The effects of chain number and state of lipid derivatives of nucleosides on hydrogen bonding and self-assembly through the investigation of Langmuir-Blodgett films

The long-chain lipid derivatives of acyclovir—a nucleoside analogue were used to prepare Langmuir-Blodgett (LB) films, including the single-chained derivative (SGSA) and the double-chained derivative (DASA). The bilayer LB film of DASA or the SGSA/cholesterol (SGSA/Chol) mixture (1:1, mol/mol) on quartz plates was investigated with ultraviolet absorption spectroscopy, and the blue-shifted absorption with 4 nm (DASA) or 18 nm (SGSA/Chol) wavelength changes was observed in comparison with their solutions in chloroform. The rigid double chains of DASA prevented adjacent molecules from approach, while the flexible single chains of SGSA did not. Then the strength of intermolecular hydrogen bonding between the nucleoside moieties of DASA was much more weaker than one of SGSA, and their blue-shifted wavelength in LB films was different. DASA and SGSA/Chol also showed the different bilayer LB films on mica according to the atomic force microscopic observation. The former was prone to tilting on solid supports while the latter would like to stand vertically with the help of cholesterol that could insert into the flexible single chains of SGSA. The chain number (one or two) and state (flexible or rigid) of lipid derivatives of nucleosides strongly impact intermolecular hydrogen bonding and self-assembly behavior.     

Ftir Studies on LB Film of Amphiphile with Schiff Base as Headgroup and Its Copper Complex

Two different ways to form monolayers and LB films (surface film and subphase film) of the complex have been used, where a novel amphiphile containing Schiff base as a headgroup was used as a ligand. the monolayer behavior at the air/water interface was characterized by π-A isotherms and two-dimensional molecular orientation of alkyl chains in LB films and thermal stability were measured by polarized and variable temperature FTIR transmission spectra, indicating that the LB film of the novel amphiphile and its copper(II) complex are very stable as well as stearic acid. Because incorporating the metal ion into the monolayer makes it more condensed, thermal stability of the LB film was enhanced. as can be compared from their structure and properties, subphase films are superior to surface films.     

Langmuir-Blodgett and Langmuir-Schaefer films of poly(5-amino-1-naphthol) conjugated polymer

Langmuir-type films of poly(5-amino-1-naphthol) conductive polymer were formed at the air/water interface. The surface pressure versus molecular area isotherms of the polymeric layers showed a high tendency to aggregate and non-monomolecular behavior on the water surface. Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) procedures have been successfully used to transfer the Langmuir films of this polymer onto hydrophilic silicon substrates. Atomic force microscopy images showed that the films obtained by the LS method have much better quality than those obtained by the LB one. In particular, we have obtained uniform and smooth LS films covering practically all the substrate, while the LB films showed rather aggregated material, only partially covering the substrate.     

Langmuir and Langmuir-Blodgett (LB) films of tetrapyridyl metalloporphyrins

We report on the formation of Langmuir films of 5,10,15,20-tetra(4-pyridyl) 21H,23H-porphine, hereafter named tetrapyridyl porphyrins with distinct central ions (2H⁺, Zn²⁺, Cu²⁺, Ni²⁺). The films were characterized with surface pressure and surface potential isotherms and in situ UV-vis absorbance. The measurements indicated strong aggregation of porphyrin monomers at the air-water interface, with a red shift of the Soret band in comparison with the spectrum obtained from CHCl₃ solutions. The shift was larger for the non-substituted H₂TPyP, and depended on the metal ion. Significantly, aggregation occurred right after spreading of the Langmuir film, with no further shifts in the UV-vis spectra upon compression of the film, or even after transferring them onto solid substrates in the form of Langmuir-Blodgett (LB) films. The buildup of LB films from H₂TPyP and ZnTPyP was monitored with UV-vis spectroscopy, indicating an equal amount of material deposited in each deposition step. Using FTIR in the transmission and reflection modes, we inferred that the H₂TPyP molecules exhibit no preferential orientation in the LB films, while for ZnTPyP there is preferential orientation, with the porphyrin molecules anchored to the substrate by the lateral pyridyl groups.     

