Adsorption isotherms of a molecular imprinted polymer prepared in the presence of a polymerisable template: Indirect evidence of the formation of template clusters in the binding site

The current opinion about molecular imprinted polymers (MIPs) is that their molecular recognition properties are due to the presence of nanocavities formed during a polymerization process developed in the presence of a template molecule. According to this principle, the shape of these nanocavities is complementary to that of the template and non-covalent interactions are established between the binding site and a single template molecule. Nevertheless, there are some experimental indications that the real molecular recognition mechanism involves clusters of template molecules being packed into the binding site. Recently, it has been proposed that template molecules covalently linked to the binding site can act as nucleation points, enhancing the formation of these molecular clusters.We have tested this hypothesis by studying the adsorption isotherms of polymers prepared by imprinting them with 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). Three different polymers were considered: P0, prepared without the template, P1, whose template was represented by 2,4,5-T molecules, and P2, whose template was 1/3 constituted by the polymerisable 2-(2,4,5-trichlorophenoxyacetoxy)-ethylmethacrylate (2,4,5-TEMA) and 2/3 by 2,4,5-T. The polymers were prepared by thermoinduced polymerization of template mixtures, 4-vinylpyridine and ethylene dimethacrylate. The crushed polymers were packed into HPLC columns and frontal chromatographic runs were performed by eluting the columns with a mobile phase containing variable amounts of 2,4,5-T.The experimental adsorption isotherms were fitted by using several isotherm models, and the Freundlich-Langmuir model was found to give the best fitting in terms of F-test. All the models considered showed a significant difference between the affinity constant values measured for the polymer P1 and P2, with a higher value for the polymer P2 (for Freundlich-Langmuir model: polymer P1, k=(2.00±0.43)×10⁴ M⁻¹; polymer P2, k=(1.93±0.0535)×10⁵ M⁻¹; ratio P2/P1, 9.65±2.09). Such experimental results support the hypothesis that a polymer prepared with a limited amount of template covalently attached to the binding site shows an increased affinity for the template itself.     

Pattern of separatrices and intrinsic reaction coordinates for degenerate thermal rearrangements

A structurally stable model of the standard adiabatic gradient field of the potential energy surface for certain pericyclic reactions is derived.These reactions are not subjected to the principles of orbital isomerism or to the Woodward-Hoffmann rules.Use is made of a principle established by Ariel Fernández and Oktay Sinanolu which precludes direct meta-IRC connections between transition states.It is shown that Jahn-Teller isomers of the singlet biradicals involved in the process are not interconvertible since the biradical configuration is not a transition state but a critical point with Hessian matrix with two negative eigenvalues.The topological features of the PES obtained by combinatorial methods are in full agreement with earlier results obtained from MINDO calculations.     

Molecular-shape recognition of polycyclic aromatic hydrocarbons in reversed phase liquid chromatography

Summary The molecular-shape recognition of polycyclic aromatic hydrocarbons has been studied on various stationary phases in reversed-phase high-performance liquid chromatography. The examined stationary phases were phenyl-, diphenyl-, triphenyl- and benzyl-bonded silicas. The results of regression analysis inidcated that triphenylsilica is the best packing material to recognize the difference in the molecular-shape of structural isomers. This fact was confirmed by the separation of 4-ring isomers.     

