LncRNA ZFAS1 Alleviated NLRP3 Inflammasome-Mediated Pyroptosis through Regulating miR-96-5p/Smad7 Signaling in Allergic Rhinitis.

INTRODUCTION: The NLR family pyrin domain containing 3 (NLRP3)-mediated pyroptosis was positively correlated with the allergic rhinitis progression and was reported to be regulated by SMAD family member 7 (Smad7). Bioinformatics analysis revealed that Smad7 might be targeted by miR-96-5p, and miR-96-5p might be targeted by long noncoding RNA zinc finger antisense 1 (ZFAS1). However, the effects and regulatory mechanisms of the ZFAS1/miR-96-5p/Smad7 functional axis in allergic rhinitis have not been investigated. METHODS: Human nasal mucosa epithelial cell line RPMI 2650 and C57BL/6 mice were obtained for in vitro and in vivo studies. Dual-luciferase reporter assay and RNA immunoprecipitation were implemented for detecting molecular interactions. Cell counting kit-8 and flow cytometry were used for measuring cell viability and pyroptosis. ELISA was obtained for monitoring cytokine secretion. RT-qPCR and Western blot were examined for determining RNA and protein expression. RESULTS: In vitro studies revealed that ZFAS1 was downregulated in interleukin (IL)-13-treated RPMI 2650 cells, while overexpression of ZFAS1 enhanced cell viability and inhibited NLRP3-mediated pyroptosis and inflammatory response. ZFAS1 directly inhibited miR-96-5p to suppress NLRP3-mediated pyroptosis in IL-13-treated RPMI 2650 cells. MiR-96-5p bound to the 3'-untranslated region of Smad7 and knockdown of Smad7 significantly reversed the effects of miR-96-5p depletion. Moreover, in vivo experiments further confirmed the findings of in vitro studies and showed ZFAS1 overexpression or miR-96-5p inhibition alleviated allergic rhinitis in vivo. CONCLUSION: ZFAS1 downregulated the expression of miR-96-5p to upregulate Smad7 level, which subsequently inhibited NLRP3-mediated pyroptosis and inflammatory response to ameliorate allergic rhinitis.

Dual Photo-/Electrochromic Pyromellitic Diimide-Based Coordination Polymer.

By the combination of N,N'-bis(carboxymethyl)-pyromellitic diimide (H2CMPMD, 1) and zinc ions, a novel PMD-based coordination polymer (CP), [Zn(CMPMD)(DMF)1.5]·0.5DMF (2) (DMF = N,N'-dimethylformamide), has been prepared and characterized. 1 and 2 exhibit completely different photochromic properties, which are mainly reflected in the photoresponsive rate (5 s for 1 vs 1 s for 2) and coloration contrast (from colorless to light green for 1 vs green for 2). This phenomenon should be attributed to the introduction of zinc ions and the consequent formation of the distinct interfacial contacts of electron donors (EDs) and electron acceptors (EAs) (dn-π = 3.404 and 3.448 Å for 1 vs dn-π = 3.343, 3.359, 3.398, and 3.495 Å for 2), suggesting a subtle modulating effect of metal ions on interfacial contacts, photoinduced intermolecular electron transfer (PIET) and photochromic behaviors. Interestingly, the photochromic performance of 2 can be enhanced after the removal of coordinated DMF, which might be ascribed to the decrease of the distance of EDs/EAs caused by lattice shrinkage, which further improves the efficiency of PIET. Meanwhile, 2 displays rapid electrochromic behavior with an obvious reversible color change from colorless to green, which can be used in an electrochromic device. This work develops a new type of EA for the construction of stimuli-responsive functional materials with excellent dual photo-/electrochromic properties.

Size Effect of Arylenediimide π-Conjugate Systems on the Photoresponsive Behaviors in Eu3+-Based Coordination Polymers.

