Enhanced stability of ZnTPPS by polymeric gold nanoparticles in acidic aqueous solutions

Novel kind of core-shell corona complex micelles were prepared, which enhanced both the hydrolytic stability and the photostability of water-soluble zinc tetrakis(4-sulfonatophenyl) porphyrin (ZnTPPS) in acidic aqueous solutions. The core-shell gold nanoparticles (AuNPS) were synthesized by reducing HAuCl₄ and di-thioester terminated block copolymer, poly(Nisopropylacrylamide)-block-poly(4-vinylpyridine) (PNIPAM-b-P4VP). The complex micelles with gold core, P4VP/ZnTPPS shell and PNIPAM corona were formed by simple mixing of gold nanoparticles and ZnTPPS. The photochemical properties of the complex micelles were studied by UV–Visiblespectroscopy and fluorescence spectroscopy. The results showed trapping of ZnTPPS in the positively charged micellar shell that effectively prevented demetallation of the ZnTPPS that would occur in acidic aqueous solutions. Furthermore, with appropriate concentration of gold nanoparticles, ZnTPPS in the complex micelle had excellent photostability by suppression of generation of reactive oxygen species (ROS). The enhanced stability of ZnTPPS in acidic aqueous media could be extensively used for photocatalysis and in solar cells.     

How does a CC double bond cleave in the gas phase? Fragmentation of protonated ketotifen in mass spectrometry

In the literature, it is reported that the protonated ketotifen mainly undergoes C?C double bond cleavage in electrospray ionization tandem mass spectrometry (ESI‐MS/MS); however, there is no explanation on the mechanism of this fragmentation reaction. Therefore, we carried out a combined experimental and theoretical study on this interesting fragmentation reaction. The fragmentation of protonated ketotifen (m/z 310) always generated a dominant fragment ion at m/z 96 in different electrospray ionization mass spectrometers (ion trap, triple quadrupole and linear trap quadrupole (LTQ)‐orbitrap). The mechanism of the generation of this product ion (m/z 96) through the C?C double bond cleavage was proposed to be a sequential hydrogen migration process (including proton transfer, continuous two‐step 1,2‐hydride transfer and ion‐neutral complex‐mediated hydride transfer). This mechanism was supported by density functional theory (DFT) calculations and a deuterium labeling experiment. DFT calculations also showed that the formation of the product ion m/z 96 was most favorable in terms of energy. This study provides a reasonable explanation for the fragmentation of protonated ketotifen in ESI‐MS/MS, and the fragmentation mechanism is suitable to explain other C?C double bond cleavage reactions in mass spectrometry. Copyright © 2016 John Wiley & Sons, Ltd.     

A Sensitive Electrochemical Sensor Based on Solution Polymerized Molecularly Imprinted Polymers for Procaine Detection

A sensitive and selective method for the determination of procaine hydrochloride using molecularly imprinted polymers (MIPs) modified glassy carbon electrodes was developed. The MIPs were prepared by solution polymerization using procaine hydrochloride as the template molecules and acrylic acid (AA) and vinyltriethoxysilane (WD‐20) as the functional monomer and cross‐linking agent, respectively. A film was formed on the surface of the glassy carbon electrodes and later cross‐linked with ethanol as solvent. Next, these electrodes were employed to detect procaine hydrochloride by differential pulse voltammetry (DPV). Under the optimized conditions, good linearity (correlation coefficient of 0.9986) was observed between the oxidation peak current and the concentration of procaine hydrochloride in the range of 4.0×10^?8 to 2.4×10^?5 M in a pH 7.0 0.04 M phosphate buffer solution, and the detection limit (S/N=3) was 1.02×10^?8 M. In addition, the stability and reproducibility of the sensors were satisfactory. Moreover, the concentration of procaine hydrochloride in human blood serum samples was detected, and its recoveries ranged from 97.5 % to 106.4 % with RSD less than 2.15 %. These results suggest that the prepared molecularly imprinted electrochemical sensors can be used for the determination of procaine in clinical studies.     

