bluuebunny/crossref_metadata_2025 huggingface dataset:
N-tert-Butylglyoxylsäureamid als neues Reagens zur Peptid-Segmentverknüpfung via Vierkomponenten-Reaktion (4CR) / N-tert-Butylglyoxylicamide, the New Reagent for Peptide Segment Coupling by Four-Component Reaction
Authors: König Stephan , Klösel Roland , Karl Rosi , Ugi Ivar
Published: February 2015

In contrast to the use of other aldehyd components, the Tetra Component Reactions (4CR) of carboxyl acids and primary amines with combinations of N-tert-butylglyoxylicamide and isocyanides produce carbonamides that yield the desired stereochemically uniform condensation products. Often a further advantage of such products is their possibility of being oxidized selectively in the presence of CuCl2 ·2H2O/NEt3/air (containing O2) into the carbonamides of the here used carboxyl acids and primary amines. In particular, such products can thus be converted selectively into α-acylamino and peptide derivatives. In case of the modelpeptide phenylaceticbenzylamide 8a quantitative cleavage yields, in the course of the appropriate dipeptide derivatives (8b-8f) cleavage yields of 56-81% are obtained.
Preparation of CuGaSe2 Thin Film Solar Cells Comprising an Electrochemical Gallium Deposition Step
Authors: Mehlin M. , Rimmasch J. , Fritz H. P.
Published: February 2015

Thin film CuGaSe2 solar cells were prepared from the elements using electrochemical deposition of Ga from an alkaline bath. Sputtered copper layers with a small gallium content (Cu0.86Ga0.14) on Mo/soda-lime glass served as a substrate. Subsequent reactive annealing of the thus created Cu/Ga precursor layer with selenium vapour yielded CuGaSe2. Chalcopyrite phase formation was studied with XRD, micro-Raman spectroscopy, SEM-EDX and Auger electron spectroscopy. It was concluded from these measurements that the binary phases Cu2Se and Ga2Se3 are generated prior to the formation of the favoured CuGaSe2 phase. Complete solar cell structures were fabricated by chemical bath deposition of CdS and chemical vapour deposition of ZnO onto the CuGaSe2 absorber layer. Promising 3.2% efficiency with Uoc = 542 mV, Isc = 12.0 mA/cm2 and FF = 0.49 were achieved, proving that electrochemical gallium deposition from an aqueous bath can contribute to the efficient thin film processing of chalcopyrite solar cells.
Synthese und Umlagerung von 2,3,5,6-Tetrakis(isopropyliden)-und 2.3-Bis(isopropyliden)-1,4-diboracycIohexan-Derivaten / Synthesis and Rearrangement of 2,3,5,6-Tetrakis(isopropylidene)-and 2.3-Bis(isopropylidene)-1,4-diboracyclohexane Derivatives
Authors: Hauß J. , Krämer A. , Pritzkow H. , Siebert W.
Published: February 2015

2,3,5,6-Tetrakis(isopropylidene)-1,4-dimethyl-1,4-diboracyclohexane (1c) is formed in 66% yield from 3,4-bis(chloromethylboryl)-2,5-dimethyl-2,4-hexadiene (4a) and (Me2C=CLi)2. Surprisingly, 1,4-dichloro-2,3,5,6-tetrakis(isopropylidene)-1,4-diboracyclohexane (1d) is obtained in 38% yield, when tetrabutyltin and 3,4-bis(dichloroboryl)-2,5-dimethyl-2,4-hexadiene (4b) are heated. Reactions of 1,2-bis(chloromethylboryl)ethane derivatives 5a, b with (Me2C=CLi)2 lead to the 2,3-bis(isopropylidene)-1,4-diboracyclohexanes 6a, b in 41 and 35% yield. The irradiation of 6a, b and 1c,d with ultraviolet light induces an antarafacial [1,5]-Hshift which leads to the formation of the diboracyclohexenes 7a, b and 8a, b, as indicated by NMR studies. On further irradiation 8a, b rearrange to form the corresponding nido-C4B2 carboranes 9a, b. The constitutions of the compounds are derived from spectroscopic data and are proven by X-ray structure analyses of 1c, d, e.
Gehinderte Ligandbewegungen in Übergangsmetallkomplexen, XLIV [1]: Photoreaktionen von Hexacarbonyl-μ-η5:5-fulvalen-dimolybdän mit Allen / Hindered Ligand Movements in Transition Metal Complexes, XLIV [1]: Photoreactions of Hexacarbonyl-μ-η5:5 -fulvalene-dimolybdenum with Allene
Authors: Kreiter Cornelius G. , Conrad Wolfgang
Published: February 2015

Hexacarbonyl-μ-η5:5-fulvalene-dimolybdenum (1) reacts photochemically with allene to η2-allene-pentacarbonyl-μ-η5:5-fulvalene-dimolybdenum (2), μ-η2:2-allene-tetracarbonyl- μ-η5:5-fulvalene-dimolybdenum (4), and dicarbonyl-μ-η5:5-fulvalene-μ-η1:2:3-2-methylene- 4-penten-1,4-diyl-dimolybdenum (5). Complex 2 rearranges readily at room temperature to pentacarbonyl-μ-η1:3-2-propen-1,2-diyl-μ-η5:5-fulvalene-dimolybdenum (3). Upon UV irradiation 4 yields with an excess of allene μ-η2:2-Allene-pentacarbonyl-μ-η5:5-fulvalene-dimolyb-denum (2) shows a hindered rotation of the allene ligand with an energy barrier of ⊿G#
303 = 53.3 ± 2 kJ/mol. Hexacarbonyl-μ-η5:5-bis(cyclopentadiendiyl)methane-dimolybdenum (6) reacts with allene to μ-η2:2-ailene-tetracarbonyl-μ-η5:5-bis(cyclopentadiendiyl)methane- dimolybdenum (7) and octacarbonyl-bis{μ-η5:5:1-(cyclopentadiendiyl-cyclopentadientriyl)-methanejdihydrido-tetramolybdenum (8). For μ-η2:2-allene-tetracarbonyl-μ-η5:5-fulvalene-dimolybdenum (4) and 7 a hindered ligand movement was detected, by which the bridging allene ligand changes from one the side of the molecule to the other. The activation barriers of these pseudo rotations were determined for 4 with ⊿G#
303 = 57.4 ± 2 kJ/mol and for 7 with ⊿G#
293 = 63.4 ± 2 kJ/mol. Hexacarbonyl-μ-η5:5-fulvalene-ditungsten, hexacarbonyl-μ-η5-bis(cyclopentadiendiyl)ethane-dimolybdenum and hexacarbonyl-μ-η5:5-bis(cyclopen- tadiendiyl)propane-dimolybdenum form no stable photoproducts with allene.
Silaheterocyclen, XXXI [1]. Spaltung von 2-Silanorbornenen: Ein einfacher Weg zu Cyclopentenylderivaten von Organochlorsilanen und zu 2-Silanorbornanen / Silaheterocycles, XXXI [1]. Allyl Cleavage of 2-Silanorbornenes: A Facile Synthesis of Cyclopentenyl- Compounds of Organochlorosilanes and of 2-Silanorbornanes
Authors: Auner Norbert , Steinberger Hans-Uwe
Published: February 2015

