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2020 Volume 38 Issue 2
2020, 38(2): 109-117
doi: 10.1007/s10118-019-2306-0
Abstract:
In this study, novel electrochromic copolymers of 3,4-ethylenedioxythiophene (EDOT) and (E)-1,2-bis(2-fluoro-4-(4-hexylthiophen-2-yl)phenyl)diazene (M1) with different monomer feed ratios were designed and synthesized electrochemically. Electrochemical and spectroelectrochemical characterizations were performed using voltammetry and UV-Vis-NIR spectrophotometry techniques to test the applicability of copolymers for electrochromic applications. In terms of electrochemical behaviors, addition of an electron-rich EDOT unit into the azobenzene-containing copolymer increased the electron density on the polymer chain and afforded copolymers with very low oxidation potentials at around 0.30 V. While the homopolymers (P1 and PEDOT) exhibited neutral state absorptions centered at 510 and 583 nm, EDOT-bearing copolymers showed red shifted absorptions compared to those of P1 with narrower optical band gaps. In addition, the poor optical contrast and switching times of azobenzene-bearing homopolymer were significantly improved with EDOT addition into the copolymer chain. As a result of the promising electrochromic and kinetic preperties, CoP1.5-bearing single layer electrochromic device that works between purple and light greenish blue colors was constructed and characterized.
In this study, novel electrochromic copolymers of 3,4-ethylenedioxythiophene (EDOT) and (E)-1,2-bis(2-fluoro-4-(4-hexylthiophen-2-yl)phenyl)diazene (M1) with different monomer feed ratios were designed and synthesized electrochemically. Electrochemical and spectroelectrochemical characterizations were performed using voltammetry and UV-Vis-NIR spectrophotometry techniques to test the applicability of copolymers for electrochromic applications. In terms of electrochemical behaviors, addition of an electron-rich EDOT unit into the azobenzene-containing copolymer increased the electron density on the polymer chain and afforded copolymers with very low oxidation potentials at around 0.30 V. While the homopolymers (P1 and PEDOT) exhibited neutral state absorptions centered at 510 and 583 nm, EDOT-bearing copolymers showed red shifted absorptions compared to those of P1 with narrower optical band gaps. In addition, the poor optical contrast and switching times of azobenzene-bearing homopolymer were significantly improved with EDOT addition into the copolymer chain. As a result of the promising electrochromic and kinetic preperties, CoP1.5-bearing single layer electrochromic device that works between purple and light greenish blue colors was constructed and characterized.
2020, 38(2): 118-125
doi: 10.1007/s10118-019-2307-z
Abstract:
In this study, two new dendronized nonlinear optical (NLO) polymers were synthesized with high FTC chromophore loading density by introduction of high generation chromophore dendrons on the side chains. Due to their suitable molecular weights, both of them possessed good solubility in common solvents. They also inherited the advantages of dendrimers (large NLO coefficient), especially for PG2 whose NLO coefficient d33 value was as high as 282 pm·V–1. Also, PG2 had a good temporal stability with 80% of its maximum value being retained at the temperature as high as 129 °C.
In this study, two new dendronized nonlinear optical (NLO) polymers were synthesized with high FTC chromophore loading density by introduction of high generation chromophore dendrons on the side chains. Due to their suitable molecular weights, both of them possessed good solubility in common solvents. They also inherited the advantages of dendrimers (large NLO coefficient), especially for PG2 whose NLO coefficient d33 value was as high as 282 pm·V–1. Also, PG2 had a good temporal stability with 80% of its maximum value being retained at the temperature as high as 129 °C.
2020, 38(2): 126-136
doi: 10.1007/s10118-019-2324-y
Abstract:
Dynamic control of mesenchymal stem cell (MSC) behaviors on biomaterial surface is critically involved in regulating the cell fate and tissue regeneration. Herein, a stimuli-responsive surface based on host-guest interaction with cell selectivity was developed to regulate migration of MSCs in situ by dynamic display of cell-specific peptides. Azobenzene-grafted MSC-affinitive peptides (EPLQLKM, Azo-E7) were grafted to β-cyclodextran (β-CD)-modified poly(2-hydroxyethyl methacrylate)-b-poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) (PHG) brushes, which were prepared by using surface-initiated atom transfer radical polymerization (SI-ATRP). X-ray photoelectron spectroscopy (XPS), quartz crystal microbalance (QCM), and water contact angle were used to characterize their structure and property. Cell adhesion assay showed that the combination effect of resisting property of PHG and MSC-affinity of E7 could promote the selective adhesion of MSCs over other types of cells such as RAW264.7 macrophages and NIH3T3 fibroblasts to some extent. UV-Vis spectroscopy proved that the competing guest molecules, amantadine hydrochloride (Ama), could release Azo-E7 peptides from the CD surface to different extents, and the effect was enhanced when UV irradiation was employed simultaneously. As a result, the decrease of cell adhesion density and migration rate could be achieved in situ. The cell density and migration rate could be reduced by over 40% by adding 20 μmol/L Ama, suggesting that this type of surface is a new platform for dynamic regulation of stem cell behaviors in situ.
