Poly(vinyl alcohol) induced chirality inversion and amplification of circularly polarized room-temperature phosphorescence in homopolypeptide aggregates

Domain: chemistry
Published: 2026-02-18
Editorial outcome: minor_revision

Abstract
Organic circularly polarized room-temperature phosphorescence (CPRTP) materials represent an emerging research frontier with broad application prospects. However, achieving efficient and controllable CPRTP remains challenging due to inefficient chirality transfer and the limited ability to regulate chiral environments. Here, we develop a strategy involving self-assembled chiral homopolypeptides to realize manipulable CPRTP. Chiral homopolypeptides functionalized with achiral phosphorescent terminals are first designed, which self-assemble into vesicles exhibiting weak CPRTP. Remarkably, dispersing these vesicles into a poly(vinyl alcohol) matrix induces structural reorganization, leading to inversion and significant amplification of CPRTP. Experimental and computational studies reveal the critical role of matrix-assistance in chirality propagation, inversion, and amplification. Moreover, multicolor afterglow films with tunable emissions are readily achieved by varying the terminal phosphor. This work not only establishes a universal platform for constructing tunable CPRTP materials through homopolypeptide self-assembly but also provides deep mechanistic insights into supramolecular chirality manipulation.

Introduction
Chirality, the fundamental geometric property of objects that are non-superimposable on their mirror images, is ubiquitous in nature and plays a critical role across various scientific areas1. This intrinsic asymmetry is of particular significance in the field of luminescent materials, where it produces circularly polarized luminescence (CPL)—a phenomenon in which light emission exhibits an inherent preference for left- or right-handed circular polarization2,3, In recent years, organic CPL-active materials have gained significant attention due to their structural diversity and biocompatibility, demonstrating potential application advantages in biological sciences4, asymmetric synthesis5, information storage6, and optoelectronics7. CPL activity of organic systems can arise through different photophysical processes, including fluorescence, thermally activated delayed fluorescence, or phosphorescence8–13. Among these, circularly polarized room-temperature phosphorescence (CPRTP) has emerged as a particularly promising frontier, combining the long-lived emission feature of phosphorescence with chiral optical functionality14–16. This unique combination enables distinctive applications ranging from multilevel information encryption to time-resolved bioimaging17,18, making CPRTP a focus of current research.

The crucial challenge in developing organic CPRTP materials lies in simultaneously achieving and coupling two key elements: efficient triplet exciton generation (achieving RTP); chiral and rigid environment (generating CPL and achieving long lifetime). In recent years, significant advances have been made in the development of organic CPRTP materials through design strategies of molecular engineering, host-guest doping, and self-assembly18–21. Among these strategies, self-assembly-induced CPRTP stands out as a particularly promising approach due to the spontaneous organization of chiral units and phosphorescent chromophores into ordered architectures with regular molecular arrangements22,23, Such assembled structures enhance chirality transfer through exciton and magnetic coupling, while simultaneously stabilizing triplet excitons via rigidified environment and facilitating precise regulation of CPRTP properties via extensive intermolecular interactions15. Despite these advantages, self-assembled CPRTP systems still face considerable limitations. Most systems rely on specific chiral motifs, restricting their versatility and applicability. Moreover, the fundamental mechanisms underlying chirality transfer, triplet exciton stabilization, and the role of intermolecular interactions remain inadequately understood, impeding the rational design of advanced CPRTP materials. Besides, the current library of CPRTP materials lacks structural and functional diversity, making it challenging to achieve tunable multicolor emission or broad applicability. Therefore, there is an urgent need for a universal design strategy with a clear mechanism to further advance the field of organic CPRTP materials.

Polypeptides, as a class of biodegradable and structurally programmable biopolymers24, offer a versatile platform for the construction of chiral functional materials25. Their inherent chirality, tunable secondary structures, and capacity for precise molecular design make them ideal scaffolds for achieving chiroptical properties26–28. Moreover, the abundant hydrogen-bonding (H-bonding) networks inherent to polypeptide backbones and side chains create a rigid microenvironment capable of stabilizing triplet excitons of incorporated phosphorescent chromophores through self-assembly—a crucial requirement for achieving efficient RTP. Despite these advantages, the unique combination of chiral structure and extensive H-bonding, utilized through polypeptide self-assembly, to generate CPRPT remains unexplored to date.

Herein, we present a facile strategy for fabricating CPRTP materials based on the self-assembly of chiral homopolypeptides bearing achiral phosphorescent terminals (Fig. 1). Specifically, we selected L- and D-type poly(glutamate)s with achiral phosphorescent terminals as chiral scaffolds, which self-assemble into vesicular architectures exhibiting weak yet detectable CPRTP. Remarkably, by doping these pre-assembled vesicles into an achiral poly(vinyl alcohol) (PVA) matrix, we observe the inversion and significant amplification of CPRTP signals. The luminescent dissymmetry factor (glum) reaches 10−2 in doped films, representing a 100-fold enhancement compared to the vesicle powders alone. Besides, this work systematically elucidates the underlying mechanisms of H-bonding-mediated chirality generation, inversion, and amplification via comprehensive experimental and computational analyses. Guided by this mechanism, we demonstrate the universality across different phosphorescent chromophores and achieve multicolor CPRTP emissions. Our findings not only present a versatile approach to achieve tunable CPRTP properties but also provide profound mechanistic insights into how an achiral matrix can manipulate chiral excited states through self-assembly.

Results
CPRTP-active homopolypeptide vesicles
4-bromo-1,8-naphthalimide (BrNI)-terminated L-/D-type poly(glutamate)s (BrNI-PLGA/BrNI-PDGA) were synthesized by deprotecting the benzyl groups of L-/D-type poly(γ-benzyl glutamate) terminated with BrNI (BrNI-PBLG/BrNI-PBDG). These precursors were synthesized via the ring-opening polymerization of L-/D-type γ-benzyl glutamate N-carboxyanhydrides (BLG NCA/BDG NCA) with 2-(2-aminoethyl)-6-bromo-1H-benzo[de]isoquinoline-1,3(2H)-dione (BrNIA) as the initiator, respectively. The detailed synthesis and characterizations of related small molecules and homopolypeptides were provided in the Supplementary Information (Supplementary Figs. 1–4 and Supplementary Table 1). The successful preparation of target homopolypeptides was indicated by proton nuclear magnetic resonance (1H NMR) spectroscopy, with characteristic peaks shifted and aromatic protons broadened. Compared with the precursor of BrNI-PBLG and BrNI-PBDG, the disappearance of typical peaks (δ = ca. 5 and 7 ppm) on 1H NMR spectra of BrNI-PLGA and BrNI-PDGA revealed the complete deprotection of benzyl groups (Supplementary Fig. 4a–d). To precisely obtain the average degree of polymerization (DP) of BrNI-PLGA and BrNI-PDGA, a Lambert-Beer law method was applied to afford the average DP of 90/80 for BrNI-PLGA/BrNI-PDGA, respectively (Supplementary Fig. 5).

Vesicle powders were obtained by the lyophilization of an aqueous solution of homopolyppeptide vesicles via a typical solvent-switching process (Fig. 2a and Supplementary Fig. 6). These off-white powders exhibited orange emissions upon UV irradiation, most likely due to the RTP behavior of the BrNI group (Fig. 2b). Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations revealed a vesicular structure of these homopolypeptide powders with the averaged diameter of ca. 5 μm (Fig. 2c and Supplementary Fig. 7). Furthermore, confocal images also confirmed the formation of giant vesicles for both BrNI-PLGA and BrNI-PDGA with typical hollow spherical structures (Fig. 2c and Supplementary Fig. 8).

Then, the photophysical properties of these vesicle powders were investigated under ambient conditions. Obvious dual-emission of fluorescence (410 nm) and RTP (580 & 617 nm) was detected from both BrNI-PLGA and BrNI-PDGA vesicle powders with RTP lifetimes of 2.44 and 3.51 ms, respectively (Fig. 2d and Supplementary Fig. 9), indicating a rigid environment formed for BrNI groups by the homopolypeptide self-assembly that can stabilize triplet excitons to realize RTP. Notably, mirror-imaged CPL signals were displayed with almost identical emission spectra for BrNI-PLGA and BrNI-PDGA vesicle powders (Fig. 2e). Despite the relatively low |glum| values reaching only 10−4 (Fig. 2f), this work demonstrate the feasibility for fabricating CPRTP-active vesicles by homopolypeptide self-assembly.

