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2015 Volume 33 Issue 7
2015, 33(7): 931-946
doi: 10.1007/s10118-015-1654-7
Abstract:
Polypeptide brushes are attractive platforms to generate functional and responsive interfaces that are of potential interest due to their possible biodegradability, biocompatibility and tunable secondary structures. Surface-initiated ring-opening polymerization (SI-ROP) of -amino acid N-carboxyanhydrides represents a powerful and versatile strategy to generate polypeptide brushes. This review is an attempt to capture the state-of-the-art in this field and highlights the latest developments in several selected areas. In addition to presenting an overview of the synthetic methods that have been used to generate polypeptide brushes via SI-ROP, this article will discuss the preparation of patterned polypeptide brushes, the conformational properties of surface-tethered polypeptides, ways to control chain orientation at surfaces as well as properties and applications of these thin polymer films.
Polypeptide brushes are attractive platforms to generate functional and responsive interfaces that are of potential interest due to their possible biodegradability, biocompatibility and tunable secondary structures. Surface-initiated ring-opening polymerization (SI-ROP) of -amino acid N-carboxyanhydrides represents a powerful and versatile strategy to generate polypeptide brushes. This review is an attempt to capture the state-of-the-art in this field and highlights the latest developments in several selected areas. In addition to presenting an overview of the synthetic methods that have been used to generate polypeptide brushes via SI-ROP, this article will discuss the preparation of patterned polypeptide brushes, the conformational properties of surface-tethered polypeptides, ways to control chain orientation at surfaces as well as properties and applications of these thin polymer films.
2015, 33(7): 947-954
doi: 10.1007/s10118-015-1642-y
Abstract:
Doxorubicin (DOX) loaded poly(lactic-co-glycolic acid) (PLGA) microparticles with internal pores (MP-D) were developed for long-acting release in pulmonary inhalation treatment. The PLGA microparticles exhibited favorable aerodynamic properties for pulmonary delivery. In vitro drug release profile suggested that MP-D have the advantage of long-term maintenance of drug concentrations. MTT assay demonstrated the in vitro anti-tumor efficiency of the DOX loaded PLGA microparticles. Furthermore, melanoma lung metastasis model was established to determine the in vivo anti-tumor efficiency. The mice treated with MP-D showed significantly fewer lesions than the untreated ones. The survival analysis indicated that MP-D prolonged the survival time of tumor-bearing mice. These results suggested that DOX loaded PLGA microparticles with internal pores have the potential to be used as long-acting release carriers in clinical lung cancer treatment.
Doxorubicin (DOX) loaded poly(lactic-co-glycolic acid) (PLGA) microparticles with internal pores (MP-D) were developed for long-acting release in pulmonary inhalation treatment. The PLGA microparticles exhibited favorable aerodynamic properties for pulmonary delivery. In vitro drug release profile suggested that MP-D have the advantage of long-term maintenance of drug concentrations. MTT assay demonstrated the in vitro anti-tumor efficiency of the DOX loaded PLGA microparticles. Furthermore, melanoma lung metastasis model was established to determine the in vivo anti-tumor efficiency. The mice treated with MP-D showed significantly fewer lesions than the untreated ones. The survival analysis indicated that MP-D prolonged the survival time of tumor-bearing mice. These results suggested that DOX loaded PLGA microparticles with internal pores have the potential to be used as long-acting release carriers in clinical lung cancer treatment.
2015, 33(7): 955-963
doi: 10.1007/s10118-015-1660-9
Abstract:
PLGA, mPEG diblock copolymer was synthesized by bulk ring-opening polymerization method. The double emulsion solvent evaporation method was used to prepare bovine serum albumin (BSA)-loaded microspheres. Optical microscopy was used to observe the whole microsphere fabrication process. It is confirmed that the proportion of inner aqueous phase is one of the most critical factors that determines the morphology of microspheres. Double emulsion droplets which have appropriate amount of inner aqueous phase can form closed and dense microspheres, while, too much inner aqueous phase will cause a collapse of the double emulsion droplets, resulting in a loss of drug. The proportion of inner aqueous phase was varied to prepare microspheres of different morphology. The results show that with increasing the amount of inner aqueous phase, a higher percent of broken microspheres and lower encapsulation efficiency appeared, and also, a more severe initial burst release and faster release rate.