Dynamic control of mesenchymal stem cell (MSC) behaviors on biomaterial surface is critically involved in regulating the cell fate and tissue regeneration. Herein, a stimuli-responsive surface based on host-guest interaction with cell selectivity was developed to regulate migration of MSCs in situ by dynamic display of cell-specific peptides. Azobenzene-grafted MSC-affinitive peptides (EPLQLKM, Azo-E7) were grafted to β-cyclodextran (β-CD)-modified poly(2-hydroxyethyl methacrylate)-b-poly(2-hydroxyethyl methacrylate-co-glycidyl methacrylate) (PHG) brushes, which were prepared by using surface-initiated atom transfer radical polymerization (SI-ATRP). X-ray photoelectron spectroscopy (XPS), quartz crystal microbalance (QCM), and water contact angle were used to characterize their structure and property. Cell adhesion assay showed that the combination effect of resisting property of PHG and MSC-affinity of E7 could promote the selective adhesion of MSCs over other types of cells such as RAW264.7 macrophages and NIH3T3 fibroblasts to some extent. UV-Vis spectroscopy proved that the competing guest molecules, amantadine hydrochloride (Ama), could release Azo-E7 peptides from the CD surface to different extents, and the effect was enhanced when UV irradiation was employed simultaneously. As a result, the decrease of cell adhesion density and migration rate could be achieved in situ. The cell density and migration rate could be reduced by over 40% by adding 20 μmol/L Ama, suggesting that this type of surface is a new platform for dynamic regulation of stem cell behaviors in situ.
2020, 38(2): 137-142
doi: 10.1007/s10118-019-2308-y
Abstract:
Poly(lactic acid) (PLA) is one of the most important bio-plastics, and chemical modification of the already-polymerized poly(lactic acid) chains may enable optimization of its material properties and expand its application areas. In this study, we demonstrated that poly(lactic acid) can be readily dissolved in acrylic acid at room temperature, and acrylic acid can be graft-polymerized onto poly(lactic acid) chains in solution with the help of photoinitiator benzophenone under 254 nm ultraviolet (UV) irradiation. Similar photo-grafting polymerization of acrylic acid (PAA) has only been studied before in the surface modification of polymer films. The graft ratio could be controlled by various reaction parameters, including irradiation time, benzophenone content, and monomer/polymer ratios. This photo-grafting reaction resulted in high graft ratio (graft ratio PAA/PLA up to 180%) without formation of homopolymers of acrylic acid. When the PAA/PLA graft ratio was higher than 100%, the resulting PLA-g-PAA polymer was found dispersible in water. The pros and cons of the photo-grafting reaction were also discussed.
Poly(lactic acid) (PLA) is one of the most important bio-plastics, and chemical modification of the already-polymerized poly(lactic acid) chains may enable optimization of its material properties and expand its application areas. In this study, we demonstrated that poly(lactic acid) can be readily dissolved in acrylic acid at room temperature, and acrylic acid can be graft-polymerized onto poly(lactic acid) chains in solution with the help of photoinitiator benzophenone under 254 nm ultraviolet (UV) irradiation. Similar photo-grafting polymerization of acrylic acid (PAA) has only been studied before in the surface modification of polymer films. The graft ratio could be controlled by various reaction parameters, including irradiation time, benzophenone content, and monomer/polymer ratios. This photo-grafting reaction resulted in high graft ratio (graft ratio PAA/PLA up to 180%) without formation of homopolymers of acrylic acid. When the PAA/PLA graft ratio was higher than 100%, the resulting PLA-g-PAA polymer was found dispersible in water. The pros and cons of the photo-grafting reaction were also discussed.
