2157193

Synthesis, structure, spectroscopic and electrochemical properties of bis(histamine-saccharinate) copper(II) complex

NASA Astrophysics Data System (ADS)

Bulut, İclal; Uçar, İbrahim; Karabulut, Bünyamin; Bulut, Ahmet

2007-05-01

Crystal structure of [Cu(hsm) 2(sac) 2] (hsm is histamine and sac is saccharinate) complex has been determined by X-ray diffraction analyses and its magnetic environment has been identified by electron paramagnetic resonance (EPR) technique. The title complex crystallizes in the monoclinic system, space group P 21/ c with a = 7.4282(4), b = 22.5034(16), c = 8.3300(5) Å, β = 106.227(4)°, V = 1336.98(14) Å 3, and Z = 2. The structure consist of discrete [Cu(hsm) 2(sac) 2] molecules in which the copper ion is centrosymmetrically coordinated by two histamine ligands forming an equatorial plane [Cu-N hsm = 2.024(2) and Cu-N hsm = 2.0338(18) Å]. Two N atoms from the saccharinate ligands coordinate on the elongated axial positions with Cu-N sac being 2.609(5) Å. The complex is also characterized by spectroscopic (IR, UV/Vis) and thermal (TG, and TDA) methods. The cyclic voltammogram of the title complex investigated in DMSO (dimethylsulfoxide) solution exhibits only metal centred electroactivity in the potential range - 1.25-1.5 V versus Ag/AgCl reference electrode. The molecular orbital bond coefficients of Cu(II) ion in d 9 state is also calculated by using EPR and optical absorption parameters.

Base free N-alkylation of anilines with ArCH2OH and transfer hydrogenation of aldehydes/ketones catalyzed by the complexes of η5-Cp*Ir(iii) with chalcogenated Schiff bases of anthracene-9-carbaldehyde.

PubMed

Dubey, Pooja; Gupta, Sonu; Singh, Ajai K

2018-03-12

The condensation of anthracene-9-carbaldehyde with 2-(phenylthio/seleno)ethylamine results in Schiff bases [PhS(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ](L1) and [PhSe(CH 2 ) 2 C[double bond, length as m-dash]N-9-C 14 H 9 ] (L2). On their reaction with [(η 5 -Cp*)IrCl(μ-Cl)] 2 and CH 3 COONa at 50 °C followed by treatment with NH 4 PF 6 , iridacycles, [(η 5 -Cp*)Ir(L-H)][PF 6 ] (1: L = L1; 2: L = L2), result. The same reaction in the absence of CH 3 COONa gives complexes [(η 5 -Cp*)Ir(L)Cl][PF 6 ] (3-4) in which L = L1(3)/L2(4) ligates in a bidentate mode. The ligands and complexes were authenticated with HR-MS and NMR spectra [ 1 H, 13 C{ 1 H} and 77 Se{ 1 H} (in the case of L2 and its complexes only)]. Single crystal structures of L2 and half sandwich complexes 1-4 were established with X-ray crystallography. Three coordination sites of Ir in each complex are covered with η 5 -Cp* and on the remaining three, donor atoms present are: N, S/Se and C - /Cl - , resulting in a piano-stool structure. The moisture and air insensitive 1-4 act as efficient catalysts under mild conditions for base free N-alkylation of amines with benzyl alcohols and transfer hydrogenation (TH) of aldehydes/ketones. The optimum loading of 1-4 as a catalyst is 0.1-0.5 mol% for both the activations. The best reaction temperature is 80 °C for transfer hydrogenation and 100 °C for N-alkylation. The mercury poisoning test supports a homogeneous pathway for both the reactions catalyzed by 1-4. The two catalytic processes are most efficient with 3 followed by 4 > 1 > 2. The mechanism proposed on the basis of HR-MS of the reaction mixtures of the two catalytic processes taken after 1-2 h involves the formation of an alkoxy and hydrido species. The real catalytic species proposed in the case of iridacycles results due to the loss of the Cp* ring.

Risk factors for persistence of lower respiratory symptoms among community members exposed to the 2001 World Trade Center terrorist attacks

PubMed Central

Jordan, Hannah T; Friedman, Stephen M; Reibman, Joan; Goldring, Roberta M; Miller Archie, Sara A; Ortega, Felix; Alper, Howard; Shao, Yongzhao; Maslow, Carey B; Cone, James E; Farfel, Mark R; Berger, Kenneth I

2017-01-01

Objectives We studied the course of lower respiratory symptoms (LRS; cough, wheeze or dyspnoea) among community members exposed to the 9/11/2001 World Trade Center (WTC) attacks during a period of 12–13 years following the attacks, and evaluated risk factors for LRS persistence, including peripheral airway dysfunction and post-traumatic stress disorder (PTSD). Methods Non-smoking adult participants in a case-control study of post-9/11-onset LRS (exam 1, 2008–2010) were recruited for follow-up (exam 2, 2013–2014). Peripheral airway function was assessed with impulse oscillometry measures of R5 and R5-20. Probable PTSD was a PTSD checklist score ≥44 on a 2006–2007 questionnaire. Results Of 785 exam 1 participants, 545 (69%) completed exam 2. Most (321, 59%) were asymptomatic at all assessments. Among 192 participants with initial LRS, symptoms resolved for 110 (57%) by exam 2, 55 (29%) had persistent LRS and 27 (14%) had other patterns. The proportion with normal spirometry increased from 65% at exam 1 to 85% at exam 2 in the persistent LRS group (p<0.01) and was stable among asymptomatic participants and those with resolved LRS. By exam 2, spirometry results did not differ across symptom groups; however, R5 and R5-20 abnormalities were more common among participants with persistent LRS (56% and 46%, respectively) than among participants with resolved LRS (30%, p<0.01; 27%, p=0.03) or asymptomatic participants (20%, p<0.001; 8.2%, p<0.001). PTSD, R5 at exam 1, and R5-20 at exam 1 were each independently associated with persistent LRS. Conclusions Peripheral airway dysfunction and PTSD may contribute to LRS persistence. Assessment of peripheral airway function detected pulmonary damage not evident on spirometry. Mental and physical healthcare for survivors of complex environmental disasters should be coordinated carefully. PMID:28341697

Complexes of plexin-A4 and plexin-D1 convey semaphorin-3C signals to induce cytoskeletal collapse in the absence of neuropilins.

PubMed

Smolkin, Tatyana; Nir-Zvi, Inbal; Duvshani, Nerri; Mumblat, Yelena; Kessler, Ofra; Neufeld, Gera

2018-05-04

Class-3 semaphorin guidance factors bind to receptor complexes containing neuropilin and plexin receptors. A semaphorin may bind to several receptor complexes containing somewhat different constituents, resulting in diverse effects on cell migration. U87MG glioblastoma cells express both neuropilins and the four class-A plexins. Here, we show that these cells respond to Sema3A or Sema3B by cytoskeletal collapse and cell contraction but fail to contract in response to Sema3C, Sema3D, Sema3G or Sema3E, even when class-A plexins are overexpressed in the cells. In contrast, expression of recombinant plexin-D1 enabled contraction in response to these semaphorins. Surprisingly, unlike Sema3D and Sema3G, Sema3C also induced the contraction and repulsion of plexin-D1-expressing U87MG cells in which both neuropilins were knocked out using CRISPR/Cas9. In the absence of neuropilins, the EC50 of Sema3C was 5.5 times higher, indicating that the neuropilins function as enhancers of plexin-D1-mediated Sema3C signaling but are not absolutely required for Sema3C signal transduction. Interestingly, in the absence of neuropilins, plexin-A4 formed complexes with plexin-D1, and was required in addition to plexin-D1 to enable Sema3C-induced signal transduction. © 2018. Published by The Company of Biologists Ltd.

A case of hereditary angioneurotic oedema, successfully treated with ε-aminocaproic acid. Studies on C'1 esterase inhibitor, C'1 activation, plasminogen level and histamine metabolism

PubMed Central

Lundh, B.; Laurell, Anna-Brita; Wetterqvist, H.; White, T.; Granerus, G.

1968-01-01

A patient with clinical and laboratory findings characteristic of hereditary angioneurotic oedema was investigated. The patient was observed for a period of 5 weeks, during which he had four attacks. ε-Aminocaproic acid (EACA) was then given continuously for 5 months, during which time the patient had no attacks. Attacks reappeared on withdrawal of EACA. Trans-4-(aminomethyl) cyclohexane carboxylic acid (AMCA®) was found to be equally effective in later therapeutic trials. C'1 esterase inhibitor was found in low concentration in defibrinated plasma also during attacks. ε-Aminocaproic acid (EACA) produced no significant change of the inhibitor content. C'1 esterase inhibitor disappeared on incubation of defibrinated plasma from the patient at 37°C for 40 min, and C'1 esterase was generated. The generation time of C'1 esterase increased with increasing the concentration of EDTA in the test solution. The C'1 esterase inhibitor content of defibrinated plasma from the patient, varied with the C'1 esterase generation time, the coefficient of correlation being higher in plasma sampled before treatment with EACA. Plasminogen and α2-macroglobulin were within the normal ranges, also during attacks. EACA markedly depressed the plasminogen level, which rapidly returned to normal on withdrawal of the drug. The studies on histamine metabolism revealed no significant changes with the exception of the urinary excretion of histamine, which was moderately increased towards the end of the period studied. On the days the patient received EACA the urine never contained 1-methylimidazole-5-acetic acid which was present in all the other specimens of urine examined. The basal gastric acid secretion was increased. PMID:5701955

Interconversion of η3-H2SiRR' σ-complexes and 16-electron silylene complexes via reversible H-H or C-H elimination.

PubMed

Lipke, Mark C; Neumeyer, Felix; Tilley, T Don

2014-04-23

Solid samples of η(3)-silane complexes [PhBP(Ph)3]RuH(η(3)-H2SiRR') (R,R' = Et2, 1a; PhMe, 1b; Ph2, 1c, MeMes, 1d) decompose when exposed to dynamic vacuum. Gas-phase H2/D2 exchange between isolated, solid samples of 1c-d3 and 1c indicate that a reversible elimination of H2 is the first step in the irreversible decomposition. An efficient solution-phase trap for hydrogen, the 16-electron ruthenium benzyl complex [PhBP(Ph)3]Ru[η(3)-CH2(3,5-Me2C6H3)] (3) reacts quantitatively with H2 in benzene via elimination of mesitylene to form the η(5)-cyclohexadienyl complex [PhBP(Ph)3]Ru(η(5)-C6H7) (4). This H2 trapping reaction was utilized to drive forward and quantify the elimination of H2 from 1b,d in solution, which resulted in the decomposition of 1b,d to form 4 and several organosilicon products that could not be identified. Reaction of {[PhBP(Ph)3]Ru(μ-Cl)}2 (2) with (THF)2Li(SiHMes2) forms a new η(3)-H2Si species [PhBP(Ph)3]Ru[CH2(2-(η(3)-H2SiMes)-3,5-Me2C6H2)] (5) which reacts with H2 to form the η(3)-H2SiMes2 complex [PhBP(Ph)3]RuH(η(3)-H2SiMes2) (1e). Complex 1e was identified by NMR spectroscopy prior to its decomposition by elimination of Mes2SiH2 to form 4. DFT calculations indicate that an isomer of 5, the 16-electron silylene complex [PhBP(Ph)3]Ru(μ-H)(═SiMes2), is only 2 kcal/mol higher in energy than 5. Treatment of 5 with XylNC (Xyl = 2,6-dimethylphenyl) resulted in trapping of [PhBP(Ph)3]Ru(μ-H)(═SiMes2) to form the 18-electron silylene complex [PhBP(Ph)3]Ru(CNXyl)(μ-H)(═SiMes2) (6). A closely related germylene complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)](H)(═GeH(t)Bu) (8) was prepared from reaction of (t)BuGeH3 with the benzyl complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)][η(1)-CH2(3,5-Me2C6H3)] (7). Single crystal XRD analysis indicated that unlike for 6, the hydride ligand in 8 is a terminal hydride that does not engage in 3c-2e Ru-H → Ge bonding. Complex 1b is an effective precatalyst for the catalytic Ge-H dehydrocoupling of (t)BuGeH3 to form ((t)BuGeH2)2 (85% yield) and H2.

Risk Factors for Depression Among Civilians After the 9/11 World Trade Center Terrorist Attacks: A Systematic Review and Meta-Analysis

PubMed Central

Chatterjee, Abhinaba; Banerjee, Samprit; Stein, Cheryl; Kim, Min-Hyung; DeFerio, Joseph; Pathak, Jyotishman

2018-01-01

Introduction: The development of depressive symptoms among the population of civilians who were not directly involved in recovery or rescue efforts following the 9/11 World Trade Center (WTC) terrorist attacks is not comprehensively understood. We performed a meta-analysis that examined the associations between multiple risk factors and depressive symptoms after the 9/11 WTC terrorist attacks in New York City among civilians including survivors, residents, and passersby.  Methods: PubMed, Google Scholar, and the Cochrane Library were searched from September, 2001 through July, 2016. Reviewers identified eligible studies and synthesized odds ratios (ORs) using a random-effects model. Results: The meta-analysis included findings from 7 studies (29,930 total subjects). After adjusting for multiple comparisons, depressive symptoms were significantly associated with minority race/ethnicity (OR, 1.40; 99.5% Confidence Interval [CI], 1.04 to 1.88), lower income level (OR, 1.25; 99.5% CI, 1.09 to 1.43), post-9/11 social isolation (OR, 1.68; 99.5% CI, 1.13 to 2.49), post-9/11 change in employment (OR, 2.06; 99.5% CI, 1.30 to 3.26), not being married post-9/11 (OR, 1.59; 99.5% CI, 1.18 to 2.15), and knowing someone injured or killed (OR, 2.02; 99.5% CI, 1.42 to 2.89). Depressive symptoms were not significantly associated with greater age (OR, 0.86; 99.5% CI, 0.70 to 1.05), no college degree (OR, 1.32; 99.5% CI, 0.96 to 1.83), female sex (OR, 1.24; 99.5% CI, 0.98 to 1.59), or direct exposure to WTC related traumatic events (OR, 1.26; 99.5% CI, 0.69 to 2.30).  Discussion: Findings from this study suggest that lack of post-disaster social capital was most strongly associated with depressive symptoms among the civilian population after the 9/11 WTC terrorist attacks, followed by bereavement and lower socioeconomic status. These risk factors should be identified among civilians in future disaster response efforts.

Equatorial Ligand Perturbations Influence the Reactivity of Manganese(IV)-Oxo Complexes.

PubMed

Massie, Allyssa A; Denler, Melissa C; Cardoso, Luísa Thiara; Walker, Ashlie N; Hossain, M Kamal; Day, Victor W; Nordlander, Ebbe; Jackson, Timothy A

2017-04-03

Manganese(IV)-oxo complexes are often invoked as intermediates in Mn-catalyzed C-H bond activation reactions. While many synthetic Mn IV -oxo species are mild oxidants, other members of this class can attack strong C-H bonds. The basis for these reactivity differences is not well understood. Here we describe a series of Mn IV -oxo complexes with N5 pentadentate ligands that modulate the equatorial ligand field of the Mn IV center, as assessed by electronic absorption, electron paramagnetic resonance, and Mn K-edge X-ray absorption methods. Kinetic experiments show dramatic rate variations in hydrogen-atom and oxygen-atom transfer reactions, with faster rates corresponding to weaker equatorial ligand fields. For these Mn IV -oxo complexes, the rate enhancements are correlated with both 1) the energy of a low-lying 4 E excited state, which has been postulated to be involved in a two-state reactivity model, and 2) the Mn III/IV reduction potentials. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Comparative Macro-Structure of Armor Plate Ingots

DTIC Science & Technology

1932-05-12

Inoluded) Bur Stock (C J4.O; Mn ,^1 3l .1251 S .0^7; P .016) l|.08 lb«. Armoo Iron{C .05) 85 " Perro -Molybdenum (C »Ol+j SI 6.I4ÜI...Mo b5.9Ü) 5.7 " perro -VBtiBdlum (c *33i Si 1.1ÖJ V« 57.68) 5 Atf " perro -Chrowlum (c .18; Cr 68.82) Ü.75 " Perro -Man^B-ieae (Mn...97.5) ^55) ^M-) 1*56) 0.55 lb. l|J+5) 1.15 n ^57) perro -Slllcon (^l 95.0) O.k w They «ere the 6th 1 7th» iith, 9th, 10th

Advanced Motor-Controller Development.

DTIC Science & Technology

1983-06-22

OUTPUTS: 16 BIT PROE:UCT IN ACCA , FiCC:B Oi:t2 -* 0011: 0172 B:7 .04E SIFY STA A MCAN:,* SF,-’E MULTIPLICAND 001t4 0175 iF CLF: A INIT RESUI_I_T AOll5...OL-:t41) 04: ELSE ACCA IS UNC:HANGED 0-142 01SF ::,A 0CI CLAMP 0’Fi A #0 TEST SIGN OF A C0It 0l91 E’E: fBM I C.LIPI EBRFNCH IF NEG 01t4 4 : : 001,15 19...ELSE S.:ET ACCA =-ACCB:1B TQJ5. 01 .’ NEG B .ESTOPE ACCE: 01155 C. l1’-9 E -9 PTI RETUR’N Al? I .9~~ _________ . .... ... | |- - - - . . rjOt :E

Heterogeneous breakpoints in patients with acute lymphoblastic leukemia and the dic(9;20)(p11~13;q11) show recurrent involvement of genes at 20q11.21

PubMed Central

An, Qian; Wright, Sarah L.; Moorman, Anthony V.; Parker, Helen; Griffiths, Mike; Ross, Fiona M.; Davies, Teresa; Harrison, Christine J.; Strefford, Jon C.

2009-01-01

The dic(9;20)(p11~13;q11) is a recurrent chromosomal abnormality in patients with acute lymphoblastic leukemia. Although it results in loss of material from 9p and 20q, the molecular targets on both chromosomes have not been fully elucidated. From an initial cohort of 58 with acute lymphoblastic leukemia patients with this translocation, breakpoint mapping with fluorescence in situ hybridization on 26 of them revealed breakpoint heterogeneity of both chromosomes. PAX5 has been proposed to be the target gene on 9p, while for 20q, FISH analysis implicated the involvement of the ASXL1 gene, either by a breakpoint within (n=4) or centromeric (deletion, n=12) of the gene. Molecular copy-number counting, long-distance inverse PCR and direct sequence analysis identified six dic(9;20) breakpoint sequences. In addition to the three previously reported: PAX5-ASXL1, PAX5-C20ORF112 and PAX5-KIF3B; we identified three new ones in this study: sequences 3’ of PAX5 disrupting ASXL1, and ZCCHC7 disrupted by sequences 3’ of FRG1B and LOC1499503. This study provides insight into the breakpoint complexity underlying dicentric chromosomal formation in acute lymphoblastic leukemia and highlights putative target gene loci. PMID:19586940

Heterogeneous breakpoints in patients with acute lymphoblastic leukemia and the dic(9;20)(p11-13;q11) show recurrent involvement of genes at 20q11.21.

PubMed

An, Qian; Wright, Sarah L; Moorman, Anthony V; Parker, Helen; Griffiths, Mike; Ross, Fiona M; Davies, Teresa; Harrison, Christine J; Strefford, Jon C

2009-08-01

The dic(9;20)(p11-13;q11) is a recurrent chromosomal abnormality in patients with acute lymphoblastic leukemia. Although it results in loss of material from 9p and 20q, the molecular targets on both chromosomes have not been fully elucidated. From an initial cohort of 58 with acute lymphoblastic leukemia patients with this translocation, breakpoint mapping with fluorescence in situ hybridization on 26 of them revealed breakpoint heterogeneity of both chromosomes. PAX5 has been proposed to be the target gene on 9p, while for 20q, FISH analysis implicated the involvement of the ASXL1 gene, either by a breakpoint within (n=4) or centromeric (deletion, n=12) of the gene. Molecular copy-number counting, long-distance inverse PCR and direct sequence analysis identified six dic(9;20) breakpoint sequences. In addition to the three previously reported: PAX5-ASXL1, PAX5-C20ORF112 and PAX5-KIF3B; we identified three new ones in this study: sequences 3' of PAX5 disrupting ASXL1, and ZCCHC7 disrupted by sequences 3' of FRG1B and LOC1499503. This study provides insight into the breakpoint complexity underlying dicentric chromosomal formation in acute lymphoblastic leukemia and highlights putative target gene loci.

29 CFR 1610.9 - Responses: timing.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 29 Labor 4 2013-07-01 2013-07-01 false Responses: timing. 1610.9 Section 1610.9 Labor Regulations... Disclosure Under 5 U.S.C. 552 § 1610.9 Responses: timing. (a) The EEOC utilizes a multitrack system for..., the complex track, or the expedited track. EEOC distinguishes between simple and complex track...

29 CFR 1610.9 - Responses: timing.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 29 Labor 4 2014-07-01 2014-07-01 false Responses: timing. 1610.9 Section 1610.9 Labor Regulations... Disclosure Under 5 U.S.C. 552 § 1610.9 Responses: timing. (a) The EEOC utilizes a multitrack system for..., the complex track, or the expedited track. EEOC distinguishes between simple and complex track...

Synergistic adsorption of heavy metal ions and organic pollutants by supramolecular polysaccharide composite materials from cellulose, chitosan and crown ether

PubMed Central

Mututuvari, Tamutsiwa M.; Tran, Chieu D.

2013-01-01

We have developed a simple one-step method to synthesize novel supramolecular polysaccharide composites from cellulose (CEL), chitosan (CS) and benzo-15-crown 5 (B15C5). Butylmethylimidazolium chloride [BMIm+Cl−], an ionic liquid (IL), was used as a sole solvent for dissolution and preparation of the composites. Since majority of [BMIm+Cl−] used was recovered for reuse, the method is recyclable. The [CEL/CS + B15C5] composites obtained retain properties of their components, namely superior mechanical strength (from CEL), excellent adsorption capability for heavy metal ions and organic pollutants (from B15C5 and CS). More importantly, the [CEL/CS + B15C5] composites exhibit truly supramolecular properties. By itself CS, CEL and B15C5 can effectively adsorb Cd2+, Zn2+ and 2,4,5-trichlorophenol. However, adsorption capability of the composite was substantially and synergistically enhanced by adding B15C5 to either CEL and/or CS. That is, the adsorption capacity (qe values) for Cd2+ and Zn2+ by [CS + B15C5], [CEL + B15C5] and [CEL + CS + B15C5] composites are much higher than combined qe values of individual CS, CEL and B15C5 composites. It seems that B15C5 synergistically interact with CS (or CEL) to form more stable complexes with Cd2+ (or Zn2+), and as a consequence, the [CS + B15C5] (or the [CEL + B15C5]) composite can adsorb relatively larger amount Cd2+ (or Zn2+). Moreover, the pollutants adsorbed on the composites can be quantitatively desorbed to enable the [CS + CEL + B15C5] composites to be reused with similar adsorption efficiency. PMID:24333678

Chemical composition and functional properties of native chestnut starch (Castanea sativa Mill).

PubMed

Cruz, Bruno R; Abraão, Ana S; Lemos, André M; Nunes, Fernando M

2013-04-15

Starch isolation methods can change their physico-chemical and functional characteristics hindering the establishment of a starch-food functionality relation. A simple high yield and soft isolation method was applied for chestnut (Castanea sativa Mill) starch consisting in steeping and fruit disintegration in a 25 mM sodium bisulfite solution and purification by sedimentation. Starch integrity, physico-chemical composition, morphology and functional properties were determined, being observed significant differences from previous described methods for chestnut starch isolation. The X-ray pattern was of B-type, with a degree of crystallinity ranging from 51% to 9%, dependent on the starch moisture content. The onset, peak, and conclusion gelatinization temperatures were 57.1°C, 61.9°C and 67.9°C, respectively. Total amylose content was 26.6%, and there was not found any evidence for lipid complexed amylose. Swelling power at 90°C was 19 g/g starch, and the amount of leached amylose was 78% of the total amylose content. Native chestnut starch presents a type B pasting profile similar to corn starch but with a lower gelatinization (56.1°C) and peak viscosity (79.5°C) temperatures, making native chestnut starch a potential technological alternative to corn starch, especially in application where lower processing temperatures are needed. Copyright © 2013 Elsevier Ltd. All rights reserved.

26. Photograph of a line drawing. 'PLAN LAYOUT AND CROSS ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

26. Photograph of a line drawing. 'PLAN LAYOUT AND CROSS SECTION OF PART I, SECTION 8, BUILDINGS NO. C-1, C-3, C-5, C-6, C-7, C-9, MIXING, MANUFACTURING AREA, PLANT B AS OF 4-24-44.' From the U.S. Army Corps of Engineers. Industrial Facilities Inventory, Holston Ordnance Works, Kingsport, Tennessee. Plant B, Parts II, III. (Nashville, TN: Office of the District Engineer, 1944). - Holston Army Ammunition Plant, RDX-and-Composition-B Manufacturing Line 9, Kingsport, Sullivan County, TN

27. Photograph of a line drawing. 'PLAN LAYOUT AND CROSS ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

27. Photograph of a line drawing. 'PLAN LAYOUT AND CROSS SECTION OF PART III, SECTION 1, EQUIPMENT LAYOUT, BUILDINGS C-1, C-3, C-5, C-6, C-7, C-9 INCL., MIXING, MANUFACTURING AREA, PLANT 'B'.' From the U.S. Army Corps of Engineers. Industrial Facilities Inventory, Holston Ordnance Works, Kingsport, Tennessee. Plant B, Parts II, III. (Nashville, TN: Office of the District Engineer, 1944). - Holston Army Ammunition Plant, RDX-and-Composition-B Manufacturing Line 9, Kingsport, Sullivan County, TN

Terrorist Attacks Escalate in Frequency and Fatalities Preceding Highly Lethal Attacks

PubMed Central

Martens, Andy; Sainudiin, Raazesh; Sibley, Chris G.; Schimel, Jeff; Webber, David

2014-01-01

Highly lethal terrorist attacks, which we define as those killing 21 or more people, account for 50% of the total number of people killed in all terrorist attacks combined, yet comprise only 3.5% of terrorist attacks. Given the disproportionate influence of these incidents, uncovering systematic patterns in attacks that precede and anticipate these highly lethal attacks may be of value for understanding attacks that exact a heavy toll on life. Here we examined whether the activity of terrorist groups escalates–both in the number of people killed per attack and in the frequency of attacks–leading up to highly lethal attacks. Analyses of terrorist attacks drawn from a state-of-the-art international terrorism database (The Global Terrorism Database) showed evidence for both types of escalation leading up to highly lethal attacks, though complexities to the patterns emerged as well. These patterns of escalation do not emerge among terrorist groups that never commit a highly lethal attack. PMID:24755753

Computational studies of complexation of nitrous oxide by borane-phosphine frustrated Lewis pairs.

PubMed

Gilbert, Thomas M

2012-08-14

Computational studies of complexes Ar(3)B-ONN-PR(3) derived from reactions between borane-phosphine frustrated Lewis pairs and N(2)O reveal several interesting facets. Natural resonance theory calculations support a change in the preferred resonance structure as the Lewis acidity of the borane increases. Potential constitutional isomers where phosphorus binds to oxygen and boron to nitrogen are predicted to be unstable with respect to loss of phosphine oxide and free N(2). Other constitutional isomers represent stationary points on the potential energy surface; most are considerably less stable than the observed complexes, but one is predicted to be as stable. This arises because the dominant resonance form combines alternating charge with the presence of a stabilizing NO double bond. The relationship between Lewis acidity and complex formation for a variety of boranes was explored; the results are consistent with the idea that greater Lewis acidity stabilizes both classical and frustrated Lewis acid-base pairs, but to differing degrees such that both types can entrap N(2)O. Calculations addressing the mechanism of complex formation suggest that N(2)O binds first through the nitrogen to the phosphine phosphorus of the FLP, whereupon boron coordinates the oxygen atom. Studies of the mechanism of the degenerate exchange reaction between (4-F-H(4)C(6))(3)B-ONN-P(t-Bu)(3) and B(C(6)H(4)-4-F)(3), involves a "transition state", with relatively short B-O distances, and so resembles a classical I(a) process. The process involves two barriers, one associated with bringing the incoming borane into proximity with the oxygen, and the other associated with isomerising from a ladle-shaped cis-trans ct conformer to the observed trans-trans tt-type structure. The overall barrier for degenerate exchange was predicted to be between 65 and 110 kJ mol(-1), in fair agreement with experiment. Similar studies of the reaction between (4-F-H(4)C(6))(3)B-ONN-P(t-Bu)(3) and B(C(6)F(5))(3) indicate that this process more closely resembles a classical I(d) process, in that the "transition state" involves long B-O distances. Derivatization of the complexed NNO fragment appears possible; interaction between (F(5)C(6))(3)B-ONN-P(t-Bu)(3) and MeLi suggests stability for the ion pairs (F(5)C(6))(3)B-ON(Me)N-P(t-Bu)(3)(-)/Li(+) and (F(5)C(6))(3)B-ONN(Me)-P(t-Bu)(3)(-)/Li(+).

