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青霉胺稳定的铜/银双金属纳米簇制备及其在银离子检测中的应用
发光学应用及交叉前沿 | 更新时间：2022-02-25
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青霉胺稳定的铜/银双金属纳米簇制备及其在银离子检测中的应用 增强出版
- Preparation of Copper/Silver Bimetallic Nanoclusters Stabilized by Penicillamine and Their Application in Silver Ion Detection
- 发光学报 2022年 43卷 第2期 (2022)
- 作者机构：长春工业大学 化学工程学院， 材料科学高等研究院,吉林,长春,130012;吉林大学化学学院 超分子结构与材料国家重点实验室,吉林,长春,130012
- 作者简介：
- 基金信息：国家自然科学基金(51603018);吉林大学超分子结构与材料国家重点实验室开放课题(sklssm2021028)
- DOI：10.37188/CJL.20210341 中图分类号： O614
纸质出版日期：2022-02，
收稿日期：2021-11-02，
修回日期：2021-11-14，
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引用本文
白金娜, 王亮, 王明慧, 等. 青霉胺稳定的铜/银双金属纳米簇制备及其在银离子检测中的应用[J]. 发光学报, 2022, 43(2):285-295.
Jin-na BAI, Liang WANG, Ming-hui WANG, et al. Preparation of Copper/Silver Bimetallic Nanoclusters Stabilized by Penicillamine and Their Application in Silver Ion Detection[J]. Chinese Journal of Luminescence, 2022, 43(2):285-295.
白金娜, 王亮, 王明慧, 等. 青霉胺稳定的铜/银双金属纳米簇制备及其在银离子检测中的应用[J]. 发光学报, 2022, 43(2):285-295. DOI： 10.37188/CJL.20210341.
Jin-na BAI, Liang WANG, Ming-hui WANG, et al. Preparation of Copper/Silver Bimetallic Nanoclusters Stabilized by Penicillamine and Their Application in Silver Ion Detection[J]. Chinese Journal of Luminescence, 2022, 43(2):285-295. DOI： 10.37188/CJL.20210341.
青霉胺稳定的铜/银双金属纳米簇制备及其在银离子检测中的应用 增强出版
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"data": "。这些重金属如汞(Hg)、铅(Pb)、铜(Cu)、银(Ag)等离子因其高活性、高毒性、长持久性、生物难分解性、易富集和对生物体作用的加和性等特点而逐渐受到了国内外相关环境保护工作者的广泛重视和关注"
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"data": "。难降解的重金属以不同的状态或者形态在进入到自然环境或者生态系统后会不断被富集积累，从而影响到生态系统的平衡，并且重金属在进入到水体环境后会在底泥中沉积下来，被鱼、虾、蟹和藻类等水生生物所吸附，继而通过食物链层层富积浓缩，最终将会对食用水产品的人造成不可估量的健康危害"
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"data": ")是重金属离子中的一柄双刃剑。一方面，Ag"
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"data": "在一定浓度范围内表现出低毒甚至无毒的特性。新版饮用水质量指导标准已于2011年7月4日在新加坡国际水资源周上由世界卫生组织发布，它明确指出当饮用水中存在的银离子浓度不高于1.0×10"
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"data": "。另一方面，它在高浓度范围内却表现出较高的毒性，会对人体以及环境造成无法忽视的危害"
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"data": "存在的液态物体，如硝酸银，这样的银离子能与血红蛋白反应，是有毒的。但有Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "存在的固态物，如氯化银，是无法与血红蛋白结合的，这种情况下Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "又是无毒的。Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "的毒害作用主要是因为其具有较强的氧化性能，在进入人体后引起五脏六腑水肿等病变症状，情况严重甚至会致人死亡"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "12",
"type": "bibr",
"rid": "R12",
"data": [
{
"name": "text",
"data": "12"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "。并且，硝酸银、蛋白银、矽炭银、磺胺嘧啶银等药剂类银离子抗菌剂，在日本、欧洲、北美等发达国家，已经不允许将其应用于皮肤粘膜及环境的杀菌消毒。"
}
]
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "目前，常见的银离子检测方法有原子荧光光谱法(AFS)"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "13",
"type": "bibr",
"rid": "R13",
"data": [
{
"name": "text",
"data": "13"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "、表面增强拉曼散射光谱法(SERS)"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "14",
"type": "bibr",
"rid": "R14",
"data": [
{
"name": "text",
"data": "14"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "、原子吸收/发射光谱法(AAS/AES)"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "blockXref",
"data": {
"data": [
{
"name": "xref",
"data": {
"text": "15",
"type": "bibr",
"rid": "R15",
"data": [
{
"name": "text",
"data": "15"
}
]
}
},
{
"name": "text",
"data": "-"
},
{
"name": "xref",
"data": {
"text": "17",
"type": "bibr",
"rid": "R17",
"data": [
{
"name": "text",
"data": "17"
}
]
}
}
],
"rid": [
"R15",
"R16",
"R17"
],
"text": "15-17",
"type": "bibr"
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "、电感耦合等离子体质谱法(ICP-MS)"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "blockXref",
"data": {
"data": [
{
"name": "xref",
"data": {
"text": "18",
"type": "bibr",
"rid": "R18",
"data": [
{
"name": "text",
"data": "18"
}
]
}
},
{
"name": "text",
"data": "-"
},
{
"name": "xref",
"data": {
"text": "21",
"type": "bibr",
"rid": "R21",
"data": [
{
