Optically Active Upconverting Nanoparticles with Induced Circularly

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Optically Active Upconverting Nanoparticles with Induced Circularly Polarized Luminescence and Enantioselectively Triggered Photopolymerization Xue Jin,†,⊥ Yutao Sang,‡,§,⊥ Yonghong Shi,∥ Yuangang Li,∥ Xuefeng Zhu,‡ Pengfei Duan,*,†,§ and Minghua Liu†,‡,§ †

CAS Center for Excellence in Nanoscience, CAS Key Laboratory of Nanosystem and Hierarchical Fabrication Division of Nanophotonics, National Center for Nanoscience and Technology (NCNST), No. 11 ZhongGuanCun BeiYiTiao, Beijing 100190, P. R. China ‡ Beijing National Laboratory for Molecular Science, CAS Key Laboratory of Colloid, Interface, and Chemical Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, No. 2 ZhongGuanCun BeiYiJie, Beijing 100190, P. R. China § University of Chinese Academy of Sciences, Beijing 100049, P. R. China ∥ College of Chemistry and Chemical Engineering, Xi’an University of Science and Technology, No. 58, Yanta Road, Xi’an 710054, P.R. China S Supporting Information *

ABSTRACT: In this work, lanthanide-doped upconversion nanoparticles (UCNPs) showing upconverted circularly polarized luminescence were demonstrated in an organic−inorganic co-assembled system. Achiral UCNPs (NaYF4:Yb/Er or NaYF4:Yb/Tm) can be encapsulated into chiral helical nanotubes through the procedure of co-gelation. These co-gel systems display intense upconverted circularly polarized luminescence (UC-CPL) ranging from ultraviolet (UV, 300 nm) to near-infrared (NIR, 850 nm) wavelength. In addition, the UV part of UC-CPL can be used to initiate the enantioselective polymerization of diacetylene. KEYWORDS: upconverted circularly polarized luminescence, self-assembly, chiral host, upconversion nanoparticles, organogel, enantioselective photopolymerization during the transition process,13−15 and almost every single wavelength of circularly polarized light needs a special setup with designed plates. On the contrary, chiral luminescent materials are enabled to directly generate circularly polarized light. While the palette of CPL-active materials obtained from

O

ptical materials with circularly polarized luminescence (CPL) properties have recently received growing attention because of the promising applications including optical probes and sensors,1−5 advanced microscopes,6 three-dimensional display,7,8 security tags,9 lasers,10 data storage,11 and spin-optoelectronic circuits.12 Generally, circularly polarized light could be produced from unpolarized light via the use of a linear polarizer and a quarterwave plate. However, this method causes a loss in energy © XXXX American Chemical Society

Received: October 29, 2018 Accepted: January 24, 2019

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DOI: 10.1021/acsnano.8b08273 ACS Nano XXXX, XXX, XXX−XXX

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Figure 1. (a) Schematic representation of upconverted circularly polarized luminescence (UC-CPL) based on achiral UCNPs and chiral nanotubes. Upon the excitation of 980 nm laser, blue and green UC-CPL could be obtained from the UCNPs-Tm and UCNPs-Er co-gels, respectively. (b) Energy level diagram and energy-transfer upconversion process for the UCNPs. The spirals represent the detected UC-CPL in this work.

Figure 2. TEM images of (a) UCNPs-Tm and (b) UCNPs-Er. SEM image of (c) LGAm and (d) LGAm/UCNPs-Er co-gels. TEM images of (e) LGAm and (f) LGAm/UCNPs-Er co-gels. [LGAm] = 26.7 mg mL−1 and [UCNPs] = 1.7 mg mL−1.

