Excitation Modulation of Upconversion Nanoparticles for Switch-like

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Excitation Modulation of Upconversion Nanoparticles for Switch-like Control of Ultraviolet Luminescence Peter Dawson, and Marek Romanowski J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b13677 • Publication Date (Web): 17 Apr 2018 Downloaded from http://pubs.acs.org on April 17, 2018

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Journal of the American Chemical Society

Excitation Modulation of Upconversion Nanoparticles for Switch-like Control of Ultraviolet Luminescence Peter Dawson and Marek Romanowski Department of Biomedical Engineering, University of Arizona, Tucson, Arizona 85721, United States.

Supporting Information Placeholder ABSTRACT: The ability to control ultraviolet (UV) luminescence intensity in a switch-like manner is demonstrated through 3+

3+

the use of 980 nm excitation pulse-width modulation in NaYF4:Yb ,Tm upconversion nanoparticles (UNPs). Varying the ytterbium doping resulted in a single order of magnitude improvement of UV luminescence intensity. The excitation pulsewidth modulation technique applied to these optimized UNPs enables three order of magnitude control over UV luminescence intensity while maintaining NIR luminescence emission at 800 nm. Controlled in the switch–like manner, these UNPs can transfer their UV energy to 9,10-diphenylanthracene (DPA). Independent control of NIR luminescence and UV energy transfer through NIR excitation modulation may find applications in the development of multifunctional theranostic systems.

Introduction Excited states generated in the energy upconversion process in certain nanoparticles may enable a range of biomedical applications. For example, upconversion to visible or near infrared (NIR) wavelengths can support optical imaging modalities that are relatively free of autofluorescence, whereas upconversion to ultraviolet (UV) offers the potential to activate photochemical processes in a manner that does 1,2 not require direct UV irradiation. Recent literature shows the use of thulium-generated UV luminescence in UNPs as 3–5 an activator of drug release in conjugated systems. However, these experiments are generally limited to imaging and 5–7 payload release at the same time. If both functions can be achieved independently in the same nanoparticle, it may lead to the realization of a true theranostic agent, an agent capable of performing diagnostic and therapeutic functions as selected by the user. Here, we describe a mechanism by which specific upconversion pathways and associated functions can be independently activated. We describe preparative and post-preparative controls of upconversion. Through the use of a novel excitation modulation scheme, we demonstrate a control of upconversion pathways in both aqueous and organic solvents, so NIR to UV upconversion can be turned on and off while maintaining NIR to NIR upconversion. As referred to in this text, upconversion is the excitation process in which real states are sequentially populated by lower energy photons leading to the eventual emission of a higher energy photon. Upconversion can occur in singular atoms, crystals, or molecules by a multitude of 8–10 mechanisms. The ability to generate ultraviolet light from NIR excitation in upconversion nanoparticles may enable a NIR activation of photochemical processes traditionally requiring UV radiation. NIR to UV upconversion may, there-

fore, enhance medical applications of UV cured polymers or photolytic drug release in live tissues where direct UV irradi11 ation is not desirable. It also adds the ability to activate said photochemical processes at greater depths where penetration of shorter wavelength light is hampered by high scatter12 ing or absorption events. In addition, the ability to maintain NIR emission independent of photochemistry activation enables mon-

Figure 1. Energy levels available in UNP showing transitions 3+ within Tm , relative intensities of luminescence emission, and putative paths of energy transfer (ET).

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Figure 2. Characterization of UNPs obtained by thermolytic method. (a) Luminescence intensity decays of the three main emission regions of UNPs. (b) The UNP size distribution histogram using dynamic light scattering. (c) XRD spectrum of UNPs and the reference hexagonal NaYF4 (00-016-0334). (d) A 105,000x TEM image of the UNPs. -itoring of the distribution of these upconversion nanoparticles (UNPs) to support various diagnostic applications or image-guided modalities in interventional medicine. Results and Discussion 3+

