Reliable and precise methods capable of unambiguously identifying target analytes in real-world samples are indispensable in various fields, ranging from biological studies and diagnosis to quality control. Among various analytic techniques, nuclear magnetic resonance (NMR) is uniquely powerful as it provides multidimensional data useful for structural analysis at the atomic level. The rich information obtained from various NMR experiments allows one to access not only molecular structures and interactions but also the dynamics and diffusional properties. However, the interpretation of NMR data in the analysis of real-world mixtures can be challenging and is often complicated by the overlap of the NMR resonances of each component. Moreover, the inherently low sensitivity of the NMR technique hampers its implementation in many detections, where the analytes of interest are present at low concentrations. By a combination of heteronuclear NMR, dedicatedly designed sensors, ingenious transduction mechanisms, and powerful NMR pulse sequences, significant advancements were made to conquer these limitations. The present review summarizes the sensing systems that effectively facilitate NMR-based detection with an emphasis on the chemical perspective of sensor design and transduction mechanism. Advances in hyperpolarized sensors to boost the sensitivity of detection will also be included where appropriate.
The discovery of uncommon DNA structures and speculation about their potential functions in genes has brought attention to specific DNA structure recognition. G-quadruplexes are four-stranded nucleic acid structures formed by G-rich DNA (or RNA) sequences. G-rich sequences with a high potential to form G-quadruplexes have been found in many important genomic regions. Porphyrin derivatives with cationic side arm substituents are important G-quadruplex-binding ligands. For example, 5,10,15,20-Tetrakis(N-methylpyridinium-4-yl)-21H,23H-porphyrin (TMPyP4), interacts strongly with G-quadruplexes, but has poor selectivity for G-quadruplex versus duplex DNA. To increase the G-quadruplex recognition specificity, a new cationic porphyrin derivative, 5,10,15,20-tetra-{4-[2-(1-methyl-1- piperidinyl)ethoxy]phenyl} porphyrin (TMPipEOPP), with large side arm substituents was synthesized, and the interactions between TMPipEOPP and different DNA structures were compared. The results show that G-quadruplexes cause large changes in the UV-Vis absorption and fluorescence spectra of TMPipEOPP, but duplex and single-stranded DNAs do not, indicating that TMPipEOPP can be developed as a highly specific optical probe for discriminating G-quadruplex from duplex and single-stranded DNA. Visual discrimination is also possible. Job plot and Scatchard analysis suggest that a complicated binding interaction occurs between TMPipEOPP and G-quadruplexes. At a low [G-quadruplex]/[TMPipEOPP] ratio, one G-quadruplex binds two TMPipEOPP molecules by end-stacking and outside binding modes. At a high [G-quadruplex]/[TMPipEOPP] ratio, two G-quadruplexes bind to one TMPipEOPP molecule in a sandwich-like end-stacking mode.
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