Light-Gating Crystalline Porous Covalent Organic Frameworks.

We report light gating in synthetic one-dimensional nanochannels of stable crystalline porous covalent organic frameworks. The frameworks consist of 2D hexagonal skeletons that are extended over the x-y plane and stacked along the z-direction to create dense yet aligned 1D mesoporous channels. The pores are designed to be photoadaptable by covalently integrating tetrafluoro-substituted azobenzene units onto edges, which protrude from walls and offer light-gating machinery confined in the channels. The implanted tetrafluoroazobenzene units are thermally stable yet highly sensitive to visible light to induce photoisomerization between the E and Z forms. Remarkably, photoisomerization induces drastic changes in intrapore polarity as well as pore shape and size, which exert profound effects on the molecular adsorption of a broad spectrum of compounds, ranging from inorganic iodine to organic dyes, drugs, and enzymes. Unexpectedly, the systems respond rapidly to visible lights to gate the molecular release of drugs and enzymes. Photoadaptable covalent organic frameworks with reversibly convertible pores offer a platform for constructing light-gating porous materials and tailorable delivery systems, remotely controlled by visible lights.

An electrochemical biosensor for Staphylococcus aureus detection based on a multilevel surface 3D micro/nanostructure.

Detection of pathogens is one of the key concerns for hospitals, the food industry, water suppliers, or other environmental engineering practices because pathogens can cause a wide range of infectious risks. Staphylococcus aureus (S. aureus) is one of the most common pathogens that are hazardous to human health and its existence is an important index to the safety of food, environmental sanitation, or medical products. In this study, we prepared an electrode with designed surface multilevel 3D micro/nano protrusions for facile and efficient S. aureus detection. The existence of these multilevel protrusions enhanced the adsorption of S. aureus. Hence, the detection limit could be as low as 10 CFU mL-1. Furthermore, the electrode was also successfully used to detect S. aureus in actual samples, such as milk and artificial human tissue fluid. It was found that the recovery of the reported approach showed no significant difference from that of the traditional plate count method. However, compared with the plate count method, the detection process of our approach is much more time-saving and easy-operating. These advantages of the approach we report, such as high sensitivity, reliability, quickness, and user-friendliness, make it a potential platform for detecting S. aureus in relation to the food industry and clinical diagnosis.

Photoresponsive Covalent Organic Frameworks: Visible-Light Controlled Conversion of Porous Structures and Its Impacts.

Covalent organic frameworks are a novel class of crystalline porous polymers that enable molecular design of extended polygonal skeletons to attain well-defined porous structures. However, construction of a framework that allows remote control of pores remains a challenge. Here we report a strategy that merges covalent, noncovalent, and photo chemistries to design photoresponsive frameworks with reversibly and remotely controllable pores. We developed a topology-guided multicomponent polycondensation system that integrates protruded tetrafluoroazobenzene units as photoresponsive sites on pore walls at predesigned densities, so that a series of crystalline porous frameworks with the same backbone can be constructed to develop a broad spectrum of pores ranging from mesopores to micropores. Distinct from conventional azobenzene-based systems, the tetrafluoroazobenzene frameworks are highly sensitive to visible lights to undergo high-rate isomerization. The photoisomerization exerts profound effects on pore size, shape, number, and environment, as well as molecular uptake and release, rendering the system able to convert and switch pores reversibly and remotely with visible lights. Our results open a way to a novel class of smart porous materials with pore structures and functions that are convertible and manageable with visible lights.

Covalent Organic Frameworks for Chemical and Biological Sensing.

Covalent organic frameworks (COFs) are a class of crystalline porous organic polymers with polygonal porosity and highly ordered structures. The most prominent feature of the COFs is their excellent crystallinity and highly ordered modifiable one-dimensional pores. Since the first report of them in 2005, COFs with various structures were successfully synthesized and their applications in a wide range of fields including gas storage, pollution removal, catalysis, and optoelectronics explored. In the meantime, COFs also exhibited good performance in chemical and biological sensing, because their highly ordered modifiable pores allowed the selective adsorption of the analytes, and the interaction between the analytes and the COFs' skeletons may lead to a detectable change in the optical or electrical properties of the COFs. In this review, we firstly demonstrate the basic principles of COFs-based chemical and biological sensing, then briefly summarize the applications of COFs in sensing some substances of practical value, including some gases, ions, organic compounds, and biomolecules. Finally, we discuss the trends and the challenges of COFs-based chemical and biological sensing.

