Introducing copper ions into zeolite Y by the thallous ion exchange method: single crystal structure of |Cu21.6Tl39.2|[Si121Al71O384]–FAU

The thallous ion exchange (TIE) method was used for the first time in an attempt to introduce copper ions into zeolite Y (FAU, Si/Al = 1.69). |Cu _10.9 ⁺ Cu _10.7 ²⁺ Tl _39.2 ⁺ |[Si₁₂₁Al₇₁O₃₈₄]–FAU was prepared by reacting fully dehydrated and fully Tl⁺-exchanged zeolite Y (Tl₇₁–Y) with CuCl₂(g) and its decomposition products CuCl(g) and Cl₂(g) at 673 K under anhydrous conditions. Its structure was determined using single-crystal crystallography with synchrotron X-radiation and was refined in the space group ${Fd}\bar{3}$ m (a = 24.769(1) Å) with all 903 unique data; the final error index, R ₁ = 0.075, was calculated using only the 858 reflections with F _o > 4σ(F _o). About 45 % of the Tl⁺ ions were replaced by 21.6 copper ions per unit cell at the following sites (distances to nearest framework oxygen atoms are given): 10.7 Cu²⁺ at site I′ in the sodalite cavity opposite double 6-rings (Cu²⁺–O = 2.093(9) Å), 3.5 Cu⁺ at site II opposite single 6-rings in the supercage (Cu⁺–O = 2.24(3) Å), and 7.4 Cu⁺ at site III near 12-rings in the supercage (Cu⁺–O = 2.45(7) Å). All Cu⁺ ions are in supercages where they are easily accessible to guest molecules. The remaining ca. 39 Tl⁺ ions per unit cell occupy three distinct positions: 12 are at a second site I′ (Tl⁺–O = 2.571(9) Å), 23 are at a second site II (Tl⁺–O = 2.732(10) Å), and 4 are at site III′ (Tl⁺–O = 2.871(16) Å) near triple 4-rings in the supercages.     

Zur Reaktionsweise von Cellulose mit Alkalimetallen in flüssigem Ammoniak; reaktionskinetische Untersuchungen und eigenschaften von 2,3,6-Tri-O-lithiumcellulose

Structural data of ammonia swollen cellulose were obtained by kinetic investigations of the reaction of lithium, sodium and potassium with cotton fibers in liquid ammonia. The alkali metals reacted in a relatively rapid initial reaction with the accessible hydroxyl groups on the surface of structural units in the cellulose. The accessibility data found corresponded to those obtained by deuterium exchange in D₂O. While K/NH₃ did not react further with the ordered NH₃-cellulose a slow attack was found by Na/NH₃ with a constant rate. Faster was the reaction with Li/NH₃ (first order in cellulose). Thereby, characteristic differences were found between the used cellulose of differently ordered structures (cellulose I, II, III). This was traced back to the formation of different NH₃- cellulose-adducts. 2,3,6-Tri-O-lithiumcellulose was obtained from cotton cellulose without chain degradation. The lithium cellulosate was characterized by infrared spectroscopy, thermoanalytic investigations and by X-ray diffractions. Following measurements showed that cellulose reacted with Li/NH3 by a sheet lattice reaction.     

Composition of Commercial Bis(2‐ethylhexyl) Sulfosuccinate Surfactant By‐Products and their Effects on an Agrochemical Formulation

Sodium bis(2‐ethylhexyl) sulfosuccinate (known as AOT) is a commercially available surfactant commonly used in agrochemicals. Besides the principal diester surfactant, the commercial AOT product contains two surface‐active isomeric monoester by‐products, which may influence the surfactant's overall properties. This work investigates whether the purity of the surfactant affects its ability to stabilize an agrochemical formulation. The concentrations of the diester and two monoester impurities in batches of commercial AOT product from several suppliers were determined quantitatively by liquid chromatography–mass spectrometry. The tested batches showed different contents of the monoesters. Samples of a model agrochemical formulation containing the AOT product formed more sediment during storage when the content of monoesters in the surfactant was high. The supplier of an commercial AOT product could be traced by analysis of the monoester content of either the raw product or the aged agrochemical formulation.     

Bioabbaubarkeit von 2‐Ethylhexylacetat,Methylisobutylketon und Methylethylketon in Biotricklingfiltern

The impact of nutrient supply and package material on the biodegradability of a waste air contaminated with a mixture of 2‐ethyl hexyl acetate, methyl isobutyl ketone and methyl ethyl ketone in biotrickling filters was analyzed. As package material PU foam cubes, Hiflow rings and woodchips were used. The data showed that PU‐cubes gave the best results in degradation, while the Hiflow rings showed the most stable usage. The discontinuous supply of nutrients helped to improve and stabilize efficiency in all three systems. Inhibitory effects based on the degradation of these components were not observed.     

