Scholarly Works, Chemical Engineering

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3D Hepatic Cultures Simultaneously Maintain Primary Hepatocyte and Liver Sinusoidal Endothelial Cell Phenotypes
Kim, Yeonhee; Rajagopalan, Padmavathy (PLOS, 2010-11-12)
Developing in vitro engineered hepatic tissues that exhibit stable phenotype is a major challenge in the field of hepatic tissue engineering. However, the rapid dedifferentiation of hepatic parenchymal (hepatocytes) and non-parenchymal (liver sinusoidal endothelial, LSEC) cell types when removed from their natural environment in vivo remains a major obstacle. The primary goal of this study was to demonstrate that hepatic cells cultured in layered architectures could preserve or potentially enhance liver-specific behavior of both cell types. Primary rat hepatocytes and rat LSECs (rLSECs) were cultured in a layered three-dimensional (3D) configuration. The cell layers were separated by a chitosan-hyaluronic acid polyelectrolyte multilayer (PEM), which served to mimic the Space of Disse. Hepatocytes and rLSECs exhibited several key phenotypic characteristics over a twelve day culture period. Immunostaining for the sinusoidal endothelial 1 antibody (SE-1) demonstrated that rLSECs cultured in the 3D hepatic model maintained this unique feature over twelve days. In contrast, rLSECs cultured in monolayers lost their phenotype within three days. The unique stratified structure of the 3D culture resulted in enhanced heterotypic cell-cell interactions, which led to improvements in hepatocyte functions. Albumin production increased three to six fold in the rLSEC-PEM-Hepatocyte cultures. Only rLSEC-PEM-Hepatocyte cultures exhibited increasing CYP1A1/2 and CYP3A activity. Well-defined bile canaliculi were observed only in the rLSEC-PEM-Hepatocyte cultures. Together, these data suggest that rLSEC-PEM-Hepatocyte cultures are highly suitable models to monitor the transformation of toxins in the liver and their transport out of this organ. In summary, these results indicate that the layered rLSEC-PEM-hepatocyte model, which recapitulates key features of hepatic sinusoids, is a potentially powerful medium for obtaining comprehensive knowledge on liver metabolism, detoxification and signaling pathways in vitro.
Ambient ammonia synthesis via palladium-catalyzed electrohydrogenation of dinitrogen at low overpotential
Wang, Jun; Yu, Liang; Hu, Lin; Chen, Gang; Xin, Hongliang; Feng, Xiaofeng (Springer Nature, 2018-05-15)
Electrochemical reduction of N2 to NH3 provides an alternative to the Haber−Bosch process for sustainable, distributed production of NH3 when powered by renewable electricity. However, the development of such process has been impeded by the lack of efficient electrocatalysts for N2 reduction. Here we report efficient electroreduction of N2 to NH3 on palladium nanoparticles in phosphate buffer solution under ambient conditions, which exhibits high activity and selectivity with an NH3 yield rate of ~4.5 μg mg−1Pd h−1 and a Faradaic efficiency of 8.2% at 0.1 V vs. the reversible hydrogen electrode (corresponding to a low overpotential of 56 mV), outperforming other catalysts including gold and platinum. Density functional theory calculations suggest that the unique activity of palladium originates from its balanced hydrogen evolution activity and the Grotthuss-like hydride transfer mechanism on α-palladium hydride that lowers the free energy barrier of N2 hydrogenation to *N2H, the rate-limiting step for NH3 electrosynthesis.
