CN105153401A - 荧光金纳米团簇及其水性聚氨酯模板法制备方法 - Google Patents
荧光金纳米团簇及其水性聚氨酯模板法制备方法 Download PDFInfo
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Abstract
荧光金纳米团簇及其水性聚氨酯模板法制备方法，涉及一种纳米材料及其制备方法。荧光型金纳米团簇，原料组成为：二异氰酸酯、二元醇、有机锡类催化剂、亲水扩链剂、小分子扩链剂、巯基乙醇、浓度10Mm/L氯金酸丙酮溶液、调节荧光型金纳米团簇的PH＝11～13的氢氧化钠，余为水。将二元醇、亲水扩链剂干燥，将其他的预聚单体干燥；将脱水处理的二元醇、二异氰酸酯、亲水扩链剂按比例加入到四口烧瓶中，在氮气保护下反应；待反应体系降温后，加入小分子扩链剂和巯基乙醇反应；待预聚物降至室温，加入氯金酸，加入NaOH溶液调节反应物的pH＝11～13，室温下反应≥12h；加入去离子水进行乳化，得荧光纳米金团簇。
Description
技术领域
本发明涉及一种纳米材料及其制备方法，尤其是涉及一种以经过高分子修饰的荧光金纳米团簇及其水性聚氨酯模板制备方法。
背景技术
金纳米团簇(Goldnanocluters，AuNCs)通常是指在一定分子层保护下，由几个到几百个金原子组成、尺寸小于2nm的分子聚集体，是原子和纳米颗粒的联系纽带。近年来，由于金纳米簇的荧光稳定性好、抗光漂白作用强、毒性小、生物相容性好、生物安全性高、荧光量子产率高、并且简单易制备等优点已成为分析科学和生命学科等领域的研究和应用热点。同时，金纳米团簇因其独特的电子结构和特别的物理、化学性质，广泛应用于生物标记、生化传感、单分子成像及光学成像研究等领域。金纳米团簇(AuNCs)是基于蛋白质或者硫醇类化合物等有机单分子模板而制备得到的。
聚氨酯是聚氨基甲酸酯的简称，英文名称是polyurethane，它是一种高分子材料。聚氨酯是由聚物多元醇与异氰酸酯反应，再经扩链交联反应而制备的一种新兴的有机高分子材料。而水性聚氨酯(WPU)是以水代替有机溶剂作为分散介质的新型聚氨酯体系，也称水分散聚氨酯、水系聚氨酯或水基聚氨酯。水性聚氨酯因以水为溶剂，无污染、安全可靠、机械性能优良、相容性好、易于改性等优点而被广泛应用于轻工、化工、电子、纺织、医疗、建筑、建材、汽车、国防、航天、航空等众多领域。在聚氨酯制备过程中，原料中的许多活性基团会被引入到聚氨酯的分子链上，如-OH、-NCO、C＝C、-COOH，再辅以人为设计，通过一些合理的化学反应可以将许多功能化的分子连接到聚氨酯分子链上，从而赋予了聚氨酯一些新的功能。基于上述，本发明在不破坏聚氨酯链的主体结构的前提下，将硫醇分子引入到分子链上，仿照蛋白质为模板制备金纳米团簇的方法，在聚氨酯中制备荧光型的金纳米团簇，不仅开拓了聚氨酯的应用市场，还赋予了聚氨酯荧光性，具有广泛的应用前景。
如中国专利CN104759636A公布了一种利用山楂籽提取液作为分散剂和生物还原剂制备纳米金的方法。该方法在常压下进行，设备简单，成本低、易于操作，但是该发明中制备的是纳米金粒子，不是纳米金团簇。2008年，研究小组通过聚合物的分子设计向分子中引入巯基，利用含巯基的高分子聚合物和谷胱甘肽为共同的模板，制备硫醇保护的金纳米团簇(RP,HuM,QianL,etal.GoldnanoparticlesizecontrolledbypolymericAu(I)thiolateprecursorsize[J].JournaloftheAmericanChemicalSociety,2008,130(3):975-982.)。