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Current ionic polymer–metal composite (IPMC) actuators have severe actuation drawbacks (i.e. low force output and poor stability), hampering their applications. To address these issues, poly(ethylene glycol)‐grafted graphene oxide (PEG‐GO) is synthesized and incorporated into a Nafion matrix, thus producing a PEG‐GO hybrid Nafion film with better physiochemical properties for fabricating a high‐performance, low‐cost IPMC actuator. The modification of PEG to GO not only prevents GO agglomeration and sedimentation, but also avoids loss of PEG in water. Driven by a 0.2 Hz, 2.5 V electric field, the hybrid IPMC actuator exhibits superior electromechanical behaviors, i.e. a swing angle of 110.3°, a blocking force of 6.89 mN and a stable working time of 485 s, respectively increasing by 92%, 209% and 294% when compared to a pure Nafion actuator. © 2024 Society of Chemical Industry. [ABSTRACT FROM AUTHOR]

ABSTRACT CO2 is a significant greenhouse gas, and is considered as a copious renewable carbon reagent. From a synthetic perspective, it can be used as a sustainable and substitute C1 building block because of its nontoxic, nonflammable, and abundant nature. The transformation of a wide range of organic molecules with CO2 into numerous efficient commodities is a defining feature of recent success in this sector. Because of its numerous applications, photocatalysts and visible light‐mediated synthesis of carbamates and cyclic carbonates using CO2 have drawn a lot of interest from researchers. This mini review mainly focusses on the different one‐pot reactions that are proven to be efficacious for chemical fixation of CO2 in producing industry‐based compounds of carbamates and carbonates with the creation of CO, CH, CC, and CN bonds. [ABSTRACT FROM AUTHOR]

A sensitive, rapid, and simple HPLC–MS/MS method was first developed and fully validated to determine the icaritin (ICT) and its novel 3‐methylcarbamate prodrug (3N) simultaneously in rat plasma. Analytes were extracted from rat plasma using a liquid–liquid extraction (LLE) method. Chromatographic separation was performed on ACE Excel 2 C18‐Amide column. Quantitation of analytes was conducted on an LCMS‐8060 triple‐quadrupole tandem mass spectrometer. The quantitation mode was the multiple reaction monitoring via positive electrospray ionization. The calibration curve was linear over the concentration range of 1 to 200 ng/ml for ICT with a correlation coefficient of r = 0.9950 and 1 to 400 ng/ml for 3N with a correlation coefficient of r = 0.9956. The intra‐precision RSDs were ≤12% for ICT and 3N. The inter‐day precision RSDs were ≤10% for ICT and 3N. The accuracy RE was between −2.6% and 7.8% for ICT and 3N. The average ICT, 3N and IS recoveries were 87.9%, 83.6%, and 84.3%. The plasma matrix of ICT and 3N complied with the guidelines. ICT and 3N were stable in rat plasma under various tested conditions. This work has been successfully applied to studying the pharmacokinetics of ICT and 3N. [ABSTRACT FROM AUTHOR]

A single-step phenylation at the non-acidic C(sp3)–H bond attached to the heteroatom of ethers and N -Boc-amines has been achieved using photoexcited 4-benzoylpyridine as a hydrogen atom transfer (HAT) catalyst. The design of electron-deficient (trifluoromethylsulfonyl)benzene derivatives, as a phenyl precursor, was critical to realizing the present transformation. Moreover, the DFT calculations indicated that the present transformation proceeds via a concerted homolytic aromatic substitution rather than via a stepwise one involving the formation of a cyclohexadienyl radical intermediate. [ABSTRACT FROM AUTHOR]

In the following study, a series of new lupeol-3-carbamate derivatives were synthesized, and the structures of all the newly derived compounds were characterized. The new compounds were screened to determine their anti-proliferative activity against human lung cancer cell line A549, human liver cancer cell line HepG2, and human breast cancer cell line MCF-7. Most of the compounds were found to show better anti-proliferative activity in vitro than lupeol. Among them, obvious anti-proliferation activity (IC50 = 5.39~9.43 μM) was exhibited by compound 3i against all three tumor cell lines. In addition, a salt reaction was performed on compound 3k (IC50 = 13.98 μM) and it was observed that the anti-proliferative activity and water solubility of compound 3k·CH3I (IC50 = 3.13 μM), were significantly enhanced subsequent to the salt formation process. The preliminary mechanistic studies demonstrated that apoptosis in HepG2 cells was induced by compound 3k·CH3I through the inhibition of the PI3K/AKT/mTOR pathway. In conclusion, a series of new lupeol-3-carbamate derivatives were synthesized via the structural modification of the C-3 site of lupeol, thus laying a theoretical foundation for the design of this new anticancer drug. [ABSTRACT FROM AUTHOR]

The method for converting epoxy carbamates to oxazolidinones is outlined in this study. This innovative approach combines intermolecular nucleophilic epoxide ring opening with intramolecular acyl substitution in a single step, thereby facilitating rapid conversion. Significantly, this method effectively addresses challenges associated with the use of expensive reagents, harsh reaction conditions, and prolonged reaction times, presenting a more efficient alternative. Demonstrating favorable reactivity across a diverse range of aryl groups, as well as benzyl or tert‐butyl carbamates, the method consistently yields satisfactory results, with oxazolidinone formation ranging from 55 % to 99 % in over 24 examples. The synthesized oxazolidinones, including 5 v–5 x, hold substantial promise as intermediates for the synthesis of crucial synthetic molecules. Furthermore, the versatility of this method is underscored by its successful application in the formation of the 6‐membered ring 1,3‐oxazinan‐2‐one. These findings not only contribute to the advancement of synthetic methodologies but also pave the way for a streamlined synthesis of important pharmaceutical compounds. [ABSTRACT FROM AUTHOR]

