Rheological Properties of the Solutions of Incompatible Polymer Blends

Sohn, Jeong-In,Ree, Taik-Yue Korean Chemical Society 1981 Bulletin of the Korean Chemical Society Vol.2 No.4

A blend polymeric system composed of poly(methyl methacrylate) (PMMA or PM) and polystyrene (PS) dissolved in chloroform was rheologically studied. The viscosities ${\eta}_{bl}$ of the blend system with various blending ratios ${\chi}$ changing from zero (pure PS solution) to unity (pure PMMA solution) were measured at $25{\circ}C$ as a function of shear rates ${\dot{s}}$ by using a Couette type viscometer. ${\eta}_{bl}$ at a given ${\dot{s}}$ decreased exponentially with ${\chi}$ reaching asymptotic constant value of ${\eta}_{bl}$ ; ${\eta}_{bl}$ at a given ${\chi}$ is greater at a smaller ${\dot{s}}$. These results are explained by using Ree-Erying's theory of viscosity, ${\eta}_{bl}=(x_1{\beta}_1/{\alpha}_1)_{b}_1+ (x_2{\beta}_2/{\alpha}_2)_{bl}[sinh^{-1}{\beta}_2(bl) {\dot{s}}]/{\beta}_2(bl){\dot{s}}$. The Gibbs activation energy ${\Delta}G_i^\neq$(i = 2 for non-Newtonian units) entering into the intrinsic relaxation time ${\beta}$ is represented by a linear combination ${\Delta}G_i^\neq(bl) ={\chi}{\Delta}G_i^{\neq}_{iPM}+(1-{\chi}){\Delta}G_i^{\neq}_{iPS}$;the intrinsic shear modulus$[[\alpha}_i]^{-1}$ is also represented by $[{\alpha}_i(bl)]^{-1}={\chi}[{\alpha}_{iPM}]^{-1}+(1-{\chi})[{\alpha}_{iPS}]^{-1}$ and the fraction of area on a shear surface occupied by the ith flow units $x_i(bl)$ is similarly represented, i.e., $x_i(bl) = {\chi}x_{iPM}+(1-{\chi})x_{iPS}$. By using these ideas the Ree-Eyring equation was rewritten which explained the experimental results satisfactorily.

The Solvolysis of Benzoyl Chloride in Water-Acetone Mixtures Under High Pressure

Jee, Jong-Gi,Ree, Taik-Yue Korean Chemical Society 1987 Bulletin of the Korean Chemical Society Vol.8 No.1

By using a complete rate constant($k_e$) which treats a solvent (water) as a reactant, and a conventional rate constant($k_c$), which ignores the solvent in describing the rate, the parameters ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were introduced. These quantities represent the volume change, the enthalpy change, and the entropy change accompanying the electrostriction which occurs when solvent molecules condense on the activated complex. The authors measured the rates of the solvolysis of benzoyl chloride in water-acetone mixtures at $15^{\circ}$ to $30^{\circ}C$ and 1 bar to 2500 bars. Applying the authors' theory to the experimental results, the parameters, ${\Delta}V^{\neq}_s,\;{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ were evaluated, and it was found that they are all negative, indicating that water dipoles condense on the activated complex. They also proposed the following equations: ${\Delta}H^{\neq}_c\;=\;{\Delta}H^{\neq}_e\;+\;{\Delta}H^{\neq}_s\;and\; {\Delta}S^{\neq}_c\;=\;{\Delta}S^{\neq}_e\;+{\Delta}S^{\neq}_s\;,\;where\;{\Delta}H^{\neq}_c\;and\;{\Delta}H^{\neq}_c\;and\;{\Delta}S^{\neq}_s $are the activation enthalpy change and the activation entropy change for the conventional reaction rate, respectively, and ${\Delta}H^{\neq}_e$ and ${\Delta}S^{\neq}_e$ are the corresponding quantities for the complete reaction rate. The authors proposed that for the $SN_1$ type, all the quantities, ${\Delta}V^{\neq}_s,\;{\Delta}S^{\neq}_s\;,{\Delta}H^{\neq}_s\;and\;{\Delta}S^{\neq}_s$ are comparatively large, and for the $SN_2$ type, these quantities are smaller than for the $SN_1$ type, and occasionally the case ${\Delta}S^{\neq}_e$ < 0 occurs. Using these criteria, the authors concluded that at high temperature, high pressure and for a high water content solvent, the SN_1$ type mechanism predominates whereas in the reversed case the $SN_2$M type predominates.

