bluuebunny/crossref_metadata_2025 huggingface dataset:
Reaktionen von Vanadiumtetrachlorid mit Trithiazylchlorid / Reactions of Vanadium Tetrachloride with Trithiazylchloride
Authors: Beber Gerhard , Hanich Jürgen , Dehnicke Kurt
Published: March 2015

[VCl3(NSCl)2]2, which is a chloro-bridged dimer, is formed by the reaction of VCl4 with (NSCl)3. Thermal decomposition of the vanadiumtrichloride-thiazylchloride adduct, as well as the reaction of VCl4 with (NSCl)3 in the presence of sulfurdichloride lead to the ionic species [N(SCl)2]3[V2Cl9]. By the reaction of the recently reported complex (AsPh4)2[(VCl5)2(N2S2)] with (NSCl)3 in CH2Cl2-solution AsPh4[VCl4(N2S2)] is prepared, which contains the anion as a polymer with N2S2-bridges. The IR spectra are reported and assigned
Synthese und Strukturuntersuchung von Polyhalogeniden im System Iod/Brom / Syntheses and Structure Analyses of Polyhalides in the System Iodine/Bromine
Authors: Parlow Axel , Hartl Hans
Published: March 2015

Several polyhalide anions containing iodine and bromine have been synthesized with 2,2′- bipyridylium (BPH+) as the cation. The crystal structures of three compounds have been investigated by X-ray crystal structure analyses. BPH+(H3O)+(IBr2)2
- (P1̄, a = 780.0(3), b = 815.4(3), c = 1547.9(6) pm, α = 75.59(7), β = 82.28(8), γ = 88.15(8)°, R = 6.5%) contains two independent, nearly linear, asymmetric IBr2
- groups. In BPH+I2Br3
- (P21/c, a = 1269.1(6), b = 673.0(4), c = 2047.4(8) pm, β = 112.39(9)°, R = 6.3%), the anion is V-shaped like other pentahalide anions. It can be characterized as consisting of two IBr molecules linked to a bromide anion with the longer I-Br bonds at the central atom. The polyhalide anions in [xxx] (P21/m, a = 435.1(2), b = 1710.6(7), c = 1349.0(6) pm, β = 97.56(9)°, R = 15.5%) form infinite zigzag layers. They are built up by IBr2
- anions which are connected by iodine molecules. The cations are enclosed in columnar cavities within these layers
Beiträge zur Chemie der Schwefelhalogenide, 6 [1] Untersuchungen an Trichlorsulfonium(IV)-Salzen / Contributions to the Chemistry of Sulfur Halides, 6 [1] Investigations on Trichlorosulfonium(IV) Salts
Authors: Minkwitz Rolf , Jänichen Klaus , Prenzel Herbert , Wölfel Volker
Published: March 2015

The crystal structure of SCl3
+AsF6
- is reported.

The mean S-Cl stretching frequency ν̄ of the SCl3
+ cations, weighted according to the degree of degeneration, in the different SCl3
+X- salts is directly proportional to the mean S-CI distance r̄scl, the force constant fSCl and the sulfur. . . anion distance (Cl3S+. . . X-).

That SCI3
+Cl- should be isostructural with PCl4
-
, the large variation in the S-CI stretching frequencies in the SCl3
+X- salts is due to cation-anion interaction forces
Phosphorverbindungen ungewöhnlicher Koordination, 3 [1] Vergleich des Cycloadditonsverhaltens von Diphenylketen und Triphenylphosphen / Phosphorus Compounds with Unusual Coordination, 3 [1] Comparison of the Cycloaddition Behaviour of Diphenylketene and Triphenylphosphene
Authors: Regitz Manfred , Urgast Klaus , Maas Gerhard
Published: March 2015

Triphenylphosphene (3b), generated thermally or photochemically from 1b, undergoes olefination reaction with 4.5-benzotropone (6) to yield 1-(diphenylmethylen)-4.5-benzocycloheptatriene (9); the oxaphosphetane 7b is assumed to be the intermediate of this reaction. In an analogous way, 4-pyrone (15) is transformed into 4-(diphenylmethylen)pyrane (16). Corresponding olefination behaviour is observed in the reactions of 6 and 15 with diphenylketene.

In the reaction of tetracyclone (20) with diphenylketene (3a), the olefination sequence leads to the formation of (diphenylmethylen)tetraphenylcyclopentadiene (21) via betain 22a and the cycloadduct 23a. The spirocyclic reaction product 26a probably arises from the same betain - like intermediate (22 a → 25 a → 26 a). The analogy in triphenylphosphene reactivity towards 20 is restricted to the [2+8]-cycloaddition step (formation of 26b)
Tetrahydrothiophen als Komplexligand; Darstellung und Charakterisierung von Spezies der Zusammensetzung M2(CO)9(C4H8S) (M = Mn, Re) und Mn2(CO)8(C4H8S). Röntgenstrukturanalysen von Mn2(CO)9(C4H8S) und Mn2(CO)8(C4H8S) / Tetrahydrothiophene as a Complex Ligand; Synthesis and Characterization of Species of Composition M2(CO)9(C4H8S) (M = Mn, Re) and Mn2(CO)8(C4H8S). X-Ray Structures of Mn2(CO)9(C4H8S) and Mn2(CO)8(C4H8S)
Authors: Guggolz Ernst , Layer Klaus , Oberdorfer Franz , Ziegler Manfred
Published: March 2015

Heating of the decacarbonyls M2(CO)10 (M = Mn, Re) in tetrahydrothiophene under reflux gave the substitution products M2(CO)9(C4H8S) (M = Mn, Re) and Mn2(CO)8(C4H8S), respectively. In the former an equatorial CO group has been substituted, while in the latter the tetra- hydrothiophene ligand bridges symmetrically two Mn-Mn bonded Mn(CO)4 units. The manganese compounds (monoclinic, P21/c) were characterized by means of X-Ray structure analysis
Bis-und Tris-aluminiumalkan-Verbindungen als Zwischenprodukte bei der Auflösung von Aluminium mit Olefinen in Gegenwart von Aluminiumtrichlorid oder Alkylaluminiumdichlorid /Bis-and Tris-aluminum-alkane Compounds as Intermediates During the Dissolution of Aluminum Metal with Olefins in the Presence of Aluminum Trichloride or Alkyl Aluminum Dichloride
Authors: Martin Heinz , Bretinger Helmut
Published: March 2015

