Kombination wirksamer Trennverfahren mit modernen analytischen Methoden in der Naturstoffchemie

Zusammenfassung Aus Crotonöl konnten durch Anwendung multiplikativer Verteilungs- und chromatographischer Verfahren die entzündlichen und cocarcinogenen Substanzen A1–A4 und B1–B7 rein dargestellt werden. Diese Substanzen sind Diester des polyfunktionellen Diterpenalkohols Phorbol, C₂₀H₂₈O₆ mit jeweils einer kurzkettigen (Essig-, (+)-S-2-Methylbutter-, Tiglinsäure) und einer langkettigen Fettsäure (Capryl-, Caprin-, Laurin-, Myristin-, Palmitinsäure). Die Teilsynthese einiger Substanzen wird angegeben. Aus den UV-, IR- und KMR-Daten und chemischen Befunden werden Teilformeln für Phorbol abgeleitet und diskutiert.

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Summary The compounds A1–A4 and B1–B 7 have been isolated from croton oil in pure state by multiplicative distribution and chromatography. These compounds are di-esters of the polyfunctional diterpene alcohol phorbol C₂₀H₂₈O₆ each with a short chain (acetic-, (+)-S-2-methyl-butanoic-, tiglic acid) and a long chain fatty acid (octanoic-, decanoic-, dodecanoic-, tetradecanoic-, hexadecanoic acid). The partial synthesis of some compounds is described. From ultraviolet-, infrared-, nmr-spectra and from chemical evidence partial structures for phorbol are being discussed.

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Für die Messung von KMR-, Massen- und CD-Spektren und anregende Diskussionen danken wir den Herren Dr. J. Sonnenbichler, München, Dr. J. Jochems, Heidelberg, Dr. A. Mannschreck, Heidelberg, Dr. H. Budzikiewicz, Braunschweig, Dipl.-Chem. C. Wünsche, Heidelberg, Doz. Dr. G. Snatzke, Bonn, und V. Scheidel, Heidelberg.

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Vorgetragen von H. Kubinyi.     

Spin squeezing and quantum correlations

We discuss the notion of spin squeezing considering two mutually exclusive classes of spin-s states, namely, oriented and non-oriented states. Our analysis shows that the oriented states are not squeezed while non-oriented states exhibit squeezing. We also present a new scheme for construction of spin-s states using 2s spinors oriented along different axes. Taking the case of s=1, we show that the ‘non-oriented’ nature and hence squeezing arise from the intrinsic quantum correlations that exist among the spinors in the coupled state.     

The gallium-site donors germanium and silicon in gallium phosphide

The node in the Bloch part of the electron wave function expected for a Ga-site donor in GaP removes the usual valley-orbit splitting and associated chemical shift. However, the T₂ ground state can still show a small spin-valley splitting into Γ₈ and Γ₇ states, as previously verified for the Sn donor. We find that the optical properties of the Ge and Si donors deviate appreciably from this “normal” behaviour. The Ge donor is anomalously deep, E_D ～ 202 meV, yet binds an exciton by ～63 meV consistent with the Haynes rule for neutral donors in GaP. We find that this exciton possesses the large oscillator strength, f～3.5 × 10^-3, Zeeman and piezo-optical splittings characteristic of a Γ₆, 1s(A₁) ground state, like a P rather than Ga-site donor. However, f and the exciton localization energy are consistent with expectation for E_D ～ 200 meV, as measured from the lowest set of X conduction band minima, if we assume a symmetric A₁-like wave function. A possible explanation for this unexpected result is advanced. The much shallower Si donor, E_D～82 meV, binds an exciton by only ～ 14 meV, also consistent with the Haynes rule. By contrast, we find this Ga-site donor to be normal except that our Zeeman and piezo-optical results indicate an inverted spin-valley splitting, about 25% of that for the still shallower Sn donor. We also discuss the numerous low-lying excited states, some anomalous phonon replicas in the Ge and Si donor bound exciton spectra and the magneto-optical properties of a sharp line near 2.24 eV, attributed to the decay of excitons bound to (S)_p-(Ge)_p donor-acceptor associates.     

Theory of sheath in a collisional multi-component plasma

The aim of this brief report is to study the behaviour of sheath structure in a multi-component plasma with dust-neutral collisions. The plasma consists of electrons, ions, micron size negatively charged dust particles and neutrals. The sheath-edge potential and sheath width are calculated for collisionally dominated sheath. Comparison of collisionless and collisionally dominated sheath are made.     

