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pH‐triggered supramolecular topology switching and interfacial characterization of VDAP‐LLC. (A) Helical wheel projection of VDAP showing its amphipathic organization, including the hydrophobic domain (blue), cationic anchoring domain (orange), and histidine‐containing pH‐sensing residues (purple). (B) Zeta potential profiles of Blank LLC and VDAP‐LLC under different pH conditions. Data are presented as mean ± SD, n = 3. Pairwise comparisons between Blank LLC and VDAP‐LLC at each pH value were performed using Mann–Whitney tests with correction for multiple comparisons; no significant differences were observed. (C) Schematic illustration of the pH‐dependent cooperative electrostatic switching mechanism. (D–G) Small‐angle X‐ray scattering profiles. (D) Superimposed 1D scattering profiles at pH 7.4. The inset shows contraction of the lattice parameter from 55.1 to 50.0 Å after VDAP loading. (E) VDAP‐LLC at pH 7.4 showing characteristic 1: √3: 2 reflections of the inverse hexagonal H <t>II</t> <t>mesophase.</t> (F) VDAP‐LLC at pH 6.5 showing an intermediate scattering pattern. The first three peak‐position ratios (1, 1.690, and 1.940) are close to the characteristic 1: √3: 2 reflections of the H II phase, whereas additional higher‐q features (2.333, 2.940, and 3.833) approximate Im 3̄ m ‐related reflections, indicating a mixed H II /cubic‐like intermediate state under weakly acidic conditions. (G) VDAP‐LLC at pH 5.0 showing √2: √6: √8: √12 reflections of the primitive bicontinuous cubic Im 3̄ m phase. The theoretical √4 (200) reflection is suppressed by the bilayer form‐factor minimum. (H–K) Polarized light microscopy (PLM) images of (H) Blank LLC at pH 7.4, (I) VDAP‐LLC at pH 7.4 showing anisotropic focal‐conic textures, and (J) VDAP‐LLC at pH 6.5 showing attenuated but still detectable birefringent textures, and (K) VDAP‐LLC at pH 5.0 showing an optically isotropic dark field. Scale bar: 100 µm.
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pH‐triggered supramolecular topology switching and interfacial characterization of VDAP‐LLC. (A) Helical wheel projection of VDAP showing its amphipathic organization, including the hydrophobic domain (blue), cationic anchoring domain (orange), and histidine‐containing pH‐sensing residues (purple). (B) Zeta potential profiles of Blank LLC and VDAP‐LLC under different pH conditions. Data are presented as mean ± SD, n = 3. Pairwise comparisons between Blank LLC and VDAP‐LLC at each pH value were performed using Mann–Whitney tests with correction for multiple comparisons; no significant differences were observed. (C) Schematic illustration of the pH‐dependent cooperative electrostatic switching mechanism. (D–G) Small‐angle X‐ray scattering profiles. (D) Superimposed 1D scattering profiles at pH 7.4. The inset shows contraction of the lattice parameter from 55.1 to 50.0 Å after VDAP loading. (E) VDAP‐LLC at pH 7.4 showing characteristic 1: √3: 2 reflections of the inverse hexagonal H <t>II</t> <t>mesophase.</t> (F) VDAP‐LLC at pH 6.5 showing an intermediate scattering pattern. The first three peak‐position ratios (1, 1.690, and 1.940) are close to the characteristic 1: √3: 2 reflections of the H II phase, whereas additional higher‐q features (2.333, 2.940, and 3.833) approximate Im 3̄ m ‐related reflections, indicating a mixed H II /cubic‐like intermediate state under weakly acidic conditions. (G) VDAP‐LLC at pH 5.0 showing √2: √6: √8: √12 reflections of the primitive bicontinuous cubic Im 3̄ m phase. The theoretical √4 (200) reflection is suppressed by the bilayer form‐factor minimum. (H–K) Polarized light microscopy (PLM) images of (H) Blank LLC at pH 7.4, (I) VDAP‐LLC at pH 7.4 showing anisotropic focal‐conic textures, and (J) VDAP‐LLC at pH 6.5 showing attenuated but still detectable birefringent textures, and (K) VDAP‐LLC at pH 5.0 showing an optically isotropic dark field. Scale bar: 100 µm.
