Controlled interconversion of macrocyclic atropisomers via defined intermediates.

Macrocyclic conformations play a crucial role in regulating their properties. Our understanding of the determinants to control macrocyclic conformation interconversion is still in its infancy. Here we present a macrocycle, octamethyl cyclo[4](1,3-(4,6)-dimethylbenzene)[4]((4,6-benzene)(1,3-dicarboxylate) (OC-4), that can exist at 298 K as two stable atropisomers with C2v and C4v symmetry denoted as C2v-OC-4 and C4v-OC-4, respectively. Heating induces the efficient stepwise conversion of C2v- to C4v-OC-4 via a Cs-symmetric intermediate (Cs-OC-4). It differs from the typical transition state-mediated processes of simple C-C single bond rotations. Hydrolysis and further esterification with a countercation dependence promote the generation of C2v- and Cs-OC-4 from C4v-OC-4. In contrast to C2v-OC-4, C4v-OC-4 can bind linear guests to form pseudo-rotaxans, or bind C60 or C70 efficiently. The present study highlights the differences in recognition behavior that can result from conformational interconversion, as well as providing insights into the basic parameters that govern coupled molecular rotations.

The Effects of Pore Defects in π-Extended Pentadecabenzo[9]helicene.

The introduction of precise pore defects into nanocarbon structures results in the emergence of distinct physicochemical characteristics. However, there is a lack of research on non-planar chiral nanographene involving precise pore defects. Herein, we have developed two analogues to the π-extended pentadecabenzo[9]helicene (EP9H) containing embedded pore defects. Each molecule, namely extended dodecabenzo[7]helicene (ED7H; 1) or extended nonabenzo[5]helicene (EN5H; 2), exhibits dual-state emission. Significantly, the value of |glum| of 1 is exceptionally high at 1.41 × 10-2 in solution and BCPL as 254 M-1 cm-1. In PMMA film, |glum| of 1 is 8.56 × 10-3, and in powder film, it is 5.00 × 10-3. This study demonstrates that nanocarbon molecules with pore defects exhibit dual-state emission properties while maintaining quite good chiral luminescence properties. It was distinguished from the aggregation-caused quenching (ACQ) effect corresponding to the nanocarbon without embedded defect. Incorporating pore defects into chiral nanocarbon molecules also simplifies the synthesis process and enhances the solubility of the resulting product. These findings suggest that the introduction of pore defects can be a viable approach to improve nanocarbon molecules.

The Process and Mechanism of Preparing Nanoporous Silicon: Helium Ion Implantation.

Ion implantation is an effective way to control performance in semiconductor technology. In this paper, the fabrication of 1~5 nm porous silicon by helium ion implantation was systemically studied, and the growth mechanism and regulation mechanism of helium bubbles in monocrystalline silicon at low temperatures were revealed. In this work, 100 keV He ions (1~7.5 × 1016 ions/cm2) were implanted into monocrystalline silicon at 115 °C~220 °C. There were three distinct stages in the growth of helium bubbles, showing different mechanisms of helium bubble formation. The minimum average diameter of a helium bubble is approximately 2.3 nm, and the maximum number density of the helium bubble is 4.2 × 1023 m-3 at 175 °C. The porous structure may not be obtained at injection temperatures below 115 °C or injection doses below 2.5 × 1016 ions/cm2. In the process, both the ion implantation temperature and ion implantation dose affect the growth of helium bubbles in monocrystalline silicon. Our findings suggest an effective approach to the fabrication of 1~5 nm nanoporous silicon, challenging the classic view of the relationship between process temperature or dose and pore size of porous silicon, and some new theories are summarized.

Extrapendicular Approach of Unilateral Percutaneous Vesselplasty for the Treatment of Kummell Disease.

BACKGROUND: Our purpose was to evaluate the efficacy of the extrapendicular approach for unilateral percutaneous vesselplasty in dealing with Kummell disease patients. METHODS: Twenty-seven patients undergoing vesselplasty at our institution were enrolled in the study. Vesselplasty was performed using percutaneous extrapendicular technique. Pain, restoration of vertebral body height, and cement leakage were evaluated in the process. RESULTS: Substantial pain relief was attained in all the patients. The visual analogue scale improved significantly from pre- to postoperation (P < .05), and remained unchanged at every follow-up. The anterior vertebral body heights were significantly corrected after operation (P < .05). No cement leakage was found. CONCLUSION: This new technique of vesselplasty offers statistically significant benefits in Kummell disease patients. It also makes vesselplasty feasible, safe, and effective.