交联β-环糊精聚合物/Fe3O4核壳结构复合纳米颗粒的制备和性能研究

以羧甲基-β-环糊精为表面修饰剂对Fe3O4纳米粒子进行包覆修饰,以环氧氯丙烷为交联剂,在β-环糊精的碱性溶液中通过Fe3O4纳米粒子表面进行的交联反应制备了交联β-环糊精聚合物/Fe3O4复合纳米颗粒.利用FTIR、XRD、TEM和TGA分剐对复合纳米颗粒的结构、形貌和尺寸进行了表征.结果表明,制备的复合纳米颗粒为近球形、核壳结构,粒径约为10～20nm,环糊精聚合物含量为29%,在水中的分散性良好.磁性能测试和包合性能测试表明,复合纳米颗粒为超顺磁性,对特定分子具有一定的包合能力,可用于靶向给药系统和特定物质分离的载体.     

磁性纳米粒子的制备及环糊精葡萄糖基转移酶的固定化

采用化学共沉淀法制备Fe_3O_4纳米粒子,并依次以正硅酸四乙酯(TEOS)为硅源、以3-氨丙基三乙氧基硅烷(APTES)为硅烷偶联剂对磁性纳米粒子进行表面修饰,最终得到氨基硅烷化的磁性纳米粒子(Fe_3O_4@SiO_2-NH_2)。采用透射电子显微镜(TEM)、扫描电子显微镜(SEM)、傅里叶红外光谱分析仪(FTIR)、X射线衍射(XRD)、振动样品磁强计(VSM)和热重分析仪(TGA)对磁性纳米粒子的形态、结构进行表征。结果表明,氨基硅烷化的磁性纳米粒子具有良好的超顺磁性,结晶度高,稳定性好,粒径约为22 nm。利用该磁性材料固定化海洋环糊精葡萄糖基转移酶(CGTase)得,固定化酶热稳定性,对酸碱的耐受性和储存稳定性明显优于游离酶。     

氨基修饰磁性氧化铁纳米粒子的制备

以聚乙二醇(PEG)为溶剂,高温热分解乙酰丙酮铁(Fe(acac)3)合成了磁性氧化铁纳米粒子。为改善氧化铁纳米粒子表面性能和生物应用潜能,分别用N,N二甲基甲酰胺和聚酰胺-胺(PAMAM)进行表面修饰,在氧化铁纳米粒子表面接枝-NH2活性官能团。分别采用X射线衍射仪(XRD)、透射电镜(TEM)、红外光谱(FT-IR)、动态光散射(DSL)对样品进行了表征测试。XRD和TEM结果表明高温热分解法合成的纳米粒子平均粒径为10nm,具有较好的结晶性和单分散性;FT-IR、DSL粒径和表面电位测试结果表明氨基官能团成功修饰在氧化铁纳米粒子表面,同时使氧化铁纳米粒子在水溶液中的稳定性增强。     

Mg(OH)_2-PMMA复合粒子的制备及表征EI北大核心

为了减小纳米氢氧化镁较严重的团聚问题,通过在氢氧化镁表面接枝大分子聚甲基丙烯酸甲酯(PMMA)来制备氢氧化镁/PMMA纳米复合粒子,以提高纳米复合粒子在有机相中的相容性和分散性。首先,通过油酸对氢氧化镁进行表面修饰,在其表面引入双键烯烃基团,然后以丙烯酸甲酯(MMA)为单体,偶氮二异丁腈(AIBN)为引发剂,聚乙烯吡咯烷酮(PVP)为稳定剂,通过分散聚合的方法在修饰过的氢氧化镁表面接枝有机大分子PMMA。通过XRD、FT-IR、TGA、FESEM、EDS和沉降实验对所得Mg(OH)2/PMMA纳米复合粒子进行了测试表征,结果表明:有机大分子PM-MA成功地接枝在了油酸修饰后的Mg(OH)2表面上,纳米复合粒子在有机相中的分散性和相容性都得到了很大的提高。     

