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In recent years, with the development of batteries, ceramics, glass and other industries, the demand for lithium has increased rapidly. Due to the rich lithium resources in seawater and salt-lake brine, the question of how to selectively adsorb and separate lithium ions from such brine has attracted the attention and research of many scholars. The Li-ion sieve stands out from other methods thanks to its excellent special adsorption and separation performance. In this paper, mesoporous titanium dioxide and lithium hydroxide were prepared by hydrothermal reaction using bacterial cellulose as a biological template. After calcination at 600 °C, spinel lithium titanium oxide Li2TiO3 was formed. The precursor was eluted with HCl eluent to obtain H2TiO3. The lithium titanate were characterized by IR, SEM and X-ray diffraction. The adsorption properties of H2TiO3 were studied by adsorption pH, adsorption kinetics, adsorption isotherm and competitive adsorption. The results show that H2TiO3 has a single-layer chemical adsorption process, and has a good adsorption effect on lithium ions at pH 11.0, with a maximum adsorption capacity of 35.45 mg g-1. The lithium-ion sieve can selectively adsorb Li+, and its partition coefficient is 2242.548 mL g-1. It can be predicted that the lithium-ion sieve prepared by biological template will have broad application prospects.
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Though the flourishment of materials with multiple resonance (MR) in blue to green regions, red-emissive MR emitters are still rare in literatures, which definitely should be resolved for further applications. Herein, we report a simple molecular design strategy for the construction of pure-red MR emitters by conjugate charge transfer, which could greatly enhance the π-conjugation degree and charge-transfer property of the target molecule while maintaining the basic feature of MR, leading to a significant redshift of more than 128â nm compared to the selected parent MR core. The proof-of-concept emitter PPZ-BN exhibited a pure-red emission with a dominant peak at 613â nm and a small full-width-at-half-maximum of 0.16â eV (48â nm). The optimized organic light-emitting diode showed a high external quantum efficiency of 26.9 %, a small efficiency roll-off, and an excellent operation stability (LT99) of more than 43â hours at an initial luminance of 10 000â cd m-2 .
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The sugarcane woolly aphid is one of the main pests of sugarcane worldwide. The Pinellia pedatisecta agglutinin (PPA) gene has been demonstrated to function towards aphid resistance in other crops. In our study, in order to investigate the PPA function towards aphid control in sugarcane and its underlying mechanism, the PPA gene was overexpressed in a sugarcane Zhongzhe 1 (ZZ1) cultivar in independent transgenic sugarcane lines. It was confirmed in this study that PPA transgenic sugarcane can resist aphids via detecting the aphids' development and tracing the survival number on PPA-transgenic sugarcane lines as well as PPA negative control lines. The mechanism of PPA lectin-associated defense against aphids was preliminarily explored. Stomatal patterning differences of sugarcane leaves between PPA-transgenic sugarcane lines and negative control lines were found. PPA overexpression led to an increase in stomata number and a decrease in stomata size that might have changed the transpiration status, which is critical for aphids' passive feeding. Moreover, the antioxidant enzyme, sugar, tannin and chlorophyll content in sugarcane leaves before and after aphid infestation was determined. The results indicated that PPA overexpression in sugarcane resulted in an increase in antioxidant enzyme activity and tannin content, as well as a reduction in the decline of certain sugars. These together may improve sugarcane resistance against the sugarcane woolly aphid.
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Afídeos , Pinellia , Saccharum , Aglutininas , Animais , Animais Geneticamente Modificados , Antioxidantes , Saccharum/genética , TaninosRESUMO
Multiple resonance (MR) emitters are promising for highly efficient organic light-emitting diodes (OLEDs) with narrowband emission; however, they still face intractable challenges with concentration-caused emission quenching, exciton annihilation, and spectral broadening. In this study, sterically wrapped MR dopants with a fluorescent MR core sandwiched by bulk substituents were developed to address the intractable challenges by reducing intermolecular interactions. Consequently, high photo-luminance quantum yields of ≥90 % and small full width at half maximums (FWHMs) of ≤25â nm over a wide range of dopant concentrations (1-20â wt %) were recorded. In addition, we demonstrated that the sandwiched MR emitter can effectively suppress Dexter interaction when doped in a thermally activated delayed fluorescence sensitizer, eliminating exciton loss through dopant triplet. Within the above dopant concentration range, the optimal emitter realizes remarkably high maximum external quantum efficiencies of 36.3-37.2 %, identical small FWHMs of 24â nm, and alleviated efficiency roll-offs in OLEDs.
