定义Definition
光学活性是手性物质使平面偏振光的振动面发生旋转的性质。使偏振面顺时针(迎着光看)旋转的称右旋(+,d),逆时针的称左旋(−,l);外消旋体和内消旋体无旋光性。
Optical rotation is the turning of the plane of plane-polarised light by a chiral substance. Clockwise rotation (viewed towards the source) is dextrorotatory (+, d), anticlockwise laevorotatory (−, l); racemates and meso compounds are optically inactive.
原理Origin
平面偏振光可看作左、右旋圆偏振光的叠加。手性介质对两者的折射率不同(圆双折射),两束光通过后产生相位差,合成的偏振面因而旋转。旋光度随波长变化(旋光色散),吸收带附近还出现圆二色性(CD)。
Plane-polarised light is a superposition of left and right circularly polarised light. A chiral medium has different refractive indices for the two (circular birefringence), so a phase difference builds up and the plane rotates. Rotation varies with wavelength (optical rotatory dispersion), and near absorption bands circular dichroism appears.
测量Measurement
用旋光仪测定观测旋光角 α,换算为比旋光度 [α] = α/(l·c),通常在钠 D 线(589 nm)、20 °C 测定,须注明溶剂和浓度。
A polarimeter measures the observed rotation α, converted to specific rotation [α] = α/(l·c), usually at the sodium D line (589 nm) and 20 °C with solvent and concentration stated.
历史History
1811 年阿拉戈在石英晶体中发现旋光;1815 年毕奥发现松节油、糖溶液等液体也有旋光性,说明旋光性源于分子本身;1848 年巴斯德把旋光性与分子的手性联系起来;1874 年范特霍夫与勒贝尔提出四面体碳给出解释。
Arago found rotation in quartz in 1811; Biot showed in 1815 that liquids such as turpentine and sugar solutions rotate light, so the effect is molecular; Pasteur linked it to molecular handedness in 1848; van ’t Hoff and Le Bel explained it with the tetrahedral carbon in 1874.
年表Timeline
- 1811
阿拉戈发现石英的旋光
Arago discovers rotation by quartz
- 1815
毕奥发现液体的旋光性
Biot finds optical activity in liquids
- 1848
巴斯德拆分酒石酸盐
Pasteur resolves tartrate
- 1874
范特霍夫与勒贝尔提出四面体碳
van ’t Hoff and Le Bel propose tetrahedral carbon
相关公式Formulas
例题Worked example
蔗糖 [α]D²⁰ = +66.5°;c = 0.10 g/mL、l = 2 dm 时 α = +13.3°。
Sucrose [α]D²⁰ = +66.5°; at c = 0.10 g/mL, l = 2 dm, α = +13.3°.