Controlled-release systems for the delivery of cyromazine into water surface

Controlled-release systems (CRSs) for the insect growth regulator cyromazine (Neporex), as a larvicide against Culex pipiens (Culicidae) mosquitoes, are under development. Despite promising results obtained previously for both in vitro (dissolution tests) and in vivo systems (mosquito larvae floating on water surfaces), it was evident that the CRSs did not remain afloat for sufficiently long times. The present study was thus conducted to determine the relationship between the process parameters and the potential contact time of the active ingredient with the mosquito larvae. A series of CRSs were prepared by an extrusion process, alone or in combination with a supplementary coating. The active ingredient was incorporated into the matrix or the coating. The matrix comprised low-density polyethylene 600 and perlite, and the coating, a polyurea with or without the addition of paraffin wax. The study showed that the cumulative release of the active ingredient into water could be controlled by manipulating the preparation techniques, the types and concentrations of inert materials, and the concentration of the active ingredient.     

Controlled release of the herbicide norflurazon into water from ethylcellulose formulations

The herbicide norflurazon was encapsulated in ethylcellulose (EC(40)) microspheres by the solvent evaporation technique to obtain controlled release formulations. The kinetics of release of the active ingredient into the aqueous solution from different preparations was determined. It was found that the percentage release of the incorporated herbicide was a function of the composition and formation conditions of the formulations (amount of emulsifying agent, EC(40)/herbicide ratio, stirring speed, and percentage of pore-forming agent). The percentage of the herbicide release was related to the properties of the different microspheres obtained, such as particle size distribution, herbicide loading, or surface morphology. The release percentage depended inversely on the particle size of the microspheres and directly on the content of active ingredient and emulsifying and pore-forming agents. An empirical equation was used to fit the herbicide release data, indicating that the release of norflurazon from the various formulations is controlled by a diffusion mechanism. The time taken for 50% of the active ingredient to be released into water (T(50)) was calculated, showing a wide variation among the different preparations (0.95-16.4 days).     

Emodin isolated from Cassia obtusifolia (Leguminosae) seed shows larvicidal activity against three mosquito species

Mosquito larvicidal activity of Cassia obtusifolia (Leguminosae) seed-derived materials against the fourth-instar larvae of Aedes aegypti, Aedes togoi, and Culex pipiens pallens was examined. The chloroform fraction of C. obtusifolia extract showed a strong larvicidal activity of 100% mortality at 25 mg/L. The biologically active component of C. obtusifolia seeds was characterized as emodin by spectroscopic analyses. The LC(50) values of emodin were 1.4, 1.9, and 2.2 mg/L against C. pipiens pallens, A. aegypti, and A. togoi, respectively. Pirimiphos-methyl acts as a positive control directly compared to emodin. Pirimiphos-methyl was a much more potent mosquito larvicide than emodin. Nonetheless, emodin may be useful as a lead compound and new agent for a naturally occurring mosquito larvicidal agent. In tests with hydroxyanthraquinones, no activity was observed with alizarin, danthron, and quinizarin, but purpurin has an apparent LC(50) value of approximately 19.6 mg/L against A. aegypti.     

Preparation and characterization of imidacloprid lignin-polyethylene glycol matrices coated with ethylcellulose

Imidacloprid, a systemic insecticide that has a water solubility of 610 mg L(-1), has been formulated in lignin-polyethylene glycol matrices by a melting process. This formulation was coated in a Wurster type fluidized-bed equipment using ethylcellulose and dibutyl sebacate. Imidacloprid has been entrapped, with an entrapment efficiency higher than 87% in all cases. Thermogravimetric analysis, differential scanning calorimetry, and Fourier transformed infrared spectroscopy studies indicate the stability and compatibility of polymers and imidacloprid. Scanning electron microscopy images show a homogeneous film of ethylcellulose in coated formulations. From T(50) values (the time taken for 50% of the active ingredient to be released into water), the release rate of imidacloprid is controlled by changing the thickness of the coating film and modifying its surface properties by adding a plasticizer. T(50) values, ranging from 3.02 to 168.6 h, allow supplying the appropriate amount of imidacloprid in each specific agronomic practice to increase the efficiency of this bioactive material and minimize the risk of environmental pollution.     

