Ionic Liquid-accelerated Growth of Covalent Organic Frameworks with Tunable Layer-stacking.

Layer-stacking behaviors are crucial for two-dimensional covalent organic frameworks (2D COFs) to define their pore structure, physicochemical properties, and functional output. So far, fine control over the stacking mode without complex procedures remains a grand challenge. Herein, we proposed a "key-cylinder lock mimic" strategy to synthesize 2D COFs with a tunable layer-stacking mode by taking advantage of ionic liquids (ILs). The staggered (AB) stacking (unlocked) COFs were exclusively obtained by incorporating ILs of symmetric polarity and matching molecular size; otherwise, commonly reported eclipsed (AA) stacking (locked) COFs were observed instead. Mechanistic study revealed that AB stacking was induced by a confined interlocking effect (CIE) brought by anions and bulky cations of the ILs inside pores ("key" and "cylinder", respectively). Excitingly, this strategy can speed up production rate of crystalline powders (e.g., COF-TAPT-Tf@BmimTf2N in merely 30 minutes) under mild reaction conditions. This work highlights the enabling role of ILs to tailor the layer stacking of 2D COFs and promotes further exploration of their stacking mode-dependant applications.

Thiophene π-Bridge Manipulation of NIR-II AIEgens for Multimodal Tumor Phototheranostics.

The fabrication of a multimodal phototheranostic platform on the basis of single-component theranostic agent to afford both imaging and therapy simultaneously, is attractive yet full of challenges. The emergence of aggregation-induced emission luminogens (AIEgens), particularly those emit fluorescence in the second near-infrared window (NIR-II), provides a powerful tool for cancer treatment by virtue of adjustable pathway for radiative/non-radiative energy consumption, deeper penetration depth and aggregation-enhanced theranostic performance. Although bulky thiophene π-bridges such as ortho-alkylated thiophene, 3,4-ethoxylene dioxythiophene and benzo[c]thiophene are commonly adopted to construct NIR-II AIEgens, the subtle differentiation on their theranostic behaviours has yet to be comprehensively investigated. In this work, systematical investigations discovered that AIEgen BT-NS bearing benzo[c]thiophene possesses acceptable NIR-II fluorescence emission intensity, efficient reactive oxygen species generation, and high photothermal conversion efficiency. Eventually, by using of BT-NS nanoparticles, unprecedented performance on NIR-II fluorescence/photoacoustic/photothermal imaging-guided synergistic photodynamic/photothermal elimination of tumors was demonstrated. This study thus offers useful insights into developing versatile phototheranostic systems for clinical trials.

Reversible Surface Engineering of Cellulose Elementary Fibrils: From Ultralong Nanocelluloses to Advanced Cellulosic Materials.

Cellulose nanofibrils (CNFs) are supramolecular assemblies of cellulose chains that provide outstanding mechanical support and structural functions for cellulosic organisms. However, traditional chemical pretreatments and mechanical defibrillation of natural cellulose produce irreversible surface functionalization and adverse effects of morphology of the CNFs, respectively, which limit the utilization of CNFs in nanoassembly and surface functionalization. Herein, this work presents a facile and energetically efficient surface engineering strategy to completely exfoliate cellulose elementary fibrils from various bioresources, which provides CNFs with ultrahigh aspect ratios (≈1400) and reversible surface. During the mild process of swelling and esterification, the crystallinity and the morphology of the elementary fibrils are retained, resulting in high yields (98%) with low energy consumption (12.4 kJ g-1). In particular, on the CNF surface, the surface hydroxyl groups are restored by removal of the carboxyl moieties via saponification, which offers a significant opportunity for reconstitution of stronger hydrogen bonding interfaces. Therefore, the resultant CNFs can be used as sustainable building blocks for construction of multidimensional advanced cellulosic materials, e.g., 1D filaments, 2D films, and 3D aerogels. The proposed surface engineering strategy provides a new platform for fully utilizing the characteristics of the cellulose elementary fibrils in the development of high-performance cellulosic materials.

Adding Flying Wings: Butterfly-Shaped NIR-II AIEgens with Multiple Molecular Rotors for Photothermal Combating of Bacterial Biofilms.

