發(fā)布時(shí)間：2018-03-09 04:04

  本文選題：Hemicryptophane　切入點(diǎn)：分子　出處：《華東師范大學(xué)》2017年博士論文　論文類(lèi)型：學(xué)位論文

【摘要】：在主客體化學(xué)研究領(lǐng)域,hemicryptophane是一類(lèi)結(jié)合了環(huán)三亞藜蘆基和另一種C3對(duì)稱(chēng)結(jié)構(gòu)單元的籠狀化合物,近年來(lái)受到了人們廣泛的關(guān)注。論文第一部分的第1章,概述了 hemicryptophane化學(xué)的研究進(jìn)展,其中包括了該類(lèi)籠狀化合物的發(fā)展簡(jiǎn)史、合成方法、以及它們?cè)诜肿幼R(shí)別、分子機(jī)器及超分子催化領(lǐng)域的應(yīng)用。第一部分的第2章,提出了本論文的設(shè)想。本研究論文的目標(biāo)是設(shè)計(jì)合成出新型的hemicrytophane化合物以達(dá)到更高效的分子識(shí)別和超分子催化性能。論文的第二部分主要研究了如何合理的設(shè)計(jì)、合成hemicryptophane化合物,以實(shí)現(xiàn)目標(biāo)分子的選擇性識(shí)別。第二部分共四章,編號(hào)分別為第3、4、5、6章。第3章設(shè)計(jì)合成了一個(gè)含萘熒光團(tuán)和Zn(Ⅱ)金屬配位中心的hemicryptophane籠狀化合物,并研究了它作為熒光探針對(duì)磷酸膽堿兩性離子在含水溶劑中的分子識(shí)別性能。因主體分子一端的環(huán)三亞藜蘆基可結(jié)合銨根陽(yáng)離子,而另一端的金屬配位中心對(duì)陰離子具有結(jié)合作用,因此該主體化合物具有明顯的兩性分子識(shí)別特性。核磁和熒光光譜等分析測(cè)試表明該主體分子對(duì)磷酸膽堿兩性分子具有選擇性包結(jié)作用。第4章合成了兩個(gè)以氟代苯環(huán)作為連接鏈的hemicryptophane主體化合物,并研究了它們對(duì)離子對(duì)客體的識(shí)別性能。該實(shí)驗(yàn)的設(shè)計(jì)目的是期望通過(guò)在苯環(huán)側(cè)鏈上引入氟原子,提高其陰離子-π的結(jié)合力,進(jìn)而提高主體分子一端對(duì)陰離子的結(jié)合能力。主體對(duì)陰離子結(jié)合性能的改變會(huì)導(dǎo)致其對(duì)離子對(duì)客體協(xié)同識(shí)別作用的調(diào)節(jié),因此這些含氟主體對(duì)離子對(duì)的識(shí)別性能均與未含氟主體的識(shí)別性能進(jìn)行了對(duì)比和結(jié)果分析。第5章合成了兩個(gè)含三(2-吡啶基甲基)胺單元、具有兩性識(shí)別特性的hemicryptophane籠狀化合物。其中一主體以苯環(huán)作為環(huán)三亞藜蘆基團(tuán)和三(2-吡啶基甲基)胺單元的連接鏈;另一主體以萘環(huán)作為連接鏈,因此該主體具有熒光性能。由于環(huán)三亞藜蘆基具有內(nèi)在的螺旋手性,通過(guò)手性高效液相色譜儀成功的將合成的hemicryptophane外消旋混合物進(jìn)行了手性拆分,分別獲得了 hemicryptophane化合物的每個(gè)對(duì)映異構(gòu)體。這些對(duì)映異構(gòu)體在通過(guò)三(2-吡啶基甲基)胺單元絡(luò)合金屬離子之后,將會(huì)被進(jìn)一步研究其對(duì)手性的兩性離子的立體識(shí)別性能。第6章設(shè)計(jì)合成了 8個(gè)光學(xué)純的hemicryptophane立體異構(gòu)體。這些立體異構(gòu)體含3種手性類(lèi)型,分別為具有螺旋手性的環(huán)三亞藜蘆基單元、具有軸手性的聯(lián)萘基團(tuán)和具有中心手性的三齒氨基三醇單元。通過(guò)化學(xué)交聯(lián)的策略成功地歸屬了 8個(gè)立體異構(gòu)體的絕對(duì)構(gòu)型,并研究了該系列主體對(duì)糖類(lèi)客體的立體選擇性識(shí)別性能。第三部分唯一的一章,第7章,研究了一系列光學(xué)純hemicrytophane化合物(第6章合成所得)分子的呼吸運(yùn)動(dòng)性能,彌補(bǔ)了 hemicryptophane在分子機(jī)器領(lǐng)域應(yīng)用較少的現(xiàn)狀。核磁和X-ray單晶衍射等分析手段表明這一系列化合物具有內(nèi)凹的空間構(gòu)型。而氧化釩與分子籠一端的三齒氨基三醇單元的配位使得內(nèi)凹的分子籠充分的膨脹鼓起,分子籠內(nèi)絡(luò)合形成的氧化釩中心又可以被外來(lái)的三乙醇胺配體移除。因此通過(guò)外在因素,這些分子籠的空腔可以在內(nèi)凹和鼓起兩種穩(wěn)定構(gòu)型中循環(huán)往復(fù)多次,這種分子構(gòu)型上的往復(fù)轉(zhuǎn)換可被看作分子的呼吸運(yùn)動(dòng)。第四部分共三章,分別為第8、9、10章,研究了 hemicryptophane在超分子催化領(lǐng)域的應(yīng)用。第8章報(bào)道了一系列氧化釩hemicryptophane絡(luò)合物(第7章合成所得)在硫醚催化氧化反應(yīng)中作為超分子催化劑的應(yīng)用。結(jié)果表明,在釩催化活性中心上側(cè)由聯(lián)萘側(cè)鏈和環(huán)三亞藜蘆基單元所圍成的疏水性空腔可極大提高硫醚氧化反應(yīng)的產(chǎn)率、選擇性和催化活性。第9章進(jìn)一步將這些超分子釩催化劑應(yīng)用于木質(zhì)素模型化合物的催化氧化反應(yīng)。與未含分子空腔的釩催化劑相比,超分子催化劑表現(xiàn)出明顯的催化活性的提高,同時(shí)伴隨著底物的非對(duì)映選擇性轉(zhuǎn)化的現(xiàn)象。第10章嘗試性的研究了將氮磷川功能化的hemicryptophane化合物作為氫鍵供體有機(jī)催化劑用于交酯的開(kāi)環(huán)聚合反應(yīng)。結(jié)果表明,由于分子空腔的空間位阻,這類(lèi)籠狀催化劑表現(xiàn)出極低的催化活性。相反,未含分子空腔的氮磷川催化劑表現(xiàn)出令人滿意的催化性能,同時(shí)我們提出了對(duì)應(yīng)的催化反應(yīng)機(jī)理。論文的第五部分僅一章,第11章,將研究的重點(diǎn)由hemicryptophane分子籠擴(kuò)展到了自組裝分子籠。通過(guò)多組分自組裝策略,成功的將第10章介紹的氮磷川模塊作為配體自組裝成四面體金屬膠囊;并且首次利用了氮磷川的氫鍵供體功能將氮磷川作為陰離子識(shí)別的受體;同時(shí)研究了氮磷川組裝的四面體籠對(duì)陰離子的識(shí)別性能。除了介紹論文研究目的的第2章,其他所有章的研究?jī)?nèi)容均已發(fā)表或已整理好論文的形式準(zhǔn)備發(fā)表。其中第1、3、4、5、6、7、8、10、11章已經(jīng)正式發(fā)表,而第9章正在準(zhǔn)備中。因此本論文的每章均保持了原發(fā)表文章的內(nèi)容和書(shū)寫(xiě)邏輯,只對(duì)其進(jìn)行了部分修改和補(bǔ)充。
