CN110724280A - 具有热响应的超分子聚合物水凝胶及其金属凝胶的制备和应用 - Google Patents
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Abstract
本发明公开了一种具有热响应的超分子聚合物水凝胶,是以邻苯二甲酰亚胺功能化柱[5]芳烃G为主体,以三足小分子化合物HQ为客体,在DMSO/H2O中通过主客体相互作用可以形成具有热响应的超分子聚合物水凝胶GHQ‑G。水凝胶GHQ‑G对Tb3+和Eu3+超灵敏检测性能。GHQ‑G和Tb3+、Eu3+相互作用以后得到的超分子聚合物金属凝胶GHQ‑GTb和GHQ‑Geu也具有聚集诱导发光特性,而且GHQ‑GTb和GHQ‑GEu可以超灵敏检测CN‑和ClO4 ‑,因此,该超分子聚合物水凝胶在离子的超灵敏响应领域具有十分重要的意义。
Description
技术领域
本发明涉及一种超分子聚合物水凝胶,尤其涉及一种具有热响应的超分子聚合物水凝胶;本发明同时还涉及该超分子聚合物水凝胶在识别、分离和去除水溶液中Tb3+和Eu3+中的应用;本发明还涉及基于该超分子聚合物水凝胶的金属凝胶及其在高灵敏识别CN-、ClO4 -的应用,属于超分子聚合物领域和离子检测领域。
背景技术
氰化物的毒性主要由其在体内释放的氰根而引起。氰化物可由呼吸道和消化道摄入体内。氰根离子在体内能很快与细胞色素氧化酶中的三价铁离子结合,抑制该酶活性,使组织不能利用氧。当大量吞入或吸入高浓度氰化物时,中毒者随即倒地,意识丧失,瞳孔放大,迅速死亡。吞服氰化物较少者,开始感到咽喉紧缩、强烈恐惧、胸内抑闷、眩晕、呕吐、眼睛凸出,肌肉痉挛、脉搏快而弱,最后因呼吸麻痹而死,前后不过20分钟左右。摄入体内低浓度的氰化物,一部分转化成硫氰酸盐随尿排出体外,一部分逐渐在体内蓄积,久而久之,引起慢性中毒。所以检测并分离吸附CN-是很有必要的。
2001年,唐本忠课题组报道了一种全新的聚集诱导发光(AIE)概念,这与传统的聚集诱导猝灭(ACQ)理论恰恰相反。AIE理论认为荧光增强是由于聚集诱导平面化和J型聚集形成的协同效应导致的,因为聚集诱导平面化和J型聚集有助于防止分子内旋转。自从该理论被提出以后,一系列具有AIE性质的分子已被用做制备化学传感器、刺激响应纳米材料、有机光二极管等。
超分子聚合物有机凝胶是聚集诱导发光领域的一个重要子集,它可以通过多种非共价的相互作用由凝胶因子组装而成。目前,由于超分子聚合物有机凝胶具有独特的结构和优异的性能,它已经被广泛应用于化学传感器、污染物去除和光催化等领域。
发明内容
本发明的目的是提供一种具有热响应的超分子聚合物水凝胶及其制备方法;
本发明的另一目的是对上述具有热响应超分子聚合物水凝胶对稀土离子Tb3+、Eu3+具有荧光响应性和识别性能进行研究;
本发明还有一个目的,就是提供一种基于上述具有热响应超分子聚合物水凝胶的金属凝及其在识别CN-、ClO4 -的应用。
一、具有热响应超分子聚合物水凝胶
本发明的超分子聚合物水凝胶,是以邻苯二甲酰亚胺钾功能化柱[5]芳烃为主体凝胶因子(G),三足小分子化合物为客体凝胶因子(HQ),在DMSO/H2O体系中通过主客体相互作用形成的具有聚集诱导发光特性的水凝胶(GHQ-G)。
主体凝胶因子(G)的结构式如下:
客体凝胶因子(HQ)的结构式如下:
主体凝胶因子(G)与客体凝胶因子(HQ)的摩尔比为1:3.1~1:3.5。
DMSO/H2O体系中,H2O的体积百分数为60~70%;该凝胶的临界凝胶浓度为33mg/ml。
超分子聚合物有机凝胶GHQ-G的和制备:将主体凝胶因子(G)与客体凝胶因子(HQ)加入到DMSO/H2O体系中,加热溶解后在冷却至室温,即得凝胶。该凝胶在室温下有强烈的黄色荧光(见图1)。
图2为GHQ-G在凝胶与溶胶之间转化的荧光谱图。结果显示,GHQ-G在凝胶状态下显示出较强的橘黄色荧光,但是将该凝胶加热溶解成溶胶后,溶胶的荧光明显减弱,说明GHQ-G具有聚集诱导发光特性。
