ABSTRACT
This study reports a novel analytical approach for the simultaneous determination of ethylene-thiourea (ETU) and propylene-thiourea (PTU) in fruits and vegetables by (reverse phase) high-performance liquid chromatography (HPLC) coupled to inductively coupled plasma-tandem mass spectrometry (ICP-QQQMS or ICP-MS/MS). A baseline separation of ETU and PTU was achieved in less than 5 min. A robust method validation by using the accuracy profile approach was performed by carrying out four measurement series in duplicate at six different levels over a timespan of 4 weeks (different days). The recovery factors ranged from 87 to 101% for ETU and from 98 to 99% for PTU (depending on the spiking level). The coefficient of variation in terms of repeatability (CVr) ranged from 1 to 4.7% for ETU and from 1.8 to 3.9% for PTU (depending also on the analyte level) while the coefficient of variation in terms of intermediate reproducibility (CVR) ranged from 3.4 to 10% for ETU and from 1.8 to 10.8% for PTU. The limit of quantification was 0.022 mg kg-1 (wet weight) for ETU and 0.010 mg kg-1 (ww) for PTU. This novel approach was proved to be highly robust and suitable for the determination of ETU and PTU in foodstuffs of vegetal origin.
Subject(s)
Ethylenethiourea , Thiourea , Thiourea/analysis , Ethylenethiourea/analysis , Chromatography, High Pressure Liquid/methods , Tandem Mass Spectrometry/methods , Reproducibility of Results , EthylenesSubject(s)
Dermatitis, Allergic Contact/etiology , Neoprene/adverse effects , Skin Diseases, Vesiculobullous/etiology , Thiourea/adverse effects , Adult , Diving , Humans , Indicators and Reagents , Male , Neoprene/chemistry , Patch Tests , Recurrence , Sports Equipment/adverse effects , Thiourea/analysisABSTRACT
Prospective antiviral molecule (2E)-N-methyl-2-[(4-oxo-4H-chromen-3-yl)methylidene]-hydrazinecarbothioamide has been probed using Fourier transform infrared (FTIR), FT-Raman and quantum chemical computations. The geometry equilibrium and natural bond orbital analysis have been carried out with density functional theory employing Becke, 3-parameter, Lee-Yang-Parr method with the 6-311G++(d,p) basis set. The vibrational assignments pertaining to different modes of vibrations have been augmented by normal coordinate analysis, force constant and potential energy distributions. Drug likeness and oral activity have been carried out based on Lipinski's rule of five. The inhibiting potency of 2(2E)-methyl-2-[(4-oxo-4H-chromen-3-yl)methylidene]-hydrazinecarbothioamide has been investigated by docking simulation against SARS-CoV-2 protein. The optimized geometry shows a planar structure between the chromone and the side chain. Differences in the geometries due to the substitution of the electronegative atom and intermolecular contacts due to the chromone and hydrazinecarbothioamide were analyzed. NBO analysis confirms the presence of two strong stable hydrogen bonded NHâ¯O intermolecular interactions and two weak hydrogen bonded CHâ¯O interactions. The red shift in NH stretching frequency exposed from IR substantiates the formation of NHâ¯O intermolecular hydrogen bond and the blue shift in CH stretching frequency substantiates the formation of CHâ¯O intermolecular hydrogen bond. Drug likeness, absorption, distribution, metabolism, excretion and toxicity property gives an idea about the pharmacokinetic properties of the title molecule. The binding energy of the nonbonding interaction with Histidine 41 and Cysteine 145, present a clear view that 2(2E)-methyl-2-[(4-oxo-4H-chromen-3-yl)methylidene]-hydrazinecarbothioamide can irreversibly interact with SARS-CoV-2 protease.
