基于Fe3O4@Au磁性纳米粒子修饰丝网印刷电极的微囊藻毒素免疫传感器研究

将核壳型Fe3O4@Au磁性纳米粒子修饰在丝网印刷工作电极表面,再通过纳米金和微囊藻毒素-(亮氨酸-精氨酸)抗体(anti-MCLR)之间的吸附作用,将抗体固定于电极表面,以牛血清白蛋白(BSA)封闭非特异性吸附位点,制得了检测MCLR的电流型免疫传感器。该传感器基于直接竞争的免疫分析模式,以辣根过氧化物酶偶联的微囊藻毒素(MCLR-HRP)为标记物,用差分脉冲伏安法检测微囊藻毒素,在优化的实验条件下,此免疫传感器响应的峰电流值与微囊藻毒素浓度在0.79～12.9μg/L范围内呈良好的线性关系,检测限为0.38μg/L。对实际水样进行了微囊藻毒素的加标回收实验,回收率在95%～107%之间。此免疫传感器具有测定速度快、灵敏高、携带方便等优点。     

磁性无机-生物复合粒子敏感膜新型电流型免疫传感器的研究

合成了磁性Fe3O4纳米粒子,利用3-氨基丙基三乙氧基硅烷(APS)进行硅烷化,形成表面带有氨基的磁性Fe3O4纳米复合粒子,再用戊二醛将羊抗人免疫球蛋白G抗体(anti-IgG)固定在该磁性粒子表面,通过磁力将其修饰于固体石蜡碳糊电极表面制作成免疫传感器。与标记HRP的二抗体anti-IgG结合,以对苯二酚作为电子媒介体,实现对人免疫球蛋白G(IgG)的定量检测。IgG测定线性范围为2.5~400μg/L,检出限为0.75μg/L。该免疫传感器制作简单,成本低,表面更新方便,可用于临床血清检测。     

配体交换法制备水中高分散稳定性的多羧基修饰Fe3O4纳米颗粒

采用油相高温分解法制备了粒径可控且单分散的油溶性Fe3O4磁性纳米粒子(MNPs-OA), 并通过配体交换对其表面进行了亲水性修饰, 制备了柠檬酸(CA)、 N-(三甲氧基硅丙基)乙二胺三乙酸钠(SiCOOH)、 丁烷四羧酸(BTCA)和乙二胺四乙酸 (EDTA)四钠4种多羧基配体修饰的水溶性Fe3O4磁性纳米粒子(MNPs-CA, MNPs-SiCOOH, MNPs-BTCA 和MNPs-EDTA), 其中首次选用四羧基配体BTCA和EDTA四钠来修饰Fe3O4磁性纳米粒子(MNPs). 对油溶性MNPs和4种水溶性MNPs的形貌、 结构、 化学组成和磁性能进行了表征, 并对4种多羧基配体修饰的水溶性MNPs在水相中的稳定性和分散性进行了表征. 结果表明, 所得MNPs的平均粒径为15 nm, 具有超顺磁性, 配体交换后的水溶性MNPs具有良好的亲水性, 并在弱酸～碱性很宽的pH范围内具备良好的分散稳定性. 此类多羧基修饰的水溶性MNPs可与适当的阳离子聚电解质进行组装, 从而得到在磁靶向载体和磁共振造影(MRI)显影中具有良好应用前景的磁性自组装微囊.     

磁性纳米粒子固定辣根过氧化物酶的生物传感器

利用FeSO4与FeCl3合成了磁性Fe3O4纳米粒子,并进一步利用3-氨丙基-3-乙氧基硅烷(APS)和戊二醛溶液将辣根过氧化物酶共价固定于该磁性纳米粒子表面,研究了该磁性颗粒的磁学性能,通过磁力将其修饰于固体石蜡碳糊电极表面制成了酶修饰电极。考察了该传感器对H2O2的电化学响应。该生物传感器可对H2O2进行测定,线性范围为1.2×10-7~8.3×10-5mol/L;检出限为4.5×10-8mol/L。利用磁性纳米粒子所制得的酶修饰电极具有催化性能高、稳定性好、造价低和修饰层易更新等优点,有望得到更多的实际应用。     

