New Application of a Known Molecule: Rhodamine B 8-hydroxy-2-quinolinecarboxaldehyde Schiff Base as a Colorimetric and Fluorescent “Off-On” Probe for Copper (II)

Rhodamine B 8-hydroxy-2-quinolinecarboxaldehyde Schiff base (1) has been investigated as a colorimetric and fluorescent “off-on” probe for the recognition of Cu²⁺ in aqueous solution. Probe 1 was synthesized by condensation of rhodamine B hydrazide and 8-hydroxy-2-quinolinecarboxaldehyde, which exhibited good selectivity for Cu²⁺ among a range of biologically and environmentally important metal ions. The Cu²⁺ recognition event undergoes a Cu²⁺ promoted hydrolysis of probe 1 to release rhodamine B and the recognition process is barely interfered by other coexisting metal ions.

A Novel Colorimetric and Fluorescent “Off-On” Chemosensor for Cu2+ Based on a Rhodamine Derivative Bearing Naphthyridine Group

A new rhodamine-based derivative bearing a naphthyridine group (compound 1) was synthesized as a colorimetric and fluorescent “off-on” chemosensor for Cu²⁺ in aqueous solutions. The sensing behaviors of 1 toward various metal ions in neutral aqueous solutions were investigated by absorption and fluorescence spectroscopies. Compound 1 is found to exhibit a significant increase in absorbance at 561 nm and an amplified fluorescence at 590 nm toward Cu²⁺ in a selective, sensitive and rapid manner. The quantification of Cu²⁺ by 1 using an absorption spectroscopy method was satisfactory in the linear working range 0.9–10 μM, with a detection limit of 5.4?×?10^?8?M for Cu²⁺ and good tolerance of other metal ions. Upon addition of Cu²⁺, the spirolactam ring (colorless and nonfluorescent) of 1 was opened to ring-opened amide (red color and fluorescent) and a 1:1 stoichiochemetry for the 1-Cu²⁺ complex was formed with an association constant of 1.57?×?10⁴?M^?1.     

The “SKATE” CO2 Gigawatt Laser for a Laser-Plasma Generator of Ions and Nuclei

A set-up of the CO₂ SKATE and its output characteristics are described. The system is based on a self-sustained gas discharge module with x-ray preionization that ensures reliability and stable repetition rate operation at 1 Hz for a long time. Measurement of the initial electron density in the discharge volume produced by an x-ray gun is presented for different gases and their mixtures, which is of independent interest for some applications of x-ray preionization. Data on measurements of the low-intensity signal gain and laser parameters for a free-running generator configuration are presented as well as long-term operation characteristics. This laser system has been used as a CO₂ generator with gigawatt peak intensity and high spatial–temporal characteristics. In particular, the laser can be used as a driver for a source of multicharged ions in contrast to the laboratory prototypes previously investigated.     

Fluorescence “Switch on” of Conjugates of CdTe@ZnS Quantum Dots with Al, Ni and Zn Tetraamino-Phthalocyanines by Hydrogen Peroxide: Characterization and Applications as Luminescent Nanosensors

In this study, we have developed a novel nanoprobe for H₂O₂ based on the conjugation of CdTe@ZnS quantum dots (QDs) to different metal tetraamino-phthalocyanine (MTAPc): (M?=?(OAc)Al, {OAc?=?acetate}, Ni and Zn). Chemical coordination of the QDs to the MTAPc resulted in the fluorescence “switch off” of the linked QDs which was associated with Förster resonance energy transfer (FRET). In the presence of varying concentration of H₂O₂, the fluorescence of the linked QDs was progressively “switched on” and the FRET mechanism between the QDs and the MTAPc was disrupted. The sensitivity/limit of detection of the nanoprobe followed the order: QDs-ZnTAPc (2.2 μM)?>?QDs-NiTAPc (4.4 μM)?>?QDs-AlTAPc (9.8 μM) while the selectivity followed the order: QDs-NiTAPc?>?QDs-AlTAPc?>?QDs-ZnTAPc. The varying degree of sensitivity/selectivity and mechanism of detection is discussed in detail.     

