Molecular rotators anchored on a rod-like anionic coordination polymer adhered by charge-assisted hydrogen bonds.

On the basis of variable-temperature single-crystal X-ray diffraction, variable-temperature/frequency dielectric analysis, variable-temperature solid-state nuclear magnetic resonance spectroscopy, and molecular dynamics simulations, here we present a new model of crystalline supramolecular rotor (i-PrNHMe2)[CdBr3], where a conformationally flexible near-spherical (i-PrNHMe2)+ cation functions as a rotator and a rod-like anionic coordination polymer {[CdBr3]-}∞ acts as the stator, and the adhesion of them is realized by charge-assisted hydrogen bonds.

A confinement-regulated (H3C-NH3)+ ion as a smallest dual-wheel rotator showing bisected rotation dynamics.

On the basis of variable-temperature single-crystal X-ray diffraction, rotational energy barrier analysis, variable-temperature/frequency dielectric response, and molecular dynamics simulations, here we report a new crystalline supramolecular rotor (CH3NH3)(18-crown-6)[CuCl3], in which the (H3C-NH3)+ ion functions as a smallest dual-wheel rotator showing bisected rotation dynamics, while the host 18-crown-6 macrocycle behaves as a stator that is not strictly stationary. This study also provides a helpful insight into the dynamics of ubiquitous -CH3/-NH3 groups confined in organic or organic-inorganic hybrid solids.

Unraveling the Mechanism of Cooperative Redox Chemistry in High-Efficient Zn2+ Storage of Vanadium Oxide Cathode.

The inferior capacity and cyclic durability of V2 O5 caused by inadequate active sites and sluggish kinetics are the main problems to encumber the widespread industrial applications of vanadium-zinc batteries (VZBs). Herein, a cooperative redox chemistry (CRC) as "electron carrier" is proposed to facilitate the electron-transfer by capturing/providing electrons for the redox of V2 O5 . The increased oxygen vacancies in V2 O5 provoked in situ by CRC offers numerous Zn2+ storage sites and ion-diffusion paths and reduces the electrostatic interactions between vanadium-based cathode and intercalated Zn2+ , which enhance Zn2+ storage capability and structural stability. The feasibility of this strategy is fully verified by some CRCs. Noticeably, VZB with [Fe(CN)6 ]3- /[Fe(CN)6 ]4- as CRC displays conspicuous specific capacity (433.3 mAh g-1 ), ≈100% coulombic efficiency and superb cyclability (≈3500 cycles without capacity attenuation). Also, the mechanism and selection criteria of CRC are specifically unraveled in this work, which provides insightful perspectives for the development of high-efficiency energy-storage devices.

Temperature-Tuned Variable Confined Space for Modulating Dipolar Polarization of a Disc-Shaped Ammonium Ion.

Free accessible confined space and loose interaction are crucial for most solid-state ionic motions. Here, by using a near-spherical anion and a disc-shaped ammonium as two distinct but rigid building blocks, we report a new ionic crystal, (HMIm)3[La(NO3)6] (HMIm = 1-methyl-1H-imidazol-3-ium), in which the different confined spaces of three (HMIm)+ ions are fine-tuned over a broad temperature range. This effect can be utilized to modulate the dipolar polarization across a wide temperature/frequency range. Additionally, small-scale substitution of (HMIm)+ by its isomer of almost identical shape/size affords molecular solid solutions, which can further tune the dipolar polarization by varying the doping ratio. It is revealed that the differences in dipole moment and hydrogen bond rather than that of shape/size lead to a distorted crystalline environment for these solid solutions. Overall, we provide an exceptional model for understanding and regulating the dipole motion of polar aromatic molecules/ions in a crystalline environment.

Tetra-Nuclear Cluster-Based Lanthanide Metal-Organic Frameworks as White Phosphor, Information Encryption, Self-Calibrating Thermometers, and Fe2+ Sensors.

