Efficient upconversion by highly water-soluble cationic sensitizer and

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Efficient upconversion by highly water-soluble cationic sensitizer and emitter in aqueous solutions with DNA Ayaka Fukuzaki, Hideki Kawai, Tomomi Sano, Kenji Takehara, and Toshihiko Nagamura ACS Biomater. Sci. Eng., Just Accepted Manuscript • DOI: 10.1021/acsbiomaterials.7b00238 • Publication Date (Web): 12 Jun 2017 Downloaded from http://pubs.acs.org on June 18, 2017

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ACS Biomaterials Science & Engineering

Efficient upconversion by highly water-soluble cationic sensitizer and emitter in aqueous solutions with DNA Ayaka Fukuzakia), Hideki Kawaib), Tomomi Sanoa), Kenji Takeharaa), and Toshihiko Nagamuraa)* a) Materials Chemistry Course, Department of Creative Engineering, National Institute of Technology, Kitakyushu College, 5-20-1, Shii, Kokuraminami-ku, Kitakyushu, Fukuoka 802-0985, Japan b) Department of Applied Chemistry and Biochemical Engineering, Faculty of Engineering, Shizuoka University, 3-5-1 Johoku, Naka-ku, Hamamatsu 432-8561, Japan

KEYWORDS Triplet-triplet

annihilation,

Palladium

meso-tetrakis(N-methylpyridinium-4-yl)porphyrin,

9,10-Bis[(trimethylammonium-4-yl)- phenyl]anthracene, Deoxyribonucleic acid sodium salt, Green

laser excitation, Blue upconverted fluorescence

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ABSTRACT Highly

water-soluble

cationic

palladium

9,10-bis(4-trimethylammoniumphenyl)anthracene synthesized.

porphyrin as

an

as

a

emitter

sensitizer were

and newly

They were shown to be bound and immobilized in DNA double helix

assembly from absorption, fluorescence, phosphorescence, and circular dichroism spectra.

Upon excitation at 532 nm in deaerated aqueous solutions they showed weak

blue upconversion

fluorescence, the efficiency of which increased dramatically in the

presence of DNA.

The threshold power density between the second order and the first

order power dependence of upconversion fluorescence decreased to less than a half upon addition of DNA.

The emitter triplet lifetime estimated from time dependences

of upconversion fluorescence at low power ns pulsed laser was found to considerably increase in the presence of DNA.

From these results, DNA was concluded to work

effectively in concentrating both sensitizer and emitter and in migrating excited triplet states, resulting in efficient upconversion.

INTRODUCTION


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Upconversion (UC) based on triplet energy transfer and triplet-triplet annihilation (TTA) by the use of two kinds of molecules, one (the sensitizer) absorbing

at longer

wavelengths and one (the emitter) with emission at shorter wavelengths, has attracted much attention for their potential applications in solar cells and bioimaging. Sensitized delayed fluorescence from anthracene was observed over 50 years ago in solutions of phenanthrene containing traces of anthracene. 1-3 as TTA-UC until Baluschev et al.4

But it was not regarded

reported upconversion photoemission in

polyfluorene film doped with platinum octaethylporphyrin in 2003. than 350 papers have been published in TTA-UC.

Since then more

In almost all cases hydrophobic or

lipophilic sensitizers and emitters have been used which are soluble only in organic solvents such as toluene, N,N-dimethylformamide, dichloromethane, acetonitrile.

For

bio-imaging applications and from an ecological point of view, they are not desirable. Efforts have been made to use these lipophilic sensitizers and emitters in aqueous media by employing micelles or polymer micelles5-7, microcapsules8-10, microemulsions11,12, vesicles or liposomes13-19 to solubilize them in hydrophobic region of microdomains. Only one report has been made so far for TTA-UC by a water-soluble anionic sensitizer and an amphiphilic cationic emitter.20 Amphiphilic diphenylanthracene derivative with 3 ACS Paragon Plus Environment


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two decyltrimethylammonium groups through amide bonds at para-position of phenyl group formed monolayer self-assemblies in water.20

UC was not observed by adding

anionic platinum tetracarboxyphenylporphyrin as a sensitizer to such monolayer self-assemblies in water.