一种可溶喹吖啶酮衍生物LB膜的光谱特性

采用表面压-分子面积(π~A)等温曲线、紫外-可见吸收谱和荧光光谱的方法研究了一种喹吖啶酮衍生物材料LB膜的制备及其光谱特性。实验表明,这种喹吖啶酮衍生物能够在水面上形成稳定的单分子膜,它与花生酸(AA)混合后不仅可以形成很好的单分子膜,而且可以较好的转移到固体基片上制备成LB膜多层膜。这种喹吖啶酮衍生物LB膜的紫外-可见吸收谱的吸收峰位较稀溶液发生了红移,这是由极性溶剂分子与其相互作用的结果。其溶液有很强的荧光效应,但LB膜没有荧光现象,原因是在LB膜中QAC16的浓度过高发生“自我猝息”而失光。它在溶液和LB膜中都是以单体的形式存在。     

荧光标记十八胺LB膜的光谱研究

正十八胺以氯化丹酰和8-苯胺基-1-萘磺酸衍生化,单独或与硬脂酸混合后拉制成LB膜,并以稳态和时间分辨荧光研究了膜中分子的微环境和微结构等光物理性质.     

1－苄基－9－氢富勒烯－60LB多层膜的制备及其光学非线性性质

利用π－Ａ等温线、小角Ｘ射线衍射（ＳＡＸＤ）和光学测量方法研究了一种取代富勒烯（Ｃ６０－Ｂｅ）ＬＢ膜的结构特性。纯Ｃ６０－Ｂｅ分子以体相（ｂｕｌｋｐｈａｓｅ）的形式存在于气－液界面上。氮冠（醚）（ＮＣ）分子作为隔层材料，与Ｃ６０－Ｂｅ分子相混合可以制备性能优良的ＬＢ膜。π－Ａ、吸收和小角Ｘ光衍射测量表明：这种混合膜结构的改善是由于Ｃ６０－Ｂｅ分子镶嵌在ＮＣ分子的双脂链之间造成的。通过测量三次谐波产生（ＴＨＧ）可以推出Ｃ６０－Ｂｅ的三阶非线性系数χ（３）＝２．１×１０－１１ｅｓｕ。     

Adsorption of a water soluble cationic dye into a cationic Langmuir monolayer

This communication reports the successful adsorption of a water soluble cationic fluorescent dye Rhodamine B (RhB) into a cationic Langmuir monolayer of Octadecylamine (ODA). Anionic nano clay platelets Hectorite played an important role in the process of adsorption. Surface pressure vs. area per molecule (π–A) isotherms were studied to monitor the adsorption process. In-situ fluorescence Imaging Microscopic (FIM) technique was employed to visualize the domain structures formed at the air–water interface. Atomic Force Microscopic (AFM) image of the monolayer Langmuir–Blodgett (LB) films were taken to study the morphology and ultrastructure of the film. Detailed spectroscopic investigations were carried out on the mono- and multilayer Langmuir–Blodgett (LB) films.     

Formation of nanoscale aggregates of a coumarin derivative in Langmuir–Blodgett film

In the present communication, we report the formation of organized nanoscale aggregates of a coumarin derivative 7 Hydroxy-N-Octadecyl Coumarin-3-Carboxamide (7HNO3C) at the air–water interface and in Langmuir–Blodgett (LB) films in the presence and absence of stearic acid (SA). A pressure-area isotherm reveals that the 7HNO3C form stable monolayer at the air–water interface. However, the stability can be improved by mixing it with a fatty acid stearic acid (SA). The miscibility study shows that the nature of interaction is strongly dependent on the mixing ratio and surface pressure. At a mole fraction of 0.4 of 7HNO3C in SA, the attractive and repulsive interaction between these two molecules balance each other forming a stable film with nanoscale aggregates. UV-Vis absorption spectroscopic studies reveal the nature of the aggregates in LB films. Scanning electron microscopy gives compelling visual evidence of formation of nanoscale aggregates in the mixed LB films.     

Monolayer characteristics and spectroscopic study of benz(b)fluoranthene assembled in Langmuir Blodgett films mixed with stearic acid

Excellent Langmuir Blodgett (LB) films of benz(b)fluoranthene (B(b)F) have been prepared by mixing with stearic acid (SA). The surface pressure vs. area per molecule isotherms (π–A) of B(b)F mixed with SA at different mole fraction reveal that the area per molecule decreases with increasing mole fractions of B(b)F. The area per molecule vs. mole fraction shows that there is positive deviation of the experimental data to the idealized one. This indicates formation of aggregation of B(b)F molecules in the SA matrix. Spectroscopic properties of B(b)F in solution and in mixed LB films have been compared by absorption, steady state fluorescence, phosphorescence spectroscopy and lifetime measurements. Bathochromic shift in absorption and emission spectrum suggests the formation of some kind of aggregates in LB film. Decrease in fluorescence and phosphorescence lifetime is compared to that of pure B(b)F also supports the formation of different sized aggregates in the mixed film.     