The application of one kind of metal-organic framework (MOF) material used in multiple fields is one of the most interesting research topics. In this work, four new tetra-nuclear cluster-based lanthanide metal-organic frameworks (LnMOFs) [Ln2(BTDB)3(DMA)(phen)]n (Ln = Tb TbMOF, Eu EuMOF, Gd GdMOF, Tb1.830Eu0.170 Tb,EuMOF, 3,5-bis(trifluoromethyl)-4',4″-dicarboxytriphenylamine = H2BTDB, 1,10-phenanthroline = phen) are obtained based on the ligand of H2BTDB that is synthesized in our laboratory, and the precise single-crystal structure of H2BTDB is obtained for the first time. The white phosphor was obtained by facilely hybridizing two components of the orange-yellow emission phosphor of Tb,EuMOF and the blue luminescence material of triphenylamine according to the trichromatic theory. At the same time, TbMOF, EuMOF, Tb,EuMOF, and the white phosphor can be used for information encryption, demonstrating their potential application in the field of anti-counterfeiting. Tb,EuMOF is also a multi-mode and self-calibrating thermometer within a broad temperature range of 110-300 K. Further studies show that EuMOF is a rapid response sensor for Fe2+, with a very low limit of detection of 2.0 nM, which is much lower than the national standards for Fe2+ (GB 5749-2005, 5.357 µM). It can achieve strong anti-interference detection of Fe2+ in actual samples of tap water and lake water. In addition, EuMOF can also be made into an easy-to-use sensing device of test paper for real-time and visual sensing of Fe2+.

Visual and Real-Time Monitoring of Cd2+ in Water, Rice, and Rice Soil with Test Paper Based on [2 + 2] Lanthanide Clusters.

Cadmium ions (Cd2+) are highly toxic to animal and human health, especially through the drinking of Cd2+-contaminated water and eating Cd2+-contaminated rice. Therefore, accurate detection of Cd2+ in water, rice, and rice soil is urgent. In this work, two [2 + 2] lanthanide clusters of Tb2Tb2 and Eu2Eu2 were synthesized and characterized in detail. Interestingly, Tb2Tb2 is a rapid sensor for Cd2+ through luminescence "turn-off". Further studies show that Tb2Tb2 is a highly sensitive and selective sensor toward Cd2+ in water, rice supernatants, and rice soil supernatants, with a very short response time of 20 s. The limit of detection (LOD) in the above three real samples is as low as 0.0112, 1.1240, and 0.1124 ppb, respectively, which is lower than the national standards for food safety in China (GB 2762-2022). More interestingly, a portable sensing device of test paper based on Tb2Tb2 is developed with a facile method, which shows visible, highly sensitive, and selective sensing toward Cd2+ in real samples of water, rice supernatants, and rice soil supernatants. Tb2Tb2 and its sensing device of test paper are an on-site analysis sensor for potentially non-expert users, especially for people in remote rural areas.

Nanostructured conversion-type anode materials of metal-organic framework-derived spinel XMn2O4 (X = Zn, Co, Cu, Ni) to boost lithium storage.

Bimetallic spinel transition metal oxides play a major part in actualizing eco-friendly electrochemical energy storage systems (ESSs). However, structural precariousness and low electrochemical capacitance restrict their actual implementation in lithium-ion batteries (LIBs). To address these demerits, the sacrificial template approach has been considered as a prospective way to strengthen electrochemical stability and rate performance. Herein, metal-organic frameworks (MOFs) derived XMn2O4-BDC (H2BDC = 1,4-dicarboxybenzene, X = Zn, Co, Cu, Ni) are prepared by a hydrothermal approach in order to discover the effects of various metal cations on the electrochemical performance. Among them, ZnMn2O4-BDC displays best electrochemical properties (1321.5 mAh g-1 at the current density of 0.1 A g-1 after 300 cycles) and high efficiency with accelerated Li+ diffusivity. Density functional theory (DFT) calculations confirm the ZnMn2O4 possesses the weakest adsorption energy on Li+ with a minimized value of -0.92 eV. In comparison with other XMn2O4 through traditional fabrication method, MOF-derived XMn2O4-BDC possesses a higher number of Li+ transport channels and better electric conductivity. This tactic provides a feasible and effective method for preparing bimetallic transition metal oxides and enhances energy storage applications.

Valence Engineering Enhancing NH4 + Storage Capacity of Manganese Oxides.

