Hybrid nanospheres of silica covalently containing yellow-emitting cationic iridium(III) complex: preparation and application in white light-emitting diodes.

A yellow-emitting cationic iridium(III) complex [(dfppy)2Ir(TBD)]PF6 (TBD: N4,N4'-bis(3-(triethoxysilyl)propyl)-[2,2'-bipyridine]-4,4'-dicarboxamide; dfppy: 2-(2,4-difluorophenyl)pyridine) containing hydrolysable alkoxysilanes was synthesized. Then, a series of silica-based hybrid nanospheres with diameters of around 400 nm was prepared via the hydrolysis of this complex together with tetraethyl orthosilicate (TEOS, a silica source). When the amount of the complex used was 5.0 wt%, hybrid nanospheres showed the best photoluminescence (PL) properties, relative to the PL quantum yield of pure solid [(dfppy)2Ir(TBD)]PF6 (12.7%), that of hybrid nanospheres increased to 26.2%. Moreover, the thermal decomposition temperature (Td) of pure solid [(dfppy)2Ir(TBD)]PF6 was 331 °C, the Td of the complex in hybrid nanospheres increased to 447 °C. However, the yellow light emission was almost unchanged and was still located at 500-750 nm with a maximum wavelength (λem,max) of 577 nm. Under the excitation of blue-emitting chips (λem,max ≈ 455 nm), cold/neutral/warm white light-emitting diodes (WLEDs) with good luminous quality can all be fabricated using these hybrid nanospheres as phosphors in epoxy resin at different blending concentrations. Compared with two or three iridium(III) complexes being contained in silica-based particles as phosphors as described in literatures, in this study, silica-based hybrid nanospheres covalently containing only one yellow-emitting cationic iridium(III) complex as phosphors provide a more effective and simpler method for preparation high-performance WLEDs.

Genome-Wide Identification and Expression Analyses of the FAR1/FHY3 Gene Family Provide Insight into Inflorescence Development in Maize.

As transcription factors derived from transposase, FAR-RED IMPAIRED RESPONSE1 (FAR1) and its homolog FHY3 play crucial roles in the regulation of light signaling and various stress responses by coordinating the expression of downstream target genes. Despite the extensive investigation of the FAR1/FHY3 family in Arabidopsis thaliana and other species, a comprehensive examination of these genes in maize has not been conducted thus far. In this study, we employed a genomic mining approach to identify 16 ZmFAR1 genes in the maize inbred line B73, which were further classified into five subgroups based on their phylogenetic relationships. The present study characterized the predicted polypeptide sequences, molecular weights, isoelectric points, chromosomal distribution, gene structure, conserved motifs, subcellular localizations, phylogenetic relationships, and cis-regulatory elements of all members belonging to the ZmFAR1 family. Furthermore, the tissue-specific expression of the 16 ZmFAR1 genes was analyzed using RNA-seq, and their expression patterns under far-red light conditions were validated in the ear and tassel through qRT-qPCR. The observed highly temporal and spatial expression patterns of these ZmFAR1 genes were likely associated with their specific functional capabilities under different light conditions. Further analysis revealed that six ZmFAR1 genes (ZmFAR1-1, ZmFAR1-10, ZmFAR1-11, ZmFAR1-12, ZmFAR1-14, and ZmFAR1-15) exhibited a response to simulated shading treatment and actively contributed to the development of maize ears. Through the integration of expression quantitative trait loci (eQTL) analyses and population genetics, we identified the presence of potential causal variations in ZmFAR1-14 and ZmFAR1-9, which play a crucial role in regulating the kernel row number and kernel volume weight, respectively. In summary, this study represents the initial identification and characterization of ZmFAR1 family members in maize, uncovering the functional variation in candidate regulatory genes associated with the improvement of significant agronomic traits during modern maize breeding.

Sensitive fluorescent detection of phosmet and chlortetracycline in animal-derived food samples based on a water-stable Cd(II) chain-based zwitterionic metal-organic framework.

