Highly Efficient Photosensitization of Mesoporous TiO_2 Electrode with a Cyanine Dye

A low cost cyanine dye, 1,1-dimethyl-3-ethyl-2-[3-(1,3-dihydro-3,3-dimethyl-1-ethyl- 5-carboxyl-2H-indol-2-ylidene)-1-propenyl]-1H-benz[e] indolium iodide (1) was synthesized and applied to sensitize mesoporous TiO2 electrode. Photoresponse of the electrode was extended to the visible and remarkably high incident photon-to-current conversion efficiency (IPCE) over 70% was achieved from 500 nm to 600 nm.

DFT Investigation on the Trans-cis Photoisomerization of Pentamethine Cyanine Dye Model Molecule

The trans-cis photoisomerization of pentamethine cyanine dye （Cy5） has been theoretically investigated by the analysis on an analogical molecule model. All possible isomers have been searched by rotating the different bridge C-C bonds of the model. The relative stability of the isomers for the ground and first excited states as well as the corresponding excitation mechanism has been envisaged by DFT and time-dependent DFT method. The results show different conjugation degree of the isomers resulting in different absorption energy upon the different C-C bridge bond rotation. From the analyses of electronic density distribution of the frontier orbitals, it is predicted that there is charge transfer besides the π-π^＊ excitation for the cyanine dye model, which makes the mechanism and photo-properties different form those of other conjugated molecules.

Synthesis and Characterization of a Squarylium Cyanine Dye with Two [60]Fullerene Units

A new [60]fullerene dimer 2 in which two C-60 units are covalently attached to a squarylium cyanine dye has been synthesized and characterized.

STUDIES ON CROWN ETHER CYANINE DYES (X). THE SYNTHESIS OF BENZOXAZOLE CROWN ETHER CYANINE DYES

A simple method for synthesis of benoxazole crown ether cyanine dyes is described.

STUDIES ON CROWN ETHER CYANINE DYES(XI)THE SYNTHESIS OF BENZOTELLURAZOLE CROWN ETHER CYANINE DYES

Three methods for synthesis of benzotellurazole crown ether(6)are described.The cyanine dye(8)can be easily obtained by treating(6) with CH_3I and CH(OEt)_3.

Synthesis and Photophysical Properties of Novel Highly Stable Zero/Bis-Zero Methine Cyanine Dyes Based on N-Bridgehead Heterocycles

Cyanine dyes of zero/bis-zero methine incorporating imid-azo(1,2-a)Pyridine (quinoline) or pyrazino(1,2-a)pyridine (quinoline) with stable C-N bond were synthesized using keto-oxime methylene C-link heterocyclic quaternary salts [1-phenyl-3-methyl-pyrazolino-4-keto-oxime-α-methylene-bis-pyridin-(quinoin)-1(4)-di-ium-iodide(ethiodide) salts and 1-phenyl-3-methyl-pyrazolino- 4-ketooxime-α-methylene-N-2-methyl-bis pyridin (quinoin)-1(4)-di-ium-iodide(ethiodide) salts]. Such heterocyclic precursors and related dyes were identified by elemental and spectral analyses. The absorption spectra properties of such dyes were investigated in 95% Ethanol to attempt and throw some light on the influence of such new heterocyclic nuclei and to compare or evaluate spectral behaviors. The absorption spectra of dyes in different pure solvents were examined in the visible region showing solvatochromism and the colour changes of dyes with solvents having different polarities. This permits a selection of the optimal solvent (fractional solvent) when such dyes are applied as photosensitizers. The spectral behavior of some selected newly synthesized cyanine dyes is observed in mixed solvents of different polarities and progressively increasing quantities of one solvent over the other were studied and showed an increase in the absorbance of CT band with increasing proportion of that solvent. Evidence for hydrogen bond formation between the solute molecules and solvent molecules allows measurement of certain energies such as hydrogen bonding, orientation, and free energies.