基于HDT自组装金纳米粒子修饰电极的微囊藻毒素-LR电化学免疫传感器研究

构建了一种新型的基于金纳米粒子(Au NPs)修饰金电极的微囊藻毒素-亮氨酸-精氨酸(MCLR)电化学免疫传感器。采用柠檬酸钠还原法制备了Au NPs溶胶,分别用透射电子显微镜和紫外-可见吸收光谱对其进行表征。将Au NPs组装到1,6-己二硫醇(HDT)自组装单分子层修饰的金电极表面,再将MCLR抗体(anti-MCLR)固定于该修饰电极上,利用扫描探针显微镜法、循环伏安法和电化学交流阻抗法(EIS)表征了自制化学修饰电极表面的形貌特征和电化学免疫传感器的电化学特征。通过辣根过氧化物酶标记的MCLR(MCLR-HRP)与MCLR竞争结合抗体,建立了检测MCLR的差分脉冲伏安法(DPV)。在最佳实验条件下,用DPV对MCLR检测的线性范围为0.01~25μg/L,检出限为0.005μg/L。对构建的免疫传感器的重现性、稳定性和选择性进行了考察。该方法对实际水样中MCLR的加标回收率为100%~102%,测定结果与高效液相色谱法的测定结果一致。     

纳米金与磁性纳米复合物构建电流型免疫传感器的研究

制备了易于磁性分离、硫堇(Thi)包覆的四氧化三铁(Fe3O4)纳米复合物。通过静电吸附作用,将萘酚(Nafion)、Thi包覆的Fe3O4复合纳米粒子层层修饰到玻碳电极表面,再利用Thi分子中的氨基吸附纳米金,最后固载甲胎蛋白抗体,从而制得灵敏度高、稳定性好的无试剂电流型甲胎蛋白免疫传感器。实验通过透射电子显微镜(TEM)对该复合纳米粒子进行表征,并用循环伏安法考察了电极的电化学特性。结果表明,Fe3O4/Thi复合纳米粒子修饰的电极在实验过程中呈现出良好的氧化还原活性,其检测范围为0.05～20μg/L,检出限为0.03μg/L。     

基于丝网印刷碳电极的微囊藻毒素-(亮氨酸-精氨酸)的电流型免疫传感器

将微囊藻毒素-(亮氨酸-精氨酸)-鸡卵白蛋白 (Microcystin-(leucinc-arginine)-ovalbumin,MCLR-OVA)固定在锇联吡啶聚(4-乙烯基吡啶)聚合物修饰的丝网印刷碳电极表面,制备了一种检测 MCLR的电流型免疫传感器.该传感器基于间接竞争免疫分析模式,以辣根过氧化物酶偶联的羊抗鼠...     

CoFe_2O_4纳米粒子对水中微囊藻毒素的去除

通过一步溶剂热合成法制备出Co Fe2O4,Fe3O4,Cu Fe2O43种磁性纳米粒子,将其用于水中生物污染物微囊藻毒素的去除,通过高效液相色谱法检测微囊藻毒素浓度。上述3种磁性粒子中,Co Fe2O4对微囊藻毒素具有最强的吸附性能。采用透射电子显微镜、红外光谱、磁滞回线和X-射线衍射等方法对Co Fe2O4纳米粒子进行表征,Co Fe2O4具有良好的磁性和分散性,粒径约为250 nm。由于具有较强的磁性,Co Fe2O4及吸附于表面的微囊藻毒素可通过施加外加磁场而从溶液中分离。考察了生物污染物初始浓度、溶液酸度、温度、离子强度和水中天然有机物浓度等条件对Co Fe2O4吸附性能的影响。结果显示,较高的分析物浓度与实验温度、较低的p H值及离子强度更有利于微囊藻毒素在磁性粒子表面的吸附。低浓度(0~2.5 mg/L)的腐植酸几乎不影响Co Fe2O4对微囊藻毒素的吸附,而较高浓度的腐植酸使得Co Fe2O4的吸附性能显著下降。静电作用和配位作用在Co Fe2O4吸附毒素的过程中起着重要作用。研究表明,Co Fe2O4纳米粒子的制备方法简单,具有较强的磁场响应性及良好的单分散性,在水环境中生物污染物的去除方面具有优越的应用前景。     

