Tunable Upconverted Circularly Polarized Luminescence in Cellulose

Jun 6, 2019 - Integrating chromophores into chiral photonic crystals to fabricate materials that exhibit circularly polarized luminescence (CPL) is pr...
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Cite This: ACS Appl. Mater. Interfaces 2019, 11, 23512−23519

Tunable Upconverted Circularly Polarized Luminescence in Cellulose Nanocrystal Based Chiral Photonic Films Wei Li,*,†,§ Mingcong Xu,†,§ Chunhui Ma,† Yushan Liu,† Jin Zhou,‡ Zhijun Chen,† Yonggui Wang,† Haipeng Yu,† Jian Li,† and Shouxin Liu*,† †

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Key Laboratory of Bio-Based Material Science and Technology of Ministry of Education, Northeast Forestry University, Harbin 150040, China ‡ CAS Key Laboratory of Nanosystem and Hierarchical Fabrication, National Center for Nanoscience and Technology (NCNST), Beijing 100190, China S Supporting Information *

ABSTRACT: Integrating chromophores into chiral photonic crystals to fabricate materials that exhibit circularly polarized luminescence (CPL) is promising as this method allows efficient manipulation of the spontaneous emission within photonic bandgaps (PBGs). However, tuning the wavelength of CPL and the dissymmetry factor (glum) in a convenient and accurate manner remains a significant challenge. Here, right-handed, tunable upconverted CPL (UC-CPL) emission was achieved by integrating multiple emissive, upconverting nanoparticles into cellulose nanocrystal based chiral photonic films that had tunable PBGs. Glycerol was used to tune the PBGs of the chiral photonic films, which yielded tunable UC-CPL emission at 450 and 620 nm with a tailored glum. Moreover, humidity responsive UC-CPL at blue wavelength was obtained from glycerol-composite photonic film, with a glum that ranged from −0.156 to −0.033. It was possible because the PBG and chirality of photonic composite was responded to the relative humidity. This work gives valuable insight into tunable and stimuli-responsive CPL photonic systems. KEYWORDS: upconverted circularly polarized luminescence, tunable, responsive, photonic band gap, cellulose nanocrystals

1. INTRODUCTION Circularly polarized luminescence (CPL) shows great potential as a probe to help understand excited-state chirality and for use in a range of practical photonic applications, including asymmetric synthesis,1,2 optical storage devices,3 biological probes4,5 and 3D displays.6 A variety of CPL materials have been reported, including small organic molecules,7−9 πconjugated polymers,10,11 chiral lanthanide complexes,12 aggregation-induced-emission gens13−15 and perovskite nanocrystals.16 To date, the main strategies used to produce CPL involve chiral blending,17,18 supramolecular assemblies19,20 and chiral liquid crystal encapsulation.21,22 However, these strategies result in a limited dissymmetry factor (glum) and unpredictable chirality.23 Hence, alternative strategies are required to ensure that CPL with defined and predictable properties can be achieved. By mimicking nature, self-assembled photonic films made from cellulose nanocrystals (CNCs) can selectively reflect circularly polarized light in a similar fashion to some crustaceans that achieve this through helically organized nanostructures.24,25 The intriguing properties of CNCs have inspired research into generating CPL by doping fluorescent chromophores into photonic cellulose films.26,27 Although this method provides a convenient and environmentally friendly way to obtain CPL materials, achieving CPL emission at © 2019 American Chemical Society

different wavelengths requires altering the type or amount of the fluorescent dopant. Moreover, since the chemical structure of a fluorescent dopant affects its interactions with the cellulose crystals within the film, the glum of the CPL is typically unpredictable. Only photons of a certain wavelength can only pass through a matched photonic bandgap (PBG) of the photonic cellulose film. The degree of overlap between the fluorescent emission and the PBG determines the glum value. Inspired by these two points, we hypothesized that the incorporation of multiple-emissive chromophores into a photonic cellulose film with an adjustable PBG, tunable CPL might be achieved simply by adjusting the PBG of chiral host. To this end, attention was paid to lanthanide-doped upconverting nanoparticles (UCNPs). Photon upconversion, the process in which low energy photons are absorbed and high energy photons are emitted, shows promise for use in photonic applications. For example, lanthanide-doped UCNPs can convert near-infrared (NIR) light into multiple UV−visible emission wavelengths owing to their rich energy level structures.28 In this work, we have combined NaYF4:TmYb UCNPs, which have multiple Received: April 4, 2019 Accepted: June 6, 2019 Published: June 6, 2019 23512

