Search

Root exudates are known signaling agents that influence legume root nodulation, but the molecular mechanisms for nonflavonoid molecules remain largely unexplored. The number of soybean root nodules during the initial growth phase shows substantial discrepancies at distinct developmental junctures. Using a combination of metabolomics analyses on root exudates and nodulation experiments, we identify a pivotal role for certain root exudates during the rapid growth phase in promoting nodulation. Phenoxyacetic acid (POA) was found to activate the expression of GmGA2ox10 and thereby facilitate rhizobial infection and the formation of infection threads. Furthermore, POA exerts regulatory control on the miR172c-NNC1 module to foster nodule primordia development and consequently increase nodule numbers. These findings collectively highlight the important role of POA in enhancing nodulation during the accelerated growth phase of soybeans. [ABSTRACT FROM AUTHOR]

The phenoxyacetic acid and its derivatives have attracted considerable attention as they have proven to be excellent bioactive herbicides. The optimized molecular geometry and the fundamental vibrational frequencies of 4-methyl-phenoxyacetic acid (4MPA), 4-acetyl-phenoxyacetic acid (4APA) and 4-tert-butyl-phenoxyacetic acid (4TBPA) have computed using density functional theory (DFT) method with 6–311++G(d,p) basis set. The theoretically predicted wavenumbers are found to be in close agreement with the experimentally determined one. The band gap energy of HOMO and LUMO depicts the charge transfer interactions occurring within the molecules. Global reactivity descriptors have utilized to assess the chemical reactivity. It has been observed that 4APA exhibits good electrophilic properties with a higher electrophilicity index (ω = 2.993 eV) compared to other compounds such as 4TBPA and 4MPA. The molecular electrostatic potential surface (MESP) has been plotted over the optimized structure to estimate the reactive sites of electrophilic and nucleophilic attacks on the phenoxyacetic acid molecule. Fukui function is also used to analyze their electrophilic and nucleophilic descriptors with Hirshfeld charges. Electron localization function (ELF) and local orbital localizer (LOL) are discussed using the multifunction wavefunction (Multiwfn) analyzer. Using the HerbiPAD tool, the herbicide-likeness parameter has exposed the good herbicide-like behaviour of the title compounds. Additionally, the Tice rule and pKa are described, providing valuable insights into the herbicidal activity of phenoxyacetic acid compounds. The 4APA compound is highly effective, which exhibits more herbicidal activity when interacting with the auxin receptor TIR1. It demonstrates a strong binding affinity of -8.56 kcal/mol. [ABSTRACT FROM AUTHOR]

2-Phenoxyethanol (PhE) is widely used as a preservative in consumer products such as cosmetics as well as at the workplace as a component of metal-working fluids and hydraulic fluids. Therefore, both industry workers and consumers may potentially be exposed to PhE. An analytical method for the quantification of PhE and three selected metabolites, namely phenoxyacetic acid (PhAA), 4-hydroxyphenoxyacetic acid (4-OH-PhAA), and 4-hydroxyphenoxyethanol (4-OH-PhE), in human urine and blood was developed and validated. The sample preparation includes enzymatic hydrolysis of urine samples or protein precipitation of blood samples, followed by liquid – liquid extraction and silylation of the target analytes. Analyses of the extracts were carried out by gas chromatography with tandem mass spectrometry (GC – MS-MS). 3,4-Hydroxyphenoxyethanol, a probably minor PhE metabolite, could not be reliably analyzed due to its instability. The limits of quantification (LOQ) of the analytes ranged between 0.5 and 6.1 μg/L and 2.0 and 3.9 μg/L in urine and blood, respectively. The method was successfully applied to spot urine samples of 50 individuals without occupational exposure to PhE and additionally to blood samples from seven volunteers. In urine, PhAA and 4-OH-PhAA could be quantified in all analyzed samples, whereas 4-OH-PhE and unchanged PhE were found in 36% and 32% of the samples, respectively. In blood, PhAA was also found in every sample in levels above the LOQ, whereas PhE itself was detected in three of seven samples only. Neither 4-OH-PhAA nor 4-OH-PhE was found in any of the analyzed blood samples. The developed method promises to be a valuable tool for PhE monitoring of urine and blood samples and may also enable an advanced investigation of PhE biotransformation pathways in humans. [ABSTRACT FROM AUTHOR]

This study focuses on the development and characterization of molecularly imprinted thin films in the absence and presence of a liquid crystal monomer, as well as the evaluation of these materials for recognition of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D). Molecular imprinted polymers (MIPs) and non-imprinted polymers (NIPs) were prepared by using two functional monomers, n-butylmethacrylate (BMA) and liquid crystalline (LC) 6-(4-cyanophenyl-4′phenoxy) hexyl acrylate (A6OCB). The resulting (MIPs) and (NIPs) materials were characterized by infrared spectroscopy (FTIR), Raman spectroscopy, polarized optical microscopy (POM), and atomic force microscopy (AFM). The entire monomer consumption, as well as the successful loading and extraction of the 2,4-D molecules, were validated by FTIR and Raman analyses. POM and AFM characterization revealed that the percentage of liquid crystal influenced the distribution of the liquid crystal domains and that the MIP films exhibited remarkable porosity. The experimental results revealed that the MIP films had a substantially higher adsorption capacity toward 2,4-D than the NIP materials and that increasing the liquid crystal content increased the adsorption capacity of both the MIP and NIP films. The selectivity tests in the presence of phenoxyacetic acid (POAc) showed that the MIP films exhibited higher affinity for 2,4-D than for the POAc. [ABSTRACT FROM AUTHOR]

2-Phenoxyethanol (PhE) is an aromatic glycol ether and is used in a variety of functions and applications, e.g., as preservative in pharmaceuticals, cosmetic and personal care products, as biocide in disinfectants (e.g. human hygiene), or as a solvent in formulations (e.g. coatings, functional fluids). Despite its widespread use, little is yet known on its biotransformation and toxicokinetics in humans. Therefore, a pilot study was conducted with oral administration of PhE (5 mg/kg body weight) to five volunteers. Blood and urine samples were collected and analyzed for PhE and three of its presumed metabolites up to 48 h post-exposure. Additionally, one volunteer was dermally exposed to PhE and monitored until 72 h post-exposure. PhE was rapidly resorbed following both oral and dermal application with tmax-levels in blood of about 1 h and 3 h, respectively. Metabolism of PhE was observed to be rather extensive with phenoxyacetic acid (PhAA) and 4-hydroxyphenoxyacetic acid (4-OH-PhAA) as the main metabolites found in blood and urine following oral and dermal exposure. PhE was excreted rapidly and efficiently via urine mostly in metabolized form: following oral exposure, on average 77% and 12% of the applied dose was excreted within 48 h as PhAA and 4-OH-PhAA, respectively. A similar metabolism pattern was observed following the single dermal exposure experiment. The obtained data on biotransformation and toxicokinetics of PhE in humans provide valuable information on this important chemical and will be highly useful for pharmacokinetic modelling and evaluation of human PhE exposure. [ABSTRACT FROM AUTHOR]

