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2016 Volume 34 Issue 6
2016, 34(6): 659-678
doi: 10.1007/s10118-016-1800-x
Abstract:
Block copolymer lithography is emerging as one of the leading technologies for patterning nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical and lamellar domains is required for pattern transfer from the block copolymer film. This review highlights the state-of-art development of brushes to modify the substrates to control the assembly behaviors of block copolymers in films. Selected important contributions to the development of self-assembled monolayers, polymer brushes and mats, and chemically patterned brushes are discussed.
Block copolymer lithography is emerging as one of the leading technologies for patterning nanoscale dense features. In almost all potential applications of this technology, control over the orientation of cylindrical and lamellar domains is required for pattern transfer from the block copolymer film. This review highlights the state-of-art development of brushes to modify the substrates to control the assembly behaviors of block copolymers in films. Selected important contributions to the development of self-assembled monolayers, polymer brushes and mats, and chemically patterned brushes are discussed.
2016, 34(6): 679-687
doi: 10.1007/s10118-016-1787-3
Abstract:
In this study, to improve hemocompatibility of biomedical materials, a waterborne polyurethane (WPU)/heparin release coating system (WPU/heparin) is fabricated via simply blending biodegradable WPU emulsions with heparin aqueous solutions. The surface compositions and hydrophilicity of these WPU/heparin blend coatings are characterized by attenuated total reflectance infrared spectroscopy (ATR-FTIR) and water contact angle measurements. These WPU/heparin blend coatings show effectively controlled release of heparin, as determined by the toluidine blue method. Furthermore, the biocompatibility and anticoagulant activity of these blend coatings are evaluated based on the protein adsorption, platelet adhesion, activated partial thromboplastin time (APTT), thrombin time (TT), hemolysis, and cytotoxicity. The results indicate that better hemocompatibility and cytocompatilibity are obtained due to blending heparin into this waterborne polyurethane. Thus, the WPU/heparin blend coating system is expected to be valuable for various biomedical applications.
In this study, to improve hemocompatibility of biomedical materials, a waterborne polyurethane (WPU)/heparin release coating system (WPU/heparin) is fabricated via simply blending biodegradable WPU emulsions with heparin aqueous solutions. The surface compositions and hydrophilicity of these WPU/heparin blend coatings are characterized by attenuated total reflectance infrared spectroscopy (ATR-FTIR) and water contact angle measurements. These WPU/heparin blend coatings show effectively controlled release of heparin, as determined by the toluidine blue method. Furthermore, the biocompatibility and anticoagulant activity of these blend coatings are evaluated based on the protein adsorption, platelet adhesion, activated partial thromboplastin time (APTT), thrombin time (TT), hemolysis, and cytotoxicity. The results indicate that better hemocompatibility and cytocompatilibity are obtained due to blending heparin into this waterborne polyurethane. Thus, the WPU/heparin blend coating system is expected to be valuable for various biomedical applications.
2016, 34(6): 688-696
doi: 10.1007/s10118-016-1791-7
Abstract:
Polystyrene (PS)/triphenyl phosphate (TPP) composites were prepared by both suspension polymerization and melt extrusion, and a comparative study of the flame retardance and mechanical properties was carried out. The results showed that suspension polymerization was a better technique than melt extrusion for obtaining good dispersity of the PS/TPP composite. The TPP nanoparticles, which were approximately 50 nm in size, were homogenously and uniformly dispersed in the PS matrix by suspension polymerization in one-step. However, the PS/TPP composite was partially agglomerated, exhibiting irregularly shaped micron-scale particles as a result of melt extrusion. In contrast to the melt extrusion, the limited oxygen index (LOI) of the PS/TPP nanocomposite by suspension polymerization increased to 22.6% from 21.8%, and time to ignition (TTI) increased by 12.3%, the peak heat release rate (PHRR) decreased by 8.5%, and the total heat release (THR) decreased by 11.0%. The mechanical properties of the PS/TPP nanocomposite by suspension polymerization also increased. The tensile strength, elongation at break, and flexural strength increased by 36.4%, 8.5%, and 108%, respectively.
