Conversion of Ethene to Propene by a Dual Function NiSO4/Re2O7/γ-Al2O3 Catalyst

A NiSO₄/Re₂O₇/γ-Al₂O₃ catalyst was prepared by co-impregnation using an aqueous solution of NiSO₄ and [NH₄][ReO₄], which catalyzes direct conversion of ethene to propene at mild reaction condition (323 K, 1 atm). Catalyst deactivation may be caused by coke formation. The two catalytic components appear to work independently of each other.     

Impact of an Altered Wnt1/β-Catenin Expression on Clinicopathology and Prognosis in Clear Cell Renal Cell Carcinoma

In renal cell carcinoma (RCC), single members of the Wnt/β-catenin signaling cascade were recently identified to contribute to cancer progression. However, the role of Wnt1, one of the key ligands in β-catenin regulation, is currently unknown in RCC. Therefore, alterations of the Wnt1/β-catenin axis in clear cell RCC (ccRCC) were examined with regard to clinicopathology, overall survival (OS) and cancer specific survival (CSS). Corresponding ccRCCs and benign renal tissue were analyzed in 278 patients for Wnt1 and β-catenin expression by immunohistochemistry in tissue microarrays. Expression scores, including intensity and percentage of stained cells, were compared between normal kidney and ccRCCs. Data was categorized according to mean expression scores and correlated to tumor and patients’ characteristics. Survival was analyzed according to the Kaplan-Meier and log-rank test. Univariable and multivariable Cox proportional hazard regression models were used to explore the independent prognostic value of Wnt1 and β-catenin. In ccRCCs, high Wnt1 was associated with increased tumor diameter, stage and vascular invasion (p ≤ 0.02). High membranous β-catenin was associated with advanced stage, vascular invasion and tumor necrosis (p ≤ 0.01). Higher diameter, stage, node involvement, grade, vascular invasion and sarcomatoid differentiation (p ≤ 0.01) were found in patients with high cytoplasmic β-catenin. Patients with a high cytoplasmic β-catenin had a significantly reduced OS (hazard ratio (HR) 1.75) and CSS (HR 2.26), which was not independently associated with OS and CSS after adjustment in the multivariable model. Increased ccRCC aggressiveness was reflected by an altered Wnt1/β-catenin signaling. Cytoplasmic β-catenin was identified as the most promising candidate associated with unfavorable clinicopathology and impaired survival. Nevertheless, the shift of membranous β-catenin to the cytoplasm with a subsequently increased nuclear expression, as shown for other malignancies, could not be demonstrated to be present in ccRCC.     

LAS glass–ceramic scaffolds by three-dimensional printing

Highly porous (>60% open porosity) glass–ceramic scaffolds with remarkable mechanical properties (compression strength of ～15 MPa) were produced by indirect 3D printing. Precursor glass powders were printed into 3D ordered structures and then heat treated to sinter and develop crystalline phases. The final glass–ceramic contained a β-spodumene solid solution together with a secondary phase of lithium disilicate.The precision of the printed geometry and the density of the struts in the scaffold depended on several processing parameters (e.g. powder size and flowability, layer thickness) and were improved by increasing the binder saturation and drying time. Two types of powders with different particle size distribution (PSD) and flowability were used. Powders with a larger PSD, could be processed within a wider range of printing parameters due to their good flowability; however, the printing precision and the struts density were lower compared to the scaffolds printed using the powder in a smaller average PSD.     

Flue gas cleaning by periodic absorption

Simulations and designs are presented of conventional and periodic SO₂ absorption from exhaust gases using salt water as absorption solvent. Operating conditions resemble those of a maritime operation, involving relatively small amounts of SO₂, so the separation is in the linear region. The advantages of periodic operation, as already demonstrated for conventional distillation remain valid for absorption processes: Less tall towers, than staged towers are possible, or substantially less salt water is required for the process employing periodic cycling.     

Evaluation of a Radiolabeled Macrocyclic Peptide as Potential PET Imaging Probe for PD−L1

The interaction between the immune checkpoint PD-1 and PD−L1 promotes T-cell deactivation and cancer proliferation. Therefore, immune checkpoint inhibition therapy, which relies on prior assessment of the target, has been widely used for many cancers. As a non-invasive molecular imaging tool, radiotracers bring novel information on the in vivo expression of biomarkers (e. g., PD−L1), enabling a personalized treatment of patients. Our work aimed at the development of a PD−L1-specific, peptide-based PET radiotracer. We synthesized and evaluated a radiolabeled macrocyclic peptide adapted from a patent by Bristol Myers Squibb. Synthesis of [⁶⁸Ga]Ga-NJMP1 yielded a product with a radiochemical purity>95 % that was evaluated in vitro. However, experiments on CHO−K1 hPD−L1 cells showed very low cell binding and internalization rates of [⁶⁸Ga]Ga-NJMP1 in comparison to a control radiopeptide (WL12). Non-radioactive cellular assays using time-resolved fluorescence energy transfer confirmed the low affinity of the reported parent peptide and the DOTA-derivatives towards PD−L1. The results of our studies indicate that the macrocyclic peptide scaffold reported in the patent literature is not suitable for radiotracer development due to insufficient affinity towards PD−L1 and that C-terminal modifications of the macrocyclic peptide interfere with important ligand/receptor interactions.     