EFFECT OF MOLECULAR WEIGHT OF PDMS ON MORPHOLOGY AND MECHANICAL PROPERTIES OF PP/PDMS BLENDS

 A series of polydimethylsiloxane (PDMS) with varied molecular weights (Mw = 3  106, 1  106 and 0.5  106) were melt blended with PP to investigate the effect of PDMS molecular weight (MW) on the morphology and mechanical properties of PP/PDMS blends. Scanning electron microscopic (SEM) examination showed that the size of PDMS domains was dependent on the MW of PDMS. It was found that the lower the value of PDMS MW, the better dispersion of the PDMS domains in the PP matrix. Tensile and Izod impact tests revealed that the addition of PDMS with lower MW would lead to a more significant increase in impact strength of the blends compared with the blends with higher MW ones, while the influence of the molecular weight on tensile strengths of the blends was relatively small in the MW range studied. Differential scanning calorimetry (DSC) results also showed that the crystallization temperature of PP was increased with decreasing PDMS MW, indicating a better nucleation capability of lower MW of PDMS. Melting flow rate (MFR) measurements indicated that the processibility of PP could be enhanced by adding PDMS, and again the lower MW PDMS resulted in better data. Our work demonstrates that not only the processibility but also the mechanical properties of PP could be enhanced to a more significant degree by using low MW PDMS than the higher ones.     

取代苯系列衍生物电子结构与毒性关系的量子化学研究

取代苯系列衍生物电子结构与毒性关系的量子化学研究苏忠民，徐贤姬，李金昶（东北师范大学化学系，长春，１３００２４）赵宝忠，盛连喜（东北师范大学环科系，长春，１３００２４）关键词：取代苯衍生物，分子毒性，ＭＮＤＯ采用量子化学半经验ＡＭＩ、ＭＮＤＯ方法，从...     

Thermodynamics of molecular interactions in ethyl iodide+toluene mixtures

The excess Gibb's free energy of mixing, G^E, for ethyl iodide+toluene at 25°C have been obtained from the measured vapor pressuure data. The H^E and G^E values for ethyl iodide+toluene are positive throughout the ethyl iodide concentration range and G^E>H^E. The results have been analyzed in terms of Flory and ideal associated model theory of nonelectrolyte solutions. It has been observed that the ideal associated model approach which assumes the presence of AN and A₂B molecular species describes well (within±10 J-mol^–1 in the worst case) the general dependence of H^E on X_A (mole fraction of ethyl iodide) over the whole composition range for ethyl iodide+toluene mixtures. The equilibrium constants for A+A AB and 2A+BA₂B reactions along with the enthalpies of formation of AB and A₂B molecular species have been calculated.     

Synthesis and Structure of(NH4)_2 [V2O_4(OCH_2COO)_2]

ＳｙｎｔｈｅｓｉｓａｎｄＳｔｒｕｃｔｕｒｅｏｆ（ＮＨ４）２［Ｖ２Ｏ４（ＯＣＨ２ＣＯＯ）２］ＺＨＯＵＺｈａｏ－ｈｕｉ，ＷＡＮＧＪｉｎｚｈｉ，ＷＡＮＨｕｉ－ｌｉｎａｎｄＴＳＡｌＫｈｉ－ｒｕｉ（ＤｅｐａｒｔｍｅｎｔｏｆＣｈｅｍｉｓｔｒｙ，ＸｉａｍｅｎＵｎｉ...     

分子量对聚丙烯等温结晶的影响

<正> 在高聚物结晶动力学的研究中,分子量对结晶速率的影响是一个有实际意义和理论兴趣的研究课题,由于聚烯烃可以得到分子量变化范围相当宽(MW从10~3到10~6)的试样,因而它是研究结晶速率分子量依赖性较合适的对象,其中研究最多的是聚乙烯和聚丙烯。从前入的研究报道看来,影响聚丙烯结晶速率的因素比聚乙烯要复杂。除了聚丙烯可生成多种晶型结构,会影响其结晶速率以外,用不同聚合方法制备的试样,由于其链结     

Molecular and nanoscale materials and devices in electronics

Over the past several years, there have been many significant advances toward the realization of electronic computers integrated on the molecular scale and a much greater understanding of the types of materials that will be useful in molecular devices and their properties. It was demonstrated that individual molecules could serve as incomprehensibly tiny switch and wire one million times smaller than those on conventional silicon microchip. This has resulted very recently in the assembly and demonstration of tiny computer logic circuits built from such molecular scale devices. The purpose of this review is to provide a general introduction to molecular and nanoscale materials and devices in electronics.