Oxidative dehydrogenation and cracking of ethane and propane over LiDyMg mixed oxides

The oxidative dehydrogenation and cracking of ethane and propane over LiDyMg mixed oxides is reported. High yields of olefins and only moderate formation of carbon oxides was observed. Both are primary products that hardly interconvert under the reaction conditions used. Addition of chloride increases the rate of reaction, while slightly decreasing the selectivity to olefins. The addition of carbon dioxide strongly decreases the rate of reaction, the negative order of 0.5 indicating that two active Li⁺sites are blocked by the adsorption of one CO₂molecule. The reaction proceeds at low oxygen pressure primarily via elimination of dihydrogen, while at higher oxygen partial pressure the hydrogen elimination occurs via water formation. It is speculated that dehydrogenation and cracking involve Li⁺and a rather nucleophilic oxygen site.     

Proposal of a New Method for Measuring F?rster Resonance Energy Transfer (FRET) Rapidly,Quantitatively and Non-Destructively

The process of radiationless energy transfer from a chromophore in an excited electronic state (the “donor”) to another chromophore (an “acceptor”), in which the energy released by the donor effects an electronic transition, is known as “Förster Resonance Energy Transfer” (FRET). The rate of energy transfer is dependent on the sixth power of the distance between donor and acceptor. Determining FRET efficiencies is tantamount to measuring distances between molecules. A new method is proposed for determining FRET efficiencies rapidly, quantitatively, and non-destructively on ensembles containing donor acceptor pairs: at wavelengths suitable for mutually exclusive excitations of donors and acceptors, two laser beams are intensity-modulated in rectangular patterns at duty cycle ½ and frequencies f₁ and f₂ by electro-optic modulators. In an ensemble exposed to these laser beams, the donor excitation is modulated at f₁, and the acceptor excitation, and therefore the degree of saturation of the excited electronic state of the acceptors, is modulated at f₂. Since the ensemble contains donor acceptor pairs engaged in FRET, the released donor fluorescence is modulated not only at f₁ but also at the beat frequency Δf: = |f₁ − f₂|. The depth of the latter modulation, detectable via a lock-in amplifier, quantitatively indicates the FRET efficiency.     

Oxide ceramic fibers via dry spinning process—From lab to fab

Oxide fibers preparation and manufacturing capabilities at Fraunhofer-Center HTL are introduced, showing the development and preparation of oxide ceramic fibers from lab scale to pilot scale up to near production scale. As a specific example, the development of an aluminosilicate fiber with mullite composition is discussed in more detail. Fiber development started from nonaqueous sol-gel precursors in the early lab scale. With increasing fiber spinning volume, precursors were switched to water-soluble systems. Transformation from green fiber to ceramic fiber was monitored by thermogravimetric and differential thermal analysis, X-ray diffraction, and scanning electron microscopy. The evolution of ceramic phases, microstructure formation, and the effects on tensile strength and Young's modulus were investigated. Weibull statistics and fracture analysis helped to understand the results. Next step will be the transition from large lab scale to pilot scale, demonstrating manufacturing capability.     

Click-Chemistry (CuAAC) Trimerization of an αvβ6 Integrin Targeting Ga-68-Peptide: Enhanced Contrast for in-Vivo PET Imaging of Human Lung Adenocarcinoma Xenografts

α_vβ₆ Integrin is an epithelial transmembrane protein that recognizes latency-associated peptide (LAP) and primarily activates transforming growth factor beta (TGF-β). It is overexpressed in carcinomas (most notably, pancreatic) and other conditions associated with α_vβ₆ integrin-dependent TGF-β dysregulation, such as fibrosis. We have designed a trimeric Ga-68-labeled TRAP conjugate of the α_vβ₆-specific cyclic pentapeptide SDM17 (cyclo[RGD-Chg-E]-CONH₂) to enhance α_vβ₆ integrin affinity as well as target-specific in-vivo uptake. Ga-68-TRAP(SDM17)₃ showed a 28-fold higher α_vβ₆ affinity than the corresponding monomer Ga-68-NOTA-SDM17 (IC₅₀ of 0.26 vs. 7.4 nM, respectively), a 13-fold higher IC₅₀-based selectivity over the related integrin α_vβ₈ (factors of 662 vs. 49), and a threefold higher tumor uptake (2.1 vs. 0.66 %ID/g) in biodistribution experiments with H2009 tumor-bearing SCID mice. The remarkably high tumor/organ ratios (tumor-to-blood 11.2; -to-liver 8.7; -to-pancreas 29.7) enabled high-contrast tumor delineation in PET images. We conclude that Ga-68-TRAP(SDM17)₃ holds promise for improved clinical PET diagnostics of carcinomas and fibrosis.     

