乙基紫-脱氧核糖核酸共振发光体系的研究及其分析应用

研究了碱性染料乙基紫与小牛胸腺脱氧核糖核酸(ctDNA)体系的结合反应及其共振发光光谱.在pH5.0～10.0范围内,乙基紫在595nm处有一特征吸收峰,加入DNA后,吸收峰消失,而在507nm处出现新的吸收峰,表明有新的结合物形成.在510nm处出现共振发光峰,其发光强度与DNA浓度呈线性关系,线性范围为0～500ng/mL;检出限(3σ)为1.54ng/mL.方法具有较高的灵敏度和准确度.将该体系用于核酸试样的测定,结果令人满意.     

Photoacoustic spectroscopy study on intramolecular energy transfer and relaxation processes of Tb(III) complexes

The photoacoustic (PA) amplitude spectra and luminescence spectra of different Tb(III) complexes (Tb(AA)3.2H2O Na[Tb(AA)4], Tb(AA)3bpy and Tb(AA)3phen) have been measured, and the PA phase shifts of the different complexes calculated. Combined with the luminescence spectra, the PA amplitude spectra reflected the variation of the luminescence efficiency and the PA phase is directly relative to the relaxation processes. According to the variation of the luminescence efficiency and the phase shift, the intramolecular energy transfer and relaxation processes of different Tb(III) complexes were discussed.     

Optical studies of the electronphonon interaction in the pyrene-PMDA complex

Low temperature phosphorescence spectra of pyrene-PMDA (pyromellitic acid dianhydride) imbedded in a naphthalene-PMDA host crystal are reported. The spectra exhibit resolved zero-phonon and multi-phonon structure which is significant since the phosphorescent state is characterized by ≈36% charge-transfer character. Several different phonons contribute to the structure with the dominant phonon having ground and excited state (from hot band analysis) frequencies of 25 and 15 cm^?1. The linear electronphonon coupling strength for the 25cm^?1 phonon is computed. This phonon is tentatively assigned to rotational motion of the rigid complex. Linewidth data yield a relaxation time of 0.4 ps at 2 K for the 25 cm^?1 phonon which is believed to be a pseudolocalized or resonant mode.     

Anharmonic metastable charge transfer vibronic exciton in potassium tantalate

This study provides an experimental evidence of a non-linear state of charge transfer vibronic excitons (CTVE) and its well-defined metastable behaviors in KTaO₃. An IR source could induce the same green CTVE-recombination luminescence band as that by a UV pumping. This up-conversion luminescence is characterized by a relaxation time τ (τ  60 s at 3 K), and theoretically explained as a result of IR-induced transfer of occupation of a metastable anharmonic CTVE state into a harmonic luminescent CTVE state. The observed temperature dependence of τsuggests that the relaxation is controlled by resonant and phonon-induced tunneling processes.     

Broadening of electronic absorption bands and the kinetics of luminescence of dapoxyl

Stationary spectra of selectively excided dapoxyl and time characteristics of the decay of its luminescence in polar solvents with the radiation excitation by picosecond pulses were studied. It was found that the absorption and luminescence stationary spectra are characterized by significant inhomogeneity, more pronounced in higher viscous solutions. Using the solvatochromic method, the change in the dipole moment of dapoxyl on the electron transition was estimated to be 18 ± 3 D. It was concluded that time characteristics of the decay of luminescence and the displacement of instantaneous luminescence spectra with time toward the range of long wavelengths are related to the mutual orientational relaxation of molecules in the solution.     

Theory of fluorescence and Raman scattering near resonance

Using a simple model for a molecular system in a bath, the cross section for Raman scattering around resonance is calculated. Without introducing constant relaxation times at the outset, the calculation yields a sharp coherent term, and a broad “hot” luminescence term. The second term is due to dephasing; its relative strength depends on the incident light frequency, and it disappears away from resonance.     

