國立高雄大學圖資館 |

語系: 繁體中文

說明(常見問題)

圖資館首頁

登入

回首頁

切換: 標籤 | MARC模式 | ISBD

對掌性小分子自我辨識之研究 = Assessing Chiral Sel...

國立高雄大學應用化學系碩士班

對掌性小分子自我辨識之研究 = Assessing Chiral Self-Recognition of Small Chiral Molecules

紀錄類型:	書目-語言資料,印刷品 : 單行本
並列題名:	Assessing Chiral Self-Recognition of Small Chiral Molecules
作者:	黃繽萱,
其他團體作者:	國立高雄大學
出版地:	[高雄市]
出版者:	撰者;
出版年:	2012[民101]
面頁冊數:	336面圖，表 : 30公分;
標題:	鏡相異構物
標題:	enantiomer
電子資源:	http://handle.ncl.edu.tw/11296/ndltd/30236694694896904199
摘要註:	大自然中有很多我們無法解釋分子的交互作用力。我們發現了一個有趣的交互作用發生在兩分子間，控制著分子辨識。這交互作用對於超分子化學、藥物開發與蛋白質設計都具有非常大的影響。因此我們將經由對掌性小分子與不同外消旋鏡像異構物的交互作用來研發簡單分子辨識之機制。根據近期對於對掌性自我辨識小分子之研究，我們將藉由研究racemate化合物分子在固相的型態下所形成的同掌性分子二聚體來找出其自我辨識之可能機制。本研究是變換苯環上的取代基，合成出N-(3,5-dinitrobenzoyl)leucine diethyl amide之衍生物，再藉由X光單晶繞射去分析，觀察其衍生物分子在單晶固相型態下，分子排列的情形。就目前合成之N-(3,5-dinitrobenzoyl)leucine diethyl amide衍生物分子模型中，因苯環上取代機不同而有兩種不同的排列: 1)拉電子基之racemate化合物分子在晶型結構排列中有某種獨特性的排列: a)兩個頭對頭的氫鍵鍵結、b)苯環與苯環間的π-π交互作用、c)同掌性分子形成的二聚體。2)推電子基之外消旋化合物分子在晶型結構排列中卻無上敘三種現象。在某些文獻上，這些交互作用可被用來當作對掌性選擇器。對掌性選擇器與非對掌性相轉移催化劑結合會影響兩相動力分離率。雙成分鏡像選擇相轉移催化作用的優勢在於可藉由未反應之物質與對掌性選擇器所混合而成的兩相溶液中分離出離子對。我們懷疑兩相鏡像選擇相轉移的研究中形成的對掌性複合物之真實性也希望可經由小分子化合物找出其鏡像選擇之機制來應證。在文獻上有三種理論，其中兩種是互相支持的，而另一理論則是跟其他兩的理論持不同的看法。Hunter-Sanders 定律認為推電子基會增加π電子雲的負電荷以至於降低與苯環的靜電交互作用。在1992年Cozzi的文獻中描述到拉電子基會加強與苯環形成二具體之鍵結，減少與苯環的靜電排斥力。相反地，推電子基會提供π系統過量的電子而削弱π堆疊。然而在2008年Wheeler 與Houk的文獻中利用電腦計算模擬出，帶有拉電子或推電子基的苯環均會有π堆疊。而我們-OMe實驗結果也正好證明了此理論。未來將合成出不同取代機之衍生物，藉由改變其取代之位置，進而觀察其在晶體中排列之方式。在未來的應用上，分子間的三種作用力可當作催化劑、對掌性選擇器，或是修飾於管柱填充物表面，使得racemate化合物分離效果更好。 In nature, there are many forces between molecules that we cannot explain. Here we found an interesting interaction between molecules which govern molecular recognition which could have a profound impact on a variety of fields including but not limited to supramolecular chemistry, drug development and protein design. To systematically study these powerful interactions, we have developed a molecular recognition system through the design of small chiral molecules that interact preferentially with the enantiomers of specified racemates. Following our recent report on the molecular basis of self-recognition of a small chiral molecule, we describe herein a possible mechanism for the formation of the homochiral dimers in the solid state. Here we use synthesized derivatives of N-(3,5-dinitrobenzoyl)leucine diethyl amide and then analyze the structures by X-ray crystallography. We observed the arrangement of compound in the unit cell of the crystal from X-ray crystallographic data.The crystal data obtained shows different arrangements for various substituents. First, for the electron-withdrawing substituent, the racemic compound crystallizes exclusively as homochiral dimers in the solid state, driven by two head to head hydrogen bonding interactions and a controlling offset-stacked π-π interaction. Second, for the electron-donating substituent, these interactions are not in every compound in the solid state. Some compounds has, but some compounds has not (for instance, 3,5-dimethoxy group and 4-methoxy).In some reports, these interactions were used to be the chiral selector that used in conjunction with achiral phase transfer catalysts can be utilized to effect biphasic kinetic resolutions. This so-called two-component enantioselective phase transfer catalysis takes advantage that one can readily separate the ion-pairs from the biphasic solution containing the unreacted substrate and the chiral selector. We suspect that two-component enantioselective phase transfer investigations of the chiral complexes of derivatives of N-(S)-(3,5-dinitrobenzoyl)leucine diethyl amide and perhaps conclusions can be drawn regarding the enantioselective mechanism involved with these small molecules. There are three theories that two of them support each other but the other theory contradicts each two theories. Hunter-Sanders rules1 posit that electron-donating substituents increase the negative charge in the π-electron cloud and thus lead to less favorable electrostatic interactions with an unsubstituted benzene. And in 1992, the report of Cozzi that describe electron-withdrawing substituents enhance binding in the benzene dimer by withdrawing electron density from the π-cloud of the substituted ring, reducing the repulsive electrostatic interaction with the non-substituted benzene. Conversely, electron-donating substituted donate excess electrons into the π-system and diminish the π-stacking interaction. However, in 2008, the report of Wheeler and Houk that result of the electron-donating substituents (-OMe) should stack with the benzene ring. In our experimental, the arrangement of methoxy substituent is stacking that proof the Wheeler’s and Houk’s study. For the future, we will do more the synthesis of the derivatives of N-(3,5-dinitrobenzoyl)leucine diethyl amide, and observe the arrangement of the compound in the single crystal. In addition, the generality of these interactions in these compounds will allow promising chiral selectors and catalysts to be developed from first principles.