A new bis-Schiff base (L) Ca(II) complex, CaL, was synthesized by the reaction of calcium perchlorate tetrahydrate, 1,3-diamino-2-hydroxypropane, and 2-formyl phenoxyacetic acid in an ethanol–water (v:v = 2:1) solution and characterized by IR, UV-vis, TG-DTA, and X-ray single crystal diffraction analysis. The structural analysis indicates that the Ca(II) complex crystallizes in the monoclinic system, space group P121/n1, and the Ca(II) ions are six-coordinated with four O atoms (O8, O9, O11, O12, or O1, O2, O4, O6) and two N atoms (N1, N2, or N3, N4) of one bis-Schiff base ligand. The Ca(II) complex forms a tetramer by intermolecular O-H...O hydrogen bonds. The tetramer units further form a three-dimensional network structure by π–π stacking interactions of benzene rings. The Hirschfeld surface of the Ca(II) complex shows that the H...H contacts represent the largest contribution (41.6%) to the Hirschfeld surface, followed by O...H/H...O and C...H/H...C contacts with contributions of 35.1% and 18.1%, respectively. To understand the electronic structure of the Ca(II) complex, the DFT calculations were carried out. The photocatalytic CO2 reduction test of the Ca(II) complex exhibited a yield of 47.9 μmol/g (CO) and a CO selectivity of 99.3% after six hours. [ABSTRACT FROM AUTHOR]

The spread of COVID-19 infection continues due to the emergence of multiple transmissible and immune-evasive variants of the SARS-CoV-2 virus. Although various vaccines have been developed and several drugs have been approved for the treatment of COVID-19, the development of new drugs to combat COVID-19 is still necessary. In this work, new 5′-O-ester derivatives of N4-hydroxycytidine based on carboxylic acids were developed and synthesized by Steglich esterification. The antiviral activity of the compounds was assessed in vitro—inhibiting the cytopathic effect of HCoV-229E, and three variants of SARS-CoV-2, on huh-7 and Vero E6 cells. Data have shown that most synthesized derivatives exhibit high activity against coronaviruses. In addition, the relationship between the chemical structure of the compounds and their antiviral effect has been established. The obtained results show that the most active compound was conjugate SN_22 based on 3-methyl phenoxyacetic acid. The results of this study indicate the potential advantage of the chemical strategies used to modify NHC as a promising avenue to be explored in vivo, which could lead to the development of drugs with improved pharmacological properties that potently inhibit SARS-CoV-2. [ABSTRACT FROM AUTHOR]

The letter to the editor responds to a recent paper by Hardell and colleagues that investigated the risks of non-Hodgkin lymphoma (NHL) and hairy cell leukemia following exposure to glyphosate and phenoxyacetic acid herbicides. The authors of the letter argue that the methodological approaches used by Hardell et al. introduced bias and limitations that impacted the validity of their findings. They highlight concerns about recall bias, the construction of the reference group, small sample sizes, regression methods, and participation rates. The authors disagree with Hardell et al.'s conclusions and suggest that cohort studies provide more reliable evidence on the risks of glyphosate exposure and NHL. [Extracted from the article]

The association between pesticide exposure and non-Hodgkin lymphoma (NHL) including hairy cell leukemia (HCL) was analyzed in a pooled study of three case-control studies. Results on exposure to pesticides were based on 1,425 cases and 2,157 controls participating in the studies. Exposures were assessed by self-administered questionnaires completed as needed by phone. In the pooled univariate analyses adjusted by age, gender and year of diagnosis, exposure to herbicides of the phenoxyacetic acid type yielded statistically significant increased risk with odds ratio (OR) = 1.9, 95% confidence interval CI) = 1.4–2.5. The herbicide glyphosate gave OR = 2.2, 95% CI = 1.3–3.8. Impregnating agents increased the risk. No clear dose-response effect was seen. OR was highest in the >10–20 years latency group for herbicides and impregnating agents. In the multivariate analysis including main pesticide groups, statistically significant increased risk was found for herbicides, OR = 1.6, 95% CI = 1.2–2.1 and impregnating agents with OR = 1.4, 95% CI = 1.1–1.8. This analysis confirmed an association between NHL including HCL and exposure to certain herbicides. [ABSTRACT FROM AUTHOR]

Beta (β)-lactam antibiotic is an industrially important molecule produced by Penicillium chrysogenum/rubens. Penicillin is a building block for 6-aminopenicillanic acid (6-APA), an important active pharmaceutical intermediate (API) used for semi-synthetic antibiotics biosynthesis. In this investigation, we isolated and identified Penicillium chrysogenum, P. rubens, P. brocae, P. citrinum, Aspergillus fumigatus, A. sydowii, Talaromyces tratensis, Scopulariopsis brevicaulis, P. oxalicum, and P. dipodomyicola using the internal transcribed spacer (ITS) region and the β-tubulin (BenA) gene for precise species identification from Indian origin. Furthermore, the BenA gene distinguished between complex species of P. chrysogenum and P. rubens to a certain extent which partially failed by the ITS region. In addition, these species were distinguished by metabolic markers profiled by liquid chromatography–high resolution mass spectrometry (LC-HRMS). Secalonic acid, Meleagrin, and Roquefortine C were absent in P. rubens. The crude extract evaluated for PenV production by antibacterial activities by well diffusion method against Staphylococcus aureus NCIM-2079. A high-performance liquid chromatography (HPLC) method was developed for simultaneous detection of 6-APA, phenoxymethyl penicillin (PenV), and phenoxyacetic acid (POA). The pivotal objective was the development of an indigenous strain portfolio for PenV production. Here, a library of 80 strains of P. chrysogenum/rubens was screened for PenV production. Results showed 28 strains capable of producing PenV in a range from 10 to 120 mg/L when 80 strains were screened for its production. In addition, fermentation parameters, precursor concentration, incubation period, inoculum size, pH, and temperature were monitored for the improved PenV production using promising P. rubens strain BIONCL P45. In conclusion, P. chrysogenum/rubens strains can be explored for the industrial-scale PenV production. [ABSTRACT FROM AUTHOR]

Biochar activation methods have attracted extensive attention due to their great role in improving sorptive properties of carbon-based materials. As a result, chemically modified biochars gained application potential in the purification of soil and water from xenobiotics. This paper describes changes in selected physicochemical properties of high-temperature wheat-straw biochar (BC) upon its deashing. On the pristine and chemically activated biochar (BCd) retention of five pesticides of endocrine disrupting activity (carbaryl, carbofuran, 2,4-D, MCPA and metolachlor) was studied. Deashing resulted in increased sorbent aromaticity and abundance in surface hydroxyl groups. BCd exhibited more developed meso- and microporosity and nearly triple the surface area of BC. Hydrophobic pesticides (metolachlor and carbamates) displayed comparably high (88–98%) and irreversible adsorption on both BCs, due to the pore filling, whereas the hydrophilic and ionic phenoxyacetic acids were weakly and reversibly sorbed on BC (7.3 and 39% of 2,4-D and MCPA dose introduced). Their removal from solution and hence retention on the deashed biochar was nearly total, due to the increased sorbent surface area and interactions of the agrochemicals with unclogged OH groups. The modified biochar has the potential to serve as a superabsorbent, immobilizing organic pollutant of diverse hydrophobicity from water and soil solution. [ABSTRACT FROM AUTHOR]

