Helix termination and chain reversal: Crystal and molecular structure of the alpha,beta-dehydrooctapeptide Boc-Val Delta Phe-Phe-Ala-Leu-Ala-Delta Phe-Leu-OH

The crystal structure of the dehydro octapeptide Boc-Val-Delta Phe-Phe-Ala-Leu-Ala-Delta Phe-Leu-OH has been determined to atomic resolution by X-ray crystallographic methods. The crystals grown by slow evaporation of peptide solution in methanol/water are orthorhombic, space group P2(1)2(1)2(1). The unit cell parameters are a = 8.404(3), b = 25.598(2) and c = 27.946(3) Angstrom, Z = 4. The agreement factor is R = 7.58% for 3636 reflections having (\F-o\) greater than or equal to 3 sigma (\F-o\). The peptide molecule is characterised by a 3(10)-helix at the N-terminus and a pi-turn at the C-terminus. This conformation is exactly similar to the helix termination features observed in proteins. The pi-turn conformation observed in the octapeptide is in good agreement with the conformational features of pi-turns seen in some proteins. The alpha(L)-position in the pi-turn of the octapeptide is occupied by Delta Phe(7), which shows that even bulky residues can be accommodated in this position of the pi-turns. In proteins, it is generally seen that alpha(L)-position is occupied by glycine residue. No intermolecular head-to-tail hydrogen bonds are observed in solid state structure of the octapeptide. A water molecule located in the unit cell of the peptide molecule is mainly used to hold the peptide molecule together in the crystal. The conformation observed for the octapeptide might be useful to understand the helix termination and chain reversal in proteins and to construct helix terminators for denovo protein design.

Systematic crystallographic investigation of hydrogen-bonded networks involving monohydrogen tartrate-amine complexes: Potential materials for nonlinear optics

Crystal structures of six binary salts involving aromatic amines as cations and hydrogen tartrates as anions are presented. The materials are 2,6-xylidinium-L-monohydrogen tartrate monohydrate, C12H18O6.5N, P22(1)2(1), a = 7.283(2) Angstrom, b = 17.030(2) Angstrom, c = 22.196(2) Angstrom, Z = 8; 2,6-xylidinium-D-dibenzoyl monohydrogen tartrate, C26H25O8N, P2(1), a = 7.906(1) Angstrom, b = 24.757(1) Angstrom, c = 13.166(1) Angstrom, beta = 105.01(1)degrees, Z = 4; 2,3-xylidinium-D-dibenzoyl monohydrogen tartrate monohydrate, C26H26O8.5N, P2(1), a = 7.837(1) Angstrom, b = 24.488(1) Angstrom, c = 13.763(1) Angstrom, beta = 105.69(1)degrees, Z = 4; 2-toluidinium-D-dibenzoyl monohydrogen tartrate, C25H23O8N, P2(1)2(1)2(1), a = 13.553(2) Angstrom, b = 15.869(3) Angstrom, c = 22.123(2) Angstrom, Z = 8; 3-toluidinium-D-dibenzoyl monohydrogen tartrate (1:1), C25H23O8N, P1, a = 7.916(3) Angstrom, b = 11.467(6) Angstrom, c = 14.203(8) Angstrom, alpha = 96.44(4)degrees, beta = 98.20(5)degrees, = 110.55(5)degrees, Z = 2; 3-toluidinium-D-dibenzoyl tartrate dihydrate (1:2), C32H36O10N, P1, a = 7.828(3) Angstrom, b = 8.233(1) Angstrom, c = 24.888(8) Angstrom, alpha = 93.98 degrees, beta = 94.58(3)degrees, = 89.99(2)degrees, Z = 2. An analysis of the hydrogen-bonding schemes in terms of crystal packing, stoichiometric variations, and substitutional variations in these materials provides insights to design hydrogen-bonded networks directed toward the engineering of crystalline nonlinear optical materials.

