聚多巴胺功能化的四氧化三钴纳米复合材料的制备及电催化性能

通过简单的自聚合反应在四氧化三钴表面包覆聚多巴胺膜,联合使用纳米铂和辣根过氧化物酶用于电催化还原过氧化氢。结果表明,聚多巴胺的使用增强后续纳米铂的负载量和辣根过氧化物酶的生物活性;四氧化三钴、纳米铂和辣根过氧化物酶的多重信号放大作用,大大增强了该复合材料的催化活性,提高了过氧化氢传感器的灵敏度。优化实验条件下,传感器对过氧化氢的检测范围为0.1~700 μmol·L^-1,检测限为0.08 μmol·L^-1。     

Sensitive electrochemical determination of α-fetoprotein using a glassy carbon electrode modified with in-situ grown gold nanoparticles,graphene oxide and MWCNTs acting as signal amplifiers

The authors describe an electrochemical immunoassay for α-fetoprotein (α-FP) using a glassy carbon electrode (GCE) modified with a nanocomposite made from gold nanoparticles, graphene oxide and multi-walled carbon nanotubes (AuNPs/GO-MWCNTs) and acting as a signal amplification matrix. The nanocomposite was synthesized in a one-pot redox reaction between GO and HAuCl₄ without using an additional reductant. The stepwise assembly of the immunoelectrode was characterized by means of cyclic voltammetry and electrochemical impedance spectroscopy. The interaction of antigen and antibody on the surface of the electrode creates a barrier for electrons and causes retarded electron transfer, this resulting in decreased signals in differential pulse voltammetry of hexacyanoferrate which is added as an electrochemical probe. Using this strategy and by working at a potential of 0.2 V (vs. SCE), a wide analytical range (0.01 - 100 ng∙mL‾¹) is covered. The correlation coefficient is 0.9929, and the limit of detection is as low as 3 pg∙mL‾¹ at a signal-to-noise ratio of 3. This electrochemical immunoassay combines the specificity of an immunological detection scheme with the sensitivity of an electrode modified with AuNPs and GO-MWCNTs.

Schematic illustration of the fabrication procedure of the immunosensor

     

Determination of tyrosine using <Emphasis Type="Italic">p</Emphasis>-sulfonated calix[<Emphasis Type="Italic">n</Emphasis>]arene modified electrode

Cyclic voltammetry was used to detect p-sulfonated calix[n]arenas (SCnA) how to immobilize on gold surface. P-sulfonated calix[n]arenes not only increased the specific surface area of the modified electrode, but also improved the enrichment ability of tyrosine. This led to a significant increase in peak current, and improved the sensitivity of tyrosine determination on the p-sulfonated calix[n]arenes-modified electrode. The modified electrode showed good catalytic ability of l-tyrosine oxidation reaction. The peak current of l-tyrosine increased and the oxidation peak potential shifted negatively with cavity size of the SCnA-modified electrode, which indicated that the catalytic ability of the modified electrode to l-tyrosine oxidation reaction was also enhanced. For the tyrosine guest molecule, the order of electrochemical activity and magnitude of catalytic ability of the oxidation reaction of the three modified gold electrodes was as follows: SC4A?>?SC6A?>?SC8A. The electrode had high selectivity and stability for the determination of tyrosine, with a wide linear range, low detection limit and high sensitivity at different concentrations under different pH values. This resulted in an accurate, fast, sensitive electrochemical method for the determination of tyrosine. The sensor was used for the determination of tyrosine in human urine with satisfactory results.     

Approximation of optimal feedback control: a dynamic programming approach

We consider the general continuous time finite-dimensional deterministic system under a finite horizon cost functional. Our aim is to calculate approximate solutions to the optimal feedback control. First we apply the dynamic programming principle to obtain the evolutive Hamilton–Jacobi–Bellman (HJB) equation satisfied by the value function of the optimal control problem. We then propose two schemes to solve the equation numerically. One is in terms of the time difference approximation and the other the time-space approximation. For each scheme, we prove that (a) the algorithm is convergent, that is, the solution of the discrete scheme converges to the viscosity solution of the HJB equation, and (b) the optimal control of the discrete system determined by the corresponding dynamic programming is a minimizing sequence of the optimal feedback control of the continuous counterpart. An example is presented for the time-space algorithm; the results illustrate that the scheme is effective.     

