本文選題：芳香螺旋聚合物 + 共價(jià)螺旋�。� 參考：《吉林大學(xué)》2017年博士論文

【摘要】：螺旋結(jié)構(gòu)是生物學(xué)研究的核心結(jié)構(gòu),也存在于自然界中。最常見(jiàn)的喇叭花的纏繞方向,海螺的螺紋等等都呈現(xiàn)螺旋結(jié)構(gòu),并且絕大多數(shù)生物遺傳的物質(zhì)基礎(chǔ)DNA也呈現(xiàn)雙螺旋結(jié)構(gòu)。受生物體中這些螺旋結(jié)構(gòu)的啟發(fā),以及其存在的巨大潛在應(yīng)用價(jià)值,人們通過(guò)合理的設(shè)計(jì),利用螺旋結(jié)構(gòu)模擬并開(kāi)發(fā)了多種多樣的高級(jí)結(jié)構(gòu)。例如,脂肪螺旋結(jié)構(gòu),脂肪-芳香螺旋結(jié)構(gòu)的開(kāi)發(fā),以及近幾年對(duì)芳香螺旋結(jié)構(gòu)的研究�；诜肿咏Y(jié)構(gòu)的多樣化,超分子化學(xué)的發(fā)展,以及化學(xué)表征手段的不斷完善,我們逐漸了解了多種螺旋結(jié)構(gòu)的折疊機(jī)制,并在此基礎(chǔ)上,利用共價(jià)鍵、動(dòng)態(tài)共價(jià)鍵以及金屬配位的超分子作用力挑戰(zhàn)新型芳香螺旋聚合物及超分子聚合物的合成及性質(zhì)研究。具體工作如下:1.基于共價(jià)鍵實(shí)現(xiàn)螺旋聚合物的構(gòu)建及利用其單雙螺旋互變性質(zhì)調(diào)節(jié)兩種螺旋至適當(dāng)比例產(chǎn)生白光,以及利用其中空孔洞實(shí)現(xiàn)單分子離子通道的構(gòu)建共價(jià)芳香螺旋聚合物由于共價(jià)芳香螺旋聚合物合成方式單一,只能通過(guò)共價(jià)反應(yīng)逐一將重復(fù)單元連接起來(lái),并且剛性芳環(huán)結(jié)構(gòu)的堆積越多,越會(huì)限制所形成聚合物的溶解度,所以得到高聚合度的芳香螺旋聚合物仍然是一個(gè)挑戰(zhàn)。我們利用三聯(lián)苯二酰肼與二酰氯的衍生物通過(guò)共價(jià)鍵連接形成芳香結(jié)構(gòu)為主鏈的高分子量螺旋聚合物,并研究其性質(zhì)。之所以用三聯(lián)苯作為主鏈結(jié)構(gòu),一是因?yàn)樵谝霅憾蚝?惡二唑與三聯(lián)苯達(dá)到能量最穩(wěn)的狀態(tài)時(shí),能夠形成一個(gè)角度,從而使得聚合物逐漸彎曲,形成螺旋結(jié)構(gòu),二是由于其彎曲后形成的孔洞必須控制在合適的尺寸,為后續(xù)工作中構(gòu)建單分子離子通道以及實(shí)現(xiàn)離子選擇性打下基礎(chǔ)。聚合物溶液中存在單雙兩種螺旋結(jié)構(gòu),通過(guò)調(diào)節(jié)濃度和溫度,可以控制聚合物體系中兩種螺旋至合適的比例,從而得到白光,經(jīng)多種光譜證明之所以發(fā)射白光是因?yàn)樽贤夤庹丈鋾r(shí),適當(dāng)比例的單螺旋發(fā)射的藍(lán)光和雙螺旋發(fā)射的黃光混合形成的,這一發(fā)現(xiàn)為單一有機(jī)白光的發(fā)射提供了新的模式。另一方面,我們利用具有適當(dāng)長(zhǎng)度的芳香螺旋聚合物的中空孔道,成功得到了離子通道。由于芳香螺旋結(jié)構(gòu)十分穩(wěn)定,能夠跨越脂雙層,因此對(duì)于質(zhì)子和陽(yáng)離子具有很高的傳輸效率。并且,這種單分子螺旋通道的壽命甚至可以與天然蛋白質(zhì)通道媲美,成功實(shí)現(xiàn)了對(duì)天然通道的模擬,這也為實(shí)現(xiàn)單分子水平的運(yùn)輸?shù)於嘶A(chǔ)。2.基于可逆動(dòng)態(tài)共價(jià)鍵的自發(fā)選擇性實(shí)現(xiàn)螺旋結(jié)構(gòu)的構(gòu)建及對(duì)其手性放大性質(zhì)的研究和利用空間位阻效應(yīng)實(shí)現(xiàn)對(duì)螺旋聚合物構(gòu)象的絕對(duì)控制及利用其孔洞內(nèi)外環(huán)境的差別實(shí)現(xiàn)對(duì)苯硫酚催化氧化的微環(huán)境的構(gòu)建這部分研究中,同樣做了兩部分工作。首先,設(shè)計(jì)了構(gòu)象最穩(wěn)態(tài)呈C型的構(gòu)筑基元,利用其本身的弧度和與喹啉分子反應(yīng)后形成的分子內(nèi)氫鍵作用得到螺旋結(jié)構(gòu)。并且當(dāng)把帶有醛基的手性與非手性喹啉衍生物分子與兩端帶有酰肼的C型分子混合時(shí),利用席夫堿形成的自發(fā)選擇性得到了手性與非手性寡聚物螺旋結(jié)構(gòu)共存的溶液,通過(guò)測(cè)定其比例,發(fā)現(xiàn)該體系存在手性放大的現(xiàn)象。這類自發(fā)手性放大的研究,無(wú)疑為未來(lái)動(dòng)態(tài)功能材料的發(fā)展以及不對(duì)稱催化劑的發(fā)展奠定了基礎(chǔ)�；趧�(dòng)態(tài)共價(jià)鍵連接的螺旋分子結(jié)構(gòu)的成功實(shí)現(xiàn),我們利用二酰肼和二醛以動(dòng)態(tài)共價(jià)鍵席夫堿連接形成芳香螺旋聚合物。并利用其結(jié)構(gòu)形成順式構(gòu)象時(shí)存在強(qiáng)烈的空間位阻,設(shè)計(jì)合成了以反式構(gòu)象控制的自折疊螺旋聚合物,實(shí)現(xiàn)了對(duì)構(gòu)象的絕對(duì)控制。并利用其折疊產(chǎn)生的中空管狀結(jié)構(gòu)作為微環(huán)境,以雙氧水為氧化劑,成功催化了苯硫酚的氧化反應(yīng)。3.基于超分子聚合物實(shí)現(xiàn)高效人工模擬酶的構(gòu)建鑒于超分子化學(xué)的發(fā)展,經(jīng)典的金屬-有機(jī)自組裝體系已成為構(gòu)建高級(jí)結(jié)構(gòu)的理想工具。而且,由于金屬配位聚合物結(jié)合了有機(jī)聚合物的功能以及金屬的磁性,電子,光學(xué)和催化等性質(zhì),將金屬配位作用納入到超分子聚合物的合成也越來(lái)越受到關(guān)注。在這部分研究中,我們利用酰胺鍵連接的金屬-有機(jī)體系,在己二胺兩端連上形成雙螺旋結(jié)構(gòu)的單鏈有機(jī)分子,當(dāng)向體系中加入Cu1+或Zn2+時(shí),己二胺兩端的單鏈分子即可與金屬離子配位,形成雙螺旋分子連接體,從而得到超分子聚合物�？紤]到雙螺旋分子兩端由Zn2+配位形成,我們將其作為金屬水解酶模型,成功實(shí)現(xiàn)了對(duì)底物PNPA的催化水解。而以雙螺旋分子為連接體形成的超分子聚合物金屬水解酶模型,由于相鄰催化位點(diǎn)空間距離的靠近,使其更加集中,當(dāng)?shù)孜锝咏鼤r(shí),與其碰撞的幾率增加,催化活性大大增強(qiáng),達(dá)到了雙螺旋分子連接體催化效率的23倍之多。