Polystyrene (PS)/triphenyl phosphate (TPP) composites were prepared by both suspension polymerization and melt extrusion, and a comparative study of the flame retardance and mechanical properties was carried out. The results showed that suspension polymerization was a better technique than melt extrusion for obtaining good dispersity of the PS/TPP composite. The TPP nanoparticles, which were approximately 50 nm in size, were homogenously and uniformly dispersed in the PS matrix by suspension polymerization in one-step. However, the PS/TPP composite was partially agglomerated, exhibiting irregularly shaped micron-scale particles as a result of melt extrusion. In contrast to the melt extrusion, the limited oxygen index (LOI) of the PS/TPP nanocomposite by suspension polymerization increased to 22.6% from 21.8%, and time to ignition (TTI) increased by 12.3%, the peak heat release rate (PHRR) decreased by 8.5%, and the total heat release (THR) decreased by 11.0%. The mechanical properties of the PS/TPP nanocomposite by suspension polymerization also increased. The tensile strength, elongation at break, and flexural strength increased by 36.4%, 8.5%, and 108%, respectively.
2016, 34(6): 697-708
doi: 10.1007/s10118-016-1796-2
Abstract:
In this work, the optimal electrospinning conditions of trans-polyisoprene (TPI) solutions were evaluated nevertheless its lower glass transition temperature than the room temperature. Subsequently, chemical crosslinking of TPI nonwovens was firstly investigated by vulcanizing at high temperatures in the case of the persistence of nanofiber structure. For this purpose, curing agents of TPI were embedded in TPI nanofibers by co-electrospinning, and then a protect layer was coated on TPI nanofibers by filtering gelatin solution going through TPI nonwoven before the vulcanization at 140-160 ℃. The results showed that the vulcanization of TPI fibrous nonwoven at high temperatures did not destroy the fiber morphology. Interestingly, TPI fibrous nonwovens after vulcanization showed excellent mechanical properties (~17 MPa of tensile strength) that could be comparable to or even higher than that of some bulk rubber materials.
In this work, the optimal electrospinning conditions of trans-polyisoprene (TPI) solutions were evaluated nevertheless its lower glass transition temperature than the room temperature. Subsequently, chemical crosslinking of TPI nonwovens was firstly investigated by vulcanizing at high temperatures in the case of the persistence of nanofiber structure. For this purpose, curing agents of TPI were embedded in TPI nanofibers by co-electrospinning, and then a protect layer was coated on TPI nanofibers by filtering gelatin solution going through TPI nonwoven before the vulcanization at 140-160 ℃. The results showed that the vulcanization of TPI fibrous nonwoven at high temperatures did not destroy the fiber morphology. Interestingly, TPI fibrous nonwovens after vulcanization showed excellent mechanical properties (~17 MPa of tensile strength) that could be comparable to or even higher than that of some bulk rubber materials.
2016, 34(6): 709-719
doi: 10.1007/s10118-016-1788-2
Abstract:
In this study, we chose corn stover hemicellulose for the preparation of hydrogels with admirable adsorption properties under mild alkaline conditions. Clay nanosheets were introduced to this system and hemicellulose/clay hybrid hydrogels were prepared. Morphological, mechanical properties and the methylene blue adsorption behaviors of the prepared hydrogels were studied. Results suggested that the addition of clay not only improved the mechanical strength of hemicellulose-based hydrogels, but also increased the adsorption capacity on methylene blue. Moreover, the adsorptions were confirmed to follow pseudo-second order equation for both gels with and without clay. The maximum adsorption capacities on methylene blue for hemicellulose-based hydrogels with or without clay reached 148.8 and 95.6 mg/g, respectively. These results implied that hemicellulose-based hydrogels could be used as promising adsorbents for the removal of methylene blue from waste water.
In this study, we chose corn stover hemicellulose for the preparation of hydrogels with admirable adsorption properties under mild alkaline conditions. Clay nanosheets were introduced to this system and hemicellulose/clay hybrid hydrogels were prepared. Morphological, mechanical properties and the methylene blue adsorption behaviors of the prepared hydrogels were studied. Results suggested that the addition of clay not only improved the mechanical strength of hemicellulose-based hydrogels, but also increased the adsorption capacity on methylene blue. Moreover, the adsorptions were confirmed to follow pseudo-second order equation for both gels with and without clay. The maximum adsorption capacities on methylene blue for hemicellulose-based hydrogels with or without clay reached 148.8 and 95.6 mg/g, respectively. These results implied that hemicellulose-based hydrogels could be used as promising adsorbents for the removal of methylene blue from waste water.
