Achieving Dual Emission of Fluorescence and Phosphorescence from Anti-Kasha's Metal-Organic Halides for Information Encryption.

Luminescent materials typically emit their fluorescence or phosphorescence at a specific wavelength with different excitation energies via the so-called Kasha's rule. If fluorescence or phosphorescence emission via anti-Kasha's rule could be achieved, it will hold great promise for applications in many fields. In this work, we report the synthesis and characterization of new metal-organic halide materials with dual emission of efficient room-temperature phosphorescence and fluorescence, which obey anti-Kasha's rule. Here, three emitting metal-organic halides with formula [ZnX2(bidpe)] (X = Cl for 1, X = Br for 2, X = I for 3, bidpe = 4,4'-bis(imidazol-1-yl)diphenyl ether) were prepared and their photophysical properties were investigated. The complexes exhibit dual emission of fluorescence and phosphorescence via anti-Kasha's rule, and their RTP properties of resultant products are modulated by halide substitution synthesis. DFT calculations indicate that the singlet states exhibit a halide-ligand charge transfer (XLCT) character while the triplet states are dominated by the intraligand π-π* transitions. Furthermore, the multilevel information encryption and anticounterfeiting applications are developed by virtue of anti-Kasha's rule emission.

Efficient purging of deleterious mutations contributes to the survival of a rare conifer.

Cupressaceae is a conifer family rich in plants of horticultural importance, including Cupressus, Chamaecyparis, Juniperus, and Thuja, yet genomic surveys are lacking for this family. Cupressus gigantea, one of the many rare conifers that are threatened by climate change and anthropogenic habitat fragmentation, plays an ever-increasing role in ecotourism in Tibet. To infer how past climate change has shaped the population evolution of this species, we generated a de novo chromosome-scale genome (10.92 Gb) and compared the species' population history and genetic load with that of a widespread close relative, C. duclouxiana. Our demographic analyses, based on 83 re-sequenced individuals from multiple populations of the two species, revealed a sharp decline of population sizes during the first part of the Quaternary. However, populations of C. duclouxiana then started to recover, while C. gigantea populations continued to decrease until recently. The total genomic diversity of C. gigantea is smaller than that of C. duclouxiana, but contrary to expectations, C. gigantea has fewer highly and mildly deleterious mutations than C. duclouxiana, and simulations and statistical tests support purifying selection during prolonged inbreeding as the explanation. Our results highlight the evolutionary consequences of decreased population size on the genetic burden of a long-lived endangered conifer with large genome size and suggest that genetic purging deserves more attention in conservation management.

Suppressing the Thermal Quenching Effect via a Cluster Conformer in Copper(I)-Iodide Coordination Polymeric Phosphors for High-Power White LED Lighting.

High-power LED lighting is a crucial challenge due to the notorious thermal quenching (TQ) effect of traditional phosphors at high operating currents, which would result in poor device performance and hamper practical optoelectronic application. Herein, we demonstrate ligand engineering of a cubane- versus staircase-like [Cu4I4] conformer as a node in coordination polymers, which remarkably suppresses the TQ effect of cluster-based photoluminescence. For complex 1 (the formula [Cu4I4(bbimb)2]n) with the cubane-like [Cu4I4] conformer as a node, the metallophilicity interaction enables ultrabright triplet emission with a photoluminescence quantum yield over 82%, and the phonon-assisted detrapping process of excitons effectively suppresses the TQ effect in the wide temperature range. In contrast, the staircase-like [Cu4I4] conformer as a node in complex 2 (the formula [Cu4I4(bbtmb)2]n) exhibits a serious TQ effect over the investigated temperature. Phosphor-converted white LEDs (pc-wLEDs) were fabricated by integrating the cluster-based coordination polymers as a color converter, and their electroluminescence performances were investigated under high bias currents. The prototype pc-wLED device by incorporating the phosphor with the suppressed TQ effect exhibits a continuous rise in brightness under a high bias current of 300 mA. The results demonstrate that ligand engineering of the cluster conformer via suppressing the TQ effect proves efficient in designing an ideal color converter for high-power pc-wLED lighting.