3+

We prepared NaYF4:Yb ,Tm nanoparticles with 0.5% thulium (see Supplemental Information for details of synthetic methods and characterization). We selected thulium for its many states whose radiative decay span the UV and NIR spectrum as seen in Figure 1. Nanoparticles were synthesized using two different methods. The first method was a 13 hydrothermal synthesis based in water and ethanol. This method was chosen for its simplicity, facilitating rapid examination of different ytterbium doping schemes. For the second set of UNPs we selected a thermolytic synthesis, cho14,15 sen for the high quality of resulting UNPs. 3+

3+

These nanoparticles are NaYF4:Yb ,Tm with ytterbium and thulium doping concentrations of 30% and 0.5% respectively. Thulium-doped NaYF4 nanoparticles, given reasonable size, absence of defects, and an optimally doped crystal, can produce UV emitting states from NIR excitation through four 16 and five photon processes. At a diameter of roughly 36 nm as seen in Figure 2b,d and upon 980 nm, 10 ms pulse width laser excitation, the thermolytic-synthesized nanoparticles 1 1 produced UV emission from both the I6 and D2 states, at 350 and 365 nm respectively. 1

3+

3+

NaYF4:Yb ,Tm UNPs are dependent on two forms of upconversion: energy transfer upconversion (ETU) and excited 17 state absorption (ESA). ESA is consecutive excitation of real states within an atom, in this case thulium, leading to a higher energy state than that which would be associated with any particular excitation wavelength. ETU is the transfer of energy from a sensitizer, ytterbium, to the activator atom, thulium, to produce a higher energy state within the activator. In theory, ETU is two orders of magnitude more effective 10 than ESA. Increased ytterbium doping should promote upconversion to higher energy states through ETU due to the

3+

The UV luminescence output of NaYF4:Yb ,Tm particles depends nonlinearly on the doping of ytterbium (Figure 3). Initially, UV luminescence intensity increases with an increased doping of ytterbium, likely as added ytterbium cooperates in energy transfer upconversion to improve luminescence yield. However, as the crystal saturates with ytterbium, substantial loss of luminescence occurs, likely due to increased contributions of energy migration through ytterbium 19,22 toward surface sites, dissipating energy from the system. Figure 3 shows approximately a single order of magnitude improvement of UV luminescence intensity achieved by the preparative controls.

1

These nanoparticles also produce emission from D2, G4 3 and H4 states, at 460, 475 and 800 nm (Figure 1), together representing the most intense and recognizable emission lines in thulium. With some of the emission lines challenging to resolve, we broadly categorize emissive lines of thulium as the UV (350, 365 nm), blue (460, 475 nm) and NIR (800 nm) luminescence. Excited state lifetimes associated with the UV, blue and NIR luminescence are 0.558, 0.695, and 1.463 ms respectively (Figure 2a). 3+

18

ability of ytterbium to transfer energy to thulium. At even higher doping rates of ytterbium, the phenomenon of cross19 relaxation energy migration occurs with higher prevalence. 3+ The corollary is also evidenced as NaYbF4:Tm UNP preparations produce significantly stronger luminescence when 40% 3+ 3+ 20 of the Yb lattice is replaced with Y . For this reason, a series of hydrothermal syntheses were performed with an incremental increase of ytterbium doping ratio, from 0 to 99.5%. Optimization of the ytterbium doping ratio served as a preparative control of luminescence intensity of these 21 UNPs.

1.0 UV Intensity (AU)

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0.5

0.0 0

25 50 75 Yb Dopant (%)

100

Figure 3. Luminescence intensities of 0.5% thulium-doped upconversion nanoparticles upon 2 ms pulse 980 nm excitation as a function of ytterbium doping. Upconversion, due to the many states and rates involved, 23–27 is highly dependent on the excitation method. Thus, excitation modulation presents itself as a promising postpreparative control of luminescence. In particular, we focus


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on the excitation pulse-width sensitivity of UNP luminescence, which reflects the complexity of the relative rates of processes populating participating excited states. UNPs have shown a unique sensitivity to pulsed excitation, in particular 23,28– to pulse widths in the microsecond to millisecond range. 30 Ability to manipulate luminescence of UNPs using excitation modulation is a phenomenon we previously observed in 3 4 the visible luminescence of erbium from the S3/2 and F9/2 states wherein the frequency of excitation pulses controlled 25 depopulation pathways. High frequency, 100 kHz, 980 nm excitation pulses produced a more intense red luminescence over green whereas lower frequency, 100 Hz, excitation pulses corresponded with a greater ratio of green to red lumines25 cence intensity. These findings were later reaffirmed with the addition of a pulse width modulation scheme to produce 23,24 similar results at fixed frequency. Here we advance these techniques with a different activator, thulium, in an attempt to provide independent control of UV and NIR luminescence.

ties observed in lipid-coated UNPs, strongly dependent on 31–33 the surface chemistry and dispersant.

