S N shift

S- N shift to amide bond with alkyne terminal modification... 

Figure 17.13 Expressed proteins containing a thioester intein tag can be specifically modified using a cysteine-alkyne derivative by transthioesterification followed by an internal S - N shift.

Other very important applications of C-terminal thioester-functionalized peptides include their usage in the condensation of large unprotected peptide fragments (ligation see Vol. E22a, Section 4.1.5). 4,5,74 In this process the thioester-modified unprotected peptide reacts with the N-terminal cysteine of a second unprotected peptide giving a thioester intermediate. This step is followed by a rapid intramolecular S—>N shift with formation of the thermodynamically favored amide bond at the ligation site. 

Calculated rr-bond orders are summarized in Table 1. These calculations are supported by chemical evidence that the S—N bond is the one most easily cleaved. Attempts have been made to relate bond orders and electron densities to NMR coupling constants (74CJC833, 77aC6i9> and CNMR (75CJC596, 75CJC1677> and NNMR (78JOC4693> chemical shifts, with limited success. 

Phosphorus has only one stable isotope, J P, and accordingly (p. 17) its atomic weight is known with extreme accuracy, 30.973 762(4). Sixteen radioactive isotopes are known, of which P is by far the most important il is made on the multikilogram scale by the neutron irradiation of S(n,p) or P(n,y) in a nuclear reactor, and is a pure -emitter of half life 14.26 days, 1.7()9MeV, rntan 0.69MeV. It finds extensive use in tracer and mechanistic studies. The stable isotope has a nuclear spin quantum number of and this is much used in nmr spectroscopy. Chemical shifts and coupling constants can both be used diagnostically to determine structural information. 

Infrared absorption bands of S (n>2) complexes are usually of low intensity, while the Raman spectra often show intense and characteristic hnes. However, the assignments are difficult because of their complexity. The absorptions in electronic spectra are often assigned to intrahgand transitions, and it is known that the increasing length of the polysulfido chain leads to an increasing red shift of the absorption band. 

Figure 1. Underlying structure of the "pulsating wave" solution two saddle-type standing waves S i and S2 that are n shifts of each other are...

Larger frequency shifts lead to more sensitive structural discriminations. In the IR, the (i-shcct amide I is distinctively lower in frequency than other structural types, particularly for aggregates, a form often seen in unfolding experiments. However, owing to the high signal-to-noise ratio (S/N) of Fourier transform IR (FTIR), one can detect components having smaller frequency separations. This effective resolution... 

To improve the S/N ratio, the modulation signal is processed by amplification with a tuned amplifier using phase-sensitive detection. This means that the detected signal must not only be at the modulation frequency, but must also be in phase with the modulation. Since the amplifier itself can introduce a bit of phase shift, there is a phase control which, in principle, should be adjusted to maximize the signal amplitude. In practice, this control needs to be adjusted only rarely and in most cases the best approach is to leave it alone. 

Radial velocities were measured by cross-correlation, using a synthetic spectrum as template. Individual spectra were shifted to rest wavelength and coadded. Effective temperatures were derived from the (V — I)o colours by means of the Alonso calibration [8], We assumed log g = 2.0 for all stars (estimated from isochrones) and with these parameters we fed the spectra to our automatic procedure for the determination of abundances [9], We found that the S/N ratio was too low to be able to determine reliably the microturbulent velocities, the weak Fe I lines could not be measured on many spectra. This resulted in a marked dependence of derived abundances on microturbulent velocities. It is well known that microturbulence is not a truly independent parameter but correlates with surface gravity and, more mildly also with effective temperature. By considering the large sample of stars studied by [10] one can be convinced that for all stars with 1.5 < logg < 3.0 (20 stars) there is no marked dependence from either Tefi or log g, and the mean value of the microturbulent velocity is 1.6 kms 1. For this reason we fixed the microturbulent velocity at 1.6 kms-1. 

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