Divalent metallocenes of the lanthanides – a guideline to properties and reactivity

Since the discovery in the early 1980s, the soluble divalent metallocenes of lanthanides have become a steadily growing field in organometallic chemistry. The predominant part of the investigation has been performed with samarium, europium, and ytterbium, whereas only a few reports dealing with other rare earth elements were disclosed. Reactions of these metallocenes can be divided into two major categories: (1) formation of Lewis acid–base complexes, in which the oxidation state remains +II; and (2) single electron transfer (SET) reductions with the ultimate formation of Ln(III) complexes. Due to the increasing reducing character from Eu(II) over Yb(II) to Sm(II), the plethora of literature concerning redox reactions revolves around the metallocenes of Sm and Yb. In addition, a few reactivity studies on Nd(II), Dy(II) and mainly Tm(II) metallocenes were published. These compounds are even stronger reducing agents but significantly more difficult to handle. In most cases, the metals are ligated by the versatile pentamethylcyclopentadienyl ligand: (C$_5$Me$_5$). Other cyclopentadienyl ligands are fully covered but only discussed in detail, if the ligand causes differences in synthesis or reactivity. Thus, the focus lays on three compounds: [(C$_5$Me$_5$)$_2$Sm], [(C$_5$Me$_5$)$_2$Eu] and [(C$_5$Me$_5$)$_2$Yb] and their solvates. We discuss the synthesis and physical properties of divalent lanthanide metallocenes first, followed by an overview of the reactivity rendering the full potential of these versatile reactants

Shrinkage vectors in flowable bulk-fill and conventional composites: bulk versus incremental application

OBJECTIVES Sufficient depth of cure allows bulk-fill composites to be placed with a 4-mm thickness. This study investigated bulk versus incremental application methods by visualizing shrinkage vectors in flowable bulk-fill and conventional composites. MATERIALS AND METHODS Cylindrical cavities (diameter = 6 mm, depth = 4 mm) were prepared in 24 teeth and then etched and bonded with OptiBond FL (Kerr, Italy). The composites were mixed with 2 wt% radiolucent glass beads. In one group, smart dentin replacement (SDR, Dentsply) was applied in bulk "SDR-bulk" (n = 8). In two groups, SDR and Tetric EvoFlow (Ivoclar Vivadent) were applied in two 2-mm-thick increments: "SDR-incrementa" and "EvoFlow-incremental". Each material application was scanned with a micro-CT before and after light-curing (40 s, 1100 mW/cm2), and the shrinkage vectors were computed via image segmentation. Thereafter, linear polymerization shrinkage, shrinkage stress and gelation time were measured (n = 10). RESULTS The greatest shrinkage vectors were found in "SDR-bulk" and "SDR-increment2," and the smallest were found in "SDR-increment1-covered" and "EvoFlow-increment1-covered." Shrinkage away from and toward the cavity floor was greatest in “SDR-bulk“ and “EvoFlow-increment2", respectively. The mean values of the shrinkage vectors were significantly different between groups (one-way ANOVA, Tamhane's T2 test, p < 0.05). The linear polymerization shrinkage and shrinkage stress were greatest in Tetric EvoFlow, and the gelation time was greatest in "SDR-bulk". CONCLUSIONS The bulk application method had greater values of shrinkage vectors and a higher debonding tendency at the cavity floor. CLINICAL RELEVANCE Incremental application remains the gold standard of composite insertion

Molecular magnetic resonance imaging (MRI) of inflamed myocardium using ferucarbotran in patients with acute myocardial infarction

Introduction: Superparamagnetic iron oxide nanoparticle (SPIO)-based molecular imaging agents targeting macrophages have been developed and successfully applied in animal models of myocardial infarction

I-BEAT: New ultrasonic method for single bunch measurement of ion energy distribution

The shape of a wave carries all information about the spatial and temporal structure of its source, given that the medium and its properties are known. Most modern imaging methods seek to utilize this nature of waves originating from Huygens' principle. We discuss the retrieval of the complete kinetic energy distribution from the acoustic trace that is recorded when a short ion bunch deposits its energy in water. This novel method, which we refer to as Ion-Bunch Energy Acoustic Tracing (I-BEAT), is a generalization of the ionoacoustic approach. Featuring compactness, simple operation, indestructibility and high dynamic ranges in energy and intensity, I-BEAT is a promising approach to meet the needs of petawatt-class laser-based ion accelerators. With its capability of completely monitoring a single, focused proton bunch with prompt readout it, is expected to have particular impact for experiments and applications using ultrashort ion bunches in high flux regimes. We demonstrate its functionality using it with two laser-driven ion sources for quantitative determination of the kinetic energy distribution of single, focused proton bunches.Comment: Paper: 17 Pages, 3 figures Supplementary Material 16 pages, 7 figure

Treatment characteristics and outcomes of pure Acinar cell carcinoma of the pancreas - A multicentric European study on radically resected patients

