Tunable Multicolor Lanthanide Supramolecular Assemblies with White Light Emission Confined by Cucurbituril[7].

Macrocyclic confinement-induced supramolecular luminescence materials have important application value in the fields of bio-sensing, cell imaging, and information anti-counterfeiting. Herein, a tunable multicolor lanthanide supramolecular assembly with white light emission is reported, which is constructed by co-assembly of cucurbit[7]uril (CB[7]) encapsulating naphthylimidazolium dicarboxylic acid (G1 )/Ln (Eu3+ /Tb3+ ) complex and carbon quantum dots (CD). Benefiting from the macrocyclic confinement effect of CB[7], the supramolecular assembly not only extends the fluorescence intensity of the lanthanide complex G1 /Tb3+ by 36 times, but also increases the quantum yield by 28 times and the fluorescence lifetime by 12 times. Furthermore, the CB[7]/G1 /Ln assembly can further co-assemble with CD and diarylethene derivatives (DAE) to realize the intelligently-regulated full-color spectrum including white light, which results from the competitive encapsulation of adamantylamine and CB[7], the change of pH, and photochromic DAE. The multi-level logic gate based on lanthanide supramolecular assembly is successfully applied in anti-counterfeiting system and information storage, providing an effective method for the research of new luminescent intelligent materials.

High-Efficiency Synergistic Effect of Supramolecular Nanoparticles Based on Cyclodextrin Prodrug on Cancer Therapy.

Novel cyclodextrin-prodrug supramolecular nanoparticles (NPs) with cooperative-enhancing cancer therapy were constructed from a reduction-sensitive disulfide bond-linked permethyl-ß-cyclodextrin-camptothecin prodrug, water-soluble adamantane-porphyrin photosensitizer, and hyaluronic acid grafted by triphenylphosphine and ß-cyclodextrin through an orthogonal host-guest recognition strategy, displaying uniform nanoparticles with a diameter around 100 nm as revealed by dynamic light scattering, transmission electron microscopy, scanning electron microscopy, and atomic force microscopy. Compared with 293T normal cells, the supramolecular NPs could be easily taken up by mitochondria of A549 cancer cells, then release the active anticancer drug camptothecin (CPT) in situ via the cleavage of the disulfide bond by the overexpressed glutathione, and could initiate the effective singlet oxygen (1O2) generation by porphyrin under light irradiation, ultimately resulting in severe mitochondrial dysfunction and a rising cell death rate with increasing micromolar concentration of NPs. These multicomponent supramolecular nanoassemblies effectively combined the two-step synergistic chemo-photodynamic therapy of reduction-release of CPT and light-triggered 1O2 generation within cancer cells presenting the synergistic effect of supramolecular nanoparticles on cancer therapy, which provide a new approach for efficient step-by-step cancer therapy.

Carbon Nitride Supramolecular Hybrid Material Enabled High-Efficiency Photocatalytic Water Treatments.

Surface defects in relation to surface compositions, morphology, and active sites play crucial roles in photocatalytic activity of graphitic carbon nitride (g-C3N4) material for highly reactive oxygen radicals production. Here, we report a high-efficiency carbon nitride supramolecular hybrid material prepared by patching the surface defects with inorganic clusters. Fe (III) {PO4[WO(O2)2]4} clusters have been noncovalently integrated on surface of g-C3N4, where the surface defects provide accommodation sites for these clusters and driving forces for self-assembly. During photocatalytic process, the activity of supramolecular hybrid is 1.53 times than pure g-C3N4 for the degradation of Rhodamine B (RhB) and 2.26 times for Methyl Orange (MO) under the simulated solar light. Under the mediation of H2O2 (50 mmol L-1), the activity increases to 6.52 times for RhB and 28.3 times for MO. The solid cluster active sites with high specific surface area (SSA) defect surface promoting the kinetics of hydroxide radicals production give rise to the extremely high photocatalytic activity. It exhibits recyclable capability and works in large-scale demonstration under the natural sunlight as well and interestingly the environmental temperature has little effects on the photocatalytic activity.

Cucurbit[8]uril Confinement-Based Secondary Coassembly for High-Efficiency Phosphorescence Energy Transfer Behavior.

