Post-synthetic modification of nano-chitosan using gibberellic acid: Foliar application on sorghum under salt stress conditions and estimation of biochemical parameters.

The challenge of desert farming with a high salt level has become an ecological task due to salt stress negatively affecting plant growth and reproduction. The current study deals with the cultivation of sorghum under salt stress conditions to counteract the effect of chitosan and gibberellic acid (GA3). Here, the effects of chitosan, GA3 and nano-composite (GA3@chitosan) on biochemical contents, growth and seed yield of sorghum under salinity stress conditions were studied. The results showed that spraying with GA3@chitosan increased sorghum grain yield by 2.07, 1.81 and 1.64 fold higher than salinity stressed plants, chitosan treatment and GA3 treatment, respectively. Additionally, compared to the control of the same variety, the GA3@chitosan spraying treatment improved the concentration of microelements in the grains of the Shandweel-1 and Dorado by 24.51% and 18.39%, respectively for each variety. Furthermore, spraying GA3@chitosan on sorghum varieties increased the accumulation of the macroelements N, P, and K by 34.03%, 47.61%, and 8.67% higher than salt-stressed plants, respectively. On the other hand, the proline and glycinebetaine content in sorghum leaves sprayed with nano-composite were drop by 51.04% and 11.98% less than stressed plants, respectively. The results showed that, in Ras Sudr, the Shandweel-1 variety produced more grain per feddan than the Dorado variety. These findings suggest that GA3@chitosan improves the chemical and biochemical components leading to a decrease in the negative effect of salt stress on the plant which reflects in the high-yield production of cultivated sorghum plants in salt conditions.

The hepato- and neuroprotective effect of gold Casuarina equisetifolia bark nano-extract against Chlorpyrifos-induced toxicity in rats.

BACKGROUND: The bark of Casuarina equisetifolia contains several active phytoconstituents that are suitable for the biosynthesis of gold nanoparticles (Au-NPs). These nanoparticles were subsequently evaluated for their effectiveness in reducing the toxicity induced by Chlorpyrifos (CPF) in rats. RESULTS: Various hematological and biochemical measurements were conducted in this study. In addition, markers of oxidative stress and inflammatory reactions quantified in liver and brain tissues were evaluated. Histopathological examinations were performed on both liver and brain tissues. Furthermore, the native electrophoretic protein and isoenzyme patterns were analyzed, and the relative expression levels of apoptotic genes in these tissues were determined. The hematological and biochemical parameters were found to be severely altered in the group injected with CPF. However, the administration of Au-C. equisetifolia nano-extract normalized these levels in all treated groups. The antioxidant system markers showed a significant decrease (P ≤ 0.05) in conjunction with elevated levels of inflammatory and fibrotic markers in both liver and brain tissues of the CPF-injected group. In comparison, the pre-treated group exhibited a reduction in these markers when treated with the nano-extract, as opposed to the CPF-injected group. Additionally, the nano-extract mitigated the severity of histopathological lesions induced by CPF in both liver and brain tissues, with a higher ameliorative effect observed in the pre-treated group. Electrophoretic assays conducted on liver and brain tissues revealed that the nano-extract prevented the qualitative changes induced by CPF in the pre-treated group. Furthermore, the molecular assay demonstrated a significant increase in the relative expression of apoptotic genes in the CPF-injected rats. Although the nano-extract ameliorated the relative expression of these genes compared to the CPF-injected group, it was unable to restore their values to normal levels. CONCLUSION: Our results demonstrated that the nano-extract effectively reduced the toxicity induced by CPF in rats at hematological, biochemical, histopathological, physiological, and molecular levels, in the group pre-treated with the nano-extract.

Selective separation of chlorophyll-a using recyclable hybrids based on Zn-MOF@cellulosic fibers.

