Tuning Mesopore Accessibility of Ce0.18Zr0.64Y0.15La0.03O2-δ by Hydrothermal Post-treatment─A Case Study for Ceria-Based Oxidation Storage Materials.

The connectivity and thermal stability of pores in heterogeneous, mesoporous metal oxide catalysts are key properties controlling their (long-term) efficacy. In this study, we investigate the influence of pH and temperature during a common hydrothermal aftertreatment step in the synthesis of mesoporous CexZr1-x-y-zYyLazO2-δ oxides obtained from molecular precursors via hydrothermal synthesis. This study has a strong focus on the methodological approach, elucidating whether and how even the smallest changes in morphology and connectivity may be unraveled and related to the underlying chemical processes to uncover key parameters for the ongoing improvement of material properties. Deep insights into the mesopore space were obtained by state-of-the-art physisorption (including hysteresis scanning), electron tomography, and small-angle X-ray scattering (SAXS) analysis. We also provide a simple tool to simulate SAXS curves from electron tomography data that allow direct comparison to experimentally obtained SAXS curves. Furthermore, the impact on surface-bound nitrate groups and the development during calcination were studied in detail by thermogravimetric analysis coupled with mass spectrometry. The key observations indicate a significant increase in thermal stability at temperatures as high as 1050 °C and improved mesopore accessibility with an increase in pH of the aftertreatment solution. The combined observations from the employed methods suggest a pH-dependent removal of surface-bound nitrate groups as well as a dissolution and reprecipitation-based fusing of the primary particles that constitute the mesopore skeleton. This transformation yields a mechanically and thermally stronger mesopore space with the capability to endure high temperatures.

Controlling Spontaneous Orientation Polarization in Organic Semiconductors─The Case of Phosphine Oxides.

Upon film growth by physical vapor deposition, the preferential orientation of polar organic molecules can result in a nonzero permanent dipole moment (PDM) alignment, causing a macroscopic film polarization. This effect, known as spontaneous orientation polarization (SOP), was studied in the case of different phosphine oxides (POs). We investigate the control of SOP by molecular design and film-growth conditions. Our results show that using less polar POs with just one phosphor-oxygen bond yields an exceptionally high degree of SOP with the so-called giant surface potential (slope), reaching more than 150 mV nm-1 in a neat bis-4-(N-carbazol(yl)phenyl)phenyl phosphine oxide (BCPO) film grown at room temperature. Additionally, by altering the evaporation rate and substrate temperature, we are able to control the SOP magnitude over a broad range from 0 to almost 300 mV nm-1. Diluting BCPO in a nonpolar host enhances the PDM alignment only marginally, but combining temperature control with dipolar doping can result in highly aligned molecules with more than 80% of their PDMs standing upright on the substrate on average.

Trochanter migrans: late complications due to displacement of the lesser trochanter in trochanteric fractures.

Complications associated with secondary displacement and migration of the lesser trochanter fragment in trochanteric fractures are rare. The complaints expressed by the patient may be misunderstood and attributed to implant-associated or patient-specific problems likely to occur after surgery. This series illustrates potentially dangerous late complications caused by secondary migration of the lesser trochanter. It may help focus the surgeon's attention on possible functional impairment and severe late complications caused by displacement of the lesser trochanter in trochanteric fractures that require prompt intervention.

Effects of Hydrothermal Treatment on Mesopore Structure and Connectivity in Doped Ceria-Zirconia Mixed Oxides.

Pore size and pore connectivity control diffusion-based transport in mesopores, a crucial property governing the performance of heterogeneous catalysts. In many cases, transition-metal oxide catalyst materials are prepared from molecular precursors involving hydrothermal treatment followed by heat treatment. Here, we investigate the effects of such a hydrothermal aftertreatment step, using an aqueous ammonia solution, on the disordered mesopore network of CexZr1-x-y-zYyLazO2-δ mixed oxides. This procedure is a common synthesis step in the preparation of such ceria-based oxygen storage materials applied in three-way catalysis, employed to improve the materials' thermal stability. We perform state-of-the-art Ar-physisorption analysis, especially advanced hysteresis scanning, to paint a detailed picture of the alterations in mesopore space caused by the hydrothermal aftertreatment and subsequent aging at 1050 °C. Furthermore, we investigate the network characteristics by electron tomography in combination with suitable statistical analysis, enabling a consistent interpretation of the desorption scans (physisorption). The results indicate that the hydrothermal aftertreatment enhances the mesopore connectivity of the continuous 3D network by widening pores and especially necks, hence facilitating accessibility to the particles' internal surface area and the ability to better withstand high temperatures.

