Oxide/water interfaces: how the surface chemistry modifies interfacial water properties

The organization of water at the interface with silica and alumina oxides is analysed using density functional theory-based molecular dynamics simulation (DFT-MD). The interfacial hydrogen bonding is investigated in detail and related to the chemistry of the oxide surfaces by computing the surface charge density and acidity. We find that water molecules hydrogen-bonded to the surface have different orientations depending on the strength of the hydrogen bonds and use this observation to explain the features in the surface vibrational spectra measured by sum frequency generation spectroscopy. In particular, 'ice-like' and 'liquid-like' features in these spectra are interpreted as the result of hydrogen bonds of different strengths between surface silanols/aluminols and water.     

十二烷基硫酸钠(SDS)增强若丹明6G水溶液激光激发荧光谱研究

报道了若丹明6G水溶液添加不同浓度的表面活性剂十二烷基硫酸钠(SDS)时激光激发染料的变化,发现较低的掺入量导致R6G荧光减弱,适量SDS的加入使荧光增强,在5×10-5 mol·L-1的R6G水溶液中,加入6×10-2 mol·L-1 SDS,荧光增强因子达到3.1。当R6G浓度为1×10-4 mol·L-1时,加入2×10-2 mol·L-1,染料激光阈值显著降低。测量了不同浓度的R6G溶液的吸收光谱及加入不同浓度SDS后的荧光谱,分析了不同SDS加入量下R6G荧光减弱及增强的物理机制。     

银纳米粒子与R6G分子间的电荷转移

本文通过吸收光谱、表面增强垃曼光谱、荧光光谱等手段研究了银纳米粒子与罗丹明6G（R6G）分子之间的相互作用,结果表明：银纳米粒子表面与R6G分子之间存在电荷转移效应。表现为吸收谱长波方向出现银粒子－R6G复合体的吸收带,R6G分子的拉曼振动模得到显著增强,而其荧光得到明显猝灭;AgN特征拉曼振动带的出现服银米粒子与R6G分子是通过银粒表面的活位与R6G分子中的氮原子配位形成复合体而发生电荷转移的。     

银/硅纳米孔柱阵列活性基底的SERS效应研究

以硅纳米孔柱阵列(Si-NPA)为衬底,采用浸渍法制备出一种具有规则表面形貌特征的银/硅纳米孔柱阵列(Ag/Si-NPA),并以R6G为探测目标材料,对其表面增强拉曼(SERS)效应进行了研究。结果表明,对于R6G浓度低至10-15M,Ag/Si-NPA均能表现出清晰的特征SERS峰。随着浓度的降低,R6G的荧光淬灭,所测拉曼光谱的基线降低,但特征峰峰位基本保持不变。在低浓度10-15M时得到的SERS光谱,理论上证明为单分子光谱。此外,Ag/Si-NPA活性基底具有较好的稳定性,在长达28天的自然老化过程中,Ag/Si-NPA能够保持对R6G较高的探测水平,光谱具有较好的信噪比和分辨率。Ag/Si-NPA是一种理想的SERS活性基底。     

Raman spectroscopic determination of the acidity constants of salicylaldoxime in aqueous solution

A sensitive and efficient method for the determination of acidity constants of salicylaldoxime (SALO) (2‐hydroxybenzaldehyde oxime), using both Raman spectroscopic and potentiometric methods, at 30 °C in 50% (wt/wt) of ethanol–water mixture and at the constant ionic strength I = 0.1 M is proposed. The effect of pH on the Raman spectra has also been studied. The Raman spectroscopic technique allows the identification of compounds in different molecular and molecular ionic structures. The limit of detection (LOD) was determined to be 0.05 mol dm⁻³ for SALO by means of Raman peak area. Copyright © 2010 John Wiley & Sons, Ltd.     

Functionalized Ultrabright Fluorescent Mesoporous Silica Nanoparticles

The problem of functionalization of recently reported ultrabright fluorescent mesoporous silica nanoparticles while preserving their fluorescent brightness is solved. This is a serious issue because of the open geometry of mesoporous channels and physical encapsulation of fluorescent dye inside those channels. Amine modification of mesoporous nanoparticles is described to preserve the brightness comparable to that of earlier reported ultrabright silica nanoparticles. Scaling to 40 nm sized particles, amine‐functionalized nanoparticle have fluorescent brightness equivalent to the one of 630 free rhodamine 6G (R6G) dye molecules in water. To demonstrate further most challenging functionalization, which relies on using organic‐solvent‐based chemistry, folic acid conjugation is developed. Two different methods are used to conjugate folites to the amine functionalities. Both methods result in a decrease of fluorescence intensity, which can nonetheless still be called ultrabright. The brightness can drop to either 310 or 80 R6G dye molecules per particle of nominal diameter of 40 nm.     

