脂肪族聚酯及其两亲性嵌段共聚物合成、表征及应用
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摘要
化学合成类可降解脂肪族聚酯及其两亲性嵌段共聚物由于具有低毒性、良好的生物相容性和细胞渗透性、可生物降解性以及降解产物无毒等优点,目前已广泛应用于药物控制释放体系以及组织工程等领域。目前用于合成脂肪族聚酯的催化体系往往存在催化活性低、毒性较大、聚合速率慢、单体转化率较低、得到的聚合物分子量低等各种问题。因此寻找高效、廉价易得、能够使得聚合工艺简单,方便可控、无毒的催化体系已成为一个非常重要的课题。
近年来,生物可降解脂肪族聚酯及其两亲性嵌段共聚物可通过各种技术,比如溶剂蒸发法制备各种形态的纳米级或微米级药物控释载体,该类药物载体具有很多优势,一方面可以延长药物在体内的循环时间,使药物在足够长的时间内保持其药效,另一方面载药颗粒在体内的这种长效循环,有助于提高药物与病变部位之间的相互作用,从而实现载体的靶向性。同时,作为药物载体,其形态对体内药物控释起着极其重要的作用,越来越多的研究表明,药物在体内不同病变组织及部位的释放行为不仅依赖于载体的尺寸、稳定性,而且还依赖于它们的形态。基于上述分析,本论文主要从以下几个方面展开研究：
(1)生物可降解星形聚己内酯及聚丙交酯-聚己内酯嵌段共聚物的合成
采用廉价易得的钛酸四丁酯和钛酸异丙酯分别作为引发剂,引发己内酯开环聚合。研究发现,在低温(10-40℃)和常压条件下,两种引发剂都能快速引发己内酯开环聚合,得到四臂星形聚己内酯。动力学研究表明,钛酸四丁酯和钛酸异丙酯都具有很高的活性,能高效,快速地引发己内酯开环聚合,聚合反应具有“活性”可控的特点。同时该种星形的聚己内酯可作为大分子引发剂,再次引发己内酯和丙交酯单体进行扩链和嵌段共聚反应。钛酸酯引发己内酯开环聚合符合“配位-插入”的机理。通过比较两种催化剂聚合速率常数,表明在相同聚合反应时间下,钛酸异丙酯引发的己内酯开环聚合反应速率要快于钛酸四丁酯。
同时,进一步研究表明,在聚合反应及后处理过程中,连接在聚合物链上的钛氧键具有相对较高的稳定性,在聚合反应结束后,所得聚合物粗产物在去离子水或醇沉淀剂中时仍然保持其星形结构,在酸性沉淀剂中钛氧键容易断裂,星形聚合物发生水解,得到线性聚己内酯。通过凝胶渗透色谱(GPC)、核磁共振光谱(NMR)、差示热量扫描仪(DSC)、ZeTa粒度分析仪对星形聚己内酯和聚丙交酯-聚己内酯进行了表征。
(2)星形聚己内酯-聚环氧丙烷嵌段共聚物的合成
以钛酸异丙酯作为引发剂,首先在室温引发环氧丙烷开环聚合,再以得到的星形聚环氧丙烷作为大分子引发剂,在40℃下,引发己内酯开环聚合得到星形聚己内酯-聚环氧丙烷嵌段共聚物。实验结果表明,使用钛酸异丙酯作为引发剂引发环氧丙烷室温开环聚合得到的星形聚环氧丙烷分子量很低且稳定性较差,只能得到一些低聚物。星形聚环氧丙烷可作为大分子引发剂引发己内酯开环聚合,动力学研究表明,星形聚环氧丙烷仍具有较高的活性,可实现星形嵌段共聚物聚己内酯-聚环氧丙烷的可控合成。
(3)聚己内酯-聚乙二醇醚(PCL-PEO-PCL)两亲性三嵌段共聚物合成及自组装研究
以双端带羟基的聚乙二醇作为引发剂,在异辛酸亚锡催化下成功合成了一系列不同组分的两亲性PCL-PEO-PCL三嵌段共聚物。采用改进的O/W溶剂抽提法,研究了两亲性嵌段共聚物在THF/H2O和THF/含有一定浓度碱金属离子的水溶液中的自组装行为,深入研究了在溶液中和固态凝聚相两种状态下嵌段共聚物自组装所得胶束聚集体形态的变化。发现在溶液中两亲性嵌段共聚物PCL-PEO-PCL都能自组装成尺寸均一的球形纳米颗粒。然而,在水相溶剂蒸发过程,随着碱金属离子浓度的增大,球形纳米颗粒聚集为多层次有序结构的胶束聚集体,其形态包括“剑麻”状胶束聚集体,“星形”胶束聚集体。有序结构的胶束聚集体形态依赖于不同碱金属离子的加入,而其尺寸则与碱金属离子的浓度有关。
深入研究发现,有序结构的胶束聚集体的形成主要是在水相溶剂蒸发的过程中,由于嵌段共聚物中亲水PEO链与碱金属离子的强烈的配位导致体系自由能的降低,使得溶液中大量的球形纳米颗粒不断移动并发生碰撞,这些发生碰撞的球形纳米颗粒很可能融合在一起,最终导致多层有序结构胶束聚集体的形成。
(4)聚丙交酯乙交酯-聚乙二醇醚(PLGA-PEO-PLGA)载药多孔微球的制备及其体外超声药物释放行为
以双端带羟基的聚乙二醇作为引发剂,在异辛酸亚锡催化下成功合成了一系列不同组分的两亲性PLGA-PEO-PLGA三嵌段共聚物。采用改进的W/OW型双乳液-溶剂蒸发法,在无任何制孔剂存在的条件下,成功制备了伊文思蓝负载的PLGA-PEO-PLGA嵌段共聚物多孔微球。考察了在自发和超声作用下多孔微球的药物释放行为,发现在超声作用下,多孔微球药物释放要明显快于在自发条件下的药物释放,而嵌段共聚物组分对微球形貌、尺寸、表面孔径、药物包封效率有着显著的影响,同时,药物暴释现象可以有效的加以控制。PLGA-PEO-PLGA嵌段共聚物多孔微球可作为新型的声控“被动靶向”的靶向药物制剂,它既能在超声辐照下下显影,又能在超声作用下释放药物。最后对多孔微球形成机理进行了讨论。
