可释放一氧化氮聚合物材料的制备及其在生物医疗器械中的应用

一氧化氮（NO）是一种很好的血小板黏附或活化的抑制剂，同时也是很有效的抗平滑肌细胞增生剂。可释放NO的聚合物材料显示出较好的抗血栓形成及抑制细胞增生的性能。本文综述了可释放NO聚合物材料的制备方法及其近年来在生物医疗器械中的应用。用来制备可释放NO聚合物材料的NO供体主要有两大类，一类是亲核NO供体N-diazeniumdiolates，另一类是S-亚硝基硫醇（RENOs）。制备可释放NO聚合物材料的方法主要有3种：（1）通过物理掺杂的方式将小分子的NO供体分散到聚合物材料中；（2）对聚合物材料的填料微粒进行化学改性，得到可释放NO的填料粒子，再将其填充到聚合物材料中；（3）通过共价键将可释放NO的基团连接到聚合物主链及侧链上。所得到的可释放NO聚合物材料在血管内传感器、体外血液循环电路和体内移植血管等生物医疗器械中有广泛的应用。     

含杯芳烃聚合物的合成与应用

杯芳烃在主客体化学中是继冠醚和环糊精之后被广泛关注的第三代主体分子,能够选择性地与客体分子或离子形成络合物。近年来,含杯芳烃聚合物逐渐受到人们的重视。结合聚合物稳定性好,易于加工的特性,含杯芳烃聚合物将有望被开发成为新型功能高分子材料。本文详细介绍了含杯芳烃聚合物的合成及其应用。     

共轭聚合物荧光传感器的研究进展

共轭聚合物具有共轭分子导线结构,局部微扰在整个聚合物分子链甚至整个聚合物体系内即能得到放大利用,这一性质决定了其具有检测超低含量待测物的能力,且表现出强于小分子荧光传感器的灵敏度.本文概述了荧光共轭聚合物的传感机理,并举例介绍了近年报道的以共轭聚合物为基础的荧光传感器在检测离子及有机小分子方面的应用.     

Adhesion promotion through controlled surface modifications

We present and discuss series of experiments conducted on systems controlled at the molecular level in order to identify the molecular mechanisms of polymer adhesion. A special emphasis is paid to 1) adhesion enhancement through block copolymers at an interface between two incompatible polymers (amorphous or semi‐crystalline); 2) adhesion promotion between an elastomer and a solid, by soft end grafted connector polymer molecules able to interdigitate into the elastomer. We show that surface modifications based on surface anchored polymer chains are efficient for adhesion enhancement because they allow the interface to sustain mechanical stresses. The coupling between surface and bulk stresses is finally what governs the adhesion energy and we examine how one can understand and optimize this coupling.     

Association of poly-N-[tris(hydroxymethyl)methyl] acrylamide with a water soluble β-cyclodextrin polymer

An acrylic polymer with pendent adamantyl groups was synthesized and its properties in an aqueous solution with a β-cyclodextrin (βCD) epichlorhydrin polymer examined. Viscosity properties of precursor and modified polymers show differences at low concentrations, but not at higher concentration probably due to very important hydrogen bonds which prevent the formation of intermolecular hydrophobic bonds. The association of both complementary polymers through the inclusion of adamantyl groups is evidenced by phases separation occurrence. Phase diagrams were established at two different concentrations of polymers. We have shown a maximal association of both polymers at these two concentrations, for the same ratio βCD moles/adamantyl groups: 2.4. Salt addition favors this association and displaces the two phases zone to smaller concentrations of modified polymer. Further, 4-nitrophenol can be extracted by the concentrated phase resulting from mixture of solutions of guest and host polymers, pointing out the availability of the associated phase to trap organic molecules.     

Crystallization of helical oligomers with chirality selection. I. A molecular dynamics simulation for bare helix

Helical polymers often exhibit pronounced chirality recognition during crystallization. By molecular dynamics simulation, we have already shown that the helical polymers crystallize with or without marked chirality selection depending on structural details of the polymer molecules. We have there classified the helical polymers into two categories: the bare helices made of only backbone atoms which show rather tolerant chirality selection, and the general helices with large side groups showing strict chirality recognition. Polymer crystallization is in general largely hampered and retarded by slow dynamics of the entangled chains, and therefore short helical oligomers are very suitable models for studying the chiral crystallization. We here report on molecular simulations of crystallization in the bare helical oligomer molecules by the use of Monte Carlo and molecular dynamics simulations. First we confirm the low temperature chiral crystal phase and the reversible order-disorder transition. We also observe frequent inversions of the helical sense, and the helix reversal defects propagating along the chains. Then we investigate crystallization from the melt into the chiral crystal phase. We find that the crystallization rate depends very sensitively on the degree of undercooling. The crystallization is found to be the first order transition that conforms well to the traditional picture of crystal growth in small molecules. Even when the crystallization directly into the chiral crystal phase is conducted, marked chirality selections are not observed at the early stage of crystallization; the chains adhere to the crystal surfaces selecting their helical senses rather at random resulting in racemic crystallites. The isothermal crystallization for a sufficiently long time, however, yields lamellar crystals composed of well-developed chiral domains, the growth of which seems to be accomplished through the transition back into the ordered chiral crystal phase.     

