Amplifying persistent luminescence in heavily doped nanopearls for bioimaging and solar-to-chemical synthesis

doi:10.21203/rs.3.rs-5192505/v1

Download PDF

Article

Amplifying persistent luminescence in heavily doped nanopearls for bioimaging and solar-to-chemical synthesis

https://doi.org/10.21203/rs.3.rs-5192505/v1

This work is licensed under a CC BY 4.0 License

Version 1

posted

You are reading this latest preprint version

Lanthanides are widely co-doped in persistent luminescence phosphors to elevate defect concentration and enhance luminescence efficiency. However, the deleterious cross-relaxation between activators and lanthanides inevitably quench persistent luminescence, particularly in heavily doped phosphors. Herein, we reported a core-shell engineering strategy to minimize the unwanted cross-relaxation but retain the charge-trapping capacity of heavily doped persistent luminescence phosphors by confining the activators and lanthanides in the core and shell, respectively. As a proof of concept, we prepared a series of codoped ZnGa₂O₄:Cr, Ln (CD-Ln, Ln = Nd, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb) and core-shell structured ZnGa₂O₄:Cr@ZnGa₂O₄:Ln (CS-Ln) nanoparticles. First-principle investigations suggested that lanthanide doping elevated the electron trap concentration for enhanceing persistent luminescence, but the energy transfer (ET) from Cr³⁺ to Ln³⁺ ions quenched the persistent luminescence. The spatial separation of Cr³⁺ and Ln³⁺ ions in the core-shell structured CS-Ln nanoparticles suppressed the ET from Cr³⁺ to Ln³⁺. Due to the efficient suppression of deleterious ET, the optimal doping concentration of Ln in CS-Ln was elevated 50 times compared to CD-Ln. Moreover, the persistent luminescence intensity of CS-5%Ln was up to 60 times that of the original ZnGa₂O₄:Cr. The CS-5%Ln displayed significantly improved signal-to-noise ratios in bioimaging. Further, the CS-Ln was interfaced with the lycopene-producing bacteria Rhodopseudomonas Palustris for solar-to-chemical synthesis and the lycopene productivity was increased by 190%. This work provides a reliable solution to fulfill the potential of lanthanides in enhancing persistent luminescence and opens opportunities for persistent luminescence phosphors in biomedicine and solar-to-chemical synthesis.

Biological sciences/Biochemistry

Biological sciences/Chemical biology

Persistent luminescence

Lanthanide

Bioimaging

Near-infrared light

Solar energy

Persistent luminescence phosphors (PLPs) can store the excitation energy in crystal defects and continuously release the trapped energy in forms such as luminescence after excitation ceases.^1–4 In the past years, the long-lived electrons and the accompanying persistent luminescence in PLPs have been widely explored in areas including biomedicine,^5–7 photocatalysis,^8,9 solar cells,¹⁰ LEDs¹¹, and decoration.¹² PLPs have brought extraordinary advantages to these areas. For instance, PLPs can easily avoid tissue autofluorescence and improve bioimaging sensitivity^13–15 Moreover, PLPs can produce sustained therapeutic activity after a single dose of light irradiation since the energy trapped in PLPs can be continuously released to produce therapeutic molecules such as reactive oxygen species.^16–18 Despite the many virtues, there still exists formidable challenges that impede the transformation of PLPs into real-world applications. One of the chief challenges is the weak persistent luminescence intensity of PLPs, particularly the visible and near-infrared (NIR) light-activated ones.^19–22

Persistent luminescence relies on crystal defects to trap charge carriers.^1,2 Due to their fascinating optical properties,^23,24 lanthanides have long been co-doped into PLPs to enrich the defect density for enhancing persistent luminescence.^1,25–27 Lanthanide doping can produce traps to store the photo-excited electrons or holes and the recombination of the trapped electron-hole pairs after excitation ceases promotes the generation of persistent luminescence.²⁸ The past years have witnessed a rapid development of lanthanide-co-doped PLPs with improved luminescence efficiencies.^28–30 Although the lanthanide co-dopant can increase the defect density, the deleterious cross-relaxation between activators and lanthanides inevitably quench persistent luminescence (Fig. 1a). Specifically, the ladder-like electronic states of lanthanides can extract the excitation energy from the matched excited states of activators,³¹ followed by depleting the excitation energy non-radiatively at lattice or surface defects.³² The unwanted cross-relaxation gets severe upon elevating the doped concentration of lanthanides,^33–35 which results in the quenching of persistent luminescence intensity. Due to such inherent limitations, a low doping concentration of lanthanides in PLPs has to be implemented to balance the beneficial and detrimental effects of lanthanides. The low doping level of lanthanides means that a limited number of defects are introduced, thus only limited enhancement of persistent luminescence can be achieved. Deleterious cross-relaxation is the key roadblock to maximizing the potential of lanthanides in improving persistent luminescence efficiency.

Herein we demonstrate the possibility of maximizing the potential of lanthanide doping in improving the persistent luminescence efficiency by circumventing the deleterious cross-relaxation between activators and lanthanides. In our design, core-shell structured persistent luminescence nanoparticles (PLNPs) were constructed, in which the activators and heavily doped lanthanides are spatially confined into the core and shell region, respectively (Fig. 1b). The spatial separation of activators and lanthanides in PLNPs not only effectively minimize the serious cross-relaxation effect but also elevates the doped amounts of lanthanides to increase the charge trapping capacity. As a proof of concept, the classic zinc gallate ZnGa₂O₄:Cr (ZGO) PLNPs with near-infrared (NIR) emission was designed into core-shell structure ZnGa₂O₄:Cr@ZnGa₂O₄:Ln (CS-Ln). The optimal doping concentration of lanthanides was increased by about 50-fold compared to the traditionally co-doped ZnGa₂O₄:Cr,Ln (CD-Ln), and the persistent luminescence intensity of CS-Ln was up to 60 times that of ZGO. The core-shell-engineered CS-Ln PLNPs displayed good promise in bioimaging with a high signal-to-background ratio. Further, the long-lived electrons and broad UV-visible absorption promised the CS-Ln PLNPs in solar-to-chemical synthesis. We demonstrated the great potential of the PLNPs for improving the productivity of fine chemicals in microbial cell factories. Our finding paves a reliable way to enhance the persistent luminescence efficiency and it can further open new opportunities for PLNPs in phototheranostics and solar-to-chemical conversion.