丙烯酸树脂包膜尿素肥料研制及其控释效果

采用丙烯酸树脂为包膜材料,以NBPT（N-丁基硫代磷酰三胺）和DCD（双氰胺）为生化抑制剂,利用流化床对尿素进行涂层生化抑制剂及包膜,制备4种包膜肥料,对这些包膜肥料在水中的控释效果进行了研究。结果表明,采用此技术制备的包膜肥料,表面成膜完整,包膜物质在成膜时分布均匀、与尿素肥心接合紧密,表面光滑。NBPT和DCD与肥心结合严密,包膜层紧覆于抑制剂的外表。包膜可有效控制尿素的溶出,在水中的控释时间为19～30d。初期溶出率远远小于15％,微分溶出率基本上在0．25％～2．5％之间;在水中尿素累积溶出特征符合一元二次方程模型,尿素释放曲线呈“S”形。     

Larvicidal activity of lignans identified in Phryma leptostachya Var. asiatica roots against three mosquito species

The insecticidal activity of phytochemicals isolated from the roots of Phryma leptostachya var. asiatica against third instar larvae of Culex pipiens pallens, Aedes aegypti, and Ocheratatos togoi was examined. The two constituents of P. leptostachya var. asiatica roots were identified as the leptostachyol acetate (I) and 8'-acetoxy-2,2',6-trimethoxy-3,4,4',5'-dimethylenedioxyphenyl-7,7'-dioxabicyclo[3.3.0]octane (II) by spectroscopic analysis. Compound I was lethal to C. pipiens pallens, A. aegypti, and O. togoi at 10 ppm. Compound II showed weak or no insecticidal activity against three mosquito species at 10 ppm. The LC(50) values of I against C. pipiens pallens, A. aegypti, and O. togoi were 0.41, 2.1, and 2.3 ppm, respectively. Naturally occurring P. leptostachya var. asiatica root-derived compounds merit further study as potential mosquito larval control agents or lead compounds.     

Bioactive aromatic compounds from leaves and stems of Vanilla fragrans.

Alcoholic extracts of leaves and stems of Vanilla fragrans were fractionated with ethyl acetate and aqueous butanol. All three fractions of ethyl acetate, butanol, and water were screened for toxic bioactivity against mosquito larvae. The results of these experiments showed that the fractions from the ethyl acetate and butanol phases were both active in the bioassay. Bioactivity of the ethyl acetate fraction was found to be much greater than that from the butanol fraction in mosquito larvae toxicity. The water phase appeared to contain no substances that impaired mosquito larval growth. Repeated column chromatography of the ethyl acetate fraction on silica gel led to the isolation of 4-ethoxymethylphenol (1), 4-butoxymethylphenol (2), vanillin (3), 4-hydroxy-2-methoxycinnamaldehyde (4), and 3,4-dihydroxyphenylacetic acid (5). Compounds 4 and 5 were isolated from Vanilla species for the first time and 2 has not been reported to have been found in a natural form. 4-Ethoxymethylphenol (1) was the predominant compound, but 4-butoxymethylphenol (2) showed the strongest toxicity to mosquito larvae. The structures of the compounds were determined on the basis of their mass spectra and (1)H or (13)C NMR data.     

Larvicidal activity of isobutylamides identified in Piper nigrum fruits against three mosquito species

The insecticidal activity of materials derived from the fruits of Piper nigrum against third instar larvae of Culex pipiens pallens, Aedes aegypti, and A. togoi was examined and compared with that of commercially available piperine, a known insecticidal compound from Piper species. The biologically active constituents of P. nigrum fruits were characterized as the isobutylamide alkaloids pellitorine, guineensine, pipercide, and retrofractamide A by spectroscopic analysis. Retrofractamide A was isolated from P. nigrum fruits as a new insecticidal principle. On the basis of 48-h LC(50) values, the compound most toxic to C. pipiens pallens larvae was pipercide (0.004 ppm) followed by retrofractamide A (0.028 ppm), guineensine (0.17 ppm), and pellitorine (0.86 ppm). Piperine (3.21 ppm) was least toxic. Against A. aegypti larvae, larvicidal activity was more pronounced in retrofractamide A (0.039 ppm) than in pipercide (0.1 ppm), guineensine (0.89 ppm), and pellitorine (0.92 ppm). Piperine (5.1 ppm) was relatively ineffective. Against A. togoi larvae, retrofractamide A (0.01 ppm) was much more effective, compared with pipercide (0.26 ppm), pellitorine (0.71 ppm), and guineensine (0.75 ppm). Again, very low activity was observed with piperine (4.6 ppm). Structure-activity relationships indicate that the N-isobutylamine moiety might play a crucial role in the larvicidal activity, but the methylenedioxyphenyl moiety does not appear essential for toxicity. Naturally occurring Piper fruit-derived compounds merit further study as potential mosquito larval control agents or as lead compounds.     