[Abstract]:In host guest chemistry field, hemicryptophane is a kind of combined cage compound ring Sanya veratryl and another C3 symmetric structural unit, in recent years has aroused widespread concern. In the first chapter, the first part, summarizes the research progress of hemicryptophane chemistry, including the development history, the cage the synthesis methods and their applications in molecular recognition, molecular machines and supramolecular catalysis. The first part of the second chapter, put forward the idea of this thesis. This thesis aims to synthesize new compounds hemicrytophane to molecular recognition and supramolecular catalysis performance more efficient. The second part mainly studies how to design reasonable, the synthesis of hemicryptophane compounds, in order to achieve the selective recognition of target molecules. The second part consists of four chapters, numbered 3,4,5,6 Chapter. A naphthalene fluorophore and Zn synthesis of the third chapter design (II) hemicryptophane clathrate metal coordination center, and studied it as a fluorescent probe for molecular recognition properties of choline phosphate amphoteric ion in aqueous solvents. Because the main body at one end of the molecule around Sanya with resveratrol based ammonium cation, and the other end of the metal coordination center has combined effect on anion, so the host compounds have obvious characteristics of amphoteric molecular recognition. NMR and fluorescence spectrum analysis tests show that the host molecules with selective inclusion of phosphorylcholine amphiphilic molecules. The fourth chapter synthesized two with fluoro benzene compounds as the main body of the hemicryptophane connection the chain, and to study their recognition performance of ion on the object. The design purpose of this experiment is to hope that through the introduction of fluorine atom on the benzene ring in side chain, improve its anion - pi The binding force, and improve the binding ability of host molecules. End of the anion binding properties of the main changes to the anion can lead to the regulation of ionic synergetic recognition of the object, so these fluorine ions on the subject on the recognition performance and the recognition performance without fluoride are analyzed and the main results. Two the fifth chapter contains three synthesis (2- pyridyl methyl) amine units, hemicryptophane clathrates with gender recognition properties. One of the main in the benzene ring Sanya as resveratrol group and three (2- pyridyl methyl) amine chain connecting unit; the other main body with naphthalene as the connection chain, so the body has fluorescence properties. Because Sanya has inherent chirality veratryl, by chiral HPLC successfully hemicryptophane racemic mixture of chiral synthesis, were obtained from he Each compound micryptophane enantiomers. These enantiomers by three (2- pyridyl methyl) amine unit after complexation with metal ions, stereo recognition performance will be further studied on the chiral zwitterion. 8 optically pure hemicryptophane stereoisomers were synthesized. The sixth chapter designs these stereoisomers containing 3 kinds of chiral types, respectively with helical chiral ring Sanya veratryl unit with axial chiral binaphthyl chiral center group and having three teeth three amino alcohol units. Through chemical cross-linking strategy successfully belongs to absolute configuration 8 stereoisomers, and studied the performance of the stereo selective recognition the main object of sugar. Chapter third, only part of the seventh chapter, a series of optically pure hemicrytophane compounds were studied (Chapter Sixth obtained) respiratory