Simple and rapid determination of N(6)-(Δ(2)-isopentenyl)adenine, zeatin, and dihydrozeatin in plants using on-line cleanup liquid chromatography coupled with hybrid quadrupole-Orbitrap high-resolution mass spectrometry.

A simple and rapid method was developed for the determination of three free cytokinins, namely, N(6)-(Δ(2)-isopentenyl)adenine, zeatin, and dihydrozeatin, in plants using TurboFlow on-line cleanup liquid chromatography combined with hybrid quadrupole-Orbitrap high-resolution mass spectrometry. The samples were extracted using acetonitrile, and then the extract was purified on a C18-p column, in which the sample matrix was removed and the analytes were retained. Subsequently, the analytes were eluted from the extraction column onto the analytical column (Hypersil Gold C18 column) prior to chromatographic separation and hybrid Q-Orbitrap detection using the targeted-MS(2) scan mode. The linearity was satisfactory with a correlation coefficient of >0.999 at concentrations ranging from 5-5000 pg/mL. The limits of quantification for the analytes ranged from 4.2-5.2 pg/mL. The intra- and inter-day average recoveries of analytes fortified at three levels ranged from 85.4-108.2%, and the intra- and inter-day relative standard deviations ranged from 4.04-8.57%. The method was successfully applied for the determination of free cytokinins in different tissue samples of Oryza sativa and Arabidopsis thaliana.

Popcorn-Inspired Expanded Graphite Microspheres with Controlled Morphology and Considerable Conductivity.

The structured processing of graphite is complex and challenging, in which expanded graphite plays a crucial role. Given its superior physical and chemical properties, expanded graphite finds extensive application in diverse domains such as electrochemistry and thermal management. However, the traditional preparation process is inconvenient in effectively meeting the design requirements on the macro and micro scales, which presents a challenge for the structured processing of expanded graphite materials. Here, an innovative method is first proposed for the controllable preparation of expanded graphite microspheres. Inspired by the explosion process of popcorn, the controlled gas release inside the natural flake graphite during chemical expansion is regulated by fuming sulfuric acid, realizing the controllable preparation of expanded graphite microspheres. Subsequently, sulfur trioxide can also intensify the degree of oxidation on the surface of the microspheres. The controllable microsphere morphology endows the composite with good isotropic network bonding, with considerable thermal conductivity of 1.703 W m-1 K-1 at low loading of 10 wt.% and reliable cyclic stability. This work opens up a new way for the morphology control of expanded graphite and provides a novel design thought for the physical and chemical structure control of carbon materials in the future.

Glass-Forming Ability, Mechanical Properties, and Energetic Characteristics of ZrCuNiAlNbHfY Bulk Metallic Glasses.

The effects of partially substituting Al for Cu in Zr59.62Cu18.4-xNi12Al6+xNb3Hf0.78Y0.2 (x = 0, 2, 4, 6, 8 at.%) bulk metallic glasses (BMGs) on their glass-forming ability (GFA), quasi-static and dynamic mechanical properties, and energy characteristics were investigated. The results showed that an appropriate substitution of Al for Cu can improve GFA and reach a critical casting size up to 10 mm. Additionally, with Al replacement of Cu, the change in the distribution and content of free volume inside the BMGs was the main reason for the quasi-static compression plasticity. In contrast, the BMGs exhibited no plasticity during dynamic compression and high-speed impact, owing to the short loading time and thermal softening effect. In terms of energy characteristics, all alloys have a high combustion enthalpy. And on the surface of the fragments collected from impact, the active elements Zr, Al, and Nb reacted because of the adiabatic temperature rise. Further, x = 4 at.% Zr-based BMG with its superior overall performance could penetrate a 6 mm Q235 plate at a speed of 1038 m/s, combining excellent mechanical properties and energy characteristics. This study contributes to the development of Zr-based BMGs as novel energetic structural materials.

Ignition and Combustion Characteristic of B·Mg Alloy Powders.

Boron and its alloys have been explored a lot and it is expected that they can replace pure aluminum powder in the energetic formulation of active materials. MgB2 compounds were prepared and characterized by a combination of mechanical alloying and heat treatment. The ignition and combustion of boron-magnesium alloys were studied with the ignition wire method and laser ignition infrared temperature measurement. The results show that MgB2 has good ignition characteristics with maximum ignition temperatures obtained by the two various methods of 1292 K and 1293 K, respectively. Compared with boron, the ignition temperature of MgB2 is greatly reduced after alloying. The ignition reaction of MgB2 mainly occurs on the surface and the ignition process has two stages. In the initial stage of ignition, the large flame morphology and combustion state are close to the combustion with gaseous Mg, whereas the subsequent combustion process is close to the combustion process of B. Compared with boron, the ignition temperature of MgB2 is greatly reduced which suggests that MgB2 may be used in gunpowder, propellant, explosives, and pyrotechnics due to its improved ignition performance.

