We present the synthesis and coordination chemistry of a bulky, tripodal N,N,O ligand, ImPh2NNOtBu (L), designed to model the 2‐His‐1‐carboxylate facial triad (2H1C) by means of two imidazole groups and an anionic 2,4‐di‐tert‐butyl‐subtituted phenolate. Reacting K‐L with MCl2 (M = Fe, Zn) affords the isostructural, tetrahedral non‐heme complexes [Fe(L)(Cl)] (1) and [Zn(L)(Cl)] (2) in high yield. The tridentate N,N,O ligand coordination observed in their X‐ray crystal structures remains intact and well‐defined in MeCN and CH2Cl2 solution. Reacting 2 with NaSPh affords a tetrahedral zinc thiolate complex, [Zn(L)(SPh)] (4), that is relevant to isopenicillin N synthase (IPNS) biomimicry. Cyclic voltammetry studies demonstrate the ligand's redox non‐innocence, where phenolate oxidation is the first electrochemical response observed in K‐L, 2 and 4. However, the first electrochemical oxidation in 1 is iron‐centred, the assignment of which is supported by DFT calculations. Overall, ImPh2NNOtBu provides access to well‐defined mononuclear, monoligated, N,N,O‐bound metal complexes, enabling more accurate structural modelling of the 2H1C to be achieved.
Introduction Optical coherence tomography (OCT) is being investigated in urologic oncology for optical diagnosis. This comprehensive review analyzes the current state of development of OCT for bladder, upper urinary tract, kidney, prostate, testis, and penis cancer. Also, the potential role of OCT with regard to the current diagnostic pathways is critically appraised to guide future developments. Methods Embase and Pubmed were systematically searched for English and German articles on OCT in humans up to December 2017. Reviews were excluded. Case reports were excluded, unless they presented a landmark in the development of OCT. Results Out of 878 articles, 17 relevant articles on bladder, seven on kidney, five on upper urinary tract, four on prostate, and two on penile cancer were included. In these organs, in vivo OCT imaging is feasible with potential for qualitative and quantitative diagnosis, grading and staging in specific organs. The development of OCT has reached IDEAL stage 2b with 2b level of evidence. Relevant articles on testis cancer were lacking. Conclusion OCT allows for non-or minimally invasive cancer diagnosis in the bladder, upper urinary tract, kidney, prostate, and penis. In some organs, OCT also may enable histologic grade and stage prediction. However, the current evidence is still at an exploratory level. With regard to the potential additional value of OCT in comparison to the current diagnostic pathways, OCT could become a diagnostic replacement or add-on test for urothelial carcinoma, penile carcinoma, and renal masses. Further research in these conditions should be encouraged.
Route design and proof of concept synthesis was conducted on a synthetically challenging atropisomeric KRASG12C inhibitor to support clinical API manufacture. Improvements to the synthesis of a chiral piperazine fragment gave reduced step count and streamlined protecting group strategy via the formation and methanol ring opening of an N-carboxy-anhydride (NCA). The complex atropisomeric nitroquinoline was accessed via an early stage salt-resolution followed by a formal two-part nitromethane-carbonylation, avoiding a high temperature Gould–Jacobs cyclization that previously led to atropisomer racemization. The substrate scope of the formal nitromethane-carbonylation strategy was further explored for a range of ortho-substituted bromo/iodo unprotected anilines.
<b><i>Background:</i></b> Patients with interstitial lung diseases (ILDs) frequently present with nondiagnostic high-resolution CT (HRCT) scan and bronchoalveolar lavage (BAL) results, resulting in the need for invasive surgical or cryo-lung biopsy that is associated with significant morbidity. Confocal laser endomicroscopy (CLE) and optical coherence tomography (OCT) are high-resolution laser and light-based techniques that provide real-time imaging of the alveolar compartment during bronchoscopy with a different depth and field of view. <b><i>Objectives:</i></b> The aim of the study was to correlate OCT and CLE imaging to HRCT imaging in ILD. <b><i>Methods:</i></b> This is a retrospective case series of 20 ILD patients who underwent alveolar CLE and OCT imaging during a standard bronchoscopy with BAL, followed by a lung biopsy when indicated. CLE and OCT imaging were compared to four main HRCT patterns and histology. The final diagnosis was based on the multidisciplinary discussion diagnosis. <b><i>Results:</i></b> Bronchoscopic CLE and OCT imaging were feasible and safe and provided additional high-detailed anatomical information compared to the HRCT. Bronchoscopic real-time CLE was capable of identification of “alveolar cells” (ground glass opacities) and lung fibrosis (increased alveolar elastin fibers). Bronchoscopic real-time OCT allowed for visualization of “patchy fibrotic disease”, “honeycombing” (microcysts), and mucosal granulomas in the airways. <b><i>Conclusions:</i></b> Bronchoscopic CLE and OCT of the alveolar compartment is feasible and safe and enables minimally invasive, high-resolution detection of specific ILD features with the potential to improve ILD diagnostics and monitoring and decrease the need for surgical or cryo-lung biopsies.
Background Poor fundus perfusion is seen as the major factor for the development of anastomotic necrosis, leakage and strictures. Quantitative imaging of tissue perfusion during reconstructive surgery, therefore, may reduce the incidence of complications. Imaging the fluorescense of intravenously administered fluorophores is an optical, non-contact method to image blood flow in real-time. However, quantitative parameters for perfusion evaluation are stil lacking. The objective of this study is to test fluorescence imaging derived quantitative parameters for perfusion evaluation of the gastric tube during surgery and to correlate these parameters to patient outcome in terms of anastomotic leakage. Methods This study included 22 patients (October 2015 - June 2016). Indocyanine green (ICG) was injected intravenously and the fluorescense intensity of the gastric tube was imaged for 2–3 minutes. At 4 locations, quantitative analysis of the fluorescent intensity over time was performed to obtain perfusion related parameters: the maximal intensity, mean slope and influx timepoint. These parameters were tested for significant differences between the four perfusion areas of the gastric tube (from normal to decreased perfusion) with a repeated ANOVA test. Furthermore, these parameters and the distance of the end of the gastroepiploic artery to the fundus and distance of the demarcation of the fluorescent signal to the fundus were compared with patient outcome in terms of anastomotic leakage development. Results The fluorescent signal could be detected in all analyzed patients (n = 20). Maximal intensity, mean slope and influx timepoint were significantly different between the base of the gastric tube and the fundus (P < 0.0001). While the distance of the watershed and the demarcation of ICG to the fundus varied between patients, the distance of the demarcation of ICG to the fundus was significantly higher in the three patients who developed anastomotic leakage (P < 0.0001). No allergic reactions on ICG were witnessed. Conclusion Intra-operative fluorescence imaging is feasible to visualize perfusion quantitatively in gastric-tube surgery, using the parameters maximal intensity, mean slope and influx timepoint. A low slope and a large distance between the fluorescence demarcation and the fundus were seen in patients who developed anastomotic leakage and could therefore allow for early risk stratification of necrosis. Disclosure All authors have declared no conflicts of interest.
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