Use of very long-distance NOEs in a fully deuterated protein: an approach for rapid protein fold determination

The high sensitivity of modern NMR instrumentation, in combination with full deuteration, enabled the measurement of long-range NOEs between amide protons in a fully deuterated protein corresponding to distances up to 8A. These are beyond the limit normally observed in protonated samples. Such long-distance NOEs could be observed using long mixing times, which became possible due to reduced spin diffusion and T1 relaxation of the amide protons in the fully deuterated sample. This information was used in combination with secondary structure restraints derived from secondary chemical shifts for structure calculations. With these backbone amide proton NOEs only, a unique fold could be obtained with positional root mean square deviations from the average of 1.30 and 2.25 A for backbone and heavy atoms, respectively. Despite the low density of restraints, no mirror image problems were observed. Addition of sidechain NOE information increased the precision of the ensemble and in particular of the core packing. The structures obtained in this way were close to the published crystal structure. NOE completeness analysis revealed that the cumulative completeness is still more than 80% for an 8.0 A cut-off distance.     

Raman detection of hydrohalite formation: Avoiding accidents on icy roads by deicing where salt will not work

The common substance Hydrohalite has a role to play in as diverse areas as Geology, Earth Climatology, Universe Cosmology, and Cryobiology. In this review, the occurrences under very different occasions are described. These relations are not commonly appreciated. During the work, we realized that there is yet an aspect that has been overlooked. Hydrohalite formed sometimes on icy roads resists common salt deicing procedures. Also, hydrohalite can be detected by rather simple Raman spectroscopy instrumentation. It means that it is possible to avoid accidents on icy roads in the following way: Common salt deicing trucks may be equipped with “artificial intelligence” based on a duel deicing system that switches between normal NaCl deicing and non-NaCl deicing based on Raman spectroscopy. The advantages are first of all less traffic accidents and lower environmental impact and corrosion from NaCl, but disadvantages are increased costs of investments and consumption of non-NaCl deicing agents.     

Extrinsic multiecho phase-contrast SSFP: evaluation on cardiac output measurements

Multiecho phase-contrast steady-state free precession (PC-SSFP) is a recently introduced sequence for flow quantification. In this multiecho approach, a phase reference and a velocity-encoded readout were acquired at different echo times after a single excitation. In this study, the sequence is validated in vitro for stationary flow. Subsequently, the sequence was evaluated on cardiac output measurements in vivo for through-plane flow in comparison to regular single gradient echo velocity quantification [phase-contrast spoiled gradient echo (PC-GE)]. In vitro results agreed with regular flow meters (RMS 0.1 cm/s). Cardiac output measurements with multiecho PC-SSFP on 10 healthy subjects gave on average the same results as the standard PC-GE. However, the limits of repeatability of PC-SSFP were significantly larger than those of PC-GE (2 l/min and 0.5 l/min, respectively, P=.001). The multiecho approach introduced some specific problems in vivo. The difference in echo times made the velocity maps sensitive for water-fat shifts and B(0)-drifts, which in turn made velocity offset correction problematic. Also, the addition of a single bipolar gradient cancelled the flow compensated nature of the SSFP sequence. In combination with the prolonged TR, this resulted in flow artifacts caused by high and pulsatile through-plane flow, affecting repeatability. Given the significantly lower repeatability of PC-SSFP, cardiac output in turn is less reliable, thus impairing the use of multiecho PC-SSFP.     

A neutron powder diffraction study of the helimagnetic structure of TlCo2Se2−xSx

The magnetic layer structure of TlCo₂Se_2−xS_x has been thoroughly re-investigated with neutron powder diffraction. The cobalt magnetic moments are ferromagnetically arranged within the layers, but the interlayer coupling differs profoundly with varying composition (x): the spins in TlCo₂Se₂ form a helix along the c-axis with a turning-angle of ∼119° at 1.4 K. This kind of helical structure prevails for 0≤x≤1.5 with a gradual decrease of the angle with increasing sulphur content, down to 34°, showing an almost linear relationship with the interlayer distance of Co-Co. For x≥1.75 the interlayer coupling changes to ferromagnetic. Unexpectedly, two helices were found to coexist at x=0.5 and x=1.0. The interaction between adjacent cobalt layers is there characterized by an incommensurate angle (106°, resp., 73°) together with a commensurate angle of 90°. The magnetic structures have been refined as two magnetic phases, each having a characteristic wave vector. A tentative model where the symmetry of the structure and the interlayer distance compete is considered for explaining the simultaneous occurrence of the two kinds of diffraction profile satellites.     

