A novel method for determination of inorganic oxyanions by electrospray ionization mass spectrometry using dehydration reactions

Novel methods for the determination of inorganic oxyanions by electrospray (ES) ionization mass spectrometry have been developed using dehydration reactions between oxyanions and carboxylic acids at the ES interface. Twelve oxyanions (VO₃^?, CrO₄^2?, MoO₄^2?, WO₄^2?, BO₃^3?, SiO₃^2?, SiO₄^4?, AsO₄^4?, AsO₂^?, SeO₄^2?, SeO₃^2? and NO₂^?), out of 16 tested, reacted with at least one of four aminopolycarboxylic acids, i.e. iminodiacetic acid (IDA), nitrilotriacetic acid (NTA), trans‐1,2‐diaminocyclohexane‐N,N,N′,N′‐tetraacetic acid and triethylenetetramine‐N,N,N′,N″,N′″,N′″‐hexaacetic acid, at the ES interface to produce the dehydration products that gave intense mass ion responses, sufficient for trace analysis. As examples, trace determinations of Cr^VI and silica in water samples were achieved after online ion exchange chromatography, where the dehydration product of CrO₄^2? and NTA (m/z 290) and that of SiO₄^4? and IDA (m/z 192) were measured. The limits of detection of the respective methods were 17 nM (0.83 ng Cr/ml) for Cr^VI and 0.17 μM (4.8 ng Si/mL) for SiO₄^4?. Copyright © 2016 John Wiley & Sons, Ltd.     

Thermal Conversion of Methane to Formaldehyde Promoted by Gold in AuNbO3+ Cluster Cations

In addition to generation of a methyl radical, formation of a formaldehyde molecule was observed in the thermal reaction of methane with AuNbO₃⁺ heteronuclear oxide cluster cations. The clusters were prepared by laser ablation and mass‐selected to react with CH₄ in an ion‐trap reactor under thermal collision conditions. The reaction was studied by mass spectrometry and DFT calculations. The latter indicated that the gold atom promotes formaldehyde formation through transformation of an Au?O bond into an Au?Nb bond during the reaction.     

Solvent‐free Liquid Crystals and Liquids from DNA

As DNA exhibits persistent structures with dimensions that exceed the range of their intermolecular forces, solid‐state DNA undergoes thermal degradation at elevated temperatures. Therefore, the realization of solvent‐free DNA fluids, including liquid crystals and liquids, still remains a significant challenge. To address this intriguing issue, we demonstrate that combining DNA with suitable cationic surfactants, followed by dehydration, can be a simple generic scheme for producing these solvent‐free DNA fluid systems. In the anhydrous smectic liquid crystalline phase, DNA sublayers are intercalated between aliphatic hydrocarbon sublayers. The lengths of the DNA and surfactant are found to be extremely important in tuning the physical properties of the fluids. Stable liquid‐crystalline and liquid phases are obtained in the ?20 °C to 200 °C temperature range without thermal degradation of the DNA. Thus, a new type of DNA‐based soft biomaterial has been achieved, which will promote the study and application of DNA in a much broader context.     

Simultaneous quantification of leukotrienes and hydroxyeicosatetraenoic acids in cell culture medium using liquid chromatography/tandem mass spectrometry

Leukotrienes (LTs) and hydroxyeicosatetraenoic acids (HETEs) are important bioactive lipid mediators that participate in various pathophysiological processes. To advance understanding of the mechanisms that regulate these mediators in physiological and pathological processes, an analytical method using liquid chromatography/tandem mass spectrometry for the simultaneous quantification of LTB₄, LTC₄, LTD₄, LTE₄, 5‐HETE_, 8‐HETE, 12‐HETE and 15‐HETE in cell culture media was developed. A Supel?‐Select HLB solid‐phase extraction cartridge was used for sample preparation. The compounds were separated on a C₁₈ column using gradient elution with acetonitrile–water–formic acid (20:80:0.1, v/v/v) and acetonitrile–formic acid (100:0.1, v/v). The calibration curves of LTB₄, LTD₄, LTE₄ and HETEs were linear in the range of 0.025–10 ng/mL, and the calibration curve of LTC₄ was linear in the range of 0.25–10 ng/mL. Validation assessment showed that the method was highly reliable with good accuracy and precision. The stability of LTs and HETEs was also investigated. Using the developed method, we measured LTs and HETEs in the culture supernatant of the human mast cell line HMC‐1. The present method could facilitate investigations of the mechanisms that regulate the production, release and signaling of LTs and HETEs. Copyright © 2014 John Wiley & Sons, Ltd.     