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pH‐triggered supramolecular topology switching and interfacial characterization of VDAP‐LLC. (A) Helical wheel projection of VDAP showing its amphipathic organization, including the hydrophobic domain (blue), cationic anchoring domain (orange), and histidine‐containing pH‐sensing residues (purple). (B) Zeta potential profiles of Blank LLC and VDAP‐LLC under different pH conditions. Data are presented as mean ± SD, n = 3. Pairwise comparisons between Blank LLC and VDAP‐LLC at each pH value were performed using Mann–Whitney tests with correction for multiple comparisons; no significant differences were observed. (C) Schematic illustration of the pH‐dependent cooperative electrostatic switching mechanism. (D–G) Small‐angle X‐ray scattering profiles. (D) Superimposed 1D scattering profiles at pH 7.4. The inset shows contraction of the lattice parameter from 55.1 to 50.0 Å after VDAP loading. (E) VDAP‐LLC at pH 7.4 showing characteristic 1: √3: 2 reflections of the inverse hexagonal H <t>II</t> <t>mesophase.</t> (F) VDAP‐LLC at pH 6.5 showing an intermediate scattering pattern. The first three peak‐position ratios (1, 1.690, and 1.940) are close to the characteristic 1: √3: 2 reflections of the H II phase, whereas additional higher‐q features (2.333, 2.940, and 3.833) approximate Im 3̄ m ‐related reflections, indicating a mixed H II /cubic‐like intermediate state under weakly acidic conditions. (G) VDAP‐LLC at pH 5.0 showing √2: √6: √8: √12 reflections of the primitive bicontinuous cubic Im 3̄ m phase. The theoretical √4 (200) reflection is suppressed by the bilayer form‐factor minimum. (H–K) Polarized light microscopy (PLM) images of (H) Blank LLC at pH 7.4, (I) VDAP‐LLC at pH 7.4 showing anisotropic focal‐conic textures, and (J) VDAP‐LLC at pH 6.5 showing attenuated but still detectable birefringent textures, and (K) VDAP‐LLC at pH 5.0 showing an optically isotropic dark field. Scale bar: 100 µm.
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pH‐triggered supramolecular topology switching and interfacial characterization of VDAP‐LLC. (A) Helical wheel projection of VDAP showing its amphipathic organization, including the hydrophobic domain (blue), cationic anchoring domain (orange), and histidine‐containing pH‐sensing residues (purple). (B) Zeta potential profiles of Blank LLC and VDAP‐LLC under different pH conditions. Data are presented as mean ± SD, n = 3. Pairwise comparisons between Blank LLC and VDAP‐LLC at each pH value were performed using Mann–Whitney tests with correction for multiple comparisons; no significant differences were observed. (C) Schematic illustration of the pH‐dependent cooperative electrostatic switching mechanism. (D–G) Small‐angle X‐ray scattering profiles. (D) Superimposed 1D scattering profiles at pH 7.4. The inset shows contraction of the lattice parameter from 55.1 to 50.0 Å after VDAP loading. (E) VDAP‐LLC at pH 7.4 showing characteristic 1: √3: 2 reflections of the inverse hexagonal H <t>II</t> <t>mesophase.</t> (F) VDAP‐LLC at pH 6.5 showing an intermediate scattering pattern. The first three peak‐position ratios (1, 1.690, and 1.940) are close to the characteristic 1: √3: 2 reflections of the H II phase, whereas additional higher‐q features (2.333, 2.940, and 3.833) approximate Im 3̄ m ‐related reflections, indicating a mixed H II /cubic‐like intermediate state under weakly acidic conditions. (G) VDAP‐LLC at pH 5.0 showing √2: √6: √8: √12 reflections of the primitive bicontinuous cubic Im 3̄ m phase. The theoretical √4 (200) reflection is suppressed by the bilayer form‐factor minimum. (H–K) Polarized light microscopy (PLM) images of (H) Blank LLC at pH 7.4, (I) VDAP‐LLC at pH 7.4 showing anisotropic focal‐conic textures, and (J) VDAP‐LLC at pH 6.5 showing attenuated but still detectable birefringent textures, and (K) VDAP‐LLC at pH 5.0 showing an optically isotropic dark field. Scale bar: 100 µm.
