bluuebunny/crossref_metadata_2025 huggingface dataset:
Kinetische Analyse zur Umwandlung von Oxirenen oder Thiirenen und ihren offenkettigen Valenzisomeren / Kinetic Analysis for the Conversion of Oxirenes or Thiirenes and their Open-Chain Valence Isomers
Authors: Meier Herbert , Kolshorn Heinz
Published: February 2015

Ring closure and ring opening reactions possess an outstanding significance for the formation and reactivity of antiaromatic heterocycles like oxirenes and thiirenes. The valence isomerisations 2 ⇆ 1 ⇆ 2' can be controlled by the product distribution 2 → P/2' → P'. A quantitative interpretation of many experimental data, published in the last years, is given on the basis of a few kinetic models, which consider thermal and photochemical pathways. Possible energy profiles of single hypersurfaces (S0 or S1) and the transition between different hypersurfaces (S1 → S0) are the most important features of these models.
Some Extensions of von Braun (BrCN) Reaction on Organic Bases
Authors: Siddiqui Salimuzzaman , Siddiqui Bina S.
Published: February 2015

von Braun Cyanogen Bromide Reaction Some extensions of von Braun cyanogen bromide reaction have been undertaken on conessine, isoconessine and two simpler bases, dimethyl a-naphthyl amine and diethyl amine. The monocyanamides of conessine and isoconessine yielded acid amides, amino-derivatives (diamines) and guanido derivatives on careful hydrolysis, reduction and treat-ment with ammonia, respectively. The simpler bases also formed the acid amides and dia-mines but failed to give the guanido derivatives under the conditions employed for conessine series. Diamines of all these bases yielded carbinol amines on reaction with nitrous acid.
Mesylhydroxylamine, III [1]. Über die Reaktion von Mesylfluorid mit Hydroxylamin / Mesylhydroxylamines, III [1]. The Reaction of Methane Sulfonyl Fluoride and Hydroxylamine
Authors: Brink Klaus , Bliefert Claus
Published: February 2015

In the reaction of CH3SO2F with hydroxylamine the products CH3SO2N(H)OH, H3NOH+CH3SO3-, and H5N2+CH3SO3- are formed. H2NO-Si(CH3)3 reacts with CH3SO2F to yield mainly H5N2
+CH3SO3_. These results are explained by consecutive reactions of the intermediate CH3SO2ONH2.
Chemisches Verhalten des Siliziumoxidfluorids F3SiOSiF3 / Chemical Behaviour of the Silicon Oxide Fluoride F3SiOSiF3
Authors: Jacob Eberhard
Published: February 2015

The stability of (SiF3)2O and the chemical behaviour with HF and CsF has been described. The reactivity of hexafluorodisiloxane with various strongly oxidizing fluorides (XeF6, XeF4, XeF2, KrF2, IF7, BrF5, ClF5, ClF3, ClF, UF6) and oxide fluorides (XeOF4, ClO2F) was investigated, particularly with respect to the preparation of oxide fluorides such

XeF6 + (SiF3)2O → XeOF4 + 2 SiF4(I)

in comparison to hydrolysis reactions with H2O or SiO2/HF. In summary, all the studied compound react more slowly with (SiF3)2O than with H2O. The reaction (1) can be recommended as a safe procedure to prepare XeOF4. By heating a mixture of UF6 and (SiF3)2O uranium oxide fluorides are obtained. With β-UV irradiation was observed. It is remarkable that many of the investigated fluorides and fluorine oxidize the (SiF3)2O to oxygen. (SiFa3)2O shows no reaction with HF. IF7 catalyzes only the decomposition of (SiF3)2O.
Isolation and Partial Characterization of Adipotropin, an Apparent New Lipolytic Peptide from Bovine Anterior Pituitary Lobes
Authors: O’Malley Karen , Folkers Karl , Trygstad Olav , Foss Irene
Published: February 2015

A peptide, apparently new, has been isolated from the anterior lobes of bovine pituitary glands by the following steps: (1) lyophilization of frozen tissue; (2) homogenization; (3) extraction with an aqueous buffer; (4) gel filtration; (5) anion and then (6) cation exchange chromatography; (7) HPLC. One antioxidant and two proteolytic inhibitors were present during buffer extraction to avoid artifactual reactions. Amino acid analyses consistently revealed the same amino acids and no others on different specimens, one year apart. The composition was estimated as: 4 Asp, 2 Thr, 5 Ser, 8 Glu(x), 5 Pro, 10 Gly, 4 Ala, 2 Val, 2 Met, 1 Ile, 2 Leu, 1 Tyr, 1 Phe, 2 His, 3 Lys, 2 Arg (5600 daltons). Cysteine and tryptophan were absent. An approximate molecular weight by gel filtration was 7200 daltons. The isoelectric point was 6.1. The peptide showed a dose-response activity in the range of 0.001-1.0 μg in a rabbit adipose system, in vitro. The peptide is tentatively designated as adipotropin, because it has no unequivocal chemical relation­ship to other relevant lipolytic peptides, and because it has the highest molar potency, in vitro, of these peptides, including pACTH.
Kernresonanzspektroskopische Untersuchungen an t-Butyl-phenyl-phosphinsäure-(—)-menthylester, II [1]1H-, 13C-und 31P-NMR-Analyse der absoluten Konfiguration am Phosphoratom / NMR Spectroscopic Investigations on t-Butyl-phenyl-phosphinic Acid(—)-Menthyl Ester, II [1] 1H, 13C and 31P NMR Analysis of Absolute Configuration at the Phosphorus Center
Authors: Hägele Gerhard , Wendisch Detlef , Luckenbach Reiner , Bechtolsheimer Hans-H.
Published: February 2015

(-)-Menthol, Diastereomeric Menthylesters of Phosphinic Acids, 31P NMR Spectra, 13C NMR Spectra, Double Resonance

(-)-Menthol and diastereomeric (-)-menthyl esters of t-butyl-phenyl-phosphinic acid are investigated by means of 1H, 13C and 31P NMR at 2.1 and 8.4. Tesla double resonance experiments are described.
Die Kristallstruktur des Bis (1,2-diaminoethan)-kupfer(II)-diiodocuprats (I), [Cu(H2NCH2CH2NH2)2(CuI4/2)2] / The Crystal Structure of [Cu(H2NCH2CH2NH2)2(CuI4/2)2]
Authors: Freckmann Bernhard , Tebbe Karl-Friedrich
Published: February 2015