motion performance of the molecule, make up for The current situation of hemicryptophane application in the field of molecular machines less. NMR and X-ray single crystal diffraction show that the spatial configuration of this series of compounds with concave and molecular. Three teeth amino vanadium oxide and molecular cage end of the three alcohol unit coordination makes concave cage heave sufficient, vanadium oxide molecular cage center the complex formation can be removed. Therefore foreign triethanolamine ligands through external factors, these molecules can include cage cavity concave and have two stable configurations in the cycle times, the molecular structure of the reciprocating change of respiratory motion can be seen as molecular. The fourth part consists of three chapters, respectively, chapter 8,9,10, research the application of hemicryptophane in the field of supramolecular catalysis. The eighth chapter reported a series of vanadium oxide hemicryptophane complex (the seventh chapter obtained) reaction in the catalytic oxidation of sulfide The application as supramolecular catalysts. The results showed that the catalytic activity of vanadium in upper center by binaphthyl side chain and ring Sanya veratryl unit formed by the hydrophobic cavity can greatly improve the sulfide oxidation reaction yield, selectivity and catalytic activity. The ninth chapter further oxidation of these supramolecular vanadium catalysts used in lignin model compounds. Compared with vanadium catalyst containing no molecular cavity, supramolecular catalysts exhibit catalytic activity obviously increased, accompanied by the substrate diastereoselective transformation phenomenon. The tenth chapter is the research on the hemicryptophane compounds of nitrogen and phosphorus Sichuan function as hydrogen bond donor organic catalyst for lactide. The ring polymerization reaction. The results show that the cavity due to the molecular steric hindrance, the cage catalyst showed low catalytic activity. On the contrary, not including the molecular cavity Nitrogen and phosphorus Sichuan catalyst showed satisfactory catalytic performance at the same time, we put forward the corresponding reaction mechanism. The fifth part is a chapter, the eleventh chapter, the focus of the study will be extended to the cage by hemicryptophane molecular self assembled molecular cage. Through multicomponent self-assembly strategies, the success of the tenth chapter n the Sichuan phosphorus module as ligand self-assembly into tetrahedral metal capsule; and the first use of nitrogen and phosphorus in the hydrogen bond donor function of nitrogen and phosphorus will Sichuan as anion recognition receptors; at the same time on the tetrahedral assembly of Sichuan cage nitrogen and phosphorus anion recognition properties. In addition to the introduction of the research purpose of the second chapter, all of the other chapters the research contents have been published or have collated the form for publication. The chapter 1,3,4,5,6,7,8,10,11 has been officially published, and the ninth chapter are prepared. Therefore this thesis of each chapter were maintained the original The content and writing logic of the article are published, and only part of it has been amended and supplemented.

【學(xué)位授予單位】：華東師范大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類(lèi)號(hào)】：O641.3
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本文編號(hào)：1586886