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Carborane compounds, known for their exceptional thermal stability and non-toxic attributes, have garnered widespread utility in medicine, supramolecular design, coordination/organometallic chemistry, and others. Although there is considerable interest among chemists, the integration of suitable carborane molecules into ferroelectric materials remains a formidable challenge. In this study, we employ the quasi-spherical design strategy to introduce functional groups at the boron vertices of the o-carborane cage, aiming to reduce molecular symmetry. This approach led to the successful synthesis of the pioneering ferroelectric crystals composed of cage-like carboranes: 9-OH-o-carborane (1) and 9-SH-o-carborane (2), which undergo above-room ferroelectric phase transitions (T c ) at approximately 367 K and 347 K. Interestingly, 1 and 2 represent uniaxial and multiaxial ferroelectrics respectively, with 2 exhibiting six polar axes and as many as twelve equivalent polarization directions. As the pioneering instance of carborane ferroelectric crystals, this study introduces a novel structural archetype for molecular ferroelectrics, thereby providing fresh insights into the exploration of molecular ferroelectric crystals with promising applications., (© 2024 Wiley-VCH GmbH.)

Halogen engineering offers a means of enhancing the physical properties of materials by fine-tuning the rotational energy barrier and dipole moment, which proved to be effective in achieving switchable phase transitions and optical responses in materials. In this work, by substituting the methyl group in ligand N -ethyl-1,5-diazabicyclo[3.3.0]octane (CH 3 CH 2 -3.3.0-Dabco) with halogen atoms X (Cl or Br) and then contining to react it with FeBr 3 in a HBr aqueous solution, we successfully synthesized three kinds of organic-inorganic hybrid switchable phase-change materials, [CH 3 CH 2 -3.3.0-Dabco]FeBr 4 ( 1 ), [ClCH 2 -3.3.0-Dabco]FeBr 4 ( 2 ), and [BrCH 2 -3.3.0-Dabco]FeBr 4 ( 3 ), which were fully characterized by single-crystal X-ray diffraction and variable-temperature powder X-ray diffraction. Compared to compound 1 , compounds 2 and 3 show two pairs of reversible phase transitions, dielectric anomalies, and a second-harmonic-generation effect, which are successfully induced due to the halogen substitution. This study offers an effective molecular design strategy for the exploration and construction of iron halide organic-inorganic hybrid materials with temperature-adjustable physical properties.

Although antiviral drugs can effectively inhibit hepatitis B virus (HBV) replication, the maintenance of chronic inflammation in the liver is still considered to be an important cause for the progression of HBV-related liver disease to liver fibrosis and advanced liver disease. As an endogenous inhibitory receptor of IL-1R and TLR signaling pathways, single immunoglobulin interleukin-1-related receptor (SIGIRR) has been proven to reduce inflammation in tissues to maintain system homeostasis. However, the relationship between SIGIRR expression and HBV replication and inflammatory pathway activation in hepatocytes remains unclear. In this study, hepatitis B virus X protein (HBx) upregulated MyD88 in liver cells, promoting NF-κB signaling and inflammatory factor production with LPS treatment, and the cell supernatant accelerated the activation and collagen secretion of hepatic stellate cells. However, SIGIRR overexpression suppressed HBx-mediated MyD88/NF-κB inflammatory signaling activation and inflammatory cytokine production induced by LPS in hepatocytes and HBV replication hepatocytes. Although we did not find any effect of SIGIRR on HBV replication in vitro, this study investigated the role of SIGIRR in blocking the proinflammatory function of HBx, which may provide a new idea for the treatment of chronic hepatitis B., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Reported herein is a photochemical strategy for C(sp 3 )-H azolation of ethers via a hydrogen-atom transfer and radical-polar crossover process, offering efficient access to valuable N -alkylated azoles under visible-light irradiation. The protocol is metal-free and photocatalyst-free, and exhibits good to excellent yields and broad substrate scope with regard to azoles. EPR experiments provide evidence for the formation of intermediates formed in situ .

Organic ferroelectrics have received a great deal of interest due to their exclusive properties. However, organic ferroelectrics have not been fully explored, which hinders their practical application. Here, we presented a novel metal-free organic molecular ferroelectric [4-MCHA][ClO 4 ] (1) (4-MCHA=trans-4-methylcyclohexylamine), which exhibits an above-room-temperature of 328 K. Strikingly, the single crystal structure analysis of 1 shows that the driving force of phase transition is related to the interesting chair-boat conformation change of 4-MCHA cation, in addition to the order-disorder transition of ClO 4 - anion. Using piezoelectric response force microscopy (PFM), the presence of domains and the implemented polarization switching were clearly observed, which explicitly determined the presence of room-temperature ferroelectricity of 1. As far as we know, the ferroelectric phase transition mechanism attributed to the conformational change in a trans isomeric cation is very rare. This research enriched the path of designing ferroelectric materials and smart materials., (© 2023 Wiley-VCH GmbH.)

Reactions of a chiral and quasi-spherical molecule [1 S ,4 S -2,5-2.2.1-H 2 dabch]I 2 ( 1 ) with alkali metal halide MX (M = Na, K, Cs; X = Cl, Br) at room temperature produced a series of organic-inorganic hybrid (OIH) materials [1 S ,4 S -2,5-2.2.1-H 2 dabch]NaBr 3 ( 2 ), [1 S ,4 S -2,5-2.2.1-H 2 dabch]CsCl 3 ·H 2 O ( 3 ) and [1 S ,4 S -2,5-2.2.1-H 2 dabch]KBr 3 ·H 2 O ( 4 ). The single-crystal X-ray diffraction analysis revealed that the organic-inorganic framework structures comprised of the templating ligand and alkali metal halides (NaBr, CsCl, KBr) displayed dimensions spanning from one-dimensional (1D) to three-dimensional (3D). Moreover, the results of both differential scanning calorimetry (DSC) and dielectric measurements demonstrated that compounds 1-4 displayed reversible, high-temperature phase transitions and noticeable dielectric anomalies. In addition, the temperature-dependent second harmonic generation (SHG) results revealed crystals 1 and 3 can switch from the SHG-ON to the SHG-OFF state, which was proved by the variable-temperature X-ray diffraction. This research aims to streamline the exploration of multifunctional second harmonic generation (SHG) and dielectric materials that have been synthesized using chiral ligands and alkali metals. This will provide researchers with enhanced opportunities to delve further into this specific research domain.

Reported herein is direct C(sp 3 )-H arylation of unprotected benzyl anilines and alkylarenes via consecutive photoinduced electron transfer by visible light irradiation. Reductive quenching cycles and radical-radical cross-coupling were involved, and electron paramagnetic resonance experiments provide evidence for the formation of radical intermediates formed in situ . The protocol highlights transition metal free, external oxidant free, broad substrate scope, and high efficiency (>60 examples, up to 96%).

Organic-inorganic hybrid metal halides have attracted significant attention in recent years due to their excellent optoelectronic properties and potential applications in solar cells. Herein, the organic-inorganic hybrid molecule [ N , N -dimethyl-1,3-propanediamine]SbBr 5 ( 1 ) was synthesized by reacting a long-chain organic diamine N , N -dimethyl-1,3-propanediamine with SbBr 3 as a metal halide precursor in HBr aqueous solution. Compound 1 possesses a one-dimensional chainlike structure with the second-harmonic generation switch and two continuous phase transitions above room temperature. The band gap of compound 1 is about 2.62 eV, exhibiting a semiconductive property, which may have important implications for the development of new optoelectronic devices.