The copper complex [Cu(en)2(Cu I4/2)2] crystallizes monoclinically in the space group C2/m with a = 1039.4(4) pm, b = 1337.5(3) pm, c = 656.7(2) pm, β = 117.51(2)° and Z = 2 formula units. The crystal structure is built up by cations [Cu(II)(en)2]2+ and anionic chains of edge-sharing tetrahedra [Cu(I) I1/2
-]n which are weakly connected by a short distance d(Cu(II) ··· I) = 340.2 pm.
Synthese S-substituierter Benzile und einiger gehinderter Biphenyle [1] / Synthesis of S-Substituted Benzils and Some Hindered Biphenyls [1]
Authors: Lüdersdorf Reinhard , Mai Jürgen , Praefcke Klaus
Published: February 2015

Three methylthio and/or methylsulfinyl substituted benzils (2, 6 and 7) have been synthesized on photo-or thermochemical routes, respectively. Photodecarboxylation of some new different substituted mesityl benzoates (1 a-e) leads to hindered biphenyls (3 a-e) accompanied sometimes by aldehyde (4a-c) and benzil formation (2) due to compatitive a-cleavage and subsequent stabilization processes of such generated free aroyl radicals. A short summary on constitutional conditions for intramolecular photoredox reactions of ortho functionalized aryl sulfinyl compounds is presented.
Konkurrenzreaktionen bei [3+2]-Cycloadditionen [1] Abfangreaktionen von Nitril-yliden mit 1.1-Diphenylethylen [2] / Competition between [3+2] Cycloaddition and 1,3-Addition Reactions [1] Trapping Reactions of Nitrile Ylides with 1,1-Diphenylethylene [2]
Authors: Burger Klaus , Goth Herbert , Roth Wolf-Dieter
Published: February 2015

Trapping reactions of bis(trifluoromethyl) substituted nitrile ylides with 1,1-diphenylethylene are described. Two regioisomeric [3 + 2] cycloadducts, and an open chain product can be isolated. The product ratio was found to be dependent on solvent polarity.
Neuartige Cycloaddition eines Benzocyclobutadiens mit Dienophilen A New Cycloaddition of a Benzocyclobutadiene with Dienophiles / A New Cycloaddition of a Benzocyclobutadiene with Dienophiles
Authors: Straub Henner , Miller Bernd
Published: February 2015

trans -1,2 -Dicy ano -and tetracyanoethylene add to 1,2-di-tert-butyl-3,4,5,6-tetramethyl-benzocyclobutadiene (1b) neither angular nor linear but give the bridged compounds across the six-membered ring 2 b and 3 b respectively.
Photoinduzierte Wasserstoffübertragungs - reaktionen der chlorierten Octahydro-1.4-endo, endo-5.8-dimethanonaphthaline / Photoinduced Hydrogentransferreactions of Chlorinated Octahydro-1,4-endo, endo-5,8-dimethanonaphthaline
Authors: Parlar H. , Korte F.
Published: February 2015

Photokinetic experiments show that a series of chlorinated octahydro-1,4-endo, endo-5,8-dimethanonaphthaline (1-4) react intramolecular and via tripletstate to their photoisomers (1 a-4a). The formation of the compounds 1 a-4a is dependent on oxygen and nature of sensitizers.
Platinum Blues - a Study of the Interaction between Potassium Tetrachloroplatinate and Asparagine
Authors: Arrizabalaga Philippe , Castan Paule , Laurent Jean-Pierre
Published: February 2015

Potassium tetrachloroplatinate and asparagine form a paramagnetic complex in aqueous solution. This complex which displays a blue green color has been studied by ESR and IR spectroscopy. The ESR spectra are interpreted to be due to tervalent platinum in a low spin d7 configuration. The IR data suggest that the doubly deprotonated ligand is coordinated through the COO- and CONH- groups.
Darstellung und Charakterisierung von Monoorganobismut(III)-und Bismut(III)-Derivaten von Mercaptocarbonsäuren /Preparation and Characterization of Monoorganobismuth(III) and Bismuth (III) Derivatives of Mercaptocarbonic Acids
Authors: Praeckel Udo , Huber Friedo
Published: February 2015

Cleavage of Bi-C-bonds in Ph3Bi (Ph = C6H5) by mercaptocarboxylic acids (H2Mc) depends on solvents and concentration. Ph3Bi in CHl3 and H2MC (= mercaptoacetic, 3-and 2-mercaptopropionic, 2-mercaptobenzoic acid) reacted to give Bi(Mc)(HMc); in acetone at lower concentrations PhBi(Mc) (H2Mc =2-mercaptopropionic, 2-mercaptobenzoic acid) was obtained. Me3Bi (Me = CH3) and H2Mc gave MeBi(Mc) at all concentrations used. Polymeric structures with bridging Mc-groups and four-coordinated Bi are proposed.
Metallomethane, IV [1] Molekül-und Kristallstruktur von Bis(chloroquecksilber)metlian CH2(HgCl)2 / Metallomethanes, IV [1] Molecular and Crystal Structure of Bis(chloromercuri)methane CH2(HgCl)2
Authors: Jensen Klaus-Peter , Breitinger Dietrich K. , Kreß Wolfram
Published: February 2015

