Microtribological Studies of Poly(ether ether ketone) by Atomic Force Microscopy (AFM)

Atomic force microscopy (AFM) and its modification-lateral force microscope (LFM) are becoming increasingly important in the understanding of microfriction and nanomechanical property measurements. In the present paper, the AFM, LFM and a modified AFM-lithography technique are described, and data on microtribilogical studies of PEEK are presented. For comparisons, macro-scale friction measurements were also made on PEEK by the use of a block-on-ring testing facility. It was observed that macro-scale friction is higher than that on the microscale. Lower value of micro-scale friction as compared to macro-scale fiction may be because of less ploughing contribution in the micro-scale measurement.     

罗丹明标记的磷脂分子聚集态的光谱与AFM研究

在不同表面压的ＬＢ膜上,应用光谱学和原子力显微镜学研究了由罗丹明标记的磷脂分子形成的多种聚集态．这些分子聚集态使光谱的峰值位移,谱带加宽．ＡＦＭ的形貌图进一步说明了膦脂单分子膜的不均一性．根据激子理论,以４５°取向角存在的罗丹明染料聚集体更符合－Ａ曲线．     

Synthesis of Poly(vinyl acetate)-block-poly(dimethylsiloxane)-block-poly(vinyl acetate) Copolymers by Iodine Transfer Photopolymerization in Miniemulsion

Summary: Iodine transfer polymerization of vinyl acetate in aqueous miniemulsion, initiated by UV radiation in the presence of an α,ω-diiodo-poly(dimethylsiloxane) macrophotoiniferter has been performed. The formation of a triblock copolymer latex PVAc-b-PDMS-b-PVAc has been evidenced by ¹H-NMR and size exclusion chromatography. The size of the PDMS and PVAc blocks were modulated thus opening the way to a wide range of copolymers with different properties. A detailed study of the reaction mechanism showed the importance of the aqueous dispersed medium to achieve a controlled polymerization.     

Mechanical Characterization of Micrometric Chitosan-Coated Vesicle by Atomic Force Microscopy

This article reports the main results obtained for the stabilization of DOPC liposomes by coating with chitosan. We investigated the compression between two planes of isolated GUV, combining force spectroscopy measurements with scanning probe microscopy (SPM) and epifluorescence microscopy observations. We obtained reproducible and reversible force-deformation curves for individual vesicles in the range of small deformation (relative deformation up to 0.3). Force-deformation curves were analyzed using a simple elastic model, which well describes the observed radius-dependency of the force response and allows determining the stretching modulus for bare vesicle and effective bending and stretching moduli for chitosan-coated membranes. Results first show that chitosan coating increases the effective stretching modulus of the lipid membranes, second, confirm that chitosan is adsorbed flat on the membrane, and finally lead us to assume that the chitosan coating structure can be regarded as a physical network of connected chitosan patches.     

Dually Responsive Poly(N-vinylcaprolactam)-b-poly(dimethylsiloxane)-b-poly(N-vinylcaprolactam) Polymersomes for Controlled Delivery

Limited tissue selectivity and targeting of anticancer therapeutics in systemic administration can produce harmful side effects in the body. Various polymer nano-vehicles have been developed to encapsulate therapeutics and prevent premature drug release. Dually responsive polymeric vesicles (polymersomes) assembled from temperature-/pH-sensitive block copolymers are particularly interesting for the delivery of encapsulated therapeutics to targeted tumors and inflamed tissues. We have previously demonstrated that temperature-responsive poly(N-vinylcaprolactam) (PVCL)-b-poly(dimethylsiloxane) (PDMS)-b-PVCL polymersomes exhibit high loading efficiency of anticancer therapeutics in physiological conditions. However, the in-vivo toxicity of these polymersomes as biocompatible materials has not yet been explored. Nevertheless, developing an advanced therapeutic nanocarrier must provide the knowledge of possible risks from the material’s toxicity to support its future clinical research in humans. Herein, we studied pH-induced degradation of PVCL₁₀-b-PDMS₆₅-b-PVCL₁₀ vesicles in-situ and their dually (pH- and temperature-) responsive release of the anticancer drug, doxorubicin, using NMR, DLS, TEM, and absorbance spectroscopy. The toxic potential of the polymersomes was evaluated in-vivo by intravenous injection (40 mg kg⁻¹ single dose) of PVCL₁₀-PDMS₆₅-PVCL₁₀ vesicles to mice. The sub-acute toxicity study (14 days) included gravimetric, histological, and hematological analyses and provided evidence for good biocompatibility and non-toxicity of the biomaterial. These results show the potential of these vesicles to be used in clinical research.     