The influence of CYP2B6, CYP2C9 and CYP2D6 genotypes on the formation of the potent antioestrogen Z-4-hydroxy-tamoxifen in human liver.

PubMed

Coller, Janet K; Krebsfaenger, Niels; Klein, Kathrin; Endrizzi, Karin; Wolbold, Renzo; Lang, Thomas; Nüssler, Andreas; Neuhaus, Peter; Zanger, Ulrich M; Eichelbaum, Michel; Mürdter, Thomas E

2002-08-01

To investigate in a large panel of 50 human liver samples the contribution of CYP2C9, CYP2D6, and CYP3A4 to the overall formation of the potent antioestrogen Z-4-hydroxy-tamoxifen, and how various genotypes affect its formation from tamoxifen. The formation of Z-4-hydroxy-tamoxifen from 10 microm tamoxifen was studied in human liver microsomes (n=50), characterized for CYP2B6, CYP2C9, CYP2D6 and CYP3A4 expression, and CYP2B6, CYP2C9 and CYP2D6 genotype. The effect of chemical and monoclonal antibody inhibitors, and the formation in supersomes expressing recombinant CYP isoforms was also investigated. Z-4-hydroxy-tamoxifen was quantified using LC-MS analysis. Z-4-hydroxy-tamoxifen was formed by supersomes expressing CYP2B6, CYP2C9, CYP2C19 and CYP2D6, but not CYP3A4. In agreement with these data, the mean formation of Z-4-hydroxy-tamoxifen was inhibited 49% by sulphaphenazole (P=0.001), 38% by quinidine (P<0.05) and 13% by monoclonal antibody against CYP2B6 (MAB-2B6, P<0.05). Furthermore, Z-4-hydroxy-tamoxifen formation significantly correlated with both CYP2C9 expression (r(s)=0.256, P<0.05) and CYP2D6 expression (r(s)=0.309, P<0.05). Genotypes of CYP2D6, CYP2B6 and CYP2C9 had an effect on metabolite formation in such a way that samples with two nonfunctional CYP2D6, or two variant CYP2C9 or CYP2B6 alleles, showed lower enzyme activity compared with those with two functional or wild-type alleles, (5.0 vs 9.9 pmol mg(-1) protein min(-1), P=0.046, 5.1 vs 9.9 pmol mg(-1) protein min(-1), P=0.053, and 6.8 vs 9.4 pmol mg(-1) protein min(-1), P=0.054, respectively). CYP2D6 and CYP2C9 contribute on average 45 and 46%, respectively, to the overall formation of Z-4-hydroxy-tamoxifen. CYP2B6, CYP2C9 and CYP2D6 genotypes all affected Z-4-hydroxy-tamoxifen formation and can predict individual ability to catalyse this reaction.

Lack of prognostic significance of C-erbB-2 expression in low- and high- grade astrocytomas.

PubMed

Muallaoglu, Saik; Besen, Ali Ayberk; Ata, Alper; Mertsoylu, Huseyin; Arican, Ali; Kayaselcuk, Fazilet; Ozyilkan, Ozgur

2014-01-01

Astrocytic tumors, the most common primary glial tumors of the central nervous system, are classified from low to high grade according to the degree of anaplasia and presence of necrosis. Despite advances in therapeutic management of high grade astrocytic tumors, prognosis remains poor. In the present study, the frequency and prognostic significance of c-erb-B2 in astrocytic tumors was investigated. Records of 72 patients with low- and high-grade astrocytic tumors were evaluated. The expression of C-erbB-2 was determined immunohistochemically and intensity was recorded as 0 to 3+. Tumors with weak staining (1+) or no staining (0) were considered Her-2 negative, while tumors with moderate (2+) and strong (3+) staining were considered Her-2 positive. Of the 72 patients, 41 (56.9%) had glioblastoma (GBM), 10 (13.9%) had diffuse astrocytoma, 15 (20.8%) had anaplastic astrocytoma, 6 (8.3%) had pilocytic astrocytoma. C-erbB-2 overexpression was detected in the tumor specimens of 17 patients (23.6%). Six (8.3%) tumors, all GBMs, exhibited strong staining, 2 (2.7%) specimens, both GBMs, exhibited moderate staining, and 9 specimens, 5 of them GBMs (12.5%), exhibited weak staining. No staining was observed in diffuse astrocytoma and pilocytic astrocytoma specimens. Median overall survival of patients with C-erbB-2 negative and C-erbB-2 positive tumors were 30 months (95%CI: 22.5-37.4 months) and 16.9 months (95%CI: 4.3-29.5 months), respectively (p=0.244). Although there was no difference in survival, C-erbB-2 overexpression was observed only in the GBM subtype.

Fibrillin 5 Is Essential for Plastoquinone-9 Biosynthesis by Binding to Solanesyl Diphosphate Synthases in Arabidopsis

PubMed Central

Kim, Eun-Ha; Lee, Yongjik

2015-01-01

Fibrillins are lipid-associated proteins in plastids and are ubiquitous in plants. They accumulate in chromoplasts and sequester carotenoids during the development of flowers and fruits. However, little is known about the functions of fibrillins in leaf tissues. Here, we identified fibrillin 5 (FBN5), which is essential for plastoquinone-9 (PQ-9) biosynthesis in Arabidopsis thaliana. Homozygous fbn5-1 mutations were seedling-lethal, and XVE:FBN5-B transgenic plants expressing low levels of FBN5-B had a slower growth rate and were smaller than wild-type plants. In chloroplasts, FBN5-B specifically interacted with solanesyl diphosphate synthases (SPSs) 1 and 2, which biosynthesize the solanesyl moiety of PQ-9. Plants containing defective FBN5-B accumulated less PQ-9 and its cyclized product, plastochromanol-8, but the levels of tocopherols were not affected. The reduced PQ-9 content of XVE:FBN5-B transgenic plants was consistent with their lower photosynthetic performance and higher levels of hydrogen peroxide under cold stress. These results indicate that FBN5-B is required for PQ-9 biosynthesis through its interaction with SPS. Our study adds FBN5 as a structural component involved in the biosynthesis of PQ-9. FBN5 binding to the hydrophobic solanesyl moiety, which is generated by SPS1 and SPS2, in FBN5-B/SPS homodimeric complexes stimulates the enzyme activity of SPS1 and SPS2. PMID:26432861

The effect of ad hominem attacks on the evaluation of claims promoted by scientists.

PubMed

Barnes, Ralph M; Johnston, Heather M; MacKenzie, Noah; Tobin, Stephanie J; Taglang, Chelsea M

2018-01-01

Two experiments were conducted to determine the relative impact of direct and indirect (ad hominem) attacks on science claims. Four hundred and thirty-nine college students (Experiment 1) and 199 adults (Experiment 2) read a series of science claims and indicated their attitudes towards those claims. Each claim was paired with one of the following: A) a direct attack upon the empirical basis of the science claim B) an ad hominem attack on the scientist who made the claim or C) both. Results indicate that ad hominem attacks may have the same degree of impact as attacks on the empirical basis of the science claims, and that allegations of conflict of interest may be just as influential as allegations of outright fraud.

The effect of ad hominem attacks on the evaluation of claims promoted by scientists

PubMed Central

2018-01-01

Two experiments were conducted to determine the relative impact of direct and indirect (ad hominem) attacks on science claims. Four hundred and thirty-nine college students (Experiment 1) and 199 adults (Experiment 2) read a series of science claims and indicated their attitudes towards those claims. Each claim was paired with one of the following: A) a direct attack upon the empirical basis of the science claim B) an ad hominem attack on the scientist who made the claim or C) both. Results indicate that ad hominem attacks may have the same degree of impact as attacks on the empirical basis of the science claims, and that allegations of conflict of interest may be just as influential as allegations of outright fraud. PMID:29381757

(Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B{sub 5}, the first examples of copper platinum borides. Observation of superconductivity in a novel boron filled β-Mn-type compound

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

Salamakha, Leonid P.; Sologub, Oksana, E-mail: oksana.sologub@univie.ac.at; Stöger, Berthold

New ternary copper platinum borides have been synthesized by arc melting of pure elements followed by annealing at 600 °C. The structures have been studied by X-ray single crystal and powder diffraction. (Pt{sub 1−x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.33) forms a B-filled β-Mn-type structure (space group P4{sub 1}32; a=0.6671(1) nm). Cu atoms are distributed preferentially on the 8c atom sites, whereas the 12d site is randomly occupied by Pt and Cu atoms (0.670(4) Pt±0.330(4) Cu). Boron is located in octahedral voids of the parent β-Mn-type structure. Pt{sub 9}Cu{sub 3}B{sub 5} (space group P-62m; a=0.9048(3) nm, c=0.2908(1) nm) adopts the Pt{sub 9}Zn{submore » 3}B{sub 5–δ}-type structure. It has a columnar architecture along the short translation vector exhibiting three kinds of [Pt{sub 6}] trigonal prism columns (boron filled, boron semi-filled and empty) and Pt channels with a pentagonal cross section filled with Cu atoms. The striking structural feature is a [Pt{sub 6}] cluster in form of an empty trigonal prism at the origin of the unit cell, which is surrounded by coupled [BPt{sub 6}] and [Pt{sub 6}] trigonal prisms, rotated perpendicularly to the central one. There is no B–B contact as well as Cu–B contact in the structure. The relationships of Pt{sub 9}Cu{sub 3}B{sub 5} structure with the structure of Ti{sub 1+x}Os{sub 2−x}RuB{sub 2} as well as with the structure families of metal sulfides and aluminides have been elucidated. (Pt{sub 1–x}Cu{sub x}){sub 3}Cu{sub 2}B (x=0.3) (B-filled β-Mn-type structure) is a bulk superconductor with a transition temperature of about 2.06 K and an upper critical field μ{sub 0}H{sub C2}(0){sup WHH} of 1.2 T, whereas no superconducting transition has been observed up to 0.3 K in Pt{sub 9}Cu{sub 3}B{sub 5} (Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure) from electrical resistivity measurements. - Highlights: • First two copper platinum borides, (Pt{sub 0.67}Cu{sub 0.33}){sub 3}Cu{sub 2}B and Pt{sub 9}Cu{sub 3}B{sub 5} were obtained. • (Pt{sub 0.67}Cu{sub 0.33}){sub 3}Cu{sub 2}B forms a B-filled β-Mn-type structure. • Pt{sub 9}Cu{sub 3}B{sub 5} adopts a Pt{sub 9}Zn{sub 3}B{sub 5–δ}-type structure. • Boron atoms exhibit octahedral and trigonal prismatic coordination. • (Pt{sub 1–x}Cu{sub x})3Cu{sub 2}B (x=0.3) is a bulk superconductor with T{sub c} 2.06 K.« less

Stage-specific expression of DDX4 and c-kit at different developmental stages of the porcine testis.

PubMed

Lee, Ran; Lee, Won-Young; Park, Hyun-Jung; Ha, Woo-Tae; Woo, Jae-Seok; Chung, Hak-Jae; Lee, Ji-Heon; Hong, Kwonho; Song, Hyuk

2018-03-01

Spermatogenesis begins with spermatogonial stem cells (SSCs), which are located in the basement membrane of the adult testes. Previous studies have described specific biomarkers for undifferentiated porcine spermatogonia or SSCs; however, these markers are not sufficient to understand spermatogenesis at different developmental stages. The objective of this study was characterize the expression of DEAD-Box polypeptide 4 (DDX4, also known as VASA) and tyrosine-protein kinase kit (c-kit), as potential markers of male germ cells in the porcine testis. In porcine testis tissue at prepubertal stages (5, 30, and 60 days), DDX4 and c-kit protein expression was detected in the most undifferentiated spermatogonia, which also express protein gene product 9.5 (PGP9.5). However, in porcine testis tissues from pubertal and postpubertal stages (90, 120, and 150 days), DDX4 and c-kit were not detected in PGP9.5-positive undifferentiated spermatogonia. The DDX4 expression pattern was similar to that of c-kit in the porcine testis. In adult porcine testes, DDX4-expressing cells were located on the lumenal side, compared to synaptonemal complex protein 3-positive primary spermatocytes, but DDX-4 was not co-expressed with acrosin, a known acrosome marker. In addition, DDX4 was detected in PGP9.5-expressing porcine SSCs in culture. Based on our results, we suggest that DDX4 and c-kit are putative markers of undifferentiated spermatogonia in the prepubertal porcine testis. While in the postpubertal porcine testis, they are markers of differentiated spermatocytes. These findings may facilitate future studies of porcine spermatogenesis. Copyright © 2018 Elsevier B.V. All rights reserved.

Shape-persistent nanosize organometallic complexes: synthesis and application in a nanofiltration membrane reactor.

PubMed

Dijkstra, Harm P; Kruithof, Cornelis A; Ronde, Niek; Van De Coevering, Rob; Ramón, Diego J; Vogt, Dieter; Van Klink, Gerard P M; Van Koten, Gerard

2003-02-07

Shape-persistent multi(NCN-palladium and/or -platinum) complexes having one- (5 and 6), two- (1 and 2), and three-dimensional (3 and 4) geometries were prepared in moderate to good yields. Two different approaches were used to construct the multimetallic materials: (i) the construction of the multisite ligands followed by the permetalation step and (ii) selective and mild one-pot coupling of monometallic buiding blocks to a multifunctional shape-persistent organic core molecule. The first approach was used to prepare the palladated and/or platinated tris- (2) and bis(NCN-pincer) (5) complexes, while the second approach afforded the palladated and platinated octakis- (3) and dodecakis(NCN-pincer) (4) complexes. Complexes 1-6 were subjected to nanofiltration (NF) experiments in order to investigate the influence of rigidity and geometry on the retention of these molecules by NF membranes. For this purpose, the corresponding (NCN-Pt-X)(n)() complexes (1c-4c, 5, and 6) were used since exposing these complexes to sulfur dioxide in solution resulted in the formation of bright orange complexes, allowing the use of UV/vis spectroscopy to accurately determine the concentrations of 1-6 in both retentate and permeate. Using the MPF-60 (MWCO = 400) NF-membrane, retention rates of 82.4 (6), 93.9 (1c), 98.7 (2c), 99.5 (3c), 99.6 (5), and >99.9% (4c) were found, while 2c and 4c in combination with the MPF-50 (MWCO = 700) NF-membrane were retained in 97.6 and 99.9%, respectively. A clear relationship is observed between the dimensions calculated by molecular modeling and the retention rates of 1-6. The one-dimensional bis(pincer-platinum) complex 5, however, shows an unexpectedly high retention rate (99.6%) that can be due to precipitation of the complex in the membrane (clogging of the membrane) and/or to the formation of larger aggregates near the membrane. In addition, comparison of 2 and 4 with flexible nickelated G0- and G1-dendrimers with similar dimensions proved that a high degree of rigidity in the backbone of macromolecular complexes indeed leads to more efficient retentions of these multimetallic materials by NF-membranes.

Hash Functions and Information Theoretic Security

NASA Astrophysics Data System (ADS)

Bagheri, Nasour; Knudsen, Lars R.; Naderi, Majid; Thomsen, Søren S.

Information theoretic security is an important security notion in cryptography as it provides a true lower bound for attack complexities. However, in practice attacks often have a higher cost than the information theoretic bound. In this paper we study the relationship between information theoretic attack costs and real costs. We show that in the information theoretic model, many well-known and commonly used hash functions such as MD5 and SHA-256 fail to be preimage resistant.

Vestibular syncope: A disorder associated with drop attack in Ménière's disease.

PubMed

Pyykkö, Ilmari; Manchaiah, Vinaya; Zou, Jing; Levo, Hilla; Kentala, Erna

2018-04-01

Experiments in humans and animals indicate that vestibular influx through vestibular sympathetic reflex is an important and vital part of the regulatory system of circulation. The otolith organ adjusts the circulatory responses through the vestibular sympathetic reflex during an upright stance and may trigger a vasovagal attack of syncope. The aim of the present study was to evaluate the prevalence and association of syncope attacks among patients with Ménière's disease (MD). Vestibular syncope was defined as a sudden and transient loss of consciousness, which subsides spontaneously in people with vestibular disorders and without localizing neurological deficit. During clinical interactions, we encountered 5 patients with syncope during a Tumarkin attack of MD. Thereafter we evaluated data from 952 patients collected with a questionnaire from the Finnish Ménière Association (FMA). The data contained case histories with special attention to Tumarkin attacks, participation restriction, migraines, and syncope attacks. The mean age of the subjects participating in the study was 60.6 years (range 25-75 years). The duration of the disease was on average 9.8 years (range 0.5-35 years). In the current study sample, attacks of syncope were reported by 38 patients (4%) in association with the vertigo attack. Syncope was associated with Tumarkin attacks (X 2 =16.7, p<0.001), migraine (X 2 =7.4, p<0.011), history of ischemic heart disease (X 2 =6.0, p<0.025), and history of cerebrovascular disease (X 2 =11.7, p<0.004). Duration of MD was correlated with syncope. Syncope was provoked by physical strain and environmental pressure, and was associated with impairment of the visual field (i.e., visual blurring). In logistic regression analysis, syncope was significantly associated with Tumarkin attacks (odds ratio 3.2), migraines (odds ratio 2.3) and nausea (odds ratio 1.3). The attack of syncope was experienced as frightening, and general health related quality of life (HRQoL) was significantly worsened. Also, the patients suffered more from fatigue. The current study indicates that patients with MD who suffer from Tumarkin attacks can suffer from syncope. It confirms the role of the otolith organ in controlling the circulatory homeostasis of the body. The actions are mediated through the vestibular sympathetic reflex. Copyright © 2017 Elsevier B.V. All rights reserved.

Isolation and Purification of Complex II from Proteus Mirabilis Strain ATCC 29245

PubMed Central

Shabbiri, Khadija; Ahmad, Waqar; Syed, Quratulain; Adnan, Ahmad

2010-01-01

A respiratory complex was isolated from plasma membrane of pathogenic Proteus mirabilis strain ATCC 29245. It was identified as complex II consisting of succinate:quinone oxidoreductase (EC 1.3.5.1) containing single heme b. The complex II was purified by ion-exchange chromatography and gel filtration. The molecular weight of purified complex was 116.5 kDa and it was composed of three subunits with molecular weights of 19 kDa, 29 kDa and 68.5 kDa. The complex II contained 9.5 nmoles of cytochrome b per mg protein. Heme staining indicated that the 19 kDa subunit was cytochrome b. Its reduced form showed absorptions peaks at 557.0, 524.8 and 424.4 nm. The α-band was shifted from 557.0 nm to 556.8 nm in pyridine ferrohemochrome spectrum. The succinate: quinone oxidoreductase activity was found to be high in this microorganism. PMID:24031557

Nine pairs of megastigmane enantiomers from the leaves of Eucommia ulmoides Oliver.

PubMed

Yan, Jiankun; Shi, Xuliu; Donkor, Paul Owusu; Zhu, Huajie; Gao, Xiumei; Ding, Liqin; Qiu, Feng

2017-10-01

Nine pairs of megastigmane enantiomers (1a/1b-9a/9b), comprising two new compounds (6S,9R)-blumenol C (7b), (6S,9S)-blumenol C (8b), two pairs of enantiomers (+)-(6R)-eucomegastigmane A (1a), (-)-(6S)-eucomegastigmane A (1b), (+)-(3S,4S)-eucomegastigmane B (5a), (-)-(3R,4R)-eucomegastigmane B (5b) isolated by chiral resolution firstly, and twelve known compounds, were isolated from the leaves of Eucommia ulmoides Oliver. Their structures were elucidated based on extensive spectroscopic analysis. Absolute configurations of the megastigmane enantiomers were assigned by comparing experimental ECD and OR with calculated ECD and OR. Docking-based virtual screening of all compounds showed that megastigmane enantiomers have weak intermolecular interactions with the binding site residues of angiotensin-converting enzyme (ACE) and angiotensin II type 1 receptor (AT 1 R).

Mechanisms of Polymer Curing and Thermal Degradation

DTIC Science & Technology

1979-12-01

respectively. 29 0)- Fi . J . IR S e t u f i ( - 3 E hy y p e o y Ph n l S f n .30 z Iii 41 rI2P6i4000 3500 3000 42500 §200010 6010 2010 0 0 0 0...Polymer X Obs.6(_pm) Obs.(ppmA H 7.9,8.0 g,h 7.8 g,h 7.5 I ,e 7.5 i ,c,2 7.3 b,e 6.0-7.2 b,d,f,j,=CH 7.2 d 7.0 f,j 3.1 a HC C =- T O" 7.9 g 7.9 g 7.3 b...e 7.4 b,e 7.1 d 6.0-7.1 c,d,f,=CH 7.0 f,c 3.1 a 3.1 a aFor X 0 H, ggh, f= i b Based on first-order analysis of multiplets. 37 t TABLE 4. SUMMARY OF 13C

Accuracy of intraoral data acquisition in comparison to the conventional impression.

PubMed

Luthardt, R G; Loos, R; Quaas, S

2005-10-01

The achievable accuracy is a decisive parameter for the comparison of direct intraoral digitization with the conventional impression. The objective of the study was therefore to compare the accuracy of the reproduction of a model situation by intraoral digitization vs. the conventional procedure consisting of impression taking, model production, and extraoral digitization. Proceeding from a die model with a prepared tooth 16, the reference data set of the teeth 15, 16 and 17 was produced with an established procedure by means ofextraoral digitization. For the simulated intraoral data acquisition of the master model (Cerec 3D camera, Sirona, Bensheim), the camera was fastened on a stand for the measurement and the teeth digitized seven times each in defined views (occlusal, and in each case inclined by 20 degrees, from the mesio-proximal, disto-proximal, vestibular and oral aspect). Matching was automated (comparative data sets B1-B5). A clinically perfect one-step putty-and-wash impression was taken from the starting model. The model produced under defined conditions was digitized extraorally five times (digi-SCAN, comparative data sets C1-C5). The data sets B1-B5 and C1-C5 were assigned to the reference data set by means of best-fit matching and the root of the mean quadratic deviation (RMS; root mean square) calculated. The deviations were visualized, and mean positive, negative and absolute deviations calculated. The mean RMS was 27.9 microm (B1-B5) or 18.8 microm (C1-C5). The mean deviations for the prepared tooth were 18 microm/-17 microm (B1-B5) and 9 microm /-9 microm (C1-C5). For tooth 15, the mean deviations were 22 microm/-19 microm (B1-B5) and 15 microm/-16 microm (C1-C5). The intraoral method showed good results with deviations from the CAD starting model of approx. 17 microm, related to the prepared tooth 16. On the whole, in this in-vitro study, extraoral digitization with impression taking and model production showed higher accuracy than intraoral digitization. Since the inaccuracies in the conventional impression under real clinical conditions may be higher than the values determined above, a comparison under clinical conditions should be performed subsequently.

Titanium isopropoxide complexes of a series of sterically demanding aryloxo based [N2O2]2- ligands as precatalysts for ethylene polymerization.

PubMed

Panda, Manas K; Kaur, Sukhdeep; Reddy, Annapureddy Rajasekhar; Shaikh, Mobin M; Butcher, Ray J; Gupta, Virendrakumar; Ghosh, Prasenjit

2010-12-07

Several titanium isopropoxide complexes [N,N'-bis(2-oxo-3-R(1)-5-R(2)-phenylmethyl)-N,N'-bis(methylene-p-R(3)-C(6)H(4))-ethylenediamine]Ti(O(i)Pr)(2) [R(1) = t-Bu, R(2) = Me, R(3) = H (1b); R(1) = R(2) = t-Bu, R(3) = H, (2b); R(1) = R(2) = Cl, R(3) = H, (3b), R(1) = t-Bu, R(2) = Me, R(3) = Cl (4b); R(1) = R(2) = t-Bu, R(3) = Cl, (5b); R(1) = R(2) = R(3) = Cl, (6b)] supported over sterically demanding aryloxy based [N(2)O(2)]H(2) ligands have been designed as precatalysts for the ethylene polymerization. Specifically, the 1b-6b complexes, when treated with methylaluminoxane (MAO) under 88 ± 0.5 psi of ethylene at 30 °C for 3 h, produced polyethylene polymers of high molecular weight (M(w) = ca. 7.2-8.3 × 10(5) g mol(-1)) having broad molecular weight distribution (PDI = ca. 13.1-14.6). The 1b-6b complexes were conveniently synthesized from the direct reaction of the [N(2)O(2)]H(2) ligands, 1a-6a, with Ti(O(i)Pr)(4) in 69-86% yield.

Using vertebral movement and intact paraspinal muscles to determine the distribution of intrafusal fiber innervation of muscle spindle afferents in the anesthetized cat.

PubMed

Reed, William R; Cao, Dong-Yuan; Ge, Weiqing; Pickar, Joel G

2013-03-01

Increasing our knowledge regarding intrafusal fiber distribution and physiology of paraspinal proprioceptors may provide key insights regarding proprioceptive deficits in trunk control associated with low back pain and lead to more effective clinical intervention. The use of vertebral movement as a means to reliably stretch paraspinal muscles would greatly facilitate physiological study of paraspinal muscle proprioceptors where muscle tendon isolation is either very difficult or impossible. The effects of succinylcholine (SCh) on 194 muscle spindle afferents from lumbar longissimus or multifidus muscles in response to computer-controlled, ramp-and-hold movements of the L(6) vertebra were investigated in anesthetized cats. Paraspinal muscles were stretched by moving the L(6) vertebra 1.5-1.7 mm in the dorsal-ventral direction. Initial frequency (IF), dynamic difference (DD), their changes (∆) following SCh injection (100-400 μg kg(-1)), and post-SCh dynamic difference (SChDD) were measured. Muscle spindle intrafusal fiber terminations were classified as primary or secondary fibers as well as bag(1) (b(1)c), bag(2) (b(2)c), b(1)b(2)c, or chain (c) fibers. Intrafusal fiber subpopulations were distinguished using logarithmic transformation of SChDD and ∆IF distributions as established by previous investigators. Increases in DD indicate strength of b(1)c influence while increases in IF indicate strength of b(2)c influence. Out of 194 afferents, 46.9 % of afferents terminated on b(2)c fibers, 46.4 % on b(1)b(2)c fibers, 1 % on b(1)c fibers, and 5.7 % terminated on c fibers. Based on these intrafusal fiber subpopulation distributions, controlled vertebral movement can effectively substitute for direct tendon stretch and allow further investigation of paraspinal proprioceptors in this anatomically complex body region.

Ruthenium(II) polypyridyl complexes as dual inhibitors of telomerase and topoisomerase.

PubMed

Liao, Guoliang; Chen, Xiang; Wu, Jingheng; Qian, Chen; Wang, Yi; Ji, Liangnian; Chao, Hui

2015-09-14

One novel ruthenium polypyridyl complex, [Ru(bpy)2(icip)](2+) (1), and two previously reported ruthenium polypyridyl complexes, [Ru(bpy)2(pdppz)](2+) ()2 and [Ru(bpy)2(tactp)](2+) (3) (bpy = 2,2'-bipyridine, icip = 2-(indeno[2,1-b]chromen-6-yl)-1H-imidazo[4,5-f][1,10]phenanthroline, pdppz = phenanthro[4,5-abc]dipyrido[3,2-h:2',3'-j]phenazine, tactp = 4,5,9,18-tetraazachryseno[9,10-b]-triphenylene), have been synthesised. As expected, these complexes show inhibition towards telomerase by inducing and stabilising the G-quadruplex structure, and behave as topoisomerase I/II poisons at the same time. Additionally, the acute and chronic cytotoxicities of the complexes are considered. Furthermore, cell apoptosis experiments are used to briefly study the mechanism. Because studies involving multi-target inhibition towards topoisomerase and telomerase of Ru(II) complexes have not been reported previously, the present research may help to develop innovative chemical strategies and therapies.