SiO2纳米颗粒对R6G-乙醇溶液荧光光谱影响

在3×10－4M和1×10－4M浓度的R6G-乙醇溶液中分别掺杂了8个不同浓度的SiO2纳米颗粒（107～1012 个/mL）.研究了SiO2纳米颗粒（100 nm）对若丹明6G（R6G）荧光光谱的影响,结果表明:n1～n4(1012～1010个/mL)浓度掺杂的SiO2纳米颗粒在549 nm处的有很好的荧光增强作用,对570 nm处的荧光峰有明显的粹灭作用|n5～n8(109~107个/mL)浓度掺杂的SiO2纳米颗粒在549 nm处没有明显的荧光增强作用,但对570 nm处的荧光峰有增强作用,荧光增强因子可达10%~20%.荧光增强与粹灭的原因在于纳米颗粒对荧光的散射作用和R6G无荧光H-型二聚体或荧光J-型二聚体的形成.     

Spectroscopic investigation on the sonodynamic activity of amsacrine (AMSA) to bovine serum albumin (BSA) damage

The sonodynamic damage of bovine serum albumin (BSA) under ultrasonic irradiation in the presence of amsacrine (AMSA) was studied by hyperchromic effect of UV-vis spectra and quenching effect of intrinsic fluorescence. In addition, several influencing factors such as ultrasonic irradiation time, AMSA concentration, system acidity and ionic strength about the damage of BSA molecules were reviewed. The results showed that the damage degree was obviously enhanced with the increase of ultrasonic irradiation time and AMSA concentration, but it was only slightly increased with the increase of solution pH value and ionic strength. Furthermore, the binding and damaging sites to BSA molecules were estimated by synchronous fluorescence spectra. The different chances to damage tryptophan (Trp) and tyrosine (Tyr) residues were found through the ratios of synchronous fluorescence quenching (R_SFQ). At last, the generation of reactive oxygen species (ROS) in sonodynamic process was estimated by the method of oxidation-extraction Spectrometry (OES). And then, several radical scavengers were used to determine the kind of ROS, which includes singlet oxygen (¹O₂) and hydroxyl radicals (·OH). Perhaps, the result would bring a certain guiding significance to use sonosensitive drugs in the fields of tumor treatment.     

若丹明6G和若丹明B混合染料荧光谱特性及染料激光行为

实验发现若丹明6G和若丹明B混合溶液的荧光谱峰值波长随两种物质的混合比例不同而有规律地变化,与单一的若丹明6G和若丹明B相比,混合溶液的荧光谱线宽度明显增宽。使用混合染料,用改变混合比的方法对染料激光进行调谐,可简化调谐方法,调谐范围为557.4-588.5nm。     

氧化石墨烯猝灭罗丹明6G荧光的机理研究

The fluorescence quenching of Rhodamine 6G (R6G) by graphene oxide (GO) was interrogated by R6G fluorescence measurements using a set of controlled GO samples with varied C/O ratios as the quencher.The carbonyl groups on the GO nanosheet turned to play a dominant role in quenching the R6G fluorescence.The quenching in the static regime can be described by the "sphere of action" model.The significant absorption of the R6G fluorescence by the ground-state complex formed between R6G and GO was identified to be responsible for the static quenching.This work offers helpful insights into the fluorescence quenching mechanisms in the R6G/GO system.     

Intermolecular Interactions. Absorption and Fluorescence Spectra of α-Naphthol

In the ground state, -naphthol interacts with water via oxygen, whereas with alcohols (ethanol and isopropanol) and acetonitrile it interacts via hydrogen from the hydroxyl group. In the excited state, -naphthol interacts much more weakly. An analysis of the dependences of positions of electronic-vibrational transitions on the solvent basicity and acidity demonstrates their nonlinearity. For the parameters describing the solvation ability of the solvent, linear dependences are observed for the following series of solvents: isopropanol, ethanol, acetonitrile, and water. The possible values of the acid number (pA*) for the excited -naphthol molecule fall within the interval from 0.4 to 1.4 depending on the chosen maximum of the absorption band. In fluorescence spectra, the band intensities differ for neutral and ionic modifications of the molecule. The fluorescence efficiency of the neutral molecule is by an order of magnitude higher than that of the ionic modification. Possible channels of quenching of the ionic modification are discussed.     