Role of Hydrodynamic Interactions in the Deformation of Star Polymers in Poiseuille Flow

Stretching polymer in fluid flow is a vital process for studying and utilizing the physical properties of these molecules,such as DNA linearization in nanofluidic channels.We studied the role of hydrodynamic interactions(His)in stretching a free star polymer in Poiseuille flow through a tube using mesoscale hydrodynamic simulations.As increasing the flow strength,star polymers migrate toward the centerline of tube due to His,whereas toward the tube wall in the absence of His.By analyzing the end monomer distribution and the perturbed flow around the star polymer,we found that the polymer acts like a shield against the flow,leading to additional hydrodynamic drag forces that compress the arm chains in the front of the star center toward the tube axis and lift the arm chai ns at the back toward the tube wall.The balanced hydrodynamic forces freeze the polymer into a trumpet structure,where the arm chains maintain a steady strongly stretched state at high flow strength.In contrast,the polymer displays remarkably large conformational change when switching off His.Our simulation results explained the coupling between His and the structure of star polymers in Poiseuille flow.     

Influence of the presence of small gas molecules in the structure of comblike polyacrylates: a Monte Carlo study

A theoretical strategy has been developed to study the motion of small molecules through ordered polymeric systems. The strategy, which has been incorporated into a computer program denoted MCDP/2, is especially useful to study comblike polymers organized in biphasic arrangements. This is because it is based on a configurational bias Monte Carlo algorithm, which is more efficient than conventional methods to study dense systems. The MCDP/2 program has been used to investigate the influence of CH(4) and CO(2) gas molecules in the structure of isotactic poly(octadecyl acrylate), a typical comblike polymer. For this purpose, the pure polymer and different molecular systems constituted by several gas molecules dissolved in the polymer matrix have been simulated. Results indicated that the structural relaxation of the polymer is not coupled to the motion of gas molecules. The importance of these results in the field of molecular modeling of transport properties in comblike polymers is discussed.     

Flow of monodisperse polystyrene solutions through porous media

In this work, we study the origin of the extension thickening commonly observed when solutions of flexible polymers flow through porous media and ideal elongational flows. We have used randomly packed beds of glass beads as porous media. We have performed experiments with closely monodisperse atactic polystyrene of different molecular weights dissolved in organic solvents. The use of a closely monodisperse polymer allowed us to make a more meaningful comparison between the results obtained using opposed jets and porous media flow, as compared to previous works on polydisperse polymers. The results indicate that the coil-stretch transition of isolated polymer molecules in solution cannot be the only mechanism responsible for the extension thickening. It is clear that part of the observed effect is due to the extension of isolated molecules, but the main factor causing a great increase in the elongation viscosity beyond a critical strain rate is the formation of transient entanglement networks.     

Plasma Polymers Applied to Chemical Sensing

The paper describes attempts to apply plasma polymers to the development of chemical sensors. The plasma polymers were used as membranes to coat conventional conducting polymer sensors, as stand-alone chemiresistive sensors and as absorbent coatings on quartz crystal microbalances. The plasma polymers were derived from combinations of pyrrole and three silicon containing monomers. In the chemiresistive sensors, conductivity was induced in the polymer matrix by doping with iodine. The paper describes the experimental polymerization conditions, the physical characteristics of the polymers, and the application of the different polymers to sensing common volatile analytes.     

DNA condensation induced by a cationic polymer studied by atomic force microscopy and electrophoresis assay

We synthesized a cationic polymer, poly(PEGMA)-4N, which has brush-like chains and four positively charged amino groups at the end of the molecules. DNA condensation induced by poly(PEGMA)-4N was investigated through electrophoresis assay by its ability to retard DNA mobility and to inhibit HindIII enzyme cleavage. The detailed structures of DNA condensates induced by poly(PEGMA)-4N were observed through atomic force microscopy (AFM). Interactions between polymers and DNA are mainly attributed into depletion effect and electrostatic interaction. Positively charged amino groups in poly(PEGMA)-4N interact with DNA through electrostatic interaction, and depletion effect also takes effect because poly(PEGMA)-4N is a flexible polymer. Comparing the contributions that the two interactions gave in DNA condensation process, we found that depletion effect played a major role compared with electrostatic interaction.     