Deleterious cross-relaxation in CD-Ln PLNPs

We first investigated the change of persistent luminescence in CD-Ln PLNPs with gradually elevated Ln³⁺ concentration. CD-Eu PLNPs with varied Eu³⁺ doping (0.05-10%) were used as the model to show the persistent luminescence quenching caused by the deleterious cross-relaxation between Cr³⁺ and Eu³⁺ (Fig. 2a).^36–38 Transmission electron microscopy (TEM) images and X-ray diffraction patterns show the good homogeneity and high crystallinity of the prepared CD-Eu PLNPs (Extended Data Figs. 1a and 1b). Elemental mapping images show the homogeneous distribution of Zn, Ga, O, Cr, and Eu across the CD-Eu nanoparticle (Fig. 2b). All of the Eu³⁺-doped PLNPs display persistent luminescence emission at around 695 nm, which is indexed to the ²E→⁴A₂ transition of the activator Cr³⁺ (Fig. 2c and Extended Data Fig. 1d).²⁰ Transient luminescence lifetime measurement was employed to elucidate the influence of Eu³⁺ doping on the luminescence of Cr³⁺. The transient luminescence lifetime of CD-Eu increases from 0.922 ms to 1.542 ms with increasing the doped amount of Eu³⁺ from 0 to 0.1% (Fig. 2d), showing the improvement of luminescence efficiency by lightly-doped Eu³⁺. However, further increasing the amount of Eu to 5% in CD-Eu leads to the decrease of luminescence lifetime to 0.296 ms, which suggests the occurrence of luminescence quenching in heavily doped PLNPs.³⁹ Persistent luminescence decay curves further confirm the decrease of afterglow intensity in heavily doped CD-5%Eu (Fig. 2e). The IVIS optical imaging system was employed to study the persistent luminescence decay of CD-Eu in detail. After illumination by a commercial 550 nm LED, the persistent luminescence intensity and the decay time of CD-Eu PLNPs increase first and then decrease with raising the doped amount of Eu³⁺ (Fig. 2f and Extended Data Fig. 1e). A similar quenching of persistent luminescence in heavily-doped CD-Eu is also evidenced in CD-Eu PLNPs pre-charged by 254 nm UV light (Supplementary Fig. S1).

To gain insight into the mechanisms behind the initial enhancement and subsequent quenching of persistent luminescence in CD-Eu with increasing Eu³⁺ dopant concentration, we performed the first-principle investigations on the defect formation in doped ZnGa₂O₄ and the electronic structures of Cr³⁺ and Eu³⁺ ions in ZnGa₂O₄. The calculated formation energies of the intrinsic defects in ZnGa₂O₄ and extrinsic Eu dopants at Ga and Zn sites reveal that the Fermi energy level shifts by ~ 0.5 eV towards lower energy after Eu³⁺ doping (Fig. 2g). Consequently, the formation energies of oxygen vacancy (V_O) and antisite defect Ga_Zn decrease, suggesting the elevated concentrations of V_O and Ga_Zn accompany Eu³⁺ doping. Electron paramagnetic resonance (EPR) spectroscopy further shows that the amount of V_O in ZGO is significantly elevated by Eu³⁺ doping (Fig. 2h). Since V_O and Ga_Zn defects are important electron traps in ZGO,^2,13,19 lightly doped Eu³⁺ enhances the persistent luminescence of CD-Eu nanoparticles by enlarging their charge trapping capacity. We further explored the cross-relaxation between Cr³⁺ and Eu³⁺ ions in ZnGa₂O₄. The total and partial density of states for pure and Cr³⁺/Eu³⁺-doped ZnGa₂O₄ were evaluated using the hybrid PBE0 functional (Extended Data Figs. 2a and 2b). The calculated band gap of the ZnGa₂O₄ host is 4.91 eV, which aligns well with the experimental range of 4.4-5.0 eV.⁴⁰ For Eu³⁺ dopants at both Zn²⁺ and Ga³⁺ sites, the first six occupied 4f orbitals with majority spin are deeply embedded in the valence band (VB) (Extended Data Fig. 2b). The seventh unoccupied orbital of Eu³⁺ at Ga³⁺ sites appears closer to the conduction band (CB) than Eu³⁺ at the Zn²⁺ site in the band gap. The remaining unoccupied 4f orbitals with minority spin are located within the CB. For Cr³⁺ ions at Ga³⁺ sites, the three-fold degenerate 3d-t_2g orbitals with majority spin are fully occupied and located within the band gap. The other unoccupied 3d orbitals of Cr³⁺ ions at Ga³⁺ sites are buried in the CB. These calculations indicate that Eu dopants can stably maintain a + 3 valence state at both Zn²⁺ and Ga³⁺ sites and Eu³⁺ can act as electron traps within the host due to their potential reduction to the divalent form. Conversely, Cr impurities can be hole traps through oxidation from + 3 to + 4 valence state. As illustrated in Fig. 2i, codoping Eu³⁺ with Cr³⁺ ions suppresses the 4f-4f luminescence of Eu³⁺ ions because the hole at the top of the VB is trapped by Cr³⁺ ions, thereby eliminating the charge transition states of Eu³⁺ ions. As a result, energy transfer (ET) from Cr³⁺ to Eu³⁺ ions is responsible for the persistent luminescence quenching, rather than electron transfer between ions reported by several previous studies.^41–44 The above charge transition level (CTL) calculations suggests that heavily doped Eu³⁺ quenches the persistent luminescence of CD-Eu nanoparticles due to the ET from Cr³⁺ to Eu³⁺ ions. Currently, it is a challenge to balance the energy storage capacity of heavy doping for persistent luminescence enhancement with the luminescence quenching caused by deleterious ET. ET efficiency decreases with increasing the distance, thus a promising approach is to maintain heavy doping while artificially increasing the distance between Cr³⁺ and Eu³⁺ ions within the PLNPs’ geometric structure. This strategy underpins the core-shell engineering employed in this work to maximize persistent luminescence efficiency.