基于双层酶信号放大及纳米功能界面的微囊藻毒素电化学免疫传感器

设计了一种基于纳米复合膜双层酶信号放大的竞争型电化学免疫传感器,用于检测痕量微囊藻毒素-LR(Microcystin-(leucine-arginine),MCLR)。在多壁碳纳米管修饰玻碳电极上电沉积金纳米粒子形成纳米复合膜,作为MCLR抗体(anti-MCLR)和辣根过氧化物酶(HRP)的固定化载体;引入HRP作为封闭剂或者通过抗体捕获HRP标记的MCLR(HRP-MCLR),起封闭活性位点及协同催化的作用。利用MCLR与HRPMCLR对纳米复合膜所固载抗体活性位点的竞争结合模式,采用微分脉冲伏安法(DPV)测定电极界面上HRP酶催化过氧化氢(H_2O_2)氧化对苯二酚(HQ)产生的还原电流,实现MCLR的定量检测。此传感器具有良好的特异性、稳定性与灵敏度,线性检测范围为0.1~100.0 μg/L,检出限为0.038 μg/L(S/N=3),对实际水样的加标回收率为72.9%~117.3%。     

Fe3O4表面原位引发可控/“活性”聚合制备磁性聚苯乙烯纳米粒子

采用化学共沉淀方法合成了Fe3O4纳米粒子, 用3-甲基丙烯酰氧基丙基三甲氧基硅烷(3-MPS)对其进行表面接枝修饰, 然后以苯乙烯(St)为单体, 过氧化苯甲酰(BPO)为引发剂, 4-羟基-2,2,6,6-四甲基哌啶-1-氧化物自由基(HTEMPO·)为稳定自由基介质, 采用可控/“活性”自由基聚合技术在修饰后的Fe3O4纳米粒子表面原位引发聚合, 制备了粒径小、分布窄、磁含量高的磁性聚苯乙烯（PS）纳米粒子. X射线衍射(XRD)研究表明, 所合成的Fe3O4粒子为尖晶石结构. 凝胶渗透色谱(GPC)分析表明, 聚苯乙烯的分子量与反应时间呈较好的线性关系. 透射电镜(TEM)观察表明, 所制备的磁性聚苯乙烯纳米粒子的粒径在20-30 nm之间. 热重(TG)分析得到磁性聚苯乙烯纳米粒子的磁含量为62.6%. 振动样品磁强计(VSM)测试结果表明, 磁性聚苯乙烯纳米粒子的比饱和磁化强度为31.7 emu·g-1, 呈现单磁畴结构.     

A carbanion induced synthesis of highly congested pyrazole and imidazole containing heterocycles

An efficient approach to the synthesis of highly congested di, penta and hexacyclic pyrazoles as well as imidazole fragment containing novel heterocyclic molecule has been developed through a carbanion induced transformation of suitably functionalized 2H-pyran-2-ones, benzo[h]chromene and thiochromeno[4,3-b]pyrans. Due to the presence of fluorescence, we report their prime application metal sensor as off/on switching in ferric ions.     

α-Amino acid derived enaminones and their application in the synthesis of N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates and other heterocycles

A new and simple synthesis of novel N-protected methyl 5-substituted-4-hydroxypyrrole-3-carboxylates, which exist in equilibrium with their 4-oxo tautomers, has been developed in two steps starting from N-protected α-amino acids. The key intermediates are enaminones, which can also be isolated, characterized, and used for the construction of other functionalized heterocycles, before they spontaneously decompose to pyrrole products. 4-Hydroxypyrroles are prone to partial aerial oxidation but can be efficiently alkylated or reduced to stable polysubstituted pyrrolidine derivatives.     

Specific intramolecular aromatic CH insertion of diazosulfonamides

The chemoselectivity in the intramolecular CH insertion of various diazosulfonamides has been experimentally studied. The results reveal that the aliphatic 1,4-, 1,5-, or 1,6-C(sp³)?H insertions of diazosulfonamides are not accessible, while the aromatic 1,5-C(sp²)?H insertion can be realized specifically by adjusting the diazo-adjacent group. In addition, the general chemoselectivities in the intramolecular CH insertions of diazosulfonyl compounds are summarized. Generally, diazosulfones undergo both aromatic 1,5-C(sp²)?H and aliphatic 1,5- and 1,6-C(sp³)?H insertions, while diazosulfonates undergo aliphatic 1,5- and 1,6-C(sp³)?H insertions. However, diazosulfonamides only undergo aromatic 1,5-C(sp²)?H insertion.     

