Pengju Pan

Layered metal phosphonate reinforced poly(L-lactide) composites with a highly enhanced crystallization rate.

Layered metal phosphonate, zinc phenylphosphonate (PPZn), reinforced poly(L-lactide) (PLLA) composites were fabricated by a melt-mixing technique. The nonisothermal and isothermal crystallization, melting behavior, spherulite morphology, crystalline structure, and static and dynamic mechanical properties of the PLLA/PPZn composites were investigated. PPZn shows excellent nucleating effects on PLLA crystallization. With incorporation of 0.02% PPZn, PLLA can finish crystallization under cooling at 10 degrees C/min. The crystallization rate of PLLA further increases with increasing PPZn concentration. Upon the addition of 15% PPZn, the crystallization half-times of a PLLA/PPZn composite decrease from 28.0 to 0.33 min at 130 degrees C, and from 60.2 to 1.4 min at 140 degrees C, compared to the neat PLLA. With the presence of PPZn, the nuclei number of PLLA increases and the spherulite size reduces significantly. Through analysis of the crystal structures of PLLA and PPZn, it was proposed that the nucleation mechanism of the PLLA/PPZn system is epitaxial nucleation. The incorporation of PPZn has no discernible effect on the crystalline structure of PLLA. Moreover, PPZn has good reinforcement effects on the PLLA matrix. The tensile strength of the composite is enhanced with the addition of a relatively small amount of PPZn (<5%). The tensile and storage moduli of composites increase with increasing PPZn loadings, and they respectively improve by 28% and 34% with the incorporation of a 15% PPZn filler, as compared to the neat PLLA.

Competitive Stereocomplexation, Homocrystallization, and Polymorphic Crystalline Transition in Poly(l-lactic acid)/Poly(d-lactic acid) Racemic Blends: Molecular Weight Effects

Competitive crystallization kinetics, polymorphic crystalline structure, and transition of poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) racemic blends with a wide range of molecular weights (MWs) were symmetrically investigated. Stereocomplex (sc) crystallites are exclusively formed in the low-MW racemic blends. However, stereocomplexation is remarkably depressed, and homocrystallization becomes prevailing with increasing MWs of PLLA and PDLA. Suppressed stereocomplexation in high-MW (HMW) racemic blends is proposed to be due to the low chain diffusion ability and restricted intermolecular crystal nucleation/growth. Equilibrium melting point of sc crystallites first increases and then decreases as MW increases. Crystallinity and relative fraction of sc crystallites in racemic blends enhance with crystallization temperature (Tc), and the sc crystallites are merely formed at Tc > 170 °C because of their higher thermodynamic stability. In situ wide-angle X-ray diffraction (WAXD) analysis reveals that the stereocomplexation and homocrystallization are successive rather than completely simultaneous, and the stereocomplexation is preceding homocrystallization in isothermal crystallization of HMW racemic blends. Both initial crystalline structure of homocrystallites (hc) and MW influence the heating-induced hc-to-sc transition of HMW racemic blend drastically; the hc-to-sc transition becomes easier with decreasing Tc and MW. After crystallization at the same temperature, sc crystallites show smaller long period than their hc counterparts.

Core-shell structure, biodegradation, and drug release behavior of poly(lactic acid)/poly(ethylene glycol) block copolymer micelles tuned by macromolecular stereostructure.

Poly(ethylene glycol)-b-poly(L-lactic acid)-b-poly(D-lactic acid) (PEG-b-PLLA-b-PDLA) stereoblock copolymers were synthesized by sequential ring-opening polymerization. Their micelle formation, precise micelle structure, biodegradation, and drug release behavior were systematically investigated and compared with the PEG-b-poly(lactic acid) (PEG-b-PLA) diblock copolymers with various PLA stereostructures and PEG-b-PLLA/PEG-b-PDLA enantiomeric mixture. Stereoblock copolymers having comparable PLLA and PDLA block lengths and enantiomerically-mixed copolymers assemble into the stereocomplexed core-shell micelles, while the isotactic and atactic PEG-b-PLA copolymers formed the homocrystalline and amorphous micelles, respectively. The PLA segments in stereoblock copolymer micelles show smaller crystallinity than those in the isotactic and enantiomerically-mixed ones, attributed to the short block length and presence of covalent junction between PLLA and PDLA blocks. As indicated by the synchrotron radiation small-angle X-ray scattering results, the stereoblock copolymer micelles have larger size, micellar aggregation number, core radius, smaller core density, and looser packing of core-forming segments than the isotactic and enantiomerically-mixed copolymer micelles. These unique structural characteristics cause the stereoblock copolymer micelles to possess higher drug loading content, slower degradation, and drug release rates.

Uracil as nucleating agent for bacterial poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)] copolymers.

