Photolysis of the dithiolactone 4-isopropylidene-3,3-dimethyl-1-thietan-2-thione; a Norrish type I reaction

The dithiolactone (1) upon excitation gives the dithione (2) in cyclohexane and other aprotic solvents and a 1 : 1 adduct in hydroxylic solvents from an n* excited singlet state via an -cleavage process.

Structure of (4S)-2,4-dimethyl-1,2-dihydropyrazino[2,1-b]quinazoline-3(4H),6-dione

C13HI3N302, orthorhombic, P2~2121, a = 17.443 (5), b = 11.650 (4), c = 5.784 (1)/~, Z = 4, d m = 1.456, d c = 1.429 Mg m -3, F(000) = 512, g(Cu Ka) = 0.843 mm-L The R index is 0.040 for 1358 significant reflections. The structure is stabilized by C-H...O interactions. The N-methylated eis peptide group which forms part of a six-membered ring is non-planar. The torsion angle about the peptide bond is -6.1 (4) ° and the peptide bond length is 1.337 (3) A.

Chelating and bridging diphosphinoamine (PPh2)(2)N(Pr-i) complexes of copper(I)

The ligand bis(diphenylphosphino) isopropylamine (dppipa) has been shown to be a versatile ligand sporting different coordination modes and geometries dictated by copper(I). Most of the molecular structures were confirmed by X-ray crystallography. It is found in a chelating mode, in a monomeric complex when the ligand to copper ratio is 2:1. A tetrameric complex is formed when low ratios of ligand to metal (1: 2) were used. But with increasing ratios of ligand to metal (1: 1 and 2: 1), a trimer or a dimer was obtained depending on the crystallization conditions. Variable temperature P-31{H-1} NMR spectra of these complexes in solution showed that the Cu-P bond was labile and the highly strained 4-membered structure chelate found in the solid state readily converted to a bridged structures. On the other hand, complexes with the ligand in a bridging mode in the solid state did not form chelated structures in solution. The effect of adding tetra-alkylammonium salts to solutions of various complexes of dppipa were probed by P-31{H-1} NMR and revealed the effect of counter ions on the stability of complexes in solution. (C) 2008 Elsevier B.V. All rights reserved.

Structure of 1,2,4-oxadiazolidine-3,5-dione monohydrate

C2H2N203.H20, Mr= 120.07, monoclinic,P21/c, a= 5.011 (1), b= 11.796(2), c= 7.689 (2)A,fl= 95.22 (2) ° , V= 452.61 A 3, Z= 4, Dx= 1.76, D m = 1.75 gcm -3, /].(Cu Ks) = 1.5418 A, g = 14-0 cm -l,F(000) = 248, T = 293 K, crystal quality was poor and the final R =0.107, wR =0.090 for 881 observed reflections. The compound is derived from a novel form of the monopropellant oxalohydroxamic acid. The two exocyclic C-O bond lengths of 1.240 (3) and 1.228 (4)A indicate double bonds. The C-N bond lengths of 1.334 (4), 1.390 (4) and 1.359 (4) A are characteristic of the amide bond. The N atom covalently bonded to the two carbonyl C atoms acts as a proton donor in an intermolecular hydrogen bond to the ring O atom: N1...O3i = 2.854 ]k (i =x-- 1,y, z), H...O = 2.15 A, N-H...O = 159 °.

Molecular structure of Lantadene-B&C, triterpenoids ofantana camara, red variety: Lantadene-B, 22β-angeloyloxy-3-oxoolean-12-en-28-oic acid; Lantadene-C, 22 β-(S)-2′-methyl butanoyloxy-3-oxoolean-12-en-28-oic acid