Chlorophyll-a as pigments, exist in the green organelles for plants that act in photosynthesis. Different studies were considered with demonstration of an effective separation technique of Chlorophyll-a without decomposition; however, the reported methods were disadvantageous with expensiveness and low quantum yield. The current work uniquely represents an investigative method for the separation of Chlorophyll-a from spinach extract using cellulosic hybrids based on ZIF-8 @cellulosic fibers (Zn-zeolitic imidazolate frameworks@cellulosic fibers) as a cost effective and recyclable absorbents. To obtain hybrids, ZIF-8 was in-situ prepared over the cellulosic fibers (bamboo, modal and cotton). The untreated and treated fibers were well characterized via FTIR, SEM, EDX, XRD, in order to approve the successive impregnation of ZIF-8. Whereas, the microscopic images showed that, microcrystalline ZIF-8 rods with length of 1.3-4.4 µm were grown over the cellulosic fibers. The obtained hybrids and the untreated fibers were exploited in the separation of Chlorophyll-a via the adsorption/desorption process. The chlorophyll-adsorption was followed Langmuir isotherm and pseudo-second order model. The Langmuir maximum capacities of Chlorophyll-a onto hybrids were followed the order of ZIF-8@cotton (583.6 mg/g) > ZIF-8@modal (561.3 mg/g) > ZIF-8@bamboo (528.7 mg/g). After incorporation of ZIF-8, the maximum adsorption capacities of cellulosic fibers were enhanced by 1.4-1.9 times. Adsorption of chlorophyll onto the applied hybrids was lowered by 27-28%, after five repetitive washing cycles. The data summarized that; chlorophyll was effectively separated by the synthesized ZIF-8@cellulosic fibers hybrids, whereas, the prepared hybrids showed good reusability for application on wider scaled purposes.

Efficient phenolic compounds adsorption by immobilization of copper-based metal-organic framework anchored polyacrylonitrile/chitosan beads.

The application of newly formulated beads from copper-benzenetricarboxylate (Cu-BTC), polyacrylonitrile (PAN), and chitosan (C), Cu-BTC@C-PAN, C-PAN, and PAN, for the removal of phenolic chemicals from water, is described in the current paper. Phenolic compounds (4-chlorophenol (4-CP) and 4-nitrophenol (4-NP)) were adsorbed using beads and the adsorption optimization looked at the effects of several experimental factors. The Langmuir and Freundlich models were used to explain the adsorption isotherms in the system. A pseudo-first and second-order equation is performed for describing the kinetics of adsorption. The obtained data fit (R2 = 0.999) supports the suitability of the Langmuir model and pseudo-second-order kinetic equation for the adsorption mechanism. Cu-BTC@C-PAN, C-PAN, and PAN beads' morphology and structure were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and Fourier transforms infrared spectroscopy (FT-IR). According to the findings, Cu-BTC@C-PAN has very high adsorption capacities of 277.02, and 324.74 mg g-1, for 4-CP and 4-NP, respectively. The Cu-BTC@C-PAN beads showed 2.55 times higher adsorption capacity than PAN in the case of 4-NP, but in the case of 4-CP, it was higher by 2.64 times.

Endocrine-Disrupting Organochlorine Pesticides in Human Breast Milk: Changes during Lactation.

The aim of the present study was to assess infant safety associated with the occurrence of endocrine-disrupting organochlorine pesticides (OCP) in breast milk. Moreover, the association between pregnant mothers' dietary habits and these compounds levels in breast milk was investigated. Breast milk was collected at various stages of lactation. The samples were analyzed by the GC-MS method. The OCP concentrations ranged from < limit of detection (LOD) to 6.81 ng/g lipids. The highest OCP concentrations in breast milk occurred primarily within the first month of lactation, and decreased over the lactation period. It was found that the maternal consumption of certain food products-in particular pork, beef, poultry, eggs, and dairy products-could have affected the content of 1,1'-(2,2,2-Trichloroethane-1,1-diyl)bis(4-chlorobenzene), called DDT and its metabolites in the breast milk. The levels of beta-endosulfan were positively correlated with fish and poultry consumption. The redundancy analysis indicated that the diets of the pregnant women had an important impact on pesticide residues in the breast milk. There is a potential possibility of lowering the content of organochlorine compounds in breast milk by adhering to nutritional recommendations, e.g., avoiding the excessive consumption of fish and other raw food materials of unknown origin.

Tracking residual organochlorine pesticides (OCPs) in green, herbal, and black tea leaves and infusions of commercially available tea products marketed in Poland.

The content of residual organochlorine pesticides (OCPs) was examined in green, herbal, and black tea leaves as well as in their infusions prepared from tea products marketed in the main supermarkets in Poland. It was found that the detected mean levels of organochlorine residues in tea leaves ranged from

Separation of bioactive chamazulene from chamomile extract using metal-organic framework.