Ammonium Bisphosphonate Polymeric Magnetic Nanocomplexes for Platinum Anticancer Drug Delivery and Imaging with Potential Hyperthermia and Temperature-Dependent Drug Release
Zhang, Rui; Fellows, Benjamin; Pothayee, Nikorn; Hu, Nan; Pothayee, Nipon; Jo, Ami; Bohórquez, Ana C.; Rinaldi, Carlos; Mefford, Olin Thompson; Davis, Richey M.; Riffle, Judy S. (Hindawi, 2018-08-05)
Novel magnetite-ammonium bisphosphonate graft ionic copolymer nanocomplexes (MGICs) have been developed for potential drug delivery, magnetic resonance imaging, and hyperthermia applications. The complexes displayed relatively uniform sizes with narrow size distributions upon self-assembly in aqueous media, and their sizes were stable under simulated physiological conditions for at least 7 days. The anticancer drugs, cisplatin and carboplatin, were loaded into the complexes, and sustained release of both drugs was observed. The transverse NMR relaxivities (s) of the complexes were 244 s−1 (mM Fe)−1 which is fast compared to either the commercial T2-weighted MRI agent Feridex IV® or our previously reported magnetite-block ionomer complexes. Phantom MRI images of the complexes demonstrated excellent negative contrast effects of such complexes. Thus, the bisphosphonate-bearing MGICs could be promising candidates for dual drug delivery and magnetic resonance imaging. Moreover, the bisphosphonate MGICs generate heat under an alternating magnetic field of 30 kA·m−1 at 206 kHz. The temperature of the MGIC dispersion in deionized water increased from 37 to 41°C after exposure to the magnetic field for 10 minutes, corresponding to a specific absorption rate of 77.0 W·g−1. This suggests their potential as hyperthermia treatment agents as well as the possibility of temperature-dependent drug release, making MGICs more versatile in potential drug delivery applications.
The assembly of integrated rat intestinal-hepatocyte cultures
Kothari, Anjaney; Rajagopalan, Padmavathy (2019-11)
The jejunum is the segment of the small intestine responsible for several metabolism and biotransformation functions. In this report, we have cultured rat jejunum explants in vitro and integrated them with hepatocyte cultures. We have also investigated the changes in jejunum function at different locations since spatial variations in intestinal functions have been reported previously. We divided the length of the rat jejunum into three distinct regions of approximately 9 cm each. We defined the regions as proximal (adjacent to the duodenum), medial, and distal (adjacent to the ileum). Spatiotemporal variations in functions were observed between these regions within the jejunum. Alkaline phosphatase activity (a marker of enterocyte function), decreased twofold between the proximal and distal regions at 4 hr. Lysozyme activity (a marker of Paneth cell function) increased from the proximal to the distal jejunum by 40% at 24 hr. Mucin-covered areas, a marker of goblet cell function, increased by twofold between the proximal and distal segments of the jejunum at 24 hr. When hepatocytes were integrated with proximal jejunum explants, statistically higher urea (similar to 2.4-fold) and mucin (57%) production were observed in the jejunum explants. The integrated intestine-liver cultures can be used as a platform for future investigations.
An atomic force microscope tip as a light source
Lulevich, V.; Honig, Christopher D. F.; Ducker, William A. (AIP Publishing, 2005-12-01)
We present a simple method for causing the end of a silicon nitride atomic force microscope (AFM) tip to emit light, and we use this emitted light to perform scanning near-field optical microscopy. Illumination of a silicon nitride AFM tip by blue (488 nm) or green (532 nm) laser light causes the sharp part of the tip to emit orange light. Orange light is emitted when the tip is immersed in either air or water; and while under illumination, emission continues for a period of many hours without photobleaching. By careful alignment of the incident beam, we can arrange the scattered light to decay as a function of the tip-substrate separation with a decay length of 100-200 nm. The exponential decay of the intensity means that the emitted light is dominated by contributions from parts of the tip that are near the sample, and therefore the emitted orange light can be used to capture high-resolution near-field optical images in air or water. (c) 2005 American Institute of Physics.
