Novel Dual-Emission Emitters Featuring Phenothiazine-S-Oxide and Phenothiazine-S,S-Dioxide Motifs.

In this study, we have successfully designed and synthesized two novel dual-emission emitters featuring phenothiazine-5-oxide and phenothiazine-5,5-dioxide motifs, characterized by highly lopsided and asymmetric conformational states. Through rigorous spectral examinations and DFT calculations, the compounds exhibit distinctive ICT phenomena, coupled with efficient emission in solid states and AIEE characteristics under high water fractions in DMF/H2O mixtures. These non-planar luminogens exhibit vibrant green and blue solid-state luminescence, with fluorescence quantum yields of 24.1% and 15.21%, respectively. Additionally, they both emit green fluorescence in THF solution, with notable emission quantum yields 36.4% and 30.4%. Comprehensive theoretical investigations unveil well-defined electron cloud density separation between the energies of HOMO/LUMO levels within the two luminogens. Notably, the targeted molecule harboring the phenothiazine-S,S-dioxide motif also demonstrates remarkable reversible mechanofluorochromic properties. Moreover, we testify their potential in applications such as solid-state rewritable information storage and live-cell imaging in solution states. Through theoretical calculations and comparative studies, we have explored the intrinsic relationship between molecular structure and performance, effectively screening and identifying new fluorescent molecules exhibiting outstanding luminescent attributes. These discoveries establish robust theoretical and technical foundation for the synthesis and application of efficient DSE-based MFC materials, opening new avenues in the realm of advanced luminescent materials.

Manufacturing of high strength and high conductivity copper with laser powder bed fusion.

Additive manufacturing (AM), known as 3D printing, enables rapid fabrication of geometrically complex copper (Cu) components for electrical conduction and heat management applications. However, pure Cu or Cu alloys produced by 3D printing often suffer from either low strength or low conductivity at room and elevated temperatures. Here, we demonstrate a design strategy for 3D printing of high strength, high conductivity Cu by uniformly dispersing a minor portion of lanthanum hexaboride (LaB6) nanoparticles in pure Cu through laser powder bed fusion (L-PBF). We show that trace additions of LaB6 to pure Cu results in an improved L-PBF processability, an enhanced strength, an improved thermal stability, all whilst maintaining a high conductivity. The presented strategy could expand the applicability of 3D printed Cu components to more demanding conditions where high strength, high conductivity and thermal stability are required.

Metallaaromatic Complexes as Candidates for Future Molecular Materials and Electronic Devices: Recent Advancements.

In recent years, the field of organometallic chemistry has made a great progress and diverse types of metallaaromatics have successively been reported. In those studies, incorporation of ligated osmium centers into metallaaromatic systems played a prominent role. The reviewed literature documents that certain metallaaromatics with unconventional photophysical properties, redox and electronic transport properties and magnetism, have potential to be widely used in diverse practical applications, with selected examples of amino acid and fluoride anion identification, photothermal effects, functional materials, photodynamic therapy (PDT) in biomedicine, single-molecule junction conductors, and electron-transport layer materials (ETLs) in solar cells.

Kinetics and Combustion Behavior of Atomized Zn-Mg Alloy Powder.

Using pyrolants instead of warhead charges can release red light and thick smoke for target practice to highlight the safety of the impact point and dud disposal. In order to find the ideal material, the combustion and kinetic properties of two Zn-Mg alloys at critical proportions were investigated. Thermogravimetry/differential scanning calorimetry (TG/DSC) experiments in pure oxygen were conducted with atomized Zn-Mg alloy powder in the ratio of 7:3 and the ratio of 8:2 with three particle diameters under different heating rates. The kinetic parameters of the six materials were obtained by ASTM E698 and Ozawa-Flynn-Wall (OFW) methods, indicating that the activation energy (Eα) of the 7:3 Zn-Mg alloy powder was lower than that of the 8:2 Zn-Mg alloy powder when the particle size distributions are similar. By the method of nonlinear multivariate regression, the oxidation reaction of Zn-Mg alloy powder was divided into two steps. The proportion of mass gain of the first-step reaction of 7:3 Zn-Mg alloy powder was 0.462-0.518, and the proportion of mass gain of the first-step reaction of 8:2 Zn-Mg alloy powder was 0.138-0.228. Reaction mechanism functions of the two-step reaction of Zn-Mg alloy oxidation were derived as f(α) = (1 - α)n(1 + kcat·α). The results of combustion experiments showed that the pyrolants composed of 7:3 alloy can burn stably to produce satisfactory smoke and light signals, while the pyrolants composed of 8:2 alloy cannot achieve this. The 7:3 Zn-Mg alloy powder is an ideal ingredient for pyrotechnic compositions.

