双酶体系的构建及其应用研究
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摘要
酶是生命活动中具有催化功能的蛋白质。由于多酶协同作用在生命过程与生命活动中的重要性,多酶协同催化成为酶催化领域中极富挑战性和创新性的研究课题。本论文立足于双酶体系,以仿生学为导向,对一些重要的双酶体系进行抗氧化、自修复以及微马达等方面的设计、构建及应用研究。
具体研究结果如下：
1)双酶抗氧化体系：以铁蛋白和卟啉为构筑基元,设计构建具有谷胱甘肽过氧化物酶(GPx)和超氧化物歧化酶(SOD)活力的双酶模拟物。首先通过计算机模拟设计了GPx的催化中心,再利用基因工程方法将硒代半胱氨酸(Sec)精确地引入铁蛋白中,得到的含硒铁蛋白单体经自组装可形成具有多催化位点的GPx模拟物Se-Fn。然后利用化学合成手段制备的具有良好水溶性并带有醛基的SOD模拟物：[Mn-THPP-(PEG2000-BA)4],通过醛基和Se-Fn的赖氨酸残基(Lys)上氨基之间的共价相互作用,使其交联形成具有双酶活力的单分散性微凝胶纳米酶模型,并最终证明了该酶模型在亚细胞水平上具备较好的协同抗氧化能力。
2)双酶自修复体系：在以动态亚胺键交联牛血清白蛋白和戊二醛形成的蛋白凝胶中,借助动态亚胺键的酸刺激响应性,向体系中引入葡萄糖氧化酶(GOx)和过氧化氢酶(CAT)协同调控pH变化,构建双酶自修复体系。其中葡萄糖氧化酶能催化氧化葡萄糖(Glu)生成葡萄酸内酯和H2O2。产物H2O2可被过氧化氢酶(CAT)酶迅速清除,产生H2O和02,避免了H2O2对体系亚胺键结构的破坏。而另一个产物葡萄酸内酯则进一步水解生成葡萄糖酸,降低体系的pH,促进亚胺键的形成。因此,通过向凝胶中加入葡萄糖,利用GOx与CAT双酶协同催化作用,可改变体系pH,从而调控牛血清白蛋白和戊二醛之间交联,实现体系的自修复。
3)双酶微马达体系：利用GOx与CAT双酶催化产生气体的反向推动原理,设计构建了微马达体系。我们以硅胶为载体,在硅胶表面修饰过氧化氢酶(CAT),然后置于葡萄糖氧化酶和葡萄糖共存的体系中。由于葡萄糖氧化酶氧化葡萄糖产生H202,过氧化氢酶分解H2O2放出氧气为动力,推动微马达运动。由于微马达表面结构的不对称性,使得该体系存在不同的运动方式,即直线运动和旋转运动。该体系的构建为其在微纳物体运输和生物传感等领域的应用提供了新的思路。
Enzymes are nature evolution of proteins with high specificity and strong catalyticability, which can catalyze certain chemistry reaction in mild conditions. Because ofthe unique supramolecular interaction between enzyme and its substrate, it becomes thefirst choice when studying the bionic system. Enzyme catalytic process is verycomplexity, but with the development of the genomics, proteomics, and computersimulation, people have a deeper understanding of the enzyme catalysis andapplication.
Multi-enzyme synergistic catalytic system is one of the challenging researchtopics in the field of enzyme-catalyzed. Due to the complexity of the systems and theunstability property of the enzyme, limiting the development of the multi-enzymesynergistic catalysis system. However, the amazing ability of native enzymesdemonstrated the efficiency and specificity under mild conditions, still attractedscientists extensive attention. Therefore, the study of multi-enzyme synergisticcatalysis and its related application, has become a common concern in chemistry,biology and life sciences. Explore of multi-enzyme synergistic catalysis system hasgreat significance in understanding the evolution process of enzyme and therelationship between the tructure and function of enzyme. Herein, as guidance ofbionics, we used the dual-enzyme system for exploring antioxidant, self-healing andmicro motor.
1. Construction of dual enzymatic antioxidant system
The antioxidant enzymes, superoxide dismutase (SOD), catalase (CAT), andglutathione peroxidase (GPx) contribute dominatingly to enhance cellularantioxidative defense against oxidative stress in the human body. Thereinto, SOD is ametalloenzyme that catalyzes the dismutation of superoxide radical anion (O2-)toH2O2and dioxygen. H2O2is then detoxified either to H2O and O2by catalase (CAT)or to H2O by glutathione peroxidase (GPx). Studies indicated that each enzyme has aspecific as well as an irreplaceable function and they act in a cooperative or synergistic way to ensure a global cell protection, and only when an appropriatebalance between the activities of these enzymes is maintained, the optimal protectionof cells could be achieved.
