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Rhein, one of the main active components of rhubarb (Dahuang) and Polygonum multiflorum (Heshouwu), has a wide range of effective pharmacological effects. Recently, increasing studies have focused on its potential hepatorenal toxicity, but the cardiotoxicity is unknown. In this study, we found that the IC

It is challenging to investigate fast supramolecular processes due to the lack of appropriate characterization methods with high structural resolution. In thisstudy, microfluidic nuclear magnetic resonance (μFNMR) spectroscopy was employed to monitor the kinetics of threading and dethreading of a pseudo[6]rotaxane system. By employing high time resolution μF-NMR, 1H and two-dimensional (2D) rotating frame nuclear Overhauser effect spectroscopy (ROESY) NMR spectra were recorded at any timepoint within 1.5 s after the onset of the process. This technique enabled the successful identification of kinetic intermediates and rate-determining steps,usually impossible to determine by other spectroscopic techniques. Thus, our study demonstrates the capability of μF-NMR in investigating the mechanismof complex supramolecular systems.

The effect of molecular symmetry on CPL properties was first demonstrated in triple heterohelicenes by the newly synthesized triple oxa[6]helicene.

Chiral nanographenes with both high fluorescence quantum yields (Φ

The development of helicene molecules with significant chiroptical responses covering a broad range of the visible spectrum is highly desirable for chiral optoelectronic applications; however, their absorption dissymmetry factors (gabs) have been mostly lower than 0.01. In this work, we report unprecedented B,N-embedded double hetero[7]helicenes with nonbonded B and N atoms, which exhibit excellent chiroptical properties, such as strong chiroptical activities from 300 to 700 nm, record high gabs up to 0.033 in the visible spectral range, and tunable circularly polarized luminescence (CPL) from red to near-infrared regions (600 ~ 800 nm) with high photoluminescence quantum yields (PLQYs) up to 100%. As revealed by theoretical analyses, the high gabs values are related to the separate molecular orbital distributions owing to the incorporation of nonbonded B and N atoms. The new type of B,N-embedded double heterohelicenes opens up an appealing avenue to the future exploitation of high-performance chiroptical materials.

Cancer is still an insurmountable problem for humans and critically attacking human health. In recent years, natural products have gained increasing attention in the field of anti-tumor due to their extensive sources and minimal side effects. Maslinic acid (MA), a pentacyclic triterpene acid mainly derived from the olive tree (Olea europaea L.) has been confirmed to possess great anti-cancer effects. This paper reviewed the inhibitory effect of MA and its derivatives on lung cancer, colon cancer, ovarian cancer, gastric cancer, lymphatic, leukemia, breast cancer, pancreatic cancer, melanoma, prostate cancer, renal cell carcinoma, gallbladder cancer, and bladder cancer, among others. MA inhibited the proliferation of various tumor cells and showed lower IC50 values in melanoma 518A2 cells and gastric cancer MKN28 cells compared with other cell lines. A series of semi-synthetic derivatives obtained by modifying MA chemical structure have been shown to have high cytotoxicity to human tumor cell lines, but low cytotoxicity to non-malignant cells, which is conducive to developing its potential as a chemotherapeutic agent. These studies suggest that MA derivatives have broad prospects in the development of antitumor therapeutics in the future and warrant further study.

We present the synthesis and characterization of the first triple oxa[6]helicene with

Trace water in organic solvents can play a crucial role in the construction of supramolecular assemblies, which has not gained enough attention until very recent years. Herein, we demonstrate that residual water in organic solvents plays a decisive role in the regulation of the evolution of assembled structures and their functionality. By adding Mg(ClO