Background Adolescents living in agricultural communities may be at risk for the adverse effects of pesticide exposure because they are involved in agriculture either as a career or to support their families. Objective The purpose of this study was to investigate the association of farm activities related to pesticide exposure on blood cholinesterase (ChE) levels among adolescents from farming families in the north of Thailand. Material and Methods This cross-sectional study included 336 adolescents aged 12-19 years from farming families in Chiang Dao District, Chiang Mai Province. Data on pesticide exposure was collected using a questionnaire, and blood ChE activity was assessed using a ChE reactive paper test kit via fingerstick blood sampling. Results Overall, 51.2% of participants had abnormal blood ChE levels. Univariable logistic regression analysis revealed that pesticide-related activities on farms associated with abnormal ChE levels were mixing/spraying (OR=10.54; 95%CI=4.63-23.99), assisting or working in areas with pesticide application (OR=5.54; 95%CI=3.45-8.89), and harvesting (OR=3.70; 95%CI=2.35-5.82). In a multivariable model (Nagelkerke R2=0.374), mixing/spraying (OR=4.90; 95%CI=2.03-11.83) and assisting or working in areas with pesticide application (OR=2.61; 95%CI=1.49-4.57) were significantly associated with abnormal ChE levels, but harvesting (OR=1.48; 95%CI=0.84-2.61) was not significant after adjusting for sex, age in years, and entering or walking through a farm. Conclusions The findings indicated that Thai adolescents living in farming families are at risk of pesticide exposure, particularly those involved in agricultural activities such as pesticide applicators. An intervention and measure to raise awareness and reduce the risk of pesticide exposure in adolescents is required.

Carbon dioxide (CO2) is one of the most abundant greenhouse gases in Earth's atmosphere and responsible for global warming. Therefore, aerial CO2 capture and sequestration has become a major task for human community. Though several adsorbents for CO2 including activated carbon, zeolites, metal‐organic frameworks (MOFs), and other surface‐modified porous materials are well developed, the supramolecular approaches using synthetic hydrogen‐bonding receptors are less explored. This review article highlights the synthetic development of various artificial receptors and their properties toward fixation of aerial CO2 as carbonate (CO32−), bicarbonate (HCO3−), or carbamate (−NHCOO−/>NCOO−) ions, induced by excess fluoride (F−) or hydroxide (OH−) ions as their tetrabutylammonium salts. The utilization of encapsulated carbonate/bicarbonate/carbamate complexes in anion exchange metathesis for separation of oxyanions from aqueous solutions are also discussed. In addition, the release of CO2 and regeneration of receptor molecules are described in a number of occasions. Most importantly, the formation of anion complexes as crystalline materials in solid‐state is described in terms of supramolecular chemistry and correlated with their solution‐state properties. Finally, the types of receptors containing various functional groups are scrutinized in CO2 uptake, storage, and release processes and hints of endeavours for future research are delineated. [ABSTRACT FROM AUTHOR]

Biocatalysis provides an attractive approach to facilitate synthetic reactions in aqueous media. Motivated by the discovery of promiscuous aminolysis activity of esterases, we exploited the esterase from Pyrobaculum calidifontis VA1 (PestE) for the synthesis of carbamates from different aliphatic, aromatic, and arylaliphatic amines and a set of carbonates such as dimethyl‐, dibenzyl‐, or diallyl carbonate. Thus, aniline and benzylamine derivatives, aliphatic and even secondary amines could be efficiently converted into the corresponding benzyloxycarbonyl (Cbz)‐ or allyloxycarbonyl (Alloc)‐protected products in bulk water, with (isolated) yields of up to 99 %. [ABSTRACT FROM AUTHOR]

Model reaction of the formation of aliphatic polyureas—the reaction of O-methyl-N-methylcarbamate with methylamine was studied at the M06 and B3LYP levels. Concerteted non-catalytic nucleophilic substitution reactions involving a monomer and dimer of methylamine proceed through large free energy barriers. Non-catalytic reactions with a monomer or dimer of methylamine proceed according to the "addition–elimination" pathway, the stages that determine the reaction rate are the formation of a tetrahedral intermediate. They also have large free energy barriers. Catalysis with zinc acetate, phenol, and 1,4-diazabicyclo[2.2.2]octane does not significantly change the energy barrier. A sharp decrease in activation barriers to the reaction occurs during catalysis with sodium hydroxide and sodium methoxide. [ABSTRACT FROM AUTHOR]

Triazoles are compounds with various biological activities, including fungicidal action. They became popular through cholinesterase studies after the successful synthesis of the dual binding femtomolar triazole inhibitor of acetylcholinesterase (AChE, EC 3.1.1.7) by Sharpless et al. via in situ click chemistry. Here, we evaluate the anticholinesterase effect of the first isopropanol triazole fungicide mefentrifluconazole (Ravystar®), developed to overcome fungus resistance in plant disease management. Mefentrifluconazole is commercially available individually or in a binary fungicidal mixture, i.e., with pyraclostrobin (Ravycare®). Pyraclostrobin is a carbamate that contains a pyrazole ring. Carbamates are known inhibitors of cholinesterases and the carbamate rivastigmine is already in use for the treatment of Alzheimer's disease. We tested the type and potency of anticholinesterase activity of mefentrifluconazole and pyraclostrobin. Mefentrifluconazole reversibly inhibited human AChE and BChE with a seven-fold higher potency toward AChE (Ki = 101 ± 19 μM). Pyraclostrobin (50 μM) inhibited AChE and BChE progressively with rate constants of (t1/2 = 2.1 min; ki = 6.6 × 103 M−1 min−1) and (t1/2 = 1.5 min; ki = 9.2 × 103 M−1 min−1), respectively. A molecular docking study indicated key interactions between the tested fungicides and residues of the lipophilic active site of AChE and BChE. Additionally, the physicochemical properties of the tested fungicides were compared to values for CNS-active drugs to estimate the blood–brain barrier permeability. Our results can be applied in the design of new molecules with a lesser impact on humans and the environment. [ABSTRACT FROM AUTHOR]

Twelve novel camptothecin derivatives with a carbamate substituent at position 20 were designed and synthesized. Most of the targeted compounds indicated potent anti-inflammatory activity in a lipopolysaccharide stimulation of peritoneal macrophage model. Among them, the benzyl(methyl)amine derivative showed the most pronounced anti-inflammatory activity at a concentration of 1 μM and TNF-α inhibitory rate is increased by 10.2% compared to the lead compound (N,N-dimethylethylenediamine derivative). [ABSTRACT FROM AUTHOR]