CPRTP-active homopolypeptide/PVA films
Subsequently, PVA was introduced as a polymeric matrix to host these vesicle powders. This is because the abundance of hydroxyl groups along the PVA backbone may facilitate the formation of H-bonding interactions with these homopolypeptides and create a more rigid environment, thus suppressing the non-radiative decay and improving the RTP property29–33. The homopolypeptide/PVA films were prepared by casting the aqueous solution of PVA (50 mg/mL) suspended respectively with BrNI-PLGA and BrNI-PDGA vesicle powders onto a quartz glass, followed by a thermal annealing treatment (Fig. 2g and Supplementary Fig. 10). To find the optimal doping conditions, a gradual increase of the vesicle concentration (Cvesicle) of BrNI-PLGA was applied to form BrNI-PLGA/PVA films. The RTP intensity displayed a positive correlation with the doping content of BrNI-PLGA, reaching nearly a plateau with Cvesicle up to 10 mg/mL (Supplementary Fig. 11a and Supplementary Table 2). Consequently, BrNI-PLGA/PVA and BrNI-PDGA/PVA films were prepared with a Cvesicle of 10 mg/mL, respectively. As shown in Fig. 2h, these films exhibited similar orange emissions upon UV irradiation, revealing an obvious RTP phenomenon. Through structure analysis by SEM and confocal techniques (Fig. 2i and Supplementary Fig. 12), bulk aggregates were clearly confirmed in these films, which displayed a solid microstructure with RTP performance. It indicates that original vesicles cannot be dissolved by PVA solution during the process of film preparation, which is most likely to go through a morphology evolution from a hollow vesicular sphere to the solid bulky aggregates. Compared to vesicle powders, the intensity ratios of phosphorescence to fluorescence were improved, and the phosphorescence lifetimes were increased to 5.90 and 5.42 ms for BrNI-PLGA/PVA and BrNI-PDGA/PVA films, respectively (Fig. 2j and Supplementary Fig. 13).

Surprisingly, almost identical absorption and emission spectra but with mirror-imaged circular dichroism (CD) and CPL signals were observed for BrNI-PLGA/PVA and BrNI-PDGA/PVA films. These films showed obvious Cotton effects at around 390 nm, which could be assigned to the absorption from the terminating chromophore (Supplementary Fig. 14). Moreover, CPL signals around 410 and 580 nm were obtained for both BrNI-PLGA and BrNI-PDGA/PVA films, which could be attributed to the circularly polarized fluorescence (CPF) and CPRTP from the terminal chromophore, respectively (Fig. 2k). The maximum glum of CPF and CPRTP were calculated to be 1.28 × 10−2 and 1.11 × 10−2 for BrNI-PLGA/PVA film, respectively (Fig. 2l). Whereas corresponding negative glum of −1.19 × 10−2 and −1.16 × 10−2 were obtained for BrNI-PDGA/PVA film, respectively. These results suggest that the introduction of a chiral PVA not only enhances the RTP performance but also leads to chirality inversion and amplification from the original vesicle powders. Furthermore, BrNI-PLGA/PVA films presented dose-dependent CD and CPL signals. The corresponding glum values progressively enhanced from 10−3 to 10−2 with Cvesicle ranging from 1 to 20 mg/mL (Supplementary Fig. 11b–d), where an unobvious enhancement was revealed with Cvesicle reaching 10 mg/mL (Supplementary Fig. 11d). Therefore, we confirmed the phenomenon of PVA-induced chirality inversion and amplification of CPRTP with homopolypeptides from vesicle powders to hybrid films, which exhibited a dose-dependent CPRTP performance.

Universality for PVA-induced chirality inversion and amplification
To demonstrate the universality of these phenomena, 4-bromobiphenyl (BrBPh, a common phosphor) was incorporated as the terminal chromophore to afford another pair of homopolypeptide enantiomers, named BrBPh-PLGA and BrBPh-PDGA, respectively. The detailed synthesis and characterizations of related homopolypeptides were provided in the Supplementary Information (Supplementary Fig. 2, Supplementary Fig. 4e–h, and Supplementary Table 1).

Through the same fabrication procedure (Fig. 3a), it was easy to obtain BrBPh-PLGA/BrBPh-PDGA vesicles and corresponding hybrid films. Both BrBPh-PLGA and BrBPh-PDGA formed vesicular structures similar to those of homopolypeptide enantiomers discussed above (Supplementary Fig. 15), indicating the insignificant influence of the terminal group on the self-assembly behavior. Consequently, it can be speculated that such assembly behavior is dominated by the peptide backbone. To confirm this, n-hexylamine was introduced as the terminal group to afford Hex-PLGA (Supplementary Fig. 2, Supplementary Fig. 16a, b, Supplementary Table 1). As expected, similar vesicles were obtained via the same solvent-switching procedure (Supplementary Fig. 16c). For BrBPh-PLGA/BrBPh-PDGA systems, both vesicle powders and hybrid films displayed obvious RTP emissions at around 512 nm with lifetimes of ~8 and ~13 ms in the powder and film state, respectively (Fig. 3b and Supplementary Fig. 17). Remarkably, it revealed that the relatively weak CPRTP property from vesicle powders can also go through an apparent inversion and amplification by introducing PVA to form hybrid films (Fig. 3c), with corresponding |glum| values enhanced from 10−4 to 10−2 (Fig. 3d). These results indicate that such chirality generation, inversion, and amplification are almost unaffected by terminal chromophores in this kind of homopolypeptide, dependent only on their different assembled states in the vesicle powder and hybrid film. Furthermore, the dose-dependent CPRTP performance was investigated in BrBPh-PLGA/PVA and BrBPh-PDGA/PVA films as well. The RTP intensity increased slightly with Cvesicle increased from 1 to 10 mg/mL, presenting similar phosphorescent lifetimes over 10 ms (Supplementary Fig. 18 and Supplementary Table 3). In addition, both CD and CPL signals were positively correlated with Cvesicle in these films (Fig. 3e, f), where the |glum| values gradually enhanced from 10−3 to 10−2 (Supplementary Fig. 19 and Fig. 3g). Consequently, it reveals three common chiroptical phenomena in this system containing the homopolypeptides: 1) CPRTP-active vesicles self-assembled from the homopolypeptides; 2) CPRTP-active homopolypeptide/PVA films with chirality inversion and amplification; 3) dose-dependent CPRTP performance in homopolypeptide/PVA films. Therefore, it demonstrates the universality of the strategy for designing CPRTP-active vesicles via homopolypeptide self-assembly, with chirality inversion and amplification upon doping the vesicles into a PVA film.

Mechanism for PVA-induced chirality inversion and amplification
It is generally acknowledged that the chirality transfer plays a crucial role in the fabrication of polymer-based CPL materials composed of a chiral host and an achiral luminescent guest34–36. However, it is intriguing that the achiral PVA can induce the chirality inversion and amplification by simply incorporating CPRTP-active vesicles into the PVA film. It is worth revealing the underlying CPRTP mechanism since the PVA matrix is scarcely employed to induce CPL property without specific post-processing37–39.

Consequently, BrNI-PLGA/PVA film drop casted with the Cvesicle of 10 mg/mL was selected as a model for further mechanism investigation. SEM measurement was employed to investigate the surface morphologies of pure PVA film, BrNI-PLGA vesicle, and BrNI-PLGA/PVA film. A featureless smooth surface was observed for pure PVA film, while some bumps were clearly located on the surface of BrNI-PLGA/PVA film, which should be ascribed to the doped BrNI-PLGA vesicles within the PVA matrix during the film casting process (Fig. 4a). By carefully examining the surface details of the BrNI-PLGA vesicle, some regular ruffles could be found, indicating a possible regular alignment of BrNI-PLGA chains within the vesicle. Given the strong RTP emission for BrNI-PLGA vesicle powder and BrNI-PLGA/PVA film, their confocal images were compared. A typical hollow structure of BrNI-PLGA vesicle was clearly presented, which was transformed into solid particles (Fig. 4b). Then, cross sections of PVA and BrNI-PLGA/PVA films were observed by SEM. A homogeneous cross-section was displayed in PVA film, while a foreign moiety was found in BrNI-PLGA/PVA film (Fig. 4c), which should be the deformed vesicle during the drop casting process. In view of the above results, it was believed that BrNI-PLGA vesicles could be extruded into a lamellar-like structure rather than become completely disintegrated into homogeneously dispersed single chains in the doped film.

