CN113493473A - 一种高效红光铕配合物发光材料及其制备方法和应用 - Google Patents
一种高效红光铕配合物发光材料及其制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种高效红光铕配合物发光材料及其制备方法及在对抗生素荧光传感方面的应用。该红光铕配合物[Eu(DPBA)(Phen)2]·H2O(H3DPBA=2‑(3',4'‑二羧基苯氧基)苯甲酸,Phen=1,10‑菲罗啉)通过水热法制备而成,属于三斜晶系,Pī空间群,晶胞参数 该高效红光铕配合物中Eu3+的配位数为8,其中每一个Eu3+分别与3个DPBA配体的4个氧原子和2个Phen配体的4个氮原子配位。配体DPBA与金属中心采用μ1:η1η0/μ2:η1η1的配位模式配位,形成一维结构。该高效红光铕配合物固体粉末量子产率高达86%。在352nm激发下可实现对几种抗生素的检测。本发明合成简单,成本低廉。
Description
技术领域
本发明涉及一种高效红光铕配合物发光材料及其制备方法,以及在对抗生素选择性检测等方面的应用,属于发光材料领域。
背景技术
稀土离子由于其独特的发光特性(发射寿命长、斯托克位移大、色纯度高),在过去二十年内已经成为了非常重要的多功能发光材料。但是,由于稀土离子f-f跃迁是禁阻的,稀土离子在紫外区对光的吸收非常弱,以至于稀土离子发光强度很弱。为了解决这一问题,通常引入在紫外区具有强吸光度的有机配体,通过有机配体将能量转移到稀土离子中心,从而敏化稀土离子发光(天线效应)。一般来说,“天线”通常需要在紫外区具有高的摩尔消光系数同时在系间窜跃和能量传递过程中也具有高的效率。因此,有机配体的选择和配合物的结构直接影响了配合物的发光。基于上述原因,π-共轭体系的芳香族或杂芳香族化合物成为了首要候选者。在过去的研究中发现,高效荧光铕配合物在发光、显示、照明、生物成像、检测等领域有着重要的应用,至今有大量高发光效率的材料被开发出来。然而迄今为止,文献报道的羧酸类高效发光铕配合物仍然较少。在近期的研究中,发明人发现了一种能够有效敏化金属铕,实现高效发光的羧酸类配体。2-(3',4'-二羧基苯氧基)苯甲酸(H3DPBA)是一种具有共轭体系及半刚性结构的有机配体,平面刚性较好;同时具有强的螯合配位能力的1,10-菲罗啉(Phen)同样具有大的共轭体系。两种配体可以共同调控配合物的结构,使得配体能够更加有效的向稀土离子中心传递能量,进而增强荧光性能。
由于高效红光铕配合物独特的荧光性质,使其在荧光检测方面具有广泛的应用,可实现对阴阳离子,有机分子,药物分子等的检测。抗生素作为畜牧业和水产养殖业中的一种常用药物,在治疗动物疾病和促进牲畜生长方面起着重要的作用。但是,抗生素的严重滥用和残留也已经造成了水资源和土壤资源的污染。更为严重的是,这些残留的抗生素最终可能被人类摄入,引起急性或慢性中毒。随着人民对公共卫生和环境保护的日益关注,对检测和去除环境污染物的需求越来越迫切。因此,在分析技术和环境科学领域中,找到可以快速检测阴阳离子、有机小分子和药物等的方法至关重要。
目前,对水体中抗生素含量进行检测分析的方法主要有液相色谱-质谱联用,紫外检测液相色谱法,毛细管电泳法,表面增强拉曼光谱法以及荧光法。传统的检测技术虽然灵敏度高,但是由于仪器昂贵不易携带等因素受到了很多限制。荧光法相比于其它检测方法具有操作简单,灵敏度高,选择性好等诸多优点。因此,越来越受到人们的重视并被广泛研究。
发明内容
针对现有技术中存在的上述不足,本发明的目的在于提供一种高效红光铕配合物的制备方法及应用。本发明中选取了H3DPBA和Phen两种具有大的共轭体系,在紫外区具有强吸光度的有机配体,通过水热法合成了一种发光效率高,热稳定好的铕配合物。其分子式为[Eu(DPBA)(Phen)2]·H2O,该新物质合成简单,性质稳定,在自然光下白色粉末,紫外激发下发射红色荧光,固体粉末量子产率高达86%。可用于红色荧光材料制备及用于检测生物及环境体系中阴阳离子、有机小分子和药物分子等。
为实现本发明的目的,通过以下技术方案实现:
一种高效红光铕配合物的制备方案如下:以Eu(NO3)3·6H2O,H3DPBA,Phen作为原料,以蒸馏水和氢氧化钠溶液作为溶剂,采用水热法制备而成。具体包括以下步骤:
(1)将Eu(NO3)3·6H2O,H3DPBA,Phen加入到带有聚四氟乙烯内胆的反应釜中,所述Eu(NO3)3·6H2O,H3DPBA,Phen的物质的量之比为1:1:1.5,加入10毫升(ml)蒸馏水和200微升(μL)浓度为1摩尔/升(mol/L)的氢氧化钠溶液作为溶剂。
将上述步骤(1)中的反应釜放置在电热恒温鼓风干燥箱中,升温至120摄氏度(℃)并持续加热72小时,然后以3摄氏度/小时(℃/h)的降温速率缓慢降至室温。
将上述步骤(2)所得到的产物过滤,干燥,得到白色粉末状固体,即为目标产物[Eu(DPBA)(Phen)2]·H2O。
采用上述方法制备的高效红光铕配合物可用于红色荧光材料制备及实现对水体中含硝基抗生素的检测。也可以用于检测生物及环境体系中阴阳离子、有机小分子和药物分子等。
与现有技术相比,本发明具有如下有益效果:
(1)由上述本发明提供的技术方案可以看出,本发明提供了一种高效红光铕配合物,该高效红光铕配合物采用了简单的一步水热法制备而成,其分子是为[Eu(DPBA)(Phen)2]·H2O。根据单晶数据分析表明,不对称晶胞单元中,包含一个晶体学独立的Eu3+离子、1个DPBA配体、2个Phen配体和1个未配位的游离水分子。热重曲线表明,该高效红光铕配合物具有很高的热稳定性,直到390℃左右骨架才开始坍塌。
(2)本发明制备的高效红光铕配合物,在自然光下呈无色,在365纳米(nm)紫外光下呈现明亮的红光。经荧光光谱测试可知,在352nm最大激发波长下,该铕配合物[Eu(DPBA)(Phen)2]·H2O固体在616nm处呈现较强的红色荧光发射峰,是铕离子的特征发射峰。固体粉末的量子产率高达86%。
(3)采用本发明的制备方法,制备出的高效红光铕配合物的产率约为60%。同时,本发明提供的高效红光铕配合物,对于环境污染治理、新型红光荧光材料的制备以及稀土元素的开发与利用都具有积极的影响。可以用于检测生物及环境体系中阴阳离子、有机小分子和药物分子等。
附图说明
图1(a)和图1(b)为本发明铕配合物[Eu(DPBA)(Phen)2]·H2O的晶体结构;其中图1(a)Eu(Ⅲ)配位环境图,图1(b)一维结构图;
图2为本发明铕配合物的X-射线粉末衍射图(横坐标—角度;纵坐标—衍射强度);
图3为本发明铕配合物的热重曲线图(空气气氛;横坐标—温度;纵坐标—残留百分比);
图4为本发明铕配合物的荧光光谱图(横坐标—波长;纵坐标—相对荧光强度;Ex为激发波长);其中插图:本发明铕配合物的激发图谱(Em为发射波长)。
图5为本发明铕配合物在不同类型抗生素溶液存在下的荧光强度变化示意图(横坐标—不同类型抗生素;纵坐标—相对荧光强度);
图6(a)-6(c)为本发明铕合物在352nm激发下,荧光强度随着滴加抗生素的量变化示意图(横坐标—波长;纵坐标—相对荧光强度);其中插图:抗生素滴定曲线所得线性回归方程(横坐标—抗生素浓度;纵坐标—(I0/I)-1;(I0为未滴加抗生素时的荧光强度,I为滴加抗生素后的荧光强度))。
具体实施方式
以下实施例用于说明本发明,但不用来限制本发明的范围。
为了更加清晰地展现出本发明所提供的技术方案及所产生的技术效果,下面结合具体实施例,对本发明方法进行详细说明。本发明中对最终产物进行X-射线单晶衍射测试,解析得其精确的晶体结构;并对最终产物进行一系列表征,如元素分析、X-射线粉末衍射、热重、荧光等。
总体来说,本发明的该高效红光铕配合物[Eu(DPBA)(Phen)2]·H2O(H3DPBA=2-(3',4'-二羧基苯氧基)苯甲酸,Phen=1,10-菲罗啉)通过水热法制备而成,属于三斜晶系,Pī空间群,晶胞参数 该铕配合物中Eu3+的配位数为8,其中每一个Eu3+分别与3个DPBA配体的4个氧原子和2个Phen配体的4个氮原子配位。配体DPBA与金属中心采用μ1:η1η0/μ2:η1η1的配位模式配位,形成一维结构。该高效红光铕配合物固体粉末量子产率高达86%。在352nm激发下可实现对几种抗生素的检测。
实施例1.
