Three spectrophotometric quantitative analysis of bisoprolol fumarate and telmisartan in fixed-dose combination utilizing ratio spectra manipulation methods.

Hypertension is a chronic condition with multiple drug regimens. Limiting these medicines is critical to patient compliance. Therefore, bisoprolol and telmisartan were recently developed in a fixed-dose combination to control blood pressure. The UV absorption spectra of bisoprolol and telmisartan overlapped significantly. Thus, three spectrophotometric methods have been developed for simultaneous determination of bisoprolol and telmisartan without prior separation. Method A is ratio difference of ratio spectra (RD), which measures the amplitude difference between (210-224) nm for bisoprolol and between (255-365) nm for telmisartan. Method B, the first derivative of ratio spectra (1DD), measures amplitude signals at 232 and 243 nm for bisoprolol and telmisartan, respectively. Method C is the mean centering of ratio spectra (MC), which measures the mean-centered ratio spectra's values at 223 nm for bisoprolol and 245 nm for telmisartan. The applied methods showed good linearity 2-20 µg/mL for bisoprolol, 4-32 µg/mL for telmisartan, with sufficient accuracy and precision. The methods were sensitive, with LOD values of 0.243 µg/mL and 0.596 µg/mL in RD method, 0.313 µg/mL and 0.914 µg/mL in 1DD method, and 0.406 and 0.707 µg/mL in MC method for bisoprolol and telmisartan, respectively, the methods were validated per ICH criteria. The novel methods are precise and accurate and can be used for routine analysis and quality control of bisoprolol and telmisartan in pure and dosage form. Furthermore, the greenness of the approaches was evaluated using Analytical Greenness assessment (AGREE), and the suggested method received a high greenness score.

Rapid, Simple and Low-Cost Analytical Method Development for Quantification of Eltrombopag Olamine in Tablet Dosage by UV Spectroscopy Method.

BACKGROUND: Eltrombopag Olamine is a drug used to treat thrombocytopenia, a disorder where blood platelet counts get lower and severe aplastic anemia. It serves as a thrombopoietin receptor agonist, which give rise to platelet production in the bone marrow. OBJECTIVES: The objective of this study is to develop a simple, specific, accurate, precise and economical Ultraviolet spectroscopy method to estimate the amount of Eltrombopag Olamine in bulk and tablet dosage form. METHODS: The developed method was performed using methanol for identification and physicochemical characterization of the drug. The validation parameters like linearity, precision, accuracy, robustness limits of detection and quantitation, and specificity were assessed as per ICH Q2 (R2). RESULTS: The maximum absorbance wavelength (λmax) of the drug was found at 247 nm in methanol. The linearity was found in the concentration range of 2-14 µg/ml with regression equation y = 0.0619x - 0.0123 and r² = 0.999. The standard addition method was used to determine the accuracy of the developed method. The result was found in the % recovery range of 98-99%. The precision was done on λmax with respect to the parameters such as repeatability, intraday, and interday. The method was found to be precise as the % RSD value was found to be <2%. The detection limit value (LOD) and quantitation limit value (LOQ) were 0.0524 µg/ml and 0.1588 µg/ml, respectively. CONCLUSION: The developed method is simple, economical, accurate and selective. The developed method was adaptable for the estimation of Eltrombopag Olamine analysis in pharmaceutical dosage form and routine quality control laboratory.

UPLC-ESI-Q-TOF-MS/MS based metabolomics investigation on chemical constituent consistency of Zhenwu Decoction before and after compatibility.