DOI: 10.1021/acsami.9b05941 ACS Appl. Mater. Interfaces 2019, 11, 23512−23519

Research Article

ACS Applied Materials & Interfaces emission wavelengths, with CNC-based chiral photonic films that have tunable and stimuli-responsive PBGs. This resulted in a material that exhibited finely controlled UC-CPL. The PBGs of these chiral photonic films can be precisely tuned using an external stimuli (glycerol).29 The photonic films are referred to as CNC-U, (glycerol, 0 g), G1-U (glycerol, 0.02 g), and G2-U (glycerol, 0.04 g) depending on their glycerol content. An illustration of the tunable UC-CPL emission (450 and 620 nm with tailored glum) from chiral photonic films following irradiation with NIR light is shown in Scheme 1a.

2. EXPERIMENTAL SECTION 2.1. Materials. All commercial reagents were used as received. CNCs29 and NaYF4:TmYb UCNPs were synthesized using reported procedures.30,31 2.2. Preparation of the UCNP@PVA Dispersion. PVA (0.1 g) was added to an aqueous dispersion of UCNPs (30 mL) with a mass ratio of 5 mg/mL, and then the mixture was stirred for 1 h at ambient temperature to give the UCNP@PVA dispersion. 2.3. Preparation of the Chiral Photonic Films. An aqueous dispersion of UCNP@PVA (5 mg/mL) and varying amounts of a glycerol solution (10 wt %) were added to a suspension of CNCs (3 wt %, 3 mL) with vigorous stirring for 5 h. UCNPs in the composites was 1 wt %, and CNC-U, G1-U, G2-U was named by the glycerol addition of 0, 0.02, 0.04 g, respectively. The composite suspension was cast in a rectangular plastic container (3 cm long by 3 cm wide) and allowed to evaporate at ambient temperature for 2−3 days, which resulted in iridescent photonic films (CNC-U, G1-U, G2-U). 2.4. Controlling the Relative Humidity. The humidityresponsive UC-CPL of the photonic films was examined by placing G1-U in a humidity chamber with relative humidity (RH) values of 33, 75, and 85%. This was adjusted using saturated anhydrous MgCl2, NaCl and KCl solutions, respectively. All samples remained in the chamber for 30 min and then their circular dichroism (CD) spectra, transmission spectra, and UC-CPL spectra were recorded. 2.5. Characterizations. Transmission electron microscopy (TEM) images of the UCNPs and CNCs were obtained using a JEM-1200EX microscope at an accelerating voltage of 120 kV. Scanning electron microscopy (SEM) images of the chiral photonic films were obtained using a Quanta 200 microscope (FEI, The Netherlands). High magnification SEM images of the photonic films were obtained on a JSM-7500F field emission scanning electron microscope. The zeta potential of a CNC suspension was measured using a Malvern Zetasizer Nano ZS90. Fourier transform infrared (FT-IR) spectra of the photonic samples were recorded on a Nicolet iS10 FT-IR instrument (Thermo Scientific, USA). Powder X-ray diffraction (PXRD) analysis was performed on a Bruker D8 ADVANCE X-ray diffractometer. Polarized optical microscopy (POM) images were obtained using a polarized light microscope (XPF-550C, Caikang Optics, China). UV−vis spectra of photonic films were performed on a Persee TU-1950 UV−vis spectrometer. The transmission spectra and CIE coordinates of the photonic films (CNC-U, G1-U and G2-U) were recorded on a UV−vis−NIR spectrometer (Ocean Optics) with the surfaces of photonic films being perpendicular to the incident beam. Fluorescence spectra and lifetimes of the UCNP@PVA dispersion and photonic films (CNC-U, G1-U and G2-U) were recorded on a FLS980 fluorescence

Scheme 1. (a) Illustration Showing the Tunable UC-CPL Emission (450 and 620 nm) with a Tailored glum That Was Obtained from the PBGs-Tunable Chiral Photonic Films; (b) Illustration Showing the Humidity Responsive UC-CPL Emission at Blue Wavelength with a Tailored glum from a Glycerol-Composite Photonic Film

The chiral photonic films were fabricated by the co-assembly of CNCs, UCNPs and glycerol. Moreover, the glycerolcomposite film, G1-U, exhibited a humidity-responsive UCCPL blue emission, as shown in Scheme 1b. The value of the glum could be tuned from −0.156 to −0.033.

