Search

Ethnopharmacological Relevance: Artemisia stechmanniana Besser, one of the most prevalent botanical medicines in Chinese, has been traditionally used for hepatitis treatment. However, the bioactive components and pharmacological mechanism on alcohol-induced liver injury remains unclear., Aim of the Study: To investigate the effect of A. stechmanniana on alcohol-induced liver damage, and further explore its mechanism., Materials and Methods: Phytochemical isolation and structural identification were used to determine the chemical constituents of A. stechmanniana. Then, the alcohol-induced liver damage animal and cell model were established to evaluate its hepato-protective potential. Network pharmacology, molecular docking and bioinformatics were integrated to explore the mechanism and then the prediction was further supported by experiments. Moreover, both compounds were subjected to ADMET prediction through relevant databases., Results: 28 compounds were isolated from the most bioactive fraction, ethyl acetate extract A. stechmanniana, in which five compounds (abietic acid, oplopanone, oplodiol, hydroxydavanone, linoleic acid) could attenuate mice livers damage caused by alcohol intragastration, reduce the degree of oxidative stress, and serum AST and ALT, respectively. Furthermore, abietic acid and hydroxydavanone exhibited best protective effect against alcohol-stimulated L-O2 cells injury among five bioactive compounds. Network pharmacology and bioinformatics analysis suggested that abietic acid and hydroxydavanone exhibiting drug likeliness characteristics, were the principal active compounds acting on liver injury treatment, primarily impacting to cell proliferation, oxidative stress and inflammation-related PI3K-AKT signaling pathways. Both of them displayed strong binding energies with five target proteins (HRAS, HSP90AA1, AKT1, CDK2, NF-κB p65) via molecular docking. Western blotting results further supported the predication with up-regulation of protein expressions of CDK2, and down-regulation of HRAS, HSP90AA1, AKT1, NF-κB p65 by abietic acid and hydroxydavanone., Conclusion: Alcohol-induced liver injury protection by A. stechmanniana was verified in vivo and in vitro expanded its traditional use, and its two major bioactive compounds, abietic acid and hydroxydavanone exerted hepatoprotective effect through the regulation of PI3K-AKT signaling pathway., Competing Interests: Declaration of competing interest The authors declare that they have no conflict of interest., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Ethnopharmacological Relevance: Corydalis decumbens (Thunb.) Pers. was used as stasis-eliminating medicine traditionally to treat cardiovascular disease potentially attributed to its antithrombotic effect, but lack of pharmacological research on it., Aim of the Study: To investigate the antithrombotic effect of C. decumbens and its preliminary mechanism., Materials and Methods: A carrageenan-induced mouse thrombus model and adenosine diphosphate stimulated platelet aggregation of rabbits were used to confirm the inhibitory effect of C. decumbens extract and compounds on thrombosis in vivo. Then, H 2 O 2 -induced human umbilical vein endothelial cells (HUVECs) injury model was further adopted to verify the effects of bioactive compounds in vitro. Moreover, in silico network pharmacology analyses and molecular docking were performed to predict the underlying mechanisms, targets, and pathways, and which were further confirmed through western blotting assay., Results: The administration of total extract (TE), total alkaloids (TA) and tetrahydropalmatine (TET) resulted in a significant reduction in black tail thrombus and congestion, along with a decreasing in platelet aggregation of rabbits. A superior antithrombotic effect indicated the bioactive fraction, and then the isolated bioactive compounds, TET and protopine (PRO) increased cell survival, and decreased reactive oxygen species (ROS) and lactate dehydrogenase (LDH) release in H 2 O 2 -induced HUVECs injury model. Moreover, the two alkaloids targeted 33 major proteins and influenced 153 pathways in network pharmacology prediction. Among these, HSP90AA1, COX-2, NF-κB/p65, MMP1 and HIF-1α were the key proteins and PI3K-Akt emerged as the major signaling pathway. Further western blotting results supported that five key proteins were downregulated by the two bioactive compounds in H 2 O 2 -stimulated HUVECs model., Conclusion: C. decumbens exerted protective effect on thrombosis through inhibiting PI3K-Akt pathway and related key proteins, which supported the traditional use and presented potential antithrombotic alkaloids for further investigation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Spin-crossover (SCO) coordination cages are at the forefront of research for their potential in crafting next-generation molecular devices. However, due to the scarcity of SCO hosts and their own limited cavities, the interplay between the SCO host and the multiple guests binding has remained elusive. In this contribution, we present a family of pseudo-octahedral coordination cages (M 6 L 4 , M = Zn II , Co II , Fe II , and Ni II ) assembled from a tritopic tridentate ligand L with metal ions. The utilization of Fe II ion leads to the successful creation of the Fe 6 L 4 -type SCO cage. Host-guest studies of these M 6 L 4 cages reveal their capacity to encapsulate four adamantine-based guests. Notably, the spin transition temperature T 1/2 of Fe 6 L 4 is dependent on the multiple guests encapsulated. The inclusion of adamantine yields an unprecedented T 1/2 shift of 54 K, a record shift in guest-mediated SCO coordination cages to date. This drastic shift is ascribed to the synergistic effect of multiple guests coupled with their optimal fit within the host. Through a straightforward thermodynamic cycle, the binding affinities of the high-spin (HS) and low-spin (LS) states are separated from their apparent binding constant. This result indicates that the LS state has a stronger binding affinity for the multiple guests than the HS state. Exploring the SCO thermodynamics of host-guest complexes allows us to examine the optimal fit of multiple guests to the host cavity. This study reveals that the T 1/2 of the SCO host can be manipulated by the encapsulation of multiple guests, and the SCO cage is an ideal candidate for determining the multiple guest fit.