method. Another approach reported very recently is the “chiral host-luminescent guest”. Luminescent inorganic nanomaterials (guests) are achiral; however, after incorporation into a chiral host, they display induced chirality and hence become CPLactive.16,28,30,38 To date, several inorganic nanomaterials have been reported to show CPL by incorporating into chiral guests, including QDs,37 perovskite nanocrystals,28 and lanthanide oxides nanoparticles.39 The chiral assembly of achiral nanomaterials in confined space of chiral host was considered to be the main reason for the induced chirality and CPL behaviors. Compared with the chiral host, there are more options for the

organic nanostructures is broad,16−27 the variety of inorganic materials used for chiral emissive material is limited. To date, only a few CPL-active inorganic nanomaterials were developed either through the tedious synthesis or with unregulated chiroptical properties.28−34 Generally, there are two feasible approaches to construct CPL-active inorganic materials. The most common approach is capping the inorganic nanostructures with chiral reagents, which has been extensively demonstrated as a general method for fabricating chiral nanomaterials.35 So far, CPL-active noble metal clusters,29,36 chalcogenide semiconductor quantum dots (QDs),36,37 and nanostructured ZnO films32 have been reported by using this B

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Figure 3. (a) Upconverted emission spectra of UCNPs before (top) and after (down) co-assembled with chiral gelator excited by 980 nm laser. (b) Upconversion emission spectra of LGAm/UCNPs-Er co-gels with different incident power density of 980 nm laser. The inset shows the double-logarithmic plots of the UC emission intensity (at 540 nm) of LGAm/UCNPs-Er co-gels as a function of excitation intensity of the 980 nm laser. (c) Optical microscopy images and (d) two-photon laser confocal scanning microscopy of LGAm/UCNPs-Er co-gels. [LGAm] = 26.7 mg mL−1 and [UCNPs-Er] = 1.7 mg mL−1.

2a,b, both UCNPs-Er and UCNPs-Tm exhibited well-defined hexagonal shapes with the mean size of about 30 nm. X-ray diffraction (XRD) pattern further confirmed the hexagonal phase of these guest UCNPs (Figure S1). The host gelator LGAm (or DGAm) is a typical amine-containing lipid, which has been proved as a versatile gelator to form chiral nanotubes through supramolecular gelation in a wide range of mixed solvents.46 The SEM image in Figure 2c shows that LGAm formed the left-handed chiral nanotubes. After co-assembly with UCNPs, the tubular morphology remains the same, showing similar uniform structures (Figure 2d). However, the TEM images indicate that UCNPs could well assemble along the chiral nanotubes after co-gelation process (Figures 2e,f and S2). In addition, the XRD patterns and Fourier transform infrared spectroscopy (FTIR) spectral results of gelator/ UCNPs confirmed that the addition of UCNPs into the gels would not disturb the formation of chiral nanotubes (Figures S3 and S4). It should be noted that the N−H stretching vibration of the gels showed a slight shift from 1525 to 1529 cm−1 after mixing with UCNPs, which might be attributed to the weak interaction between gelators and UCNPs (Figure S4). This might be the main driving force for the encapsulation of UCNPs into chiral nanotubes. The Realization of UC-CPL. To evaluate the influence of co-gelation process toward the emission behavior of the UCNPs, the relative emission spectra of DMF solution and its co-gels were carefully compared. As shown in Figure 3a, upon excitation with a 980 nm laser, the emission peaks of UCNPsTm are mainly located at 360, 476, and 802 nm, which can be ascribed to the 1D2 → 3H6, 1G4 → 3H6, 3H4 → 3H6 transitions of Tm3+ irons (Figure 1b left), respectively.40,47 On the other hand, the UCNPs-Er mainly exhibited characteristic sharp emissions at 540 and 654 nm, which can be attributed to 4S3/2