The FFP-classification: From eminence to evidence.

Fragility fractures of the pelvis (FFP) are a clinical entity with a rapidly growing incidence among elderly women. The characteristics of these fractures are different from those appearing after high-energy trauma. In 2013, the comprehensive FFP-classification provided a new framework for analysis of these fractures. It is based on the estimation of loss of stability in the pelvic ring. It is connected with recommendations for surgical treatment, justified by the fact that higher instabilities will need surgical stabilization. Since it's appearance, we can observe an increasing clinical-scientific interest in FFP. Multiple publications use the FFP-classification studying the characteristics of fractures, choice of treatment and outcome. Other studies focus on minimal-invasive techniques for stabilization. The actual knowledge describes higher mortality rates as the reference population, lower mortality rates after operative treatment but for the price of surgery-related complications. Mobility, independency and quality of life are worse than before the fracture, independent of the FFP-classification and the type of treatment. The classification triggered a rapid increase of expertise. This publication gives a detailed overview on the evolution from eminence to evidence.

Isolation of Hepatocytes from Liver Tissue by a Novel, Semi-Automated Perfusion Technology.

Primary hepatocytes are a major tool in biomedical research. However, obtaining high yields of variable hepatocytes is technically challenging. Most protocols rely on the two-step collagenase perfusion protocol introduced by Per Ottar Seglen in 1976. In this procedure, the liver is perfused in situ with a recirculating, constant volume of calcium-free buffer, which is maintained at 37 °C and continuously oxygenated. In a second step, the liver is removed from the carcass and perfused with a collagenase solution in order to dissociate the extracellular matrix of the liver and liberate individual cells. Finally, the dissected hepatocytes are further purified and concentrated by density-based centrifugation. However, failure in proper cannulation, incomplete enzymatic digestion or over-digestion can result in low cell yield and viability. Here we present a novel semi-automated perfusion device, which allows gentle, rapid and efficient generation of a single-cell suspension from rodent livers. In combination with prefabricated buffers, the system allows reliable and highly reproducible isolation of primary hepatocytes.

Lock-In Pixel CMOS Image Sensor for Time-Resolved Fluorescence Readout of Lateral-Flow Assays.

We present a CMOS image sensor (CIS) based time-resolved fluorescence (TRF) measurement system for filter-less, highly sensitive readout of lateral-flow assay (LFA) test strips. The CIS contains a 256 × 128 lock-in pixel (LIP) sensor array. Each pixel has a size of 10 µm × 10 µm and includes a photodiode acting as signal transducer. The LIP CIS was designed in a standard 0.18 µ m CMOS technology specifically for TRF applications. The LIP architecture blocks interfering light when fluorophores are excited and accumulates the emitted fluorescence light to be measured over multiple cycles after excitation. This allows to detect even small amounts of fluorescence light over a wide analyte concentration range. The LIP CIS based TRF reader was characterized in terms of reproducible and uniform signal intensities with use of appropriate Europium(III) [Eu 3+] chelate particles as fluorescence standards. We measured different concentrations of Eu-based nanoparticles (NP) on test strips with the TRF reader. The sensor system shows 5.1 orders of magnitude of detection dynamic range (DDR) with a limit of detection (LoD) of [Formula: see text]. In addition, using human C-reactive protein (hCRP) as a model analyte, we compared the developed TRF reader with a commercial colorimetric LFA reader. For the quantification of CRP, the LIP CIS based TRF reader demonstrates a DDR of 3.6 orders of magnitude with an excellent LoD of [Formula: see text], which is 14 times better than the LoD of the commercial LFA reader.

Development of Pore Morphology During Nitrate Group Removal by Calcination of Mesoporous CexZr1-x-y-zYyLazO2-δ Powders.