Synthesis and flammability testing of epoxy functionalized phosphorous‐based flame retardants

Several potential new phosphorus‐containing flame retardant molecules were evaluated for heat release reduction potential by incorporation of the molecules into a polyurethane, generated from methylene diphenyl diisocyanate and 1,3‐propane diol. The heat release reduction potential of these substances was evaluated using the pyrolysis combustion flow calorimeter (PCFC). The polyurethanes were prepared in the presence of the potential flame retardants via solvent mixing and copolymerization methods to qualitatively evaluate their potential reactivity into the polyurethane prior to heat release testing. The functionality of the flame retardants was epoxide based that would potentially react with the diol during polyurethane synthesis. Flammability testing via PCFC showed that the heat release reduction potential of each of the flame retardants was structure dependent, with phosphates tending to show more effectiveness than phosphonates in this study, and alkyl functionalized phosphorus groups (phosphate or phosphonate) being more effective at heat release reduction than cyclic functionalized groups. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42296.     

Towards Understanding Directed Evolution: More than Half of All Amino Acid Positions Contribute to Ionic Liquid Resistance of Bacillus subtilis Lipase A

Ionic liquids (ILs) are attractive (co‐)solvents for biocatalysis. However, in high concentration (>10 % IL), enzymes usually show decreased activity. No general principles have been discovered to improve IL resistance of enzymes by protein engineering. We present a systematic study to elucidate general engineering principles by site saturation mutagenesis on the complete gene bsla. Screening in presence of four [BMIM]‐based ILs revealed two unexpected lessons on directed evolution: 1) resistance improvement was obtainable at 50–69 % of all amino acid positions, thus explaining the success of small sized random mutant libraries; 2) 6–13 % of substitutions led to improved resistance. Among these, 66–95 % were substitutions by chemically different amino acids (e.g., aromatic to polar/aliphatic/charged amino acids), thus indicating that mutagenesis methods introducing such changes should, at least for lipases like BSLA, be favored to improve IL resistance.     

Intratumoral Canine Distemper Virus Infection Inhibits Tumor Growth by Modulation of the Tumor Microenvironment in a Murine Xenograft Model of Canine Histiocytic Sarcoma

Histiocytic sarcomas refer to highly aggressive tumors with a poor prognosis that respond poorly to conventional treatment approaches. Oncolytic viruses, which have gained significant traction as a cancer therapy in recent decades, represent a promising option for treating histiocytic sarcomas through their replication and/or by modulating the tumor microenvironment. The live attenuated canine distemper virus (CDV) vaccine strain Onderstepoort represents an attractive candidate for oncolytic viral therapy. In the present study, oncolytic virotherapy with CDV was used to investigate the impact of this virus infection on tumor cell growth through direct oncolytic effects or by virus-mediated modulation of the tumor microenvironment with special emphasis on angiogenesis, expression of selected MMPs and TIMP-1 and tumor-associated macrophages in a murine xenograft model of canine histiocytic sarcoma. Treatment of mice with xenotransplanted canine histiocytic sarcomas using CDV induced overt retardation in tumor progression accompanied by necrosis of neoplastic cells, increased numbers of intratumoral macrophages, reduced angiogenesis and modulation of the expression of MMPs and TIMP-1. The present data suggest that CDV inhibits tumor growth in a multifactorial way, including direct cell lysis and reduction of angiogenesis and modulation of MMPs and their inhibitor TIMP-1, providing further support for the concept of its role in oncolytic therapies.     

The Role of Tenascin C in Cardiac Reverse Remodeling Following Banding–Debanding of the Ascending Aorta

Background: Tenascin-C (TN-C) plays a maladaptive role in left ventricular (LV) hypertrophy following pressure overload. However, the role of TN-C in LV regression following mechanical unloading is unknown. Methods: LV hypertrophy was induced by transverse aortic constriction for 10 weeks followed by debanding for 2 weeks in wild type (Wt) and TN-C knockout (TN-C KO) mice. Cardiac function was assessed by serial magnetic resonance imaging. The expression of fibrotic markers and drivers (angiotensin-converting enzyme-1, ACE-1) was determined in LV tissue as well as human cardiac fibroblasts (HCFs) after TN-C treatment. Results: Chronic pressure overload resulted in a significant decline in cardiac function associated with LV dilation as well as upregulation of TN-C, collagen 1 (Col 1), and ACE-1 in Wt as compared to TN-C KO mice. Reverse remodeling in Wt mice partially improved cardiac function and fibrotic marker expression; however, TN-C protein expression remained unchanged. In HCF, TN-C strongly induced the upregulation of ACE 1 and Col 1. Conclusions: Pressure overload, when lasting long enough to induce HF, has less potential for reverse remodeling in mice. This may be due to significant upregulation of TN-C expression, which stimulates ACE 1, Col 1, and alpha-smooth muscle actin (α-SMA) upregulation in fibroblasts. Consequently, addressing TN-C in LV hypertrophy might open a new window for future therapeutics.     

Stable linker peptides for a cellulose-binding domain-lipase fusion protein expressed in Pichia pastoris

Fusion proteins composed of a cellulose-binding domain fromNeocallimastix patriciarum cellulase A and Candida antarcticalipase B were constructed using different linker peptides. Theaim was to create proteolytically stable linkers that were ableto join the functional modules without disrupting their function.Six fusion variants containing linkers of 4–44 residueswere expressed in Pichia pastoris and analysed. Three variantswere found to be stable throughout 7-day cultivations. The cellulose-bindingcapacities of fusion proteins containing short linkers wereslightly lower compared with those containing long linkers.The lipase-specific activities of all variants, in solutionor immobilized on to cellulose, were equal to that of the wild-typelipase.