"name": "text",
"data": "21"
}
]
}
}
],
"rid": [
"R18",
"R19",
"R20",
"R21"
],
"text": "18-21",
"type": "bibr"
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "、伏安法"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "blockXref",
"data": {
"data": [
{
"name": "xref",
"data": {
"text": "22",
"type": "bibr",
"rid": "R22",
"data": [
{
"name": "text",
"data": "22"
}
]
}
},
{
"name": "text",
"data": "-"
},
{
"name": "xref",
"data": {
"text": "23",
"type": "bibr",
"rid": "R23",
"data": [
{
"name": "text",
"data": "23"
}
]
}
}
],
"rid": [
"R22",
"R23"
],
"text": "22-23",
"type": "bibr"
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "、电感耦合等离子体原子发射光谱法(ICP-AES)"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "blockXref",
"data": {
"data": [
{
"name": "xref",
"data": {
"text": "24",
"type": "bibr",
"rid": "R24",
"data": [
{
"name": "text",
"data": "24"
}
]
}
},
{
"name": "text",
"data": "-"
},
{
"name": "xref",
"data": {
"text": "25",
"type": "bibr",
"rid": "R25",
"data": [
{
"name": "text",
"data": "25"
}
]
}
}
],
"rid": [
"R24",
"R25"
],
"text": "24-25",
"type": "bibr"
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "、分光光度法"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "26",
"type": "bibr",
"rid": "R26",
"data": [
{
"name": "text",
"data": "26"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "等。虽然这些方法检测结果精准，但它们也存在着分析仪器设备占地面积大、检测人员技术要求高、测试费用昂贵、操作复杂和检测时间长等诸多问题"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "27",
"type": "bibr",
"rid": "R27",
"data": [
{
"name": "text",
"data": "27"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "。基于此，我们研发出一种价格低廉、分析速度快速、选择性高的荧光传感器"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "28",
"type": "bibr",
"rid": "R28",
"data": [
{
"name": "text",
"data": "28"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "。"
}
]
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "在材料科学中，可以通过各种不同的金属混合来形成合金，由于合金中不同金属的协同作用，能够使这些金属产生一些新的性质。双金属纳米簇正是一种合金型的金属纳米簇，其与单金属纳米簇相比，由于组分之间相互耦合产生等离子体激元带和电磁热点，具有优于单金属纳米簇的电子、化学和等离子体特性，以及有着更大的表面积、更好的催化活性和生物相容性，可被广泛用在催化、光学、磁学和生物诊断器等领域。"
}
]
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "在本工作中，我们为了得到铜/银双金属纳米簇的有序结构以及强发光性质，应用了青霉胺作为稳定剂和还原剂，因为D-青霉胺分子不仅能够提供有效的氢键和静电作用，而且有利于形成有序的铜/银双金属纳米簇结构。我们采用一锅法一步合成了青霉胺稳定的铜/银双金属纳米簇(DPA-Cu/Ag NCs)。首先，以过量的青霉胺(DPA)为稳定剂和还原剂制备了具有微弱红色荧光的铜纳米簇(DPA-Cu NCs)；然后通过向其中加入硝酸银溶液，制备得到了具有强烈明亮黄色荧光的DPA-Cu/Ag NCs。这种合成方法简单、绿色、价格低廉，并且制备得到的DPA-Cu/Ag NCs具有较强的荧光性能和良好的稳定性。此外，我们还对荧光性质变化的原因进行了简单的探讨，并将制备得到的DPA-Cu/Ag NCs作为荧光探针，应用于水溶液体系中，建立了一种具有高灵敏度、高选择性的Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "传感器。"
}
]
}
]
},
{
"name": "sec",
"data": [
{
"name": "sectitle",
"data": {
"label": [
{
"name": "text",
"data": "2"
}
],
"title": [
{
"name": "text",
"data": "实验"
}
],
"level": "1",
"id": "s2"
}
},
{
"name": "sec",
"data": [
{
"name": "sectitle",
"data": {
"label": [
{
"name": "text",
"data": "2.1"
}
],
"title": [
{
"name": "text",
"data": "试剂与仪器"
}
],
"level": "2",
"id": "s2a"
}
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "青霉胺(DPA)、硝酸银(AgNO"
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "3"
}
]
},
{
"name": "text",
"data": ")购于西格玛奥德里奇贸易有限(Aldrich)公司，五水合硫酸铜(CuSO"
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "4"
}
]
},
{
"name": "text",
"data": "·5H"
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "2"
}
]
},
{
"name": "text",
"data": "O)购于山东旭晨化工科技有限公司，所有参与实验的药物都为分析级。实验用水均采用去离子水。"
}
]
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "测试仪器包括：UV-2450型紫外-可见分光光度计(日本Shimadzu公司);LS-55型荧光分光光度计(PerkinElmer股份有限公司);JEOL-2000EX型透射电子显微镜(TEM，日本JEOL公司);iS50型傅里叶变换红外光谱仪(FT-IR，美国尼高力仪器公司);JEOL JSM-7610F型高分辨热场发射扫描电镜(SEM，日本JEOL公司);Smartlab型X射线衍射仪(XRD，日本Rigaku公司);FD-1-50型真空冷冻干燥器(北京博医康实验仪器有限公司)。"
}
]
}
]
},
{
"name": "sec",
"data": [
{
"name": "sectitle",
"data": {
"label": [
{
"name": "text",
"data": "2.2"
}
],
"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs制备"
}
],
"level": "2",
"id": "s2b"
}
