Antioxidant, antibacterial, enzyme inhibition and fluorescence characteristics of unsymmetrical thiourea derivatives.

A series of six unsymmetrical thiourea derivatives, namely 1-cyclohexyl-3-(pyridin-2-yl) thiourea (1), 1-cyclohexyl-3-(3-methylpyridin-2-yl)thiourea (2), 1-cyclohexyl-3-(2,4-dimethylphenyl) thiourea (3), 1-(4-chlorophenyl)-3-cyclohexylthiourea (4), 1-(3-methylpyridin-2-yl)-3-phenylthiourea (5), and 1-(3-chlorophenyl)-3-phenylthiourea (6), were successfully synthesized via reaction between different amines with isothiocyanates under a non-catalytic environment. Structural elucidation of compounds (1-6) was performed using FT-IR and NMR (1H and 13C) spectroscopy. The infrared spectra displayed characteristic stretching vibrations, while the 13C NMR chemical shifts of the thiourea moiety (C[bond, double bond]S) were observed in the range of 179.1-181.4 ppm. The antioxidative and antimicrobial properties of the compounds were assessed, as well as their inhibitory effects on acetylcholinesterase and butyrylcholinesterase were evaluated. In order to analyze the fluorescence characteristics of each compound (1-6), the excitation (λex) and emission (λem) wavelengths were scanned within the range of 250-750 nm, with the solvent blank serving as a standard. It was observed that when dissolved in acetone, toluene, tetrahydrofuran, and ethyl acetate, these compounds exhibited emission peaks ranging from 367 to 581 nm and absorption peaks ranging from 275 to 432 nm.

Efficient green silver nanoparticles-antibiotic combinations against antibiotic-resistant bacteria.

Antibiotic-resistant bacterial strains and the consequent surge in infections caused by them have become major public health concerns. Silver nanoparticles (AgNPs) exhibit antibacterial properties and have wide applications in biomedical sciences. In this study, AgNPs were synthesized in the presence of antibiotics: Ceftazidime (Cft), Cefotaxime (Cef), Ceftriaxone (Cfx), and Cefepime (Cpm), along with the extract of Mentha longifolia. Mentha longifolia-based AgNPs were kept as the control for all experiments. The associated metabolites, structural properties, surface charges, and antibacterial activity of the AgNPs were also evaluated. Overall, a blue-shift of SPR peaks was observed for control AgNPs (λmax = 421 nm, 422 nm, 426 nm, and 406 nm for Cft-AgNPs, Cef-AgNPs, Cfx-AgNPs, and Cpm-AgNPs, respectively), compared to the control (λmax = 438 nm). Fourier-transform infrared spectroscopy showed that antibiotic-based AgNPs had distinct peaks that corresponded to the respective antibiotics, which were not observed in the control. XRD analysis showed that there were observed changes in crystallinity in antibiotic-based AgNPs compared to the control. TEM images revealed that all samples had spherical nanoparticles with different sizes and distributions compared to the control. The Zeta potential for extract-based AgNPs was - 33.6 mV, compared to -19.6 mV for Cft-AgNPs, -2 mV for Cef-AgNPs, -21.1 mV for Cfx-AgNPs, and - 24.2 mV for Cpm-AgNPs. The increase in the PDI value for antibiotic-based AgNPs also showed a highly polydisperse distribution. However, the antibiotic-AgNPs conjugates showed significantly higher activity against pathogenic bacteria. The addition of antibiotics to AgNPs brought significant changes in structural properties and antibacterial activities.

Synthesis of fructose bound Fe(iii) integrated carbon dots as a robust turn-off detection sensor for chlortoluron.

A simple, sensitive, and robust fluorescent sensor for chlortoluron detection has been developed. Fluorescent carbon dots were synthesized using ethylene diamine and fructose via a hydrothermal protocol. The molecular interaction between fructose carbon dots and Fe(iii) resulted in a fluorescent metastable state exhibiting remarkable fluorescence quenching at λem of 454 nm and interestingly, further quenching occurred upon the addition of chlortoluron. The quenching in the fluorescence intensity of CDF-Fe(iii) towards chlortoluron occurred in the concentration range of 0.2-5.0 µg mL-1 where the limit of detection was found to be 0.0467 µg mL-1, the limit of quantification was 0.14 µg mL-1, and the relative standard deviation was 0.568%. The selective and specific recognitive nature of the Fe(iii) integrated fructose bound carbon dots towards the chlortoluron make it a suitable sensor for real sample applications. The proposed strategy was applied for the determination of chlortoluron in soil, water, and wheat samples with recoveries in the range of 95% to 104.3%.