Chemical synthetic degradable aliphatic polyesters and their amphiphilic copolymers have attracted much attention in drug controlled release systems and tissue engineering due to their excellent biodegradable, biocompatible, permeable and low toxicity properties. However, in current strategy for the synthesis of aliphatic polyesters there are various problems, which primarily involve low catalytic activity, higher toxicity, the sluggish polymerization reaction rate, lower monomer conversion and lower polymer molecule weight etc. Therefore, to investigate a more efficient, inexpensive, simpler polymerization process, more controllable and non-toxic catalytic systems have developed an important subject.
In recent years, biodegradable aliphatic polyesters and their amphiphilic copolymers have been used to prepare nano or macroscopic scale drug delivery carrier with various morphologies by various technologies, such as solvent evaporation method. These drug delivery carrier prossess many ascendancies, on the one hand, it can prolong the drug circulation times in vivo, and make its effectiveness in an enough times, on the other hand, the long-acting circulation of drug-loaded particles is favored to improve the interaction between drug and diseased region. Meanwhile, there is an increasing evidence to suggest that the drug release behaviors of drug-loaded particles in different diseased region or tissues dependent not only on their size and stability but also on their morphology. Based on these, the thesis including several aspects:
(1) Syntheis of biodegradable star-shaped poly(ε-caprolactone) and poly (lactide-b-caprolactone) block copolymer.
In present study, four-arm star-shaped aliphatic polyesters poly(ε-caprolactone)(PCL) was synthesized via using tetrabutyl titanate (TBT) and isopropyl titanate (iPT) as initiator to mediate controlled ring-opening polymerization (ROP) of ε-caprolactone (CL) at ambient temperature of10-40℃under the normal atmosphere. The kinetic indicated that tetrabutyl titanate(TBT) and isopropyl titanate (iPT) controlled ring-opening polymerization (ROP) of ε-CL exhibited living and controlling features. Moreover, the star-shaped Ti(O-PCL)4can act as a macroinitiator for successive propagation and block copolymerization with CL and LA, respectively. The mechanism of titanium ester controlled ring-opening polymerization (ROP) of ε-CL is accorded with the "coordination-insertion". The polymerization kinetics comparison of CL initiated by tetrabutyl titanate and isopropyl titanate manifested that the isopropyl titanate-catalyzed ROP of CL is faster than the tetrabutyl titanate initiated ROP at40℃.