A highly efficient lanthanide coordination polymer luminescent material for the multi-task detection of environmental pollutants.

It is challenging to explore novel-structure lanthanide coordination polymers (Ln-CPs) for sensing environmental pollutants. Herein, we designed and synthesized an organic bridging linker 3-(carboxymethoxy)-1-(carboxymethyl) pyrazole-4-carboxylic acid (H3ccpc), and then successfully prepared and characterized a novel Ln-CP, namely [Tb2(ccpc)2(H2O)6]·1.5H2O (ccpcTb). Structural analysis indicates that ccpcTb exhibits a two-dimensional structure, in which Tb ions are in an eight-coordinated environment. The photoluminescence performance of ccpcTb was discussed in detail. The ccpcTb displays bright green luminescence and behaves as a multi-responsive luminescent sensor toward Fe3+ ions, Cr2O72- ions and 2,4,6-trinitrophenol with high selectivity and low detection limits. Furthermore, the possible luminescence sensing mechanisms have been addressed in detail. The luminescence quenching mechanism of sensing Fe3+ and Cr2O72- is attributed to the energy competitive absorption, while that of sensing TNP is due to the synergistic effect of energy competitive absorption and photo-induced electron transfer.

π-Sticked Metal-Organic Monolayers for Single-Metal-Site Dependent CO2 Photoreduction and Hydrogen Evolution Reaction.

Hierarchical self-assembly of 2D metal-organic layers (MOLs) for the construction of advanced functional materials have witnessed considerable interest, due to the increasing atomic utilizations and well-defined atom-property relationship. However, the construction of atomically precise MOLs with mono-/few-layered thickness through hierarchical self-assembly process remains a challenge, mostly because the elaborate long-range order is difficult to control via conventional noncovalent interaction. Herein, a quadruple π-sticked metal-organic layer (πMOL) is reported with checkerboard-like lattice in ≈1.0 nanometre thickness, on which the catalytic selectivity can be manipulated for highly efficient CO2 reduction reaction (CO2 RR) and hydrogen evolution reaction (HER) over a single metal site. In saturated CO2 aqueous acetonitrile, Fe-πMOL achieves a highly effective CO2 RR with the yield of ≈3.98 mmol g-1  h-1 and 91.7% selectivity. In contrast, the isostructural Co-πMOL as well as mixed metallic FeCo-πMOL exhibits a high activity toward HER under similar conditions. DFT calculations reveal that single metal site exhibits the significant difference in CO2 adsorption energy and activation barrier, which triggers highly selective CO2 RR for Fe site and HER for Co site, respectively. This work highlights the potential of supramolecular π… π interaction for constructing monolayer MOL materials to uniformly distribute the single metal sites for artificial photosynthesis.

Drug-drug interaction prediction based on local substructure features and their complements.

The properties of drugs may undergo changes when multiple drugs are co-administered to treat co-existing or complex diseases, potentially leading to unforeseen drug-drug interactions (DDIs). Therefore, predicting potential drug-drug interactions has been an important task in pharmaceutical research. However, the following challenges remain: (1) existing methods do not work very well in cold-start scenarios, and (2) the interpretability of existing methods is not satisfactory. To address these challenges, we proposed a multi-channel feature fusion method based on local substructure features of drugs and their complements (LSFC). The local substructure features are extracted from each drug, interacted with those of another drug, and then integrated with the global features of two drugs for DDI prediction. We evaluated LSFC on two real-world DDI datasets in worm-start and cold-start scenarios. Comprehensive experiments demonstrate that LSFC consistently improved DDI prediction performance compared with the start-of-the-art methods. Moreover, visual inspection results showed that LSFC can detect crucial substructures of drugs for DDIs, providing interpretable DDI prediction. The source codes and data are available at https://github.com/Zhang-Yang-ops/LSFC.

Spin Manipulation in a Metal-Organic Layer through Mechanical Exfoliation for Highly Selective CO2 Photoreduction.

