The thermodynamics of small-molecule (H2, arene, alkane, and CO) addition to pincer-ligated iridium complexes of several different configurations (three-coordinate d8, four-coordinate d8, and ...five-coordinate d6) have been investigated by computational and experimental means. The substituent para to the iridium (Y) has been varied in complexes containing the (Y-PCP)Ir unit (Y-PCP = η3-1,3,5-C6H2CH2PR22Y; R = methyl for computations; R = tert-butyl for experiments); substituent effects have been studied for the addition of H2, C−H, and CO to the complexes (Y-PCP)Ir, (Y-PCP)Ir(CO), and (Y-PCP)Ir(H)2. Para substituents on arenes undergoing C−H bond addition to (PCP)Ir or to (PCP)Ir(CO) have also been varied computationally and experimentally. In general, increasing electron donation by the substituent Y in the 16-electron complexes, (Y-PCP)Ir(CO) or (Y-PCP)Ir(H)2, disfavors addition of H−H or C−H bonds, in contradiction to the idea of such additions being oxidative. Addition of CO to the same 16-electron complexes is also disfavored by increased electron donation from Y. By contrast, addition of H−H and C−H bonds or CO to the three-coordinate parent species (Y-PCP)Ir is favored by increased electron donation. In general, the effects of varying Y are markedly similar for H2, C−H, and CO addition. The trends can be fully rationalized in terms of simple molecular orbital interactions but not in terms of concepts related to oxidation, such as charge-transfer or electronegativity differences.
The infinite potential of lanthanide in optoelectronic research has triggered the search for ideal host materials. Herein, based on the excellent lanthanide compatibility of double perovskite ...La2MgTiO6, light-responsive multifunctional phosphors with four modes were successfully constructed (Modes I–IV: Tm–Yb; Er–Yb; Ho–Yb; Er/Tm–Yb). After systematically exploring the internal mechanism of high-purity and brightness upconversion (UC) photoluminescence behind the four modes, intense green, blue and near-white lighting-emitting diodes (LEDs) were fabricated. Besides, aiming at the different emission energy levels of the monitored bands, the temperature-sensing performance of Modes I–IV was strictly evaluated utilizing thermally coupled or non-thermally-coupled luminescence intensity ratio (LIR) techniques. All the modes demonstrate excellent temperature measurement potential, stability and repeatability. Especially in Mode IV, a novel self-calibrating partition thermometer with dual-emitting centers originating from Er/Tm was designed successfully, which can provide specific LIR for three regions of low temperature, medium temperature and high temperature, and finally achieve high relative sensitivity over an ultra-wide temperature range. The results testify that the as-synthesized multifunctional phosphors break through the limitation of lanthanide doping types in a single material, which can realize the diversification of application functions and launch a new chapter for the design of advanced multifunctional materials.
Studies on the role of programmed death-1(PD-1) and its main ligand (PD-L1) during experimental models of sepsis have shown that the PD-1/PD-L1 pathway plays a pathologic role in altering microbial ...clearance, the innate inflammatory response and accelerated apoptosis in sepsis. However, the expression of PD-1 and PD-L1 and their role during the development of immune suppression in septic patients have not been elucidated. The present study was designed to determine whether the expression of PD-1 and PD-L1 is upregulated in septic shock patients and to explore the role of this pathway in sepsis-induced immunosuppression.
Nineteen septic shock patients and 22 sex-matched and age-matched healthy controls were prospectively enrolled. Apoptosis in lymphocyte subpopulations and PD-1/PD-L1 expression on peripheral T cells, B cells and monocytes were measured using flow cytometry. Apoptosis of T cells induced by TNFα or T-cell receptor ligation in vitro and effects of anti-PD-L1 antibody administration were measured by flow cytometry. CD14+ monocytes of septic shock patients were purified and incubated with either lipopolysaccharide, anti-PD-L1 antibody, isotype antibody, or a combination of lipopolysaccharide and anti-PD-L1 antibody or isotype antibody. Supernatants were harvested to examine production of cytokines by ELISA.
Compared with healthy controls, septic shock induced a marked increase in apoptosis as detected by the annexin-V binding and active caspase-3 on CD4+ T cells, CD8+ T cells and CD19+ B cells. Expression of PD-1 on T cells and of PD-L1 on monocytes was dramatically upregulated in septic shock patients. PD-1/PD-L1 pathway blockade in vitro with anti-PD-L1 antibody decreased apoptosis of T cells induced by TNFα or T-cell receptor ligation. Meanwhile, this blockade potentiated the lipopolysaccharide-induced TNFα and IL-6 production and decreased IL-10 production by monocytes in vitro.
The expression of PD-1 on T cells and PD-L1 on monocytes was upregulated in septic shock patients. The PD-1/PD-L1 pathway might play an essential role in sepsis-induced immunosuppression.