To observe clear UC for a mixed aqueous dispersion of

anionic platinum tetracarboxyphenylporphyrin with cationic monolayer self-assemblies, microwave heating at 393 K for 30 min and incubation at room temperature with stirring for 48 h, was found necessary20 DNA is water-soluble and is well known to immobilize various molecules by intercalation between planar base pairs of the double helix, by groove binding and by electrostatic binding, DNA can thus be used as a host with well-ordered and rigid structure to concentrate dyes and control their physical properties.

We have utilized

DNA ultrathin films for very sensitive detection of nitrogen oxide gasses through electron transfer quenching of fluorescent dyes immobilized in the double helix.21 We have also demonstrated highly efficient energy transfer and excitation energy migration along the DNA double helix.22,23 UC

fluorescence

in

DNA-based

assembly

was

recently

reported

by

tris(2,2’-bipyridine)ruthenium, [Ru(bpy)3]2+, as a sensitizer and (R)-1-O-[4-(1-pyrenyl4 ACS Paragon Plus Environment

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ethynyl)phenylmethyl]glycerol, PEPy, chemically attached at the 3’ and 5’ positions of oligonucleotides with 12 base pairs as an emitter, either one or two units at each position.24

It was reported that UC fluorescence was observed for three kinds of

emitter-modified oligonucleotides and [Ru(bpy)3]2+ in aqueous solutions deaerated with argon for 24 h, whereas no UC was observed in dichloromethane solutions of [Ru(bpy)3]2+ and PEPy in the same conditions.24 Similar DNA-based assembly with zinc meso-tetrakis(N-methylpyridinium-4-yl)-porphyrin as a sensitizer and PEPy as an emitter did not result in UC fluorescence. 25 In the present study, we employed a highly water-soluble cationic sensitizer and emitter and achieved efficient TTA-UC in aqueous solutions from them by just adding DNA.

EXPERIMENTAL METHODS Materials.

Water

soluble

meso-tetrakis(N-methylpyridinium-4-yl)porphyrin,

sensitizer, PdTMPyP,

was

palladium prepared

by

refluxing aqueous solutions of free base form with sodium tetrachloropalladate. 9,10-Dibromoanthracene was coupled with 4-(dimethylamino)phenylboronic acid 5 ACS Paragon Plus Environment

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the presence of tetrakis(triphenylphosphine) palladium and cesium carbonate to form 9,10-bis[4-(dimethylamino)phenyl]anthracene.

9,10-Bis[(trimethylammonium-4-yl)-

phenyl]anthracene (abbreviated as TAPA) was obtained by reacting it with methyliodide. Counter ions of both final products were exchanged to chloride by passing through an ion exchange column. Details of synthesis, purification and characterization are given in supporting information.

Deoxyribonucleic acid (DNA) sodium salt from salmon

testes (D1626, Sigma-Aldrich) was used as received. Aqueous solutions of 0.01 mM PdTMPyP with 0 - 0.5 mM TAPA were prepared in the absence and presence of 0.4 mM DNA based on an average molecular weight of base pairs using deionized water. Measurements Absorption spectra, fluorescence and phosphorescence spectra were measured with JASCO V-770 spectrophotometer and Hamamatsu Photonics C10083CAH high resolution mini-spectrometer, respectively.

UC measurements were made for

deaerated samples by repeated freeze-pump cycles upon excitation with MGL-III-532-10 mW green TPPS laser (CNI Optoelectronics Technology, China) through NDHN-50 variable ND filter (SIGMA KOKI, Japan). 6 ACS Paragon Plus Environment

The emission was

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observed through NF-25C05-40-532 notch filter (SIGMA KOKI, Japan) and an optical fiber by Hamamatsu Photonics C10083CAH high resolution mini-spectrometer or PMA-11 Photonic Multichannel Spectral Analyzer.

The UC quantum yield was

evaluated by the relative method using cresyl violet as a standard in a similar manner as for UC measurements. Time-resolved UC measurements were made by a system composed of a Q-switched Nd:YAG laser, a monochromator equipped with a photomultiplier and a digital oscilloscope.

Circular dichroism (CD) spectra of

PdTMPyP and TAPA in aqueous solutions with DNA were measured by JASCO J-820 CD spectrometer at room temperature.

RESULTS AND DISCUSSION Structures of PdTMPyP 1 and TAPA 2 are shown in Fig. 1 together with their absorption spectra in aqueous solutions without (blue line) or with (red line) DNA (0.4 mM).

