羧甲基纤维素-大豆分离蛋白农药缓释颗粒的制备及性能

为提高农药利用率、精确控制农药释放,设计了一种pH响应型缓释颗粒。以3-氨丙基三乙氧基硅烷（APTES）为桥连接羧甲基纤维素（CMC）与大豆分离蛋白（SP）得到羧甲基纤维素-大豆分离蛋白（CMC-SP）,然后利用分子自组装法负载阿维菌素（AVM）形成载药颗粒（CMC-SP@AVM）。采用红外光谱（FTIR）、扫描电镜（SEM）、热重分析（TGA）等手段对改性产物结构和形貌进行表征,并对CMC-SP@AVM的载药性能、缓释性能、抗紫外性能、杀虫活性进行了探究。结果表明,CMC-SP@AVM具有近似椭圆形的结构,CMC-SP@AVM的平均粒径为104nm;对AVM的包封率达41.9%,并赋予AVM优异的抗紫外光分解性能,强紫外光照射120h后,CMC-SP@AVM中AVM的残留率比未包封的AVM高117%,其药物释放具有pH响应特性,pH越大,释放速率越快;药物释放过程符合Elovich模型。在相同AVM浓度下CMC-SP@AVM的杀虫活性与原药无显著差异。     

羧甲基壳聚糖-蓖麻油基聚氨酯农药缓释微球的制备及性能

以羧甲基壳聚糖（CMCS）、蓖麻油（CO）和异佛尔酮二异氰酸酯（IPDI）为原料，自乳化法制备了羧甲基壳聚糖-蓖麻油基聚氨酯微球（CO-CMCS-PU），通过分子自组装法负载阿维菌素（AVM）得到载药微球（CO-CMCS-PU@AVM）。采用FTIR、1HNMR、SEM、TGA等对产品结构及形貌进行表征，并探究了不同药量载药微球的包封率、缓释性能、抗紫外性能、叶面接触角和黏附性能。结果表明，相比AVM分散液，紫外照射后载药微球中AVM的保留率提高到43%，说明CO-CMCS-PU载体的抗紫外性能良好；载药微球比AVM分散液在黄瓜叶面上的接触角降低了20%以上，滞留量提高了40%以上，说明其在叶面上有较好的黏附性和润湿性；载药微球包封率可达80%以上，具有良好的缓释和pH响应释放性能，释药行为符合First-order动力学模型，药物释放受Fickian扩散控制。     

叶面亲和型阿维菌素微胶囊的制备及pH响应性释放性能

为减少农药流失，设计了一种叶面亲和型缓释微胶囊。以甲基丙烯酸甲酯（MMA）接枝改性羧甲基纤维素（CMC）得到羧甲基纤维素-聚甲基丙烯酸甲酯（CMC-g-PMMA），然后利用自组装负载阿维菌素（AVM）形成载药微胶囊（CMC-g-PMMA@AVM），通过多巴胺（DA）包覆提高CMC-g-PMMA@AVM的叶面亲和性。采用扫描电镜、红外光谱、热重分析等对其结构和形貌进行表征，研究了微胶囊的载药性能、叶面亲和性及响应释放性能。结果显示，DA/CMC-g-PMMA@AVM为平均粒径126nm的球形粒子，多巴胺的包覆可有效提高微胶囊的载药性能，包封率可达88.56%；增强AVM的叶面亲和性，使其叶面滞留量相对于阿维菌素水乳液提升30.56%；赋予AVM优异的抗紫外光分解性能，强紫外光照射60min后，由AVM水乳液中AVM的残留率14.03%提高到DA/CMC-g-PMMA@AVM中的59.55%。载药微胶囊中药物释放具有pH响应，在pH=5条件下出现爆释，药物释放过程符合Weibull模型，受Fick扩散控制。     

木质素季铵盐-海藻酸钠聚合物负载阿维菌素粉体的制备及抗紫外光性能分析

以三甲基木质素季铵盐-海藻酸钠(QL-SA)为载体,用物理混合法制备了阿维菌素缓释聚合物(AVM-QL-SA),利用FT-IR对其结构进行了表征,探讨了交联剂用量、药物加入量、体系pH值等因素对载药量和包封率的影响,并对其缓释性能和抗紫外光降解进行了研究。结果表明:阿维菌素(AVM)均匀的混合在QL-SA载体中,主要以物理混合为主;最佳制备条件为:戊二醛为5%(以单体质量分数计)、药物加入量为1%(以单体质量分数计)、体系pH值为8.5,载药量和包封率分别达到1.36%和73.36%;阿维菌素缓释聚合物粒径符合正态分布,平均粒径为83.90 μm;阿维菌素缓释聚合物具有很好的缓释性能,在乙醇/水(体积比1:1)中释放30 h,累计释放率为88.97%;经8 h紫外光照射,阿维菌素原药中AVM残留量为6.24%,阿维菌素缓释聚合物中AVM残留量为37.75%,具有良好的抗紫外分解性能。     

