Aiming at the construction of novel platforms with excellent performances in both circularly polarized photoluminescence (CP-PL) and electrochemiluminescence (CP-ECL), a new family of pyrenophanes with rigidly locked pyrene dimers and varied bridges has been designed and synthesized. Attributed to densely packed pyrene excimers, the resultant pyrenophanes revealed tunable bridge-dependent emission behaviors, as investigated by femtosecond time-resolved transient absorption spectroscopy. More importantly, all these planar chiral pyrenophanes display strong CP-PL with large dissymmetry factor (gPL) values up to 0.
View Article and Find Full Text PDFAttributed to their unique dynamic planar chirality, pillar[n]arenes, particularly pillar[5]arenes, have evolved as promising platforms for diverse applications such as circularly polarized luminescence (CPL) emitters. However, due to the unit flipping and swing, the achievement of excellent CPL performances of pillar[5]arenes in solution state remains a formidable challenge. To deal with this key issue, a mechanically locking approach has been successfully developed, leading to boosted dissymmetry factor (g) values of pyrene-tiaraed pillar[5]arenes up to 0.
View Article and Find Full Text PDFStarting from AIEgen-functionalized chiral [2]rotaxane building block, we have successfully synthesized a new class of chiral rotaxane-branched dendrimers through controllable divergent strategy for the first time, based on which novel chiral artificial light-harvesting systems (LHSs) were successfully constructed in aqueous phase by sequentially introducing achiral donor and acceptor. More importantly, accompanied by the two-step Förster resonance energy transfer (FRET) process in the resultant artificial LHSs, the sequentially amplified circularly polarized luminescence (CPL) performances were achieved, highlighting that the chiral rotaxane-branched dendrimers could serve as excellent relay for both energy transfer and chirality transmission. Impressively, compared with the sole chiral rotaxane-branched dendrimers, the dissymmetry factors (g) values of the resultant artificial LHSs were amplified by one order of magnitude up to 0.
View Article and Find Full Text PDFAiming at the fabrication of circularly polarized organic light-emitting diodes (CP-OLEDs) with high dissymmetry factors (g) and color purity through the employment of novel chiral source, topologically chiral [2]catenanes were first utilized as the key chiral skeleton to construct novel multi-resonance thermally activated delayed fluorescence (MR-TADF) emitters. Impressively, the efficient chirality induction and unique switchable feature of topologically chiral [2]catenane not only lead to a high |g| value up to 1.6×10 but also facilitate in situ dynamic switching of the full-width at half-maximum (FWHM) and circularly polarized luminescence (CPL).
View Article and Find Full Text PDFAs a novel type of macrocycles with attractive planar chirality, pillar[5]arenes have gained increasing research interest over the past decades, enabling their widespread applications in diverse fields such as porous materials, molecular machines, and chiral luminescence materials. However, the catalytic methodology towards the enantioselective synthesis of planar chiral pillar[5]arenes remains elusive. Here we report a novel method for the enantioselective synthesis of planar chiral pillar[5]arenes via asymmetric Sonogashira coupling, giving access to a wide range of highly functionalized planar chiral pillar[5]arenes, including both homo- and hetero-rimmed ones, with excellent enantioselectivities.
View Article and Find Full Text PDFAiming at the further extension of the application scope of traditional molecular muscles, a novel bispyrene-functionalized chiral molecular [c2]daisy chain was designed and synthesized. Taking advantage of the unique dimeric interlocked structure of molecular [c2]daisy chain, the resultant chiral molecular muscle emits strong circularly polarized luminescence (CPL) attributed to the pyrene excimer with a high dissymmetry factor (g) value of 0.010.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
September 2024
To explore the chirality induction and switching of topological chirality, poly[2]catenanes composed of helical poly(phenylacetylenes) (PPAs) main chain and topologically chiral [2]catenane pendants are described for the first time. These poly[2]catenanes with optically active [2]catenanes on side chains were synthesized by polymerization of enantiomerically pure topologically chiral [2]catenanes with ethynyl polymerization site and/or point chiral moiety. The chirality information of [2]catenane pendants was successfully transferred to the main chain of polyene backbones, leading to preferred-handed helical conformations, while the introduction of point chiral units has negligible effect on the overall helices.
View Article and Find Full Text PDFIn order to investigate the effect of macrocyclization and catenation on the regulation of vibration-induced emission (VIE), the typical VIE luminogen 9,14-diphenyl-9,14-dihydrodibenzo[a, c]phenazine (DPAC) was introduced into the skeleton of a macrocycle and corresponding [2]catenane to evaluate their dynamic relaxation processes. As investigated in detail by femtosecond transient absorption (TA) spectra, the resultant VIE systems revealed precisely tunable emissions upon changing the solvent viscosity, highlighting the key effect of the formation of [2]catenane. Notably, the introduction of an additional pillar[5]arene macrocycle featuring unique planar chirality endows the resultant chiral VIE-active [2]catenane with attractive circularly polarized luminescence in different states.
