High efficiency palladium catalysts supported on multi-wall carbon nanotubes synthesized with 1,3-bis(diphenylphosphino) propane for ethanol oxidation

In this paper, a facile and effective method is introduced to prepare palladium electrocatalysts for the oxidation of ethanol in alkaline media. According to the transmission electron microscopy measurement, the as-prepared Pd nanoparticles with the average particle size of 2.5 nm are evenly deposited on the surface of the multi-wall carbon nanotubes by using 1,3-bis(diphenylphosphino) propane as a special additive. Electrochemical measurements demonstrate that the as-prepared catalyst exhibits good electrocatalytic activity and stability for the electrooxidation of ethanol.     

A Hairpin Electrochemical Aptasensor for Sensitive and Specific Detection of Thrombin Based on Homogenous Target Recognition

An electrochemical aptasensor was developed for sensitive and specific detection of thrombin by combining homogenous recognition strategy and gold nanoparticles (AuNPs) amplification. Streptavidin‐alkaline phosphatase was used as reporter molecule. Compared with the traditional hairpin aptasensor monitoring the distance of the redox molecule from the electrode surface, the proposed aptasensor successfully overcome the limitations of distance and improved the stability and high affinity of the aptamer hairpin through homogenous recognition, which enhanced the sensitivity and selectivity of the sensors effectively. Additionally, AuNPs were employed to increase the active area and conductivity of the electrode, thus, improving the sensitivity of the aptasensor. As a result, the designed thrombin detection sensor obtained a lower detection limit of 0.52 pM in buffer and 6.9 pM in blood serum.     

Electrochemical Recognition of Chiral Molecules with Poly(4‐bromoaniline) Modified Gold Electrode

A poly(4‐bromoaniline) (PBA) film is electrochemically synthesized on a gold electrode for the recognition of amino acids enantiomers. Scanning electron microscopy measurements show that the porous PBA films are made up of nano‐ribbons. At the PBA modified Au electrode differential pulse voltammograms of L ‐ and D ‐glutamic acids not only have very different current densities, but also produce different waveforms, providing an intuitive way to differentiate the two chiral molecules. Similar results are obtained in analyzing L ‐ and D ‐aspartic acids. Control experiments suggest that the observed sensing behavior arises from synergistic interactions between Au and the PBA film, where polymerization at the meta‐position creates a steric structure needed for differentiating chiral molecules.     

Detection of dopamine in the presence of excess ascorbic acid at physiological concentrations through redox cycling at an unmodified microelectrode array

The electrochemical behavior of dopamine was examined under redox cycling conditions in the presence and absence of a high concentration of the interferent ascorbic acid at a coplanar, microelectrode array where the area of the generator electrodes was larger than that of the collector electrodes. Redox cycling converts a redox species between its oxidized and reduced forms by application of suitable potentials on a set of closely located generator and collector electrodes. It allows signal amplification and discrimination between species that undergo reversible and irreversible electron transfer. Microfabrication was used to produce 18 individually addressable, 4-μm-wide gold band electrodes, 2 mm long, contained in an array having an interelectrode spacing of 4 μm. Because the array electrodes are individually addressable, each can be selectively biased to produce an overall optimal electrochemical response. Four adjacent microbands were shorted together to serve as the collector, and were flanked on each side by seven microbands shorted as the generator (a ratio of 1:3.5 of electroactive area, respectively). This configuration achieved a detection limit of 0.454?±?0.026 μM dopamine at the collector in the presence of 100 μM ascorbic acid in artificial cerebrospinal fluid buffer, concentrations that are consistent with physiological levels. Enhancement by surface modification of the microelectrode array to achieve this detection limit was unnecessary. The results suggest that the redox cycling method may be suitable for in vivo quantification of transients and basal levels of dopamine in the brain without background subtraction.

