Moving the frontiers in solution and solid-state bioNMR

A major research field in mechanistic systems biology is represented by the development of methods for investigating the structural and dynamic features of systems with multiple interacting components, in order to understand their function. A combination of NMR techniques can be used in such respect, among which the employment of paramagnetic metal ions, ¹³C direct detection, and solid-state NMR, possibly supported by other techniques like small angle X-ray scattering. Among the results, the information on the conformational heterogeneity experienced by multicomponent systems in solution can be mentioned. The structural and functional characterization of large biological systems, not affordable with standard solution NMR techniques, can be tackled through a synergistic use of solution and MAS solid-state NMR. ¹³C direct detection NMR spectroscopy is on the other hand advantageous for improving the quality and quantity of observed nuclear signals, for their intrinsically smaller linewidths and larger signal breadth. Details on these approaches are reviewed here.     

Density and Volume Properties of Ethane-1,2-diol + 1,2-Dimethoxyethane + Water Ternary Mixtures from −10° to 80°

Thermodynamic interactions in the ethane-1,2-diol (1) + 1,2-dimethoxyethane(2) + water (3) ternary system have been investigated in terms of the excessmolar volume, derived from density measurements at 19 different temperaturesfrom –10;dg to 80;dgC. Fourteen three-component mixtures have been considered,covering the entire composition range. The excess molar volumes are discussedin terms of conformational changes induced in each component by the presenceof another one. The results obtained support the hypothesis of the absence of anythree-component complex adducts under all experimental conditions investigated.     

On the Conformation of a Sterically Congested Amide Group in the Crystalline State and in Solution

The conformation in the crystalline state and in solution of the sterically congested tetramethylpiperidinederived amide group of the symmetric diamide I formed from 2,2,6,6-tetramethylpiperidine ( b ) and 1,2,5-thiadiazole-3,4-dicarbonyl dichloride ( c ), and of the mixed diamide II derived from b , c , and piperidine ( a ) has been investigated. In crystals, as observed with II , this group is strongly bent out-of-plane at both the N-atom and the carbonyl C-atom, and there is also a sizable twisting around the amide bond. Furthermore, the amide bond is abnormally long (1.37 Å). In CD₂Cl₂ (or CDCl₃) solution, the group is apparently planar in its ground-state conformation, but the energy barrier to rotation around the amide bond is low. This conclusion is based on low-temperature ¹H-NMR measurements on I , II , and on the symmetric diamide III derived from a and c .     

A convenient preparation of 3-isopropyl-1-methylcyclopentylmethanol and 1-isopropyl-3-methylcyclopentylmethanol via Favorskii rearrangement

The Favorskii rearrangement of suitable α-chloro derivatives of commercially available (+)- and (−)-carvone, and (−)-menthone served efficiently to prepare the title compounds featuring delicious fruity, floral olfactory notes.     

Inclusive ∑±(1385) production inK − p interactions at 110 GeV/c

Results are presented on inclusive production of ∑⁺(1385) and ∑^?(1385) inK ^? p interactions at 110 GeV/c. The inclusive and topological cross sections have been estimated and compared with published results at lower energies. The inclusive cross section of ∑⁺(1385) seems to decrease with c.m. energy, while that of the ∑^?(1385) is nearly constant. The mean charged multiplicity associate to Σ(1385) increases with c.m. energy. The ∑⁺(1385) is produced both in the target fragmentation region and in the central region where ∑^?(1385) is predominantly produced in the central region. Approximately 16% of the Λ's stem from the decay of ∑^±(1385) and the kinematic distributions of these Λ's are not very different from the inclusive Λ's.     

Evaluation of different rhodium modifiers and coatings on the simultaneous determination of As, Bi, Pb, Sb, Se and of Co, Cr, Cu, Fe, Mn in milk by electrothermal atomic absorption spectrometry

Different kinds of modifiers and coatings on the integrated platform of transversely heated graphite atomizer (THGA) have been tested for the simultaneous determination of two group of elements: the first, the more volatile, formed by arsenic, bismuth, lead, antimony and selenium; the second, the less volatile, formed by cobalt, chromium, cupper, iron and manganese in milk by electrothermal atomic absorption spectrometry. Different Rh-modifiers were studied, such as Rh-coated platforms (Rh), carbide plus rhodium coated platforms (W-Rh, Zr-Rh), carbide-coated platforms (W and Zr) with co-injection of RhCl₃, solutions and uncoated platforms with injection of solutions of Pd(NO₃)₂, Mg(NO₃)₂, and RhCl₃. Milk samples were diluted 1:10 in 1.0% HNO₃ and injected into the tube. The mass of modifier deposited and co-injected in the tube and the use of end capped tubes were also evaluated in order to improve the electrothermal behavior of analytes. Integrated platform pretreated with W plus co-injection RhCl₃ for first group and pretreated with W-Rh for second group were elected. For 20 μL injected samples the analytical curves in the 5.0–20.0 μg L⁻¹ concentration range have good linear correlation coefficients (r > 0.998). Relative standard deviations (n = 12) are <6% and the calculated characteristic masses are between 5 pg and 62 pg. Correspondence: Gian Paulo G. Freschi, Faculdade de Ciências Exatas e Tecnologia, Universidade Federal da Grande Dourados, PO Box 332, 79.804-970, Dourados-MS, Brazil; Instituto de Química, Universidade Estadual Paulista, PO Box 355, 14801-970 Araraquara-SP, Brazil