Cellulolytic Streptomyces Strains Associated with Herbivorous Insects Share a Phylogenetically Linked Capacity To Degrade Lignocellulose

PubMed Central

Book, Adam J.; Lewin, Gina R.; McDonald, Bradon R.; Takasuka, Taichi E.; Doering, Drew T.; Adams, Aaron S.; Blodgett, Joshua A. V.; Clardy, Jon; Raffa, Kenneth F.; Fox, Brian G.

2014-01-01

Actinobacteria in the genus Streptomyces are critical players in microbial communities that decompose complex carbohydrates in the soil, and these bacteria have recently been implicated in the deconstruction of plant polysaccharides for some herbivorous insects. Despite the importance of Streptomyces to carbon cycling, the extent of their plant biomass-degrading ability remains largely unknown. In this study, we compared four strains of Streptomyces isolated from insect herbivores that attack pine trees: DpondAA-B6 (SDPB6) from the mountain pine beetle, SPB74 from the southern pine beetle, and SirexAA-E (SACTE) and SirexAA-G from the woodwasp, Sirex noctilio. Biochemical analysis of secreted enzymes demonstrated that only two of these strains, SACTE and SDPB6, were efficient at degrading plant biomass. Genomic analyses indicated that SACTE and SDPB6 are closely related and that they share similar compositions of carbohydrate-active enzymes. Genome-wide proteomic and transcriptomic analyses revealed that the major exocellulases (GH6 and GH48), lytic polysaccharide monooxygenases (AA10), and mannanases (GH5) were conserved and secreted by both organisms, while the secreted endocellulases (GH5 and GH9 versus GH9 and GH12) were from diverged enzyme families. Together, these data identify two phylogenetically related insect-associated Streptomyces strains with high biomass-degrading activity and characterize key enzymatic similarities and differences used by these organisms to deconstruct plant biomass. PMID:24837391

Robustness and structure of complex networks

NASA Astrophysics Data System (ADS)

Shao, Shuai

This dissertation covers the two major parts of my PhD research on statistical physics and complex networks: i) modeling a new type of attack -- localized attack, and investigating robustness of complex networks under this type of attack; ii) discovering the clustering structure in complex networks and its influence on the robustness of coupled networks. Complex networks appear in every aspect of our daily life and are widely studied in Physics, Mathematics, Biology, and Computer Science. One important property of complex networks is their robustness under attacks, which depends crucially on the nature of attacks and the structure of the networks themselves. Previous studies have focused on two types of attack: random attack and targeted attack, which, however, are insufficient to describe many real-world damages. Here we propose a new type of attack -- localized attack, and study the robustness of complex networks under this type of attack, both analytically and via simulation. On the other hand, we also study the clustering structure in the network, and its influence on the robustness of a complex network system. In the first part, we propose a theoretical framework to study the robustness of complex networks under localized attack based on percolation theory and generating function method. We investigate the percolation properties, including the critical threshold of the phase transition pc and the size of the giant component Pinfinity. We compare localized attack with random attack and find that while random regular (RR) networks are more robust against localized attack, Erdoḧs-Renyi (ER) networks are equally robust under both types of attacks. As for scale-free (SF) networks, their robustness depends crucially on the degree exponent lambda. The simulation results show perfect agreement with theoretical predictions. We also test our model on two real-world networks: a peer-to-peer computer network and an airline network, and find that the real-world networks are much more vulnerable to localized attack compared with random attack. In the second part, we extend the tree-like generating function method to incorporating clustering structure in complex networks. We study the robustness of a complex network system, especially a network of networks (NON) with clustering structure in each network. We find that the system becomes less robust as we increase the clustering coefficient of each network. For a partially dependent network system, we also find that the influence of the clustering coefficient on network robustness decreases as we decrease the coupling strength, and the critical coupling strength qc, at which the first-order phase transition changes to second-order, increases as we increase the clustering coefficient.

Effects of ambient temperature on stroke hospital admissions: Results from a time-series analysis of 104,432 strokes in Guangzhou, China.

PubMed

Guo, Pi; Zheng, Murui; Feng, Wenru; Wu, Jiagang; Deng, Changyu; Luo, Ganfeng; Wang, Li; Pan, Bingying; Liu, Huazhang

2017-02-15

Stroke is a main cause of death and public health burden in China. The evidence on the burden of different strokes attack attribute to ambient temperature in China is limited. This study aimed to show the characteristics of stroke attack and the attributable risk due to temperature based on hospital admission data in Guangzhou, one of the most developed cities in China. From January 1, 2013 to December 31, 2015, 104,432 stroke hospitalizations in Guangzhou residents from 67 hospitals for stroke sentinel surveillance were registered. Characteristics of hospital admissions by gender, age group, calendar year and stroke subtype were analyzed, and distributed lag non-linear models were applied to evaluate the effects of temperature on stroke attack admissions. Stroke attack admissions increased from 31,851 to 36,755 through 2013 to 2015, increasing by 15.4%. An increasing trend in the risk of stroke attack with age was observed, irrespectively of stroke subtype and calendar year. People with hypertension were more likely to have an associated stroke than people without that. The effects of cold temperature on attack admissions for CBI and ICH strokes were significant. Overall, the percentages of CBI and ICH attack admissions attribute to cold temperature were 9.06% (95% CI: 1.84, 15.00) and 15.09% (95% CI: 5.86, 21.96), respectively. Besides, elderly people were more vulnerable to cold temperature than the young. Measures should be taken to increase public awareness about the ill effects of cold temperature on stroke attack, and educate the public about self-protection. Copyright © 2016 Elsevier B.V. All rights reserved.

Initial bridges between two ribosomal subunits are formed within 9.4 milliseconds, as studied by time-resolved cryo-EM.

PubMed

Shaikh, Tanvir R; Yassin, Aymen S; Lu, Zonghuan; Barnard, David; Meng, Xing; Lu, Toh-Ming; Wagenknecht, Terence; Agrawal, Rajendra K

2014-07-08

Association of the two ribosomal subunits during the process of translation initiation is a crucial step of protein synthesis. The two subunits (30S and 50S) of the bacterial 70S ribosome are held together by 12 dynamic bridges involving RNA-RNA, RNA-protein, and protein-protein interactions. The process of bridge formation, such as whether all these bridges are formed simultaneously or in a sequential order, is poorly understood. To understand such processes, we have developed and implemented a class of microfluidic devices that mix two components to completion within 0.4 ms and spray the mixture in the form of microdroplets onto an electron microscopy grid, yielding a minimum reaction time of 9.4 ms before cryofixation. Using these devices, we have obtained cryo-EM data corresponding to reaction times of 9.4 and 43 ms and have determined 3D structures of ribosomal subunit association intermediates. Molecular analyses of the cryo-EM maps reveal that eight intersubunit bridges (bridges B1a, B1b, B2a, B2b, B3, B7a, B7b, and B8) form within 9.4 ms, whereas the remaining four bridges (bridges B2c, B4, B5, and B6) take longer than 43 ms to form, suggesting that bridges are formed in a stepwise fashion. Our approach can be used to characterize sequences of various dynamic functional events on complex macromolecular assemblies such as ribosomes.

Co-expression, purification and characterization of the lipase and foldase of Burkholderia contaminans LTEB11.

PubMed

Alnoch, Robson Carlos; Stefanello, Adriano Alves; Paula Martini, Viviane; Richter, Jeferson Luiz; Mateo, Cesar; Souza, Emanuel Maltempi de; Mitchell, David Alexander; Muller-Santos, Marcelo; Krieger, Nadia

2018-05-30

Genes encoding lipase LipBC (lipA) and foldase LifBC (lipB) were identified in the genome of Burkholderia contaminans LTEB11. Analysis of the predicted amino acid sequence of lipA showed its high identity with lipases from Pseudomonas luteola (91%), Burkholderia cepacia (96%) and Burkholderia lata (97%), and classified LipBC lipase in the lipase subfamily I.2. The genes lipA and lipB were amplified and cloned into expression vectors pET28a(+) and pT7-7, respectively. His-tagged LipBC and native LifBC were co-expressed in Escherichia coli and purified. LipBC and LifBC have molecular weights of 35.9 kDa and 37 kDa, respectively, and remain complexed after purification. The Lip-LifBC complex was active and stable over a wide range of pH values (6.5-10) and temperatures (25-45 °C), with the highest specific activity (1426 U mg -1 ) being against tributyrin. The Lip-LifBC complex immobilized on Sepabeads was able to catalyze the synthesis of ethyl-oleate in n‑hexane with an activity of 4 U g -1 , maintaining high conversion (>80%) over 5 reaction cycles of 6 h at 45 °C. The results obtained in this work provide a basis for the development of applications of recombinant LipBC in biocatalysis. Copyright © 2018 Elsevier B.V. All rights reserved.

Impact of constitutional isomers of (BMes(2))phenylpyridine on structure, stability, phosphorescence, and Lewis acidity of mononuclear and dinuclear Pt(II) complexes.

PubMed

Rao, Ying-Li; Wang, Suning

2009-08-17

The impact of two constitutional isomers, 2-(4-BMes(2)-Ph)-pyridine (p-B-ppy, 1) and 5-BMes(2)-2-ph-pyridine (p-ppy-B, 2), as N,C-chelate ligands on the structures, stabilities, electronic and photophysical properties, and Lewis acidities of Pt(II) complexes has been investigated. Six Pt(II) complexes, Pt(p-B-ppy)Ph(DMSO) (1a), Pt(p-B-ppy)Ph(py) (1b), [Pt(p-B-ppy)Ph](2)(4,4'-bipy) (1c), Pt(p-ppy-B)Ph(DMSO) (2a), Pt(p-ppy-B)Ph(py) (2b), and [Pt(p-ppy-B)Ph](2)(4,4'-bipy) (2c), have been synthesized and fully characterized. The structures of 1a, 1c, 2a, and 2c were established by single-crystal X-ray diffraction analysis. All complexes adopt a cis geometry with the phenyl ligand being cis to the phenyl ring of the ppy chelate. The dinuclear complexes 2a and 2c were found to exist in two isomeric forms in solution, syn and anti, with respect to the relative orientation of the two BMes(2) groups in the molecule. While all complexes are stable in solution under ambient air, compound 2a was found to react with H(2)O slowly in solution and form complex 2a-OH, where one of the mesityl groups on the boron center was replaced by an OH group. This instability of 2a is attributed to an internal dimethylsulfoxide-directed hydrolysis process via hydrogen bonds. The electron-accepting ability of the free ligands and the complexes were examined by cyclic voltammetry, establishing that, for p-ppy-B, Pt(II) chelation enhances the electron-accepting ability while, for p-B-ppy, Pt(II) chelation has little impact. All Pt(II) complexes display oxygen-sensitive phosphorescence in solution at ambient temperature, dominated by B-ppy or ppy-B centered pi --> pi* transitions. The Lewis acidity of the complexes was examined by fluoride titration experiments using UV-vis, phosphorescence, and NMR spectroscopic methods, establishing that the p-ppy-B complexes have similar and strong binding constants while the p-B-ppy complexes have a much lower affinity toward F(-), compared to the free ligands. In the dinuclear complexes, weak electronic communication between the two Pt(II) units is evident in 1c but absent in 2c, attributable to the different steric interactions in the two molecules.

Application of the solid phase C1q and Raji cell radioimmune assays for the detection of circulating immune complexes in glomerulonephritis.

PubMed Central

Tung, K S; Woodroffe, A J; Ahlin, T D; Williams, R C; Wilson, C B

1978-01-01

The C1q solid phase and Raji cell radioimmune assays were used to determine the frequency of detectable circulating immune complexes in patients with glomerulonephritis. In this study, 46% of 56 patients with glomerulonephritis had evidence of circulating immune complexes. More important, circulating immune complexes were associated with some, but not other, types of glomerulonephritis. Thus, immune complexes were detected in lupus glomerulonephritis (9/9 patients), rapidly progressive glomerulonephritis (5/6 patients), and acute nephritis (5/6 patients), but not in IgA-IgG glomerulonephritis (0/7 patients), or membranous glomerulonephritis (0/8 patients). The Raji cell radioimmune assay and the C1q solid phase radioimmune assay showed concordance of 79% in the detection of circulating immune complexes. Serial determinations, in general, showed either persistence of a negative or positive result of conversion of positive to negative. PMID:659639

Kinetic studies on the oxidation of cytochrome b(5) Phe35 mutants with cytochrome c, plastocyanin and inorganic complexes.

PubMed

Yao, Ping; Wang, Yun-Hua; Sun, Bing-Yun; Xie, Yi; Hirota, Shun; Yamauchi, Osamu; Huang, Zhong-Xian

2002-04-01

To illustrate the functions of the aromatic residue Phe35 of cytochrome b(5) and to give further insight into the roles of the Phe35-containing hydrophobic patch and/or aromatic channel of cytochrome b(5), we studied electron transfer reactions of cytochrome b(5) and its Phe35Tyr and Phe35Leu variants with cytochrome c, with the wild-type and Tyr83Phe and Tyr83Leu variants of plastocyanin, and with the inorganic complexes [Fe(EDTA)](-), [Fe(CDTA)](-) and [Ru(NH(3))(6)](3+). The changes at Phe35 of cytochrome b(5) and Tyr83 of plastocyanin do not affect the second-order rate constants for the electron transfer reactions. These results show that the invariant aromatic residues and aromatic patch/channel are not essential for electron transfer in these systems.

Genetic Networks Activated by Blast Injury to the Eye

DTIC Science & Technology

2018-03-01

em be r 7 C hr 4: 1 4. 42 95 77 7. 98 0. 89 C ar 12 ca rb on...12 .2 8 -0 .8 6 Tm em 16 1b tr an sm em br an e pr ot ei n 16 1B C hr 13 : 8 4. 36 19 01 10 .9 1 0. 86 Pd cd 5 pr og ra m m ed c el l d ea th 5...sy nt he ta se fa m ily m em be r 3 C hr 8: 1 25 .2 99 40 5 9. 51 -0 .8 6 Sl c1 7a 7 so lu te c ar rie r f am

Observation of B{sup +}{yields}{xi}{sub c}{sup 0}{lambda}{sub c}{sup +} and evidence for B{sup 0}{yields}{xi}{sub c}{sup -}{lambda}{sub c}{sup +}

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

Chistov, R.; Aushev, T.; Balagura, V.

We report the first observation of the decay B{sup +}{yields}{xi}{sub c}{sup 0}{lambda}{sub c}{sup +} with a significance of 8.7{sigma} and evidence for the decay B{sup 0}{yields}{xi}{sub c}{sup -}{lambda}{sub c}{sup +} with a significance of 3.8{sigma}. The product B(B{sup +}{yields}{xi}{sub c}{sup 0}{lambda}{sub c}{sup +})xB({xi}{sub c}{sup 0}{yields}{xi}{sup +}{pi}{sup -}) is measured to be (4.8{sub -0.9}{sup +1.0}{+-}1.1{+-}1.2)x10{sup -5}, and B(B{sup 0}{yields}{xi}{sub c}{sup -}{lambda}{sub c}{sup +})xB({xi}{sub c}{sup -}{yields}{xi}{sup +}{pi}{sup -}{pi}{sup -}) is measured to be (9.3{sub -2.8}{sup +3.7}{+-}1.9{+-}2.4)x10{sup -5}. The errors are statistical, systematic and the error of the {lambda}{sub c}{sup +}{yields}pK{sup -}{pi}{sup +} branching fraction, respectively. The decay B{sup +}{yields}{xi}{sub c}{sup 0}{lambda}{sub c}{supmore » +} is the first example of a two-body exclusive B{sup +} decay into two charmed baryons. The data used for this analysis was accumulated at the {upsilon}(4S) resonance, using the Belle detector at the e{sup +}e{sup -} asymmetric-energy collider KEKB. The integrated luminosity of the data sample is equal to 357 fb{sup -1}, corresponding to 386x10{sup 6} BB pairs.« less

Interaction of hydrated electron with dietary flavonoids and phenolic acids: rate constants and transient spectra studied by pulse radiolysis.

PubMed

Cai, Z; Li, X; Katsumura, Y

1999-10-01

The reaction rate constants and transient spectra of 11 flavonoids and 4 phenolic acids reacting with e(aq)- at neutral pH were measured. Absorption bands of the transients of e(aq)- reacting with the above compounds all located at a wavelength shorter than 400 nm. The e(aq)- scavenging abilities were divided into three groups: (+)catechin ((1.2 +/-0.1) x 10(8) M(-1)s(-1)) < 4-chromanol ((4.4 +/- 0.4) x 10(8) M(-1)s(-1)) < genistein ((6.2+/-0.4) x 10(9) M (-1) s(-1) approximately genistin ((8 +/- 1) x 10(9) M(-1)s(-1)) approximately rutin ((7.6 +/- 0.4) x M(-1)s(-1) approximately caffeic acid ((8.3 +/- 0.5) x 10(9)M(-1)s(-1)) < transcinnamic acid((1.1 +/- 0.1) x 10(10) M(-1)s(-1)) approximately p-coumaric acid ((1.1 +/- 0.1) x 10(10) M(-1)s(-1) approximately 2,4,6-trihydroxylbenzoic acid((1.1 +/- 0.1) x 10(10) M(-1)s(-1)) approximately baicalein ((1.1 +/- 0.5) x 10(10) M(-1)s(-1)) approximately baicalin((1.3 + 0.1) X 10(10) M(-1)s(-1)) approximately naringenin ((1.2 +/- 0.1) x 10(10) M(-1)s(-1)) approximately naringin ((1.0 +/- 0.1) x 10(10) M(-1)s(-1)) approximately gossypin((1.2 +/- 0.1) x 10(10) M(-1)s(-1)) approximately quercetin((1.3 +/- 0.5) x 10(10) M(-1)s(-1)). These results suggested that C4 keto group is the active site for e(aq)- to attack on flavonoids and phenolic acids, whereas the o-dihydroxy structure in B ring, the C2,3 double bond, the C3-OH group, and glucosylation, which are key structures that influence the antioxidant activities of flavonoids and phenolic acids, have little effects on the e(aq)- scavenging activities.

Piano-stool lutetium amido and imido compounds supported by a constrained bis(oxazoline)cyclopentadienyl ligand

DOE PAGES

Lampland, Nicole L.; Zhu, Jing; Hovey, Megan; ...

2015-06-25

{Bo MCp tet}Lu(CH 2Ph) 2 ( 1; Bo MCp tet = MeC(Ox Me2 2C 5Me 4; Ox Me2 = 4,4-dimethyl-2-oxazoline) was prepared in 95% yield from the reaction of Bo MCp tetH and Lu(CH 2Ph) 3THF 3. Compound 1 reacts with 1 or 2 equiv of H 2NCH 2R (R = C 6H 5, 1-C 10H 7) to give the corresponding imido complexes [{Bo MCp tet}LuNCH 2R] 2 (R = C 6H 5 ( 2a), 1-C 10H 7 ( 2b)) or amido complexes {Bo MCp tet}Lu(NHCH 2R) 2 (R = C 6H 5 ( 3a), 1-C 10H 7 ( 3b)).more » When isolated, the imido species are insoluble in nonprotic organic solvents. Crystallographic characterization reveals dimeric [{Bo MCp tet}LuNCH 2(1-C 10H 7)] 2 in the solid state. The reaction of 1 and NH3B(C6F5)3 affords crystallographically characterized {Bo MCp tet}Lu{NHB(C 6F 5) 2}C 6F 5. This species is proposed to form via a transient lutetium imido, which undergoes C6F5 migration to the lutetium center.« less

Personalized biomarkers to monitor disease progression in advanced non-small-cell lung cancer patients treated with icotinib.

PubMed

Song, Gaoguang; Liu, Yujie; Wang, Yanying; Ren, Guanjun; Guo, Shuai; Ren, Junling; Zhang, Li; Li, Zhili

2015-02-02

Disease-specific humoral immune response-related protein complexes in blood are associated with disease progression. Thirty-one patients with stage IIIB and IV non-small-cell lung cancer (NSCLC) were administered with oral dose of icotinib hydrochloride (150 mg twice daily or 125 mg 3 times daily) for a 28-continuous-day cycle until diseases progressed or unacceptable toxicity occurred. The levels of immunoinflammation-related protein complexes (IIRPCs) in a series of plasma samples from 31 NSCLC patients treated with icotinib hydrochloride were determined by an optimized native polyacrylamide gel electrophoresis. Three characteristic patterns of the IIRPCs, named as patterns a, b, and c, respectively, were detected in plasma samples from 31 patients. Prior to the treatment, there were 18 patients in pattern a consisting of 5 IIRPCs, 9 in pattern b consisting of six IIRPCs, and 4 in pattern c without the IIRPCs. The levels of the IIRPCs in 27 patients were quantified. Our results indicate that the time length of humoral immune and inflammation response (TLHIIR) was closely associated with disease progression, and the median TLHIIR was 22.0 weeks, 95% confidence interval: 16.2 to 33.0 weeks, with a lead time of median 11 weeks relative to clinical imaging evidence confirmed by computed tomography or magnetic resonance imaging (the median progression-free survival, 34.0 weeks, 95% confidence interval: 27.9 to 49.0 weeks). The complex relationships between humoral immune response, acquired resistance, and disease progression existed. Personalized IIRPCs could be indicators to monitor the disease progression. Copyright © 2014 Elsevier B.V. All rights reserved.

Structural comparative studies on new MnII, CrIII and RuIII complexes derived from 2,4,6-tri-(2-pyridyl)-1,3,5-triazine (TPTZ)

NASA Astrophysics Data System (ADS)

Al-Assy, Waleed H.; El-Askalany, Abdel Moneum H.; Mostafa, Mohsen M.

2013-12-01

The structure of a new MnII complex, [Mn(TPTZ)Cl2(H2O)]ṡH2O, was established by a single crystal X-ray diffraction. Crystal data are as follow: monoclinic, P21/c, a = 8.7202 (3) Å, b = 11.5712 (4) Å, c = 20.8675 (9) Å, β = 11 (18) × 1010, V = 2029.27 (13) Å3, Z = 4. The HOMO, LUMO and other DFT parameters on the atoms have been calculated to confirm the geometry of the ligand and its complexes using material studio program. The complexes were characterized by elemental analyses, spectral, magnetic, thermal and cyclic voltammetry measurements. Electronic spectra and magnetic moments of the complexes suggest distorted-octahedral structures around the metal ions (MnII, CrIII and RuIII). The redox properties were investigated by cyclic voltammetry. Kinetic parameters were determined using Coats-Redfern and Horowitz-Metzger methods. The results of DNA studies of the metal complexes promised to be effective in tumour treatment.

The new silver borate Ag{sub 3}B{sub 5}O{sub 9}

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

Sohr, Gerhard; Falkowski, Viktoria; Huppertz, Hubert, E-mail: hubert.huppertz@uibk.ac.at

2015-05-15

Single crystals of Ag{sub 3}B{sub 5}O{sub 9} were obtained via high-pressure synthesis at 3 GPa and 600 °C, using a Walker-type multianvil high-pressure device. Ag{sub 3}B{sub 5}O{sub 9} crystalizes with a=674.7(2), b=943.5(2), c=1103.5(2) pm, V=0.7025(2) nm{sup 3}, and Z=4 in the noncentrosymmetric space group P2{sub 1}2{sub 1}2{sub 1} (no. 19). The orthorhombic structure was refined from 3740 independent reflections with R1=0.0496 and wR2=0.587 (all data). It is built up from infinite corner-sharing chains of BO{sub 4} tetrahedra along the a axis, which are interconnected by BO{sub 3} groups to form a network. In the structure, three crystallographically independent sites aremore » occupied with Ag{sup +} cations exhibiting argentophillic interactions. The synthetic conditions as well as the results of the single crystal structure analysis are presented. - Graphical abstract: Noncentrosymmetric silver borate: During investigations in the system Ag–B–O, a new noncentrosymmetric silver borate Ag{sub 3}B{sub 5}O{sub 9} was discovered. The new structure type is built up from corner-sharing BO{sub 3} and BO{sub 4} groups, forming a network. Argentophillic interactions are clearly indicated by the Ag{sup +}⋯Ag{sup +} distances present in the structure. - Highlights: • A noncentrosymmetric borate Ag{sub 3}B{sub 5}O{sub 9} is accessible via high-pressure synthesis. • Ag{sub 3}B{sub 5}O{sub 9} is the second high-pressure silver borate. • Ag{sup +}⋯Ag{sup +} distances in Ag3B5O9 clearly indicate the presence of argentophillic interactions.« less

Incidence of hepatocellular carcinoma according to hepatitis B virus genotype in Alaska Native people.

PubMed

Ching, Lance K; Gounder, Prabhu P; Bulkow, Lisa; Spradling, Philip R; Bruce, Michael G; Negus, Susan; Snowball, Mary; McMahon, Brian J

2016-10-01

Most regions of the world have ≤3 co-circulating hepatitis B virus (HBV) genotypes, which limits direct comparisons of hepatocellular carcinoma (HCC) risk among HBV-infected persons by genotype. We evaluated HCC incidence by HBV genotype in a cohort of Alaska Native (AN) persons where five HBV genotypes (A, B, C, D, F) have been identified. Our cohort comprised AN persons with chronic HBV infection identified during 1983-2012 who consented to participate in this study. Cohort persons were offered annual hepatitis B e antigen (HBeAg) testing and semi-annual HCC screening. We developed a logistic regression model to compare HCC risk by genotype, adjusting for age, sex, region and HBeAg status. Among the 1235 consenting study participants, 711 (57.6%) were male, 510 (41.3%) were HBeAg positive at cohort entry and 43 (3.5%) developed HCC. The HBV genotype was known for 1142 (92.5%) persons (13.5% A, 3.9% B, 6.7% C, 56.9% D, 19.0% F). The HCC incidence/1000 person-years of follow-up for genotypes A, B, C, D and F was 1.3, 0, 5.5, 0.4 and 4.2 respectively. Compared with persons with HBV genotype B/D infection, the HCC risk was higher for persons with genotypes A [adjusted odds ratio (aOR): 3.9, 95% confidence interval (CI): 1.14-13.74], C (aOR: 16.3, 95% CI: 5.20-51.11) and F (aOR: 13.9, 95% CI: 5.30-36.69). HBV genotype is independently associated with HCC risk. AN persons with genotypes A, C and F are at higher risk compared with genotypes B or D. Published 2016. This article is a U.S. Government work and is in the public domain in the USA.

