Protein adsorption drastically reduces surface‐enhanced Raman signal of dye molecules

There is an increasing interest in developing surface enhancement Raman spectroscopy methods for intracellular biomolecule and for in vitro protein detection that involve dye or protein–dye conjugates. In this work, we have demonstrated that protein adsorption on silver nanoparticle (AgNP) can significantly attenuate the surface‐enhanced Raman spectroscopy (SERS) signal of dye molecules in both protein/dye mixtures and protein/dye conjugates. SERS spectra of 12 protein/dye mixtures were acquired using 4 proteins [bovine serum albumin (BSA), lysozyme, trypsin, and concanavalin A] and three dyes [Rhodamine 6G, adenine, and fluorescein isothiocyanate (FITC)]. Besides the protein/dye mixtures, spectra were also obtained for the free dyes and four FITC‐conjugated proteins. While no SERS signal was observed in protein/FITC mixtures or conjugates, a significantly reduced SERS intensity (up to 3 orders of magnitude) was observed for both R6G and adenine in their respective protein mixtures. Quantitative estimation of the number of dye molecules absorbed onto AgNP implied that the degree of R6G SERS signal reduction in the R6G/BSA sample is 2 to 3 orders of magnitude higher than what could be accounted for by the difference in the amount of the absorbed dyes. This finding has significant implications for both intracellular SERS analyses and in vitro protein detection using SERS tagging strategies that rely on Raman dyes as reporter molecules. Copyright © 2009 John Wiley & Sons, Ltd.     

Unusual induction of optical anisotropy in polymer media by low-intensity polarized x-rays

The induction of linear dichroism in (poly) methylmetacrylate films activated with Rhodamine 6G and its base in the spectral range of absorption of these dyes under the action of plane-polarized x-rays with wavelength 0.70Å and intensity 7.5·10⁴ quanta per second has been revealed. The phenomenon is discussed from the standpoint of the radiochemical analog of the photochemical polarization-induced selection of organic molecules with allowance for the structural characteristics of the polymer film components.     

Optical properties of Rhodamine B and Rhodamine 6G on silver surfaces

The transmission spectra of Rhodamine B and Rhodamine 6G dyes coated on silver island films for various thickness were recorded. A strong coupling between the silver particle plasma resonance and the dye molecules is observed. The absorption of dye molecules increases when the absorption band of individual dyes and silver particles overlaps. In higher silver film thicknesses, transmission increases. The theoretical calculation using Maxwell-Garnett theory and Wang and Kerker’s results qualitatively supports the observed phenomenon. A red shift in the absorption peak of dyes on silver surfaces in comparison to solution phase absorption peak indicates photobleaching.     

Ultrafast measurement of two-photon absorption by loss modulation

We demonstrate a direct and sensitive technique for measuring two-photon absorption (TPA). An intensity-modulated femtosecond laser beam passes through a sample exhibiting TPA. A TPA signal at twice the modulation frequency is then generated and subsequently measured by a lock-in amplifier. The absolute TPA cross section of Rhodamine 6G at 800nm is found to be (15.3+/-2.0)x10(-50) cm(4) s/photon and agrees well with previously published results obtained with much higher intensity [J.Chem.Phys.112, 9201 (2000)]. Our method may be especially useful in measuring nonlinear absorptions of nonfluorescent materials.     

Spectral-Kinetic Properties of Laser Dyes in Active Elements on the Basis of Sol-Gel Matrices

The absorption and photoluminescence spectra as well as the photoluminescence lifetimes of laser dyes (Phenylamine 430, Rhodamine 6G, Rhodamine 6G zwitterion, Rhodamine 4C, and Rhodamine 101) in new matrices are studied. These matrices represent the hybrid of two types of porous glasses (microporous and sol-gel glass). Chemical transformations of the dye molecules in the matrices are not found. The dye dimers mentioned above are also absent for concentrations up to 10^-4 M. The luminescence efficiencies of the dyes in the matrix and in the ethanol solutions are compared. The difference in concentration dependences of the photoluminescence spectrum of Rhodamine 6G in the matrix and ethanol solution is found and discussed. The collective emission of the dyes in new matrices is observed at a power density of exciting radiation of 10²⁵ cm^-2s^-1 and a concentration of 10^-4 M. The energies and collective emission spectra of the dyes in the matrix are compared with those in the solutions.     

不同构型罗丹明分子拉曼光谱的密度泛函理论研究

利用密度泛函理论研究了罗丹明6G、罗丹明123和罗丹明B分子的拉曼光谱. BP86泛函计算的罗丹明系列分子的阳离子在气相中的拉曼光谱与相应的分子在水溶液中的实验光谱符合很好. 结果显示氯离子以及氢键的引入对罗丹明B分子的拉曼光谱有较明显的影响,该影响可以部分地解释罗丹明B分子在水溶液中和在金表面上拉曼光谱的不同. 精确描述罗丹明分子在金属表面的表面增强拉曼光谱,需要考虑由界面相互作用而导致的变化.     