Aluminum can be dissolved by ethylene in the presence of aluminum trichloride to form primarily bis-(dichloro-aluminum)-ethanes (1) and (2) or in the presence of ethyl aluminum dichloride to form chloro-aluminum-ethyl-(dichloroaluminum)-ethane (3) and/or a tris-aluminum compound Cl2A1-C2H4-Al(Cl)-C2H4-Al(Cl)Et (4). 1-4 react further with olefins, with elimination of alkyl aluminum dichloride and/or dialkyl aluminum chloride, which are practically inert towards olefins. The C2H4 -bridge is available to the growth and displacement reaction with olefins.
Kupplungsreaktionen von Diazoniumsalzen mit 3-tert-Butoxy- 1,6-methano[10]annulen und Röntgenstrukturanalyse eines Vertreters /Coupling Reactions of Diazonium Salts with 3-tert-Butoxy-1,6-methano[10]annulene and X-Ray Structure Analysis of one Compound
Authors: Neidlein Richard , Gottfried Reiner , Gieren Alfred , Kaerlein Carsten-P. , Hübner Thomas
Published: March 2015

The syntheses of 5a-c by coupling reactions of 3-tert-butoxy-1,6-methano[10]annulene with different aryldiazonium salts as well as their spectroscopic properties are described; an X-ray structure analysis of 5c is reported.
Preparation of Haloselenium and Halotellurium Trithiocarbonates
Authors: Kato Shinzi , Kaga Kouichi , Ishida Masaru , Murai Toshiaki
Published: March 2015

Selenium (1) and tellurium bis(trithiocarbonates) (2) were found to react with bromine and iodine to give the corresponding haloselenium (11) and halotellurium trithiocarbonates (7, 8). Reaction of 2 with excess of bromine give tribromotellurium trithiocarbonates (9).
Pentakoordiniertes Silicium: Intramolekulare Koordination bei O-Fluorsilylderivaten von N.N-disubstituierten Aminoethanolen bzw. N-fluorsilylsubstituierten Derivaten des Trimethylethylendiamins/Penta-co-ordinate Silicon: Intramolecular Coordination of O-Fluorosilyl Derivatives of N.N-Disubstituted Aminoethanols and of N-Fluorosilyl Substituted Derivatives of Trimethylethylenediamine
Authors: Krebs Roland , Schomburg Dietmar , Schmutzler Reinhard
Published: March 2015

Tetrafluorosilane and phenyltrifluorosilane react with the O-trimethylsilyl derivatives of N.N-disubstituted aminoethanols and with the N-trimethylsilyl derivative of N.N.N′-trimethylethylene diamine to give the corresponding monosubstituted fluorosilyl compounds in which, on the basis of 19F NMR spectroscopic studies, intramolecular N -Si bonding raises the coordination number of silicon from four to five (i.e. λ4Si -> λ5Si). The low temperature 19F NMR data suggest a trigonal-bipyramidal configuration at λ5 Si with an axial N -Si coordinate bond.
Untersuchungen an quartären Pyridinium-Salzen, XVII Cyclopeptidartige Verbindungen aus Salzen von Nikotinoylaminosäureamiden/Investigations of Quaternary Pyridinium Salts, XVII Cyclopeptide-like Substances from Salts of the Amides of Nicotinoylamino Acids
Authors: Gündel Wolf-H.
Published: March 2015

The amides of nicotinoylamino acids were prepared and alkylated to the quaternary salts 1f-n. The α-amino acid moiety in 1 is S configurated. The salts 1 cyclise under the influence of base to give the cyclopeptide-like substances 4, 5 and 7, with seven-or fourteen (sixteen, eighteen-) membered rings, respectively.
Notizen: Epoxide Assisted Displacement of Triflyl Group by Fluoride Ion. An Efficient Approach to Fluorodeoxy Sugars
Authors: Latif Farzana , Malik Abdul , Voelter Wolfgang
Published: March 2015

Displacement of triflyl group by fluoride ion in benzyl 2,3-anhydro sugars leads with stereochemical inversion to fluorodeoxy sugars, providing a general method for the introduction of fluorine in the neighbourhood of oxirane ring in anhydro sugars. This procedure is mild, convenient, and does not experience difficulties which sometime are encountered in nucleophilic fluoride displacements in carbohydrate systems.
Reaktive E=C (p-p)π-Systeme III [1]: Diels-Alder-Reaktionen mit F3CP=CF2 als Dienophil / Reactive E=C (p-p)π-Systems III [1]: Diels Alder Reactions with F3CP=CF2 as Dienophile
Authors: Grobe Joseph , Le Van Due
Published: March 2015

The perfluorophosphaalkene F3CP=CF2 (1) reacts as a dienophile at temperatures between -20 and +15 °C with cyclopentadiene, 1,3-cyclohexadiene, butadiene and 2,3-dimethyl- butadiene, respectively, giving the corresponding Diels-ALder adducts 2 to 5 in high yields. The observed reactivity proves the close relationship of P=C and C=C systems.
Azido(imidazole)bis(acetylacetonato)cobalt(III) Complexes — Facile trans ⇋ cis Interconversion in Solution
Authors: Das J. K. , Dash K. C.
Published: March 2015

A number of mixed-ligand complexes of cobalt(III) containing coordinated azide ion, acetyl- acetonatc anion and the neutral base imidazole and, having the general formula [Co(acac)2(N3)(Im)] (Im = imidazole or its derivatives) have been synthesised by the reaction of K[trans-Co(acac)2(N3)2] with the biologically active ligand imidazole or its derivatives. IR and electronic spectra alongwith 1H and 13C NMR spectra have been employed to characterise the complexes and determine their geometry. In contrast to the stable trans-[Co(acac)2(NO2)(Im)] complexes, these azido complexes arc shown to undergo facile trans ⇋ cis interconversion in CHCl3 solution. The NMR spectra (1H and 13C) can be interpreted by assuming the presence of an equilibrium mixture of the cis- and trans-isomers in solution.
Low-Temperature Matrix Photochemistry of (η4 -Diene)tetracarbonylchromium Complexes
Authors: Gerhartz Wolfgang , Grevels Friedrich-Wilhelm , Klotzbiicher Werner E. , Koerner von Gustorf Ernst A. , Perutz Robin N.
Published: March 2015