Synthesis, structure and mechanofluorochromic properties of phenothiazine-S-oxide and phenothiazine-S,S-dioxide derivatives.

In this work, two novel luminescent molecules containing distorted phenothiazine-S-oxide and phenothiazine-S,S dioxide skeletons were synthesized by oxidation reactions using different oxidants (m-chloroperoxybenzoic acid, acetic acid /hydrogen peroxide). The target compounds were all confirmed by 1H NMR, 13C NMR and EI-MS. Combined with the results of UV-vis absorption spectra and fluorescence emission spectra, we found that the different oxidation states of S-atom, from sulfide (+2) to sulfoxide (+4) and sulfone (+6), led to the blue, yellow-green and yellowish fluorescence of these compounds in the solid states. Subsequent studies showed that the molecule containing the phenothiazine-S-oxide skeleton exhibited obvious solvatochromism, and the increase of solvent polarity induced a red-shift in the emission wavelength. Moreover, this molecule also exhibited a rare self-recovery mechanochromatic behavior. In addition, these properties were further confirmed by theoretical calculations and X-ray single-crystal diffraction analysis.

[Ameliorative Effects of Cang-ai Volatile Oil on Left Ventricular Remodeling in Rats].

Objective: To evaluate with 7T cardiac magnetic resonance tissue tracking imaging (CMR-TT) the ameliorative effect of Cang-ai volatile oil (CAVO) on left ventricular remodeling (LVR) in rats induced by isoproterenol (ISO), and to make preliminary investigation into CAVO's effects on endothelial dysfunction in LVR. Methods: A total of 35 healthy male Sprague-Dawley (SD) rats were randomly assigned to two groups, the experimental group ( n=27) and the normal control group ( n=8). The rat model of LVR was established by subcutaneous injection of ISO solution at 10 mg·kg -1·d -1 at multiple sites for 10 consecutive days. After modeling was completed, the surviving rats ( n=24) in the experimental group were then randomly assigned to the blank experimental group, CAVO group, and Shexiang Baoxin pill (SXBXP) group ( n=8 in each group). Rats in each group were given via gavage the corresponding intervention medicine or an equivalent amount of normal saline solution for 28 consecutive days. At the end of modeling and intragastric intervention, 7T CMR cine sequence scanning was conducted to collect data. Then, post-processing software CVI42 was used to analyze the images and to compare and contrast the changes in the parameters of left ventricular cardiac function and myocardial strain in each group before and after the administration of the medication. The rats were sacrificed after MRI scanning, and their hearts were harvested for pathological examination. The levels of serum biochemical indicators were measured by enzyme-linked immunosorbent assay (ELISA). Results: CAVO significantly increased LV ejection fraction and overall myocardial strain parameters in LVR rats, while it decreased LV volume, mass, and serum levels of endothelial function indicators in LVR rats. In addition, pathological staining showed marked improvements in the hypertrophy, necrosis and interstitial fibrosis of cardiomyocytes. Conclusion: Through the regulation of myocardial vascular endothelial function, CAVO can significantly improve cardiac functions in LVR rats, delay the process of ventricular remodeling, and have a certain amount of protective effect on cardiac structure and function in rats.

Pentacyclic and Hexacyclic Osmaarynes and Their Derivatives.