In this study, uracil has been introduced as the nucleating agent (NA) for bacterially synthesized poly[(3-hydroxybutyrate)-co-(3-hydroxyhexanoate)] (PHBHHx) copolymers with HHx content of 5, 10, 18 mol-%, and poly(3-hydroxybutyrate) (PHB) homopolymer for the first time. Its effect was compared with the conventional NA of PHB, that is, boron nitride (BN), and two other naturally occurring pyrimidine derivatives, i.e., thymine and cytosine. The effects of uracil on the crystallization kinetics, melting behavior, spherulite morphology, and crystalline structure of PHBHHx and PHB were investigated by differential scanning calorimetry (DSC), polarized optical microscopy (POM), and wide-angle X-ray diffraction (WAXD). Uracil and BN exhibit the comparable nucleation efficiency on the crystallization of PHB, whereas uracil shows much more effective nucleation ability than BN for PHBHHx copolymers. With incorporation of 1 wt.-% uracil, PHBHHx with 0-10 mol-% HHx units can finish crystallization upon cooling at 10 degrees C x min(-1). The crystallization half-times (t(1/2)) of all the PHB and PHBHHx samples decrease significantly with presence of uracil. The crystallization rate of polymers further enhances with increase in uracil concentration. With addition of 1 wt.-% uracil, the t(1/2) value of PHBHHx with 10 mol-% HHx units melt-crystallizing at 80 degrees C decreases to approximately 4.0% of the neat polymer, and the nucleation density increases by 3-4 orders of magnitude. The incorporation of uracil has no discernable effect on the crystalline structure of PHBHHx, as evidenced by WAXD results. It was proposed that the nucleation mechanism of the uracil/PHBHHx (or PHB) system might be the epitaxial nucleation.

Exclusive Stereocomplex Crystallization of Linear and Multiarm Star-Shaped High-Molecular-Weight Stereo Diblock Poly(lactic acid)s.

Linear, 3-arm, and 6-arm star-shaped stereo diblock copolymers of l- and d-lactic acid (PLLA-b-PDLA) with high molecular weights (MWs) were synthesized via two-step ring-opening polymerization (ROP) with 1-dodechanol, glycerol, and d-sorbitol as the initiators, respectively. The chemical structure, nonisothermal and isothermal crystallization kinetics, crystalline structure, lamellar morphology, and mechanical thermal properties of PLLA-b-PDLAs with different macromolecular topologies were investigated. Compared to the high-molecular-weight (MW) poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) racemic blends, PLLA-b-PDLAs exhibit faster crystallization upon cooling and isothermal melt crystallization; they crystallize exclusively in stereocomplex (sc) crystallites under all of the conditions investigated. This is attributable to the enhanced interactions between enantiomeric blocks linked covalently. Macromolecular topology influences the crystallization kinetics and crystalline structure of PLLA-b-PDLAs significantly. The crystallization temperature upon cooling, melting temperature, degree of crystallinity, spherulitic growth rate, crystallite size, long period, and crystalline layer thickness of PLLA-b-PDLA decrease with increasing branching number because of the retarding effect of branching on the crystallization rate and crystallizability. Because of the formation of high-melting-point sc crystallites, both the linear and star-shaped PLLA-b-PDLAs exhibit better thermal resistance and higher storage moduli at high temperature than does homocrystalline PLLA.

Interactions between an anticancer drug and polymeric micelles based on biodegradable polyesters.

Interactions between the anticancer drug quercetin and biodegradable polyesters within micelles were investigated by DSC, WAXD, and UV analyses. For micelles based on poly(ethylene glycol) methyl ether-block-poly(epsilon-caprolactone) (MPEG-PCL), DSC analysis indicated that the interactions were between the hydrophobic core and the drug within the micelle. For micelles based on poly(ethylene glycol) methyl ether-block-poly(L-lactide) (MPEG-PLLA), the interactions were between the hydrophobic core and the drug and between hydrophilic segments and the drug. WAXD results indicated that no crystalline phase of the drug was found in either of the micelle types. Based on the DSC and WAXD results, two probable micelle structures were proposed. The UV spectra revealed the presence of hydrogen bonding as the main interaction between the drug and the polyesters. In vitro studies demonstrated that quercetin release from micelles was sustained and was affected by the polymer-drug interaction.

Conformational and microstructural characteristics of poly(L-lactide) during glass transition and physical aging.

The glass transition and physical aging processes of poly(L-lactide) (PLLA) were studied by variable-temperature Fourier transform infrared (FTIR) spectroscopy and (13)C solid-state NMR spectroscopy. The glass transition temperature (T(g)) of PLLA can be well determined from the temperature-dependent FTIR intensity. Nearby T(g), a distinct change in the slope of spectral intensity versus temperature plot is detected. FTIR results suggest that the energy-favorable gauche-trans (gt) conformers rearrange into the less energy-favorable gauche-gauche (gg) counterparts with heating over the glass transition region, which becomes more distinct at temperature above T(g). Besides, the 1267 cm(-1) band, which shows different trends of variation from the other bands upon heating, was assigned to be more sensitive to the nu(as)(C-O-C)+delta(CH) vibration mode of the less energy-favorable gg conformers in PLLA. By comparing the FTIR spectra of the aged and deaged PLLA, it was demonstrated that the rearrangement from the high- to low-energy conformers, i.e., gg to gt, occurs with physical aging. (13)C spin-lattice relaxation measurements indicate that the relaxation rate distribution broadens with aging, which agrees with the previous suggestion that the locally ordered domains are formed during physical aging. Because of the larger variation in the conformational state and microstructure, the FTIR intensities vary much more abruptly for the aged sample with heating to nearby T(g).

