Investigations on Selectivity of Gas-Liquid Reactions in Capillaries

Biocatalysis offers a broad spectrum of possible ecological and economic advantages over conventional chemical catalysis processes, e.g., lower energy consumption and high enantio selectivity. The focus of this work is on gas-liquid reactions. These are of great importance in the chemical and biochemical industry and subject of current research since they are often limited by mass transfer or show low selectivity. Different suitable biocatalytically gas-liquid reaction systems were tested in capillary reactor designs in order to obtain information about the interaction between reaction and fluid mechanics. Furthermore, an optical measuring method was established. The experiments were performed in batch mode in a glass beaker with a flow cuvette for UV/Vis measurement of product concentration.     

Entwicklung eines Transformationsmodells – Modularisierung schrittweise gedacht

For some years now, the process industry has been meeting the challenges of the markets with modular production and logistics concepts. This article presents this development process in the form of a four-stage transformation model. It is shown that the path towards modular production environments can be taken step by step. The motto is “evolution instead of revolution”. First, an overview of the state of the art of modularized production and logistics systems is given. Based on this, the article describes and classifies the four different stages of modularization.     

Genomic Instability Is an Early Event in Aluminium-Induced Tumorigenesis

Genomic instability is generally considered as a hallmark of tumorigenesis and a prerequisite condition for malignant transformation. Aluminium salts are suspected environmental carcinogens that transform mammary epithelial cells in vitro through unknown mechanisms. We report here that long-term culture in the presence of aluminium chloride (AlCl₃) enables HC11 normal mouse mammary epithelial cells to form tumours and metastases when injected into the syngeneic and immunocompetent BALB/cByJ strain. We demonstrate that AlCl₃ rapidly increases chromosomal structural abnormalities in mammary epithelial cells, while we failed to detect direct modulation of specific mRNA pathways. Our observations provide evidence that clastogenic activity—a well-recognized inducer of genomic instability—might account in part for the transforming abilities of aluminium in mammary epithelial cells.     

Customizing the comonomer incorporation distribution in Ziegler–Natta-based LLDPE: Harnessing the influences of the titanation temperature during catalyst synthesis and of polymerization process parameters

The microstructure of linear low-density polyethylene (LLDPE) is strongly influenced by short-chain branches (SCBs) incorporated into the polymer backbone. Varying the number, distribution, and length of SCBs allows the properties of the resulting polymer to be tailored to meet specific requirements. Using Ziegler–Natta (ZN) catalysts for synthesis has disadvantages in terms of the comonomer incorporation distribution (CID) compared to, for instance, metallocene and post–metallocene catalysts. Nevertheless, ZN catalysts continue to be widely used, as many of the new generations of catalysts are more difficult to handle and cannot match the cheap cost of ZN catalysts. To improve this aspect of ZN catalysts, we investigated the influence of catalyst titanation temperature and polymerization process parameters on the CID. Our results show that it is possible to manipulate the process parameters of the present ZN catalyst system to yield a desired comonomer amount and CID in the polymer. Varying the titanation temperature clearly influenced the titanium content of the catalyst. Molecular-weight distribution analysis and deconvolution results indicate that changes in the amounts of comonomer incorporated and in the CID are directly related to the catalyst's active site that produces the lowest-molecular-weight fraction.     

Kinetics of Solid-State Reactions in Heterogeneous Catalysis from Time-Resolved X-Ray Absorption Spectroscopy

The potentials of X-ray absorption spectroscopy (XAS) (quantitative phase composition and average valence together with a short-range order structure analysis) combined with a time-resolution in the second range make time-resolved (TR-) XAS a powerful tool for investigating the reactivity of solids in catalysis and solid-state chemistry. General aspects of TR-XAS investigations are discussed (i.e., instrumentation, data analysis). In addition, some experiments illustrate how the kinetics of solid-state reactions in heterogeneous catalysis can be elucidated from TR-XAS studies.     

