【Angew.Chem.】中科院刘鸣华、河北科技大学朱华结、中国人民大学欧阳光辉|超声触发构建手性异质结螺旋结构:实现手性翻转与圆偏振发光40倍显著放大($g_{\text{lum}}$达0.2、荧光量子产率50%)
【Angew.Chem.】中科院刘鸣华、河北科技大学朱华结、中国人民大学欧阳光辉|超声触发构建手性异质结螺旋结构:实现手性翻转与圆偏振发光40倍显著放大(达0.2、荧光量子产率50%)
文章标题:Ultrasound‐Triggered Heterojunction Helices With Inverted Supramolecular Chirality and Significantly Amplified Circularly Polarized Luminescence 文章作者:Jinqi Li, Jingxiao Ren, Qi Feng, Jie Lu, Tianyi Li, Li Zhang, Guanghui Ouyang, Huajie Zhu, Minghua Liu 文章链接:https://doi.org/10.1002/anie.7074723

研究背景与破局思路:破解圆偏振发光“偏振度与亮度难以兼得”的瓶颈
圆偏振发光(CPL)是指发光材料在受到激发后,发出的光波像旋转的开瓶器一样,主要朝左旋或右旋某一个特定方向旋转振动。这种特殊的光学特性在3D立体显示、防伪加密、光学信息存储以及生物探针等前沿技术中具有巨大的应用潜力。衡量这类发光材料优劣有两个核心指标:一个是发光不对称因子(),用来衡量光旋转偏振的纯度与强度(理论极限为 );另一个是荧光量子产率(FLQY),用来衡量发光的亮度与发光效率。然而,在现有的分子发光体系中,单个分子发出的偏振信号往往极其微弱( 通常仅在 到 量级),而且往往提高偏振度就会牺牲发光亮度,难以同时实现超高发光偏振纯度与高发光效率。
为了解决这一难题,科学家通常尝试将发光小分子像搭积木一样组装成具有特定旋转方向的超分子纳米螺旋。但传统通过温度控制的组装方式,产物往往容易落入热力学平衡的稳定形态,限制了性能的进一步突破。本项研究打破了常规思路,首次利用超声波提供的外加机械力能量,精准调控单一手性分子在自组装过程中的分子折叠与生长路径,成功构建出自然界中极为罕见的“手性异质结微米螺旋”,在同一根微米螺旋上实现了手性翻转,并大幅放大了光学性能。

Fig.1 Molecular structures and schematic diagram of self-assembly. (a) Molecular structures of L-TPEAla and D-TPEAla. (b) Space filling model of DFT-optimized L-TPEAla. (c) Schematic illustration of heating-cooling protocol: L-TPEAla was dissolved in DMSO at 373K and then allowed to naturally cool to 298K, blue dots and helical rods represent monomers and nanohelices, respectively. (d) After adding MeCN (MeCN/DMSO = 2<3>3>, v/v) and aging over 2 h, the vial-inversion test showed the formation of an organogel, which was composed of left-handedness (M) microhelices with negative CPL. (e) After adding MeCN and performing ultrasound treatment for 3–5 min, a suspension is formed, which consisted of chiral heterojunction microstructures with amplified positive CPL. P indicates right-handedness.
核心机制与实验发现:超声诱导分子折叠与手性异质结螺旋的组装过程
研究团队设计合成了一种结合了聚集诱导发光(AIE)特性的四苯基乙烯基团与手性丙氨酸衍生物分子(命名为 TPEAla)。在常规组装过程中,将 型 TPEAla 分子溶解在热的二甲基亚砜(DMSO)中并自然冷却,分子会自发组装成左旋的手性纳米螺旋“晶种”。如果此时仅加入促沉淀溶剂乙腈(MeCN)并静置陈化,剩余的游离分子会顺着原有的模式继续生长,最终形成均一的左旋微米螺旋凝胶,其发光偏振度较低,发光不对称因子仅为 。
研究团队的关键突破在于:在加入乙腈后立即施加3至5分钟的超声波机械振荡处理。实验与密度泛函理论(DFT)计算表明,超声产生的瞬态机械力并非单纯加热,而是提供了克服能垒的能量,促使体系中原本呈“伸展构象”的游离分子通过分子内氢键重构,快速转变为“折叠构象”。这些新生成的折叠分子并没有独立形成新聚集体,而是特异性地跑到预先生成的左旋纳米螺旋两端进行分枝状二次生长。最终,体系生长成了一种全新的手性异质结结构——主干部分为左旋(型)螺旋核心,而两端分叉的树枝状结构则翻转为了右旋(型)螺旋。
这一独特的异质结结构带来了惊人的光学放大效应:
- 圆偏振发光信号翻转并实现40倍放大:发光信号由微米螺旋的负值转变为强烈的正值,发光不对称因子达到 。
- 高发光效率同步维持:得益于聚集诱导发光特性与高度有序的体心立方(BCC)紧密堆积模式,其荧光量子产率达到了约 50%,比未超声处理的微米螺旋提升了近一倍。

