Tai-Shung Chung

Morphology, drug distribution, and in vitro release profiles of biodegradable polymeric microspheres containing protein fabricated by double-emulsion solvent extraction/evaporation method.

The surface and internal morphology, drug distribution and release kinetics at 22 degrees C of polyesters such as PCL (polycaprolactone) and PLGA (poly(DL-lactic-co-glycolic acid)) 65:35 microspheres containing BSA (bovine serum albumin) have been investigated in order to understand the relationship amongst morphology, drug distribution and in vitro release profiles and to develop controlled release devices for marine fishes in tropical area. CLSM (confocal laser scanning microscope) micrographs reveal that the polyvinylalcohol (PVA as an emulsifier) concentration in the external water phase strongly influences drug distribution within microspheres and release profiles. The presence of PVA in the internal water phase enhances the stabilization of inner water droplets against coalescence. This results in a more uniform drug distribution and a slower BSA release. Different oil-phase volumes and polymer concentrations yield different solvent exchange and precipitation mechanisms, which lead to different morphologies. A low oil-phase volume yields microspheres with a porous matrix and defective skin surface, which gives a high initial BSA burst as well as a fast release profile. Microspheres fabricated from a low polymer concentration have less defective skin surface, but with a less tortuous inner matrix which results in a more rapid BSA release. A higher BSA loading yields a larger concentration gradient between the emulsion droplet and the continuous water phase as well as between the microspheres and the in vitro medium. The former results in a lower encapsulation efficiency, whereas the latter yields a faster initial burst and a more rapid release profile. High stirring speed can reduce microsphere size, but decreases the yield of microspheres.

Effect of preparation temperature on the characteristics and release profiles of PLGA microspheres containing protein fabricated by double-emulsion solvent extraction/evaporation method

This study describes the influence of preparation temperature on the various characteristics and release profiles of poly(DL-lactide-co-glycolide) (PLGA) microspheres. The bovine serum albumin (BSA)-loaded microspheres were prepared using the water-in-oil-in-water (w/o/w) technique with poly(vinyl alcohol) as surfactant in the external aqueous phase. We have varied the preparation temperature to observe its effect on microsphere characteristics such as the microsphere shrinking rate during formation, particle size, density, surface and internal morphology, BSA encapsulation efficiency, BSA initial release, microsphere degradation and BSA in vitro release behaviour. During fabrication, a low preparation temperature of 5 degrees C gives the fastest initial but the slowest overall shrinking rate. Microspheres formed at high temperatures of 38 degrees C and 42 degrees C on the other hand have the lowest initial yet the highest overall shrinking rate. Subsequently, microsphere mean size increases and the particle size distribution widens with increase in the preparation temperature. Although all the microspheres have a porous surface as well as internal structure, microspheres fabricated at high temperatures have a uniform internal pore distribution and a very thin dense skin layer, while microspheres fabricated at lower temperatures have a thicker but porous skin layer and bigger pores in the middle of the sphere. Microspheres formed at 33 degrees C are found to give the highest initial burst release. In terms of in vitro release, microspheres fabricated at low temperatures (5 degrees C, 15 degrees C and 22 degrees C) exhibit similar, steady rates. Microspheres formed at higher temperatures however give very low release rates after their initial release. The results obtained suggest that preparation temperature significantly affects microsphere formation, resulting in their structural and protein release profile differences. These differences ultimately work together to affect the initial release and overall release patterns of the microspheres.

Gas transport properties of 6FDA-durene/1,4-phenylenediamine (pPDA) copolyimides

We have determined the gas transport properties of He, H2, O2, N2, and CO2 for 6FDA-durene homopolymer and 6FDA-durene/pPDA copolyimides. The 6FDA-durene exhibits the highest permeability with the lowest selectivity. Permeability of copolymers decreases with increasing 6FDA–pPDA content, while permselectivity increases with an increase in 6FDA–pPDA content. 6FDA-durene/pPDA (50/50) and 6FDA-durene/pPDA (20/80) materials have O2 and CO2 permeabilities greater than those calculated from the addition rule of the semilogarithmic equation. These higher deviations from the additional rule of the semilogarithmic equation are mainly attributed to the fact that these copolyimides have higher solubility coefficients than those calculated from the additive rule. The Tg s of 6FDA-durene/pPDA copolyimides decrease with an increase in 6FDA–pPDA content. Tg s predicted from the Fox equation are lower than the experimental data, and the their difference increases with an increase in pPDA content, implying the copolyimides of 6FDA-durene/pPDA may have greater interstitial space among chains because of the conformation difference, and thus create more fraction free volume compared with the ideal case of simple volume addition. Density measurements also suggest these two copolymers have greater free volumes and the fractions of free volume, which supporting the gas transport results. The thermal stability and β-relaxation temperature have also been studied for these copolymers.