A novel solid-state second harmonic generation (SHG) organic-inorganic hybrid switch [Me 3 NCH 2 CH 2 F]FeBr 4 (1) exhibits genuine three-step "on-off-on-off" SHG-switching above-room temperature, which has potential applications in multi-step optical devices.

Direct N -allylation of azoles with hydrogen evolution has been achieved through the synergistic combination of organic photocatalysis and cobalt catalysis. The protocol bypasses stoichiometric oxidants and prefunctionalization of alkenes and produces hydrogen (H 2 ) as the byproduct. This transformation highlights high step- and atom-economy, high efficiency, and broad functional group tolerance for further derivatization, which opens a door for C-N bond formation that is valuable in heterocyclic chemistry.

Three-dimensional (3D) hybrid organic-inorganic perovskites (HOIPs) have attracted tremendous research interest due to their unique structure and promising applications. However, research on the design, synthesis and properties of this kind of metal-free crystalline material is still in the exploratory stage. Herein, two 3D perovskite molecules [1,4-3.2.2-dabcn]NH 4 Br 3 (1) and [1,4-3.2.2-dabcn]NH 4 I 3 ·0.5H 2 O (2) were obtained by reacting 1,4-diazabicyclo[3.2.2]nonane (1,4-3.2.2-dabcn) with NH 4 X (X = Br and I) in the corresponding concentrated halogen acids. The single X-ray diffraction results demonstrated that the inorganic framework structures in compounds 1 and 2 constructed with NH 4 Br and NH 4 I are completely different, caused by the radius of the bromide ion being smaller than that of the iodide ion. The 3D framework of compound 1 is constructed with a coplanar dimer [(NH 4 ) 2 Br 6 ] 2- as the basic building unit, leading to the expanded 3D perovskite framework structure with a larger cavity to accommodate the 1,4-3.2.2-dabcn molecule. Nevertheless, compound 2 adopts a familiar 3D crystal framework structure with corner-sharing [(NH 4 )I 6 ] octahedra, where the [1,4-3.2.2-dabcn] cations and water solvent molecule are confined in the cavities enclosed by the octahedra. Notably, both compounds exhibit reversible phase transition, dielectric anomaly and the second harmonic generation (SHG) effect. From the perspective of molecular design, this work is of great significance to guide the construction of new 3D metal-free perovskite molecular materials with reversible properties.

Switchable second harmonic generation (SHG) materials have potential applications in information storage, signal processing, and so on because they can switch between SHG-on and SHG-off states. In this work, we designed and synthesized three organic-inorganic hybrid Rb halide three-dimensional (3D) perovskite materials [1 S ,4 S 2,5-2.2.1-H 2 dabch]RbX 3 ·0.5H 2 O (X = Cl, 1 ; Br, 2 ; I, 3 ) based on the chiral 1 S ,4 S -2,5-diazabicyclo[2.2.1]heptane (1 S ,4 S -2,5-2.2.1-dabch). The selection of homochiral organic cations ensures that the compounds 1 ∼ 3 crystallize in the noncentrosymmetric and chiral space group P 2 1 2 1 2 1 , which further leads to reversible SHG responses of the three compounds. Through differential scanning calorimetry (DSC) and dielectric measurements, it revealed that the phase transition point of the compounds 1 ∼ 3 increased with RbCl, RbBr, and RbI. This is because the hydrogen interaction H···X between the inorganic framework [RbX 3 ] n and the organic cation [1 S ,4 S -2,5-2.2.1-H 2 dabch] 2+ is increased with the order of I > Br > Cl. This study can provide an effective molecular design strategy for the exploration and construction of temperature-tunable SHG switching materials.

The emergence of (CH 3 NH 3 )PbI 3 has brought the development of three-dimensional (3D) organic-inorganic hybrid perovskite (OIHP) structures with ABX 3 type to a higher level; however, most 3D frameworks are constructed by corner-sharing of BX 6 octahedra. Herein, we substituted the spherical molecule 1,4-diazabicyclo[2.2.2]octane (2.2.2-dabco) with 1,4-diazabicyclo[3.2.2]nonane (1,4-3.2.2-dabcn) as a template to react with RbX (X=Br, I) in the corresponding HX acids under the consideration of reducing the molecular symmetry. Two 3D OIHP compounds [1,4-3.2.2-H 2 dabcn]RbI 3 ⋅H 2 O (1) and [1,4-3.2.2-H 2 dabcn]RbBr 3 (2) crystallized in non-centrosymmetric point group mm2 before the phase transition point were isolated. Among them, the 3D inorganic framework of 1 is constructed by sharing the corner of [RbI 6 ] octahedra, while that of 2 is constructed by sharing the corner and face of [RbBr 6 ] octahedra to acquire large cavities to accommodate the organic amine cation [1,4-3.2.2-H 2 dabcn] 2+ ; this 3D framework type is unprecedented in the OIHPs. As expected, compounds 1 and 2 exhibit reversible phase transition, dielectric and second harmonic generation (SHG) and ferroelectric properties, in which the phase transition temperature of 2 at 374 K is much higher than compound 1 at 280 K., (© 2022 Wiley-VCH GmbH.)

Even though hybrid organic-inorganic perovskites (HOIPs) have been studied by many scholars in recent years, there are not many reports on three-dimensional (3D) alkali metal cesium halide perovskites. Here, we report an unprecedented 3D HOIP molecule (1,5-3.2.2-H 2 dabcn)CsBr 3 ( 1 ), in which the 3D anionic framework is constructed by corner-sharing CsBr 6 octahedra and organic cations [1,5-3.2.2-H 2 dabcn] 2+ are located in the cavities formed by the octahedra. Organic cations interact with an inorganic metal frame via two N-H···Br hydrogen bonds. Compound 1 undergoes a reversible order-disorder phase transition and exhibits switchable dielectric and second-harmonic generation (SHG) properties. Interestingly, product 1 crystallizes in a non-centrosymmetric space group Pmn 2 1 at the low-temperature phase (LTP) and transforms into a centrosymmetric space group P 2/ m at the high-temperature phase (HTP). The space group Pmn 2 1 in the LTP has a higher symmetry than P 2/ m in the HTP. This inverted symmetry breaking is very unusual.

The excellent properties of host-guest crown ether inclusions in phase transition, dielectric and second-order nonlinear optical properties have attracted much attention. In this paper, we successfully designed and prepared two novel host-guest crown ether supramolecules [(DFBA)(15-crown-5)]X (X = ClO 4 - , 1; ReO 4 - , 2) by reactions of 2,6-difluorobenzylamine (DFBA) with 1,4,10,13-pentaoxacyclopentadecane (15-crown-5) in HClO 4 , or HReO 4 aqueous solution. By the introduction of difluoro-substituted benzylamine as a guest cation, the phase transition temperatures are greatly increased to 377 K for 1 and 391 K for 2. More importantly, the space group of 1 has changed from centrosymmetric (CS) P 2/ c to the non-centrosymmetric (NCS) Pca 2 1 in 2 when substituting perchlorate (ClO 4 - ) with the larger and heavier perrhenate (ReO 4 - ), which leads to 2 showing a switchable and stable second-harmonic generation (SHG) effect. According to the principle of momentum matching between a cation and anion, the perrhenate group increases the energy barrier of the molecular thermal motion, which not only significantly increases the phase transition temperature of 2 but also causes it to be frozen and crystallized in a NCS space group at room temperature. This research demonstrates that a polar molecule can adjust the suitability of anions and cations inside the crystal by practical chemical means.