luminescent guest. However, endowing inorganic materials with CPL is still challenging. Lanthanide-doped upconversion nanoparticles (UCNPs), which can convert low-energy NIR light into high-energy UV or visible light (anti-Stokes shift) through the absorption of two or multiple low-energy photons,40,41 have found diverse applications such as sensing, bioimaging, and near-infrared light-driven actuators due to their distinctive properties, including low autofluorescence, no photobleaching, large anti-Stokes shift, and high penetration depths.42−45 However, UCNPs with CPL-activity have never been reported. In this work, by using a well-demonstrated chiral lipid gelator N,N′bis(octadecyl)-L-glutamic diamide (LGAm) and its enantiomer DGAm, which have been reported to form uniform chiral nanotubes during the gelation,46 we successfully realized the “chiral host-UCNPs guest” composite, as shown in Figure. 1a. Two kinds of achiral UCNPs stabilized by oleic acid, NaYF4:Yb/Er (UCNPs-Er) and NaYF4:Yb/Tm (UCNPsTm), were helically encapsulated into chiral nanotubes. Hence, the upconverted CPL (UC-CPL) could be observed under the excitation of nonpolarized 980 nm laser (Figure 1b). The comparison experiment results indicated that the wellordered arrangement of UCNPs along the chiral nanotubes is crucial for the induced UC-CPL. In addition, the ultraviolet parts of UC-CPL generated from the co-gels can be used to trigger the enantioselective photopolymerization of diacetylene (DA) derivatives.

RESULTS AND DISCUSSION Self-Assembled Chiral Host-UCNPs Guest Composite. To clarify the morphologies of UCNPs and gels, we measured the morphology by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). As shown in Figure C

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Figure 4. (a) UC-CPL emission spectra of co-gels excited by 980 nm laser. The DC value in the bottom spectrum stands for fluorescence intensity. To obtain clear UC-CPL spectra, the co-gel systems were tested in several parts of wavelength (300−490, 490−700, and 700−850 nm), wherein the maximum emission peaks were modulated around 0.5 V. [LGAm] = [DGAm] = 26.7 mg mL−1 and [UCNPs-Er] = [UCNPs-Tm] = 1.7 mg mL−1. (b) Illustration of the possible mechanism for the UC-CPL. The unassembled state of LGAm/UCNPs was achieved from a chlorobenzene solution. To illustrate the importance of chirality from gelator, achiral BAm with similar structure was synthesized. Corresponding spectra could be found in the Figure S11.

→ 4I15/2 and 4F9/2 → 4I15/2 transitions of Er3+ (Figure 1b right), respectively.40,48 When these UCNPs were mixed with the gelator, the co-gel systems exhibited the identical spectra of UCNPs solution at same concentrations, except the luminescence intensities slightly decreased due to the scattering (Figures 3a and S5). Comparing with the lifetime of UCNPs in solution (289 μs), the luminescence lifetime of the co-gels extended to 473 μs, indicating that the nonradiative decay of the UCNPs was significantly suppressed (Figure S6). In addition, the upconverted emission intensity was found to be closely dependent on the excitation power density with the slope of 2.0 (Figure 3b), which indicated that the two-photon absorption based upconversion was preserved during the cogelation process.27 To further confirm the encapsulation of UCNPs in the cogel system, we measured the two-photon laser scanning microscopy of gelator/UCNPs co-gel in DMF solvent. As shown in Figure 3c,d, we could observe the green fluorescence in the tubular structures. The emission color is consistent with spectral measurements (Figure 3a). It should be noted that the recognizable structures and emission color further confirmed that the UCNPs perfectly dispersed into the co-gel system without phase separation or serious aggregation.

More intriguingly, we observed the mirror-image UC-CPL signals, which covers a wide range from 300 nm (UV part) to 850 nm (near-infrared), as shown in Figure 4a. Since the intensity of emission peaks varied significantly under the same excitation, it was hard to observe the clear UC-CPL spectra of weak emission (Figure S7). Therefore, the co-gel systems were tested in several parts of wavelength (300−490 nm, 490−700 nm and 700−850 nm), wherein the maximum emission peaks were modulated around 0.5 V (Figure 4a). The magnitude of CPL can be evaluated by the luminescence dissymmetry factor (glum), which is defined as glum = 2 × (IL − IR)/(IL + IR), where IL and IR refer to the intensity of left- and right-handed CPL, respectively. Experimentally, the value of glum is defined as glum = [ellipticity/(32980/ln 10)]/total fluorescence intensity at the CPL extremum. Since glum is independent of luminesce intensity, the quantitative analysis of glum value clearly indicate the optical activity of co-gel systems. In general, more UCNPs in the system should give rise to stronger CPL (Figure S8). However, too many UCNPs could also destroy the coassembly and lead to the decline of CPL intensity. The sample with mass ratio of gelator/UCNPs equal to 16 gave the maximum glum value upon the CPL spectral measurement. As expected, the UC-CPL intensity was dependent on the excitation intensity (Figure S9). Although the UC-CPL D

