Permeability characteristic of polyelectrolyte complex capsule membranes: Effect of preparation condition on permeability

Because polyelectrolyte complex formation is known to depend on charge densities of polyelectrolytes, influence of pH condition in the preparation of the polyelectrolyte complex capsules on their permeability characteristic for phenylethylene glycol was examined. Partly crosslinked polyelectrolyte complex capsules were prepared by addition of an aqueous poly(acrylic acid) solution into an aqueous poly(ethylenimine) or L-histidine attached poly(ethylenimine) (ethylenimine unit/L-histidine residue: 5/1, mol/mol) solution and subsequent crosslinking under various pH conditions. Although poly(acrylic acid) and poly(ethylenimine) change their charge density depending on pH in an aqueous solution, the resultant capsules prepared at pHs 7, 6, and 5 show similar permeation properties under neutral and acidic conditions. By contrast, when L-histidine-attached poly(ethylenimine) was used instead of the unmodified polymer as the capsule membrane component, the resultant capsules prepared at pHs 8, 7, and 6 revealed remarkable difference in the permeability under neutral and acidic conditions. Because the ionization of an imidazolyl group, whose pKa is 6, on the L-histidine-attached poly(ethylenimine) is influenced significantly by pH near its pKa, such situation might affect density of networks formed by the ionic bonds in the polyelectrolyte complex membrane and resulted in the permeability difference. © 1996 John Wiley & Sons, Inc.     

Effect of hydrophobic units on the pH‐responsive release property of polyelectrolyte complex capsules

Copolymers of acrylic acid and styrene with styrene unit contents of 2.7, 5.7, and 9.5% were synthesized by free radical copolymerization. Poly(ethylenimine)s with benzylated unit contents of 2.4, 6.0, 10.6, and 16.7% were obtained by the reaction of poly(ethylenimine) with benzyl bromide. Polyelectrolyte complex capsules consisting of these polymers were prepared. Influence of the hydrophobic units on pH‐responsive release property of the capsules was studied using phenylethylene glycol as a permeant. When the copolymer with styrene unit content of 5.7% or the poly(ethylenimine) with the benzylated unit content of 2.4–10.6% was used as the membrane components, the permeability of the capsule membrane became minimum and was 10–20 fold lower than that of the poly(acrylic acid)–poly(ethylenimine) complex capsule membrane in the pH region between 3 and 7. In contrast, the hydrophobic units did not lower the permeability of the capsule membranes significantly below pH 3 and above pH 7. Thus, the capsule membranes containing hydrophobic units exhibited remarkable permeability changes in the narrow pH regions of 2–3 and 7–9. Also, the capsule containing the benzylated PEI in the membrane changed the release rate of the contents very quickly, in response to the ambient pH alteration. Therefore, polyelectrolyte complex capsules, which are highly sensitive to pH change, were obtained by using the polyelectrolytes with the hydrophobic units as membrane components. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 72: 1763–1773, 1999     

Photoresponsive permeability of polyelectrolyte complex capsule membrane containing triphenylmethane leucohydroxide residues

To develop a functional capsule, which can be controlled to release materials entrapped in the inner aqueous space responding to light, partly crosslinked poly(acrylic acid)–poly-ethylenimine complex capsules containing a copolymer of acrylic acid and bis[4-(dimethylamino)phenyl](4-vinylphenyl)methyl leucohydroxide as an additional membrane component with radii of ca. 3 mm have been prepared. The triphenylmethane derivative on the copolymer dissociated into an ion pair under ultraviolet light irradiation in the weak alkaline region. Permeation of p-toluenesulfonate through the capsule membrane was enhanced significantly by the photoirradiation after a several minutes time lag under a weak alkaline condition. The photoinduced increase in permeability of the capsule was pH-dependent. The maximum effect of light on the permeability was observed near pH 8, whereas less enhancement was observed above or below the pH value. When the irradiation of the light was stopped, permeation of the permeant decreased. The photoresponsive permeability change of the capsule membrane can be carried out reversibly. © 1995 John Wiley & Sons, Inc.     