二、GHQ-G对稀土金属的超灵敏检测
1、GHQ-G对Tb3+和Eu3+的荧光响应
用微量荧光比色皿配制一系列体积为200μL的超分子聚合物水凝胶GHQ-G,向每份凝胶中加入1倍当量的不同金属离子水溶液(Fe3+,Hg2+,Ag+,Ca2+,Cu2+,Co2+,Ni2+,Cd2+,Pb2+,Zn2+,Cr3+,Mg2+,Ba2+,Al3+,Eu3+,Tb3+,La3+和Th4+),离子的浓度为0.1mol/L。加热溶解,观察GHQ-G的荧光变化情况。结果发现,只有Tb3+和Eu3+可以使GHQ-G的荧光猝灭(或减弱),而其余金属离子的加入对GHQ-G的荧光没有明显影响。说明GHQ-G能对Tb3+和Eu3+有单一选择性识别性能。
2、GHQ-G对Tb3+的荧光滴定实验
用微量荧光比色皿配制一份体积为200μL的GHQ-G,并在加热条件下,向其中逐渐加入Tb3+水溶液(浓度为0.1mol/L),用荧光分光光度计测定凝胶荧光强度的变化。图3为GHQ-G对Tb3+离子的荧光滴定图像(λ ex = 290nm)。由图3可知,随着Tb3+的逐渐加入,GHQ-G的荧光逐渐减弱。通过计算可知,GHQ-G对Tb3+的荧光检测限为64.4 nmol/L(图5)。
3、GHQ-G对Eu3+的荧光滴定实验
用微量荧光比色皿配制一份体积为200μL的GHQ-G,并在加热条件下,向其中逐渐加入Eu3+水溶液(浓度为0.1mol/L),用荧光分光光度计测定凝胶荧光强度的变化。图4为GHQ-G对Eu3+离子的荧光滴定图像(λ ex = 290nm)。由图4可知,随着Eu3+的逐渐加入,GHQ-G的荧光逐渐减弱。通过计算可知,GHQ-G对Eu3+的荧光检测限为13.3 nmol/L(图5)。
4、GHQ-G对Tb3+、Eu3+和CN-、ClO4 -的识别机理
首先,三足客体HQ上的吡啶分别进入主体化合物G的柱五芳烃空腔中,一个三足客体与三个柱五芳烃相结合,而客体HQ的苯环与另外一个客体HQ的苯环之间是π-π堆积,主体G的柱五芳烃与柱五芳烃之间形成了外墙π-π作用,形成的这种超分子二维网状凝胶。当向主体G中加入Tb3+、Eu3+,由于Tb3+、Eu3+能与邻苯二甲酰亚胺产生阳离子-π作用,破坏了主体G凝胶因子之间的外墙π-π作用,导致GHQ-G的荧光猝灭;当向荧光猝灭的金属凝胶GHQ-G中加入CN-、ClO4 -时,由于CN-与Tb3+的络合和ClO4 -与Eu3+的络合,使GHQ-G的外墙π-π作用再次恢复,导致聚集态诱导荧光重新出现,从而实现对Tb3+、Eu3+和CN-、ClO4 -检测。
基于该机理,GHQ-G可用于水溶液中Tb3+和Eu3+的吸附与分离。
三、稀土金属超分子凝胶的制备及对阴离子的荧光响应
1、稀土金属超分子凝胶的制备
在实验过程中,当在凝胶GHQ-G中加入Eu3+、Tb3+水溶液并加热时,凝胶GHQ-G的荧光猝灭。随后,针对这一现象,我们设计了制备了金属凝胶GHQ-GTb、GHQ-GEu。具体操作如下,在超分子聚合物有机凝胶GHQ-G中,分别加入1倍当量的Eu3+、Tb3+水溶液,加热溶解后在冷却至室温,GHQ-G与金属离子Tb3+、Eu3+络合形成金属凝胶GHQ-GTb、GHQ-GEu。
2、GHQ-GTb对CN-的专一性荧光响应
用微量荧光比色皿配制一系列体积为200μL的GHQ-GTb,在加热成溶胶后,分别向每份凝胶中加入1倍当量的不同阴离子AcO-,HSO4 -,H2PO4 -,F-,Cl-,Br-,I-,ClO4 -,SCN-,CN-,S2 -,N3 -的水溶液(离子的浓度为0.1mol/L)。观察GHQ-GTb的荧光变化情况。结果发现,只有CN-的加入可以使金属凝胶GHQ-GTb的荧光恢复到打开状态。而其余阴离子的加入对GHQ-GTb的荧光无明显影响。说明GHQ-GTb能选择性识别CN-。
3、GHQ-GTb对CN-的荧光滴定实验
