Highly regioselective Diels-Alder reactions toward oroidin alkaloids: use of a tosylvinyl moiety as a nitrogen masking group with adjustable electronics

[reaction: see text] The use of the p-toluenesulfonyl (Ts) and tosylvinyl (Tsv) groups as nitrogen masking groups imparted high regioselectivity in Diels-Alder reactions directed toward members of the oroidin-derived marine alkaloid family. The electron-withdrawing Tsv group was utilized as an electronically adjustable nitrogen-protecting group as subsequent hydrogenation provided the more electron-rich tosylethyl (Tse) group. This electronic adjustment strategy avoided a protecting group exchange and provided the required electronics for the key chlorination/ring-contraction sequence.     

Identification of a set of genes showing regionally enriched expression in the mouse brain

Background

We have recorded responses from single neurons in murine visual cortex to determine the effectiveness of the input from the two murine cone photoreceptor mechanisms and whether there is any unique selectivity for cone inputs at this higher region of the visual system that would support the possibility of colour vision in mice. Each eye was stimulated by diffuse light, either 370 (strong stimulus for the ultra-violet (UV) cone opsin) or 505 nm (exclusively stimulating the middle wavelength sensitive (M) cone opsin), obtained from light emitting diodes (LEDs) in the presence of a strong adapting light that suppressed the responses of rods.

Results

Single cells responded to these diffuse stimuli in all areas of striate cortex. Two types of responsive cells were encountered. One type (135/323 – 42%) had little to no spontaneous activity and responded at either the on and/or the off phase of the light stimulus with a few impulses often of relatively large amplitude. A second type (166/323 – 51%) had spontaneous activity and responded tonically to light stimuli with impulses often of small amplitude. Most of the cells responded similarly to both spectral stimuli. A few (18/323 – 6%) responded strongly or exclusively to one or the other spectral stimulus and rarely in a spectrally opponent manner.

Conclusion

Most cells in murine striate cortex receive excitatory inputs from both UV- and M-cones. A small fraction shows either strong selectivity for one or the other cone mechanism and occasionally cone opponent responses. Cells that could underlie chromatic contrast detection are present but extremely rare in murine striate cortex.     

Inverse Cerenkov acceleration and inverse free-electron laserexperimental results for staged electron laser acceleration

The goal of the staged electron laser acceleration (STELLA) experiment is to demonstrate staging of the laser acceleration process whereby an inverse free electron laser (IFEL) will be used to prebunch the electrons, which are then accelerated in an inverse Cerenkov accelerator (ICA). As preparation for this experiment, a new permanent magnet wiggler for the IFEL was constructed and the ICA system was modified. Both systems have been tested on a new beamline specifically built for STELLA. The improved electron beam (e-beam) with its very low emittance (0.8 mm-mrad normalized) enabled focusing the e-beam to an average radius (1σ) of 65 μm, within the ICA interaction region. This small e-beam focus greatly enhanced the ICA process and resulted in electron energy spectra that have demonstrated the best agreement to date in both overall shape and magnitude with the model predictions. The electron energy spectrum using the new wiggler in the IFEL was also measured. These results will be described as well as future improvements to the STELLA experiment     

Effects of deafness on acoustic characteristics of American English tense/lax vowels in maternal speech to infants

Recent studies have demonstrated that mothers exaggerate phonetic properties of infant-directed (ID) speech. However, these studies focused on a single acoustic dimension (frequency), whereas speech sounds are composed of multiple acoustic cues. Moreover, little is known about how mothers adjust phonetic properties of speech to children with hearing loss. This study examined mothers' production of frequency and duration cues to the American English tense/lax vowel contrast in speech to profoundly deaf (N?=?14) and normal-hearing (N?=?14) infants, and to an adult experimenter. First and second formant frequencies and vowel duration of tense (/i/,?/u/) and lax (/I/,?/?/) vowels were measured. Results demonstrated that for both infant groups mothers hyperarticulated the acoustic vowel space and increased vowel duration in ID speech relative to adult-directed speech. Mean F2 values were decreased for the /u/ vowel and increased for the /I/ vowel, and vowel duration was longer for the /i/, /u/, and /I/ vowels in ID speech. However, neither acoustic cue differed in speech to hearing-impaired or normal-hearing infants. These results suggest that both formant frequencies and vowel duration that differentiate American English tense/lx vowel contrasts are modified in ID speech regardless of the hearing status of the addressee.     

ULTRASTRUCTURAL STUDIES OF THE LIGHT-INDUCED CHLOROPLAST SHRINKAGE*

Both Class I (intact) and Class II (without the outer plastid membrane) chloroplasts of Spinacea oleracea exhibit a shrinkage of the thylakoid volume under conditions which lead to the well known light-induced light scattering increases. In the present report this shrinkage has been measured on micrographs prepared by the freeze-etch technique. In cloroplasts kept in darkness through the freezing or in those treated with DCMU prior to exposure to red light, the thylakoids are in a slightly swollen condition: in plastids exposed to red light and no inhibitor, the thylakoid membranes are closely appressed, giving the thylakoid a shrunken appearance relative to the control. It is further shown that Class I chloroplasts which are actively fixing CO₂ do not give appreciable light scattering changes, but lowering the pH away from the optimum for ATP formation (and CO₂ fixation) or adding the uncoupler quinacrine restores the light-induced scattering increases.     

Non-Fermi liquid regimes in U1−xMxPd2Al3(M=Y,Th)

The temperature-composition (T–x) phase diagram and NFL characteristics in the electrical resistivity ρ(T), specific heat C(T), and magnetic susceptibility χ(T) at low temperatures for the systems U_1−xM_xPd₂Al₃ (M=Y,Th) are described. The T–x phase diagram, the NFL characteristics, and the underlying mechanism for the NFL behavior are distinctly different for M=Y³⁺ and Th⁴⁺, apparently reflecting the difference in valence of the M atom substituents, and suggesting that U is tetravalent in these two systems.