The exo/endo[4+2]-cycloadducts of Cl2Si=CHCH2
tBu and cyclopentadiene 1 are transformed into the Si-dimethoxy- and chloro-methyl-substituted derivatives 2 and 4. In the case of the 2-silabicyclo[2.2.1] compounds 2 (R1 = R2 = OCH3), 3 (R1 = R2 = CH3) and 4 (R1 = Cl; R2 = CH3) the allyl cleavage with HCl/ether gives the ring opened products 8, 9, and 10 in good yields. The reaction can also be carried out with HBr/ether. In 1 the cleavage of the allyl-silicon bond is disfavoured due to the two chlorine atoms at silicon. Instead HCl adds to the C=C double bond and stereospecifically gives the exo-6-chloro-2,2-dichloro-3-exo/endo-neopentyl-2-silabicyclo[2.2.1]heptanes 5. When the stronger acid CF3SO3H is used no addition to the double bond is observed but only the allyl cleavage takes place to give the triflate 7. The ring opened cyclopentene compounds can be reduced by LiAlH4 to give the corresponding Si-H-compounds 19 and 20. Intramolecular hydrosilylation of 19 leads to the exo/endo-2,2-dimethyl-3-neopentyl-2-silabicyclo[2.2.1]heptanes 21 and so the former bicyclic structure is regenerated.
Conformational Aspects of the p-Nitrosophenolate Anion and Related Compounds: NMR Study and ab initio 6-31G Optimizations of Molecular Structures
Authors: Albert Klaus , Häfelinger Günter , Milart Piotr , Krygowski Tadeusz Marek , Kühn Till , Pursch Matthias , Strohschein Sabine
Published: February 2015

The p-nitrosophenolate anion, PNPA (3), represents an excellent example of variable π-electron transfer demanded by a network of different hydrogen bonds. The limiting structures of mono-protonation in the solid state and in solution are either the p-nitrosophenol (1) or the p-quinonoxime (2) molecules. For the systems 1 to 3 and the related compounds 4 to 7 are results of ab initio 6-31G HF MO optimizations of molecular structures presented which are calculated additionally in variously rotated conformations. Solid state 13C-CP/MAS NMR spectra of two PNPA salts 8 and 9 have been recorded at 7.0 Tesla. The protonation of 8 and 9 was studied in solution using a 400 MHz NMR spectrometer recording the variations in 1H and 13C NMR chemical shifts on changing the solvent from DMSO-d6 to D2O in steps of 25%. The 2D 1H-13C correlated spectrum leads to unambigous assignment of NMR signals. From the coalescence temperature of 1H signals of 9 the experimental barrier of rotation in D2O was determined as 16.9 ± 0.1 kcal mol-1. The calculated gas phase rotational barrier for free PNPA is with 26.9 kcal mol-1 much higher, but is lowered by calculations for the Li-salt 6 c to 14.5 kcal mol-1 and to 11.8 kcal mol-1 for the protonated PNP If. The in-plane inversion of PNPA through 3c is calculated to be extremely high with 52.4 kcal mol-1. The effects of rotation of substituents to orthogonal conformations on calculated energies and on intramolecular distances were studied thoroughly.
Synthese dreizähniger Liganden durch Spaltung von 3,5-Diphenyl-1,2-dithioliumsalzen mit (Thio)benzoylhydrazin oder 2-Hydroxy-5-methyl-anilin. Strukturen der gebildeten Nickelchelate / Synthesis of Tridentate Ligands by Cleavage of 3.5-Diphenyl-1.2-dithiolium Salts with (Thio)benzoylhydrazine or 2-Hydroxy-5-methyl-aniline. Structures of the Corresponding Nickel Chelates
Authors: Kraudelt Heide , Schilde Uwe , Uhlemann Erhard , Weller Frank
Published: February 2015

Tridentate ligands having the donor set S⌒ N⌒ O(S ) were synthesized by cleavage of 3.5-diphenyl-1.2-dithiolium salts with (thio)benzoylhydrazine or 2-hydroxy-5-methyl-aniline. The ligands were characterized as their nickel chelates formed in the presence of triphenylphosphane. The same nickel compounds result by template reactions of dithiolium salt, nickel acetate and the corresponding amine component. Crystal structures were determined for thiodibenzoylmethane benzoylhydrazone 1a, [thiodibenzoylmethane benzoylhydrazonato(2-)]-triphenylphosphane-nickel(II) 1b, [thiodibenzoylmethane thiobenzoylhydrazonato(2-)]-triphenylphosphane-nickel(II) 2b and [thiodibenzoylm ethane 2- hydroxy-5-methyl-anilato(2-)] triphenylphosphane-nickel(II)ethanol 3.
Calorimetrie an Lanthantrihalogeniden und Ammoniumlanthanhalogeniden / Calorimetry of Lanthanum Trihalides and of Ammonium Lanthanum Halides
Authors: Oppermann H. , Morgenstern A. , Ehrlich S.
Published: February 2015

By determination of the enthalpies of solution of lanthanum oxide and of lanthanum trihalides in 4n HX we derived the enthalpies of formation of the trihalides at 298 K using tabulated data. On the basis of these data and measured enthalpies of solution in 4n HX of diammonium lanthanum pentahalides, the enthalpies of formation of (NH4)2LaX5 were obtained.

ΔH°B(LaCl3,f,298) = -258,5 ± 0,8 kcal/mol; ΔH°B((NH4)2LaCl5,f,298) = -411,5 ± 1,4 kcal/mol;

ΔH°B(LaBr3,f,298) = -218,7 ± 1,7 kcal/mol; ΔH°B((NH4)2LaBr5,f,298) = -352,8 ± 2,5 kcal/mol;

ΔH°B(LaI3,f,298) = -166,9 ± 2,0 kcal/mol; ΔH°B((NH4)2LaI5,f,298) = -264,7 ± 3,0 kcal/mol.
Ligandenaustauschreaktionen von Molybdänhexacarbonyl mit dreizähnigen diaciden Liganden / Ligand Exchange Reactions of Molybdenum Hexacarbonyl with Tridentate Diacidic Ligands
Authors: Banße W. , Fliegner J. , Hennig H. , Lehmann A. , Starke I. , Tschwatschal F. , Uhlemann E.
Published: February 2015

Ligand exchange reactions of molybdenum hexacarbonyl with tridentate diacidic ligands were studied by means of photochemical and thermal activation. The reaction products were characterized by mass spectrometry. Species such as MoL2, MoH2L2 and MoO2L could be identified.
NMR-spektroskopische Untersuchungen zur Hydrolyse von funktionellen Trialkoxysilanen/ NMR-Spectroscopic Investigations on the Hydrolysis of Functional Trialkoxysilanes
Authors: Brand Marcus , Frings Albert , Jenkner Peter , Lehnert Robert , Mettemich Hans Jürgen , Monkiewicz Jaroslaw , Schram Jürgen
Published: February 2015