Zhenwu Decoction (ZWD), a classic formula from Zhang Zhongjing's "Treatise on Typhoid Fever" in the Han Dynasty, consists of five traditional Chinese medicines: Aconiti Lateralis Radix Praeparata (ALRP), Paeoniae Radix Alba, Poria Cocos, Ginger, and Rhizoma Atractylodis Macrocephalae. To evaluate the chemical constituent consistency of ZWD before and after compatibility, an ultra-performance liquid chromatography-electrospray ionization-quadrupole time-of-flight mass spectrometry was established to comprehensively study the constituents of ZWD. By normalizing the peak area, the pairwise compatibility of ALRP and the other four medicinal herbs, as well as the compatibility of the entire formula were studied, respectively. Multivariate statistical analysis was used to identify the differences. The processed data were analyzed by principal component analysis and supervised orthogonal partial least squared discriminant analysis, and an S-plot was generated to compare the differences in the chemical composition of the two types of decoction samples. The results showed that during the decoction process of ZWD, a total of seven components were recognized as differential compounds before and after compatibility of ZWD, namely 6-gingerol, zingerone, benzoylhypaconine, hypaconitine, benzoylaconine, paeoniflorin and fuziline. The results of this study provide basic data reference for understanding the law of ZWD compatibility and are valuable for the compatibility study of other herbal medicines.

Systematic evaluation of benzoylation for liquid chromatography-mass spectrometry analysis of different analyte classes.

LC-MS is an indispensable tool for small molecule analysis in many fields; however, many small molecules require chemical derivatization to improve retention on commonly used reversed-phase columns and increase ionization. Benzoyl chloride (BzCl) derivatization is commonly used for derivatization of primary and secondary amines and phenolic alcohols, though evidence exists that with proper reaction conditions (i.e., specific bases), other hydroxyl groups may be derivatized too. Previous studies have examined BzCl concentration, reaction times, and reaction temperatures for derivatization of amines and phenols for LC-MS analysis; however, use of different bases, base concentration, and extending to conditions to hydroxyl groups for LC-MS analysis has not been well-studied. To address this understudied area and identify reaction conditions for both amino and hydroxyl groups, we performed a systematic study of reaction conditions on multiple classes of potential targets. For selected derivatization methods, detection limits and performance in a variety of biological matrices were assessed. Results highlight the importance of tailoring derivatization methods for a given application as they varied by molecule and/or molecule class. Compared to the standard BzCl method commonly used, alternative methods were identified to better derivatize challenging analytes (glucosamine, choline, cortisol, uridine, cytidine) with detection limits reaching 1100, 9, 38, 170, and 67 nM compared to undetectable, 170, 86, 1000, and 86 nM respectively. Sub-nanomolar detection limits were achieved for norepinephrine with alternative derivatization approaches. Improved derivatization methods for several classes and molecules including nucleosides, steroids, and molecules containing hydroxyl groups were also identified.

Benzoates and in situ formed benzene in food supplements and risk assessment.

Upward trend in the use of food supplements urged the assessment of their safety. Eighty-eight liquid herbal supplements collected in Novi Sad (Serbia) in 2018 (36 samples) and 2021 (52 samples) were analysed for the presence of benzoates and sorbates (HPLC-UV) and benzene (HS-GC/MS). Benzoic acid varied from 599 to 9253 mg/kg and sorbic acid between 185 and 1658 mg/kg. The acceptable daily intake of sorbic acid was not reached, but in case of benzoic acid, it was exceeded by 5.3% of the samples. The presence of benzene was confirmed in 41.2% of benzoate preserved supplements (0.9-51.7 µg/kg). Benzene exposure revealed no health concern: maximum hazard quotients ranged from 0.39% (toddlers) to 0.84% (adolescents); minimum margins of exposure were between 35,680 (adolescents) and 77,419 (toddlers); estimates of lifetime cancer risk did not reach one extra cancer case per 100 000 persons. However, measures to mitigate benzene presence in food should be considered.

Screening of in Vitro Inhibition of Lactoperoxidase Enzyme by Methyl Benzoate Derivatives with Molecular Docking Studies.

Lactoperoxidase enzyme (LPO) is secreted from salivary, mammary, and other mucosal glands including the bronchi, lungs, and nose, which had functions as a natural and the first line of defense towards viruses and bacteria. In this study, methyl benzoates were examined in LPO enzyme activity. Methyl benzoates are used as precursors in the synthesis of aminobenzohydrazides used as LPO inhibitors. For this purpose, LPO was purified in a single step using sepharose-4B-l-tyrosine-sulfanilamide affinity gel chromatography with a yield of 9.91 % from cow milk. Also, some inhibition parameters including the half maximal inhibitory concentration (IC50 ) value and an inhibition constant (Ki ) values of methyl benzoates were determined. These compounds inhibited LPO with Ki values ranging from 0.033±0.004 to 1540.011±460.020 µM. Compound 1 a (methyl 2-amino-3-bromobenzoate) showed the best inhibition (Ki =0.033±0.004 µM). The most potent inhibitor (1 a) showed with a docking score of -3.36 kcal/mol and an MM-GBSA value of -25.05 kcal/mol, of these methyl benzoate derivatives (1 a-16 a) series are established H-bond within the binding cavity with residues Asp108 (distance of 1.79 Å), Ala114 (distance of 2.64 Å), and His351 (distance of 2.12 Å).