The X-ray structure analysis of bis(chloromercuri)methane CH2(HgCl)2 has been performed. CH2(HgCl)2 crystallizes in Prnma with a = 713.7(4) pm, b - 643.6(4) pm, c = 1221.7(8) pm, Z = 4; the isotypic CH2(HgBr)2 has a = 731.1(3) pm, b = 668.6(1) pm, c - 1260.1(4) pm. The CH2(HgCl)2 molecules (site symmetry m) contain asymmetric CHg2 entities with bond lengths R(C-Hg(l)) = 203.9(17) pm and R(C-Hg(2)) = 212.2(18) pm, respectively, whereas the two independent Hg-Cl bonds are almost the same (average (Hg-Cl) = 233.3(5) pm). The bond angles Hg-C-Hg (111.6(3)°) and C-Hg-Cl (average 177.8(5)°) fall into the expected range. The molecules are held together by two independent systems of short van der Waals contacts Cl →···Hg forming zig-zag chains along the 6-axis, and a wide variety of van der Waals interactions Cl →···Hg in planes parallel to (010). The arrangements in these planes produce maximum density molecular layers with coordination number six; including the molecules of two adjacent layers each molecule reaches a total coordination number of fourteen. Depending on the van der Waals radius assumed for mercury a packing coefficient 0.663 ≤ k ≤ 0.733 comparable to that of close-packing of spheres results.
ÜbergangsmetaU-Schwefelylid-Komplexe, XI [1] Struktur und Reaktivität von n5 -Thiacyclohexadienyl-1-oxid-chrom-KompIexeii / Transition Metal Sulfur Ylide Complexes, XI [1] Structure and Reactivity of n5-Thiacyclohexadienyl-1-oxide Complexes of Chromium
Authors: Weber Lothar , Vehreschild-Yzermann Dorothee , Krüger Carl , Wolmershäuser Gotthelf
Published: February 2015

The X-ray crystal and molecular structure of tetraethylammonium-tricarbonyl-(3,5-diphenylthiacyclohexadienyl-1-oxide)chromate has been determined. This organo-metallic anion can be nitrosylated to yield neutral [n5-C5H3(C6H5)2SO](CO)2(NO)Cr. Further carbonyl displacement in this compound is achieved by treatment with pyridin or phosphanes in the presence of triethylamineoxide.
Alkoxohalogenotellurate(IV): Darstellung und Struktur von Tetraphenylphosphonium-trichloro(dioxo-ethylen-O.O')tellurat(rV) / Alkoxohalogenotellurates(IV): Preparation and Structure of Tetraphenylphosphonium Trichloro(dioxo-ethylene-O,O')tellurate(IV)
Authors: Büscher Klaus , Heuer Susanne , Krebs Bernt
Published: February 2015

The deprotonated glycolate dianion (OCH2CH2O)2- is shown to react as a bidentate chelating ligand towards chalcogen(IV) halides. With TeCl4, the anion TeCl3(O2C2H4)- is formed. According to a single crystal X-ray analysis of the tetraphenylphosphonium salt (P21/c, a = 7.501, b = 26.328, c = 13.582 A, β= 104.55°, Z = 4) Te is in a tetragonal pyramidal (ψ octahedral) coordination with the alcoholate ligands in the apical (Te-O 1.919 Å) and in one of the equatorial positions (Te O 1.973 Å), the Te-Cl bond lengths being between 2.495 and 2.590 Å. The trans bond lengthening effect of the equatorial alcoholate ligand (i.e. the polarizing effect towards the lone pair) is unusually low. Vibrational spectra are reported.
UV Photoelectron Spectra of Some Bent Bis(η5 -cyclopentadienyl) Niobium and Tantalum Complexes
Authors: Dam Henk van , Terpstra Andries , Oskam Ad , Teuben Jan H.
Published: February 2015

He(I) and He(II) photoelectron spectra are reported for (η5-C5H5)2MLX (M = Nb, Ta; L = H, CO; X - propene, 1-butene, propyl) and some methylcyclopentadienyl deriva-tives. Also the spectra of some π-allyl and dihalide complexes are reported. Unambiguous assignments could be made of the metal d a1 orbital, the Cp orbitals, the olefin π ionization and the M-hydride and π-allyl orbitals. Very regular trends are observed in the ionization energies upon substitution of the ligands. The olefin π ionization is found at very low energy indicating that the π backbonding to the olefin is very important. He(I)/He(II) cross section differences show clearly differences in metal character of the various M.O.'s.
Cyclisation of 1-Phenyl-4-carboxymethylmercapto-5-arylazo-hydantoins
Authors: Shalaby A. F. A. , Aziz M. A. Abdel , Boghdadi S. S. M.
Published: February 2015

Abstract 1

-Phenyl-4-carboxymethylmercapto-5-arylazo-hydantoin derivatives (3a-f) were cyclised with acetic anhydride to give the bicyclic products (4a-f). Compounds 4 a, b condensed with aromatic aldehydes in acetic acid and in presence of anhydrous sodium acetate yielding the corresponding arylidene derivatives (5a-c). Compounds 4a, b also couple with aryldiazonium salts to give the expected coloured arylazo compounds (6a-j). 4 a, b reacted with formaldehyde and primary aromatic amines in ethanol to give the corresponding Mannich bases (7a-f).
Beiträge zur Synthese von Cystinpeptiden, dargestellt am Beispiel der Totalsynthese von Humaninsulin* / Contributions to the Synthesis of Cystine Peptides Illustrated by the Total Synthesis of Human Insulin
Authors: Kamber Bruno
Published: February 2015

The formation of disulfide bonds in separate chemical steps in a cystine peptide containing several cystine residues is exemplified by the synthesis of human insulin. The synthetic methods which made this approach feasible were 1) the thiol-induced fragmentation of sulfenyl thiocarbonate derivatives and 2) the conversion of S-trityl- and S-acetamidomethyl cysteine peptides to cystine peptides by oxidation with iodine.
Isolierung von Dihydrokämpferol aus Silybum marianum L. Gaertn. / Isolation of Dihydrokaempferol from Silybum marianum L. Gaertn.
Authors: Kaloga Macki
Published: February 2015

Dihydrokaempferol ((2R, 3R)-2-(4-Hydroxy-phenyl)-3,5,7-trihydroxy-4-chromanon) has been isolated from the fruit of Silybum marianum L. Gaertn. and identified by UV, CD, MS and PMR spectra.
Schwefel-Stickstoff-Verbindungen, VIII. Darstellung und Charakterisierung einiger aromatischer Schwefeldiimide / Sulfur-Nitrogen-Compounds, VIII Synthesis and Characterization of Some Aromatic Sulfurdiimines
Authors: Brands Gilbert , Golloch Alfred
Published: February 2015