Short-bite chiral diphosphazanes derived from (S)-?-methyl benzyl amine and their Pd, Pt and Rh metal complexes

New chiral diphosphazane ligands of the type Ph(2)PN(S-*CHMePh)PYY' {YY'= Ph(2) (2), O2C6H4 (3); Y= Ph, Y'= Cl {4a (SS), 4b (SR)}, N(2)C(3)HMe(2)-3,5 {5a (SR), 5b (SS)} are synthesised starting from a chiral aminophosphine, Ph(2)PNH(S-*CHMePh) (1). The structure of one of the diastereomer 5a has been confirmed by single crystal X-ray diffraction {Orthorhombic system, P2(1)2(1)2(1); a=10.456 (4), b=15.362 (7), c=17.379 (6) Angstrom, Z=4}. Transition metal mononuclear complexes [Rh{eta(2)-(Ph(2)P)(2)N- (S-*CHMePh)}(2)](+)(BF4)(-) (6), [PdCl2{eta(2)-(Ph(2)P)(2)N(S-*CHMePh)}] (7) and [PtCl2{eta(2)-(Ph(2)P)(2)N- (S-*CHMePh)}] (8) have also been synthesised. The structure of the palladium complex 7 is solved by X-ray crystallography {Orthorhombic system, P2(1)2(1)2(1); a=8.746 (2), b=18.086 (2), c=20.811 (3) Angstrom, Z=4}. All these compounds are characterised by micro analyses, IR and NMR spectroscopic data.

Transformations of morphine, codeine and their analogues by Bacillus sp

A bacterial strain belonging to the genus Bacillus isolated by enrichment culture technique using morphine as a sole source of carbon transforms morphine and codeine into 14-hydroxymorphinone and 14-hydroxycodeinone as major and 14-hydroxymorphine and 14-hydroxycodeine as minor metabolites, respectively. When the N-methyl group in morphine and codeine are replaced by higher alkyl groups, the organism still retains its ability to carry out 14-hydroxylation as well as oxidation of the C-6-hydroxyl group in these N-variants, although the level of metabolites formed are considerably low. The organism readily transforms dihydromorphine and dihydrocodeine into only dihydromorphinone and dihydrocodeinone, respectively; suggesting that the 7,8-double bond is a necessary structural feature to carry out 14-hydroxylation reaction. The cell free extract (20,000 x g supernatant), prepared from morphine grown cells, transforms morphine into 14-hydroxymorphinone in the presence of NAD(+), but fails to show activity against testosterone. However, the cell free extract prepared from testosterone grown cells contains significant levels of 17 beta- hydroxysteroid dehydrogenase but shows no activity against morphine.

Hydrothermal synthesis and structure of organically templated one-dimensional and three-dimensional iron fluorophosphate

Two new open-framework iron fluorophosphates, [C(4)N(2)H(12)](0.5) [FeF(HPO(4))(H(2)PO(4))] (I) and [C(4)N(2)H(12)][Fe(4)F(2)(H(2)O)(4)(PO(4))(4)]. 0.5H(2)O (II), were synthesized hydrothermally using piperazine as a templating agent. The structures were determined by single-crystal X-ray diffraction. Compound I crystallizes in the orthorhombic space group Pbca, a = 7.2126(2) Angstrom, b = 14.2071(4) Angstrom, c = 17.1338(2) Angstrom, Z = 8. The structure is composed of infinite anionic chains of [FeF(HPO(4))(H(2)PO(4))](n)(-) built by trans-fluorine sharing FeF(2)O(4) octahedra. These chains are similar to those found in tancoite-type minerals. Compound II crystallizes in the monoclinic space group P2(1)/n, a = 9.9045(3) Angstrom, b = 12.3011(3) Angstrom, c = 17.3220(4) Angstrom, beta = 103.7010(10)degrees, Z = 4. The structure of compound II has a three-dimensional (3D) architecture with an eight-membered channel along the b axis, in which protonoted piperazine molecules reside. The complex framework is built from two types of secondary building unit (SBU): one hexamer [Fe(3)F(2)(H(2)O)(2)(PO(4))(3)] (SBU6), and one dimer [FeO(4)(H(2)O)(2)PO(4)] (SBU2). The vertex sharing between these SBUs create the 3D structure.

