The Role of Microenvironment Reagent Solubility on Reaction Kinetics of 4-Nitrophenol Reduction

The Role of Microenvironment Reagent Solubility on Reaction Kinetics of 4-Nitrophenol Reduction Michael Zeevi1 with Andrew Harrison1 and Christina Tang, PhD1 1Department of Chemical and Life Science Engineering, VCU School of Engineering Introduction: Nanoparticles are of increasing interest due to their high surface area to volume ratio, as well as that they enable fine-tuning of the reaction microenvironment. Through flash nanoprecipitation, core-shell polymer nanoreactors were formed by directed self-assembly. Using the reduction of 4-nitrophenol as a model reduction reaction, we investigated the effect of reagent solubility in the nanoreactor microenvironment’s on nanoreactor kinetics. Methods: The standard reaction was conducted at room temperature, with a 1000-fold excess of sodium borohydride in a quartz cuvette for real-time in situ­ UV-Vis analysis. Reagent concentrations were varied to examine the resulting effect on the calculated reaction rate constant. Reagent solubility limits in the nanoreactor microenvironment were estimated from solubility measurements in solvents with similar Hansen solubility parameters. Ethanol was chosen to represent the hydrophilic poly(ethylene) glycol phase and chloroform was chosen to represent the hydrophobic polystyrene phase. The hydrophilic phase had a visual absorbance at nm, and thus UV-Vis spectrometry was used to determine the saturation concentration. 1H NMR analysis with chloroform-D containing an internal standard (v/v TMS 0.03%) was used to measure the reagent solubility in the hydrophobic phase. Results: 4-nitrophenol solubility in ethanol was determined by UV-Vis spectrometry to be . The solubility in chloroform-D was determined by 1H NMR to be . When 4-nitrophenol concentration is varied independently of sodium borohydride, an inverse relationship is observed with respect to the rate constant. However, when 4-nitrophenol and sodium borohydride concentrations are varied concurrently, no change is witnessed in the rate constant above the standard reaction concentration. Conclusions: This experiment demonstrated that the rate of reaction in polystyrene core nanoreactors is not dependent on the reagent concentrations above the standard concentration. Solubility in each phase was measured in an effort to explain this behavior. The differences in solubility observed between the hydrophobic and hydrophilic phases may serve to explain this behavior if the interior, hydrophobic phase is saturated by 4-nitrophenol at the standard concentration. Future work should include study of concentrations at lower values than the standard concentration to determine when a change in the observed rate constant occurs.https://scholarscompass.vcu.edu/uresposters/1287/thumbnail.jp

Shear Force Fiber Spinning: Process Parameter and Polymer Solution Property Considerations

For application of polymer nanofibers (e.g., sensors, and scaffolds to study cell behavior) it is important to control the spatial orientation of the fibers. We compare the ability to align and pattern fibers using shear force fiber spinning, i.e. contacting a drop of polymer solution with a rotating collector to mechanically draw a fiber, with electrospinning onto a rotating drum. Using polystyrene as a model system, we observe that the fiber spacing using shear force fiber spinning was more uniform than electrospinning with the rotating drum with relative standard deviations of 18% and 39%, respectively. Importantly, the approaches are complementary as the fiber spacing achieved using electrospinning with the rotating drum was ~10 microns while fiber spacing achieved using shear force fiber spinning was ~250 microns. To expand to additional polymer systems, we use polymer entanglement and capillary number. Solution properties that favor large capillary numbers (\u3e50) prevent droplet breakup to facilitate fiber formation. Draw-down ratio was useful for determining appropriate process conditions (flow rate, rotational speed of the collector) to achieve continuous formation of fibers. These rules of thumb for considering the polymer solution properties and process parameters are expected to expand use of this platform for creating hierarchical structures of multiple fiber layers for cell scaffolds and additional applications

Considering data on a patient-reported outcome measure (PROM) for Chinese patients with thyroid diseases who speak Mandarin in China

The current study examined a newly-translated Simplified Chinese version of the Thyroid-Specific Patient-Reported Outcome Short Form (SC ThyPRO-39) among 179 thyroid patients in Mainland China. This study investigated whether the ceiling/floor effect (CFE) is present in responses to the SC ThyPRO-39. The appropriateness of regression modelling strategies for data with and without CFE were considered for a variety of predictor sets, and models were compared among six distributional models. With different predictor sets, the effect of gender and mode of administration (electronic interview versus self-administration) were of particular interest. Results suggested the use of Negative Binomial or Zero-inflated Negative Binomial as modelling strategies to fit the data with significant floor effect. There were also gender and mode effects on the scale scores. Findings indicated that overall, the SC ThyPRO-39 can be used as a patient-reported outcome measure among thyroid patients who speak Mandarin or read Simplified Chinese in China

Cantonese dichotic digit test: normative findings for young adults

"A dissertation submitted in partial fulfilment of the requirements for the Bachelor of Science (Speech and Hearing Sciences), The University of Hong Kong, June 30, 2006."Also available in print.Thesis (B.Sc)--University of Hong Kong, 2006.published_or_final_versionSpeech and Hearing SciencesBachelorBachelor of Science in Speech and Hearing Science

