Stereochemistry of Polynuclear Cadmium(II)thioglycolates: Crystal Structure of [ICd8(SCH2CH2OH)12]3+ · 3I− · H2O

Crystals of the title compound are triclinic, a = 27.87 Å, b = 10.77 Å, c = 12.94 Å, α 73.1°, β 116.1°, γ 120.0°, space group P1 . The structure consists of octanuclear ions: Eight Cd(II) ions are found at the corners of a distorted cube, the center of the cube is occupied by an iodide, the twelve thioglycolate sulfur atoms bridge the twelve edges of the cube thereby forming a distorted icosahedron. Cadmium ions are either five or seven coordinate. The phase problem for this structure was solved using a combination of very high and very low E-values.     

Mechanism of formation of organic carbonates from aliphatic alcohols and carbon dioxide under mild conditions promoted by carbodiimides. DFT calculation and experimental study

Dicyclohexylcarbodiimide (CyN=C=NCy, DCC) promotes the facile formation of organic carbonates from aliphatic alcohols and carbon dioxide at temperatures as low as 310 K and moderate pressure of CO2 (from 0.1 MPa) with an acceptable rate. The conversion yield of DCC is quantitative, and the reaction has a very high selectivity toward carbonates at 330 K; increasing the temperature increases the conversion rate, but lowers the selectivity. A detailed study has allowed us to isolate or identify the intermediates formed in the reaction of an alcohol with DCC in the presence or absence of carbon dioxide. The first step is the addition of alcohol to the cumulene (a known reaction) with formation of an O-alkyl isourea [RHNC(OR')=NR] that may interact with a second alcohol molecule via H-bond (a reaction never described thus far). Such an adduct can be detected by NMR. In alcohol, in absence of CO2, it converts into a carbamate and a secondary amine, while in the presence of CO2, the dialkyl carbonate, (RO)2CO, is formed together with urea [CyHN-CO-NHCy]. The reaction has been tested with various aliphatic alcohols such as methanol, ethanol, and allyl alcohol. It results in being a convenient route to the synthesis of diallyl carbonate, in particular. O-Methyl-N,N'-dicyclohexyl isourea also reacts with phenol in the presence of CO2 to directly afford for the very first time a mixed aliphatic-aromatic carbonate, (MeO)(PhO)CO. A DFT study has allowed us to estimate the energy of each intermediate and the relevant kinetic barriers in the described reactions, providing reasonable mechanistic details. Calculated data match very well the experimental results. The driving force of the reaction is the conversion of carbodiimide into the relevant urea, which is some 35 kcal/mol downhill with respect to the parent compound. The best operative conditions have been defined for achieving a quantitative yield of carbonate from carbodiimide. The role of temperature, pressure, and catalysts (Lewis acids and bases) has been established. As the urea can be reconverted into DCC, the reaction described in this article may further be developed for application to the synthesis of organic carbonates under selective and mild conditions.     

Die umsetzung von azlactonen mit CH-aciden verbindungen. 2. Mitteil

Alkyl cyanoacetate, malonate, acetoacetate and methylsulfonyl acetic acid ethyl ester are acylated by alkylidenazlactones. The acyl compounds easily form alkylideneteramic acids by condensations. The acylcyanoacetates 2 isomerize into aminopyrrolinones 3 via acid catalysis.     

1H and 13C NMR signal assignment of cucurbitacin derivatives from Citrullus colocynthis (L.) Schrader and Ecballium elaterium L. (Cucurbitaceae)

2D NMR-derived 1H and 13C NMR signal assignments of six structurally closely related cucurbitacin derivatives are presented. The investigated 2-O-beta-D-glucopyranosylcucurbitacins I, J, K, and L were obtained from Citrullus colocynthis (L.) Schrader whereas the aglyca cucurbitacin E and I were isolated from Ecballium elaterium L.     

Femtosecond Spectroscopic Studies on the Red Light-Absorbing Form of Oat Phytochrome and 2,3-Dihydrobiliverdin

Abstract— The excited state behavior of the red light-absorbing form of phytochrome (Pr) was studied on the femtosecond time scale. After excitation of Pr with 75 fs laser pulses at 616 nm the kinetics of the transient absorption changes was recorded at selected wavelengths probing mainly the bleaching of the Pr ground-state absorption and the stimulated emission. The kinetic data obtained indicate the population of an excited state with a 3 ps lifetime immediately after excitation. This state precedes the formation of another excited state with a 32 ps lifetime. The decay of the latter state is followed by the appearance of a first product state that is assumed to represent lunii-R. In addition, 2,3-dihydrobiliverdin, which is considered to be an adequate model of the Pr chro-mophore, was included in the femtosecond studies. The absorption difference spectra recorded at various delay times show an immediate bleaching of the ground-state absorption. Simultaneously with bleaching a broad transient absorption appears between 410 and 525 nm. The data analysis yields similar kinetic components as they were observed in the decay of Pr. It is suggested from this finding that within the first tens of picoseconds after excitation the excited-state properties of Pr are mainly determined by the properties of the chromophore itself.     