Although osmabenzyne, osmanaphthalyne, osmaphenanthryne, and osmaanthracyne have been previously reported, the synthesis of polycyclic osmaarynes is still a challenge. Herein, we report the successful synthesis of the first pentacyclic osmaarynes (pyreno[b]osmabenzynes 1 a and 2 a) and hexacyclic osmaaryne (peryleno[b]osmabenzyne 3 a). Nucleophilic reaction of osmaarynes was used to obtain the corresponding pyreno[b]osmium complexes (1 and 2) and peryleno[b] osmium complex (3), which exhibited near-infrared luminescence and aggregation-induced emission (AIE) properties. Complexes 2 and 3 are resistant to photodegradation, and complex 2 has better photothermal conversion properties than 3.

Designing against phase and property heterogeneities in additively manufactured titanium alloys.

Additive manufacturing (AM) creates digitally designed parts by successive addition of material. However, owing to intrinsic thermal cycling, metallic parts produced by AM almost inevitably suffer from spatially dependent heterogeneities in phases and mechanical properties, which may cause unpredictable service failures. Here, we demonstrate a synergistic alloy design approach to overcome this issue in titanium alloys manufactured by laser powder bed fusion. The key to our approach is in-situ alloying of Ti-6Al-4V (in weight per cent) with combined additions of pure titanium powders and iron oxide (Fe2O3) nanoparticles. This not only enables in-situ elimination of phase heterogeneity through diluting V concentration whilst introducing small amounts of Fe, but also compensates for the strength loss via oxygen solute strengthening. Our alloys achieve spatially uniform microstructures and mechanical properties which are superior to those of Ti-6Al-4V. This study may help to guide the design of other alloys, which not only overcomes the challenge inherent to the AM processes, but also takes advantage of the alloy design opportunities offered by AM.

Accumulation of dysfunctional tumor-infiltrating PD-1+ DCs links PD-1/PD-L1 blockade immunotherapeutic response in cervical cancer.

Various predictive biomarkers are needed to select candidates for optimal and individualized treatments. Tumor-infiltrating immune cells have gained increasing interest in cancer research for the prediction of therapeutic response and survival. However, the role of dendritic cells (DCs) in PD-1 blockade immunotherapy remains unclear. In this study, we identified a population of PD-1+ DCs in the tumor microenvironment (TME) of cervical cancer (CC). The accumulation of PD-1+ DCs in cervical tumors was correlated with advanced stages, elevated preoperative squamous cell carcinoma antigen levels and lymph-vascular space invasion. PD-1 expression was induced on activated tumor-associated DCs (TADCs) in vitro compared with their resting counterparts. This PD-1+ DC population was characterized by reduced secretion of cytokines (IL-12, TNF-α, and IL-1ß) and dysfunctional induction of T cell proliferation and cytotoxic reaction. PD-1 blockade significantly reinvigorated PD-1+ DCs to release IL-12, TNF-α, and IL-1ß compared with PD-1- DCs. TILs from samples with higher PD-1+ DC infiltration could be induced to achieve a greater killing effect of PD-1 blockade treatment. Our findings suggested a role for PD-1+ DCs in immune surveillance dysfunction and CC progression. PD-1+ DC density in the TME may serve as a diagnostic factor for predicting the optimal beneficiaries of PD-1/PD-L1 blockade immunotherapy in CC.

A naphthimide-based ratiometric fluorescent probe for selective and visual detection of phosgene in solution and the gas phase.

As a colorless, highly toxic and widely used chemical reagent, phosgene poses a potentially serious threat to public health and environmental safety. Therefore, there is an urgent need to develop a simple and sensitive method for detecting phosgene. In this work, a ratiometric fluorescent probe (NED) for phosgene was developed by utilizing 4-substituted 1,8-naphthimide unit as the fluorophore and ethylenediamine as the recognition moiety. The probe NED undergoes intramolecular cyclization reaction with phosgene, resulting in a remarkable ratiometric fluorescence response. The probe NED displays high sensitivity (LOD = 4.9 nM), excellent ratiometric fluorescence signal, and high selectivity toward phosgene over other relevant analytes. In addition, paper test strip capable of visually detecting gaseous phosgene has also been fabricated.

YgfY Contributes to Stress Tolerance in Shewanella oneidensis Neither as an Antitoxin Nor as a Flavinylation Factor of Succinate Dehydrogenase.