N-Heterocyclic carbene-palladacyclic complexes: synthesis,characterization and their applications in the C-N coupling and α-arylation of ketones using aryl chlorides

N-Heterocyclic carbene-palladacyclic complexes 3 were successfully achieved in a one-pot procedure under mild conditions. The structure of 3a was unambiguously confirmed by X-ray single crystal diffraction and it was an active catalyst in the Buchwald-Hartwig amination and α-arylation of ketones even at very low catalyst loadings (0.01?mol%).     

Selective synthesis of 4,5-dihydroimidazo- and imidazo[1,5-a]quinoxalines via modified Pictet–Spengler reaction

An efficient tandem approach for the selective synthesis of 4,5-dihydroimidazo[1,5-a]quinoxalines 6a–g and imidazo[1,5-a]quinoxalines 7a–h by the reaction of 2-imidazolyl anilines 4a–c with aryl aldehydes 5a–k under mild reaction conditions is described. Introduction of electron releasing alkyl groups in substrates 4a–b was found to be instrumental for the success of the reaction.     

Understanding the Diels-Alder reactivity of 1,2-azaborine analogues

The Diels-Alder reactivity of 1,2-heteroborines (H₄C₄B(H)X, X?=?NH, PH, AsH; O, S, Se) has been computationally explored by means of Density Functional Theory (DFT) calculations. The influence of the HB?=?X fragment on the reactivity of the system has been quantitatively analyzed in detail by means of the so-called Activation Strain Model (ASM) of reactivity. It is found that the interaction between these species and the dienophile is significantly stronger than that computed for their all-carbon isoelectronic counterpart, benzene. In addition, the strain energy plays a key role in the observed reactivity trends. The role of the aromaticity strength of these heteroarenes on the reactivity is also assessed.     

Synthesis of N-substituted carbazolones from α-iodo enaminones via Pd(0)-catalyzed intramolecular coupling under microwave irradiation

A variety of N-aryl and N-alkyl carbazolones were conveniently achieved in good to high yields via Pd₂(dba)₃-mediated intramolecular coupling of N-substituted α-iodo enaminones under microwave irradiation. The Pd(0)-catalyzed cyclization was found to proceed favorably with the more electron-deficient phenyl ring during the reactions involving unsymmetrical N,N-diaryl α-iodo enaminones. This unique property enables the construction of carbazolone skeleton containing nitro substituted benzenoid ring.     

Iodine-mediated oxidative Pictet-Spengler reaction using terminal alkyne as the 2-oxoaldehyde surrogate for the synthesis of 1-aroyl-β-carbolines and fused-nitrogen heterocycles

An efficient iodine-mediated oxidative Pictet-Spengler reaction in dimethyl sulphoxide (DMSO) using terminal alkynes as the 2-oxoaldehyde surrogate for the synthesis of aryl (9H-pyrido[3,4-b]indol-1-yl)methanones is described. The scope of the protocol includes the total synthesis of Fascaplysin, Eudistomins Y₁ and Y₂. The methodology is extended for preparing pyrrolo[1,2-a]-quinoxaline and indolo[1,5-a]quinoxaline derivatives. The utility of 1-aroyl-β-carbolines was demonstrated by performing palladium-catalyzed β-carboline directed ortho-C(sp2)-H functionalization of the phenyl ring with thiomethyl (SMe) group using DMSO as source and for accessing 4-aryl-canthin-6-ones.     

Facile synthesis of bicyclic 1-arylpyrazol-5-ones

In this Letter, we described a facile method for constructing fused bicyclic 1-arylpyrazol-5-one ring system. We employed various methylene-containing carboxylic acids as the substrates and proved that the pyrazolone ring closure requires activated methylene group in intermediate II. Accordingly, a series of structurally diversified, fused bicyclic 1-arylpyrazol-5-ones was prepared in moderate to high yields using the requisite substrates.     

Synthesis of substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles by intramolecular nitrilimine cycloaddition

Both substituted 2,4,5,6-tetrahydrocyclopenta[c]pyrazoles and 2,4,5,6-tetrahydropyrrolo[3,4-c]pyrazoles have been synthesized by the 3+2 intramolecular dipolar cycloaddition of nitrilimines to alkynes. This cyclization has been extended to more versatile 3-bromo derivatives by the use of alkynylbromides as dipolarophiles.