Compared with the spherical molecule 1,4-diazoniabicyclo[2.2.2]-octane (2.2.2-dabco), 1,5-diazabicyclo[3.2.2]nonane (3.2.2-dabcn) bears a lower symmetry and larger size. As expected, reactions of 3.2.2-dabcn with rubidium halides gave two 3D molecular ferroelectrics [3.2.2-H 2 dabcn]RbX 3 (X = Br for 1; X = I for 2) with T c at 342 K (1) and 293 K (2).

An organic-inorganic hybrid molecule [3.3.0-H 2 dabco]ZnBr 4 ( 1 ) with switchable phase transition, dielectric anomaly, and second harmonic generation (SHG) effect was synthesized by reaction of 1,5-diazabicyclo[3.3.0]octane (3.3.0-dabco) with ZnBr 2 in concentrated hydrobromic acid aqueous solution. Differential scanning calorimetry (DSC) and dielectric measurements revealed that 1 exhibits a reversible high-temperature phase transition, accompanied by a distinct step-like dielectric anomaly at 373 K. Exceptionally, the single crystal structure analysis at different temperatures revealed that 1 undergoes reverse symmetry breaking during the phase transition, in which the high-symmetry space group Cc in the low temperature phase (LTP) is transformed to the low-symmetry space group P 1̅ in the high temperature phase (HTP). In addition, with the conversion from the non-centrosymmetric (NCS) to the centrosymmetric (CS) space group, the SHG of 1 can switch from SHG-ON to SHG-OFF for at least four cycles without obvious decay.

A one-dimensional organic-inorganic hybrid perovskite material [3.3.0-dabco]PbBr 3 (1) was synthesized by the reaction of 1,5-diazabicyclo[3.3.0]octane (3.3.0-dabco) with PbBr 2 in concentrated HBr aqueous solution. Differential scanning calorimetry, dielectric measurements, and variable-temperature structural analyses revealed that compound 1 exhibits two successive structural phase transitions from P 2 1 2 1 2 1 to Pbcm at 387 K ( T 1 ) and then to P 6/ mmc at 436 K ( T 2 ), accompanied by two pairs of dielectric anomalies with a clear one at T 1 and an unobvious one at T 2 . In addition, compound 1 shows a robust second harmonic generation (SHG) effect between SHG-OFF and SHG-ON states during its centrosymmetric to non-centrosymmetric symmetry breaking phase transition at T 1 .

Background and Aim: Metabolic reprogramming is characterized by dysregulated levels of metabolites and metabolic enzymes. Integrated metabolomic and transcriptomic data analysis can help to elucidate changes in the levels of metabolites and metabolic enzymes, screen the core metabolic pathways, and develop novel therapeutic strategies for cancer., Methods: Here, the metabolome of gastric cancer tissues was determined using liquid chromatography-mass spectrometry. The transcriptome data from The Cancer Genome Atlas dataset were integrated with the liquid chromatography-mass spectrometry data to identify the common dysregulated gastric cancer-specific metabolic pathways. Additionally, the protein expression and clinical significance of key metabolic enzymes were examined using a gastric cancer tissue array., Results: Metabolomic analysis of 16 gastric cancer tissues revealed that among the 15 dysregulated metabolomic pathways, the aminoacyl-tRNA biosynthesis pathway in the gastric tissues was markedly upregulated relative to that in the adjacent noncancerous tissues, which was consistent with the results of transcriptome analysis. Bioinformatic analysis revealed that among the key regulators in the aminoacyl-tRNA biosynthesis pathway, the expression levels of threonyl-tRNA synthetase (TARS) and phenylalanyl-tRNA synthetase (FARSB) were correlated with tumor grade and poor survival, respectively. Additionally, gastric tissue array data analysis indicated that TARS and FARSB were upregulated in gastric cancer tissues and were correlated with poor prognosis and tumor metastasis., Conclusions: This study demonstrated that the aminoacyl-tRNA biosynthesis pathway is upregulated in gastric cancer and both TARS and FARSB play key roles in the progression of gastric cancer. Additionally, a novel therapeutic strategy for gastric cancer was proposed that involves targeting the aminoacyl-tRNA biosynthesis pathway., (© 2021 The Authors. Journal of Gastroenterology and Hepatology published by Journal of Gastroenterology and Hepatology Foundation and John Wiley & Sons Australia, Ltd.)

Although research on organic-inorganic hybrid perovskites (OIHPs) has grown exponentially in the past two decades, the high phase transition temperature of OIHP materials is still one of the insurmountable difficulties. Herein, a series of A 2 BX 4 type OIHP materials [(2, n -DFBA) 2 PbCl 4 ] ( n = 3, for 1 ; n = 4, for 2 ; n = 5, for 3 ; n = 6, for 4 ) have been prepared by reactions of double-substituted difluorobenzylamine (difluorobenzylamine = DFBA) with lead chloride in concentrated HCl aqueous solution. It was found the OIHP compounds 1 - 3 proceed a switchable phase transition with phase transition temperatures ( T c ) at 449 K ( 1 ), 462 K ( 2 ) and 500 K ( 3 ), higher than that of the parent compound [(BA) 2 PbCl 4 ] (BA = benzylammonium) at 438 K, but compound 4 exhibits no phase transition. A crystal structure analysis elucidated that the organic template ligands DFBA lead in the inorganic part in compounds 1 - 3 to a two-dimensional (2D) perovskite structure, while that in compound 4 leads to a one-dimensional (1D) chain structure. The different double-substituted positions of fluorine atoms on benzylamine have important influences on the phase transition in compounds 1 - 4 .

Background and Aim: Serum pepsinogens (PGs) are biomarkers for gastric mucosal damage and have been reported to be associated with atherosclerosis. Its correlation with atherosclerotic cardiovascular disease (ASCVD) is still unknown. This study aimed to explore the association between serum PGs and ASCVD for providing physicians with an integrative picture to make rational plans in the diagnosis and treatment of ASCVD., Methods and Results: The concentrations of serum PGs and their distributions between ASCVD and non-ASCVD were compared by non-parametric test, Chi-squared test and Fisher exact test. The correlation between variables was analyzed by Spearman's correlation test. The association of serum PGs with ASCVD was analyzed by the binary logistic regression and two-piecewise linear regression. A total of 8355 recruited cases were eligible for the study. The concentrations of serum PGs were significantly different between the ASCVD and non-ASCVD groups (P = 0.025, P < 0.001). The lower PGI and PGR levels were significantly correlated with a high risk of ASCVD presence after adjustment for 26 potential covariates. Moreover, there was a linear relationship between the high level of PGII and the high risk of ASCVD [adjusted OR = 1.16 (1.00, 1.37), P = 0.07]. A nonlinear relationship of PGI/PGR and ASCVD (P = 0.08/<0.001) was also revealed. The risk of ASCVD increased with a range of log PGI ≥2.13 (PGI≥131 ng/mL) [adjusted OR = 4.67 (1.00, 23.17)], and decreased with a range of log PGR ≥0.22 (1.65) [adjusted OR = 0.59 (0.48, 0.74), P < 0.001]., Conclusions: Serum PGI and PGR are nonlinearly correlated with ASCVD, while PGII is linearly correlated with ASCVD. Among all PGs, PGR may serve as a reliable biomarker for ASCVD., Competing Interests: Declaration of competing interest The authors declare that they have no competing interests. Patient data is held by the authors, which is available from the corresponding author on reasonable request., (Copyright © 2020 The Italian Diabetes Society, the Italian Society for the Study of Atherosclerosis, the Italian Society of Human Nutrition and the Department of Clinical Medicine and Surgery, Federico II University. Published by Elsevier B.V. All rights reserved.)

