Study of UV-shielding properties of novel porous hollow silica nanoparticle carriers for avermectin

The shielding protection given by self-prepared porous hollow silica nanoparticles (PHSN) to pesticides from degradation by UV light was investigated using avermectin as a model pesticide. It was demonstrated that PHSN carriers with a shell thickness of approximately 15 nm and a pore diameter of 4-5 nm have an encapsulation capacity of 625 g kg(-1) for avermectin using a supercritical fluid loading method. PHSN carriers exhibited remarkable UV-shielding properties for avermectin. This was affected by the intensity of UV light, the pH and the temperature of the release medium. Rises in UV intensity, pH and/or temperature reduced the UV protection of PHSN for avermectin. In addition, avermectin loaded into the inner core of the PHSN carriers was released slowly into the release medium for about 30 days following a typical sustained-release pattern. It thus appears that PHSN carriers have a promising future in applications requiring sustained pesticide release.     

Improved biological effects of uniconazole using porous hollow silica nanoparticles as carriers

BACKGROUND: The aim of this work is to prepare a controlled‐release formulation of uniconazole using porous hollow silica nanoparticles (PHSNs) as carrier, and to investigate the biological effects on rice growth. RESULTS: PHSNs with a shell thickness of ～15 nm and a particle size of 80–100 nm were synthesised through a sol–gel route using nanosized calcium carbonate particles as templates. Simple immersing (SI) and supercritical fluid drug loading (SFDL) technologies were employed to load uniconazole into PHSNs with loading efficiencies of ～22 and ～26% respectively. The prepared uniconazole‐loaded PHSNs (UCZ‐PHSNs) by SI and SFDL both demonstrated sustained release properties, and the latter showed better controlled release ability with a slower release rate. Compared with free uniconazole, UCZ‐PHSNs exhibited a weaker growth retardation effect in the early stage but more significant retardation ability in later stages for agar‐cultured rice seedlings. For the rice that grew in clay, UCZ‐PHSNs demonstrated a weaker plant height retardation effect than free uniconazole at the early jointing stage by foliar spraying, but exhibited a stronger retardation capacity than free uniconazole by being applied into soil before seedling transplantation. CONCLUSION: The results indicated that the prepared UCZ‐PHSNs possessed good controlled‐release properties and had improved retardation effects on rice growth. It is recommended that UCZ‐PHSNs be applied into soil before seedling transplantation rather than administered by foliar spraying at the early jointing stage. Copyright © 2011 Society of Chemical Industry     

新型阿维菌素纳米控释剂的制备及性能研究

提出利用无机-有机双模板法,即以纳米碳酸钙(平均粒径为70 nm左右)作为无机模板,表面活性剂吸附在其表面作为有机模板,以硅酸钠为硅源,通过溶胶-凝胶法,制备出空心多孔SiO2纳米颗粒,其粒径很小,平均约100 nm,壁厚大约15 nm,孔径约4.5 nm。首次采用空心多孔SiO2纳米颗粒作为控释载体对阿维菌素进行载药研究。结果表明:空心多孔SiO2纳米颗粒对阿维菌素有较强的吸附能力,包埋率高达62.5%;其对阿维菌素的吸附主要为物理吸附;初步观察发现,空心多孔SiO2纳米颗粒能够保护阿维菌素不被紫外光降解。阿维菌素纳米控释剂(Av-PHSN)在连续不断搅拌的溶出介质中的控制释放时间可长达33 h以上,这表明新型空心多孔SiO2纳米控释剂具有很好的缓释效果。因此,空心多孔SiO2纳米颗粒可望作为理想的新一代农药保护型控释载体。     

基于介孔二氧化硅纳米粒子的农药可控释放研究进展

鉴于介孔二氧化硅纳米粒子（mesoporous silica nanoparticles,MSNs）具有比表面积大、孔径可调节、孔道均匀、内外表面易于修饰和生物相容性好等优点,其在药物控释方面的应用已成为当前国内外研究的热点。本文综述了介孔二氧化硅纳米粒子的制备方法（软模板法、硬模板法和自模板法）,表征技术[扫描电镜分析（SEM）、透射电镜分析（TEM）、X射线衍射分析（XRD）、物理吸附分析、热重和差热分析（TGA-DTA）和傅里叶红外光谱分析（FT-IR）]及其在农药领域的研究应用状况,探讨了以介孔二氧化硅纳米粒子作为农药载体时存在的问题,并对其应用前景进行了展望。     

