Amperometric Study of Au‐Colloid Function on Xanthine Biosensor Based on Xanthine Oxidase Immobilized in Polypyrrole Layer

Four kinds of xanthine oxidase (XOD) based amperometric biosensors were fabricated and their analytical performances were compared. Polypyrrole (PPY)/XOD biosensor was constructed by electrochemical oxidation of pyrrole in the solution containing xanthine oxidase and pyrrole in this paper. Colloidal Au was then immobilized on the biosensor. On the other hand, electron mediator, Prussian Blue (PB), was deposited on the electrode before the immobilization of PPY/XOD to enhance electron‐transfer rate and current response. The results showed that PPY/XOD, PPY/XOD/Au‐colloid, PB/PPY/XOD and PB/PPY/XOD/Au‐colloid biosensors exhibit good response to xanthine in 1×10^?6 M and 2×10^?5 M and Michaelis‐Menten constants (K_m) of these biosensors were 242.2, 113.4, 144.5, 43.2 μmol?L^?1, respectively. The dependence of current responses with applied voltages was discussed, and different mechanisms of these biosensors were discussed. It has been found that colloidal Au can enhance the current response at the same concentration of xanthine solution and decrease the energy‐barrier of electron‐transfer reaction on the electrode.     

Computational analyses of singlet-singlet and singlet-triplet transitions in mononuclear gold-capped carbon-rich conjugated complexes

Density functional theory and CASSCF calculations have been used to determine equilibrium geometries and vibrational frequencies of metal-capped one-dimensional pi-conjugated complexes (H3P)Au(C[triple chemical bond]C)(n)(Ph) (n = 1-6), (H3P)Au(C[triple chemical bond]CC6H4)(C[triple chemical bond]CPh), and H3P--Au(C[triple chemical bond]CC6H4)C[triple chemical bond]CAu--PH3 in their ground states and selected low-lying pi(pi)* excited states. Vertical excitation energies for spin-allowed singlet-singlet and spin-forbidden singlet-triplet transitions determined by the time-dependent density functional theory show good agreement with available experimental observations. Calculations indicate that the lowest energy 3(pi(pi)*) excited state is unlikely populated by the direct electronic excitation, while the low-lying singlet and triplet states, slightly higher in energy than the lowest triplet state, are easily accessible by the excitation light used in experiments. A series of radiationless transitions among related excited states yield the lowest 3(pi(pi)*) state, which has enough long lifetimes to exhibit its photochemical reactivities.     

A coumarin-based colorimetric and fluorescent probe for the highly selective detection of Au3+ ions

We develop a novel coumarin-alkyne derivative(NC7-AL), which can specifically react with Au~(3+) and give a colorimetric and fluorescent ‘‘turn-on' response toward Au~(3+). Notably, other alkynophilic metal species such as Au+, Ag+, Pd~(2+), Ni~(2+), Cu~(2+), and Hg~(2+) do not produce an interfering signal. A good linear relationship between emission intensity at 420 nm and Au~(3+) concentration from 0 to 2 equivalent is observed, and the detection limit(3s/k) is estimated to be ca. 3.58 nmol/L. Harnessing the Au~(3+)-induced color change from light yellow to colorless, we find that NC7-AL-based modified TLC plate can be used for convenient naked-eye detection of Au~(3+).     

An ultra-sensitive and colorimetric sensor for copper and iron based on glutathione-functionalized gold nanoclusters

Here, we report an ultra-sensitive and colorimetric sensor for the detection of Fe³⁺ or Cu²⁺ successively using glutathione-functionalized Au nanoclusters (GSH-AuNCs). For GSH-AuNCs can catalytically oxidize peroxidase substrates, such as 3, 3′, 5, 5′-tetramethylbenzidine (TMB), colored products are formed in the presence of H₂O₂. While upon the addition of Fe³⁺ or Cu²⁺ into the GSH-AuNCs-TMB-H₂O₂ system, diverse color and absorbance of the system was obtained due to the self oxidation of Fe³⁺ and the inhibition of peroxidase-like activity of GSH-AuNCs. With the introduction of ethylene diamine tetraacetic acid (EDTA) or ammonium fluoride (NH₄F) to GSH-AuNCs-TMB-H₂O₂+Cu²⁺ system or GSH-AuNCs-TMB-H₂O₂+Fe³⁺ system respectively, a restoration of color and absorbance of system was realized. On the basis of above phenomenon, a colorimetric and quantitative approach for detecting Fe³⁺ and Cu²⁺ was developed with detection limit of 1.25 × 10⁻⁹ M and 1.25 × 10⁻¹⁰ M respectively. Moreover, the concentration of Fe³⁺ and Cu²⁺ in human serums was also accurate quantified by this method. So this design strategy realized the simple and simultaneous detection of Fe³⁺ and Cu²⁺, suggesting significant potential in clinical diagnosis.     

亚纳米厚的氧化铝包裹层可以显著提高负载型金纳米颗粒催化剂的热稳定性

负载型金纳米颗粒催化剂在许多催化反应中展现出非常好的催化活性,但是金纳米颗粒在高温等反应条件下容易烧结团聚,极大地限制了金催化剂的应用。利用原子层沉积技术在Au/TiO₂催化剂表面分别精确沉积了一层超薄的二氧化钛和氧化铝包裹层,并对比研究了包裹层对金纳米颗粒的热稳定性影响。原位红外漫反射CO吸附和x-射线光电子能谱数据证实了氧化物包裹层的存在。发现亚纳米厚的氧化铝包裹层能够在600 C完全避免金纳米颗粒的团聚;相反,二氧化钛包裹层对金纳米颗粒稳定性的提高没有明显效果。通过CO氧化探针反应的活性测试,发现随着煅烧温度的升高氧化铝包裹的Au/TiO₂ 催化剂的活性逐渐提高,表明高温处理可以促进被包裹金原子的暴露并表现出催化活性。提供了提高金纳米颗粒稳定性的有效方法,为拓展金催化剂在条件苛刻的反应中的应用奠定了技术基础.     

