Fluorescence studies of some protonated cinchona alkaloids in polymers

In the present paper we report spectral and photophysical properties of two probes viz. cinchonidine and quinidine in two different polymers viz. polyvinyl alcohol (PVA) and polymethylmethacrylate (PMMA). The emission spectra exhibit edge excitation red shift (EERS) for both the probes and multiexponential decays are observed. Presence of various conformers and geometries is suggested to explain the observed results. The photophysical properties and excited state behavior of Cd++ are more sensitive towards the microenvironment of the polymer.     

Site-selection optical spectra of bacteriochlorophyll and bacteriopheophytin in frozen solutions

Site-selection spectra of title compounds in different frozen solvents at 5K have been obtained: fluorescence spectra on selective excitation in vibronic as well as in the O-O absorption region and excitation spectra with narrow-band fluorescence recording. Frequencies of vibrational modes active in fluorescence and excitation spectra of bacteriochlorophyll a (BChl) and its metal-free derivative have been determined from these fine-line spectra. Most favourable vibronic line-to-background intensity ratios have been found in non-polar aprotic glassy environments (triethylamine, di-iso-amylether). The intensity of zero-phonon lines in microcrystallic protic matrices was low, indicating strong electron-phonon coupling. The vibrational frequencies of the excited electronic state characteristic of axially (at Mg atom) mono- and disolvated BChl species have been identified. Narrow spectral holes of about 20% of the initial absorption could be burned with ≈10^-4 quantum yield within the O-O band of BChl and bacteriopheophytin.     

Excited and ground state conformations of p-dimethylamino-benzaldehyde and p-dimethylaminoacetophenone

p-dimethylaminobenzaldehyde (DMABA) and p-dimethylaminoacetophenone (DMAA) were investigated in nonpolar and polar protic and aprotic solvents over a wide temperature range. The sequence of the lower lying excited states was established. The temperature dependence of the fluorescence yields was interpreted within the irreversible reaction kinetics scheme b¹→TICT (twisted internal charge transfer) state. The activation energies and the rate constants were evaluated. Differences between the low-temperature fluorescence or phosphorescence excitation spectra and the absorption spectrum were found to be due to the existence of different rotamers in the ground state. Quantum chemical (INDO) calculations of the energies of electronic transitions, oscillator strengths and dipole moments were performed for flat and twisted conformations of DMABA.     

Spectral dependent kinetics of the EHD luminescence in As-doped Ge

Following pulsed laser excitation of As-doped Ge with impurity concentrations between 10¹⁵-10¹⁷cm^-3, we observe the electron-hole drop (EHD) and excitonic luminescence decay. The spectrum resolved no-phonon (NP) EHD luminescence kinetics are found to depend on its spectral position. “Plateaus” on the kinetic curves for the high energy side of NP-spectrum are observed at high excitation. The data suggest this luminescence is due to the states which are in dynamical equilibrium during some time after excitation pulse.     

Synthesis and spectroscopic investigation of a novel solvatochromic dye

Optical response of a novel dye has been studied in various media like neat and mixed binary solvents, aqueous SDS micelles and β-cyclodextrin (β-CD) nanocavities. Fluorescence parameters in pure and mixed binary solvents have been found to be sensitive to the nature of the microenvironment. The emitting state of the dye in protic solvent is different from that in aprotic solvents. In presence of cations (H⁺, Mg²⁺), the dye exists in two tautomeric forms at equilibrium in solution. The values of the equilibrium constant (K) and ΔH⁰ have been measured. Values of local dielectric constant (ε) and microviscosity (η) at the region of solubilisation of the dye in aqueous SDS micellar media have been found out. The dye has also been found to form complex with β-CD. The equilibrium constant and the energy of maximum fluorescence of the dye encapsulated by β-CD have been determined.     

Solvent effects on the structure of the triplet excited state of xanthone: a time‐resolved resonance Raman study

