靶向光敏剂NaYF4:Yb,Tm@ NaGdF4:Yb@TiO2@PEI-PAA-FA的制备和性能

采用水解法用TiO_2包覆上转换纳米粒子Na YF4:Yb,Tm@NaGdF4:Yb,然后修饰聚乙烯亚胺(PEI)和聚丙烯酸(PAA)并偶联叶酸(FA),制备了叶酸受体靶向纳米光敏剂(NaYF4∶Yb,Tm@NaGdF4∶Yb@TiO_2@PEIPAA-FA)。借助XRD和TEM表征NaYF4∶Yb,Tm@NaGdF4∶Yb@TiO_2的物相和形貌,FTIR和Zeta电位证实有机成分的成功修饰,并测试了产物的上转换发光光谱。结果表明:在980 nm近红外光(NIR)下,纳米光敏剂存在下的1,3-二苯基异苯并呋喃溶液吸收光谱的降低证明了单线态氧的产生。此外,纳米光敏剂可以载带阿霉素(DOX),最大载药率为50.8%,包封率为84.7%。载药后的纳米光敏剂中DOX释放对介质具有pH响应性,在NIR照射的酸性介质(pH=5.0)中12 h的累积缓释率为38.1%,远高于中性介质(pH=7.4)的10.4%。     

Lu2O3:Yb,Tm/MC540纳米材料的制备及研究

以水热反应及后续的高温煅烧过程为合成手段,成功制备了Lu₂O₃:Yb,Tm纳米材料。XRD结果显示所得样品为纯Lu₂O₃晶相。且SEM结果表明所得样品由不规则形状组成,粒径在100nm左右。随后通过搅拌吸附过程负载部花青(MC540)光敏剂,得到Lu₂O₃:Yb,Tm/MC540纳米材料。然后以肺癌细胞(A-549细胞)为模型,研究了Lu₂O₃:Yb,Tm/MC540纳米材料的抗肿瘤活性。结果表明,在650nm的红光照射下,上述材料对肺癌A-549细胞具有明显的光动力杀伤疗效。     

g-C3N4/TiO2复合材料制备及其处理罗丹明B研究

为高效去除有机染料，分别以g-C₃N₄和TiO₂为有机半导体和无机半导体原料，通过水热法合成一系列不同质量配比的g-C₃N₄/TiO₂复合材料，利用正交实验L₁₆(4⁵)探究g-C₃N₄/TiO₂复合材料处理罗丹明B模拟印染废水的最适宜工艺条件。结果表明，最适宜工艺条件为：光照时间为180 min、m(g-C3N4)∶m(TiO2)为20∶30、投加量为2.0 g/L、罗丹明B模拟印染废水质量浓度为20 mg/L、pH为6.50，此时罗丹明B去除率可达98.86%。而单一使用g-C₃N₄或TiO₂对比处理罗丹明B模拟印染废水的去除率分别为52.27%和89.71%，说明TiO₂掺杂g-C₃N₄后可以更好地发挥协同去除性...     

SiO2/C60/环氧树脂阻燃涂层的制备及性能表征

以十六烷基三甲基溴化铵(CTAB)、正硅酸乙酯(TEOS)、NaOH溶液、无水乙醇为原料，制得纳米SiO₂。将环氧树脂(EP)分别与SiO₂、富勒烯(C₆₀)通过超声法分散制备出3种涂层(SiO₂/EP、C₆₀/EP、SiO₂/C₆₀/EP)，并用X射线衍射仪(XRD)、扫描电子显微镜(SEM)对所制纳米SiO₂及涂层进行表征，通过差式扫描量热仪(DSC)、氧指数测定仪等对涂层热稳定性及阻燃性能进行测试。结果表明：SiO₂/C₆₀/EP涂层的综合性能最佳，当SiO₂、C₆₀、EP、聚酰胺固化剂651的质量比为25∶6∶300∶150时，涂层的综合性能最佳，其残炭率、氧指数、垂直燃烧等级、硬度分别为21.5%、32.5%、V-0级、6H。     

