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Abstract Coordination cages have been widely reported to bind a variety of guests, which are useful for chemical separation. Although the use of cages in the solid state benefits the recycling, the flexibility, dynamicity, and metal-ligand bond reversibility of solid-state cages are poor, preventing efficient guest encapsulation. Here we report a type of coordination cage-integrated solid materials that can be swelled into gel in water. The material is prepared through incorporation of an anionic FeII 4L6 cage as the counterion of a cationic poly(ionic liquid) (MOC@PIL). The immobilized cages within MOC@PILs have been found to greatly affect the swelling ability of MOC@PILs and thus the mechanical properties. Importantly, upon swelling, the uptake of water provides an ideal microenvironment within the gels for the immobilized cages to dynamically move and flex that leads to excellent solution-level guest binding performances. This concept has enabled the use of MOC@PILs as efficient adsorbents for the removal of pollutants from water and for the purification of toluene and cyclohexane. Importantly, MOC@PILs can be regenerated through a deswelling strategy along with the recycling of the extracted guests.

Abstract Developing synthetic molecular devices for controlling ion transmembrane transport is a promising research field in supramolecular chemistry. These artificial ion channels provide models to study ion channel diseases and have huge potential for therapeutic applications. Compared with self‐assembled ion channels constructed by intermolecular weak interactions between smaller molecules or cyclic compounds, metallacage‐based ion channels have well‐defined structures and can exist as single components in the phospholipid bilayer. A naphthalene diimide‐based artificial chloride ion channel is constructed through efficient subcomponent self‐assembly and its selective ion transport activity in large unilamellar vesicles and the planar lipid bilayer membrane by fluorescence and ion‐current measurements is investigated. Molecular dynamics simulations and density functional theory calculations show that the metallacage spans the entire phospholipid bilayer as an unimolecular ion transport channel. This channel transports chloride ions across the cell membrane, which disturbs the ion balance of cancer cells and inhibits the growth of cancer cells at low concentrations.

Abstract Background We conducted a systematic review and meta-analysis to evaluate the efficacy and safety of blonanserin and risperidone for the treatment of schizophrenia and to provide reliable pharmacotherapeutic evidence for in the clinical treatment of schizophrenia. Methods We systematically searched the PubMed, Cochrane Library, Embase, Chinese Biomedical Literature Database (CBM), and China National Knowledge Infrastructure (CNKI) databases for head-to-head randomized controlled trials that compared blonanserin with risperidone for the treatment of schizophrenia. We extracted the following data: author, year, country, diagnostic criteria, sample size, course of treatment, dosage and outcomes. Our main endpoint was the changes in the Positive and Negative Syndrome Scale (PANSS) total scores. Meta-analysis of the included data was conducted by RevMan 5.3 software. We used the GRADE criteria to evaluate the certainty of the evidence. Results A total of 411 studies were initially; 8 trials were eligible and were included in our analysis (N = 1386 participants). Regarding efficacy, there was no difference in changes in the PANSS total scores between the two groups (P > 0.05). In terms of safety, compared to risperidone, the incidence of serum prolactin increases and weight gain in the blonanserin group was lower (P

As the representative of flexibility in optical imaging media, in recent years, fiber bundles have emerged as a promising architecture in the development of compact visual systems. Dedicated to tackling the problems of universal honeycomb artifacts and low signal-to-noise ratio (SNR) imaging in fiber bundles, the iterative super-resolution reconstruction network based on a physical model is proposed. Under the constraint of solving the two subproblems of data fidelity and prior regularization term alternately, the network can efficiently “regenerate” the lost spatial resolution with deep learning. By building and calibrating a dual-path imaging system, the real-world dataset where paired low-resolution (LR) - high-resolution (HR) images on the same scene can be generated simultaneously. Numerical results on both the United States Air Force (USAF) resolution target and complex target objects demonstrate that the algorithm can restore high-contrast images without pixilated noise. On the basis of super-resolution reconstruction, compound eye image composition based on fiber bundle is also embedded in this paper for the actual imaging requirements. The proposed work is the first to apply a physical model-based deep learning network to fiber bundle imaging in the infrared band, effectively promoting the engineering application of thermal radiation detection.