PLGA, mPEG diblock copolymer was synthesized by bulk ring-opening polymerization method. The double emulsion solvent evaporation method was used to prepare bovine serum albumin (BSA)-loaded microspheres. Optical microscopy was used to observe the whole microsphere fabrication process. It is confirmed that the proportion of inner aqueous phase is one of the most critical factors that determines the morphology of microspheres. Double emulsion droplets which have appropriate amount of inner aqueous phase can form closed and dense microspheres, while, too much inner aqueous phase will cause a collapse of the double emulsion droplets, resulting in a loss of drug. The proportion of inner aqueous phase was varied to prepare microspheres of different morphology. The results show that with increasing the amount of inner aqueous phase, a higher percent of broken microspheres and lower encapsulation efficiency appeared, and also, a more severe initial burst release and faster release rate.
2015, 33(7): 964-975
doi: 10.1007/s10118-015-1649-4
Abstract:
The relationship between microphase structure and mechanical response of the binary blends consisting of polystyrene-block-polyisoprene-block-polystyrene copolymer and low molecular weight polystyrene has been investigated. Low molecular weight polystyrene was chosen to obtain uniformly solubilized nano-blends without macrophase separation. The specimens were solution-cast by adding different amounts of homo-polystyrene to acquire different microphase structures. Small angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and atom force microscopy (AFM) have been used to study the microdomain and grain structure. It is observed that the structural changes in d-spacing and grain size on account of different amounts of polystyrene alter the mechanical behavior in both monotonic tensile and cyclic tests. The elastic and the Mullins effects are strongly sensitive to the changes in d-spacing and grain sizes. Moreover, the sample with bi-continuous structure shows the largest tensile strength and Mullins effect. In addition, the Mooneye-Rivlin phenomenological model was used to evaluate and explore the relationship between the polymer topological networks and the rubber elasticity of these styrenic nano-blends.
The relationship between microphase structure and mechanical response of the binary blends consisting of polystyrene-block-polyisoprene-block-polystyrene copolymer and low molecular weight polystyrene has been investigated. Low molecular weight polystyrene was chosen to obtain uniformly solubilized nano-blends without macrophase separation. The specimens were solution-cast by adding different amounts of homo-polystyrene to acquire different microphase structures. Small angle X-ray scattering (SAXS), transmission electron microscopy (TEM) and atom force microscopy (AFM) have been used to study the microdomain and grain structure. It is observed that the structural changes in d-spacing and grain size on account of different amounts of polystyrene alter the mechanical behavior in both monotonic tensile and cyclic tests. The elastic and the Mullins effects are strongly sensitive to the changes in d-spacing and grain sizes. Moreover, the sample with bi-continuous structure shows the largest tensile strength and Mullins effect. In addition, the Mooneye-Rivlin phenomenological model was used to evaluate and explore the relationship between the polymer topological networks and the rubber elasticity of these styrenic nano-blends.
2015, 33(7): 976-987
doi: 10.1007/s10118-015-1650-y
Abstract:
To enhance the ultraviolet resistance of ZnO based polymer materials, ZnO-supported mesoporous zeolite (M-ZnO) was prepared and characterized by atomic absorption spectroscopy and scanning electron microscopy. The ultraviolet resistance, crystallization behavior and melting characteristics of ZnO and M-ZnO filled PPR composites were compared by FTIR spectra and differential scanning calorimetry. The ultraviolet resistance of M-ZnO filled PPR composites is higher than that of ZnO filled PPR composites, indicating higher ultraviolet resistance of M-ZnO than that of ZnO. The crystallization temperatures of mesoporous zeolite filled PPR were higher than those of M-ZnO and decreased with increasing UV-irradiation time. But the crystallization temperatures of M-ZnO filled PPR composites were not influenced by UV-irradiation time. The ZnO supported on the surface of zeolite is effective in enhancing the ultraviolet resistance of ZnO based polymer materials.
