A Rotaxane-like Cage-in-Ring Structural Motif for a Metallosupramolecular Pd6L12\mathrm{Pd_{6}L_{12}} Aggregate

A BODIPY‐based bis(3‐pyridyl) ligand undergoes self‐assembly upon coordination to tetravalent palladium(II) cations to form a Pd$_6$L$_{12}$ metallosupramolecular assembly with an unprecedented structural motif that resembles a rotaxane‐like cage‐in‐ring arrangement. In this assembly the ligand adopts two different conformations—a C‐shaped one to form a Pd$_2$L$_4$ cage which is located in the center of a Pd$_4$L$_8$ ring consisting of ligands in a W‐shaped conformation. This assembly is not mechanically interlocked in the sense of catenation but it is stabilized only by attractive π‐stacking between the peripheral BODIPY chromophores and the ligands’ skeleton as well as attractive van der Waals interactions between the long alkoxy chains. As a result, the co‐arrangement of the two components leads to a very efficient space filling. The overall structure can be described as a rotaxane‐like assembly with a metallosupramolecular cage forming the axle in a metallosupramolecular ring. This unique structural motif could be characterized via ESI mass spectrometry, NMR spectroscopy, and X‐ray crystallography

Voxel-based analyses of magnetization transfer imaging of the brain in hepatic encephalopathy

AIM: To evaluate the spatial distribution of cerebral abnormalities in cirrhotic subjects with and without hepatic encephalopathy (HE) found with magnetization transfer imaging (MTI)

Dynamic Complex-to-Complex Transformations of Heterobimetallic Systems Influence the Cage Structure or Spin State of Iron(II) Ions

Two new heterobimetallic cages, a trigonal‐bipyramidal and a cubic one, were assembled from the same mononuclear metalloligand by adopting the molecular library approach, using iron(II) and palladium(II) building blocks. The ligand system was designed to readily assemble through subcomponent self‐assembly. It allowed the introduction of steric strain at the iron(II) centres, which stabilizes its paramagnetic high‐spin state. This steric strain was utilized to drive dynamic complex‐to‐complex transformations with both the metalloligand and heterobimetallic cages. Addition of sterically less crowded subcomponents as a chemical stimulus transformed all complexes to their previously reported low‐spin analogues. The metalloligand and bipyramid incorporated the new building block more readily than the cubic cage, probably because the geometric structure of the sterically crowded metalloligand favours the cube formation. Furthermore it was possible to provoke structural transformations upon addition of more favourable chelating ligands, converting the cubic structures into bipyramidal ones

A Family of Heterobimetallic Cubes Shows Spin‐Crossover Behaviour Near Room Temperature

Using 4-(4′-pyridyl)aniline as a simple organic building block in combination with three different aldehyde components together with metal(II) salts gave three different Fe8Pt6-cubes and their corresponding Zn$_8$Pt$_6$ analogues by employing the subcomponent self-assembly approach. Whereas the use of zinc(II) salts gave rise to diamagnetic cages, iron(II) salts yielded metallosupramolecular cages that show spin-crossover behaviour in solution. The spin-transition temperature T$_{1/2}$ depends on the incorporated aldehyde component, giving a construction kit for the deliberate synthesis of spin-crossover compounds with tailored transition properties. Incorporation of 4-thiazolecarbaldehyde or N-methyl-2-imidazole-carbaldehyde yielded cages that undergo spin-crossover around room temperature whereas the cage obtained using 1H-4-imidazolecarbaldehyde shows a spin-transition at low temperatures. Three new structures were characterized by synchrotron X-ray diffraction and all structures were characterized by mass spectrometry, NMR and UV/Vis spectroscopy

Delayed gadolinium-enhanced magnetic resonance imaging of cartilage (dGEMRIC), after slipped capital femoral epiphysis

OBJECTIVE: The aim of this study was to assess the glycosaminoglycan (GAG) content in hip joint cartilage in mature hips with a history of slipped capital femoral epiphysis (SCFE) using delayed gadolinium-enhanced MRI of cartilage (dGEMRIC). METHODS: 28 young-adult subjects (32 hips) with a mean age of 23.8+/-4.0 years (range: 18.1-30.5 years) who were treated for mild or moderate SCFE in adolescence were included into the study. Hip function and clinical symptoms were evaluated with the Harris hip score (HHS) system at the time of MRI. Plain radiographic evaluation included Tonnis grading, measurement of the minimal joint space width (JSW) and alpha-angle measurement. The alpha-angle values were used to classify three sub-groups: group 1=subjects with normal femoral head-neck offset (alpha-angle 60 degrees ). RESULTS: There was statistically significant difference noted for the T1(Gd) values, lateral and central, between group 1 and group 3 (p-values=0.038 and 0.041). The T1(Gd) values measured within the lateral portion were slightly lower compared with the T1(Gd) values measured within the central portion that was at a statistically significance level (p-value <0.001). HHS, Tonnis grades and JSW revealed no statistically significant difference. CONCLUSION: By using dGEMRIC in the mid-term follow-up of SCFE we were able to reveal degenerative changes even in the absence of joint space narrowing that seem to be related to the degree of offset pathology. The dGEMRIC technique may be a potential diagnostic modality in the follow-up evaluation of SCFE