Theoretical and Experimental Study of the Mechanism of Reaction Formation of Cyanine Dyes

To study the theoretical bases of the mechanism of reaction formation of cyanine dyes, special importance is gained by methods of quantum chemistry. The use of these methods is provided with the known molecular and dynamic HyperChem program. The purpose of studying was quantum and chemical studying of features of a geometrical and electronic structure of model molecules of penicillin acid, of derivative of glutaconic dialdehyde (DGD), and the cyanine dyes, and also an assessment of power of process of their formation. For studying was carried out the experimental mark of chemism of course of reaction with theoretical justification of the mechanism of reaction formation of cyanine dyes. The results show that all studied model molecules are thermodynamic steady systems to what values of enthalpies of their formation, rather high on an absolute value, testify negative on a sign. Reaction goes by the mechanism of nucleophilic addition.

Unusual Spectral Change Due to a Cyanine Dye Adsorbed on an Inorganic Layered Material upon Photoirradiation

Photoinduced spectral change can be utilized for various optical devices. The photoinduced spectral change due to an organic dye was demonstrated for the organic-inorganic hybrid film without the aid of photochromism with a simple preparation method for the first time. By the hybridization of a cyanine dye of 2-[5-(1,3-dihydro-3,3-dimethyl-1-octadecyl-2H-indol-2-ylidene)-1,3-pentadienyl]-3,3-dimethyl-1-octadecyl-3H-indolium perchlorate (NK3175) with an inorganic layered material of cation-exchangeable clay, smectite (SWN), a spectral change attributed to NK3175 was generated upon the irradiation of UV light. This result might serve as useful information on the methodology to produce optically controlled function for photoresponsive systems. Furthermore, the hybrid film of SWN and NK3175 was characterized by the use of XRD and FT-IR measurements. NK3175 molecules adsorbed onto external surfaces of SWN were confined by oriented SWN. It was suggested that the enhanced intermolecular interaction between NK3175 molecules caused by the hybridization with SWN resulted in the change of the aggregation state of NK3175 upon the UV light irradiation, which accounts for the spectral change of NK3175.

Study on the Direct Photooxidation of Near-Infrared Absorbing Benzothiazolone Cyanine Dye

In this paper, direct photooxidation of benzothiazolone cyanine dye: in acetonitrile was studied. The photoproducts had been identified by (HNMR)-H-1 and fast atom bombardment (FAB) mass spectrometry. The results showed that the N-ethylbenzothiazolone (I), the ionic acid (II), and ionic aldehyde (III) are the principal photoproducts.

Squarylium Cyanine Dyes for Photoelectric Conversion

Two squarylium cyanine dyes (Sqs) were synthesized to explore their applications in photoelectrochemical solar cells. Nanocrystalline TiO2 electrodes modified with Sqs have been prepared to probe the photosensitization effects. A rather high photoelectric conversion efficiency of up to 2.17% and the top incident monochromatic photon-to-photocurrent conversion efficiency (IPCE) of 6.2% at 650nm were obtained from the Sq2-modified nanocrystalline TiO2 electrode.

Anisotropy in Third-Order Nonlinear Optical Susceptibility of a Squarylium Dye in a Nematic Liquid Crystal

A squarylium dye is dissolved in 4-cyano-4＇-pentylbiphenyl （SCB） and oriented by sandwiching mixtures between two pieces of rubbed glass plates. The optical absorption spectra of the oriented squarylium dye-5CB layers exhibit high anisotropy. The third-order nonlinear optical responses and susceptibilities X^（3）e of squarylium dye in 5CB are measured with light polarizations parallel and perpendicular to the orientational direction by the resonant femtosecond degenerate four-wave mixing （DFWM） technique. Temporal profiles of the DFWM signal of the oriented squarylium dye-5CB layers with light polarizations parallel and perpendicular to the orientational direction are measured with a time resolution of 0.3ps （FWHM）, and are found to consist of two components, i.e., the coherent instantaneous nonlinear response and slow response due to the formation of excited molecules. A high anisotropic ratio of x^（3）e, 10.8 ：k 1.2, is observed for the oriented layers.

