壳聚糖纳米粒子荧光探针的制备和表征

通过低分子量的壳聚糖(LCS)聚阳离子与三聚磷酸钠(TPP)的静电作用制备纳米级壳聚糖微球,并利用壳聚糖链上丰富的氨基与荧光素异硫氰酸酯(FITC)反应从而制备纳米壳聚糖微球荧光探针(NFCS)。结果表明,当壳聚糖分子量为60000,LCS与TPP的质量比为6∶1时,可得到粒度均一的球形纳米粒子,平均粒径为40±3 nm。荧光倒置显微镜观察证实FITC结合到壳聚糖微球上。荧光光谱分析显示NFCS的最大激发波长、最大发射波长与游离态FITC无显著差异。光漂白实验证实NFCS的稳定性比游离态FITC有显著提高。     

The effect of carboxymethyl-chitosan nanoparticles on proliferation of keloid fibroblast

In this study, different molecular weight (MW) carboxymethyl chitosans (CM-chitosan) nanoparticles were prepared by ionic gelification. The particle size of nanoparticles was around 180–250 nm by dynamic light scattering (DLS) and transmission electron microscope (TEM). With the increase of CM-chitosan nanoparticles concentration from 2 to 200 μg/mL, the growth inhibition effects on the keloid fibroblast increased. At the concentration of 100 μg/mL, CM-chitosan nanoparticles with MW6.3 kDa had a significant inhibitory effect (inhibition ratio 48.79%) of the proliferation of keloid fibroblast. Compared with CM-chitosan solution, the inhibition of CM-chitosan nanoparticles were lower in prior period and similar in later period. By analyzing the different effects of chitosan, CM-chitosan solution and CM-chitosan nanoparticles on proliferation of keloid fibroblast, we have found that the carboxylmethyl groups of CM-chitosan play an important role in inhibition of proliferation of keloid fibroblast.     

Cytotoxicity of liver targeted drug-loaded alginate nanoparticles

In this study, novel liver targeted doxorubicin (DOX) loaded alginate (ALG) nanoparticles were prepared by CaCl₂ crosslinking method. Glycyrrhetinic acid (GA, a liver targeted molecule) modified alginate (GA-ALG) was synthesized in a heterogeneous system, and the structure of GA-ALG and the substitution degree of GA were analyzed by ¹H NMR, FT-IR and elemental analysis. The drug release profile under the simulated physiological condition and cytotoxicity experiments of drug-loaded GA-ALG nanoparticles were carried out in vitro. Transmission electron micrographs (TEM) and dynamic light scattering (DLS) analysis showed that drug-loaded GA-ALG nanoparticles have spherical shape structure with the mean hydrodynamic diameter around 214 ± 11 nm. The drug release was shown to last 20 days, and the MTT assay suggested that drug-loaded GA-ALG nanoparticles had a distinct killing effect on 7703 hepatocellular carcinoma cells.     

Ionic conductivity and tensile properties of hydroxyethyl and hydroxypropyl chitosan membranes

Hydroxyethyl chitosan and hydroxypropyl chitosan were prepared through the reaction of alkali‐chitosan with 2‐chloroethanol and propylene epoxide, respectively. Fourier transform infrared and ¹³C NMR measurements were made to examine the substitution on the chitosan unit. According to a comparison of the peak areas between the modified chitosan and unmodified chitosan and the integration of peak areas of ¹H NMR spectra, for both modified chitosans, the maximum degree of substitution was less than 25%. The ionic conductivity and mechanical properties of modified chitosan membranes were investigated. In comparison with the unmodified chitosan membrane, hydrated hydroxyethyl and hydroxypropyl chitosan membranes with a higher degree of substitution showed an increase in ionic conductivity of about one order of magnitude; moreover, the crystallinity of hydroxyethyl and hydroxypropyl chitosan membranes was remarkably reduced, and their swelling indices increased significantly. However, these modified membranes did not exhibit significant changes in their tensile strength and breaking elongation. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 1379–1397, 2004     

Study on facile designing,swelling properties and structural relationship of gelatin nanoparticles

