Condensation Product of Phenylalanine and Salicylaldehyde: Fluorescent Sensor for Zn<Superscript>2+</Superscript>

The condensation product of phenylalanine and salicylaldehyde (L) was synthesised and characterised which was found to be selective fluorescent “off-on” sensor for Zn²⁺ ion with the detection limit 10^?5 M. The sensor is free of interferences from metal ions - Na⁺, K⁺, Al³⁺, Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Pb²⁺, Cd²⁺ and Hg²⁺. The Fluorescence and the UV/visible spectral data reveals a 1:1 interaction between the sensor and Zn²⁺ ion with binding constant 10⁸. The DFT and TDDFT calculations confirm the structures of the sensor and the sensor-Zn²⁺ complex.     

A Colorimetric and Fluorescent Indicator for Hg<Superscript>2+</Superscript> Detection Based on Cinnamamide Group-Containing Rhodamine Derivative

A colorimetric and fluorescent indicator based on cinnamamide group-containing rhodamine derivative was synthesized for the detection of Hg²⁺. The rhodamine B and cinnamamide were connected via ethylenediamine as a bridging molecule through a condensation reaction to obtain a colorimetric and fluorescent indicator for the detection of Hg²⁺ in H₂O-EtOH (4:1, v/v). The indicator was excellent in the selectivity of Hg²⁺ and was almost unaffected by other common ions such as Na⁺, K⁺, Mg²⁺, Fe³⁺, Cu²⁺, Zn²⁺, Cr³⁺. The Hg²⁺-containing aqueous solution turned from colorless to red within 7 min after the addition of the indicator, and had an absorption peak at 564 nm in UV-vis, which implies a significant colorimetric phenomenon. Their characteristic peaks varied with the Hg²⁺ content, and they reached a linear relationship at low concentrations. The binding stoichiometry proved to be 1:1. The lowest detection limit was 4.1?×?10^?7 mol/L, ranging from acidic to neutral.     

A New Fluorescent Chemosensor Detecting Co<Superscript>2+</Superscript> and K<Superscript>+</Superscript> in DMF Buffered Solution

A new fluorescent chemosensor 2-(2-thiophene)imidazo [4,5,f]-1,10-phenanthroline (L) was prepared and characterized. By adding univalent or divalent metal ions such as Na⁺, K⁺, Mg²⁺, Ba²⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Ag⁺, Zn²⁺, Cd²⁺ and Hg²⁺ ions into the solution of L in DMF under buffered conditions with the working pH ranging from 7.0 to 8.0, we found that L could be used to detect K⁺ ratiometricly and it could also be applied to sense Co²⁺ with the phenomenon of fluorescence quenching of L. While the response behavior of L was not discernibly affected by other examined metal ions.     

A Novel Naphthalene-Immobilized Nanoporous SBA-15 as a Highly Selective Optical Sensor for Detection of Fe<Superscript>3+</Superscript> in Water

A novel organic-inorganic hybrid optical sensor (SBA-NCO) was designed and synthesized through immobilization of isocyanatopropyl-triethoxysilane and 1-amino-naphthalene onto the surface of SBA-15 by post-grafting method. The characterization of materials using XRD, TEM, N₂ adsorption-desorption, and FT-IR techniques confirmed the successful attachment of organic moieties and preserving original structure of SBA-15 after modification step. Fluorescence experiments demonstrated that SBA-NCO was a highly selective optical sensor for the detection of Fe³⁺ directly in water over a wide range of metal cations including Na⁺, Mg²⁺, Al³⁺, K⁺, Ca²⁺, Cr³⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺, Hg²⁺, and Pb²⁺ in a wide pH values.     