(I)Lantadene-B: C35H52O5,M r =552.80, MonoclinicC2,a=25.65(1),b=6.819(9),c=18.75(1) Å,beta=100.61(9),V=3223(5) Å3,Z=4,D x =1.14 g cm–3 CuKagr (lambda=1.5418A),mgr=5.5 cm–1,F(000)=1208,R=0.118,wR=0.132 for 1527 observed reflections withF o ge2sgr(F o ). (II)Lantadene-C: C35H54O5·CH3OH,Mr=586.85, Monoclinic,P21,a=9.822(3),b=10.909(3),c=16.120(8)Å,beta=99.82(4),V=1702(1)Å3,Z=2,D x =1.145 g cm–3, MoKagr (lambda=0.7107Å), mgr=0.708 cm–1 F(000)=644,R=0.098, wR=0.094 for 1073 observed reflections. The rings A, B, C, D, and E aretrans, trans, trans, cis fused and are in chair, chair, sofa, half-chair, chair conformations, respectively, in both the structures. In the unit cell the molecules are stabilized by O-HctdotO hydrogen bonds in both the structures, however an additional C-HctdotO interaction is observed in the case of Lantadene-C.

Structure of N-nitroso-r-2,c-7-diphenylhexahydro-1,4-diazepin-5-one

C17H17N3O2, M(r) = 295.34, orthorhombic, P2(1)2(1)2(1), a = 7.659 (1), b = 12.741 (1), c = 15.095 (1) angstrom, V = 1473.19 (2) angstrom 3, Z = 4, D(m) = 1.33, D(x) = 1.32 Mg m-3, lambda(Cu K-alpha) = 1.5418 angstrom, mu = 0.68 mm-1, F(000) = 624, T = 295 K, R = 0.031 for 1549 unique observed reflections with I > 2.5-sigma(I). The seven-membered heterocyclic ring adopts a boat conformation flattened at the nitroso end of the ring. The substituent phenyl rings occupy pseudo-axial positions and the nitroso group is coplanar with the C(2), N(1), C(7) plane of the central ring. The crystal structure is stabilized by intermolecular N-H...O and weak C-H...O hydrogen bonds.

A quantitative analysis of the phytoplankton of the Gulf of Panama: I. Results of the regional phytoplankton surveys during July and November 1957 and March 1958