Aqueous supramolecular long-lived near-infrared (NIR) material is highly attractive but still remains great challenge. Herein, we report cucurbit[8]uril confinement-based secondary coassembly for achieving NIR phosphorescence energy transfer in water, which is fabricated from dicationic dodecyl-chain-bridged 4-(4-bromophenyl)-pyridine derivative (G), cucurbit[8]uril (CB[8]), and polyelectrolyte poly(4-styrene-sulfonic sodium) (PSS) via the hierarchical confinement strategy. As compared to the dumbbell-shaped G, the formation of unprecedented linear polypseudorotaxane G⊂CB[8] with nanofiber morphology engenders an emerging phosphorescent emission at 510 nm due to the macrocyclic confinement effect. Moreover, benefiting from the following secondary assembly confinement, such tight polypseudorotaxane G⊂CB[8] can further assemble with anionic polyelectrolyte PSS to yield uniform spherical nanoparticle, thereby significantly strengthening phosphorescence performance with an extended lifetime (i.e., 2.39 ms, c.f., 45.0 µs). Subsequently, the organic dye Rhodamine 800 serving as energy acceptor can be slightly doped into the polyelectrolyte assembly, which enables the occurrence of efficient phosphorescence energy transfer process with efficiency up to 80.1% at a high donor/acceptor ratio, and concurrently endows the final system with red-shifted and long-lived NIR emission (710 nm). Ultimately, the as-prepared assembly is successfully exploited as versatile imaging agent for NIR window labeling and detecting in living cells.

Laponite-activated AIE supramolecular assembly with modulating multicolor luminescence for logic digital encryption and perfluorinated pollutant detection.

Recently, the non-covalently activated supramolecular scaffold method has become a prominent research area in the field of intelligent materials. Here, the inorganic clay (LP) promoted the AIE properties of 4,4',4″,4‴-(ethene-1,1,2,2-tetrayltetrakis(benzene-4,1-diyl))tetrakis(1-ethylpyridin-1-ium) (P-TPE), showing an astonishing 42-fold enhancement of the emission intensity of the yellow-green luminescence and a 34-fold increase of the quantum yield via organic-inorganic supramolecular strategy as well as the efficient light-harvesting properties (energy transfer efficiency up to 33 %) after doping with the dye receptor Rhodamine B. Furthermore, the full-color spectral regulation, including white light, was achieved by adjusting the ratio of the donor to the acceptor component and co-assembling with the carbon dots (CD). Interestingly, this TPE-based non-covalently activated full-color supramolecular light-harvesting system (LHS) could be achieved not only in aqueous media but also in the hydrogel and the solid state. More importantly, this panchromatic tunable supramolecular LHS exhibited the multi-mode and quadruple digital logic encryption property as well as the specific detection ability towards the perfluorobutyric acid and the perfluorobutanesulfonic acid, which are harmful to human health in drinking water. This result develops a simple, convenient and effective approach for the intelligent anti-counterfeiting and the pollutant sensing.

A pillar[5]arene noncovalent assembly boosts a full-color lanthanide supramolecular light switch.

A photo-responsive full-color lanthanide supramolecular switch was constructed from a synthetic 2,6-pyridine dicarboxylic acid (DPA)-modified pillar[5]arene (H) complexing with lanthanide ion (Ln3+ = Tb3+ and Eu3+) and dicationic diarylethene derivative (G1) through a noncovalent supramolecular assembly. Benefiting from the strong complexation between DPA and Ln3+ with a 3 : 1 stoichiometric ratio, the supramolecular complex H/Ln3+ presented an emerging lanthanide emission in the aqueous and organic phase. Subsequently, a network supramolecular polymer was formed by H/Ln3+ further encapsulating dicationic G1via the hydrophobic cavity of pillar[5]arene, which greatly contributed to the increased emission intensity and lifetime, and also resulted in the formation of a lanthanide supramolecular light switch. Moreover, full-color luminescence, especially white light emission, was achieved in aqueous (CIE: 0.31, 0.32) and dichloromethane (CIE: 0.31, 0.33) solutions by the adjustment of different ratios of Tb3+ and Eu3+. Notably, the photo-reversible luminescence properties of the assembly were tuned via alternant UV/vis light irradiation due to the conformation-dependent photochromic energy transfer between the lanthanide and the open/closed-ring of diarylethene. Ultimately, the prepared lanthanide supramolecular switch was successfully applied to anti-counterfeiting through the use of intelligent multicolored writing inks, and presents new opportunities for the design of advanced stimuli-responsive on-demand color tuning with lanthanide luminescent materials.

Supramolecular assembly confined purely organic room temperature phosphorescence and its biological imaging.

Purely organic room temperature phosphorescence, especially in aqueous solution, is attracting increasing attention owing to its large Stokes shift, long lifetime, low preparation cost, low toxicity, good processing performance advantages, and broad application value. This review mainly focuses on macrocyclic (cyclodextrin and cucurbituril) hosts, nanoassembly, and macromolecule (polyether) confinement-driven RTP. As an optical probe, the assembly and the two-stage assembly strategy can realize the confined purely organic RTP and achieve energy transfer and light-harvesting from fluorescence to delayed fluorescence or phosphorescence. This supramolecular assembly is widely applied for luminescent materials, cell imaging, and other fields because it effectively avoids oxygen quenching. In addition, the near-infrared excitation, near-infrared emission, and in situ imaging of purely organic room temperature phosphorescence in assembled confinement materials are also prospected.