A New Reactive 1,8-Naphthalimide Derivative for Highly Selective and Sensitive Detection of Hg<Superscript>2+</Superscript>

A 1,8-naphthalimide derivative with a reactive aliphatic hydroxyl was designed and synthesized as a fluorescent probe. Its structure was characterized by IR, ¹H NMR, ¹³C NMR, LC-MS and HPLC. The probe showed high selectivity and sensitivity to Hg²⁺ over other metal ions such as Pb²⁺, Na⁺, K⁺, Cd²⁺, Cr³⁺, Zn²⁺, Cu²⁺, Ni²⁺, Ca²⁺, Fe³⁺, Fe²⁺, Co²⁺, Mn²⁺ and Mg²⁺ in MeCN/H₂O (15/85, v/v). The increase in fluorescence intensity was linearly proportional to the concentration of Hg²⁺ in the range of 18–40 μM with a detection limit of 1.38 × 10^?7 mol/L. The probe could work in a pH span of 4.3–9.0 and respond to Hg²⁺ quickly with strong anti-interference ability. Job’s plot suggested a 1:2 complex of the probe and Hg²⁺.     

Coumarin Based Fluorescent Probe for Colorimetric Detection of Fe<Superscript>3+</Superscript> and Fluorescence Turn On-Off Response of Zn<Superscript>2+</Superscript> and Cu<Superscript>2+</Superscript>

A new coumarin based Schiff-base chemosensor-(E)-7-(((8-hydroxyquinolin-2-yl)methylene) amino)-4-methyl-2H-chromen-2-one (H ₁₁ L) was synthesized and evaluated as a colorimetric sensor for Fe³⁺ and fluorescence “turn on-off” response of Zn²⁺ and Cu²⁺ using absorption and fluorescence spectroscopy. Upon treatment with Fe³⁺ and Zn²⁺, the absorption intensity as well as the fluorescence emission intensity increases drastically compared to other common alkali, alkaline earth and transition metal ions, with a distinct color change which provide naked eye detection. Formation of 1:1 metal to ligand complex has been evaluated using Benesi-Hildebrand relation, Job’s plot analyses, ¹H NMR titration as well as ESI-Mass spectral analysis. The complex solution of H ₁₁ L with Zn²⁺ ion exhibited reversibility with EDTA and regenerate free ligand for further Zn²⁺ sensing. H ₁₁ L exhibits two INHIBIT logic gates with two different chemical inputs (i) Zn²⁺ (IN1) and Cu²⁺ (IN2) and (ii) Zn²⁺ (IN1) and EDTA (IN2) and the emission as output. Again, an IMPLICATION logic gate is obtained with Cu²⁺ and EDTA as chemical inputs and emission as output mode. Both free ligand as well as metal-complexes was optimized using density functional theory to interpret spectral properties. The corresponding energy difference between HOMO-LUMO energy gap for H ₁₁ L, H₁₁L-Zn²⁺ and H₁₁L-Cu²⁺ are 2.193, 1.834 and 0.172 eV, respectively.     

A Rhodamine Derivative Based Chemosensor with High Selectivity and Quick Respond to Cr<Superscript>3+</Superscript> in Aqueous Solution

In this paper, a new kind of colorimetric chemsensor aiming at detecting Cr³⁺ has been synthesized, and it is based on the “Off-On” effect of a rhodamine derivative. Comparing with other metal irons (Na⁺, K⁺, Ni²⁺, Hg²⁺, Fe³⁺, Mn²⁺, Co²⁺, Cd²⁺, Cu²⁺, Pb²⁺, Zn²⁺, Mg²⁺, Ba²⁺, Ag⁺, Fe²⁺, Ce³⁺), the chemsensor has a quick and accurate response to Cr³⁺ in H₂O-EtOH solution (4/1, v/v). There is an obvious change in color, from colorless to bright pink when Cr³⁺ is detected. According to the fitting curve based on Benesi-Hildebrand equation and working curve of absorption strength in UV-vis spectrum, the binding pattern of Cr³⁺ and the rhodamine derivative follows a 1:1 stoichiometry. The chemsensor shows great potential in monitoring Cr³⁺ in the aqueous medium with high efficiency, which is supposed to complete the recognition in the minimum as 5.2?×?10^?7 mol/L within 5 min.     

