Temperature dependence proton

Figure B2.4.3. Proton NMR spectrum of the aldehyde proton in N-labelled fonnainide. This proton has couplings of 1.76 Hz and 13.55 Hz to the two amino protons, and a couplmg of 15.0 Hz to the nucleus. The outer lines in die spectrum remain sharp, since they represent the sum of the couplings, which is unaffected by the exchange. The iimer lines of the multiplet broaden and coalesce, as in figure B2.4.1. The other peaks in the 303 K spectrum are due to the NH2 protons, whose chemical shifts are even more temperature dependent than that of the aldehyde proton.

The temperature dependence of the rate constant of rapid hydrogen transfer, measured by Mordzinski and Kuhnle [1986], is given in fig. 1. A similar dependence has been found by Grellmann et al. [1989] for one-proton transfer in half of the above molecule (6.16), which does not include the two rightmost rings. 

If the amount of the sample is sufficient, then the carbon skeleton is best traced out from the two-dimensional INADEQUATE experiment. If the absolute configuration of particular C atoms is needed, the empirical applications of diastereotopism and chiral shift reagents are useful (Section 2.4). Anisotropic and ring current effects supply information about conformation and aromaticity (Section 2.5), and pH effects can indicate the site of protonation (problem 24). Temperature-dependent NMR spectra and C spin-lattice relaxation times (Section 2.6) provide insight into molecular dynamics (problems 13 and 14). 

Likewise, temperature dependent H NMR spectroscopic studies on yV-phenyl-3//-azepin-2-amine indicate that one of the C3 protons is highly shielded, the other strongly deshielded.82... 

As a measure of the stereoregularity, an index EQ-H% was defined as the precent of the equatorial acetal protons to the total acetal protons. Figure 2 illustrates the temperature dependence of EQ-H% s of the polymer obtained in toluene (A), methylene chloride (B), and 1-nitropropane (C). No significant difference is observed at... 

Four strongly downshifted signals in each spectrum, between 50 and 110 ppm, were assigned to the four CB protons of the cysteines coordinating the Fe ". The contact shifts of the protons reflect the coordination of cysteine to the Fe " of the antiferromagnetically coupled Fe "-Fe" pair as the cysteine protons sense the spin down orientation of the Fe " (S = ) site. This is supported by the observation that the temperature dependence of the cysteine H" protons (measured between 276 and 308 K) follows Curie behavior (decreasing contact shift with increasing temperature). 

Fig. 4. Top Theoretical temperature dependence of the hyperfine shift of the H/3 protons of reduced spinach [Fe2S2] ferredoxin 151). The solid line corresponds to the situation where only one species exists in solution, whereas the dashed line corresponds to a situation where there is fast equilibrium between two species (in a 20/80 ratio) differing for the location of the extra electron 151). Bottom.-. Experimental temperature dependence of the H NMR shifts. The signals are labeled as in Fig. 2B.

The ESR spectrum of methanesulfinyl radical (CH3SO), identified in a y-irradiated single crystal of dimethyl sulfoxide , indicates that the unpaired electron resides essentially (72%) on the sulfur 3p orbital with modest population on the sulfur 3s (0.65%) A detailed analysis of the temperature dependence leads to 2.6 kcal mol barrier height for the hindered internal rotation of the methyl group. At low temperature (88 K) the radical adopts a fixed conformation in which one proton lies in the nodal plane of the sulfur 3p orbital however, it was not possible to distinguish either experimentally or by ab initio SCF-MO calculations between the two possible conformations, that is, 2 and 3. 

Fig. 2.11. The temperature dependence of cation/proton activity ratios of geothermal well discharges in Japan. The lines in the figure are recalculated temperature dependences of cation/proton ratios in Icelandic geothermal waters. The dashed curve in B represents the reaction 1.5 K-feldspar + H+ = 0.5 K-mica + 3 quartz (or chalcedony) + K+ (Chiba, 1991). Open circle Takigami, open triangle Kakkonda, open square Okuaizu, solid circle Kirishima, solid triangle Sumikawa, solid square Nigoiikawa.

Garcia-Viloca, M., Gelabert, R., Gonzalez-Lafont, A., Moreno, M., Lluch, J. M., 1998, Temperature Dependence of Proton NMR Chemical Shift as a Criterion to Identify Low-Barrier Hydrogen Bonds , J. Am. Chem. Soc., 120, 10203. 

First calculations of the optimum distance between the reactants, R, taking into account the dependence of the probability of proton transfer between the unexcited vibrational energy levels on the transfer distance have been performed in Ref. 42 assuming classical character of the reactant motion. Effects of this type were considered also in Ref. 43 in another model. It was shown that R depends on the temperature and this dependence leads to a distortion of the Arrhenius temperature dependence of the transition probability. 

Leiderman P, Huppert D, Agmon N (2006) Transition in the temperature-dependence of GFP fluorescence From proton wires to proton exit. Biophys J 90 1009-1018... 

The 140-residue protein AS is able to form amyloid fibrils and as such is the main component of protein inclusions involved in Parkinson s disease. Full-length 13C/15N-labelled AS fibrils and AS reverse-labelled for two of the most abundant amino acids, K and V, were examined by homonuclear and heteronuclear 2D and 3D NMR.147 Two different types of fibrils display chemical shift differences of up to 13 ppm in the l5N dimension and up to 5 ppm for the backbone and side-chain 13C chemical shifts. Selection of regions with different mobility indicates the existence of monomers in the sample and allows the identification of mobile segments of the protein within the fibril in the presence of monomeric protein. At least 35 C-terminal residues are mobile and lack a defined secondary structure, whereas the N terminus is rigid starting from residue 22. In addition, temperature-dependent sensitivity enhancement is also noted for the AS fibrils due to both the CP efficiency and motional interference with proton decoupling.148... 

---