固体基质室温燐光猝灭法测定人发和水中痕量汞

基于水杨基荧光酮羧甲基纤维素铅发光分子微球(Pb(CMC)2-THBF)在滤纸基质上可发射强而稳定的室温燐光,由此建立了Pb(CMC)2-THBF固体基质室温燐猝灭测定痕量汞的新方法.Hg2 的含量在2.5~100.0(pg/mL)内与ΔIp值成线性关系,其线性回归方程为ΔIp=12.73 0.4699CHg2 (pg/mL),r=0.9991,检出限为3.2×10-13g/mL.该方法用于人发和水样中痕量汞的测定,结果满意.同时探讨了固体基质室温燐光猝灭测定痕量汞的机理.     

催化过氧化氢氧化邻苯三酚红固体基质室温燐光猝灭法测定痕量钴

基于硼砂缓冲液中聚丙烯酰胺(PAM)存在下,邻苯三酚红(PGR)于滤纸固体基质上能发射强而稳定的室温燐光,PAM可活化钴离子催化H2O2氧化PGR反应,使PGR的室温燐光猝灭,从而建立了测定痕量钴的新方法。该方法的线性范围为4.8~960(×10-18g/斑)Co2+(浓度范围0.012~2.40×10-9g/L,0.4μL/斑),工作曲线的回归方程ΔIp=12.76+0.1248 mCo2+(×10-18g/斑),n=7,相关系数r=0.9993;检出限为1.2×10-18g/斑(对应浓度为3.0×10-12g/L)。对4.8和960(×10-18g/斑)Co2+重复测定11次(0.4μL点样量),RSD分别为3.6%和4.7%。用PAM比不加PAM时ΔIp增加4.6倍。本方法灵敏、准确、简便快速、重现性好,用于党参、当归、川芎、金银花和VB12中的痕量钴测定,结果满意。     

反相胶束介质中敏化双乙酰室温燐光——α-萘乙酸为敏化剂

本文报道了AOT-C_6H_(12)-H_2O反相胶束介质中α-萘乙酸(α-NAA)敏化双乙酰(BIAC)的室温燐光.详细讨论了琥珀酸二(2-乙基己基)酯磺酸钠(AOT)浓度和水泡大小(W值)对敏化燐光的影响.吸收、发光性质和微粘度性质的实验表明AOT浓度对敏化燐光强度的影响由敏化燐光寿命、能量转移效率和Poisson分布决定;一定范围内,随着水浓度增大,由于粘度下降和内腔半径增大作用的相互抵销,水泡大小仅有微弱影响.当W([H_2O]/[AOT])大于20后,内腔半径增大起主要作用,敏化燐光强度快速下降.与普通SDS胶束相比,燐光强度约增强13倍,检出限约下降一个数量级.建立了灵敏的测定α-萘乙酸和双乙酰的敏化室温燐光法,检出限分别达2.0×10~(-8)mol·dm~(-3)(α-NAA)和8.5×10~(-9)mol·dm~(-3)(BIAC).     

以阴离子交换纤维素膜作基质室温燐光法测定痕量2,6-二氨基嘌呤的研究

本文对2,6-二氨基嘌呤(DAP)在不同的基质上和不同的重原子微扰剂存在下的室温燐光(RTP)强度进行比较,结果表明,NaI-NaAc是有效的重原子体系。适宜的固体基质为阴离子交换纤维素(二乙氨基乙基纤维素)膜(DEAE)和慢速定量滤纸。前者对酸度的变化具有较好的缓冲能力,本文提出了以DEAE为固体基质,测定痕量DAP的RTP法。     

在不同重原子存在下α-萘乙酸的固体基质室温燐光法研究

本文以滤纸为固体基质,详细讨论并比较了碘,铅和铊盐作重原子时α-萘乙酸的室温燐光特性,定量线性范围和检出限,并研究了重原子浓度对RTP强度的影响。结果表明,NaI作重原子时α-萘乙酸有较低的检出限和较宽的线性范围。Pb(Ac)_2和TlNO_3虽能较显著地增强α-萘乙酸的RTP强度,但同时也较显著地增强了滤纸地RTP背景。     

催化H2O2氧化2, 3, 4, 9-四氢-9-羟基-1, 10-蒽醌荧光猝灭法测定痕量砷

基于HCl介质中和α,α-联吡啶存在下,As(V)可催化H2O2氧化2,3,4,9-四氢-9-羟基-1,10-蒽醌(R)转化无荧光化合物,导致体系荧光急剧猝灭,据此建立了催化H2O2氧化R荧光猝灭法测定痕量砷的新方法.在最佳条件下,As(V)含量在0.004 0~0.400 0 ng/mL范围内与荧光光强度的△If值符合比尔定律,工作曲线的回归方程△If=11.94 233.7 CAs(V)(ng/mL),n=7,相关系数r=0.9994,检出限为6.2×10-13g As(V)/mL,n=11.对0.004 0和0.400 0 ng/mL As(V)分别进行11次的测定,其RSD为2.6%与3.8%.该方法重现性好、灵敏、准确,用于实际中砷含量的测定,结果满意.还报道了R的合成,并借助核磁共振谱、红外光谱及质谱等谱学方法确定了其结构.     