This work investigated the photocatalytic degradation of the 4-chloro-2-methylphenoxyacetic acid herbicide and its primary intermediate (4-chloro-2-methyl phenol) using the coupled catalyst TiO2 modified with the iron oxide species, FeOOH and Fe2O3 (FeOx, 0.5 wt.%), under UV–Vis radiation assisted with persulfate or peroxymonosulfate. The FeOx–TiO2 composite prepared by microwave-assisted sol–gel method was characterized by X-Ray Diffraction, Nitrogen Physisorption, UV–Vis Diffuse Reflectance Spectroscopy, Fourier Transform Infrared Spectroscopy, Atomic Absorption Spectroscopy, Photoluminescence, X-Ray Photoelectron Spectroscopy, Thermogravimetric Analysis, Scanning Electron Microscopy, and Transmission Electron Microscopy. The anatase phase was conserved in the FeOx–TiO2 material. The coupling of FeOx in TiO2 decreased the crystallite size and enhanced the specific surface area and visible light response. A response surface methodology based on Central Composite Design was used to obtain the optimal oxidant agent (persulfate or peroxymonosulfate), oxidant dosage, and solution pH conditions to enhance the 4-chloro-2-methylphenoxyacetic acid mineralization. The 87.04% of 4-chloro-2-methylphenoxyacetic acid mineralization was achieved by FeOx–TiO2 composite with persulfate (5 mM) under UV–Vis radiation at pH 7 in 150 min showing a synergic effect. This result allowed the complete elimination of 4-chloro-2-methylphenoxyacetic acid and the by-product 4-chloro-2-methyl phenol generated during the reaction compared to 61.6 and 27.9% mineralization obtained with FeOx–TiO2 + hυ and persulfate oxidation + hυ, respectively. The photogenerated electrons in FeOx–TiO2 improved mineralization efficiency that allows the persulfate activation. Besides, the coupling between FeOx and TiO2 suppresses the electron/hole (e−/h+) pair recombination of FeOx–TiO2 photocatalyst. [ABSTRACT FROM AUTHOR]

Recently, 2,4-dichlorophenoxyacetic acid, 4-chlorophenoxyacetic acid, and 2-methyl-4-chlorophenoxyacetic acid have been extensively used as herbicides in field crops and they can also act as a plant growth regulator at low concentrations. However, these compounds possess high vapor pressure and high volatility. In this regard, the introduction of ionic liquids (ILs) has emerged as an effective approach to overcome these shortcomings. The present study aimed to prepare a series of ILs with bactericidal activity cations and phenoxyacetic acid series compounds as anions. The synthesized compounds were tested for their physicochemical properties, antibacterial activity and citrus preservation through experiments. ILs showed lower volatility, better soil adsorption capacity, and dual functions of plant growth regulation and antibacterial activity. The tested ILs effectively delayed the aging rate of citrus, reduced the decay rate, inhibited citrus storage diseases, and improved the storage quality of citrus. Overall, the study results provide a theoretical basis for the development of sustainable multifunctional ILs by introducing anions and cations with targeted effects. These newly synthesized ILs allowed us to achieve benefits far exceeding the simple additive rule, improving the physical and chemical properties and reducing environmental pollution by decreasing the amount of chemicals. [ABSTRACT FROM AUTHOR]

A novel sorbent (SiO2‐(CH2)3‐DABCO) for solid‐phase extraction (SPE) was successfully prepared by chemical‐bonding formation of diazabicyclo[2.2.2]octane ionic liquid onto silica gel. The structure of SiO2‐(CH2)3‐DABCO sorbent was characterized by FT‐IR, TGA, SEM, EDX, and BET methods. Cartridges packed with the synthetic SiO2‐(CH2)3‐DABCO were used for the preconcentration of trace‐level of phenoxyacetic acid herbicides in water samples for the first time. The factors influencing on the recovery were investigated, such as type of ion liquids, loading volume, eluents, elution volume, loading rate, and capacity. After the enrichment, the phenoxyacetic acid herbicides were analyzed by high‐performance liquid chromatography with an ultraviolet detector. Four model phenoxyacetic acid herbicides, including 2‐methyl‐4‐chlorophenoxyacetic acid (MCPA), 2,4,5‐trichlorophenoxyacetic acid (2,4,5‐T), fenoprop (2,4,5‐TP) and haloxyfop were well retained and separated by this material with a recovery efficiency from 77 to 103 %. The SiO2‐(CH2)3‐DABCO demonstrated a good capacity corresponding to 0.56 mg of the analyte adsorbed per 100 mg of the material. The mixture of phosphate buffer (pH 7) : MeOH (50 : 50, v/v) was used to elute the analytes and provided the highest recovery with the standard deviations from 2.4 to 6.5. The high sensitivity with detection limits of 1.070–9.587 μg/L can be achieved. [ABSTRACT FROM AUTHOR]

Microbial metabolism is an important driving force for the elimination of 4-chlorophenoxyacetic acid residues in the environment. The α-Ketoglutarate-dependent dioxygenase (TfdA) or 2,4-D oxygenase (CadAB) catalyzes the cleavage of the aryl ether bond of 4-chlorophenoxyacetic acid to 4-chlorophenol, which is one of the important pathways for the initial metabolism of 4-chlorophenoxyacetic acid by microorganisms. However, strain Cupriavidus sp. DL-D2 could utilize 4-chlorophenoxyacetic acid but not 4-chlorophenol for growth. This scarcely studied degradation pathway may involve novel enzymes that has not yet been characterized. Here, a gene cluster (designated cpd) responsible for the catabolism of 4-chlorophenoxyacetic acid in strain DL-D2 was cloned and identified, and the dioxygenase CpdA/CpdB responsible for the initial degradation of 4-chlorophenoxyacetic acid was successfully expressed, which could catalyze the conversion of 4-chlorphenoxyacetic acid to 4-chlorocatechol. Then, an aromatic cleavage enzyme CpdC further converts 4-chlorocatechol into 3-chloromuconate. The results of substrate degradation experiments showed that CpdA/CpdB could also degrade 3-chlorophenoxyacetic acid and phenoxyacetic acid, and homologous cpd gene clusters were widely discovered in microbial genomes. Our findings revealed a novel degradation mechanism of 4-chlorophenoxyacetic acid at the molecular level. [Display omitted] • 4-chlorophenoxyacetic acid-degrading strain Cupriavidus sp. DL-D2 was isolated. • The cpd gene cluster was involved in 4-CPA degradation. • The initial catabolism of 4-CPA in strain DL-D2 was performed by CpdA/CpdB. • CpdA/CpdB could catalyze the conversion of 4-CPA to 4-chlorocatechol. • Homologous cpd gene clusters have been discovered in different microbial genomes. [ABSTRACT FROM AUTHOR]

The determination of plant growth regulators is of great importance for the quality monitoring of crops. In this work, 4-bromophenoxyacetic acid (4-BPA), one of the phenoxyacetic acids, was detected via the electrochemical method for the first time. A CeO2-decorated electrochemical exfoliated graphene (eGr) composite (CeO2/eGr) was constructed as the sensor for sensitive detection of 4-BPA due to the synergistic effect of the excellent catalytic active sites of CeO2 and good electron transference of the eGr. The developed CeO2/eGr sensor displayed a good linearity in a wide range from 0.3 to 150 μmol/L and the lowest detection limit of 0.06 μmol/L for 4-BPA detection. Electrochemical oxidation of 4-BPA follows a mix-controlled process on the CeO2/eGr electrode, which involves 2e in the transference process. This developed CeO2/eGr sensor has excellent repeatability with a relative standard deviation (RSD) of 2.35% in 10 continuous measurements. Moreover, the practical application of the sensor for 4-BPA detection in apple juice has recoveries in the range of 90–108%. This proposed CeO2/eGr sensor has great potential for detecting plant growth regulators in the agricultural industry. [ABSTRACT FROM AUTHOR]

Root exudates are known signaling agents that influence legume root nodulation, but the molecular mechanisms for nonflavonoid molecules remain largely unexplored. The number of soybean root nodules during the initial growth phase shows substantial discrepancies at distinct developmental junctures. Using a combination of metabolomics analyses on root exudates and nodulation experiments, we identify a pivotal role for certain root exudates during the rapid growth phase in promoting nodulation. Phenoxyacetic acid (POA) was found to activate the expression of GmGA2ox10 and thereby facilitate rhizobial infection and the formation of infection threads. Furthermore, POA exerts regulatory control on the miR172c-NNC1 module to foster nodule primordia development and consequently increase nodule numbers. These findings collectively highlight the important role of POA in enhancing nodulation during the accelerated growth phase of soybeans., Competing Interests: Competing interests statement:The authors declare no competing interest.