Suppression of ET by core-shell engineering

To eliminate the detrimental ET, core-shell structured CS-Eu was further prepared by a seed-mediated strategy (Fig. 3a).⁴⁵ Elemental mapping images indicate the distribution of Eu in the outer layer of the nanoparticle (Fig. 3b). Energy dispersive X-ray line scan analysis further shows the accumulation of Eu in the 3–4 nm surface region of the nanoparticle (Fig. 3c), which confirms the successful construction of core-shell structured CS-Eu PLNPs. The ZGO core and CS-Eu nanoparticles are about 9 nm and 13 nm in diameter respectively, suggesting a 4 nm ZnGa₂O₄:Eu³⁺ shell was grown on the ZGO surface (Fig. 3d). We prepared a series of CS-Eu with different Eu doping concentrations (Extended Data Figs. 4a-4d) and investigated whether the unwanted ET between Cr³⁺ and Eu³⁺ was suppressed by core-shell engineering. The CS-Eu with both lightly and heavily doped Eu display stronger NIR persistent luminescence emissions at around 695 nm than ZGO (Fig. 3e and Extended Data Fig. 4d). Persistent luminescence decay curves (Fig. 3f) and decay images (Fig. 3g, Extended Data Fig. 4e and Supplementary Fig. 2) confirm the significantly enhanced luminescence intensity and prolonged decay time in heavily-doped CS-Eu PLNPs. In sharp contrast to the co-doped CD-Eu, CS-Eu PLNPs display drastically improved persistent luminescence efficiency even increasing the doped concentration of Eu to 10% (Extended Data Fig. 4e), which is a convincing indicator for the suppression of concentration quenching effect.^46,47 The CS-5%Eu PLNPs show the strongest persistent luminescence and the over 50-fold increase in the optimal Eu³⁺ doping concentration compared to CD-0.1%Eu, which can be attributed to the effective suppression of ET by spatially separating the Cr³⁺ and Eu³⁺ in core-shell structured nanoparticles. The enhancement of the persistent luminescence intensity by core-shell structure engineering was further quantified by measuring the persistent luminescence intensity of ZGO, CD-Eu, and CS-Eu at different time points. After excitation by a 550 nm LED, the persistent luminescence intensity of CS-5%Eu and CD-0.1%Eu at 1 min is about 13.0 and 3.5 times that of ZGO, respectively (Fig. 3h), suggesting the much stronger capacity of core-shell engineering in enhancing persistent luminescence intensity compared to the traditional co-doped strategy. Although the persistent luminescence intensity decays over time, the enhancement factor of CS-5%Eu to ZGO was kept over 8.4 even at 2 h post excitation. We studied the thermoluminescence properties of ZGO, CD-0.1%Eu, and CS-5%Eu PLNPs. As presented in Fig. 3i, CD-0.1%Eu shows a slightly stronger and broader emission band ranging from 50 to 150 ℃ than the ZGO. The stronger thermoluminescence suggests that Eu³⁺ doping can create defects for trapping charge carriers in the ZnGa₂O₄ lattice, which is in good agreement with the above first-principle calculations. The thermoluminescence band of CS-5%Eu is much stronger than that of ZGO and CD-0.1%Eu, which suggests that large amounts of defects are created in the hosts by the heavily doped Eu³⁺.^1,19 Under the premise of efficient suppression of detrimental ET by the designed core-shell structure, the elevated defect density in heavily-doped CS-5%Eu boosts the charge trapping capacity of ZGO, thus leading to the improvement of persistent luminescence efficiency. The above results demonstrate that core-shell engineering efficiently minimized the deleterious ET but retained the energy trapping capacity of lanthanide-associated defects in heavily-doped PLNPs, which affords drastically enhanced persistent luminescence and prolonged decay time.

We further explored the contribution of the significantly enhanced persistent luminescence in CS-5%Eu to the signal-to-background ratio (SBR) in bioimaging. Specifically, ZGO, CD-0.1%Eu, and CS-5%Eu were injected subcutaneously into the back of a mouse, respectively. The injected PLNPs were charged in situ by a commercial 550 nm LED. By collecting the persistent luminescence signal from the injected PLNPs after excitation ceases, the interference from tissue autofluorescence is efficiently eliminated, as evidenced by the photos in Fig. 3j. We quantified the SBR of the injected ZGO, CD-0.1%Eu and CS-5%Eu PLNPs. The SBR of CS-5%Eu is as high as 5.7 and 2.2 times that of the ZGO and CS-0.1%Eu, respectively (Fig. 3k). The above results thus demonstrate the capability of the core-shell engineered PLNPs in improving the sensitivity of bioimaging.

Expanding core-shell engineering to other lanthanides

To test the generality of core-shell engineering in enhancing persistent luminescence in heavily doped PLNPs, we further expanded the strategy to ZnGa₂O₄:Cr³⁺ doped with other lanthanides. We first prepared co-doped CD-Yb, CD-Er, core-shell structured CS-Yb, and CS-Er with varied doping concentrations, respectively (Extended Data Figs. 5 and 6). The CD-Yb, CS-Yb, CD-Er, and CS-Er PLNPs produce the typical persistent luminescence emission of Cr³⁺ at 695 nm (Fig. 4a, Extended Data Figs. 5d and 6d). The persistent luminescence decay curves in Figs. 4b and 4c reveals that the lightly-doped CD-0.2%Yb and CD-0.2%Er produce stronger persistent luminescence than the ZnGa₂O₄:Cr³⁺. Whereas, the persistent luminescence in the heavily doped CS-5%Ln is much stronger than that of lightly doped CD-Ln. The persistent luminescence decay images presented in Figs. 4d and 4e confirm the drastically enhanced luminescence intensity and prolonged decay time in heavily doped CS-Ln. The persistent luminescence intensity in CS-Yb and CS-Er at 1 min after excitation was measured to be about 13 times and 12 times that of ZGO, respectively (Figs. 4d, 4e, Extended Data Figs. 5f and 6f), demonstrating the great capability of the core-shell structure engineering in fulfill the potential of lanthanides in boosting persistent luminescence.

A step further, we prepared a series of CS-5%Ln (Ln: Ho, Gd, Dy, Nd, Tb, Tm) PLNPs and measured their persistent luminescence decay properties (Extended Data Fig. 7). As presented in Fig. 4f, all the heavily-doped CS-5%Ln nanoparticles display drastically increased persistent luminescence intensity compared to ZGO after 550 nm light excitation, among which Dy³⁺ show the strongest ability in improving persistent luminescence efficiency. The persistent luminescence enhancement factors at 5 min post-excitation further reveal that the persistent luminescence in ZnGa₂O₄:Cr³⁺ can be amplified by up to about 25 times with the core-shell structure engineering (Fig. 4g). Compared to 550 nm excitation, UV light is more efficient in charging PLNPs by directly pumping the electrons from the valence band to the conduction band, followed by the trapping of charge carriers by lattice defects. At 1 min post UV excitation, all the CS-5%Ln PLNPs produce persistent luminescence over 35 times that of ZGO, and the maximum persistent luminescence enhancement factor reaches about 60 (Supplementary Fig. 8). Based on the electronic structures of Eu ions doped in ZnGa₂O₄, the ground energy levels of other divalent and trivalent lanthanide ions (Ln = Nd, Gd, Tb, Dy, Ho, Er, Tm, Yb) were calculated using Dorenbos’s zigzag model for lathniades⁴⁸ (Extended Data Fig. 3). These results reveal two key facts: (1) all investigated lanthanide ions, except for Yb³⁺, Eu³⁺, and Tb³⁺, remain in the + 3 valence state, because the 4f ground states of their trivalent and divalent forms are buried into the VB and CB, respectively; (2) Eu³⁺ and Yb³⁺ ions can act as electron traps, while Tb³⁺ ions serve as hole traps. However, Cr³⁺ doping captures holes from the top of the VB due to the deeper impurity level of Cr³⁺ within the band gap. This inhibits the formation of the ligand-to-metal CT states for Eu³⁺ and Yb³⁺ ions (i.e., Eu²⁺/Yb²⁺ + h_ligand) and the metal-to-metal CT states for Tb³⁺ ions (i.e., Tb⁴⁺ + e_metal). Consequently, it suppresses the 4f-4f luminescence of these three ions through their CT states. As a result, all the studied lanthanide ions in this work mainly utilize the ET from codoped Cr³⁺ ions to exhibit the 4f-4f luminescence. Additionally, formation energy calculations suggest that high-concentration doping of lanthanides enhances the number of V_O and Ga_Zn electron traps. Therefore, from both experimental and theoretical perspectives, these findings highlight the significant advantages of the core-shell engineering strategy over the traditional co-doping approach in maximizing the persistent luminescence of lanthanide-doped PLNPs.