Meanwhile, we found that Ti-alkoxide bonds included in the polymer chains was relative stabilized when the crude polymer precipitated in de-ionized water or alcohol, and it hydrolyzed to linear PCL when precipitated in acidic alcoholic solution. The star-shaped Ti(O-PCL)4and Ti(O-PLA-PCL)4block copolymers were characterized by1H NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and ZeTa particle-size analyzer.
(2) Synthesis of star-shaped poly (caprolactone-b-propylene oxide) block copolymer.
Firstly, four-arm star-shaped poly(propylene oxide) macroinitiator was synthesized via using isopropyl titanate (iPT) as initiator to mediate controlled ring-opening polymerization (ROP) of propylene oxide (PO) at room temperature under the normal atmosphere. Then, the star-shaped poly(propylene oxide) act as a macroinitiator for successive block copolymerization with CL at40℃. The results indicated that only oligomer could be obtained after polymerization of PO iniated by iPT, and the obtained star-shaped poly(propylene oxide) prossess much lower molecule weight and stability. The kinetic indicated that four-arm star-shaped poly(propylene oxide) macroinitiator still sustained much higher activity, which can achive the controlling synthesis of poly (caprolactone-b-propylene oxide) block copolymer.
(3) Synthesis and characterization of poly(ε-caprolactone)-b-poly(ethylene oxide)-b-poly(ε-caprolactone) amphiphilic triblock copolymer and their self-assembly behavior.
A serials of poly(s-caprolactone)-b-poly(ethylene oxide)-b-poly(s-caprolactone)(PCL-PEO-PCL) triblock copolymers were synthesized by a ring-opening polymerization of ε-caprolactone in the presence of hydroxyl-terminated poly(ethylene oxide) with stannous octoate catalyst, where PEO served as initiator. The self-assembly behavior of amphiphilic block copolymers in THF/H2O and THF/a certain concentration of alkali metal ions aqueous solution are carried out by a O/W modified solvent extraction method. The morphologies transform of PCL-PEO-PCL triblock copolymers self-assembly from aqueous media to condensed aggregates is extensively investigated. It was found that the monoporous spherical micelles formed both in di-ionized water and alkali metal ions aqueous solution. However, with the increase of alkali metal ions concentration, the spherical micelles assembled into different hierarchical mesostructures during the water evaporation from the block copolymer. The morphologies of aggregates included "sisal-like" and "satr-shaped" mesostructures. The morphologies of mesostructures aggregates strongly depended on the addition of different alkali metal ions, but the size of aggregates have to do with the alkali metal ions concentrations.
The mechanism for the self-assembly of PCL-PEO-PCL amphiphilic triblock copolymer are attributed to the continuous increase of alkali metal salt concentration and thus the stronger coordination between alkali metal ions and PEO ligands in the block copolymer during water evaporation process. The strong binding of PEO with alkali metal ion leads to the decrease of free energy in the system. In this case, with the support of the driving force from the strong coordination between PEO and alkali metal ions, a large number of spherical micelles move and merge, and some of the micelles possibly fuse together, resulting the formation of aggregates mesostructures.
(4) Preparation of porous drug-loaded poly(lactide-co-glycolide-b-ethylene glycol-b-lactide-co-glycolide)(PLGA-PEO-PLGA) microspheres and their drug release behavior under ultrasound in vitro.
A series of amphiphilic tri-block copolymer PLGA-PEO-PLGA were synthesized by a ring-opening polymerization of LA and GA in the presence of hydroxyl-terminated poly(ethylene oxide) with stannous octoate catalyst, where PEO served as initiator. The drug-loaded porous microspheres was successfully prepared by a modified double emulsion (W/O/W)-solvent evaporation technique without any porogen present. The spontaneous and ultrasound promoted drug releases were studied. Compared with spontaneous drug release behavior, the capacity of ultrasonic drug release was significantly faster from PLGA-PEO-PLGA porous microspheres. It was found that the compositions of PLGA-PEO-PLGA have great influence on the morphologies of microspheres, size, surface apertures and drug entrapment efficiency. Moreover, the initially bursts could be controlled by adjusting the surface apertures of microspheres. The PLGA-PEO-PLGA could be used as a novel acoustic control "passive target" pharmaceutical agent, which can not only contrast-enhanced under ultrasound, but also promote the drug release. Finally, the formation mechanism of PLGA-PEO-PLGA porous microspheres was discussed.
