Toxicity of silver nanoparticles to rainbow trout: A toxicogenomic approach

Silver (Ag) nanoparticles are used as antimicrobial adjuvant in various products such as clothes and medical devices where the release of nano-Ag could contaminate the environment and harm wildlife. The purpose of this study was to examine the sublethal effects of nano-Ag and dissolved Ag on Oncorhynchus mykiss rainbow trout. Hepatic Ag contents and changes in gene expression were monitored to provide insights on bioavailability and mode of action of both forms of silver. Fish were exposed to increasing concentrations (0.06, 0.6 and 6 μg L⁻¹) of nano-Ag (20 nm) and silver nitrate (AgNO₃) for 96 h at 15 °C. A gene expression analysis was performed in the liver using a DNA microarray of 207 stress-related genes followed by a quantitative polymerase chain reaction on a selection of genes for validation. The biochemical markers consisted of the determination of labile zinc, metallothioneins, DNA strand breaks, lipid peroxidation (LPO) and vitellogenin-like proteins. The analysis of total Ag in the aquarium water revealed that nano-Ag was mostly aggregated, with 1% of the total Ag being dissolved. Nevertheless, hepatic Ag content was significantly increased in exposed fish. Indeed, dissolved Ag was significantly more bioavailable than nano-Ag only at the highest concentration with 38 ± 10 and 11 ± 3 ng Ag mg⁻¹ proteins for dissolved and nano-Ag respectively. Exposure to both forms of Ag led to significant changes in gene expression for 13% of tested gene targets. About 12% of genes responded specifically to nano-Ag, while 10% of total gene targets responded specifically to dissolved Ag. The levels of vitellogenin-like proteins and DNA strand breaks were significantly reduced by both forms of Ag, but DNA break levels were lower with nano-Ag and could not be explained by the presence of ionic Ag. Labile zinc and the oxidized fraction of metallothioneins were increased by both forms of Ag, but LPO was significantly induced by nano-Ag only. A discriminant function analysis revealed that the responses obtained by biochemical markers and a selection of ten target genes were able to discriminate completely (100%) the effects of both forms of Ag. Exposure to nano-Ag involved genes in inflammation and dissolved Ag involved oxidative stress and protein stability. Hence, the toxicity of Ag will differ depending on the presence of Ag nanoparticles and aggregates.     

Transport of silver nanoparticles (AgNPs) in soil

The effect of soil properties on the transport of silver nanoparticles (AgNPs) was studied in a set of laboratory column experiments, using different combinations of size fractions of a Mediterranean sandy clay soil. The AgNPs with average size of ∼30 nm yielded a stable suspension in water with zeta potential of −39 mV. Early breakthrough of AgNPs in soil was observed in column transport experiments. AgNPs were found to have high mobility in soil with outlet relative concentrations ranging from 30% to 70%, depending on experimental conditions. AgNP mobility through the column decreased when the fraction of smaller soil aggregates was larger. The early breakthrough pattern was not observed for AgNPs in pure quartz columns nor for bromide tracer in soil columns, suggesting that early breakthrough is related to the nature of AgNP transport in natural soils. Micro-CT and image analysis used to investigate structural features of the soil, suggest that soil aggregate size strongly affects AgNP transport in natural soil. The retention of AgNPs in the soil column was reduced when humic acid was added to the leaching solution, while a lower flow rate (Darcy velocity of 0.17 cm/min versus 0.66 cm/min) resulted in higher retention of AgNPs in the soil. When soil residual chloride was exchanged by nitrate prior to column experiments, significantly improved mobility of AgNPs was observed in the soil column. These findings point to the importance of AgNP-soil chemical interactions as a retention mechanism, and demonstrate the need to employ natural soils rather than glass beads or quartz in representative experimental investigations.     

Influence of liberated silver from silver nanoparticles on nitrification inhibition of Nitrosomonas europaea