Tuberculosis (TB), a serious disease caused by Mycobacterium tuberculosis (Mtb), remains the world's top infectious killer. It is well-established that TB can circumvent the host's immune response for long-term survival. Macrophages serve as the major host cells for TB growth and persistence and their altered functions are critical for the response of the host defense against TB exposure (elimination, latency, reactivation, and bacillary dissemination). Noncoding RNAs are crucial posttranscriptional regulators of macrophage discrimination. Therefore, this review highlights the regulatory mechanism underlying the relationship between noncoding RNAs and macrophages in TB infection, which may facilitate the identification of potential therapeutic targets and effective diagnosis biomarkers for TB disease., (Copyright © 2020 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Diabetes mellitus (DM) is characterized by the irreversible destruction of insulin-secreting pancreatic β-islet cells and requires life-long exogenous insulin therapy. Umbilical cord Wharton's jelly-derived mesenchymal stem cells (WJ-MSCs) have been shown to improve islet function in animal models of diabetes. However, inadequate MSC homing to injured sites has limited their efficacy. Since efficient cell therapy heavily relies on appropriate homing to target tissues, increasing the specificity to the target organ and the extent of homing of the injected WJ-MSCs is paramount to successful clinical outcomes. Therefore, in this study, we synthesized Fe 3 O 4 @polydopamine nanoparticle (NP)-labeled MSCs and evaluated their therapeutic efficacy in a clinically relevant rat model of streptozotocin-induced diabetes using an external magnetic field. We found that NPs were successfully incorporated into WJ-MSCs and did not negatively affect stem cell properties. Magnetic targeting of WJ-MSCs contributed to long-term cell retention in pancreatic tissue and improved the islet function of diabetic rats, compared to injection of WJ-MSC alone. In addition, anti-inflammatory effects and the anti-apoptotic capacity of WJ-MSCs appeared to play a major role in the functional and structural recovery of the pancreas. Thus, therapy relying on the magnetic targeting of WJ-MSCs may serve as an effective approach for DM treatment.

Background: One forth whole-world population is infected with Mycobacterium tuberculosis (Mtb), but 90% of them are asymptotic latent infection without any symptoms but positive result in IFN-γ release assay. There is lack of ideal strategy to distinguish active tuberculosis (TB) and latent tuberculosis infection (LTBI). Some scientist had focused on a set of cytokines as biomarkers besides interferon- gamma (IFN-γ) to distinguish active TB and LTBI, but with considerable variance of results. This meta-analysis aimed to evaluate the overall discriminative ability of potential immune molecules to distinguish active TB and LTBI., Methods: PubMed, the Cochrane Library, and Web of Science databases were searched to identify studies assessing diagnostic roles of cytokines for distinguishing active TB and LTBI published up to August 2018. The quality of enrolled studies was assessed using Quality Assessment of Diagnostic Accuracy Studies-2 (QUADAS-2). The pooled diagnostic sensitivity and specificity of each cytokine was calculated by using Meta-DiSc software. Area under the summary receiver operating characteristic curve (AUC) was used to summarize the overall diagnostic performance of each biomarker., Results: Fourteen studies with 982 subjects met the inclusion criteria, including 526 active TB and 456 LTBI patients. Pooled sensitivity, specificity and AUC for discriminating between active TB and LTBI were analyzed for IL-2 (0.87, 0.61 and 0.9093), IP-10 (0.77, 0.73 and 0.8609), IL-5 (0.64, 0.75 and 0.8533), IL-13 (0.75, 0.71 and 0.8491), IFN-γ (0.67, 0.75 and 0.8031), IL-10 (0.68, 0.74 and 0.7957) and TNF-α (0.67, 0.64 and 0.7783). The heterogeneous subgroup analysis showed that cytokine detection assays, TB incidence, and stimulator with Mtb antigens are main influence factors for their diagnostic performance., Conclusions: The meta-analysis showed cytokine production could assist the distinction between active TB and LTBI, IL-2 with the highest overall accuracy. No single biomarker is likely to show sufficiently diagnostic performance due to limited sensitivity and specificity. Further prospective studies are needed to identify the optimal combination of biomarkers to enhanced diagnostic capacity in clinical practice.

Human mesenchymal stem cell (MSC)-derived exosomes (Exos) are a promising therapeutic agent for cell-free regenerative medicine. However, their poor organ-targeting ability and therapeutic efficacy have been found to critically limit their clinical applications. In the present study, we fabricated iron oxide nanoparticle (NP)-labeled exosomes (Exo + NPs) from NP-treated MSCs and evaluated their therapeutic efficacy in a clinically relevant model of skin injury. We found that the Exos could be readily internalized by human umbilical vein endothelial cells (HUVECs), and could significantly promote their proliferation, migration, and angiogenesis both in vitro and in vivo. Moreover, the protein expression of proliferative markers (Cyclin D1 and Cyclin A2), growth factors (VEGFA), and migration-related chemokines (CXCL12) was significantly upregulated after Exo treatment. Unlike the Exos prepared from untreated MSCs, the Exo + NPs contained NPs that acted as a magnet-guided navigation tool. The in vivo systemic injection of Exo + NPs with magnetic guidance significantly increased the number of Exo + NPs that accumulated at the injury site. Furthermore, these accumulated Exo + NPs significantly enhanced endothelial cell proliferation, migration, and angiogenic tubule formation in vivo; moreover, they reduced scar formation and increased CK19, PCNA, and collagen expression in vivo. Collectively, these findings confirm the development of therapeutically efficacious extracellular nanovesicles and demonstrate their feasibility in cutaneous wound repair.

Introduction: Mesenchymal stem cells (MSCs) are a promising resource for tissue regeneration and repair. However, their clinical application is hindered by technical limitations related to MSC enrichment at the target sites., Methods: MSCs were labeled with magnetic Fe 3 O 4 nanoparticles (NPs). We analyzed the effects of NP on cell proliferation, stem cell characteristics, and cytokine secretion. Furthermore, we induced NP-labeled MSC migration with an external magnetic field toward laser-induced skin wounds in rats and evaluated the associated anti-inflammatory effects., Results: Fe 3 O 4 NP application did not adversely affect MSC characteristics. Moreover, Fe 3 O 4 NP-labeled MSCs presented increased anti-inflammatory cytokine and chemokine production compared with unlabeled MSCs. Furthermore, MSCs accumulated at the injury site and magnetic targeting promoted NP-labeled MSC migration toward burn injury sites in vivo. On day 7 following MSC injection, reduced inflammation and promoted angiogenesis were observed in the magnetically targeted MSC group. In addition, anti-inflammatory factors were upregulated, whereas pro-inflammatory factors were downregulated within the magnetically targeted MSC group compared with those in the PBS group., Conclusion: This study demonstrates that magnetically targeted MSCs contribute to cell migration to the site of skin injury, improve anti-inflammatory effects and enhance angiogenesis compared with MSC injection alone. Therefore, magnetically targeted MSC therapy may be an effective treatment approach for epithelial tissue injuries., Competing Interests: The authors declare no conflicts of interest in this work., (© 2020 Li et al.)

