Extraction of parabens by melamine sponge with determination by high-performance liquid chromatography

In the present study, we propose a novel method for the extraction of parabens in personal care products. A new, simple adsorptive material was obtained by combining metal-organic frameworks and melamine sponges using the adhesive property of polyvinylidene fluoride. This new material, metal-organic frameworks/melamine sponges, was found to be particularly suitable for solid-phase extraction. The structural characteristics of metal-organic frameworks/melamine sponges were first analyzed by scanning electron microscopy. Subsequently, solid-phase extraction was performed on sample solutions, and the extracted substances were then analyzed by high-performance liquid chromatography. Following optimization of important experimental conditions, excellent recovery rates were obtained. Our novel method was then applied to the extraction of four parabens (methylparahydroxybenzoates, ethylparahydroxybenzoates, propylparahydroxybenzoates, and butylparahydroxybenzoates) from real samples. The results yielded limits of detection of 0.26–0.41 ng/mL. The inter- and intra-day recoveries were 104.0–109.7% and 91.2–98.1%, respectively (relative standard deviation, <13.8%).     

In-situ grown metal organic framework synergistic system for the enantioseparation of three drugs in open tubular capillary electrochromatography

Metal organic frameworks have received great attention as the chiral stationary phase for racemic drug separation because of their fascinating structures and properties. However, the most homochiral metal organic frameworks were constructed by rare and precious chiral organic ligands. In this work, an achiral metal organic framework, together with a natural chiral selector carboxymethyl β-cyclodextrin built a synergistic separation system in the open tubular capillary electrochromatography. The novel coated columns were developed by inducing metal organic framework nanoparticles to grow on the imidazolyl functional capillary inner wall. The baseline separations of hydroxychloroquine, ofloxacin, and atenolol were achieved in the synergistic separation system. The effects of the concentration of chiral selector, pH, voltage, and the concentration of organic additives were studied. Compared with chiral selector auxiliary bare capillary, the resolutions of three drugs were remarkably improved. The relative standard deviations for the retention time of intraday (n = 6), interday (n = 6), and column-to-column were less than 2.1, 2.6, and 5.2%, respectively. These results demonstrate that affordable synergistic separation systems are prospective for racemic drug enantioseparation in capillary electrochromatography.     

Facile synthesis of a novel magnetic covalent organic frameworks for extraction and determination of five fungicides in Chinese herbal medicines

A novel magnetic covalent organic framework was synthesized via a one-step coating approach with solvothermal reaction employing 2,4,6-tris(4-aminophen-yl)-1,3,5-triazine and 2,4,6-triformylphloroglucinol as two building blocks by covalent bonding. The prepared magnetic covalent organic frameworks were properly characterized by different techniques and employed as adsorbents of magnetic solid-phase extraction. An analytical method was developed for the simultaneous determination of five fungicides in two Chinese herbal medicine samples via magnetic solid-phase extraction coupled to ultra high performance liquid chromatography with tandem mass spectrometry analysis. Under optimized magnetic solid-phase extraction conditions, the method exhibited satisfactory recoveries (74.0−109.6%) with relative standard deviations of 0.4−4.6%, low limits of detection (0.003−0.015 μg/kg), and good linearity (R² > 0.9960). Compared with the traditional extraction method, the proposed method required a lower amount of adsorbent (3 mg) and extraction time (5 min). The adsorbent also had favorable reusability (not less than eight times). Therefore, the magnetic covalent organic frameworks could be a promising adsorbent for the extraction and quantitation of fungicides in Chinese herbal medicines.     

热熔灌输法制备三维骨架支撑金属锂复合负极

金属锂因具有极高的理论比容量(3860 mAh/g)和最低的电化学势(相对于标准氢电极为-3.04 V),被认为是下一代高比能锂离子电池的首选负极材料。然而,金属锂负极在电池循环过程中发生的刺状枝晶生长和体积变化等问题严重阻碍了其产业化应用进程。近年来研究表明,通过在金属锂中引入具有三维(3D)结构的宿主骨架,不但能有效抑制锂枝晶的生长,而且可以缓解金属锂负极的体积变化,从而提高金属锂电池的循环性能与安全性。因此,设计3D骨架/金属锂复合负极被认为是一种能有效解决金属锂问题的新兴策略。本文综述了热熔灌输法制备3D骨架/金属锂复合负极的研究进展。首先讨论了当前基于3D骨架的预存金属锂技术,然后着重分析了热熔灌输策略中3D骨架锂润湿性的影响因素,以及不同3D骨架修饰特征和改性方法。最后对3D骨架/金属锂复合负极和热熔灌输策略现存问题进行了总结并提出未来的发展方向。     