Bioactive Cellulose Nanocrystal-Poly(epsilon-Caprolactone) Nanocomposites for Bone Tissue Engineering Applications
Hong, Jung Ki; Cooke, Shelley L.; Whittington, Abby R.; Roman, Maren (2021-02-25)
3D-printed bone scaffolds hold great promise for the individualized treatment of critical-size bone defects. Among the resorbable polymers available for use as 3D-printable scaffold materials, poly(epsilon-caprolactone) (PCL) has many benefits. However, its relatively low stiffness and lack of bioactivity limit its use in load-bearing bone scaffolds. This study tests the hypothesis that surface-oxidized cellulose nanocrystals (SO-CNCs), decorated with carboxyl groups, can act as multi-functional scaffold additives that (1) improve the mechanical properties of PCL and (2) induce biomineral formation upon PCL resorption. To this end, an in vitro biomineralization study was performed to assess the ability of SO-CNCs to induce the formation of calcium phosphate minerals. In addition, PCL nanocomposites containing different amounts of SO-CNCs (1, 2, 3, 5, and 10 wt%) were prepared using melt compounding extrusion and characterized in terms of Young's modulus, ultimate tensile strength, crystallinity, thermal transitions, and water contact angle. Neither sulfuric acid-hydrolyzed CNCs (SH-CNCs) nor SO-CNCs were toxic to MC3T3 preosteoblasts during a 24 h exposure at concentrations ranging from 0.25 to 3.0 mg/mL. SO-CNCs were more effective at inducing mineral formation than SH-CNCs in simulated body fluid (1x). An SO-CNC content of 10 wt% in the PCL matrix caused a more than 2-fold increase in Young's modulus (stiffness) and a more than 60% increase in ultimate tensile strength. The matrix glass transition and melting temperatures were not affected by the SO-CNCs but the crystallization temperature increased by about 5.5 degrees C upon addition of 10 wt% SO-CNCs, the matrix crystallinity decreased from about 43 to about 40%, and the water contact angle decreased from 87 to 82.6 degrees. The abilities of SO-CNCs to induce calcium phosphate mineral formation and increase the Young's modulus of PCL render them attractive for applications as multi-functional nanoscale additives in PCL-based bone scaffolds.
Blood Serum Affects Polysaccharide Production and Surface Protein Expression in S. Aureus
Islam, Nazrul; Hossain, Khwaja G.; Ross, Julia M.; Marten, Mark R. (Juniper Publishers, 2017-01)
S. aureus biofilm serves a major role in pathogenesis. Two of the major components of bacterial biofilm are Polysaccharides intercellular adhesions (PIA) and surface proteins. It is not known how PIA and surface proteins expressions are affected in presence of blood serum. Analyses of surface proteins expressions will provide more effective biomarker discovery that might lead to development of antimicrobial therapeutics to meet the challenges of biofilm-related infections.Secondary cultures of S. aureus Philips, a biofilm-forming bacterium, were generated by inoculating 1 ml of overnight culture into 50 ml of TSB. Bacteria were cultured at several concentrations of blood serum and found that 12.5% supplemented blood serum provide s similar growth curve as normal TSB (100%). One and 2 D SASPAGE were used to separate proteins and the differentially expressed proteins were identified by nano-LC/MS.Polysaccharide intercellular adhesions production was significantly increased due to the addition of blood serum in the media. We also identified two serum proteins, apolipoprotein and globulin (Fc and Fab), that remained attached with the membrane fraction of bacterial proteins.These results have strongly demonstrated that blood serum influences the exopolysaccharide expression in S. aureus.