2020, 38(2): 143-150
doi: 10.1007/s10118-019-2332-y
Abstract:
Cross-linked polyamides (cPAs) were prepared through direct bulk Michael addition and subsequent polycondensation. Several mixed hexanediamine multi-esters (HDAMEs) were generated through the Michael addition of 1,6-hexanediamine (HDA) and methyl acrylate (MA) at 50 °C with different HDA/MA molar ratios. Melt polycondensation of HDAMEs then proceeded at 150 or 170 °C in flasks to obtain viscous fluids, and curing was continued in tetrafluoroethylene molds to obtain cPA films. The Michael addition was monitored on the basis of FTIR and ESI-MS spectra. The cPA films were characterized by DSC, TGA, dynamic mechanical analysis, and tensile test. These directly prepared cPAs exhibited Tg of 1–39 °C, tensile strength of up to 45 MPa, and strain at break from 18% to 40%. The cPAs with high tensile strength and good toughness were successfully synthesized through the direct bulk Michael addition from HDA and MA followed with polycondensation.
Cross-linked polyamides (cPAs) were prepared through direct bulk Michael addition and subsequent polycondensation. Several mixed hexanediamine multi-esters (HDAMEs) were generated through the Michael addition of 1,6-hexanediamine (HDA) and methyl acrylate (MA) at 50 °C with different HDA/MA molar ratios. Melt polycondensation of HDAMEs then proceeded at 150 or 170 °C in flasks to obtain viscous fluids, and curing was continued in tetrafluoroethylene molds to obtain cPA films. The Michael addition was monitored on the basis of FTIR and ESI-MS spectra. The cPA films were characterized by DSC, TGA, dynamic mechanical analysis, and tensile test. These directly prepared cPAs exhibited Tg of 1–39 °C, tensile strength of up to 45 MPa, and strain at break from 18% to 40%. The cPAs with high tensile strength and good toughness were successfully synthesized through the direct bulk Michael addition from HDA and MA followed with polycondensation.
2020, 38(2): 151-157
doi: 10.1007/s10118-019-2321-1
Abstract:
Four truxene-based conjugated microporous polymers (Tr-CMPs) were prepared via different synthetic methods and their structure-property relationships were studied. The polymer networks have high Brunauer-Emmett-Teller (BET) specific surface areas ranging from 554 m2·g–1 to 1024 m2·g–1. Pore sizes of the CMPs with different linkers are mainly located between 0.60 and 1.96 nm. Among all the Tr-CMPs, Tr-CMP4 has the highest BET surface area of 1024 m2·g–1 and exhibits the highest H2 uptake of 0.88 wt%. Tr-CMP2 prepared by Suzuki-Miyaura coupling reaction has the highest photoluminescence quantum yields (PLQYs) of 13.06% and CO2 uptake of 6.25 wt%.
Four truxene-based conjugated microporous polymers (Tr-CMPs) were prepared via different synthetic methods and their structure-property relationships were studied. The polymer networks have high Brunauer-Emmett-Teller (BET) specific surface areas ranging from 554 m2·g–1 to 1024 m2·g–1. Pore sizes of the CMPs with different linkers are mainly located between 0.60 and 1.96 nm. Among all the Tr-CMPs, Tr-CMP4 has the highest BET surface area of 1024 m2·g–1 and exhibits the highest H2 uptake of 0.88 wt%. Tr-CMP2 prepared by Suzuki-Miyaura coupling reaction has the highest photoluminescence quantum yields (PLQYs) of 13.06% and CO2 uptake of 6.25 wt%.
2020, 38(2): 158-163
doi: 10.1007/s10118-020-2338-5
Abstract:
Two octaisobutyl-polyhedral oligomeric silsesquioxanes (oib-POSS) reinforced biodegradable poly(ε-caprolactone) (PCL) composites were prepared via two different methods, i.e., melt compounding and solution casting, which were named as mPCL/oib-POSS and sPCL/oib-POSS, respectively, in this work. Oib-POSS dispersed finely in both composites; moreover, oib-POSS aggregates were larger in mPCL/oib-POSS than in sPCL/oib-POSS. Despite the different preparation methods, oib-POSS obviously promoted the crystallization of PCL, especially in sPCL/oib-POSS, but did not modify the crystal structure of PCL. The storage moduli of PCL were improved significantly in both composites. PCL/oib-POSS composites with enhanced crystallization behavior and improved dynamic mechanical properties were successfully prepared through both methods; moreover, the solution casting method was more effective than the melt compounding method.
