本文主要研究内容
作者杜曼（2019）在《硅杂蒽近红外荧光分子探针的设计合成与分子识别检测研究》一文中研究指出：随着荧光化学的不断研究发展,发光分子功能材料的合成及其器件的制备逐渐引起了科研工作者的广泛关注。由于荧光检测的高灵敏度和可实时及远程检测等优越性,在分子识别与传感中的应用得到蓬勃发展,设计合成高灵敏、高选择性的荧光化学探针近年来备受关注。与具有较短吸收和发射波长的荧光探针相比,近红外荧光探针具有光毒性低、光散射小、组织穿透能力强、受生物体自发荧光影响小、有利于进行多荧光染色等优点。虽然已合成的近红外荧光探针种类较多,但大多存在水溶性差、光稳定性差、生物适应性差和可修饰性差等问题。基于此,发展新型的近红外小分子荧光识别检测探针具有重要的研究和应用价值。硅取代氧杂蒽类荧光探针是近几年来发展起来的一类新型荧光染料,是用硅原子取代氧杂蒽结构中的10位桥连O原子而得到的。通过将氧杂蒽分子中O桥原子用Si代替,得到了一类新型的探针分子—硅杂蒽类荧光探针在保留氧杂蒽荧光染料优越光学性质的同时,荧光波长大于600 nnm,红移至NIR区域,满足近红外荧光检测的要求,并具有良好的生物相容性。本论文以硅杂蒽结构为母体,设计合成了三种近红外荧光分子探针,分别识别检测F-、光气和战争毒剂芥子气气体,研究了它们的光学性能和对实际样品的识别检测,充分验证了这三种硅杂蒽近红外荧光分子探针的实用价值。首先,设计合成了一种硅杂蒽近红外F-荧光识别检测探针SiROPS。该探针对F-的识别具有很高的选择性和灵敏性。探针荧光信号on/off的过程,是由待测底物F-亲核进攻具有强荧光的探针SiROPS,其meso-位上芳基邻位的硫代磷酰酯官能团和F-反应,引起P-O键裂解,生成了一个无荧光水解产物SiROH。SiROH在meso位置有一个ortho取代的酚羟基o-OH,不足以限制meso-位链接芳环键的自由旋转,由此造成非辐射能量的耗散,导致水解产物SiROH荧光减弱。通过UV-vis光谱,荧光光谱,1H NMR和13C NMR图谱以及HRMS图谱验证了 F-诱导探针分子P-O键断裂的机理。通过Job’s曲线得到探针SiROPS与F-识别配比为1:1。在动态范围0.5 μM-20 μM内检测F-的检出限为48 nM,最佳响应时间为6 min,在365 nm紫外下裸眼可观察到探针DMSO溶液由紫红色荧光到无荧光变化。同时,制备了探针SiROPS试纸条,并且探针对实际环境水样和牙膏样品中的F-的识别检测应川也展示出潜在的应用价值。这些均充分说明了探针对于F-的识别检测具有很强的选择性和专一性。其次,设计合成一个硅杂蒽近红外光气荧光识别检测探针SiR-amide。当该探针识别并作用于光气时,探针上的酰胺官能基团转化为腈基官能团,产生较大程度的荧光增强响应,从而实现了对光气的快速和灵敏识别检测。探针SiR-amide在乙腈溶液中识别光气的检出限为8.9 nM,响应时间为4 min。并且对于光气具有专一性和选择性,其他干扰物,例如三光气、神经性毒剂类似物和酰氯类化合物等不干扰对光气的识别和检测。同时,还制备了探针SiR-amide试纸条,能够选择性检测较低浓度水平(0.1 mg/L)的光气气体。并且,无论是对一定浓度的光气溶液还是气体光气的识别检测中,均可在365 nm紫外下裸眼观察到探针溶液由无荧光到紫红色荧光的变化。这些均说明本论文设计合成的探针SiR-amide,可以分别在液相和气相中,快速和灵敏的对光气识别检测,并具有很强的选择性和专一性。最后,设计合成了两种硅杂蒽近红外识别检测战争毒剂芥子气的荧光探针SiRXT-1和SiRXT-2。两种探针,它们自身荧光强度均较弱,但通过和芥子气分子发生亲核作用后,均生成荧光强度显著增强的硅杂蒽硫代烷基化产物,此时其荧光激发波长和发射波长均在近红外波长区域。对比两种探针的光学性质及和芥子气分子的作用结果,我们发现含有烯丙基官能团的探针SiRXT-2,相对SiRXT-1具有更长的识别发射波长和更高的荧光量子产率。并通过探针SiRXT-2识别芥子气分子UV光谱、荧光光谱、1H NMR和MS谱,研究并验证了其识别芥子气分子的机理。探针SiRXT-2对芥子气乙腈溶液的检出限为3.2 μM,响应时间小于1 min,可见光下可裸眼观察到探针溶液由黄色到蓝色的颜色变化。并且对于芥子气分子具有专一性和选择性,其他干扰物DCP、CESF、DCNP、DBE、BMB、IE和POCl3等不干扰对芥子气分子的识别和检测。为了评估探针的实用性,我们又制备了探针SiRXT-2负载的TLC板,也实现了快速、灵敏、选择性荧光识别检测芥子气气体。对芥子气气体的最低浓度为0.5 ppm,响应时间小于1 min,365 nm紫外下可裸眼观察到TLC板由无荧光到紫红色荧光的变化。研究结果表明探针SiRXT-2是一种具有较高选择性和灵敏性并能现场使用的近红外芥子气分子识别检测荧光探针。
Abstract
sui zhao ying guang hua xue de bu duan yan jiu fa zhan ,fa guang fen zi gong neng cai liao de ge cheng ji ji qi jian de zhi bei zhu jian yin qi le ke yan gong zuo zhe de an fan guan zhu 。you yu ying guang jian ce de gao ling min du he ke shi shi ji yuan cheng jian ce deng you yue xing ,zai fen zi shi bie yu chuan gan zhong de ying yong de dao peng bo fa zhan ,she ji ge cheng gao ling min 、gao shua ze xing de ying guang hua xue tan zhen jin nian lai bei shou guan zhu 。yu ju you jiao duan xi shou he fa she bo chang de ying guang tan zhen xiang bi ,jin gong wai ying guang tan zhen ju you guang du xing di 、guang san she xiao 、zu zhi chuan tou neng li jiang 、shou sheng wu ti zi fa ying guang ying xiang xiao 、you li yu jin hang duo ying guang ran se deng you dian 。sui ran yi ge cheng de jin gong wai ying guang tan zhen chong lei jiao duo ,dan da duo cun zai shui rong xing cha 、guang wen ding xing cha 、sheng wu kuo ying xing cha he ke xiu shi xing cha deng wen ti 。