Ln 2 L 3 -type supramolecular architectures have received significant attention recently due to their unique magnetism and optical properties. Herein, we report the triple-stranded Ln 2 L 3 -type lanthanide molecular quasi-lanterns, which are fabricated by the deprotonation self-assembly of a linear ligand featuring a β-diketone chelating claw and 2,2'-bipyridine (bpy) moiety with lanthanide ions (Ln = Eu 3+ and Dy 3+ ). The crystal structure analysis indicates that Eu 3+ and Dy 3+ ions are all coordinated by eight oxygen donors but in different coordination geometries. The eight oxygen donors in Eu 2 L 3 and Dy 2 L 3 are arranged in a square antiprism and triangular dodecahedron geometry, respectively. Taking into account the fact that the bpy moiety has a strong coordination affinity for transition metal ions, luminescence sensing toward Cu 2+ ions has been demonstrated with Eu 2 L 3 , bearing a detection of limit as low as 2.84 ppb. The luminescence sensing behavior of Eu 2 L 3 is ascribed to the formation host-guest complex between Eu 2 L 3 and Cu 2+ ions with a 1:2 binding ratio. Dynamic AC susceptibility measurements for Dy 2 L 3 reveal the relaxation of magnetization in it. This work provides a potential way for design and fabrication of lanthanide-based molecular materials with functions endowed by the ligands., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Well-defined 3d-4f heterometallic supramolecular architectures have attracted attention because of their applications in the field of luminescence and magnetism. However, covalent metallo-supramolecular discrete complexes, decorated with hetero-metallic vertices, have never been reported because of the difficulties in design and control. Herein, we report a series of covalent metallo-supramolecular discrete complexes with 3d-4f vertices synthesized by hierarchical subcomponent self-assembly of tris(2-aminoethyl)amine, 2,6-diformyl- p -cresol, and lanthanide ions (Ln) with different amines and transition metal ions. The programmable self-assembly process results in the formation of triple-stranded hetero-metallic covalent organic discrete complexes, namely 3a-3c-(Ln, Zn) (Ln = Sm III , Eu III , Dy III , Yb III and Lu III ) and 3a'-(Dy, Co), which are characterized by nuclear magnetic resonance (NMR) analysis, electrospray ionization time-of-flight mass spectrometry (ESI-TOF-MS), and single-crystal X-ray analysis. Photophysical investigations disclose that the organic skeleton of 3a-(Ln, Zn) exhibits an excellent sensitizing ability toward Sm III , Eu III , and Yb III ions, displaying characteristic luminescence emission in both the visible and near-infrared (NIR) regions. AC susceptibility measurements of 3a'-(Dy, Co) reveal the frequency-independent performance under zero dc field, suggesting the absence of slow relaxation of magnetization. This work offers a new approach for the fabrication of discrete metallic covalent architectures with 3d-4f vertices.

Discrete organopalladium coordination cages have shown great potential in applications ranging from molecular recognition and sensing, drug delivery to enzymatic catalysis. While many of the known organopalladium cages are homoleptic structures with regular polyhedral shapes and symmetric inner cavities, heteroleptic cages with complex architectures and new functions coming from their anisotropic cavities have received an increasing attention recently. In this concept article, we discuss a powerful combinatorial coordination self-assembly strategy toward the construction of a family of organopalladium cages, including both homoleptic and heteroleptic ones, from a given library of ligands. Within such a cage family, the heteroleptic cages often feature systematically fine-tuned structures and emergent properties, distinct from their parent homoleptic counterparts. We hope the concepts and examples provided in this article can offer some rational guidance for the design of new coordination cages toward advanced functions., (© 2023 Wiley-VCH GmbH.)