YgfY(SdhE/CptB) is highly conserved while has controversial functions in bacteria. It works as an antitoxin and composes a type IV toxin-antitoxin system with YgfX(CptA) typically in Escherichia coli, while functions as an flavinylation factor of succinate dehydrogenase and fumarate reductase typically in Serratia sp. In this study, we report the contribution of YgfY in Shewanella oneidensis MR-1 to tolerance of low temperature and nitrite. YgfY deficiency causes several growth defects of S. oneidensis MR-1 at low temperature, while YgfX do not cause a growth defect or morphological change of S. oneidensis MR1-1 and E. coli. YgfY do not interact with FtsZ and MreB nor with YgfX examined by bacterial two-hybrid assay. YgfY effect on growth under low temperature is not attributed to succinate dehydrogenase (SDH) because a mutant without SDH grows comparably with the wild-type strain in the presence of succinate. The ygfY mutant shows impaired tolerance to nitrite. Transcription of nitrite reductase and most ribosome proteins is significantly decreased in the ygfY mutant, which is consistent with the phenotypes detected above. Effects of YgfY on growth and nitrite tolerance are closely related to the RGXXE motif in YgfY. In summary, this study demonstrates pleiotropic impacts of YgfY in S. oneidensis MR-1, and sheds a light on the physiological versatility of YgfY in bacteria.

Atractylenolide-I Sensitizes Triple-Negative Breast Cancer Cells to Paclitaxel by Blocking CTGF Expression and Fibroblast Activation.

This investigation was conducted to elucidate whether atractylenolide-I (ATL-1), which is the main component of Atractylodes macrocephala Koidz, can sensitize triple-negative breast cancer (TNBC) cells to paclitaxel and investigate the possible mechanism involved. We discovered that ATL-1 could inhibit tumor cell migration and increase the sensitivity of tumor cells to paclitaxel. ATL-1 downregulated the expression and secretion of CTGF in TNBC cells. Apart from inhibiting TNBC cell migration via CTGF, ATL-1 downregulated the expression of CTGF in fibroblasts and decreased the ability of breast cancer cells to transform fibroblasts into cancer-associated fibroblasts (CAFs), which in turn increased the sensitivity of TNBC cells to paclitaxel. In a mouse model, we found that ATL-1 treatments could enhance the chemotherapeutic effect of paclitaxel on tumors and reduce tumor metastasis to the lungs and liver. Primary cultured fibroblasts derived from inoculated tumors in mice treated with ATL-1 combined with paclitaxel expressed relatively low levels of CAF markers. Collectively, our data indicate that ATL-1 can sensitize TNBC cells to paclitaxel by blocking CTGF expression and fibroblast activation and could be helpful in future research to determine the value of ATL-1 in the clinical setting.

Osmaindenes: Synthesis and Reversible Mechanochromism Characteristics.

A series of novel osmaindenes 1-6 bearing different substituents (CF3 , H, I, Br, OCH3 , N(Ph)2 ) has been synthesized by nucleophilic reaction of water with the corresponding aromatic osmanaphthalyne complexes. All osmaindenes 1-6 have been characterized by elemental analysis (EA) and nuclear magnetic resonance (NMR) spectroscopy, although the low solubilities of 3 and 4 precluded the accumulation of their 13 C NMR spectra. Osmaindenes 2, 3 and 5 have also been characterized by single-crystal X-ray diffraction analysis. Subsequently, through solid-state fluorescence spectroscopy, mechanochromic studies, and powder X-ray diffraction (XRD) analysis, we found that osmaindenes 1-6 fluoresce at wavelengths in the range 500-800 nm, while also displaying reversible mechanochromic properties. The solid-state fluorescence emission of 1 after grinding extends into the near-infrared region. This research provides new insight into the design and synthesis of metallic materials with excellent mechanochromic properties.

Nucleophilic Reactions of Osmanaphthalynes with PMe3 and H2 O.