用微量荧光比色皿配制一份体积为200μL的GHQ-GTb,在加热条件下,向其中逐渐加入CN-水溶液(浓度为0.1mol/L),用荧光分光光度计测定该凝胶荧光强度的变化。图6为GHQ-GTb对CN-离子的荧光滴定图像(λ ex = 290nm)。由图6可知,随着CN-的逐渐加入,GHQ-GTb的荧光逐渐逐渐增强。通过计算可知,GHQ-GTb对CN-的荧光检测限为69.02 nmol/L(图8)。
4、GHQ-GEu对ClO4 -的专一性荧光响应
用微量荧光比色皿配制一系列体积为200μL的GHQ-GEu,在加热成溶胶后,分别向每份凝胶中加入1倍当量的不同阴离子AcO-,HSO4 -,H2PO4 -,F-,Cl-,Br-,I-,ClO4 -,SCN-,CN-,S2 -,N3 -的水溶液(离子的浓度为0.1mol/L)。观察GHQ-GEu的荧光变化情况。结果发现,只有ClO4 -的加入可以使金属凝胶GHQ-GEu的荧光恢复到打开状态。而其余阴离子的加入对GHQ-GEu的荧光无明显影响。说明GHQ-GEu能选择性识别ClO4 -。
5、GHQ-GEu对ClO4 -的荧光滴定实验
用微量荧光比色皿配制一份体积为200μL的GHQ-GEu,在加热条件下,向其中逐渐加入ClO4 -水溶液(浓度为0.1mol/L),用荧光分光光度计测定该凝胶荧光强度的变化。图7为GHQ-GEu对ClO4 -离子的荧光滴定图像(λ ex = 290nm)。由图7可知,随着ClO4 -的逐渐加入,GHQ-GEu的荧光逐渐恢复。通过计算可知,GHQ-GEu对ClO4 -的荧光检测限为204.76 nmol/L(图8)。
综上所述,本发明以邻苯二甲酰亚胺功能化柱[5]芳烃G为主体,以三足小分子化合物HQ为客体,在DMSO/H2O中通过主客体相互作用可以形成具有热响应的超分子聚合物水凝胶GHQ-G。水凝胶GHQ-G对Tb3+和Eu3+超灵敏检测性能。GHQ-G和Tb3+、Eu3+相互作用以后产生的热响应超分子聚合物金属凝胶GHQ-GTb和GHQ-Geu也具有聚集诱导发光特性,而且GHQ-GTb和GHQ-GEu可以超灵敏检测CN-和ClO4 -,因此,该超分子聚合物水凝胶在离子的超灵敏响应领域具有十分重要的意义。
附图说明
图1为GHQ-G的成凝胶图。
图2为GHQ-G在成凝胶过程中荧光强度随温度的变化谱图(λ ex =290nm)。
图3为GHQ-G对Tb3+离子的荧光滴定图像(λ ex = 290nm)。
图4为GHQ-G对Eu3+离子的荧光滴定图像(λ ex = 290nm)。
图5为GHQ-G对Eu3+和Tb3+的最低检测限(λ ex = 290nm)
图6为GHQ-GTb对CN-离子的荧光滴定图像(λ ex = 290nm)。
图7为GHQ-GEu对ClO4 -离子的荧光滴定图像(λ ex = 290nm)。
图8为GHQ-GEu对ClO4 -离子的最低检测线和GHQ-GTb对CN-离子的最低检测限(λ ex =290nm)。
具体实施方式
下面通过具体实施方式对本发明具有热响应的超分子聚合物水凝胶GHQ-G的之额比及在离子检测领域等应用做进一步说明。
实施例一、具有热响应的超分子聚合物水凝胶GHQ-G的合成
1、主体凝胶因子G的合成:首先,先将1,10-二溴癸烷(24.0056g,80mmol)和碘化钾(3.3200g,20mmol)加入到500mL的圆底烧瓶中在室温下搅拌20分钟后,再加入碳酸钾(8.2926g,60mmol)继续室温下搅拌10分钟后,将对甲氧基苯酚(2.4828g,20mmol)加入至此圆底烧瓶中,氮气保护下加热(65℃)搅拌48 h,得到产物溴代烷烃取代的对甲氧基苯酚。接着将溴代烷烃取代的对甲氧基苯酚称取(1.7586g,5mmol)于250mL圆底烧瓶中加入对甲氧基苯(5.2503g,38mmol)再加入200mL二氯甲烷于该烧瓶中,放在油浴锅(30℃)中搅拌,再加入多聚甲醛(2.8904g),然后再5mL三氟化硼乙醚反应1h左右,就会得到产物单取代的柱五芳烃。接下来,向100mL圆底烧瓶中分别加入单取代的柱五芳烃(0.95g,1.0mmol)、邻苯二甲酰亚胺钾(0.37g,2.0mmol)和DMF(30mL),氮气保护下加热(90℃)搅拌24h。