荧光介孔二氧化硅负载丙硫菌唑纳米颗粒的制备及性能研究

近年来,丙硫菌唑作为一种新颖的广谱杀菌剂备受关注,但由于其代谢产物对操作人员存在健康风险,导致其在中国的使用和登记受到限制。将丙硫菌唑制备为具有缓慢释放、可提高农药稳定性等特点的缓释制剂可有效改善其带来的健康风险问题。本研究采用纳米荧光介孔二氧化硅制备了丙硫菌唑缓释纳米颗粒,通过扫描电镜(SEM)、透射电镜(TEM)、傅里叶变换红外光谱(FTIR)、X-射线光电子能谱(XPS)、Brunauer-Emmett-Teller(BET)比表面积分析、热重分析(TGA)、荧光光谱以及高效液相色谱仪等手段对其结构与特性进行表征。采用透析袋法探讨了丙硫菌唑在释放介质中的释放行为;利用菌丝生长速率法测定了该载药颗粒对小麦赤霉病原菌的杀菌活性;通过激光共聚焦研究了荧光二氧化硅在小麦赤霉病菌菌丝体以及小麦中的传输情况。结果表明:所制备的载药纳米颗粒外观形貌较为规整,平均粒径为139 nm,其最大载药量可达27.14%;该纳米载药颗粒具有缓释性能,释放曲线符合Ritger-Peppas方程;载药颗粒与丙硫菌唑原药相比具有相同的毒力效果。此外,激光共聚焦结果表明,该荧光二氧化硅纳米颗粒可以在菌丝体以及小麦植株根部吸收和传导。     

Stabilized polymeric nanoparticles for controlled and efficient release of bifenthrin

BACKGROUND: Nanoparticle formulations of pesticides have been proposed to produce a better spatial distribution of the pesticide on leaf surfaces, which provides better efficiency. Nanoparticles are well studied for drug delivery and sustained release but not in the agricultural sciences, because of the difficulty in generating stable pesticide nanoparticles with controlled particle size distribution and because the processes to generate nanoparticles are usually costly. In this paper, a model pesticide, bifenthrin, has been prepared in nanoparticle form by using the Flash NanoPrecipitation process. The process involves rapid micromixing to effect supersaturation, and polymer assembly to control particle size. RESULTS: A multi-inlet vortex mixer (MIVM) was developed to provide rapid micromixing, high supersaturation and rapid nucleation and growth of bifenthrin nanoparticles. Several polymeric stabilizers were tested. With an increase in pesticide loading from 50 to 91%, nanoparticle size increased from 100 to 200 nm. The stability of the nanoparticle dispersions was followed for more than 12 days. The steric stability caused by the corona structure of the hydrophilic block of the polymers prevents nanoparticles aggregation. Ostwald ripening is responsible for the slow particle size growth observed. CONCLUSION: Flash NanoPrecipitation using an MIVM provides a cost-effective process to produce stable pesticide nanoparticle suspensions. Nanoparticle size depends on supersaturation, pesticide loading and type of polymer. Nanoparticle pesticides potentially provide higher efficiency, better uniformity of coverage for highly active compounds and less exposure to workers, relative to compounds solubilized in organic solvents.     

Controlled release of isoproturon from an alginate–bentonite formulation: water release kinetics and soil mobility

The herbicide isoproturon [3‐(4‐isopropylphenyl)‐1,1‐dimethylurea] was incorporated in alginate‐based granules to obtain controlled‐release (CR) properties. The basic formulation (sodium alginate (1.87%)–isoproturon (0.67%) in water) was modified by addition of different sorbents. The effect on isoproturon release rate, modified by the incorporation of natural and acid‐treated bentonite in alginate formulation, was studied by immersion of the granules in water while shaking. The release of isoproturon was diffusion‐controlled. The time taken for 50% of the active ingredient to be released into water, T₅₀, was longer for those formulations containing added bentonite (5.98 and 7.43 days, for natural and acid‐treated (1 M H₂SO₄) bentonite, respectively) than for the preparation without bentonite (3.78 days). The mobilities of non‐formulated technical grade (98%) and formulated isoproturon were compared using soil columns. The use of alginate‐based CR formulations containing bentonite reduced isoproturon movement compared with the technical product. Sorption capacity of the soil for isoproturon was measured using batch experiments (0.29 litre kg⁻¹) and the results obtained here in agreement with those obtained under dynamic conditions. © 2000 Society of Chemical Industry     

