Directed deposition of functional polymers onto porous substrates using metal salt inhibitors

This paper demonstrates the ability to control the location of polymer deposition onto porous substrates using vapor phase polymerization in combination with metal salt inhibitors. Functional polymers such as hydrophobic poly(1H,1H,2H,2H-perfluorodecyl acrylate), click-active poly(pentafluorophenyl methacrylate), and light-responsive poly(ortho-nitrobenzyl methacrylate) were patterned onto porous hydrophilic substrates using metal salts. A combinatorial screening approach was used to determine the effects of different transition metal salts and reaction parameters on the patterning process. It was found that CuCl(2) and Cu(NO(3))(2) were effective at uniformly inhibiting the deposition of all three polymers through the depth of the porous substrate and along the entire cross section. This study offers a new and convenient method to selectively deposit a wide variety of functional polymers onto porous materials and will enable the production of next-generation multifunctional paper-based microfluidic devices, polymeric photonic crystals, and filtration membranes.     

Ligand-Accelerated Activation of Strong CH Bonds of Alkanes by a (Salen)ruthenium(VI)-Nitrido Complex

Kinetic and mechanistic studies on the intermolecular activation of strong C?H bonds of alkanes by a (salen)ruthenium(VI) nitride were performed. The initial, rate-limiting step, the hydrogen atom transfer (HAT) from the alkane to Ru(VI) ?N, generates Ru(V) ?NH and RC(.) HCH(2) R. The following steps involve N-rebound and desaturation.     

Oxidation states of Cu in the CuO/CeO2/Al2O3 catalyst in the methanol steam reforming process

The biomorphic CuO/CeO₂/Al₂O₃ was used as a catalyst in methanol steam reforming (SRMe), and the reaction mechanism was studied. It was found that the oxidation states of Cu in the biomorphic sample would vary with the reaction temperature and they also affected the rate of the reaction. Below 200 °C, SRMe would not occur, and the X-ray diffractometry study indicated that the CuO/CeO₂/Al₂O₃ sample remained unchanged. Above 200 °C, the SRMe occurred when CuO started to be reduced to Cu. As the reaction temperature increased, Cu reacted with CO₂ and led to the formation of Cu₂O during the reversed water gas shift reaction. Above 250 °C, the conversion of MeOH to CO₂ and H₂ reached to a saturation of 95% even if the amount of metallic Cu was reduced to half of its original portion. This confirmed that both Cu and Cu₂O were active components for promoting SRMe.     

Iron complex-catalyzed N-arylation of pyrazoles under aqueous medium

Commercially available FeCl₃·6H₂O with conformationally rigid diamine ligand is a highly effective catalyst for N-arylation of pyrazoles using aryl and heteroaryl iodides. It is notable to show that this complex is tolerable under aqueous medium and particularly the whole reaction utilizes water as the sole solvent without any additional organic co-solvents and surfactants. Attempted study using other nitrogen nucleophiles is described. This newly developed system provides an alternative protocol to Cu- and Pd-catalyzed N-arylation reactions.     

Strongly Luminescent Tungsten Emitters with Emission Quantum Yields of up to 84 %: TADF and High‐Efficiency Molecular Tungsten OLEDs

Metal‐TADF (thermally activated delayed fluorescence) emitters hold promise in the development of next generation light‐emitting materials for display and lighting applications, examples of which are, however, largely confined to Cu^I and recently Au^I, Ag^I, and Au^III emitters. Herein is described the design strategy for an unprecedented type of metal‐TADF emitter based on inexpensive tungsten metal chelated with Schiff base ligand that exhibit high emission quantum yields of up to 56 % in solutions and 84 % in thin‐film (5 wt % in 1,3‐bis(N‐carbazolyl)benzene, mCP) at room temperature. Femtosecond time‐resolved emission (fs‐TRE) spectroscopy and DFT calculations were undertaken to decipher the TADF properties. Solution‐processed OLEDs fabricated with the W‐TADF emitter demonstrated external quantum efficiency (EQE) and luminance of up to 15.6 % and 16890 cd m^?2, respectively.     

基于GIS与确定性系数分析方法的汶川地震滑坡易发性评价

鱼类经常采用垂直流向的摆动进行游动, 这种摆动可以用行进波来表示. 应用浸入边界方法模拟了低雷诺数条件下水翼NACA65-010在水中摆动时的流场,并研究了雷诺数对水生动物推进效率的影响. 结果表明：随着雷诺数的增大,推力系数和推进效率增大,而功率系数减小;在Re<20时,推力系数,推进效率和功率系数的变化尤为剧烈. 随雷诺数增加,由于水翼摆动诱导的流场变化也更加复杂,水翼后缘处的涡量场强度逐渐增强. 摆动诱导反卡门涡街产生推力.     

