Monomolecular films of pluronic-cyclodextrin inclusion complexes at the water-gas interface

This paper reports the synthesis and characteristics of inclusion type complexes between amphiphilic block copolymer of ethylene and propylene oxides (pluronic) and -, -, and heptakis-(2,6-di-O-methyl)--cyclodextrins. The process was investigated in monolayers at the water-gas interface according to Langmuir-Blodgett technique. Pluronic forms a monolayer, stable at the surface pressure 5 mN/m, which reacts with heptakis-(2,6-di-O-methyl)--cyclodextrin and does not react with - and -cyclodextrins. The absence of the reaction in the case of -cyclodextrin is explained by the fact that the polymer guest does not fit into a small cavity of the macrocyclic host, but for -cyclodextrin it may be explained by its low surface activity and, hence, its low local concentration in the vicinity of the pluronic monolayer. After introducing heptakis-(2,6-di-O-methyl)--cyclodextrin into the aqueous subphase under the pluronic monolayer an instant increase in the area is observed. An increase in the amount of heptakis-(2,6-di-O-methyl)--cyclodextrin in the aqueous phase causes first steep linear increase in the monolayer area, then its leveling off at the polymer-heptakis-(2,6-di-O-methyl)--cyclodextrin ratio equal to about 1:15. This value correlates well with a stoichiometric composition of the similar complex in solution.     

Ultraviolet-visible and Surface-enhanced Raman Scattering Spectroscopy Studies on Ruthenium Phthalocyanine Monolayer Films Formed on Terephthalonitrile-modified Silver Substrates

A self-assembled monolayer film(SAM) of ruthenium phthalocyanine (RuPe) fabricated on a silver sub-strate premodified with an SAM of terephthalonitrile (TPN) was studied by means of surface-enhanced Ra-man seattering(SERS) and ultraviolet-visible (UV-Vis) speetroseopies. TPN was used as a ligand to linkRuPe since it can not only modify the silver suhstrate but also deliver the nitrile groups protruding from thesilver surface. Therefore, we can explore the relationship between the structure and the orientation of RuPeand the TPN-modified substrate. The UV-Vis spectra indicate a strong interaction between RuPe and TPN inthe composite film. The result is further confirmed by the SERS spectra of RuPe-TPN SAM, in which the vi-brational bands arising from both the RuPe and TPN moieties appear clearly, indicating that the RuPe is suc-cessfully assembled on the TPN film.     

硅表面复合自组装膜的制备及其摩擦性能

采用自组装技术在单晶硅表面制备了3-氨基丙基三乙氧基硅烷(APTES)-SiO2-APTES复合膜,并对其表面的组成、结构及摩擦性能进行了表征.结果表明:复合膜表面对水的接触角约为63°,且表面平整、致密,其平均粗糙度(Ra)约为0.963nm.通过原子力显微镜(AFM)和透射电子显微镜(TEM)观察到夹层中SiO2颗粒的粒径约为20-50nm,较均匀地分布在第一层APTES膜的表面.与APTES自组装单层膜(SAMs)相比,APTES-SiO2-APTES复合膜由于纳米SiO2颗粒的引入而表现出更低的摩擦系数和更长的耐磨寿命.     

有机HTDIOO分子LB膜结构的AFM研究

利用原子力显微镜（ＡＦＭ）对有机分子ＨＴＤＩＯＯ单层和多层ＬＢ膜结构进行了观察。实验结果表明，针尖与ＬＢ膜表面分子间的相互作用力会对成像的膜结构有影响。当悬臂针尖与ＬＢ膜表面分子的相互作用力较大时，针尖会扰动ＨＴＤＩＯＯ分子在单层ＬＢ膜中的有序排列。ＨＴＤＩＯＯ单层ＬＢ膜具有有序结构；而在多层ＬＢ膜中，ＨＴＤＩＯＯ分子则聚集在一起形成了一定的畴结构。     