對掌性小分子自我辨識之研究 = Assessing Chiral Self-Recognition of Small Chiral Molecules
黃, 繽萱

對掌性小分子自我辨識之研究 = Assessing Chiral Self-Recognition of Small Chiral Molecules / 黃繽萱撰 - [高雄市] : 撰者, 2012[民101]. - 336面 ; 圖，表 ; 30公分.
參考書目：面90-95.
鏡相異構物enantiomer

對掌性小分子自我辨識之研究 = Assessing Chiral Self-Recognition of Small Chiral Molecules
LDR:07367nam0a2200277 450 001 322953
005 20170214100130.0
009 322953
010 0 $b 精裝
010 0 $b 平裝
100 $a 20170214y2012 k y0chiy50 e
101 1 $a eng $d chi $d eng
102 $a tw
105 $a ak am 000yy
200 1 $a 對掌性小分子自我辨識之研究 $d Assessing Chiral Self-Recognition of Small Chiral Molecules $z eng $f 黃繽萱撰
210 $a [高雄市] $c 撰者 $d 2012[民101]
215 0 $a 336面 $c 圖，表 $d 30公分
314 $a 指導教授：蘇楷立博士
320 $a 參考書目：面90-95
328 $a 碩士論文--國立高雄大學應用化學系碩士班
330 $a 大自然中有很多我們無法解釋分子的交互作用力。我們發現了一個有趣的交互作用發生在兩分子間，控制著分子辨識。這交互作用對於超分子化學、藥物開發與蛋白質設計都具有非常大的影響。因此我們將經由對掌性小分子與不同外消旋鏡像異構物的交互作用來研發簡單分子辨識之機制。根據近期對於對掌性自我辨識小分子之研究，我們將藉由研究racemate化合物分子在固相的型態下所形成的同掌性分子二聚體來找出其自我辨識之可能機制。本研究是變換苯環上的取代基，合成出N-(3,5-dinitrobenzoyl)leucine diethyl amide之衍生物，再藉由X光單晶繞射去分析，觀察其衍生物分子在單晶固相型態下，分子排列的情形。就目前合成之N-(3,5-dinitrobenzoyl)leucine diethyl amide衍生物分子模型中，因苯環上取代機不同而有兩種不同的排列: 1)拉電子基之racemate化合物分子在晶型結構排列中有某種獨特性的排列: a)兩個頭對頭的氫鍵鍵結、b)苯環與苯環間的π-π交互作用、c)同掌性分子形成的二聚體。2)推電子基之外消旋化合物分子在晶型結構排列中卻無上敘三種現象。在某些文獻上，這些交互作用可被用來當作對掌性選擇器。對掌性選擇器與非對掌性相轉移催化劑結合會影響兩相動力分離率。雙成分鏡像選擇相轉移催化作用的優勢在於可藉由未反應之物質與對掌性選擇器所混合而成的兩相溶液中分離出離子對。我們懷疑兩相鏡像選擇相轉移的研究中形成的對掌性複合物之真實性也希望可經由小分子化合物找出其鏡像選擇之機制來應證。在文獻上有三種理論，其中兩種是互相支持的，而另一理論則是跟其他兩的理論持不同的看法。Hunter-Sanders 定律認為推電子基會增加π電子雲的負電荷以至於降低與苯環的靜電交互作用。在1992年Cozzi的文獻中描述到拉電子基會加強與苯環形成二具體之鍵結，減少與苯環的靜電排斥力。相反地，推電子基會提供π系統過量的電子而削弱π堆疊。然而在2008年Wheeler 與Houk的文獻中利用電腦計算模擬出，帶有拉電子或推電子基的苯環均會有π堆疊。而我們-OMe實驗結果也正好證明了此理論。未來將合成出不同取代機之衍生物，藉由改變其取代之位置，進而觀察其在晶體中排列之方式。在未來的應用上，分子間的三種作用力可當作催化劑、對掌性選擇器，或是修飾於管柱填充物表面，使得racemate化合物分離效果更好。 In nature, there are many forces between molecules that we cannot explain. Here we found an interesting interaction between molecules which govern molecular recognition which could have a profound impact on a variety of fields including but not limited to supramolecular chemistry, drug development and protein design. To systematically study these powerful interactions, we have developed a molecular recognition system through the design of small chiral molecules that interact preferentially with the enantiomers of specified racemates. Following our recent report on the molecular basis of self-recognition of a small chiral molecule, we describe herein a possible mechanism for the formation of the homochiral dimers in the solid state. Here we use synthesized derivatives of N-(3,5-dinitrobenzoyl)leucine diethyl amide and then analyze the structures by X-ray crystallography. We observed the arrangement of compound in the unit cell of the crystal from X-ray crystallographic data.The crystal data obtained shows different arrangements for various substituents. First, for the electron-withdrawing substituent, the racemic