One-dimensional zinc phosphates with linear chain structure

Three one-dimensional zinc phosphates, [C5N2H14][Zn(HPO4)2], I, [C10N4H26][Zn(HPO4)2].2H2O II, and [C4N2H6]2[Zn(HPO4)], III, have been prepared employing hydro/solvothermal methods in the presence of organic amines. While I and II consist of linear chains of corner-shared four-membered rings, III is a polymeric wire where the amine molecule is directly bonded to the metal center. The wire, as well as the chain in these structures, are held together by hydrogen bond interactions involving the amine and the framework oxygens. The polymeric zinc phosphate with wire-like architecture, III, is only the second example of such architecture. Crystal data: I, monoclinic, P21/c (no. 14), a=8.603(2), b=13.529(2), c=10.880(1) Å, β=94.9(1)°, V=1261.6(1) Å3, Z=4, ρcalc.=1.893 gcm−3, μ(MoKα)=2.234 mm−1, R1=0.032, wR2=0.086, [1532 observed reflections with I>2σ(I)], II, orthorhombic, Pbca (no. 61), a=8.393(1), b=15.286(1), c=22.659(1) Å, V=2906.9(2) Å3, Z=8, ρcalc.=1.794 gcm−3, μ(MoKα)=1.957 mm−1, R1=0.055, wR2=0.11, [1565 observed reflections with I>2σ(I) and III, monoclinic, P21/c (no. 14), a=8.241(1), b=13.750(2), c=10.572(1) Å, β=90.9(1)°, V=1197.7(2) Å3, Z=4, ρcalc.=1.805 gcm−3, μ(MoKα)=2.197 mm−1, R1=0.036, wR2=0.10, [1423 observed reflections with I>2σ(I)].

Cellular uptake and remarkable photocytotoxicity of pyrenylter pyridine oxovanadium(IV) complexes of dipyridophenazine bases

Pyrenylterpyridine (pytpy) oxovanadium(IV) complexes VO(pytpy)(L)]Cl-2 (1-6) of the dipyridophenazine bases (L), viz., dipyrido-6,7,8,9-tetrahydrophenazine (dpqC in 1), dipyrido3,2-a:2',3'-c]phenazine-2-carboxylic acid (dppzc in 2), dipyrido3,2-a:2',3'-c]phenazine-11-sulfonic acid (dppzs in 3), 7-aminodipyrido3,2-a:2',3'-c]phenazine (dppza in 4), benzo-i]dipyrido3,2-a:2',3'-c]phenazine (dppn in 5) and dipyrido3,2-a:2',3'-c]phenazine (dppz in 6) were prepared, characterized and their DNA binding, photocleavage activity and photocytotoxicity studied. The complexes which showed a d-d band near 750 nm in DMF are efficient binders to calf thymus DNA (K-b: 3.2 x 10(5)-2.9 x 10(6) M-1). The complexes showed significant pUC19 DNA cleavage in near-IR light of 785 nm forming center dot OH radicals and photocytotoxicity in HeLa cells in visible light with the benzo-i] dipyrido3,2-a:2',3'-c]phenazine complex 5 showing a remarkably low IC50 value of 0.036 mu M. Flow-cytometric analysis shows a high sub-G1 phase cell cycle arrest in HeLa cells by the complexes on photo-irradiation. The photocytotoxicity correlates well with the hydrophobicity, photosensitizing ability and DNA binding propensity of the complexes. (C) 2012 Elsevier B.V. All rights reserved.

Lithium D-Isoascorbate Monohydrate, a New Nonlinear Optical Material

Single crystals of lithium D-isoascorbate monohydrate (LDAM), (C6H7O6Li center dot H2O), are grown by a solution growth method. The crystal structure of LDAM is solved using single crystal X-ray diffraction. The space group is orthorhombic P2(1)2(1)2(1) with four formula units per unit cell and lattice parameters a = 7.7836(3) angstrom, b = 8.7456(3) angstrom, and c = 11.0368(4) angstrom. Solubility of the material in water is determined thermogravimetrically and found to have a positive temperature coefficient of solubility. Large optical quality single crystals are subsequently grown from aqueous solution by a slow cooling method. The crystal has a bulky prismatic habit and among the prominent faces the c face appears as the only principal morphological face. The crystal exhibits a (010) cleavage. Dielectric spectroscopy reveals a nearly Debye type Cole-Cole behavior with anisotropy in relaxation. Optical transmission range is found to be from 300 to 1400 nm. The principal refractive indices of this biaxial crystal, measured using Brewster's angle method, at wavelengths 405, 543, and 632.8 nm, show high dispersion. The crystal is negative biaxial with 2V(z) = 107.8 degrees (405 nm) and belongs to the Hobden class 3. Theoretically generated type 1 and type 2 second order phase matching curves match very well with the experimental results. The second-order nonlinear coefficient d(14) was determined to be 7 x 10(-13) m/V. For the optimum phase matching direction (type 2), the second-order effective nonlinear coefficient and the walk off angle are determined to be 0.84 times d(14) and 3.5 degrees respectively. The crystal possesses high multiple surface damage thresholds of 18 GW/cm(2) and 8 GW/cm(2) at laser wavelengths 1064 and 532 nm, respectively.