A Novel Hg<Superscript>2+</Superscript> Selective Ratiometric Fluorescent Chemodosimeter Based on an Intramolecular FRET Mechanism

A irreversible Hg²⁺ selective ratiometric fluorescence probe FR, a fluorescein fluorophore linked to a rhodamine B hydrazide by a thiourea spacer, was designed and synthesized. The developed probe FR exhibited great ratiometric fluorescence enhancement and remarkable yellow-magenta color change toward Hg²⁺ with excellent selectivity in aqueous acetone solution, and the ratiometric fluorescence response to Hg²⁺ was not interfered by other metal cations including Fe³⁺, Co²⁺, Ni²⁺, Cr³⁺, Zn²⁺, Pb²⁺, Cd²⁺, Ca²⁺, Mg²⁺, Ba²⁺ and Mn²⁺. The linear range and the detection limit of this supposed ratiometric fluorescence method for Hg²⁺ were 0.0–10.0 × 10⁻⁶ and 5 × 10⁻⁸ M, respectively.     

Laser cooling and isotope-shift measurement of Zn<Superscript>+</Superscript> with 202-nm ultraviolet coherent light

We have laser-cooled all even isotopes of Zn⁺ ions confined in a linear radio-frequency ion trap, and measuredoptical isotope shifts in the 4s ² S _1/2-4p ² P _3/2 transition. Tunable continuous-wave coherent light near 202 nm was generated for this experiment by means of frequency conversion of light from diode and solid-state lasers. The measured isotope shifts are as follows: ⁶⁶Zn⁺-⁶⁴Zn⁺, 0.676(6) GHz; ⁶⁸Zn⁺-⁶⁶Zn⁺, 0.670(4) GHz; and ⁷⁰Zn⁺-⁶⁸Zn⁺, 0.568(10) GHz. In all cases, the transition line of the heavier isotope was observed at the higher frequency. The mass and the field shifts were estimated using a King plot. This is the first isotope-shift measurement in the transition involving the ground (4s ² S _1/2) state of Zn⁺ ions. Received: 18 July 2002 / Revised version: 20 October 2002 / Published online: 5 February 2003 RID="*" ID="*"Corresponding author. Fax: +81-42/327-6694, E-mail: matubara@crl.go.jp Present address: Communications Research Laboratory, 4-2-1 Nukui-Kitamachi, Koganei, Tokyo 184-8795, Japan     

Novel Turn-on Fluorescence Probes for Al<Superscript>3+</Superscript> Based on Conjugated Pyrazole Schiff Base

One novel turn-on fluorescence probe founded on conjugated pyrazole Schiff base for detecting Al³⁺ was invented. The UV–vis and fluorescence spectrometer were employed to explore optical properties of this probe. The results got from those experiments indicated that this fluorescence probe manifested excellent sensitivity and selectivity for Al³⁺ compared with other cations examined(Ag⁺, Co²⁺, Mg²⁺, Cu²⁺, Ni²⁺, Pb²⁺,and Zn²⁺). In addition, this probe displayed a more rapid response and remained stable between pH 6 and 9 by investigating the fluorescence intensity under different response time and various pH values. Remarkably, the detection limit for Al³⁺ could lower to 1.0×10^?9M. Therefore, the probe could be potentially applied to the environment for the detection of Al³⁺, and the availability in biological range of pH that could be further studied to make this probe apply to biological systems in the future.     

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.     

Synthesis of Two Coumarin-Derived Schiff Bases and Investigation of theirs Selectivity for Zn<Superscript>2+</Superscript>

In this study, the coumarin-derived schiff bases (HL₁ and HL₂) have been designed and synthesized. Upon the addition of Zn²⁺, both of them show significant fluorescence enhancement owing to inhibits PET and ESIPT process respectively. However, the receptor HL₂ response toward Cd²⁺, Mg²⁺, Ba²⁺, Ca²⁺ besides Zn²⁺ and exhibits fluorescence enhancement but not enough to detection of the concentration levels of Zn²⁺.     