The ever-increasing threats of multidrug-resistant bacteria and their biofilm-associated infections have bred a desperate demand for alternative remedies to combat them. Near-infrared (NIR)-absorbing photothermal agent (PTAs)-mediated photothermal therapy (PTT) is particularly attractive for biofilm ablation thanks to its superiorities of noninvasive intervention, satisfactory antibacterial efficiency, and less likelihood to develop resistance. Herein, three butterfly-shaped aggregation-induced emission luminogens (AIEgens) with balanced nonradiative decay (for conducting PTT) and radiative decay (for supplying fluorescence in the NIR-II optical window) are rationally designed for imaging-assisted photothermal obliteration of bacterial biofilms. After being encapsulated into cationic liposomes, AIEgens-fabricated nanoparticles can eradicate a wide spectrum of biofilms formed by Gram-positive bacteria (methicillin-resistant Staphylococcus aureus and Enterococcus faecalis) and Gram-negative bacteria (Escherichia coli and Pseudomonas aeruginosa) upon an 808 nm laser irradiation. In vivo experiments firmly demonstrate that the NIR-II AIE liposomes with excellent biocompatibility perform well in both the P. aeruginosa biofilm-induced keratitis mouse model and the MSRA biofilm-induced skin infection mouse model.

Strong and Tough Nanostructured Hydrogels and Organogels Prepared by Polymerization-Induced Self-Assembly.

In nature, the hierarchical structure of biological tissues endows them with outstanding mechanics and elaborated functions. However, it remains a great challenge to construct biomimetic hydrogels with well-defined nanostructures and good mechanical properties. Herein, polymerization-induced self-assembly (PISA) is for the first time exploited as a general strategy for nanostructured hydrogels and organogels with tailored nanodomains and outstanding mechanical properties. As a proof-of-concept, PISA of BAB triblock copolymer is used to fabricate hydrogels with precisely regulated spherical nanodomains. These nanostructured hydrogels are strong, tough, stretchable, and recoverable, with mechanical properties correlating to their nanostructure. The outstanding mechanical properties are ascribed to the unique network architecture, where the entanglements of the hydrophilic chains act as slip links that transmit the tension to the micellar crosslinkers, while the micellar crosslinkers dissipate the energy via reversible deformation and irreversible detachment of the constituting polymers. The general feasibility of the PISA strategy toward nanostructured gels is confirmed by the successful fabrication of nanostructured hydrogels, alcogels, poly(ethylene glycol) gels, and ionogels with various PISA formulations. This work has provided a general platform for the design and fabrication of biomimetic hydrogels and organogels with tailorable nanostructures and mechanics and will inspire the design of functional nanostructured gels.

Anionic polymerization of nonaromatic maleimide to achieve full-color nonconventional luminescence.

Nonconventional or nonconjugated luminophore without polycyclic aromatics or extended π-conjugation is a rising star in the area of luminescent materials. However, continuously tuning the emission color within a broad visible region via rational molecular design remains quite challenging because the mechanism of nonconventional luminescence is not fully understood. Herein, we present a new class of nonconventional luminophores, poly(maleimide)s (PMs), with full-color emission that can be finely regulated by anionic polymerization even at ambient temperature. Interestingly, the general characteristics of nonconventional luminescence, cluster-triggered emission, e.g., concentration-enhanced emission, are not observed in PMs. Instead, PMs have features similar to aggregation-caused quenching due to boosted intra/inter-molecular charge transfer. Such a biocompatible luminescent material synthesized from a low-cost monomer shows great prospects in large-scale production and applications, including security printing, fingerprint identification, metal ion recognition, etc. It also provides a new platform of rational molecular design to achieve full-color nonconventional luminescence without any aromatics.

In situ generation and evolution of polymer toroids by liquid crystallization-assisted seeded dispersion polymerization.

An effective method is presented for preparing high solid content azobenzene-containing triblock copolymer toroidal assemblies by liquid crystallization-assisted seeded dispersion polymerization. Vesicles are prepared via polymerization-induced self-assembly (PISA), and used as seeds for further chain extension. By introducing smectic liquid crystalline (LC) ordering into the core-forming block, toroids are formed in situ during the polymerization. The morphological transformation from toroids to barrels is observed under ultraviolet irradiation due to the photo-isomerization of the azobenzene mesogens. This strategy expands the scope of tunable anisotropic morphologies for potential functional nanomaterials based on a LC copolymer by seeded dispersion polymerization.

Tough all-polysaccharide hydrogels with uniaxially/planarly oriented structure.