The missing compounds of the series of sulfurdiimines R1 - N = S = N-R2 with R1/2 = C6H5, C6F5, C6H5S, C6F5S were prepared, and all ten compounds investigated. Thermal stability, UV/VIS-, IR-and 19F-NMR-spectra depend strongly on the combination of the substituents
Studien über Wespengift, I Niedermolekulare Bestandteile des Giftblasenextraktes von Paravespula vulgaris / Studies on Wasp Venom, I Low Molecular Weight Constituents of Venom Sac Extracts from Paravespula vulgaris
Authors: Klein Hartmut , Francke Wittko , König Wilfried A.
Published: February 2015

Low molecular weight constituents of 3400 venom sacs of Paravespula vulgaris were extracted with water, diluted acetic acid, and methanol. After conversion to volatile derivatives carbohydrates, amino acids, fatty acids, other constituents of phospho lipids, and biogenic amines were identified by gas chromatography and mass spectrometry. Quantitative analysis was achieved for amino acids by amino acid analysis and for glucose by an enzymatic assay. Results are discussed with regard to biosynthesis of wasp toxins and phylogenetic aspects of hymenopteran venoms.
Notizen: Über Erdalkalimetalloxogallate, IX Zum Aufbau von β-SrGa2O4/ Oxogallates of Alkaline Earth Metals, IX The Structure of β-SrGa2O4
Authors: Schulze A.-R. , Müller-Buschbaum Hk.
Published: February 2015

Abstract β-SrGa2O4 was prepared and investigated by X-ray single crystal methods. It crystallizes with monoclinic symmetry: C2h
5-P21/c, a - 839.2; b = 901.8; c = 1069.7 pm; β = 93.9°, Z - 8. The orientation of the tetrahedra is discussed in comparison with other well-known members of the stuffed tridymite structure.
Stability Constants of Metal Ion Complexes of Cyclopentadienyltris(diethylphosphito-P)cobaltate(1-), [(C5H5)CO{P(O)(OC2H5 )2 }3 ]-, an Oxygen Tripod Ligand
Authors: Anderegg Giorgio , Kläui Wolfgang
Published: February 2015

The formation of metal ion complexes ML(n-1)+ and ML2
(n-2)+ of the oxygen tripod ligand L- = cyclopentadienyltris(diethylphosphito-P)cobaltate(l-) with metal ions Mn+ = Li+, Na+ , K+ , Mg2+ , Ca2+ , Sr2+ , Ba2+ , Mn2+ , Co2+ , Ni2+ , Cu2+ , Zn2+ ,Cd2+ , Hg2+ , Pb2+ , Ag+ ,and La3+ has been studied by pH titration at 25 °C in 95/5 methanol/water solutions kept at an ionic strength of 0.1 by means of tetramethylammonium chloride. The stability of the alkali metal ion complexes increases with decreasing metal ion radii. The sodium complex NaL is more stable than the known crown ether sodium complexes. The K1 values of the transition metal complexes ML+ are ≈ 109 [1/mol]. For H+ , Na+, Mg2+ , and La3+ the enthalpies and entropies of complex formation have been determined by calorimetric measurements. The results are comparable to those of the tripolyphosphate anion. The complex formation is slightly endothermic and the stability of the complexes arises from a large positive ⊿S of reaction.
Untersuchungen an quartären Pyridinium-Salzen, XIV Dihydropyridyl-oximether/Investigations of Quaternary Pyridinium Salts, XIV Dihydropyridyl-oxime-ethers
Authors: Gündel Wolf-H.
Published: February 2015

Pyridinium Salts with electron-withdrawing groups in the 3-position react with aliphatic ketoximes under basic conditions to lipophilic addition products, 6-(alkylideniminoxy)-1,6-dihydropyridines.
Notizen:The Reaction of Dithiocarboxylic Acids with Imines
Authors: Ishida Masaru , Kato Shinzi , Mizuta Masateru
Published: February 2015

Aromatic dithiocarboxylic acids 1 react with imines 4 to give the corresponding adducts 5, aminomethyl dithiocarboxylates, in good yields. The adducts 5 react with phenacyl bromide to give the corresponding phenacyl dithiocarboxy-lates 6.
Darstellung und Eigenschaften der ferf-ButyHminovanadin(V)-Verbindungen tC4H9N =VX3 (X = Cl, RCOO) / Synthesis and Properties of Jerf -Butylimino vanadium (V) Compounds tC4H9N = VX3 (X = Cl, RCOO)
Authors: Preuss Fritz , Towae Willi
Published: February 2015

1C4H9N = V(OSiMe3)3 has been prepared by reaction of NH4VO3 with HNSiMe3(tC4H9). This compound is the starting material for the synthesis of C6H5N = V(OSiMe3)3 and tG4H9N = VCl3 by transamination with aniline or redistribution with VOCl3, respectively. The properties of the trichloride are studied by chemical reactions such as redistribution, complex formation and substitution with silver carboxylates. All compounds are mono-meric in solution, probably containing a nitrogen vanadium triple bond. The structure of 2,2'-dipyridyl complexes [tC4H9N = VX3 · C10H8N2] (X = Cl, CH3COO) has been found to be octahedral with meridional arrangement of chloride or acetate ligands.
Isolierung und Strukturuntersuchungen an der Ribonuclease T2 aus Aspergillus oryzae, I. / Isolation and Structure Investigations on the Ribonuclease T2 from Aspergillus oryzae, I
Authors: Klemer A. , Künnemeyer H.-M. , Matern H.
Published: February 2015

From aspergillus oryzae extracts via 100 g preparations each 80 mg pure ribonuclease T2 were obtained. The enzyme contains 16-17% carbohydrate (12-13% neutralsugars and 4% glucosamine). G. c. analysis results mannose, glucose, fucose, glucosamine, galactose and xylose in ratio 14:8:6:6:4:1. Proteolytic degradation of the enzyme gave a glyco-peptide with a uniform heteropolysaccharide containing the total carbohydrate amount.
Organoborierung von Alkinylstannanen, XI [1] Synthese von substituierten Alkenen ausgehend von 9-Borabicyclo [3.3.1] nonan-Derivaten / Organoboration of Alkynylstannanes, XI [1] Synthesis of Substituted Alkenes from 9-Borabicyclo[3,3,l]nonane Derivatives
Authors: Bihlmayer Christoph , Wrackmeyer Bernd
Published: February 2015

