Cross-coupling reactions of phenylmagnesium halides with fluoroazines and fluorodiazines

The first nickel-catalyzed cross-coupling reactions between fluoroarenes and aryl organometallics using commercially available ligands are described. The nickel-catalyzed cross-coupling reactions between aryl Grignard reagents and fluoroazines and -diazines occurred in THF at room temperature using commercially available 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, or 1,1'-bis(diphenylphosphino)ferrocene as ligand. Various fluoro substrates such as pyridines, diazines (pyrazine, pyridazine), benzodiazines (quinoxaline), and quinolines were successfully involved in the reaction with phenylmagnesium halides (phenylmagnesium chloride, 2-methoxyphenylmagnesium bromide, and 4-methoxyphenylmagnesium bromide). The conditions used also allowed the cross-coupling of 4-fluorotoluene with arylmagnesium reagents.     

Two N,N′‐diaryl‐2,2,2‐trichloroethane‐1,1‐diamines: hydrogen‐bonded supramolecular structures in one and two dimensions

The molecules of 2,2,2‐trichloro‐N,N′‐diphenylethane‐1,1‐diamine, C₁₄H₁₃Cl₃N₂, are linked into (040) sheets by a combination of C—H...Cl and C—H...π(arene) hydrogen bonds. In 2,2,2‐trichloro‐N,N′‐bis(4‐methylphenyl)ethane‐1,1‐diamine, C₁₆H₁₇Cl₃N₂, the molecules are linked into C(7) chains by two independent C—H...Cl hydrogen bonds and one Cl...Cl contact.     

大气采样器检定规程探讨及修订建议

通过对大气采样器流量示值误差进行计量检定发现,是否有吸收负栽检定结果差别较大,而计量检定规程并没有详细说明,因此对大气采样器检定规程进行了探讨并提出修改建议.     

肌醇在氯化钠水溶液中的稀释焓和焓对相互作用

应用微量热法测定了298.15K时肌醇在纯水和氯化钠水溶液中的稀释焓,根据McMillan-Mayer理论计算了肌醇在不同浓度的氯化钠溶液中的2到4阶焓相互作用系数.结果表明,肌醇在氯化钠溶液中的焓对相互作用系数h2均为负值,并且随着氯化钠浓度的增大,h2的值呈增大趋势.根据溶质-溶质相互作用和溶质-溶剂相互作用对焓对相互作用系数的变化趋势进行了解释.     

Robust Laminated Anode with an Ultrathin Titanium Nitride Layer for High-Efficiency Top-Emitting Organic Light-Emitting Diodes

The effective reflective anode remains a highly desirable component for the fabrication of reliable top-emitting organic light-emitting diodes (TE-OLEDs) which have the potential to be integrated with complementary metal-oxide-semiconductor (CMOS) circuits for microdisplays. This work demonstrates a novel laminated anode consisting of a Cr/Al/Cr multilayer stack. Furthermore, we implement an ultra-thin titanium nitride (TiN) layer as a protective layer on the top of the Cr/Al/Cr composite anode, which creates a considerably reflective surface in the visible range, and meanwhile improves the chemical stability of the electrode against the atmosphere or alkali environment. Based on [2-(2-pyridinyl-N)phenyl-C](acetylacetonate)iridium(III) as green emitter and Mg/Ag as transparent cathode, our TE-OLED using the TiN-coated anode achieves the maximum current efficiency of 71.2 cd/A and the maximum power efficiency of 66.7 lm/W, which are 81% and 90% higher than those of the reference device without TiN, respectively. The good device performance shows that the Cr/Al/Cr/TiN could function as a promising reflective anode for the high-resolution microdisplays on CMOS circuits.     