Considering that the poor mechanical performances of polysaccharide hydrogels always limit their practical applications, herein, we design and fabricate tough all-polysaccharide hydrogels by incorporating uniaxially/planarly oriented tunicate cellulose nanocrystals in physically cross-linked alginate networks. Firstly, alginate chains were loosely cross-linked by surface quaternized tunicate cellulose nanocrystals (Q-TCNCs) and Ca2+ through electrostatic interaction. Secondly, the loosely cross-linked hydrogel was pre-stretched and immersed into CaCl2 solution, obtaining uniaxially oriented hydrogel, whose tensile strength was 31.6 MPa along the pre-stretching direction. After biaxial stretching, the orientation of TCNCs in hydrogel networks converted from dominantly uniaxially oriented structure to planarly oriented structure. The tensile strength, elastic modulus, and toughness of the planarly oriented hydrogels were about 6.6-, 44- and 3.3-folds of those of isotropic Q-TCNC/alginate hydrogel. This work provided a facile and efficient strategy for developing tough hydrogels with uniaxially/planarly oriented structure from biodegradable polymers.

Stretch-Induced Crystallization of Cellulose Spun from Ionic Liquid Solution.

With the emergence of efficient green solvents, structural regulation of regenerated cellulose is highly desired in the solution process from an industrial perspective. Cellulose fiber and films are viewed as a "composite" comprising amorphous and crystalline fractions. The regulation of the crystalline structure is of great importance for the properties of cellulose materials. In this study, we found stretch-induced crystallization behavior during the transition from solution to gel via coagulation. The crystallinity index of the hydrogel fiber increases with the stretch ratio (SR). X-ray diffraction revealed that the cellulose II hydrate formed in the stretched hydrogel fibers. The mechanical properties and thermal stability of the dry fibers greatly improved against the SR. This crystallization behavior depends on the concentration of the solution and the type of ionic liquid. This stretch-induced crystallization provides an efficient method for structural regulation in cellulose solution processing.

Time-Dependent Elastic Tensor of Cellulose Nanocrystal Probed by Hydrostatic Pressure and Uniaxial Stretching.

The elastic properties of crystals are fundamental for structural material. However, in the absence of macroscopic single crystals, the experimental determination of the elastic tensor is challenging because the measurement depends on the transmission of stress inside the material. To avoid arbitrary hypotheses about stress transfer, we combine hydrostatic pressure and uniaxial-stretching experiments to investigate the elastic properties of cellulose Iß. Three orthogonal compressibilities are 50.0, 6.6, and 1.71 TPa-1. Combining Poisson's ratios from a uniaxial stretching experiment directly gives the Young's modulus along the chain direction (E33). However, Poisson's ratio depends on the deformation rate leading to apparent modulus E33 = 113 GPa using a slow cycle (hours) and 161 GPa using a fast cycle (minutes). The lattice deformation along the chain is not time-dependent, so the off-diagonal elements are time-dependent on the scale of minutes to hours.

A biaxially stretched cellulose film prepared from ionic liquid solution.

A biaxially stretched cellulose film with high performance was manufactured from ionic liquid solution through an environmentally friendly, cost effective and facile process. As the transverse stretching ratio (TSR) is increased, the tensile strength and elastic modulus of the biaxially stretched cellulose film in transverse direction (TD) are significantly improved and the coefficient of thermal expansion in TD is reduced while the performance achieves balance in the machine direction (MD) and TD. The transverse stretching regulates the microfibril orientation in the gel film from dominantly uniaxial orientation in MD to homogeneous planar orientation. This microfibril orientation may further play a role in the orientation of the chains in the films during gel drying as evidenced from the birefringence and 2D XRD results. These results indicate cellulose film prepared from ionic liquid process could be utilized with improved structural and mechanical properties by biaxial stretching, and thus serves in various applications.

Rational Design of a Polymer-Based Ratiometric K+ Indicator for High-Throughput Monitoring Intracellular K+ Fluctuations.

Highly selective fluorescent K+ sensors are of great importance for monitoring K+ fluctuations in various biological processes. In particular, highly efficient ratiometric K+ sensors that can emit in dual wavelengths and facilitate the quantitative determination of K+ are highly anticipated. Herein, we present the first polymer-based ratiometric fluorescent K+ indicator (PK1) for quantitatively detecting K+ in aqueous solutions and high-throughput monitoring K+ fluctuations in living cells. PK1 was synthesized by conjugating a small molecular K+ probe and a red emission reference dye to a hydrophilic polymer skeleton. The newly synthesized PK1 can form highly stable nanoparticles in aqueous solutions and work in 100% water without the aid of any organic solvents or surfactants. PK1 is sensitive to K+ with a fluorescence enhancement of sevenfold after interactions with K+ at 1000 mM and inert to other metal ions, physiological pH, or dye concentration vibrations. More importantly, the fluorescence intensity ratio at 572 and 638 nm is linearly correlated with log [K+] in the range of 2-500 mM (R2 = 0.998), which will facilitate the quantitative detection of K+. Practical application of PK1 in detecting different K+-rich samples demonstrates its great potential in quantitative detection of K+. PK1 can be quickly internalized by live cells and shows no obvious cytotoxicity. We also demonstrate that PK1 could be used for monitoring K+ fluctuations under different stimulations by using a confocal microscope and especially a microplate reader, which is high throughput and time saving. The rational design of PK1 will broaden the design concept of ratiometric fluorescent K+ sensors and facilitate the quantitative detection of K+.

