Highly sensitive electrochemical sensor for nitric oxide using the self-assembled monolayer of 1,8,15,22-tetraaminophthalo-cyanatocobalt(II) on glassy carbon electrode

Glassy carbon (GC) electrode modified with a self-assembled monolayer (SAM) of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) was used for the selective and highly sensitive determination of nitric oxide (NO). The SAM of 4α-CoIITAPc was formed on GC electrode by spontaneous adsorption from DMF containing 1 mM 4α-CoIITAPc. The SAM showed two pairs of well-defined redox peaks corresponding to CoIII/CoII and CoIIIPc−1/CoIIIPc−2 in 0.2 M phosphate buffer (PB) solution (pH 2.5). The SAM modified electrode showed excellent electrocatalytic activity towards the oxidation of nitric oxide (NO) by enhancing its oxidation current with 310 mV less positive potential shift when compared to bare GC electrode. In amperometric measurements, the current response for NO oxidation was linearly increased in the concentration range of 3×10−9 to 30×10−9 M with a detection limit of 1.4×10−10 M (S/N=3). The proposed method showed a better recovery for NO in human blood serum samples.

Adsorption thermodynamics and kinetics study for the self-assembly of 1,8,15,22-tetraaminophthalocyanatocobalt(II) on glassy carbon surface

Spontaneous adsorption of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) on glassy carbon (GC) electrode leads to the formation of a stable self-assembled monolayer (SAM). Since the SAM of 4α-CoIITAPc is redox active, its adsorption on GC electrode was followed by cyclic voltammetry. SAM of 4α-CoIITAPc on GC electrode shows two pairs of well-defined redox peaks corresponding to CoIII/CoII and CoIIIPc−1/CoIIIPc−2. The surface coverage (Γ) value, calculated by integrating the charge under CoII oxidation, was used to study the adsorption thermodynamics and kinetics of 4α-CoIITAPc on GC surface. Cyclic voltammetric studies show that the adsorption of 4α-CoIITAPc on GC electrode has reached the saturation coverage (Γs) within 3 h. The Γs value for the SAM of 4α-CoIITAPc on GC electrode was found to be 2.37 × 10−10 mol cm−2. Gibbs free energy (ΔGads) and adsorption rate constant (kad) for the adsorption of 4α-CoIITAPc on GC surface were found to be −16.76 kJ mol−1 and 7.1 M−1 s−1, respectively. The possible mechanism for the self-assembly of 4α-CoIITAPc on GC surface is through the addition of nucleophilic amines to the olefinic bond on the GC surface in addition to a meager contribution from π stacking. The contribution of π stacking was confirmed from the adsorption of unsubstituted phthalocyanatocobalt(II) (CoPc) on GC electrode. Raman spectra for the SAM of 4α-CoIITAPc on carbon surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Raman and CV studies suggest that 4α-CoIITAPc is adopting nearly a flat orientation or little bit tilted orientation.

Electrochemical and spectral studies of self-assembled monolayer of 1,8,15,22-tetraaminophthalocyanatocobalt(II) on indium tin oxide surface

Self-assembled monolayer (SAM) of 1,8,15,22-tetraaminophthalocyanatocobalt(II) (4α-CoIITAPc) was prepared on indium tin oxide (ITO) electrode by spontaneous adsorption from dimethylformamide (DMF) solution containing 4α-CoIITAPc. The SAM of 4α-CoIITAPc formed on ITO electrode was characterized by cyclic voltammetry, Raman and UV–visible spectroscopic techniques. The cyclic voltammogram (CV) of 4α-CoIITAPc SAM shows two pairs of well-defined redox peaks corresponding to CoIII/CoII and CoIIIPc−1/CoIIIPc−2. The surface coverage (Γ) was calculated by integrating the charge under the anodic wave corresponding to CoII oxidation and it was found to be 2.25 × 10−10 mol cm−2. Raman spectrum obtained for the SAM of 4α-CoIITAPc on ITO surface shows strong stretching and breathing bands of Pc macrocycle, pyrrole ring and isoindole ring. Further, the –NH2 bending mode of vibration was absent for the SAM of 4α-CoIITAPc on ITO surface which indirectly confirmed that all the amino groups of 4α-CoIITAPc are involved in bonding with ITO surface. UV–visible spectrum for the SAM of 4α-CoIITAPc on ITO surface shows an intense B-band, Q-band and n–π∗ transition with slight broadening when compared to that of 4α-CoIITAPc in DMF.

