Paper-based assays such as lateral flow assays are good candidates for portable diagnostics owing to their user-friendly format and low cost. In terms of analytical detection, lateral flow assays usually require dedicated instruments to obtain quantitative results. Here we demonstrate a lateral flow assay with handheld pressure meter readout for the rapid detection of disease-related protein with high sensitivity and selectivity. Based on the pressure change produced by the catalytic reaction of Pt nanoparticles related to the concentration of the target, a quantitative reaction platform was established. During the lateral flow assay, the Pt nanoparticles are aggregated in the test line to form a gray band by biomolecular recognition and finally convert the recognition signal into highly sensitive pressure readout for quantitative analysis. Without sophisticated instrumentation and complicated operations, the whole detection process can be completed within 20 minutes. The limit of detection for myoglobin (2.9 ng mL in diluted serum samples) meets the requirements of clinical monitoring. With the advantages of low cost, ease of operation, high sensitivity and selectivity, the method represents a versatile platform for point-of-care testing of disease biomarkers.
Here we demonstrate how the hydrogen-bonding ability of a BINOL-based dialdehyde subcomponent dictated the stereochemical outcome of its subsequent self-assembly into one diastereomeric helicate form when bearing free hydroxy groups, and another in the case of its methylated congener. The presence of methyl groups also altered the self-sorting behavior when mixed with another, short linear dialdehyde subcomponent, switching the outcome of the system from narcissistic to integrative self-sorting. In all cases, the axial chirality of the BINOL building block also dictated helicate metal center handedness during stereospecific selfassembly. A new family of stereochemically pure heteroleptic helicates were thus prepared using the new knowledge gained. We also found that switching from Fe II to Zn II , or the incorporation of a longer linear ligand, favored heteroleptic structure formation.
An enantiopure ligand with four bidentate metal-binding sites and four ( S )-carbon stereocenters self-assembles with octahedral Zn II or Co II to produce O -symmetric M 8 L 6 coordination cages. The Λ- or Δ-handedness of the metal centers forming the corners of these cages is determined by the solvent environment: the same ( S )-ligand produces one diastereomer, ( S ) 24 -Λ 8 -M 8 L 6 , in acetonitrile but another with opposite metal-center handedness, ( S ) 24 -Δ 8 -M 8 L 6 , in nitromethane. Van ’t Hoff analysis revealed the Δ stereochemical configuration to be entropically favored but enthalpically disfavored, consistent with a loosening of the coordination sphere and an increase in conformational freedom following Λ-to-Δ transition. The binding of 4,4′-dipyridyl naphthalenediimide and tetrapyridyl Zn-porphyrin guests did not interfere with the solvent-driven stereoselectivity of self-assembly, suggesting applications where either a Λ- or Δ-handed framework may enable chiral separations or catalysis.
Biomolecular systems show how host–guest binding can induce changes in molecular behavior, which in turn impact the functions of the system. Here we report an artificial host–guest system where dynamic adaptation during guest binding alters both host conformation and guest dynamics. The self-assembled cage host employed here possesses concave walls and a chirotopic cavity. Complementarity between the curved surfaces of fullerenes and the inner surface of the host cavity leads the host to reconfigure stereochemically in order to bind these guests optimally. The curved molecule corannulene undergoes rapid bowl-to-bowl inversion at room temperature. Its inversion barrier is increased upon binding, however, and increased further upon formation of a ternary complex, where corannulene and a cycloalkane are both bound together. The chiral nature of the host also leads to clear differences in the NMR spectra of ternary complexes involving corannulene and one or the other enantiomer of a chiral guest, which enables the determination of enantiomeric excess by NMR.
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