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "我们利用青霉胺(DPA)作为本次实验过程的稳定剂和还原剂制备了Cu/Ag NCs。首先，将47.5 mL DPA溶液(160 mmol/L)加入到1.25 mL五水合硫酸铜溶液(0.1 mmol/L)中，在室温下以800 r/min的转速搅拌1.5 h，在搅拌过程中可以观察到有白色沉淀逐渐生成；之后向所得的混合溶液中加入3.75 mL硝酸银溶液(0.1 mmol/L)继续搅拌25 min，即可得到DPA-Cu/Ag NCs。为进一步优化实验效果，我们将所得到的DPA-Cu/Ag NCs溶液进行了离心处理，除去未参与反应的青霉胺等杂质，收集沉淀部分并将其重新分散在水溶液中。将DPA-Cu/Ag NCs溶液部分冻干，储存在冰箱内备用。青霉胺在反应过程中主要有三个作用：通过两个金属离子之间强烈的d10亲金属相互作用形成DPA-Cu(Ⅰ)Ag(Ⅰ)配合物；还原DPA-Cu(Ⅰ)Ag(Ⅰ)配合物；最终稳定Cu/Ag NCs。"
}
]
}
]
},
{
"name": "sec",
"data": [
{
"name": "sectitle",
"data": {
"label": [
{
"name": "text",
"data": "2.3"
}
],
"title": [
{
"name": "text",
"data": "选择性检测银离子"
}
],
"level": "2",
"id": "s2c"
}
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "为了考察DPA-Cu/Ag NCs对于Ag(Ⅰ)相比于其他金属离子的选择性，使用了以下金属离子：Ag(Ⅰ)、Ca(Ⅱ)、K(Ⅰ)、Hg(Ⅱ)、Fe(Ⅱ)、Mg(Ⅱ)、Pb(Ⅱ)、Na(Ⅰ)、Cr(Ⅲ)、Cr(Ⅵ)、Ni(Ⅱ)、Cu(Ⅱ)、Co(Ⅱ)、Al(Ⅲ)和Fe(Ⅲ)，研究了在这些金属离子存在下DPA-Cu/Ag NCs的荧光强度是否发生明显变化。我们将不同金属离子溶液(1.5 mL,470 μmol/L)和不同浓度的银离子溶液(1.5 mL,0~500 μmol/L)分别加入到新制备的DPA-Cu/Ag NCs溶液(1.5 mL)中，于室温下孵育5 min后测定其荧光强度。"
}
]
}
]
},
{
"name": "sec",
"data": [
{
"name": "sectitle",
"data": {
"label": [
{
"name": "text",
"data": "2.4"
}
],
"title": [
{
"name": "text",
"data": "实际水样分析"
}
],
"level": "2",
"id": "s2d"
}
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "为了验证DPA-Cu/Ag NCs传感器在实际水样中对Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "的检测性能，我们采用标准加入法对来自吉林省长春市南湖湖水、自来水以及瓶装矿泉水(泉阳泉)等样品进行了一系列的测试。自来水和瓶装矿泉水分别来自于实验室和当地超市，不需要任何预处理即可直接使用。湖水水样需经过10 000 r/min离心15 min，收集上清液并过滤。取加入不同浓度(15,50,85 μmol/L)Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "的水样1.5 mL，加入1.5 mL DPA-Cu/Ag NCs溶液中，测定其回收率，分别测定3次并取其平均值。"
}
]
}
]
}
]
},
{
"name": "sec",
"data": [
{
"name": "sectitle",
"data": {
"label": [
{
"name": "text",
"data": "3"
}
],
"title": [
{
"name": "text",
"data": "结果与讨论"
}
],
"level": "1",
"id": "s3"
}
},
{
"name": "sec",
"data": [
{
"name": "sectitle",
"data": {
"label": [
{
"name": "text",
"data": "3.1"
}
],
"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs制备及其表征"
}
],
"level": "2",
"id": "s3a"
}
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "在本工作中，分别以硝酸银和五水合硫酸铜作为Ag和Cu的前驱体，以青霉胺作为还原剂和稳定剂，采用一锅法一步合成了合金化DPA-Cu/Ag NCs，并将其作为荧光探针应用于银离子的检测。DPA-Cu/Ag NCs的制备及其对银离子的特异性检测流程如"
},
{
"name": "xref",
"data": {
"text": "图1",
"type": "fig",
"rid": "F1",
"data": [
{
"name": "text",
"data": "图1"
}
]
}
},
{
"name": "text",
"data": "所示。"
}
]
},
{
"name": "fig",
"data": {
"id": "F1",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图1"
}
],
"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs制备及其对Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "检测示意图"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.1"
}
],
"title": [
{
"name": "text",
"data": "The preparation of DPA-Cu/Ag NCs and its detection diagram of Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
}
]
}
],
"subcaption": [],
"note": [],
"graphics": [
{
"print": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=24623286&type=",
"small": "http://html.publish.founderss.cn/rc-pub/api/common/picture?pictureId=24623294&type=",
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},
{
"name": "p",
"data": [
{
"name": "text",
"data": "为了解DPA-Cu/Ag NCs的微观形貌，我们使用以镍网为载网的透射电子显微镜(TEM)等对其进行表征，结果如"
},
{
"name": "xref",
"data": {
"text": "图2(a)",
"type": "fig",
"rid": "F2",
"data": [
{
"name": "text",
"data": "图2(a)"
}
]
}
},
{
"name": "text",
"data": "所示。DPA-Cu/Ag NCs的形貌近乎于球形并且具有明显的单分散状态。其插图中相应的粒径分布图表明DPA-Cu/Ag NCs的平均粒径约为8 nm。"
},
{
"name": "xref",
"data": {
"text": "图2(b)",
"type": "fig",
"rid": "F2",
"data": [
{
"name": "text",
"data": "图2(b)"
}
]
}
},
{
"name": "text",
"data": "中的X射线能谱图(EDS)是与以镍网为载网的TEM同时测得的，从图中可以观察到所制备的DPA-Cu/Ag NCs含有C、N、O、S、Cu和Ag元素。"
}
]
},
{
"name": "fig",
"data": {
"id": "F2",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图2"
}
],
"title": [
{
"name": "text",
"data": "(a)DPA-Cu/Ag NCs的TEM图，比例尺：50 nm，插图为DPA-Cu/Ag NCs的粒径分布图；(b)DPA-Cu/Ag NCs的EDS图。"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.2"
}
],
"title": [
{
"name": "text",
"data": "(a)TEM image of DPA-Cu/Ag NCs, scale: 50 nm, illustration is the grain diameter distribution map of DPA-Cu/Ag NCs. (b)EDS patterns of DPA-Cu/Ag NCs."