ji yu ci ,fa zhan xin xing de jin gong wai xiao fen zi ying guang shi bie jian ce tan zhen ju you chong yao de yan jiu he ying yong jia zhi 。gui qu dai yang za en lei ying guang tan zhen shi jin ji nian lai fa zhan qi lai de yi lei xin xing ying guang ran liao ,shi yong gui yuan zi qu dai yang za en jie gou zhong de 10wei qiao lian Oyuan zi er de dao de 。tong guo jiang yang za en fen zi zhong Oqiao yuan zi yong Sidai ti ,de dao le yi lei xin xing de tan zhen fen zi —gui za en lei ying guang tan zhen zai bao liu yang za en ying guang ran liao you yue guang xue xing zhi de tong shi ,ying guang bo chang da yu 600 nnm,gong yi zhi NIRou yu ,man zu jin gong wai ying guang jian ce de yao qiu ,bing ju you liang hao de sheng wu xiang rong xing 。ben lun wen yi gui za en jie gou wei mu ti ,she ji ge cheng le san chong jin gong wai ying guang fen zi tan zhen ,fen bie shi bie jian ce F-、guang qi he zhan zheng du ji gai zi qi qi ti ,yan jiu le ta men de guang xue xing neng he dui shi ji yang pin de shi bie jian ce ,chong fen yan zheng le zhe san chong gui za en jin gong wai ying guang fen zi tan zhen de shi yong jia zhi 。shou xian ,she ji ge cheng le yi chong gui za en jin gong wai F-ying guang shi bie jian ce tan zhen SiROPS。gai tan zhen dui F-de shi bie ju you hen gao de shua ze xing he ling min xing 。tan zhen ying guang xin hao on/offde guo cheng ,shi you dai ce de wu F-qin he jin gong ju you jiang ying guang de tan zhen SiROPS,ji meso-wei shang fang ji lin wei de liu dai lin xian zhi guan neng tuan he F-fan ying ,yin qi P-Ojian lie jie ,sheng cheng le yi ge mo ying guang shui jie chan wu SiROH。SiROHzai mesowei zhi you yi ge orthoqu dai de fen qiang ji o-OH,bu zu yi xian zhi meso-wei lian jie fang huan jian de zi you xuan zhuai ,you ci zao cheng fei fu she neng liang de hao san ,dao zhi shui jie chan wu SiROHying guang jian ruo 。tong guo UV-visguang pu ,ying guang guang pu ,1H NMRhe 13C NMRtu pu yi ji HRMStu pu yan zheng le F-you dao tan zhen fen zi P-Ojian duan lie de ji li 。tong guo Job’squ xian de dao tan zhen SiROPSyu F-shi bie pei bi wei 1:1。zai dong tai fan wei 0.5 μM-20 μMnei jian ce F-de jian chu xian wei 48 nM,zui jia xiang ying shi jian wei 6 min,zai 365 nmzi wai xia luo yan ke guan cha dao tan zhen DMSOrong ye you zi gong se ying guang dao mo ying guang bian hua 。tong shi ,zhi bei le tan zhen SiROPSshi zhi tiao ,bing ju tan zhen dui shi ji huan jing shui yang he ya gao yang pin zhong de F-de shi bie jian ce ying chuan ye zhan shi chu qian zai de ying yong jia zhi 。zhe xie jun chong fen shui ming le tan zhen dui yu F-de shi bie jian ce ju you hen jiang de shua ze xing he zhuan yi xing 。ji ci ,she ji ge cheng yi ge gui za en jin gong wai guang qi ying guang shi bie jian ce tan zhen SiR-amide。dang gai tan zhen shi bie bing zuo yong yu guang qi shi ,tan zhen shang de xian an guan neng ji tuan zhuai hua wei jing ji guan neng tuan ,chan sheng jiao da cheng du de ying guang zeng jiang xiang ying ,cong er shi xian le dui guang qi de kuai su he ling min shi bie jian ce 。