2016, 34(6): 720-729
doi: 10.1007/s10118-016-1795-3
Abstract:
A series of random copolymers (PCLAs) were synthesized by ring-opening polymerization of D,L-lactide (LA) and ε-caprolactone (CL) with different molar ratios. PCLA based polyurethanes (PCLAUs) were obtained by chain-extending of PCLA and polytetramethylene ether (PTMEG) with hexamethylene diisocyanate (HDI). All the PCLAUs exhibit good shape memory properties with high shape fixity ratios above 98% and shape recovery ratios above 82% in the first cycle and 91% in the second cycle. PCLAUs with less CL content show faster recovery speed and PCLAUs with more CL content show higher shape recovery ratio. The trigger temperature can be tuned or controlled around body temperature by adjusting the molar ratio of LA to CL. The PCLAUs have potential applications in implant biomedical devices, especially for minimally invasive deployable devices.
A series of random copolymers (PCLAs) were synthesized by ring-opening polymerization of D,L-lactide (LA) and ε-caprolactone (CL) with different molar ratios. PCLA based polyurethanes (PCLAUs) were obtained by chain-extending of PCLA and polytetramethylene ether (PTMEG) with hexamethylene diisocyanate (HDI). All the PCLAUs exhibit good shape memory properties with high shape fixity ratios above 98% and shape recovery ratios above 82% in the first cycle and 91% in the second cycle. PCLAUs with less CL content show faster recovery speed and PCLAUs with more CL content show higher shape recovery ratio. The trigger temperature can be tuned or controlled around body temperature by adjusting the molar ratio of LA to CL. The PCLAUs have potential applications in implant biomedical devices, especially for minimally invasive deployable devices.
2016, 34(6): 730-738
doi: 10.1007/s10118-016-1789-1
Abstract:
A series of β-cyclodextrin-conjugated 4-arm poly(ethylene glycol)-poly(lactide-co-glycolide) (4-arm PEG-PLGA) copolymers were synthesized by a ring-opening polymerization of D,L-lactide and glycolide using 4-arm PEG as initiator, and then conjugated with mono(6-ethylenediamine-6-deoxy)-β-cyclodextrin (CDen) or ethylenediamino-bridged bis-β-CD (BCDen). The chemical structures of copolymers were confirmed by 1H-NMR and FTIR spectroscopy. The β-CD-conjugated PEG-PLGA formed stable reverse micelles due to the formation of β-CD and bovine serum albumin (BSA) inclusion complexation, which could accommodate BSA in the organic solvent with improved encapsulation efficiency. Moreover, we demonstrated a one-step approach to construct macroporous protein-containing films using these reverse micelles. The films with ordered pore arrays were directly prepared from reverse micelles. Interestingly, the protein was totally located in the whole matrix except for the pores.
A series of β-cyclodextrin-conjugated 4-arm poly(ethylene glycol)-poly(lactide-co-glycolide) (4-arm PEG-PLGA) copolymers were synthesized by a ring-opening polymerization of D,L-lactide and glycolide using 4-arm PEG as initiator, and then conjugated with mono(6-ethylenediamine-6-deoxy)-β-cyclodextrin (CDen) or ethylenediamino-bridged bis-β-CD (BCDen). The chemical structures of copolymers were confirmed by 1H-NMR and FTIR spectroscopy. The β-CD-conjugated PEG-PLGA formed stable reverse micelles due to the formation of β-CD and bovine serum albumin (BSA) inclusion complexation, which could accommodate BSA in the organic solvent with improved encapsulation efficiency. Moreover, we demonstrated a one-step approach to construct macroporous protein-containing films using these reverse micelles. The films with ordered pore arrays were directly prepared from reverse micelles. Interestingly, the protein was totally located in the whole matrix except for the pores.
