Subdominant H60 antigen-specific CD8 T-cell response precedes dominant H4 antigen-specific response during the initial phase of allogenic skin graft rejection

In allogeneic transplantation, including the B6 anti-BALB.B settings, H60 and H4 are two representative dominant minor histocompatibility antigens that induce strong CD8 T-cell responses. With different distribution patterns, H60 expression is restricted to hematopoietic cells, whereas H4 is ubiquitously expressed. H60-specific CD8 T-cell response has been known to be dominant in most cases of B6 anti-BALB.B allo-responses, except in the case of skin transplantation. To understand the mechanism underlying the subdominance of H60 during allogeneic skin transplantation, we investigated the dynamics of the H60-specific CD8 T cells in B6 mice transplanted with allogeneic BALB.B tail skin. Unexpectedly, longitudinal bioluminescence imaging and flow cytometric analyses revealed that H60-specific CD8 T cells were not always subdominant to H4-specific cells but instead showed a brief dominance before the H4 response became predominant. H60-specific CD8 T cells could expand in the draining lymph node and migrate to the BALB.B allografts, indicating their active participation in the anti-BALB.B allo-response. Enhancing the frequencies of H60-reactive CD8 T cells prior to skin transplantation reversed the immune hierarchy between H60 and H4. Additionally, H60 became predominant when antigen presentation was limited to the direct pathway. However, when antigen presentation was restricted to the indirect pathway, the expansion of H60-specific CD8 T cells was limited, whereas H4-specific CD8 T cells expanded significantly, suggesting that the temporary immunodominance and eventual subdominance of H60 could be due to their reliance on the direct antigen presentation pathway. These results enhance our understanding of the immunodominance phenomenon following allogeneic tissue transplantation.     

Mono‐ and Dinuclear Phosphorescent Rhenium(I) Complexes: Impact of Subcellular Localization on Anticancer Mechanisms

Elucidation of relationship among chemical structure, cellular uptake, localization, and biological activity of anticancer metal complexes is important for the understanding of their mechanisms of action. Organometallic rhenium(I) tricarbonyl compounds have emerged as potential multifunctional anticancer drug candidates that can integrate therapeutic and imaging capabilities in a single molecule. Herein, two mononuclear phosphorescent rhenium(I) complexes ( Re1 and Re2 ), along with their corresponding dinuclear complexes ( Re3 and Re4 ), were designed and synthesized as potent anticancer agents. The subcellular accumulation of Re1–Re4 was conveniently analyzed by confocal microscopy in situ in live cells by utilizing their intrinsic phosphorescence. We found that increased lipophilicity of the bidentate ligands could enhance their cellular uptake, leading to improved anticancer efficacy. The dinuclear complexes were more potent than the mononuclear counterparts. The molecular anticancer mechanisms of action evoked by Re3 and Re4 were explored in detail. Re3 with a lower lipophilicity localizes to lysosomes and induces caspase‐independent apoptosis, whereas Re4 with higher lipophilicity specially accumulates in mitochondria and induces caspase‐independent paraptosis in cancer cells. Our study demonstrates that subcellular localization is crucial for the anticancer mechanisms of these phosphorescent rhenium(I) complexes.     

Direct Synthesis of Adipic Esters and Adiponitrile via Photoassisted Cobalt-Catalyzed Alkene Hydrodimerization

The direct hydrodimerization of acrylates and acrylonitrile offers a general streamlined access to industrially important intermediates to nylon 6,6. However, a practical catalytic method for this process has thus far underdeveloped owing to the challenges in regioselectivity and environmental compatibility of applied reagents. Here, we report a cobalt-catalyzed tail-to-tail hydrodimerization of activated alkenes driven by a visible-light photoredox catalysis at ambient temperature, which is applicable to both adipates and adiponitrile synthesis from potentially renewable feedstocks. This protocol utilizes half equivalent of hantzsch ester as a recyclable two-electron and two-proton donor with the assistance of catalytic amount of base as a proton shuttle, and has been shown to be highly regioselective and efficient for hydrodimerizing various activated alkenes to 1,4-difunctionalized butane derivatives.     

Stable Heterometallic Cluster‐Based Organic Framework Catalysts for Artificial Photosynthesis

A series of stable heterometallic Fe₂M cluster‐based MOFs ( NNU‐31‐M , M=Co, Ni, Zn) photocatalysts are presented. They can achieve the overall conversion of CO₂ and H₂O into HCOOH and O₂ without the assistance of additional sacrificial agent and photosensitizer. The heterometallic cluster units and photosensitive ligands excited by visible light generate separated electrons and holes. Then, low‐valent metal M accepts electrons to reduce CO₂, and high‐valent Fe uses holes to oxidize H₂O. This is the first MOF photocatalyst system to finish artificial photosynthetic full reaction. It is noted that NNU‐31‐Zn exhibits the highest HCOOH yield of 26.3 μmol g^?1 h^?1 (selectivity of ca. 100 %). Furthermore, the DFT calculations based on crystal structures demonstrate the photocatalytic reaction mechanism. This work proposes a new strategy for how to design crystalline photocatalyst to realize artificial photosynthetic overall reaction.     