Members of a new class of complexes, 2(CF3 ), 2(H), 2(Br), 2(I), and 2(OCH3 ), have been synthesized in a one-pot method involving the treatment of osmanaphthalynes bearing corresponding substituents (1(CF3 ), 1(H), 1(Br), 1(I), and 1(OCH3 )) with trimethylphosphine (PMe3 ) and water. The main reaction process involves two steps, namely a ligand-exchange with trimethylphosphine and nucleophilic addition of water to the Os≡C bond of the osmanaphthalyne. The substituents have a significant influence on the rate of the reaction, as befits a nucleophilic addition. Fortunately, the key intermediate [1(OCH3 )]' could be successfully captured, and the detailed reaction mechanism has been explored with the aid of density functional theory (DFT) calculations, which were in excellent agreement with the experimental findings. All of the target complexes have been fully characterized by 1 H, 31 P{1 H}, and 13 C{1 H} NMR spectroscopy, high-resolution mass spectrometry, and elemental analysis.

Pyruvate accelerates palladium reduction by regulating catabolism and electron transfer pathway in Shewanella oneidensis.

Shewanella oneidensis is a model strain of the electrochemical active bacteria (EAB) because of its strong capability of extracellular electron transfer (EET) and genetic tractability. In this study, we investigated the effect of carbon sources on EET in S. oneidensis by using reduction of palladium ions (Pd(II)) as a model and found that pyruvate greatly accelerated the Pd(II) reduction compared with lactate by resting cells. Both Mtr pathway and hydrogenases played a role in Pd(II) reduction when pyruvate was used as a carbon source. Furthermore, in comparison with lactate-feeding S. oneidensis, the transcriptional levels of formate dehydrogenases involving in pyruvate catabolism, Mtr pathway, and hydrogenases in pyruvate-feeding S. oneidensis were up-regulated. Mechanistically, the enhancement of electron generation from pyruvate catabolism and electron transfer to Pd(II) explains the pyruvate effect on Pd(II) reduction. Interestingly, a 2-h time window is required for pyruvate to regulate transcription of these genes and profoundly improve Pd(II) reduction capability, suggesting a hierarchical regulation for pyruvate sensing and response in S. oneidensis IMPORTANCE The unique respiration of EET is crucial for the biogeochemical cycling of metal elements and diverse applications of EAB. Although a carbon source is a determinant factor of bacterial metabolism, the research into the regulation of carbon source on EET is rare. In this work, we reported the pyruvate-specific regulation and improvement of EET in S. oneidensis and revealed the underlying mechanism, which suggests potential targets to engineer and improve the EET efficiency of this bacterium. This study sheds light on the regulatory role of carbon sources in anaerobic respiration in EAB, providing a way to regulate EET for diverse applications from a novel perspective.

The Gut Microbiota and Its Relevance to Peripheral Lymphocyte Subpopulations and Cytokines in Patients with Rheumatoid Arthritis.

Growing experimental and clinical evidence suggests that a chronic inflammatory response induced by gut microbiome critically contribute to the development of rheumatoid arthritis (RA). Previous studies demonstrated the disturbance of lymphocyte subpopulations in RA patients. The purpose of this study was to explore the characteristics of gut microbiome and the associations between bacterium and lymphocyte subpopulations as well as cytokines in patients with RA. Fecal samples from 205 RA patients and 199 healthy controls (HCs) were collected for bacterial DNA extraction and 16S ribosomal RNA (rRNA) gene sequencing. The levels of peripheral lymphocyte subpopulation such as T, B, CD4+T, CD8+T, NK, T helper 1 (Th1), Th2, Th17, and regulatory T cells (Tregs) of these subjects were detected by flow cytometry combined with standard absolute counting beads. The serum levels of cytokines interleukin-2 (IL-2), IL-4, IL-6, IL-10, IL-17, tumour necrosis factor-α (TNF-α), and interferon-γ (INF-γ) were tested by flow cytometric bead array (CBA). Alpha and beta diversity of gut microbiome were explored by bioinformatics analysis. Spearman rank correlation test was used to explore the relationships between gut microbiome and lymphocyte subsets as well as serum cytokines. The diversity and relative abundance of intestinal microbiota in patients with RA were significantly different from those in HCs. Detailly, the abundant of phylum Proteobacteria in RA patients was more than that in HCs, while Firmicutes was less than in HCs. There was increased relative abundance of genus Clostridium_XlVa as well as genus Blautia, more abundance of Ruminococcus2 in patients with lower levels of T, B, CD4+T, and Tregs. In addition, the relative abundances of Pelagibacterium, Oxalobacter, ClostridiumXlVb, and ClostridiumXVIII were correlated with cytokines. Gut microbiome of RA patients was clearly different from that of HCs. Abnormal bacteria communities are associated with the altered levels of lymphocyte subpopulation and cytokines, which might be one of the pathogenesis of RA.