Organoboration, 9-Borabicyclo[3.3.1]nonanes, NMR Spectra New alkene derivatives are obtained from the reaction between 9-ethyl-borabicyclo-[3.3.1]nonane and alkynyl stannanes under kinetic or thermodynamic control. NMR evidence for a borate type intermediate is presented.
Struktur und Reaktivität von Carbonyl(cyclopentadienyl) (allenyliden) -Komplexen / Structure and Reactivity of Carbonylcyclopentadienylallenylidene Complexes
Authors: Berke Heinz , Huttner Gottfried , Seyerl Joachim v.
Published: February 2015

The X-ray structure of a Dicarbonyl(dicyclohexylallenylidene)(cyclopentadienyl)manganese( I) complex was determined. The reactivity of a variety of nucleophiles, as OCH3-, N(CH3)2-, t-BuS-, P(CeH5)3 and P(C2H5)3, towards Dicarbonyl(methylcyclopentadienyl)- (diorganylallenylidene)manganese(I) compounds was investigated. The addition of anionic bases and subsequent protonation leads to vinylcarbene or vinylidene complexes. Phosphanes result in the attack of the terminal position of the cumulenic chain. An MO explanation for the regioselectivity of the base attack is provided
Die Kinetik und der Mechanismus der thermischen Reaktion zwischen Schwefeltetrafluorid und Fluor / The Kinetics and the Mechanism of the Thermal Reaction between Sulfurtetrafluoride and Fluorine
Authors: Gonzalez Alicia Cristina , Schumacher Hans Joachim
Published: February 2015

The kinetics of the thermal reaction between SF4 and F2 has been investigated between − 2.4 °C and + 24.0 °C, SF6 and very small amounts of S2F10 being the only products. The reaction is a chain reaction of medium length. Total pressure and surface have only insignificant influence.

The reaction rate follows the equation:

Under the experimental conditions less than 15% of the SF5 radicals are consumed by r (4b). Therefore

Oxygen inhibits the reaction eliminating the SF5 radicals, the final products being now SF5O3SF5 and SF6. From the data obtained in the experiments with high oxygen pressures the rate constant of the primary process and the chain length (v) are determined.

E = 10.8 ± 0.7 kcal, E1 = 11.9 ± 0.6 kcal and E4 ≃ 0. E2 = 5.0 ± 2.0 kcal (estimated value) and E3 = 4.7 ± 2.5 kcal.
Käfigverbindungen im System P4S3-As4S3 / Cage Compounds in the System P4S3-AS4S3
Authors: Blachnik R. , Hoppe A. , Rabe U. , Wickel U.
Published: February 2015

Mixtures of P4S3 and As4S3 were investigated. The system reveals a broad metastable region of solid solubility. At the composition PAs3S3 new structures are obtainable after various thermal treatments. In the mixtures six different cage molecules (P4-xAsxS3 (x=1−3)) were found. PAs3S3 is the most stable of the mixed cages. At higher temperature a plastic-crystalline modification, at the composition PAs3S3 two further high temperature modifications are observed. NMR and mass spectra, and d-values of the modifications are reported, and the high temperature behaviour of all mixed cages is described.
Mesylhydroxylamine, V [1] Mehrfach mesylierte N-Mesylhydroxylamine / Mesylhydroxylamines, V Polysubstituted N-Mesylhydroxylamines
Authors: Boldhaus Michael , Bliefert Claus , Brink Klaus , Mattes Rainer
Published: February 2015

The preparation and characterization of the following N-mesylhydroxylamines are reported:

(CH3SO2)2NOSO2CH3 (1), (CH3SO2)2NOCH3 (2),CH3SO2N(CH 3)OSO2CH3 (3),

CH3SO2N(H)OCH3 (4),

Na+CH3SO2NOCH3-·1/2H2O (5),

CH3SO2N(CH3)OCH3 (6).
Darstellung und Kristallstruktur des Cs2S5 · H2O / Synthesis and Crystal Structure of Cs2S5 · H2O
Authors: Böttcher P. , Trampe G.
Published: February 2015

Cs2S5 · H2O has been synthesized from aqueous solutions of Cs2S and stoichiometric quantities of sulfur. Cs2S solutions result from the reaction between Ba(OH)2·8H20, Cs2SO4, and H2S.

Cs2S5-H2O crystallizes triclinicly, space group P1̄ , with Z = 2. The lattice constants are as follows:

a = 6.974(3) Å, b = 7.870(4) Å, c = 10.413(4) Å, α = 108.72(4)°, β = 111,23(4)°, γ = 82,00(4)°.

Characteristic features are the unbranched zig-zag-chains of S5
2- like in other known pentachalcogenides M2X5. Hydrogen bridges occur between the terminal sulfur atoms of the chains and the oxygen atoms of water molecules.
Übergangsmetallkomplexe mit Schwefelliganden, XIII* Synthesen und Reaktionen der 1,2-Benzoldithiolatomolybdat-Komplexe [MO(C6H4S2)3]n- (n = 0, 1, 2) und des Hydrid-Komplexes [Mo(H)(C6H4S2)3]3- / Transition Metal Complexes with Sulfur Ligands, XIII* Syntheses and Reactions of the 1,2-Benzenedithiolato Molybdate Complexes [MO(C6H4S2)3]n- - (n = 0 , 1, 2 ) and the Hydride Complex [Mo(H)(C6H4S2)3]3-
Authors: Sellmann Dieter , Zapf Lothar
Published: February 2015