一、本发明高效红光铕配合物的制备
一种高效红光铕配合物,采用以下方法制备而成:将Eu(NO3)3·6H2O(0.1mmol),H3DPBA(0.1mmol),Phen(0.15mmol)放入25ml的反应釜中,加入10ml去离子水,200μL浓度为1mol/L的NaOH溶液,拧紧反应釜金属外称后放置在电热恒温鼓风干燥箱中,加热至120℃并持续72小时,以3℃/h降温速度降至室温,过滤,蒸馏水洗涤,干燥后,得到白色粉末状固体,产率约为60%。
选择质量好,大小合适,透明度高的晶体置于Bruker Smart APE XII CCD型X-射线单晶衍射仪上,用经石墨单色器单色化的Cu-Kα辐射光源对晶体进行扫描并收集衍射点,采用olex2程序由直接法解出晶体结构,由理论加氢法确定氢原子的坐标,并对氢原子和非氢原子分别采用各向同性和各向异性温度因子进行全矩阵最小二乘法修正。主要晶体学数据见表1。
表1.主要晶体学数据
解析数据得其晶体结构(图1(a)和图1(b))。结构分析结果表明,中心金属铕和DPBA的4个氧原子以及2个Phen的4个氮原子配位,形成八配位的一维金属-有机配位聚合物。PXRD测试图谱的峰与晶体结构拟合图谱(软件Mercury)的衍射峰可以很好的匹配,表明所得晶体即为目标产物,且样品纯度较高(图2)。
主要对称操作:11-X,-Y,1-Z;21+X,1+Y,+Z;3-1+X,-1+Y,+Z
目标产物化学式为C39H27N4O9Eu,分子质量为847.6,其元素分析理论值:C(55.21%),H(2.71%),N(6.61%),实际值:C(55.23%),H(2.69%),N(6.58%)。
空气气氛中,所得配合物产品热重数据分析显示,主要有两次失重,第一次在100℃左右,失去了游离水分子,失重百分率为2.21%(理论失重率为2.13%);390℃之后骨架开始分解,表明此高效红光铕配合物具有较高的热稳定性(图3)。
固态荧光测试表明,该铕配合物[Eu(DPBA)(Phen)2]·H2O的最大激发波长为352nm。以此波长作为激发波长,该铕配合物在593nm和616nm处出现荧光发射峰,为铕离子的特征发射峰(图4),固体粉末的荧光量子产率高达86%。
将本实施例重复多次,基于Eu(Ⅲ)的用量,计算得到配合物[Eu(DPBA)(Phen)2]·H2O产品产率约为60%。重复实验得到的晶体衍射数据与拟合得到的数据一致,制得的晶体结构未发生变化且产品较纯(图2),可见实施例1的操作可重复性很高。
二、本发明高效红光铕配合物对含硝基类抗生素的检测
称取本发明实例1所制的铕配合物粉末3毫克(mg),充分研磨后溶于3毫升(mL)水中,将其分散于阿莫西林,阿奇霉素,奥硝唑,磺胺二甲嘧啶,磺胺甲恶唑,磺胺嘧啶,磺胺噻唑甲砜霉素,甲硝唑,罗红霉素,洛硝哒唑,青霉素(浓度均为1×10-3mol/L)中,超声溶解30分钟,并老化三天。在352nm波长激发下得到荧光强度示意图(图5);
加入奥硝唑、甲硝唑和洛硝哒唑抗生素溶液后,铕配合物的荧光强度几乎被完全猝灭(图5)。因此,在一定范围内,本发明制备的高效红光铕配合物可以对水溶液中含硝基抗生素进行检测。也可以应用检测环境污染物中其它物质如阴阳离子、有机小分子等。