Solar-to-chemical synthesis with heavily doped PLNPs

The heavily doped CS-Ln PLNPs possess long-lived electrons and broad absorption across 200–700 nm (Extended Data Fig. 7a), promising the nanoparticles in inorganic-biological hybrid systems for solar-to-chemical conversion.^49–51 We then explored CS-Ln nanoparticles for accelerating the production of fine chemicals by interfacing their versatile optical properties with biosynthetic microorganisms.⁸ Specifically, CS-5%Eu nanoparticles were combined with Rhodopseudomonas palustris TIE-1 (R. palustris) to accelerate the lycopene production under visible light illumination.^50,52,53 R. palustris are phototrophic microorganisms that can accept electrons from the external environment to sustain cellular metabolism.⁵⁴ As illustrated in Fig. 5a, CS-5%Eu nanoparticles produce long-lived electrons under illumination, and the electrons further pass to R. palustris to power the carotenoid biosynthetic pathway for accelerated production of lycopene, which realizes solar-to-chemical production. The phototrophic R. palustris was grown under the illumination of a commercially available LED for greenhouse plant growth, and CS-5%Eu nanoparticles were simply added into the R. palustris broth. The excitation spectrum of the CS-5%Eu nanoparticles well matches the emission of the LED (Fig. 5b), which is beneficial for the generation of long-lived electrons in the nanoparticles. TEM and elemental mapping images in Fig. 5c show the attachment of CS-5%Eu nanoparticles to the surface of R. palustris, which can promote the direct transfer of electrons from PLNPs to R. palustris. We then studied the photosynthetic performance of the hybrid photo-biosynthesis system. Figure 5d shows that bare R. palustris produces a modest amount of lycopene, about 1.69 mg/L. In the presence of CS-5%Eu nanoparticles, the lycopene produced by R. palustris hybrid system is drastically increased to 4.92 mg/L, 2.9 times that of the bare R. palustris. The improved lycopene productivity in R. palustris can be attributed to the sustained supply of electrons from the CS-5%Eu nanoparticles. It is also noted that CD-0.1%Eu nanoparticles also elevated the lycopene yield to 3.08 mg/L, showing the great promise of persistent luminescence phosphors in improving the productivity of microbial cell factories.

The lycopene production kinetics were further investigated by monitoring the accumulated amount of lycopene over time. As shown in Fig. 5e, neglectable lycopene is produced in the first 48 hours. The lycopene production increases rapidly from 48 h and reaches the plateau after 120 h of photo-synthetic reaction. Notably, CS-5%Eu/R. palustris hybrid system exhibits faster and higher lycopene production than the bare R. palustris or the CD-0.1%Eu/R. palustris hybrid system. The CS-5%Eu/R. palustris hybrid system was further subjected to an alternating light-dark cycle to imitate natural light. The intermittent light illumination slows down the growth of R. palustris since R. palustris are phototrophic microorganisms. The lycopene produced by the CS-5%Eu/R. palustris hybrid system is detected after 3.5 days of culture, and sustained production of lycopene is observed during the following light-dark cycles (Fig. 5f). The production rate of lycopene by the CS-5%Eu/R. palustris hybrid system in dark is similar to that in light, which can be ascribed to the sustained reaction of the accumulated metabolic intermediates produced during light illumination.^49,55 Previous studies have shown that the electrons of semiconductors can be passed to microorganisms for biosynthesis, whereas the holes in semiconductors can be annihilated by reductive molecules in the culture broth. Cysteine (Cys) was added to the CS-5%Eu/R. palustris hybrid system to annihilate the holes and the lycopene yield was recorded. As shown in Fig. 5g, the lycopene productivity is elevated by about 1.3 times in the presence of Cys, suggesting that the reductive molecules in broth are capable of annihilating the holes produced by PLNPs to assist the photo-biosynthesis reaction. The cell viability in the PLNPs/R. palustris hybrid photo-biosynthesis system was determined by measuring the OD₆₀₀ over time and counting the cell numbers (Fig. 5h). The R. palustris in the hybrid system exhibits a similar growth curve and cell number to bare R. palustris, suggesting the good biocompatibility of the CS-5%Eu. The above results demonstrate the infinite opportunities of the core-shell engineered PLNPs in elevating the productivity of microbial cell factories with solar energy.

In conclusion, we demonstrated that core-shell engineering is a reliable solution to the contradiction between enlarged charge trapping capacity and unwanted ET in lanthanide-doped PLNPs. By spatially confining the activators and lanthanides in core and shell, respectively, the applicable doping ratio of lanthanides was elevated by over 50 folds, accompanied by the drastic enhancement of persistent luminescence in PLNPs by up to 60 times. We further demonstrated the future applications of the core-shell structured PLNPs in solar-to-chemical synthesis. By interfacing PLNPs with microorganisms, the productivity of fine chemicals was increased by 190%, showing the good promise of our designed PLNPs in boosting the production of microbial cell factories. Our findings will open up a new avenue for developing highly emissive persistent luminescence phosphors and further contribute to areas including biomedicine and solar-to-chemical synthesis.

Materials. Zinc nitrate hexahydrate (Zn(NO₃)₂·6H₂O), gallium nitrate (Ga(NO₃)₃·9H₂O, 99.99%), europium oxide (Eu₂O₃, 99.99%), holmium oxide (Ho₂O₃, 99.99%), erbium oxide (Er₂O₃, 99.99%), ytterbium oxide (Yb₂O₃, 99.99%), neodymium oxide (Nd₂O₃, 99.99%), terbium oxide (Tb₂O₃, 99.99%), thulium oxide (Tm₂O₃, 99.99%), gadolinium oxide (Gd₂O₃, 99.99%), dysprosium oxide (Dy₂O₃, 99.99%) and chromic nitrate (Cr(NO₃)₃ ·9H₂O) were obtained from Aladdin (China). Sodium hydroxide (NaOH), ammonium hydroxide (NH₃·H₂O), concentrated nitric acid (HNO₃), glycerol, and sodium chloride (NaCl) were purchased from Sinopharm Chemical Reagent Co. (China). Tryptone, soytone and agar were purchased from Sangon Biotech (Shanghai) Co., Ltd (China). Cysteine (Cys), ascorbic acid (AA) were purchased from Aladdin (China). Ln₂O₃ powder was dissolved in HNO₃ to obtain the Ln(NO₃)₃ solution. Zn(NO₃)₂ solution (1 mol L^− 1), Ga(NO₃)₃ solution (0.4 mol L^− 1), Ln(NO₃)₃ solution (0.1 mol L^− 1) and Cr(NO₃)₃ solution (0.08 mol L^− 1) were used as the precursor solutions in all the experiments. Rhodopseudomonas palustris (BMZ147042) were obtained from Mingzhoubio Co., Ltd (China).