Multivalent supramolecular assembly with ultralong organic room temperature phosphorescence, high transfer efficiency and ultrahigh antenna effect in water.

Multivalent supramolecular assemblies have recently attracted extensive attention in the applications of soft materials and cell imaging. Here, we report a novel multivalent supramolecular assembly constructed from 4-(4-bromophenyl)pyridine-1-ium bromide modified hyaluronic acid (HABr), cucurbit[8]uril (CB[8]) and laponite® clay (LP), which could emit purely organic room-temperature phosphorescence (RTP) with a phosphorescence lifetime of up to 4.79 ms in aqueous solution via multivalent supramolecular interactions. By doping the organic dyes rhodamine B (RhB) or sulfonated rhodamine 101 (SR101) into the HABr/CB[8]/LP assembly, phosphorescence energy transfer was realized with high transfer efficiency (energy transfer efficiency = 73-80%) and ultrahigh antenna effect (antenna effect value = 308-362) within the phosphorescent light harvesting system. Moreover, owing to the dynamic nature of the noncovalent interactions, a wide-range spectrum of phosphorescence energy transfer outputs could be obtained not only in water but also on filter paper and a glass plate by adjusting the donor-acceptor ratio and, importantly, white-light emission was obtained, which could be used in the application of information encryption.

Luminescent lanthanide-macrocycle supramolecular assembly.

A series of macrocyclic compounds, including crown ether, cyclodextrin, cucurbituril and pillararene, bound to various specific organic/inorganic/biological guest molecules and ions through various non-covalent interactions, can not only make a single system multifunctional but also endow the system with intelligence, especially for luminescent materials. Due to their excellent luminescence properties, such as long-lived excited states, sharp linear emission bands and large Stokes shift, lanthanides have shown great advantages in luminescence, and have been more and more applied in the design of advanced functional luminescent materials. Based on reported research, we summarize the progress of lanthanide luminescent materials based on different macrocyclic compounds from ion or molecule recognition to functional nano-supramolecular assembly of the lanthanide-macrocycle supramolecular system including photo-reaction mediated switch of lanthanide luminescent molecules, multicolor luminescence, ion detection and cell imaging of rare-earth up-conversion of macrocyclic supramolecular assembly. Finally, we put forward the prospects of future development of lanthanide luminescent macrocyclic supramolecular materials.

High-efficiency dynamic sensing of biothiols in cancer cells with a fluorescent ß-cyclodextrin supramolecular assembly.

A unique fluorescent supramolecular assembly was constructed using coumarin-modified ß-cyclodextrin as a reversible ratiometric probe and an adamantane-modified cyclic arginine-glycine-aspartate peptide as a cancer-targeting agent via host-guest inclusion complexation. Importantly, the coumarin-modified ß-cyclodextrin not only showed higher sensitivity than the parent coumarin derivatives owing to the presence of numerous hydroxyl groups on the cyclodextrin but also provided a hydrophobic cavity for encapsulation of a cancer-targeting agent. The assembly showed a reversible and fast response to biothiols with a micromolar dissociation constant, as well as outstanding cancer cell permeability, which can be used for high-efficiency real-time monitoring of biothiols in cancer cells. This supramolecular assembly strategy endows the fluorescent probe with superior performance for dynamic sensing of biothiols.

Mitochondrion-targeting chemiluminescent ternary supramolecular assembly for in situ photodynamic therapy.

The development of smart supramolecular self-assemblies for photodynamic therapy (PDT) and organelle-targeting cell imaging has become a hot topic of research due to their rapid and intelligent responses. Herein, we report a novel ternary supramolecular assembly of nanoparticles, composed specifically of photosensitizer molecules 4,4'-(dibenzo[a,c]phenazine-9,14-diyl)pyridin-1-ium bromide (DPAC-S) and cucurbit[7]uril (CB[7]) co-assembled with bis[2,4,5-trichloro-6-(pentyloxycarbonyl)phenyl]oxalate (CPPO). Overexpressed hydrogen peroxide in tumor cells was used to rapidly stimulate these nanoparticles to produce chemiluminescence and simultaneously sensitize oxygen molecules to singlet oxygen (1O2) for in situ PDT. A cell imaging experiment further confirmed the ability of the nanoparticle assembly to effectively target mitochondria, a feature beneficial for enhancing PDT.

Ultralong purely organic aqueous phosphorescence supramolecular polymer for targeted tumor cell imaging.

