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The novel spectral changes from the coordination polymers of Ag+ with a chiral cysteine-based ligand containing a TPE AIEgen.

Natural light-harvesting (LH) systems can divide identical dyes into unequal aggregate states, thereby achieving intelligent "allocation of labor". From a synthetic point of view, the construction of such kinds of unequal and integrated systems without the help of proteinaceous scaffolding is challenging. Here, we show that four octatetrayne-bridged ortho-perylene diimide (PDI) dyads (POPs) self-assemble into a quadruple assembly (POP)4 both in solution and in the solid state. The two identical PDI units in each POP are compartmentalized into weakly coupled PDIs (P520) and closely stacked PDIs (P550) in (POP)4 . The two extreme pools of PDI chromophores were unambiguously confirmed by single-crystal X-ray crystallography and NMR spectroscopy. To interpret the formation of the discrete quadruple assembly, we also developed a two-step cooperative model. Quantum-chemical calculations indicate the existence of multiple couplings within and across P520 and P550, which can satisfactorily describe the photophysical properties of the unequal quadruple assembly. This finding is expected to help advance the rational design of dye stacks to emulate functions of natural LH systems.

Na+, Cl− and K+ are the most abundant electrolytes present in biological fluids that are essential to the regulation of pH homeostasis, membrane potential and cell volume in living organisms. Herein, we report synthetic crown ether-thiourea conjugates as a cation/anion symporter, which can transport both Na+ and Cl− across lipid bilayers with relatively high transport activity. Surprisingly, the ion transport activities were diminished when high concentrations of K+ ions were present outside the vesicles. This unusual behavior resulted from the strong affinity of the transporters for K+ ions, which led to predominant partitioning of the transporters as the K+ complexes in the aqueous phase preventing the transporter incorporation into the membrane. Synthetic membrane transporters with Na+, Cl− and K+ transport capabilities may have potential biological and medicinal applications. [Figure not available: see fulltext.]

The 2,5-thiophenediamide motif that contains two intramolecular S⋯OC chalcogen bonds was taken to maintain cis-conformation of β-turn structured helical azapeptide that is good to form a supramolecular helix via intermolecular halogen bonding.

Spontaneous resolution leading to conglomerate crystals remains a significant challenge. Here we propose the formation of orthogonal homochiral supramolecular helices in at least two dimensions to allow spontaneous resolution. We suggest the design rationale that the chiral species is made into helical building blocks to allow the helix formation. As a proof-of-concept, acetylalanine was made into a helical short azapeptide, its N-amidothiourea derivative containing a β-turn structure, to which a halogen atom was further introduced at the phenylthiourea aromatic ring. The resultant folded species undergoes both intermolecular hydrogen and halogen bonding across the turn structure to form orthogonal intermolecular hydrogen-bonded and halogen-bonded supramolecular helices in two dimensions, and undergoes chiral resolution upon crystallization. Meanwhile, counterparts containing either an F-substituent with weak halogen bonding or no halogen atom crystallize as racemic compounds.

We report a new scheme for chiral recognition using coordination polymers of Ag+ with a chiral thiol ligand that contains a binding group. N-Benzoyl-l-cysteine ethyl ester equipped with a boronic acid group at the para position of the phenyl ring forms coordination polymers with Ag+ in alkaline aqueous solutions that exhibit excellent selectivity toward a d-glucose enantiomer over l-glucose, while the coordination polymers from the d-cysteine-based thiol ligand are specific for l-glucose. It is assumed that a conformation change occurs upon interaction of a saccharide molecule with the polymeric chain receptor, for which the next binding is promoted, leading to the highly effective chiral recognition, despite the flexible nature of the polymeric receptor.

We report a supramolecular nanosphere with a diameter of 8.65 nm built in an aqueous solution via dynamic binding of glucose to a thiol ligand bearing a phenylboronic acid group, 4-mercaptophenylboronic acid (4-MPBA), as a hydrophilic component in combination with a hydrophobic thiol ligand, 1-octanethiol (n-C8H17SH), in the presence of Ag+. Highly hydrophilic glucose binding to two neighboring boronic acid groups from 4-MPBA ligands on their Ag+ coordination polymeric backbone, on which the hydrophobic n-C8H17SH ligands locate inwards, drives the coordination polymers into nanospheres. The supramolecular nanospheres are of small diameters with narrow size distribution characteristic of glucose among the tested monosaccharides including fructose and xylose.

