Die Fehlordnung des Natriumazides und deren Einfluß auf die thermische Zersetzung, 4. Mitt.: Über die Programmierung von Zersetzungsreaktionen mit Hilfe von Korngrößenverteilungen

It is shown that in the case of thermal decomposition of sodium azide the overall kinetics can be predicted by defined particle size of the decomposed sodium azide crystals. This is always the case if the rate constant is a function of the particle size. Hence this special example can be generalized for similar decomposition reactions. It is necessary that the particles decompose independently which could be proved experimentally with sodium azide. If for this reason we state for true that the pressure/time-function of each particle size add together it is possible to set up a formula for the pressure/time-function of any particle size distribution. With the pressure/time function holding for sodium azide of uniform particle size, the total function for a Gauß distribution can be calculated exactly. Moreover, the trivial case of one single particle size and the case of two different particle sizes are discussed. Furthermore an approximation method for any arbitrary pressure/time-functions and distribution by means of “Schwerpunktdeutung” are discussed which can be carried out graphically as well as numerically. The numerical approximation is illustrated by an example. Pressure/time-functions then loose their characteristic form because of their dependence on the particle size distributions under consideration. In this case, reaction mechanism cannot be derived from pressure/time functions.     

Investigations in the fie ld of substituted furanurona ldehydes steric directivity of the nitromethane condensation

Summary 1. The condensation of the anomeric methyl 2,3-di-O-benzyl-D-xylofuranosiduronaldehydes with nitromethane has been studied.2. It has been shown that the position of the substituent at the glycosidic center has an influence on the steric directivity of this reaction.3. The structure of the 6-nitro-6-deoxyhexofuranosides synthesized has been confirmed by their conversion into known derivatives of methyl D-glucofuranosides.Translated from Khimiya Prirodnykh Soedinenii, No. 1, pp. 8–12, January–February, 1972.     

Die Kristallstrukturen der Diquecksilber(I)-Salze von Aminobenzolsulfonsäuren

Crystal Structures of Dimercuri (I) Salts of p- and m-Sulfanilic Acids The crystal structures of the compounds Hg₂(p-H₂N–C₆H₄–SO₃)₂ ( 1 ), Hg₂(m-H₂N–C₆H₄–SO₃)₂ ( 2 ), and Hg₂(m-H₂N–C₆H₄–SO₃)₂ · 2H₂O ( 3 ) contain leaf-structures ( 1 and 3 ) or chain-structures ( 2 ), with nearly linear groups N–Hg–Hg–N, Hg–O-contacts and hydrogen-bridging bonds. The smaller density of 3 compared with 1 –caused by the steric hindrance through the ligand – declared the incorporation of water for raising the stabilising interaction in the crystals. The compound 3 is the kinetic controlled, the compound 2 the thermodynamic controlled product.     

Thiophosphinatokomplexe der Lanthanoiden. II. Dicyclohexylthiophosphinatokomplexe des NdIII und ErIII

Thiophosphinate Complexes of Lanthanides. II. Molecular Structures of [Nd((cyclo-C₆H₁₁)₂POS)₃(H₂O)]₂ and NH₄[Er((cyclo-C₆H₁₁)₂POS)₄(H₂O)₂] The title compounds are formed by the reaction of NH₄((C₆H₁₁)₂POS) and Ln(ClO₄)₃ (Ln ? Nd³⁺, Er³⁺). Their structures have been determined by single crystal X-ray diffraction. In the dimeric compound, the (C₆H₁₁)₂POS^? ions act partly as bidentate chelates and partly as monodentate O-donors. The dimers are formed by doubly coordinating oxygen atoms of two ligands. In the ionic compound, Er is only sixfold (octahedrally) coordinated by the oxygen atoms of 4 ligands and two water molecules. The structures of so far known thiophosphinate complexes of lanthanides are discussed with respect to stereochemistry and ligand bonding.     

Kalorimetrische messungen zur ermittlung der spezifischen grenzflächenenergie einer zweiphasigen Cu-7,5 At.-% In-legierung

With the help of a commercial heat-flux calorimeter the enthalpy change was measured as a function of the interlamellar spacing for lamellar precipitated Cu-In samples. This is related to the replacement of the two-phase structure (α + δ) by the homogeneous solid solution (α₀. From this, the specific interfacial enthalpy of the α-δ interface was determined to be ΔH^δ = 1100 ± 550 mJ m^?2. A value of ΔH^c = 1320 ± 60 J mol^?1 results for the chemical part of the total measured transformation enthalpy. A value of ΔS^δ = 0.66 mJ m^?2 K^?1 was estimated for the specific interfacial entropy and using the Gibbs-Helmholtz equation the specific interfacial free energy was calculated as ΔG^δ = 700 ± 400 mJ m^?2 at 600 K.     