Here, we present a study of the development of the micro- and mesoporosity of a CexZr1-x-y-zYyLazO2-δ oxygen storage material upon treatment at temperatures up to 1050 °C. The investigated powder, obtained from nitrate-based metal oxide precursors in a specially developed hydrothermal synthesis, is highly crystalline, features a high surface area and does not show phase segregation at high temperatures. By employing an advanced methodology, consisting of state-of-the-art argon physisorption, thermogravimetric analysis coupled with mass spectrometry (TG-MS) and X-ray powder diffraction (XRD) along with Raman spectroscopy, we correlate the stability of the mesopore system to the presence of surface-bound nitrate groups introduced during synthesis, which prevent sintering up to a temperature of 600 °C. In addition, the connectivity of mesopores was further studied by hysteresis scanning within the argon physisorption measurements. These advanced physisorption experiments suggest a three-dimensionally interconnected pore system and, in turn, a 3D network of the material itself on the nanometer scale which appears to be beneficial to endow the mesopore space with enhanced stability against sintering and mesopore collapse once the removal of nitrate groups is completed.

[Minimally invasive stabilization of fragility fractures of the pelvis with transsacral bar and retrograde transpubic screw]. / Minimal-invasive Stabilisierung von Fragilitätsfrakturen des Beckens mittels transsakralem Stab und retrograder transpubischer Schraube.

OBJECTIVE: Stabilization of fragility fractures of the pelvis (FFP) using a minimally invasive technique. Insertion of a transsacral rod into the transsacral corridor of S1. Insertion of a retrograde transpubic screw through the superior branch of the pubic bone. INDICATIONS: Uni- or bilateral displaced fragility fractures of the sacrum or sacroiliac joint. Nondisplaced fractures of the sacrum or sacroiliac joint in case of nonsuccessful conservative treatment. Uni- or bilateral fractures of the superior branch of the pubic bone, which are present in combination with a posterior pelvic instability. CONTRAINDICATIONS: Fragility fractures of the pelvis, which can be successfully treated conservatively. Absence of transsacral corridor in sacral body S1. Major displacement, nonreducible fractures of the superior branch of the pubic bone. Soft tissue infection at insertion site of implants. SURGICAL TECHNIQUE: The transsacral bar is inserted under fluoroscopic control from ilium to ilium through the transsacral corridor of the sacral body S1. The retrograde transpubic screw is inserted from the pubic tubercle through the superior branch of the pubic bone past the acetabulum into the body of the ilium. POSTOPERATIVE MANAGEMENT: An early mobilization with weight bearing of both lower extremities as tolerated by the patient is allowed. Conventional radiographs for control of the position of the implants and fractures are taken after mobilization RESULTS: In all, 64 patients with FFP type II, FFP type III or FFP type IV were stabilized with a transacral bar osteosynthesis in the posterior pelvis. In 32 patients (50%), additional sacroiliac screws were inserted. In 29 patients (45.3%) the transsacral bar osteosynthesis was combined with a transpubic retrograde screw. Median length of hospital stay was 17.5 days. In all, 20 patients (31.3%) suffered general, 10 patients (15.6%) suffered surgery-related complications, and 41 patients (64.1%) were mobile in the room or on the ward at discharge. One-year mortality was 10.9%. The values of the SF­8 Physical and Mental Component Scores, Parker Mobility Score and Numeric Rating Scale were moderate, yet comparable with the values of patients of the same age.

Tibial plateau fracture: does fracture classification influence the choice of surgical approach? A retrospective multicenter analysis.

PURPOSE: The role of classification systems for the choice of surgical approach and the management of tibial plateau fractures remains unclear. The purpose of this study was to investigate the potential of classification systems to choose the appropriate operative approach. Current surgical management strategies were investigated in a large multicenter assessment. METHODS: In this study, we retrospectively analyzed all patients with tibial plateau fractures that have received surgical treatment in one of the five Level I trauma facilities between 2012 and 2015. Fractures were classified in each center by a senior orthopedic surgeon using the AO/OTA and the Luo classification. Demographics, trauma mechanism, as well as the surgical approach were recorded. RESULTS: 538 patients (46.1% male, 53.9% female) were included. The anterolateral approach was used most frequently with 54.8% of all single approaches; 76.2% of all combined approaches used anterolateral as part of the approach. Combined approaches were used in 22.5% of the cases; a combination of the anterolateral and medial (10%), anterolateral, and posteromedial approach (5.8%) were used most frequently. The lowest number was found for the posterolateral (1.3%) and the combined approaches dorsal/anterolateral and medial/dorsal (1.7%, 1.1%). The AO/OTA classification showed a peak for 41.B2 (21.9%) and B3 (35.5%) fractures. Regarding the Luo classification, the dorsal column was involved in 45.7%. In contrast, only 14.7% of the surgical approaches used were able to address the dorsal tibial plateau potentially. CONCLUSION: The use of dorsal approach seems to be of minor importance than expected in daily clinical practice in this multicenter study. It was not possible to specify whether the AO/OTA or the Luo classification can reliably predict the choice of surgical approach. The operative treatment strategy of tibial plateau fractures seems to rather rely on the surgeons' experience, education, and preferences.

