Regulating Gelation and Luminescence Behaviors of Single Pyridine-Functionalized Cyanostilbene via Metal Ions.

Luminescent metal-organic gels (LMOGs) have gained much attention due to their crucial role in visual recognition and information encryption. However, it is still a challenge to simplify the design of ligands and enrich the stimuli responses in LMOGs simultaneously. Herein, although a single pyridine ligand cannot form gel alone, after coordination with metal ions, two kinds of LMOGs have been obtained with pyridine-metal complexes, where metal ions can act as cogelators and regulate luminescence of the pyridine-functionalized cyanostilbene ligand at the same time. The effects of metal types on the fluorescence emission color, the fluorescence quantum yield, the fibril network, and the assembly mode of the gel have been investigated systematically. In addition, two competitive ligands were used to regulate the fluorescence and phase transition of the gel. Finally, the logic gates and the information encryption and decryption have been successfully constructed. This kind of material is expected to be applied to fluorescence display, advanced information encryption, high-tech anticounterfeit, and so forth.

Photoswitching in a Liquid Crystalline Pt(II) Coordination Complex.

Photoswitching of photoluminescence has sparked tremendous research interests for super-resolution imaging, high-security-level anti-counterfeiting, and other high-tech applications. However, the excitation of photoluminescence is usually ready to trigger the photoswitching process, making the photoluminescence readout unreliable. Herein, we report a new photoswitch by the marriage of spiropyran with platinum(II) coordination complex. Viable photoluminescence can be achieved upon excitation by 480 nm visible light while the photoswitching can be easily triggered by 365 nm UV light. The feasible photoswitching may be benefited from the formed liquid crystalline (LC) phase of the designed photoswitch as a crystalline spiropyran is normally unable to implement photoswitching. Compared to the counterparts, this LC photoswitch can show distinct and reliable apparent colors and emission colors before and after photoswitching, which may promise the utility in high-security-level anti-counterfeiting and other advanced information technologies.

Extending Conjugation of Linear Cyanostilbene Derivatives via a Pyridine Moiety for Multi-Stimuli-Responsive Fluorescence Organogels.

In the design of effective gelators with aggregation-induced emission behavior, amide and cholesterol moieties are generally used to provide multiple driving forces for gelation. In this work, a series of linear cyanostilbene gelators with a pyridine moiety and different lengths of the alkoxyl group, i.e., CSpy-Cn, have been synthesized through nucleophilic substitution and Knoevenagel reaction. The direct connection of pyridine extends the conjugation of the cyanostilbene moiety, while the alkoxyl group can regulate the solubility of the compounds so that the compounds can serve as gelators for common solvents such as acetonitrile, dimethyl sulfoxide, and ethanol at ultra-low concentrations. At the same time, the cyanostilbene group makes the compounds undergo photoisomerization and emit fluorescence under UV light, while the pyridine group can serve as an acid-base responsive group due to easy protonation. The gels can respond to temperature, light, and organic acid/base. The fluorescence intensity and color can reversibly change during the gel-sol transitions. Finally, a thin film based on the CSpy-C8 xerogel has been prepared and utilized as a multi-stimuli-responsive fluorescence display for information storage and anti-counterfeiting.

NIR-Cleavable and pH-Responsive Polymeric Yolk-Shell Nanoparticles for Controlled Drug Release.

Responsive drug release and low toxicity of drug carriers are important for designing controlled release systems. Here, a double functional diffractive o-nitrobenzyl, containing multiple electron-donating groups as a crosslinker and methacrylic acid (MAA) as a monomer, was used to decorate upconversion nanoparticles (UCNPs) to produce robust poly o-nitrobenzyl@UCNP nanocapsules using the distillation-precipitation polymerization and templating method. Poly o-nitrobenzyl@UCNP nanocapsules with a robust yolk-shell structure exhibited near-infrared (NIR) light-/pH-responsive properties. When the nanocapsules were exposed to 980 nm NIR irradiation, the loaded drug was efficiently released by altering the shell of the nanocapsules. The photodegradation kinetics of the poly o-nitrobenzyl@UCNP nanocapsules were studied. The anticancer drug, doxorubicin hydrochloride (DOX), was loaded at pH 8.0 with a loading efficiency of 13.2 wt %. The Baker-Lonsdale model was used to determine the diffusion coefficients under different release conditions to facilitate the design of dual-responsive drug release devices or systems. Additionally, cytotoxicity studies showed that the drug release of DOX could be efficiently triggered by NIR to kill cancer cells in a controlled manner.