}
]
}
],
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"data": [
{
"name": "text",
"data": "此外，我们还通过傅立叶变换红外光谱(FT-IR)测试方法对DPA-Cu/Ag NCs中存在的官能团进行了表征，不同化学基团的存在会产生对应于不同波数的特征峰。结果如"
},
{
"name": "xref",
"data": {
"text": "图3(a)",
"type": "fig",
"rid": "F3",
"data": [
{
"name": "text",
"data": "图3(a)"
}
]
}
},
{
"name": "text",
"data": "所示，与DPA的FT-IR曲线相比，可以观察到DPA-Cu/Ag NCs的FT-IR曲线上对应的S—H键伸缩振动带在2 527 cm"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "-1"
}
]
},
{
"name": "text",
"data": "附近消失，这表明S—Ag(Cu)键的形成是由于巯基与Ag(Cu)之间存在较强的相互作用"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "29",
"type": "bibr",
"rid": "R29",
"data": [
{
"name": "text",
"data": "29"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "。同时，在DPA-Cu/Ag NCs的FT-IR曲线上可观察到位于3 000 cm"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "-1"
}
]
},
{
"name": "text",
"data": "和1 630 cm"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "-1"
}
]
},
{
"name": "text",
"data": "的特征峰是由于—NH"
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "2"
}
]
},
{
"name": "text",
"data": "和羰基在—COOH上的伸缩振动所致，表明DPA-Cu/Ag NCs中含有较多的氨基和羧基。DPA-Cu/Ag NCs的XRD图谱如"
},
{
"name": "xref",
"data": {
"text": "图3(b)",
"type": "fig",
"rid": "F3",
"data": [
{
"name": "text",
"data": "图3(b)"
}
]
}
},
{
"name": "text",
"data": "所示，可以观察到38.1°(111)(fcc-Ag)、42.9°(200)(fcc-Cu)两个"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "θ"
}
]
},
{
"name": "text",
"data": "值，这些峰证实了DPA-Cu/Ag NCs的合成。这些峰的锐度和强度反映了所制备的NCs的结晶度和纯度"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "30",
"type": "bibr",
"rid": "R30",
"data": [
{
"name": "text",
"data": "30"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "。"
}
]
},
{
"name": "fig",
"data": {
"id": "F3",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图3"
}
],
"title": [
{
"name": "text",
"data": "(a)DPA和DPA-Cu/Ag NCs的FT-IR图；(b)DPA-Cu/Ag NCs的XRD图。"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.3"
}
],
"title": [
{
"name": "text",
"data": "(a)FT-IR spectra of the DPA and DPA-Cu/Ag NCs. (b)XRD pattern of DPA-Cu/Ag NCs."
}
]
}
],
"subcaption": [],
"note": [],
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"label": [
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"data": "3.2"
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"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs制备条件优化"
}
],
"level": "2",
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"data": [
{
"name": "text",
"data": "在本次实验过程中DPA-Cu/Ag NCs性能会因为不同的实验条件而产生不同的效果，为了获得最佳的荧光性能，我们对DPA-Cu/Ag NCs的一些制备条件进行了进一步的探索和优化。在制备DPA-Cu/Ag NCs的过程中，我们使用了过量的青霉胺来还原Cu"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "2+"
}
]
},
{
"name": "text",
"data": "和Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "并维持其稳定。在这一过程中我们发现，不同量比的Cu"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "2+"
}
]
},
{
"name": "text",
"data": "与Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "会对DPA-Cu/Ag NCs的荧光性能产生影响。因此，首先，在其他实验条件保持一致的情况下，我们对不同物质的量比进行了研究。其结果如"
},
{
"name": "xref",
"data": {
"text": "图4(a)",
"type": "fig",
"rid": "F4",
"data": [
{
"name": "text",
"data": "图4(a)"
}
]
}
},
{
"name": "text",
"data": "所示，可以看出在不同量比(［Cu"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "2+"
}
]
},
{
"name": "text",
"data": "］∶［Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "］)的情况下DPA-Cu/Ag NCs的荧光发射波长位置几乎没有发生变化；并且我们从"
},
{
"name": "xref",
"data": {
"text": "图4(b)",
"type": "fig",
"rid": "F4",
"data": [
{
"name": "text",
"data": "图4(b)"
}
]
}
},
{
"name": "text",
"data": "中还得到了当Cu"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "2+"
}
]
},
{
"name": "text",
"data": "与Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "的量比为1∶3时，制备得到的DPA-Cu/Ag NCs具有最好的荧光性能。其次，我们还对DPA-Cu/Ag NCs制备过程中硝酸银溶液加入后反应的时间进行了一系列的分析研究。结果如"
},
{
"name": "xref",
"data": {
"text": "图4(c)",
"type": "fig",
"rid": "F4",
"data": [
{
"name": "text",
"data": "图4(c)"
}
]
}
},
{
"name": "text",
"data": "所示，将硝酸银加入混合溶液后持续搅拌25 min获得的DPA-Cu/Ag NCs的荧光强度最高，而在反应时间达到25 min之后，DPA-Cu/Ag NCs的荧光强度随着反应时间增加呈现出持续下降的趋势。但在该过程中，荧光发射峰峰位置(555 nm)没有发生显著的位置变化，这说明引发荧光强度变化的原因并不是颗粒大小的改变。因此，从"
},
{
"name": "xref",
"data": {
"text": "图4(d)",
"type": "fig",
"rid": "F4",
"data": [
{
"name": "text",
"data": "图4(d)"
}
]
}
},
{
"name": "text",
"data": "中得到我们制备DPA-Cu/Ag NCs的最佳反应时间是25 min。"
}
]
},
{
"name": "fig",
"data": {
"id": "F4",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图4"
}
],
"title": [
{
"name": "text",
"data": "不同［Cu"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "2+"
}
]
},
{
"name": "text",
"data": "］∶［Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "］量比的DPA-Cu/Ag NCs荧光光谱(a)及其与荧光强度之间的关系(b)；不同反应时间的DPA-Cu/Ag NCs的荧光光谱(c)及其与荧光强度之间的关系(d)。"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.4"
}
],
"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs fluorescence spectra of different ［Cu"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "2+"
}
]
},
{
"name": "text",
"data": "］∶［Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "］ molar ratios(a) and their relationship with fluorescence intensity(b). DPA-Cu/Ag NCs fluorescence spectra with different reaction time(c) and their relationship with fluorescence intensity(d)."