A study of the interaction between polyvinylpyrrolidone and gemini surfactant G12-3-12 by NMR

The interaction between a water-soluble polymer polyvinylpyrrolidone (PVP) and a gemini surfactant N,N'-didodecyl-N,N,N',N'-tetramethyl-N,N'-propanediyl-diammonium dibromide (G12-3-12) was investigated by means of NMR in a D₂O solution at 298 K. The critical micelle concentration (СMC), critical aggregation concentration (СAC) and adsorption reached the saturated concentration (C2) were confirmed by chemical shift and self-diffusion coefficients, respectively. The results of the relaxation time ratio (T_R = T₂/T₁) of G12-3-12 show that the motion of the ionic head N⁺–CH₃^* proton (G6) is seriously restricted, and thus, it can be proved that the cationic head groups are situated in the hydrophilic layer of the micelle. The size of the mixed-aggregates in the G12-3-12/PVP solution is larger than pure G12-3-12 micelles according to self-diffusion coefficients, indicating that the G12-3-12 and PVP has formed mixed micelles, and ionic heads N⁺–CH₃^* become more tightly packed in the hydrophilic layer of the micelle shell. On the other hand, strong cross peaks, such as G1-P2, G1-P3, and G2-P3, appear in the 2D nuclear Overhauser enhancement spectroscopy (2D NOESY) spectra of the G12-3-12/PVP system, further indicating that the interaction sites are located between the hydrophobic tail of G12-3-12 and PVP ring.     

Asymmetric Total Synthesis of Propindilactone G,Part 1: Initial Attempts towards the Synthesis of Schiartanes

Our first‐generation synthetic study towards the total synthesis of propindilactone G ( 1 ) and its analogues is reported. The key synthetic steps were an intramolecular Pauson–Khand reaction (PKR) and a vinylogous Mukaiyama reaction (VMAR). The stereoselective synthesis of the CDE ring moiety with an all‐carbon quaternary center through a PKR was difficult, whilst a VMAR afforded a product with the opposite stereochemistry at the C20 position on the side chain. These results led us to redesign our synthetic strategy for the total synthesis of compound 1 .     

Self-sacrificial template method to MnO2 microspheres as highly efficient electrocatalyst for oxygen evolution reaction

Journal of Solid State Electrochemistry - ε-MnO2 microspheres have been synthesized using a self-sacrificial template method by annealing MnCO3 microspheres. The transformation process from...     

Hybrid porous Ni(OH)2-MnO2 nanosheets/plasma-grafted MWCNTs for boosted supercapacitor performance

The utilization of nickel hydroxide and manganese dioxide solely as high-performance supercapacitive materials is hindered by their low capacitance retention and electrical conductivity. As Ni(OH)₂ and MnO₂ give a synergistic effect, porous Ni(OH)₂-MnO₂ nanosheets with a thickness of 9 nm are successfully grown on carbon fiber (CF) via a single-step hydrothermal co-deposition method. Multi-walled carbon nanotubes (CNT) are grafted with maleic anhydride (MA) through plasma-grafted process, followed by thiol-ene reaction to synthesize CNT-MA−S (CMS) to increase their aqueous dispersion behavior. The electrochemical properties of Ni(OH)₂-MnO₂ are further enhanced by dip-coating CMS on nanosheets. The composition and morphology of CMS and Ni(OH)₂-MnO₂ nanosheets are characterized using scanning electron microscopy (SEM), fourier transform infrared spectroscopy (FTIR), electron spectroscopy for chemical analysis (ESCA), transmission electron microscopy (TEM), thermogravimetric analyses (TGA), nuclear magnetic resonance (NMR), and Raman spectroscopy. The electrochemical characteristics of fabricated electrodes are analyzed using cyclic voltammetry and chronopotentiometry methods. CF−Ni(OH)₂-MnO₂/CMS electrode is successfully synthesized without using any binder, exhibited ultrahigh specific capacitance (2049 F g⁻¹ at a current density of 1 A g⁻¹), and excellent capacitance retention (>80 %) at 2 A g⁻¹ charge/discharge rate after 5000 cycles.     