The hydrolysis of functional trialkoxysilanes was studied under various conditions by 1H NMR spectroscopy. The silane concentration was 1 - 2% by weight in a water/acetonesystem. Under these conditions, the reaction was found to be first order. In detail, influence of pH, grade of stirring, and size and structure of functional groups of the alkyltrialkoxysilanes were investigated in order to compare the relative reaction rates of the different compounds.
Zur Darstellung von Organosiliciumpolymeren mit (-SiH2-)n-Gnippen/Synthesis of Organosilicon Polymers Containing ( – SiH2- )n-Units
Authors: Uhlig Wolfram
Published: February 2015

Organosilicon polymers containing (SiH2) or (SiH2)2 units have been prepared via silyltriflate intermediates. Two methods of the formation of silicon-hydrogen bonds are described. Polysilaethylene [SiH2-CH2- ]n has been prepared by ring-opening polymerization of tetraphenyl-1,3-disilacyclobutane followed by a protodesilylation reaction with triflic acid and reduction with LiAlH4. The reaction of H2Si(OTf)2 or (TfO )H2Si- SiH2(OTf) with organolithium or organomagnesium compounds gave poly(silyleneethyne)s [(SiH2)n-C≡C]n and poly(silylenephenylene)s [(SiH2)n-C6H4 -]n. These polymers may serve as suitable precursors for ceramic materials. The TGA studies gave remarkably high ceramic yields. NMR measurements (29Si, 13C, 1H) indicate an regular alternating arrangement of silicon atoms and organic groups in the polymer backbone.
Metal Complexes of Biologically Important Ligands, CX. Orthopalladation of N-(Diphenylmethylene) Schiff Bases from Peptide Esters - C,N versus C,N,O Coordination - Crystal Structure of ClPd[C6H4(C6H5)C=N(Gly-L-Pro -L-Ala-OMe)-C,N,O] with cis/trans Peptide Bonds
Authors: Böhm Andreas , Polborn Kurt , Beck Wolfgang
Published: February 2015

The reaction of the N-(diphenylmethylene) Schiff base from glycyl-L-prolyl-L-alanine methyl ester 1 with tetrachloropalladate in the presence of sodium acetate affords the orthopalladated bicyclic C ,N ,O chelate 2. Complex 2 was characterized by X-ray diffraction. Remarkably, the unit cell contains two independent molecules, the cis isomer 2a and the trans isomer 2b (referring to the peptide bond). 2 reacts with PPh3 by substitution of the carbonyl oxygen atom to give the C,N chelate 3.
Kristallstruktur und thermische Phasenumwandlung von Tetramethylammoniumcyanid, (CH3)4N+CN- / Crystal Structure and Thermal Phase Transition of Tetramethylammonium Cyanide, (CH3)4N+CN-
Authors: Komath Andreas , Blecher Oliver
Published: February 2015

Tetramethylammonium cyanide crystallizes in the tetragonal space group P4/nmm, Z = 2, with cell dimensions a = 773.6(1), c = 546.8(1) pm. The cyanide ion is disordered in the plane perpendicular to the c-axis indicating a rotation. The room temperature phase undergoes a thermal phase transition at -59.9°C probably caused by an order-disorder transition of the cyanide ion.
Synthese und Struktur von Prolinring-modifizierten Actinomycinen des X-Typs / Synthesis and Structure of Proline Ring Modified Actinomycins of the X-Type
Authors: Lifferth Axel , Bahner Isabel , Lackner Helmut , Schäfer Martina
Published: February 2015

The first total synthesis of actinomycins containing L-4-hydroxyproline (1) and the separation and NMR spectroscopic assignment of the regioisomers XOβ and iso-XOβ (1c, 1e) are described. The synthetic XOβ proves, that the oxidized proline ring of the natural actinomycins XOβ , XOδ and X2 (1c, 1d, 1b ) is situated in position 3' of the (β)-peptide chain. The new nonnatural variants iso-XOβ (1e ) and Bis(hyp)-X1 (1f) permitted interesting structure/activity studies. Furthermore, the amino acid sequence of the actinomycins X2 (1b) and X1a (1g) could be derived from NMR correlation spectra. A crystal structure analysis confirmed the complete structure of 1b (and thus that of 1c - e ) and showed the characteristical ,,A “-type conformation present in the depsipeptide rings. This corresponds to the solution conformation, which is clearly verified by typical NMR data.
Cascade Reaction of Camphor-Derived Diynes with Transition Metal Compounds
Authors: Carvalho M. Fernanda N. N. , Pombeiro Armando J. L. , Wagner Gabriele , Pedersen Bjørn , Herrmann Rudolf
Published: February 2015

Platinum(II) catalyzes the isomerization of camphor sulfonamide diynes in a cascade reaction involving annulation of a five-membered ring to the camphor skeleton, ring-enlargement by C-C bond cleavage, reduction of sulfur(VI) to sulfur(IV), and oxidation of a hydroxy group to a ketone. The reactions of the diynes with other transition metal compounds were also studied. Copper, gold and rhenium give final products similar to those obtained with simple Brønsted acids or halogens, mainly by annulation o f a five-membered ring to the camphor moiety, accompanied by reduction of a sulfonamide to a sulfinamide group, but lacking the ring-enlargement step. Palladium(II) occupies an intermediate position as both types o f products are obtained. The reaction mechanism and intermediates are discussed
Zur Reaktion von 2,4-Dioxo-4-ferrocenyl-butansäureethylester mit primären aromatischen Aminen / On the Reaction of Ethyl 2,4-Dioxo-4-ferrocenyl-butanoate with Primary Aromatic Amines
Authors: Prokop Petra , Richter Rainer , Beyer Lothar
Published: February 2015

Starting from ethyl 2,4-dioxo-4-ferrocenyl-butanoate (1) a series of new ferrocene derivatives has been prepared. While the reaction with o-phenylene diamine leads to two ferrocene-containing heterocyclic compounds, 4-ferrocenyl-3H-1,5-benzodiazepine-2-carbonic acid ethyl ester (3) and 3-(2-ferrocenyl-2-oxo-ethylidene)-3,4-dihydro-1H-quinoxalin-2-one · H20 (4), reactions with m- and p-phenylene diamine give both the mono- and disubstituted products 5 - 8, respectively. The conversion of 4 by Lawesson’s reagent results in 2-ferrocenvl-thieno[2,3- b]quinoxaline (9). The new compounds have been characterized by their 1H, 13C NMR, and mass spectra. The molecular structures of 4-ferrocenyl-4-oxo-2-phenylamino-but-2-enoic acid ethyl ester 2, and of 4 and 9 have been determined by X-ray crystal structure analysis.
Synthesis and Electronic Spectra of Tricarbonylrhenium(I) Chloride Complexes with 9,10-Phenanthrenequinone and 9,10-Phenanthrenequinone Diimine as Acceptor Ligands
Authors: Leirer Markus , Knör Günther , Vogler Amd
Published: February 2015