Formation of ultrathin high-performance polyethersulfone hollow-fiber membranes

Abstract We have demonstrated, for the first time, that ultrathin skin-layer hollow-fiber membranes with a skin layer of 474 A can be prepared using mainly a one-polymer and one-solvent system. This is one of the thinnest skin-layer asymmetric hollow-fiber membranes that have ever been reported in the literature for air and gas separation. This work implies that, in order to yield a high-permeance polyethersulfone (PES) membrane with a skin layer of approximately 500 A, the addition of non-solvents into spinning dopes may not be the pre-condition to form ultrathin skin-layer hollow-fiber membranes for gas separation. The keys to fabricate ultrathin skin-layer hollow-fiber membranes are (1) to control the chemistry of the internal coagulant and the borefluid flow rate and (2) to have a dope exhibiting significant chain entanglement. The newly developed polyethersulfone (PES) hollow fibers have an O 2 N 2 selectivity of 5.80 with a permeance of 9.3 × 10 −6 cc(STP)/cm 2 s cmHg for O 2 at room temperature. The skin layer thickness was calculated to be 474 A. These hollow fibers were wet-spun from a 35 75 (weight ratio) PES/ N -methyl-pyrrolidone (NMP) dope using water as the external coagulant and 80 20 NMP/H 2 O as the bore fluid. The hollow fiber must be coated with a silicone elastomer. This work also suggests that in order to yield a high-permeance PES membrane with a skin layer of approximately 500 A, there might not exist a critical solvent molar volume when preparing the dope solvent mixture, as previously suggested by the Permea research group. SEM observation of skin nodules suggests that the skin layer thickness is less than 700 A.

Poly-/metal-benzimidazole nano-composite membranes for hydrogen purification

In this study, a novel scheme to fabricate nano-composite membrane materials containing fully dispersed nano-size zeolitic imidazolate frameworks (ZIFs) has been proposed for the first time. By mixing the as-synthesized ZIF-7 nano-particles without the traditional drying process with polybenzimidazole (PBI), the resultant membranes not only achieve an unprecedented ZIF-7 loading as high as 50 wt%, but also overcome the low permeability nature of PBI. The membranes exhibit characteristics of high transparency and mechanical flexibility, together with enhanced H2 permeability and ideal H2/CO2 permselectivity surpassing both neat PBI and ZIF-7 membranes. Advanced instrument analyses have confirmed the unique ZIF–polymer interface and elucidated the mixed matrix structure that contributes to the high ZIF loading and enhanced gas separation performance superior to the prediction from the Maxwell model. The high thermal stability, good dispersion of ZIF nanoparticles with minimal agglomeration and the attractive gas separation performance at elevated temperatures up to 180 °C indicate the practicability of this nano-composite material for hydrogen production and CO2 capture in realistic industrial applications under harsh and extreme environments.

High Performance Thin-Film Composite Forward Osmosis Hollow Fiber Membranes with Macrovoid-Free and Highly Porous Structure for Sustainable Water Production

The development of high-performance and well-constructed thin-film composite (TFC) hollow fiber membranes for forward osmosis (FO) applications is presented in this study. The newly developed membranes consist of a functional selective polyamide layer formed by highly reproducible interfacial polymerization on a polyethersulfone (PES) hollow fiber support. Using dual-layer coextrusion technology to design and effectively control the phase inversion during membrane formation, the support was designed to possess desirable macrovoid-free and fully sponge-like morphology. Such morphology not only provides excellent membrane strength, but it has been proven to minimize internal concentration polarization in a FO process, thus leading to the water flux enhancement. The fabricated membranes exhibited relatively high water fluxes of 32-34 LMH and up to 57-65 LMH against a pure water feed using 2 M NaCl as the draw solution tested under the FO and pressure retarded osmosis (PRO) modes, respectively, while consistently maintaining relatively low salt leakages below 13 gMH for all cases. With model seawater solution as the feed, the membranes could display a high water flux up to 15-18 LMH, which is comparable to the best value reported for seawater desalination applications.