Temperature‐dependent permeability of polyelectrolyte complex capsule membranes having N‐isopropylacrylamide domains

As a microcapsule with temperature sensitivity, poly(methacrylic acid)–polyethylenimine complex capsules containing N‐isopropylacrylamide units were designed. Two kinds of copolymers of methacrylic acid and N‐isopropylacrylamide were synthesized by free‐radical copolymerization. Partly crosslinked poly(methacrylic acid)–polyethylenimine complex capsules containing the methacrylic acid–N‐isopropylacrylamide copolymers were prepared at 40 or 25°C. The permeation of phenylethylene glycol through the capsule membranes was investigated. Permeability of the capsules prepared at 25°C increased monotonously with increasing temperature from 10 to 50°C. Permeability of the capsules prepared at 40°C also increased with increasing temperature up to 25°C but decreased above 30°C. Also, the degree of swelling of the membranes prepared at 40°C decreased above 30°C. Differential scanning calorimetry measurement showed that N‐isopropylacrylamide units underwent more efficient transition in the capsule membranes prepared at 40°C than in the membranes prepared at 25°C. The capsule membranes prepared at 40°C might have domains in which N‐isopropylacrylamide units are concentrated, whereas these units should distribute uniformly in the capsule membranes made at 25°C. Such a difference in distribution of N‐isopropylacrylamide units might result in the different permeation property of the capsule membranes. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2703–2710, 2000     

Separation of liquid mixtures by using polymer membranes. III. Grafted poly(vinyl alcohol) membranes in vacuum permeation and dialysis

A series of poly(vinyl alcohol) membranes were modifed by radiation-induced graft copolymerization with acrylic acid and methacrylic acid monomers. These grafted poly(vinyl alcohol) membranes were then tested for their separation and permeability characteristics in vacuum permeation and dialysis experiments. The permselectivity of the membranes toward methanol and water was studied on a vacuum permeation apparatus at 30, 40, and 50°C. The permeation process was found to be a temperature-activated process. The logarithm of the permeation rate varied linearly with the reciprocal of the absolute temperature. The permeability of the grafted membranes was found to increase with the degree of grafting, with no appreciable selectivity toward water in binary mixtures. The acrylic acid-grafted membranes generally showed greater improvement in permeability than the methacylic-grafted membranes. The permeability of the grafted membranes toward methanol, sodium chloride, urea, creatinine, and uric acid was studied in a dialyzer. In all cases, the grafted membranes showed an improved permeability toward these solutes over the commercial poly(vinyl alcohol) membranes. The dialysis results were then compared with those obtained for dialysis-grade cellophane membranes. For the case of sodium chloride, urea, and methanol, the permeability of the grafted membranes was comparable to that of cellophane. A comparison of commercial and grafted poly(vinyl alcohol) membranes in their permeability toward ionic solutes exhibited somewhat anomalous behavior in that the permeability of the commercial membranes was higher than that of the grafted membranes. This related to the ionic nature of the modified membrane. The permeability coefficients determined in the dialysis experiments were found to be directly related to the degree of hydration of the grafted membrane. This behavior was attributed to changes in the size and shape of voids within the membrane structure.     

Effects of different parameters on the characteristics of chitosan–poly(acrylic acid) nanoparticles obtained by the method of coacervation

Chitosan–poly(acrylic acid) polyelectrolyte complex nanoparticles were prepared by coacervation under mild experimental conditions without the use of any organic solvents or surfactants. The influence of some experimental parameters such as the pH of the polyelectrolyte solutions, their concentrations, and the purification procedure on the particle dimensions and their size distribution was studied in detail. The physicochemical properties of the obtained complex were characterized with Fourier transform infrared spectroscopy, transmission electron microscopy, scanning electron microscopy, and dynamic light scattering. It was found that for solution concentrations below 0.1 wt %, it was possible to obtain suspensions of nanometer‐sized particles. Furthermore, it was established that the pH values of the reactant solutions had a great influence on both the particle size and the yield of the complex that was formed. The most convenient pH values for obtaining chitosan–poly(acrylic acid) particles with a nanometric size and optimum yield (near 90%) were found to be 4.5–5.5 for chitosan and 3.2 for poly(acrylic acid). Additionally, the effects of dialysis and ultrasonic treatment on the stability of complex suspensions, prepared under different experimental conditions, were clarified so that recommendations could be made to bring this system into practical use. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Membrane properties of porous and expanded poly(tetrafluoroethylene) films grafted with hydrophilic monomers and their permeation behavior