On the formation and structure of rare-earth element complexes in aqueous solutions under hydrothermal conditions with new data on gadolinium aqua and chloro complexes

USGS Publications Warehouse

Mayanovic, Robert A.; Anderson, Alan J.; Bassett, William A.; Chou, I.-Ming

2007-01-01

Synchrotron X-ray spectroscopy experiments were made on the Gd(III) aqua and chloro complexes in low pH aqueous solutions at temperatures ranging from 25 to 500????C and at pressures up to 480??MPa using a hydrothermal diamond anvil cell. Analysis of fluorescence Gd L3-edge X-ray absorption fine structure (XAFS) spectra measured from a 0.006m Gd/0.16m HNO3 aqueous solution at temperatures up to 500????C and at pressures up to 260??MPa shows that the Gd-O distance of the Gd3+ aqua ion decreases steadily at a rate of ??? 0.007??A??/100????C whereas the number of coordinated H2O molecules decreases from 9.0 ?? 0.5 to 7.0 ?? 0.4. The loss of water molecules in the Gd3+ aqua ion inner hydration shell over this temperature range (a 22% reduction) is smaller than exhibited by the Yb3+ aqua ion (42% reduction) indicating that the former is significantly more stable than the later. We conjecture that the anomalous enrichment of Gd reported from measurement of REE concentrations in ocean waters may be attributed to the enhanced stability of the Gd3+ aqua ion relative to other REEs. Gd L3-edge XAFS measurements of 0.006m and 0.1m GdCl3 aqueous solutions at temperatures up to 500????C and pressures up to 480??MPa reveal that the onset of significant Gd3+-Cl- association occurs around 300????C. Partially-hydrated stepwise inner-sphere complexes most likely of the type Gd(H2O)??-nCln+3-n occur in the chloride solutions at higher temperatures, where ?? ??? 8 at 300????C decreasing slightly to an intermediate value between 7 and 8 upon approaching 500????C. This is the first direct evidence for the occurrence of partially-hydrated REE Gd (this study) and Yb [Mayanovic, R.A., Jayanetti, S., Anderson, A.J., Bassett, W.A., Chou, I-M., 2002a. The structure of Yb3+ aquo ion and chloro complexes in aqueous solutions at up to 500 ??C and 270 MPa. J. Phys. Chem. A 106, 6591-6599.] chloro complexes in hydrothermal solutions. The number of chlorides (n) of the partially-hydrated Gd(III) chloro complexes increases steadily with temperature from 0.4 ?? 0.2 to 1.7 ?? 0.3 in the 0.006m chloride solution and from 0.9 ?? 0.7 to 1.8 ?? 0.7 in the 0.1m GdCl3 aqueous solution in the 300-500????C range. Conversely, the number of H2O ligands of Gd(H2O)??-nCln+3-n complexes decreases steadily from 8.9 ?? 0.4 to 5.8 ?? 0.7 in the 0.006m GdCl3 aqueous solution and from 9.0 ?? 0.5 to 5.3 ?? 1.0 in the 0.1m GdCl3 aqueous solution at temperatures from 25 to 500????C. Analysis of our results shows that the chloride ions partially displace the inner-shell water molecules during Gd(III) complex formation under hydrothermal conditions. The Gd-OH2 bond of the partially-hydrated Gd(III) chloro complexes exhibits slightly smaller rates of length contraction (??? 0.005??A??/100????C) for both solutions. The structural aspects of chloride speciation of Gd(III) as measured from this study and of Yb(III) as measured from our previous experiments are consistent with the solubility of these and other REE in deep-sea hydrothermal fluids. ?? 2006 Elsevier B.V. All rights reserved.

Periplasmic Cytophaga hutchinsonii Endoglucanases Are Required for Use of Crystalline Cellulose as the Sole Source of Carbon and Energy

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

Zhu, Yongtao; Han, Lanlan; Hefferon, Kathleen L.

2016-06-03

The soil bacteriumCytophaga hutchinsoniiactively digests crystalline cellulose by a poorly understood mechanism. Genome analyses identified nine genes predicted to encode endoglucanases with roles in this process. No predicted cellobiohydrolases, which are usually involved in the utilization of crystalline cellulose, were identified. Chromosomal deletions were performed in eight of the endoglucanase-encoding genes:cel5A,cel5B,cel5C,cel9A,cel9B,cel9C,cel9E, andcel9F. Each mutant retained the ability to digest crystalline cellulose, although the deletion ofcel9Ccaused a modest decrease in cellulose utilization. Strains with multiple deletions were constructed to identify the critical cellulases. Cells of a mutant lacking bothcel5Bandcel9Cwere completely deficient in growth on cellulose. Cell fractionation and biochemical analyses indicatemore » that Cel5B and Cel9C are periplasmic nonprocessive endoglucanases. The requirement of periplasmic endoglucanases for cellulose utilization suggests that cellodextrins are transported across the outer membrane during this process. Bioinformatic analyses predict that Cel5A, Cel9A, Cel9B, Cel9D, and Cel9E are secreted across the outer membrane by the type IX secretion system, which has been linked to cellulose utilization. These secreted endoglucanases may perform the initial digestion within amorphous regions on the cellulose fibers, releasing oligomers that are transported into the periplasm for further digestion by Cel5B and Cel9C. The results suggest that both cell surface and periplasmic endoglucanases are required for the growth ofC. hutchinsoniion cellulose and that novel cell surface proteins may solubilize and transport cellodextrins across the outer membrane. IMPORTANCEThe bacteriumCytophaga hutchinsoniidigests crystalline cellulose by an unknown mechanism. It lacks processive cellobiohydrolases that are often involved in cellulose digestion. Critical cellulolytic enzymes were identified by genetic analyses. Intracellular (periplasmic) nonprocessive endoglucanases performed an important role in cellulose utilization. The results suggest a model involving partial digestion at the cell surface, solubilization and uptake of cellodextrins across the outer membrane by an unknown mechanism, and further digestion within the periplasm. The ability to sequester cellodextrins and digest them intracellularly may limit losses of soluble cellobiose to other organisms.C. hutchinsoniiuses an unusual approach to digest cellulose and is a potential source of novel proteins to increase the efficiency of conversion of cellulose into soluble sugars and biofuels.« less

Cation-poor complex metallic alloys in Ba(Eu)–Au–Al(Ga) systems: Identifying the keys that control structural arrangements and atom distributions at the atomic level

DOE PAGES

Smetana, Volodymyr; Steinberg, Simon; Mudryk, Yaroslav; ...

2015-10-19

Four complex intermetallic compounds BaAu 6±xGa 6±y (x = 1, y = 0.9) (I), BaAu 6±xAl 6±y (x = 0.9, y = 0.6) (II), EuAu 6.2Ga 5.8 (III), and EuAu 6.1Al 5.9 (IV) have been synthesized, and their structures and homogeneity ranges have been determined by single crystal and powder X-ray diffraction. Whereas I and II originate from the NaZn 13-type structure (cF104–112, Fm3C), III (tP52, P4/nbm) is derived from the tetragonal Ce 2Ni 17Si 9-type, and IV (oP104, Pbcm) crystallizes in a new orthorhombic structure type. Both I and II feature formally anionic networks with completely mixed site occupationmore » by Au and triel (Tr = Al, Ga) atoms, while a successive decrease of local symmetry from the parental structures of I and II to III and, ultimately, to IV correlates with increasing separation of Au and Tr on individual crystallographic sites. Density functional theory-based calculations were employed to determine the crystallographic site preferences of Au and the respective triel element to elucidate reasons for the atom distribution (“coloring scheme”). Chemical bonding analyses for two different “EuAu 6Tr 6” models reveal maximization of the number of heteroatomic Au–Tr bonds as the driving force for atom organization. The Fermi levels fall in broad pseudogaps for both models allowing some electronic flexibility. Spin-polarized band structure calculations on the “EuAu 6Tr 6” models hint to singlet ground states for europium and long-range magnetic coupling for both EuAu 6.2Ga 5.8 (III) and EuAu 6.1Al 5.9 (IV). This is substantiated by experimental evidence because both compounds show nearly identical magnetic behavior with ferromagnetic transitions at T C = 6 K and net magnetic moments of 7.35 μB/f.u. at 2 K. As a result, the effective moments of 8.3 μB/f.u., determined from Curie–Weiss fits, point to divalent oxidation states for europium in both III and IV.« less

Detection of Phase Transition in Generalized Pólya Urn in Information Cascade Experiment

NASA Astrophysics Data System (ADS)

Hino, Masafumi; Irie, Yosuke; Hisakado, Masato; Takahashi, Taiki; Mori, Shintaro

2016-03-01

We propose a method of detecting a phase transition in a generalized Pólya urn in an information cascade experiment. The method is based on the asymptotic behavior of the correlation C(t) between the first subject’s choice and the t + 1-th subject’s choice, the limit value of which, c ≡ limt to ∞ C(t), is the order parameter of the phase transition. To verify the method, we perform a voting experiment using two-choice questions. An urn X is chosen at random from two urns A and B, which contain red and blue balls in different configurations. Subjects sequentially guess whether X is A or B using information about the prior subjects’ choices and the color of a ball randomly drawn from X. The color tells the subject which is X with probability q. We set q in { 5/9,6/9,7/9,8/9} by controlling the configurations of red and blue balls in A and B. The (average) lengths of the sequence of the subjects are 63, 63, 54.0, and 60.5 for q in { 5/9,6/9,7/9,8/9} , respectively. We describe the sequential voting process by a nonlinear Pólya urn model. The model suggests the possibility of a phase transition when q changes. We show that c > 0 (= 0) for q = 5/9,6/9 (7/9,8/9) and detect the phase transition using the proposed method.

Pilot Designed Aircraft Displays in General Aviation: An Exploratory Study and Analysis

NASA Astrophysics Data System (ADS)

Conaway, Cody R.

From 2001-2011, the General Aviation (GA) fatal accident rate remained unchanged (Duquette & Dorr, 2014) with an overall stagnant accident rate between 2004 and 2013. The leading cause, loss of control in flight (NTSB, 2015b & 2015c) due to pilot inability to recognize approach to stall/spin conditions (NTSB, 2015b & 2016b). In 2013, there were 1,224 GA accidents in the U.S., accounting for 94% of all U.S. aviation accidents and 90% of all U.S. aviation fatalities that year (NTSB, 2015c). Aviation entails multiple challenges for pilots related to task management, procedural errors, perceptual distortions, and cognitive discrepancies. While machine errors in airplanes have continued to decrease over the years, human error still has not (NTSB, 2013). A preliminary analysis of a PC-based, Garmin G1000 flight deck was conducted with 3 professional pilots. Analyses revealed increased task load, opportunities for distraction, confusing perceptual ques, and hindered cognitive performance. Complex usage problems were deeply ingrained in the functionality of the system, forcing pilots to use fallible work arounds, add unnecessary steps, and memorize knob turns or button pushes. Modern computing now has the potential to free GA cockpit designs from knobs, soft keys, or limited display options. Dynamic digital displays might include changes in instrumentation or menu structuring depending on the phase of flight. Airspeed indicators could increase in size to become more salient during landing, simultaneously highlighting pitch angle on Attitude Indicators and automatically decluttering unnecessary information for landing. Likewise, Angle-of-Attack indicators demonstrate a great safety and performance advantage for pilots (Duquette & Dorr, 2014; NTSB, 2015b & 2016b), an instrument typically found in military platforms and now the Icon A5, light-sport aircraft (Icon, 2016). How does the design of pilots' environment---the cockpit---further influence their efficiency and effectiveness? To explore the possibilities for small aircraft displays, a participatory design investigation was conducted with 9 qualified instrument pilots. Aviators designed mock cockpits on a PC using pictorial cutouts of analog (e.g., mechanical dials) and digital (e.g., dynamic displays) controls. Data was analyzed qualitatively and compared to similar work. Finally, a template for GA displays was developed based on pilot input.

Trans- and cis-2-phenylindole platinum(II) complexes as cytotoxic agents against human breast adenocarcinoma cell lines

NASA Astrophysics Data System (ADS)

Tomé, Maria; López, Concepción; González, Asensio; Ozay, Bahadir; Quirante, Josefina; Font-Bardía, Mercè; Calvet, Teresa; Calvis, Carme; Messeguer, Ramon; Baldomá, Laura; Badía, Josefa

2013-09-01

The synthesis and characterization of the new 2-phenylindole derivative: C8H3N-2-C6H5-3NOMe-5OMe (3c) and the trans- and cis-isomers of [Pt(3c)Cl2(DMSO)] complexes (4c and 5c, respectively) are described. The crystal structures of 4c·CH2Cl2 and 5c confirm: (a) the existence of a Pt-Nindole bond, (b) the relative arrangement of the Cl- ligands [trans- (in 4c) or cis- (in 5c)] and (c) the anti-(E) configuration of the oxime. The cytotoxic assessment of C8H3N-2-(C6H4-4‧R1)-3NOMe-5R2 [with R1 = R2 = H (3a); R1 = Cl, R2 = H (3b) and R1 = H, R2 = OMe (3c)] and the geometrical isomers of [Pt(L)Cl2(DMSO)] with L = 3a-3c [trans- (4a-4c) and cis- (5a-5c), respectively] against human breast adenocarcinoma cell lines (MDA-MB231 and MCF-7) is also reported and reveals that all the platinum(II) complexes (except 4a) are more cytotoxic than cisplatin in front of the MCF7 cell line. Electrophoretic DNA migration studies of the synthesized compounds in the absence and in the presence of topoisomerase-I have been performed, in order to get further insights into their mechanism of action.

An Archeological Survey, Initial Site Testing and Geomorphic Study of Ditches 7, 13 and Lower Buffalo Creek in Craighead, Mississippi and Poinsett Counties, Arkansas.

DTIC Science & Technology

1988-04-01

of the Rebellion. Government Printing Office, Washington, D.C. United States Department of the Interior 1974 hLa Lak Wilderness Study Summary. Fish...2 9 2 X 13 50 B25 3 12 X 15 51 B26 3 18 5 26 52 B27 3 27 1 X 31 53 B28 5 16 9 X 30 54 B29 6 20 7 4 X 37 55 B30 9 12 X 21 56 B31 7 21 12 1 X 41 FSN LOC...20 A18 1 I 25 A23 1 1 26 A24 1 1 FSN LOC 0 DR UP H C PFLK SFLK IFLK FCR BT UNNOD TOTAL 30 84 1 1 49 B24 1 1 50 B25 2 2 51 B26 1 1 52 B27 1 1 57 B33 1

Octahedral d[sup 6] Bis(maleimide) and Bis(maleic anhydride) complexes of molybdenum

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

Lai, Chen-Hsing; Cheng, Chien-Hong; Liao, Fen-Ling

1993-12-08

Mo(CO)[sub 3](CH[sub 3]CN)[sub 3] reacts with 2 equiv of alkene, where the alkene is maleimide (MI), N-phenylmaleimide (PhMI), or N-methylmaleimide, to give the corresponding Mo(CO)[sub 2](alkene)[sub 2](CH[sub 3]CN)[sub 2] complex (1a-c, respectively) in excellent yield. Dissolution of 1 in DMSO led to the substitution of acetonitrile ligands by DMSO to form the corresponding cis bis(DMSO) complexes 2a-c. Addition of 1 equiv of NN to 1 yields MO(CO)[sub 2](alkene)[sub 2](alkene)[sub 2](NN) (NN = en, alkene = PhMI (3b), MeMI (3c); NN = o-phenylenediamine, alkene = PhMI (4)). Treatment of Mo-(CO)[sub 4](NN) (NN = phen or bpy), with 2 equiv of alkenemore » in refluxed acetonitrile for 2 h gave Mo(CO)[sub 2]-(alkene)[sub 2](NN) (NN = phen, alkene = MI (5a), PhMI (5b); NN = bpy, alkene = MI (6a), PhMI (6b)). Treatment of Mo(CO)[sub 3](CH[sub 3]CN)[sub 3] with 2 equiv of maleic anhydride (MA) gave Mo(CO)[sub 2](MA)[sub 2](CH[sub 3]CN)[sub 2] (7). The acetonitrile ligands in 7 were replaced by DMSO molecules to give complex 8 as 7 was dissolved in DMSO. Similarly, the reaction of 7 with a bidentate ligand NN (phen or bpy) gave the substituted product Mo(CO)[sub 2](MA)[sub 2](NN) (9 or 10). The structures and conformations of 1b and 7 were determined by X-ray diffraction. Both molecules adopt an octahedral geometry with mutually perpendicular trans alkene ligands and each alkene ligand eclipses a N-Mo-CO vector. Each PhMI or MA is oriented so that the central nitrogen or oxygen atom points to a carbonyl group. 1b crystallizes in triclinic space group P1. There are three possible conformations for a trans bis(maleimide) or bis(maleic anhydride) complex (I-III). The results of X-ray and NMR studies indicated that the main conformation of complexes 1-10 is I both in the solid state and in solution.« less

EnviroAtlas One Meter Resolution Urban Land Cover Data (2008-2012) Web Service

EPA Pesticide Factsheets

This EnviroAtlas web service supports research and online mapping activities related to EnviroAtlas (https://www.epa.gov/enviroatlas ). The EnviroAtlas One Meter-scale Urban Land Cover (MULC) Data were generated individually for each EnviroAtlas community. Source imagery varies by community. Land cover classes mapped also vary by community and include the following: water, impervious surfaces, soil and barren land, trees, shrub, grass and herbaceous, agriculture, orchards, woody wetlands, and emergent wetlands. Accuracy assessments were completed for each community's classification. For specific information about methods and accuracy of each community's land cover classification, consult their individual metadata records: Austin, TX (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7B91A32A9D-96F5-4FA0-BC97-73BAD5D1F158%7D); Cleveland, OH (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7B82ab1edf-8fc8-4667-9c52-5a5acffffa34%7D); Des Moines, IA (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7BA4152198-978D-4C0B-959F-42EABA9C4E1B%7D); Durham, NC (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7B2FF66877-A037-4693-9718-D1870AA3F084%7D); Fresno, CA (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7B87041CF3-05BC-43C3-82DA-F066267C9871%7D); Green Bay, WI (https://edg.epa.gov/metadata/catalog/search/resource/details.page?uuid=%7BD602E7C9-7F53-4C24

The C1Σ+ , A1Σ+ , and b3Π0+ states of LiRb

NASA Astrophysics Data System (ADS)

Stevenson, Ian; Blasing, David; Chen, Yong; Elliott, Daniel

2017-04-01

We present the first spectroscopic studies of the C1Σ+ electronic state and the A1Σ+ - b3Π0+ complex in 7Li - 85Rb. Using resonantly-enhanced, two-photon ionization, we observed v = 7 , 9, 12, 13 and 26 - 45 of the C1Σ+ state. We augment the REMPI data with a form of depletion spectra in regions of dense spectral lines. The A1Σ+ - b3Π0+ complex was observed with depletion spectroscopy, depleting to vibrational levels v = 0 -> 29 of the A1Σ+ state and v = 8 -> 18 of the b3Π0+ state. For all three series, we determine the term energy and vibrational constants. Finally, we outline several possible future projects in ultracold molecules based on the data presented here.

C 1Σ+ , A 1Σ+ , and b 3Π0+ states of LiRb

NASA Astrophysics Data System (ADS)

Stevenson, I. C.; Blasing, D. B.; Chen, Y. P.; Elliott, D. S.

2016-12-01

We present the first spectroscopic studies of the C 1Σ+ electronic state and the A 1Σ+ -b 3Π0+ complex in 7Li-85Rb. Using resonantly enhanced, two-photon ionization, we observed v =7 , 9, 12, 13, and 26-45 of the C 1Σ+ state. We augment the REMPI data with a form of depletion spectra in regions of dense spectral lines. The A 1Σ+ -b 3Π0+ complex was observed with depletion spectroscopy, depleting to vibrational levels v =0 →29 of the A 1Σ+ state and v =8 →18 of the b 3Π0+ state. For all three series, we determine the term energy and vibrational constants. Finally, we outline several possible future projects based on the data presented here.

Crystallization and x-ray diffraction analysis of a putative bacterial class I labdane-related diterpene synthase [Crysallization and preliminary x-ray diffraction analysis of a bacterial class I labdane-related diterpene synthase

DOE PAGES

Serrano-Posada, Hugo; Centeno-Leija, Sara; Rojas-Trejo, Sonia; ...

2015-08-25

Here, labdane-related diterpenoids are natural products with potential pharmaceutical applications that are rarely found in bacteria. Here, a putative class I labdane-related diterpene synthase (LrdC) identified by genome mining in a streptomycete was successfully crystallized using the microbatch method. Crystals of the LrdC enzyme were obtained in a holo form with its natural cofactor Mg 2+ (LrdC-Mg 2+) and in complex with inorganic pyrophosphate (PP i) (LrdC-Mg 2+–PP i). Crystals of native LrdC-Mg 2+ diffracted to 2.50 Å resolution and belonged to the trigonal space group P3 221, with unit-cell parameters a = b = 107.1, c = 89.2 Å.more » Crystals of the LrdC-Mg 2+–PP i complex grown in the same conditions as the native enzyme with PEG 8000 diffracted to 2.36 Å resolution and also belonged to the trigonal space group P3 221. Crystals of the LrdC-Mg 2+–PP i complex grown in a second crystallization condition with PEG 3350 diffracted to 2.57 Å resolution and belonged to the monoclinic space group P2 1, with unit-cell parameters a = 49.9, b = 104.1, c = 66.5 Å, β = 111.4°. The structure was determined by the single-wavelength anomalous dispersion (SAD) technique using the osmium signal from a potassium hexachloroosmate (IV) derivative.« less

Expression, purification, crystallization and preliminary X-ray crystallographic analysis of a resuscitation-promoting factor from Mycobacterium tuberculosis

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

Ruggiero, Alessia; Tizzano, Barbara; Geerlof, Arie

2007-10-01

The first crystallization of a resuscitation-promoting factor has been performed. Multiwavelength anomalous dispersion experiments have been carried out to obtain experimental phases using data at 2.9 Å resolution from a selenomethionine derivative. The resuscitation-promoting factor RpfB, the most complex of the five resuscitation-promoting factors produced by M. tuberculosis, is devoted to bacterial reactivation from the dormant state. RpfB consists of 362 residues predicted to form five domains. An RpfB fragment containing the protein catalytic domain and a G5 domain has been successfully crystallized using vapour-diffusion methods. This is the first crystallographic study of a resuscitation-promoting factor. Crystals of this proteinmore » belong to space group I422, with unit-cell parameters a = 97.63, b = 97.63, c = 114.87 Å. Diffraction data have also been collected from a selenomethionine derivative at 2.9 Å resolution. Model building using the phases derived from the multiwavelength anomalous dispersion experiment is in progress.« less

Synthesis and Properties of "Sandwich" Diimine-Coinage Metal Ethylene Complexes.

PubMed

Klimovica, Kristine; Kirschbaum, Kristin; Daugulis, Olafs

2016-09-12

Synthesis and full characterization of cationic isostructural "sandwich" diimine-coinage metal ethylene complexes are reported. Ethylene self-exchange kinetics proceeds by an associative exchange mechanism for Cu and Au complexes. The fastest ligand exchange was observed for Ag complex 8a . The upper limit of Δ G ‡ , assuming associative ligand exchange, was found to be ca. 5.0 kcal/mol. Ethylene self-exchange in Cu complex 7b proceeds with Δ G 298 ‡ = 12.9 ± 0.1 kcal/mol, while the exchange is the slowest in Au complex 9 , with Δ G 298 ‡ = 16.7 ± 0.1 kcal/mol. Copper complex 7b is unusually stable and can survive in air for years.

Cold Lake Airport, Canada. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F.

DTIC Science & Technology

1983-03-01

b.3 b O.’ 5C.l a:.4 61.?6Z.4 62.7 63.1 63.16 3.. 63.5 * 635 . 63.5 63.5 63.5. 63.S 63.5 63.66 b.,6 65.9 67.8 68.3 68.7 69.8 6 9.8 7’).6 70.1 7".1 7 .1...o Q 99.6 98.5 92.8 1 76.1 , -1.0 86.6 ..- 11 .1 22, -1 z.L i.i i__ .L_ , . 75.3 54.9 3 1 l-J. 7,.. B .1 Z - 14 .1I- 0 - bO*5 43L.I Bi8 1’..3 6.8 5

Propylene glycol-linked amino acid/dipeptide diester prodrugs of oleanolic acid for PepT1-mediated transport: synthesis, intestinal permeability, and pharmacokinetics.

PubMed

Cao, Feng; Gao, Yahan; Wang, Meng; Fang, Lei; Ping, Qineng

2013-04-01

In our previous studies, ethylene glycol-linked amino acid diester prodrugs of oleanolic acid (OA), a Biopharmaceutics Classification System (BCS) class IV drug, designed to target peptide transporter 1 (PepT1) have been synthesized and evaluated. Unlike ethylene glycol, propylene glycol is of very low toxicity in vivo. In this study, propylene glycol was used as a linker to further compare the effect of the type of linker on the stability, permeability, affinity, and bioavailability of the prodrugs of OA. Seven diester prodrugs with amino acid/dipeptide promoieties containing L-Val ester (7a), L-Phe ester (7b), L-Ile ester (7c), D-Val-L-Val ester (9a), L-Val-L-Val ester (9b), L-Ala-L-Val ester (9c), and L-Ala-L-Ile ester (9d) were designed and successfully synthesized. In situ rat single-pass intestinal perfusion (SPIP) model was performed to screen the effective permeability (P(eff)) of the prodrugs. P(eff) of 7a, 7b, 7c, 9a, 9b, 9c, and 9d (6.7-fold, 2.4-fold, 1.24-fold, 1.22-fold, 4.15-fold, 2.2-fold, and 1.4-fold, respectively) in 2-(N-morpholino)ethanesulfonic acid buffer (MES) with pH 6.0 showed significant increase compared to that of OA (p < 0.01). In hydroxyethyl piperazine ethanesulfonic acid buffer (HEPES) of pH 7.4, except for 7c, 9a, and 9d, P(eff) of the other prodrugs containing 7a (5.2-fold), 7b (2.0-fold), 9b (3.1-fold), and 9c (1.7-fold) exhibited significantly higher values than that of OA (p < 0.01). In inhibition studies with glycyl-sarcosine (Gly-Sar, a typical substrate of PepT1), P(eff) of 7a (5.2-fold), 7b (2.0-fold), 9b (3.1-fold), and 9c (2.3-fold) had significantly reduced values (p < 0.01). Compared to the apparent permeability coefficient (P(app)) of OA with Caco-2 cell monolayer, significant enhancement of the P(app) of 7a (5.27-fold), 9b (3.31-fold), 9a (2.26-fold), 7b (2.10-fold), 7c (2.03-fold), 9c (1.87-fold), and 9d (1.39-fold) was also observed (p < 0.01). Inhibition studies with Gly-Sar (1 mM) showed that P(app) of 7a, 9b, and 9c significantly reduced by 1.3-fold, 1.6-fold, and 1.4-fold (p < 0.01), respectively. These results may be attributed to PepT1-mediated transport and their differential affinity toward PepT1. According to the permeability and affinity, 7a and 9b were selected in the pharmacokinetic studies in rats. Compared with group OA, C(max) for group 7a and 9b was enhanced to 3.04-fold (p < 0.01) and 2.62-fold (p < 0.01), respectively. AUC(0→24) was improved to 3.55-fold (p < 0.01) and 3.39-fold (p < 0.01), respectively. Compared to the ethylene glycol-linked amino acid diester prodrugs of OA in our previous work, results from this study revealed that part of the propylene glycol-linked amino acid/dipeptide diester prodrugs showed better stability, permeability, affinity, and bioavailability. In conclusion, propylene glycol-linked amino acid/dipeptide diester prodrugs of OA may be suitable for PepT1-targeted prodrugs of OA to improve the oral bioavailability of OA.

Effects of the microbial siderophore DFO-B on Pb and Cd speciation in aqueous solution.

PubMed

Mishra, Bhoopesh; Haack, Elizabeth A; Maurice, Patricia A; Bunker, Bruce A

2009-01-01

This study investigates the complexation environments of aqueous Pb and Cd in the presence of the trihydroxamate microbial siderophore, desferrioxamine-B (DFO-B) as a function of pH. Complexation of aqueous Pb and Cd with DFO-B was predicted using equilibrium speciation calculation. Synchrotron-based X-ray absorption fine structure (XAFS) spectroscopy at Pb L(III) edge and Cd K edge was used to characterize Pb and Cd-DFO-B complexes at pH values predicted to best represent each of the metal-siderophore complexes. Pb was not found to be complexed measurably by DFO-B at pH 3.0, but was complexed by all three hydroxamate groups to form a totally "caged" hexadentate structure at pH 7.5-9.0. At the intermediate pH value (pH 4.8), a mixture of Pb-DFOB complexes involving binding of the metal through one and two hydroxamate groups was observed. Cd, on the other hand, remained as hydrated Cd2+ at pH 5.0, occurred as a mixture of Cd-DFOB and inorganic species at pH 8.0, and was bound by three hydroxamate groups from DFO-B at pH 9.0. Overall, the solution species observed with EXAFS were consistent with those predicted thermodynamically. However, Pb speciation at higher pH values differed from that predicted and suggests that published constants underestimate the binding constant for complexation of Pb with all three hydroxamate groups of the DFO-B ligand. This molecular-level understanding of metal-siderophore solution coordination provides physical evidence for complexes of Pb and Cd with DFO-B, and is an important first step toward understanding processes at the microbial- and/or mineral-water interface in the presence of siderophores.

76 FR 36610 - Self-Regulatory Organizations; The NASDAQ Stock Market LLC; Notice of Filing and Immediate...

Federal Register 2010, 2011, 2012, 2013, 2014

2011-06-22

... rather than by series; (b) adopt a $5 quotation spread parameter; and (c) amend the quoting requirement... additional time to adapt to the enhancements. \\4\\ The Exchange has also filed other proposed rule changes in... additional time to adapt to the enhancements. \\8\\ 15 U.S.C. 78f(b). \\9\\ 15 U.S.C. 78f(b)(5). B. Self...