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Figure 5. (a) Schematic setup of the enantioselective photopolymerization of HA. Excitation power density of the 980 nm laser is 120 mW. A short-pass filter was used to cut the upconverted light from 400 to 808 nm. (b) Illustration of the polymerization of HA. (c) CD spectra of PDA films after exposing to the UC-CPL generated from UCNPs-Tm doped co-gels.

emission increased with increasing excitation intensity, the glum value was almost the same (the average value of glum is 5.48 × 10−3 at 534 nm), showing independence to the excitation intensity, which indicated the inherent property of UC-CPL. However, due to the minor content of UCNPs in the co-gels and the strong scattering in the near-infrared region, it is hard to observe the induced circular dichroism (CD) signals of UCNPs (Figure S10). To investigate the mechanism of the induced UC-CPL in the co-gels, we tested the spectral properties of the unassembled state of the chiral gelator/UCNPs mixtures. LGAm and DGAm are well soluble in chlorobenzene when the concentration is below 20 mM. After blending UCNPs-Er and DGAm (20 mm) in chlorobenzene, a transparent solution was obtained. Although strong emission was observed for this solution under the 980 nm excitation, no CPL was detected (Figure S11a). The effect of chirality on UC-CPL was tested by using the LGAm/DGAm analogue BAm, which was an achiral molecule (Figure 4b). Interestingly, no UC-CPL was observed for BAm/UCNPs co-assemblies even at the same experimental condition of LGAm/UCNPs (Figure S11b). Based on these results, the mechanism for UC-CPL in our “chiral host-UCNPs guests” system is illustrated in Figure 4b. To achieve UC-CPL, the chiral arrangement of UCNPs is necessary and critical. The unequal left- and right-handed UCCPL were generated from a supramolecular level rather than the monomers. In the unassembled state, although LGAm and DGAm has the inherent chirality from glutamate part, the chirality transfer from the chiral monomer to UCNPs seems impossible. Therefore, no UC-CPL was observed from the unassembled state of chiral gelator/UCNPs mixtures. On the other hand, if the arrangement of UCNPs is disordered, then it is hard to exhibit UC-CPL as well. For example, the complex of achiral BAm and UCNPs shows UC-CPL silent. As shown in Figure S12, a micron-sized sphere structure that consisted of

smaller spherule was observed for the BAm/UCNPs. Compared with the sphere morphology, the hollow structures of chiral tubes provided a confined space for the encapsulation of UCNPs, which is more effective for the chirality transfer. Thus, the arrangement of UCNPs along the chiral tubes might be the key reason for the induced UC-CPL in our work. UC-CPL Triggered Enantioselective Photopolymerization. To further extend the application of the UV part of UC-CPL that generated from the co-gel systems, we constructed the irradiation setup, as shown in Figure 4a. Particularly, the induced CPL at UV part might be possible for initiating the enantioselective photopolymerization of diacetylene (Figure 5).49,50 In a typical run, the UCNPs-Tm doped co-gels were prepared and kept in cuvettes in the dark. The 2,4-heneicosadiynoic acid (HA) film was prepared by a spincoating method and placed right behind the cuvettes. Then, the UC-CPL that generated from the co-gels could directly irradiate on the HA film. After exposing to the UC-CPL for 120 min, the HA film turned blue which indicated the formation of polydiacetylene (PDA).49,51 Interestingly, the obtained PDA showed a mirror-image Cotton effect in the CD spectra, depending on the handedness of circularly polarized light, as shown in Figure 5c. More importantly, the CD signals were found to follow the molecular chirality of the gelator. The PDA film irradiated from LGAm/UCNPs-Tm co-gel exhibited the positive CD signals, while the PDA film irradiated with DGAm/UCNPs-Tm co-gel showed the opposite signals (Figure 5c). The authenticity of CD spectra obtained from PDA films could be confirmed by the linear dichroism (LD) measurements (Figure S13). The results indicated that the LD contribution to CD spectra could be neglected. These results clearly indicated that the molecular chirality of the gelator controlled the handedness of the UC-CPL generated from the LGAm or DGAm/UCNPs-Tm co-gels and then subsequently controlled the enantioselective polymerization of diacetylene. E

