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sc5000鐵桿木蟲(chóng) (初入文壇)
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[求助]
急求助,文獻(xiàn)翻譯
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The immobilization of dinuclear copper(II) acetate complexes (Cu2(CH3COO)4 3 2H2O) on self-assembled monolayers (SAMs) of different aliphatic and aromatic thiols with oxygen and nitrogen donors at the end group is investigated on preferentially oriented (111) gold surfaces (Au(111)). The Cu species are immobilized at the outer plane of these terminal groups by the interaction of the terminal moiety of the functionalized SAMs. The highest electrochemical activity for the Cu(II)/Cu(I) redox couple is found for the metallic complexes immobilized on SAMs of short thiols, irrespective of their aliphatic or aromatic character, or the nature of the terminal group of the linking molecule, suggesting that direct tunneling is the main path for charge transfer to the Au substrate. Even though a progressive demetalation of the copper acetate complex immobilized on N-terminated SAMs by the release of Cu ions to the solution is induced by repeated potential scans, this process is negligible for Cu species immobilized on O-terminated thiols. The Cu(I)/Cu(0) reaction is not observable in the overall potential range where thiol SAMs are stable on the Au(111) surface. In contrast, this reaction is clearly visible by using nanostructured Au, a substrate that exhibits a wider potential window of SAM stability and larger capture areas than ordered smooth metal surfaces. Finally, spatial 2D and 3D confinement of the copper complex can be performed by SAMs of mixed thiols with different immobilization abilities and by building complex electrochemically active supramolecular structures. Our results are important to understand the behavior of Cu centers of enzymes, the electrochemical metallization of thin organic films with Cu, and the preparation of complex three-dimensional supramolecular Cu-containing structures with spatial order. |
金蟲(chóng) (小有名氣)
金蟲(chóng) (小有名氣)
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供參考: 固定的雙核銅(II)醋酸配合物在不同的脂肪族和芳香族硫醇與氧和氮的捐助者在年底組的自組裝膜(SAMS)(銅(CH3COO)3· 2H2O)是調(diào)查優(yōu)先導(dǎo)向(111)金表面(金(111))。 銅物種是固定的終端基團(tuán)的功能化自組裝的相互作用,在這些終端組外平面。最高的電化學(xué)活性的銅(II)/銅(一)氧化還原夫婦發(fā)現(xiàn)短硫醇自組裝固定的金屬配合物,不論其脂肪族或芳香族的性格,或連接分子的終端組的性質(zhì),表明直接隧道是電荷轉(zhuǎn)移到金基板的主要路徑。醋酸銅復(fù)雜的漸進(jìn)demetalation即使對(duì)N -終止自組裝固定到解決方案中的銅離子的釋放是通過(guò)反復(fù)的潛在掃描誘導(dǎo),這個(gè)過(guò)程是可以忽略不計(jì)固定在O型終止硫醇的銅物種。在Cu(I)/銅(0)的反應(yīng)是觀察不到的巰基自組裝在Au(111)表面的穩(wěn)定的整體潛力范圍。相反,這種反應(yīng)是使用納米金清晰可見(jiàn),具有更廣泛的SAM的穩(wěn)定性和更大的捕獲地區(qū)比下令光滑的金屬表面的電位窗基板。最后,空間的二維和三維銅配合物的約束,可以執(zhí)行不同的固定能力的混合硫醇自組裝,并通過(guò)建立復(fù)雜的電化學(xué)活性的超分子結(jié)構(gòu)。我們的結(jié)果是重要的,了解酶,薄的有機(jī)薄膜與銅的電化學(xué)金屬,并編制了復(fù)雜的三維超分子結(jié)構(gòu)與空間秩序含有銅銅中心的行為 |
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