}
]
}
],
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"title": [
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"data": "DPA-Cu/Ag NCs性能分析"
}
],
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{
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"data": [
{
"name": "text",
"data": "对DPA-Cu/Ag NCs进行了光学性质表征，"
},
{
"name": "xref",
"data": {
"text": "图5(a)",
"type": "fig",
"rid": "F5",
"data": [
{
"name": "text",
"data": "图5(a)"
}
]
}
},
{
"name": "text",
"data": "是在不同激发波长下得到的DPA-Cu/Ag NCs发射光谱，从图中我们可以看出DPA-Cu/Ag NCs的最佳激发波长为300 nm。从"
},
{
"name": "xref",
"data": {
"text": "图5(b)",
"type": "fig",
"rid": "F5",
"data": [
{
"name": "text",
"data": "图5(b)"
}
]
}
},
{
"name": "text",
"data": "中可知DPA-Cu/Ag NCs在560~600 nm处没有任何吸收峰，这意味着没有Cu纳米粒子生成。我们还观察到，当激发波长为300 nm时，DPA-Cu/Ag NCs溶液在555 nm处有明显的荧光发射峰。此外，"
},
{
"name": "xref",
"data": {
"text": "图5(b)",
"type": "fig",
"rid": "F5",
"data": [
{
"name": "text",
"data": "图5(b)"
}
]
}
},
{
"name": "text",
"data": "中的插图显示DPA-Cu/Ag NCs溶液在日光下为乳白色悬浊液(图左)，在紫外灯照射下呈现出明亮的黄色荧光(图右)。"
}
]
},
{
"name": "fig",
"data": {
"id": "F5",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图5"
}
],
"title": [
{
"name": "text",
"data": "(a)不同激发波长下DPA-Cu/Ag NCs的荧光发射光谱；(b)DPA-Cu/Ag NCs的荧光激发(Ex)和发射(Em)光谱与紫外吸收光谱(Abs)，插图为DPA-Cu/Ag NCs在可见光下(左)与紫外光下(右)的图像。"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.5"
}
],
"title": [
{
"name": "text",
"data": "(a)Fluorescence emission spectra of DPA-Cu/Ag NCs at different excitation wavelengths. (b)Fluorescence excitation(Ex) and emission(Em) spectra and ultraviolet absorption spectra(Abs) of DPA-Cu/Ag NCs. The illustration is the image of DPA-Cu/Ag NCs under visible light(left) and ultraviolet light(right)."
}
]
}
],
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"note": [],
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"data": [
{
"name": "text",
"data": "此外，我们还对制备得到的DPA-Cu/Ag NCs进行了稳定性能研究，分别测试了其在不同浓度盐溶液体系中、不同时间紫外光照射下以及室温环境中放置一段时间后荧光强度的变化。首先，以每5 mmol/L为一个增量配制了5~30 mmol/L浓度范围内的氯化钠盐溶液，测试了DPA-Cu/Ag NCs在不同浓度盐溶液体系中的荧光强度，实验结果如"
},
{
"name": "xref",
"data": {
"text": "图6",
"type": "fig",
"rid": "F6",
"data": [
{
"name": "text",
"data": "图6"
}
]
}
},
{
"name": "text",
"data": "所示。结果表明，DPA-Cu/Ag NCs的荧光强度在盐溶液体系中具有较高的稳定性。其次，我们将制备得到的DPA-Cu/Ag NCs溶液放置于发光波长为365 nm的紫外灯下进行照射，对其荧光强度值记录的间隔设为10 min，总照射时长为60 min。测得的"
},
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"data": "f/f"
}
]
},
{
"name": "sub",
"data": [
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"name": "text",
"data": "0"
}
]
},
{
"name": "text",
"data": "值如"
},
{
"name": "xref",
"data": {
"text": "图7",
"type": "fig",
"rid": "F7",
"data": [
{
"name": "text",
"data": "图7"
}
]
}
},
{
"name": "text",
"data": "所示，其中"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "f"
}
]
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "0"
}
]
},
{
"name": "text",
"data": "和"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "f"
}
]
},
{
"name": "text",
"data": "分别代表紫外灯照射前和紫外灯照射后的荧光强度值，从结果观察到DPA-Cu/Ag NCs在紫外灯照射下的"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "f/f"
}
]
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "0"
}
]
},
{
"name": "text",
"data": "值在0.94~1之间，该结果证实了该双金属纳米簇具有良好的抗紫外光性。最后，我们对DPA-Cu/Ag NCs的储存稳定性进行了测试，将制备得到的DPA-Cu/Ag NCs储存于室温环境条件下，在半个月的时间里每隔两天进行一次荧光强度测定。结果如"
},
{
"name": "xref",
"data": {
"text": "图8",
"type": "fig",
"rid": "F8",
"data": [
{
"name": "text",
"data": "图8"
}
]
}
},
{
"name": "text",
"data": "所示，其荧光强度几乎没有发生变化，光学性质稳定。综上所述，制备得到的DPA-Cu/Ag NCs具有良好的稳定性，可以广泛地应用于各种环境中，具有极强的实际应用价值。"
}
]
},
{
"name": "fig",
"data": {
"id": "F6",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图6"
}
],
"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs在不同浓度NaCl溶液中的荧光强度折线图"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.6"
}
],
"title": [
{
"name": "text",
"data": "The fluorescence intensity line diagram of DPA-Cu/Ag NCs in different concentrations of NaCl solution"
}
]
}
],
"subcaption": [],
"note": [],
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"data": {
"id": "F7",
"caption": [
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"lang": "zh",
"label": [
{
"name": "text",
"data": "图7"
}
],
"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs在紫外灯(365 nm)下照射不同时间的相对荧光强度"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.7"
}
],
"title": [
{
"name": "text",
"data": "The relative fluorescence intensity of DPA-Cu/Ag NCs irradiated by UV lamp(365 nm) for different time"
}
]
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"label": [
{
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"data": "图8"
}
],
"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs在室温环境下放置不同天数相对应的荧光强度折线图"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.8"