In the presence of perchloric acid, the kinetics and oxidation of phenol, phenoxy acetic acid, and a few para-substituted phenols and phenoxyacetic acids by pyrazinium chlorochromate (PzCC) were investigated in acetic acid and water medium. The reaction was fractional-order for both the substrates and unit order for oxidant and acid. The products of oxidation are quinone. Comparing the reaction rate for phenols and their derivatives revealed a similar behavior. The oxidation and kinetics of phenol and its derivatives are established using the non-linear Hammett plots plot which reveal that para-methyl groups slow down the reaction rate and para-nitro and para-chloro groups speed up the reaction rate. Based on the kinetic data and product analyses, an appropriate mechanism has been provided. [ABSTRACT FROM AUTHOR]

The micellar liquid chromatography technique and quantitative retention (structure)–activity relationships method were used to predict properties of carbamic and phenoxyacetic acids derivatives, newly synthesized in our laboratory and considered as potential pesticides. Important properties of the test substances characterizing their potential significance as pesticides as well as threats to humans were considered: the volume of distribution, the unbonded fractions, the blood–brain distribution, the rate of skin and cell permeation, the dermal absorption, the binding to human serum albumin, partitioning between water and plants' cuticles, and the lethal dose. Pharmacokinetic and toxicity parameters were predicted as functions of the solutes' lipophilicities and the number of hydrogen bond donors, the number of hydrogen bond acceptors, and the number of rotatable bonds. The equations that were derived were evaluated statistically and cross-validated. Important features of the molecular structure influencing the properties of the tested substances were indicated. The QSAR models that were developed had high predictive ability and high reliability in modeling the properties of the molecules that were tested. The investigations highlighted the applicability of combined chromatographic technique and QS(R)ARs in modeling the important properties of potential pesticides and reducing unethical animal testing. [ABSTRACT FROM AUTHOR]

2,4-dichlorophenoxyacetic acid (2,4-D) is a widely used herbicide for controlling broad-leaved weeds. The development of an efficient process for treating the refractory 2,4-D wastewater is necessary. In this study, liquid-phase degradation of 2,4-D induced by radio frequency discharge (RFD) was studied. Experimental results showed that the degradation was more effective in acidic than in neutral or alkaline solutions. During the degradation, a large amount of hydrogen peroxide (H2O2, 1.2 mM/min, almost equal to that without 2,4-D) was simultaneously produced, and catalytic effects of both ferric (Fe3+) and ferrous (Fe2+) ions on the degradation were examined and compared. It was found that 2,4-D degraded more rapidly in the case of Fe3+ than the that of Fe2+. Such a scenario is explained that Fe3+ was successively reduced to Fe2+ by the atomic hydrogen (•H) and •OH-adducts of 2,4-D resulting from RFD, which in turn catalyzed the H2O2 to form more •OH radicals through Fenton's reaction, indicating that Fe3+ not only accelerates the degradation rate but also increases the amount of •OH available for 2,4-D degradation by suppressing the back reaction between the •H and •OH. 2,4-dichlorophenol, 4,6-dichlororesorcinol, 2-hydroxy-4-chloro- and 2-chloro-4-hydroxy- phenoxyacetic acids, hydroxylated 2,4-Ds, and carboxylic acids (glycolic, formic and oxalic) were identified as the byproducts. Energy yields of RFD have been compared with those of other nonthermal plasma processes. [ABSTRACT FROM AUTHOR]

This work aims to evaluate the potential of raw lignite as a low-cost adsorbent material for the removal of phenoxy herbicides including phenoxyacetic acid (PAA), 4-chlorophenoxyacetic acid (4-CPA), 2,4-dichlorophenoxyacetic acid (2,4-D), and 4-chloro-2-methylphenoxyacetic acid (MCPA) from aqueous solutions. Batch adsorption experiments at different operating parameters such as pH and ionic strength were carried out, and the results revealed that adsorption of the herbicides was strongly pH- and ionic strength dependent. The adsorption kinetics was fitted with the pseudo-first-order and pseudo-second-order models, while adsorption equilibrium data were fitted using Langmuir, Freundlich, and Langmuir-Freundlich isotherm equations. The obtained data obeyed the pseudo-second-order kinetic and Freundlich isotherm type. Adsorption efficiency of the herbicides increased in the order PAA < 4-CPA < 2,4-D < MCPA and the monolayer adsorption capacities were 20.53, 27.10, 35.21, and 37.04 µmol/g, respectively. The results showed that the raw lignite may be used as an effective low-cost adsorbent without any treatment or any other modification for the removal of phenoxy herbicides from the aqueous solutions. [ABSTRACT FROM AUTHOR]

A physiologically based pharmacokinetic (PBPK) model for the important chemical phenoxyethanol (PhE) and its metabolite phenoxyacetic acid (PhAA) was built via GastroPlusTM software (version 9.0) using currently available analytically measured plasma and urinary time-courses of both PhE and its metabolite PhAA. This model was validated and used to predict tissue and urine concentrations of PhE and its metabolite PhAA in rats and humans after oral and dermal exposures. The prediction results showed that most predicted tissue concentrations of PhE or PhAA were lower than the experimental tissue concentrations based on total radioactivity. The predicted cumulative excretion of PhAA in both rats and humans fits very well with most experimental data. With this GastroPlusTM-based model, the margins of exposure (MOE) of PhE and PhAA were also calculated as 194 and 73.7, respectively. The predicted MOE of PhE is two-fold higher than the previous PBPK model built using total radioactivity-based tissue time courses, and the predicted MOE of PhAA was comparable to the previous PBPK model. These data indicate that for chemicals like PhE, GastroPlusTM can integrate multiple data sets into PBPK models to predict PK parameters for parent and metabolites in both rats and humans following intravenous, dermal, or oral exposures. [ABSTRACT FROM AUTHOR]

• Theoretical investigation on the noncovalent MIPs used in aqueous environment. • A modified suspension polymerization was proposed to synthesize 2,4- d -MIP. • 2,4- d -MIP has high adsorption capacity, excellent selectivity and reusability. • 2,4- d -MIP shows strong anti-protein adsorption in aqueous environment. Herein, 2,4-dichlorophenoxyacetic acid (2,4-D) was used as a model template in a rational design strategy to produce water-compatible noncovalent imprinted microspheres. The proposed approach involved computational modelling for screening functional monomers and a simple method for preparing monodisperse and highly cross-linked microspheres. The fabricated non-imprinted polymer (NIP) and 2,4- d -imprinted polymer (2,4- d -MIP) were characterised, and their adsorption capabilities in an aqueous environment were evaluated. Results reveal that the pseudo-second-order kinetics model was appropriate for representing the adsorption of 2,4-D on NIP and 2,4- d -MIP, with R2 values of 0.97 and 0.99, respectively. The amount of 2,4-D adsorbed on 2,4- d -MIP (97.75 mg g −1) was considerably higher than those of phenoxyacetic acid (35.77 mg g −1), chlorogenic acid (9.72 mg g −1), spiramycin (1.56 mg g −1) and tylosin (1.67 mg g −1). Furthermore, it exhibited strong resistance to protein adsorption in an aqueous medium. These findings confirmed the feasibility of the proposed approach, providing a reference for the development of water-compatible noncovalent imprinted polymers. [ABSTRACT FROM AUTHOR]