Regulating silver nanowire size enables efficient photoelectric conversion

The increasing demand for the state-of-the-art transparent conductive electrodes has received great interest in synthesizing silver nanowires(AgNWs) with a uniform diameter that exhibit excellent conductance, transparency, flexibility and mechanical ductility. Herein, we report the controllable synthesis of ultrathin AgNWs with high aspect ratio via a polyol-assisted process.The diameter of AgNWs can be continuously modulated from 20 to 80 nm by simply adjusting the aging time. The selfassembled films fabricated by using AgNWs with a diameter of 20 nm as building blocks enable an excellent performance and show a sheet resistance of ～30 Ω/sq and an optical transmittance of 94%. In addition, such nanowire-based conductive films can keep the excellent flexibility and resistance after bending 10,000 cycles. Similarly, the intelligent dimming films prepared by this AgNW films also have excellent flexibility and stability.     

Hollow ternary PtPdCu nanoparticles: a superior and durable cathodic electrocatalyst

Hollow alloyed nanoparticles (NPs) represent one kind of promising fuel cell electrocatalyst. However, the formation of single-cavity hollow structures by a dealloying process is quite challenging owing to the random leaching/dissolution of transition metals, surface passivation and the limited diffusion distance of the noble metals. Here we present a facile method to prepare hollow PtPdCu NPs derived from monodisperse alloy NPs by an acetic acid-assisted dealloying process. Here, acetic acid not only acts as a chemical etching agent but also plays an important role in the removal of the residual surfactants for colloidal NPs. Our findings rectify the current knowledge that hollow alloyed NPs cannot be prepared by a dealloying strategy and provide further understanding of the dealloying process in a ternary system. Such unique hollow ternary PtPdCu NPs exhibit outstanding durability and improved catalytic activity toward the oxygen reduction reaction.     

Study on the Supramolecular Interactions of p-Sulfonated Calix[4, 6, 8]arenes with Lomefloxacin

The supramolecular interactions between a homologous series of p-sulfonated calix[n]arenes (SCnA, n = 4, 6, 8) as hosts and lomefloxacin (LFLX) were studied by spectrofluorometry. LFLX was found to react with SCnA to produce stable complexes. The fluorescence intensity of the complexes decreased gradually with increasing SCnA concentration. The formation of complexes was further confirmed by ¹H NMR studies and molecular modeling calculations. Data of the stability constants and thermodynamic parameters of the obtained complex showed that the stability of the SC8A-LFLX complex is superior to that of SC6A-LFLX and SC4A-LFLX. A mechanism was proposed to explain the inclusion process.     

Quantitative analysis of pyrrolizidine alkaloids in Gynura procumbens by liquid chromatography–tandem quadrupole mass spectrometry after enrichment by PCX solid-phase extraction

ABSTRACT

Gynura procumbens is commonly consumed as a vegetable and has been approved as an ingredient for food and dietary supplements in China. However, Gynura species are known to contain toxic pyrrolizidine alkaloids (PAs) and the PA profiles in G. procumbens are not known. This study was to extract and enrich PA from G. procumbens or health care products using PCX solid-phase extraction (SPE) cartridges identify the main PAs in the herb and to develop an liquid chromatography–mass spectrometry (LC-MS/MS) method for assaying the PA contents in the plant and its derived products. Upon using multiple reaction monitoring (MRM) acquisition together with comparison to the characteristics of mass fragmentations and retention times of reference standards, 11 PAs were identified as the main PAs in the plant. After clean-up and enrichment with PCX solid-phase extraction (SPE) cartridges, which resulted in better PA recoveries than either C18 or SCX cartridges, the LC-MS/MS method was subjected to validation in terms of linearity, repeatability, limits of quantification (LOQ) and recovery. The validated method was applied to quantify PAs in 12 plant samples and 7 commercial finished products. The total amounts of targeted PAs were found to vary from 15.6 to 848 μg/kg in the herbs and from 9.9 μg/kg to 33.9 mg/kg in the commercial products. The present work was the first to demonstrate that G. procumbens contained PAs in the herb and its derived products and the PA contents might exceed the daily dose limits in food and herbal medicinal products proposed by the European Medicines Agency (i.e. 0.35 μg PA per day for 50 kg adult).     

ZIF-8原位负载Pd纳米粒子及其在Suzuki-Miyaura反应中的应用(英文)

将PdCl2与ZIF-8的反应原料ZnO和2-甲基咪唑按照一定的比例,采用机械化学法原位将Pd2+负载在ZIF-8上(Pd2+/ZIF-8)。然后用NaBH4将Pd2+/ZIF-8进行还原,得到均匀分散的Pd纳米颗粒(Pd/ZIF-8)。通过XRD、N2吸附、透射电镜、ICP-AES、XPS等对Pd/ZIF-8的结构、形貌、价态等进行了表征。结果表明用机械化学法原位制备的Pd/ZIF-8具有分散均匀、容易大量制备的优点。该催化剂不仅能高效催化Suzuki-Miyaura交叉偶联反应,并且能够多次循环利用。