Construction of the Systems with Memory of Molecules and Thir Application to Artificial antibody Catalysts

在这项研究中，人们试图开发一种新的分子印迹方法，使可溶宿主具有客体分子的大小和形状的记忆。β-环糊精(β-CD)在水溶液中充当宿主分子，是实现这一目标的关键化合物。首先，在1-萘乙酸(模板客体)和b-CD的混合物中加入戊二酸氯化物、丙二酸氯化物和琥珀酸氯化物。围绕所含客体分子发生的分子内交联会形成具有客体大小和形状记忆的空腔。反应结束后，不溶物质被过滤掉--溶液被脱盐。将溶液加入丙酮，收集沉淀物。通过添加具有记忆能力的修饰CD引起的荧光强度的变化，通过获得结合常数(1：1化学计量比)来评价记忆能力的程度。客体诱导的荧光强度变化可以用1：1主-客体化学计量学来分析。客体选择性用相对结合常数来评价，以萘为100作为标准。以间苯乙酸为模板客体时，L-甲氧基萘与修饰后的CD的结合强度是J3-CD的两倍。另一方面，当模板客体为2-萘基乙酸时，2-甲氧基萘和2-乙氧基萘的结合强度是修饰后CD的两倍。作为另一种尝试，使用模板客体结合到柱凝胶和含有7个氨基或乙二胺单元的CDS上进行柱层析。在这种情况下，磨损S碱的形成是交联反应。该方法已被证明是一种很有前途的新型分子印迹方法。

In this study, attempts have been made to develop a new molecular imprinting method that gives soluble hosts with a memory of size and shape of guest molecules. beta-CycIodextrin (beta-CD), which acts as .a host molecule in aqueous solution, has been used as a key compound to reach the aim. First, to a mixture of 1-naphthaleneacetic acid (template guest) and b-CD were added glutalalic acid chloride, malonyl acid chloride, and succinic acid chloride. The intramolecular crosslinking occurring around the included guest molecule may form the cavity which has a memory of the-size and shape of the guest. After the reaction, insoluble matter was removed by filtration-and the solution was desalted. The solution was added to acetone, and the precipitates were collected. The extents in memory ability were evaluated by obtaing binding constants (1 : 1 stoichiometry) from the changes in the fluorescence intensity induced by addition of the modified CD with memory ability. The guest induced variations in the fluorescence intensity could be analized by 1 : 1 host-guest stoichiometry. The guest selectivities were evaluated by the relative binding vonstants, making 100 for naphthalene as a standard. When I-naphthaleneacetic acid was used as the template guest, l-methoxynaphthalene was bound two-times stronger to the modified CD than to j3-CD itself. On the other hand, when 2-naphihaleneacetic acid was a template guest, 2-methoxynaplithalene and 2-ethoxynaphthalene were bound two times stronger to the modified CD.As another attempt, column chromatography was performed by using template guest bound to column gel and CDs with seven amino or ethylendiamine units. In this case, Scuff s base formation is the crosslinking reaction. This method has been proven to be a promissing method as new molecular imprinting method.