Understanding Selective Oxidations

Functionalizing organic molecules is an important value-creating step throughout the entire chemical value-chain. Oxyfunctionalization of value-chain. Oxyfunctionalization of e.g. C–H or C=C bonds is one of the most important functionalization technologies used industrially. The major challenge in this field is the prevention of side reactions and/or the consecutive over-oxidation of the desired products. Despite its importance, a fundamental understanding of the intrinsic chemistry, and the subsequent design of a tailored engineering environment, is often missing. Industrial oxidation processes are indeed to a large extent based on empirical know-how. In this mini-review, we summarize some of our previous work to help to bridge this knowledge gap and elaborate on our ongoing research

Malunion deformity of the forearm: Three-dimensional length variation of interosseous membrane and bone collision

It remains unclear to what extent the interosseous membrane (IOM) is affected through the whole range of motion (ROM) in posttraumatic deformities of the forearm. The purpose of this study is to describe the ligament- and bone-related factors involved in rotational deficit of the forearm. Through three-dimensional (3D) kinematic simulations on one cadaveric forearm, angular deformities of 5° in four directions (flexion, extension, valgus, varus) were produced at two locations of the radius and the ulna (proximal and distal third). The occurrence of bone collision in pronation and the linear length variation of six parts of the IOM through the whole ROM were compared between the 32 types of forearm deformities. Similar patterns could be observed among four groups: 12 types of deformity presented increased bone collision in pronation, 8 presented an improvement of bone collision with an increase of the mean linear lengthening of the IOM in neutral rotation, 6 had an increased linear lengthening of the IOM in supination with nearly unchanged bone collision in pronation and 6 types presented nearly unchanged bone collision in pronation with a shortening of the mean linear length of IOM in supination or neutral rotation. This kinematic analysis provides a better understanding of the ligament- and bone-related factors expected to cause rotational deficit in forearm deformity and may help to refine the surgical indications of patient-specific corrective osteotomy

Aerobic Oxidation of Cyclohexane Catalyzed by Flame-Made Nano-Structured Co/SiO2 Materials

The aerobic oxidation of cyclohexane was studied at 130°C in the presence of a Co/SiO2 catalyst, synthesized by flame-spray pyrolysis. Characterization of the material indicates that at low Co-loadings, CoII is predominantly present as tetrahedral species, whereas at higher loadings also small amounts of octahedral species can be found at the surface of the agglomerated nano-particles. Catalytic experiments demonstrate high activity, causing a complete in situ deperoxidation of the intermediate cyclohexylhydroperoxide. Hot-separation and catalyst-recycle tests corroborate the heterogeneous nature of the catalys

Silica-supported Z-selective Ru olefin metathesis catalysts

Under embargo until: 2022-01-17Recently reported thiolate-coordinated ruthenium alkylidene complexes show promise in Z-selective and stereoretentive olefin metathesis reactions. Herein we describe the immobilization of three Ru complexes containing a bulky aryl thiolate on mesostructured silica via surface organometallic chemistry. The applied methodology gives isolated catalytic sites homogeneously distributed on the silica surface. The catalytic results with two model substrates show comparable Z-selectivities to those of the homogeneous counterparts.acceptedVersio

Thermal restructuring of silica-grafted -CrO2Cl and -VOCl2 species

The volatile molecular precursors CrO2Cl2 and VOCl3 were grafted to thermally dehydrated silica in order to obtain site-isolated, monopodal [triple bond, length as m-dash]SiO–MOxCly−1 species (M = V, Cr). Thermal restructuring under dynamic vacuum was investigated up to 450 °C with different spectroscopic techniques (viz., NMR, UV-Vis, IR, Raman and XPS). During this thermal restructuring, VOCl3 or CrO2Cl2 is partially eliminated from the surface, whilst the remaining surface species become multiply bound to the silica surface. This restructuring increases both the chemical and thermal stability of these materials, and has significant consequences for their performance as heterogeneous catalysts