In the present work glutaraldehyde crosslinked gelatin (Type-A and Type-B) nanoparticles were fabricated following a microemulsion crosslinking technique. The structural, morphological, and stability features of nanoparticles were investigated using the techniques like FTIR, TEM, XRD, DLS, and surface charge measurements. The spectral peaks appeared in the FTIR spectra of gelatin nanoparticles confirmed the crosslinking of gelatin molecules with glutaraldehyde. The SEM analysis of the nanoparticles suggested that the size of gelatin nanoparticles was nearly 300 nm whereas the TEM analysis revealed their size around 200?nm. The size of nanoparticles was found to increase with increasing amounts of gelatin while it showed a decrease when the concentration of crosslinker was increased. An increase in percent crystallinity was observed when gelatin was crosslinked with glutaraldehyde. The water uptake capacity of the gelatin nanoparticles was evaluated under varying experimental conditions like, pH, temperature, presence of simulated physiological fluids and varying composition of the gelatin nanoparticles. To study the cytotoxic behavior of gelatin nanoparticles in vitro cytotoxicity analysis were performed. The gelatin nanoparticles demonstrated good stability and biocompatibility which suggested that these particles can be used as drug carrier in fabricating a swelling controlled drug delivery system.     

Preparation and properties of ionically cross‐linked chitosan nanoparticles

Chitosan nanoparticles were fabricated by a method of tripolyphosphate (TPP) cross‐linking. The influence of fabrication conditions on the physical properties and drug loading and release properties was investigated by transmission electron microscopy (TEM), dynamic light scattering (DLS), and UV–vis spectroscopy. The nanoparticles could be prepared only within a zone of appropriate chitosan and TPP concentrations. The particle size and surface zeta potential can be manipulated by variation of the fabrication conditions such as chitosan/TPP ratio and concentration, solution pH and salt addition. TEM observation revealed a core–shell structure for the as‐prepared nanoparticles, but a filled structure for the ciprofloxacin (CH) loaded particles. Results show that the chitosan nanoparticles were rather stable and no cytotoxicity of the chitosan nanoparticles was found in an in vitro cell culture experiment. Loading and release of CH can be modulated by the environmental factors such as solution pH and medium quality. Copyright © 2008 John Wiley & Sons, Ltd.     

Synthesis,Characterization of Copper-Loaded Carboxymethyl-Chitosan Nanoparticles with Effective Antibacterial Activity

Summary: Copper-loaded carboxymethyl-chitosan (CMCS-Cu) nanoparticles were successfully prepared by chelation under aqueous conditions. The effect of degree of deacetylation and substitution, the molecular weight of CMCS, CMCS concentration, Cu(II) ions concentration, pH value of the solution, as well as temperature, on the morphology of the yielded particles were systematically investigated. The physicochemical properties of the particles were determined by size and zeta potential analysis, FTIR analysis, DLS, TEM, SEM and XRD pattern. FTIR and XRD revealed that Cu (II) ions and CMCS formed a chelate complex. The size of CMCS-Cu particles shows a good consistency by DLS, TEM, and SEM. The nanoparticles with the size of about 70 nm have been prepared at 0.13 wt% CMCS, 16 mmol/L Cu(II) ions, pH value 4.56 at 25 °C. The antibacterial activity of CMCS, CMCS-Cu normal particles with the size of about 1000 nm and CMCS-Cu nanoparticles with the size of less than 100 nm against Staphylococcus aureus was evaluated by vibration method. Results show that the antibacterial efficiency of nanoparticles reached 99%, which is much more efficient than 68.9% of the normal one and 6.1% of CMCS. CMCS-Cu nanoparticles were proved to be a good novel antibacterial material.     

纤维素苯甲酸酯接枝二乙二醇十六烷基醚的制备及性能

分别以1-烯丙基-3-甲基咪唑氯盐([Amim]Cl)和1-乙基-3-甲基咪唑醋酸盐([Emim]Ac)/N,N-二甲基乙酰胺(DMAc)为溶剂体系,以微晶纤维素(聚合度为220)和苯甲酰氯(BC)为原料制备纤维素苯甲酸酯(CB).探索了溶剂体系、反应温度和投料比对产物取代度、溶解性和熔融性能的影响.结果表明,以[Amim]Cl为溶剂时,随着反应温度的升高(60~80℃)或体系中苯甲酰氯与葡萄糖单元环(AGU)投料量的增加(3∶1~9∶1),产物的溶解性和熔融性能均提高,取代度也随之升高(0.13~2.98);以[Emim]Ac/DMAc为溶剂时,产物中苯甲酰基的接枝度较低,且共聚物中引入乙酰基不适合制备纤维素-g-苯甲酰氯.初步探讨了在[Amim]Cl中合成纤维素苯甲酸酯接枝二乙二醇十六烷基醚(CB-g-E_2C_(16))固-固相变材料的性能,研究结果表明,CB-g-E_2C_(16)相变材料的相变温度为12.7~29.1℃,相变焓为12~24 J/g,在294℃仍能保持热稳定性,为该类纤维素基固-固相变材料的可熔融加工奠定了理论基础.     