Photolysis of (η4-diene)Cr(CO)4 complexes (diene = butadiene, trans,trans-2A-hexadiene, 2,3-dimethylbutadiene) in Ar, N2, and CO matrices at 10-12 K was monitored by infrared and UV-Vis spectroscopy. In argon and dinitrogen matrices loss of CO ist the predominant photoreaction. The resulting fac-(η4-diene)Cr(CO)3 can take up N2 from the matrix to form (η4-diene)Cr(CO)3(N2). In the case of the hexadiene complex this process requires matrix an­nealing subsequent to photolytic loss of CO. Photolysis in CO matrices, by contrast, results in stepwise displacement of the diene ligand, yielding (η2-diene)Cr(CO)5 and ultimately Cr(CO)6.
Dimere Naphthochinone, 13. Synthese m-substituierter 4-Methoxy-1-naphthole – β-Halogenalkylether als Schutzgruppen für Phenole / Dimeric Naphthoquinones, 13. Synthesis of m-Substituted 4-Methoxy-1-naphthols – β-Haloalkyl Ethers as Protective Groups in Phenols
Authors: Laatsch Hartmut
Published: March 2015

m-Substituted naphthohydroquinone monoethers are difficult to synthesize by direct alkyla­tion. They are conveniently obtainable now in the following way: Acid-catalyzed reaction of naphthohydroquinones with β-haloethyl alcohols affords monoethers 5 in high yield which are conventionally alkylated forming 6. In 6 the protective group is cleaved off via the vinyl ether or, under milder conditions, by bromine/iodine exchange and fragmentation with zink.
Phytochemical Investigation of Cassia spectablis Seeds Isolation and Structural Studies of Two New Flavone Glycosides
Authors: Singh M. , Singh J.
Published: March 2015

From the seeds of Cassia spectablis 6-hydroxy-4′-methoxy flavone-6-0-arabinopyranoside and 3,5-dihydroxy-7,3′,4′-trimethoxy flavone-3-0-arabinopyranoside have been isolated and their structure elucidated.
On the Elimination of the 3-Benzylthioenol Ether of Pregn-4-ene-3,20-dione by W-2 Raney Nickel
Authors: Gonzalez Mario D. , Burton Gerardo
Published: March 2015

Reaction of 3-benzylthiopregna-3,5-dien-20-one or of pregna-3,5-dien-20-one with W-2 Raney nickel in acetone afforded a mixture of 20-ketopregnanes with different degrees of insaturation on rings A and B, of which the main component was identified as pregn-2-en-20-one. When deactivated Raney nickel was used, the main product was the expected pregna-3,5-dien-20-one with minor amounts of pregn-4-en-20-one and pregn-5-en-20-one.
Studien zum Vorgang der Wasserstoffübertragung, 76 [1]. Der anomale Verlauf der Elektroreduktion von Cumarin mit Lithium als Leitsalzkation: Versuche zur Reaktionslenkung durch Mediatoren / Studies on the Occurrence of Hydrogen Transfer, 76 [1] The Anomal Course of the Electroreduction of Coumarine with Supporting Electrolyts Containing Li+: Experiments to Influence the Reaction by Mediators
Authors: Horner Leopold , Franz Christoph
Published: March 2015

In contradiction to the experience the hydrodimer is formed as the main product in the electroreduction of coumarine using lithium compounds as a supporting electrolyt. It is assumed that the lithium ions are coordinated internally with the radicalanion A resp. B derived from coumarine. In this way the hydrodimerization is favoured. From 18 different compounds added as possible mediators to the catholyt only pyridine influences moderately the ratio: hydrodimerizationproduct/dihydroproduct.
Phosphonium Ylides, V.Wittig Reaction with 2,3,4(1H̲ )-QuinoIinetriones
Authors: Sidky M. M. , Boulos L. S.
Published: March 2015

Quinolinetriones, Phosphonium Ylides, Wittig Reaction Quinolinetrione (1a) reacts with phosphonium ylides (2a-c) to yield the corresponding ethylenes (3a-c) together with triphenylphosphine oxide. Treatment of trione (lb) with ylides (2a-b) affords, on the other hand, the cyclobuta (c) quinoline derivatives (4a) and (4b), respectively. Structural assignments are based on analytical and spectroscopic evidence.
Spin Trapping of Radicals in Gas-Phase Cigarette Smoke
Authors: Halpern Alexander , Knieper Josef
Published: March 2015

Spin trapping with N-t-butyl-α-phenyl nitrone (PBN) and 5,5-dimethyl-1-pyrroline-oxide (DMPO) has been utilized to identify the radicals in the gas phase of cigarette smoke. ESR spectra reveal predominantly alkoxy radicals which are continuously formed in smoke, but not directly in the flame.
Metallorganische Verbindungen der Lanthanoide, 27 [1]. Die Kristall- und Molekülstruktur von (C5H5)2Lu(μ-CH3)2Li(tmed) / Organometallic Compounds of the Lanthanides, 27 [1]. The Crystal and Molecular Structure of (C5H5)2Lu(μ-CH3)2Li(tmed)
Authors: Schumann H. , Reier F.-W. , Hahn Ekkehardt
Published: March 2015

The title compound, 1, is obtained as colorless crystals by reaction of LuCl3, NaC5H5 and LiCH3 in the molar ratio 1:1:4 in diethylether in the presence of tmed. 1 crystallizes in the tetragonal space group P412121 a = 8.375(8) Å, c = 28.78(4) Å, V = 2018.6 Å3 and Z = 4. The molecular structure of 1 possesses crystallographically imposed C2-symmetry and consists of a (C5H5)2Lu-moiety joined to a Li(tmed)-unit by two methyl bridges. Principal dimensions are as follows: Lu-C(br) 2.461(12) Å, Li-C(br) 2.24(2) Å. Cp-Lu-Cp′ 131.9(3)°, C(br)-Lu-C′(br) 95.0(3)°.
Synthese und spektroskopische Charakterisierung neuer Bis(thiolato)- und Endithiolato-bis(η5-cyclopentadienyl)hafnium(IV)-Komplexe / Synthesis and Spectroscopic Characterisation of New Bis(thiolato)- and Endithiolato-bis(η5-cyclopentadienyl)hafnium(IV) Complexes
Authors: Köpf Hartmut , Klapötke Thomas
Published: March 2015

