Contamination, dynamics, and health risk assessment of pesticides in seawater and marine samples from the Seto Inland Sea, Japan.

We assessed the contamination, dynamics, and health risks of the pesticides cyanazine, simetryn, fenarimol, isoprothiolane, diazinon, irgarol, fenitrothion, and diuron in marine samples (seawater, sediments, plankton, fish, and other edible organisms) at various locations in the Seto Inland Sea in Japan in 2016 and 2017. Pesticide concentrations were highest at sampling sites close to the coastline, and mean concentrations in seawater were slightly higher in surface water than in bottom water. All eight pesticides were detected in plankton. Diazinon concentrations (77-387 ng/g dw) were highest in sediments and cyanazine was the most frequently detected pesticide (88%, n = 17) in sediments. Only cyanazine (2.7-41.9 ng/g dw), simetryn (1.0-34.3 ng/g dw), and diazinon (6.3-308.8 ng/g dw) were detected in fish and other edible marine organisms. Based on the calculated bioconcentration factor, the results showed that plankton, fish, and marine animals bioaccumulated pesticides. The highest hazard quotients were calculated for diazinon in red seabream and greenling, indicating a possible risk to consumers. It is, therefore, imperative to promote strict implementation of pollution control, integrated pest management practices, and policy formulation on pesticides. Usage of diazinon must be controlled and monitored to ensure large residues do not reach aquatic ecosystems and marine coastlines.

Endoscopic Mucosal Resection of Adenocarcinoma at the Minor Duodenal Papilla: A Case Report and Suggestions for the Optimal Treatment Strategy.

We herein report an extremely rare case of adenocarcinoma of the minor duodenal papilla (MiDP) which was successfully treated by endoscopic mucosal resection (EMR). An asymptomatic 84-year-old man underwent upper gastrointestinal endoscopy, which revealed a slightly elevated lesion at the MiDP. The biopsy findings were suggestive of adenocarcinoma. Computed tomography, magnetic resonance images and endoscopic ultrasonography did not reveal pancreatic tumor infiltration nor any apparent distant metastases. Therefore, we treated the lesion using EMR with complete resection. No recurrence or metastasis has been detected at 13 months after EMR. Total resection of the MiDP can thus serve as a relatively safe and simple treatment.

Aerosols Produced by Upper Gastrointestinal Endoscopy: A Quantitative Evaluation.

INTRODUCTION: During the coronavirus disease 2019 pandemic, whether endoscopy generates aerosols needs to be determined. METHODS: In patients undergoing upper gastrointestinal endoscopy with an enclosure covering their heads, 0.3-10-µm aerosols were measured for 60 seconds before, during, and after endoscopy by an optical counter. Whether aerosols increased in the situation with and without endoscopy was examined. RESULTS: The analysis included 103 consecutive patients undergoing endoscopy and 90 control patients. Aerosols increased significantly during endoscopy compared with the control group. Body mass index and burping were significant factors related to increased aerosols during endoscopy. DISCUSSION: Upper gastrointestinal endoscopy was an aerosol-generating procedure.

Nickel-Catalyzed Asymmetric Friedel-Crafts Propargylation of 3-Substituted Indoles with Propargylic Carbonates Bearing an Internal Alkyne Group.

The nickel-catalyzed highly enantioselective Friedel-Crafts propargylation of 3-substituted indoles with propargylic carbonates bearing an internal alkyne group was developed. A wide array of the propargylic carbonates as well as 3-substituted indoles can be applicable to the asymmetric nickel catalysis, providing the corresponding chiral C-3 propargylated indolenine derivatives bearing two vicinal chiral centers in up to 89% yield with up to >99% ee and 94:6 dr (24 examples).

Nickel-Catalyzed Hydroarylation of in Situ Generated 1,3-Dienes with Arylboronic Acids Using a Secondary Homoallyl Carbonate as a Surrogate for the 1,3-Diene and Hydride Source.

The nickel-catalyzed hydroarylation of 1,3-dienes with arylboronic acids using a secondary homoallyl carbonate as a surrogate for the 1,3-diene and hydride source has been developed. The synthetic strategy allowed an efficient access to a wide array of hydroarylation products in high yields with high functional group compatibility without the use of an external hydride source. Mechanistic experiments indicated that the alkene-directed oxidative addition and subsequent ß-hydride elimination would be a critical process in this transformation.

Nickel-Catalyzed Transformation of Alkene-Tethered Oxime Ethers to Nitriles by a Traceless Directing Group Strategy.