2016, 34(6): 739-754
doi: 10.1007/s10118-016-1786-4
Abstract:
This article addresses the synthesis of organically tailored Ni-Al layered double hydroxide (ONi-Al LDH) and its use in the fabrication of exfoliated poly(methyl methacrylate) (PMMA) nanocomposites. The pristine Ni-Al LDH was initially synthesized by co-precipitation method and subsequently modified using sodium dodecyl sulfate to obtain ONi-Al LDH. Nanocomposites of PMMA containing various amounts of modified Ni-Al LDH (3 wt%-7 wt%) were synthesized via solvent blending method to investigate the influence of LDH content on the properties of PMMA matrix. Several characterization methods such as X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), rheological analysis, differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA), were employed to examine the structural, viscoelastic and thermal properties of PMMA/OLDH nanocomposites. The results of XRD and TEM examination confirm the formation of partially exfoliated PMMA/OLDH nanocomposites. The FTIR results elucidate that the characteristic bands for both pure PMMA and modified LDH are present in the spectra of PMMA/OLDH nanocomposites. Rheological analyses were carried out to examine the adhesion between polymer matrix and fillers present in the nanocomposite sample. The TGA data indicate that the PMMA nanocomposites exhibit higher thermal stability when compared to pure PMMA. The thermal decomposition temperature of PMMA/OLDH nanocomposites increases by 28 K compared to that of pure PMMA at 15% weight loss as a point of reference. In comparison with pure PMMA, the PMMA nanocomposite containing 7 wt% LDH demonstrates improved glass transition temperature (Tg) of around 3 K. The activation energy (Ea), reaction orders (n) and reaction mechanism of thermal degradation of PMMA/OLDH nanocomposites were evaluated using different kinetic models. Water uptake capacity of the PMMA/OLDH nanocomposites is less than that of the pure PMMA.
This article addresses the synthesis of organically tailored Ni-Al layered double hydroxide (ONi-Al LDH) and its use in the fabrication of exfoliated poly(methyl methacrylate) (PMMA) nanocomposites. The pristine Ni-Al LDH was initially synthesized by co-precipitation method and subsequently modified using sodium dodecyl sulfate to obtain ONi-Al LDH. Nanocomposites of PMMA containing various amounts of modified Ni-Al LDH (3 wt%-7 wt%) were synthesized via solvent blending method to investigate the influence of LDH content on the properties of PMMA matrix. Several characterization methods such as X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), rheological analysis, differential scanning calorimetry (DSC) and thermo gravimetric analysis (TGA), were employed to examine the structural, viscoelastic and thermal properties of PMMA/OLDH nanocomposites. The results of XRD and TEM examination confirm the formation of partially exfoliated PMMA/OLDH nanocomposites. The FTIR results elucidate that the characteristic bands for both pure PMMA and modified LDH are present in the spectra of PMMA/OLDH nanocomposites. Rheological analyses were carried out to examine the adhesion between polymer matrix and fillers present in the nanocomposite sample. The TGA data indicate that the PMMA nanocomposites exhibit higher thermal stability when compared to pure PMMA. The thermal decomposition temperature of PMMA/OLDH nanocomposites increases by 28 K compared to that of pure PMMA at 15% weight loss as a point of reference. In comparison with pure PMMA, the PMMA nanocomposite containing 7 wt% LDH demonstrates improved glass transition temperature (Tg) of around 3 K. The activation energy (Ea), reaction orders (n) and reaction mechanism of thermal degradation of PMMA/OLDH nanocomposites were evaluated using different kinetic models. Water uptake capacity of the PMMA/OLDH nanocomposites is less than that of the pure PMMA.
