Thianthrene/TfOH-catalyzed electrophilic halogenations using N-halosuccinimides as the halogen source.

Organohalides are vital organic building blocks with applications spanning various fields. However, direct halogenation of certain neutral or unreactive substrates by using solely the regular halogenating reagents has proven challenging. Although various halogenation approaches via activating halogenating reagents or substrates have emerged, a catalytic system enabling broad substrate applicability and diverse halogenation types remains relatively underexplored. Inspired by the halogenation of arenes via thianthrenation of arenes, here we report that thianthrene, in combined use with trifluoromethanesulfonic acid (TfOH), could work as an effective catalytic system to activate regular halogenating reagents (NXS). This new protocol could accomplish multiple types of halogenation of organic compounds including aromatics, olefins, alkynes and ketones. The mechanism study indicated that a highly reactive electrophilic halogen thianthrenium species, formed in situ from the reaction of NXS with thianthrene in the presence of TfOH, was crucial for the efficient halogenation process.

Preparation of a benziodazole-type iodine(III) compound and its application as a nitrating reagent for synthesis of furazans via a copper-catalyzed cascade process.

The existing hypervalent I(III) reagents bearing ONO2 group are limited in types and their applications primarily focused on the nitrooxylation reactions featuring a fully-exo fashion. Herein, a benziodazole-type O2NO-I(III) compound was prepared and its reaction with ß-monosubstituted enamines in the presence of CuI could trigger a radical nitration/cyclization/dehydration cascade to provide a series of less explored but biologically interesting furazan heterocycles. Mechanistically, the benziodazole-type O2NO-I(III) compound acts as a nitrating reagent and incorporates its NO moiety into the final furazan product in a fully-endo model, a process of which was proposed to involve nitration, cyclization and dehydration.

DNA Methylation of the Autonomous Pathway Is Associated with Flowering Time Variations in Arabidopsis thaliana.

Plant flowering time is affected by endogenous and exogenous factors, but its variation patterns among different populations of a species has not been fully established. In this study, 27 Arabidopsis thaliana accessions were used to investigate the relationship between autonomous pathway gene methylation, gene expression and flowering time variation. DNA methylation analysis, RT-qPCR and transgenic verification showed that variation in the flowering time among the Arabidopsis populations ranged from 19 to 55 days and was significantly correlated with methylation of the coding regions of six upstream genes in the autonomous pathway, FLOWERING LOCUS VE (FVE), FLOWERING LOCUS Y (FY), FLOWERING LOCUS D (FLD), PEPPER (PEP), HISTONE DEACETYLASE 5 (HAD5) and Pre-mRNA Processing Protein 39-1 (PRP39-1), as well as their relative expression levels. The expression of FVE and FVE(CS) was modified separately through degenerate codon substitution of cytosine and led to earlier flowering of transgenic plants by 8 days and 25 days, respectively. An accurate determination of methylated sites in FVE and FVE(CS) among those transgenic plants and the recipient Col-0 verified the close relationship between the number of methylation sites, expression and flowering time. Our findings suggest that the methylation variation of these six key upstream transcription factors was associated with the gene expression level of the autonomous pathway and flowering time in Arabidopsis. The FVE(CS) and FVE genes in transgenic plants tended to be hypermethylated, which could be a protective mechanism for plants. However, modification of gene sequences through degenerate codon substitution to reduce cytosine can avoid hypermethylated transferred genes in transgenic plants. It may be possible to partially regulate the flowering of plants by modified trans-epigenetic technology.

Locality Preservation for Unsupervised Multimodal Change Detection in Remote Sensing Imagery.

Multimodal change detection (MCD) is a topic of increasing interest in remote sensing. Due to different imaging mechanisms, the multimodal images cannot be directly compared to detect the changes. In this article, we explore the topological structure of multimodal images and construct the links between class relationships (same/different) and change labels (changed/unchanged) of pairwise superpixels, which are imaging modality-invariant. With these links, we formulate the MCD problem within a mathematical framework termed the locality-preserving energy model (LPEM), which is used to maintain the local consistency constraints embedded in the links: the structure consistency based on feature similarity and the label consistency based on spatial continuity. Because the foundation of LPEM, i.e., the links, is intuitively explainable and universal, the proposed method is very robust across different MCD situations. Noteworthy, LPEM is built directly on the label of each superpixel, so it is a paradigm that outputs the change map (CM) directly without the need to generate intermediate difference image (DI) as most previous algorithms have done. Experiments on different real datasets demonstrate the effectiveness of the proposed method. Source code of the proposed method is made available at https://github.com/yulisun/LPEM.

Experimental Investigation on Magnetic Abrasive Finishing for Internal Surfaces of Waveguides Produced by Selective Laser Melting.

To enhance the surface quality of metal 3D-printed components, magnetic abrasive finishing (MAF) technology was employed for post-processing polishing. Experimental investigation employing response surface methodology was conducted to explore the impact of processing gap, rotational speed of the magnetic field, auxiliary vibration, and magnetic abrasive particle (MAP) size on the quality enhancement of internal surfaces. A regression model correlating roughness with crucial process parameters was established, followed by parameter optimization. Ultimately, the internal surface finishing of waveguides with blind cavities was achieved, and the finishing quality was comprehensively evaluated. Results indicate that under optimal process conditions, the roughness of the specimens decreased from Ra 2.5 µm to Ra 0.65 µm, reflecting a reduction rate of 74%. Following sequential rough and fine processing, the roughnesses of the cavity bottom, side wall, and convex surface inside the waveguide reduced to 0.59 µm, 0.61 µm, and 1.9 µm, respectively, from the original Ra above 12 µm. The findings of this study provide valuable technical insights into the surface finishing of metal 3D-printed components.