Effects of Cerium Doping on the Mechanical Properties and Energy-Releasing Behavior of High-Entropy Alloys.

Energetic structural materials play an important role in improving the damage performance of future weapons. To improve the energy-releasing behavior, Al0.5NbZrTi1.5Ta0.8Cex high-entropy alloys were prepared by vacuum-arc melting. The results showed the presence of BCC and FCC phases in the alloy with dendritic-morphology-element segregation and there were significant dislocations in the alloys. The current study focused on the effects of cerium content on the dynamic compressive mechanical and energetic characteristics. Cerium doping enhanced the energy-releasing characteristics of high-entropy alloys. The severity of the reaction increased with the increase in the cerium content, while the dynamic compressive strength generally decreased with the increase in cerium content. The Al0.5NbZrTi1.5Ta0.8Ce0.25 showed excellent mechanical and energy-releasing characteristics. The ballistic experiments indicated that Al0.5NbZrTi1.5Ta0.8Ce0.25 can penetrate 6-millimeter A3 plates and ignite the cotton behind the target at a velocity of 729 m/s, making it an ideal energetic structural material.

Preparation and Characterization of Mg-Al-B Alloy (Mg0.5Al0.5B2) Via High-Temperature Sintering.

Boron and its alloys have long been explored as potential fuel and increasingly replace pure aluminum powder in high-energy formulations. The ignition and burning properties of boron can be improved by making boron alloys. In this study, an Mg-Al-B alloy was synthesized from magnesium, aluminum and boron powders in a 1:1:4 molar ratio by preheating to 600 °C for 30 min, followed by high-temperature sintering in a tube furnace. The effects of sintering temperature (700-1000 °C) and holding time (0.5-10 h) on the phase composition of mixed powders were studied. After the samples were cooled to room temperature, they were ground into powder. The phase composition, micromorphology and the bonding forms of elements of the synthesized samples were studied using XRD, SEM and XPS. The results show that each element exists in the form of simple substance in the alloy. The influence of the sintering temperature on the synthesis reaction of Mg0.5Al0.5B2 is very important, but holding time has little effect on it. With the increase of sintering temperature, the content of the Mg0.5Al0.5B2 phase gradually increases, and the phase content of residual metal gradually decreases. The phase and morphology analyses show that the optimum sintering temperature is 1000 °C with a minimum holding time of 0.5 h. It is expected to be used in gunpowder, propellant, explosives and pyrotechnics with improved characteristics.

[Determination of 15 amide herbicides in rice using monolith column for on-line solid-phase extraction coupled with liquid chromatography-tandem mass spectrometry].

A method based on on-line solid-phase extraction (SPE) coupled with high performance liquid chromatography-tandem mass spectrometry was developed for the simultaneous determination of 15 amide herbicides in rice. A poly(butyl methacrylate-co-ethylene dimethacrylate) monolithic column was utilized as the solid-phase column. The sample was extracted with acetonitrile, cleaned up with the monolithic column in online mode. Subsequently, the analyte was eluted from the extraction column onto the analytical column (Hypersil GOLD column) by 0.5%(v/v) formic acid aqueous solution-acetonitrile in gradient elution mode. Electrospray ionization mass spectrometry was performed in the positive mode and multiple reaction monitoring (MRM) mode. Under the optimized conditions, good linearities were obtained with correlation coefficients of more than 0.998. The limits of detection (LODs) and limits of quantification (LOQs) were in the range 0.20-2.0 µg/kg and 0.50-5.0 µg/kg, respectively. The average recoveries were in the range 75.5% to 121.3% at spiked levels of 2.0, 5.0, 10.0, and 50.0 µg/kg for 14 amide herbicides and 5.0, 10.0, 50.0, and 100.0 µg/kg for propanil. The relative standard deviations ranged from 2.89% to 12.38%. The proposed method is simple, rapid, and highly sensitive, and it can be applied to the simultaneous identification and quantification of the 15 amide herbicides in rice.

[Determination of 213 pesticide residues in milk and milk power by gas chromatography-triple quadrupole tandem mass spectrometry].