Figure 1. (a) TEM image of the UCNPs. (b) TEM image of the CNCs. (c,d) Side view SEM images of the chiral photonic films: (c) CNC-U and (d) G1-U. (e,f) Cross-sectional SEM images of the chiral photonic films: (e) CNC-U and (f) G1-U. (g,h) High magnification SEM images showing the cross-section of fractures within the chiral photonic films: (g) CNC-U and (h) G1-U. 23513

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Figure 2. (a) UV−vis spectra of the CNC-U, G1-U and G2-U photonic films. (b) CD spectra of the CNC-U, G1-U and G2-U photonic films. spectrophotometer using an external laser (974 nm). CD spectra were measured on a JASCO J-1500 CD spectrometer. UC-CPL spectra were recorded on a JASCO CPL-200 spectrophotometer with an external laser (974 nm).

interactions. Therefore, the FT-IR analysis revealed that hydrogen bond interactions were likely to be important in the co-assembly process. PXRD analysis was also used to examine the photonic cellulose films. Diffraction peaks that were characteristic of the cellulose I crystal were observed at 16.5° and 22.5° in all samples (Figure S8). This result confirmed that the addition of UCNP@PVA, glycerol or both did not destroy the cellulosic crystal structure.32 Moreover, additional peaks that were characteristic of the lanthanidedoped UCNPs were observed in the composite films. UV−vis spectra was used as a quantitative analysis of the structural coloration in these iridescent films. The maximum extinction wavelength was 414, 509 and 639 nm for CNC-U, G1-U and G2-U, respectively, corresponding to distinct coloration in these photonic films. CD was used to determine the intrinsic charity of the photonic nanocomposites (Figure 2). Strong, positive cotton effects appeared in all samples, which was consistent with the left-handed microstructures observed in the SEM images. These results indicated that these photonic films have strong left-handed intrinsic chirality. Moreover, the peak wavelength in the CD spectra red-shifted from 410 to 638 nm as the glycerol content was increased, which confirmed that the chirality of ground state could be tuned in the visible spectrum. POM was used to understand the formation of the chiral photonic structures by monitoring the anisotropic liquid crystal mesogens. During the EISA process, anisotropic baby tactoids were created from the isotropic composite suspension as the CNC concentration was increased over the critical value (Figure 3a). This can be attributed to electrostatic repulsion

3. RESULTS AND DISCUSSION 3.1. Preparation of CNC Based Chiral Photonic Films. NaYF4:TmYb UCNPs were synthesized using published procedures.30,31 The as-prepared UCNPs had an average diameter of 50 nm (Figure 1a). PVA was used as a coating material to give hydrophilic UCNPs (UCNP@PVA). Rod-like CNCs with a high aspect ratio were prepared via traditional H2SO4 hydrolysis (Figure 1b). The UCNPs were found to be randomly distributed in the colloid CNC suspension (Figure S1). The negatively-charged CNCs (zeta potential, −40.7 mV) created a sufficiently charged environment for self-assembly to occur (Figure S2). Transparent cellulose films that encapsulated the UCNP@PVA exhibited iridescent colors and upconverted photoluminescence were obtained via an evaporation-induced self-assembly (EISA) from the homogeneous CNC/UCNPs dispersion (Figures S3 and S4). Redshifted structural colors of these photonic films was tuned by the glycerol content in the composites (Figure S5), which was consistent with the CIE coordinates of these iridescent films (Figure S6). Chiral photonic microstructures within these photonic films were subsequently investigated by SEM. Side view SEM images showed that periodically aligned chiral nematic layers with a helical pitch of several hundred nanometers were present in both CNC-U and G1-U (Figure 1c,d), corresponding to the visible iridescent colors to the naked eyes. The helical pitch increased upon addition of glycerol, which was consistent with the red-shift in the iridescent color of these photonic films. Cross-sectional views of fractures showed left-handed twisting orientations (Figure 1e,f), which indicated that the samples had left-handed helical structures. UCNPs were observed in the chiral nematic layers in the high magnification SEM images of the photonic films (Figure 1g,h), which showed that the UCNPs were indeed encapsulated in the CNC chiral nematic host. FT-IR was used to understand the interactions in the photonic films (Figure S7). The absorption bands between 3300 and 3500 cm−1 in the spectrum of the CNC film broadened after the addition of the UCNP@PVA. This can be attribute to the interactions between the O−H groups of the CNCs and UCNP@PVA that decreased the intermolecular hydrogen bond interactions between the CNCs. However, following the addition of glycerol, the O−H stretching vibrations narrowed owing to the increased hydrogen bond