Efficient determination of enantiomeric ratios of α-hydroxy/amino acids from fermented milks via ion mobility-mass spectrometry.

Chiral analysis of food components can provide important information for food quality, bioactivity and safety. Determination of enantiomeric ratios in food is a tedious task, due to the poor resolution and insufficient sensitivity for simultaneous discrimination and quantification of trace amounts of d-form metabolites. Herein, a high-throughput, high-sensitive and high-resolution method was developed for simultaneously determining enantiomeric ratios of multiple chiral α-hydroxy/amino acids (HA/AAs) from fermented milks in one-run by [d0]/[d5]-estradiol-3-benzoate-17ß-chloroformate labeling-assisted ion mobility - mass spectrometry. Results revealed extensive variation in chiral HA/AA profiles among 15 fermented milks. A total of 14 D-HA/AAs were identified. d-Lactic acid and d-alanine appeared as the most discriminatory in fermented milks with live lactic acid bacteria (LAB). Results suggested that glycolysis, casein hydrolysis and enantioisomerization of HA/AAs were most likely affected by various starter culture LAB. It may contribute to entail a valuable step forward in food quality control and discovering functional-related chiral biomarkers.

Method for trace determination of N-nitrosamines impurities in metronidazole benzoate using high-performance liquid chromatography coupled with atmospheric-pressure chemical ionization tandem mass spectrometry.

Genotoxic impurity control has been a great concern in the pharmaceutical industry since the recall of the large round of sartans worldwide in 2018. In these sartans, N-nitrosamines were the main contaminants in active pharmaceutical ingredients and formulations. Numerous analytical methods have been developed to detect N-nitrosamines in food, drugs, and environmental samples. In this study, a sensitive method is developed for the trace determination of N-nitrosamine impurities in metronidazole benzoate pharmaceuticals using high-performance liquid chromatography/atmospheric-pressure chemical ionization tandem mass spectrometry in the multiple reaction monitoring mode. The method was validated regarding system suitability, selectivity, linearity, accuracy, precision, sensitivity, solution stability, and robustness. The method showed good linearity with R2 ≥ 0.999 and FMandel  < Ftab(95%) ranging from 0.33 to 8.00 ng/ml. The low limits of detection of N-nitrosamines were in the range of 0.22-0.80 ng/ml (0.0014-0.0050 ppm). The low limits of quantification were in the range of 0.33-1.20 ng/ml (0.0021-0.0075 ppm), which were lower than the acceptable limits in metronidazole benzoate pharmaceuticals and indicated the high sensitivity of the method. The recoveries of N-nitrosamines ranged from 84% to 97%. Thus, this method exhibits good selectivity, sensitivity, and accuracy. Moreover, it is a simple, convenient, and scientific strategy for detecting N-nitrosamine impurities in pharmaceuticals to support the development of the pharmaceutical industry.

Effects of acute arginine supplementation on neuroendocrine, metabolic, cardiovascular, and mood outcomes in younger men: A double-blind, placebo-controlled trial.