缺位的Wells-Dawson型磷钨酸盐和Eu(Ⅲ)构筑的一维链状多金属氧酸盐化合物

在水溶液条件下以六缺位的[H2P2W12O48)]12-和Eu髥为反应前躯体得到了1个新的多金属氧酸盐化合物[Eu3(H2O)17(α2-HP2W17O61)].5H2O(1),对其进行了元素分析、红外光谱、热重、荧光等表征,并用X-射线单晶衍射测定了它的晶体结构。化合物1含有双支撑的多阴离子簇[{Eu(H2O)7}2{Eu(H2O)3(α2-P2W17)}2]8-,并进一步通过Eu髥连接形成了延c轴方向的一维链。室温条件下的荧光光谱研究表明:化合物1显示了强的红光发射。     

一种新的滤纸基质固体表面低温荧光(燐光)测定装置

对自行研制的铜制滤纸基质低温荧光（燐光）测定的样品支架，进行了滤纸基质固体表面低温荧光测定的可行性研究。与同类冷冻装置和室温装置比较，本装置用于滤纸基质固体表面低温荧光（燐光）测定具有以下优点；样品的分析周期大大地缩短，由45min缩短为5-6min；装置简单、便宜耐用；操作简便，简化了室温测定时的滤纸干燥程序，应用范围广，方法的重现性好，检样分析结果的相对标准偏差RSD%小于10%，荧光（燐光）分析灵敏度高，检出限低，线性范围宽。     

基于一种三角柔性羧酸配体构筑的含镍配位聚合物的水热合成、结构和光化学性质

通过水热法合成了一种配位聚合物{[Ni(H2BCPBA)2(H2O)4]}n(1,H3BCPBA=3,5-二(4-羧酸-酚氧基)-苯甲酸),并对其进行了元素分析、红外光谱、紫外光谱、热重和X射线单晶衍射表征。{[Ni(H2BCPBA)2(H2O)4]}n属于三斜晶系,P1空间群。中心Ni(Ⅱ)和来自于2个配体与4个水分子配位,形成八面体结构。固体紫外光谱表明配合物有一个强的光谱吸收。     

（＋）-α-苯乙胺磷钨杂多化合物的合成、表征和催化不对称环氧化性能

以Keggin型12-磷钨酸和( )-α-苯乙胺为原料,通过水热法合成了具有Keggin结构的( ).α-苯乙胺磷钨酸盐(C8H12-N)3PW12O40.通过红外光谱、核磁共振波谱、紫外光谱、元素分析和热重分析等技术对合成产物进行了结构、组成和热稳定性的表征和考察,证实了合成产物为( )-α-苯乙胺磷钨酸盐.以顺丙烯磷酸-α-苯乙胺盐环氧化合成(1R,2S).环氧丙基磷酸-a-苯乙胺盐为探针反应,考察了(C8H12N)3PW12O40催化不对称环氧化性能.结果表明,在催化剂用量为2.00%和反应温度为50℃时,产物环氧丙基磷酸苯乙胺盐的收率为64%,(1R,2S)-环氧丙基磷酸苯乙胺盐的对映选择性ee值为10.8%.     

Determination of Trace Titanium by Solid Substrate－Room Temperature Phosphorimetry with 4,5－Dibromophenylfluorone as Luminescent Ligand and Triton X－100 as Sensitizer

A new highly sensitive solid substrate room temperature phosphorimetry for the determination of trace titanium is proposed based on the sensitization of Triton X-100 to the SS-RTP intensity of 4, 5-dibro-mophenylfluorone-titanium complex adsorbed on the filter paper substrate modified by gelatin. When Triton X-100 was added into the luminescence system, the RTP intensity was raised 3 times stronger than that of the system without Triton X-100. The linear dynamic range of the new method is 0. 64 ～ 3.2 fg/spot (0. 4 μL) with a detection limit of 12.8 ag/spot, and the regression equation of the working curve is △Ip = 482. 0 119.5mTi（Ⅳ) (fg/spot), the correlation coefficient r= 0. 9992, n = 6. The phosphorescence lifetime (r= 0. 85 ms) was also determined. The recoveriesCand RSD) for the determinations of titanium in human hair and tea samples were 101.0% (3. 0%) and 99. 97% (4. 2%), respectively.     