Plate fixation of the anterior pelvic ring in patients with fragility fractures of the pelvis.

INTRODUCTION: In fragility fractures of the pelvis (FFP), fractures of the posterior pelvic ring are nearly always combined with fractures of the anterior pelvic ring. When a surgical stabilization of the posterior pelvis is performed, a stabilization of the anterior pelvis is recommended as well. In this study, we aim at finding out whether conventional plate osteosynthesis is a valid option in patients with osteoporotic bone. MATERIALS AND METHODS: We retrospectively reviewed medical charts and radiographs of all patients with a FFP, who underwent a plate osteosynthesis of the anterior pelvic ring between 2009 and 2019. Patient demographics, fracture characteristics, properties of the osteosynthesis, complications and revision surgeries were documented. Single plate osteosynthesis (SPO) at the pelvic brim was compared with double plate osteosynthesis (DPO) with one plate at the pelvic brim and one plate anteriorly. We hypothesized that the number and severity of screw loosening (SL) or plate breakage in DPO are lower than in SPO. RESULTS: 48 patients with a mean age of 76.8 years were reviewed. In 37 cases, SPO was performed, in 11 cases DPO. Eight out of 11 DPO were performed in patients with FFP type III or FFP type IV. We performed significantly more DPO when the instability was located at the level of the pubic symphysis (p = 0.025). More patients with a chronic FFP (surgery more than one month after diagnosis) were treated with DPO (p = 0.07). Infra-acetabular screws were more often inserted in DPO (p = 0.056). Screw loosening (SL) was seen in the superior plate in 45% of patients. There was no SL in the anterior plate. There was SL in 19 of 37 patients with SPO and in 3 of 11 patients with DPO (p = 0.16). SL was localized near to the pubic symphysis in 19 of 22 patients after SPO and in all three patients after DPO. There was no SL in DPO within the first month postoperatively. We performed revision osteosynthesis in six patients (6/48), all belonged to the SPO group (6/37). The presence of a bone defect, unilateral or bilateral anterior pelvic ring fracture, post-operative weight-bearing restrictions, osteosynthesis of the posterior pelvic ring, and the presence of infra- or supra-acetabular screws did not significantly influence screw loosening in SPO or DPO. CONCLUSION: There is a high rate of SL in plate fixation of the anterior pelvic ring in FFP. In the vast majority, SL is located near to the pubic symphysis. DPO is associated with a lower rate of SL, less severe SL and a later onset of SL. Revision surgery is less likely in DPO. In FFP, we recommend DPO instead of SPO for fixation of fractures of the anterior pelvic ring, which are located in or near to the pubic symphysis.

Operative treatment of fragility fractures of the pelvis: a critical analysis of 140 patients.

BACKGROUND: Fragility fractures of the pelvis (FFP) are a clinical entity with an increasing frequency. Indications for and type of surgical treatment are still a matter of debate. PURPOSE: This retrospective study presents and critically analyses the results of operative treatment of 140 patients with FFP. SETTING: Level-I trauma center. MATERIALS AND METHODS: Demographic data, comorbidities, FFP-classification, type of surgical stabilization (percutaneous (P-group) versus open procedure (O-group)), length of hospital stay (LoS), general in-hospital complications, surgery-related complications, living environment before admission, mobility and destination at discharge were retracted from the medical and radiographic records. Patients were asked participating in a survey by telephone call about their quality of life. SF-8 Physical Component Score (PCS) and SF-8 Mental Component Score (MCS) were calculated as well as the Parker Mobility Score (PMS) and the Numeric Rating Scale (NRS). RESULTS: Mean age was 77.4 years and 89.3% of patients were female. 92.1% presented with one comorbidity, 49.3% with two or more comorbidities. Median length of hospital stay was 18 days, postoperative length of hospital stay was 12 days. 99 patients (70.7%) received a percutaneous operative procedure, 41 (29.3%) an open. Patients of the O-group had a significantly longer LoS than patients of the P-group (p = 0.009). There was no in-hospital mortality. There were significantly more surgery-related complications in the O-group (43.9%) than in the P-group (19.2%) (p = 0.006). Patients of the O-group needed more often surgical revisions (29.3%) than patients of the P-group (13.1%) (p = 0.02). Whereas 85.4% of all patients lived at home before admission, only 28.6% returned home at discharge (p < 0.001). The loss of mobility at discharge was not influenced by the FFP-classes (p = 0.47) or type of treatment (p = 0.13). One-year mortality was 9.7%. Mortality was not influenced by the FFP-classes (p = 0.428) or type of treatment (p = 0.831). Median follow-up was 40 months. SF-8 PCS and SF-8 MCS were moderate (32.43 resp. 54.42). PMS was 5 and NRS 4. Follow-up scores were not influenced by FFP-classes or type of treatment. CONCLUSION: Patients with FFP, who were treated operatively, suffered from a high rate of non-lethal general, in-hospital complications. Open surgical procedures induced more surgery-related complications and surgical revisions. Mental and physical follow-up scores are low to moderate. Condition at follow-up is not influenced by FFP-classes or type of treatment. Indications for operative treatment of FFP must be critically examined. Surgical fixation should obtain adequate stability, yet be as less invasive as possible. The advantages and limitations of different surgical techniques have to be critically evaluated in prospective studies.