The hafnocene thiophenolates Cp2Hf(SC6H4R)2 (Cp = η5-C5Hs; R = H, o-Me,p-Me, p-NH2) and cis- 1.2-endithiolates Cp2Hf(S2C6H4), Cp2Hf(S2C6H3Me-4), and Cp2Hf{S2C2(CN)2} were prepared by reaction of Cp2HfCl2 with equivalent amounts of the appropriate lithium thiolates or endithiolates, or with Na2S2C2(CN)2. respectively. From variable temperature 1H NMR studies of the endithiolate complexes with aromatic ligands a folded (“envelope”) conformation of the five-membered chelate rings, undergoing rapid inversion at room temperature, can be derived.
Metallkomplexe mit Tetrapyrrol-Liganden, XXXVIII [1]. Zur Kenntnis der Alkyl- und Arylimidovanadium(IV)-Porphyrine / Metal Complexes with Tetrapyrrole Ligands, XXXVIII [1]. On the Knowledge of Alkyl- and Arylimidovanadium(IV) Porphyrins
Authors: Buchler Johann W. , Pfeifer Stefan
Published: March 2015

A series of novel alkyl or aryiimidovanadium(IV) 5,10,15,20-tetra(p-tolyl)porphyrinates, VNR(TTP) (4a-4g), is described. They are obtained from the vanadyl complex, VO(TTP) (2a) via the reactive intermediate VCl2(TTP) (3b) which undergoes aminolysis with the respective primary amines RNH2 (R = tBu, Ph, pTol, pClPh, pAnis, pBiph, ptBuPh)**. The formulae are proved by elemental analyses and mass spectra. The paramagnetic complexes are stable to water and may thus be purified by chromatography but are hydrolyzed to give 2 a on treatment with acetic acid. The UV/VIS and 1H NMR spectra of 4a-4g are of the same type as 2a, but the former are slightly hypsochromically shifted, and the latter do not show the proton resonances of the organylimide ligands due to the proximity of the paramagnetic metal center.
Bimetallic Alkoxides of Nickel(II) with Niobium(V) and Tantalum(V)
Authors: Jain R. , Rai A. K. , Mehrotra R. C.
Published: March 2015

A new class of bimetallic isopropoxides of nickel(II) with niobium and tantalum with the general formula, Ni[M(OPri)6]2, (where M = Nb or Ta) have been synthesized by the reaction of nickel chloride isopropanolate, NiCl2·ϰPriOH, with potassium hexaisopropoxy metalates, KM(OPri)6, (M = Nb or Ta) in the molar ratio 1:2. These derivatives have been characterized by elemental analyses, molecular weight determinations, infrared and visible reflectance spectroscopy in addition to magnetic susceptibility measurements. Alcohol interchange reactions of these bimetallic alkoxides have also been studied. On the basis of above studies, an octahedral geometry has been assigned to Ni(II) in primary bimetallic alkoxides while in secondary derivatives, it appears that there exists an equilibrium between octahedral and tetrahedral forms.
Die Reaktion von Tri-t-butylphosphan und Tri-t-butylarsan mit Selen und Tellur: Bildung inerter und labiler Chalkogenophosphorane und -arsorane / The Reaction of Tri-t-butylphosphane and Tri-t-butylarsane with Selenium and Tellurium: Formation of Inert and Labile Chalcogenophosphoranes and -arsoranes
Authors: du Mont Wolf-W.
Published: March 2015

The reactions of tri-t-butylphosphane 1 with selenium and tellurium proceed quantitatively with formation of seleno- and the telluro-tri-t-butylphosphorane. respectively (3, 4). Tri-t-butylarsane 2 reacts with selenium to give seleno-tri-t-butylarsorane (5), but no significant interaction is observed between 2 and elemental tellurium. 1H and 31P NMR spectra provide evidence for rapid tellurium transfer between telluro-tri-t-butylphosphorane (4) and tri-t-butylphosphane (1), tri-t-butylarsane (2) or tris(dimethylamino)phosphane.

Selenium transfer between seleno-tri-t-butylarsorane (5) and tri-t-butylarsane (2) leads to 1H and 13C NMR line broadening. Vibrational spectra of t-Bu3E−Y (3: E = P, Y = Se; 4: E = P, Y = Te; 5: E = As, X = Se) indicate coupling of E−C and E−Y stretching vibrations in 3 and 4.
Synthesen neuer methanoüberbrückter Diphosphaheterocyclen und Röntgenstrukturanalyse eines Vertreters / Synthesis and X-Ray Structure Analysis of a New Methano-Bridged Diphosphaheterocycle
Authors: Neidlein Richard , Degener Hans-Joachim , Gieren Alfred
Published: March 2015

The syntheses of 3, 4a, 4b by reaction of Methylenebis(dichlorphosphane) (1) with silylated substituted ureas are described as well as their spectroscopic properties; an X-ray structure analysis of 3 is reported.
„Second messenger″ höherer Pflanzen / Second Messenger of Higher Plants
Authors: Schildknecht Hermann , Hein Martin , Bender Wolfgang
Published: March 2015

Cyclic mononucleotides − 2′,3′ cAMP and 2′,3′ cGMP − were found in several higher plants. They seem to be widespread, naturally occurring compounds. 2′ AMP, 3′ AMP, 2′ GMP and 3′ GMP, which were also isolated from several plants, are possibly artifacts of the cyclic nucleo­tides. In small amounts ApA was isolated from Abutilon grandiflorum, UpA and UpG from Mimosa pudica L.