To enhance the ultraviolet resistance of ZnO based polymer materials, ZnO-supported mesoporous zeolite (M-ZnO) was prepared and characterized by atomic absorption spectroscopy and scanning electron microscopy. The ultraviolet resistance, crystallization behavior and melting characteristics of ZnO and M-ZnO filled PPR composites were compared by FTIR spectra and differential scanning calorimetry. The ultraviolet resistance of M-ZnO filled PPR composites is higher than that of ZnO filled PPR composites, indicating higher ultraviolet resistance of M-ZnO than that of ZnO. The crystallization temperatures of mesoporous zeolite filled PPR were higher than those of M-ZnO and decreased with increasing UV-irradiation time. But the crystallization temperatures of M-ZnO filled PPR composites were not influenced by UV-irradiation time. The ZnO supported on the surface of zeolite is effective in enhancing the ultraviolet resistance of ZnO based polymer materials.
2015, 33(7): 988-999
doi: 10.1007/s10118-015-1645-8
Abstract:
The molecular structure of SEBS grafted with maleic anhydride (SEBS-g-MAH) through ultrasound initiation was investigated by nuclear magnetic resonance (NMR). It can be confirmed that the grafting groups mainly exist on the terminus of the ultrasound initiated SEBS-g-MAH. However, it was difficult to detailedly confirm the block of the SEBS on which MAH is grafted through characterization of 1H-NMR due to the complex structure of the SEBS. Moreover, the temperature-dependent infrared spectra of the ultrasound initiated SEBS-g-MAH were also analyzed by the perturbation correlation moving window 2D (PCMW2D) correlation spectroscopy. It could confirm that the broken point existed at the joint between poly(ethylene-co-1-butene) (EB block) and polystyrene block (S block). Therefore, the grafting groups were attached to not only the S block but also the EB block. In addition, in order to well understand the aggregation structure of the ultrasound initiated SEBS-g-MAH, the possible grafting mechanism and aggregation model of the ultrasound initiated SEBS-g-MAH at room temperature were also proposed.
The molecular structure of SEBS grafted with maleic anhydride (SEBS-g-MAH) through ultrasound initiation was investigated by nuclear magnetic resonance (NMR). It can be confirmed that the grafting groups mainly exist on the terminus of the ultrasound initiated SEBS-g-MAH. However, it was difficult to detailedly confirm the block of the SEBS on which MAH is grafted through characterization of 1H-NMR due to the complex structure of the SEBS. Moreover, the temperature-dependent infrared spectra of the ultrasound initiated SEBS-g-MAH were also analyzed by the perturbation correlation moving window 2D (PCMW2D) correlation spectroscopy. It could confirm that the broken point existed at the joint between poly(ethylene-co-1-butene) (EB block) and polystyrene block (S block). Therefore, the grafting groups were attached to not only the S block but also the EB block. In addition, in order to well understand the aggregation structure of the ultrasound initiated SEBS-g-MAH, the possible grafting mechanism and aggregation model of the ultrasound initiated SEBS-g-MAH at room temperature were also proposed.
2015, 33(7): 1000-1008
doi: 10.1007/s10118-015-1648-5
Abstract:
A series of copolymers of ethylene with 1-hexene synthesized using a metallocene catalyst are selected and mixed. The blend is fractionated via preparative temperature rising elution fractionation (P-TREF). All fractions are characterized via high-temperature gel permeation chromatography (GPC), 13C nuclear magnetic resonance spectroscopy (13C-NMR), and differential scanning calorimetry (DSC). The changes in the DSC melting peak temperatures of the fractions from P-TREF as a function of elution temperature are almost linear, thereby providing a reference through which the elution temperature of TREF experiments could be selected. Moreover, the standard calibration curve (ethylene/1-hexene) of P-TREF is established, which relates to the degree of short-chain branching of the fractions. The standard calibration curve of P-TREF is beneficial to study on the complicated branching structure of polyethylene. A convenient method for selecting the fractionation temperature for TREF experiments is elaborated. The polyethylene sample is fractionated via successive self-nucleation and annealing (SSA) thermal fractionation. A multiple-melting endotherm is obtained through the final DSC heating scan for the sample after SSA thermal fractionation. A series of fractionation temperatures are then selected through the relationship between the DSC melting peak temperature and TREF elution temperature.
