A turn-on fluorescent chemosensor for Hg based on phenanthroline fluorophore

Dipyrido[3,2-a:2′,3′-c]-phenazine (L) was employed as a selectively fluorescent chemosensor for Hg²⁺ in DMF solution under buffered conditions with its fluorescence being strongly increased. The fluorescence increasing was attributed to the formation of L–Hg²⁺ by 1:1 complex ratio (K=3.7×10⁵ M⁻¹), which constitutes the basis for the determination of Hg²⁺ with the prepared chemosensor. The experiment results also show that the response behavior of L to Hg²⁺ is pH independent in the range of pH 6.0–9.0 and show excellent sensitivity and selectivity for Hg²⁺ over other examined metal ions.     

A Sensitive Fluorimetric Method for the Determination of Epinephrine

A sensitive fluorimetric method for the determination of epinephrine (E) is described in this paper. The experiments indicate that epinephrine can react with formaldehyde (HCHO) in an acid medium to form a condensation product, which can be oxidized by potassium hexacyanoferrate(III) (K₃[Fe(CN)₆]) in borax buffer (pH = 9.5). The reaction product can emit strong fluorescence. Ascorbic acid (AA) is used in order to consume excess potassium hexacyanoferrate and stabilize the fluorescent product. Under optimum conditions, a linear relationship has been obtained between the fluorescence intensity and the concentration of epinephrine in the range of 1.4×10^–9–2.1×10^–6 mol/l, and the detection limit is 2.4×10^–10 mol/l (4.3×10^–11 g/ml, S/N = 3). The method is applied for the determination of E in both actual sample and the synthetic sample with E and norepinephrine (NE) by using the coupling technique of synchronous fluorimetry and H-point standard addition method, and the results obtained are satisfactory.     

Radiative and non-radiative decays from the excited state of Ti3+ ions in oxide crystals

The fluorescence spectra of Ti³⁺ in Y₃Al₅O₁₂ (YAG), Al₂O₃ (sapphire), YAlO₃ (YAP) observed at 10 K are composed of zero-phonon lines accompanied by the broad vibronic sidebands. The temperature dependence of the fluorescence lifetime and of the total intensity of the broadband measured in YAG and Al₂O₃ indicate that the radiative decay times from the excited states are nearly constant in the range 10–300 K. This demonstrates that the broadband radiative emissions in Ti³⁺:YAG and Ti³⁺:Al₂O₃ are due to magnetic dipole transitions or to electric dipole transitions induced by static odd-parity distortion, respectively. The decrease of the fluorescence lifetime with increasing temperature in Ti³⁺:YAG and Ti³⁺:Al₂O₃ is due to non-radiative decay from the excited state which occurs through phonon-assisted tunnelling between the excited and ground states. The radiative decay of Ti³⁺:YAP is enhanced with increasing temperature, indicating that radiative decay rate contains a term associated with odd-parity phonons. Nevertheless, a non-radiative decay rate of 3.6 × 10⁴ s^–1 observed in the temperature range 10–300 K is due to excited state absorption, which depopulates the excited state and quenches the fluorescence at the laser wavelength.     

A Pyrene-based Highly Selective Turn-on Fluorescent Sensor for Copper(II) Ion and its Application in Live Cell Imaging

A new pyrene derivative (chemosensor 1) containing a picolinohydrazide moiety exhibits high selectivity for Cu²⁺ ion detection in mixed aqueous media (CH₃OH:H₂O = 7:3). Significant fluorescence enhancement was observed with chemosensor 1 in the presence of Cu²⁺. However, the metal ions Ag⁺, Ca²⁺, Cd²⁺, Co²⁺, Cu²⁺, Fe²⁺, Fe³⁺, Hg²⁺, K⁺, Mg²⁺, Mn²⁺, Ni²⁺, Pb²⁺, and Zn²⁺ produced only minor changes in fluorescence for the system. The apparent association constant (K _a) of Cu²⁺ binding in chemosensor 1 was found to be 2.75*10³ M⁻¹. The maximum fluorescence enhancement caused by Cu²⁺ binding in chemosensor 1 was observed over the pH range 5–8. Moreover, by means of fluorescence microscopy experiments, it is demonstrated that 1 can be used as a fluorescent probe for detecting Cu²⁺ in living cells.     