Two octaisobutyl-polyhedral oligomeric silsesquioxanes (oib-POSS) reinforced biodegradable poly(ε-caprolactone) (PCL) composites were prepared via two different methods, i.e., melt compounding and solution casting, which were named as mPCL/oib-POSS and sPCL/oib-POSS, respectively, in this work. Oib-POSS dispersed finely in both composites; moreover, oib-POSS aggregates were larger in mPCL/oib-POSS than in sPCL/oib-POSS. Despite the different preparation methods, oib-POSS obviously promoted the crystallization of PCL, especially in sPCL/oib-POSS, but did not modify the crystal structure of PCL. The storage moduli of PCL were improved significantly in both composites. PCL/oib-POSS composites with enhanced crystallization behavior and improved dynamic mechanical properties were successfully prepared through both methods; moreover, the solution casting method was more effective than the melt compounding method.
2020, 38(2): 164-173
doi: 10.1007/s10118-020-2337-6
Abstract:
For the solid-solid transformation from form II to form I of isotactic polybutene-1 (iPB), the temperature dependence of form I nucleation and growth was deemed to control the transformation process. However, the relationship between form I formation and form II disappearance in the transformation process is not clear. In this work, the spontaneous crystal transformation from form II to I of iPB with 81 mol% mmmm sequence concentration is studied firstly by tracking the two processes, the decay of form II and the yielding of form I in a wide range of temperature spanning from 0 °C to 50 °C and in a long transformation time ranging from 5 min to 65 days with in situ FTIR and WAXD. Unlike the literature reports, the decay rate of form II is firstly found to be lower than the yielding rate of form I at all studied temperatures, especially at low transition temperature. This is attributed to the amorphous chains which locate near crystal lamella participating into the nucleation of form II. The regular chain folding and growth of iPB form I from amorphous chains containing short isotactic sequences also lead to an increase in crystallinity of form I compared with that of initial form II crystallized at 60 °C. An increase in the annealing temperature results in decrease in crystallinity and increase in lamellae thickness of iPB form I.
For the solid-solid transformation from form II to form I of isotactic polybutene-1 (iPB), the temperature dependence of form I nucleation and growth was deemed to control the transformation process. However, the relationship between form I formation and form II disappearance in the transformation process is not clear. In this work, the spontaneous crystal transformation from form II to I of iPB with 81 mol% mmmm sequence concentration is studied firstly by tracking the two processes, the decay of form II and the yielding of form I in a wide range of temperature spanning from 0 °C to 50 °C and in a long transformation time ranging from 5 min to 65 days with in situ FTIR and WAXD. Unlike the literature reports, the decay rate of form II is firstly found to be lower than the yielding rate of form I at all studied temperatures, especially at low transition temperature. This is attributed to the amorphous chains which locate near crystal lamella participating into the nucleation of form II. The regular chain folding and growth of iPB form I from amorphous chains containing short isotactic sequences also lead to an increase in crystallinity of form I compared with that of initial form II crystallized at 60 °C. An increase in the annealing temperature results in decrease in crystallinity and increase in lamellae thickness of iPB form I.
2020, 38(2): 174-178
doi: 10.1007/s10118-019-2314-0
Abstract:
Liquid-liquid (L-L) de-mixing and vitrification of solutions of either crystallizable poly(L-lactic acid) (PLLA) or non-crystallizable poly(D/L-lactic acid) (PDLLA) with 50 m% N,N-diethyl-3-methylbenzamide (DEET) were analyzed by calorimetry and cloud-point measurements, which allows drawing conclusions about the effect of polymer stereochemistry on the phase behavior. Regardless of the PLA stereochemistry, vitrification of the solutions on fast cooling, hindering crystallization of PLLA, occurred below −20 °C and suppressed prior L-L de-mixing. The experimental results prove that crystallization in samples containing crystallizable PLLA, observed at around 55 °C on slow cooling, is not preceded by L-L de-mixing.
Liquid-liquid (L-L) de-mixing and vitrification of solutions of either crystallizable poly(L-lactic acid) (PLLA) or non-crystallizable poly(D/L-lactic acid) (PDLLA) with 50 m% N,N-diethyl-3-methylbenzamide (DEET) were analyzed by calorimetry and cloud-point measurements, which allows drawing conclusions about the effect of polymer stereochemistry on the phase behavior. Regardless of the PLA stereochemistry, vitrification of the solutions on fast cooling, hindering crystallization of PLLA, occurred below −20 °C and suppressed prior L-L de-mixing. The experimental results prove that crystallization in samples containing crystallizable PLLA, observed at around 55 °C on slow cooling, is not preceded by L-L de-mixing.
2020, 38(2): 179-186
doi: 10.1007/s10118-019-2322-0
Abstract:
We focus on the distribution and free energy of a wormlike polymer confined between two parallel hard walls. The variation in the distribution and free energy of the wormlike chain as the spacing between the walls decreases (or as the total contour length of the wormlike chain increases or as the persistence length of the chain increases) is simulated. The main reason for these changes is a degradation of the long wormlike chain into a Gaussian long chain under weak confinement.