Phase Evolution in the AuCu/Sn System by Solid-State Reactive Diffusion

The interfacial reactions between several Au(Cu) alloys and pure Sn were studied experimentally at 200A degrees C. Amounts of Cu in the AuSn4 and AuSn2 phases were as low as 1 at.%. On the basis of these experimental results there is no continuous solid solution between (Au,Cu)Sn and (Cu,Au)(6)Sn-5. The copper content of (Au,Cu)Sn was determined to be approximately 7-8 at.%. Substantial amounts of Au were present in the (Cu,Au)(6)Sn-5 and (Cu,Au)(3)Sn phases. Two ternary compounds were formed, one with stoichiometry varying from (Au40.5Cu39)Sn-20.5 to (Au20.2Cu59.3)Sn-20.5 (ternary ``B''), the other with the composition Au34Cu33Sn33 (ternary ``C''). The measured phase boundary compositions of the product phases are plotted on the available Au-Cu-Sn isotherm and the phase equilibria are discussed. The complexity and average thickness of the diffusion zone decreases with increasing Cu content except for the Au(40 at.%Cu) couple.

Fluoranthene-Based Molecules as Electron Transport and Blue Fluorescent Materials for Organic Light-Emitting Diodes

Herein we report the synthesis, characterization, and potential application of his (4- (7,9,10-triphenylfluoranthen-8-yl)pheny)sulfone (TPFDPSO2) and 2,8-bis (7,9,10-triphenylfluoranthen-8-yl) dibenzo b, d]-thiophene 5,5-dioxide (TPFDBTO2) as electron transport as well as light-emitting materials. These fluoranthene derivatives were synthesized by oxidation of their corresponding parent sulfide compounds, which were prepared via Diels-Alder reaction. These materials exhibit deep blue fluorescence emission in both solution and thin film, high photoluminescence quantum yield (PLQY), thermal and electrochemical stability over a wide potential range. Hole- and electron-only devices were fabricated to study the charge transport characteristics, and predominant electron transport property comparable with that of a well-known electron transport material, Alq(3), was observed. Furthermore, bilayer electroluminescent devices were fabricated utilizing these fluoranthene derivatives as electron transport as well as emitting layer, and device performance was compared with that of their parent sulfide molecules. The electroluminescence (EL) devices fabricated with these molecules displayed bright sky blue color emission and 5-fold improvement in external quantum efficiency (EQE) with respect to their parent compounds.

Linking monazite geochronology with fluid infiltration and metamorphic histories: Nature and experiment

Migmatised metapelites from the Kodaikanal region, central Madurai Block, southern India have undergone ultrahigh-temperature metamorphism (950-1000 degrees C; 7-8 kbar). In-situ electron microprobe Th-U-Pb isochron (CHIME) dating of monazites in a leucosome and surrounding silica-saturated and silica-poor restites from the same outcrop indicates three principal ages that can be linked to the evolutionary history of these rocks. Monazite grains from the silica-saturated restite have well-defined, inherited cores with thick rims that yield an age of ca. 1684 Ma. This either dates the metamorphism of the original metapelite or is a detrital age of inherited monazite. Monazite grains from the silica-poor restite, thick rims from the silica-saturated restite, and monazite cores from the leucosome have ages ranging from 520 to 540 Ma suggesting a mean age of 530 Ma within the error bars. In the leucosome the altered rim of the monazite gives an age of ca. 502 Ma. Alteration takes the form of Th-depleted lobes of monazite with sharp curvilinear boundaries extending from the monazite grain rim into the core. We have replicated experimentally these altered rims in a monazite-leucosome experiment at 800 degrees C and 2 kbar. This experiment, coupled with earlier published monazite-fluid experiments involving high pH alkali-bearing fluids at high P-T, helps to confirm the idea that alkali-bearing fluids, in the melt and along grain boundaries during crystallization, were responsible for the formation of the altered monazite grain rims via the process of coupled dissolution-reprecipitation. (C) 2015 Elsevier B.V. All rights reserved.

