Asymmetric Arrangement of Monolayer in the Multilayer Films of 2-Hydroxy-4,4＇-dihexyloxy-azobenzene

Multilayer films of 2-hydroxy-4,4‘‘-dihexyloxy-azobenzene (HAB) on silicon substrates have been studied with atomic force microscopy, temperature-dependent FTIR, and X-Ray diffraction technique. The results show that the multilayer films are formed by stacking of HAB monolayers via π-π interactions and the adjacent two monolayers in the film are arranged in an asymmetric way in the multilayer films.     

3-羟基4，4-二甲基-1-苯基-2-吡咯烷酮的不对称合成

乙醛酸苄酯与异丁醛间在L-脯氨酰胺催化下发生不对称交叉羟醛缩合反应,以93%的产率得到e.e.值为52%的3-甲酰基-2-羟基-3-甲基丁酸苄酯(1).经过一步还原氨解关环,1很容易转化成3-羟基-4,4-二甲基-1-苯基-2-吡咯烷酮.     

自组装成膜技术制备TiO2薄膜的XPS研究

采用自组装成膜技术制备里TiO2薄膜,应用X射线光电子能谱研究自组装膜及其氧化膜和淀积的TiO2薄膜，结果表明，硅烷偶联剂成功地组装在玻璃基片上，足够长时间的氧化对使端基（-SH）完全氧化为磺酸基，淀积在基片上的TiO2膜牢固性好，平均膜厚在10nm．淀积膜中的钛可能有几种不同的氧化态，不同的酸度影响TiO2的淀积效果     

Impact of Linear Alkyl Length on the Assembly of Twisted Perylene Bisimides: From Molecular Arrangement to Nanostructures

The effect of the length of linear alkyl chains substituted at imine positions on the assembly of tetrachlorinated perylene bisimides ( 1 : PBI with −C₆H₁₃; 2 : PBI with −C₁₂H₂₅) has been investigated. Solvent‐induced assembly was performed in solutions of THF and methanol with varying volume ratios. Morphological (SEM, AFM, and TEM) and spectral (UV/Vis, fluorescence, FTIR, and XRD) methods were used to characterize the assembled nanostructures and the molecular arrangement in the aggregates. It was found that uniform structures could be obtained for both molecules in solutions with a high ratio of methanol. PBI 1 formed rigid nanosheets, whereas 2 assembled into longer nanostripes with a high ratio of length to width. On combining the morphological data with the spectral data, it was suggested that π–π stacking predominated in assemblies of 1 , and the synergetic effect of van der Waals interactions from the long alkyl chains and π–π stacking between neighboring building blocks facilitated the growth of the long‐range‐ordered nanostructures of 2 . By changing the linear chain length, the hierarchical assembly of PBIs modified on bay positions could be manipulated effectively.     

Surface Core Level Shifts of Yb Films in the Multilayer,Monolayer and Submonolayer Range

Surface core level shifts in Yb and other rare earth elements, as well as in their compounds, arise from a reduced band width of the 5d band, caused by the reduced coordination at surface sites, with the strength and direction of the shifts depending on the occupation of the 5d band. If the coordination, or more exactly, the local symmetry is considered to be the decisive factor for changing the band width, it is obvious to look for core level shifts even at the interface of two solids. In order to investigate such interface core level shifts, thin Yb films of thicknesses from the multilayer down to the submonolayer range, grown on a polycristalline W substrat, were investigated by photoelectronspectroscopy. It was found, that for decreasing film thicknesses, the ratio of the surface to bulk related 4f intensities increases systematically, and finally, for thicknesses of one up to two monolayers, only the broad, surface related part of the Yb 4f doublet can be observed. For Yb coverages fewer than one monolayer, there is a sudden shift of this remaining doublet towards the Fermi energy, which must result from a reduced occupation of the Yb 5d band due to an electron transfer from Yb to W at the interface.     

OTS自组装单层膜诱导生长Sb_2S_3薄膜及其生长机理

在接近室温的水溶液中通过采用OTS-自组装单分子层制备了Sb2S3薄膜。利用X-射线粉末衍射(XRD)、扫描电子显微镜(SEM)、X-射线能量色散谱(EDS)和紫外-可见分光光度计(UV-Vis)对Sb2S3薄膜的结构、形貌和光学性能进行了表征。结果表明,低温下所制备的薄膜为非晶态结构,当薄膜在空气中200~300℃热处理1h时,非晶态薄膜转化成具有正交晶相结构的多晶结构。光学性能测试表明,沉积的Sb2S3薄膜和在空气中200℃热处理1h后Sb2S3薄膜的能带值分别为2.05和1.78eV。功能化OTS自组装单分子层(SAMs)在Sb2S3薄膜的生长过程中起到了诱导生长的作用。通过实验结果,进一步分析了Sb2S3薄膜的形成机理。     

Study of Titanium–Silver Monolayer and Multilayer Films for Protective Applications in Biomedical Devices

The search for coatings that extend the useful life of biomedical devices has been of great interest, and titanium has been of great relevance due to its innocuousness and low reactivity. This study contributes to the investigation of Ti/Ag films in different configurations (monolayer and multilayer) deposited by magnetron sputtering. The sessile droplet technique was applied to study wettability; greater film penetrability was obtained when Ag is the external layer, conferring high efficiency in cell adhesion. The morphological properties were characterized by SEM, which showed porous nuclei on the surface in the Ag coating and crystals embedded in the Ti film. The structural properties were studied by XRD, revealing the presence of TiO₂ in the anatase crystalline phase in a proportion of 49.9% and the formation of a silver cubic network centered on the faces. Tafel polarization curves demonstrated improvements in the corrosion current densities of Ag/Ti/Ag/Ti/Ag/Ti/Ag/Ti and Ti/Ag compared to the Ag coating, with values of 0.1749, 0.4802, and 2.044 nA.m⁻², respectively. Antimicrobial activity was evaluated against the bacteria Pseudomonas aeruginosa and Bacillus subtilis and the yeasts Candida krusei and Candida albicans, revealing that the Ti/Ag and Ag/Ti/Ag/Ti/Ag/Ti/Ag/Ti coatings exhibit promise in biomedical material applications.     

