Pesticide residue levels in peppers cultivated in Souss Masa valley (Morocco) after multiple applications of azoxystrobin and chlorothalonil

Residue levels of azoxystrobin and chlorothalonil were determined in peppers grown in an experimental greenhouse. These two pesticides were selected on the basis of previous excesses of 26 and 24%, respectively, found in peppers samples cultivated in 2008 in eastern Morocco. The measurements were made over a 7 week period in which up to three successive treatments with azoxystrobin and a 4 week period in which up to three successive treatments with chlorothalonil were carried out. In all cases, plants were sprayed separately with azoxystrobin and chlorothalonil with application rates of active ingredients of 50 and 200?cc?hl^?1, respectively. Sampling was carried out at 0, 2, 4, 7, 12, 15 and 22 days for azoxystrobin and 0, 1, 3, 7, 8 and 10 days for chlorothalonil. Residue levels of azoxystrobin and chlorothalonil were determined by liquid–liquid extraction (LLE) and gas chromatography with electron-capture detector (GC-ECD). During the study, residue levels in the plantation ranged between 1.14 and 0.02?mg?kg^?1 for azoxystrobin and between 0.55 and 0.04?mg?kg^?1 for chlorothalonil. The application of an intensive washing process to the pepper samples did not lead to a significant reduction in the residue levels of either pesticide. Likewise, significant differences were not found between the residue levels in the ‘edible’ and ‘inedible’ parts of the peppers.     

Microstructural and Potential Dependence Studies of Urease-Immobilized Gold Nanoparticles–Polypyrrole Composite Film for Urea Detection

Gold nanoparticle–polypyrrole nanocomposite film was electrochemically deposited in a single-step polymerization of pyrrole in the presence of 3-mercaptopropionic acid (MPA)-capped gold nanoparticles (GNPs) and p-toluenesulfonic acid (pTSA) on the surface of an indium tin oxide (ITO)-coated glass plate. The carboxyl functional groups surrounding the GNPs within the polymer matrix were utilized for the immobilization of urease enzyme through carbodiimide coupling reaction for the construction of a Urs/GNP(MPA)–PPy/ITO-glass bioelectrode for urea detection in Tris–HCl buffer. The resulting bioelectrode film was characterized by atomic force microscopy (AFM), high-resolution transmission electron microscopy (HRTEM), contact angle measurement, Fourier transform infrared spectroscopy (FTIR), and electrochemical techniques. The potentiometric response of the bioelectrode made of polymer nanocomposite films of two different thicknesses prepared at 100 and 250 mC cm^?2 charge densities, respectively, was studied towards the urea concentration in Tris–HCl buffer (pH 7.4). The thin polymer nanocomposite film-based bioelectrode prepared at 100 mC cm^?2 charge density exhibited a comparatively good potentiometric response than a thick 250 mC cm^?2 charge density film with a linear range of urea detection from 0.01 to 10 mM with a sensitivity of 29.7 mV per decade.     

Comparative studies for selective deprotection of the N-arylideneamino moiety from heterocyclic amides: kinetic and theoretical studies. Part 2

4-Benzylideneamino-1,2,4-triazine-3,5(2H,4H)-diones (2-5), 6-styryl-1,2,4-triazine-3,5(2H,4H)-dione (6), and 6-styryl-2,3-dihydro-3-thioxo-1,2,4-triazin-5(4H)-one (7) were synthesized and pyrolyzed in the gas phase. The kinetic effect of changing the substituent on the triazine ring from hydrogen to methyl, phenyl, and styryl was measured. Analyses of the pyrolyzates of 2-5 showed the elimination products to be benzonitrile and the triazine fragment, while the pyrolyzates of 6 and 7 reveal the formation of cis- and trans-cinnamonitriles. Theoretical study of the pyrolysis reactions of 2-5 using an ab initio SCF method was investigated.     

Tuning the hydrophilicity of gold nanoparticles templated in star block copolymers

We report on a simple procedure to tune the hydrophilicity of hybrid gold nanoparticles. The nanoparticles have been prepared in the core of a poly(ethylene glycol)-block-poly(epsilon-caprolactone) (PEG-b-PCL) five-arm star block copolymer. A hydrophilic corona was then added to these hybrid gold nanoparticles by direct chemisorption of trithiocarbonate-containing poly(acrylic acid) chains. These polymers were synthesized by RAFT polymerization with a trithiocarbonate as the chain-transfer agent. The efficiency of the grafting was evidenced by TEM, AFM, and DLS and by the successful transfer of these nanoparticles from organic solvent to water.     

