冷冻爆破制备壳聚糖溶胀体及其机理的研究
摘要
(1)采用正交实验法研究了甲壳素脱乙酰工艺对产物壳聚糖性质的影响，并结合实验结果设计工艺条件制备了脱乙酰度分别为64．2％(CS65)、71．9％(CS70)、76．7％(CS75)和81．4％(CS80)的壳聚糖，它们在4．8 wt％LiOH溶液中经冷冻爆破均能高度溶胀。
(2)采用红外、XRD、SEM等方法研究了甲壳素和可溶胀壳聚糖的结构。异相-近均相脱乙酰不仅改变了甲壳素的脱乙酰度，还破坏了甲壳素的氢键及其结晶结构，使其致密的网络结构遭到破坏，表面产生许多孔洞，结构变得更加疏松无序。甲壳素的结晶度随脱乙酰度的增大先降后增，结构先变得疏松又开始变得致密，导致它们的可溶胀性CS65＞CS70≈CS75＞CS80。
(3)以CS65、CS70、CS75和CS80为对象，研究了壳聚糖在碱性溶剂体系中的溶胀行为和壳聚糖在碱液中的稳定性，并对其溶胀机理进行了研究。壳聚糖对LiOH和水分的吸附对其脱乙酰度有依赖性，壳聚糖的冷冻爆破溶胀度随碱液浓度的增大先增后减，LiOH比NaOH对壳聚糖具有更好的溶胀力。在尿素浓度(?)4wt％时，尿素开始起增溶作用，且尿素对弱溶胀剂的增溶作用较强。壳聚糖在LiOH／尿素溶液中比较稳定，4．8 wt％LiOH／8．0 wt％尿素水溶液可能是壳聚糖较为理想的溶剂组成。
(4)以甲壳素和壳聚糖为原料，制备了既能溶于碱又能溶于酸壳聚糖CSa和CSd，研究了其结构、溶解行为和溶解机理。
根据实验结果，推测壳聚糖的溶胀和溶解机理如下：
壳聚糖在LiOH水溶液中的溶胀或溶解从较疏松的无定形区向较致密的结晶区进行。实验室自制壳聚糖结晶度的降低、结晶结构的扩张、氢键的破坏及其更加无序和疏松的结构，都将有利于水、LiOH水合物及尿素水合物等向其内部的扩散和渗透，因而实验室自制的壳聚糖常温下能够吸附的大量的自由水和其它小分子。然后，在冷冻时壳聚糖吸附的自由水可以结晶成冰，体积膨胀，从而将壳聚糖的结构撑开，削弱壳聚糖分子间的相互作用，使小分子向壳聚糖内部的扩散更易于进行。另外，[Li(H_2O)_m]~+和[OH(H_2O)_n]~-在低温下比较稳定，能够更有效地向壳聚糖内部扩散，低温下，LiOH与壳聚糖上的乙酰基和羟基发生反应，破坏了壳聚糖的分子内和分子间氢键，最终使得壳聚糖溶胀或溶解。
LiOH是壳聚糖溶胀或溶解的主要动力；冷冻爆破处理对改变壳聚糖本身的氢键，在LiOH和壳聚糖间形成新的相互作用上起着重要的作用；尿素与LiOH和壳聚糖形成包合配合物，提高了壳聚糖／LiOH体系的稳定性。
(1) The effect of deacetylation process conditions on the properties of the finalproduct-chitosan was investigated by orthogonal experiment,and then four chitosanwith different DD (CS65,CS70,CS75,and CS80) were prepared by the optimizedpreparing conditions according to the obtained results.The prepared chitosans canswell highly in 4.8wt% LiOH aqueous solution and form transparent gels afterfreezing-blasting treatment,with the swelling degree CS65＞CS70≈CS75＞CS80.
(2) The structures of prepared chitosan were studied by FT-IR,XRD and TEM.The two-step deacetylation not only changed the DD of chitin,but also destroyed thehydrogen bonds in chitin and the crystal structure.The rigid network of chitin wasdestroyed,and numerous micro voids formed during the N-deacetylation treatment.The crystalinity of chitin first decreased and then increased with the increase of DD,and the structure of chitin grew looser at first and then became denser with theincrease of DD.