Killing machines: three pore-forming proteins of the immune system

PubMed Central

McCormack, Ryan; de Armas, Lesley; Shiratsuchi, Motoaki

2014-01-01

The evolution of early multicellular eukaryotes 400–500 million years ago required a defensive strategy against microbial invasion. Pore-forming proteins containing the membrane-attack-complex-perforin (MACPF) domain were selected as the most efficient means to destroy bacteria or virally infected cells. The mechanism of pore formation by the MACPF domain is distinctive in that pore formation is purely physical and unspecific. The MACPF domain polymerizes, refolds, and inserts itself into bilayer membranes or bacterial outer cell walls. The displacement of surface lipid/carbohydrate molecules by the polymerizing MACPF domain creates clusters of large, water-filled holes that destabilize the barrier function and provide access for additional anti-bacterial or anti-viral effectors to sensitive sites that complete the destruction of the invader via enzymatic or chemical attack. The highly efficient mechanism of anti-microbial defense by a combined physical and chemical strategy using pore-forming MACPF-proteins has been retargeted during evolution of vertebrates and mammals for three purposes: (1) to kill extracellular bacteria C9/polyC9 evolved in conjunction with complement, (2) to kill virus infected and cancer cells perforin-1/polyperforin-1 CTL evolved targeted by NK and CTL, and (3) to kill intracellular bacteria transmembrane perforin-2/putative polyperforin-2 evolved targeted by phagocytic and nonphagocytic cells. Our laboratory has been involved in the discovery and description of each of the three pore-formers that will be reviewed here. PMID:24293008

Hybrid Finite Element Analysis of Free Edge Effect in Symmetric Composite Laminates

DTIC Science & Technology

1983-06-01

SJ3 (i,j = 1,2,4,5,6) (A.1.7)i Sij - S3 3 For symmetric angle ply case 814 : B24 = B34 = B54 : 0 (A.1.8)I B16 B 2 6 =B 3 6 =B 6 =0 In matrix form, eq...A.1.6) can be written as c = B a + co (A.l.9) 36 wi th c Xx c yy yz (A.1.10) zx c xy B 1 . B16 B = 5 x 5 matrix (A . I) B61 B6 6 axx yy (A..12...3.38) u rc+l 6 Ca+l *wU +l E: Aku rk (Ck)k=l where u 2 Pk = B 1 u ( uku) + B2 u - Bl6 Uuk u+xku(Bl5u k uB14 U) uB u qu= B u u + B22 - B26 + ku (B25U

Fatty acid and hydrocarbon composition in tropical marine Shewanella amazonensis strain SB2B(T).

PubMed

Motoigi, Taro; Okuyama, Hidetoshi

2011-10-01

Shewanella amazonensis strain SB2B(T) is an isolate from shallow-water marine sediments derived from the Amazon River delta. This bacterium contained a long-chain polyunsaturated hydrocarbon, all-cis -3,6,9,12,16,19,22,25,28 hentriacontanonaene (C31:9), constituting 1-2% of the total fatty acid methyl ester and hydrocarbon fraction, which was produced dependently of decreased growth temperature. Analysis of its cellular fatty acid composition demonstrated that isopentadecanoic acid was the major fatty acid component and that all the main monounsaturated fatty acids had straight chains with a cis configuration. However, monoenoic cyclopropyl fatty acids, which were previously reported to be present in this bacterium, were not detected by mass spectrometric analysis. The growth temperature affected the content of Δ9-cis -hexadecenoic [16:1(Δ9c)], palmitic, and heptadecanoic acids. These results suggest that C31:9, as well as 16:1(Δ9c) might be involved in adaptation to low temperature in S. amazonensis strain SB2B(T) . Our result suggests that polyunsaturated fatty acid synthase protein complex may be involved in synthesis of C31:9 but not in production of eicosapentaenoic acid. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Group 1 and group 2 metal complexes supported by a bidentate bulky iminopyrrolyl ligand: synthesis, structural diversity, and ε-caprolactone polymerization study.

PubMed

Kottalanka, Ravi K; Harinath, A; Rej, Supriya; Panda, Tarun K

2015-12-14

We report here a series of alkali and alkaline earth metal complexes, each with a bulky iminopyrrolyl ligand [2-(Ph3CN=CH)C4H3NH] (1-H) moiety in their coordination sphere, synthesized using either alkane elimination or silylamine elimination methods or the salt metathesis route. The lithium salt of molecular composition [Li(2-(Ph3CN=CH)C4H3N)(THF)2] (2) was prepared using the alkane elimination method, and the silylamine elimination method was used to synthesize the dimeric sodium and tetra-nuclear potassium salts of composition [(2-(Ph3CN=CH)C4H3N)Na(THF)]2 (3) and [(2-(Ph3CN=CH)C4H3N)K(THF)0.5]4 (4) respectively. The magnesium complex of composition [(THF)2Mg(CH2Ph){2-(Ph3CN=CH)C4H3N}] (5) was synthesized through the alkane elimination method, in which [Mg(CH2Ph)2(OEt2)2] was treated with the bulky iminopyrrole ligand 1-H in 1 : 1 molar ratio, whereas the bis(iminopyrrolyl)magnesium complex [(THF)2Mg{2-(Ph3CN=CH)C4H3N}2] (6) was isolated using the salt metathesis route. The heavier alkaline earth metal complexes of the general formula {(THF)nM(2-(Ph3CN=CH)C4H3N)2} [M = Ca (7), Sr (8), and n = 2; M = Ba (9), n = 3] were prepared in pure form using two synthetic methods: in the first method, the bulky iminopyrrole ligand 1-H was directly treated with the alkaline earth metal precursor [M{N(SiMe3)2}2(THF)n] (where M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent at ambient temperature. The complexes 7-9 were also obtained using the salt metathesis reaction, which involves the treatment of the potassium salt (4) with the corresponding metal diiodides MI2 (M = Ca, Sr and Ba) in 2 : 1 molar ratio in THF solvent. The molecular structures of all the metal complexes (1-H, 2-9) in the solid state were established through single-crystal X-ray diffraction analysis. The complexes 5-9 were tested as catalysts for the ring-opening polymerization of ε-caprolactone. High activity was observed in the heavier alkaline earth metal complexes 7-9, with a very narrow polydispersity index in comparison to that of magnesium complexes 5 and 6.

Highly sensitive sandwich immunoassay and immunochromatographic test for the detection of Clostridial epsilon toxin in complex matrices.

PubMed

Féraudet-Tarisse, Cécile; Mazuet, Christelle; Pauillac, Serge; Krüger, Maren; Lacroux, Caroline; Popoff, Michel R; Dorner, Brigitte G; Andréoletti, Olivier; Plaisance, Marc; Volland, Hervé; Simon, Stéphanie

2017-01-01

Epsilon toxin is one of the four major toxins of Clostridium perfringens. It is the third most potent clostridial toxin after botulinum and tetanus toxins and is thus considered as a potential biological weapon classified as category B by the Centers for Disease Control and Prevention (CDC). In the case of a bioterrorist attack, there will be a need for a rapid, sensitive and specific detection method to monitor food and water contamination by this toxin, and for a simple human diagnostic test. We have produced and characterized five monoclonal antibodies against common epitopes of epsilon toxin and prototoxin. Three of them neutralize the cytotoxic effects of epsilon toxin in vitro. With these antibodies, we have developed highly sensitive tests, overnight and 4-h sandwich enzyme immunoassays and an immunochromatographic test performed in 20 min, reaching detection limits of at least 5 pg/mL (0.15 pM), 30 pg/mL (0.9 pM) and 100 pg/mL (3.5 pM) in buffer, respectively. These tests were also evaluated for detection of epsilon toxin in different matrices: milk and tap water for biological threat detection, serum, stool and intestinal content for human or veterinary diagnostic purposes. Detection limits in these complex matrices were at least 5-fold better than those described in the literature (around 1 to 5 ng/mL), reaching 10 to 300 pg/mL using the enzyme immunoassay and 100 to 2000 pg/mL using the immunochromatographic test.

Highly sensitive sandwich immunoassay and immunochromatographic test for the detection of Clostridial epsilon toxin in complex matrices

PubMed Central

Mazuet, Christelle; Pauillac, Serge; Krüger, Maren; Lacroux, Caroline; Popoff, Michel R.; Dorner, Brigitte G.; Andréoletti, Olivier; Plaisance, Marc; Volland, Hervé; Simon, Stéphanie

2017-01-01

Epsilon toxin is one of the four major toxins of Clostridium perfringens. It is the third most potent clostridial toxin after botulinum and tetanus toxins and is thus considered as a potential biological weapon classified as category B by the Centers for Disease Control and Prevention (CDC). In the case of a bioterrorist attack, there will be a need for a rapid, sensitive and specific detection method to monitor food and water contamination by this toxin, and for a simple human diagnostic test. We have produced and characterized five monoclonal antibodies against common epitopes of epsilon toxin and prototoxin. Three of them neutralize the cytotoxic effects of epsilon toxin in vitro. With these antibodies, we have developed highly sensitive tests, overnight and 4-h sandwich enzyme immunoassays and an immunochromatographic test performed in 20 min, reaching detection limits of at least 5 pg/mL (0.15 pM), 30 pg/mL (0.9 pM) and 100 pg/mL (3.5 pM) in buffer, respectively. These tests were also evaluated for detection of epsilon toxin in different matrices: milk and tap water for biological threat detection, serum, stool and intestinal content for human or veterinary diagnostic purposes. Detection limits in these complex matrices were at least 5-fold better than those described in the literature (around 1 to 5 ng/mL), reaching 10 to 300 pg/mL using the enzyme immunoassay and 100 to 2000 pg/mL using the immunochromatographic test. PMID:28700661

Thermal response to firefighting activities in residential structure fires: impact of job assignment and suppression tactic.

PubMed

Horn, Gavin P; Kesler, Richard M; Kerber, Steve; Fent, Kenneth W; Schroeder, Tad J; Scott, William S; Fehling, Patricia C; Fernhall, Bo; Smith, Denise L

2018-03-01

Firefighters' thermal burden is generally attributed to high heat loads from the fire and metabolic heat generation, which may vary between job assignments and suppression tactic employed. Utilising a full-sized residential structure, firefighters were deployed in six job assignments utilising two attack tactics (1. Water applied from the interior, or 2. Exterior water application before transitioning to the interior). Environmental temperatures decreased after water application, but more rapidly with transitional attack. Local ambient temperatures for inside operation firefighters were higher than other positions (average ~10-30 °C). Rapid elevations in skin temperature were found for all job assignments other than outside command. Neck skin temperatures for inside attack firefighters were ~0.5 °C lower when the transitional tactic was employed. Significantly higher core temperatures were measured for the outside ventilation and overhaul positions than the inside positions (~0.6-0.9 °C). Firefighters working at all fireground positions must be monitored and relieved based on intensity and duration. Practitioner Summary: Testing was done to characterise the thermal burden experienced by firefighters in different job assignments who responded to controlled residential fires (with typical furnishings) using two tactics. Ambient, skin and core temperatures varied based on job assignment and tactic employed, with rapid elevations in core temperature in many roles.

Two clonal cell lines of immortalized human corneal endothelial cells show either differentiated or precursor cell characteristics.

PubMed

Valtink, Monika; Gruschwitz, Rita; Funk, Richard H W; Engelmann, Katrin

2008-01-01

Access to primary human corneal endothelial cells (HCEC) is limited and donor-derived differences between cultures exacerbate the issue of data reproducibility, whereas cell lines can provide sufficient numbers of homogenous cells for multiple experiments. An immortalized HCEC population was adapted to serum-free culture medium and repeated cloning was performed. Clonally grown cells were propagated under serum-free conditions and growth curves were recorded. Cells were characterized immunocytochemically for junctional proteins, collagens, Na,K-ATPase and HCEC-specific 9.3.E-antigen. Ultrastructure was monitored by scanning and transmission electron microscopy. Two clonal cell lines, HCEC-B4G12 and HCEC-H9C1, could be isolated and expanded, which differed morphologically: B4G12 cells were polygonal, strongly adherent and formed a strict monolayer, H9C1 cells were less adherent and formed floating spheres. The generation time of B4G12 cells was 62.26 +/- 14.5 h and that of H9C1 cells 44.05 +/- 5.05 h. Scanning electron microscopy revealed that B4G12 cells had a smooth cell surface, while H9C1 cells had numerous thin filopodia. Both cell lines expressed ZO-1 and occludin adequately, and little but well detectable amounts of connexin-43. Expression of HCEC-specific 9.3.E-antigen was found commensurately in both cell lines, while expression of Na,K-ATPase alpha1 was higher in H9C1 cells than in B4G12 cells. B4G12 cells expressed collagen IV abundantly and almost no collagen III, while H9C1 cells expressed both collagens at reasonable amounts. It is concluded that the clonal cell line B4G12 represents an ideal model of differentiated HCEC, while H9C1 may reflect features of developing or transitional HCEC. Copyright 2008 S. Karger AG, Basel.

Photophysics of N,N-Dimethyldihydrophenazine and Benzoannelated Analogues. Structurally Dependent Excited State Hierarchy,

DTIC Science & Technology

1980-02-26

phenazine (DrOIAC), 9,14-dimethyl-9,14-dihydrophenanthro[4,5-J] phenazine -(D!IPP) L.A- and 6,13-dimethyl-6,13-dihydrobibenzo[b,i] phenazine (DMBI) hie been...electrochemical oxidation,3 photochemical oxidation,4 and photoionization5 of 5,10-dlmethyl-5,10-dihydro- phenazine (DMP)’ have been studied. Our initial interest...dihydrodibenzo[a,c] phenazine (DMAC) 9,14-dlmethyl-9,14-dihydrophenanthro[4,5-abcphenazine (DMPP) and 6,13-di- methyl-6,13-dihydrodibenzo[b,ilphenazine

The relationship between anxiety and quality of life in children with hereditary angioedema.

PubMed

Kessel, Aharon; Farkas, Henriette; Kivity, Shmuel; Veszeli, Nóra; Kőhalmi, Kinga V; Engel-Yeger, Batya

2017-11-01

The severe life-threatening characteristics of hereditary angioedema (HAE) with C1-inhibitor deficiency (C1-INH-HAE) can affect anxiety levels among pediatric patients. This emotional burden together with the physical restrictions of C1-INH-HAE may decrease children's health-related quality of life (HRQoL). (i) To compare anxiety state and trait between children with C1-INH-HAE and healthy controls; (ii) to examine the relationship between the level of anxiety of children with C1-INH-HAE, their disease activity/affected sites and their HRQoL; and (iii) to predict the HRQoL of children with C1-INH-HAE based on their anxiety level and disease activity/affected sites METHODS: Thirty-three children with C1-INH-HAE (aged 5-18 years) and 52 healthy controls were recruited from Israel and Hungary. All children completed the State-Trait Anxiety Inventory for Children (STAIC), the Pediatric Quality of Life Inventory (Peds-QL) demographic questionnaire and a disease activity and site questionnaire . Disease activity was defined as the number of attacks in last year. Both anxiety state and trait were significantly higher among children with C1-INH-HAE as compared to the controls (44.74±10.56 vs 38.76±10.67, P<.01, 29.21±5.16 vs 25.23±4.09, P<.001 in comparison). Significant differences were found between C1-INH-HAE patients with HAE attacks, asymptomatic C1-INH-HAE patients, and healthy controls in both anxiety state (F 56,2 =4.69, P=.001) and trait (F 56,2 =9.06, P<.0001). A higher anxiety trait was correlated with the number of angioedema-affected sites (r=.52, P=.003). The presence of HAE attacks and higher anxiety trait predicted a lower HRQoL in children with C1-INH-HAE. C1-INH-HAE children have higher anxiety trait and state, which correlate with reduced HRQoL domains. © 2017 EAACI and John Wiley and Sons A/S. Published by John Wiley and Sons Ltd.

The effects of Bacillus thuringiensis Cry6A on the survival, growth, reproduction, locomotion, and behavioral response of Caenorhabditis elegans.

PubMed

Luo, Hui; Xiong, Jing; Zhou, Qiaoni; Xia, Liqiu; Yu, Ziquan

2013-12-01

Several families of crystal proteins from Bacillus thuringiensis exhibit nematicidal activity. Cry5B protein, a pore-forming toxin, has been intensively studied yielding many insights into the mode of action of crystal protein at molecular level and pathogenesis of pore-forming toxins. However, little attention was paid to Cry6A, another representative nematicidal crystal protein. Cry6A shares very low homology with Cry5B at amino acid sequence and probably acts in a distinct pathway from Cry5B and even the other main commercial crystal proteins. In the current study, we comprehensively investigated the nematicidal properties of Cry6Aa2 against the free-living soil nematode Caenorhabditis elegans and examined the physical response of C. elegans to Cry6Aa2 attack. Our results indicate that Cry6Aa2 exhibits high lethal activity to C. elegans and could cause detrimental effects on C. elegans, including obviously suppressed growth, decreased brood size, and even abnormal motility. Meanwhile, our study additionally shows that C. elegans could defend against the Cry6Aa2 toxin harmful threat through behavioral defense responses, such as reduced oral uptake and physical avoidance. In general, this study suggests that Cry6Aa2 possesses diverse nematicidal properties, which strongly indicates that Cry6Aa2 is a promising potential candidate of nematicidal agent. Moreover, this study highlights the importance of behavioral responses in defense of C. elegans for survival and demonstrates the key role of crystal protein in the interaction of B. thuringiensis-C. elegans. These findings could shed light on understanding the interaction of C. elegans with B. thuringiensis and provide a perfect model to study the role of pathogenic factor in the interaction of pathogen-host.

Evidence for a $$B_s^0 \\pi^\\pm$$ state

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

Abazov, V. M.

Here, we report evidence for a narrow structure, X(5568), in the decay sequence X(5568)→more » $$B_s^0 \\pi^\\pm$$, B$$_s^0$$ →J/ψΦ, J/ψ→μ+μ-, Φ→K+K-. This is evidence for the first instance of a hadronic state with valence quarks of four different flavors. The mass and natural width of this state are measured to be m=5567.8±2.9(stat) $$+0.9\\atop{-1.9}$$ (syst) MeV/c 2 and Γ=21.9±6.4(stat)$$+5.0\\atop{-2.5}$$ (syst) MeV/c 2. If the decay is X(5568)→B$$*\\atop{s}$$ π ±→B$$0\\atop{s}$$ γπ ± with an unseen γ, m(X(5568)) will be shifted up by m(B$$*\\atop{s}$$ )-m(B$$0\\atop{s}$$)~49 MeV/c 2. This measurement is based on 10.4 fb -1 of $$p\\bar{p}$$ collision data at $$\\sqrt{s}$$ =1.96 TeV collected by the D0 experiment at the Fermilab Tevatron collider.« less

Evidence for a $$B_s^0 \\pi^\\pm$$ state

DOE PAGES

Abazov, V. M.

2016-07-07

Here, we report evidence for a narrow structure, X(5568), in the decay sequence X(5568)→more » $$B_s^0 \\pi^\\pm$$, B$$_s^0$$ →J/ψΦ, J/ψ→μ+μ-, Φ→K+K-. This is evidence for the first instance of a hadronic state with valence quarks of four different flavors. The mass and natural width of this state are measured to be m=5567.8±2.9(stat) $$+0.9\\atop{-1.9}$$ (syst) MeV/c 2 and Γ=21.9±6.4(stat)$$+5.0\\atop{-2.5}$$ (syst) MeV/c 2. If the decay is X(5568)→B$$*\\atop{s}$$ π ±→B$$0\\atop{s}$$ γπ ± with an unseen γ, m(X(5568)) will be shifted up by m(B$$*\\atop{s}$$ )-m(B$$0\\atop{s}$$)~49 MeV/c 2. This measurement is based on 10.4 fb -1 of $$p\\bar{p}$$ collision data at $$\\sqrt{s}$$ =1.96 TeV collected by the D0 experiment at the Fermilab Tevatron collider.« less

Pentaarylcyclopentadienyl Iron, Cobalt, and Nickel Halides.

PubMed

Chakraborty, Uttam; Modl, Moritz; Mühldorf, Bernd; Bodensteiner, Michael; Demeshko, Serhiy; van Velzen, Niels J C; Scheer, Manfred; Harder, Sjoerd; Wolf, Robert

2016-03-21

The preparation of new stable half-sandwich transition metal complexes, having a bulky cyclopentadienyl ligand C5(C6H4-4-Et)5 (Cp(Ar1)) or C5(C6H4-4-nBu)5 (Cp(Ar2)), is reported. The tetrahydrofuran (THF) adduct [Cp(Ar1)Fe(μ-Br)(THF)]2 (1a) was synthesized by reacting K[Cp(Ar1)] with [FeBr2(THF)2] in THF, and its molecular structure was determined by X-ray crystallography. Complex 1a easily loses its coordinated THF molecules under vacuum to form the solvent-free complex [Cp(Ar1)Fe(μ-Br)]2 (1b). The analogous complexes [Cp(Ar1)Co(μ-Br)]2 (2), [Cp(Ar1)Ni(μ-Br)]2 (3), and [Cp(Ar2)Ni(μ-Br)]2 (4) were synthesized from CoBr2 and [NiBr2(1,2-dimethoxyethane)]. The mononuclear, low-spin cobalt(III) and nickel(III) complexes [Cp(Ar2)MI2] (5, M = Co; 6, M = Ni) were prepared by reacting the radical Cp(Ar2) with NiI2 and CoI2. The complexes were characterized by NMR and UV-vis spectroscopies and by elemental analyses. Single-crystal X-ray structure analyses revealed that the dimeric complexes 1a, 1b, and 3 have a planar M2Br2 core, whereas 2 and 4 feature a puckered M2Br2 ring.

The first 3':5'-cyclic nucleotide-amino acid complex: L-His-cIMP.

PubMed

Slepokura, Katarzyna

2012-08-01

In the crystal structure of the L-His-cIMP complex, i.e. L-histidinium inosine 3':5'-cyclic phosphate [systematic name: 5-(2-amino-2-carboxyethyl)-1H-imidazol-3-ium 7-hydroxy-2-oxo-6-(6-oxo-6,9-dihydro-1H-purin-9-yl)-4a,6,7,7a-tetrahydro-4H-1,3,5,2λ(5)-furo[3,2-d][1,3,2λ(5)]dioxaphosphinin-2-olate], C(6)H(10)N(3)O(2)(+)·C(10)H(10)N(4)O(7)P(-), the Hoogsteen edge of the hypoxanthine (Hyp) base of cIMP and the Hyp face are engaged in specific amino acid-nucleotide (His···cIMP) recognition, i.e. by abutting edge-to-edge and by π-π stacking, respectively. The Watson-Crick edge of Hyp and the cIMP phosphate group play a role in nonspecific His···cIMP contacts. The interactions between the cIMP anions (anti/C3'-endo/trans-gauche/chair conformers) are realized mainly between riboses and phosphate groups. The results for this L-His-cIMP complex, compared with those for the previously reported solvated L-His-IMP crystal structure, indicate a different nature of amino acid-nucleotide recognition and interactions upon the 3':5'-cyclization of the nucleotide phosphate group.

Solid-State Synthesis and Structure of the Enigmatic Ammonium Octaborate: (NH4)2[B7O9(OH)5]·3/4B(OH)3·5/4H2O.

PubMed

Neiner, Doinita; Sevryugina, Yulia V; Schubert, David M

2016-09-06

The compound known since the 19th century as ammonium octaborate was structurally characterized revealing the ammonium salt of the ribbon isomer of the heptaborate anion, [B7O9(OH)5](2-), with boric acid and water molecules. Of composition (NH4)2B7.75O12.63·4.88H2O, it approximates the classical ammonium octaborate composition (NH4)2B8O13·6H2O and has the structural formula {(NH4)2[B7O9(OH)5]}4·3B(OH)3·5H2O. It spontaneously forms at room temperature in solid-state mixtures of ammonium tetraborate and ammonium pentaborate. It crystallizes in the monoclinic space group P21/c with a = 11.4137(2) Å, b = 11.8877(2) Å, c = 23.4459(3) Å, β = 90.092(1)°, V = 3181.19(8) Å(3), and Z = 2 and contains well-ordered ammonium cations and [B7O9(OH)5](2-) anions and disordered B(OH)3 and H2O molecules linked by extensive H bonding. Expeditious solid-state formation of the heptaborate anion under ambient conditions has important implications for development of practical syntheses of industrially useful borates.

Generating Lookup Tables from the AE9/AP9 Models

DTIC Science & Technology

2015-06-16

AP9 Models 5a. CONTRACT NUMBER FA8802-14-C-0001 5b. GRANT NUMBER na 5c. PROGRAM ELEMENT NUMBER 5811 6. AUTHOR( S ) Joshua P. Davis 5d. PROJECT...NUMBER 11 5e. TASK NUMBER na 5f. WORK UNIT NUMBER na 7. PERFORMING ORGANIZATION NAME( S ) AND ADDRESS(ES) The Aerospace Corporation 2310 E. El...Segundo Blvd. El Segundo, CA 90245-4609 8. PERFORMING ORGANIZATION REPORT NUMBER TOR-2015-00893 9. SPONSORING/MONITORING AGENCY NAME( S ) AND ADDRESS

Ruthenium complexes containing 2-(2-nitrosoaryl)pyridine: structural, spectroscopic, and theoretical studies.

PubMed

Chan, Siu-Chung; Cheung, Ho-Yuen; Wong, Chun-Yuen

2011-11-21

Ruthenium complexes containing 2-(2-nitrosoaryl)pyridine (ON(^)N) and tetradentate thioether 1,4,8,11-tetrathiacyclotetradecane ([14]aneS4), [Ru(ON(^)N)([14]aneS4)](2+) [ON(^)N = 2-(2-nitrosophenyl)pyridine (2a), 10-nitrosobenzo[h]quinoline (2b), 2-(2-nitroso-4-methylphenyl)pyridine, (2c), 2-(2-nitrosophenyl)-5-(trifluoromethyl)pyridine (2d)] and analogues with the 1,4,7-trithiacyclononane ([9]aneS3)/tert-butylisocyanide ligand set, [Ru(ON(^)N)([9]aneS3)(C≡N(t)Bu)](2+) (4a and 4b), have been prepared by insertion of a nitrosonium ion (NO(+)) into the Ru-aryl bond of cyclometalated ruthenium(II) complexes. The molecular structures of the ON(^)N-ligated complexes 2a and 2b reveal that (i) the ON(^)N ligands behave as bidentate chelates via the two N atoms and the bite angles are 86.84(18)-87.83(16)° and (ii) the Ru-N(NO) and N-O distances are 1.942(5)-1.948(4) and 1.235(6)-1.244(5) Å, respectively. The Ru-N(NO) and N-O distances, together with ν(N═O), suggest that the coordinated ON(^)N ligands in this work are neutral moiety (ArNO)(0) rather than monoanionic radical (ArNO)(•-) or dianion (ArNO)(2-) species. The nitrosated complexes 2a-2d show moderately intense absorptions centered at 463-484 nm [ε(max) = (5-6) × 10(3) dm(3) mol(-1) cm(-1)] and a clearly discriminable absorption shoulder around 620 nm (ε(max) = (6-9) × 10(2) dm(3) mol(-1) cm(-1)), which tails up to 800 nm. These visible absorptions are assigned as a mixing of d(Ru) → ON(^)N metal-to-ligand charge-transfer and ON(^)N intraligand transitions on the basis of time-dependent density functional theory (TD-DFT) calculations. The first reduction couples of the nitrosated complexes range from -0.53 to -0.62 V vs Cp(2)Fe(+/0), which are 1.1-1.2 V less negative than that for [Ru(bpy)([14]aneS4)](2+) (bpy = 2,2'-bipyridine). Both electrochemical data and DFT calculations suggest that the lowest unoccupied molecular orbitals of the nitrosated complexes are ON(^)N-centered. Natural population analysis shows that the amount of positive charge on the Ru centers and the [Ru([14]aneS4)] moieties in 2a and 2b is larger than that in [Ru(bpy)([14]aneS4)](2+). According to the results of the structural, spectroscopic, electrochemical, and theoretical investigations, the ON(^)N ligands in this work have considerable π-acidic character and behave as better electron acceptors than bpy.