Background: Hepatitis B virus (HBV) infection is a crucial medical issue worldwide. The dependence of HBV replication on host cell machineries and their co-evolutionary interactions prompt the codon usage pattern of viral genes to translation selection and mutation pressure., Objective: The evolutionary characteristics of HBV and the natural selection effects of the human genome on the codon usage characteristics were analyzed to provide a basis for medication development for HBV infection., Methods: The codon usage pattern of sequences from different HBV genotypes of our isolates and reference HBV genome sequences downloaded from the National Center for Biotechnology Information (NCBI) database were analyzed by computing the relative synonymous codon usage (RSCU), nucleotide content, codon adaptation index (CAI) and the effective number of codons (ENC)., Results: The highest ENC values were observed in the C genotypes, followed by the B genotypes. The ENC values indicated a weak codon usage bias (CUB) in HBV genome. The number of codons differentially used between the three genotypes was markedly higher than that of similarly used codons. High CAI values indicated a good adaptability of HBV to its host. The ENC plot indicated the occurrence of mutational pressure in the three genotypes. The mean Ka/Ks ratios in the three genotypes were lower than 1, which indicated a negative selection pressure. The CAI and GC3% plot indicated the existence of CUB in the HBV genome., Conclusions: Nucleotide composition, mutation bias, negative selection and mutational pressure are key factors influencing the CUB and phylogenetic diversity in HBV genotypes. The data provided here could be useful for developing drugs for HBV infection.

BACKGROUND Germline mutations of BRCA2 have been reported in various malignancies. We investigated BRCA2 germline mutations in familial clusters with esophageal squamous cell carcinoma (ESCC). MATERIAL AND METHODS We screened the DNA of familial ESCC patients for BRCA2 germline mutations with whole gene sequencing. Multiple BRCA2 mutations including one novel splice variant, c.426-2A>G were identified. Other family members, sporadic ESCC patients, and controls were also assessed for the novel mutation. RESULTS The mutation c.426-2A>G was found in 2 affected ESCC sisters and 7 other family members. The splice variant mutation results in exon 5 skipping with a frame shift leading to a premature stop codon in exon 6 and truncation. Novel mutation tracking ruled out single nucleotide polymorphism (SNP) in 100 chromosomes of healthy individuals. CONCLUSIONS BRCA2 germline mutation in ESCC patients may play a role in genetic susceptibility to familial ESCC. Genetic analysis of BRCA2 in patients with familial ESCC could provide opportunities for targeted therapies.

Organic-inorganic hybrid materials with perovskite structure have recently attracted tremendous interest due to their structural tunability and rich functional properties, such as phase transition and photoelectric properties. Within this context, two discrete tin-based organic-inorganic hybrid compounds [(FMBA)2SnCl6] (1) and [(FMBA)2SnBr6] (2) were prepared by the reaction of 3-fluoro-N-methylbenzylamine (FMBA) with SnX4 (X = Cl, Br) in the corresponding concentrated halogen acids HX. Differential scanning calorimetry (DSC) and dielectric measurements showed that both compounds underwent reversible phase transition and dielectric anomaly at a phase transition point above 400 K. Crystal structure analyses revealed that the phase transition mainly originated from the order and disorder of a fluorine-substituted organic amine structure at low and high temperatures. Meanwhile, both compounds showed a semiconducting property with optical bandgaps of 4.24 eV for 1 and 2.58 eV for 2. This finding of two Sn(iv)-based metal halides with prominent phase transition and semiconducting behaviors will expand an executable pathway for designing multifunctional perovskite-type switchable materials.

Hypothalamic dysfunction is a key pathological factor in inflammation-associated depression. In the present study, isobaric tags for relative-absolute quantitation (iTRAQ) combined with mass spectrometry and gas chromatography-mass spectrometry (GC-MS) were employed to detect the proteomes and metabolomes in the hypothalamus of the lipopolysaccharide (LPS)-induced depression mouse, respectively. A total of 187 proteins and 27 metabolites were differentially expressed compared with the control group. Following the integration of bi-omics data, pertinent pathways and molecular interaction networks were further identified. The results indicated altered molecules were clustered into Ephrin receptor signaling, glutamatergic transmission, and inflammation-related signaling included the LXR/RXR activation, FXR/RXR activation, and acute phase response signaling. First discovered in the hypothalamus, Ephrin receptor signaling regulates N -methyl-D-aspartate receptor (NMDAR)-predominant glutamatergic transmission, and further acted on AKT signaling that contributed to changes in hypothalamic neuroplasticity. Ephrin type-B receptor 2 (EPHB2), a transmembrane receptor protein in Ephrin receptor signaling, was significantly elevated and interacted with the accumulated NMDAR subunit GluN2A in the hypothalamus. Additionally, molecules involved in synaptic plasticity regulation, such as hypothalamic postsynaptic density protein-95 (PSD-95), p-AKT and brain-derived neurotrophic factor (BDNF), were significantly altered in the LPS-induced depressed group. It might be an underlying pathogenesis that the EPHB2-GluN2A-AKT cascade regulates synaptic plasticity in depression. EPHB2 can be a potential therapeutic target in the correction of glutamatergic transmission dysfunction. In summary, our findings point to the previously undiscovered molecular underpinnings of the pathophysiology in the hypothalamus of inflammation-associated depression and offer potential targets to develop antidepressants., (Copyright © 2019 Wu, Wei, Li, Wei, Li, Cheng, Xu, Li, Guo, Qi, Jia, Jia, Wang and Gao.)

Aim: This study aimed to assess the clinical effectiveness of video-assisted thoracoscopic surgery (VATS) in early-stage lung cancer by indocyanine green (ICG) for tumor mapping., Material and Methods: Thirty patients with early-stage lung cancer with peripheral nodules smaller than 2 cm scheduled for computed tomography (CT)-guided microcoil placement followed by ICG tumor mapping by VATS wedge resection were enrolled. After microcoil deployment, 100 to 150 ml of diluted ICG was injected percutaneously near the nodule. The nodule initially was localized solely by using a near-infrared ray (NIR) thoracoscope to visualize ICG fluorescence. Thoracoscopic instruments were used to determine the staple line. Wedge resection was performed after confirmation of the location of the microcoil using fluoroscopy and pathology results., Results: Thirty patients underwent VATS resection. The median tumor size was 1.3 cm by CT. The median depth from the pleural surface was 1.7 cm (range: 0.5-3.8 cm). The median CT-guided intervention time was 25 min, and VATS procedural time was 50 min. ICG fluorescence was clearly identified in 30 of 30 patients (100%). The surgical margins were all negative on final pathology in all included cases. The final diagnoses were 30 primary lung cancers; none needed additional resection., Conclusions: CT-guided percutaneous ICG injection and intraoperative NIR localization of small nodules are safe and feasible. These offer surgeons the ease of localization through direct indocyanine green fluorescence imaging without the use of fluoroscopy and may be a complementary technique to preoperative microcoil placement for nonvisible, nonpalpable intrapulmonary nodules., Competing Interests: The authors declare no conflict of interest., (Copyright: © 2019 Fundacja Videochirurgii.)