In recent years, there were considerable interests in preparing the enzyme mimicswith the properties of SOD or GPx for elucidating catalytic mechanism and forpotential pharmaceutical application. In order to further study the cooperation of theseenzymes in antioxidation and to generate efficient therapeutic agents, somebifunctional artificial enzymes with antioxidant enzyme activities have beenconstructed by chemical methods.
Here, based on the understanding of the synergy of the natural antioxidant enzymes,we have carried out work as follow. Using computational design and geneticengineering methods, the main catalytic components of GPx were fabricated onto thesurface of ferritin. The resulting seleno-ferritin (Se-Fn) monomers can self-assembleinto nanocomposites which exhibit remarkable GPx activity due to the well organizedmulti-GPx catalytic centers. Subsequently, a porphyrin derivative was synthesized asSOD mimic to crosslink Se-Fn nanocomposites for the formation of a synergistic dualenzyme microgel, and this dual enzyme microgel has been proven to displaysignificantly better antioxidant ability than single GPx or SOD mimic in protectingcell from oxidative damage.
2. Construction of dual enzymatic self-healing system
The abilities to spontaneously heal injury and recover functionality are keyfeatures that increase the survivability and lifetime of the organism. In contrast,synthetic materials usually fail after damage or fracture. Inspired by nature, thedemand for self-healing materials is rapidly development because they can offer anew rote toward safer, longer-lasting products and lower production costs. Over thepast few decades, there were three kinds of conceptual self-healing systems have beenreported, such as capsule system, vascular system, and intrinsic system.
As one of the acidity reversible covalent bonds, imine bond—from an amine andan aldehyde has been widely used in the construction of exotic molecules and extendstructures on account of the inherent ‘proof-reading’ and ‘error-checking’ associatedwith these reversible reactions. But more importantly, the equilibrium of imine bondformation between an imine and its corresponding precursor(s) can influenced by theexternal considerations, such as solvent, pH, and temperature.
Herein, we reasoned that one such reaction, the glutaraldehyde by the reversible covalent attachment of the GOx and the bovine serum albumin (BSA) to the lysineresidue, could be well suited for the formation and functionalization of proteinhydrogels system. The BSA as a scaffolding sustain the hydrogels system and theGOx as a catalytic center play a key role to adjust the pH of the system by add extratraces of glucose. The glucose is oxidized to gluconolactone under the catalytic of theGOx, then gluconolactone hydrolyzed to gluconic acid to reduce the system pH. TheH2O2that generated by the catalytic reaction will be decomposition by the enzymecatalase (CAT) to avoid the glutaraldehyde is oxidized. With the change of the pH, theimine bonds provide us the opportunity to drive the reaction forward or backwards.
3. Construction of dual enzymatic micro-motor system
Life is movement. For the nature forms, the material transport in cellular, DNAreplication, cell division and differentiation, muscle contraction, a series of importantlife activities are dependent on the movement of the biological molecular motors inthe cytoplasm. These motors are nanomachines which can be transform the energy ofbiochemistry to mechanical. In the natural world, the autonomous motion of biomotoris common. Protein motors and bacteria have formed a variety of sophisticated andperfect systems fuelled with chemical energy, and well-controlled nanomachines canexecute translational and rotational movement precisely. The outstanding performanceof these biomotors in nature has stimulated interest in synthesis of manmademicro-/nano-motors which can mimic the behaviors of biomotors to operate inlocally-supplied chemical fuels and achieve various functions. The first generation ofcatalytic motors on the micro-/nano-scale which exhibit autonomous self-propulsionin the presence of hydrogen peroxide makes this idea promising and exhibits potentialapplications in small cargo delivery and biosensing.
Based on the catalytic decomposition of H2O2, we constructed a dual enzymemicro-motor system. The system applications the bubbles promote motor model.Motors that utilize this type of motion create bubbles on their catalytic side and theforce from the release of the bubbles causes the motion. This is a gradientlikemechanism since bubbles need to be generated on one side and not the other so thereis a change in bubble concentration with distance. We take silica gel as a carrier, anddecorate catalase (CAT) on the surface of silica. Then the silica gel was placed intothe system of glucose oxidase and glucose. Due to the glucose oxidase oxidation ofglucose, H2O2was generated. Catalase decomposition of H2O2release oxygen can bedriving silica sports. Due to the inhomogeneity of the silica surface, there are different sports ways in the system, such as linear motion and rotary motion. We anticipate thatthis system could provide a new approach for micro-and nano objects transport,bio-sensing and other areas in vivo application.