Thermally Stable Schiff Base and its Metal Complexes: Molecular Docking and Protein Binding Studies

In this paper, interaction of Schiff base and its metal complexes carrying naphthalene ring in the structure with bovine serum albumin (BSA) were investigated using UV-vis absorption, fluorescence spectroscopies and molecular docking methods. The effect on the binding mechanism and properties of these compounds containing metal-free, iron and copper ions were also investigated. The fluorescence spectroscopy results showed that fluorescence intensity of BSA in the presence of different concentration of ligands was decreased through a static quenching mechanism. Binding constants (KSV, Kbin and Ka) and thermodynamic parameters (ΔG, ΔH and ΔS) for the ligand-protein interactions were also determined. ΔG values of ligand-protein interaction were calculated in the range ? 6.3 to ?5.5 kcal/mol. These negative values showed that binding process is spontaneous and, hydrogen bonding and van der Waals force were main interaction of the protein and ligands. ΔH and ΔS value were also calculated in the range of 1.10 to 1.26 kJ/mol and 0.133 to 0.135 kJ/mol. K, respectively. These positive values indicated that the binding process between ligands and BSA are endothermic and electrostatic interaction, respectively.     

Photoacoustic studies on excitation transfer in Rh6G and RhB dye mixture

The photoacoustic spectra of Rhodamine 6G (Rh6G), Rhodamine B (RhB) dyes and their mixtures were recorded at different concentrations. It is observed that in the mixture the photoacoustic signal increases due to excitation transfer from Rh6G to RhB in the wavelength region 480–530 nm. The excitation transfer rate estimated from these data show that resonance is dominant rather than the collisional transfer process.     

Experimental and theoretical studies on the one‐photon and two‐photon properties of a series of carbazole derivatives containing styrene

Symmetric‐type carbazole derivatives show great potential for application in two‐photon absorption (TPA) materials and organic light‐emitting diodes. The absorption spectra and fluorescence emission spectra of three different N‐alkyl symmetric‐type carbazole derivatives were investigated. The density functional theory (DFT) time‐dependent‐DFT//Becke, three‐parameter, Lee–Yang–Parr/6‐31 G* method has been used to theoretically study one‐photon absorption properties. The computational results are in good agreement with the available experimental values. The two‐photon excited fluorescence of the compounds was surveyed by 120 fs pulse at 790 nm Ti: sapphire laser operating at 1 kHz repetition rate. Two‐photon excited fluorescence was obtained in the range of 380–600 nm, and TPA cross‐sections were calculated. The TPA properties of the series of compounds were investigated by the ZINDO/single and double electronic excitation configuration interaction method. The influence of the chemical structure of the compounds on two‐photon optical properties was discussed. The results show how the different changes in one‐photon absorption and TPA properties on the basis of lengthening the conjugated bridge and the different carbazole N‐alkyl substituents are attributed to the transition dipole moment in the excited process. Copyright © 2011 John Wiley & Sons, Ltd.     

Solid‐State Active Elements Based on Dyes and Prepared by a Sol‐Gel Method

A new method is suggested for producing the solgel matrices with the molecules of laser dyes introduced into them. The curves of tuning lasing in Rhodamine 6G, Rhodamine 4S, Rhodamine 101, and phenylamine 430 in these matrices are obtained. The total range of tuning is 550–650 nm at a pumping energy of 4 mJ. The halfwidth of the generation spectrum is independent of the pumping energy to 4 mJ and comprises 0.3 ± 0.1 nm. The main factors forming the generation spectrum are noted.     

Theoretical study of one‐ and two‐photon absorption properties of expanded donor–acceptor calix[4]arenes

Two types of donor(D)–acceptor(A) calix[4]arenes have been theoretically studied using DFT//B3LYP/6‐31G(d) method and ZINDO/CISD method. The calculations show that the substitution of C? C by the conjugation bridge C?C and N?N plays an important part in altering one‐photon absorption (OPA) and two‐photon absorption (TPA) properties. The maximum OPA wavelengths of all studied compounds are less than 400 nm, which means high transparency. The geometry of the calixarenes strongly influences the TPA properties of the studied compounds. In addition, the nitro derivatives have a wider TPA response range than other non‐nitro derivatives. The tetrasubstituted calix[4]arenes (type B calixarenes) have a larger TPA cross‐section values than the bisubstituted calix[4]arenes (type A calixarenes). Copyright © 2009 John Wiley & Sons, Ltd.     