Selective Hydrogenation of Biomass-Derived Succinic Acid: Reaction Network and Kinetics

The conversion of bio-based succinic acid (SA) to the value-added chemicals 1,4-butanediol (BDO), γ-butyrolactone (GBL), and tetrahydrofuran (THF) can replace the corresponding petrochemical production routes to achieve a sustainable process. The reaction network for aqueous-phase catalytic hydrogenation of succinic acid over a supported Re-Pd catalyst was identified and the reaction kinetics was determined. With the developed kinetic model, the composition of the product mixture regarding the desired products (BDO, GBL, THF) can be described as a function of educt concentration, temperature, and pressure. The maximum BDO yield was achieved at high pressure and low temperature, while low pressure and high temperature favored GBL and THF production.     

Integrating superstructure-based design of molecules,processes, and flowsheets

The key to many chemical and energy conversion processes is the choice of the right molecule, for example, used as working fluid. However, the choice of the molecule is inherently coupled to the choice of the right process flowsheet. In this work, we integrate superstructure-based flowsheet design into the design of processes and molecules. The thermodynamic properties of the molecule are modeled by the PC-SAFT equation of state. Computer-aided molecular design enables considering the molecular structure as degree of freedom in the process optimization. To consider the process flowsheet as additional degree of freedom, a superstructure of the process is used. The method results in the optimal molecule, process, and flowsheet. We demonstrate the method for the design of an organic Rankine cycle considering flowsheet options for regeneration, reheating, and turbine bleeding. The presented method provides a user-friendly tool to solve the integrated design problem of processes, molecules, and process flowsheets.     

Synthesis,Chiral Separation,Absolute Configuration Assignment,and Biological Activity of Enantiomers of Retro‐1 as Potent Inhibitors of Shiga Toxin

The Shiga toxin (Stx) family is composed of related protein toxins produced by the bacteria Shigella dysenteriae and certain pathogenic strains of E. coli. No effective therapies for Stx intoxication have been developed yet. However, inhibitors that act on the intracellular trafficking of these toxins may provide new options for the development of therapeutic strategies. This study reports the synthesis, chromatographic separation, and pharmacological evaluation of the two enantiomers of Retro‐1, a compound active against Stx and other such protein toxins. Retro‐1 works by inhibiting retrograde transport of these toxins inside cells. In vitro experiments proved that the configuration of the stereocenter at position 5 is not crucial for the activity of this compound. X‐ray diffraction data revealed (S)‐Retro‐1 to be slightly more active than (R)‐Retro‐1.     

One Question,Multiple Answers: Biochemical and Biophysical Screening Methods Retrieve Deviating Fragment Hit Lists

Fragment‐based lead discovery is gaining momentum in drug development. Typically, a hierarchical cascade of several screening techniques is consulted to identify fragment hits which are then analyzed by crystallography. Because crystal structures with bound fragments are essential for the subsequent hit‐to‐lead‐to‐drug optimization, the screening process should distinguish reliably between binders and non‐binders. We therefore investigated whether different screening methods would reveal similar collections of putative binders. First we used a biochemical assay to identify fragments that bind to endothiapepsin, a surrogate for disease‐relevant aspartic proteases. In a comprehensive screening approach, we then evaluated our 361‐entry library by using a reporter‐displacement assay, saturation‐transfer difference NMR, native mass spectrometry, thermophoresis, and a thermal shift assay. While the combined results of these screening methods retrieve 10 of the 11 crystal structures originally predicted by the biochemical assay, the mutual overlap of individual hit lists is surprisingly low, highlighting that each technique operates on different biophysical principles and conditions.