Thermoresponsive Water-in-Oil-in-Water Pickering Double Emulsions Stabilized with Biodegradable and Semicrystalline Poly(ethylene glycol)-b-poly(ε-caprolactone-co-δ-valerolactone) Diblock Copolymer Micelles for Controlled Release.

Water-in-oil-in-water (W/O/W) Pickering double emulsions are promising materials for the construction of carriers for water-soluble and oil-soluble molecules or drug delivery systems if the contradictive trade-off between their extreme stability and controlled release properties can be resolved. In this study, biodegradable and biocompatible poly(ethylene glycol)-b-poly(ε-caprolactone-co-δ-valerolactone) (PEG-b-PCVL) diblock copolymers with predesigned hydrophilic to hydrophobic block length ratios and nearly identical ε-caprolactone/δ-valerolactone molar ratio (8/2), were synthesized by ring-opening copolymerization. Then, they self-assembled to create semicrystalline micelles. The melting points of PEG-b-PCVL copolymers and their lyophilized micelles were within a physiological range of temperatures, as determined by differential scanning calorimetry. Water contact angle measurements provided evidence that the surface wettability of PEG-b-PCVL micelles could be tuned by the PCVL block mass fractions or temperature stimulus. Such PEG-b-PCVL micelles were employed as a single particulate stabilizer to develop Pickering double emulsions through a one-step emulsification technique. W/O/W Pickering double emulsions could be generated using relatively hydrophobic PEG-b-PCVL micelles with high mass fractions (exceeding about 89%) of PCVL blocks, and they displayed excellent long-term physical stabilities at room temperature. However, the Pickering double emulsions underwent a rapid microstructural transition into simple oil-in-water Pickering emulsions instead of complete demulsification at elevated temperature (37 °C), which was attributed to the hydrophilicity of micelles enhanced when the core-forming PCVL melted realized by temperature stimulus. Consequently, such W/O/W Pickering double emulsions stabilized solely with semicrystalline PEG-b-PCVL micelles exhibit thermal responsiveness, enabling them to release vitamin B12 encapsulated within the internal aqueous phase rapidly.

Dual-Crosslink Physical Hydrogels with High Toughness Based on Synergistic Hydrogen Bonding and Hydrophobic Interactions.

Constructing dual or multiple noncovalent crosslinks is highly effective to improve the mechanical and stimuli-responsive properties of supramolecular physical hydrogels, due to the synergistic effects of different noncovalent bonds. Herein, a series of tough physical hydrogels are prepared by solution casting and subsequently swelling the films of poly(ureidopyrimidone methacrylate-co-stearyl acrylate-co-acrylic acid). The hydrophobic interactions between crystallizable alkyl chains and the quadruple hydrogen bonds between ureidopyrimidone (UPy) motifs serve as the dual crosslinks of hydrogels. Synergistic effects between the hydrophobic interactions and hydrogen bonds render the hydrogels excellent mechanical properties, with tensile breaking stress up to 4.6 MPa and breaking strain up to 680%. The UPy motifs promote the crystallization of alkyl chains and the hydrophobic alkyl chains also stabilize UPy-UPy hydrogen bonding. The resultant hydrogels are responsive to multiple external stimuli, such as temperature, pH, and ion; therefore, they show the thermal-induced dual and metal ion-induced triple shape memory behaviors.

Effects of Complementary DNA and Salt on the Thermoresponsiveness of Poly(N-isopropylacrylamide)-b-DNA.

The thermoresponsive structural transition of poly(N-isopropylacrylamide) (PNIPAAm)-b-DNA copolymers was explored. Molecular assembly of the block copolymers was facilitated by adding salt, and this assembly was not nucleated by the association between DNA strands but by the coil-globule transition of PNIPAAm blocks. Below the lower critical solution temperature (LCST) of PNIPAAm, the copolymer solution remained transparent even at high salt concentrations, regardless of whether DNA was hybridized with its complementary partner to form a double-strand (or single-strand) structure. At the LCST, the hybridized copolymer assembled in spherical nanoparticles, surrounded by double-stranded DNA; subsequently, the non-cross-linking aggregation occurred, while the nanoparticles were dispersed if the salt concentration was low or DNA blocks were unhybridized. When the DNA duplex was denatured to a single-stranded state by heating, the aggregated nanoparticles redispersed owing to the recovery of the steric repulsion of the DNA strands. The changes in the steric and electrostatic effects by hybridization and the addition of salt did not result in any specific attraction between DNA strands but merely decreased the repulsive interactions. The van der Waals attraction between the nanoparticles overcame such repulsive interactions so that the non-cross-linking aggregation of the micellar particles was mediated.