Determinación del índice de área foliar, radiación solar no interceptada por especies forestales y concentración de magnesio en hojas de café (Coffea arabica L.) en sistemas agroforestales, localizados en Masaya, Nicaragua

La presente investigación se realizó en sistemas agroforestales con Café Coffea arábiga L.)en el Municipio de Masatepe, Nicaragua, determinando el índice de área foliar, radiación solar no interceptada por especies forestales y concentración de magnesio en hojas de Café. Para determinar índice de área foliar se utilizó una metodología no destructiva y una destructiva; la medición no destructiva se basó en la técnica de fotografías hemisféricas para lo cual se utilizó una cámara Nikon Coolpix 4500 que permitió tomar fotografías de cuatro árboles de Samanea saman, Inga laurina, Simarouba glauca, Tabebuia rosea respectivamente. Porcada árbol se tomaron cuatro imágenes sobre lados opuestos del tronco (Norte, Sur, Este y Oeste), para el análisis de fotografías hemisféricas se empleó el software Gap Light Analyzer. Para contrastar la medición de índice de área foliar por método no destructivo (fotografías hemisféricas) se empleó un método destructivo basado en la recolección de 300 hojas, se tomó el peso húmedo del total de hojas de cada uno de los árboles en estudio. Del total de hojas de cada árbol se pesaron separadamente tres muestras; utilizando el planímetro LI-3000 se calculó en cada caso el área de la hoja. Una vez obtenida el área foliar de la hoja, las muestras se secaron en horno a 65° C, durante 72 h y promediadas para obtener biomasa del follaje. Dividiendo el área foliar de las muestras entre su peso seco se obtuvo el área foliar específica, posteriormente el promedio de área foliar específica de las muestras multiplicado por el peso seco total de hojas permitió calcular el área foliar del árbol. Finalmente, se obtuvo el índice de área foliar dividiendo área foliar entre el área de suelo asignada . La medición de la cantidad de radiación incidente sobre el follaje de las plantas de Café se realizó en la réplica II en CENECOOP en dos puntos de muestreo; el criterio de selección de los sitios se basó en la combinación de árboles ubicados diagonalmente y en la uniformidad de distancia entre las especies para la combinación T. rosea + S. glaucae I. laurina + S. saman. En esta réplica se realizaron análisis del contenido de magnesio en hojas de Café en las subparcelas 5, 6, 7, 8, 9, 10, 11 y 12 más dos muestras testigos en las subparcelas 13 y 14 a pleno sol. El índice de área foliar promedio para especies tropicales estimado por el método destructivo fue de 2,52 y por el método no destructivo fue de 0,85; debido a estas diferencias es necesario aplicar un factor de corrección o calibración al método no destructivo para validar ambos resultados. En la combinación I. laurina + S. saman se detectó un mayor paso de radiación solar al cafetal (29911,11lux) posiblemente debido a las características morfológicas del dosel. La concentración de magnesio más alta es de 2% la cual se encontró en las hojas de Café de la combinación T. rosea + S. glauca en nivel de insumo orgánico moderado.

Evaluación comparativa de concentrados pre-iniciadores comerciales vs. ración convencional para cerdos en etapa de iniciación