Fuel-Driven Dissipative Self-Assembly of a Supra-Amphiphile in Batch Reactor.

Dissipative self-assembly is an intriguing but challenging research topic in chemistry, materials science, physics, and biology because most functional self-assembly in nature, such as the organization and operation of cells, is actually an out-of-equilibrium system driven by energy dissipation. In this article, we successfully fabricated an I2-responsive supra-amphiphile by a PEGylated poly(amino acid) and realize its dissipative self-assembly in batch reactor by coupling it with the redox reaction between NaIO3 and thiourea, in which I2 is an intermediate product. The formation and dissipative self-assembly of the supra-amphiphile can be repeatedly initiated by adding the mixture of NaIO3 and thiourea, which herein acts as "chemical fuel", while the lifetime of the transient nanostructures formed by the dissipative self-assembly is easily tuned by altering thiourea concentration in the "chemical fuel". Furthermore, as an application demo, the dissipative self-assembly of the supra-amphiphile is examined to control dispersion of multiwalled carbon nanotubes in water, exhibiting a good performance of organic pollutant removal.

A Supramolecularly Activated Radical Cation for Accelerated Catalytic Oxidation.

Tuning the activity of radicals is crucial for radical reactions and radical-based materials. Herein, we report a supramolecular strategy to accelerate the Fenton reaction through the construction of supramolecularly activated radical cations. As a proof of the concept, cucurbit[7]uril (CB[7]) was introduced, through host-guest interactions, onto each side of a derivative of 1,4-diketopyrrolo[3,4-c]pyrrole (DPP), a model dye for Fenton oxidation. The DPP radical cation, the key intermediate in the oxidation process, was activated by the electrostatically negative carbonyl groups of CB[7]. The activation induced a drastic decrease in the apparent activation energy and greatly increased the reaction rate. This facile supramolecular strategy is a promising method for promoting radical reactions. It may also open up a new route for the catalytic oxidation of organic pollutants for water purification and widen the realm of supramolecular catalysis.

Tuning the surface activity of gemini amphiphile by the host-guest interaction of cucurbit[7]uril.

This research is aimed to develop an effective supramolecular route for tuning the surface activity of the surfactant. To this end, cationic gemini amphiphiles and cucurbit[7]uril (CB[7]) were complexed in water, and each hydrophobic chain of the gemini amphiphiles was bound with a CB[7]. The steric hindrance of CB[7] prevented the two hydrophobic chains from getting closed to each other, leading a significant change of surface activity. Before supramolecular complexation, the surface activity of the gemini amphiphile is relatively high, which can generate the foams easily. However, the foam generated by gemini amphiphile can be destructed by adding CB[7], suggesting that the suface activity is lowed after the supramolecular complexation. The surface activity can recover after adding 1-adamantanamine hydrochloride, which has a stronger ability to bind CB[7]. Therefore, a controllable foaming and defoaming process can be realized. It is highly anticipated that supramolecular chemistry for tuning amphiphilicity of surfactants may find application in the fields that fast foaming and defoaming are needed.

Asymmetric and symmetric bolaform supra-amphiphiles: formation of imine bond influenced by aggregation.

A series of bolaform supra-amphilphiles with different symmetries were fabricated through dynamic benzoic imine bond formation. The pH dependence of imine formations of these supra-amphiphiles were characterazied. We found that the extent of the imine formation of these supra-amphiphies were different. The supra-amphiphiles with a poorer symmetry always exhibited a lower imine formation at a given pH. Therefore, the varied extent of imine bond formation indicate the different aggregations of these supra-amphilphiles, which are controlled by the molecular symmetry of the supra-amphiphiles.

Novel Acid-Driven Bioinspired Self-Resettable Bilayer Hydrogel Actuator Mimicking Natural Muscles.

