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Angewandte Chemie / International edition e202202492 (2022). doi:10.1002/anie.202202492, Published by Wiley-VCH, Weinheim

The interest in two-dimensional conjugated polymers (2D CPs) has increased significantly in recent years. In particular, vinylene-linked 2D CPs with fully in-plane sp2-carbon-conjugated structures, high thermal and chemical stability, have become the focus of attention. Although the Horner-Wadsworth-Emmons (HWE) reaction has been recently demonstrated in synthesizing vinylene-linked 2D CPs, it remains largely unexplored due to the challenge in synthesis. In this work, we reveal the control of crystallinity of 2D CPs during the solvothermal synthesis of 2D-poly(phenylene-quinoxaline-vinylene)s (2D-PPQVs) and 2D-poly(phenylene-vinylene)s through the HWE polycondensation. The employment of fluorinated phosphonates and rigid aldehyde building blocks is demonstrated as crucial factors in enhancing the crystallinity of the obtained 2D CPs. Density functional theory (DFT) calculations reveal the critical role of the fluorinated phosphonate in enhancing the reversibility of the (semi)reversible C−C single bond formation.

Objective To validate with a prospective study a decision-supporting coding system for the surgical approach for multilevel degenerative cervical myelopathy. Methods Ten cases were presented on an internet platform, including clinical and imaging data. A single-approach (G1), a choice between 2 (G2), or 3 approaches (G3) were options. Senior and junior spine surgeons analyzed 7 parameters: location and extension of the compression of the spinal cord, C-spine alignment and instability, general morbidity and bone diseases, and K-line and multilevel corpectomy. For each parameter, an anterior, posterior, or combined approach was suggested. The most frequent letter or the last letter (if C) of the resulting 7-letter code (7LC) suggested the surgical approach. Each surgeon performed 2 reads per case within 8 weeks. Results G1: Interrater reliability between junior surgeons improved from the first read (κ = 0.40) to the second (κ = 0.76, p < 0.001) but did not change between senior surgeons (κ = 0.85). The intrarater reliability was similar for junior (κ = 0.78) and senior (κ = 0.71) surgeons. G2: Junior/senior surgeons agreed completely (58%/62%), partially (24%/23%), or did not agree (18%/15%) with the 7LC choice. G3: junior/senior surgeons agreed completely (50%/50%) or partially (50%/50%) with the 7LC choice. Conclusion The 7LC showed good overall reliability. Junior surgeons went through a learning curve and converged to senior surgeons in the second read. The 7LC helps less experienced surgeons to analyze, in a structured manner, the relevant clinical and imaging parameters influencing the choice of the surgical approach, rather than simply pointing out the only correct one.

In this study, we examined the residual doses of the quartz electron spin resonance (ESR) signals from eight young fluvial sediments with known luminescence ages from the Lower Rhine terraces. The single aliquot regenerative (SAR) protocol was applied to obtain the residual doses for both the aluminium (Al) and titanium (Ti) impurity centres. We show that all of the fluvial samples carry a significant amount of residual dose with a mean value of 1270 ± 120 Gy for the Al centre (including the unbleachable signal component), 591 ± 53 Gy for the lithium-compensated Ti centre (Ti-Li), 170 ± 21 Gy for the hydrogen-compensated Ti centre (Ti-H) and 453 ± 42 Gy for the signal that originated from both the Ti-Li and Ti-H centres (termed Ti-mix). To test the accuracy of the ESR SAR protocol, a dose recovery test was conducted and this confirmed the validity of the Ti-Li and Ti-mix signal results. The Al centre shows a dose recovery ratio of 1.75 ± 0.18, whereas the Ti-H signal shows a ratio of 0.55 ± 0.17, suggesting that the rate of signal production per unit dose changed for these signals after the thermal annealing. Nevertheless, all fluvial sediments investigated in this study carry a significant residual dose. Our result suggests that more direct comparisons between luminescence and ESR equivalent doses should be carried out, and, if necessary, the subtraction of residual dose obtained from the difference is essential to obtain reliable ESR ages.