Effects of crystallization temperature of poly(vinylidene fluoride) on crystal modification and phase transition of poly(butylene adipate) in their blends: a novel approach for polymorphic control.

Effects of the isothermal crystallization temperatures of poly(vinylidene fluoride), T(IC,PVDF), on polymorphic crystalline structure, phase transition, fractional crystallization, and enzymatic degradation of poly(butylene adipate) (PBA) in crystalline/crystalline blends have been investigated. The crystal modifications of PBA can be regulated by T(IC,PVDF). Lower T(IC,PVDF) (e.g., 80 °C) facilitates the formation of PBA α crystals in both the isothermal and nonisothermal melt crystallizations and also favors the β-to-α phase transition of PBA upon annealing at elevated temperatures. This might be attributable to the decreased equilibrium melting temperature of PBA when T(IC,PVDF) is decreased. Higher T(IC,PVDF) is favorable for the fractional crystallization of PBA, which tends to segregate in the interlamellar regions of the PVDF matrix under these conditions. PBA shows faster enzymatic degradation in the blends with a lower T(IC,PVDF) than those with a higher T(IC,PVDF), attributable to the preferential formation of α crystals at a lower T(IC,PVDF). This study provides a new method to control the crystal modification and physical properties of polymorphic polymers in their blend systems.

In situ formation and gelation mechanism of thermoresponsive stereocomplexed hydrogels upon mixing diblock and triblock poly(lactic acid)/poly(ethylene glycol) copolymers.

A novel in situ formed gel system with potential biodegradability and biocompatibility is developed by mixing the diblock and triblock poly(lactic acid)/poly(ethylene glycol) (PLA/PEG) copolymers with opposite configurations of PLA blocks. In situ gelation of such system is extremely fast, which happens within 10 s after mixing. In situ gelation, gel-to-sol transition, crystalline structure, microstructures, and mechanical properties of PLA-PEG/PLA-PEG-PLA enantiomerically mixed gels are significantly influenced by the mixing ratio, degree of polymerization for PEG block in triblock (DPPEG,tri) and diblock copolymers (DPPEG,di). It is found that in situ gelation of PLA-PEG/PLA-PEG-PLA enantiomeric mixture just happen at relatively smaller PLA-PEG/PLA-PEG-PLA mass ratio and larger DPPEG,tri. Hydrodynamic diameters of PLA-PEG and PLA-PEG-PLA copolymers in dilute solution increase remarkably upon mixing, indicating the formation of bridging networks. Stereocomplexed crystallites are formed for the PLA hydrophobic domains in PLA-PEG/PLA-PEG-PLA enantiomeric mixtures. As indicated by synchrotron-radiation SAXS analysis, the enantiomeric mixture changes from a compactly to loosely aggregated structure and the intermicellar distance enhances with increasing DPPEG,tri, DPPEG,di, or PLA-PEG-PLA fraction. Gelation mechanism of PLA-PEG/PLA-PEG-PLA enantiomeric mixture is proposed, in which part of PLA-PEG-PLA chains act as the connecting bridges between star and flower-like micelles and the stereocomplexed crystallites in micelle cores act as physically cross-linked points.

Thermoresponsive micellization and micellar stability of poly(n -isopropylacrylamide)- b -DNA diblock and miktoarm star polymers

Linear and miktoarm star-shaped diblock copolymers consisting of single-stranded DNA and poly(N-isopropylacrylamide) (PNIPAAm) with various compositions were synthesized via atom transfer radical polymerization and click chemistry. The temperature-responsive phase transition behavior, micellization, was systematically examined using UV-vis spectrometry, high-sensitivity differential scanning calorimetry, dynamic light scattering, and small-angle X-ray scattering. The lower critical solution temperature (LCST) increased, and its enthalpy decreased with decreasing PNIPAAm content. The copolymers self-assembled into well-defined nanoparticles having a core composed of PNIPAAm and a coronal layer of DNA above LCST. The particle size and micellar aggregation number of copolymer chains depended on the macromolecular composition and chain architecture. On the other hand, regardless of their factors, the surface area occupied by one DNA strand was found to be almost unchanged. The hybridization of DNA on the nanoparticles with fully complementary one induced the aggregation of the particles in a non-cross-linking configuration. The nanoparticle composed of miktoarm star copolymer showed a quicker DNA-hybridization response in this non-cross-linking aggregation compared with the case of a linear analogue.