High-resolution 17O NMR spectroscopy of wadsleyite (beta-Mg2SiO4)

The sensitivity of high-resolution 17O (I = 5/2) NMR spectroscopy of solids has advanced significantly in recent years. Here, we show that excellent results are now obtainable from milligram quantities of 17O-enriched materials, thereby allowing the technique to be applied to silicate phases synthesized under very high pressures in a multiple-anvil apparatus. We report the first 17O NMR study of beta-Mg2SiO4 (9.6 mg of 35% 17O-enriched material, synthesized at p = 16 GPa and T = 1873 K), a dense phase believed to have a significant role in the Earth's mantle. Using STMAS at magnetic fields of B0 = 9.4 and 11.7 T and MQMAS at B0 = 18.8 T, we have resolved and assigned all four crystallographically distinct O sites and determined their chemical shift and quadrupolar parameters.     

Link between adatom resonances and the Cu(111) Shockley surface state

Low-temperature scanning tunneling microscopy and spectroscopy at 7 K was used to assemble and characterize native adatom islands of successive size on the Cu(111) surface. Starting from the single adatom we observe the formation of a series of quantum states which merge into the well known two-dimensional Shockley surface state in the limit of large islands. Our experiments reveal a natural physical link between this fundamental surface property and the sp(z) hybrid resonance associated with the single Cu/Cu(111) adatom.     

Recent approaches towards the asymmetric synthesis of alpha,alpha-disubstituted alpha-amino acids

The class of alpha,alpha-disubstituted alpha-amino acids has gained considerable attention in the past decades and continues doing so. The ongoing interest in biological and chemical properties of the substance class has inspired the development of many new methodologies for their asymmetric construction, which have not found their way into the general focus of organic chemistry yet. The aim of this review is to provide an overview of the developments in the field since 1998.     

Acid-degradable solid-walled microcapsules for pH-responsive burst-release drug delivery

Acid-degradable microcapsules were prepared via an interfacial polymerization. Degradation of the thin wall of the capsules leads to all-or-nothing cargo release. The only byproducts of degradation are acetone, and a non-toxic triamide. Proof-of-concept experiments showed that cargo can be delivered to and released in cells.     

Direct contact versus solvent-shared ion pairs in NiCl2 electrolytes monitored by multiplet effects at Ni(II) L edge X-ray absorption

We investigate the local electronic structure in aqueous NiCl2 electrolytes by Ni L edge X-ray absorption spectroscopy. The experimental findings are interpreted in conjunction with multiplet calculations of the electronic structure and the resulting spectral shape. In contrast to the situation in the solid, the electronic structure in the electrolyte reflects the absence of direct contact Ni-Cl ion pairs. We observe a systematic change of the intensity ratio of singlet- and triplet-related spectral features as a function of electrolyte concentration. These changes can be described theoretically by a change in the weight of transition matrix contributions with different symmetries. We interpret these findings as being due to progressive distortions of the local symmetry induced by solvent-shared ion pairs.     

The Contribution of the Activation Entropy to the Gas-Phase Stability of Modified Nucleic Acid Duplexes

Tricyclo-DNA (tcDNA) is a sugar-modified analogue of DNA currently tested for the treatment of Duchenne muscular dystrophy in an antisense approach. Tandem mass spectrometry plays a key role in modern medical diagnostics and has become a widespread technique for the structure elucidation and quantification of antisense oligonucleotides. Herein, mechanistic aspects of the fragmentation of tcDNA are discussed, which lay the basis for reliable sequencing and quantification of the antisense oligonucleotide. Excellent selectivity of tcDNA for complementary RNA is demonstrated in direct competition experiments. Moreover, the kinetic stability and fragmentation pattern of matched and mismatched tcDNA heteroduplexes were investigated and compared with non-modified DNA and RNA duplexes. Although the separation of the constituting strands is the entropy-favored fragmentation pathway of all nucleic acid duplexes, it was found to be only a minor pathway of tcDNA duplexes. The modified hybrid duplexes preferentially undergo neutral base loss and backbone cleavage. This difference is due to the low activation entropy for the strand dissociation of modified duplexes that arises from the conformational constraint of the tc-sugar-moiety. The low activation entropy results in a relatively high free activation enthalpy for the dissociation comparable to the free activation enthalpy of the alternative reaction pathway, the release of a nucleobase. The gas-phase behavior of tcDNA duplexes illustrates the impact of the activation entropy on the fragmentation kinetics and suggests that tandem mass spectrometric experiments are not suited to determine the relative stability of different types of nucleic acid duplexes.

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Measurement of the pion form factor for M_(ππ)～2 between 0.1 and 0.85 GeV~2 with the KLOE detector

The KLOE experiment at the φ-factory DAΦNE has measured the pion form factor in the range between 0.1M_(ππ)～2 0.85 GeV2 using events taken at s～(1/2)=1 GeV with a photon emitted at large polar angles in the initial state.This measurement extends the M_(ππ)～2 region covered by KLOE ISR measurements of the pion form factor down to the two pion production threshold.The value obtained in this measurement of the dipion contribution to the muon anomalous magnetic moment of aμππ =(478.5±2.0stat±4.8syst±2.9theo)·10-10 further confirms the discrepancy between the Standard Model evaluation for aμ and the experimental value measured by the(g-2) collaboration at BNL.     

Shear induced relaxation of polymer micelles at the solid-liquid interface

A 20% aqueous solution of (ethylene oxide) 99-(propylene oxide) 65-(ethylene oxide) 99, F127, was investigated by combining rheology in a cone/plate-geometry and surface-sensitive grazing incident neutron scattering. The crystalline structure formed by the polymer micelles becomes less pronounced for low shear rates, but correlations increase for higher shear rates. After stopping shear a slow relaxation of the micelles is found in the vicinity (50 mum thick layer) of a hydrophilic silicon wall (strong micelle-wall interaction), while a fast relaxation is observed in the boundary layer against the hydrophobic silicon wall (weak micelle-wall interaction). The results show that in the vicinity of the interface wall-particle interactions compete heavily with the shear force acting on the liquid.