Purely organic room-temperature phosphorescence has attracted attention for bioimaging but can be quenched in aqueous systems. Here we report a water-soluble ultralong organic room-temperature phosphorescent supramolecular polymer by combining cucurbit[n]uril (CB[7], CB[8]) and hyaluronic acid (HA) as a tumor-targeting ligand conjugated to a 4-(4-bromophenyl)pyridin-1-ium bromide (BrBP) phosphor. The result shows that CB[7] mediated pseudorotaxane polymer CB[7]/HA-BrBP changes from small spherical aggregates to a linear array, whereas complexation with CB[8] results in biaxial pseudorotaxane polymer CB[8]/HA-BrBP which transforms to relatively large aggregates. Owing to the more stable 1:2 inclusion complex between CB[8] and BrBP and the multiple hydrogen bonds, this supramolecular polymer has ultralong purely organic RTP lifetime in water up to 4.33 ms with a quantum yield of 7.58%. Benefiting from the targeting property of HA, this supramolecular polymer is successfully applied for cancer cell targeted phosphorescence imaging of mitochondria.

Cucurbit[8]uril-Mediated Polypseudorotaxane for Enhanced Lanthanide Luminescence Behavior in Water.

A novel supramolecular polypseudorotaxane was successfully constructed with pseudo[3]rotaxanes between pyridine-2,6-dicarboxylic acid imidazolium (G1) and cucurbit[8]uril (CB[8]) and the subsequent coordination with lanthanide ions. Significantly, compared with the pyridine-2,6-dicarboxylic acid imidazolium complex G1@Tb3+, CB[8]-mediated polypseudorotaxane CB[8]@G12@Tb3+ not only displayed enhanced lanthanide luminescence behavior with a 29.1-fold time enhancement (from 45.76 µs to 1.33 ms) of the excited-state lifetime (τ) and a 8.7-fold increase (from 0.89% to 7.81%) in the quantum yield (Φ) but also exhibited a specific fluorescence response to antibiotics in an aqueous solution and a solid film.

Photo-responsive cyclodextrin/anthracene/Eu3+ supramolecular assembly for a tunable photochromic multicolor cell label and fluorescent ink.

A photo-responsive supramolecular assembly was successfully constructed through the stoichiometric 2 : 1 non-covalent association of two 4-(anthracen-2-yl)pyridine-2,6-dicarboxylic acid (1) units in one γ-cyclodextrin (γ-CD) cavity, followed by the subsequent coordination polymerization of the γ-CD·1 2 (1 2 = two 1) inclusion complex with Eu(iii). Interestingly, owing to the photodimerization behavior of anthracene units and the excellent luminescence properties of Eu(iii), the Eu3+⊂γ-CD·1 2 system showed multicolor fluorescence emission from cyan to red by irradiation for 0-16 minutes. Moreover, white light emission with CIE coordinates (0.32 and 0.36) was achieved at 4 min. Importantly, white light-containing multicolor emission could be obtained in water, solid films and living cells. Especially, the Eu3+⊂γ-CD·1 2 system could tag living cells with marvelous white fluorescence and display no obvious cytotoxicity. Thus, this supramolecular assembly offers a new pathway in the fields of tunable photochromic fluorescent ink and cell labelling.

Morphology control of the produced Ag nanoparticles by soft-template technique.

The morphology of the produced Ag nanoparticle is controlled successfully by UV irradiating the reaction solution of AgAc/ethyl alcohol/1-octadeconal/1-dodecanethiol. With use of a novel solution such as soft template, Ag nanorods with different sizes and different ratios of length to diameter can be obtained by adjusting the concentrations of the solution compositions.

Reproductive characteristics of a Populus euphratica population and prospects for its restoration in China.

Populus euphratica is a dominant tree in riparian ecosystems in arid areas of northwest China, but it fails to regenerate in these systems. This study evaluates causes for the failure of sexual and asexual regeneration of this species in the wild. P. euphratica disperses as many as 85743 seeds/m(2) during summer, and the seeds germinate to 92.0% in distilled water and to 60.8% on silt. However, very few seeds (3.6%) can germinate on unflooded soil. The seed-rain season is prolonged by temporal variability in seed dispersal among individuals, which ensures that seedling emergence can occur during favorable conditions (i.e., floods and rainfall). As a result of water shortage and river channeling due to water usage and altered river flows, there are no safe sites on river banks for seed germination, which has led to the failure of P. euphratica to regenerate from seed. Root suckers of P. euphratica were present in 86% of the forest gaps investigated. However, extensive grazing has destroyed many of them and thus has reduced this form of regeneration. This research suggests that human activities are resulting in the failure of P. euphratica to regenerate. Changes in land management such as reduced use of concrete canals in Populus forests and/or reduced sheep grazing in these areas may promote their regeneration.