Energy transfer studies in dye mixtures in different solvent environments

The energy transfer mechanism in C 540–rhodamine 6G and C 540–rhodamine B donor–acceptor (D–A) pairs is investigated. The good spectral overlap and the proximity of D–A pair molecules, which is around 60 Å, denote the possibility of resonance energy transfer between the D–A pairs. Energy transfer is studied in two solvent environments. C 540–Rh 6G and C 540–RhB D–A pairs behave in quite different manner in different solvent environments.     

Photoacoustic spectra of some laser dyes

Photoacoustic spectra of rhodamine 110, rhodamine 6 G, rhodamine B, rhodamine 101 and coumarin 102 laser dyes have been recorded at room temperature of 25°C in the spectral range of 350–750 nm. These samples were taken in powder as well as in solution forms. For this purpose the closed and the open photoacoustic cells have been used. It is hoped the present study would be useful for characterization of these dyes.     

Theoretical investigation of the ground and excited state of silylated coumarin

We present ground and excited state properties of silylated coumarin dyes. We have calculated the energies and dipole moments of ground and excited states of silylated coumarins and some coumarin derivatives. Using CIS we find a good agreement with experimental S₀→S₁ excitation energies. Silylation of dye molecules had minor effect on the transition energies. On the basis of theoretical results, we conclude that silylated dye will have improved long-term photostability compared to its unsilylated counterpart due to its covalent bonding with the host matrix.     

Time resolved spectroscopy in laser grade organic dyes

Time resolved spectroscopy is discussed along with the theoretical and experimental methods used to measure the fluorescence lifetimes in various laser grade organic dyes. The role of solvents and their viscosities in the fluorescence life time is also discussed. Different photophysical parameters have been obtained in rigid and non-rigid dye molecules.     

NaK分子激发态的预离解和碰撞激发转移

用Ar+激光器固定频率488.0nm线激发Na-K混合蒸汽,NaK分子激发态通过自发辐射、预离解和与基态原子的碰撞激发转移而去布居,测量在不同K原子密度下原子荧光对分子荧光的强度比,结合NaK(E)态寿命,得到了预离解率和碰撞激发转移率.     

Energy transfer processes in two different bifluorophoric laser dyes

The mechanism of intramolecular energy transfer in two bifluorophoric laser dyes has been investigated by measurements of laser parameters, excited state absorption and phosphorescence spectra. The new value found for the dimethyl-POPOP triplet energy (48.0 kcal/mole) accounts for the different behaviour of the two classes of bifluorophoric dyes used in this investigation.     

Ultraviolet emissions from Gd ions excited by energy transfer from Ho ions

Ultraviolet (UV) upconversion (UC) emissions of Gd³⁺ ion were investigated in Y_1.838−xGd_xYb_0.16Ho_0.002O₃ (x=0, 0.16, 0.4, 1, 1.4) bulk ceramics under 976 nm laser diode (LD) excitation. The UC emissions centered at 309 and 315 nm are assigned to the transition of ⁶P_5/2→⁸S_7/2 (Gd) and ⁶P_7/2→⁸S_7/2 (Gd). The ⁶P_J levels of Gd³⁺ ions are populated by an energy transfer (ET) process from ⁸S_7/2 (Gd)+(³P₁, ³L₈, ³M₁₀) (Ho)→⁶P_J (Gd)+⁵I₈ (Ho). A four-photon ET UC process was confirmed by the dependence of the ⁶P_7/2 level emission intensity on the pumping power. We found that the intensity of the UC emissions increased with Gd³⁺ ion concentration and peaked at 8 mol%, then starts to decrease until the Gd³⁺ ion concentration reached 70 mol%. The variation in the UV emission intensity is the result of the competition between the ET process and concentration quenching effect. Theoretical calculations based on steady-state equations validated the proposed UC mechanisms.     

Time-resolved fluorescence of cationic dyes covalently bound to poly(methacrylic acid) in rigid media

Atactic poly(methacrylic acid) labeled with acridine and Nile blue (NB) were studied by photophysical techniques in bulk solid state and in solution-cast films over different surfaces (glass, ITO, and polymethylmethacrylate). In the systems with both dyes, energy transfer from acridine to NB occurs with an efficiency depending on the type of substrate (solid or film). The films are more disordered fluorescent rigid media than the bulk chromophoric or bichromophoric polymers, and this effect is ascribed to inhomogeneous distribution of the dyes in the film. This effect enhances dye bimolecular interactions and increases the energy transfer rates between acridine donor and NB acceptor. Bimodal distributions of donor fluorescence lifetimes are observed.     

