Formation of phosphorus-nitrogen bonds by reduction of a titanium phosphine complex under molecular nitrogen

The reduction of high oxidation state metal complexes in the presence of molecular nitrogen is one of the most common methods to synthesize a dinitrogen complex. However, the presence of strong reducing agents combined with the poor binding ability of N2 can lead to unanticipated outcomes. For example, the reduction of [NPN]ZrCl2(THF) (where NPN = PhP(CH2SiMe2NPh)2) with KC8 under N2 leads to the formation of the side-on bridged dinuclear dinitrogen complex ([NPN]Zr(THF))2(mu-eta2:eta2-N2) with an N-N bond distance of 1.503(3) A; however, reduction of the corresponding titanium precursor, [NPN]TiCl2, under N2 does not generate a dinitrogen complex, rather the bis(phosphinimide) derivative, ([N(PN)N]Ti)2, is isolated in which the added N2 is incorporated between the titanium and phosphine centers. Performing the reaction under 15N2 results in the 15N label being incorporated in the phosphinimide unit. A suggested mechanism for this process involves an initially formed dinitrogen complex being over reduced to generate a species with bridging nitrides that undergoes nucleophilic attack by the coordinated phosphine ligands and formation of the P=N bond of the phosphinimide.     

Self‐Powered Multimodal Temperature and Force Sensor Based‐On a Liquid Droplet

Herein we report a self‐powered multimodal temperature and force sensor based on the reverse electrowetting effect and the thermogalvanic effect in a liquid droplet. The deformation of the droplet and the temperature difference across the droplet can induce an alternating pulse voltage and a direct voltage, respectively, which is easy to separate/analyze and can be utilized to sense the external force and temperature simultaneously. In addition, an integral display system that can derive information from external temperature/force concurrently is constructed. Combined with advantages of excellent sensing properties and a simple structure, the droplet sensor has promising applications in a wide range of intelligent electronics.     

N-氯苯基-2-脱氧-α-D-吡喃核糖亚胺的合成及其晶体结构

在水与甲醇的混合体系中, 2-脱氧-D-核糖与氯代苯胺反应立体选择性地合成了三种N-氯苯基-2-脱氧-α-D-吡喃核糖亚胺(化合物1, 2, 3), 它们的结构经过1H NMR和13C NMR的表征. 将单一构型的N-对氯苯基-2-脱氧-α-D-吡喃核糖亚胺(1)溶于氘代DMSO加入几滴重水, 1H NMR 和13C NMR分析显示1异构化为四种构型的混合物. 培养了化合物1, 2, 3的单晶, 并用X射线衍射法测定了它们的晶体结构. 对晶体结构进行分析, 对反应形成单一构型产物的原因进行了探讨. 并提出了1异构化过程的机理.     

Edge-Preserving Denoising of Image Sequences

To monitor the Earth’s surface, the satellite of the NASA Landsat program provides us image sequences of any region on the Earth constantly over time. These image sequences give us a unique resource to study the Earth’s surface, changes of the Earth resource over time, and their implications in agriculture, geology, forestry, and more. Besides natural sciences, image sequences are also commonly used in functional magnetic resonance imaging (fMRI) of medical studies for understanding the functioning of brains and other organs. In practice, observed images almost always contain noise and other contaminations. For a reliable subsequent image analysis, it is important to remove such contaminations in advance. This paper focuses on image sequence denoising, which has not been well-discussed in the literature yet. To this end, an edge-preserving image denoising procedure is suggested. The suggested method is based on a jump-preserving local smoothing procedure, in which the bandwidths are chosen such that the possible spatio-temporal correlations in the observed image intensities are accommodated properly. Both theoretical arguments and numerical studies show that this method works well in the various cases considered.     