Various arylenediimides (ADIs) have been applied to construct photoresponsive coordination polymers (CPs), while the size effect of ADI π-conjugate systems on the photoresponsive behaviors in CPs has been overlooked in the past few years. Herein, we emphasize the size effect of ADI π-conjugate systems on photoinduced electron transfer (ET) in CPs, taking two Eu3+-based CPs, [Eu(H2BINDI)(BINDI)0.5(H2O)2]·NH2(CH3)2·8H2O (1) and [Eu2(BIPMDI)(DMF)4(NO3)2]·H2O·2DMF (2) [H4BINDI = N,N'-bis(5-isophthalic acid)naphthalenediimide; H4BIPMDI = N,N'-bis(5-isophthalic acid)pyromellitic diimide; DMF = N,N-dimethylformamide], as a case. Both 1 and 2 display ET-based photochromic behaviors with distinct photoresponsive rates and coloration contrast, which can contribute to the size effect of diimide cores on the interfacial contacts of electron donors/acceptors. Meanwhile, ET between the neighboring larger NDI cores of the H4BINDI ligands can block ligand-to-metal charge transfer and quench luminescence of the Eu3+ metal center in 1. Therefore, this work will provide a theoretical basis for the development and exploration of photoresponsive materials.

Lattice Water Controlled Photo- and Thermochromism of N-Protonated Carbomethoxypyridinium Iodoargentate Hybrids.

Two iodoargentate hybrids, {[HNOM][AgI2]·H2O} (1) and {[HINOM][AgI2]·H2O} (2) (HNOM+ = N-protonated 3-carbomethoxypyridinium; HINOM+ = N-protonated 4-carbomethoxypyridinium), have been designed and prepared, which were constructed from typical [AgI2]- inorganic chains and cationic hydrogen-bonding supramolecular networks (one-dimensional for 1 and three-dimensional for 2) of lattice water and positional isomeric N-protonated carbomethoxypyridinium. Two hybrids exhibit sensitive photochromism based on intermolecular electron transfer (ET) and thermochromism due to reversible hydration and dehydration and the consequent variation of intermolecular charge transfer (CT). Furthermore, loss of lattice water gives rise to improved photochromic dehydrated form 1T and optically inert dehydrated form 2T, suggesting a delicate modulating effect of lattice contraction on the intermolecular CT and ET as well as consequently photoresponsive behaviors.

Bipyridyltriazolium Chlorobismuthate with Thermo-/Photochromic and Photoluminescent Switching Behaviors Based on ET and CT†.

Matched with 3,5-bis(pyridine-2-yl)-1,2,4-triazole (2-bpt), a new electron donor-acceptor-based chlorobismuthate(III) hybrid, [2-bpt]2[Bi2Cl10(H2O)]·5H2O was prepared solvothermally and characterized. The title compound (hydrated form) and its dehydrated form exhibit photo- and thermo-induced intermolecular electron transfer (ET), which correspond to dual ET photo/thermochromism for hydrated form, charge transfer thermochromism during dehydration, and simultaneously photoluminescent responses, respectively.

Ultrasensitive Photochromic Iodocuprate(I) Hybrid.

By employing in situ methylnicotinohydrazide dication (MNH(2+)) as an electron acceptor, we have constructed an iodocuprate(I) hybrid {[MNH][Cu2I3]2}n (1), which exhibits charge transfer (CT) thermochromism due to the intense absorption of CT and electron transfer (ET) photochromism with high photocoloration contrast and fast response to UV irradiation due to the synergetic effect of valence change of copper ions.

Ultrahigh power factor and enhanced thermoelectric performance of individual Te/TiS2 nanocables.

Here, we present the successful fabrication of Te/TiS2 heterostructure nanocables with enhanced thermoelectric (TE) performance by a two-step route (a facile solvothermal approach for Te nanowires and then the Te nanowires are used as templates for the controllable growth of the Te/TiS2 nanocables), which is scalable for practical nanodevice applications. The heterostructure nanocables of different sizes can be prepared by varying the synthetic composition. Measurements of the Seebeck coefficient (S), electrical conductivity (σ), and thermal conductivity (κ) are carried out on the same nanowires over a temperature range of 2-350 K. The heterostructure nanocables show an ultrahigh power factor (S(2) σ) with a maximum value of 0.58 Wm(-1) K(-2), which comes from a high electrical conductivity and a strongly enhanced Seebeck coefficient. The figure of merit (ZT) can reach 1.91 at room temperature from a single nanocable with a diameter of 60 nm, which is thought to contribute to the formation of the hetero-phase core/shell structure. These results are expected to open up new application possibilities in nanoscale TE devices based on individual Te/TiS2 heterostructure nanocables.