The ecotoxicity of silver nanoparticles (Ag-NPs) to wastewater biota, including ammonia oxidizing bacteria (AOB), is gaining increasing interest as the number of products containing Ag-NPs continues to rise exponentially and they are expected to accumulate in wastewater treatment plants. This research demonstrated that the addition order of Ag-NP and the media constituents had a profound influence on the stability of the Ag-NP suspension and the corresponding repeatability of results and sensitivity of Nitrosomonas europaea. N. europaea, a model AOB, was found to be extremely sensitive to ionic silver (Ag⁺) and two sizes of Ag-NPs (20 and 80 nm). Ag⁺ exposures resulted in the highest level of toxicity with smaller Ag-NPs (20 nm) being more toxic than larger Ag-NPs (80 nm). The increased sensitivity of N. europaea to smaller Ag-NPs was caused by their higher rates of dissolved silver (dAg) release, via dissolution, due to a greater surface area to volume ratio. dAg was shown to be responsible for the vast majority of the observed Ag-NP toxicity, as determined by abiotic Ag-NP dissolution tests. For the sizes of Ag-NP studied (20 and 80 nm), there appears to be a negligible nanoparticle-specific toxicity. This was further supported by similarities in inhibition mechanisms between Ag⁺ and Ag-NP, with both causing decreases in AMO activity and destabilization of the outer-membrane of N. europaea. Finally, equal concentrations of total silver were found to be tightly associated to both Ag⁺ and Ag-NP-exposed cells despite Ag-NP concentrations being five times greater, by mass, than Ag⁺ concentrations.     

Release of silver nanoparticles from outdoor facades

In this study we investigate the release of metallic silver nanoparticles (Ag-NP) from paints used for outdoor applications. A facade panel mounted on a model house was exposed to ambient weather conditions over a period of one year. The runoff volume of individual rain events was determined and the silver and titanium concentrations of 36 out of 65 runoff events were measured. Selected samples were prepared for electron microscopic analysis. A strong leaching of the Ag-NP was observed during the initial runoff events with a maximum concentration of 145 μ Ag/l. After a period of one year, more than 30% of the Ag-NP were released to the environment. Particles were mostly <15 nm and are released as composite colloids attached to the organic binders of the paint. Microscopic results indicate that the Ag-NP are likely transformed to considerably less toxic forms such as Ag₂S.     

Arsenic release from arsenic-bearing Fe-Mn binary oxide: effects of E(h) condition

Ferric and manganese binary oxide (FMBO) has been successfully used to remediate arsenic-polluted river, but there still lacks sufficient data to evaluate its effects on environments. The release behaviors of iron (Fe), manganese (Mn), and arsenic (As) in different E_h ranges were investigated for As-bearing FMBO sediment after remediating As-polluted DaSha River by FMBO. Under high E_h range (+550 to +400 mV), slight dissolution of Fe and Mn, which corresponded to 12.2% and 25.6%, and less than 5% of As release were observed in 336 h. Under lower E_h range (+50 to −100 mV), elevated extent of the dissolution of Mn and Fe were observed, which corresponded to as high as 61.3% and 70.1%. Under such conditions, the dissolution rate of Mn was higher than that of Fe. Furthermore, from the established relationship of As release and the dissolution of Fe and Mn, the release of As seemed dominated by the dissolution of Fe. X-ray photoelectron spectroscopy (XPS) analysis demonstrated the release of Fe, Mn, As(III), and As(V) after sodium ascorbate-treatment, and the re-adsorption of As(V), as indicated from the increased binding energy of As 3d from 44.78 to 45.83 eV. Surface element composition analysis indicated significant decrease of Mn from 3.22% to 0.54%, slight increase of Fe from 12.45% to 13.67%, and elevated ratio of As from 0.11% to 0.32% accordingly. The main reactions of Fe and Mn dissolution and the pathways of As release under different E_h ranges were also proposed.     

Long-term records of cadmium and silver contamination in sediments and oysters from the Gironde fluvial-estuarine continuum - evidence of changing silver sources

The Gironde fluvial estuarine system is impacted by historic metal pollution (e.g. Cd, Zn, Hg) and oysters (Crassostrea gigas) from the estuary mouth have shown extremely high Cd concentrations for decades. Based on recent work (Chiffoleau et al., 2005) revealing anomalously high Ag concentrations (up to 65 mg kg⁻¹; dry weight) in Gironde oysters, we compared long-term (∼1955-2001) records of Ag and Cd concentrations in reservoir sediment with the respective concentrations in oysters collected between 1979 and 2010 to identify the origin and historical trend of the recently discovered Ag anomaly. Sediment cores from two reservoirs upstream and downstream from the main metal pollution source provided information on (i) geochemical background (upstream; Ag: ∼0.3 mg kg⁻¹; Cd: ∼0.8 mg kg⁻¹) and (ii) historical trends in Ag and Cd pollution. The results showed parallel concentration-depth profiles of Ag and Cd supporting a common source and transport. Decreasing concentrations since 1986 (Cd: from 300 to 11 mg kg⁻¹; Ag: from 6.7 to 0.43 mg kg⁻¹) reflected the termination of Zn ore treatment in the Decazeville basin followed by remediation actions. Accordingly, Cd concentrations in oysters decreased after 1988 (from 109 to 26 mg kg⁻¹, dry weight (dw)), while Ag bioaccumulation increased from 38 up to 116 mg kg⁻¹, dw after 1993. Based on the Cd/Ag ratio (Cd/Ag ∼ 2) in oysters sampled before the termination of zinc ore treatment (1981-1985) and assuming that nearly all Cd in oysters originated from the metal point source, we estimated the respective contribution of Ag from this source to Ag concentrations in oysters. The evolution over the past 30 years clearly suggested that the recent, unexplained Ag concentrations in oysters are due to increasing contributions (>70% after 1999) by other sources, such as photography, electronics and emerging Ag applications/materials.     