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pH‐triggered supramolecular topology switching and interfacial characterization of VDAP‐LLC. (A) Helical wheel projection of VDAP showing its amphipathic organization, including the hydrophobic domain (blue), cationic anchoring domain (orange), and histidine‐containing pH‐sensing residues (purple). (B) Zeta potential profiles of Blank LLC and VDAP‐LLC under different pH conditions. Data are presented as mean ± SD, n = 3. Pairwise comparisons between Blank LLC and VDAP‐LLC at each pH value were performed using Mann–Whitney tests with correction for multiple comparisons; no significant differences were observed. (C) Schematic illustration of the pH‐dependent cooperative electrostatic switching mechanism. (D–G) Small‐angle X‐ray scattering profiles. (D) Superimposed 1D scattering profiles at pH 7.4. The inset shows contraction of the lattice parameter from 55.1 to 50.0 Å after VDAP loading. (E) VDAP‐LLC at pH 7.4 showing characteristic 1: √3: 2 reflections of the inverse hexagonal H <t>II</t> <t>mesophase.</t> (F) VDAP‐LLC at pH 6.5 showing an intermediate scattering pattern. The first three peak‐position ratios (1, 1.690, and 1.940) are close to the characteristic 1: √3: 2 reflections of the H II phase, whereas additional higher‐q features (2.333, 2.940, and 3.833) approximate Im 3̄ m ‐related reflections, indicating a mixed H II /cubic‐like intermediate state under weakly acidic conditions. (G) VDAP‐LLC at pH 5.0 showing √2: √6: √8: √12 reflections of the primitive bicontinuous cubic Im 3̄ m phase. The theoretical √4 (200) reflection is suppressed by the bilayer form‐factor minimum. (H–K) Polarized light microscopy (PLM) images of (H) Blank LLC at pH 7.4, (I) VDAP‐LLC at pH 7.4 showing anisotropic focal‐conic textures, and (J) VDAP‐LLC at pH 6.5 showing attenuated but still detectable birefringent textures, and (K) VDAP‐LLC at pH 5.0 showing an optically isotropic dark field. Scale bar: 100 µm.
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pH‐triggered supramolecular topology switching and interfacial characterization of VDAP‐LLC. (A) Helical wheel projection of VDAP showing its amphipathic organization, including the hydrophobic domain (blue), cationic anchoring domain (orange), and histidine‐containing pH‐sensing residues (purple). (B) Zeta potential profiles of Blank LLC and VDAP‐LLC under different pH conditions. Data are presented as mean ± SD, n = 3. Pairwise comparisons between Blank LLC and VDAP‐LLC at each pH value were performed using Mann–Whitney tests with correction for multiple comparisons; no significant differences were observed. (C) Schematic illustration of the pH‐dependent cooperative electrostatic switching mechanism. (D–G) Small‐angle X‐ray scattering profiles. (D) Superimposed 1D scattering profiles at pH 7.4. The inset shows contraction of the lattice parameter from 55.1 to 50.0 Å after VDAP loading. (E) VDAP‐LLC at pH 7.4 showing characteristic 1: √3: 2 reflections of the inverse hexagonal H <t>II</t> <t>mesophase.</t> (F) VDAP‐LLC at pH 6.5 showing an intermediate scattering pattern. The first three peak‐position ratios (1, 1.690, and 1.940) are close to the characteristic 1: √3: 2 reflections of the H II phase, whereas additional higher‐q features (2.333, 2.940, and 3.833) approximate Im 3̄ m ‐related reflections, indicating a mixed H II /cubic‐like intermediate state under weakly acidic conditions. (G) VDAP‐LLC at pH 5.0 showing √2: √6: √8: √12 reflections of the primitive bicontinuous cubic Im 3̄ m phase. The theoretical √4 (200) reflection is suppressed by the bilayer form‐factor minimum. (H–K) Polarized light microscopy (PLM) images of (H) Blank LLC at pH 7.4, (I) VDAP‐LLC at pH 7.4 showing anisotropic focal‐conic textures, and (J) VDAP‐LLC at pH 6.5 showing attenuated but still detectable birefringent textures, and (K) VDAP‐LLC at pH 5.0 showing an optically isotropic dark field. Scale bar: 100 µm.