Spin manipulation of transition-metal catalysts has great potential in mimicking enzyme electronic structures to improve activity and/or selectivity. However, it remains a great challenge to manipulate room-temperature spin state of catalytic centers. Herein, we report a mechanical exfoliation strategy to in situ induce partial spin crossover from high-spin (s=5/2) to low-spin (s=1/2) of the ferric center. Due to spin transition of catalytic center, mixed-spin catalyst exhibits a high CO yield of 19.7 mmol g-1 with selectivity of 91.6 %, much superior to that of high-spin bulk counterpart (50 % selectivity). Density functional theory calculations reveal that low-spin 3d-orbital electronic configuration performs a key function in promoting CO2 adsorption and reducing activation barrier. Hence, the spin manipulation highlights a new insight into designing highly efficient biomimetic catalysts via optimizing spin state.

Multicomponent Anti-Kasha's Rule Emission from Nanotubular Metal-Organic Frameworks for Selective Detection of Small Molecules.

The peak photoluminescence (PL) of conventional fluorophores is independent of the excitation wavelength (called Kasha's rule), while the search of metal-organic framework materials with the so-called anti-Kasha's rule emission remains very limited. Herein, we report the observation of anti-Kasha's rule emission in a multicomponent PL three-dimensional nanotubular metal-organic framework (abbr. MOF-NT), [Zn(µ-L)(µ-bix)]n·0.33nH2O [H2L = biphenyl-3,5-dicarboxylic acid; bix = 1,4-bis(imidazole-1-ylmethyl)benzene]. The MOF-NT crystalline sample represents a notable example of strong excitation-dependent fluorescence from the ultraviolet to the visible spectral region. Moreover, by virtue of electronic flexibility and high PL efficiency, MOF-NT shows a discriminative PL response between isomeric nitroaromatic compounds. The work demonstrated the intrinsic anti-Kasha's rule emission in the crystalline-state MOF materials, providing new visions for the development of advanced solid-state emissive materials.

High-temperature negative thermal quenching phosphors from molecular-based materials.

High-temperature negative thermal quenching (NTQ) phosphors are crucial to high-performance light-emitting devices. Herein, we report the high-temperature NTQ effect in deep-red to near-infrared (NIR) emitting copper iodide cluster-based coordination polymers as unconventional phosphors, whose NTQ operating temperature can reach as high as 500 K, the highest temperature reached by NTQ molecular-based materials.

High-contrast reversible multiple color-tunable solid luminescent ionic polymers for dynamic multilevel anti-counterfeiting.

Dynamic color-tunable luminescent materials, which possess huge potential applications in advanced multilevel luminescence anti-counterfeiting, are of considerable interest. However, it remains challenging to develop simple high-contrast reversible multiple (triple or more than triple) color-tunable high-efficiency solid luminescent materials with low cost, facile synthesis, and good processability. Herein, by simply grafting charged multi-color AIEgen-based chromophores into polymers, a series of high-efficiency multiple color-tunable luminescent single ionic polymers are constructed through tuning feed ratios, counter anions and reaction solvents. Remarkably, some ionic polymers can not only achieve rare high-contrast reversible multiple color-tunable emission in solid states in response to different solvent stimuli, but also could realize excitation-dependent color-tunable emission. To the best of our knowledge, such charming multiple (triple or more than triple) color-tunable solid polymers responding to multiple external stimuli are still rare. Based on comparative studies of emission spectra, excitation spectra and fluorescence lifetimes before and after swelling, it could be inferred that solvent stimuli could induce microstructure changes of these ionic polymers and then change the aggregated-states of their corresponding AIE-active emission centers. Moreover, the different solvent stimuli could induce to produce different degrees of microstructure changes, resulting in their unique multiple color-tunable emission. More significantly, these smart color-tunable ionic polymers show great promise for applications in dynamic multilevel (three-level or even more than three-level) anti-counterfeiting.

A Copper Iodide Cluster-Based Coordination Polymer as an Unconventional Zero-Thermal-Quenching Phosphor.