Determination of trace copper by solid substrate-room temperature phosphorescence quenching method based on activating effect of alpha,alpha'-dipyridyl on Vitamin C reducing beryllon

A new solid substrate-room temperature phosphorescence quenching method for the determination of trace copper has been established. It is based on the fact that beryllon (R) can emit strong and stable solid substrate-room temperature phosphorescence on the filter paper, and Vitamin C (Vc) reduces R to non-phosphorescent compound that leads to solid substrate-room temperature phosphorescence (SS-RTP) quenching of R, and alpha,alpha'-dipyridyl can activate copper catalyzing Vitamin C reducing R. The DeltaI(p) of the system with alpha,alpha'-dipyridyl is 3.3 times higher than that without alpha,alpha'-dipyridyl, which shows the reaction of alpha,alpha'-dipyridyl activating copper catalyzing Vitamin C reducing R. The reducing value of phosphorescence intensity (DeltaI(p)) is directly proportional to the content of Cu(II) in the range of 0.040-4.0 fg spot(-1) (corresponding concentration: 0.10-10.0 pg ml(-1), sample volume: 0.40 microlspot(-1)). The regression equation of working curve can be expressed as DeltaI(p)=69.99+41.00 m Cu(2+) (fg spot(-1)) (r=0.9980, n=6), and the detection limit is 0.0088 fg spot(-1)(corresponding concentration: 2.2 x 10(-14) g ml(-1)). This sensitive and accurate method with good repeatability and high selectivity has been applied to the determination of trace copper in real samples with satisfactory results. The reaction mechanism for the determination of trace copper by solid substrate-room temperature phosphorescence quenching method based on the activating effect of alpha,alpha'-dipyridyl on Vitamin C reducing beryllon is also discussed.     

Determination of trace silver by solid substrate room temperature phosphorescence quenching method based on lead carboxymethyl cellulose particles (Pb(CMC)2) containing luminescent salicyl fluorenes molecules

Luminescent particles of lead carboxymethyl cellulose (Pb(CMC)2) containing salicyl fluorones (THBF), Pb(CMC)2-THBF were synthesized by the sol-gel method, using sodium carboxymethyl cellulose (NaCMC) as precursor and Pb2+ as precipitant. Pb(CMC)2-THBF can emit the intense and stable solid substrate room temperature phosphorescence (SS-RTP) on filter paper. And EDTA can chelate Pb2+ in Pb(CMC)2-THBF, causing it to decompose into aqueous soluble components PbY2-, CMC- and THBF, which can react with Ag+ to form Ag(CMC)2-THBF, causing the decrease of phosphorescence intensity. Based on the facts above, a new method for the determination of trace silver by SS-RTP quenching method was established. The linear range of this method is 8.0-40.0 fg spot(-1) (20.0-100.0 pg ml(-1)), with a detection limit (LD) of 2.2 fg spot(-1) (corresponding to a concentration range of 5.5 x 10(-13) g ml(-1)), and the regression equation of working curve is DeltaI(p) = 12.56 + 0.5527C(Ag+) (fg spot(-1), 0.4 microl spot(-1)), n = 8, r = 0.9992. This method has been applied to the determination of trace silver in human hair and tea sample with satisfactory results. The mechanism of SS-RTP emission is also discussed.     

Determination of trace lead by solid substrate room temperature phosphorescence enhancing method based on heavy atom effect and dissoluble manganese supramolecule containing rhodamine 6G luminescent particles

Dissoluble manganese supramolecule containing rhodamine 6G luminescent particles (M2) are synthesized, based on dissoluble manganese supramolecule (M1) doping rhodamine 6G (R.6G), by crystalline method. The particle diameters of M1 and M2 determined by ETM are both of micron degree. M1 and M2 can emit solid substrate room temperature phosphorescence (SS-RTP) on filter paper. The transition probability from the singlet state (S1) to triplet state (T1) of the luminescent molecules was greatly enhanced, based on the increment of luminescent molecules for each spot and the heavy atom effect of certain amount of Pb2+. As a result, the phosphorescence intensity (Ip) of M2 was increased sharply, and the enhancing value of phosphorescence intensity (DeltaIp) is directly proportional to the concentration of Pb2+. Thus, a new method of SS-RTP enhancing for the determination of trace lead is established based on manganese supramolecule containing rhodamine 6G luminescent particles. The linear range of this method is 0.0040-0.400 pg spot-1 of Pb2+ (corresponding concentration, 0.01-1.0 ng mL-1; sample volume, 0.4 microL spot-1), with a detection limit (LD) of 0.0011 pg spot-1 (corresponding concentration, 2.8x10(-12) g mL-1 of Pb2+, n=11). For the working solutions containing 0.0040 and 0.40 ng mL-1 of Pb2+, they were determined repeatedly for seven times, respectively. The R.S.D.s were 3.2 and 3.8%, respectively. This method has good repeatability, sensitivity and high precision. It has been applied to the determination of trace lead in human hair and tea samples with satisfactory results.     

