Amorphous nanoparticles of supramolecular coordination polymer networks are spontaneously self-assembled from nucleotides and lanthanide ions in water. They show intrinsic functions such as energy transfer from nucleobase to lanthanide ions and excellent performance as contrast enhancing agents for magnetic resonance imaging (MRI). Furthermore, adaptive inclusion properties are observed in the self-assembly process: functional materials such as fluorescent dyes, metal nanoparticles, and proteins are facilely encapsulated. Dyes in these nanoparticles fluoresce in high quantum yields with a single exponential decay, indicating that guest molecules are monomerically wrapped in the network. Gold nanoparticles and ferritin were also wrapped by the supramolecular shells. In addition, these nucleotide/lanthanide nanoparticles also serve as scaffolds for immobilizing enzymes. The adaptive nature of present supramolecular nanoparticles provides a versatile platform that can be utilized in a variety of applications ranging from material to biomedical sciences. As examples, biocompatibility and liver-directing characteristics in in vivo tissue localization experiments are demonstrated.
Dynamic covalent functionality has been acknowledged as a powerful tool for the construction of organised architectures, the reversible nature thermodynamically facilitates self-control and self-correction. The use of boronic acids complexation with diols and their congeners has already shown great promise in realising and developing reversible boron-containing multicomponent systems with dynamic covalent functionality. The structure-directing potential has lead to the development of a variety of self-organisation involving not only macrocycles, cages and capsules, but also porous covalent organic frameworks and polymers. Structure controls as well as remarkable synthesis are highlighted in this feature article.
The self-aggregation of cationic porphyrins in aqueous solution has been studied by means of absorption, 1 H NMR, and resonance light scattering spectroscopy. The aim of the present study is clarification of the factors which most influence porphyrin self-aggregation in water. Cationic 5,10,15,20-tetrasubstituted porphyrins [PorSub 4 : PC3Py (Sub ) -(CH 2 ) 3 -Py + Cl -), PC5Py (Sub ) -(CH 2 ) 5 -Py + Cl -), PC7Py (Sub ) -(CH 2 ) 7 -Py + Cl -), TPPOC2Py (Sub ) p-C 6 H 4 -O(CH 2 ) 2 -Py + Br -), and TPPOC3Py (Sub ) p-C 6 H 4 -O(CH 2 ) 3 -Py + Br -), where Py + ) N-alkylpyridinium] were used. PC3Py forms a dimer in aqueous solution with or without an added inorganic salt. In the presence of KNO 3 , dimer formation of PC3Py is dominated by a large and negative enthalpy change. The entropy change for aggregation increases with increasing concentrations of added KNO 3 , while enthalpy changes are almost constant. The thermodynamic parameters suggest that dimer formation of PC3Py is the result of a large enthalpic gain due to extended van der Waals interactions, in cooperation with enhanced hydrophobic interactions. Electrostatic repulsion suppresses further association. However, other cationic porphyrins studied show evidence of higher self-aggregate formation. X-ray crystallographic studies of PC5Cl (Sub ) -(CH 2 ) 5 -Cl), a precursor of PC5Py, show the formation of a slipped face-to-face dimer as the basic unit for forming a crystal lattice, while that of TPP (Sub ) -C 6 H 5 ) indicates the absence of face-to-face stacking interaction in the crystals. Judging from these results, it is assumed that the slipped face-to-face dimer is the unit of the higher self-aggregates of PC5Py or PC7Py in water with or without KNO 3 . Elongated alkyl chains of PC5Py and PC7Py may be responsible by enhancing hydrophobic interaction of the porphyrins studied. TPPOC2Py alone forms a J-aggregate, characterized by a sharp and red-shifted Soret band and a strongly enhanced resonance light scattering signal. Higher self-aggregates having face-to-face arrangement are formed with TPPOC3Py; these provide no enhanced RLS feature. The present study reveals the dependence of aggregate formation of water-soluble porphyrins on the peripheral mesosubstituents.
In this feature article the use of boronic acids to monitor, identify and isolate analytes within physiological, environmental and industrial scenarios is discussed. Boronic acids recognise diol motifs through boronic ester formation and interact with anions generating boronates, as such they have been exploited in sensing and separation protocols for diol appended molecules such as saccharides and anions alike. Therefore robust molecular sensors with the capacity to detect chosen molecules selectively and signal their presence continues to attract substantial attention, and boronic acids have been exploited with some success to monitor the presence of various analytes. Reversible boronic acid-diol interactions have also been exploited in boron affinity chromatography realising new separation domains through the same binding events. Boronic acid diol and anion interactions pertaining to sensing and separation are surveyed.
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