Low temperature solid-state NMR experiments of half-integer quadrupolar nuclides: caveats and data analysis

Solid-state NMR spectroscopy of half-integer quadrupolar nuclides has received a lot of interest recently with the advent of new methodologies and higher magnetic fields. We present here the extension of our previous low temperature method to an 18.8T system. This new probe entailed a total redesign including a cross coil and variable capacitors that are operational at cryogenic temperatures. The limitations to sensitivity are also discussed; including a new diode network, the utilization of a cryogenic band pass filter, and the consequences of the RF profiles of the coil. Further, details of the spectroscopy of quadrupolar nuclei in a protein are discussed, such as the observation of the outer transitions and how to distinguish them from the desired +/-1/2 transition.     

Dipolar and quadrupolar detection using an FT-ICR MS setup at the MPIK Heidelberg

Dipolar and single-phase two-electrode quadrupolar detection schemes have been investigated at a Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) setup built for the KATRIN experiment at the Max-Planck-Institute for Nuclear Physics (MPIK) in Heidelberg. We present first experimental results of ⁷Li^?+? signals from a cylindrical Penning trap configuration for both detection schemes. While the prominent signal of the conventional dipolar detection scheme marks the reduced cyclotron frequency, the main signal for the quadrupolar detection appears at the sum of the reduced cyclotron frequency and the magnetron frequency. For ideal trapping fields, this sum frequency equals the ion cyclotron frequency ?? _c ?=?qB/(2??m). Sidebands due to the combined motions of the cyclotron mode and magnetron mode are observed by quadrupolar detection which allows the determination of the respective combinations of eigenfrequencies.     

1-(1-Alkenyl)benzotriazoles: Novel α-Hydroxyacyl Anion Equivalents for the Synthesis of α-Hydroxy Ketones

α-Lithiated 1-(1-alkenyl)benzotriazoles, generated from the reactions of 1-(1-alkenyl)benzotriazoles with n-BuLi, react with a variety of electrophiles to afford α-substituted 1-(1-alkenyl)benzotriazoles which undergo epoxidation with m-CPBA followed by hydrolysis to give α-hydroxy ketones in good yields. Thus, 1-(1-alkenyl)benzotriazoles behave as α-hydroxyacyl anion equivalents.     

Gas phase bimolecular chemistry of isomeric C3H6Br+ cations

The gas phase chemistry of C₃H₆Br⁺ cations generated via low energy electron impact on various dibromopropanes has been studied by using Fourier transform ion cyclotron resonance mass spectrometry. Neutral substrate molecules that have been selected to probe the bimolecular reactivity of the C₃H₆Br⁺ isomers are ammonia, methylamine, trimethylamine, cis-butene, and 2, 3-dimethyl-2-butene. At least three different isomers are characterized on the basis of their different reactivity toward the various substrate molecules. It is suggested that these isomers have (a) the 2-bromo-2-propyl cation structure, (b) the propylenebromomum ion structure, and (c) the cyclic four-membered trimethylenebromonium ion structure. The 2-bromo-2-propyl cations react predominantely via proton transfer. This reaction is hampered for the propylenebromonium ions, which react mainly as electrophiles or bromanyl cation donors. Cyclic trimethylenebromoruum ions react predominantly via adduct formation, even under low pressure conditions, which implies that tturd body collisions are not the only stabilization mechanism.     

Landau-Level Quantization of the Yellow Excitons in Cuprous Oxide

Lately, the yellow series of P-excitons in cuprous oxide could be resolved up to the principal quantum number n = 25. Adding a magnetic field, leads to additional confinement normal to the field. Thereby, the transition associated with the exciton n is transformed into the transition between the electron and hole Landau levels with quantum number n, once the associated magnetic length becomes smaller than the related exciton Bohr radius. The magnetic field of this transition scales roughly as n^–3. As a consequence of the extended exciton series, we are able to observe Landau level transitions with unprecedented high quantum numbers of more than 75.     