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quartz plate, and spin-coating at a higher speed of 1000 rpm for 60 s was conducted. The HA film was kept in the dark and at room temperature prior to further use.

CONCLUSION In summary, we reported UC-CPL from lanthanide-doped nanoparticles by the approach of chiral nanotube encapsulation. Two kinds of achiral UCNPs were confined into the assembled chiral nanotubes during the process of co-assembly, enabling the emission of UC-CPL with a large range of wavelength from UV to NIR. The chiral arrangement of the doped UNCPs in the chiral nanotubes plays the leading role for the induced UC-CPL. By applying the upconverted circularly polarized UV light generated from UCNPs-Tm doped co-gels, enantioselective photopolymerization of diacetylene was successfully achieved. This work underlines the importance of UC-CPL concept and inspires the exploration of functional CPL-active materials toward a highly efficient and large dissymmetry factor, which may find a variety of applications in the future.

ASSOCIATED CONTENT S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsnano.8b08273. Experimental details; TEM images, XRD patterns, FTIR spectra, and additional UC-CPL spectra (PDF)

AUTHOR INFORMATION Corresponding Author

*E-mail: [email protected]. ORCID

Pengfei Duan: 0000-0002-5971-7546 Minghua Liu: 0000-0002-6603-1251

MATERIALS AND METHODS Materials. All the starting materials and solvents were obtained from commercial suppliers and used as received. Lanthanide-doped upconversion nanoparticles (UCNPs) were acquired from Hangzhou Fluo Nanotech Co., Ltd. N,N-Dimethylformamide (DMF) was acquired from Sigma-Aldrich. 2,4-Heneicosadiynoic Acid (HA) was purchased from TCI and purified by dissolution in toluene and subsequent filtration to remove polymer before use. The gelator N,N′bis(octadecyl)-L-glutamic diamide (LGAm) and its enantiomer DGAm were synthesized according to previous reported methods.52 Characterizations. The 1H NMR spectra were recorded on a Bruker AV400 (400 MHz) spectrometer. Mass spectral data were obtained by using a BIFLEIII matrix-assisted laser desorption/ ionization time of fight mass spectrometry (MALDI-TOF-MS) instrument. UV−vis and CD spectra were conducted on Hitachi U3900 spectrophotometer and JASCO J-1500 spectrophotometers, respectively. Confocal laser scanning microscope (CLSM) images were obtained from an Olympus FV1000 equipped with MaiTai Deepsee two-photon laser. Upconverted emission spectra were recorded on a Zolix Omin-λ500i monochromator with photomultiplier tube PMTH-R 928 using an external excitation source, 980 nm semiconductor laser. Upconverted CPLs were recorded on JASCO CPL-200 spectrophotometer with an external excitation source, 980 nm semiconductor laser. Fluorescence lifetime measurements were recorded on the same spectrometer using time-correlated single photon counting (TCSPC). X-ray diffraction (XRD) was achieved on Rigaku D/Max-2500 X-ray diffractometer (Japan) with Cu/Kα radiation (λ = 1.5406 Å). Scanning electron microscopy (SEM) was performed on a Hitachi S-4800 FE-SEM with an accelerating voltage of 10 kV. Before SEM measurements, the samples on silicon wafers were coated with a thin layer of Pt to increase the contrast. TEM was performed on Tecnai G2 20 S-TWIN at accelerating voltages of 200 kV, respectively. The samples were cast on carbon-coated Cu grids (unstained) and then evaporated under ambient conditions before the TEM measurements. FT-IR spectra were recorded on a JASCO FTIR-660 plus spectrophotometer with the resolution of 4 cm−1 at room temperature. Samples were first vacuum-dried and made into plates with KBr for FT-IR spectral measurements. Preparation of UCNPs/LGAm Gel. To produce the chiral luminescence nanocomposites supramolecular co-gels, different volumes of UCNPs (5 mg/mL) and 8 mg LGAm or DGAm were added to a capped test tube with DMF solution (300 μL), and the mixture was heated until the solid was dissolved completely. The solution was subsequently cooled down to room temperature under ambient conditions. After 30 min, the gel formed. The formation of co-gels was determined by the absence of flow of the solvent when the tube was inverted. Preparation of the HA Film. In brief, the filtered HA molecules were dissolved in toluene, the solution was added dropwise to the