采用荧光滴定法,分别对奥硝唑、甲硝唑和洛硝哒唑三种抗生素进行滴定(浓度均为1×10-3mol/L),滴定范围为0-720μL,每次滴加后摇匀,检测配合物荧光发射谱。该铕配合物对对奥硝唑检测限为7.4×10-6mol/L,对甲硝唑检测限为1.2×10-7mol/L,对洛硝哒唑检测限为3.1×10-6mol/L(图6(a)-6(c))。
以上所述,仅为本发明的具体实施方式,但本发明的保护范围并不局限于此,任何熟悉本技术领域的技术人员在本发明揭露的技术范围内,可轻易想到变化或替换,都应涵盖在本发明的保护范围之内。
Claims (9)
1.一种高效红光铕配合物发光材料,其特征在于,该铕配合物的分子式为[Eu(DPBA)(Phen)2]·H2O(H3DPBA=2-(3',4'-二羧基苯氧基)苯甲酸,Phen=1,10-菲罗啉)。
3.根据权利要求1或2所述的高效红光铕配合物发光材料,其特征在于,根据单晶数据分析表明,该铕配合物的不对称晶胞单元中,包含一个晶体学独立的Eu3+离子、1个DPBA配体、2个Phen配体和1个未配位的游离水分子。
4.根据权利要求1所述的红光铕配合物发光材料,其特征在于,该铕配合物的中心金属铕和DPBA的4个氧原子以及2个Phen的4个氮原子配位,形成八配位的一维金属-有机配位聚合物。
5.根据权利要求1或2所述的红光铕配合物发光材料,其特征在于,热重曲线表明,该铕配合物具有很高的热稳定性,直到390℃左右骨架才开始坍塌。
6.根据权利要求1或2所述的红光铕配合物发光材料,其特征在于,经荧光光谱测试可知,在352nm紫外光激发下,该铕配合物[Eu(DPBA)(Phen)2]·H2O固体在616nm处呈现较强的红色荧光发射峰,固体粉末的量子产率高达86%。
7.一种红光铕配合物发光材料的制备方法,其特征在于,该方法以Eu(NO3)3·6H2O,H3DPBA,Phen作为原料,以蒸馏水和氢氧化钠溶液作为溶剂,采用水热法制备而成。
8.根据权利要求7所述的方法,其特征在于,该方法包括如下步骤:
步骤一:将Eu(NO3)3·6H2O,H3DPBA,Phen加入到带有聚四氟乙烯内胆的反应釜中,所述Eu(NO3)3·6H2O,H3DPBA,Phen的物质的量之比为1:1:1.5,加入10ml蒸馏水和200μL浓度为1mol/L的氢氧化钠溶液作为溶剂;
步骤二:将上述步骤一中的反应釜放置在电热恒温鼓风干燥箱中,升温至120℃并持续加热72小时,然后以3℃/h的降温速率缓慢降至室温;
将上述步骤二所得到的产物过滤,干燥,得到白色粉末状固体,即为目标产物[Eu(DPBA)(Phen)2]·H2O。
9.一种应用权利要求1所述的红光铕配合物发光材料的方法,其特征在于,该铕配合物可用于红色荧光材料制备及实现对水体中含硝基抗生素的检测,或者检测生物及环境体系中阴阳离子、有机小分子和药物分子。
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