A Protein‐Based Encapsulation System with Calcium‐Controlled Cargo Loading and Detachment

Protein‐based encapsulation systems have a wide spectrum of applications in targeted delivery of cargo molecules and for chemical transformations in confined spaces. By engineering affinity between cargo and container proteins it has been possible to enable the efficient and specific encapsulation of target molecules. Missing in current approaches is the ability to turn off the interaction after encapsulation to enable the cargo to freely diffuse in the lumen of the container. Separation between cargo and container is desirable in drug delivery applications and in the use of capsids as catalytic nanoparticles. We describe an encapsulation system based on the hepatitis B virus capsid in which an engineered high‐affinity interaction between cargo and capsid proteins can be modulated by Ca²⁺. Cargo proteins are loaded into capsids in the presence of Ca²⁺, while ligand removal triggers unbinding inside the container. We observe that confinement leads to hindered rotation of cargo inside the capsid. Application of the designed container for catalysis was also demonstrated by encapsulation of an enzyme with β‐glucosidase activity.     

The multicomponent reactions and their libraries for natural and preparative chemistry

It was recently recognized that three different types of multi-component reactions (MCRs) exist. In preparative chemistry, the MCRs of type II form their products particularly efficiently. These reactions correspond to equilibria of educts and intermediate products, whose final products are formed practically irreversibly. In recent years, the four component reaction of the isocyanides (U-4CR) of type II and their unions with various reactions and MCRs have become an important industrial process for preparing products and their libraries. It has been demonstrated that all conceivable collections of U-4CR educts can be converted into the corresponding products. In the usual chemical reactions, only the substituents of the products can be varied, whereas the U-4CR and related reactions can also produce skeletally different types of products with diverse substituents. The preparative advantages of forming products by the one-pot MCRs and the great variety of the possible products are illustrated in this review.     

Electronic coupling through intramolecular π-π interactions in biscobaltocenes: a structural, spectroscopic, and magnetic study

The paramagnetic dinuclear complexes 1,8-bis(cobaltocenyl)naphthalene (2) and 1,8-bis[(pentamethyl-η(5)-cyclopentadienyl)(η(5)-cyclopentadiendiyl)cobalt(II)]naphthalene (4) were synthesized. The molecular structures were characterized by X-ray structure analysis and consisted of two cobaltocenes linked through a distorted naphthalene clamp. Electronic interactions between the two cobalt atoms were observed by cyclic voltammetric studies. Superconducting quantum interference device (SQUID) measurements of the pure compounds and diluted in their diamagnetic iron derivatives, as well as variable-temperature NMR spectroscopy experiments in solution are presented. Magnetic measurements revealed an antiferromagnetic coupling of the electrons in complexes 2 and 4. From NMR spectroscopy experiments, Curie behavior in the temperature range from -60 to +60 °C can be deduced. The electronic structure and magnetic behavior is supported by results of broken-symmetry DFT and multireference calculations along with UV/Vis spectroscopic data, which revealed an intramolecular through space π-π interaction between the cobaltocene units.     

Factors affecting gas-phase deuterium scrambling in peptide ions and their implications for protein structure determination

In this report, we evaluate the validity of using hydrogen/deuterium exchange in combination with collision-induced dissociation mass spectrometry (CID MS) for the detailed structural and conformational investigation of peptides and proteins. This methodology, in which partly deuterated peptide ions are subjected to collision-induced dissociation in the vacuum of a mass spectrometer, has emerged as a useful tool in structural biology. It may potentially provide quantitatively the extent of deuterium incorporation per individual amino acid in peptides and proteins, thus providing detailed structural information related to protein structure and folding. We report that this general methodology has limitations caused by the fact that the incorporated deuterium atoms migrate prior or during the CID MS analysis. Our data are focused on a variety of transmembrane peptides, incorporated in a lipid bilayer, in which the near-terminal amino acids that anchor at the lipid-water interface are systematically varied. Our findings suggest that, under the experimental conditions we use, the extent of intramolecular hydrogen scrambling is strongly influenced by experimental factors, such as the exact amino acid sequence of the peptide, the nature of the charge carrier, and therefore most likely by the gas-phase structure of the peptide ion. Moreover, the observed scrambling seems to be independent of the nature of the peptide fragment ions (i.e., protonated B and Y' ' ions, and sodiated A and Y' ions). Our results strongly suggest that scrambling may be reduced by using alkali metal cationization instead of protonation in the ionization process.