Synthesis of Chiral Tertiary α,α-Difluoromethyl Carbinols by Cu-Catalyzed Asymmetric Propargylation

Chiral α,α-difluoromethyl carbinols are recurring structural motifs in many therapeutic agents. Despite the indubitable interest in the catalytic asymmetric synthesis of such compounds, this research field still remains largely underexplored. Herein, an efficient approach to a range of chiral homopropargylic α,α-difluoromethyl carbinols has been developed, through a Cu-catalyzed enantioselective propargylation of α,α-difluoroketones with (pinacolato)allenylboron. In the presence of a cuprous complex, generated in situ from CuCl and a spiroketal-based diphosphine (SKP) ligand, a variety of aryl-, heteroaryl-, alkyl-, alkynyl, alkenyl, or benzyloxycarbonyl-substituted α,α-difluoromethyl carbinols were obtained in 75–99 % yields with 84–98 % ee values. The catalytic system was further investigated using a combined dynamic NMR spectroscopic, X-ray crystallographic, and non-linear effect studies. The origin of the enantioselectivity was rationalized based on DFT calculations. Finally, several efficient transformations were showcased to highlight the utilities of the protocol in synthesis of complex compounds bearing an α,α-difluoromethyl carbinol moiety.     

LaNiO3/Pd复合薄膜电极材料在碱性溶液中的电化学行为研究

用射频磁控溅射法在Si(111)衬底上沉积制备金属Pd膜、LaNiO3单层膜和Pd/LaNiO3复合薄膜,利用XRD,SEM,EDS能谱、四元探针和电化学方法系统研究了退火处理和表面覆Pd对Pd/LaNiO3复合薄膜电极的相组织结构、表面形貌、电学以及电化学储氢行为的影响。结果表明,700℃退火1 h后,LaNiO3薄膜具有结晶度较佳的钙钛矿型菱方结构组织和最小的电阻率(0.79 mΩ·cm),退火温度高于800℃后,LaNiO3菱方型结构组织开始分解,电阻率增加。LaNiO3薄膜在空气中退火后其表面化学吸附氧转变为晶格氧,导致LaNiO3薄膜氧元素含量明显增加。电化学测试结果表明,在碱液中金属Pd膜具有良好的析氢电催化活性和较好的电化学储氢性能,其最大放电容量为130 mAh·g-1。退火态LaNiO3单膜电极放电容量很小(27 mAh·g-1),当表面覆Pd后退火态LaNiO3/Pd复合薄膜电极放电容量增加至181 mAh·g-1,扣除其表面Pd膜吸氢容量后LaNiO3薄膜电极的实际放电容量最高达到400 mAh·g-1。LaNiO3表面镀Pd后能极大改善和提高LaNiO3薄膜电极的电催化活性和电化学储氢容量。     

柳杨沟泥石流特征及其工程影响分析

2001年7月11日晚11点至12日凌晨,位于小天都水电站下闸址以下约600 m的柳杨沟爆发泥石流,造成数十万元的经济损失,对小天都电站下闸址造成了一定影响。通过现场调查和室内计算,研究了柳杨沟泥石流的发育特征和运动特征,并分析在各种设计概率下发生泥石流对水电工程可能造成的影响。     

温度对菱形花纹的影响

研究了温度对蜂蜡和樟脑制成的尖锥模型上的菱形花纹的影响。烧蚀实验在超音速风洞中进行,得到了温度与花纹波长、压力与花纹波长的关系,并分析了温度和压力对出现花纹的起始位置、出现花纹和形成稳定花纹所需要的时间的影响。     

Porphyrin-appended europium(III) bis(phthalocyaninato) complexes: synthesis, characterization, and photophysical properties

Mixed cyclization of 3-mono-, 4-mono-, or 4,5-di(porphyrinated) phthalonitrile compounds 2, 3, or 6 and unsubstituted phthalonitrile with the half-sandwich complex [EuIII(acac)(Pc)] (Pc=phthalocyaninate, acac=acetylacetonate) as the template in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in n-pentanol afforded novel porphyrin-appended europium(III) bis(phthalocyaninato) complexes 7-9 in 30-40% yield. These mixed tetrapyrrole triads and tetrad were spectroscopically and electrochemically characterized and their photophysical properties were also investigated with steady-state and transient spectroscopic methods. It has been found that the fluorescence of the porphyrin moiety is quenched effectively by the double-decker unit through an intramolecular photoinduced electron-transfer process, which takes place in several hundred femtoseconds, while the recombination of the charge-separated state occurs in several picoseconds. By using different phthalocyanines containing different numbers of porphyrin substituents at the peripheral or nonperipheral position(s) of the ligand, while the other unsubstituted phthalocyanine remains unchanged in these double-deckers, the effects of the number and the position of the porphyrin substituents on these photophysical processes were also examined.