Soft robots have great potential applications in manufacturing, disaster rescue, medical treatment, etc. Artificial muscle is one of the most important components of a soft robot. In previous years, hydrogel actuators that can be controllably deformed by the stimuli of external signals have been developed as good candidates for muscle-like materials. In this article, we successfully prepared a chemical fuel-driven self-resettable bilayer hydrogel actuator mimicking natural muscles with the aid of a new negative feedback reaction network. The actuator can temporarily deform upon the addition of H+ (chemical fuel). Subsequently, H+ accelerated the reaction between BrO3- and Fe(CN)64-, which consume H+. It resulted in the spontaneous recovery of the pH as well as the shape of the actuator. Such an actuator exhibits a great similarity with natural muscles in actuation mechanisms and automaticity in the manipulation compared to the widely reported stimuli-responsive hydrogel actuators. This illustrates that fuel-driven self-resettable hydrogel is a promising dynamic material for mimicking the functions of living creatures.

Design and preparation of fluorescent covalent organic frameworks for biological sensing.

Covalent organic frameworks (COFs) are a new class of functional solids featuring several fantastic structural characteristics, including a great diversity of building units and cross-linking patterns, precise integration of building blocks, and adjustable topology of porous architecture. In addition to the above features, some COF samples are constructed with high-density conjugated fragments, which have unique potential advantages in fluorescence imaging, and thus may have great potential applications in bioimaging. Herein, this article summarizes the recent progress in the design and preparation of fluorescent covalent organic frameworks. We investigate the systemic correlation between the structural qualities of COF networks and biological sensors. Finally, the significant advantages, major challenges, and future opportunities of fluorescent covalent organic frameworks are discussed for the development of next-generation porous materials for sensing applications.

Polymer-Based Self-Assembled Drug Delivery Systems for Glaucoma Treatment: Design Strategies and Recent Advances.

Glaucoma has become the world's leading cause of irreversible blindness, and one of its main characteristics is high intraocular pressure. Currently, the non-surgical drug treatment scheme to reduce intraocular pressure is a priority method for glaucoma treatment. However, the complex and special structure of the eye poses significant challenges to the treatment effect and safety adherence of this drug treatment approach. To address these challenges, the application of polymer-based self-assembled drug delivery systems in glaucoma treatment has emerged. This review focuses on the utilization of polymer-based self-assembled structures or materials as important functional and intelligent carriers for drug delivery in glaucoma treatment. Various drug delivery systems, such as eye drops, hydrogels, and contact lenses, are discussed. Additionally, the review primarily summarizes the design strategies and methods used to enhance the treatment effect and safety compliance of these polymer-based drug delivery systems. Finally, the discussion delves into the new challenges and prospects of employing polymer-based self-assembled drug delivery systems for the treatment of glaucoma.

Neural Representation of Collective Self-esteem in Resting-state Functional Connectivity and its Validation in Task-dependent Modality.

INTRODUCTION: Collective self-esteem (CSE) is an important personality variable, defined as self-worth derived from membership in social groups. A study explored the neural basis of CSE using a task-based functional magnetic resonance imaging (fMRI) paradigm; however, task-independent neural basis of CSE remains to be explored, and whether the CSE neural basis of resting-state fMRI is consistent with that of task-based fMRI is unclear. METHODS: We built support vector regression (SVR) models to predict CSE scores using topological metrics measured in the resting-state functional connectivity network (RSFC) as features. Then, to test the reliability of the SVR analysis, the activation pattern of the identified brain regions from SVR analysis was used as features to distinguish collective self-worth from other conditions by multivariate pattern classification in task-based fMRI dataset. RESULTS: SVR analysis results showed that leverage centrality successfully decoded the individual differences in CSE. The ventromedial prefrontal cortex, anterior cingulate cortex, posterior cingulate gyrus, precuneus, orbitofrontal cortex, posterior insula, postcentral gyrus, inferior parietal lobule, temporoparietal junction, and inferior frontal gyrus, which are involved in self-referential processing, affective processing, and social cognition networks, participated in this prediction. Multivariate pattern classification analysis found that the activation pattern of the identified regions from the SVR analysis successfully distinguished collective self-worth from relational self-worth, personal self-worth and semantic control. CONCLUSION: Our findings revealed CSE neural basis in the whole-brain RSFC network, and established the concordance between leverage centrality and the activation pattern (evoked during collective self-worth task) of the identified regions in terms of representing CSE.