Atraumatic femoral head necrosis: a biomechanical, histological and radiological examination compared to primary hip osteoarthritis.

INTRODUCTION: Atraumatic necrosis of the femoral head (AFHN) is a common disease with an incidence of 5000-7000 middle-aged adults in Germany. There is no uniform consensus in the literature regarding the configuration of the bone in AFHN. The clinical picture of our patients varies from very hard bone, especially in idiopathic findings, and rather soft bone in cortisone-induced necrosis. A better understanding of the underlying process could be decisive for establishing a morphology-dependent approach. The aim of this study is the closer examination of the condition of the bone in the AFHN compared to the primary hip osteo arthritis (PHOA). MATERIALS AND METHODS: The preparations were obtained as part of elective endoprosthetic treatment of the hip joint. Immediately after sample collection, thin-slice CT of the preserved femoral heads was performed to determine the exact density of the bone in the necrosis zone. Reconstruction was done in 0.8-1 mm layers in two directions, coronary and axial, starting from the femoral neck axis. Density of the femoral heads was determined by grey value analysis. The value in Hounsfield units per sample head was averaged from three individual measurements to minimize fluctuations. For biomechanical and histomorphological evaluation, the samples were extracted in the load bearing zone perpendicular to the surface of the femoral head. Group-dependent statistical evaluation was performed using single factor variance analysis (ANOVA). RESULTS: A total of 41 patients with a mean age of 64.44 years were included. The mean bone density of the AFHN samples, at 1.432 g/cm3, was about 7% higher than in the PHOA group with a mean value of 1.350 g/cm3 (p = 0.040). The biomechanical testing in the AFHN group showed a 22% higher-but not significant-mean compressive strength (20.397 MPa) than in the PHOA group (16.733 MPa). On the basis of histological analysis, no differentiation between AFHN and PHOA samples was possible. CONCLUSIONS: The present study (NCT, evidence level II) shows that AFHN has a very well detectable higher bone density compared to PHOA. However, neither biomechanical stress tests nor histomorphological evaluation did show any significant difference between the groups. The results allow the conclusion that there is no "soft" necrosis at all in the AFHN group.

Lab-scale and full-scale industrial composting of biodegradable plastic blends for packaging.

Background: The acceptance of compostable plastic packaging in industrial composting plants is not universal despite available certification due to the persistence of plastic residues after composting. To better understand this discrepancy, this study compared the disintegration rates of two blends designed for rigid packaging (polylactic acid based) and soft packaging (polybutylene succinate based) in lab-scale composting tests and in an industrial composting plant. Methods: A lab-scale composting test was conducted in triplicates according to ISO 20200 for 4, 8 and 12 weeks to check the disintegration potential of the blends. Duplicate test material were then exposed in the compost pile of an industrial composting plant for a duration of 3 weeks and compared with a supplementary lab-scale test of the same duration. Results: The rigid packaging samples (1 mm thickness) retained on average 76.4%, 59.0% and 55.7% of its mass after 4, 8 and 12 weeks respectively in the lab-scale. In the plant, the average remaining mass was 98.3%, much higher compared to the average of 68.9% after 3 weeks in the supplementary lab-scale test. The soft packaging samples (109±9 µm sample thickness) retained on average 45.4%, 10.9% and 0.3% of its mass after 4, 8 and 12 weeks respectively in the lab-scale. In the plant, a high average remaining mass was also observed (93.9%). The supplementary lab-scale test showed similar remaining mass but higher fragmentation after 3 weeks. Conclusions: The results show that the samples achieved significant disintegration in the lab-scale but not in the plant. The difference between the tests that might further contribute to the differing degradation rates is the composition and heterogeneity of the composting substrate. Therefore, the substrate composition and thermophilic composting duration of individual plants are important considerations to determine the suitability of treating compostable plastic in real-world conditions.