Symmetrically Related Construction and Optical Properties of Two Noncentrosymmetric 3D Iodides of d(10) Cation (Cu(+), Ag(+)) Based on the N-Benzylpyridinium and Its Supramolecular Interactions.

Two noncentrosymmetric compounds, namely, [N-Bz-Py]2[Cu6I8] (1) and [N-Bz-Py]4[Ag9I13] (2) (N-Bz-Py(+) = N-benzylpyridinium), with three-dimensional open frameworks, were synthesized solvothermally via in situ benzylation of pyridine. 1 is constructed from 3-connected Cu3I7 secondary building units (SBUs) with chiral (10,3)-a topology, while the occluded N-Bz-Py(+) forms a complementary supramolecular (10,3)-a net via π-π interactions. 2 is characteristic of acentric connections of trimeric Ag3I8 and hexamer Ag6I12 SBU, while N-Bz-Py(+) in the channels aggregates into asymmetrically supramolecular chains via π-π interactions. Remarkable structural correlations imply the unique amplification and transfer of asymmetric information from V-shaped N-Bz-Py(+) to organic supramolecular nets and inorganic frameworks, which are confirmed by their second harmonic generation responses. Adsorption spectra reveal their semiconductive nature (2.52 eV for 1 and 3.02 eV for 2) and interesting reversible thermochromism for 1 based on the intermolecular charge transfer.

Supramolecular interaction of two tryptophans with p-sulfonated calix[4,6,8]arene.

The complex characteristics of p-sulfonated calix[n]arene (SCnA) and two tryptophans N-[(tert-butoxy) carbonyl]-tryptophan (trp-A) and N-carbobenzoxy-tryptophane (trp-B) were examined through various techniques. Spectrofluorimetry was performed at different temperatures to determine the stability constants and evaluate the thermodynamic parameters of the two complexes. The effect of pH on complex formation was estimated. According to the fluorescence data, the assumption about the steric hindrance of the tert-butyl group of trp-A and the phenyl group of trp-B was put forward. (1)H NMR was also performed to determine the binding interaction mechanism. Results showed that the indole benzene rings of the two tryptophans partly penetrated into the cavity of p-sulfonated calix[n]arene. The shift in Ha, Hb and Hc, Hd positions became more significant as the number of phenolic units of the calixarene ring increased. Molecular modeling of the complexes elucidated the assumption about the steric hindrance of the tert-butyl group of trp-A and the phenyl group of trp-B. These observations of molecular modeling computation are consistent with previous fluorescence data and (1)H NMR results.

The human microbiome and benign prostatic hyperplasia: Current understandings and clinical implications.

The research of the human microbiome in the preceding decade has yielded novel perspectives on human health and diseases. Benign prostatic hyperplasia (BPH) is a common disease in middle-aged and elderly males, which negatively affects the life quality. Existing evidence has indicated that the human microbiome, including urinary, intra-prostate, gut, oral and blood microbiome may exert a significant impact on the natural progression of BPH. The dysbiosis of the microbiome may induce inflammation at either a local or systemic level, thereby affecting the BPH. Moreover, metabolic syndrome (MetS) caused by the microbiome can also be involved in the development of BPH. Additionally, alterations in the microbiome composition during the senility process may serve as another cause of the BPH. Here, we summarize the influence of human microbiome on BPH and explore how the microbiome is linked to BPH through inflammation, MetS, and senility. In addition, we propose promising areas of investigation and discuss the implications for advancing therapeutic approaches.

Epigenetic-related gene-based prognostic model construction and validation in prostate adenocarcinoma.

Prostate adenocarcinoma (PRAD), driven by both genetic and epigenetic factors, is a common malignancy that affects men worldwide. We aimed to identify and characterize differentially expressed epigenetic-related genes (ERGs) in PRAD and investigate their potential roles in disease progression and prognosis. We used PRAD samples from The Cancer Genome Atlas (TCGA) and Gene Expression Omnibus (GEO) to identify prognosis-associated ERGs. Thirteen ERGs with two distinct expression profiles were identified through consensus clustering. Gene set variation analysis highlighted differences in pathway activities, particularly in the Hedgehog and Notch pathways. Higher epigenetic scores correlated with favorable prognosis and improved immunotherapeutic response. Experimental validation underscored the importance of CBX3 and KAT2A, suggesting their pivotal roles in PRAD. This study provides crucial insights into the epigenetic scoring approach and presents a promising prognostic tool, with CBX3 and KAT2A as key players. These findings pave the way for targeted and personalized interventions for the treatment of PRAD.