Orientation of the Azobenzene Spacer of Carboxylic Methyl Ester Gemini Surfactants in Langmuir Monolayer

The Langmuir monolayer of carboxylic methyl ester Gemini surfactants with the azobenzene spacer, referred to as MC_m(azo)MC_m, was prepared and the π‐A isotherms were measured. The result revealed an orientational picture of the azobenzene spacer at the air/water interface. Before irradiation, the planar trans‐azobenzene group adopted an approximate configuration parallel to the interface and lay on the air/water interface. After UV‐light irradiation, the spacer became the twisted cis‐one. Because of the location of the polar headgroups at the air/water interface, the two phenyl rings were also forced to take a near‐parallel orientation with the interface to reduce the free energy. As a result, the spacer thin‐layer was "thickened", which caused an elevation in collapse pressure.     

DNA在氨基功能化偶氮苯自组装膜表面的固定

采用简单快速的方法制备出将DNA固定在其表面的单分子层敏感膜.首先采用表面自组装技术将硅氧烷基偶氮苯衍生物H2NAzoCONHC3Si(OCH3)3(APDA-N-TMSPBA)组装在硅表面,在详细考察单分子层薄膜的化学结构、表面浸润性和分子表面形貌之后,又通过紫外吸收光谱(UV)在位考察了硅氧烷基偶氮苯衍生物的光学异构特性.在DNA在自组装薄膜固定后,X光电子能谱仪(XPS)结果显示出现了明显的磷元素信号,表明DNA分子可以成功固定在自组装膜表面.     

Interfacial Organization of Y‐Shaped Rod–Coil Molecules Packed into Cylindrical Nanoarchitectures

The behavior at the air/water interface and the structures of Langmuir–Blodgett monolayers at different surface pressures of rod–coil molecules, which consist of a Y‐shaped rigid aromatic segment containing peripheral tetradecyloxy groups and a flexible poly(ethylene oxide) (PEO) chain with 17, 21, 34, or 45 repeating ethylene oxide units (Y17, Y21, Y34, and Y45), were investigated. For the Y21 and Y34 molecules, AFM images revealed two kinds of cylindrical nanoarchitectures formed upon compression. The nanostructured films were further investigated by UV/Vis and FTIR spectroscopy. The formation of the cylindrical nanoarchitectures was due to different tilting angles offered by the mismatch of the cross‐sectional areas of the PEO chain and the benzene ring with attached alkyl chains, and the different PEO contents of the molecules. The multiple π–π stacking and hydrophobic interactions provide exceptional stability of the nanostructures and allow them to be preserved in the course of flipping. For the shortest PEO chain of the Y17 molecule, spontaneous aggregation occurred. The Y45 molecule revealed the formation of 2D circular domains caused by entanglement of the longest PEO chains and coiling at the air/water interface. In addition, an interesting vortical morphology was obtained for the Y21 molecule upon deposition of the film onto a mica substrate, which indicates that the substrate chemistry also has an effect on the morphologies during the film‐transfer process.     

Catalytic Asymmetric Iodoesterification of Simple Alkenes

Catalytic asymmetric iodoesterification of simple alkenes was achieved using a dinuclear zinc‐3,3′‐(R,S,S)‐bis(aminoimino)binaphthoxide ( di‐Zn ) complex. For iodoesterification using p‐methoxybenzoic acid, the N‐iodonaphthalenimide (NIN)‐I₂ system was effective for producing iodoesters in a highly enantioselective manner. The synthetic utility of chiral iodo‐p‐methoxybenzoates was also demonstrated. The quartet of metal ionic bond, hydrogen bond, halogen bond, and π‐π stacking is harmonized on the single reaction sphere of di‐Zn catalyst for enabling the highly enantioselective catalytic asymmetric iodoesterification of simple alkenes for the first time.     

Stacking of Self‐Assembled Surface Micelles in Ultrathin Films

Nonpolar fluorophilic/lipophilic tetrablock amphiphiles are investigated on the surface of water and on solid substrates using compression isotherms, Brewster angle microscopy, and atomic force microscopy. At low pressures, the tetrablocks form monolayers of closely packed surface hemimicelles. Further compression causes a 2D/3D transition. At the end of the plateau, half of the deposited material is expelled forming a second monolayer on top of the initially formed monolayer. Both layers of the films consist of surface micelles, thus providing the first example of spontaneous or compression‐driven stacking of self‐assembled nano‐objects.     

Spectroellipsometric Characterization of Multilayer Sol-Gel Fe2O3 Films

Multilayer Fe₂O₃ films were deposited by the sol-gel method on glass substrates using three successive deposition procedures. The films were thermally treated for 1 h at 300°C.The optical and microstructural properties of these films were investigated by spectroscopic ellipsometry (SE) in the 500–1000 nm range. The optical gap was found by fitting the dispersion of the film refractive index (n) with the Wemple-DiDomenico (WDD) formula.The ellipsometric measurements showed also that the Fe₂O₃ films are anisotropic. The birefringence values (n) of the sol-gel films (0.05–0.08) are smaller than the large values of the Fe₂O₃ (which are around 0.28) but increase with the crystalization of the films. AFM mesurements showed that the films treated at 300°C start to crystallize.