We propose to create nanospheres in aqueous solutions from coordination polymers of Ag+ with a combination of a hydrophilic and a hydrophobic thiol, of diameter ca. 2.7 nm in the case of using cysteine and n-butanethiol. A spectral probe for the formation of the nanospheres is a reversal of the CD signal at 253 nm from negative in the case of cysteine alone to positive when cysteine and n-BuSH are both employed, together with an amplification.

Supramolecular helices from helical building blocks represent an emerging analogue of the α-helix. In cases where the helicity of the helical building block is well propagated, the head-to-tail intermolecular interactions that lead to the helix could be enhanced to promote the formation and the stability of the supramolecular helix, wherein homochiral elongation dominates and functional helical channel structures could also be generated. This feature article outlines the supramolecular helices built from helical building blocks, i.e., helical aromatic foldamers and helical short peptides that are held together by intermolecular π-π stacking, hydrogen/halogen/chalcogen bonding, metal coordination, dynamic covalent bonding and solvophobic interactions, with emphasis on the influence of efficient propagation of helicity during assembly, favouring homochirality and channel functions.

We report supramolecular helical assembly in water of β-turn structured bis(N-amidothioureas) containing Br-substitutes of moderate halogen bonding ability, promoted by stronger hydrophobic interaction. The helical polymers show an unusual negative nonlinear CD-ee dependence.

Supramolecular chirality of aggregates can be described in terms of the CD signals of the aggregates as a function of the enantiomeric excess of the chiral building block or chiral inducer. While many examples have been reported that show a positive nonlinear CD- ee relationship, indicating chiral amplification, the negative nonlinear dependence has rarely been observed. We recently proposed to build such supramolecular aggregates by using the mesomer of the enantiomeric inducers. Indeed we found that in the presence of enantiomeric dibenzoyltartaric acids (DboTar), achiral perylenebisimide (PBI) dye equipped with two terminal guanidinium groups in alkaline aqueous buffer solution is induced to form chiral supramolecular aggregates, via the known guanidinium-carboxylate salt bridge, that show a positive nonlinear CD- ee relationship, and is turned into negatively nonlinear when 40% or more molar fraction of meso -DboTar was introduced. Absorption and CD spectral titrations suggest that the aggregates led by enantiomers and by mesomer are similar in terms of the supramolecular structure and stability, and when the two kinds of aggregates are mixed no molecular exchange occurs between them. Fluorescence spectral traces of the aggregates show that the mesomer is more powerful in inducing the aggregation of the PBI dyes, and thus dominates the aggregation. Our findings that the mesomer of the enantiomeric inducer could lead to aggregates to exhibit a negative nonlinear CD- ee relationship provide a promising approach to such supramolecular aggregates, which could be of significance for better insight into the mechanism leading to the negative nonlinear dependence and eventually a comprehensive understanding of the supramolecular chirality.

A C-terminal amidothiourea motif is shown to promote a β-turn-like folded conformation in a series of β-amino acid-based short peptides in both the solid state and solution phase by an intramolecular 11-membered ring hydrogen bond.

Conventionally, z-direction modulation of two-dimensional covalent organic frameworks (2D-COFs) is difficult to achieve because they rely on spontaneous π-π interactions to form 3D architectures. Herein, we report a facile construction of a novel intercalated covalent organic framework (Intercalated-COF) by synchronizing operations of supramolecular donor-acceptor (D-A) interactions (A unit: 2,5,8,11-tetra(p-formylphenyl)-perylene diimide (PDI) 1; D unit: perylene 3, as intercalator) in the vertical directions, with polymerizations (by only reacting 1 with p-phenylenediamine 2) in the lateral directions. In this Intercalated-COF, the PDI-based covalent 2D layers are uniformly separated by perylene guest layers. This supramolecular strategy opens the possibility for z-direction modulation of 2D-COFs through "intercalating" various guest molecules and thus may contribute to the exploration of advanced applications of these porous and crystalline frameworks.