Characterization. Transmission electron microscope (TEM) measurements were performed on a HITACHI TEM (120 kV, HT-7700, Japan). The high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and elemental mapping were obtained on a TEM (Thermo Scientific, Holland) working at 300 kV. The structure of the crystal was analyzed by a D8 Advance X-ray powder diffractometer (Bruker, Germany). The photoluminescence curves and decay spectra of PLNPs were measured on an F-4600 fluorescence spectrometer (Hitachi, Japan). The transient lifetime of PLNPs was measured on a fluorescence spectrometer (Edinburgh Instruments, FLS920, England). The persistent luminescence decay images were captured by an IVIS imaging system (Perkin-Elmer, USA). Zeta potential measurements were tested on a Malvern Zetasizer Nano ZS system (Malvern, Zetasizer Nano ZS, UK). The elemental analysis was measured by an inductively coupled plasma optical emission spectrometer (Bruker, USA). In vivo mouse imaging experiments were conducted on an IVIS Lumina XR Series III Imaging System (Perkin-Elmer, USA). A green LED was used as the excitation source for the PLNPs. Electron paramagnetic resonance (EPR) characterization was measured on a JES-X320 EPR spectrometer (JEOL, Japan) at room temperature. The concentration of lycopene and OD₆₀₀ were measured on a UV-VIS-NIR Spectrophotometer (Shimadzu, Japan). The elemental mapping of bacterial and CS-5%Eu PLNPs mixtures was obtained on a field emission transmission electron microscope (Thermo Scientific, Czechia) working at 200 kV.

Synthesis of ZnGa ₂ O ₄:1%Cr (ZGO) PLNPs. The ZGO nanoparticles were synthesized via a hydrothermal process. In brief, 2 mmol of Ga(NO₃)₃, 1 mmol of Zn(NO₃)₂, and 0.01 mmol of Cr(NO₃)₃ were added into 10 mL of deionized water under vigorous stirring. NH₃·H₂O (28 wt%) was added into the above solution to adjust the pH value to 8.5. After keeping the mixture solution agitated for 1 h at room temperature, the mixture solution was added into a 20 mL Teflon-lined stainless autoclave and reacted for 10 h at 220 ℃. Lastly, the suspension was centrifuged and ZGO PLNPs were washed with DI water for three times.

Synthesis of ZGO:1%Cr,x%Ln (CD-Ln) (Ln: Eu, Yb, Er) PLNPs. Ga(NO₃)₃ (2 mmol), Zn(NO₃)₂ (1 mmol), Cr(NO₃)₃ (0.01 mmol), and Ln(NO₃)₃ (0.1 mol L^− 1) of appropriate quantity were added to 10 mL of DI water. The pH value of the mixture was adjusted to 8.5 by NH₃·H₂O (28 wt%) under vigorous stirring. After keeping the prepared solution agitated under the room atmosphere for 1 h, the mixture was further decanted into a 20 mL Teflon-lined stainless autoclave and reacted for another 10 h at 220 ℃. After that, the acquired suspension was centrifuged to collect CD-x%Ln PLNPs, followed by washing with DI water three times.

First-principle calculations. Our first-principles calculations were conducted within the density functional theory framework using the Vienna ab initio simulation package (VASP).⁵⁶ A \(\:1\times\:1\times\:2\) supercell containing 112 atoms was employed to model defect effects in ZnGa₂O₄, including intrinsic vacancies, antisite defects, and extrinsic Cr³⁺ and Eu³⁺ dopants. Structural relaxations of the supercells were carried out using the Perdew Burke Ernzerof (PBE) functional.⁵⁷ The PBE + U method was applied to account for the strongly correlated 4f orbitals of Eu³⁺ ions, with U_eff = 6 eV. A single \(\:\varGamma\:\)-point was adopted for Brillouin zone sampling. Projector augment wave pseudopotentials were employed to describe atomic interactions, with valence-electron configurations of Cr, Eu, Zn, Ga, and O set as 3p⁶3d⁵4s¹, 4f⁶5s²5p⁶5d¹6s², 3d¹⁰4s², 3d¹⁰4s²4p¹, and 2s²2p⁴, respectively.^58,59 The plane-wave cutoff energy was set to 520 eV, and the convergence criteria were \(\:{10}^{-5}\) eV for electronic energy minimization and 0.02 eV/Å for Hellman-Feynman forces on each atom. Based on the relaxed equilibrium geometries, the hybrid PBE0 functional was utilized for a more accurate description of the electronic structure of the material.⁶⁰ The calculation of formation energies and thermodynamic charge transition levels followed the standard model as outlined in the classical reference.⁶¹ To model the excited states ²E and ⁴T₂ of Cr³⁺ ions doped in ZnGa₂O₄, the ΔSCF-DFT method was employed, following our recent work.⁶²

Synthesis of core-shell structured ZGO:1%Cr@ZGO:x%Ln (CS-Ln) (Ln: Eu, Yb, Er) PLNPs. ZGO nanoparticles (0.1 g), Ga(NO₃)₃ (0.50 mmol), Zn(NO₃)₂ (0.25 mmol), and Ln(NO₃)₃ (0.1 mol L^− 1) of appropriate quantity were added to 10 mL DI water. Concentrated NH₃·H₂O (28 wt%) was instantly added to regulate the pH value of the mixed solution to 8.5. The prepared mixture was stirred for 1 h under the room atmosphere. After transferring into a 20 mL Teflon-lined stainless autoclave, the mixed solution was allowed to react for 10 h at 220 ℃. Finally, the obtained suspension was centrifuged, and the prepared CS-x%Ln PLNPs were collected and washed with DI water three times.