The biological influence of 2′,3′ cAMP and 2′,3′ cGMP on the nyctinastic leaf movement was tested. There is some evidence that both substances shift and dampen the circadian rhythm of Albizia lophanta.
Conformational Studies of Synthetic Polyethylene Glycol Bound Substance P and its Lower Analogues
Authors: Koziej Piotr , Mutter Manfred
Published: March 2015

The synthesis of Substance P (SP) bound at the C-terminal methionine to polyethylene glycol monomethyl ether (M-PEG) is described. SP-PEG-M is obtained in good yield by the liquidphase peptide synthesis. Gel permeation chromatography reveals that aggregated forms of the PEG-bound peptides are absent in CHCl3. CD and IR spectra point to a β-turn located at the N-terminal part of SP-PEG-M. In binding studies and in vivo assays the described compounds are devoid of biological activity.
NOTIZEN: Mono-, Di- und Trichloracetylditolylund -dicyclohexylphosphane / Mono-, Di- and Trichloroacetylditolyland -dicyclohexylphosphanes
Authors: Lindner Ekkehard , Merkle Ralf Dieter
Published: March 2015

Reaction of the acid chlorides X1X2X3CC(O)CI (1ax-bz) with the silylphosphanes Me3SiPR2 (2a, b) [R = 4-CH3C6H4 (a), c-C6H11 (b)] results in the for­mation of the mono-, di- and trichloroacetylditolyl- and -dicyclohexylphosphanes X1X2X3CC(O)PR2 (3ax-bz). 3bx-bz are thermally unstable and decompose at 20 °C to give ClP(c-C6H11)2. Stereochemical effects cause the 31P signal in the spectra of the series 3 ax-az and 3bx-bz to shift to higher fields with increasing content of chlorine in the acetyl group.
Darstellung und Molekülstruktur des ersten Thiohydroxyphosphorans / Preparation and Molecular Structure of the First Thiohydroxyphosphorane
Authors: Röschenthaler Gerd-Volker , Bohlen Rainer , Schomburg Dietmar
Published: March 2015

Hydrophosphorane 1 reacts with elementary sul­fur in the presence of triethylamine to yield phosphorane sulfide 4 which is converted by hydrogen chloride into the corresponding acid, thiohydroxy- phosphorane 5. The X-ray structure determination exhibits an almost undistorted trigonal bipyramide, the five membered rings in axial/equatorial positions and the hydrogen in close contact to one axial oxygen.
Elektronenmikroskopische Untersuchung in Hochauflösung an CaTa2O6 und CaTa4O11 — Vergleich mit der rechnerischen Simulation / High Resolution Electron Microscopy Investigation of CaTa2O6 and CaTa4O11 - A Comparison with Calculated Images
Authors: Langenbach-Kuttert B. , Mertin W. , Gruehn R.
Published: March 2015

The phases CaTa2O6 and CaTa4O11 were prepared at high temperature; electron micrographs of their well known structures were taken by high resolution transmission electron m icroscopy. A comparison with simulated images using different values of crystal thickness and defocus shows the validity of the described computation method
Übergangsmetall-substituierte Acylphosphane und Phosphaalkene, VI [1] Phosphaalkenyl-Eisen- und -Rutheniumkomplexe mit Metall-Kohlenstoffkoordination / Transition Metal Substituted Acylphosphines and Phosphaalkenes, VI [1] Phosphaalkenyl Iron and Ruthenium Complexes with Metal-Carbon Coordination
Authors: Weber Lothar , Reizig Klaus , Meine Georg
Published: March 2015

Treatment of the cationic complexes [(η5-C5Me5)M(CO)3]⊕BF4
⊖ (M = Fe, Ru) (1a , b) with the bulky lithium silyl phosphide LiP(Ar')(SiMe3) (Ar' = 2,4,6-tri-fert-butylphenyl) (2) leads to the phosphaalkenyl complexes (η5-C5Me5)(CO)2M - C(OSiMe3) = P ~ Ar' (4a, b). The presence of C = P double bonds in 4a, b was ascertained by 13C- and 31P NMR spectra. The geometry at the C = P bond was also deduced from the analysis o f the NMR spectra (1H , 13C, 31P)
4-AryIazo-3,5-diaminoisoxazoIe: Synthesis and Some Chemical Reactions
Authors: Zayed Ezzat Mohamed , Ghozlan Said Ahmed Soliman
Published: March 2015

Several new isoxazole derivatives were prepared from the newly synthesized 4-arylazo-3,5- diaminoisoxazole
Reaction of Harmidine/Harmaline with BrCN — a Facile Mono- and Di-Bromination at a-Carbon of the Imine Tautomer
Authors: Siddiqui Salimuzzaman , Siddiqui Bina S. , Begum Sabira
Published: March 2015

Reaction of harmidine/harmaline with BrCN has afforded mono- and di-bromo derivatives I and II respectively indicating the substitution of bromine at the α-carbon of imine through its enamine tautomer
Kristallstruktur von RbNaO / Crystal Structure of RbNaO
Authors: Sabrowsky Horst , Vogt-Mertens Petra , Thimm Alfred
Published: March 2015

The colourless compound RbNaO has been prepared as described earlier [1 ], but single crystals were not yet available at that time. N ow its crystal structure was determined by X-ray diffraction techniques. The very hygroscopic RbNaO crystallizes in the tetragonal space group P4/nmm (Z = 2) with the cell parameters a - 406.8(1), c = 649.4(1) pm. The structure was solved from 1031 counter reflections (375 symmetry independent reflections) by using differential Fourier syntheses. Refining gives a least squares residue o f 0.086.

The structure forms an am/-PbFCl-type geom etry with c-centered squares of sodium interspersed by antiparallel ordered pairs of R b-O
Behavioral and hormonal pattern of repeat breeder cows around estrus
Authors: Sood P , Zachut M , Dube H , Moallem U
Published: March 2015

Repeat breeder (RB) cows were compared with normal (CTRL) ones with respect to behavioral estrus intensity, endocrine patterns and concentrations of plasma estradiol, progesterone and LH around estrus, and ovulation timing. A total of 27 and 31 cycles in 12 RB and 18 CTRL cows, respectively, were synchronized by means of the Ovsynch protocol followed by a single PG injection after 7 days. Behavioral estrus and ovulation were observed in 81.5 and 83.8% of the synchronized cycles in the RB and CTRL cows respectively. The RB and CTRL groups had similar estrus durations of 21.4 and 19.6 h respectively, but estrus was more intense in the RB, as indicated by numerically higher overall activity indexes and higher peak neck activity. The interval from PG injection to estrus onset (considered as proestrus) was 8.2 h shorter in RB than in CTRL cows, at 47.9 and 56.1 h respectively (P<0.007), but the average preovulatory follicle size was similar. The estradiol concentration at peak was numerically higher (21%) and the AUC tended to be higher in the RB cows than in the CTRL cows. LH secretion during the period from 18 to 3 h before the LH peak was also lower in RB than in CTRL cows: 2.5 and 4.6 ng/ml respectively (P<0.01). In conclusion, the behavioral estrus was more intense in the RB cows; nevertheless, short proestrus and subdued LH concentrations before the LH peak, which could impair oocyte competence and development, were first reported in RB cows.
Government Health Care Spending and Child Mortality
Authors: Maruthappu Mahiben , Ng Ka Ying Bonnie , Williams Callum , Atun Rifat , Zeltner Thomas
Published: March 2015

BACKGROUND:

Government health care spending (GHS) is of increasing importance to child health. Our study determined the relationship between reductions in GHS and child mortality rates in high- and low-income countries.