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pH‐triggered supramolecular topology switching and interfacial characterization of VDAP‐LLC. (A) Helical wheel projection of VDAP showing its amphipathic organization, including the hydrophobic domain (blue), cationic anchoring domain (orange), and histidine‐containing pH‐sensing residues (purple). (B) Zeta potential profiles of Blank LLC and VDAP‐LLC under different pH conditions. Data are presented as mean ± SD, n = 3. Pairwise comparisons between Blank LLC and VDAP‐LLC at each pH value were performed using Mann–Whitney tests with correction for multiple comparisons; no significant differences were observed. (C) Schematic illustration of the pH‐dependent cooperative electrostatic switching mechanism. (D–G) Small‐angle X‐ray scattering profiles. (D) Superimposed 1D scattering profiles at pH 7.4. The inset shows contraction of the lattice parameter from 55.1 to 50.0 Å after VDAP loading. (E) VDAP‐LLC at pH 7.4 showing characteristic 1: √3: 2 reflections of the inverse hexagonal H <t>II</t> <t>mesophase.</t> (F) VDAP‐LLC at pH 6.5 showing an intermediate scattering pattern. The first three peak‐position ratios (1, 1.690, and 1.940) are close to the characteristic 1: √3: 2 reflections of the H II phase, whereas additional higher‐q features (2.333, 2.940, and 3.833) approximate Im 3̄ m ‐related reflections, indicating a mixed H II /cubic‐like intermediate state under weakly acidic conditions. (G) VDAP‐LLC at pH 5.0 showing √2: √6: √8: √12 reflections of the primitive bicontinuous cubic Im 3̄ m phase. The theoretical √4 (200) reflection is suppressed by the bilayer form‐factor minimum. (H–K) Polarized light microscopy (PLM) images of (H) Blank LLC at pH 7.4, (I) VDAP‐LLC at pH 7.4 showing anisotropic focal‐conic textures, and (J) VDAP‐LLC at pH 6.5 showing attenuated but still detectable birefringent textures, and (K) VDAP‐LLC at pH 5.0 showing an optically isotropic dark field. Scale bar: 100 µm.
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pH‐triggered supramolecular topology switching and interfacial characterization of VDAP‐LLC. (A) Helical wheel projection of VDAP showing its amphipathic organization, including the hydrophobic domain (blue), cationic anchoring domain (orange), and histidine‐containing pH‐sensing residues (purple). (B) Zeta potential profiles of Blank LLC and VDAP‐LLC under different pH conditions. Data are presented as mean ± SD, n = 3. Pairwise comparisons between Blank LLC and VDAP‐LLC at each pH value were performed using Mann–Whitney tests with correction for multiple comparisons; no significant differences were observed. (C) Schematic illustration of the pH‐dependent cooperative electrostatic switching mechanism. (D–G) Small‐angle X‐ray scattering profiles. (D) Superimposed 1D scattering profiles at pH 7.4. The inset shows contraction of the lattice parameter from 55.1 to 50.0 Å after VDAP loading. (E) VDAP‐LLC at pH 7.4 showing characteristic 1: √3: 2 reflections of the inverse hexagonal H <t>II</t> <t>mesophase.</t> (F) VDAP‐LLC at pH 6.5 showing an intermediate scattering pattern. The first three peak‐position ratios (1, 1.690, and 1.940) are close to the characteristic 1: √3: 2 reflections of the H II phase, whereas additional higher‐q features (2.333, 2.940, and 3.833) approximate Im 3̄ m ‐related reflections, indicating a mixed H II /cubic‐like intermediate state under weakly acidic conditions. (G) VDAP‐LLC at pH 5.0 showing √2: √6: √8: √12 reflections of the primitive bicontinuous cubic Im 3̄ m phase. The theoretical √4 (200) reflection is suppressed by the bilayer form‐factor minimum. (H–K) Polarized light microscopy (PLM) images of (H) Blank LLC at pH 7.4, (I) VDAP‐LLC at pH 7.4 showing anisotropic focal‐conic textures, and (J) VDAP‐LLC at pH 6.5 showing attenuated but still detectable birefringent textures, and (K) VDAP‐LLC at pH 5.0 showing an optically isotropic dark field. Scale bar: 100 µm.
