Changes in the surfaces of adsorbed p-nitrophenol on methyltrioctadecylammonium bromide organoclay--an XRD, TG, and infrared spectroscopic study

Water purification is of extreme importance worldwide. p-Nitrophenol was used as a test chemical to design and test an organoclay for the removal of p-nitrophenol from an aqueous solution. Synthesis of the organoclay with methyltrioctadecylammonium bromide [CH(3)(CH(2))(17)](3)NBr(CH(3)) labeled as MTOAB results in multiple expansions of the montmorillonite clay from 1.24 nm to a maximum of 5.20 nm as is evidenced by the XRD patterns. Thermal analysis shows strong bonding of the surfactant to the clay siloxane layers and the interaction of the p-nitrophenol with the clay surfaces. It is proposed that the p-nitrophenol penetrates the siloxane layer of the clay and bonds through the ditrigonal space of the siloxane hexagonal units to the inner OH units. Such a concept is supported by the observation of an additional infrared band at 3652 cm(-1) for the organoclay. Shifts in the p-nitrophenol OH stretching vibrations mean a strong interaction of the p-nitrophenol molecule. Significant changes in the siloxane stretching bands are also observed.     

Modification of the surfaces of Wyoming montmorillonite by the cationic surfactants alkyl trimethyl, dialkyl dimethyl, and trialkyl methyl ammonium bromides

Surfaces of a Wyoming SWy-2 sodium montmorillonite were modified using microwave radiation through intercalation with the cationic surfactants octadecyl-trimethyl ammonium bromide, dimethyldioctadecylammonium bromide, and methyl-tri-octadecyl ammonium bromide by an ion exchange mechanism. Changes in the surfaces and structure were characterized using X-ray diffraction (XRD), thermal analysis (TG) and infrared (IR) spectroscopy. Different configurations of surfactants within montmorillonite interlayer are proposed based on d(001) basal spacings. A range of surfactant molecular environments within the surface-modified montmorillonite are proposed based upon their thermal decomposition. IR spectroscopy using a smart endurance single bounce diamond attenuated total reflection (ATR) cell has been used to study the changes in the spectra of CH asymmetric and symmetric stretching modes of the surfactants to provide more information of the surfactant molecular configurations.     

Preparation, structure, magnetic properties and special magnetoresistance effect of Lao.67Sr0.33Mn03+δ/Pr0.7Cao.3 Mn03+δ/Lao.67Sro.33Mn03+δ trilayered thin films

The La_0,67Sr_0.33Mn0_{3 +δ}/Pr_0.7Ca_o.3Mn0_3+δ/La_0.67Sr_0.33Mn0_3+δ(LPL) trilayered films on (100)LaA-1O₃ substrates are prepared by using direct current (DC) magnetron sputtering method. The results obtained by means of X-ray powder diffractometer show that all films are the high quality epitaxial films. The results gained by SQUID magnetometer indicate that there is a magnetic coupling in the LPL trilayered films. The resistivities of LSMO, PC-MO and LPL films are measured using standard four-probe method and analyzed log_p-1/T curve. From the results it is concluded that the middle-layered PCMO which is ferromagnetic may play a role of intra-magnetic field, which weakens the paramagnetism of LSMO film, lowersp _max and enlargesT _p which is the transition temperature from metal to insulator, just as the applied magnetic field does. And the middle-layered PCMO may induce the change of the density of states in the LSMO’s gap. The two reasons above make the resistivity andT _p of the samples in zero field change with the thickness of PCMO layers. Project supported by the Chinese Academy of Sciences and the Foundation of State Science and Technology Commission of China.     

Finite element analysis and experiment on high pressure apparatus with split cylinder

Ultra-high pressure belt-type die was designed with a large sample volume prism cavity and a split cylinder which was divided into eight segments to eliminate circumferential stress. The cylinder of this type die has no cambered surface on inner wall, and the inner hole is a hexagonal prism-type cavity. The divided bodies squeeze with each other, providing the massive support and lateral support effect of the cylinder. Simulation results indicate that the split cylinder with the prism cavity possesses much smaller stress and more uniform stress distribution. The split cylinder with the prism cavity has been shown to bear larger compressive stresses in radial, circumferential and axial directions due to its structure, and tungsten carbide is most effective in pure compression so this type cylinder could bear higher pressure. Experimental results prove that the high pressure apparatus with a prism-type cavity could bear higher pressure. The apparatus with a prism cavity could bear 52.2% more pressure than the belt-type die.     

Ultrafast Saturable Absorption of Core/Shell Colloidal Quantum Dots

Ultrafast saturable absorption (SA) materials that are capable of blocking the optical absorption under strong excitation have extensive applications in photonic devices. This work presents core/shell colloidal quantum dots (CQDs) which have the quantized energy levels, excellent band gap tunability, and possess significant SA performance. When the band gap is close to the pump pulse energy, the CQDs show significant resonant SA response. At the same excitation conditions, the core/shell CQDs dispersions show better SA response than graphene dispersions, and comparable to the recently reported molybdenum disulfide. The carrier dynamics of the SA of the CQDs is analyzed systematically. The research has also found that the two‐photon absorption of the CQDs show nearly cubic power law of the band gap, while the SA performance keeps almost the same in the nonresonant regime. Further, superior passive Q‐switched laser behavior is observed using the CQDs as a saturable absorber. The results directly reveal the physical processes of this basic problem and broaden the applications of CQDs in photonic devices.     

