普鲁士蓝纳米修饰电极的制备及表征

采用激光加热拉伸的方法制备铂纳米电极,并通过交流电刻蚀的方法制备纳米孔电极,在这两种电极上可通过电化学方法原位合成单颗普鲁士蓝微晶. 结果表明,普鲁士蓝微晶在纳米微孔电极上的机械附着强度增强. 这种方法可用于制备纳米修饰电极或研究功能微晶体材料的电化学性质.     

普鲁士蓝薄膜的电积法制备及其化学组成

在金属和石墨基底电极上用恒电位沉积法制备出普鲁士蓝(PB)薄膜,研究了影响膜生长的多种因素;观察到PB膜的电化学活性。用红外光谱及电子能谱对膜的化学组成作了分析,结果表明,最初制备的膜为不溶性PB:Fe_4[Fe(CN)_6]_3,在含K~+的电解质溶液中经电化学反应后膜部分转变为可溶性PB:KFeFe(CN)_6,由此确定了PB膜的电化学反应式。     

普鲁士蓝在化学传感器中的研究及应用

综述了普鲁士蓝化学传感器的研究和应用进展。介绍了传感器敏感膜的制备方法，在电化学传感器和光学传感器中的应用及机理研究方面的成果。普鲁士蓝优越的氧化还原性质使普鲁士蓝化学传感器对于许多物质的检测有着重要的意义。     

Co-Fe普鲁士蓝类配合物纳米颗粒的微乳液法制备与表征

Highly oriented cubic, hollow cubic and spherical nanoparticles of cobalt-iron Prussian blue analogues were synthesized in poly oxyethylene tertoctylphenyl ether (TritonX-100)/n-hexanol/cyclohexane microemulsion. The effects of the water-to-surfactant molar ratio (w), the reactant concentration and the reaction temperature on the morphology of cobalt-iron Prussian blue analogues were studied. The samples were characterized by transmission electron microscopy (TEM), field emission scan electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD) and infrared spectroscopy (IR).     

分步电沉积普鲁士蓝、纳米铜复合膜修饰玻碳电极测定芦丁

采用分步电沉积方法,依次将普鲁士蓝膜(PB)和纳米铜(CuNPs)电沉积在玻碳电极(GCE)表面,制备了相应的修饰电极(CuNPs/PB/GCE)。考察了实验条件,并采用循环伏安(CV)法和差分脉冲伏安(DPV)法研究了芦丁在CuNPs/PB/GCE上的电化学行为,求解了相关的电化学参数。最佳条件下,采用DPV法,芦丁的还原峰电流与其浓度在1.0×10-8~1.0×10-4 mol/L范围内呈现良好的线性关系,其检出限(S/N=3)为2.8×10-9 mol/L。结果表明,电极表面PB和CuNPs的存在有效提高了芦丁的电化学响应。该修饰电极的选择性和重现性好,可以应用于水样中芦丁的检测。     

基于聚苯胺-普鲁士蓝/普鲁士蓝复合膜的过氧化氢电化学传感器的制备及表征

利用聚苯胺和普鲁士蓝的协同作用,构建了聚苯胺-普鲁士蓝/普鲁士蓝复合膜的H2O2电化学传感器.聚苯胺的带正电骨架和带负电的普鲁士蓝粒子相互吸引,且聚苯胺提供了很多氧化还原位点,有利于普鲁士蓝粒子的进一步均匀生长,使制备的传感器具备优异的电催化性能.采用扫描电镜和电化学方法对修饰电极进行了表征.在最佳实验条件下,该修饰电...     

普鲁士蓝纳米碳管修饰玻碳电极测定吡虫啉的研究

用纳米碳管修饰的玻碳电极以0.1 mol/L NH3-NH4Cl缓冲溶液为底液,用线性扫描伏安法对吡虫啉农药进行了测定。吡虫啉在-1.04 V出现的还原峰电流的大小与吡虫啉的浓度在1.34×10-7~2.94×10-5mol/L范围内呈良好的线性关系。本方法的检出限为5.0×10-8mol/L。本文对不同的修饰电极性能进行了研究,结果发现在玻碳电极上先修饰普鲁士蓝再修饰纳米碳管的电极对吡虫啉的响应最好,峰型最好,峰电流最大,测定最灵敏。     