H-shaped supra-amphiphiles based on a dynamic covalent bond.

The imine bond, a kind of dynamic covalent bond, is used to bind two bolaform amphiphiles together with spacers, yielding H-shaped supra-amphiphiles. Micellar aggregates formed by the self-assembly of the H-shaped supra-amphiphiles are observed. When pH is tuned down from basic to slightly acidic, the benzoic imine bond can be hydrolyzed, leading to the dissociation of H-shaped supra-amphiphiles. Moreover, H-shaped supra-amphiphiles have a lower critical micelle concentration than their building blocks, which is very helpful in enhancing the stability of the benzoic imine bond being hydrolyzed by acid. The surface tension isotherms of the H-shaped supra-amphiphiles with different spacers indicate their twisty conformation at a gas-water interface. The study of H-shaped supra-amphiphiles can enrich the family of amphiphiles, and moreover, the pH-responsiveness may make them apply to controlled or targetable drug delivery in a biological environment.

Dissipative self-assembly of a dual-responsive block copolymer driven by a chemical oscillator.

HYPOTHESIS: Coupling stimuli-responsive building blocks with an oscillating reaction is an effective strategy to realize and investigate dissipative self-assembly. More importantly, since there is usually more than one component of which concentration periodically changes in a chemical oscillator, it can be expected that this strategy has the advantage of achieving dissipative self-assembly of the building blocks with dual- or even multi-responsiveness. EXPERIMENTS: We realized the dissipative self-assembly of a pH- and iodine-responsive block copolymer, poly(ethylene oxide)-b-poly(2-vinyl pyridine) (PEO-P2VP), by coupling it with the IO3--SO32--Fe(CN)62- (ISF) oscillator, and investigated its rhythmic self-assembly behavior. Furthermore, we proposed a mechanistic model to simulate the kinetics of the ISF oscillator coupling with different amounts of PEO-P2VP. FINDINGS: Rhythmic core-shell reversal of the polymer micelles formed by PEO-P2VP was found in the ISF oscillator. The mechanistic model we proposed successfully reproduced the experimental oscillation and provided some data on the kinetics of the dual responsive self-assembly of PEO-P2VP. This line of research provided an example of realizing dissipative self-assembly of dual-responsive building blocks, which was seldom reported previously. It once again suggested that coupling with a suitable chemical oscillator is a promising strategy to have an insight into the kinetics of stimuli-responsive self-assembly.

Bolaform superamphiphile based on a dynamic covalent bond and its self-assembly in water.

We have employed a dynamic covalent bond to fabricate a bolaform superamphiphile, which can be used as building blocks for controlled assembly and disassembly. In alkaline environment, one building block bearing a benzoic aldehyde group can react with the other building block bearing an amino group to form a bolaform superamphiphile. It is found that the bolaform superamphiphiles can self-assemble in water to form micellar aggregates. When the pH is tuned down to slightly acidic values, the benzoic imine bond can be hydrolyzed, leading to the dissociation of the superamphiphile. The micellar aggregates will also disassemble, and the loaded guest molecules are released subsequently. This line of research has enriched the family of bolaform amphiphiles, and the resulting assemblies may find application in the field of controlled and targetable drug-delivery in a biological environment.

Mechanically Robust, Self-Healing, Polymer Blends and Polymer/Small Molecule Blend Materials with High Antibacterial Activity.