酞菁铜衍生物在酞菁酮—氧化铁纳米粒子交替LB膜中的分子取向

通过Langmuir-Blodett技术制备了酞菁酮－氧化铁纳米粒子交替LB膜,利用偏振紫外－可见光谱对酞菁铜衍生物在不同制膜条件下所制得的交替膜中的分子取向进行了研究。结果表明,在同一氧化铁溶胶亚相中,随着表面压的增大,或在相同的表面压下,随着亚相中氧化铁浓度的减小,酞菁铜分子在其复合LB膜中倾斜程度变大。     

Fabrication and Spectroscopic Characterization of Langmuir-Blodgett Films with Luminescent Rare Earth Complexes of Long Chain Double Functional Ligands Mono-L Phthalate (L = Hexadecyl, Octadecyl and Eicosyl)

In this paper, some novel long chain amphiphillic monoester molecules were designed to afford double functions: film-formation ability and luminescent sensitization ability. Subsequently organized molecular films of rare earth complexes with these functional ligands formulated as ML2NO3 were fabricated by the Langmuir-Blodgett film (LB) technology, where RE denotes rare earth ions Eu3+, Tb3+ and Dy3+; L denotes the long chain carboxylic ligands monohexadecyl phthalate (16-Phth), monooctadecyl phthalate (18-Phth) and monoeicosyl phthalate (20-Phth). The average molecular area was obtained according to the π-A isotherms. The layer structure of the LB films was demonstrated by low-angle X-ray diffraction and the average layer spacing was determined from the Bragg equation. UV absorption intensity increases linearly with the number of LB films layers, which indicates that the LB films are homogeneously deposited. The fluorescence spectra of these LB films were quite different from those of their solid complexes. It reveals that the long chain ester ligands are suitable for the excited states of Tb3+ and Dy3+ in the LB films as well as in the solid complexes, but not match with the europium ion in the LB films.     

Formation and Deposition of Langmuir-Blodgett Films with Thiol-Stabilized CdTe Nanoparticles

Incorporation of the thiol-stabilized CdTe nanoparticles into mono- and multilayer films produced by Langmuir-Blodgett (LB) technique was investigated using “pressure-area” isotherms, Quartz Crystal Microbalance, FTIR, UV/Vis absorption and photoluminescence spectroscopy. LB films were formed from cationic (octadecyltrinonylammonium iodide—ODTNA) and anionic (behenic acid) surfactants. Both noticeable increase of limiting surface area of behenic acid monolayer and simultaneous decrease of film strength have been established when the aqueous solution of CdTe nanoparticles was used as a subphase. LB films deposition on solid substrates depends on the type of stabilizing ligands (1-thioglycerol or 2-mercaptoethanol) for CdTe nanoparticles. Optical absorption and photoluminescence properties of the films obtained from behenic acid monolayers that has thioglycerol-stabilized CdTe nanoparticles incorporated into them acquire the same properties as the size-quantized CdTe nanoparticles. The bonding of the cadmium ions, that released as a result of a partial dissociation of ligand-stabilized CdTe nanoparticles with carboxylic group, is considered to be responsible for the incorporation in case of behenic acid surfactant, and in case of ODTNA the incorporation proceeds by means of a weak “nanoparticle-LB matrix” interaction.     

Fabrication and spectroscopic properties of Langmuir-Blodgett films of novel zinc complexes with long chain mono (hexadecyl, octadecyl, eicosyl, and docosyl) phthalate

In this paper, some novel long chain amphiphillic monoester molecules were designed to afford double functions: film-formation and luminescent sensitization. Subsequently, organized molecular films of zinc complexes with these functional ligands formulated as ZnL₂ were fabricated by the Langmuir-Blodgett film (LB) technology, where L denoted the long chain carboxylic ligands monohexadecyl phthalate (16-Phth), monooctadecyl phthalate (18-Phth), monoeicosyl phthalate (20-Phth) and monodocosyl phthalate (22-Phth). The average molecular area was obtained according to the π-A isotherms. The layer structure of the LB films was demonstrated by low-angle X-ray diffraction and the average layer spacing were obtained according to the Bragg equation. The characteristic luminescence behaviors of LB films have been discussed compared with those of their corresponding solid complexes.     