2016, 34(6): 755-765
doi: 10.1007/s10118-016-1792-6
Abstract:
Capture and detection of metastatic cancer cells are crucial for diagnosis and treatment of malignant neoplasm. Here, we report the use of folic acid (FA) modified electrospun poly(vinyl alcohol) (PVA)/polyethyleneimine (PEI) nanofibers for cancer cell capture applications. Electrospun PVA/PEI nanofibers crosslinked by glutaraldehyde vapor were modified with FA via a poly(ethylene glycol) (PEG) spacer, followed by acetylation of the fiber surface PEI amines. The formed FA-modified nanofibers were well characterized. The morphology of the electrospun PVA/PEI nanofibers is smooth and uniform despite the surface modification. In addition, the FA-modified nanofibers display good hemocompatibility as confirmed by hemolysis assay. Importantly, the developed FA-modified nanofibers are able to specifically capture cancer cells overexpressing FA receptors, which were validated by quantitative cell counting assay and qualitative confocal microscopy analysis. The developed FA-modified PVA/PEI nanofibers may be used for capturing circulating tumor cells for cancer diagnosis applications.
Capture and detection of metastatic cancer cells are crucial for diagnosis and treatment of malignant neoplasm. Here, we report the use of folic acid (FA) modified electrospun poly(vinyl alcohol) (PVA)/polyethyleneimine (PEI) nanofibers for cancer cell capture applications. Electrospun PVA/PEI nanofibers crosslinked by glutaraldehyde vapor were modified with FA via a poly(ethylene glycol) (PEG) spacer, followed by acetylation of the fiber surface PEI amines. The formed FA-modified nanofibers were well characterized. The morphology of the electrospun PVA/PEI nanofibers is smooth and uniform despite the surface modification. In addition, the FA-modified nanofibers display good hemocompatibility as confirmed by hemolysis assay. Importantly, the developed FA-modified nanofibers are able to specifically capture cancer cells overexpressing FA receptors, which were validated by quantitative cell counting assay and qualitative confocal microscopy analysis. The developed FA-modified PVA/PEI nanofibers may be used for capturing circulating tumor cells for cancer diagnosis applications.
2016, 34(6): 766-776
doi: 10.1007/s10118-016-1798-0
Abstract:
Three diamine monomers with different derivatives of imidazole heterocyclic ring, aryl ethers and electron withdrawing trifluoromethyl groups in the backbone were synthesized and used in polycodensation reaction with various aliphatic and aromatic dicarboxylic acids for preparation of a series of novel polyamides (PAs). The PAs were obtained in high yields and possessed inherent viscosities in the range of 0.26-0.75 dL/g. All of the polymers were amorphous in nature, showed outstanding solubility and could be easily dissolved in amide-type polar aprotic solvents. They showed good thermal stability with glass transition temperatures between 162-302 ℃. Thermogravimetric analysis showed that all polymers were stable, with 10% weight loss recorded above 421 ℃ in N2 atmospheres. All the PAs presented fluorescence upon irradiation with ultraviolet light and thus showed promise for applications in electroluminescent devices. The monomers and PAs were also screened for antibacterial activity against Gram positive and Gram negative bacteria.
Three diamine monomers with different derivatives of imidazole heterocyclic ring, aryl ethers and electron withdrawing trifluoromethyl groups in the backbone were synthesized and used in polycodensation reaction with various aliphatic and aromatic dicarboxylic acids for preparation of a series of novel polyamides (PAs). The PAs were obtained in high yields and possessed inherent viscosities in the range of 0.26-0.75 dL/g. All of the polymers were amorphous in nature, showed outstanding solubility and could be easily dissolved in amide-type polar aprotic solvents. They showed good thermal stability with glass transition temperatures between 162-302 ℃. Thermogravimetric analysis showed that all polymers were stable, with 10% weight loss recorded above 421 ℃ in N2 atmospheres. All the PAs presented fluorescence upon irradiation with ultraviolet light and thus showed promise for applications in electroluminescent devices. The monomers and PAs were also screened for antibacterial activity against Gram positive and Gram negative bacteria.
2016, 34(6): 777-784
doi: 10.1007/s10118-016-1790-8
Abstract:
A betaine-type styrene monomer with the quaternary ammonium-borate anion inner-salt pair was synthesized through the quaternization reaction and polymerized to afford the target polybetaine of poly(4-vinylbenzyl methyl-diethanol ammonium borate) (PVMAB). The chemical structures of the monomer and polymer were well demonstrated with 1H-NMR and 11B-NMR spectra analysis. The thermal-sensitive experiment showed that PVMAB in water afforded gradually well-defined sigmoidal transmittance-temperature (T-t) curves along with the increasing polymer concentration. However, the phase transition temperatures at the bottom of the S-shaped curves were always below 10 ℃ due to the very weak zwitterionic association of the ammonium-borate inner-salt pairs. The UCST phase transition could also be tuned by changing the ethanol content in the ethanol/water mixture. And the cytotoxicity experiment demonstrated the good biomimetic property of PVMAB. This study enriches the toolbox of polybetaines by introducing the quaternary ammonium-borate anion zwitterionic pair in the repeat units, therefore broadens the scope of synthetic polybetaines.