Abstract Aiming 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.

The electronic structures and open-shell diradical character of organic diradicaloids endow them with potentially useful optical, electronic and magnetic properties. Here, an open-shell nitrogen-centered diradicaloid is reported and shown to readily react with Lewis and Brønsted acids to form acid-base adducts, allowing for tuning of ground-state electronic structure, diradical character and spin density distribution.

Abstract Microfluidics has received extensive attention due to its ability to rapidly prepare a large number of microdroplets with controlled sizes and defined morphologies. In addition to having large surface areas and controllable confinement environments, these prepared microdroplets can be used as analytical detection devices to screen and optimize various kinetic parameters. This review summarizes recent advances in the microfluidic control of droplet‐based catalytic reactions and discusses the role of these droplets in both homogeneous and heterogeneous catalyzes and in the catalysis of macromolecular biological enzymes in water‐in‐oil and oil‐in‐oil environments. Additionally, the existing problems and future development directions of droplets in catalysis are highlighted to promote the development of catalytic reactions in droplet media and provide guidance for the high‐throughput screening of catalysts and the directed evolution of biological enzymes.

Chemosensation of tarsi provides moths with the ability to detect chemical signals which are important for food recognition. However, molecular mechanisms underlying the chemosensory roles of tarsi are still unknown. The fall armyworm Spodoptera frugiperda is a serious moth pest that can damage many plants worldwide. In the current study, we conducted transcriptome sequencing with total RNA extracted from S. frugiperda tarsi. Through sequence assembly and gene annotation, 23 odorant receptors 10 gustatory receptors and 10 inotropic receptors (IRs) were identified. Further phylogenetic analysis with these genes and homologs from other insect species indicated specific genes, including ORco, carbon dioxide receptors, fructose receptor, IR co-receptors, and sugar receptors were expressed in the tarsi of S. frugiperda. Expression profiling with RT-qPCR in different tissues of adult S. frugiperda showed that most annotated SfruORs and SfruIRs were mainly expressed in the antennae, and most SfruGRs were mainly expressed in the proboscises. However, SfruOR30, SfruGR9, SfruIR60a, SfruIR64a, SfruIR75d, and SfruIR76b were also highly enriched in the tarsi of S. frugiperda. Especially SfruGR9, the putative fructose receptor, was predominantly expressed in the tarsi, and with its levels significantly higher in the female tarsi than in the male ones. Moreover, SfruIR60a was also found to be expressed with higher levels in the tarsi than in other tissues. This study not only improves our insight into the tarsal chemoreception systems of S. frugiperda but also provides useful information for further functional studies of chemosensory receptors in S. frugiperda tarsi.

Abstract A–π–D–π–A type conjugated small molecules play an indispensable role in organic photovoltaics. Understanding the relationship between the molecular structure and performance is a fundamental question for the further rational design of high-performance organic materials. To red-shift the absorption spectrum of benzo[1,2-b:4,5-b']dithiophene (BDT) based A–π–D–π–A type compounds, an electron-donating 3,4-ethylenedioxythiophene (EDOT) moiety was introduced into the π-conjugation bridge unit. Two new compounds with EDOT next to the central BDT core (COOP-2HT-EDOT-BDT) or next to the terminal electron acceptor unit (COOP-EDOT-2HT-BDT) were synthesized and characterized. The compound COOP-2HT-EDOT-BDT showed higher molar extinction coefficient (εabs max = 1.06 × 105 L mol−1 cm−1), lower optical band gap (E g = 1.56 eV) and high HOMO energy level (E HOMO = −5.08 eV) than COOP-EDOT-2HT-BDT (εabs max = 0.96 × 105 L mol−1 cm−1, E g = 1.71 eV, E HOMO = −5.26 eV), which is attributed to the intensive interaction between the EDOT unit and the HOMO orbital, as confirmed by the theoretical calculation results. However, the higher power conversion efficiency of 3.58% was achieved for the COOP-EDOT-2HT-BDT:PC61BM-based solar cells, demonstrating that the electron-donating EDOT unit adjacent to the electron-withdrawing end-capped group (COOP) is a better way to achieve high-performance photovoltaic materials.