An ultrasensitive colorimetric and fluorescent "turn-on" chemosensor based on Schiff base for the detection of Cu2+ in the aqueous medium.

We designed and synthesized a fluorescent "turn-on" and colorimetric chemosensor ((E)-1-((p-tolylimino)methyl)naphthalen-2-ol) SB. The structure of the synthesized chemosensor was investigated by 1H NMR, FT-IR, and fluorescence spectroscopy, and its sensing properties were studied toward Mn2+, Cu2+, Pb2+, Cd2+, Na+, Ni2+, Al3+, K+, Ag+, Zn2+, Co2+, Cr3+, Hg2+, Ca2+, and Mg2+. SB showed an excellent colorimetric (yellow to yellowish brown) in MeOH and fluorescence "turn-on" sensing response to Cu2+ in MeOH/Water (10/90, v/v) media. The sensing mechanism of SB toward Cu2+ was investigated by FT-IR, 1H NMR titration, DFT studies, and Job's plot analysis. The detection limit was calculated to be very low 0.0025 µg mL-1 (0.0025 ppm). Furthermore, the test strip containing SB also showed excellent selectivity and sensitivity toward Cu2+ in a solution medium and when supported on a solid medium.

Development of Fluorescent Co (II)-Integrated Carbon Dots and Their Application as a Off-On Mesotrione Detection Sensor.

A very simple mesotrione-sensing medium with enhanced sensitivity detection limits has been proposed. A renovated hydrothermal method was adopted for synthesizing fluorescent carbon dots from ethylenediamine and glucose using a Teflon-lined simple autoclave in a GC oven. The resultant carbon dots were characterized via TEM, FTIR, UV-vis, particle size distribution, and EDX and evaluated in a fluorimeter as the sensing medium for mesotrione detection. The binding approach of the Co (II)-integrated glucose-bound carbon dots toward mesotrione is selective, making them an effective sensor for the real sample applications, where majority of the coexisting substances showed insignificant interference effect. Formation of the metastable state due to the molecular interaction between carbon dots and Co (II) resulted in fluorescence quenching at 456 nm. Enhancement in the fluorescence intensity occurred when mesotrione was added in the concentration range of 0.2-5.0 µg mL-1, with a limit of detection, limit of quantification, standard deviation, and relative standard deviation of 0.054, 0.164, 0.00082 µg mL-1, and 0.682%, respectively. Mesotrione determination was demonstrated in soil, water, and tomato samples with recoveries in the range of 95.38-104.7%. The selectivity of the sensor was found to be good enough when checked for the complex tomato sample spiked with different pesticides of the triketone family having structural similarities to mesotrione.

Synthesis of monolith silica anchored graphene oxide composite with enhanced adsorption capacities for carbofuran and imidacloprid.

Highly efficient adsorbent was prepared for the removal of carbofuran and imidacloprid pesticides from wastewater. The silica monolith anchored graphene oxide composite was synthesized by the modified Fischer esterification protocol. The composite showed improved adsorption capacity for the removal of pesticides from wastewater. Graphene oxide was synthesized using the modified Hummer's method, while the silica monolith was prepared via sol-gel method. The composite was characterized via X-ray diffraction, Fourier transform infra-red, Brunauer Emmett and Teller (BET/BJH) analysis, zeta potential, and FESEM imaging. Different adsorption parameters such as pH, contact time, adsorbate and adsorbent concentration, and temperature were optimized for the adsorption of pesticides. The equilibrium and kinetic models were applied to the adsorption process of the pesticides. Qe of the composite as found to be 342.46 mg g-1 for imidacloprid and 37.15 mg g-1 for carbofuran. The adsorption process followed the pseudo 2nd order kinetic model for carbofuran (R2~0.9971) and imidacloprid (R2~0.9967). The Freundlich isotherm best fitted to the adsorption data of the pesticides with R2 value of 0.9956 for carbofuran and 0.95 for imidacloprid. The resultant adsorbent/composite material came out with very good results for the removal of pesticides.