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A novel macrocycle of B/N-doped calix[4]arene (C-BN) was synthesized by a one-shot double boronation. Owing to the structural tension and electron-donating properties of the nitrogen atoms in the macrocycle, reaction selectively proceeds between the adjacent benzene rings outside the macrocycle. C-BN shows a highly centrosymmetric structure with two multiple resonance (MR) fragments bridged by tertiary amine groups at the 1,3 positions of the benzene ring. Benefiting from the large intermolecular distance (>4.6â Å) between adjacent MR-emitting cores, C-BN also exhibits excellent narrowband emitting features against aggregation-induced quenching and spectrum broadening. Optimized organic light-emitting diode devices based on C-BN exhibit high maximum external quantum efficiencies of 24.7-26.6 % and small full width at half maximums of 25-28â nm over a wide doping range of 1-12â wt %.
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Herein, we report a general strategy for achieving ultra-pure green emissions by suppressing the shoulder peaks in the emission spectra of conventional polycyclic aromatic hydrocarbons (PAHs). Through precise synthetic fusion of multi-resonance (MR) fragments with conventional PAH, extended π-conjugation lengths, increased molecular rigidity, and reduced vibrational frequency could be simultaneously realized. The proof-of-concept emitters exhibited ultra-pure green emissions with dominant peaks at ca. 521â nm, photoluminescence quantum yields that are greater than 99 %, a small full-width-at-half-maximum of 23â nm, and CIE coordinates of (0.16, 0.77). The bottom-emitting organic light-emitting diode (OLED) exhibited a record-high CIEy value of 0.74 and a high maximum external quantum efficiency of 30.5 %. The top-emitting OLED not only achieved a BT.2020 green color (CIE: 0.17, 0.78) for the first time but also showed superior performance among all green OLED devices, with a current efficiency of 220â cd A- .
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Nitrogen-containing polycyclic heteroaromatics have exhibited fascinating multi-resonance (MR) characteristics for efficient narrowband emission, but strategies to bathochromic shift their emissions while maintaining the narrow bandwidths remain exclusive. Here, homogeneous hexatomic rings are introduced into nitrogen-embedded MR skeletons to prolong the π-conjugation length for low-energy electronic transitions while retaining the non-bonding character of the remaining parts. The proof-of-the-concept emitters exhibit near unity photoluminescence quantum yields with peaks at 598â nm and 620â nm and small full-width-at-half-maximums of 28â nm and 31â nm, respectively. Optimal organic light-emitting diodes exhibit a high external quantum efficiency of 18.2 %, negligible efficiency roll-off, and ultra-long lifetime with negligible degradation at an initial luminance of 10 000â cd m-2 after 94â hours.
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Despite the remarkable multiple resonance (MR) optoelectronic properties of organic nanographenes with boron and nitrogen atoms disposed para to each other, the synthetic procedures are sophisticated with low yields and the molecular skeletons are limited. Here, a new paradigm of easy-to-access MR emitter is constructed by simplifying the multiborylation through amine-directed formation of B-N bonds while introducing an additional para-positioned nitrogen atom to trigger the MR effect. The proof-of-concept molecules exhibit narrowband emissions at 480 and 490â nm, with full width at half maxima (FWHMs) of only 29 and 34â nm. The devices based on them showed external quantum efficiencies (EQE) of >33.0 %, which remained above 24.0 % even at a high brightness of 5000â cd m-2 . This is the first example of MR emitters with a B-N covalent bond, not only decreasing the synthesis difficulty but also increasing the diversity of MR skeletons for emerging new optoelectronic properties.
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Polycyclo-heteraborin multi-resonance (MR) emitters are promising for high color-purity organic light-emitting diodes (OLEDs). Here, unlike the most common heteroatom ternary-doped (X/B/N) frameworks, a binary-doped (B/N) skeleton is reported with a large energy band for wide-range color tunability. Based on this parent-segment, a "one-pot" catalyst-free borylation method is developed which generates deep blue to pure green MR emitters from readily available starting materials, with peaks at 426-532â nm and full-width-at-half-maxima of 27-38â nm. Impressively, a maximum external quantum efficiency of nearly 40 % is recorded for the corresponding device with Commission Internationale de l'Eclairage coordinates of (0.14, 0.16), representing the state-of-the-art performances. This work presents a new paradigm and synthesis of B/N-doped MR emitters and will motivate the study of other novel frameworks.