With the development of hypersonic technology, the demand for thermal protection material is continuously increasing. Carbon/carbon composites are widely used as thermal protection materials in the nose and in the leading edge of hypersonic vehicles owing to their high latent heat and good resistance to high temperatures. The flow field around the aircraft affects the heat transfer and ablation of carbon/carbon composites, changing the thickness and shape of the thermal protection layer. The ablation of carbon/carbon composites alters the flow field distribution, thus conversely affecting the ablation of carbon/carbon composites. To predict the heat transfer and ablation of carbon/carbon composites, a multi-field coupling model was established to predict the transient temperature distribution, ablation rate, and ablation profile of carbon/carbon composites in hypersonic aerothermal environments. The thermochemical non-equilibrium effects of the flow field, heat transfer of the material, and ablation of the material surface were considered in the modeling. The wall temperature and heat flux in the stagnation area change significantly. The initial heat flux is higher and the stagnation heat flux at 1 s is 17.22 MW·m−2. As time passes, the wall temperature increases, the temperature gradient in the stagnation area decreases, the heat flux decreases, and the stagnation heat flux at 30 s is 10.22 MW·m−2. As the temperature of the stagnation area is high, the material at the surface reacts actively and the ablation is more serious, whereas only a small amount of ablation occurs on the side of the model. The shape of the material model changes after the ablation, the leading-edge radius increases, and the ablation depth at the material stagnation point is 17.47 mm at 30 s. The results show that, in the hypersonic aerodynamic thermal environment, the carbon/carbon composites have a certain ablation recession, which leads to change in the external flow field and thermal load. The multi-field flow-heat-ablation coupling model can be used to predict the response of thermal protection materials, which can provide some reference for the design of thermal protection systems.

Precise assembly of heterometallic complexes is a challenge. Here, the authors design a heterometallic triangular necklace through a highly efficient threading-and-ring-closing approach driven by metal-ligand coordination, which shows strong bacterium-binding and cell wall/plasma membrane-disrupting capacity for killing bacterial cells.

Fluorescent supramolecular coordination complexes are of interest for chemical sensing and optical devices. Here the authors synthesize nine organoplatinum metallacycles with high quantum yields, whose fluorescence wavelengths are tuned through manipulation of their photoinduced electron transfer and intramolecular charge transfer properties.

Chemoreception by moth ovipositors has long been suggested, but underlying molecular mechanisms are mostly unknown. To reveal such chemosensory systems in the current study, we sequenced and assembled the pheromone gland-ovipositor (PG-OV) transcriptome of females of the fall armyworm, Spodoptera frugiperda, a pest of many crops. We annotated a total of 26 candidate chemosensory receptor genes, including 12 odorant receptors (ORs), 4 gustatory receptors (GRs), and 10 ionotropic receptors (IRs). The relatedness of these chemosensory receptors with those from other insect species was predicted by phylogenetic analyses, and specific genes, including pheromone receptors, ORco, CO2 receptors, sugar receptors, and IR co-receptors, were reported. Although real-time quantitative-PCR analyses of annotated genes revealed that OR and IR genes were mainly expressed in S. frugiperda antennae, two ORs and two IRs expressed in antennae were also highly expressed in the PG-OV. Similarly, GR genes were mainly expressed in the proboscis, but two were also highly expressed in the PG-OV. Our study provides the first large-scale description of chemosensory receptors in the PG-OV of S. frugiperda and provides a foundation for exploring the chemoreception mechanisms of PG-OV in S. frugiperda and in other moth species.