Studies on electrochemical recovery of silver from simulated waste water from Ag(II)/Ag(I) based mediated electrochemical oxidation process

In the Ag(II)/Ag(I) based mediated electrochemical oxidation (MEO) process, the spent waste from the electrochemical cell, which is integrated with the scrubber columns, contains high concentrations of precious silver as dissolved ions in both the anolyte and the catholyte. This work presents an electrochemical developmental study for the recovery of silver from simulated waste water from Ag(II)/Ag(I) based MEO process. Galvanostatic method of silver deposition on Ti cathode in an undivided cell was used, and the silver recovery rate kinetics of silver deposition was followed. Various experimental parameters, which have a direct bearing on the metal recovery efficiency, were optimized. These included studies with the nitric acid concentration (0.75-6M), the solution stirring rate (0-1400 rpm), the inter-electrode distance between the anode and the cathode (2-8 cm), the applied current density (29.4-88.2 mA cm(-2)), and the initial Ag(I) ion concentration (0.01-0.2M). The silver recovered by the present electrodeposition method was re-dissolved in 6M nitric acid and subjected to electrooxidation of Ag(I) to Ag(II) to ascertain its activity towards Ag(II) electrogeneration from Ag(I), which is a key factor for the efficient working of MEO process. Our studies showed that the silver metal recovered by the present electrochemical deposition method could be reused repeatedly for MEO process with no loss in its electrochemical activity. Some work on silver deposition from sulfuric acid solution of different concentrations was also done because of its promising features as the catholyte in the Ag(II) generating electrochemical cell used in MEO process, which include: (i) complete elimination of poisonous NO(x) gas liberation in the cathode compartment, (ii) reduced Ag(+) ion migration across Nafion membrane from anolyte to catholyte thereby diminished catholyte contamination, and (iii) lower cell voltage and hence lesser power consumption.     

Ozone affects pollen viability and NAD(P)H oxidase release from Ambrosia artemisiifolia pollen

Air pollution is frequently proposed as a cause of the increased incidence of allergy in industrialised countries. We investigated the impact of ozone (O₃) on reactive oxygen species (ROS) and allergen content of ragweed pollen (Ambrosia artemisiifolia). Pollen was exposed to acute O₃ fumigation, with analysis of pollen viability, ROS and nitric oxide (NO) content, activity of nicotinamide adenine dinucleotide phosphate (NAD[P]H) oxidase, and expression of major allergens. There was decreased pollen viability after O₃ fumigation, which indicates damage to the pollen membrane system, although the ROS and NO contents were not changed or were only slightly induced, respectively. Ozone exposure induced a significant enhancement of the ROS-generating enzyme NAD(P)H oxidase. The expression of the allergen Amb a 1 was not affected by O₃, determined from the mRNA levels of the major allergens. We conclude that O₃ can increase ragweed pollen allergenicity through stimulation of ROS-generating NAD(P)H oxidase.     

Characterization of bacteria with phenol-oxidase activity from soil in the La Laguna area (Spain)

A total of 168 bacterial strains isolated from soil of the La Laguna area (Tenerife Island, Spain) were characterized and assayed for phenol-oxidase enzymes (as an indicator of lignolytic capability).     

Effect of bone meal (calcium phosphate) amendments on metal release from contaminated soils--a leaching column study

Metal-contaminated soil may be remediated in situ by the formation of highly insoluble metal phosphates if an appropriate phosphorus (P) source can be found. Leaching column experiments have been carried out to assess the suitability of bone meal as such a source. Bone meal additions reduced metal release from a contaminated soil, increased soil and leachate pH and decreased soil leachate toxicity. Minimal P leaching occurred from the soil. The data are consistent with a proton consuming bone meal (calcium phosphate) dissolution reaction followed by the formation of metal phosphates. Although, no metal phosphates were observed to form using X-ray diffraction of scanning electron microscopy this could be due to their low concentration. Relatively low (1:50 bone meal:soil) concentrations of fine (90-500 microns) bone meal would appear to be an effective treatment for metal-contaminated soils.     

