Biomedical subjects

Taihyun Chang

Publications and source records attributed to Taihyun Chang.

13 recordsLinked to original sources

PubMed2006

Characterization of polydisperse poly(vinyl chloride) by temperature gradient interaction chromatography.

Temperature gradient interaction chromatography (TGIC) was employed to fractionate a commodity polymer, poly(vinyl chloride) (PVC) with wide molecular weight distribution (MWD). The TGIC fractionation was carried out with C18 bonded silica and dimethylformamide (DMF) as the stationary and mobile phase, respectively. TGIC exhibited a high resolution to fractionate the PVC into the fractions with a narrow MWD comparable to the anionically polymerized standards. In combination with light scattering detection, TGIC is able to characterize the polymers with wide MWD and shows a good potential to be further developed as a new preparative fractionation method of synthetic polymers.

Chromatography, Gel↗

PubMed2005

Separation of branched polystyrene by comprehensive two-dimensional liquid chromatography.

Branched polystyrenes (PS) featuring a bivariate distribution in the molecular weight and in the number of branches were characterized by comprehensive two-dimensional liquid chromatography (2D-LC). The branched PS were prepared by anionic polymerization using n-butyl Li as an initiator and a subsequent linking reaction with p-(chlorodimethylsilyl)styrene (CDMSS). The n-butyl Li initiator yields polystyryl anions with broad molecular weight distribution (MWD) and the linking reaction with CDMSS yields branched PS with different number of branches. For the first dimension (1st-D) separation, reversed-phase temperature gradient interaction chromatography (RP-TGIC) was employed to separate the branched polymer according to mainly the molecular weight. In the second dimension (2nd-D) separation, the effluents from the RP-TGIC separation are subjected to liquid chromatography at chromatographic critical conditions (LCCC), in which the separation was carried out at the critical condition of linear homo-PS to separate the branched PS in terms of the number of branches. The 2D-LC resolution of RP-TGICxLCCC combination worked better than the common LCCCxsize-exclusion chromatography (SEC) configuration due to the higher resolution of RP-TGIC in molecular weight than SEC. Furthermore, by virtue of using the same eluent in RP-TGIC and LCCC (only the column temperature is different), RP-TGICxLCCC separation is free from possible 'break through' and large system peak problems. This type of 2D-LC separation could be utilized efficiently for the analysis of branched polymers with branching units distinguishable by LC separation.

Chromatography, Liquid↗

PubMed2005

Thermodynamic prediction of polymer retention in temperature-programmed HPLC.

Temperature programming has been used increasingly in liquid chromatography in recent years. In particular, temperature gradient elution has shown great potential in the analysis of complex polymers. In this study, the polymer retention behavior in temperature gradient interaction chromatography is investigated based on thermodynamic consideration of the retention factor. The polymer retention predicted by the model calculation is in good agreement with the experimental results, and the model allows devising a temperature program for designed retention behaviors such as a linear dependence of retention volume on log(molecular weight) of polymers. In addition, the migration behavior of polymeric solute along the separation column can be simulated, which shows strong molecular weight dependence. The migration behavior is also confirmed experimentally by employing different length columns or delayed injection.

Journal Article↗

PubMed2005

Rapid molecular weight analysis of polymers by temperature gradient interaction chromatography.

Temperature gradient interaction chromatography (TGIC) has been established as a high-resolution technique for the characterization of synthetic polymers. So far, most of the TGIC investigations focused on the high-resolution analysis and little effort has been made on the reduction of the analysis time. In this study, we examined the effect of the column heating rate, the eluent flow rate, and the column length on the TGIC analysis time. We found that the heating rate is the most important experimental parameter to control the TGIC retention time. With a C18 silica column (50 mm x 4.6mm I.D.), a set of PS standards of wide molecular weight range (5 - 648 kg/mol) could be separated within 4 min at a heating rate of 8 degrees C/min.

Molecular Weight↗

PubMed2005

Nucleoside-based phospholipids and their liposomes formed in water.

Phospholipids and liposomes have been the subjects of considerable attention because of their importance in biological systems. We have efficiently synthesized novel nucleoside-based phospholipids in six-step sequences starting from their corresponding nucleosides. These nucleoside-based phospholipids self-assemble into liposome-like structures in aqueous solutions. We have analyzed the structures of these liposomes by dynamic light scattering, transmission electron microscopy, and confocal microscopy.

Fluorescein-5-isothiocyanate↗

PubMed2004

Interaction-controlled HPLC for block copolymer analysis and separation.