玉米淀粉/TiO2纳米复合薄膜制备与性能

以玉米淀粉为基质,结合纳米Ti O₂,通过超声分散采用流延法制备了可生物降解的淀粉/Ti O₂纳米复合薄膜,研究了纳米Ti O₂对薄膜拉伸性能、阻隔性能及抗菌活性的影响,采用扫描电子显微镜(SEM)、红外光谱仪(FTIR)和X射线衍射仪(XRD)对复合膜的微观形貌和结构进行了表征。结果表明,淀粉/Ti O₂纳米复合膜中Ti O₂与淀粉分子间存在缔合作用,含适量Ti O₂的复合膜组分之间有良好的相容性,与淀粉膜相比,纳米复合膜的拉伸性能和水蒸气阻隔性能得到有效改善,含0.8%Ti O₂(质量分数,下同)的纳米复合膜拉伸强度为7.54 MPa,比淀粉膜提高了53.9%,水蒸气透过系数为5.50×10^-5 g/(mm·d),较淀粉膜降低了23.5%,该复合膜同时表现出较好的紫外线隔离性能及抗菌活性。     

H3PW12O40/TiO2-SiO2光催化降解甲基红

采用溶胶-凝胶法制备TiO₂-SiO₂,用浸渍法将H₂PW₁₂O₄₀负载在TiO₂-SiO₂上,制得H₃PW₁₂O₄₀/TiO₂-SiO₂光催化剂。探究在模拟自然光条件下,光照时间、甲基红溶液初始浓度、催化剂用量和溶液pH对甲基红可见光催化降解的的影响。实验结果显示,在光照时间为15min.甲基红溶液初始浓度为15mg/L.催化剂用量为1.8g/L以及pH为2的优化条件下,甲基红的光降解率高达99.7%。光催化降解甲基红溶液为一级动力学反应。     

Ag3PO4/WO3复合光催化剂的制备及其可见光催化性能

通过原位沉淀法制备了Ag₃PO₄/WO₃复合光催化材料并用于降解盐酸四环素(TC),利用SEM、XRD、FTIR、XPS和UV-vis DRS等手段对合成材料的表观形貌、化学组成和分子结构等进行了表征,并以可见光下催化降解TC(10 mg/L)的效果来评价材料的光催化性能。与单一Ag₃PO₄和WO₃相比,可见光照射60 min后,Ag₃PO₄/WO₃复合材料对TC具有更高的光降解性能,WO₃质量分数为25%时性能最优,TC降解率达到最高84.82%,且经5次循环后仍具有较好的光催化活性。通过对自由基捕获试验以及对电子顺磁共振(ESR)光谱的分析,明确h⁺和O₂^·-为Ag₃PO₄/WO₃复合材料光催化降解TC过程中的主要活性物质,推断出Ag<...     

上转换@聚多巴胺纳米光热剂的制备及载药与抗菌性能

癌症和致病菌感染成为公共安全健康的严重威胁。采用反相微乳液法对上转换粒子NaYF₄∶Yb, Nd, Er@NaGdF₄∶Nd, Yb包裹聚多巴胺(PDA)并接枝聚乙烯亚胺(PEI),制备了核-壳结构纳米光热剂NaYF₄∶Yb, Nd, Er@NaGdF₄∶Nd, Yb@PDA-PEI,表征了产物的形貌、化学组成、光学性质、光热和药载/释药性能。结果表明，光热剂的光热能力随PDA壳的增厚而增强。在PEI接枝后，光热剂在水中的分散效果获得改善，但光热性能轻微减弱，对盐酸阿霉素(DOX)的载药量高达26.6%,体外药物释放过程具有pH依赖和近红外光响应特征。载带盐酸四环素的纳米光热剂在808 nm激光照射下对大肠杆菌的抗菌活性优于光热剂或盐酸四环素。研究结果为发展应用于抗肿瘤或抗感染治疗的纳米光热剂提供了新思路。     