BRCA1 mutations attenuate super-enhancer function and chromatin looping in haploinsufficient human breast epithelial cells
Zhang, Xiaowen; Wang, Yao; Chiang, Huai-Chin; Hsieh, Yuan-Pang; Lu, Chang; Park, Ben H.; Jatoi, Ismail; Jin, Victor X.; Hu, Yanfen; Li, Rong (2019-04-17)
Background BRCA1-associated breast cancer originates from luminal progenitor cells. BRCA1 functions in multiple biological processes, including double-strand break repair, replication stress suppression, transcriptional regulation, and chromatin reorganization. While non-malignant cells carrying cancer-predisposing BRCA1 mutations exhibit increased genomic instability, it remains unclear whether BRCA1 haploinsufficiency affects transcription and chromatin dynamics in breast epithelial cells. Methods H3K27ac-associated super-enhancers were compared in primary breast epithelial cells from BRCA1 mutation carriers (BRCA1mut/+) and non-carriers (BRCA1+/+). Non-tumorigenic MCF10A breast epithelial cells with engineered BRCA1 haploinsufficiency were used to confirm the H3K27ac changes. The impact of BRCA1 mutations on enhancer function and enhancer-promoter looping was assessed in MCF10A cells. Results Here, we show that primary mammary epithelial cells from women with BRCA1 mutations display significant loss of H3K27ac-associated super-enhancers. These BRCA1-dependent super-enhancers are enriched with binding motifs for the GATA family. Non-tumorigenic BRCA1mut/+ MCF10A cells recapitulate the H3K27ac loss. Attenuated histone mark and enhancer activity in these BRCA1mut/+ MCF10A cells can be partially restored with wild-type BRCA1. Furthermore, chromatin conformation analysis demonstrates impaired enhancer-promoter looping in BRCA1mut/+ MCF10A cells. Conclusions H3K27ac-associated super-enhancer loss is a previously unappreciated functional deficiency in ostensibly normal BRCA1 mutation-carrying breast epithelium. Our findings offer new mechanistic insights into BRCA1 mutation-associated transcriptional and epigenetic abnormality in breast epithelial cells and tissue/cell lineage-specific tumorigenesis.
Characterizing glucose, illumination, and nitrogen-deprivation phenotypes of Synechocystis PCC6803 with Raman spectroscopy
Tanniche, Imen; Collakova, Eva; Denbow, Cynthia J.; Senger, Ryan S. (2020-03-30)
Background. Synechocystis sp. PCC6803 is a model cyanobacterium that has been studied widely and is considered for metabolic engineering applications. Here, Raman spectroscopy and Raman chemometrics (Rametrix (TM)) were used to (i) study broad phenotypic changes in response to growth conditions, (ii) identify phenotypic changes associated with its circadian rhythm, and (iii) correlate individual Raman bands with biomolecules and verify these with more accepted analytical methods. Methods. Synechocystis cultures were grown under various conditions, exploring dependencies on light and/or external carbon and nitrogen sources. The Rametrix (TM) LITE Toolbox for MATLAB (R) was used to process Raman spectra and perform principal component analysis (PCA) and discriminant analysis of principal components (DAPC). The Rametrix (TM) PRO Toolbox was used to validate these models through leave-oneout routines that classified a Raman spectrum when growth conditions were withheld from the model. Performance was measured by classification accuracy, sensitivity, and specificity. Raman spectra were also subjected to statistical tests (ANOVA and pairwise comparisons) to identify statistically relevant changes in Synechocystis phenotypes. Finally, experimental methods, including widely used analytical and spectroscopic assays were used to quantify the levels of glycogen, fatty acids, amino acids, and chlorophyll a for correlations with Raman data. Results. PCA and DAPC models produced distinct clustering of Raman spectra, representing multiple Synechocystis phenotypes, based on (i) growth in the presence of 5 mM glucose, (ii) illumination (dark, light/dark [12 h/12 h], and continuous light at 20 mE), (iii) nitrogen deprivation (0-100%NaNO3 of native BG-11 medium in continuous light), and (iv) throughout a 24 h light/dark (12 h/12 h) circadian rhythm growth cycle. Rametrix (TM) PRO was successful in identifying glucose-induced phenotypes with 95.3% accuracy, 93.4% sensitivity, and 96.9% specificity. Prediction accuracy was above random chance values for all other studies. Circadian rhythm analysis showed a return to the initial phenotype after 24 hours for cultures grown in light/dark (12 h/12 h) cycles; this did not occur for cultures grown in the dark. Finally, correlation coefficients (R > 0.7) were found for glycogen, all amino acids, and chlorophyll a when comparing specific Raman bands to other experimental results.