• A novel SDES was prepared for green extraction of phenoxyacetic acid herbicides in water and food matrices. • Switching property of SDES was characterized by FT-IR and 1H NMR. • Cytotoxicity of SDES was studied to verify the safety and greenness. • The method displays advantages of green, sensitive and efficient. In this work, a switchable deep eutectic solvent (SDES) based on fatty acid and polyetheramine ion pair was prepared for liquid-phase microextraction (LPME) of phenoxyacetic acid herbicides in drinking water, beverage and honey matrices. The as-synthesized SDES equipped with an interesting characteristic of fast and reversible polarity switching, achieving homogeneous extraction and rapid bi-phase separation simultaneously. Several key parameters affecting the extraction performance were investigated comprehensively by Box-Behnken design. Under the optimal conditions, the method exhibited excellent linearity (15–4000 μg L−1), low detection limits (3–5 μg L−1), desirable precision (RSD < 8.1 %), and satisfactory recovery (72.6–98.7 %). More importantly, the introduction of SDES can simplify the pre-treatment procedure, shorten extraction time (4 min), and avoid the usage of traditional organic solvent during the whole extraction process. In addition, the switching mechanism of SDES was characterized by FT-IR and 1H NMR, and the forming mechanism of SDES was investigated using density-functional theory. The green of the method was estimated using the analytical ecological scale, the analytical green calculator, and the green analytical procedure index. The cytotoxicity of SDES was investigated and the result displayed that toxicity of the SDES was very low with the EC 50 > 500 mg/L. Therefore, the proposed method was green and efficient and revealed considerable application prospects for the extraction of trace analytes from complex materials. [ABSTRACT FROM AUTHOR]

Radiotherapy is a vital approach for brain tumor treatment. The standard treatment for glioblastoma (GB) is maximal surgical resection combined with radiotherapy and chemotherapy. However, the non-sensitivity of tumor cells in the hypoxic area of solid tumors to radiotherapy may cause radioresistance. Therefore, radiotherapy sensitizers that increase the oxygen concentration within the tumor are promising for increasing the effectiveness of radiation. Inspired by hemoglobin allosteric oxygen release regulators, a series of novel phenoxyacetic acid analogues were designed and synthesized. A numerical method was applied to determine the activity and safety of newly synthesized compounds. In vitro studies on the evaluation of red blood cells revealed that compounds 19c (∆P50 = 45.50 mmHg) and 19t (∆P50 = 44.38 mmHg) improve the oxygen-releasing property effectively compared to positive control efaproxiral (∆P50 = 36.40 mmHg). Preliminary safety evaluation revealed that 19c exhibited no cytotoxicity towards HEK293 and U87MG cells, while 19t was cytotoxic toward both cells with no selectivity. An in vivo activity assay confirmed that 19c exhibited a radiosensitization effect on orthotopically transplanted GB in mouse brains. Moreover, a pharmacokinetic study in rats showed that 19c was orally available. [ABSTRACT FROM AUTHOR]

Novel hydrazones based on (‒)-carvone were synthesized via condensation of terpenoid with 4-R-phenoxyacetic acid hydrazides. The structure of target compounds was established by FT-IR, Raman, 1H-NMR and 13C-NMR spectral analysis, FAB/ESI mass spectrometry. (‒)-Carvone hydrazones were proven to exist as Z/E geometrical isomers about C = N bond using ion mobility-tandem mass spectrometry (IM-MS/MS). Single crystal X-ray diffraction study was applied to determine molecular and crystal structure of compound 3e. Hydrazones 3a-3e were evaluated as potential anticonvulsant agents after their oral administration against maximal electroshock (MES) and pentylenetetrazole (PTZ)-induced seizures in mice. Analgesic activity of compounds was investigated by topical application on models of capsaicin and AITC-induced pain. The present findings indicate that (‒)-carvone derivatives afforded seizure protection both at short (1 h) and long (24 h) time period by blocking electroshock- and chemical-induced convulsions. Hydrazones binding to TRPA1/TRPV1 ion channels was proposed as possible mechanism explaining significant analgesic effect of compounds. [ABSTRACT FROM AUTHOR]

A series of novel (−)-verbenone hydrazones was designed and synthesized via condensation of terpenoid with hydrazides derived from phenoxyacetic acid. The structure of target compounds was confirmed by 1H-NMR and 13C-NMR analysis, Raman and FT-IR spectroscopy, electrospray ionization method and fast atom bombardment (FAB) mass spectrometry. Thermal properties of (−)-verbenone hydrazones 3a–3e were estimated by differential scanning calorimetry and their purity by HPLC coupled to mass spectrometry. Verbenone hydrazones were revealed to exist as Z/E geometrical isomers about C═N bond and cis/trans amide conformers. Verbenone derivatives were estimated as potential anticonvulsant agents after their oral administration against pentylenetetrazole and maximal electroshock-induced seizures in mice. Analgesic effect of hydrazones was studied by topical application on models of allyl isothiocyanate and capsaicin-induced pain. The present findings indicate that verbenone hydrazones contribute to seizure protection both at short (6 h) and long (24 h) time periods by blocking chemical- and electroshock-induced convulsions. Binding of compounds 3a–3e to TRPA1/TRPV1 ion channels was suggested as a feasible mechanism explaining their significant analgesic activity.

A novel extractant, 2‐(2‐heptanoylphenoxy)acetic acid (HA), was synthesized and applied to extract La, Ce, Pr, and Nd from the hydrochloric acid solution. The extraction parameters including pH, temperature, concentrations of HA and chloride ion were investigated and discussed in detail. The extraction mechanism was studied with Fourier‐transform infrared (FT‐IR) spectroscopy. Compared with the extractant of sec‐octylphenoxy acetic acid (CA12), HA showed excellent performance and different extraction order in extracting La, Ce, Pr, and Nd. All the rare‐earth metals (REs) were extracted by the cation exchange mechanism and loaded as REs(A)3. The stripping test showed that the loaded REs in the organic phase can be effectively stripped with sulfuric acid at medium acidity. This work revealed that HA is an effective extractant for REs. [ABSTRACT FROM AUTHOR]

A new binary ZnII coordination polymer, [Zn(2-cpa)(H2O)]n (2D-Zn) has been prepared by a 120 °C hydrothermal reaction of zinc(II) sulfate heptahydrate and 2-carboxy phenoxyacetic acid (2-H2cpa) in the presence of potassium hydroxide. Single-crystal X-ray diffraction analysis shows that the ZnII ion is located in a deformed ZnO6 octahedron bonded by one water and three 2-carboxy phenoxyacetate (2-cpa) ligands. The 2-cpa exhibits pentadentate double bridging chelate-μ3 coordination mode and connects adjacent ZnII ions to generate a corrugated (4,4)-connected layer structure. The structures, conformation of 2-cpa and photoluminescence spectra for 2D-Zn have been carefully analyzed and compared with its two closely related compounds ̶ 1D [Zn(2-cpa)(H2O)]n (1D-Zn) and mononuclear [Zn(2-cpa)(H2O)3] (0D-Zn). The results showed that the conformation of 2-cpa in 2D-Zn has the maximum alteration and the corresponding fluorescence emission peak of 2D-Zn has the largest red-shift of 62 nm compared with that of free 2-H2cpa. [ABSTRACT FROM AUTHOR]