An interaction-controlled HPLC technique has been developed to analyze homopolymer precursors in block copolymer systems that are not easily identified by size exclusion chromatography (SEC) and to obtain block copolymers that are homopolymer-free and compositionally narrower than the as-synthesized ones. We demonstrate that a "single peak" in SEC does not necessarily mean that the block copolymers are free of homopolymers (due to limitations in the SEC analysis of block copolymers) and propose to employ the interaction-controlled HPLC strategy for rigorous analysis and purification of block copolymers in terms of their chemical heterogeneity.

Journal Article↗

PubMed2004

Self-assembling molecular trees containing octa-p-phenylene: from nanocrystals to nanocapsules.

Tree-shaped molecules consisting of octa-p-phenylene as a stem segment and oligoether dendrons as a flexible head were synthesized and characterized. The molecular tree based on a small flexible head self-assembles into a lamellar structure, whereas the molecule based on a larger headgroup self-assembles into a discrete heptameric bundle that organizes into a 3-D primitive orthorhombic supercrystals, as confirmed by X-ray scatterings and transmission electron microscopic (TEM) observations. Optical studies revealed that the absorption and emission maxima and absorption edge of the 3-D structure shift to higher energy compared to those of the lamellar structure. The molecules in dilute solution (THF/water = 1:10 v/v) were observed to self-assemble into capsule-like hollow aggregates, as confirmed by dynamic and static light scatterings, scanning electron microscopy (SEM), and TEM investigations. These results demonstrate that tree-shaped molecules are capable of packing into organized discrete nanocrystals with parallel arrangement as well as hollow nanocapsules with radial arrangement, depending on the presence of selective solvents for flexible headgroup.

Journal Article↗

PubMed2004

HPLC and MALDI-TOF MS analysis of highly branched polystyrene: resolution enhancement by branching.

Temperature gradient interaction chromatography (TGIC) and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) were applied for the characterization of highly branched polystyrenes (PS) prepared by linking living polystyryl anions using 4-chlorodimethylsilylstyrene. Reversed-phase (RP)-TGIC showed an unexpectedly high resolution according to the number of branches despite significant overlap of the molecular weight as confirmed by MALDI-TOF MS. The enhancement of the resolution is ascribed to the contribution of the nonpolar groups in the branched PS: the dimethylsilyl groups in the branching unit as well as the sec-butyl initiator groups. As the number of branches increases, the number of nonpolar groups increases, which in turn increases the RP-TGIC retention synergistically with increasing molecular weight. In contrast, a poorer resolution was found in normal-phase-TGIC, in which the nonpolar groups reduce the retention. The resolution in RP-TGIC appears superior to that of liquid chromatography at the chromatographic critical condition (LCCC) of PS. It is seemingly due to the synergistic contribution of the incremental PS molecular weight to the functionality in the branched PS in RP-TGIC while only the functionality contributes to the separation in LCCC. This type of resolution enhancement could be utilized efficiently for the analysis of highly branched polymers such as dendrimers or hyperbranched polymers.

Chromatography, High Pressure Liquid↗

PubMed2003

Retention mechanism of poly(ethylene oxide) in reversed-phase and normal-phase liquid chromatography.

The retention behavior of low- and high-molecular-mass poly(ethylene oxide) (PEO) in reversed-phase (RP) and normal-phase (NP) liquid chromatography was investigated. In RPLC using a C18 bonded silica stationary phase and an acetonitrile-water mixture mobile phase, the sorption process of PEO to the stationary phase showed deltaH(o) > 0 and deltaS(o) > 0. Therefore, PEO retention in RPLC separation is an energetically unfavorable, entropy-driven process, which results in an increase of PEO retention as the temperature increases. In addition, at the enthalpy-entropy compensation point the elution volume of PEO was very different from the column void volume. These observations are quite different from the RPLC retention behavior of many organic polymers. The peculiar retention behavior of PEO in RPLC separation can be understood in terms of the hydrophobic interaction of this class of typical amphiphilic compounds with the non-polar stationary phase, on the one hand, and with the aqueous mobile phase, on the other. The entropy gain due to the release of the solvated water molecules from the PEO chain and the stationary phase is believed to be responsible for the entropy-driven separation process. On the other hand, in NPLC using an amino-bonded silica stationary phase and an acetonitrile-water mixture mobile phase, PEO showed normal enthalpy-driven retention behavior: deltaH(o) < 0 and deltaS(o) < 0, with the retention decreasing with increasing temperature and PEO eluting near the column void volume at the enthalpy-entropy compensation point. Therefore, high-resolution temperature gradient NPLC separation of high-molecular-mass PEO samples can be achieved with relative ease. The molecular mass distribution of high-molecular-mass PEO was found to be much narrower than that measured by size-exclusion chromatography.

Chromatography, Liquid↗

PubMed2003

Retention mechanism of fatty alcohol ethoxylates in reversed-phase liquid chromatography.

