693 research outputs found
Dynamic response studies on aggregation and breakage dynamics of colloidal dispersions in stirred tanks
Aggregation and breakage of aggregates of fully destabilized polystyrene latex particles in turbulent flow was studied experimentally in both batch and continuous stirred tanks using small-angle static light scattering. It was found that the steady-state values of the root-mean-square radius of gyration are fully reversible upon changes of stirring speed as well as solid volume fraction. Steady-state values of the root-mean-square radius of gyration were decreasing with decreasing solid volume fraction as well as with increasing stirring speed. Moreover, it was found that the steady-state structure and shape of the aggregates is not influenced by the applied stirring speed
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Chain-end modifications and sequence arrangements of antimicrobial peptoids for mediating activity and nano-assembly
Poly(N-substituted glycine) âpeptoidsâ are an interesting class of peptidomimics that can resist proteolysis and mimic naturally found antimicrobial peptides (AMPs), which exhibit wide spectrum activity against bacteria. This work investigates the possibility of modifying peptoid AMP mimics (AMPMs) with aliphatic lipid âtailsâ to generate âlipopeptoidsâ that can assemble into micellar nanostructures, and evaluates their antimicrobial activities. Two families of AMPMs with different distributions of hydrophobic and cationic residues were employedâone with a uniform repeating amphiphilicity, the other with a surfactant-like head-to-tail amphiphilicity. To further evaluate the interplay between self-assembly and activity, the lipopeptoids were variously modified at the AMPM chain ends with a diethylene glycol (EG2) and/or a cationic group (Nlys-Nlys dipeptoid) to adjust amphiphilicity and chain flexibility. Self-assembly was investigated by critical aggregation concentration (CAC) fluorescence assays and dynamic light scattering (DLS). The structure of a key species was also verified by small-angle X-ray scattering (SAXS) and cryo-electron microscopy (cryo-EM). To screen for antibacterial properties, we measured the minimum inhibitory concentrations (MIC) against S. aureus, E. coli, and P. aeruginosa. We found that certain combinations of lipid tail and AMPM sequences exhibit increased antibacterial activity (i.e., decreased MICs). Perhaps counter-intuitively, we were particularly interested in increased MICs in combination with low CACs. Concealing antimicrobial interactions due to packing of AMPMs in nano-assemblies could pave the way to AMPMs that may be âinertâ even if unintentionally released and prevent microbes from gaining resistance to the lipopeptoids. Overall, incorporation of EG2 significantly improved lipopeptoids packing while the hydrophobic tail length was found to have a major influence over the MIC. One particular sequence, which we named C15-EG2-(kss)4, exhibited a very low CAC of 34 ÎŒM (0.0075 wt.%) and a significantly increased MIC above values for the unmodified AMPM. With the sequence design trends uncovered from this study, future work will focus on discovering more species such as C15-EG2-(kss)4 and on investigating release mechanisms and the potency of the released lipopeptoids
Measurement of adsorption of a single component from the liquid phase : modelling investigation and sensitivity analysis
In this work, we consider an alternative approach for the measurement of adsorption from the liquid phase. Consider a mixture consisting of a non-adsorbed component (B) and an adsorbed component (A) present at some low concentration. Initially, a feed of component B only flows through a column packed with an adsorbent. Then, the feed is switched to the mixture of A and B. As soon as the mixture enters the column, there will be a reduction in the outlet flow rate as component A leaves the liquid phase and passes into the adsorbed phase. There are three stages to this work. The first is to develop overall and component balances to show how the amount adsorbed of component A can be determined from the variation in the column outlet flow rate. The second is to determine the actual variation in the column outlet flow rate for both plug flow and axial-dispersed plug flow. The final stage is to consider the suitability of a gravity-fed system to deliver the feed to the column. An analysis of the results shows that the experimental arrangement should be able to accurately monitor adsorption from the liquid phase where the mass fraction of the solute is of the order of 1%: the limiting experimental factor is how constant the volumetric flow rate of the liquid feed can be maintained
Structure of laponite-styrene precursor dispersions for production of advanced polymer-clay nanocomposites
One method for production of polymer-clay nanocomposites involves dispersal of surface-modified clay in a polymerisable monomeric solvent, followed by fast in situ polymerisation. In order to tailor the properties of the final material we aim to control the dispersion state of the clay in the precursor solvent. Here, we study dispersions of surface-modified Laponite, a synthetic clay, in styrene via large-scale Monte-Carlo simulations and experimentally, using small angle X-ray and static light scattering. By tuning the effective interaction between simulated laponite particles we are able to reproduce the experimental scattering intensity patterns for this system, with good accuracy over a wide range of length scales. However, this agreement could only be obtained by introducing a permanent electrostatic dipole moment into the plane of each Laponite particle, which we explain in terms of the distribution of substituted metal atoms within each Laponite particle. This suggests that Laponite dispersions, and perhaps other clay suspensions, should display some of the structural characteristics of dipolar fluids. Our simulated structures show aggregation regimes ranging from networks of long chains to dense clusters of Laponite particles, and we also obtain some intriguing âglobularâ clusters, similar to capsids. We see no indication of any âhouse-of-cardsâ structures. The simulation that most closely matches experimental results indicates that gel-like networks are obtained in Laponite dispersions, which however appear optically clear and non-sedimenting over extended periods of time. This suggests it could be difficult to obtain truly isotropic equilibrium dispersion as a starting point for synthesis of advanced polymer-clay nanocomposites with controlled structures
