Oxygen evolution reaction: a perspective on a decade of atomic scale simulations

Multiple strategies to overcome the intrinsic limitations of the oxygen evolution reaction (OER) have been proposed by numerous research groups. Despite the substantial efforts, the driving force required for water oxidation is largely making the reaction inefficient. In the present work, we collected published studies involving DFT calculations for the OER, with the purpose to understand why the progress made so far, for lowering the overpotential of the reaction, is relatively small. The data revealed that the universal scaling relationship between HO* and HOO* intermediates is still present and robust, despite the variety in methods and structures used for calculating the binding energies of the intermediates. On the other hand, the data did not show a clear trend line regarding the O* binding. Our analysis suggested that trends in doped semiconducting oxides behave very differently from those in other oxides. This points towards a computational challenge in describing doped oxides in a realistic manner. We propose a way to overcome these computational challenges, which can be applied to simulations corresponding to doped semiconductors in general.

Multiple strategies to overcome the intrinsic limitations of the oxygen evolution reaction (OER) have been proposed by numerous research groups.     

高效液相色谱法测定大鼠血浆中的原儿茶酸

建立了大鼠血浆中原儿茶酸含量测定的高效液相色谱方法。采用的色谱柱为DiamondsilTM C18 柱(150 mm×4.6 mm,5 μm);流动相为乙腈-水(体积比为9∶91,用H3PO4 调pH至2.5);流速1.2 mL/min;检测波长260 nm;内标为对羟基苯甲酸。原儿茶酸的线性范围为0.050~3.20 mg/L,线性相关系数为0.9978，最低定量限为0.050 mg/L,日内和日间测定的精密度（以相对标准偏差表示）均低于7.0%,准确度（以相对误差表示）为-1.4%～2.6%；在0.050,0.40,3.20 mg/L低、中、高3个添加浓度水平下，血浆样品的提取回收率分别为83.4%,87.3%,91.1%。该方法简便,灵敏,准确,适用于大鼠体内原儿茶酸的药物动力学研究。     

The quenching of CdSe quantum dots photoluminescence by gold nanoparticles in solution

The photoluminescence (PL) of CdSe quantum dots (QD) in aqueous media has been studied in the presence of gold nanoparticles (NP) with different shapes. The steady state PL intensity of CdSe QD (1.5-2 nm in size) is quenched in the presence of gold NP. Picosecond bleach recovery and nanosecond time-resolved luminescence measurements show a faster bleach recovery and decrease in the lifetime of the emitting states of CdSe QD in the presence of quenchers. Surfactant-capped gold nanorods (NR) with aspect ratio of 3 and surfactant-capped and citrate-capped nanospheres (NS) of 12 nm diameter were used as quenchers in order to study the effect of shape and surface charge on the quenching rates. The Stern-Volmer kinetics model is used to examine the observed quenching behavior as a function of the quencher concentration. It was found that the quenching rate of NR is more than 1000 times stronger than that of NS with the same capping material. We also found that the quenching rate decreases as the length of the NR decreases, although the overlap between the CdSe emission and the NR absorption increases. This suggests that the quenching is a result of electron transfer rather than long-range (Forster-type) energy transfer processes. The quenching was attributed to the transfer of electron with energies below the Fermi level of gold to the trap holes of CdSe QD. The observed large difference between NR and NS quenching efficiencies was attributed to the presence of the [110] facets only in the NR, which have higher surface energy.     