近年来,生物可降解脂肪族聚酯及其两亲性嵌段共聚物可通过各种技术,比如溶剂蒸发法制备各种形态的纳米级或微米级药物控释载体,该类药物载体具有很多优势,一方面可以延长药物在体内的循环时间,使药物在足够长的时间内保持其药效,另一方面载药颗粒在体内的这种长效循环,有助于提高药物与病变部位之间的相互作用,从而实现载体的靶向性。同时,作为药物载体,其形态对体内药物控释起着极其重要的作用,越来越多的研究表明,药物在体内不同病变组织及部位的释放行为不仅依赖于载体的尺寸、稳定性,而且还依赖于它们的形态。基于上述分析,本论文主要从以下几个方面展开研究：
(1)生物可降解星形聚己内酯及聚丙交酯-聚己内酯嵌段共聚物的合成
采用廉价易得的钛酸四丁酯和钛酸异丙酯分别作为引发剂,引发己内酯开环聚合。研究发现,在低温(10-40℃)和常压条件下,两种引发剂都能快速引发己内酯开环聚合,得到四臂星形聚己内酯。动力学研究表明,钛酸四丁酯和钛酸异丙酯都具有很高的活性,能高效,快速地引发己内酯开环聚合,聚合反应具有“活性”可控的特点。同时该种星形的聚己内酯可作为大分子引发剂,再次引发己内酯和丙交酯单体进行扩链和嵌段共聚反应。钛酸酯引发己内酯开环聚合符合“配位-插入”的机理。通过比较两种催化剂聚合速率常数,表明在相同聚合反应时间下,钛酸异丙酯引发的己内酯开环聚合反应速率要快于钛酸四丁酯。
同时,进一步研究表明,在聚合反应及后处理过程中,连接在聚合物链上的钛氧键具有相对较高的稳定性,在聚合反应结束后,所得聚合物粗产物在去离子水或醇沉淀剂中时仍然保持其星形结构,在酸性沉淀剂中钛氧键容易断裂,星形聚合物发生水解,得到线性聚己内酯。通过凝胶渗透色谱(GPC)、核磁共振光谱(NMR)、差示热量扫描仪(DSC)、ZeTa粒度分析仪对星形聚己内酯和聚丙交酯-聚己内酯进行了表征。
(2)星形聚己内酯-聚环氧丙烷嵌段共聚物的合成
以钛酸异丙酯作为引发剂,首先在室温引发环氧丙烷开环聚合,再以得到的星形聚环氧丙烷作为大分子引发剂,在40℃下,引发己内酯开环聚合得到星形聚己内酯-聚环氧丙烷嵌段共聚物。实验结果表明,使用钛酸异丙酯作为引发剂引发环氧丙烷室温开环聚合得到的星形聚环氧丙烷分子量很低且稳定性较差,只能得到一些低聚物。星形聚环氧丙烷可作为大分子引发剂引发己内酯开环聚合,动力学研究表明,星形聚环氧丙烷仍具有较高的活性,可实现星形嵌段共聚物聚己内酯-聚环氧丙烷的可控合成。
(3)聚己内酯-聚乙二醇醚(PCL-PEO-PCL)两亲性三嵌段共聚物合成及自组装研究
以双端带羟基的聚乙二醇作为引发剂,在异辛酸亚锡催化下成功合成了一系列不同组分的两亲性PCL-PEO-PCL三嵌段共聚物。采用改进的O/W溶剂抽提法,研究了两亲性嵌段共聚物在THF/H2O和THF/含有一定浓度碱金属离子的水溶液中的自组装行为,深入研究了在溶液中和固态凝聚相两种状态下嵌段共聚物自组装所得胶束聚集体形态的变化。发现在溶液中两亲性嵌段共聚物PCL-PEO-PCL都能自组装成尺寸均一的球形纳米颗粒。然而,在水相溶剂蒸发过程,随着碱金属离子浓度的增大,球形纳米颗粒聚集为多层次有序结构的胶束聚集体,其形态包括“剑麻”状胶束聚集体,“星形”胶束聚集体。有序结构的胶束聚集体形态依赖于不同碱金属离子的加入,而其尺寸则与碱金属离子的浓度有关。
深入研究发现,有序结构的胶束聚集体的形成主要是在水相溶剂蒸发的过程中,由于嵌段共聚物中亲水PEO链与碱金属离子的强烈的配位导致体系自由能的降低,使得溶液中大量的球形纳米颗粒不断移动并发生碰撞,这些发生碰撞的球形纳米颗粒很可能融合在一起,最终导致多层有序结构胶束聚集体的形成。
(4)聚丙交酯乙交酯-聚乙二醇醚(PLGA-PEO-PLGA)载药多孔微球的制备及其体外超声药物释放行为
以双端带羟基的聚乙二醇作为引发剂,在异辛酸亚锡催化下成功合成了一系列不同组分的两亲性PLGA-PEO-PLGA三嵌段共聚物。采用改进的W/OW型双乳液-溶剂蒸发法,在无任何制孔剂存在的条件下,成功制备了伊文思蓝负载的PLGA-PEO-PLGA嵌段共聚物多孔微球。考察了在自发和超声作用下多孔微球的药物释放行为,发现在超声作用下,多孔微球药物释放要明显快于在自发条件下的药物释放,而嵌段共聚物组分对微球形貌、尺寸、表面孔径、药物包封效率有着显著的影响,同时,药物暴释现象可以有效的加以控制。PLGA-PEO-PLGA嵌段共聚物多孔微球可作为新型的声控“被动靶向”的靶向药物制剂,它既能在超声辐照下下显影,又能在超声作用下释放药物。最后对多孔微球形成机理进行了讨论。
Chemical synthetic degradable aliphatic polyesters and their amphiphilic copolymers have attracted much attention in drug controlled release systems and tissue engineering due to their excellent biodegradable, biocompatible, permeable and low toxicity properties. However, in current strategy for the synthesis of aliphatic polyesters there are various problems, which primarily involve low catalytic activity, higher toxicity, the sluggish polymerization reaction rate, lower monomer conversion and lower polymer molecule weight etc. Therefore, to investigate a more efficient, inexpensive, simpler polymerization process, more controllable and non-toxic catalytic systems have developed an important subject.
