Angell C Austen
Department of Chemistry and Biochemistry, Arizona State University, Tempe, AZ 85287, USA.
Philos Trans A Math Phys Eng Sci. 2005 Feb 15;363(1827):415-30; discussion 431-2. doi: 10.1098/rsta.2004.1500.
We describe basic phenomenology in the physics of supercooling liquids at constant volume (most simulations), and at constant pressure (most laboratory experiments) before focusing attention on the exceptional cases that exhibit liquid-liquid phase transitions on constant-pressure cooling. We give evidence for point defects in glasses and liquids near T(g). Models based on defects predict transitions with density gaps in constant-pressure systems. We describe the energy landscape representation of such systems. Water, in these terms, is post-critical, and its nearly ideal glass formation can be related to nucleation-free protein 'funnel-folding'. For nucleated folding of proteins, a pseudo-gap should be present. Experimental methods of distinguishing between alternative folding scenarios are described.
我们先描述了在等容(大多数模拟情况)和等压(大多数实验室实验情况)下过冷液体物理中的基本现象学,然后将注意力集中在等压冷却时出现液 - 液相转变的特殊情况上。我们给出了玻璃态和接近玻璃化转变温度(T(g))的液体中点缺陷的证据。基于缺陷的模型预测了等压系统中存在密度间隙的转变。我们描述了此类系统的能量景观表示。从这些方面来看,水处于临界后状态,其近乎理想的玻璃形成可能与无核蛋白的“漏斗折叠”有关。对于有核的蛋白质折叠,应该存在一个准能隙。文中还描述了区分不同折叠情况的实验方法。