Exercise programs have been introduced to improve cognitive function, whereas studies showed inconsistent results regarding the effectiveness of exercise programs on patients with dementia. This study aimed to summarize randomized controlled trials (RCTs) to assess the effect of exercise programs on cognition, activities of daily living (ADL), and depression in elderly with dementia. We systematically screened PubMed, Embase, and the Cochrane library for relevant studies throughout November 21, 2018. The pooled standardized mean differences (SMDs) with 95% confidence intervals (CIs) were employed to calculate cognition, ADL, and depression by using random-effects model. A total of 20 RCTs with 2,051 dementia patients were included in final quantitative meta-analysis. There were no significant differences between exercise programs and control regarding cognition (SMD: 0.44; 95% CI: -0.21-1.09; P =0.183), ADL (SMD: 0.50; 95% CI: -0.03-1.02; P =0.066), and depression (SMD: -0.43; 95% CI: -0.90-0.05; P =0.077). Sensitivity analysis results indicated that exercise programs might play an important role in cognition and ADL, whereas the depression level was unaltered by the exclusion of any particular study. Subgroup analyses indicated that exercise programs were associated with increased cognitive levels if the mean age of patients was <80.0 years when compared with usual care and studies with low quality. Moreover, the ADL level was significantly increased in patients receiving exercise programs versus usual care. These results suggested that exercise programs might play an important role in cognition and ADL in patients with dementia. These results required further verification by large-scale RCTs, especially for depression outcomes., Competing Interests: The authors declare that they have no conflicts of interest., (Copyright © 2019 Xudong Li et al.)

Background: In recent years, studies on the diagnostic accuracy of in-house real-time PCR (hRT-PCR) assay for the detection of Mycobacterium tuberculosis (Mtb) have been reported with unignorable discrepancies. To assess the overall accuracy of the hRT-PCR assay for Mtb diagnosis in different samples for individuals with active pulmonary and extra-pulmonary Mtb infection, a systematic review and meta-analysis were performed., Methods: The PUBMED, EMBASE, Web of Science, and Cochrane databases were searched up to June 2017 for eligible studies that estimated diagnostic sensitivity and specificity with the hRT-PCR assay in respiratory and non-respiratory samples in pulmonary and extra-pulmonary Mtb infection patients, with Mtb culture as the reference standard. Bivariate random effect models were used to provide pooled estimation of diagnostic accuracy. Further, subgroup and meta-regression analyses were performed to explore sources of heterogeneity. The risk of bias was assessed by the QUADAS-2 tool., Results: Of the 3589 candidate studies, 18 eligible studies met our inclusion criteria. Compared to Mtb culture data, the pooled sensitivity and specificity were 0.96 and 0.92, respectively. The diagnostic odds ratio (DOR) was 192.96 (95% CI 68.46, 543.90), and the area under the summary ROC curve (AUC) was 0.9791. There was significant heterogeneity in sensitivity and specificity among the enrolled studies (p < 0.001). The studies with high-quality assessment and application of respiratory specimen were associated with better accuracy., Conclusions: In low-income/high-burden settings, our results suggested that the hRT-PCR assay could be a useful test for the diagnosis of TB with high sensitivity and specificity.

Mesenchymal stem cell (MSC)-based therapy has emerged as a promising therapeutic strategy for tissue regeneration and repair. However, efficient targeted delivery to specific tissues remains an open challenge. Here, we non-invasively monitored the migration of MSCs labeled with Fe3O4@polydopamine nanoparticles (Fe3O4@PDA NPs) toward laser burn injury sites in a living rat model and evaluated the effects of the labeled MSCs at the injury site. The Fe3O4@PDA NPs could be effectively incorporated into the MSCs without any negative effects on stem cell properties. Furthermore, they enhanced the migration ability of the MSCs by up-regulating the expression level of C-X-C chemokine receptor type 4 (CXCR4). They also increased the secretion of some cytokines and the expression of healing-related genes in comparison with unlabeled MSCs. Labeled MSCs were intravenously administered into injured rats, and live imaging was performed to monitor MSC migration. Fluorescent signals of the labeled MSCs appeared at burn injury lesions 1 day after injection and then gradually increased up to 7 days. After 7 days, the group injected with the labeled MSCs showed less inflammation compared with those injected with the unlabeled MSCs. Additionally, the labeled MSC group showed increased cytokines and reduced pro-inflammatory factors compared with the unlabeled MSC group. The Fe3O4@PDA NPs enhanced stromal cell-derived factor-1/CXCR4-mediated MSC migration in vivo. Thus, we demonstrated the safety, feasibility, and potential efficacy of using the Fe3O4@PDA NPs for optimizing MSC-based therapeutic strategies for burn wound healing.

BCG, the only registered vaccine against Mycobacterial Tuberculosis (TB) infection, has been questioned for its protective efficacy for decades. Although lots of efforts were made to improve the BCG antigenicity, few studies were devoted to understand the role of host factors in the variability of the BCG protection. Using the IL-10KO mice and pulmonary tuberculosis infection model, we have addressed the role of IL-10 in the BCG vaccination efficacy. The data showed that IL-10-deficient dendritic cells (DCs) could promote the immune responses through upregulation of the surface costimulatory molecule expression and play an orchestra role through activating CD4 + T cell. IL-10-deficient mice had higher IFN γ , TNF α , and IL-6 production after BCG vaccination, which was consistent with the higher proportion of IFN γ + CD3 + , IFN γ + CD4 + , and IFN γ + CD8 + T cells in the spleen. Particularly, the BCG-vaccinated IL-10KO mice showed less inflammation after TB challenge compared to WT mice, which was supported by the promoted Th1 and Tc, as well as the downregulated Treg responses in IL-10 deficiency. In a conclusion, we demonstrated the negative relationship between Th1/Tc responses with IL-10 production. IL-10 deficiency restored the type 1 immune response through DC activation, which provided better protection against TB infection. Hence, our study offers the first experimental evidence that, contrary to the modulation of BCG, host immunity plays a critical role in the BCG protective efficacy against TB.