Subject(s)
Antiviral Agents , COVID-19 Drug Treatment , Chromones , Coronavirus 3C Proteases/antagonists & inhibitors , Drugs, Investigational , SARS-CoV-2/drug effects , Thiourea , Antiviral Agents/analysis , Antiviral Agents/chemical synthesis , Antiviral Agents/chemistry , Antiviral Agents/pharmacokinetics , Chromones/analysis , Chromones/chemical synthesis , Chromones/chemistry , Chromones/pharmacokinetics , Computational Chemistry , Coronavirus 3C Proteases/metabolism , Crystallography, X-Ray , Drugs, Investigational/analysis , Drugs, Investigational/chemical synthesis , Drugs, Investigational/chemistry , Drugs, Investigational/pharmacokinetics , Humans , Hydrazines/chemistry , Hydrogen/chemistry , Hydrogen Bonding , Models, Molecular , Molecular Docking Simulation , Molecular Structure , Protein Binding , Quantum Theory , Spectroscopy, Fourier Transform Infrared , Spectrum Analysis, Raman , Thioamides/analysis , Thioamides/chemical synthesis , Thioamides/chemistry , Thioamides/pharmacokinetics , Thiourea/analysis , Thiourea/chemical synthesis , Thiourea/chemistry , Thiourea/pharmacokinetics , VibrationABSTRACT
This study was conducted to design an electrochemical sensor for detection of l-glutamate (L-Glu) and Aspartate (Asp), which contribute largely to the umami taste of beef. Using N, N'-diphenylthiourea (DPTU), polypyrrole (PPy), and polyvinyl chloride (PVC), a composite electrode (DPTU/PVC/PPy/Pt) was prepared for rapidly electrochemical detection of l-Glu and Asp. The surface morphology of the synthesized functionalized electrode was characterized by Field Emission Scanning Electron Microscopy (FESEM). Potentials of umami amino acids accounted for 97.8%, while six interferential amino acids existed. The linear correlation between the content of l-Glu and Asp in beef broth was studied under different treatment conditions. The sensor compared with an amino acid analyzer well detected the contents of l-Glu and Asp in beef broths, with a coefficient of 0.991 in Pearson correlation analysis and an accuracy of 88.9%. The proposed electrochemical sensor showed good concurrence with previously reported methods and was effectively employed for the quantification of l- Glu and Asp in beef. PRACTICAL APPLICATION: The sensor exhibits the good performance with high stability and high accuracy. And it is a potential sensing platform with good reproducibility, making the proposed method suitable and reliable for routine analysis of L-Glu and Asp in beef. This method was proved promising for quantitative detecting amino acids in beef.
Subject(s)
Aspartic Acid/analysis , Electrochemical Techniques/methods , Glutamic Acid/analysis , Red Meat/analysis , Thiourea/analogs & derivatives , Animals , Cattle , Reproducibility of Results , Thiourea/analysisABSTRACT
A new and efficient anodic Ru(bpy)32+ ECL system by using acridine orange (3,6-Bis(dimethylamino)acridine, AO) as a coreactant was reported in a neutral medium. The developed Ru(bpy)32+-AO system displayed a higher ECL intensity than that of the classic Ru(bpy)32+- oxalate ECL system, and was further exploited for the ECL detection of thiourea for the first time.
Subject(s)
Acridine Orange/chemistry , Luminescence , Organometallic Compounds/chemistry , Thiourea/analysis , Luminescent Measurements , Molecular Structure , Organometallic Compounds/chemical synthesisABSTRACT
Herein, a facile and quick strategy to detect thiourea was conducted based on the reversion of fluorescence quenching of nitrogen doped carbon dots (NCDs) by Hg2+. The NCDs with good water solubility and 17% of quantum yield was synthesized by one-step hydrothermal method, using ammonium citrate and dextrin as carbon source and nitrogen source, respectively. The fluorescence of NCDs was obviously quenched by Hg2+ and can be recovered, due to stronger interaction between thiourea and Hg2+. There was a good linear relationship between the recovered fluorescence and the concentration of thiourea within range of 0.90-10.0⯵M and the detection limit for thiourea detection was 0.15⯵M. The as-prepared NCDs can be used for determination of thiourea in tap water, lake water and rice flour products, and the spike recoveries were between 91.6 and 108%.
Subject(s)
Carbon/chemistry , Mercury/analysis , Nitrogen/chemistry , Quantum Dots/chemistry , Thiourea/analysis , Flour/analysis , Fluorescence , Hydrogen-Ion Concentration , Ions , Quantum Dots/ultrastructure , Spectrometry, Fluorescence , Spectrophotometry, Ultraviolet , Water/chemistryABSTRACT
In this study, we developed a novel bioelectronic taste sensor for the detection of specific bitter substances. A human bitter taste receptor, hT2R4, was efficiently expressed in Escherichia coli (E. coli), which was used as the primary recognition element. A simple and low-cost electrochemical device based on ITO-based electrolyte-semiconductor (ES) structure was innovatively employed as the transducer to assess bacterial metabolic consequences of receptor activation in real time. An apparent increase in extracellular acidification rate was observed, which was resulted from the triggering of hT2R4 receptors by their target ligand of denatonium. The sensor showed dose-dependent responses to denatonuim ranging from 50â¯nM to 500â¯nM, while non-bioengineered bacteria without hT2R4 receptors exhibited negligible responses to the same stimulus. In addition, the specificity of the proposed taste biosensor was verified using other typical bitter substances such as quinine and alpha-naphthylthiourea (ANTU). This research provides a simple and inexpensive approach for the construction of bioelectronic taste sensors.