Both spectra showed red-shift and hypochromic effects in the

presence of DNA. Emission spectra of 1 (0.005 mM) in deaerated aqueous solutions with 0.2 mM DNA (red line) and without DNA (blue line) are shown in Fig. 2.

In the presence of DNA, the phosphorescence peak is red-shifted from 7 ACS Paragon Plus Environment


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690 to 706 nm and its intensity increases approximately 5-fold.

The

corresponding fluorescence peak shows a similar red-shift but little change intensity.

in

These results together with CD spectra shown in Fig. S3 and S4

clearly indicate that both cationic dyes are immobilized in double helix DNA assembly either by intercalation, groove-binding or electrostatic binding in accordance with previous reports. 26-28 Phosphorescence from 1 at 690 nm was quenched by 2 in aqueous solutions without DNA as shown in Fig. S5 with a Stern-Volmer constant, kSV = 5.1x103 M-1.

In the

presence of DNA, phosphorescence from 1 at 706 nm was quenched more effectively by 2 as shown in Fig. S6, which gave kSV = 1.6x104 M-1.

These results strongly

suggested that triplet energy transfer from 1 to 2 was facilitated by concentration and/or immobilization of 1 and 2 in DNA double helix assembly.

These results indicate that

energy transfer from triplet state of cationic 1 to the cationic emitter 2 occurred in aqueous solutions with or without DNA and that its efficiency was increased in the presence of DNA.

Upconversion fluorescence from 2 was observed in concomitant

quenching of phosphorescence of 1 as shown in Fig. S5 and S6, the intensity of which depended on the concentration of 2 and/or the presence of DNA. 8 ACS Paragon Plus Environment

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Similar effects of DNA were more remarkably observed in UC fluorescence as shown below. Emission spectra for 1 (0.01 mM) and 2 (0.2 mM) in aqueous solutions are shown in Fig. 3 (a) with DNA (0.4 mM) and (b) without it at various excitation powers.

UC fluorescence with a peak at 450 nm in the presence of DNA is fairly

strong at this concentration (0.01 mM sensitizer; 0.2 mM emitter) with 820 mWcm-2 excitation power, and is about 80.4 % of corresponding phosphorescence at 705 nm. Meanwhile, UC fluorescence with a peak at 435 nm is extremely weak in aqueous solutions without DNA, only about 4.1 % of phosphorescence at 691 nm at the same condition. By increasing the ratio of the sensitizer and emitter to 1:50, UC fluorescence can be clearly observed even without DNA, though its intensity is much lower than that observed in the presence of DNA.

The power density dependences of

phosphorescence at 705 nm and UC fluorescence at 450 nm for 1 (0.01 mM) and 2 (0.5 mM) in aqueous solutions with DNA (0.4 mM) are shown in Fig. 4(a).

The slope

(0.84) of the double-logarithmic plot of phosphorescence emission intensity vs. power density is close to the expected value of unity.

For UC fluorescence the corresponding

plot has a lope of 1.18 for power densities higher than about 150 mWcm-2, but is 1.65 for lower power densities.

At the same concentrations of 1 and 2 in aqueous solutions 9 ACS Paragon Plus Environment


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without DNA, the observed UC fluorescence intensity at 435 nm was much weaker as shown in Fig. 4(b). It was only about 10 – 20 % of that with DNA, depending on the power density. In contrast with the slope of 0.94 for phosphorescence in all power ranges, that for UC fluorescence is 1.21 in the higher power region above about 300 mWcm-2, but 2.22 below that power. It is known that UC fluorescence intensity has a quadratic dependence on excitation power as expected for bimolecular reactions when the power is low.29-32 This is the case when kT>> kTT[3E*]0, where kT is the first-order rate constant of emitter excited triplet 3E*, kTT is the second-order rate constant corresponding to TTA, and[3E*]0 is the initial concentration of 3E*.

The UC fluorescence intensity dependence on excitation

power approaches linear when kT> kTT[3E*]0 at low excitation powers, where kT is the first-order rate constant of emitter excited triplet 3E*, kTT is the second-order rate constant corresponding to TTA, and[3E*]0 is the initial concentration of 3E*. (1) Then, time-dependent TTA-UC fluorescence is expressed by eq. (2), (2) The lifetime of UC fluorescence is defined from this equation by (3) Therefore, the emitter triplet lifetime, τt, is given by eq. (4). 13 ACS Paragon Plus Environment


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(4)

The triplet lifetime of 2 was thus evaluated to be 69.2 µs (100%) in the presence of DNA, 2.7 µs (86.6%) and 12.8 µs (13.4%) in the absence of DNA. DNA was thus found to increase the triplet lifetime of emitter 2 by 5.4 – 25.7 times, which most probably contributed to highly efficient UC fluorescence and lower threshold power in aqueous solutions with DNA by cationic sensitizer and emitter observed in the present study for the first time.