原位聚合法制备水溶性高聚物修饰的NaYF4：Yb,Er

采用原位聚合法,以聚丙烯酸（PAA）和聚乙烯吡咯烷酮（PVP）为壳层材料,对NaYF4上转换发光材料表面进行了PAA和PVP的修饰,傅立叶红外吸收光谱和热重分析证明了NaYF4纳米粒子表面有PAA和PVP的存在,透射电镜显示,当反应温度在0℃,丙烯酸单体含量为8.0wt%,反应时间130min时,PAA修饰的纳米粒子微观形貌最佳;当反应温度在60℃,乙烯基吡咯烷酮单体含量在12.0wt%,反应时间在150min的条件下,PVP修饰的纳米粒子微观形貌最佳。上转换荧光测试结果证明,在对材料进行NaYF4无机壳层包覆后再进行水溶性高聚物修饰,能够使其荧光性能保持不变。     

ZnS/PVA纳米复合薄膜的制备与表征

采用提拉真空干燥的方法制备出以石英玻璃为基板的ZnS/PVA纳米复合薄膜.ZnS/PVA纳米复合溶胶是通过直接混合法将ZnS纳米粒子与聚乙烯醇(PVA)高分子材料水溶液直接混合制备得到.ZnS纳米粒子由微乳液法制备得到.利用透射电子显微镜(TEM)和X射线衍射(XRD)分析表征了ZnS纳米粒子的微观形貌和晶型,TEM结果表明C12H25SH与Zn2 的比例越大,ZnS粒子的粒径越小且在PVA中的分散越好,当C12H25SH/Zn2 的比例为8∶1时,ZnS纳米粒子的粒径为50 nm,呈球状;XRD分析表明,PVA中ZnS纳米粒子具有类似于立方β-ZnS晶相.用紫外-可见(UV-VIS)吸收光谱和荧光光谱(PL)对其光学性能进行了表征,结果表明随着C12H25SH/Zn2 的摩尔比从4:1增长到8:1,ZnS/PVA纳米复合薄膜的吸收峰的强度逐渐增强,峰位也逐渐向短波长方向偏移.在280 nm下激发,PL中出现了峰位位于365 nm处的荧光发射峰;并且发现随着C12H25SH/Zn2 摩尔比从2:1增大到8:1,在C12H25SH/Zn2 摩尔比为4:1时,荧光发射峰的强度相对较大, 其余的荧光发射峰蓝移并且强度增大,表现出较为明显的量子尺寸效应;当C12H25SH/Zn2 摩尔比较大时,出现了低能发光(450 nm～467 nm)的现象.     

新型纳米基因载体(PEI/Mn0.5Zn0.5Fe2O4)的制备、表征及体外实验

采用改良的化学共沉淀法制备锰锌铁氧体磁性纳米粒子,聚乙烯亚胺(PEI)对其进行表面修饰.利用XRD、EDS、TEM、SEM、FTIR、XPS、UV-vis、Zeta电位仪、电泳仪、荧光显微镜等手段对其形貌、物象、成份、表面包覆功能团、元素组成、表面电位、磁响应性、DNA结合保护、体外释放及转染能力进行表征.体外加热实验验证其升温恒温能力.XRD及EDS确认已成功制备锰锌铁氧体磁性纳米粒子.修饰后的磁性纳米粒子具有良好的分散性、磁响应性及升温恒温能力.红外光谱及XPS分析验证了PEI在磁性纳米粒子表面的吸附.修饰后磁性纳米粒子的等电点由pH=7.0移至pH=11.0.具有良好的DNA结合保护转染能力.有利于其在生物医学领域的应用.     

静电纺纳米粘土/亚麻复合纳米纤维的制备及表征

利用静电纺丝技术制备了纳米粘土/亚麻落麻复合纳米纤维,其中亚麻落麻纤维溶解在分散有纳米粘土的4-甲基吗啉-N-氧化物(NMMO)/水的混合体系中。探究了纳米粘土和亚麻落麻的浓度、纺丝条件对纺丝工艺的影响。采用光学显微镜、SEM、TEM、FTIR、XRD和TGA测试了复合纳米纤维的微观形貌、结构及热学行为。结果表明:亚麻纤维浓度为1%时,可纺制成丝,且纳米粘土的加入可有效地改善纤维的细度和均匀性;TEM测试结果表明:纳米粘土已成功附着在纳米纤维上,但分散性有待进一步提高;FTIR和XRD结果表明:纳米粘土成功附着在亚麻纤维中,且存在于亚麻纳米纤维和粘土/亚麻复合纳米纤维中的纤维素为纤维素II型结晶;TGA分析表明:纳米粘土的引入可显著提高亚麻纤维的热稳定性。     