compound crystallizes exclusively as homochiral dimers in the solid state, driven by two head to head hydrogen bonding interactions and a controlling offset-stacked π-π interaction. Second, for the electron-donating substituent, these interactions are not in every compound in the solid state. Some compounds has, but some compounds has not (for instance, 3,5-dimethoxy group and 4-methoxy).In some reports, these interactions were used to be the chiral selector that used in conjunction with achiral phase transfer catalysts can be utilized to effect biphasic kinetic resolutions. This so-called two-component enantioselective phase transfer catalysis takes advantage that one can readily separate the ion-pairs from the biphasic solution containing the unreacted substrate and the chiral selector. We suspect that two-component enantioselective phase transfer investigations of the chiral complexes of derivatives of N-(S)-(3,5-dinitrobenzoyl)leucine diethyl amide and perhaps conclusions can be drawn regarding the enantioselective mechanism involved with these small molecules. There are three theories that two of them support each other but the other theory contradicts each two theories. Hunter-Sanders rules1 posit that electron-donating substituents increase the negative charge in the π-electron cloud and thus lead to less favorable electrostatic interactions with an unsubstituted benzene. And in 1992, the report of Cozzi that describe electron-withdrawing substituents enhance binding in the benzene dimer by withdrawing electron density from the π-cloud of the substituted ring, reducing the repulsive electrostatic interaction with the non-substituted benzene. Conversely, electron-donating substituted donate excess electrons into the π-system and diminish the π-stacking interaction. However, in 2008, the report of Wheeler and Houk that result of the electron-donating substituents (-OMe) should stack with the benzene ring. In our experimental, the arrangement of methoxy substituent is stacking that proof the Wheeler’s and Houk’s study. For the future, we will do more the synthesis of the derivatives of N-(3,5-dinitrobenzoyl)leucine diethyl amide, and observe the arrangement of the compound in the single crystal. In addition, the generality of these interactions in these compounds will allow promising chiral selectors and catalysts to be developed from first principles.
510 1 $a Assessing Chiral Self-Recognition of Small Chiral Molecules $z eng
610 0 $a 鏡相異構物 $a 同掌性分子 $a 取代基效應 $a 掌性自我辨識 $a π-π交互作用
610 1 $a enantiomer $a homochiral $a chiral chromatography $a substituted effects $a chiral recognition $a π-π interaction
681 $a 008M/0019 $b 421202 4424 $v 2007年版
700 1 $a 黃 $b 繽萱 $4 撰 $3 546975
712 0 2 $a 國立高雄大學 $b 應用化學系碩士班 $3 166131
801 0 $a tw $b NUK $c 20120503 $g CCR
856 7 $z 電子資源 $2 http $u http://handle.ncl.edu.tw/11296/ndltd/30236694694896904199