Three Short Stories about Hexaarylbenzene–Porphyrin Scaffolds

A feasible two‐step synthesis and characterization of a full series of hexaarylbenzene (HAB) substituted porphyrins and tetrabenzoporphyrins is presented. Key steps represent the microwave‐assisted porphyrin condensation and the statistical Diels–Alder reaction to the desired HAB‐porphyrins. Regarding their applications, they proved to be easily accessible and effective high molecular mass calibrants for (MA)LDI mass spectrometry. The free‐base and zinc(II) porphyrin systems, as well as the respective tetrabenzoporphyrins, demonstrate in solid state experiments strong red‐ and near‐infrared‐light emission and are potentially interesting for the application in “truly organic” light‐emitting devices. Lastly, they represent facile precursors to large polycyclic aromatic hydrocarbon (PAH) substituted porphyrins. We prepared the first tetra‐hexa‐peri‐hexabenzocoronene substituted porphyrin, which represents the largest prepared PAH‐porphyrin conjugate to date.     

A rapid dissolution procedure to aid initial nuclear forensics investigations of chemically refractory compounds and particles prior to gamma spectrometry

A rapid and effective preparative procedure has been evaluated for the accurate determination of low-energy (40–200 keV) gamma-emitting radionuclides (²¹⁰Pb, ²³⁴Th, ²²⁶Ra, ²³⁵U) in uranium ores and uranium ore concentrates (UOCs) using high-resolution gamma ray spectrometry. The measurement of low-energy gamma photons is complicated in heterogeneous samples containing high-density mineral phases and in such situations activity concentrations will be underestimated. This is because attenuation corrections, calculated based on sample mean density, do not properly correct where dense grains are dispersed within a less dense matrix (analogous to a nugget effect). The current method overcomes these problems using a lithium tetraborate fusion that readily dissolves all components including high-density, self-attenuating minerals/compounds. This is the ideal method for dissolving complex, non-volatile components in soils, rocks, mineral concentrates, and other materials where density reduction is required. Lithium borate fusion avoids the need for theoretical efficiency corrections or measurement of matrix matched calibration standards. The resulting homogeneous quenched glass produced can be quickly dissolved in nitric acid producing low-density solutions that can be counted by gamma spectrometry. The effectiveness of the technique is demonstrated using uranium-bearing Certified Reference Materials and provides accurate activity concentration determinations compared to the underestimated activity concentrations derived from direct measurements of a bulk sample. The procedure offers an effective solution for initial nuclear forensic studies where complex refractory minerals or matrices exist. It is also significantly faster, safer and simpler than alternative approaches.     

A sensitive and efficient method for trace analysis of some phenolic compounds using simultaneous derivatization and air‐assisted liquid–liquid microextraction from human urine and plasma samples followed by gas chromatography–nitrogen phosphorous detection

In present study, a simultaneous derivatization and air‐assisted liquid–liquid microextraction method combined with gas chromatography–nitrogen phosphorous detection has been developed for the determination of some phenolic compounds in biological samples. The analytes are derivatized and extracted simultaneously by a fast reaction with 1‐flouro‐2,4‐dinitrobenzene under mild conditions. Under optimal conditions low limits of detection in the range of 0.05–0.34 ng mL^?1 are achievable. The obtained extraction recoveries are between 84 and 97% and the relative standard deviations are less than 7.2% for intraday (n = 6) and interday (n = 4) precisions. The proposed method was demonstrated to be a simple and efficient method for the analysis of phenols in biological samples. Copyright © 2015 John Wiley & Sons, Ltd.     

电气材料铜及铜合金中痕量杂质砷元素的氢化物发生-原子荧光光谱法测定

本文建立了氢化物发生-原子荧光光谱法测定电气材料铜及铜合金中痕量杂质元素砷的方法。通过使用L-半胱氨酸与铜基体形成络合物,抗坏血酸充分预还原砷,消除了基体干扰,并实现了铜及铜合金中痕量杂质砷的准确测定。在经过优化的实验条件下,砷的检出限为0.12 ng·m L-1,线性相关系数优于0.999,相对标准偏差小于4%。用加标回收法测定实际样品,回收率在92%到103%之间。该法操作简便,灵敏度高,无需基体预分离。     

Ambiguous anti-fouling surfaces: Facile synthesis by light-mediated radical polymerization

In an attempt to create a polymer brush-based platform for the systematic study for anti-biofouling surfaces, the benefits of surface initiated, visible light-mediated radical polymerization are utilized to fabricate well-defined, chemically ambiguously patterned surfaces. A variety of analytical tools are used to illustrate the precise tuning of surface chemistry and thoroughly characterize spatially well-defined, hydrophilic/hydrophobic surfaces composed of poly(ethylene glycol methacrylate) and poly(trifluoroethyl methacrylate) with chemical definition on the micron scale. Advantages of both visible light-mediated photopolymerization and traditional copper-catalyzed atom transfer radical polymerization are combined to achieve both high spatial control and expanded monomer tolerance. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 253–262