Hepatitis B virus (HBV) infection remains a severe clinical concern in China. Of note, the progression of HBV infection varies between different populations. To identify the factors that influence the disease progression and prognosis, a total of 478 chronic HBV-infected patients were enrolled, and liver function parameters, HBV DNA levels and hepatic fibrosis indices were analyzed. First, the results demonstrated a significant difference in hepatitis B e antigen (HBeAg) expression between male and female patients (χ 2 =4.061, P=0.044). Furthermore, when comparing either HBeAg-negative or -positive male and female patients, males exhibited a greater variation in HBV DNA levels. Although significant differences between male and female patients in certain abnormal ratios of liver function parameters were identified, a trend in the differences was observed in the HBeAg-negative and -positive groups. When considering age, the results of the present study confirmed that HBV DNA levels decreased with advanced age, and the values of the majority of biomarkers exhibited an evident decreasing trend with increasing age. In addition, it was demonstrated that all HBeAg seropositive patients had higher levels of hepatic fibrosis indexes and higher abnormal ratios of hepatic fibrosis values in their serum when compared with those of HBeAg seronegative patients, particularly with regard to serum IV collagen. The present results revealed that HBV DNA replication was closely associated with liver function; however, it was notable that in HBeAg-negative patients, the association between HBV DNA levels and liver function was particularly significant among subjects aged <61. Furthermore, this result was not observed in HBeAg-positive patients. In conclusion, the present study indicated the importance of host factors (including sex and age) and viral factors (including HBeAg expression pattern and HBV DNA levels) in the progression of chronic HBV infection, and its influence regarding prognosis and treatment. The present results provide a foundation for clinical management strategies for chronic HBV infection, particularly in individual schemes.

Background: Developing new methods to deliver cells to the injured tissue is a critical factor in translating cell therapeutics research into clinical use; therefore, there is a need for improved cell homing capabilities., Materials and Methods: In this study, we demonstrated the effects of labeling rat bone marrow-derived mesenchymal stem cells (MSCs) with fabricated polydopamine (PDA)-capped Fe 3 O 4 (Fe 3 O 4 @PDA) superparticles employing preassembled Fe 3 O 4 nanoparticles as the cores., Results: We found that the Fe 3 O 4 @PDA composite superparticles exhibited no adverse effects on MSC characteristics. Moreover, iron oxide nanoparticles increased the number of MSCs in the S-phase, their proliferation index and migration ability, and their secretion of vascular endothelial growth factor relative to unlabeled MSCs. Interestingly, nanoparticles not only promoted the expression of C-X-C chemokine receptor 4 but also increased the expression of the migration-related proteins c-Met and C-C motif chemokine receptor 1, which has not been reported previously. Furthermore, the MSC-loaded nanoparticles exhibited improved homing and anti-inflammatory abilities in the absence of external magnetic fields in vivo., Conclusion: These results indicated that iron oxide nanoparticles rendered MSCs more favorable for use in injury treatment with no negative effects on MSC properties, suggesting their potential clinical efficacy., Competing Interests: Disclosure The authors report no conflicts of interest in this work.

Background: Fluorescent carbon-based nanomaterials have promising properties such as biosensing, cell imaging, tracing and drug delivery. However, carbon dots (CDs) with specific inherent biological functions have not been investigated. Ginsenosides are the components with multiple bioactivities found in plants of the genus Panax , which have attracted a lot of attention for their anticancer effect., Materials and Methods: In this study, we prepared a kind of novel photoluminescent CDs from ginsenoside Re by one-step hydrothermal synthesis method. The conventional methods including transmission electron microscopy, Fourier transform infrared spectroscopy, HPLC and fluorescence spectrum were used for characterization of CDs. In vitro anticancer effect was investigated by cytotoxicity assay, flow cytometry and Western blot analysis., Results: The as-prepared Re-CDs had an average diameter of 4.6±0.6 nm and excellent luminescent properties. Cellular uptake of Re-CDs was facilitated by their tiny nanosize, with evidence of their bright excitation-dependent fluorescent images. Compared with ginsenoside Re, the Re-CDs showed greater inhibition efficiency of cancer cell proliferation, with lower toxicity to the normal cells. The anticancer activity of Re-CDs was suggested to be associated with the generation of large amount of ROS and the caspase-3 related cell apoptosis., Conclusion: Hopefully, the dual functional Re-CDs, which could both exhibit bioimaging and anticancer effect, are expected to have great potential in future clinical applications., Competing Interests: Disclosure The authors report no conflicts of interest in this work.

Natural killer (NK)-cell-based immunotherapy has been reported to have promising prospects in the treatment of non-small cell lung cancer, one of the most common malignancies in the world. It has been proven that higher the NK cell infiltration into the tumor, the better is the curative effect. Therefore, it would be beneficial to develop a method that increases NK cell recruitment and infiltration into the tumor site. The purpose of this study was to establish an immune-cell delivery system for clear lung cancer cells based on magnetic nanoparticle (NP)-labeled NK cells that can be accumulated at the tumor site by placing a tiny external magnetic device inside animals. We developed superparamagnetic iron oxide NPs consisting of a magnetic Fe3O4 core and a shell of polydopamine (PDA) for magnetic targeting therapy. Fe3O4@PDA NPs possess favorable physiological stability and biocompatibility that facilitate their active uptake by NK cells. The biology of NK cells was not affected by the presence of NPs. In vitro and in vivo studies showed that Fe3O4@PDA NP-labeled NK cells significantly inhibited tumor growth and reduced the expression of Ki-67 and increased the apoptosis of A549 cancer cells. H&E staining showed Fe3O4@PDA NP-labeled NK cells, under a magnetic field, had higher intra-tumoral iron density and increased accumulation of CD56+ NK cells. Our results suggest that Fe3O4@PDA NPs are a promising magnetic nanomaterial that can manipulate immune cells, thereby inhibiting tumor growth.

The perovskite structure is rich in ferroelectricity. In contrast, ferroelectric antiperovskites have been scarcely confirmed experimentally since the discovery of M 3 AB-type antiperovskites in the 1930s. Ferroelectricity is now revealed in an organic-inorganic hybrid X 3 AB antiperovskite structure, which exhibits a clear ferroelectric phase transition 6/mmmF6mm with a high Curie point of 480 K. The physical properties across the phase transition are obviously changed along with the symmetry requirements, providing solid experimental evidence for the ferroelectric phase transition. More interestingly, the discovered antiperovskite shows intense photoluminescence and triboluminescence properties. The confirmation of the triboluminescent ferroelectric antiperovskite will open new avenues to explore excellent optoelectronic properties in the antiperovskite family., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Versatile and practical Ag/Cu-mediated decarboxylative halogenation between readily available aryl carboxylic acids and abundant NaX (X = I, Br, Cl) has been achieved under aerobic conditions in moderate to good yields. The halodecarboxylation is shown to be an effective strategy for S-containing heteroaromatic carboxylic acid and benzoic acids with nitro, chloro and methoxyl substituents at the ortho position. A gram-scale reaction and a three-step procedure to synthesize iniparib have been performed to evaluate the practicality of this protocol. A preliminary mechanistic investigation indicates that Cu plays a vital role and a radical pathway is involved in the transformation.

It is known that perovskites with the general chemical formula of ABX 3 (A, B = cations, X = anion) have been intensively studied over the last half century because of their diverse functional properties, such as ferroelectricity in BaTiO 3 , piezoelectricity in PZT (lead zirconate titanate), and recently developed photovoltaic properties in CH 3 NH 3 PbI 3 . However, rather less attention has been paid to their "inverse" analogs, antiperovskites, which have a chemical formula X 3 BA, where A and B are anions and X is a cation. Although most of important ferroelectrics are perovskites, no antiperovskite ferroelectrics have been found since the discovery of antiperovskites in 1930. Here, for the first time, we report a X 3 BA antiperovskite ferroelectric [(CH 3 ) 3 NH] 3 (MnBr 3 )(MnBr 4 ) (where (CH 3 ) 3 NH is X, MnBr 3 is B, and MnBr 4 is A), which shows outstanding ferroelectricity with a significantly high phase transition temperature of 458 K as well as fascinating photoluminescence properties with two intense emissions. This finding opens a new avenue to explore the golden area of antiperovskites for high-performance functional materials.