Phosphor-converted white light-emitting diodes (pc-wLEDs) are promising candidates for next-generation solid-state lighting and display technologies. However, most of the conventional phosphors in pc-wLED devices suffer from serious thermal quenching (TQ) at high temperatures. Herein, we investigate an unconventional high-efficiency metal-halide cluster-based phosphor with dynamic Cu-Cu interactions that can resist the TQ effect of photoluminescence. The temperature-dependent structure and solid-state and in situ NMR spectroscopy reveal that the weakening of the Cu-Cu interaction in such a phosphor system enables the electronic structural transition from a bonding to a nonbonding state and hence sustains the PL efficiency at high temperatures (up to 100 °C). The pc-wLEDs incorporating the zero-TQ phosphor show a rapid brightness rise even at a high bias current (1000 mA) with a color rendering index as high as 90, comparable to the commercial phosphor-based prototype LEDs (e.g., YAG:Ce3+). This work establishes a novel prototype of a cluster-based phosphor featuring dynamic intermetallic interactions, which paves the way for the exploration of pc-wLEDs against thermal quenching.

Roles of Bromodomain Extra Terminal Proteins in Metabolic Signaling and Diseases.

BET proteins, which recognize and bind to acetylated histones, play a key role in transcriptional regulation. The development of chemical BET inhibitors in 2010 greatly facilitated the study of these proteins. BETs play crucial roles in cancer, inflammation, heart failure, and fibrosis. In particular, BETs may be involved in regulating metabolic processes, such as adipogenesis and metaflammation, which are under tight transcriptional regulation. In addition, acetyl-CoA links energy metabolism with epigenetic modification through lysine acetylation, which creates docking sites for BET. Given this, it is possible that the ambient energy status may dictate metabolic gene transcription via a BET-dependent mechanism. Indeed, recent studies have reported that various BET proteins are involved in both metabolic signaling regulation and disease. Here, we discuss some of the most recent information on BET proteins and their regulation of the metabolism in both cellular and animal models. Further, we summarize data from some randomized clinical trials evaluating BET inhibitors for the treatment of metabolic diseases.

A Red-Emitting Cu(I)-Halide Cluster Phosphor with Near-Unity Photoluminescence Efficiency for High-Power wLED Applications.

Solid-state lighting technology, where light-emitting diodes (LEDs) are used for energy conversion from electricity to light, is considered a next-generation lighting technology. One of the significant challenges in the field is the synthesis of high-efficiency phosphors for designing phosphor-converted white LEDs under high flux operating currents. Here, we reported the synthesis, structure, and photophysical properties of a tetranuclear Cu(I)-halide cluster phosphor, [bppmCu2I2]2 (bppm = bisdiphenylphosphinemethane), for the fabrication of high-performance white LEDs. The PL investigations demonstrated that the red emission exhibits a near-unity photoluminescence quantum yield at room temperature and unusual spectral broadening with increasing temperature in the crystalline state. Considering the excellent photophysical properties, the crystalline sample of [bppmCu2I2]2 was successfully applied for the fabrication of phosphor-converted white LEDs. The prototype white LED device exhibited a continuous rise in brightness in the range of a high bias current (100-1000 mA) with CRI as high as 84 and CCT of 5828 K, implying great potential for high-quality white LEDs.

Seeing through the hedge: Phylogenomics of Thuja (Cupressaceae) reveals prominent incomplete lineage sorting and ancient introgression for Tertiary relict flora.

The Eastern Asia (EA) - North America (NA) disjunction is a well-known biogeographic pattern of the Tertiary relict flora; however, few studies have investigated the evolutionary history of this disjunction using a phylogenomic approach. Here, we used 2369 single copy nuclear genes and nearly full plastomes to reconstruct the evolutionary history of the small Tertiary relict genus Thuja, which consists of five disjunctly distributed species. The nuclear species tree strongly supported an EA clade Thuja standishii-Thuja sutchuenensis and a "disjunct clade", where western NA species T. plicata is sister to an EA-eastern NA disjunct Thuja occidentalis-Thuja koraiensis group. Our results suggested that the observed topological discordance among the gene trees as well as the cytonuclear discordance is mainly due to incomplete lineage sorting, probably facilitated by the fast diversification of Thuja around the Early Miocene and the large effective population sizes of ancestral lineages. Furthermore, approximately 20% of the T. sutchuenensis nuclear genome is derived from an unknown ancestral lineage of Thuja, which might explain the close resemblance of its cone morphology to that of an ancient fossil species. Overall, our study demonstrates that single genes may not resolve interspecific relationships for disjunct taxa, and that more reliable results will come from hundreds or thousands of loci, revealing a more complex evolutionary history. This will steadily improve our understanding of their origin and evolution.

