Molecular Engineering Regulation Achieving Out-of-Plane Polarization in Rare-Earth Hybrid Double Perovskites for Ferroelectrics and Circularly Polarized Luminescence.

Out-of-plane polarization is a highly desired property of two-dimensional (2D) ferroelectrics for application in vertical sandwich-type photoferroelectric devices, especially in ultrathin ferroelectronic devices. Nevertheless, despite great advances that have been made in recent years, out-of-plane polarization remains unrealized in the 2D hybrid double perovskite ferroelectric family. Here, from our previous work 2D hybrid double perovskite HQERN ((S3HQ)4EuRb(NO3)8, S3HQ = S-3-hydroxylquinuclidinium), we designed a molecular strategy of F-substitution on organic component to successfully obtain FQERN ((S3FQ)4EuRb(NO3)8, S3FQ = S-3-fluoroquinuclidinium) showing circularly polarized luminescence (CPL) response. Remarkably, compared to the monopolar axis ferroelectric HQERN, FQERN not only shows multiferroicity with the coexistence of multipolar axis ferroelectricity and ferroelasticity but also realizes out-of-plane ferroelectric polarization and a dramatic enhancement of Curie temperature of 94 K. This is mainly due to the introduction of F-substituted organic cations, which leads to a change in orientation and a reduction in crystal lattice void occupancy. Our study demonstrates that F-substitution is an efficient strategy to realize and optimize ferroelectric functional characteristics, giving more possibility of 2D ferroelectric materials for applications in micro-nano optoelectronic devices.

Rational Design of 2D Metal Halide Perovskites with Low Congruent Melting Temperature and Large Melt-Processable Window.

Metal halide perovskites (MHPs) have garnered significant attention due to their distinctive optical and electronic properties, coupled with excellent processability. However, the thermal characteristics of these materials are often overlooked, which can be harnessed to cater to diverse application scenarios. We showcase the efficacy of lowering the congruent melting temperature (Tm) of layered 2D MHPs by employing a strategy that involves the modification of flexible alkylammonium through N-methylation and I-substitution. Structural-property analysis reveals that the N-methylation and I-substitution play pivotal roles in reducing hydrogen bond interactions between the organic components and inorganic parts, lowering the rotational symmetry number of the cation and restricting the residual motion of the cations. Additional I···I interactions enhance intermolecular interactions and lead to improved molten stability, as evidenced by a higher viscosity. The 2D MHPs discussed in this study exhibit low Tm and wide melt-processable windows, e.g., (DMIPA)2PbI4 showcasing a low Tm of 98 °C and large melt-processable window of 145 °C. The efficacy of the strategy was further validated when applied to bromine-substituted 2D MHPs. Lowering the Tm and enhancing the molten stability of the MHPs hold great promise for various applications, including glass formation, preparation of high-quality films for photodetection, and fabrication of flexible devices.

Probing distribution and dynamics of lithium ions in supermolecule ß-CD-PEO/Li+ solid polymer electrolytes via solid-state NMR.

In this work, the distribution and dynamics of Li+ ions in ß-CD-PEO/Li+ (ß-CD, ß-cyclodextrin; PEO, polyethylene-oxides) crystalline polymer electrolytes were investigated by solid-state NMR to enlighten the ionic conduction mechanism. Specifically, 7Li-6Li REDOR NMR and variable-contact-time 1H-6Li CP/MAS NMR were adopted for the study. The results demonstrate that Li+ ions coordinated by polymer chains have relatively compact spatial density and fast dynamics, which facilitate the improvement of the electrochemical properties. Additionally, the variation of the distribution and dynamics of the Li+ ions and the ionic conduction mechanism were studied and discussed by altering the amount of the Li+ ions. This work deepens our understanding of the distribution and dynamics of Li+ ions in ß-CD-PEO/Li+ crystals and demonstrates possible future applications of solid-state NMR on the study of the polymer electrolytes.

A-Site Mixing to Adjust the Photovoltaic Performance of a Double-Cation Perovskite: It Is Not Always the Simple Way.