Toluenesulfonate-acyl esters of ethylene glycol and other 1,2-diols as industrial antioxidants with cupric ion

Ethylene glycol esters of soybean oil FA increased in viscosity much more slowly than methyl or glycerol esters when oxidized at 105°C in the presence of flowing air and colloidal copper. This increased stability was caused by a minor constituent of the ethylene glycol esters, which was shown by MS to be a mixed ethanediol fatty acylate p-toluenesulfonate (EFAT). The p-toluenesulfonate group came from the catalyst used in the formation of the ethylene glycol esters. EFAT was quantified by UV spectrometry, HPLC, or GC of the acyl group that it contains. EFAT could be synthesized in good yield by reacting ethylene glycol, a FA, and p-toluenesulfonic acid (TSA) in a 1∶1∶1 molar ratio using a benzene azeotrope to remove water of esterification. EFAT increased the time required for the polymerization of soybean oil by about 27 times but required concentrations of 2–5% by weight. EFAT made with a variety of FA were active in delaying viscosity increase. Ethyl and decyl p-toluenesulfonate were inactive. Replacing ethylene glycol by glycerol and 1,2-propylene glycol but not by 1,3-propylene glycol resulted in active EFAT. TSA itself delayed the polymerization of soybean oil, especially in the presence of free ethylene glycol and FA, but this probably was caused by formation of EFAT during the oxidation test. Colloidal copper could be replaced by cupric ion. EFAT-copper appeared to act as an antioxidant by destroying hydroperoxides without initiation of free radical chains.     

Correlation between electrochemical characteristics and thermal stability of advanced lithium-ion batteries in abuse tests—short-circuit tests

The shutdown function of a separator is an important factor in the safety of advanced lithium-ion batteries (ALB). When a separator without proper shutdown function is used, battery safety would depend on the thermal stability of electrode materials. Results show that thermal stability of a battery, contributed from both the anode and cathode, decreases noticeably after cycling. DSC shows that exothermicity from SEI decomposition and the reaction of the lithiated graphite and electrolyte around 140 °C increases as cycle number increase; main reason is the gradual thickening of passivation film, observed through three-electrode ac impedance measurements. DSC also shows a similar trend of exothermicity for Li_xCoO₂ cathode. The lesser the amount of lithium (x-value) in Li_xCoO₂, the larger the exothermicity and the lower the decomposition temperature. Using a three-electrode system to observe the changes of open-circuit potential in Li_xCoO₂ cathode, thermal instability is a consequence of decreased lithium content as cycle increases.     

Unipolar Fatigue Behavior of BCTZ Lead‐Free Piezoelectric Ceramics

(Ba,Ca)(Ti,Zr)O₃ lead‐free piezoelectric ceramics have been considered to be one of the most potential lead‐free alternatives for PZT in the room‐temperature range. The stability of the piezoelectric performance during unipolar cycling is investigated in this study. It is found that the unipolar fatigue behavior is similar to soft PZT. Developments of bias field, offset polarization, asymmetry in strain, and dielectric hysteresis loops are observed during bipolar measurements. The changes are mainly contributed to the migration of charge carriers to the grain boundaries driven by the unscreened depolarization field. Redistribution of the accumulated charge carriers by bipolar electric cycling or thermal annealing can significantly recover the unipolar fatigued state. The unipolar strain response stabilized after 1000 cycles at 0.053% for an electric field of 0.6 kV/mm (d₃₃*= 883 pm/V), which is a good characteristic for actuator applications.     

Remendable polymers via reversible Diels–Alder cycloaddition of anthracene‐containing copolymers with fullerenes

Poly(lauryl methacrylate)s with anthracene moieties in the side chain were converted with C₆₀‐fullerene and phenyl‐C₆₁‐butyric acid methyl ester (PCBM), resulting in new remendable (self‐healing) polymeric materials. The utilization of differently substituted anthracene monomers enabled the tuning of the reactivity and the resulting mechanical properties. Copolymers with different contents of the anthracene moieties were synthesized and characterized using size exclusion chromatography, ¹H nuclear magnetic resonance (NMR) spectroscopy as well as differential scanning calorimetry (DSC). ¹H NMR spectroscopic studies were utilized in order to investigate the reversibility of the Diels–Alder reaction between copolymers with C₆₀‐fullerene and PCBM, respectively, in solution. In order to investigate the conversion of the polymers with C₆₀‐fullerene and PCBM in bulk, additionally, DSC, nanoindentation, rheology, atomic force microscopy (AFM), 3D microscopy, simultaneous thermal analysis (STA) and FT‐Raman investigations were performed. The fullerene‐containing copolymers could be healed in a temperature range of 40–80 °C. Consequently, a new generation of low temperature remendable polymers could be established. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45916.