Characterizing metabolic stress-induced phenotypes of Synechocystis PCC6803 with Raman spectroscopy
Tanniche, Imen; Collakova, Eva; Denbow, Cynthia J.; Senger, Ryan S. (2020-03-30)
Background. During their long evolution, Synechocystis sp. PCC6803 developed a remarkable capacity to acclimate to diverse environmental conditions. In this study, Raman spectroscopy and Raman chemometrics tools (Rametrix (TM)) were employed to investigate the phenotypic changes in response to external stressors and correlate specific Raman bands with their corresponding biomolecules determined with widely used analytical methods. Methods. Synechocystis cells were grown in the presence of (i) acetate (7.5-30 mM), (ii) NaCl (50-150 mM) and (iii) limiting levels of MgSO4 (0-62.5 mM) in BG-11 media. Principal component analysis (PCA) and discriminant analysis of PCs (DAPC) were performed with the Rametrix (TM) LITE Toolbox for MATLABR (R). Next, validation of these models was realized via Rametrix (TM) PRO Toolbox where prediction of accuracy, sensitivity, and specificity for an unknown Raman spectrum was calculated. These analyses were coupled with statistical tests (ANOVA and pairwise comparison) to determine statistically significant changes in the phenotypic responses. Finally, amino acid and fatty acid levels were measured with well-established analytical methods. The obtained data were correlated with previously established Raman bands assigned to these biomolecules. Results. Distinguishable clusters representative of phenotypic responses were observed based on the external stimuli (i.e., acetate, NaCl, MgSO4, and controls grown on BG-11 medium) or its concentration when analyzing separately. For all these cases, Rametrix (TM) PRO was able to predict efficiently the corresponding concentration in the culture media for an unknown Raman spectra with accuracy, sensitivity and specificity exceeding random chance. Finally, correlations (R > 0.7) were observed for all amino acids and fatty acids between well-established analytical methods and Raman bands.
Comparison Of Flow Birefringence Data with A Numerical-Simulation Of The Hole Pressure
Baird, Donald G.; Read, M. D.; Reddy, Junuthula N. (AIP Publishing, 1988-08-01)
The penalty_Galerkin finite_element method is used to simulate the flow of a polystyrene melt over a rectangular slot placed perpendicular to the flow direction. The White_Metzner constitutive equation is used with a Carreau model viscosity function and a shear rate_dependent relaxation time defined so that the primary normal stress difference is exactly reproduced by the model in simple shear flow. Values of the stress field predicted by the simulation are compared with those obtained experimentally by means of flowbirefringence. As observed by others, the limiting elasticity value as determined by the Weissenberg number (We) for convergence of the algorithm decreased with increased refinement of the mesh. However, good agreement is still found between predicted values of stress using the coarse mesh and those measured by means of flowbirefringence. This work suggests that there may be an optimum mesh for a given flow and constitutive equation which will still give physically realistic results. The Weissenberg number for the melt used in the experimental study asymptotically approached a value of about 1.5 with increasing shear stress, suggesting that it may not be necessary to reach excessively high values of We for simulations involving some polymer melts.