ABSTRACT: This study aimed to use ultra-high-performance liquid chromatography coupled to a triple-quadrupole mass spectrometer to detect 11 carbamate pesticide residues in raw and pasteurized camel milk samples collected from the United Arab Emirates. A method was developed and validated by evaluating limits of detection, limits of quantitation, linearity, extraction recovery, repeatability, intermediate precision, and matrix effect. Due to the high protein and fat content in camel milk, a sample preparation step was necessary to avoid potential interference during analysis. For this purpose, 5 different liquid–liquid extraction techniques were evaluated to determine their efficiency in extracting carbamate pesticides from camel milk. The established method demonstrated high accuracy and precision. The matrix effect for all carbamate pesticides was observed to fall within the soft range, indicating its negligible effect. Remarkably, detection limits for all carbamates were as low as 0.01 μg/kg. Additionally, the coefficients of determination were >0.998, demonstrating excellent linearity. A total of 17 camel milk samples were analyzed, and only one sample was found to be free from any carbamate residues. The remaining 16 samples contained at least one carbamate residue, yet all detected concentrations were below the recommended maximum residue limits set by Codex Alimentarius and the European Union pesticide databases. Nonetheless, it is worth noting that the detected levels of ethiofencarb in 3 samples were close to the borderline of the maximum residue limit. To assess the health risk for consumers of camel milk, the hazard index values of carbofuran, carbaryl, and propoxur were calculated. The hazard index values for these 3 carbamate pesticides were all below 1, indicating that camel milk consumers are not at risk from these residues.

Isoprocarb (IPC) is one of the most important carbamate pesticides for white flea control in coffee plants. The prevalence of isoprocarb pesticide residues in coffee, i.e., green coffee beans, is a cause for concern. Green coffee beans were intentionally contaminated with isoprocarb at concentrations >0.01 mg/kg, which was investigated in this research. Quantitative analysis of isoprocarb with the QuEChERS method and qualitative analysis for metabolite formation was characterized using UV-Vis, FTIR, 1H-NMR, GC-MS, and LC-QTOF-MS. Based on the data, the metabolite formed is o-cumenol through the hydrolysis reaction of o-aryl carbamate with the enzyme carboxylesterase. o-cumenol or 2- isopropylphenol as a phenol derivative. To verify the existence of metabolite analytes that are believed to be there in coffee tainted with isoprocarb, more reliable analytical techniques utilizing analytical standards must be developed. Isoprocarb concentrations decreased along the storage time, especially in unsterilized conditions. As a toxic compound, a quantitative structural activity relationship study (QSAR) was initially carried out through a software application for estimating toxicity (TEST) provided by the US Environmental Protection Agency (EPA). For additional information, based on the LC50 and LD50 data confirmed from the TEST application, it was concluded that isoprocarb is more toxic than o-cumenol.

Organophosphorus poisoning is a critical condition that can cause central nervous system depression, respiratory failure, and death early on. As its clinical manifestations closely resemble those of carbamate pesticide poisoning, the aim of this case study is to present a case of misdiagnosis, initially identifying carbofuran poisoning as organophosphate in a patient suspect of a heatstroke. We also present a case of intentional self-poisoning with organophosphate dichlorvos to underline the likelihood of pesticide poisoning in patients exhibiting acute cholinergic symptoms when the ingested substance is not known. In such cases, empirical treatment with atropine and oxime can be started pending timely differential diagnosis to adjust treatment as necessary.

Herein, we report triflic anhydride mediated synthesis of ureas starting from hydroxamic acids. The scope of triflic anhydride was also expanded to encompass carbamates. In addition, this reaction is applicable to activation of hydroxamic acid derivative of dipeptide giving α‐uriedopeptidomimetics in good yield. The mechanistic study of reaction was carried out by DFT. This study is important because it demonstrates that Tf2O has the potential to be effective when used on a substrate that possesses amide bond. A broad substrate scope and mild conditions render this protocol a promising approach to the synthesis of diverse types of ureas. [ABSTRACT FROM AUTHOR]

This study aimed to use ultra-high-performance liquid chromatography coupled to a triple-quadrupole mass spectrometer to detect 11 carbamate pesticide residues in raw and pasteurized camel milk samples collected from the United Arab Emirates. A method was developed and validated by evaluating limits of detection, limits of quantitation, linearity, extraction recovery, repeatability, intermediate precision, and matrix effect. Due to the high protein and fat content in camel milk, a sample preparation step was necessary to avoid potential interference during analysis. For this purpose, 5 different liquid–liquid extraction techniques were evaluated to determine their efficiency in extracting carbamate pesticides from camel milk. The established method demonstrated high accuracy and precision. The matrix effect for all carbamate pesticides was observed to fall within the soft range, indicating its negligible effect. Remarkably, detection limits for all carbamates were as low as 0.01 μg/kg. Additionally, the coefficients of determination were >0.998, demonstrating excellent linearity. A total of 17 camel milk samples were analyzed, and only one sample was found to be free from any carbamate residues. The remaining 16 samples contained at least one carbamate residue, yet all detected concentrations were below the recommended maximum residue limits set by Codex Alimentarius and the European Union pesticide databases. Nonetheless, it is worth noting that the detected levels of ethiofencarb in 3 samples were close to the borderline of the maximum residue limit. To assess the health risk for consumers of camel milk, the hazard index values of carbofuran, carbaryl, and propoxur were calculated. The hazard index values for these 3 carbamate pesticides were all below 1, indicating that camel milk consumers are not at risk from these residues. [ABSTRACT FROM AUTHOR]

The limited solubility of natural cellulose in water and common organic solvents hinders its diverse applications, despite being one of the most abundant and easily accessible biopolymers on Earth. Chemical derivatization, such as cellulose carbamate (CC), offers a pathway to enhance both solubility and industrial processability. In this study, CC was synthesized by exploiting a novel type IV deep eutectic solvent (DES) composed of erbium trichloride and urea. This DES was shown to be not only an environmentally friendly reaction medium/catalyst but also actively participated in the synthetic process as a reagent. The resultant cellulose carbamate samples were characterized through FT-IR and elemental analysis. A nitrogen content value of 1.59% was afforded determining a degree of substitution corresponding to a value of 0.19. One of the key scientific advancements lies in the preparation of cellulose carbamate using a straightforward and cost-effective method. This approach utilizes non-toxic compounds, aligning with the principles of green chemistry and contributing to sustainable development in cellulose derivative production. [ABSTRACT FROM AUTHOR]