OBJECTIVES: Arginine is an amino-acid supplement and precursor for nitric-oxide synthesis, which affects various biologic processes. The objective of this study was to determine the effects of arginine supplementation on growth hormone (GH) and metabolic parameters. METHODS: Thirty physically active, healthy men (age 18-39 y; body mass index: 18.5-25 kg/m2) were randomized in a double-blind, placebo-controlled, crossover trial. Arginine (10 g) and placebo (0 g) beverages were consumed after an overnight fast. Blood samples were collected at baseline and 1.5, 3.0, and 24 h after supplementation. The primary outcomes were serum GH and metabolomics. Also, amino acids, glucose, insulin, triacylglycerols, thyroid hormones, testosterone, cortisol, dehydroepiandrosterone, and mood state were assessed. Individuals with detectable increases in GH were analyzed separately (responders: n = 16; < 0.05 ng/mL at 1.5 h). Repeated-measure analyses of variance estimated the treatment effects at each timepoint. RESULTS: Arginine levels increased at 1.5 h (146%) and 3.0 h (95%; P ≤ 0.001) and GH (193%) and thyroid-stimulating hormone (TSH; 10%) levels at 24 h (P < 0.05) after arginine versus placebo consumption. Arginine versus placebo increased glucose levels at 1.5 h (5%) and 3.0 h (3%; P ≤ 0.001). Arginine versus placebo did not affect other dependent measures, including mood state (P > 0.05), but changes in the urea, glutamate, and citric-acid pathways were observed. Among responders, arginine versus placebo increased GH at 1.5 h (37%), glucose at 1.5 h (4%) and 3.0 h (4%), and TSH at 24 h (9%; P < 0.05). Responders had higher levels of benzoate metabolites at baseline and 1.5 h, and an unknown compound (X-16124) at baseline, 1.5 h, and 24 h that corresponds to a class of gut microbes (P < 0.05). CONCLUSIONS: Arginine supplementation modestly increased GH, glucose, and TSH levels in younger men. Responders had higher benzoate metabolites and an unknown analyte attributed to the gut microbiome. Future studies should examine whether the increased prevalence of these gut microorganisms corresponds with GH response after arginine supplementation.

Taxonomic profiling and functional gene annotation of microbial communities in sediment of river Ganga at Kanpur, India: insights from whole-genome metagenomics study.

The perennial river Ganga is recognized as one of India's largest rivers of India, but due to continuous anthropogenic activities, the river's ecosystem is under threat. Next-generation sequencing technology has transformed metagenomics in the exploration of microbiome and their imperative function in diverse aquatic ecosystems. In this study, we have uncovered the structure of community microbiome and their functions in sediments of river Ganga at Kanpur, India, at three polluted stretches through a high-resolution metagenomics approach using Illumina HiSeq 2500. Among the microbes, bacteria dominate more than 82% in the three polluted sediment samples of river Ganga. Pseudomonadota (alpha, beta, and gamma) is the major phylum of bacteria that dominates in three sediment samples. Genes involved in degradation of xenobiotic compounds involving nitrotoluene, benzoate, aminobenzoate, chlorocyclohexane, and chlorobenzene were significantly enriched in the microbiome of polluted stretches. Pathway analysis using KEGG database revealed a higher abundance of genes involved in energy metabolism such as oxidative phosphorylation, nitrogen, methane, sulfur, and carbon fixation pathways in the sediment metagenome data from the river Ganga. A higher abundance of pollutant degrading enzymes like 4-hydroxybenzoate 3-monooxygenase, catalase-peroxidase, and altronate hydrolase in the polluted microbiome indicates their role in degradation of plastics and dyes. Overall, our study has provided bacterial diversity and their dynamics in community structure and function from polluted river microbiome, which is expected to open up better avenues for exploration of novel functional genes/enzymes with potential application in health and bioremediation.

Optically active plasmonic cellulose fibers based on Au nanorods for SERS applications.

Cellulose might be a promising material for surface-enhanced Raman scattering (SERS) substrates due to its wide availability, low cost, ease of fabrication, high flexibility and low optical activity. This work shows, for the first time development of the cellulose-based substrate, that owes its SERS activity to the presence of gold nanorods in its internal structure, and not only on the surface, as it is shown elsewhere, thus ensuring superior stability of the obtained material. This flexible cellulose-based substrate exhibiting plasmonic activity, provide easy and reproducible detection of different analytes via SERS technique. The substrate was prepared by introduction of gold nanorods into the cellulose fibers matrix using an eco-friendly process based on N-Methylmorpholine-N-Oxide. Au-modified cellulose fibers were used for the detection of p-Mercaptobenzoic acid and Bovine Serum Albumin by the SERS method. The obtained results show that this substrate offers large signal enhancement of 6-orders of magnitude, and high signal reproducibility with a relative standard deviation of 8.3%. Additionally, washing tests (90 °C, 20 h) showed superior stability of the as prepared plasmonic fibers, thus proving the good reusability of the substrates and the long shelf life.