反应结束后,加水将产物逼出,抽滤,干燥。将干燥后的产物溶于CH2Cl2中,加入硅胶,拌样,旋干。用柱层析法纯化(石油醚:乙酸乙酯 = 4:1),得到的淡黄色产物即为G(0.82g)。产率:80%,熔点:60 ~62℃。1H-NMR(CDCl3,600 MHz,δ/ppm:7.88-7.86(m,1H),7.84-7.83(m,1H),7.76-7.75(m,H),7.70-7.68(m,1H),6.78-6.75(m,10H),3.83-3.81(t,J = 6.5Hz,2H),3.77-3.74(m,10H),3.65-3.63(m,27H),3.58-3.56(t,J = 6.1Hz,2H),1.77-1.74(m,2H),1.66-1.64(m,2H),1.48-1.44(m,2H),1.25-1.23(m,10H)。13C-NMR(CDCl3,151 MHz),δ/ppm:168.41,150.61,150.49,150.01,133.79,132.18,128.26,128.21,128.18,128.10,123.10,113.78,68.40,55.63,38.05,31.76,31.49,29.78,29.47,29.39,29.12,28.58,26.90,26.84,26.26。HR-MS m/z:calcd for C62H75N2O12[G + NH4]+:1039.53;found:1039.37。
其合成式如下:
2、客体凝胶因子HQ的合成:向DMF(10mL)中加入均苯三甲酰氯(0.2655g,1.0mmol),室温搅拌使其充分溶解。然后,向一份新的DMF(10mL)中加入4-氨基吡啶(0.3106g,3.3mmol),室温搅拌使其充分溶解。将溶解了4-氨基吡啶的DMF溶液倒入一个圆底烧瓶中,加入三乙胺(1mL)做催化剂,用恒压滴液漏斗向该圆底烧瓶中缓慢滴加溶解了均苯三甲酰氯的DMF溶液,同时,室温搅拌24小时。反应结束后,对产物进行重结晶,得到的TA的质量为0.3943g,产率为90%。。1H NMR (400 MHz,DMSO-d 6),δ/ppm:10.98 (s,3H),8.79-8.75 (t,J = 8.6 Hz,6H),8.55-8.52 (t,J = 5.4 Hz, 6H),7.84-7.82 (t,J = 4.4 Hz,6H)。13C NMR (151 MHz,DMSO-d 6),δ/ppm:166.05,165.66,150.87,150.78,146.26,146.13,145.41,135.38,134.92,132.15,131.03,114.60,109.24。HRMS:m/z [TA + H]+ calcd for C24H19N6O3,439.1519;found 439.1515。其合成式如下:
3、超分子聚合物水凝胶GHQ-G的合成:
取0.01g主体凝胶因子G,0.0056g客体凝胶因子HQ,加入1mL的小瓶子中,先加入0.15mL的DMSO加热将G和HQ溶解后,再加入0.15mL的H2O中,此时再进行加热,将加水后析出的溶质,再一次加热溶解后,冷却至室温,得到具有二维网状超分子聚合物有机凝水胶GHQ-G。该凝胶GHQ-G的临界凝胶浓度为33 mg/m。该超分子聚合物水凝胶在凝胶状态下具有较强的橘黄色荧光,该凝胶加热溶解成溶胶后,溶胶的荧光明显减弱。
实施例二、超分子聚合物水凝胶GHQ-G识别Tb3+和Eu3+
在超分子聚合物水凝胶中,分别加入金属离子Fe3+,Hg2+,Ag+,Ca2+,Cu2+,Co2+,Ni2+,Cd2+,Pb2+,Zn2+,Cr3+,Mg2+,Ba2+,Al3+,Eu3+,Tb3+,La3+,Th4+的水溶液,加热溶解后,若GHQ-G的荧光猝灭或减弱,说明加入的是Tb3+和Eu3+,否则加入的是其他金属离子。
实施例三、金属凝胶GHQ-GTb的制备及应用