A betaine-type styrene monomer with the quaternary ammonium-borate anion inner-salt pair was synthesized through the quaternization reaction and polymerized to afford the target polybetaine of poly(4-vinylbenzyl methyl-diethanol ammonium borate) (PVMAB). The chemical structures of the monomer and polymer were well demonstrated with 1H-NMR and 11B-NMR spectra analysis. The thermal-sensitive experiment showed that PVMAB in water afforded gradually well-defined sigmoidal transmittance-temperature (T-t) curves along with the increasing polymer concentration. However, the phase transition temperatures at the bottom of the S-shaped curves were always below 10 ℃ due to the very weak zwitterionic association of the ammonium-borate inner-salt pairs. The UCST phase transition could also be tuned by changing the ethanol content in the ethanol/water mixture. And the cytotoxicity experiment demonstrated the good biomimetic property of PVMAB. This study enriches the toolbox of polybetaines by introducing the quaternary ammonium-borate anion zwitterionic pair in the repeat units, therefore broadens the scope of synthetic polybetaines.
2016, 34(6): 785-796
doi: 10.1007/s10118-016-1799-z
Abstract:
To minimize the loading level of the char-forming phosphorus based flame retardants in the poly(lactic acid) (PLA) with reduced flammability, we have developed the flame-retarded PLA nanocomposites by melt blending method incorporating organically modified montmorillonite (OMMT) and aluminium diethylphosphinate (AlPi) additives. The influence of AlPi and OMMT on flame retardancy and thermal stability of PLA was thoroughly investigated by means of the limiting oxygen index (LOI), UL94 test, cone calorimeter, X-ray diffraction (XRD), thermogravimetric analysis and scanning electronic microscopy (SEM). The experimental results show that the PLA/AlPi/OMMT system has excellent fire retardancy. The LOI value increases from 19% for pristine PLA to 28% for the flame-retarded PLA. Cone calorimeter analysis of the PLA/AlPi/OMMT exhibits a reduction in the peak heat release rate values by 26.2%. Thermogravimetric analysis and SEM of cone calorimeter residues indicate that OMMT significantly enhances the thermal stability, promotes char-forming and suppresses the melt dripping. The research of this study implies that the combining of the flame retardant and organoclay results in a synergistic effect. In addition, the flame-retarded PLA nanocomposite also exhibits notable increase in the impact strength and the elongation at break.
To minimize the loading level of the char-forming phosphorus based flame retardants in the poly(lactic acid) (PLA) with reduced flammability, we have developed the flame-retarded PLA nanocomposites by melt blending method incorporating organically modified montmorillonite (OMMT) and aluminium diethylphosphinate (AlPi) additives. The influence of AlPi and OMMT on flame retardancy and thermal stability of PLA was thoroughly investigated by means of the limiting oxygen index (LOI), UL94 test, cone calorimeter, X-ray diffraction (XRD), thermogravimetric analysis and scanning electronic microscopy (SEM). The experimental results show that the PLA/AlPi/OMMT system has excellent fire retardancy. The LOI value increases from 19% for pristine PLA to 28% for the flame-retarded PLA. Cone calorimeter analysis of the PLA/AlPi/OMMT exhibits a reduction in the peak heat release rate values by 26.2%. Thermogravimetric analysis and SEM of cone calorimeter residues indicate that OMMT significantly enhances the thermal stability, promotes char-forming and suppresses the melt dripping. The research of this study implies that the combining of the flame retardant and organoclay results in a synergistic effect. In addition, the flame-retarded PLA nanocomposite also exhibits notable increase in the impact strength and the elongation at break.