Synthesis of Graphene Nanoparticles and Their Application in Surface Raman Enhancement

Multilayer graphene-enclosed nickel nanoparticles have been prepared on the SiO₂/Si substrate using chemical vapor deposition. Rhodamine 6 G was used as a molecule probe to detect if the multilayer graphene-enclosed nickel nanoparticles can be applied in surface-enhanced Raman spectroscopy. The experimental results indicated that the Raman signals of C-C stretching within the benzene ring of rhodamine 6 G can be observed only on the multilayer graphene-enclosed nickel nanoparticle substrate rather than on reference substrates such as SiO₂/Si and Ni/SiO₂/Si. This suggests that the mechanism of Raman enhancement for rhodamine 6 G molecules on graphene is through the π–π bond coupling between them.     

Optimum spectral window for imaging of art with optical coherence tomography

Optical coherence tomography (OCT) has been shown to have potential for important applications in the field of art conservation and archaeology due to its ability to image subsurface microstructures non-invasively. However, its depth of penetration in painted objects is limited due to the strong scattering properties of artists’ paints. VIS–NIR (400–2,400 nm) reflectance spectra of a wide variety of paints made with historic artists’ pigments have been measured. The best spectral window with which to use OCT for the imaging of subsurface structure of paintings was found to be around 2.2 μm. The same spectral window would also be most suitable for direct infrared imaging of preparatory sketches under the paint layers. The reflectance spectra from a large sample of chemically verified pigments provide information on the spectral transparency of historic artists’ pigments/paints as well as a reference set of spectra for pigment identification. The results of the paper suggest that broadband sources at ~2 μm are highly desirable for OCT applications in art and potentially material science in general.     

基于银纳米三角片与罗丹明6G的荧光共振能量转移法检测钴离子

以罗丹明6G和牛血清白蛋白的复合物为荧光探针,银纳米三角片为猝灭剂,研究了银纳米三角片与荧光复合物的荧光共振能量转移现象,建立了测定钴离子的荧光分析法。研究发现,一定浓度的荧光复合物与银纳米三角片混合后,由于荧光复合物在银纳米三角片上吸附而发生荧光共振能量转移,荧光猝灭达到80%左右。当钴离子存在时,银纳米三角片与罗丹明6G荧光共振能量转移被破坏,荧光逐渐恢复。随着钴离子浓度的增加,体系荧光值的恢复率(I/I₀)与钴离子的浓度(c_Co2+)有良好的线性关系,线性回归方程为I/I₀=1.054+21.72 c_Co2+,相关系数r2为0.996 2。通过对自然水样进行加标回收检测,实现了钴离子的定量检测,回收率在90.4%～115.1%之间。建立了一种可靠的选择性检测钴离子的荧光分析方法。     

Rapid Clearance of IR783 and Methyl-β-cyclodextrin Complex for Improved Tumor Imaging

Near-infrared (NIR) fluorescence cancer imaging with targeted NIR fluorophores holds considerable promise for accurate detection and cancer diagnosis. Among the various NIR heptamethine cyanine dyes reported previously, IR783 as a single small molecule has been widely used for tumor-targeted imaging without the additional conjugation of targeting moieties. Despite the potential advantages of IR783, the major problems, such as its non-specific uptake in normal tissues/organs and slow clearance, remain to be solved. A key determinant of sensitivity and detectability in tumor imaging is the improvement of the tumor-to-background ratio (TBR). Herein, a simple and effective supramolecular complex self-assembled from IR783 and methyl-β-cyclodextrin is developed to improve tumor imaging accompanied by rapid clearance from the body. The IR783-cyclodextrin complex allowed for rapid whole body biodistribution, which remarkably reduced non-specific background uptake, and thus increased the TBR value within 24 h post-injection. Therefore, this strategy is applicable in combination with many different types of carbocyanine dyes for improved tumor imaging.     

Comparative study on the process behavior and reaction kinetics in sonocatalytic degradation of organic dyes by powder and nanotubes TiO2

Sonocatalytic degradation of various organic dyes (Congo Red, Reactive Blue 4, Methyl Orange, Rhodamine B and Methylene Blue) catalyzed by powder and nanotubes TiO₂ was studied. Both catalysts were characterized using transmission electron microscope (TEM), surface analyzer, Raman spectroscope and thermal gravimetric analyzer (TGA). Sonocatalytic activity of powder and nanotubes TiO₂ was elucidated based on the degradation of various organic dyes. The former catalyst was favorable for treatment of anionic dyes, while the latter was more beneficial for cationic dyes. Sonocatalytic activity of TiO₂ nanotubes could be up to four times as compared to TiO₂ powder under an ultrasonic power of 100 W and a frequency of 42 kHz. This was associated with the higher surface area and the electrostatic attraction between dye molecules and TiO₂ nanotubes. Fourier transform-infrared spectrometer (FT-IR) was used to identify changes that occurred on the functional group in Rhodamine B molecules and TiO₂ nanotubes after the reaction. Sonocatalytic degradation of Rhodamine B by TiO₂ nanotubes apparently followed the Langmuir-Hinshelwood adsorption kinetic model with surface reaction rate of 1.75 mg/L min. TiO₂ nanotubes were proven for their high potential to be applied in sonocatalytic degradation of organic dyes.     