Tuning of Ti-doped mesoporous silica for highly efficient enrichment of phosphopeptides in human placenta mitochondria

Extraction of phosphopeptides from rather complex biological samples has been a tough issue for deep and comprehensive investigation into phosphoproteomes. In this paper, we present a series of Ti-doped mesoporous silica (Ti-MPS) materials with tunable composition and controllable morphology for highly efficient enrichment of phosphopeptides. By altering the molar ratio of silicon to titanium (Si/Ti) in the precursor, the external morphology, Ti content, internal long-rang order, and surface area of Ti-MPS were all modulated accordingly with certain regularity. Tryptic digests of standard phosphoprotein α- and β-casein were employed to assess the phosphopeptide enrichment capability of Ti-MPS series. At the Si/Ti molar ratio of 8:1, the optimum enrichment performance with admirable sensitivity and capacity was achieved. The detection limit for β-casein could reach 10 fmol, and 15 phosphopeptides from the digest of α-casein were resolved in the spectrum after enrichment, both superior to the behavior of commercial TiO₂ materials. More significantly, for the digest of human placenta mitochondria, 396 phosphopeptides and 298 phosphoproteins were definitely detected and identified after enrichment with optimized Ti-MPS material, demonstrating its remarkable applicability for untouched phosphoproteomes. In addition, this research also opened up a universal pathway to construct a composition-tunable functional material in pursuit of the maximum performance in applications.

Synthesis and self-assembly behaviors of four-armed amphiphilic polystyrene-b-poly(N-isopropylacrylamide) copolymers

Four-armed amphiphilic block copolymers polystyrene-b-poly(N-isopropyl acrylamide) (PSt-b-PNIPAAM)₄ were synthesized by atom transfer radical polymerization (ATRP) in two steps. Star narrow dispersed polystyrene, (PSt-Br)₄, with controlled number-average molecular weight was firstly synthesized by ATRP of styrene (St) using pentaerythritol tetrakis (2-bromoisobutyrate) (4Bri-Bu) as four-armed initiator. Then, (PSt-b-PNIPAAM)₄ was prepared using (PSt-Br)₄ as macroinitiator by ATRP. The structures of (PSt-Br)₄ and (PSt-b-PNIPAAM)₄ were confirmed by characterization by nuclear magnetic resonance (¹H NMR). The apparent viscosity of the four-armed (PSt-b-PNIPAAM)₄ was significantly lower than that of the linear PSt-b-PNIPAAM with the same amount of repeat units of PSt and PNIPAAM. The self-assembly behavior of the four-armed amphiphilic block copolymers (PSt-b-PNIPAAM)₄ in mixed solution (DMF/H₂O) and the lower critical solution temperature (LCST) of the resulting micelles were investigated by scanning electron microscopy (SEM), dynamic light scattering (DLS) and UV-VIS spectroscopy. The results show that the size of the mono-dispersed spherical micelles decreased with the increment of the chain length of PNIPAAM in the block copolymers, while LCST increased.     

Coupling of ultrasound‐assisted extraction and expanded bed adsorption for simplified medicinal plant processing and its theoretical model: Extraction and enrichment of ginsenosides from Radix Ginseng as a case study

A high‐efficient and environmental‐friendly method for the preparation of ginsenosides from Radix Ginseng using the method of coupling of ultrasound‐assisted extraction with expanded bed adsorption is described. Based on the optimal extraction conditions screened by surface response methodology, ginsenosides were extracted and adsorbed, then eluted by the two‐step elution protocol. The comparison results between the coupling of ultrasound‐assisted extraction with expanded bed adsorption method and conventional method showed that the former was better than the latter in both process efficiency and greenness. The process efficiency and energy efficiency of the coupling of ultrasound‐assisted extraction with expanded bed adsorption method rapidly increased by 1.4‐fold and 18.5‐fold of the conventional method, while the environmental cost and CO₂ emission of the conventional method were 12.9‐fold and 17.0‐fold of the new method. Furthermore, the theoretical model for the extraction of targets was derived. The results revealed that the theoretical model suitably described the process of preparing ginsenosides by the coupling of ultrasound‐assisted extraction with expanded bed adsorption system.