Improving Productivity of Multiphase Flow Aerobic Oxidation Using a Tube-in-Tube Membrane Contactor

The application of flow reactors in multiphase catalytic reactions represents a promising approach for enhancing the efficiency of this important class of chemical reactions. We developed a simple approach to improve the reactor productivity of multiphase catalytic reactions performed using a flow chemistry unit with a packed bed reactor. Specifically, a tube-in-tube membrane contactor (sparger) integrated in-line with the flow reactor has been successfully applied to the aerobic oxidation of benzyl alcohol to benzaldehyde utilizing a heterogeneous palladium catalyst in the packed bed. We examined the effect of sparger hydrodynamics on reactor productivity quantified by space time yield (STY). Implementation of the sparger, versus segmented flow achieved with the built in gas dosing module (1) increased reactor productivity 4-fold quantified by space time yield while maintaining high selectivity and (2) improved process safety as demonstrated by lower effective operating pressures

Vortex-enabled Andreev processes in quantum Hall-superconductor hybrids

Quantum Hall-superconductor heterostructures provide possible platforms for intrinsically fault-tolerant quantum computing. Motivated by several recent experiments that successfully integrated these phases, we investigate transport through a proximitized integer quantum Hall edge--paying particular attention to the impact of vortices in the superconductor. By examining the downstream conductance, we identify regimes in which sub-gap vortex levels mediate Andreev processes that would otherwise be frozen out in a vortex-free setup. Moreover, we show that at finite temperature, and in the limit of a large number of vortices, the downstream conductance can average to zero, indicating that the superconductor effectively behaves like a normal contact. Our results highlight the importance of considering vortices when using transport measurements to study superconducting correlations in quantum Hall-superconductor hybrids.Comment: 16 pages, 9 figure

Rapid Self-Assembly of Polymer Nanoparticles for Synergistic Codelivery of Paclitaxel and Lapatinib Via Flash Nanoprecipitation

Taxol, a formulation of paclitaxel (PTX), is one of the most widely used anticancer drugs, particularly for treating recurring ovarian carcinomas following surgery. Clinically, PTX is used in combination with other drugs such as lapatinib (LAP) to increase treatment efficacy. Delivering drug combinations with nanoparticles has the potential to improve chemotherapy outcomes. In this study, we use Flash NanoPrecipitation, a rapid, scalable process to encapsulate weakly hydrophobic drugs (logP \u3c 6) PTX and LAP into polymer nanoparticles with a coordination complex of tannic acid and iron formed during the mixing process. We determine the formulation parameters required to achieve uniform nanoparticles and evaluate the drug release in vitro. The size of the resulting nanoparticles was stable at pH 7.4, facilitating sustained drug release via first-order Fickian diffusion. Encapsulating either PTX or LAP into nanoparticles increases drug potency (as indicated by the decrease in IC-50 concentration); we observe a 1500-fold increase in PTX potency and a six-fold increase in LAP potency. When PTX and LAP are co-loaded in the same nanoparticle, they have a synergistic effect that is greater than treating with two single-drug-loaded nanoparticles as the combination index is 0.23 compared to 0.40, respectively

Rapid, Single-Step Protein Encapsulation via Flash NanoPrecipitation

Flash NanoPrecipitation (FNP) is a rapid method for encapsulating hydrophobic materials in polymer nanoparticles with high loading capacity. Encapsulating biologics such as proteins remains a challenge due to their low hydrophobicity (logP \u3c 6) and current methods require multiple processing steps. In this work, we report rapid, single-step protein encapsulation via FNP using bovine serum albumin (BSA) as a model protein. Nanoparticle formation involves complexation and precipitation of protein with tannic acid and stabilization with a cationic polyelectrolyte. Nanoparticle self-assembly is driven by hydrogen bonding and electrostatic interactions. Using this approach, high encapsulation efficiency (up to ~80%) of protein can be achieved. The resulting nanoparticles are stable at physiological pH and ionic strength. Overall, FNP is a rapid, efficient platform for encapsulating proteins for various applications

A Contingency Analysis of Post-Bureaucratic Controls in IT-Related Change

Recent developments in IT-enabled change have sparked many discussions on the emergence of a new management paradigm beyond bureaucracy. However, many of these studies are anecdotal or descriptive in nature, with few empirical studies. This research attempts to address this problem by developing a contingency framework within which the impact of information technology (IT) implementation on forms of post- bureaucratic controls is examined. It identifies post-bureaucratic control as a portfolio comprising empowerment, and panoptic or ideological control and argues that the emergence of these controls will differ, depending on the nature of the task structuredness and the context of IT-enabled change. It argues that the panoptic visibility afforded by the new technology enables management to decentralize power to employees without completely losing control. However, the ability to textualize behaviors in unstructured tasks is limited. In compensation, management will use ideological control to ensure that organization goals are met. Using a mixed methodology of qualitative and quantitative methods, two organizations, one undergoing an automational change and another a transformational change, were selected as cases to illustrate the framework. This study should prove interesting to researchers as it undertakes an empirical examination of post-bureaucratic controls and proposes a contingency framework to tie up apparent contradictions in findings. It also identifies new forms of control beyond bureaucracy, which practitioners may find are becoming increasingly relevant in a more fluid, uncertain “new economy.