Comparison Of The Rheological Properties Of Concentrated-Solutions Of A Rodlike And A Flexible Chain Polyamide
Baird, Donald G.; Ballman, R. L. (AIP Publishing, 1979)
The steady state shear rheological properties of solutions of a rodlike polyamide, poly_p_phenyleneterephthalamide (PPT), in 100% sulfuric acid have been compared with those of solutions of a flexible chain polyamide, nylon 6,6 in the same solvent. For solutions of similar concentration (c) and molecular weight (M), it was found that the primary normal stress difference (N1) and the viscosity (_), compared at the same shear rate (__), were an order of magnitude greater for solutions of PPT. It was believed that this behavior could be accounted for through the formation of an enhanced entanglement network in the PPT solutions. Plots of the zero shear viscosity(_0) versus cM_w, where M_w is the weight average molecular weight, for both systems revealed that "bends" occurred in the data corresponding to a critical entanglement molecular weight (Mc) of 1180 for PPT (this corresponds to 30 main chain atoms (z)) and to 5260 (z=330) for nylon 6,6. More significantly, _0 was found to be proportional to (cM_u)6.8 for solutions of PPT and to (cM_w)3.4 for nylon 6,6 solutions. _ versus __ curves were similar in shape for both systems and could be reduced to the same master curve with the only difference being that the relaxation times or shifting factors were considerably greater for the PPT solutions. This suggested that the process of destroying entanglements may be similar for both polymers. The overlap parameter c[_], where [_] is the intrinsic viscosity, provided a much better correlation of _0 data from the two sets of solutions than did the segment contact parameter cM_w. This suggested that the structural variable controlling the onset of entanglements may be a parameter such as the radius of gyration. Because of the inability of rodlike molecules to coil around each other, further insight into the nature of entanglements is obtained.
Complex receptor-ligand dynamics control the response of the VEGF system to protease injury
Forsten-Williams, Kimberly; Kurtagic, Elma; Nugent, Matthew A. (2011-10-21)
Background Vascular homeostasis and response to injury are dependent on the coordinated activity of growth factors such as vascular endothelial growth factor-A (VEGF). VEGF signaling is mediated by VEGF receptors 1 (VEGFR1) and 2 (VEGFR2). VEGF also binds to extracellular matrix (ECM) and neuropilin (NP), a cell surface glycoprotein that enhances VEGF binding to VEGFR2 while inhibiting VEGF-VEGFR1 interactions. Proteases such as neutrophil elastase release VEGF bound to ECM; however, this results in proteolytic processing of VEGF to a smaller species termed VEGF fragment (VEGFf). We hypothesized that the generation and presence of VEGFf would have significant effects on the binding distribution of VEGF. Results We show that VEGFf, unlike VEGF, does not bind ECM, fibronectin, or NP-1. Using computational simulations, we find that excess VEGFf can lead to increased binding of VEGF to VEGFR2 through VEGFf binding to VEGFR1 and subsequent liberation of NP-1. We show experimentally that VEGF-induced migration has a biphasic response to conversion of VEGF to VEGFf. Simulations suggest that a simple change in VEGFR1 or VEGFR2 complexes are unlikely to be responsible and that a more complex integration of signals is more likely involved. Conclusions These findings suggest that proteolytic damage at sites of tissue injury and inflammation has the potential to modulate the VEGF system through a complex process and highlight the need for quantitative analysis to reveal mechanisms of growth factor control.
Computational models in plant-pathogen interactions: the case of Phytophthora infestans
Pinzón, Andrés; Barreto, Emiliano; Bernal, Adriana; Achenie, Luke E. K.; González Barrios, Andrés Fernando; Isea, Raúl; Restrepo, Silvia (2009-11-12)
Background Phytophthora infestans is a devastating oomycete pathogen of potato production worldwide. This review explores the use of computational models for studying the molecular interactions between P. infestans and one of its hosts, Solanum tuberosum. Modeling and conclusion Deterministic logistics models have been widely used to study pathogenicity mechanisms since the early 1950s, and have focused on processes at higher biological resolution levels. In recent years, owing to the availability of high throughput biological data and computational resources, interest in stochastic modeling of plant-pathogen interactions has grown. Stochastic models better reflect the behavior of biological systems. Most modern approaches to plant pathology modeling require molecular kinetics information. Unfortunately, this information is not available for many plant pathogens, including P. infestans. Boolean formalism has compensated for the lack of kinetics; this is especially the case where comparative genomics, protein-protein interactions and differential gene expression are the most common data resources.