二硫化钼纳米花球负载阿霉素对癌细胞的光热-化疗协同治疗作用

以钼酸钠、硫脲、柠檬酸及PEG-400为原料,通过水热法制备纳米MoS₂,考察了材料的光热转换性能及其对阿霉素（DOX）的负载及控释性能,并探讨了该载药体系对癌细胞的光热-化疗协同治疗作用。结果表明,通过该水热反应体系制备的尺寸约500 nm花球状MoS₂纳米材料具有良好的光热转换性能,对DOX的负载率可以达到136.8%,且其释药行为具有pH响应性,pH=5.8时DOX的累积释放量达到70.29%,约为pH=7.4条件下的7倍,表明该材料在药物负载/控释方面具有一定应用价值。此外,负载DOX后的MoS₂-DOX的纳米复合物在近红外光照射下对肝癌细胞HuH-7的抑制率高达92.09%,抑制效果明显高于单一的光热治疗和化疗。     

5-氟脲嘧啶载O-羧甲基壳聚糖自组装pH敏感纳米粒的体外释放

为了提高抗癌药物5-氟脲嘧啶(5-FU)对肿瘤细胞的靶向性及选择性,采用超声-透析法制备了具有pH敏感性的纳米药物载体5β-胆烷酸/O-羧甲基壳聚糖/磺胺地托辛(5β-CHA/OCMC/SDM)自组装水凝胶纳米粒,并用同样的方法将5-FU包载于纳米载体中进行体外释放研究。利用紫外分光光度计于269nm波长下检测5-FU的载药量和包封率以及释放浓度。结果表明,对于5β-CHA/OCMC/SDM纳米粒,药载比(药物和载体的质量比)增加到0.6时,载药量和包封率分别高达51.3%和85.4%。体外释药结果表明,在pH=7.4(人体正常组织的pH值)的磷酸盐缓冲溶液中,接枝5β-CHA的OCMC水凝胶纳米粒对5-FU具有良好的缓释效果,且随接枝量的增加缓释效果增强。pH6.8(肿瘤组织的pH值)时,接枝SDM的载药纳米粒迅速聚集并强烈释放,表现出良好的pH敏感性。     

β-环糊精/海藻酸钠水凝胶的制备及性能研究

将海藻酸钠(SA)和β-环糊精(β-CD)共混制备了复合水凝胶,并讨论了交联剂浓度、原料配比对水凝胶溶胀性能的影响。结果表明,当两者的共混比例为1∶2、w(交联剂)为6%、交联时间为1h时,水凝胶的溶胀性能较好。水凝胶在pH=1.2时的溶胀率仅为1.2,而在pH=7.4时的溶胀率达到14.2,具有良好的pH敏感性。以牛血清蛋白(BSA)为模型药物,研究了β-CD/SA水凝胶作为药物载体对BSA的负载及释放性能,结果表明:在模拟胃液中的累计释放量较小(21.5%),且释放速率较慢;在模拟肠液中的累计释放量为70.2%,具有良好的pH敏感控制释放性能。     

pH响应性阿维菌素/介孔硅的一步合成与释放

以三嵌段共聚物F127（(EO)106(PO)70(EO)106）为模板剂,正硅酸甲酯（TMOS）为硅源,阿维菌素(AVM)为模型药物,通过一步法合成载药介孔硅材料(HOMS),采用铜、锌、锰3种金属离子改性,形成具有pH响应性的缓释材料AVM/Zn-HOMS、AVM/Cu-HOMS和AVM/Mn-HOMS,借助FTIR、SEM、N2吸附-脱附法和TGA表征了缓释材料,并研究了其在不同pH下的释放行为。结果表明,AVM/Zn-HOMS、AVM/Cu-HOMS和AVM/Mn-HOMS材料表面分别呈现层状、疏松多孔状以及气泡状结构,比表面积分别为308.581、101.218和318.011 m2/g,氮气吸附-脱附等温线类型为具有H2型滞后环的Langmuir Ⅳ型。AVM/Zn-HOMS和AVM/Cu-HOMS呈现良好的pH响应性,AVM/Mn-HOMS则未表现出明显的pH响应性,3种材料的缓释行为均可用Higuchi动力学模型描述,释放过程受扩散机制控制。     

