Bombyx mori silk fibroin-based materials have good biocompatibility and biodegradability. In order to maximize their utility while maintain appropriate features, silk fibroin (SF) films were modified with reduced glutathione (GSH) (NH2)–ECG–(COOH), using the carbodiimide chemistry method, for the introduction of thiol groups onto surfaces. The effects of this modification on SF films’ chemical and physical properties, and cytotoxicity were assessed. The chemical and elemental composition analysis results suggested that reduced glutathione (GSH) was covalently coupled onto the surface of silk fibroin films. Atomic force microscopy (AFM) results indicated the surface roughness of silk fibroin film was increased after the modification by GSH. The GSH-modified silk fibroin films also showed the smaller contact angle due to the hydrophilic peptides coupled on the film surface. Through MTT assay, it was shown that the chemically modified SF film was not cytotoxic to HEK293 cells, and it had no adverse influence on the growth of HEK293 cells. Our approach provides a new option to engineer SF-based material surface with thiol groups in order to allow for secondary reactions and holds great promise for applications of SF-based materials in the biomedical field.

Volatile halogenated hydrocarbons (VHHs) are annually produced and released into the environment, posing a threat to public health. In this study, a simple, rapid, sensitive and automated method based on headspace and gas chromatography (GC) with electron-capture detection was described for the determination of VHHs in different concentration levels in water samples. The proposed headspace GC method was initially optimized, and the optimum experimental conditions found were 10-mL water sample containing 20% w/v sodium chloride placed in a 20-mL vial and stirred at 60°C for 35 min, and then 14 VHHs were well separated on DB-35 MS capillary column with a split ratio of 12.5: 1. The limits of detection were in the low μg/L level, ranging between 0.01 and 0.6 μg/L. Finally optimized method was applied for determination 14 VHHs in drinking and environmental waters. The total mean concentrations of VHHs were 34.962, 26.183, 3.228 and 647.344 μg/L in tap water, purified water with 1-year-old filter element, seawater and effluents, respectively. However, no VHHs was detected in purified water with a new filter element. The main composition is different among different water matrix, which may be attributed to their different sources.

A simple, rapid and novel method has been developed and validated for determination of 16 phthalates in marine sediment samples by gas chromatography coupled to mass spectrometry. Freeze dried samples were first ultrasonic extraction by n-hexane:methylene chloride (1:1, v/v) and n-hexane:ethyl acetate (1:1, v/v) and followed by dispersive solid-phase extraction cleanup. The linearity of this method ranged from 1 to 1,000 μg/L, with regression coefficients ranging between 0.9993 and 0.9999. The limits of detection were in ng/g level, ranging between 0.1 and 0.25 ng/g (dry weight). The concentration of the total phthalates in marine sediment samples from Waters of Dongji (Zhoushan, China), Yueqing Bay (Wenzhou, China) and Coastal Waters of Yuhuan (Taizhou, China) ranged from 235.4 to 608.7 μg/kg with diisobutyl phthalate, dibutyl phthalate and di(2-ethylhexyl) phthalate being the major species, which constitutes of 94.6 and 98.1% of the total phthalates. The recoveries of spiked 16 phthalates at different concentration levels in sediment sample 3 of Waters of Dongji (Zhoushan, China) and sediment sample 3 of Yueqing bay (Wenzhou, China) were in the range of 78–117% and 83–114%, respectively, with relative standard deviations of 2.4–6.8% and 3.4–7.5% (n = 5), respectively. The performance of the proposed method was also compared with traditional Soxhlet extraction and column chromatography cleanup on the same genuine sediment samples and comparable efficiencies were obtained. It is concluded that this method can be successfully applied for the determination of phthalates in different marine sediment samples.