Porous and expanded poly(tetrafluoroethylene) (pPTFE and ePTFE) films grafted with methacrylic acid (MAA) and 2-(dimethylamino)ethyl methacrylate (DMA) were prepared by the combined use of the plasma treatment and photografting. Their membrane properties and permeation behavior to saccharides and dextrans were investigated. Water absorptivity and electrical conductivity considerably increased around the grafted amounts at which the individual grafted polymer chains reached the center of each PTFE film. The glucose permeability of all four types of grafted pPTFE and ePTFE films showed the maximum values at pH 8, and grafted ePTFE films had higher permeabilities than grafted pPTFE films. It was made clear from the viscometric measurements of the aqueous solutions of polyMAA (PMAA) and polyDMA (PDMA) that the glucose permeability of MAA-grafted pPTFE (MAA-g-pPTFE) and MAA-grafted ePTFE (MAA-g-ePTFE) films increased more as grafted PMAA chains expanded. Those of DMA-grafted pPTFE (DMA-g-pPTFE) and DMA-grafted ePTFE (DMA-g-ePTFE) films increased more as grafted PDMA chains contracted. These results explain that the glucose permeability of the grafted pPTFE and ePTFE films depend not only on the grafted amount but also on the distribution of the corresponding grafted polymer chains in the direction of depth inside both PTFE films. The on-off regulation of permeation for DMA-g-pPTFE and DMA-g-ePTFE films could be repeated in response to the alternate temperature change and their on-off regulation patterns were completely opposite to those of many other hydrogel samples consisting of thermosensitive polymers with lower critical solution temperatures. In addition, it was found from permeation experiments, using three types of saccharides and dextrans with different molecular weights as a permeant, that permeation flux of DMA-g-ePTFE films decreased with an increase in molecular weight of the permeant. Separation factors showed the maximum value at the grafted amount of 0.8 mmol/g. The tensile strength measurements showed the grafted pPTFE and ePTFE films possessed adequate strength in the waterswollen state to be of use for a functional membrane. DMA-g-ePTFE films are most suitable for a separation membrane of polymeric species of four grafted PTFE films. © 1996 John Wiley & Sons, Inc.     

Poly(acrylic acid)–poly(vinyl alcohol) semi- and interpenetrating polymer network pervaporation membranes

A series of poly(acrylic acid) (PAA)–poly(vinyl alcoho) (PVA) semiinterpenetrating (SIPN) and interpenetrating (IPN) polymer network membranes were prepared by crosslinking PVA alone or by crosslinking both PVA and PAA. Glutaraldeyde and ethylene glycol were used as crosslinking agents for the PVA and PAA networks, respectively. The presence of PAA increases the permeability of the membranes while the presence of PVA improves their mechanical and film-forming properties. The mechanical properties of the membranes were investigated via tensile testing. These hydrophilic membranes are permselective to water from ethanol–water mixture and to ethanol from ethanol–benzene mixtures. The IPN membranes were employed for the former mixtures and the SPIN membranes for the latter, because the IPN ones provided too low permeation rates. The permeation rates and seperation factors were determined as functions of the IPN or SIPN composition, feed composition, and temperature. For the azeotropic ethanol–water mixture (95 wt % ethanol), the separation factor and permeation rate at 50°C of the PAA-PVA IPN membrane, containing 50 wt % PAA, were 50 and 260 g/m²h, respectively. For the ethanol–benzene mixture, the PAA–PVA SIPN membranes had separation factors between 1.4 and 1200 and permeation rates between 6 and 550 g/m²h, respectively, depending on the feed composition and temperature. © 1996 John Wiley & Sons, Inc.     