Solvent effects, especially intermolecular hydrogen bonding, play a central role in the photophysics and photochemistry of aromatic ketones. To gain insight into the solute–solvent interactions and their implications for structure and reactivity, we studied xanthone (XT) in two different solvents of similar dipolarity: acetonitrile (ACN; aprotic) and methanol (MeOH; protic), using time‐resolved resonance Raman (TR³) spectroscopy in conjunction with time‐dependent density functional theory calculations. Raman excitation profiles of XT in ACN followed the triplet‐triplet absorption band with a shoulder at the blue end, but for MeOH, they followed the triplet‐triplet absorption band quite closely; therefore, we propose that the resonance enhancement of Raman peaks are from two states in ACN and from a single state in the MeOH solvent. Furthermore, a resonance Raman peak at 614 cm⁻¹ (a₂ symmetry) that appeared in ACN but not in the MeOH solvent has been identified as a vibronic active mode that could be involved in coupling the two lowest 1³ππ* (1³A₁) and 1³nπ* (1³A₂) excited states. This was further confirmed by depolarization ratio measurements of some of the representative TR³ peaks in ACN, which showed a depolarized intensity for the 614 cm⁻¹ peak while the other peaks were polarized. Interestingly, we also observed blue shifting of some of the vibrational frequencies of XT in the 1³ππ* state compared with the ground state with increasing solvent polarity. This anomalous blue shift casts doubt on the general use of the resonance canonical structure to explain the structure of the excited states. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet states of XT separate them further in energy and that this can contribute to its low reactivity towards H atom abstraction in protic solvents. Copyright © 2016 John Wiley & Sons, Ltd.     

Cooperative luminescence and absorption in ytterbium doped aluminosilicate glass optical fibres and preforms

The cooperative luminescence and absorption properties of Yb³⁺ doped aluminosilicate glass optical fibres and preforms are investigated in detail. In accordance with previous investigations, both the visible cooperative luminescence and the infrared luminescence decay measurements have been resolved into a single exponential decay component. We show that for a glass with similar Yb³⁺ dopant concentration but more Al³⁺, the glass emits less visible luminescence. Absorption loss measurements completed on fibre samples revealed a broad absorption in the 350-500 nm range, which we propose is due to a combination of Yb²⁺ absorption and cooperative absorption from Yb³⁺ ion pairs.     

Optimization in Solvent Selection for Chlorin e6 in Photodynamic Therapy

The photophysical properties of chlorin e6 (Ce6) in twelve different protic, aprotic and non-polar solvents were investigated using ultraviolet–visible and fluorescence spectroscopic methods. Solvatochromic effects were determined by the changes in quantum yield, Stokes shift, fluorescence half-life and excited state dipole moments of Ce6 in the different solvents. The absorption shifts observed in different solvents were further analyzed using the Kamlet-Abboud-Taft model and the nature of solute-solvent interactions between Ce6 and different protic and aprotic solvents was elucidated. The quantum yields were found highest in protic solvents (except water), followed by aprotic and non-polar solvents. Solvent polarity parameters showed a linear increasing trend with Stokes shift and fluorescence half-life, which indicated the presence of Ce6-solvent interaction. Using the Kamlet-Abboud-Taft model, a direct correlation between the solvent polarity parameters and absorption shift was observed, which substantiated the existence of Ce6-solvent interaction by hydrogen bond formation. The excited state dipole moments in specific protic and aprotic solvents were found to be higher than the ground state dipole moments, implying a more polar nature of Ce6 during excited state transition.     

Pyrene-Naftylamide Bifluorophore for Spectra-Converting Media

New bifluorophore containing pyrene as an excitation energy donor and naphtylamide as an acceptor is synthesized and its optical properties are studied. It is founded that excitation spectrum of the bifluorophore is almost the sum of its constituents—pyrene and naftylamide. At the same time, in the luminescence spectrum there only the peak of acceptor luminescence is observed, which indicates the effective radiationless energy transfer from the donor to the acceptor. This is also proved by time resolved measurements of bifluorophore decay. The decay rate was calculated from decay curve and appear to be 0.25 нс^?1. The same value obtained from the Förster’s theory is almost by an order as high. It indicates that Förster’s does not applicable in this particular case. Instead, we have to use the electron excitation density functions approach.     

Laser and absorption saturation measurements of Cr crystals, pumped by broadband pulsed 940 nm radiation

The characteristics of a 940 nm pumped Cr⁴⁺:forsterite laser have been investigated using a pulsed colour centre laser as the excitation source. Laser threshold, slope efficiency and temporal behaviour have been determined for high and low Cr⁴⁺ doped material. 940 nm pumping is found to be more efficient than 532 and 730–770 nm excitation. Discrepancies with 1064 nm pumping are attributed to excited state absorption. Absorption saturation measurements have been used to assess the potential applications of Cr⁴⁺:forsterite, Cr⁴⁺:YAG and Cr⁴⁺: Lu₃A1₅O₁₂ (LuAG) as passive Q-switches for Nd lasers in the 940 nm region.     