磁性普鲁士蓝纳米颗粒的合成及其化学修饰电极的制作

利用FeSO₄与FeCl₃合成了超细磁性Fe₃O₄纳米颗粒, 并进一步利用该纳米颗粒与铁氰酸钾在酸性溶液(pH～2)中的化学反应成功制备了一种新型的磁性普鲁士蓝纳米颗粒; 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化学修饰电极, 考察了该电极对过氧化氢的电催化还原及对水合肼的电催化氧化特性. 该化学修饰电极可对过氧化氢和水合肼进行测定, 线性范围分别为过氧化氢2×10^－6～5×10^－3 mol/L, 水合肼7.2×10^－7～3.6×10^－4 mol/L. 利用磁性普鲁士蓝纳米颗粒制得的修饰电极具有催化性能高、稳定性好、表面易更新等优点.     

新型普鲁士蓝纳米方块-离子液体复合纳米界面协同检测鸟嘌呤

本文利用离子液体(IL)和普鲁士蓝(PB)纳米方块的协同作用测定鸟嘌呤。首先制备了IL-PB修饰电极,用循环伏安法对修饰电极进行了表征。为了使PB自身的信号达到最大,优化了各种制备条件,如IL和PB的比例,KCl溶液和HCl的浓度等。使用制备的修饰电极催化鸟嘌呤,优化了鸟嘌呤的测定条件如B-R缓冲溶液pH值;疏水性离子液体和亲水性离子液体对鸟嘌呤的影响,结果表明疏水性离子液体催化效果更好。该法在最优化条件下检测鸟嘌呤,在4.0×10-7～1.4×10-6 mol/L范围内与氧化峰电流呈现良好的线性关系,检出限为6.0×10-8 mol/L。     

酶功能化聚多巴胺包覆纳米普鲁士蓝的制备及电化学分析应用

在纳米金表面原位沉积普鲁士蓝,然后在核壳结构纳米金-普鲁士蓝的表面包覆一层易氧化聚合的多巴胺保护膜,利用多巴胺聚合表面残留的大量氨基和羟基进一步将纳米铂粒子修饰于聚多巴胺膜表面制得普鲁士蓝-聚多巴胺-纳米铂多层纳米复合材料。将此复合材料修饰于金电极表面,协同使用辣根过氧化物酶用于H_2O_2浓度的检测。结果表明:聚多巴胺的引入有效增加了普鲁士蓝的稳定性,增大了纳米铂的负载量以及辣根过氧化物酶的生物活性;由于普鲁士蓝、纳米铂和辣根过氧化物酶的多重信号放大作用,酶功能化纳米复合材料修饰电极对H_2O_2表现出良好的电还原活性。优化条件下,对H_2O_2的检测范围为2.0×10~(-7)~1.0×10~(-3)mol·L~(-1),检出限(S/N=3)为1.2×10~(-7)mol·L~(-1)。     

普鲁士蓝类似物修饰多孔陶瓷球的制备及其As吸附能力

通过粉末烧结和添加造孔剂法制备了直径为3～5 mm的多孔陶瓷球, 烧结温度为1573 K, 烧结时间1 h. 利用碱处理法对该多孔陶瓷球进行了脱硅处理, 降低了多孔陶瓷表面的Si/Al的物质的量之比, 并且利用扫描电镜对碱处理前后多孔陶瓷球的表面形貌进行了表征. 通过脱硅后陶瓷球与亚铁氰化钾溶液的反应, 对多孔陶瓷球进行了表面修饰, 在其表面生成了蓝色的普鲁士蓝类似物, 并且利用X射线粉末衍射分析、X射线能谱分析和红外光谱分析对该蓝色物质进行了表征. 利用砷酸二氢钠为砷源研究了修饰后陶瓷球的As离子吸附能力.     