Fourier-transform infrared (FTIR) spectra showed different vibration peaks located respectively at 3273 cm−1, 3347 cm−1, and 3280 & 3331 cm−1 for PVA film, BrNI-PLGA vesicle, and BrNI-PLGA/PVA film (Fig. 4d), which revealed different H-bonding interactions existed in these structures. It indicates that BrNI-PLGA chains, consisting of the vesicle, can interact with PVA chains during the film casting process. One should notice that typical peaks originated from α-helical conformation (~1545 cm−1, ~1645 cm−1) of BrNI-PLGA still existed in the doped film40–42, suggesting that the introduction of PVA mainly affect the intermolecular rather than the intramolecular H-bonding of BrNI-PLGA chains. Furthermore, X-ray diffraction (XRD) patterns demonstrated a relatively regular alignment of BrNI-PLGA chains in the isolated vesicle, which may lead to the helical packing of the terminated BrNI groups and afford the chiral emission. However, such regular signals could not be found after forming the doped film (Fig. 4e), which may be covered up by the too strong semi-crystalline signal peak of PVA in the film state.

Therefore, the chirality inversion and amplification induced by PVA most likely arise from the hydrogen bonding that forms between PVA and the homopolypeptide chains. It may change the alignment mode of homopolypeptide chains formed in the vesicle to a more stable state with an inversed chiral packing mode of the terminated BrNI groups, affording the chirality inversion and amplification.

Furthermore, PVA was replaced with poly(ethylene glycol) (PEG) to prepare BrNI-PLGA/PEG film via a similar procedure (Supplementary Fig. 20a), where a decreased H-bonding between PEG and homopolypeptide chains should be achieved since PEG serves only as an acceptor. Despite the similar RTP behavior, the phosphorescence intensity and lifetime were decreased in BrNI-PLGA/PEG film compared with those in BrNI-PLGA/PVA film (Supplementary Fig. 20b, c). Importantly, quite weak chiral signals were observed under CD and CPL measurements (Supplementary Fig. 20d–f), revealing a dramatically reduced ability of PEG to induce chirality inversion and amplification in the vesicle-doped system. In contrast, poly(acrylic acid) (PAA) — a stronger hydrogen-bond donor than PVA — was also employed to prepare a BrNI-PLGA/PAA film (Supplementary Fig. 21a). This composite likewise exhibited obvious RTP (Supplementary Fig. 21b, c), yet its chiral absorption and emission signals remained relatively weak, with a glum value reaching only 1.25 × 10−3 (Supplementary Fig. 21d–f). These results collectively suggest that moderately strong H-bonding interactions provided by PVA play a crucial role in enabling effective chirality inversion and amplification.

To investigate whether the preassembly of homopolypeptides into CPRTP-active vesicles is essential, we designed another film of BrNI-PLGA@PVA containing the same amount of BrNI-PLGA and PVA as that in the BrNI-PLGA/PVA film. As shown in Fig. 4f, the co-assembly of BrNI-PLGA and PVA was realized by gradually dropping the solution of BrNI-PLGA dissolved in N,N-dimethylformamide (DMF) into the PVA solution, followed by a similar drop casting process to form the hybrid film of BrNI-PLGA@PVA. A smoother surface was found in BrNI-PLGA@PVA film compared with that of BrNI-PLGA/PVA film, but no Cotton effect was found in the absorption region of BrNI (Fig. 4g). Moreover, the orange phosphorescence was observed in the whole film under excitation (Supplementary Fig. 22a, b), exhibiting no chiral emission signals in either fluorescence or phosphorescence regions (Fig. 4h and Supplementary Fig. 22c). It indicates that the alignment of homopolypeptide chains in the preformed vesicle is essential for the PVA-induced chirality inversion and amplification.

To further examine the importance of the covalent linkage between the terminal phosphor and the homopolypeptide backbone in this CPRTP system, Hex-PLGA and tert-butyl (2-(6-bromo-1,3-dioxo-1H-benzo[de]isoquinolin-2(3H)-yl)ethyl)carbamate (BrNIB) were co-assembled to obtain Hex-PLGA@BrNIB vesicles (Supplementary Fig. 23a, b). These vesicles showed a markedly lower phosphorescence-to-fluorescence intensity ratio compared with BrNI-PLGA vesicle powders (Supplementary Fig. 23c, d), and CPL measurements revealed nearly no discernible chiral emission in either spectral region (Supplementary Fig. 23e, f). This confirms that covalent tethering of the phosphor to the homopolypeptide backbone not only promotes phosphorescence generation but also plays a key role in enabling CPRTP. Subsequently, Hex-PLGA@BrNIB vesicles were mixed with PVA solution and processed similarly to fabricate the Hex-PLGA@BrNIB/PVA film (Supplementary Fig. 24a). Although the phosphorescence lifetime reached 5.98 ms, the phosphorescence-to-fluorescence intensity ratio remained low (Supplementary Fig. 24b, c), indicating inferior RTP performance relative to the BrNI-PLGA/PVA film. Meanwhile, PVA-induced CPRTP was also observed in the Hex-PLGA@BrNIB/PVA film (Supplementary Fig. 24d–f), but its performance was weaker than that of the BrNI-PLGA/PVA film. Together, these findings demonstrate that covalent attachment of the phosphor to the homopolypeptide terminus is advantageous for achieving enhanced CPRTP properties in both vesicle and film states within these homopolypeptide/PVA systems.

To gain deeper insights into the atomic-level details of structures assembled by BrNI-PLGA, molecular dynamics (MD) simulations were conducted (Supplementary Data 1). Given that the terminal groups of interest are all π-conjugated C-terminal groups, and to directly investigate the assembly mechanism, the Br atom was replaced with an H atom in the simulations for simplification. Our previous MD studies used a truncated 25-amino acid model to elucidate the assembly mechanism of benzyl ester-modified PBLG systems26. These results indicate that short homopolypeptide chains are sufficient to obtain representative assembled structures. Accordingly, in this study, we selected a truncated 25-amino acid unit of PLGA and NI as the C-terminal group (NI-PLGA25) as the simulation model. All-atom force fields can accurately describe the formation of intermolecular hydrogen bonds of protonated PLGA chains. Simulating large supramolecular aggregates with all-atom detail remains challenging due to computational cost and sampling limitations. To balance realism and tractability, we therefore focused on dimeric assemblies, which enable us to analyze interstrand interactions such as backbone H-bonding and terminal chromophore interactions. We randomly inserted two NI-PLGA25 chains (Fig. 5a) and performed MD simulations ten times to explore the possible assembled structures of NI-PLGA25. By analyzing the simulation trajectories, we observed the occurrence of π–π stacking between the two C-terminal NI groups (Fig. 5b). Based on these observations, we defined the dihedral angle (θ) and distance (d) to characterize the relative orientation of the stacked NI groups (Fig. 5b). The handedness of the assembly was evaluated based on θ, with θ > 0° corresponding to left-handed stacks and θ < 0° to right-handed stacks. Interestingly, both chiral packing modes were observed across the ten parallel simulations. Figure 5c shows two representative NI-PLGA25 dimer configurations corresponding to the left- and right-handed packing modes, respectively. As the simulation progressed beyond 40~50 ns, a significant decrease in d was observed, indicating the formation of π–π stacking between the two C-terminal NI groups in both assembly types (Fig. 5d). Analysis of the terminal 10 ns of the trajectories yielded average d values of 4.58 ± 0.08 Å for the left-handed assembly and 3.96 ± 0.03 Å for the right-handed assembly. Concurrently, the θ stabilized at 64.8 ± 2.5° for the left-handed assembly and −37.6 ± 1.1° for the right-handed assembly (Fig. 5e). This π–π stacking further induced rapid intermolecular contacts through hydrogen bonding between the protonated PLGA segments. Notably, among the ten simulations (Supplementary Fig. 25), four resulted in right-handed assemblies, one in a left-handed assembly, and five showed no π–π stacking, with a large d. Therefore, in pure water, the experimentally observed weak R-CPL signal is likely due to the slightly higher proportion of R-CPL assemblies compared to L-CPL assemblies. Moreover, to assess the propagation of the chiral packing mode from dimer to larger assemblies, we constructed a right-handed hexamer with an in-house script that reproduced the C-terminal NI group arrangement. The hexamer remained stable throughout a 100 ns simulation, with θ and d values matching the right-handed dimer (Supplementary Fig. 26), demonstrating that the chiral packing mode can propagate and is scalable within larger assemblies.

