Self-assembled soft alloy with Frank-Kasper phases beyond metals.

Soft building blocks, such as micelles, cells or soap bubbles, tend to adopt near-spherical geometry when densely packed together. As a result, their packing structures do not extend beyond those discovered in metallic glasses, quasicrystals and crystals. Here we report the emergence of two Frank-Kasper phases from the self-assembly of five-fold symmetric molecular pentagons. The µ phase, an important intermediate in superalloys, is indexed in soft matter, whereas the ϕ phase exhibits a structure distinct from known Frank-Kasper phases in metallic systems. We find a broad size and shape distribution of self-assembled mesoatoms formed by molecular pentagons while approaching equilibrium that contribute to the unique packing structures. This work provides insight into the manipulation of soft building blocks that deviate from the typical spherical geometry and opens avenues for the fabrication of 'soft alloy' structures that were previously unattainable in metal alloys.

Molecular Face-Rotating Polyhedra: Chiral Cages Inspired by Mathematics.

ConspectusMolecular polyhedral cages, notable for their enclosed inner cavities, can possess varying degrees of symmetry, spanning from regular Platonic polyhedra to lower symmetry forms that may display chirality. Crafting chiral molecular cages typically involves using building blocks containing stereogenic elements or arranging achiral components in a manner that lacks mirror and inversion symmetries. Achieving precise control over their chirality poses both significance and challenges.In this Account, we present an overview of our research endeavors in the realm of chiral molecular polyhedral cages, drawing inspiration from Buckminster Fuller's "Face-Rotating Polyhedra (FRP)". Mathematically, FRP introduce a unique form of chirality distinguished by a rotating pattern around the center of each face, setting it apart from regular polyhedra.Molecular FRP can be constructed using two types of facial building blocks. The first includes rigid, planar molecules such as truxene and triazatruxene, which exhibit either clockwise or counterclockwise rotations in two dimensions. The second category involves propeller-like molecules, e.g., tetraphenylethylene, 1,2,3,4,5-penta(4-phenylaldehyde)pyrrole, and tridurylborane, displaying dynamic stereochemistry.The synthesis of FRP may potentially yield a diverse array of stereoisomers. Achieving high stereoselectivity becomes feasible through the selection of building blocks with specific substitution patterns and rigidity. Prominent noncovalent repulsive forces within the resulting cages often play a pivotal role in the dynamic covalent assembly process, ultimately leading to the formation of thermodynamically stable FRP products.The capacity to generate a multitude of stereoisomers, combined with the integration of chiral vertices, has facilitated investigations into phenomena such as chiral self-sorting and the "sergeant and soldiers" chiral amplification effect in FRP. Even the inclusion of one chiral vertex significantly impacts the stereochemical configuration of the entire cage. While many facial building blocks establish a stable rotational pattern in FRP, other units, such as tridurylborane, can dynamically transition between P and M configurations within the cage structures. The kinetic characteristics of such stereolabile FRP can be elucidated through physicochemical investigations.Our research extends beyond the FRP concept to encompass mathematical analysis of these structures. Graph theory, particularly the coloring problem, sheds light on the intricate facial patterns exhibited by various FRP stereoisomers and serves as an efficient tool to facilitate the discovery of novel FRP structures. This approach offers a fresh paradigm for designing and analyzing chiral molecular polyhedral cages, showcasing in our work the synergy between mathematics and molecular design.

What can molecular assembly learn from catalysed assembly in living organisms?

Molecular assembly is the process of organizing individual molecules into larger structures and complex systems. The self-assembly approach is predominantly utilized in creating artificial molecular assemblies, and was believed to be the primary mode of molecular assembly in living organisms as well. However, it has been shown that the assembly of many biological complexes is "catalysed" by other molecules, rather than relying solely on self-assembly. In this review, we summarize these catalysed-assembly (catassembly) phenomena in living organisms and systematically analyse their mechanisms. We then expand on these phenomena and discuss related concepts, including catalysed-disassembly and catalysed-reassembly. Catassembly proves to be an efficient and highly selective strategy for synergistically controlling and manipulating various noncovalent interactions, especially in hierarchical molecular assemblies. Overreliance on self-assembly may, to some extent, hinder the advancement of artificial molecular assembly with powerful features. Furthermore, inspired by the biological catassembly phenomena, we propose guidelines for designing artificial catassembly systems and developing characterization and theoretical methods, and review pioneering works along this new direction. Overall, this approach may broaden and deepen our understanding of molecular assembly, enabling the construction and control of intelligent assembly systems with advanced functionality.