2008汶川大地震极端滑坡事件初步研究

  为了分析汶川地震诱发滑坡灾害事件强度和影响,本文以汶川地震诱发滑坡极端事件为线索,在统计分析前10个规模最大、位移最远、危害最重及最大滑坡堰塞湖分布特征的基础上,重点研究前三甲极端滑坡事件的简要特征,初步揭示： (1)汶川地震诱发的极端滑坡事件主要沿龙门山中央断裂（映秀—北川断裂带）和Ⅹ-Ⅺ高烈度地段分布,强震的振动力、地震主传播方向和发震断裂NE向扩展作用是启动极端滑坡事件的主要原因;  (2)规模最大的前10个滑坡和距离最大的前10个高速远程滑坡具有很好的重合特征,两者都反映汶川地震诱发的高能量滑坡事件; 其中,规模最大的绵竹市安县大光包滑坡,初步估算体积约742×108m3,最大运动距离达到35km,距离排名第二; 距离最大的绵竹文家沟高速远程滑坡,初步估算最大位移为42km,其体积约15×108m3,规模排名第二,这两个滑坡都属于世界上罕见的大型高能量高速远程滑坡;  (3)前10个最大的灾难性滑坡事件,累计导致3751人死亡,单个滑坡引起的人员死亡超过100人,最多的达到1600人,属于世界上罕见的灾难性滑坡事件;  （4）潜在危险性最大的10个滑坡堰塞湖,曾经威胁几十万人的生活安全,其中,最大的北川唐家山滑坡堰塞湖,曾经威胁下游绵阳市30万人的生活安全,这些滑坡堰塞湖都及时采取人工开挖措施排除了潜在危险。     

世界三大典型水库型顺层岩质滑坡工程地质比较研究

通过对瓦依昂滑坡、塘岩光滑坡、千将坪滑坡滑坡三大滑坡工程地质比较研究,找出了其地形地质条件、诱发因素、变形特征的基本规律和共性,揭示了库水浮托与滑带浸泡软化及二者耦合的滑坡诱发机制; 提出了水库顺层岩质滑坡的基于易滑地质结构的空间预测模型; 初步总结了水库顺层岩质滑坡短期及临滑变形特征。     

清江大龙潭水利枢纽防渗帷幕设计及效果监测分析

大龙潭水电站坝址位于碳酸盐岩地区,岩溶发育受岩性和构造控制：在奥陶系南津关组第一段(O1n1)页岩夹灰岩、第二段第一层(O1n2-1)泥质条带灰岩及寒武系第四段第二层硅质条带灰岩(∈4-23m)中岩溶不发育,其他地层的灰岩中岩溶发育; 岩溶发育方向主要沿岩层层面和顺河向的断层发育,形成岩溶通道。因此水库渗漏主要沿岩溶发育的断层产生,防渗帷幕设计以奥陶系底部188m页岩为防渗依托,并重点加大断层部位的工程量。后期地下水长期观测分析表明,帷幕防渗效果良好,不存在大的库水渗漏,仅在局部断层构造发育部位渗漏量略大。大龙潭水电站防渗帷幕工程成功的范例为碳酸盐岩地区其他工程的防渗优化设计提供了很好的借鉴意义。     

倒虹吸形成深饱水带大型充填溶洞的典型实例——圆梁山隧道毛坝向斜深饱水带特大型充填溶洞的形成及充填物成灾机制分析

圆梁山深埋特长隧道是渝怀铁路越岭线路方案的关键性控制工程,隧道总长11.070km。隧道穿越四周被志留系和泥盆系泥岩包围的二叠系及三叠系碳酸盐岩构成且受众多NW～NWW向横张断裂切割的毛坝紧密向斜。穿越毛坝向斜碳酸盐岩长度约2.2km。地表多为岩溶洼地及槽谷,岩溶泉、泉群、暗河多出露于横张断裂端部碳酸盐岩与下伏泥岩接触带。泉出露高程,亦即向斜岩溶水局部排水基准面,多在850～900m以上。隧道高程低于局部排水基准面400～450m。隧道施工开挖揭示,向斜核部和东翼在隧道洞身附近当地地下水位400m以下发育有3个罕见的特大型充填溶洞。其中平切面积达6000m2充填有紫红色粉细砂的2#溶洞多次发生涌砂突水灾害,总涌砂量高达6×10⁴m³。3#溶洞则发生过极其特殊的黏性土爆喷型突出灾害。初步综合分析认为：向斜核部的层间滑脱和纵向张裂隙以及东翼茅口碳酸盐岩中部的层间错动带,被NW～NWW向横张断裂所交切,为岩溶水的深循环提供了较通畅的原始通道; 横断层间的水头差,导致岩溶水在此通道中做倒虹吸循环; 长期差异溶蚀使原始导水能力强的裂隙或断裂发展为溶洞,其中的水流转化为管道流。强烈溶蚀冲刷与顶板坍塌导致向斜核部吴家坪组碳酸盐岩中的层间滑脱与纵向张裂隙分别发育为1#、2#溶洞,东翼茅口碳酸盐岩中的层间错动带则发展为3#溶洞; 后因深部径流条件改变而被充填,形成现今这种罕见的深饱水带特大型充填溶洞。