Hydrolysis and Condensation of Alkyltrimethoxysilanes in Monomolecular Films

Hydrolysis and condensation of monomolecular alkyloxysilane films by the Langmuir technique is presented. Octadecyltrimethoxysilane formed monolayers on aqueous subphases with different properties depending on the bulk pH. At pH 1 a solid condensed film was directly formed with a molecular area of 23 Ų and a surface pressure/surface area variation similar to that on non-ionized stearic acid. At pH 5.6 and 11 several phase transitions were observed during the compression of the monolayer with a final collapse at a molecular area of 20 Ų. Relaxation measurements confirmed the stability of the films for longer than 12 hours at different surface pressures below a critical value.     

Enhancement of Raman Scattering of 1,4-Benzenedithiol by CdS Nanoparticles Assembled on a Silver Surface

CAS nanoparticles were assembled on the smooth surface of a piece of silver by using 1,4-benzenedithiol as coupling molecules. The SEM and resonance Raman spectroscopic characterizations demonstrate that the nanosized structure of CdS was still preserved upon assembly, and a two-dimensional structure of CdS nanoparticles was formed on the substrate surface. The FT-Raman spectra indicate that 1,4-benzenedithiol was coupled between CAS nanoparticles and the silver surface with a tilted orientation. The Raman scattering of 1,4-benzenedithiol was substantially enhanced by the assembled CdS nanoparticles, probably due to the alteration of the polarizability of 1,4-benzenedithiol and the electromagnetic interaction between the dipoles of the CdS particle with its image in the metal substrate.     

有机HTDIOO分子LB膜结构的AFM研究

利用原子力显微镜（AFM）对有机分子HTDIOO单层和多层LB膜结构进行了观察·实验结果表明，针尖与LB膜表面分子间的相互作用力会对成像的膜结构有影响．当悬臂针尖与LB膜表面分子的相互作用力较大时，针尖会扰动HTDIOO分子在单层LB膜中的有序排列．HTDIOO单层LB膜具有有序结构；而在多层LB膜中，HTDIOO分子则聚集在一起形成了一定的畴结构．     

Magnetically Deformable Liquid Mirrors from Surface Films of Silver Nanoparticles

This article describes the development of a magnetically deformable mirror composed of a reflective monolayer of silver nanoparticles deposited at the surface of a ferrofluid. In order to be commercially competitive, this mirror must surpass existing technologies with respect to optical performance. Several important characteristics of the mirror, including reflectivity, deformability and long term stability, are determined in large part by the constituent chemical components. This article describes recent progress in the optimisation of these components. As outlined below, several important objectives have been met and the mirror has clearly passed the proof‐of‐concept stage. Challenges, however, remain, particularly with respect to the stability of the surface layer of silver nanoparticles that imparts reflectivity to the mirror. This interdisciplinary project underscores the role that fundamental colloid and surface chemistry can play in the development of a unique optical element.     

表面压测量及LB膜转移装置的研制

自Blodgelt开创了通过单分子层的连续转移制做多层组合膜的技术(即LB膜转移技术)以来,由单分子膜的组装来建造分子水平的有序结构已成为可能。国内研究LB膜所用的仪器一般都是进口的,且价格昂贵。我们研制了一种经济实用、高性能的LB膜压测量及转移装置,其性能指标达到国外同类仪器水平。     

Preparation of Different Poly 3-Alkylthiophene Ultrathin Films at the Surface of Chemically Adsorbed Monolayer Having Thienyl Group

Polymerization processes of two types ultrathin films containing polythienyl groups anchored to the substrate surface through siloxane bonds were investigated. When the oxidative polymerization on the Chemically Adsorbed (CA) monolayer prepared with 11-(3-thienylundecyl)trichlorosilane (TTS) was performed in the acetonitrile solution containing 3-octylthiophene monomer and FeCl₃, the thienyl groups in the CA monolayer and the outer 3-octylthiophene monomers were polymerized each other along the directions of both in-plane and out-of-plane of the CA monolayer. On the other hand, when the oxidative polymerization was performed without the additive 3-octylthiophene monomer, the long conjugated linkage of the thienyl groups was not formed in the CA monolayer. The highest conductivity of the film prepared with the additive 3-octylthiophene of about 10 nm thickness was 10^?2 S/cm.     