Serotonin transporter imaging agent as a probe for ß-cells of pancreas.

OBJECTIVE: Diabetes mellitus (DM) is one of the major diseases in the world. Nuclear medicine imaging may be able to detect functional status of pancreatic ß cells in vivo, which might elucidate the pathological mechanisms of diabetes and develop individualized treatment plans. In this study, we evaluated the ability of [125I]ADAM, a serotonin transporter (SERT) imaging agent, as a probe for detecting pancreatic ß-cell mass (BCM). METHODS: In vitro cell studies were evaluated in INS-1 cells (rat islet ß cell line). Biodistribution studies were performed in male normal Sprague-Dawley rats and alloxan-induced type 1 diabetes mellitus (T1DM) rats. Distribution and expression of SERT protein in pancreas of rats were also measured by immunofluorescence staining and Western blot. RESULTS: In vitro cell studies showed that the concentration of [125I]ADAM associated with the INS-1 cells was increased gradually with incubation time, and the SERT specific inhibitor, escitalopram, exhibited the inhibitory effect on this interaction. Biodistribution studies also showed that the uptake of [125I]ADAM in the pancreas of normal rats was decreased in the presence of escitalopram. However, in the T1DM rat model with a significant ß cells reduction, the uptake of pancreas was increased when compared with the control. Through immunofluorescence staining and Western blot, it was found that both the endocrine and exocrine cells of the normal pancreas expressed SERT protein, and the level of SERT protein in the exocrine cells was higher than islets. In the diabetic state, the expression of SERT in the exocrine cells was further increased. CONCLUSIONS: The SERT imaging agent, [125I]ADAM, at the present form will not be suitable for imaging ß cells, specifically because there were extraordinarily high non-specific signals contributing from the exocrine cells of pancreas. In addition, we noticed that the level of SERT expression was abnormally elevated in the diabetic state, which might provide an unexpected target for studying the pathological mechanisms of diabetes.

Synthesis of Fluoromethylated Chromones and Their Heteroatom Analogues via Sodium Fluoromethanesulfinate-Enabled Direct Fluoromethylation.

An array of biologically interesting tri/difluoromethylated chromones and their heteroatom analogues were conveniently synthesized from the reaction of chromones and their heteroatom analogues with CF3SO2Na or HCF2SO2Na in the presence of tert-butyl hydroperoxide under mild conditions. A mechanistic pathway involving the generation of the electrophilic tri/difluoromethyl radical, followed with the radical substitution of chromones and their heteroatom analogues, was postulated.

Deep vein thrombosis and pulmonary embolism: a prospective, observational study to evaluate diagnostic performance of the Tina-quant D-Dimer Gen.2 assay.

Background: D-Dimer testing is a diagnostic tool for exclusion of deep vein thrombosis (DVT) and pulmonary embolism (PE). This study evaluated the diagnostic performance of the Tina-quant® D-Dimer Gen.2 assay (Roche Diagnostics International Ltd, Rotkreuz, Switzerland) in patients with low/intermediate pre-test probability of DVT/PE using standard, age-, and clinical probability-adjusted cut-offs. Methods: In this prospective, observational, multicenter study (July 2017-August 2019), plasma samples were collected from hospital emergency departments and specialist referral centers. DVT/PE was diagnosed under hospital standard procedures and imaging protocols. A standard D-dimer cut-off of 0.5 µg fibrinogen equivalent units (FEU)/ml was combined with the three-level Wells score; cut-offs adjusted for age (age × 0.01 µg FEU/ml for patients >50 years) and clinical probability (1 µg FEU/ml for low probability) were also evaluated. An assay comparison was conducted in a subset of samples using the Tina-quant D-Dimer Gen.2 assay and the previously established routine laboratory assay, STA-Liatest D-Di Plus assay (Stago Deutschland GmbH, Düsseldorf, Germany). Results: 2,897 patients were enrolled; 2,516 completed the study (DVT cohort: 1,741 PE cohort: 775). Clinical assessment plus D-dimer testing using the standard cut-off resulted in 317 (DVT) and 230 (PE) false positives, and zero (DVT) and one (PE) false negatives. Negative predictive value (NPV) was 100.0% (95% confidence interval [CI]: 99.7%-100.0%) and 99.8% (95% CI: 98.8%-100.0%) for DVT and PE, respectively. After age-adjustment, NPV was 99.9% (95% CI: 99.6%-100.0%) and 99.1% (95% CI: 97.8-99.7) for DVT and PE, respectively. False positive rates decreased (>50%) in clinical probability-adjusted analyses vs. primary analysis. In the assay comparison, the performances of the two assays were comparable. Conclusion: The Tina-quant D-Dimer Gen.2 assay and standard D-dimer cut-off level combined with the three-level Wells score accurately identified patients with a very low probability of DVT/PE.