Ammonium ions (NH4 + ), as non-metallic charge carriers, are attracting attention in aqueous batteries due to its low molar mass, element sufficiency, and non-toxicity. However, the host materials for NH4 + storage are still limited. Herein, an oxygen defects-rich manganese oxide (MnO2-x ) for NH4 + storage are reported. The oxygen defects can endow the MnO2-x sample with improved electric conductivity and low interface activation energy. The electrochemical reaction mechanism is also verified by using ex situ X-ray photoelectron spectroscopy (XPS) and fourier transform infrared spectroscopy (FT-IR), demonstrating the insertion and extraction of NH4 + in the MnO2-x by formation/breaking of a hydrogen bond. As a result, MnO2-x delivers a high capacity of 109.9 mAh g-1 at the current density of 0.5 A g-1 and retention of 24 mAh g-1 after 1000 cycles at the current density of 4 A g-1 , outperforming the pristine MnO2 sample.

Detection of heavy metal ion in real samples with fiber based paper based on new rare earth cluster.

Chromium (Cr) is an important material, but also one of the most toxic heavy metal pollutants, showing great threat to human health and ecological environment, thus, accurate and rapid detection of Cr3+ has far-reaching significance. In this work, based on the ligand of 2,3,4,5,6-pentafluorobenzoic acid (HPFBA) that does not contains oscillation effect group such as "CH, OH, and NH bond", three rare earth dinuclear cluster of Ln2(PFBA)6(phen)2(H2O)2 (Ln = Tb3+1-Tb, Eu3+1-Eu, Gd3+1-Gd, phen = 1,10-phenanthroline) were obtained. 1-Tb shows excellent stability and luminescence properties. In depth investigation reveals that 1-Tb shows quick detection towards Cr3+ in water through luminescence "turn-off", with extremely short response time of 1.0 min, very low limit of detection (LOD) of 5.2 ppb and no interference from other ions. The LOD value is much lower than the total content of chromium for water in China (15 ppm, GB9078-1996). In the actual environment such as tap water, lake water, human, and serum, 1-Tb shows excellent detection and recovery rate for Cr3+. More interestingly, a fiber based paper of test paper that based on 1-Tb and ordinary filter paper was fabricated, which can probe Cr3+ by visible color changes to the naked eye under UV light.

NRF2/HO-1 pathway activation by ATF3 in a noise-induced hearing loss murine model.

BACKGROUND: Excessive oxidative stress of the inner ear as a result of high, intense noise exposure is regarded as a major mechanism underlying the development of noise-induced hearing loss (NIHL). The present study was designed to explore the effect and mechanism of activated transcription factor 3 (ATF3) in reduction/oxidation homeostasis of NIHL. METHOD: In vitro and in vivo assays were performed to investigate the functional role of ATF3 in the inner ear. Mice hearing was measured using auditory brainstem response. ATF3 short hairpin RNA (shRNA) was transfected into House Ear Institute-Organ of Corti 1 (HEI-OC1) cells to decrease ATF3 expression. Western blotting and quantitative real-time polymerase chain reaction (RT-qPCR) were performed to quantify ATF3, NRF2, HO-1 and NQO1 expression. Glutathione (GSH) assay was performed to detect intracellular GSH levels. ATF3 immunofluorescence analysis was carried out in cochlear cryosectioned samples and HEI-OC1 cells to localize ATF3 expression. Cell counting kit 8 assay and flow cytometry were performed to analyze cell viability. RESULT: ATF3 was upregulated in noise-exposed cochleae and HEI-OC1 cells treated with H2O2. NRF2 is a key factor regulated by ATF3. NRF2, HO-1, NQO1, and GSH expression was significantly downregulated in shATF3 HEI-OC1 cells. ATF3 silencing promoted reactive oxygen species accumulation and increased apoptosis and necrosis with H2O2 stimulus. CONCLUSION: ATF3 functions as an antioxidative factor by activating the NRF2/HO-1 pathway.

Highly sensitive sensing device based on highly luminescent lanthanide nanocluster for biomarker in human urine and serum.