A series of copolymers of ethylene with 1-hexene synthesized using a metallocene catalyst are selected and mixed. The blend is fractionated via preparative temperature rising elution fractionation (P-TREF). All fractions are characterized via high-temperature gel permeation chromatography (GPC), 13C nuclear magnetic resonance spectroscopy (13C-NMR), and differential scanning calorimetry (DSC). The changes in the DSC melting peak temperatures of the fractions from P-TREF as a function of elution temperature are almost linear, thereby providing a reference through which the elution temperature of TREF experiments could be selected. Moreover, the standard calibration curve (ethylene/1-hexene) of P-TREF is established, which relates to the degree of short-chain branching of the fractions. The standard calibration curve of P-TREF is beneficial to study on the complicated branching structure of polyethylene. A convenient method for selecting the fractionation temperature for TREF experiments is elaborated. The polyethylene sample is fractionated via successive self-nucleation and annealing (SSA) thermal fractionation. A multiple-melting endotherm is obtained through the final DSC heating scan for the sample after SSA thermal fractionation. A series of fractionation temperatures are then selected through the relationship between the DSC melting peak temperature and TREF elution temperature.
2015, 33(7): 1009-1017
doi: 10.1007/s10118-015-1646-7
Abstract:
Here, we introduce the design of the structure of RR (RYYAAFFARR), an inhibitor of A aggregation, using molecular docking, and compare the inhibitory ability between RR and LPFFD, which interacts with A mainly depending on hydrophobic interaction. Our results showed that RR which can target multiple regions of A with multiple weak interactions is better than those that only target a single region with the single driving force mainly.
Here, we introduce the design of the structure of RR (RYYAAFFARR), an inhibitor of A aggregation, using molecular docking, and compare the inhibitory ability between RR and LPFFD, which interacts with A mainly depending on hydrophobic interaction. Our results showed that RR which can target multiple regions of A with multiple weak interactions is better than those that only target a single region with the single driving force mainly.
2015, 33(7): 1018-1027
doi: 10.1007/s10118-015-1647-6
Abstract:
The capacitance performances of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) supramolecular hydrogels have been investigated systematically. The materials show a specific capacitance of 67 F/g and display excellent rate capability at the scan rate as high as 5000 mV/s in the cyclic voltammogram measurements, accompanied by good cycle stability. On the basis of the measurements of the microscale morphologies, specific areas and electrical conductivities, the mechanisms for the improvement of the electrochemical properties are discussed and ascribed to the novel porous microstructures of the hydrogels and the synergetic effect of the rigid PEDOT and soft PSS components. Furthermore, polyaniline (PAn) is compounded with the PEDOT-PSS hydrogels through an interfacial polymerization process, endowing the hydrogel materials with a higher specific capacitance of 160 F/g at the scan rate of 5000 mV/s. The significance of this work lies in the demonstration of a novel method to solve the problems of conducting polymers in electrochemical applications.
The capacitance performances of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT-PSS) supramolecular hydrogels have been investigated systematically. The materials show a specific capacitance of 67 F/g and display excellent rate capability at the scan rate as high as 5000 mV/s in the cyclic voltammogram measurements, accompanied by good cycle stability. On the basis of the measurements of the microscale morphologies, specific areas and electrical conductivities, the mechanisms for the improvement of the electrochemical properties are discussed and ascribed to the novel porous microstructures of the hydrogels and the synergetic effect of the rigid PEDOT and soft PSS components. Furthermore, polyaniline (PAn) is compounded with the PEDOT-PSS hydrogels through an interfacial polymerization process, endowing the hydrogel materials with a higher specific capacitance of 160 F/g at the scan rate of 5000 mV/s. The significance of this work lies in the demonstration of a novel method to solve the problems of conducting polymers in electrochemical applications.