A Review on Low-Molecular-Weight Gels Driven by Halogen-Effect.

As a new type of non-covalent interaction similar to hydrogen bond, halogen bond has become an important supramolecular tool in crystal engineering, material chemistry, biological science, etc., due to its unique properties. In fact, halogen bond has been confirmed on the effect of molecular assemblies and soft materials, and widely used in various functional soft materials including liquid crystals, gels and polymers. In recent years, halogen bonding has aroused strong interest in inducing molecular assembly into low-molecular-weight gels (LMWGs). To the best of our knowledge, there is still a lack of in-depth review of this field. So, in this paper, the recent progress of LMWGs driven by halogen bonding is reviewed. According to the number of components forming halogen bonded gels, the structural characteristics of halogen bonded supramolecular gels, the relationship between halogen bonding and other non-covalent interactions, as well as the application fields of halogen bonded gels are introduced, respectively. In addition, the challenges faced by halogenated supramolecular gels at present and their development prospects in future have been proposed. We believe that the halogen bonded gel will have more impressive applications in the next few years, opening exciting new opportunities for the development of soft materials.

One-pot synthesis of hyperbranched polymers via visible light regulated switchable catalysis.

Switchable catalysis promises exceptional efficiency in synthesizing polymers with ever-increasing structural complexity. However, current achievements in such attempts are limited to constructing linear block copolymers. Here we report a visible light regulated switchable catalytic system capable of synthesizing hyperbranched polymers in a one-pot/two-stage procedure with commercial glycidyl acrylate (GA) as a heterofunctional monomer. Using (salen)CoIIICl (1) as the catalyst, the ring-opening reaction under a carbon monoxide atmosphere occurs with high regioselectivity (>99% at the methylene position), providing an alkoxycarbonyl cobalt acrylate intermediate (2a) during the first stage. Upon exposure to light, the reaction enters the second stage, wherein 2a serves as a polymerizable initiator for organometallic-mediated radical self-condensing vinyl polymerization (OMR-SCVP). Given the organocobalt chain-end functionality of the resulting hyperbranched poly(glycidyl acrylate) (hb-PGA), a further chain extension process gives access to a core-shell copolymer with brush-on-hyperbranched arm architecture. Notably, the post-modification with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) affords a metal-free hb-PGA that simultaneously improves the toughness and glass transition temperature of epoxy thermosets, while maintaining their storage modulus.

Balancing Compatibility and Gelability for High-Performance Cholesteric Liquid Crystalline Physical Gels.

Liquid crystalline physical gels (LCPGs) have attracted increasing interest because of their mechanical properties and stimulus-response behaviors. However, due to their gelator properties such as thermal stability, gelation capability, and compatibility in liquid crystals, development of LCPGs with high performances still remains a huge challenging task. Herein, four novel gelators ((l)-PH, (d)-PH, (l)-P2H, and (d)-P2H) based on 1,4-benzenedicarboxamide phenylalanine derivatives containing one or two ethylene glycol groups have been designed and synthesized. It is found that the ethylene glycol group plays a significant role in improving the compatibility between the gelator and the liquid crystal. All of the prepared compounds can form stable LCPGs in P0616A. In particular, the storage modulus of LCPG with 9.0 wt % of (l)-PH with one ethylene glycol unit is higher than 106 Pa, which is similar to SmC gels and advantageous over previously reported nematic LCPGs. Furthermore, the prepared gels display a strong Cotton effect with hand-preferred twisted fiber networks and the self-assembled aggregates of (l)-PH can induce P0616A to form a cholesteric fingerprint structure. Thus, these low molecular weight gelators provide a strategy to construct high-performance cholesteric LCPGs for the realization of LC device applications.