Synthesis of core-shell structured ZGO:1%Cr@ZGO:5%Ln (CS-5%Ln) (Ln: Ho, Gd, Dy, Nd, Tb, Tm) PLNPs. ZGO nanoparticles (0.1 g), Ga(NO₃)₃ (0.50 mmol), Zn(NO₃)₂ (0.25 mmol), and Ln(NO₃)₃ (0.0125 mmol) were added to 10 mL of DI water. Concentrated NH₃·H₂O (28 wt%) was added to adjust the pH value of the mixed solution to 8.5. The mixture was stirred for 1 h under room the temperature and further transferred to a 20 mL Teflon-lined stainless autoclave for reaction at 220 ℃ for 10 h. Finally, CS-5%Ln PLNPs were centrifuged and washed three times with DI water.

Characterization of the persistent luminescence of PLNPs. Firstly, PLNPs (0.03 g) were put into a 96-plate well. The PLNPs were illuminated by a commercial LED (550 nm) for 3 min. Then the 96-plate well was placed immediately in the IVIS imaging system to obtain attenuation images at 1 min, 5 min, 10 min, 30 min, 60 min, 90 min and 120 min, respectively. Bioluminescence mode and automatic exposure was used in the measurements.

In vivopersistent luminescence imaging. Briefly, 4 ~ 6 weeks of female balb/c nude mice were obtained from the Laboratory Animal Center of Soochow University (Suzhou, China). ZGO, CD-0.1%Eu, and CS-5%Eu (50 µL, 2 mg L^− 1) was injected subcutaneously into different positions on the back of healthy mice. The mice were irradiated with an LED (550 nm) for 3 min, and the persistent luminescence signals in the mice were detected by bioluminescence mode with an IVIS imaging system. All animal experiments were approved by the Animal Ethics Committee of Soochow University. All animal experiments followed the national guidelines (certificate no. 20020008, grade II) for the Care and Use of Laboratory Animals.

Bacteria culture. R. palustris was cultured at 30 ℃ under light irradiation in the TSA medium that contains 15 g tryptone, 5 g soytone and 5 g NaCl per liter. A full-spectrum lamp (100 W) was used as the light source.

Viability test. To test the toxicity of PLNPs, PLNPs and R. palustris were mixed and co-cultured in a shaker. The optical density of R. palustris and R. palustris/PLNPs at 600 nm (OD₆₀₀) was monitored at different time points.

Lycopene production. R. palustris was cultured in TSA medium until the OD₆₀₀ reached around 0.5, then CD-0.1%Eu or CS-5%Eu was added to a final concentration of about 1 mg mL^− 1. The R. palustris and the hybrid photo-biosynthesis systems were placed into a shaker and cultured at a speed of 200 rpm at 30 ℃. A full-spectrum LED was used as the light source. After incubation, the R. palustris were centrifuged at 8000 rpm for 6 min, and the supernatant was removed to obtain the bacteria. Subsequently, the R. palustris were washed twice with 1.0 g L^− 1 of NaCl. After removing the supernatant, the bacteria cells were dried at 80 ℃ for 12 h. Then 6 mL of n-hexane and methanol (2:1 v/v) mixture was added to extract the lycopene at room temperature with a shaking rate of 200 rpm for 30 min in dark. The cell fragments were removed by centrifugation at 12000 rpm for 10 min and the supernatant was collected. The concentration of lycopene in the supernatant was determined using a UV-VIS-NIR spectrophotometer.

Lycopene production in light-dark cycles. A full-spectrum fluorescent lamp (100 W) was used as the light source to illuminate the bacteria. After 60 h of incubation, the illumination and darkness were alternately conducted every 12 h. At different time points, lycopene was extracted from the bacteria and the lycopene productivity was measured on a UV-VIS-NIR spectrophotometer.

Reporting Summary. Further information on research design is available in the Nature Research Reporting Summary linked to this article.

Author Contributions

⁺B.Q. and W.D. contributed equally. J.W. designed the project. B.Q. and W.D. synthesized the zinc gallate nanoparticles. B.S. was responsible for HAADF TEM measurement. B.Q. and W.D. conducted the luminescence properties measurement and the bioimaging experiments. B.Q. drew all the schematic illustrations. B.Q. and W.D. conducted the lycopene biosynthesis experiments. B.Q. and W.D. were primarily responsible for data collection. B.L. and C.M. conducted the fisrt-principle calculations. J.W., C.M. and Y.W. participated in the discussion on the organization of the manuscript. J.W., B.Q. and C.M. prepared the manuscript, figures, and Supplementary Information.

ACKNOWLEDGMENT

The authors acknowledge support from the National Natural Science Foundation of China (52161135110, 12274048, and 22274105), the State Key Laboratory of Chemo/Biosensing and Chemo-metrics Foundation (20240611), the Gusu Innovation and Entrepreneurship Leading Talent Plan (ZXL2023199), the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (grant no. 22KJB150034), and the start-up grant of Soochow University (No. NH10900624).

Data availability

The data that support the plots within this paper and other findings of this study are available from the corresponding author upon reasonable request. Source data are provided with this paper.

