Department of Chemistry, New York University, New York, New York 10003, USA.
Acc Chem Res. 2010 May 18;43(5):684-92. doi: 10.1021/ar900288m.
We have made images of crystals illuminated with polarized light for almost two decades. Early on, we abandoned photosensitive chemicals in favor of digital electrophotometry with all of the attendant advantages of quantitative intensity data. Accurate intensities are a boon because they can be used to analytically discriminate small effects in the presence of larger ones. The change in the form of our data followed camera technology that transformed picture taking the world over. Ironically, exposures in early photographs were presumed to correlate simply with light intensity, raising the hope that photography would replace sensorial interpretation with mechanical objectivity and supplant the art of visual photometry. This was only true in part. Quantitative imaging accurate enough to render the separation of crystalloptical quantities had to await the invention of the solid-state camera. Many pioneers in crystal optics were also major figures in the early history of photography. We draw out the union of optical crystallography and photography because the tree that connects the inventors of photography is a structure unmatched for organizing our work during the past 20 years, not to mention that silver halide crystallites used in chemical photography are among the most consequential "crystals in light", underscoring our title. We emphasize crystals that have acquired optical properties such as linear birefringence, linear dichroism, circular birefringence, and circular dichroism, during growth from solution. Other crystalloptical effects were discovered that are unique to curiously dissymmetric crystals containing embedded oscillators. In the aggregate, dyed crystals constitute a generalization of single crystal matrix isolation. Simple crystals provided kinetic stability to include guests such as proteins or molecules in excited states. Molecular lifetimes were extended for the preparation of laser gain media and for the study of the photodynamics of single molecules. Luminophores were used as guests in crystals to reveal aspects of growth mechanisms by labeling surface structures such as steps and kinks. New methods were adopted for measuring and imaging the optical rotatory power of crystals. Chiroptical anisotropies can now be compared with the results of quantum chemical calculations that have emerged in the past 10 years. The rapid determination of the optical rotation and circular dichroism tensors of molecules in crystals, and the interpretation of these anisotropies, remains a subject of future research. Polycrystalline patterns that form far from equilibrium challenged the quantitative interpretation of micrographs when heterogeneities along the optical path and obliquely angled interfaces played large roles. Resulting "artifacts" were nevertheless incisive probes of polycrystalline texture and mesoscale chemistry in simple substances grown far from equilibrium or in biopathological crystals such as Alzheimer's amyloid plaques.
我们已经制作了近二十年用偏振光照明的晶体图像。早期,我们放弃了感光化学物质,转而采用具有定量强度数据的全数字静电测量法。准确的强度是一个优势,因为它们可用于在存在较大影响的情况下分析性地辨别较小的影响。我们数据形式的变化遵循着摄影技术的发展,这种技术改变了全球的摄影方式。具有讽刺意味的是,早期照片中的曝光被认为与光强度简单相关,这增加了摄影将用机械客观性取代感官解释并取代视觉光度测定艺术的希望。这在一定程度上是正确的。要实现晶体光学量的分离,定量成像必须等待固态相机的发明。晶体光学的许多先驱者也是摄影早期历史上的重要人物。我们之所以要阐述光学晶体学和摄影术的结合,是因为连接摄影术发明者的树是一种无与伦比的结构,它可以组织我们在过去 20 年中的工作,更不用说在化学摄影中使用的卤化银微晶是最重要的“光中的晶体”之一,突出了我们的标题。我们强调在溶液中生长过程中获得线性双折射、线性二色性、圆双折射和圆二色性等光学性质的晶体。其他晶体光学效应是在含有嵌入式振荡器的奇特非对称晶体中发现的独特效应。总的来说,染色晶体构成了单晶基质隔离的推广。简单晶体为包括处于激发态的蛋白质或分子在内的客体提供了动力学稳定性。分子寿命延长,可用于制备激光增益介质和研究单分子的光动力学。生色团被用作晶体中的客体,通过标记表面结构(如台阶和扭结)来揭示生长机制的各个方面。现已采用新的方法来测量和成像晶体的旋光能力。手性各向异性现在可以与过去 10 年中出现的量子化学计算结果进行比较。晶体中分子的旋光率和圆二色性张量的快速测定以及这些各向异性的解释仍然是未来研究的课题。远离平衡形成的多晶图案对微观照片的定量解释提出了挑战,因为光程和倾斜界面处的各向异性对微观照片的定量解释起着重要作用。由此产生的“伪影”仍然是对远离平衡生长的简单物质或阿尔茨海默氏症淀粉样斑块等生物病理晶体的多晶织构和介观化学的锐利探针。