Modes of formation as well as redox and substitution reactions of the 1,2-benzenedithiolate complexes [Mo(C6H4S2)3]n- (n = 0, 1, 2, (3)) are described. [MoCl4(THF)2] with neutral C6H4(SH)2 gives the Mo(VI) complex [Mo(C6H4S2)3]; with C6H4S2
2-, however, the Mo(IV) complex [Mo(C6H4S2)3]2- can be isolated as the PPh4
+ or NR4
+ salt; in the course of the synthesis of (NMe4)2[Mo(C6H4S2)3] in MeOH/THF, the complex salt trans-(NMe4)2[Mo(C6H4S2)2(OCH3)2] is also obtained. Directly and controlled by pH, [Mo(VI)(C6H4S2)3] can be reduced by NaOH/MeOH to afford [Mo(V)(C6H4S2)3]- or [Mo(IV)(C6H4S2)3]2-. [Mo(VI)(C6H4S2)3] and (NMe4)2[Mo(IV)(C6H4S2)3] symproportionate in MeOH to yield (NMe4)[Mo(V)(C6H4S2)3] , which was isolated for the first time. When butyllithium reacts with [Mo(VI)(C6H4S2)3] in the molar ratio of 1:1, 2 :1 or 3:1, one obtains the Mo(V), Mo(IV) dithiolates or an orange complex, respectively. The latter is extremely H2O - as well as O2-sensitive; it is identified by its reactions with H2O , ROH, O2 , alkyl halides and NO as well as by 1H NMR spectroscopy as a salt containing the [MO(H)(C6H4S2)3]3- anion. [Mo(H)(C6H4S2)3]3- is the first example of an exclusively sulfur coordinated metal hydride complex. With NO it reacts in several steps yielding first N2O and [Mo(IV)(C6H4S2)3]2-; subsequently the Mo(IV) complex is reductively nitrosylated by further NO yielding cis-[Mo(NO)2(C6H4S2)2]2-, which is isolated as NMe4
+ salt.
Shared Neural Markers of Decision Confidence and Error Detection
Authors: Boldt Annika , Yeung Nick
Published: February 2015

Empirical evidence indicates that people can provide accurate evaluations of their own thoughts and actions by means of both error detection and confidence judgments. This study investigates the foundations of these metacognitive abilities, specifically focusing on the relationship between confidence and error judgments in human perceptual decision making. Electroencephalography studies have identified the error positivity (Pe)—an event-related component observed following incorrect choices—as a robust neural index of participants' awareness of their errors in simple decision tasks. Here we assessed whether the Pe also varies in a graded way with participants' subjective ratings of decision confidence, as expressed on a 6-point scale after each trial of a dot count perceptual decision task. We observed clear, graded modulation of the Pe by confidence, with monotonic reduction in Pe amplitude associated with increasing confidence in the preceding choice. This effect was independent of objective accuracy. Multivariate decoding analyses indicated that neural markers of error detection were predictive of varying levels of confidence in correct decisions, including subtle shifts in high-confidence trials. These results suggest that shared mechanisms underlie two forms of metacognitive evaluation that are often treated separately, with consequent implications for current theories of their neurocognitive basis.
Controlling Your Impulses: Electrical Stimulation of the Human Supplementary Motor Complex Prevents Impulsive Errors
Authors: Spieser Laure , van den Wildenberg Wery , Hasbroucq Thierry , Ridderinkhof K. Richard , Burle Borís
Published: February 2015

To err is human. However, an inappropriate urge does not always result in error. Impulsive errors thus entail both a motor system capture by an urge to act and a failed inhibition of that impulse. Here we show that neuromodulatory electrical stimulation of the supplementary motor complex in healthy humans leaves action urges unchanged but prevents them from turning into overt errors. Subjects performed a choice reaction-time task known to trigger impulsive responses, leading to fast errors that can be revealed by analyzing accuracy as a function of poststimulus time. Yet, such fast errors are only the tip of the iceberg: electromyography (EMG) revealed fast subthreshold muscle activation in the incorrect response hand in an even larger proportion of overtly correct trials, revealing covert response impulses not discernible in overt behavior. Analyzing both overt and covert response tendencies enables to gauge the ability to prevent these incorrect impulses from turning into overt action errors. Hyperpolarizing the supplementary motor complex using transcranial direct current stimulation (tDCS) preserves action impulses but prevents their behavioral expression. This new combination of detailed behavioral, EMG, and tDCS techniques clarifies the neurophysiology of impulse control, and may point to avenues for improving impulse control deficits in various neurologic and psychiatric disorders.
Influence of Motivation on Control Hierarchy in the Human Frontal Cortex
Authors: Bahlmann Jörg , Aarts Esther , D'Esposito Mark
Published: February 2015

The frontal cortex mediates cognitive control and motivation to shape human behavior. It is generally observed that medial frontal areas are involved in motivational aspects of behavior, whereas lateral frontal regions are involved in cognitive control. Recent models of cognitive control suggest a rostro-caudal gradient in lateral frontal regions, such that progressively more rostral (anterior) regions process more complex aspects of cognitive control. How motivation influences such a control hierarchy is still under debate. Although some researchers argue that both systems work in parallel, others argue in favor of an interaction between motivation and cognitive control. In the latter case it is yet unclear how motivation would affect the different levels of the control hierarchy. This was investigated in the present functional MRI study applying different levels of cognitive control under different motivational states (low vs high reward anticipation). Three levels of cognitive control were tested by varying rule complexity: stimulus-response mapping (low-level), flexible task updating (mid-level), and sustained cue-task associations (high-level). We found an interaction between levels of cognitive control and motivation in medial and lateral frontal subregions. Specifically, flexible updating (mid-level of control) showed the strongest beneficial effect of reward and only this level exhibited functional coupling between dopamine-rich midbrain regions and the lateral frontal cortex. These findings suggest that motivation differentially affects the levels of a control hierarchy, influencing recruitment of frontal cortical control regions depending on specific task demands.
Pharmacologically Distinct Nicotinic Acetylcholine Receptors Drive Efferent-Mediated Excitation in Calyx-Bearing Vestibular Afferents
Authors: Holt J. Chris , Kewin Kevin , Jordan Paivi M. , Cameron Peter , Klapczynski Marcin , McIntosh J. Michael , Crooks Peter A. , Dwoskin Linda P. , Lysakowski Anna
Published: February 2015