Condensation Product of 1-Naphthaldehyde and 3-Aminophenol: Fluorescent “on” Probe for Ce3+and “off” Probe for Dichromate (Cr2O72−)

A new probe (Z)-3-((naphthalen-1-ylmethylene)amino)phenol has been synthesized by condensation reaction between 1-naphthaldehyde and 3-aminophenol for the fluorescent sensing of Ce³⁺ by “on” mode and dichromate (Cr₂O₇^2?) by “off” mode. Metal ions—Ag⁺, Al³⁺, As³⁺, Ba²⁺, Ca²⁺, Cd²⁺, Ce⁴⁺, Co²⁺, Cr³⁺, Cr⁶⁺, Cu²⁺, Fe²⁺, Fe³⁺, Hg²⁺, K⁺, La⁺, Li⁺, Mg²⁺, Mn²⁺, Na⁺, Ni²⁺, Pb²⁺, Zn²⁺and anions Br^?, C₂O₄^2?, CH₃COO^?, Cl^?, CO₃^2?, F^?, H₂PO₄^?, HCO₃^?, HF₂^?, HPO₄^2?, I^?, MnO₄^?, NO₃^?, OH^?, S^2?, S₂O₃^2?, SCN^?, SO₄^2? do not interfere. The limit of detection (LOD) for sensing Ce³⁺ and Cr₂O₇^2? ions are 1.286?×?10^–7 M and 6.425?×?10^–6 M, respectively.

     

Perylene Diimide Appended with 8-Hydroxyquinoline for Ratiometric Detection of Cu2+ Ions and Metal Displacement Driven “Turn on” Cyanide Sensing

Perylene diimide (PDI) 3 and 4 appended with 8-hydroxyquinoline derivatives have been synthesized and their photophysical and spectroscopic properties have been experimentally determined. Moreover, PDIs 3 and 4 show ratiometric behavior to detect Cu²⁺ colorimetrically with visible color change from coral red to light pink, whereas 3 and 4 show “turn-off” behavior in fluorescence with lowest limit of detection 5?×?10^?7 M. The PDI 3 could be further utilized for ratiometric CN^? detection colorimetrically and as “turn-on” sensor for CN^? detection fluorometrically with lowest limit of detection 8?×?10^?6 M. The comparison of spectroscopic properties of PDI 1-4 highlights the importance of linking 8-hydroxyquinoline units on the PDI core at bay position for achieving Cu²⁺ recognition event into ratiometric signal.

Luminescent Benzothiazole-Based Fluorophore of Anisidine Scaffoldings: a “Turn-On” Fluorescent Probe for Al<Superscript>3+</Superscript> and Hg<Superscript>2+</Superscript> Ions

A new anisidine possessing benzothiaozle-based chemosensor (1) has been designed and synthesized. The chemosensor 1 was designed to provide hard base environment for ratiometric detection of comparatively less studied Al³⁺ ions. In CH₃CN, the fluorescence spectra of chemosensor 1 red shifted from 368 to 430 nm with addition of Al³⁺ and Hg²⁺ ions; while Cu²⁺ ions caused quenching of emission intensity of 1. These differential changes observed with Al³⁺ and Cu²⁺ ions addition enabled chemosensor 1 to construct “NOR” and “TRANSFER” logic gates.     

The High Sensitive and Selective “Off-On” Fluorescent Zn2+ Sensor Based on the Bis(2,4,7,8,9-pentamethyldipyrrolylmethene-3-yl)methane

A fluorescent chemosensor based on the 3,3′-bis(dipyrrin) bearing two chromophoric dipyrrin units was synthesized, which showed a strongly enhanced fluorescent intensity in the presence of Zn²⁺ ions and a high selectivity toward Zn²⁺ ions over a wide range of tested metal ions in organic solvents.     

