Practical Aspects of Carbon-13 Double Quantum NMR
We want to address an erroneous view that has recently been advanced on 13C double quantum NMR. A recent publication (I) introduced a modified version (I) of the original double quantum NMR experiments; this new version claims to offer an attractive increase in sensitivity by a factor of three, or a decrease in the size of the required data matrix by a factor of four. To avoid disappointment among spectroscopists we wish to make it clear that this modified version offers no gain in sensitivity whatsoever in comparison with the other double quantum experiments (2-6), provided they are properly optimized. It is shown here that the sensitivity of this modified experiment can be even slightly lower. The claim of a reduction of the size of the required data matrix is also shown to be incorrect. In the original two-dimensional double quantum “C experiments, the acquisition time t2 starts immediately after the final “read pulse” (Fig. 1), and the time during which the double quantum coherence evolves is labeled ti. The detected 13C-13C satellites (7) are modulated in amplitude as a function of tl with the double quantum frequencies (2). In the quadrature-Fi-detection version of this experiment (3), results are combined with those of a second experiment which contains a composite 45: pulse (8) in the evolution period. This allows the sign of the modulation frequency to be determined, which simplifies the interpretation of the results. A simpler and more sensitive alternative to obtain quadrature F, detection has been proposed more recently (6); an increase of the flip angle of the final “read pulse” to 135” provides directly satellite signals which are modulated in phase as a function oft,. In either case, data acquisition is started after the final read pulse and the coherence transfer echo (9) is detected (4, 6). The time domain signal of a carbon A, directly coupled to carbon X, is then given by sA(tl, t2) = c exp[-i(nA + &)t,] exp[i& + d&2]
1H Indirect detected 13C Low-Abundance Single-transition correlation Spectroscopy (HICLASS)-13C homonuclear correlation at natural abundance.
A novel proton-detected (13)C homonuclear correlation experiment is reported at natural abundance, viz., (1)H Indirect detected (13)C Low-Abundance Single-transition correlation Spectroscopy (HICLASS). HICLASS is based on the evolution of (13)C single-quantum single transitions, followed by their mixing, and (1)H detection subsequent to heteronuclear transfer. Reduced relaxation losses during the evolution time and partial selectivity in the (1)H multiplet structure result in enhanced sensitivity of HICLASS. The superior performance of HICLASS is demonstrated for (1)H-detected (13)C correlation work.
Palaeomicrobiology: current issues and perspectives
Palaeomicrobiology is an emerging field that is devoted to the detection, identification and characterization of microorganisms in ancient remains. Data indicate that host-associated microbial DNA can survive for almost 20,000 years, and environmental bacterial DNA preserved in permafrost samples has been dated to 400,000–600,000 years. In addition to frozen and mummified soft tissues, bone and dental pulp can also be used to search for microbial pathogens. Various techniques, including microscopy and immunodetection, can be used in palaeomicrobiology, but most data have been obtained using PCR-based molecular techniques. Infections caused by bacteria, viruses and parasites have all been diagnosed using palaeomicrobiological techniques. Additionally, molecular typing of ancient pathogens could help to reconstruct the epidemiology of past epidemics and could feed into current models of emerging infections, therefore contributing to the development of appropriate preventative measures.