METHODS:

The authors used comparative country-level data for 176 countries covering the years 1981 to 2010, obtained from the World Bank and the Institute for Health Metrics and Evaluation. Multivariate regression analysis was used to determine the association between changes in GHS and child mortality, controlling for differences in infrastructure and demographics.

RESULTS:

Data were available for 176 countries, equating to a population of ∼5.8 billion as of 2010. A 1% decrease in GHS was associated with a significant increase in 4 child mortality measures: neonatal (regression coefficient [R] 0.0899, P = .0001, 95% confidence interval [CI] 0.0440–0.1358), postneonatal (R = 0.1354, P = .0001, 95% CI 0.0678–0.2030), 1- to 5-year (R = 0.3501, P < .0001, 95% CI 0.2318–0.4685), and under 5-year (R = 0.5207, P < .0001, 95% CI 0.3168–0.7247) mortality rates. The effect was evident up to 5 years after the reduction in GHS (P < .0001). Compared with high-income countries, low-income countries experienced greater deteriorations of ∼1.31 times neonatal mortality, 2.81 times postneonatal mortality, 8.08 times 1- to 5-year child mortality, and 2.85 times under 5-year mortality.

CONCLUSIONS:

Reductions in GHS are associated with significant increases in child mortality, with the largest increases occurring in low-income countries.
Late Preterm Birth and Neurocognitive Performance in Late Adulthood: A Birth Cohort Study
Authors: Heinonen Kati , Eriksson Johan G. , Lahti Jari , Kajantie Eero , Pesonen Anu-Katriina , Tuovinen Soile , Osmond Clive , Raikkonen Katri
Published: March 2015

OBJECTIVES:

We studied if late preterm birth (34 weeks 0 days–36 weeks 6 days of gestation) is associated with performance on the Consortium to Establish a Registry for Alzheimer’s Disease Neuropsychological Battery (CERAD-NB) in late adulthood and if maximum attained lifetime education moderated these associations.

METHODS:

Participants were 919 Finnish men and women born between 1934 and 1944, who participated in the Helsinki Birth Cohort Study. They underwent the CERAD-NB at a mean age of 68.1 years. Data regarding gestational age (late preterm versus term) were extracted from hospital birth records, and educational attainment data were gathered from Statistics Finland.

RESULTS:

After adjustment for major confounders, those born late preterm scored lower on word list recognition (mean difference: –0.33 SD; P = .03) than those born at term. Among those who had attained a basic or upper secondary education, late preterm birth was associated with lower scores on word list recognition, constructional praxis, constructional praxis recall, clock drawing, Mini–Mental State Examination, and memory total and CERAD total 2 compound scores (mean differences: >0.40 SD; P values <.05), and had a 2.70 times higher risk of mild cognitive impairment (Mini–Mental State Examination score: <26 points) (P = .02). Among those with tertiary levels of education, late preterm birth was not associated with CERAD-NB scores.

CONCLUSIONS:

Our findings offer new insight into the lifelong consequences of late preterm birth, and they add late preterm birth as a novel risk factor to the list of neurocognitive impairment in late adulthood. Our findings also suggest that attained lifetime education may mitigate aging-related neurocognitive impairment, especially among those born late preterm.
Checklist of horse flies (Diptera: Tabanidae) from Taquaruçu, Tocantins, Brazil, with new records for the state
Authors: Lima Helena Iris Leite de , Krolow Tiago Kütter , Henriques Augusto Loureiro
Published: March 2015

A list of horse fly species is presented for the district of Taquaruçu, Palmas, Tocantins, Brazil . A total of 34 species and three varieties were recorded over one year of collections. From those, 21 species and one variety were new records for the state.
Pemetrexed and Gemcitabine Versus Carboplatin and Gemcitabine in Non-Small Cell Lung Cancer: A Randomized Noninferiority Phase II Study in One Center
Authors: Branden Eva , Hillerdal Gunnar , Kolbeck Karl , Koyi Hirsh
Published: March 2015

Author Summary

Background.

The standard treatment for non-small cell lung cancer (NSCLC) stages IIIb and IV is a platinum compound combined with a third-generation cytotoxic agent. We decided to conduct a phase II study to assess whether the platinum compound could be replaced with pemetrexed with similar results and without an increase in side effects.

Methods.

Consecutive eligible patients were randomized to either the standard arm of gemcitabine plus carboplatin (GC) or the experimental arm of gemcitabine plus pemetrexed (GP).

Results.

Fifty evaluable patients were enrolled in the GC arm, and 44 received GP. There were 10 partial responses in the GC arm and 16 in the GP arm. With GC, mean survival was 9 months compared with 15 months with GP. The side effects were similar in both groups.

Conclusion.

