Compensated second-order recoupling: application to third spin assisted recoupling

We consider the effect of phase shifts in the context of second-order recoupling techniques in solid-state NMR. Notably we highlight conditions leading to significant improvements for the Third Spin Assisted Recoupling (TSAR) mechanism and demonstrate the benefits of resulting techniques for detecting long-distance transfer in biomolecular systems. The modified pulse sequences of PAR and PAIN-CP, Phase-Shifted Proton Assisted Recoupling (AH-PS-PAR) and Phase-Shifted Proton-Assisted Insensitive Nuclei Cross Polarization (ABH-PS-PAIN-CP), still rely on cross terms between heteronuclear dipolar couplings involving assisting protons that mediate zero-quantum polarization transfer between low-γ nuclei ((13)C-(13)C, (15)N-(15)N, (15)N-(13)C polarization transfer). Using Average Hamiltonian Theory we show that phase inversion compensates off-resonance contributions and yields improved polarization transfer as well as substantial broadening of the matching conditions. PS-TSAR greatly improves on the standard TSAR based methods because it alleviates their sensitivity to precise RF settings which significantly enhances robustness of the experiments. We demonstrate these new methods on a 19.6 kDa protein (U-[(15)N, (13)C]-YajG) at high magnetic fields (up to 900 MHz (1)H frequency) and fast sample spinning (up to 65 kHz MAS frequency).     

Speciation Analysis of Mercury in Aquatic Environment

Abstract

This review considers methods for mercury speciation with low limits of detection that can be applied to real aquatic environmental samples (waters, sediments, biological tissues). Special attention is given to the necessity of clean sampling procedures and the proper storage of the samples. In this review, different extraction techniques for sediments and biological tissues are considered. The performance of different separation techniques, like liquid chromatography and off‐line and on‐line gas chromatography, are compared for their environmental applications.     

Development of Dissolution DNP-MR Substrates for Metabolic Research

Dissolution dynamic nuclear polarization (DNP) provides a broadly applicable and rather simple means of developing probes for the real-time molecular imaging of cellular functions in vivo. The development of novel dissolution DNP substrate formulations is only rewarding for substrates that yield detectable metabolism within few minutes. In addition, in vivo preparations usually require amorphous samples at molar substrate concentrations for an efficient and reproducible DNP step with sufficient material. The composition ranges of novel substrate preparations need to be established experimentally owing to the solute’s impact on vitrification behavior. Here, we describe simple rationales employed in the development of novel substrate preparations for dissolution DNP-magnetic resonance. Solution state substrate polarizations between 10 and 40?% have been obtained for ~40 metabolic substrates in highly concentrated preparations that yield physiologically tolerable solutions with sufficient T ₁ for in vivo nuclear magnetic resonance. Substrate metabolism is observed for novel in vivo substrates such as 3-hydroxybutyrate and aspartate.     

Hyperpolarizability effects in a Sr optical lattice clock

We report the observation of a higher-order frequency shift due to the trapping field in a (87)Sr optical lattice clock. We show that, at the magic wavelength of the lattice, where the first-order term cancels, the higher-order shift will not constitute a limitation to the fractional accuracy of the clock at a level of 10(-18). This result is achieved by operating the clock at very high trapping intensity up to 400 kW/cm(2) and by a specific study of the effect of the two two-photon transitions near the magic wavelength.     

Prediction of human dietary δ15N intake from standardised food records: validity and precision of single meal and 24-h diet data

Natural stable isotope ratios (δ¹⁵N) of humans can be used for nutritional analyses and dietary reconstruction of modern and historic individuals and populations. Information about an individual’s metabolic state can be obtained by comparison of tissue and dietary δ¹⁵N. Different methods have been used to estimate dietary δ¹⁵N in the past; however, the validity of such predictions has not been compared to experimental values. For a total of 56 meals and 21 samples of 24-h diets, predicted and experimental δ¹⁵N values were compared. The δ¹⁵N values were predicted from self-recorded food intake and compared with experimental δ¹⁵N values. Predicted and experimental δ¹⁵N values were in good agreement for meals and preparations (r?=?0.89, p?r?=?0.76, p?δ¹⁵N was mainly determined by the amount of fish, whereas the contribution of meat to dietary δ¹⁵N values was less pronounced. Prediction of human dietary δ¹⁵N values using standardised food records and representative δ¹⁵N data sets yields reliable data for dietary δ¹⁵N intake. A differentiated analysis of the primary protein sources is necessary when relating the proportion of animal-derived protein in the diet by δ¹⁵N analysis.     

The synthetic challenge of diazonamide A, a macrocyclic indole bis-oxazole marine natural product

The complex structure of the marine metabolic diazonamide A comprises a dichlorinated indole bis-oxazole heteroaromatic fragment, and a [b]-fused dihydrobenzofuran-dihydroindole unit containing an animal carbon, all incorporated within a strained double macrocyclic array. This review details the synthetic studies on this fascinating natural product starting from early studies on the original structure (1991-2001), through the synthesis of the originally proposed structure and the subsequent structural revision, to the eventual successful syntheses of the natural product itself. Throughout we focus on the innovative ways in which synthetic chemists have approached the challenges posed by this natural product.     

6π/10π-Electrocyclization of ketene-iminium salts for the synthesis of substituted naphthylamines

An intramolecular 6π/10π-electrocyclization from ketene-iminium salts was developed for the preparation of naphthylamines. Various substituents on the nitrogen, on the aromatic ring, and on the olefin were studied. Tricyclic skeletons were obtained in few steps and good overall yields. The electrocyclization of ketene-iminium salts has been computationally explored by means of DFT calculations and their activation barriers were compared to the parent triene as well as the corresponding dienyl allenes and dienyl ketenes. Electrocyclizations for ketene-iminium salts were shown to be highly exergonic and have much smaller barriers to activation.     

Mercury speciation analysis in human hair by species-specific isotope-dilution using GC–ICP–MS

We optimized a mercury (Hg) speciation extraction method for human hair in combination with species-specific isotope-dilution analysis by gas chromatography–inductively coupled plasma–mass spectrometry (GC–ICP–MS). The method was validated on human hair reference material RM (IAEA-086), which is recommended for analysis of monomethylmercury (MMHg) and inorganic mercury (IHg). Three reagents, hydrochloric acid (HCl), nitric acid (HNO₃), and tetramethylammonium hydroxide (TMAH), and three extraction procedures, at ambient temperature for 12 h, microwave-assisted at 75 °C for 6 min, and oven heated at 80 °C for 2 h were tested. Extraction efficiency, recovery, and potential species transformations were evaluated for each method. The most efficient procedures, with recovery of ~90 % for each species with limited demethylation (<5 %) and methylation (0 %), were HNO₃ digestion, irrespective of temperature, and microwave-assisted TMAH extraction. Acidic extraction with HCl induces significant demethylation, with production of artifacts. To correct for potential demethylation artifacts we recommend spiking with isotopically enriched standards before the extraction step.     

Metallorganische Lewis-säuren: XXI. Tetracarbonyl(η4 -tetramethylcyclobutadien)mangan(I)-tetrafluoroborat

Pentacarbonyltetrafluoroboratomanganese(I), (OC)₅MnFBF₃, reacts with 2-butyne at 15°C in dichloromethane to give tetracarbonyl(η⁴-tetramethylcyclobutadiene)manganese(I) tetrafluoroborate, [(OC)₄Mn(C₄Me₄)]⁺ BF₄^?