In recent years, biodegradable aliphatic polyesters and their amphiphilic copolymers have been used to prepare nano or macroscopic scale drug delivery carrier with various morphologies by various technologies, such as solvent evaporation method. These drug delivery carrier prossess many ascendancies, on the one hand, it can prolong the drug circulation times in vivo, and make its effectiveness in an enough times, on the other hand, the long-acting circulation of drug-loaded particles is favored to improve the interaction between drug and diseased region. Meanwhile, there is an increasing evidence to suggest that the drug release behaviors of drug-loaded particles in different diseased region or tissues dependent not only on their size and stability but also on their morphology. Based on these, the thesis including several aspects:
(1) Syntheis of biodegradable star-shaped poly(ε-caprolactone) and poly (lactide-b-caprolactone) block copolymer.
In present study, four-arm star-shaped aliphatic polyesters poly(ε-caprolactone)(PCL) was synthesized via using tetrabutyl titanate (TBT) and isopropyl titanate (iPT) as initiator to mediate controlled ring-opening polymerization (ROP) of ε-caprolactone (CL) at ambient temperature of10-40℃under the normal atmosphere. The kinetic indicated that tetrabutyl titanate(TBT) and isopropyl titanate (iPT) controlled ring-opening polymerization (ROP) of ε-CL exhibited living and controlling features. Moreover, the star-shaped Ti(O-PCL)4can act as a macroinitiator for successive propagation and block copolymerization with CL and LA, respectively. The mechanism of titanium ester controlled ring-opening polymerization (ROP) of ε-CL is accorded with the "coordination-insertion". The polymerization kinetics comparison of CL initiated by tetrabutyl titanate and isopropyl titanate manifested that the isopropyl titanate-catalyzed ROP of CL is faster than the tetrabutyl titanate initiated ROP at40℃.