}
],
"title": [
{
"name": "text",
"data": "The fluorescence intensity line chart corresponding to different days were placed by DPA-Cu/Ag NCs at room temperature"
}
]
}
],
"subcaption": [],
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"data": {
"label": [
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"name": "text",
"data": "3.4"
}
],
"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs对银离子的特异性识别和检测"
}
],
"level": "2",
"id": "s3d"
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},
{
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"data": [
{
"name": "text",
"data": "在实验条件最优的情况下，我们对Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "传感器的灵敏度和选择性进行了测评。如"
},
{
"name": "xref",
"data": {
"text": "图9",
"type": "fig",
"rid": "F9",
"data": [
{
"name": "text",
"data": "图9"
}
]
}
},
{
"name": "text",
"data": "所示，为了评价DPA-Cu/Ag NCs检测Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "的灵敏度，我们检测了加入不同浓度的Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "后DPA-Cu/Ag NCs在300 nm处的荧光强度。随着银离子浓度从0~500 μmol/L不断增加，DPA-Cu/Ag NCs的荧光强度逐渐减弱，"
},
{
"name": "xref",
"data": {
"text": "图10",
"type": "fig",
"rid": "F10",
"data": [
{
"name": "text",
"data": "图10"
}
]
}
},
{
"name": "text",
"data": "所示的在可见光(上)和365 nm紫外灯(下)照射下观察到DPA-Cu/Ag NCs溶液随着银离子浓度增加而发生的明显颜色变化也证实了这一结果。鉴于巯基与金属银之间的强相互作用，我们推测在DPA-Cu/Ag NCs 溶液中加入Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "后，Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "与纳米簇表面的巯基配体相互作用，降低了纳米簇的稳定性，破坏了原始纳米簇的结构特性"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "31",
"type": "bibr",
"rid": "R31",
"data": [
{
"name": "text",
"data": "31"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "。"
}
]
},
{
"name": "fig",
"data": {
"id": "F9",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图9"
}
],
"title": [
{
"name": "text",
"data": "不同银离子浓度下DPA-Cu/Ag NCs的荧光光谱"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.9"
}
],
"title": [
{
"name": "text",
"data": "Fluorescence spectra of DPA-Cu/Ag NCs at different silver ion concentrations"
}
]
}
],
"subcaption": [],
"note": [],
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"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图10"
}
],
"title": [
{
"name": "text",
"data": "在不同浓度的银离子存在下DPA-Cu/Ag NCs在日光灯下(上)与紫外光下(下)的图像"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.10"
}
],
"title": [
{
"name": "text",
"data": "The images of DPA-Cu/Ag NCs in ultraviolet lamp(top) and fluorescent lamp(bottom) in the presence of different concentrations of silver ions"
}
]
}
],
"subcaption": [],
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{
"name": "p",
"data": [
{
"name": "text",
"data": "为了解添加Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "后DPA-Cu/Ag NCs荧光猝灭的原因并验证我们的假设，采用紫外-可见吸收光谱和Zeta电位测试对反应体系进行了表征。"
},
{
"name": "xref",
"data": {
"text": "图11",
"type": "fig",
"rid": "F11",
"data": [
{
"name": "text",
"data": "图11"
}
]
}
},
{
"name": "text",
"data": "显示DPA-Cu/Ag NCs溶液在300 nm附近有一个尖锐的峰；而在体系中加入Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "后，300 nm附近的峰变为较宽一些的肩峰，吸收强度明显增加，表明溶液的透光率降低。这表明Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "与DPA-Cu/Ag NCs形成了稳定的络合物，其机理主要是Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "与DPA-Cu/Ag NCs表面的氨基和巯基配体发生配位作用形成了配合物。上述结果表明，本研究中DPA-Cu/Ag NCs的荧光猝灭可能是由于Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "与DPA-Cu/Ag NCs表面的氨基和巯基配体相互作用，降低了纳米簇的稳定性，破坏了原始纳米簇的结构，并且形成非荧光基态配合物而导致的静态猝灭"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "30",
"type": "bibr",
"rid": "R30",
"data": [
{
"name": "text",
"data": "30"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "。在"
},
{
"name": "xref",
"data": {
"text": "图12",
"type": "fig",
"rid": "F12",
"data": [
{
"name": "text",
"data": "图12"
}
]
}
},
{
"name": "text",
"data": "的Zeta电位测试中发现，加入Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "后DPA-Cu/Ag NCs的表面电位增加，说明Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "主要作用于氨基和负电荷的屏蔽部分。以上实验结果进一步证明了Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "对DPA-Cu/Ag NCs荧光静态猝灭的机理"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "32",
"type": "bibr",
"rid": "R32",
"data": [
{
"name": "text",
"data": "32"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "。"
}
]
},
{
"name": "fig",
"data": {
"id": "F11",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图11"
}
],
"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs、Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "及其络合物的紫外吸收光谱。"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.11"
}
],
"title": [
{
"name": "text",
"data": "Absorption spectra of Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": ", DPA-Cu/Ag NCs and their mixture."