Controlled release of aldicarb from carboxymethyl cellulose microspheres: in vitro and field applications

Aldicarb is a carbamate pesticide that is widely used throughout the world in the protection of crops (eg cotton, nuts, potatoes, onion, tobacco, sugar beet and sugar cane). In Turkey, especially in the Çukurova region, it is used for the control of the cotton white fly (Bemisia tabaci) which attacks cotton plants cultivated in this region. Aldicarb contamination in surface and ground water is a serious problem in several countries, partly due to its high water solubility. It is also highly toxic to mammals. In order to overcome these problems, microspheres of aldicarb were prepared using carboxymethyl cellulose (CMC) as the biodegradable support material cross-linked with aluminium chloride. A strong hysteresis behaviour was observed upon drying and reswelling. Encapsulation efficiency was in the range 12–23% and aldicarb contents of 5.7–10.3 mg per 100 mg of microspheres was achieved. In vitro release was distinctly Fickian, and Higuchi constants were very close to 0.5. Release in pots revealed that only one sample had a release capability for more than four weeks. In the cotton plot much longer durations of release (more than seven weeks) were observed while a commercial granular formulation released its content immediately. It was thus possible to construct a controlled pesticide release system that prolonged the bioavailability to about eight weeks. © 1999 Society of Chemical Industry     

环境响应型控制释放农药技术研究进展

为提高农药利用率,以菜籽粕 (rapeseed meal, RSM) 为基材,十八烷基三氯硅烷 (OTS) 与对氨基偶氮苯 (AAB) 为改性剂,通过浸涂法使OTS水解、自组装与缩聚,产生的聚十八烷基硅氧烷(PODS)通过自组装作用附着在RSM表面,同时将具有光致异构性的AAB附着在RSM表面,合成了具有光响应性的RSM-PODS/AAB唑啉草酯 (pinoxaden) 载体。采用傅立叶变换红外光谱、扫描电子显微镜、紫外-可见光谱(UV-Vis)和接触角测量装置对其结构和组成进行了表征。结果表明：改性后的RSM农药负载率比原始RSM提高了21.4%,在黑暗中72 h内唑啉草酯的累积释放率为83%,UV-Vis照射4 h累积释放率为95%,在阳光照射下6 h内累积释放率达92%。表明负载农药的RSM-PODS/AAB具有良好的UV-Vis和太阳光控制释放性能,此光响应亲脂农药载体通过UV-Vis和阳光响应行为可有效控制药物释放行为。     

可降解聚碳酸亚丙酯-毒死蜱微胶囊的制备及缓释性能评价

以聚碳酸亚丙酯(PPC)为壁材,聚乙烯醇-1788(PVA-1788)为连续相稳定剂,采用乳化溶剂挥发法制备了包裹毒死蜱的可降解微胶囊。测定了PVA-1788的质量分数、PPC的质量浓度以及PPC与毒死蜱的质量比对微胶囊性能的影响。采用土壤悬浊拟环境实验法评价了PPC的降解性能;通过光学显微镜(OM)、扫描电子显微镜(SEM)、广角X射线衍射(W-XRD)、激光粒度分布仪和高效液相色谱(HPLC)等表征了PPC-毒死蜱微胶囊的性能,同时采用柱层析法探讨了其缓释性能。结果表明:PPC具有生物可降解性;PVA-1788质量分数、PPC质量浓度以及PPC与毒死蜱的质量比对微胶囊的性能有显著影响,当PVA-1788的质量分数为1.0%、PPC的质量浓度为110 mg/mL,PPC与毒死蜱的质量比为1∶2时,可获得球形规整、粒径较小、包封率与载药量较高的微胶囊,其平均粒径为7.3 μm,载药量为16.75%,包封率为89.34%。缓释性能研究结果表明,PPC微胶囊对毒死蜱具有明显的缓释效应, 27 d的累积释药率达86.87%。     