The residues of pesticides and antibiotics have always been a major concern in agriculture and food safety. In order to provide a new method for the rapid detection of organophosphorus pesticides and antibiotics, a novel Cd(II) chain-based zwitterionic metal-organic framework MOF 1 with high sensitivity fluorescence sensing performance was successfully synthesized. A series of researches showed that the water- and pH-stable bifunctional MOF 1 has a great ability to detect phosmet (PSM) and chlortetracycline (CTC) in water through fluorescence quenching effect, with high detection sensitivity, low detection limits (0.0124 µM and 0.0131 µM), short response time (40 s) and reusability. Practical application results revealed that MOF 1 could detect PSM and CTC in milk, beef, chicken and egg samples, with satisfactory recoveries (95.2%-103.7%). As a novel fluorescence probe, MOF 1, is known the first case that can detect PSM in animal-derived samples, and the first dual-function material capable of detecting PSM and CTC. Mechanism studies displayed that competitive absorption and photoinduced electron transfer clearly authenticate the high quenching performance of the material.

QTL mapping for flowering time in a maize-teosinte population under well-watered and water-stressed conditions.

Maize grain yield can be greatly reduced when flowering time coincides with drought conditions, which delays silking and consequently increases the anthesis-silking interval. Although the genetic basis of delayed flowering time under water-stressed conditions has been elucidated in maize-maize populations, little is known in this regard about maize-teosinte populations. Here, 16 quantitative trait loci (QTL) for three flowering-time traits, namely days to anthesis, days to silk, and the anthesis-silking interval, were identified in a maize-teosinte introgression population under well-watered and water-stressed conditions; these QTL explained 3.98-32.61% of phenotypic variations. Six of these QTL were considered to be sensitive to drought stress, and the effect of any individual QTL was small, indicating the complex genetic nature of drought resistance in maize. To resolve which genes underlie the six QTL, 11 candidate genes were identified via colocalization analysis of known associations with flowering-time-related drought traits. Among the 11 candidate genes, five were found to be differentially expressed in response to drought stress or under selection during maize domestication, and thus represented the most likely candidates underlying the drought-sensitive QTL. The results lay a foundation for further studies of the genetic mechanisms of drought resistance and provide valuable information for improving drought resistance during maize breeding. Supplementary Information: The online version contains supplementary material available at 10.1007/s11032-023-01413-0.

A graphitic-C3N4 derivative containing heptazines merged with phenyls: synthesis, purification and application as a high-efficiency metal-free quasi-green phosphor for white LEDs.

Because rare-earth elements are scarce, expensive, and unsustainable, it is of great significance to develop rare-earth-free (even metal-free) luminescent materials as phosphors for LEDs. Here, a graphitic-C3N4 (g-C3N4) derivative containing some heptazines merged with phenyls has been synthesized via thermal polymerization of melamine and quinazoline-2,4(1H,3H)-dione at an optimal mole ratio of 18 : 1. In comparison with g-C3N4 synthesized from melamine only, the photoluminescent (PL) emission colour changed from blue to green, the maximum emission wavelength (λ em,max) changed from 467 nm to 508 nm, and the PL quantum yield (PLQY) increased from 8.0% to 24.0%. It was further purified via vacuum sublimation, and a product with yellowish green emission (λ em,max = 517 nm) and PLQY up to 45.5% was obtained. This sublimated product had high thermal stability and low thermal quenching; its thermal decomposition temperature was as high as 527 °C, and its relative PL emission intensity at 100 °C was 90.8% of that at 20 °C. Excited by blue light chips (λ em,max ≈ 460 nm), cold, neutral and warm white LEDs can be fabricated using the sublimated product and orange-emitting (Sr,Ba)3SiO5:Eu2+ as phosphors. The good performances of these white LEDs (for example, the CIE coordinates, color rendering index and correlated color temperature were (0.31, 0.33), 84.4 and 6577 K, respectively) suggest that the low-efficiency blue-emitting g-C3N4 had been successfully converted into a high-efficiency metal-free quasi-green phosphor.

Luminescence properties of Cr3+-doped near-infrared emissive fluoroyttrates for light-emitting diodes.