The level of L-kynurenine (L-kyn) can reflect the health state of human body, and the determination of L-kyn can be used for the medical diagnosis of several cancers and neurological diseases. In this work, a series of air-, water-, and thermo-stable dinuclear lanthanide nanoclusters [Ln2(2,5-DFBA)6(phen)2] (Tb 1, Eu 2, Gd 3, 2,5-DFBA = 2,5-difluorobenzoic acid, phen = 1,10-phenanthroline) are obtained by a facial method. 1 and 2 show very high luminescence quantum yields (QYs) of 71.7% and 81.8%, respectively. Interestingly, investigation reveals that 1 is a quick, highly sensitive and selective sensor for L-kyn in real samples of urine and serum. Furthermore, transmission electron microscope (TEM) results reveal that nanocluster 1 is stable in solution and can be uniform distributed on the base, suggesting it can be deposited on various supports to fabricate sensing devices. Thus, 1 is fabricated into a sensitive test paper for the eye-readable detection of L-kyn in real samples of human urine and serum. The limit of detection (LOD) as low as 0.3 µM, which is enough to rapidly determine L-kyn in human body liquor (usually 5 µM in healthy human body).

Real-time and visual sensing devices based on pH-control assembled lanthanide-barium nano-cluster.

Real-time and visual monitoring of pollutants in the air is of great importance since they are usually cannot be seen, smelled, or touched. Lanthanide nano-cluster is a kind of luminescent sensor for various species. However, controlling synthesis of lanthanide nano-cluster remains experimentally challenging. In this work, four series of lanthanide-barium (Ln-Ba) nano-clusters of Dy2Ba (1), Tb2Ba2 (2), Ln4Ba3 (Ln = Tb, 3a; Eu, 3b), Tb4Ba4 (4) were assembled through precisely controlling the pH of the reactant solutions. The work features the first example that the number of cluster's nuclei changes regularly with the pH. Moreover, investigation reveals that nano-cluster 3a is a highly selective and sensitive sensor towards acetylacetone (acac) and aniline. Interestingly, easy-to-use sensing devices of test paper, agarose gel, and five kinds of film on CaCO3, polyfoam, coin, mask, and wall that based on 3a were fabricated by facile methods. The seven sensing devices showed remarkable ability to sense aniline and acac vapors with visibility to the naked eyes. This is the first work on multiple real-time and visual sensing devices based on the lanthanide nano-cluster.

Metal-Organic Framework-Derived Hierarchical MnO/Co with Oxygen Vacancies toward Elevated-Temperature Li-Ion Battery.

Transition metal oxides for high-temperature lithium-ion batteries have captivated orchestrated efforts for next-generation high-energy-density anodes. However, due to inherent low tap density, poor conductivity, and structural instability, their poor cyclability capacity and rate performance at elevated temperatures hinder further implementation. Oxygen vacancies (Ov) engineered by manipulating the active sites and electrical conductivity is a promising method for superior lithium storage. Herein, hierarchical MnO/Co nanoparticle-embedded N-doped carbon nanotube (CNT)-assembled carbonaceous micropolyhedrons (Ov-MnO/Co NCPs) are constructed by a "4S" self-assembly, self-template, self-adaptive, and self-catalytic metal-organic framework template method with in situ oxygen vacancies introduced. Impressively, the internal nanoparticles with metallic Co and the external N-doped carbonaceous matrix entangled by fluffy self-generated CNTs synchronously constructed hierarchical micro/nano-secondary hybrids, facilitating highly compacted density, staggered conductive network, multidirectional diffusion pathways, and accelerated electrochemical kinetics. Experimental and density functional theory investigations systematically manifested that the Ov alongside the local built-in electric field within the crystal lattice induced the boosted electrical conductivity, additional active sites, and alleviated structural expansion, further achieving the exceptional diffusivity coefficient and pseudocapacitive capacity. Benefiting from the integrated structural and compositional optimization, the Ov-MnO/Co NCPs achieved distinguished "3C" performance with superior ultralong cyclability (a volumetric capacity of 1713.5 mAh cm-3 at 1 A g-1 up to 1000 cycles), good rate capacity (a well-maintained capacity of 670.2 mAh g-1 even at 10 A g-1), and considerable high-temperature capability at 60 °C.

CNT-Assembled Octahedron Carbon-Encapsulated Cu3P/Cu Heterostructure by In Situ MOF-Derived Engineering for Superior Lithium Storage: Investigations by Experimental Implementation and First-Principles Calculation.