3D Printed Microfluidic Device for Magnetic Trapping and SERS Quantitative Evaluation of Environmental and Biomedical Analytes.

Surface-enhanced Raman scattering (SERS) is an ideal technique for environmental and biomedical sensor devices due to not only the highly informative vibrational features but also to its ultrasensitive nature and possibilities toward quantitative assays. Moreover, in these areas, SERS is especially useful as water hinders most of the spectroscopic techniques such as those based on IR absorption. Despite its promising possibilities, most SERS substrates and technological frameworks for SERS detection are still restricted to research laboratories, mainly due to a lack of robust technologies and standardized protocols. We present herein the implementation of Janus magnetic/plasmonic Fe3O4/Au nanostars (JMNSs) as SERS colloidal substrates for the quantitative determination of several analytes. This multifunctional substrate enables the application of an external magnetic field for JMNSs retention at a specific position within a microfluidic channel, leading to additional amplification of the SERS signals. A microfluidic device was devised and 3D printed as a demonstration of cheap and fast production, with the potential for large-scale implementation. As low as 100 µL of sample was sufficient to obtain results in 30 min, and the chip could be reused for several cycles. To show the potential and versatility of the sensing system, JMNSs were exploited with the microfluidic device for the detection of several relevant analytes showing increasing analytical difficulty, including the comparative detection of p-mercaptobenzoic acid and crystal violet and the quantitative detection of the herbicide flumioxazin and the anticancer drug erlotinib in plasma, where calibration curves within diagnostic concentration intervals were obtained.

WinMLR program for the determination of sorbic and benzoic acids in food samples.

The program WinMLR has been developed to quantify sorbic and benzoic acids in soft drinks, fruit juices, and soy sauce by making a multilinear regression treatment of experimental data to a linear combination of standard signals. The spectra of sorbic and benzoic acid and samples were obtained from a conventional spectrophotometer, which has been saved in an ASCII file to be applied with the WinMLR program. Before to determine sorbic and benzoic acids in samples, the wavelength validation and calibration parameters were studied. Standard solutions of sorbic and benzoic acids were used for the calibration parameters to measure the individual analyte. If the sample has simultaneously both compounds, it is better to choose the synthetic mixture for the calibration parameters. This technique provides a good recovery in the range of 80.4-104.8% without a complicated and expensive instrument.

Quantitative vapor delivery for improved canine threshold testing.

The canine olfactory system is a highly efficient and intricate tool often exploited by humans for detection for its many attributes, including impressive sensitivity to trace analyte vapors. Canine detectors are often touted as having lower limits of detection, or olfactory detection threshold (ODT), than other field-relevant detection technologies; however, previous attempts to quantify canine ODTs have resulted in reported estimates spanning multiple orders of magnitude, even for the same analyte. A major contributor to these discrepancies is the vapor delivery method used for testing, where losses due to adsorption and dilution are often unaccounted for, and the presence of unattended compounds in the vapor stream due to carryover may go unnoticed. In this research, a trace vapor generator (TV-Gen) was used to deliver quantitatively accurate amounts of vapor reproducibly over time for canine testing. Analyte losses due to adsorption to surfaces in the flow path, dilution in the sniff port at the outlet, and analyte carryover were considered. Computational fluid dynamic (CFD) modeling was used to visualize analyte vapor spread throughout the port. CFD simulations revealed the need for a diffuser to encourage the diffusion of the analyte throughout the port. As a result, the modified vapor generator provides analyte air as a diffuse flow that is evenly distributed through the custom sampling orifice, as opposed to a narrow stream of air at the chosen concentration which exits directly into the environment. Laboratory validations were carried out for three analytes, amyl acetate, 2,4-dinitrotoluene (DNT), and methyl benzoate. A linear response across more than two orders of magnitude vapor concentration range was achieved for all analytes. These efforts will be applied in further research utilizing this TV-Gen vapor delivery system for canine ODT testing, eliminating many quantitative changes seen previously. Graphical abstract.