Solvent effects on the gain of rhodamine 6G

The effect of solvents on the gain and the peaks of gain spectra is investigated for rhodamine 6G (R6G) under nitrogen laser pumping. The non-specific solute-solvent interaction for R6G is found to be mainly dispersive. Additional shifts produced for R6G in certain solvents are explained as due to hydrogen bonding. The gain characteristics are interpreted on the basis of the position and overlap of absorption and fluorescence spectra, the quantum yield, the absorption at the pumping wavelength and the refractive index of the solvent. For the solvents studied it is found that R6G has high gain in solvents with low refractive index and high polarity. Amongst the solvents studied the alcohols displayed the highest gain with methanol being the most suitable solvent. The lowest gain amongst the alcohols was with capryllic alcohol which gave a gain that was 69% of that obtained with methanol. Amongst all the solvents studied the lowest gain was with chloroform, being only 34% of the gain in methanol.     

醋酸N-正辛基吡啶离子液体在不同溶剂中的荧光光谱分析

离子液体具有熔点低、可忽略的蒸气压、电化学窗口宽、热稳定性高和良好的导电性等独特性能,引起了化学工业和相关领域的广泛关注。离子液体具有低蒸气压,不会造成空气污染,但这并不意味着它们对环境完全无害。大多数离子液体易溶于水,可能会因为意外泄漏或通过污水进入水生环境。常用离子液体[BMIM][PF₆]和[BMIM][BF₄]的水溶液中,很容易形成氢氟酸,磷酸,具有一定的腐蚀性。将离子液体列为绿色溶剂,也需要提供其关于代谢和降解的毒性、生态毒性研究数据,或者其对环境影响的数据,离子液体在不同溶剂中的检测方法是非常重要的。离子液体的光谱分析法用量较少、方法简单、结果准确。离子液体和许多有机溶剂互溶,可形成均一、稳定的溶液。荧光检测法具有灵敏度高,选择性好,线性范围宽和受外界干扰少等优点。本工作研究了醋酸N-正辛基吡啶（OP-OAc）离子液体在水、乙醇、乙腈、乙酸等4种溶剂中的荧光光谱。研究结果表明,OP-OAc离子液体在不同溶剂中的荧光强度：I_乙酸＞I_乙腈＞I_乙醇＞I_水;最大发射波长的大小顺序：λ_{em, 水}＞λ_{em, 乙醇}＞λ_{em, 乙腈}＞λ_{em, 乙酸};它们的最大发射波长相对于激发波长发生红移;水中OP-OAc的荧光强度与浓度存在较高的相关性;当加入的甲醇、乙醇、乙腈溶剂不断增加时,OP-OAc离子液体的荧光强度增加,溶剂与水的比例为8∶2时,OP-OAc离子液体的荧光强度最强,溶剂的比例超过80%时,荧光强度突然降低;水中OP-OAc离子液体在pH 10时,荧光强度最高,在pH 14时,荧光强度最低。     

The Synthesis of Magnetic and Fluorescent Bi-functional Silica Composite Nanoparticles via Reverse Microemulsion Method

In this paper, a simple synthesis method of small-size( about 50 nm in diameter), high magnetic and fluorescent bi-functional silica composite nanoparticles were developed, in which water-soluble Fe₃O₄ magnetic nanoparticlels (MNs) and CdTe quantum dots (QDs) were directly incorporated into a silica shell by reverse microemulsion method. The high luminescent QDs can be used as luminescent marker, while the high magnetic MNs allow the manipulation of the bi-functional silica composite nanoparticles by external magnetic field. Poly (dimethyldiallyl ammonium chloride) was used to balance the electrostatic repulsion between CdTe QDs and silica intermediates to enhance the fluorescence intensity of MNs-QDs/SiO₂ composite nanoparticles. The optical property, magnetic property, size characterization of the bi-functional composite nanoparticles were studied by UV-Vis and PL emission spectra, VSM, TEM, SEM. The stabilities toward time, pH and ionic strength and the effect of MNs on the fluorescence properties of bi-functional silica composite nanoparticles were also studied in detail. By modifying the surface of MNs-QDs/SiO₂ composite nanoparticles with amino and methylphosphonate groups, biologically functionalized and monodisperse MNs-QDs/SiO₂composite nanoparticles can be obtained. In this work, bi-functional composite nanoparticles were conjugated with FITC labeled goat anti-rabbit IgG, to generate novel fluorescent-magnetic-biotargeting tri-functional composite nanoparticles, which can be used in a number of biomedical application.     