Pemetrexed can replace platinum compounds in the first-line treatment of stage IIIb and IV NSCLC without increasing the side effects. A trend toward better survival was observed in the patients receiving pemetrexed instead of a platinum compound, and this should be studied further.
Anisotropic silver nanoparticles deposited on zeolite a for selective Hg2+ colorimetric sensing and antibacterial studies
Authors: Khorshidi Alireza , Heidari Behrooz , Inanlu Hamidreza
Published: March 2015

Silver nanoparticles deposited on the surface of zeolite A were prepared via
post ion-exchange reduction, and reduction-deposition methods. Formation of
the silver nanoparticles on the surface of zeolite A was verified by surface
plasmon spectra using diffuse reflectance spectroscopy and
ultraviolet-visible spectroscopy. Morphology of the prepared samples was
characterized by X-ray diffraction and scanning electron microscopy.
Furthermore, silver nanoparticles deposited on the zeolite A, after fixation
of Rhodamine B dye molecules over themselves, were successful in detecting
Hg2+ ions selectively. After treatment with the so-obtained sensor, color
change from colorless to pink was visible to the naked eye for the Hg2+
solution concentrations down to 1.0?10-8 mol.L-1. Antibacterial tests
demonstrated the multifunctional application of the silver nanoparticles
deposited on zeolite A.
Comparison of LMS adaptive beamforming techniques in microphone arrays
Authors: Bjelic Milos , Stanojevic Miodrag
Published: March 2015

This paper discusses principles of microphone array beamforming, specifically
the use of LMS algorithm with training sequence. The problem of wideband
nature of acoustical signals and its impact on the techniques of beamforming
are discussed. Detailed explanation of classic narrowband and wideband LMS
beamformers is presented, as well as the modification of narrowband algorithm
with pre-steering. Experimental testing and comparison of algorithm
performances was conducted and measurement results are presented. The used
microphone array is part of Br?el & Kj?r acoustical camera, and is comprised
of 18 omnidirectional non-uniformly spaced microphones.
The theorem about the transformer excitation current waveform mapping into the dynamic hysteresis loop branch for the sinusoidal magnetic flux case
Authors: Petrovic Nenad , Pjevalica Velibor , Vujicic Vladimir
Published: March 2015

This paper analyses aspects of the approximation theory application on the
certain subsets of the measured samples of the transformer excitation current
and the sinusoidal magnetic flux. The presented analysis is performed for
single-phase transformer case, Epstein frame case and toroidal core case. In
the paper the theorem of direct mapping the transformer excitation current in
the stationary regime is proposed. The excitation current is mapped to the
dynamic hysteresis loop branch (in further text DHLB) by an appropriate
cosine transformation. This theorem provides the necessary and satisfactory
conditions for above described mapping. The theorem highlights that the
transformer excitation current under the sinusoidal magnetic flux has
qualitatively equivalent information about magnetic core properties as the
DHLB. Furthermore, the theorem establishes direct relationship between the
number of the transformer excitation current harmonics and their coefficients
with the degree of the DHLB interpolation polynomial and its coefficients.
The DHLB interpolation polynomial is calculated over the measured subsets of
samples representing Chebyshev nodes of the first and the second kind. These
nonequidistant Chebyshev nodes provides uniform convergence of the
interpolation polynomial to the experimentally obtained DHLB with an
excellent approximation accuracy and are applicable on the approximation of
the static hysteresis loops and the DC magnetization curves as well.
Hill’s and Huxley’s muscle models - tools for simulations in biomechanics
Authors: Jovanovic Kosta , Vranic Jovana , Miljkovic Nadica
Published: March 2015

Numerous mathematical models of human skeletal muscles have been developed.
However, none of them is adopted as a general one and each of them is
suggested for some specific purpose. This topic is essential in humanoid
robotics, since we firstly need to understand how human moves and acts in
order to exploit human movement patterns in robotics and design human like
actuators. Simulations in biomechanics are intensively used in research of
locomotion, safe human-robot interaction, development of novel robotic
actuators, biologically inspired control algorithms, etc. This paper presents
two widely adopted muscle models (Hill?s and Huxley?s model), elaborates
their features and demonstrates trade-off between their accuracy and
efficiency of computer simulations. The simulation setup contains
mathematical representation of passive muscle structures as well as
mathematical model of an elastic tendon as a series elastic actuation
element. Advanced robot control techniques point out energy consumption as
one of the key issues. Therefore, energy store and release mechanism in
elastic elements in both tendon and muscle, based on the simulation models,
are considered.
Frequency scanning antenna arrays with pentagonal dipoles of different impedances
Authors: Boskovic Nikola , Jokanovic Branka , Nesic Aleksandar
Published: March 2015

In this work we present the benefits of using pentagonal dipoles as radiating
elements instead of classical printed dipoles in the design of frequency
scanning antenna arrays. We investigate how impedance of pentagonal dipoles,
which can be changed in a wide range, influences the overall characteristics
of the uniform antenna array. Some very important antenna characteristics
such as side lobe level, gain and scanning angle are compared for three
different antenna arrays consisting of identical pentagonal dipoles with
impedances of 500 ?, 1000 ? and 1500 ?.
Photoinduced Charge Accumulation in Molecular Systems
Authors: Bonn Annabell G. , Wenger Oliver S.
Published: March 2015

Fuel-forming reactions such as CO2 reduction or water splitting require multiple redox equivalents. When aiming at light-driven production of energy-rich chemicals, nowadays often referred to as solar fuels, it therefore becomes important to master the photoinduced accumulation
of electrons or holes on individual molecular components. Featured in this short review are some of the key molecular systems explored in this emerging field of research. This includes for example a trinuclear Ru(II)-Rh(III)-Ru(III) complex or an Ir(III)-sensitized polyoxotungstate hybrid,
but also several systems in which electron or hole collection occurs at organic moieties such as perylenebis(dicarboximide), quinone-containing or oligotriarylamine-based units. In many cases the photodriven accumulation of charge requires the use of sacrificial electron donors, but there
exist also a handful of studies in which redox equivalents can be accumulated without the use of such additives.
Scientific Basis for Regulatory Decision-Making of Nanomaterials Report on the Workshop, 20–21 January 2014, Center of Applied Ecotoxicology, Dübendorf
Authors: Studer Christoph , Wick Peter , Vermeissen Etienne , Schneider Gregor , Schirmer Kristin , Rothen-Rutishauser Barbara , Nowack Bernd , Kobe Andrej , Kase Robert , Kägi Ralf , Huwyler Jörg , Hoet Peter , Von Goetz Natalie , Gasic Bojan , Aicher Lothar , Walser Tobias
Published: March 2015

The key findings of a workshop jointly organized by the Swiss Centre of Applied Ecotoxicity, the Swiss Centre for Applied Human Toxicology (SCAHT), and the Federal Office of Public Health (FOPH) are summarized and provide a critical analysis of the current regulatory framework for nanomaterials and a snapshot of some hot topics in nanoscience.
The impact of early-summer snow properties on Antarctic landfast sea-ice X-band backscatter
Authors: Paul Stephan , Willmes Sascha , Hoppmann Mario , Hunkeler Priska A. , Wesche Christine , Nicolaus Marcel , Heinemann Günther , Timmermann Ralph
Published: March 2015

