Stepwise Self‐Assembly and Dynamic Exchange of Supramolecular Snowflakes

Snowflake, a highly symmetrical hexagram figure, is challenging to be expressed by chemistry/supramolecular chemistry due to the complex structure. Herein, we have constructed super snowflake supramolecules using terpyridine (tpy)‐based metal‐organic building blocks with tpy‐Ru(II)‐tpy and tpy‐Zn(II)‐tpy connectivities through stepwise strategies in high yield. The structures were characterized by multi‐dimensional mass spectrometry and multi‐dimensional NMR spectrometry. In order to address the stability/tolerance of our designed super snowflake structures, ligand exchange behaviors between different supramolecules with various arm length were fully investigated by mass spectrometry. The study revealed that three modes could exist in such binary systems, including full exchange, partial exchange and self‐sorting (no exchange) depending on the length difference of ligands.     

超分子堵水-防砂一体化评价及应用

疏松砂岩油藏在我国分布范围广、储量大。随着油田进入高含水开发期,堵水难度日益加大,堵水有效期缩短,这不仅严重制约了油田的高效开发,对原油稳产构成了威胁,同时,也造成巨大的作业费用。研制出的超分子堵水-防砂剂对地层水具有感应性,使其对地层亲水岩石表面作用时能够自动进行且吸附能力强,同时解决油田防砂和堵水问题;具有良好的防砂和选择性堵水的能力。超分子堵水-防砂一体化现场施工工艺简单、风险小、有效期长,是国内外首次将超分子应用在油田堵水、防砂中。     

页岩气井用乳液型超分子压裂液制备与应用

为满足页岩气高效化、清洁化生产的需求,采用反相乳液聚合制备乳液状疏水缔合聚合物ASNP,与自制增效剂SD-Z复配形成页岩用乳液型超分子压裂液SMF-1。该体系满足现配现用需求,无需额外添加剂,仅改变加量就能实现滑溜水、线性胶、胶液的自由切换。SMF-1滑溜水体系具有优异的降阻效果,0.08%加量下对清水和返排液的降阻率在70%左右,抗盐能力高达10000 mg/L。SMF-1胶液体系具有良好的耐温抗剪切性能,0.6%的SMF-1胶液在110℃、170 s-1下剪切120 min,黏度始终保持在120 mPa·s以上。SMF-1压裂液属于低黏高弹流体,具有良好的携砂性能,其破胶液黏度低于1.5 mPa·s,残渣含量仅为12.8 mg/L,对岩心伤害率低至11.8%。现场应用切换方便,性能稳定,加砂强度高于同井邻段和邻井同段。      

Crystal and Supramolecular Structure of a Novel Organotin Sulphate: {[(Ph3Sn)2SO4]2 · (H2O)3} · 2EtOH

A novel sulphate of organotin was synthesized by the reaction of triphenyltin chloride with silver sulphate. The structure of {[(Ph₃Sn)₂SO₄]₂ · H₂O)₃} · 2EtOH has been determined by X-ray crystallography. The crystal data parameters are as follows: monoclinic, space group Cc, a = 14.146(6), b = 23.844(11), c = 23.777(11) Å, Z = 4. The title compound displays a dimeric tetra-tin nuclear structure. The geometry about tin is trigonal bipyramidal with a trans-O₂SnC₃ stereochemistry about the metal. Hydrogen bonding between the oxygen atoms of the anion and the solvate water produces a graphite-like 3D network lattice.     

Structure and dynamics of polyrotaxane and slide-ring materials

Polyrotaxane (PR), in which cyclic molecules are threaded into a linear polymer chain, has generated great interest because the sliding and rotation of the cyclic molecules on the axial polymer chain lead to unique functional nanomaterials with novel dynamical properties. A typical example of the functional materials is a polyrotaxane network, called slide-ring (SR) material, prepared by cross-linking the cyclic molecules on different PRs. The cross-links composed of two cyclic molecules in a shape of figure-of-eight slide along the polymer chains and the sliding motion gives rise to remarkable physical properties of the SR materials. In order to understand the unique features of the functional materials including SR materials and develop novel applications of PR, it is necessary to reveal the physical properties of PR, especially the sliding motion of the cyclic molecules in PR. In this article, we review the static structure and molecular dynamics of PR based primarily on our recent studies. Furthermore, the difference between SR materials and usual chemical gels in deformation behavior is also described. The findings summarized in this review indicate the significance of the sliding motion of cyclic molecules characterizing PR and SR materials.     