Two-Color Cholesteric Liquid Crystalline Gels for Reversible Writing and Erasing Information Encryption.

Bright structural color derived from the unique helical superstructure of cholesteric liquid crystals (CLCs) has attracted much attention. In addition, fluorescence color is an intrinsic emission upon excitation, which can be observed often under UV light. However, it is a challenge to combine the fluorescence and structural colors to construct a self-supporting system at the same time. In this work, a photoresponsive cyanostilbene-based gelator (CSpy-C10) is synthesized, which emits blue fluorescence in LC. CSpy-C10 can gel LCs and further construct thermo-/photoresponsive CLC physical gels. The structural color of the CLCs, fluorescence, and mechanical properties of the gels can be independently regulated due to the separation of the chiral unit and photoresponsive unit with aggregation-induced emission behavior. Finally, the reversible information encryption including writing and erasing based on the changes in fluorescence are explored. This kind of two-color material can be applied in the fields ranging from information encryption, fluorescent display to high-tech anticounterfeiting.

Apolipoprotein L Domain Containing 1 Inhibits Tissue Factor to Impede Thrombus Formation in a Rat Model of Deep Vein Thrombosis via Activating PI3K/Akt Pathway.

BACKGROUND: Deep venous thrombosis (DVT) is one of the major health problems worldwide. Apolipoprotein L domain containing 1 (APOLD1) was reported to be downregulated in DVT. The present study intended to investigate whether APOLD1 affects thrombus formation in a rat model of DVT. METHODS: The rat model of DVT was established by inferior vena cava (IVC) stenosis. At 6 hr, 12 hr, 24 hr, and 48 hr after IVC stenosis, the gross IVC with thrombus was dissected and observed. Then, the rats were preinjected with the lentiviral overexpression vector, APOLD1-LVs, 1 hr before IVC stenosis, to evaluate the influence of APOLD1 on thrombosis in rats. The serum levels of D-dimer and TAT as well as the content of TF in IVC tissues were detected by enzyme-linked immunosorbent assay (ELISA). RESULTS: IVC stenosis resulted in thrombus formation in rats, increased serum levels of D-dimer and TAT, and decreased APOLD1 expression. APOLD1 overexpression inhibited in vivo thrombosis, reduced serum levels of D-dimer, and downregulated tissue factor (TF) activity and level. APOLD1 overexpression also increased p-PI3K and p-Akt protein levels. CONCLUSIONS: APOLD1 suppresses thrombus formation in a rat model of DVT via downregulating TF expression by activating the PI3K/Akt pathway.

Cascade Reaction of "Mn2+ -Catechol" Triggered by H2 O2 to Integrate Firm Tumor Vessel Embolization and Hypoxic Response Relief.

Transcatheter arterial embolization (TAE) therapy requires firm and long-term vessel embolization without recanalization. However, firm embolization usually leads to unanticipated hypoxic response which promotes tumor recurrence and metastasis. Herein, an injectable thermosensitive hydrogel containing catechol groups and Mn2+ (PNDM) has been developed to enhance embolization and inhibit hypoxic response utilizing augmented H2 O2 after TAE. This novel embolic agent converts H2 O2 into hydroxyl radicals via Mn2+ -dependent Fenton-like reaction, which are subsequently scavenged through a "catechol-quinone" transition to suppress hypoxic responses. Quinone structure can not only make hydrogel internal structure more compact, but also enhance hydrogel adhesion to vessel wall. In vivo experiments confirm that the rabbit renal artery can be firmly embolized for 84 days. Studies in liver VX2 tumor-bearing rabbits demonstrate that the PNDM-based TAE can promote tumor necrosis, inhibit angiogenesis and tumor metastasis, and greatly prolong rabbit survival. This strategy opens new sights in the TAE therapy for liver cancer.