Polyelectrolyte-Promoted Forward Osmosis–Membrane Distillation (FO–MD) Hybrid Process for Dye Wastewater Treatment

Polyelectrolytes have proven their advantages as draw solutes in forward osmosis process in terms of high water flux, minimum reverse flux, and ease of recovery. In this work, the concept of a polyelectrolyte-promoted forward osmosis-membrane distillation (FO-MD) hybrid system was demonstrated and applied to recycle the wastewater containing an acid dye. A poly(acrylic acid) sodium (PAA-Na) salt was used as the draw solute of the FO to dehydrate the wastewater, while the MD was employed to reconcentrate the PAA-Na draw solution. With the integration of these two processes, a continuous wastewater treatment process was established. To optimize the FO-MD hybrid process, the effects of PAA-Na concentration, experimental duration, and temperature were investigated. Almost a complete rejection of PAA-Na solute was observed by both FO and MD membranes. Under the conditions of 0.48 g mL(-1) PAA-Na and 66 °C, the wastewater was most efficiently dehydrated yet with a stabilized PAA-Na concentration around 0.48 g mL(-1). The practicality of PAA-Na-promoted FO-MD hybrid technology demonstrates not only its suitability in wastewater reclamation, but also its potential in other membrane-based separations, such as protein or pharmaceutical product enrichment. This study may provide the insights of exploring novel draw solutes and their applications in FO related processes.

Effect of Air-Gap Distance on the Morphology and Thermal Properties of Polyethersulfone Hollow Fibers

By using 30/70 polyethersulfone/NMP (N-methyl-2-pyrrolidone) solutions as an example, we have determined the role of air-gap distance on nascent fiber mor- phology, performance, and thermal properties. An increase in air-gap distance results in a hollow fiber with a less layer of fingerlike voids and a significant lower permeance. For the first time we have reported that the Tg of a dry-jet wet-spun fiber prepared from one-polymer/one-solvent systems is lower than that of a wet-spun fiber, and Tg decreases with an increase in air-gap distance. These interesting phenomena arise from the fact that different precipitation paths take place during the wet-spinning and dry-jet wet-spinning processes. Wet-spun fibers experience vigorous and almost instantaneous coagulations; it results in hollow fiber skins with a long-range random, unoriented chain entanglement, but loose structure. Dry-jet wet-spun fibers first go through a moisture-induced phase separation process and then a wet-phase inversion process; it results in external fiber skins with a short-range random, compact, and slightly oriented or stretched structure. As a result, the outskin of wet-spun fibers have a greater free volume and a higher first Tg than that of the dry-jet wet-spun ones. Both SEM (scanning electronic microscope) photomicrographs and DSC (differential scanning calorimeter) analyses support our conclusion. q 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1067-1077, 1997

Hyperbranched polyethyleneimine induced cross-linking of polyamide-imide nanofiltration hollow fiber membranes for effective removal of ciprofloxacin.

This study aims to develop a positively charged nanofiltration (NF) hollow fiber membrane for effective removal of ciprofloxacin from water. A novel NF membrane was fabricated by hyperbranched polyethyleneimine (PEI) induced cross-linking on a polyamide-imide hollow fiber support. The spongy-like, fully porous membrane support provides minimal transport resistance and sufficient mechanical strengths for water permeation under high pressures. It is found that the PEI modification significantly influences NF performance through the mechanisms of size exclusion, charge repulsion, and solute-membrane affinity. Specifically, after PEI induced cross-linking, the membrane pore size is significantly reduced. The membrane surface becomes more hydrophilic and positively charged. As a result of these synergic effects, the rejection of ciprofloxacin is substantially enhanced. Furthermore, experimental results show that the molecular weight of PEI has tremendous effect on NF performance of the as-modified membrane. The NF membrane modified by a high molecular weight PEI_60K exhibits the highest rejection, the lowest fouling tendency, and keeps a constant flux over the whole pH range. This study may have great potential for developing high-performance antifouling NF hollow fiber membranes for various industrial applications.

Morphological architecture of dual-layer hollow fiber for membrane distillation with higher desalination performance.

A new strategy to enhance the desalination performance of polyvinylidene fluoride (PVDF) hollow fiber membrane for membrane distillation (MD) via architecture of morphological characteristics is explored in this study. It is proposed that a dual-layer hollow fiber consisting of a fully finger-like macrovoid inner-layer and a sponge-like outer-layer may effectively enhance the permeation flux while maintaining the wetting resistance. Dual-layer fibers with the proposed morphology have been fabricated by the dry-jet wet spinning process via careful choice of dopes composition and coagulation conditions. In addition to high energy efficiency (EE) of 94%, a superior flux of 98.6 L m(-2) h(-1) is obtained during the direct contact membrane distillation (DCMD) desalination experiments. Moreover, the liquid entry pressure (LEP) and long-term DCMD performance test show high wetting resistance and long-term stability. Mathematical modeling has been conducted to investigate the membrane mass transfer properties in terms of temperature profile and apparent diffusivity of the membranes. It is concluded that the enhancement in permeation flux arises from the coupling effect of two mechanisms; namely, a higher driving force and a lower mass transfer resistance, while the later is the major contribution. This work provides an insight on MD fundamentals and strategy to tailor making ideal membranes for DCMD application in desalination industry.