Furthermore, to investigate the structural changes of the assemblies in the PVA phase, we randomly inserted two PVA chains (each with a DP of 50) into the pre-assembled left-handed assembly and right-handed assembly dimers. The analysis of θ revealed a disparity in structural stability between the two assemblies. While the left-handed dimer maintained a consistently positive θ value, the right-handed dimer exhibited a distinct handedness inversion, characterized by a shift in θ from negative to positive values (Fig. 5f, Supplementary Movies 1 and 2). Specifically, in the presence of PVA, the initially right-handed configuration (Frame 46, θ = −11.5°) experienced a temporary breakdown of π–π stacking (Frame 52, θ = −6.7°), followed by the adoption of a near face-to-face geometry (Frame 57, θ = 48.4°), and ultimately a flip of the upper molecule (Frame 58, θ = 72.8°), leading to re-stacking with reversed helicity (Fig. 5g). Meanwhile, the d for both dimers stablized to approximately 4.5 Å (Fig. 5h). To elucidate the mechanistic basis for the handedness inversion unique to the right-handed dimer, we quantified the number of hydrogen bonds of PLGA25 chains within the dimer and the number of hydrogen bonds between the dimer and PVA chains. The right-handed assembly’s less stable hydrogen bond network of ~10 hydrogen bonds vs. ~20 in the left-handed form (Fig. 5i, j and Supplementary Fig. 27) appear to facilitate greater interfacial contacts with PVA chains, as evidenced by the larger interaction area (Supplementary Fig. 28). PVA formed hydrogen bonds with the PLGA25 chain of both assemblies and reduced hydrogen bonds within the PLGA25 chains. In the right-handed assembly, hydrogen bonds with PVA exceeded those within PLGA25 chains, thereby disrupting the original hydrogen bond network and triggering molecular rearrangement, resulting in the transformation of the inherently right-handed assembly into a left-handed structure. In contrast, in the inherently left-handed assembly, hydrogen bonds within PLGA25 chains were stronger than those formed with PVA, making the structure hardly disrupted by the addition of PVA and allowing its chirality to remain unchanged. Therefore, in the PVA phase, the experimentally observed weak R-CPL signal changed to a higher L-CPL signal.

CPRTP-active films with multicolor afterglows
According to this strategy, CPRTP-active films can be theoretically fabricated with multicolor afterglows by replacing different terminal phosphor chromophores of long phosphorescence lifetime. Consequently, five typical phosphor chromophores were selected to design corresponding homopolypeptides of MPh-PLGA, TPB-PLGA, SNp-PLGA, SNPh-PLGA, and PY-PLGA (Fig. 6a), which should be suitable for fabricating homopolypeptide/PVA films that exhibit muticolor afterglows of blue, green, yellow, orange, and red, respectively. The detailed synthesis and characterization of related homopolypeptides were provided in the Supplementary Information (Supplementary Figs. 1 and 2, Supplementary Figs. 3c, 4i–r, 29 and Supplementary Table 1).

Through the same film preparation procedure, five hybrid films were successfully obtained with multicolor afterglows ranging from blue to red, with long phosphorescence lifetimes of 658, 1347, 429, 187, and 43 ms, respectively (Fig. 6b–d). All films displayed the positive Cotton effect, indicating the chiral packing of terminal chromophores in the ground state (Fig. 6e). Under the suitable excitation, all films presented left-handed CPL matched with their emission, with relatively large glum values (≥ 0.01) in the corresponding phosphorescence region (Fig. 6f, g). The unique combination of color-tunable, long-lived, and circularly polarized emission in these supramolecular films suggests promising application prospects. The multicolor CPRTP afterglow could be exploited in advanced anti-counterfeiting and multilevel information encryption, where time-resolved and polarization-dependent signals provide enhanced security dimensions. Additionally, such materials may serve as chiral light sources in circularly polarized optoelectronics or as functional components in smart displays and optical sensors.

Methods
Materials
4-Bromo-1,8-naphthalic anhydride (96%), tert-butyl N-(2-aminoethyl) carbamate (98%), L-glutamic acid γ-benzyl ester (98%), D-glutamic acid γ-benzyl ester (≥ 98%), triphosgene (99%), (−)-α-pinene (98%), trifluoroacetic acid (TFA, 98%), hydrobromic acid (HBr, 33 wt% in acetic acid), 4’-bromo-1,1’-biphenyl-4-amine (95%), hexylamine (99%), 4-aminobenzoic methyl ester (≥ 98%), p-phenylenediamine (≥ 97%), 4-sulfo-1,8-naphthalic anhydride potassium salt (≥ 98%), 2-amino-naphthalene-6-sulfonic acid (≥ 98%), 4-(3,5-diphenylphenyl)aniline (≥ 97%), 1-pyrenamine (≥ 98%), poly(vinyl alcohol) (PVA, Mw = 89000-98000, 99% hydrolysis), poly(ethylene glycol) (PEG, Mw = 20000), and poly(acrylic acid) (PAA, Mw = 450000) were purchased from Aladdin. CDCl3 and DMSO-d6 was purchased from J&K Scientific Ltd. Tetrahydrofuran (THF), n-hexane, anhydrous N, N-dimethylformamide (DMF), DMF, acetone, methanol, ethanol, dichloromethane (DCM), sodium chloride (NaCl), sodium sulfate anhydrous (Na2SO4) and sodium hydroxide (NaOH) were purchased from Sinopharm Chemical Reagent Co., Ltd and used without further purification.

Instrumentations
1H NMR and 13C NMR spectra were recorded on Bruker AVANCE NEO NMR spectrometers. Chemical shifts are reported in units (ppm) by assigning the TMS resonance in the 1H spectrum as 0.00 ppm and the DMSO-d6 resonance in the 13C spectrum as 39.50 ppm. High resolution mass spectrometry (HRMS) was carried out on a GCT Premier CAB048 mass spectrometer. Gel permeation chromatography (GPC) measurements for the weight (Mw) and number-average molecular weights (Mn) and the molecular weight dispersity (Đ, Mw/Mn) of the obtained homopolypeptides were estimated by Waters 1525 gel permeation chromatography system using a reactive index (RI) detector and calibrated using a set of monodispersed polystyrene standards. Ultraviolet-visible (UV-Vis) measurements were conducted on a PerkinElmer LAMBDA 365 spectrophotometer. PL measurements were conducted on an Edinburgh FLS1000 Spectrofluorometer with a dwell time of 0.1 s and a step of 1 nm. TEM images were recorded on the JEM-F200 multi-purpose electron microscope with a 200 kV electron source. For the aqueous dispersed solution, the sample was prepared by dropping 10 μL of the solution onto a copper grid covered by a carbon layer and dried at room temperature. SEM images were recorded on the TESCAN Mira 3 field emission SEM instrument with an accelerating voltage of 10 kV. For the aqueous-dispersed solution, the sample was prepared by dropping 50 μL of the solution onto a freshly cleaned silicon wafer and drying it at room temperature. ATR-FTIR measurements were conducted by the Thermo Scientific Nicolet iS10 spectrometer in the range of 4000–400 cm−1. XRD patterns were collected on a Rigaku Smartlab diffractometer with a D/tex Ultra 250 detector (Cu Kα radiation, room temperature, scanning step: 10° min−1). CD spectra were collected on an Applied Photophysics Chirascan spectropolarimeter using ‘Circular Dichroism’ signal mode at a step size of 1 nm, a bandwidth of 1 nm, and a response time of 0.5 s. CPL spectra were collected on a Jasco CPL-300 spectropolarimeter based on ‘Continuous’ scanning mode at 200 nm/min scan speed. The test mode adopts “Slit” mode with the Ex and Em slit width 3000 μm and the digital integration time (D.I.T.) is 2.0 s with multiple accumulations (3 times or more). Confocal fluorescence microscopy images were obtained on a confocal microscope (Leica STELLARIS 8 FALCON). λex = 390 nm. λem = 550–700 nm.