Aims: C1q/tumor necrosis factor (TNF)-related protein 5 (CTRP5) belongs to the C1q/TNF-α related protein family and regulates glucose, lipid metabolism, and inflammation production. However, the roles of CTRP5 in ischemia/reperfusion (I/R) associated with cardiac injuries and heart failure (HF) needs to be elaborated. This study aimed to investigate the roles of CTRP5 in I/R associated cardiac injuries and heart failure.Materials and Methods: Adeno-associated virus serum type 9 （AAV9）vectors were established for CTRP5 overexpression in a mouse heart (AAV9-CTRP5 mouse). AAV9-CTRP5, AMPKα2 global knock out （AMPKα2−/−）and AAV9-CTRP5+ AMPKα2−/− mice were used to establish cardiac I/R or infarction associated HF models to investigate the roles and mechanisms of CTRP5 in vivo. Isolated neonatal rat cardiomyocytes (NRCMS) transfected with or without CTRP5 adenovirus were used to establish a hypoxia/reoxygenation (H/O) model to study the roles and mechanisms of CTRP5 in vitro.Key Findings: CTRP5 was up-regulated after MI but was quickly down-regulated. CTRP5 overexpression significantly decreased I/R induced IA/AAR and cardiomyocyte apoptosis, and attenuated infarction area, and improved cardiac functions. Mechanistically, CTRP5 overexpression markedly increased AMPKα2 and ACC phosphorylation and PGC1-α expression but inhibited mTORC1 phosphorylation. In in vitro experiments, CTRP5 overexpression could also enhance AMPKα2 and ACC phosphorylation and protect against H/O induced cardiomyocytes apoptosis. Finally, we showed that CTPR5 overexpression could not protect against I/R associated cardiac injuries and HF in AMPKα2−/− mice.Significance: CTRP5 overexpression protected against I/R induced mouse cardiac injuries and attenuated myocardial infarction induced cardiac dysfunction by activating the AMPKαsignaling pathway.

Although the preparation of artificial light-harvesting systems (ALHs) has attracted increasing attention, dynamic regulation of antenna effect in ALHs has been still a major challenge. Herein, we constructed a family of new rotaxane dendrimers containing up to fifty-six anthracene moieties (energy donor) on the wheels of the rotaxane units and one zinc(II) porphyrin moiety (energy acceptor) at the central core. Notably, the resultant rotaxane dendrimers incorporate a large number of rotaxane subunits on the dendritic skeleton in a monodisperse manner, which thus allowed for the high energy transfer efficiencies and antenna effects. More importantly, with the addition and removal of acetate anions, the directional and reversible motion of rotaxane unit on each axis was realized, thus leading to dynamic regulation of antenna effect in resultant rotaxane dendrimers.

Melatonin has been shown to inhibit myocardial infarction-induced apoptosis, its function in heart failure with preserved ejection fraction (HFpEF) has not been investigated. This study aimed to investigate whether melatonin attenuates obesity-related HFpEF. Male mice were fed a high-fat diet (HFD) from weaning to 6 months of age to induce HFpEF. The mice were orally administered melatonin (50 mg/kg) by 3 weeks. Diastolic function was significantly improved by melatonin supplementation in mice fed an HFD. Melatonin attenuated obesity-induced myocardial oxidative stress and apoptosis and promoted the secretion of C1q/tumour necrosis factor-related protein 3 (CTRP3) by adipose tissue. And depletion of circulating CTRP3 largely abolished melatonin-mediated cardio-protection. Melatonin-mediated secretion of adipocyte-derived CTRP3 activated NF-E2-related factor 2 (Nrf2), which were largely abrogated by knocking down CTRP3 in adipocytes or Nrf2 in cardiomyocytes. Nrf2 activation was mediated by miR-200a, and a miR-200a antagomir offset the effects of melatonin-conditioned medium on Nrf2 expression. Our results indicate that melatonin can be used to treat and prevent obesity-related HFpEF. Keywords: Melatonin, HFpEF, CTRP3, Adipocyte, Oxidative stress, Apoptosis

Mechanically interlocked molecules are extensively applied as artificial molecular machines but rotaxane-branched dendrimers are rarely explored because of synthetic challenges. Here the authors present the construction of dual stimuli-responsive rotaxane-branched dendrimer which can be stimulated by DMSO or acetate ions.

