Metal coordinating-induced self-assembly of cyclic lipopeptides into high-performance antimicrobial supramolecules.

This study designed a green hydrothermally-chelating approach to generate robust antimicrobial complexes via metal-coordinated supramolecular self-assembly of cyclic lipopeptides (CLs). The metal ion (Ca2+ and Zn2+)-coordinated CL (Ca/CL or Zn/CL complex; 1 mg/mL) demonstrated potent antibacterial activity against fungi (A. niger) and bacteria (E. coli and S. aureus) respectively, and in particular, completely suppressed the microbial resistance. Further physicochemical and spectal analysis showed that this coordination approach led to CL with enhanced hydrophobic and intermolecular electrostatic interactions, forming ß-sheet-rich secondary structures allowing the complexes easily contact with and destroy the membrane of microorganisms. Practical application experiments validated that the Ca/CL and Zn/CL complexes strongly avoided table grape and fresh tomato from the contamination of pathogen. The findings of this study laid foundation for the utilization of metal ions to improve the biological activity of natural antimicrobial peptides.

A highly sensitive octopus-like azobenzene fluorescent probe for determination of abamectin B1 in apples.

The development of detecting residual level of abamectin B1 in apples is of great importance to public health. Herein, we synthesized a octopus-like azobenzene fluorescent probe 1,3,5-tris (5'-[(E)-(p-phenoxyazo) diazenyl)] benzene-1,3-dicarboxylic acid) benzene (TPB) for preliminary detection of abamectin B1 in apples. The TPB molecule has been characterized by ultraviolet-visible absorption spectrometry, 1H-nuclear magnetic resonance, fourier-transform infrared (FT-IR), electrospray ionization mass spectroscopy (ESI-MS) and fluorescent spectra. A proper determination condition was optimized, with limit of detection and limit of quantification of 1.3 µg L-1 and 4.4 µg L-1, respectively. The mechanism of this probe to identify abamectin B1 was illustrated in terms of undergoing aromatic nucleophilic substitution, by comparing fluorescence changes, FT-IR and ESI-MS. Furthermore, a facile quantitative detection of the residual abamectin B1 in apples was achieved. Good reproducibility was present based on relative standard deviation of 2.2%. Six carboxyl recognition sites, three azo groups and unique fluorescence signal towards abamectin B1 of this fluorescent probe demonstrated reasonable sensitivity, specificity and selectivity. The results indicate that the octopus-like azobenzene fluorescent probe can be expected to be reliable for evaluating abamectin B1 in agricultural foods.

IrCo alloy nanoparticles supported on N-doped carbon for hydrogen evolution electrocatalysis in acidic and alkaline electrolytes.

Designing efficient and low-cost electrocatalysts for the hydrogen evolution reaction (HER) is of great importance to advance water splitting technology towards practical applications. Herein, we report the preparation of IrCo nanoparticles supported on nitrogen-doped carbon (IrCo/NC) as a HER electrocatalyst in acidic and alkaline electrolytes. The IrCo/NC composite is obtained by pyrolyzing an Ir-doped Co(OH)2 precursor on g-C3N4, and is endowed with N-doped carbon and uniform IrCo alloy nanoparticles via a crystal confinement resulting from the Ir-doping into the Co(OH)2 layer. Electrocatalytic analysis shows that the IrCo/NC electrode requires low overpotentials of 32 mV at 10 mA cm-2 in 0.5 M H2SO4 and 33 mV in 1 M KOH, which are superior to those of the Co/NC and IrCo alloys that are free of Ir-doping or N-doped carbon. The results provide a strategy for designing and preparing active noble-transition bimetallic alloy electrocatalysts as efficient HER catalysts.

Tumor targeted, stealthy and degradable bismuth nanoparticles for enhanced X-ray radiation therapy of breast cancer.

Nanoparticles of heavy elements can be used as radiosensitizers to enhance X-ray radiation therapy, but a major roadblock in translating nanoparticle radiosensitizers into clinical practice of cancer treatment is related to the non-degradable nature of the nanoparticles, which can cause accumulation inside body and long-term toxicity. This paper reports the use of a folate-inserted, red blood cell membrane-modified bismuth (i.e., F-RBC bismuth) nanoparticles in X-ray radiation therapy for breast cancer, where cell membrane coating provides long blood circulation time, folate acts as tumor targeting agent, X-ray and bismuth nanoparticles interaction generates more free radicals for cancer cells damage, and physiological condition helps dissolve bismuth nanoparticles after treatment. Significant tumor inhibition and improved survival ratio in mice was confirmed when F-RBC bismuth nanoparticles were used to sensitize X-ray radiation. In vivo bio-distribution and histological analysis indicated F-RBC bismuth nanoparticles were excreted from animal body after 15 days and no evident damage or inflammatory was observed in major organs. Cell membrane modification and dissolution of bismuth nanoparticles in body allow the fine tune of the circulation, radiation enhancement and body clearance in such a way that treatment effect can be maximized and long term toxicity can be minimized.

Electrically Modulated Localized Surface Plasmon around Self-Assembled-Monolayer-Covered Nanoparticles.

This article reports the observation of electrical modulation of localized surface plasmon around self-assembled monolayer (SAM)-modified gold nanoparticles and the establishment of a new spectroscopy technique, that is, dynamic electro-optical spectroscopy (DEOS). The gold nanoparticles are deposited onto a transparent conductive substrate, and an electrical bias applied on the conductive substrate can cause shift of resonance plasmon response, where the direction of peak shift is related to the polarity of applied bias. The peak shift observed at 2.4 V is approximately ten times larger than those reported in previous work. It is postulated that significant peak shift is the result of reorientation of adsorbed water on electrode, which can change local dielectric environment of nanoparticles. An energy barrier is identified when adsorbed water molecules are turned from oxygen-down to oxygen-up. Frequency-dependent peak shifts on surface-modified gold nanoparticles show that reorientation is a fast reversible process with rich dynamics.

Synthesis and Scanning Tunneling Microscopy Observation of 1,3,5-Triazine Bearing Azo-Carboxylate.

A new compound (2,4,6-tris-(3,5-di-methyl formate-4'-hydroxy azobenzene)-1,3,5-triazine,TDHAT) has been synthesized and the scanning tunneling microscopy (STM) is utilized to clarify the geometrical configuration on the highly oriented pyrolytic graphite (HOPG) surface. The star-shaped molecule self-assembles into uniform and regular triangular petal structure at liquid­solid interface, and high-resolution images has been obtained, which implied a high stability of this two dimensional configuration. The distance between the scattered bright spot and the center of the petal is measured to be about 1.2 nm (L2), which corresponds to the actual size of each arm. Moreover, a comparison has been made between the TDHAT molecule and the TMA 4a molecule which has similar star-shaped structure with a long alkyl chain at the each end of the three arms, drawing a conclusion that both the structure of arms and the substituent groups would impact the nanoarchitecture. The results give us insight into a better comprehension of the self-assembly of the star-shaped molecule, which benefits the construction of functional nanostructures.