Cyanostilbene-based fluorescent paper array for monitoring fish and meat freshness via amino content detection.

The detection of biogenic amines released from degraded meats is an effective method for evaluating meat freshness. However, existing traditional methods like titration are deemed tedious, while the use of sophisticated analytical instruments is not amenable to field testing. Herein, a cyanostilbene-based fluorescent array was rapidly fabricated using macroarray synthesis on a cellulose paper surface to detect amines liberated from spoiled beef, fish, and chicken. The fluorescence changes of immobilized molecules from the interaction with gaseous amines were used to monitor changes in freshness levels. Thanks to the high-throughput nature of macroarray synthesis, a set of highly responsive molecules such as pyridinium and dicyanovinyl moieties were quickly revealed. Importantly, this method offers flexibility in sensing applications including (1) sensing by individual sensor molecules, where the fluorescence response correlated well with established titration methods, and (2) collective sensing whereby chemometric analysis was used to provide a cutoff of freshness with 73-100% accuracy depending on meat types. Overall, this study paves the way for a robust and cost-effective tool for monitoring meat freshness.

Highly Chiral Selective Resolution in Pillar[6]arenes Functionalized Microchannel Membranes.

High flux microchannel membranes have the potential for large scale separations. However, it is prevented by poor enantioselectivity. Therefore, the development of a high-enantioselective microchannel membrane is of great importance for large scale chiral separations. In this work, chiral gold nanoparticles are incorporated into the microchannel membrane to astringe the large pores and improve the enantioselectivity. Here, the gold nanoparticles are functionalized by l-phenylalanine-derived pil-lararenes (l-Phe-P6@AuNPs) as the chiral receptor of R-phenylglycinol (R-PGC) over its enantiomer. This chiral Au NPs coated microchannel membrane (l-Phe-P6@AuNPs microchannel) shows a selectivity of 5.40 for R-PGC and a flux of 140.35 nmol·cm-2·h-1, where the enantioselectivity is improved, ensuring its flux. Compared with the enantioselectivity and flux of nanochannel membranes reported in literatures, the l-Phe-P6@AuNPs microchannel has the advantage for enantioselectivity and flux for chiral separation.

A Funnel-Shaped Chloride Nanochannel Inspired By ClC Protein.

Chloride transport participates in a great variety of physiological activities, such as regulating electrical excitability and maintaining acid-base equilibrium. However, the high flux is the prerequisite to ensure the realization of the above functions. Actually, the high flux of ion transport is significant, not only for living things but also for practical applications. Herein, inspired by chloride channel (ClC) protein, a novel NH2-pillar[5]arene functionalized funnel-shaped nanochannel was designed and constructed. The introduction of functional molecules changed surface charge property and endowed the nanochannel with Cl- selectivity, which facilitated Cl- transport. Moreover, by adjusting the asymmetric degree of the nanochannel, the Cl- transport flux can be improved greatly. The successful construction of an artificial ion channel with high flux will be much useful for practical applications like microfluidic devices, sensors, and ion separation.

A Visible-Light-Regulated Chloride Transport Channel Inspired by Rhodopsin.

Inspired by the light-regulating capabilities of naturally occurring rhodopsin, we have constructed a visible-light-regulated Cl- -transport membrane channel based on a supramolecular host-guest interaction. A natural retinal chromophore, capable of a visible-light response, is used as the guest and grafted into the artificial channel. Upon introduction of an ethyl-urea-derived pillar[6]arene (Urea-P6) host, threading or de-threading of the retinal and selective bonding of Cl- can be utilized to regulate ion transport. Based on the visible-light responsiveness of the host-guest interaction, Cl- transport can be regulated by visible light between ON and OFF states. Visible-light-regulated Cl- transport as a chemical model permits to understand comparable biological ion-selective transport behaviors. Furthermore, this result also supplies a smart visible-light-responsive Cl- transporter, which may have applications in natural photoelectric conversion and photo-controlled delivery systems.

Pillar[5]arene Promoted Selective Spreading of Chlormequat Droplets on a Hydrophobic Surface.

