식물성 오일에서 구현되는 삼중항-삼중항 소멸법에 의한 Upconversion 분석

신성주; 최현석; 박은경; 현규; 한상일; 김재혁; Sung Ju Shin; Hyun Seok Choe; Eun-Kyoung Park; Hyun Kyu; Sangil Han; Jae Hyuk Kim

Applied Chemistry for Engineering, Vol.27, No.6, 639-645, December, 2016

DOI10.14478/ace.2016.1102 Export Citation

식물성 오일에서 구현되는 삼중항-삼중항 소멸법에 의한 Upconversion 분석

Efficient Triplet-triplet Annihilation-based Upconversion in Vegetable Oils

신성주, 최현석, 박은경, 현규, 한상일¹, 김재혁^†

부산대학교 화공생명⋅환경공학부
¹창원대학교 화공시스템공학과

Sung Ju Shin, Hyun Seok Choe, Eun-Kyoung Park, Hyun Kyu, Sangil Han¹, and Jae Hyuk Kim^†

Department of Chemical and Environmental Engineering, Pusan National University, Busan 46241, Korea
¹Department of Chemical Engineering, Changwon National University, Gyeongam 51140, Korea

E-mail:

초록

본 연구는 음용가능한 수준의 비독성, 비휘발성 식물성 오일에서 PtOEP와 DPA를 광감응제와 전자수용체로 이용해 구현되는 효율적인 TTA-UC현상에 대해 보고하고 있다. 다양한 종류의 식물성 오일에 PtOEP/DPA를 담지시켰을 때, 탈산소 공정없이도 532 nm의 입사 레이저에서 430 nm 영역의 선명한 green-to-blue UC현상이 관측되었으며, 양자수율은 약 8%로 측정되었다. 이러한 UC의 효율은 식물성 오일의 화학적 조성, 특히 불포화 탄화수소의 함량과 점도에 크게 의존하는 것으로 나타났다. 식물성 오일에서의 Stern-Volmer 상수값은 유기용매에 비해 다소 낮은 값을 보였으나, 전환효율은 93% 정도로 여전히 높은 수치를 보여주었다. 해바라기씨유에서 UC의 전환 입사광 강도(Ith)는 약 100mW/cm2로 태양광의 직접활용에는 아직 무리가 있으나, 산소포화조건에서 비독성 매질을 통해 즉각적으로 구현되는 UC는 비전통적인 방식의 bioimaging과 같은 기술에의 응용가능성이 높을 것으로 생각된다.

We herein report efficient triplet-triplet annihilation upconversion (TTA-UC) achieved in various non-toxic and non-volatile vegetable oils as a UC media using platinum-octaethylporphyrin (PtOEP) and 9,10-diphenylanthracene (DPA) as a sensitizer and acceptor, respectively. Green-to-blue UC was readily achieved from PtOEP/DPA solution in vegetable oils with the quantum yield of 8% without any deoxygenation process. The UC efficiency was found to be significantly dependent on the contents of unsaturated hydrocarbon in vegetable oils and viscosity of the solution, as well. Though the Stern-volmer constant and quantum yield in vegetable oils were measured to be lower than those measured in the deaerated organic solvent, the quenching efficiency was still high enough to be 93%. In the sunflower oil, the UC threshold intensity (Ith) was approx. 100 mW/cm2, which is far larger than the sunlight intensity, but we believe that the UC achieved in non-toxic and air-saturated media was still highly applicable to nontraditional visualization techniques such as bioimaging.

Keywords:upconversion;vegetable oils;anti-stokes emission;triplett-triplet annihilation

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[1] Kim JH, Kim JH, J. Am. Chem. Soc., 134(42), 17478 (2012)

[2] Liu Q, Yin BR, Yang TS, Yang YC, Shen Z, Yao P, Li FY, J. Am. Chem. Soc., 135(13), 5029 (2013)

[3] Schulze TF, Czolk J, Cheng Y, Fuckel B, MacQueen RW, Khoury T, Crossley MJ, Stannowski B, Lips K, Lemmer U, Colsmann A, Schmidt TW, J. Phys. Chem. C, 116, 22794 (2012)

[4] Schulze TF, Schmidt TW, Energy Environ. Sci., 8, 103 (2015)

[5] Singh-Rachford TN, Castellano FN, Coord. Chem. Rev., 254, 2560 (2010)

[6] Islangulov RR, Kozlov DV, Castellano FN, Chem. Commun., 30, 3776 (2005)

[7] Zhao W, Castellano FN, J. Phys. Chem. A, 110, 11440 (2006)

[8] Singh-Rachford TN, Haefele A, Ziessel R, Castellano FN, J. Am. Chem. Soc., 130(48), 16164 (2008)

[9] Kim JH, Deng F, Castellano FN, Kim JH, Chem. Mater., 24, 2250 (2012)

[10] Kim JH, Kim JH, ACS Photonics, 2, 633 (2015)

[11] Monguzzi A, Bianchi F, Bianchi A, Mauri M, Simonutti R, Ruffo R, Tubino R, Meinardi F, Adv. Eng. Mater., 3, 680 (2013)

[12] Peng J, Guo X, Jiang X, Zhao D, Ma Y, Chem. Sci., 7, 1233 (2016)

[13] Merkel PB, Dinnocenzo JP, J. Lumines., 129, 303 (2009)

[14] Penconi M, Ortica F, Elisei F, Gentili PL, J. Lumines., 135, 265 (2013)

[15] Ogawa T, Yanai N, Monguzzi A, Kimizuka N, Sci. Rep., 5, 10882 (2015)