Proline based receptors (1-14) attached with phenylboronic acid and benzaldehyde binding groups at the N-/C- or C-/N-termini of the proline residue were created for chiral recognition of l-/d-DOPA, in an attempt to examine if balancing the two binding events would influence the recognition. By changing the positions of boronic acid and aldehyde groups substituted on the phenyl rings (1-4, 5-8) and the site at which phenylboronic acid and benzaldehyde moieties attached respectively to the N- and C-termini or C- and N-termini of the proline residue (1-4vs.5-8), and by introducing an electron-withdrawing fluorine atom in the phenyl ring of the weaker binder the benzaldehyde moiety (11vs.1, 14vs.5), we were able to show that a better balance of the two binding events does improve the chiral recognition. This finding can only be made with the current version of receptors that were equipped with two different binding groups. Together with the finding that the chiral recognition performance in mixed organic-aqueous solutions is tunable by varying the solvent composition, we have now arrived at a protocol for designing proline based receptors for extended applications in chiral recognition.

We propose using the formation of coordination polymers of Ag+ to probe differences between the perfluorinated alkyl chain and the alkyl chain by deriving a thiol ligand, N-(perfluoroalkanoyl)cysteine. Rapid formation in EtOH of P-/M-helical nanofibrils of high thermostability was found for N-(perfluorooctanoyl)-L-/D-cysteine ethyl esters at the μM level upon mixing with Ag+, but not for the octanoyl counterpart. This difference was also observed in terms of circular dichroism-enantiomeric excess dependence.

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 “at 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.

Supramolecular helices from helical building blocks represent an emerging analogue of the α-helix. In cases where the helicity of the helical building block is well propagated, the head-to-tail intermolecular interactions that lead to the helix could be enhanced to promote the formation and the stability of the supramolecular helix, wherein homochiral elongation dominates and functional helical channel structures could also be generated. This feature article outlines the supramolecular helices built from helical building blocks

To explore whether chalcogen bonding was able to drive the formation of supramolecular helices, alanine-based azapeptides containing a β-turn structure, with a thiophene group, respectively, incorporated in the N- or C-terminus, were employed as helical building blocks. While the former derivative formed a supramolecular M-helix via intermolecular S⋯S chalcogen bonding in crystals, the latter formed P-helix via intermolecular S⋯O chalcogen bonding.

The synthesis, structures, and properties of [4]cyclonaphthodithiophene diimides ([4]C-NDTIs) are described. NDTIs as important n-type building blocks were catenated in the α-positions of thiophene rings via an unusual electrochemical-oxidation-promoted macrocyclization route. The thiophene-thiophene junction in [4]C-NDTIs results in an ideal pillar shape. This interesting topology, along with appealing electronic and optical properties inherited from the NDTI units, endows the [4]C-NDTIs with both near-infrared (NIR) light absorptions, strong excitonic coupling, and tight encapsulation of C60 . Stable orientations of the NDTI units in the nanopillars lead to stable inherent chirality, which enables detailed circular dichroism studies on the impact of isomeric structures on π-conjugation. Remarkably, the [4]C-NDTIs maintain the strong π-π stacking abilities of NDTI units and thus adopt two-dimensional (2D) lattice arrays at the molecular level. These nanopillar molecules have great potential to mimic natural photosynthetic systems for the development of multifunctional organic materials.

We report a new scheme for chiral recognition using coordination polymers of Ag

The natural DNA double helix consists of two strands of nucleotides that are held together by multiple hydrogen bonds. Here we propose to build an artificial double helix from fragments of two strands connected by covalent linkages therein, but with halogen bonding as the driving force for self-assembling the fragments to the double helix. We succeed in building such a double helix in both solution and solid state, by using a bilateral N-(p-iodobenzoyl)alanine based amidothiourea which in its folded cis-form allows double and crossed C−I···S halogen bonds that lead to right- or left-handed double helix when the two alanine residues are of the same L,L- or D,D-configuration. The double helix forms in dilute CH3CN solution of the micromolar concentration level, e.g., 5.6 μM from 2D NOESY experiments and exhibits a high thermal stability in solution up to 75 °C, suggesting cooperative and thereby strong intermolecular double crossed halogen bonding that makes the double helix stable. This is supported by the observed homochiral self-sorting in solution., Building an artificial double helix is a compelling challenge, and most strategies rely on the intertwining of two helical strands. Here, in a very different approach, the authors construct a supramolecular double helix from multiple synthetic small molecules chained together by double crossed halogen bonds.