In this work, a series of Cr3+-doped A2NaYF6 (denoted as ANYF:Cr; A = K, Rb, and Cs) fluoroyttrate double-perovskites with broad blue excitation and near-infrared (NIR) emission bands were prepared using a high-temperature solid-state reaction method. The physicochemical and spectroscopic properties of the as-prepared products, including crystal structure, bandgap, morphology, luminescence behaviour and optical performance, were studied in detail. The results show that the Cr3+ activators undergo a decreasing crystal field in ANYF in the direction from K to Cs, yielding a red shift of the emission peak position from 758 to 786 nm, whilst the full-width-at-half-maximum (FWHM) expands from 98 to 104 nm. By virtue of the broadband NIR emission, clear structural images of the tangerine section, mini LED flashlight and circuit board were obtained by merging the optimal RNYF:Cr phosphor on a blue InGaN chip, implying its potential use in light-emitting diodes for non-destructive testing.

A cationic iridium(III) complex containing a thiosemicarbazide unit: Synthesis and application for turn-on chemiluminescent detection of Hg2.

A novel cationic iridium(III) complex [(ppy)2Ir(bPCPC)]PF6 (ppy: 2-phenylpyridine; bPCPC: 2-([2,2'-bipyridine]-4-carbonyl)-N-phenylhydrazinecarbothioamide) containing a thiosemicarbazide unit was designed and synthesized. The thiosemicarbazide unit was a sensitive functional group to Hg2+, when it reacted with Hg2+, it was desulphurized and thus led to the formation of 1,3,4-oxadiazole, [(ppy)2Ir(bPCPC)]PF6 resultantly was used as a "turn-on" chemodosimeter for luminescent detection of Hg2+ in DMF/PBS buffer solution at pH = 7-11. Except for Ag+, recognition capability of [(ppy)2Ir(bPCPC)]PF6 to Hg2+ was not interfered by other common metal ions (Co2+, Li+, Zn2+, Pb2+, K+, Al3+, Na+, Mn2+, Cu2+, Fe2+, Fe3+, Cr3+, Ba2+, Mg2+, Ni2+ and Ca2+). The detection limit was 1.83 × 10-9 mol∙L-1 (0.37 ppb), which indicated the complex was a highly sensitive chemiluminescent detection reagent of Hg2+.

Structural evolution of organic-inorganic hybrid crystals for high colour-rendering white LEDs.

Luminescent crystals with high efficiency have huge potential in applications for white light-emitting diodes (LEDs). Herein, organic-inorganic hybrid crystals doped with Mn4+, [N(CH3)4]2XF6:Mn4+ (X = Si, Ge, and Ti), were grown under mild conditions. Their crystal structural evolution was confirmed by single-crystal X-ray diffraction at different temperatures. These crystals exhibit intense red emission with a high external quantum efficiency (73.0% for [N(CH3)4]2TiF6:Mn4+) and good thermal stability. The warm white LEDs were fabricated by combining these red-emitting phosphors with a YAG:Ce3+ ceramic chip. As-grown crystals can significantly optimize the performances of white LEDs (colour rendering index up to 95). Hence, this work provides a new strategy to explore Mn4+-activated organic-inorganic hybrid materials for white LEDs.

Genome-wide identification and comparative analysis of drought-related microRNAs in two maize inbred lines with contrasting drought tolerance by deep sequencing.

Drought has become one of the most serious abiotic stresses influencing crop production worldwide. Understanding the molecular regulatory networks underlying drought adaption and tolerance in crops is of great importance for future breeding. microRNAs (miRNAs), as important components of post-transcriptional regulation, play crucial roles in drought response and adaptation in plants. Here, we report a miRNome analysis of two maize inbred lines with contrasting levels of drought tolerance under soil drought in the field. Differential expression analysis showed 11 and 34 miRNAs were uniquely responded to drought in H082183 (drought tolerant) and Lv28 (drought sensitive), respectively, in leaves. In roots, 19 and 23 miRNAs uniquely responded to drought in H082183 and Lv28, respectively. Expression analysis of these drought-responsive miRNA-mRNA modules revealed miR164-MYB, miR164-NAC, miR159-MYB, miR156-SPL and miR160-ARF showed a negative regulatory relationship. Further analysis showed that the miR164-MYB and miR164-NAC modules in the tolerant line modulated the stress response in an ABA (abscisic acid)-dependent manner, while the miR156-SPL and miR160-ARF modules in the sensitive line participated in the inhibition of metabolism in drought-exposed leaves. Together, our results provide new insight into not only drought-tolerance-related miRNA regulation networks in maize but also key miRNAs for further characterization and improvement of maize drought tolerance.

