Nanoscale Control of Polyoxometalate Assembly: A {Mn8W4} Cluster within a {W36Si4Mn10} Cluster Showing a New Type of Isomerism

Two near isomeric clusters containing a novel {Mn₈W₄} Keggin cluster within a [W₃₆Mn₁₀Si₄O₁₃₆(OH)₄(H₂O)8]^24? cluster are reported: K₁₀Li₁₄ [W₃₆Si₄O₁₃₆Mn^II₁₀(OH)₄(H₂O)₈] ( 1 ) and K₁₀Li1_3.5Mn_0.25[W₃₆Si₄O₁₃₆Mn^II₁₀(OH)₄(H₂O)₈] ( 1′ ). Bulk characterization of the clusters has been carried out by single crystal X‐ray structure analysis, ICP‐MS, TGA, ESI‐MS, CV and SQUID‐magnetometer analysis. X‐ray analysis revealed that 1′ has eight positions within the central Keggin core that were disordered W/Mn whereas 1 contained no such disorder. This subtle difference is due to a differences is how the two clusters assemble and recrystallize from the same mother liquor and represents a new type of isomerism. The rapid recrystallization process was captured via digital microscopy and this uncovered two “intermediate” types of crystal which formed temporarily and provided nucleation sites for the final clusters to assemble. The intermediates were investigated by single crystal X‐ray analysis and revealed to be novel clusters K₄Li₂₂[W₃₆Si₄Mn₇O₁₃₆(H₂O)₈]?56 H₂O ( 2 ) and Mn₂K₈Li₁₄[W₃₆Si₄Mn₇O₁₃₆(H₂O)₈]?45 H₂O ( 3 ). The intermediate clusters contained different yet related building blocks to the final clusters which allowed for the postulation of a mechanism of assembly. This demonstrates a rare example where the use X‐ray crystallography directly facilitated understanding the means by which a POM assembled.     

Application of ZnO nanoparticles to enhance the antimicrobial activity and ultraviolet protective property of bamboo pulp fabric

Hyperbranched polymer HSDA was synthesized from methyl acrylate, tetraethylenepentamine, and dodecanoic acid by melt polycondensation. ZnO nanoparticle colloidal solution was prepared in one step by mixing Zn(NO₃)₂ and HSDA aqueous solution under hydrothermal condition. The results of transmission electron microscopy and ultraviolet–visible (UV–Vis) spectroscopy indicated that ZnO nanoparticles were formed in colloidal solution. Bamboo pulp fabric was treated with ZnO nanoparticle colloidal solution by an impregnation method to provide the bamboo pulp fabric with antibacterial and UV protective properties. The whiteness, antibacterial activity, UV protective property, and washing durability of the ZnO nanoparticle-treated fabrics were determined. The results indicated that the bamboo pulp fabric treated with ZnO nanoparticles showed good UV protective properties and its ultraviolet protection factor (UPF) can reach 90.38. The UPF value of treated fabric drops to 70.42 after washing for 20 times, but it retains good UV protective properties. The ZnO nanoparticle-treated fabric showed 99.91 % bacterial reduction of Staphylococcus aureus and 99.97 % bacterial reduction of Escherichia coli. The fabric retained over 98.93 % reduction level even after being exposed to 20 consecutive home-laundering conditions. In addition, the results of scanning electron microscopy and X-ray spectroscopy confirmed that ZnO nanoparticles were fixed and well dispersed on bamboo pulp fabric.     

悬浮聚合制备大尺寸梭形聚苯乙烯粒子新方法及机理研究

利用氢氧化钾对苯乙烯-马来酸酐交替共聚物(SMA)进行水解,所得中等皂化程度的SMA水解产物(SMAA)在水溶液中具有刚性棒状直链构型;将此特殊结构的大分子作为分散剂用于苯乙烯悬浮聚合,通过控制搅拌速度和油水比,可得到梭形聚苯乙烯粒子;在优化条件下,粒子平均长度6.8 mm,宽度1.4 mm,厚度0.5 mm,长径比约5.0.其可能的机理为,中等皂化程度的刚棒直链型SMAA在聚合物"软粒子"表面能形成难以"回复"的有效保护层,使由剪切形成的变形聚合物"软粒子"在聚合过程中能保持形状和尺寸的稳定,从而得到梭形聚合物粒子.     