Helix Induction and Inversion of Polymeric Foldamer Regulated by the Single Enantiomers.

Generally, a single enantiomer can induce a foldamer into a preferred-handed helix, while another condition is required for the helical inversion. Herein, it is found that the helix induction and subsequent inversion of poly(m-phenylene diethynylene)-based foldamer bearing aza-18-crown-6 pendants (Poly-1) can be realized by increasing the concentration of sterically hindered l-amino acid perchlorate salts. When the amount of chiral enantiomers is small, one enantiomer tends to complex with two non-adjacent aza-18-crown-6 rings via three N+ H···O hydrogen bonds in a sandwich mode. Notably, the transition dipole moment is perpendicular to the aza-18-crown-6 ring, so that the induced helical chirality in Poly-1 backbone is opposite to the chirality of enantiomers. When the amount of chiral enantiomers is large enough, each aza-18-crown-6 is occupied by one enantiomer, which causes the transition dipole moment in a parallel direction to aza-18-crown-6 ring. In this case, the increased steric hindrance can facilitate the inversion of screw sense of Poly-1 backbone, which is directed by chiral center of enantiomers. As a result, a helix inversion has been achieved successfully. This work not only provides a novel strategy for regulating the two-stage folded helical conformations by the single enantiomers, but opens a window to develop chiral recognition materials.

Configuration-Dependent Liquid Crystal and Gel Behaviors of Tetraphenylethene-Containing Main-Chain Copolyesters.

The construction of aggregation-induced emission-active (AIE-active) gelators with liquid crystal properties remains a challenge. Moreover, the effects of AIE configuration on liquid crystal, gel and AIE behaviors in one system are unclear. Herein, two main-chain liquid crystalline copolyester gelators with a single configuration of AIEgen TPE, mesogen biphenyl, and pendent amide groups are synthesized through melt polycondensation. Both copolyesters display smectic phase, while E-P20 possesses a wider temperature range of liquid crystal and a narrower layer distance owing to the more serious nonlinear "defect" of Z-TPE than E-TPE units. In addition, E-P20 and Z-P20 can form AIE-active gels with the minimum gelation concentration (MGC) values of 10 and 4 wt% in ethyl acetate mainly via hydrogen bonds between the pendent amide groups, respectively. These AIE-active gels show potential applications in temperature sensor, information storage, and so on.

Injectable Thermosensitive Iodine-Loaded Starch-g-poly(N-isopropylacrylamide) Hydrogel for Cancer Photothermal Therapy and Anti-Infection.

Although photothermal therapy (PTT) can effectively eliminate tumors, the normal tissues near tumors are inevitably damaged by heat and infected by bacteria, which greatly limits the therapeutic effect. In this work, an injectable thermosensitive hydrogel based on iodine-loaded starch-g-poly(N-isopropylacrylamide) (PNSI) is developed to overcome this problem. FTIR, 1 H NMR, and UV-vis spectra confirm the graft copolymerization of poly(N-isopropylacrylamide) with starch and the formation of "iodine-starch" complex. Transmission electron microscope images show PNSI polymer self-assembles into regular spherical nanogel with a size of ≈50 nm. The concentrated nanogel dispersion is a sol at room temperature and transforms to hydrogel at body temperature. Under NIR laser irradiation for 10 min, the ΔT of the nanogel dispersion approachs about 20 °C with excellent thermal stability and high cytotoxicity due to the photothermal effect of the "iodine-starch" complex. After intratumor injection, this injectable hydrogel efficiently inhibites the tumor growth under 808 nm laser irradiation. Furthermore, it can also suppress Staphylococcus aureus infection in the wound post-PTT due to the release of iodine, which promotes wound healing. Therefore, this injectable thermosensitive "iodine-starch" composite hydrogel with advantages of good biocompatible and easy preparation possesses potential application for tumor photothermal therapy and antibacterial infection.

Naked-eye sensing and target-guiding treatment of bacterial infection using pH-tunable multicolor luminescent lanthanide-based hydrogel.