Conspicuously, metal-organic frameworks (MOFs) serve as homogenously and periodically atom-dispersed self-sacrificial template for in situ engineering of hierarchical porous carbon-encapsulated micro/nanoheterostructure materials, integrating the merits of micro/nanostructure to high-volumetric energy storage. Copper phosphide represents a promising candidate due to its compact material density compared to commercial graphite. Herein, micro/nanostructured Cu3P/Cu encapsulated by carbon-nanotube-assembled hierarchical octahedral carbonaceous matrix (Cu3P/Cu@CNHO) is constructed by an in situ MOF-derived engineering for novel anode material in LIBs, which achieves an extraordinary cycling stability (a well-maintained gravimetric/volumetric capacity of 463.2 mAh g-1/1878.4 mAh cm-3 at 1 A g-1 up to 1600 cycles) and distinguished rate capability (an ameliorated capacity of 317.7 mAh g-1 even at 10 A g-1), together with unprecedented heat-resistant capability (an elevated temperature of 50 °C for 1000 cycles maintaining 434.7 mAh g-1 at 0.5 A g-1). The superior electrochemical performance of Cu3P/Cu@CNHO is credited to the large specific surface area, conductive carbon matrix and metallic copper dopants, synergistic effects of the intrinsic Cu3P/Cu heterostructure, and well-defined micro/nanostructure, facilitating a boosted electrochemical conductivity and accelerated diffusion kinetics.

Copper nanowires and copper foam multifunctional bridges in zeolitic imidazolate framework-derived anode material for superior lithium storage.

Herein, a synthetic strategy for growing trimetallic zeolitic imidazolate framework (ZIF) polyhedrons on copper foam (CF) and interweaving with copper nanowires (CNWs) is proposed. Subsequently, in situ annealing under N2 atmosphere leads to the formation of multi-doped CNWs/Cu0.39Zn0.14Co2.47O4-ZnO/CF (CNWs/CZCOZ/CF). The unique structural characteristics of CNWs/CZCOZ/CF allow it to be directly assembled as a working electrode, without additional conductive additives or binders. When it's used as the lithium-ion battery (LIB) anode, this electrode exhibits a significantly high capacity of 2305 mAh g-1 at 0.1 A g-1 after 500 cycles. More importantly, kinetic analysis on the basis of cyclic voltammograms (CVs) indicates that the pseudocapacitive effect is the primary contributor to the high lithium storage capacity and also accounts for the exceptionally high rate capacity of 713 mAh g-1 even if the current density is at a maximum of 10 A g-1. Moreover, the superior battery performance originates from their advantageous structural diversity and unique compositional features, including synergistic effects among polymetallic components and two highly conductive substrates (CNWs and CF), forming unhindered paths for fast charge transfer.

Luminescent lanthanide metal-organic framework test strip for immediate detection of tetracycline antibiotics in water.

Tetracycline antibiotics (TCs) are a kind of commonly used antibiotics for treating infections, however, the overuse of TCs has adversely affected human health and the ecosystem. Thus, detection of TCs in water is important but challenging. In this work, a luminescent lanthanide metal-organic framework (LnMOF) sensor (1) for immediate detection of oxytetracycline (OTC) and tetracycline (TC) is developed. The sensor has high acid-base and water stability. Investigation reveals that among the 27 species of antibiotics, anions and cations under investigation, 1 shows highly selective sensing towards OTC and TC, and the detection is not disturbed by the presence of other species. The limit of detection (LOD) for OTC and TC are ultra-sensitive value of 1.95 and 2.77 nM, respectively. Investigation reveals the sensing mechanism is due to the inner filter effect. Further studies reveal that the sensor can be used in real sample monitoring. More importantly, test strips based on 1 are manufactured. They are an easy-to-use, low-cost, highly selective and sensitive sensing device for detecting OTC and TC. The sensing can be distinguished immediately and easily by the naked eyes, making it an excellent candidate to monitor OTC and TC in real use.

Analysis on spatial-temporal distribution characteristics of smear positive pulmonary tuberculosis in China, 2004-2015.

