超分子光化學(xué)分子器件【精品-PPT】

第七章超分子光化學(xué)分子器件主要內(nèi)容：

引言分子器件與超分子光化學(xué)

超分子光化學(xué)分子器件展望引言

自然界中復(fù)雜的光生物過程諸如：光合作用、視覺機理，這些自然界精巧的光化學(xué)反應(yīng)和光功能都是在天然的超分子體系內(nèi)進行的，但我們對它們的結(jié)構(gòu)，有序排列、力能學(xué)和動力學(xué)等方面的奧秘了解的甚少近年來受到廣泛重視的分子電子學(xué)研究的興起以及光電子功能材料的出現(xiàn)，不僅要求從機理上對存在的種種問題給以闡明，而且還要獲得具體可用的實際材料要求科學(xué)家們設(shè)計、制造出人工體系模擬上述過程，研究其作用機理，以滿足人類不斷增長的多種需要，而超分子光化學(xué)分子器件的研究提供了一個良好的模型體系

“器件”是指各種具有不同功能的元件經(jīng)組裝后用來完成特定復(fù)雜功能的組合件，概念延伸到分子水平，就形成了分子器件分子器件的研究最近十幾年才得到迅速的發(fā)展，主要得益于以下各科學(xué)領(lǐng)域的研究突破：

分子器件分子器件與超分子光化學(xué)探測顯微技術(shù)的迅速發(fā)展（BinnigandRohrer，1986，物理學(xué)諾貝爾獎）超分子簡單易行的合成方法的實現(xiàn)（Pederson,Cram,andLehn，1987，化學(xué)諾貝爾獎）生物系統(tǒng)的光合成工作原理的闡明（Deisenhofer,Huber,andMichel，1988，化學(xué)諾貝爾獎）和ATP的合成（Boyer,Skou,andWalker，1997，化學(xué)諾貝爾獎）均相和多相體系中的熱和光致的電子轉(zhuǎn)移反應(yīng)機理研究的巨大進展（Marcus，1992，化學(xué)諾貝爾獎）(物理)從上向下(top-down)方法內(nèi)在局限性,(化學(xué))自下而上(bottom-up)方法優(yōu)點超分子化學(xué)：研究超出于分子實體之外的化學(xué)，主要是研究那些通過分子間非共價鍵相互作用而組織起來的化學(xué)物種所表現(xiàn)的物理、化學(xué)以及生物特性和行為的科學(xué)超分子光化學(xué)：研究超分子物種與光作用而產(chǎn)生的光物理、光化學(xué)以及光生物特性和行為的科學(xué)

超分子光化學(xué)超分子與大分子的區(qū)別超分子體系的種類超分子光化學(xué)與分子器件的關(guān)系Fig.1Schematicrepresentationaddressingthedifferencebetweensupermoleculesandlargemoleculesaccordingtothephotochemicalapproach

超分子與大分子的區(qū)別LLLLM籠狀化合物(cagetypesystem)HHG主客體系(host-guestsystem)旋轉(zhuǎn)體(rotaxanessystem)聯(lián)鎖體(catenanessystem)ABCD共價鍵聯(lián)結(jié)的四元體系(covalently-linkedmolecularcomponents)Fig.2.Schematicrepresentionoffivetypesofsupramolecularspecies

超分子體系的種類受體底物絡(luò)合或分子間鍵超分子識別催化傳遞分子器件多分子有序集合體化學(xué)調(diào)控光化學(xué)調(diào)控電化學(xué)調(diào)控超分子光化學(xué)分子器件Fig.3.Schematicrepresentationofrelationship

betweensupramoleculeandmoleculardevices超分子光化學(xué)與分子器件的關(guān)系超分子光化學(xué)分子器件光能轉(zhuǎn)換分子器件熒光分子傳感器分子開關(guān)分子機器超分子光化學(xué)分子天線或?qū)Ь€：具有光電轉(zhuǎn)換或光致電子轉(zhuǎn)移功能的分子器件其主要是通過電子給體－光敏劑－電子受體三元或多元體系超分子在光的作用下發(fā)生電荷分離來實現(xiàn)這也是光合作用機理中最基本的過程．光能轉(zhuǎn)換分子器件hνQPCe-e-Q.-PC.+Fig.4.Q-P-CtriadsupramolecularsystemandschematicdiagramoftrimerchargeseparationFig.5.Schematicrepresentationofanartificialphotosyntheticmembrane.Thelipidbilayerofaliposomevesiclecontainsthe

