花生酸-钌有机螯合物Ru(phen)_3~(2+)的单分子膜和LB膜中分子聚集行为的研究

以功能性的钌有机螯合物Ru(phen) 2 + 3 作为亚相离子 ,花生酸在亚相表面上形成稳定的单分子膜 .π A等温线和动态弹性测量表明 ,此膜因花生酸与钌螯离子发生了静电相互作用而有更大的可压缩性 ,并在固态区发生了分子聚集 .用垂直法成功地制备了嵌有Ru(phen) 2 + 3 离子的超薄有序Y 型LB膜 .光谱实验表明 ,所得LB膜是稳定、均匀的层状三明治结构 ,在层面内Ru(phen) 2 + 3 与花生酸结合成相对稳定的分子基团并形成了J 聚体     

花生酸-钌有机螯合物Ru(phen)2 3+的单分子膜和LB膜中分子聚集行为的研究

以功能性的钌有机螯合物Ru(phen)2 3+作为亚相离子,花生酸在亚相表面上形成稳定的单分子膜.π-A等温线和动态弹性测量表明,此膜因花生酸与钌螯离子发生了静电相互作用而有更大的可压缩性,并在固态区发生了分子聚集.用垂直法成功地制备了嵌有Ru(phen)2 3+离子的超薄有序Y-型LB膜.光谱实验表明,所得LB膜是稳定、均匀的层状三明治结构,在层面内Ru(phen)23+与花生酸结合成相对稳定的分子基团并形成了J-聚体.     

用“表面离子”法制备组分可控的LB膜超分子体系

综述了LB膜超分子体系中“表面离子”法的概念及其与传统的“亚相离子”法的区别. 分别以钌螯合物(Ru(ph2phen)32＋)和金属β-二酮螯合物为例,详细描述这两类不同的“表面离子”在水面上的成膜作用机理,并举例说明“表面离子”法在铺展膜和LB膜中,功能分子二维密度和凝聚态结构精确可调,并对“表面离子”法在多功能分子体系中的应用作了详细描述.     

组份可控的钌螯合物功能单分子膜

用作“表面离子”的钌螯合物Ru(dpphen)32+与脂肪酸类成膜分子以1:2混合时能够得到稳定的混合单分子膜.以十八烷基三氯硅烷（octadecayl trichloro silane, OTS）分子部分取代Ru(dpphen)32+,得到功能分子组份可控的混合单分子膜.研究表明,OTS分子在纯水表面上可以形成交联网状单分子膜结构,混入硬脂酸（SA）分子后,网状结构逐渐被破坏.SA含量增加,破坏的程度就增大,直至SA/OTS为3:1时,完全没有网状交联结构,形成可以用来沉积LB膜的均匀致密的单分子膜.表面离子Ru(dpphen)32+与OTS和SA一起构成三组份混合单分子膜,OTS和Ru(dpphen)32+为表面离子.单分子膜中混有Ru(dpphen)32+分子,可以有效地阻止OTS的交联发生,同时Ru(dpphen)32+/SA基团与OTS/SA基团是均匀共混的.改变Ru(dpphen)32+/SA基团与OTS/SA基团的混合比,即可以做到Ru(dpphen)32+的组份精确可控,得到可用来沉积LB膜的均一、稳定的单分子膜.     

二价钌有机螯合物Ru(dpphen)2+3与花生酸混合LB膜的结构及光谱特性

对不同组分的Ru(dpphen)2+3［简称Ru(Ⅱ)］与花生酸(AA)在纯水亚相上的混合单分子膜的相容性、分子间相互作用以及凝聚单分子膜的结构进行了研究. 成功地将这种功能单体分子膜转移到固体载片上,制备成混合LB膜. 紫外-可见光谱、发射光谱及小角X光衍射表明这种混合LB膜是一种稳定、均一、具有良好的层状结构, 并且在可见光范围内具有很强的吸收及发射峰的功能膜.     

