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Despite increased interest in microplasma-induced vapor generation (μPIVG) over the past several years, applications in real sample analyses remain limited due to their relatively low vapor generation efficiency and ambiguous mechanism. In this work, a novel method using methanol for significantly enhancing the liquid electrode discharge μPIVG efficiency was developed for the simultaneous and sensitive determination of Hg, Cd, and Zn by atomic fluorescence spectrometry (AFS). It is worth noting that the possible enhancement mechanism was investigated via the characterizations of volatile products by AFS, microplasma optical emission spectrometry, online gas chromatography, and gas chromatography-mass spectrometry, which involved the reductive species such as electrons, hydrogen radicals (·H), methyl radicals (·CH 3 ), and other intermediates in the argon plasma adding methanol. Under the optimized conditions, the limits of detection of 0.007, 0.05, and 0.5 μg L -1 were obtained for Hg, Cd, and Zn, respectively, with relative standard deviations of 3.1, 3.7, and 5.2% for these elements, respectively. Vapor generation efficiencies of 90, 83, and 55% were achieved for Hg, Cd, and Zn, respectively, and improved 2.7-, 4.8-, and 7.9-fold, respectively, compared to those obtained in the absence of methanol. The accuracy and practicability of the proposed method were validated by the determination of Hg, Cd, and Zn in a certified reference material (CRM, Lobster hepatopancreas, TORT-3) and crayfish samples collected from three different provinces of China.

Background: Thus far, the association of tumor size with prognosis in colon cancer has not been considered and has remained unclear. This study, therefore, aimed to investigate the association between tumor size as a continuous variable and prognosis in colon cancer using Cox models with restricted cubic splines., Methods: Using the Surveillance, Epidemiology, and End Results database, we selected 128,369 patients with colon cancer who underwent surgery. Overall survival and colon cancer-specific survival were separately analyzed, and tumor size was separately evaluated as a continuous variable and a categorical variable. To investigate the relationship after adjusting for covariates, we used the proportional hazards models. The restricted cubic splines model was used to determine the presence of nonlinear or linear association and flexibly visualize the association., Results: The adjusted covariate model showed that the hazard ratio of colon cancer rapidly increased with a tumor size of 4 cm and slowly increased with a tumor size larger than 4 cm. When tumor size was analyzed as a categorical variable, the multivariable-adjusted model demonstrated a nearly linear relationship between tumor size and hazard ratio regardless of overall survival or cancer-specific survival, and the hazard ratio of group 5 (4.1-5 cm) was nearly a turning point. Subgroup analysis with respect to lymph node metastasis showed that the relationship between tumor size and prognosis in colon cancer was evident in lymph node metastasis., Conclusion: There was a strong negative relationship between tumor size and prognosis in colon cancer. However, when tumor size was less than 4 cm, the relationship between tumor size and prognosis was steep compared with that when tumor size was larger than 4 cm, especially in lymph node metastasis., (Copyright © 2020. Published by Elsevier Inc.)

DNAzymes have emerged as a powerful class of sensors for metal ions due to their high selectivity over a wide range of metal ions, allowing for on-site and real-time detection. Despite much progress made in this area, detecting and quantifying tightly bound metal ions, such as those in the blood serum, remain a challenge because the DNAzyme sensors reported so far can detect only mobile metal ions that are accessible to bind the DNAzymes. To overcome this major limitation, we report the use of a photocaged chelator, XDPAdeCage to extract the Zn 2+ from the blood serum and then release the chelated Zn 2+ into a buffer using 365 nm light for quantification by an 8-17 DNAzyme sensor. Protocols to chelate, uncage, extract, and detect metal ions in the serum have been developed and optimized. Because DNAzyme sensors for other metal ions have already been reported and more DNAzyme sensors can be obtained using in vitro selection, the method reported in this work will significantly expand the applications of the DNAzyme sensors from sensing metal ions that are not only free but also bound to other biomolecules in biological and environmental samples.