2009年，Xie研究小组在碱性条件(pH>12.0)下，首次以牛血清蛋白为模板合成了QYs为6.0％的BSA-Au25NCs，其中，BSA不仅可以稳定金离子，而且可以通过BSA中酪氨酸残基与金离子发生氧化还原反应而还原金离子(XieJ,ZhengY,YingJY.Protein-directedsynthesisofhighlyfluorescentgoldnanoclusters[J].JournaloftheAmericanChemicalSociety,2009,131(3):888-889.)。2012年，Luo研究小组以鸡蛋清蛋白为模板合成了金纳米团簇(LuoZ,YuanX,YuY,etal.Fromaggregation-inducedemissionofAu(I)–thiolatecomplexestoultrabrightAu(0)Au(I)–thiolatecore–shellnanoclusters[J].JournaloftheAmericanChemicalSociety,2012,134(40):16662-16670.)。
发明内容
本发明的目的在提供一种具有较强的光致发光效应，可广泛应用在传感器、金属离子检测、生物显影，生物检测，药物追踪，化学检测等方面的荧光金纳米团簇及其水性聚氨酯模板法制备方法。
为实现上述目的，本发明通过以下技术方案予以实现：
荧光型金纳米团簇，其制备原料组成按质量百分比为：二异氰酸酯17％～30％，二元醇62％～73％，有机锡类催化剂0.04％～0.06％，亲水扩链剂4％～5％，小分子扩链剂3.8％～4.2％，巯基乙醇1.7％～2.6％，浓度10Mm/L氯金酸丙酮溶液3.2％～4.2％，调节荧光型金纳米团簇的PH＝11～13的氢氧化钠，余为水；
所述二异氰酸酯与二元醇的摩尔比为(2～4):1。
所述有机锡类催化剂可为二月桂酸二丁基锡、辛酸亚锡中的至少一种。
所述二异氰酸酯可为异佛尔酮二异氰酸酯(IPDI)、甲苯二异氰酸酯(TDI)、4，4-亚甲基-二苯基二异氰酸酯(MDI)、六亚甲基二异氰酸酯(HDI)、4,4-亚甲基-二环己基二异氰酸酯(H12MDI)中的至少一种。
所述二元醇可为聚丙二醇(PPG)、聚乙二醇(PEG)、聚四氢呋喃二醇(PTMG)、聚己二酸1,6-己二醇酯、聚碳酸酯、聚丁二烯二醇中的至少一种，分子量为1500～2500。
所述亲水扩链剂可有磺酸型和羧酸型，可为1,2-二羟基-3-丙磺酸钠、二羟甲基丙酸、二羟甲基丁酸中的至少一种。这里优选二羟甲基丙酸。
所述小分子扩链剂可为一缩二乙二醇、1,4-丁二醇(BDO)、聚醚改性氢醌(HQEE)、环己烷二甲醇、甲基丙二醇、乙二胺和异佛尔酮二胺中的至少一种；这里优选1,4-丁二醇。
所述巯基乙醇作为硫醇基团的载体。
所述氢氧化钠水溶液的浓度可为1～3mol/L。
荧光金纳米团簇的水性聚氨酯模板法制备方法，所述荧光金纳米团簇为上述荧光金纳米团簇，所述制备方法包括以下步骤：
a.将二元醇、亲水扩链剂置于真空烘箱中干燥，将其他的预聚单体加入分子筛进行干燥；
所述真空烘箱的温度可为100～120℃；所述干燥的时间可为3～5h；所述分子筛可为4A分子筛；所述分子筛干燥的时间可为24h以上。
b.将脱水处理的二元醇、二异氰酸酯、亲水扩链剂按比例加入到四口烧瓶中，在氮气保护下，继续反应；
所述升温的温度可至70～80℃，所述继续反应的时间可为3～4h。
c.待反应体系降温后，加入小分子扩链剂和巯基乙醇，继续进行反应，此过程用丙酮降粘；
所述下降温度为50～60℃，所述继续反应时间2～3h。
d.待预聚物降至室温，加入氯金酸，充分搅拌30min以上；
e.加入NaOH溶液调节反应物的PH＝11～13，室温下反应≥12h；
f.在剧烈搅拌下，缓慢加入经冷藏处理的去离子水进行乳化，得到水性聚氨酯模板法制备的纳米金团簇。
所述剧烈搅拌的搅拌速度可为1700～2000r/min，所述乳化时间为10min以上。
与现有技术比较，本发明具有如下突出优点：