Single vibronic level resonant Raman scattering of molecular ions in solid glass: PMDA anion and naphthalene cation

Resonant Raman spectra were obtained for the radical anion of pyromellitic dianhydride (PMDA) in MTHF glass and the radical cation of naphthalene in alkyl halide glass at 77 K by using a pulsed tunable dye laser. The intensity pattern of the single vibronic level resonant Raman resembles that of hot fluorescence when the homogeneous line width of the intermediate level is narrow. Overtones and combinations of the excited vibrational mode prevail in the spectra.     

Photoacoustic and luminescence spectra study on the effects of chlorine substituent on the energy transfer of Eu(III)-chlorobenzoic acid

The photoacoustic (PA) amplitude spectra of three complexes of Eu(III) combined with chlorobenzoic acid (Eu(o-ClC6H4CO2)3.H2O, Eu(m-ClC6H4CO2)3.H2O and Eu(p-ClC6H4CO2)3.H2O) have been measured, and the PA phase of the different complexes have been calculated. Both the PA amplitude spectra and the luminescence spectra reflect the variation of the luminescent properties, and the PA phase is directly relative to the relaxation time. Since the relaxation is the process of the intramolecular energy transfer between the ligands and the central ion, the molecular structure of ligand is the important factor to decide the energy gap between the lowest triplet state of ligand and the resonance level of central ion. The effects of chlorine substituent on the molecular structure and energy gap of the complexes have been studied by PA phase and luminescence spectra.     

Solvent structural relaxation dynamics in dipolar solvation studied by resonant pump polarizability response spectroscopy

Resonant pump polarizability response spectroscopy (RP-PORS) was used to study the isotropic and anisotropic solvent structural relaxation in solvation. RP-PORS is the optical heterodyne detected transient grating (OHD-TG) spectroscopy with an additional resonant pump pulse. A resonant pump excites the solute-solvent system and the subsequent relaxation of the solute-solvent system is monitored by the OHD-TG spectroscopy. This experimental method allows measuring the dispersive and absorptive parts of the signal as well as fully controlling the beam polarizations of incident pulses and signal. The experimental details of RP-PORS were described. By performing RP-PORS with Coumarin 153(C153) in CH(3)CN and CHCl(3), we have successfully measured the isotropic and anisotropic solvation polarizability spectra following electronic excitation of C153. The isotropic solvation polarizability responses result from the isotropic solvent structural relaxation of the solvent around the solute whereas the anisotropic solvation polarizability responses come from the anisotropic translational relaxation and orientational relaxation. The solvation polarizability responses were found to be solvent-specific. The intramolecular vibrations of CHCl(3) were also found to be coupled to the electronic excitation of C153.     

High-resolution optical spectroscopy of Na(3)[Ln(dpa)(3)].13H(2)O with Ln = Er(3+), Tm(3+), Yb(3+)

The title compounds were synthesized and studied by solution and single-crystal absorption, luminescence, and excitation spectroscopy. The f-f luminescence is induced in the Tm(3+) and Yb(3+) complexes in solution by exciting into the (1)Pi-(1)Pi absorptions of the ligand in the UV. A single-configurational coordinate model is proposed to rationalize the nonradiative relaxation step from ligand-centered to metal-centered excited states in [Yb(dpa)(3)](3-) (dpa = 2,6-pyridinedicarboxylate). Direct f-f excitation is used in crystals of Na(3)[Tm(dpa)(3)].13H(2)O and Na(3)[Yb(dpa)(3)].13H(2)O to induce f-f luminescence. From low-temperature, high-resolution absorption, luminescence, and excitation spectra, the ligand-field splittings in the relevant states can be determined. It was impossible to induce NIR to VIS upconversion in any of the complexes. This is mainly due to the fact that nonradiative relaxation among the f-f excited states is highly competitive, even in [Yb(dpa)(3)](3-) with an energy gap between (2)F(5/2) and (2)F(7/2) of about 10000 cm(-1). It can be rationalized on the basis of an adapted energy gap law. No luminescence at all could be detected in Na(3)[Er(dpa)(3)].13H(2)O.     