Subject(s)
Escherichia coli/genetics , Quaternary Ammonium Compounds/analysis , Quinine/analysis , Receptors, G-Protein-Coupled/metabolism , Thiourea/analogs & derivatives , Base Sequence , Biosensing Techniques/methods , Electrochemical Techniques/methods , Humans , Hydrogen-Ion Concentration , Quaternary Ammonium Compounds/metabolism , Quinine/metabolism , Receptors, G-Protein-Coupled/genetics , Thiourea/analysis , Thiourea/metabolismABSTRACT
Selenate (Se(VI)) and selenite (Se(IV)) are common soluble wastewater pollutants in natural and anthropogenic systems. We evaluated the reduction efficiency and removal of low (0.02 and 2 mg/L) and high (20 and 200 mg/L) Se(IV)(aq) and Se(VI)(aq) concentrations to elemental (Se0) via the use of ascorbic acid (AA), thiourea (TH), and a 50-50% mixture. The reduction efficiency of AA with Se(IV)(aq) to nano- and micro-crystalline Se0 was ≥ 95%, but ≤ 5% of Se(VI)(aq) was reduced to Se(IV)(aq) with no Se0. Thiourea was able to reduce ≤ 75% of Se(IV)(aq) to bulk Se0 at lower concentrations but was more effective (≥ 90%) at higher concentrations. Reduction of Se(VI)(aq)âSe (IV)(aq) with TH was ≤ 75% at trace concentrations which steadily declined as the concentrations increased, and the products formed were elemental sulfur (S0) and SnSe8-n phases. The reduction efficiency of Se(IV)(aq) to bulk Se0 upon the addition of AA+TH was ≤ 81% at low concentrations and ≥ 90% at higher concentrations. An inverse relation to what was observed with Se(IV)(aq) was found upon the addition of AA+TH with Se(VI)(aq). At low Se(VI)(aq) concentrations, AA+TH was able to reduce more effectively (≤ 61%) Se(VI)(aq)âSe(IV)(aq)âSe0, while at higher concentrations, it was ineffective (≤ 11%) and Se0, S0, and SnSe8-n formed. This work helps to guide the removal, reduction effectiveness, and products formed from AA, TH, and a 50-50% mixture on Se(IV)(aq) and Se(VI)(aq) to Se0 under acidic conditions and environmentally relevant concentrations possibly found in acidic natural waters, hydrometallurgical chloride processing operations, and acid mine drainage/acid rock drainage tailings. Graphical Abstract á .
Subject(s)
Ascorbic Acid/chemistry , Models, Chemical , Selenic Acid/chemistry , Selenious Acid/chemistry , Thiourea/chemistry , Ascorbic Acid/analysis , Mining , Oxidation-Reduction , Selenic Acid/analysis , Selenious Acid/analysis , Selenium/analysis , Selenium Compounds , Sulfur , Thiourea/analysisABSTRACT
Two simple, selective and rugged liquid chromatography-tandem mass spectrometry (LC-MS/MS) methods were developed and validated for determination of propineb and propylenethiourea (PTU) in infant formula, fruit-based and cereal-based baby food and raw materials used in production of infant formula, including carbohydrates, protein isolates, vegetable oils and emulsifiers. The sample preparation procedure for propineb analysis was based on streamlined derivatisation to form and stabilise the target analyte (propylenebisdithiocarbamate-dimethyl), followed by extraction using a modified QuEChERS procedure with a dispersive solid phase extraction (d-SPE). The PTU determination employed an aqueous extraction with optimised protein precipitation and single-step SPE clean-up. To achieve maximum sensitivity, electrospray ionisation and atmospheric-pressure chemical ionisation were employed for LC-MS/MS analysis of propineb and PTU, respectively. Validation of the developed methods was performed in accordance with Document SANTE/11813/2017. Mean recoveries were in the range of 86-120% for propineb and PTU, respectively, with interday and intraday repeatabilities below 13%. A limit of quantification (LOQ) of 0.003 mg kg-1 was validated for most of the evaluated analyte/sample matrix combinations with the exception of PTU in soy protein isolate and soybean oil, for which an LOQ of 0.01 mg kg-1 was obtained. This is the first report that provides validated methods for monitoring propineb and PTU in infant formula and baby foods at concentrations compliant with the maximum residue levels established in the EU legislation.