Purpose: Tumors with lymphovascular invasion (LVI) are thought to be associated with lymph node metastasis and to lead to a worse prognosis. However, the effect of LVI on the prognosis of adenocarcinoma of esophagogastric junction (AEG) is still unclear., Patients and Methods: We retrospectively analyzed 224 consecutive patients with non-metastatic AEG who underwent radical surgery in our hospital from 2004 to 2018. Inverse probability weighting (IPW) analysis was used to eliminate the selection bias. IPW-adjusted Kaplan-Meier curves and Cox proportional hazards models were used to compare disease-specific survival (DSS) and overall survival (OS) between patients with and without LVI., Results: A total of 224 patients with non-metastatic AEG who underwent radical resection were included in the study and 96 (42.9%) patients developed LVI. Survival analysis showed that LVI were associated with worse DSS (hazard ratio (HR) = 3.12; 95% CI: 1.93-5.03) and worse OS (HR = 2.33; 95% CI: 1.61-3.38). The results were consistent across subgroups stratified by pathologic N stage. Subgroup analysis demonstrated that Siewert type III (HR= 3.20, 95% CI: 1.45-7.06) was associated with worse DSS, but not Siewert type I/II (HR= 1.46, 95% CI: 0.94-2.31, P-interaction=0.047)., Conclusion: LVI are associated with worse prognosis in AEG. LVI had a worse effect on DSS in Siewert type III AEG than Siewert type I/II AEG., Competing Interests: All authors declare no conflicts of interest related to this article., (© 2020 Zheng et al.)

A simple, portable and battery-powered trapping device (iTrap) consisting of a purification tube, a trapping unit and a miniature air pump was developed for the pre-concentration of volatile organic sulfur compounds (VOSCs). The tested VOSCs, including methanthiol (MT), ethanethiol (ET), dimethyl sulfide (DMS), diethyl sulfide (DES) and dimethyl disulfide (DMDS), were firstly purged from water samples and then in situ pre-concentrated with the iTrap prior to their analysis by thermal desorption gas chromatography coupling with a sulfur chemiluminescence detector (TD-GC-SCD). Twenty-six adsorbents were studied to find the most suitable adsorbent for the efficient pre-concentration of VOSCs. Under optimal conditions, limits of detection of 6, 8, 6, 2 and 3 ng L -1 were obtained for MT, ET, DMS, DES and DMDS, respectively. The precisions were better than 5.3% (relative standard deviations, RSDs). The iTrap was successfully applied for the analysis of VOSCs in Certified Reference Materials, several surface water, underground water and wastewater samples collected from Pengzhou city, Sichuan, China. Moreover, the VOSCs trapped in the iTrap were much more stable than those directly stored in water samples and the recoveries for all samples could be maintained at acceptable levels (>73%), even their preservation time as long as 8 h., Competing Interests: Declaration of Competing Interest We declare that we have no conflicts of interest to this work. Meanwhile, we also declare that we do not have any commercial or associative interest that represents a conflict of interest in connection with the work submitted., (Copyright © 2020. Published by Elsevier B.V.)

Recently, the use of atomic spectrometry (AS) for biochemical analysis has attracted considerable attention due to its high sensitivity, selectivity and anti-interference ability. In this work, we conducted a detailed study on a phenomenon of thiol inhibition of mercury (Hg 2+ ) cold vapor generation (CVG) and found L -cysteine ( L -Cys), glutathione (GSH), dithiothreitol, N-Acetyl-L-cysteine, 3-mercaptopropionic acid, β-mercaptoethanol, and NaI can inhibit the CVG of Hg 2+ , while EDTA has no inhibitory effect. Furthermore, changing the content of -SH can effectively adjust the CVG atomic fluorescence spectrometer (CVG-AFS) signal of Hg 2+ . As as a consequence, an AS-based homogeneous bioassay was constructed by adjusting the oxidation ratio and production quantity of -SH in the system. The quantitative analysis of the system was demonstrated by using AFS as a representative detector. Hydrogen peroxide (H 2 O 2 ) and glucose were used as representative analytes for the validation of Hg 2+ atomic fluorescence signal turn-off strategy, and butyrylcholinesterase (BChE) as well as parathion (organophosphorus pesticides, OPs) as utilized as representative targets for the signal turn-on strategy. Under optimal experimental conditions, the homogeneous CVG-AFS sensor can be successfully used to detect 3 μM H 2 O 2 , 30 μM glucose, 0.25 U/L BChE, and 0.4 μg/mL parathion. In addition, the detection results of glucose and BChE in human serum samples agreed well with those obtained by using glucometer and kit, showing the promising potential of this method for practical applications. Therefore, this work provides a perspective for the construction of AS-based homogeneous bioassays and shows great potential for the detection of biomarkers., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier B.V. All rights reserved.)