Growth defect W<Superscript>3+</Superscript>-W<Superscript>2+</Superscript> of CdWO<Subscript>4</Subscript> crystals

CdWO₄ crystals grown by the Czochralski method at the low-temperature gradient were investigated with electron spin resonance (ESR) spectroscopy. ESR spectra did not contain the spectra of impurity ions typical for the CdWO₄ structure, i.e., Fe³⁺, Mn²⁺, and Cr³⁺. At the same time, in the studied crystals a complex ESR spectrum having the hyperfine structure due to two nonequivalent tungsten atoms was observed (W¹⁸³;I=1/2; natural abundance, 14.28%). Angular dependence analysis and simulation of ESR spectra have shown that this novel spectrum is described by a spin-Hamiltonian with the following parameters:D=839 G,E=80 G,g _xx=2.01,g _yy=1.97,g _zz=1.987 and electron spinS=7/2. There is one magnetically nonequivalent position of the center in the crystal structure and the direction ofD _zz andg _zz corresponds to the direction of W_n-W_n+2 (or Cd_n-Cd_n+2) in the crystal structure. Because of the fact that it is in principle impossible to achieve the electron stateS=7/2 for the d-shell of one transition metal ion and taking into account the fact that such electron state is realized for two nonequivalent tungsten atoms, we suppose the defect structure to be the chain W²⁺-M⁺-W³⁺. In the structure of this defect the ion M⁺ is diamagnetic, the ions W²⁺ and W³⁺ have electron spinS=2 andS=3/2, respectively. The necessary condition for such defect to exist is to place this chain of ions in cadmium positions for the charge compensation. the reason for such defects to form is supposed to be the incorporation of M⁺ ions into the CdWO₄ lattice. The presence of W²⁺ and W³⁺ in Cd positions in the defect structure provides the charge compensation and the lowering of the lattice stress.     

Electron-impact ionization and dissociation of C<Subscript>2</Subscript>D<Superscript>+</Superscript>

Absolute cross sections for electron-impact single ionization, dissociative excitation and dissociative ionization of the ethynyl radical ion (C₂D⁺)^+) have been measured for electron energies ranging from the corresponding reaction thresholds to 2.5 keV. The animated crossed electron-ion beam experiment is used and results have been obtained for the production of C₂D²⁺, C²⁺, C₂⁺_2^+ , CD⁺, C⁺ and D⁺. The maximum of the cross section for single ionization is found to be (2.01 ± 0.02) × 10^-17 cm², at the incident electron energy of 105 eV. Absolute total cross sections for the various singly charged fragments production are observed to decrease by a factor of almost three, from the largest cross-section measured for C⁺, over C₂⁺_2^+ and CD⁺ down to that of D⁺. The maxima of the cross sections are obtained to be (14.5 ± 0.5) × 10^-17 cm² for C₂⁺_2^+, (12.1 ± 0.1) × 10^-17 cm² for CD⁺, (27.7 ± 0.2) × 10^-17 cm² for C⁺ and (11.1 ± 0.8) × 10^-17 cm² for D⁺. The smallest cross section is measured to be (1.50 ± 0.04) × 10^-18 cm² for the production of the doubly charged ion C²⁺. Individual contributions for dissociative excitation and dissociative ionization are determined for each singly-charged product. The cross sections are presented in closed analytic forms convenient for implementation in plasma simulation codes. Kinetic energy release distributions of dissociation fragments are seen to extend from 0 to 6 eV for the heaviest fragment C₂⁺_2^+, up to 11.0 eV for CD⁺, 14.2 eV for C⁺ and 11.2 eV for D⁺ products.     

N-benzoate-N′ salicylaldehyde ethynelediamine: A new fluorescent sensor for Zn2+ ion by “off-on” mode

Imbalance of zinc ion (Zn²⁺) in human body causes diseases like Alzheimer’s and Parkinson’s and therefore Zn²⁺ estimation in biological fluids has diagnostic values. Fluorescence “off-on” sensors have advantages of high sensitivity and in situ application over other sensors. A new fluorescent “off-on” Zn²⁺ sensor, N-benzoate-N′ salicylaldehyde ethynelediamine (L), has been synthesisied. In 1:1(v/v) CH₃OH:PBS (PBS?=?phosphate buffer solution), L shows ca. 20 times enhancement in fluorescence intensity on interaction with Zn²⁺, due to snapping of photoinduced electron transfer (PET) process, which is selective over metal ions - Na⁺, K⁺, Ca²⁺, Ni²⁺, Cu²⁺, Cd²⁺, Hg²⁺ and Pb²⁺. These metal ions either individually or all together does not interfere the sensing ability of L towards Zn²⁺. A 1:1 interaction between L and Zn²⁺ ion with binding constant 10^4.25 has been established from spectroscopic data.     