Figure 3. (a−c) POM images of the CNC-U composite suspension that contained increasing CNC concentration during the EISA process.

and coulombic attraction.33 The baby tactoids then grew and merged to form larger tactoids with stronger birefringence (Figure 3b). Finally, fingerprint patterns with uniform pitches were observed (Figure 3c), corresponding to the chiral nematic structures observed in the SEM images. These results revealed that the upconverted luminescent guest was effectively 23514

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Figure 4. (a) Upconverted luminescence spectra from the chiral photonic films (CNC-U, G1-U G2-U). (b) Schematic diagram showing the energy levels involved in the photon upconversion of the NaYF4:TmYb UCNPs. (c) Upconverted luminescent lifetime decay curves of the 450 nm emission from the chiral photonic films. (d) Upconverted luminescent lifetime decay curves of the 646 nm emission from the chiral photonic films.

Figure 5. (a) Photographs of the CNC-U, G1-U and G2-U films observed under natural light, a L-CPF and a R-CPF. (b) POM images of the CNC-U, G1-U and G2-U films taken under L-CPF and R-CPF.

(Figure S9), except that the peak intensities were a little different. The upconverted photoluminescence lifetime decay behavior of the photonic films at 450 and 646 nm were fitted using double exponential functions (Figure 4c,d, respectively). The lifetimes of the CNC-U, G1-U and G2-U films at 450 nm were 192, 182 and 189 μs, respectively. These values were equal to the lifetime of the UCNP@PVA dispersion (188 μs, Figure S10a). The lifetimes of the CNC-U, G1-U and G2-U films at 646 nm were 453, 458 and 473 μs, respectively. Similarly, these values were also close to that of the UCNP@PVA dispersion (490 μs, Figure S10b). These results indicated that the CNC based film is a suitable chiral photonic host for the upconverting luminophores.

encapsulated in the cholesteric liquid crystal host, as has been reported for other NPs,34,35 which allowed CPL to occur. 3.2. Upconverted Photoluminescence Performance of the Chiral Photonic Films. The upconverted photoluminescence properties of the chiral photonic films are shown in Figure 4. When excited at 974 nm, the photonic films underwent emission at 450, 474 and 646 nm within the visible spectrum (Figure 4a). These emission peaks were attributed to 1 D2 → 3F4 (four-photon process), 1G4 → 3H6 (three-photon process), and 1G4 → 3F4 (three-photon process) transitions of the Tm3+ ions (Figure 4b), respectively. The peak positions in upconverted photoluminescence spectra of the chiral photonic films were identical to that of the UCNP@PVA dispersion 23515

DOI: 10.1021/acsami.9b05941 ACS Appl. Mater. Interfaces 2019, 11, 23512−23519

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Figure 6. Tunable UC-CPL emission from the chiral photonic films. (a−c) CPL spectra and DC curves of the chiral photonic films: (a) CNC-U, (b) G1-U, and (c) G2-U. (d) Transmission spectra of the chiral photonic films. (e) Illustration showing the tunable UC-CPL emission that was regulated by the PBGs of the chiral photonic films.

3.3. CPL Reflection in the Chiral Photonic Films. CNC based chiral photonic films can reflect circularly polarized light according to previous report.36 The ability of these photonic films to reflect CPL was investigated by photographing the films using circularly polarizing filters (CPF) on a black background (Figure 5a). The iridescent colors from all films were brighter when observed through the left-handed CPF (LCPF), when compared with the right-handed CPF (R-CPF). Moreover, the POM images of the photonic films observed through the L-CPF and R-CPF were clearly different (Figure 5b). The birefringence of the cholesteric liquid crystals was not observed when taken using the R-CPF. All these points demonstrated that the selective reflection of L-CPL in chiral photonic films owing to their left-handed chiral photonic structures. 3.4. Tunable UC-CPL Emission from the Chiral Photonic Films. The UC-CPL emission from G1-U, G2-U and CNC-U was examined following excitation at 974 nm. Since UCNPs can convert NIR to UV, blue and red emission, the samples exhibited multiple right-handed UC-CPL emission peaks, as evidenced by negative CPL signals at a variety of wavelengths (Figure 6a−c). Specifically, the UC-CPL emission from CNC-U was dominated by a fluorescent signal at 450 nm, G1-U exhibited dual-emission UC-CPL that included both blue (450 nm) and red emission (620 nm), while the primary UC-CPL emission from G2-U occurred at 620 nm. Although these films exhibited different CPL emission, their DC spectra were almost identical. This suggested that the differences in their CPL spectra were caused by changes in the chiroptical properties of the photonic host rather than the fluorescent properties of the upconverting guest. The glum was used as an indicator of CPL, according to the following equation glum = 2 × (IL − IR )/(IL + IR )