The silvering process of European eel (Anguilla anguilla) influences PAH metabolite concentrations in bile fluid: consequences for monitoring

The stock of the catadromous European eel (Anguilla anguilla L.) continues to decline and there is growing evidence that poor health status due to contaminants might be a key element in this decrease. Organic contaminants such as polycyclic aromatic hydrocarbons (PAHs) belong to the major threats to yellow eel in their growth habitat and their metabolites are detectable in the bile. Starting the silvering process eels undergo physiological and morphological changes including cessation of feeding and downstream migration back to their spawning grounds. Reduced feed intake results in a diminishment of bile production and induces accumulation of e.g. PAH-metabolites in bile. Therefore, the aim of the present study was to demonstrate the impact of silvering on biliary PAH metabolite concentrations and to utilize normalization procedures to overcome silvering related accumulation effects of PAH-metabolites in eel bile. We investigated the hydroxyl-metabolites of pyrene (1-OH Pyr) and phenantrene (1-OH Phen) in the bile of different maturation stages of eels (silvering index I-V) from nine German rivers. We detected increasing absolute PAH metabolite levels in bile during the silvering process. The highest rise could be observed at the transition from pre migration stage III to the migrating stage IV, suggesting the onset of cessation of feeding at this stage. A cessation bias in PAH metabolite measurement could be diminished by normalization of absolute values against bile pigments (A₃₈₀, biliverdin). In conclusion, we demonstrated the impact of silvering on PAH metabolite concentrations in eel bile and present suitable normalization procedures to overcome silvering related accumulation effects. Thus, for a future eel monitoring we recommend (1) to regularly monitor PAH metabolites in bile, (2) to determine silvering index of eel and (3) to normalize PAH metabolite values in bile based on maturation/silvering stages. The knowledge of the silvering stage is mandatory for an unbiased evaluation of PAH contamination of European eel towards an international harmonized eel monitoring program.     

Detrital control on the release of dissolved organic nitrogen (DON) and dissolved inorganic nitrogen (DIN) from the forest floor under chronic N deposition

The role of detrital quantity and quality in forest floor N leaching was investigated in a litter manipulation experiment at a deciduous forest under chronic N deposition. Dissolved inorganic nitrogen (DIN) comprised the bulk of nitrogen leaching from the control except a short period following autumn litterfall. The dominance of DIN was strengthened by litter exclusion, whereas the addition of glucose or fresh litter led to a small increase in dissolved organic nitrogen (DON) and either a temporary or gradual reduction in NO(3)(-) release, respectively. Changes in soluble organic C and microbial C in the forest floor implied that increased availability of C sources might have enhanced microbial immobilization of DIN, either temporarily following glucose application or over the longer term following litter addition. The results suggest that detrital quantity and quality can play a crucial role in determining the balance between DIN and DON in N-enriched forest soils.     

Uptake from water, release and tissue distribution of 54Mn in the Rainbow trout (Oncorhynchus mikiss Walbaum)

As part of a research programme on the transfer of several radionuclides along a pelagic trophic chain, two groups of 12 trout were kept for 8 weeks in water contaminated with 30 Bq ml(-1) of (54)Mn. In order to simulate chronic contamination and limit alterations in the physical and chemical characteristics of the medium, the water was renewed every 2 days. The kinetics of the accumulation and elimination of the radionuclide were monitored in one group of fish. The second group was used to study the contamination of the main organs and tissues at the end of the accumulation phase. The dynamics of contamination can be described by a bi-compartmental model, taking into account the fluctuations in the concentration of (54)Mn in the water, as well as the biological dilution resulting from the growth of the fish. The theoretical value of the steady-state concentration factor for zero growth is 13 (w.w.) and the radionuclide release is characterised by two biological half-lives of 6 and 97 days. At the end of the accumulation phase, the (54)Mn is preferentially fixed in the bone, gills, skin and brain. The data obtained at the end of the depuration phase allow one to classify the organs in two groups with different elimination kinetics. The first group consists of organs of penetration or transit, such as the skin, gills, kidneys, liver, primary and secondary gut and viscera, whereas the second group is made up of the receptor and storage organs and tissues such as the bone, head, fins and muscle.     

