Tuning protonation states of tripelennamine antihistamines by cucurbit[7]uril

The formation of host–guest complexes of cucurbit[7]uril (CB7) with the antihistamine drug tripelennamine (TRP) was studied by optical and NMR spectroscopy. The experimental and computational results are consistent with inclusion of a single TRP molecule in CB7. Addition of CB7 has tuned drug protonation states associated with (de)protonation of the ethyldimethylammonium and exocyclic nitrogens with an increase in the associated pK_a values by 1.5 and 2.5 units, respectively. The incorporation of antihistamines drugs such as TRP in cucurbiturils could be utilized for switching their capability for selective binding to histamine H₁‐receptors, in the future. Copyright © 2015 John Wiley & Sons, Ltd.     

Model based prediction of the trap limited diffusion of hydrogen in post‐hydrogenated amorphous silicon

The diffusion of hydrogen within an hydrogenated amorphous silicon (a‐Si:H) layer is based on a trap limited process. Therefore, the diffusion becomes a self‐limiting process with a decreasing diffusion velocity for increasing hydrogen content. In consequence, there is a strong demand for accurate experimental determination of the hydrogen distribution. Nuclear resonant reaction analysis (NRRA) offers the possibility of a non‐destructive measurement of the hydrogen distribution in condensed matter like a‐Si:H thin films. However, the availability of a particle accelerator for NRR‐analysis is limited and the related costs are high. In comparison, Fourier transform infrared spectroscopy (FTIR) is also a common method to determine the total hydrogen content of an a‐Si:H layer. FTIR spectrometers are practical table‐top units but lack spatial resolution. In this study, an approach is discussed that greatly reduces the need for complex and expensive NRR‐analysis. A model based prediction of hydrogen depth profiles based on a single NRRA measurement and further FTIR measurements enables to investigate the trap limited hydrogen diffusion within a‐Si:H. The model is validated by hydrogen diffusion experiments during the post‐hydrogenation of hydrogen‐free sputtered a‐Si. The model based prediction of hydrogen depth profiles in a‐Si:H allows more precise design of experiments, prevents misinterpretations, avoids unnecessary NRRA measurements and thus saves time and expense. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Occurrence of rotation domains in heteroepitaxy

Heteroepitaxy can involve materials with a misfit of crystal structure. Rotation domains in the epilayer are a fundamental consequence. We derive a general expression for their (minimum) number which is determined by the mismatch of the rotational symmetries of the substrate and epilayer. In the case of a mismatch of rotational symmetry, the number of rotation domains of material A on material B is different from that of B on A. A larger number of rotation domains can occur due to domain structure or nearly fulfilled additional symmetries of the substrate surface.     

Efficient single-photon counting at 1.55 microm by means of frequency upconversion

We demonstrate efficient single-photon detection at 1.55 microm by means of sum-frequency mixing with a strong pump at 1.064 microm in periodically poled lithium niobate followed by photon counting in the visible region. This scheme offers significant advantages over existing InGaAs photon counters: continuous-wave operation, higher detection efficiency, higher counting rates, and no afterpulsing. We achieved single-photon upconversion efficiency of 90% at 21.6 W of circulating power in a resonant pump cavity with a 400-mW Nd:YAG laser. We observed high background counts at strong circulating pump powers due to efficient upconversion of pump-induced fluorescence photons.     

A new polar nephelometer for measurement of atmospheric aerosols

The angular dependence of light scattered by aerosol particles in the atmosphere—the aerosol phase function—is one of the key properties of every radiative transfer and climate model. Side-scattering in the atmosphere is currently believed to be underestimated by most of the radiative transfer models in certain cases. The aerosol phase function can be measured with polar nephelometers.An innovative polar nephelometer able to measure the phase function of ambient aerosol directly is presented in this publication. The performance of the device was simulated completely using ray-tracing techniques. The results of these simulations are used to interpret the measurement data precisely. The measurements with the new polar nephelometer are fully automated. The quality of the measurement results was verified using different approaches. The values of the statistical and systematic error in measuring atmospheric aerosol are about 4% each. Scattering angles from 10° to 160° were measured and it is shown that with the same design this range can be extended to 3-177° in steps of 0.16° with an aperture of less than 1.8°.Measurements of the aerosol phase function are presented and compared with data taken with an integrating nephelometer and measurements of the particulate matter concentration. All data correlate very well. The described polar nephelometer can measure the phase function and the scattering coefficient of atmospheric aerosol with high accuracy and can be used for continuous monitoring measurements as well as in field campaigns.     