}
]
}
],
"subcaption": [],
"note": [],
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{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图12"
}
],
"title": [
{
"name": "text",
"data": "DPA-Cu/Ag NCs体系中加入Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "前后的Zeta电位图谱"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.12"
}
],
"title": [
{
"name": "text",
"data": "Zeta potential map before and after adding Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": " in DPA-Cu/Ag NCs system"
}
]
}
],
"subcaption": [],
"note": [],
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},
{
"name": "p",
"data": [
{
"name": "text",
"data": "取波长为555 nm(峰值)处的荧光强度值，利用Stern-Volmer方程得到了相对荧光强度("
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "F"
}
]
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "0"
}
]
},
{
"name": "text",
"data": "-"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "F"
}
]
},
{
"name": "text",
"data": ")/"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "F"
}
]
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "0"
}
]
},
{
"name": "text",
"data": "值，并在0~500 μmol/L浓度范围内对这些数值进行了线性拟合，结果如"
},
{
"name": "xref",
"data": {
"text": "图13",
"type": "fig",
"rid": "F13",
"data": [
{
"name": "text",
"data": "图13"
}
]
}
},
{
"name": "text",
"data": "所示，相对荧光强度和Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "的浓度在0.03~0.6 μmol/L范围内表现出良好的线性关系("
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "R"
}
]
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "2"
}
]
},
{
"name": "text",
"data": "=0.996 92)。拟合线性曲线方程为("
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "F"
}
]
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "0"
}
]
},
{
"name": "text",
"data": "-"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "F"
}
]
},
{
"name": "text",
"data": ")/"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "F"
}
]
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "0"
}
]
},
{
"name": "text",
"data": "=0.3317［Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "］-0.00926,"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "F"
}
]
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "0"
}
]
},
{
"name": "text",
"data": "和"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "F"
}
]
},
{
"name": "text",
"data": "分别代表不存在和存在Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "情况下的荧光强度，检测限(LOD)由3"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "s/k"
}
]
},
{
"name": "text",
"data": "方程确定，其中"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "s"
}
]
},
{
"name": "text",
"data": "为空白样品的标准差，"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "k"
}
]
},
{
"name": "text",
"data": "为"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "F"
}
]
},
{
"name": "sub",
"data": [
{
"name": "text",
"data": "0"
}
]
},
{
"name": "text",
"data": "/"
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "F"
}
]
},
{
"name": "text",
"data": "的斜率，通过计算得到银离子的检测限为0.3 μmol/L"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "["
},
{
"name": "xref",
"data": {
"text": "33",
"type": "bibr",
"rid": "R33",
"data": [
{
"name": "text",
"data": "33"
}
]
}
},
{
"name": "text",
"data": "]"
}
]
},
{
"name": "text",
"data": "。"
}
]
},
{
"name": "fig",
"data": {
"id": "F13",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图13"
}
],
"title": [
{
"name": "text",
"data": "相对荧光强度与银离子浓度(0~500 μmol/L)的关系，插图为相对荧光强度与银离子浓度(0.03~0.6 μmol/L)的线性关系。"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.13"
}
],
"title": [
{
"name": "text",
"data": "The relationship between relative fluorescence intensity and silver ion concentration(0-500 μmol/L). The illustration shows the linear relationship between relative fluorescence intensity and silver ion concentration(0.03-0.6 μmol/L)."
}
]
}
],
"subcaption": [],
"note": [],
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},
{
"name": "p",
"data": [
{
"name": "text",
"data": "为了考察该银离子传感器的离子选择性和抗干扰能力，我们研究了其他金属离子的存在对DPA-Cu/Ag NCs荧光强度的影响以及在有其他金属离子存在的情况下银离子对DPA-Cu/Ag NCs的特异性检测，结果如"
},
{
"name": "xref",
"data": {
"text": "图14(a)、(b)",
"type": "fig",
"rid": "F14",
"data": [
{
"name": "text",
"data": "图14(a)、(b)"
}
]
}
},
{
"name": "text",
"data": "所示。在体系中加入其他金属离子后，DPA-Cu/Ag NCs并没有发生十分强烈的荧光强度变化；而当体系中加入Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "后引起了DPA-Cu/Ag NCs荧光的急剧猝灭。这表明DPA-Cu/Ag NCs对银离子具有选择特异性，基于此可建立灵敏检测银离子的分析方法。"
}
]
},
{
"name": "fig",
"data": {
"id": "F14",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "图14"
}
],
"title": [
{
"name": "text",
"data": "(a)DPA-Cu/Ag NCs(470 μmol/L)在不同金属离子存在下的荧光强度变化；(b)在银离子存在和不存在时DPA-Cu/Ag NCs对不同金属离子的荧光响应。"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Fig.14"
}
],
"title": [
{
"name": "text",
"data": "(a)The fluorescence intensity changes of DPA-Cu/Ag NCs(470 μmol/L) in the presence of different metal ions. (b)The fluorescence response of DPA-Cu/Ag NCs to different metal ions in the presence and absence of Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "."