[Abstract]:Spiral structure is the core structure of biological research. It also exists in nature. The most common direction of floral winding, the screw thread of the conch, and so on are spiral structures, and the vast majority of biological genetic material base DNA also presents a double helix structure. Inspired by these spiral structures in the organism, and the huge potential of its existence In application value, a variety of advanced structures have been simulated and developed by rational design, using the spiral structure. For example, the development of the fat spiral structure, the fatty aromatic spiral structure, and the research on the aromatic spiral structure in recent years. We gradually understand the folding mechanism of a variety of spiral structures, and on this basis, we use covalent bonds, dynamic covalent bonds and metal coordination supramolecular forces to challenge the synthesis and properties of new aromatic spiral polymers and supramolecular polymers. The specific work is as follows: 1. the construction of spiral polymers based on covalent bonds And using its single and double helix interchanging properties to adjust two kinds of helix to the appropriate proportion to produce white light, and the construction of the single molecular ion channel by the hollow hole to construct the covalent aromatic spiral polymer because of the covalent aromatic spiral polymer synthesis method alone, can only be connected by the covalent reaction one by one, and the rigid aromatics. The more accumulation of the ring structure, the more the solubility of the polymer will be limited, so it is still a challenge to get the high degree of polymerization of aromatic spiral polymers. We use the derivatives of triphenyl two hydrazine and two acyl chloride to form a high fraction helical polymer with aromatic structure as the main chain through covalent bond, and study its properties. Three biphenyl is used as the main chain structure, one is that when the bad two azole is introduced, when the evil two azole and triphenyl reach the most stable state of energy, it can form an angle, thus making the polymer bending gradually and forming a spiral structure. Two is that the hole formed after its bending must be controlled in the appropriate size, and the single molecule is constructed for the follow-up work. In the polymer solution there are two kinds of spiral structures in the polymer solution. By adjusting the concentration and temperature, the two kinds of helix in the polymer system can be controlled and the white light is obtained. This discovery provides a new model for the emission of a single organic white light. On the other hand, we have successfully obtained the ion channel by using the hollow channel with an appropriate length of aromatic helix polymer. Therefore, the proton and cations have high transmission efficiency, and the lifetime of this single molecular spiral channel can even be comparable to the natural protein channel, and the simulation of natural channels has been successfully realized. This also lays the foundation for the realization of the.2. based on the spontaneous selectivity of reversible dynamic covalent bonds for the transport of single molecule level. The construction of the structure, the study of its chiral amplification properties and the absolute control of the conformation