Automated and rapid online determination of 15N abundance and concentration of ammonium, nitrite, or nitrate in aqueous samples by the SPINMAS technique

On the basis of the principle of reaction continuous-flow quadrupole mass spectrometry, an automated sample preparation unit for inorganic nitrogen (SPIN) species was developed and coupled to a quadrupole Mass Spectrometer (MAS). The SPINMAS technique was designed for an automated, sensitive, and rapid determination of 15N abundance and concentration of a wide variety of N-species involved in nitrogen cycling (e.g. NH4+, NO3-, NH2OH etc.). In this paper, the SPINMAS technique is evaluated with regard to the determination of 15N abundance and concentration of the most fundamental inorganic nitrogen compounds in ecosystems such as NH4+, NO2-, and NO3-. The presented paper describes the newly developed system in detail and demonstrates the general applicability of the system. For a precise determination of 15N abundance and concentration, a minimum total N-amount of 10 microg NH4+ - N, 0.03 microg NO2- - N, or 0.3 microg NO3- - N has to be supplied. Currently, the SPINMAS technique represents the most rapid and only fully automated all-round method for a simultaneous determination of 15N abundance and total N-amount of NH4+, NO2-, or NO3- in aqueous samples.     

Solid-supported reagents and catalysts for the preparation of large ring compounds

Parallel combinatorial synthesis in solution using immobilized reagents, catalysts, and scavengers has emerged as a powerful technique for the preparation of diverse libraries of compounds. This technique has only recently been applied to the synthesis of large-ring compounds. In this comprehensive review several strategies are presented and discussed, including Pd-catalyzed allylic alkylation, Stille-coupling, macrolactonization and macrolactamization using solid supported reagents and catalysts. In several cases site isolation has allowed operation of these macrocyclization reactions in concentrated solution (pseudo-dilution effect).     

Vibrational Spectra of Ethylenediamine Salts. I. Tentative Assignments of Infrared and Far Infrared Spectra

Abstract

We wish to report on some hitherto partly unnoticed and unexplained features in the infrared spectra of hydrogen halides of ethylenediamine. We have prepared normal, C-, N-, and perdeuterated ethylenediammonium chlorides and bromides and measured their infrared spectra in the range 4000–10 cm^?1.     

Towards a finite element simulation of coating by means of thermal spraying

Metal sheet forming processes like deep drawing are applied in order to produce carriage parts in mass production. Therefore, forming tools are required that are well protected against wear. For such forming tools, wear resistant surfaces are, e.g., produced by thermal spraying of hard material coatings. The thermal spraying process itself is a highly transient thermo-mechanical process. In order to gain a better understanding of the heat input and transfer during thermal spraying, a simulation framework for thermal spraying processes is presented. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Synthetic and Biological Studies on New Urea and Triazole Containing Cystobactamid Derivatives

Cystobactamids belong to the group of arene-based oligoamides that effectively inhibit bacterial type IIa topoisomerases. Cystobactamid 861-2 is the most active member of these antibiotics. Most amide bonds present in the cystobactamids link benzoic acids with anilines and it was found that some of these amide bonds undergo chemical and enzymatic hydrolysis, especially the one linking ring C with ring D. This work reports on the chemical synthesis and biological evaluation of thirteen new cystobactamids that still contain the methoxyaspartate hinge. However, we exchanged selected amide bonds either by the urea or the triazole groups and modified ring A in the latter case. While hydrolytic stability could be improved with these structural substitutes, the high antibacterial potency of cystobactamid 861-2 could only be preserved in selected cases. This includes derivatives, in which the urea group is positioned between rings A and B and where the triazole is found between rings C and D.