Vakuumspektrometrische Analyse gepre?ter Stahlsp?ne

Zusammenfassung Die Vakuumspektrometrische Analyse von Stahlspanpreßlingen wird verbessert und ausgedehnt. Es wird das Abfunkverhalten der Preßlinge unter verschiedenen atmosphärischen Bedingungen in der Funkenkammer beschrieben. Der Zusatz von Wasserstoff zum Argon wirkt sich günstig aus, die Reproduzierbarkeit der Abfunkergebnisse ist gut. Unter den angegebenen Bedingungen lassen sich Spanbriketts aus unberuhigten und beruhigten Stählen einwandfrei vakuumspektrometrisch analysieren.Unberuhigte und beruhigte schwefel-bleihaltige Automatenstähle lassen sich ebenfalls analysieren, wenn die Probenvorgeschichte durch starke Warmverformung und Zerspanung, mit anschließender Mischung und Brikettierung der Späne ausgelöscht wird. Neben der Form hat auch die Größe der Mangansulfid-Bleieinschlüsse einen großen Einfluß auf den Zeit-Intensitätsverlauf aller Spektrallinien.

---

Vacuumspectrometric analysis of briquetted steel chips

Improvements on vacuumspectrometric analysis of briquetted steel chips are dealth with. The influence of different atmospheric conditions in the spark chamber on sparking behaviour of briquettes is shown. An addition of hydrogen to the argon gas will give better results, the reproducibility of analysis is very good. A method is given for vacuumspectrometric analysis of briquetted chips, taken from rimming or killed steels.After hot working, milling and briquetting, samples of rimming and killed sulphurized, leaded free-cutting steel can be analysed, too. There is a great influence of the dimension and the shape of the MnS-Pb inclusions on the pre-spark curves.

---

---

Auszug aus der Doktordissertation, Montanistische Hochschule Leoben, 1967.     

Metallophilic interactions in closed-shell copper(I) compounds--a theoretical study

Cuprophilic interactions in neutral perpendicular model dimers of the type (CH3CuX)2 (X = OH2, NH3, SH2, PH3, N2, CO, CS, CNH, CNLi) were analyzed by ab initio quantumchemical methods. The basis set superposition error for the weakly interacting CH3CuX subunits is significant and is discussed in detail. A new correlation-consistent pseudopotential valence basis set for Cu. derived at the second-order M?ller-Plesset level suppresses considerably the basis set superposition error in Cu-Cu interactions compared to the standard Hartree-Fock optimized valence basis set. This allowed the first accurate predictions of cuprophilicity, which has been the subject of considerable debate in the past. The dependence of the strength of cuprophilic interactions on the nature of the ligand X was addressed. The Cu-Cu interaction increases with increasing sigma-donor and pi-acceptor capability of the ligand and is approximately one-third of the well-documented aurophilic interactions. By fitting our potential-energy data to the Hershbach-Laurie equation, we determined a relation between the Cu-Cu bond length and the Cu-Cu force constant; this is important for future studies on vibrational behaviour. The role of relativistic effects on the structure and the interaction energy is also discussed. Finally we investigated cuprophilic interactions in (CH3Cu)4 as a model species for compounds isolated and characterized by X-ray diffraction.     

Preparative high-performance liquid chromatography of peptides on a new reversed-phase packing material, Kromasil C18

Preparative reversed-phase high-performance liquid chromatography has found wide use in the production of peptides for pharmaceutical formulations. Purity of the substance and overall economy of the chromatographic system are the most important criterias. In this sense optimized, silica particles and production process with capability to separately control parameters important to chromatography, are essential to high-performance chromatography. Kromasil C18 packing material was tested and evaluated in respect of its selectivity, flow and pressure properties, resolution, load capacity, recovery, adsorption effects, mechanical strength and chemical degradation.     

Interpolation of operator ideals with an application to eigenvalue distribution problems

We derive results on the interpolation of complete quasinormed operator ideals, mainly for the absolutelyp-summing and thes-number idealsS _p ^s defined by Pietsch. By estimating theK-Functional of Peetre, we get that the interpolation ideal (S _p1 ^s ,S _p2 ^s ),_,p is contained inS _p ^s and is even equal to it in the case of the approximation numbers. A similar fact is proved for absolutely (p, q)-summing operators, interpolating the first index. We show further that the absolutelyp-summing operators onc ₀ are contained in the complex interpolation space ( _p1 (c _o), _p2 (c _o))_[].The previous results are then applied to prove summability properties for the eigenvalues of operators in Banach spaces, which are products ofS _p1 ^s -type and absolutelyp _j -summing operators. Roughly speaking, the summability order is the harmonic sum of thep _i - andp _j -indices, wherep _j 2. In the case of Hilbert spaces, this reduces to the well-known Weyl-inequality. The method uses an abstract interpolation estimate for ideal quasinorms which may be useful also for other operator ideals.