冶金法生产太阳能级硅的除硼方法、技术及工艺

太阳能作为一种绿色可再生能源受到了广泛关注,而杂质去除是从冶金级硅中获得太阳能级硅所需的纯化过程,对硅基太阳能电池的制备至关重要。冶金法制备太阳能级多晶硅新工艺技术由于其能耗低、成本低和污染少等优点,成为研究开发的热点,但如何有效地去除硼是我们面临的最严峻的挑战之一。本文综述了硼的热力学和动力学性质(溶解度、扩散率、扩散系数、传质系数和活度系数)以及近年来除硼的相关课题研究(吹气、炉渣处理、等离子体处理、酸浸和溶剂精炼)。研究发现,溶剂精炼是一种很有前途的获取高纯硅的方法,硅的富集率以及硼的去除率均可达到90%以上,而添加剂能够加强硼化物的形成和析出来改进除硼工艺,且后续几乎可被完全消除,不会对精炼硅造成污染,这将更加有效除硼并增加工艺实用性。最后本文对几种除硼工艺进行了比较分析,并对冶金法的应用前景进行了展望。     

LC–MS3 Strategy for Quantification of Carbamazepine in Human Plasma and Its Application in Therapeutic Drug Monitoring

This study developed a detection method based on the strategy of HPLC/MS³ and verified its suitability by quantifying carbamazepine in human plasma. The high-performance liquid chromatography–tandem mass spectrometry (HPLC/MS³) system was performed using a Shimadzu UFLC XR liquid chromatography and a SCIEX QTRAP^® 5500 linear ion trap triple quadrupole mass spectrometer. The specific operation was as follows: the sample protein was firstly precipitated using methanol, then carbamazepine and carbamazepine-D₂N¹⁵ were separated on an ACQUITY UPLC HSS T3 column using the gradient elution with solvent A (0.1% formic acid) and solvent B (0.1% formic acid in acetonitrile) at a flow rate of 0.25 mL/min. Each sample was run for 7 min. This method was validated for various parameters including accuracy, precision, selectivity, linearity, LLOQ, etc. Only 5 μL of sample plasma could obtain the result of LLOD 0.5 µg/mL. The intra-day and inter-day precision was <8.23%, and accuracy was between −1.74% and 2.92%. This method was successfully used for monitoring the blood concentration of epilepsy patients after carbamazepine treatment.     

Recent advances of organometallic complexes in emerging photovoltaics

Organometallic complexes (OMCs) consisting of organic and metal active moieties have shown immense potential for application in solar cells. The diverse structure, rich porosity, and unique charge centers of OMCs enable them to be functional in solar cells. In this review, we introduced four types of OMCs, such as crown organometallic complexes, β-diketone metal complexes, cyclometallic complexes, and main chain metal-containing polymers, providing an in-depth analysis of the structure-performance relationship. OMCs could serve as active or interlayer materials in a variety of solar cell systems such as organic solar cells, perovskite solar cells, and dye-sensitized solar cells, especially some metals to improve the photoelectric performance of the device as dopants. In the end, perspectives on the opportunities and challenges of OMCs are given.     

High-efficient surface tailoring via reverse atom transfer radical polymerization and reversible addition-fragmentation chain-transfer polymerization in an aqueous system initiated by a monocenter redox pair

The commonly used multi-center initiation methods always lead to the formation of quantities of homopolymer in the surface tailoring based on reverse atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain-transfer (RAFT) polymerization. In this study, a monocenter redox pair constructed of silica bearing tert-butyl hydroperoxide groups and ascorbic acid (SiO₂-TBHP/AsAc) was applied to substitute the commonly used initiation method of R-supported RAFT grafting polymerization. All the propagating radicals were restricted on the surface of solid particles during the whole procedure theoretically, resulting in a higher grafting efficiency of 95.1% combined with the “controllable” feature at 10 h. This redox pair was also used to initiate the reverse ATRP in miniemulsion successfully with a grafting efficiency of 86.3% at 10 h. The grafting efficiency obtained under this monocenter initiation method was significantly higher than that of the frequently reported surface modification by reverse ATRP and RAFT polymerization. In addition, the high-efficient surface tailoring was traced and confirmed by nuclear magnetic resonance, Fourier transform infrared, X-ray photoelectron spectroscopy, thermogravimetric analysis, transmission electron microscopy, and other analysis tests. The advantage of this monocenter redox pair will open a new avenue for the potential “high-efficient” surface tailoring of various materials.     

On-surface synthesis of porous graphene nanoribbons containing nonplanar [14]annulene pores

The precise introduction of nonplanar pores in the backbone of graphene nanoribbon represents a great challenge. Here, we explore a synthetic strategy toward the preparation of nonplanar porous graphene nanoribbon from a predesigned dibromohexabenzotetracene monomer bearing four cove-edges. Successive thermal annealing steps of the monomers indicate that the dehalogenative aryl-aryl homocoupling yields a twisted polymer precursor on a gold surface and the subsequent cyclodehydrogenation leads to a defective porous graphene nanoribbon containing nonplanar [14]annulene pores and five-membered rings as characterized by scanning tunneling microscopy and noncontact atomic force microscopy. Although the C–C bonds producing [14]annulene pores are not achieved with high yield, our results provide new synthetic perspectives for the on-surface growth of nonplanar porous graphene nanoribbons.