Subject(s)
Food Contamination/analysis , Infant Food/analysis , Infant Formula/analysis , Thiourea/analogs & derivatives , Zineb/analogs & derivatives , Chromatography, Liquid , Humans , Infant , Tandem Mass Spectrometry , Thiourea/analysis , Zineb/analysisABSTRACT
BACKGROUND/AIM: Tumours of astroglial origin are the most common primary brain malignancy characterized by infiltrative growth and resistance to standard antitumour therapy. Glioma progression is thought to be related to various intracellular signal transduction pathways that involve the activation of protein kinases. Protein kinases play important roles in cell differentiation, proliferation, and survival. Recently, novel, specific inhibitors of constitutively active serine/threonine kinases and structurally similar isothiourea derivatives were suggested to induce apoptosis and inhibit proliferation in several types of human cancer cells. MATERIALS AND METHODS: In this study, we examined the cytotoxic and proapoptotic activities of selected modified pentabromobenzyl isothioureas (ZKKs) in an adult human glioblastoma (T98G) and a subependymal giant cell astrocytoma cell (SEGA) line. We evaluated cell proliferation, viability, and apoptosis. RESULTS: Two pentabromobenzyl isothiourea bromide derivatives, ZKK-13 and N,N,N'-trimethyl-ZKK1 (TRIM), exhibited the most potent cytotoxic and proapoptotic efficacies against human glioma-derived cells, even at a very low concentration (1 µM). ZKK-13 (25-50 µM) inhibited cell growth by approximately 80-90% in 24 and 48 h of treatment. We showed that selected ZKKs exerted antiproliferative activity against astroglial neoplastic cells of both low- and high-grade tumour malignancy classes. No synergistic effects were detected when ZKKs were combined with serine/threonine kinase inhibitors. CONCLUSION: Our findings indicated that modified ZKKs show promise for the treatment of glioma-derived brain tumours.
Subject(s)
Antineoplastic Agents/pharmacology , Astrocytes/pathology , Isothiuronium/analogs & derivatives , Protein Kinase Inhibitors/pharmacology , Thiourea/analysis , Thiourea/pharmacology , Adult , Apoptosis/drug effects , Astrocytoma/pathology , Brain Neoplasms/pathology , Casein Kinase II/antagonists & inhibitors , Cell Division/drug effects , Cell Line, Tumor , Drug Screening Assays, Antitumor , Glioblastoma/pathology , Humans , Isothiuronium/chemical synthesis , Isothiuronium/pharmacology , Molecular Targeted Therapy , Neoplasm Proteins/antagonists & inhibitors , Protein Kinase Inhibitors/chemical synthesis , Protein Serine-Threonine Kinases/antagonists & inhibitors , Thiourea/chemistryABSTRACT
A sensitive and specific method for the determination of propineb and its metabolites, propylenethiourea (PTU) and propylenediamine (PDA), using gas chromatography with flame photometric detection (GC-FPD) and LC-MS/MS was developed and validated. Propineb and its metabolite residue dynamics in supervised field trials under Good Agricultural Practice (GAP) conditions in banana and soil were studied. Recovery of propineb (as CS2), PDA and PTU ranged from 75.3 to 115.4% with RSD (n = 5) of 1.3-11.1%. The limit of quantification (LOQ) of CS2, PDA and PTU ranged from 0.005 to 0.01 mg kg-1, and the limit of detection (LOD) ranged from 0.0015 to 0.0033 mg kg-1. Dissipation experiments showed that the half-life of propineb in banana and soil ranged from 4.4 to 13.3 days. PTU was found in banana with a half-life of 31.5-69.3 days, while levels of PDA were less than 0.01 mg kg-1 in banana and soil. It has been suggested that PTU is the major metabolite of propineb in banana. The method was demonstrated to be reliable and sensitive for the routine monitoring of propineb and its metabolites in banana and soil. It also serves as a reference for the detection and monitoring of dithiocarbamates (DTCs) residues and the evaluation of their metabolic pathway.