40 CFR Table 9 to Subpart Uuuuu of... - Applicability of General Provisions to Subpart UUUUU

Code of Federal Regulations, 2013 CFR

2013-07-01

...-Fired Electric Utility Steam Generating Units Pt. 63, Subpt. UUUUU, Table 9 Table 9 to Subpart UUUUU of... Review and Notification Requirements Yes. § 63.6(a), (b)(1)-(b)(5), (b)(7), (c), (f)(2)-(3), (g), (h)(2...

40 CFR Table 9 to Subpart Uuuuu of... - Applicability of General Provisions to Subpart UUUUU

Code of Federal Regulations, 2014 CFR

2014-07-01

...-Fired Electric Utility Steam Generating Units Pt. 63, Subpt. UUUUU, Table 9 Table 9 to Subpart UUUUU of... Review and Notification Requirements Yes. § 63.6(a), (b)(1)-(b)(5), (b)(7), (c), (f)(2)-(3), (g), (h)(2...

40 CFR Table 9 to Subpart Uuuuu of... - Applicability of General Provisions to Subpart UUUUU

Code of Federal Regulations, 2012 CFR

2012-07-01

...-Fired Electric Utility Steam Generating Units Pt. 63, Subpt. UUUUU, Table 9 Table 9 to Subpart UUUUU of... Review and Notification Requirements Yes. § 63.6(a), (b)(1)-(b)(5), (b)(7), (c), (f)(2)-(3), (g), (h)(2...

Copper (II) and 2,2'-bipyridine complexation improves chemopreventive effects of naringenin against breast tumor cells.

PubMed

Filho, Júlio César Conceição; Sarria, André Lúcio Franceschini; Becceneri, Amanda Blanque; Fuzer, Angelina Maria; Batalhão, Jaqueline Raquel; da Silva, Caio Marcio Paranhos; Carlos, Rose Maria; Vieira, Paulo Cezar; Fernandes, João Batista; Cominetti, Márcia Regina

2014-01-01

Cancer is the second leading cause of death worldwide and there is epidemiological evidence that demonstrates this tendency is emerging. Naringenin (NGEN) is a trihydroxyflavanone that shows various biological effects such as antioxidant, anticancer, anti-inflammatory, and antiviral activities. It belongs to flavanone class, which represents flavonoids with a C6-C3-C6 skeleton. Flavonoids do not exhibit sufficient activity to be used for chemotherapy, however they can be chemically modified by complexation with metals such as copper (Cu) (II) for instance, in order to be applied for adjuvant therapy. This study investigated the effects of Cu(II) and 2,2'-bipyridine complexation with naringenin on MDA-MB-231 cells. We demonstrated that naringenin complexed with Cu(II) and 2,2'-bipyridine (NGENCuB) was more efficient inhibiting colony formation, proliferation and migration of MDA-MB-231 tumor cells, than naringenin (NGEN) itself. Furthermore, we verified that NGENCuB was more effective than NGEN inhibiting pro-MMP9 activity by zymography assays. Finally, through flow cytometry, we showed that NGENCuB is more efficient than NGEN inducing apoptosis in MDA-MB-231 cells. These results were confirmed by gene expression analysis in real time PCR. We observed that NGENCuB upregulated the expression of pro-apoptotic gene caspase-9, but did not change the expression of caspase-8 or anti-apoptotic gene Bcl-2. There are only few works investigating the effects of Cu(II) complexation with naringenin on tumor cells. To the best of our knowledge, this is the first work describing the effects of Cu(II) complexation of a flavonoid on MDA-MB-231 breast tumor cells.

Basic mechanisms of migraine and its acute treatment.

PubMed

Edvinsson, Lars; Villalón, Carlos M; MaassenVanDenBrink, Antoinette

2012-12-01

Migraine is a neurovascular disorder characterized by recurrent unilateral headaches accompanied by nausea, vomiting, photophobia and phonophobia. Current theories suggest that the initiation of a migraine attack involves a primary event in the central nervous system (CNS), probably involving a combination of genetic changes in ion channels and environmental changes, which renders the individual more sensitive to environmental factors; this may, in turn, result in a wave of cortical spreading depression (CSD) when the attack is initiated. Genetically, migraine is a complex familial disorder in which the severity and the susceptibility of individuals are most likely governed by several genes that vary between families. Early PET studies have suggested the involvement of a migraine active region in the brainstem. Migraine headache is associated with trigeminal nerve activation and calcitonin gene-related peptide (CGRP) release from the trigeminovascular system. Administration of triptans (5-HT(1B/1D) receptor agonists) causes the headache to subside and the levels of CGRP to normalize. Moreover, administration of CGRP receptor antagonists aborts the headache. Recent immunohistochemical and pharmacological results suggest that the trigeminal system has receptors for CGRP; further, 5-HT(1B/1D) receptors, which inhibit the action of CGRP in pain transmission when activated, have been demonstrated. This offers an explanation for the treatment response. The present review provides an updated analysis of the basic mechanisms involved in the pathophysiology of migraine and the various pharmacological approaches (including 5-HT(1B/1D) receptor agonists, CGRP receptor antagonists and glutamate receptor antagonists) that have shown efficacy for the acute treatment of this disorder. Copyright © 2012 Elsevier Inc. All rights reserved.

\\varvec{B^0→ K^{*0}μ ^+μ ^-} decay in the aligned two-Higgs-doublet model

NASA Astrophysics Data System (ADS)

Hu, Quan-Yi; Li, Xin-Qiang; Yang, Ya-Dong

2017-03-01

In the aligned two-Higgs-doublet model, we perform a complete one-loop computation of the short-distance Wilson coefficients C_{7,9,10}^{(' )}, which are the most relevant ones for b→ sℓ ^+ℓ ^- transitions. It is found that, when the model parameter | σ u| is much smaller than | σd| , the charged scalar contributes mainly to chirality-flipped C_{9,10}^' , with the corresponding effects being proportional to | σd| ^2. Numerically, the charged-scalar effects fit into two categories: (A) C_{7,9,10}^{H^± } are sizable, but C_{9,10}^' {H^± }}˜eq 0, corresponding to the (large | σu| , small | σd| ) region; (B) C_7^{H^± } and C_{9,10}^' {H^± }} are sizable, but C_{9,10}^{H^± }˜eq 0, corresponding to the (small | σu| , large | σd| ) region. Taking into account phenomenological constraints from the inclusive radiative decay B→ Xs{γ }, as well as the latest model-independent global analysis of b→ sℓ ^+ℓ ^- data, we obtain the much restricted parameter space of the model. We then study the impact of the allowed model parameters on the angular observables P_2 and P_5' of B^0→ K^{*0}μ ^+μ ^- decay, and we find that P_5' could be increased significantly to be consistent with the experimental data in case B.

Site-selective As-P substitution and hydrogen bonding in the crystal structure of philipsburgite, Cu5Zn((As,P)O4)2(OH)6·H2O

NASA Astrophysics Data System (ADS)

Krivovichev, Sergey V.; Zhitova, Elena S.; Ismagilova, Rezeda M.; Zolotarev, Andrey A.

2018-05-01

Philipsburgite, Cu5Zn((As,P)O4)2(OH)6·H2O, from the Middle Pit, Gold Hill Mine, Tooele Co., Utah, USA, was studied by single-crystal X-ray diffraction and scanning electron microscopy. The empirical formula of the studied sample is (Cu4.69Zn1.23)(As0.86P0.18O4)2(OH)5.61·H2O, which agrees well with the previous reports on the mineral. Philipsburgite is monoclinic, P21/c, a = 12.385(6), b = 9.261(4), c = 10.770(5) Å, β = 97.10(1)o, V = 1225.7(9) Å3 (at 100 K), and Z = 4. The crystal structure was refined to R 1 = 0.046 for 2563 unique observed reflections with |F o| ≥ 4σ F . The crystal structure of philipsburgite is isotypic to that of kipushite and can be considered as a complex three-dimensional framework consisting of two types of layers stacked parallel to the a-axis. The A-type layer is formed by the edge-sharing Jahn-Teller-distorted Cuφ6 octahedra [φ = O2-, (OH)-, H2O]. Two adjacent octahedral layers are linked via (As2O4) tetrahedra. The B-type layer is built by corner-sharing (ZnO4) and (As1O4) tetrahedra and is formed by the four- and eight-membered tetrahedral rings. The A:B ratio of the A and B layers is equal to 2:1. The hydrogen bonding network in philipsburgite is rather complex and consists of two- and three-center hydrogen bonds. The As1 site accommodates ca. 18% of P and is a preferable position for the P substitution in philipsburgite. The observed selectivity of the As1 site for P may indicate that, for the intermediate compositions with the P:As ratios close to 1:1, there is a fully ordered species with P prevalent at the As1 site and As prevalent at the As2 site. The intermediate composition would, therefore, be Cu5Zn(AsO4)(PO4)(OH)6·H2O and such a mineral can be considered as a separate species, according to the rules of the International Mineralogical Association (IMA). Philipsburgite should be considered as structurally complex with the Shannon information contents of 4.954 bits/atom and 614.320 bits/cell. The obvious reason for the structural complexity of the mineral is its modularity, i.e., the presence of two structurally distinct modules, the octahedral-tetrahedral (A) and tetrahedral (B) layers.

Attack Coverage in High-Level Men’s Volleyball: Organization on the Edge of Chaos?

PubMed Central

Laporta, Lorenzo; Nikolaidis, Pantelis; Thomas, Luke; Afonso, José

2015-01-01

Change is pervasive, but emerging patterns are occasionally detectable through analysis of systemic behaviors. Match analysis uses these patterns in order to reduce the degree of improvisation and to optimize the training process. However, it is possible that certain game phases elude systematic patterning. In this vein, our aim was to analyze the case of attack coverage in men’s volleyball, as we suspected it would elude systematic patterning and has received negligible attention in scientific research. We analyzed the occurrence of attack coverage in 4544 plays of the 2011 Volleyball World League. A Chi-square test with residual adjusted values was applied to explore significant associations between variables. A Monte Carlo correction was applied, as some cells had n<5. Effect sizes were determined using Cramer’s V. Overall, attack coverage occurred in 3.89% of ball possessions, and 23 distinct structures emerged. These structures lacked significant associations with the game complex, setting zone, and effect of attack coverage. Conversely, attack coverage structures showed significant associations with the attack zone and tempo, with very strong effect sizes (V=0.472 and V=0.521, respectively). As certain attack zones are deeply associated with attack tempo, it is apparent that quicker attack plays affect attack coverage structuring, promoting the formation of less complex structures. Ultimately, attack coverage structures seem to depend on momentary constraints, thereby rendering rigid systematization impracticable. Still, we contended that a principle-based approach might be suitable. This invites researchers to rethink how to interpret game regularities. PMID:26557208

Predicting and Controlling Complex Networks

DTIC Science & Technology

2015-06-22

vulnerability and to generate a global view of network security against attacks. By deploying network sensors at particular points in the Internet ...48006, 1-6 (2011). 2 13. L. Huang and Y.-C. Lai, “Cascading dynamics in complex quantum networks,” Chaos 21, 025107, 1-6 (2011). This work was selected...by July 2011 issue of Virtual Journal of Quantum Information (http://www.vjquantuminfo.org). 14. W.-X. Wang, Y.-C. Lai, and D. Armbruster, “Cascading

Elucidation of the transcription network governing mammalian sex determination by exploiting strain-specific susceptibility to sex reversal

PubMed Central

Munger, Steven C.; Aylor, David L.; Syed, Haider Ali; Magwene, Paul M.; Threadgill, David W.; Capel, Blanche

2009-01-01

Despite the identification of some key genes that regulate sex determination, most cases of disorders of sexual development remain unexplained. Evidence suggests that the sexual fate decision in the developing gonad depends on a complex network of interacting factors that converge on a critical threshold. To elucidate the transcriptional network underlying sex determination, we took the first expression quantitative trait loci (eQTL) approach in a developing organ. We identified reproducible differences in the transcriptome of the embryonic day 11.5 (E11.5) XY gonad between C57BL/6J (B6) and 129S1/SvImJ (129S1), indicating that the reported sensitivity of B6 to sex reversal is consistent with a higher expression of a female-like transcriptome in B6. Gene expression is highly variable in F2 XY gonads from B6 and 129S1 intercrosses, yet strong correlations emerged. We estimated the F2 coexpression network and predicted roles for genes of unknown function based on their connectivity and position within the network. A genetic analysis of the F2 population detected autosomal regions that control the expression of many sex-related genes, including Sry (sex-determining region of the Y chromosome) and Sox9 (Sry-box containing gene 9), the key regulators of male sex determination. Our results reveal the complex transcription architecture underlying sex determination, and provide a mechanism by which individuals may be sensitized for sex reversal. PMID:19884258

Cryptophane Nanoscale Assemblies Expand 129Xe NMR Biosensing.

PubMed

Zemerov, Serge D; Roose, Benjamin W; Greenberg, Mara L; Wang, Yanfei; Dmochowski, Ivan J

2018-06-19

Cryptophane-based biosensors are promising agents for the ultrasensitive detection of biomedically relevant targets via 129 Xe NMR. Dynamic light scattering revealed that cryptophanes form water-soluble aggregates tens to hundreds of nanometers in size. Acridine orange fluorescence quenching assays allowed quantitation of the aggregation state, with critical concentrations ranging from 200 nM to 600 nM, depending on the cryptophane species in solution. The addition of excess carbonic anhydrase (CA) protein target to a benzenesulfonamide-functionalized cryptophane biosensor (C8B) led to C8B disaggregation and produced the expected 1:1 C8B-CA complex. C8B showed higher affinity at 298 K for the cytoplasmic isozyme CAII than the extracellular CAXII isozyme, which is a biomarker of cancer. Using hyper-CEST NMR, we explored the role of stoichiometry in detecting these two isozymes. Under CA-saturating conditions, we observed that isozyme CAII produces a larger 129 Xe NMR chemical shift change (δ = 5.9 ppm, relative to free biosensor) than CAXII (δ = 2.7 ppm), which indicates the strong potential for isozyme-specific detection. However, stoichiometry-dependent chemical shift data indicated that biosensor disaggregation contributes to the observed 129 Xe NMR chemical shift change that is normally assigned to biosensor-target binding. Finally, we determined that monomeric cryptophane solutions improve hyper-CEST saturation contrast, which enables ultrasensitive detection of biosensor-protein complexes. These insights into cryptophane-solution behavior support further development of xenon biosensors, but will require reinterpretation of the data previously obtained for many water-soluble cryptophanes.

Synthesis, structure, photoluminescence and antitumour activity of zinc complex based on 2-(2-(1H-benzo-[d]imidazol-2-yl)benzyl)-1H-benzo-[d]imidazole

NASA Astrophysics Data System (ADS)

Che, Zhijian; Wang, Shaoxiang; Liu, Shenggui; Li, Guobi; Wu, Qiting; Lin, Chunyu; Kong, Linglang; Wang, Sheng

2015-01-01

A new complex [Zn(bbb)Cl2]·DMF, where bbb is 2-(2-(1H-benzo[d]imidazol-2-yl)benzyl)-1H-benzo[d]imidazole, was synthesized and characterized by element analysis, 1H NMR and X-ray single crystal structure analyses. For complex: crystal system, triclinic, space group, P-1, a = 9.4661(13), b = 10.3534(14), c = 13.0025(18) Å, α = 73.477(2), β = 80.743(2), γ = 88.658(2)°, V = 1205.5(3) Å3, Z = 2. In this complex, the Zn2+ distorted tetrahedron geometry is coordinated by two nitrogen atoms from 2-(2-(1H-benzo[d]imidazol-2-yl)benzyl)-1H-benzo[d]imidazole and two Cl-. The complex emits yellow green luminescence with the maximal emission peak at 550 nm in DMF solution. The complex exhibits inhibition on the growth of Eca109 cancer cell with IC50 value of 8.9 ± 1.1 μM, which was lower than that of cisplatin (14.3 ± 1.4 μM). This complex has potential application in treatment of esophageal cancer.

Luminescent zinc and cadmium complexes incorporating 1,3,5-benzenetricarboxylate and a protonated kinked organodiimine: From a hydrogen-bonded layer motif to thermally robust two-dimensional coordination polymers

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

Braverman, Maxwell A.; Supkowski, Ronald M.; LaDuca, Robert L.

2007-06-15

Hydrothermal treatment of zinc chloride, 1,3,5-benzenetricarboxylic acid (H{sub 3}BTC), and 4,4'-dipyridylamine (dpa) afforded two different complexes depending on reaction conditions, which were characterized by single-crystal X-ray diffraction, infrared spectroscopy, and elemental analysis. Under acidic conditions, a discrete neutral molecular species with formulation [Zn(HBTC){sub 2}(Hdpa){sub 2}] (1) was isolated, which aggregates into two-dimensional hydrogen-bonded layers. Under more basic conditions, the two-dimensional layered coordination polymer [Zn(BTC)(Hdpa)] (2) is obtained, which manifests covalent linkage of [Zn(BTC)(Hdpa)] serpentine chain motifs into 3-connected undulating 4.8{sup 2} topology 2-D layers. Both 1 and 2 possess tetrahedral coordination at Zn. Use of cadmium nitrate in the synthesismore » resulted in [Cd(BTC)(H{sub 2}O)(Hdpa)] (3), which displays a similar layer topology as 2 but with significant adjustments imparted by octahedral coordination at Cd. In all cases, supramolecular hydrogen bonding promoted by Hdpa ligands provide an important assistive structure-directing role. All materials display blue luminescence upon excitation with ultraviolet light, ascribed to intraligand transitions. Crystallographic data: 1: monoclinic, C2/c, a=25.389(6) A, b=9.811(2) A, c=17.309(4) A, and {beta}=128.957(3){sup o}, 2: monoclinic, P2{sub 1}/c, a=13.212(17)c, b=17.15(2) A, c=7.506(10) A, and {beta}=93.71(2){sup o}, and 3: monoclinic, C2/c, a=14.241(6) A, b=15.218(6) A, c=17.976(7) A, and {beta}=109.330(6){sup o}. - Graphical abstract: Hydrothermal synthesis has afforded a family of luminescent complexes based on divalent d {sup 10} cations with 1,3,5-benzenetricarboxylate (BTC) and 4,4'-dipyridylamine (dpa) ligands. [Zn(HBTC){sub 2}(Hdpa){sub 2}] (1) is a discrete neutral molecular species. [Zn(BTC)(Hdpa)] (2, pictured) and [Cd(BTC)(H{sub 2}O)(Hdpa)] (3) are 2-D coordination polymers with different morphologies depending on coordination geometry at the metal. All three materials exhibit blue-violet luminescence on exposure to ultraviolet radiation.« less

The expanding host tree species spectrum of Cryptococcus gattii and Cryptococcus neoformans and their isolations from surrounding soil in India.

PubMed

Randhawa, H S; Kowshik, T; Chowdhary, Anuradha; Preeti Sinha, K; Khan, Z U; Sun, Sheng; Xu, Jianping

2008-12-01

This study reports the widespread prevalence of Cryptococcus neoformans and Cryptococcus gattii in decayed wood inside trunk hollows of 14 species representing 12 families of trees and from soil near the base of various host trees from Delhi and several places in the Indian states of Uttar Pradesh, Haryana, Tamil Nadu and Chandigarh Union Territory. Of the 311 trees from which samples were obtained, 64 (20.5%) were found to contain strains of the C. neoformans species complex. The number of trees positive for C. neoformans var grubii (serotypeA) was 51 (16.3%), for C. gattii (serotype B) 24 (7.7%) and for both C. neoformans and C. gattii 11 (3.5%). The overall prevalence of C. neoformans species complex in decayed wood samples was 19.9% (111/556). There was no obvious correlation between the prevalence of these two yeast species and the species of host trees. The data on prevalence of C. gattii (24%) and C. neoformans (26%) in soil around the base of some host trees indicated that soil is another important ecologic niche for these two Cryptococcus species in India. Among our sampled tree species, eight and six were recorded for the first time as hosts for C. neoformans var grubii and C. gattii, respectively. A longitudinal surveillance of 8 host tree species over 0.7 to 2.5 years indicated long term colonization of Polyalthia longifolia, Mimusops elengi and Manilkara hexandra trees by C. gattii and/or C. neoformans. The mating type was determined for 153 of the isolates, including 98 strains of serotype A and 55 of serotype B and all proved to be mating type alpha (MAT alpha). Our observations document the rapidly expanding spectrum of host tree species for C. gattii and C. neoformans and indicate that decayed woods of many tree species are potentially suitable ecological niches for both pathogens.

Characterization of beryllium-boron-bearing materials by Parallel Electron Energy-Loss Spectroscopy (PEELS)

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

Garvie, L.A.J.; Buseck, P.R.; Rez, P.

The stoichiometry of a set of commercial and laboratory-synthesized Be-B-bearing materials was determined by parallel electron energy-loss spectroscopy (PEELS). The Be and B K edges are well separated in energy, allowing easy determination of the elemental ratios. PEELS analyses of materials with reported compositions of {open_quotes}Be{sub 2}B{close_quotes} and {open_quotes}Be{sub 2}B{sub 3}{close_quotes} provided stoichiometries near Be{sub 2.8}B and Be{sub 4}B{sub 5}, respectively. We confirmed an earlier report of Be{sub 0.6({+-}0.1)} B{sub 5.9({+-}0.7)}C, a material with the {alpha}-rhombohedral B structure. We also synthesized and characterized Be{sub 0.5({+-}0.1)}B{sub 4.9({+-}0.3)}N, a new ternary material with the {alpha}-rhombohedral B structure with refined hexagonal cell parametersmore » of a{sub h} = 5.487(5) {alpha} and c{sub h} = 12.486(14) {angstrom}. By comparison of the features at the core-loss edges of Be{sub 0.5({+-}0.1)} B{sub 4.9({+-}0.3)}N, we conclude the most N forms N{sub 2} pairs between the icosahedra and Be substitutes for B within the icosahedra.« less

Robustness of non-interdependent and interdependent networks against dependent and adaptive attacks

NASA Astrophysics Data System (ADS)

Tyra, Adam; Li, Jingtao; Shang, Yilun; Jiang, Shuo; Zhao, Yanjun; Xu, Shouhuai

2017-09-01

Robustness of complex networks has been extensively studied via the notion of site percolation, which typically models independent and non-adaptive attacks (or disruptions). However, real-life attacks are often dependent and/or adaptive. This motivates us to characterize the robustness of complex networks, including non-interdependent and interdependent ones, against dependent and adaptive attacks. For this purpose, dependent attacks are accommodated by L-hop percolation where the nodes within some L-hop (L ≥ 0) distance of a chosen node are all deleted during one attack (with L = 0 degenerating to site percolation). Whereas, adaptive attacks are launched by attackers who can make node-selection decisions based on the network state in the beginning of each attack. The resulting characterization enriches the body of knowledge with new insights, such as: (i) the Achilles' Heel phenomenon is only valid for independent attacks, but not for dependent attacks; (ii) powerful attack strategies (e.g., targeted attacks and dependent attacks, dependent attacks and adaptive attacks) are not compatible and cannot help the attacker when used collectively. Our results shed some light on the design of robust complex networks.

Belgian coca-cola-related outbreak: intoxication, mass sociogenic illness, or both?

PubMed

Gallay, A; Van Loock, F; Demarest, S; Van der Heyden, J; Jans, B; Van Oyen, H

2002-01-15

An epidemic of health complaints occurred in five Belgian schools in June 1999. A qualitative investigation described the scenario. The role of soft drinks was assessed by using a case-control study. Cases were students complaining of headache, dizziness, nausea, vomiting, abdominal pain, diarrhea, or trembling. Controls were students present at school on the day of the outbreak but not taken ill. An analysis was performed separately for school A, where the outbreak started, and was pooled for schools B-E. In school A, the attack rate (13.2%) was higher than in schools B-E (3.6%, relative risk = 3.6, 95% confidence interval (CI): 2.5, 5.3). Exclusive consumption of regular Coca-Cola (school A: odds ratio (OR) = 29.7, 95% CI: 1.32, 663.6; schools B-E: OR = 7.3, 95% CI: 2.9, 18.0) and low mental health score (school A: OR = 16.1, 95% CI: 1.3, 201.9; schools B-E: OR = 3.1, 95% CI: 1.5, 6.6) were independently associated with the illness. In schools B-E, consumption of Fanta, consumption of Coca-Cola light, and female gender were also associated with the illness. It seems reasonable to attribute the first cases of illness in school A to regular Coca-Cola consumption. However, mass sociogenic illness could explain the majority of the other cases.

Refractory Degradation by Slag Attack in Coal Gasification

DTIC Science & Technology

2009-02-01

REFRACTORY DEGRADATION BY SLAG ATTACK IN COAL GASIFICATION Jinichiro Nakano 1,2 , Sridhar Seetharaman 1,2 , James Bennett 3 , Kyei-Sing...and two synthetic slags (coal and petcoke). Pulverized slag samples were placed at specific microstructure locations on refractory substrates and...heated to 1500 ºC at log(Po2) = -9, using a high-speed heating chamber. Cross-sections of the slag /refractory interface indicated unique slag

Hancock IAP, Syracuse, New York. Revised Uniform Summary of Surface Weather Observations (RUSSWO). Parts A-F.

DTIC Science & Technology

1982-04-06

57.3 57.4 57." 57.4 5 7 .4 57.4 57.4 57.. 57.4 57.4 , 5 5 56.9 5§. 0-9.35.1 .- ,Z 2.l 5,;.8 54,C c .2 60.3 bJb 61.3 bl.4 61.4, 61.4 61.’. 61. 4 t .4...SUMMARY OF SURPR b2ti UNC.LASSIFIED U SAFETAC/OS-82/O2O SB1-AD-ESSO 164 N I hh Ih,,h ii1 111111111m 4I o5 AO_ IWA 1008 ’LAL CLIMATCLOGY BRACH -LTAC EXTREME...TEMPERATURE OEPRESSION (F) TOTAL TOTAL () 0 1-2 3-4 5 .6 7 5 9.I .2 22. (231S -67 I8I.02.2 2? 2 26127 2 29.-30 * 31OS’S. jb ., W..,I .b0. P..n* 7 / 77

Heart Rate Variability in Sleep-Related Migraine without Aura

PubMed Central

Vollono, Catello; Gnoni, Valentina; Testani, Elisa; Dittoni, Serena; Losurdo, Anna; Colicchio, Salvatore; Di Blasi, Chiara; Mazza, Salvatore; Farina, Benedetto; Della Marca, Giacomo

2013-01-01

Objectives: This is an observational study aimed to investigate the activity of autonomic nervous system during sleep in patients with sleep-related migraine. Methods: Eight consecutive migraineurs without aura were enrolled (6 women and 2 men), aged 30 to 62 years (mean 48.1 ± 9.3 years). Inclusion criteria were: high frequency of attacks (> 5 per month) and occurrence of more than 75% of the attacks during sleep causing an awakening. Patients were compared with a control group of 55 healthy subjects (23 men and 32 women, mean age 54.2 ± 13.0 years), and with a further control group of 8 age- and gender-matched healthy controls. Patient and controls underwent polysomnography and heart rate variability analysis. Results: A significant reduction of the LF/HF ratio during N2 and N3 sleep stages was observed in migraineurs compared with controls. No differences in sleep macrostructure were observed; cyclic alternating pattern (CAP) time and CAP rate were lower in migraineurs than in controls. Conclusions: These findings indicate a peculiar modification of the autonomic balance during sleep in sleep-related migraine. The reduction of LF/HF ratio in NREM sleep was observed in controls, but it was quantitatively much more evident in migraineurs. Changes in LF/HF could be consequent to an autonomic unbalance which could manifest selectively (or alternatively become more evident) during sleep. These findings, together with the reduction in CAP rate, could be an expression of reduced arousability during sleep in patients with sleep-related migraine. The simultaneous involvement of the autonomic, arousal, and pain systems might suggest involvement of the hypothalamic pathways. Citation: Vollono C; Gnoni V; Testani E; Dittoni S; Losurdo A; Colicchio S; Di Blasi C; Mazza S; Farina B; Della Marca G. Heart rate variability in sleep-related migraine without aura. J Clin Sleep Med 2013;9(7):707-714. PMID:23853566

Characterization of Three Novel Linear Neutralizing B-Cell Epitopes in the Capsid Protein of Swine Hepatitis E Virus.