where IL and IR indicate the intensity of L-CPL and R-CPL, respectively.37 The |glum| values at 450 nm were 0.038, 0.028, 0.019 for CNC-U, G1-U and G2-U, respectively. However, the |glum| values at 620 nm were 0.021, 0.025 and 0.071 in the redshifted photonic films, respectively (Figure S11). This result confirmed that tuning the PBGs of the photonic films did indeed allow their UC-CPL emission to be tuned with a tailored glum. To determine the mechanism of the PBG-tuned UC-CPL emission, the transmission spectra of the films were analyzed (Figure 6d). CNC-U, G1-U and G2-U exhibited PBG peak maxima at 413, 512 and 634 nm, respectively. This result suggested that the addition of glycerol tuned the PBGs of these films. An illustration showing photon emission from the chiral photonic crystals is shown in Figure 6e. Photon propagation is forbidden when the photon emission occurs inside the PBGs of the photonic crystal, while spontaneous emission can occur from photons outside the PBGs.38 Specifically, the forbidden nature of the L-CPL emission was a major factor in the PBGs of chiral photonic films, which was consistent with the transmission spectra obtained when probed with L-CPL and R-CPL (Figure S12). Hence, tunable right-handed UC-CPL emission from the photonic films was realized by the selective chiral amplification of the PBG effect. For CNC-U, upconverted fluorescent emission at 450 nm overlapped with its PBG. Owing to the forbidden propagation of the L-CPL emission within the PBG that reduced IL at 450 nm, a greater | g lum | value was observed. However, the upconverted fluorescence at 620 nm was far away from its PBG, and so the |glum| value was much smaller. The PBG effect can also explain the glycerol-tuned UC-CPL emission from the other photonic films. This work has shown that glycerol can be used to tune the ratio of the CPL emission (blue emission/red emission) via tuning of the PBGs of these films.

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DOI: 10.1021/acsami.9b05941 ACS Appl. Mater. Interfaces 2019, 11, 23512−23519

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Figure 7. Humidity-responsive UC-CPL from the glycerol-composite photonic film G1-U. (a) CPL spectra of G1-U at different RH. (b) The glum distribution curves of G1-U at different RH. (c) Transmission spectra of G1-U at different RH. (d) CD spectra of G1-U at different RH.

3.5. Humidity-Responsive UC-CPL from the Chiral Photonic Films. Interestingly, a humidity-responsive UCCPL emission was observed from the glycerol-composite photonic film. We have previously shown that the chiroptical properties of CNC/glycerol composite films are sensitive to humidity because glycerol is strongly hygroscopic.26 Therefore, the glycerol composite film, G1-U, was exposed to different RH and then the UC-CPL was examined. When the RH was increased from 33 to 85%, the CPL peaks decreased significantly (Figure 7a). The |glum| value also decreased from 0.156 to 0.033 with the increased RH, echoing the declining CPL peaks (Figure 7b). Slight changes in the DC spectra suggested that the humidity-sensitive CPL was not related to the upconverting guest (Figure S13). Humidity-induced bathochromic shifts of the PBGs of G1-U explained this phenomenon (Figure 7c). The peak maxima of PBG from G1U red-shifted from 505 to 581 nm as the RH was increased. The decreased overlap of the upconverted fluorescence at 450 nm with the red-shifted PBGs allowed L-CPL emission to occur within the PBG and increased IL at 450 nm. Therefore, a smaller |glum| value was observed. An alternative explanation relates to the decreased helical sense in the photonic composite with increasing RH. The CD peak intensity decreased significantly as the RH was increased from 33 to 85%, as shown in Figure 7d. As a result, the decreased helical sense at higher RH allowed L-CPL to occur over the entire PBGs, which limited the R-CPL emission from the photonic films.

