CN115007113B - 一种掺杂碳点的壳聚糖膜及其制备与应用 - Google Patents
一种掺杂碳点的壳聚糖膜及其制备与应用 Download PDFInfo
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Abstract
本发明涉及一种掺杂碳点的壳聚糖膜及其制备与应用。具体是采用“一锅法”策略，将壳聚糖和碳点溶解于乙酸溶液中，在液氮下迅速冷冻，然后放置于冷冻干燥机中，通过胺醛缩合反应，得到掺杂碳点的壳聚糖膜材料。该材料中含有大量的亲水基团，如羟基和氨基等，具有良好的亲水性能。该亲水材料的制备简单，仅需要一步反应完成，无需二次修饰，直接可作为亲水相互作用色谱的吸附剂应用于复杂生物样品(人或动物的体液、组织和细胞酶解液等)的糖肽富集。
Description
技术领域
本发明涉及一种掺杂碳点的壳聚糖膜及其制备与应用。具体是采用“一锅法”策略，将壳聚糖和碳点溶解于乙酸溶液中，在液氮下迅速冷冻，然后放置于冷冻干燥机中，通过胺醛缩合反应，得到掺杂碳点的壳聚糖膜材料。该材料中含有大量的亲水基团，如羟基和氨基等，具有良好的亲水性能，可直接作为亲水相互作用色谱的吸附剂，用于复杂生物样品中糖肽的分离富集。
背景技术
蛋白质的糖基化是一种普遍的蛋白质翻译后修饰，参与了几乎所有的生命活动，其与细胞免疫、体液免疫以及多种疾病的发生都有着密切的关系。近年来的研究表明，糖基化蛋白质是许多疾病的生物标志物，糖基化蛋白质的分析与鉴定以及其生物学功能研究已经成为当前关注人类生命健康的热门研究方向(文献1.Ohtsubo K.,et.al.“Glycosylation in cellular mechanisms of health and disease”Cell,2006,126,855-867)。糖基化蛋白质因连接糖链的位置、糖型数目和糖基序列的不同，可携带众多的生物信息，具有更多生物功能。因此，对糖基化蛋白质的分析具有重要的理论和现实意义。在“鸟枪法”策略中，质谱分析是最重要的研究手段，而糖肽在蛋白质酶解液中的丰度很低，动态分布范围广，直接分析具有很大的挑战，因此在质谱分析前有必要进行富集。目前，已经发展出了多种糖肽富集的方法，主要包括：凝集素亲和法、亲水相互作用色谱法、酰肼化学法和硼酸亲和法等(文献2.Zhang L.W.,et.al.“Facile fabrication of biomimeticchitosan membrane with honeycomb-like structure for enrichment ofglycosylated peptides”Anal.Chem.2019,91,2985-2993；文献3.江静,等.“亲水相互作用色谱结合串联质谱多重碎裂模式在完整糖肽研究中的应用”分析化学，2014,2,159-165)。其中亲水相互作用色谱法可对生物样品中的糖肽进行无差别式富集，同时在富集分析过程中无化学反应发生，操作简单，可重复性强且与质谱高度兼容，因此得到了广泛的应用。