Nucleation and growth kinetics of sodium chloride crystallization from water and deuterium oxide
Despite the ubiquity of the crystallization of sodium chloride (NaCl) throughout history, few detailed, well-controlled quantitative studies of the kinetics of NaCl crystallization have been published. Taking advantage of recent advances in technology such as image analysis for crystallite counting and âhigh-throughputâ techniques for characterizing the highly stochastic nucleation process, we report on a detailed examination of the primary and secondary nucleation kinetics of NaCl, crystallized from solution, in water (H 2O) and in the isotopologue D 2O. We show that crystallization conditions, especially sample agitation, have a very significant effect on crystallization kinetics. We also critically evaluate the workflow employed and the associated nucleation/growth models used to interpret its results, comparing outcomes from NaCl with those from organic crystal systems with which the workflow was originally developed and demonstrated. For primary nucleation, some key assumptions of the workflow and data interpretation are called into question for the NaCl system. Even so, it can still provide direct measurements of secondary nucleation and crystal growth from crystal counting and sizing, providing valuable characterization under consistent controlled conditions to enhance and âbring up to dateâ the literature on the crystallization of this ubiquitous system
Nucleation and growth kinetics of sodium chloride crystallization from water and deuterium oxide
Despite the ubiquity of crystallization of sodium chloride (NaCl) throughout history, few detailed, well-controlled quantitative studies of the kinetics of NaCl crystallization have been published. Taking advantage of recent advances in technology such as image analysis for crystallite counting and âhigh-throughputâ techniques for characterizing the highly stochastic nucleation process, we report on a detailed examination of primary and secondary nucleation kinetics of NaCl, crystallizing from solution, in water (H2O) and in the isotopologue D2O. We show that crystallization conditions, especially sample agitation, have a very significant effect on crystallization kinetics. We also critically evaluate the workflow employed and the associated nucleation/growth models used to interpret its results, comparing outcomes from NaCl with those fromorganic crystal systems with which the workflow was originally developed and demonstrated. For primary nucleation, some key assumptions of the workflow and data interpretation are called into question for the NaCl system. Even so it can still provide direct measurements of secondary nucleation and crystal growth from crystal counting and sizing, providing valuable characterisation under consistent controlled conditions to enhance and âbring up to dateâ the literature on the crystallization of this ubiquitous system
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Fast Gate: Subnanosecond Gate Detectors for Laser Radiography
X-ray radiography is used as a principal diagnostic in a wide range of hydrodynamic tests relevant to the weapons program and also for basic materials and equation-of-state science studies. The quality of the x-ray radiograph can be significantly degraded by the scattering of x-rays within the object and by components of the test system itself. Elimination of these scattered x-rays from the recorded images can either substantially improve the image contrast and signal-to-noise or allow smaller, lower-cost x-ray sources to be used. The scattered x-rays could be minimized through the use of a much shorter-duration x-ray pulse and a fast, gated detector. The short duration x-ray pulse and the fast gated detector allow detection of only those x-rays which pass through the object being radiographed. X-rays which are the result of scattering have longer path lengths and take longer to reach the target. Most of these can be eliminated if the detector if gated off before they arrive at the detector. Until recently there were no sources of high energy x-rays (1-10 MeV) with short duration (sub 100 picosecond) pulses. Now the Petawatt Laser Facility (ref 1) at Lawrence Livermore National Laboratory has been able to produce 0.1 rads at 1 meter of MeV energy x-rays in 1-0 picoseconds. Efforts are underway to significantly increase this x-ray output. The combination of the existing short-duration, Petawatt-produced x-ray pulses and an x-ray detector with sub-100-ps gate times could eliminate most of the scattered x-rays from the radiograph image and allow highly improved radiography particularly for larger, high density test objects
Effect of synthesis conditions on formation pathways of metal organic framework (MOF-5) Crystals
Metal Organic Frameworks (MOFs) represent a class of nanoporous crystalline materials with far reaching potential in gas storage, catalysis, and medical devices. We investigated the effects of synthesis process parameters on production of MOF-5 from terephthalic acid and zinc nitrate in diethylformamide. Under favorable synthesis conditions, we systematically mapped a solid formation diagram in terms of time and temperature for both stirred and unstirred conditions. The synthesis of MOF-5 has been previously reported as a straightforward reaction progressing from precursor compounds in solution directly to the final MOF-5 solid phase product. However, we show that the solid phase formation process is far more complex, invariably transferring through metastable intermediate crystalline phases before the final MOF-5 phase is reached, providing new insights into the formation pathways of MOFs. We also identify process parameters suitable for scale-up and continuous manufacturing of high purity MOF-5
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