Characterization of a fatty acid-binding protein from the Pacific oyster (Crassostrea gigas): pharmaceutical and toxicological implications

Environmental Science and Pollution Research - Pharmaceuticals and their metabolites constitute a class of xenobiotics commonly found in aquatic environments which may cause toxic effects in...     

Characterization of Tagaran natural clay and its efficiency for removal of cadmium (II) from Sulaymaniyah industrial zone sewage

Environmental Science and Pollution Research - The fine fraction of the Tagaran natural clay (TC) from the Kurdistan region of Iraq-Sulaimani was characterized and used to remove Cd ions from...     

Acidic pharmaceuticals in domestic wastewater and receiving water from hyper-urbanization city of China (Shanghai): environmental release and ecological risk

The occurrence, behavior, and release of five acidic pharmaceuticals, including ibuprofen (IBP), naproxen (NPX), ketoprofen (KEP), diclofenac (DFC), and clofibric acid (CA), have been investigated along the different units in a tertiary-level domestic wastewater treatment plant (WWTP) in hyper-urbanization city of China (Shanghai). IBP was the most abundant chemicals among the measured in raw wastewater. The loads of the acidic pharmaceuticals in the WWTP influent ranged from 7.5 to 414 mg/day/1,000 inh, which were lower than those reported in the developed countries suggesting a less per capita consumption of pharmaceuticals in Shanghai. IBP obtained by highest removal (87 %); NPX and KEP were also significantly removed (69–76 %). However, DFC and CA were only moderately removed by 37–53 %, respectively. Biodegradation seemed to play a key role in the elimination of the studied pharmaceuticals except for DFC and CA. An annual release of acidic pharmaceuticals was estimated at 1,499 and 61.7 kg/year through wastewater and sludge, respectively, from Shanghai. Highest pharmaceuticals concentrations were detected in the effluent discharge point of the WWTP, indicating that WWTP effluent is the main source of the acidic pharmaceuticals to its receiving river. Preliminary results indicated that only DFC in river had a high risk to aquatic organisms. Nevertheless, the joint toxicity effects of these chemicals are needed to further investigate.     

Toxicological response of silver catfish (Rhamdia quelen) after acute exposure to a commercial insecticide containing thiamethoxam

Abstract

This study assessed the hematological, enzymatic and osmoregulatory responses of silver catfish (Rhamdia quelen) exposed to sublethal concentrations (1.125 and 3.750?µg/L) of a commercial thiamethoxam-containing insecticide used on rice crops. Groups of 6 fish per tank (in triplicate, n?=?3, total 54 fish) were exposed for up to 96?h to different concentrations of the compound. After this period, fish were placed in clean water for 48?h. Two fish from each tank (6 per treatment) that had been exposed to the insecticide for 24?h were anesthetized with eugenol and blood was collected to evaluate hematological and biochemical parameters. Blood, liver and muscle were collected for determination of metabolic parameters, plasma cortisol, Cl^-, Na⁺ and K⁺ levels and H⁺-ATPase and Na⁺/K⁺-ATPase activity in the gill. H⁺-ATPase activity was higher in fish exposed to 1.125?µg/L insecticide at 24?h compared to control (0.0?µg/L). Differences in cortisol levels were evidenced throughout the experimental period. These results indicated that exposure to the insecticide changed the hematological, biochemical and metabolic profile of the animals, suggesting concern about environmental safety. Therefore, we discourage the use of this pesticide in areas that come into contact with water bodies inhabited by fish.     

Characterization of primary precipitate composition formed during co-removal of Cr(VI) with Cu(II) in synthetic wastewater