Manipulating the degradation rate of PVA nanoparticles by a novel chemical‐free method

The high water solubility of poly (vinyl alcohol) (PVA) is one of the challenging problems in its application. In order to rectify this problem, PVA needs to be crosslinked. Freeze‐thawing in solid state as a novel physical crosslinking method was employed for enhancement the stability of PVA nanoparticles in aqueous solutions during this study. PVA nanoparticles were successfully prepared by electrospraying and electrospray conditions were optimized in the view points of polymer concentration and solvent system. The morphology of nanoparticles was tailored from collapsed particles and mixture of particles/fibers to spherical particle by manipulating of polymer solution concentration and solvent system. After preparation of PVA nanoparticles in optimum condition, they were frozen at ?20°C and subsequently thawed at 25°C for different cycles of 1, 2, and 3. Field‐emission scanning electron microscope (FE‐SEM), Fourier‐transform infrared (FTIR), X‐ray diffraction (XRD), differential scanning calorimeter (DSC), and biodegradation were used to evaluate the effect of freeze‐thawing on properties of PVA nanoparticles. FE‐SEM showed the spherical morphology of the PVA nanoparticles with sizes ranging from 200 to 300 nm. The FTIR spectroscopy indicated that the crystallinity of PVA nanoparticles increases after freeze‐thawing process. Moreover, by increasing the number of cycles, degree of crystallinity of nanoparticles increases. The XRD and DSC analysis of PVA nanoparticles again demonstrated the increasing of crystallinity of nanoparticles after freeze‐thawing process. The biodegradation behavior of PVA nanoparticles after freeze‐thawing exhibited the decreasing of degradation rate by increasing the number of cycles. Our overall results present a solvent‐less and safe method for crosslinking of PVA nanoparticles in solid state, which make it suitable for biomedical applications.     

纳米ZnS在KGM-AE高分子模板中的可控制备与光限幅性能研究

设计了一种新的乙酸酐改性魔芋葡苷聚糖(KGM-AE)作为高分子模板，通过调节模板剂的改性度、模板剂溶液浓度以及Zn²⁺离子浓度，探讨了ZnS纳米粒子形成的机理，制备出了大小及形貌可控的纳米ZnS。利用IR、ICP-AES、XRD、TEM等对ZnS结构进行了表征，并测定了纳米ZnS光限幅性能，结果显示纳米ZnS溶液均呈现出明显的光限幅性能。     

Synthesis and characterization of PEG modified N-trimethylaminoethylmethacrylate chitosan nanoparticles

Chitosan-N-trimethylaminoethylmethacrylate chloride-PEG (CS-TM-PEG) copolymers were synthesized in order to improve the solubility of chitosan in physiological environment, and enhance the biocompatibility of quaternized chitosan. The result of ¹H NMR confirmed that PEG had been combined with amino groups of quaternized chitosan. The profile of hemolysis assay showed that Chitosan-N-trimethylaminoethylmethacrylate chloride (CS-TM) copolymer exhibited hemolytic activity from 10.31% to 13.58%, while CS-TM-PEG copolymer had hemolytic activity from 4.76% to 7.05% at copolymer concentrations from 250 to 2000 μg/ml. Through PEG modification, the hemolytic activity could be reduced to a half. CS-TM-PEG copolymer-insulin nanoparticles were prepared based on ionic gelation process of positively charged copolymers and negatively charged insulin. The nanoparticles were characterized in terms of particle size, TEM, association efficiency and in vitro release. These nanoparticles were 200-400 nm in size and insulin association efficiency of optimal formulations was found up to 90%. In vitro release showed that the nanoparticles provided an initial burst release followed by a sustained release with the sensitivity of ionic strength and pH values.     