Subject(s)
Diamines/analysis , Musa/chemistry , Soil Pollutants/analysis , Thiourea/analogs & derivatives , Zineb/analogs & derivatives , Agriculture/methods , Chromatography, Gas/methods , Chromatography, Liquid/methods , Diamines/metabolism , Food Analysis/methods , Food Contamination/analysis , Fungicides, Industrial/analysis , Fungicides, Industrial/metabolism , Half-Life , Limit of Detection , Pesticide Residues/analysis , Reproducibility of Results , Tandem Mass Spectrometry/methods , Thiourea/analysis , Zineb/analysis , Zineb/metabolismABSTRACT
This paper describes the synthesis of a novel series of acridine thiosemicarbazones through a two-step reaction between various isothiocyanates and hydrazine followed by treatment with acridin-9-carbaldehyde. The properties of this series of seven new derivatives are studied using NMR and biochemical techniques, and the DNA-binding properties of the compounds are determined using spectrophotometric studies (UV-vis absorption, fluorescence, and circular/linear dichroism) and viscometry. The binding constants K are estimated as being in the range of 2.2 to 7.8×104M-1 and the percentage of hypochromism was found to be 22.11-49.75% (from UV-vis spectral titration). Electrophoretic experiments prove that the novel compounds demonstrate moderate inhibitory effects against Topo I activity at a concentration of 60×10-6M.
Subject(s)
Acridines , Thiourea , Topoisomerase I Inhibitors , Acridines/analysis , Acridines/chemistry , Acridines/metabolism , Circular Dichroism , DNA/chemistry , DNA/metabolism , DNA Topoisomerases, Type I , Magnetic Resonance Spectroscopy , Models, Molecular , Spectrophotometry, Ultraviolet , Thiosemicarbazones/analysis , Thiosemicarbazones/chemistry , Thiosemicarbazones/metabolism , Thiourea/analysis , Thiourea/chemistry , Thiourea/metabolism , Topoisomerase I Inhibitors/analysis , Topoisomerase I Inhibitors/chemistry , Topoisomerase I Inhibitors/metabolismABSTRACT
BACKGROUND: Contact allergy to chloroprene rubber products is well known. Thiourea compounds are considered the cause of allergy. Diethylthiourea commonly occurs in this type of product and can decompose to the sensitizer ethyl isothiocyanate. OBJECTIVES: To investigate the clinical importance of degradation products and metabolites from organic thioureas in contact allergy to chloroprene rubber with a focus on isothiocyanates and isocyanates. METHODS: Patients with contact allergy to diphenylthiourea were patch tested with phenyl isothiocyanate and phenyl isocyanate. Patients with known contact allergy to diethylthiourea were retested with diethylthiourea, while chemical analyses of their chloroprene rubber products were performed. The stability of diethylthiourea, diphenylthiourea and dibutylthiourea in patch-test preparations was investigated. Liquid chromatography/mass spectrometry and solid-phase microextraction/gas chromatography were used for determination of organic thioureas and isothiocyanates. RESULTS: All patients allergic to diphenylthiourea reacted to phenyl isothiocyanate, two of eight reacted to phenyl isocyanate and six of eight reacted to diphenylthiourea. Four patients allergic to diethylthiourea reacted at retest; diethylthiourea was detected in all chloroprene rubber samples, with levels of 2-1200 nmol cm-2 . At 35 °C, ethyl isothiocyanate was emitted from all samples. Patch-test preparations of diethylthiourea, diphenylthiourea and dibutylthiourea all emitted the corresponding isothiocyanate, with diethylthiourea showing the highest rate of isothiocyanate emission. CONCLUSIONS: Thiourea compounds are degraded to isothiocyanates, which are generally strong or extreme sensitizers, thus acting as prehaptens. This process occurs in both chloroprene rubber products and patch-test preparations. Positive reactions to phenyl isocyanate indicate cutaneous metabolism, as the only known source of exposure to phenyl isocyanate is through bioactivation of diphenylthiourea.
