新型旋转挤出流变仪

聚合物加工是决定塑料制品最终结构性能的中心环节,其重要的理论基础是聚合物流变学,研究聚合物流变行为的关键仪器是流变仪.但现有流变仪大多基于简化的流动模型,与实际复杂加工条件不符,难有效揭示聚合物在复杂应力场/温度场作用下的流变行为.我们基于前期发明的聚合物管旋转挤出加工技术和装备,研制了新型旋转挤出流变仪,可实现挤出/旋转的不同组合和管内外壁双冷,实施和调控旋转挤出中多种运动模式和应力场及温度场,实时检测挤出/旋转速度、应力、温度场,显示记录有关数据,既可用于研究实际加工复杂条件下聚合物加工流变行为,也可用于制备高性能多功能聚合物微导管.本文综述了新型旋转挤出流变仪的结构特点和原理及其在流变测试与聚合物微导管制备方面的应用.     

聚合物限域和预有序熔体的结晶行为及结构调控

高分子物理领域的挑战性难题之一是调控高分子的结晶行为.高分子结构具有多尺度的特点,且易受到各种本征因素以及加工过程中引入的外场与受限作用的影响.高分子的结晶过程复杂多变,为避免最终产品性能的良莠不齐,促进高分子材料的实际生产和应用,需要建立高分子结构与性能的直接关系并实现对高分子结晶结构的精细化调控.本文以几种典型高分子为例,重点阐述了我们课题组在有关薄膜和纳米孔道构筑的限域空间与分子链预有序熔体对高分子结晶行为的影响、相关结晶结构调控机制以及结构-性能关系等方面的研究工作,阐明了聚合物多层次结构调控领域存在的科学问题,并展望了其未来发展方向.     

基于单苯环分子的多晶相发光超分子弹性晶体

提出了一种利用超分子相互作用实现多晶型及晶体机械柔性制备的策略,通过对5-氨基间苯二甲酸二甲酯的结晶条件进行微调,得到了2种具有弹性的单苯环发光有机超分子晶体1B和1G.引人注目的是2种晶型的晶体均能在直形及弹性弯曲状态下有效地传导光信号,证明了它们在柔性光学器件中的实用性.本研究不仅对设计有机超分子晶体的多晶型和机械柔性具有重要的科学意义,而且对柔性晶体在光学领域的应用也具有重要的指导意义.     

Synthesis and Crystal Structure of 7-Amino-2,3,4,5-tetrahydro- 1,3-dimethyl- 5-（2-nitrophenyl）-2,4-dioxo-lH-pyrano[2,3- d]pyrimidine-6-carbonitrile DMF Solvate

The title compound 7-amino-2,3,4,5-tetrahydro-1,3-dimethyl-5-（2-nitrophenyl）- 2,4- dioxo-1H-pyrano[2,3-d] pyrirnidine-6-carbonitrile DMF solvate 1 （C19H20N6O6, Mr = 428.41） was synthesized and crystallized. The crystal belongs to the monoclinic system, space group P2 1/c with a = 11.383（2）, b = 13.372（2）, c = 13.673（2）A, β = 97.380（4）°, Z = 4, V = 2063.8（6）A^3, Dc = 1.379 g/cm^3,μ（MoKα） = 0.105 mm^-1, F（000） = 896, the final R = 0.0738 and wR = 0.1647 for 2964 observed reflections （I〉 2σ（I））. X-ray analysis reveals that the new pyran ring is coplanar, which is obviously different from those of other similar compounds. In addition, the unclassical hydrogen bonds of C-H…O and C-H…N are presented in the crystals except for the normal hydrogen bonds of N-H…O.     

Synthesis and Crystal Structure of a Novel Tetranuclear Complex [Pb4（HQ）6（NO3）2]

Reaction of 8-hydroxyquinoline （HQ） with Pb（NO3）2 in water resulted in the formation of a tetranuclear complex [Pb4（HQ）6（NO3）2] 1. It has been characterized by IR, elemental analyses and X-ray diffraction. Crystal data for this complex： triclinic system, space group P1, a = 9.7399（6）, b = 11.6535（8）, c = 12.6806（8） A, α = 62.8050（10）, β = 78.4910（10）, γ = 80.5490（10）°, C54H36N8O12Pb4, Mr= 1817.67, Z = 1, V = 1250.04（14）A^3, Dc = 2.415 g/cm^3,μ = 13.503 mm^-1, -12≤h≤8, -14≤k≤13, -15≤1≤15, F（000） = 840, Rint = 0.0217, R= 0.0348 and wR = 0.0927. X-ray crystal structure analysis revealed that in 1 each Pb（ II ） contains a stereo- chemically active lone pair of electrons. The Pb…C interaction, C-H……O weak interaction and π…π stacking interactions are observed in the complex. In the solid state, the complex possesses strong photoluminescent emission at 485 and 528 nm.     

