A Green's function approach to the photoelectron spectrum of bis(π-allyl)nickel[1]

The vertical ionization potentials of bis(-allyl)nickel (see (1) in Fig. 1) are calculated by means of the Green's function approach within a semiempirical INDO extension to the first transition metal series. The computed ionization potentials are in good agreement with an experimentally deduced assignment. In contrast to earlier theoretical and experimental studies, the 7a _u () level is predicted on top of the levels corresponding to the Ni 3d orbitals. Our approach leads to a complete assignment of the PE spectrum of (1) in the outer valence region.     

51VNMR研究磷钼钒系杂多酸的热稳定性

用NMR及IR、TG-DTA等手段研究具有Keggin结构的磷钼钒系杂多酸在空气中的热稳定性。实验结果表明:合成的杂多酸在各个Keggin单元中具有不同的钒含量。样品的热稳定性与其钒含量有关.随着钒含量的增加,keggin结构的热稳定性逐渐降低,但H_4PMo_(11)V_1O_(40)具有比H_3PMo_(12)O_(40)还要高的热稳定性。由于钒的取代,钼钒磷酸的热分解过程不同于钼磷酸。失去结构水使Keggin结构遭到破坏,但在室温下与水重新作用可使钼钒磷酸的Keggin结构恢复。     

Borchelate und Bormetallchelate, 4. Mitt.

The i.r., u. v.,¹H n.m.r.,¹³C n.m.r., and¹¹B n.m.r. spectra of several substituted diphenylboron chelates derived from salicylaldehyde azomethines were compared with respect to the influence of the amine substituentR. O–B–N-6-ring constitution of the chelates29–32 [R=OH, NH₂, NHC₆H₅, N(CH₃)₂] can be deduced from the spectra.

Als 3. Mitt. gilt:F. Umland undE. Hohaus mit Beiträgen vonW. Riepe, K. Brodte, C. Schleyerbach undD. Szonn. Untersuchungen über borhaltige Ringsysteme vom Chelattyp. Forschungsbericht des Landes Nordrhein-Westfalen Nr. 2538. Opladen: Westdeutscher Verlag. 1976.     

Determination of phenol and catechol concentrations with oxygen probes coated with immobilized enzymes or immobilized cells

The enzyme phenol 2-hydroxylase was immobilized on Sepharose and used in conjunction with an O₂ electrode for quantitating phenol. Similarly, catechol 1,2-oxygenase was used for quantitating catechol. A third probe was prepared by immobilization ofTrichosporon cutaneum cells rather than purified phenol 2-hydroxylase for phenol quantitation. The whole cell system gave results comparable to the immobilized enzyme system.     

MSINDO study of water adsorption on NiO surfaces

The dissociation of water adsorbed on the surface of NiO was investigated by using the semi-empirical SCF MO method MSINDO. Simulations were based on embedded cluster models representing the (100) surface, with and without a monatomic step. The angle formed between the metal adsorption site and the O–H bond associated with water has been found to be critical to the energetics of the dissociation process. Based on this criterion, it was shown that water dissociation is favorable on the stepped surface, but highly unlikely on the planar surface. In addition, the activation energy required for water dissociation in a monatomic NiO step was considerably lower than for dissociation at the planar surface. The high activation energy associated with water dissociation on the planar surface is attributed to the rigidity of the NiO lattice. Dedicated to Prof. K. Jug in honor of his 65th birthday     

THE POLYMERIZATION OF AROMATIC AND HETEROCYCLIC DINITRILES

This review is a concise survey about the works in our laboratory on the polymerization of aromatic and heterocyclic dinitriles, including the polymerization kinetics and mechanism, synthesis of heterocyclic dinitriles, the structure of polymers, and the correlation between the structures of dinitriles and polymerization rates and thermal performances of Polymers.     

Effect of iron-containing catalysts on thermal decomposition of cured GAP-AP propellants

The effects of various burning rate catalysts on thermal decomposition of cured glycidyl azide polymer (GAP)-ammonium perchlorate (AP) propellants have been studied by means of thermal analysis and a modified vacuum stability test (MVST). Four types of iron-containing catalysts examined in this paper are catocene, ferrocenecarboxaldehyde (FCA), ferrocene, and ferric oxide. Results of differential thermal analysis (DTA) and thermogravimetric analysis (TG) revealed that the catalysts play an important role in the decomposition of both AP and GAP. The peak decomposition temperature (T _m) of DTA curves and onset decomposition temperature (T _o) of TG patterns considerably shifted to a lower temperature as the concentration of catalysts increased in the propellants. The endothermic temperature of AP, however, is unaffected by the presence of burning rate catalysts in all cases. The activation energy of decomposition of the propellants in range of 80 to 120°C is determined, based on the MVST results.     

Decomposition of hexafluoropropylene oxide in a strong IR field

Multiphoton dissociation (MPD) of hexafluoropropylene oxide (HFPO) under focused CO₂-laser radiation was studied. A high-energy channel of HFPO decomposition was revealed. The dependences of the MPD yield and the ratio between various channels of HFPO decomposition on the laser radiation frequency in the range from 967.7 to 1090.0 cm^–1, the incident radiation energy, and the initial pressure of HFPO were obtained. A considerable contribution of thermal decomposition of HFPO occurring outside of the irradiated zone to the total yield of its decomposition was established. An explanation for the pressure dependence of the yield of HFPO decomposition was suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2174–2180, November, 1995.The authors are grateful to the Russian Foundation for Basic Research for financial support of this work (Project No. 94-03-09059).     

Phase equilibria in the ternary system PbO−P2O5−PbCl2

Journal of Thermal Analysis and Calorimetry - In the ternary system PbO?P2O5?PbCl2, the partial ternary system Pb5Cl2O4?Pb3Cl2O2?Pb10(PO4)6Cl2 was examined by thermal,...     

Photo-initiated base-formation in a polymer matrix

It was found that amines were formed efficiently by the photolysis of O-acyloximes followed by hydrolysis in polystyrene films and the relationship between structures of O-acyloximes and yields of amines were investigated. O-phenylacetyl acetophenone oxime (PaApO), O-pivaloyl acetophenone oxime (PApO), and O-benzoyl acetophenone oxime (BApO) as monofunctional O-acyloximes and O,O′-succinyl diacetophenone oxime (SDApO) and O,O′-glutaryl diacetophenone oxime (GDApO) as bifunctional O-acyloximes were examined. The yields of amines for PaApO and SDApO under N₂ were ca. 70%, which was the highest among O-acyloximes examined in this experiment. On the other hand, the yields for PApO, BApO, and GDApO were less than 15% and it was verified that the hydrogen abstraction by imino radicals via 6-membered cyclic intermediates resulted in the lowering of yields. Although the effect of oxygen under photolysis on the yields of amine for PaApO was negligible under 50% conversion of PaApO, the yield decreased with further increase in the conversion and was 50% at 90% conversion. © 1994 John Wiley & Sons, Inc.