Up to now, snow cover on Antarctic sea ice and its impact on radar backscatter, particularly after the onset of freeze/thaw processes, are not well understood. Here we present a combined analysis of in situ observations of snow properties from the landfast sea ice in Atka Bay, Antarctica, and high-resolution TerraSAR-X backscatter data, for the transition from austral spring (November 2012) to summer (January 2013). The physical changes in the seasonal snow cover during that time are reflected in the evolution of TerraSAR-X backscatter. We are able to explain 76-93% of the spatio-temporal variability of the TerraSAR-X backscatter signal with up to four snowpack parameters with a root-mean-squared error of 0.87-1.62 dB, using a simple multiple linear model. Over the complete study, and especially after the onset of early-melt processes and freeze/thaw cycles, the majority of variability in the backscatter is influenced by changes in snow/ice interface temperature, snow depth and top-layer grain size. This suggests it may be possible to retrieve snow physical properties over Antarctic sea ice from X-band SAR backscatter.
Eyes at the Back of His Head: Precarious Masculinity and the Modern Tracking Shot
Authors: Barker Jennifer M. , Cottrel Adam
Published: March 2015

This paper examines masculinity in relation to the modern tracking shot in Daren Aronofsky's The Wrestler (2008) and Derek Cianfrance's The Place Beyond the Pines (2012). These films make prominent use of a particular tracking shot in which the camera floats behind a male character, his head neatly centred in the frame. The camera in these ‘follow-shots’ seems unmistakably but loosely tethered to the character's body. This paper attempts to ascertain the phenomenological nature and critical significance of that relationship, which in recent films expresses the intimate distance and dissonance between mobile cameras, masculinity and the male body in the twenty-first century.
Unsettling Perception: Screening Surveillance and the Body in Red Road
Authors: Watkins Liz
Published: March 2015

The association of colour, sensation and the body, which is noted by Jacqueline Lichtenstein and Merleau-Ponty through their insights on colour as the disturbing of structure and form, offers a way in which to foreground a series of questions about embodiment and the discourse of vision. An analysis of the chromatics of Red Road (Dir. Andrea Arnold, UK/Denmark, 2006), which features a female protagonist who works as a surveillance officer in a CCTV control room, offers a way to echo and disrupt the ‘mechanisms and techniques of reality-control’ (de Lauretis 1984, 84) and to challenge what constitutes socially acceptable bodies and the cinematic institution of the image of woman. In Red Road the legible architecture of the film image emerges through the myriad colours of light reflected by a camera lens and the effacement of details in areas affected by shadow and variations in focus. The camera is almost always in motion and responsive to the gestures of the protagonist's body, signalling the potential of the chromatics of Red Road to trouble the structures of seeing familiar to cinematic representation. Colour and perception remain open to contingency and change, fostering alternative subject positions that trace the interrelations of the body — its senses and sensations — and the discourse of vision. The unsettling of perception refigures the encounter between the self and others through the imaginary or fictional worlds that remind us of the uncertainties and vulnerability of such interactions.
TNFR1 and TNFR2 Expression and Induction on Human Treg Cells from Type 1 Diabetic Subjects
Authors: Heinrich Melanie , Burger Douglas , Wang Limei , Tahhan Georges , Reinhold Peter , Zhao Menghan , Hsu Elise , Warden Sarah , Baum Danielle , Faustman Denise
Published: March 2015

Several autoimmune diseases are marked by a deficiency of soluble tumor necrosis factor (TNF). The TNF deficiency is caused in at least one autoimmune disease, multiple sclerosis, by an overabundance of TNF receptor 1 (TNFR1). Excess TNFR1 binds and inactivates TNF and this leaves less TNF bioavailable. This study sought to determine if expression of fresh or IL2-stimulated TNF receptors on Tregs cells, an important immunoregulatory cell involved in autoimmunity, is altered in type I diabetes. Standard fluorescence analysis was used to examine the levels of TNFR1 and TNFR2 on human Tregs in patients with type I diabetes (T1D) or controls. Fresh Tregs from T1D compared to control Tregs had identical levels of TNFR1. In marked contrast, Type 1 diabetic patients Treg cells had statistically elevated levels of TNFR2 compared to controls. Tregs stimulated with IL2 from both T1D and controls showed marked increase of TNFR2 expression in a dose-response manner, but the dose response increase in TNFR2 was significantly higher for T1D Treg cells. No IL2 dose-response was present for TNFR1 on either T1D or control Tregs exposed to IL2. A large study of serum for secreted levels of TNFR2 also revealed elevated circulating levels consistent with the elevated surface expression on Tregs. These findings suggest that abnormal regulation of TNFR2 expression with elevated cellular and secreted levels of TNFR2 is a characteristic of Type 1 diabetes. It is possible that the relative deficiency of TNF in type I diabetes, in contrast to multiple sclerosis, is caused by excess expression of TNFR such as TNFR2, a binding structure for inactivating TNF.
The Microbiome and Sustainable Healthcare
Authors: Dietert Rodney , Dietert Janice
Published: March 2015

Increasing prevalences, morbidity, premature mortality and medical needs associated with non-communicable diseases and conditions (NCDs) have reached epidemic proportions and placed a major drain on healthcare systems and global economies. Added to this are the challenges presented by overuse of antibiotics and increased antibiotic resistance. Solutions are needed that can address the challenges of NCDs and increasing antibiotic resistance, maximize preventative measures, and balance healthcare needs with available services and economic realities. Microbiome management including microbiota seeding, feeding, and rebiosis appears likely to be a core component of a path toward sustainable healthcare. Recent findings indicate that: (1) humans are mostly microbial (in terms of numbers of cells and genes); (2) immune dysfunction and misregulated inflammation are pivotal in the majority of NCDs; (3) microbiome status affects early immune education and risk of NCDs, and (4) microbiome status affects the risk of certain infections. Management of the microbiome to reduce later-life health risk and/or to treat emerging NCDs, to spare antibiotic use and to reduce the risk of recurrent infections may provide a more effective healthcare strategy across the life course particularly when a personalized medicine approach is considered. This review will examine the potential for microbiome management to contribute to sustainable healthcare.