The complexes Re(L-L)(CO)3Cl with L-L = 9,10-phenanthrenequinone (PHQ) and 9,10- phenanthrenequinone diimine (PHI) were prepared and characterized spectroscopically. Both compounds show intense Re(I) to L-L metal-to-ligand charge transfer (MLCT) absorptions. In chloroform, the MLCT bands appear at 711 nm (L-L = PHQ) and 553 nm (L-L = PHI).
Die Kristallstruktur von Bis(bromotriphenyl) arsen(V)-hexabromotellurat( IV), [Ph3AsBr]2[TeBr6]
Authors: Chitsaz Soheila , Neumüller Bernhard , Dehnicke Kurt
Published: February 2015

Yellow-orange single crystals of [Ph3AsBr]2[TeBr6] have been prepared from saturated solutions of Ph3AsBr2 and TeBr4 in acetonitrile and characterized by a crystal structure determination. Space group R3̄c, Z = 12, lattice dimensions at -70 °C: a = b = 1337.9(2), c = 7953.8(4) pm, R = 0.0691. The structure consists of discrete ions [Ph3AsBr]+ and nearly perfectly octahedral [TeBr6]2-.
Darstellung, Schwingungsspektren und Normalkoordinatenanalyse von bindungsisomeren Halogenoselenocyanatorhenaten(IV) sowie Kristallstrukturen von mer-(Ph4P)2[ReCl3(NCSe)2
cis (SeCN)] und mer-(n-Bu4N)2[ReCl3I(NCSe)2
cis] / Synthesis, Vibrational Spectra and Normal Coordinate Analysis of Linkage Isomeric Halogenoselenocyanatorhenates(IV) and Crystal Structures of mer-(Ph4P)2[ReCl3(NCSe)2
cis (SeCN)] and mer-(n-Bu4N)2[ReCl3I(NCSe)2
cis]
Authors: Strueß S. , Preetz W.
Published: February 2015

By treatment of fac-[ReCl3I3]2- with (SeCN)2 indichloromethane fac-[ReCl3(NCSe)3]2- (1), mer-[ReCl3(NCSe)2
cis (SeCN)]2- (2) and mer-[ReCl3I(NCSe)2
cis]2- (3) are formed which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The crystal structures of mer-(Ph-P)2[ReCl3(NCSe)2
cis(SeCN)] (triclinic, space group Pl̅, a = 16.099(1), b = 16.729(3), c =21.026(2) Å, α = 70.194(10), ß = 73.958(10), γ = 83.929(10)°, Z = 4) and mer-(n-Bu4N)2[ReCl3|(NCSe)2
cis] (monoclinic, space group P21/c, a = 11.838(1), b = 12.796(2), c = 30.767(2) Å, ß = 97.419(6)°, Z = 4) have been determined by single crystal X-ray diffraction analysis. Based on the molecular parameters of the X-ray determinations the low temperature (10 K) IR and Raman spectra of the (n-Bu4N) salts have been assigned by normal coordinate analysis. The valence force constants are fd(ReN) = 1.79 (1), 1.71 (2), 1.71 (3) and fd(ReSe) = 1.15 (2) mdyn/Å.
Octachalcogen Cations Te8
2+, Se8
2+, and Mixed (Te8-xSex)8
2+ Stabilized by Chlorometallates of Bi, Zr, and Hf: Synthesis and Crystal Structures of Se8[Bi4Cl14] and E8[MCl6] (E = Se, Te; M = Zr, Hf)
Authors: Baumann A. , Beck J. , Hilbert T.
Published: February 2015

The title compounds were obtained by the reaction of elemental chalcogens E (E = Se, Te) with the respective tetrachlorides ECl4 and the Lewis acidic metal halides ZrCl4, HfCl4, and BiCl3. An alternative way, particularly for the preparation of mixed Se/Te-species, is the enlargement of smaller cationic rings in E4MCl6] (M = Zr, Hf) by adding the respective complementary chalcogen. All reactions were carried out in sealed, evacuated glass ampoules at temperatures between 120 °C and 220 °C, and yielded black crystals of Se8[Bi4Cl14], (Te5.0Se3.0)[HfCl6], (Te5.3 Se2.7)[ZrCl6], (Te6.5Se1.5)[ZrCl6] and Te8[HfCl6], which have been identified by crystal structure analyses. All five compounds contain eight-membered chalcogen rings in an endo-exo-conformation which are isostructural to the known octachalcogen dications E8
2+ (E = S, Se, Te). While in (Te5 .0Se3.0)[HfCl6], (Te5.3Se2 .7 )[ZrCl6], (Te6 .5Se1.5 )[ZrCl6] and Te8[HfCl6] the molecular polycations are surrounded by discrete, octahedral [MCl6]2- counterions, Se4[Bi4Cl14] contains a two-dimensional polymeric anion ([Bi4Cl14]2-)n built of a variety of vertex and edge-sharing BiClx-polyhedra (x = 6, 7). The Bi-Cl bond lengths are spread over a wide range between 250 and 350 pm.
Synthese und Kristallstruktur neuer 1,1,1,3,3,3-Hexaamino-1λ5,3λ5- diphosphazenium-Salze/ Synthesis and Crystal Structure of Novel 1,1,1,3,3,3-Hexaamino-1λ5,3λ5- diphosphazenium Salts
Authors: Landskron Kai , Schnick Wolfgang
Published: February 2015

1,1,1,3,3,3-Hexaamino-1λ5,3λ5-diphosphazenium bromide [(NH2)3PNP(NH2)3]Br, nitrate [(NH2)3PNP(NH2)3][NO3], and toluene-4-sulfonate [(NH2)3PNP(NH2)3][CH3C6H4SO3] have been prepared by anion exchange in aqueous solution. Single crystals were obtained from acetonitrile solutions in a temperature gradient between 60 °C and room temperature. The crystal structures were determined by single crystal X-ray methods at room temperature. ([(NH2)3PNP(NH2)3]Br: P1̄̄ , Z = 2, a = 596.2( 1 ),b = 744.5( 1), c = 1114.4( 1) pm, α = 108.78( 1), β = 104.18(1), γ = 90.64(1)°, R 1 = 0.048, wR2 = 0.104; [(NH2)3PNP(NH2)3][NO3]: P1̄̄, Z = 2, a = 550.9( 1), b = 796.3( 1), c = 1115.7( 1) pm, α = 94.45( 1), β= 99.55( 1), γ = 101,53( 1)°, R1 = 0.033, wR2 = 0.095; [(NH2)3PNP(NH2)3][CH3C6H4SO3]: P21/c, Z = 4, a = 804.1(1), b = 596.1(1), c = 3218.7(3) pm, β = 94.59(1)°, R1 = 0.052, wR2 = 0.136). In the solid the three salts consist of discrete [(NH2)3PNP(NH2)3]+ cations and their corresponding anions. The PN4 tetrahedra in [(NH2)3PNP(NH2)3]Br are staggered, while in [(NH2)3PNP(NH2)3][NO3] the eclipsed conformation is preferred. The PN4 tetrahedra of [(NH2)3PNP(NH2)3][CH3C6H4SO3] show gauche conformation.
Structure and Properties of the Stannides CeAuSn, Ce3Rh4Sn13, and Ce3Ir4Sn13
Authors: Niepmann Dirk , Pöttgen Rainer , Poduska Kristin M. , DiSalvo Francis J. , Trill Henning , Mosel Bernd D.
Published: February 2015