the selective chiral amplification of UC-CPL emission. Moreover, the glycerol composite film exhibited a stimuliresponsive UC-CPL at 450 nm with |glum| values changed from 0.156 to 0.033 because of the humidity-sensitive PBGs and the handedness of the photonic host. This strategy of using one dimensional chiral photonic crystals for the production of tunable UC-CPL emission provides a simple and efficient method for the fabrication of smart CPL devices by mimicking nature.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acsami.9b05941. Fluorescence spectra and lifetime decays of the UCNPs; the zeta potential of the CNCs; time-lapse photographs of the EISA process of CNC-U; photographs, CIE coordinates, FT-IR, PXRD and glum curves of chiral photonic films; transmission spectra of CNC-U, G1-U and G2-U probed with L-CPL and R-CPL; DC spectra of the glycerol-composite film G1-U at different RH (PDF)

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected] (W.L.). *E-mail: [email protected] (S.L.).

4. CONCLUSION In summary, we have demonstrated tunable UC-CPL emission with tailored glum by modulating the PBGs of CNC-based chiral photonic films. These films were fabricated via the coassembly of CNCs, glycerol and UCNPs. The PBGs of the films were precisely regulated by the controlled addition of glycerol, which resulted in tunable blue and red UC-CPL emission with controllable glum. The PBG effect is crucial for

ORCID

Wei Li: 0000-0002-3008-9865 Chunhui Ma: 0000-0001-9590-3891 Zhijun Chen: 0000-0001-7203-5788 Yonggui Wang: 0000-0002-5135-1367 Haipeng Yu: 0000-0003-0634-7913 Shouxin Liu: 0000-0002-0491-8885 23517