Chemomechanical Production of Functional Structure on Silicon Surfaces

"The chemomechanical method was used to scribe the silicon surface with a diamond-tipped instrument in the presence of aryldiazonium salt, the silicon and the arenes was connected with covalent bond, and realize simultaneously functionalizing and patterning silicon. This provided experiment basis for building nano-scale functional structure. At first we scribe the silicon with a diamond-tipped instrument in the atmospheric, and get the micro-structure with better surface quality, which was then used as substrate for the next functionalizing and patterning silicon. By the silicon's controlled self-assembly experiments in the solution, the cutting speed, cutting assembly time in accord with the self-assembled monolayers' quality (SAMs), and more parameters suitable for the film growth are obtained. X-ray photoelectron spectroscopy was used to test the self-assembly monolayers, and atomic force microscopy as well as scanning electron microscopy to characterize the surface morphology. Results show that this method can eoiently achieve simultaneously functionalizing and patterning silicon. We also connect the carbon nanotubes to the SAMs, and charatrerize the surface with AFM. This will provide experimental basis for the further study using SAMs to function silicon surface."     

非对称八烷氧基取代酞菁聚硅氧烷的合成及其单分子膜

非对称八烷氧基取代酞菁聚硅氧烷的合成及其单分子膜穆劲，夏强，华玉晶，周伟东，肖童（山东大学胶体与界面化学研究所，济南，２５０１００）关键词酞菁聚硅氧烷，ＬＢ膜，π－Ａ曲线酞菁化合物是具有高稳定性的大π键共轭体系。目前，酞菁ＬＢ膜研究大多采用单体小分子...     

Structural Surface Features of Paramagnetic Multifunctional Nanohybrids Based on Silver Oleic Acid

Sols of core–shell silver nanoparticles (AgNPs) are synthesized by electrochemical method. The method provides the ability to adjust the particle size by changing both the concentration of oleic acid and the residence time τ₀ in the organic phase. We synthesized AgNPs with oleic acid (OA) concentration of 0.25% (AgNPs & 0.25% OA) and 0.75% (AgNPs & 0.75% OA). These nanoparticles have been studied using modern physical–chemical methods. Differential thermal analysis curves indicate the chemical nature of bond ligand in the secondary shell; this conclusion is confirmed by quantum chemical simulation and semi-empirical calculation. In the electron paramagnetic resonance spectra of silver-containing sols AgNPs & 0.25% OA and AgNPs & 0.75% OA complex wide asymmetric signals of 500–800 G and g-factor of 2.09–2.13 are recorded, in addition, in the spectra of AgNPs with bilayer the pronounced ferromagnetic contribution is observed. The change of the oleic acid layers of the particles affects the dimension of the nanocrystallites that are being formed and the manifestation of their magnetism.

Trial registration number and date of registration JCS-P-20-03-0188.R1, 22-Sep-2020 (02-Mar-2020)

Graphic Abstract

     

Deriving the colloidal synthesis of crystalline nanosheets to create self-assembly monolayers of nanoclusters

Two-dimensional (2D) nanomaterials with the thickness at atomic level are promising candidates for a wide range of applications, and now reach the point to create diversified 2D architectures. The colloidal synthesis route is powerful to produce crystalline nanosheets, nanoribbons and nanoplatelets, and the self-assembly strategy is robust to integrate the functionalities of different nano-objects. In this review, we bridge the colloidal synthesis of nanosheets and the 2D self-assembly of nanoclusters (NCs) with the aim to further optimize the physical and chemical properties of 2D nanomaterials. Ultrasmall NCs, the intermediate for synthesizing nanosheets, are highlighted to show the similarity of 2D crystallization and 2D self-assembly. The modification of conventional 2D colloidal synthesis route greatly permits the controlled self-assembly of NCs into free-standing monolayers in colloidal solutions.     