View Article and Find Full Text PDFHuan Jing Ke Xue
February 2024
In order to clarify the impact of no-tillage on the quality of farmland soil aggregates in China and promote the adaptive application of no-tillage practices, a Meta-analysis was conducted by collecting data from 116 published studies. The effects of no-tillage on aggregate size distribution, mean weight diameter (MWD), and aggregate-associated C were studied. The results showed that compared with that under tillage, no-tillage significantly increased the proportion of macroaggregates (10.
View Article and Find Full Text PDFAiming at the construction of novel stimuli-responsive fluorescent system with precisely tunable emissions, the typical 9,14-diphenyl-9,14-dihydrodibenzo[a, c]phenazine (DPAC) luminogen with attractive vibration-induced emission (VIE) behavior has been introduced into [2]rotaxane as a stopper. Taking advantage of their unique dual stimuli-responsiveness towards solvent and anion, the resultant [2]rotaxanes reveal both tunable VIE and switchable circularly polarized luminescence (CPL). Attributed to the formation of mechanical bonds, DPAC-functionalized [2]rotaxanes display interesting VIE behaviors including white-light emission upon the addition of viscous solvent, as evaluated in detail by femtosecond transient absorption (TA) spectra.
View Article and Find Full Text PDFAs a soil amendment, biochar has been widely used to ameliorate agricultural soil. To ensure the effect of biochar on the carbon sequestration of farmlands in China, a Meta-analysis was carried out via collecting published literatures. We quantitatively analyzed the response of biochar application to soil aggregates, aggregate carbon, and soil organic carbon to different experimental conditions.
View Article and Find Full Text PDFAiming at the creation of polymers with attractive dynamic properties, herein, rotaxane-branched dendronized polymers (DPs) with rotaxane-branched dendrons attached onto the polymer chains are proposed. Starting from macromonomers with both rotaxane-branched dendrons and polymerization site, targeted rotaxane-branched DPs are successfully synthesized through ring-opening metathesis polymerization (ROMP). Interestingly, due to the existence of multiple switchable [2]rotaxane branches within the attached dendrons, anion-induced reversible thickness modulation of the resultant rotaxane-branched DPs is achieved, which further lead to tunable thermal and rheological properties, making them attractive platform for the construction of smart polymeric materials.
View Article and Find Full Text PDFAiming at the construction of novel soft actuators through the amplified motions of molecular machines at the nanoscale, the design and synthesis of a new family of photoresponsive rotaxane-branched dendrimers through an efficient controllable divergent approach was successfully realized for the first time. In the third-generation rotaxane-branched dendrimers, up to 21 azobenzene-based rotaxane units located at each branch, thus making them the first successful synthesis of light-control integrated artificial molecular machines. Notably, upon alternative irradiation with UV and visible light, photoisomerization of the azobenzene stoppers leads to the collective and amplified motions of the precisely arranged rotaxane units, resulting in controllable and reversible dimension modulation of the integrating photoresponsive rotaxane-branched dendrimers in solution.
View Article and Find Full Text PDFThis study was conducted to clarify the structure and function of the fungal community and the microecology change characteristics of farmland soil fertility response to different fallow rotation patterns. It aimed to provide a reference for promoting farmland ecological restoration and farmland quality improvement in the alluvial plain of the lower Yellow River. Farmland soil subject to a long-term rotation fallow experiment since 2018 was studied using Illumina MiSeq high-throughput sequencing technology, and the 'FUNGuild' fungal function prediction tool was used to analyze differences in soil fungal community structure and function under the following four rotation fallow regimes: long fallow (LF), winter wheat and summer fallow (WF), winter fallow and summer maize (FM), and annual rotation of winter wheat and summer maize (WM).
View Article and Find Full Text PDFDendritic cell (DC)-mediated immune dysfunction is involved in the process of severe hemorrhagic shock that leads to sepsis. Although post-hemorrhagic shock mesenteric lymph (PHSML) induces immune organs injuries and apoptosis, whether PHSML exerts adverse effects on splenic DCs remains unknown. In this study, we established a hemorrhagic shock model (40 ± 2 mm Hg for 60 min) followed by fluid resuscitation with the shed blood and equal Ringer's solution and drained the PHSML after resuscitation.