Determination of human IgG by solid substrate room temperature phosphorescence immunoassay based on an antibody labeled with nanoparticles containing Rhodamine 6G luminescent molecules

Luminescent silicon dioxide nanoparticles (R-SiO2) with size of 50 nm containing Rhodamine 6G (R) were synthesized by sol-gel method. In the presence of Pb(Ac)2 as a heavy atom perturber, the particle can emit intense and stable room temperature phosphorescence signal of R, respectively, on polyamide membrane, with the lambda(ex)(max)/lambda(em)(max) = 470/635 nm for R. Our research indicates that the specific immune reaction between goat-anti-human IgG antibody labeled with R-SiO2 and human IgG can be carried on polyamide membrane quantitatively, and the phosphorescence intensity was enhanced after the immunoreactions. Thus, a new method of solid substrate room temperature phosphorescence immunoassay (SS-RTP-IA) for the determination of human IgG was established basing on antibody labeled with the nanoparticles containing binary luminescent molecules. The linear range of this method is 0.0624-20.0 pg spot(-1) of human IgG (corresponding concentration, 0.156-50.0 ng mL(-1); sample volume, 0.40 microL spot(-1)). The regression equations of working curves are delta I(p) = 88.16. + 16.79 m(IgG) (pg spot(-1)) (485/646 nm, r = 0.9997). Detection limits calculated by 3Sb/k are 0.017 pg spot(-1). For samples containing 0.156 and 50.0 ng mL(-1) of IgG, we measured repeatedly for 11 times, RSDs are 3.9 and 2.8%, respectively. This method is sensitive, accurate and of high precision.     

Determination of trace gastrin and diagnosis of human diseases using CdTe quantum dots labelled gastrin antibodies as phosphorescence sensors

CdTe quantum dots (CdTe-QDs) can emit strong and stable room temperature phosphorescence (RTP) via the perturbation effect of a Pb(2+) ion on the surface of a nitrocellulose membrane (NCM). CdTe-QDs-Ab(GAS), the product of CdTe-QDs labelled gastrin antibodies (Ab(GAS)), can not only maintain good RTP characteristics, but can also be used as a RTP sensor and carry out highly specific immunoreactions with gastrin (GAS) to form GAS-Ab(GAS)-CdTe-QDs causing the ΔI(p) of the system to sharply enhance. Thus, a new solid substrate room temperature phosphorescence immunoassay (SSRTPIA) for the determination of GAS was established based on the linear relativity between the ΔI(p) of the system and the content of GAS. The limit of quantification (LOQ) of this method was 0.43 fg spot(-1) with the corresponding concentration being 1.1 × 10(-12) g mL(-1) and sampling quantity being 0.40 per spot(-1). This highly specific, accurate, selective and sensitive RTP sensor has been applied to the determination of GAS in biological samples and the diagnosis of diseases, and the results agreed well with those obtained by radioimmunometric assay (RIA). Meanwhile, the mechanism of SSRTPIA for the determination of GAS using CdTe-QDs-Ab(GAS) as the RTP sensor was discussed.     

Determination of trace mercury by solid substrate-room temperature phosphorimetry based on catalytic effect of Hg(2+) on formation of the ion association complex [Fe(bipy)(3)](2+)[(FinBr(4))(2)](2-)

A new solid substrate-room temperature phosphorimetry method for the determination of trace mercury has been established. It bases on the fact that in acetic acid medium, Hg²⁺ ion can catalyze the substitute reaction of CN⁻ ligand in [Fe(CN)₆]⁴⁻ by 2,2′-bipyridyl (bipy), and the resultant [Fe(bipy)₃]²⁺ cation can react with FinBr₄⁻ anion of tetrabromofluorescein (HFinBr₄) to form ion association complex [Fe(bipy)₃]²⁺[(FinBr₄)₂]²⁻ which can emit phosphorescent signal on filter paper substrate. Under the optimum condition, the linear dynamic range of this method is 1.6-16 fg per spot with a detection limit (LD) of 0.18 fg per spot (0.4 μl sample solution per spot), and the regression equation of working curve is ΔI_p=1.058+7.671 C_Hg²⁺ (fg per spot ), n=7, correlation coefficient is 0.9990. This method has been applied to the determination of trace mercury in hair and cigarette samples with satisfactory result. The reaction mechanism for formation of the ion association complex is also discussed.     