Liang LL, Chen JY, Shao K, Qin X, Pan ZF, Liu XG (2023) Controlling persistent luminescence in nanocrystalline phosphors. Nat Mater 22:289–304
Li Y, Gecevicius M, Qiu JR (2016) Long persistent phosphors-from fundamentals to applications. Chem Soc Rev 45:2090–2136
Ou XY, Qin X, Huang BL, Zan J, Wu QX, Hong ZZ, Xie LL, Bian HY, Yi ZG, Chen XF, Wu YM, Song XR, Li J, Chen QS, Yang HH, Liu XG (2021) High-resolution X-ray luminescence extension imaging. Nature 590:410–415
Xu C, Huang JS, Jiang Y, He SS, Zhang C, Pu K (2023) Y. Nanoparticles with ultrasound-induced afterglow luminescence for tumour-specific theranostics. Nat Biomed Eng 7:298–312
Liu YC, Teng LL, Lou XF, Zhang XB, Song GS (2023) Four-in-one design of a hemicyanine-based modular scaffold for high-contrast activatable molecular afterglow imaging. J Am Chem Soc 145:5134–5144
Pei P, Chen Y, Sun CX, Fan Y, Yang YM, Liu X, Lu LF, Zhao MY, Zhang HX, Zhao DY, Liu XG, Zhang F (2021) X-ray-activated persistent luminescence nanomaterials for NIR-II imaging. Nat Nanotechnol 16:1011–1018
Wang YJ, Yi ZG, Guo J, Liao SY, Li Z, Xu S, Yin BL, Liu YC, Feng YR, Rong QM, Liu XG, Song GS, Zhang XB, Tan WH (2024) In vivo ultrasound-induced luminescence molecular imaging. Nat Photon 18:334–343
Wang J, Chen N, Bian G, Mu X, Du N, Wang W, Ma CG, Fu S, Huang B, Liu TG, Yang YB, Yuan Q (2022) Solar-driven overproduction of biofuels in microorganisms. Angew Chem Int Ed 61:e202207132
Wang J, Chen N, Wang W, Li Z, Huang B, Yang Y, Yuan QJ (2023) C. C. Room-temperature persistent luminescence in metal halide perovskite nanocrystals for solar-driven CO₂ bioreduction. CCS Chem 5:164–175
Tang Q, Wang J, He B, Yang P (2017) Can dye-sensitized solar cells generate electricity in the dark? Nano Energy 33:266–271
Norrbo I, Carvalho JM, Laukkanen P, Mäkelä J, Mamedov F, Peurla M, Helminen H, Pihlasalo S, Härmä H, Sinkkonen J, Lastusaari M (2017) Lanthanide and heavy metal free long white persistent luminescence from Ti doped Li-hackmanite: a versatile, low-cost material. Adv Funct Mater 27:1606547
Zhuang YX, Wang L, Lv Y, Zhou TL, Xie RJ (2018) Optical data storage and multicolor emission readout on flexible films using deep-trap persistent luminescence materials. Adv Funct Mater 28:1705769
Yang ST, Qi B, Sun MZ, Dai WJ, Miao ZY, Zheng W, Huang BL, Wang J (2024) Broadband near-infrared light excitation generates long-lived near-infrared luminescence in gallates. ACS Nano 18:22465–22473
Huang JS, Su LC, Xu C, Ge XG, Zhang RP, Song JB, Pu K (2023) Y. Molecular Radio afterglow probes for cancer radiodynamic theranostics. Nat Mater 22:1421–1429
Sun SK, Wang HF, Yan XP (2018) Engineering persistent luminescence nanoparticles for biological applications: from biosensing/bioimaging to theranostics. Acc Chem Res 51:1131–1143
Liu J, Lécuyer T, Seguin J, Mignet N, Scherman D, Viana B, Richard C (2019) Imaging and therapeutic applications of persistent luminescence nanomaterials. Adv Drug Delivery Rev 138:193–210
Kang F, Sun G, Boutinaud P, Wu H, Ma FX, Lu J, Gan J, Bian H, Gao F, Xiao S (2021) Recent advances and prospects of persistent luminescent materials as inner secondary self-luminous light source for photocatalytic applications. Chem Eng J 403:126099
Huang K, Le N, Wang JS, Huang L, Zeng L, Xu WC, Li ZJ, Li Y, Han G (2022) Designing next generation of persistent luminescence: recent advances in uniform persistent luminescence nanoparticles. Adv Mater 34:2107962
Yang ST, Dai WJ, Zheng W, Wang J (2023) Non-UV-activated persistent luminescence phosphors for sustained bioimaging and phototherapy. Coord Chem Rev 475:214913
Ming J, Chen Y, Miao H, Fan Y, Wang SF, Chen ZH, Guo ZH, Guo ZX, Qi LY, Wang XS, Yun BF, Pei P, He HS, Zhang HX, Tang Y, Zhao DY, Wong GKL, Bünzli JCG, Zhang F (2024) High-brightness transition metal-sensitized lanthanide near-infrared luminescent nanoparticles. Nat Photon. https://doi.org/10.1038/s41566-024-01517-9
Chen X, Li Y, Huang K, Huang L, Tian X, Dong H, Kang R, Hu Y, Nie J, Qiu J, Han J (2021) Trap energy upconversion-like near‐infrared to near‐infrared light rejuvenateable persistent luminescence. Adv Mater 33:2008722
Yang H, Zhao W, Song E, Hu K, Zhang H, Yun R, Huang H, Zhong J, Li Y, Li X (2022) Efficient visible light charging for rare earth-free persistent phosphor. Adv Opt Mater 10:2102496
Huang P, Zheng W, Gong Z, You W, Wei J, Chen X (2019) Rare earth ion-and transition metal ion-doped inorganic luminescent nanocrystals: from fundamentals to biodetection. Mater Today Nano 5:100031
Liang LL, Qin X, Zheng KZ, Liu XG (2019) Energy flux manipulation in upconversion nanosystems. Acc Chem Res 52:228–236
Zhou JJ, Zheng GJ, Liu XF, Dong GP, Qiu JR (2021) Defect engineering in lanthanide doped luminescent materials. Coord Chem Rev 448:214178
Matsuzawa T, Aoki Y, Takeuchi N, Murayama Y (1996) A new long phosphorescent phosphor with high brightness, SrAl₂O₄:Eu²⁺,Dy³⁺. J Electrochem Soc 143:2670–2673
Huang K, Li Z, Li Y, Yu N, Gao X, Huang L, Lim SF, Han G (2021) Three-dimensional colloidal controlled growth of core-shell heterostructured persistent luminescence nanocrystals. Nano Lett 21:4903–4910
Rodríguez Burbano DC, Sharma SK, Dorenbos P, Viana B, Capobianco JA (2015) Persistent and photostimulated red emission in CaS:Eu²⁺,Dy³⁺. Nanophosphors 3:551–557
Ueda J, Miyano S, Tanabe S (2018) Formation of deep electron traps by Yb³⁺ codoping leads to super-long persistent luminescence in Ce³⁺-doped yttrium aluminum gallium garnet phosphors. ACS Appl Mater Interfaces 10:20652–20660
Zhuang Y, Lv Y, Wang L, Chen W, Zhou T-L, Takeda T, Hirosaki N, Xie RJ (2018) Trap depth engineering of SrSi₂O₂N₂:Ln²⁺,Ln³⁺ (Ln²⁺ = Yb, Eu; Ln³⁺ = Dy, Ho, Er) persistent luminescence materials for information storage applications. ACS Appl Mater Interfaces 10:1854–1864
Chen Q, Xie X, Huang B, Liang L, Han S, Yi Z, Wang Y, Li Y, Fan D, Huang L (2017) Confining excitation energy in Er³⁺-sensitized upconversion nanocrystals through Tm³⁺‐mediated transient energy trapping. Angew Chem Int Ed 56:7605–7609