A stable 3 d -4 f heterometallic cluster, namely, {Dy 4 Ni 5 L 10 (NO 3 ) 4 (CO 3 ) 4 (CH 3 OH) 2 }·CH 3 CN (Dy 4 Ni 5 , HL = 8-hydroxyquinoline), has been solvothermally synthesized and structurally characterized. The compound exhibits an interesting structure in which a tetrahedron based on 4 f ions interpenetrates with a square pyramid based on 3 d ions. Besides, a unique intermolecular interaction was found in Dy 4 Ni 5 , giving rise to its high stability not only when it is in the solid state but also when it dissolves in organic solvents. In addition, the magnetic behavior of solid Dy 4 Ni 5 and the magneto-optical activity of the Dy 4 Ni 5 solution were also studied.

Lanthanide supramolecular chemistry is a fast growing and intriguing research field due to the unique photophysical, magnetic, and coordination properties of lanthanide ions (Ln III ). Compared with the intensively investigated mononuclear Ln-complexes, polymetallic lanthanide supramolecular assemblies offer more structural superiority and functional advantages. In recent decades, significant progress has been made in polynuclear lanthanide supramolecules, varying from structural evolution to luminescent and magnetic functional materials. This review summarizes the design principles in ligand-induced coordination-driven self-assembly of polynuclear Ln-structures and intends to offer guidance for the construction of more elegant Ln-based architectures and optimization of their functional performances. Design principles concerning the water solubility and chirality of the lanthanide-organic assemblies that are vital in extending their applications are emphasized. The strategies for improving the luminescent properties and the applications in up-conversion, host-guest chemistry, luminescent sensing, and catalysis have been summarized. Magnetic materials based on supramolecular assembled lanthanide architectures are given in an individual section and are classified based on their structural features. Challenges remaining and perspective directions in this field are also briefly discussed.

Spin-crossover (SCO) active compounds have received much attention due to their potential application in molecular devices. Herein, a family of solvent-free Fe II compounds, formulated as (A) 2 [FeL 2 ], (H 2 L = pyridine-2,6-bi-tetrazolate, A = (Me) 4 N + 1, Et 2 NH 2 + 2, i Pr 2 NH 2 + 3 and i PrNH 3 + 4), were synthesized and characterized. Single-crystal X-ray diffraction studies reveal that 1-4 are all supramolecular frameworks containing the same [FeL 2 ] 2- center, which is arranged into two packing modes via inter-molecular interactions, that is, a 3D architecture in 1 and 1D chain in 2-4. The spin states of 1-4 at different temperatures are assigned on the basis of the single-crystal X-ray diffraction data. Solid state magnetic investigations indicate that 1 and 4 exhibit a low spin state (below 350 K) and high spin state (2-400 K), respectively. 2 and 3 display clear SCO behavior in the measured temperature, but with different profiles and critical temperatures. 2 undergoes a complete gradual SCO with a critical temperature of T 1/2 = 260 K. 3 has an abrupt near room temperature transition between T 1/2 cooling = 278 K and T 1/2 warming = 286, centered at 282 K (9 °C). This study reveals the importance of organic cations in the modulation of SCO behavior and offers a new insight for the design of SCO compounds with near room temperature spin transitions.

A series of 3d-4f heterometallic cluster incorporated polyoxoniobates (PONbs) with different magnetic properties were first made and characterized. This work not only provides a promising strategy to make new heterometallic cluster incorporated PONbs but also demonstrates an ideal model to probe how transition-metal ions influence the magnetic property of PONbs.

Molecular cages have attracted great attention because of their fascinating topological structures and well-defined functional cavities. These discrete cages were usually fabricated by coordination assembly approach, a process employing directional metal-ligand coordination bonds due to the nature of the divinable coordination geometry and the required lability to encode dynamic equilibrium/error-correction. Compared to these coordination molecular cages with mononulcear metal-nodes, an increasing number of molecular cages featuring dinuclear and then polynuclear metal-cluster nodes have been synthesized. These metal-cluster-based coordination cages (MCCCs) combine the merits of both metal clusters and the cage structure, and exhibit excellent performances in catalysis, separation, host-guest chemistry and so on. In this review, we highlight the syntheses of MCCCs and their potential functions that is donated by the metal-cluster nodes., (© 2020 The Chemical Society of Japan & Wiley-VCH GmbH.)

