卟啉及荧光素衍生物模拟的分子逻辑器件的设计，制备与研究
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摘要
自从分子逻辑的布尔逻辑被阐述以来，分子逻辑器件以其优于传统电子逻辑器件的诸多优势得到了广泛的发展，首先我们可以通过改变构成分子逻辑器件的分子的结构来改变分子逻辑器件的逻辑功能，换言之我们可以通过分子设计来实现对目标逻辑功能的模拟，然后我们也可以通过自组装等方式得到各向同性的分子阵列来实现传统意义上的功能化集成。分子逻辑器件在很多方面都取得了优异的成果，例如二进制计算器，分子键盘锁，加码解码器等。
分子逻辑器件就其功能而论分成两种逻辑器件：组合逻辑器件以及时序逻辑器件，前者在操作过程中不考虑输出历史且不具有记忆功能，而后者在操作过程中要考虑历史且具有记忆功能。本文设计并合成了卟啉类衍生物以及荧光素酰腙类衍生物来模拟这两种逻辑器件。
1、我们将具有氨基功能团的不对称中位四苯基卟啉以共价嫁接的形式固载到介孔二氧化硅薄膜上，由于卟啉化合物对酸碱的特异性响应，当我们将含有卟啉化合物的介孔薄膜材料置于酸性或碱性溶液中并取出时，卟啉在酸性或碱性介质中的状态会被完整的保存下来，进而实现对具有逻辑记忆功能的RS触发器的模拟，因为卟啉化合物是通过共价嫁接的形式固载到介孔薄膜材料上，所以使得分子逻辑器件兼具了介孔薄膜材料的优异性质：
a.相对较大的表面积，不但有利于输入介质与响应单元更有效的接触，还有益于输入介质的彻底清除，避免其残留下来影响下次逻辑输入。
b.周期性排布的均一孔道结构，更加有利于器件的后期加工。
c.高的透过性使得该分子逻辑器件的输出（output）更容易被光学检测仪器所监听。
2、为了提高已知分子逻辑器件的安全性，我们设计并合成了荧光素酰腙类衍生物，对已知由荧光素模拟的二进制计算器逻辑功能进行逻辑加密，并且由于自毁装置的存在使得这种逻辑加密更加安全，这一逻辑功能是由荧光素酰腙类衍生物在二价铜离子催化下，与酸反应部分分解并生成二价铜离子配合物，而与碱反应完全分解并释放出具有模拟二进制计算器逻辑功能的荧光素分子，进而实现了对已知分子逻辑器件进行加密，在酸性介质中生成了稳定的二价铜离子配合物，既不会还原成原化合物，在加入过量碱时也不会释放出荧光素，所以不能对该分子逻辑器件进行暴力破解。
Since the concept of Boolean logic of molecular logic has been depicted, lots ofefforts has been carried out and achieved viarious of developments due to itsadvantagements over traditional electronic device. They appear at that we can firelydesign molecular with special structure to achieve aim logic function, we can alsofunctionally integrate these molecular logic via self-asssembling process et al.Molecular logic device achieves lots of considerable results at different aspects, eg:elementary arithmetic, key-pad lock, and coder-decoder et al.
Based on the function of logic device, it can be categorized into two types:combinational logic device and sequential logic device. During processing, the laterone different from the former one needs to take operational history or outputs inconsideration, like the functions of memory. Herein, we design and synthesiscorresponding porphyrin and fluorescein derivatives to mimic these two types oflogic device.
1. Here, an asymmetric porphyrin derivative of5-(4-aminophenyl)-10,15,20-triphenyl-porphyrin (H2ATPP) has been successfully covalently connected tophoto-permeable mesoporous silica thin films as a unit to mimic logic function. Thishybrid mesoporous structure is not only advantageous to the interaction between inputs and response materials, but also to separation of the response materials andinputs without information lost. Then several molecular logics with the function ofmemory, based on its characteristic of being sensitive to acid and base, are achieved.With different initial states, it could be handily described as feedback loop andRS-latch for sequential logic.
2, Afluorescein derivative named fluorescein hydrizido4-imidophenol (FHP) hasbeen designed to build a molecular logic device. The device is composed of two parts:lock-part and calculate-part. In this derivative, fluorescein is reffered to ascalculate-part owing to it was previously adopted to mimic calculator. And the restportion of this derivative is reffered to as lock-part. The operational principle of thisdevice is that if input combination is optimal, calculate-part fluorescein is releasedand ready for calculating; if not, calculate-part remains locked. It effectively improvesthe security of calculator simulated by molecular logic. In addition, lock-part will betotally destroyed like self-distruction under a special input combination, resulting inthat calculate-part can’t be unlocked at all events. Hence, it’s more sufficient to makebrute-force attack on this device unrealistic.