Fig.2 Characterization of nanohelices. (a) Variable-temperature UV-Vis spectra, (b) Variable-temperature fluorescence spectra and (d) DLS data of L-TPEAla in DMSO cooling from 373 to 343 K and finally to 298 K. The dashed gray lines are intermediate curves between these temperatures, the cuvette inserted in (d) showed Tyndall effect. The cooling rates are 5 K/min. (c) L-TPEAla dissolved in D6-DMSO was analyzed by variable-temperature nuclear magnetic resonance (NMR) spectroscopy, and the NMR integrals of proton A (labeled in Figure 1a) versus temperature and aging time were plotted (see Figure S6 for the original NMR spectra). Cryo-TEM images of L-TPEAla assemblies after cooling to (e) 343 K and (f) 298 K indicated the formation of nanohelices. (g) Variable-temperature CD of L-TPEAla assemblies at a cooling rate of 5 K/min. (h) Variable-temperature CD of D-TPEAla assemblies at a cooling rate of 5 K/min. The dashed lines are intermediate lines at different temperatures. (i) The CD spectra of L-TPEAla assemblies (red line) and D-TPEAla assemblies (blue line) after cooling to 298 K by naturally cooling in room temperature. [TPEAla] = 9.52 mM in DMSO, cuvette path length 10 mm. λex = 320 nm for FL measurements.

Fig.3 SEM and fluorescent microscopy images of microhelices and heterojunction helices. SEM images of (a) L-TPEAla and (b) D-TPEAla gels. (c) Fluorescent microscopy image of L-TPEAla gels. SEM images of (d, e) L-TPEAla and (f, g) D-TPEAla suspensions obtained by 40 kHz sonication. (h, i) Bright field and fluorescent microscopy images of L-TPEAla suspensions. All the samples were made in DMSO/MeCN co-solvents (v/v, 3<2>2>), [TPEAla] = 5.71 mM.

Fig.4 Comparison of optical and chiroptical properties of microhelices and heterojunction helices. (a) UV-Vis spectra, (b) Fluorescence spectra, (c) fluorescence lifetime, (d) CD spectra, (e) CPL spectra of microhelices (blue lines) and heterojunction helices (red lines). (f) glum values and quantum yields of microhelices (blue columns) and heterojunction helices (red columns). The optical path lengths for UV-Vis, FL, CD and CPL measurements are all 1 mm (while those for quantum yield and fluorescence lifetime measurements are 10 mm).

Fig.5 Control experiments. (a, b, d) Schematic illustration of disassembly and reassembly of heterojunction helices at different temperatures. The red and blue dots indicate folded and extended monomers, respectively. SEM image of L-TPEAla assemblies obtained by (c) heating heterojunction helices to 343 K and then cooling to 298 K, (e) heating heterojunction helices to 373 K and then cooling to 298 K. (f) DLS data of L-TPEAla assemblies after heating heterojunction helices to 343 K. (g) CPL spectra of L-TPEAla assemblies obtained by heating heterojunction helices to 343 K then cooling to 298 K (blue line) or heating to 373 K and then cooling to 298 K (green line). [L-TPEAla] = 5.71 mM in DMSO/MeCN (v/v, 3<2>2>). (h) CPL spectrum of L-TPEAla assemblies obtained in DMSO without the addition of MeCN, the assembly was performed by heating-cooling procedure and then ultrasound treatment. [L-TPEAla] = 9.52 mM in DMSO. The optical path lengths for CPL and DLS measurements are 1 mm.
理论价值、实际应用意义与现存局限展望
该研究在理论层面首次证实了仅由单一手性小分子出发,通过外场动力学调控即可构筑出包含相反手性亚基的超分子异质结螺旋。这不仅揭示了机械力改变分子内/分子间氢键竞争、重定向自组装途径的底层物理化学机制,也为设计高不对称因子、高亮度的先进手性光学功能材料提供了全新的通用平台。在实际应用上,这类具备超高 值的圆偏振发光材料可直接赋能下一代超高清3D裸眼显示面板、高安全性光学防伪标签以及手性光电传感器。
在客观局限性方面,研究发现超声驱动生成的异质结螺旋属于动力学亚稳态产物,在室温悬浮液中放置 5 天后 CPL 强度会出现一定程度的衰减;此外,超声处理的介入时机和温度窗口较为敏感(必须在加入不良溶剂后的初始阶段于室温或低温下进行,若完全陈化形成微米螺旋后再超声则无法诱导异质结转变)。未来的研究方向将聚焦于进一步优化分子侧链以提升异质结纳米结构的长期热力学稳定性,并探索将该机械力组装策略拓展到更多具有不同发光波段的智能光电材料体系中。
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