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The purpose of this study is to analyze the characteristics of wild birds fell victim to pesticides poisoning in South Korea. The main outbreak of pesticide poisoning intensively occurred in winter, when food is rapidly reduced, and hungry birds easily fell victim to food contaminated with pesticides, resulting in ecologically fatal mass mortality. From 2017 to 2018 in South Korea, 1379 wild birds fell victim to pesticide poisoning. In detail, 832 (60.33%) waterfowls such as Baikal teals, and 547 (39.67%) forest birds such as brown-eared bulbuls died. The major pesticides identified in wild birds died of acute pesticide poisoning were carbofuran, monocrotophos and phosphamidon. Taken together, it is pesticide poisoning caused by artificially spraying rice seeds contaminated with pesticides that gives rise to mass death of wild birds in winter in South Korea, and continuous public education and dedicated institutions are needed to prevent this accident. [ABSTRACT FROM AUTHOR]

A series of 20 novel acylsulfonimide derivatives 3a-3t were synthesized from phthalic anhydride, sulfonamide and butyl chloroformate by means of active substructure splicing. Their structures were confirmed by ¹H NMR, 13C NMR and high resolution mass spectrometry. The fungicidal and herbicidal activities of the target compounds were determined using the mycelial growth rate method and the stem and leaf spray method, respectively. The results of fungicidal activity showed that most of the compounds had good inhibitory effects against Sclerotinia sclerotiorum, Colletotrichum camalliae, Sclerotium rolfii and Phytophthora capsici at 50 mg/L. The inhibition rates of 3f, 3n and 3q against S. sclerotiorum were 63.98%, 79.56% and 77.83%, respectively, which were better than that of the commercial asulox (58.78%). The EC50 values of compound 3q against C. camalliae and S. sclerotiorum were 21.57 mg/L and 10.49 mg/L, respectively, which were better than asulox. The herbicidal activity results showed that, the fresh weight control effect of compound 3a against Echinochloa crus-galli was 52.48% at 150 mg/L, which was lower than asulox (71.68%). The novel compounds synthesized in this study displayed fungicidal activities, which can provide reference for the study of biological activities of novel acyl sulfonimide derivatives. [ABSTRACT FROM AUTHOR]

Isoprocarb (IPC) is one of the most important carbamate pesticides for white flea control in coffee plants. The prevalence of isoprocarb pesticide residues in coffee, i.e., green coffee beans, is a cause for concern. Green coffee beans were intentionally contaminated with isoprocarb at concentrations >0.01 mg/kg, which was investigated in this research. Quantitative analysis of isoprocarb with the QuEChERS method and qualitative analysis for metabolite formation was characterized using UV-Vis, FTIR, 1H-NMR, GC-MS, and LC-QTOF-MS. Based on the data, the metabolite formed is o-cumenol through the hydrolysis reaction of o-aryl carbamate with the enzyme carboxylesterase. o-cumenol or 2-isopropylphenol as a phenol derivative. To verify the existence of metabolite analytes that are believed to be there in coffee tainted with isoprocarb, more reliable analytical techniques utilizing analytical standards must be developed. Isoprocarb concentrations decreased along the storage time, especially in unsterilized conditions. As a toxic compound, a quantitative structural activity relationship study (QSAR) was initially carried out through a software application for estimating toxicity (TEST) provided by the US Environmental Protection Agency (EPA). For additional information, based on the LC50 and LD50 data confirmed from the TEST application, it was concluded that isoprocarb is more toxic than o-cumenol. [ABSTRACT FROM AUTHOR]

The carbamate post-translational modification (PTM), formed by the nucleophilic attack of carbon dioxide by a dissociated lysine epsilon-amino group, is proposed as a widespread mechanism for sensing this biologically important bioactive gas. Here, we demonstrate the discovery and in vitro characterization of a carbamate PTM on K9 of Arabidopsis nucleoside diphosphate kinase (AtNDK1). We demonstrate that altered side chain reactivity at K9 is deleterious for AtNDK1 structure and catalytic function, but that CO2 does not impact catalysis. We show that nucleotide substrate removes CO2 from AtNDK1, and the carbamate PTM is functionless within the detection limits of our experiments. The AtNDK1 K9 PTM is the first demonstration of a functionless carbamate. In light of this finding, we speculate that non-functionality is a possible feature of the many newly identified carbamate PTMs. [ABSTRACT FROM AUTHOR]

The review is devoted to the methods of synthesis of pyridine-substituted ureas and carbamates. The classical synthetic approaches to such compounds together with the features of the synthetic procedures associated with the structure of the target compounds are considered. Close attention is focused on the new methods of synthesis of the title compounds. The main directions of application of pyridine-substituted ureas and carbamates are analyzed. The latest achievements in the application of these compounds in both medicinal chemistry and materials science are covered. [ABSTRACT FROM AUTHOR]

As emerging organic agricultural pollutants, carbamate pesticides can react with other contaminants in aquatic environments to produce new toxic compounds threatening aquatic life and ecosystems. This study introduces a novel, nonhazardous, and greener method to synthesize a cross-linked ZnO/αFe2O3 nano-photocatalyst to treat carbamate pesticides via ball milling. ZnO/αFe2O3 was characterized through various methods, including XRD, EDX, XRF, DRS, BET, FE-SEM, PL, and FTIR analyses. Using the Response Surface Methodology (RSM), the ability of ZnO/αFe2O3 nano-photocatalyst to remove carbamate from synthesized wastewater was assessed. The BET result indicated a decrease in the diameter of the nanocomposite size after the synthesis. At the same time, the BET surface area and total pores increased from 4.9871 m2.g−1 and 0.02806 cm3.g−1 to 6.8524 m2.g−1 and 0.069497 cm3.g−1, respectively. In addition, the band-gap energy decreased from 3.179 eV for ZnO to 1.907 eV for ZnO/αFe2O3 and eventually reached 1.878 eV for heat-treated ZnO/αFe2O3 nanocomposite. The catalyst concentrations used in the experiments were 0.5, 1, and 1.5 g/L. The solution pH was set to 5, 8, and 11, and three different residence times of 1, 2, and 3 h were used. The model's results indicated a strong agreement between the experimental and predicted data (R2 = 0.99). When the nanocomposite's concentration, pH, and retention time were set at 1 g/L ZnO/αFe2O3, 8.51, and 3 h respectively, the optimized conditions predicted a removal efficiency of 89%. In addition, the cost of COD removal was reduced by 50% using ball milling and heat-treatment synthesis. The photocatalyst's reusability was tested in three stages, and the outcomes demonstrated its stability throughout these three stages. [ABSTRACT FROM AUTHOR]