Evidence for line nodes in the superconducting energy gap of noncentrosymmetric CePt3Si from magnetic penetration depth measurements

We report measurements of the magnetic penetration depth lambda(T) in high-quality CePt3Si samples down to 0.049 K. We observe a linear temperature dependence below T approximately equal to 0.16Tc, which is interpreted as evidence for line nodes in the energy gap of the low-temperature phase of this material. A kink in lambda(T) at about 0.53 K may be associated with the second superconducting transition recently reported. The results are discussed in terms of the symmetry of the superconducting order parameter.     

Organocatalysis: quantum chemical modeling of nucleophilic addition to α,β‐unsaturated carbonyl compounds

One of the successful transformations within the field of organocatalysis, the organocatalytic asymmetric addition of nitromethane to α,β‐unsaturated aldehydes and ketones, has been studied by quantum chemical modeling. The level of accuracy of the hybrid density functional theory method B3LYP/6‐31G(d) was compared to a high level ab initio benchmark for this reaction. It is concluded that B3LYP/6‐31G(d) performs very well for this reaction type, giving good estimates of critical energies. The reaction between acrolein and nitromethane was studied in detail. The reaction mechanism revealed an intermediate oxazolidin structure, which is currently unknown. Alkyl substitution in various positions on the amine catalyst or α,β‐unsaturated carbonyl compound influences the reactivity in a predictive fashion. The iminium ion, prop‐2‐en‐iminium, is less activated towards nucleophilic attack compared to protonated acrolein. Copyright © 2007 John Wiley & Sons, Ltd.     

Inversion domain boundaries in ZnO with additions of Fe2O3 studied by high-resolution ADF imaging

Columns of metal atoms in the polytypoid compound Fe2O3(ZnO)15 could be resolved by high angle annular dark field imaging in a transmission electron microscopy (TEM)/STEM electron microscope--a result which could not be realized by high-resolution bright field imaging due to inherent strain from inversion domains and inversion domain boundaries (IDBs) in the crystals. The basal plane IDB was imaged in [11 00] yielding the spacing of the two adjacent ZnO domains, while imaging in [21 1 0] yields the position of single metal ions. The images allow the construction of the entire domain structure including the stacking sequence and positions of the oxygen ions. The IDB consists of a single layer of octahedrally co-ordinated Fe3+ ions, and the inverted ZnO domains are related by point symmetry at the iron position. The FeO6 octahedrons are compressed along the ZnO c-axis resulting in a FeO bond length of 0.208 nm which is in the range of FeO distances in iron containing oxides. The model of the basal plane boundary resembles that of the IDB in polytypoid ZnO-In2O3 compounds.     

Practical aspects of (1)H transverse paramagnetic relaxation enhancement measurements on macromolecules

The use of (1)H transverse paramagnetic relaxation enhancement (PRE) has seen a resurgence in recent years as method for providing long-range distance information for structural studies and as a probe of large amplitude motions and lowly populated transient intermediates in macromolecular association. In this paper we discuss various practical aspects pertaining to accurate measurement of PRE (1)H transverse relaxation rates (Gamma(2)). We first show that accurate Gamma(2) rates can be obtained from a two time-point measurement without requiring any fitting procedures or complicated error estimations, and no additional accuracy is achieved from multiple time-point measurements recorded in the same experiment time. Optimal setting of the two time-points that minimize experimental errors is also discussed. Next we show that the simplistic single time-point measurement that has been commonly used in the literature, can substantially underestimate the true value of Gamma(2), unless a relatively long repetition delay is employed. We then examine the field dependence of Gamma(2), and show that Gamma(2) exhibits only a very weak field dependence at high magnetic fields typically employed in macromolecular studies. The theoretical basis for this observation is discussed. Finally, we investigate the impact of contamination of the paramagnetic sample by trace amounts (5%) of the corresponding diamagnetic species on the accuracy of Gamma(2) measurements. Errors in Gamma(2) introduced by such diamagnetic contamination are potentially sizeable, but can be significantly reduced by using a relatively short time interval for the two time-point Gamma(2) measurement.