A comparison of the properties of two structurally equivalent but regiochemically different mono‐alkylated polybithiophenes prepared through AABB‐type stille polycondensation

Previous routes to polymers with mono‐alkylated bithiophenes have proceeded through polymerization of monoalkyl‐2,2′‐bithiophene monomers through oxidative or AB‐type cross‐coupling polymerizations. The resulting polymer regiochemistry affects both the location and orientation of the polymer side‐chains. In contrast, AABB‐type cross‐coupling polymerizations can control the location and in some cases the orientation of the side‐chains. To study how this control can impact polymer properties, two poly(monodecyl‐2,2′‐bithiophene) polymers have been synthesized through Stille AABB‐type polycondensations of 2,5‐bis(trimethylstannyl)thiophene with different monomers. The alkyl side‐chains are located on every other thiophene, but polymer 1 consists of both head‐to‐tail and head‐to‐head dyads, whereas polymer 2 is made up of only head‐to‐head dyads. ¹H NMR, ¹³C NMR, and heteronuclear single quantum correlation spectroscopy are used to confirm and contrast the polymer regiochemistries. The physical properties of the two polymers are analyzed using UV–vis spectroscopy, differential scanning calorimetry, and grazing‐incidence X‐ray diffraction. Polymer 2 is found to display significantly more aggregation in solution than 1, and it displays different thermal properties. The film properties of polymers 1 and 2, however, are very similar, with nearly identical UV–vis profiles and d‐spacing values as determined by grazing incidence X‐ray diffraction. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

重氮偶合反应合成超支化偶氮聚合物的光响应性能研究

利用重氮偶合反应和后重氮偶合反应制备了主链和端基含有不同假芪型偶氮苯生色团的超支化偶氮聚合物.利用氢核磁共振、紫外光谱、红外光谱等分析手段确定了合成聚合物的结构、玻璃化转变温度和光谱特性等.研究了聚合物光致二向色性的性能,此聚合物的取向有序度为0.063.用两束相干的P偏振Ar+激光对聚合物膜进行光加工,得到形状规则的正弦波形表面起伏光栅,末端偶氮苯基团的引入极大地增加了超支化偶氮聚合物的光响应速度.     

The theta-temperature depression caused by topological effect in ring polymers studied by Monte Carlo simulation

We studied equilibrium conformations of linear and ring polymers in dilute solutions over the wide range of segment number N of up to 2048 with Monte Carlo simulation, and evaluated N dependence of the radii of gyration, R(g), of chains. The polymer molecules treated in this study are assumed to be composed of beads and bonds, and they are put in a three-dimensional face-centered cubic (FCC) lattice. The values of Flory's critical exponent, ν, for linear and ring polymers were estimated from the N dependence of R(g), and the temperatures at which ν reach 1/2 were obtained. Here we define those as Θ-temperatures in this report. The simulation result shows that the Θ-temperature for ring polymers is evidently lower than that of the linear polymers, and the origin of the Θ-temperature depression is discussed. Since R(g) of a ring polymer is smaller than that for a linear polymer at the same N and temperature, the segment density for a ring polymer is increased by the topological effect and the repulsive force between segments of a ring polymer at the Θ-temperature for a linear polymer is stronger. Thus, the origin of the Θ-temperature depression for ring polymers is the repulsive force emphasized by the topological effect of rings.     

Threading synthetic polyelectrolytes through protein pores

We have measured the ionic current signatures of sodium poly(styrene sulfonate) as its single molecules translocate through an alpha-hemolysin pore embedded into a bilayer in a salty aqueous medium under an externally applied electric field. As in the previous experiments involving DNA and RNA, the pore current, which is a measure of the ionic conductivity of the low molar mass electrolyte ions, is significantly reduced when the polymer molecule translocates through the pore. The magnitude and the duration of the reduction in the pore current are measured for each of the translocation events. By studying thousands of events of reduction in the ionic current, we have constructed distribution functions for the extent of the reduced current and for the translocation time. The details of these distribution functions are significantly different from those for DNA and RNA. By investigating over two orders of magnitude in the molecular weight of the polymer, the average translocation time is found to be proportional to the molecular weight and inversely proportional to the applied voltage. This demonstration of threading a synthetic polyelectrolyte through a protein pore opens up many opportunities to systematically explore the fundamental physical principles behind translocation of single macromolecules, by resorting to the wide variety of synthetically available polymers without the complexities arising from the sequences of biological polymers. In addition, the present experiments suggest yet another experimental protocol for separation of polymer molecules directly in aqueous media.     