Geometries, Electronic Structures, and Electron Detachment Energies of Small Boron Sulfide Anions： A Density Functional Theory Investigation

A density functional theory investigation on the geometries, electronic structures, and electron detachment energies of BS, BS2, B（BS）2 and B（BS）3 has been performed in this work. The linear ground-state structures of BS （C∞v, ^1∑^＋） and BS2^- （O∞h, ^1∑g^＋） prove to be similar to the previously reported BO and BO2 with systematically lower electron detachment energies. Small boron sulfide clusters are found to favor the formation of -B=S groups which function basically as a-radicals and dominate the ground-state structures of the systems. The perfect linear B（BS）2^-（D∞h, ^3∑g） and beautiful equilateral triangle B（BS）3^- （D3h,^2A1”） turn out to be analogous to the well-known C2v BH2 and O3h BH3, respectively. The electron affinities of BS, BS2, B（BS）2 and B（BS）3 are predicted to be 2.3, 3.69, 3.00 and 3.45 eV, respectively. The electron detachment energies calculated for BS^-, BS2^-, B（BS）2^-, and B（BS）3^- may facilitate future photoelectron spectroscopy measurements to characterize the geometrical and electronic structures of these anions.     

Morphology Control of SrCO3 Crystals using Complexons as Modifiers in the Ethanol-water mixtures

Using SrC12-6H2O and Na2CO3 as the main raw materials and adding different complexons as modifiers with simple co-precipitation method, SrCO3 crystals with distinct morphologies like spherical, bundle-like, overlapping plate-like, hexagonal star-like, dumbbell-like, etc. can be synthesized in the ethanol-water mixtures. The samples were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM） and Fourier transform infrared spectrograph （FT-IR）. The interrelated effect mechanism is presented in the end. Results show that the modifier carboxyl groups play a significant role in controlling the SrCO3 crystal morphologies, which can alter the crystal growth unit （Sr^2＋） supply mode and induce the crystal formation with the morphologies matching their spatial configurations.     

柔性一体化电化学传感器检测汗液的pH值及尿酸浓度

分别以木犀草素和L-精氨酸作为pH值和尿酸(Uric acid, UA)的功能选择性试剂,与碳粉混合,掺杂在聚氯乙烯(PVC)成膜液内,制成pH柔性薄膜电极(pH flexible electrode, pH/FE)和尿酸柔性薄膜电极(UA flexible electrode, UA/FE)。将pH/FE、UA/FE、自制薄膜凝胶型Ag/AgCl参比电极、Pt丝电极平放在塑料薄膜上,用含有饱和KCl的聚乙烯醇-琼脂膜包埋四电极,露出工作电极表面,构成贴敷式柔性一体化电化学传感器(Flexible integrated electrochemical sensor, FIES)。连接pH/FE,将pH 2.00～8.00的磷酸盐缓冲溶液(PBS)分别滴涂在FIES表面,结果表明,在方波伏安曲线上出现一个氧化峰,峰电位与pH值呈线性关系。将含有UA的PBS滴涂在FIES表面,连接UA/FE,采用方波伏安法研究了UA的电化学行为,氧化峰电流与UA浓度在5.0×10^-6～1.3×10^-4 mol/L范围内呈线性关系,检出限为2.0×10^-...     

核-壳式雌二醇磁性分子印迹聚合物的制备及其吸附性能研究

采用稳定性好且亲水性强的苯胺(AN)为功能单体,过硫酸铵(APS)为引发剂,雌二醇(E2)为模板分子,羧基磁球(Fe₃O₄-COOH)为载体,通过固定模板印迹策略制备新型核-壳式雌二醇磁性分子印迹聚合物(MIPs-E2),用于选择性吸附雌二醇。采用透射电子显微镜(TEM)、傅里叶变换红外光谱仪(FT-IR)、X射线衍射仪(XRD)以及振动样品磁强计(VSM)对材料进行表征。结果表明,MIPs-E2粒径均一、晶型结构稳定,并且具有良好的磁性能。动力学吸附、等温吸附、选择性吸附和重复利用性实验结果表明,MIPs-E2具有大的吸附量(21.34 mg/g)、高的选择性(IF=2.65,SC>1.89)、快的传质速率(30 min)以及好的可重复利用性(6次循环使用后吸附效率为93.4%)。本研究为检测环境水样品中雌二醇的含量提供了新方法。