Negatively Curved Octagon-Incorporated Aza-nanographene and its Assembly with Fullerenes.

A negatively curved aza-nanographene (NG) containing two octagons was synthesized by a regioselective and stepwise cyclodehydrogenation procedure, in which a double aza[7]helicene was simultaneously formed as an intermediate. Their saddle-shaped structures with negative curvature were unambiguously confirmed by X-ray crystallography, thereby enabling the exploration of the structure-property relationship by photophysical, electrochemical and conformational studies. Moreover, the assembly of the octagon-embedded aza-NG with fullerenes was probed by fluorescence spectral titration, with record-high binding constants (Ka=9.5×103 M-1 with C60, Ka=3.7×104 M-1 with C70) found among reported negatively curved polycyclic aromatic compounds. The tight association of aza-NG with C60 was further elucidated by X-ray diffraction analysis of their co-crystal, which showed the formation of a 1 : 1 complex with substantial concave-convex interactions.

Chiral Molecular Cage with Tunable Stereoinversion Barriers.

The manipulation of chirality in molecular entities that rapidly interconvert between enantiomeric forms is challenging, particularly at the supramolecular level. Advances in controlling such dynamic stereochemical systems offer opportunities to understand chiral symmetry breaking and homochirality. Herein, we report the synthesis of a face-rotating tetrahedron (FRT), an organic molecular cage composed of tridurylborane facial units that undergo stereomutations between enantiomeric trefoil propeller-like conformations. After resolution, we show that the racemization barrier of the enantiopure FRT can be regulated in situ through the reversible binding of fluoride anions onto the tridurylborane moieties. Furthermore, the addition of an enantiopure phenylethanol to the FRT can effectively induce chirality of the molecular cage by preferentially binding to one of its enantiomeric conformers. This study presents a new paradigm for controlling dynamic chirality in supramolecular systems, which may have implications for asymmetric synthesis and dynamic stereochemistry.

Synthesis of Highly Luminescent Chiral Nanographene.

Chiral nanographenes with both high fluorescence quantum yields (ΦF ) and large dissymmetry factors (glum ) are essential to the development of circularly polarized luminescence (CPL) materials. However, most studies have been focused on the improvement of glum , whereas how to design highly emissive chiral nanographenes is still unclear. In this work, we propose a new design strategy to achieve chiral nanographenes with high ΦF by helical π-extension of strongly luminescent chromophores while maintaining the frontier molecular orbital (FMO) distribution pattern. Chiral nanographene with perylene as the core and two dibenzo[6]helicene fragments as the wings has been synthesized, which exhibits a record high ΦF of 93 % among the reported chiral nanographenes and excellent CPL brightness (BCPL ) of 32 M-1 cm-1 .

Evolution of Transient Luminescent Assemblies Regulated by Trace Water in Organic Solvents.

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(ClO4)2 into a multi-component organic solution containing terpyridine-based ligand 3Tpy and monodentate imidazole-based ligand M2, the system underwent an unexpected kinetic evolution. Metallo-supramolecular polymers (MSP) formed first by the coordination of 3Tpy and Mg2+, but they subsequently decomposed due to the interference of M2, resulting in a transient MSP system. Further investigation revealed that this occurred because residual water in the solvent and M2 cooperatively coordinated with Mg2+. This allowed M2 to capture Mg2+ from MSP, which led to depolymerization. However, owing to the slow reaction between trace water/M2/Mg2+, the formation of MSP still occurred first. Therefore, water regulated both the thermodynamics and kinetics of the system and was the key factor for constructing the transient MSP. Fine-tuning the water content and other assembly motifs regulated the assembly evolution pathway, tuned the MSP lifetime, and made the luminescent color of the system undergo intriguing transition processes over time.

Grid-Type Quaternary Metallosupramolecular Compounds Inhibit Human Cholinesterases through Dynamic Multivalent Interactions.

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.