Transition from Micelles to Microemulsions in Sugar-Based Surfactant Systems Probed by Fluorescence Spectroscopy and Atomic Force Microscopy

The systems investigated by fluorescence spectroscopy and atomic force microscopy were water/sucrose laurate/oil + ethanol. The oils were R (+)-limonene and isopropylmyristate. The mixing ratio (w/w) of ethanol/oil equals unity. The fluorescent probes auramine-O and 8-anilino-1-naphthalenesulfonic acid were used to determine the minimum ω′ value for the transition of reverse micelles to microemulsions in the systems based on the two oils, as well as at different surfactant contents. The fluorescence quenching of Safranine-T (3, 6-diamino-2,7-dimethyl-5 phenyl phenazinium chloride) by the inorganic ions Fe²⁺, Fe³⁺, and Cu²⁺ was studied in reverse micelles and microemulsions. The Stern-Volmer quenching constants at different water/surfactant molar ratios (ω values) were calculated from the data of the quenching process. Atomic force microscopy was used to image the systems based on the two oils for different water to surfactant molar ratios below and above the minimum ω′ value.     

原子力显微镜技术对生物样品的研究

评述了近几年原子力显微镜在生物样品中的应用情况。主要涉及利用原子力显微镜研究核酸,包括脱氧核糖核酸和核糖核酸、蛋白质、核酸与蛋白质复合物、细胞和病毒等5个方面的最新进展。     

Synthesis of Poly(Styrene)-block-poly(methacrylate)-block-poly(styrene) via Site Transformation Reaction

Abstract

Triblock copolymers with polystyrene outer blocks and an inner polymethacrylate block were synthesized by a site transformation reaction using anionic and cationic polymerization techniques. In order to obtain such ABA block copolymers, two synthetic routes have been applied. In the first case, different methacrylates (methyl methacrylate, 2-ethylhexyl methacrylate) were polymerized anionically with a bifunctional initiator to get poly(methacrylate) dianions later forming the inner block whereas in the second case poly(styrene)-block-poly(methacrylate) anions were synthesized by monofunctional initiation via sequential monomer addition. In a subsequent step, the living chain ends of the methacrylate dianions on one side, and the diblock copolymer anions on the other side, were functionalized with 1,4-bis(l-bromoethyl)benzene in order to obtain a potential bifunctional or monofunctional macroinitiator for the cationic polymerization of styrene. Then, styrene was polymerized cationically with the macroinitiator in the presence of SnCl₄ as coinitiator and _n Bu₄NBr as a common ion salt in CH₂Cl₂ at -15°C. Block formation was proven by SEC measurements, preparative SEC and NMR characterization.     

聚甲基丙烯酸甲酯/苯乙烯-丙烯腈无规共聚物薄膜表面原位原子力显微镜相图

采用原位原子力显微镜在线跟踪方法,研究了聚甲基丙烯酸甲酯/苯乙烯 丙烯腈无规共聚物共混体系表面相分离行为,得到了具有下临界共溶温度（临界温度约为175 ℃）原位相图。 与文献报道的用离位方法所得结果的主要差别是原位的临界相分离温度稍有提高,以及离位结果中存在的组成对称性。 这些差别主要来源于离位和原位实验方法上的差别,薄膜厚度减小导致的相容性,热力学历史的变化以及基底效应的加剧。     

电化学原子力显微镜的应用

评述了电化学原子力显微镜的原理和技术及其在现场电化学和电分析化学领域的应用,如观察电镀、腐蚀和防腐的过程,电化学沉积膜的形成和特点,测定两表面间的静电力等,指出其存在的一些缺陷,并对经过改造后的电化学原子力显微镜进行了综述。     

Atomic Force Microscopy Characterization and Interpretation of Thin‐Film Poly(butylene adipate) Spherulites with Ring Bands

Atomic force microscopy characterization has been conducted to reveal the morphological difference between single‐ring bands in poly(butylene adipate) (PBA). Furthermore, morphological features of the ring‐less Maltese‐cross spherulites are compared to the ring‐band spherulites. Periodic changes in height seem to be common for either the ring‐band or ring‐less (Maltese‐cross) crystal domains; however, the steepness in height change is greater for the ring‐band crystal, while height change in the ring‐less crystal exhibits a terrace‐like layer pattern. In the ring‐band crystal region, the lamellar stalks, which taper off to pointed needle‐like stalks, monotonously protrude out of the layers of softer materials, with no signs of twisting, bending, or turning. In contrast, all lamellae in the ring‐less (Maltese‐cross) crystal region are uniform platelets arranged like flower petals in a layered pattern.

     

Study of Ultrafine Iron Powders by Atomic Force Microscopy

The particles of ultrafine iron powders obtained by three different methods (electrolytic deposition, reduction in hydrogen flow, and grinding in a planetary ball mill in heptane medium) were studied by the atomic force microscopy and the results were compared with the data of electron microscopy and X-ray diffraction analysis. The shape and size of particles were determined from three-dimensional images obtained by atomic force microscopy, and the grain structure of the particle surface layer was studied by measuring the lateral friction forces.     