Stimuli-responsive structural transformations between discrete coordination supramolecular architectures not only are essential to construct smart functional materials but also provide a versatile molecular-level platform to mimic the biological transformation process. We report here the controlled self-assembly of three topologically unprecedented conjoined twin-cages, i.e., one stapled interlocked Pd 12 L 6 cage ( 2 ) and two helically isomeric Pd 6 L 3 cages ( 3 and 4 ) made from the same cis-blocked palladium corners and a new bis-bidentate ligand ( 1 ). While cage 2 features three mechanically coupled cavities, cages 3 and 4 are topologically isomeric helicate-based twin-cages based on the same metal/ligand stoichiometry. Sole formation of cage 2 or a dynamic mixture of cages 3 and 4 can be controlled by changing the solvents employed during the self-assembly. Structural conversions between cages 3 and 4 can be triggered by changes in both temperature/solvent and induced-fit guest encapsulations. Well-controlled interconversion between such topologically complex superstructures may lay a solid foundation for achieving a variety of functions within a switchable system.

In our previous study, we reported a high temperature adapted strain (HTAS) of the predatory mite Neoseiulus barkeri was artificially selected via a long-term heat acclimation (35°C) and frequent heat hardenings. To understand the molecular basis of heat acclimation, 'omics' analyses were performed to compare the differences between HTAS female adults to conventional strain (CS) at transcriptional and translational levels. We obtained a total of 5,374 differentially expressed genes and 500 differentially expressed proteins. Among them, 119 transcripts had concurrent transcription and translation profiles. It's conserved that some processes, such as high expression of heat shock protein (HSP) genes, involved in heat tolerance of transcriptome analyses, while many protective enzymes including glutathione S-transferase, superoxide dismutase, peroxidase, and cytochrome P450 displayed down-regulated expression. KEGG analysis mapped 4,979 and 348 differentially expressed genes and proteins, to 299 and 253 pathways, respectively. The mitogen-activated protein kinases (MAPK) signaling pathway may provide new insights for the investigation of the molecular mechanisms of heat tolerance. Correlation enriched pathways indicated that there were four pathways associated with heat acclimation involving in energy metabolism and immunity. In addition, the expression patterns of ten randomly selected genes including HSP were consistent with the transcriptome results obtained through quantitative real-time PCR. Comparisons between transcriptome and proteome results indicated the upregulation of HSPs and genes participated in ATP production, immunity and energy metabolism process. A majority of antioxidant-related genes and detoxication-related genes were down-regulated suggesting a fitness cost of heat acclimation. Our results demonstrated that heat tolerance during a long-time acclimation of N. barkeri is a fairly complicated process of physiological regulations. These findings also contribute to a better understanding of the mechanisms of thermal responses of phytoseiid mites which could provide useful information for biological control through natural enemies., (Copyright © 2020 Tian, Li, Huang, Chu, Wang and Liu.)

By introduction of trilacunary Keggin-type polyoxometalate to the hydrothermal reaction system of Cr 3+ , Ln 3+ and phthalic acid, a series of novel {Cr 4 Ln 4 } heterometallic clusters with the formula Cs 2 [Cr 4 Ln 4 (μ 4 -O) 4 (μ 3 -O) 4 (C 8 H 4 O 4 ) 4 (H 2 O) 12 ](H 3 SiW 12 O 40 )Cl·23H 2 O (1-Ln, Ln = Ce, Pr, Nd) and [Cr 4 Ln 4 (μ 4 -O) 4 (μ 3 -O) 4 (C 8 H 4 O 4 ) 4 (H 2 O) 10 ](H 6 SiW 12 O 40 )Cl 2 ·18H 2 O (2-Ln, Ln = Sm, Eu, Gd, Tb, Dy, Ho, Er) have been obtained. Single-crystal structural analyses show that 1-Ln and 2-Ln constitute the first cases of Cr-Ln heterometallic clusters stabilized by inorganic polyoxometalate anions and organic ligands. Optical spectra studies demonstrate that 1-Ln and 2-Ln are narrow-gap semiconductors with band gaps of about 1.5 eV. Magnetic investigation shows that compound 2-Dy is a potential single molecule magnet., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