在超分子聚合物水凝胶GHQ中分别加入1倍当量的金属离子Tb3+,加热形成溶胶,在冷却至室温,得到具有聚集诱导发光特性的金属凝胶GHQ-GTb。
在加热下,分别向金属凝胶GHQ-GTb中加入阴离子AcO-,HSO4 -,H2PO4 -,F-,Cl-,Br-,I-,ClO4 -,SCN-,CN-,S2 -,N3 -的水溶液,若金属凝胶GHQ-GTb的荧光打开,则说明加入的是CN-,否则加入的是其他阴离子。
实施例四、金属凝胶GHQ-GEu的制备及应用
在超分子聚合物水凝胶GHQ中分别加入1倍当量的金属离子Eu3+,加热形成溶胶,在冷却至室温,得到具有聚集诱导发光特性的金属凝胶GHQ-GEu。
在加热下,分别向金属凝胶GHQ-GEu中加入阴离子AcO-,HSO4 -,H2PO4 -,F-,Cl-,Br-,I-,ClO4 -,SCN-,CN-,S2 -,N3 -的水溶液,若金属凝胶GHQ- GEu的荧光打开,则说明加入的是ClO4 -,否则加入的是其他阴离子。
实施例四、GHQ-G对水溶液中Tb3+和Eu3+的吸附与分离
称取一份GHQ-G(0.001g)的干凝胶粉末放入含有Tb3+的水溶液中(5mL,1×10-4mol/L)。称取一份GHQ-G(0.001g)的干凝胶粉末放入含有Eu3+的水溶液中(5mL,1×10-4mol/L)。将两者室温搅拌24小时,用离心机离心10分钟(1000r/min),取上清液。经电感耦合等离子体技术分析可知,GHQ-G的干凝胶粉末对Tb3+的吸附率为99.20~99.82%。GHQ-G的干凝胶粉末对Eu3+的吸附率为99.25~99.95%。说明GHQ-G的干凝胶粉末对水溶液中的Tb3+和Eu3+具有较好的吸附和分离能力。
Claims (10)
2.如权利要求1所述具有热响应的超分子聚合物水凝胶,其特征在于:主体凝胶因子与客体凝胶因子的摩尔比为1:3.1~1:3.5。
3.如权利要求1所述具有热响应的超分子聚合物水凝胶,其特征在于:DMSO/H2O体系中,H2O的体积百分数为60~70%。
4.如权利要求1所述具有热响应的超分子聚合物水凝胶,其特征在于:DMSO/H2O体系中,该凝胶的临界凝胶浓度为33 mg/ml。
5.如权利要求1所述具有热响应的超分子聚合物水凝胶,其特征在于:在凝胶状态下具有较强的橘黄色荧光,该凝胶加热溶解成溶胶后,溶胶的荧光明显减弱。
6.如权利要求1所述具有热响应的超分子聚合物水凝胶在识别Tb3+和Eu3+中的应用,其特征在于:在超分子聚合物水凝胶中,分别加入金属离子Fe3+,Hg2+,Ag+,Ca2+,Cu2+,Co2+,Ni2 +,Cd2+,Pb2+,Zn2+,Cr3+,Mg2+,Ba2+,Al3+,Eu3+,Tb3+,La3+,Th4+的水溶液,加热溶解后,只有Tb3+和Eu3+可以使超分子聚合物水凝胶的荧光猝灭或减弱,而其余金属离子的加入对超分子聚合物水凝胶的荧光没有影响。
7.如权利要求1所述具有热响应的超分子聚合物水凝胶在分离去除水溶液中Tb3+和Eu3+中的应用。
8.一种基于如权利要求1所述具有热响应的超分子聚合物水凝胶的金属凝胶的制备方法,是在超分子聚合物水凝胶中分别加入1倍当量的金属离子Tb3+、Eu3+,加热形成溶胶,在冷却至室温,得到具有聚集诱导发光特性的金属凝胶GHQ-GTb、GHQ-GEu。
9.如权利要求8所述方法制备的金属凝胶GHQ-GTb在识别CN-的应用,其特征在于:在加热下,分别向金属凝胶GHQ-GTb中加入阴离子AcO-,HSO4 -,H2PO4 -,F-,Cl-,Br-,I-,ClO4 -,SCN-,CN-,S2 -,N3 -的水溶液,只有CN-的加入可以使金属凝胶GHQ-GTb的荧光打开。