Atomic Force Microscopy Studies of SnO2 Thin Film Microstruc tures Deposited by Atomic Layer Epitaxy

 ALE-grown, rutile-type SnO₂ thin films and gas sensor structures based thereupon were studied by AFM with main emphasis on cross-sectional investigations (X-AFM). On glass substrates the polycrystalline films showed a preferred orientation which depended on the film thickness and growth temperature while on single crystal sapphire () the growth was heteroepitaxial. For the X-AFM studies various sample preparation techniques were investigated but only ion beam etching gave satisfactory results and revealed substructures in the sensor structure consisting of Pt and SnO₂ layers on a silicon substrate.     

Atomic Force Microscopy Study of TiO2 Films Obtained by the Sol-Gel Method

Atomic Force Microscopy (AFM) was used to study the influence of thermal treatments on the structural and textural properties of the sol-gel TiO2 films obtained from Ti(OC3H7i)4. X-ray diffraction (XRD), ellipsometric and porosity measurements have also been made.The TiO2 sol-gel films were homogeneous, transparent and amorphous. Heat treatments in the 400–600°C range indicate that the films have a strong tendency to crystallization. The high initial homogeneity of the TiO2 films was preserved during the crystallization process. AFM shows that the thermally treated films exhibit uniform, monodispersed crystals.     

原子力显微镜的基本原理及应用

先进的测试表征技术是认识微观世界的重要手段，对于尺度和维度观的培养具有重要意义。不同于传统光学显微镜和电子显微镜，原子力显微镜是通过其探针原子与样品的表面原子的作用力来实现对样品表面形貌观测的。简述了原子力显微镜的基本原理和基本构造，阐释了其核心部件及功能。原子力显微镜主要有4种工作模式，比较了它们的优劣及应用范围。最后对原子力显微镜在分析测试中的实际应用进行了简述，展现了原子力显微镜的优越性与广阔的应用前景。     

Sublimation and Diffusion Kinetics of 2,4,6-Trinitrotoluene (TNT) Single Crystals by Atomic Force Microscopy (AFM)

In this article, we report the in-situ nanoscale experimental measurement of sublimation rates, activation energy of sublimation, and diffusion coefficients of 2,4,6-trinitrotoluene (TNT) single crystals in air using atomic force microscopy (AFM). The crystals were prepared by slow evaporation at 5 °C using acetone-dissolved TNT. The mass loss was calculated by monitoring the shrinkage of the surface area of layered islands formed on the surface of the TNT crystals due to sublimation upon isothermal heating at temperatures below the melting point. The results suggest the sublimation process occurs via two-dimensional detachment of TNT molecules from the non-prominent facets on the crystal surface which imitates the nucleation and crystal growth process. Sublimation rates are one order of magnitude smaller than previously reported values. However, the calculated activation energy (112.15 ± 3.2 kJ/mol) and temperature-dependent sublimation rates agree well with the reported values for TNT thin films and microcrystals determined by UV-vis absorbance spectroscopy and quartz crystal microscopy (QCM) (90–141 kJ/mol). The average diffusion coefficient is (4.35 × 10^–6 m²/s) which is within the range of the reported theoretical values with an average of 5.59 × 10^–6 m²/s, and about 25% less than that determined using thermogravimetric analysis for powder TNT.     

Observation of Organic Thin Film Surface by Atomic Force Microscopy

The 8-hydroxyquinoline neodymium(Ndq3) organic thin films deposited on the cleaned indium/tin oxide (ITO) at different deposition rates with the same vacuity (133.3×10^-5 Pa) were revealed by atomic force microscopy (AFM). Organic devices with one layer of Ndq3 as the e-type conductive material at different deposition rates sandwiched between ITO and aluminum electrodes have been fabricated. respectively. Evidence suggests that the current-voltage (I-V) characteristics were determined by the uniformity of organic film which was controlled by the deposition conditions.     

Synthesis and Characterization of Thermo-responsive Poly(N-vinyl-2-pyrrolidinone)-block-poly(N-isopropylacrylamide) Micelles

A novel thermo-responsive diblock copolymer of poly(N-vinyl-2-pyrrolidinone)-block-poly(N-isopropylacrylamide) (PNVP-b-PNIPAM) was synthesized. FT-IR, ¹H-NMR and SEC results confirmed the successful synthesis of PNVP-b-PNIPAM diblock copolymer via anionic polymerization. The polymeric micelles formed from PNVP-b-PNIPAM copolymer in aqueous solution were developed and characterized as a potential thermo-responsive and biocompatible drug delivery system. Micellization of the diblock copolymer in aqueous solution was characterized by dynamic laser scattering (DLS), turbidity measurement, tension measurement and transmission electron microscopy (TEM). The thermo-responsive polymeric micelles with the size ranges of 200 to 260 nm and thickness of 30 nm are localized, selected and targeted for drug release, having a great potential in response to external-stimulus such as temperatures from 35 to 39°C. The critical micellization concentration (cmc) of PNVP-b-PNIPAM in aqueous solution is 0.0026 wt% determined by turbidity measurement. The size of micelles determined by DLS increased from 163 to 329 nm with increasing concentration of PNVP-b-PNIPAM from 0.25 to 0.5 wt% in aqueous solution at 40°C, which is determined by DLS.