Spectroscopic Study of Solvent Polarity on the Optical and Photo-Physical Properties of Novel 9,10-bis(coumarinyl)anthracene

Novel 7,7′-((anthracene-9,10-diylbis(methylene))bis(oxy))bis(4-methyl-2H-chromen-2-one) (BisCA) was prepared as fluorescent probe. The chemical structure of the novel BisCA was confirmed by spectroscopic data as well as elemental analyses. The solvatochromic characteristics of the new proble and its precursors were investigated in different solvents including, ethanol, DMF and toluene as protic polar, aprotic polar and non-polar solvents, respectively. Photo-physical parameters of probes, such as fluorescence quantum yields, fluorescence lifetime of excited state, radiative and non-radiative decay, were assessed in different media. The intermolecular H-bond effect on absorption and excitation spectra of the novel probe was reported in different solvents. Also, Onsager cavity radius and dipole moment of ground state and excited state of the probe were calculated as described by Bakhshiev and Reichardt methods.     

Time-resolved fluorescence spectra of a bichromophoric molecule, 2-methyl-1,2,3,4-tetrahydroisoquinoline in various media

Time-resolved fluorescence spectra of a title molecule (with benzene and aliphatic amine parts) in various media, after excitation by several lasers were observed to complement the previous work by conventional spectroscopy [N. Kanamaru, J. Tanaka, J. Phys. Chem. 95 (1991) 6441]. Though complex with many new features, the results were roughly consistent with the previous ones. The significant conclusions are as follows: (1) The emission to be ascribed to the amine (N) part, with more than one component (of nN and aN types) is observed not only for the acetonitrile solution (as previously reported) but also for all the other media. (2) Contrary to the case of a nonpolar hexane solution, both of N fluorescences in the other media reveal unusually long-lived decay components. This can be interpreted by assuming the so-called charge-transfer-to-solvent (CTTS) state that is nonfluorescent and lies just below the fluorescent state. (3) This observation in the protic media can also be taken as another evidence of the peculiar hydrogen bonding between this amine and the protic solvent molecules [N. Kanamaru, J. Tanaka, J. Phys. Chem. 95 (1991) 6441]. (4) Thus, the unexpectedly large quantum yields of N fluorescences in the polar media are now interpreted as arising due to the slow S₁^N→(CTTS)→S₀ internal conversions.     

Beta decay of 125Sb and level structures in 125Te

The decay of 2.76y ¹²⁵Sb to levels of ¹²⁵Te has been studied using an HPGe detector for gamma-ray and a mini orange electron spectrometer for conversion electron measurements. We identify 38 transitions in this decay, including 13 gamma rays and 4 conversion electron lines being reported for the first time. New results also include E1 multipolarity assignments to 3 newly observed transitions and M-shell conversion coefficient for the 109 keV M4 transition. A revised ¹²⁵Te level scheme is constructed using Ritz combination principle. While confirming the existence of 10 well established levels below 700 keV excitation, we introduce 3 other levels at 402.0, 538.6 and 652.9 keV. Interpretation of the observed levels in terms of various theoretical approaches is briefly discussed. The newly introduced 538.6 keV (1/2⁺) and 652.9 keV (3/2⁺) levels are seen as the two missing members of the (s _1/2 ⊗ 2⁺) and (d _3/2 ⊗ 2⁺) sextuplet in the quasiparticle-phonon coupling scheme.     

Rate equation modelling of erbium luminescence dynamics in erbium-doped silicon-rich-silicon-oxide

Erbium doped silicon-rich silica offers broad band and very efficient excitation of erbium photoluminescence (PL) due to a sensitization effect attributed to silicon nanocrystals (Si-nc), which grow during thermal treatment. PL decay lifetime measurements of sensitised Er³⁺ ions are usually reported to be stretched or multi exponential, very different to those that are directly excited, which usually show a single exponential decay component.In this paper, we report on SiO₂ thin films doped with Si-nc's and erbium. Time resolved PL measurements reveal two distinct 1.54 μm Er decay components; a fast microsecond component, and a relatively long lifetime component (10 ms). We also study the structural properties of these samples through TEM measurements, and reveal the formation of Er clusters. We propose that these Er clusters are responsible for the fast μs decay component, and we develop rate equation models that reproduce the experimental transient observations, and can explain some of the reported transient behaviour in previously published literature.     

Synthesis and Spectral Properties of Novel Fluorescent Poly(oxyethylene Phosphate) Tris(β-diketonate) Europium (III) Complexes

Novel poly(oxyethylene phosphate) tris(β-diketonate) europium (III) complexes have been synthesized by an improved procedure using the Atherton–Todd reaction conditions. N-ethyldiisopropylamine has been used as a mild base and propylene oxide as an acid scavenger in order to obtain poly(oxyethylene phosphate) in yield and purity higher than those achieved by conventional methods. The compounds have been characterized by ¹H, ¹³C, and ³¹P NMR and FTIR techniques. Their absorption, fluorescent excitation and emission spectra of chloroform and abs. ethanol solutions have been recorded and studied. The luminescent quantum yields and decay times have been determined and a dependence on the length of the oxyethylene spacer between phosphate groups has been established. The new polymer complexes are water soluble and have increased luminescence decay time in comparison with corresponding ternary complexes.     