Isolation of bioactive compounds from extracts of pharmaceutical plant is very important. In this work, copper benzene-1,3,5-tricarboxylate metal organic framework (Cu-BTC MOF) has been synthesized. It is used in separating of chamazulene from chamomile extract. The Cu-BTC MOF not only shows good chamazulene adsorption but also maintains good desorption properties. However, the research on this field is still new and the maturation of novel MOFs or the enhancements of known ones are required.The chamomile extract obtained after each stage of the treatments was carefully characterized by thin-layer chromatography (TLC), Fourier-transform infrared spectroscopy (FTIR), UV-vis spectrometry and gas chromatography-mass spectrometry (GC-MS). The morphology and the crystallinity of Cu-BTC MOF were investigated using scanning electron microscopy (SEM) and powder X-ray diffraction (PXRD), respectively. Breakthrough experiments in a column was investigated and the data was fitted with Bohart-Adams model. Monte Carlo simulation was conducted to investigate the preferential adsorption sites of Cu-BTC for chamazulene molecules.

Fate of 14C-ethion insecticide in the presence of deltamethrin and dimilin pesticides in cotton seeds and oils, removal of ethion residues in oils, and bioavailability of its bound residues to experimental animals.

Ethyl-1-(14)C-ethion and some of its degradation products have been prepared for comparison purposes. Cotton plants were treated with (14)C-ethion alone and in the presence of deltamethrin and dimilin pesticides under conditions simulating local agricultural practice. (14)C-Residues in seeds were determined at harvest time; about 47.5% of (14)C-activity was associated with oil. After further extraction of seeds with ethanol, the ethanol-soluble (14)C-residues accounted for 10.6% of the total seed residues, whereas the cake contained about 37.3% of the total residues as bound residues in the case of ethion only. The bound residues decreased in the presence of deltamethrin and dimilin pesticides and amounted to 8.1 and 10.4% of the total residues, respectively. About 95% of the (14)C-activity in the crude oil could be eliminated by simulated commercial processes locally used for oil refining. Chromatographic analysis of crude cotton oil revealed the presence of ethion monooxon, O,O-diethyl phosphorothioate, and O,O-diethyl phosphoric acid in addition to one unknown compound in the case of ethion alone or ethion and dimilin. The same degradation products are found in the case of ethion and deltamethrin in addition to ethion dioxon, whereas ethanol extract revealed the presence of ethion dioxon and O,O-diethyl phosphoric acid as free metabolites. Acid hydrolysis of the conjugated metabolites in the ethanol extract yielded O,O-diethyl S-hydroxymethyl phosphorodithioate. The bound residues were quite readily bioavailable to the rats. After feeding rats with the cake containing ethion-bound residues, a substantial amount (60%) of (14)C-residues was eliminated in the urine, whereas the (14)C-residues excreted in expired air and feces were 10 and 9%, respectively. About 11% of the radioactive residues were distributed among various organs.

Assessment of health risk from organochlorine pesticides residues in high-fat spreadable foods produced in Poland.

Currently, butter and margarine are food products attracting wide customer interest. Every day, consumers around the world buy these products for human consumption. Butter is obtained from milk fat, while margarine is derived from vegetable oils. The content of organochlorine pesticide (OCP) residues was examined in both types of these high fatty products. A gas chromatograph with MSD (HP 5973) detector was used for the determination of pesticides such as α-HCH, ß-HCH, γ-HCH, DDT, DDD, DDE, aldrin, dieldrin, endrin, heptachlor and heptachlor epoxide. The examined products had diverse concentrations of the analyzed compounds. Visible was the division based on the origin of the product, which might be composed of animal or vegetable fats. The research has revealed the presence of OCP residues in all examined spreads. Quantities of organochlorine compounds did not pose an immediate danger to the consumers' health. Human and environmental health risk assessment was carried out by the estimation of lifetime average daily dose (LADD) and non-carcinogenic health hazard quotient (HQ). Total estimated LADD ranged between 1.3 × 10(-5) and 3.1 × 10(-5) mg kg(-1) d(-1) for butter, and 1.9 × 10(-6) and 4.6 × 10(-6) mg kg(-1) d(-1) for margarine and mix spread. The HQ ranged between 1.1 × 10(-4) and 3.7 × 10(-4) for butter, and 1.4 × 10(-5) and 9.0 × 10(-6) for margarine and mix spread for adults. These estimated HQs were within the safe acceptable limits, indicating a negligible risk to the residents of the study area.