Computational study of HIV gp120 as a target for polyanionic entry inhibitors: Exploiting the V3 loop region
Hollingsworth, Louis R. IV; Brown, Anne M.; Gandour, Richard D.; Bevan, David R. (PLOS, 2018-01-18)
Multiple approaches are being utilized to develop therapeutics to treat HIV infection. One approach is designed to inhibit entry of HIV into host cells, with a target being the viral envelope glycoprotein, gp120. Polyanionic compounds have been shown to be effective in inhibiting HIV entry, with a mechanism involving electrostatic interactions with the V3 loop of gp120 being proposed. In this study, we applied computational methods to elucidate molecular interactions between the repeat unit of the precisely alternating polyanion, Poly(4,40-stilbenedicarboxylate- alt±maleic acid) (DCSti-alt-MA) and the V3 loop of gp120 from strains of HIV against which these polyanions were previously tested (IIIb, BaL, 92UG037, JR-CSF) as well as two strains for which gp120 crystal structures are available (YU2, 2B4C). Homology modeling was used to create models of the gp120 proteins. Using monomers of the gp120 protein, we applied extensive molecular dynamics simulations to obtain dominant morphologies that represent a variety of open-closed states of the V3 loop to examine the interaction of 112 ligands of the repeating units of DCSti-alt-MA docked to the V3 loop and surrounding residues. Using the distance between the V1/V2 and V3 loops of gp120 as a metric, we revealed through MD simulations that gp120 from the lab-adapted strains (BaL and IIIb), which are more susceptible to inhibition by DCSti-alt-MA, clearly transitioned to the closed state in one replicate of each simulation set, whereas none of the replicates from the Tier II strains (92UG037 and JR-CSF) did so. Docking repeat unit microspecies to the gp120 protein before and after MD simulation enabled identification of residues that were key for binding. Notably, only a few residues were found to be important for docking both before and after MD simulation as a result of the conformational heterogeneity provided by the simulations. Consideration of the residues that were consistently involved in interactions with the ligand revealed the importance of both hydrophilic and hydrophobic moieties of the ligand for effective binding. The results also suggest that polymers of DCSti-alt-MA with repeating units of different configurations may have advantages for therapeutic efficacy.
Continuous flow synthesis of a pharmaceutical intermediate: a computational fluid dynamics approach
Armstrong, Cameron T.; Pritchard, Cailean Q.; Cook, Daniel W.; Ibrahim, Mariam; Desai, Bimbisar K.; Whitham, Patrick J.; Marquardt, Brian J.; Chen, Yizheng; Zoueu, Jeremie T.; Bortner, Michael J.; Roper, Thomas D. (2019-03-01)
Continuous flow chemistry has the potential to greatly improve efficiency in the synthesis of active pharmaceutical ingredients (APIs); however, the optimization of these processes can be complicated by a large number of variables affecting reaction success. In this work, a screening design of experiments was used to compare computational fluid dynamics (CFD) simulations with experimental results. CFD simulations and experimental results both identified the reactor residence time and reactor temperature as the most significant factors affecting product yield for this reaction within the studied design space. A point-to-point comparison of the results showed absolute differences in product yield as low as 2.4% yield at low residence times and up to 19.1% yield at high residence times with strong correlation between predicted and experimental percent yields. CFD was found to underestimate the product yields at low residence times and overestimate at higher residence times. The correlation in predicted product yield and the agreement in identifying significant factors in reaction performance reveals the utility of CFD as a valuable tool in the design of continuous flow tube reactors with significantly reduced experimentation.