An NBD-based Sensitive and Selective Fluorescent Sensor for Copper(II) Ion

A new 7-nitrobenz-2-oxa-1,3-diazole (NBD) derived fluorescent probe (1) exhibiting high selectivity for Cu²⁺ detection, produced significant fluorescence quenching in the presence of Cu²⁺ ion, while the metal ions Ca²⁺, Cd²⁺, Co²⁺, Fe²⁺, Hg²⁺, Mg²⁺, Mn²⁺, Ni²⁺ and Zn²⁺ produced only minor changes in fluorescence. The apparent association constant (K _a) for Cu²⁺ binding in chemosensor 1 was found to be 1.22 × 10³ M⁻¹. The maximum fluorescence quenching activity caused by Cu²⁺ binding to 1 was observed over the pH range 6–10.     

Fluorescence studies and semiempirical calculations on alkali ion indicators

Two newly synthesized cryptands act as sensitive Na⁺- and K⁺-selective indicators for cation concentrations above 20 M. The fluorescence properties change markedly upon cation binding. In addition, the free ligands exhibit a pronounced sensitivity to pH, which is considerably lower for the cation complexes. Time resolved fluorescence is characterized by a decay time of about 5 ns that is attributed to the diprotonated protolytic state of the uncomplexed ligands. Semiempirical calculations show the systematic influence of the nitrogen lone pairs or the N–H bond on the stability of the system. The cause of the strong fluorescence intensity increase observed upon protonation of the fluorescent cryptands may be attributed to an increase in the S₁–T _x energy gap as a consequence of bridgehead nitrogen protonation.This is a peer-reviewed conference proceeding article from the Third Conference on Methods and Applications of Fluorescence Spectroscopy, Prague, Czech Republic, October 18–21, 1993.     

Preparation,Characterization and Application of Fluorescent Terbium Complex-Doped Zirconia Nanoparticles

Novel zirconia-based fluorescent terbium nanoparticles have been prepared as a fluorescent nanoprobe for time-resolved fluorescence bioassay. The nanoparticles were prepared in a water-in-oil (W/O) microemulsion consisting of a strongly fluorescent Tb³⁺ complex, N,N,N¹, N¹-[2,6-bis(3′-aminomethyl-1′-pyrazolyl)-phenylpyridine]tetrakis(acetate)-Tb³⁺(BPTA-Tb³⁺), Triton X-100, hexanol, and cyclohexane by controlling co-condensation of Zr(OCH₂CH₃)₄ and ZrOCl_2. The characterizations by transmission electron microscopy and fluorometric methods indicate that the nanoparticles are uniform in size, 33± 4 nm in diameter, and have a fluorescence quantum yield of 8.9% and a long fluorescence lifetime of 2.0 ms. The zirconia-based fluorescent terbium nanoparticles show high stability against basic dissolution in a high pH aqueous buffer compared to the silica-based nanoparticles. A surface modification and bioconjugation method for the fluorescent nanoparticles was developed, and the nanoparticle-conjugated streptavidin (SA) was used for time-resolved floroimmunoassy (TR-FIA) of human prostate specific antigen (PSA). The result shows that the zirconia-based fluorescent terbium nanoparticles are useful as a fluorescent nanoprobe for time-resolved fluorescence bioassay.     

Luminescence decay of rare earth ions in an orthophosphate matrix

Abstract

Investigations of the luminescence decay of Ce³⁺- and Tb³⁺-ions in solid solutions of the system K₃La_1?x?yCe_xTb_y(P0₄)₂ were carried out at 298 K and 10 K using a laser pulse spectrometer or synchrotron radiation as excitation sources. A comparison of the decay times determined in the host absorption range (160 nm) and in the Ce³⁺- and Tb³⁺- ion levels shows a delayed decay of the host excitation. The results are discussed in regard to energy transfer.     

The A(K-stop,Λd )A'' reaction, a tool to observe [ˉNNN] clusters

This work presents experimental results obtained from a study of the K ^- _stop A → ΛdA' reaction, where A = ⁶ Li . The study concerns the distributions of the Λd invariant mass, which allows us to determine the structure of bound [K ^- ppn] systems in nuclei. A candidate of such clusters is identified in the present measurement, and its mass (binding energy), decay width and yield are reported. The experiment was performed at the DAΦ NE φ -facility (LNF) by using the FINUDA spectrometer. The study depended on the capability of FINUDA to reconstruct the traces of all the particles involved in the decay of the nuclear cluster.     

Energy levels of vanadium ions in CdTe

In CdTe doped with vanadium the photoluminescence due to the ³ T ₂(F) ³ A ₂(F) transition of V³⁺(d ²) is detected. Its decay time is determined as (630±20) s, a result comparable to the analogous emissions in various host lattices. Further emissions around 5000 cm^–1 and 9000 cm^–1 are caused by charge-transfer transitions or bound-exciton decay. Excitation and sensitization spectra yield information on the positions of the energy levels within the gap, which are discussed using two different models. At T=4.2 K, the distance of the V²⁺/V³⁺ donor level is 7300 cm^–1 and 5700 cm^–1 referred to the valence and the conduction band edges, respectively. The absence of V²⁺(d ³) centres is tentatively ascribed to the existence of deeply bound excitons.     

