Visible-Light-Promoted Radical Cascade Cyclization of 2-Vinyl Benzimidazoles: Access to Benzo[4,5]imidazo[1,2-b]isoquinolin- 11(6H)-ones.

A visible-light-enabled photoredox radical cascade cyclization of 2-vinyl benzimidazole derivatives is developed. This chemistry is applicable to a wide range of N-aroyl 2-vinyl benzimidazoles as acceptors, and halo compounds, including alkyl halides, acyl chlorides and sulfonyl chlorides, as radical precursors. The Langlois reagent also serves as an effective partner in this photocatalytic oxidative cascade process. This protocol provides a robust alternative for rendering highly functionalized benzo[4,5]imidazo[1,2-b]isoquinolin-11(6H)-ones.

The Enhanced Performance of Oxide Thin-Film Transistors Fabricated by a Two-Step Deposition Pressure Process.

It is usually difficult to realize high mobility together with a low threshold voltage and good stability for amorphous oxide thin-film transistors (TFTs). In addition, a low fabrication temperature is preferred in terms of enhancing compatibility with the back end of line of the device. In this study, α-IGZO TFTs were prepared by high-power impulse magnetron sputtering (HiPIMS) at room temperature. The channel was prepared under a two-step deposition pressure process to modulate its electrical properties. X-ray photoelectron spectra revealed that the front-channel has a lower Ga content and a higher oxygen vacancy concentration than the back-channel. This process has the advantage of balancing high mobility and a low threshold voltage of the TFT when compared with a conventional homogeneous channel. It also has a simpler fabrication process than that of a dual active layer comprising heterogeneous materials. The HiPIMS process has the advantage of being a low temperature process for oxide TFTs.

Occurrence differences of hexachlorobutadiene and chlorobenzenes in road dust and roadside soil media in an industrial and residential mixed area in Eastern China.

The road dust and roadside soil can act as both sinks and sources of hexachlorobutadiene (HCBD) and chlorobenzenes (CBzs), but comparative research on these two adjacent media is extremely limited. In this study, HCBD and CBzs were simultaneously analyzed in road dust and roadside soil samples from an area containing both industrial factories and residential communities in Eastern China. The road dust there was found to have 2-6 times higher contents of HCBD (mean 1.14 ng/g, maximum 6.44 ng/g) and ∑Cl3-Cl6CBzs (22.8 ng/g, 90.6 ng/g) than those in the roadside soil. The spatial distributions of HCBD and CBzs in road dusts were affected by various types of sources, showing no significant discrepancy among the sites. On the contrast, HCBD and CBzs contamination in roadside soils occurring near several factories were strongly correlated to their industrial point sources. Risk assessments showed, at current contamination levels in the road dust and roadside soil, HCBD and CBzs are not likely to induce carcinogenic or non-carcinogenic risks to residents in the studied area. Nevertheless, road dust ingestion, as the major exposure pathway of HCBD and CBzs, should be avoided to reduce the exposure risk. These findings based on the contamination differences between two media provide a new perspective and evidence for screening important sources and exposure pathway of HCBD and CBzs, which would be helpful to their source identification and risk control.

Diazotization-Enabled Deaminative Late-Stage Functionalization of Primary Sulfonamides.

We, for the first time, disclosed a simple and efficient strategy for the late-stage functionalization of primary sulfonamides by diazotization, leading to sulfonyl chlorides, sulfonates, and complex sulfonamides. This protocol obviates the requirement for the prefunctionalization of sulfonamides. Its applicability is exemplified by the late-stage functionalization of sulfonamide-type drugs.

Biotic and Abiotic Transformation Pathways of a Short-Chain Chlorinated Paraffin Congener, 1,2,5,6,9,10-C10H16Cl6, in a Rice Seedling Hydroponic Exposure System.