The title molecule, C12H15NO5, is a methyl carbamate derivative obtained by reacting (R)-2-phenylglycinol and methyl chloroformate, with calcium hydroxide as heterogeneous catalyst. Supramolecular chains are formed in the [100] direction, based on N—H...O hydrogen bonds between the amide and carboxylate groups. These chains weakly interact in the crystal, and the phenyl rings do not display significant π–π interactions.

In the following study, a series of new lupeol-3-carbamate derivatives were synthesized, and the structures of all the newly derived compounds were characterized. The new compounds were screened to determine their anti-proliferative activity against human lung cancer cell line A549, human liver cancer cell line HepG2, and human breast cancer cell line MCF-7. Most of the compounds were found to show better anti-proliferative activity in vitro than lupeol. Among them, obvious anti-proliferation activity (IC50 = 5.39~9.43 μM) was exhibited by compound 3i against all three tumor cell lines. In addition, a salt reaction was performed on compound 3k (IC50 = 13.98 μM) and it was observed that the anti-proliferative activity and water solubility of compound 3k·CH3I (IC50 = 3.13 μM), were significantly enhanced subsequent to the salt formation process. The preliminary mechanistic studies demonstrated that apoptosis in HepG2 cells was induced by compound 3k·CH3I through the inhibition of the PI3K/AKT/mTOR pathway. In conclusion, a series of new lupeol-3-carbamate derivatives were synthesized via the structural modification of the C-3 site of lupeol, thus laying a theoretical foundation for the design of this new anticancer drug.

Triazoles are compounds with various biological activities, including fungicidal action. They became popular through cholinesterase studies after the successful synthesis of the dual binding femtomolar triazole inhibitor of acetylcholinesterase (AChE, EC 3.1.1.7) by Sharpless et al. via in situ click chemistry. Here, we evaluate the anticholinesterase effect of the first isopropanol triazole fungicide mefentrifluconazole (Ravystar®), developed to overcome fungus resistance in plant disease management. Mefentrifluconazole is commercially available individually or in a binary fungicidal mixture, i.e., with pyraclostrobin (Ravycare®). Pyraclostrobin is a carbamate that contains a pyrazole ring. Carbamates are known inhibitors of cholinesterases and the carbamate rivastigmine is already in use for the treatment of Alzheimer’s disease. We tested the type and potency of anticholinesterase activity of mefentrifluconazole and pyraclostrobin. Mefentrifluconazole reversibly inhibited human AChE and BChE with a seven-fold higher potency toward AChE (Ki = 101 ± 19 μM). Pyraclostrobin (50 μM) inhibited AChE and BChE progressively with rate constants of (t1/2 = 2.1 min; ki = 6.6 × 103 M−1 min−1) and (t1/2 = 1.5 min; ki = 9.2 × 103 M−1 min−1), respectively. A molecular docking study indicated key interactions between the tested fungicides and residues of the lipophilic active site of AChE and BChE. Additionally, the physicochemical properties of the tested fungicides were compared to values for CNS-active drugs to estimate the blood–brain barrier permeability. Our results can be applied in the design of new molecules with a lesser impact on humans and the environment.

The limited solubility of natural cellulose in water and common organic solvents hinders its diverse applications, despite being one of the most abundant and easily accessible biopolymers on Earth. Chemical derivatization, such as cellulose carbamate (CC), offers a pathway to enhance both solubility and industrial processability. In this study, CC was synthesized by exploiting a novel type IV deep eutectic solvent (DES) composed of erbium trichloride and urea. This DES was shown to be not only an environmentally friendly reaction medium/catalyst but also actively participated in the synthetic process as a reagent. The resultant cellulose carbamate samples were characterized through FT-IR and elemental analysis. A nitrogen content value of 1.59% was afforded determining a degree of substitution corresponding to a value of 0.19. One of the key scientific advancements lies in the preparation of cellulose carbamate using a straightforward and cost-effective method. This approach utilizes non-toxic compounds, aligning with the principles of green chemistry and contributing to sustainable development in cellulose derivative production.

The carbamate post-translational modification (PTM), formed by the nucleophilic attack of carbon dioxide by a dissociated lysine epsilon-amino group, is proposed as a widespread mechanism for sensing this biologically important bioactive gas. Here, we demonstrate the discovery and in vitro characterization of a carbamate PTM on K9 of Arabidopsis nucleoside diphosphate kinase (AtNDK1). We demonstrate that altered side chain reactivity at K9 is deleterious for AtNDK1 structure and catalytic function, but that CO2 does not impact catalysis. We show that nucleotide substrate removes CO2 from AtNDK1, and the carbamate PTM is functionless within the detection limits of our experiments. The AtNDK1 K9 PTM is the first demonstration of a functionless carbamate. In light of this finding, we speculate that non-functionality is a possible feature of the many newly identified carbamate PTMs.