High antibacterial activity and low toxicity of pyridoxal derivatives of chitosan and their nanoparticles

The pyridoxal derivatives of chitosan with various degrees of substitution (DS) were synthesized from low-, moderate- and high-molecular-weight chitosans by their reaction with pyridoxal followed by treatment with NaBH₄. The derivative of moderate molecular weight and high DS demonstrated a maximum antibacterial activity against S. aureus and E. coli. The nanoparticles of this derivative obtained by ionic gelation are nontoxic, and they exhibit a high in vitro antibacterial effect, which slightly exceeds that of ampicillin and gentamicin.     

Controlling the size of magnetic nanoparticles using pluronic block copolymer surfactants

We have successfully controlled the size of magnetic nanoparticles by adjusting the surfactant/solvent ratio. Gamma-Fe(2)O(3) nanoparticles of 5.6 and 12.7, and Fe(0) nanoparticles of 22.3 nm in diameter were prepared, all having spherical shape and uniform size as confirmed by TEM. M?ssbauer spectra confirmed Fe(3+) for the 5.6 and 12.7 nm particles and Fe(3+) and Fe(0) for 22.3 nm particles, in good agreement with synchrotron XRD patterns. Both room temperature and 5 K H-M measurements show that 22.3 nm particles have much higher magnetization than their oxide counterparts, in agreement with their being Fe(0). T-M measurements show superparamagnetism for 5.6 and 12.7 nm particles and ferromagnetism for 22.3 nm particles.     

离子液体[Bmim]BF4中单分散Ru纳米粒子的制备及选择加氢性能

采用化学还原法在离子液体1-丁基-3-甲基咪唑四氟硼酸盐([BMim]BF₄)中制备了单分散纳米金属Ru粒子。采用X射线衍射(XRD)、透射电镜(TEM)、傅里叶红外光谱(FTTR)及热重(TG)对所制备样品的形貌和结构进行了表征。XRD表征结果显示：在[BMim]BF₄中制备的Ru具有六方紧密堆积结构,无氧化物峰出现;TEM结果显示：采用正滴法制备的Ru纳米粒子为球形颗粒,呈现良好的单分散状态,粒径分布窄,为2~5 nm,而采用反滴法制备的Ru纳米粒子则发生了严重的团聚,团聚体粒径大于10 nm;FTIR表征表明：Ru纳米粒子表面存在[BMim]BF₄液体层,分析二者之间存在较强的物理吸附作用,[BMim]BF₄在Ru纳米粒子的制备中起到了修饰剂和保护剂的双重作用,这一推论通过TG分析得到了进一步验证。将分散于[BMim]BF₄的Ru纳米粒子作为催化剂应用于苯选择加氢反应,结果分析表明：Ru-离子液体-苯反应体系中,苯转化率仅有0.3%;Ru-离子液体-苯-水反应体系中加氢活性较高,但环己烯选择性较低,在一定条件下,加氢30 min,苯转化率为27.3%,环己烯选择性仅为14.5%。     

Physical and chemical characterization insulin-loaded chitosan-TPP nanoparticles

The purpose of this study was to develop and characterize insulin nanoparticles systems using chitosan. Insulin-loaded nanoparticles were prepared by ionic gelation of chitosan with tripolyphosphate anions (TPP). The interactions between insulin and chitosan were evaluated by differential scanning calorimetry (DSC), thermogravimetry/derivative thermogravimetry (TG/DTG), and Fourier-transform infrared (FTIR) spectroscopy. Besides, particle size distribution, polydispersity index (PDI), zeta potential, and association efficiency (AE%) of the nanoparticles were evaluated. In general, inert nanoparticles and insulin-loaded nanoparticles showed an average size of 260.56 nm (PDI 0.502) and 312.80 nm (PDI 0.481), respectively. Both nanoparticles showed positive charge, but after insulin incorporation the zeta potential was reduced, evidencing its incorporation. Nanoparticles obtained also showed AE% around 70%, measured by high-performance liquid chromatography (HPLC). The results of FTIR, DSC, and TG/DTG corroborated the data presented suggesting that insulin was successfully encapsulated. However, drug incorporation seems to be related not only to electrostatic interactions, but also to physical process and/or adsorption phenomena.     