Thermoresponsive physical hydrogels of poly(lactic acid)/poly(ethylene glycol) stereoblock copolymers tuned by stereostructure and hydrophobic block sequence.

CBABC-type poly(lactic acid) (PLA)/poly(ethylene glycol) (PEG) pentablock copolymers composed of a central PEG block (A) and enantiomeric poly(l-lactic acid) (PLLA, B), poly(d-lactic acid) (PDLA, C) blocks were synthesized. Such pentablock copolymers form physical hydrogels at high concentrations in an aqueous solution, which stem from the aggregation and physical bridging of copolymer micelles. These gels are thermoresponsive and turn into sols upon heating. Physical gelation, gel-to-sol transition, crystalline state, microstructure, rheological behavior, biodegradation, and drug release behavior of PLA/PEG pentablock copolymers and their gels were investigated; they were also compared with PLA-PEG-PLA triblock copolymers containing the isotactic PLLA or atactic poly(d,l-lactide) (PDLLA) endblocks and PLLA-PEG-PLLA/PDLA-PEG-PDLA enantiomeric mixtures. PLA hydrophobic domains in pentablock copolymer gels changed from a homocrystalline to stereocomplexed structure as the PLLA/PDLA block length ratio approached 1/1. The gel of symmetric pentablock copolymer exhibited a wider gelation region, higher gel-to-sol transition temperature, higher hydrophobic domain crystallinity, larger intermicellar distance, higher storage modulus, and slower degradation and drug release rate compared to those of the asymmetric PLA/PEG pentablock copolymers or triblock copolymers. SAXS results indicated that the PLLA/PDLA blocks stereocomplexation in pentablock copolymers facilitated the intermicellar aggregation and bridging. Cylindrical ordered structures were observed in all the gels formed from the PLA/PEG pentablock and triblock copolymers. The stereocomplexation degree and intermicellar distance of the pentablock copolymer gels increased with heating.

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.

Development of ultra-thin poly(L-lactic acid)-based films integrating toughness, barrier properties, and gas selectivity: Towards gas-permeation controllable green food packaging.

High costs and low performance have constrained the application of bio-based materials in food packaging. Herein, a series of ultra-thin poly(L-lactic acid-iconic acid N-diol) (P(LA-NI)) copolymer films were developed using a "one-step" polycondensation process with integrated toughness, barrier properties, gas selectivity, and quality control features. The massive branched structure and gg conformers in P(LA-NI) act as "internal chain expansion" and "internal plasticization". Meanwhile, P(LA-NI) contains numerous polar groups and unique nanoscale microphase structures to realize excellent CO2, O2 barrier, CO2/O2 selectivity, anti-fogging, and UV shielding functions. The atmosphere within the package spontaneously achieves the desirable low O2 and high CO2 levels when packaging button mushrooms with high respiratory metabolism. Eventually, the shelf life of button mushrooms reached 24 days, >3-fold extended. This PLLA-based film meets "dual carbon" and "food safety" goals and has vast potential for fresh food preservation.

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.

Microstructurally tunable pickering emulsions stabilized by poly(ethylene glycol)-b-poly(ε-caprolactone) diblock biodegradable copolymer micelles with predesigned polymer architecture.

Poly(ethylene glycol)-b-poly(ε-caprolactone) diblock copolymers (PEG-b-PCL) with predesigned hydrophilic/hydrophobic block length ratios have been synthesized and self-assembled to form micelles, then used to emulsify medium-chain triglycerides with an aqueous phase. The morphologies and sizes of PEG-b-PCL copolymer micelles have been characterized by transmission electron microscopy and dynamic light scattering. Interfacial tension testing between micellar dispersions and oil, combined with water contact angle measurements, have been performed to assess the ability of these micelles to adjust interfacial tension and micellar hydrophobicity, respectively. Relationship between the wettability of PEG-b-PCL copolymer micelles and their emulsification properties has been proved through phase diagram, optical microscopic observation, droplet sizes evolution and phase separation behavior of Pickering emulsion samples. Results show that both oil-in-water and water-in-oil Pickering emulsions, as well as water-in-oil-in-water (W/O/W) double-Pickering emulsions, may be controllably prepared through one-step homogenization. Double microstructure of W/O/W Pickering emulsion has proved to be extremely stable during long-term storage.

Light-Induced Crystalline Size Heterogeneity of Polymers Enables Programmable Writing, Morphing, and Mechanical Performance Designing.