Controlling the Emissive, Chiroptical, and Electrochemical Properties of Double [7] Helicenes through Embedded Aromatic Rings.

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) from <1 % 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.

[Research progress on mechanism of Carthamus tinctorius in ischemic stroke therapy].

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-3ß(GSK3ß) 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.

B,N-Embedded Double Hetero[7]helicenes with Strong Chiroptical Responses in the Visible Light Region.

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.

Differential phase shift quantum secret sharing using a twin field.

Quantum secret sharing (QSS) is essential for multiparty quantum communication, which is one of cornerstones in the future quantum internet. However, a linear rate-distance limitation severely constrains the secure key rate and transmission distance of QSS. Here, we present a practical QSS protocol among three participants based on the differential phase shift scheme and twin field ideas for the solution of high-efficiency multiparty communication task. In contrast to a formerly proposed differential phase shift QSS protocol, our protocol can break the linear rate-distance bound, theoretically improving the secret key rate by three orders of magnitude in a 300-km-long fiber. Furthermore, the new protocol is secure against Trojan horse attacks that cannot be resisted by previous differential phase shift QSS.

Efficient quantum digital signatures without symmetrization step.

Quantum digital signatures (QDS) exploit quantum laws to guarantee non-repudiation, unforgeability and transferability of messages with information-theoretic security. Current QDS protocols face two major restrictions, including the requirement of the symmetrization step with additional secure classical channels and the quadratic scaling of the signature rate with the probability of detection events. Here, we present an efficient QDS protocol to overcome these issues by utilizing the classical post-processing operation called post-matching method. Our protocol does not need the symmetrization step, and the signature rate scales linearly with the probability of detection events. Simulation results show that the signature rate is three orders of magnitude higher than the original protocol in a 100-km-long fiber. This protocol is compatible with existing quantum communication infrastructure, therefore we anticipate that it will play a significant role in providing digital signatures with unconditional security.

Overcoming the rate-distance limit of device-independent quantum key distribution.

Device-independent quantum key distribution (DIQKD) exploits the violation of a Bell inequality to extract secure keys even if users' devices are untrusted. Currently, all DIQKD protocols suffer from the secret key capacity bound, i.e., the secret key rate scales linearly with the transmittance of two users. Here we propose a heralded DIQKD scheme based on entangled coherent states to improve entangling rates whereby long-distance entanglement is created by single-photon-type interference. The secret key rate of our scheme can significantly outperform the traditional two-photon-type Bell-state measurement scheme and, importantly, surpass the above capacity bound. Our protocol therefore is an important step towards a realization of DIQKD and can be a promising candidate scheme for entanglement swapping in the future quantum internet.

Overcoming the rate-distance limit of device-independent quantum key distribution: erratum.

In this Erratum the funding and references sections of Opt. Lett.46, 1632 (2021)OPLEDP0146-959210.1364/OL.417851 have been updated.

Cyclopentadienone Derivative Dimers as Tunable Photoswitches.

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. 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.

Characteristics of Acquired Inhibitors to Factor VIII and Von Willebrand Factor Secondary to Systemic Lupus Erythematosus: Experiences From a Chinese Tertiary Medical Center.

OBJECTIVE: Because acquired hemophilia (AH) is a rare entity in systemic lupus erythematosus (SLE), we aimed to investigate the clinical features of SLE-related AH in Chinese patients. METHODS: This is a medical records review study carried out at a large tertiary care hospital in China from years 1986 to 2018. We searched the case database in Peking Union Medical College Hospital using the International Classification of Diseases. The clinical data on SLE-related AH patients were collected. RESULTS: A total of 9282 SLE patients had been hospitalized. Six female SLE-related AH patients were identified. Four patients had acquired hemophilia A (AHA), and 2 patients had acquired von Willebrand syndrome. Their mean age was 33.67 ± 13.77 years. Five patients had active disease. The mean SLE disease activity index measured at the time of diagnosis of AH was 10.50 ± 5.28. The average level of activated partial thromboplastin time was 86.5 seconds. Coexistence of secondary antiphospholipid syndrome and AHA was found in one case, and pulmonary embolism was observed 3 years later. After immunosuppressive therapy and symptomatic treatment, an overall remission rate of 83.3% was achieved. CONCLUSIONS: The frequency of SLE-related AH was low. The development of AH in SLE patients frequently occurs with active disease. The AH could be the first clinical presentation of SLE. Secondary antiphospholipid syndrome and AHA could appear in the same SLE patient. Early and aggressive treatment contributes to a favorable prognosis.