表面活性剂对纳米ZnS电极材料电化学性能的影响

采用溶剂热法通过表面活性剂PVP改性所合成纳米ZnS电极材料。XRD、SEM、TEM测试结果表明,经表面活性剂PVP改性后的纳米ZnS结晶度明显提升,具有更完整的晶体结构;并且改性后产物晶粒尺寸更加均一,球形形貌更加完整,团聚现象明显改善。电化学性能测试结果表明,PVP改性后的纳米ZnS负极材料表现出更佳的循环稳定性,其首次可逆比容量可达到557.7 mAh/g,循环50次后可逆比容量仍保持在420 mAh/g,电化学性能明显高于改性前ZnS电极材料。     

Fe掺杂ZnS半导体纳米晶的微乳液法制备及其性能研究

采用Span 80/Tween 80/cyclohexane/wa-ter微乳液体系合成了ZnS∶Fe纳米晶,分别利用XRD、TEM、荧光光谱对其相结构、形貌及光学性能进行了研究。结果表明合成的ZnS∶Fe纳米晶为球形,平均粒度约3nm。随着Fe离子掺杂浓度的增加,发光峰强度先增大后减小,浓度为1%的时候发光峰强最大。对ZnS∶Fe纳米晶的荧光衰减曲线进行测试并计算得到其荧光寿命为3.07ns。     

水溶性ZnS量子点的共沉淀法制备、 表征及其光学性能

以硫化钠和乙酸锌为反应物,3-巯基丙酸为表面包覆剂,利用共沉淀法制备了水溶性ZnS量子点。并采用X射线衍射仪、透射电子显微镜和荧光分光光度计等对样品的结构、形貌、粒径和光学性能进行了表征。结果表明:所得样品为ZnS立方型闪锌矿结构,量子点的形状呈不规则球形,粒径主要集中在4.8nm左右;样品在585～590nm之间出现了黄色荧光发射波峰。同时,利用红外光谱对ZnS量子点的合成机理进行了初步分析。     

Effect of swift heavy ion irradiation on bare and coated ZnS quantum dots

The present study compares structural and optical modifications of bare and silica (SiO₂) coated ZnS quantum dots under swift heavy ion (SHI) irradiation. Bare and silica coated ZnS quantum dots were prepared following an inexpensive chemical route using polyvinyl alcohol (PVA) as the dielectric host matrix. X-ray diffraction (XRD) and transmission electron microscopy (TEM) study of the samples show the formation of almost spherical ZnS quantum dots. The UV-Vis absorption spectra reveal blue shift relative to bulk material in absorption energy while photoluminescence (PL) spectra suggests that surface state and near band edge emissions are dominating in case of bare and coated samples, respectively. Swift heavy ion irradiation of the samples was carried out with 160 MeV Ni¹²⁺ ion beam with fluences 10¹² to 10¹³ ions/cm². Size enhancement of bare quantum dots after irradiation has been indicated in XRD and TEM analysis of the samples which has also been supported by optical absorption spectra. However similar investigations on irradiated coated quantum dots revealed little change in quantum dot size and emission. The present study thus shows that the coated ZnS quantum dots are stable upon SHI irradiation compared to the bare one.     

In-situ polymerization approach for preparation of rare earth fluoride phosphors coated with PAA

Up-conversion nanoparticles (UCNPs), which can convert a radiation from a longer wavelength to a shorter wavelength, have great potential uses as bio-labels in biological detection. However, these NPs usually cannot be used directly unless their surfaces are further modified. In this paper, NaYF4:Yb, Er nanoparticles (NPs) were coated with poly(acrylic acid) (PAA) by in situ polymerization for the first time. Accordingly, NaYF4:Yb, Er/NaYF4 NPs were synthesized before PAA coating to avoid the decay of optical intensity. The resulting UCNPs were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), and up-conversion photoluminescence spectrometry. The XRD results indicated that the resultant UCNPs exhibited a pure hexagonal phase. The FT-IR spectra and TGA curves revealed that these NPs were coated successfully with PAA. Meanwhile, the TEM results showed that well-dispersed UCNPs with the best morphology and an average size of about 90 nm were obtained with 8.0 wt% acrylic acid content (the content percentage in the whole reaction system) at 0 degrees C within 130 min. Fluorescence tests showed that the UCNPs had a strong UC fluorescence intensity. Settlement tests revealed that PAA-coated NaYF4 UCNPs had more favorable dispersion stability than uncoated UCNPs in an aqueous system. These functionalized nanocomposites could be used for further bio-conjugation.     