Selective electrochemical epinephrine sensor using self-assembled monomolecular film of 1,8,15,22-tetraaminophthalocyanatonickel(II) on gold electrode

This article describes the highly sensitive and selective determination of epinephrine (EP) using self-assembled monomolecular film (SAMF) of 1,8,15,22-tetraamino-phthalocyanatonickel(II) (4α-NiIITAPc) on Au electrode. The 4α-NiIITAPc SAMF modified electrode was prepared by spontaneous adsorption of 4α-NiIITAPc from dimethylformamide solution. The modified electrode oxidizes EP at less over potential with enhanced current response in contrast to the bare Au electrode. The standard heterogeneous rate constant (k°) for the oxidation of EP at 4α-NiIITAPc SAMF modified electrode was found to be 1.94×10−2 cm s−1 which was much higher than that at the bare Au electrode. Further, it was found that 4α-NiIITAPc SAMF modified electrode separates the voltammetric signals of ascorbic acid (AA) and EP with a peak separation of 250 mV. Using amperometric method the lowest detection limit of 50 nM of EP was achieved at SAMF modified electrode. Simultaneous amperometric determination of AA and EP was also achieved at the SAMF modified electrode. Common physiological interferents such as uric acid, glucose, urea and NaCl do not interfere within the potential window of EP oxidation. The present 4α-NiIITAPc SAMF modified electrode was also successfully applied to determine the concentration of EP in commercially available injection.

Vc二步发酵新组合菌系B_(15-14)的筛选及其条件优化

筛选出了一组Vc二步发酵的新组合菌系(命名为B15-14),研究了环境因子对新菌系产酸的影响。结果显示:新组合菌系的最适底糖浓度为7%;温度为29~33℃,31℃为最适;适当增加通气量(20~30 mL装液量,250 mL三角瓶)有利于产酸;起始pH值范围为6.0~7.5;以B t菌做伴生菌时,发酵40 h就已达到终点,明显缩短了发酵时间。

La_(1-x)Pr_xP_5O_(14) 晶体的光谱性质

分析了室温下晶体在紫外、可见区的吸收、荧光和红外光谱,利用Judd Ofeld理论计算了PrPP和La0.2Pr0.8PP晶体中Pr3+的实验振子强度,PrPP和La0.2Pr0.8PP晶体中Pr3+离子振子强度变化不大,说明在该晶体中Pr3+的浓度猝灭效应较小。红外光谱和结构分析确定了晶体的结构为单斜晶系,并观察到Pr3+的3P0 3H6跃迁的红色发射很强。

La(1-x)Pr_xP_5O_(14)晶体的研究

用水热法研究了La12xPr xP5O14(LaPrPP)(0 < x < 1,原子百分含量)晶体的生长,测定了La0.2Pr0.8PP晶体结构为 单斜晶系,空间群为P21/c。晶体的密度为3.27g/cm3,分解温度为915℃。分析了室温下晶体在紫外、可见区的吸 收、荧光和红外光谱,利用Judd2Ofeld 理论计算了PrPP 和La0. 2Pr0. 8PP 晶体中Pr3 + 的实验振子强度,得到一些规律性结果,观察到Pr3 + 的3 P0 —3 H6 跃迁的红色发射很强。

La_(1-x)Pr_xP_5O_(14)晶体的发光

Pr~(3+)离子的能级结构丰富,在紫外可见区有很好的荧光发射。因此,以Pr~(3+)为激活离子的发光材料研究工作引起了人们的关注。轻稀土五磷酸盐晶体结构为单斜晶系,空间群为P_(1/2)/C,稀土离子处在隔离的多面体中,离子间的作用减弱,即使在化学计量比的PrP_5O_(14)仍得到激光输出。本文采用水热法生长出La_(1-x)Pr_xP_5O_(14)

Ce_xGd_(1-x)P_5O_(14)晶体的生长及其发光特性的光谱研究

本文采用蒸发溶液法生长出一系列 Ce_xGd_(1-x)P_5O_(14)晶体,测定了它们的结构均属于单斜晶系、空间群 P2_1/c,用稳态和时间分辨荧光光谱法研究了该晶体中不同 Gd 含量时的发光性能,观察到随着(1-x)值增加,包含有 Gd~(3+)发射在内的314nm 峰增强和 Ce~(3+)的荧光寿命的有规律递减,说明了存在着 Ce~(3+)至 Gd~(3+)的能量传递。