In this work, a typical congener of short-chain chlorinated paraffins (SCCPs) with six chlorine atoms (CP-4, 1,2,5,6,9,10-C10H16Cl6, 250 ng/mL) was selected to elaborate the comprehensive environmental transformation of SCCPs in rice seedling exposure system. CP-4 was quickly absorbed, translocated, and phytovolatilized by seedlings with a small quality of CP-4 (5.81-36.5 ng) being detected in the gas phase. Only 21.4 ± 1.6% of an initial amount (10,000 ng) of CP-4 remained in the exposure system at the end of exposure. Among the transformed CP-4, some were attributed to the degradation of the rhizosphere microorganism (9.1 ± 5.8%), root exudates (2.2 ± 4.2%), and abiotic transformation (3.0 ± 2.8%) that were proved by several transformation products found in the root exudate exposure groups and unplanted controls, and a majority was phytotransformed by rice seedlings. Here, 61 products were determined through complex transformation pathways, including multihydroxylation, -HCl elimination, dechlorination, acetylation, sulfation, glycosylation, and amide acid conjugation. The acetylated and amide acid conjugates of CPs were first observed. Phase I and Phase II phytometabolic reactions of CPs were found intertwining. These findings demonstrate that multiactive transformation reactions contribute to the overlook of CPs accumulated in plants and are helpful for the environmental and health risk assessments of SCCPs in agricultural plants.

[Research progress on analytical methods for the determination of hexachlorobutadiene].

Hexachlorobutadiene (HCBD) is one of persistent organic pollutants (POPs) listed in Annex A and Annex C of the Stockholm Convention in 2015 and 2017, respectively. Research on the sources, environmental occurrences, and biological effects of HCBD has a great significance in controlling this newly added POPs. Sensitive and credible methods for the determination of HCBD are preconditions and form the basis for related research work. In recent years, many researchers have included HCBD as one of the analytes in monitoring or methodological studies. Based on the results of these studies, this paper reviews the research progress on analytical methods for the determination of HCBD and focuses on sample pretreatment methods for the analysis of HCBD in various matrices such as air, water, soil, sewage sludge, and biological tissues. The advantages and disadvantages of the methods are also compared to provide reference for further research in this field.For air samples, HCBD was usually collected by passing air through sorbent cartridges. Materials such as Tenax-TA, Carbosieve, Carbopack, Carboxen 1000, or their mixtures were used as the sorbent. HCBD was thermally desorbed and re-concentrated in a trap and finally transferred for instrumental analysis. Limits of detection (LODs) for HCBD in these methods were at the ng/m3 scale. Compared to sampling using pumps, passive air samplers (PAS) such as polyurethane foam PAS (PUF-PAS) do not require external power supply and are more convenient for sampling POPs in air at a large scale. The LOD of the sorbent-impregnated PUF PAS (SIP-PAS) method was much lower (0.03 pg/m3) than that of the PUF-PAS method (20 pg/m3). However, the sampling volumes in the SIP-PAS and PUF-PAS methods (-6 m3) calculated from the log KOA value of HCBD have significant uncertainty, and this must be confirmed in the future.For water samples, HCl or copper sulfate was added to the sample immediately after sampling to prevent any biological activities. HCBD can be extracted from water using methods such as the purge and trap method, liquid-liquid extraction (LLE) method, and solid phase extraction (SPE) method. Among these methods, SPE enabled the simultaneous extraction, purification, and concentration of trace HCBD in a single step. Recoveries of HCBD on Strata-X and Envi-Carb SPE cartridges (63%-64%) were higher than those on Envi-disk, Oasis HLB, and Strata-C18 cartridges (31%-46%). Drying is another key step for obtaining high recoveries of HCBD. Disk SPE involving the combination of a high-vacuum pump and a low-humidity atmosphere is an effective way to eliminate the residual water. In addition, a micro SPE method using functionalized polysulfone membranes as sorbents and employing ultrasonic desorption was developed for extracting HCBD from drinking water. The recovery of HCBD reached 102%, with a relative standard deviation (RSD) of 3.5%.For solid samples such as dust, soil, sediment, sewage sludge, fly ash, and biota tissue, multiple pretreatment methods were used in combination, owing to the more complex matrix. Freeze or air drying, grinding, and sieving of samples were commonly carried out before the extraction. Soxhlet extraction is a typical extraction method for HCBD; however, it requires many organic reagents and is time consuming. The accelerated solvent extraction (ASE) method requires a small amount of organic reagent, and the extraction can be performed rapidly. It was recently applied for the extraction of HCBD from solid samples under 10.34 MPa and at 100 ℃. Purification could be achieved simultaneously by mixing florisil materials with samples in the ASE pool. Nevertheless, employing the ASE methods widely is difficult because of their high costs. Ultrasonic-assisted extraction (UAE) has the same extraction efficiency for HCBD, with much lower costs compared to ASE, and is therefore adopted by most researchers. The type of extraction solvent, solid-to-liquid ratio, ultrasonic temperature, and power affect the extraction efficiency. Ultrasonic extraction at 30 ℃ and 200 W using 30 mL dichloromethane as the extraction solvent resulted in acceptable recoveries (64.0%-69.4%) of HCBD in 2 g fly ash. After extraction, a clean-up step is necessary for the extracts of solid samples. Column chromatography is frequently used for purification. The combined use of several columns or a multilayer column filled with florisil, silica gel, acid silica gel, or alumina can improve the elimination efficiency of interfering substances.Instrumental analysis for HCBD is mainly performed with a gas chromatograph equipped with a mass spectrometer operating in selected ion monitoring mode. DB-5MS, HP-5MS, HP-1, ZB-5MS, and BP-5 can be used as the chromatographic columns. Qualification ions and quantification ions include m/z 225, 223, 260, 227, 190, and 188. GC-MS using an electron ionization (EI) source was more sensitive to HCBD than GC-MS using a positive chemical ionization source (PCI) and atmospheric pressure chemical ionization source (APCI). Gas chromatography-tandem mass spectrometry (GC-MS/MS), gas chromatography-high-resolution mass spectrometry (GC-HRMS), and high-resolution gas chromatography-high-resolution mass spectrometry (HRGC-HRMS) have recently been used for the separation and determination of HCBD and various other organic pollutants. Instrumental detection limits for HCBD in GC-MS/MS, GC-HRMS, and HRGC-HRMS were more than ten times lower than that in GC-MS, indicating the remarkable application potential of these high-performance instruments in HCBD analysis.