Considerable progress has been made in improving the performance of optoelectronic devices based on hybrid organic-inorganic perovskites of the form ABX3. However, the influences of A-site doping on the structure and dynamics of the inorganic perovskite crystal lattice and, in turn, on the optoelectronic performance of the resulting devices remain poorly understood at an atomic level. This work addresses this issue by combining the results of several experimental characterization methods for three-dimensional MA1-xDMAxPbBr3 perovskite single crystals (MA, methylammonium; DMA, dimethylammonium). The results reveal a two-stage change in lattice with an increase in DMA content, which has completely opposite effects on the optoelectronic performance of the double-cation perovskite. At low DMA concentrations, fast reorientation of incorporated DMA cations strengthens the interaction between MA cations and the lattice without significant lattice distortion, which could suppress lattice fluctuation and thus improve the photovoltaic performance. At high DMA concentrations, the lattice get a severe distortion, leading to poorer photovoltaic performance.

Chemical structure of semiochemicals and key binding sites together determine the olfactory functional modes of odorant-binding protein 2 in Eastern honey bee, Apis cerana.

Insects can exhibit flexible olfaction that is sensitive to complex natural chemical environments. Odorant-binding proteins (OBPs) in insects' antennal chemosensilla can act as transporters of plant volatiles and pheromones across the sensillar lymph. Although the physiological functions of OBPs have been widely reported, it is still unclear how OBP binds to ligands with various structures in detail. Here, we further investigated the ligand-binding modes and characteristics of AcerOBP2 from the Eastern honey bee (Apis cerana). The results showed that, as a specific protein distributed below the base of chemosensilla on the antennal surface, AcerOBP2 was strongly bound with the candidate floral volatiles and bee pheromones. By docking analysis and site-directed mutagenesis, four different binding modes were found in the five AcerOBP2 mutants between six ligands. Two key amino acids, Ser123 and Lys51, play a key role in AcerOBP2 binding to odors, depending on the presence or absence of hydrogen bonds. In addition, the binding modes depend on their chemical structures and the binding poses of the diverse ligands. These results not only further prompted the functional basis of the relationship between the chemical structures of odorants and bee OBPs, but also revealed the complexity of the flexible behavioral modes of odor binding in insect olfactory systems.

A Small Lattice Change Induces Significant Dynamic Changes of CH3NH3+ Caged in Hybrid Perovskite Crystals: Toward Understanding the Interplay between Host Lattices and Guest Molecules.

Two perovskite-type compounds, (MA)2[B'Co(CN)6] (MA = methylammonium, B' = K(I) and Na(I)), have very similar structures, but exhibit marked differences in the phase and dielectric transitions. Solid state 2H NMR studies reveal the detailed dynamic changes of the caged methylammonium (MA) cations before and after the phase transitions, which are correlated with the different dielectric states of the compounds. Using solid state 59Co NMR, the dynamic changes of the host lattices before and after the transitions, which accompany the changes in the dynamics of the caged MA cations, are unveiled, demonstrating the intriguing interplay between the MA cations and the host lattices. On the basis of these observations, the molecular origins of the dielectric transitions are discussed in detail.

Physicochemical Basis and Comparison of Two Type II Sex Pheromone Components Binding with Pheromone-Binding Protein 2 from Tea Geometrid, Ectropis obliqua.

Lepidopteran geometrid moth can produce complex Type II sex pheromone components to attract males and trigger mating behavior. Although several sex pheromone components have been identified, it remains unclear whether their physicochemical roles in sex pheromone sensing are the same. Therefore, we utilized tea geometrid ( Ectropis obliqua) as an example model to investigate and compare the physicochemical basis of two key Type II sex pheromone components, cis-6,7-epoxy-(3Z,9Z)-3,9-octadecadiene ( Z3 Z9-6,7-epo-18:Hy) and ( Z, Z, Z)-3,6,9-octadecatriene (Z3Z6Z9-18:Hy), interacting with pheromone-binding protein 2 ( EoblPBP2) from E. obliqua. Multispectral, thermodynamic, docking, and site-directed mutagenesis indicated that the major sex pheromone component Z3Z9-6,7-epo-18:Hy is more susceptible to pH-tuned than the minor component Z3Z6Z9-18:Hy, whereas Z3Z6Z9-18:Hy seems to be more susceptible to temperature and amino acid mutations than Z3Z9-6,7-epo-18:Hy. Our study suggests that different components of Type II sex pheromone play different binding characters under specific conditions in the physicochemical behavior. This deeply supplements the theoretical knowledge of Type II pheromones involved in the recognition and discrimination in the Lepidopteran sex pheromones family.