PubMed

Chen, Yiyang; Liu, Baoyuan; Sun, Yani; Li, Huixia; Du, Taofeng; Nan, Yuchen; Hiscox, Julian A; Zhou, En-Min; Zhao, Qin

2018-07-01

Hepatitis E virus (HEV) causes liver disease in humans and is thought to be a zoonotic infection, with domestic animals, including swine and rabbits, being a reservoir. One of the proteins encoded by the virus is the capsid protein. This is likely the major immune-dominant protein and a target for vaccination. Four monoclonal antibodies (MAbs), three novel, 1E4, 2C7, and 2G9, and one previously characterized, 1B5, were evaluated for binding to the capsid protein from genotype 4 swine HEV. The results indicated that 625 DFCP 628 , 458 PSRPF 462 , and 407 EPTV 410 peptides on the capsid protein comprised minimal amino acid sequence motifs recognized by 1E4, 2C7, and 2G9, respectively. The data suggested that 2C7 and 2G9 epitopes were partially exposed on the surface of the capsid protein. Truncated genotype 4 swine HEV capsid protein (sp239, amino acids 368 to 606) can exist in multimeric forms. Preincubation of swine HEV with 2C7, 2G9, or 1B5 before addition to HepG2 cells partially blocked sp239 cell binding and inhibited swine HEV infection. The study indicated that 2C7, 2G9, and 1B5 partially blocked swine HEV infection of rabbits better than 1E4 or normal mouse IgG. The cross-reactivity of antibodies suggested that capsid epitopes recognized by 2C7 and 2G9 are common to HEV strains infecting most host species. Collectively, MAbs 2C7, 2G9, and 1B5 were shown to recognize three novel linear neutralizing B-cell epitopes of genotype 4 HEV capsid protein. These results enhance understanding of HEV capsid protein structure to guide vaccine and antiviral design. IMPORTANCE Genotype 3 and 4 HEVs are zoonotic viruses. Here, genotype 4 HEV was studied due to its prevalence in human populations and pig herds in China. To improve HEV disease diagnosis and prevention, a better understanding of the antigenic structure and neutralizing epitopes of HEV capsid protein are needed. In this study, the locations of three novel linear B-cell recognition epitopes within genotype 4 swine HEV capsid protein were characterized. Moreover, the neutralizing abilities of three MAbs specific for this protein, 2C7, 2G9, and 1B5, were studied in vitro and in vivo Collectively, these findings reveal structural details of genotype 4 HEV capsid protein and should facilitate development of applications for the design of vaccines and antiviral drugs for broader prevention, detection, and treatment of HEV infection of diverse human and animal hosts. Copyright © 2018 American Society for Microbiology.

Combat Medals, Streamers, and Campaigns

DTIC Science & Technology

1990-01-01

he served honorably in the U.S. Army Air Service between April 6, 1917, the date of the American declaration of war against Germany , and November 11...LUXEM9Q.RG,\\\\ German Advance to Ap 5, 1918 rSe.-daSf R’. Iod Sol onsBattle Line Mar 21,1918 (. GERMANY 49 C iaea-Tirro ,RIV erdun Metz 490 48...Headquarters, he dispatched pursuit aircraft to strafe enemy troops crossing the Marne on pontoon bridges . Attacking between Soissons, on the Aisne River, and

Flight Reynolds number effects on a fighter-type, circular-arc-19 deg conic boattail nozzle at subsonic speeds

NASA Technical Reports Server (NTRS)

Chamberlin, R.

1974-01-01

A circular-arc - conic boattail nozzle, typical of those used on a twin engine fighter, was tested on an underwing nacelle mounted on an F-106B aircraft. The boattail had a radius ratio r/r sub c of 0.41 and a terminal boattail angle of approximately 19 deg. The gas generator was a J85-GE-13 turbojet engine. The effects of Reynolds number and angle of attack on boattail pressure drag and boattail pressure profiles were investigated. Increasing Reynolds number resulted in reduced boattail drag at both Mach numbers of 0.6 and 0.9.

Synthesis of 1,2,4-trioxepanes via application of thiol-olefin co-oxygenation methodology.

PubMed

Amewu, Richard; Stachulski, Andrew V; Berry, Neil G; Ward, Stephen A; Davies, Jill; Labat, Gael; Rossignol, Jean-Francois; O'Neill, Paul M

2006-12-01

Thiol-olefin co-oxygenation (TOCO) of substituted allylic alcohols generates beta-hydroxy peroxides that can be condensed in situ with various ketones, to afford a series of functionalised 1,2,4-trioxepanes in good yields. Manipulation of the phenylsulfenyl group in 8a-8c allows for convenient modification to the spiro-trioxepane substituents. Surprisingly, and in contrast to the 1,2,4-trioxanes examined, 1,2,4-trioxepanes are inactive as antimalarials up to 1000 nM and we rationalize this observation based on the inherent stability of these systems to ferrous mediated degradation. FMO calculations clearly show that the sigma* orbital of the peroxide moiety of 1,2,4-trioxane derivatives 4a and 14b are lower in energy and more accessible to attack by Fe(II) compared to their trioxepane analogues 8b and 9b.

Characterization of active reverse transcriptase and nucleoprotein complexes of the yeast retrotransposon Ty3 in vitro.

PubMed

Cristofari, G; Gabus, C; Ficheux, D; Bona, M; Le Grice, S F; Darlix, J L

1999-12-17

Human immunodeficiency virus (HIV) and the distantly related yeast Ty3 retrotransposon encode reverse transcriptase (RT) and a nucleic acid-binding protein designated nucleocapsid protein (NCp) with either one or two zinc fingers, required for HIV-1 replication and Ty3 transposition, respectively. In vitro binding of HIV-1 NCp7 to viral 5' RNA and primer tRNA(3)(Lys) catalyzes formation of nucleoprotein complexes resembling the virion nucleocapsid. Nucleocapsid complex formation functions in viral RNA dimerization and tRNA annealing to the primer binding site (PBS). RT is recruited in these nucleoprotein complexes and synthesizes minus-strand cDNA initiated at the PBS. Recent results on yeast Ty3 have shown that the homologous NCp9 promotes annealing of primer tRNA(i)(Met) to a 5'-3' bipartite PBS, allowing RNA:tRNA dimer formation and initiation of cDNA synthesis at the 5' PBS (). To compare specific cDNA synthesis in a retrotransposon and HIV-1, we have established a Ty3 model system comprising Ty3 RNA with the 5'-3' PBS, primer tRNA(i)(Met), NCp9, and for the first time, highly purified Ty3 RT. Here we report that Ty3 RT is as active as retroviral HIV-1 or murine leukemia virus RT using a synthetic template-primer system. Moreover, and in contrast to what was found with retroviral RTs, retrotransposon Ty3 RT was unable to direct cDNA synthesis by self-priming. We also show that Ty3 nucleoprotein complexes were formed in vitro and that the N terminus of NCp9, but not the zinc finger, is required for complex formation, tRNA annealing to the PBS, RNA dimerization, and primer tRNA-directed cDNA synthesis by Ty3 RT. These results indicate that NCp9 chaperones bona fide cDNA synthesis by RT in the yeast Ty3 retrotransposon, as illustrated for NCp7 in HIV-1, reinforcing the notion that Ty3 NCp9 is an ancestor of HIV-1 NCp7.

0.5-45GHz Simultaneous Transmit and Receive (STAR) Antenna System for Electronic Attack

DTIC Science & Technology

2016-03-17

0.5-45GHz Simultaneous Transmit and Receive (STAR) Antenna System for Electronic Attack Mohamed Elmansouri, Prathap Valaleprasannakumar, Elie...Colorado, US, 80309 Abstract: A shared antenna aperture for simultaneous transmit and receive (STAR) operating from 0.5 to 45GHz with isolation...50dB over the entire band is discussed. The co-located antenna aperture system is designed across 4 overlapping bands: 0.5-2.5GHz, 2-7GHz, 6-19GHz

Electronic Structure and Multisite Basicity of the Pyramidal Phosphinidene-Bridged Dimolybdenum Complex [Mo2(η(5)-C5H5)(μ-κ(1):κ(1),η(5)-PC5H4)(η(6)-C6H3(t)Bu3)(CO)2(PMe3)].

PubMed

Albuerne, Isabel G; Alvarez, M Angeles; García, M Esther; García-Vivó, Daniel; Ruiz, Miguel A

2015-10-19

The title phosphinidene complex could be sequentially protonated with HBF4·OEt2 or [H(OEt2)2](BAr'4) to give the phosphido-bridged derivatives [Mo2Cp(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X and then the hydrides [Mo2Cp(H)(μ-κ(1):κ(1),η(5)-HPC5H4)(η(6)-HMes*)(CO)2(PMe3)]X2 (X = BF4, BAr'4; Ar' = 3,5-C6H3(CF3)2; Mes* = 2,4,6-C6H2(t)Bu3). Density functional theory (DFT) calculations revealed that the most favored site for initial electrophilic attack is the metallocene Mo atom, but attachment of the electrophile to the phosphinidene P atom gives more stable products. This was in agreement with all other reactions investigated, which invariably involved the attachment of the added electrophile at the P site. Thus, the title compound reacted with S8 at 223 K to give the thiophosphinidene-bridged complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(S)C5H4}(η(6)-HMes*)(CO)2(PMe3)], a poorly stable molecule which reacted with MeI at room temperature to give the corresponding thiolatophosphido derivative, isolated as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(SMe)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4) (P-S = 2.128(4) Å) after anion exchange with Na(BAr'4). Reaction of the title compound with MeI proceeded smoothly to give the corresponding methylphosphido derivative, isolated analogously as [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe3)](BAr'4). The related complex [Mo2Cp{μ-κ(1):κ(1),η(5)-P(Me)C5H4}(η(6)-HMes*)(CO)2(PMe2Ph)](BAr'4) (P-C(Me) = 1.841(5) Å) could be prepared analogously from the neutral precursor [Mo2Cp{μ-κ(1):κ(1),η(5)-PC5H4}(η(6)-HMes*)(CO)2(PMe2Ph)]. In contrast, reaction of the title complex with ethylene sulfide involved opening of the C2S ring and formation of new P-C and Mo-S bonds (1.886(7) and 2.493(2) Å, respectively), with displacement of the PMe3 ligand, to give the phosphido-thiolato complex [Mo2Cp{μ-κ(2)(P,S):κ(1)P,η(5)-P(C2H4S)C5H4}(η(6)-HMes*)(CO)2]. All these derivatives of the title complex displayed an unusual trigonal pyramidal-like environment around the bridging P atom, with the added electrophile placed in the Mo2P plane as a result of the directionality of the relevant frontier orbital of the phosphinidene complex, according to DFT calculations.

Measurement of resonance parameters of orbitally excited narrow B0 mesons.

PubMed

Aaltonen, T; Adelman, J; Akimoto, T; Albrow, M G; González, B Alvarez; Amerio, S; Amidei, D; Anastassov, A; Annovi, A; Antos, J; Apollinari, G; Apresyan, A; Arisawa, T; Artikov, A; Ashmanskas, W; Attal, A; Aurisano, A; Azfar, F; Azzurri, P; Badgett, W; Barbaro-Galtieri, A; Barnes, V E; Barnett, B A; Bartsch, V; Bauer, G; Beauchemin, P-H; Bedeschi, F; Beecher, D; Behari, S; Bellettini, G; Bellinger, J; Benjamin, D; Beretvas, A; Beringer, J; Bhatti, A; Binkley, M; Bisello, D; Bizjak, I; Blair, R E; Blocker, C; Blumenfeld, B; Bocci, A; Bodek, A; Boisvert, V; Bolla, G; Bortoletto, D; Boudreau, J; Boveia, A; Brau, B; Bridgeman, A; Brigliadori, L; Bromberg, C; Brubaker, E; Budagov, J; Budd, H S; Budd, S; Burke, S; Burkett, K; Busetto, G; Bussey, P; Buzatu, A; Byrum, K L; Cabrera, S; Calancha, C; Campanelli, M; Campbell, M; Canelli, F; Canepa, A; Carls, B; Carlsmith, D; Carosi, R; Carrillo, S; Carron, S; Casal, B; Casarsa, M; Castro, A; Catastini, P; Cauz, D; Cavaliere, V; Cavalli-Sforza, M; Cerri, A; Cerrito, L; Chang, S H; Chen, Y C; Chertok, M; Chiarelli, G; Chlachidze, G; Chlebana, F; Cho, K; Chokheli, D; Chou, J P; Choudalakis, G; Chuang, S H; Chung, K; Chung, W H; Chung, Y S; Chwalek, T; Ciobanu, C I; Ciocci, M A; Clark, A; Clark, D; Compostella, G; Convery, M E; Conway, J; Cordelli, M; Cortiana, G; Cox, C A; Cox, D J; Crescioli, F; Almenar, C Cuenca; Cuevas, J; Culbertson, R; Cully, J C; Dagenhart, D; Datta, M; Davies, T; de Barbaro, P; De Cecco, S; Deisher, A; De Lorenzo, G; Dell'orso, M; Deluca, C; Demortier, L; Deng, J; Deninno, M; Derwent, P F; di Giovanni, G P; Dionisi, C; Di Ruzza, B; Dittmann, J R; D'Onofrio, M; Donati, S; Dong, P; Donini, J; Dorigo, T; Dube, S; Efron, J; Elagin, A; Erbacher, R; Errede, D; Errede, S; Eusebi, R; Fang, H C; Farrington, S; Fedorko, W T; Feild, R G; Feindt, M; Fernandez, J P; Ferrazza, C; Field, R; Flanagan, G; Forrest, R; Frank, M J; Franklin, M; Freeman, J C; Furic, I; Gallinaro, M; Galyardt, J; Garberson, F; Garcia, J E; Garfinkel, A F; Genser, K; Gerberich, H; Gerdes, D; Gessler, A; Giagu, S; Giakoumopoulou, V; Giannetti, P; Gibson, K; Gimmell, J L; Ginsburg, C M; Giokaris, N; Giordani, M; Giromini, P; Giunta, M; Giurgiu, G; Glagolev, V; Glenzinski, D; Gold, M; Goldschmidt, N; Golossanov, A; Gomez, G; Gomez-Ceballos, G; Goncharov, M; González, O; Gorelov, I; Goshaw, A T; Goulianos, K; Gresele, A; Grinstein, S; Grosso-Pilcher, C; Grundler, U; da Costa, J Guimaraes; Gunay-Unalan, Z; Haber, C; Hahn, K; Hahn, S R; Halkiadakis, E; Han, B-Y; Han, J Y; Happacher, F; Hara, K; Hare, D; Hare, M; Harper, S; Harr, R F; Harris, R M; Hartz, M; Hatakeyama, K; Hays, C; Heck, M; Heijboer, A; Heinrich, J; Henderson, C; Herndon, M; Heuser, J; Hewamanage, S; Hidas, D; Hill, C S; Hirschbuehl, D; Hocker, A; Hou, S; Houlden, M; Hsu, S-C; Huffman, B T; Hughes, R E; Husemann, U; Huston, J; Incandela, J; Introzzi, G; Iori, M; Ivanov, A; James, E; Jayatilaka, B; Jeon, E J; Jha, M K; Jindariani, S; Johnson, W; Jones, M; Joo, K K; Jun, S Y; Jung, J E; Junk, T R; Kamon, T; Kar, D; Karchin, P E; Kato, Y; Kephart, R; Keung, J; Khotilovich, V; Kilminster, B; Kim, D H; Kim, H S; Kim, H W; Kim, J E; Kim, M J; Kim, S B; Kim, S H; Kim, Y K; Kimura, N; Kirsch, L; Klimenko, S; Knuteson, B; Ko, B R; Kondo, K; Kong, D J; Konigsberg, J; Korytov, A; Kotwal, A V; Kreps, M; Kroll, J; Krop, D; Krumnack, N; Kruse, M; Krutelyov, V; Kubo, T; Kuhr, T; Kulkarni, N P; Kurata, M; Kusakabe, Y; Kwang, S; Laasanen, A T; Lami, S; Lammel, S; Lancaster, M; Lander, R L; Lannon, K; Lath, A; Latino, G; Lazzizzera, I; Lecompte, T; Lee, E; Lee, H S; Lee, S W; Leone, S; Lewis, J D; Lin, C-S; Linacre, J; Lindgren, M; Lipeles, E; Lister, A; Litvintsev, D O; Liu, C; Liu, T; Lockyer, N S; Loginov, A; Loreti, M; Lovas, L; Lucchesi, D; Luci, C; Lueck, J; Lujan, P; Lukens, P; Lungu, G; Lyons, L; Lys, J; Lysak, R; Macqueen, D; Madrak, R; Maeshima, K; Makhoul, K; Maki, T; Maksimovic, P; Malde, S; Malik, S; Manca, G; Manousakis-Katsikakis, A; Margaroli, F; Marino, C; Marino, C P; Martin, A; Martin, V; Martínez, M; Martínez-Ballarín, R; Maruyama, T; Mastrandrea, P; Masubuchi, T; Mathis, M; Mattson, M E; Mazzanti, P; McFarland, K S; McIntyre, P; McNulty, R; Mehta, A; Mehtala, P; Menzione, A; Merkel, P; Mesropian, C; Miao, T; Miladinovic, N; Miller, R; Mills, C; Milnik, M; Mitra, A; Mitselmakher, G; Miyake, H; Moggi, N; Moon, C S; Moore, R; Morello, M J; Morlok, J; Fernandez, P Movilla; Mülmenstädt, J; Mukherjee, A; Muller, Th; Mumford, R; Murat, P; Mussini, M; Nachtman, J; Nagai, Y; Nagano, A; Naganoma, J; Nakamura, K; Nakano, I; Napier, A; Necula, V; Nett, J; Neu, C; Neubauer, M S; Neubauer, S; Nielsen, J; Nodulman, L; Norman, M; Norniella, O; Nurse, E; Oakes, L; Oh, S H; Oh, Y D; Oksuzian, I; Okusawa, T; Orava, R; Griso, S Pagan; Palencia, E; Papadimitriou, V; Papaikonomou, A; Paramonov, A A; Parks, B; Pashapour, S; Patrick, J; Pauletta, G; Paulini, M; Paus, C; Peiffer, T; Pellett, D E; Penzo, A; Phillips, T J; Piacentino, G; Pianori, E; Pinera, L; Pitts, K; Plager, C; Pondrom, L; Poukhov, O; Pounder, N; Prakoshyn, F; Pronko, A; Proudfoot, J; Ptohos, F; Pueschel, E; Punzi, G; Pursley, J; Rademacker, J; Rahaman, A; Ramakrishnan, V; Ranjan, N; Redondo, I; Rekovic, V; Renton, P; Renz, M; Rescigno, M; Richter, S; Rimondi, F; Ristori, L; Robson, A; Rodrigo, T; Rodriguez, T; Rogers, E; Rolli, S; Roser, R; Rossi, M; Rossin, R; Roy, P; Ruiz, A; Russ, J; Rusu, V; Safonov, A; Sakumoto, W K; Saltó, O; Santi, L; Sarkar, S; Sartori, L; Sato, K; Savoy-Navarro, A; Schlabach, P; Schmidt, A; Schmidt, E E; Schmidt, M A; Schmidt, M P; Schmitt, M; Schwarz, T; Scodellaro, L; Scribano, A; Scuri, F; Sedov, A; Seidel, S; Seiya, Y; Semenov, A; Sexton-Kennedy, L; Sforza, F; Sfyrla, A; Shalhout, S Z; Shears, T; Shepard, P F; Shimojima, M; Shiraishi, S; Shochet, M; Shon, Y; Shreyber, I; Sidoti, A; Sinervo, P; Sisakyan, A; Slaughter, A J; Slaunwhite, J; Sliwa, K; Smith, J R; Snider, F D; Snihur, R; Soha, A; Somalwar, S; Sorin, V; Spalding, J; Spreitzer, T; Squillacioti, P; Stanitzki, M; St Denis, R; Stelzer, B; Stelzer-Chilton, O; Stentz, D; Strologas, J; Strycker, G L; Stuart, D; Suh, J S; Sukhanov, A; Suslov, I; Suzuki, T; Taffard, A; Takashima, R; Takeuchi, Y; Tanaka, R; Tecchio, M; Teng, P K; Terashi, K; Thom, J; Thompson, A S; Thompson, G A; Thomson, E; Tipton, P; Ttito-Guzmán, P; Tkaczyk, S; Toback, D; Tokar, S; Tollefson, K; Tomura, T; Tonelli, D; Torre, S; Torretta, D; Totaro, P; Tourneur, S; Trovato, M; Tsai, S-Y; Tu, Y; Turini, N; Ukegawa, F; Vallecorsa, S; van Remortel, N; Varganov, A; Vataga, E; Vázquez, F; Velev, G; Vellidis, C; Veszpremi, V; Vidal, M; Vidal, R; Vila, I; Vilar, R; Vine, T; Vogel, M; Volobouev, I; Volpi, G; Wagner, P; Wagner, R G; Wagner, R L; Wagner, W; Wagner-Kuhr, J; Wakisaka, T; Wallny, R; Wang, S M; Warburton, A; Waters, D; Weinberger, M; Weinelt, J; Wester, W C; Whitehouse, B; Whiteson, D; Wicklund, A B; Wicklund, E; Wilbur, S; Williams, G; Williams, H H; Wilson, P; Winer, B L; Wittich, P; Wolbers, S; Wolfe, C; Wright, T; Wu, X; Würthwein, F; Wynne, S M; Xie, S; Yagil, A; Yamamoto, K; Yamaoka, J; Yang, U K; Yang, Y C; Yao, W M; Yeh, G P; Yoh, J; Yorita, K; Yoshida, T; Yu, G B; Yu, I; Yu, S S; Yun, J C; Zanello, L; Zanetti, A; Zhang, X; Zheng, Y; Zucchelli, S

2009-03-13

We report a measurement of resonance parameters of the orbitally excited (L=1) narrow B0 mesons in decays to B;{(*)+}pi;{-} using 1.7 fb;{-1} of data collected by the CDF II detector at the Fermilab Tevatron. The mass and width of the B_{2};{*0} state are measured to be m(B_{2};{*0})=5740.2_{-1.8};{+1.7}(stat)-0.8+0.9(syst) MeV/c;{2} and Gamma(B_{2};{*0})=22.7_{-3.2};{+3.8}(stat)-10.2+3.2(syst) MeV/c;{2}. The mass difference between the B_{2};{*0} and B10 states is measured to be 14.9_{-2.5};{+2.2}(stat)-1.4+1.2(syst) MeV/c;{2}, resulting in a B10 mass of 5725.3_{-2.2};{+1.6}(stat)-1.5+1.4(syst) MeV/c;{2}. This is currently the most precise measurement of the masses of these states and the first measurement of the B_{2};{*0} width.

The role of TcdB and TccC subunits in secretion of the Photorhabdus Tcd toxin complex.

PubMed

Yang, Guowei; Waterfield, Nicholas R

2013-01-01

The Toxin Complex (TC) is a large multi-subunit toxin encoded by a range of bacterial pathogens. The best-characterized examples are from the insect pathogens Photorhabdus, Xenorhabdus and Yersinia. They consist of three large protein subunits, designated A, B and C that assemble in a 5∶1∶1 stoichiometry. Oral toxicity to a range of insects means that some have the potential to be developed as pest control technology. The three subunit proteins do not encode any recognisable export sequences and as such little progress has been made in understanding their secretion. We have developed heterologous TC production and secretion models in E. coli and used them to ascribe functions to different domains of the crucial B+C sub-complex. We have determined that the B and C subunits use a secretion mechanism that is either encoded by the proteins themselves or employ an as yet undefined system common to laboratory strains of E. coli. We demonstrate that both the N-terminal domains of the B and C subunits are required for secretion of the whole complex. We propose a model whereby the N-terminus of the C-subunit toxin exports the B+C sub-complex across the inner membrane while that of the B-subunit allows passage across the outer membrane. We also demonstrate that even in the absence of the B-subunit, that the C-subunit can also facilitate secretion of the larger A-subunit. The recognition of this novel export system is likely to be of importance to future protein secretion studies. Finally, the identification of homologues of B and C subunits in diverse bacterial pathogens, including Burkholderia and Pseudomonas, suggests that these toxins are likely to be important in a range of different hosts, including man.

Growth of Highly c-axis Oriented and/or Epitaxial Single-Domain b-axis Oriented La5Ca9Cu24O41 Thin Films by Pulsed Laser Deposition

DTIC Science & Technology

2016-04-01

project attempted to grow La5Ca9Cu24O41 (LCCO) films on important substrates with the high- thermal -conductivity direction parallel or perpendicular...to the surface of the substrate, counting success as demonstration of b-axis or c-axis oriented LCCO films along with measurement of bulk thermal ...deposition, LCCO, La5Ca9Cu24O41, thermal conductivity, epitaxy 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT SAR 18. NUMBER OF PAGES 24

Do burns increase the severity of terror injuries?

PubMed

Peleg, Kobi; Liran, Alon; Tessone, Ariel; Givon, Adi; Orenstein, Arie; Haik, Josef

2008-01-01

The use of explosives and suicide bombings has become more frequent since October 2000. This change in the nature of terror attacks has marked a new era in the Israeli-Palestinian conflict. We previously reported that the incidence of thermal injuries has since risen. However, the rise in the incidence of burns among victims of terror was proportionate to the rise in the incidence of burns among all trauma victims. This paper presents data from the Israeli National Trauma Registry during the years 1997--2003, to compare the severity of injuries and outcome (mortality rates) in terror victims with and without burn injuries. We also compare the severity of injuries and outcome (mortality rates) for patients with terror-attack related burns to non terror-attack related burns during the same period. Data was obtained from the Israeli National Trauma Registry for all patients admitted to 8 to 10 hospitals in Israel between 1997 and 2003. We analyzed and compared demographic and clinical characteristics of 219 terror-related burn patients (terror/burn), 2228 terror patients with no associated burns (Terror/no-burn) and 6546 non terror related burn patients (burn/no-terror). Severity of injuries was measured using the injury severity score, and burn severity by total body surface percentage indices. Admission rates to Intensive Care Units (ICU) and total length of hospitalization were also used to measure severity of injuries. In-hospital mortality rates were used to indicate outcome. Of burn/terror patients, 87.2% suffered other accompanying injuries, compared with 10.4% of burn/no-terror patients. Of burn/terror patients, 49.8% were admitted to ICU compared with only 11.9% of burn/no-terror patients and 23.8% of no-burn/terror patients. Mean length of hospital stay was 18.5 days for the terror/burn group compared with 11.1 days for the burn/no-terror group and 9.5 days for the terror/no-burn group. Burn/terror patients had a significantly higher injury severity score compared with the other groups. In-hospital mortality rate for the burn/no-terror group was 3.4%. The burn/terror group had a mortality rate of 6.4% which was similar to the no-burn/terror group (6.6%). Terror-attack injuries with accompanying burns have a more complex presentation, are of higher severity, and are associated with increased length of hospital stay and a higher ICU admissions rate, compared with terror-attack injuries without burns and non terror-attack related burns. However, mortality rates in terror-attack injuries are not affected by burns.

