Comb Polymer Architecture Effects on the Rheological Property Evolution of Concentrated Cement Suspensions

We have studied the rheological behavior of concentrated cement suspensions in the absence and presence of comb polymers comprised of a polyacrylic acid (PAA) backbone and charge-neutral, poly(ethylene oxide) (PEO) teeth. These species possessed a uniform backbone molecular weight and graft density, with varying teeth molecular weight. Both PAA, a linear polyelectrolyte, and PAA/PEO comb polymers imparted initial stability to concentrated cement suspensions above a critical weight fraction, w * of 4 mg/(g of cement). Cement–PAA suspensions, however, set prematurely. Their rapid, irreversible stiffening stemmed from deleterious interactions between PAA and multivalent counterions in solution. Interestingly, the presence of PEO teeth comprised of only a few monomer units in length mitigated such interactions. The rheological property evolution of concentrated cement–PAA/PEO suspensions exhibited complex behavior ranging from the reversible gel-like response observed at short teeth lengths to a remarkable gel-to-fluid transition observed during the deceleratory period for systems comprised of longer PEO teeth. At longer hydration times, all cement–PAA/PEO suspensions exhibited initial elastic modulus values, G_i '∼ exp( t /τ_c) before the onset of the acceleratory period, followed by initial set. Their characteristic hydration time, τ_c, and set time depended strongly on the concentration of "free" carboxylic acid groups [COO⁻] arising from non-adsorbed polyelectrolyte species in solution.     

Influence of normal contact force model on simulations of spherocylindrical particles

How the choice of elastic normal contact force model affects predictions from discrete element method simulations of spherocylindrical particles is investigated in this article. Three force models were investigated: (1) a Hertzian force model (HFM) which assumes a circular contact area; (2) a linear force model (LFM) with a constant stiffness; and (3) a modified HFM (MFM) that accounts for various contact areas and contact transitions. With the MFM, transitions between contact area types must be accounted for otherwise discontinuities in the contact force can occur. It is found that simple force models (HFM, LFM) can be substituted for more accurate force models if only force data and bulk properties are of interest. However, if more detailed contact information, such as contact area, contact overlap, contact duration, or collision frequency, are needed, for example, in population balance models and transient liquid bridge modeling, then a more accurate force model should be used. © 2018 American Institute of Chemical Engineers AIChE J, 64: 1986–2001, 2018     

Biocatalytic Asymmetric Phosphorylation Catalyzed by Recombinant Glycerate‐2‐Kinase

The efficient synthesis of pure d ‐glycerate‐2‐phosphate is of great interest due to its importance as an enzyme substrate and metabolite. Therefore, we investigated a straightforward one‐step biocatalytic phosphorylation of glyceric acid. Glycerate‐2‐kinase from Thermotoga maritima was expressed in Escherichia coli, allowing easy purification. The selective glycerate‐2‐kinase‐catalyzed phosphorylation was followed by ³¹P NMR and showed excellent enantioselectivity towards phosphorylation of the d ‐enantiomer of glyceric acid. This straightforward phosphorylation reaction and subsequent product isolation enabled the preparation of enantiomerically pure d ‐glycerate 2‐phosphate. This phosphorylation reaction, using recombinant glycerate‐2‐kinase, yielded d ‐glycerate 2‐phosphate in fewer reaction steps and with higher purity than chemical routes.     

Aerosol Dynamics in Atmospheric Aromatic Photooxidation

Aerosol formation and growth in aromatic hydrocarbon / NO_x systems was studied in a series of outdoor smog chamber experiments. Analysis of the aerosol size distributions in those experiments that exhibited steady condensational growth provides estimates for the gas-phase partial pressures of the condensing species. Saturation ratios during these growth periods are estimated by comparing these partial pressures with vapor pressures obtained from an analysis of nucleation (Stern et al., 1987), and are found to be in the range of 5 to 20. Modeling of the size–distribution dynamics during the experiments is carried out using the sectional model ESMAP (Warren and Seinfeld, 1985). The full size-distribution model predicts more nucleation than an integral model (Stern et al., 1987), because the polydisperse aerosol representation leads to a lower condensation rate than that predicted for a monodisperse aerosol.     