利用水性聚氨酯为模板制备金纳米团簇的方法，由于金(Au)和硫(S)之间强烈的作用和反应能力使得巯基化合物非常适用于制备金纳米团簇。该发明利用这一性质，通过对聚氨酯分子链的设计，将硫醇分子接枝到聚氨酯分子链上，建立以硫醇型聚氨酯作为合成金纳米团簇的保护剂和还原剂还原氯金酸，原位合成硫醇型聚氨酯保护的强荧光金纳米团簇。
根据本发明通过水性聚氨酯模板法制备的荧光型金纳米团簇具有较强的光致发光效应，因此该发明可以广泛的应用在传感器、金属离子检测、生物显影，生物检测，药物追踪，化学检测等方面。
附图说明
图1为实施例1通过水性聚氨酯模板法制备的荧光型金纳米团簇的TEM图。在图1中，图的刻度尺为5nm。
图2为实施例2通过水性聚氨酯模板法制备的荧光型金纳米团簇的紫外-近红外吸收光谱。在图2中，横坐标为波长(单位：nm)；纵坐标为吸光度。
图3为实施例3通过水性聚氨酯模板法制备的荧光型金纳米团簇的荧光光谱。在图3中，横坐标为发射光波长(单位：nm)；纵坐标为发射光的强度(单位：a.u.)。
具体实施方式
下面通过具体实施例对本发明作进一步解释说明：
实施例1
采用本发明方法制备金纳米簇。(1)按照IPDI17％，PTMG71％的比例加入到烧瓶中，再将质量百分数为4％的二羟甲基丙酸加入到四口烧瓶中，在氮气保护下，升温至85℃加入0.04％二月桂酸二丁基锡，继续反应4h；(2)将反应体系降温至60℃，加入3.8％的1,4-丁二醇和1.7％巯基乙醇，恒温反应3h，此过程用少量丙酮降粘；(3)待预聚物降至室温，按照3.4％加入配制的氯金酸-丙酮溶液，充分搅拌半h；用1mol/LNaOH溶液调节反应物的PH＝12，室温下反应12h；(4)在1700r/min搅拌速度下，缓慢加入冷却的去离子水(固含量为40％)，乳化15min，得到水性聚氨酯模板法制备的荧光型金纳米团簇。
参见图1可知，本实施例中通过水性聚氨酯模板法制备的荧光型金纳米团簇的粒径在2～3nm。
实施例2
采用本发明方法制备金纳米簇。(1)按照IPDI30％，PTMG55％的比例加入到四口烧瓶中，再将质量百分数为4.5％的二羟甲基丙酸加入到四口烧瓶中，在氮气保护下，升温至90℃加入0.05％二月桂酸二丁基锡，继续反应4h；(2)将反应体系降温至60℃，加入4％的1,4-丁二醇和2.3％巯基乙醇，恒温反应3h，此过程用少量丙酮降粘；(3)待预聚物降至室温，按照4.2％的量加入配制的氯金酸-丙酮溶液，充分搅拌半h；加入2mol/LNaOH溶液调节反应物的PH＝13，室温下反应14h；(4)在1700r/min搅拌速度下，缓慢加入冷却的去离子水(固含量为40％)，乳化15min，得到水性聚氨酯模板法制备的荧光型金纳米团簇。
参见图2可知，通过水性聚氨酯模板法制备的荧光型金纳米团簇的光学性能与金颗粒明显不同，图2是典型的金纳米团簇的紫外吸收光谱。
实施例3
采用本发明方法制备金纳米簇。(1)按照IPDI25％，PTMG60％的比例加入到四口烧瓶中，再将质量百分数为5％的二羟甲基丙酸加入到四口烧瓶中，在氮气保护下，升温至90℃加入0.06％二月桂酸二丁基锡，继续反应4h；(2)将反应体系降温至60℃，加入4.2％的1,4-丁二醇和2.6％巯基乙醇，恒温反应3h，此过程用少量丙酮降粘；(3)待预聚物降至室温，按照3.2％的浓度值加入配制的氯金酸-丙酮溶液，充分搅拌半h；加入3mol/LNaOH溶液调节反应物的PH＝11，室温下反应18h；(4)在1700r/min搅拌速度下，缓慢加入冷却的去离子水(固含量为40％)，乳化15min，得到水性聚氨酯模板法制备的金纳米团簇。
参见图3，可以看到通过水性聚氨酯模板法制备的荧光型金纳米团簇的发射波波长在700nm左右，并且表现出很高的荧光强度。
实施例4