Rheological Properties of Polystyrene Degraded by Mechanical Forces

Oh, In-Joon,Ree, Taik-Yue Korean Chemical Society 1981 Bulletin of the Korean Chemical Society Vol.2 No.4

Polystyrene was degraded by using a vibrating ball mill. The viscosities and molecular weights of the degraded products were measured, and the decrease of viscosity $[\eta}$ with ${\dot{s}}$ (rate of shear) observed for the degraded products were analyzed by applying the Ree-Eyring equation for viscous flow. The variation of the parameters $x_2$/{\alhpa}_2,{\beta}_2$ and $x_1{\beta}_1/{\alpha}_1$ in the equation were explained by the fracture of polymer molecules by mechanical force. The electron paramagnetic resonance spectrum of the degraded sample was taken, and it was confirmed that free radicals were produced by the chain-scission of polystyrene.

Non-Newtonian Intrinsic Viscosities of Biopolymeric and Non-biopolymeric Solutions (II)

Jang, Chun-Hag,Kim, Chang-Hong,Ree, Taik-Yue Korean Chemical Society 1987 Bulletin of the Korean Chemical Society Vol.8 No.4

This paper is a continuation of our previous $paper,^1$ and deals with Eq.(1) (see the text), which was theoretically derived in the $paper,^1$$ [{\eta}]^f\; and\; [{\eta}]^0$ is the intrinsic viscosity at stress f and f = O, respectively. Equation (1) predicts how $[{{\eta}}]^f / [{\eta}]^0$ changes with stress f, relaxation time ${\beta}_2$ of flow unit 2 and a constant $c_2$ related with the elasticity of molecular spring of flow unit 2. In this paper, Eq.(1) is applied to a biopolymer, e.g., poly (${\gamma}$-benzyl L-glutamate), and nonbiopolymers, e.g., polyisobutylene, polystyrene, polydimethylsiloxane and cellulose triacetate. It was found that the $c_2$ factor is zero for non-biopolymers while $c_2{\neq}0$ for biopolymers as found $previously.^1$ Because of the non-Newtonian nature of the solutions, the ratio $[{{\eta}}]^f / [{\eta}]^0$ drops from its unity with increasing f. We found that the smaller the ${\beta}_2,$ the larger the $f_c$ at which the viscosity ratio drops from the unity, vice versa.

Effect of Zeta-Potential on the Viscosity of Clay-Water Suspension

Lee, Young-Seek,Ree, Jong-Baik,Ree, Taik-Yue Korean Chemical Society 1982 Bulletin of the Korean Chemical Society Vol.3 No.3

Viscosity and zeta-potential of 11.0 wt. % aqueous bentonite suspension containing various electrolytes and hydrogen-ion concentration were measured by using a Couette type automatic rotational viscometer and Zeta Meter, respectively. The effects of pH and elcctrolytes on the rheological properties of the suspension were investigated. A system, which has a large zeta-potcntial, has a small intrinsic relaxation time ${\beta}$ and a small intrinsic shear modulus $1/{\alpha}$ in the Ree-Eyring generalized viscosity equation, i.e., such a system has a small viscosity value, since ${\eta}={\beta}/{\alpha}$. In general, a stable suspension system has large zeta-potential. The stability condition of clay-water suspension can be estimated by viscometric method since stable suspension generally has small viscosity. The correlation between the stability, viscosity and zeta-potential has been explained by the Ree-Eyring theory of viscous flow.