En las instalaciones de Porcina Gallo Solo S.A. ubicadas en el Departamento de León, se efectuó una prueba de alimentación durante el periodo comprendido del 31 de Enero al 21 de Abril, para verificar la calidad de tres concentrados comerciales (A,B,C), al compararlos con una ración convencional (D), en cerdos en etapa de iniciación. El experimento comprendió 2 etapas. Inicialmente se utilizaron las camadas provenientes de 24 cerdas, distribuidas al azar en 4 grupos, a las cuales se llevo registro de peso semanal y consumo de alimentos, hasta los 42 días, fecha de destete. El diseño utilizado fue completamente azarizado. Como segunda etapa se seleccionaron 72 cerdos de 7-8 semanas de edad, se desparasitaron y fueron distribuidos en 4 tratamientos, y continuaron recibiendo sus respectivos concentrados pre-iniciadores durante 3 semanas, hasta alcanzar aproximadamente 23 kilogramos de peso vivo. El numero de cerdos destetados por camada fue sometido a análisis de varianza; y las ganancias de peso vivo en ambos periodos analizados fueron sometidos a análisis de covarianza y prueba de Duncan. La ganancia de peso vivo, de 5.45 kilogramos obtenida por los lechones en el tratamiento "D", durante el periodo de lactancia, fue similar a la de los tratamientos "A" y "C", pero significativamente diferente P(.05), con la lograda por el tratamiento "B", de 3.78 kilogramos. La mayor ganancia de peso vivo, durante el periodo post-destete, se obtuvo con los cerdos que recibian la racion comercial "B" (9.59 kgs), la que fue similar a la del tratamiento "D"; siendo diferentes de las obtenidas con los tratamientos "A" (6.09 kgs.) y "C" (7.52 kgs.). El mayor promedio, de 8.66 lechones destetados por camada, se obtuvo con el tratamiento "C". Sin embargo no se encontraron diferencias significativas al compararlo con los resultados obtenidos con los tratamientos A, B y D respectivamente. El tratamiento "B" resulto ser la ración comercial mas económica, revelando un costo unitario de C$ 3.. por kilogramo de cerdo producido durante el periodo post-destete. Los costos unitarios obtenidos con los tratamientos "A" (C$ 3.93) y "C" (3.88) fueron mayores a los obtenidos con el testigo "D" (3.36).

A Preliminary Check-List of the Marine Algae of the Moss Landing Jetty: An Annotated Floristic Compilation. Annual Report, Part 7, 1973

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Resource survey of Looe Key National Marine Sanctuary, 1983

Forward: Looe Key National Marine Sanctuary (LKNMS) was designated in 1981 to protect and promote the study, teaching, and wise use of the resources of Looe Key Sanctuary (Plate A). In order to wisely manage this valuable resource, a quantitative resource inventory was funded by the Sanctuary Programs Division (SPD), Office of Ocean and Coastal Resource Management, National Oceanic and Atmospheric Administration (NOAA) in cooperation with the Southeast Fisheries Center, National Marine Fisheries Service, NOAA; the Cooperative Institute for Marine and Atmospheric Studies (CIMAS), University of Miami; the Fisher Island Laboratory, United States Geological Survey; and the St. Petersburg Laboratory, State of Florida Department of Natural Resources. This report is the result of this cooperative effort. The objective of this study was to quantitatively inventory selected resources of LKNMS in order to allow future monitoring of changes in the Sanctuary as a result of human or natural processes. This study, referred to as Phase I, gives a brief summary of past and present uses of the Sanctuary (Chapter 2); and describes general habitat types (Chapter 3), geology and sediment distribution (Chapter 4), coral abundance and distribution (Chapter 5), the growth history of the coral Montastraea annularis (Chapter 6), reef fish abundance and distribution (Chapter 7), and status of selected resources (Chapter 8). An interpretation of the results of the survey are provided for management consideration (Chapter 9). The results are expected to provide fundamental information for applied management, natural history interpretation, and scientific research. Numerous photographs and illustrations were used to supplement the report to make the material presented easier to comprehend (Plate B). We anticipate the information provided will be used by managers, naturalists, and the general public in addition to scientists. Unless otherwise indicated, all photographs were taken at Looe Key Reef by Dr. James A. Bohnsack. The top photograph in Plate 7.8 was taken by Michael C. Schmale. Illustrations were done by Jack Javech, NMFS. Field work was initiated in May 1983 and completed for the most part by October 1983 thanks to the cooperation of numerous people and organizations. In addition to the participating agencies and organizations we thank the Newfound Harbor Marine Institute and the Division of Parks and Recreation, State of Florida Department of Natural Resources for their logistical support. Special thanks goes to Billy Causey, the Sanctuary Manager, for his help, information, and comments. We thank in alphabetical order: Scott Bannerot, Margie Bastian, Bill Becker, Barbara Bohnsack, Grant Beardsley, John Halas, Raymond Hixon, Irene Hooper, Eric Lindblad, and Mike Schmale. We dedicate this effort to the memory of Ray Hixon who participated in the study and who loved Looe Key. (PDF contains 43 pages)