The vast potential of organic materials for electronic, optoelectronic and spintronic devices entails substantial interest in the fabrication of π-conjugated systems with tailored functionality directly at insulating interfaces. On-surface fabrication of such materials on non-metal surfaces remains to be demonstrated with high yield and selectivity. Here we present the synthesis of polyaromatic chains on metallic substrates, insulating layers, and in the solid state. Scanning probe microscopy shows the formation of azaullazine repeating units on Au(111), Ag(111), and h-BN/Cu(111), stemming from intermolecular homo-coupling via cycloaddition reactions of CN-substituted polycyclic aromatic azomethine ylide (PAMY) intermediates followed by subsequent dehydrogenation. Matrix-assisted laser desorption/ionization (MALDI) mass spectrometry demonstrates that the reaction also takes place in the solid state in the absence of any catalyst. Such intermolecular cycloaddition reactions are promising methods for direct synthesis of regioregular polyaromatic polymers on arbitrary insulating surfaces., This work was financially supported by the European Research Council Consolidator Grant NanoSurfs (no. 615233), the Advanced Grant (no. 694097), the Horizon 2020 research and innovation program 2D ink (no. 664878) and the National Science Foundation of China (no. 11974403 and Sino-German Project no. 51761135130). W.A. acknowledges funding by the DFG via a Heisenberg professorship. M.R., R.B., and X.F. thank the German Research Foundation (DFG) within the Cluster of Excellence “Center for Advancing Electronics Dresden (cfaed)” and EnhanceNano (No. 391979941). A.P.P. and A.Ru. thank the Cluster of Excellence "Advanced Imaging of Matter (AIM)" and Grupos Consolidados (IT1249-19). M.G. acknowledges funding by the H2020-MSCA-IF−2014 program under GA no. 658070 (2DNano).

Nanographenes, namely polycyclic aromatic hydrocarbons (PAHs) with nanoscale dimensions (>1 nm), are atomically precise cutouts from graphene. They represent prime models to enhance the scope of chemical and physical properties of graphene through structural modulation and functionalization. Defined nitrogen doping in nanographenes is particularly attractive due to its potential for increasing the number of π-electrons, with the possibility of introducing localized antiaromatic ring elements. Herein we present azomethine ylide homocoupling as a strategy to afford internally nitrogen-doped, non-planar PAH in solution and planar nanographene on surfaces, with central pyrazine rings. Localized antiaromaticity of the central ring is indicated by optical absorption spectroscopy in conjunction with theoretical calculations. Our strategy opens up methods for chemically tailoring graphene and nanographenes, modified by antiaromatic dopants., Polyaromatic hydrocarbons can be precisely manipulated to yield ever more complex and discrete graphene analogs, such as nanographenes. Here, the authors use azomethine ylide homocoupling to insert an antiaromatic pyrazine ring into the core of a nanographene, and characterize the molecule’s unique electronic character.

With regard to the literature, several factors are considered to have an impact on postoperative mobility after lumbar total disc replacement (TDR). As TDR results in a distraction of the ligamentous structures, theoretically the postoperatively disc height and ligamentous integrity have also an influence on biomechanics of a treated segment. The purpose of the study was to evaluate the influence of posterior longitudinal ligament (PLL) resection and segmental distraction on range of motion (ROM). Six human, lumbar spines (L2–L3) were tested with pure moments of ±7.5 Nm in a spine loading apparatus. The ROM was determined in all three motion planes. Testing sequences included: (1) intact state, (2) 10 mm prosthesis (PLL intact), (3) 10 mm prosthesis (PLL resected), (4) 12 mm prosthesis (PLL resected). The prosthesis used was a prototype with a constrained design using the ball-and-socket principle. The implantation of the 10 mm prosthesis already increased the disc height significantly (intact: 9.9 mm; 10 mm prosthesis: 10.6 mm; 12 mm prosthesis: 12.7 mm). Compared to the intact status, the implantation of the 10 mm prosthesis resulted in an increase of ROM for flexion/extension (8.6° vs 10.8°; P = 0.245) and axial rotation (2.9° vs 4.5°; P = 0.028), whereas lateral bending decreased (9.0° vs 7.6°; P = 0.445). The resection of the PLL for the 10 mm prosthesis resulted in an increase of ROM in all motion planes compared to the 10 mm prosthesis with intact PLL (flexion/extension: 11.4°, P = 0.046; axial rotation: 5.1°, P = 0.046; lateral bending: 8.6°, P = 0.028). The subsequent implantation of a 12 mm prosthesis, with resected PLL, resulted in a significant decrease of ROM in all motion planes compared to the 10 mm prosthesis with intact PLL (flexion/extension: 8.4°, P = 0.028; axial rotation: 3.3°, P = 0.028; lateral bending: 5.1°, P = 0.028). Compared to the intact status, the 12 mm prosthesis with resected PLL only decreased lateral bending significantly while the 10 mm prosthesis with intact PLL increased axial rotation significantly. The resection of the PLL during TDR results in a significant increase of ROM in all three principle motion planes. But it still remains unclear if this increase which is in median not more than 1° may alter the clinical results. Moreover, the destabilizing effect of PLL resection can be reversed using a higher implant. The prosthesis height seems more crucial than PLL preservation to maintain the primary stability after TDR.