PDMDAAC改性玉米醇溶蛋白负载阿维菌素纳米颗粒的制备与性能

为提高阿维菌素叶面沉积率及其抗紫外分解性能,本文设计构建了叶面亲和的纳米载体。通过自由基聚合将聚二甲基二烯丙基氯化铵（PDMDAAC）改性玉米醇溶蛋白（Zein）,得到表面携带正电荷的改性玉米醇溶蛋白,并将其用于负载阿维菌素。采用红外光谱（FTIR）、扫描电镜（SEM）等手段对改性产物结构和形貌进行表征。通过反溶剂沉淀法制备了平均粒径为64.92nm的载药纳米粒子,载体对阿维菌素的包封率为(34.75±0.18)%。与植物表面的静电作用提升了纳米粒子悬浮液在植物表面的润湿性能,接触角大小随PDMDAAC接枝量增大而降低,由77.38°减小到64.60°;叶面滞留量可达33.69mg/cm²。改性玉米醇溶蛋白对阿维菌素的包覆提升了其抗紫外性能,半衰期由15min延长至40min,且阿维菌素的释放速率可通过PDMDAAC接枝率进行调控。     

六元瓜环对乌纠中黄酮类成分芦丁的缓释性能研究

为研究六元瓜环对芦丁的溶解度及其缓释性能,利用紫外-可见吸收光谱法研究了六元瓜环与芦丁的相互作用以及pH对其作用的影响。结果表明,六元瓜环与芦丁形成了摩尔比1:1的主客体包结物,包结平衡常数为3.6×105L/mol。芦丁原药,Q[6]-芦丁包结物在人工胃液(pH=1.2)中60 min内的累计释放度分别为60.19%、46.71%,在人工肠液(pH=6.8)中的累计释放度分别为73.76%、48.58%,且缓释曲线非常相似。瓜环-芦丁主客体包结物的体外累积释放度明显低于芦丁原药,Q[6]对芦丁均有明显的体外缓释作用。     

Synthesis of pH-responsive isolated soy protein/carboxymethyl chitosan microspheres for sustained pesticide release

In order to improve the utilization rate of avermectin (AVM), a complex was prepared by electrostatic self-assembly using isolated soy protein (ISP) and carboxymethyl chitosan (CMCS) for loading AVM to obtain ISP/CMCS@AVM microspheres. The encapsulation efficiency (EE), sustained release property, ultraviolet (UV) protective ability, and toxicity of the microspheres were evaluated, and the release kinetics of AVM from the microsphere at different pHs were investigated. The results demonstrated that the average particle size of ISP/CMCS@AVM was 283.95 nm, and the EE reached 88.42% for AVM after denaturation. After 70 h of exposure to UV light, the residual rate of AVM in ISP/CMCS@AVM was 78.12%, which was significantly higher than 35.18% in the AVM emulsion. Moreover, the formulation imparted pH sensitivity and sustained-release property to AVM and was consistent with the Korsmeyer–Peppas model, controlled by Fick diffusion. Finally, the insecticidal toxicity of ISP/CMCS@AVM did not differ significantly from that of unmodified AVM. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48358.     

基于静电纺丝技术的农药传递体系的制备与性能表征

为获得一种新型高载药量、易分散型农药制剂,基于药物传递理论,以阿维菌素（AVM）为农药模型,以乙基纤维素（EC）为主要农药载体,以卡波姆（CB）为改性材料,利用静电纺纳米纤维载药技术构建一种具有微纳结构的农药传递体系。通过对复配比例、溶解参数及纺丝条件的探索,结果表明：采用N,N-二甲基乙酰胺与乙醇以体积比3∶1的混合溶剂对载体材料EC与CB分别进行溶解,EC与CB纺丝液的体积复配比为1∶1时,农药传递体系的载药量可高达35.7%,包封率接近100%,耐光解性大幅提升。并且,该农药传递体系的水分散性非常优异,具有长效释药性。     

Elaboration of a feather keratin/carboxymethyl cellulose complex exhibiting pH sensitivity for sustained pesticide release