2015, 33(7): 1028-1037
doi: 10.1007/s10118-015-1643-x
Abstract:
In this work, the effects of annealing conditions on the microstructure of polypropylene (PP) precursor films and further on the porous structure and permeability of stretched membranes were investigated. Combinations of WAXD, FTIR, DSC and DMA results clearly showed the crystalline orientation and crystallinity of the precursor film increased with annealing temperature, while the molecular chain entanglements in the amorphous phase decreased. Changes in the deformation behavior suggested more lamellar separation occurred for the films annealed at higher temperatures. Surface morphologies of the membranes examined by SEM revealed more pore number and uniform porous structure as the annealing temperature increased. In accordance with the SEM results, the permeability of the membranes increased with annealing temperature. On the other hand, it was found that 10 min was almost enough for the annealing process to obtain the microporous membranes with an optimal permeability.
In this work, the effects of annealing conditions on the microstructure of polypropylene (PP) precursor films and further on the porous structure and permeability of stretched membranes were investigated. Combinations of WAXD, FTIR, DSC and DMA results clearly showed the crystalline orientation and crystallinity of the precursor film increased with annealing temperature, while the molecular chain entanglements in the amorphous phase decreased. Changes in the deformation behavior suggested more lamellar separation occurred for the films annealed at higher temperatures. Surface morphologies of the membranes examined by SEM revealed more pore number and uniform porous structure as the annealing temperature increased. In accordance with the SEM results, the permeability of the membranes increased with annealing temperature. On the other hand, it was found that 10 min was almost enough for the annealing process to obtain the microporous membranes with an optimal permeability.
2015, 33(7): 1038-1047
doi: 10.1007/s10118-015-1656-5
Abstract:
The hybrid micelles of polystyrene-b-poly((N-isopropyl acrylamide)-co-(4-vinylbenzyl chloride)) block copolymer (PS-b-P(NIPAM-co-VBC)) with Prussian blue (PB) in the corona were prepared by reaction of pentacyano(4-(dimethylamino)-pyridine)ferrate (Fe-DMAP)-attached PS-b-P(NIPAM-co-VBC) with FeCl3. The formation of the PB framework inside the micelles was verified by UV-Vis, FTIR and TGA. The morphology of the hybrid micelles was studied by TEM and compared with that of the neat and Fe-DMAP-attached PS-b-P(NIPAM-co-VBC). It is found that attachment of Fe-DMAP may change the short rod-like micelles of the neat PS-b-P(NIPAM-co-VBC) into spherical ones and lead to a smaller micelle size. The morphology of the hybrid micelles may be altered or remain unchanged after formation of the PB framework, depending on the chain structure of PS-b-P(NIPAM-co-VBC) and starting concentration. The thermoresponsive behavior of different micelles was studied using DLS. It is observed that attachment of Fe-DMAP can improve the hydrophilicity of the P(NIPAM-co-VBC) block, leading to weaker hysteresis of the micelle size during the heating and cooling cycle. However, the crosslinked PB framework in the micellar corona may result in a more evident hysteresis phenomenon and blur the two-stepwise change of the micellar size with temperature.
The hybrid micelles of polystyrene-b-poly((N-isopropyl acrylamide)-co-(4-vinylbenzyl chloride)) block copolymer (PS-b-P(NIPAM-co-VBC)) with Prussian blue (PB) in the corona were prepared by reaction of pentacyano(4-(dimethylamino)-pyridine)ferrate (Fe-DMAP)-attached PS-b-P(NIPAM-co-VBC) with FeCl3. The formation of the PB framework inside the micelles was verified by UV-Vis, FTIR and TGA. The morphology of the hybrid micelles was studied by TEM and compared with that of the neat and Fe-DMAP-attached PS-b-P(NIPAM-co-VBC). It is found that attachment of Fe-DMAP may change the short rod-like micelles of the neat PS-b-P(NIPAM-co-VBC) into spherical ones and lead to a smaller micelle size. The morphology of the hybrid micelles may be altered or remain unchanged after formation of the PB framework, depending on the chain structure of PS-b-P(NIPAM-co-VBC) and starting concentration. The thermoresponsive behavior of different micelles was studied using DLS. It is observed that attachment of Fe-DMAP can improve the hydrophilicity of the P(NIPAM-co-VBC) block, leading to weaker hysteresis of the micelle size during the heating and cooling cycle. However, the crosslinked PB framework in the micellar corona may result in a more evident hysteresis phenomenon and blur the two-stepwise change of the micellar size with temperature.