Subject(s)
Chloroprene/adverse effects , Dermatitis, Allergic Contact/etiology , Isothiocyanates/adverse effects , Rubber/adverse effects , Adult , Chloroprene/chemistry , Female , Haptens/adverse effects , Humans , Isocyanates/adverse effects , Male , Middle Aged , Patch Tests , Rubber/chemistry , Thiourea/adverse effects , Thiourea/analogs & derivatives , Thiourea/analysisABSTRACT
Transcriptional co-activator with PDZ-binding motif (TAZ) plays versatile roles in cell proliferation and differentiation. It is phosphorylated by large tumor suppressor kinases, the core kinases of the tumor-suppressive Hippo pathway. Phosphorylation induces the cytoplasmic accumulation of TAZ and its degradation. In human cancers, the deregulation of the Hippo pathway and gene amplification enhance TAZ activity. TAZ interacts with TEA domain family members (TEAD), and upregulates genes implicated in epithelial-mesenchymal transition. It also confers stemness to cancer cells. Thus, TAZ activation provides cancer cells with malignant properties and worsens the clinical prognosis. Therefore, TAZ attracts attention as a therapeutic target in cancer therapy. We applied 18 606 small chemical compounds to human osteosarcoma U2OS cells expressing GFP-fused TAZ (GFP-TAZ), monitored the subcellular localization of GFP-TAZ, and selected 33 compounds that shifted GFP-TAZ to the cytoplasm. Unexpectedly, only a limited number of compounds suppressed TAZ-mediated enhancement of TEAD-responsive reporter activity. Moreover, the compounds that weakened TEAD reporter activity did not necessarily decrease the unphosphorylated TAZ. In this study, we focused on three compounds that decreased both TEAD reporter activity and unphosphorylated TAZ, and treated several human cancer cells with these compounds. One compound did not show a remarkable effect, whereas the other two compounds compromised the cell viability in certain cancer cells. In conclusion, the GFP-TAZ-based assay can be used as the first screening for compounds that inhibit TAZ and show anticancer properties. To develop anticancer drugs, we need additional assays to select the compounds.
Subject(s)
Drug Evaluation, Preclinical/standards , Green Fluorescent Proteins/metabolism , PDZ Domains/drug effects , Small Molecule Libraries/analysis , Small Molecule Libraries/pharmacology , Transcription Factors/antagonists & inhibitors , Transcription Factors/chemistry , Transcription, Genetic/drug effects , Amino Acid Motifs , Cell Line, Tumor , Cell Nucleus/drug effects , Cell Nucleus/metabolism , Cell Survival/drug effects , Cytoplasm/drug effects , Cytoplasm/metabolism , Dobutamine/pharmacology , Drug Evaluation, Preclinical/methods , Ethanolamines/analysis , Ethanolamines/pharmacology , Genes, Reporter , Green Fluorescent Proteins/genetics , HEK293 Cells , Heterocyclic Compounds, 3-Ring/analysis , Heterocyclic Compounds, 3-Ring/pharmacology , Hippo Signaling Pathway , Humans , Phosphoric Monoester Hydrolases/metabolism , Phosphorylation/drug effects , Protein Binding/drug effects , Protein Serine-Threonine Kinases/metabolism , Pyridines/analysis , Pyridines/pharmacology , Recombinant Fusion Proteins/chemistry , Recombinant Fusion Proteins/genetics , Recombinant Fusion Proteins/metabolism , Signal Transduction/drug effects , Thiourea/analogs & derivatives , Thiourea/analysis , Thiourea/pharmacology , Time Factors , Transcription Factors/genetics , Transcription Factors/metabolism , ortho-Aminobenzoates/analysis , ortho-Aminobenzoates/pharmacologyABSTRACT
Graft copolymer of alginate and acrylamide was synthesized by grafting acrylamide chains on to alginate by free radical polymerization using potassium bromate/thiourea redox system in an inert atmosphere. The reaction conditions for maximum grafting have been optimized by varying the reaction variables, including the concentration of acrylamide (3.0×10(2)-9.3×10(2)moldm(-3)), potassium bromate (8×10(-3)-16×10(-3)moldm(-3)), thiourea (1.6×10(-3)-4.8×10(-3)moldm(-3)), sulphuric acid (3.0×10(-3)-7×10(-3)moldm(-3)), alginate (0.6-1.6gdm(-3)) along with time duration (60-180min) and temperature (30-50°C). Water swelling capacity, metal ion sorption, flocculation and resistance to biodegradability studies of synthesized graft copolymer have been performed with respect to the parent polymer. The grafted polymers were characterized by FTIR spectroscopy and thermo gravimetric analysis.