Highly selective and sensitive spectrofluorimetric method for determination of cypermethrin in different environmental samples.

A sensitive, selective, and simple spectrofluorimetric method for the detection and determination of cypermethrin (CYP) in various samples based on thioglycolic acid-caped Mn-doped ZnS quantum dots (TGA@Mn-ZnS-QDs) is reported. These quantum dots were synthesized using the Gonzalez method. The synthesized quantum dots were structurally characterized with the help of different spectroscopic techniques including X-ray diffraction (XRD) and energy dispersive X-ray (EDX) techniques and fluorescence spectroscopy. The quantum dots were used for spectrofluorimetric detection and determination of CYP. The emission peak of these quantum dots at 632 nm showed a linear quenching with increasing the concentration of CYP, noticing an excellent linear relationship between F°/F values and CYP in the range of 0.5-12 µg mL-1 with a correlation coefficient (R2) of 0.992. The influence of different physiochemical parameters such as time, pH, the concentration of quantum dots, and other pesticides interference on the fluorescence quenching was investigated. The detection limit was calculated to be 0.132 µg mL-1. The developed method was successfully applied for the detection and determination of CYP in various spiked samples (tomato, okra, pea, spinach, soil, and water) using the spike and recovery methods. The percent recoveries of CYP from these samples were found to be 77 ± 0.05% to 95 ± 0.12% at various levels.

Synthesis, Characterization and Applications of Schiff Base Chemosensor for Determination of Cr(III) Ions.

The development of a highly sensitive, selective, and efficient sensor for the determination and detection of Cr(III) ions remains a great challenge. Recently, some fluorescent chemosensors have been developed for the recognition of Cr(III) ions. But, the main drawbacks of the reported fluorescent chemosensors are the lack of selectivity and interference of anions and other trivalent cations. Herein, we designed and synthesized a novel thiazole-based fluorescent and colorimetric Schiff base chemosensor SB2 for the detection of Cr(III) ion by chemodosimetric approach. Using different analytical techniques including UV-vis, 13C-NMR, 1H-NMR, and FT-IR analysis the chemosensor SB2 was structurally characterized. The fully characterized chemosensor SB2 was used for the spectrofluorimetric and colorimetric detection of Cr(III) ions. Interestingly, chemosensor SB2 upon interaction with various metal cations including Ni2+, Na+, Cd2+, Ag+, Mn2+, K+, Zn2+, Cu2+, Hg2+, Co2+, Pb2+, Mg2+, Sn2+, Al3+ and Cr3+ displays highly selective and sensitive fluorescent (turn-on) and colorimetric (yellow to colorless) response toward Cr(III) ions. The fluorescence and UV-vis techniques confirmed the selective hydrolysis of azomethine group (-C = N-) of Schiff base chemosensor SB2 by Cr(III) ions. As a result, the fluorescence enhancement was observed that is corresponding to 2-hydroxy-1-nepthaldehyde (fluorophore). The chemosensor SB2 exhibits high interference performance towards Cr(III) ions over other metal cations in a wide pH range. Mover, the quite low detection limit was calculated to be 0.027 µg ml-1 (0.5 µM) (3σ/slop), lower than the maximum tolerable limits of Cr(III ions (10 µM) in drinking water permitted by the United States Environmental Protection Agency (EPA). These results show that chemosensor SB2 has great potential to detect selectively Cr(III) ions in the agricultural, environmental and biological analysis system.

Charge-transfer complex-based spectrophotometric method for the determination of mesotrione in environmental samples.

A simple, accurate, sensitive, and selective spectrophotometric method has been developed for the determination of mesotrione. This method is based on the reaction of mesotrione with Fe(III) to form a charge transfer metal complex having λmax at 348 nm. Beer's law was obeyed in the concentration range of 0.2-10.0 µg mL-1 with limit of detection (LOD) and limit of quantification (LOQ) equal to 0.053 and 0.162 µg mL-1, respectively. The percent recovery of mesotrione from different environmental and agricultural samples was found to be 95.00-106.50% at various levels. Notably, the developed method was successfully employed for the determination of mesotrione in environmental (pond water, canal water, tap water, and soil) and agricultural (maize grains) samples.

