Lithiation of a Silyl Ether: Formation of an ortho‐Fries Hydroxyketone

A hydroxy‐directed alkylation of an N,N‐diethylarylamide using CIPE‐assisted α‐silyl carbanions (CIPE=complex‐induced proximity effect) has been developed using a simple reagent combination of LDA (lithium diisopropylamide) and chlorosilane. A study of the mechanism, and the application of the procedure to an anionic Snieckus–Fries rearrangement for a highly efficient synthesis of the potent phosphatidylinositol 3‐kinase (PI3K) inhibitor LY294002, are reported.     

Stripping the latex: the challenge of miniemulsion polymerization without initiator,costabilizer and surfactant

When finally processed to provide the function for which the latex was selected―binding, protecting, finishing―components such as surfactant, costabilizer or initiator become generally useless, not to say detrimental. In this study, we show that miniemulsion photopolymerization provides a suitable method to create latex without the apparent addition of these three compounds. Indeed, UV-driven monomer self-initiation can create initiating radicals without the aid of initiator, the fast in situ photogenerated polymer can hinder Ostwald ripening with the assistance of external costabilizer, and finally, UV-transparent clay can replace conventional surfactant to ensure colloidal stabilization. Each strategy has been developed individually before being combined together to end up with a unique miniemulsion procedure free of initiator, costabilizer and surfactant. Such approach paves the way to a simplified and environmentally improved pathway towards aqueous polymer dispersions.     

Nephrotoxicity assessments of benzo(a)pyrene during zebrafish embryogenesis

Benzo(a)pyrene is a chemical produced during the process of making fried, roasted, and smoked foods. It remains unclear whether benzo(a)pyrene affects the early development of human organs. In this study, we used the transgenic zebrafish line Tg(wt1b:GFP) as a model to assess benzo(a)pyrene-induced kidney malformation. By soaking zebrafish embryos in benzo(a)pyrene at various doses (2, 20, and 200 ppb), only a minor effect on the survival rate was detected (0 ppb: 97.8 ± 1.9 %; 2–200 ppb: 89.1 ± 5.8–91.5 ± 8.3 %). However, benzo(a)pyrene significantly affected the development of the kidney (malformation rates ranges from 50.0 ± 3.5 to 77.4 ± 5.3 %). Various abnormalities, such as unusual curving of pronephric tubes, swollen glomerulus, and incomplete development of pronephric ducts, were observed. This study provides a rapid and effective protocol for the evaluation of the notable effects of benzo(a)pyrene on embryonic kidney development.     

Thermal and Nonthermal Effects in Plasmon-Mediated Electrochemistry at Nanostructured Ag Electrodes

Hot carriers (HCs) and thermal effects, stemming from plasmon decays, are crucial for most plasmonic applications. However, quantifying these two effects remains extremely challenging due to the experimental difficulty in accurately measuring the temperature at reaction sites. Herein, we provide a novel strategy to disentangle HCs from photothermal effects based on the different traits of heat dissipation (long range) and HCs transport (short range), and quantitatively uncover the dominant and potential-dependent role of photothermal effect by investigating the rapid- and slow-response currents in plasmon-mediated electrochemistry at nanostructured Ag electrode. Furthermore, the plasmoelectric surface potential is found to contribute to the rapid-response currents, which is absent in the previous studies.     

Ferric Ion Driven Assembly of Catalase-like Supramolecular Photosensitizing Nanozymes for Combating Hypoxic Tumors

A facile approach to assemble catalase-like photosensitizing nanozymes with a self-oxygen-supplying ability was developed. The process involved Fe³⁺-driven self-assembly of fluorenylmethyloxycarbonyl (Fmoc)-protected amino acids. By adding a zinc(II) phthalocyanine-based photosensitizer (ZnPc) and the hypoxia-inducible factor 1 (HIF-1) inhibitor acriflavine (ACF) during the Fe³⁺-promoted self-assembly of Fmoc-protected cysteine (Fmoc-Cys), the nanovesicles Fmoc-Cys/Fe@Pc and Fmoc-Cys/Fe@Pc/ACF were prepared, which could be disassembled intracellularly. The released Fe³⁺ could catalyze the transformation of H₂O₂ enriched in cancer cells to oxygen efficiently, thereby ameliorating the hypoxic condition and promoting the photosensitizing activity of the released ZnPc. With an additional therapeutic component, Fmoc-Cys/Fe@Pc/ACF exhibited higher in vitro and in vivo photodynamic activities than Fmoc-Cys/Fe@Pc, demonstrating the synergistic effect of ZnPc and ACF.     