Determination of paraquat in water samples using a sensitive fluorescent probe titration method.

Paraquat (PQ), a nonselective herbicide, is non-fluorescent in aqueous solutions. Thus, its determination through direct fluorescent methods is not feasible. The supramolecular inclusion interaction of PQ with cucurbit[7]uril was studied by a fluorescent probe titration method. Significant quenching of the fluorescence intensity of the cucurbit[7]uril-coptisine fluorescent probe was observed with the addition of PQ. A new fluorescent probe titration method with high selectivity and sensitivity at the ng/mL level was developed to determine PQ in aqueous solutions with good precision and accuracy based on the significant quenching of the supramolecular complex fluorescence intensity. The proposed method was successfully used in the determination of PQ in lake water, tap water, well water, and ditch water in an agricultural area, with recoveries of 96.73% to 105.77%. The fluorescence quenching values (deltaF) showed a good linear relationship with PQ concentrations from 1.0 x 10(-8) to 1.2 x 10(-5) mol/L with a detection limit of 3.35 x 10(-9) mol/L. In addition, the interaction models of the supramolecular complexes formed between the host and the guest were established using theoretical calculations. The interaction mechanism between the cucurbit[7]uril and PQ was confirmed by 1H NMR spectroscopy.

The modulation effect of auxiliary ligands on photochromic properties of 3D naphthalene diimide coordination polymers.

Two novel naphthalene diimide (NDI) coordination polymers (CPs), [Cd(NicNDI)(4,4'-SBC)] (1) and [Cd(NicNDI)(2,2'-BPC)] (2) (NicNDI = (3-pyridylacylamino)-1,4,5,8-naphthalene diimide, 4,4'-SBC = 4,4'-stilbene dicarboxylic acid, 2,2'-BPC = 2,2'-biphenyl dicarboxylic acid), were designed and prepared by the combination of electron-deficient NicNDI and electron-rich aromatic carboxylic acid ligands in the presence of cadmium ions. The usage of aromatic carboxylic acid ligands with different conjugation degrees, sizes, shapes and charge densities leads to the generation of distinct interpenetrated three-dimensional (3D) frameworks. Interestingly, photochromism of 1 and weak photoactivity of 2 should be attributed to the introduction of different auxiliary ligands and consequently the formation of distinct interfacial contacts of electron donors (EDs)/electron acceptors (EAs) (dπ-π = 3.427 Å, infinite -ED-EA-ED-EA- for 1vs. dπ-π = 3.634 Å, discrete ED-EA-ED for 2), suggesting a subtle modulating effect of auxiliary ligands on interfacial contacts, photoinduced intermolecular electron transfer (PIET) and photoresponsive behaviors.

The effect of conjugation degree of aromatic carboxylic acids on electronic and photo-responsive behaviors of naphthalenediimide-based coordination polymers.

Three novel naphthalenediimide-based (NDI-based) coordination polymers (CPs), namely [Cd(3-PMNDI)(2,2'-BPDC)] (1), [Cd2(3-PMNDI)1.5(4,4'-BPDC)2(H2O)3]·DMF (2) and [Cd(3-PMNDI)(4,4'-SDC)] (3) (2,2'-H2BPDC = 2,2'-biphenyldicarboxylic acid, 4,4'-H2BPDC = 4,4'-biphenyldicarboxylic acid, 4,4'-H2SDC = 4,4'-stilbenedicarboxylic acid, 3-PMNDI = N,N'-bis(3-pyridylmethyl)-1,4,5,8-naphthalenediimide, and DMF = N,N'-dimethylformamide), have been designed and synthesized here from electron-deficient PMNDI (electron acceptors, EAs) and electron-rich aromatic carboxylic acids (electron donors, EDs) in the presence of cadmium ions. The introduction of aromatic carboxylic acids with different sizes and conjugation degrees leads to the generation of a two-dimensional (2D) layer in 1, a two-fold interpenetrated three-dimensional (3D) network in 2 and an eight-fold interpenetrated 3D framework in 3. Furthermore, the use of distinct electron-donating aromatic carboxylic acids and the consequent different numbers and strengths of lone pair-π and π-π interactions in the interfacial contacts of EDs/EAs give rise to distinct intermolecular charge transfer (ICT) and initial colors of the three CPs, and consequently cause different photoinduced intermolecular electron transfer (PIET) and distinguishing photo-responsive behaviors (weak photochromic performance for 1, excellent photochromic properties for 2 and non-photochromism for 3). This study indicates that an appropriate ICT is beneficial for PIET, but too weak or too strong ICT is not conducive to PIET, which provides an effective strategy for the construction of functional CPs with distinguishing photo-responsive properties through the subtle balance of ICT and PIET.