A Characteristic Decay Semigroup for the Resonances of Trace Class Perturbations with Analyticity Conditions of Semibounded Hamiltonians

To asymptotic complete scattering systems {M ₊+V,M ₊} on H₊:=L²(R₊,K{\mathcal{H}}_{+}:=L^{2}(\mathbf{R}_{+},{\mathcal{K}}, d λ), where M ₊ is the multiplication operator on H₊{\mathcal{H}}_{+} and V is a trace class operator with analyticity conditions, a decay semigroup is associated such that the spectrum of the generator of this semigroup coincides with the set of all resonances (poles of the analytic continuation of the scattering matrix into the lower half plane across the positive half line), i.e. the decay semigroup yields a “time-dependent” characterization of the resonances. As a counterpart a “spectral characterization” is mentioned which is due to the “eigenvalue-like” properties of resonances.     

Swift heavy ions-induced degradation on the electrical characteristics of silicon NPN power transistors

ABSTRACT

The pre- and post-irradiation effects on the DC electrical characteristics of 100?MeV Phosphorous (P⁷⁺) and 80?MeV Nitrogen (N⁶⁺) ion-irradiated NPN transistors were studied in the dose range from 600?krad (Si) to 100?Mrad (Si). The different electrical characteristics, such as Gummel characteristics, excess base current (ΔI_B?=?I_B-Post?–?I_B-Pre), current gain (h_FE), damage constant (K) and output characteristics, were measured in situ after ion irradiation. The considerable increase in the base current (I_B) at lower V_BE and slight decrease in the collector current (I_C) at higher V_BE were observed after ion irradiation. The C–V measurements revealed that the doping concentration (N_d) was found decreased, while the built-in potential (V_bi) increased after irradiation. The ion-irradiated results are compared with ⁶⁰Co gamma-irradiated results in the same dose range. The SRIM simulation was performed to understand the range of ions and energy loss in the transistor structure. The SRIM simulation showed that 100?MeV P⁷⁺ and 80?MeV N⁶⁺ ions can easily pass through the active region of transistors by creating ionization and displacement damages in the device structure. The irradiation results showed that ions induce more degradation in the electrical characteristics when compared to ⁶⁰Co gamma radiation at the same dose range.     

The Dynamics of Intramolecular Excited State Relaxation of <Emphasis Type="Italic">N</Emphasis>-Anthryl Substituted Pyridinium Cations

N-(1-Anthryl)-2,4,6-trimethyl-pyridinium (I), N-(2-anthryl)-2,4,6-trimethyl-pyridinium (II) and 10-(1-anthryl)-1,2,3,4,5,6,7,8-octahydro-acridinium cations (III) with anomalously high fluorescence Stokes shift have been investigated. Fluorescence kinetics analysis at various temperatures showed that in the range 293–77 K, the radiative deactivation rate constants (k_f) increase by 5.5 to 30 times. The low-temperature time-resolved emission spectra of I–III were found to be consistent with the model: A A^* B^* where A^* is the local excited twisted form and B^* is the relaxed more planar, bent conformer of the molecule. The rate constants of the excited relaxed state formation (k₁) and back reaction (k_–1) of compounds studied were estimated.     

Acoustical and excess properties of {1-hexanol + n-hexane, or n-octane, or n-decane} at (298.15, 303.15, and 308.15) K

Densities (ρ) and speeds of sound (u) for the binary mixtures of 1-hexanol with n-hexane, n-octane and n-decane have been measured over the entire composition range at 298.15, 303.15 and 308.15 K. The dynamic viscosities (η) for these systems have been measured at 298.15 K. From experimental data, excess molar volumes (V_m^E), molar isentropic compressibility (K_s,m), excess molar isentropic compressibility (K_s,m^E), deviation in speed of sound (u^D) from their ideal values (u^id) in an ideal mixture, and excess free volumes (V_f^E) have been calculated. The excess functions have also been correlated with the Redlich–Kister polynomial equation. The viscosity data have been analysed in terms of some semi-empirical equations. The theoretical values of speed of sound (u) and isentropic compressibility (κ_S) have also been estimated using the Prigogine–Flory–Patterson (PFP) theory with the van der Waals (vdW) potential energy model and the results have been compared with experimental values. The effect of chain-length of n-alkanes as well as the temperature on the excess properties has also been studied.     

