Determination of 48 fragrance allergens in toys using GC with ion trap MS/MS

This paper presents a method for the simultaneous determination of 48 fragrance allergens in four types of toys (plastic toys, play clays, plush toys, and paper toys) based on GC with ion trap MS/MS. Compared with single‐stage MS, MS/MS is superior in terms of the qualification and quantification of a large range of compounds in complicated matrices. Procedures for extraction and purification were optimized for each toy type. The method proved to be linear over a wide range of concentrations for all analytes with correlation coefficients between 0.9768 and 0.9999. Validation parameters, namely, LODs and LOQs, ranged from 0.005–5.0 and from 0.02–20 mg/kg, respectively. Average recoveries of target compounds (spiked at three concentration levels) were in the range of 79.5–109.1%. Intraday and interday repeatabilities of the proposed method varied from 0.7–10.5% and from 3.1–13.4%, respectively. The proposed method was used to monitor fragrance allergens in commercial toy products. Our findings indicate that this method is an accurate and effective technique for analyzing fragrance allergens in materials composed of complex components.     

Regular arrays of triangular‐microstructure formed on silicon (111) surface via ultrafast laser irradiation in KOH solution

The regular micrometer‐scale triangular arrays were formed using ultrafast femtosecond laser irradiation on (111) surface of silicon wafer immersed in KOH solution (0.1 g/ml). At low laser fluence, the resulting surface is covered by triangular pits microstructures, whereas at high laser fluence, the structures are transformed to multilayer‐triangular stacks‐microstructures. The number of triangular stacks layer increased as the laser fluence increased. The formation of triangle microstructure arrays depends on both silicon surface crystallographic orientation and the concentration of KOH solution. Either for lower KOH solution concentration (0.02 g/ml) or other silicon crystallographic orientation, triangle arrays cannot be obtained. We attribute the formation of triangular microstructure arrays to the laser‐assisted chemical etching process. Copyright © 2013 John Wiley & Sons, Ltd.     

The Structure–Property Correlations in the Isomerism of Au21(SR)15 Nanoclusters by Density Functional Theory Study

Isomerism of atomically precise noble metal nanoclusters provides an excellent platform to investigate the structure–property correlations of metal nanomaterials. In this study, we performed density functional theory (DFT) and time‐dependent (TD‐DFT) calculations on two Au₂₁(SR)₁₅ nanoclusters, one with a hexagonal closed packed core (denoted as Au₂₁ ^hcp ), and the other one with a face‐centered cubic core (denoted as Au₂₁ ^fcc ). The structural and electronic analysis on the typical Au–Au and Au–S bond distances, bond orders, composition of the frontier orbitals and the origin of optical absorptions shed light on the inherent correlations between these two clusters.     

Synthesis and Infrared Multi‐band Absorption Properties of Core‐shell NaYF4:Yb3+, Er3+@SiO2 Nanoparticles

Due to the unique size effects, nanomaterials in infrared absorption have attracted much attention for their strong absorption in the infrared region. To achieve the infrared multi‐band absorption, we propose to synthesize a core‐shell structure nanomaterial consisting of NaYF₄:Yb³⁺, Er³⁺ core and a layer of SiO₂ as shell. A series of NaYF₄:Yb³⁺, Er³⁺ nanocrystals were synthesized through hydrothermal method by adjusting the ratio of citric acid(CA)‐to‐NaOH, and the effects of CA concentration, and NaOH concentration were studied in detail. NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanoparticles were synthesized by sol‐gel method using TEOS as silica source. The results show that the core‐shell NaYF₄:Yb³⁺, Er³⁺@SiO₂ nanoparticles were successfully synthesized. Up‐conversion spectra of these nanoparticles were recorded with 980 nm laser excitation under room temperature. There are no changes of the emission centers of nanoparticles before or after silica coating, but the emission intensities of nanoparticles after silica coating are weakened. Furthermore, the property of infrared multi‐band absorption was tested through ultraviolet‐visible‐near infrared spectrophotometer and infrared absorption spectra. The results illustrate that the multi‐band infrared absorption nanomaterial was successfully synthesized.     