Simultaneous determination of tetra-, penta- and hexachlorobutadienes in shellfish by gas chromatography-triple quadrupole mass spectrometry.

Polychloro-1,3-butadienes (polyCBDs) are attracting increasing concern due to their high toxicity. However, research on multiple polyCBDs in aquatic biota is still extremely limited. In this study, a sensitive method for simultaneous determination of nine polyCBD (Cl4-Cl6) congeners, including six tetrachlorobutadiene (TeCBD) isomers, two pentachlorobutadiene (PeCBD) isomers, and hexachlorobutadiene (HCBD), in shellfish was developed based on accelerated solvent extraction (ASE), solid-phase extraction (SPE) clean-up and gas chromatography-triple quadrupole mass spectrometry (GC-QqQ-MS/MS). Low method limits of detection (MDLs) in the range 0.03-0.21 ng/g dry weight for target analytes with satisfactory recoveries (47.7 %-70.6 %) were achieved. The valid method was then applied to analyze nine polyCBDs congeners in 42 shellfish and 11 fish samples collected from markets in eight coastal cities, China. Trace HCBD was detected in 14 samples, while TeCBDs and PeCBDs were under the MDLs in all the samples, indicating little contamination of these pollutants in the marketed shellfish and fish in China. Multiple polyCBDs especially TeCBDs and PeCBDs were firstly involved in the proposed method and investigation here, which lay the groundwork for future research on the environmental behavior and exposure risks of polyCBDs in aquatic biotas.