In this work, a pH-tunable multicolor luminescent lanthanide-based hydrogel (CS/DEX/CP) was prepared based on lanthanide coordination polymer (CP), dextran aldehyde (DEX) and chitosan (CS). The CP was obtained by the self-assembly of guanosine acid (GMP), ciprofloxacin (CIP), Eu3+, and Tb3+. As-prepared CS/DEX/CP hydrogel could emit blue, green, and red luminescence of CIP, Tb3+, and Eu3+, respectively. It was also found that the luminescence of CS/DEX/CP hydrogel exhibited visual color change in the pH range of 5.5 to 8. Such pH-sensitive hydrogel was multicolor-responsive to protons produced by bacterial growth, therefore, it could provide early warning of bacterial infection by naked-eye. In addition, the increased acidity resulted in not only the degradation of acid-labile Schiff base linkages between DEX and CS, but also the fracture of coordination between CIP and lanthanide ions. As a result, the released CIP and CS showed significantly antibacterial activity against both S. aureus and E. coli.

Carboxymethyl chitosan‒promoted luminescence of lanthanide metallogel and its application in assay of multiple metal ions.

In this work, the luminescence of lanthanide supramolecular metallogel formed by the self-assembly of 5,5',5″-(1,3,5-triazine-2,4,6-triyl)tris(azanediyl)triisophthalate (H6L) and Tb3+ was efficiently promoted by carboxymethyl chitosan (CMCS). The total quantum yield of the resultant metallogel (denoted as H6L/Tb3+/CMCS gel) was 9 times higher than the gel without CMCS. The average lifetime of H6L/Tb3+/CMCS gel increased from 0.51 ms to 1.20 ms. More importantly, the aqueous dispersion of H6L/Tb3+/CMCS xerogels showed a stable and pH-dependent luminescence. Based on the selective affinity of CMCS to different metal ions as well as with the aid of principal component analysis, H6L/Tb3+ /CMCS can be used as a sensor array to distinguish 11 metal ions (P < 0.05). This work provides a new strategy for the design and development of bio-based functional luminescent lanthanide supramolecular metallogels.

Light regulation and long-lived stability of RGB colors in cholesteric liquid crystal physical gels via a mixing strategy.

Photo-responsive cholesteric liquid crystals (CLCs) have attracted much attention due to the dynamic tunability of their unique helical superstructure. However, it is still a challenge to endow the mechanical properties and to regulate the reflection colors at the same time. In this work, a simple strategy is developed for the construction of thermo-responsive CLC physical gels via the direct mixing of photo-responsive dopants and a gelator with nematic LCs. The reflection colors of CLCs and the mechanical properties of gels can be independently regulated due to the separation of the photo-responsive chiral group from the gelator. In addition, the CLC reflection colors can be regulated via visible light in the range of RGB with long-lived thermal stability. Finally, the information storage properties of this kind of CLC gel have been investigated.

Luminescence sensitization of terbium-loaded supramolecular gels by hydroxybenzoic acids and used for salicylates sensing.

The luminescent terbium (Tb3+)-loaded supramolecular gels were facilely prepared through the self-assembly of Fmoc-diphenylalanine (FmocPhePhe) at room temperature. Hydroxybenzoic acid (HA, the isomers are denoted as 2-HA, 3-HA, and 4-HA depending upon the positions of hydroxyl groups) was used as a sensitizer to Tb3+. The luminescence sensitization of Tb3+ in the gels was realized by the coordination with hydroxybenzoic acids. The spectra of luminescence, UV-vis, FT-IR, and 1H NMR verified that this sensitization was attributed to the energy transfer from hydroxybenzoic acids to Tb3+. The results of XRD, SEM, and phase transfer temperature further indicated that the initial molecule arrangement of the gels was significantly changed by 2-HA, resulting in more ordered and more compact morphology of the gels. 2-HA exhibited more effective sensitization to Tb3+ in the gels than 3-HA and 4-HA. It was also found that 2-HA did not affect the self-assembly of FmocPhePhe. Due to the effective fluorescence sensitization by 2-HA, the as-prepared gels can be used for salicylic acid sensing with 6.8 µM of the detection limit. This strategy has been successfully used for the detection of salicylates in pharmaceuticals and cosmetics.