一种高温耐剪切超分子缔合弱凝胶清洁压裂液体系

超分子聚合物化学是超分子化学与高分子化学相互交叉融合形成的新方向,因此基于前期对超分子压裂液的研究成果,采用对疏水单体增溶性能好的ASF-1两性离子表面活性剂,与自制的LCM长碳链阳离子不饱和成链单体、自制的HTM抗高温单体等进行胶束共聚合反应,合成了一种高温耐剪切的超分子聚合物稠化剂SPM-2。通过复配具有蠕虫状胶束的物理交联剂PCA-1,制备出一种超分子缔合弱凝胶压裂液（0.8% SPM-2+0.5% PCA-1）。该压裂液具有超分子“蜂巢”网格结构,表观黏度随物理交联剂加量增大而持续增加,达到了胶束与聚合物链的强物理交联效果。该压裂液在150℃、170 s-1、2 h下表观黏度保持在58 mPa·s左右,相比超分子聚合物溶液提高了30 mPa·s ;剪切速率从40 s-1增至1 000 s-1,再降到40 s-1后,压裂液黏度迅速降低并快速恢复,剪切回复性好;在0.01~10 Hz内进行频率扫描,压裂液弹性明显优于黏性;支撑剂沉降速率小于8×10-3 mm/s,悬砂能力相比稠化剂溶液提高了一个数量级;在90℃、2 h下破胶液黏度小于2 mPa·s,未检出残渣;岩心伤害率小于10%。室内实验结果表明,该压裂液可满足致密砂岩气藏高温储层压裂需求。      

DNA-like interactions enhance the miscibility of supramolecular polymer blends

We have investigated the miscibility behavior, specific interactions, and supramolecular structures of blends of the DNA-like copolymers poly(vinylbenzylthymine-co-butyl methacrylate) (T-PBMA) and poly(vinylbenzyladenine-co-styrene) (A-PS) with respect to their vinylbenzylthymine (VBT) and vinylbenzyladenine (VBA) contents. ¹H nuclear magnetic resonance spectroscopy and one- and two-dimensional Fourier transform infrared spectroscopy revealed that hydrogen bonding occurred exclusively between the VBA and VBT units. In addition, size exclusion chromatography, dynamic light scattering, and viscosity analyses provided evidence for the formation of supramolecular network structures in these binary blend systems. A miscibility window existed in the A-PS/T-PBMA blend system when the VBT and VBA fractions in the copolymers were greater than 11 mol%, as predicted using the Painter-Coleman association model.     

超分子化学识别与光化学传感器

具有光学响应的化学传感器日益受到人们的重视。这类光化学传感器的关键技术是要发展新型识别技术。即在选择性识别分析对象的同时，要求伴有光学性质的变化。冠醚、穴醚、环糊精、杯芳烃这样的超分子化合物具有很强的分子识别功能，但通常不具有光学活性。对这些分子修饰合适的生色团，使之同时具有光谱响应功能。由这些经过修饰的新型超分子，可望发展一批具有高选择性的重要的光化学传感器。     

Thermal properties of novel supramolecular polymer networks based on poly(4-vinylpyridine) and disulfonic acids

Novel supramolecular polymer networks were prepared by the reaction of poly(4-vinylpyridine) (P4VP) with 1,5-naphthalenedisulfonic acid (NDS), 1,3-propanedisulfonic acid (PDS), or adipic acid (AA). The IR and XPS analyses of the polymer networks revealed that the P4VP/NDS complex has a higher ionic interaction between pyridinium cation and sulfonate anion than the P4VP/PDS complex, and that hydrogen bonding interaction between pyridine and carboxylic acid predominantly contributes for the P4VP/AA complex. When the glass transition temperatures of P4VP and P4VP/proton donor (1/1) complexes are compared, the higher order was P4VP/NDS>P4VP/PDS>P4VP>P4VP/AA, in agreement with a higher degree of ionic interaction. The P4VP/PDS complex had a melting endothermic peak in the DSC thermograms, which was not observed for the P4VP/NDS complex. The thermal decomposition temperature of the P4VP complexes is also investigated in relation to the intermolecular interaction.     

Synthesis and magnetic property of a dual μ-[N(CN)2] bridged copper(II) supramolecule with dinuclear unit

A dicyanamide (dca) Cu(II) supramolecular complex constructed by hydrogen-bond interactions and weak Cu–N bond interactions has been prepared and the structure was determined by X-ray diffraction analysis. The magnetic studies indicate that strong antiferromagnetic interactions exist between two Cu(II) ions of the dca-bridged dimer.