Organoclays for controlled release of the herbicide fenuron

Organoclays were assayed as matrices in which to associate herbicides, with the aim of decreasing product losses that could give rise to water contamination from agricultural activities. Fenuron was selected as model of a very mobile and highly water-soluble herbicide. Two different organoclays of high (A-HDT) and low (H-C18) reversible fenuron sorption were selected. Herbicide-organoclay complexes were prepared from the two organoclays and with two different fenuron contents (20 and 40 g AI kg-1) and two different mixing times, so as to form a series of weak and strong complexes. The release of fenuron from those complexes into water and water/soil suspensions gave values of T50 (time to release 50% of the fenuron content) ranging from 0.3 min to 2400 h. The total fenuron released in these closed systems ranged from 48 to 80% of the fenuron in the complex. The organoclay type (high or low sorptivity) had the greatest influence on fenuron release, followed by the strong or weak complex, suggesting that herbicide-organoclay interactions are the main factors controlling release. Soil column leaching experiments showed fenuron-organoclay complexes to be effective in reducing the peak herbicide concentration in the leachate to a half (6 microns) or a quarter (3 microns) of that obtained from the free technical compound (12 microns). Herbicide lost through leaching was reduced from 78% for the free technical fenuron to 50-30%, depending on the organoclay used as carrier and the strength of the complex. Bioassay with ryegrass showed that the weak fenuron/H-C18 complex (40 g AI kg-1) gave the same herbicidal activity as technical fenuron. The potential suitability of low-sorptive organoclays for conferring slow-release properties on the fenuron complex has been demonstrated.     

载体中蓟马聚集信息素组分的释放速率测定及其储藏温度筛选

为明确蓟马聚集信息素组分在2种常用载体中的释放规律,应用固相微萃取(SPME)和气相色谱-质谱联用技术测定不同聚集信息素剂量(1、10、100μg)和萃取时间(30、60、120 min)下SPME萃取头对载体中3种蓟马聚集信息素组分的萃取效率,筛选最佳萃取条件,并分析储藏温度对载体中蓟马聚集信息素组分释放速率的影响。结果表明,在橡胶塞和PVC管2种载体中,相同聚集信息素剂量下,与萃取30 min处理相比,萃取60、120 min时SPME萃取头对载体释放的3种聚集信息素组分的萃取效率或无显著差异,或随萃取时间增加而呈现降低趋势;相同萃取时间下,SPME萃取头对载体释放的3种聚集信息素组分的萃取效率均随剂量增加而显著增大。因此,测定载体中聚集信息素释放速率的最佳条件为萃取时间30 min、剂量100μg。室温25℃储藏条件下,橡胶塞和PVC管中3种聚集信息素组分的释放速率均在存储2 d时最高,之后随存放时间的延长而逐渐降低;-20℃储藏条件下,载体中3种聚集信息素组分的释放速率随着存放时间的延长相对稳定,56 d内释放速率均处于较高水平,且显著高于室温下储藏载体中聚集信息素组分的释放速率。表明-20℃储藏可有效减少载体中聚集信息素组分的损耗,即-20℃是聚集信息素载体储藏的适宜温度。     

磁性纳米粒子的制备及在转基因大豆检测中的应用

利用热分解法和表面4-羧基苯硼酸修饰,制备了用于转基因大豆提取基因组DNA的纳米粒子。制备的纳米粒子分散性好,磁响应性高。对比磁性纳米粒子和植物基因组DNA提取试剂盒提取转基因大豆基因组DNA的提取效果,结果表明,磁性纳米粒子提取转基因大豆基因组DNA的浓度明显高于试剂盒,实时荧光PCR检测转基因大豆的Ct值低于植物基因组提取试剂盒。     

汾河中下游土地生态系统固碳释氧动态测评

本文基于光能利用率模型测算净第一性生产(NPP)物质量,通过光合作用方程式换算固定CO_2和释放O_2的物质量,并采用造林成本法和工业制氧法对汾河中下游流域的固碳释氧价值量进行估算,旨在定量评价其固碳释氧价值的时空动态,为改善区域生态环境提供一定的参考。结果表明:(1)2000—2010年汾河中下游流域NPP物质总量共增加了18.3%,耕地的NPP物质总量占研究区NPP物质总量的50%以上,主要在于汾河下游为山西省主要的粮棉产区;(2)从固碳释氧来看,释氧O_2物质量随着固定CO_2物质量的增加而增加。固碳释氧价值总量由2000年的467.38×10~7元增加到552.24×10~7元,净增84.86×10~7元,增长率为18.16%。从大到小排序为:耕地草地林地其他地。(3)从县域行政空间来看,万荣县的单位面积NPP价值量和单位面积固碳释氧价值量均最高,而介休市均最低。表明汾河下游固碳释氧价值量较高,中游由于城市化进程的加快固碳释氧价值量较低,近年来退耕还林政策的落实使研究区生态环境趋势出现好转。但由于水热条件限制,区域林地增加不明显,以草地增加较为显著。