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As an antioxidant, procyanidin B1(PB1) can improve the development of somatic cell nuclear transfer (SCNT) embryos; PB1 reduces the level of oxidative stress (OS) during the in vitro development of SCNT embryos by decreasing the level of reactive oxygen species (ROS) and increasing the level of glutathione (GSH) and mitochondrial membrane potential (MMP). Metabolite hydrogen peroxide (H2O2) produces OS. Catalase (CAT) can degrade hydrogen peroxide so that it produces less toxic water (H2O) and oxygen (O2) in order to reduce the harm caused by H2O2. Therefore, we tested the CAT level in the in vitro development of SCNT embryos; it was found that PB1 can increase the expression of CAT, indicating that PB1 can offset the harm caused by oxidative stress by increasing the level of CAT. Moreover, if H2O2 accumulates excessively, it produces radical-(HO-) through Fe2+/3+ and damage to DNA. The damage caused to the DNA is mainly repaired by the protein encoded by the DNA damage repair gene. Therefore, we tested the expression of the DNA damage repair gene, OGG1. It was found that PB1 can increase the expression of OGG1 and increase the expression of protein. Through the above test, we proved that PB1 can improve the repairability of DNA damage. DNA damage can lead to cell apoptosis; therefore, we also tested the level of apoptosis of blastocysts, and we found that PB1 reduced the level of apoptosis. In summary, our results show that PB1 reduces the accumulation of H2O2 by decreasing the level of OS during the in vitro development of SCNT embryos and improves the repairability of DNA damage to reduce cell apoptosis. Our results have important significance for the improvement of the development of SCNT embryos in vitro and provide important reference significance for diseases that can be treated using SCNT technology.
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Biflavonoides/farmacologia , Catequina/farmacologia , Desenvolvimento Embrionário/efeitos dos fármacos , Proantocianidinas/farmacologia , Animais , Antioxidantes/farmacologia , Apoptose/efeitos dos fármacos , Biflavonoides/metabolismo , Catalase/análise , Catalase/efeitos dos fármacos , Catequina/metabolismo , China , Feminino , Peróxido de Hidrogênio/farmacologia , Potencial da Membrana Mitocondrial/efeitos dos fármacos , Camundongos/embriologia , Camundongos Endogâmicos C57BL , Camundongos Endogâmicos DBA , Técnicas de Transferência Nuclear , Oócitos/efeitos dos fármacos , Estresse Oxidativo/efeitos dos fármacos , Proantocianidinas/metabolismo , Espécies Reativas de Oxigênio/metabolismoRESUMO
Efficient organic emitters in the deep-red region are rare due to the "energy gap law". Herein, multiple boron (B)- and nitrogen (N)-atoms embedded polycyclic heteroaromatics featuring hybridized π-bonding/ non-bonding molecular orbitals are constructed, providing a way to overcome the above luminescent boundary. The introduction of B-phenyl-B and N-phenyl-N structures enhances the electronic coupling of those para-positioned atoms, forming restricted π-bonds on the phenyl-core for delocalized excited states and thus a narrow energy gap. The mutually ortho-positioned B- and N-atoms also induce a multi-resonance effect on the peripheral skeleton for the non-bonding orbitals, creating shallow potential energy surfaces to eliminate the high-frequency vibrational quenching. The corresponding deep-red emitters with peaks at 662 and 692â nm exhibit narrow full-width at half-maximums of 38â nm, high radiative decay rates of ca. 108 â s-1 , ≈100 % photo-luminescence quantum yields and record-high maximum external quantum efficiencies of ca. 28 % in a normal planar organic light-emitting diode structure, simultaneously.
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Pure green emitters are essential for realizing an ultrawide color gamut in next-generation displays. Herein, by fusing the difficult-to-access aza-aromatics onto B (boron)-N (nitrogen) skeleton, a hybridized multi-resonance and charge transfer (HMCT) molecule AZA-BN was successfully synthesized through an effective one-shot multiple cyclization method. AZA-BN shows pure green fluorescence with photoluminance quantum yield of 99.7 %. The corresponding green device exhibits a maximum external quantum efficiency and power efficiency of 28.2 % and 121.7â lm W-1 , respectively, with a full width half maximum (FWHM) of merely 30â nm and Commission Internationale de l'Eclairage (CIE) coordinate y of 0.69, representing the purest green bottom-emitting organic light-emitting diode.
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Introduction: Traditional chemical control methods pose a damaging effect on farmland ecology, and their long-term use has led to the development of pest resistance. Methods: Here, we analyzed the correlations and differences in the microbiome present in the plant and soil of sugarcane cultivars exhibiting different insect resistance to investigate the role played by microbiome in crop insect resistance. We evaluated the microbiome of stems, topsoil, rhizosphere soil, and striped borers obtained from infested stems, as well as soil chemical parameters. Results and Discussion: Results showed that microbiome diversity was higher in stems of insect-resistant plants, and contrast, lower in the soil of resistant plants, with fungi being more pronounced than bacteria. The microbiome in plant stems was almost entirely derived from the soil. The microbiome of insect-susceptible plants and surrounding soil tended to change towards that of insect-resistant plants after insect damage. Insects' microbiome was mainly derived from plant stems and partly from the soil. Available potassium showed an extremely significant correlation with soil microbiome. This study validated the role played by the microbiome ecology of plant-soil-insect system in insect resistance and provided a pre-theoretical basis for crop resistance control.