氮掺杂石墨烯量子点/Ru(phen)32+杂化体系电致化学发光法测定诺氟沙星

制备了氮掺杂石墨烯量子点(NGQDs)并表征了其形貌和结构。利用诺氟沙星(NFX)充当主发光体Ru(phen)_3~(2+)共反应剂的条件下,NGQDs能够促进其自身与受体Ru(phen)_3~(2+)之间的共振能量转移并催化Ru(phen)_3~(2+)与NFX之间的电极反应,从而导致体系电致化学发光(ECL)信号显著增强的效果,构建了测定NFX的NGQDs/Ru(phen)_3~(2+)杂化新体系。体系ECL增量的对数值与NFX的浓度在1.0×10~(-8)～1.0×10~(-4)mol/L之间呈良好的线性关系,检测限为3.3 nmol/L。该方法可用于两种商业药品制剂中NFX的测定。     

二价钌有机螯合物Ru（dpphen）3^2＋与花生酸混合LB膜的结构及光谱特性

对不同组分的Ru(dpphen)3^2 [简称Ru(Ⅱ）]与花生酸（AA）在纯水来相上的混合单分子膜的相容性、分子间相互作用以及凝聚单分子膜的结构进行了研究,成功地将这种功能单体分子膜转移到固体载片上,制备成混合LB膜、紫外－可见光谱、发现光谱及小角X光笛射表明这种混合LB膜是一种稳定、均一、具有良好的层状结构,并且可在可见江范围内具有很强的吸收及发射峰的功能膜。     

稀土离子掺杂铕三元配合物探针分子及其温敏漆的制备和性能研究

以氧化铕(Eu_2O_3)、氧化镝(Dy_2O_3)、氧化钇(Y_2O_3)、氧化钕(Nd_2O_3)、甲基丙烯酸(MAA)和邻菲罗啉(phen)为原料制备了Eu(MAA)_3phen,Eu_(0.5)Dy_(0.5)(MAA)_3phen,Eu_(0.5)Y_(0.5)(MAA)_3phen和Eu_(0.5)Nd_(0.5)(MAA)_3phen探针分子,并将不同探针分子分别加到甲基丙烯酸甲酯(MMA)中,在过氧化苯甲酰(BPO)引发下聚合,制得一系列温敏漆样品。采用红外光谱仪、能量色散谱仪、荧光光谱仪和扫描电子显微镜对探针分子的结构、发光性能、形貌和温敏漆的温度猝灭性能进行了表征,研究了掺杂不同稀土离子对探针分子发光性能和温敏漆温度猝灭性能的影响。结果表明,稀土离子(RE~(3+))与MAA配位,phen参与了配位,且掺杂离子未改变Eu(MAA)_3phen结构,Y~(3+)对Eu(MAA)_3phen发光具有敏化作用,Dy~(3+),Nd~(3+)对Eu(MAA)_3phen发光具有不同程度的猝灭作用,所制备的温敏漆在25~65℃范围内均具有良好的温度猝灭性能。综合分析得出,以Eu_(0.5)Y_(0.5)(MAA)_3phen为探针分子的温敏漆具有更好的应用前景。     

Ru~(3+)增敏的化学发光新体系测定呋塞米的研究

Ru~(3+)存在下,呋塞米能够大幅度增强三(1,10-菲咯啉)钌(Ⅱ)(Ru(phen)_3~(2+))-Ce(Ⅳ)体系的化学发光,且当体系中Ru~(3+)的浓度从0增至15μmol/L时,呋塞米对体系发光的增强值提高1个数量级,基于此,建立了高灵敏测定呋塞米的Ru(phen)_3~(2+)-Ce(Ⅳ)-Ru~(3+)体系化学发光方法。在优化实验条件下,该法测定呋塞米的线性范围为5. 0×10~(-9)~2. 0×10~(-6)mol/L,检出限为3. 8×10~(-9)mol/L。方法具有较高的分析灵敏度,将其应用于呋塞米片剂和呋塞米注射液的分析,结果满意。结合紫外光谱的研究结果,对化学发光反应机理进行了探讨。     

血红素在有序分子膜中的行为研究

本文研究了血红素(Heme)在硬脂酸(SA)单分子膜和Langmuir-B1odgett(LB)膜中的行为。Heme及其与SA的混合物均能在纯水亚相形成稳定的单分子膜。当摩尔分数x     

