High-temperature gradient HPLC for the separation of polyethylene–polypropylene blends

A high-temperature gradient HPLC method has been developed for the analysis of polyethylene–polypropylene blends. For the first time it was possible to separate these polyolefin blends by a chromatographic technique which is operating at 140 °C. Blends of a commercial polypropylene and a medium molar mass linear polyethylene were separated using a mobile phase of ethylene glycol monobutylether (EGMBE) and 1,2,4-trichlorobenzene (TCB) and silica gel as the stationary phase. With the use of n-decanol as sample solvent, a precipitation–redissolution mechanism for polyethylene (PE) was established while polypropylene (PP) is eluted in size exclusion mode.     

Melt spun matrix fibers of toughened polypropylene copolymers modified by high energy electrons

Binary blends of polypropylene (PP) and ethylene‐octene copolymer (EOC) are prepared by continuous electron‐induced reactive processing at various mass ratios of the blend components and various doses without adding of any grafting agents. The influence of mass ratio and dose is investigated in order to get the optimum processing behavior of toughened PP as well as optimum properties of resulting fibers. It is found that toughened PP with a PP/EOC blend ratio of 97.5–2.5  mass % can be used advantageously as a matrix component for the process of online spinning of glass fiber/toughened PP hybrid yarns. Such hybrid yarns belong to one of the most advanced production methods for the manufacturing of fiber reinforced thermoplastic composites with an increased mechanical performance. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44011.     

Controlling micro‐ and nanofibrillar morphology of polymer blends in low‐speed melt spinning process. Part II: Influences of extrusion rate on morphological changes of a PLA/PVA blend through a capillary die

The effects of the extrusion rate on the morphological changes of poly(lactic acid) (PLA)/poly(vinyl alcohol) (PVA) blend through a capillary die were investigated. In this study, the extrusion rate or mass flow rate is altered from 0.5 g min^?1 to 2 g min^?1 with an increment of 0.5 g min^?1. The PLA/PVA blend with a composition of 30/70 (wt %) exhibits a particle matrix morphology with dispersed PLA droplets within the PVA matrix. It is found that, the spherical or ellipsoidal dispersed PLA droplets are elongated and coalesced into rod‐like or longer ellipsoidal droplets when they pass through the capillary die. When the extrusion rate increases, the coalescence between the large PLA droplets occurs more intense. However, the changes of the extrusion rate have no strong effect on the coalescence of small droplets having diameter less than about 150 nm. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44257.     

Poly(pent‐1‐ene) Synthesized with the Syndiospecific Catalyst i‐Pr(Cp)(9‐Flu)ZrCl2/MAO

1‐Pentene was polymerized with the syndiospecific catalyst system i‐PrC(Cp)(9‐fluorenyl)ZrCl₂/MAO. The molar mass of the resulting polymers depends strongly on the reaction temperature and decreases from M̄_w = 126 000 at 0°C to M̄_w = 46 000 at 100°C, but is more or less independent of the monomer and the MAO concentration. The influence of reaction temperature and concentrations of MAO and monomer on the type of end‐groups generated during the chain termination, as well as on the type of stereoerror, was investigated. The degree of tacticity was dependent on the polymerization temperature with [rrrr] > 0.99 at 0°C and [rrrr] = 0.75 at 100°C.     

Solution Structure and Dynamics of the Small Protein HVO_2922 from Haloferax volcanii

Past sequencing campaigns overlooked small proteins as they seemed to be irrelevant due to their small size. However, their occurrence is widespread, and there is growing evidence that these small proteins are in fact functionally very important in organisms found in all kingdoms of life. Within a global proteome analysis for small proteins of the archaeal model organism Haloferax volcanii, the HVO_2922 protein has been identified. It is differentially expressed in response to changes in iron and salt concentrations, thus suggesting that its expression is stress-regulated. The protein is conserved among Haloarchaea and contains an uncharacterized domain of unknown function (DUF1508, UPF0339 family protein). We elucidated the NMR solution structure, which shows that the isolated protein forms a symmetrical dimer. The dimerization is found to be concentration-dependent and essential for protein stability and most likely for its functionality, as mutagenesis at the dimer interface leads to a decrease in stability and protein aggregation.     