A Novel Polymethyl Methacrylate Derivative Grafted with Cationic Iridium(III) Complex Units: Synthesis and Application in White Light-Emitting Diodes.

A novel orange-yellow-emitting polymethyl methacrylate derivative grafted with cationic iridium(III) complex units was synthesized and used as down-conversion luminescent materials in light-emitting diodes (LEDs). The polymer had a thermal decomposition temperature (Td) of 275 °C. With the temperature increasing from 20 to 100 °C, its photoluminescent intensity decreased to 76.8% with thermal quenching activation energy (Ea) of 0.2775 eV. A series of LEDs was fabricated by 460 nm blue GaN chips and the polymer blended in silicone at different concentrations. At 4.0 wt %, a cold white LED was obtained, the correlated color temperature (CCT) was 10,050 K, color rendering index (CRI) was 71.2, luminous efficiency (ηL) was 5.3 lm·w-1, and Commission Internationale de L'Eclairage (CIE) chromaticity coordinates were (0.30, 0.24). At 5.0 wt.%, the LED emitted neutral white light, its CCT was 4938 K, CRI was 75, ηL was 13.8 lm·w-1, and the CIE value was (0.34, 0.27). At 5.5 wt %, 6.0 wt %, 7.0 wt %, and 8.0 wt %, the LEDs all emitted warm white light; their CCTs were 3446, 3093, 2557, and 2337 K, respectively; their CRIs were 73.6, 71.8, 63.8, and 59.0, respectively; their ηL were 18.1, 16.3, 14.8, and 13.7 lm·w-1, respectively; and their CIE values were (0.36, 0.30), (0.40, 0.35), (0.45, 0.38), and (0.50, 0.42), respectively. At 9.0 wt %, the blue light of GaN chip was completely absorbed by the polymer and only the orange-yellow light of the polymer emitted. The results suggested the polymer was a promising orange-yellow-emitting phosphor candidate for white LEDs, especially for warm white LEDs.

Warm White Light-Emitting Diodes Based on a Novel Orange Cationic Iridium(III) Complex.

A novel orange cationic iridium(III) complex [(TPTA)2Ir(dPPOA)]PF6 (TPTA: 3,4,5-triphenyl-4H-1,2,4-triazole, dPPOA: N,N-diphenyl-4-(5-(pyridin-2-yl)-1,3,4-oxadiazol-2-yl)aniline) was synthesized and used as a phosphor in light-emitting diodes (LEDs). [(TPTA)2Ir(dPPOA)]PF6 has high thermal stability with a decomposition temperature (Td) of 375 °C, and its relative emission intensity at 100 °C is 88.8% of that at 25°C. When only [(TPTA)2Ir(dPPOA)]PF6 was used as a phosphor at 6.0 wt % in silicone and excited by a blue GaN (GaN: gallium nitride) chip (450 nm), an orange LED was obtained. A white LED fabricated by a blue GaN chip (450 nm) and only yellow phosphor Y3Al5O12:Ce3+ (YAG:Ce) (1.0 wt % in silicone) emitted cold white light, its CIE (CIE: Commission International de I'Eclairage) value was (0.32, 0.33), color rendering index (CRI) was 72.2, correlated color temperature (CCT) was 6877 K, and luminous efficiency (ηL) was 128.5 lm∙W-1. Such a cold white LED became a neutral white LED when [(TPTA)2Ir(dPPOA)]PF6 was added at 0.5 wt %; its corresponding CIE value was (0.35, 0.33), CRI was 78.4, CCT was 4896 K, and ηL was 85.2 lm∙W-1. It further became a warm white LED when [(TPTA)2Ir(dPPOA)]PF6 was added at 1.0 wt %; its corresponding CIE value was (0.39, 0.36), CRI was 80.2, CCT was 3473 K, and ηL was 46.1 lm∙W-1. The results show that [(TPTA)2Ir(dPPOA)]PF6 is a promising phosphor candidate for fabricating warm white LEDs.