A new rhodamine B-based “off–on” fluorescent chemosensor for Cu2+ in aqueous media

A new fluorescent probe 1 (P1) for Cu²⁺ based on rhodamine B was designed and synthesized. P1 exhibits high sensitivity and selectivity for sensing Cu²⁺ and color changes from colorless to pink in aqueous media. Selective fluorescent enhancement of P1 was attributed to ring-opening from the spirolactam (nonfluorescent) to ring-opened amide (fluorescent). A chemosensor based on rhodamine B has a good potential application to the determination of Cu²⁺ in environmental and biological systems.     

New Selective Fluorescent “Turn-On” Sensor for Detection of Hg2+ Based on a 1,8-Naphthalimide Schiff Base Derivative

Journal of Applied Spectroscopy - A new fluorescent “turn-on” sensor for Hg2+, N-allyl-4-(ethylenediamine-5-methylsalicylidene)-1,8-naphthalimide (HL) has been designed by combining a...     

Double Quantum Coherence EPR Reveals the Structure–Function Relationships of the Cardiac Troponin C–Troponin I Complex Regulated by Ca<Superscript>2+</Superscript> Ions and a Phosphomimetic

Troponin (Tn) is a protein that consists of three subunits, troponin C (TnC), troponin I (TnI), and troponin T (TnT), and Tn controls cardiac muscle contraction by calcium ion binding and phosphorylation. The Ca²⁺-binding site is the E–F hand motif (C helix–loop–D helix) in the N-terminal domain of TnC, and the structural transition induced by Ca²⁺ is the opening of these helices and the interaction with TnI, probably at the A and B helices. In this paper, we studied structural changes in the TnC–TnI binary complex on Ca²⁺ binding by double quantum coherence (DQC) distance measurements. We used a binary complex of the cardiac troponin C and I (cTnC and cTnI) complexes, chose four positions of nitroxide spin label at helices A, B, C, and D in the N-terminal domain and chose the E helix in the C-terminal domain as the reference position to study the structural changes on Ca²⁺ addition. The label positions were (A22C/S98C), (M47C/S98C), (Q58C/S98C), and (C84/S98C) for the A, B, C, and D helices, respectively. The effects of phosphorylation of the cardiac-specific N-terminal region of cTnI were studied using a phosphomimetic cTnI mutant. Analysis of the modulation of the DQC echo signals provided the distribution of the spin–spin distance. The distances averaged over the distribution showed that the labels on the A, B, and C helices decreased, i.e., moved to the E helix, on Ca²⁺ binding, while the distance of the label on the D helix showed almost no change. Shoulders and/or small separate peaks were observed in the shape of the distribution and were analyzed as the sum of a few Gaussian functions. The Gaussian functions were grouped into two components, components 1 and 2, at the longer and shorter distances, respectively, separated by 0.7–1.5 nm. The fractions of component 2 were ca. 0.1–0.2 in the Ca²⁺-free state and increased by 0.2–0.3 on Ca²⁺ addition, suggesting that the increase in component 2 is related to physiological control of cardiac muscle contraction. The phosphomimetic-modification effects on the Ca²⁺-induced changes of the fraction of components and the distances of the C- and D-helix labels are small. On the other hand, in the A and B helices, there are significant effects on the Ca²⁺-induced changes in the distances of the components. The different behaviors of A/B and C/D helices support the current model of the phosphorylation effects in which both N-terminal region and regulatory domain of cTnI interact with the A and B helices of cTnC.     