ENGLISH: 1. Quantitative phytoplankton samples were collected by the Inter-American Tropical Tuna Commission at the surface and ten meters in the Gulf of Panama, as follows: a) 18-21 March, 1958 (31 stations)-during the height of the upwelling season, b) 10-12 July, 1957 (10 stations)-during the transition to the rainy season at a time when mild upwelling winds reappear, c) 7-8 November, 1957 (15 stations)-during the height of the rainy season. 2. Maximum phytoplankton populations occurred during the upwelling season, followed by a considerable decline during July, and a further Subsidence during November. 3. A remarkable regional uniformity in species composition was observed during the surveys despite regional differences in growth conditions. Diatoms overwhelmingly dominated the communities. 4. During all surveys, the innermost regions, generally north of 8°30'N, were the most productive. The least productive areas were in the offing of San Miguel Bay and Parita Bay, suggesting that nutrient accretion via runoff is inadequate to sustain sizeable autotrophic plant populations in those regions. 5. During all surveys, phytoplankton growth appeared to be limited by nutrient availability. 6. During all surveys, phytoplankton growth appeared to be related to depth of the water column. 7. Although below average rainfall contributed to unusually favorable growth conditions (reduced stability, increased transparency and, presumably, nutrient reserves) during the November survey relative to November 1955 and 1956 at 8°45'N, 79°23'W, the anticipated heightened phytoplankton response was not observed. 8. During the November survey, the local diatom responses and their regional fluctuations could be satisfactorily related to the accompanying surface salinity conditions. However, this correspondence is undoubtedly attributable to factors associated with the observed salinity levels, probably nutrients, rather than salinity directly. 9. Unusually warm conditions occurred during the March survey, attributable to considerably weaker upwelling winds than normally occurring then, which contributed to a considerably lower standing crop and a retardation in succession of three to five weeks relative to that observed during 1955-1957 at 8°45'N, 79°23'W in the Gulf of Panama. 10. During the March survey, a well defined inverse relationship existed between mean temperature and mean diatom abundance in the upper ten meters, and between transparency and mean diatom abundance. A direct relationship occurred between surface salinity and mean diatom abundance in the upper ten meters. These relationships are interpreted to indicate that diatom abundance primarily reflected the nutrient concentrations associated with a given upwelling intensity, rather than describing casual relationships. 11. The survey results indicate that the phytoplankton dynamics observed at 8°45'N, 79°23'W from November, 1954 through May, 1957 are generally representative of the Gulf of Panama. 12. The following new forms, to be described in a later publication, were observed during the surveys: Actinoptychus undulatus f. catenata n.f., Asterionella japonica f. tropicum n.f., Leptocylindrus maximus n. sp., Skeletonema costatum f. tropicum n.f. SPANISH: 1. La Comisión Interamericana del Atun Tropical recolectó en el Golfo de Panama muestras cuantitativas de fitoplancton en la superficie y a los diez metros, como sigue: a) Del 18 al 21 de marzo de 1958 (31 estaciones)-durante el maximum de la estación de afloramiento. b) Del 10 al 12 de julio de 1957 (10 estaciones)-durante la epóca de transición a la estación lluviosa cuando reaparecen los vientos ligeros que causan el afloramiento. c) Del 7 al 8 de noviembre de 1957 (15 estaciones)-durante el maximum de la estación lluviosa. 2. Las poblaciones maximas de fitoplancton aparecieron durante la estación de afloramiento, seguido por una considerable disminución durante el mes de julio y una calma durante noviembre. 3. Durante la investigación se observó una remarcable uniformidad regional en la composición de las especies a pesar de las diferencias regionales en las condiciones de crecimiento. Las diatomeas predominaban en gran numero en las comunidades. 4. Durante todas las investigaciones, las regiones mas cerca de la costa, generalmente al norte de los 8°30'N, eran las mas productivas. Las areas menos productivas fueron las mar afuera de las Bahias de San Miguel y Parita, lo que sugiere que el aumento en las sales nutritivas causado por las escorrentias es inadecuado para sostener poblaciones grandes de plantas autotróficas en estas regiones. 5. Durante todas las investigaciones, el crecimiento del fitoplancton parecio estar limitado por la disponibilidad de las. sales nutritivas. 6. Durante todas las investigaciones el crecimiento del fitoplancton parecio estar relacionado con la profundidad de la columna de agua. 7. Aunque las precipitacion por debajo del promedio normal contribuyo a condiciones desusadamente favorables de crecimiento (estabilidad reducida, aumento de la transparencia y, presumiblemente, de la reserva de sales nutritivas) durante la investigación de noviembre en relación a noviembre de 1955 y de 1956 en los 8°45'N, 79°23'W, no se observo-la alta reacción de fitoplancton que se esperaba. 8. Durante la investigación de noviembre, las reacciones locales de las diatomeas y sus fluctuaciones regionales pudieron relacionarse en forma satisfactoria con condiciones asociadas con la salinidad de la superficie. Sin embargo, esta correspondencia puede atribuirse sin duda a factores asociados con los niveles observados de salinidad, probablemente con las sales nutritivas, en lugar de directamente con la salinidad. 9. Condiciones calurosas no comunes ocurrieron durante la investigación de marzo, las que pueden atribuirse a que los vientos que ocasionan el afloramiento fueran mas debiles que los normales, lo que contribuyó a que la cosecha estable fuera considerablemente mas baja y a la demora de tres a cinco semanas en la sucecion relativa a la que se observó durante 1955-1957 en los 8°45'N, 8°23'W, en el Golfo de Panama. 10. Durante la investigación de marzo, existió una relación inversa bien definida entre la temperatura y la abundancia media de las diatomeas en los diez metros superiores, y entre la transparencia y la abundancia media de las diatomeas. Una relación directa ocurrio entre la salinidad de superficie y la abundancia media de las diatomeas en los diez metros superiores. Estas relaciones se interpretan como indicadoras de que la abundancia de diatomeas refleja primeramente las concentraciones de las sales nutritivas asociadas con una intensidad de afloramiento dada, en lugar de describir relaciones causales. 11. Los resultados de la investigacion indican que la dinamica del fitoplancton observada en los 8°45'N, 79°23'W, desde noviembre de 1954 a mayo de 1957, es generalmente representativa del Golfo de Panama. 12. Durante las investigaciones se observaron las siguientes formas nuevas, las que seran descritas en una publicación posterior: Actinoptychus undulatus f. catenata n.f., Asterionella japonica f. tropicum n.f., Leptocylindrus maximus n. sp., Skeletonema costatum f. tropicum n.f.