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]
}
],
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"label": [
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"data": "3.5"
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"title": [
{
"name": "text",
"data": "实际水样检测"
}
],
"level": "2",
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}
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "为了证实DPA-Cu/Ag NCs作为Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "传感器的实用性和准确性，我们把DPA-Cu/Ag NCs作为探针，对实际水环境中的Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "进行了检测。实际水样来自实验室自来水、当地湖水和瓶装矿泉水。银离子的测定结果如"
},
{
"name": "xref",
"data": {
"text": "表1",
"type": "table",
"rid": "T1",
"data": [
{
"name": "text",
"data": "表1"
}
]
}
},
{
"name": "text",
"data": "所示，湖水、瓶装矿泉水和实验室自来水中银离子的平均回收率分别为98.48%~106.53%、95.48%~100.47%和97.96%~102.53%,Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "检测的相对标准偏差("
},
{
"name": "italic",
"data": [
{
"name": "text",
"data": "n"
}
]
},
{
"name": "text",
"data": "=3)可控制在0.5%以下，表明该探针具有较好的准确度和重现性。以上实验数据表明，DPA-Cu/Ag NCs可以用于实际水样中Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "的检测。我们相信，DPA-Cu/Ag NCs在水溶液中Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
},
{
"name": "text",
"data": "的检测方面具有良好的应用前景。"
}
]
},
{
"name": "table",
"data": {
"id": "T1",
"caption": [
{
"lang": "zh",
"label": [
{
"name": "text",
"data": "表1"
}
],
"title": [
{
"name": "text",
"data": "水样中的银离子测定"
}
]
},
{
"lang": "en",
"label": [
{
"name": "text",
"data": "Tab. 1"
}
],
"title": [
{
"name": "text",
"data": "Determination of silver ion in water samples"
}
]
}
],
"note": [],
"table": [
{
"head": [
[
{
"colspan": "1",
"rowspan": "2",
"align": "center",
"style": "border-top:1px solid #000;border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "Sample"
}
]
},
{
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"align": "center",
"style": "border-top:1px solid #000;border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "Ag"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "+"
}
]
}
]
}
],
[
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"style": "border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "Spiked/(μmol·L"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "-1"
}
]
},
{
"name": "text",
"data": ")"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"style": "border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "Detected/(μmol·L"
},
{
"name": "sup",
"data": [
{
"name": "text",
"data": "-1"
}
]
},
{
"name": "text",
"data": ")"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"style": "border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "Recovery/%"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"style": "border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "RSD/%"
}
]
}
]
],
"body": [
[
{
"colspan": "1",
"rowspan": "3",
"align": "left",
"data": [
{
"name": "text",
"data": "Lake water"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "15.00"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "15.98"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "106.53"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "0.47"
}
]
}
],
[
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "50.00"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "51.77"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "103.54"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "0.26"
}
]
}
],
[
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "85.00"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "83.71"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "98.48"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "0.18"
}
]
}
],
[
{
"colspan": "1",
"rowspan": "3",
"align": "left",
"data": [
{
"name": "text",
"data": "Mineral water"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "15.00"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "15.07"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "100.47"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "0.32"
}
]
}
],
[
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "50.00"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "48.99"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "97.98"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "0.28"
}
]
}
],
[
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "85.00"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "81.16"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "95.48"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "0.14"
}
]
}
],
[
{
"colspan": "1",
"rowspan": "3",
"align": "left",
"style": "border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "Tap water"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "15.00"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "15.38"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "102.53"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "0.41"
}
]
}
],
[
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "50.00"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "50.51"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "101.02"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"data": [
{
"name": "text",
"data": "0.35"
}
]
}
],
[
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"style": "border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "85.00"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"style": "border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "83.27"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"style": "border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "97.96"
}
]
},
{
"colspan": "1",
"rowspan": "1",
"align": "center",
"style": "border-bottom:1px solid #000;",
"data": [
{
"name": "text",
"data": "0.22"
}
]
}
]
],
"foot": []
}
]
}
}
]
}
]
},
{
"name": "sec",
"data": [
{
"name": "sectitle",
"data": {
"label": [
{
"name": "text",
"data": "4"
}
],
"title": [
{
"name": "text",
"data": "结论"
}
],
"level": "1",
"id": "s4"
}
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "本文通过一锅法一步制备得到了以青霉胺为稳定剂和还原剂的具有强烈黄色荧光的铜/银双金属纳米簇，并通过一系列仪器设备对制备得到的DPA-Cu/Ag NCs进行了表征和分析，证明DPA-Cu/Ag NCs的合成是通过青霉胺中的巯基与Ag(Cu)之间发生了强烈的相互作用实现的，基于此建立了一种检测银离子的高灵敏传感器。DPA-Cu/Ag NCs传感器的检测限可以低达0.3 μmol/L，说明该传感器具有简单快速、选择性好、灵敏度高等优点。将其应用于检测实际样品(当地湖水、瓶装矿泉水和实验室自来水)中的银离子，获得了十分优异的准确度和重现性，因此可以将该DPA-Cu/Ag NCs传感器应用于实际水样的检测，拓宽其实用性能。"
}
]
},
{
"name": "p",
"data": [
{
"name": "text",
"data": "本文专家审稿意见及作者回复内容的下载地址：http://cjl.lightpublishing.cn/thesisDetails#10.37188/CJL.20210341."
}
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}
]
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"text": [
{
"name": "text",
"data": "国家自然科学基金（51603018）；吉林大学超分子结构与材料国家重点实验室开放课题（sklssm2021028）资助项目"
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"text": [
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"name": "text",
"data": "Supported by National Natural Science Foundation of China (51603018); State Key Laboratory of Supramolecular Structure and Materials of Jilin University (sklssm2021028)"
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],
"history": {
"received": "2021-11-02",
"revised": "2021-11-14",
"opub": "2022-02-24"
},
"copyright": {
"data": [],
"year": "2022"
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},
"appendix": [],
"type": "research-article",
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"supplementary": [],
"journalTitle": "发光学报",
"issue": "02",
"volume": "43",
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}
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