The objective of this study was to determine which discoligamentous structures of the lower cervical spine provide significant stability with regard to different loading conditions. Accordingly, the load-displacement properties of the normal and injured lower cervical spine were tested in vitro. Four artificially created stages of increasing discoligamentous instability of the segment C5/6 were compared to the normal C5/6 segment. Six fresh human cadaver spine segments C4-C7 were tested in flexion/extension, axial rotation, and lateral bending using pure moments of +/- 2.5 Nm without axial preload. Five conditions were investigated consecutively: (1) the intact functional spinal unit (FSU) C5/6; (2) the FSU C5/6 with the anterior longitudinal ligament and the intertransverse ligaments sectioned; (3) the FSU C5/6 with an additional 10-mm-deep incision of the anterior half of the anulus fibrosus and the disc; (4) the FSU C5/6 with additionally sectioned ligamenta flava as well as interspinous and supraspinous ligaments; (5) the FSU C5/6 with additional capsulotomy of the facet joints. In flexion/extension, significant differences were observed concerning range of motion (ROM) and neutral zone (NZ) for all four stages of instability compared to the intact FSU. In axial rotation, only the stage 4 instability showed a significantly increased ROM and NZ compared to the intact FSU. For lateral bending, no significant differences were observed. Based on these data, we conclude that flexion/extension is the most sensitive load-direction for the tested discoligamentous instabilities.

Transarticular C1/2 screws are widely used in posterior cervical spine instrumentation. The use of pedicle screws in the cervical spine remains uncommon. Due to superior biomechanical stability compared to lateral mass screws, pedicle screws can be used, especially for patients with poor bone quality or defects in the anterior column. Nevertheless there are potential risks of iatrogenic damage to the spinal cord, nerve roots or the vertebral artery associated with both posterior cervical spine instrumentation techniques. Therefore, the aim of this study was to evaluate whether C1/2 transarticular screws as well as transpedicular screws in C3 and C4 can be applied safely and with high accuracy using a computer-assisted surgery (CAS) system. We used 13 human cadaver C0-C5 spine segments. We installed 1.4-mm Kirschner wires transarticular in C 1/2, using a specially designed guide, and drilled 2.5-mm pedicle holes in C3 and C4 with the assistance of the CAS system. Hole positions were evaluated by palpation, CT and dissection. Forty-eight (92%) of the 52 drilled pedicles were correctly positioned after palpation, imaging and dissection. The vertebral artery was not injured in any specimen. All of the 26 C1/2 Kirschner wires were placed properly after imaging and dissection evaluations. No injury to vascular or bony structures was observed. C /2 transarticular screws as well as transpedicular screws in the cervical spine can be applied safely and with high accuracy using a CAS system in vitro. Therefore, this technique may be used in a clinical setting, as it offers improved accuracy and reduced radiation dose for the patient and the medical staff. Nevertheless, users should take note of known sources of possible faults causing inaccuracies in order to prevent iatrogenic damage. Small pedicles, with a diameter of less than 4.0 mm, may not be suitable for pedicle screws.

The rapid development of on-surface synthesis provides a unique approach toward the formation of carbon-based nanostructures with designed properties. Herein, we present the on-surface formation of CN-substituted phenylene vinylene chains on the Au(111) surface, thermally induced by annealing the substrate stepwise at temperatures between 220 °C and 240 °C. The reaction is investigated by scanning tunneling microscopy and density functional theory. Supported by the calculated reaction pathway, we assign the observed chain formation to a Knoevenagel condensation between an aldehyde and a methylene nitrile substituent.

Polycyclic aromatic azomethine ylides (PAMY, 1) are versatile building blocks for the bottom-up synthesis of nitrogen-containing polycyclic aromatic hydrocarbons (N-PAHs). Although the chemistry of PAMY was already established few years ago, the cycloaddition of a double PAMY building block has not been reported so far. In this work, we demonstrate the first cycloaddition of a PAMY-dimer (6), which opens the access to three different alkyl ester-substituted N-PAHs with a laterally extended double ullazine scaffold (DU-1, DU-2 and DU-3). Interestingly, the cyclic voltammetry of DU-1–3 exhibited three reversible oxidation waves, which confirmed the electron-rich nature of the double ullazine scaffold. Furthermore, in situ spectroelectrochemistry study of ethylhexyl ester-substituted DU-3 revealed the formation of different cationic species with new absorption bands up to 1689 nm. Additionally, the influence of the attached substituents on the film formation and supramolecular organization in the thin films was investigated by polarized optical microscopy and grazing incidence wide-angle X-ray scattering.