双语化学辞典Chem Lexicon
技术 · 分析化学 · 光谱 Analytical chemistry · Spectroscopy

紫外-可见光谱Ultraviolet–visible spectroscopy

拼音Pinyin zǐ wài kě jiàn guāng pǔ 别名Also UV-Vis;电子吸收光谱;UV-Vis; electronic absorption spectroscopy

定义Definition

紫外-可见光谱是分子吸收紫外光(约 200–400 nm)和可见光(约 400–800 nm)后,价电子从基态跃迁到激发态所形成的吸收光谱。它用于有色或含共轭体系物质的定量分析,并能提供分子共轭结构的信息。

UV–visible spectroscopy records the absorption of ultraviolet (about 200–400 nm) and visible (about 400–800 nm) light by molecules as valence electrons are excited from ground to excited states. It is used to quantify coloured or conjugated substances and gives information on conjugated structures.

电子跃迁类型Types of transition

σ→σ*(能量最高,< 200 nm,饱和烃,真空紫外区);n→σ*(约 150–250 nm,含杂原子的饱和化合物如醇、胺);π→π*(不饱和和共轭体系,ε 大,共轭越长 λ_max 越长:乙烯 165 nm,1,3-丁二烯 217 nm,β-胡萝卜素 450 nm 呈橙色);n→π*(羰基等,约 270–300 nm,ε 小);还有过渡金属配合物的 d-d 跃迁和电荷转移跃迁(如 MnO₄⁻ 呈紫色)。由于振动和转动能级叠加,分子紫外光谱是宽的谱带。

σ→σ* transitions need the most energy (below 200 nm, in the vacuum UV, for saturated hydrocarbons); n→σ* occur at about 150–250 nm in saturated compounds with heteroatoms such as alcohols and amines; π→π* occur in unsaturated and conjugated systems with large ε, and longer conjugation shifts λ_max longer (ethylene 165 nm, 1,3-butadiene 217 nm, β-carotene 450 nm and orange); n→π* occur in carbonyls and similar groups at about 270–300 nm with small ε; and transition-metal complexes add d–d and charge-transfer bands (MnO₄⁻ is purple from the latter). Superimposed vibrational and rotational levels make molecular UV spectra broad bands.

经验规律与历史Empirical rules and history

1941 年伍德沃德总结了共轭二烯和 α,β-不饱和酮 λ_max 的经验计算规则,后经菲泽尔推广(伍德沃德-菲泽尔规则),在核磁共振普及前是推测天然产物结构的重要手段。物质的颜色是其吸收光的互补色:吸收蓝光(约 450 nm)显黄色,吸收绿光显紫红色。

In 1941 Woodward set out empirical rules for calculating λ_max of conjugated dienes and α,β-unsaturated ketones, later extended by Fieser (the Woodward–Fieser rules), an important tool for deducing natural-product structures before NMR. A substance's colour is complementary to the light it absorbs: absorbing blue (about 450 nm) it looks yellow, absorbing green it looks purple-red.

应用Applications

UV-Vis 是最常用的定量分析方法之一,用于测定金属离子(显色后)、药物含量、核酸和蛋白质浓度、酶活性、反应动力学和平衡常数(如 pKa);作为 HPLC 的检测器;表征共轭聚合物、量子点、金属纳米颗粒的表面等离子体共振和半导体禁带宽度(陶克图)。

UV-Vis is among the most used quantitative methods: metal ions after colour development, drug content, nucleic acids and proteins, enzyme activity, reaction kinetics and equilibrium constants such as pKa; it is the standard HPLC detector; and it characterises conjugated polymers, quantum dots, plasmon resonance of metal nanoparticles and semiconductor band gaps (Tauc plots).

年表Timeline

  • 1852

    比尔定律

    Beer's law

  • 1940

    贝克曼 DU 紫外分光光度计

    The Beckman DU UV spectrophotometer

  • 1941

    伍德沃德规则

    Woodward's rules