Since the concentration

of 2 is 1.25 times that of average base pairs of DNA, all base pairs will contain an emitter 2 and one out of four base pairs contain two emitter molecules. Based on the

distance between base pairs, 0.34 nm34, the average distance among emitters

on DNA backbone is estimated to be equal to it or less.

Energy migration

among emitters well organized and immobilized in DNA double helix assembly22,23 is presumed to contribute to such positive effects. Schematic representation of efficient TTA-UC from highly water-soluble sensitizers and emitters, which are concentrated and immobilized in DNA double helix assembly, is shown in Fig. 7. 14 ACS Paragon Plus Environment

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CONCLUSIONS Considerable enhancement of UC fluorescence was observed using highly water-soluble cationic sensitizer and emitter, for the first time, in aqueous

solutions with DNA.

From spectroscopic data, excitation power dependence

and dynamic results, it was concluded that DNA concentrated and immobilized these dyes into double helix assembly and facilitated triplet energy transfer and triplet-triplet annihilation.

ASSOCIATED CONTENT Supporting Information The Supporting Information is available free of charge on the ACS Publications website at DOI: Figures S1−S6 (PDF)

AUTHOR INFORMATION Corresponding Author 15 ACS Paragon Plus Environment


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E-mail: [email protected]

Notes The authors declare no competing financial interest.

ACKNOWLEDGMENTS This study was partly supported by Grants-in-Aid for Scientific Research (B) 16H03838 and 2016 Cooperative Research Project of Research Institute of Electronics, Shizuoka University.

Authors would like to acknowledge Dr. John D. Wright for

carefully reading the manuscript, and Dr. T. Okawara, Mr. T. Atsumi, Mr. S. Uda, Mr. M. Nagata, and Mr. H. Morita for their partial contributions.


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Figure captions Fig. 1 Structure of PdTMPyP 1 and TAPA 2, absorption spectra of (a) 1 (0.01 mM) and (b) 2 (0.2 mM) in aqueous solutions without (blue line) or with (red line) DNA (0.4 mM). Fig. 2 Emission spectra of 1 (0.005 mM) in the absence (blue line) and presence (red line) of DNA (0.2 mM) in deaerated aqueous solutions excited at 532 nm. Fig. 3

Emission spectra for 1 (0.01 mM) and 2 (0.2 mM) in aqueous solutions (a)

with DNA (0.4 mM) and (b) without DNA excited at 532 nm with several powers. Fig. 4 Power density dependences of phosphorescence (a) at 705 nm and UC fluorescence at 450 nm for 1 (0.01 mM) and 2 (0.5 mM) in aqueous solutions with DNA (0.4 mM), and (b).at 690 nm and UC fluorescence at 435 nm for 1 (0.01 mM) and 2 (0.5 mM) in aqueous solutions without DNA. Fig. 5 . Time dependences of phosphorescence of 1 (0.01 mM) (a) at 705 nm in deaerated aqueous solutions with DNA (0.4 mM), and (b) at 690 nm in deaerated aqueous solutions without DNA. Fig. 6 Time dependences of UC fluorescence for 1 (0.01 mM) and 2 (0.5 mM) in aqueous solutions (a) with DNA (0.4 mM) and (b) without DNA excited by ns pulsed 24 ACS Paragon Plus Environment

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laser at 532 nm with (a) 0.4 and (b) 1.0 mJ/pulse. Fig. 7 Schematic representation of sensitizer 1 and emitter 2 molecules concentrated and immobilized in DNA double helix assembly.

Counter sodium cations of DNA are not

shown for simplicity.



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Fig. 1

Fig. 2


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Fig. 3

Fig. 4

Fig. 5



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The TOF graphic

Efficient upconversion by highly water-soluble cationic sensitizer and emitter in aqueous solutions with DNA Ayaka Fukuzaki, Hideki Kawai, Tomomi Sano, Kenji Takehara, and Toshihiko Nagamura

sensitizer


emitter

Efficient upconversion by highly water-soluble cationic sensitizer and

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