C36多元醇改良C18多元醇包膜肥料缓控释性能

为探讨C36多元醇(简称C36)对C18多元醇(简称C18,对照)包膜材料缓控释性能的影响,该文以C18为对照膜材,将C36与C18分别按照质量比1:2、2:3、1:1共混聚合制备成3种新型包膜材料,在相同工艺下依次制造成包膜厚度均为2.5%(膜材占核芯肥料的百分比)的包膜尿素,分别记作PCU1、PCU2、PCU3、PCU4,其中PCU1为对照。通过坠落撞击前、后包膜尿素的释放率评价C36作为包膜材料的效果。研究结果表明:C36与C18共混聚合包膜尿素的外观及耐撞击性能明显优于对照处理的,表现为包膜层光泽明亮、膜质均匀、膜层韧性好,同期静水培养的颗粒表面积较对照的增加了23%。该文提出了肥效期保持率(tR)的概念,并用其评价包膜肥料耐撞击性能。共混聚合物C36:C18比例为2:3时,包膜尿素耐撞击性能最优,受撞击后肥效期保持率tR可高达88%左右,为对照处理的2.5倍以上。该处理包膜尿素的初期溶出率、微分溶出率最小,与对照PCU1处理的无明显差异。C36嵌入C18共混聚合生成的新包膜材料对包膜尿素肥效期的影响与两者的比例和包膜材料的用量有关,当C36:C18为2:3,包膜材料用量(2.5%)小于常规用量(3%~4%)时,虽然包膜尿素的肥效期没有延长,但是包膜完整、膜层均匀、韧性强,在包膜肥受到强烈撞击的情况下能够很好地保持原有肥料的肥效期,即能保持包膜肥料的缓控释性能。因此,在C18多元醇嵌入适量C36多元醇是改良C18多元醇包膜材料,增加其包膜肥肥效期保持率的有效方法。     

In vivo sodium release and saltiness perception in solid lipoprotein matrices. 1. Effect of composition and texture

Reducing the sodium content in foods is complex because of their multidimensional sensory characteristics and the multifunctionality of sodium chloride. The aim of this study was to elucidate how food composition may influence in-mouth sodium release and saltiness perception. Lipoprotein matrices (LPM) were produced using milk constituents and characterized by means of rheological measurements, texture, and taste sensory profiles. Texture and taste perceptions were affected differently by variations in the salt level, dry matter, and fat contents. Composition and textural changes also modified temporal sodium release and saltiness perception recorded in five subjects, but the effects varied as a function of the salt content. The water content mainly appeared to influence the amount of sodium released, whereas saltiness perception was mainly related to fat content. Elasticity, coating, and granularity were found to be correlated with temporal sodium release and/or saltiness parameters.     

含氮、磷包膜缓释肥的制备及其缓释性能研究

采用红外光谱(FTIR)对以尿素、甲醛和磷酸一铵为原料,制备了以磷酸一铵为核心,脲醛肥为膜材料,同时含有氮、磷两种营养元素的包膜缓释肥的结构进行了研究。通过其在土壤中的养分释放特性表明,在土壤中,氮元素的缓释期为100 d,磷元素的缓释期为30 d;而在水中,氮元素在100 d时只释放了70%,磷元素在10 d时则达到100%。说明作为膜材料的缓释肥通过聚合物降解的化学过程,使氮元素获得了明显的缓释效果;作为核心的磷酸一铵,受包膜的物理保护,其分子中的磷元素也获得了一定的缓释效果。     

Preparation and properties of a double-coated slow-release and water-retention urea fertilizer

A double-coated, slow-release, and water-retention urea fertilizer (DSWU) was prepared by cross-linked poly(acrylic acid)-containing urea (PAAU) (the outer coating), polystyrene (PS) (the inner coating), and urea granule (the core). Elemental analysis results showed that the nitrogen content of the product was 33.6 wt %. The outer coating (PAAU) regulated the nitrogen release rate and protected the inner coating from damage. The slow-release property of the product was investigated in water and in soil. The possible mechanism of nitrogen release was proposed. The influences of PS coating percentage, temperature, water absorbency, and pH on the release of nitrogen were also investigated. It was found that PS coating percentage, temperature, and water absorbency had a significant influence on the release of nitrogen. However, the pH had no effect. The water-retention property of the product was also investigated. The results showed that the product not only had a good slow-release property but also excellent water-retention capacity, which could effectively improve the utilization of fertilizer and water resources. The results of the present work indicated that the DSWU would find good application in agriculture and horticulture, especially in drought-prone areas where the availability of water is insufficient.     