From 2001 to 2014, 13 surveys were conducted in the Baltic Sea, to determine its pollution of 50 micropollutants. The investigations focused mostly on the German western Baltic Sea; in 2008, one survey covered the entire Baltic Sea. Various groups of herbicides (such as triazines, phenoxyacetic acid, phenylurea), perfluoroalkyl substances, pharmaceuticals, and industrial products were analyzed during these surveys. The highest concentrations (median 1 to 4 ng/L) were observed for atrazine, simazine, chloridazone, 2,4-dichlorophenoxyacetic acid, benzotriazole, primidone, and carbamazepine. Most micropollutants exhibited a relatively homogenous spatial distribution, though some herbicides show elevated concentrations in certain regions (e.g., Odra estuary), indicating a riverine input. The data set was analyzed, both for seasonal influences and long-time trends. Some herbicides exhibited higher concentrations during summertime. Both upward- and downward-directed time trends could be identified for some herbicides and perfluorinated compounds. For most of the detected compounds, a low-risk quotient was calculated. Only the occurrence of carbendazim could potentially pose a higher risk to the Baltic Sea. [ABSTRACT FROM AUTHOR]

2-Phenoxyethanol (PE), ethylene glycol monophenyl ether, is widely used as a preservative in cosmetic products as well as in non-cosmetics. Since PE has been used in many types of products, it can be absorbed via dermal or inhaled route for systemic exposures. In this study, the pharmacokinetic (PK) studies of PE and its major metabolite, phenoxyacetic acid (PAA), after dermal (30 mg and 100 mg) and inhaled administration (77 mg) of PE in rats were performed. PE was administered daily for 4 days and blood samples were collected at day 1 and day 4 for PK analysis. PE was rapidly absorbed and extensively metabolized to form PAA. After multiple dosing, the exposures of PE and PAA were decreased presumably due to the induction of metabolizing enzymes of PE and PAA. In dermal mass balance study using [14C]-phenoxyethanol ([14C]PE) as a microtracer, most of the PE and its derivatives were excreted in urine (73.03%) and rarely found in feces (0.66%). Based on these PK results, a whole-body physiologically-based pharmacokinetic (PBPK) model of PE and PAA after dermal application and inhalation in rats was successfully developed. Most of parameters were obtained from the literatures and experiments, and intrinsic clearance at steady-state (CLint,ss) were optimized based on the observed multiple PK data. With the developed model, systemic exposures of PE and PAA after dermal application and inhalation were simulated following no-observed-adverse-effect level (NOAEL) of 500 mg/kg/day for dermal application and that of 12.7 mg/kg/day for inhalation provided by the Environmental Protection Agency. The area under the concentration–time curve at steady state (AUCss) in kidney and liver (and lung for inhalations), which are known target organs of exhibiting toxicity of PE, as well as AUCss in plasma of PE and PAA were obtained from the model. [ABSTRACT FROM AUTHOR]

Members of the Raoultella planticola species isolated from soils contaminated with chemical waste were able to use 2,4-dichlorophenoxyacetic/2,4,5-trichlorophenoxyacetic acid as the sole source of carbon and energy. It was found that cells of strains 33-4ch, 36D, and 36T contained plasmids that were designated as pRP33-4ch, pRP36D and pRP36T, respectively. Restriction fragment length polymorphism (RFLP) analysis showed that pRP33-4ch and pRP36T were probably the same plasmid, while pRP36D contained additional fragments in the restriction profiles. Plasmid elimination showed that the genes for the degradation of chlorophenoxyacetic acids have extrachromosomal localization. Polymerase chain reaction (PCR) demonstrated the absence in the genomes of the studied strains of known initiation genes (tfdA and tftA) for the conversion of chlorophenoxyacetic acids. The identified intermediate metabolites (chlorophenoxyacetic and phenoxyacetic acids and 2-keto-3-methylmuconic semialdehyde) indicated that the strains 33-4ch, 36D, and 36T perform complete dechlorination of the aromatic ring of the substrate with its subsequent meta-cleavage. [ABSTRACT FROM AUTHOR]

2-Methyl-4-chlorophenoxyacetic acid (MCPA) is a pervasive phenoxyacetic acid herbicide, frequently identified in environmental matrices. This study undertakes a systematic investigation of the atmospheric environmental transformation behavior and potential ecological risks of hydroxyl radical (HO•) induced MCPA for the first time, employing computational chemistry and computational toxicology methodologies. Our findings indicate that the initial degradation of MCPA can be triggered by both HO•-addition and hydrogen-abstraction reactions, with the latter being more likely to occur. The primary reaction pathways were identified as R2, R3, R8, and R13. The total rate constant for the gas-phase reaction of MCPA with HO• was calculated as 8.59 × 10−12 cm3 molecule −1 s−1 at 298 K. This total rate constant displayed a distinct positive temperature dependence within the temperature range of 250–375 K. Structures of 25 transformation products, which include 7 experimentally observed compounds, were determined from further reactions of crucial intermediates. The toxicity assessment of MCPA and its transformation products indicated that most of the hydroxyl oxidation products exhibit toxicity to aquatic organisms and possess mutagenic, developmental toxic, non-genotoxic carcinogenic, and skin irritating or corrosive properties. This research contributes to a comprehensive understanding of the transformation mechanisms, kinetics, and environmental repercussions of gas-phase MCPA, enhancing our ability to predict and mitigate its ecological impact. • H-abstraction occurring on the methyl group is the most favorable initial pathway. • Rate constants and branching ratios were determined for the MCPA+HO • reaction. • Ecological risk assessment of MCPA and its products were conducted. [ABSTRACT FROM AUTHOR]

Radiotherapy is a vital approach for brain tumor treatment. The standard treatment for glioblastoma (GB) is maximal surgical resection combined with radiotherapy and chemotherapy. However, the non-sensitivity of tumor cells in the hypoxic area of solid tumors to radiotherapy may cause radioresistance. Therefore, radiotherapy sensitizers that increase the oxygen concentration within the tumor are promising for increasing the effectiveness of radiation. Inspired by hemoglobin allosteric oxygen release regulators, a series of novel phenoxyacetic acid analogues were designed and synthesized. A numerical method was applied to determine the activity and safety of newly synthesized compounds. In vitro studies on the evaluation of red blood cells revealed that compounds 19c (∆P50 = 45.50 mmHg) and 19t (∆P50 = 44.38 mmHg) improve the oxygen-releasing property effectively compared to positive control efaproxiral (∆P50 = 36.40 mmHg). Preliminary safety evaluation revealed that 19c exhibited no cytotoxicity towards HEK293 and U87MG cells, while 19t was cytotoxic toward both cells with no selectivity. An in vivo activity assay confirmed that 19c exhibited a radiosensitization effect on orthotopically transplanted GB in mouse brains. Moreover, a pharmacokinetic study in rats showed that 19c was orally available.