Subject(s)
Acrylamide/chemistry , Alginates/chemistry , Metals/isolation & purification , Polymers/chemistry , Water/chemistry , Adsorption , Biodegradation, Environmental , Bromates/analysis , Flocculation , Glucuronic Acid/chemistry , Hexuronic Acids/chemistry , Hydrogen-Ion Concentration , Ions , Spectroscopy, Fourier Transform Infrared , Temperature , Thermogravimetry , Thiourea/analysis , Time FactorsABSTRACT
In this work, a flow injection analysis (FIA) method was introduced for the determination of trace amounts of thiourea in tap water. This method is based upon the inhibition effect of thiourea on the reaction between meta-cresol purple (MCP) and potassium bromate catalyzed by bromide ions in a sulfuric acid medium. In the presence of thiourea, an induction period appears in the reaction system, and as a result, the absorbance of MCP increases at 525 nm in the FIA manifold. The chemical and FIA variables are studied and optimized using the univariate and Simplex optimization methods. Under the optimum conditions, thiourea can be determined in the range of 0.100-13.0 µg mL(-1). The limit of detection (3σ) for thiourea was found to be 0.0310 µg mL(-1). The relative standard deviations (RSDs) for six replicate determinations of 0.500, 5.00, and 12.0 µg mL(-1) of thiourea were 4.0%, 1.8%, and 1.2%, respectively. The proposed method was also applied for the determination of thiourea in orange juice and orange peel samples with recoveries in the range of 98.0-101%. The analytical speed of the method was calculated to be about 120 sample per hour.
Subject(s)
Beverages/analysis , Citrus sinensis/chemistry , Flow Injection Analysis/methods , Online Systems , Spectrophotometry/methods , Thiourea/analysis , Water/chemistry , Bromates/analysis , Bromides/analysis , Indicators and Reagents , Osmolar Concentration , Potassium Compounds/analysis , Rheology , Sulfuric Acids/analysis , TemperatureABSTRACT
BACKGROUND: Exposure to chloroprene rubber has resulted in numerous cases of allergic contact dermatitis, attributed to organic thiourea compounds used as vulcanization accelerators. However, thiourea compounds are not considered to be strong haptens. OBJECTIVES: To analyse common commercial chloroprene materials for their contents of diethylthiourea (DETU), dibutylthiourea (DBTU), diphenylthiourea (DPTU), and their degradation products, isothiocyanates; and to investigate the sensitization potencies of possible degradation products of the mentioned thiourea compounds. METHODS: Liquid chromatography/mass spectrometry (MS) was used for quantification of organic thiourea compounds in chloroprene products, such as medical, sports and diving gear; isothiocyanates were measured by solid-phase microextraction/gas chromatography/MS. Sensitization potencies were determined with the murine local lymph node assay (LLNA). RESULTS: DETU was identified at concentrations of 2.7-9.4 µg/cm(2) in all samples, whereas neither DBTU nor DPTU was detected. At 37°C, degradation of DETU in the materials to ethyl isothiocyanate (EITC) was detected. EITC and ethyl isocyanate showed extreme and strong sensitization potencies, respectively, in the LLNA. CONCLUSIONS: DETU can act as a prehapten, being degraded to EITC when subjected to body temperature upon skin contact. EITC could thus be the culprit behind allergic contact dermatitis caused by chloroprene rubber.
Subject(s)
Allergens/analysis , Dermatitis, Allergic Contact/etiology , Isothiocyanates/analysis , Neoprene/chemistry , Thiourea/analogs & derivatives , Allergens/immunology , Humans , Isothiocyanates/immunology , Local Lymph Node Assay , Thiourea/analysis , Thiourea/immunologyABSTRACT
Lignins and their cross-linking to hemicelluloses detrimentally affect the cellulose-to-ethanol conversion of grass lignocelluloses. Screening appropriate grass cell walls and their compositional changes during the various steps of the process calls for a high-throughput analytical technique. Such a performance can be fulfilled by Fourier transform mid-infrared (FT-MIR) spectroscopy. In the present paper, a set of maize cell walls from mature stems were selected, including brown midrib samples. Lignin fractions were isolated by mild acidolysis to obtain a set of purified maize lignin standards. The lignin content and the percentage of lignin-derived p-hydroxyphenyl (H), guaiacyl (G), and syringyl (S) thioacidolysis monomers were determined. In addition, the composition of cell wall polysaccharides, as well as the amount of ester-linked p-coumaric (CA) and ferulic (FA) acids, was measured by wet chemistry. Partial least square (PLS) analyses were applied to infrared and chemical data of cell walls. The resulting models showed a good predictive ability with regard to the lignin content, to the frequency of S (or G) thioacidolysis monomers, and to the level of ester-linked CA of maize cell walls. The loading plots and regression coefficients revealed relevant infrared absorption bands.