目前已报道的亲水材料有很多，例如亲水化的有机硅杂化整体材料、二氧化硅微球、聚丙烯酰胺微球等(文献4.杨铎,等.“基于巯基-烯烃点击化学的聚丙烯酰胺型亲水作用色谱固定相的制备”分析化学,2015,43,1439-1444；文献5.Liang Y,et al.“Goldnanoparticles immobilized hydrophilic monoliths with variable functionalmodification for highly selective enrichment and on-line deglycosylation ofglycopeptides”Analytica Chimica Acta,2015,900,83-89)。这些材料通常是经过二次修饰来增强材料的亲水性能，制备过程复杂。
发明内容
本发明的目的在于提供一种具有亲水性能的掺杂碳点的壳聚糖膜材料，其可直接作为亲水相互作用色谱的吸附剂，用于复杂生物样品中糖肽的分离富集。
为实现上述目的，可按如下步骤操作：
(1)碳点的制备：加入15～50mL(优选25～35mL)的无水乙醇和10～30mL(优选15～20mL)戊二醛于反应釜中，120～180℃(优选140～150℃)条件下反应2～5h(优选2～3h)合成戊二醛碳点；将得到的戊二醛碳点溶液在45～60℃(优选45～50℃)下，旋转蒸发除去溶剂，得到戊二醛碳点；
(2)掺杂碳点的壳聚糖膜的制备：将50～500mg(优选300～400mg)壳聚糖分散于10～50mL(优选30～40mL)水中，在50～150r/min(优选60～80r/min)的转速下，进行机械搅拌2～8min(优选3～5min)；然后加入100～500μL(优选200～350μL)乙酸，继续搅拌使其形成澄清均一溶液；接着加入步骤(1)中所得到的碳点10～500mg(优选30～100mg)，继续搅拌10～25min(优选12～15min)后，将溶液转移至平底(内部底面为平面)的金属模具中，于液氮中冷冻5～25min(优选15～20min)使溶液完全冷冻成固体，最后将其置于温度为-45～-55℃的冷冻干燥机中(真空度低于20Pa)16～24h，以去除溶剂，得到掺杂碳点的壳聚糖膜。
所制备掺杂碳点的壳聚糖膜可作为亲水相互作用色谱的吸附剂，用于复杂生物样品中糖肽的分离富集。
该材料中含有大量的亲水基团，如羟基和氨基等，具有良好的亲水性能。该亲水材料的制备简单，仅需要一步反应完成，无需二次修饰，直接可作为亲水相互作用色谱的吸附剂应用于复杂生物样品(人或动物的体液、组织和细胞酶解液等)的糖肽富集。
本发明具有如下优点：
(1)该方法制备过程简单，仅经一步反应即可得到具有良好亲水性能的壳聚糖膜材料。
(2)所制备的亲水膜材料，具有的大孔结构有利于快速传质，且不需要二次修饰即可直接作为亲水相互作用色谱的吸附剂，用于复杂生物样品中糖肽的高效富集。
附图说明
图1为掺杂碳点的壳聚糖膜的制备示意图。
图2为壳聚糖膜及其制备单体的傅里叶变换-红外光谱对比图。
图3为壳聚糖膜的外观图以及其表面和横截面的氦离子扫描电镜图；图3a-c为实施例1制备的掺杂碳点的壳聚糖膜(Ⅰ)；图3d-f为实施例2制备的掺杂碳点的壳聚糖膜(Ⅱ)；图3g-i为实施例3制备的未掺杂碳点的壳聚糖膜。
图4为人免疫球蛋白酶解液富集前后的质谱对比图；图4a为富集前酶解液的质谱图；图4b为采用实施例1制备的掺杂碳点的壳聚糖膜(Ⅰ)为吸附剂富集后的质谱图；图4c为采用实施例2制备的掺杂碳点的壳聚糖膜(Ⅱ)为吸附剂富集后的质谱图；图4d为采用商品化吸附材料为吸附剂富集后的质谱图；图中圆点(·)代表鉴定到的糖肽信号。
具体实施方式
实施例1：掺杂碳点的壳聚糖膜材料的制备及应用：