CeAuSn, Ce3Rh4Sn13, and Ce3lr4Sn13 were prepared by reaction of the elements in an arc-melting furnace and subsequent annealing at 970 K for two weeks. The three stannides were investigated by X-ray powder and single crystal techniques. CeAuSn crystallizes with the NdPtSb type, space group P63mc: a = 472.7(2), c = 771.6(3) pm, wR2 = 0.0230,208 F2 values, 11 variable parameters, and BASF = 0.40(2). The gold and tin atoms form a pronounced two-dimensional [AuSn] polyanion which consists of slightly puckered Au3Sn3 hexagons. ,19Sn Mössbauer data at 78 K show one signal at an isomer shift of δ = 1.90(7) mm/s subjected to unresolved quadrupole splitting of ΔEQ = 0.55(2) mm/s. Ce3Rh4Sn13 and Ce3lr4Sn13 adopt the cubic Yb3Rh4Sn13 type structure, space group Pm3n: a = 970.51(3) pm, wR2 = 0.0721, 267 F2 values (Ce3Rh4Sn13) and a = 972.29(6) pm, wR2 = 0.0850, 267 F2 values (Ce3lr4Sn13) with 14 variable parameters for each refinement. Striking structural motifs in Ce3Rh4Sn13 are condensed distorted trigonal [RhSn6] prisms with Rh-Sn distances of 266 pm. The polyhe­dral network leaves two different cages which are occupied by cerium (6c position) and tin (2a position) atoms. The Sn2 atoms show occupancy parameters of only 92% (Ce3Rh4Sn13) and 76% (Ce3Ir4Sn13) and an extremely large displacement parameter indicating a rattling of these atoms within the icosahedral Sn12 cages. Magnetic susceptibility measurements of Ce3Rh4Sn13 show paramagnetic behavior down to 2 K with an experimental magnetic moment of 2.45(2) μB/Ce. No magnetic ordering is observed. Magnetization measurements show a moment of 0.78(2) μB/Ce at 2 K and 5.5 T. Resistivity data reveal only a very weak tem­perature dependence. The two crystallographically different tin sites are resolved in the 119Sn Mössbauer spectrum which shows a signal at δ = 2.12(1) mm/s subject to quadrupole splitting of 1.54(1) mm/s, superimposed by a singlet at δ = 2.47(1) mm/s. The Seebeck coefficient of Ce3Rh4Sn13 is within a few μ V/K of zero over the temperature range of 10 - 300 K.
Metallkomplexe mit biologisch wichtigen Liganden, CXXXI*. Pentamethylcyclopentadienyl-Halbsandwich-Komplexe von Rhodium und Iridium mit Glycosyl-«-iminocarboxylaten als Chelat-Liganden / M etal C om plexes of Biologically Im portant Ligands, CXXXI*. Pentam ethylcyclopentadienyl Halfsandwich Complexes of Rhodium and Iridium with Glycosyl-a-im inocarboxylates as Chelate Ligands
Authors: Krawielitzki Stefan , Beck Wolfgang
Published: February 2015

The N-glycosyl-iminocarboxylate complexes Cp*M(Cl)N(R)=C(R')CO2 (M = Rh, Ir; R = glycosyl, R ’ = Me, Ph, CH2CHMe2) with a chiral metal atom are formed in a template reaction from [Cp*MCl2]2 (M = Rh, Ir), the 2-keto carboxylic acid and tetra-O-acetyl-β-Dglucosamine, D-glucosamine or D-glucamine as mixtures of two diastereoisomers and were characterized by analytical and spectroscopic methods.
Wechselwirkungen in Molekülkristallen, 167 [1, 2]. Kristallzüchtung und Strukturbestimmung von σ-Donator/Akzeptor- Komplexen zwischen 1,4-Dioxan und den Polyiod-Molekülen I2,I2C=CI2, (IC)4S sowie (IC)4NR (R = H, CH3) / Interaction in Molecular Crystals, 167 [1, 2]. C rystallization and Structure Determination of σ -Donor/Acceptor Complexes between 1,4-Dioxane and the Polyiodine Molecules I2,I2C=CI2, (IC)4S and (IC)4NR (R = H, CH3)
Authors: Bock Hans , Holl Sven
Published: February 2015

With 1,4-dioxane as the constant donor, five new donor/acceptor complexes with the polyiodine compounds I-I, I2C=CI2, tetraiodothiophene and two tetraiodopyrrole derivatives could be crystallized and their structures determined despite their decomposition in air. They provide interesting facets for selforganisation on crystallization: The 1,4-dioxane addition causes at best small structural changes of the polyiodine compounds. All adducts crystallize in chains of alternating donors and acceptors, which also staple separatedly. The direction of the contacts O···I depends on the incorporation of the 1,4-dioxane molecules into the iodine acceptor layers. The structural results correlate with those obtained for donor/acceptor complexes with organosulfur donors and, therefore, add to the rationalization of intermolecular interactions.
Remarkably Large 15N, 13C and 18O Isotope NMR Shifts of the Mono-coordinate Phosphorus Atoms in the Compounds (Me3 Si)iPrNCP, K+[iPrNCP]-and KOCP · 2 DME (DME = 1,2-Dimethoxyethane)
Authors: Heckmann Gemot , Becker Gerd , Homer Stephen , Richard Herbert , Kraft Hans , Dvortsak Peter
Published: February 2015

The 31P and 13C NMR spectra of the heteroatom-substituted λ3-phosphaalkynes (Me3Si)- iPrNCP (1), K+ [iPrNCPl- (2) and KOCP · 2 DME (3) are described (Me = methyl; iPr = isopropyl). In addition,15N NMR data of 1 and 2 as well as further NMR results of all accessible nuclei of 1 to 3 are reported. The absolute values of the coupling constants 1J(31P13C) of 1, 2 and 3, 18.2, 45.7 and 57.2 Hz, respectively, are considerably different; the geminal coupling constants 2J( 31P15N) of the first two compounds show a decrease in the reverse order, 15.1 and 3.3 Hz. 13C, 29Si,15N, and 18O isotope effects on the nuclear shielding of the 31P nucleus in the non isotope-enriched compounds 1, 2 or 3 are presented and discussed. The [mono-13C]isotopomers of 1, 2 and 3 exhibit extremely negative 31P13C one-bond isotope shifts varying from -211 to -223 ppb. Remarkably, for 1 and 2 large two-bond 31P15N isotope shifts of -32 and -84 ppb, respectively, are observed. An unexpectedly large two-bond 31P180 isotope effect of -124 ppb was assigned to the [mono-180]isotopomer of compound 3. A three-bond 31P13C isotope shift of -27 ppb was found in 2.
Darstellung, Reaktionen und 51V-NMR-spektroskopische Untersuchungen der Imidovanadium(V)-trichloride: RN=VCl3 (R = H, SiMe3, Alkyl)
Authors: Preuss Fritz , Fischbeck Uwe , Tabellion Frank , Pemer Jens , Frank Walter , Reiss Guido
Published: February 2015