2015, 33(7): 1048-1057
doi: 10.1007/s10118-015-1655-6
Abstract:
Thermal and salt dual stimuli-responsive filter-paper-based membranes were prepared by UV-induced grafting of NIPAM-based polymers on paper surface. The grafting ratio could be controlled by monomer concentration during grafting polymerization. The results from pressure drop measurement of the mobile phase flowed cross the membrane demonstrate that an appropriate grafting ratio would be 8%-10%. Protein adsorption on the membrane through hydrophobic interaction could be promoted by increasing temperature and lyotropic salt concentration. The effect of grafted polymer structure on protein binding performance was studied. Filter paper grafted with NIPAM-based branched copolymer consisting of hydrophobic monomer moieties shows ten times higher protein binding capacity than that of the original filter paper. The separation of plasma proteins using the dual stimuli-responsive membrane was examined to demonstrate feasible application for hydrophobic interaction chromatographic separation of proteins.
Thermal and salt dual stimuli-responsive filter-paper-based membranes were prepared by UV-induced grafting of NIPAM-based polymers on paper surface. The grafting ratio could be controlled by monomer concentration during grafting polymerization. The results from pressure drop measurement of the mobile phase flowed cross the membrane demonstrate that an appropriate grafting ratio would be 8%-10%. Protein adsorption on the membrane through hydrophobic interaction could be promoted by increasing temperature and lyotropic salt concentration. The effect of grafted polymer structure on protein binding performance was studied. Filter paper grafted with NIPAM-based branched copolymer consisting of hydrophobic monomer moieties shows ten times higher protein binding capacity than that of the original filter paper. The separation of plasma proteins using the dual stimuli-responsive membrane was examined to demonstrate feasible application for hydrophobic interaction chromatographic separation of proteins.
2015, 33(7): 1058-1068
doi: 10.1007/s10118-015-1652-9
Abstract:
An effective procedure has been developed to synthesize the functionalized graphene oxide grafted by maleic anhydride grafted liquid polybutadiene (MLPB-GO). Fourier transform spectroscopy and X-ray photoelectron spectroscopy indicate the successful functionalization of GO. The NR/MLPB-GO composites were then prepared by the co-coagulation process. The results show that the mechanical properties of NR/MLPB-GO composites are obviously superior to those of NR/GO composites and neat NR. Compared with neat NR, the tensile strength, modulus at 300% strain and tear strength of NR composite containing 2.12 phr MLPB-GO are significantly increased by 40.5%, 109.1% and 85.0%, respectively. Dynamic mechanical analysis results show that 84% increase in storage modulus and 2.9 K enhancement in the glass transition temperature of the composite have been achieved with the incorporation of 2.12 phr MLPB-GO into NR. The good dispersion of GO and the strong interface interaction in the composites are responsible for the unprecedented reinforcing efficiency of MLPB-GO towards NR.
An effective procedure has been developed to synthesize the functionalized graphene oxide grafted by maleic anhydride grafted liquid polybutadiene (MLPB-GO). Fourier transform spectroscopy and X-ray photoelectron spectroscopy indicate the successful functionalization of GO. The NR/MLPB-GO composites were then prepared by the co-coagulation process. The results show that the mechanical properties of NR/MLPB-GO composites are obviously superior to those of NR/GO composites and neat NR. Compared with neat NR, the tensile strength, modulus at 300% strain and tear strength of NR composite containing 2.12 phr MLPB-GO are significantly increased by 40.5%, 109.1% and 85.0%, respectively. Dynamic mechanical analysis results show that 84% increase in storage modulus and 2.9 K enhancement in the glass transition temperature of the composite have been achieved with the incorporation of 2.12 phr MLPB-GO into NR. The good dispersion of GO and the strong interface interaction in the composites are responsible for the unprecedented reinforcing efficiency of MLPB-GO towards NR.