Energy transfer and quantum correlation dynamics in FMO light-harvesting complex

The dynamics of energy transfer in Fenna–Matthews–Olson (FMO) light-harvesting complex interacting with a phonon bath is investigated. In this contribution, by considering the phonon bath as a source of stochastic noise, a new approach is proposed. Also, by calculating the global quantum entanglement and global quantum discord, the time evolution of the quantum correlation during the process is evaluated. The effects of temperature and initial excited state on the energy transfer and the quantum correlation are studied. It is shown, in agreement with the previous results, that the increasing of the temperature gives rise to the faster delocalisation of energy transfer and global quantum entanglement in the FMO complex. The proposed model predicts that the global discord is resistance versus the raising temperature. Furthermore, it is demonstrated that the quantum entanglement with respect to the global quantum discord has a significant role in the process of energy transfer in the FMO complex.     

A new coumarin laser dye 3-(benzothiazol-2-yl)-7-hydroxycoumarin

The electronic absorption, and emission spectra as well as fluorescence quantum yield of 3-(benzothiazol-2-yl)-7-hydroxycoumarin (BTHC) were measured in different solvents and are affected by solvent polarity (Δf). The deprotonation of BTHC by triethylamine is a reversible process. BTHC is relatively photostable, the quantum yield of photodecomposition (φ_c) was found to be 2×10⁻⁴ and 2.7×10⁻⁴ in EtOH and DMF, respectively. The fluorescence lifetimes of BTHC were measured in the absence and in the presence of molecular oxygen and were found to be 2.82 and 2.78 ns, respectively. BTHC acts as good laser dye upon pumping with nitrogen laser (λ_ex=337.1 nm) in ethanol and gives laser emission with maxima at 508 and 522 nm.     

Photophysical properties, laser activity and photoreactivity of a heteroaryl chalcone: A model of solvatochromic fluorophore

The absorption and fluorescence characteristics of 3-(4′-dimethylaminophenyl)-1-(2-thienyl)prop-2-en-1-one (DMATP) have been investigated in different solvents. DMATP dye exhibits a large red shift in both absorption and emission spectra as solvent polarity increases, indicating a large change in the dipole moment of molecules upon excitation due to an intramolecular charge transfer interaction. The fluorescence quantum yield depends strongly on the properties of the solvents, which was attributed to positive and negative solvatokinetic effects. A crystalline solid of DMATP gave an excimer like emission at 570 nm due to the excitation of molecular aggregates. This is expected from the idealized crystal structure of the dye that belongs to the B-type class of Steven's classification. A dye solution ca. 10⁻³ mol dm⁻³ in CHCl₃ gave a good laser emission in the range 480–560 nm with emission maximum at 530 nm upon pumping by nitrogen laser (λ_ex=337.1 nm). The excitation energy transfer from 7-dimethylamino-4-methyl coumarine (DMC) to DMATP has been also studied in CHCl₃ and the values of energy transfer rate constant and critical transfer distance indicate a Főrster-type mechanism. The photoreactivity and net photochemical quantum yield of DMATP in chloromethane solvents are also determined. We applied semiempirical MO calculation using AMI and ZINO/S calculation to understand the geometric and electronic structure of DMATP molecule in both ground and excited states.     

Energy transfer between excitons and plasmons in semiconductor-metal hybrid nanostructures

We summarized our recent optical studies on semiconductor nanoparticle (NP) based hybrid nanostructures: isolated CdSe NPs on Au substrates, close-packed CdSe NP monolayers on Au substrates, and close-packed monolayers of mixed CdSe/Au NPs. Luminescence properties of semiconductor-metal hybrid nanostructures were studied by space-resolved optical imaging spectroscopy and time-resolved luminescence spectroscopy. The luminescence spectra and dynamics of isolated and assembled NPs depend on the local environments. We discuss exciton-plasmon interactions in semiconductor-metal hybrid nanostructures.     

激发态分子内质子转移有机分子HBT的三阶非线性光学特性

以532nm皮秒脉冲作抽运光,采用单光束Z-扫描技术对具有激发态分子内质子转移效应的有机分子2-(2′-羟基苯基)苯并噻唑(HBT)在其双光子吸收区的非线性光学特性进行了研究.实验结果表明,对532nm波长的光,HBT分子存在明显的双光子吸收.通过拟合开孔Z-扫描实验数据,求解了HBT分子在其双光子吸收区的非线性吸收系数,并探讨了抽运光强度对介质双光子吸收效应的影响.采用高斯分解法,通过拟合闭孔Z-扫描除以开孔Z-扫描数据,理论推导并计算了在介质对抽运光存在非线性吸收的情况下HBT分子的非线性折射率,以及不同入射光强度时HBT分子的三阶非线性极化率实部和虚部的值.计算结果表明,理论分析与实验结果较好地符合,这些结果为进一步研究和开发此类材料的应用提供了理论与实验依据.     

Study on the chemiluminescence resonance energy transfer between luminol and fluorescent dyes using a linear CCD spectrometer

Chemiluminescence (CL) has been a useful tool for analytical applications. Fluorescein can be used to enhance CL emission of luminol. With three-dimensional (3D) dynamic CL spectrum obtained from a linear CCD (charge-coupled device) flow-injection CL spectrometer, the fluorescein enhanced CL analysis was studied. The enhanced process can be described with chemiluminescence resonance energy transfer (CRET) at certain fluorescein concentrations. In the process of CRET, fluorescein enlarges CL intensity but does not join the CL reaction. Compared with classic luminol-Co²⁺ CL system, the fluorescein-enhanced system exhibits stronger CL signal with the linear range and detection limit for traces of Co²⁺ unchanged.     