Figure 5: Luminescence intensity spectra of UNPs as well as UNPs with DPA in suspension at (a) longer (2 ms) and (b) shorter (10 µs) excitation pulse widths.

Figure 4. Emission intensity of thermolytic decomposition 3+ 3+ 3+ 3+ synthesized NaYF4:Yb ,Tm (30% Yb , 0.5% Tm ) UNPs by region dependent on pulse width of 980 nm excitation. Intensities are normalized to 1 at 2000 µs pulse width. We investigated NIR and UV luminescence from these UNPs under conditions of pulsed 980 nm excitation, with the pulse width varied from 10 to 2000 µs. The duty cycle was 2 kept constant at 10%, so the average power of 142 mW/cm delivered by excitation was the same for any of the pulse widths tested. The UV and NIR emission intensities have vastly different responses to changes in the pulse width (Figure 4). NIR emission intensity decreases relatively little, approximately 50%, with the excitation pulse width changing from the longest to the shortest. In stark juxtaposition, UV luminescence intensity falls off three orders of magnitude when changing excitation regimen from a long pulse width to a short one. The highly nonlinear luminescence response to pulse width enables control of UV luminescence intensity in the manner resembling a binary switch while retaining intensity NIR luminescence of UNP. The switch-like behavior was then studied in aqueous buffer. UNPs were lipidcoated, dispersed in PBS, and exposed to pulsed 980 nm excitation using the same pulse regimen and power. Lipid-coated UNPs in PBS demonstrate a similar switching a behavior, with UV luminescence intensity falling off two orders of magnitude upon switching (Figure 4). We attribute the less pronounced difference to overall lower luminescence intensi-

We then investigated whether the energy of the excited UV states of UNP generated by the long excitation pulses is available to an energy acceptor introduced to the system. This energy acceptor can represent a photochemical substrate of interest, participating in photolysis or polymerization. In our demonstration, we selected 9,10diphenylanthracene (DPA), a fluorescent probe with excitation at 372 nm and emission at 402 nm. DPA can participate in energy transfer, for example, as energy acceptor in pair with platinum octaethylporphyrin, an energy donor in tri8,34 plet-triplet annihilation. Because of the long lifetime of the excited states of UNP, the energy transfer may occur through collisions of free nanoparticles and DPA, taking place within the lifetime of the excited state. The diffusioncontrolled bimolecular collision rate constant k0 can be calculated from the Smoluchowski equation (1), with the diffusion coefficients obtained from the Stokes-Einstein equation (2)

4

1000 /6

where k is the Boltzmann constant, T, the temperature is a fixed 296 K, η is medium viscosity, and R is the radius. In this 5 -1 approximation, the collisional rate constant k0 = 6.8×10 s is much greater than the apparent rate of the UV luminescence 3 -1 decay, 2×10 s (Figure 2a). Therefore, even though the energy donor and acceptor are not covalently bound, we expect that energy transfer may occur between free UNP and DPA