Spectroscopic properties of Cs2NaLa1−xNdxCl6 crystal. Concentration quenching of fluorescence

The results of the absorption, infrared, Raman and fluorescence spectra of the title compound are reported. An assignment of the vibronic peaks of the fluorescence spectra is proposed. It was found that the concentration dependence of the fluorescence decay times was temperature dependent. The mechanism of concentration quenching of Nd³⁺ fluorescence is discussed in terms of resonant and non-resonant cross relaxation.     

Relaxation Kinetics of Excitonic States in ZnSe Quantum Dots: A Femtosecond Laser Spectroscopy Study

Relaxation processes in ZnSe quantum dots upon excitation by a 30-fs pulse at a wavelength of 360 nm have been studied by broadband femtosecond absorption spectroscopy. The diameter of ZnSe nanoparticles was 3.7 ± 0.6 nm. A colloidal solution of ZnSe in cyclohexane was used. In the differential spectra, a bleaching band at the edge of the excitonic absorption band of ZnSe, an absorption band of the biexcitonic transition with a peak at about 420 nm, and a broad structureless absorption band in the region from 440 to 750 nm have been revealed. From the analysis of the absorption and luminescence spectra, the shift of the excitonic luminescence band δ_XX = 127 meV has been measured. From the femtosecond photolysis data, an estimate of the biexcitonic interaction Δ_XX ≈ 75 meV has been obtained. It has been shown that the relaxation kinetics of the differential spectra is described by three-exponential dependences with time constants and corresponding amplitude contributions of 1 ps (42%), 13 ps (22%), and 91 ps (17%). The kinetic component of 1 ps (42%) is presumably due to hole transport to surface traps. The kinetic components of 13 ps (22%) and 91 ps (17%) apparently describe the processes of electron transport to shallow and deep traps.     

Non-markovian theory of diffusion-controlled excitation transfer

The non-markovian encounter theory is extended to kinetic calculations of an exciton (electron) contact transfer between an energy (charge) donor and acceptor. This process is shown to be non-stationary from the beginning to the end if the donor state relaxation time is shorter than the encounter time. The theory is applied to calculations of hot luminescence quantum yield in liquid solutions with a quenching impurity.     

The molecular mechanism of dual emission in terpyridine transition metal complexes--ultrafast investigations of photoinduced dynamics

Temperature dependent luminescence experiments are combined with femtosecond time-resolved transient absorption spectroscopy to decipher the photoinduced excited-state relaxation pathway in mononuclear Fe, Ru and Os terpyridine complexes bearing a conjugated chromophore within the ligand framework. The herein presented complexes constitute a class of coordination compounds, which overcome the poor emission properties commonly observed for most terpyridine transition metal complexes. As reported earlier, the complexes reveal dual emission at room temperature stemming from ligand centered and metal-to-ligand charge-transfer states. The molecular mechanism of the room temperature dual luminescence is addressed experimentally in this contribution. The experimental results indicate an ultrafast branching reaction within the excited-state manifold upon photoexcitation of the ligand-centered S(1) state. This branching occurs from a "hot" excited state geometry close to the Franck-Condon point of absorption and within ～100 fs, i.e. the temporal resolution of our experimental setup. The combination of ultrafast differential absorption experiments and temperature-dependent luminescence data allows not only to draw conclusions about the molecular mechanism underlying the observed dual emission but also to construct quantitative Jablonski diagrams and, thereby, to detail the excited-state topology determining the remarkable luminescence properties of the systems at hand.     

Magnetic resonance of short-lived triplet exciton pairs detected by fluorescence modulation at room temperature

The possibility of resonant electromagnetic field modulation of the rate of reactions between paramagnetic particles in a condensed medium lasting for 10^?8–10^?10 sand shorter than the spin-lattice relaxation time has been demonstrated experimentally. The EPR spectra of triplet exciton pairs in tetracene and charge transfer crystals have been recorded at room temperature.     