Total Internal Reflection Fluorescence Spectroscopy for Investigating the Adsorption of a Porphyrin at the Glass/Water Interface in the Presence of a Cationic Surfactant Below the Critical Micelle Concentration

Total internal reflection fluorescence (TIRF) spectroscopy was used to investigate the adsorption behavior of meso-tetrakis(p-sulfonatophenyl)porphyrin (TPPS) at the glass/water interface in the presence of a cationic surfactant (cetyltrimethylammonium bromide, CTAB) far below the critical micelle concentration. The adsorption model of TPPS at the glass/water interface in the presence of low concentration of CTAB was proposed, which was different from the adsorption of TPPS in the presence of micelles of CTAB at the glass/water interface. TPPS and CTAB did not form stable complex at the interface in dilute system. The interfacial species of TPPS were analyzed by comparing the spectra of TPPS at the glass/water interface and in the aqueous phase. The influences of the TPPS concentration, the CTAB concentration, and the pH values on the interfacial fluorescence spectra and intensities were studied. It was demonstrated that electrostatic interaction and hydrophobicity performed an important role on the adsorption of TPPS in the presence of CTAB. The different effects of TPPS concentration on the adsorption behaviour of TPPS at different pH were observed for the first time. It was found that the adsorption isotherms of TPPS at glass/water interface could fit Freundlich equation at pH 7.1.     

XPS with fast-frozen samples: A renewed approach to study the real mineral/solution interface

The procedure for XPS study of quick-frozen solutions developed at the end of 1970s [K. Burger, E. Fluck, Inorg. Nucl. Chem. Lett. 10 (1974) 171] was modified and applied to investigate the mineral/solution interface formed at the surface of silica, gibbsite, goethite and manganite in aqueous sodium chloride solution at variable pH and ionic strength.The Na/Cl atomic ratio (frozen samples) allows determination of the pH range where the mineral surface charge is close to zero. This ratio can be used also to prove an ion pair formation at the surface. From the intensity of the O 1s component corresponding to water, an interface thickness of 0.5 nm was estimated. A “built-in” potential at the interface, evincing as matrix elements photoelectron lines shifts after water loss, was found. This potential arises due to the spatial separation of the charged mineral surface and counter-ions in the electrical double layer (EDL). Its value does not exceed 250 mV and the sign depends on the charge of the mineral surface.     

Optical properties of Coumarin 314 doped sol-gel silica rods

Silica rods containing Coumarin 314 have been fabricated by the sol-gel method and their optical properties have been investigated under a linear Xenon flashlamp excitation. The fluorescence spectra of Coumarin 314 peaked at 508 nm in sol-gel silica while they peaked at 476 nm in ethanol. The fluorescence spectra of Coumarin 314 doped sol-gel silica rods were measured as function of heat treatment temperature. As heat treatment temperature of the rods increases, the fluorescence spectra band becomes somewhat broader. The photodegration of Coumarin 314 doped sol-gel silica rods was also studied under linear Xenon flashlamp excitation. The bulk transmission losses of the rods immersed in water were measured to be 0.51–0.57%/cm.     

Surface-enhanced resonance Raman scattering spectroscopy of single R6G molecules

Surface-enhanced resonance Raman scattering (SERRS) of Rhodamine 6G (R6G) adsorbed on colloidal silver clusters has been studied. Based on the great enhancement of the Raman signal and the quench of the fluorescence, the SERRS spectra of R6G were recorded for the samples of dye colloidal solution with different concentrations. Spectral inhomogeneity behaviours from single molecules in the dried sample films were observed with complementary evidences, such as spectral polarization, spectral diffusion, intensity fluctuation of vibrational lines and even ``breathing' of the molecules. Sequential spectra observed from a liquid sample with an average of 0.3 dye molecules in the probed volume exhibited the expected Poisson distribution for actually measuring 0, 1 or 2 molecules. Difference between the SERRS spectra of R6G excited by linearly and circularly polarized light were experimentally measured.     

环己烷/水界面自组装纳米银膜及性能研究

在环己烷/水界面以自组装的方式将单层密排的银纳米粒子膜转移到亲水性的硅片上,以罗丹明6G(R6G)为探针分子,通过与直接滴加银胶溶液和混合R6G后的银胶溶液得到的两种SERS基底对比,密排银纳米粒子膜展现了极高的灵敏度(R6G的检测极限为10-9 mol/L)和信号再现性。结合有限时域差分法(FDTD)对其增强原因进行了模拟分析,实验结果与理论模拟基本相符。     

Application of Fluorescence with Polarized Light to Evaluate the Orientation of Dyes Adsorbed in Layered Materials

A new method of fluorescence polarization is applied to evaluate the angle of the preferential orientation of Rhodamine 6G (R6G) dye adsorbed in supported thin films of Laponite (Lap) clay. The method is based in the determination of the fluorescence dichroic ratio, obtained from the recorded fluorescence spectra with the detection polarizer horizontally and vertically oriented, as a function of the twisted angle of the film around its vertical axis, keeping the excitation polarizer in a fixed direction. The validity of the method is checked by comparing the experimental results obtained with both vertically and horizontally polarized excitations to that previously provided by absorption spectroscopy with linearly polarized light. A preferential orientation angle with respect to the normal to the clay layer of 62° is derived for R6G monomers adsorbed in Lap films.