Bone marrow stromal cells-derived exosomes target DAB2IP to induce microglial cell autophagy, a new strategy for neural stem cell transplantation in brain injury.

Bone marrow stromal cells (MSCs) are a useful source of stem cells for the treatment of various brain injury diseases due to their abundant supply and fewer ethical problems compared with transplant treatment. However, the clinical application of MSCs is limited due to allograft rejection and immunosuppression in the process of MSCs transplantation. According to previous studies, microglial cell autophagy occurs following co-culture with MSCs. In the present study, exosomes were obtained from MSCs and subsequently characterized using transmission electron microscopy, atomic force microscopy and dynamic light scattering particle size analysis. The type of microRNAs (miRs) found in the exosomes was then analyzed via gene chip. The results demonstrated that microglial cell autophagy could be induced by exosomes. This mechanism was therefore investigated further via reverse transcription-quantitative PCR, western blotting and luciferase assays. These results demonstrated that exosomes from MSCs could induce microglial cell autophagy through the miR-32-mediated regulation of disabled homolog 2-interacting protein, thus providing a theoretical basis for the clinical application of miRs in MSCs.

Tissue Imaging of Glutathione-Specific Naphthalimide-Cyanine Dye with Two-Photon and Near-Infrared Manners.

Molecular probes suitable for different fluorescence imaging technologies can meet the requirements of different scientific research in biological applications. In this work, a naphthalimide-cyanine-based sulfonamide was used to specifically visualize the glutathione of mouse tissues with a two-photon manner for the naphthalimide moiety and a near-infrared manner for the cyanine moiety, respectively. The results showed that this probe served as a dual-model tissue-imaging agent for visualization of glutathione with around 200 µm imaging depth in a two-photon manner and 120 µm imaging depth in a near-infrared manner, which provided a model for tissue imaging in the visible and near-infrared channels.

Overexpression of PRR11 promotes tumorigenic capability and is associated with progression in esophageal squamous cell carcinoma.

INTRODUCTION: Esophageal squamous cell carcinoma (ESCC) is one of the most common malignancies of gastrointestinal tract in the world, and the long-term prognosis for ESCC patients still remains dismal due to the lack of effective early diagnosis biomarkers. MATERIALS AND METHODS: Western blot and immunochemistry were used to determine the expression of PRR11 in 201 clinicopathologically characterized ESCC specimens. The effects of PRR11 on stem cell-like traits and tumorigenicity were examined by tumor sphere formation assay and SP assays in vitro and by a tumorigenesis model in vivo. The mechanism by which PRR11 mediated Wnt/ß-catenin signaling was explored using luciferase reporter, immuno-chemistry, and real time-PCR (RT-PCR) assays. RESULTS: We found that PRR11 was markedly upregulated, at the level of both transcription and translation, in ESCC cell lines as compared with normal esophageal epithelial cells (NECCs). Immunohistochemical analysis showed that 69.2% paraffin-embedded archival ESCC specimens exhibited high levels of PRR11 expression, and multivariate analysis revealed that PRR11 upregulation might be an independent prognostic indicator for the survival of patients with ESCC. Furthermore, overexpression of PRR11 dramatically enhanced, whereas inhibition of PRR11 reduced the capability of cancer stem cell (CSC)-like phenotypes and tumorigenicity of ESCC cells both in vitro and in vivo. Mechanically, we demonstrated PRR11-enhanced tumorigenicity of ESCC cells via activating Wnt/ß-catenin signaling, and PRR11 expression is found to be significantly correlated with ß-catenin nuclear location in ESCC. CONCLUSION: Our findings suggest that the PRR11 might represent a novel and valuable prognostic marker for ESCC progression and play a role during the development and progression of this malignancy.