Electrical stimulation of vestibular efferent neurons rapidly excites the resting discharge of calyx/dimorphic (CD) afferents. In turtle, this excitation arises when acetylcholine (ACh), released from efferent terminals, directly depolarizes calyceal endings by activating nicotinic ACh receptors (nAChRs). Although molecular biological data from the peripheral vestibular system implicate most of the known nAChR subunits, specific information about those contributing to efferent-mediated excitation of CD afferents is lacking. We sought to identify the nAChR subunits that underlie the rapid excitation of CD afferents and whether they differ from α9α10 nAChRs on type II hair cells that drive efferent-mediated inhibition in adjacent bouton afferents. We recorded from CD and bouton afferents innervating the turtle posterior crista during electrical stimulation of vestibular efferents while applying several subtype-selective nAChR agonists and antagonists. The α9α10 nAChR antagonists, α-bungarotoxin and α-conotoxin RgIA, blocked efferent-mediated inhibition in bouton afferents while leaving efferent-mediated excitation in CD units largely intact. Conversely, 5-iodo-A-85380, sazetidine-A, varenicline, α-conotoxin MII, and bPiDDB (N,N-dodecane-1,12-diyl-bis-3-picolinium dibromide) blocked efferent-mediated excitation in CD afferents without affecting efferent-mediated inhibition in bouton afferents. This pharmacological profile suggested that calyceal nAChRs contain α6 and β2, but not α9, nAChR subunits. Selective blockade of efferent-mediated excitation in CD afferents distinguished dimorphic from calyx afferents by revealing type II hair cell input. Dimorphic afferents differed in having higher mean discharge rates and a mean efferent-mediated excitation that was smaller in amplitude yet longer in duration. Molecular biological data demonstrated the expression of α9 in turtle hair cells and α4 and β2 in associated vestibular ganglia.
Activity in Human Visual and Parietal Cortex Reveals Object-Based Attention in Working Memory
Authors: Peters Benjamin , Kaiser Jochen , Rahm Benjamin , Bledowski Christoph
Published: February 2015

Visual attention enables observers to select behaviorally relevant information based on spatial locations, features, or objects. Attentional selection is not limited to physically present visual information, but can also operate on internal representations maintained in working memory (WM) in service of higher-order cognition. However, only little is known about whether attention to WM contents follows the same principles as attention to sensory stimuli. To address this question, we investigated in humans whether the typically observed effects of object-based attention in perception are also evident for object-based attentional selection of internal object representations in WM. In full accordance with effects in visual perception, the key behavioral and neuronal characteristics of object-based attention were observed in WM. Specifically, we found that reaction times were shorter when shifting attention to memory positions located on the currently attended object compared with equidistant positions on a different object. Furthermore, functional magnetic resonance imaging and multivariate pattern analysis of visuotopic activity in visual (areas V1–V4) and parietal cortex revealed that directing attention to one position of an object held in WM also enhanced brain activation for other positions on the same object, suggesting that attentional selection in WM activates the entire object. This study demonstrated that all characteristic features of object-based attention are present in WM and thus follows the same principles as in perception.
Melanin-Concentrating Hormone Neurons Release Glutamate for Feedforward Inhibition of the Lateral Septum
Authors: Chee Melissa J.S. , Arrigoni Elda , Maratos-Flier Eleftheria
Published: February 2015

Melanin-concentrating hormone (MCH) regulates vital physiological functions, including energy balance and sleep. MCH cells are thought to be GABAergic, releasing GABA to inhibit downstream targets. However, there is little experimental support for this paradigm. To better understand the synaptic mechanisms of mouse MCH neurons, we performed neuroanatomical mapping and characterization followed by optogenetics to test their functional connectivity at downstream targets. Synaptophysin-mediated projection mapping showed that the lateral septal nucleus (LS) contained the densest accumulation of MCH nerve terminals. We then expressed channelrhodopsin-2 in MCH neurons and photostimulated MCH projections to determine their effect on LS activity. Photostimulation of MCH projections evoked a monosynaptic glutamate release in the LS. Interestingly, this led to a feedforward inhibition that depressed LS firing by a robust secondary GABA release. This study presents a circuit analysis between MCH and LS neurons and confirms their functional connection via monosynaptic and polysynaptic pathways. Our findings indicate that MCH neurons are not exclusively GABAergic and reveal a glutamate-mediated, feedforward mechanism that inhibits LS cells.
DUYGUSAL ZEKA VE ÖRGÜT İKLİMİNE ETKİSİ
Authors: Yılmaz Ceyda , Fidan Yahya , Yıldıran Canan
Published: February 2015

Günümüz kurumları içinde, artık çalışanların sadece IQ düzeylerinin yüksek olması yeterli olmamakta, başarının sağlanmasında çalışanların belirli bir düzeyde duygusal zekâya da sahip olmaları gerekmektedir. Bu nedenle yapılan çalışmanın amacı, kamu kurumlarında duygusal zekâ kavramının varlığının belirlenmesi ve kurumsal duygusal zekânın örgütsel iklime etkisinin ölçülmesidir. Bu amaçla, Karabük ilinde kamu kurumlarında çalışan 180 memurun katılımı ile bir çalışma yapılmıştır. Araştırma sonucunda kamu kurumlarında çalışan memurların duygusal zekâ eğiliminin yüksek olduğu tespit edilmiştir. Bunun sonucu olarak da çalışanların, örgüt ikliminde pozitif davranışlar sergileyerek, örgütün başarısının artmasını sağladıkları anlaşılmıştır.
Intellectual and Academic Functioning of School-Age Children With Single-Suture Craniosynostosis
Authors: Speltz Matthew L. , Collett Brent R. , Wallace Erin R. , Starr Jacqueline R. , Cradock Mary Michaeleen , Buono Lauren , Cunningham Michael , Kapp-Simon Kathleen
Published: February 2015

OBJECTIVE:

We compared the developmental status of school-age children with single-suture craniosynostosis (case group) and unaffected children (control group). Within the case group we compared the performance of children distinguished by location of suture fusion (sagittal, metopic, unicoronal, lambdoid).

METHODS:

We administered standardized tests of intelligence, reading, spelling, and math to 182 case participants and 183 control participants. This sample represented 70% of those tested during infancy before case participants had corrective surgery.