tan zhen SiR-amidezai yi jing rong ye zhong shi bie guang qi de jian chu xian wei 8.9 nM,xiang ying shi jian wei 4 min。bing ju dui yu guang qi ju you zhuan yi xing he shua ze xing ,ji ta gan rao wu ,li ru san guang qi 、shen jing xing du ji lei shi wu he xian lv lei hua ge wu deng bu gan rao dui guang qi de shi bie he jian ce 。tong shi ,hai zhi bei le tan zhen SiR-amideshi zhi tiao ,neng gou shua ze xing jian ce jiao di nong du shui ping (0.1 mg/L)de guang qi qi ti 。bing ju ,mo lun shi dui yi ding nong du de guang qi rong ye hai shi qi ti guang qi de shi bie jian ce zhong ,jun ke zai 365 nmzi wai xia luo yan guan cha dao tan zhen rong ye you mo ying guang dao zi gong se ying guang de bian hua 。zhe xie jun shui ming ben lun wen she ji ge cheng de tan zhen SiR-amide,ke yi fen bie zai ye xiang he qi xiang zhong ,kuai su he ling min de dui guang qi shi bie jian ce ,bing ju you hen jiang de shua ze xing he zhuan yi xing 。zui hou ,she ji ge cheng le liang chong gui za en jin gong wai shi bie jian ce zhan zheng du ji gai zi qi de ying guang tan zhen SiRXT-1he SiRXT-2。liang chong tan zhen ,ta men zi shen ying guang jiang du jun jiao ruo ,dan tong guo he gai zi qi fen zi fa sheng qin he zuo yong hou ,jun sheng cheng ying guang jiang du xian zhe zeng jiang de gui za en liu dai wan ji hua chan wu ,ci shi ji ying guang ji fa bo chang he fa she bo chang jun zai jin gong wai bo chang ou yu 。dui bi liang chong tan zhen de guang xue xing zhi ji he gai zi qi fen zi de zuo yong jie guo ,wo men fa xian han you xi bing ji guan neng tuan de tan zhen SiRXT-2,xiang dui SiRXT-1ju you geng chang de shi bie fa she bo chang he geng gao de ying guang liang zi chan lv 。bing tong guo tan zhen SiRXT-2shi bie gai zi qi fen zi UVguang pu 、ying guang guang pu 、1H NMRhe MSpu ,yan jiu bing yan zheng le ji shi bie gai zi qi fen zi de ji li 。tan zhen SiRXT-2dui gai zi qi yi jing rong ye de jian chu xian wei 3.2 μM,xiang ying shi jian xiao yu 1 min,ke jian guang xia ke luo yan guan cha dao tan zhen rong ye you huang se dao lan se de yan se bian hua 。bing ju dui yu gai zi qi fen zi ju you zhuan yi xing he shua ze xing ,ji ta gan rao wu DCP、CESF、DCNP、DBE、BMB、IEhe POCl3deng bu gan rao dui gai zi qi fen zi de shi bie he jian ce 。wei le ping gu tan zhen de shi yong xing ,wo men you zhi bei le tan zhen SiRXT-2fu zai de TLCban ,ye shi xian le kuai su 、ling min 、shua ze xing ying guang shi bie jian ce gai zi qi qi ti 。dui gai zi qi qi ti de zui di nong du wei 0.5 ppm,xiang ying shi jian xiao yu 1 min,365 nmzi wai xia ke luo yan guan cha dao TLCban you mo ying guang dao zi gong se ying guang de bian hua 。yan jiu jie guo biao ming tan zhen SiRXT-2shi yi chong ju you jiao gao shua ze xing he ling min xing bing neng xian chang shi yong de jin gong wai gai zi qi fen zi shi bie jian ce ying guang tan zhen 。
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论文详细介绍
论文作者分别是来自北京科技大学的杜曼，发表于刊物北京科技大学2019-01-16论文，是一篇关于硅杂蒽论文,近红外论文,荧光分子探针论文,分子识别论文,北京科技大学2019-01-16论文的文章。本文可供学术参考使用，各位学者可以免费参考阅读下载，文章观点不代表本站观点，资料来自北京科技大学2019-01-16论文网站，若本站收录的文献无意侵犯了您的著作版权，请联系我们删除。
标签：硅杂蒽论文; 近红外论文; 荧光分子探针论文; 分子识别论文; 北京科技大学2019-01-16论文;