Genome-wide identification of gene expression in contrasting maize inbred lines under field drought conditions reveals the significance of transcription factors in drought tolerance.

Drought is a major threat to maize growth and production. Understanding the molecular regulation network of drought tolerance in maize is of great importance. In this study, two maize inbred lines with contrasting drought tolerance were tested in the field under natural soil drought and well-watered conditions. In addition, the transcriptomes of their leaves was analyzed by RNA-Seq. In total, 555 and 2,558 genes were detected to specifically respond to drought in the tolerant and the sensitive line, respectively, with a more positive regulation tendency in the tolerant genotype. Furthermore, 4,700, 4,748, 4,403 and 4,288 genes showed differential expression between the two lines under moderate drought, severe drought and their well-watered controls, respectively. Transcription factors were enriched in both genotypic differentially expressed genes and specifically responsive genes of the tolerant line. It was speculated that the genotype-specific response of 20 transcription factors in the tolerance line and the sustained genotypically differential expression of 22 transcription factors might enhance tolerance to drought in maize. Our results provide new insight into maize drought tolerance-related regulation systems and provide gene resources for subsequent studies and drought tolerance improvement.

A highly-efficient blue-light excitable red phosphor: intramolecular π-stacking interactions in one dinuclear europium(iii) complex.

A series of ternary dinuclear europium(iii) complexes [Eu2(2,7-BTFDBC)3-n(DBM)2n(Phen)2] (n = 0, 1, or 2) were synthesized by using 2,7-bis(4'4'4'-trifluoro-1,3-dioxobutyl)-(9-ethyl-9H-carbazole) (2,7-BTFDBC), dibenzoylmethane (DBM), 1,10-phenanthroline (Phen) and europium(iii) ions. All these complexes display a broad excitation band in the blue region and high intensity emission with high colour purity. The intensity of emission significantly increases with the increase of DBM in [Eu2(2,7-BTFDBC)3-n(DBM)2n(Phen)2] (n = 0, 1, or 2). The theoretical predictions of the molecular geometry and electronic absorption spectrum of [Eu2(2,7-BTFDBC)(DBM)4(Phen)2] confirm that the pendant phenyl domains engage in multiple T-shaped and parallel-displaced π-stacking interactions with the coordination sphere of two europium(iii) centers. Using [Eu2(2,7-BTFDBC)(DBM)4(Phen)2] as a red phosphor, a single red LED has been obtained with a ∼460 nm-emitting GaN chip.

The Photoluminescent Properties of New Cationic Iridium(III) Complexes Using Different Anions and Their Applications in White Light-Emitting Diodes.

Three cationic iridium(III) complexes [Ir(ppy)2(phen)][PF6] (C1), [Ir(ppy)2(phen)]2SiF6 (C2) and [Ir(ppy)2(phen)]2TiF6 (C3) (ppy: 2-phenylpyridine, phen: 1, 10-phenanthroline) using different anions were synthesized and characterized by ¹H Nuclear magnetic resonance (¹HNMR), mass spectra (MS), Fourier transform infrared (FTIR) spectra and element analysis (EA). After the ultraviolet visible (UV-vis) absorption spectra, photoluminescent (PL) properties and thermal properties of the complexes were investigated, complex C1 and C3 with good optical properties and high thermal stability were used in white light-emitting diodes (WLEDs) as luminescence conversion materials by incorporation with 460 nm-emitting blue GaN chips. The integrative performances of the WLEDs fabricated with complex C1 and C3 are better than those fabricated with the widely used yellow phosphor Y3Al5O12:Ce3+ (YAG). The color rendering indexes of the WLEDs with C1 and C3 are 82.0 and 82.6, the color temperatures of them are 5912 K and 3717 K, and the maximum power efficiencies of them are 10.61 Lm·W-1 and 11.41 Lm·W-1, respectively.