Imidovanadium(V) Trichlorides The reactions of Me3SiN=VCl3 (1) with MeOH, PhOH, HCl, PyH+Cl- or LiOtBu have been studied. The reductive decomposition of 1 by hydrogen chloride in toluene yields HN=VCl3 as a labile intermediate which could be isolated only in a small amount. The syntheses of RN=VCl3 (R = neopent, nPr, cyclohex, CPh3, 1-Ad) and [(tBuN)2V2Cl4(μ-OC13H9)2] (15) are also described. All compounds obtained are characterized by 51V NMR spectroscopy, the fluorenolato complex 15 by X-ray diffraction analysis.
Wechselwirkungen in Molekülkristallen, 174 [1, 2]. Kristallzüchtung und Strukturbestimmung verschiedenartig Methyl-substituierter Imidodiphosphorsäuretetraphenylester / Interaction in Molecular Crystals, 174 [1, 2]. Crystal Growth and Structure Determination of Differently Methyl-Substituted Tetraphenyl Imidodiphosphates
Authors: Bock Hans , Heigel Erik
Published: February 2015

Four differently methyl-substituted tetraphenyl imidodiphosphates [(H3C)nC6H5-n]2PO-NH-PO[C6H5-n(C3)n] (n = 1, 2), i. e. the 4-, 3,4-, 3,5-and 2,3-derivatives, have been crystallized and their structures determined to gain information on the spatial requirements as ligands in the corresponding cesium salts. According to the packing coefficients calculated from the structural data, they increase in the sequence 4<3,5<3,4<2,3. The most perturbed structural motif is the hydrogen bonded, eight-membered of each the dimer subunits.
Transition Metal Complexes with Sulphur Ligands, Part 151 [1]. Ligand Enforced Configurations and Low-Spin States of [FeNS4] Cores in [FeII(L)('pyS4')] Complexes with σ and σ-π Ligands (L = N2H4, pyridine, PMe3, PnPr3; 'pyS4'2- = 2,6-bis(2-mercaptophenylthiomethyl)pyridine (2-))
Authors: Sellmann Dieter , Blum Nicole , Heinemann Frank W.
Published: February 2015

The reactions of [Fe('pyS4')]2 with PMe3 , PnPr3 , N2H4 and pyridine afforded mononuclear [Fe(L)('pyS4')] complexes with L = PMe3 ( 1 ), PnPr3 (2 ), N2H4 (3) and pyridine (4). NMR spectroscopy, magnetic measurements and X-ray structure determinations revealed that all complexes exhibit frans-thiolate donors and low-spin FeII centres, irrespective of the σ-π or σ ligand character of L. In this regard, the properties of [Fe(L)('pyS4')] complexes strongly contrast with those of [Fe(L)('NHS4')] complexes ('NHS4'2- = 2 ,2 '-bis(2 -mercaptophenylthio)- diethylamine(2 -)) and indicate that the rigid py(CH2)2 entity of the 'pyS4
2- ligand is able to enforce trans configurations and low-spin states of complexes with [FeNS4 ] cores. In spite of their diamagnetism, confirming the absence of antibonding electrons, all complexes 1 to 4 are highly reactive and rapidly exchange their L ligands for CO to give [Fe(CO)('pyS4')]. Evidence was obtained that the oxidation of [Fe(N'-H4)('pyS4')] (3) yields the diazene complex [μ-N2 H2 {Fe('pyS4’)}2] (5).
Synthesis, Structure, and Magnetic Properties of EuAgCd and YbAgCd
Authors: Fickenscher  , Kotzyba Gunter , Hoffmann Rolf-Dieter , Pöttgen Rainer
Published: February 2015

New intermetallic compounds EuAgCd and YbAgCd were synthesized in quantitative yield by reaction of the elements in sealed tantalum tubes in a high-frequency furnace. Both com­ pounds were investigated by X-ray diffraction on powders and single crystals: KHg2 type, Imma, a = 490.41(8), b = 771.0(1), c = 834.4(2) pm, wR2 = 0.0624, 255 F2 values, 12 variables for EuAgCd, and MgZn2 type, Pb3/mmc, a = 584.66(5), c = 946.83(9) pm, wR2 = 0.0502, 187 F2 values, 11 variables for YbAgCd. Owing to the very small difference in scattering power, no long range ordering of the silver and cadmium atoms is evident from the X-ray data, although Ag-Cd ordering is expected. The silver and cadmium atoms randomly occupy the mercury and zinc positions of the KHg2 and MgZn2 type structures, respectively. In EuAgCd the [AgCd] substructure consists of strongly puckered, orthorhombically distorted Ag3 Cd3 hexagons, while a three-dimensional network of face-and comer-sharing tetrahedra is observed in YbAgCd. The rare earth atoms fill the space between the Ag3 Cd3 hexagons (EuAgCd) or within the three-dimensional tetrahedral network (YbAgCd). Magnetic susceptibility measurements in­ dicate Pauli paramagnetism for YbAgCd and Curie-Weiss behavior above 60 K for EuAgCd with an experimental magnetic moment of 7.82(3) μB/Eu indicating divalent ytterbium and europium. Ferromagnetic ordering at Tc = 28.0(5) K is observed for EuAgCd. At 2 K and 5 T the saturation magnetization is 5.85(5) μB/Eu.
Supersilyltrielane R nEHal3-n (E = Triel, R = SitBu3): Synthesen, Charakterisierung, Reaktionen, Strukturen [1] / Supersilyltrielanes R nEHal3-n (E = Triel, R = SitBu3): Syntheses, Characterization, Reactions, Structures [1]
Authors: Wiberg Nils , Amelunxen Kerstin , Blank Thomas , Lerner Hans-Wolfram , Polborn Kurt , Nöth Heinrich , Littger Ralf , Rackl Manfred , Schmidt-Amelunxen Martin , Schwenk-Kircher Holger , Warchold Markus
Published: February 2015