Time resolved fluorescence spectroscopy

Time correlated single photon counting was used to investigate solvent dynamics of laser dyes in a polar, viscous solvent. The resolved total luminescence spectra of oxazine 4 in 2-methyltetrahydrofuran (2-MTHF) have been measured and solvent relaxation observed.     

Ultrafast vibrational dynamics of interfacial water

We report investigations of the vibrational dynamics of water molecules at the water–air and at the water–lipid interface. Following vibrational excitation with an intense femtosecond infrared pulse resonant with the O–H stretch vibration of water, we follow the subsequent relaxation processes using the surface-specific spectroscopic technique of sum frequency generation. This allows us to selectively follow the vibrational relaxation of the approximately one monolayer of water molecules at the interface. Although the surface vibrational spectra of water at the interface with air and lipids are very similar, we find dramatic variations in both the rates and mechanisms of vibrational relaxation. For water at the water–air interface, very rapid exchange of vibrational energy occurs with water molecules in the bulk, and this intermolecular energy transfer process dominates the response. For membrane-bound water at the lipid interface, intermolecular energy transfer is suppressed, and intramolecular relaxation dominates. The difference in relaxation mechanism can be understood from differences in the local environments experienced by the interfacial water molecules in the two different systems.     

Analysis of the Electronic Structure of Aqueous Urea and Its Derivatives: A Systematic Soft X‐Ray–TD‐DFT Approach

Soft X‐ray emission (XE), absorption (XA), and resonant inelastic scattering (RIXS) experiments have been conducted at the nitrogen K‐edge of urea and its derivatives in aqueous solution and were compared with density functional theory and time‐dependent density functional theory calculations. This comprehensive study provides detailed information on the occupied and unoccupied molecular orbitals of urea, thiourea, acetamide, dimethylurea, and biuret at valence levels. By identifying the electronic transitions that contribute to the experimental spectral features, the energy gap between the highest occupied and the lowest unoccupied molecular orbital of each molecule is determined. Moreover, a theoretical approach is introduced to simulate resonant inelastic X‐ray scattering spectra by adding an extra electron to the lowest unoccupied molecular orbital, thereby mimicking the real initial state of the core‐electron absorption before the subsequent relaxation process.     

Excitation relaxation in films of dipolar N,N-dimethylaminobenzylidene 1,3-indandione molecules

Ultrafast relaxation of self-trapped (ST) excitons in polycrystalline film of N,N-dimethylaminobenzylidene 1,3-indandione (DMABI) molecules, which possess pronounced donor–acceptor properties, is studied by using femtosecond luminescence up-conversion spectroscopy. Exciton relaxation dynamics is compared to excitation decay obtained for DMABI molecules embedded in a rigid transparent matrix. Excitons in the film undergo rapid self-trapping on the time scale below 100 fs. A strong nonradiative recombination of ST excitons is observed on the subpicosecond time scale, which is shown to occur concurrently with their final localization. This final localization is attributed to the cooling of locally heated (up to 600 K) ST excitons, that occurs with the time constant τ_c=800 fs. The fast nonradiative relaxation is assigned to the thermally activated transition of the hot excitons to the ground state during their thermalization. After the fast relaxation stage is completed, the second, slow exciton relaxation stage emerges, which is attributed to one-dimensional migration of excitons and their nonradiative decay on structural defects.     

Luminescent determination of automobile petrol in hexane solutions

The work deals with the problem of determination of automobile petrol of various octane numbers and petroleum contamination of some objects on the basis of analysis of photoluminescence spectra of automobile petrol samples. For this purpose steady state luminescence properties of samples of automobile petrol of different types being in sale were measured. Samples of automobile petrol diluted in hexane were prepared and their luminescence spectra were measured at room and liquid nitrogen temperatures of samples. We constructed concentration dependences of luminescence intensity of both wide band luminescence of liquid solutions obtained at room temperature and peak intensities of luminescence lines of quasi linear spectra of solutions frozen at 77 K. Possibility to use luminescence method for analysis of petrol pollutions on some objects is illustrated by results of investigation of pine-wood pieces contaminated by automobile petrol.