Au nanorods (AuNRs) have attracted extensive attention in diagnosis and therapy, because of their excellent photothermal effects. Although many of attempts have been employed to prepare AuNRs with a good-size monodispersity, facile and feasible preparation methods are still welcomed in consideration of theranostics-related photothermal applications. In this work, AuNRs are prepared through a seedless method using hydroquinone as the reductant. The longitudinal located surface plasmon resonance peak of the as-prepared AuNRs can be tuned from 650 to 840 nm and the AuNRs indicate a good photothermal conversion efficiency. To lower the toxicity, natural red blood cell membranes are employed to coat the AuNRs. In the primary experiment in vitro , red blood cell membrane-coated AuNRs exhibit good biocompatibility and photothermal treatment effect., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

T helper 17 cells (Th17) constitute a distinct subset of helper T cells with a unique transcriptional profile (STAT3, ROR γ , and ROR α ), cytokine production pattern (IL17 family), and requirement of specific cytokines for their differentiation (TGF- β , IL6, IL21, and IL23). Recent studies involving experimental animals and humans have shown that Th17/IL17 plays a crucial role in host defense against a variety of pathogens, including bacteria and viruses. The underlying mechanisms by which Th17 performs include dendritic cell (DC) regulation, neutrophil recruitment, Th1 modulation, and T regulatory cell (Treg) balance. In recent years, researchers have generated an accumulating wealth of evidence on the role of Th17/IL17 in protective immunity to intracellular bacterial pathogens, such as Mycobacterium tuberculosis and Chlamydia trachomatis , which are one of the most important pathogens that inflict significant socioeconomic burden across the globe. In this article, we reviewed the current literature on the functions and mechanisms by which Th17/IL17 responds to intracellular bacterial infections. A better understanding of Th17/IL17 immunity to pathogens would be crucial for developing effective prophylactics and therapeutics.

Narrow band gaps and excellent ferroelectricity are intrinsically paradoxical in ferroelectrics as the leakage current caused by an increase in the number of thermally excited carriers will lead to a deterioration of ferroelectricity. A new molecular ferroelectric, hexane-1,6-diammonium pentaiodobismuth (HDA-BiI 5 ), was now developed through band gap engineering of organic-inorganic hybrid materials. It features an intrinsic band gap of 1.89 eV, and thus represents the first molecular ferroelectric with a band gap of less than 2.0 eV. Simultaneously, low-temperature solution processing was successfully applied to fabricate high-quality ferroelectric thin films based on HDA-BiI 5 , for which high-precision controllable domain flips were realized. Owing to its narrow band gap and excellent ferroelectricity, HDA-BiI 5 can be considered as a milestone in the exploitation of molecular ferroelectrics, with promising applications in high-density data storage and photovoltaic conversion., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein, six copper(ii) complexes with multidentate ligands, [Cu(HL 1 )(OAc)(HOAc)] (1), [Cu(HL 2 )(OAc)] (2), [Cu(HL 3 )(OAc)] (3), [CuL 4 (OAc)] (4), [Cu(HL 2 )Cl] (5), and [Cu(HL 3 )Cl] (6) {H2L1 = [bis(3-tert-butyl-2-hydroxybenzyl)](2-pyridylmethyl)amine, H2L2 = [(3-tert-butyl-2-hydoxybenzyl)(3-trifluoromethyl-2-hydroxybenzyl) (2-pyridylmethyl)]amine, H2L3 = [bis(3-trifluoromethyl-2-hydroxybenzyl)] (2-pyridylmethyl)amine, and HL4 = [bis(2-pyridylmethyl)] (3-tert-butyl-2-hydroxybenzyl)amine}, are reported. The complexes were characterized by UV-vis spectroscopy, high-resolution mass spectrometry, X-ray single-crystal diffraction analysis and electrochemistry. These copper(ii) complexes have been investigated as catalysts for the aerobic oxidation of benzyl alcohol to benzaldehyde mediated by TEMPO (2,2,6,6-tetramethylpiperidinyl-1-oxyl) radical in water at ambient temperature. Mechanistic investigations have revealed that the phenolate/phenol is involved in the intramolecular proton transfer with a bound substrate in catalysis. Hence, the presence of the trifluoromethyl group on the phenol ring significantly affects the catalysis process since the substituent affects the acidity of phenol, and subsequently, the intramolecular proton transfer from the bound substrate. During catalysis, the dissociation of the auxiliary ligand (Cl - or OAc - ) occurred in the S N 1 pathway, and it is necessary for the substrate to bind. To complete the catalytic cycle, the cleaved auxiliary ligand rebinds to the metal center to regenerate the catalyst.

The reaction of manganese (II) halides MnX 2 and benzothiazole (btz) in the concentrated acids HX (X = Cl, Br) at 80 °C resulted in the formation of two inorganic-organic hybrid complexes: [(btz) 2 (MnX 4 )]·2H 2 O (X = Cl, 1; X = Br, 2). Both compounds showed green luminescence and exhibited moderate quantum yields of 43.17 % for 1 and 26.18 % for 2, which were directly originated from the tetrahedral coordination of Mn 2+ ion. Two organic - inorganic hybrids [(btz) 2 (MnX 4 )]·2H 2 O based on MnCl 2 , benzothiazole and halide acids emitted green light with the moderate quantum efficiencies when excited by 365 nm light. Graphical abstract Two organic-inorganic hybrids [(btz) 2 (MnX 4 )]·2H 2 O based on MnCl 2 , benzothiazole and halide acids emitted green light with the moderate quantum efficiencies when excited by 365 nm light.

Four copper(ii) complexes with multidentate ligands, ([CuL1Cl2]), ([Cu(HL2)Cl2]), ([Cu2(L2)2](ClO4)2) and ([CuL3(HOCH3)ClO4]) {L1 = N,N-bis((pyridin-2-yl)methyl) prop-2-yn-1-amine, HL2 = 2-((((1-methyl-1H-imidazol-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)phenol and HL3 = 2-((((1-methyl-1H-imidazol-2-yl)methyl)(pyridin-2-ylmethyl)amino)methyl)-2-t-butyl-phenol} are reported. The complexes were characterized by UV-vis spectroscopy, elemental analysis and electrochemical analysis. Complexes and were further characterized by X-ray single crystal diffraction analysis. The catalytic performances of these complexes were evaluated in the direct hydroxylation of benzene to phenol with hydrogen peroxide as an oxidant in aqueous acetonitrile media. Under optimized reaction conditions, complex with the most negative reduction potential exhibited the highest conversion without considering the dinuclear complex . A correlation between the catalytic efficiency and the reduction potentials of these complexes was observed, that is the more negative the reduction potential, the higher the benzene conversion. A radical mechanism for the catalysis was confirmed by the fact that addition of radical scavengers such as TEMPO into the reaction mixture could severely suppress the catalysis.

A copper-mediated tandem reaction of β-ketoesters/ketones with tertiary amines was achieved, which provides a simple and efficient approach to the synthesis of 2,3-dihydrofuran derivatives. In this tandem reaction, the tertiary amine not only offers the methylene moiety but also serves as the base.