There is resistance from industrial composting plants to the treatment of compostable biodegradable plastics. This study aims to compare the disintegration rates of two new biodegradable plastic blends developed for rigid and soft packaging applications in controlled industrial composting conditions in the lab as well as under actual industrial composting conditions in a composting plant. Results show significant disintegration of the material in the lab-scale up to 12 weeks. However, there were notable differences in the degree of disintegration of the samples in the lab compared to real-world conditions after 3 weeks. The 1 mm thick polylactic acid-based blend for rigid packaging experienced much higher disintegration in the lab with 68.9% remaining mass after 3 weeks compared to 97.2% remaining mass in the industrial composting plant. The 109 µm thick polybutylene succinate-based blend for soft packaging had similar remaining masses comparing the lab and full-scale tests. However, the lab-test showed higher fragmentation after 3 weeks. The characteristics of the organic waste inputs are potential causes of the lower disintegration rates. The study highlights the need to better understand the real-world industrial composting conditions and their variations when evaluating composting as a treatment method for biodegradable plastics.

Correction: Operative treatment of fragility fractures of the pelvis is connected with lower mortality. A single institution experience.

[This corrects the article DOI: 10.1371/journal.pone.0253408.].

Cyclo-Dipnictadialanes.

Using the AlI precursor Cp3t Al in conjunction with triphosphiranes (PAr)3 (Ar=Mes, Dip, Tip) we have succeeded in preparing Lewis base-free cyclic diphosphadialanes with both the Al and P atoms bearing three substituents. Using the sterically more demanding Dip and Tip substituents the first 1,2-diphospha-3,4-dialuminacyclobutanes were obtained, whereas with Mes substituents [Cp3t Al(µ-PMes)]2 is formed. This divergent reactivity was corroborated by DFT studies, which indicated the thermodynamic preference for the 1,2-diphospha-3,4-dialuminacyclobutane form for sterically more demanding groups on phosphorus. Using Cp*Al we could extend this concept to the corresponding cyclic diarsadialanes [Cp*Al(µ-AsAr)]2 (Ar=Dip, Tip) and additionally add the phosphorus variants [Cp*Al(µ-PAr)]2 (P=Mes, Dip, Tip). The reactivity of one variant [Cp3t Al(µ-PPh)]2 towards NHCs was tested and resulted in double NHC-stabilised [Cp3t (IiPr2 )Al(µ-PPh)]2 .

Synthesis of novel six-, seven- and eight-membered aluminum-containing rings by alumole ring expansion.

The chemistry of aluminacyclopentadienes, also known as alumoles, has experienced a resurgence in recent years, resulting in the preparation of a number of new entries in this class of compound. In contrast, their reactivity remains relatively unexplored. Thus far, their Lewis acid-base chemistry has been studied, as well as various ring-insertion reactions with unsaturated species such as alkynes and azides. Herein we present a range of new ring expansion reactions of an alumole with heteroatom-containing unsaturated species, providing novel six-, seven- and eight-membered cyclic products with high heteroatom content. Additionally, an unusual reaction was observed when the alumole was treated with morpholine-N-oxide, involving a stepwise insertion of two oxygen atoms, first into the exocyclic Al-C bond and then the endocyclic Al-C bond.

Synthesis, structure and insertion reactivity of Lewis acidic 9-aluminafluorenes.

9-Aluminafluorenes have only been sparingly investigated and their properties still remain largely unexplored. Herein, we report the synthesis of five aluminafluorene derivatives with a diverse array of aluminium substituents and probe their Lewis acid properties and reactivity. We show that 9-bromo-9-aluminafluorene readily forms Lewis acid-base adducts with N-heterocyclic carbenes (NHCs), cyclic (alkyl)(amino)carbenes (CAACs) and pyridines and that it undergoes a selective ring expansion reaction with the iminoborane tBuN[triple bond, length as m-dash]BMes to give a seven-membered ring, which can be viewed as a boron-nitrogen analogue of alumepins.