Assessing the exchange coupling in binuclear lanthanide(iii) complexes and the slow relaxation of the magnetization in the antiferromagnetically coupled Dy2 derivative† †Electronic supplementary information (ESI) available: Additional magnetic data, additional figures and computational details. CCDC 1020818–1020822. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5sc01029b

PubMed Central

Chow, Chun Y.; Bolvin, Hélène; Campbell, Victoria E.; Guillot, Régis; Kampf, Jeff W.; Wernsdorfer, Wolfgang; Gendron, Frédéric; Autschbach, Jochen

2015-01-01

We report here the synthesis and the investigation of the magnetic properties of a series of binuclear lanthanide complexes belonging to the metallacrown family. The isostructural complexes have a core structure with the general formula [Ga4Ln2(shi3–)4(Hshi2–)2(H2shi–)2(C5H5N)4(CH3OH)x(H2O)x]·xC5H5N·xCH3OH·xH2O (where H3shi = salicylhydroxamic acid and Ln = GdIII1; TbIII2; DyIII3; ErIII4; YIII5; YIII0.9DyIII0.16). Apart from the Er-containing complex, all complexes exhibit an antiferromagnetic exchange coupling leading to a diamagnetic ground state. Magnetic studies, below 2 K, on a single crystal of 3 using a micro-squid array reveal an opening of the magnetic hysteresis cycle at zero field. The dynamic susceptibility studies of 3 and of the diluted DyY 6 complexes reveal the presence of two relaxation processes for 3 that are due to the excited ferromagnetic state and to the uncoupled DyIII ions. The antiferromagnetic coupling in 3 was shown to be mainly due to an exchange mechanism, which accounts for about 2/3 of the energy gap between the antiferro- and the ferromagnetic states. The overlap integrals between the Natural Spin Orbitals (NSOs) of the mononuclear fragments, which are related to the magnitude of the antiferromagnetic exchange, are one order of magnitude larger for the Dy2 than for the Er2 complex. PMID:29218180

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

Ben Smida, Youssef; Marzouki, Riadh; Georges, Samuel

A new sodium cobalt (II) arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} has been synthesized by a solid-state reaction and its crystal structure determined from single crystal X-ray diffraction data. It crystallizes in the monoclinic system, space group C2/m, with a=10.7098(9) Å, b=14.7837(9) Å, c=6.6845(7) Å, and β=105.545(9)°. The structure is described as a three-dimensional framework built up of corner-edge sharing CoO{sub 6}, CoO{sub 4} and AsO{sub 4} polyhedra, with interconnecting channels along [100] in which the Na{sup +} cations are located. The densest ceramics with relative density of 94% was obtained by ball milling and optimization of sintering temperature, andmore » its microstructure characterized by scanning electron microscopy. The electrical properties of the ceramics were studied over a temperature interval from 280 °C to 560 °C using the complex impedance spectroscopy over the range of 13 MHz–5 Hz. The ionic bulk conductivity value of the sample at 360 °C is 2.51 10{sup −5} S cm{sup −1} and the measured activation energy is Ea=1 eV. The sodium migration pathways in the crystal structure were investigated computationally using the bond valence site energy (BVSE) model and classical molecular dynamics (MD) simulations. - Graphical abstract: Correlation between crystal structure, microstructure and ionic conductivity . Display Omitted - Highlights: • A new arsenate Na{sub 4}Co{sub 7}(AsO{sub 4}){sub 6} was prepared by solid state reaction. • Its crystal structure was determined by powder X-ray diffraction. • Na{sup +} ionic conductivity was probed by complex impedance spectroscopy. • Na{sup +} conduction pathways were modeled by bond-valence method and molecular dynamics.« less

Statistics on Aircraft Gas Turbine Engine Rotor Failures That Occurred in U.S. Commercial Aviation During 1989

DTIC Science & Technology

1992-06-01

CF6 920 2.9464 5 2 3 10 1.70 0.68 1.02 3.39 P.8211 412 1.2878 6 0 6 12 4.66 0.00 4.66 9.32 PW2037/2040 218 0.4853 3 0 3 6 6.18 0.00 6.18 12.36 TFE731 ...SRAA L382 501 T N 7 N 4 S-90021200109 SRAA 1382 501 C N 3 N 3 S-890509033 NMO1 L35A TFE731 T B 7 C 5 S-891019049 EA21 135 TFE731 C N 2 N 5 S-890301001...BKXA L35A TFE731 T N 7 N 4 A-890818049979C CE03 DC9 JT8D/1 T B 7 NC 4 A-890624033059C EA27 B727 JT8D/2 C D 7 NC 3 A-890719023719B CE01 DCIO CF6/2 F D 7

Hydrogen attack in Cr-Mo steels. [3Cr-1. 5Mo and 2. 25Cr-1Mo steels

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

Ruoff, S.; Stone, D.; Wanagel, J.

Experiments conducted upon 3Cr-1.5Mo steel at elevated temperatures (600 C), and high pressure hydrogen (2000 psi), have shown a greater resistence to hydrogen attack compared with similar studies of 2.25Cr-lMo steels. Hydrogen exposure tests with and without an applied stress have been performed on both types of steels. Results of similar conditions show clear evidence of hydrogen attack in 2.25Cr-lMo steel, however, for the 3Cr-1.5Mo steel with exposure time up to 80 days without an applied stress no evidence of hydrogen attack is observed. For stress-rupture tests using stresses of 14 and 16 ksi, the 3Cr-1.5Mo steel showed no effectsmore » of hydrogen attack, and no damage was observed using a SEM.« less

Oxidation Chemistry of Inorganic Benzene Complexes.

PubMed

Fleischmann, Martin; Dielmann, Fabian; Balázs, Gábor; Scheer, Manfred

2016-10-17

The oxidation of the 28 VE cyclo-E 6 triple-decker complexes [(Cp R Mo) 2 (μ,η 6 :η 6 -E 6 )] (E=P, Cp R =Cp(2 a), Cp*(2 b), Cp Bn (2 c)=C 5 (CH 2 Ph) 5 ; E=As, Cp R =Cp*(3)) by Cu + or Ag + leads to cationic 27 VE complexes that retain their general triple-decker geometry in the solid state. The obtained products have been characterized by cyclic voltammetry (CV), EPR, Evans NMR, multinuclear NMR spectroscopy, MS, and structural analysis by single-crystal X-ray diffraction. The cyclo-E 6 middle decks of the oxidized complexes are distorted to a quinoid (2 a) or bisallylic (2 b, 2 c, 3) geometry. DFT calculations of 2 a, 2 b, and 3 persistently result in the bisallylic distortion as the minimum geometry and show that the oxidation leads to a depopulation of the σ-system of the cyclo-E 6 ligands in 2 a-3. Among the starting complexes, 2 c is reported for the first time including its preparation and full characterization. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Space shuttle: High angle of attack transition and low angle of attack launch phase aerodynamic stability and control of GD/C B-18E-2, B-18E-3 delta wing booster, and launch configuration of MSC-040A orbiter and twin pressure fed boosters

NASA Technical Reports Server (NTRS)

Debevoise, J. M.; Mcginnis, R. F.

1972-01-01

The test was a conventional stability and control test except for two aspects. One was the very high angles of attack at which the delta wing configurations were tested (up to 60 degrees) at Mach numbers of 3 and 4.96. The other was the installation of the orbiter and twin boosters in a manner that caused the support system to induce normal forces and side forces on the aft portion of the boosters at all Mach numbers; i.e., the support and the booster bodies were close together, side by side.

Binding mode of cytochalasin B to F-actin is altered by lateral binding of regulatory proteins.

PubMed

Suzuki, N; Mihashi, K

1991-01-01

The binding of cytochalasin B (CB) to F-actin was studied using a trace amount of [3H]-cytochalasin B. F-Actin-bound CB was separated from free CB by ultracentrifugation and the amount of F-actin-bound CB was determined by comparing the radioactivity both in the supernatant and in the precipitate. A filament of pure F-actin possessed one high-affinity binding site for CB (Kd = 5.0 nM) at the B-end. When the filament was bound to native tropomyosin (complex of tropomyosin and troponin), two low-affinity binding sites for CB (Kd = 230 nM) were created, while the high-affinity binding site was reserved (Kd = 3.4 nM). It was concluded that the creation of low-affinity binding sites was primarily due to binding of tropomyosin to F-actin, as judged from the following two observations: (1) a filament of F-actin/tropomyosin complex possessed one high-affinity binding site (Kd = 3.9 nM) plus two low-affinity binding sites (Kd = 550 nM); (2) the Ca2(+)-receptive state of troponin C in F-actin/native tropomyosin complex did not affect CB binding.

[Comorbidity in panic disorders and alcoholism (II). Alcoholism in a sample of 148 patients with panic disorders].

PubMed

Segui, J; Salvador, L; Canet, J; Aragón, C; Herrera, C

1995-01-01

Among 148 patients presenting Panic Disorder (DSM-III-R), 18.9% have an alcohol disorder, 8.8% present abuse and 10.1% dependence. Mean age of onset of alcoholism was much earlier than panic disorder. Patients with alcoholism: a) are males more frequently (0.001); b) present more alcoholism in first grade relatives (0.05); c) use more often other drugs like: tobacco (0.01), coffee (p < 0.01), cocaine (p < 0.01) and cannabis (p < 0.001), d) patients with alcoholism refer a greater severity of their panic attacks when drinking large amounts of alcohol (25%) than the group without these problems (2.5%) (x2:14.8) (p < 0.001) e) according to the GAS the overall level of performance is lower in alcoholics (p < 0.005); f) present more anxiety measured by the HARS (p < 0.01), and therefore have more comorbid anxiety disorders according to DSM-III-R (p < 0.01). The clinical significance of these findings is discussed.

Luminescent cyclometalated iridium(III) polypyridine indole complexes--synthesis, photophysics, electrochemistry, protein-binding properties, cytotoxicity, and cellular uptake.

PubMed

Lau, Jason Shing-Yip; Lee, Pui-Kei; Tsang, Keith Hing-Kit; Ng, Cyrus Ho-Cheong; Lam, Yun-Wah; Cheng, Shuk-Han; Lo, Kenneth Kam-Wing

2009-01-19

A series of luminescent cyclometalated iridium(III) polypyridine indole complexes, [Ir(N--C)(2)(N--N)](PF(6)) (HN--C = 2-phenylpyridine (Hppy), N--N = 4-((2-(indol-3-yl)ethyl)aminocarbonyl)-4'-methyl-2,2'-bipyridine (bpy-ind) (1a), N--N = 4-((5-((2-(indol-3-yl)ethyl)aminocarbonyl)pentyl)aminocarbonyl)-4'-methyl-2,2'-bipyridine (bpy-C6-ind) (1b); HN--C = 7,8-benzoquinoline (Hbzq), N--N = bpy-ind (2a), N--N = bpy-C6-ind (2b); and HN--C = 2-phenylquinoline (Hpq), N--N = bpy-ind (3a), N--N = bpy-C6-ind (3b)), have been synthesized, characterized, and their photophysical and electrochemical properties and lipophilicity investigated. Photoexcitation of the complexes in fluid solutions at 298 K and in alcohol glass at 77 K resulted in intense and long-lived luminescence (lambda(em) = 540-616 nm, tau(o) = 0.13-5.15 mus). The emission of the complexes has been assigned to a triplet metal-to-ligand charge-transfer ((3)MLCT) (dpi(Ir) --> pi*(N--N)) excited state, probably with some mixing of triplet intraligand ((3)IL) (pi --> pi*) (pq) character for complexes 3a,b. Electrochemical measurements revealed that all the complexes showed an irreversible indole oxidation wave at ca. +1.1 V versus SCE, a quasi-reversible iridium(IV/III) couple at ca. +1.3 V, and a reversible diimine reduction couple at ca. -1.3 V. The interactions of these complexes with an indole-binding protein, bovine serum albumin (BSA), have been studied by emission titrations, and the K(a) values are on the order of 10(4) M(-1). Additionally, the cytotoxicity of the complexes toward human cervix epithelioid carcinoma (HeLa) cells has been examined by the 3-(4,5-dimethyl-2-thiazolyl)-2,5-diphenyltetrazolium bromide (MTT) assay. The IC(50) values of the complexes ranged from 1.1 to 6.3 microM, which are significantly smaller than that of cisplatin (30.7 microM) under the same experimental conditions. Furthermore, the cellular uptake of the complexes has been investigated by flow cytometry and laser-scanning confocal microscopy. The microscopy images indicated that complex 3a was localized in the perinuclear region upon interiorization. Temperature-dependence experiments suggested that the internalization of the complex was an energy-requiring process such as endocytosis. This has been confirmed by cellular-uptake experiments involving the luminescent conjugates Ir-BSA and Ir-TF (TF = holo-transferrin), which were prepared by conjugation of the proteins with the complex [Ir(pq)(2)(phen-NCS)](PF(6)) (phen-NCS = 5-isothiocyanato-1,10-phenanthroline).

Middle East coastal ecosystem response to middle-to-late Holocene abrupt climate changes.

PubMed

Kaniewski, D; Paulissen, E; Van Campo, E; Al-Maqdissi, M; Bretschneider, J; Van Lerberghe, K

2008-09-16

The Holocene vegetation history of the northern coastal Arabian Peninsula is of long-standing interest, as this Mediterranean/semiarid/arid region is known to be particularly sensitive to climatic changes. Detailed palynological data from an 800-cm alluvial sequence cored in the Jableh plain in northwest Syria have been used to reconstruct the vegetation dynamics in the coastal lowlands and the nearby Jabal an Nuşayriyah mountains for the period 2150 to 550 B.C. Corresponding with the 4.2 to 3.9 and 3.5 to 2.5 cal kyr BP abrupt climate changes (ACCs), two large-scale shifts to a more arid climate have been recorded. These two ACCs had different impacts on the vegetation assemblages in coastal Syria. The 3.5 to 2.5 cal kyr BP ACC is drier and lasted longer than the 4.2 to 3.9 cal kyr BP ACC, and is characterized by the development of a warm steppe pollen-derived biome (1100-800 B.C.) and a peak of hot desert pollen-derived biome at 900 B.C. The 4.2 to 3.9 cal kyr BP ACC is characterized by a xerophytic woods and shrubs pollen-derived biome ca. 2050 B.C. The impact of the 3.5 to 2.5 cal kyr BP ACC on human occupation and cultural development is important along the Syrian coast with the destruction of Ugarit and the collapse of the Ugarit kingdom at ca. 1190 to 1185 B.C.

Middle East coastal ecosystem response to middle-to-late Holocene abrupt climate changes

PubMed Central

Kaniewski, D.; Paulissen, E.; Van Campo, E.; Al-Maqdissi, M.; Bretschneider, J.; Van Lerberghe, K.

2008-01-01

The Holocene vegetation history of the northern coastal Arabian Peninsula is of long-standing interest, as this Mediterranean/semiarid/arid region is known to be particularly sensitive to climatic changes. Detailed palynological data from an 800-cm alluvial sequence cored in the Jableh plain in northwest Syria have been used to reconstruct the vegetation dynamics in the coastal lowlands and the nearby Jabal an Nuşayriyah mountains for the period 2150 to 550 B.C. Corresponding with the 4.2 to 3.9 and 3.5 to 2.5 cal kyr BP abrupt climate changes (ACCs), two large-scale shifts to a more arid climate have been recorded. These two ACCs had different impacts on the vegetation assemblages in coastal Syria. The 3.5 to 2.5 cal kyr BP ACC is drier and lasted longer than the 4.2 to 3.9 cal kyr BP ACC, and is characterized by the development of a warm steppe pollen-derived biome (1100–800 B.C.) and a peak of hot desert pollen-derived biome at 900 B.C. The 4.2 to 3.9 cal kyr BP ACC is characterized by a xerophytic woods and shrubs pollen-derived biome ca. 2050 B.C. The impact of the 3.5 to 2.5 cal kyr BP ACC on human occupation and cultural development is important along the Syrian coast with the destruction of Ugarit and the collapse of the Ugarit kingdom at ca. 1190 to 1185 B.C. PMID:18772385

Dynamic NMR study of ethene exchange in cationic CNN-type platinum(II) complexes.

PubMed

Plutino, M Rosaria; Fenech, Lucia; Stoccoro, Sergio; Rizzato, Silvia; Castellano, Carlo; Albinati, Alberto

2010-01-18

Cationic ethylene platinum(II) complexes of the type [Pt(CNN)(C(2)H(4))](+), containing a methyl fragment and different diimines (NN), or terdentate (kappaC-kappa(2)NN') anionic ligands, were synthesized and fully characterized both as solids and in solution [NN = 2,2'-dipyridylamine, 1; 2,2'-dipyridylsulfide, 2; 1,10-phenanthroline, 3; 4,7-diphenyl-1,10-phenanthroline, 4; 3,4,7,8-tetramethyl-1,10-phenanthroline, 5; 2,2'-bipyridine, 6; HC-NN = 6-tert-butyl-2,2'-bipyridine, 7; 6-neo-pentyl-2,2'-bipyridine, 8; 6-phenyl-2,2'-bipyridine, 9; 6-(alpha-methyl)benzyl-2,2'-bipyridine, 10; 6-(alpha-ethyl)benzyl-2,2'-bipyridine, 11; 6-(alpha,alpha-dimethyl)benzyl-2,2'-bipyridine, 12]. Crystals suitable for X-ray analysis of complexes 5 and 7 were obtained. Ethene exchange at the cyclometalated platinum(II) complexes 7, 8, and 10-12 was studied by (1)H NMR line-broadening experiments in chloroform-d, as a function of both temperature and olefin concentrations. For the other prepared complexes the process was too fast to be monitored on the NMR time scale even at the lowest temperature. The ethylene exchange rates show a linear dependence on the concentration of the free ligand, with a negligible k(1) term indicating that either a solvolytic or a dissociative pathway to the products is absent or negligible. The values of the second-order rate constants k(exc), as obtained by linear regression analysis of the experimental data at 298 K, are in a range of ca. 10(4)-10(5) s(-1) m(-1). The activation entropies are negative, ranging between -129 and -112 J K(-1) mol(-1), as expected for associative processes. The activation process is largely entropy controlled: the TDeltaS()() contribution to the free energy of activation is extremely large, amounting to more than 80% for all complexes, with a smaller enthalpy contribution. All the experimental findings evidence that the mechanism takes place via an associative attack by the entering olefin, through a well-ordered, stable pentacoordinated transition state with the two ethene molecules on the trigonal plane. The reactivity of [Pt(CNN)(C(2)H(4))](+) complexes is strongly dependent on the choice of coordinated 6-substituted-2,2'-bipyridines, especially when the terdentate anionic fragment is capable of generating steric crowding and congestion on the coordination plane.

[Effects of high cholic acid on fetal brains of pregnant rats].

PubMed

Tan, Li; Ding, Yi-ling

2007-12-01

To investigate the effects of morphous on fetal brains in pregnant rat of high cholic acid. Randomly deviding 30 SD pregnant rats to three groups A, B and C, every group is 10. From 13th to 20th days of pregnancy, injecting 5.5 mg x kg(-1) x d(-1) cholic acid to pregnant rats of group A, 1.4 mg x kg(-1) x d(-1) cholic acid to group B and the partes aequales normal saline to group C by intraperitoneal injection one time every day. In the 21st day of pregancy, to cut the belly open and take the fetus out and record the total fetus, live fetus and the weight. Determine the serum concentration of total bile acid (TBA) in pregnant rats and fetal rats. Enzyme linked immunosorbent assay(ELISA) was used to detect the serum level of neuron-specific enolase (NSE) in fetal rats. Fix and embed the brain after decapitation, then to observe the pathological change of the fetal cerebrum under light microscope and electron microscope. (1) The serum concentration of TBA of pregnant rats and fetal rats in group A is (22.3 +/- 8.1) micromol/L and (28.8 +/- 8.1) micromol/L, in group B is (9.8 +/- 3.6) micromol/L and (9.3 +/- 3.5) micromol/L, in group C is (3.6 +/- 1.8) micromol/L and (4.0 +/- 1.2) micromol/L. There is significant defference in every two groups, P < 0.01. The serum concentration of TBA between pregnant rats and fetal rats were positively correlated with each other, (r = 0.875, P < 0.01). (2) The mortinatality of fetus in group A, B and C are 30.1%, 16.9% and 7.1%, there is significant defference in every two groups, P < 0.05. (3) The serum lever of NSE of fetus in group A was significantly higher than that of group B and C, [(31.9 +/- 13.1) ng/L vs. (13.9 +/- 5.9) ng/L and (9.3 +/- 3.9) ng/L, both are P < 0.05]. But there is no significant difference between group B and C, P > 0.05. The serum level of TBA and NSE in fetus were positively correlated with each other, (r = 0.758, P < 0.01). (4) By the light microscope we found that the neuronal degeneration and necrosis. The level of organization disorder, the density of nerve cells decrease and the cell nucleus pyknosis and anachromasis. The neuronal degeneration area in group A and B are significantly higher than group C[(1.4 +/- 0.6) and (1.5 +/- 0.7) vs. (0.7 +/- 0.3), both are P < 0.05]. But there is no significant difference between group A and B, P > 0.05. The is no apparente correlation between the neuronal degeneration area and the serum level of NSE in fetus, r = 0.282, P > 0.05. The neuronal necrosis area in group A are significantly higher than group B and C [(1.8 +/- 0.7) vs. (0.9 +/- 0.4) and (0.6 +/- 0.3), both are P < 0.05]. But there is no significant defference between group B and C, P > 0.05. The neuronal necrosis area and the level of NSE in fetus were positively correlated with each other, r = 0.798, P < 0.01. (5) Under the electron microscope we found that the neuronal nuclear membrance ambiguity, karyopycnosis, nucleolus disappeared, nuclear chromatin rarefaction. The number of endoplasmic reticulum and mitochondria decrease, the residual mitochondria swelling, cristae quassation. The number density of mitochondria of nerve cells in group A is significantly lower than that of group B and C [(21.9 +/- 9.0) microm(-3) vs. (45.5 +/- 13.1) microm(-3) and (36.1 +/- 12.1) mcirom(-3), both are P < 0.01]. But there is no significant difference between group B and C, P > 0. 05. The volume of mitochondria of nerve cells in group A and B are significantly higher than that of group C [7.0 +/-1.8) x 10(-4) microm3 and (5.7 +/- 1.6) x 10(-4) microM3 vs. (3.2 +/- 1.2) x 10(-4) microm(3), both are P < 0.01]. But there is no significant difference between group A and B (P > 0.05). There is apparente pathological change of fetal rats brain in cholic acid groups, the neuronal degeneration and the mitochondria swelling was mainly found in low cholic acid group, the neuronal necrosis and the mitochondria decrease was mainly found in high cholic acid group. The serum concentration of TBA and NSE in fetal rats were positively correlated with each other.

Analysis of Major Item Redistribution/Substitution Policies. Volume 2

DTIC Science & Technology

1980-05-01

juv11ld4vvb I 1 ki vat) 1 7A u,1 I / , Uju a I A,4/ FfA /1ILV)o 13bAvulu9db4 I 1 G vd 5utlA ’I b~𔃽 AAZ)I Ad-IUbC/H KC 5 jJuuu3337S 9 I I G~ v 2/ U)’ A...bblUut)1� 14 1 Do A I U(1b b150t) bbP ,(DV23g29bl 113 dj vb 4 It ’qvII lri U 4LJ I ebO 0b/5IUU~ddd5 I 1 d I~0d i’"Ikj O’.VI it/ II Ft-C;Ao beP 0e

Naphtho[1,2-b:5,6-b']dithiophene-Based Conjugated Polymers for Fullerene-Free Inverted Polymer Solar Cells.

PubMed

Jiang, Zhaoyan; Li, Huan; Wang, Zhen; Zhang, Jianqi; Zhang, Yajie; Lu, Kun; Wei, Zhixiang

2018-03-23

Three novel copolymers based on zigzag naphthodithiophene (zNDT) with different aromatic rings as π bridges and different core side substitutions are designed and synthesized (PzNDT-T-1,3-bis(4-(2-ethylhexyl)-thiophen-2-yl)-5,7-bis(2-ethylhexyl)benzo[1,2-c:4,5-c']-dithiophene-4,8-dione (BDD), PzNDT-TT-BDD, and PzNDTP-T-BDD, respectively). The 2D conjugation structure and molecular planarity of the polymers can be effectively altered through the modification of conjugated side chains and π-bridges. These alterations contribute to the variation in energy levels, light absorption capacity, and morphology compatibility of the polymers. When blended with the nonfullerene acceptor (2,2'-[(4,4,9,9-tetrahexyl-4,9-dihydro-sindaceno[1,2-b:5,6-b']dithiophene-2,7-diyl)bis[methylidyne(3-oxo-1H-indene-2,1(3H)-diylidene)

Corrosion in Magnesium and a Magnesium Alloy

NASA Astrophysics Data System (ADS)

Akavipat, Sanay

Magnesium and a magnesium alloy (AZ91C) have been ion implanted over a range of ions energies (50 to 150 keV) and doses (1 x 10('16) to 2 x 10('17) ions/cm('2)) to modify the corrosion properties of the metals. The corrosion tests were done by anodic polarization in chloride -free and chloride-containing aqueous solutions of a borated -boric acid with a pH of 9.3. Anodic polarization measurements showed that some implantations could greatly reduce the corrosion current densities at all impressed voltages and also increased slightly the pitting potential, which indicated the onset of the chloride attack. These improvements in corrosion resistance were caused by boron implantations into both types of samples. However, iron implantations were found to improve only the magnesium alloy. To study the corrosion in more detail, Scanning Auger Microprobe Spectrometer (SAM), Scanning Electron Microscope (SEM) with an X-ray Energy Spectrometry (XES) attachment, and Transmission Electron Microscope (TEM) measurements were used to analyze samples before, after, and at various corrosion stages. In both the unimplanted pure magnesium and AZ91C samples, anodic polarization results revealed that there were three active corrosion stages (Stages A, C, and E) and two passivating stages (Stages B and D). Examination of Stages A and B in both types of samples showed that only a mild, generalized corrosion had occurred. In Stage C of the TD samples, a pitting breakdown in the initial oxide film was observed. In Stage C of the AZ91C samples, galvanic and intergranular attack around the Mg(,17)Al(,12) intermetallic islands and along the matrix grain boundaries was observed. Stage D of both samples showed the formation of a thick, passivating oxygen containing, probably Mg(OH)(,2) film. In Stage E, this film was broken down by pits, which formed due to the presence of the chloride ions in both types of samples. Stages A through D of the unimplanted samples were not seen in the boron or iron implanted samples. Instead one low current density passivating stage was formed, which was ultimately broken down by the chloride attack. It is believed that the implantation of boron modified the initial surface film to inhibit corrosion, whereas the iron implantation modified the intermetallic (Mg(,17)Al(,12)) islands to act as sacrificial anodes.

Mitomycin C binding to poly[d(G-m5C)].

PubMed Central

Portugal, J; Sánchez-Baeza, F J

1995-01-01

Poly[d(G-m5C)] was modified by reductively activated mitomycin C, an anti-tumour drug, under buffer conditions which are known to favour either the B or the Z conformations of DNA. C.d. and 31P-n.m.r. were used to characterize the poly[d(G-m5C)]-mitomycin cross-linked complexes, as well as the effects on the equilibrium between the B and Z forms of the polynucleotide. Mitomycin C appears to inhibit the B-->Z transition, even in the presence of 3 mM MgCl2, while the Z-form of poly[d(G-m5C)] does not interact significantly with the drug under bifunctionally activating conditions; thus no reversion from the Z-form to the B-form of the polynucleotide can be observed under the salt conditions which are required for the Z-form to exist. PMID:7864808

Molecular Structure of WlbB, a Bacterial N-Acetyltransferase Involved in the Biosynthesis of 2,3-Diacetamido-2,3-dideoxy-d-mannuronic Acid

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

Thoden, James B.; Holden, Hazel M.

2010-09-08

The pathogenic bacteria Pseudomonas aeruginosa and Bordetella pertussis contain in their outer membranes the rare sugar 2,3-diacetamido-2,3-dideoxy-D-mannuronic acid. Five enzymes are required for the biosynthesis of this sugar starting from UDP-N-acetylglucosamine. One of these, referred to as WlbB, is an N-acetyltransferase that converts UDP-2-acetamido-3-amino-2,3-dideoxy-D-glucuronic acid (UDP-GlcNAc3NA) to UDP-2,3-diacetamido-2,3-dideoxy-D-glucuronic acid (UDP-GlcNAc3NAcA). Here we report the three-dimensional structure of WlbB from Bordetella petrii. For this analysis, two ternary structures were determined to 1.43 {angstrom} resolution: one in which the protein was complexed with acetyl-CoA and UDP and the second in which the protein contained bound CoA and UDP-GlcNAc3NA. WlbB adopts a trimericmore » quaternary structure and belongs to the L{beta}H superfamily of N-acyltransferases. Each subunit contains 27 {beta}-strands, 23 of which form the canonical left-handed {beta}-helix. There are only two hydrogen bonds that occur between the protein and the GlcNAc3NA moiety, one between O{sup {delta}1} of Asn 84 and the sugar C-3{prime} amino group and the second between the backbone amide group of Arg 94 and the sugar C-5{prime} carboxylate. The sugar C-3{prime} amino group is ideally positioned in the active site to attack the si face of acetyl-CoA. Given that there are no protein side chains that can function as general bases within the GlcNAc3NA binding pocket, a reaction mechanism is proposed for WlbB whereby the sulfur of CoA ultimately functions as the proton acceptor required for catalysis.« less