Various coating strategies have been explored in the past to prevent the ingress of aggressive substances into concrete. However, either the durability or performance is still far from satisfaction. Here, carbamate solutions were prepared by pre-absorbing CO 2 into amino acid salts (AASs) to carbonize the surface of cementitious materials. The high concentration of carbonate ions provided by the carbamate induced rapid surface carbonation, resulting in the formation of an AAS-CaCO 3 composite barrier with a thickness of 2–3 μm and possessing high micromechanical properties. Additionally, it was observed that the barrier's effectiveness depends on the molecular structures of the amino acids employed. Coatings formed by arginine-based carbamates demonstrated excellent performances, likely due to the highly compacted calcite particles they produced. This easy-to-operate and effective strategy has the potential to open new avenues for the development of highly durable and impermeable coating barriers for practical applications. • The carbamates prepared by amino acid salts (AASs) were used for rapid carbonation. • An AAS-CaCO 3 composite layer was covered on the cementitious substrate surface. • The dense coating layer of Ser or Arg group showed opposite water barrier properties. • The barrier's effectiveness depended on the AA molecules in the carbonation products. • The Arg-based coating exhibited excellent moisture barrier and mechanical property. [ABSTRACT FROM AUTHOR]

FAAH inhibition can indirectly enhance endocannabinoid signaling to therapeutic levels, effectively preventing or slowing its progression of Alzheimer's disease (AD). Hence, the search for effective dual FAAH/cholinesterase inhibitors is considerable need for disease-modifying therapies. To this aim, we designed, synthesized, and tested three series of natural phenol carbamates. The majority of carbamates proved to be potent on a single target, amongst them, compound D12 containing paeonol motif was identified as an effective dual BuChE/FAAH inhibitor, with well-balanced nanomolar activity (IC 50  = 81 and 400 nM for hBuChE and hFFAH, respectively). D12 possessed BBB penetrating ability, benign safety, neuroprotection and pseudo-irreversible BuChE inhibition (K d  = 2.11 μM, k 2  = 2.27 min -1 ), showing good drug-like properties. D12 also modulated the BV2 microglial polarization to inhibit neuroinflammation. In vivo study verified that D12 improved Aβ 1-41 -induced learning impairments in AD mouse model for both short- and long-term memory responses. Thus, the dual activity of D12 could lead to a potentially more effective treatment for the counteraction of AD progression., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: The authors declare that they have no conflict of interests., (Copyright © 2024 Elsevier Masson SAS. All rights reserved.)

Pesticides are used to kill, repel or control any animal or plant species which are considered pests, but have also been associated with intentional and unintentional human fatalities. A rapid increase in pesticide suicides was observed during 'The Green Revolution' after pesticides were introduced into low- and middle-income rural households without appropriate guidelines for safe use and storage. While national pesticide bans have contributed to a significant decrease in pesticide-related suicides, such cases still comprise a large proportion of all suicides around the world. The aim of the current study was to provide a profile of pesticide suicides in a high-income country as a point of comparison against studies from low- and middle-income countries. Statistical analyses were performed using R (version 4.2.3). Over the 20-year study period, there were a low, yet consistent number of pesticide suicides which were most common among males over the age of 40. Paraquat and methomyl pesticides collectively contributed to almost half (48.8%) of all fatalities. Consistent with the literature, such cases often occurred with little premeditation in response to an acute emotional crisis. While interpretation of autopsy findings was mostly limited, there were some pesticides that demonstrated findings consisted with previously reported characteristics (e.g., gastroesophageal erosions with paraquat). Given the high proportion of cases where paraquat and methomyl pesticides were implicated, it may be appropriate to review the availability and accessibility of such compounds to reduce the occurrence of pesticide suicides in South Australia and potentially the wider Australian population., Competing Interests: Declaration of conflicting interestsThe authors declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Background: The aim of the study was to investigate the effect of baicalin and baicalin-bovine serum albumin nanoparticles against bendiocarb exposure in rats., Methods: Eighty male Wistar Albino rats aged 4-6 weeks were used. Corn oil (vehicle) alone was administered to the control group. To other groups, BSA-nanoparticle equivalent to that binding baicalin at a dose of 20 mg/kg.bw, 20 mg/kg.bw baicalin, baicalin-BSA nanoparticle equivalent to that binding baicalin at a dose of 20 mg/kg.bw, 4 mg/kg.bw bendiocarb, combination of 4 mg/kg.bw bendiocarb and 20 mg/kg.bw baicalin, combination of 4 mg/kg.bw bendiocarb and BSA-nanoparticle equivalent to that binding baicalin at a dose of 20 mg/kg.bw and combination of 4 mg/kg.bw bendiocarb and baicalin-BSA nanoparticle equivalent to that binding baicalin at a dose of 20 mg/kg.bw was administered to animals by oral gavage with vehicle for 21 days, after which organs (liver, kidney, brain, testes, heart and lung) and blood samples were collected. Blood/tissue oxidative stress (MDA, NO, GSH, SOD, CAT, GSH-Px, GR, GST, G6PD), serum biochemical (glucose, triglyceride, cholesterol, BUN, creatinine, uric acid, total protein, albumin, LDH, AST, ALT, ALP and pseudocholinesterase ) and liver and kidney apoptotic/anti-apoptotic (caspase 3, 9, p53, Bcl-2 and Bax) parameters were evaluated. Body weights/organ weights and plasma/liver bendiocarb analyses were obtained., Conclusion: While bendiocarb administered alone caused oxidative stress/tissue damage, baicalin and baicalin-BSA nanoparticle showed a mitigating effect. However, this effect was more pronounced in the baicalin-BSA nanoparticle group. BSA-nanoparticle alone did not have a significant effect in reversing the adverse effect caused by bendiocarb., (© The Author(s) 2024. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.)

Background: Adolescents living in agricultural communities may be at risk for the adverse effects of pesticide exposure because they are involved in agriculture either as a career or to support their families., Objective: The purpose of this study was to investigate the association of farm activities related to pesticide exposure on blood cholinesterase (ChE) levels among adolescents from farming families in the north of Thailand., Material and Methods: This cross-sectional study included 336 adolescents aged 12-19 years from farming families in Chiang Dao District, Chiang Mai Province. Data on pesticide exposure was collected using a questionnaire, and blood ChE activity was assessed using a ChE reactive paper test kit via fingerstick blood sampling., Results: Overall, 51.2% of participants had abnormal blood ChE levels. Univariable logistic regression analysis revealed that pesticide-related activities on farms associated with abnormal ChE levels were mixing/spraying (OR=10.54; 95%CI=4.63-23.99), assisting or working in areas with pesticide application (OR=5.54; 95%CI=3.45-8.89), and harvesting (OR=3.70; 95%CI=2.35-5.82). In a multivariable model (Nagelkerke R2=0.374), mixing/spraying (OR=4.90; 95%CI=2.03-11.83) and assisting or working in areas with pesticide application (OR=2.61; 95%CI=1.49-4.57) were significantly associated with abnormal ChE levels, but harvesting (OR=1.48; 95%CI=0.84-2.61) was not significant after adjusting for sex, age in years, and entering or walking through a farm., Conclusions: The findings indicated that Thai adolescents living in farming families are at risk of pesticide exposure, particularly those involved in agricultural activities such as pesticide applicators. An intervention and measure to raise awareness and reduce the risk of pesticide exposure in adolescents is required.