Baclofen (BAC, (R/S)-4-amino-3-(4-chlorophenyl)butanoic acid), was used to form multicomponent crystals (MCCs) with coformers (CFs) of different acidic strength and molecular size. The crystallisation of BAC with oxalic acid (OXA), salicylic acid (SAL), phenoxyacetic acid (POA), 2,4-dichlorophenoxyacetic acid (2,4ClPOA), 4-picoline (4PIC) and 3,4-lutidine (3,4LUT) yielded seven MCCs. The bulk materials were analysed by thermoanalytical methods (thermogravimetry and differential scanning calorimetry), powder X-ray diffraction analysis and Fourier transform infrared spectrometry. Liquid assisted grinding was also applied to form the MCCs. X-ray analysis of the single crystal structures revealed that BAC exists in zwitterionic or cationic form, and the MCCs represent a large variety of crystal classes, such as salts, salt solvates, cocrystal salt solvates or solvates with different stoichiometry. It was noted that BAC appeared in many different conformations in the MCCs, but comparative crystal packing analysis revealed similarities in the packing arrangement of the MCCs. This structural feature can be used for crystal engineering purposes when MCCs of BAC are designed. [ABSTRACT FROM AUTHOR]

Copyright of Journal of Faculty of Pharmacy of Ankara University / Ankara Üniversitesi Eczacilik Fakültesi Dergisi is the property of Ankara University and its content may not be copied or emailed to multiple sites or posted to a listserv without the copyright holder's express written permission. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.)

In the present study, peanut shell, a green waste raw material, was used to prepare biochar (BC) and to obtain BC‐supported nano‐palladium/iron (BC‐nPd/Fe) composites for removing 2,4‐dichlorophenoxyacetic acid (2,4‐D) from water. Characterization analysis demonstrated that nPd/Fe particles were well dispersed on the BC surface with weakened magnetic properties. The average particle diameter and specific surface area of nPd/Fe were 101.3 nm and 6.7 m2 g−1, whereas the corresponding values of the BC‐nPd/Fe materials were 88.8 nm and 14.8 m2 g−1, respectively. Several factors were found to influence the dechlorination of 2,4‐D, including the weight ratio of BC to Fe, Pd loading ratio, initial solution pH, 2,4‐D concentration, and reaction temperature. Dechlorination results indicated that the 2,4‐D removal and phenoxyacetic acid (PA) generation rates were 44.1% and 20.1%, respectively, in the nPd/Fe system, and 100.0% and 92.1%, respectively, in the BC‐nPd/Fe system. The dechlorination of 2,4‐D was well described by the pseudo‐first‐order kinetic model (R2 > 0.97), and the observed rate constants kobs were 0.0042 min (nPd/Fe) and 0.0578 min (BC‐nPd/Fe), respectively. The reaction mechanism indicated that the dechlorination hydrogenation was the main process to remove 2,4‐D from water in the BC‐nPd/Fe system. In addition, BC inhibited the formation of a passivation layer on the particle surface during the reaction, thus maintaining the high reactivity of BC‐nPd/Fe. The easy preparation technique, high 2,4‐D dechlorination capacity, and mild reaction conditions suggest that BC‐nPd/Fe may be a promising alternative composite to remove 2,4‐D from water. [ABSTRACT FROM AUTHOR]

Batch and packed bed adsorption of 4-chloro-2-methylphenoxyacetic acid (MCPA) herbicide was performed using bagasse fly ash (BFA) as an adsorbent. In batch process, characteristics of adsorbent, and the influence of adsorbent dosage, initial herbicide concentration, time, pH, particle size of adsorbent and temperature on adsorption were studied. Results disclose higher removal of MCPA on bigger particles of BFA owing to higher specific surface area because of greater carbon and lesser silica percentage in bigger particles. Application of isotherm models in present study indicates the best fitting of Langmuir and Temkin isotherms whereas the kinetic models suggest the suitability of pseudo second order and Elovich models. Thermodynamic study specifies the temperature preferred adsorption process. In packed bed technique, the effect of influent concentration, flow rate and bed height were investigated. The deactivation kinetic model which was previously considered only for studies in gas-solid adsorption is applied in this study to solid-liquid adsorption along with conventional packed bed models. In packed bed study, Bohart-Adams and Wolborska models are appropriate to explain the experimental data upto 60% saturation of the column. The deactivation kinetic model is found the best to elucidate the nature of breakthrough curves till the complete saturation of column. Batch capacity and packed bed capacity per m2 specific surface area of BFA is found about two and three times greater than the previously used adsorbents for MCPA respectively. [ABSTRACT FROM AUTHOR]

The synthesis of three kinds of sorbents is described. The first kind was a hydrophobic nanofiber as a specific sorbent for non-polar compounds. The second one was a hydrophilic nanofiber as a specific sorbent for polar compounds and the third one was a generic sorbent synthesized from hydrophilic and hydrophobic compounds. The functional groups were natural compounds extracted from aloin plant and gum of pine tree. The aloin/polyacrylonitrile (PAN), rosin/PAN, and aloin/rosin/PAN electrospun nanofibers were synthesized through electrospinning strategy and then characterized using field emission scanning electron microscopy and Fourier transform infrared spectroscopy. Thereafter, the synthesized sorbents were used in microextraction using the packed syringe (MEPS) method. The determination was conducted using gas chromatography with flame ionization detection (GC-FID). Under the optimum condition, the method using aloin/rosin/PAN nanofibers as a sorbent showed a good linearity in the range 1.0–250 ng mL−1 for polycyclic aromatic hydrocarbons (PAHs) (as a model for non-polar compounds) and 1.0–200 ng mL−1 for phenoxyacetic acid herbicides (CAPs) (as a model for polar compounds) with correlation coefficient (R2) higher than 0.997. Limits of detections (LODs) for PAHs and CAPs were in the range 0.1–0.3 ng mL−1 and 0.3–0.5 ng mL−1, respectively. The intra-day (n = 3) and inter-day (between 3 days) relative standard deviations (RDSs%) were in the range 6.3–12.3% for a single syringe. Finally, the MEPS-GC-FID method was applied as a simple, facile, and time and cost-effective method to analyze environmental, farm, and industrial water samples. [ABSTRACT FROM AUTHOR]

Real-time measurements and adjustments of critical process parameters are essential for the precise control of fermentation processes and thus for increasing both quality and yield of the desired product. However, the measurement of some crucial process parameters such as biomass, product, and product precursor concentrations usually requires time-consuming offline laboratory analysis. In this work, we demonstrate the in-line monitoring of biomass, penicillin (PEN), and phenoxyacetic acid (POX) in a Penicilliumchrysogenum fed-batch fermentation process using low-cost microspectrometer technology operating in the near-infrared (NIR). In particular, NIR reflection spectra were taken directly through the glass wall of the bioreactor, which eliminates the need for an expensive NIR immersion probe. Furthermore, the risk of contaminations in the reactor is significantly reduced, as no direct contact with the investigated medium is required. NIR spectra were acquired using two sensor modules covering the spectral ranges 1350–1650 nm and 1550–1950 nm. Based on offline reference analytics, partial least squares (PLS) regression models were established for biomass, PEN, and POX either using data from both sensors separately or jointly. The established PLS models were tested on an independent validation fed-batch experiment. Root mean squared errors of prediction (RMSEP) were 1.61 g/L, 1.66 g/L, and 0.67 g/L for biomass, PEN, and POX, respectively, which can be considered an acceptable accuracy comparable with previously published results using standard process spectrometers with immersion probes. Altogether, the presented results underpin the potential of low-cost microspectrometer technology in real-time bioprocess monitoring applications. [ABSTRACT FROM AUTHOR]