Challenges in nucleic acid‐lipid films for transfection

The use of surface‐based methods for the delivery of therapeutics has recently generated increasing interest. These platforms have tremendous potential to minimize detrimental side effects associated with systemic delivery by localizing the therapeutic vehicle, and thus provide higher local doses for improved efficacy. Cationic lipids are one of the most commonly used synthetic carriers for the delivery of genetic cargo, such as DNA and RNA. However, reports on the use of lipid‐based films for gene delivery are scarce. Here we investigate the use of a lipid‐based film for the in vitro delivery of plasmid DNA. Solid DNA‐lipid films show very low levels of transfection, while identical complexes prepared for bolus delivery provide high levels of transfection when used directly. We investigate the mechanism, whereby the activity of these solid‐state films is lost and suggest methods for circumventing these challenges and restoring the efficacy of these films as gene delivery platforms. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3203–3213, 2013     

A Micro-manipulation Technique for the Purification of Diatoms for Isotope and Geochemical Analysis

A method is described for the purification and extraction of diatom samples for isotope and geochemical analysis. The technique involves a micro-manipulator attached to an inverted microscope with a cellular micro-injector system used to remove contaminants or separate assemblages into single-species samples. Whilst time consuming, the advances associated with this technique, eliminating issues related to contamination and the impact of species-dependent fractionation factor/isotopic effect, allows ultra-clean as well as species and/or size specific diatom samples to be analysed in palaeoenvironmental research down to seasonal timescale resolution. By further altering the inner dimensions of the commercially available capillary tubes, (3.5–150  $\upmu $ m) this technique can be extended for use with other microfossils including radiolaria (30  $\upmu $ m to 1 mm), pollen (6–100  $\upmu $ m) and phytolith samples (1–200  $\upmu $ m).     

Colloidal Processing of Ceramics

Colloidal processing of ceramics is reviewed with an emphasis on interparticle forces, suspension rheology, consolidation techniques, and drying behavior. Particular attention is given to the scientific concepts that underpin the fabrication of particulate-derived ceramic components. The complex interplay between suspension stability and its structural evolution during colloidal processing is highlighted.     

Surrogate endpoints for overall survival in advanced colorectal cancer: a clinician's perspective

Surrogate endpoints in oncology research and practice have garnered increasing attention over the past two decades. This activity has largely been driven by the promise surrogate endpoints appear to hold: the potential to get new therapies to seriously ill patients more rapidly. However, uncertainties abound. Even agreeing upon a definition of a "valid" surrogate endpoint has not been a straightforward exercise; this article begins by highlighting differences in how this term has been previously captured and applied, as well as laying out the basic criteria essential for its application in advanced colorectal cancer. Ideally, these elements include (but are not limited to) ease of measurement, rapid indication of treatment effect, and, most importantly, reliable and consistent prediction of the true impact of a treatment on the ultimate outcome of interest: overall survival. The strengths and weaknesses of current potential surrogate endpoints in advanced colorectal cancer, including performance status, carcinoembryonic antigen plasma level, overall response rate, time to progression, and disease-free survival, are each considered in turn. Finally, limitations of surrogate endpoints in the clinical setting, including challenges in extrapolation to new therapies, and the incomplete provision of information about potential adverse effects, are discussed. Work remains to be done between physicians and statisticians to bridge the gap between that which is statistically demonstrable and that which will be clinically useful.The term ;surrogate endpoint' was virtually unknown by most oncologists 15 years ago. A search in PubMed [http://www.ncbi.nlm.nih.gov] based on the words ;surrogate and cancer' shows that more than 2000 papers were published in medical journals in the last 20 years, with a dramatic increase of interest in the last five years. Interestingly, the same trend is observed when the words ;surrogate and heart' are entered into PubMed, suggesting that the issue of surrogate endpoints goes beyond the field of oncology, although the frequency of discussion varies (Figure 1; note different y-axis scales for oncology and cardiology).The goal of the present paper is to discuss the main issues surrounding surrogate endpoints from a clinician's point of view, using as an example surrogate endpoints of overall survival (OS) in advanced colorectal cancer (ACC).