Promoting the spreading and deposition of agricultural sprays on the crop surface is of great significance for effective utilization of these chemicals. Selective host-guest interaction established between chlormequat and hydroxyl pillar[5]arene was well utilized in the present work for effective spreading of chlormequat droplets over the hydrophobic surface, which was silanized with triethoxy (octyl) silane and then assembled with hydroxybenzene pillar[5]arene molecules. Therefore, this surface was facile for the assembly of chlormequat in droplets and ultimately increased the selective adhesion of chlormequat through host-guest interactions. Moreover, the pillar[5]arene-fabricated surface shows considerable potential applications for rapid detection of chlormequat in environmental monitoring and also provides a novel approach for improving the chlormequat efficiency.

Supramolecular gel from self-assembly of a C3-symmetrical discotic molecular bearing pillar[5]arene.

A novel C3-symmetric benzene-1,3,5-tricarboxamide (BTAs) decorated with three identical pillar[5]arene tails was designed, synthesized and characterized. The compound can gelate acetonitrile at low concentration (0.2 wt%) upon sonication at room temperature, but a precipitate was obtained by a conventional heating-cooling process. Scanning electron microscopy revealed that the gel and precipitate were constructed by entangled, high-aspect-ratio flexible bundles of nanofibrils. UV-vis spectroscopy, circular dichroism, Fourier transform infrared microscopy and powder X-ray diffraction showed that the compound formed chiral, elongated, columnar aggregates with nanofiber morphology by a combination of intermolecular hydrogen bonding between the N-H and C[double bond, length as m-dash]O of amides, π-π stacking (H-aggregates) and hydrophobic interactions of peripheral groups.

A novel smart supramolecular organic gelator exhibiting dual-channel responsive sensing behaviours towards fluoride ion via gel-gel states.

A novel smart supramolecular organic gelator G-16 containing anion and metal-coordination ability has been designed and synthesized. It shows excellent and robust gelation capability as a strong blue fluorescent supramolecular organic gel OG in DMF. Addition of Zn(2+) produced Zn(2+)-coordinated supramolecular metallogel OG-Zn. Organic gel OG and organometallic gel OG-Zn exhibited efficient and different sensing behaviors towards fluoride ion due to the variation in self-assembling nature. Supramolecular metallogel OG-Zn displayed specific selectivity for fluoride ion and formed OG-Zn-F with dramatic color change from blue to blue green in solution and gel to gel states. Furthermore after directly addition of fluoride into OG produced fluoride containing organic gel OG-F with drastically modulation in color from blue to greenish yellow fluorescence via strong aggregation-induced emission (AIE) property. A number of experiments were conducted such as FTIR, (1)H NMR, and UV/Vis spectroscopies, XRD, SEM and rheology. These results revealed that the driving forces involved in self-assembly of OG, OG-Zn, OG-Zn-F and OG-F were hydrogen bonding, metal coordination, π-π interactions, and van der Waal forces. In contrast to the most anion responsive gels, particularly fluoride ion responsive gels showed gel-sol state transition on stimulation by anions, the gel state of OG and OG-Zn did not show any gel-to-sol transition during the whole F(-) response process.

Two bent-shaped π-organogelators: synthesis, fluorescence, self-assembly and detection of volatile acid vapours in gel films and in gel-gel states.

Two novel bent-shaped π-organogelators 6a and 6b having different terminal pyridine rings as responsive sites were designed, synthesized and fully characterized. A subtle difference in the position of the N atom at the pyridine ring greatly affected their fluorescence and gelation properties. 6b showed remarkably stronger fluorescence both in solution and in the solid state as compared to 6a. Theoretical calculation revealed a clear discrepancy in the electron distribution between them. Furthermore, driven by π­π stacking interaction and hydrophobic interaction, both 6a and 6b can gelate several organic solvents with different polarities. Rheological studies, spectroscopic tests and powder X-ray diffraction showed that 6a displayed a closer stacking mode leading to stronger gel robustness. The xerogel films of 6a and 6b were prepared and utilized to detect acid vapours. Both of them can fulfil the detection of acid vapours through a distinct fluorescence change which could be seen by the naked eye under a UV lamp, but with different sensing modes. A rare gel to gel transformation was also observed upon exposure to acid vapours accompanied by a morphological change.