We report coordination polymers forming from Ag+ and a chiral thiol ligand that bears a β-turn structure, exhibiting supramolecular chirality showing both the majority rules effect (MRE) and the racemate rules effect (RRE).

The classic spectral molecular sensor consists of a binding site linked to a chromophore via a conjugate or nonconjugate spacer, thus a spectral background may exist. It is therefore demanded to have a spectral sensing scheme with in situ formed chromophore when the sensing species is present with the sensory molecule that the spectral sensing is in principle background free. Metal cations of d8 or d10 electronic configuration when brought into close proximity would facilitate the metallophilic interaction, exhibiting characteristic spectral signals from the chromophore in situ generated upon the occurrence of metal … metal interaction. This Review discusses four spectral sensing platforms with chromophores in situ generated, i.e., the homoatomic metallophilic complexes such as multinuclear Au+ complexes, cofacial stacking of Pt2+ ensembles, Ag+-thiol coordination polymers, and heterometallic complexes. These sensing platforms represent a new scheme that relies on the signalling chromophore in situ generated only when the sensing species is present.

Chiral recognition remains a major challenge in the area of molecular receptor design. With this research, we set out to explore the use of proline-based receptors for chiral recognition. Importantly, the proline structure allows for the introduction of at least two different binding groups due to the availability of both an amine and carboxylic acid group. Here we report a proof-of-concept exploration into the chiral recognition of d/l-glucose as a model chiral species, which prefers to bind to at least two boronic acid groups. We evaluated several proline-based receptors incorporating two phenylboronic acid groups, respectively, at the N- and C-termini of the amino acid residue, via amide bonds. We confirmed that the receptors exhibited chiral recognition using CD, 1H NMR, and 19F NMR spectroscopy. Given the derivation diversity available, our strategy to use proline-based receptors for chiral recognition holds significant promise for extension to other chiral systems.

We show herein the phosphatase-like catalytic activity of coordination polymers obtained after adding Ag + -ions to thiols bearing hydrophobic alkyl chains terminated with a 1,4,7-triazacyclononane (TACN) group. The subsequent addition of Zn 2+ -ions to the self-assembled polymers resulted in the formation of multivalent metal coordination polymers capable of catalysing the transphosphorylation of an RNA-model compound (2-hydroxypropyl-4-nitrophenyl phosphate, HPNPP) with high reactivity. Analysis of a series of metal ions showed that the highest catalytic activity was obtained when Ag + -ions were used as the first metal ions to construct the backbone of the coordination polymer through interaction with the -SH group followed by Zn 2+ -ions as the second metal ions complexed by the TACN-macrocycle. Furthermore, it was demonstrated that the catalytic activity could be modulated by changing the length of the hydrophobic alkyl chain.

Diverse classes of anion transporters have been developed, most of which focus on the transmembrane chloride transport due to its significance in living systems. Fluoride transport has, to some extent, been overlooked despite the importance of fluoride channels in bacterial survival. Here, we report the design and synthesis of a cyclic azapeptide (a peptide-based N-amidothiourea, 1), as a transporter for fluoride transportation through a confined cavity that encapsulates fluoride, together with acyclic control compounds, the analogs 2 and 3. Cyclic receptor 1 exhibits more stable β-turn structures than the control compounds 2 and 3 and affords a confined cavity containing multiple inner –NH protons that serve as hydrogen bond donors to bind anions. It is noteworthy that the cyclic receptor 1 shows the capacity to selectively transport fluoride across a lipid bilayer on the basis of the osmotic and fluoride ion-selective electrode (ISE) assays, during which an electrogenic anion transport mechanism is found operative, whereas no transmembrane transport activity was found with 2 and 3, despite the fact that 2 and 3 are also able to bind fluoride via the thiourea moieties. These results demonstrate that the encapsulation of an anionic guest within a cyclic host compound is key to enhancing the anion transport activity and selectivity.