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Research on recycling of used rare earth elements has been of great interest. Adsorption is one of the advantageous methods to recover gadolinium with high value. In the process of adsorption and separation of gadolinium from materials, the selectivity of materials for gadolinium can be significantly improved by using ion imprinting technique. However, gadolinium elution process is a traditional pickling process, which may affect the construction of imprinting sites. In this study, bacterial cellulose with three-dimensional spatial structure was used as the base material of aerogel material, and functional materials containing a large number of carboxyl groups were introduced by chemical grafting method. In combination with ion imprinting technology and N-polyacrylamide as intelligent temperature control valve, intelligent imprinting aerogel (PNBC-IIPS) with specific selectivity to gadolinium was prepared. The properties of aerogel materials were analyzed by SEM, FT-IR, and BET characterization. The experimental analysis shows that the desorption of gadolinium can be achieved by controlling the temperature change. The adsorption experiments show that PNBC-IIPS can selectively adsorb gadolinium ions from aqueous solution. The maximum adsorption capacity reached 95.51 mg g-1. Compared with unimprinted aerogel, the maximum adsorption capacity of gadolinium ion is significantly increased, which proves that the introduced ion imprinting technique plays a key role in the adsorption process. Cyclic experiments show that the adsorption capacity of PNBC-IIPS can still maintain 88% of the original adsorption capacity after 5 times of adsorption and desorption. In conclusion, PNBC-IIPS is a green adsorbent for selective recovery of gadolinium ions.
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Celulose , Águas Residuárias , Celulose/química , Adsorção , Espectroscopia de Infravermelho com Transformada de Fourier , Gadolínio , ÁguaRESUMO
Emitters with narrowband emissions are essential to improve the color purity of organic light-emitting diodes (OLEDs). Boron difluoride (BF) derivatives have preliminarily exhibited small full width at half-maximum (FWHM) values in electroluminescent devices, which, however, still face formidable challenges in recycling triplet excitons and realizing full-color emissions covering the whole visible spectra. Here, a systematic molecular engineering on the aza-fused aromatic emitting core and peripheral substitutions is made, affording a family of full-color BF emitters spanning from blue (461 nm) to red (635 nm), with high photoluminescence quantum yields of >90% and a small FWHM of 0.12 eV. The device architectures are delicately manipulated to form effective thermally activated sensitizing emissions, first affording the highest maximum external quantum efficiency of >20% for BF-based OLEDs with negligible efficiency roll-off.
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High-efficiency and stable deep-blue bottom-emitting organic light-emitting diodes with Commission Internationale de l'Eclairage y coordinates (CIE y s) < 0.08 remain exclusive in the literature owing to the high excited-state energy of the emitters. Here, we propose the utilization of narrowband emitters to lower the excited-state energy for stable deep-blue devices by taking advantage of their high color purity. Two proof-of-concept deep-blue emitters with nitrogen-containing spiro-configured polycyclic frameworks are thereafter developed to introduce a multi-resonance effect for narrow emissions and sterically orthogonal configurations for alleviated molecular interactions. Both emitters show bright ultrapure deep-blue emissions with an extremely small full-width-at-half-maxima of only 18-19 nm, which can be maintained even in heavily doped films. Small CIE y s of 0.054 and 0.066 are therefore measured from the corresponding electroluminescence devices with peak energies of only 2.77 eV (448 nm) and 2.74 eV (453 nm), accounting for the remarkably long LT80s (lifetime to 80% of the initial luminance) of 18 900 and 43 470 hours at 100 cd m-2, respectively. Furthermore, by adopting a thermally activated delayed fluorescence sensitizer, impressive maximum external quantum efficiencies of 25% and 31% are recorded respectively, representing state-of-the-art performances for deep-blue devices.