尿酸在普鲁士蓝修饰电极上的电化学行为及其分析应用

用恒电位电解法制备了普鲁士蓝修饰玻碳电极,研究了尿酸(UA)在该电极上的电化学行为,并提出了一种新的用于检测UA的方法。在 0. 1mol/L(pH5. 0 )的醋酸缓冲溶液中, 0. 100mol/LKCl作为支持电解质,UA在普鲁士蓝修饰电极上于 0. 470V处产生一灵敏的氧化峰,方波伏安法测定其氧化峰电流与UA浓度在 2. 5×10-6 ~2. 0×10-4 mol/L范围内呈良好的线性关系,相关系数为 0. 9986,检出限为 1. 1×10-6 mol/L。该电极制作简单,重现性良好,可用于UA的测定。     

有机高价碘化学简介及其应用

近几十年来,有机高价碘化学蓬勃发展,有机高价碘试剂也受到化学合成工作者的广泛关注,关于有机高价碘试剂的反应性研究也获得了迅猛发展。有机高价碘试剂作为绿色、高效、多功能化的氧化剂,通常容易制备且操作简单,与已有的合成方法相比,该类试剂参与的反应表现出了许多独特的优点,并且具有与汞、铬、铅、铊等重金属试剂类似的反应性,但却没有这些试剂所带来的毒性和环境污染问题。本文介绍了有机高价碘化学的起源与发展,高价碘试剂的结构特点与分类,高价碘试剂在有机合成、材料化学及工业合成中的应用。     

Electrochemistry of Prussian Blue in silica sol-gel electrolytes doped with polyamidoamine dendrimers

The inclusion of a generation-4 polyamidoamine (G4-PAMAM) dendrimer in a silica sol-gel yielded a solid electrolyte that was used to encapsulate Prussian Blue (PB), iron(III) hexacyanoferrate(II), and cobalt hexacyanoferrate. The PB was synthesized in the doped silica by sequential immersion of a monolith in 0.1 M K₄Fe(CN)₆, water, and 0.1 M FeCl₃. Inclusion of G4-PAMAM resulted in a nanoporous anion-exchange material with a capacity of 10.1 mmol g^–1, which is about four times greater than the capacity of silica alone. Relative to its G0 counterpart, the G4-PAMAM doped silica increased the rate of formation of PB by a factor of ca. 20. The solid state voltammetry of PB in the doped silica had the usual features for this compound. At 0.1 V vs. a Ag quasi-reference electrode, a reversible reduction was seen; the relationship between current and scan rate was that for a surface-confined redox couple. The quasi-reversible oxidation of PB was observed at 0.85 V. Inclusion of G4-PAMAM increased the lifetime of silica as a solid electrolyte from a few days to at least three months. Raman microprobe mapping analysis demonstrated that PB was homogeneously distributed across the entire width (ca. 1 mm) of the G4-doped monolith with 20-h immersions. Electronic Publication     

Role of acidity on the electrochemistry of Prussian Blue at plain and Nation filmcoated electrodes

Prussian Blue (PB) coated on plain platinum (Pt) shows a redox wave at 0.44V vs SCE in addition to the two usual redox waves at 0.82 and 0.12 V vs SCE when the electrodes were dipped in acidic KC1 solution. PB incorporated into Nation film-coated on Pt electrode exhibited the same behaviour even in the presence of neutral KG solution. In acidic KC1, the additional redox wave observed for PB incorporated into Nation film shifted positively to 0.39V vs SCE and the peak separation was reduced to 30mV. The observed additional redox wave for PB coated on plain Pt electrode and incorporated into Nafion film-coated Pt electrodes was assigned to the partial reduction of PB occurring due to the insertion of protons into the film. The effect of various cations on the electrochemistry of PB incorporated into Nafion film-coated electrode was also studied.     

色氨酸在普鲁士蓝修饰玻碳电极上的电化学行为研究

采用电沉积法制备了普鲁士蓝修饰玻碳电极(PB/GCE),使用循环伏安法(CV)研究了色氨酸(Trp)在修饰电极上的电化学特性,并建立了一种电化学检测色氨酸的新方法。实验结果表明,在优化实验条件下,色氨酸在8.0×10-6～5.0×10-4mol·L-1浓度范围内与峰电流呈良好线性关系,线性回归方程为Ip(μA)=5.8954c(μmol·L-1)-32.91,相关系数r=0.9999(n=8),方法检出限(S/N=3)为3.5×10-7mol·L-1。将该修饰电极用于色氨酸样品的测定,结果满意。初步的反应机理探讨表明,色氨酸在普鲁士蓝电极上的反应可能是以两步进行的两电子氧化过程。     