Theoretical study of excited state proton transfer in pyrrole-2-carboxylic acid

Pyrrole 2-carboxylic acid (PCA) shows dual emission (310 nm and 430 nm) in water on photo-excitation, which indicates that more than one species is in the excited state. This paper reports on the quantum chemical analysis of pyrrole 2-carboxylic acid (PCA) in the light of a possible excited state proton transfer. Dipole moment, excited state energy and findings in molecular orbital calculations (HOMO, LUMO) establish that PCA is a likely candidate for transfer of a proton from the pyrrole moiety to the C=O of carboxylic moiety (possible zwitterionic form) in the excited state. Overall, the computed predicted results of intramolecular and intermolecular excited state proton transfer corroborates the experimental results.     

Intermolecular energy transfer in mixed laser dyes: photophysical properties of triplet states

Triplet-singlet energy transfer in laser dyes have been studied in EPA at 77K using N₂ laser as an excitation source. Phosphorescence of the donor (D) and the delayed fluorescence of the acceptor (A) and their lifetimes have been measured for coumarin 102 (D)-rhodamine B(A) and 9(10H)-acridone (D)-rhodamine 6G(A) dye systems as a function of acceptor concentration. These data yield energy transfer rate constants of ∼10³ dm³ mol⁻¹ s⁻¹ for the donor acceptor combinations, consistent with the Forster mechanism. The phosphorescence quantum efficiency and other spectral parameters are also reported.     

Excimer laser forward transfer of mammalian cells using a novel triazene absorbing layer

We present a novel laser-based approach for developing tissue engineered constructs and other cell-based assembly's. We have deposited mesoscopic patterns of viable B35 neuroblasts using a soft direct approach of the matrix assisted pulsed laser evaporation direct write (MAPLE DW) process. As a development of the conventional direct write process, an intermediate layer of absorbing triazene polymer is used to provide gentler and efficient transfers. Transferred cells were examined for viability and proliferation and compared with that of as-seeded cells to determine the efficacy of the process. Results suggest that successful transfers can be achieved at lower fluences than usual by the incorporation of the intermediate absorbing layer thus avoiding any damage to cells and other delicate materials. MAPLE DW offers rapid computer-controlled deposition of mesoscopic voxels at high spatial resolutions, with extreme versatility in depositing combinations of natural/synthetic, living/non-living, organic/inorganic and hard/soft materials. Our approach offers a gentle and efficient transfer of viable cells which when combined with a variety of matrix materials allows development of constructs and bioactive systems in bioengineering.     

Laser induced reverse transfer of gold thin film using femtosecond laser

Laser induced reverse transfer (LIRT) has been executed first time using a Mega Hertz pulse frequency femtosecond laser radiation under ambient conditions. Research has been conducted to understand the evolution of deposited structures with regard to pulse energy. Solid deposition of gold could be deposited on quartz substrate only if pulse energy falls within a certain range. For the experiment conducted in this work, it is 36-40 nJ. For energies above this range, crests appear in the middle of the deposition. There is a threshold in maximum applicable pulse energy, 82 nJ in this exepriment, beyond which further increase in pulse energy results in only traces of deposited material. Results also show that the width of deposited line increases with the increase in pulse energy and decreases with the increase in scan speed. These observations have been explained using the dynamics of ablated plume.     

Energy migration and transfer between chromophores embedded in Gaussian space

We have used a Monte Carlo method to investigate energy migration and transfer between chromophores embedded in Gaussian space. In using this method we have obtained fluorescence quantum yields, fluorescence depolarization, and the respective decay profiles of donor fluorescence. It was shown that all photophysical observables are dependent upon the number of donor and acceptor chromophores and upon the Förster radii ratio. The latter feature is particularly interesting, and it indicates the existence of correlations between donor and acceptor chromophores. It was shown that the excitation of the donor chromophore at the origin leads to different values of observables, in comparison with an excitation of a randomly selected donor chromophore. The results presented show the importance of the averaging procedures needed to be developed while dealing with specific distribution functions, as, for example, in the case of energy migration and trapping in aromatic polymers and copolymers.     

Energy transfer rate in double-layer graphene systems: Linear regime

We theoretically investigate the energy transfer phenomenon in a double-layer graphene (DLG) system. We use the balance equation approach in linear regime and random phase approximation screening function to obtain energy transfer rates at different electron temperatures, densities and interlayer spacings. We find that the rate of energy transfer in the DLG is qualitatively similar to that obtained in the double-layer two-dimensional electron gas but its values are an order of magnitude greater. Also, at large electron temperature differences between two graphene layers, the electron density dependence of energy transfer is significantly different, particularly in case of unequal electron densities.