Fluorescent carbon dots: facile synthesis at room temperature and its application for Fe<Superscript>2+</Superscript> sensing

A new route for one-pot preparation of carbon dots (CDs) was developed at room temperature using PEG400 as both the carbon source and passitive agent. The new method possesses the advantages of facile, rapid, energy-saving, without any external stimulus and environment friendly. By changing the content of NaOH, the PEG400-CDs with blue-emitting, yellow-emitting, orange red-emitting and red-emitting were obtained, and the formation mechanism were carefully investigated. In addition, a sensitive fluorescence sensor were developed for Fe²⁺ detection based on PEG400-CDs since the fluorescence of PEG400-CDs could be enhanced by Fe²⁺. It was found that there is a good linear relationship between the enhanced fluorescence and Fe²⁺ concentration in the range of 0.5 to 2.0 μmol·L^?1 with the detection limit of 6.0 × 10^?8 mol·L^?1, and Fe²⁺ in water samples was also determined with high accuracy and repeatability.     

Paramagnetic Complexes in Zinc Selenide Crystals with Iron Admixture

Paramagnetic resonance of ZnSe: Fe single crystals was studied at 120 K. Parameters of the spin Hamiltonian were determined for the monoclinic dimer complex Fe³⁺–Cu⁺ and a second discovered Fe³⁺ center, which appears due to association of the iron ion with a K⁺ ion in a Zn²⁺ position or with a zinc vacancy. Effect of illumination of the zinc selenide samples by blue, green and red light on the paramagnetic resonance spectrum was investigated.     

A Pyrene-based Highly Selective Turn-on Fluorescent Chemosensor for Iron(III) Ions and its Application in Living Cell Imaging

A new pyrene-based chemosensor (1) exhibits excellent selectivity for Fe³⁺ ions over a wide range of tested metal ions Ag⁺, Ca²⁺, Cd²⁺, Co²⁺, Cu²⁺, Fe²⁺, Hg²⁺, K⁺, Mg²⁺, Mn²⁺, Ni²⁺, Pb²⁺, and Zn²⁺. The binding of Fe³⁺ to chemosensor 1 produces an emission band at 507 nm due to the formation of a Py-Py* excimer that is induced by Fe³⁺-binding. The binding ratio of 1-Fe³⁺ was determined to be 1:1 from a Job plot. The association constant of 1-Fe³⁺ complexes was found to be 1.27?×?10⁴ M^?1 from a Benesi-Hildebrand plot. In addition, fluorescence microscopy experiments show that 1 can be used as a fluorescent probe for detecting Fe³⁺ in living cells.     

Theoretical study of charge-exchange and excitation processes in collisions of He<Superscript>+</Superscript> ions with C<Superscript>5+</Superscript>, N<Superscript>6+</Superscript>, and O<Superscript>7+</Superscript> hydrogen-like ions

Data on the cross sections for single-electron charge exchange and excitation in collisions of He⁺ ions with C⁵⁺, N⁶⁺, and O⁷⁺ ions in the He⁺ ion energy range of 0.2–3.0 MeV are obtained for the first time. The cross sections for the single-electron charge transfer into the singlet and triplet 1snl states of C⁴⁺, N⁵⁺, and O⁶⁺ (2≤n≤5) ions and for the 1s → 2p _{0, ±1} electronic excitation of He⁺(1s) ions are calculated. The calculations were performed by solving close-coupling equations on the basis of ten two-electron quasi-molecular states.