Rational construction of self-assembly azobenzene derivative monolayers with photoswitchable surface properties

hoto-responsive azobenzene (ABZ) derivatives with different end groups (R) were employed to construct selfassembled monolayers (SAMs) on silicon substrates. The SAMs based on hydrophilic (4-(4'-aminophenylazo) benzoic acid, ABZ-COOH) show excellent reversible photoswitching performance with a large contact angle change of 35° under optimized process.     

Electrochemical Surface Plasmon Resonance Spectroscopy at Bilayered Silver/Gold Films

Bilayered silver/gold films (gold deposited on top of the silver film) were used as substrates for electrochemical surface plasmon resonance spectroscopy (EC-SPR). EC-SPR responses of electrochemical deposition/stripping of copper and redox-induced conformation changes of cytochrome c immobilized onto self-assembled monolayers preformed at these substrates were measured. Influence of the Ag layer thickness and the double-layer capacitance on the EC-SPR behavior was investigated. The results demonstrated that the bilayered Ag/Au metal films produce a sharper SPR dip profile than pure Au films and retain the high chemical stability of Au films. Contrary to the result by the Fresnel calculation that predicts a greater fraction of Ag in the bilayered film should result in a greater signal-to-noise ratio, the EC-SPR sensitivity is dependent on both the Ag/Au thickness ratio and the chemical modification of the surface. Factors affecting the overall SPR sensitivity at the bilayered films, such as the film morphology, potential-induced excess surface charges, and the adsorbate layer were investigated. Forming a compact adsorbate layer at the bilayered film diminishes the effect of potential-induce excess surface charges on the SPR signal and improves the overall EC-SPR sensitivity. For the case of redox-induced conformation changes of cytochrome c, the SPR signal obtained at the bilayered silver/gold film is 2.7 times as high as that at a pure gold film.     

Surface Fixing Effect of Vacuum Evaporated Particles on Polyethylene Single Crystals

Summary: The recrystallization behavior of high density polyethylene (HDPE) single crystals with vacuum evaporated metal chromium or carbon on their surface has been investigated by transmission electron microscopy (TEM) and electron diffraction (ED) techniques. The results indicate that the particle‐coated HDPE single crystals can retain their single crystal structure after complete melting and subsequent recrystallization, with the heat‐treated temperature as high as 200 °C. This phenomenon is attributed to a surface fixing effect of vacuum evaporated Cr or carbon on the single crystals.

A bright‐field electron micrograph and the corresponding electron diffraction pattern of recrystallized Cr‐coated HDPE single crystals.     

Self-Organization and Analysis of the Morphology of Vacuum Evaporated Polyaniline Films

By using formal estimation methods, it is shown that heterogeneous redox structures, which are formed in the course of oxidation of vacuum evaporated thin polyaniline layers in the temperature range of 0–30°C, become more ordered with the increase in the oxidation temperature.     

胆红素及其两亲衍生物的Langmuir-Blodgett膜研究

研究了亚相酸度和金属离子对胆红素(1)及其两个两亲衍生物胆红素二(十八烷基)酯(2)和胆红素二(十八烷基)酰胺(3)的单分子膜和LB膜性能的影响.通过π-A等温线、X射线光电子能谱、紫外-可见光谱等方法,研究了它们在有序分子膜中的分子伸展及与金属离子的配位方式.胆红素及其两亲衍生物与金属离子在有序分子膜中的配位(生成1:1型配合物)明显不同于其在本体溶液中的配位(1:1,1:2或2:1型配合物).小角X射线衍射表明1,2和3形成双层膜间距分别为2.15,5.55和5.65nm的Y型LB膜.