Studies on a novel class of triaryl pyridine N-glycosylamine amphiphiles as super gelators.

A novel class of six different triaryl pyridine N-glycosylamine amphiphiles was synthesised and characterized based on different spectral techniques, such as NMR and mass analysis. Gelation properties in different aromatic and aliphatic solvents were studied and gelation was observed predominantly in aliphatic solvents with CGC of 0.5% (w/v) and is attributed to the presence of long alkyl chain. All the gels thus obtained were studied using FE-SEM and powder XRD techniques which reveal fibrous entanglement of the molecules in the gel state with intermolecular spaces of 3.62 nm and 0.43 nm.

Light-responsive nanochannels based on the supramolecular host-guest system.

The light-responsive nanochannel of rhodopsin gained wider research interest from its crucial roles in light-induced biological functions, such as visual signal transduction and energy conversion, though its poor stability and susceptibility to inactivation in vitro have limited its exploration. However, the fabrication of artificial nanochannels with the properties of physical stability, controllable structure, and easy functional modification becomes a biomimetic system to study the stimulus-responsive gating properties. Typically, light-responsive molecules of azobenzene (Azo), retinal, and spiropyran were introduced into nanochannels as photo-switches, which can change the inner surface wettability of nanochannels under the influence of light; this ultimately results in the photoresponsive nature of biomimetic nanochannels. Furthermore, the fine-tuning of their stimulus-responsive properties can be achieved through the introduction of host-guest systems generally combined with a non-covalent bond, and the assembling process is reversible. These host-guest systems have been introduced into the nanochannels to form different functions. Based on the host-guest system of light-responsive reversible interaction, it can not only change the internal surface properties of the nanochannel and control the recognition and transmission behaviors but also realize the controlled release of a specific host or guest molecules in the nanochannel. At present, macrocyclic host molecules have been introduced into nanochannels including pillararenes, cyclodextrin (CD), and metal-organic frameworks (MOFs). They are introduced into the nanochannel through chemical modification or host-guest assemble methods. Based on the changes in the light-responsive structure of azobenzene, spiropyran, retinal, and others with macrocycle host molecules, the surface charge and hydrophilic and hydrophobic properties of the nanochannel were changed to regulate the ionic and molecular transport. In this study, the development of photoresponsive host and guest-assembled nanochannel systems from design to application is reviewed, and the research prospects and problems of this photo-responsive nanochannel membrane are presented.

Enantioselective Antiport in Asymmetric Nanochannels.

Enantioselective sensing and separation are major challenges. Nanochannel technologies are energy-saving and efficient for membrane separation. Herein, inspired by biological antiporter proteins, artificial nanochannels with antiporter behavior were fabricated for chiral sensing and separation. Tyrosine enantiomers were incorporated into hourglass-shaped nanochannels via stepwise modifications to fabricating multiligand-modified asymmetric channels. Chiral distinction of naproxen enantiomers was amplified in the l-Tyr/d-Tyr channels, with an enantioselectivity coefficient of 524, which was over 100-fold that of one-ligand-modified nanochannels. Furthermore, transport experiments evidenced the spontaneous antiport of naproxen enantiomers in the l-Tyr/d-Tyr channels. The racemic naproxen sample was separated via the chiral antiport process, with an enantiomeric excess of 71.2%. Further analysis using electro-osmotic flow experiments and finite-element simulations confirmed that the asymmetric modified multiligand was key to achieving separation of the naproxen enantiomers. We expect these multiligand-modified asymmetric nanochannels to provide insight into mimicking biological antiporter systems and offer an approach to energy-efficient and robust enantiomer separation.

Chiral Nanochannels of Ordered Mesoporous Silica Constructed by a Pillar[5]arene-Based Host-Guest System.

