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The biomonitoring of hydroxy polycyclic aromatic hydrocarbons in urine, as a direct way to access multiple exposures to polycyclic aromatic hydrocarbons, has raised great concerns due to their increasing hazardous health effects on humans. Solidphase extraction is an effective and useful technique to preconcentrate trace analytes from biological samples. Here, we report a novel solid-phase extraction method using a graphene oxide incorporated monolithic syringe for the determination of six hydroxy polycyclic aromatic hydrocarbons in urine coupled with liquid chromatographytandem mass spectrometry. The effect of graphene oxide amount, washing solvent, eluting solvent, and its volume on the extraction performance were investigated. The fabricated monoliths gave higher adsorption efficiency and capacity than the neat polymer monolith and commercial C 18 sorbent. Under the optimum conditions, the developed method provided the detection limits (S/N = 3) of 0.02-0.1 ng/mL and the linear ranges of 0.1-1500 ng/mL for six analytes in urine sample. The recoveries at three spiked levels ranged from 77.5 to 97.1%. Besides, the intra column-to-column (n = 3) and inter batch-to-batch (n = 3) precisions were ≤ 9.8%. The developed method was successfully applied for the determination of hydroxy polycyclic aromatic hydrocarbons in urine samples of coke oven workers.

Background:For Chinese patients with hepatocellular carcinoma (HCC), surgical resection is the most important treatment to achieve long-term survival for patients with an early-stage tumor, and yet the prognosis after surgery is diverse. We aimed to construct a scoring system (Shanghai Score) for individualized prognosis estimation and adjuvant treatment evaluation.Methods:A multivariate Cox proportional hazards model was constructed based on 4166 HCC patients undergoing resection during 2001–2008 at Zhongshan Hospital. Age, hepatitis B surface antigen, hepatitis B e antigen, partial thromboplastin time, total bilirubin, alkaline phosphatase, γ-glutamyltransferase, α-fetoprotein, tumor size, cirrhosis, vascular invasion, differentiation, encapsulation, and tumor number were finally retained by a backward step-down selection process with the Akaike information criterion. The Harrell's concordance index (C-index) was used to measure model performance. Shanghai Score is calculated by summing the products of the 14 variable values times each variable's corresponding regression coefficient. Totally 1978 patients from Zhongshan Hospital undergoing resection during 2009–2012, 808 patients from Eastern Hepatobiliary Surgery Hospital during 2008–2010, and 244 patients from Tianjin Medical University Cancer Hospital during 2010–2011 were enrolled as external validation cohorts. Shanghai Score was also implied in evaluating adjuvant treatment choices based on propensity score matching analysis.Results:Shanghai Score showed good calibration and discrimination in postsurgical HCC patients. The bootstrap-corrected C-index (confidence interval [CI]) was 0.74 for overall survival (OS) and 0.68 for recurrence-free survival (RFS) in derivation cohort (4166 patients), and in the three independent validation cohorts, the CIs for OS ranged 0.70–0.72 and that for RFS ranged 0.63–0.68. Furthermore, Shanghai Score provided evaluation for adjuvant treatment choices (transcatheter arterial chemoembolization or interferon-α). The identified subset of patients at low risk could be ideal candidates for curative surgery, and subsets of patients at moderate or high risk could be recommended with possible adjuvant therapies after surgery. Finally, a web server with individualized outcome prediction and treatment recommendation was constructed.Conclusions:Based on the largest cohort up to date, we established Shanghai Score – an individualized outcome prediction system specifically designed for Chinese HCC patients after surgery. The Shanghai Score web server provides an easily accessible tool to stratify the prognosis of patients undergoing liver resection for HCC.

A novel diatomite-supported zeolitic imidazolate framework-8 sorbent (ZIF-8@Dt-COOH) was in situ fabricated and developed for solid-phase extraction of three benzodiazepines (triazolam, midazolam and diazepam) in urine followed by high-performance liquid chromatography. ZIF-8@Dt-COOH was easily prepared by coating ZIF-8 on the surface of Dt-COOH and characterized by Fourier transform infrared spectra, X-ray powder diffractometry and scanning electron microscopy. Compared with bare Dt-COOH, the extraction efficiency of ZIF-8@Dt-COOH for the target was significantly increased from 20.1–39.0% to 100%. Main extraction parameters, including ionic strength and pH of solution, loading volume, washing solution, elution solvent and elution volume, were optimized in detail. Under optimum conditions, the developed method gave linearity of three BZDs in 2–500 ng/mL (r ≥ 0.9995). Limits of detection (S/N = 3), and limits of quantification (S/N = 10) were 0.3–0.4 ng/mL and 1.0–1.3 ng/mL, respectively. In addition, the average recoveries at three spiked levels (5, 10 and 20 ng/mL) varied from 80.0% to 98.7%, with the intra-day and inter-day precisions of 1.4–5.2% and 1.5–8.2%, respectively. The proposed method provided an effective purification performance and gave the enrichment factors of 24.0–29.6. The proposed method was successfully employed for the accurate and sensitive determination of benzodiazepines in urine.

A poly(N,N-dimethylaminoethyl methacrylate-co-ethylene glycol dimethacrylate) monolith was successfully synthesized and applied for direct solid-phase extraction of benzodiazepines from undiluted urine samples.