Nickel-catalyzed transformation of alkene-tethered oxime ethers to nitriles using a traceless directing group strategy has been developed. A series of alkene-tethered oxime ethers derived from benzaldehyde and cinnamyl aldehyde derivatives were converted into the corresponding benzonitriles and cinnamonitriles in 46-98% yields using the nickel catalyst system. Control experiments showed that the alkene group tethered to an oxygen atom on the oximes via one methylene unit plays a key role as a traceless directing group during the catalysis.

Nickel-Catalyzed Benzylic Substitution of Benzyl Esters with Malonates as a Soft Carbon Nucleophile.

The nickel-catalyzed benzylic substitution of benzyl alcohol derivatives with a soft carbon nucleophile is extremely rare compared to that with a hard carbon nucleophile. We have achieved the nickel-catalyzed benzylic substitution of benzyl esters with malonates as a soft carbon nucleophile. Primary and secondary benzyl 2,3,4,5,6-pentafluorobenzoates as well as a wide variety of malonate derivatives were well tolerated in the nickel-catalyzed reaction, providing the corresponding alkylation products in 46-86% yields (34 examples). Additionally, we propose a possible reaction mechanism that would undergo via the η1- and η3-benzylnickel intermediates.

Nickel-Catalyzed Asymmetric Propargylic Amination of Propargylic Carbonates Bearing an Internal Alkyne Group.

We have achieved the nickel-catalyzed asymmetric propargylic amination of propargylic carbonates bearing an internal alkyne group. A wide variety of propargylic carbonates and N-methylaniline derivatives were tolerated under the reaction conditions, providing the corresponding chiral propargylic amines in up to 97% yield with up to 97% ee.

Endoscopic ultrasound-guided transduodenal drainage of idiopathic retroperitoneal abscess in an immunocompromised patient: A case report.

RATIONALE: Idiopathic retroperitoneal abscesses are insidious, occult illnesses with high mortality if inadequately drained. Endoscopic ultrasound-guided drainage is an alternative to percutaneous or surgical drainage, it is not widely performed for retroperitoneal abscesses other than peripancreatic fluid collection. PATIENT CONCERNS: We present a 76-year-old Japanese woman with abdominal pain, high fever, and a history of rheumatism on treatment with immunosuppressants. DIAGNOSES: The patient was diagnosed with idiopathic retroperitoneal abscess based on results obtained from her clinical course and findings on computed tomography. INTERVENTIONS: We performed Endoscopic ultrasound-guided drainage. After we performed needle puncture via the descending portion of the duodenum, the fistula was expanded using a dilator, and a double-pigtail stent and endoscopic nasobiliary drainage tube were inserted. OUTCOMES: The patient was kept nil by mouth, together with intravenous antibiotic therapy, and repeated washing of the abscess cavity with saline was performed. After that, we confirmed disappearance of the cavity, and, after removing the tubes, commenced oral feeding. We were able to avoid surgery in this immunosuppressed patient. LESSONS: Endoscopic ultrasound (EUS)-guided abscess drainage can be overall considered a safe and useful procedure. We also propose the double-stent method, with both internal and external stents, for the treatment of idiopathic retroperitoneal abscesses.

The C-terminal fragment of prostate-specific antigen, a 2331 Da peptide, as a new urinary pathognomonic biomarker candidate for diagnosing prostate cancer.

BACKGROUND AND OBJECTIVES: Prostate cancer (PCa) is one of the most common cancers and leading cause of cancer-related deaths in men. Mass screening has been carried out since the 1990s using prostate-specific antigen (PSA) levels in the serum as a PCa biomarker. However, although PSA is an excellent organ-specific marker, it is not a cancer-specific marker. Therefore, the aim of this study was to discover new biomarkers for the diagnosis of PCa. MATERIALS AND METHODS: We focused on urine samples voided following prostate massage (digital rectal examination [DRE]) and conducted a peptidomic analysis of these samples using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF/MS(n)). Urinary biomaterials were concentrated and desalted using CM-Sepharose prior to the following analyses being performed by MALDI-TOF/MS(n): 1) differential analyses of mass spectra; 2) determination of amino acid sequences; and 3) quantitative analyses using a stable isotope-labeled internal standard. RESULTS: Multivariate analysis of the MALDI-TOF/MS mass spectra of urinary extracts revealed a 2331 Da peptide in urine samples following DRE. This peptide was identified as a C-terminal PSA fragment composed of 19 amino acid residues. Moreover, quantitative analysis of the relationship between isotope-labeled synthetic and intact peptides using MALDI-TOF/MS revealed that this peptide may be a new pathognomonic biomarker candidate that can differentiate PCa patients from non-cancer subjects. CONCLUSION: The results of the present study indicate that the 2331 Da peptide fragment of PSA may become a new pathognomonic biomarker for the diagnosis of PCa. A further large-scale investigation is currently underway to assess the possibility of using this peptide in the early detection of PCa.