Ab initio predictions of zeolite structures and Si NMR chemical shifts

A recent shell-model potential parameterized on ab initio data is used for predicting the all-silica structures of zeolites MFI, MEI, MTW, TON, FAU and of α-quartz. Cluster models are defined around each site and the ²⁹Si NMR shielding constants are calculated by ab initio techniques (GIAO-HF). Good agreement with observed ²⁹Si NMR chemical shifts is found. Comparison is made with shifts calculated for observed structures. The structures predicted by the ab initio shell-model potential prove as accurate as the observed ones when judged on the quality of the calculated ²⁹Si NMR spectra.     

Gaucher disease-associated glucocerebrosidases show mutation-dependent chemical chaperoning profiles

Gaucher disease is a lysosomal storage disorder caused by deficient glucocerebrosidase activity. We have previously shown that the cellular activity of the most common Gaucher disease-associated glucocerebrosidase variant, N370S, is increased when patient-derived cells are cultured with the chemical chaperone N-nonyl-deoxynojirimycin. Chemical chaperones stabilize proteins against misfolding, enabling their trafficking from the endoplasmic reticulum. Herein, the generality of this therapeutic strategy is evaluated with other glucocerebrosidase variants and with additional candidate chemical chaperones. Improved chemical chaperones are identified for N370S glucocerebrosidase. Moreover, we demonstrate that G202R, a glucocerebrosidase variant that is known to be retained in the endoplasmic reticulum, is also amenable to chemical chaperoning. The L444P variant is not chaperoned by any of the active site-directed molecules tested, likely because this mutation destabilizes a domain distinct from the catalytic domain.     

Extended phonon collapse and the origin of the charge-density wave in 2H-NbSe2

We report inelastic x-ray scattering measurements of the temperature dependence of phonon dispersion in the prototypical charge-density-wave (CDW) compound 2H-NbSe2. Surprisingly, acoustic phonons soften to zero frequency and become overdamped over an extended region around the CDW wave vector. This extended phonon collapse is dramatically different from the sharp cusp in the phonon dispersion expected from Fermi surface nesting. Instead, our experiments, combined with ab initio calculations, show that it is the wave vector dependence of the electron-phonon coupling that drives the CDW formation in 2H-NbSe2 and determines its periodicity. This mechanism explains the so far enigmatic behavior of CDW in 2H-NbSe2 and may provide a new approach to other strongly correlated systems where electron-phonon coupling is important.     

PAC-studies of Sn-doped In2O3: electronic defect relaxation following the 111In(EC)111Cd-decay

Perturbed γ-angular correlation measurements as function of the measuring temperature and the Sn-content have been performed in Sn-doped cubic In₂O₃ using ¹¹¹In(EC)¹¹¹Cd and ^111m Cd probes. By comparing the spectra of both isotopes, electronic relaxation phenomena, socalled decay after-effects, following the electron capture radioactive decay of ¹¹¹In, were established. A time independent loss of the static quadrupole interaction amplitudes was found to be characteristic for the electronic relaxation, and its temperature and doping dependence were measured. The high statistical accuracy of the PAC-data allowed a separation between structural and dynamic effects and the observation of each lattice site’s behaviour. Relaxation rates were extracted from numerical simulations based on Blume’s theory and related to the predominant electron transport mechanisms in In₂O₃, especially, with rising Sn-content, to the transition to metallic conduction.     

Stereoselective Ring Opening of Electronically Excited Cyclohexa-2, 4-dienones: Cause and effect

The two conformers of a cyclohexa-2, 4-dienone with different substituents at C(6) on irradiation are believed to undergo ring opening stereospecifically affording a mixture of two configurationally isomeric diene-ketenes (and descendents thereof)- Exceptions are generally found for those dienones with one C and one O substituent or even with two C substituents, if one of them carries a polar group at a site able to interact through space with the ring C?O group. In these cases, only one of the two anticipated diene-ketenes (and descendents thereof) is produced. A thorough investigation of the photochemistry of a series of structurally different cyclohexa-2, 4-dienones on analytical as well as on preparative scale extends our mechanistic knowledge of the various routes from diene-ketenes into a variety of compound classes. Novel compound classes accessible to diene-ketenes are seven-membered carbocycles (by intramolecular aldolization of the zwitterion of appropriately substituted, transiently formed diene-(N, O)-ketene acetals) and β-lactams (by Staudinger reaction).