氧化石墨烯负载纳米Fe3O4类芬顿处理制药废水

采用改进Hummer法制备了氧化石墨烯(GO)负载纳米Fe₃O₄磁性催化剂(Fe₃O₄/GO),对其进行了X射线衍射仪、扫描电子显微镜和能量-色散光谱表征,并将其应用于多相类芬顿处理高浓化学原料药生产废水。结果表明,Fe₃O₄颗粒成功负载在GO表面,且没有出现明显的团聚现象。当废水的pH为3,双氧水(H₂O₂的质量分数30%)投加量10 mL/L,催化剂投加量2 g/L,反应120 min后COD去除率达78%,UV254去除率高达81%。三维荧光光(3D-EEM)分析可知,芳香类和富里酸类物质在催化降解过程中得到有效去除。     

g-C3N4/BiVO4异质结的制备及其在环境治理中的应用

通过负载法成功制备了g-C₃N₄/BiVO₄异质结,采用XRD、SEM、BET、UV-Vis DRS、Mott Schottky、SPV等技术对样品的结构与性质进行分析,以光催化降解RhB和光催化还原CO₂评价其光催化活性。结果表明,g-C₃N₄和BiVO₄能带结构匹配,能够组成“Z”型异质结,并有效提高光生载流子的分离效率,同时保留g-C₃N₄导带电子较强的还原性和BiVO₄价带空穴较强的氧化性,最终提高光催化活性,其中当g-C₃N₄的负载量为3%时,样品展现了最佳的光催化活性,在光催化降解RhB实验中,经过180min光照后,降解率达到95.3%,反应速率常数达到0.0166min^-1;而在光催化还原CO₂的实验中,经过4h光照后,CO和O₂的产量达到70....     

Rational design and synthesis of upconversion luminescence-based optomagnetic multifunctional nanorattles for drug delivery

Optomagnetic multifunctional composite based on upconversion luminescence nanomaterial is regarded as a promising strategy for bioimaging,disease diagnosis and targeted delivery of drugs.To explore a mesoporous nanostructure with excellent water dispersibility and high drug-loading capacity,a novel nanorattle-structured Fe3O4@SiO2@NaYF4∶Yb,Er magnetic upconversion nanorattle (MUCNR) was suc-cessfully designed by using Fe3O4 as core and NaYF4∶Yb,Er nanocrystals as shell.The microstructures and crystal phase of the as-prepared MUCNRs were evaluated by transmission electron microscopy,X-ray powder diffraction and N2 adsorption/desorption isotherms.The Kirkendall effect was adapted to explain the formation mechanism of the MUCNRs.The loading content and encapsulation efficiency of doxorubicin hydrochloride (DOX) could reach as high as 18.2％ and 60.7％,respectively.Moreover,the DOX loading MUCNR (DOX-MUCNR) system showed excellent sustained drug release and strong pH-dependent performance,which was conducive to drug release at the slightly acidic microenvironment of tumor.Microcalorimetry was used to quantify the interactions between the carrier structure and drug release rate directly.The heat release rates in the heat-flow diagrams are basically consistent with the DOX release rate,thereby showing that microcalorimetry assay not only provides a unique thermody-namic explanation for the structure-activity relationship of Fe3O4@SiO2@NaYF4∶Yb,Er MUCNRs but also provides powerful guidance to avoid the blind selection or design of drug carriers.Therefore,our work firmly provided a comprehensive perspective for using Fe3O4@SiO2@NaYF4∶Yb,Er MUCNRs as a remark-able magnetic targeted drug carrier.     

Preparation and characterization of tetracycline‐loaded interpenetrating polymer networks of carboxymethyl cellulose and poly(acrylic acid): water sorption and drug release study

Tetracycline (TC)‐loaded ionic interpenetrating polymer networks (IPNs) of carboxymethyl cellulose (CMC) and crosslinked poly(acrylic acid) (PAA) were prepared and characterized by infrared spectral analysis, differential scanning calorimetry and scanning electron microscopy techniques. The prepared IPNs were evaluated for in vitro blood compatibility by clot formation and hemolysis methods and their water imbibitions capacity was determined. Fractional release dynamics of tetracycline was also investigated from loaded IPNs of CMC and PAA. The entrapped drug was examined for antibacterial activity and structural integrity and effects of various parameters such as percentage loading of the drug, chemical composition of the carrier IPN, pH and temperature of the release medium were investigated on the release profiles of TC. The drug was also released in different simulated biological fluids. Copyright © 2005 Society of Chemical Industry     