•Effect of β-nucleating agent on crystallization of post-consumer PP is studied.•Post-consumer PP with relative β-phase content higher than 0.80 is able to prepare.•It is possible to apply ...polymorphic modification in post-consumer PP recycling.
The effect of two kinds of β-nucleating agents, an aryl amide derivative β-nucleating agent (TMB-5) and a rare earth complex (WBG), on crystallization of post-consumer polypropylene (PCW-PP) were investigated by differential scanning calorimetry (DSC), wide-angle X-ray diffraction (XRD) and polarized-light optical microscopy (POM). The results indicate that introduction of TMB-5 and WBG is able to increase the crystallization temperature of PCW-PP and to induce a large amount of β-crystals. TMB-5 has stronger β-nucleating effect than WBG at low content, while the β-nucleating effect of WBG exceeds that of TMB-5 at a content of about 0.7 wt%, referring to the calculated relative content of β-phase and the concentration of nuclei in PCW-PP. Through adding 0.3 wt% TMB-5 or 0.7 wt% WBG, PCW-PP with β-phase content higher than 0.80 can be prepared, which provides a promising method to realize high-value added recycling of PCW-PP.
Rice stripe disease is one of the most devastating and widespread rice viral diseases caused by rice stripe virus (RSV). Some rice cultivars have been shown to be resistant to RSV; however, the ...proteins and genes responsible for the resistance are rarely characterized. To explore this resistance mechanism, in this study we employed proteomic tools including two-dimensional electrophoresis (2-DE) and mass spectrometry (MS) to globally identify differential proteins between a RSV-resistant rice cultivar Xudao 3 (O. sativaL.spp. japonica, cv. Xudao 3)and a RSV-susceptible rice cultivar Wuyujing 3 (O. sativaL.spp. japonica, cv. Wuyujing 3).Our data showed that 27 proteins were statistically different during the three-leaf stage of seedlings between Xudao3 and Wuyujing 3. 15 of them were up-regulated and the other 12 proteins were down-regulated in Wuyujing 3. 20 differential proteins were successfully identified through mass spectrometry and database search. Interestingly, some proteins related to stress and/or defense responses were down-regulated in Wuyujing 3, such as heat shock protein, protein disulfide isomerase, glyoxalase and Os04g0435700, which may be implicated in its susceptibility to RSV.Together, our work for the first time successfully identified some differential proteins related to RSV-resistance or susceptibility, providing candidate proteins and genes for subsequent investigations of their roles in rice resistance against RSV.
Research has shown that personality is associated with anxiety levels in the general population. However, little is known about the relationship between personality and preoperative anxiety and the ...subsequent health outcomes in patients undergoing surgery. Therefore, this review aimed to identify studies that explored the relationship between personality traits and preoperative anxiety, as well as their association with postoperative outcomes. Existing literature shows that anxiety may play an intermediary role in the relationship between personality and postoperative outcomes. Severe anxiety may partially explain the adverse effects of certain personality traits, such as neuroticism, on postoperative outcomes. However, the relationship between personality traits, preoperative anxiety, and postoperative outcomes remains unclear. Interventions such as clinical evaluation, preoperative counseling, and management strategies can be of great value in identifying and resolving patients' anxiety and negative emotions to improve postoperative outcomes.
Lymphocyte apoptosis and monocyte dysfunction play a pivotal role in sepsis-induced immunosuppression. Programmed death-1 (PD1) and its ligand programmed death ligand-1 (PD-L1) exert inhibitory ...function by regulating the balance among T cell activation, tolerance, and immunopathology. PD-1 deficiency or blockade has been shown to improve survival in murine sepsis. However, PD-L1 and PD-1 differ in their expression patterns and the role of PD-L1 in sepsis-induced immunosuppression is still unknown.
Sepsis was induced in adult C57BL/6 male mice via cecal ligation and puncture (CLP). The expression of PD-1 and PD-L1 expression on peripheral T cells, B cells and monocytes were measured 24 hours after CLP or sham surgery. Additionally, the effects of anti-PD-L1 antibody on lymphocyte number, apoptosis of spleen and thymus, activities of caspase-8 and caspase-9, cytokine production, bacterial clearance, and survival were determined.
Expression of PD-1 on T cells, B cells and monocytes and PD-L1 on B cells and monocytes were up-regulated in septic animals compared to sham-operated controls. PD-L1 blockade significantly improved survival of CLP mice. Anti-PD-L1 antibody administration prevented sepsis-induced depletion of lymphocytes, increased tumor necrosis factor (TNF)-α and interleukin (IL)-6 production, decreased IL-10 production, and enhanced bacterial clearance.
PD-L1 blockade exerts a protective effect on sepsis at least partly by inhibiting lymphocyte apoptosis and reversing monocyte dysfunction. Anti-PD-L1 antibody administration may be a promising therapeutic strategy for sepsis-induced immunosuppression.
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