Biological control of spider mites in hot and dry weather is a serious technical issue. A high-temperature adapted strain (HTAS) of the predatory mite Neoseiulus barkeri Hughes was selected from its conventional strain (CS), via long-term heat acclimation and frequent heat hardenings in our previous studies. However, the environment of high temperature is usually associated with enhanced ultraviolet (UV) radiation. In the present study, the physiological effects of UV-B radiation on survival rate and egg damage of N. barkeri were investigated, as well as the activities and expression profiles of antioxidant enzymes to UV-B radiation stress. UV-B radiation had deleterious effects on egg hatchability and survival of N. barkeri. Adults of the HTAS strain were less UV-B resistant than those of the CS strain; they also had lower levels of enzymatic activity of superoxide dismutase (SOD) and catalase against oxidative damage and weaker upregulation of SOD genes. The mRNA expression of three SOD genes of CS adult females immediately increased whereas that of HTAS showed almost no difference under UV-B stress for 1 h. The results showed the HTAS of N. barkeri had lower fitness under UV-B stress compared with the CS of N. barkeri. These results suggested that long-term heat acclimation may exert a profound impact on the developmental physiology of N. barkeri.

Mixed-anion chalcohalides have attracted significant attention lately, attributable to their unique structure compositions and captivating physicochemical properties. Herein, an unprecedented pentanary chalcohalide, Cs2[Mn2Ga3S7Cl] (1), was discovered by solid-state reaction at 1223 K. It is constructed by alternately stacked layers, each of which is made by a 2D [Ga3S9]9- ribbon embedded with 1D [Mn2S8Cl]13- chains. The coexistence of two Mn-coordinated polyhedra ([MnS6] octahedra and hetero-ligand [MnS3Cl] tetrahedra) in one material is surprisingly observed for the first time in the Mn-containing inorganic chalcogenides or chalcohalides. More interestingly, it exhibits ferrimagnetic (FIM) behaviour, which could be correlated to the magnetic sub-lattice sites with different coordination geometries. This work suggests a new route for designing and searching for unique functional chalcohalides with different chemical environments.

Organic pollutants have attracted increasing attention due to their strong persistence and extensive diffusivity. Plasticizers (PAEs) and organophosphorus pesticides (OPs), as the vital part of organic pollutants, have made extensive damage to the environment with the rapid development of modern agriculture and industry. Therefore, we have, for the first time, carried out a quantitative analysis of the PAEs and OPs by fluorescence recognition. A series of isostructural lanthanide organic frameworks, [Ln(tftpa)1.5(2,2'-bpy)(H2O)] (Ln = Gd 1, Eu 2 and Tb 3, H2tftpa = tetrafluoroterephthalic acid), were hydrothermally synthesized, of which 3 exhibited excellent hydrolytic resistance to both boiling acidic and basic aqueous solutions. Moreover, luminescence investigations show that 3 can be used as a highly sensitive and recyclable luminescence sensor for the detection of DBP (di-n-butyl phthalate) in simulated seawater and chlorpyrifos in ethanol with the detection limits of 2.07 and 0.14 ppb, respectively.

Objective: The aim of this study was to explore the effects of acupuncture on mild postpartum depression (PPD)., Methods: 15 patients diagnosed with PPD were enrolled in the study. Patients who satisfied the inclusion criteria received acupuncture therapy eight times over 4 weeks in the form of two 20-min treatment sessions per week. The treatment site was the BL67 acupuncture point (on the outside of the fifth toenail). After disinfecting the skin on the toes, sterile steel needles were gently inserted into the acupuncture point until the patient started to feel numb or swollen, a sensation known as de qi . Acupuncture was performed by the same doctor using HuanQiu stainless steel needles that were 0.2 mm in diameter and 40 mm in length. The Hamilton Depression Scale (HAMD) was used to evaluate the clinical effects of this therapy. Questionnaires were distributed to patients before therapy and 1 week after therapy and were immediately completed and checked., Results: Treatment was associated with symptomatic improvement for all patients who adhered to therapy. The nine patients who completed treatment had an average pain score of 6.66 (SD 0.86); these patients' average pre-treatment pain score was 10.83 (SD 1.47). Six patients who did not complete treatment had an average pain score of 11.23 (SD 1.48); the average pre-treatment pain score of these patients was 10.5 (SD 2.21). Thus, symptoms did not significantly improve for patients who failed to adhere to the therapy. There was no significant difference between the two groups with respect to HAMD score before treatment (P=0.363). By contrast, asignificant between-group difference in post-treatment HAMD score was detected (P=0.001). Two patients discontinued treatment due to haemorrhage at the site of needling, and four patients discontinued treatment due to the inconvenience of traffic. There were no significant complications., Conclusion: Acupuncture therapy at BL67 may alleviate symptoms of mild PPD, however controlled clinical investigations are required to confirm its efficacy and effectiveness for this condition., Competing Interests: Competing interests: None declared., (© Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.)