Performance of a portable biosensor for the analysis of ethion residues.

Sensitive disposable potentiometric sensors for determination of the organophosphorus pesticide (OPs), ethion and its degradation residues have been constructed. The fabricated screen printed sensors are based on multi-walled carbon nanotube-polyvinyl chloride (MWNT-PVC) composite incorporated with α-cyclodextrin (α-CD) ionophore for butyrylcholine (BuCh) determination. Butyrylcholinesterase (BuChE) activity was measured through monitoring the BuCh hydrolysis using the fabricated sensors. The electrode potential changes linearly with BuChE concentration over the range from 0.04 to 0.4 U in phosphate buffer solution. This approach can also be used to analyze ethion and its degradation products in the concentration range from 0 to 330 ng mL(-1) by measuring the relative inhibition percentage of BuChE. From different ethion degradation products, inhibition by dioxon and monooxon were more potent than the parent pesticide. The proposed method was applied for determination of ethion in different samples with good accuracy and precision. The relative simple fabrication protocol of biosensor, high sensitivity and stability represents a promising approach for determination of environmental pollutants in field conditions.

Distribution, fate and histopathological effects of ethion insecticide on selected organs of the crayfish, Procambarus clarkii.

This study aims to investigate the fate and histopathological effects of ethion on selected organs of the crayfish, Procamabrus clarkii. Crayfish were exposed to 1 mg l(-1) (14)C-ethion and the concentrations of ethion and its possible degradation products were measured in water and different organs of the crayfish over both the exposure and recovery periods. Chromatographic analysis revealed that ethion was degraded into ethion monooxon, ethion dioxon, O,O-diethyl phosphorothioate, O-ethyl phosphorothioate and one unknown compound. At the end of exposure period, ethion was accumulated in different organs of the crayfish especially in the hepatopancreas and gills. Following the transfer of crayfish to clean water for seven days, the concentration of insecticide residues were decreased in both the hepatopancreas and gills suggesting that these organs play an important role in elimination of ethion. On the other hand, the exposure of the crayfish to » 96 h-LC(50) (0.36 mg l(-1)) of ethion caused extensive ultrastructural alterations to both hepatopancreas and gill epithelial cells. In the hepatopancreas, the most notable pathological features included vacuolation, degradation and distinct cell lysis. In the gill epithelium, the histopathological alterations included infiltration of hemocytes, cytoplasmic vacuolation and a decrease in the number of basal plasma membrane infoldings.

Comparison of organochlorine pesticides and polychlorinated biphenyls residues in vegetables, grain and soil from organic and conventional farming in Poland.

Organic and conventional crops were studied by identifying the relationship between persistent organic pollutants in cereals, vegetables and soil. The residues of organochlorine pesticides and polychlorinated biphenyls (PCBs) were determined in grains (rye and wheat), vegetables (carrots and beets) and soil collected from the fields. PCB residues recorded in the beets from organic farming were as high as 3.71 ppb dry weight (dry wt.), while in the soil from conventional farming of beets 0.53 ppb dry wt. Among vegetables, higher concentrations of pesticides were detected in organically grown beets (190.63 ppb dry wt.). Soil samples from the organic farming contained lower levels of organochlorine pesticide residues compared to the conventional farming. Taking into account toxicity equivalent (TEQ), the conventionally grown carrots accumulated the most toxic PCBs. Non-ortho and mono-ortho PCBs were also noted in the grain of conventionally grown rye and amounted to 3.05 pg-TEQ/g wet wt.

Bioavailability and toxicological potential of sunflower-bound residues of (14)C-chlorpyrifos insecticide in rats.