Spectral–Luminescent and Generation Characteristics of a Gel–Like Gelatin Doped with a Dye

We present the results of comparative measurements of spectral–luminescent characteristics of Rhodamine 6G and Rhodamine C in water and water–gelatin solutions. We found that gelatin added to a water solution disaggregates the molecules of the dye. The maxima of the absorption and luminescence spectra of the solution shift then to the longwave region. The quantum yield of luminescence and the efficiency of generation of the solutions investigated are measured. The generation intensity of the gel is shown to depend on its composition and the dye selected. Measurement of spectral–luminescent characteristics of water–gelatin solutions makes it possible to select dyes that would generate most efficiently in gel solutions.     

Spectroscopic study of interaction of styrylcyanine dye Sbt and its derivatives with bovine serum albumin

The spectral-fluorescent characteristics of styrylcyanine dye Sbt ((E)-2-(4-(dimethylamino) styryl)-3-methylbenzo[d]thiazol-3-ium iodide) and homodimers, dyes conjugated with two chromophores in aqueous solutions without and in the presence of bovine serum albumin (BSA), are studied. It is established that in the presence of BSA for dyes Dbt-5 and Dbt-10, an increase of the absorptivity, a slight broadening and the emergence of new band on the short wavelength range with λ_max=410 nm is observed; also hypsochromic shift of the absorption and fluorescence at 30 nm and 7 nm, respectively for the dye D-183 is observed. The intensity of the fluorescence emission fundamental band in all the studied dyes in the presence of BSA increases by 3.5 to 55 times. The binding constant (K) and number of binding sites (N) of studied dyes with BSA are determined. The dependence of the binding constants with BSA from the dipole moment of dye molecules is identified, which shows that in addition to the electrostatic attraction forces between molecules of styrylcyanine dyes with BSA, hydrophobic interactions are essential. It is shown that the aggregation of dye affects the processes of interaction of the dyes with the BSA.     

Nonlinear optical properties of a new two-photon-absorption organic dye: HEASPS

Trans-4-[p-(N-hydroxyethyl-N-ethylamino)styryl]-N-methylpyridinium p-toluene sulfonate (abbreviated as HEASPS) is a two-photon-absorption (TPA) dye newly synthesized by our research group. It possesses a much larger TPA cross-section and much stronger upconversion fluorescence emission than those of common organic dyes (such as rhodamine) when excited with near-infrared (IR) radiation. TPA spectrum and upconversion efficiency spectrum of HEASPS solution at different wavelengths have been measured. The largest molecular TPA cross-section σ₂ ^′ is measured to be 2.06×10^-47 cm⁴ s/photon at 930 nm. At 1064 nm, σ₂ ^′ is 2.71×10^-48 cm⁴ s/photon, which is only one-ninth of that at 930 nm. The upconverted lasing efficiency spectrum has been measured at different wavelengths. The highest efficiency is 5.1% at 1020 nm, whereas it is 3.5% at 1064 nm. Its optical-power-limiting properties at 930 nm have also been illustrated. Received: 30 November 2000 / Published online: 27 April 2001     

TDDFT Investigation of the Electronic Structures and Photophysical Properties of Fluorescent Extended Styryl Push-Pull Chromophores Containing Carbazole Unit

Push-pull chromophores attached to carbazole based π-conjugating spacers bearing N-alkylamino donors, cyanovinyl and carbethoxy acceptors have been studied by the means of UV-Visible measurements. The intramolecular charge transfer (ICT) of these π-conjugated systems has also been tested by investigating the ability of the solute molecules to undergo shifts in their fluorescence emission maxima with increasing solvent polarity. Density Functional Theory [B3LYP/6-31G(d)] and Time Dependent Density Functional Theory [TD-B3LYP/6-31G(d)] computations have been used to have more understanding of the structural, molecular, electronic and photophysical parameters of push-pull dyes. The largest wavelength difference between the experimental and computed electronic absorption maxima was 45 nm. For emission, a largest difference of 61 nm was observed. The ground state and excited state dipole moments in different solvents were determined using experimental solvatochromic data and computed Onsager radii. The dipole moments of the molecules in the excited state were observed to be higher than in the ground state.