Different chromatographic methods for determination of alogliptin benzoate, metformin hydrochloride, and metformin impurity in bulk and pharmaceutical dosage form.

Two simple, sensitive, and reproducible methods were developed for the determination of alogliptin and metformin hydrochloride in presence of metformin impurity "melamin" in pure form and in pharmaceutical formulation. Method (A) was a thin layer chromatographic method in which separation was achieved using ethyl acetate-methanol-formic acid (6:3.8:0.2, by volume) as a developing system followed by densitometric scanning at 230 nm. Method (B) was a high-performance liquid chromatography method; separation was achieved on C18 column, the mobile phase consisted of a mixture of sodium lauryl sulfate buffer 0.1% w/v, pH 3: methanol in the ratio 70:30, v/v and measurement was done at 220 nm. System suitability testing parameters were calculated to ascertain the quality performance of the developed chromatographic methods. The proposed methods have been validated regarding accuracy, precision, and selectivity, moreover they have been successfully applied to Westirizide tablets containing both alogliptin and metformin hydrochloride, results indicate that there was no interference from additives. No significance difference was found when these methods were compared to the reported one.

Biomacromolecular-Assembled Nanoclusters: Key Aspects for Robust Colloidal SERS Sensing.

Superstructures of gold nanospheres offer augmented surface-enhanced Raman scattering (SERS) activities beyond the limits of their individual building blocks. However, for application as reliable and quantitative colloidal SERS probes, some key aspects need to be considered to combine efficiency and robustness with respect to hotspot excitation, analyte adsorption, signal stability, and colloidal stability. For this purpose, we studied core/satellite superstructures with spherical cores as a simple optically isotropic model system. Superstructures of different core sizes were assembled using bovine serum albumin (BSA), which serves as a non-specific biomacromolecular linker and provides electrosteric stabilization. We show that the "noisy" spectral footprint of the protein coating may serve as an internal standard, which allows accurate monitoring of the adsorption kinetics of analytes. The SERS activity was quantified using 4-mercaptobenzoic acid (MBA) as an aromatic low-molecular-weight model analyte. The molar SERS efficiency was studied by variation of the particle (Au0) and analyte concentrations with a limit of detection of 10-7 M MBA. The practical importance of colloidal stability for robust measurement conditions was demonstrated by comparing the superstructures with their citrate-stabilized or protein-coated building blocks. We explain the theoretical background of hotspot formation by a leader/follower relationship of asymmetric control between the core and the satellites and give practical guidelines for robust colloidal SERS sensing probes.

Surface-Enhanced Raman Spectroscopy of Organic Molecules and Living Cells with Gold-Plated Black Silicon.

Black silicon (bSi) refers to an etched silicon surface comprising arrays of microcones that effectively suppress reflection from UV to near-infrared (NIR) while simultaneously enhancing the scattering and absorption of light. This makes bSi covered with a nm-thin layer of plasmonic metal, i.e., gold, an attractive substrate material for sensing of bio-macromolecules and living cells using surface-enhanced Raman spectroscopy (SERS). The performed Raman measurements accompanied with finite element numerical simulation and density functional theory analysis revealed that at the 785 nm excitation wavelength, the SERS enhancement factor of the bSi/Au substrate is as high as 108 due to a combination of electromagnetic and chemical mechanisms. This finding makes the SERS-active bSi/Au substrate suitable for detecting trace amounts of organic molecules. We demonstrate the outstanding performance of this substrate by highly sensitive and specific detection of a small organic molecule of 4-mercaptobenzoic acid and living C6 rat glioma cell nucleic acids/proteins/lipids. Specifically, the bSi/Au SERS-active substrate offers a unique opportunity to investigate the living cells' malignant transformation using characteristic protein disulfide Raman bands as a marker. Our findings evidence that bSi/Au provides a pathway to the highly sensitive and selective, scalable, and low-cost substrate for lab-on-a-chip SERS biosensors that can be integrated into silicon-based photonics devices.

Ultimate fate of herbicide tembotrione and its metabolite TCMBA in soil.