• A molecularly imprinted graphene coated stainless steel sheets (MIGOCS) were synthesized. • MIGOCS can be used as a selective adsorbent and as a solid-substrate electrospray ion source. • A dual-use ionization source of mass spectrometry was developed for determination of trace carbamate pesticides. Directly determining trace compounds in actual sample by ambient ionization mass spectrometry (AIMS) has always been a challenge. Due to the excellent adsorption and desorption properties of nanomaterials, AIMS combined with nanomaterials can improve the adsorption and desorption properties of MS. In this work, we developed a molecularly imprinted graphene oxide coated steel sheet (MIGOCS) to be used as a solid phase extraction adsorbent. Graphene oxide was characterized by its strong adsorption abilities, and the surface molecularly imprinted polymer has high selectivity. Here, the MIGOCS coupled with the ambient electrospray ion source was used to detect trace carbamate pesticides in water samples. Meanwhile, the extraction and spray parameters were systematically optimized. The newly developed molecularly imprinted graphene oxide-steel sheet spray-mass spectrometry (MIGO-SS-MS) method has low detection limits (0.05 ∼ 0.4 ng mL−1) and satisfactory recoveries (83.23 ∼ 97.98 %) for carbamates (CMs). The method can be potentially applied to the determination of CMs in water and food samples. [ABSTRACT FROM AUTHOR]

In this study, we present a facile method for introducing hydrophilic ureido groups (NH 2 -CO-NH-) into chitosan using a microwave-assisted reaction with molten urea, with the aim of enhancing chitosan's interaction with blood components for improved hemostasis. The formation of the ureido groups through nucleophilic addition reaction between the amine groups in chitosan and in situ generated isocyanic acid was confirmed by FTIR, CP/TOSS 13C NMR, and CP/MAS 15N NMR spectroscopic techniques. However, in stark contrast to the glucans, the said modification introduced extensive crosslinking in chitosan. Spectroscopic studies identified these crosslinks as carbamate bridges (-NH-COO-), which were likely formed by the reaction between the ureido groups and hydroxyl groups of adjacent chains through an isocyanate intermediate. These carbamate bridges improved ureido chitosan's environmental stability, making it particularly resistant to changes in pH and temperature. In comparison to chitosan, the crosslinked ureido chitosan synthesized here exhibited good biocompatibility and cell adhesion, rapidly arrested the bleeding in a punctured artery with minimal hemolysis, and induced early activation and aggregation of platelets. These properties render it an invaluable material for applications in hemostasis, particularly in scenarios that necessitate stability against pH variations and degradation. [Display omitted] • Ureido chitosan was prepared by reacting chitosan with molten urea using microwaves. • Unlike glucans, chitosan underwent extensive crosslinking during the reaction. • Crosslinking was due to carbamate bridges formed through the ureido-hydroxyl reaction. • Crosslinked ureido chitosan was biocompatible, and rapidly arrested the bleeding. • Crosslinked ureido chitosan can act as pH/degradation-resistant haemostatic material. [ABSTRACT FROM AUTHOR]

• Secondary and tertiary carbamates are prepared in high efficiency in an unprecedentive strategy. • Active transition metal-functionalized MOFs are synthesized via an in situ -grown protocolunder solvent-free mechanochemical conditions. • Both aminesand aniline are well tolerated. The solvent-free synthesis of MOF represents a promising and environmentally benign protocol. This paper outlines a green one-pot mechanochemical method for the synthesizing of UiO-66 in the absence of solvent, along with the implantation of three different metals (Cu, Ni, and Pd) into the defect sites. The materials have proven to be effective catalysts in the transformation between azidocarbonate and amines/anilines in moderate to excellent isolated yields (up to 94%), exhibiting better advantages compared with the exiting methodologies. More interestingly, Cu and Ni exhibited very good catalytic performance towards primary and secondary amines, respectively. It also should be noted that high yield was still observed after six cycles. Our work presents a novel and straightforward strategy for the preparation of secondary and tertiary carbamates in an unprecedented fashion, greatly enriched the toolbox for the synthetic community. Moreover, the combination of experimental studies and density functional theory (DFT) calculations gave more insight and evidence for the mechanism. Accompanied by the advantages of the effective and recyclable catalyst, the broad substrate scope, good functional group tolerance, and excellent reaction yields made the established method attractive in heterogeneous catalysis and the carbamates synthesis. [Display omitted] [ABSTRACT FROM AUTHOR]

The title mol-ecule, C 12 H 15 NO 5 , is a methyl carbamate derivative obtained by reacting ( R )-2-phenyl-glycinol and methyl chloro-formate, with calcium hydroxide as heterogeneous catalyst. Supra-molecular chains are formed in the [100] direction, based on N-H⋯O hydrogen bonds between the amide and carboxyl-ate groups. These chains weakly inter-act in the crystal, and the phenyl rings do not display significant π-π inter-actions., (© Mendoza Herrera et al. 2024.)