Single molecule fluorescence fluctuations of the cyanine dyes linked covalently to DNA

The intersystem crossing and isomerization dynamics of free-Cy3,Cy3-ssDNA,free-Cy5 and Cy5-ssDNA are obtained through simple analysis of rapid on/off blinking from single molecule fluorescence intensity time-traces and the fluorescence correlation spectroscopy(FCS).The on-and off-times observed in fluorescence time traces of single cyanine dyes are due to the formation of the triplet state and isomerization,where both the interaction with DNA and long central polymethine chain of cyanine dyes increase the barriers of isomerization,leading to long off-time.The results indicate that the single molecule fluorescence fluctuation together with the resulting second autocorrelation analysis are powerful methods for determining the triplet state and isomerization dynamics,which could be the simple techniques and complementary to other spectroscopic techniques,such as fluorescence decay measurement and laser flash photolysis to study the photophysical processes of complex molecules.

Investigation of a cyanine dye assay for the evaluation of the biocompatibility of magnesium alloys by direct and indirect methods

Magnesium and its alloys are promising candidates for a new generation of biodegradable metals in orthopaedic applications due to their excellent biocompatibility,biodegradability,and mechanical properties that are similar to natural bone.However,direct in vitro assessment of these materials in the presence of cells is complicated by degradation products from the alloy that lead to a false positive for the most commonly used cell adhesion and cell proliferation assays.In this paper,a cyanine dye was used to quantitatively evaluate the in vitro biocompatibility of a Mg AZ31 alloy by both direct and indirect methods.The cytotoxicity of the corrosion products was evaluated via an indirect method;a 25%decrease in cell viability compared to control samples was observed.Moreover,direct assessment of cell adhesion and proliferation showed a statistically significant increase in cell number at the surface after 72 h.In addition,the degradation rate and surface characteristics of the Mg AZ31 alloy were evaluated for both direct and indirect tests.The degradation rate was unaffected by the presence of cells while evidence of an increase in calcium phosphate deposition on the magnesium alloy surface in the presence of cells was observed.This study demonstrates that a cyanine dye based assay provides a more accurate assessment of the overall in vitro biocompatibility of biodegradable metals than the more commonly used assays reported in the literature to date.

One-Pot Preparation of Highly Dispersed Second Near-Infrared J-Aggregate Nanoparticles Based on FD-1080 Cyanine Dye for Bioimaging and Biosensing

Bioimaging and biosensing in the second nearinfrared(NIR-II)window have attracted great attention due to their unprecedented high temporal–spatial resolution,sensitivity,and penetration depth.Although some organic fluorescence dyes have been developed in this window,it is still a great challenge to synthesize hydrophilic organic contrast agents with both absorbance and emission wavelengths beyond 1300 nm.J-aggregation is a facile pathway to achieve the wavelength red-shift of organic dyes to the NIR-II window and simultaneously improve their hydrophilicity.Here,we report FD-1080 J-aggregates(FD-J)with absorbance of 1360 nm and emission of 1370 nm through heating H-aggregated FD-1080 cyanine dyes in an aqueous solution.With FD-J administration,real-time imaging of mice brain and hindlimb vasculatures can be performed beyond 1500 nm.Meanwhile,arterial and venous vessels can be clearly distinguished through dynamic imaging after injection of FD-J.In addition,reactive oxygen species-responsive NIR-II ratiometric fluorescence sensors were available based on FD-J and lanthanide nanoparticles to enable the detection of inflammation in living mice.