Antiproliferative Efficacy of N-(3-chloro-4-fluorophenyl)-6,7-dimethoxyquinazolin-4-amine,DW-8, in Colon Cancer Cells Is Mediated by Intrinsic Apoptosis

A novel series of 4-anilinoquinazoline analogues, DW (1–10), were evaluated for anticancer efficacy in human breast cancer (BT-20) and human colorectal cancer (CRC) cell lines (HCT116, HT29, and SW620). The compound, DW-8, had the highest anticancer efficacy and selectivity in the colorectal cancer cell lines, HCT116, HT29, and SW620, with IC₅₀ values of 8.50 ± 2.53 µM, 5.80 ± 0.92 µM, and 6.15 ± 0.37 µM, respectively, compared to the non-cancerous colon cell line, CRL1459, with an IC₅₀ of 14.05 ± 0.37 µM. The selectivity index of DW-8 was >2-fold in colon cancer cells incubated with vehicle. We further determined the mechanisms of cell death induced by DW-8 in SW620 CRC cancer cells. DW-8 (10 and 30 µM) induced apoptosis by (1) producing cell cycle arrest at the G2 phase; (2) activating the intrinsic apoptotic pathway, as indicated by the activation of caspase-9 and the executioner caspases-3 and 7; (3) nuclear fragmentation and (4) increasing the levels of reactive oxygen species (ROS). Overall, our results suggest that DW-8 may represent a suitable lead for developing novel compounds to treat CRC.     

Contribution of Aldehydes and Their Derivatives to Antimicrobial and Immunomodulatory Activities

Essential oils (EOs) are intricate combinations of evaporative compounds produced by aromatic plants and extracted by distillation or expression. EOs are natural secondary metabolites derived from plants and have been found to be useful in food and nutraceutical manufacturing, perfumery and cosmetics; they have also been found to alleviate the phenomenon of antimicrobial resistance (AMR) in addition to functioning as antibacterial and antifungal agents, balancing menstrual cycles and being efficacious as an immune system booster. Several main aldehyde constituents can be found in different types of EOs, and thus, aldehydes and their derivatives will be the main focus of this study with regard to their antimicrobial, antioxidative, anti-inflammatory and immunomodulatory effects. This brief study also explores the activity of aldehydes and their derivatives against pathogenic bacteria for future use in the clinical setting.     

Antioxidant and Antimicrobial Activities of Erodium arborescens Aerial Part Extracts and Characterization by LC-HESI-MS2 of Its Acetone Extract

The phytochemical analysis of antioxidant and antibacterial activities of Erodium arborescens aerial part extracts constitute the focus of this research. The chemical composition of an acetone extract was investigated using LC-HESI-MS², which revealed the presence of 70 compounds. The major identified components were tannin derivatives. Total polyphenol and total flavonoid contents were assessed in plant extracts (hexane, ethyl acetate, acetone and methanol). The results showed that the acetone extract exhibited the highest contents of polyphenols and flavonoids, 895.54 and 36.39 mg QE/g DE, respectively. Furthermore, when compared to other extracts, Erodium arborescens acetone extract was endowed with the highest antioxidant activity with 2,2-diphenyl-1-picrylhydrazyl (DPPH), ferric reducing antioxidant power (FRAP) and total antioxidant capacity (TAC) tests. In addition, the four extracts of Erodium arborescens showed variable degrees of antimicrobial activity against the tested strains, and the interesting activity was obtained with acetone and methanol extracts.     

Simultaneous Hydrogen Generation and Exciplex Stimulated Emission in Photobasic Carbon Dots

Photocatalytic water splitting is a promising approach to generating sustainable hydrogen. However, the transport of photoelectrons to the catalyst sites, usually within ps-to-ns timescales, is much faster than proton delivery (∼μs), which limits the activity. Therefore, the acceleration of abstraction of protons from water molecules towards the catalytic sites to keep up with the electron transfer rate can significantly promote hydrogen production. The photobasic effect that is the increase in proton affinity upon excitation offers means to achieve this objective. Herein, we design photobasic carbon dots and identify that internal pyridinic N sites are intrinsically photobasic. This is supported by steady-state and ultrafast spectroscopic measurements that demonstrate proton abstraction within a few picoseconds of excitation. Furthermore, we show that in water, they form a unique four-level lasing scheme with optical gain and stimulated emission. The latter competes with photocatalysis, revealing a rather unique mechanism for efficiency loss, such that the stimulated emission can act as a toggle for photocatalytic activity. This provides additional means of controlling the photocatalytic process and helps the rational design of photocatalytic materials.     

Rapid multi-attribute characterization of intact bispecific antibodies by a microfluidic chip-based integrated icIEF-MS technology

Rapid, direct identification and quantitation of protein charge variants, and assessment of critical quality attributes with high sensitivity are important drivers required to accelerate the development of biotherapeutics. We describe the use of an enhanced microfluidic chip-based integrated imaged capillary isoelectric focusing-mass spectrometry (icIEF-MS) technology to assess multiple quality attributes of intact antibodies in a single run. Results demonstrate comprehensive detection of multiple charge variants of an aglycosylated knob-into-hole bispecific antibody. Upfront, on-chip separation by icIEF coupled to MS provides the orthogonal separation required to resolve and identify acidic posttranslational modifications including difficult-to-detect deamidation and glycation events at the intact protein level. In addition, on-chip UV detection enables pI determination and relative quantitation of charge isoforms. Six charge variant peaks were resolved by icIEF, mobilized toward the on-chip electrospray tip and directly identified by in-line icIEF-MS using a connected quadrupole time-of-flight mass spectrometer. In addition to acidic charge variants, basic variants were identified as C-terminal lysine, N-terminal cyclization, proline amidation, and the combination of modifications (not typically identified by other intact methods), including lysine and one or two hexose additions. Nonspecific chain cleavages were also resolved, along with their acidic charge variants, demonstrating highly sensitive and comprehensive intact antibody multi-attribute characterization within a 15-min run time.