An induced-fit model for asymmetric organocatalytic reactions: a case study of the activation of olefins via chiral Brønsted acid catalysts

We elucidate the stereo-controlling factors of the asymmetric intramolecular hydroalkoxylation of terminal olefins catalyzed by bulky Brønsted acids [Science2018, 359 (6383), 1501–1505] using high-level electronic structure methods. The catalyst–substrate interaction is described using a dispersion-driven induced-fit model, in which the conformational changes of the catalyst and of the substrate in the transition states are governed to a large extent by London dispersion forces. The distortion energy of the catalyst is dominated by the change in the intramolecular dispersion interactions, while intermolecular catalyst–substrate dispersion interactions are the major stabilizing contribution in the transition state. This model provides a new general framework in which to discuss the stereoselectivity of transformations catalyzed by such confined organocatalysts.

We elucidate the stereo-controlling factors of the asymmetric intramolecular hydroalkoxylation of terminal olefins catalyzed by bulky Brønsted acids [Science2018, 359 (6383), 1501–1505] using high-level electronic structure methods.     

Optimization toward a high-average-brightness soft-x-ray laser pumped at grazing incidence

We report the near-field imaging characterization of a 10 Hz Ni-like 18.9 nm molybdenum soft-x-ray laser pumped in a grazing incidence pumping (GRIP) geometry with a table-top laser driver. We investigate the effect of varying the GRIP angle on the spatial behavior of the soft-x-ray laser source. After multiparameter optimization, we were able to find conditions to generate routinely a high-repetition-rate soft-x-ray laser with an energy level of up to 3 microJ/pulse and to 6x10(17) photons/s/mm2/mrad2/(0.1% bandwidth) average brightness and 1x10(28) photons/s/mm2/mrad2/(0.1% bandwidth) peak brightness.     

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Non-standard gauge-boson self-interactions within a gauge invariant model

We examine dimension-six extensions of the standard electroweak Lagrangian which are invariant under localSU(2) _L ×U(1) _Y -transformations. The dimensionfour trilinear and quadrilinear effective interactions of the vector bosons with one another are found to coincide with the vector boson interactions previously derived from globalSU(2) weak isospin symmetry broken by electromagnetism. Supplementing the model by a well-known dimension-six single-parameter quadrupole interaction leads to the most general vector boson self-couplings that can be obtained by addition of dimension-six terms to the standard Lagrangian. We examine in some detail anotherSU(2) _L ×U(1) _Y -symmetric interaction which containsW ₃ B mixing and modifies both vector boson self-couplings and fermionic interactions. Independently of being strongly constrained by the LEP 1 data, the addition of this interaction to the above-mentioned non-standard ones does not change the form of the trilinear and quadrilinear non-standard self-couplings of the vector bosons. Therefore, while being interesting in itself with respect to LEP 1 physics, this term is irrelevant with respect to the phenomenology of the vector-boson self-interactions.     

Cost-optimal multistage sampling plans in statistical quality control

Multistage Bayesian decision procedures in statistical quality control are known from attribute sampling. In this paper they are introduced in a more general framework occuring in lot-control by using the theory of Bayesian sequentially planned decision procedures. We show that under sufficiency and transitivity assumptions and monotonicity properties concerning the distribution and cost set-up these Bayes-procedures have (z, c ^–,c ⁺)-structure which, on one hand, generalizes results of K.-H. Waldmann and, on the other hand, reduces computational effort significantly. Finally, examples taken from attribute sampling and life testing for an outgoing lot are presented.The theory presented in this paper is taken from [11].     

Influence of acceptor and donor adsorbates (CO,K, NH3) on Pt surface core-level shifts

4f core-level shifts have been measured for clean surfaces of Pt(111), Pt(331), and Pt(557). Surface peaks due to terrace sites are shifted toward lower binding energy (0.32 ± 0.05 eV) from the bulk peak, whereas peaks from step atoms are shifted by 0.58 ± 0.05 eV also to lower binding energy. The intensity ratios for the two sites differ considerably between the stepped Pt surfaces. Chemisorption of carbon monoxide on the Pt(331) surface is preferential to step sites, with a Pt 4f binding energy shift of ～ 1.29 eV toward higher binding energy. Chemisorption of potassium and ammonia also produces Pt 4f surface shifts which are at higher binding energy than the bulk peak. These experiments do not support the concept of electron donation by these adsorbates into metal d orbitals. The results are discussed in view of, and supported by, tight-binding LCAOMO calculations of potassium and ammonia interacting with a Pt(111) thin film.     

Photoemission studies of clean and oxygen-covered Pt 6(111) × (100)

Employing the enhanced sensitivity obtained by using synchrotron radiation near the Cooper minimum for the 5d valence electrons, we have located the oxygen 2p and 2s levels for oxygen chemisorbed on a Pt 6(111) × (100) crystal. We find the oxygen 2p level located ?6 eV with a FWHM of 3 eV and the 2s at ?21.6 eV. A factor of four difference in saturation coverage is measured between temperatures of 300 and 120 K, but the position and width of the 2p level is independent of temperature. We observe also the 1b₁ orbital of weakly adsorbed H₂O molecules, which has pure O 2p parentage; from the intensity of this orbital, we are able to suggest why it is difficult to observe the oxygen 2p signal at low photon energies. In addition, we note a strong preferential attenuation in the Pt states near E_f for the adsorbed H₂O in spite of the weak nature of the bond.     

Photoemission studies of the electronic structure of III–V semiconductor surfaces

The photoemission technique using synchroton radiation in the photon energy range 5–450 eV has been applied to the study of the electronic structure of some III–V semiconductor surfaces, prepared by cleavage in situ under ultrahigh vacuum conditions, ? 10^?11 Torr. For p-type GaAs(110), the Fermi level is pinned at the top of the valence band and thus no filled surface states extend into the band-gap. The situation is more complicated for n-type GaAs(110), where band bending easily can be introduced by extrinsic effects (impurities, cleavage quality, etc.) and push the Fermi level down to about midgap. Chemical shifts of inner core levels (3d for Ga and As) are used to obtain information on the bonding site of oxygen on the (110) surface. GaAs(110) can be exposed to atmospheric pressure of molecular oxygen without breaking the bonds between the surface atoms and the bulk. Oxygen is predominantly bonded to the As atoms on the surface. The oxidation behavior is strikingly different for GaSb(110) with formation of gallium and antimony oxides on the surface directly upon oxygen exposure. Heavier oxidation of GaAs(110) and breaking of the surface bonds will also be reported.     

A new combination of the ring oven method with chromatography - the rotating ring oven

Chromatographic techniques have been used in combination with the ring oven method in various ways. The use of a rotating ring oven in combination with column chromatography is proposed. Separations are done on a chromatographic column fixed vertically above the rotating ring oven. Thus the various substances leaving the column are concentrated successively in sharply outlined distinct segments. The apparatus is described in detail. Its use is illustrated by the example of the separation of four amino acids (0.3 μg each).Other applications (dyes, gel chromatography on Sephadex) are mentioned briefly.