Sunflower plants were treated with (14)C-chlorpyrifos under conditions simulating local agricultural practice. Residues present in the oil, methanol extract and cake of the treated sunflower seeds were 7.2, 2.8, and 12 ppm, respectively. When rats fed on sunflower cake containing bound residues for three days, the animals eliminated 46 % of the radioactivity in urine, 25 % in feces and 10 % in the expired air. A further bioavailable amount of 8 % was found in selected organs indicating that the bound residues were highly bioavailable. Chromatographic analysis of urine extract revealed the presence of the parent compound, its oxon, desethyl chlorpyrifos and desethyl chlorpyrifos oxon as free metabolites in addition to a conjugated metabolite. It was liberated by acid hydrolysis and identified as 3,5,6-trichloro-2-hydroxypyridine. Bound residues were found to have biological effects such as inhibition of rat plasma ChE, elevations of liver parameters (ALT, AST, and ALP), decrease in total protein and albumin content suggesting a hepatotoxic potential. A significant increase in the values of creatinine, urea, cholesterol, triglycerides and significant decrease in Catalase and Glutathion-S-Transfrase were observed in treated rats.

Synthesis and antiviral activity of new indole-based heterocycles.

New 1,2,4-triazolo[3,4-b]-1,3,4-thiadiazine and 1,3-thiazole derivatives incorporating indole nucleus were prepared using 3-acetylindole as precursor and evaluated for their antiviral activity against herpes simplex type 1 (HSV-1).

Fate of 14C-ethyl prothiofos insecticide in canola seeds and oils.

Canola plants were treated with (14)C- prohiofos under conditions simulating local agricultural practices. (14)C-residues in seeds were determined at different time intervals. At harvest time about 32 % of (14)C-activity was associated with oil. The methanol soluble (14)C-residues accounted for 12 % of the total seed residues after further seeds extraction, while the cake contained about 49 % of the total residues. About 69 % of the (14)C-activity in the crude oil could be eliminated by simulated commercial processes locally used for oil refining. Chromatographic analysis of crude and refined oil revealed the presence of the parent compound together with three metabolites which were identified as prothiofos oxon, O-ethyl phosphorothioate and O-ethyl S-propyl phosphorothioate, besides one unknown compound. While methanol extract revealed the presence of despropylthio prothiofos and O-ethyl phosphoric acid as free metabolites acid hydrolysis of the conjugated metabolites in the methanol extract yielded 2, 4-dichlorophenole which was detected by color. When rats were fed the extracted cake for 72 hours, the bound residues were found to be bioavailable. The main excretion route was via the expired air (42 %), while the (14)C-residues excreted in urine and feces were 30 % and 11 %, respectively. The radioactivity detected among various organs accounted to 7.5 %.Chromatographic analysis of urine indicated the presence of prothiofos oxon, O-ethyl phosphoric acid and 2, 4-dichlorophenole as main degradation products of prothiofos in free and conjugated form.

Synthesis, anticonvulsant, and anti-inflammatory activities of some new benzofuran-based heterocycles.

Treatment of 2-bromoacetylbenzofuran (2) with pyridine afforded its corresponding pyridinium bromide 3. The latter salt reacted with some activated alkenes and acetylenes to give the corresponding indolizine derivatives. Treatment of the salt 3 with benzylidenemalononitriles 9 afforded polysubstituted aniline derivatives, however with arylidenecyanothioacetamides 15 it gave the corresponding 4,5-dihydrothiophenes. Bromide 3 also coupled with p-chlorobenzenediazonium salt followed by ammonium acetate to give the corresponding 1,2,4,5-tetrazine derivative. The biological activity of the newly synthesized compounds was examined and some of them were found to possess anticonvulsant and anti-inflammatory activities.

Synthesis, anticonvulsant, and anti-inflammatory evaluation of some new benzotriazole and benzofuran-based heterocycles.

Treatment of 2-bromoacetylbenzofuran with 1H-benzotriazole afforded 1-(benzofuran-2-yl)-2-(benzotriazol-1-yl)ethanone which reacted with phenylisothiocyanate to give the corresponding thioacetanilide derivatives. Treatment of the latter ethanone and thioacetanilide derivatives with hydrazonoyl chlorides afforded the corresponding pyrazole and 1,3,4-thiadiazole derivatives. The thioacetanilide derivative reacted with alpha-haloketones and alpha-halodiketones to afford thiophene and thiazole derivatives, respectively. The newly synthesized compounds were found to possess anticonvulsant and anti-inflammatory activities with the same mechanism of action of selective COX-2 inhibitors.