Self-assembly of homopolypeptides into vesicles
The self-assembly of BrNI-PLGA from DMF was performed as follows: BrNI-PLGA was dissolved in DMF with a concentration of 50 mg/mL, which was then transferred into a dialysis bag with a molecular weight cut-off of 8000–14000. The self-assembly was conducted by direct dialysis against water for 2 days to obtain the aqueous solution with obvious precipitation, where a white powder of BrNI-PLGA vesicle was harvested after lyophilization. The self-assembly of other homopolypeptides was performed with a similar procedure.

Preparation of homopolypeptide/PVA films
The BrNI-PLGA/PVA film drop casted from BrNI-PLGA vesicles suspended in PVA solution of a concentration of 10 mg/mL (Cvesicle = 10 mg/mL) was obtained as follows: PVA powder (1.5 g) was added into 30 mL deionized water and stirred at 95°C until PVA was dissolved to afford the PVA solution with a concentration of 50 mg/mL. BrNI-PLGA vesicle powders (10 mg) were dispersed in the above PVA solution (1 mL) and stirred vigorously at 75°C for 2 h. After that, the mixture was drop casted onto the preheated quartz substrate, followed by a post-thermal annealing treatment at 75°C for 1 h. Other homopolypeptide/PVA films with certain Cvesicle were prepared with a similar procedure accordingly.

Preparation of BrNI-PLGA/PEG film
The BrNI-PLGA/PEG film with a Cvesicle of 10 mg/mL was obtained as follows: PEG powder (1.5 g) was added to 30 mL of deionized water and stirred at 75°C until PEG was dissolved to afford the PEG solution with a concentration of 50 mg/mL. BrNI-PLGA vesicle powders (10 mg) were dispersed in the above PEG solution (1 mL) and stirred vigorously at 75°C for 2 h. After that, the mixture was drop casted onto the preheated quartz substrate, followed by a post-thermal annealing treatment at 75°C for 1 h.

Preparation of BrNI-PLGA/PAA film
The BrNI-PLGA/PAA film with a Cvesicle of 10 mg/mL was obtained as follows: PAA powder (1.5 g) was added to 30 mL of deionized water and stirred at 75°C until PAA was dissolved to afford the PAA solution with a concentration of 50 mg/mL. BrNI-PLGA vesicle powders (10 mg) were dispersed in the above PAA solution (1 mL) and stirred vigorously at 75°C for 2 h. After that, the mixture was drop casted onto the preheated quartz substrate, followed by a post-thermal annealing treatment at 75°C for 1 h.

Preparation of BrNI-PLGA@PVA film by co-assembly
The BrNI-PLGA@PVA film was obtained as follows: PVA powder (50 mg) was added to 900 μL deionized water and stirred at 75°C until PVA was dissolved. BrNI-PLGA vesicle powders (10 mg) were dissolved in 100 μL DMF at 75°C. Then the solution of BrNI-PLGA was added into the PVA solution drop by drop under stirring at 75°C. When finished, the mixture was continuously stirred at 75°C for 2 h. After that, the mixture was drop casted onto the preheated quartz substrate, followed by a post-thermal annealing treatment at 75°C for 1 h.

Preparation of Hex-PLGA@BrNIB vesicle by co-assembly
The Hex-PLGA@BrNIB vesicle was obtained as follows: Hex-PLGA powder (100 mg) was mixed with BrNIB (3.6 mg) and dissolved in 2 mL DMF, which was then transferred into a dialysis bag with a molecular weight cut-off of 8000–14000. The self-assembly was conducted by direct dialysis against water for 2 days to obtain the aqueous solution with obvious precipitation, where a white powder of Hex-PLGA@BrNIB vesicle was harvested after lyophilization.

Preparation of Hex-PLGA@BrNIB/PVA film
The Hex-PLGA@BrNIB/PVA film drop casted from Hex-PLGA@BrNIB vesicles suspended in PVA solution of a concentration of 10 mg/mL (Cvesicle = 10 mg/mL) was obtained as follows: Hex-PLGA@BrNIB vesicle powders (10 mg) were dispersed in the PVA solution (1 mL, CPVA = 50 mg/mL) and stirred vigorously at 75oC for 2 h. After that, the mixture was drop casted onto the preheated quartz substrate, followed by a post-thermal annealing treatment at 75°C for 1 h.

All-atom simulations
All the simulations were conducted using the GROMACS software package (version 2023)43. All the files needed for this simulation, including force field parameters, molecular topologies, initial coordinates, and simulation parameters, are included in the Supplementary Data 1. The initial coordinates were generated from a homopolypeptide consisting of 25 glutamate residues in an ideal helical conformation. Protonation was performed using pdb2gmx, and an NI cap was introduced at the C-terminus using in-house scripts. The helix was then placed in a 10 × 10 × 10 nm³ box filled with TIP3P water molecules44. The helix was modeled using the modified CHARMM36 force field45, while the C-terminal NI group and PVA were parameterized with CGENFF46.

Nonbonded interactions were truncated beyond 14 Å. Long-range electrostatic interactions were described using the particle-mesh Ewald (PME) method. The system underwent an initial 100,000-step energy minimization. All bonds involving hydrogen atoms were constrained using the LINCS algorithm, and the timestep was set to 2 fs. The simulation temperature and pressure were maintained at 310 K and 1 bar using the V-rescale thermostat and isotropic C-rescale barostat, respectively. The simulation lasted for one microsecond, and the trajectory after 100 ns was used for analysis.