AFM studies on Langmuir-Blodgett films of cholesterol

The Langmuir monolayer of cholesterol at the air-water interface exhibits a condensed phase in which the cholesterol molecules are aligned normal to the water surface. We have transferred the monolayer from water surface to different substrates by Langmuir-Blodgett (LB) technique and have studied their assembly by atomic force microscope (AFM). Our studies reveal that the aggregation of cholesterol molecules on hydrophobic surfaces leads to interesting structures. The cholesterol molecules assemble into a uniform film, elongated domains and uniformly distributed torus-shaped domains (doughnuts) for one, two and four cycles of deposition, respectively. Beyond four cycles, the molecules adsorb and desorb by an equal amount resulting in no further deposition. The formation of uniformly distributed doughnuts can be attributed to the hydrophobic interaction and reorganization of the molecules due to successive adsorption and desorption during deposition cycles. Our studies on hydrophilic surfaces show that cholesterol cannot form more than one layer of deposition.PACS: 68.47.Pe Langmuir-Blodgett films on solids; polymers on surfaces; biological molecules on surfaces - 68.37.Ps Atomic force microscopy (AFM) - 68.43.Mn Adsorption/desorption kinetics     

红外光谱研究聚硅氧烷侧链手性液晶及其单体的单层LB膜

一种聚硅氧烷侧链手性液晶P及其单体M的单层LB膜分别在11mN/m和8mN/m的表面压力下,从水汽界面成功地转移到在镀金玻璃片和氟化钙基片上。π-A曲线表明P及其单体M在水汽界面上单层膜的崩溃压力分别是35和11mN/m。红外透过和反射吸收光谱表明两者的生色团部分及烷基链部分倾斜排列在固体基片上,但其倾斜角不同。M比P有更大的倾斜角。同时,不论P或M其烷基链的轴向与芳香核部分的长轴方向并不重合。P的烷基链比M的烷基链更有序。     

小牛胸腺DNA分子Langmuir-Blodgett复合膜的表面增强拉曼光谱研究

本文利用Langmuir-Blodgett(LB)技术将小牛胸腺DNA分子沉积在银基底上,测试并讨论了它的π-A等温曲线,原子力图及表面增强拉曼光谱(SERS)。通过利用LB技术,获得了DNA分子的LB复合膜的高质量的SERS。在DNA分子LB膜的表面增强拉曼光谱中,DNA的核糖和碱基腺嘌呤是吸附活性部位,它们的振动光谱得到增强。DNA的其它碱基和磷酸基团的拉曼光谱强度也明显的得到增强。分析认为DNA分子增强的拉曼光谱主要是由于LB膜的有序结构的贡献,使得SERS效应得到进一步的增强。因此利用LB技术是得到DNA的高质量SERS很好的方法。     

一种液晶化合物LB膜中的分子取向及膜结构

"利用LB技术制备出MPUOPM的Langmuir和LB膜．随着表面压力的升高,在?-A曲线上的可观察到一个明显的折点．通过与分子刚性基团的理论截面积相比较,发现该折点反映的是单层膜向多层膜的转变．紫外可见、偏振红外等光谱被用来研究膜的结构,发现烷基链与基片法线夹角为48o,C＝N基团互相平行,与基片法线呈51o夹角排列．"     

Fourier Transform Infrared Studies of Novel LB Films of Iridium Monoalkoxystilbazole

Grazing Incidence Reflection Fourier Transform Infrared Spectroscopy (GIR-FTIR) has been applied to the determination of the structures of Langmuir-Blodgett (LB) films of iridium monoalkoxystilbazole on aluminised glass. Band assignments, peak positions and relative intensities are given for some characteristic groups. These results indicated that the hydrocarbon chains tend to the orient perpendicular to the film surface. Further, the high relative intensity of C_φ-O asymmetric stretch shows, in a qualitative way, that the transition moment of this vibration is oriented approximately perpendicular to the substrate surface.     

两种烷基取代喹吖啶酮衍生物LB膜的荧光特性

制备了两种烷基取代喹吖啶酮衍生物C6DHQA和C16DMQA的X型Langmuir-Blodgett(LB)膜,采用紫外-可见吸收、稳态荧光和时间分辨荧光的方法研究其溶液及LB的光学特性。研究结果表明,C16DMQA比C6DHQA的吸收谱整体红移,说明烷基链加长减小了分子的能级间隔;两者LB膜的吸收谱较溶液整体红移,说明在LB膜中形成了"J-聚集体"。两种材料的溶液及LB膜都有较强的荧光发射,溶液的荧光谱与吸收谱有很好的镜像对称关系,形成LB膜后,镜像对称关系被打破,两者第三个荧光峰相对强度差别很大。C6DHQA溶液中的荧光寿命为21ns左右,C16DMQA溶液中的荧光寿命为22ns左右,形成LB膜后,荧光寿命明显较少,两者第三个荧光峰对应的荧光寿命差别较大。其原因应归于C16DMQA分子在基板上的排列更密,分子间的相互作用力强,从而对能级结构的影响更大。