Water- and oxygen-sensitive compounds R*EHal2•D, R*EHal2 and R*2EHal (R* = SitBu3; E = B, Al, Ga, In, TI; Hal = F, Cl, Br, I; D = OR2, NR3) have been synthesized by reaction of EHal3 with NaR* in the absence or presence of donors as well as by substitution of D, Hal or R* by other substituents, or by reaction of R*2E-ER*2 (E = Al, In) with I2, H2, AgF2 or HBr. Thermal decomposition of the compounds in solution or in the gas phase leads to elimination of D from R*EHal2•D, or of R*Hal from R*EHal2 and R*2EHal, respectively. The dihalides R*EHal2 act as Lewis acids with respect to donors OR2 or NR3 (formation of adducts R*EHal2•D), the monohalides R*2EHal as Lewis bases with respect to acceptors EHal3 (formation of R*2E+ EHal4
-). Dehalogenations of R*2EHal and R*EHal2 with alkali metals or NaR* leads to compounds R*4E2 (E = AI, In, Tl), R*3E2• (E = AI, Ga), R*4E3
• (E = Al, Ga), R*4E4 (E = AI, Ga), R*6Ga8, R*8In12, (R*2B- ), R*2A- , R*3Ga2
-, R*4Ga3
-, R*4Ga4
2-, R*4Tl3Cl, or R*6Tl6Cl2. The structures of R*BBr2•Py, R*AlBr2•NEtMe2, (R*AlClOBu)2, R*2BF as well as R*2ECl (E = B, Al, Ga, Tl) have been determined by X-ray structure analyses.
Polysulfonylamine, CXL [1]. N-Cycloalkyldimesylamine C„H2n-1/N(SO2CH3)2: Synthesen (n = 3 -6 ), Festkörper-Molekülstrukturen (n = 4 -6 ) Und Rolle Schwacher Wasserstoffbrücken C-H···O In Den Kristallstrukturen
Authors: Schaper Wiebke , Lange Ilona , Henschel Dagmar , Moers Oliver , Blaschette Armand , Jones Peter G.
Published: February 2015

The new disulfonylamines R -N (SO2Me)2, where R = cyclopropyl (1), cyclobutyl (2), cyclopentyl (3) or cyclohexyl (4), were prepared according to an established one-step procedure (condensation of RNH2 with two equivalents of MeSO2Cl, NaH as basic auxiliary). Whereas the structure determination for 1 was marred by severe disorder, compounds 2 -4 have been characterized by low-temperature X-ray diffraction (2: monoclinic, space group P21 Z ' = 2, pseudo-P21/c packing; 3: triclinic, P1̄, Z' - 1; 4: orthorhombic, Pbca, Z ' = 1). The four independent molecules display puckered carbocycles, whereby the electronegative (MeSO2)2N substituent occupies an equatorial position, leading to short intramolecular C - H···O contacts (2: angles of ring pucker φ ≈ 30-33°; 3: envelope conformation, φ ≈ 40°; 4: chair conformation, φ1 ≈ φ2 51°). In accordance with known congener structures, the C(sp3)-N (S)2 moieties feature trigonal-planar N configurations and unusually long C -N bonds (ranges for 2-4: C -N 148.8-150.8 pm, S -N 166.6-168.9 pm, S -N -S 118.3-119.3°). The three crystal packings are governed by a plethora of weak intermolecular hydrogen bonds C(sp3)-H···O , and a thorough survey of these interactions reveals that the inductively activated methyl groups are distinctly more efficient hydrogen bond donors than the methine and methylene ring groups. In each structure, the principal hydrogen bonds create layer substructures parallel to a unit cell face, which are cross-linked by the remaining C -H···O contacts to form three-dimensional networks
Crystal Structure and Magnetic Properties of an Oxygen-Bridged Trinuclear Copper(II) Complex
Authors: Elerman Y. , Kavlakoglu E. , Elmali A. , Kendi E.
Published: February 2015

[Cu3 (L)3].3(C1O4) (LH = l,3-diaminopropan-2-ol) was synthesized and its crystal structure determined. It crystallizes in the triclinic space group P1̅ with a = 10.504(2), b = 10.856(2), c = 12.519(2) Å, a = 74.41(1), ß = 70.60(1), γ = 63.60(1)°, V = 1193.6(3) Å3, Z = 2. The structure consists of trimeric [Cu3(L)3]+3 units and three perchlorate anions in the asymmetric unit. In the compound three copper(II) ions are linked by 1,3-diamino-2-propanol molecules in such a way that an almost equilateral triangle is formed. The coordination spheres of the three copper(II) ions are slightly different from each other. The coordination geometry of Cu1 is a distorted square pyramid, and that of Cu2 is almost square planar while that of Cu3 is tetrahedrally distorted square planar. The copper(II) centers are separated by average 3.481(2) Å and antiferromagnetically coupled (-J = 100 cm-1), which follows from temperature- dependent magnetic susceptibility measurements in the temperature range 4.4 to 299 K. The average Cu-O-Cu angle is 128.1(1)° in the super-exchange pathway. As the temperature is increased, the magnetic moment rises from 1.41 μB at 4.4 K to 2.22 μB at 299 K. In the X(T ) curve no characteristic maximum was observed. The magnetic super-exchange interaction for the title compound is due to the effective overlap of the magnetic orbitals (dx²-y²) with orbitals of bridging alkoxide oxygen atoms
7-Azoniafluorenonderivate durch elektrostatisch aktivierte SNAr-Reaktionen / 7-Azoniafluorenone Derivatives by Electrostatically Activated SNAr-Reactions
Authors: Weiss Robert , Pühlhofer Frank , Hampel Frank
Published: February 2015

Various fluorosubstituted benzoylchlorides 1a-c are transformed into the corresponding acylpyridinium triflates 2a-c by one equivalent of the reagent pair 4-dimethyl-aminopyridine/ trimethylsilyltriflate (DMAP/TMSOTf). Due to the combined electrostatic and mesomeric effect of the acylpyridinium function, fluorine substituents in o- and p-positions can be subsequently substituted with a pyridinio group by additional equivalents of DMAP/ TMSOTf via an SNAr mechanism. Whereas the p-substitution product can be isolated as the highly electrophilic dication salt 3b, the corresponding mono- and bis-orthosubstituted polycation salts 3a and 3c are transformed under the reaction conditions to the 7-azoniafluorenone derivatives 4a,c by a novel cyclo-acylation. Structural and electrochemical data of these compounds are presented.
The Synthesis and Crystal Structure of a Dinuclear μ-Pyrazolato-N,N'-Bridged Dinickel(II) Complex of 1,3-Bis(2-hydroxy-4-methoxybenzylideneamino)propan-2-ol
Authors: Elmali A. , Kavlakoglu E. , Elerman Y.
Published: February 2015

Ligand The asymmetric unit of crystal of the title compound, [Ni2(L)(C3H3N2)] (L = 1,3-Bis(2-hydroxy-4-methoxybenzylideneamino)propan-2-ol, C3H3N2 = pyrazolate) contains two inde­pendent dinickel(II) complexes. In both molecules, the nickel(II) ions are bridged by the alkoxo group of the ligand and the N atoms of the pyrazolate group. Each nickel(II) ion is coordinated by two N and two O atoms, forming a square with trans-N2O2 geometry.
Bildung und Struktur von Tris(diphenylstibino)amin/Formation and Structure of Tris(diphenylstibino)amine
Authors: Balázs Lucia , Breunig Hans Joachim , Krüger Tamara , Lork Enno
Published: February 2015