Carthamus tinctorius is proved potent in treating ischemic stroke. Flavonoids, such as safflower yellow, hydroxysafflor yellow A(HSYA), nicotiflorin, safflower yellow B, and kaempferol-3-O-rutinoside, are the main substance basis of C. tinctorius in the treatment of ischemic stroke, and HSYA is the research hotspot. Current studies have shown that C. tinctorius can prevent and treat ischemic stroke by reducing inflammation, oxidative stress, and endoplasmic reticulum stress, inhibiting neuronal apoptosis and platelet aggregation, as well as increasing blood flow. C. tinctorius can regulate the pathways including nuclear factor(NF)-κB, mitogen-activated protein kinase(MAPK), signal transducer and activator of transcription protein 3(STAT3), and NF-κB/NLR family pyrin domain containing 3(NLRP3), and inhibit the activation of cyclooxygenase-2(COX-2)/prostaglandin D2/D prostanoid receptor pathway to alleviate the inflammatory development during ischemic stroke. Additionally, C. tinctorius can relieve oxidative stress injury by inhibiting oxidation and nitrification, regulating free radicals, and mediating nitric oxide(NO)/inducible nitric oxide synthase(iNOS) signals. Furthermore, mediating the activation of Janus kinase 2(JAK2)/STAT3/suppressor of cytokine signaling 3(SOCS3) signaling pathway and phosphoinositide 3-kinase(PI3 K)/protein kinase B(Akt)/glycogen synthase kinase-3β(GSK3β) signaling pathway and regulating the release of matrix metalloproteinase(MMP) inhibitor/MMP are main ways that C. tinctorius inhibits neuronal apoptosis. In addition, C. tinctorius exerts the therapeutic effect on ischemic stroke by regulating autophagy and endoplasmic reticulum stress. The present study reviewed the molecular mechanisms of C. tinctorius in the treatment of ischemic stroke to provide references for the clinical application of C. tinctorius.

We report the implementation of coordination complexes containing two types of cationic moieties, i. e. pyridinium and ammonium quaternary salt, as potential inhibitors of human cholinesterase enzymes. Utilization of ligands containing NNO-coordination site and binding zinc metal ion allowed mono- and tetra-nuclear complexes to be obtained with corner and grid structural type, respectively, thus affecting the overall charge of the compounds (from +1 to +8). We were able to examine for the first time the multivalency effect of metallosupramolecular species on their inhibitory abilities towards acetylcholinesterase (AChE) and butyrylcholinesterase (BChE). Importantly, resolution of the crystal structures of the obtained enzyme-substrate complexes provided a better understanding of the inhibition process at the molecular level.

Self-assembly of host molecules in aqueous media via metal-ligand coordination is well developed. However, the preparation of purely covalent counterparts in water has remained a formidable task. An anionic tetrahedron cage was successfully self-assembled in a [4+4] manner by condensing a trisamine and a trisformyl in water. Even although each individual imine bond is rather labile and apt to hydrolyze in water, the tetrahedron is remarkably stable or inert due to multivalence. The tetrahedral cages, as well as its neutral counterparts dissolved in organic solvent, have homochirality, namely that their four propeller-shaped trisformyl residues adopt the same rotational conformation. The cage is able to take advantage of hydrophobic effect to accommodate a variety of guest molecules in water. When a chiral guest was recognized, the formation of one enantiomer of the cage became more favored relative to the other. As a consequence, the cage could be produced in an enantioselective manner. The tetrahedron is able to maintain its chirality after removal of the chiral guest-probably on account of the cooperative occurrence of intramolecular forces that restrict the intramolecular flipping of phenyl units in the cage framework.

A series of photoswitchable cyclopentadienone derivative dimers bearing bromo, thienyl, 4-(dimethylamino)phenyl, 3-pyridinyl, 4-nitrophenyl and cyano groups was designed and facilely synthesized. Their photoswitching properties such as the photoconversions in the photostationary state (PSS), the thermal kinetics and thermal half-lives of photoisomers were systematically investigated. These photoswitches show high fatigue resistance and large photoconversions in the PSS. This work proves that the photoswitching properties of photoswitches based on cyclopentadienone dimers can be tuned by substitution groups and also pave the way to functionalize the cyclopentadienone derivative dimer-based photoswitch, which is important for its future applications.