Preparation of pH‐sensitive poly(vinyl alcohol‐g‐methacrylic acid) and poly(vinyl alcohol‐g‐acrylic acid) hydrogels by gamma ray irradiation and their insulin release behavior

A series of pH‐responsive hydrogels were studied as potential drug carriers for the protection of insulin from the acidic environment of the stomach before releasing in the small intestine. Hydrogels based on poly(vinyl alcohol) networks grafted with acrylic acid or methacrylic acid were prepared by a two‐step process. Poly(vinyl alcohol) hydrogels were prepared by gamma ray irradiation (50 kGy) and then followed by grafting either acrylic acid or methacrylic acid onto these poly(vinyl alcohol) hydrogels with subsequent irradiation (5–20 kGy). These graft hydrogels showed pH‐sensitive swelling behavior and were used as carriers for the controlled release of insulin. The in vitro release of insulin was observed for the insulin‐loaded hydrogels in a simulated intestinal fluid (pH 6.8) but not in a simulated gastric fluid (pH 1.2). The release behavior of insulin in vivo in a rat model confirmed the effectiveness of the oral delivery of insulin to control the level of glucose. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 636–643, 2004     

Permeation of solutes through interpenetrating polymer network hydrogels composed of poly(vinyl alcohol) and poly(acrylic acid)

The swelling behaviors of poly(vinyl alcohol)–poly(acrylic acid) (PVA–PAAc) interpenetrating networks (IPN) hydrogels in the presence of electrolytes were studied. The ionized carboxylic group within IPN hydrogels at pH 7 strongly interacted with electrolytes in the medium and caused anomalous swelling pattern. The permeabilities of 5 representative solutes were regulated as a function of temperature, pH, ionic strength, solute size, and ionic properties of solutes. The permeation of nonionic solutes followed the swelling behaviors dependent on external stimuli, including the above factors. However, the ionic solutes showed different trends in their permeation through IPN hydrogels. © 1998 John Wiley & Sons, Inc. J Appl Polm Sci 69: 479–486, 1998     

Permeability of synthetic poly(α-amino acid) membranes to oxygen dissolved in water

Membranes of synthetic poly(α-amino acids), namely, poly(γ-methyl L -glutamate) (PMLG), poly(γ-benzyl L -glutamate) (PBLG), poly(L -glutamic acid) (PLGA), poly(L -methionine) (PLM), and poly(N^?-carbobenzoxy-L -lysine) (PCLL), were prepared and their permeabilities of oxygen dissolved in water were measured in the 8–50°C temperature range using an oxygen electrode. Permeation curves for the poly(α-amino acid) membranes did not approach steady-state currents because of membrane degradation. To eliminate this, the membranes were laminated between polystyrene membranes; thus, the poly(α-amino acid) membranes came in direct contact with neither cathode surface nor electrolyte solution. No effect of membrane thickness on the permeability was observed. The Arrhenius plots of permeability coefficients for PCLL appear to change slope at about 22°C. This is consistent with the diffusion of oxygen in PCLL through the side-chain regions between helices. Comparisons between the permeability of oxygen dissolved in water and permeability of gaseous oxygen obtained by the high-vacuum method and between the activation energy of permeation of dissolved oxygen and that of gaseous oxygen were made in order to elucidate the effect of water on the oxygen permeation of each polymer. The permeability of the poly(α-amino acid) membranes to dissolved oxygen appears to depend on the properties of the side chains of the polymers.     

Synthesis of double‐hydrophilic poly(methylacrylic acid)–poly(ethylene glycol)–poly(methylacrylic acid) triblock copolymers and their micelle formation

The aim of the work reported was to synthesize a series of double‐hydrophilic poly(methacrylic acid)‐block‐poly(ethylene glycol)‐block‐poly(methacrylic acid) (PMAA‐b‐PEG‐b‐PMAA) triblock copolymers and to study their self‐assembly behavior. These copolymeric self‐assembly systems are expected to be potential candidates for applications as carriers of hydrophilic drugs. Bromo‐terminated difunctional PEG macroinitiators were used to synthesize well‐defined triblock copolymers of poly(tert‐butyl methacrylate)‐block‐poly(ethylene glycol)‐block‐poly(tert‐butyl methacrylate) via reversible‐deactivation radical polymerization. After the removal of the tert‐butyl group by hydrolysis, double‐hydrophilic PMAA‐b‐PEG‐b‐PMAA triblock copolymers were obtained. pH‐sensitive spherical micelles with a core–corona structure were fabricated by self‐assembly of the double‐hydrophilic PMAA‐b‐PEG‐b‐PMAA triblock copolymers at lower solution pH. Transmission electron microscopy and laser light scattering studies showed the micelles were of nanometric scale with narrow size distribution. Solution pH and micelle concentration strongly influenced the hydrodynamic radius of the spherical micelles (48–310 nm). A possible reason for the formation of the micelles is proposed. Copyright © 2010 Society of Chemical Industry     