10.如权利要求8所述方法制备的金属凝胶GHQ-GEu在识别ClO4 -的应用,其特征在于:在加热下,分别向金属凝胶GHQ-GEu中加入阴离子AcO-,HSO4 -,H2PO4 -,F-,Cl-,Br-,I-,ClO4 -,SCN-,CN-,S2 -,N3 -的水溶液,只有ClO4 -的加入可以使金属凝胶GHQ-GEu的荧光打开。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107827818A (zh) * | 2017-11-20 | 2018-03-23 | 西北师范大学 | 一种基于柱[5]芳烃的凝胶因子及有机凝胶的应用 |
CN108658804A (zh) * | 2018-05-04 | 2018-10-16 | 西北师范大学 | 一种基于三柱[5]芳烃的超分子凝胶因子及其有机凝胶的制备和应用 |
CN109369921A (zh) * | 2018-09-13 | 2019-02-22 | 西北师范大学 | 具有二维网状结构的多重响应超分子聚合物凝胶的制备和应用 |
CN109400900A (zh) * | 2018-10-30 | 2019-03-01 | 西北师范大学 | 基于柱[5]芳烃主客体组装的超分子凝胶及其在检测和吸附铁离子的应用 |
CN109679119A (zh) * | 2018-12-24 | 2019-04-26 | 西北师范大学 | 一种基于季胺化水溶性柱[5]芳烃的主-客体超分子水凝胶的合成及应用 |
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN107827818A (zh) * | 2017-11-20 | 2018-03-23 | 西北师范大学 | 一种基于柱[5]芳烃的凝胶因子及有机凝胶的应用 |
CN108658804A (zh) * | 2018-05-04 | 2018-10-16 | 西北师范大学 | 一种基于三柱[5]芳烃的超分子凝胶因子及其有机凝胶的制备和应用 |
CN109369921A (zh) * | 2018-09-13 | 2019-02-22 | 西北师范大学 | 具有二维网状结构的多重响应超分子聚合物凝胶的制备和应用 |
CN109400900A (zh) * | 2018-10-30 | 2019-03-01 | 西北师范大学 | 基于柱[5]芳烃主客体组装的超分子凝胶及其在检测和吸附铁离子的应用 |
CN109679119A (zh) * | 2018-12-24 | 2019-04-26 | 西北师范大学 | 一种基于季胺化水溶性柱[5]芳烃的主-客体超分子水凝胶的合成及应用 |
Non-Patent Citations (1)
Title |
---|
QI LIN等: ""A novel supramolecular polymer π-gel based on bis-naphthalimide functionalized-pillar[5]arene for fluorescence detection and separation of aromatic acid isomers"", 《POLYM. CHEM.》 * |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111393370A (zh) * | 2020-03-30 | 2020-07-10 | 山西大学 | 一种基于柱[5]芳烃和咪唑衍生物的ab单体及超分子聚合物网络的构筑和应用 |
CN111393370B (zh) * | 2020-03-30 | 2022-07-19 | 山西大学 | 一种基于柱[5]芳烃和咪唑衍生物的ab单体及超分子聚合物网络的构筑和应用 |
CN114486838A (zh) * | 2022-02-18 | 2022-05-13 | 吉林大学 | 一种四环素类抗生素的检测方法 |
CN114486838B (zh) * | 2022-02-18 | 2024-03-15 | 吉林大学 | 一种四环素类抗生素的检测方法 |
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