Background: Nonculprit lesions are the major cause of future cardiovascular events. However, the natural course of nonculprit lesions and angiographic predictors of plaque progression are not well-studied. The purpose of our study was to observe the natural course of nonculprit lesions, and to identify predictors of unanticipated future events and angiographic progression in nonculprit lesions., Methods: We analyzed 640 nonculprit lesions with a length of ≥2 mm and luminal narrowing ≥30% from 320 patients who had two serial angiographic follow-ups; 9 to 13 months post-PCI and 24 months post-PCI. The study endpoints were nonculprit-ischemia driven revascularization (IDR) and the rate of diameter stenosis (DS) progression. Those with progression of DS > 12%/year were defined as 'rapid progressors'., Results: During the median follow-up period of 737 days, 20 lesions in 20 patients (6.3%) required nonculprit-IDR. Independent predictors of nonculprit-IDR were diabetes (hazard ratio [HR] 2.93, 95% confidence interval [CI] 1.072-8.007, p = 0.036) and lesion type B2/C (HR 4.017, 95% CI 1.614-9.997, p = 0.003). The presence of one or both of the two major risk factors was associated with significant DS progression (3.0 ± 6.8% vs. 3.5 ± 6.1% vs. 6.8 ± 9.9% for lesions with 0, 1 and both risk factors, p < 0.001). Among the 640 lesions, 38 lesions (5.9%) in 33 patients were rapid progressors, while risk factors of rapid progressors included lesion type B2/C as a lesion-related risk factor (HR 1.998, 95% CI 1.006-3.791, p = 0.048) and diabetes mellitus as a patient-related risk factor (HR 3.725, 95% CI 1.937-7.538, p < 0.001). Lesions with both risk factors (type B2/C lesions in diabetic patients) were at the highest risk of rapid progression (odds ratio 3.250, 95% CI 1.451-7.282), compared to type A/B1 lesions in non-diabetic patients., Conclusion: Nonculprit-IDR was not uncommon during the 2-year follow up period in our population. The major risk factors of nonculprit lesion progression were diabetes and lesion type B2/C., Trial Registration: Retrospectively registered and approved by the institutional review board of Seoul National University Hospital (No.: 1801-138-918) on February 2nd, 2018.

A low-cost, simple, and highly selective analytical method was developed for sensitive visual detection of selenium in human urine both outdoors and at home, by coupling hydride generation with headspace solid-phase extraction using quantum dots (QDs) immobilized on paper. The visible fluorescence from the CdTe QDs immobilized on paper was quenched by H2Se from hydride generation reaction and headspace solid-phase extraction. The potential mechanism was investigated by using X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) as well as Density Functional Theory (DFT). Potential interferences from coexisting ions, particularly Ag(+), Cu(2+), and Zn(2+), were eliminated. The selectivity was significantly increased because the selenium hydride was effectively separated from sample matrices by hydride generation. Moreover, due to the high sampling efficiency of hydride generation and headspace solid phase extraction, the sensitivity and the limit of detection (LOD) were significantly improved compared to conventional methods. A LOD of 0.1 μg L(-1) and a relative standard deviation (RSD, n = 7) of 2.4% at a concentration of 20 μg L(-1) were obtained when using a commercial spectrofluorometer as the detector. Furthermore, a visual assay based on the proposed method was developed for the detection of Se, 5 μg L(-1) of selenium in urine can be discriminated from the blank solution with the naked eye. The proposed method was validated by analysis of certified reference materials and human urine samples with satisfactory results.

It is critically important to accurately determine histidine since it is an indicator for many diseases when at an abnormal level. Here, an inexpensive and simple method using an amine-functionalized magnetic nanoparticle-based Ni(2+)-histidine affinity pair system was developed for highly sensitive and selective detection of histidine in human urine by photochemical vapor generation atomic spectrometry. Ni(2+) was first bound to the amine groups of the amine-functionalized magnetic nanoparticles and then liberated to solution via the highly specific interaction between the histidine and Ni(2+) in the presence of histidine. The liberated histidine-Ni(2+) complex was exposed to UV irradiation in the presence of formic acid to form gaseous nickel tetracarbonyl, which was separated from the sample matrix and determined by atomic absorption/fluorescence spectrometry. Compared to other methods, this approach promises high sensitivity, simplicity in design, and convenient operation. The need for organic solvents, enzymatic reactions, separation processes, chemical modification, expensive instrumentations, and sophisticated and complicated pretreatment is minimized with this strategy. A limit of detection of 1 nM was obtained and provided tens-to-hundreds of fold improvements over that achieved with conventional methods. The protocol was evaluated by analysis of several urine samples with good recoveries and showed great potential for practical application.