Negative/Zero Thermal Quenching of Luminescence via Electronic Structural Transition in Copper-Iodide Cluster-Based Coordination Networks.

Photoluminescence (PL) intensity in organic or metal-organic emitters usually suffers from thermal quenching (TQ), which severely hinders their industrial applications. The development of negative thermal quenching (NTQ) and/or zero thermal quenching (ZTQ) materials depends on a better understanding of the mechanisms underpinning TQ in luminescent solids. In this work, we investigated the temperature dependence of thermally activated delayed fluorescence (TADF) in copper(I)-organic coordination polymers (CP) ligated with an imidazole or triazole derivative over a broad temperature range. The efficient PL emission of CP1 is heavily quenched as the crystalline samples are cooled to 77 K; the PL intensity shows the NTQ effect in the region of 77-238 K followed by a ZTQ effect in the temperature range of 238-318 K. No NTQ or ZTQ effect is observed for reference coordination polymer CP2, where the 1,2,4-triazole group was used instead of the imidazole one. Our work highlights the important role of the ligand's electronic structure in optimizing photophysical properties of coordination polymer emitters and may stimulate new efforts to design luminescent materials exhibiting NTQ and ZTQ effect at higher temperature.

Controlling dynamic magnetic properties of coordination clusters via switchable electronic configuration.

Large-sized coordination clusters have emerged as a new class of molecular materials in which many metal atoms and organic ligands are integrated to synergize their properties. As dynamic magnetic materials, such a combination of multiple components functioning as responsive units has many advantages over monometallic systems due to the synergy between constituent components. Understanding the nature of dynamic magnetism at an atomic level is crucial for realizing the desired properties, designing responsive molecular nanomagnets, and ultimately unlocking the full potential of these nanomagnets for practical applications. Therefore, this review article highlights the recent development of large-sized coordination clusters with dynamic magnetic properties. These dynamic properties can be associated with spin transition, electron transfer, and valence fluctuation through their switchable electronic configurations. Subsequently, the article also highlights specialized characterization techniques with different timescales for supporting switching mechanisms, chemistry, and properties. Afterward, we present an overview of coordination clusters (such as cyanide-bridged and non-cyanide assemblies) with dynamic magnetic properties, namely, spin transition and electron transfer in magnetically bistable systems and mixed-valence complexes. In particular, the response mechanisms of coordination clusters are highlighted using representative examples with similar transition principles to gain insights into spin state and mixed-valence chemistry. In conclusion, we present possible solutions to challenges related to dynamic magnetic clusters and potential opportunities for a wide range of intelligent next-generation devices.

Characteristics and prognosis of acute basilar artery occlusion in minor to moderate stroke and severe stroke after endovascular treatment: A multicenter retrospective study.

OBJECTIVE: We aimed to investigate characteristics and outcomes of patients receiving mechanical thrombectomy (MT) between minor to moderate stroke and severe stroke caused by acute basilar artery occlusion (BAO). METHODS: We retrospectively reviewed the data of all patients with BAO who underwent MT from three stroke centers between January 2016 and January 2020. The patients were dichotomized as minor to moderate or severe stroke group according to their admission National Institutes of Health Stroke Scale (NIHSS) score <21and ≥21. Patient characteristics, imaging findings, and outcomes were compared between the two groups. RESULTS: A total of 72 patients were included in this study. The posterior circulation Alberta Stroke Program Early CT Score (PC-ASPECTS) in the minor to moderate stroke patients were significantly higher than that of patients with severe stroke (P = 0.013). The good posterior circulation collateral scores (PC-CS) (6-10) were more commonly found in patients with minor to moderate stroke than in patients with severe stroke (58.14 % vs 10.34 %,P < 0.001). There were similar rates of successful recanalization between the two groups. Patients with minor to moderate stroke had a higher rate of favorable outcomes (mRS score 0-2, 60.47 % vs 20.69 %, P = 0.002) and a lower rate of periprocedural complications (4.65 % vs 31.03 %, P = 0.005) and mortality (4.65 % vs 24.14 %, P = 0.026) at 3 months after MT compared with the patients with severe stroke. CONCLUSIONS: Acute BAO patients with minor to moderate stroke had better posterior circulation collateral and had better outcomes after MT than those patients with severe stroke.

