The Application of 2D NMR Techniques in the Structural Assignment of the Diterpenoid Alkaloid,Delphinine

The two dimensional inverse detected heteronuclear correlation experiment HMQC and the homonuclear correlation experiments COSY and ROESY were performed on the natural alkaloid, delphinine enabling complete assignments of the ¹H and ¹³C spectra. The stereochemistry of ring A and B have been determined in solution. The results suggest that the application of direct correlation multipulse NMR techniques allows for unambiguous structural assignment of delphinine.     

Peptide prefractionation is essential for proteomic approaches employing multiple‐reaction monitoring of fruit proteomic research

Off‐gel? IEF has become a popular tool in proteomics research to fractionate peptides or proteins. We conducted a detailed investigation on the fruit proteomics of apple, banana, and strawberry fruit employing Off‐gel? electrophoresis (OGE) as a crucial step to improve the proteome coverage and quantitative proteomic workflows including multiple‐reaction monitoring (MRM). We provide technical details concerning the application of Off‐gel?IEF, nano‐LC–MS detection, and MRM optimization and analysis. Our results demonstrated that the application of OGE is an effective method for peptide fractionation and increased significantly the number of proteins identified by at least ten times, with more total peptides detected and collected. Furthermore, we developed a protocol combining OGE and MRM studies to identify and quantitatively investigate monodehydroascorbate reductase, a key enzyme in the redox and antioxidant system of apple fruit during fruit ripening. Using this method, the quantitative changes in this protein during ripening and in response to ethylene treatment was investigated. Our results provide direct and comprehensive evidence demonstrating the benefits of OGE and its application for both shotgun and quantitative proteomics research.     

Cooling overall spin temperature: protein NMR experiments optimized for longitudinal relaxation effects

In experiments performed on protonated proteins at high fields, 80% of the NMR spectrometer time is spent waiting for the ¹H atoms to recover their polarization after recording the free induction decay. Selective excitation of a fraction of the protons in a large molecule has previously been shown to lead to faster longitudinal relaxation for the selected protons [K. Pervushin, B. Vögeli, A. Eletsky, Longitudinal ¹H relaxation optimization in TROSY NMR spectroscopy, J. Am. Chem. Soc. 124 (2002) 12898–12902; P. Schanda, B. Brutscher, Very fast two-dimensional NMR spectroscopy for real-time investigation of dynamic events in proteins on the time scale of seconds, J. Am. Chem. Soc. 127 (2005) 8014–8015; H.S. Attreya, T. Szyperski, G-matrix Fourier transform NMR spectroscopy for complete protein resonance assignment, Proc. Natl. Acad. Sci. USA 101 (2004) 9642–9647]. The pool of non-selected protons acts as a “thermal bath” and spin-diffusion processes (“flip-flop” transitions) channel the excess energy from the excited pool to the non-selected protons in regions of the molecule where other relaxation processes can dissipate the excess energy. We present here a sensitivity enhanced HSQC sequence (COST-HSQC), based on one selective E-BURP pulse, which can be used on protonated ¹⁵N enriched proteins (with or without ¹³C isotopic enrichment). This experiment is compared to a gradient sensitivity enhanced HSQC with a water flip-back pulse (the water flip-back pulse quenches the spin diffusion between ¹H^N and ¹H^α spins). This experiment is shown to have significant advantages in some circumstances. Some observed limitations, namely sample overheating with short recovery delays and complex longitudinal relaxation behaviour are discussed and analysed.     

Aqueous partial molar heat capacities and volumes for NaTcO4 and NaReO4

A flow microcalorimeter/densimeter system has been commissioned to measure heat capacities and densities of solutions containing radioactive species as a function of temperature. Measurements were made for NaTcO₄(aq) at six temperatures (189.15 K to 373.15 K for the heat capacities, 287.43 K to 396.67 K for the densities) over the molality range 0.01 to 0.29 mol-kg^–1. Measurements for NaReO₄(aq) (NaReO₄ is a common nonradioactive analogue for NaTcO₄) were made under similar conditions, but for eight temperatures and a more extensive range of molalities, 0.05 to 0.65 mol-kg^–1. Heat capacities of NaCl(aq) reference solutions were also measured from 293.15 K to 398.15 K.The heat capacity and density data are analysed using Pitzer's ioninteraction model. Equations for the apparent molar heat capacities and volumes are reported. Values of the NaReO₄(aq) partial molar heat capacities are compared to literature values based on integral heats of solution. The agreement between the two sets of NaReO₄ results is good below 330 K, but only fair at the higher temperatures. Values of the partial molar volumes have also been derived. Using literature values and the results of our experiments, it is calculated that the disproportionation of hydrated TcO₂(s) to form TcO ₄ ^– (aq) and Tc(cr) occurs more readily at high temperatures. The uncertainties introduced by using thermodynamic values for ReO ₄ ^– (aq), in the absence of values for TcO ₄ ^– (aq), are discussed.     

Enantiomerically pure alpha-amino acid synthesis via hydroboration-suzuki cross-coupling

The Garner aldehyde-derived methylene alkene 5 and the corresponding benzyloxycarbonyl compound 25 undergo hydroboration with 9-BBN-H followed by palladium-catalyzed Suzuki coupling reactions with aryl and vinyl halides. After one-pot hydrolysis-oxidation, a range of known and novel nonproteinogenic amino acids were isolated as their N-protected derivatives. These novel organoborane homoalanine anion equivalents are generated and transformed under mild conditions and with wide functional group tolerance: electron-rich and -poor aromatic iodides and bromides (and a vinyl bromide) all undergo efficient Suzuki coupling. The extension of this methodology to prepare meso-DAP, R,R-DAP, and R,R-DAS is also described.     

Property A and affine buildings

Yu's Property A is a non-equivariant generalisation of amenability introduced in his study of the coarse Baum Connes conjecture. In this paper we show that all affine buildings of type , and have Property A. Together with results of Guentner, Higson and Weinberger, this completes a programme to show that all affine building have Property A. In passing we use our technique to obtain a new proof for groups acting on buildings.     

Wirkung der Salpeters?ure auf pyrophosphorsaure Magnesia

Ohne Zusammenfassung     

Elementaranalyse

Ohne Zusammenfassung