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through the non-radiative process of diffusion enhanced 35 luminescence resonant energy transfer (DELRET). Indeed, in the system comprising UNP and DPA, upon excitation by long pulses (pulse width of 2 ms) at 980 nm, we observed a new emission band at 402 nm with concomitant loss of UNP luminescence intensity at 360 nm (Figure 5a). We attribute the 402 nm emission band to fluorescence from 1 DPA excited by the energy transfer from the D2 state in UNP. In comparison, using short pulses (10 µs) at 980 nm, we observed no transfer of UV energies (Figure 5b). Both excitation pulse regimens retained the characteristic UNP NIR emission at 800 nm, with no noticeable change of intensities upon energy transfer to DPA (Figure 5a, b). Conclusions In this work, we demonstrated that one can turn on and off the UV emission from UNPs via modulation of the excitation pulse width. Short pulse width of 10 µs produces nearly undetectable UV luminescence, while 2 ms pulse width produces UV intensity comparable to that of NIR emission. NIR intensity remains fairly insensitive to this change of pulse width. In a tentative model, this pulse width control is ena3 bled by the H4 manifold leading to NIR emission or, upon excitation using a longer pulse width, to population of higher 3+ energy states in Tm (Figure 1). Moreover, presented results demonstrate the possibility of selectively turning on and off UV-activated processes while maintaining NIR luminescence of UNP. In the biomedical field, this possibility points to unique applications that may combine imaging and ondemand photochemistry, more broadly categorized as diagnostic and therapeutic modalities, in one functional nanoparticle. While originally UNPs were recognized primarily for their benefits in biological imaging, their newer applications in3,6,9,36,37 clude various forms of conjugated therapeutic agents. The binary response to excitation pulse width described here positions these particles as a potential theranostic platform, with independently accessible diagnostic and therapeutic modalities as illustrated in Figure 6. It bares acknowledgment that certain UNP systems that rely on photothermal conversion for therapeutic effect would be able to achieve similarly independent control of therapy and imaging by precise dosing of excitation flux rather than any spe37 cific control of the excitation pulse width or frequency. The capabilities of pulse width modulation-based control are not limited to therapeutics or even biomedical applications. The crux of this work is centered on broad control of delivery of UV energy, to eliminate or minimize unnecessary exposure to UV radiation. Enhancing the switch-like control of UV luminescence or photochemistry may depend on the synthetic method used for the preparation of the particles as well as the optimization of particle doping. Notably, crystal phase, particle size, surface and dispersant play critical roles 22,31,38 in luminescent properties of UNP. Experimentally observed radiative processes represent a convolution of several, some competing, processes, each with its own rate constant. A complete understanding of radiative as well as nonradiative rate constants in UNPs, while experimentally challenging, may enable various manipulation of energy pathways in support of specialized applications.

Figure 6. Cartoon representation of switching behavior usage to allow for independent imaging and UV activated functions may include photolysis of a drug, polymerization of medical adhesive, or luminescence.

ASSOCIATED CONTENT Supporting Information A transmission electron micrograph and powder XRD of the sample, details of the synthetic methods, methodology for the spectral measurements and instrumentation used are provided. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author [email protected]

Notes The authors declare no competing financial interests.

ACKNOWLEDGMENT Funding was provided in part by grants T32 training grants GM084905 and EB000809 from the National Institutes of Health. A special thanks to Dr. Urs Utzinger for use of shared instruments and to University Research Services for use of TEM and XRD.

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Energy levels available in UNP showing transitions within Tm3+, relative intensities of luminescence emission, and putative paths of energy transfer (ET). 135x140mm (96 x 96 DPI)



Characterization of UNPs obtained by thermolytic method. (a) Luminescence intensity decays of the three main emission regions of UNPs. (b) The UNP size distribution histogram using dynamic light scattering. (c) XRD spectrum of UNPs and the reference hexagonal NaYF4 (00-016-0334). (d) A 105,000x TEM image of the UNPs. 218x52mm (300 x 300 DPI)


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Luminescence intensities of 0.5% thulium-doped upconversion nanoparticles upon 2 ms pulse 980 nm excitation as a function of ytterbium doping. 89x62mm (300 x 300 DPI)



Emission intensity of thermolytic decomposition synthesized NaYF4:Yb3+,Tm3+ (30% Yb3+, 0.5% Tm3+) UNPs by region dependent on pulse width of 980 nm excitation. Intensities are normalized to 1 at 2000 µs pulse width. 89x62mm (300 x 300 DPI)


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Luminescence intensity spectra of UNPs as well as UNPs with DPA in suspension at (a) longer (2 ms) and (b) shorter (10 µs) excitation pulse widths. 97x126mm (300 x 300 DPI)



Cartoon representation of switching behavior usage to allow for independent imaging and UV activated functions may include photolysis of a drug, polymerization of medical adhesive, or luminescence. 219x157mm (150 x 150 DPI)


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Excitation Modulation of Upconversion Nanoparticles for Switch-like

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