BACKGROUND, AIMS AND SCOPE: Hexavalent chromium [Cr(VI)] cannot react with either carbonate or hydroxide to form chromium precipitates. However, by using a precipitation technology to treat plating wastewater containing Cr(VI), Cu(II), Ni(II) and Zn(II), approximately 78% of Cr(VI) (initial 60 mg/L) was co-removed with the precipitation of Cu(II), Ni(II) and Zn(II) (each 150 mg/L) by dosing with Na2CO3 (Sun 2003). Direct precipitation by forming Cu(II)-Cr(VI) precipitates followed by adsorption of Cr(VI) onto freshly formed Cu-precipitates was subsequently found to be the main mechanism(s) involved in Cr(VI) co-removal with Cu(II) precipitation by dosing Na2CO3 stepwise to various pH values (Sun et al. 2003). This study was. carried out to further characterize the formation of primary precipitates during the early stages of copper precipitation and simultaneous removal of Cr(VI) with Cu(II). METHODS: Test metal-solutions were prepared with industrial grade chemicals: CuCl2 x 2H2O, Na2SO4 and K2Cr2207. NaCO3 was added drop-wise to synthetic metal-solution to progressively increase pH. For each pH increment, removal of soluble metals was detected by atomic absorption spectrophotometer (AAS) and surface morphology of precipitates was analyzed by scanning electron microscope (SEM). To further characterize the formation of primary precipitates, a series of MINEQL+ thermodynamic calculations/analyses and equilibrium calculations/ analyses were conducted. RESULTS AND DISCUSSION: MINEQL+ thermodynamic calculation indicated that, for a system containing 150 mg/L Cu(II) and 60 mg/L Cr(VI) with gradual Na2CO3 dosing, if any precipitates can be formed at pH 5.0 or lower, it should be in the form of CuCrO4. Comparison tests using systems containing the same equivalent of Cu(II) plus Cr(VI) and Cu(II) plus SO4(2-) showed that the precipitation occurred at a pH of around 5.0 in the Cu(II)-Cr(VI) system and around 6.0 in the Cu(II)-SO4(2-) system. The discrepancy of the precipitation was indeed caused by the formation of Cu-Cr precipitates. The initiation of copper removal at pH around 5.0 for the Cu-Cr co-removal test was not attributable to the formation of Cu-CO3 precipitates, instead, it was most likely through the formation of insoluble Cu-Cr precipitates, such as CuCrO4 and CuCrO4 x 2Cu(OH)2. Experimental tests, equilibrium calculations, MINEQL+ thermodynamic calculations and surface morphologies for systems using higher concentrations of Cu(II) and Cr(VI) further verified the most probable composition of primary precipitates is copper-chromate. CONCLUSION: In the Cu-Cr co-removal test with Na2O3 dosing to increase pH and induce metal precipitation, copper-chromate precipitates are the primary precipitates produced and contribute to the initial simultaneous removal of copper and chromium.     

Effect of clomazone herbicide on biochemical and histological aspects of silver catfish (Rhamdia quelen) and recovery pattern

The effects of the herbicide, clomazone, on acetylcholinesterase (AChE), catalase and TBARS formation in teleost fish (Rhamdia quelen) were studied. The fish were exposed to 0.5 or 1.0 mg L⁻¹ of clomazone for 12, 24, 48, 96 and 192 h. After 192 h of exposure period, fish were transferred to clean water and kept in the same for 192 h to study the recovery response. Same parameters as that of exposure period were assayed after 96 and 192 h of recovery period. Specific AChE activity was reduced in the brain and muscle after treatments, reaching a maximum inhibition of 47% in the brain and 45% in the muscle after 12 h of exposure. Fish exposed to clomazone increased TBARS production in the liver for all exposure periods. The brain presented elevated TBARS levels after 12, 24 and 48 h, but after 96 and 192 h, these levels decreased. The decrease of TBARS levels persisted in brain tissue after 96 h of recovery and returned to the control value after 192 h in clean water. Catalase activity was reduced for all periods of exposure. Histological analysis showed vacuolation in the liver after herbicide exposure. Some of the alterations observed were completely restored after recovery period.     

Development of controlled release formulations of azadirachtin-A employing poly(ethylene glycol) based amphiphilic copolymers

Controlled release (CR) formulations of azadirachtin-A, a bioactive constituent derived from the seed of Azadirachta indica A. Juss (Meliaceae), have been prepared using commercially available polyvinyl chloride, polyethylene glycol (PEG) and laboratory synthesized poly ethylene glycol–based amphiphilic copolymers. Copolymers of polyethylene glycol and various dimethyl esters, which self assemble into nano micellar aggregates in aqueous media, have been synthesized. The kinetics of azadirachtin-A, release in water from the different formulations was studied. Release from the commercial polyethylene glycol (PEG) formulation was faster than the other CR formulations. The rate of release of encapsulated azadirachtin-A from nano micellar aggregates is reduced by increasing the molecular weight of PEG. The diffusion exponent (n value) of azadirachtin-A, in water ranged from 0.47 to 1.18 in the tested formulations. The release was diffusion controlled with a half release time (t_1/2) of 3.05 to 42.80 days in water from different matrices. The results suggest that depending upon the polymer matrix used, the application rate of azadirachtin-A can be optimized to achieve insect control at the desired level and period.