Constructing the spatio-selective crystalline structures has been an effective strategy to diversify the functions and applications of polymers. However, it is still challenging to program the crystalline heterogeneity into commercialized polymers and realize associate functions by a simple yet generalizable method. Herein, we propose a facile approach to fabricate multifunctional materials by programming the spatial distribution of crystal size in semicrystalline polymers. Various crystal size patterns in both plane and depth directions are introduced by the photothermal effect of printed ink and subsequent crystallization at different temperatures, which can be reprogrammed by repeated melting and crystallization. These obtained materials with well-defined crystal size heterogeneities exhibit diverse and regulable optics, mechanical and swelling properties, as manifested in applications including rewritable polymer paper, programmed mechanics, and advanced morphing devices. The light-induced crystal size heterogeneity of polymers has provided insights into developing advanced multifunctional materials.

Role of Chain Entanglements in the Stereocomplex Crystallization between Poly(lactic acid) Enantiomers.

Stereocomplex (SC) crystallization between polymer enantiomers has opened a promising avenue for preparing high-performance materials. However, high-crystallinity SCs are difficult to achieve for high-molecular-weight (HMW) enantiomeric blends of chiral polymers [e.g., poly(lactic acid)]. Despite extensive studies, why HMW enantiomeric blends have difficulty in SC crystallization has not been clarified. Herein, we chose the HMW poly(l-lactic acid)/poly(d-lactic acid) (PLLA/PDLA) 1/1 blend as the model system and demonstrated the crucial role of chain entanglement in regulating SC crystallization. PLLA/PDLA blends with various entanglement degrees were prepared by freeze-drying. We observed that disentangling promoted not only the crystallization rate but also the crystallinity of SCs in both the nonisothermal and isothermal processes. The less-entangled samples crystallized exclusively as the high-crystallinity SCs at different temperatures, in contrast to the predominant homocrystallization that occurred in the common entangled samples. This study provides deep insight into the SC crystallization mechanism of polymers and paves the way for future research attempting to prepare SC materials.

Stereocomplexed and homocrystalline thermo-responsive physical hydrogels with a tunable network structure and thermo-responsiveness.

The widespread application of thermo-responsive hydrogels requires materials with robust mechanical properties and tunable responsiveness. Herein, we report robust thermo-responsive physical hydrogels with a tunable network structure and responsiveness by controlling the manner of crystallization of hydrophobic blocks. Biocompatible, stereocomplexable poly(l-lactic acid) (PLLA) and poly(d-lactic acid) (PDLA) were introduced into thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) to obtain the enantiomeric grafted copolymers PNIPAM-g-PLLA and PNIPAM-g-PDLA and their corresponding hydrogels. The hydrophobic PLLA/PDLA domains served as physical crosslinking junctions in the hydrogels. The crystalline structure of the hydrogels can be facilely tuned by varying the ratio of PLLA/PDLA enantiomeric blocks. Stereocomplex (SC) crystallization between PLLA and PDLA facilitates the formation of H-bonded hydrophobic domains with denser chain packing, which endows the racemic hydrogels with a stronger network structure, higher mechanical strength, and better solvent resistance compared to enantiopure examples. The hydrogels exhibit good thermo-sensitivity in water; the stronger racemic hydrogel network restricts volume shrinkage and water desorption at high temperatures, enabling the facile control of thermo-responsiveness. The crystallization-tuned thermo-responsiveness of racemic and enantiopure hydrogels also allows for the design of assembled bilayer hydrogels capable of thermally triggered reversible shape morphing.

High strength of hybrid double-network hydrogels imparted by inter-network ionic bonds.

Interaction between networks has been proven to be of importance for mechanical property enhancement of double-network (DN) hydrogels. In this work, inter-network ionically cross-linked hybrid DN hydrogels have been prepared using poly(sodium 2-acrylamide-2-methylpropanesulfonate) (PNaAMPS) as the first network, and a co-polymer of a cationic monomer and acrylamide (AM) as the second network. Ionic complexes were formed between the two oppositely charged networks after dialyzing the hydrogels in water. Near the ion-balance point, hybrid DN hydrogels with enhanced strengths were achieved compared to the unmodified PNaAMPS/polyacrylamide (PAM) DN hydrogel. Synchrotron radiation small-angle X-ray scattering (SAXS) analyses were performed on the DN hydrogels. It was found that large and compact cross-linked domains were formed in the hybrid DN hydrogels, especially near the ion-balance point, as demonstrated by the SAXS results. These large and compact cross-linked domains, which indicate enhanced interactions between networks containing ionic bonds besides physical entanglements, dissipate additional concentrated stress, resulting in high strength of the hybrid DN hydrogels.