We focus on the distribution and free energy of a wormlike polymer confined between two parallel hard walls. The variation in the distribution and free energy of the wormlike chain as the spacing between the walls decreases (or as the total contour length of the wormlike chain increases or as the persistence length of the chain increases) is simulated. The main reason for these changes is a degradation of the long wormlike chain into a Gaussian long chain under weak confinement.
2020, 38(2): 187-194
doi: 10.1007/s10118-019-2326-9
Abstract:
Intermolecular synergistic adsorption of indole and carbonyl groups induced by intermolecular hydrogen bonding makes microporous organic polymer (PTICBL) exhibit high CO2 uptake capacity (5.3 mmol·g−1 at 273 K) and selectivities (CO2/CH4 = 53, CO2/N2 = 107 at 273 K). In addition, we find that indole units in the PTICBL networks inhibit the attachment of bacteria (E. coil and S. aureus) on the surface of PTICBL and extend its service life in CO2 capture.
Intermolecular synergistic adsorption of indole and carbonyl groups induced by intermolecular hydrogen bonding makes microporous organic polymer (PTICBL) exhibit high CO2 uptake capacity (5.3 mmol·g−1 at 273 K) and selectivities (CO2/CH4 = 53, CO2/N2 = 107 at 273 K). In addition, we find that indole units in the PTICBL networks inhibit the attachment of bacteria (E. coil and S. aureus) on the surface of PTICBL and extend its service life in CO2 capture.
2020, 38(2): 195-204
doi: 10.1007/s10118-019-2323-z
Abstract:
Poly(L-lactic acid) (PLLA)-based composites exhibit wide applications in many fields. However, most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA, which is unfavorable for the prolonging of the service life of the articles. In this work, a small quantity of poly(methyl methacrylate) (PMMA) (2 wt%−10 wt%) was incorporated into the PLLA/carbon nanotubes (CNTs) composites. The effects of PMMA content on the dispersion of CNTs as well as the microstructure and hydrolytic degradation behaviors of the composites were systematically investigated. The results showed that PMMA promoted the dispersion of CNTs in the composites. Amorphous PLLA was obtained in all the composites. Largely enhanced hydrolytic degradation resistance was achieved by incorporating PMMA, especially at relatively high PMMA content. Incorporating 10 wt% PMMA led to a dramatic decrease in the hydrolytic degradation rate from 0.19 %/h of the PLLA/CNT composite sample to 0.059 %/h of the PLLA/PMMA-10/CNT composite sample. The microstructure evolution of the composites was also detected, and the results showed that no crystallization occurred in the PLLA matrix. Further results based on the interfacial tension calculation showed that the enhanced hydrolytic degradation resistance of the PLLA matrix was mainly attributed to the relatively strong interfacial affinity between PMMA and CNTs, which prevented the occurrence of hydrolytic degradation at the interface between PLLA and CNTs. This work provides an alternative method for tailoring the hydrolytic degradation ability of the PLLA-based composites.
Poly(L-lactic acid) (PLLA)-based composites exhibit wide applications in many fields. However, most of hydrophilic fillers usually accelerate the hydrolytic degradation of PLLA, which is unfavorable for the prolonging of the service life of the articles. In this work, a small quantity of poly(methyl methacrylate) (PMMA) (2 wt%−10 wt%) was incorporated into the PLLA/carbon nanotubes (CNTs) composites. The effects of PMMA content on the dispersion of CNTs as well as the microstructure and hydrolytic degradation behaviors of the composites were systematically investigated. The results showed that PMMA promoted the dispersion of CNTs in the composites. Amorphous PLLA was obtained in all the composites. Largely enhanced hydrolytic degradation resistance was achieved by incorporating PMMA, especially at relatively high PMMA content. Incorporating 10 wt% PMMA led to a dramatic decrease in the hydrolytic degradation rate from 0.19 %/h of the PLLA/CNT composite sample to 0.059 %/h of the PLLA/PMMA-10/CNT composite sample. The microstructure evolution of the composites was also detected, and the results showed that no crystallization occurred in the PLLA matrix. Further results based on the interfacial tension calculation showed that the enhanced hydrolytic degradation resistance of the PLLA matrix was mainly attributed to the relatively strong interfacial affinity between PMMA and CNTs, which prevented the occurrence of hydrolytic degradation at the interface between PLLA and CNTs. This work provides an alternative method for tailoring the hydrolytic degradation ability of the PLLA-based composites.