Feather keratin (FK) and carboxymethyl cellulose (CMC) were used as raw materials to prepare a FK/CMC polyelectrolyte complex via electrostatic interactions. Using avermectin (AVM) as a model drug and elevated temperature, an FK/CMC@AVM drug-carrying complex was obtained. The structure and morphology of FK/CMC@AVM were both analyzed by Fourier transform infrared spectroscopy, dynamic light scattering, and scanning electron microscopy (SEM). Furthermore, the encapsulation efficiency, anti-ultraviolet, sustained release, and toxicity properties of FK/CMC@AVM were studied. The results showed that the average particle size of FK/CMC@AVM was 386.57 nm and the encapsulation efficiency was 67.06%. Under UV light irradiation, FK/CMC@AVM significantly improved the stability of AVM and the half-life of AVM was found to be delayed from 354 to 1800 min. Moreover, the sustained release of AVM featured pH sensitivity and was consistent with the Korsmeyer–Peppas model. Upon increasing the pH from 1.5 to 9.5, the release mechanism of AVM changed from Fick diffusion to non-Fick diffusion. Finally, the toxicity characteristics of FK/CMC@AVM were not significantly different from those of nonmodified AVM. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47160.     

Time-dependent pH sensing phenomena using CdSe/ZnS quantum dots in EIS structure

Time-dependent pH sensing phenomena of the core-shell CdSe/ZnS quantum dot (QD) sensors in EIS (electrolyte insulator semiconductor) structure have been investigated for the first time. The quantum dots are immobilized by chaperonin GroEL protein, which are observed by both atomic force microscope and scanning electron microscope. The diameter of one QD is approximately 6.5 nm. The QDs are not oxidized over a long time and core-shell CdSe/ZnS are confirmed by X-ray photon spectroscopy. The sensors are studied for sensing of hydrogen ions concentration in different buffer solutions at broad pH range of 2 to 12. The QD sensors show improved sensitivity (38 to 55 mV/pH) as compared to bare SiO₂ sensor (36 to 23 mV/pH) with time period of 0 to 24 months, owing to the reduction of defects in the QDs. Therefore, the differential sensitivity of the QD sensors with respect to the bare SiO₂ sensors is improved from 2 to 32 mV/pH for the time period of 0 to 24 months. After 24 months, the sensitivity of the QD sensors is close to ideal Nernstian response with good linearity of 99.96%. Stability and repeatability of the QD sensors show low drift (10 mV for 10 cycles) as well as small hysteresis characteristics (<10 mV). This QD sensor is very useful for future human disease diagnostics.     

Preparation and release of avermectin‐loaded cellulose acetate ultrafinefibers

In this study, avermectin (AVM) was successfully dispersed in a cellulose acetate (CA) solution. CA/AVM composite fibers were fabricated by electrospinning the blending solution containing different amounts of AVM. Further investigation indicated that the composite fibers showed continuously changed morphologies with the concentration of AVM increasing. The electrospun fibers were characterized by field emission scanning electron microscope, X‐ray diffraction, Fourier transform infrared spectroscopy, and thermal gravimetric analysis. The release behavior of the composite fibers was studied at pH = 7.4 and buffer media at 27°C and the amounts of AVM at different release steps were determined by high performance liquid chromatography analysis. Furthermore, AVM release from the CA/AVM samples showed two stages‐initial fast and later slow release. The two stages supplied a continuous release to achieve the effective utilization of AVM. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Synthesis of hyperbranched poly(3‐methyl‐3‐hydroxymethyloxetane) and their application to separate basic proteins by adsorption coated column

A series of hyperbranched poly(3‐methyl‐3‐hydroxymethyloxetane)s with different degree of branching were synthesized using BF₃·OEt₂ as initiator and coated on the inner surface of the fused‐silica capillaries. In the pH range of 3–9, the coated capillaries reduced electro‐osmotic flow by about four times lower than the bare fused‐silica capillary. The coated capillaries also displayed good resistance to adsorption of cationic proteins, providing clean separations of a mixture of Lysozyme, Cytochrome c, and Ribonuclease A around pH 3–6 in phosphate buffer. The separation efficiency in terms of peak shape was excellent compared with bare fuse‐silica capillary. The separation efficiency of hyperbranched poly(3‐methyl‐3‐hydroxymethyloxetane) with degree of branching of 0.43‐coated capillary column for Lysozyme reached 10⁶ plates/m with a resolution of 7.1, and the coated capillary column had good migration time reproducibility. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010