HNTs-NaClO2复合材料的制备及抑菌效果

由于抗生素耐药性的流行,新型抗菌材料日益受到关注。本文利用埃洛石（HNTs）独特的结构和性质,以经过碱法预处理的HNTs为载体,通过真空抽吸法制备了HNTs-NaClO₂复合材料。采用XRD、FTIR、TEM、EDS等手段对复合材料结构和化学组成进行表征,TEM显示负载NaClO₂的HNTs管体表面有明显的晶体出现。探索了不同负载工艺对NaClO₂负载量的影响,研究了HNTs-NaClO₂的释放性能和抑菌性能,通过急性经口毒性实验考察了HNTs-NaClO₂的生物安全性。结果表明,改变HNTs在饱和亚氯酸钠溶液中的搅拌时间和负载比例可以提高NaClO₂的负载量,在搅拌时间为2h时负载量为4.91%,在负载比例为1∶4时负载量为7.61%;释放在第4天时趋于稳定,释放的亚氯酸钠质量分数为1.43%;抑菌活性评价表明,该复合材料对大肠杆菌和金黄色葡萄球菌均有抑制作用;HNTs-NaClO₂对雌雄小鼠的LD₅₀均大于5.00g/kg_BW。HNTs-NaClO₂复合材料可稳定持续释放,且具有一定的抑菌性,属于低毒级别。     

One‐pot combustion synthesis and efficient broad spectrum photoactivity of Bi/BiOBr:Yb,Er/C photocatalyst

A highly efficient broad spectrum responsive Bi/BiOBr:Yb,Er/C ternary composite was synthesized by a simple one‐pot combustion method using nitrates and citric acid as raw materials. Experimental results show that Er³⁺/Yb³⁺ were successfully doped into BiOBr lattice, and metallic Bi nanoparticles and carbon species were formed simultaneously. Compared with pure BiOBr and Bi/BiOBr/C, as‐synthesized Bi/BiOBr:Yb,Er/C ternary photocatalyst is highly responsive in the UV‐visible‐NIR range, and possesses the best photodegradation performance for Rhodamine B, phenol, and imidacloprid under visible, NIR, or solar light irradiation, which can be attributed to the synergetic effects of surface plasma resonance of metallic Bi, up‐conversion transition of Er³⁺ and heterojunctions (Bi/BiOBr, Bi/C, and BiOBr/C). Moreover, a plausible mechanism was given, the main active species, and photostability of samples were studied. The solar light photoactivity and influences of pH value and anions (Cl^?, SO₄^2?, CO₃^2?, HCO₃^?, and NO₃^?) were also investigated. This study highlights the advantages of synergetic effects of SPR, up‐conversion and heterojunctions, which provides a useful guide toward the rational design of broad spectrum (UV‐visible‐near infrared) photocatalysts.     

In2S3/g-C3N4复合光催化剂的制备及其光催化降解四环素

本文分别采用热缩聚法和水热法合成了g-C₃N₄和In₂S₃,再用简单的机械研磨工艺制备出了In₂S₃/g-C₃N₄复合光催化剂。采用X射线衍射(XRD)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶变换红外光谱(FTIR)和紫外可见漫反射光谱(UV-Vis DRS)对In₂S₃/g-C₃N₄复合光催化剂的晶体结构、形貌、微观结构和光学性质进行了表征,在可见光照射下,通过降解四环素(TC)来评价其光催化活性。结果表明,研磨比例为1∶4(摩尔比)的In₂S₃/g-C₃N₄复合光催化剂表现出最佳的光催化性能,在氙灯下TC的光降解表观速率常数是0.025 1 min^-1,分别是In₂S₃和g-C₃N₄的2.9倍和1.6倍,在自然光下TC的光降解表观速率常数是0.010 4 min^-1,分别是In₂S₃和g-C₃N₄的2.6倍和1.4倍。In₂S₃/g-C₃N₄复合光催化剂优异的光催化性能归功于载流子的高效迁移和分离以及增强的光吸收能力。本研究为设计和开发用于抗生素废水处理的可见光响应光催化剂提供了一条有前景的途径。     