Binding and cytotoxicity of 131I-labeled gastrin-releasing peptide receptor antagonists modified by cell penetrating peptides

Gastrin releasing peptide receptors (GRPRs) are one of the most interesting targets over expressed in various tumors. Due to the superior potential of the GRPR antagonist analogs, they have been studied in the tumor radio imaging and therapy field. However, typical antagonists suffered the shortcomings of no internalization and poor binding affinity which hampered their applications in radiotherapy. Therefore, we attempted to introduce Oligoarginines (cell penetrating peptides) to RM26, aiming to increase the binding affinity or even trigger the internalization of the peptides on cells. The results showed Arg₆ as the most potent CPP, significantly enhanced the binding avidity of RM26 to the GRPR.

     

Facile synthesis of a porous network-like silver film for electrocatalytic detection of nitrate

We have developed a method for in-situ construction of a porous network-like silver film on the surface of a glassy carbon electrode (GCE). It is based on a galvanic replacement reaction where a layer of copper nanoparticles is first electrodeposited as a sacrificial template. The silver film formed possesses a porous network-like structure and consists of an assembly of numerous nanoparticles with an average size of 200 nm. The electrode displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward the reduction of nitrate at a working potential of −0.9 V. The catalytic currents linearly increase with the nitrate concentrations in the range of 0.08–6.52 mM, with a detection limit of 3.5 μM (S/N = 3) and a repeatability of 3.4 % (n = 5).

A facile method was developed for in situ construction of a porous network-like Ag film on a glassy carbon electrode by a galvanic replacement reaction, where a layer of Cu nanoparticles previously electrodeposited as a sacrificial template. Thus-formed Ag film displays excellent electrocatalytic activity, good stability, and fast response (within 2 s) toward nitrate reduction.

     

Elucidation of the binding sites of sodium dodecyl sulfate to β-lactoglobulin using hydrogen/deuterium exchange mass spectrometry combined with docking simulation

Hydrogen/deuterium exchange mass spectrometry (H/DX MS) has become a powerful tool to investigate protein-protein and protein-ligand interactions, but it is still challenging to localize the interaction regions/sites of ligands with pepsin-resistant proteins such as lipocalins. β-Lactoglobulin (BLG), a member of the lipocalin family, can bind a variety of small hydrophobic molecules including retinols, retinoic acids, and long linear fatty acids. However, whether the binding site of linear molecules locates in the external groove or internal cavity of BLG is controversial. In this study we used H/DX MS combined with docking simulation to localize the interaction sites of a tested ligand, sodium dodecyl sulfate (SDS), binding to BLG. H/DX MS results indicated that SDS can bind to both the external and the internal sites in BLG. However, neither of the sites is saturated with SDS, allowing a dynamic ligand exchange to occur between the sites at equilibrium state. Docking studies revealed that SDS forms H-bonds with Lys69 in the internal site and Lys138 and Lys141 in the external site in BLG via the sulfate group, and interacts with the hydrophobic residues valine, leucine, isoleucine and methionine within both of the sites via its hydrocarbon tail, stabilizing the BLG-SDS complex.     

Isoselective Ring-opening Polymerization of Racemic Lactide Catalyzed by N-heterocyclic Olefin/(Thio)urea Organocatalysts

The isoselective ring-opening polymerization of racemic lactide was achieved by combining N-heterocyclic olefin(NHO) with mono(thio)ureas or bis(thio)ureas as catalytic systems. The polymerization process shows high stereoselectivity, controllability and reactivity,delivering multi-block isotactic polylactides with high chain-end fidelity and narrow molecular weight distributions. The enhancement of catalytic performance was observed in the following order: bisthiourea(DTU) monothiourea(TU) bisurea(DU) urea(U). The highest Pm(probability of forming a meso dyad) = 0.91 was observed at-70 °C when using NHO/U1 catalytic system and the high stereoselectivity was attributed to chain-end control mechanism.