RESULTS:

After adjustment for demographics, case participants’ average scores were lower than those of control participants on all measures. The largest observed differences were in Full-Scale IQ and math computation, where case participants’ adjusted mean scores were 2.5 to 4 points lower than those of control participants (Ps ranged from .002 to .09). Adjusted mean case–control differences on other measures of achievement were modest, although case deficits became more pronounced after adjustment for participation in developmental interventions. Among case participants, 58% had no discernible learning problem (score <25th percentile on a standardized achievement test). Children with metopic, unicoronal, and lambdoid synostosis tended to score lower on most measures than did children with sagittal fusions (Ps ranged from <.001 to .82).

CONCLUSIONS:

The developmental delays observed among infants with single-suture craniosynostosis are partially evident at school age, as manifested by lower average scores than those of control participants on measures of IQ and math. However, case participants’ average scores were only slightly lower than those of control participants on reading and spelling measures, and the frequency of specific learning problems was comparable. Among case participants, those with unicoronal and lambdoid fusions appear to be the most neurodevelopmentally vulnerable.
Child Sex Trafficking and Commercial Sexual Exploitation: Health Care Needs of Victims
Authors: Greenbaum Jordan , Crawford-Jakubiak James E. ,   COMMITTEE ON CHILD ABUSE AND NEGLECT, Christian Cindy W. , Crawford-Jakubiak James E. , Flaherty Emalee G. , Leventhal John M. , Lukefahr James L. , Sege Robert D.
Published: February 2015

This Clinical Report was reaffirmed October 2020.

Child sex trafficking and commercial sexual exploitation of children (CSEC) are major public health problems in the United States and throughout the world. Despite large numbers of American and foreign youth affected and a plethora of serious physical and mental health problems associated with CSEC, there is limited information available to pediatricians regarding the nature and scope of human trafficking and how pediatricians and other health care providers may help protect children. Knowledge of risk factors, recruitment practices, possible indicators of CSEC, and common medical and behavioral health problems experienced by victims will help pediatricians recognize potential victims and respond appropriately. As health care providers, educators, and leaders in child advocacy, pediatricians play an essential role in addressing the public health issues faced by child victims of CSEC. Their roles can include working to increase recognition of CSEC, providing direct care and anticipatory guidance related to CSEC, engaging in collaborative efforts with medical and nonmedical colleagues to provide for the complex needs of youth, and educating child-serving professionals and the public.
El poder en las relaciones de género desde la perspectiva de las mujeres
Authors: Martínez  Esquivel Daniel
Published: February 2015

Introducción. El poder está determinado por las relaciones interpersonales, por tanto, hombres  y mujeres tienen poder. Sin embargo, el poder en el sistema de las mujeres se ve disminuido por la cultura y los valores sociales, lo cual provoca desigualdad e inequidad que afecta directamente su salud mental, al punto de que disminuye su participación y empoderamiento social.Método. La presente investigación buscó responder a la pregunta ¿cuál es la influencia del poder en las relaciones de género de un grupo de mujeres? Para lo cual, se planteó una investigación cualitativa fenomenológica, la muestra se tomó  a conveniencia. En cuanto a los datos, se recolectaron mediante la técnica de grupo focal y su análisis se efectuó desde un enfoque interpretativo que incluyó una triangulación entre la teoría, la información obtenida y la posición del investigador.Resultado. La principal función que ejerce el sistema de las mujeres es el trabajo doméstico, sin embargo, tienen oportunidades de educación y de trabajo. La toma de decisiones se limita al hogar y se da tan solo frente a personas que tienen un rol inferior. Las relaciones interpersonales son buenas siempre y cuando ejerzan un rol de mujer y madre socialmente aceptado.Conclusión. El sistema de mujeres tiene poder pero está determinado por la cultura, de modo que  las mujeres todavía sufren del poder de dominación de la sociedad patriarcal, por tanto, sus oportunidades de desarrollo disminuyen y sus funciones sociales se determinan a partir de su clase, posición en el sistema familiar, educación y producción económica.
Orientation-dependent Pattern Formation in a 1.5D Continuum Model of Curved Dislocations
Authors: Sandfeld Stefan , Verbeke Vanessa , Devincre Benoit
Published: February 2015

Dislocation pattern formation is a phenomenon where during significant plastic deformation dislocations organize themselves into (meta)stable structures. Modeling such systems is a non-trivial task, because the number of interacting dislocations is high, bringing discrete simulation models to their computational limits. Continuum models, although more efficient, generally do not contain sufficient information for a physically detailed representation of such systems. In this paper we show how a continuum dislocation dynamics theory can be used to model idealized pattern formation. Furthermore, we show how discrete dislocation dynamics (DD) simulations can be used to provide physical input for our continuum model.
The trochanter tertius in a dog
Authors: Grandis A. , Spadari A. , Pinna S.
Published: February 2015

The tuberositas glutaea is a rudimentary structure in the dog’s os femoris. It gives attachment to the superficial gluteal muscle, and is known by veterinary anatomists and orthopedic surgeons as trochanter tertius. We report an atypical eminence exposed through a surgical approach on a Cane Corso Dog. Anatomic and radiographic investigations led us to recognize this eminence as an abnormally grown tuberositas glutaea.
Gas consumption forecasting: evidence from the Croatian gas market
Authors: Vištica Nikola , Banovac Eraldo , Pavlović Darko
Published: February 2015

This paper analyses the deviations between nominated and realised gas quantities, for the balancing group consisting of 36 members in the Croatian gas market. The imbalance distribution among the balancing group members regarding the absolute deviation of a single member and the causer–helper principle is presented. In total, 458 calculations using different architectures of artificial neural networks were conducted to complete the research. The combined analysis of accuracy obtained with the best combination of input variables for the defined datasets is presented in this paper. The results are represented according to the multi input multi output (MIMO) and two multi input single output (MISO) architectures used for the day-ahead and intraday forecasts. The results decrease the gap in knowledge in the field of gas consumption forecasting. Furthermore, the accuracy of gas consumption forecasting using different neural network architectures is calculated. There is a clear benefit for balancing group members if they are organised in the balancing group with the aim of calculating the imbalance based on the group effect. Finally, the results show that the deviation tolerances between nominated and realised gas quantities for a single member can be higher compared to the deviation for its balancing group without significant economic penalty for the member.