低密度泡沫金提升黑腔腔壁再发射率的实验研究

提高黑腔辐射温度对高能量密度物理研究,尤其是惯性约束聚变研究至关重要.提高黑腔腔壁再发射率是增强黑腔辐射温度的一个有效措施.理论研究发现低密度泡沫材料能够降低腔壁能量损失,进而提高再发射率.在神光II原型激光装置上开展了泡沫金和固体金再发射能流对比测量实验,证实了该理论研究.实验利用透射光栅得到具有空间分辨和谱分辨的X射线发射,测量结果表明在190 eV的黑腔辐射场作用下,0.4 g/cc密度的泡沫金可比固体金提升约20%的X射线能流发射,并且增加的发射以1 keV以下的低能能段为主.自相似解得到的理论结果和MULTI 1D模拟计算的结果均表明泡沫金可提高腔壁再发射能流,与实验结果定性一致.研究结果表明,泡沫金作为黑腔腔壁材料可提高腔壁再发射率,增强黑腔辐射温度,具有诱人的应用前景.     

聚硫堇为探针与固定化载体的适配体传感器用于双酚A的检测研究

研制了一种简单和灵敏地检测环境激素双酚A(BPA)的电化学适配体传感器。首先在玻碳电极(GCE)表面采用电沉积法沉积一层多孔纳米金(NP-Au),再采用电聚合法将硫堇(TH)和适配体(APT)一步聚合到电极表面,以聚硫堇(PTH)作为电化学探针和APT的固定化载体,以牛血清白蛋白(BSA)抑制非特异性吸附,构筑GCE/NP-Au/PTH+APT/BSA传感器。采用差分脉冲伏安法对该传感器的电化学性能进行探究,发现双酚A在10.0 fg/mL~1.0 ng/mL浓度范围内有较好的信号响应,检出限为5.3 fg/mL。以GCE/PTH+APT/BSA传感器作为对照,其对双酚A在10.0 fg/mL~1.0 ng/mL浓度范围内呈线性关系,检出限为9.0 fg/mL。结果表明多孔纳米金的引入可有效提高传感器的灵敏度。GCE/NP-Au/PTH+APT/BSA传感器具有选择性高和检出限低等优点。     

L-半胱氨酸/纳米金/DNA/壳聚糖修饰金电极测定布洛芬

用电沉积和滴涂的方法依次将L-半胱氨酸、纳米金、DNA、壳聚糖修饰在金电极表面,制备了稳定性、响应性良好的修饰电极(L-Cys/Au colloid/DNA/CS/Au/CME)。考察了影响实验结果的关键因素,确定了最佳实验条件,进一步采用循环伏安法和差分脉冲伏安法研究了布洛芬在L-Cys/Au colloid/DNA/CS/Au/CME上的电化学行为。在最佳实验条件下,当布洛芬浓度在1.0×10~(-7)~1.0×10~(-4) mol/L范围内时相应的氧化还原峰电流与浓度呈现良好的线性关系,检出限(S/N=3)达2.3×10~(-8) mol/L。结果表明,该修饰电极对布洛芬有良好的响应性能,据此建立了一种测定布洛芬的新方法。     

赖氨酸辅助高分散金粒子修饰氮掺杂TiO_2纳米管催化剂的合成及光催化性能

通过溶胶-凝胶法联合水热合成法制备了氮掺杂TiO_2纳米管,并以该纳米管为载体,采用绿色无毒的赖氨酸作为链接剂和螯合剂,一步实现金粒子在TiO_2纳米管上的高度分散,制备得到高分散金粒子修饰氮掺杂TiO_2纳米管催化剂(Au/N-TiO_2纳米管).表征了产物的形貌、结构、光学特性及组成,通过紫外光下甲基橙水溶液的光降解率评价产物的光催化活性,讨论了氮掺杂量、金负载量、赖氨酸及焙烧对合成催化剂光催化性能的影响.结果显示,在赖氨酸存在下,金粒子在TiO_2纳米管上呈高度分散状态,未发生聚集.且与纯TiO_2纳米管相比,Au/N-TiO_2纳米管显示出更高的光催化活性.Au/N-TiO_2纳米管的高催化活性是由于氮掺杂后引起的TiO_2带隙能窄化、金粒子在载体上的高分散状态及金与TiO_2形成的肖特恩势垒引起的低电子-空穴复合率共同作用导致的.     

焙烧方法和焙烧条件对纳米Au/HZSM-5催化剂金粒径和催化性能的影响

采用负压沉积沉淀法制备了纳米Au/HZSM-5催化剂前体,研究了深床焙烧和等离子体焙烧两种方法,以及焙烧温度和焙烧气氛对催化剂中纳米金粒径和催化性能的影响,并采用ICP、TEM、XRD、UV-vis、XPS等表征方法对催化剂金粒子进行了物化性能表征,采用合成气羰基化制乙酸甲酯反应表征催化性能。结果表明,不同焙烧方法和不同焙烧温度及气氛对负载型纳米Au/HZSM-5催化剂中金粒径、形貌、物化性质和催化性能有明显影响。其中,以等离子体焙烧方法在500℃氮气气氛下制备的纳米1.86%Au/HZSM-5催化剂中的金粒径最小,为2-5 nm。用于催化合成气羰基化制乙酸甲酯反应,原料中CO的转化率为67%,乙酸甲酯选择性可达78%。