掺杂碳点的壳聚糖膜材料的制备：
(1)碳点的制备：依次加入30mL的无水乙醇和15mL戊二醛于反应釜中，150℃反应2h合成戊二醛碳点；将得到的碳点溶液转移至圆底烧瓶中，45℃条件下旋转蒸发除去溶剂，得到戊二醛碳点；
(2)掺杂碳点的壳聚糖膜(Ⅰ)的制备：在圆底烧瓶中，将350mg壳聚糖分散于35mL水中，然后在70r/min的转速下进行机械搅拌5min，再加入350μL乙酸，搅拌至溶液澄清透明；接着加入步骤(1)中得到的碳点35mg，继续搅拌15min使溶液混合均匀，然后将其转移至平底的铜盘模具中，在液氮中冷冻20min；待其完全冷冻后，置于-45℃冷冻干燥机(真空度低于20Pa)中20h去除溶剂，得到掺杂碳点的壳聚糖膜(Ⅰ)。掺杂碳点的壳聚糖膜的应用：
人免疫球蛋白G(IgG)酶解液的制备：将2.0mg的IgG溶解于1.0mL含有8M的尿素和100mM NH4HCO3的变性剂水溶液中；然后加入20μL浓度为1M二硫苏糖醇水溶液，8000r/min离心20min后，在37℃恒温2h；在避光状态下继续加入7.4mg碘代乙酰胺，避光反应35min；取出后，加入7.0mL的Tris-HCl缓冲液，将尿素浓度稀释为1M；按照酶与蛋白质量比为1：25加入胰蛋白酶，在37℃的水浴中反应18h，获得的酶解液进行除盐，冻干后保存在-20℃的冰箱中备用。
掺杂碳点的壳聚糖膜对于人免疫球蛋白G酶解液中糖肽的富集：首先，将制备好的膜材料剪成长方形片状(长：0.5～1.0cm；宽：0.2～0.5cm，约1mg)至于离心管中；然后，分别用200μL上样溶液(ACN/H2O/TFA，83/16/1，v/v/v)在室温下平衡材料2次，每次15min离心弃去上清液；平衡材料后，将200μL含有10μg IgG酶解液的上样溶液(ACN/H2O/TFA，83/16/1，v/v/v)加入材料中，震荡30min后离心，除去上清液；之后分别用上述上样溶液200μL进行非特异性洗脱两次，每次15min，除去非糖肽；最后用100μL洗脱溶液(ACN/H2O/TFA，30/69/1，v/v/v)进行特异性洗脱，震荡15min离心后取上清液(糖肽富集液)用MALDI TOF 5800质谱，进行基质辅助激光解吸电离飞行时间质谱(MALDI-TOF/MS)分析。
产物表征
壳聚糖膜及其单体的红外表征结果如图2所示。在碳点谱图中出现的波数为1719cm-1处的醛基特征峰(C＝O键伸缩振动峰)，同时出现在了掺杂碳点的壳聚糖膜的谱图中，而没有出现在不掺杂碳点的壳聚糖膜谱图中。在壳聚糖单体谱图中，波数为3356cm-1和3288cm-1分别归属于-OH和-NH2的伸缩振动吸收峰，这些信号也出现在碳点掺杂壳聚糖膜的谱图中。另外在掺杂碳点的壳聚糖膜谱图中，在波数为1632cm-1处出现了C＝N伸缩振动峰，该峰的出现表明戊二醛碳点中的醛基与壳聚糖单体中的氨基发生了胺醛缩合反应。这些结果说明了掺杂碳点的壳聚糖膜是由碳点与壳聚糖单体通过胺醛缩合反应而制得的。
如图3a所示，制备的掺杂碳点的壳聚糖膜(Ⅰ)的外观呈浅红色，冻干后有裂纹；其氦离子扫描电镜结果如图3b-c所示，图中可以清晰看到膜材料表面含有网状大孔(图3b)，横截面呈现出类似蜂窝状的有序大孔结构(图3c)；该材料的孔径50～150μm，孔隙率约为88％；该材料用手触摸，质地较柔软。
产物应用