具体研究结果如下：
1)双酶抗氧化体系：以铁蛋白和卟啉为构筑基元,设计构建具有谷胱甘肽过氧化物酶(GPx)和超氧化物歧化酶(SOD)活力的双酶模拟物。首先通过计算机模拟设计了GPx的催化中心,再利用基因工程方法将硒代半胱氨酸(Sec)精确地引入铁蛋白中,得到的含硒铁蛋白单体经自组装可形成具有多催化位点的GPx模拟物Se-Fn。然后利用化学合成手段制备的具有良好水溶性并带有醛基的SOD模拟物：[Mn-THPP-(PEG2000-BA)4],通过醛基和Se-Fn的赖氨酸残基(Lys)上氨基之间的共价相互作用,使其交联形成具有双酶活力的单分散性微凝胶纳米酶模型,并最终证明了该酶模型在亚细胞水平上具备较好的协同抗氧化能力。
2)双酶自修复体系：在以动态亚胺键交联牛血清白蛋白和戊二醛形成的蛋白凝胶中,借助动态亚胺键的酸刺激响应性,向体系中引入葡萄糖氧化酶(GOx)和过氧化氢酶(CAT)协同调控pH变化,构建双酶自修复体系。其中葡萄糖氧化酶能催化氧化葡萄糖(Glu)生成葡萄酸内酯和H2O2。产物H2O2可被过氧化氢酶(CAT)酶迅速清除,产生H2O和02,避免了H2O2对体系亚胺键结构的破坏。而另一个产物葡萄酸内酯则进一步水解生成葡萄糖酸,降低体系的pH,促进亚胺键的形成。因此,通过向凝胶中加入葡萄糖,利用GOx与CAT双酶协同催化作用,可改变体系pH,从而调控牛血清白蛋白和戊二醛之间交联,实现体系的自修复。
3)双酶微马达体系：利用GOx与CAT双酶催化产生气体的反向推动原理,设计构建了微马达体系。我们以硅胶为载体,在硅胶表面修饰过氧化氢酶(CAT),然后置于葡萄糖氧化酶和葡萄糖共存的体系中。由于葡萄糖氧化酶氧化葡萄糖产生H202,过氧化氢酶分解H2O2放出氧气为动力,推动微马达运动。由于微马达表面结构的不对称性,使得该体系存在不同的运动方式,即直线运动和旋转运动。该体系的构建为其在微纳物体运输和生物传感等领域的应用提供了新的思路。
Enzymes are nature evolution of proteins with high specificity and strong catalyticability, which can catalyze certain chemistry reaction in mild conditions. Because ofthe unique supramolecular interaction between enzyme and its substrate, it becomes thefirst choice when studying the bionic system. Enzyme catalytic process is verycomplexity, but with the development of the genomics, proteomics, and computersimulation, people have a deeper understanding of the enzyme catalysis andapplication.
Multi-enzyme synergistic catalytic system is one of the challenging researchtopics in the field of enzyme-catalyzed. Due to the complexity of the systems and theunstability property of the enzyme, limiting the development of the multi-enzymesynergistic catalysis system. However, the amazing ability of native enzymesdemonstrated the efficiency and specificity under mild conditions, still attractedscientists extensive attention. Therefore, the study of multi-enzyme synergisticcatalysis and its related application, has become a common concern in chemistry,biology and life sciences. Explore of multi-enzyme synergistic catalysis system hasgreat significance in understanding the evolution process of enzyme and therelationship between the tructure and function of enzyme. Herein, as guidance ofbionics, we used the dual-enzyme system for exploring antioxidant, self-healing andmicro motor.
1. Construction of dual enzymatic antioxidant system
The antioxidant enzymes, superoxide dismutase (SOD), catalase (CAT), andglutathione peroxidase (GPx) contribute dominatingly to enhance cellularantioxidative defense against oxidative stress in the human body. Thereinto, SOD is ametalloenzyme that catalyzes the dismutation of superoxide radical anion (O2-)toH2O2and dioxygen. H2O2is then detoxified either to H2O and O2by catalase (CAT)or to H2O by glutathione peroxidase (GPx). Studies indicated that each enzyme has aspecific as well as an irreplaceable function and they act in a cooperative or synergistic way to ensure a global cell protection, and only when an appropriatebalance between the activities of these enzymes is maintained, the optimal protectionof cells could be achieved.