Ionothermal synthesis of octahedral lanthanoid coordination networks exhibiting slow magnetization relaxation and efficient photoluminescence.

An ionothermal reaction of lanthanoid salts with tetraethyl-p-xylenediphosphonate (tepxdp) in ionic liquids, such as choline chloride and malonic acid, resulted in the formation of three novel lanthanoid-organic coordination networks with the formula [Ln(H2pxdp)1.5]n {Ln = Tb (1), Dy (2) and Ho(3) and H4pxdp = p-xylenediphosphonic acid}. The structures, photoluminescence and magnetic properties of the three compounds were investigated in detail. Single crystal X-ray diffraction analysis revealed that the three compounds are isostructural and the Ln3+ ions show an unusual six-coordinate environment with the {LnO6} octahedron. In these compounds, each {PO3C} tetrahedron is corner-shared with two {LnO6} octahedra and each {LnO6} octahedron is corner-shared with six {PO3C} tetrahedra, thus forming an inorganic layer in the crystallographic ab plane. The inorganic layers are further connected by a phenyl group, leading to a three-dimensional framework. Compound 1 exhibits the strong and characteristic emission of TbIII with an impressive quantum yield of 46.2%. Detailed magnetic analysis demonstrated that compound 2 displays a slow magnetic relaxation of magnetization with multiple relaxation mechanisms. The anisotropic energy barrier and the pre-exponential factor τ0 are 51.2 K and 3.9 × 10-7 s, respectively, in the presence of a direct-current field of 500 Oe. This work demonstrates a successful strategy to isolate octahedrally coordinated lanthanoid complexes through ionothermal synthesis to exhibit the single-ion-magnet-like behaviour and photoluminescence properties.

Azo-Label Heterometal-Organic Rhomboids Exhibiting Photoswitchable NIR Luminescence in Crystalline State.

Photochromism is an important strategy for realizing reversible light-controllable fluorescence switching. In spite of several reports on fluorescence switching via a photochromic process, the success of photochromic multimetallic complexes reversibly showing fluorescence switching in the solid or crystalline state has been limited for their application importance. Here, we report a photoswitchable near-infrared (NIR) fluorescence based on photochromism in the azo-label 3d/4f heterometal-organic rhomboids, azo-Zn2Ln2 (Ln = Eu (1), Yb (2), and Er (3)), in the crystalline state. An individual metallorhomboid contains up to four azobenzene fragments, which is prepared via the three-component assembly of a trans-azobenzene-grafted multifunctional ligand, and 3d and 4f metal ions. The photoisomerization quantum yields of azo-Zn2Ln2 complexes can be retained or even higher when compared to the free ligand due to the modification of electronic structure. The impressive crystalline-state NIR luminescence is observed for the complexes of azo-Zn2Yb2 (2) and azo-Zn2Er2 (3) at room temperature. Intriguingly, the switchable NIR luminescence can be effectively regulated by photochromism in the crystalline state. These features endow the self-assembly of the 3d/4f metallorhomboid with synergetic multifunctional behavior between photochromism and NIR luminescence.

Negative thermal quenching of photoluminescence in a copper-organic framework emitter.

Negative thermal quenching (NTQ), an abnormal phenomenon that the intensity of photoluminescence (PL) increases with increasing temperature, has essentially been restricted to either bulk semiconductors or very low temperatures. Here, we report a delayed fluorescence copper-organic framework exhibiting negative thermal quenching (NTQ) of photoluminescence, which is driven by the fluctuation between the localized and delocalized form of its imidazole ligand. The process is completely reversible on cooling/heating cycles. This study opens a new avenue to explore the electronically switchable NTQ effect in coordination networks and further to develop the NTQ-based light-emitting diodes.