Synthesis of highly stable silver nanoparticles using imidazolium-based ionic liquid

Highly stable, aqueous dispersions, and hydrophilic ionic liquid-capped silver nanoparticles with positive surface charge were synthesized by in situ reduction of AgNO₃ with NaBH₄ in the presence of an imidazolium-based ionic liquid, viz., 1-dodecyl-3-methylimidazolium chloride ([C₁₂mim][Cl]) at room temperature. Prepared silver nanoparticles were characterized by UV–vis spectra, transmission electron microscopy (TEM), and zeta potential. UV–visible spectrum of the aqueous medium peaked at 407 nm corresponding to the plasmon absorbance of silver nanoparticles. TEM analysis revealed the spherical shape of the particles with sizes about 9 nm and low polydispersed. The surface charge of the synthesized silver nanoparticles was determined as +5.0 mV. The ionic liquid ([C₁₂mim][Cl]) capped silver nanoparticles were stable for at least 8 months.     

Preparation of chitosan nanoparticles by TPP ionic gelation combined with spray drying,and the antibacterial activity of chitosan nanoparticles and a chitosan nanoparticle–amoxicillin complex

Chitosan nanoparticles were prepared from chitosan with various molecular weights by tripolyphosphate (TPP) ionic gelation combined with a spray drying method. The morphologies and characteristics of chitosan nanoparticles were determined by TEM, FE-SEM and from their mean sizes and zeta potentials. The effect of chitosan molecular weight (130, 276, 760 and 1200 cPs) and size of spray dryer nozzle (4.0, 5.5 and 7.0 µm) on mean size, size distribution and zeta potential values of chitosan nanoparticles was investigated. The results showed that the mean size of chitosan nanoparticles was in the range of 166–1230 nm and the zeta potential value ranged from 34.9 to 59 mV, depending on the molecular weight of chitosan and size of the spray dryer nozzles. The lower the molecular weight of chitosan, the smaller the size of the chitosan nanoparticles and the higher the zeta potential. A test for the antibacterial activity of chitosan nanoparticles (only) and a chitosan nanoparticle–amoxicillin complex against Streptococcus pneumoniae was also conducted. The results indicated that a smaller chitosan nanoparticle and higher zeta potential showed higher antibacterial activity. The chitosan nanoparticle–amoxicillin complex resulted in improved antibacterial activity as compared to amoxicillin and chitosan nanopaticles alone. Using a chitosan nanoparticle–amoxicillin complex could reduce by three times the dosage of amoxicillin while still completely inhibiting S. pneumoniae.     

聚合物纳米微球的合成及摩擦学行为

润滑油添加剂;抗磨性;缓存;聚合物纳米微球的合成及摩擦学行为     

Synthesis and characterization of catalytic iridium nanoparticles in imidazolium ionic liquids

The reduction of [Ir(cod)Cl](2) (cod=1,5-cyclooctadiene) dissolved in 1-n-butyl-3-methyl tetrafluoroborate, hexafluorophosphate and trifluoromethane sulphonate ionic liquids in the presence of 1-decene by molecular hydrogen produces Ir(0) nanoparticles. The formation of these nanoparticles follows the two-step [A-->B, A+B-->2B (k(1),k(2))] autocatalytic mechanism. The same mean diameter values of around 2-3 nm were estimated from in situ TEM and SAXS analyses of the Ir(0) nanoparticles dispersed in the ionic liquids and by XRD of the isolated material. XPS and EXAFS analyses clearly show the interactions of the ionic liquid with the metal surface demonstrating the formation of an ionic liquid protective layer surrounding the iridium nanoparticles. SAXS analysis indicated the formation of an ionic liquid layer surrounding the metal particles with an extended molecular length of around 2.8-4.0 nm depending on the type of the anion.     

W/O型微乳法制备淀粉基纳米粒

在正己烷、Span-60和NaOH水溶液的W／O型淀粉微乳液中,进行淀粉与环氧氯丙烷交联反应制备淀粉微球,用质量分数为1％的淀粉水浆液制备出微球的流体力学半径Rb为7．08—113nm,其中粒径不超过100nm的纳米粒在整个微粒体系中占69％,平均粒径为92．2nm。TEM和DLS结果表明,制得的微粒呈圆球形,且微粒的流体力学半径随淀粉水浆液浓度的增加而增大并分布变宽,淀粉水浆液的浓度低有利于淀粉基纳米粒的形成。