On the basis of the optimization of solid phase extraction adsorbent, eluting solvent types and amounts, a gas chromatography-triple quadrupole tandem mass spectrometry (GC-MS/MS) method was established for the determination of 213 pesticide residues in milk and milk power. The samples were extracted by acetonitrile, cleaned-up with an ENVI-Carb/NH2 solid-phase extractant, and determined by GC-MS/MS using external standard method. The linear ranges were from 10 to 1 000 µg/L for 197 pesticides, from 50 to 1 000 µg/L for the other 16 pesticides with the correlation coefficients higher than 0.99. The limits of detection (LODs, S/N = 3) varied over the range of 0.03 to 7.59 µg/kg, and limits of quantification (LOQs, S/N = 10) ranged from 0.10 to 21.94 µg/kg. The average recoveries in different matrices were in the range of 66.9% - 120.1% with the relative standard deviations (RSDs) of 1.23% - 17.6%. This method is simple, rapid, sensitive and reliable for meeting the requirements for the simultaneous identification and quantification of the multi-residues in milk and milk power.

[Simultaneous determination of penicillin and their major enzymatic metabolites in milk and milk powder by high performance liquid chromatography-tandem mass spectrometry].

A high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/ MS) method has been developed for the determination of eight compounds in milk and milk powder. They are four penicillins (penicillin G, penicillin V, amoxicillin and ampicillin) and four major beta-lactamase enzymatic metabolites of them (penilloic acid G, penilloic acid V, amoxiilloic acid and ampilloic acid). The compounds were extracted from the samples with acetonitrile and water, cleaned-up by HLB solid-phase extraction cartridges, and then detected by HPLC-MS/MS and quantified by external standard method. The linearities were satisfactory with the correlation coefficients > 0.99 at the mass concentrations ranging from 4 microg/L to 200 microg/L for penicillins and from 10 microg/L to 500 microg/L for enzymatic metabolites. The limits of detection and the limits of quantification were 5-50 microg/kg (S/N > or = 3) and 8-100 microg/kg (S/N > or = 10), respectively. The average recoveries of the eight compounds were 83.48%-96.97% in milk and 82.70%-95.14% in milk powder. The relative standard deviations (RSDs) in milk and milk powder were 3.86%-10.87% and 3.02%-9.81%, respectively. In conclusion, the established method is convenient, accurate and sensitive so that it can be applied to the determination of penicillin residues and enzymatic metabolites in milk and milk powder.

[Determination of 46 plasticizers in food contact polyvinyl chloride packaging materials and their migration into food simulants by gas chromatography-mass spectrometry].

A gas chromatography-mass spectrometry (GC-MS) method was developed for the determination of 46 plasticizers in food contact polyvinyl chloride (PVC) packaging materials and their migration into food simulants, i. e. water, 3% acetic acid, 10% ethanol and olive oil. Plasticizers in the PVC packaging materials, aqueous food simulants and olive oil food simulants were extracted by the dissolution-precipitation, liquid-liquid extraction and gel permeation chromatography (GPC) approaches, respectively. The extracts were analyzed by GC-MS in selective ion monitoring (SIM) mode and quantified using the external standard method. The cal-ibration curves were linear in the ranges of 0.1-2.0 mg/L with the correlation coefficients of 0.9910-0. 999 9. The limits of detection were from 0. 005 mg/kg to 0. 05 mg/kg ( S/N = 5 ). The recoveries at 3 spiked levels were 69.51%-107. 21% and the relative standard deviations (RSDs n = 6) ranged from 3.53% to 18.95%. These results show that this method is fast, sensitive and accurate for the qualitative and quantitative determination of plasticizers in food contact plastic products and 4 types of food simulants.

[Analysis of pesticide multiresidues in rice by gas chromatography-mass spectrometry coupled with solid phase extraction].

A new analytical method was developed to simultaneously determine multiple pesticide residues in rice including organophosphorus, organochlorine, carbamate and pyrethroid. First, the solvents for pesticide extraction were selected for optimization. Eight solvents were screened to find that the extraction efficiency with dichloromethane was the best. Second, clean-up was performed by solid phase extraction using a Florisil cartridge. Various mixtures of hexane and acetone were tested to show that the mixture of hexane-acetone (4:1, v/v) had the best performance. The clean-up helped the sample purification significantly. The prepared sample was analyzed using gas chromatography-mass spectrometry (GC-MS) in selected ion monitoring (SIM) mode. The pesticides were identified with retention time and selected ions and their relative abundances, and they were quantified based on extract of spiking standards in a blank sample. The limits of detection (LODs) were evaluated on the values of the lower concentration fortified sample under the signal-to-noise ratio of 3:1. The recoveries and relative standard deviations (RSDs) were checked by adding pesticide standard solution at two levels to untreated samples, and the triplicate analysis of the samples were carried out for each spiked level. The LODs were at microg/kg level. The average recoveries of most pesticides were from 75% to 120 %. The RSDs were less than 10.4% (n = 3). These results indicated that this method is simple, rapid, sensitive for the simultaneous determination requirements of multiple pesticide residues in rice.