A new 3D MOF [MnLi 2 (ip) 2 (H 2 O) 2 ] (1) with a 1D heterometallic inorganic Mn(ii)-Li(i) chain is reported. With the assistance of diamagnetic {LiO 4 } connectors, which separate the paramagnetic Mn(ii) ions and act as magnetic spacers, very weak magnetic interactions were obtained. Remarkably, 1 showed a significant magnetocaloric effect (MCE) with a large entropy change value of 30.4 J kg -1 K -1 for ΔH = 8 T at 2 K.

An iodoplumbate-based organic-inorganic hybrid ferromagnetic semiconductor, [Pb 3 Cu 2 I 10 (phen) 4 ] n , has been solvothermally synthesized. The ferromagnetic exchange interaction is resulting from the multiple aromatic π-π stacking interactions between the adjacent phen molecules.

With the aid of a bifunctional 6-mercaptonicotinic acid ligand, a novel {Ni 12 Gd 24 } cage-based (6, 12)-c alb-MROF that is assembled from a {Gd 4 (OH) 4 (COO) 6 } trigonal-prism building unit and a {Ni 6 S 12 } hexagonal-prism molecular building block has been synthesized for the first time. It exhibits a large MCE value of 29.86 J kg -1 K -1 for ΔH = 8 T at 2 K.

The predatory mite Neoseiulus barkeri (Hughes) is a good biological control agent for many small sucking pests. We aimed to determine whether rearing long term on alternative prey versus target prey species affected the performance of N. barkeri. Therefore, we investigated the prey preference, life tables, and population parameters of N. barkeri between alternative prey Tyrophagus putrescentiae (Schrank) and three species of spider mites, Tetranychus urticae Koch, Panonychus citri (McGregor), and Eotetranychus kankitus Ehara. We found that N. barkeri preferred the tetranychid mites to the alternative prey. Between the tetranychid mites, the predator consumed more P. citri and E. kankitus than T. urticae. When reared on T. urticae, the total developmental time and longevity of N. barkeri were the longest, whereas the intrinsic rate of increase was the lowest, indicating that the biotic fitness of predatory mite preyed on target of T. urticae was higher than on alternative prey of T. putrescentiae. However, total developmental time, longevity, and fecundity did not differ between N. barkeri reared on T. putrescentiae and P. citri, although these parameters were higher than those for mites reared on E. kankitus, indicating that the predatory mite reared on T. putrescentiae may not be affected to control P. citri, and that coexistence of P. citri and E. kankitus may enhance the control efficiency of N. barkeri. Altogether, our results demonstrated that long-term feeding on the alternative prey T. putrescentiae did not affect the performance of the predatory mite N. barkeri on various target spider mites., (© The Authors 2017. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Eotetranychus kankitus Ehara (Acari: Tetranychidae) is an important pest in Chinese citrus orchards. In the present study, we aimed to evaluate the potential of Neoseiulus barkeri (Hughes) (Acari: Phytoseiidae) for the biological control of E. kankitus. A two-sex life table of E. kankitus and N. barkeri was constructed to estimate development and fecundity. The functional response and stage-specific predation rate were analyzed to evaluate predation capacity. In addition, a timing model was used to project populations of E. kankitus with release of N. barkeri. Results showed that N. barkeri was able to develop and reproduce when fed on E. kankitus. The functional responses of N. barkeri on different stages of E. kankitus all fit the Holling II disc equation. When mixed stages of E. kankitus coexisted, N. barkeri mainly consumed larvae and nymphs. Based on the life tables and stage-specific predation rates, population projection revealed the stage structure and growth rate of N. barkeri on E. kankitus. Although E. kankitus had the higher growth rate, it was maintained at a low population level for several weeks after release of N. barkeri. The results highlighted the potential for utilizing N. barkeri as a biological control agent of E. kankitus., (© The Authors 2017. Published by Oxford University Press on behalf of Entomological Society of America. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