Fourier-Transform Infrared and Calorimetric Studies about the Influence of Tacticity of Poly(methyl methacrylate) on the Compatibility with Poly(ethylene oxide)

John, Eun-Sook,Jeon, Seung-Ho,Ree, Taik-Yue Korean Chemical Society 1989 Bulletin of the Korean Chemical Society Vol.10 No.2

Calorimetric study in conjunction with Fourier-transform infrared (FTIR) spectroscopic study was carried out on the blends of poly(ethylene oxide) (PEO) with isotactic, atactic and syndiotactic poly(methyl methacrylate) (i-, a-, and s-PMMA). From the differential scanning calorimetric (DSC) measurements, the three types of blends show a depression of the melting temperatures. This indicates that PEO is compatible with i-, a-, and s-PMMA. But the largest melting point depressions of PEO are always found in the blends with s-PMMA. For PEO/a-PMMA and PEO/s-PMMA, the degree of crystallinity as a function of composition deviates substantially from that of the ideal blend in which no interaction between the components exists. The FTIR spectra of all three types of blends are recorded. In order to observe the microstructural changes of PEO in blends, we analyzed the spectra using digital weighted subtraction and addition techniques. It was concluded that the microstructures of PEO are strongly perturbed by the PMMA's. Among these blends PEO microstructure in PEO/s-PMMA blends is most greatly influenced. It indicates that the blending is most preferred with s-PMMA than a- and i-PMMA. It can be explained on the basis of the molecular structure of PMMA's.

Enhanced Cancer Immunotherapy by In situ Nanomicelle-generating Dissolving Microneedles

Nak Won Kim,Sun-Young Kim,Jung Eun Lee,Yue Yin,Jong Han Lee,Su Yeon Lim,E Seul Kim,Hong Kee Kim,Sohyun Kim,Jung-Eun Kim,Min Sang Lee,Yong Taik Lim,Ji Hoon Jeong 한국고분자학회 2018 한국고분자학회 학술대회 연구논문 초록집 Vol.43 No.2

Targeted cellular delivery of robust enzyme nanoparticles for the treatment of drug-induced hepatotoxicity and liver injury

Lee, Min Sang,Kim, Nak Won,Lee, Jung Eun,Kim, Myung Goo,Yin, Yue,Kim, Sun Young,Ko, Bo Sung,Kim, Aeseon,Lee, Jong Han,Lim, Su Yeon,Lim, Dong Woo,Kim, Sun Hwa,Park, Ji Won,Lim, Yong Taik,Jeong, Ji Hoon Elsevier 2018 Acta Biomaterialia: structure-property-function re Vol.81 No.-

<P><B>Abstract</B></P> <P>Direct delivery of proteins into cells has been considered an effective approach for treating the protein-related diseases. However, clinical use of proteins has still been limited due to their instability in the blood and poor membrane permeability. To achieve an efficient cellular delivery of the protein to target cells via a systemic administration, a multifunctional carrier system having desirable stability both in the blood stream and the cells, specific cell-targeting property and endosomal escape functions may be required. In this study, we prepared a catalytic nanoparticle containing an active enzyme by cross-tethering multiple superoxide dismutase (SOD) molecules with catechol-derivatized hyaluronic acid (HA). The permeable shell of hydrophilic HA chains effectively protects the enzyme from degradation in the blood after intravenous administration and provides an additional function for targeting hepatocytes expressing HA receptor (CD44). The structure and catalytic activity of the enzyme molecules in the nanoparticle were not significantly compromised in the nanoparticle. In addition, ultra-small calcium phosphate nanoparticles (USCaP, 2–5 nm) were crystalized and decorated on the surface of the nanoparticle for the efficient endosomal escape after cellular uptake. The SOD-containing nanoparticle fortified with USCaP was used for the treatment of acetaminophen (APAP)-induced fulminant hepatotoxicity and liver injury. The nanoparticle achieved the efficient hepatic cellular delivery of SOD via a systemic administration and resulted in efficient removal of reactive oxygen species (ROS) in the liver and remarkable improvement of APAP-induced hepatotoxicity and liver injury in animals.</P> <P><B>Statement of Significance</B></P> <P>Despite the enormous therapeutic potential, the intracellular delivery of proteins has been limited due to their poor membrane permeability and stability. In this study, we demonstrated an active enzyme-containing nanoparticle functionalized by hyaluronic acid and ultra-small size calcium phosphate nanoparticles (2–5 nm) for targeted cellular delivery of superoxide dismutase (SOD). The nanoparticle was designed to integrate all the essential functions, including serum stability, target specificity, and endosomal escape capability, for a systemic delivery of a therapeutic protein to the cells of the liver tissue. The intravenous administration of the nanoparticle efficiently removes reactive oxygen species (ROS) in the liver and remarkably improves the drug-induced hepatotoxicity and the progress of fulminant liver injury in an acetaminophen-overdose animal model.</P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>