The ionization energies of bent and twisted double bonds. Part II. Tricyclo[4.2.2.22,5] Dodecadiene-1 (2),5 (6)

The electronic structure of the title compound (1) has been investigated using He(Iα) PE spectroscopy and assuming the validity of Koopmans' theorem. It is found that: (a) in analogy to the situation prevailing in the cyclophanes, hyperconjugation of the out-of-phase linear combination of the π-orbitals with the ethano-bridge σ orbitals is symmetry-forbidden; (b) in agreement with the ideas developed in Part I of this series [1], the strong local B_1u-type bending of the ethylene moieties does not affect their basis energy significantly; and (c) the “through-space” coupling of the two double-bond π orbitals is of the same order as the benzene π-orbital coupling in [2ⁿ] cyclophanes, even if the net contribution to the repulsion of the two double bonds is probably small. Because of the near degeneracy of the HOMO and HOMO — 1 of 1, the ground state of the radical cation 1⁺ cannot be determined uniquely: it is either²A_g or²B_1u.     

Field-theoretic Weyl Quantization as a Strict and Continuous Deformation Quantization

For an arbitrary (possibly infinite-dimensional) pre-symplectic test function space the family of Weyl algebras , introduced in a previous work [1], is shown to constitute a continuous field of C^*-algebras in the sense of Dixmier. Various Poisson algebras, given as abstract (Fréchet-) ^*-algebras which are C^*-norm-dense in , are constructed as domains for a Weyl quantization, which maps the classical onto the quantum mechanical Weyl elements. This kind of a quantization map is demonstrated to realize a continuous strict deformation quantization in the sense of Rieffel and Landsman. The quantization is proved to be equivariant under the automorphic actions of the full affine symplectic group. The relationship to formal field quantization in theoretical physics is discussed by suggesting a representation dependent direct field quantization in mathematically concise terms. Communicated by Joel FeldmanSubmitted 07/10/03, accepted 07/11/03     

The Role of the Cricothyroid Joint Anatomy in Cricothyroid Approximation Surgery

Objectives/Hypothesis

Cricothyroid approximation (CTA) surgery aims at raising the voice pitch in male-to-female transsexuals. However, 30% of the patients are not satisfied with the result. The purpose of our study was to examine the cricothyroid joint (CTJ) biomechanics and to analyze if (and how) the CTJ anatomy influences the movement of the cricoid and, consequently, the elongation of the vocal fold and the voice pitch after CTA.

Methods

Twenty-four cadaver larynges were examined with high-resolution computerized tomography and MIMICS three-dimensional imaging software (Materialise Interactive Medical Image Control System, Leuven, Belgium). After superimposing the two scans taken in “neutral” and in “CTA” positions, vector geometrical analysis was used to determine the effective rotation axis of the CTJ and to calculate the elongation of the vocal folds after CTA.

Results

Our results showed that the cricoid rotates around an axis, the position of which depends on the anatomical structure of the CTJ. Based on the location of this effective rotation axis, we could distinguish three groups. In group I (N = 13), the rotation axis was located in the lower third; in group II (N = 5), it was located in the middle third; and in group III (N = 6), it was located in the upper third of the cricoid. The elongations of the vocal fold were 12%, 8%, and 3%, in groups I, II, and III, respectively.

Conclusions

The anatomical structure of the CTJ influences directly (1) the position of the effective rotation axis and (2) the elongation of the vocal folds.     

The Electronic Structure of Pentaprismane (C10H10), as Revealed by its Photoelectron Spectrum

The photoelectron (PE.) spectrum of the title compound has been assigned by comparison with the PE. spectrum of cubane ( 2 ), aided by ab initio STO-3G calculations using localized molecular orbitals. On the basis of the information available to date, the most satisfactory orbital sequence, Koopmans theorem implied, is, in descending order of energy: band system : (2e″₂, 3e′₂ 2e″₁, 3e′₁); band system : 3a′₁ (2e′₂, 2a″₂); band : 2e′₁.(Sequence of orbitals in parenthesis uncertain).     

Interaction between Oxygen Lone-Pair Orbitals of Ether and α,β-Unsaturated Ketone Functions in 3,5,6-Trimethylidene-7-oxabicyclo[2.2.1]heptan-2-one and 3,6-Dimethylidene-7-oxabicyclo[2.2.1]heptane-2,5-dione: A PE-Spectroscopic Investigation

Controlled ozonolysis of 2,3,5,6-tetramethylidene-7-oxabicyclo[2.2.1]heptane ( 1 ) afforded 3,5,6-trimethylidene-7-oxabicyclo[2.2.1]heptan-2-one ( 2 ). Ozonolysis of 2 gave a 1:1 mixture of 3,5-dimethylidene-7-oxa-bicyclo[2.2.1]heptane-2,6-dione ( 3 ) and 3,6-dimethylidene-7-oxabicyclo[2.2.1]heptane-2,5-dione ( 4 ). The He(Iα) photoelectron (PE) spectra of 2 and 4 have been recorded. Comparison with the PE data of related systems, and with the result of ab initio STO-3G calculations, confirm the existence of significant through-bond interactions between the oxygen lone-pair orbitals n(CO) of the carbonyl functions and n(O) of the O(7) ether bridge.     

Milch

Ohne Zusammenfassung     

Automated high-performance liquid chromatographic method with column switching for the determination of neurotransmitters and related compounds, ascorbic acid and uric acid in tissue extracts

An automated high-performance liquid chromatographic method with electrochemical and fluorimetric detection and on-line data evaluation is described for the simultaneous measurement of indoleaminergic and catecholaminergic neurotransmitters, some of their metabolites and precursors and ascorbic and uric acids. Deproteinized tissue extracts from the central nervous system or peripheral organs are injected without prior purification (recovery greater than 90%). A switching system enables the compounds to be passed as necessary through one, two or three reversed-phase columns, which are then eluted simultaneously (analysis time 25 min). Fifty samples per day can be analysed with a precision of 95% for neurotransmitters and about 90% for ascorbic and uric acids.