双层和夹层包膜工艺对水基树脂包膜材料控释性能的影响

为了优化水基树脂的包膜控释性能,该文以脂溶性树脂为配合包膜材料,利用底喷风动流化床制造多层包膜控释尿素,并通过包膜控释尿素养分释放率的测定评价双层和夹层包膜工艺对水基树脂包膜材料控释性能的影响.研究结果表明:两种工艺相比,夹层包膜工艺能显著延长包膜控释尿素的肥效期,其肥效期是双层包膜工艺的5倍.在夹层包膜工艺中,内保护层厚度在5～15 g/m2的范围内对包膜控释尿素的肥效期无明显影响,50 g/m2水基树脂控释层和10g/m2脂溶性树脂外保护层夹层控释尿素的肥效期均约为260 d.但是,夹层包膜控释尿素的养分释放模式与内保护层厚度有关,内保护层厚度达到10 g/m2以上时,养分释放模式由抛物线型变成了S型.综上可知,脂溶性树脂内保护层较适宜的厚度为5～10 g/m2,采用夹层包膜工艺能更好的发挥水基树脂的控释性能.     

Controlled release of diuron from an alginate-bentonite formulation: water release kinetics and soil mobility study

The herbicide diuron was incorporated in alginate-based granules to obtain controlled release (CR) properties. The standard formulation (alginate-herbicide-water) was modified by the addition of different sorbents. The effect on diuron release rate caused by incorporation of natural and acid-treated bentonites in alginate formulation was studied by immersion of the granules in water under static conditions. The release of diuron was diffusion-controlled. The time taken for 50% release of active ingredient to be released into water, T(50), was calculated for the comparison of formulations. The addition of bentonite to the alginate-based formulation produced the higher T(50) values, indicating slower release of the diuron. The mobility of technical and formulated diuron was compared by using soil columns. The use of alginate-based CR formulations containing bentonite produced a less vertical distribution of the active ingredient as compared to the technical product and commercial formulation. Sorption capacities of the various soil constituents for diuron were also determined using batch experiments.     

Herbicide solubilization in micelle-clay composites as a basis for controlled release sulfentrazone and metolachlor formulations

Sulfentrazone and metolachlor have been detected in groundwater due to extensive leaching. To reduce herbicide leaching and increase weed control, we have developed, designed, and tested controlled release formulations (CRFs) for both herbicides based on their solubilizion in cationic micelles and adsorption of the mixed micelles (surfactant and herbicide) on a clay mineral, montmorillonite. A better understanding of solubilizing anionic (sulfentrazone) and nonionic (metolachlor) organic molecules in cationic micelles was reached. The percent of active ingredient in the formulations was much higher than previously designed CRFs due to the enhanced solubilization of the herbicides in the micelles and due to their adsorption on the clay. Both CRFs demonstrated controlled release (compared to the commercial formulations) when applied to a thin soil layer. A bioassay in soil columns determined that the new sulfentrazone and metolachlor CRFs significantly improve weed control and reduce leaching (for the latter) in comparison with the commercial formulations.     

粒径膜厚与控释肥料的氮素养分释放特性

利用专利技术,以芬兰长之道Uki厂生产的粒径分别为2.5～3.0、3.0～4.0、4.0～5.0mm的氮磷钾复合肥制造控释肥料。在25℃和40℃恒温条件下培养0、1、2、3、4、5、6、7、14、21、28、35、42d后测定氮素释放率,以探讨粒径、包膜厚度(膜材用量)、交联剂等对氮素释放率的影响。结果表明,常温和高温下,包膜厚度相同时,氮素释放率随着肥料粒径的增加而明显增加;但氮素释放率随粒径增长的幅度在膜材用量增大的情况下减小。无论是小粒还是大粒控释肥料,其氮素释放的速率随膜材用量的增多而减小。包膜材料添加交联剂可以明显增加氮素释放率,交联剂S的用量对氮素释放率的影响小于交联剂P。同一包膜厚度和单位质量下,用大粒径核心肥料制造的控释肥料可明显减少包膜材料的用量;但要改进大粒径控释肥料的氮素释放率,应利用表面平滑的核心肥料制造包膜控释肥料。     

