Synthesis and characterization of homochiral cholesteryl 1-alkenesulfinate esters

A number of ,β-unsaturated sulfinyl chlorides 1 has been separately prepared and treated with (−)-cholesterol under various conditions some of which incorporated chiral amines quinine or quinidine. Some (R_S) vinylic sulfinates could be isolated in enantiopure form following one or two recrystallizations of the resulting diastereomeric mixtures of (−)-cholesteryl 1-alkenesulfinates 2. Access to diastereomerically enriched (S_S) vinylic sulfinates (66–75% de) was achieved in three instances. Absolute stereochemical assignments were made with the assistance of the chiral solvating agent (R)-2,2,2-trifluoro-1-(9-anthryl)ethanol.     

Tuning Optical and Electron Donor Properties by Peripheral Thio–Aryl Substitution of Subphthalocyanine: A New Series of Donor–Acceptor Hybrids for Photoinduced Charge Separation

Subphthalocyanine (SubPc), a unique ring‐reduced member of the common phthalocyanines family, although known for its higher absorptivity, reveals narrow absorption with peak maxima around 570 nm thus limiting its utility in light‐energy‐harvesting applications. In the present study, by peripheral thio–aryl substitution of SubPc macrocycle, the spectral properties have been modulated to extend the absorption and emission well into the visible/near‐IR region. Additionally, for α‐ring‐substituted derivatives, facile oxidation of SubPc was witnessed, thus making these derivatives better electron donors. Next, the preparation of donor–acceptor dyads containing the well‐known electron acceptor C₆₀ connected to the central boron atom of SubPc was accomplished by making use of the 1,3‐dipolar cycloaddition reaction. Control experiments and free‐energy calculations using the redox and spectral data suggested that the observed fluorescence quenching of SubPc in these dyads is due to electron transfer. Accordingly, transient spectral studies performed both in polar and nonpolar solvents conclusively proved electron transfer to be the quenching mechanism in these dyads. The measured rate constants by fitting kinetic data revealed efficient charge separation and charge recombination processes, suggesting that these dyads could be useful materials for the construction of light‐to‐electricity or light‐to‐fuel production devices.     

β-Sulfinyl acrylate esters as a convenient source of alkane- and arenesulfenate anions

Methyl acrylate esters bearing alkane- and arenesulfinyl units on the 2-carbon liberate sulfenate anions upon nucleophilic attack. The sulfenates are readily captured through sulfur alkylation. When a sulfenate derived from R-cysteine is generated, diastereoselective benzylation is observed.     

Über die thermische Trimorphie von KGaCl4

On the Thermal Trimorphism of KGaCl₄ KGaCl₄ exists in three enantiotropic forms: KGaCl₄-I is stable below ?25°C, KGaCl₄-II between ?25 and about 130°C, KGaCl₄-III above 130°C up to the melting point (259°C). KGaCl₄-III belongs to the baryte type of structure, KGaCl₄-II crystallizes with the KAlCl₄-type (distorted baryte). Thermal expansion of both forms (II, III) and the phase transition II ? III are investigated thoroughly.     

Next-to-leading-order results for five, six, and seven jets in electron-positron annihilation

We present next-to-leading order corrections in the leading color approximation for jet rates in electron-positron annihilation up to seven jets. The results for the two-, three-, and four-jet rates agree with known results. The NLO jet rates have been known previously only up to five jets. The results for the six- and seven-jet rate are new. The results are obtained by a new and efficient method based on subtraction and numerical integration.     

Perspektivitäten in allgemeinen Verbänden

Ohne ZusammenfassungAnmerkung der Redaktion. Die Arbeit wurde am 25. Dezember 1943 eingereicht, vor dem Druck jedoch umgearbeitet, um den Zusammenhang mit nachfolgenden Arbeiten zu verdeutlichen und diese vorzubereiten.     

Ein allgemeiner Mengenisomorphiesatz der Theorie der Verbände

Ohne Zusammenfassung     

Brain-derived neurotrophic factor modulation of Kv1.3 channel is disregulated by adaptor proteins Grb10 and nShc

Background

Developmental dyslexia is a specific cognitive disorder in reading acquisition that has genetic and neurological origins. Despite histological evidence for brain differences in dyslexia, we recently demonstrated that in large cohort of subjects, no differences between control and dyslexic readers can be found at the macroscopic level (MRI voxel), because of large variances in brain local volumes. In the present study, we aimed at finding brain areas that most discriminate dyslexic from control normal readers despite the large variance across subjects. After segmenting brain grey matter, normalizing brain size and shape and modulating the voxels' content, normal readers' brains were used to build a 'typical' brain via bootstrapped confidence intervals. Each dyslexic reader's brain was then classified independently at each voxel as being within or outside the normal range. We used this simple strategy to build a brain map showing regional percentages of differences between groups. The significance of this map was then assessed using a randomization technique.

Results

The right cerebellar declive and the right lentiform nucleus were the two areas that significantly differed the most between groups with 100% of the dyslexic subjects (N = 38) falling outside of the control group (N = 39) 95% confidence interval boundaries. The clinical relevance of this result was assessed by inquiring cognitive brain-based differences among dyslexic brain subgroups in comparison to normal readers' performances. The strongest difference between dyslexic subgroups was observed between subjects with lower cerebellar declive (LCD) grey matter volumes than controls and subjects with higher cerebellar declive (HCD) grey matter volumes than controls. Dyslexic subjects with LCD volumes performed worse than subjects with HCD volumes in phonologically and lexicon related tasks. Furthermore, cerebellar and lentiform grey matter volumes interacted in dyslexic subjects, so that lower and higher lentiform grey matter volumes compared to controls differently modulated the phonological and lexical performances. Best performances (observed in controls) corresponded to an optimal value of grey matter and they dropped for higher or lower volumes.

Conclusion

These results provide evidence for the existence of various subtypes of dyslexia characterized by different brain phenotypes. In addition, behavioural analyses suggest that these brain phenotypes relate to different deficits of automatization of language-based processes such as grapheme/phoneme correspondence and/or rapid access to lexicon entries.