Context Chronic diabetic foot ulcers (DFUs) are associated with the collapse of endogenous bioelectric field gradients and redox-compromised wound microenvironments, conditions under which externally applied electroceutical stimulation and reactive oxygen species (ROS)–dominated photodynamic therapies become ineffective or deleterious. This limitation motivates the search for intrinsic, bias-free mechanisms capable of generating localized bioelectric-scale fields using benign external energy inputs. At photoactive organic–semiconductor interfaces, excited-state intramolecular proton transfer (ESIPT) offers a pathway by which molecular photophysics may be converted into interfacial electrostatic modulation, yet this transduction mechanism has not been formulated within a rigorous quantum–electrostatic framework. Method Here, we develop a first-principles quantum modeling framework establishing the Stokes-Induced Stark Effect (SISE) at quercetin–ZnO interfaces as a bias-free mechanism for interfacial electric field generation. Visible-light excitation of chemisorbed quercetin induces ultrafast ESIPT-driven Stokes relaxation, accompanied by excited-state dipole reconfiguration (Δµ ≈ 5–15 D, τ ≈ 100 fs). This time-dependent dipole couples electrostatically to ZnO surface states, generating localized interfacial Stark fields of order 105–106 V·m⁻1. Using a composite molecular–semiconductor Hamiltonian incorporating dielectric screening and surface-state quantization, we show that although instantaneous fields are strongly attenuated in physiological media (Debye length <InlineEquation ID="IEq1"> <EquationSource Format="TEX">${\lambda }_{D} \approx 0.8$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <msub> <mi>λ</mi> <mi>D</mi> </msub> <mo>≈</mo> <mn>0.8</mn> </mrow> </math></EquationSource> </InlineEquation> nm), spatiotemporal integration via dipole-density gradients and continuous low-intensity illumination yields effective quasi-static comparable in magnitude to endogenous bioelectric signals at the interface (<InlineEquation ID="IEq2"> <EquationSource Format="TEX">$E_{eff}\approx50-500V\cdot m^{-1}$</EquationSource> <EquationSource Format="MATHML"><math> <mrow> <msub> <mi>E</mi> <mrow> <mi mathvariant="italic">eff</mi> </mrow> </msub> <mo>≈</mo> <mn>50</mn> <mo>-</mo> <mn>500</mn> <mi>V</mi> <mo>·</mo> <msup> <mi>m</mi> <mrow> <mo>-</mo> <mn>1</mn> </mrow> </msup> </mrow> </math></EquationSource> </InlineEquation>). The model explicitly avoids assumptions of static field penetration and instead delineates a defined operational window (coverage factor η ≈ 0.3–0.7; illumination < 10 mW·cm⁻2) in which electrostatic guidance dominates over ROS-driven photochemistry. The framework provides quantitative design constraints and experimentally testable predictions, establishing SISE as a physically plausible molecular photophysics–driven route for bias-free bioelectric modulation, with chronic wound repair serving as a representative application context.

Quantum modeling of Stokes-Induced Stark Fields in quercetin–ZnO nanohybrids for bias-free bioelectric repair of chronic diabetic foot ulcers

期刊论文
发表日期：

2026年3月30日

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Moses Udoisoh,
Ediomo M. Ekanem,
Williams Obinna Obiya,
Chisimdindu Goodness Ofoezie,
Hannah Yahaya,
Lucky Endas,
Nathaniel Okpara

摘要

Context

Chronic diabetic foot ulcers (DFUs) are associated with the collapse of endogenous bioelectric field gradients and redox-compromised wound microenvironments, conditions under which externally applied electroceutical stimulation and reactive oxygen species (ROS)–dominated photodynamic therapies become ineffective or deleterious. This limitation motivates the search for intrinsic, bias-free mechanisms capable of generating localized bioelectric-scale fields using benign external energy inputs. At photoactive organic–semiconductor interfaces, excited-state intramolecular proton transfer (ESIPT) offers a pathway by which molecular photophysics may be converted into interfacial electrostatic modulation, yet this transduction mechanism has not been formulated within a rigorous quantum–electrostatic framework.

Method

Here, we develop a first-principles quantum modeling framework establishing the Stokes-Induced Stark Effect (SISE) at quercetin–ZnO interfaces as a bias-free mechanism for interfacial electric field generation. Visible-light excitation of chemisorbed quercetin induces ultrafast ESIPT-driven Stokes relaxation, accompanied by excited-state dipole reconfiguration (Δµ ≈ 5–15 D, τ ≈ 100 fs). This time-dependent dipole couples electrostatically to ZnO surface states, generating localized interfacial Stark fields of order 10⁵–10⁶ V·m⁻¹. Using a composite molecular–semiconductor Hamiltonian incorporating dielectric screening and surface-state quantization, we show that although instantaneous fields are strongly attenuated in physiological media (Debye length ${\lambda }_{D} \approx 0.8$ $λ_{D} \approx 0.8$ nm), spatiotemporal integration via dipole-density gradients and continuous low-intensity illumination yields effective quasi-static comparable in magnitude to endogenous bioelectric signals at the interface ( $E_{eff}\approx50-500V\cdot m^{-1}$ $E_{eff} \approx 50 - 500 V \cdot m^{- 1}$ ). The model explicitly avoids assumptions of static field penetration and instead delineates a defined operational window (coverage factor η ≈ 0.3–0.7; illumination < 10 mW·cm⁻²) in which electrostatic guidance dominates over ROS-driven photochemistry. The framework provides quantitative design constraints and experimentally testable predictions, establishing SISE as a physically plausible molecular photophysics–driven route for bias-free bioelectric modulation, with chronic wound repair serving as a representative application context.