Peer review rounds
[{"round": 1, "reviewer_comments": {"reviewer_1": "In this work, authors used chiral homopolypeptides and achiral phosphorescent terminals to get vesicles with weak CPRTP. Then, dispersing these vesicles into PVA induces CPRTP. Although there is an amplification effect, the g is only 10-2. The phosphorescent terminals are common chemicals. The longest observable phosphorescence time is 1.5 s by eyes. Considering the limited innovation and performance, it is not recommended to consider this article.", "reviewer_2": "This manuscript presents a notable strategy for achieving programmable circularly polarized room-temperature phosphorescence (CPRTP) through the self-assembly of chiral homopolypeptides. Structural reorganization of the pre-assembled vesicles, induced by an achiral PVA matrix, leads to the inversion and significant amplification of the chiral emission signals. A comprehensive mechanistic study combining experimental and computational approaches was conducted to elucidate the underlying processes. Furthermore, multicolor CPRTP films with emissions tunable from blue to red were successfully fabricated by incorporating various phosphorescent terminal groups. This work establishes a versatile platform for developing high-performance organic CPRTP materials and offers valuable insights into supramolecular chirality transfer and manipulation. It is recommended for publication after minor revisions.\n1. Several images in the manuscript (e.g., Figure 1b and Figure 1h) lack scale bars; their inclusion would facilitate the accurate data interpretation.\n2. It is recommended that the authors should provide merged confocal images (combining bright-field and fluorescence channels) for both the vesicle powders and hybrid films in the SI. Such images would more directly demonstrate the correlation between the observed luminescence and the specific morphologies, thereby reinforcing the morphological analysis.\n3. The authors show that vesicle formation is largely unaffected by the choice of aromatic terminal group. To further decouple the roles of the homopolypeptide backbone and the terminal π-system in driving self-assembly, it would be informative to investigate a homopolypeptide bearing a non-aromatic terminal group, such as an alkyl chain. Determining whether vesicular structures persist in the absence of terminal π–π interactions could provide deeper insight into the primary driving forces of the assembly process.\n4. If vesicular structures are maintained with a non-aromatic terminal group, a subsequent and highly informative experiment would involve a co-assembly system. Specifically, physically doping a phosphorescent guest molecule into vesicles formed by such a \"blank\" homopolypeptide (e.g., n-hexyl-terminated) could test whether covalent attachment is essential for efficient chirality transfer. Successfully observation of PVA-induced chiral inversion and amplification in this non-covalent system would significantly broaden the generality and applicability of the proposed strategy.\n5. By incorporating different phosphors, the authors successfully achieved color-tunable CPRTP systems, demonstrating both the generality of their strategy and the reliability of the proposed mechanism. It is also suggested that the authors discuss potential application prospects and practical scenarios for such systems.", "reviewer_3": "The manuscript presents an interesting phenomenon in the field of circularly polarized room-temperature phosphorescence (CPRTP) on chiral inversion and amplification induced by achiral poly(vinyl alcohol) (PVA) matrix. The authors demonstrate that vesicles self-assembled from chiral homopolypeptides exhibit weak yet detectable CPRTP. Remarkably, when these pre-assembled vesicles are incorporated into the achiral PVA matrix to form hybrid films, the system undergoes an inversion of chirality accompanied by the amplification of the CPRTP signal. The manuscript is supported by a comprehensive set of data, with strength in the mechanistic investigation that combines experimental evidence and molecular dynamics simulations. The core innovation of this work lies in its demonstration that supramolecular chirality can be controlled via intermolecular interactions of chiral assemblies with achiral polymer matrix, which may provide a new thinking for regulating chirality in CPRTP-active materials using commercially available polymers. I recommend publication after the authors address the following points to further strengthen the manuscript.\n1. The study clearly demonstrates that chirality arises from the self-assembly of chiral homopolypeptides in both vesicle and film states. However, it remains unclear whether the covalent attachment of the phosphor terminal is essential for the observed chirality inversion and amplification. A relevant control experiment—such as physically mixing the phosphor with the homopolypeptide and PVA—could help determine if non-covalent systems exhibit similar behavior, as recently illustrated in supramolecular chirality studies (e.g., Science 2025, 389, eadu0296). Clarifying this point would significantly strengthen the mechanistic claims.\n2. The authors attribute the chiral inversion and amplification to the hydrogen-bonding capability of PVA. To further substantiate this mechanism, it would be compelling to investigate other hydrogen-bonding polymers. For instance, employing a matrix like poly(acrylic acid), which can act as both a donor and acceptor of hydrogen bonds, could serve as a critical experiment to test the generality of the proposed mechanism and clarify the specific role of hydrogen-bonding topology.\n3. The molecular dynamics (MD) simulations of peptide dimers provide valuable insight into chiral generation and PVA-induced chiral inversion, attributed to different chiral packing of peptide terminals. I’m wondering whether it is possible to display the chiral packing mode using more peptide chains? Of course, such simulation may be quite complex and computationally demanding. If feasible, it may enhance the structural relevance of the conclusions.\n4. The manuscript contains several typographical errors (e.g., “targe” in Line 122, “homopolypepitde” in Line 146) and inconsistencies in formatting (e.g., font size of “Figure” and “Figure S.”). To meet the high publication standards expected by the journal, a thorough, line-by-line revision of the entire text is strongly recommended to ensure linguistic accuracy and stylistic consistency."}, "author_response": "Responses to the Comments and Suggestions of Reviewers\nThe followings are our point-by-point responses to the reviewers’ comments and suggestions. The modifications in the revised manuscript and supplementary information are marked in blue.\nReviewer #1 (Remarks to the Author):\nIn this work, authors used chiral homopolypeptides and achiral phosphorescent terminals to get vesicles with weak CPRTP. Then, dispersing these vesicles into PVA induces CPRTP. Although there is an amplification effect, the g is only 10-2. The phosphorescent terminals are common chemicals. The longest observable phosphorescence time is 1.5 s by eyes. Considering the limited innovation and performance, it is not recommended to consider this article.\nReply: Thank you for your rigorous review. We fully acknowledge that the absolute performance metrics of our system may not individually break records. However, we respectfully contend that the principal value of this work lies in its addressing of a fundamental scientific question, the delivery of novel mechanistic insights, and the establishment of a generalizable design principle. To more clearly articulate the significance of our findings, we provide below a detailed discussion contextualized within the current research landscape.\n1. Core Innovation: Discovery and Elucidation of a New \"Matrix-Induced Chiral Reconfiguration\" Mechanism\nThe current frontiers in chiral supramolecular systems emphasize precise control over chirality induction, transfer, and amplification (e.g., Science 2025, 389, eadu0296). Concurrently, achieving CPRTP in pure organic materials is an emerging, high-impact goal due to its application potential (e.g., Nat. Photonics 2024, 18, 1276-1284). Notably, achiral polymer matrices like poly(vinyl alcohol) (PVA) are widely used to enhance RTP by forming rigid hydrogen-bonded networks. A critical, yet overlooked, question is whether such an achiral matrix can fundamentally alter the chiroptical properties of embedded chiral emitters.\nOur primary contribution transcends the development of a new CPRTP system via homopolypeptide self-assembly. We report the discovery and systematic investigation of a novel phenomenon: an achiral PVA matrix can induce a \"chiral reconfiguration\" of pre-assembled chiral superstructures, leading to both inversion and significant amplification (>100-fold) of CPL signals.\nWe demonstrate that PVA, through extensive hydrogen bonding with chiral polypeptide chains, alters their packing within vesicles. This reorganization flips the helical orientation of the terminal chromophores' π-π stacks. All-atom MD simulations corroborate that stronger PVA interactions with the right-handed dimer disrupt its native hydrogen-bond network, stabilizing a left-handed conformation. Therefore, this work represents: (i) the first use of achiral-phosphor-modified chiral homopolypeptides as chiral centers for pure organic CPRTP via supramolecular assembly, and (ii) the first report of a commercial PVA matrix enabling efficient, controllable chirality inversion and amplification via simple physical doping.\n2. Performance in Context: A Competitive Benchmark in Pure Organic CPRTP\nWithin the field of pure organic CPRTP materials, a g on the order of 10−2 combined lum with a phosphorescent lifetime (τ) exceeding 1 second is widely recognized as high performance. As summarized in the provided tables, most reported g values fall between lum 10−3 and 10−2, with higher values typically confined to liquid crystal systems (Table Response 1&2).\nOur maximum values of g = 0.031 and τ = 1.347 s are therefore competitive. More importantly, the ~100-fold amplification of the g value (from ~10−4 for vesicle powders lum to ~10−2 for PVA/homopolypeptide films) powerfully validates the proposed “chiral reconfiguration” mechanism. This dramatic enhancement underscores a scientific significance that surpasses the pursuit of an isolated record value.