Close Temporal Relationship between Oscillating Cytosolic K+ and Growth in Root Hairs of Arabidopsis.

Root hair elongation relies on polarized cell expansion at the growing tip. As a major osmotically active ion, potassium is expected to be continuously assimilated to maintain cell turgor during hair tip growth. However, due to the lack of practicable detection methods, the dynamics and physiological role of K+ in hair growth are still unclear. In this report, we apply the small-molecule fluorescent K+ sensor NK3 in Arabidopsis root hairs for the first time. By employing NK3, oscillating cytoplasmic K+ dynamics can be resolved at the tip of growing root hairs, similar to the growth oscillation pattern. Cross-correlation analysis indicates that K+ oscillation leads the growth oscillations by approximately 1.5 s. Artificially increasing cytoplasmic K+ level showed no significant influence on hair growth rate, but led to the formation of swelling structures at the tip, an increase of cytosolic Ca2+ level and microfilament depolymerization, implying the involvement of antagonistic regulatory factors (e.g., Ca2+ signaling) in the causality between cytoplasmic K+ and hair growth. These results suggest that, in each round of oscillating root hair elongation, the oscillatory cell expansion accelerates on the heels of cytosolic K+ increment, and decelerates with the activation of antagonistic regulators, thus forming a negative feedback loop which ensures the normal growth of root hairs.

A mitochondria-targeting NIR fluorescent potassium ion sensor: real-time investigation of the mitochondrial K+ regulation of apoptosis in situ.

The first NIR fluorescent mitochondria-targeting K+ sensor, denoted as TAC-Rh, was developed. The produced sensor consists of a rhodamine analog as the fluorophore and triazacryptand (TAC) as the K+ recognition unit. Compared to the K+ sensors reported previously, TAC-Rh exhibits two unique optical properties: the largest Stokes shifts (120 nm) and the longest emission peak wavelength (720 nm). With the assistance of this novel sensor, real-time changes of K+ concentrations in mitochondria during apoptosis were monitored for the first time. Moreover, it was also the first time that the relationship between mitochondrial K+ flux and apoptosis was investigated in real time using fluorescence imaging.

Tricolor dual sensor for ratiometrically analyzing potassium ions and dissolved oxygen.

A potassium ion­oxygen (K+-O2) dual fluorescent sensing film was developed. The film contains three probes, which are K+ probe (KS), O2 probe (OS), and reference probe (RP) in a polymer film composed of poly(ethylene glycol) methyl ether methacrylate (PEGMA), poly(ethylene glycol) dimethacrylate (PEGDMA) and methacrylic acid (MAA). The RP showed blue emission, the KS exhibited green emission, and the OS showed red emission. The emission peaks of three probes do not interfere with each other, which enable the sensing film to be used for ratiometrically and quantitatively detecting the concentrations of K+ and dissolved oxygen (DO). The sensing films showed high sensitivity and selectivity to potassium ions over other metal ions and also good sensitivity for DO from deoxygenated to oxygenated conditions. The sensing film was demonstrated to be capable of analyzing K+ and DO concentrations with experimental errors smaller than ±8.5% in aqueous solutions, showing the potential applications of the sensing films.

An ultrasensitive electrochemical sensor based on cotton carbon fiber composites for the determination of superoxide anion release from cells.

A sensor is described for determination of superoxide anion (O2˙-). The electrode consists of nitrogen-doped cotton carbon fiber (NCFs) modified with silver nanoparticles (AgNPs) which have excellent catalytic capability. The resulting sensor, best operated at working potentials around -0.5 V (vs. SCE), can detect O2˙- over an extraordinarily wide range that covers 10 orders of magnitude, and the detection limit is 2.32 ± 0.07 fM. The electrode enables the release of O2˙- from living cells under normal or under oxidative stress conditions to be determined. The ability to scavenge the superoxide anions of antioxidants was also investigated. In the authors' perception, the method represents a viable tool for studying diseases related to oxidative stress. Graphical abstract Schematic presentation of the construction of an electrochemical sensor based on Nitrogen-doped cotton carbon fiber and silver nanoparticles. It can be used for the direct detection of superoxide anions released from Glioma cells (U87) under normal or under oxidative stress conditions.