由组分可控的LB膜前驱物法制备Y2O3稳定立方相ZrO2的超薄陶瓷膜

由有机LB膜技术发展了一种制备组分、厚度可控的无机超薄陶瓷膜的方法.以Zr、 Y的β-二酮络合物的作为"表面离子"代替传统的亚相离子,沉积它们与花生酸的混合LB膜.并将它作为前驱物,经臭氧处理和热处理,成功制得了Y2O3稳定的立方相ZrO2超薄膜(YSZ).用X射线衍射(XRD)、 X射线光电子能谱(XPS)等手段研究了YSZ薄膜的相结构和其组成.结果表明,超薄陶瓷膜中Zr与Y的含量比率控制得很好,且形成Y2O3稳定的立方相ZrO2.说明这种方法可以成功地用来制备组分和膜厚均可控的纳米陶瓷膜.     

Electron transfer through clay monolayer films fabricated by the Langmuir-Blodgett technique

Hybrid films composed of amphiphilic molecules and clay particles were constructed by the modified Langmuir-Blodgett (LB) method. Clays used were sodium montmorillonite (denoted as mont) and synthetic smectite containing Co(II) ions in the octahedral sites (denoted as Co). Two kinds of amphiphilic molecules were used-[Ru(dC(18)bpy)(phen)2](ClO4)2 (dC(18)bpy = 4,4'-dioctadecyl-2,2'-bipyridyl and phen = 1,10-phenanthroline) (denoted as Ru) and octadecylammonium choloride (ODAH+Cl- or denoted as ODAH). Three kinds of hybrid films (denoted as Ru-mont, Ru-Co, and ODAH-Co films) were prepared by spreading an amphiphilic molecule onto an aqueous suspension of a clay. Atomic force microscopy (AFM) analyses of the films deposited on silicon wafers indicated that closely packed films were obtained at 20 ppm for all the above three cases. Cyclic voltammetry (CV) was measured on an ITO electrode modified with a hybrid film or a monolayer film of pure Ru(II) complex salt (denoted as Ru film). The Ru(II) complexes incorporated in the Ru-mont film lost their redox activity, indicating that montmorillonite layers acted as a barrier against electron transfer. In contrast, the same complexes in the Ru-Co film were electrochemically active with the simultaneous appearance of the redox peaks due to the Co(II)/Co(III) (or Co(II)/Co(IV)) couple. The results implied that electron transfer through cobalt clay layers was possible via mediation by Co(II) ions in a clay sheet. For an aqueous solution containing nitrite ions (NO2-) at pH 3.0, a large catalytic oxidation current was observed for both the electrodes modified with the Ru-mont and Ru-Co films. The results were interpreted in terms of the mechanisms that the charge separation of an incorporated Ru(II) complex took place to produce a pair of a Ru(III) complex and an electron and that the generated Ru(III) complex was reduced by a nitrite ion before it recombined with the electron.     

Effect of Metal Ions on the Formation and Properties of Monolayers and Nanosized Langmuir-Blodgett Films Based on Diphilic Aminomethylated Calix[4]resorcinarenes

The behavior of the monolayers of three diphilic aminomethylated calix[4]resorcinarene (CRA) derivatives on the surface of a pure aqueous subphase and subphase containing copper(II), nickel(II), europium(III), terbium(III), and lanthanum(III) ions was investigated. The monolayer transfer to the quartz and single-crystal silicon substrates was accomplished by the Langmuir-Blodgett (LB) technique. The films were studied by ellipsometry and mass-spectrometry. Metal ions were found to exert effect on the limit area per one CRA molecule in the monolayer, on the surface collapse pressure and transfer coefficient of monolayer, and on the thickness and refractive index of the CRA-based LB films.     