Preparation and purification of Semi-Methylthymol Blue

A direct extractive method has been developed for preparation of pure Semi-Methylthymol Blue (SMTB) from a synthetic mixture containing ca. 30% of SMTB in presence of Thymol Blue (TB, ca. 45%), Methylthymol Blue (MTB, ca. 10%) and other components such as acetic acid and iminodiacetic acid (IDA). The method is based on the dependence of the extraction coefficients of the individual components on the pH of an aqueous phase in equilibrium with butanol phase. The separation of TB from the mixture is best at pH 9.5–10.5 and the separation of SMTB is best at pH 2.9–4.5. At pH 10.2 the ratio of the extraction coefficient of TB to that of SMTB is 213 and to that of MTB is 776. At pH 2.9 the ratio of the extraction coefficient of SMTB to that of MTB is ca. 20 and at pH 4.5 is ca. 100, but the absolute values of the extraction coefficient for SMTB are only 3.4 at pH 4.5 and ca. 10 at pH 2.9. This means the quantitative transfer of SMTB to the butanol phase is much easier at pH 2.9. Then a more complete separation of SMTB from the mixture with MTB can be achieved by stripping of the latter into a pH 4.5 aqueous medium. The method for obtaining of anhydrous SMTB is also given. About 70% of the original amount SMTB present can be obtained as the dry product (containing over 99% SMTB).     

组氨酸修饰普鲁士蓝的制备及与银离子的作用

利用水热法合成了组氨酸修饰的普鲁士蓝(HisPB).通过扫描电子显微镜(SEM),X射线衍射(XRD)以及紫外-可见分光光度计(UV-Vis)等对合成的HisPB样品进行了形貌和结构表征.与未经修饰的普鲁士蓝(PB)相比,组氨酸修饰的普鲁士蓝粒子体积更大,表面更光滑,表面官能团增多,这些因素显著提升了普鲁士蓝在碱性溶液中的稳定性.确定了HisPB用于检测银离子的最佳pH值为10,通过监测HisPB与银离子反应后其紫外光谱在800 nm处的吸收峰强度变化以及溶液颜色的改变,实现了对6～40μmol/L浓度范围内银离子的检测.     

Thermal expansion in 3d-metal Prussian Blue Analogs—A survey study

We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions M^II₃[(M′)^III(CN)₆]₂·nH₂O and M^II₂[Fe^II(CN)₆]·nH₂O, where M^II=Mn, Fe, Co, Ni, Cu and Zn, (M′)^III=Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between −150 °C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3?m, F4?3m and Pm3?m. The temperature dependence of the lattice parameters was taken to compute an average coefficient of linear thermal expansion in the studied temperature range. Of the 17 compounds, 9 display negative values for the average coefficient of linear thermal expansion, which can be as large as 39.7×¹0⁻⁶ K⁻¹ for Co₃[Co(CN)₆]₂·12H₂O. All of the M^II₃[Co^III(CN)₆]₂·nH₂O compounds show negative thermal expansion behavior, which correlates with the Irving–Williams series for metal complex stability. The thermal expansion behavior for the PBAs of the M^II₃[Fe^III(CN)₆]₂·nH₂O family are found to switch between positive (for M=Mn, Co, Ni) and negative (M=Cu, Zn) behavior, depending on the choice of the metal cation (M). On the other hand, all of the M^II₂[Fe^II(CN)₆]·nH₂O compounds show positive thermal expansion behavior.     

纳米材料在蛋白质分离中的应用

蛋白质的分离技术不仅在药物检测和制药工程中具有重要意义,而且还是生化工程和蛋白质分析的一个研究热点.纳米材料具有许多与众不同的特性,广泛应用于化工、生物、医药、航天等多个领域,被认为是21世纪最有前途的材料.本文作者从非金属氧化物纳米材料、非金属单质纳米材料、金属氧化物纳米材料、金属单质纳米材料、纳米聚合物、纳米复合材料等方面综述了纳米材料在蛋白质分离方面的应用现状,总结了其在蛋白质分离中的优缺点,并就其在蛋白质固定和分离领域的应用前景进行了展望.