Electron density effect of aromatic carboxylic acids in naphthalenediimide-based coordination polymers: from thermal electron transfer and charge transfer to photoinduced electron transfer.

Various naphthalenediimide (NDI) based electron donor-acceptor coordination polymers (D-A CPs) have been constructed and used to explore charge transfer (CT) and electron transfer (ET) behaviors. Up to now, significant progress has been made in the interface contact and electron donor-acceptor ability matching mechanism, while the electronic density effect of the electron donors on the CT and ET behaviors is still not known. Herein, two NDI-based D-A CPs, [Cd2(H2NDI)(IPA)2(H2O)2] (1) and [Cd2(H2NDI)(IPA-OH)2(H2O)2] (2), are constructed using an NDI-based ligand and two aromatic carboxylic acid ligands (H2NDI = 2,7-bis(3,5-dimethyl) dipyrazol-1,4,5,8-naphthalene tetracarboxydiimide, H2IPA = isophthalic acid; and H2IPA-OH = 5-hydroxyisophthalic acid). UV-vis and EPR spectroscopy and DFT calculations analyses reveal that the occurrence of themal electron transfer (TET) in 1 and 2 results from the HOMO of the IPA and IPA-OH lying higher than the LUMO of the NDI. Meanwhile, compared to 1, the UV-vis absorption spectrum of 2 exhibits a significant red shift, which suggests higher electron density of the donor and more electron transfer pathways are beneficial for the occurrence of intermolecular CT. After UV light irradiation, the comparison of the photochromic behavior of 1 and 2 confirms the negative effect of the stronger CT on photoinduced electron transfer (PET). The present study illustrates the delicate modulating effect of electron density on the CT and ET behaviors in D-A CPs.

The modulation effect of carboxylic acid ligands on the electron transfer photochromism of NDI-derived coordination polymers.

Four naphthalene diimide (NDI)-derived coordination polymers (CPs), [Cd(3-DPNDI)(o-BDC)] (1), [Cd(3-DPNDI)2(p-BDC)(NO3)] (2), [Cd(3-DPNDI)(NDC)(H2O)2] (3), [Cd(3-DPNDI)(BPC)(H2O)] (4) (3-DPNDI = N,N'-di-(3-pyridyl)-1,4,5,8-naphthalene diimide, o-BDC = phthalic acid, p-BDC = terephthalic acid, NDC = 2,6-naphthalenedicarboxylic acid, BPC = biphenyl-4,4'-dicarboxylic acid), have been designed and prepared. The usage of carboxylic acid ligands with different sizes, shapes and charge densities leads to the distinct resultant architectures of four CPs and divergent weak interactions (lone pair⋯π, π⋯π and C-H⋯π interactions) of electron donors/acceptors, which further lead to the completely different photoinduced electron transfer (PET) and consequent photochromic properties. More specifically, 1 and 2 display excellent photochromic behaviors with a fast photoresponsive rate and high coloration contrast, which are attributed to the suitable interfacial contacts of electron donors/acceptors. However, 3 and 4 are basically optical inert, which could be attributed to the negative effect of the stronger charge transfer (CT) on PET. The present study illustrates the delicate modulating effect of carboxylic acid ligands on the resultant networks, interfacial relationship and PET together with photoresponsive behaviors.

An electron-deficient naphthalene diimide-based metal-organic framework for detecting electron-rich molecules through photo-/chemo-induced chromism.

