双语化学辞典Chem Lexicon
研究生Graduate 化学动力学 Chemical kinetics

斯特恩–福尔默方程Stern–Volmer equation

\[\frac{I_0}{I} = \frac{\tau_0}{\tau} = 1 + k_q\tau_0[\mathrm Q] = 1 + K_\mathrm{SV}[\mathrm Q]\]

含义Meaning

猝灭剂 Q 与激发态碰撞使其非辐射失活,荧光强度和寿命随 [Q] 下降;I₀/I 对 [Q] 为直线(动态猝灭)。用于测氧传感器、蛋白质中色氨酸的可及性等。

A quencher Q deactivates excited states by collision, lowering fluorescence intensity and lifetime; I₀/I is linear in [Q] (dynamic quenching). Used in oxygen sensors and tryptophan-accessibility studies.

符号说明Symbols

符号Symbol含义 Meaning单位 Unit
\(I_0, I\)无 / 有猝灭剂时的荧光强度intensity without / with quencher
\(k_q\)双分子猝灭速率常数bimolecular quenching constantL·mol⁻¹·s⁻¹
\(\tau_0\)无猝灭时寿命unquenched lifetimes
\(K_\mathrm{SV}\)斯特恩–福尔默常数Stern–Volmer constantL·mol⁻¹

推导Derivation

  1. 激发态 M* 衰减:\(k_r + k_{nr} + k_q[\mathrm Q]\);荧光量子产率 \(\Phi = k_r/(k_r + k_{nr} + k_q[\mathrm Q])\)。

    M* decays by k_r + k_nr + k_q[Q].

  2. 无猝灭剂时 \(\Phi_0 = k_r\tau_0\),相除得 \(\Phi_0/\Phi = 1 + k_q\tau_0[\mathrm Q]\)。

    Dividing by the unquenched yield gives the result.

  3. \(k_q\) 接近扩散控制(约 10¹⁰ L·mol⁻¹·s⁻¹)说明每次碰撞都猝灭。

    k_q near 10¹⁰ means quenching on every encounter.

适用条件与局限Assumptions & limitations

  • 静态猝灭(基态络合)只降低强度不改变寿命,图线上弯;同时存在两种猝灭时需二次式。

    Static quenching lowers intensity but not lifetime and bends the plot upward.