componentsofalight-drivenprotonpump:avectoriallyinsertedtriadleadstotransportofhydrogenionsintotheliposomeinterior,establishingaprotonmotiveforce.ThemembranealsocontainsavectoriallyinsertedATPsynthaseenzyme.TheflowofprotonsoutoftheliposomethroughthisenzymedrivestheproductionofATP.方法簡便靈敏度高選擇性高響應(yīng)時間快可現(xiàn)場測定（熒光成像技術(shù)）利用光纖可遠距離檢測

超分子光化學(xué)熒光分子傳感器在各種離子檢測技術(shù)中具有突出的優(yōu)點：熒光分子傳感器Fig.6.Mainaspectsoffluorescentmolecularsensorsforcationrecognition.Fig.7.Schematicillustrationofvariousstructuresoffluoroionophores.Fig.8.PrincipleofcationrecognitionbyfluorescentPETsensors.Fig.9.variousstructuresoffluoroionophores.超分子光化學(xué)分子開光就是通過光誘導(dǎo)電子轉(zhuǎn)移、能量轉(zhuǎn)移等使超分子發(fā)生結(jié)構(gòu)變化而使其具有開光作用的分子器件：光控磁開關(guān)基于電子轉(zhuǎn)移的光控開關(guān)基于光誘導(dǎo)分子構(gòu)型變化的開關(guān)分子開關(guān)光控磁開關(guān)Fig.10.Photoswitchofmagneticinteraction.（diarylethene)基于電子轉(zhuǎn)移的光控開關(guān)Fig.11.Light-drivendethreadingofpseudorotaxanesbyexcitationofaphotosensitizerPas(a)anexternalreactant(MeCNorH2O,roomtemperature),(b)astopperinthewire-typecomponent(EtOH,roomtemperature),and(c)acomponentofthemacrocyclicring(H2O,roomtemperature).基于光誘導(dǎo)分子構(gòu)型變化的開關(guān)Fig.12.Thephotoinducedinclusionof4,4’-bipyridine(45)insidethecavityoftheazobenzene-cappedcyclodextrinderivative44(H2O,pH7.2,298K).The4,4’-dicarbonylazobenzeneunitisattachedtotwooftheprimaryoxygenatomsofthecyclodextrinderivative

超分子光化學(xué)分子機器就是在光的驅(qū)動下能夠執(zhí)行類似機械運動功能的超分子體系：分子轉(zhuǎn)動裝置分子梭分子機器Fig.13.Thelight-fueledrotarymotor19undergoesunidirectionalrotationinn-hexaneat333Kuponirradiationatappropriatewavelengths.

Fig.14.Rotaxane76+andschematicrepresentationoftheintramolecularmechanismforthephotoinducedabacus-likemovementofmacrocycleRbetweenthetwostationsA1andA2.Fig.15.Theshuttlingofthemacrocycliccomponentof554+alongitsdumbbell-shapedcomponentcanbecontrolledreversiblybyphotoisotherizingtheazobenzeneunit超分子光化學(xué)器件研究已成為世界性前沿課題，新型光控分子水平機器的研究具有獨特的吸引力，并取得了一定的進展：人工光合成ATP人工分子機器的藥物運送人工分子開關(guān)執(zhí)行邏輯運算超分子光化學(xué)分子器件仍還處在基礎(chǔ)研究階段，要實現(xiàn)宏觀實際應(yīng)用還有很多問題要解決，如分子器件固態(tài)環(huán)境下應(yīng)用是個難題但隨著該領(lǐng)域研究范圍不斷擴大，新型超分子光化學(xué)器件將在生命科學(xué)、材料科學(xué)、環(huán)境科學(xué)和信息技術(shù)方面發(fā)揮巨大作用展望謝謝！$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4gsEQ$4dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1dpBNZ1doAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0coAMY0clxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV)9lxJV&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6iuGS&6irDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP!3frDP#2eqCO#2eqCO#2eqCO#2eqCO#2eqCO#2eqCO#2eqCO#2e