Interfacial host–guest complexation offers a versatile way to functionalize nanomaterials. However, the complicated interfacial environment and trace amounts of components present at the interface make the study of interfacial complexation very difficult. Herein, taking the advantages of near-single-molecule level sensitivity and molecular fingerprint of surface-enhanced Raman spectroscopy (SERS), we reveal that a cooperative effect between cucurbit[7]uril (CB[7]) and methyl viologen (MV2+2I−) in aggregating Au NPs originates from the cooperative adsorption of halide counter anions I−, MV2+, and CB[7] on Au NPs surface. Moreover, similar SERS peak shifts in the control experiments using CB[n]s but with smaller cavity sizes suggested the occurrence of the same guest complexations among CB[5], CB[6], and CB[7] with MV2+. Hence, an unconventional exclusive complexation model is proposed between CB[7] and MV2+ on the surface of Au NPs, distinct from the well-known 1:1 inclusion complexation model in aqueous solutions. In summary, new insights into the fundamental understanding of host–guest interactions at nanostructured interfaces were obtained by SERS, which might be useful for applications related to host–guest chemistry in engineered nanomaterials.

Condensation of an inherently C3 -symmetric polychlorotriphenylmethyl (PTM) radical trisaldehyde with tris(2-aminoethyl)amine (TREN) yields a [4+4] tetrahedral radical cage as a racemic pair of homochiral enantiomers in 75 % isolated yield. The structure was characterized by X-ray crystallography, confirming the homochirality of each cage framework. The homochirality results from intramolecular [CH⋅⋅⋅π] and hydrogen-bonding interactions within the cage framework. The four PTM radicals in a cage undergo weak through-space coupling. Magnetic measurements demonstrated that each cage bears 3.58 spins.

We present here the synthesis and in-depth physicochemical characterization of a double hetero[7]helicene fused with four triazole rings at both helical ends. The comparison of this triazole-fused double helicene with the previously reported all-carbon and thiadiazole-fused analogs revealed the huge impact of the embedded aromatic rings on the photophysical features. The small structural variation of the terminal rings from thiadiazole to triazole caused a dramatic change of the photoluminescence quantum yields (PLQYs) from1 % to 96 %, while the replacement of the terminal benzene rings with triazole rings induced a tenfold enhancement of the circularly polarized luminescence dissymmetry factor. These observations were well corroborated with transient absorption analysis and/or theoretic calculations. In addition, the triazole-fused double helicene exhibited ambipolar redox behavior, enabling the generation of radical cation and anion species by electrochemical and chemical methods and showing its potential for spin-related applications.

The security of quantum key distribution (QKD) is severely threatened by discrepancies between realistic devices and theoretical assumptions. Recently, a significant framework called the reference technique was proposed to provide security against arbitrary source flaws under current technology such as state preparation flaws, side channels caused by mode dependencies, the Trojan horse atttacks and pulse correlations. Here, we adopt the reference technique to prove security of an efficient four-phase measurement-device-independent QKD using laser pulses against potential source imperfections. We present a characterization of source flaws and connect them to experiments, together with a finite-key analysis against coherent attacks. In addition, we demonstrate the feasibility of our protocol through a proof-of-principle experimental implementation and achieve a secure key rate of 253 bps with a 20 dB channel loss. Compared with previous QKD protocols with imperfect devices, our study considerably improves both the secure key rate and the transmission distance, and shows application potential in the practical deployment of secure QKD with device imperfections., Comment: 16 pages, 7 figures, 6 tables. Comments are welcome!

The development of helicenes with strong chiroptical response and controlled photophysics is highly desirable but challenging. In this work, double thia/sulfone[7]helicenes were synthesized to investigate the heteroatom effect on the photophysical and chiroptical properties of double heterohelicenes through comparison with the previously reported double oxa[7]helicene. By variation of the embedded heteroatoms from oxygen to sulfur, the absorption and emission were significantly red-shifted, along with the improved luminescence dissymmetry factor (g

An X-shaped double [7]heterohelicene 1 bearing four thiadiazole units is synthesized by regioselective cyclodehydrogenation. Enantiopure 1 exhibits excellent chiroptical properties with an impressive absorption dissymmetry factor of up to 0.027, as well as a compact π-stacked homochiral assembly which is unprecedented in the realm of double helicenes.