Studies on optical absorption and photoluminescence of thioglycerol-stabilized ZnS nanoparticles

ZnS quantum dots of size 3 nm are prepared at 303 K using ZnSO₄ and Na₂S₂O₃ precursors with thioglycerol as stabilizing agent. Cd²⁺ doped ZnS were prepared by varying doping concentration from 1 to 8 wt.%. ZnS quantum dots were mixed with CdS quantum dots of size 4 nm in the 3:1, 2:1, 1:1, 1:2, 1:3 and 1:4 M ratio. The nanoparticles were characterized by UV–vis, photoluminescence (PL), XRD and high-resolution TEM measurements. The XRD pattern, high-resolution TEM image and SAED pattern reveal that the nanoparticles are in well-crystallized cubic phase. The band gap of ZnS has increased from the bulk value 3.7 to 4.11 eV showing quantum size effect. Excitonic transition is observed at 274 nm in UV absorption and PL emission at 411 nm. Doping with Cd²⁺ red-shifts both UV and PL spectral bands and enhances the PL band of ZnS nanoparticles. Mixing CdS and ZnS quantum dots in different molar ratios shows red-shift of the band edge in the CdS/ZnS hybrid system. In the 1:1 hybrid system of CdS/ZnS nanoparticles, PL band is red-shifted and the intensity is almost doubled with respect to that of CdS nanoparticles.     

碳纳米管/ZnS复合材料的制备及其性能表征

碳纳米管用氨水、乙二胺四乙酸(EDTA)进行表面改性, 然后通过硫代乙酰胺、醋酸锌、水和表面改性的碳纳米管在水浴超声条件下发生溶液化学反应, 在碳纳米管表面包裹了一层分布均匀、致密的ZnS纳米晶粒. 用XRD、TEM、SAED、SEM、FTIR、PL等表征手段对材料进行了结构及性能表征. 研究结果表明: 对碳纳米管进行乙二胺四乙酸处理是实现ZnS纳米晶粒在碳纳米管表面均匀、致密包裹的重要因素, 碳纳米管/ZnS复合材料的光致发光性较之相同方法合成的ZnS, 俘获态发射峰蓝移6nm, 而能带边缘发射峰蓝移16nm. 通过对FTIR及不同表面改性碳纳米管的对比试验研究, 给出了碳纳米管/ZnS复合材料的形成机理.     

Co2+掺杂水溶性ZnS量子点的制备及其光致发光性能

采用共沉淀法,以3-巯基丙酸为表面修饰剂,成功制备出Co2+掺杂水溶性ZnS量子点。采用X射线衍射仪、透射电子显微镜、原子发射光谱仪、紫外-可见吸收光谱仪和荧光分光光度计等,研究了Co2+掺杂剂及掺杂量对ZnS量子点的晶体结构、形貌和发光性能等的影响。结果表明:所得产物均为ZnS立方型闪锌矿结构,量子点呈不规则球形,粒径主要集中在5.2 nm左右;掺杂样品发红色荧光,发光性能明显增强,属于Co2+形成的杂质能级(4A1—4T1)与缺陷的复合发光。同时,利用红外吸收光谱对Co2+掺杂水溶性ZnS量子点的形成机理进行了初步探讨。     

Investigation on one-pot hydrothermal synthesis,structural and optical properties of ZnS quantum dots

The advantage of hydrothermal synthesis of semiconductor quantum dots (QDs) over the control of particles size, morphology and stability is reported here. In a typical synthesis procedure, the zinc and sulfur precursor molar ratio of 1:3 was used in an aqueous solution at 150 °C. The cubic phase of ZnS with average particles size of 5 nm was confirmed and estimated from the X-ray diffraction (XRD) analysis. The composition and purity of the sample were analyzed from (energy dispersive-ray analysis) EDAX and (X-ray photoelectron spectroscopy analysis) XPS spectra. The absorption spectrum shows the large shift in the absorption band over 90 nm due to the quantum confinement of carriers. The emission spectrum of quantum dots carry more evidence on the presence of shallow trap, deep trap in the band gap of the material responsible for weak emission in the spectral region of 450–500 nm. High resolution transmission electron microscope and scanning electron microscope studies reveal the structural and morphological features of ZnS with slightly distorted spherical morphology. We found that the coordinating ability of solvent strongly influences the reaction process and morphology of the products.     