Spin-Hamiltonian parameters and tetragonal distortion due to the Jahn–Teller effect for Cu2+ centres in trigonal Zn(BrO3)·6H2O crystal

The spin-Hamiltonian parameters (g factors g_//, g_⊥ and hyperfine structure constants ⁶⁵A_// and ⁶⁵A_⊥) for the tetragonal Cu²⁺ centres in trigonal Zn(BrO₃)·6H₂O crystal are calculated from the complete diagonalization (of energy matrix) method (CDM) based on the cluster approach. In the CDM, the Zeeman and hyperfine interaction terms are added to the Hamiltonian in the conventional CDM and the contributions to the spin-Hamiltonian parameters from both the spin-orbit coupling parameter of central d⁹ ion and that of ligand ion are included. The calculated spin-Hamiltonian parameters of Zn(BrO₃)·6H₂O: Cu²⁺ show good agreement with the experimental values and the tetragonal elongation (characterized by ΔR=R_// ? R _⊥, where R_// and R _⊥ represent the metal-ligand distances parallel with and perpendicular to the C₄ axis) due to the static Jahn–Teller effect is obtained from the calculations. The results are discussed.     

Mix-substituted phthalocyanines of a “push–pull”-type and their metal complexes as prospective nanostructured materials for optoelectronics

To study the influence of structural features of phthalocyanine (Pc) derivatives on their physico-chemical properties in bulk and thin films, 23 new phthalocyanines with different quantity and ratio of donor (alkyloxy-groups, in fragment “A”) and acceptor (Cl-, in fragment “B”) substituents in one molecule of the A₃B, ABAB and AABB types with varied length of alkyloxy-substituents and their metal complexes were designed and synthesized. A comparative analysis of spectral, mesomorphic and photoelectric properties of these mix-substituted phthalocyanines of a “push–pull” type was performed. It was shown that non-peripheral substitution by alkyloxy-fragments in hetero-substituted Pcs (similar to homo-substituted Pc) leads to red-shifting of the Q-band into near-IR region. The intensity of photoluminescence, position of peaks and their splitting are strongly connected with chemical structure of Pcs and the type of solvent. In contrast to non-mesogenic octyloxy-Pc (A4) having alkyloxy-substituents in non-peripheral positions, 22 of 23 synthesized compounds possess columnar mesomorphism. The change of donor–acceptor ratio can influence the type of mesophase. A new approach to the creation of materials for optoelectronics is proposed and implemented, which includes design of compounds possessing vitrification from mesophase with maintenance of a columnar order, absorption in the near IR-region of the spectrum and good performance electrophysical characteristics simultaneously.     

Reply to comment on “On the controversy around Daganzo’s requiem for and Aw-Rascle’s resurrection of second-order traffic flow models” by H.M. Zhang

This contribution compares several different approaches allowing one to derive macroscopic traffic equation directly from microscopic car-following models. While it is shown that some conventional approaches lead to theoretical problems, it is proposed to use an approach reminding of smoothed particle hydrodynamics to avoid gradient expansions. The derivation circumvents approximations and, therefore, demonstrates the large range of validity of macroscopic traffic equations, without the need of averaging over many vehicles. It also gives an expression for the “traffic pressure”, which generalizes previously used formulas. Furthermore, the method avoids theoretical inconsistencies of macroscopic traffic models, which have been criticized in the past by Daganzo and others.     

On the solution of a “2D Coulomb + Aharonov-Bohm” problem: oscillator strengths in the discrete spectrum and scattering

In this paper we present an exact analytic solution of the Schrödinger equation both inthe discrete and continuous spectra for the combination of a 2D Coulomb potential and theAharonov-Bohm flux. We analyze the influence of the Aharonov-Bohm flux on the energyspectrum of such a system and show that its presence leads to the broadening of theelectron density in the bound states with the given value of the principal quantum number.We have shown that the scattering phase shift, which determines theS-matrix, can be represented as a sum of the Aharonov-Bohm scatteringphase, first obtained by Henneberger, and a “modified” 2D Coulomb phase. We have noticed,that the Aharonov-Bohm scattering phase has a full analogy with the “quantum defect” forsuch a system. We have shown also, that the presence of the Aharonov-Bohm flux affects theradiation spectrum of the electron in this case, and this fact is demonstrated bycalculations of the corresponding oscillator strengths. The explicit analytic expressionfor the scattering cross section on such a system is found in the frame of the eikonalapproach. Obtained formula contains the two exact limiting cases, namely, the “pure” 2DCoulomb scattering as well as the “pure” Aharonov-Bohm effect. The mutual influence of a2D Coulomb potential and the Aharonov-Bohm flux is also discussed.     