Quantum cryptography is a major ingredient of the future quantum internet that promises various secure communication tasks. Quantum conference key agreement (CKA) is an important cryptographic primitive of quantum cryptography, which provides the conference key among multiple users simultaneously. However, quantum CKA is currently far from practical application due to the low conference key rate. Here, we propose a quantum CKA protocol of three users with information-theoretic security. Our protocol only requires phase-randomized weak coherent sources and threshold single-photon detectors, and is anticipated to be experimentally demonstrated over 600 km under current technology. Our scheme can be widely implemented in the approaching large-scale quantum network., Comment: 6 pages, 3 figures, accepted by IEEE Access

Molecular face-rotating polyhedra (FRP) exhibit complex stereochemistry, rendering it challenging to manipulate their assembly in a stereoselective manner. In our previous work, stereocontrolled FRP were gained at the cost of losing the confined inner space, which hampers their host–guest interactions and potential applications. Through a rational design approach, herein we demonstrate the successful construction of hollow FRP with high diastereoselectivity. Whereas the [4 + 4] imine condensation of meta-formyl substituted C3h-symmetric TAT-m and C3-symmetric Tri-NH2 led to the formation of all feasible FRP-12 diastereoisomers; the para-substituted constitutional isomer, TAT-p, exclusively assembled into a pair of homo-directional enantiomeric FRP-13-CCCC/AAAA with a cavity size larger than 600 Å3. Detailed structural characterizations and theoretical investigations revealed the thermodynamic landscape of FRP assembly can be effectively shaped by modulating the van der Waals repulsive forces among the facial building blocks. Our work provided a novel strategy towards stereospecific assembly of pure organic cages, opening up new opportunities for further applications of these chiral materials., The rationally engineered facial units, TAT-m and TAT-p, resulted in distinct diastereoselectivity of face-rotating polyhedra (FRP).

An unprecedented furan-based double oxa[7]helicene 1 was achieved, featuring a stable twisted conformation with π-overlap at both helical ends. The excellent conformational stability allowed for optical resolution of 1, which provided a pair of enantiomers exhibiting pronounced mirror-imaged circular dichroism and circularly polarized luminescence activity. The radical cation of 1 was obtained by chemical oxidation as evidenced by UV-Vis-NIR absorption, electron paramagnetic resonance spectroscopy and in situ spectroelectrochemistry. The present work is the starting point for the investigation of open-shell oxahelicenes.

Molecular assembly plays a critical role in constructing the physical world beyond molecules. Living organism shows the highest level of molecular assembly, inside which complex subunits assemble into functional assemblies through complex intermolecular interactions. Self-assembly is the dominant paradigm in the research of artificial molecular assembly, whereas most molecular assemblies in living organism are multi-pathway, multi-step, and hierarchical, thus requiring the assistance and guidance of other molecules. Among these assisting methods, catassembly uses catassemblers to modulate the kinetics and pathways of the assembly processes, exhibiting high efficiency and selectivity. In living organisms, catassemblers such as molecular chaperones, histone chaperones and allosteric factors are critical to protein folding, chromatin remodeling, and regulation of enzyme activities, respectively. In this review, we analyzed and then summarized various catassembly cases in living organisms, and envisioned that catassembly will be more important in more complex molecular assemblies. These investigations may provide a new perspective for the development of catassembly in artificial and living systems, and further improve the complexity, controllability and function of molecular assembly to a higher level.

Discovering novel families of molecular polyhedra through graph theory has attracted increasing interest. Nevertheless, the design principles of molecular polyhedra based on graph theory remain elusive, especially for those containing five-node units. Herein, we construct a series of chiral truncated face-rotating polyhedra (T-FRP) from pentagonal pentaphenylpyrrole (PPP) derivatives and chiral diamines. Graph theory is used to elucidate the geometry of these novel T-FRP, which represent a new family of molecular polyhedra. The phenyl flipping of PPP faces in these T-FRP is significantly restricted, thus making T-FRP chiral and strongly emissive in solution. In addition, T-FRP also generate circularly polarized luminescence. This study provides new insights into the rational design of novel molecular polyhedra through graph theory.