Effect of variability in level on forward masking and on increment detection

In the first of four experiments, all with the same four subjects, varying the level of a forward masker from interval to interval in a two-interval forced-choice (2IFC) adaptive procedure had little effect on threshold. In the second experiment, the signal level was fixed and performance was measured in units of d'. Varying the level of the forward masker again had little effect. Analyses of trial-by-trial data indicated that subjects did not vote for the interval with the higher-level masker, as would an energy detector. Performance was better on trials where the masker level in the interval with the signal was lower and was relatively independent of masker level in the nonsignal interval. In the third experiment, these results were replicated for a wider range of masker variability and with maskers lower in frequency than the signal. In the fourth experiment, the same range of variability from interval to interval was imposed on the level of the pedestal in an increment-detection task. Results were similar to those observed in forward masking. The results suggest that decision processes involved in both forward masking and increment detection are similar and that neither is based on energy detection. Template matching remains a viable alternative.     

Analysis of a shielded TE011 mode composite dielectric resonator for stable frequency reference

Analysis of a TE₀₁₁ mode composite sapphire-rutile dielectric resonator has been carried out to study the temperature variation of resonance frequency, close to the Cs atomic clock hyperfine frequency of 9.192 GHz. The complementary behavior of dielectric permittivity with temperature of the composite has been exploited to obtain the desired turning point in the resonant frequency. The frequency of the composite structure is found to be independent of the shield diameter beyond four times the puck diameter.     

Wideband ipsilateral measurements of middle-ear muscle reflex thresholds in children and adults

The goals of the current study were to: 1) evaluate the feasibility of a new wideband approach to measuring middle-ear muscle reflex (MEMR) status, and 2) to test the hypothesis that ipsilateral thresholds elicited with 1 or 2 kHz tones and broadband noise activators on a wideband acoustic transfer function (WATF) system are lower than thresholds elicited on a clinical system. Clinical MEMR tests have limitations, including the need for high activator levels to elicit a shift in a narrowband probe (e.g., a 0.226 or 1 kHz tone). Wideband MEMR tests using WATFs may elicit the reflex at lower levels because a wideband probe (click) is used and the threshold detection criterion can be wideband. Mean wideband MEMR thresholds across 40 normal-hearing adult ears were 2.2-4.0 dB lower than clinical MEMR thresholds, depending on the activator and specific WATF test used (admittance magnitude or energy reflectance). Wideband MEMR has potential clinical utility beyond the adult population, including use in newborn and preschool hearing screenings. In a newborn hearing screening, for example, wideband MEMR could be completed with the same system as otoacoustic emissions. However, further investigations in infants and young children are needed.     

Simultaneous recording of stimulus-frequency and distortion-product otoacoustic emission input-output functions in human ears

Stimulus frequency otoacoustic emission (SFOAE) input-output (I/O) functions were elicited in normal-hearing adults using unequal-frequency primaries in equal-level and fixed-suppressor level (Ls) conditions. Responses were repeatable and similar across a range of primary frequency ratios in the fixed-Ls condition. In comparison to equal-frequency primary conditions [Schairer, Fitzpatrick, and Keefe, J. Acoust. Soc. Am. 114, 944-966 (2003)], the unequal-frequency, fixed-Ls condition appears to be more useful for characterizing SFOAE response growth and relating it to basilar-membrane response growth, and for testing the ability to predict audiometric thresholds. Simultaneously recorded distortion-product OAE (DPOAE) I/O functions had higher thresholds than SFOAE I/O functions, and they identified the onset of the nonlinear-distortion mechanism in SFOAEs. DPOAE threshold often corresponded to nonmonotonicities in SFOAE I/O functions. This suggests that the level-dependent nonmonotonicities and associated phase shifts in SFOAE I/O functions were due to varying degrees of cancellation of two sources of SFOAE, such as coherent reflection and distortion mechanisms. Level-dependent noise was observed on-band (at the frequencies of the stimuli) but not off-band, or in the DPOAEs. The variability was observed in ears with normal hearing and ears with cochlear implants. In general, these results indicate the source of the variability is biological, possibly from within the middle ear.     

Use of stimulus-frequency otoacoustic emission latency and level to investigate cochlear mechanics in human ears

Stimulus frequency otoacoustic emission (SFOAE) sound pressure level (SPL) and latency were measured at probe frequencies from 500 to 4000 Hz and probe levels from 40 to 70 dB SPL in 16 normal-hearing adult ears. The main goal was to use SFOAE latency estimates to better understand possible source mechanisms such as linear coherent reflection, nonlinear distortion, and reverse transmission via the cochlear fluid, and how those sources might change as a function of stimulus level. Another goal was to use SFOAE latencies to noninvasively estimate cochlear tuning. SFOAEs were dominated by the reflection source at low stimulus levels, consistent with previous research, but neither nonlinear distortion nor fluid compression become the dominant source even at the highest stimulus level. At each stimulus level, the SFOAE latency was an approximately constant number of periods from 1000 to 4000 Hz, consistent with cochlear scaling symmetry. SFOAE latency decreased with increasing stimulus level in an approximately frequency-independent manner. Tuning estimates were constant above 1000 Hz, consistent with simultaneous masking data, but in contrast to previous estimates from SFOAEs.