Thiourea Derivatives, Simple in Structure but Efficient Enzyme Inhibitors and Mercury Sensors.

In this study six unsymmetrical thiourea derivatives, 1-isobutyl-3-cyclohexylthiourea (1), 1-tert-butyl-3-cyclohexylthiourea (2), 1-(3-chlorophenyl)-3-cyclohexylthiourea (3), 1-(1,1-dibutyl)-3-phenylthiourea (4), 1-(2-chlorophenyl)-3-phenylthiourea (5) and 1-(4-chlorophenyl)-3-phenylthiourea (6) were obtained in the laboratory under aerobic conditions. Compounds 3 and 4 are crystalline and their structure was determined for their single crystal. Compounds 3 is monoclinic system with space group P21/n while compound 4 is trigonal, space group R3:H. Compounds (1-6) were tested for their anti-cholinesterase activity against acetylcholinesterase and butyrylcholinesterase (hereafter abbreviated as, AChE and BChE, respectively). Potentials (all compounds) as sensing probes for determination of deadly toxic metal (mercury) using spectrofluorimetric technique were also investigated. Compound 3 exhibited better enzyme inhibition IC50 values of 50, and 60 µg/mL against AChE and BChE with docking score of -10.01, and -8.04 kJ/mol, respectively. The compound also showed moderate sensitivity during fluorescence studies.

Particle packed mixed-mode chromatographic stationary phase for the separation of peptide in liquid chromatography.

A particle-based stationary phase has been prepared for the separation of five synthetic peptides and a mixture containing tryptic digest of cytochrome C in liquid chromatography. Particles originating from silica monolith were differentially sedimented to obtain 1-2 µm particles. A stationary phase was achieved by the coating of poly(styrene-methacrylic acid-N-phenylacrylamide) copolymer onto the particles via reversible addition-fragmentation chain transfer polymerization reaction. Stainless steel column (30 cm long and 1 mm internal diameter) was packed with stationary phase. Very high separation efficiency (ca. 351 000 plates/m) was achieved for five commercial peptides with a percent relative standard deviation of less than 1%. Protocol for the synthesis and modification of silica monolith particles has been well optimized with a good reproducibility both in particle and pore size. The column resolved about 21 peptide components from a mixture containing tryptic digest of cytochrome C, under the elution conditions of acetonitrile/15 mM ammonium format (65/35 v/v%) with a flow rate of 28 µL/min.

Medicinal Importance, Coordination Chemistry with Selected Metals (Cu, Ag, Au) and Chemosensing of Thiourea Derivatives. A Review.

Thiourea and its derivatives are versatile compounds used in several fields of life ranging from medicinal to chemosensor applications. In this review article, generally used preparative methods of thiourea, its coordination compounds with selected metals (Cu, Ag, Au) for biological and medicinal applications and the potentials of thiourea derivatives in analytical chemistry as chemosensors have been discussed. The improved activities of these derivatives in the field of pharmaceutical chemistry can be achieved by coordination with a suitable metal ion. The two fields, selected coordination chemistry and chemosensing of thiourea derivatives are discussed. Since thiourea derivatives are biologically active therefore, their use as chemosensors can be useful to detect anions and cations in environmental and biological samples. The review contains 212 references.

Determination of Isoproturon in Environmental Samples using the QuEChERS Extraction-Spectrofluorimetric Method.