An anionic Co II -MOF, (Me 2 NH 2 )[Co 3 (Me 2 NH) 3 (OH)(SDBA) 3 ] (1) (H 2 SDBA=4,4'-sulfonyldibenzoic acid) consisting of highly symmetric Co II 3 (μ 3 -OH) triangles exhibits spin-canting, spin-flop, and easy-plane magnetic anisotropy. Measurement on a single crystal shows that the ab plane of 1 is the easy magnetization plane. After structural modification through simultaneous removal of the coordinated dimethylamine (DMA) molecule at the Co center and the ionic groups DMA + and OH - , the resulting neutral amorphous framework 2 displays an enhanced spin frustration effect. The deionization of 1 does not result in the collapse of the framework, showing the high stability of the backbone structure., (© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Curvature prevalently exists in the world of carbon materials (e.g., fullerenes, buckyl bowls, carbon nanotubes, and onions), but traditional C2-addition mechanisms fail to elucidate the mechanism responsible for the formation of carbon curvature starting from a pentagonal carbon ring in currently available chemical-physical processes such as combustion. Here, we show a complete series of nascent pentagon-incorporating C5-C18 that are online produced in the flame of acetylene-cyclopentadiene-oxygen and in situ captured by C60 or trapped as polycyclic aromatic hydrocarbons for clarifying the growth of the curved subunit of C20H10. A mechanism regarding C1-substitution and C2-addition has been proposed for understanding the formation of curvature in carbon materials, as exemplified by the typical curved molecule containing a single pentagon completely surrounded by five hexagons. The present mechanism, supported by the intermediates characterized by X-ray crystallography as well as NMR, has been experimentally validated for the rational synthesis of curved molecule in the commercially useful combustion process.

In the male reproductive system of insects, the male accessory glands and ejaculatory duct (MAG/ED) are important organs and their primary function is to enhance the fertility of spermatozoa. Proteins secreted by the MAG/ED are also known to induce post-mating changes and immunity responses in the female insect. To understand the gene expression profile in the MAG/ED of the oriental fruit fly Bactrocera dorsalis (Hendel), that is an important pest in fruits, we performed an Illumina-based deep sequencing of mRNA. This yielded 54,577,630 clean reads corresponding to 4.91Gb total nucleotides that were assembled and clustered to 30,669 unigenes (average 645bp). Among them, 20,419 unigenes were functionally annotated to known proteins/peptides in Gene Orthology, Clusters of Orthologous Groups, Kyoto Encyclopedia of Genes and Genomes pathway databases. Typically, many genes were involved in immunity and these included microbial recognition proteins and antimicrobial peptides. Subsequently, the inducible expression of these immunity-related genes was confirmed by qRT-PCR analysis when insects were challenged with immunity-inducible factors, suggesting their function in guaranteeing fertilization success. Besides, we identified some important reproductive genes such as juvenile hormone- and ecdysteroid-related genes in this de novo assembly. In conclusion, this transcriptomic sequencing of B. dorsalis MAG/ED provides insights to facilitate further functional research of reproduction, immunity and molecular evolution of reproductive proteins in this important agricultural pest., (Copyright © 2015 Elsevier Inc. All rights reserved.)

A new approach to prepare heterometallic cluster organic frameworks has been developed. The method was employed to link Anderson-type polyoxometalate (POM) clusters and transition-metal clusters by using a designed rigid tris(alkoxo) ligand containing a pyridyl group to form a three-fold interpenetrated anionic diamondoid structure and a 2D anionic layer, respectively. This technique facilitates the integration of the unique inherent properties of Anderson-type POM clusters and cuprous iodide clusters into one cluster organic framework., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In insects, the accessory gland proteins (Acps) secreted by male accessory glands (MAGs) account for the majority of seminal fluids proteins. Mixed with sperm, they are transferred to the female at mating and so impact reproduction. In this project, we identified 2,927 proteins in the MAG secretions of the oriental fruit fly Bactrocera dorsalis, an important agricultural pest worldwide, using LC-MS analysis, and all sequences containing open reading frames were analyzed using signalP. In total, 90 Acps were identified. About one third (26) of these 90 Acps had a specific functional description, while the other two thirds (64) had no functional description including dozens of new classes of proteins. Hence, several of these novel Acps were abundant in the MAG secretions, and we confirmed their MAG-specific expression by qPCR. Finally and interestingly, one of these novel proteins was functionally predicted as juvenile hormone-binding protein, suggesting the impact of Acps with reproductive events in the female. Our results will aid in the development of an experimental method to identify Acps in insects, and in turn this information with new Acps in B. dorsalis will pave the way of further exploration their function in reproduction and potential development as new insecticide targets.

A pair of chiral template induced anionic homochiral frameworks constructed from achiral components has been synthesized. Ion-exchange of counter cations with polar or chiral organic cations enhances the SHG efficiency of the frameworks. The enantioselective sensing of chiral alkamines can be achieved by the SHG response.