Two new mononuclear complexes, [Zn(3-Hcpa)2(H2O)4] (1) and [Zn(3,5,6-tcpa)2(H2O)4] [Zn(3,5,6-tcpa)2(H2O)2] (2) (3-H2cpa = 3-carboxy-phenoxyacetic acid, 3,5,6-Htcpa = 3,5,6-trichloro pyridine-2-oxyacetic acid), were synthesized and structurally characterized. The single-crystal X-ray diffraction analysis showed that in 1 the ZnII ion lies on an inversion center of an octahedron formed by four aqua ligands and two carboxy oxygen atoms of two unidentate 3-Hcpa− anions in trans-arrangement. Complex 2 is a co-crystal consisting of two discrete and stereochemically different complexes: one with an octahedrally, and the other a tetrahedrally coordinated zinc center. The six-coordination about the first ZnII ion comprises four oxygen atoms from water (H2O) molecules and two from the carboxy groups of monodentate trans-related 3,5,6-tcpa− ligands. The four-coordination about the second ZnII ion is comprised of two H2O ligands and two unidentate carboxy oxygen atoms from 3,5,6-tcpa− ligands. O–HLO hydrogen bond and/or ClLCl halogen bond interactions play an important part in construction of the three-dimensional (3D) networks for 1 and 2. The photoluminescence spectra reveal that both 1 and 2 display luminescent properties in the violet region. [ABSTRACT FROM AUTHOR]

Two dinuclear lanthanide complexes [Dy2(L1)6(L²)2]2EtOH (1) and [Tb2(L¹)6(L²)2]2EtOH (2) (HL1 = phenoxyacetic acid and L² = 2,2'-bipyridine) were synthesized and the crystal structures were determined. In both complexes, the lanthanide centers are nine-coordinated and have a muffin geometry. Detailed magnetic study reveals the presence of field-induced single molecule magnet (SMM) behavior for complex 1, whereas complex 2 is non-SMM in nature. Further magnetic study with 10, yttrium doped magnetically diluted sample of 1, disclosed the presence of Orbach and Raman relaxation processes with effective energy barrier, DE = 16.26 cm-1 and relaxation time, o = 2.42 10-8 s. Luminescence spectra for complexes 1 and 2 in acetonitrile were studied which show characteristic emission peaks for DyIII and TbIII ions, respectively. [ABSTRACT FROM AUTHOR]

Free fatty acid receptor 1 (FFAR1 or GPR40) is a potential target for treating type 2 diabetes mellitus (T2DM) and related disorders that have been extensively researched for many years. GPR40/FFAR1 is a promising anti-diabetic target because it can activate insulin, promoting glucose metabolism. It controls T2DM by regulating glucose levels in the body through two separate mechanisms: glucose-stimulated insulin secretion and incretin production. In the last few years, various synthetic GPR40/FFAR1 agonists have been discovered that fall under several chemical classes, viz. phenylpropionic acid, phenoxyacetic acid, and dihydrobenzofuran acetic acid. However, only a few synthetic agonists have entered clinical trials due to various shortcomings like poor efficacy, low lipophilicity and toxicity issues. As a result, pharmaceutical firms and research institutions are interested in developing synthetic GPR40/FFAR1 agonists with superior effectiveness, lipophilicity, and safety profiles. This review encompasses the most recent research on synthetic GPR40/FFAR1 agonists, including their chemical classes, design strategies and structure-activity relationships. Additionally, we have emphasised the structural characteristics of the most potent GPR40/FFAR1 agonists from each chemical class of synthetic derivatives and analysed their chemico-biological interactions. This work will hopefully pave the way for developing more potent and selective synthetic GPR40/FFAR1 agonists for treating T2DM and related disorders. [Display omitted] • Recent findings on synthetic GPR40/FFAR1 agonists are extensively covered. • Different chemical classes and their SAR are presented in detail. • Identified the most promising compounds from each chemical class. • This study may be effective in designing synthetic GPR40/FFAR1 agonists in future. [ABSTRACT FROM AUTHOR]

Hydrazones were obtained in 76−78% yield via condensation of (2S,5R)-2-isopropyl-5-methylcyclohexanone with 4-R-phenoxyacetic acid hydrazides in the presence of a catalytic amount of glacial acetic acid. The structure of the target compounds has been established by FTIR-ATR, Raman, 1H-NMR and 13C-NMR spectral analysis and EI/FAB/ESI mass spectrometry. Thermal properties of hydrazones 3a−3e were elucidated by differential scanning calorimetry (DSC) and their purity by HPLC coupled to mass spectrometry. Synthesized compounds were found to exist as Z/E geometrical isomers about C=N bond and cis/trans amide conformers.

Based on an old phenoxyacetic acid scaffold, CPU014 (compound 14) has been identified as a superior agonist by comprehensive exploration of structure-activity relationship. In vitro toxicity study suggested that CPU014 has lower risk of hepatotoxicity than TAK-875. During acute toxicity study (5–500 mg/kg), a favorable therapeutic window of CPU014 was observed by evaluation of plasma profiles and liver slices. Moreover, CPU014 promotes insulin secretion in a glucose-dependent manner, while no GLP-1 secretion has been enhanced. Other than good pharmacokinetic properties, CPU014 significantly improved glucose tolerance both in normal and diabetic models without the risk of hypoglycemia. These subversive findings provided a safer candidate CPU014, which is currently in preclinical study to assess its potential for the treatment of diabetes. Starting from previously abandoned phenoxyacetic acid moiety, we identified a superior agonist 14 (CPU014, EC 50 = 15.7 nM) based on SAR study and toxicity screening. Image 1 • CPU014 was identified by comprehensive exploration of structure-activity relationship. • CPU014 revealed significantly reduced risk of hepatotoxicity compared to TAK-875. • CPU014 exhibited an excellent therapeutic window from 5 to 500 mg/kg. • CPU014 showed enhanced glucose-dependent insulin secretion. • CPU014 has good pharmacokinetic profiles. [ABSTRACT FROM AUTHOR]

Softening ammonia sulfate wastewater is one of the vital issues in the rare earth industry. In this article, a novel softening process using [4,4′-isopropylidenebis (phenoxyacetate)] (H 2 IPOAA) for Ca2+ and Mg2+ (M2+) is developed. The effect factors, i.e., equilibrium time, pH value of aqueous phase and saponification degree are investigated. The extraction mechanism is proposed to be cation exchange. With a saponification degree of 85%, H 2 IPOAA is successfully used for the precipitation of Ca2+ and Mg2+ from ammonia sulfate wastewater within 10 min. The process can form precipitated particles with an average size of 35 μm, which are much larger than the precipitates formed by H 2 C 2 O 4 , Na 2 C 2 O 4 and Na 2 CO 3. The precipitated particles can be easily separated from the raffinate. In addition, H 2 IPOAA is repeatedly used for five times with a little loss. To a considerable extent, the reuse of H 2 IPOAA contributes to lowering the cost and reducing the pollution. The concentrations of Ca2+ and Mg2+ in the raffinate extracted by H 2 IPOAA are up to the MVR standard for wastewater treatment. The economical and efficient softening process meets the need of green chemistry, which is expected to replace traditional industrial processes for water softening based on H 2 C 2 O 4 , Na 2 C 2 O 4 and Na 2 CO 3. A novel softening process using [4,4'-isopropylidenebis (phenoxyacetate)] (H 2 IPOAA) for Ca2+ and Mg2+ (M2+) is developed. Unlabelled Image • A novel softening strategy for ammonia nitrogen wastewater is developed. • Extraction mechanism is proposed to be cation exchange. • The precipitated particles can be easily separated. • The strategy contributes to lowering the cost and reducing the pollution. [ABSTRACT FROM AUTHOR]