采用人免疫球蛋白G酶解液为样品，评价材料的糖肽富集性能。图4为IgG酶解液富集前后的MALDI-TOF/MS分析对比图。如图4a所示，富集前的酶解液质谱图中较高的信号峰均为非糖肽信号峰，糖肽的信号几乎观察不到。而使用掺杂碳点的壳聚糖膜(Ⅰ)进行富集后，质谱图中非糖肽信号峰基本消失，糖肽信号明显增强(图4b)。在信噪比为10时，可检测到20条N-糖肽的信号(表1)。该结果表明本实施例制备的掺杂碳点的壳聚糖膜(Ⅰ)对糖肽具有非常良好的富集效率与选择性。
表1掺杂碳点的壳聚糖膜(Ⅰ)富集到的IgG酶解液中糖肽的质荷比及糖型组成
N#表示糖基化位点；Hex:甘露糖；HexNAc:N-乙酰葡糖胺；Fuc:岩藻糖。
实施例2：掺杂碳点的壳聚糖膜(Ⅱ)的制备及应用：
(1)掺杂碳点的壳聚糖膜(Ⅱ)的制备：制备过程和条件同实施例1，与实施例1不同之处在于，制备过程中反应液中碳点加入量提高到70mg，其它过程同实施例1。
(2)掺杂碳点的壳聚糖膜(Ⅱ)应用于酶解液中糖肽的分离富集：富集实验过程和方法同实施例1。
产物表征
掺杂碳点的壳聚糖膜(Ⅱ)的外观如图3d所示，膜材料显暗红色，与实施例1中得到的壳聚糖膜(I)颜色略有不同；氦离子扫描电镜图显示，该膜表面也含有孔，但是非常致密(图3e)，其横截面也呈规则的类似蜂窝状的孔道结构(图3f)；该材料孔径范围50～150μm，孔隙率约为82％，低于实施例1制备的膜材料的对应值；用手触摸，质地较硬，比实施例1中得到的膜(I)材料硬度要高，这可能是因为碳点作为交联剂时，反应液中其含量越高，交联度越大。
产物应用
使用该膜材料作为吸附剂，对人免疫球蛋白G酶解液中的糖肽进行富集，结果如图4c所示，质谱图中非糖肽信号基本消失，糖肽信号很强。在信噪比为10时，可检测到15条典型的N-糖肽(表2)。该结果表明，该材料对酶解液中的糖肽也具有良好的选择性与富集效率，但与实施例1中的富集结果相比，富集到的糖肽信号值和数量均偏低，这可能是因为反应液中碳点含量的增加，虽可以增加合成膜的硬度，但其亲水性不及壳聚糖，从而导致合成膜的亲水性下降，对于糖肽的富集效率降低。
表2掺杂碳点的壳聚糖膜(Ⅱ)富集到的IgG酶解液中糖肽的质荷比及糖型组成
实施例3：未掺杂碳点的壳聚糖膜的制备及应用：
(1)壳聚糖膜材料的制备：制备过程和条件同实施例1，与实施例1不同之处在于，反应液中不加入碳点，其它过程同实施例1。
(2)壳聚糖膜材料应用于糖肽分离富集，实验过程和方法同实施例1。
产物表征
所制备的未掺杂碳点的壳聚糖膜材料的红外表征结果如图2所示，纯壳聚糖膜与壳聚糖单体的谱图中均存在-OH(3356cm-1)和-NH2(3288cm-1)的特征伸缩振动吸收峰。壳聚糖单体经交联成膜后，由于氢键作用增强，位于1556cm-1及1405cm-1处的C-N键变形振动吸收峰信号明显增强，说明该膜由壳聚糖单体自聚交联而成。
得到的壳聚糖膜的外观如图3g所示，膜呈乳白色，明显不同于实施例1和2中得到的红色膜；氦离子扫描电镜图显示，该材料也具有大孔结构(图3h-i)；孔径范围10～50μm，孔隙率约为89％；用手触摸，质地很软，比实施例1和2中得到的膜材料硬度都低，进一步说明了碳点的加入可以提高合成膜的强度。
产物应用
实验中发现不掺杂碳点的壳聚糖膜材料在酸性溶液中极易溶解，即使平衡溶液中三氟乙酸的含量仅有1％(v％)，平衡30min后，壳聚糖膜已经在溶液中发生溶解，无法进行后续的富集过程，不能应用于糖肽富集。