The separation of racemic compounds by chiral nanochannels has attracted extensive attention. However, the fabrication of high-performance chiral nanochannels is still a challenge owing to the difficulty in magnifying the weak chiral interaction to macroscopic properties of materials. Herein, by introducing a l-alanine-pillar[5]arene host to achiral ordered mesoporous silica (OMS), chiral OMS nanochannels were fabricated, which exhibited excellent selectivity (ee value up to 90.2%) to separate racemic drugs with promising reusability and stability. Besides, it was identified that enantioselective separation took place through a molecular-recognition-adsorbed transport mechanism. This work highlights the great potential of chiral OMS nanochannels as a platform for enantioselective separation.

Recent advances in chiral discrimination on host-guest functionalized interfaces.

Chiral discrimination has gained much focus in supramolecular chemistry, since it is one of the fundamental processes in biological systems, enantiomeric separation and biochemical sensors. Though most of the biochemical processes can routinely recognize biological enantiomers, enantioselective identification of chiral molecules in artificial systems is currently one of the challenging topics in the field of chiral discrimination. Inaccuracy, low separation efficiency and expensive instrumentation were considered typical problems in artificial systems. Recently, chiral recognition on the interfaces has been widely used in the fields of electrochemical detection and biochemical sensing. For the moment, a series of macrocyclic host functionalized interfaces have been developed for use as chiral catalysts or for enantiomeric separation. Here, we have briefly exposited the most recent advances in the fabrication of supramolecular functionalized interfaces and their application for chiral recognition.

Selective transmembrane transport of Aß protein regulated by tryptophan enantiomers.

Tryptophan enantiomers (d/l-Trp) were introduced into artificial nanochannels to regulate the chiral selective transport of Aß proteins. The l-Trp channel performs effectively selectivity for the transport of Aß protein, which would provide a new perspective for the pathological studies of Alzheimer's disease.

The light-driven macroscopic directional motion of a water droplet on an azobenzene-calix[4]arene modified surface.

A novel photo-responsive surface was constructed via modifying azobenzene-calix[4]arene (ABC4) on a microstructured silicon surface. Asymmetric UV light irradiation could drive the macroscopic directional motion of a water droplet on this photo-responsive surface.

Phenethylamine@Pillar[5]arene Biointerface for Highly Enantioselective Adsorption of Protein.

In the life system, the biointerface plays an important role in cell adsorption, platelet adsorption and activation. Therefore, the study of protein adsorption on the biointerface is of great significance for understanding life phenomena and treatment in vitro. In this paper, a chiral biointerface was constructed by the virtue of host-guest interaction between a water-soluble pillar[5]arene (WP5) and phenethylamine (PEA) over a gold surface for adsorption of lysozyme proteins. From the experimental results it was identified that the host-guest biointerface has a high adsorption capacity and strong chiral selectivity. Furthermotre, it was identified that the host-guest interaction plays the decisive role in the enhancement of chirality of the interface, which was much beneficial for increasing protein adsorption and amplifying the capacity of chiral discrimination. Therefore, this work provides a new idea for the construction of biointerface materials with high protein adsorption capacity and high chiral selectivity through supramolecular interaction, which will have potential applications in the fields of biosensors, biocatalysts, biomaterials.

Spreading of benquitrione droplets on superhydrophobic leaves through pillar[5]arene-based host-guest chemistry.

Spreading of agricultural sprays on plant surfaces is a significant task as it helps decrease pesticide usage and thereby reduces the risk of environmental pollution. Here, we report a method of increasing the spreading of herbicide benquitrione droplets on superhydrophobic surfaces through its selective dynamic self-assembly with amino pillar[5]arenes. Supramolecular interaction such as host-guest interaction was utilized for the complete diffusion of benquitrione over the hydrophobic plant surface. Furthermore, molecular dynamics simulations were used to verify that AP5A improved the spreading of benquitrione droplets on superhydrophobic interfaces. Moreover, complexation of benquitrione did not affect its biological activity. The present work provides a new method for improving the utilization rate of pesticides and reducing pesticide use.

A pyrophosphate-activated nanochannel inspired by a TRP ion channel.

A pyrophosphate (PPi) selectively activated potassium channel was constructed via introducing the isoniazid functionalized calix[4]arene (C4NP) into a biomimetic nanochannel. The activation mechanism is mainly due to the changing of the inner surface charge and wettability of the nanochannel caused by PPi binding.