采用本发明方法制备金纳米簇。(1)按照IPDI25％，PTMG60％的比例加入到四口烧瓶中，再将质量百分数为4.8％的二羟甲基丙酸加入到四口烧瓶中，在氮气保护下，升温至90℃加入0.06％二月桂酸二丁基锡，继续反应4h；(2)将反应体系降温至60℃，加入4％的1,4-丁二醇和2％巯基乙醇，恒温反应3h，此过程用少量丙酮降粘；(3)待预聚物降至室温，按照4％的百分比加入配制的氯金酸-丙酮溶液，充分搅拌半h；加入1mol/LNaOH溶液调节反应物的PH＝11.8，室温下反应14h；(4)在1700r/min搅拌速度下，缓慢加入冷却的去离子水(固含量为40％)，乳化15min，得到水性聚氨酯模板法制备的纳米金团簇。
经过紫外可见光谱和荧光光谱的分析，该实施例中制备的荧光型金纳米团簇的发射波长在650nm，并且同样具有较高的荧光效应。
Claims (10)
1.荧光型金纳米团簇，其特征在于，制备原料按质量百分比为：二异氰酸酯17％～30％，二元醇62％～73％，有机锡类催化剂0.04％～0.06％，亲水扩链剂4％～5％，小分子扩链剂3.8％～4.2％，巯基乙醇1.7％～2.6％，浓度10Mm/L氯金酸丙酮溶液3.2％～4.2％，调节荧光型金纳米团簇的PH＝11～13的氢氧化钠，余为水；
所述二异氰酸酯与二元醇的摩尔比为(2～4)∶1。
2.如权利要求1所述荧光型金纳米团簇，其特征在于，所述二异氰酸酯中的-NCO与二元醇中-OH的摩尔比为(2～4)∶1。
3.如权利要求1所述荧光型金纳米团簇，其特征在于，所述有机锡类催化剂为二月桂酸二丁基锡、辛酸亚锡中的至少一种，加入量为原料总质量的0.04％～0.06％。
4.如权利要求1所述荧光型金纳米团簇，其特征在于，所述二异氰酸酯为异佛尔酮二异氰酸酯、甲苯二异氰酸酯、4，4-亚甲基-二苯基二异氰酸酯、六亚甲基二异氰酸酯、4,4-亚甲基-二环己基二异氰酸酯中的至少一种。
5.如权利要求1所述荧光型金纳米团簇，其特征在于，所述二元醇为聚丙二醇、聚乙二醇、聚四氢呋喃二醇、聚己二酸1,6-己二醇酯、聚碳酸酯、聚丁二烯二醇中的至少一种，分子量为1500～2500。
6.如权利要求1所述荧光型金纳米团簇，其特征在于，所述亲水扩链剂有磺酸型和羧酸型，为1,2-二羟基-3-丙磺酸钠、二羟甲基丙酸、二羟甲基丁酸中的至少一种；优选二羟甲基丙酸。
7.如权利要求1所述荧光型金纳米团簇，其特征在于，所述小分子扩链剂为一缩二乙二醇、1,4-丁二醇、聚醚改性氢醌、环己烷二甲醇、甲基丙二醇、乙二胺和异佛尔酮二胺中的至少一种；优选1,4-丁二醇。
8.如权利要求1所述荧光型金纳米团簇，其特征在于，所述氢氧化钠水溶液的浓度为1～3mol/L。
9.荧光金纳米团簇的水性聚氨酯模板法制备方法，其特征在于，所述荧光型金纳米团簇为权利要求1所述荧光型金纳米团簇，所述制备方法包括以下步骤：
1)将二元醇、亲水扩链剂置于真空烘箱中干燥，将其他的预聚单体加入分子筛进行干燥；
2)将脱水处理的二元醇、二异氰酸酯、亲水扩链剂按比例加入到四口烧瓶中，在氮气保护下，继续反应；
3)待反应体系降温后，加入小分子扩链剂和巯基乙醇，继续进行反应，此过程用丙酮降粘；
4)待预聚物降至室温，加入氯金酸，充分搅拌30min以上；
5)加入NaOH溶液调节反应物的pH＝11～13，室温下反应≥12h；
6)在剧烈搅拌下，缓慢加入经冷藏处理的去离子水进行乳化，得到水性聚氨酯模板法制备的纳米金团簇。
10.如权利要求9所述水性聚氨酯模板制备荧光金纳米团簇，其特征在于，步骤1)中，所述真空烘箱的温度可为100～120℃；所述干燥的时间可为3～5h；所述分子筛可为4A分子筛；所述分子筛干燥的时间可为24h以上；步骤2)中，所述升温的温度可至70～80℃，所述继续反应的时间可为3～4h；步骤3)中，所述下降温度可为50～60℃，所述继续反应时间可为2～3h；步骤6)中，所述剧烈搅拌的搅拌速度可为1700～2000r/min，所述乳化时间可为10min以上。
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