A New Thiosemicarbazone-Based Fluorescence “Turn-on” Sensor for Zn<Superscript>2+</Superscript> Recognition with a Large Stokes Shift and its Application in Live Cell Imaging

Selective fluorescence turn on Zn²⁺ sensor with long-wavelength emission and a large Stokes shift is highly desirable in Zn²⁺ sensing area. We reported herein the synthesis and Zn²⁺ recognition properties of a new thiosemicarbazone-based fluorescent sensor L. L displays high selectivity and sensitivity toward Zn²⁺ over other metal ions in DMSO-H₂O (1:1, v/v, HEPES 10 mM, pH = 7.4) solution with a long-wavelength emission at 572 nm and a large Stokes shift of 222 nm. Confocal fluorescence microscopy experiments demonstrate that L is cell-permeable and capable of monitoring intracellular Zn²⁺.

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Graphical Abstract We report a new thiosemicarbazone-based fluorescent sensor (L) for selective recognition of Zn²⁺ with a long wavelength emission and a large Stokes shift.

     

Hamilton’s equations of motion of a vortex filament in the rotating Bose–Einstein condensate and their “soliton” solutions

The equation of motion of a quantized vortex filament in a trapped Bose–Einstein condensate [A. A. Svidzinsky and A. L. Fetter, Phys. Rev. A 62, 063617 (2000)] has been generalized to the case of an arbitrary anharmonic anisotropic rotating trap and presented in the variational form. For condensate density profiles of the form ρ = f(x² + y² + ReΨ(x + iy)) in the presence of the plane of symmetry y = 0, the solutions x(z) describing stationary vortices of U and S types coming to the surface and solitary waves have been found in quadratures. Analogous three-dimensional configurations of the vortex filament uniformly moving along the z axis have also been found in strictly cylindrical geometry. The dependence of solutions on the form of the function f(q) has been analyzed.     

An Efficient Fluorescence “Turn-On” Chemosensor Comprising of Coumarin and Rhodamine Moieties for Al<Superscript>3+</Superscript> and Hg<Superscript>2+</Superscript>

A potent fluorescence ‘turn-on’ receptor (HL) based on rhodamine and coumarin moieties for the detection of Hg²⁺ and Al³⁺ is synthesized by condensation of rhodamine 6G hydrazide and 4-hydroxy-3-acetylcoumarin. In presence of Al³⁺ and/or Hg²⁺ the receptor (HL) exhibits deep pink colouration and a sharp band at 528 nm is appeared in UV–vis titration. Upon gradual addition of Al³⁺ and/or Hg²⁺ to the solution of HL significant enhancement of fluorescence intensity is observed at 564 nm in MeCN:H₂O (1:5, v/v) medium. The receptor is strongly bound to Al³⁺ and/or Hg²⁺ and the association constants (K_a) are found to be 1.74?×?10⁴ and 1.04?×?10⁴ M^??1 for Al³⁺ and Hg²⁺ respectively.

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Graphical Abstract A potent fluorescence ‘turn-on’ receptor (HL) based on rhodamine and coumarin moieties for the detection of Hg²⁺ and Al³⁺ is synthesized and characterized. In presence of Al³⁺ and/or Hg²⁺ the receptor (HL) exhibits deep pink colouration and significant enhancement of fluorescence intensity is observed at 564 nm in MeCN:H₂O (1:5, v/v) medium. The receptor is strongly bound to Al³⁺ and/or Hg²⁺ and the association constants (K_a) are found to be 1.74?×?10⁴ and 1.04?×?10⁴ M^??1 for Al³⁺ and Hg²⁺ respectively.