Tembotrione is a triketone group herbicide having worldwide applications for weed management in maize. It is considered to be less stable in the environment and its degradation products may have toxicological consequences due to longer persistence and off-site movements. We studied the persistence behavior and leaching potential of tembotrione and its major metabolite TCMBA in clay loam and sandy loam soils having different physico-chemical properties. The rapid transformation of parent tembotrione to degradation products and their high interactions with soil provided challenging task of residues separation from complex soil matrix. Therefore, a novel sample preparation method (modified QuEChERS) was optimized for trace estimation of tembotrione and TCMBA which offered 86.6-95.6% recoveries with limit of detection (LOD) and quantification (LOQ) as 0.001 and 0.003 µg/g, respectively in both soils without any matrix interference. A first order dissipation kinetics was followed by tembotrione and TCMBA residues with half-life ranged from 7.2 to 13.4 days in both soils. Residues reached below detectable limit on 45-60 days after treatments in two application doses. Leaching experiment revealed maximum retention of tembotrione residues from 15 to 25 cm depth in both soils whereas TCMBA show appreciable leaching potential. It was concluded that tembotrione can be phytotoxic to the succeeding crops if applied at late post-emergence stage. TCMBA can contaminate surface and ground water due to continuous and prolonged use of tembotrione particularly in light textured soils.

Pyrethroid Insecticides in Households from Urban Areas: An Association of the 3-PBA Metabolite and Hand Wipes.

Background: Pyrethroid exposure in the household environment affects children directly via inhalation or dermal exposure. Hand wipes can effectively predict pyrethroid exposure to young children along with the children's activities. The main purpose of this study is to identify the relationship between 3-PBA metabolites, hand wipe sample concentrations and multiple exposure factors, within the population of households with young children in urban Bangkok, Thailand. Methods: Interviews were conducted with the parents of 80 children (aged 2-3 years). Urine was collected to analyze for 3-PBA metabolites and hand wipe samples were collected to analyze for cypermethrin. Both were analyzed by gas chromatography (GC/MS). Results: A Spearmen's correlation test of the increase of 3-PBA metabolites was significantly associated with an increase in hand wipe samples (cypermethrin) in children (rs = 0.226-0.274, p-value < 0.05). The binary logistic regression test presented an association between exposure factors with 3-PBA metabolite concentration. Gender presented a significant association with 3-PBA metabolites (p-value = 0.035, OR = 0.326, 95% CI 0.115-0.926), and frequency of bare feet inside the household presented a significant association with 3-PBA metabolites (p-value < 0.01, OR = 7.072, 95% CI 1.707-29.291). In addition, exposure factors were not significantly associated with wipe sample concentration (cypermethrin) but showed high risk of exposure to young children. Conclusions: Suggestions to reduce the risk from long-term pyrethroid insecticide exposure to children living in households include increased education, awareness, and management.

In-vitro evaluation of rice straw biochars' effect on bispyribac-sodium dissipation and microbial activity in soil.

Dissipation of bispyribac-sodium was estimated in an unamended sandy loam soil and soil amended with rice straw and its biochars in pot culture experiment. Effect of herbicide and amendments on abundance and activity of soil microbial parameters was also assessed by determining soil biological parameters. Amendment type, application rate and soil moisture had differential influence on bispyribac-sodium dissipation and soil's microbial parameters. Amendment of soil with rice straw and its biochars enhanced the dissipation of bispyribac-sodium (DT50 = 7.55-18.44 days) as compared to unamended soil (DT50 = 23.13-28.60 days) and dissipation decreased in this order: rice straw >350BC > 550BC > CBC amended soil > unamended soil. Dissipation of bispyribac-sodium decreased with increase in amendment level of rice straw and its biochars in soil. Irrespective of amendment type and application rate, bispyribac sodium was more persistent under submerged conditions than at field capacity and its DT50 was 10.13 to 28.60 and 7.55-27.14 days, respectively. Dehydrogenase, alkaline phosphatase activity and bacterial population indicated that application of the organic amendment decreased negative effects of the herbicide on soil enzymatic activities. These findings prove that biostimulation using rice straw and its biochars has the potential to decrease the persistence of bispyribac-sodium and minimize its environmental hazards.