Di- and Tri-organotin(IV) Complexes of N-Acetyltriglycine and N-Benzoyltriglycine: Synthesis and Spectroscopic Characterization

Di- and tri-organotin(IV) derivatives of N -acetyltriglycine and N -benzoyltriglycine (HA) were obtained by refluxing equimolar mixtures of the ligand and the organotin(IV) oxide or hydroxide in methanol or acetone. According to the spectroscopic data, triorganotin(IV) derivatives adopt a trigonal-bipyramidal structure in which the planar R₃Sn^IV unit is bonded by a monodentate carboxylate group and a donor group, presumably the amide CO. The reaction of HA with the appropriate diorganotin(IV) compounds gave both dicarboxylates R₂SnA₂, with six-coordinated tin, and dimeric tetraorganodistannoxanes {[R₂SnA]₂O}₂, in which the tin atoms are essentially five-coordinated.     

Permutation Entropy-Based Interpretability of Convolutional Neural Network Models for Interictal EEG Discrimination of Subjects with Epileptic Seizures vs. Psychogenic Non-Epileptic Seizures

The differential diagnosis of epileptic seizures (ES) and psychogenic non-epileptic seizures (PNES) may be difficult, due to the lack of distinctive clinical features. The interictal electroencephalographic (EEG) signal may also be normal in patients with ES. Innovative diagnostic tools that exploit non-linear EEG analysis and deep learning (DL) could provide important support to physicians for clinical diagnosis. In this work, 18 patients with new-onset ES (12 males, 6 females) and 18 patients with video-recorded PNES (2 males, 16 females) with normal interictal EEG at visual inspection were enrolled. None of them was taking psychotropic drugs. A convolutional neural network (CNN) scheme using DL classification was designed to classify the two categories of subjects (ES vs. PNES). The proposed architecture performs an EEG time-frequency transformation and a classification step with a CNN. The CNN was able to classify the EEG recordings of subjects with ES vs. subjects with PNES with 94.4% accuracy. CNN provided high performance in the assigned binary classification when compared to standard learning algorithms (multi-layer perceptron, support vector machine, linear discriminant analysis and quadratic discriminant analysis). In order to interpret how the CNN achieved this performance, information theoretical analysis was carried out. Specifically, the permutation entropy (PE) of the feature maps was evaluated and compared in the two classes. The achieved results, although preliminary, encourage the use of these innovative techniques to support neurologists in early diagnoses.     

Sampling and analysis of volatile organics emitted from wastewater treatment plant and drain system of an industrial science park

Volatile organic compounds (VOCs) were monitored in the different sections of a wastewater treatment plant (WWTP), the outlet of both the WWTP and rainfall water, and the downstream of the WWTP joining the river in the area or vicinity of an industrial science park located in Hsinchu, Taiwan. Levels of VOCs were determined by collecting air samples over several sampling points and analyzed using gas chromatography. Among VOCs identified in the drainage and effluent system in each season, acetone, isopropanol (IPA) and dimethyl sulfide (DMS) were the major emission species and maximum concentrations were 400.4, 22.8 and 641.2 ppbv, respectively. The ambient air and wastewater sample analysis from neighboring wastewater streams identified pollutants being discharged from unaccounted sources other than the industrial park. According to the 24 h semi-continuous monitoring data (27/7/2002-29/7/2002), the total VOC concentration was an average of 93 ppbv (acetone contributed ∼78%) with a dramatic variation during the day and night. The emission rate of measured VOCs estimated using fixed box model projected an average of 2-4 μg m⁻² h⁻¹) during the day and 9-17 μg m⁻² h⁻¹ during the night. In addition, the isopleth maps show that the acetone and DMS emissions influence adversely the nearby residential area located at less than 100 m downwind from the plant. Eventually, based on this study, an on-line monitoring and alerting system could be built for a long-term performance, and with regular information on the varying pollutants over time construction of a green strategy and creation of a sustainable environment can be achieved.     

Measurement of non-methane hydrocarbons in Taipei city and their impact on ozone formation in relation to air quality

Air pollutants data from semi-continuous measurements at multiple sampling sites in Taipei metropolitan area of Taiwan was obtained by collecting air samples in canisters. The hydrocarbon composition was determined by using GC/MS and GC/FID. The air samples were pre-concentrated onto glass beads prior to separation by PLOT and DB-1 columns of GC. The method showed detection limit of <1 ppb and relative standard deviation in the range of 5-30% for different compounds. Aromatic hydrocarbons (toluene, benzene, etc.) and aliphatic hydrocarbons (ethylene, acetylene, propane, etc.) were correlated primarily to determine the source of emission. The estimated hydrocarbons were ranked according to their abundance and photochemical reactivity. The criteria pollutants, ozone and NO₂ were measured by UV-differential optical absorption spectroscopy (UV-DOAS), and were utilized to determine the relative importance of non-methane hydrocarbons (NMHC) and significant contribution of NO₂ in limiting ozone formation. The obtained results suggest that ozone formation in Taipei city is probably limited by the supply of non-methane hydrocarbons. The concentration profile of targeted pollutants was compared to other metropolitan areas to determine air quality and the pollutant sources.