Enhancement effect of some phosphorylated compounds on fluorescence of quinazoline-based chelating ligand complexed with gallium ion

The chelating ligand, 2,4-[bis-(2,4-dihydroxybenzylidene)]-dihydrazinoquinazoline (DBHQ) can form a fluorescence complex with Ga³⁺ ions. The fluorescence intensity of the obtained DBHQ–Ga³⁺ complex increases in the presence of some phosphorylated compounds. The addition of phosphorylated serine and tyrosine, pyridoxal-5′-phosphate (PLP), and glucose-6-phosphate (G6P) leads to an increase in the fluorescence quantum yield (φ) of the complex by 1.38–1.59 times, while the addition of serine, tyrosine, pyridoxal, and glucose leads to a small increase in φ (1.02–1.04). This is the first report on the fluorescence enhancement effect of phosphorylated compounds on a Ga³⁺ ion complex.     

Luminescence enhancement in (Nd+Ce) doped SiO2 : Al2O3 sol–gel glasses

An enhancement in NIR luminescence from Nd³⁺-doped Ce³⁺ co-doped SiO₂+Al₂O₃ sol–gel glasses has been observed. The lasing transition (⁴F_3/2→⁴I_11/2) at 1072 nm from the dual rare-earth Nd³⁺+Ce³⁺-doped glasses has shown an emission strength of about five times that of the single rare-earth ion Nd³⁺-doped glass. From the measurement of lifetimes of the transition at 1072 nm, the transfer rate (W_tr), critical distance (R₀) and energy transfer efficiency (η) of the neodymium glasses have been calculated.     

Decay Law of Moving Unstable Particle

Quantum relativistic decay law of moving unstable particle is analytically calculated in the model case of the Breit–Wigner mass distribution. It turns out that Einstein time dilation of the moving particle decay holds approximately at times when the decay is exponential. The related correction is calculated analytically. Being very small at these times it is practically unobservable. It is shown that Einstein dilation fails for large times t when decay is not exponential. An unstable system of the kind of K ₀-meson (which is the superposition of K _s and K _I) is also considered. In this case, the violation of Einstein dilation is shown to be appreciable at all times under some condition     

A Fe<Superscript>3+</Superscript>/Hg<Superscript>2+</Superscript>-Selective Anthracene-Based Fluorescent PET Sensor with Tridentate Ionophore of Amide/β-Amino Alcohol

A new anthracene-based fluorescent PET sensor 1 with a tridentate ionophore of amide/β-amino alcohol displays very good selectivity and sensitivity for Fe³⁺ (K _a = 1.6 × 10³ M⁻¹) and Hg²⁺ (K _a = 2.1 × 10³ M⁻¹) in CH₃CN–H₂O (3:7, v/v) with detection limit of 1 μM. More fluorescence enhancement was observed when 1 selectively detected Fe³⁺ or Hg²⁺ in CH₃CN and its detection limit was up to 0.03 μM.     

Thermal lens spectrometry in pyroelectric lithium niobate crystals

In this work, the light-induced lens effect due to thermal and/or photorefractive processes was studied in pyroelectric (undoped and Fe²⁺-doped) lithium niobate crystals (LiNbO₃) using thermal lens spectrometry with a two-beam (pump–probe) mode-mismatched configuration. The measurements were carried out at two pump beam wavelengths (514.5 and 750 nm) to establish a full understanding of the present effects in this material (thermal and/or photorefractive). We present an easy-to-implement method to determine quantitative values of the pyroelectric coefficient (dP _s/dT), its contribution to the thermal effect and other thermo-optical parameters like thermal diffusivity (D), thermal conductivity (K) and temperature coefficient of the optical path length change (ds/dT). These measurements were performed in LiNbO₃ and LiNbO₃:Fe (0.1 ppm Fe²⁺) crystals with c axis along the direction of laser propagation.     

Electrical properties of perovskite-type La(Cr1−xMnx)O3+δ

Perovskite-type La(Cr_1−xMn_x)O_3+δ (0.0x1.0) was synthesized using a sol–gel process. The crystal structure of La(Cr_1−xMn_x)O_3+δ changes from orthorhombic to rhombohedral at x=0.6. The Mn⁴⁺ ion content increases monotonically in the range 0.2x1.0. The magnetic measurement of La(Cr_1−xMn_x)O_3+δ indicates that a Mn³⁺ ion is a high-spin state with (d)³(dγ)¹. The variation of the average (Cr, Mn)-O distance is explained by ionic radii of the Cr³⁺, the Mn³⁺, the Mn⁴⁺ ions. Since the log σT–1/T curve is linear and the Seebeck coefficient (α) is independent of temperature, it is considered that La(Cr_1−xMn_x)O_3+δ is a p-type semiconductor and exhibits the hopping conductivity.