An accurate and sensitive method has been developed for determination of the herbicide isoproturon using the Quick Easy Cheap Effective Rugged Safe (QuEChERS) extraction-spectrofluorimetric technique. The method involves the reaction of 2-cyanoacetamide with isoproturon in basic medium (NH3 ; 15 mol/L). The resulting fluorescent product was found to show maximum emission at 378 nm and maximum excitation at 333 nm. Fluorescence intensity under the influence of different parameters was investigated. The linear range of analyte concentrations was found to be 0.5 to 15 µg/mL, with a limit of detection of 0.144 µg/mL, a limit of quantification of 0.437 µg/mL (signal to noise ratio = 3), and a regression coefficient of 0.9991, under optimized conditions. The proposed method was effectively applied for determination of isoproturon in different matrices; the percentage of recovery varied from 85.00 ± 1.2% to 96.00 ± 0.5%. The method was also applied for residue analysis of isoproturon in real soil samples collected from a pilot field. For extraction of isoproturon, the QuEChERS extraction approach was used, and the average residue in the soil samples was found to be 0.81 ± 0.07 µg/g. To show the potential of this approach, our results were compared with those of other methods reported in the literature. Environ Toxicol Chem 2019;38:2614-2620. © 2019 SETAC.

Kinetic and equilibrium profile of the adsorptive removal of Acid Red 17 dye by surfactant-modified fuller's earth.

In the present study, fuller's earth (FE) was modified with sodium dodecyl sulfate for removal of Acid Red 17 (AR 17) dye from aqueous solutions. The surfactant-modified FE and FE were characterized by a Fourier transform infrared spectrometer, thermogravimetric analyzer and scanning electron microscope. Batch adsorption experiments were carried out as a function of contact time, pH, initial concentration of AR 17 and adsorbent dosage. About 99.1% adsorption efficiency was achieved within 60 min at adsorbent dose of 0.1 g for initial dye concentration of 1,000 mg L-1 at pH 10. The adsorption data were well fitted with the Dubinin-Radushkevich isotherm model implying physisorption as the major phenomenon for adsorption. The kinetic data were analyzed using four kinetic equations: pseudo-first-order, pseudo-second-order, intraparticle diffusion and Elovich equations. The rates of adsorption confirmed the pseudo-second-order kinetics with good correlation value (R2 = 0.999). The results indicate that the modified adsorbent can effectively be used for the removal of AR 17 from wastewater with high absorption capacity of 2164.61 mg g-1.

Spectrofluorimetric Method for Quantification of Triazine Herbicides in Agricultural Matrices.

A spectrofluorimetric method for determination of triazine herbicides was developed. The method involves reaction of ammonical 2-cyanoacetamide with the herbicide. The net fluorescent intensity (FI) of the product was measured at 376 nm using 330 nm as excitation wavelength. A linear relationship between concentration and FI was found in the range of 0.3 - 10 µg mL(-1) for atrazine and 0.2 - 10 µg mL(-1) for terbutryn. The LOD and LOQ were found to be 0.07 ± 0.023 µg mL(-1) and 0.23 ± 0.023 µg mL(-1), respectively, with %RSD <12.1% for atrazine and 0.027 ± 0.009 µg mL(-1) and 0.091 ± 0.009 µg mL(-1), respectively, with %RSD <5% for terbutryn. The %recoveries of the subject triazines from soil and wheat grains were found in the range of 90.0 ± 0.14 to 96.0 ± 0.15% for atrazine and 95.0 ± 0.05 to 98 ± 0.02% for terbutryn.

Glyphosate herbicide residue determination in samples of environmental importance using spectrophotometric method.

A simple selective spectrophotometric method has been developed for the determination of glyphosate herbicide in environmental and biological samples. Glyphosate was reacted with carbon disulphide to form dithiocarbamic acid which was further followed for complex formation with copper in the presence of ammonia. The absorbance of the resulting yellow coloured copper dithiocarbamate complex was measured at 435 nm with molar absorptivity of 1.864 x 10(3) L mol(-1)cm(-1).The analytical parameters were optimized and Beer's law was obeyed in the range of 1.0-70 microg mL(-1). The composition ratio of the complex was glyphosate: copper (2:1) as established by Job's method with a formation constant of 1.06 x 10(5). Glyphosate was satisfactorily determined with limit of detection and quantification of 1.1 and 3.7 microg mL(-1), respectively. The investigated method was applied successfully to the environmental samples. Recovery values in soil, wheat grains and water samples were found to be 80.0+/-0.46 to 87.0+/-0.28%, 95.0+/-0.88 to 102.0+/-0.98% and 85.0+/-0.68 to 92.0+/-0.37%, respectively.