We propose using the formation of coordination polymers of Ag+ to probe differences between the perfluorinated alkyl chain and the alkyl chain by deriving a thiol ligand, N-(perfluoroalkanoyl)cysteine. Rapid formation in EtOH of P-/M-helical nanofibrils of high thermostability was found for N-(perfluorooctanoyl)-l-/d-cysteine ethyl esters at the μM level upon mixing with Ag+, but not for the octanoyl counterpart. This difference was also observed in terms of circular dichroism-enantiomeric excess dependence.

Building folded short peptides that are driven by the intramolecular hydrogen bonding in aqueous solutions remains challenging because of their highly competitive intermolecular hydrogen-bonding interactions with water solvent molecules that would have favored the extended conformations. Here, we show folded β-turn structures in acyl amino acid-based N-amidothioureas, the nonclassic azapeptides, in aqueous solutions, as well as in solid-state and organic solvents, by X-ray crystal structures, DFT calculations, 1D and 2D NMR spectra, and absorption and CD spectra. The achiral phenylthiourea chromophore acts as a CD reporter for the β-turn structure that communicates the chirality of the amino acid residue to the achiral thiourea moiety and the relative intensity of the intramolecular hydrogen bond that stabilizes the turn structure. The amidothiourea moiety represents a versatile structural framework for folded short peptides in aqueous environments.

Traditionally, fluorescence probes have focused on the detection of a single biomarker for a specific process. In this work, we set out to develop a number of fluorescence probes that enable the detection of a chosen analyte in the presence of reactive oxygen/nitrogen species (ROS/RNS). These fluorescence probes when activated result in the formation of the highly fluorescent pink dye, resorufin. Therefore, we have labelled these fluorescent probes as ‘Pinkments’. Our first ‘Pinkment’ was shown to detect biologically relevant concentrations of ONOO− and have an excellent selectivity against other ROS/RNS. Pinkment-OH was developed to provide a core unit which could be easily functionalised to produce a range of ‘AND’ based fluorescence probes for the detection of ROS/RNS and a second analyte. For proof of concept, we synthesised Pinkment-OTBS and Pinkment-OAc. These ‘AND’-based probes were successfully shown to detect ROS/RNS and F− or esterase, respectively.

As emerging sensory ensembles, Ag(I)-thiolate coordination polymers have been drawing great research interests in the past few years. Ag(I)-thiolate coordination polymers feature unique physical properties such as semiconductivity, luminescence, photothermal and thermochromic effects, which could be leveraged to build physical and chemical sensors, as well as novel multifunctional biomaterials. This review summarizes the synthesis, structures and applications of Ag(I)-thiolate coordination polymers as sensory ensembles towards physical parameters such as temperature and light and chemical analytes including ions, VOCs, amino acids and saccharides. Developments of functional hydrogels for chemosensing and in situ drug delivery are also discussed.

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.

Herein, we report a conformation switching-based fluorescence sensing scheme using dipeptide-based amidothioureas (azapeptides) that contain a folded β-turn structure. Amidothiourea is equipped at its two termini with an electron acceptor and an electron donor or two fluorophores, such that it exhibits enhanced exciplex or excimer emission because of the turn structure in which the two termini are brought into close proximity; on the other hand, it exhibits a dramatic ratiometric fluorescence response upon anion binding to the thiourea moiety because of the resultant extended conformation of the anion binding complex.

We report that in the Ag+ coordination polymers of a chiral thiol ligand containing an AIE fluorophore, tetraphenylethene (TPE), the TPE chromophores experience H-type aggregation, and yet a substantial enhancement of the fluorescence is observed, though to a lesser extent than that in the aggregates of the thiol ligand itself, which undergoes J-type aggregation. We show that this is not due to the difference in the freedom of the rotation of the fluorophore in the two types of aggregate, but is due to a small increase in the radiation rate constant in the coordination polymers while the much higher radiationless rate constant remains more or less unchanged.

The formation of well-defined finite-sized aggregates represents an attractive goal in supramolecular chemistry. In particular, construction of discrete π-stacked dye assemblies remains a challenge. Reported here is the design and synthesis of a novel type of discrete π-stacked aggregate from two comparable perylenediimide (PDI) dyads (PEP and PBP). The criss-cross PEP-PBP dimers in solution and (PBP-PEP)-(PEP-PBP) tetramers in the solid state are well elucidated using single-crystal X-ray diffraction, dynamic light scattering, and diffusion-ordered NMR spectroscopy. Extensive π–π stacking between the PDI units of PEP and PBP as well as repulsive interactions of swallow-tailed alkyl substituents are responsible for the selective formation of discrete dimer and tetramer stacks. Our results reveal a new approach to preparing discrete π stacks that are appealing for making assemblies with well-defined optoelectronic properties.