对比例：商品化亲水材料应用于糖肽分离富集：
为了进行对比，从博纳艾杰尔科技有限公司购买了商品化亲水材料(VenusilHILIC，10μm)，使用与实施例1中相同的步骤对人免疫球蛋白G酶解液中的糖肽进行富集。结果显示(图4d)，该材料作为吸附剂时，虽然可富集到21条糖肽(表3所示，信噪比为10)，但谱图信号值偏低，非糖肽信号不可忽视，说明其对糖肽的选择较差。与实施例1和2的结果对比，掺杂碳点的壳聚糖膜对糖肽具有更高的选择性。
表3商品化材料富集到的IgG酶解液中糖肽的质荷比及糖型组成
以上结果表明，本发明以戊二醛碳点为交联剂制备的掺杂碳点的壳聚糖膜，具有有序的大孔结构以及良好的亲水性。作为亲水富集材料，对糖肽具有优异的富集效率和选择性，可用于复杂生物样品中糖肽的高效富集。
Claims (7)
1.一种掺杂碳点的壳聚糖膜的制备方法，该材料由壳聚糖和戊二醛碳点，通过氨醛缩合反应一步制备而成；其制备可按如下步骤进行：
（1）碳点的制备：加入15~50 mL的无水乙醇和10~30 mL戊二醛于反应釜中，120~180 ℃条件下反应2~5 h合成戊二醛碳点；将得到的戊二醛碳点溶液在45~60℃下，旋转蒸发除去溶剂，得到戊二醛碳点；
（2）掺杂碳点的壳聚糖膜的制备：将50~500 mg壳聚糖分散于10~50 mL水中，在50~150r/min的转速下，进行机械搅拌2~8 min；然后加入100~500 μL乙酸，继续搅拌使其形成澄清均一溶液；接着加入步骤（1）中所得到的碳点10~500 mg，继续搅拌10~25 min后，将溶液转移至平底的模具中，于液氮中冷冻5~25 min使溶液完全冷冻成固体，最后将其冷冻干燥，以去除溶剂，得到掺杂碳点的壳聚糖膜。
2.根据权利要求1所述的制备方法，其特征在于：
步骤（1）中碳点的制备：加入25~35 mL的无水乙醇和15~20 mL戊二醛于反应釜中， 140~150 ℃条件下反应2~3 h合成戊二醛碳点；将得到的戊二醛碳点溶液在45~50 ℃下，旋转蒸发除去溶剂，得到戊二醛碳点；
步骤（2）中掺杂碳点的壳聚糖膜的制备：将300~400 mg壳聚糖分散于 30~40 mL水中，在60~80 r/min的转速下，进行机械搅拌3~5 min；然后加入200~350 μL乙酸，继续搅拌使其形成澄清均一溶液；接着加入步骤（1）中所得到的碳点30~100 mg，继续搅拌12~15 min后，将溶液转移至平底的模具中，于液氮中冷冻15~20 min使溶液完全冷冻成固体，最后将其冷冻干燥，以去除溶剂，得到掺杂碳点的壳聚糖膜。
3.根据权利要求1所述的制备方法，其特征在于：于冷冻干燥机中进行冷冻干燥，冷冻干燥时间16~24 h，冷冻干燥温度条件为-45~-55℃，真空度低于20 Pa。
4.一种权利要求1~3任一所述方法制备获得的掺杂碳点的壳聚糖膜。
5.一种权利要求4所述掺杂碳点的壳聚糖膜的应用，其作为亲水相互作用色谱的吸附剂或填料。
6.根据权利要求4所述掺杂碳点的壳聚糖膜的应用，其特征在于：该材料具有良好的亲水性能，直接作为亲水相互作用色谱的吸附剂或填料，用于生物样品中的糖肽富集。
7.根据权利要求6所述的应用，其特征在于：所述的生物样品为人体和/或动物的体液、组织以及细胞酶解液中的一种或二种以上。
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