Tumor Lesion Glycolysis and Tumor Lesion Proliferation for Response Prediction and Prognostic Differentiation in Patients With Advanced Non-Small Cell Lung Cancer Treated With Erlotinib

Purpose: The aim was to assess the value of tumor lesion glycolysis (TLG) and tumor lesion proliferation (TLP) determined by FDG and 3'-deoxy-3'-F-18-fluorothymidine (FLT) PET for response prediction and prognostic differentiation in patients with advanced non-small cell lung cancer (NSCLC) treated with erlotinib. Patients and Methods: FDG-PET and FLT-PETwere performed in 30 patients with untreated Stage IV NSCLC before start of therapy, 1 (early) and 6 (late) weeks after erlotinib treatment. Functional tumor volume parameters including TLG in FDG-PET and TLP in FLT-PET were measured in the sum of up to 5 lesions per scan. Metabolic response was assessed using different cutoff values for percentage changes of TLG and TLP. Absolute baseline and residual levels of TLG and TLP were used for dichotomizing the patients into 2 groups. Kaplan-Meier analysis and the log-rank test were performed to analyze the association with progression-free survival (PFS). Results: Patients with a metabolic response measured by early changes of TLP and late changes of TLG and TLP showed a significantly better PFS than metabolically nonresponding patients. A lower cutoff value of 20% or 30% for definition of metabolic response showed better differentiation between metabolically responding and nonresponding patients in cases where the 45% cutoff value revealed no significant results. Furthermore, patients with lower absolute early and late residual TLG and TLP levels had a significantly prolonged PFS. In contrast, absolute baseline TLG and TLP levels showed no significant association with PFS. Conclusions: In patients with advanced NSCLC, percentage changes of TLG and TLP and absolute residual TLG and TLP levels under erlotinib treatment emerged as strong predictive factors for PFS. Our findings indicate that a cutoff value of 20% or 30% for definition of metabolic response measured by percentage changes of TLG and TLP provides suitable results for response prediction, which should be further validated

Polymorphic chiral squaraine crystallites in textured thin films

An enantiomerically pure (R)‐2‐methylpyrrolidine‐based anilino squaraine crystallizes in two chiral polymorphs adopting a monoclinic C2 and an orthorhombic P212121 structure, respectively. By various thin‐film preparation techniques, a control of the polymorph formation is targeted. The local texture of the resulting textured thin films is connected to the corresponding optical properties. Special attention is paid to an unusual Davydov splitting, the anisotropic chiroptical response arising from preferred out‐of‐plane orientation of the crystallites, and the impact of the polymorph specific excitonic coupling.peerReviewe

Quantitative Analysis of Response to Treatment with Erlotinib in Advanced Non-Small Cell Lung Cancer Using F-18-FDG and 3 '-Deoxy-3 '-F-18-Fluorothymidine PET

The purpose of this study was to evaluate the relevance for the prediction of clinical benefit of first-line treatment with erlotinib using different quantitative parameters for PET with both F-18-FDG and 3'-deoxy-3'-F-18-fluorothymidine (F-18-FLT) in patients with advanced non-small cell lung cancer. Methods: Data were used from a prospective trial involving patients with untreated stage IV non-small cell lung cancer. F-18-FDG PET and F-18-FLT PET were performed before and 1 (early) and 6 (late) weeks after erlotinib treatment. Several quantitative standardized uptake values (SUVs) using different definitions of volumes of interest with varying isocontours (maximum SUV [SUVmax], 2-dimensional peak SUV [SUV2Dpeak], 3-dimensional [3D] peak SUV [SUV3Dpeak], 3D isocontour at 50% of the maximum pixel value [SUV50], 3D isocontour at 50% adapted for background [SUVA50], 3D isocontour at 41% of the maximum pixel value adapted for background [SUVA41], 3D isocontour at 70% of the maximum pixel value [SUV70], 3D isocontour at 70% adapted for background [SUVA70], and relative SUV threshold level [SUVRTL]) and metabolically active volume measurements were obtained in the hottest single tumor lesion and in the sum of up to 5 lesions per scan in 30 patients. Metabolic response was defined as a minimum reduction of 30% in each of the different SUVs and as a minimum reduction of 45% in metabolically active volume. Progression-free survival (PFS) was compared between patients with and without metabolic response measured with each of the different parameters, using Kaplan-Meier statistics and a log-rank test. Results: Patients with a metabolic response on early F-18-FDG PET and F-18-FLT PET in the hottest single tumor lesion as well as in the sum of up to 5 lesions per scan had a significantly longer PFS, regardless of the method used to calculate SUV. However, the highest significance was obtained for SUVmax, SUV50, SUVA50, and SUVA41. Patients with a metabolic response measured by SUVmax and SUV3Dpeak on late F-18-FDG PET in the hottest single tumor lesion had a significantly longer PFS. Furthermore, Kaplan-Meier analyses showed a strong association between PFS and response seen by metabolically active volume, measured either in early F-18-FLT or in late F-18-FDG. Conclusion: Early F-18-FDG PET and F-18-FLT PET can predict PFS regardless of the method used for SUV calculation. However, SUVmax, SUV50, SUVA50, and SUVA41 measured with F-18-FDG might be the best robust SUV to use for early response prediction. Metabolically active volume measurement in early F-18-FLT PET and late F-18-FDG PET may have an additional predictive value in monitoring response in patients with advanced non-small cell lung cancer treated with erlotinib