Fatty alcohol ethoxylates (FAEs) are widely used nonionic surfactants that have distributions in both alkyl and poly(ethylene oxide) (PEO) chain length. Generally, two-dimensional liquid chromatography technique is required for the complete characterization of both distributions. By selecting a proper stationary and mobile phase condition, however, we can obtain fully resolved chromatograms of a FAE sample (Brij 30) with respect to both alkyl and PEO chain length by using a single reversed-phase C18 column and aqueous acetonitrile mobile phase. FAEs show a peculiar reversed-phase liquid chromatography (RPLC) retention behavior with an aqueous-organic mobile phase, the retention mechanism of which has not been fully elucidated. For a fixed alkyl chain length, FAEs with higher-molecular-mass PEO block elutes first and the van't Hoff plot of the retention factor shows a curvature. The unique retention behavior can be understood from the opposite thermodynamic characteristics associated with RPLC retention of PEO block and alkyl chain: the sorption process of PEO to the non-polar stationary phase shows deltaH(o) > 0 and deltaS(o) > 0 while the alkyl chain shows deltaH(o) < 0 and deltaS(o) < 0 in contrast. The relative magnitude of the two contributions can change the elution order of the FAE. Therefore the often found, inverted elution order of FAEs (the early elution of FAEs with longer PEO block) is due to the positive enthalpic interaction of PEO blocks, which is a characteristic of the hydrophobic interaction. And the curvature of the van't Hoff plots was analyzed assuming the temperature dependent thermodynamic variables.

Fatty Alcohols↗

PubMed2002

Temperature gradient interaction chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry analysis of air terminated polystyryllithium.

The reaction products of polystyryllithium with air were characterized by size-exclusion chromatography, temperature gradient interaction chromatography and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Polystyryllithium was prepared by anionic polymerization of styrene initiated with sec-butyllithium in cyclohexane under an Ar atmosphere. It was confirmed that polystyryl ketone, polystyryl alcohol, and directly coupled polystyrene were the major products in addition to the normally terminated polystyrene, which is consistent with the results in the literature. We could also identify the presence of methoxy and carboxylic acid end capped polystyrenes as well as dipolystyryl ether as minor products. Among the minor products, dipolystyryl ether has not been reported yet.

Air↗

PubMed2002

Temperature gradient interaction chromatography and MALDI-TOF mass spectrometry analysis of stereoregular poly(ethyl methacrylate)s.

Temperature gradient interaction chromatography (TGIC) was applied for the separation of stereoregular poly(ethyl methacrylate) (PEMA) according to the tacticity. The three PEMA samples with differing tacticity (rr triad content 0, 53, and 91%) prepared by anionic polymerization were used. C18 bonded silica and a mixture of CH2Cl2 and CH3CN (30/70, v/v) were used as stationary and mobile phase, respectively. TGIC was able to separate the PEMA samples, showing the increasing retention in the order of decreasing rr triad contents; however TGIC elution peaks of the three PEMAs were not fully resolved but, rather, were partially overlapped. To isolate the tacticity effect from the molecular weight effect on the TGIC retention, the PEMA samples were fractionated by TGIC, and the accurate molecular weight of the fractions was determined by MALDI-TOF mass spectrometry. The fractions showed a much narrower molecular weight distribution than the mother PEMAs. The TGIC fractions of similar molecular weight but with different tacticity were fully resolved by TGIC, but mother PEMAs were not. These results indicate that the retention in TGIC is affected by both tacticity and molecular weight.

Journal Article↗

PubMed2002

Poly(D,L-lactic acid-co-glycolic acid)-b-poly(ethylene glycol)-b-poly (D,L-lactic acid-co-glycolic acid) triblock copolymer and thermoreversible phase transition in water.

Novel thermoreversible gelation behavior of aqueous solutions of ABA-type triblock copolymers composed of the central polyethylene oxide (PEG) block and two poly(D,L-lactic acid-co-glycolic acid) side blocks was found. Phase transition characteristics, such as critical gel concentration (CGC) and lower and upper critical gel temperature (CGT), are closely related to the molecular structure of the triblock copolymers. The CGC and the lower CGT both increases with increasing PEG/PLGA molecular weight ratio. Increasing the GA content in PLGA block induces a somewhat higher CGC. The copolymer forms micelles with a PLGA loop core and a PEG shell in water. Also grouped micelles are identified seemingly due to the bridging of two micelles sharing two PLGA blocks of a block copolymer chain. As the temperature increases the association of micelles increases, which results in gelation. The ABA-type copolymers exhibit a relatively low CGC (<10%) and low sol-gel transition temperatures compared to BAB-type copolymers. As the temperature increases further gel-sol transition is observed, which would result from the shrinkage of micelles with temperature increase. The hydrodynamic size of the micelles is monitored by dynamic laser scattering, and a possible gelation mechanism was suggested.

Gels↗