电场对金属串配合物M3(dpa)4Cl2 (M=Co,Rh, Ir; dpa=dipyridylamide)结构的影响

应用密度泛函理论PBE0 方法研究具有分子导线潜在应用的金属串配合物M₃(dpa)₄Cl₂ (1: M=Co, 2: M=Rh, 3: M=Ir; dpa=dipyridylamide)在电场作用下的几何和电子结构. 结果表明: 配合物基态均是二重态. 1和2的M₃⁶⁺金属链形成三中心三电子σ键, 3 中M₃⁶⁺形成三中心四电子σ键且存在弱的δ键. 随金属原子周期数增大其M―M键增强、LUMO与HOMO能隙减小、金属原子的反铁磁耦合减弱以至消失且自旋密度向配体的离域增强. 在Cl4→Cl5 电场作用下, 低电势端的M3－Cl5 键缩短, 高电势端的M2―Cl4 键增长, M―M平均键长略为缩短, M―M键增强, 有利于分子线的电子传递; 分子能量降低, 偶极矩线性增大. 低电势端Cl5的负电荷向高电势端Cl4 转移, 且3 中金属原子的正电荷由高电势端向低电势端的转移较明显, 自旋电子由低电势端向高电势端金属原子移动, 但桥联配体dpa^-与M和Cl 所在的分子轴间没有电荷转移. 电场使LUMO与HOMO能隙减小, 有利于分子的电子输运. 随金属原子周期数增大, 电场作用下M―M平均键长变化减小, LUMO、HOMO的能级交错现象减少.     

分光光度法测定婴幼儿食品中硫氰酸钠

采用分光光度法测定婴幼儿食品中硫氰酸钠的含量。详细叙述了不同样品的溶样方法,超声溶解时间及蛋白质沉淀剂的选择等。样品溶液中的SCN-与Fe3+生成血红色的络合物,其最大吸收波长位于457nm处。硫氰酸钠的质量浓度在20mg·L-1以内与其吸光度呈线性关系,方法的检出限为1.670g·kg-1。方法用于婴幼儿食品中硫氰酸钠的测定,加标回收率在91.8%～98.7%之间。     

一维配位聚合物{[Co(dpa)(H2O)4]·(dpdo)·(H2O)}n(H2dpa=2,2’-联苯二酸,dpdo=N,N’-二氧化-4,4’-联吡啶)的晶体结构和光谱性质

采用水热合成法制备了一个一维配位聚合物{[Co(dpa)(H2O)4].(dpdo).(H2O)}n(1)(H2dpa=2,2′-联苯二酸,dpdo=N,N′-二氧化-4,4′-联吡啶),通过红外光谱、紫外光谱、元素分析、XRPD、TGA和X-射线单晶衍射进行了表征。Co(Ⅱ)原子采取了畸变的八面体构型,6个配位氧原子分别来自于2个dpa2-配体和4个配位水分子。每一个dpa2-配体桥联2个Co髤中心,每一个Co(Ⅱ)原子与2个dpa2-配体配位进而形成了21螺旋链结构。借助溶剂水分子的连接作用,螺旋链之间通过多种O-H…O氢键作用形成了2D网格,通过dpdo和2D网格之间多种类型的氢键作用形成了三维超分子结构。测定了室温下聚合物1的固体荧光光谱。     

室内环境中脑控轮椅的路径跟踪控制

为了实现室内环境中脑控轮椅的自主导航,提出了一种简单有效的路径跟踪控制方法。给定的路径通常被表示为一系列离散点,根据这一特点,提出了分段直线路径跟踪方法,即依次跟踪由前后两个路径点构成的直线路径到达目标点。基于预瞄点技术并结合模糊算法和传统的PID控制方法设计控制器,完成各分段直线路径的跟踪,并给出了有效的切换条件。实验结果表明,本文提出的路径跟踪控制方法能够使脑控轮椅在室内环境中精确地跟踪给定路径。     

Entanglement transfer from two-mode squeezed vacuum light to spatially separated mechanical oscillators via dissipative optomechanical coupling

In this paper, we propose a scheme to generate an entangled state between two spatially separated movable mirrors by injecting the two-mode squeezed optical reservoir to the dissipative optomechanics, in which the movable mirrors can modulate the linewidth of the cavity modes. When the coupling between the mirrors and the corresponding cavity modes is weak, the two driven cavity fields can respectively behave as the squeezed-vacuum reservoir for the two movable mirrors by utilizing the effect of completely destructive interference of quantum noise. Thus the mechanical modes are prepared in a two-mode squeezed vacuum state. Moreover,when the coupling between the two mirrors and the cavities modes is strong, the entanglement between the two movable mirrors decreases because photonic excitation can preclude the completely destructive interference of quantum noise, but the movable mirrors are still entangled.     

MFCAV近似Riemann解法器在相容拉氏方法中的熵条件分析

 对基于MFCAV(Multi Fluid Channel on Averaged Volume)近似Riemann解法器的相容拉氏方法的熵条件进行了分析. 结果表明与满足声学形式Riemann解法器的熵不同, 前者只能在每个网格边界左、右两侧网格的熵随时间变化的和保证大于零, 即能保证整体熵增, 但不保证传统意义上的在每个网格中的熵增;而后者不仅保证整体熵增, 而且还满足传统意义上的熵增. 因此MFCAV的熵增相对声学形式解法器而言要弱一些, 由此表明其熵增可能要小些, 使得格式的耗散可能要小些.数值算例也验证了分析的正确性.