A piperidine amide extracted from Piper longum L. fruit shows activity against Aedes aegypti mosquito larvae

Mosquito larvicidal activity of Piper longum fruit-derived materials against the fourth-instar larvae of Aedes aegypti was examined. A crude methanol extract of P. longum fruits was found to be active against the larvae, and the hexane fraction of the methanol extract showed a strong larvicidal activity of 100% mortality. The biologically active component of P. longum fruits was characterized as pipernonaline by spectroscopic analyses. The LC(50) value of pipernonaline was 0.25 mg/L. The toxicity of pipernonaline is comparable to that of pirimiphos-methyl as a mosquito larvicide. In tests with available components derived from P. longum, no activity was observed with piperettine, piperine, or piperlongumine.     

Detection and quantification of roundup ready soy in foods by conventional and real-time polymerase chain reaction

Transgenic soybean line GTS-40-3-2, marketed under the trade name Roundup Ready (RR) soy, was developed by Monsanto (USA) to allow for the use of glyphosate, the active ingredient of the herbicide Roundup, as a weed control agent. RR soy was first approved in Canada for environmental release and for feed products in 1995 and later for food products in 1996 and is widely grown in Canada. Consumer concern issues have resulted in proposed labeling regulations in Canada for foods derived from genetically engineered crops. One requirement for labeling is the ability to detect and accurately quantify the amount of transgenic material present in foods. Two assays were evaluated. A conventional qualitative Polymerase Chain Reaction (PCR) assay to detect the presence of soy and RR soy and a real-time PCR to quantify the amount of RR soy present in samples that tested positive in the first assay. PCR controls consisted of certified RR soy reference material, single transgenic soybeans, and a processed food sample containing a known amount of RR soy. To test real-world applicability, a number of common grocery store food items that contain soy-based products were tested. For some samples, significant differences in amplification efficiencies during the quantitative PCR assays were observed compared to the controls, resulting in potentially large errors in quantification. A correction factor was used to try to compensate for these differences.     

Effect of soil moisture on the release of alachlor from alginate-based controlled-release formulations

The release of alachlor from controlled-release formulations (CRFs) based on alginate-montmorillonite matrices into aqueous polyethylene glycol (PEG) solutions of different concentrations and into a soil at different moisture contents was studied. In distilled water and in PEG-containing solutions displaying -0.1 MPa potential and up, the beads imbibe water and swell. The ensuing increase in weight is about 5%, and the increase in the bead's diameter is about 10%. At water potentials of -0.5 MPa and lower, loss of weight and shrinkage of the beads were observed. The changes in weight and diameter of the alginate-clay beads incubated in a Hamra loamy sand soil at 26.5% moisture content (w/w; -0.18 MPa) were similar to those observed in PEG solutions of >-0.5 MPa moisture potential. The weight and diameter losses observed in the drier soils (12.0 and 7.1% water content; -0.49 and -1.11 MPa) were similar to those in the more concentrated PEG solutions. A decrease in the rate of release of the active ingredient from the beads into soil was observed as the water potential decreased (drier soils). The release of the active ingredient from the investigated CRFs displayed a linear relationship to the square root of time, suggesting a diffusion-controlled-release rate. Data extracted from this relationship enabled the formulation of a mathematical model that correlates rate of release to water content.     

保水剂与肥料互作及保水缓/控释肥料研究展望

保水剂在农业上的作用日益重要,肥料与保水剂一体化使用是水肥调控的重要技术,是肥料研究的国际前沿。保水剂是吸水量超过自身重量数百倍以上的亲水性高聚物。保水剂一般分为天然的,合成的及半合成的。保水剂与肥料可以通过物理混合、包膜或化学合成三种方式结合为一体化的保水缓/控释肥料。保水剂具有吸水吸肥功能,保水剂可吸附大量中性分子,对阳离子养分也有较强吸附作用,对阴离子养分吸附弱。肥料种类与盐浓度影响保水剂的吸附作用与膨胀能力。保水缓/控释肥料在土壤中对肥料养分有延迟释放作用。保水缓/控释肥料可改善土壤持蓄水分和水肥交互作用,促进植物对养分的吸收和作物增产。保水缓/控释肥料发展方向是包膜和化成保水缓/控释肥料。保水缓/控释肥料湿润及养分控释机理研究也需要加强。