Various Bee Pheromones Binding Affinity, Exclusive Chemosensillar Localization, and Key Amino Acid Sites Reveal the Distinctive Characteristics of Odorant-Binding Protein 11 in the Eastern Honey Bee, Apis cerana.

Odorant-binding proteins (OBPs) are the critical elements responsible for binding and transporting odors and pheromones in the sensitive olfactory system in insects. Honey bees are representative social insects that have complex odorants and pheromone communication systems relative to solitary insects. Here, we first cloned and characterized OBP11 (AcerOBP11), from the worker bees antennae of Eastern honey bee, Apis cerana. Based on sequence and phylogenetic analysis, most sequences homologous to AcerOBP11 belong to the typical OBPs family. The transcriptional expression profiles showed that AcerOBP11 was expressed throughout the developmental stages and highly specifically expressed in adult antennae. Using immunofluorescence localization, AcerOBP11 in worker bee's antennae was only localized in the sensilla basiconica (SB) near the fringe of each segment. Fluorescence ligand-binding assay showed that AcerOBP11 protein had strong binding affinity with the tested various bee pheromones components, including the main queen mandibular pheromones (QMPs), methyl p-hydroxybenzoate (HOB), and (E)-9-oxo-2-decanoic acid (9-ODA), alarm pheromone (n-hexanol), and worker pheromone components. AcerOBP11 also had strong binding affinity to plant volatiles, such as 4-Allylveratrole. Based on the docking and site-directed mutagenesis, two key amino acid residues (Ile97 and Ile140) were involved in the binding of AcerOBP11 to various bee pheromones. Taken together, we identified that AcerOBP11 was localized in a single type of antennal chemosensilla and had complex ligand-binding properties, which confer the dual-role with the primary characteristics of sensing various bee pheromones and secondary characteristics of sensing general odorants. This study not only prompts the theoretical basis of OBPs-mediated bee pheromones recognition of honey bee, but also extends the understanding of differences in pheromone communication between social and solitary insects.

Functional Characteristics, Electrophysiological and Antennal Immunolocalization of General Odorant-Binding Protein 2 in Tea Geometrid, Ectropis obliqua.

As one of the main lepidopteran pests in Chinese tea plantations, Ectropisobliqua Warren (tea geometrids) can severely decrease yields of tea products. The olfactory system of the adult tea geometrid plays a significant role in seeking behaviors, influencing their search for food, mating partners, and even spawning grounds. In this study, a general odorant-binding protein (OBP) gene, EoblGOBP2, was identified in the antennae of E. obliqua using reverse transcription quantification PCR (RT-qPCR). Results showed that EoblGOBP2 was more highly expressed in the antennae of males than in females relative to other tissues. The recombinant EoblGOBP2 protein was prepared in Escherichia coli and then purified through affinity chromatography. Ligand-binding assays showed that EoblGOBP2 had a strong binding affinity for some carbonyl-containing tea leaf volatiles (e.g., (E)-2-hexenal, methyl salicylate, and acetophenone). Electrophysiological tests confirmed that the male moths were more sensitive to these candidate tea plant volatiles than the female moths. Immunolocalization results indicated that EoblGOBP2 was regionally confined to the sensilla trichoid type-II in the male antennae. These results indicate that EoblGOBP2 may be primarily involved in the olfactory activity of male E. obliqua moths, influencing their ability to sense tea leaf volatiles. This study provides a new perspective of insect GOBPs and implies that olfactory function can be used to prevent and control the tea geometrid.

Fast Lithium-Ion Transportation in Crystalline Polymer Electrolytes.