In this study, a series of carbamate derivatives incorporating multifunctional carrier scaffolds were designed, synthesized, and evaluated as potential therapeutic agents for Alzheimer's disease (AD). We used tacrine to modify the aliphatic substituent, and employed rivastigmine, indole and sibiriline fragments as carrier scaffolds. The majority of compounds exhibited good inhibitory activity for cholinesterase. Notably, compound C7 with sibiriline fragment exhibited potent inhibitory activities against human acetylcholinesterase (h AChE, IC 50 = 30.35 ± 2.07 nM) and human butyrylcholinesterase (h BuChE, IC 50 = 48.03 ± 6.41 nM) with minimal neurotoxicity. Further investigations have demonstrated that C7 exhibited a remarkable capacity to safeguard PC12 cells against H 2 O 2 -induced apoptosis and effectively suppressed the production of reactive oxygen species (ROS). Moreover, in an inflammation model of BV2 cells induced by lipopolysaccharide (LPS), C7 effectively attenuated the levels of pro-inflammatory cytokines. After 12 h of dialysis, C7 continued to exhibit an inhibitory effect on cholinesterase activity. An acute toxicity test in vivo demonstrated that C7 exhibited a superior safety profile and no hepatotoxicity compared to the parent nucleus tacrine. In the scopolamine-induced AD mouse model, C7 (20 mg/kg) significantly reduced cholinesterase activity in the brain of the mice. C7 was tested in a pharmacological AD mouse model induced by Aβ 1-42 and attenuated memory deficits at doses as low as 5 mg/kg. The pseudo-irreversible cholinesterase inhibitory properties and multifunctional therapeutic attributes of C7 render it a promising candidate for further investigation in the treatment of AD. [Display omitted] • This study provides a novel perspective for the structural modification of carbamate and presents a promising carrier scaffold. • C7 was confirmed as a potent dual inhibitor of both h AChE (IC 50 = 30.35 ± 2.07 nM) and h BuChE (IC 50 = 48.03 ± 6.41 nM). • C7 demonstrated potent antioxidant and anti-inflammatory properties, along with characteristics of pseudo-irreversible inhibition. • In brain of mice, C7 exhibited significant inhibitory effects on cholinesterase activity without acute toxicity or hepatotoxicity in vivo. • C7 showed significant mitigation of cognitive impairments in Aβ 1-42 -induced AD mice at doses as low as 5 mg/kg. [ABSTRACT FROM AUTHOR]

[Display omitted] • Twenty-nine 20(R)-Panaxadiol derivatives with carbamate structures were designed and synthesized and characterized. • In vitro neuroprotective activity was assessed using an Aβ 25-35 -induced PC12 cell injury model. • Molecular docking studies revealed a stronger binding affinity of compound Q4 for β-secretase. • In vivo experiments, Q4 significantly alleviated learning and memory deficits in mice. • Q4 is a potential multifunctional neuroprotective agent. It is reported that panaxadiol has neuroprotective effects. Previous studies have found that compound with carbamate structure introduced at the 3-OH position of 20 (R) -panaxadiol showed the most effective neuroprotective activity with an EC 50 of 13.17 μM. Therefore, we designed and synthesized a series of ginseng diol carbamate derivatives with ginseng diol as the lead compound, and tested their anti-AD activity. It was found that the protective effect of compound Q4 on adrenal pheochromocytoma was 80.6 ± 10.85 % (15 μM), and the EC 50 was 4.32 μM. According to the ELISA results, Q4 reduced the expression of Aβ 25-35 by decreasing β-secretase production. Molecular docking studies revealed that the binding affinity of Q4 to β-secretase was −49.67 kcal/mol, indicating a strong binding affinity of Q4 to β-secretase. Western blotting showed that compound Q4 decreased IL-1β levels, which may contribute to its anti-inflammatory effect. Furthermore, compound Q4 exhibits anti-AD activities by reducing abnormal phosphorylation of tau protein and activation of the mitogen activated protein kinase pathway. The learning and memory deficits in mice treated with Q4 in vivo were significantly alleviated. Therefore, Q4 may be a promising multifunctional drug for the treatment of AD, providing a new way for anti-AD drugs. [ABSTRACT FROM AUTHOR]

The H 1 -antihistamine diphenhydramine antagonizes cholinesterase inhibitor poisoning in various animal species. One aspect of acute antidotal actions of diphenhydramine is increasing the median lethal doses (LD50) of toxicants. The objective of this meta-analysis was to assess the antidotal action of diphenhydramine against short-term toxicity (LD50) of cholinesterase inhibitors in experimental animals. The experimental studies selected were according to the Preferred Reporting Items for Systematic Reviews and Meta-Analysis (PRISMA) guidelines. They were conducted in laboratory animals (mice, rats, and chicks) to determine acute LD50 values of cholinesterase inhibitors (organophosphates, carbamates, and imidocarb) under the influence of diphenhydramine vs. controls. Twenty-eight records were selected from 12 studies on mice (n= 242), rats (n= 27), and young chicks (n= 128). The forest plot of randomized two-group meta-analysis assessed effect size, subgroup analysis, drapery prediction, heterogeneity, publication bias-funnel plot as well as one-group proportions meta-analysis of percent protection. Diphenhydramine significantly increased the combined effect size (i.e. increased LD50) in intoxicated experimental animals in comparison to controls (-3.71, standard error (SE) 0.36, 95%CI -4.46, -2.97). The drapery plot proposed a wide range of confidence intervals. The I 2 index of heterogeneity of the combined effect size was high at 81.03% ( Q = 142.3, p < 0.0001). Galbraith regression also indicated data heterogeneity; however, the normal quantile plot indicated no outliers. Subgroup analysis indicated significantly high heterogeneity with organophosphates (I 2 = 63.72%) and carbamates (I 2 = 76.41%), but low with imidocarb (I 2 = 51.48%). The funnel plot and Egger regression test (t= -13.7, p < 0.0001) revealed publication bias. The median of the diphenhydramine protection ratio was 1.655, and the related forest plot of one group proportion meta-analysis revealed a statistically high level of protection (0.594, SE 0.083, 95%CI 0.432, 0.756), with high heterogeneity (I 2 = 99.86). The risk of bias assessment was unclear, while the total score (16 out of 20) of each study leaned towards the side of the low risk of bias. In conclusion, the meta-analysis of LD50 values indicated that diphenhydramine unequivocally protected experimental animals from the acute toxicity of cholinesterase inhibitors. The drug could be an additional antidote against acute poisoning induced by cholinesterase inhibitors, but a word of caution: it is not to be considered as a replacement for the standard antidote atropine sulfate. Further studies are needed to examine the action of diphenhydramine on adverse chronic effects of cholinesterase inhibitors., Competing Interests: The authors have declared that no competing interests exist., (Copyright © 2024, Mohammad et al.)