View Article and Find Full Text PDFAiming at the construction of novel circularly polarized luminescence (CPL) switches with multiple switchable emission states and high dissymmetry factors (g ), topologically chiral [2]catenanes were employed as the key platform to construct a novel multistate CPL switching system. Taking advantage of the precise co-conformation regulations of the resultant pyrene-functionalized [2]catenanes under different external stimuli, reversible transformations between three emission states with different CPL performances, i.e.
View Article and Find Full Text PDFThe precise synthesis of novel rotaxane-branched radical dendrimers Gn-TEMPO ( = 1-3) with up to 24 TEMPO radicals as termini was successfully achieved, from which nanoparticles with a good longitudinal relaxivity were further prepared, thus making them potential candidates as promising contrast agents for magnetic resonance imaging.
View Article and Find Full Text PDFDuring recent decades, the blossoming of the field of mechanically interlocked molecules (MIMs), i.e., molecules containing mechanical or topological bonds such as rotaxanes, catenanes, and knots, has been reported in the literature.
View Article and Find Full Text PDFThe aim of this study was to provide a reference for promoting ecological restoration of farmland and the green development of agriculture in the alluvial plain of the lower Yellow River by determining the effects of different rotation fallow patterns on the bacterial community of the fluvo-aquic soil. Farmland soil subject to a long-term rotation fallow experiment since 2018 was studied using Illumina MiSeq high-throughput sequencing technology, and the 'Tax4Fun' bacterial function prediction tool was used to analyze differences in soil bacterial community structure and function under the following four rotation fallow regimes:long fallow(LF), winter wheat and summer fallow(WF), winter fallow and summer maize(FM), and annual rotation of winter wheat and summer maize(WM). The environmental factors affecting changes in the soil bacterial community structure and function were also analyzed.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
December 2021
Accurate control of the layer number of orderly stacked 2D polymers has been an unsettled challenge in self-assembly. Herein we describe the fabrication of a bilayer 2D supramolecular organic framework from a monolayer 2D supramolecular organic framework in water by utilizing the cooperative coordination of a rod-like bipyridine ligands to zinc porphyrin subunits of the monolayer network. The monolayer supramolecular framework is prepared from the co-assembly of an octacationic zinc porphyrin monomer and cucurbit[8]uril (CB[8]) in water through CB[8]-encapsulation-promoted dimerization of 4-phenylpyridiunium subunits that the zinc porphyrin monomer bear.
View Article and Find Full Text PDFAiming at the construction of novel platform for efficient light harvesting, the precise synthesis of a new family of AIEgen-branched rotaxane dendrimers was successful realized from an AIEgen-functionalized [2]rotaxane through a controllable divergent approach. In the resultant AIE macromolecules, up to twenty-one AIEgens located at the tails of each branches, thus making them the first successful example of AIEgen-branched dendrimers. Attributed to the solvent-induced switching feature of the rotaxane branches, the integrated rotaxane dendrimers displayed interesting dynamic feature upon the aggregation-induced emission (AIE) process.
View Article and Find Full Text PDFThe selective and efficient capture of phosphopeptides is critical for comprehensive and in-depth phosphoproteome analysis. Here we report a new switchable two-dimensional (2D) supramolecular polymer that serves as an ideal platform for the enrichment of phosphopeptides. A well-defined, positively charged metallacycle incorporated into the polymer endows the resultant polymer with a high affinity for phosphopeptides.
View Article and Find Full Text PDFParastichy, the spiral arrangement of plant organs, is an example of the long-range apparent order seen in biological systems. These ordered arrangements provide scientists with both an aesthetic challenge and a mathematical inspiration. Synthetic efforts to replicate the regularity of parastichy may allow for molecular-scale control over particle arrangement processes.
View Article and Find Full Text PDFThe precise operation of molecular motion for constructing complicated mechanically interlocked molecules has received considerable attention and is still an energetic field of supramolecular chemistry. Herein, we reported the construction of two tris[2]pseudorotaxanes metallacycles with acid-base controllable molecular motion through self-sorting strategy and host-guest interaction. Firstly, two hexagonal Pt(II) metallacycles and decorated with different host-guest recognition sites have been constructed via coordination-driven self-assembly strategy.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
April 2021
The construction of circularly polarized luminescence (CPL) switches with multiple switchable emission states and high dissymmetry factors (g ) has attracted increasing attention due to their broad applications in diverse fields such as the development of smart devices and sensors. Herein, a new family of AIE-active chiral [3]rotaxanes were designed and synthesized, from which a novel CPL switching system was successfully constructed. The switching process was realized through the controlled motions of the chiral pillar[5]arene macrocycles along the axle through the addition or removal of the acetate anions, which not only modulated the chirality information transfer but also tuned the aggregations of the integrated [3]rotaxanes, thus resulting in reversible transformations between two emission states with both high photoluminescence quantum yields (PLQYs) and high dissymmetry factors (g ) values.
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