Comparison of Fatty Acid Contents and MMP-1 Inhibitory Effects of the Two Antarctic Fish,Notothenia rossii and Champsocephalus gunnari

Total fatty-acid (FA) contents of different organs (stomach, liver, brain, and skin) of two Antarctic fish, marbled rockcod (Notothenia rossii) and mackerel icefish (Champsocephalus gunnari), were examined using gas chromatography–mass spectrometry (GC–MS). N. rossii possessed higher contents of total omega-3, where eicosapentaenoic acid (EPA) and docosahexaenoic acid (DHA), the most represented omega-3 FAs, were distributed throughout all parts of the fish. The highest level of EPA was observed in the skin and that of DHA was observed in the brain of N. rossii. C. gunnari showed organ peculiarity in that most of the omega-3 FAs were found in stomach and skin. Specifically, the highest levels of EPA and DHA were both observed in the stomach. Although N. rossii and C. gunnari both inhabit the Antarctic Southern Oceans, their characteristics in terms of the composition of fatty acids were shown to vary. The extracts were also evaluated for matrix metalloproteinase-1 (MMP-1)-inhibitory activities in UVB-induced human dermal fibroblasts, where extracts of the skin and liver of N. rossii showed the most significant inhibition upon MMP-1 production. These findings provide experimental evidence that the extracts of the Antarctic fish could be utilized as bioactive nutrients, particularly in the enhancement of skin health.     

水性乳液/聚氨酯模型缔合增稠剂的触变性机理

以异佛尔酮二异氰酸酯(IPDI)与聚乙二醇(PEG,分子量为4000,6000和8000)为原料,以直链醇(C12,C14,C16和C18)为封端剂,合成了疏水改性乙氧基化氨基甲酸酯(HEUR),并将其应用于乳液增稠.采用核磁共振波谱(¹H NMR)、傅里叶变换红外光谱(FTIR)及凝胶渗透色谱(GPC)表征了HEUR的结构、分子量及其分布,研究了其在水性乳液中的流变行为.研究结果表明,当HEUR封端基团为C14,C16和C18,且质量分数增加到1. 0%以上时,增稠的乳液(Latex/HEUR)的流变曲线出现触变环,为触变性流体.当HEUR亲疏水比值(R_h)减小时,疏水性增强,触变环向低剪切速率(γ˙)方向移动,黏度下降率(Δη)增大;当HEUR用量增加时,触变环面积(S_loop)也增大.这些触变性特点归因于HEUR在乳液中的缔合作用、氢键作用及链缠结.利用扫描电子显微镜(SEM)和原子力显微镜(AFM)对Latex/HEUR的聚集态和表面形貌进行了表征.结果表明,随着HEUR封端基团链长增加,Latex/HEUR颗粒...     

波纹结构迎爆面泡沫金属对甲烷-空气混合气体爆炸能量的吸收特性

为进一步探究气体爆炸荷载下异构迎爆面泡沫金属的吸能特性,在前期开展锯齿结构迎爆面材料吸能特性实验的基础上,以3种波纹结构迎爆面（凸面型、凹面型和凹凸连续型）泡沫金属材料为研究对象,利用自主搭建的气体爆炸管网实验平台,开展了该泡沫金属材料在甲烷-空气混合气体爆炸荷载下的吸能特性测定实验。采用不同波纹结构迎爆面阻隔爆材料,测定了管道内爆炸冲击波超压、火焰传播速度和火焰温度等随时间和空间的变化,分析了不同波纹结构迎爆面阻隔爆材料的吸能效果。结果表明：(1)迎爆面为波纹结构的泡沫金属材料对爆炸超压的衰减效果优于迎爆面为锯齿结构的泡沫金属材料和迎爆面为平面结构的泡沫金属材料,且迎爆面为凸面型波纹结构和凹凸连续型波纹结构的泡沫金属材料对超压衰减的速率高于迎爆面为锯齿结构和凹面型波纹结构的泡沫金属材料;迎爆面为锯齿结构的泡沫金属材料对火焰传播速度的衰减略强于迎爆面为波纹结构和平面结构的泡沫金属材料;迎爆面为波纹结构的泡沫金属材料对火焰温度的衰减效果优于迎爆面为锯齿结构及平面结构的泡沫金属材料。(2)在本文实验条件下,3种波纹结构（凸面型、凹面型和凹凸连续型）迎爆面泡沫金属材料的熄爆参数分别为5.338、4.340和6.090 MPa·℃,低于锯齿结构迎爆面材料的熄爆参数17.680 MPa·℃,且远低于熄爆参数安全值390 MPa·℃,波纹结构迎爆面材料具有良好的防护效果。(3)这3种迎爆面为波纹结构的泡沫金属材料均具有良好的吸能特性,均优于迎爆面为锯齿形结构的泡沫金属材料,且明显优于迎爆面为平面结构的泡沫金属材料。