DEM‐CFD modeling of particle systems with long‐range electrostatic interactions

To investigate dynamic behaviors of monocharged particle systems, a direct truncation (DT) method and a hybrid particle‐cell (HPC) method are implemented into the discrete element method coupled with computational fluid dynamics (DEM‐CFD) with defined cutoff distances. The DT method only considers electrostatic interactions between particles within the cutoff distance while the HPC method computes electrostatic interactions in the entire computational domain. The deposition process of monocharged particles in a container in air was simulated using the developed DEM‐CFD. It was found that using the DT method, the macrostructure, evolution of granular temperature, and radial distribution function of the particle system were sensitive to the specified cutoff distance. In contrast, using the HPC method, these results were independent of the specified cutoff distance, as expected. This implies that, although electrostatic interactions between particles with large separation distances are weak, they should be considered in DEM‐CFD for accurate modeling of charged particle systems. © 2015 The Authors AIChE Journal published by Wiley Periodicals, Inc. on behalf of American Institute of Chemical Engineers AIChE J, 61: 1792–1803, 2015     

Screening,Molecular Cloning,and Biochemical Characterization of an Alcohol Dehydrogenase from Pichia pastoris Useful for the Kinetic Resolution of a Racemic β‐Hydroxy‐β‐trifluoromethyl Ketone

The stereoselective synthesis of chiral 1,3‐diols with the aid of biocatalysts is an attractive tool in organic chemistry. Besides the reduction of diketones, an alternative approach consists of the stereoselective reduction of β‐hydroxy ketones (aldols). Thus, we screened for an alcohol dehydrogenase (ADH) that would selectively reduce a β‐hydroxy‐β‐trifluoromethyl ketone. One potential starting material for this process is readily available by aldol addition of acetone to 2,2,2‐trifluoroacetophenone. Over 200 strains were screened, and only a few yeast strains showed stereoselective reduction activities. The enzyme responsible for the reduction of the β‐hydroxy‐β‐trifluoromethyl ketone was identified after purification and subsequent MALDI‐TOF mass spectrometric analysis. As a result, a new NADP⁺‐dependent ADH from Pichia pastoris (PPADH) was identified and confirmed to be capable of stereospecific and diastereoselective reduction of the β‐hydroxy‐β‐trifluoromethyl ketone to its corresponding 1,3‐diol. The gene encoding PPADH was cloned and heterologously expressed in Escherichia coli BL21(DE3). To determine the influence of an N‐ or C‐terminal His‐tag fusion, three different recombinant plasmids were constructed. Interestingly, the variant with the N‐terminal His‐tag showed the highest activity; consequently, this variant was purified and characterized. Kinetic parameters and the dependency of activity on pH and temperature were determined. PPADH shows a substrate preference for the reduction of linear and branched aliphatic aldehydes. Surprisingly, the enzyme shows no comparable activity towards ketones other than the β‐hydroxy‐β‐trifluoromethyl ketone.     

A Catalytic Nanoreactor Based on in Vivo Encapsulation of Multiple Enzymes in an Engineered Protein Nanocompartment

Bacterial protein compartments concentrate and sequester enzymes, thereby regulating biochemical reactions. Here, we generated a new functional nanocompartment in Escherichia coli by engineering the MS2 phage capsid protein to encapsulate multiple cargo proteins. Sequestration of multiple proteins in MS2‐based capsids was achieved by SpyTag/SpyCatcher protein fusions that covalently crosslinked with the interior surface of the capsid. Further, the functional two‐enzyme indigo biosynthetic pathway could be targeted to the engineered capsids, leading to a 60 % increase in indigo production in vivo. The enzyme‐loaded particles could be purified in their active form and showed enhanced long‐term stability in vitro (about 95 % activity after seven days) compared with free enzymes (about 5 % activity after seven days). In summary, this engineered in vivo encapsulation system provides a simple and versatile way for generating highly stable multi‐enzyme nanoreactors for in vivo and in vitro applications.     

Avoiding filter cake cracking: Influence of consolidation on desaturation characteristics

In cake filtration processes with an air-blowing step, cracking is an undesirable phenomenon as it leads to deterioration of the filtration process by highly increasing gas throughput. This leads to higher residual moisture if the pressure difference cannot be maintained and an increase in overall cost. Crack formation can be avoided by compacting the filter cake before desaturation. While this action will make the separation process applicable by highly reducing gas consumption, there are also potential negative effects. Compaction increases filter cake resistance and might therefore slow down desaturation kinetics. Therefore, the authors investigated how the filter cake characteristics governing desaturation change from the nonconsolidated to the consolidated state of the filter cake and compared these findings to the actual dewatering kinetics. The results showed that for the case where cracking could be oppressed, dewatering kinetics of the consolidated cake are actually faster than for the nonconsolidated cake, despite higher resistance of the consolidated cake. Thus, compaction is an appropriate action when dealing with filter cake cracking.