大麻中3种酚类成分测定专用固相萃取柱的设计与应用

大麻中的主要成分大麻二酚(CBD)、大麻酚(CBN)和Δ9-四氢大麻酚(Δ9-THC)的含量决定了其性质和应用。在液相色谱分析中,由于大麻提取液中含有较多杂质,需要净化。该文基于大麻中CBD、CBN和Δ9-THC的结构特征及样品基质组成,根据中性氧化铝、硅酸镁和石墨化炭黑的不同表面特征,考察了这3种吸附剂对大麻提取液中叶绿素、多糖、高级脂肪酸酯及重金属离子的去除率和对3种大麻酚的回收率,确定了3种吸附剂的用量分别为1.80 g、0.15 g、0.05 g混合装填成的2 g/6 mL小柱为3种大麻酚类化合物测定的专用固相萃取柱。该小柱对大麻乙酸乙酯-甲醇提取液样品中CBD、CBN和Δ9-THC的回收率分别为98.9%, 95.7%和99.2%,对叶黄素、叶绿素a和叶绿素b的去除率分别为96.3%、99.2%和95.5%,对总糖的去除率为98.5%,对脂肪酸甘油酯的去除率为96.9%,对重金属离子的平均去除率为85.4%。优化了色谱分析条件,采用Eclipse Plus C18色谱柱(50 mm×2.1 mm, 1.8 μm),在1%乙酸水溶液-乙腈(30∶70, v/v)流动相条件下等度洗脱,流速为0.5 mL/min,柱温为30 ℃,检测波长为210 nm,进样量为1 μL,在10 min内可完成样品分析。方法学考察表明,在0.5~50 mg/L范围内,CBD、CBN和Δ9-THC的液相色谱峰面积与其质量浓度呈良好的线性关系,相关系数(R²)分别为0.9983、0.9995和0.9981,检出限分别为0.45 μg/L、0.53 μg/L和0.38 μg/L,加标回收率为90.3%~97.0%、93.7%~95.6%、90.8%~96.1%,相对标准偏差(RSD)分别为2.2%~6.1%、4.1%~8.0%、2.4%~4.8%。研究结果表明,该文以中性氧化铝、硅酸镁和石墨化炭黑制作的复合型大麻酚类成分测定专用固相萃取柱在大麻植物中3种酚类化合物的测定中具有净化杂质、防止色谱柱污染的功能。由于大麻不同部位的化学成分存在差异,在后续的研究中,还要进一步考察小柱对其他杂质的去除情况,使得制备的固相萃取小柱更具有普适性。     

LC-AFS法对动物源性食品中硫柳汞残留量的测定

建立了动物源性食品中硫柳汞残留量的LC-AFS分析方法.样品经酸、碱提取液提取,液相色谱分离后,先与氧化剂混合,再与空气混合,通过紫外光照射,硫柳汞被氧化成无机汞,最后与还原剂和盐酸发生氢化反应,进入原子化器,进行原子荧光测定.对样品前处理条件、液相色谱条件、氧化剂和原子荧光工作条件进行了考察.在优化实验条件下,硫柳汞...     

固相萃取/液相色谱-串联质谱法检测医院废水中21种抗生素药物残留

应用固相萃取及高效液相色谱-串联质谱技术,建立了医院废水中12种磺胺、4种喹诺酮、3种四环素以及罗红霉素和甲氧苄氨嘧啶等21种抗生素的定性定量方法。水样经HLB小柱萃取富集,使用10%甲醇溶液净化,经甲醇洗脱定容后,以高效液相色谱-串联质谱多反应监测离子模式(MRM)对目标物进行分析。在优化实验条件下,21种抗生素的线性范围为1.0～500μg/L,相关系数r2>0.99,方法检出限为0.005～0.022μg/L。在加标量为0.05μg/L和1.0μg/L时,空白加标回收率分别为71%～105%和76%～111%,RSD均小于15%。以医院废水为基质,21种抗生素的加标回收率为71%～135%,RSD小于25%。该方法简捷、快速、准确,能够实现医院废水中多种抗生素药物残留的同时分析。