A mucoadhesive polymer prepared by template polymerization of acrylic acid in the presence of poly(ethylene glycol) macromer

A new mucoadhesive polymer complex was prepared by the template polymerization of acrylic acid with poly(ethylene glycol) macromer (PEGM) as a template polymer. Fourier transform infrared results showed that the poly(acrylic acid) (PAA)/PEGM mucoadhesive polymer complex was formed by hydrogen bonding between the carboxyl groups of PAA and the ether groups of PEGM. The glass‐transition temperature of the PAA/PEGM mucoadhesive polymer complexes was shifted to a lower temperature as the repeating unit ratio of PAA/PEGM in the complex decreased. The dissolution rate of the PAA/PEGM mucoadhesive polymer complex was much slower than that of the PAA/poly(ethylene glycol) (PEG) mucoadhesive polymer complex and was dependent on the pH and molecular weight of PEGM. The mucoadhesive force of the PAA/PEGM mucoadhesive polymer complexes was stronger than that of commercial Carbopol 971P NF and almost the same as that of the PAA/PEG mucoadhesive polymer complex. The PAA/PEGM interpolymer complex seemed to be a better mucoadhesive polymer matrix than the PAA/PEG interpolymer complex. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1904–1910, 2002     

Structure and properties of the polyelectrolyte complex of chitosan with poly(methacrylic acid)

The structure and properties of the polyelectrolyte complex composed of chitosan (CS) and poly(methacrylic acid) (PMAA) were studied in aqueous solutions using UV‐visible transmittance measurements, a fluorescence probe technique, and transmission electron microscopy. The thermal properties of the solid complex were measured using differential scanning calorimetry. The results showed that the complex optimum molar ratio (in monomer unit) of CS to PMAA is 1:4 at pH = 4.0, that is, there is an optimum complex between CS and PMAA when the feed ratio (in molar monomer unit) of CS to PMAA is 1:4 and an ionic bond between the amino ion group and carboxylate group can be formed on average every four carboxylate (or carboxyl) groups. The conformation of PMAA changed from a hypercoiled to a loose coil on complexation, and the pH‐ and salt‐sensitive range of the polyelectrolyte complex was obviously different from that of CS or PMAA. The formation process of the complex under various external conditions is discussed in detail. Transmission electron microscopy revealed that the sizes of CS–PMAA complex particles increased with increasing pH or salt concentration, and a change in morphology of the complex was observed. Thermal analysis further revealed that there was a change of structure and properties on blending in aqueous solutions. Copyright © 2007 Society of Chemical Industry     

Complexation between poly(methacrylic acid) and poly(vinylpyrrolidone)

The complexation between poly(methacrylic acid) (PMAA) and poly(vinylpyrrolidone) (PVP) in aqueous phase was studied by various fluorescence techniques, including fluorescence anisotropy measurements, fluorescence probe studies, and nonradiation energy transfer. It was demonstrated that the complexation of PMAA with PVP occurs within a pH range of 1 to 5 and along with complexation, the conformation of PMAA changed from a hypercoiled to a loosely coiled form. The complex ratio between the two polymers is 2:1 (PMAA/PVP, in monomer unit). Salt effect studies showed that the complexation occurred due to formation of hydrogen bonds between the two polymers. Based on these conclusions and the “connected cluster model” for PMAA at low pH, a “ladder with connected cluster” model was proposed for the structure of PMAA/PVP complex formed at low pH. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 620–627, 2001     

Moisture sorption of polyelectrolyte complex between poly(acrylic acid) and poly(4-vinylpyridine)