(3) The swelling behaviors of four chitosans (CS65,CS70,CS75,and CS80) inalkali solvent system were systematically studied.The effects of several factors suchas the concentration of alkali solution,the kind of alkali solution,added smallmolecule reagents and freezing-blasting treatment on the swelling behavior ofchitosan as well as the mechanism of swelling were investigated.The results indicatedthat the absorption behavior of chitosan to LiOH and water was dependent on itsdeacetylation degree (DD).The swelling degree of chitosan grew at first with theincrease of concentration of alkali and then decreased.When the concentration of ureaincreased over 4 wt%,urea started to act as a solubilizer and urea had a strongersolubilization effect towards weak swelling agent.Chitosan was stable in LiOH/ureaaqueous solution,and 4.8 wt% LiOH/ 8.0 wt% urea solution may be potentialfavorable solvent for chitosan.
(4)Two kinds of chitosan (CSd and CSa) were prepared from chitin or chitosan byN-deacetylation or N-acetylation,respectively,which can dissolve in both alkali andacid.Then their structures and dissolution behaviors in alkali solution were studied,as well as the mechanism of the dissolution.
The mechanism of swelling and dissolution was concluded as following:
The swelling of chitosan in alkali solution took place from the amorphous regionto the crystal region.Their diminished crystallinity,increased amorphous region,expanded crystal structure,destroyed inter- and intra-molecular hydrogen bonds aswell as the more disordered and much looser structures made it much easier for water,LiOH hydrate and urea hydrate to disperse and penetrate into the internal of theprepared chitosans,and therefore,the prepared chitosan can adsorb large amount offree water and small molecules.Under the freezing treatment,the free water absorbedby chitosan can freeze,with the volume of it increasing,which effectively expandedthe structure of chitosan and weakened the interaction between chitosan molecules,making it much easier for small molecules to disperse into the internal of chitosan.Moreover,[Li(H_2O)_m]~+ and [OH(H_2O)_n]~-were more stable at low temperature,they can diffuse and penetrate into the internal of chitosan more effectively.With thecomplex reaction between Li~+ and the acetyl group on the chitosan,and the additionreaction between Li~+ and OH~-on the chitosan,the hydrogen the hydrogen bonds ofthe chitosan can be destroyed,making chitosan swell or dissolute eventually.
The main motivation of the swelling or dissolution of chitosan is the destructionof hydrogen bonds in chitosan caused by LiOH.The freezing-blasting treatment has agreat impact on the shift of hydrogen bonds between chitosan and LiOH hydrate,contributes to the swelling of chitosan.Urea improved the stability of chitosan/LiOHsystem by forming an inclusion compound with chitosan and LiOH.
(2)采用红外、XRD、SEM等方法研究了甲壳素和可溶胀壳聚糖的结构。异相-近均相脱乙酰不仅改变了甲壳素的脱乙酰度，还破坏了甲壳素的氢键及其结晶结构，使其致密的网络结构遭到破坏，表面产生许多孔洞，结构变得更加疏松无序。甲壳素的结晶度随脱乙酰度的增大先降后增，结构先变得疏松又开始变得致密，导致它们的可溶胀性CS65＞CS70≈CS75＞CS80。
(3)以CS65、CS70、CS75和CS80为对象，研究了壳聚糖在碱性溶剂体系中的溶胀行为和壳聚糖在碱液中的稳定性，并对其溶胀机理进行了研究。壳聚糖对LiOH和水分的吸附对其脱乙酰度有依赖性，壳聚糖的冷冻爆破溶胀度随碱液浓度的增大先增后减，LiOH比NaOH对壳聚糖具有更好的溶胀力。在尿素浓度(?)4wt％时，尿素开始起增溶作用，且尿素对弱溶胀剂的增溶作用较强。壳聚糖在LiOH／尿素溶液中比较稳定，4．8 wt％LiOH／8．0 wt％尿素水溶液可能是壳聚糖较为理想的溶剂组成。
(4)以甲壳素和壳聚糖为原料，制备了既能溶于碱又能溶于酸壳聚糖CSa和CSd，研究了其结构、溶解行为和溶解机理。
根据实验结果，推测壳聚糖的溶胀和溶解机理如下：
壳聚糖在LiOH水溶液中的溶胀或溶解从较疏松的无定形区向较致密的结晶区进行。实验室自制壳聚糖结晶度的降低、结晶结构的扩张、氢键的破坏及其更加无序和疏松的结构，都将有利于水、LiOH水合物及尿素水合物等向其内部的扩散和渗透，因而实验室自制的壳聚糖常温下能够吸附的大量的自由水和其它小分子。然后，在冷冻时壳聚糖吸附的自由水可以结晶成冰，体积膨胀，从而将壳聚糖的结构撑开，削弱壳聚糖分子间的相互作用，使小分子向壳聚糖内部的扩散更易于进行。另外，[Li(H_2O)_m]~+和[OH(H_2O)_n]~-在低温下比较稳定，能够更有效地向壳聚糖内部扩散，低温下，LiOH与壳聚糖上的乙酰基和羟基发生反应，破坏了壳聚糖的分子内和分子间氢键，最终使得壳聚糖溶胀或溶解。
LiOH是壳聚糖溶胀或溶解的主要动力；冷冻爆破处理对改变壳聚糖本身的氢键，在LiOH和壳聚糖间形成新的相互作用上起着重要的作用；尿素与LiOH和壳聚糖形成包合配合物，提高了壳聚糖／LiOH体系的稳定性。
(1) The effect of deacetylation process conditions on the properties of the finalproduct-chitosan was investigated by orthogonal experiment,and then four chitosanwith different DD (CS65,CS70,CS75,and CS80) were prepared by the optimizedpreparing conditions according to the obtained results.The prepared chitosans canswell highly in 4.8wt% LiOH aqueous solution and form transparent gels afterfreezing-blasting treatment,with the swelling degree CS65＞CS70≈CS75＞CS80.