A strategy to differentiate dopamine and levodopa based on their cyclization reaction regulated by pH.

Levodopa is often used to treat Parkinson's disease. It coexists with dopamine in human fluids and is electrochemically oxidized at the same potential as dopamine. Differentiating levodopa from dopamine is difficult via electrochemical techniques. Taking advantage of the differences in the rate constants of levodopa and dopamine for the intramolecular cyclization reaction, we observed that the cyclization reaction of dopamine-quinone was completely suppressed under pH 4.8, while that of levodopa-quinone occurred. The product of cyclization caused a new cathodic peak at negative potential. Its peak current was dependent on the concentration of levodopa but not that of dopamine. As a result, we developed a method of detecting levodopa in the presence of dopamine with a bare glassy carbon electrode.

Mapping epileptic directional brain networks using intracranial EEG data.

The human brain is a directional network system, in which brain regions are network nodes and the influence exerted by one region on another is a network edge. We refer to this directional information flow from one region to another as directional connectivity. Seizures arise from an epileptic directional network; abnormal neuronal activities start from a seizure onset zone and propagate via a network to otherwise healthy brain regions. As such, effective epilepsy diagnosis and treatment require accurate identification of directional connections among regions, i.e., mapping of epileptic patients' brain networks. This article aims to understand the epileptic brain network using intracranial electroencephalographic data-recordings of epileptic patients' brain activities in many regions. The most popular models for directional connectivity use ordinary differential equations (ODE). However, ODE models are sensitive to data noise and computationally costly. To address these issues, we propose a high-dimensional state-space multivariate autoregression (SSMAR) model for the brain's directional connectivity. Different from standard multivariate autoregression and SSMAR models, the proposed SSMAR features a cluster structure, where the brain network consists of several clusters of densely connected brain regions. We develop an expectation-maximization algorithm to estimate the proposed model and use it to map the interregional networks of epileptic patients in different seizure stages. Our method reveals the evolution of brain networks during seizure development.

Total mercury, methylmercury, and selenium in aquatic products from coastal cities of China: Distribution characteristics and risk assessment.

This study analyzed total mercury (THg), methylmercury (MeHg) and selenium (Se) in 114 aquatic product samples (representing 39 species) from eight coastal cities of China. The THg and MeHg levels in different parts of the same sample species were in the order of muscle ≥ skin/shell > roe, whereas Se levels were much higher in roe. Concentrations of THg, MeHg, and Se in the muscles were between 2.27-154, 0.36-135, and 57.8-1.20 × 103 ng g-1 wet weight (ww), respectively. Although significant differences in analyte concentrations were not observed among cities, they existed among three species; marine fish, freshwater fish, and shellfish. Shellfish had generally lower Hg content (mean: 20.2 ng g-1 ww THg, 6.71 ng g-1 ww MeHg, and 30.9% MeHg/THg ratio); however it had higher Se content (528 ng g-1 ww) than the other types of fish (mean: 33.3 ng g-1 ww THg, 28.2 ng g-1 ww MeHg, and 79.2% MeHg/THg ratio, 257 ng g-1 ww Se). In addition to species, the individual growth and HgSe interaction influenced Hg distribution. Evident correlations were observed between several individual body features and Hg content, and between Se and THg concentrations (p < 0.05). The greater correlation coefficient between two elements for fish indicated stronger HgSe antagonism through HgSe compound formation in fish. Relatively low THg daily intakes (mean 0.013-0.080 µg kg-1 day-1) and MeHg daily intakes (0.006-0.065 µg kg-1 day-1) along with Se:Hg molar ratios >1 and positive HBVSe values suggest that aquatic products from these sites will not pose immediate health problems to consumers. Fish was the dominating contributor for MeHg intake whereas shellfish was the dominating contributor for Se intake. To safeguard against mercury exposure, residents in these areas can appropriately increase shellfish intake (especially bivalves), rather than exclusively consuming marine fish.