DOI: 10.1021/acsami.9b05941 ACS Appl. Mater. Interfaces 2019, 11, 23512−23519

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Luminogens with Amplified Chirality and Delayed Fluorescence. Adv. Funct. Mater. 2018, 28, 1800051. (15) Li, J.; Yang, C.; Huang, C.; Wan, Y.; Lai, W.-Y. Tuning Circularly Polarized Luminescence of an AIE-Active Pyrene Luminogen from Fluidic Solution to Solid Thin Film. Tetrahedron Lett. 2016, 57, 1256−1260. (16) Shi, Y.; Duan, P.; Huo, S.; Li, Y.; Liu, M. Endowing Perovskite Nanocrystals with Circularly Polarized Luminescence. Adv. Mater. 2018, 30, 1705011. (17) Geng, Y.; Trajkovska, A.; Culligan, S. W.; Ou, J. J.; Chen, H. M. P.; Katsis, D.; Chen, S. H. Origin of Strong Chiroptical Activities in Films of Nonafluorenes with a Varying Extent of Pendant Chirality. J. Am. Chem. Soc. 2003, 125, 14032−14038. (18) Cheng, J.; Hao, J.; Liu, H.; Li, J.; Li, J.; Zhu, X.; Lin, X.; Wang, K.; He, T. Optically Active CdSe-Dot/CdS-Rod Nanocrystals with Induced Chirality and Circularly Polarized Luminescence. ACS Nano 2018, 12, 5341−5350. (19) Yang, D.; Duan, P.; Zhang, L.; Liu, M. Chirality and Energy Transfer Amplified Circularly Polarized Luminescence in Composite Nanohelix. Nat. Commun. 2017, 8, 15727. (20) Yang, D.; Duan, P.; Liu, M. Dual Upconverted and Downconverted Circularly Polarized Luminescence in Donor-Acceptor Assemblies. Angew. Chem., Int. Ed. 2018, 57, 9357−9361. (21) San Jose, B. A.; Yan, J.; Akagi, K. Dynamic Switching of the Circularly Polarized Luminescence of Disubstituted Polyacetylene by Selective Transmission through a Thermotropic Chiral Nematic Liquid Crystal. Angew. Chem., Int. Ed. 2014, 53, 10641−10644. (22) Yang, X.; Han, J.; Wang, Y.; Duan, P. Photon-Upconverting Chiral Liquid Crystal: Significantly Amplified Upconverted Circularly Polarized Luminescence. Chem. Sci. 2019, 10, 172−178. (23) Han, J.; Guo, S.; Lu, H.; Liu, S.; Zhao, Q.; Huang, W. Recent Progress on Circularly Polarized Luminescent Materials for Organic Optoelectronic Devices. Adv. Opt. Mater. 2018, 6, 1800538. (24) Sharma, V.; Crne, M.; Park, J. O.; Srinivasarao, M. Structural Origin of Circularly Polarized Iridescence in Jeweled Beetles. Science 2009, 325, 449−451. (25) Chiou, T.-H.; Kleinlogel, S.; Cronin, T.; Caldwell, R.; Loeffler, B.; Siddiqi, A.; Goldizen, A.; Marshall, J. Circular Polarization Vision in a Stomatopod Crustacean. Curr. Biol. 2008, 18, 429−434. (26) Zheng, H.; Li, W.; Li, W.; Wang, X.; Tang, Z.; Zhang, S. X.-A.; Xu, Y. Uncovering the Circular Polarization Potential of Chiral Photonic Cellulose Films for Photonic Applications. Adv. Mater. 2018, 30, 1705948. (27) Zheng, H.; Ju, B.; Wang, X.; Wang, W.; Li, M.; Tang, Z.; Zhang, S. X.-A.; Xu, Y. Circularly Polarized Luminescent Carbon Dot Nanomaterials of Helical Superstructures for Circularly Polarized Light Detection. Adv. Opt. Mater. 2018, 6, 1801246. (28) Li, X.; Zhang, F.; Zhao, D. Lab on Upconversion Nanoparticles: Optical Properties and Applications Engineering via Designed Nanostructure. Chem. Soc. Rev. 2015, 44, 1346−1378. (29) Xu, M.; Li, W.; Ma, C.; Yu, H.; Wu, Y.; Wang, Y.; Chen, Z.; Li, J.; Liu, S. Multifunctional Chiral Nematic Cellulose Nanocrystals/ Glycerol Structural Colored Nanocomposites for Intelligent Responsive Films, Photonic Inks and Iridescent Coatings. J. Mater. Chem. C 2018, 6, 5391−5400. (30) He, S.; Krippes, K.; Ritz, S.; Chen, Z.; Best, A.; Butt, H.-J.; Mailänder, V.; Wu, S. Ultralow-Intensity Near-Infrared Light Induces Drug Delivery by Upconverting Nanoparticles. Chem. Commun. 2015, 51, 431−434. (31) Ma, P.; Xiao, H.; Li, X.; Li, C.; Dai, Y.; Cheng, Z.; Jing, X.; Lin, J. Rational Design of Multifunctional Upconversion Nanocrystals/ Polymer Nanocomposites for Cisplatin (IV) Delivery and Biomedical Imaging. Adv. Mater. 2013, 25, 4898−4905. (32) Nishiyama, Y.; Sugiyama, J.; Chanzy, H.; Langan, P. Crystal Structure and Hydrogen Bonding System in Cellulose Iα from Synchrotron X-ray and Neutron Fiber Diffraction. J. Am. Chem. Soc. 2003, 125, 14300−14306.

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W.L. and M.X. contributed equally to this work.

Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was financially supported by the National Natural Science Foundation of China (31890773, 31570567, 31500467) and the Fundamental Research Funds for the Central Universities (2572017ET02, 2572017CB12).