Expressional induction of Paralichthys olivaceus cathepsin B gene in response to virus, poly I:C and lipopolysaccharide

Cathepsin B is a lysosomal cysteine protease of the papain-like enzyme family with multiple biological functions. In this study, Paralichthys olivaceus cathepsin B (PoCatB) cDNA was isolated from flounder embryonic cells (FEC) treated with UV-inactivated grass carp hemorrhage virus (GCHV) and subsequently identified as a vitally induced gene. The full length cDNA of PoCatB is 1801 bp encoding 330-amino acids. The deduced protein has high homology to all known cathepsin B proteins, containing an N-terminal signal peptide, cysteine protease active sites, the occluding loop segment and a glycosylation site, all of which are conserved in the cathepsin B family. PoCatB transcription of FEC cells could be induced by turbot (Scophthalmus maximus) rhabdovirus (SMRV), UV-inactivated SMRV, UV-inactivated GCHV, poly I:C or lipopolysaccharide (LPS), and SMRV or poly I:C was revealed to be most effective among the five inducers. In normal flounder, PoCatB mRNA was detectable in all examined tissues. Moreover, SMRV infection could result in significant upregulation of PoCatB mRNA, predominantly in spleen, head kidney, posterior kidney, intestine, gill and muscle with 18.2,10.9, 24.7,12, 31.5 and 18 fold increases at 72 h post-infection respectively. These results provided the first evidence for the transcriptional induction of cathepsin B in fish by virus and LPS, indicating existence of a novel function in viral defense. (C) 2008 Elsevier Ltd. All rights reserved.

Polymerization of ethylene by zirconocene-B(C6F5)(3) catalysts with aluminum compounds

Ethylene polymerization by zirconocene-B(C6F5)(3) catalysts with various aluminum compounds has been investigated. It is found that the catalytic activity depended on zirconocenes used, and especially on the type of aluminum compounds. For Et(H(4)Ind)(2)ZrCl2 (H(4)Ind : tetrahydroindenyl), the activity decreases in the following order: Me3Al > i-Bu3Al > Et3Al much greater than Et2AlCl. While for Cp2ZrCl2(Cp : cyclopentadienyl), it varies as follows: i-Bu3Al > Me3Al much greater than Et3Al. Furthermore, the activity is significantly affected by the addition mode of the catalytic components, which may imply that the formation of active centers is associated with an existing concentration of catalytic components. Results of thermal behavior of polyethylene (PE) studied by differential scanning calorimetry(DSC) show that crystallinity of the polymer prepared with Et3Al is higher than that with Me3Al or i-Bu3Al. It is also found that the number-average molecular weight ((M) over bar) of the polymers prepared with Me3Al or i-Bu3Al is much higher than that with Et3Al. H-1-NMR studies substantiate that i-Bu3Al is a more efficient alkylation agent of Cp2ZrCl2 in comparison with Me3Al. (C) 1997 John Wiley & Sons, Inc.