Thermal restructuring of silica-grafted TiClx species and consequences for epoxidation catalysis

Anchoring titanium: Grafting of TiCl4 to site-isolated silanol groups on silica initially leads to freely rotating species. Upon heating, a thermal restructuring takes place, causing the elimination of TiCl4 and the formation of more strongly anchored titanium species, which were found to be highly active and stable epoxidation catalysts

Influence of femoral tunnel exit on the 3D graft bending angle in anterior cruciate ligament reconstruction

PURPOSE To quantify the influence of the femoral tunnel exit (FTE) on the graft bending angle (GBA) and GBA-excursion throughout a full range of motion (ROM) in single-bundle anterior cruciate ligament (ACL) reconstruction. METHODS Three-dimensional (3D) surface models of five healthy knees were generated from a weight-bearing CT obtained throughout a full ROM (0, 30, 60, 90, 120°) and femoral and tibial ACL insertions were computed. The FTE was simulated for 16 predefined positions, referenced to the Blumensaat's line, for each patient throughout a full ROM (0, 30, 60, 90, 120°) resulting in a total of 400 simulations. 3D GBA was calculated between the 3D directional vector of the ACL and the femoral tunnel, while the intra-articular ACL insertions remained unchanged. For each simulation the 3D GBA, GBA-excursion, tunnel length and posterior tunnel blow-out were analysed. RESULTS Overall, mean GBA decreased with increasing knee flexion for each FTE (p < 0.001). A more distal location of the FTE along the Blumensaat's line resulted in an increase of GBA and GBA-excursion of 8.5 ± 0.6° and 17.6 ± 1.1° /cm respectively (p < 0.001), while a more anterior location resulted in a change of GBA and GBA-excursion of -2.3 ± 0.6° /cm (+ 0.6 ± 0.4°/ cm from 0-60° flexion) and 9.8 ± 1.1 /cm respectively (p < 0.001). Mean tunnel length was 38.5 ± 5.2 mm (range 29.6-50.5). Posterior tunnel blow-out did not occur for any FTE. CONCLUSION Aiming for a more proximal and posterior FTE, with respect to Blumensaat's line, reliably reduces GBA and GBA-excursion, while preserving adequate tunnel length. This might aid to reduce excessive graft stress at the femoral tunnel aperture, decrease femoral tunnel widening and promote graft-healing. LEVEL OF EVIDENCE IV

Aerobic Oxidation of Cyclohexane Catalyzed by Flame-Made Nano-Structured Co/SiO2 Materials

ISSN:1022-5528ISSN:1572-902

Supported Ru olefin metathesis catalysts via a thiolate tether

International audienc

Impaired IFNγ-signaling and mycobacterial clearance in IFNγR1-deficient human iPSC-derived macrophages

Mendelian susceptibility to mycobacterial disease (MSMD) is caused by inborn errors of interferon gamma (IFNγ) immunity and is characterized by severe infections by weakly virulent mycobacteria. Although IFNγ is the macrophage-activating factor, macrophages from these patients have never been studied. We demonstrate the generation of heterozygous and compound heterozygous (iMSMD-cohet) induced pluripotent stem cells (iPSCs) from a single chimeric patient, who suffered from complete autosomal recessive IFNγR1 deficiency and received bone-marrow transplantation. Loss of IFNγR1 expression had no influence on the macrophage differentiation potential of patient-specific iPSCs. In contrast, lack of IFNγR1 in iMSMD-cohet macrophages abolished IFNγ-dependent phosphorylation of STAT1 and induction of IFNγ-downstream targets such as IRF-1, SOCS-3, and IDO. As a consequence, iMSMD-cohet macrophages show impaired upregulation of HLA-DR and reduced intracellular killing of Bacillus Calmette-Guérin. We provide a disease-modeling platform that might be suited to investigate novel treatment options for MSMD and to gain insights into IFNγ signaling in macrophages