Background: Acinar cell carcinomas (ACC) belong to the exocrine pancreatic malignancies. Due to their rarity, there is no consensus regarding treatment strategies for resectable ACC. Methods: This is a retrospective multicentric study of radically resected pure pancreatic ACC. Primary endpoints were overall survival (OS) and disease-free survival (DFS). Further endpoints were oncologic outcomes related to tumor stage and therapeutic protocols. Results: 59 patients (44 men) with a median age of 64 years were included. The median tumor size was 45.0&nbsp;mm. 61.0% were pT3 (n&nbsp;=&nbsp;36), nodal positivity rate was 37.3% (n&nbsp;=&nbsp;22), and synchronous distant metastases were present in 10.1% of the patients (n&nbsp;=&nbsp;6). 5-Years OS was 60.9% and median DFS 30 months. 24 out of 31 recurred systemically (n&nbsp;=&nbsp;18 only systemic, n&nbsp;=&nbsp;6 local and systemic). Regarding TNM-staging, only the N2-stage negatively influenced OS and DFS (p&nbsp;=&nbsp;0.004, p&nbsp;=&nbsp;0.001). Adjuvant treatment protocols (performed in 62.7%) did neither improve OS (p&nbsp;=&nbsp;0.542) nor DFS (p&nbsp;=&nbsp;0.159). In 9 cases, radical resection was achieved following neoadjuvant therapy. Discussion: Radical surgery is currently the mainstay for resectable ACC, even for limited metastatic disease. Novel (neo)adjuvant treatment strategies are needed, since current systemic therapies do not result in a clear survival benefit in the perioperative setting

Right-Sided Location Not Associated With Missed Colorectal Adenomas in an Individual-Level Reanalysis of Tandem Colonoscopy Studies

Background & Aims Interval cancers occur more frequently in the right colon. One reason could be that right-sided adenomas are frequently missed in colonoscopy examinations. We reanalyzed data from tandem colonoscopies to assess adenoma miss rates in relation to location and other factors. Methods We pooled data from 8 randomized tandem trials comprising 2218 patients who had diagnostic or screening colonoscopies (adenomas detected in 49.8% of patients). We performed a mixed-effects logistic regression with patients as cluster effects with different independent parameters. Factors analyzed included location (left vs right, splenic flexure as cutoff), adenoma size, form, and histologic features. Analyses were controlled for potential confounding factors such as patient sex and age, colonoscopy indication, and bowel cleanliness. Results Right-side location was not an independent risk factor for missed adenomas (odds ratio [OR] compared with the left side, 0.94; 95% CI, 0.75–1.17). However, compared with adenomas ≤5 mm, the OR for missing adenomas of 6–9 mm was 0.62 (95% CI, 0.44–0.87), and the OR for missing adenomas of ≥10 mm was 0.51 (95% CI, 0.33–0.77). Compared with pedunculated adenomas, sessile (OR, 1.82; 95% CI, 1.16–2.85) and flat adenomas (OR, 2.47; 95% CI, 1.49–4.10) were more likely to be missed. Histologic features were not significant risk factors for missed adenomas (OR for adenomas with high-grade intraepithelial neoplasia, 0.68; 95% CI, 0.34–1.37 and OR for sessile serrated adenomas, 0.87; 95% CI, 0.47–1.64 compared with low-grade adenomas). Men had a higher number of adenomas per colonoscopy (1.27; 95% CI, 1.21–1.33) than women (0.86; 95% CI, 0.80–0.93). Men were less likely to have missed adenomas than women (OR for missed adenomas in men, 0.73; 95% CI, 0.57–0.94). Conclusions In an analysis of data from 8 randomized trials, we found that right-side location of an adenoma does not increase its odds for being missed during colonoscopy but that adenoma size and histologic features do increase risk. Further studies are needed to determine why adenomas are more frequently missed during colonoscopies in women than men

Extending the Automation Pyramid for Industrial Demand Response

Industrial demand response uses a multitude of energy flexibility measures. Their planning and control requires various production IT systems. A widely accepted approach to classify these inhouse IT systems are the levels of the automation pyramid in companies. This paper broadens the scope of this concept to overcome the limitation to companies’ (virtual) borders by including required IT systems that refine and monetarize a company’s energy flexibility, e.g. energy markets, aggregators, etc. Therefore, a holistic approach for the classification of functionalities for industrial demand response across companies and energy markets is developed and applied exemplarily

Feasibility and Efficacy of Adjuvant Chemotherapy With Gemcitabine After Liver Transplantation for Perihilar Cholangiocarcinoma: A Multi-Center, Randomized, Controlled Trial (pro-duct001)

Background Liver transplantation (LT) is considered a therapeutic option for unresectable perihilar cholangiocarcinoma (PHC) within defined criteria. It remains uncertain whether patients can safely receive adjuvant chemotherapy after LT. Methods We performed a prospective, multi-center, randomized, non-blinded two-arm trial (pro-duct001). Patients after LT for unresectable PHC within defined criteria were randomized to adjuvant gemcitabine (LT-Gem group) and LT alone (LT alone group). The primary objective was to investigate if adjuvant chemotherapy is feasible in ≥ 85% of patients after LT. The primary endpoint was the percentage of patients completing the 24 weeks course of adjuvant chemotherapy. Secondary endpoints included overall survival (OS) and disease-free (DFS), and complication rates. Results Twelve patients underwent LT for PHC, of which six (50%) were eligible for randomization (LT-Gem: three patients, LT alone: three patients). Two out of three patients discontinued adjuvant chemotherapy after LT due to intolerance. The study was prematurely terminated due to slow enrollment. One patient with PHC had underlying primary sclerosing cholangitis (PSC). Tumor-free margins could be achieved in all patients. In both the LT-Gem and the LT alone group, the cumulative 1-, 3-, and 5-year OS and DFS rates were 100%, 100%, 67%, and 100%, 67% and 67%, respectively. Conclusions This prospective, multi-center study was prematurely terminated due to slow enrollment and a statement on the defined endpoints cannot be made. Nevertheless, long-term survival data are consistent with available retrospective data and confirm defined criteria for LT. Since more evidence of LT per se in unresectable PHC is urgently needed, a prospective, non-randomized follow-up study (pro-duct002) has since been launched