固态纳米孔对蛋白质易位的实验研究

蛋白质因其多样性和功能性,是生物体内一类非常重要的分子.通常蛋白质的表征需要借助荧光或者酶的标记.而纳米孔技术,得益于免标记、单分子检测等优势,为蛋白质的表征提供了新方向.我们使用固态纳米孔完成了单个蛋白质分子及蛋白质-蛋白质结合物的检测.可以发现,外部电压和电解质溶液的酸碱度会直接影响蛋白质分子表面带电量,从而加快或延迟其在孔内的易位时间.抗原、抗体本质上都是蛋白质,两者之间具有高度特异性.通过比较抗体溶液在添加特异性抗原前后的易位事件,实现了单个蛋白质分子和蛋白质-蛋白质结合物的区分.未来,纳米孔技术有望应用于多蛋白质分子的辨识、蛋白质分子相互作用机制等方面的研究.     

2-苯并咪唑吡啶镍配合物的合成、晶体结构及与DNA相互作用的共振散射光谱研究

合成了2.苯并咪唑吡啶镍配合物[Ni(C12H9N3)3](C1O4)2·H2O,通过IR,UV-Vis和元素分析对其进行了表征,并通过X射线单晶衍射确定了其晶体结构.单品结构分析表明,该晶体属十三斜晶系,空间群为P1,a=1.20076(5)nm,b=1.22545(5)nm,c=1.49077(5)nm,α=88.2430(10)°,β=71.7970(10)°,γ=72.544(2)°,Z=2,最终偏离因子R1=0.0608,wR2=0.1859.配合物的金属中心与6个配位氮原子形成八面体的几何构型.用共振瑞利散射(RRS)研究了配合物与DNA的作用,配合物与DNA相互作用形成复合产物并出现了相应的新的RRS光谱,且随着配合物浓度的增大引起共振瑞利散射增强,在低离子强度的环境下与DNA的作用比较明显.这些实验结果表明了配合物与DNA之间存在较强的相互作用.     

Hydrodynamic lubrication in nanoscale bearings under high shear velocity

The setting up process in a nanoscale bearing has been modeled by molecular dynamics simulation. Contrary to the prediction from the classical Reynolds' theory, simulation results show that the load capacity of the nanoscale bearing does not increase monotonically with the operation speed. This is attributed to the change of the local shear rate, which will decrease with the shear velocity of the bearing as the shear velocity exceeds a critical value, i.e., the local shear rate has an upper limit. A simple nonlinear dynamic model indicates that the momentum exchange between the liquid and the solid wall is reduced with the shear velocity when the shear velocity is above a critical value. The weak momentum exchange results in a decrease of the local shear rate, which in turn causes a sharp increase of the slip length.     

ACL单束/双束重建对多屈曲角位姿的胫股关节力学特性影响

进行膝关节的轴移仿真, 在证实了单例个体膝关节的重建模型能反映不同重建术后膝关节力学特性有效性的基础上, 应用SONATA MAESTRO 1.5T扫描得到的屈曲角位姿为0°/25°/60°/80° 的膝关节MRI图像数据, 建立了对应屈曲角的正常/ACL(anterior cruciate ligament)单束/双束重建胫股关节3D模型, 通过对该系列关节模型施加轴向压力与压扭载荷, 来分析多屈曲角度位姿的ACL单束/双束重建法对胫股关节软骨、半月板和韧带应力分布影响及韧带张力特性影响. 结果表明: (1) ACL单束/双束重建关节的软骨与半月板上的应力分布改变跟屈曲角度相关, 某些角度位姿下软骨应力分布改变显著; (2) 单束重建关节的软骨和半月板上的最大等效应力有较明显的增大, 最大增幅达40%左右; 双束重建关节在各屈曲角位姿下软骨和半月板上的最大等效应力值更接近于正常关节; (3) ACL单束重建虽降低了PCL(posterior cruciate ligament)的最大等效应力值, 却使高屈曲角位姿的内侧/外侧副韧带等效应力明显增大; 双束重建后MCL(medial collateral ligament)上的最大等效应力随屈曲角的变化明显, 但LCL(lateral collateral ligament)和PCL的最大等效应力随屈曲角度的变化趋势与正常关节相一致性; (4) 单束/双束重建后MCL上平均张力要高于另外两条韧带, 而双束重建的韧带张力特性比单束重建更接近于正常关节. 总之, 综合ACL重建后软骨、半月板和3条韧带随屈曲角度的等效应力分布、张力变化等多种特性表明: ACL双束重建的胫股关节力学特性比单束重建更接近于正常关节, 且无论ACL单束还是双束重建, 都引起术后关节软骨与韧带上应力分布变化与等效应力峰值增大, 这将是诱发术后关节慢性退变与膝关节并发症的根源.     

巯基-环氧点击化学及其在高分子材料中的应用

巯基-环氧反应作为一类典型的“点击化学”具有反应速度快、选择性高且反应条件温和等优点,近年来备受关注。本文首先阐述了巯基-环氧反应的碱催化机理,并评述了碱性催化剂、取代基团以及溶剂等因素对于巯基-环氧反应速率的影响。归纳认为,无机碱如氢氧化锂以及有机碱如四丁基氟化铵具有较高催化活性,并比较了无机碱和有机碱催化剂的优缺点;与供电子基团连接的巯基化合物以及与吸电子基团连接的环氧化合物具有较高的反应活性,位阻效应也对其有影响;在无溶剂的本体条件下反应活性较高。同时,重点介绍了巯基-环氧反应在高分子材料领域中应用的最新进展,并将其分为在溶剂中合成结构可控的高分子（包括线型或复杂结构高分子的合成和高分子或表面的修饰改性）以及本体条件下制备性能优良且具有应用价值的高分子网络两大类进行讨论。最后,简要展望了其发展前景。