Highly Conducting Polythiophene Thin Films with Less Ordered Microstructure Displaying Excellent Thermoelectric Performance.

Polythiophene (PTh) with highly regular molecular structure is synthesized as nearly amorphous thin films by electrochemical methods in a BFEE/DTBP mixed medium (BFEE = boron fluoride ethyl ether; DTBP = 2,6-di-tert-butypyridine). The doping level and film morphology of PTh are modulated through adjusting the current density applied during the polymerization process. A combined analysis with solid-state NMR, FT-IR, and Raman spectra reveals the molecular structural regularity of the resulted PTh films, which leads to the highest electrical conductivity up to 700 S cm-1 for films obtained under an optimized current density of 1 mA cm-2 . By applying the self-heating 3ω-method, thermal conductivities are measured along the in-plane direction. A highly reduced Lorenz number of 6.49 × 10-9 W Ω K-2 and low lattice thermal conductivity of 0.21 W m-1 K-1 were extracted based on the analyses of the electrical and thermal conductivities according to the Wiedemann-Franz Law; the former is about one-third of the Sommerfeld value. Finally, the maximized ZT value can reach up to 0.10 under room temperature, which shows that the highly conducting polymers with less ordered structure is the practical direction for developing organic thermoelectric materials.

Semi-Fluorinated Methacrylates: A Class of Versatile Monomers for Polymerization-Induced Self-Assembly.

A series of polymerization-induced self-assembly (PISA) formulations are developed based on reversible addition-fragmentation chain-transfer (RAFT) dispersion polymerization of semi-fluorinated methacrylates. Alcoholic RAFT dispersion polymerization of 2-(perfluorobutyl)ethyl methacrylate (FBEMA), 2-(perfluorohexyl)ethyl methacrylate (FHEMA), and 2-(perfluorooctyl)ethyl methacrylate (FOEMA) is systematically evaluated to extend the general usability of semi-fluorinated methacrylates to PISA. The nanostructure of the assemblies is correlated to the side-chain length of the monomer: RAFT dispersion polymerization of FBEMA produces spherical micelles, wormlike micelles, and vesicles depending on its degree of polymerization (DP), while only spheres are generated for the PISA of FHEMA. PISA of FOEMA generates liquid crystalline cylindrical micelles, whose diameter increases with the DP of FOEMA. These results demonstrate the general feasibility of semi-fluorinated methacrylates to PISA. Besides, PISA of FHEMA is also realized in a variety of solvents, including iso-propanol, toluene, dioxane, and dimethyl formamide, exhibiting the superior solvent serviceability of the PISA formulations based on semi-fluorinated methacrylates.

Nonspherical Liquid Crystalline Assemblies with Programmable Shape Transformation.

Liquid crystalline (LC) assemblies with tailored shape and programmable shape transformation were prepared via polymerization-induced self-assembly. The influence of polymerization temperature and solvent on the shape of the LC assemblies indicated that shape of the LC assemblies could be delicately regulated by the repulsive interaction among the solvophilic chains and LC ordering. Programmable shape transformation of ellipsoidal LC assemblies was achieved, taking advantage of the smectic-to-isotropic phase transition. The ellipsoidal assemblies could remain ellipsoids or transform to faceted spheres and spheres, depending on the temperature procedure used. Besides, the generated spheres could be reshaped to ellipsoids with high shape recovery ratio. Small angle X-ray scattering study indicated that the interplay of the reversible smectic-to-isotropic phase transition and kinetic trapping underpins the programmed shape transformation. As a general approach to LC assemblies with programmable shape transformation, our strategy would provide a reliable platform for nanoactuators, nanomotors, and adaptive colloidal devices.

A highly selective, colorimetric, and environment-sensitive optical potassium ion sensor.

Potassium ions (K+) play vital roles in many biological processes and thus highly selective sensors for K+ are critical for disease diagnosis and health monitoring. Herein, we report a colorimetric K+ sensor (KS7) in which a hemicyanine dye was used as a fluorophore and phenylaza-[18]crown-6 lariat ether (ACLE) was utilized as a K+ ligand. The maximum absorption peak of KS7 shifted hypsochromically by 77 nm (from 515 to 438 nm) with an isosbestic point at 452 nm upon the addition of K+ to its aqueous solution accompanied by a color change from red to yellow. This sensor exhibited a linear response range to K+ from 1 to 200 mM, indicating its wide detection range for cellular, urinary, and environmental potassium ions. Further, this sensor is solvent-sensitive, implying its environmental sensitivity. For the demonstration of its applications, we prepared filter paper-based K+ test strips, which were used to detect K+ in urine conveniently.