(2) The structures of prepared chitosan were studied by FT-IR,XRD and TEM.The two-step deacetylation not only changed the DD of chitin,but also destroyed thehydrogen bonds in chitin and the crystal structure.The rigid network of chitin wasdestroyed,and numerous micro voids formed during the N-deacetylation treatment.The crystalinity of chitin first decreased and then increased with the increase of DD,and the structure of chitin grew looser at first and then became denser with theincrease of DD.
(3) The swelling behaviors of four chitosans (CS65,CS70,CS75,and CS80) inalkali solvent system were systematically studied.The effects of several factors suchas the concentration of alkali solution,the kind of alkali solution,added smallmolecule reagents and freezing-blasting treatment on the swelling behavior ofchitosan as well as the mechanism of swelling were investigated.The results indicatedthat the absorption behavior of chitosan to LiOH and water was dependent on itsdeacetylation degree (DD).The swelling degree of chitosan grew at first with theincrease of concentration of alkali and then decreased.When the concentration of ureaincreased over 4 wt%,urea started to act as a solubilizer and urea had a strongersolubilization effect towards weak swelling agent.Chitosan was stable in LiOH/ureaaqueous solution,and 4.8 wt% LiOH/ 8.0 wt% urea solution may be potentialfavorable solvent for chitosan.
(4)Two kinds of chitosan (CSd and CSa) were prepared from chitin or chitosan byN-deacetylation or N-acetylation,respectively,which can dissolve in both alkali andacid.Then their structures and dissolution behaviors in alkali solution were studied,as well as the mechanism of the dissolution.
The mechanism of swelling and dissolution was concluded as following:
The swelling of chitosan in alkali solution took place from the amorphous regionto the crystal region.Their diminished crystallinity,increased amorphous region,expanded crystal structure,destroyed inter- and intra-molecular hydrogen bonds aswell as the more disordered and much looser structures made it much easier for water,LiOH hydrate and urea hydrate to disperse and penetrate into the internal of theprepared chitosans,and therefore,the prepared chitosan can adsorb large amount offree water and small molecules.Under the freezing treatment,the free water absorbedby chitosan can freeze,with the volume of it increasing,which effectively expandedthe structure of chitosan and weakened the interaction between chitosan molecules,making it much easier for small molecules to disperse into the internal of chitosan.Moreover,[Li(H_2O)_m]~+ and [OH(H_2O)_n]~-were more stable at low temperature,they can diffuse and penetrate into the internal of chitosan more effectively.With thecomplex reaction between Li~+ and the acetyl group on the chitosan,and the additionreaction between Li~+ and OH~-on the chitosan,the hydrogen the hydrogen bonds ofthe chitosan can be destroyed,making chitosan swell or dissolute eventually.
The main motivation of the swelling or dissolution of chitosan is the destructionof hydrogen bonds in chitosan caused by LiOH.The freezing-blasting treatment has agreat impact on the shift of hydrogen bonds between chitosan and LiOH hydrate,contributes to the swelling of chitosan.Urea improved the stability of chitosan/LiOHsystem by forming an inclusion compound with chitosan and LiOH.
引文
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