Metal coordination of multitopic ligands is a powerful approach to building complex, functional architectures. Here, the authors construct three generations of fluorescent supramolecular rosettes by coordination of aggregation-induced emissive ligands, including a 2nd-generation macrocycle that emits pure white light.

Implementation of the water-sediment regulation (WSR) scheme, mainly focused on solving the sedimentation problems of reservoirs and the lower reaches of the Yellow River, has inevitably influenced the sediment distribution and coastal morphology of the Yellow River Estuary. Using coastline delineation and suspended sediment concentration (SSC) retrieval methods, this study investigated water and sediment changes, identified detailed inter-annual and intra-annual variations of the coastline and SSC in the normal period (NP: 1986–2001, before and after the flood season) and WSR period (WSRP: 2002–2013, before and after WSR). The results indicate that (1) the sedimentation in the low reaches of the Yellow River turned into erosion from 2002 onward; (2) the inter-annual coastline changes could be divided into an accretion stage (1986–1996), a slow erosion stage (1996–2002), and a slow accretion stage (2002–2013); (3) an intra-annual coastline extension occurred in the river mouth in most years of the WSRP; and (4) the mean intra-annual accretion area was 0.789 km2 in the NP and 4.73 km2 in the WSRP, and the mean SSC increased from 238 mg/L to 293 mg/L in the NP and from 192 mg/L to 264 mg/L in the WSRP.

The 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 M1 and M2 decorated with different host–guest recognition sites have been constructed via coordination-driven self-assembly strategy. The binding of metallacycles M1 and M2 with dibenzo-24-crown-8 (DB24C8) to form tris[2]pseudorotaxanes complexes TPRM1 and TPRM2 have been investigated. Furthermore, by taking advantage of the strong binding affinity between the protonated metallacycle M2 and DB24C8, the addition of trifluoroacetic acid (TFA) as a stimulus successfully induces an acid-activated motion switching of DB24C8 between the discrete metallacycles M1 and M2. This research not only affords a highly efficient way to construct stimuli-responsive smart supramolecular systems but also offers prospects for precisely control multicomponent cooperative motion.

Benzo[1,2-b:4,5-b′]dithiophene (BDT) is an excellent building block for constructing π-conjugated molecules for the use in organic solar cells. In this paper, four 4,8-bis(5-alkyl-2-thienyl)benzo[1,2-b:4,5-b′]dithiophene (TBDT)-containing A–π–D–π–A-type small molecules (COOP-nHT-TBDT, n = 1, 2, 3, 4), having 2-cyano-3-octyloxy-3-oxo-1-propenyl (COOP) as terminal group and regioregular oligo(3-hexylthiophene) (nHT) as the π-conjugated bridge unit were synthesized. The optical and electrochemical properties of these compounds were systematically investigated. All these four compounds displayed broad absorption bands over 350–600 nm. The optical band gap becomes narrower (from 1.94 to 1.82 eV) and the HOMO energy levels increased (from −5.68 to −5.34 eV) with the increase of the length of the π-conjugated bridge. Organic solar cells using the synthesized compounds as the electron donor and PC61BM as the electron acceptor were fabricated and tested. Results showed that compounds with longer oligothiophene π-bridges have better power conversion efficiency and higher device stability. The device based on the quaterthiophene-bridged compound 4 gave a highest power conversion efficiency of 5.62% with a VOC of 0.93 V, JSC of 9.60 mA·cm−2, and a FF of 0.63.

We provide a fast approach incorporating the usage of deep learning for studying the effects of the number of photon sensors in an antineutrino detector on the event reconstruction performance therein. This work is a first attempt to harness the power of deep learning for detector designing and upgrade planning. Using the Daya Bay detector as a case study and the vertex reconstruction performance as the objective for the deep neural network, we find that the photomultiplier tubes (PMTs) at Daya Bay have different relative importance to the vertex reconstruction. More importantly, the vertex position resolutions for the Daya Bay detector follow approximately a multiexponential relationship with respect to the number of PMTs and, hence, the coverage. This could also assist in deciding on the merits of installing additional PMTs for future detector plans. The approach could easily be used with other objectives in place of vertex reconstruction.