A Negative Deviation from Stern–Volmer Equation in Fluorescence Quenching

A negative deviation from the normal Stern-Volmer equation shown in the fluorescence quenching of doxorubicin by adenosine 5' monophosphate is interpreted in terms of doxorubicin exists in two different conformers in the ground state. An estimate of the Stem-Volmer constant for the excited-state quenching is about 218 M(-1). The fluorescence decay of free doxorubicin is a bi-exponential in polar protic and polar aprotic solvents. In the presence of adenosine 5' monophosphate, doxorubicin shows a tri-exponential decay in water.     

Intra-dot relaxation and dephasing rates from time-resolved photoluminescence from InAs quantum dot ensembles

An ensemble of InAs quantum dots with ground state transition energies centered at 1.216 eV and density 10¹¹dots/cm² has been studied by time-resolved photoluminescence (PL). The wavelength of the 100-fs excitation pulse was tuned through the ground (excited) state transitions, resulting in resonant (optical phonon sideband) PL. The decay of the PL was time resolved with a streak camera in the interval 1.5–3 ns to avoid scattered laser light. The intensity of the PL was recorded with its polarization both parallel with and perpendicular to the excitation polarization (along one of the crystal’s cleave axes); the ratio is 2.22 at low temperatures and low excitation. A phenomenological rate equation analysis is made, separating the excitations into two classes, one polarized along the excitation polarization and the other unpolarized (either that way immediately after the excitation pulse or scattered from the first class). Excellent fits to the data lead to the conclusion that both classes decay radiatively with a lifetime of 1 ns, and a transfer from the polarized to the unpolarized species takes place with a distribution time of 12 ns at low temperatures and low excitation, dropping rapidly toward zero for temperatures above 30 K and for intense excitation levels. The polarization of a coherently excited ground state exciton should dephase with a rate equal to the sum of the radiative rate plus the inverse of this distribution time.     

Spectrophotometric Characteristics of New Pyridylindolizine Derivatives Solutions

Three new pyridylindolizine derivatives, 1, 2, 3-tricarbometoxi-7-(4-pyridyl)-pyrrolo[1, 2-a]pyridine (I), 1,2-dicarboethoxy-3-(4-bromobenzoyl)-7-(4-pyridyl)-pyrrolo[1,2-a]pyridine (II) and its isomer 1,2-dicarboethoxy-3- (4-bromobenzoyl) -5- (2-pyridyl) -pyrrolo[1, 2-a]pyridine (III) have been investigated in different solutions by UV-VIS absorption, steady-state, and time-resolved fluorescence methods. The effects of the substituent and solvent on the spectroscopic properties have been demonstrated. The fluorescence decay data could be fitted to a single-exponential function. The lifetime values are higher in protic polar than in aprotic apolar solvents for compound I. In the case of compounds II and III the fluorescence intensities and lifetimes are very low, with the exception of III in aprotic solvents. The absorption and fluorescence properties of the compounds showed a solvent dependence.     

Relaxation of the pulsed opto-galvanic current signal in a helium positive column

Transient behaviour of an opto-galvanic (OG) current signal induced by pulsed dye laser excitation has been investigated on the He I 388.9-nm (2³S-3³P) transition in a He positive column. The OG current signal is composed of a sharp spike at the early time stage followed by a slowly-varying component. The decay time of the sharp OG current signal has been found to be almost independent of the dc current substaining the discharge and to depend sensitivity on a product of pressure and column-radius. The experimental results show that the dominant decay process of the OG current consists in an ion current to the walls, as has been previously referred to in a mmodel of a cw OG effect in a He positive column. A model for the pulse OG effect in the early time stage is presented on the basis of the experimental results. The decay times of the OG current signals calculated with the model are in agreement with the measurements within an accuracy of 30%.     

Study of the correlation of scintillation decay and emission wavelength

In photoluminescence which directly excites the emission center of phosphor material is known to have a correlation between the emission wavelength and the decay time based on quantum mechanics. In scintillation phenomenon, host lattice of the material is first excited by ionizing radiation and then the excitation energy is transferred to emission centers. For the first time, we investigated the correlation between the scintillation decay and the emission wavelength by using pulse X-ray equipped streak camera system which could observe time and wavelength resolved scintillation phenomenon. Investigated materials were Ce³⁺, Pr³⁺ and Nd³⁺ doped oxides and fluorides which all showed 5d-4f transition based emission. As a result, we obtained the relation that τ (scintillation decay time) was proportional to the λ^2.15 (emission wavelength).