Carbene-Catalyzed Intermolecular Dehydrogenative Coupling of Aldehydes with C(sp3)−H Bonds

The development of catalyst-controlled methods for direct functionalization of two distinct C−H bonds represents an appealing approach for C−C formations in synthetic chemistry. Herein, we describe an organocatalytic approach for straightforward acylation of C(sp³)−H bonds employing readily available aldehyde as “acyl source” involving dehydrogenative coupling of aldehydes with ether, amine, or benzylic C(sp³)−H bonds. The developed method affords a broad range of ketones under mild conditions. Mechanistically, simple ortho-cyanoiodobenzene is essential in the oxidative radical N-heterocyclic carbene catalysis to give a ketyl radical and C(sp³) radical through a rarely explored intermolecular hydrogen atom transfer pathway, rendering the acylative C−C formations in high efficiency under a metal- and light-free catalytic conditions. Moreover, the prepared products show promising anti-bacterial activities that shall encourage further investigations on novel agrochemical development.     

Emergence of a Lanthanide Chalcogenide as an Ideal Scintillator for a Flexible X-ray Detector

The development of high-performance X-ray detectors requires scintillators with fast decay time, high light yield, stability, and X-ray absorption capacity, which are difficult to achieve in a single material. Here, we present the first example of a lanthanide chalcogenide of LaCsSiS₄ : 1 % Ce³⁺ that simultaneously integrates multiple desirable properties for an ideal scintillator. LaCsSiS₄ : 1 % Ce³⁺ demonstrates a remarkably low detection limit of 43.13 nGy_air s⁻¹ and a high photoluminescence quantum yield of 98.24 %, resulting in a high light yield of 50480±1441 photons/MeV. Notably, LaCsSiS₄ : 1 % Ce³⁺ exhibits a fast decay time of only 29.35±0.16 ns, making it one of the fastest scintillators among all lanthanide-based inorganic scintillators. Furthermore, this material shows robust radiation and moisture resistance, endowing it with suitability for chemical processing under solution conditions. To demonstrate the X-ray imaging capacity of LaCsSiS₄ : 1 % Ce³⁺, we fabricated a flexible X-ray detector that achieved a high spatial resolution of 8.2 lp mm⁻¹. This work highlights the potential of lanthanide chalcogenide as a promising candidate for high-performance scintillators.     

Ligand Modulation of Active Sites to Promote Cobalt-Doped 1T-MoS2 Electrocatalytic Hydrogen Evolution in Alkaline Media

Highly efficient hydrogen evolution reaction (HER) electrocatalyst will determine the mass distributions of hydrogen-powered clean technologies, while still faces grand challenges. In this work, a synergistic ligand modulation plus Co doping strategy is applied to 1T−MoS₂ catalyst via CoMo-metal-organic frameworks precursors, boosting the HER catalytic activity and durability of 1T−MoS₂. Confirmed by Cs corrected transmission electron microscope and X-ray absorption spectroscopy, the polydentate 1,2-bis(4-pyridyl)ethane ligand can stably link with two-dimensional 1T−MoS₂ layers through cobalt sites to expand interlayer spacing of MoS₂ (Co−1T−MoS₂-bpe), which promotes active site exposure, accelerates water dissociation, and optimizes the adsorption and desorption of H in alkaline HER processes. Theoretical calculations indicate the promotions in the electronic structure of 1T−MoS₂ originate in the formation of three-dimensional metal-organic constructs by linking π-conjugated ligand, which weakens the hybridization between Mo-3d and S-2p orbitals, and in turn makes S-2p orbital more suitable for hybridization with H-1s orbital. Therefore, Co−1T−MoS₂-bpe exhibits excellent stability and exceedingly low overpotential for alkaline HER (118 mV at 10 mA cm⁻²). In addition, integrated into an anion-exchange membrane water electrolyzer, Co−1T−MoS₂-bpe is much superior to the Pt/C catalyst at the large current densities. This study provides a feasible ligand modulation strategy for designs of two-dimensional catalysts.