PREPARATION OF PHOTOFUNCTIONAL POLYMER THIN FILMS BY LANGMUIR-BLODGETT TECHNIQUE

Polymer LB films containing photofuntional groups were prepared by the copolymerization of N-dodecylacrylamide (DDA), which has an excellent property to form a stable monolayer and LB multilayerswith photofunctional monomers. Tris(2, 2'-bipyridine) ruthenium complex, Ru(bpy)_3~(2+), one of the most well-known redox-active sensitizer, was incorporated into the DDA copolymer. The photogalvanic effect based onthe photoinduced electron transfer using the ruthenium complex in the polymer LB monolayer was discussed.     

Thermodynamic and spectroscopic studies on the nickel arachidate-RNA polymerase Langmuir-Blodgett monolayer

The Langmuir-Blodgett (LB) monolayers offer a unique system to study molecular interaction at the air-water interface with reduced dimensionality. In order to develop this further to follow macromolecular interactions at equilibrium, we first characterized the Ni (II)-arachidate (NiA) monolayer at varying conditions. Subsequently, the interaction between NiA and histidine-tagged RNA polymerase (HisRNAP) were also studied. LB films of arachidic acid-NiA and NiA-RNAP with different mole fractions were fabricated systematically. Surface pressure versus area per molecule (P-A) isotherms were registered, and the excess Gibbs energy of mixing was calculated. The LB films were then deposited on solid supports for Fourier transform infrared (FTIR) spectroscopic measurements. The FTIR spectra revealed the change in the amount of incorporated Ni (II) ions into the arachidic acid monolayer with the change in pH and the increasing mole fraction of RNAP in the NiA monolayer with its increasing concentration in the subphase. The system developed here seems to be robust and can be utilized to follow macromolecular interactions.     

表面离子法制备多组分LB膜和CeO_2-Gd_2O_3陶瓷膜

以铈、钆的β二酮螯合物Ce(tmhd)_4和Gd(tmhd)_3(tmhd = tetramethylheptanedionate)为表面离子,与花生酸（AA）在水面上共铺展,可 形成具有良好相容性、稳定性和可压缩性的混合Langmuir膜,这是由于稀土螯合物 与AA间发生了新的配合,而且Gd(tmhd)_3与AA间的相互作用更强。用垂直法将它们 的三组分混合Langmuir膜沉积,制得了具有良好周期性结构的Y型三组分混合LB膜 。以它作前驱物,经过紫外臭氧（UVO）和热处理,制得了CeO_2-Gd_2O_3(CGO)超 薄陶瓷膜。X射线光电子能谱（XPS）表明,由于两种稀土螯合物和AA间的结合强度 不同,在沉积LB膜时表面离子发生了选择性转移,而且温度对表面离子的转移选择 性有影响。这对制备组分和厚度可控的应用薄膜很有意义。     

Single molecular detection of a perylene dye dispersed in a Langmuir-Blodgett fatty acid monolayer using surface-enhanced resonance Raman scattering

The Langmuir-Blodgett (LB) monolayer technique was used to fabricate single molecule LB monolayer containing bis(phenethylimido)perylene (PhPTCD), a red dye dispersed in arachidic acid (AA) with an average doping of 1 molecule per microm2. The monolayer was transferred onto Ag island films to obtain spatially resolved surface-enhanced resonance Raman scattering (SERRS) spectra. The mixed LB monolayers were fabricated with a concentration, on average, of 1, 6, 19 and 118 PhPTCD molecules per microm2 in AA. The AA provides a two-dimensional host matrix whose background signal does not interfere with the detection of the probe molecule's SERRS signal. The properties of the single molecule detection were investigated using micro-Raman with a 514.5-nm laser line. The Ag island surfaces coated with the LB monolayer were mapped with spatial steps of 3 microm and global chemical imaging of the most intense SERRS band in the spectrum was also recorded. The SERRS and surface-enhanced fluorescence (SEF) of the neat and single molecule LB monolayer were recorded in a temperature range from liquid nitrogen to + 200 degrees C. Neat PhPTCD LB monolayer spectra served as reference for the identification of characteristic signatures of the single molecule behavior. The spatial resolution of Raman-microscopy experiments, the multiplicative effect of resonance Raman and SERRS, and the high sensitivity of the new dispersive Raman instruments, allow SERRS to be part of the family of single molecular spectroscopies.