A correlation force spectrometer for single molecule measurements under tensile load
Radiom, Milad; Honig, Christopher D. F.; Walz, John Y.; Paul, Mark R.; Ducker, William A. (American Institute of Physics, 2013-01-07)
The dynamical-mechanical properties of a small region of fluid can be measured using two closely spaced thermally stimulated micrometer-scale cantilevers. We call this technique correlation force spectroscopy (CFS). We describe an instrument that is designed for characterizing the extensional properties of polymer molecules that straddle the gap between the two cantilevers and use it to measure the stiffness and damping (molecular friction) of a dextran molecule. The device is based on a commercial atomic force microscope, into which we have incorporated a second antiparallel cantilever. The deflection of each cantilever is measured in the frequency range dc-1 MHz and is used to generate the cross-correlation at equilibrium. The main advantage of cross-correlation measurements is the reduction in thermal noise, which sets a fundamental noise limit to force resolution. We show that the thermal noise in our cross-correlation measurements is less than one third of the value for single-cantilever force microscopy. The dynamics of the cantilever pair is modeled using the deterministic motion of a harmonic oscillator initially displaced from equilibrium, which yields the equilibrium auto and cross-correlations in cantilever displacement via the fluctuation-dissipation theorem. Fitted parameters from the model (stiffness and damping) are used to characterize the fluid at equilibrium, including any straddling molecules. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4772646]
Correlations between the thermal vibrations of two cantilevers: Validation of deterministic analysis via the fluctuation-dissipation theorem
Honig, Christopher D. F.; Radiom, Milad; Robbins, Brian A.; Walz, John Y.; Paul, Mark R.; Ducker, William A. (AIP Publishing, 2012-02-01)
We validate a theoretical approach for analyzing correlations in the fluctuations of two cantilevers in terms of a deterministic model, using the fluctuation-dissipation theorem [M. R. Paul and M. C. Cross, Phys. Rev. Lett. 92, 235501 (2004)]. The validation has been made possible through measurement of the correlations between the thermally stimulated vibrations of two closely spaced micrometer-scale cantilevers in fluid. Validation of the theory enables development of a method for characterizing fluids, which we call correlation force spectrometry. (C) 2012 American Institute of Physics. [doi:10.1063/1.3681141]
Creation of a gradient polymer-fullerene interface in photovoltaic devices by thermally controlled interdiffusion
Drees, M.; Premaratne, K.; Graupner, W.; Heflin, James R.; Davis, Ruth M.; Marciu, D.; Miller, M. (AIP Publishing, 2002-12-01)
Efficient polymer-fullerene photovoltaic devices require close proximity of the two materials to ensure photoexcited electron transfer from the semiconducting polymer to the fullerene acceptor. We describe studies in which a bilayer system consisting of spin-cast 2-methoxy-5-(2(')-ethylhexyloxy)-1,4-phenylenevinylene copolymer (MEH-PPV) and sublimed C-60 is heated above the MEH-PPV glass transition temperature in an inert environment, inducing an interdiffusion of the polymer and the fullerene layers. With this process, a controlled, bulk, gradient heterojunction is created bringing the fullerene molecules within the exciton diffusion radius of the MEH-PPV throughout the film to achieve highly efficient charge separation. The interdiffused devices show a dramatic decrease in photoluminescence and concomitant increase in short circuit currents, demonstrating the improved interface. (C) 2002 American Institute of Physics.
Design Of A High-Temperature And High-Pressure Liquid Flow Cell For X-Ray Absorption Fine Structure Measurements Under Catalytic Reaction Conditions
Kawai, T.; Chun, W. J.; Asakura, K.; Koike, Y.; Nomura, M.; Bando, K. K.; Oyama, Shigeo Ted; Sumiya, H. (AIP Publishing, 2008-01-01)
The design and performance of a new high-pressure and high-temperature cell for measurement of x-ray absorption fine structure (XAFS) spectra of solid catalysts working in a flowing liquid are presented. The cell has flat, high-purity sintered cubic boron nitride (c-BN) windows which can tolerate high temperature (900 K) and high pressure (10 MPa). The c-BN is a new material which has the highest tensile strength, second only to diamond, and is also chemically and thermally stable. The use of the cell is demonstrated for measurements of PtPd/Al(2)O(3) and Ni(2)P/SiO(2) hydrodesulfurization catalysts at reaction conditions. A technique called delta chi (Delta chi), involving determining the difference between XAFS spectra of the sample at reaction conditions and the bare sample, is introduced. (c) 2008 American Institute of Physics.

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