\nWhile the afterglow duration may be optimized further via chromophore design and processing, the current performance is already suitable for certain applications like information encryption. As a novel system, it holds substantial promise for performance enhancement through continued exploration.\nTable Response 1 Overview of CPRTP materials (Adv. Funct. Mater. 2025, 35, 2414086).\nTable Response 2 Photophysical parameters of circularly polarized phosphorescence materials (Angew. Chem. Int. Ed. 2025, 64, e202417906).\n3. Systematic Depth and Generalizable Design: A Platform Beyond a Single Material\nThe robustness and broader implications of our work are evidenced by its systematic methodology and generalizability. We employed a comprehensive strategy spanning synthesis, self-assembly, multi-scale characterization (SEM/TEM/confocal), photophysical analysis (steady-state/time-resolved, CD/CPL), interaction probing (FTIR, XRD), and all-atom MD simulations. This convergent, multi-faceted approach provides compelling evidence, transforming a phenomenological observation into a well-substantiated mechanistic case study.\nFurthermore, we successfully extended the terminal phosphor from BrNI to BrBPh and others, achieving full-color CPRTP from blue to red. This demonstrates the exceptional versatility of our \"chiral polypeptide template + matrix-induced reconfiguration\" strategy for diverse phosphorescent cores, addressing a key challenge of limited color tunability in current CPRTP libraries.\nAs highlighted in recent reviews (e.g., Angew. Chem. Int. Ed. 2025, 64, e202417906), a core challenge is developing high-performance, processable, low-cost, and stable CPRTP materials. Our system, based on commercially available PVA and phosphors fabricated via a simple solution-casting process, offers clear practical advantages over strategies requiring complex synthesis or harsh processing. It thus establishes a general and facile platform for the development of advanced chiroptical materials.\nIn summary, the core contributions of this work are threefold:\n1. Discovery of a New Mechanism: We unveil a previously unreported \"matrix-induced chiral reconfiguration\" mechanism. This process, driven by hydrogen-bonding interactions, demonstrates how an achiral matrix can fundamentally reshape pre-assembled chiral superstructures, providing a novel pathway for controlling supramolecular chirality.\n2. Realization of Competitive Performance: Our system achieves a g up to lum 0.031 and an τ exceeding 1 second, which represent competitive figures of merit within the field of pure organic CPRTP materials.\n3. Establishment of a Versatile Platform: We have developed a generalizable material platform based on biocompatible polypeptides and a commercial polymer. This platform readily enables controllable chirality inversion, significant signal amplification, and tunable multicolor emission. The strategy is notable for its simplicity, cost-effectiveness, and strong potential for practical applications and paradigm extension.\nWe are confident that the work presented is mechanistically original, performance-wise competitive, and broadly applicable. We sincerely hope that this elaborate discussion allows for a reconsideration of the manuscript's scientific significance.\nOnce again, we are deeply grateful for your time and insightful comments, which have been invaluable in helping us clarify and strengthen the presentation of our work.\nReviewer #2 (Remarks to the Author):\nThis manuscript presents a notable strategy for achieving programmable circularly polarized room-temperature phosphorescence (CPRTP) through the self-assembly of chiral homopolypeptides. Structural reorganization of the pre-assembled vesicles, induced by an achiral PVA matrix, leads to the inversion and significant amplification of the chiral emission signals. A comprehensive mechanistic study combining experimental and computational approaches was conducted to elucidate the underlying processes. Furthermore, multicolor CPRTP films with emissions tunable from blue to red were successfully fabricated by incorporating various phosphorescent terminal groups. This work establishes a versatile platform for developing high-performance organic CPRTP materials and offers valuable insights into supramolecular chirality transfer and manipulation. It is recommended for publication after minor revisions.\nReply: Thanks for your comments, and we appreciate your recognition of our work.\n1. Several images in the manuscript (e.g., Figure 1b and Figure 1h) lack scale bars; their inclusion would facilitate accurate data interpretation.\nReply: Thanks for your kind remind. We have added related scale bars in the revised Fig. 1.\nFig. 1 Preparation, morphological characterization, and photophysical properties of BrNI-PL(D)GA vesicles and BrNI-PL(D)GA/PVA films, respectively. (a, g) Illustration for the preparation procedure. (b, h) The photographs under daylight and UV (365 nm) irradiation. Scale bar: 1 mm. (c, i) Scanning electron microscopy (SEM, Top) and confocal (Merge field, bottom) images. λ = 390 nm. λ = 550–650 nm. (d, j) Prompt and delayed Photoluminescence (PL) spectra. λ = 330 nm. Inset: phosphorescent lifetime at the λ of 580 nm. (e, k) Circularly polarized luminescence (CPL) spectra. (f, l) Luminescence dissymmetry factor (g ) curves. λ = 330 nm. To prepare the homopolypeptide/PVA film, the concentration of homopolypeptide vesicles suspended in PVA solution was 10 mg/mL (C = 10 mg/mL), where the concentration of PVA was kept as 50 mg/mL.\n2. It is recommended that the authors should provide merged confocal images (combining bright-field and fluorescence channels) for both the vesicle powders and hybrid films in the SI. Such images would more directly demonstrate the correlation between the observed luminescence and the specific morphologies, thereby reinforcing the morphological analysis.\nReply: Thanks for your kind remind. We have provided merged confocal images for the vesicle powders (Supplementary Fig. 8) and corresponding hybrid films (Supplementary Fig. 12) in the revised SI.\nSupplementary Fig. 8 Confocal images of vesicle powders self-assembled from BrNI-PLGA and BrNI-PDGA. λ = 390 nm. λ = 550–650 nm. Scale bar: 50 μm.\nSupplementary Fig. 12 Confocal images of BrNI-PLGA/PVA and BrNI-PDGA/PVA films. C = 10 mg/mL. λ = 390 nm. λ = 550–650 nm. Scale bar: 50 μm.\n3. The authors show that vesicle formation is largely unaffected by the choice of aromatic terminal group. To further decouple the roles of the homopolypeptide backbone and the terminal π-system in driving self-assembly, it would be informative to investigate a homopolypeptide bearing a non-aromatic terminal group, such as an alkyl chain. Determining whether vesicular structures persist in the absence of terminal π–π interactions could provide deeper insight into the primary driving forces of the assembly process.\nReply: Thanks for your suggestions. In this work, we have confirmed that vesicles can still be obtained by replacing the BrNI terminal group with the BrBPh chromophore. Consequently, it can be speculated that such assembly behavior is dominated by the peptide backbone. To confirm this, n-hexylamine was introduced as the terminal group to afford Hex-PLGA (Supplementary Fig. 16a-b). As expected, similar vesicles were obtained via the same solvent-switching procedure (Supplementary Fig. 16c). Therefore, it reveals that the primary driving force for the vesicle formation comes from the homopolypeptide backbone in this work.\nSupplementary Fig. 16 Chemical structures of homopolypeptides and SEM image of the assembled vesicle. a, b 1H NMR spectra of Hex-PBLG and Hex-PLGA in DMSO-d, respectively. c SEM image of vesicles self-assembled from Hex-PLGA.\n4. If vesicular structures are maintained with a non-aromatic terminal group, a subsequent and highly informative experiment would involve a co-assembly system. Specifically, physically doping a phosphorescent guest molecule into vesicles formed by such a \"blank\" homopolypeptide (e.g., n-hexyl-terminated) could test whether covalent attachment is essential for efficient chirality transfer. Successfully observation of PVA-induced chiral inversion and amplification in this non-covalent system would significantly broaden the generality and applicability of the proposed strategy.\nReply: Thanks for your valuable suggestion. To further examine the importance of the covalent linkage between the terminal phosphor and the homopolypeptide backbone in this CPRTP system, Hex-PLGA and BrNIB were co-assembled to obtain Hex-PLGA@BrNIB vesicles (Supplementary Fig. 23a-b). These vesicles showed a markedly lower phosphorescence-to-fluorescence intensity ratio compared with BrNI-PLGA vesicle powders (Supplementary Fig. 23c-d), and CPL measurements revealed nearly no discernible chiral emission in either spectral region (Supplementary Fig. 23e-f). This confirms that covalent tethering of the phosphor to the homopolypeptide backbone not only promotes phosphorescence generation but also plays a key role in enabling CPRTP. Subsequently, Hex-PLGA@BrNIB vesicles were mixed with PVA solution and processed similarly to fabricate the Hex-PLGA@BrNIB/PVA film (Supplementary Fig. 24a). Although the phosphorescence lifetime reached 5.98 ms, the phosphorescence-to-fluorescence intensity ratio remained low (Supplementary Fig. 24b-c), indicating inferior RTP performance relative to the BrNI-PLGA/PVA film. Meanwhile, PVA-induced CPRTP was also observed in the Hex-PLGA@BrNIB/PVA film (Supplementary Fig. 24d-f), but its performance was weaker than that of the BrNI-PLGA/PVA film. Therefore, these findings demonstrate that covalent attachment of the phosphor to the homopolypeptide terminus is advantageous for achieving enhanced CPRTP properties in both vesicle and film states within these homopolypeptide/PVA systems.\nSupplementary Fig. 23 Photophysical properties of Hex-PLGA@BrNIB vesicle. a Illustration for the co-assembly. b SEM image. c Normalized PL spectra. λ = 330 nm. d Time-resolved phosphorescent decay curves. λ = 330 nm. λ = 580 nm. e CPL spectra. λ = 330 nm. f g curves. λ = 330 nm.