Lipozyme IM‐catalyzed interesterification for the production of margarine fats in a 1 kg scale stirred tank reactor

Lipozyme IM‐catalyzed interesterification of the oil blend between palm stearin and coconut oil (75/25 w/w) was studied for the production of margarine fats in a 1 kg scale batch stirred tank reactor. Parameters such as lipase load, water content, temperature, and reaction time were investigated. The reusability of Lipozyme IM was also studied under optimized conditions. The interesterification products were monitored by analysis of triacylglycerol profiles, the contents of diacylglycerols, free fatty acids (FFA), and solid fat contents. The contents of some triacylglycerol species, which were categorized by equivalent carbon number (ECN), namely ECN34, 36, 48, and 50, decreased by 6.0, 5.9, 5.8, and 13.7%, respectively, after enzymatic interesterification, similar to the reduction of those species after chemical interesterification, 6.6, 6.0, 7.1, and 12.9%, respectively. On the other hand, those of ECN38, 40, 42, 44, and 46 increased by 1.1, 1.6, 6.8, 16.7, and 6.5%, respectively, in comparison with the increase of those species after chemical interesterification, 0.2, 1.5, 6.5, 17.0, and 9.2%, respectively. Lipase load and reaction time had great influence on the degree of interesterification. A Lipozyme IM load of 6% was required for a reaction of 6 h and at 60 °C, to reach a stable degree of interesterification. Temperature variation in the range of 50—75 °C did not affect the reaction degree as well as the contents of diacylglycerols, but the content of FFA slightly increased with higher temperature. Addition of water to the enzyme increased the contents of diacylglycerols and FFA in the products linearly. However, it had no effect on the degree of interesterification for the first batch when the enzyme was reused. Lipozyme IM was stable in the 10‐batch test after adjusting the water content in the system. The relationship between the content of water in the system and that of FFAs in the products was evaluated and discussed.     

Synthesis and structural studies of “branched” 2-linked trisaccharides related to h-type 2 blood group determinants

A series of fucosylated trisaccharides l-Fuc-(1→2)-ß-d-Gal-(1→4)-ß-X-OMe (1-6, X = d-GlcNAc, d-Qui (6-deoxy-Glc), d-Xyl) related to H type 2 blood group determinant have been synthesized both as their α- and ß- L-Fuc anomers together with the component disaccharide starting compounds (7-11). The conformational properties of the trisaccharides together with their parent disaccharides have been investigated by NMR spectroscopy (proton and carbon chemical shifts and proton NOEs) in combination with computer modeling using the Monte Carlo approach and the HSEA force field using the GEGOP program with the main focus on the α-linked fucose series. The series of compounds allow for the investigation of interaction between the sugar units in the—in principle—linear structures, which in practice behave as branched trisaccharides. The interaction between the terminal fucose unit and the unit at the reducing end has been probed by substitution of the bulky CH₂OH group with CH₃ and H substituents, respectively. Compounds with severe steric interactions can be identified by the non-additivity of their carbon chemical shifts and subsequently confirmed by the detailed conformational assessment by NOEs and computer modeling. The most severe contacts arise in the GlcNAc and Qui trisaccharide series, whereas the Xyl-containing trisaccharide derivatives only exhibit weak steric interaction as probed by the NMR parameters.     

Sintering Mechanisms of Zirconium and Hafnium Carbides Doped with MoSi2

The microstructure of two pressureless-sintered ultra-high-temperature ceramics, namely ZrC+20 vol% MoSi₂ and HfC+20 vol% MoSi₂, was characterized by scanning and transmission electron microscopy. With regard to the ZrC–MoSi₂ system, Zr _x Si _y compounds and SiC were detected. In the HfC–MoSi₂ system, a mixed phase was detected at the triple points and identified as (Mo,Hf)₅Si₃. For both the systems investigated, the high wettability of the silicide-based phases on the matrix grains suggests that sintering is assisted by a liquid phase. This contribution reports for the first time on the sintering mechanisms of early transition metal carbides doped with MoSi₂ as a sinter additive, on the basis of the microstructural evolution observed upon sintering and in the light of phase diagrams and thermodynamical calculations.