分子逻辑器件就其功能而论分成两种逻辑器件：组合逻辑器件以及时序逻辑器件，前者在操作过程中不考虑输出历史且不具有记忆功能，而后者在操作过程中要考虑历史且具有记忆功能。本文设计并合成了卟啉类衍生物以及荧光素酰腙类衍生物来模拟这两种逻辑器件。
1、我们将具有氨基功能团的不对称中位四苯基卟啉以共价嫁接的形式固载到介孔二氧化硅薄膜上，由于卟啉化合物对酸碱的特异性响应，当我们将含有卟啉化合物的介孔薄膜材料置于酸性或碱性溶液中并取出时，卟啉在酸性或碱性介质中的状态会被完整的保存下来，进而实现对具有逻辑记忆功能的RS触发器的模拟，因为卟啉化合物是通过共价嫁接的形式固载到介孔薄膜材料上，所以使得分子逻辑器件兼具了介孔薄膜材料的优异性质：
a.相对较大的表面积，不但有利于输入介质与响应单元更有效的接触，还有益于输入介质的彻底清除，避免其残留下来影响下次逻辑输入。
b.周期性排布的均一孔道结构，更加有利于器件的后期加工。
c.高的透过性使得该分子逻辑器件的输出（output）更容易被光学检测仪器所监听。
2、为了提高已知分子逻辑器件的安全性，我们设计并合成了荧光素酰腙类衍生物，对已知由荧光素模拟的二进制计算器逻辑功能进行逻辑加密，并且由于自毁装置的存在使得这种逻辑加密更加安全，这一逻辑功能是由荧光素酰腙类衍生物在二价铜离子催化下，与酸反应部分分解并生成二价铜离子配合物，而与碱反应完全分解并释放出具有模拟二进制计算器逻辑功能的荧光素分子，进而实现了对已知分子逻辑器件进行加密，在酸性介质中生成了稳定的二价铜离子配合物，既不会还原成原化合物，在加入过量碱时也不会释放出荧光素，所以不能对该分子逻辑器件进行暴力破解。
Since the concept of Boolean logic of molecular logic has been depicted, lots ofefforts has been carried out and achieved viarious of developments due to itsadvantagements over traditional electronic device. They appear at that we can firelydesign molecular with special structure to achieve aim logic function, we can alsofunctionally integrate these molecular logic via self-asssembling process et al.Molecular logic device achieves lots of considerable results at different aspects, eg:elementary arithmetic, key-pad lock, and coder-decoder et al.
Based on the function of logic device, it can be categorized into two types:combinational logic device and sequential logic device. During processing, the laterone different from the former one needs to take operational history or outputs inconsideration, like the functions of memory. Herein, we design and synthesiscorresponding porphyrin and fluorescein derivatives to mimic these two types oflogic device.
1. Here, an asymmetric porphyrin derivative of5-(4-aminophenyl)-10,15,20-triphenyl-porphyrin (H2ATPP) has been successfully covalently connected tophoto-permeable mesoporous silica thin films as a unit to mimic logic function. Thishybrid mesoporous structure is not only advantageous to the interaction between inputs and response materials, but also to separation of the response materials andinputs without information lost. Then several molecular logics with the function ofmemory, based on its characteristic of being sensitive to acid and base, are achieved.With different initial states, it could be handily described as feedback loop andRS-latch for sequential logic.
2, Afluorescein derivative named fluorescein hydrizido4-imidophenol (FHP) hasbeen designed to build a molecular logic device. The device is composed of two parts:lock-part and calculate-part. In this derivative, fluorescein is reffered to ascalculate-part owing to it was previously adopted to mimic calculator. And the restportion of this derivative is reffered to as lock-part. The operational principle of thisdevice is that if input combination is optimal, calculate-part fluorescein is releasedand ready for calculating; if not, calculate-part remains locked. It effectively improvesthe security of calculator simulated by molecular logic. In addition, lock-part will betotally destroyed like self-distruction under a special input combination, resulting inthat calculate-part can’t be unlocked at all events. Hence, it’s more sufficient to makebrute-force attack on this device unrealistic.
引文
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