Meanwhile, we found that Ti-alkoxide bonds included in the polymer chains was relative stabilized when the crude polymer precipitated in de-ionized water or alcohol, and it hydrolyzed to linear PCL when precipitated in acidic alcoholic solution. The star-shaped Ti(O-PCL)4and Ti(O-PLA-PCL)4block copolymers were characterized by1H NMR, gel permeation chromatography (GPC), differential scanning calorimetry (DSC) and ZeTa particle-size analyzer.
(2) Synthesis of star-shaped poly (caprolactone-b-propylene oxide) block copolymer.
Firstly, four-arm star-shaped poly(propylene oxide) macroinitiator was synthesized via using isopropyl titanate (iPT) as initiator to mediate controlled ring-opening polymerization (ROP) of propylene oxide (PO) at room temperature under the normal atmosphere. Then, the star-shaped poly(propylene oxide) act as a macroinitiator for successive block copolymerization with CL at40℃. The results indicated that only oligomer could be obtained after polymerization of PO iniated by iPT, and the obtained star-shaped poly(propylene oxide) prossess much lower molecule weight and stability. The kinetic indicated that four-arm star-shaped poly(propylene oxide) macroinitiator still sustained much higher activity, which can achive the controlling synthesis of poly (caprolactone-b-propylene oxide) block copolymer.
(3) Synthesis and characterization of poly(ε-caprolactone)-b-poly(ethylene oxide)-b-poly(ε-caprolactone) amphiphilic triblock copolymer and their self-assembly behavior.
A serials of poly(s-caprolactone)-b-poly(ethylene oxide)-b-poly(s-caprolactone)(PCL-PEO-PCL) triblock copolymers were synthesized by a ring-opening polymerization of ε-caprolactone in the presence of hydroxyl-terminated poly(ethylene oxide) with stannous octoate catalyst, where PEO served as initiator. The self-assembly behavior of amphiphilic block copolymers in THF/H2O and THF/a certain concentration of alkali metal ions aqueous solution are carried out by a O/W modified solvent extraction method. The morphologies transform of PCL-PEO-PCL triblock copolymers self-assembly from aqueous media to condensed aggregates is extensively investigated. It was found that the monoporous spherical micelles formed both in di-ionized water and alkali metal ions aqueous solution. However, with the increase of alkali metal ions concentration, the spherical micelles assembled into different hierarchical mesostructures during the water evaporation from the block copolymer. The morphologies of aggregates included "sisal-like" and "satr-shaped" mesostructures. The morphologies of mesostructures aggregates strongly depended on the addition of different alkali metal ions, but the size of aggregates have to do with the alkali metal ions concentrations.
The mechanism for the self-assembly of PCL-PEO-PCL amphiphilic triblock copolymer are attributed to the continuous increase of alkali metal salt concentration and thus the stronger coordination between alkali metal ions and PEO ligands in the block copolymer during water evaporation process. The strong binding of PEO with alkali metal ion leads to the decrease of free energy in the system. In this case, with the support of the driving force from the strong coordination between PEO and alkali metal ions, a large number of spherical micelles move and merge, and some of the micelles possibly fuse together, resulting the formation of aggregates mesostructures.
(4) Preparation of porous drug-loaded poly(lactide-co-glycolide-b-ethylene glycol-b-lactide-co-glycolide)(PLGA-PEO-PLGA) microspheres and their drug release behavior under ultrasound in vitro.
A series of amphiphilic tri-block copolymer PLGA-PEO-PLGA were synthesized by a ring-opening polymerization of LA and GA in the presence of hydroxyl-terminated poly(ethylene oxide) with stannous octoate catalyst, where PEO served as initiator. The drug-loaded porous microspheres was successfully prepared by a modified double emulsion (W/O/W)-solvent evaporation technique without any porogen present. The spontaneous and ultrasound promoted drug releases were studied. Compared with spontaneous drug release behavior, the capacity of ultrasonic drug release was significantly faster from PLGA-PEO-PLGA porous microspheres. It was found that the compositions of PLGA-PEO-PLGA have great influence on the morphologies of microspheres, size, surface apertures and drug entrapment efficiency. Moreover, the initially bursts could be controlled by adjusting the surface apertures of microspheres. The PLGA-PEO-PLGA could be used as a novel acoustic control "passive target" pharmaceutical agent, which can not only contrast-enhanced under ultrasound, but also promote the drug release. Finally, the formation mechanism of PLGA-PEO-PLGA porous microspheres was discussed.
引文
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