Tris(diphenylstibino)amine (Ph2Sb)3N (1) is formed in 49.5% yield by ammonolysis of Ph2SbCl in liquid NH3, and as a side product of the synthesis o f Ph4Sb2 by reactions of Ph3Sb with Na and BrCH2CH2Br in liquid NH3. The structure of 1 was determined by single crystal X-ray diffraction. The crystals consist of molecules with an almost planar Sb3N core (sum of the angles at nitrogen: 352.14°).
Electrolysis of Tetrakis(4-N,N-dimethylammophenyl)methane -Fragmentation of a Tetraarylmethane under Oxidative Conditions
Authors: Zimmermann Thomas J. , Müller Thomas J. J.
Published: February 2015

Upon anodic oxidation tetrakis(4-N,N-dimethylaminophenyl)methane (3) fragments to give the stable species crystal violet (6), N,N,N′,N′- and Michler’s hydrol blue (12) that can be readily absorption bands.
KLF5 regulates infection- and inflammation-induced pro-labour mediators in human myometrium
Authors: Lappas Martha
Published: February 2015

The transcription factor Kruppel-like factor 5 (KLF5) has been shown to associate with nuclear factor kappa B (NFκB) to regulate genes involved in inflammation. However, there are no studies on the expression and regulation of KLF5 in the processes of human labour and delivery. Thus, the aims of this study were to determine the effect of i) human labour on KLF5 expression in both foetal membranes and myometrium; ii) the pro-inflammatory cytokine interleukin 1 beta (IL1β), bacterial product flagellin and the viral dsRNA analogue poly(I:C) on KLF5 expression and iii) KLF5 knockdown by siRNA in human myometrial primary cells on pro-inflammatory and pro-labour mediators. In foetal membranes, there was no effect of term or preterm labour on KLF5 expression. In myometrium, the term labour was associated with an increase in nuclear KLF5 protein expression. Moreover, KLF5 expression was also increased in myometrial cells treated with IL1β, flagellin or poly(IC), likely factors contributing to preterm birth. KLF5 silencing in myometrial cells significantly decreased IL1β-induced cytokine expression (IL6 and IL8 mRNA expression and release), COX2 mRNA expression, and subsequent release of prostaglandins PGE2 and PGF2α. KLF5 silencing also significantly reduced flagellin- and poly(I:C)-induced IL6 and IL8 mRNA expression. Lastly, IL1β-, flagellin- and poly(I:C)-stimulated NFκB transcriptional activity was significantly suppressed in KLF5-knockout myometrial cells. In conclusion, this study describes novel data in which KLF5 is increased in labouring myometrium, and KLF5 silencing decreased inflammation- and infection-induced pro-labour mediators.
THE USE OF HIGH-PERFORMANCE LIQUID CHROMATOGRAPHY AS SCREENING TECHNIQUE FOR PECTIN AND PECTIN SUBSTANCES OF DIETARY FIBERS
Authors: Ignatyeva G.N. , Melgarejo Juan Patricia , Monera Picazo Sandra , Follana Álvarez DesirÃ©e
Published: February 2015

The peak of the unspecified compound of quantitative analysis of organic acids in biological materials by using high-performance liquid chromatography was identified. This peak corresponded to polygalacturonic acid. A High-performance liquid chromatographic method was developed to identify and quantify of water soluble pectin fraction and insoluble pectin fraction, galacturonic acid and polygalacturonic acid. The method based on the extraction of free water soluble fraction with phosphate buffer (pH 4.8) or with 0.01 N phosphoric acid and on the acid hydrolysis of insoluble pectin fraction in presence 0.1 N HNO3. The pectin fractions were separated and determined on a C610H column using elution with 0.01 N phosphoric acids and ultraviolet detection at 210 nm. Galacturonic acid and polygalacturonic acid were used as internal standard. The calibration curves were presented for each of the standards. The determinations were performed in the linear range of 0.04÷0.17% w/v for both pectin fractions. Proposed procedure can considered as a rapid method for quantitative pectin determination in the food, food nutrition’s food, and pharmaceutical agents.
Improved Nutrition Delivery and Nutrition Status in Critically Ill Children With Heart Disease
Authors: Kaufman Jon , Vichayavilas Piyagarnt , Rannie Michael , Peyton Christine , Carpenter Esther , Hull Danielle , Alpern Jennifer , Barrett Cindy , da Cruz Eduardo M. , Roosevelt Genie
Published: February 2015

BACKGROUND:

This initiative sought to improve nutrition delivery in critically ill children with heart disease admitted to the cardiac ICU (CICU) and neonates undergoing stage 1 palliation (S1P) for single-ventricle physiology through interdisciplinary team interventions. Specific goals were increased caloric and protein delivery for all patients and a more nourished state for infants with single ventricles at the time of discharge.

METHODS:

We developed a nutrition flow sheet in the electronic health record to track whether daily nutrition goals were met. Interventions included nurses reporting daily whether caloric and protein goals were met, mandatory involvement of feeding specialists, and introduction of an enteral nutrition guideline. For infants undergoing S1P, weight-for-age z score (as an indicator for assessing malnutrition) was calculated at admission and discharge.

RESULTS:

The percentage of patient days per month when daily caloric goals were met increased from 50.1% to 60.7%, and protein goals met increased from 51.6% to 72.7%. Hospital length of stay, need for ventilation, and mortality did not differ. Patients undergoing S1P demonstrated a statistically significant improvement in weight-for-age z score compared with the preintervention group (P = .003). Thirteen S1P patients were discharged undernourished in the preintervention group; 5 were severely undernourished. In the intervention group, 4 patients were discharged undernourished, and none were severely undernourished.

CONCLUSIONS:

This initiative resulted in improved nutrition delivery for a heterogeneous population of cardiac patients in the CICU as well as significant improvements in weight gain and nourishment status at discharge in infants undergoing S1P.
Understanding the 1600°C Fuel Temperature Limit of TRISO Coated Fuel Particles
Authors: Trejo Félix Cancino , Padilla Mariana Sáenz , López-Honorato Eddie
Published: February 2015

The TRISO (tristructural isotropic) coated fuel particle is made of a uranium oxide kernel coated with three layers of pyrolytic carbon and one of silicon carbide. This fuel, originally used in High Temperature Reactors, has been proposed as accident tolerant fuel for Light Water Reactors after the accident in Fukushima. Although this fuel is capable of retaining fission products within the particle up to 1600°C, little is known on the origin of this temperature limit. Therefore, in order to increase the safety of this type of fuel, it is necessary to understand the origin of the degradation of the materials that compose this fuel. We have studied the effect of temperature on the microstructure and diffusion of silver in pyrolytic carbon coatings produced by fluidized bed chemical vapor deposition. Samples were heat treated at 1000°C, 1400°C and 1700°C for 200 hrs. under inert atmosphere. The effect of temperature on the microstructure and silver diffusion behavior were analyzed by Raman spectroscopy, X-Ray diffraction, optical microscopy, SEM and TEM. We observed that the microstructure of PyC changed drastically above 1400°C, showing the increase in anisotropy and the re-orientation of the graphene planes. The diffusion of silver appears to be also correlated with this change in microstructure.