     

兰州重离子医疗装置同步环安装控制网设计

介绍了兰州重离子医疗装置（HIMM）建造中准直安装方案里核心的测量控制网设计。同步环准直测量控制网是基于Leica AT401激光跟踪仪和综合测量软件SA建立的三维测量控制网,在控制网设计中采用9个基准柱和2个激光干涉测量得到的基准长度参考,以及Leica DNA03数字水准仪协同测量,使全局三维控制网设计精度达到0.04 mm,最终确保同步环四极磁铁安装精度达到0.10 mm的要求指标,为将来束流的稳定运行做好可靠的保证。     

鱼藤中抗肿瘤活性化合物的追踪分离及与DNA的相互作用

采用活性追踪分离的方法, 从鱼藤中分离鉴定出了2个抗肿瘤活性化合物, 即羟基鱼藤素(1)和鱼藤酮(2). 用丽丝胺罗丹明B(SRB)法评价其抗肿瘤活性, 用紫外光谱和荧光光谱等方法探讨了化合物与DNA的相互作用. 结果发现, 羟基鱼藤素(1)与鱼藤酮(2)为鱼藤的抗肿瘤活性成分, 对人大肠癌细胞HCT8、人肝癌细胞BEL7402、人胃癌细胞BGC823、人肺癌细胞A549和人卵巢癌细胞A2780的半数抑制浓度(IC₅₀) 在0.1~90.0 μmol/L之间. 这两种化合物的紫外吸收强度随着HS-DNA的加入均呈现减色效应, 并使EB-HS-DNA复合体系荧光强度减弱, 表明化合物的抗肿瘤活性与DNA以插入方式作用有关.     

Numerical investigation on the heat transfer performance inside sublimator driven coldplate for aerospace applications

Journal of Thermal Analysis and Calorimetry - Sublimator offers effective heat rejection for the spacecraft, which work in warm environments or with peak heat loads, by evaporating or sublimating...     

Strategies for the construction of supramolecular assemblies from poly-NHC ligand precursors

The field of supramolecular assemblies has developed rapidly in the last few decades, thanks in a large part to their diverse applications. These assemblies have been mostly based on Werner-type coordination motifs in which metal centres are coordinated by nitrogen or oxygen donors. Recently, N-heterocyclic carbene(NHC) ligands have been employed as carbon donors not only because of their appealing structures but also due to the extensive applications in catalysis, biomedicine and material science of the resulting assemblies. During the last decade, NHC-based supramolecular assemblies have witnessed rapid growth and extensive application in molecular recognition, luminescent materials and catalysis. For different topological systems, a diverse selection of poly-NHC precursors and synthetic strategies is crucial to precisely control the synthesis of supramolecular architectures. Several synthetic strategies have been developed to synthesise two-dimensional(2D) molecular metallacycles and three-dimensional(3D) metallacages from a wide range of poly-NHC precursors, including a straightforward one-pot strategy,supramolecular transmetalation, stepwise synthesis, an improved one-pot strategy involving self-sorting behaviour of 3D metallacages and a subtle variation strategy of poly-NHC ligand precursors. This review offers a summary of the synthetic strategies applied for the construction of different poly-NHC-based supramolecular assemblies, particularly emphasizes recent progress in the synthesis of large and complex supramolecular assemblies from poly-NHC precursors, and further attention is given to their application in postsynthetic modifications(PSMs), host-guest chemistry, luminescent properties and biomedical applications.