It was found that carbon atomic emission can be excited in low temperature dielectric barrier discharge (DBD), and an atmospheric pressure, low power consumption, and compact microplasma carbon atomic emission spectrometer (AES) was constructed and used as a universal and sensitive gas chromatographic (GC) detector for detection of volatile carbon-containing compounds. A concentric DBD device was housed in a heating box to increase the plasma operation temperature to 300 °C to intensify carbon atomic emission at 193.0 nm. Carbon-containing compounds directly injected or eluted from GC can be decomposed, atomized, and excited in this heated DBD for carbon atomic emission. The performance of this new optical detector was first evaluated by determination of a series of volatile carbon-containing compounds including formaldehyde, ethyl acetate, methanol, ethanol, 1-propanol, 1-butanol, and 1-pentanol, and absolute limits of detection (LODs) were found at a range of 0.12-0.28 ng under the optimized conditions. Preliminary experimental results showed that it provided slightly higher LODs than those obtained by GC with a flame ionization detector (FID). Furthermore, it is a new universal GC detector for volatile carbon-containing compounds that even includes those compounds which are difficult to detect by FID, such as HCHO, CO, and CO2. Meanwhile, hydrogen gas used in conventional techniques was eliminated; and molecular optical emission detection can also be performed with this GC detector for multichannel analysis to improve resolution of overlapped chromatographic peaks of complex mixtures.

Because of its unique properties and capability of formation of well-dispersed aqueous colloids in aqueous phase, graphene oxide can be used for the efficient preconcentration of heavy metal ions prior to their determination. The complete collection of graphene oxide colloids from water has generally been considered to be insurmountable. Here, graphene oxide aggregation triggered by introducing NaCl was used to develop a novel organic solvent-free cloud point extraction-like method for the determination of trace toxic metals. The graphene oxide sheets were uniformly dispersed in aqueous samples or standard solutions for a fast and efficient adsorption of Pb(II), Cd(II), Bi(III), and Sb(III) owing to its hydrophilic character and the electrostatic repulsion among the graphene oxide sheets, and its aggregation immediately occurred when the electrostatic repulsion was eliminated via adding NaCl to neutralize the excessive negative charges on the surface of graphene oxide sheets. The aggregates of graphene oxide and analytes ions were separated and treated with hydrochloric acid to form a slurry solution. The slurry solution was pumped to mix with KBH4 solution to generate hydrides, which were subsequently separated from the liquid phase and directed to an atomic fluorescence spectrometer or directly introduced to an inductively coupled plasma optical emission spectrometer for detection. On the basis of a 50 mL sample volume, the limits of detection of 0.01, 0.002, 0.01, and 0.006 ng mL(-1) were obtained for Pb, Cd, Bi, and Sb, respectively, when using atomic fluorescence spectrometry, providing 35-, 8-, 36-, and 37-fold improvements over the conventional method. Detection limits of 0.6, 0.15, 0.1, and 1.0 ng mL(-1) were obtained with the use of slurry sampling inductively coupled plasma optical emission spectrometry. The method was applied for analysis of two Certified Reference Materials and three water samples for these elements.