Four new inorganic-organic hybrid manganese frameworks, formulated as [Mn(Am-Hip)2]·3H2O (1), [Mn2(ip)2(H2O)]·CH3OH (2), [Mn2(OH-ip)2(DMF)]·DMF (3), and (Me2NH2)[Mn4(sdba)4(Hsdba)(H2O)]·3H2O·2DMF (4) (Am-H2ip = 5-aminoisophthalic acid, H2ip = isophthalic acid, OH-H2ip = 5-hydroxyisophthalic acid, and H2sdba = 4,4'-sulfonyldibenzoic acid), have been prepared by solvothermal reactions of Mn(II) ions with different polycarboxylate acids in the presence of LiNO3 or NH4NO3. Single-crystal X-ray diffraction studies reveal that the frameworks of 1-4 contain diverse Mn(II)-oxygen inorganic magnetic chain's sequences, -J1J1J1J1- for 1, -J1J2J1J2- for 2, -J1J1J2J2- for 3, and -J1J2J3J3- for 4. The sequence in 4 has never been seen for the magnetic chain compounds and is a new type of magnetic alternating sequence. Magnetic investigations indicate that these compounds all show weak antiferromagnetic couplings between the adjacent Mn(II) ions. Magnetostructural analyses based on the data of 1-4 and other related Mn(II) chain compounds imply that the magnitude of the magnetic coupling has some relationship with the Mn-O-Mn angle of the μ2-O bridge and the average Mn-O-C-O torsion angle of the carboxylate bridges. Compounds 2 and 4 crystallize in chiral and acentric space groups, and they both exhibit powder second harmonic generation (SHG) efficiencies approximately 0.6 and 0.9 times, respectively, that of the standard potassium dihydrogen phosphate (KDP) powder. In addition, the dielectric properties of 2 and 4 were also investigated.

Temperature is one of the most important environmental variables affecting growth, reproduction and distribution of insects. The rise of comparative proteomics provides a powerful tool to explore the response in proteins to thermal stress. As an important worldwide pest, the oriental fruit fly Bactrocera dorsalis causes severe economic losses to crops. To understand the response of B. dorsalis to thermal stress, we performed a comparative proteome analysis of this insect after exposure to extreme low and high temperatures using two-dimensional electrophoresis. Among the separated proteins, 51 diverse protein spots were present differently in response to extreme temperatures. Using tandem mass spectrometry sequencing analysis 39 proteins were successfully identified, which included 13 oxidoreductases, 10 binding proteins, 5 transferases, and 2 each of lyases, isomerases, ligases, and developmental proteins. Subsequently, the expression of these protein transcripts was studied by RT-qPCR to validate the proteomic results. In conclusion, this study provides a first look into the thermal stress response of B. dorsalis at the protein level, and thus it paves the way for further functional studies in the physiological mechanism related to thermal stress., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A pair of enantiomorphic frameworks featuring rare chiral 3D inorganic connectivity and a {Pb18} wheel, has been obtained via spontaneous resolution. They exhibit rapid and highly selective and sensitive sensing of Co(2+) ions.

An improved algorithm based on a fiber loop optical structure is proposed for measurement of water vapor concentration. Compared with the traditional algorithm, the intrinsic loss of optical devices in the loop is no longer necessary to be accurately measured but instead is directly eliminated by normalization. The concentration of the analyte can be determined by only two pulses without the need for exponential curve fitting, which leads to a significant reduction in the amount of data required to make a measurement. The restriction on the inherent loss of the fiber loop system also can be eased. In addition, a background absorption problem caused by the water vapor existing inside internal end-face gaps of optical components is solved. The mean absolute error of 29 parts per million by volume has been achieved with a 6.5 cm gas gap by using the new algorithm.

Reversible crystal-to-amorphous-to-crystal phase transition accompanied by changes in magnetic and NLO properties was first observed in a rigid non-porous spongelike MOF material. The crystal phase exhibits a high magnetocaloric effect, while the amorphous phase has potential application as a magnetic DMF sensor.

A novel tetradecanuclear mixed-valent cobalt cluster, formulated as [Co(II)(10)Co(III)(4)(OH)(2)O(6)(hmp)(10)(pdm)(4)(CH(3)OH)(2)]·5H(2)O (1), was obtained using mixed ligands of 2-(hydroxymethyl)pyridine (hmpH) and 2,6-pyridinedimethanol (pdmH(2)). The cobalt ions in 1 are connected by ten chelating hmp(-) ligands, four tris-chelating pdm(2-) ligands and six μ(3)-oxide/hydroxide anions, forming a unique shield-like planar structure that is rarely observed for Co-based clusters. Compound 1 displays slight frequency dependence at static zero field below 4.5 K, suggesting that it might be a single molecule magnet (SMM)., (This journal is © The Royal Society of Chemistry 2012)