A novel naphthalene diimide-based metal-organic framework (MOF) {[Zn(3-DPMNI)0.5(NDC)]·3DMF} (1@DMF), (H2NDC = 2,6-naphthalenedicarboxylic acid, DPMNI = N,N'-bis(3-pyridylmethyl)-1,4,5,8-naphthalene diimide, DMF = N,N'-dimethylformamide), has been synthesized, which shows a 3D pillar-layer architecture built of carboxylate layers and naphthalene diimide pillars. The compound exhibits outstanding photochromic performance due to photoinduced electron transfer (ET) between the electron-rich guest molecules and electron-deficient host framework (host-guest ET). Of note, the host framework of 1 cannot show a macroscopic color change owing to the absence of the ET pathway. Nevertheless, it exhibits discriminative photochromic behavior in the presence of electron-rich solvents, which is mainly attributed to different electron-donating abilities of guest solvents and distinct interfacial contacts of electron donors/acceptors. Furthermore, the MOF can also show discriminative ET chemochromic response to different sizes and shapes of organic amines, which can be potentially used for the visual detection of electron-rich organic amines, especially n-butylamine (n-BUA).

In Situ Formation of Laser-Cladded Layer on Thin-Walled Tube of Aluminum Alloy in Underwater Environment.

The first study of thin-walled aluminum-alloy tubes with underwater-laser-nozzle in situ melting technology was carried out. The study mainly covered the influence of the water environment on the laser melting process, melting appearance, geometric characteristics, microstructure, regional segregation and microhardness. During the transfer of the cladding environment from air to water, the uniformity of the cladding layer became poor, but excellent metallurgical bonding was still obtained. The dilution rate (D) decreased from 0.46 to 0.33, while the shape factor (S) increased from 4.38 to 5.98. For the in-air and underwater samples, the microstructure of the melting zone (MZ) and the cladding zone (CZ) were columnar dendrites and equiaxed grains, respectively. In addition, the microstructure of the overlapping zone (OZ) was composed of columnar dendrites and equiaxed grains. The underwater average grain size was smaller than that of in-air. In addition, the water environment was beneficial for reducing the positive segregation in the columnar dendrite region. Compared with the in-air cladding sample, the precipitated phases in the OZ of the underwater cladding sample reduced. Under the combined action of grain refinement and precipitated phase reduction, the microhardness value of the underwater OZ was higher than that of the in-air OZ.

Photochromic and luminescent switchable iodoargentate hybrids directed by solvated lanthanide cations.

Four iodoargentate hybrids, [Eu(DMSO)8]2[Ag2I5][Ag5I8] (1), [Eu(DMSO)8][Ag7I10] (2), [Tb(DMSO)8]2[Ag2I5][Ag5I8] (3) and [Tb(DMSO)8][Ag6I9] (4) (DMSO = dimethyl sulfoxide), have been rationally synthesized, which display simultaneous photochromic and luminescent switchable performances. Photochromism is due to the photolysis of iodoargentate anions and the consequent generation of Ag0 particles with surface plasmon resonance (SPR) absorption. Meanwhile, luminescent switchable performance is ascribed to intermolecular fluorescence resonance energy transfer (FRET) from fluorescent solvated lanthanide cations to photochromic iodoargentate anions.

Non-transient thermo-/photochromism of iodobismuthate hybrids directed by solvated metal cations.

Two iodobismuthate-based organic-inorganic hybrids, [M(DMSO)8][Bi2I9] (M = La (1), Bi (2)), have been successfully designed and synthesized by using solvated metal cations as structure-directing agents (SDAs). 1 displays transient high-temperature thermochromism, which is similar to that of the characteristic low-temperature thermochromic properties of bulk bismuth iodide and iodobismuthate hybrids. In contrast, 2 exhibits distinguishing non-transient thermochromic properties stimulated by the different temperature ranges of the thermal treatments. More importantly, a comparison of the optical inertness of 1 and 2 also reveals novel photochromic behavior. The completely different thermo-/photo-responsive properties of 1 and 2 are mainly ascribed to the different binding abilities of the central metal cations with DMSO molecules, which cause a distinct transformation of the inorganic moiety and consequent modulation of band gaps.