Fan Y, Liu L, Zhang F (2019) Exploiting lanthanide-doped upconversion nanoparticles with core/shell structures. Nano Today 25:68–84
Liu X, Chen ZH, Zhang H, Fan Y, Zhang F (2021) Independent luminescent lifetime and intensity tuning of upconversion nanoparticles by gradient doping for multiplexed encoding. Angew Chem Int Ed 60:7041–7045
Wang F, Deng R, Wang J, Wang Q, Han Y, Zhu H, Chen X, Liu X (2011) Tuning upconversion through energy migration in core-shell nanoparticles. Nat Mater 10:968–973
Xie X, Gao N, Deng R, Sun Q, Xu Q-H, Liu X (2013) Mechanistic investigation of photon upconversion in Nd³⁺-sensitized core-shell nanoparticles. J Am Chem Soc 135:12608–12611
Wang J, Ma QQ, Hu XX, Liu HY, Zheng W, Chen XY, Yuan Q, Tan WH (2017) Autofluorescence-free targeted tumor imaging based on luminous nanoparticles with composition-dependent size and persistent luminescence. ACS Nano 11:8010–8017
Ma QQ, Wang J, Zheng W, Wang Q, Li ZH, Cong HJ, Liu HJ, Chen XY, Yuan Q (2018) Controlling disorder in host lattice by hetero-valence ion doping to manipulate luminescence in spinel solid solution phosphors. Sci China: Chem 61:1624–1629
Li Z, Zhang Y, Wu X, Huang L, Li D, Fan W, Han G (2015) Direct aqueous-phase synthesis of sub-10 nm luminous pearls with enhanced in vivo renewable near-infrared persistent luminescence. J Am Chem Soc 137:5304–5307
Liang L, Qin X, Zheng K, Liu X (2018) Energy flux manipulation in upconversion nanosystems. Acc Chem Res 52:228–236
Dixit H, Tandon N, Cottenier S, Saniz R, Lamoen D, Partoens B, Van Speybroeck V, Waroquier M (2011) Electronic structure and band gap of zinc spinel oxides beyond LDA: ZnAl₂O₄, ZnGa₂O₄ and ZnIn₂O₄. New J Phys 13:063002
Wang Y, You Z, Li J, Zhu Z, Ma E, Tu C (2012) Crystal growth and optical properties of Cr³⁺, Er³⁺, RE³⁺: Gd₃Ga₅O₁₂ (RE = Tm, Ho, Eu) for mid-IR laser applications. J Lumin 132:693–696
Teng Y, Zhou J, Nasir Khisro S, Zhou S, Qiu J (2014) Persistent luminescence of SrAl₂O₄: Eu²⁺, Dy³⁺, Cr³⁺ phosphors in the tissue transparency window. Mater Chem Phys 147:772–776
Yang J, Jiang R, Meng Y, Zhao Y, Wang M, Zhu H, Yan D, Liu C, Xu C, Liu Y (2021) NIR-I/III afterglow induced by energy transfers between Er and Cr codoped in ZGGO nanoparticles for potential bioimaging. J Am Ceram Soc 104:4637–4648
Yin Y, Yang W, Wang Z, Zhang Y, Zhu M, Dou C, Che Y, Sun S, Hu C, Teng B et al (2022) Achieving zero-thermal quenching luminescence in ZnGa₂O₄: 0.02Eu³⁺ red phosphor. J Alloys Compd 898:162786
Fu LN, Wang J, Chen N, Ma QQ, Lu DQ, Yuan Q (2020) Enhancement of long-lived luminescence in nanophosphors by surface defect passivation. Chem Commun 56:6660–6663
Zhuo Z, Liu Y, Liu D, Huang P, Jiang F, Chen X, Hong MC (2017) Manipulating energy transfer in lanthanide-doped single nanoparticles for highly enhanced upconverting luminescence. Chem Sci 8:5050–5056
Wen S, Zhou J, Zheng K, Bednarkiewicz A, Liu X (2018) Jin, D. Advances in highly doped upconversion nanoparticles. Nat Commun 9:2415
Dorenbos P (2017) Charge transfer bands in optical materials and related defect level location. Opt Mater 69:8–22
Kornienko N, Zhang JZ, Sakimoto KK, Yang P, Reisner E (2018) Interfacing nature’s catalytic machinery with synthetic materials for semi-artificial photosynthesis. Nat Nanotechnol 13:890–899
Sakimoto KK, Wong AB, Yang P (2016) Self-photosensitization of nonphotosynthetic bacteria for solar-to-chemical production. Science 351:74–77
Guo J, Suástegui M, Sakimoto KK, Moody VM, Xiao G, Nocera DG, Joshi NS (2018) Light-driven fine chemical production in yeast biohybrids. Science 362:813–816
Zhao Z, Pan DC, Qi QM, Kim J, Kapate N, Sun T, Shields IV, Wang CW, Wu LLW, Kwon D, He CJ, Guo W, Mitragotri J (2020) Engineering of living cells with polyphenol-functionalized biologically active nanocomplexes. Adv Mater 32:2003492
Pan J, Gong G, Wang Q, Shang J, He Y, Catania C, Birnbaum D, Li Y, Jia Z, Zhang Y, Joshi NS, Guo J (2022) A single-cell nanocoating of probiotics for enhanced amelioration of antibiotic-associated diarrhea. Nat Commun 13:2117
Chen N, Du N, Wang W, Liu T, Yuan Q, Yang Y (2022) Real-time monitoring of dynamic microbial Fe(III) respiration metabolism with a living cell-compatible electron-sensing probe. Angew Chem Int Ed 61, e202115572
Zhang H, Liu H, Tian Z, Lu D, Yu Y, Cestellos-Blanco S, Sakimoto KK, Yang P (2018) Bacteria photosensitized by intracellular gold nanoclusters for solar fuel production. Nat Nanotechnol 13:900–905
Kresse G, Furthmüller J (1996) Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys Rev B 54:11169–11186
Perdew JP, Burke K, Ernzerhof M (1996) Generalized gradient approximation made simple. Phys Rev Lett 77:3865–3868
Kresse G, Joubert D (1999) From ultrasoft pseudopotentials to the projector augmented-wave method. Phys Rev B 59:1758–1775
Blochl PE (1994) Projector augmented-wave method. Phys Rev B 50:17953–17979
Adamo C, Barone V (1999) Toward reliable density functional methods without adjustable parameters: The PBE0 model. J Chem Phys 110:6158–6170
Freysoldt C, Grabowski B, Hickel T, Neugebauer J, Kresse G, Janotti A, Van de Walle CG (2014) First-principles calculations for point defects in solids. Rev Mod Phys 86:253–305
Kurboniyon MS, Lou BB, Zafari U, Rahimi F, Srivastava AM, Yamamoto T, Brik MG, Ma CG (2023) First-principles study of geometric and electronic structures, and optical transition energies of Mn⁴⁺ impurity ions: K₂SiF₆ as a prototype. J Lumin 263:120103

There is NO Competing Interest.

Download PDF

Version 1

posted

You are reading this latest preprint version

Amplifying persistent luminescence in heavily doped nanopearls for bioimaging and solar-to-chemical synthesis

Status:

Version 1

Abstract

Figures

Introduction

Results and discussion

Deleterious cross-relaxation in CD-Ln PLNPs

Suppression of ET by core-shell engineering

Expanding core-shell engineering to other lanthanides

Solar-to-chemical synthesis with heavily doped PLNPs

Conclusions

Methods

Declarations

Author Contributions

ACKNOWLEDGMENT

Data availability

References

Additional Declarations

Supplementary Files

Status:

Version 1