Design of Chiral Supramolecular Polymers Exhibiting a Negative Nonlinear Response.

Many synthetic and supramolecular chiral polymeric systems are known to exhibit the "majority rules effect" (MRE), a positive nonlinear response in which a small enantiomeric excess (ee) of the chiral building blocks leads to unproportionally large chiroptical signals near zero ee. In contrast, the opposite "racemate rules effect" (RRE), a negative nonlinear response in which the chiroptical signals are flat near zero ee, while giving large nonlinear chiroptical responses to ee at high values, has only been occasionally observed. The origin of this unusual ee dependence remains elusive largely because few systems have been established that exhibit this effect. Herein, we present a design approach that enables the development of chiral supramolecular polymers with a pronounced negative nonlinear response akin to RRE. This is achieved by in situ generating a bidentate inducer for supramolecular polymerization that exists in both meso- and homochiral forms upon reacting with chiral guests. The presence of the meso-inducer creates an aggregate structure that has a little response in the circular dichroism (CD) spectra as a function of ee at a particular wavelength, but a homochiral inducer gives large changes in response to ee at this wavelength. This allowed for an RRE-like response to be observed when the CD intensity of the supramolecular polymers was plotted against the ee of the chiral guests that generate the meso- and homochiral inducers without the necessity of the racemic guest preferentially being incorporated into the polymer.

Recent advances in boronic acid-based optical chemosensors.

Reversible covalent binding of boronic acids with polyols and Lewis bases has facilitated the development of robust chemosensors for many biologically important species under physiologically or environmentally relevant conditions. This minireview covers selected examples of advances reported in this area from 2014 to 2016. While the discovery of new boron-containing binding motifs and identification of new analytical targets have expanded the ultility of boronic acid-based molecular recognition, unconventional sensing strategies such as exploitation of nanoscale self-assembly, multicomponent dynamic covalent assembly, and coupling boronate ester formation with a further chemical reaction have led to significantly improved sensor performance, enabling real-world applications in various areas such as cell biology and asymmetric catalysis.

Induced helical chirality of perylenebisimide aggregates allows for enantiopurity determination and differentiation of α-hydroxy carboxylates by using circular dichroism.

We have developed a working strategy for accurate enantiomeric excess (ee) determination based on induced helical aggregation of achiral perylenebisimide (PBI) dyes. PBI dyes functionalized with boronic acid moieties were shown to be effective chirality sensors for α-hydroxy carboxylates. Seven α-hydroxy carboxylates tested showed strong induced Cotton effects in the perylene absorption region around λ=500 nm, which were utilized for enantiomeric excess determination and chemo-discrimination of the analytes, with an average absolute error of 2 % in ee determination and 100 % correctness in analyte classification. Responses in the absorption spectra, which arise from the guest-enhanced aggregation, allow the determination of the sample concentration, thus enabling analysis of samples of unknown concentration and ee. The simplicity of the strategy, the ease of sample preparation, and the accuracy demonstrated, can potentially facilitate screening procedures in asymmetric synthesis.

Selective sensing of saccharides using simple boronic acids and their aggregates.

The reversible boronic acid-diol interaction empowers boronic acid receptors' saccharide binding capacities, rendering them a class of lectin mimetic, termed "boronlectins". Boronic acids follow lectin functions not just in being able to bind saccharides, but in multivalent saccharide binding that enhances both affinity and selectivity. For almost a decade, efforts have been made to achieve and improve selectivity for given saccharide targets, most notably glucose, by using properly positioned boronic acids, offering multivalent interactions. Incorporation of several boronic acid groups into a covalent framework or non-covalent assembly of boronic acid are two general methods used to create such smart sensors, of which the latter resembles lectin oligomerisation that affords multivalent saccharide-binding architectures. In this review, we discuss supramolecular selective sensing of saccharides by using simple boronic acids in their aggregate forms, after a brief survey of the general aspects of boronic acid-based saccharide sensing.

A racemate-rules effect supramolecular polymer for ee determination of malic acid in the high ee region.

A supramolecular polymeric system that shows an unusual "racemate-rules" chiroptical property, an effect opposite to the well-known "majority-rules", has been utilized for accurate determination of malic acid enantiopurity at high ee values.

Self-assembly of a "double dynamic covalent" amphiphile featuring a glucose-responsive imine bond.

Glucose binding via boronate ester linkages selectively triggers imine bond formation between 4-formylphenylboronic acid and octylamine, leading to the formation of vesicular aggregates in aqueous solutions. This "double dynamic covalent assembly" allows the facile selective sensing of glucose against the otherwise serious interferant fructose, without the need to resort to synthetic effort.

Multicomponent covalent dye assembly for tight binding and sensitive sensing of L-DOPA.

A mixture of two simple perylene-containing receptors was found to bind bifunctional L-DOPA synergistically and tightly via orthogonal boronate ester and imine bond formation in neutral aqueous solutions, the resulting three-component assembly forming optically active long fibrous aggregates.

Direct sensing of fluoride in aqueous solutions using a boronic acid based sensor.

Binding of the fluoride ion triggers aggregation of a pyreneboronic acid-catechol ensemble in acidic aqueous solutions, giving rise to intense excimer emission, allowing for sensitive fluoride ion sensing at ppm levels, with an apparent fluoride binding constant higher than 10(3) M(-1) which is unprecedented for boronic acid sensors in water.