Stevenson Steven, Dorn Harry C
Department of Chemistry, FIRST Molecules Center of Research, Purdue University Fort Wayne, Fort Wayne, Indiana 46805, United States.
Department of Chemistry, Virginia Tech, Blacksburg, Virginia 24060, United States.
Acc Chem Res. 2024 Aug 6;57(15):2154-2165. doi: 10.1021/acs.accounts.4c00302. Epub 2024 Jul 23.
ConspectusDuring the last 30 years, theoretical scientists imagined segmental families of monolayer carbon tubules with fullerene-based end-caps. These molecules would possess structural features of both enes (hemispherical end-caps) and tubular belts of single-walled carbon nano (SWCNTs). Yet, their experimental verification remained elusive for decades. It was not until 2020-2023 that segmental of fullertubes were finally confirmed in the lab. The shocking irony is that these fullertubes were unwittingly coproduced alongside fullerenes (e.g., C C C) in both flame and electric arc soot since the 1990s. Yet, nobody knew these "hidden" families of fullertubes were experimentally present in their extracted soot due to their low abundance and the absence of isolation methodology.This eruption of fullertube discoveries in 2020-2023 was brought to fruition by structural data, both DFT and experimental. This "Treasure Trove" of new molecules during this four-year window occurred with only quantities. Typically, milligram levels of purified samples are required for X-ray crystallography and C NMR structural analysis. The breakthrough for experimentally verifying the missing fullertubes was an aminopropanol reagent to selectively react with and remove spheroidal carbon (e.g., C, C, C) as hydrophilic derivatives. In contrast, there was suppressed reaction with fullertubes, which remained in organic solvent. It is well established that high symmetry (3-, 5-, and 6-fold) hemispheres for C-I and other fullerenes and metallofullerenes are prerequisite end-caps for fullertubes. For the case of [5,5] C fullertubes, this requirement results in only eight 3-, 5-, and 6-fold symmetry structural isomers possible from a total of 39,393 possible isolated pentagon rule (IPR) isomers. From this C list of 8 candidate isolated pentagon rule (IPR) high symmetry isomers, surprisingly only one structure matched the DFT polarizability versus chromatographic retention parameter (a new gold standard for isomer identification). The simultaneous emergence of DFT computations of other properties (e.g., total energy, HOMO-LUMO gap, UV-vis) for large carbon molecules provided support for structural determination. Experimental approaches (e.g., mass spectrometry, UV-vis, XPS, Raman, and STEM) provided additional layers of structural elucidation at the microgram level. For the first time, we developed a chemical isolation protocol that would allow the preparation and isolation of soluble pristine fullertubes in the range of C-C. To date, applications of SWCNTs for use in nanoscale computer applications requires purities greater than 99.999%. Although this stringent mandate has not yet been demonstrated using SWCNT samples, this high level of purity appears achievable for metallic [5,5] -C and semiconductor [10,0] -C [10,766] fullertubes. Moreover, commercial production of pristine fullertubes should easily be feasible by the flame method due to its continuous operation and inexpensive feedstock. For application development, theoretical and electrochemical experimental data show that fullertubes exhibit high catalytic activity in oxygen reduction reactions. In the medical sector, pristine fullertube dispersions exhibit antimicrobial effects on and .
综述
在过去30年里,理论科学家设想了具有富勒烯端帽的单层碳管的分段家族。这些分子将同时具备烯类(半球形端帽)和单壁碳纳米管(SWCNTs)管状带的结构特征。然而,几十年来它们的实验验证一直难以实现。直到2020年至2023年,富勒管的分段才最终在实验室中得到证实。令人震惊的讽刺是,自20世纪90年代以来,这些富勒管在火焰和电弧烟灰中都与富勒烯(如C、C、C)一起无意间共同产生。然而,由于其丰度低且缺乏分离方法,没有人知道这些“隐藏”的富勒管家族在提取的烟灰中是通过实验存在的。
2020年至2023年富勒管发现的爆发是由密度泛函理论(DFT)和实验的结构数据实现的。在这个四年的时间段内,这些新分子的“宝库”仅在少量情况下出现。通常,X射线晶体学和碳核磁共振(C NMR)结构分析需要毫克级别的纯化样品。实验验证缺失富勒管的突破是一种氨基丙醇试剂,它能与球形碳(如C、C、C)选择性反应并将其作为亲水性衍生物去除。相比之下,与富勒管的反应受到抑制,富勒管仍留在有机溶剂中。众所周知,C-I和其他富勒烯及金属富勒烯的高对称性(3、5和6重)半球是富勒管的必备端帽。对于[5,5] C富勒管的情况,这一要求导致在总共39393种可能的孤立五边形规则(IPR)异构体中,只有8种3、5和6重对称结构异构体是可能的。从这8种候选的孤立五边形规则(IPR)高对称性异构体的C列表中,令人惊讶的是只有一种结构与DFT极化率与色谱保留参数(一种新的异构体鉴定金标准)相匹配。同时出现的针对大型碳分子的其他性质(如总能量、HOMO-LUMO能隙、紫外可见光谱)的DFT计算为结构确定提供了支持。实验方法(如质谱、紫外可见光谱、X射线光电子能谱、拉曼光谱和扫描透射电子显微镜)在微克级别提供了额外的结构解析层面。我们首次开发了一种化学分离方案,该方案能够制备和分离C-C范围内的可溶性原始富勒管。迄今为止,用于纳米级计算机应用的单壁碳纳米管的应用要求纯度大于99.999%。虽然使用单壁碳纳米管样品尚未证明这一严格要求,但对于金属性的[5,5] -C和半导体性的[10,0] -C [10766]富勒管来说,这种高纯度似乎是可以实现的。此外,由于火焰法具有连续操作和廉价原料的特点,原始富勒管的商业化生产应该很容易实现。对于应用开发,理论和电化学实验数据表明,富勒管在氧还原反应中表现出高催化活性。在医疗领域,原始富勒管分散体对和表现出抗菌作用。