Subject(s)
Lignin/chemistry , Spectroscopy, Fourier Transform Infrared/methods , Sulfinic Acids/chemistry , Thiourea/analogs & derivatives , Zea mays/chemistry , Lignin/analysis , Plant Extracts/analysis , Plant Extracts/chemistry , Sulfinic Acids/analysis , Thiourea/analysis , Thiourea/chemistryABSTRACT
In 2030, the World Health Organization estimates that more than 350 million people will be diagnosed with diabetes. Consequently, Metformin - the biguanide drug of choice orally administered for diabetes type II - is anticipated to see a spike in production. Unlike many pharmaceutical drugs, Metformin (Met) is not metabolized by humans but passes through the body unchanged. Entering aquatic compartments, such as in sewage, it can be bacterially transformed to the ultimate transformation product Guanylurea (Gua). Sampling over one week (n=5) from a Southern German sewage treatment plant revealed very high average (AV) concentrations in influent (AVMet=111,800ng/L, AVGua=1300ng/L) and effluent samples (AVMet=4800ng/L, AVGua=44,000ng/L). To provide a more complete picture of the distribution and potential persistence of these compounds in the German water cycle, a new, efficient and highly sensitive liquid chromatography mass spectrometric method with direct injection was used for the measurement of Metformin and Guanylurea in drinking, surface, sewage and seawater. Limits of quantification (LOQ) ranging from 2-10ng/L allowed the detection of Metformin and Guanylurea in different locations such as: Lake Constance (n=11: AVMet=102ng/L, AVGua=16ng/L), river Elbe (n=12: AVMet=472ng/L, AVGua=9ng/L), river Weser (n=6: AVMet=349ng/L, AVGua=137ng/L) and for the first time in marine North Sea water (n=14: AVMet=13ng/L, AVGua=11ng/L). Based on daily water discharges, Metformin loads of 15.2kg/d (Elbe) and 6.4kg/d (Weser) into the North Sea were calculated. Lake Constance is used to abstract potable water which is further purified to be used as drinking water. A first screening of two tap water samples contained 2ng/L and 61ng/L of Metformin, respectively. The results of this study suggest that Metformin and Guanylurea could be distributed over a large fraction of the world's potable water sources and oceans. With no natural degradation processes, these compounds can be easily reintroduced to humans as they enter the food chain.
Subject(s)
Hypoglycemic Agents/analysis , Metformin/analysis , Thiourea/analysis , Water Pollutants, Chemical/analysis , Bacteria/metabolism , Biotransformation , Drinking Water/analysis , Drinking Water/microbiology , Environmental Monitoring , Hypoglycemic Agents/metabolism , Kinetics , Metformin/metabolism , Rivers/chemistry , Rivers/microbiology , Sewage/chemistry , Sewage/microbiology , Water Pollutants, Chemical/metabolismABSTRACT
A method of solid phase extraction-liquid chromatography-tandem mass spectrometry (SPE-LC-MS/MS) was developed to determine thiourea dioxide which was illegally added into lotus seed paste fillings. An amount of 0.05% (v/v) acetic acid was used to extract thiourea dioxide from fillings, and the BOND ELUT PLEXA column (60 mg/3 mL) was used as the SPE column to clean-up the extraction. Then, an Agilent HILIC column (100 mm x 2.1 mm, 3.5 microm) was applied to separate target compounds by using the mobile phases of 0.01 mol/L ammonium acetate (pH 3.5) and acetonitrile. Qualitative and quantitative analyses were operated by the multiple reaction monitoring (MRM) mode. The calibration curve showed a good linearity for the target compound in the detection range of 10 - 1 000 microg/L. The limit of detection (LOD) and limit of quantitation (LOQ) of this method were 8.0 microg/kg and 30.0 microg/kg, respectively. The recoveries were in the ranges of 75.3% - 80.7% with the RSDs of no more than 4.83%. This proposed method was rapid, highly specific and suitable for the confirmation and quantitative determination of thiourea dioxide in lotus seed paste fillings.