BACKGROUND: In China, tuberculosis (TB) is still a major infectious disease threatening people's health. Smear positive pulmonary TB is one of the most common infectious forms of TB and it might easily cause the outbreak in some areas. With a better understanding of the spatial-temporal variations of smear positive PTB, we would reach the targets for TB prevention and controlling, identify high-risk areas and periods. Thus, the aim of this study was to investigate the spatial-temporal variations of smear positive PTB. METHODS: Provincial level data of reported smear positive PTB monthly cases and incidence from January 2004 to December 2015 were obtained from the National Scientific Data Sharing Platform for Population and Health of China. Purely spatial-temporal descriptive analysis was used to characterize the distribution patterns of smear positive PTB. The global spatial auto-correlation statistics (Moran's I) and the local indicators of spatial association (LISA) were conducted to identify the spatial auto-correlation and high risk areas of smear positive PTB cases. Furthermore, the space-time scan statistic was adopted to detect the spatial-temporal clusters in different periods. RESULTS: A total of 4,711,571 smear positive PTB cases were notified in China with an average annual incidence of 29.59/100,000. The proportion of male in different age groups were obviously higher than that of women. The largest number of cases was reported in the 20-24 years age group. Time-series analysis indicated that monthly incidence appeared a clearly seasonality and periodicity, which the seasonal peaks occurred in January and March. Smear positive PTB cases had a positive global spatial auto-correlation in 2013-2015 (Moran's I=0.186, P=0.046). Spatial clusters were identified in four periods, located in the different regions. The time period of 2004-2006, the most likely spatial-temporal cluster (RR=1.69, P<0.001) was mainly located in Hubei, Hunan, Jiangxi and Anhui of central China, clustering in the time frame from January 2005 to June 2006. During 2007-2009, the most likely spatial-temporal cluster (RR=5.65, P<0.001) was located in Guizhou, clustering in the time frame from January to December 2009. The spatial-temporal clustering in the years 2010-2012 showed the most likely cluster (RR=1.44, P<0.001) was distributed in Anhui, Hunan, Hubei, Jiangxi and Guangdong with the time frame from January 2010 to June 2011. During 2013-2015, the most likely cluster (RR=1.86, P<0.001) was detected in Hunan, Hubei, Jiangxi and Guangdong from February 2013 to June 2014. CONCLUSIONS: This study identified the spatial-temporal patterns of smear positive PTB in China and demonstrated the capability and utility of the spatial-temporal approach in epidemiology. The results of this study would contribute to estimating the high risk periods and areas, and to providing more useful information for policy-making.

Ultrahigh luminescence quantum yield lanthanide coordination polymer as a multifunctional sensor.

The investigation and development of advanced multifunctional and sensitive sensors with high luminescent quantum yield and the capability of detecting different analytes, such as metal ions, is imperative. Due to its inherent properties the lanthanide coordination complex is one candidate for sensing applications, particularly for multifunctional sensors. Herein, we present two series of alkali ion decorated lanthanide coordination polymers (Ln-CPs), which show ultrahigh luminescence quantum yields (QYs) of 77% (1a) and 92% (2a). To the best of our knowledge, 1a represents the first trifunctional lanthanide complex sensor that can simultaneous detect and discriminate three different analytes, namely H+/Cd2+/Cr3+ through a multimode optical response. Furthermore, the limit of detection (LOD) for Cr3+ is an ultralow value of 2.0 × 10-9 M with a sensing time of 2 h, which is comparable to the most sensitive Cr3+ chemosensor. More interestingly, 92% (2a) is an unprecedented luminescence QY among the reported lanthanide coordination complexes.

Detailed structure information a highly thermostable Tb-cluster that based on a prodrug ligand of 2,4,5-trifluoro-3-methoxybenzoic acid.

In this brief data article, we present the precise structural information, PARD data and thermographic analysis of the Tb-cluster. Detailed structure, luminescence and detecting properties were discussed in our previous study (Zhao et al., 2017) [1]. The data includes the coordination modes of ligand, PXRD patterns of these Ln-MOFs, thermostability, detailed bond lengths and bond angles of the Tb-cluster.

Structural data of structure variation and luminescence of 3D, 2D and 1D lanthanide coordination polymers with 1,3-adamantanediacetic acid.

In this data article, we report the structure, Fourier transform infrared spectroscopy(FT-IR), powder X-ray diffraction (PARD), luminescence decay, thermogravimetric analysis (TGA) and UV-vis data of three series Ln-MOFs. Detailed structure and luminescence properties were discussed in our previous study (Zhao et al., 2018) [1]. The data includes the structure patterns of ligand H2ADA, FT-IR, PXRD and thermostability of Ln-MOFs in the air, detailed structure information for these structures are listed in Table 1, Table 2, Table 3, Table 4, Table 5, Table 6, Table 7.