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Thermally activated delayed fluorophores (TADF) with donor-acceptor (D-A) structures always face strong conjugation between donor and acceptor segments, rendering delocalized new molecular orbitals that go against blue emission. Developing TADF emitters with blue colors, high efficiencies, and long lifetimes simultaneously is therefore challenging. Here, a D-void-A structure with D and A moieties connected at the void-position where the frontier orbital from donor and acceptor cannot be distributed, resulting in nonoverlap of the orbitals is proposed. A proof-of-the-concept TADF emitter with 3,6-diphenyl-9H-carbazole (D) connected at the 3'3-positions of 9H-xanthen-9-one (A), the void carbon-atom with no distribution of the highest occupied molecular orbital (HOMO) of A-segment, realizes more efficient and blue-shifted emission compared with the contrast D-A isomers. The deeper HOMO-2 of A is found to participate into conjugation rather than HOMO, providing a wider-energy-gap. The corresponding blue device exhibits a y color coordinate (CIEy ) of 0.252 and a maximum external quantum efficiency of 27.5%. The stability of this compound is further evaluated as a sensitizer for a multiple resonance fluorophore, realizing a long lifetime of ≈650 h at an initial luminance of 100 cd m-2 with a CIEy of 0.195 and a narrowband emission with a full-width-at-half-maxima of 21 nm.
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Thermally activated delayed fluorescence (TADF) emitters featuring preferential horizontal emitting dipole orientation (EDO) are in urgent demand for enhanced optical outcoupling efficiency in organic light-emitting diodes (OLEDs). However, simultaneously manipulating EDO and optoelectronic properties remains a formidable challenge. Here, an extended linear D-A-D structure with both enlarged donor (D) and acceptor (A) π-systems is established, not only elaborately manipulating parallel horizontal molecular orientation and EDO along its long axis by multi-driving-forces for a high horizontal dipole ratio (Θ// ), but also delocalizing distribution of frontier energy levels for optimized electronic properties. The proof-of-the-concept emitter simultaneously affords a high Θ// of 92%, a high photoluminescence quantum yield of 95%, and a fast reverse intersystem crossing rate of 1.16 × 106 s-1 . The corresponding OLED achieves a champion maximum external quantum efficiency of 39.1% among all green TADF devices without any external light-extraction techniques, together with a maximum power efficiency of 112.0 lm W-1 and alleviated efficiency roll-off. These findings may inspire even better full-color TADF emitters that push the device efficiency toward the theoretical limits.
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Multiple donor-acceptor-type carbazole-benzonitrile derivatives that exhibit thermally activated delayed fluorescence (TADF) are the state of the art in efficiency and stability in sky-blue organic light-emitting diodes. However, such a motif still suffers from low reverse intersystem crossing rates (kRISC ) with emission peaks <470 nm. Here, a weak acceptor of cyanophenyl is adopted to replace the stronger cyano one to construct blue emitters with multiple donors and acceptors. Both linear donor-π-donor and acceptor-π-acceptor structures are observed to facilitate delocalized excited states for enhanced mixing between charge-transfer and locally excited states. Consequently, a high kRISC of 2.36 × 106 s-1 with an emission peak of 456 nm and a maximum external quantum efficiency of 22.8% is achieved. When utilizing this material to sensitize a blue multiple-resonance TADF emitter, the corresponding device simultaneously realizes a maximum external quantum efficiency of 32.5%, CIEy ≈ 0.12, a full width at half maximum of 29 nm, and a T80 (time to 80% of the initial luminance) of > 60 h at an initial luminance of 1000 cd m-2 .
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Two new deep-red iridium(III) complexes, (fpiq)2Ir(dipba) (fIr1) and (f2piq)2Ir(dipba) (dfIr2), comprising two cyclometaling ligands of fluorophenyl-isoquinoline derivatives (fpiq and f2piq) and a N-heterocyclic carbene (NHC)-based ancillary ligand of N,N'-diisopropylbenzamidinate (dipba) are designed, synthesized, and characterized. Given the unique four-membered Ir-N-C-N backbone built by the metal center and the ancillary ligand, both phosphors achieve significant improvement for their comprehensive optoelectronic characteristics. Density function theory (DFT) calculations and electrochemical measurements support the genuine pure red phosphorescent emission of fIr1 and dfIr2 based on their clearly distinct electron density distributions of the HOMO/LUMO orbitals compared with other red-emitting Ir(III) derivatives. Both new phosphors show deep-red emission with λmax values in the region of 650-660 nm with high PLQYs and short excited-state lifetimes. The phosphorescent organic light emitting diodes (PhOLEDs) based on fIr1 and dfIr2 realize deep-red EL with the stable CIEx,y coordinates of (0.70, 0.30) and (0.69, 0.31), the peak EQE/PE values of 15.4%/9.3 lm W-1 and 16.7%/10.4 lm W-1, respectively, which maintain such high levels as 10.6%/3.5 lm W-1 and 10.8%/3.6 lm W-1 at the practical luminance of 1000 cd m-2. They are the highest EL values reported for the OLEDs with such deep-red CIE coordinates.