In recent years, there were considerable interests in preparing the enzyme mimicswith the properties of SOD or GPx for elucidating catalytic mechanism and forpotential pharmaceutical application. In order to further study the cooperation of theseenzymes in antioxidation and to generate efficient therapeutic agents, somebifunctional artificial enzymes with antioxidant enzyme activities have beenconstructed by chemical methods.
Here, based on the understanding of the synergy of the natural antioxidant enzymes,we have carried out work as follow. Using computational design and geneticengineering methods, the main catalytic components of GPx were fabricated onto thesurface of ferritin. The resulting seleno-ferritin (Se-Fn) monomers can self-assembleinto nanocomposites which exhibit remarkable GPx activity due to the well organizedmulti-GPx catalytic centers. Subsequently, a porphyrin derivative was synthesized asSOD mimic to crosslink Se-Fn nanocomposites for the formation of a synergistic dualenzyme microgel, and this dual enzyme microgel has been proven to displaysignificantly better antioxidant ability than single GPx or SOD mimic in protectingcell from oxidative damage.
2. Construction of dual enzymatic self-healing system
The abilities to spontaneously heal injury and recover functionality are keyfeatures that increase the survivability and lifetime of the organism. In contrast,synthetic materials usually fail after damage or fracture. Inspired by nature, thedemand for self-healing materials is rapidly development because they can offer anew rote toward safer, longer-lasting products and lower production costs. Over thepast few decades, there were three kinds of conceptual self-healing systems have beenreported, such as capsule system, vascular system, and intrinsic system.
As one of the acidity reversible covalent bonds, imine bond—from an amine andan aldehyde has been widely used in the construction of exotic molecules and extendstructures on account of the inherent ‘proof-reading’ and ‘error-checking’ associatedwith these reversible reactions. But more importantly, the equilibrium of imine bondformation between an imine and its corresponding precursor(s) can influenced by theexternal considerations, such as solvent, pH, and temperature.
Herein, we reasoned that one such reaction, the glutaraldehyde by the reversible covalent attachment of the GOx and the bovine serum albumin (BSA) to the lysineresidue, could be well suited for the formation and functionalization of proteinhydrogels system. The BSA as a scaffolding sustain the hydrogels system and theGOx as a catalytic center play a key role to adjust the pH of the system by add extratraces of glucose. The glucose is oxidized to gluconolactone under the catalytic of theGOx, then gluconolactone hydrolyzed to gluconic acid to reduce the system pH. TheH2O2that generated by the catalytic reaction will be decomposition by the enzymecatalase (CAT) to avoid the glutaraldehyde is oxidized. With the change of the pH, theimine bonds provide us the opportunity to drive the reaction forward or backwards.
3. Construction of dual enzymatic micro-motor system
Life is movement. For the nature forms, the material transport in cellular, DNAreplication, cell division and differentiation, muscle contraction, a series of importantlife activities are dependent on the movement of the biological molecular motors inthe cytoplasm. These motors are nanomachines which can be transform the energy ofbiochemistry to mechanical. In the natural world, the autonomous motion of biomotoris common. Protein motors and bacteria have formed a variety of sophisticated andperfect systems fuelled with chemical energy, and well-controlled nanomachines canexecute translational and rotational movement precisely. The outstanding performanceof these biomotors in nature has stimulated interest in synthesis of manmademicro-/nano-motors which can mimic the behaviors of biomotors to operate inlocally-supplied chemical fuels and achieve various functions. The first generation ofcatalytic motors on the micro-/nano-scale which exhibit autonomous self-propulsionin the presence of hydrogen peroxide makes this idea promising and exhibits potentialapplications in small cargo delivery and biosensing.
Based on the catalytic decomposition of H2O2, we constructed a dual enzymemicro-motor system. The system applications the bubbles promote motor model.Motors that utilize this type of motion create bubbles on their catalytic side and theforce from the release of the bubbles causes the motion. This is a gradientlikemechanism since bubbles need to be generated on one side and not the other so thereis a change in bubble concentration with distance. We take silica gel as a carrier, anddecorate catalase (CAT) on the surface of silica. Then the silica gel was placed intothe system of glucose oxidase and glucose. Due to the glucose oxidase oxidation ofglucose, H2O2was generated. Catalase decomposition of H2O2release oxygen can bedriving silica sports. Due to the inhomogeneity of the silica surface, there are different sports ways in the system, such as linear motion and rotary motion. We anticipate thatthis system could provide a new approach for micro-and nano objects transport,bio-sensing and other areas in vivo application.
引文
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