Preparation and in vitro characterization of poly(sebacic acid‐co‐ricinoleic acid)‐based tamoxifen citrate‐loaded microparticles for breast cancer

This study was aimed to develop an injectable polymeric drug delivery system for tamoxifen citrate (TC) using poly(sebacic acid‐co‐ricinoleic acid) [poly(SA‐RA) 70 : 30 w/w] as a drug carrier for the treatment of estrogen receptor positive breast cancer. Injectable biodegradable microparticles of TC were produced by solvent displacement technique of microencapsulation and were characterized by surface morphology (scanning electron microscopy), particle size, size distribution, physical and chemical interaction (Fourier transform infrared), nature and physical state of drug [DSC and X‐ray diffraction (XRD)], and in vitro release studies. TC loading over different concentrations was analyzed by high performance liquid chromatography (HPLC) technique. Polyanhydride microparticles obtained after lyophilization were nearly spherical in shape with smooth surface and size less than 2.5 μm. TC was dispersed in the form of amorphous state, and TC remains intact and stable during the process of microencapsulation. In vitro drug release studies demonstrated prolonged controlled release of TC with zero‐order kinetics. Stability studies revealed that the production process of microparticles itself did not affect the chemical stability of the drug and polymer forming the particle matrix. Significant difference in drug release capacity was observed in microparticles with different drug loadings, and the drug release was more sustained in microparticles prepared with high TC. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Triple-functional core-shell structured upconversion luminescent nanoparticles covalently grafted with photosensitizer for luminescent, magnetic resonance imaging and photodynamic therapy in vitro

Upconversion luminescent nanoparticles (UCNPs) have been widely used in many biochemical fields, due to their characteristic large anti-Stokes shifts, narrow emission bands, deep tissue penetration and minimal background interference. UCNPs-derived multifunctional materials that integrate the merits of UCNPs and other functional entities have also attracted extensive attention. Here in this paper we present a core-shell structured nanomaterial, namely, NaGdF(4):Yb,Er@CaF(2)@SiO(2)-PS, which is multifunctional in the fields of photodynamic therapy (PDT), magnetic resonance imaging (MRI) and fluorescence/luminescence imaging. The NaGdF(4):Yb,Er@CaF(2) nanophosphors (10 nm in diameter) were prepared via sequential thermolysis, and mesoporous silica was coated as shell layer, in which photosensitizer (PS, hematoporphyrin and silicon phthalocyanine dihydroxide) was covalently grafted. The silica shell improved the dispersibility of hydrophobic PS molecules in aqueous environments, and the covalent linkage stably anchored the PS molecules in the silica shell. Under excitation at 980 nm, the as-fabricated nanomaterial gave luminescence bands at 550 nm and 660 nm. One luminescent peak could be used for fluorescence imaging and the other was suitable for the absorption of PS to generate singlet oxygen for killing cancer cells. The PDT performance was investigated using a singlet oxygen indicator, and was investigated in vitro in HeLa cells using a fluorescent probe. Meanwhile, the nanomaterial displayed low dark cytotoxicity and near-infrared (NIR) image in HeLa cells. Further, benefiting from the paramagnetic Gd(3+) ions in the core, the nanomaterial could be used as a contrast agent for magnetic resonance imaging (MRI). Compared with the clinical commercial contrast agent Gd-DTPA, the as-fabricated nanomaterial showed a comparable longitudinal relaxivities value (r(1)) and similar imaging effect.     