一种新型菁类功能染料的合成

2,3,3-三甲基-3H-吲哚与1,4-丁磺酸内酯反应得到4-(2,3,3-三甲基吲哚)丁烷磺酸盐(1);苯胺与1,1,3,3-四乙氧基丙烷反应得到盐酸-N-(3-苯氨基-2-丙烯亚基)苯胺(2);最后4-(2,3,3-三甲基吲哚)丁烷磺酸盐与盐酸-N-(3-苯氨基-2-丙烯亚基)苯胺反应得到一种新型菁类染料。通过对反应条件中的碱的种类、碱的用量和温度的影响,探究不同条件下分离产率的变化,对比不同条件下分离产率提高或降低的趋势。反应条件的考察确定最佳反应条件:化合物1与2的投料比为2:1;乙酸钠用量为苯胺的2倍当量;适量乙酸酐;反应温度110℃;反应时间1 h;产率为65%。

Structure of Cyanine Dye Aggregates Observed by Scanning Tunneling Microscopy

In solution and on a variety of substrates, the ability of spectral sensitizing dyes to form molecular aggregates with close intermolecular spacings and strong coupling is a well-known phenomenon. A given dye may form several different types of aggregates, which exhibits spectral shifts of±100 nm from the monomer spectrum in the solution. Aggregate of dye ab-

Phase Transition of Cyanine Dye Monolayer on the Air/Water Surface Observed Under Brewster Angle Microscope

It is an extensively used method recently to prepare the mixed monolayer of cyanine dye by spreading a mixed solution of short chain cyanine dye and long chain fatty acid on a water surface. The method is very important for the molecular architecture because it makes non-amphiphilic molecules form monolayer on water surface. But the molecular arrangement of this kind of mixed monolayer is unclear under different surface pressures.

A comparative study of assembly and disassembly process of dimeric and monomeric cyanine dyes with DNA templates

Cyanine dyes have attracted more and more interest due to their controllable assembly and disassembly process with biomolecular templates. The self-assembly of cyanine dye not only depend on the environment, but also on their structures. Here, we report assembly and disassembly of two cyanine dyes,a dimeric cyaine dye(TC-P4) and its corresponding monomer(TC). In PBS, these dyes could form aggregates. The parallel c-myc G-quadruplex as a template causes the transformation of TC-P4 from Haggregates to dimer and monomer; while duplex and single-stranded DNAs could not. The interaction between these DNAs motifs and TC could all induce the appearance of monomer band. Parallel c-myc Gquadruplex could enhance the fluorescence intensity of TC-P4 and TC. The self-assembly and disassembly of TC and TC-P4 could be regulated and used as probes for G-quadruplex recognition from duplex and single-stranded DNAs in solution.

Photostabilizing effects of singlet oxygen quenchers on long chain cyanine dyes

The total rate constants of the reaction of six antioxidants with singlet oxygen were measured by fluorospectroscopy,and the effects of these antioxidants on the photostability of the dyes were also investigated kinetically.The results reveal that the six antioxidants are the effective quenchers of singlet oxygen (~1O_2)and can increase the photostability of the dyes.The power of metal chelates to quench ~1O_2 is the strongest,and the chelates show the most effects on the photostability of the dyes.The photostability of the dyes has something to do with the relative amount of the antioxidant used.

Synthesis and light absorption of benzotellurazole crown ether cyanine dye

Various methods for synthesis of 2-methyl-5,6-(1,4, 7,10,13-pentaoxatridecamethylene)benzotellurazole (8) are described. Under different conditions, alkylation of compound 8 with methyl iodide gave telluronium salt 1,2-dimethyl-5,6-(1,4,7,10,13-pentaoxatridecamethylene)benzotellurazolium iodide (15) or quaternary ammonium salt 2,3-dimethyl-5,6-(1,4,7,10,13-pentaoxatridecamethylene)benzotellurazolium iodide (14) in high yields, repectively. The cyanine dye 3,3'-dimethyl-5,6,5',6'-bis(1,4,7,10,13-pentaoxatridecamethylene)telluracarbocyanine iodide (16) is obtained by condensation of 14 with ethyl orthoformate in acetic anhydride, The visible absorption of the cyanine dye is also discussed.