Mn‐doped ZnS quantum dots‐chlorin e6 shows potential as a treatment for chondrosarcoma: an in vitro study

Chondrosarcoma is the second‐most malignant cancer of the bone and routine treatments such as chemotherapy and radiotherapy have not responded to the treatment of this cancer. Due to the resistance of chondrosarcoma to radiotherapy, the combination of therapeutic methods has been considered in recent years. In this study, a novel combination approach is used that allows photodynamic therapy to be activated by X‐rays. The synthesis of Mn‐doped zinc sulphide (ZnS) quantum dots was carried out and chlorin e6 photosensitiser attached by covalent and non‐covalent methods and their application as an intracellular light source for photodynamic activation was investigated. The toxicity of each nanoparticles was evaluated on chondrosarcoma cancer cells (SW1353) before and after radiation. Also, the effect nanoparticle‐photosensitiser conjugated type was investigated in the therapeutic efficacy. The characterisation test (SEM, TEM, EDS, TGA, XRD and ICP analyses) was shown successful synthesis of Mn‐doped ZnS quantum dots. Chondrosarcoma cancer cell viability was significantly reduced when cells were treated with MPA‐capped Mn‐doped ZnS quantum dots‐chlorin e6 with spermine linker and with covalent attachment (P  ≤ 0.001). These results indicate that X‐ray can activate the quantum dot complexes for cancer treatment, which can be a novel method for treatment of chondrosarcoma.Inspec keywords: semiconductor quantum dots, X‐ray diffraction, transmission electron microscopy, cadmium compounds, cellular biophysics, drugs, manganese, biomedical materials, cancer, quantum dots, nanofabrication, ultraviolet spectra, zinc compounds, fluorescence, scanning electron microscopy, nanoparticles, nanomedicine, bone, photochemistry, photodynamic therapy, tumours, II‐VI semiconductors, laser applications in medicineOther keywords: noncovalent methods, photodynamic activation, chondrosarcoma cancer cells, chondrosarcoma cancer cell viability, quantum dot complexes, cancer treatment, malignant cancer, routine treatments, radiotherapy, therapeutic methods, Mn‐doped zinc sulphide quantum dots, in vitro study, MPA‐capped Mn‐doped ZnS quantum dots‐chlorin e6, nanoparticle‐photosensitiser conjugated type, ZnS, Mn, ZnS:Mn     

Synthesis of ZnS nanoparticles into the pore of mesoporous silica spheres

The ZnS nanoparticles were exclusively synthesized in the pores of the mesoporous silica (MS) particles which had been coated with two bilayers of poly(allylamine hydrochloride) (PAH)/poly(styrene sulfonate) (PSS) via the layer-by-layer (LbL) self-assembly technique. Measurements and analysis of XRD and TEM showed that the ZnS nanocrystals were inserted into the pores of the MS spheres. This approach can be used to prepare composite materials involving functional inorganic nanoparticles which have potential application in biological immunoassay and photoelectronic fields.     

Structural and luminescence characterization of Eu3+/ZnS nanoparticle-doped ZrO2/PEG composites

ZnS nanoparticles of varying concentrations were incorporated into Eu³⁺ doped ZrO₂/PEG composite system through non-hydrolytic sol–gel method. The presence of the nanoparticles was confirmed by XRD and TEM analyses. The elemental composition of the prepared sample was verified using EDX analysis. Different vibrational modes of the composite system were found out by FTIR spectra. Thermal stability of the as-prepared sample was measured using TGA and DTA analyses. The optical bandgap of the composite system was calculated from the absorption spectrum. The excitation spectrum shows the broad excitation bands of the sensitizer (ZnS) and Host (ZrO₂/PEG) as well as the characteristic excitation peaks of the activator (Eu³⁺). The emission spectra reveal that the characteristic emission of Eu³⁺ can be obtained using 392 nm as well as the excitation wavelength of the sensitizer (275 nm). The CIE chromaticity analysis shows a change in the emission colour of the co-doped samples from yellow to reddish orange corresponding to a change in the excitation wavelength from 392 to 275 nm. These results suggest the applicability of the as-synthesized composite system as a potential candidate in various optoelectronic devices.