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REFERENCES

(1) Sato, I.; Sugie, R.; Matsueda, Y.; Furumura, Y.; Soai, K. Asymmetric Synthesis Utilizing Circularly Polarized Light Mediated by the Photoequilibrium of Chiral Olefins in Conjunction with Asymmetric Autocatalysis. Angew. Chem., Int. Ed. 2004, 43, 4490− 4492. (2) Wu, S.-T.; Cai, Z.-W.; Ye, Q.-Y.; Weng, C.-H.; Huang, X.-H.; Hu, X.-L.; Huang, C.-C.; Zhuang, N.-F. Enantioselective Synthesis of a Chiral Coordination Polymer with Circularly Polarized Visible Laser. Angew. Chem. 2014, 126, 13074−13078. (3) Wagenknecht, C.; Li, C.-M.; Reingruber, A.; Bao, X.-H.; Goebel, A.; Chen, Y.-A.; Zhang, Q.; Chen, K.; Pan, J.-W. Experimental Demonstration of a Heralded Entanglement Source. Nat. Photonics 2010, 4, 549−552. (4) 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. (5) Chen, C.; Chen, J.; Wang, T.; Liu, M. Fabrication of Helical Nanoribbon Polydiacetylene via Supramolecular Gelation: Circularly Polarized Luminescence and Novel Diagnostic Chiroptical Signals for Sensing. ACS Appl. Mater. Interfaces 2016, 8, 30608−30615. (6) Srivastava, A. K.; Zhang, W.; Schneider, J.; Rogach, A. L.; Chigrinov, V. G.; Kwok, H.-S. Photoaligned Nanorod Enhancement Films with Polarized Emission for Liquid-Crystal-Display Applications. Adv. Mater. 2017, 29, 1701091. (7) Sánchez-Carnerero, E. M.; Agarrabeitia, A. R.; Moreno, F.; Maroto, B. L.; Muller, G.; Ortiz, M. J.; de la Moya, S. Circularly Polarized Luminescence from Simple Organic Molecules. Chem. Eur. J. 2015, 21, 13488−13500. (8) Li, M.; Zhang, C.; Fang, L.; Shi, L.; Tang, Z.; Lu, H.-Y.; Chen, C.-F. Chiral Nanoparticles with Full-Color and White CPL Properties Based on Optically Stable Helical Aromatic Imide Enantiomers. ACS Appl. Mater. Interfaces 2018, 10, 8225−8230. (9) Li, J.; Yang, C.; Peng, X.; Qi, Q.; Li, Y.; Lai, W.-Y.; Huang, W.; Huang, W. Stimuli-Responsive Circularly Polarized Luminescence from an Achiral Perylenyl Dyad. Org. Biomol. Chem. 2017, 15, 8463− 8470. (10) Haraguchi, S.; Numata, M.; Li, C.; Nakano, Y.; Fujiki, M.; Shinkai, S. Circularly Polarized Luminescence from Supramolecular Chiral Complexes of Achiral Conjugated Polymers and a Neutral Polysaccharide. Chem. Lett. 2009, 38, 254−255. (11) Li, J.; Peng, X.; Huang, C.; Qi, Q.; Lai, W.-Y.; Huang, W. Control of circularly polarized luminescence from a boron ketoiminate-based π-conjugated polymer via conformational locks. Polym. Chem. 2018, 9, 5278−5285. (12) Zinna, F.; Giovanella, U.; Bari, L. D. Highly Circularly Polarized Electroluminescence from a Chiral Europium Complex. Adv. Mater. 2015, 27, 1791−1795. (13) Han, J.; You, J.; Li, X.; Duan, P.; Liu, M. Full-Color Tunable Circularly Polarized Luminescent Nanoassemblies of Achiral AIE gens in Confined Chiral Nanotubes. Adv. Mater. 2017, 29, 1606503. (14) Song, F.; Xu, Z.; Zhang, Q.; Zhao, Z.; Zhang, H.; Zhao, W.; Qiu, Z.; Qi, C.; Zhang, H.; Sung, H. H. Y.; Williams, I. D.; Lam, J. W. Y.; Zhao, Z.; Qin, A.; Ma, D.; Tang, B. Z. Highly Efficient Circularly Polarized Electroluminescence from Aggregation-Induced Emission 23518

DOI: 10.1021/acsami.9b05941 ACS Appl. Mater. Interfaces 2019, 11, 23512−23519

Research Article

ACS Applied Materials & Interfaces (33) Wang, P.-X.; Maclachlan, M. J. Liquid Crystalline Tactoids: Ordered Structure, Defective Coalescence and Evolution in Confined Geometries. Philos. Trans. R. Soc., A 2018, 376, 20170042. (34) Liu, Q.; Campbell, M. G.; Evans, J. S.; Smalyukh, I. I. Orientationally Ordered Colloidal Co-dispersions of Gold Nanorods and Cellulose Nanocrystals. Adv. Mater. 2014, 26, 7178−7184. (35) Nguyen, T.-D.; Hamad, W. Y.; MacLachlan, M. J. Near-IRSensitive Upconverting Nanostructured Photonic Cellulose Films. Adv. Opt. Mater. 2017, 5, 1600514. (36) Hiratani, T.; Hamad, W. Y.; MacLachlan, M. J. Transparent Depolarizing Organic and Inorganic Films for Optics and Sensors. Adv. Mater. 2017, 29, 1606083. (37) Richardson, F. S.; Riehl, J. P. Circularly Polarized Luminescence Spectroscopy. Chem. Rev. 1977, 77, 773−792. (38) López, C. Materials Aspects of Photonic Crystals. Adv. Mater. 2003, 15, 1679−1704.

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DOI: 10.1021/acsami.9b05941 ACS Appl. Mater. Interfaces 2019, 11, 23512−23519