Author Contributions ⊥

These authors contributed equally.

Notes

The authors declare no competing financial interest.

ACKNOWLEDGMENTS This work was supported by the Ministry of Science and Technology of the People’s Republic of China (2017YFA0206600, 2016YFA0203400), National Natural Science Foundation of China (21802027, 51673050), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB12020200), Key Research Program of Frontier Sciences, CAS, (QYZDJ-SSW-SLH044), and New Hundred-Talent Program research fund of the Chinese Academy of Sciences. REFERENCES (1) Sun, M.; Xu, L.; Qu, A.; Zhao, P.; Hao, T.; Ma, W.; Hao, C.; Wen, X.; Colombari, F. M.; de Moura, A. F.; Kotov, N. A.; Xu, C.; Kuang, H. Site-Selective Photoinduced Cleavage and Profiling of DNA by Chiral Semiconductor Nanoparticles. Nat. Chem. 2018, 10, 821−830. (2) Zinna, F.; Di Bari, L. Lanthanide Circularly Polarized Luminescence: Bases and Applications. Chirality 2015, 27, 1−13. (3) Song, F.; Wei, G.; Jiang, X.; Li, F.; Zhu, C.; Cheng, Y. Chiral Sensing for Induced Circularly Polarized Luminescence Using an Eu(III)-Containing Polymer and D- or L-Proline. Chem. Commun. 2013, 49, 5772−5774. (4) Iwamura, M.; Kimura, Y.; Miyamoto, R.; Nozaki, K. Chiral Sensing Using an Achiral Europium(III) Complex by Induced Circularly Polarized Luminescence. Inorg. Chem. 2012, 51, 4094− 4098. (5) Okutani, K.; Nozaki, K.; Iwamura, M. Specific Chiral Sensing of Amino Acids Using Induced Circularly Polarized Luminescence of Bis(diimine)dicarboxylic Acid Europium(III) Complexes. Inorg. Chem. 2014, 53, 5527−5537. (6) Imai, Y.; Nakano, Y.; Kawai, T.; Yuasa, J. A Smart Sensing Method for Object Identification Using Circularly Polarized Luminescence from Coordination-Driven Self-Assembly. Angew. Chem., Int. Ed. 2018, 57, 8973−8978. (7) Schadt, M. Liquid Crystal Materials and Liquid Crystal Displays. Annu. Rev. Mater. Sci. 1997, 27, 305−379. (8) Zinna, F.; Giovanella, U.; Di Bari, L. Highly Circularly Polarized Electroluminescence from a Chiral Europium Complex. Adv. Mater. 2015, 27, 1791−1795. F

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DOI: 10.1021/acsnano.8b08273 ACS Nano XXXX, XXX, XXX−XXX

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DOI: 10.1021/acsnano.8b08273 ACS Nano XXXX, XXX, XXX−XXX