Reported here is the induced helical aggregation of an achiral cationic perylene-3,4-dicarboximide (1) that contains a phenylboronic acid group, together with UMP that bears a cis-diol moiety able to interact with boronic acid and an imide group known to coordinate with Hg2+. In selected solvents, 1 exists in monomer form, even in the presence of either UMP or Hg2+. Helical aggregation only takes place if 1 is mixed with both UMP and Hg2+, which is shown to result from the formation of a building block consisting of five components in the form 1–U–Hg2+–U–1. Strong exciton-coupled circular dichroism signals were observed in the absorption window of the achiral dye chromophore, demonstrating the transfer of the chirality of UMP to the supramolecular aggregates of P-helicity. Synergism was shown to occur upon aggregation of the 1–U–Hg2+–U–1 building block, as substantially enhanced affinity and binding selectivity were observed for UMP and Hg2+, despite the otherwise weak and less selective interactions of 1–UMP and UMP–Hg2+. In support of this synergism, the g-factor of the aggregates was found to be 1.4×10−2, which represents a high value. We thus show a strategy of in situ construction of a building block from multiple components, among which the interactions can be weak and less selective. Therefore, the design and syntheses of the constituent components are substantially simplified, yet diverse functions can be expected from their supramolecular aggregates.

As a new emerging area in chemical sensing, sensing using supramolecular aggregates exhibits unique advantages over that using conventional small-molecule chemical sensors, in terms of high sensitivity and selectivity, and the simplicity of the sensory building blocks. This Feature Article outlines the recent research progress made in sensing based on induced supramolecular aggregation-disaggregation. The reviewed sensory building blocks, in general, in the form of a small molecular sensor, yet with a much simpler structure, which form aggregates, are those of perylene derivatives, pyrene derivatives, tetraphenylethylene derivatives, metallophilic species and metal-organic frameworks.

Although a linear relationship between the optical activity (normally the CD signal) and the enantiomeric excess (ee) of chiral auxiliaries has been the most commonly observed dependence in dynamic supramolecular helical aggregates, positive nonlinear CD-ee dependence, known as the "majority-rules effect" (MRE), indicative of chiral amplification, has also been well documented and to some extent understood. In sharp contrast, the negative nonlinear CD-ee dependence has been much less reported and is not well understood. Here, the state of the art of both the positive and negative nonlinear CD-ee dependence in noncovalently bound supramolecular helical aggregates is summarized, with the hope that the vast examples of supramolecular aggregates showing positive nonlinear dependence, in terms of the methods of investigations, variations in the structure of the building block (single species or multiple species), and theoretical modeling using the mismatch penalty energy and helix reversal penalty energy, would help to guide the design of building blocks to form aggregates showing negative nonlinear dependence, and thus to understand the mechanisms. The potential applications of those functional supramolecular aggregates are also discussed.

We report a dynamic covalent approach to transmembrane transport of amino acids by the formation of a three-component assembly. A mixture of a squaramide and a lipophilic and electrophilic aldehyde is shown to synergistically transport highly polar glycine (Gly) across vesicle membranes. The transport was investigated by a 13C NMR assay, an osmotic response assay and a newly-developed fluorescence assay suitable for measuring Gly influx, and other fluorescence assays for leakage and pH change. The transport is proposed to occur via a hydrogen-bonded anionic glycine hemiaminal/imine, accompanied by transport of OH- in the opposite direction. Several control experiments support the role of hemiaminal/imine in the observed facilitated Gly transport. Proton NMR studies of a biphasic system show the presence of both the hemiaminal and imine formed between Gly and an aldehyde. Interestingly, the synergistic effect has also been observed for sarcosine (Sar) that can form hemiaminals but not imines. The results demonstrate the potential of hemiaminal formation for the facilitated transport of substrates containing primary and secondary amino groups.

A biocompatible fluoride receptor has been developed where the interaction between the boronic acid ester and amine (NH) results in fluoride ion selectivity and enhanced fluorescence quenching.

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.