Premodification of Pt/γAl2O3 with Cinchonidine for the Enantioselective Hydrogenation of Ethyl Pyruvate: Effect of Premodification Conditions on Reaction Rate and Enantioselection

The premodification of a 5 wt% Pt/-Al₂O₃ catalyst with cinchonidine (0.01 and 0.2 g g^-1 _catalyst) is described and discussed. Premodification is carried out by treating the catalyst with a solution of cinchonidine followed by solvent removal. Catalysts premodified in this way give the same ee and initial rate of reaction for the enantioselective hydrogenation of ethyl pyruvate as those using the standard in situ modification procedure. Investigations of different solvents for premodification and reaction (dichloromethane, ethanol) show that it is the solvent used for the reaction that controls the observed enantioselection. Premodified catalysts also display the initial transient behavior typically observed with in situ modified catalysts in which the ee increases with conversion in the early part of the reaction. Premodified catalysts show an enhanced rate of reaction when ethanol is used as the reaction solvent compared with in situ modified catalysts under the same conditions. Premodification using aerobic conditions gives the best results and premodified catalysts can be stored prior to use for up to a week without loss of catalytic performance.     

Model-based control of titer and glycosylation in fed-batch mAb production: Modeling and control system development

Therapeutic monoclonal antibodies (mAbs) are typically manufactured using mammalian cell cultures in fed-batch bioreactors, with increasing emphasis on meeting productivity and product quality attribute targets that depend strongly on such process variables as nutrient feed rates and bioreactor operating conditions. In this article, we identify, categorize, and address the challenges of achieving both productivity and product quality goals simultaneously, by developing a multivariable, model-based control system that can satisfy multiple production objectives in a fed-batch cell culture process. Here, we discuss model development and present theoretical concepts of observability and controllability that are essential to understanding and handling effectively these intrinsic challenges. Subsequently, we evaluate via simulation the performance of the outer-loop model predictive control and demonstrate the overall capability to satisfy complex production objectives in a laboratory scale bioreactor, as a first step toward the ultimate goal of creating an advanced control system for fed-batch mAb manufacturing processes.     

Prediction of Polymer Properties in LDPE Reactors

Summary: A new analysis tool is presented that uses the governing kinetic scheme to predict properties of low‐density polyethylene (LDPE) such as the detailed shape of the molecular weight distribution (MWD). A model that captures mixing details of autoclave reactor operation is used to provide a new criterion for the onset of MWD shouldering. Kinetic effects are shown to govern the existence of MWD shoulders in LDPE reactors, even when operation is far from perfectly‐mixed. MWD shoulders occur when the mean reaction environment has a relatively high radical concentration and has a high polymer content, and is at a low temperature. Such conditions maximize long chain formation by polymer transfer and combination‐termination, while limiting chain scission. For imperfectly‐mixed reactors, the blending of polymer‐distributions produced in different spatial locations has a small effect on the composite MWD. However, for adiabatic LDPE autoclaves, imperfect mixing broadens the stable range of mean reactor conditions, and thereby increases the possibility for MWD shouldering.

Polymer MWD produced in an LDPE autoclave reactor by various kinetic mechanisms.     

Printability of elastomer latex for additive manufacturing or 3D printing

Additive manufacturing, sometimes referred to as 3D printing is a new, rapidly developing technology which has the potential to revolutionize fabrication of certain high value, complex products. Until now conventional elastomers have not been widely used in the additive manufacturing process. The goal of our work was to determine the feasibility of additive manufacturing using ink jet printing of elastomeric latex materials. Particle size, viscosity, and surface tension were measured for five different latex materials—poly(2‐chloro‐1,3‐butadiene), carboxylated styrene‐butadiene rubber, carboxylated butadiene‐acrylonitrile copolymer, natural rubber, and prevulcanized natural rubber. The XSBR latex was predicted as the one most likely to be printable. Printing trials carried out with the XSBR as the ink proved it to be printable, although technical problems of agglomeration and print head clogging need to be addressed and both the material and process need to be optimized for consistent printing to be achieved. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 42931.     

Identification of 4-Anilinoquin(az)oline as a Cell-Active Protein Kinase Novel 3 (PKN3) Inhibitor Chemotype**

Deep annotation of a library of 4-anilinoquin(az)olines led to the identification of 7-iodo-N-(3,4,5-trimethoxyphenyl)quinolin-4-amine 16 as a potent inhibitor (IC₅₀=14 nM) of Protein Kinase Novel 3 (PKN3) with micromolar activity in cells. Compound 16 is a potential tool compound to study the cell biology of PKN3 and its role in pancreatic and prostate cancer and T-cell acute lymphoblastic leukemia. These 4-anilinoquin(az)olines may also be useful tools to uncover the therapeutic potential of PKN3 inhibition in a broad range of diseases.     

Relay and sequential cropping corn with winter oilseed crops in northern climates

Nutrient Cycling in Agroecosystems - Winter oilseed crops camelina [Camelina sativa (L.) Crantz] and field pennycress (Thlaspi arvense L.) are potential candidates for diversifying the...     

Phase Stability and Optoelectronic Properties of the Bixbyite Phase in the Gallium–Indium–Tin–Oxide System

X‐ray diffraction techniques were used to determine the phase boundaries of the In₂O₃ solid solution phase in the Ga₂O₃–In₂O₃–SnO₂ ternary system. The effects of Ga and Sn content on the unit cell dimensions of the bixbyite phase were calculated by a linear regression fit, the results of which indicate the two substitutive cations have opposite and independent effects on the lattice parameter. These results suggest that the cations do not strongly interact with each other in the crystal. Measurements of optoelectronic properties were also taken on single‐phase bulk specimens within the solid solution to establish their dependence on composition. As anticipated, Sn doping yields corresponding increases in conductivity, reduction in the absolute value of Seebeck coefficient, and increase in optical band gap. In contrast, these properties are not significantly affected by varying Ga content, confirming that Ga behaves as an isovalent dopant at the low doping levels involved.