[Clinical Features of Relapsing Polychondritis Patients Presented with Arthropathy].

Objective To explore the clinical characteristics of relapsing polychondritis(RP)patients presented with arthropathy. Methods We retrospectively analyzed the clinical data of 201 RP patients who were hospitalized in our center between December 2005 and February 2019.After 16 patients with co-existing other autoimmune diseases and malignancies were ruled out,185 RP patients entered the final analysis,among whom 16 RP patients were presented with arthropathy and 169 without arthropathy.The demographic data,clinical manifestations,laboratory findings,and prognosis were compared between these two groups. Results Five of the 16 RP patients with arthropathy at presentation were misdiagnosed as rheumatoid arthritis.Compared with RP patients without arthropathy at presentation,RP patients with arthropathy at presentation had a longer disease course[(37.50±66.50)months vs.(9.00±11.00)months,z=-3.186,P =0.001],longer time of diagnostic delay[(24.00±41.25)months vs.(7.00±9.00)months,z=-2.890,P=0.004],and higher incidence of eye(62.50% vs. 36.09%,χ2=4.309,P=0.038)and nervous system involvements(43.75% vs. 15.38%,χ2=6.205,P=0.013). Conclusions RP patients with arthropathy at presentation are most likely to be misdiagnosed as rheumatoid arthritis.These patients are characterized by longer disease course and diagnostic delay and more frequrent eye and nervous system involvements.

π-Extended Pyrene-Fused Double [7]Carbohelicene as a Chiral Polycyclic Aromatic Hydrocarbon.

A π-extended double [7]carbohelicene 2 with fused pyrene units was synthesized, revealing considerable intra- and intermolecular π-π interactions as confirmed with X-ray crystallography. As compared to the previous double [7]carbohelicene 1, the π-extended homologue 2 demonstrated considerably red-shifted absorption with an onset at 645 nm (1: 550 nm) corresponding to a smaller optical gap of 1.90 eV (1: 2.25 eV). A broad near-infrared emission from 600 to 900 nm with a large Stokes shift of ∼100 nm (2.3 × 103 cm-1) was recorded for 2, implying formation of an intramolecular excimer upon excitation, which was corroborated with femtosecond transient absorption spectroscopy. Moreover, 2 revealed remarkable chiral stability with a fairly high isomerization barrier of 46 kcal mol-1, according to density functional theory calculations, which allowed optical resolution by chiral HPLC and suggests potential applications in chiroptical devices.

Triindolo-Truxene Derivatives: Design, Synthesis, and Fine-Tuning of Electronic Properties and Molecular Assembly through Molecular Engineering.

Triindolo-truxene, a C3 -symmetric molecule with a large π-conjugated plane, has six methylene carbon atoms and three aromatic carbon atoms that can be facilely functionalized. Herein, butyl, carbonyl, cyano, and/or malononitrile groups were introduced at six methylene carbon atoms (6-, 14-, 22- or 8-, 16-, 24-positions) and/or three aromatic carbon atoms (2-, 10-, and 18-positions) of triindolo-truxene to produce eight derivatives. Their photophysical properties, electrochemical properties, and molecular assembly can be effectively modulated by substituents and substitution patterns. Incorporation of electron-deficient groups led to redshifts in both the absorption and emission of these derivatives and also lowered their HOMO and LUMO levels. Different substitution patterns resulted in the different intramolecular donor-acceptor interactions. Electron-deficient substituents at the methylene carbon atoms in the 6-, 14-, and 22-positions led to intramolecular charge transfer from the fluorene arms to the truxene core, whereas the corresponding substitutions at the methylene carbon atoms in the 8-, 16-, and 24-positions resulted in intramolecular charge transfer from the truxene core to the fluorene arms. The molecular packing in single crystals and molecular aggregation in solution are also influenced by the substituents and substitution patterns. This work provides a straightforward strategy to alter the properties of triindolo-truxene.