High-Performance Photochromic Hydrogels for Rewritable Information Record.

Rewritable information record materials usually demand not only reversibly stimuli-responsive ability, but also strong mechanical properties. To achieve one photochromic hydrogel with super-strong mechanical strength, hydrophobic molecule spiropyran (SP) has been introduced into a copolymer based on ion-hybrid crosslink. The hydrogels exhibit both photoinduced reversible color changes and excellent mechanical properties, i.e., the tensile stress of 3.22 MPa, work of tension of 12.8 MJ m-3 , and modulus of elasticity of 8.6 MPa. Moreover, the SP-based Ca2+ crosslinked hydrogels can be enhanced further when exposed to UV-light via ionic interaction coordination between Ca2+ , merocyanine (MC) with polar copolymer chain. In particular, hydrogels have excellent reversible conversion behavior, which can be used to realize repeatable writing of optical information. Thus, the novel design is demonstrated to support future applications in writing repeatable optical information, optical displays, information storage, artificial intelligence systems, and flexible wearable devices.

Injectable zwitterionic thermosensitive hydrogels with low-protein adsorption and combined effect of photothermal-chemotherapy.

Injectable hydrogels have been developed as biomedical materials in various fields but the biofouling on their surface limits applications in vivo. In this work, a zwitterionic structure was introduced into an injectable hydrogel based on thermosensitive nanogels to overcome the foreign body reaction. The hydrodynamic diameter of the resultant poly(N-isopropylacrylamide-co-sulfobetaine methacrylate) (PNS) nanogels was ca. 105 nm. The aqueous dispersion with a high content of PNS nanogels showed a flowable sol state at room temperature, and turned into a hydrogel in situ at ∼36 °C due to the thermosensitivity of the PNS nanogels. In particular, the resulting hydrogel exhibited lower biofouling both in vitro and in vivo in comparison with similar hydrogels without a zwitterionic structure. Polydopamine nanoparticles (PDA NPs) as a photothermal agent and an anti-tumour drug could be easily co-loaded in the injectable hydrogel. Under near-infrared (NIR) irradiation for 10 min, the temperature of the PNS system containing PDA NPs could reach ca. 38 °C. The drug release from the in situ-forming hydrogel could be accelerated by NIR laser irradiation, and showed a sustainable release behavior and adjustability. The results of intratumoral injection of the as-prepared injectable hydrogel containing PDA NPs and an anti-tumour drug showed significant anticancer effects combining photothermal therapy and local chemotherapy. This constructed injectable zwitterionic thermosensitive hydrogel is easy to use with the advantage of low-fouling and may become a promising platform for various biomedical applications.

Intrinsically Visible Light-Responsive Liquid Crystalline Physical Gels Driven by a Halogen Bond.

Photoresponsive physical gels using liquid crystals (LCs) as solvents have attracted great interest owing to their potential applications. But, current investigations mainly focus on UV light, which is not environment-friendly enough. On the other hand, the halogen bond is a novel tool for constructing supramolecular gels because of good hydrophobicity, high directionality, tunable strength, and large size of halogen atoms. Herein, to construct an LC physical gel with both the advantages of a halogen bond and visible light response, azopyridine-containing Azopy-C10 is chosen as a halogen bond acceptor, while 1,2-bis(2,3,5,6-tetrafluoro-4-iodophenyl)diazene is selected both as the halogen bond donor and for the intrinsically visible light response. Such a binary gelator can self-assemble in the anisotropic solvent of nematic LC 5CB to form an LC physical gel. It experiences the gel-to-sol transition by green light irradiation. As the gelator concentration increases, the saturation voltage increases, but the switch-off time decreases. The combination of the halogen bond and controllable visible light-responsive LC physical gel provides the feasibilities of manipulating these smart soft materials.