Development of Biocompatible and Antibacterial Collagen Hydrogels via Dialdehyde Polysaccharide Modification and Tetracycline Hydrochloride Loading

Nowadays, collagen hydrogels with both good physicochemical and antibacterial properties for tissue engineering have drawn broad attention. Herein, a biocompatible and antibacterial collagen hydrogel is developed via alginate dialdehyde (ADA) modification and tetracycline hydrochloride (TC) loading based on Schiff's base formation. Fourier transform infrared spectroscopy and X‐ray diffraction spectra suggest the maintenance of collagen structure integrity after ADA modification. The modification significantly contributes to the improved swelling property, resistance against type I collagenase, and strengthens storage modulus of hydrogels with an increase of ADA concentrations. Meanwhile, dynamic release curves of tetracycline hydrochloride (TC)‐loaded hydrogels describe the burst release at the first 15 min then a gradual release, hydrogels act ideally as carriers in antibacterial activity. Furthermore, in vitro biocompatibility and antibacterial properties are successfully confirmed from the fabricated collagen hydrogels. This physicochemical‐ and antibacterial‐property–improved collagen hydrogel would be a potential candidate for wound healing as a scaffold.     

Near-infrared (1550 nm) in vivo bioimaging based on rare-earth doped ceramic nanophosphors modified with PEG-b-poly(4-vinylbenzylphosphonate)

A novel poly(ethylene glycol) (PEG)-based block copolymer possessing a 4-vinylbenzylphosphonate repeating unit in another segment (PEG-block-poly(4-vinylbenzylphosphonate)) (PEG-b-PVBP) was designed and successfully synthesized. As a control, an end-functionalized PEG possessing a mono-phosphonate group (PEG-PO(3)H(2)) was also synthesized. The surface of near-infrared (NIR) phosphors (i.e., ytterbium (Yb) and erbium (Er) ion-codoped Y(2)O(3) nanoparticles (YNPs)) were modified with PEG-b-PVBP (PEG-YNP(b)s) and PEG-PO(3)H(2) (PEG-YNP(1)s). The adsorption of PEG-b-PVBP and PEG-PO(3)H(2) was estimated by Fourier transform infrared (FT-IR) measurements and thermal gravimetric analysis (TGA). The physicochemical characteristics of the obtained YNP samples were analyzed by ζ-potential and dynamic light scattering (DLS) measurements. The ζ-potentials of YNPs modified by these polymers were close to zero, indicating the effective coverage of the YNP surface by our new PEG derivatives. However, the dispersion stability of the PEGylated YNPs was strongly affected by the structure of the PEG terminus. The average diameter of the PEG-YNP(1)s increased, and aggregates precipitated after less than 1 h in phosphate buffer saline (PBS). In contrast, the size did not change at all in the case of PEG-YNP(b)s and the dispersion in PBS was stable for over 1 week. PEG-YNP(b)s also showed high erosion resistance under acidic conditions. The multiple coordinated PVBP segment of the block copolymer on the YNP surface plays a substantial role in improving such dispersion stability. The excellent dispersion stability and strong NIR luminescence of the obtained PEG-YNP(b)s were also confirmed in fetal bovine serum (FBS) solution over 1 week. Furthermore, in vivo NIR imaging of live mice was performed, and the 1550 nm NIR emission of PEG-YNP(b)s from the organ of live mice was confirmed without dissection.     

改性BaFe2O4载氧体生物质化学链气化特性

以溶胶凝胶法制备了BaFe₂O₄载氧体以及Ni、Ce、K修饰的BaFe₂O₄载氧体,筛选出最佳载氧体为10%(质量)K修饰的BaFe₂O₄载氧体(10K-BF),探究了不同反应条件对其性能的影响,通过H₂-TPR、XRD、SEM、BET对载氧体表征。实验结果表明,Ni、Ce、K的添加均提高了载氧体的合成气产率,10K-BF载氧体在水蒸气与生物质质量比(S/B)等于3,过氧系数α=0.20,反应温度800℃时,气化效果最好,合成气产率1.864 m³/(kg Biomass),氢气产率1.038 m³/(kg Biomass),碳转化率90.49%,积炭率1.33%,10次循环后仍有较高的气体产率及碳转化率。H₂-TPR表明10K-BF载氧体在300℃开始释氧,在生物质热解的初始阶段即可参与反应,有利于焦油的裂解;XRD表明10K-BF载氧体再生后可以恢复部分尖晶石结构。