Electrochemical sensors and biosensors based on redox polymer/carbon nanotube modified electrodes: A review

The aim of this review is to present the contributions to the development of electrochemical sensors and biosensors based on polyphenazine or polytriphenylmethane redox polymers together with carbon nanotubes (CNT) during recent years. Phenazine polymers have been widely used in analytical applications due to their inherent charge transport properties and electrocatalytic effects. At the same time, since the first report on a CNT-based sensor, their application in the electroanalytical chemistry field has demonstrated that the unique structure and properties of CNT are ideal for the design of electrochemical (bio)sensors. We describe here that the specific combination of phenazine/triphenylmethane polymers with CNT leads to an improved performance of the resulting sensing devices, because of their complementary electrical, electrochemical and mechanical properties, and also due to synergistic effects. The preparation of polymer/CNT modified electrodes will be presented together with their electrochemical and surface characterization, with emphasis on the contribution of each component on the overall properties of the modified electrodes. Their importance in analytical chemistry is demonstrated by the numerous applications based on polymer/CNT-driven electrocatalytic effects, and their analytical performance as (bio) sensors is discussed.     

部分水解聚丙烯酰胺与蠕虫状胶束在微米级毛细管中的驱替粘度

部分水解聚丙烯酰胺(HPAMs)被大量地用作三次采油中驱替液的增稠剂,表面活性剂在一定的条件下可以通过自组装形成蠕虫状胶束,具有与高分子相似的增稠的作用。本文在半径为1–10 μm的毛细管中,分别考察了HPAMs与蠕虫状胶束的微观驱替行为,研究结果表示毛细管内腔的尺寸限制了这些非牛顿流体的增稠作用。随着毛细管半径的减小,聚合物溶液的剪切变稀越剧烈,甚至从非牛顿流体转变为牛顿流体的流体行为。结合驱替研究和超滤、电镜的结果,证明了高分子的缠绕结构在毛细管中已被破坏。通过对比驱替数据,蠕虫状胶束在毛细管中能够更大程度地保留宏观的粘度,我们提出表面活性剂能够通过自组装修复被破坏的缠绕结构,比高分子聚合物在微观有限空间中有更好的增稠能力。     

Chemical Biological Sensors Based on Advances in Conducting Electroactive Polymers

Advances in conducting electroactive polymers (CEPs) have driven the design of novel chemical and biochemical sensors. The redox properties of CEPs have been intensely studied for more than two decades with emphasis on their synthesis and characterization. Little attention has been paid to the importance of mechanism in sensor designs. However, in order to design robust and stable sensors, it is important to understand how the polymer structure, morphology, adhesion properties and microenvironment affect sensor performance. This work describes how chemical and biological sensors have been designed, fabricated, characterized and tested based on the fundamental understanding in CEPs. The use of photopolymerized conducting polymers in sensor designs is described. Four focus areas are presented in which the electronic properties of CEPs have enabled the design of novel sensors for organics, nucleic acids, biological molecules, vapors and metal ions.     

Relaxation phenomena of hydrolyzed polyvinylamine molecules adsorbed at the silica/water interface I. Saturated homogeneous polymer layers

Surface area exclusion chromatography was used to investigate the adsorption and reconformation characteristics of hydrolyzed polyvinylamine molecules at silica/water interfaces employing radiolabeled polymers. The polymer solution was injected at the inlet of the column, whereas the polymer was successively adsorbed on the stacked glass-fiber filters constituting the stationary phase of the column. The filters and effluent samples collected at the outlet were individually analyzed for radioactivity content, which provided the adsorption histogram and the relative affinity of the various polymers. For saturated polymer layers, the relaxation process was demonstrated when the exceedingly adsorbed molecules desorbed. Modifications in the adsorption on the successive filters were thus converted into changes in the interfacial area of adsorbed molecules, taking into account the deviation from the plateau adsorption expected for nonrelaxing systems. Adsorption characteristics of nonrelaxed polymer layers were determined from the adsorption values determined before relaxation occurred. Adsorption and relaxation characteristics were determined to depend strongly on molecular weight and degree of hydrolysis of the polyvinylamine molecules. Half-hydrolyzed polymers had adsorption and relaxation characteristics close to those of the fully hydrolyzed polyvinylamine. Accordingly, adsorption isotherms on the cellulose/water interface were carried out to possibly extend the main conclusions of the study.     

Preparation and application of hollow molecularly imprinted polymers with a super‐high selectivity to the template protein

Protein‐imprinted polymers with hollow cores that have a super‐high imprinting factor were prepared by etching the core of the surface‐imprinted polymers that used silica particles as the support. Lysozyme as template was modified onto the surface of silica particles by a covalent method, and after polymerization and the removal of template molecules, channels through the polymer layer were formed, which allowed a single‐protein molecule to come into the hollow core and attach to the binding sites inside the polymer layer. The adsorption experiments demonstrated that the hollow imprinted polymers had an extremely high binding capacity and selectivity, and thus a super‐high imprinting factor was obtained. The as‐prepared imprinted polymers were used to separate the template lysozyme from egg white successfully, indicating its high selectivity and potential application in the field of separation of protein from real samples.