基于八面体理论的岩石循环加-卸载本构模型及修正

探究岩石的受力特点及破坏特性是研究岩石地下工程安全性的关键,诸多学者都期望能在岩石本构模型的研究上取得突破性进展。在此背景下,提出了一种能够描述循环加-卸载条件下岩石的本构模型。首先,假设岩石的微元强度服从八面体剪应力理论并且微元破坏服从Weibull概率公式,将岩石本构中的损伤变量以及岩石微元强度表达式里包含的损伤因子进行本构变换,得到关于应力、应变等其他表现加-卸载下岩石损伤本构模型的参数,表示出岩石微元强度和损伤变量,再将得到的岩石微元强度和损伤变量代入所提出的岩石本构模型中,并进行等式变换得到一个函数表达式。通过将其与实验数据进行拟合对比分析,得出修正后的拟合参数,将其代入函数式中,得到损伤本构模型的修正式。最后将拟合参数进行必要的敏感性分析,得出各拟合参数的实际物理意义。     

Efficient deep blue organic light emitting diodes based on [2,7,7,13,13-pentamethyl-9-(10-phenylanthracen-9-yl)-7,13-dihydrobenzo[5,6]-s-indaceno[1,2-g]quinoline] derivatives

Abstract

In this study, as the ongoing effort to develop efficient blue OLEDs, two deep blue emitters based on indenoquinoline-substituted anthracene derivatives have been synthesized and characterized. Multilayer organic light emitting diodes were fabricated with the following sequence: indium-tin-oxide (ITO)/4,4’,4’’-tris[2-naphthyl(phenyl)amino (2-TNATA)/4,4’-bis(N-(1-naphthyl)-N-phenylamino) biphenyl (NPB)/Blue emitting materials/Bathophenanthroline (Bphen)/lithium quinolate (Liq)/Al. All the devices showed efficient blue emissions. Particularly, a device using ‘2,7,7,13,13-pentamethyl-9-(10-phenylanthracen-9-yl)?7,13-dihydrobenzo[5,6]-s-indaceno[1,2-g] quinoline’ as an emitter showed a maximum external quantum efficiency (EQE) of 4.92% with the Commission Internationale De L’Énclairage (CIE) coordinates of (0.15, 0.10) at 8.0?V.     

Persistent Room Temperature Phosphorescence from Triarylboranes: A Combined Experimental and Theoretical Study

Achieving highly efficient phosphorescence in purely organic luminophors at room temperature remains a major challenge due to slow intersystem crossing (ISC) rates in combination with effective non‐radiative processes in those systems. Most room temperature phosphorescent (RTP) organic materials have O‐ or N‐lone pairs leading to low lying (n, π*) and (π, π*) excited states which accelerate k_isc through El‐Sayed's rule. Herein, we report the first persistent RTP with lifetimes up to 0.5 s from simple triarylboranes which have no lone pairs. RTP is only observed in the crystalline state and in highly doped PMMA films which are indicative of aggregation induced emission (AIE). Detailed crystal structure analysis suggested that intermolecular interactions are important for efficient RTP. Furthermore, photophysical studies of the isolated molecules in a frozen glass, in combination with DFT/MRCI calculations, show that (σ, B p)→(π, B p) transitions accelerate the ISC process. This work provides a new approach for the design of RTP materials without (n, π*) transitions.     

Interchange-turbulence-based radial transport model for SOLPS-ITER: A COMPASS case study

Mean-field plasma edge transport codes such as SOLPS-ITER heavily rely on ad-hoc radial diffusion coefficients to approximately model anomalous transport. Such coefficients are experimentally determined and vary between different machines, and also depend on the operational regime and plasma location within the same device. Therefore, to match experimental data the modeller is required to manually tune several free parameters in expensive simulations, and the code's predictive capabilities are significantly downgraded. As a solution, a new model has been developed for SOLPS-ITER, solving an additional transport equation for the turbulent kinetic energy k, derived by consistently time-averaging the Braginskii equations, and including a diffusive closure for the anomalous particle flux. This closure model relates the anomalous diffusion coefficient to the local k value. The resulting equation structure and its closure are inspired by TOKAM2D isothermal interchange turbulence simulation results. Within this model, fewer and hopefully more universal free parameters are retained, thus improving the code's predictive capabilities. The new model has been tested on a COMPASS case for which upstream plasma profiles were available. Experimental data and a reference solution, obtained by matching the profiles through manual tuning of radial diffusivities, have been used to estimate the parameters of our new transport model. A ballooned particle diffusivity profile is retrieved by the new radial transport model, thanks to the proposed interchange drive. The obtained upstream profiles qualitatively agree with the experiment and prove the new model is a promising first attempt to be further refined.