of the spiral polymer by the space hindrance effect and the construction of the microenvironment for the catalytic oxidation of benzenthiol by the difference of the inner and outer environment of the hole to realize the micro environment of the catalytic oxidation of benzenthiol are also done in two parts. First, the most stable state of the conformation is designed to be C type. The construction base element is spiral structure with its own arc and intramolecular hydrogen bonding with quinoline molecules. And when the chiral and chiral quinoline derivatives with aldehyde group are mixed with the C molecules with acyl hydrazine at both ends, the chiral and achiral oligomerization is obtained by the spontaneous selectivity of the Schiff base formation. It is found that the system exists chiral amplification by measuring the ratio of coexistent structures. This kind of spontaneous chiral amplification will undoubtedly lay the foundation for the development of future dynamic functional materials and the development of asymmetric catalysts. Two hydrazine and two aldehyde are connected with the dynamic covalent Schiff base to form aromatic spiral polymers. There is a strong spatial steric resistance when using the structure to form a cis conformation. A self folding spiral polymer controlled by the trans conformation is designed and synthesized. The absolute control of the conformation is realized. The hollow tubular structure produced by its folding is used as a micro structure. Environment, with hydrogen peroxide as oxidant, the oxidation reaction of benzol was successfully catalyzed by.3.. The construction of highly efficient artificial mimic enzyme based on supramolecular polymer was constructed in view of the development of supramolecular chemistry. The classical metal organic self-assembly system has become an ideal tool for the construction of advanced structures. The function of the compound and the properties of metal magnetic, electronic, optical, and catalysis, and the integration of metal coordination into the synthesis of supramolecular polymers are becoming more and more concerned. In this part of the study, we use the metal organic system connected by the amide bond to form a single strand organic molecule with double helix structure at both ends of hexadamine. When Cu1+ or Zn2+ is added to the system, the single chain molecules at both ends of the hexane can coordinate with metal ions to form a double helix molecular junction to get a supramolecular polymer. Considering that both ends of the double helix are formed by the Zn2+ coordination, we use it as a metal hydrolase model to catalyze the catalytic hydrolysis of the substrate PNPA. The supramolecular polymer metallo hydrolase model, formed by the conjunction, makes it more concentrated due to the proximity of the space distance of the adjacent catalytic sites. When the substrate is close, the probability of the collision is increased and the catalytic activity is greatly enhanced to reach 23 times as much as the catalytic efficiency of the double helix molecular connection.

【學(xué)位授予單位】：吉林大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O631

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