Dynamic and structural models of pyrimidine in the lowest excited singlet state

Problems on the normal vibrations of pyrimidine in the ground and excited states are solved. The matrices of rotation and shift of normal coordinates due to electronic excitation and Franck-Condon integrals are calculated. The vibronic spectra of pyrimidine are interpreted. Based on this interpretation, bond lengths and bond angles in the electronically excited first singlet state of the molecule are calculated: C₁C₂ 1.388 å, C₂N₃ 1.366 å, N₃C₄ 1.352 å, C-H 1.099 å; C₆C₁C₂ 105.5?, N₃C₄N₅ 127.8?, H₂C₂N₃ 110.1?.     

Comparison of formats for the development of fiber-optic biosensors utilizing sol-gel derived materials entrapping fluorescently-labelled protein

The development of fiber-optic biosensors requires that a biorecognition element and a fluorescent reporter group be immobilized at or near the surface of an optical element such as a planar waveguide or optical fiber. In this study, we examined a model biorecognition element-reporter group couple consisting of human serum albumin that was site-selectively labelled at Cys 34 with iodoacetoxy-nitrobenzoxadiazole (HSA-NBD). The labelled protein was encapsulated into sol-gel derived materials that were prepared either as monoliths, as beads that were formed at the distal tip of a fused silica optical fiber, or as thin films that were dipcast along the length of a glass slide or optical fiber. For fiber-based studies, the entrapped protein was excited using a helium-cadmium laser that was launched into a single optical fiber, and emission was separated from the incident radiation using a perforated mirror beam-splitter, and detected using a monochromator-photomultiplier tube assembly. Changes in fluorescence intensity were generated by denaturant-induced conformational changes in the protein or by iodide quenching. The analytical parameters of merit for the different encapsulation formats, including minimum protein loading level, response time and limit-of-detection, were examined, as were factors such as protein accessibility, leaching and photobleaching. Overall, the results indicated that both beads and films were suitable for biosensor development. In both formats, a substantial fraction of the entrapped protein remained accessible, and the entrapped protein retained a large degree of conformational flexibility. Thin films showed the most rapid response times, and provided good detection limits for a model analyte. However, the entrapment of proteins into beads at the distal tip of fibers provided better signal-to-noise and signal-to-background ratios, and required less protein for preparation. Hence, beads appear to be the most viable method for interfacing of proteins to optical fibers.     

Reactions of dithiocarbamic acids derived from alkaloids, morpholine, and piperidine with acrylic acid and its derivatices

-(Thiocarbamoylthio)propionic acids derived from alkaloids, morpholine, and piperidine and their esters, amides, and nitriles were prepared by reactions of the corresponding dithiocarbamic acids with acrylic acid and its derivatives. Some of the compounds were tested for insecticidal activity.Translated from Zhurnal Prikladnoi Khimii, Vol. 77, No. 8, 2004, pp. 1336–1339.Original Russian Text Copyright © 2004 by Zhivotova, Gazaliev, Ibraev, Fazylov, Kasenov.     

Regioselective hydroborations of methylvinylchlorosilanes

The regioselectivity of the hydroboration of the methylchlorovinylsilanes, Cl_nMe_3?nSiCHCH₂ (n= 0 ? 3), has been investigated using BH₃←THF, 9-BBN, disiamyl- and dicyclohexylborane. Methylation of the adducts with methylmagnesium bromide is complicated by formation of tetraalkylboronates. Alkaline hydrogen peroxide oxidation of the boronates gives reasonable yields of the corresponding α- and β-trimethylsilylethanols forn= 0 and 1. Forn= 2 and 3, conversion of the adducts to the corresponding α- and β- deuteroethylsilanes by treatment with excess sodium methoxide in methanol-0-d provides a more effective means of derivatization. Addition of the alkenes,n= 2 or 3, to excess BH₃←THF givesca. 90% of the α-boro-organo-chlorosilanes. For all of the alkenes, the dialkylboranes giveca. 80% of the β-boron adducts.     

The study of coordinative interaction in the organoaluminium derivatives of substituted phenols

Intramolecular coordination in dimethylaluminium phenoxides (with an ortho-substituted ring) was investigated. Only strongly donating groups in the phenoxy ring (COOMe) displayed strong intramolecular coordination. All compounds investigated formed donor-acceptor complexes with hexamethylphosphoramide (HMPA). Dimethylaluminium methylsalicilate coordinated HMPA without splitting the intramolecular carbonyl oxygen—aluminium bond, which suggests formation of the pentacoordinated aluminium atom.