\nSupplementary Fig. 24 Photophysical properties of Hex-PLGA@BrNIB/PVA film. a Illustration for the fabrication of Hex-PLGA@BrNIB/PVA film. C = 10 mg/mL. b Normalized PL spectra. λ = 330 nm. c Time-resolved phosphorescent decay curves. λ = 330 nm. λ = 580 nm. d CD spectra. e CPL spectra. λ = 330 nm. f g curves. λ = 330 nm.\n5. By incorporating different phosphors, the authors successfully achieved color-tunable CPRTP systems, demonstrating both the generality of their strategy and the reliability of the proposed mechanism. It is also suggested that the authors discuss potential application prospects and practical scenarios for such systems.\nReply: Thanks for your suggestion. Based on the unique combination of long-lived emission, circular polarization, and color tunability, we envision two main promising directions described in Section 2.5 in the revised manuscript.\n“The unique combination of color-tunable, long-lived, and circularly polarized emission in these supramolecular films suggests promising application prospects. The multicolor CPRTP afterglow could be exploited in advanced anti-counterfeiting and multilevel information encryption, where time-resolved and polarization-dependent signals provide enhanced security dimensions. Additionally, such materials may serve as novel chiral light sources in circularly polarized optoelectronics or as functional components in smart displays and optical sensors.”\nReviewer #3 (Remarks to the Author):\nThe manuscript presents an interesting phenomenon in the field of circularly polarized room-temperature phosphorescence (CPRTP) on chiral inversion and amplification induced by achiral poly(vinyl alcohol) (PVA) matrix. The authors demonstrate that vesicles self-assembled from chiral homopolypeptides exhibit weak yet detectable CPRTP. Remarkably, when these pre-assembled vesicles are incorporated into the achiral PVA matrix to form hybrid films, the system undergoes an inversion of chirality accompanied by the amplification of the CPRTP signal. The manuscript is supported by a comprehensive set of data, with strength in the mechanistic investigation that combines experimental evidence and molecular dynamics simulations. The core innovation of this work lies in its demonstration that supramolecular chirality can be controlled via intermolecular interactions of chiral assemblies with achiral polymer matrix, which may provide a new thinking for regulating chirality in CPRTP-active materials using commercially available polymers. I recommend publication after the authors address the following points to further strengthen the manuscript.\nReply: Thanks for your comments, and we appreciate your recognition of our work.\n1. The study clearly demonstrates that chirality arises from the self-assembly of chiral homopolypeptides in both vesicle and film states. However, it remains unclear whether the covalent attachment of the phosphor terminal is essential for the observed chirality inversion and amplification. A relevant control experiment—such as physically mixing the phosphor with the homopolypeptide and PVA—could help determine if non-covalent systems exhibit similar behavior, as recently illustrated in supramolecular chirality studies (e.g., Science 2025, 389, eadu0296). Clarifying this point would significantly strengthen the mechanistic claims.\nReply: Thanks for your suggestion. To further examine the importance of the covalent linkage between the terminal phosphor and the homopolypeptide backbone in this CPRTP system, Hex-PLGA and BrNIB were co-assembled to obtain Hex-PLGA@BrNIB vesicles (Supplementary Fig. 23a-b). These vesicles showed a markedly lower phosphorescence-to-fluorescence intensity ratio compared with BrNI-PLGA vesicle powders (Supplementary Fig. 23c-d), and CPL measurements revealed nearly no discernible chiral emission in either spectral region (Supplementary Fig. 23e-f). This confirms that covalent tethering of the phosphor to the homopolypeptide backbone not only promotes phosphorescence generation but also plays a key role in enabling CPRTP. Subsequently, Hex-PLGA@BrNIB vesicles were mixed with PVA solution and processed similarly to fabricate the Hex-PLGA@BrNIB/PVA film (Supplementary Fig. 24a). Although the phosphorescence lifetime reached 5.98 ms, the phosphorescence-to-fluorescence intensity ratio remained low (Supplementary Fig. 24b-c), indicating inferior RTP performance relative to the BrNI-PLGA/PVA film. Meanwhile, PVA-induced CPRTP was also observed in the Hex-PLGA@BrNIB/PVA film (Supplementary Fig. 24d-f), but its performance was weaker than that of the BrNI-PLGA/PVA film. Therefore, these findings demonstrate that covalent attachment of the phosphor to the homopolypeptide terminus is advantageous for achieving enhanced CPRTP properties in both vesicle and film states within these homopolypeptide/PVA systems.\nSupplementary Fig. 23 Photophysical properties of Hex-PLGA@BrNIB vesicle. a Illustration for the co-assembly. b SEM image. c Normalized PL spectra. λ = 330 nm. d Time-resolved phosphorescent decay curves. λ = 330 nm. λ = 580 nm. e CPL spectra. λ = 330 nm. f g curves. λ = 330 nm.\nSupplementary Fig. 24 Photophysical properties of Hex-PLGA@BrNIB/PVA film. a Illustration for the fabrication of Hex-PLGA@BrNIB/PVA film. C = 10 mg/mL. b Normalized PL spectra. λ = 330 nm. c Time-resolved phosphorescent decay curves. λ = 330 nm. λ = 580 nm. d CD spectra. e CPL spectra. λ = 330 nm. f g curves. λ = 330 nm.\n2. The authors attribute the chiral inversion and amplification to the hydrogen-bonding capability of PVA. To further substantiate this mechanism, it would be compelling to investigate other hydrogen-bonding polymers. For instance, employing a matrix like poly(acrylic acid), which can act as both a donor and acceptor of hydrogen bonds, could serve as a critical experiment to test the generality of the proposed mechanism and clarify the specific role of hydrogen-bonding topology.\nReply: Thanks for your suggestions. As a stronger hydrogen-bond donor than PVA, poly(acrylic acid) (PAA) was also employed to prepare a BrNI-PLGA/PAA film (Supplementary Fig. 21a). This composite likewise exhibited obvious RTP (Supplementary Fig. 21b-c), yet its chiral absorption and emission signals remained relatively weak, with a g value reaching only 1.25 × 10−3 (Supplementary Fig. 21d-f). These results collectively suggest that moderately strong hydrogen-bonding interactions provided by PVA play a crucial role in enabling effective chirality inversion and amplification.\nSupplementary Fig. 21 Photophysical properties of BrNI-PLGA/poly(acrylic acid) (PAA) film. a Illustration for the fabrication of BrNI-PLGA/PAA film. C = 10 mg/mL. b Normalized PL spectra. λ = 330 nm. c Time-resolved phosphorescent decay curves. λ = 330 nm. λ = 580 nm. d CD spectra. e CPL spectra. λ = 330 nm. f g curves. λ = 330 nm.\n3. The molecular dynamics (MD) simulations of peptide dimers provide valuable insight into chiral generation and PVA-induced chiral inversion, attributed to different chiral packing of peptide terminals. I’m wondering whether it is possible to display the chiral packing mode using more peptide chains? Of course, such simulation may be quite complex and computationally demanding. If feasible, it may enhance the structural relevance of the conclusions.\nReply: Thank you for this important suggestion. To investigate whether the chiral packing mode persists in assemblies containing more peptide chains, we constructed a six-chain hexamer using an in-house script, propagating the terminal packing geometry observed in our right-assembly dimer simulations. A subsequent 100-ns simulation confirmed the structural stability of this hexamer (Supplementary Fig. 26a). It retained the same right-handed chiral π–π stacking of the C-terminal NI groups. As shown in Supplementary Fig. 26b-c, the mean dihedral angle (θ) was -55.18 ± 0.14° and the mean π–π distance (d) was 4.08 ± 0.01 Å (mean ± standard error of the mean, calculated from the five C-terminal NI–NI stacking pairs in the hexamer), both in excellent agreement with the values obtained for the dimer. This result demonstrates that the chiral packing mode identified in the dimer can indeed extend to larger assemblies. We have added a corresponding description in Section 2.4.\n“Moreover, to assess the propagation of the chiral packing mode from dimer to larger assemblies, we constructed a right-handed hexamer with an in-house script that reproduced the C-terminal NI group arrangement. The hexamer remained stable throughout a 100 ns simulation, with θ and d values matching the right-handed dimer (Supplementary Fig. 26), demonstrating that the chiral packing mode can propagate and is scalable within larger assemblies.”\nSupplementary Fig. 26 Molecular dynamics (MD) simulations for a hexameric assembly. a Structural snapshots at 0, 40, 80, and 100 ns of the simulation. b Evolution of the mean θ over time. c Evolution of the mean d over time.\n4. The manuscript contains several typographical errors (e.g., “targe” in Line 122, “homopolypepitde” in Line 146) and inconsistencies in formatting (e.g., font size of “Figure” and “Figure S.”). To meet the high publication standards expected by the journal, a thorough, line-by-line revision of the entire text is strongly recommended to ensure linguistic accuracy and stylistic consistency.\nReply: Thanks for your careful reading and valuable feedback. We sincerely apologize for the typographical errors and formatting inconsistencies. We have now conducted a thorough, line-by-line revision of the entire manuscript and supporting information, correcting all typographical errors (e.g., “targe” to “target,” “homopolypepitde” to “homopolypeptide”) and unifying the formatting (including figure labels, font sizes, and stylistic elements). We believe the revised manuscript now meets the journal's high standards of linguistic accuracy and presentation."}, {"round": 2, "reviewer_comments": {"reviewer_2": "The revision has satisfactorily addressed the reviewer’s concerns, and I recommend its publication in its present form.", "reviewer_3": "we are satisfied with the revisions made by the authors."}, "author_response": ""}]

Decision letter