There is a growing demand for antibacterial materials around the world in recent years because they can be used for preventing pathogen infection, which is one of the major threats to human health. However, the mechanical damage of the antibacterial materials may weaken their protective effect since bacteria can invade through the cracks of the material. Therefore, antibacterial materials with self-healing ability, in which the mechanical damage can be spontaneously healed, exhibit better reliability and a longer lifespan. In this article, we prepared a series of low-cost antibacterial polymer blends and polymer/small molecule blend materials with excellent self-healing ability and high mechanical strength by a one-pot reaction under mild conditions. These materials were facilely obtained by blending a tiny amount of commercialized cationic antibacterial chemicals, poly(ethylene imine) (PEI) or cetyltrimethylammonium bromide (CTAB), into a self-healing, mechanically robust polymer, poly(ether-thioureas) (PETU). It can be found that they can effectively kill Escherichia coli (Gram-negative) and Staphylococcus aureus (Gram-positive) on their surface. Meanwhile, the distinguished advantages of PETU, including self-healing property, excellent mechanical robustness, recyclability, and transparency, were perfectively maintained. Furthermore, it was shown that their cytotoxicity was satisfactory and their hemolytic activity was insignificant. The above advantages of the blend materials suggested their potential applications in health care, food industry, and environmental hygiene.

Electrochemical biosensor for cancer cell detection based on a surface 3D micro-array.

The detection of rare circulating tumour cells (CTCs) in patients' blood is crucial for the early diagnosis of cancer, highly precise cancer therapy and monitoring therapeutic outcomes in real time. In this study we have developed an efficient strategy to capture and detect CTCs from the blood of cancer patients using a benzoboric acid modified gold-plated polymeric substrate with a regular 3D surface array. Compared with the smooth substrate, the substrate with the surface 3D microarrays exhibited a higher capture efficiency, i.e. 3.8 times that afforded by the smooth substrate. Additionally, due to the reversible reaction between the benzoboric acid on the 3D microarray and the sialic acid on CTCs, our strategy allowed for easy detachment of the captured CTCs from the substrate without causing critical damage to the cells. This will be of benefit for gaining further access to these rare cells for downstream characterization. The proposed strategy provides several advantages, including enhanced capture efficiency, high sensitivity, low cost and recovery of isolated CTCs, and could become a promising platform for early stage diagnosis of cancer.

An Amylase-Responsive Bolaform Supra-Amphiphile.

An amylase-responsive bolaform supra-amphiphile was constructed by the complexation between ß-cyclodextrin and a bolaform covalent amphiphile on the basis of host-guest interaction. The bolaform covalent amphiphile could self-assemble in solution, forming sheet-like aggregates and displaying weak fluorescence because of aggregation-induced quenching. The addition of ß-cyclodextrin led to the formation of the bolaform supra-amphiphile, prohibiting the aggregation of the bolaform covalent amphiphile and accompanying with the significant recovery of fluorescence. Upon the addition of α-amylase, with the degradation ß-cyclodextrin, the fluorescence of the supra-amphiphile would quench gradually and significantly, and the quenching rate linearly correlated to the concentration of α-amylase. This study enriches the field of supra-amphiphiles on the basis of noncovalent interactions, and moreover, it may provide a facile way to estimate the activity of α-amylase.

The fabrication of a supra-amphiphile for dissipative self-assembly.

Dissipative self-assembly is a challenging but attractive field of supramolecular science, because it generally concerns complex systems but is more close to the self-assembly of living bodies. In this article, we realized dissipative self-assembly by coupling a supra-amphiphile with a chemical oscillator. The supra-amphiphile was fabricated with iodine and a double hydrophilic block copolymer containing PEG segments, as the non-covalent interaction between PEG and iodine could turn PEG hydrophobic, leading to the formation of the supra-amphiphile. The self-assembly and disassembly of the supra-amphiphile could be controlled by varying the concentration of iodine. Therefore, the dissipative self-assembly of the supra-amphiphile was realized when it was coupled with the IO3--NH3OH+-OH- chemical oscillator, which was able to produce iodine periodically. Meanwhile, the kinetic data of the self-assembly and disassembly of the supra-amphiphile could be estimated by the theoretical simulation of the chemical oscillations. This line of research promotes the self-assembly of supra-amphiphiles one step forward from thermodynamic statics to a dissipative system, and also suggests a new strategy to investigate the kinetics of stimuli-responsive molecular self-assembly.