Polymorphic packing and dynamics of biodegradable poly(3-hydroxypropionate).

The packing and dynamics of the beta-, gamma-, and delta-forms of poly(3-hydroxypropionate) (P3HP), which represents the basic skeleton of bacterial poly(3-hydroxyalkanoate)s, were investigated by the variable-temperature FTIR and (13)C solid-state NMR measurements (SNMR). Under cooling, most of IR bands in the 1500-750 cm(-1) region were noted to be distinctively blueshifted and enhanced, which should reflect the increased intermolecular interaction and depend on the chain packing of each crystal form. Furthermore, the temperature-dependent splitting of vibration were found to occur at the CH2 bending and rocking for the gamma-form, and at the CH2 bending and C-O-C stretching for the delta-form, while be absent for the beta-form. All the FTIR results indicate that the gamma-form has a stronger intermolecular interaction than the beta-form, although both adopt the all-trans conformation. The IR evidence measured during heating further reveal that the melting of the tightly packed gamma-form would pass through some mesophase, which lacks the regular packing but hold the long-range order along the chains. The delta-form was also found to be tightly packed, and contain at least and most possibly two chains in one unit cell. The CP/MAS (13)C SNMR spectrum of the delta-form was compared with those of the beta- and gamma-forms, and was well explained by combining the gamma-gauche and gamma-eclipsed effects. With considering possible differences in the magnetic dipole-dipole interaction among three crystal forms, the molecular mobilities of crystalline phases were estimated by the values of (13)C spin-lattice relaxation time to rank as delta << gamma << beta. The diversified mobilities of three polymorphic crystalline phases, which is the key to crystalline-structure dependent biodegradability of P3HP, were discussed with considering the packing and conformation.

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).

Preferential Stereocomplex Crystallization in Enantiomeric Blends of Cellulose Acetate-g-Poly(lactic acid)s with Comblike Topology.

Although stereocomplex (sc) crystallization is highly effective for improving the thermal resistance of poly(lactic acid) (PLA), it is much less predominant than homocrystallization in high-molecular-weight (HMW) poly(l-lactic acid)/ poly(d-lactic acid) (PLLA/PDLA) racemic blends. In this contribution, the sc crystallization of HMW PLLA/PDLA racemic blends was facilitated by using comblike PLAs with cellulose acetate as the backbone. Competing crystallization kinetics, polymorphic crystalline structure, and structural transition of comblike PLLA/PDLA blends with a wide range of MWs were investigated and compared with the corresponding linear/comblike and linear blends. The HMW comblike blend is preferentially crystallized in sc polymorphs and exhibits a faster crystallization rate than does the corresponding linear blend. The sc crystallites are predominantly formed in nonisothermal cold crystallization and isothermal crystallization at temperatures above 120 °C for the comblike blends. Except for the facilitated sc formation in primary crystallization, synchrotron radiation WAXD analysis indicates that the presence of a comblike component also facilitates the transition or recrystallization from homocrystallite (hc) to sc crystallite upon heating. Preferential sc formation of comblike blends is probably attributable to the favorable interdigitation between enantiomeric branches and the increased mobility of polymer segments. After crystallization under the same temperature, the comblike blends, which mainly contain sc crystallites, show smaller long periods and thinner crystalline lamellae than do the corresponding PLLA with homocrystalline structures.

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.

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 ß-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.

Structural characterization of nanoparticles from thermoresponsive poly(N-isopropylacrylamide)-DNA conjugate.

Poly(N-isopropylacrylamide) (PNIPAAm) grafted with single-stranded (ss) DNA conjugate (PNIPAAm-g-DNA) self-assembles above its lower critical solution temperature to form colloidal particles. When the ssDNA within the particle hybridizes with its complementary DNA, the particles aggregate above a certain threshold of salt concentration with drastically increased turbidity in solution. Detailed structural information of the particle was obtained mainly by small-angle X-ray scattering. The influence of copolymer composition on the morphology of particle and non-crosslinking aggregation was examined. The particle consists of hydrophobic PNIPAAm core surrounded by hydrophilic DNA strands. The increase in DNA fraction brought about a significant decrease in core size, whereas the shell thickness little changed and corresponded to the length of DNA. A structural model with a sticky potential was applied to the analysis of particle aggregate. This analysis provided that the particles aggregate while the coronal layers interpenetrate each other. The interaction between the particles was quantified in terms of the sticky potential and showed a trend to be influenced by the particle size rather than the graft density of DNA strands on the particle.

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.

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.