A novel, sensitive method is described for the accurate determination of Ni, Se, and Fe in biological tissues by isotope dilution inductively coupled plasma mass spectrometry (ID ICPMS) based on sample introduction arising from online UV photochemical vapor generation (UV-PVG). Volatile species of Ni, Se, and Fe were liberated from a formic acid medium following exposure to a UV source. Sensitivities were enhanced 27- to 355-fold compared to those obtained using pneumatic nebulization sample introduction. Although precision was slightly degraded (a factor of 2) with ultraviolet photochemical mediated vapor generation (UV-PVG), limits of detection (LODs) of 0.18, 1.7, and 1.0 pg g(-1) for Ni, Se, and Fe, respectively, based on an external calibration, provided 28-, 150-, and 29-fold improvements over that realized with conventional pneumatic solution nebulization. Method validation was demonstrated by determination of Ni, Se, and Fe in biological tissue certified reference materials (CRMs) TORT-2 and DORM-3. Concentrations of 2.33 +/- 0.03, 5.80 +/- 0.28, and 109 +/- 2 microg g(-1) (1SD, n = 4) and 1.31 +/- 0.04, 3.35 +/- 0.18, and 353 +/- 5 microg g(-1) (1SD, n = 4) for Ni, Se, and Fe, respectively were obtained in TORT-2 and DORM-3, in good agreement with certified values.

A novel approach to the generation of volatile iron compounds (likely the pentacarbonyl) with high efficiency is described, wherein solutions containing either Fe(2+) or Fe(3+) and low molecular weight organic acids such as formic, acetic or propionic are exposed to a UV source. An optimum generation efficiency of 60 +/- 2% was achieved in 50% formic acid at pH 2.5 with an irradiation time of 250 s by use of a 17 W low-pressure mercury grid lamp. Compared to conventional solution nebulization, sensitivity and limit of detection were improved 80- and 100-fold, respectively, at the 238.204 nm Fe II emission line. A precision of 0.75% RSD was achieved at a concentration of 100 ng/mL. Photochemical vapor generation sample introduction was used for the determination of trace iron in several environmental Certified Reference Materials, including National Research Council Canada DORM-3 fish muscle tissue, DOLT-3 and DOLT-4 fish liver tissues, and SLRS-5 river water, providing analytical results in excellent agreement with certified values based on a simple external calibration.

A novel thin-film reactor is described and evaluated for its analytical performance with photochemical vapor generation (TF-PVG). The device, comprising both the generator and a gas-liquid separator, utilizes a vertical central quartz rod onto which the sample is pumped to yield a thin liquid film conducive to the rapid escape of generated hydrophobic species. The rod is housed within a concentric quartz tube through which a flow of argon carrier/stripping gas is passed to remove and transport the generated species to a detector, which in this study is an inductively coupled argon plasma optical emission spectrometer (ICP-OES). The concentric quartz tube is itself surrounded by a 78-turn 0.5 m long quartz coil low-pressure mercury discharge lamp operating at 20 W. The performance of this thin-film photoreactor was evaluated through comparison of analytical figures of merit for detection of a number of elements undergoing PVG in the presence of formic or acetic acid with those arising from conventional solution nebulization under optimized conditions. The TF-PVG reactor provided sensitivity enhancements, of 110-, 120-, 130-, 250-, 120-, 230-, 78-, 1.3-, 16-, and 32-fold for As, Sb, Bi, Se, Te, Hg, Ni, Co, Fe, and I, respectively, and detection limit enhancements of 110-, 140-, 170-, 270-, 200-, 300-, 160-, 2.7-, 50-, and 44-fold for these same elements. Vapor generation efficiencies ranged from 20-100% for this suite of analytes. The utility of this technique was demonstrated by the determination of Fe and Ni in Certified Reference Materials DORM-3 (fish protein) and DOLT-4 (dogfish liver tissue).

Chemical vapor generation (CVG) is a widely adopted sample introduction method for analytical atomic spectrometry. Nonvolatile precursors (usually ionic, metallic or organometallic species) can be transferred from the condensed phase to the gas phase, yielding the advantages of efficient matrix separation, high analyte transport efficiency, high selectivity, simple instrumentation, and ease of automation. Hydride generation enjoys the greatest popularity as a consequence of its ease of implementation, fast reaction and high yield; but photo-CVG, a newly emerging research field in analytical chemistry, may provide a powerful alternative to conventional CVG due to its simplicity, versatility and cost effectiveness. Although photocatalytic pre-reduction has been used for a number of years, the most attractive aspect of this newly emerging area is the direct generation of volatile species using photochemical reactions. Recent studies undertaken with flow through and batch reactors employing low molecular weight organic acids as photochemical agents are highlighted in this study for such systems as mercury and selenium, as well as reaction mechanisms considered for these processes. Discussion is focused on recent advances in photo-CVG, which we believe will become the subject of intensive future research initiatives.