COMPATIBILIZING EFFECT OF POLY(ETHYLENE OXIDE)-B-POLYSTYRENE-B-POLY(ETHYLENE OXIDE) IN PHENOLPHTHALEIN POLY(ETHER ETHER KETONE) POLY(2,6-DIMETHYL-1,4-PHENYLENE OXIDE) BLENDS

The morphology and mechanical behaviour of phenolphthalein poly(ether ether ketone) (PEK-C)/poly(2,6-dimethyl-1,4-phenylene oxide) (PPO) blends has been investigated. A poly(ethylene oxide)-b-polystyrene-b-poly(ethylene oxide) (PEO-PS-PEO) triblock copolymer was used as compatibilizer. It was found that PEO-PS-PEO has a compatibilizing effect on the PEK-C/PPO blends. The addition of PEO-PS-PEO to the blends greatly improves phase dispersion and interfacial interfacial adhesion and also enhances the ultimate tensile strength and Young's modulus at compositions ranging from 30 to 70% PEK-C. However, all the values of the ultimate tensile strength within the whole composition range are lower than those expected by simple additivity, probably owing to the poor mechanical properties of PEO-PS-PEO copolymer.

Androgenic 17β-hydroxysteroid dehydrogenase activity of expressed rat type I 3β-hydroxysteroid dehydrogenase/Δ5-Δ4 isomerase

Transient expression in nonsteroidogenic mammalian cells of the rat wild type I and type II 3β-hydroxysteroid dehydrogenase/Δ5-Δ4-isomerase (3β- HSD) cDNAs shows that the encoded proteins, in addition to being able to catalyze the oxidation and isomerization of Δ5-3β-hydroxysteroid precursors into the corresponding Δ4-3-ketosteroids, interconvert 5α- dihydrotestosterone (DHT) and 5α-androstane-3β,17β-diol (3β-diol). When homogenate from cells transfected with a plasmid vector containing type I 3β-HSD is incubated in the presence of DHT using NAD+ as cofactor, a somewhat unexpected metabolite is formed, namely 5α-androstanedione (A- dione), thus indicating an intrinsic androgenic 17β-hydroxysteroid dehydrogenase (17β-HSD) activity of this 3β-HSD isoform. Although the relative Vmax of 17β-HSD activity is 14.9-fold lower than that of 3β-HSD activity, the Km value for the 17β-HSD activity of type I 3β-HSD is 7.97 μM, a value which is in the same range as the conversion of DHT into 3β- diol which shows a Km value of 4.02 μM. Interestingly, this 17β-HSD activity is highly predominant in unbroken cells in culture, thus supporting the physiological relevance of this 'secondary' activity. Such 17β-HSD activity is inhibited by the classical substrates of 3β-HSD, namely pregnenolone (PREG), dehydroepiandrosterone (DHEA), Δ5-androstene-3β,17β- diol (Δ5-diol), 5α-androstane-3β,17β-diol (3β-diol) and DHT, with IC50 values of 2.7, 1.0, 3.2, 6.2, and 6.3 μM, respectively. Although dual enzymatic activities have been previously reported for purified preparations of other steroidogenic enzymes, the present data demonstrate the multifunctional enzymatic activities associated with a recombinant oxidoreductase enzyme. In addition to its well known 3β-HSD activity, this enzyme possesses the ability to catalyze DHT into A-dione thus potentially controlling the level of the active androgen DHT in classical steroidogenic as well as peripheral intracrine tissues.

Synthesis of a 1,4-benzodiazepine containing palladacycle with in vitro anticancer and cathepsin B activity

The reaction of the five-membered C,N-palladacycle [(L)PdCl](2), where LH = 1-methyl-5-phenyl-1H-1,4-benzodiazepin-2(3H)-one, with 1,2-ethanebis(diphenylphosphine), dppe, leads to the formation of the bridged palladacycle. [Pd(2)L(2)(mu-dppe)Cl(2)] 3, which was characterised in solution by (1)H and (31)P NMR spectroscopy and in the solid state by X-ray crystallography. Complex 3 was tested in vitro against a number of cell lines. For example, it inhibited K562 leukaemia cells with an IC(50) value of 4.3 microM (1 h exposure) and displayed cathepsin B inhibitory action with an IC(50) value of 3 microM.