Front Transparent Passivation of CIGS-Based Solar Cells via AZO

We report a novel strategy for the front passivation of solar cells via aluminum-doped zinc oxide (AZO) films in the case of CIGS solar cells, leading to the highest efficiency of 15.07% without alkali metal post treatment and anti−reflective layer. The good passivation of CIGS solar cells via AZO films is attributed to the field passivation simulated by the SCAPS−1D software. The AZO films also exhibit high optical transparency both in visible and near infrared wavelength region, high conductivity, and cost−effective fabrication advantage. Importantly, the AZO films are deposited at room temperature via radio−frequency magnetron sputtering, showing that the AZO films are also applicable to other solar cells such as perovskite solar cells. Our work is of significance for advancing the development of CIGS−based photovoltaics devices by the well front passivation of AZO. The wide application of AZO in other solar cells such as perovskite solar cells and related tandem solar cells may also accelerate the development of these solar cells because of potential passivation of AZO, low deposition temperature, and high optical transparency of AZO.     

Organic/Inorganic Species Synergistically Supported Unprecedented Vanadomolybdates

Vanadomolybdates (VMos), comprised of Mo and V in high valences with O bridges, are one of the most important types of polyoxometalates (POMs), which have high activity due to their strong capabilities of gaining/losing electrons. Compared with other POMs, the preparation of VMos is difficult due to their relatively low structural stability, especially those with unclassical architectures. To overcome this shortcoming, in this study, triol ligands were applied to synthesize VMos through a beaker reaction in the presence of V₂O₅, Na₂MoO₄, and organic species in the aqueous solution. The single-crystal X-ray diffraction results indicate that two VMo clusters, Na₄{V₅Mo₂O₁₉[CH₃C(CH₂O)₃]}∙13H₂O and Na₄{V₅Mo₂O₁₉[CH₃CH₂C(CH₂O)₃]}∙13H₂O, with a similar architecture, were synthesized, which were both stabilized by triol ligand and {MoO₆} polyhedron. Both clusters are composed of five V ions and one Mo ion in a classical Lindqvist arrangement with an additional Mo ion, showing an unprecedented hepta-nuclear VMo structure. The counter Na⁺ cations assemble into one-dimensional channels, which facilitates the transport of protons and was further confirmed by proton conductivity experiments. The present results provide a new strategy to prepare and stabilize VMos, which is applicable for developing other compounds, especially those with untraditional architectures.     

Mesoporous sodium four-coordinate aluminosilicate nanoparticles modulate dendritic cell pyroptosis and activate innate and adaptive immunity

Pyroptosis is a programmed cell death widely studied in cancer cells for tumour inhibition, but rarely in dendritic cell (DC) activation for vaccine development. Here, we report the synthesis of sodium stabilized mesoporous aluminosilicate nanoparticles as DC pyroptosis modulators and antigen carriers. By surface modification of sodium-stabilized four-coordinate aluminium species on dendritic mesoporous silica nanoparticles, the resultant Na-^IVAl-DMSN significantly activated DC through caspase-1 dependent pyroptosis via pH responsive intracellular ion exchange. The released proinflammatory cellular contents further mediated DC hyperactivation with prolonged cytokine release. In vivo studies showed that Na-^IVAl-DMSN induced enhanced cellular immunity mediated by natural killer (NK) cells, cytotoxic T cells, and memory T cells as well as humoral immune response. Our results provide a new principle for the design of next-generation nanoadjuvants for vaccine applications.

Na-^IVAl-DMSN acts as both antigen carriers and modulators to “hyperactivate” dendritic cells (DCs) via potassium (K⁺) efflux dependent pyroptosis, eventually leading to enhanced adaptive and innate immunity.     

基于单透镜的空间光-单模光纤耦合方法

将自由空间光耦合进单模光纤产生超连续谱的实验中,空间光与单模光纤的耦合效率是其中的一个关键问题。常采用的单透镜或显微物镜进行耦合存在耦合效率低、调整难度大、端面易损伤等问题。提出了先将自由空间的光耦合进纤芯尺寸较大的单模光纤,然后将纤芯较大的单模光纤和纤芯较小的单模光纤进行熔接。实验结果表明,改进的耦合系统耦合效率大大提高,达到60％以上,且调整难度降低,光纤端面的损伤概率降低,大大提高了超连续谱产生的效率。