Successive differential sorptions have been measured for the system polyelectrolyte complex of poly(acrylic acid)/poly(4-vinylpyridine) + water vapor. The sorption data revealed that the sorption process of water vapor in the complex is controlled not only by diffusion mechanism but also by relaxation mechanism of polymer chains. It has been considered that the complex is composed of a loosely crosslinked, slightly ionized, and relatively homogeneous network structure. The sorption–desorption kinetics have also been investigated for the region of intermediate and high vapor pressures. The interval sorption–desorption curves demonstrated that the complex has the nature of the hysteresis effect in sorptions. It has been concluded that the appearance of sorption hysteresis is due to the depression of mobility of polymer chains resulting from crosslinks between carboxyl groups and pyridine rings.     

pH‐controlled uphill transport of boric acid through a poly(vinyl alcohol) (PVA) membrane

The uphill transport of boric acid in aqueous solutions through a thermal‐crosslinked poly(vinyl alcohol) (PVA) membrane was investigated. A normal permeation caused by the concentration difference of the boron along the PVA membrane was observed for equal pH conditions at both sides of the membrane, and higher flux was observed under an acidic condition at pH = 5.0 than under a basic condition at pH = 10.0. When the pH of one side is kept pH = 5.0 (acid side) and the other side was kept at pH = 10.0 (base side), uphill transport of boric acid from the acid side to the base side was observed under an equal initial concentration of both sides. Such an uphill transport was also observed against the concentration difference under the condition in which the initial concentration of the base side was higher than that of the acid side. The uphill transport could be explained by the difference in the permeation rates through the PVA membrane between B(OH)₃, the dominant form under lower pH, and B(OH)₄^?, the dominant form under higher pH, which makes a complex with diols in PVA. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1451–1455, 2007     

Proton conductivity and methanol permeability of sulfonated poly(vinyl alcohol) membranes modified by using sulfoacetic acid and poly(acrylic acid)

Sulfonated poly(vinyl alcohol) (PVA) for use as a proton conductive membrane in a direct methanol fuel cell (DMFC) was prepared by reacting the PVA with sulfoacetic acid and poly(acrylic acid). The effects of the amount of sulfoacetic acid and poly(acrylic acid) on proton conductivity, methanol permeability, water uptake, and ion exchange capacity (IEC) of the sulfonated PVA membranes were investigated by using impedance analysis, gas chromatography, gravimetric analysis, and titration techniques, respectively. The water uptake of the membranes decreased with the amount of the sulfoacetic acid and the amount of poly(acrylic acid) used. The proton conductivity and the IEC values of the membranes initially increased and then decreased with the amount of the sulfoacetic acid. The methanol permeability of the sulfonated PVA membranes decreased continuously with the amount of the sulfoacetic acid. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Release of diclofenac through gluteraldehyde crosslinked poly(vinyl alcohol)/poly(acrylic acid) alloy membranes

A controlled‐release preparation of diclofenac sodium for transdermal administration has been developed. Poly(vinyl alcohol) (PVA) and PVA/poly(acrylic acid) (PAA) alloy membranes were prepared from a solvent‐casting technique using different PVA/PAA (v/v) ratios. The release of the drug from the membrane was evaluated under in vitro conditions at pH 7.4. The delivery system provided linear release without time lag, burst effect, and boundary layer resistance. Effects of variables such as film thickness and PVA/PAA ratio on the permeation behavior of the polymeric membranes were discussed. The optimal PVA/PAA was determined as 50/50. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 72–77, 2004     

Phase Behavior of Polyelectrolyte Complexes and Rheological Behavior of Alumina suspensions for Direct Ink Writing

Polyelectrolyte complexes have a bright prospect for fabricating 3D periodic structures by direct ink writing. The phase behavior of complexes containing poly(acrylic acid) and poly(ethylenimine) and rheological behavior of Al₂O₃ colloidal suspensions are characterized. The results reveal that the pH value of solution takes an important role on the phase behavior of polyelectrolyte complexes. When the [COOH]:[NH_x] ratio is higher than or lower than the critical value of 0.6, the pH range of turbid complex solutions narrows down and meanwhile moves to acidic or alkaline region, respectively. The addition of pH regulators prompts polyelectrolyte exchange reaction and soluble complexes are suitable for preparation of cera‐mic suspensions. The polyelectrolyte suspensions with linear viscoelasticity at lower shear stress and good fluidity at higher shear stress are identified for direct ink writing of 3D structures with microsized feature.