Fast lithium-ion transportation is found in the crystalline polymer electrolytes, α-CD-PEOn /Li+ (n=12, 40), prepared by self-assembly of α-cyclodextrin (CD), polyethylene oxide (PEO) and Li+ salts. A detailed solid-state NMR study combined with the X-ray diffraction technique reveals the unique structural features of the samples, that is, a) the tunnel structure formed by the assembled CDs, providing the ordered long-range pathway for Li+ ion transportation; b) the all-trans conformational sequence of the PEO chains in the tunnels, attenuating significantly the coordination between Li+ and the EO segments. The origin of the fast lithium-ion transportation has been attributed to these unique structural features. This work demonstrates the first example in solid polymer electrolytes (SPEs) for "creating" fast ion transportation through material design and will find potential applications in the design of new ionconducting SPE materials.

Three-Component Supramolecular System with Multistimuli-Responsive Properties in Water.

Hyperbranched polyethylenimine terminated with isobutyramide groups (HPEI-IBAm), 4-(phenylazo)benzoic acid (PABA), and α-cyclodextrin (α-CD) were assembled together at pH≈7 to form the three-component supramolecular complexes that were verified by (1) H and 2D ROESY (1) H NMR spectroscopy. UV/Vis spectrometric titration experiments showed that the content of α-CD in the three-component complexes was less than the feed amount and it was difficult for all the PABA units in the complexes to further form complexes with α-CD. The obtained three-component supramolecular complexes exhibited thermoresponsive properties in water. Increasing the α-CD concentration led to a sharp increase in the cloud point temperature (Tcp ) at the beginning, but after the [α-CD]/[PABA] ratio was in the region of 1.3-1.6, the Tcp increased gradually When the concentration of α-CD was low, a higher concentration of PABA led to a lower Tcp , however, the opposite was observed when the concentration of α-CD was high. For the three-component complex, increasing the α-CD concentration at pH≈7 or at pH≈9 led to different Tcp temperatures. In the low α-CD concentration range, adjusting the pH from ≈7-≈9 resulted in an increase in the Tcp , similar but not so pronounced as that of the two-component system of HPEI-IBAm/[PABA]. When the concentration of α-CD was high, adjusting the pH from ≈7-≈9 decreased the Tcp ; this observation is different to that of the two-component system of HPEI-IBAm/[PABA]. Reversible trans-to-cis photoisomerization of azobenzene units in the complexes occurred, following irradiation with UV or visible light. Trans-to-cis isomerization of azobenzene units decreased the Tcp . However, this result differed to that of the two-component system of HPEI-IBAm/PABA.

Ionic conductivity of ß-cyclodextrin-polyethylene-oxide/alkali-metal-salt complex.

Highly conductive, crystalline, polymer electrolytes, ß-cyclodextrin (ß-CD)-polyethylene oxide (PEO)/LiAsF6 and ß-CD-PEO/NaAsF6 , were prepared through supramolecular self-assembly of PEO, ß-CD, and LiAsF6 /NaAsF6 . The assembled ß-CDs form nanochannels in which the PEO/X(+) (X=Li, Na) complexes are confined. The nanochannels provide a pathway for directional motion of the alkali metal ions and, at the same time, separate the cations and the anions by size exclusion.

Protective effects of luteolin on cognitive impairments induced by psychological stress in mice.

In the present study, the protective effects of luteolin were investigated against psychological stress-induced cognitive impairment. To emulate the psychological stress, mice received restraint stress for six hours daily, between 9:00 and 15:00 hours, for 21 consecutive days. The results of step-through test, open-field test and Morris Water Maze test demonstrated that psychological stress treatment could result in cognitive impairments in mice. This cognition dysfunction was improved by treatment with low- and medium-dose luteolin. In addition, psychological stress induced an increased serum corticosterone concentration with a decreased serum norepinephrine and dopamine concentration. These alterations were attenuated by treatment with luteolin. Also, psychological stress significantly decreased the glutathione (GSH) concentrations and superoxide dismutase (SOD) activities in prefrontal cortex and hippocampus, while the malondialdehyde (MDA) concentrations were enhanced. However, these oxidative alterations in prefrontal cortex and hippocampus induced by psychological stress were significantly reversed by treatment of luteolin. Further, the current study indicated a decline of catalase (CAT) activities in the hippocampus of the ST group, which was significantly prevented by low, medium and high dose of luteolin. On the other hand, there was no significance in CAT activities of the prefrontal cortex among the six groups. Collectively, the present results suggest that luteolin treatment serves as a key role in improving the psychological stress-induced cognitive impairments.