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pH‐triggered supramolecular topology switching and interfacial characterization of VDAP‐LLC. (A) Helical wheel projection of VDAP showing its amphipathic organization, including the hydrophobic domain (blue), cationic anchoring domain (orange), and histidine‐containing pH‐sensing residues (purple). (B) Zeta potential profiles of Blank LLC and VDAP‐LLC under different pH conditions. Data are presented as mean ± SD, n = 3. Pairwise comparisons between Blank LLC and VDAP‐LLC at each pH value were performed using Mann–Whitney tests with correction for multiple comparisons; no significant differences were observed. (C) Schematic illustration of the pH‐dependent cooperative electrostatic switching mechanism. (D–G) Small‐angle X‐ray scattering profiles. (D) Superimposed 1D scattering profiles at pH 7.4. The inset shows contraction of the lattice parameter from 55.1 to 50.0 Å after VDAP loading. (E) VDAP‐LLC at pH 7.4 showing characteristic 1: √3: 2 reflections of the inverse hexagonal H II mesophase. (F) VDAP‐LLC at pH 6.5 showing an intermediate scattering pattern. The first three peak‐position ratios (1, 1.690, and 1.940) are close to the characteristic 1: √3: 2 reflections of the H II phase, whereas additional higher‐q features (2.333, 2.940, and 3.833) approximate Im 3̄ m ‐related reflections, indicating a mixed H II /cubic‐like intermediate state under weakly acidic conditions. (G) VDAP‐LLC at pH 5.0 showing √2: √6: √8: √12 reflections of the primitive bicontinuous cubic Im 3̄ m phase. The theoretical √4 (200) reflection is suppressed by the bilayer form‐factor minimum. (H–K) Polarized light microscopy (PLM) images of (H) Blank LLC at pH 7.4, (I) VDAP‐LLC at pH 7.4 showing anisotropic focal‐conic textures, and (J) VDAP‐LLC at pH 6.5 showing attenuated but still detectable birefringent textures, and (K) VDAP‐LLC at pH 5.0 showing an optically isotropic dark field. Scale bar: 100 µm.

Journal: Advanced Science

Article Title: Therapeutic Peptide‐Programmed Liquid‐Crystalline Topology Switching for pH‐Gated Postoperative Cancer Immunotherapy

doi: 10.1002/advs.78360

Figure Lengend Snippet: pH‐triggered supramolecular topology switching and interfacial characterization of VDAP‐LLC. (A) Helical wheel projection of VDAP showing its amphipathic organization, including the hydrophobic domain (blue), cationic anchoring domain (orange), and histidine‐containing pH‐sensing residues (purple). (B) Zeta potential profiles of Blank LLC and VDAP‐LLC under different pH conditions. Data are presented as mean ± SD, n = 3. Pairwise comparisons between Blank LLC and VDAP‐LLC at each pH value were performed using Mann–Whitney tests with correction for multiple comparisons; no significant differences were observed. (C) Schematic illustration of the pH‐dependent cooperative electrostatic switching mechanism. (D–G) Small‐angle X‐ray scattering profiles. (D) Superimposed 1D scattering profiles at pH 7.4. The inset shows contraction of the lattice parameter from 55.1 to 50.0 Å after VDAP loading. (E) VDAP‐LLC at pH 7.4 showing characteristic 1: √3: 2 reflections of the inverse hexagonal H II mesophase. (F) VDAP‐LLC at pH 6.5 showing an intermediate scattering pattern. The first three peak‐position ratios (1, 1.690, and 1.940) are close to the characteristic 1: √3: 2 reflections of the H II phase, whereas additional higher‐q features (2.333, 2.940, and 3.833) approximate Im 3̄ m ‐related reflections, indicating a mixed H II /cubic‐like intermediate state under weakly acidic conditions. (G) VDAP‐LLC at pH 5.0 showing √2: √6: √8: √12 reflections of the primitive bicontinuous cubic Im 3̄ m phase. The theoretical √4 (200) reflection is suppressed by the bilayer form‐factor minimum. (H–K) Polarized light microscopy (PLM) images of (H) Blank LLC at pH 7.4, (I) VDAP‐LLC at pH 7.4 showing anisotropic focal‐conic textures, and (J) VDAP‐LLC at pH 6.5 showing attenuated but still detectable birefringent textures, and (K) VDAP‐LLC at pH 5.0 showing an optically isotropic dark field. Scale bar: 100 µm.

Article Snippet: The nanoscale mesophase organization was analyzed by SAXS using a Xeuss 3.0 C system (Xenocs, France) equipped with a Cu Kα source(λ = 0.154 nm).

Techniques: Zeta Potential Analyzer, MANN-WHITNEY, Small Angle X-ray Scattering, Light Microscopy